CN113409991B - Flexible composite conductive film and preparation method and application thereof - Google Patents

Abstract

The disclosure relates to a high-performance flexible composite conductive film and its preparation method and application. The high-performance flexible composite conductive film includes a substrate, a metal nanowire layer, a metal grid layer and a first anchor layer, a metal nanowire layer and a metal nanowire layer. The metal grid layers are arranged between the substrate and the first anchor layer, and the arrangement order of the metal nanowire layer and the metal grid layer can be exchanged; a conductive path is formed between the metal nanowire layer and the metal grid layer; The metal grid layer includes a grid-like conductive structure composed of a plurality of metal wires, the nanowire layer includes a network-like conductive structure composed of a plurality of metal nanowires, and the network gaps in the network-like conductive structure are smaller than those of the grid-like conductive structure Grid gaps in . The high-performance flexible composite conductive film may also include a planar conductive layer and a second anchor layer. The high-performance flexible composite conductive film provided by the invention has both excellent conductivity and good light transmittance, and can meet the application requirements of large-scale flexible touch displays and optoelectronic devices.

Description

Flexible composite conductive film and its preparation method and application

technical field

The disclosure relates to a conductive film, a method for manufacturing the conductive film and applications of the conductive film, in particular to a flexible composite conductive film and its preparation method and application.

Background technique

In recent years, with the rise of the flexible electronics industry, flexible touch and devices have become the development trend of the electronics industry. Under this industry trend, soft transparent conductive films with flexibility, high light penetration, and high conductivity It is the basis of many flexible optoelectronic products. As we all know, the conductive layer of ITO (Indium-Tin-Oxide, indium tin oxide) transparent conductive film used in traditional touch products is fragile and easy to break, lacks flexibility and has the problem of voltage drop in the application of large-scale electrodes, which limits its application in large Size flexible touch and device applications.

Nano-silver wire transparent conductive film has the advantages of excellent photoelectric properties, flex resistance properties, and simple preparation process. and other fields have been widely used. However, the silver nanowire transparent conductive film also has some defects, such as limited by the insufficient conductivity of the silver nanowire and the characteristics of network conduction, it cannot be applied in some devices that require high conductivity.

Contents of the invention

In view of the defects of the prior art, the purpose of this disclosure is to provide a flexible composite conductive film and its preparation method and application, to improve the conductive performance of the flexible composite conductive film, so that the flexible composite conductive film can meet the needs of large-scale flexible touch and high conductivity in devices. sexual needs.

The first aspect of the present invention provides a flexible composite conductive film, the flexible composite conductive film includes a substrate, a metal nanowire layer, a metal grid layer and a first anchor layer, the metal nanowire layer and the The metal grid layers are all arranged between the substrate and the first anchor layer, and the arrangement order of the metal nanowire layer and the metal grid layer can be exchanged;

A conductive path is formed between the metal nanowire layer and the metal mesh layer;

The metal grid layer includes a grid-shaped conductive structure composed of a plurality of metal wires, and grid gaps are formed between adjacent multiple metal wires, and the metal nanowire layer includes a network-shaped conductive structure composed of a plurality of metal nanowires. In the conductive structure, network gaps are formed between a plurality of adjacent metal nanowires, and the network gaps are smaller than the grid gaps.

In a feasible implementation manner, the flexible composite conductive film further includes a planar conductive layer, and the planar conductive layer is a planar conductive structure,

The planar conductive layer is disposed between any two layers of the substrate, the metal nanowire layer, the metal mesh layer and the first anchor layer or on the first anchor layer ;

A conductive path is formed among the metal nanowire layer, the metal mesh layer and the planar conductive layer.

In a feasible implementation manner, the flexible composite conductive film further includes a second anchor layer,

The second anchor layer is disposed between any two layers of the metal nanowire layer, the metal mesh layer and the planar conductive layer.

A second aspect of the present invention provides a method for preparing a flexible composite conductive film, the method comprising:

Form a conductive composite layer on the substrate, the conductive composite layer includes a metal nanowire layer and a metal grid layer, the positions of the metal nanowire layer and the metal grid layer can be exchanged, the metal nanowire layer and the metal grid layer A conductive path is formed between the metal grid layers;

A first anchor layer is formed on the conductive composite layer.

In a feasible implementation, the method also includes:

forming a planar conductive layer between any two layers of the substrate, the metal nanowire layer, the metal mesh layer, and the first anchor layer or on the first anchor layer;

A conductive path is formed among the metal nanowire layer, the metal mesh layer and the planar conductive layer.

In a feasible implementation, the method also includes:

A second anchor layer is formed between any two layers of the metal nanowire layer, the metal mesh layer and the planar conductive layer.

The third aspect of the present invention provides an application of a flexible composite conductive film, including the application of the flexible composite conductive film described in the first aspect above in touch screens, displays, mobile phone antenna circuits, infrared optical imaging components, photoelectric sensors, electromagnetic Applications in shielding, smart windows, smart tablet and solar cells.

The flexible composite conductive film provided by the present invention includes a layered structure formed by a substrate, a metal nanowire layer, an anchor layer and a metal grid layer, and the flexible composite conductive film is formed by compounding the metal nanowire layer and the metal grid layer At the same time, it has good electrical conductivity, flexible bending characteristics and good light transmittance; in the flexible composite conductive film provided by the present invention, the surface of the metal nanowire layer is covered by other layer structures, so the metal nanowire layer will not be exposed On the outside, the flexible composite conductive film has better oxidation resistance, the durability of the flexible composite conductive film is improved, and the flexible composite conductive film has better surface smoothness.

The flexible composite conductive film prepared by the method provided by the invention has both good light transmittance and good conductivity, and can be widely used in touch screens, displays, mobile phone antenna circuits, infrared optical imaging elements, photoelectric sensors, In terms of electromagnetic shielding, smart windows, smart tablet and solar cells, it can meet the needs of large-scale flexible touch and high conductivity in devices.

Description of drawings

In order to illustrate the technical solutions of the present disclosure more clearly, the following will briefly introduce the drawings that are required in the embodiments or the description of the prior art. Apparently, the drawings in the following description are only some embodiments of the present disclosure, and those skilled in the art can obtain other drawings according to these drawings without creative efforts.

FIG. 1 is a schematic diagram of a structure of a flexible composite conductive film provided by an embodiment of the present disclosure;

2 is a schematic diagram of a structure of a flexible composite conductive film provided by an embodiment of the present disclosure;

3 is a schematic diagram of a structure of a flexible composite conductive film provided by an embodiment of the present disclosure;

Fig. 4 is a schematic diagram of a structure of a flexible composite conductive film provided by an embodiment of the present disclosure;

5 is a schematic diagram of a structure of a flexible composite conductive film provided by an embodiment of the present disclosure;

6 is a schematic diagram of a structure of a flexible composite conductive film provided by an embodiment of the present disclosure;

Fig. 7 is a schematic diagram of a structure of a flexible composite conductive film provided by an embodiment of the present disclosure;

8 is a schematic diagram of a structure of a flexible composite conductive film provided by an embodiment of the present disclosure;

9 is a schematic diagram of a structure of a flexible composite conductive film provided by an embodiment of the present disclosure;

Fig. 10 is a schematic diagram of a structure of a flexible composite conductive film provided by an embodiment of the present disclosure;

Fig. 11 is a schematic diagram of a structure of a flexible composite conductive film provided by an embodiment of the present disclosure;

Fig. 12 is a schematic diagram of a structure of a flexible composite conductive film provided by an embodiment of the present disclosure;

Fig. 13 is a schematic diagram of a structure of a flexible composite conductive film provided by an embodiment of the present disclosure;

Fig. 14 is a schematic diagram of a structure of a flexible composite conductive film provided by an embodiment of the present disclosure;

Fig. 15 is a schematic diagram of a structure of a flexible composite conductive film provided by an embodiment of the present disclosure;

Fig. 16 is a schematic diagram of a structure of a flexible composite conductive film provided by an embodiment of the present disclosure.

In the figure: 1-substrate, 2-metal nanowire layer, 3-metal grid layer, 4-first anchoring layer, 5-plane conductive layer, 6-second anchoring layer.

Detailed ways

In order to enable those skilled in the art to better understand the present disclosure, the technical solutions in the embodiments of the present disclosure will be clearly and completely described below in conjunction with the drawings in the embodiments of the present disclosure. Obviously, the described embodiments are only It is an embodiment of a part of the present disclosure, but not all of the embodiments. Based on the embodiments in the present disclosure, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts shall fall within the protection scope of the present disclosure.

It should be noted that the terms "first" and "second" in the specification, claims and drawings of the present disclosure are used to distinguish similar objects, but not necessarily used to describe a specific sequence or sequence. It is to be understood that the data so used are interchangeable under appropriate circumstances such that the embodiments of the disclosure described herein can be practiced in sequences other than those illustrated or described herein. Furthermore, the terms "comprising" and "having", as well as any variations thereof, are intended to cover a non-exclusive inclusion.

At present, most capacitive touch panels use ITO (Indium Tin Oxide) conductive film with mature manufacturing process, but ITO conductive film has defects such as high resistance value and fragility, so it is not suitable for making medium and large size touch panels and flexible panels. Metal mesh conductive film (Metal Mesh) has lower resistance than ITO conductive film, better light transmittance, and fast response speed, especially suitable for making medium and large size touch panels and flexible panels, making it a One of the very competitive alternatives to ITO conductive film. In addition, nano-silver wire conductive film has been widely used in the fields of touch screen, handwriting tablet, heating film and electromagnetic shielding due to its good photoelectric characteristics and flexural resistance, but it is not suitable for the weak conductivity. This limits its application in some devices with high conductivity requirements. With the development of science and technology, the demand for large-size touch panels and flexible panels has increased. However, good results have not been achieved in exploring the production of large-size touch panels and flexible panels. The invention innovatively combines the metal grid conductive structure and the nano-silver wire network conductive structure to obtain a flexible composite conductive film, on the premise that the flexible composite conductive film meets the light transmittance requirements in the application of large-size touch panels and flexible panels , through the combination of layer structure and the selection of layer thickness, the resistance of the composite transparent conductive film can be reduced as much as possible, and the conductive performance can be improved. The structure and manufacturing method of the flexible composite conductive film provided by the present invention will be described below.

The invention provides a flexible composite conductive film, the flexible composite conductive film includes a substrate, a metal nanowire layer, a metal grid layer and a first anchor layer, the metal nanowire layer and the metal grid layer are both It is arranged between the substrate and the first anchor layer, and the arrangement order of the metal nanowire layer and the metal grid layer can be exchanged; the metal nanowire layer and the metal grid layer A conductive path is formed between the layers; the metal grid layer includes a grid-like conductive structure composed of a plurality of metal wires, and grid gaps are formed between adjacent metal wires, and the metal nanowire layer includes a plurality of metal wires. In the network-shaped conductive structure composed of metal nanowires, network gaps are formed between a plurality of adjacent metal nanowires, and the network gaps are smaller than the grid gaps. Wherein, the first anchor layer covers at least one surface of the metal mesh layer or at least one surface of the metal nanowire layer, or even wraps the metal mesh layer or the metal nanowire layer. The flexible composite conductive film integrates the advantages of the metal nanowire layer and the metal grid layer, has excellent electrical conductivity, flexible bending characteristics and good light transmittance, and the upper and lower surfaces of the metal nanowire layer are covered by other layer structures. Coating makes the metal nanowire layer have better oxidation resistance.

Specifically, the flexible composite conductive film formed by the substrate, the metal nanowire layer, the first anchor layer and the metal grid layer can exhibit two different layer structures as shown in FIG. 1 and FIG. 2 .

Please refer to Fig. 1, which shows a structure of a flexible composite conductive film, the flexible composite conductive film is a substrate 1, a metal mesh layer 3, a metal nanowire layer 3 and a first anchor layer 4 from bottom to top. , wherein a conductive path is formed between the metal nanowire layer and the metal grid layer, the first anchor layer covers at least one surface of the metal nanowire layer, and fills or inlays the network voids of the metal nanowire layer.

Please refer to Fig. 2, which shows another structure of the flexible composite conductive film, the flexible composite conductive film is a substrate 1, a metal nanowire layer 2, a metal grid layer 3 and a first anchor layer from bottom to top. 4. Wherein, a conductive path is formed between the metal nanowire layer and the metal grid layer, and the first anchor layer covers at least one surface of the metal grid layer, and fills or inlays grid gaps in the metal grid layer.

Further, the flexible composite conductive film may also include a planar conductive layer. The arrangement of the planar conductive layer makes the flexible composite conductive film change from network conduction to planar conduction. Specifically, the planar conduction layer may be arranged on the substrate, the Between any two layers of the metal nanowire layer, the metal mesh layer and the first anchor layer or on the first anchor layer. The flexible composite conductive film formed by the substrate, the metal nanowire layer, the first anchor layer, the metal grid layer and the planar conductive layer can exhibit eight different layer structures as shown in FIGS. 3 to 10 .

Please refer to FIG. 3 , which shows a structure of a flexible composite conductive film. The flexible composite conductive film includes a substrate 1, a metal nanowire layer 2, a metal grid layer 3, and a first anchor layer 4 from bottom to top. and a planar conductive layer 5 . Wherein, the plane conductive layer, the metal grid layer and the metal nanowire layer form a conductive path. The first anchor layer covers at least one surface of the metal grid layer, and fills or inlays the grid gaps in the metal grid layer to improve the oxidation resistance of the flexible composite conductive film; the planar conductive layer covers the first anchor layer, so as to Improve the surface flatness of the flexible composite conductive film.

Please refer to FIG. 4, which shows a structure of a flexible composite conductive film, the flexible composite conductive film is a substrate 1, a metal grid layer 3, a metal nanowire layer 2, and a first anchor layer 4 in sequence from bottom to top. and a planar conductive layer 5 . Wherein, the metal mesh layer, the planar conductive layer and the metal nanowire layer form a conductive path. The first anchor layer covers at least one surface of the metal nanowire layer, and fills or inlays the network gap of the metal nanowire layer to improve the oxidation resistance of the flexible composite conductive film; the planar conductive layer covers the first anchor layer to improve Surface flatness of flexible composite conductive films.

Please refer to FIG. 5 , which shows a structure of a flexible composite conductive film. The flexible composite conductive film includes a substrate 1, a metal nanowire layer 2, a metal grid layer 3, a plane conductive layer 5 and a first flexible conductive film from bottom to top. an anchor layer 4 . Wherein, the plane conductive layer, the metal grid layer and the metal nanowire layer form a conductive path. The plane conductive layer covers the metal grid layer, and the first anchor layer covers the plane conductive layer, so as to improve the surface smoothness and oxidation resistance of the flexible composite conductive film.

Please refer to FIG. 6, which shows a structure of a flexible composite conductive film, which is a substrate 1, a metal nanowire layer 2, a plane conductive layer 5, a metal mesh layer 3 and a first flexible composite conductive film from bottom to top. an anchor layer 4 . Wherein, the plane conductive layer, the metal grid layer and the metal nanowire layer form a conductive path. The planar conductive layer is arranged between the metal nanowire layer and the metal grid layer to improve the surface smoothness of the flexible composite conductive film, and the first anchor layer covers the surface of the metal grid layer and fills or inlays the metal grid The grid gap of the layer is used to improve the surface flatness and oxidation resistance of the flexible composite conductive film.

Please refer to FIG. 7 , which shows a structure of a flexible composite conductive film. The flexible composite conductive film includes a substrate 1, a metal grid layer 3, a plane conductive layer 5, a metal nanowire layer 2 and a first flexible conductive film from bottom to top. an anchor layer 4 . Wherein, the plane conductive layer, the metal grid layer and the metal nanowire layer form a conductive path. The planar conductive layer is arranged between the metal nanowire layer and the metal grid layer to improve the surface smoothness of the flexible composite conductive film, and the first anchor layer covers the surface of the metal nanowire layer and fills or inlays the metal nanowire In order to improve the surface flatness and oxidation resistance of the flexible composite conductive film.

Please refer to FIG. 8 , which shows a structure of a flexible composite conductive film. The flexible composite conductive film includes a substrate 1, a metal grid layer 3, a metal nanowire layer 2, a planar conductive layer 5 and a first flexible conductive film from bottom to top. an anchor layer 4 . Wherein, the plane conductive layer, the metal grid layer and the metal nanowire layer form a conductive path. The planar conductive layer is arranged on the metal nanowire layer to improve the surface smoothness and oxidation resistance of the flexible composite conductive film. The first anchor layer covers the planar conductive layer, which can further improve the surface smoothness of the flexible composite conductive film.

Please refer to FIG. 9, which shows a structure of a flexible composite conductive film. The flexible composite conductive film is a substrate 1, a plane conductive layer 5, a metal nanowire layer 2, a metal mesh layer 3 and a first flexible conductive film from bottom to top. an anchor layer 4 . Wherein, the plane conductive layer, the metal grid layer and the metal nanowire layer form a conductive path. The first anchor layer covers the surface of the metal grid layer and fills or inlays the grid gaps of the metal grid layer, thereby improving the oxidation resistance and surface smoothness of the flexible composite conductive film.

Please refer to FIG. 10 , which shows a structure of a flexible composite conductive film. The flexible composite conductive film consists of a substrate 1, a plane conductive layer 5, a metal grid layer 3, a metal nanowire layer 2 and a first flexible composite conductive film from bottom to top. an anchor layer 4 . Wherein, the plane conductive layer, the metal grid layer and the metal nanowire layer form a conductive path. The first anchor layer covers the surface of the metal nanowire layer, and fills or inlays the network voids of the metal nanowire layer, thereby improving the oxidation resistance and surface smoothness of the flexible composite conductive film.

Further, the flexible composite conductive film may also include a second anchor layer, and the second anchor layer is arranged on any two of the metal nanowire layer, the metal grid layer and the planar conductive layer. between layers. The flexible composite conductive film formed by the substrate, the metal nanowire layer, the first anchor layer, the metal mesh layer, the second anchor layer and the planar conductive layer can exhibit six different layer structure.

Please refer to FIG. 11 , which shows a structure of a flexible composite conductive film. The flexible composite conductive film is a substrate 1, a metal nanowire layer 2, a second anchor layer 6, and a metal mesh layer 3 from bottom to top. , a planar conductive layer 5 and a first anchor layer 4 . Wherein, the plane conductive layer, the metal grid layer and the metal nanowire layer form a conductive path. The second anchor layer covers the surface of the metal nanowire layer, and fills or inlays the network voids of the metal nanowire layer, the plane conductive layer covers the surface of the metal grid layer, and the first anchor layer covers the surface of the plane conductive layer. The structure can improve the oxidation resistance and surface smoothness of the flexible composite conductive film.

Please refer to FIG. 12 , which shows a structure of a flexible composite conductive film. The flexible composite conductive film includes substrate 1, metal nanowire layer 2, second anchor layer 6, planar conductive layer 5, Metal grid layer 3 and first anchor layer 4. Wherein, the plane conductive layer, the metal grid layer and the metal nanowire layer form a conductive path. The second anchor layer covers the surface of the metal nanowire layer and fills or inlays the network gaps in the metal nanowire layer to improve the oxidation resistance and surface smoothness of the metal nanowire layer. The first anchor layer covers the metal grid layer, and fill or inlay the grid gaps in the metal grid layer to improve the oxidation resistance and surface smoothness of the metal grid layer, and the flat conductive layer covers the second anchor layer, which can further improve the flexibility of the composite conductive film. surface flatness.

Please refer to FIG. 13 , which shows a structure of a flexible composite conductive film. The flexible composite conductive film includes a substrate 1, a metal grid layer 3, a metal nanowire layer 2, and a second anchor layer 6 from bottom to top. , a planar conductive layer 5 and a first anchor layer 4 . Wherein, the plane conductive layer, the metal grid layer and the metal nanowire layer form a conductive path. The second anchor layer covers the surface of the metal nanowire layer and fills or inlays the network gaps in the metal nanowire layer, which can improve the oxidation resistance and surface smoothness of the metal nanowire layer. In addition, the planar conductive layer covers the second anchor layer. An anchor layer, the first anchor layer covers the plane conductive layer, further improving the surface flatness of the flexible composite conductive film.

Please refer to FIG. 14 , which shows a structure of a flexible composite conductive film. The flexible composite conductive film includes substrate 1, planar conductive layer 5, metal nanowire layer 2, second anchor layer 6, Metal grid layer 3 and first anchor layer 4. Wherein, the plane conductive layer, the metal grid layer and the metal nanowire layer form a conductive path. The second anchor layer covers the surface of the metal nanowire layer and fills or inlays the network gaps in the metal nanowire layer, which can improve the oxidation resistance and surface smoothness of the metal nanowire layer. The first anchor layer covers the metal grid The surface of the metal mesh layer, and fill or inlay the mesh gaps in the metal mesh layer, which can improve the oxidation resistance and surface smoothness of the metal mesh layer.

Please refer to FIG. 15 , which shows a structure of a flexible composite conductive film. The flexible composite conductive film includes a substrate 1, a metal nanowire layer 2, a metal grid layer 3, and a second anchor layer 6 from bottom to top. , a planar conductive layer 5 and a first anchor layer 4 . Wherein, the plane conductive layer, the metal grid layer and the metal nanowire layer form a conductive path. The second anchor layer covers the surface of the metal grid layer and fills or inlays the grid gaps in the metal grid layer, which can improve the oxidation resistance and surface smoothness of the metal grid layer. In addition, the planar conductive layer covers the second The anchor layer, the first anchor layer covers the planar conductive layer, further improving the surface smoothness of the flexible composite conductive film.

Please refer to FIG. 16 , which shows a structure of a flexible composite conductive film. The flexible composite conductive film includes a substrate 1, a metal grid layer 3, a metal nanowire layer 2, and a second anchor layer 6 from bottom to top. , a planar conductive layer 5 and a first anchor layer 4 . Wherein, the plane conductive layer, the metal grid layer and the metal nanowire layer form a conductive path. The second anchor layer covers the surface of the metal nanowire layer and fills or inlays the network gaps in the metal nanowire layer, which can improve the oxidation resistance and surface smoothness of the metal nanowire layer. In addition, the planar conductive layer covers the second anchor layer. An anchor layer, the first anchor layer covers the plane conductive layer, further improving the surface flatness of the flexible composite conductive film.

Each layer constituting the flexible composite conductive film will be described below.

(1) Substrate

The substrate is a flexible substrate, and its material can be PET (Polyethylene terephthalate, polyester resin), CPI (polyimide film; PI film, polyimide film), PI (polyimide, polyimide resin), PC (Polycarbonate, Polycarbonate), PMMA (polymethyl methacrylate material), PP (polypropylene, polypropylene), PE (polyethylene, polyethylene) and EVA (Ethylene Vinyl Acetate Copolymer, ethylene-vinyl acetate copolymer) one or a combination of several. The flexural resistance of the flexible composite conductive film can be enhanced by using a flexible substrate to prepare the flexible composite conductive film.

(2) Metal nanowire layer

The metal nanowires in the metal nanowire layer may be any one or a combination of nano-copper wires, nano-gold wires and nano-silver wires. Since the length of the metal nanowire directly affects the contact resistance of the composite transparent conductive film, the longer the wire, the fewer the contact points and the smaller the square resistance of the film. However, if the metal nanowire is too long, it is easy to form entanglement and affect the uniformity of the coating. Therefore, in this embodiment, the metal nanowire preferably has a diameter of 5 nm˜100 nm and an aspect ratio of 500˜2500. In particular, the diameter of the metal nanowire is preferably 10-30 nm, and the aspect ratio is 1000-1200, so as to improve the uniformity of the metal nanowire layer and reduce the square resistance. Considering the light transmittance requirements of large-size touch screens, and the superposition of the metal nanowire layer and the metal grid layer may reduce the light transmittance, the thickness of the metal nanowire layer can be adjusted according to the light transmittance of the application scene. It is set according to requirements, preferably 20nm to 300nm.

(3) The first anchor layer

When the first anchor layer covers the metal nanowire layer or metal grid layer, the first anchor layer mainly protects the covered metal nanowire layer or metal grid layer, improving the oxidation resistance of the flexible composite conductive film performance.

When the first anchor layer is between the plane conductive layer and the metal nanowire layer or the metal grid layer, the first anchor layer not only plays a protective role, but also has an electrical conduction function, so that the metal nanowire layer and the plane conduct electricity. Conductive paths are formed between layers or metal mesh layers.

In the embodiment of the present invention, the first anchor layer is made of a material with good weather resistance, transparency and good light transmittance after film formation, preferably acrylic resin, polypyrrole, polythiophene, polyacetylene, polyparaphenylene, polyaniline , perylene pigments, azo pigments, phthalocyanine and phthalocyanine compounds, derivatives of pentacene, derivatives of benzothiophene, rubrene, C60, poly 3-hexylthiophene, polyparaphenylene Any one or a combination of vinyl and polyphenol. The first anchor layer can enhance various properties of the conductive film, including increasing the light transmittance of the conductive film, reducing optical haze, increasing electrical stability, increasing surface adhesion and surface tension, improving the anti-aging performance of the conductive film, Prevent oxidation and ion migration of metal nanowires in the metal nanowire layer.

Preferably, a tunneling effect occurs between the metal nanowire layer and the planar conductive layer or the metal grid layer to realize electrical conduction. The two conductive layers in contact with the first anchoring layer form a conductive path through the tunneling electrons in the first anchoring layer. In order to achieve the effect of electron tunneling, the thickness of the first anchoring layer meets the requirements of strengthening the two layers in contact with it. Adhesion between them is sufficient. Preferably, the thickness of the first anchor layer can be set to 0.1 nm to 5 nm.

(4) Metal grid layer

The metal grid layer is a grid-like conductive structure, which has the advantages of low resistance and fast response. The metal grid layer is made of copper and/or silver. The thickness of the metal grid layer is 50nm-500nm, the line width is 1um-30um, and the line distance is 30um-500um.

(5) Plane conductive layer

The planar conductive layer makes the flexible composite conductive film transform from mesh conduction to full-surface conduction. The planar conductive layer is prepared by selecting materials that can realize full-surface conduction, good weather resistance, and good light transmittance after film formation. The material of the planar conductive layer is preferably Any one or a combination of transparent oxide films, metal films, graphene films and transparent organic conductive films. The thicker the planar conductive layer is, the better its conductivity is. The thickness of the planar conductive layer can be determined according to the conductive requirements of the conductive film in different applications, and is preferably 5nm-200nm.

(6) The second anchor layer

The second anchor layer is arranged on the metal nanowire layer or the metal grid layer, on the one hand, it can protect the covered metal nanowire layer or metal grid layer, improve the oxidation resistance of the flexible composite conductive film, and on the other hand On the one hand, a conductive path can be formed between the metal nanowire layer and the planar conductive layer or the metal grid layer. In the embodiment of the present invention, the material of the second anchoring layer is the same as that of the first anchoring layer, please refer to the above, and details will not be described here.

In a possible implementation, a functional composite layer is provided between the substrate and the metal nanowire layer or the metal grid layer, and the functional composite layer is an optical adaptation layer, an electrical adaptation layer, a mechanical adaptation layer, a refractive Any one or a combination of multiple rate adaptation layers. The optical adaptation layer is a metal layer or ceramic layer formed by sputtering, evaporation, coating, etc., so that the substrate and the optical adaptation layer form a refractive index compensation, and reduce the reflectivity difference between the conductive area and the non-conductive area after etching value to reduce visual contrast. Optical adaptation layer materials include metals, alloys, oxide nanomaterials and combinations thereof. The mechanical adaptation layer is used to reduce the stress between the substrate and the coating, between the coating and the coating, and improve the adhesion between the substrate and the coating, and between the coating and the coating. The refractive index adaptation layer is a functional layer that can enhance the light transmittance of the composite transparent conductive film in the visible light region. Its principle is to redistribute the transmitted light, reflected light and light in other directions to increase the proportion of incident light.

The above-mentioned flexible composite conductive film can be prepared by the following method, which includes the following steps:

S172: Form a conductive composite layer on the substrate, the conductive composite layer includes a metal nanowire layer and a metal grid layer, the positions of the metal nanowire layer and the metal grid layer can be exchanged, and the metal nanowire layer A conductive path is formed between the layer and the metal mesh layer.

S174: Form a first anchor layer on the conductive composite layer.

Further, the method further includes between any two layers of the substrate, the metal nanowire layer, the metal mesh layer and the first anchor layer or the first anchor layer The step of forming a planar conductive layer on top. A conductive path is formed among the metal nanowire layer, the metal grid layer and the planar conductive layer.

Furthermore, the method further includes the step of forming a second anchor layer between any two layers of the metal nanowire layer, the metal grid layer and the planar conductive layer.

Specifically, in the case where the flexible composite conductive film includes a substrate, a metal nanowire layer, a metal grid layer and a first anchor layer, the flexible composite conductive film is prepared by the following method:

The following three-layer structures were fabricated on the flexible substrate:

(1) The metal nanowire layer is made by coating the metal nanowire ink;

(2) The metal grid layer is made by nanoimprinting, inkjet printing, silk screen printing or magnetron sputtering and orthogonal etching;

(3) The first anchor layer is produced by coating the anchor layer solution. Specifically, the anchor layer solution can be coated on the metal nanowire layer, so that the anchor layer solution can fill the network gaps formed between adjacent metal nanowires in the metal nanowire layer, and then dry and solidify; or, An anchor layer solution is coated on the metal grid layer so that the anchor layer solution fills the grid gaps formed between adjacent metal wires in the metal grid layer, and then dried and cured to obtain a first anchor layer.

In the above-mentioned three-layer structure, the positions of the metal nanowire layer and the metal grid layer can be exchanged, as long as the metal nanowire layer and the metal grid layer are between the flexible substrate and the first anchoring layer.

In the case where the flexible composite conductive film includes a substrate, a metal nanowire layer, a metal grid layer, a planar conductive layer and a first anchor layer, the flexible composite conductive film can be prepared by the following method:

The following four-layer structures were fabricated on the flexible substrate:

(1) The metal nanowire layer is made by coating the metal nanowire ink;

(2) The metal grid layer is made by nanoimprinting, inkjet printing, silk screen printing or magnetron sputtering + orthogonal etching;

(3) The flat conductive layer is made by magnetron sputtering or coating;

(4) The first anchor layer is produced by coating the anchor layer solution. Specifically, the anchor layer solution can be coated on the metal nanowire layer, so that the anchor layer solution can fill the network gaps formed between adjacent metal nanowires in the metal nanowire layer, and then dry and solidify; or, An anchor layer solution is coated on the metal grid layer so that the anchor layer solution fills the grid gaps formed between adjacent metal wires in the metal grid layer, and then dried and cured to obtain a first anchor layer.

In the above structure, the metal nanowire layer and the metal grid layer must be between the first anchor layer and the substrate; the planar conductive layer can be between the first anchor layer and the substrate, or as the last layer of the flexible composite conductive film. The outer layer is on top of the first anchor layer.

In the case where the flexible composite conductive film includes a substrate, a metal nanowire layer, a metal grid layer, a planar conductive layer, a first anchor layer and a second anchor layer, the flexible composite conductive film can be prepared by the following method:

Fabricate the following five-layer structures on the flexible substrate:

(1) The metal nanowire layer is made by coating the metal nanowire ink;

(2) The metal grid layer is made by nanoimprinting, inkjet printing, silk screen printing or magnetron sputtering and orthogonal etching;

(3) Plane conductive layer, made by magnetron sputtering and coating;

(4) The first anchor layer is made by coating the anchor layer solution on the metal grid layer or the plane conductive layer. When the anchor layer is located on the metal grid layer, the anchor layer solution is filled with grid gaps formed between adjacent metal lines in the metal grid layer;

(5) The second anchor layer is made by coating the anchor layer solution on the metal nanowire layer or the metal grid layer. When the second anchor layer is located on the metal nanowire layer, the anchor The layer solution fills the network gaps formed between adjacent metal nanowires in the metal nanowire layer, and when the second anchor layer is located on the metal grid layer, the anchor layer solution fills the metal grid layer Grid voids formed between adjacent metal lines;

In the above five-layer structure, the metal nanowire layer, the second anchor layer, the metal grid layer and the planar conductive layer are all located between the flexible substrate and the first anchor layer, and the metal nanowire layer, the second anchor layer The arrangement order among layers, metal grid layer and plane conductive layer can be exchanged arbitrarily.

In a possible implementation, the anchor layer solution includes one or more of acrylic monomers, silicone-epoxys, siloxanes, phenolic resins, polyurethane prepolymers, and polyimide prepolymers. Several combinations, further, the anchor layer can also contain polypyrrole, polythiophene, polyacetylene, polyparaphenylene, polyaniline, perylene pigments, azo pigments, phthalocyanine and phthalocyanine compounds, derivatives of pentacene Compounds, derivatives of benzothiophenes, rubrene, C60, poly-3-hexylthiophene, poly-p-phenylene vinylene and polyphenol, or any one or a combination of more. The anchor layer is made by photocuring or thermal curing. The metal nanowires in the metal nanowire layer are any of nano-copper wires, nano-gold wires, nano-silver wires, nano-tungsten wires, nano-platinum wires, nano-palladium wires, nano-iron wires, nano-cobalt wires and nano-nickel wires. one or a combination of several. The material of the planar conductive layer is any one or a combination of transparent oxide film, metal film, graphene film and transparent organic conductive film. The material of the metal mesh layer is one or a combination of silver, copper, silver alloy and copper alloy. The metal grid layer is made by nanoimprinting, inkjet printing, silk screen printing or magnetron sputtering and orthogonal etching.

Wherein, the nanoimprinting to make a metal grid layer refers to pressing a master mold or a template into a substrate loaded with a conformal material. The conformal material is solidified by the method, and after removing the master mold or template, the graphic information opposite to the height and position of the template can be obtained. By scraping and coating nano-conductive ink on the surface of the graphic information, the groove is filled with conductive ink, and the metal grid layer can be obtained after thermal curing; this method is suitable for directly making the metal grid layer on the flexible substrate.

The inkjet printing to make the metal grid layer is to use the inkjet printing technology to directly print the conductive ink containing metal nanoparticles on the substrate, and form the metal grid layer after drying and subsequent treatment.

The metal grid layer is made by the screen printing method, which is to transfer the conductive ink containing metal nanoparticles to the substrate through the mesh holes of the screen printing screen grid through the extrusion of the scraper to form the metal grid layer.

The metal grid layer is made by the magnetron sputtering and orthogonal etching, which means that the metal layer is made on the substrate by the method of magnetron sputtering, and then the surface of the metal layer is coated with a photosensitive substance (also known as photoresist or Photoresist), the grid pattern left after exposure and development protects the bottom layer, and finally the unprotected metal layer is etched away by orthogonal etching, and then the metal grid layer is obtained by stripping.

The flexible composite conductive film prepared by the above method can meet the optical performance requirements of large-scale touch devices, has the advantages of oxidation resistance, good flexibility, good electrical conductivity, and high stability, and can be widely used in touch screens, displays, Mobile phone antenna circuits, infrared optical imaging components, photoelectric sensors, electromagnetic shielding, smart windows, smart tablet and solar cells.

Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these.

Example 1

As shown in FIG. 1 , the flexible composite conductive film provided in this embodiment sequentially includes a substrate, a metal nanowire layer, a metal mesh layer and a first anchor layer. in:

The substrate is a PET flexible substrate with a thickness of 125um.

The metal nanowire layer is a network conductive structure composed of a plurality of silver nanowires, gaps are formed between the silver nanowires, the silver nanowires have a diameter of 25nm and a length of 30um; the thickness of the metal nanowire layer is 75nm.

The metal grid layer is a grid-shaped conductive structure composed of a plurality of copper wires, and the gaps formed between the copper wires in the metal grid layer are larger than the gaps formed between the nano silver wires in the metal nano wire layer. Among them, the thickness of the metal grid is 50nm, the line width is 15um, and the line spacing is 50um.

The material of the first anchor layer is acrylic resin, and its thickness is 1 nm. The first anchor layer covers the surface of the metal nanowires and fills the gaps between the metal nanowires.

The flexible composite conductive film is prepared through the following steps:

S11. Configure silver nano wire ink with a content of 0.09wt%, wherein the silver nano wire has a diameter of 25nm and a length of 30 microns; the silver nano wire ink is coated in a network shape on a PET substrate by slit coating A conductive structure was obtained to obtain a metal nanowire layer with a dry film thickness of 75 nm.

S12. Magnetron sputtering copper layer above the nano-silver wire layer made in step S11, then coating photosensitive material (also known as photoresist or photoresist) on the surface of the metal layer, through exposure, development, and finally using orthogonal The metal copper layer is etched by etching, and then the metal grid layer is obtained by stripping. The thickness of the metal grid is 50nm, the line width is 15um, and the line spacing is 50um. The etching solution for etching the metal grid only etches copper but not silver.

S13. Apply the anchor layer solution with a solid content of 2.0 wt% on the metal grid layer by slit coating, so that the anchor layer solution fills the gaps in the metal grid line layer, and then dry, The first anchor layer was obtained by ultraviolet curing, and the thickness of the cured coating was 1 nm.

Example 2

The flexible composite conductive film provided in this embodiment is shown in FIG. 2 , including a substrate, a metal mesh layer, a metal nanowire layer and a first anchor layer. in:

The substrate is a PET flexible substrate with a thickness of 150um.

The metal grid layer is a grid-like conductive structure composed of multiple silver wires, and grid-like gaps are formed between the silver wires in the metal grid layer.

The metal nanowire layer is a network-like conductive structure composed of a plurality of nano-copper wires. The gap formed between each nano-copper wire is smaller than the gap between each silver wire in the metal grid layer. The nano-copper wire has a diameter of 100nm and a length of 250um; the thickness of the metal nanowire layer is 300nm.

The material of the first anchor layer is acrylic resin, and its thickness is 3nm. The first anchor layer covers the surface of the metal nanowires and fills the gaps between the metal nanowires.

The flexible composite conductive film is prepared through the following steps:

S21. Vacuum-evaporate a silver layer above the PET substrate, then coat a photosensitive substance (also known as photoresist or photoresist) on the surface of the metal layer, expose and develop, and finally etch metal copper by orthogonal etching layer, and then the metal grid layer is obtained by stripping the film. The thickness of the metal grid is 500nm, the line width is 30um, and the line spacing is 500um.

S22. Configure nano-copper wire ink with a content of 0.09wt%, wherein the nano-copper wire has a diameter of 100nm and a length of 250 microns; the nano-copper wire ink is coated on the metal grid layer to form a network by slit coating shape conductive structure to obtain a metal nanowire layer with a dry film thickness of 300 nm.

S23, using the method of slit coating, coating the anchor layer solution with a solid content of 2.0wt% on the metal nanowire layer, so that the anchor layer solution fills the gaps in the metal nanowire layer, and then drying and ultraviolet ray After curing, the first anchor layer was obtained, and the thickness of the cured coating was 3 nm.

Example 3

The flexible composite conductive film provided in this embodiment is shown in FIG. 5 , including a substrate, a metal nanowire layer, a metal grid layer, a planar conductive layer and a first anchor layer. in:

The substrate is a PP flexible substrate with a thickness of 125um.

The metal nanowire layer is a network conductive structure composed of a plurality of silver nanowires, gaps are formed between the silver nanowires, the silver nanowires have a diameter of 15nm and a length of 20um; the thickness of the metal nanowire layer is 60nm.

The metal grid layer is a grid-shaped conductive structure composed of multiple copper wires, and the gaps formed between the copper wires in the metal grid layer are larger than the gaps formed between the metal nanowires in the metal nanowire layer.

The material of the first anchor layer is acrylic resin, and its thickness is 0.1 nm. The first anchor layer covers the surface of the metal grid and fills the gaps between the metal lines in the metal grid layer.

The flexible composite conductive film is prepared through the following steps:

S31. Configure silver nano wire ink with a content of 0.09wt%, wherein the silver nano wire has a diameter of 15nm and a length of 20um; the silver nano wire ink is coated on the PP substrate in a network-like conductive manner by slit coating structure to obtain a metal nanowire layer with a dry film thickness of 60 nm.

S32. Vacuum-deposit a copper layer above the metal nanowire layer, then coat a photosensitive substance (also known as photoresist or photoresist) on the surface of the metal copper layer, expose, develop, and finally etch by orthogonal etching The metal copper layer is then stripped to obtain the metal grid layer. The thickness of the metal grid layer is 80nm, the line width is 10um, and the line spacing is 80um. Wherein, the etchant for etching the metal grid only etches copper but not silver.

S33 , magnetron sputtering an ITO layer on the metal grid layer to obtain a planar conductive layer with a thickness of 80 nm.

S34, using the method of slit coating, coating the anchor layer solution with a solid content of 2.0wt% on the metal grid layer, so that the anchor layer solution fills the gaps in the metal grid layer, and then cured by ultraviolet light to obtain The thickness of the first anchor layer after curing is 0.1 nm.

Example 4

As shown in FIG. 11 , the flexible composite conductive film provided in this embodiment sequentially includes a substrate, a metal nanowire layer, a second anchor layer, a metal mesh layer, a planar conductive layer, and a first anchor layer. in:

The substrate is a PET flexible substrate with a thickness of 188um.

The metal nanowire layer is a network-like conductive structure composed of a plurality of nano-gold wires, gaps are formed between each nano-gold wire, the diameter of the nano-gold wire is 5nm, and the length is 10um; the thickness of the metal nanowire layer is 30nm.

The second anchor layer is made of acrylic resin. The second anchor layer covers the surface of the metal nanowires and fills the gaps between the metal nanowires.

The metal grid layer is a grid-like conductive structure composed of multiple copper wires. The gap formed between the copper wires in the metal grid layer is larger than the gap formed between the metal nanowires in the metal nanowire layer. The metal grid The thickness of the layer is 200 nm.

The plane conductive layer is a transparent oxide film with a thickness of 100nm;

The material of the first anchor layer is acrylic resin, and the first anchor layer covers the plane conductive layer.

The flexible composite conductive film is prepared through the following steps:

S41. Configure nano-gold wire ink with a content of 0.09wt%, wherein the diameter of the nano-gold wire is 5nm and the length is 10um; adopt the method of slit coating to coat the nano-gold wire ink on the PET substrate to form a conductive network structure to obtain a metal nanowire layer with a dry film thickness of 30 nm.

S42. Using the method of slit coating, coating the anchor layer solution with a solid content of 2.0wt% on the metal nanowire layer, so that the anchor layer solution fills the gaps in the metal nanowire layer, and then cured by ultraviolet light to obtain The thickness of the second anchor layer after curing is 4nm.

S43, using a corona treatment method to perform surface treatment on the cured second anchor layer.

S44. Vacuum vapor-deposit a copper layer above the second anchor layer made in step S43, then coat a photosensitive substance (also known as photoresist or photoresist) on the surface of the metal copper layer, expose and develop, and finally use positive The metal copper layer is etched by cross-etching, and then the metal grid layer is obtained by stripping. The thickness of the metal grid layer is 200nm, the line width is 20um, and the line spacing is 150um. The etching solution for etching the metal grid only etches copper but not gold.

S45 , magnetron sputtering an ITO layer on the metal grid layer to obtain a plane conductive layer with a thickness of 100 nm.

S46. Prepare the first anchor layer on the planar conductive layer obtained in step S45. The method is: apply the anchor layer solution with a solid content of 2.0 wt% on the planar conductive layer by slit coating, and then The first anchor layer was obtained after drying and ultraviolet curing, and the thickness of the cured coating was 5 nm.

Example 5

The flexible composite conductive film provided in this embodiment, as shown in FIG. 12 , sequentially includes a substrate, a metal nanowire layer, a second anchor layer, a planar conductive layer, a metal grid layer, and a first anchor layer. in:

The substrate is an EVA flexible substrate with a thickness of 150um.

The metal nanowire layer is a network conductive structure composed of a plurality of silver nanowires, gaps are formed between the silver nanowires, the silver nanowires have a diameter of 30nm and a length of 40um; the thickness of the metal nanowire layer is 90nm.

The material of the second anchor layer is acrylic resin, and its thickness is 2nm. The second anchor layer covers the surface of the metal nanowire layer and fills the gaps between the metal nanowires.

The plane conductive layer is a transparent oxide film with a thickness of 120nm.

The metal grid layer is a grid-like conductive structure composed of a plurality of silver wires, and the gaps formed between the silver wires in the metal grid layer are larger than the gaps formed between the metal nanowires in the metal nanowire layer;

The material of the first anchor layer is acrylic resin, and its thickness is 5 nm. The first anchor layer covers the surface of the metal grid layer and fills the gaps between the metal grid lines.

The flexible composite conductive film is prepared through the following steps:

S51. Configure nano-silver ink with a content of 0.09wt%, wherein the diameter of the nano-silver is 30nm and the length is 40um; adopt the method of slit coating to coat the nano-gold ink on the EVA substrate to form a conductive network structure to obtain a metal nanowire layer with a dry film thickness of 90 nm.

S52, using the method of slit coating, coating the anchor layer solution with a solid content of 2.0wt% on the metal nanowire layer, so that the anchor layer solution fills the gaps in the metal nanowire layer, and then cured by ultraviolet light to obtain The thickness of the second anchor layer after curing is 2nm.

S53, using a corona treatment method to perform surface treatment on the cured second anchor layer.

S54 , magnetron sputtering an ITO layer on the metal grid layer to obtain a planar conductive layer with a thickness of 120 nm.

S55, magnetron sputtering copper layer above the plane conductive layer made in step S54, adopt yellow light process to etch the copper layer into a grid-like conductive structure, and obtain a metal grid layer with a thickness of 150nm, a line width of 5um, and a line spacing It is 100um, wherein, the etchant for etching the metal grid only etches copper but not silver and ITO.

S56. Prepare the first anchor layer on the metal grid layer obtained in step S55, the method is: apply the anchor layer solution with a solid content of 2.0 wt% on the metal grid layer by means of slit coating , and then the first anchor layer was obtained by ultraviolet curing, and the thickness of the cured coating was 5 nm.

Example 6

The flexible composite conductive film provided in this embodiment, as shown in FIG. 3 , sequentially includes a substrate, a metal grid layer, a metal nanowire layer, a first anchor layer and a planar conductive layer. in:

The substrate is a CPI flexible substrate with a thickness of 25um.

The metal grid layer is a grid-shaped conductive structure composed of a plurality of copper wires, and gaps are formed between the copper wires in the metal grid layer.

The metal nanowire layer is a network-like conductive structure composed of a plurality of silver nanowires. The gaps formed between the silver nanowires are smaller than the gaps formed between the copper wires in the metal mesh layer. The silver nanowires have a diameter of 20nm and a length of is 35um; the thickness of the metal nanowire layer is 80nm.

The material of the first anchor layer is acrylic resin, and its thickness is 3nm. The first anchor layer covers the surface of the metal nanowires and fills the gaps between the metal nanowires.

The planar conductive layer is a transparent oxide film with a thickness of 5 nm.

The flexible composite conductive film is prepared through the following steps:

S61. A copper layer is vacuum evaporated on the CPI substrate, and the copper layer is etched into a grid-like conductive structure by using a yellow light process to obtain a metal grid layer with a thickness of 100nm, a line width of 1um, and a line spacing of 30um.

S62. Configure silver nano wire ink with a content of 0.09wt%, wherein the silver nano wire has a diameter of 20nm and a length of 35um; the silver nano wire ink is coated in a network shape on the metal grid layer by slit coating A conductive structure was obtained to obtain a metal nanowire layer with a dry film thickness of 80 nm.

S63, using the slit coating method, coating the anchor layer solution with a solid content of 2.0 wt% on the metal nanowire layer, so that the anchor layer solution fills the gaps in the metal nanowire layer, and then cured by ultraviolet light to obtain The thickness of the first anchor layer after curing is 3nm.

S64. Surface treatment is performed on the cured first anchor layer by means of corona treatment.

S65 , magnetron sputtering an ITO layer above the first anchor layer to obtain a planar conductive layer with a thickness of 5 nm.

The light transmittance and resistance values of the flexible composite conductive films of Examples 1-6 were tested respectively, and the following film performance data were obtained.

Example Transmittance(%) Square resistance (Ω/□) Example 1 84.9 ≤0.3 Example 2 76.2 ≤0.1 Example 3 81.7 ≤0.3 Example 4 80.8 ≤0.2 Example 5 81.3 ≤0.3 Example 6 85.4 ≤0.5

It can be seen from the above that the average light transmittance of the flexible composite conductive film provided by the present invention in the visible light range of 400nm to 800nm is greater than 75%, which can meet the requirements for light transmittance in the application of large-scale touch devices, and has a higher than traditional silver nanometer. Line conductive film and metal grid conductive film have lower resistance and better conductivity.

The technical features of the above embodiments can be combined arbitrarily. To make the description concise, all possible combinations of the technical features in the above embodiments are not described. However, as long as there is no contradiction in the combination of these technical features, they should be It is considered to be within the range described in this specification.

The above examples only express several implementations of the present disclosure, and the descriptions thereof are more specific and detailed, but should not be construed as limiting the scope of the patent for the invention. It should be noted that those skilled in the art can make several modifications and improvements without departing from the concept of the present disclosure, and these all belong to the protection scope of the present disclosure. Therefore, the scope of protection of the disclosed patent should be based on the appended claims.

Claims (19)

1. A flexible composite conductive film, comprising a substrate, a metal nanowire layer, a metal mesh layer, a planar conductive layer, a first anchoring layer, and a second anchoring layer, wherein the metal nanowire layer and the metal mesh layer are disposed between the substrate and the first anchoring layer, and the arrangement order of the metal nanowire layer and the metal mesh layer is changeable, the planar conductive layer is a planar conductive structure, and the planar conductive layer is disposed between any two of the substrate, the metal nanowire layer, the metal mesh layer, and the first anchoring layer or on the first anchoring layer; the second anchoring layer is disposed between any two of the metal nanowire layer, the metal mesh layer, and the planar conductive layer;

a conductive path is formed among the metal nanowire layer, the metal grid layer and the planar conductive layer;

the metal grid layer comprises a grid-shaped conductive structure formed by a plurality of metal wires, grid gaps are formed between the adjacent metal wires, the metal nanowire layer comprises a grid-shaped conductive structure formed by a plurality of metal nanowires, and the grid gaps are smaller than the grid gaps;

the first anchoring layer has an electric conduction function when being arranged between the planar conducting layer and the metal nanowire layer or the metal grid layer, and the second anchoring layer enables the metal nanowire layer and the planar conducting layer or the metal grid layer to form an electric conduction path;

when the first anchoring layer is disposed on the metal nanowire layer, the first anchoring layer fills or is embedded in network voids in the metal nanowire layer;

when the first anchoring layer is arranged on the metal grid layer, the first anchoring layer is filled or embedded in grid gaps in the metal grid layer;

when the first anchoring layer is disposed on the planar conductive layer, the first anchoring layer covers a surface of the planar conductive layer.

2. The flexible composite conductive film of claim 1, wherein the first anchoring layer covers at least one surface of the metal mesh layer, at least one surface of the metal nanowire layer, or at least one surface of the planar conductive layer.

3. The flexible composite conductive film of claim 2, wherein the first anchor layer wraps around the metal mesh layer, the metal nanowire layer, or the planar conductive layer.

4. The flexible composite conductive film according to claim 1, wherein a functional composite layer is further disposed between the substrate and the metal nanowire layer or the metal mesh layer, and the functional composite layer is any one or a combination of more of an optical adaptation layer, an electrical adaptation layer, a mechanical adaptation layer, a planar conductive layer, and a refractive index adaptation layer.

5. The flexible composite conductive film according to claim 1, wherein the metal nanowire is any one or a combination of several of a nano copper wire, a nano gold wire, a nano silver wire, a nano tungsten wire, a nano platinum wire, a nano palladium wire, a nano iron wire, a nano cobalt wire and a nano nickel wire.

6. The flexible composite conductive film according to claim 1, wherein the metal nanowires have a diameter of 5nm to 100nm and an aspect ratio of 500 to 2500.

7. The flexible composite conductive film according to claim 1, wherein the thickness of the metal nanowire layer is 20nm to 300nm.

8. The flexible composite conductive film according to claim 1, wherein the first anchor layer comprises one or a combination of several of acrylic, silicone-epoxy, siloxane, phenolic, epoxy, polyurethane and polyimide, and further comprises any one or a combination of several of polypyrrole, polythiophene, polyacetylene, polyparaphenylene, polyaniline, perylene pigment, azo pigment, phthalocyanine and phthalocyanine compound, derivative of pentacene, derivative of benzothiophene, rubrene, C60, poly 3-hexylthiophene, polyparaphenylene vinylene and polyphenol.

9. The flexible composite conductive film according to claim 1, wherein the second anchor layer comprises one or a combination of several of acrylic, silicone-epoxy, siloxane, phenolic, epoxy, polyurethane and polyimide, and further comprises any one or a combination of several of polypyrrole, polythiophene, polyacetylene, polyparaphenylene, polyaniline, perylene pigment, azo pigment, phthalocyanine and phthalocyanine compound, derivative of pentacene, derivative of benzothiophene, rubrene, C60, poly 3-hexylthiophene, polyparaphenylene vinylene and polyphenol.

10. The flexible composite conductive film of claim 1, wherein the first anchoring layer is fabricated from a photo-or thermally-cured prepolymer.

11. The flexible composite conductive film according to claim 1, wherein the thickness of the first anchoring layer is 0.1nm to 5nm.

12. The flexible composite conductive film according to claim 1, wherein the planar conductive layer comprises any one or a combination of transparent oxide film, metal film, graphene film, and transparent organic conductive thin film.

13. The flexible composite conductive film according to claim 1, wherein the thickness of the planar conductive layer is 5nm to 200nm.

14. The flexible composite conductive film according to claim 1, wherein the metal wires in the metal mesh layer comprise one or more of silver, copper, silver alloy and copper alloy, the thickness of the metal mesh layer is 50nm to 500nm, the line width is 1um to 30um, and the line distance is 30um to 500um.

15. The flexible composite conductive film of claim 1, wherein the metal mesh layer is fabricated by nanoimprint, printing, screen printing, or magnetron sputtering and orthogonal etching.

16. The flexible composite conductive film according to claim 1, wherein the surface of the metal mesh layer is further provided with a passivation layer and/or a blackening layer, and the passivation layer and/or the blackening layer is used for preventing the metal mesh layer from being oxidized and failing.

17. A method for preparing a flexible composite conductive film is characterized by comprising the following steps:

forming a conductive composite layer on a substrate, wherein the conductive composite layer comprises a metal nanowire layer and a metal grid layer, the positions of the metal nanowire layer and the metal grid layer can be exchanged, and a conductive path is formed between the metal nanowire layer and the metal grid layer;

forming a first anchoring layer on the conductive composite layer;

further comprising:

forming a planar conductive layer between or over any two of the substrate, the metal nanowire layer, the metal mesh layer, and the first anchoring layer;

a conductive path is formed among the metal nanowire layer, the metal grid layer and the planar conductive layer;

forming a second anchoring layer between any two of the metal nanowire layer, the metal mesh layer, and the planar conductive layer;

the first anchoring layer has an electric conduction function when being arranged between the planar conducting layer and the metal nanowire layer or the metal grid layer, and the second anchoring layer enables the metal nanowire layer and the planar conducting layer or the metal grid layer to form an electric conduction path;

when the first anchoring layer is disposed on the metal nanowire layer, the first anchoring layer fills or is embedded in network voids in the metal nanowire layer;

when the first anchoring layer is arranged on the metal grid layer, the first anchoring layer is filled or embedded in grid gaps in the metal grid layer;

when the first anchoring layer is disposed on the planar conductive layer, the first anchoring layer covers a surface of the planar conductive layer.

18. The method of claim 17, wherein the first anchoring layer comprises one or a combination of acrylic monomers, silicone-epoxy, siloxane, phenolic resin, polyurethane prepolymer, and polyimide prepolymer, and further comprises any one or a combination of polypyrrole, polythiophene, polyacetylene, polyparaphenylene, polyaniline, perylene pigments, azo pigments, phthalocyanine and phthalocyanine compounds, pentacene derivatives, benzothiophene derivatives, rubrene, C60, poly 3-hexylthiophene, poly p-phenylene vinylene, and polyphenol;

the first anchoring layer is manufactured in a way of over-light curing or heat curing;

the metal nanowire in the metal nanowire layer is any one or a combination of several of a nano copper wire, a nano gold wire, a nano silver wire, a nano tungsten wire, a nano platinum wire, a nano palladium wire, a nano iron wire, a nano cobalt wire and a nano nickel wire;

the material of the planar conducting layer is any one or combination of a plurality of transparent oxide films, metal films, graphene films and transparent organic conducting thin films;

the material of the metal grid layer is one or a combination of more of silver, copper, silver alloy and copper alloy;

the metal grid layer is manufactured in a nano-imprinting mode, an ink-jet printing mode, a silk-screen printing mode or a magnetron sputtering mode and an orthogonal etching mode.

19. Use of a flexible composite conductive film according to any one of claims 1 to 16 in a touch panel, a display, a mobile phone antenna circuit, an infrared optical imaging element, a photosensor, an electromagnetic shield, a smart window, a smart tablet, and a solar cell.

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