阅读说明：本技术 一种柔性导电膜及电路板的制备方法 (Preparation method of flexible conductive film and circuit board ) 是由 廖勇志 于 2021-09-28 设计创作，主要内容包括：本发明公开了一种柔性导电膜及电路板的制备方法。包括以下几个步骤：(1)将含铜原料填充到粉体仓中待用；(2)将包含有还原性气体、惰性气体和碳源气体的混合气体置入气体仓内待用；(3)打开激光,同时含铜原料在混合气体的带动下进入成型舱体,在激光的照射下,含铜原料与混合气体的还原气体反应生成铜单质,生成的铜单质在激光条件下诱导混合气体中的碳源生成石墨烯膜包裹铜的导电粒子。本发明采用气态碳源、铜源粉体,还原性气体在激光状态下进行反应,生成铜单质,生成的铜单质在激光条件下诱导混合气体中的碳源生成石墨烯膜包裹铜的导电粒子,从而形成导电通路。采用气态碳源不易在纳米铜表面团聚,导电均匀。(The invention discloses a flexible conductive film and a preparation method of a circuit board. The method comprises the following steps: (1) filling a copper-containing raw material into a powder bin for later use; (2) placing mixed gas containing reducing gas, inert gas and carbon source gas into a gas bin for standby; (3) and opening the laser, enabling the copper-containing raw material to enter the forming cabin under the drive of the mixed gas, reacting the copper-containing raw material with the reducing gas of the mixed gas to generate a copper simple substance under the irradiation of the laser, and inducing a carbon source in the mixed gas to generate conductive particles of which the copper is wrapped by the graphene film under the laser condition. According to the invention, a gaseous carbon source, copper source powder and reducing gas are adopted to react in a laser state to generate a copper simple substance, and the generated copper simple substance induces the carbon source in the mixed gas to generate conductive particles with copper wrapped by a graphene film under the laser condition, so that a conductive path is formed. The gaseous carbon source is not easy to agglomerate on the surface of the nano copper, and the electric conduction is uniform.)

1. A preparation method of a flexible conductive film is characterized by comprising the following steps:

(1) filling a copper-containing raw material into a powder bin for later use;

(2) placing mixed gas containing reducing gas, inert gas and carbon source gas into a gas bin for standby;

(3) and opening the laser, enabling the copper-containing raw material to enter the forming cabin under the drive of the mixed gas, reacting the copper-containing raw material with the reducing gas of the mixed gas to generate a copper simple substance under the irradiation of the laser, and inducing a carbon source in the mixed gas to generate conductive particles of which the copper is wrapped by the graphene film under the laser condition.

2. The method for manufacturing a conductive circuit board according to claim 1, wherein the copper-containing material is one or more of nano copper oxide, nano copper hydroxide, nano cuprous oxide, nano basic copper carbonate or nano copper oxalate.

3. The method of claim 2, wherein the nano copper oxide, nano copper hydroxide, nano cuprous oxide, nano copper carbonate hydroxide, nano copper oxalate, etc. have the shape of nano sphere, nano rod or nano wire.

4. The method of claim 1, wherein the mixed gas is a mixture of a reducing gas, an inert gas and a carbon source gas in any ratio.

5. The method of manufacturing a conductive circuit board according to claim 1, wherein the reducing gas is hydrogen, carbon monoxide or methane; the inert gas is nitrogen or helium; the carbon source gas is carbon dioxide, methane, ethane or natural gas.

6. A method of making a flexible conductive film according to any of claims 1-5 comprising the steps of:

(1) preparing a substrate: uniformly coating an ultraviolet-polymerizable monomer or high-molecular polymer solution on the transparent film to form a liquid film;

(2) filling a base material: filling a copper-containing raw material into a powder bin for later use;

(3) preparing mixed gas: placing mixed gas containing reducing gas, inert gas and carbon source gas into a gas bin for standby;

(4) and (2) turning on the laser, enabling the copper-containing raw material to enter the forming cabin under the drive of the mixed gas, enabling the copper-containing raw material to react with the reducing gas of the mixed gas to generate a copper simple substance under the irradiation of the laser, inducing a carbon source in the mixed gas to generate conductive particles with copper wrapped by the graphene film under the laser condition, and spraying the conductive particles onto the transparent film in the step (1) under the drive of the air flow to obtain the conductive film.

7. The method of claim 6, wherein the transparent film of step (1) is PET, PC, PI or transparent glass.

8. The method according to claim 6, wherein in the step (1), the ultraviolet polymer is an acrylate liquid monomer and a photoinitiator, the polymer solution is formed by dissolving a polymer in water or an organic solvent, the polymer comprises polyester, polyurethane or polyolefin, and the solvent comprises one or more of water, alcohols, ethers or esters.

9. The method of claim 6, wherein in step (1), the liquid film has a thickness of 0.5 to 50 μm.

10. A preparation method of a conductive circuit board is characterized by comprising the following steps:

(1) preparing a substrate: uniformly coating an ultraviolet-polymerizable monomer or high-molecular polymer solution on the transparent film to form a liquid film;

(2) preparing a circuit pattern mask: printing a pattern on a thin film or a metal sheet of an organic polymer, and then etching and removing the pattern according to the size of the pattern by using laser to form a hollow pattern; fixing a pattern mask above the base material coated with the liquid film;

(3) filling a base material: filling a copper-containing raw material into a powder bin for later use;

(4) preparing mixed gas: placing mixed gas containing reducing gas, inert gas and carbon source gas into a gas bin for standby;

(5) and (2) opening the laser, enabling the copper-containing raw material to enter the forming cabin under the drive of the mixed gas, enabling the copper-containing raw material to react with the reducing gas of the mixed gas to generate a copper simple substance under the irradiation of the laser, inducing a carbon source in the mixed gas to generate conductive particles with copper wrapped by a graphene film under the laser condition, and spraying the conductive particles onto the transparent film in the step (1) through a circuit pattern mask under the drive of the air flow to obtain the conductive circuit board.

Technical Field

The invention relates to a flexible conductive film and a preparation method of a circuit board, and belongs to the technical field of conductive films.

Background

Transparent conductive films (transparent electrodes) are widely used in various electronic devices, including touch screens, displays, thin-film solar cells, etc., such as mobile phones, pads, computers, electronic skins, etc., which can touch sensitive screens. The touchable sensing screen adopts a capacitive screen sensing mode, and sensing signals are transmitted in a mode of changing capacitance through touch. The traditional capacitive screen adopts a transparent conductive film as an electrode of a capacitor, for example, the screens of mobile phones and pads mostly adopt vacuum sputtering Indium Tin Oxide (ITO) to form the transparent conductive electrode on the surface of glass.

The traditional method for manufacturing the touch screen by using the ITO glass transparent electrode has the advantages of high requirements on process equipment, low production efficiency and high cost. Because the ITO resistance is high, when making super large touch-sensitive screen, the response time delay is poor, and glass weight is big moreover, and is with high costs and transportation installation difficulty. Due to the brittle characteristics of metal oxides, the metal oxides cannot be applied to flexible devices which are increasingly popular nowadays, such as flexible thin film solar cells, flexible touch screen displays, electronic skins and other fields.

In recent years, there are many technological applications of silver materials instead of ITO to meet the requirement of flexibility of transparent electrodes, but silver is a precious metal and expensive, and the problem of low-cost manufacturing cannot be solved.

The circuit in the Printed Circuit Board (PCB) and flexible printed circuit board (FPC) is made up of copper or aluminium, PCB and FPC connect various active and passive components in the devices such as electronic apparatus, communication, etc., such as resistance, electric capacity, inductance, and various power chips, play effects such as connecting, conducting, signal transmission, etc.; such a conductor circuit may also form a loop coil as an inductor coil, which generates a current by electromagnetic induction in a changing magnetic field, such as a coil in wireless charging.

The PCB and the FPC are manufactured into a conductive circuit by adopting a chemical etching method, wherein a copper film or an aluminum film is covered on an epoxy resin plate, a PI film or a PET film, and the conductive circuit is formed on the epoxy resin plate, the PI film or the PET film through the processes of photomask, exposure, etching, development molding and the like.

The method has the disadvantages of overlong process flow and high manufacturing cost, and needs to use chemical etching liquid containing acid, alkali and various additives, and the generated waste liquid contains harmful components such as acid, alkali, copper, aluminum and the like, thereby causing environmental pollution.

Disclosure of Invention

In order to overcome the defects of the prior art, the invention provides a preparation method of a flexible conductive film and a circuit board, which adopts cheap and easily-obtained raw materials and combines a 3D printing technology to efficiently prepare a high-quality transparent conductive film or a conductive circuit board, thereby simplifying the process and improving the production efficiency, and further reducing the production cost; meanwhile, the preparation process is environment-friendly.

The invention is realized by the following technical scheme:

a preparation method of a flexible conductive film comprises the following steps:

(1) preparing a substrate;

a. uniformly coating an ultraviolet-polymerizable acrylate liquid monomer (containing a photoinitiator) on a transparent PET or PC film to form a liquid film with the thickness of 0.5-50 microns; or coating a layer of high molecular polymer solution with the thickness of 0.5-50 microns, wherein the solution is formed by dissolving high molecular polymer in water or organic solvent, the high molecular polymer comprises polyester, polyurethane, polyolefin and the like, and the solvent comprises water, alcohols, ethers, esters or a mixture of the water, the alcohols, the ethers and the esters.

b. Placing the coated substrate in a roll-to-roll apparatus;

(2) filling the base material;

filling one or more mixed powder of nano copper oxide, nano copper hydroxide, nano cuprous oxide, nano basic copper carbonate, nano copper oxalate and the like into a powder bin in a 3D metal printing device for later use; wherein the appearance characteristics of the nano copper oxide, the nano copper hydroxide, the nano cuprous oxide, the nano basic copper carbonate, the nano copper oxalate and the like comprise a nano ball shape, a nano rod shape and a nano line shape;

(3) preparing mixed gas;

placing mixed gas containing reducing gas, inert gas and carbon source gas into a gas cabin of a 3D metal printing device for standby; wherein the reducing gas includes but is not limited to hydrogen, carbon monoxide, methane, etc., and the mixing ratio is any ratio; inert gases include, but are not limited to, nitrogen, helium, and the like; the mixing proportion is any proportion; the carbon source gas includes but is not limited to carbon dioxide, methane, ethane, natural gas and the like, and the mixing ratio of the gases is any ratio;

(4) driving oxygen in the formed cabin body;

and opening the nitrogen valve to completely drive the air in the formed cabin body, thereby reducing the oxygen content in the cabin body to the maximum extent. So as to ensure the smooth operation of the forming process;

(5) forming the transparent electrode in one step;

c. opening a mixed gas switch, and pre-ventilating for a certain time;

d. opening the roll-to-roll device and controlling the proper speed;

e. turning on a laser switch;

f. the method comprises the following steps of opening a powder conveying switch, enabling powder to enter a forming cabin body under the driving of mixed gas, reacting with reducing gas of the mixed gas to generate a copper simple substance under the action of laser, inducing a carbon source in the mixed gas to generate conductive particles with copper wrapped by a graphene film under the laser condition, and spraying the conductive particles onto a prepared transparent film such as PET, PC and the like coated with an ultraviolet-polymerizable acrylate liquid monomer or a prepared transparent film such as PET, PC and the like coated with a high polymer solution under the driving of air flow. If the liquid film layer on the film is a mixture of an acrylate monomer and a photoinitiator, ultraviolet irradiation is carried out to initiate the acrylate monomer to polymerize into a macromolecule, the macromolecule is solidified into the liquid film layer on the light-permeable conductive path film, if the liquid film layer is a macromolecule polymer solution, the solvent is removed by a method of baking and drying at the temperature of 80-200 ℃, and the polymer is solidified and fixes the graphene coated conductive particles on transparent PET and PC.

A preparation method of a conductive circuit board comprises the following steps:

(1) preparing a substrate;

a. uniformly coating an ultraviolet-polymerizable acrylate liquid monomer (containing a photoinitiator) on a transparent film such as PET (polyethylene terephthalate), PC (polycarbonate) and the like to form a liquid film with the thickness of 0.5-50 microns; or coating a high molecular polymer solution liquid film with the thickness of 0.5-50 microns, wherein the solution is formed by dissolving high molecular polymers in water or an organic solvent, the high molecular polymers comprise polyester, polyurethane, polyolefin and the like, and the solvent comprises water, alcohols, ethers, esters or a mixture of the water, the alcohols, the ethers and the esters.

b. Preparing a circuit pattern mask: the pattern is printed on a thin film of an organic polymer (PET, PE, PC, PP, etc.) or a metal sheet (copper plate, aluminum plate, etc.), and then etched and removed by laser according to the size of the pattern to form a through pattern.

c. Fixing the pattern mask above the base material coated with the liquid film, and placing the pattern mask and the base material together in a roll-to-roll device;

(2) filling the base material;

filling one or more mixed powder of nano copper oxide, nano copper hydroxide, nano cuprous oxide, nano basic copper carbonate, nano copper oxalate and the like into a powder bin in a 3D metal printing device for later use; wherein the appearance characteristics of the nano copper oxide, the nano copper hydroxide, the nano cuprous oxide, the nano basic copper carbonate, the nano copper oxalate and the like comprise a nano ball shape, a nano rod shape and a nano line shape;

(3) preparing mixed gas;

placing mixed gas containing reducing gas, inert gas and carbon source gas into a gas cabin of a 3D metal printing device for standby; wherein the reducing gas includes but is not limited to hydrogen, carbon monoxide, methane, etc., and the mixing ratio is any ratio; inert gases include, but are not limited to, nitrogen, helium, and the like; the mixing proportion is any proportion; the carbon source gas comprises but is not limited to carbon dioxide, methane, ethane, natural gas and the like, and the mixing ratio is any ratio;

(4) driving oxygen in the formed cabin body;

and opening the nitrogen valve to completely drive the air in the formed cabin body, thereby reducing the oxygen content in the cabin body to the maximum extent. So as to ensure the smooth operation of the forming process;

(5) forming the transparent electrode in one step;

c. opening a mixed gas switch, and pre-ventilating for a certain time;

d. opening the roll-to-roll device and controlling the proper speed;

e. turning on a laser switch;

f. the method comprises the steps of opening a powder conveying switch, enabling powder to enter a forming cabin body under the driving of mixed gas, reacting with reducing gas of the mixed gas to generate a copper simple substance under the action of laser, inducing a carbon source in the mixed gas to generate graphene-coated copper conductive particles under the laser condition, and spraying the graphene-coated copper conductive particles onto transparent films such as PET and PC coated with ultraviolet-polymerizable acrylate liquid monomers or onto prepared transparent films such as PET and PC coated with high polymer solution through a pattern mask under the driving of air flow. If the liquid film layer on the film is a mixture of an acrylate monomer and a photoinitiator, the acrylate monomer is initiated to polymerize into a polymer by ultraviolet irradiation, and the polymer is solidified into a light-permeable conductive path; if the liquid film layer on the film is a high molecular polymer solution, the solvent is removed by a method of baking and drying at the temperature of 80-200 ℃, and the polymer is solidified and graphene particles are fixed on transparent PET and PC.

The content of the reducing gas is preferably 1 to 20 parts by weight, 60 to 80 parts by weight, and 1 to 2080 to 99 parts by weight, respectively, of the inert gas and the carbon source gas.

The invention achieves the following beneficial effects:

when the conductive film is manufactured, a gaseous carbon source and copper source powder are adopted, reducing gas reacts in a laser state to generate a copper simple substance, the generated copper simple substance induces the carbon source in mixed gas to generate conductive particles with copper wrapped by the graphene film under the laser condition, and a conductive path is formed on the surface of the film, so that the conductive film is obtained. The gaseous carbon source is not easy to agglomerate on the surface of the nano copper, the electric conduction is uniform, and the safety is high because the metal oxide is used as the source of the copper simple substance.

The raw materials are cheap and easy to obtain, rare earth is not used, noble metal is not used, the process is simple and efficient, the automation degree is high, the resistance of the prepared transparent electrode is small (less than 50mohm/□/mil), the transmittance is high (more than 90 percent), the resistance is increased by less than 300 percent after the transparent electrode is folded for many times, the project breaks through the requirement of the traditional technology on the industrial development, and the high-quality transparent electrode is prepared from cheap materials and is suitable for different materials and application fields. Therefore, the invention has good social and economic benefits.

The flexible conductive circuit prepared by the invention has small resistance (less than 50mohm/□/mil) and high flexibility, and the resistance is increased by less than 300 percent after being folded for many times.

Detailed Description

The invention is further described below. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.

Example 1

(1) Preparing a substrate;

a. uniformly coating an ultraviolet-polymerizable acrylate liquid monomer (containing a photoinitiator) on a transparent PET film to form a liquid film with the thickness of 0.5-50 microns;

b. placing the coated substrate in a roll-to-roll apparatus;

(2) filling the base material;

filling the nano copper oxide powder into a powder bin in a 3D metal printing device for later use; wherein the nano copper oxide is in a nano ball shape;

(3) preparing mixed gas;

placing mixed gas containing reducing gas, inert gas and carbon source gas mixed in any proportion into a gas cabin of a 3D metal printing device for standby; wherein the reducing gas is carbon monoxide, and the inert gas is nitrogen; the carbon source gas is carbon dioxide;

(4) driving oxygen in the formed cabin body;

and opening the nitrogen valve to completely drive the air in the formed cabin body, thereby reducing the oxygen content in the cabin body to the maximum extent. So as to ensure the smooth operation of the forming process;

(5) forming the transparent electrode in one step;

c. opening a mixed gas switch, and pre-ventilating for a certain time;

d. opening the roll-to-roll device and controlling the proper speed;

e. turning on a laser switch;

f. the method comprises the following steps of opening a powder conveying switch, enabling powder to enter a forming cabin body under the driving of mixed gas, reacting with reducing gas of the mixed gas to generate a copper simple substance under the action of laser, inducing a carbon source in the mixed gas to generate conductive particles with copper wrapped by a graphene film under the laser condition, spraying the conductive particles onto a pre-prepared PET (polyethylene terephthalate) film coated with an ultraviolet-polymerizable acrylate liquid monomer under the driving of air flow, initiating polymerization of the acrylate monomer into high molecules through ultraviolet irradiation, and solidifying the high molecules into a light-permeable conductive passage.

Example 2

(1) Preparing a substrate;

a. uniformly coating a layer of high molecular polymer solution with the thickness of 0.5-50 microns on a transparent PC film, wherein the solution is formed by dissolving polyester in alcohol;

b. placing the coated substrate in a roll-to-roll apparatus;

(2) filling the base material;

filling the nano copper hydroxide powder into a powder bin in a 3D metal printing device for later use; wherein the appearance characteristics of the nano copper hydroxide are a nano rod shape and a nano wire;

(3) preparing mixed gas;

placing mixed gas containing reducing gas, inert gas and carbon source gas into a gas cabin of a 3D metal printing device for standby; wherein the reducibility is hydrogen, the inert gas is helium, and the carbon source gas is methane, and the weight parts are respectively 51 parts, 80 parts and 1580 parts.

(4) Driving oxygen in the formed cabin body;

and opening the nitrogen valve to completely drive the air in the formed cabin body, thereby reducing the oxygen content in the cabin body to the maximum extent. So as to ensure the smooth operation of the forming process;

(5) forming the transparent electrode in one step;

c. opening a mixed gas switch, and pre-ventilating for a certain time;

d. opening the roll-to-roll device and controlling the proper speed;

e. turning on a laser switch;

f. and opening a powder conveying switch, enabling the powder to enter the forming cabin body under the driving of the mixed gas, reacting with the reducing gas of the mixed gas to generate a copper simple substance under the action of laser, inducing a carbon source in the mixed gas to generate conductive particles with copper wrapped by a graphene film under the laser condition, and spraying the conductive particles onto a PC transparent film which is prepared in advance and coated with a high polymer solution under the driving of air flow. And (3) removing the solvent by a method of baking and drying at the temperature of 80-200 ℃, solidifying the polymer and fixing the conductive particles of the graphene coated copper on the transparent PC.

Example 3

(1) Preparing a substrate;

a. a layer of high molecular polymer solution with the thickness of 0.5-50 microns is uniformly coated on a transparent film of transparent glass, the solution is formed by dissolving high molecular polymer in an organic solvent, the high molecular polymer is polyurethane, and the organic solvent is ether.

b. Placing the coated substrate in a roll-to-roll apparatus;

(2) filling the base material;

filling the nano cuprous oxide powder into a powder bin in a 3D metal printing device for later use; wherein the appearance characteristic of the nano cuprous oxide is a nanowire type;

(3) preparing mixed gas;

placing mixed gas containing reducing gas, inert gas and carbon source gas into a gas cabin of a 3D metal printing device for standby; wherein the reducing gas is methane, the inert gas is nitrogen, and the carbon source gas is natural gas, and the weight parts of the reducing gas are 20 parts, 60 parts and 20 parts respectively.

(4) Driving oxygen in the formed cabin body;

and opening the nitrogen valve to completely drive the air in the formed cabin body, thereby reducing the oxygen content in the cabin body to the maximum extent. So as to ensure the smooth operation of the forming process;

(5) forming the transparent electrode in one step;

c. opening a mixed gas switch, and pre-ventilating for a certain time;

d. opening the roll-to-roll device and controlling the proper speed;

e. turning on a laser switch;

f. the method comprises the steps of opening a powder conveying switch, enabling powder to enter a forming cabin body under the driving of mixed gas, reacting with reducing gas of the mixed gas to generate a copper simple substance under the action of laser, inducing a carbon source in the mixed gas to generate conductive particles with copper coated by a graphene film under the laser condition, spraying the conductive particles onto prepared transparent glass coated with a high-molecular polymer solution under the driving of air flow, discharging a solvent through a method of baking and drying at the temperature of 80-200 ℃, and solidifying a polymer and fixing the conductive particles with copper coated by graphene on the transparent glass.

Example 4

A preparation method of a conductive circuit board comprises the following steps:

(1) preparing a substrate;

a. uniformly coating an ultraviolet-polymerizable acrylate liquid monomer (containing a photoinitiator) on the PI transparent film to form a liquid film with the thickness of 0.5-50 microns.

b. Preparing a circuit pattern mask: printing a pattern on the PP film, and then etching and removing the pattern according to the size of the pattern by using laser to form a hollow pattern.

c. Fixing the pattern mask above the base material coated with the liquid film, and placing the pattern mask and the base material together in a roll-to-roll device;

(2) filling the base material;

filling the nano basic copper carbonate powder into a powder bin in a 3D metal printing device for later use; wherein the appearance characteristics of the nanometer basic copper carbonate comprise nanometer ball type;

(3) preparing mixed gas;

placing mixed gas containing reducing gas, inert gas and carbon source gas into a gas cabin of a 3D metal printing device for standby; wherein the reducing gas is hydrogen, the inert gas is nitrogen, the carbon source gas is ethane, and the mixing proportion is any proportion; the weight portions are respectively 1 portion, 80 portions and 19 portions.

(4) Driving oxygen in the formed cabin body;

and opening the nitrogen valve to completely drive the air in the formed cabin body, thereby reducing the oxygen content in the cabin body to the maximum extent. So as to ensure the smooth operation of the forming process;

(5) forming the transparent electrode in one step;

c. opening a mixed gas switch, and pre-ventilating for a certain time;

d. opening the roll-to-roll device and controlling the proper speed;

e. turning on a laser switch;

f. and opening a powder conveying switch, enabling the powder to enter the forming cabin body under the driving of the mixed gas, reacting with the reducing gas of the mixed gas to generate a copper simple substance under the action of laser, inducing a carbon source in the mixed gas to generate conductive particles with copper wrapped by a graphene film under the laser condition, and spraying the conductive particles onto the PI transparent film coated with the ultraviolet-polymerizable acrylate liquid monomer through the pattern mask under the driving of air flow. And (3) initiating the acrylate monomer to polymerize into high polymer through ultraviolet irradiation, and solidifying into a conductive path to obtain the final conductive circuit board.

Example 5

A preparation method of a conductive circuit board comprises the following steps:

(1) preparing a substrate;

a. a layer of high molecular polymer solution liquid film with the thickness of 0.5-50 microns is uniformly coated on a PET transparent film, the solution is formed by dissolving polymer macromolecules in water or an organic solvent, the polymer macromolecules are polyolefin, and the solvent is esters.

b. Preparing a circuit pattern mask: and printing a pattern on the copper plate, and then etching and removing the pattern according to the size of the pattern by using laser to form a hollow pattern.

c. Fixing the pattern mask above the base material coated with the liquid film, and placing the pattern mask and the base material together in a roll-to-roll device;

(2) filling the base material;

filling nano copper oxalate powder into a powder bin in a 3D metal printing device for later use; wherein the appearance characteristic of the nano copper oxalate is a nano rod type;

(3) preparing mixed gas;

placing mixed gas containing reducing gas, inert gas and carbon source gas into a gas cabin of a 3D metal printing device for standby; wherein the reducing gas is carbon monoxide, and the inert gas is nitrogen; the carbon source gas is natural gas, and the weight parts of the natural gas are respectively 15 parts, 70 parts and 15 parts.

(4) Driving oxygen in the formed cabin body;

and opening the nitrogen valve to completely drive the air in the formed cabin body, thereby reducing the oxygen content in the cabin body to the maximum extent. So as to ensure the smooth operation of the forming process;

(5) forming the transparent electrode in one step;

c. opening a mixed gas switch, and pre-ventilating for a certain time;

d. opening the roll-to-roll device and controlling the proper speed;

e. turning on a laser switch;

f. and opening a powder conveying switch, enabling the powder to enter the forming cabin body under the driving of the mixed gas, reacting with the reducing gas of the mixed gas to generate a copper simple substance under the action of laser, inducing a carbon source in the mixed gas to generate conductive particles with copper wrapped by a graphene film under the laser condition, and spraying the conductive particles onto the PET transparent film coated with the high-molecular polymer solution through a pattern mask under the driving of air flow. And (3) removing the solvent by a method of baking and drying at the temperature of 80-200 ℃, solidifying the polymer and fixing the conductive particles of copper wrapped by the graphene film on the transparent PET. And obtaining the final conductive circuit board.

Example 6

A preparation method of a conductive circuit board comprises the following steps:

(1) preparing a substrate;

a. a layer of high molecular polymer solution liquid film with the thickness of 0.5-50 microns is uniformly coated on a PC transparent film, the solution is formed by dissolving polymer macromolecules in water or an organic solvent, and the polymer macromolecules are a mixture of polyester, solvent water and alcohols.

b. Preparing a circuit pattern mask: printing a pattern on a PE film, and then etching and removing the pattern according to the size of the pattern by using laser to form a hollow pattern.

c. Fixing the pattern mask above the base material coated with the liquid film, and placing the pattern mask and the base material together in a roll-to-roll device;

(2) filling the base material;

filling one or more mixed powder of nano copper oxide, nano copper hydroxide, nano cuprous oxide, nano basic copper carbonate, nano copper oxalate and the like into a powder bin in a 3D metal printing device for later use; wherein the appearance characteristics of the nano copper oxide, the nano copper hydroxide, the nano cuprous oxide, the nano basic copper carbonate, the nano copper oxalate and the like comprise a nano ball shape, a nano rod shape and a nano line shape;

(3) preparing mixed gas;

placing mixed gas containing reducing gas, inert gas and carbon source gas into a gas cabin of a 3D metal printing device for standby; wherein the reducing gas is carbon monoxide, the inert gas is nitrogen, and the carbon source gas is methane, and the weight parts are respectively 20 parts, 75 parts and 595 parts.

(4) Driving oxygen in the formed cabin body;

and opening the nitrogen valve to completely drive the air in the formed cabin body, thereby reducing the oxygen content in the cabin body to the maximum extent. So as to ensure the smooth operation of the forming process;

(5) forming the transparent electrode in one step;

c. opening a mixed gas switch, and pre-ventilating for a certain time;

d. opening the roll-to-roll device and controlling the proper speed;

e. turning on a laser switch;

f. and opening a powder conveying switch, enabling the powder to enter the forming cabin body under the driving of the mixed gas, reacting with the reducing gas of the mixed gas to generate a copper simple substance under the action of laser, inducing a carbon source in the mixed gas to generate conductive particles with copper wrapped by a graphene film under the laser condition, and spraying the conductive particles onto the PC transparent film coated with the high-molecular polymer solution through the graphic mask under the driving of airflow. And (3) removing the solvent by a method of baking and drying at the temperature of 80-200 ℃, solidifying the polymer and fixing the conductive particles of copper wrapped by the graphene film on the transparent PC. And obtaining the final conductive circuit board.

The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.