CN115976501A - Metal pattern on surface of insulating base material and additive manufacturing method - Google Patents
Metal pattern on surface of insulating base material and additive manufacturing method Download PDFInfo
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Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
Abstract
The invention provides a metal pattern on the surface of an insulating base material and an additive manufacturing method, and at present, the problems of strong interface and weak binding force between the base material and a deposition layer exist in metal additive manufacturing on the surface of a flexible base material.
Description
Technical Field
The invention belongs to the field of chemical activation and chemical plating, and particularly relates to a method for manufacturing a metal pattern on the surface of an insulating base material and an additive.
Background
The flexible conductive circuit is mainly used for connecting components in flexible electronics, can ensure the normal work of electronic products in bending, folding and stretching states, and is an important component of the flexible electronics. The metal film, especially copper, has the advantages of high conductivity, good flexibility and low price, and is the most commonly used flexible metal conductive material at present. The method for activating the flexible substrate and catalyzing copper deposition by using the soluble modified solution can deposit the copper conducting circuit on the surface of the flexible substrate, and realize the accurate manufacture of the flexible conducting circuit.
To perform copper line deposition on a flexible substrate, the flexible substrate must be pre-coated with a catalytically active pattern. Due to the inertness and low surface energy of the substrate surface, the substrate is usually subjected to surface-selective modification treatment, so that a catalyst (palladium, silver, cobalt, copper, and the like) is fixed at a preset position on the substrate to start an electroless copper plating reaction, the newly deposited copper is further subjected to catalytic copper deposition by the catalyst, and finally a copper conductive circuit and a device are formed at the preset position. Therefore, the fabrication and research of the catalytic layer on the surface of the flexible substrate plays a key role in the chemical deposition of copper circuits.
The surface modification of the flexible base material generally comprises the steps of preparing a modification solution to coarsen the surface of the base material and change the surface components of the base material, and the modification method is economical, efficient and suitable for batch production. The fact that an electronic product can normally work in a bent and folded state of a flexible conductive circuit is an important index for measuring the flexible conductive circuit, but the existing surface treatment method for additive manufacturing has the problems of strong interface and weak interface bonding force, for example, as disclosed in Chinese patent 'an activator for electroless copper plating, a preparation method thereof and a method for manufacturing a circuit by full addition based on the activator' (application publication No. CN 109487249A): and activating and treating the surface of the substrate by using air plasma, and reducing the catalytic metal ions into a metal simple substance. The metal additive product obtained by the method has an obvious interface, and the bonding force between the base material and the deposition layer is relatively weak. However, the interfacial effect should be reduced as much as possible to improve the adhesion of the deposited layer to the substrate. The modified base material is subjected to reducing treatment by adopting a chemical activation mode, catalytic metal ions in the activation layer of the base material are reduced into a catalytic metal simple substance, and the metal simple substance is embedded in the activation layer to be used as a catalyst for subsequent chemical plating. The chemical surface activation method has the advantages of convenient operation, uniform activation, easy regulation and control of reaction rate, easy control of reaction time, low cost, cheap and easily obtained raw materials and the like. The temperature of chemical copper plating is usually about 45 ℃, the flexible substrate is not damaged, a copper conducting circuit deposited by a chemical plating method has good conductivity, and the conductivity of the circuit can reach more than 60% of that of bulk copper generally. Therefore, the surface modified catalytic copper deposition of the flexible substrate has wide application prospect and research value in the aspect of flexible electronic manufacturing.
Disclosure of Invention
Aiming at the defects of plasma treatment and other modes in the surface modification process of the conventional flexible base material, the invention provides a method for additive manufacturing of a metal pattern on the surface of an insulating base material.
In order to solve the problems, the invention adopts the following technical scheme:
a method for manufacturing an additive of a metal pattern on the surface of an insulating substrate comprises the following steps:
(1) Preparing a modified solution: firstly, adding 10g of propylene glycol methyl ether and 1g of thiourea into a closed container, carrying out magnetic stirring at room temperature to obtain a colorless transparent solution, then adding 10g of bisphenol A diglycidyl ether into the obtained colorless transparent solution, continuing to carry out magnetic stirring until the diglycidyl ether is completely dissolved, and then adding 0.724g of silver nitrate into the reaction solution, and continuing to carry out magnetic stirring to obtain a light yellow transparent solution;
(2) Pretreatment of the surface of a PET base material: immersing the PET film into a beaker filled with absolute ethyl alcohol, and cleaning the PET film at room temperature by using an ultrasonic cleaner; washing the PET film cleaned by the ethanol bath with deionized water to remove residual ethanol on the surface of the PET, then putting the PET film into a drying oven, and drying to obtain a clean PET film;
(3) Surface modification of the PET film: adding an epoxy resin curing agent into the light yellow transparent solution obtained in the step (1) at room temperature, magnetically stirring for 30min, uniformly coating the solution on the PET film obtained in the step (2), and curing the coated solution to obtain a modified PET film;
(4) Surface activation of the PET film: the activator comprises a resin microetching agent and a reducing agent; firstly, placing the modified PET film in a resin micro-etching agent at 50-80 ℃ for treatment for 30-120 min, then washing the surface of the PET film with deionized water, and then placing the PET film in a reducing agent solution at 40-75 ℃ for 10-60 min to obtain the PET film with black silver simple substance attached to the surface;
(5) And (3) depositing copper on the surface of the PET film: and (4) placing the PET film activated in the step (4) in a chemical plating solution to deposit copper, and introducing air into the plating solution to improve the stability of the plating solution in the chemical plating process, thereby finally obtaining the PET substrate product with the copper layer deposited on the surface.
Preferably, the resin microetching agent of the activator in the step (4) is used for etching the epoxy resin formed by polymerizing the bisphenol A diglycidyl ether to expose the catalytic metal ions embedded therein; the reducing agent is used for reducing the exposed catalytic metal ions into a metal simple substance through strong reducibility and is used as a catalyst in chemical plating.
Preferably, the resin microetching agent in the activator in the step (4) is any one of acetone and ethylene glycol.
Preferably, the reducing agent in the activating agent in the step (4) is sodium borohydride solution, and the molar concentration is preferably 0.2-1.0 mol/L.
Preferably, in step (1), 10g of propylene glycol methyl ether and 1g of thiourea are charged into a closed vessel and magnetically stirred at room temperature at 200rpm for 15min to obtain a colorless transparent solution.
Preferably, 2 grams of epoxy resin curing agent 593 is added in step (3).
Preferably, the electroless plating solution in step (5) has the following formulation: 32g/L of potassium sodium tartrate tetrahydrate, 2.5g/L of disodium ethylenediamine tetraacetic acid dihydrate, 12.5g/L of copper sulfate pentahydrate, 3.5g/L of nickel sulfate hexahydrate, 10mg/L of 2,2' -bipyridine, 23mg/L of potassium ferrocyanide trihydrate, 10g/L of sodium hydroxide and 12ml/L of formaldehyde solution.
Preferably, in the step (5), air is blown into the plating solution during the electroless copper plating process, and the air flow is preferably 2.5 to 5cm 3 The temperature of the plating solution is controlled between 36 and 45 ℃, and the chemical plating time is controlled between 30 and 60min.
The invention also provides a metal pattern on the surface of the insulating base material obtained by the method.
The principle of the invention is as follows:
the activator system for reducing metal ions acts on a modified flexible base material system, and in a modified solution of the modified base material, a complexing agent is utilized to adsorb catalyst ions (namely metal ions), so that the catalyst ions can stably exist in the system. The modification system avoids the phenomenon that catalyst ions are reduced into metal nanoparticles by epoxy groups in epoxy resin to cause the agglomeration of metal nanoparticle catalysts, and prevents an activating agent from blocking pinholes in the ink-jet printing process so as to cause the unevenness of a chemically plated copper layer. The ionic activator can ensure that catalyst ions are uniformly distributed, and when the activator acts, the resin microetching agent firstly acts on the surface of a sample to etch the resin in the modified activation layer, so that the catalytic metal ions embedded in the modified activation layer are exposed. After the subsequent reducing agent reduces the catalyst metal ions into metal atoms in situ, the reduced metal atoms also serve as copper ions in the catalyst catalytic plating solution, and the copper ions are reduced into metal copper by the metal reducing agent and deposited on the surface of the base material to form a uniform copper plating layer.
Compared with other activation technologies, the method has the following beneficial effects:
in the invention, the modified solution is used as a bridging layer and is adhered to the surface of the flexible base material through the adhesive effect, the chemical bonding effect of the modified solution and the flexible base material enhances the bonding force, the catalyst metal ions are uniformly distributed in the modified solution, the surface of the modified flexible base material is etched through the resin microetching agent, and then the chemical reducing agent sodium borohydride solution reduces the catalyst metal ions uniformly distributed in the bridging layer to obtain the catalytic metal layer, and a compact, bright and strong-adhesion coating can be formed by matching with the subsequent chemical plating process. The plasma surface activation treatment technology has the defects of overlong treatment time, short timeliness, easy generation of secondary pollution, complex treatment process, expensive equipment and the like caused by insufficient strength, and the conventional technology for activating the modified layer has the advantages of simplicity and convenience in operation, uniform activation, easiness in regulating and controlling reaction strength, easiness in controlling reaction time, low cost, low price and easiness in obtaining raw materials and the like through a chemical activation treatment technology.
Drawings
FIG. 1 is a schematic view of an additive manufacturing process of a metal pattern on the surface of an insulating substrate according to the present invention;
FIG. 2 is a schematic view of the overall structure of a metal pattern on the surface of an insulating substrate according to the present invention;
FIG. 3 is a metallographic microscope photograph of a cross section of a metal pattern on the surface of an insulating base material according to the present invention;
FIG. 4 is a Scanning Electron Microscope (SEM) view of a section of a metal pattern on the surface of an insulating substrate according to the present invention.
Reference numerals: 101-printed circuit flexible substrate, 102-modified activation layer, 103-metal particles, and 104-deposited metal layer.
Detailed Description
The following embodiments of the present invention are provided by way of specific examples, and other advantages and effects of the present invention will be readily apparent to those skilled in the art from the disclosure herein. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
As shown in fig. 1, an embodiment provides a method for additive manufacturing of a metal pattern on a surface of an insulating substrate, comprising the following steps:
(1) Preparing a modified solution: firstly, adding 10g of propylene glycol methyl ether and 1g of thiourea into a closed container, carrying out magnetic stirring at room temperature to obtain a colorless transparent solution, then adding 10g of bisphenol A diglycidyl ether into the obtained colorless transparent solution, continuing to carry out magnetic stirring until the diglycidyl ether is completely dissolved, and then adding 0.724g of silver nitrate into the reaction solution, and continuing to carry out magnetic stirring to obtain a light yellow transparent solution;
(2) Pretreatment of the surface of a PET base material: immersing the PET film into a beaker filled with absolute ethyl alcohol, and cleaning the PET film at room temperature by using an ultrasonic cleaner; washing the PET film cleaned by the ethanol bath with deionized water to remove residual ethanol on the surface of the PET, then putting the PET film into a drying oven, and drying to obtain a clean PET film;
(3) Surface modification of the PET film: adding an epoxy resin curing agent into the light yellow transparent solution obtained in the step (1) at room temperature, magnetically stirring for 30min, uniformly coating the solution on the PET film obtained in the step (2), and curing the coated solution to obtain a modified PET film;
(4) Surface activation of the PET film: the activator comprises a resin microetching agent and a reducing agent; firstly, placing the modified PET film in a resin micro-etching agent at 50-80 ℃ for treatment for 30-120 min, then washing the surface of the PET film with deionized water, and then placing the PET film in a reducing agent solution at 40-75 ℃ for 10-60 min to obtain the PET film with black silver simple substance attached to the surface;
(5) And (3) depositing copper on the surface of the PET film: and (4) placing the PET film activated in the step (4) in a chemical plating solution to deposit copper, and introducing air into the plating solution to improve the stability of the plating solution in the chemical plating process, thereby finally obtaining the PET substrate product with the copper layer deposited on the surface.
In some embodiments, the resin microetching agent of the activator in step (4) is used to etch an epoxy resin formed by polymerization of bisphenol a diglycidyl ether, exposing catalytic metal ions embedded therein; the reducing agent is used for reducing the exposed catalytic metal ions into a metal simple substance through strong reduction, and is used as a catalyst in chemical plating.
In some embodiments, the resin microetching agent in the activator of step (4) is any one of acetone and ethylene glycol.
In some embodiments, the reducing agent in the activating agent in step (4) is sodium borohydride solution, and the molar concentration is preferably 0.2 to 1.0mol/L.
In some examples, 10g of propylene glycol methyl ether and 1g of thiourea were added to the closed vessel in step (1) and magnetically stirred at 200rpm for 15min at room temperature to give a colorless transparent solution.
In some embodiments, step (3) adds 2 grams of epoxy curing agent 593.
In some embodiments, the electroless plating solution of step (5) is specifically formulated as follows: 32g/L of potassium sodium tartrate tetrahydrate, 2.5g/L of disodium ethylene diamine tetraacetate dihydrate, 12.5g/L of copper sulfate pentahydrate, 3.5g/L of nickel sulfate hexahydrate, 10mg/L of 2,2' -bipyridine, 23mg/L of potassium ferrocyanide trihydrate, 10g/L of sodium hydroxide and 12ml/L of formaldehyde solution.
In some embodiments, step (5) is carried out by blowing air into the plating solution during the electroless copper plating process, and the air flow is preferably 2.5-5 cm 3 The temperature of the plating solution is controlled between 36 and 45 ℃, and the chemical plating time is controlled between 30 and 60min.
The metal pattern on the surface of the insulating base material obtained in the embodiment is shown in fig. 2, and sequentially includes a printed circuit flexible substrate 101, a modified activation layer 102, and a deposition metal layer 104 from bottom to top, where the modified activation layer 102 has metal particles 103 thereon.
Example 1:
the embodiment provides an additive manufacturing method of a metal pattern on the surface of an insulating base material, which comprises the following steps:
(1) Preparing a modification solution: first, 10g of propylene glycol methyl ether and 1g of thiourea were put in a closed vessel and magnetically stirred at room temperature at 200rpm for 15min to obtain a colorless transparent solution. Then, 10g of bisphenol A diglycidyl ether was added to the colorless transparent solution obtained above, and magnetic stirring was continued until it was completely dissolved. Subsequently, 0.724g of silver nitrate was further added to the above reaction solution and magnetic stirring was continued to obtain a pale yellow transparent solution.
(2) Pretreatment of the surface of a PET base material: the PET film (80 mm. Times.30 mm) was immersed in a beaker containing anhydrous ethanol, and washed with an ultrasonic cleaner at room temperature for 5min. Washing the PET film cleaned by the ethanol bath with a large amount of deionized water to remove residual ethanol on the surface of the PET, and then putting the PET film into a drying oven to dry for 30min at 80 ℃ to obtain a clean PET film.
(3) Surface modification of PET film: and (2) adding 2g of epoxy resin curing agent 593 into the light yellow transparent solution obtained in the step (1) at room temperature, uniformly coating the light yellow transparent solution on the treated PET film after magnetic stirring for 30min, and curing the modified solution to obtain the modified PET film.
(4) Surface activation of the PET film: the activator comprises resin microetching agent acetone and reducing agent sodium borohydride solution. Firstly, the modified PET film is placed in acetone at 50 ℃ for treatment for 30min, then the surface of the modified PET film is washed by deionized water, and then the modified PET film is placed in 0.5mol/L sodium borohydride solution at 40 ℃ for 10min to obtain the PET film with the black silver simple substance attached to the surface. The resin micro-etching agent of the activator is used for etching the epoxy resin formed by polymerizing the bisphenol A diglycidyl ether to expose the catalytic metal ions embedded in the epoxy resin; the reducing agent is used for reducing the exposed catalytic metal ions into a metal simple substance through strong reduction, and is used as a catalyst in chemical plating.
(5) Depositing copper on the surface of the PET film: the activated PET film is placed in an electroless plating solution to deposit copper (deposition is carried out for 30min at 45 ℃). The chemical plating solution comprises the following specific formula: 32g/L of potassium sodium tartrate tetrahydrate, 2.5g/L of disodium ethylene diamine tetraacetate dihydrate, 12.5g/L of copper sulfate pentahydrate, 3.5g/L of nickel sulfate hexahydrate, 10mg/L of 2,2' -bipyridine, 23mg/L of potassium ferrocyanide trihydrate, 10g/L of sodium hydroxide and 12ml/L of formaldehyde solution. In the chemical plating process, 2.5cm of plating solution is introduced into the plating solution 3 The stability of the plating solution is improved by the air in min, and finally the PET substrate product with the copper layer deposited on the surface is obtained.
As can be seen from FIG. 3, the copper metal is uniformly distributed on the surface of the PET film after electroless copper plating.
Example 2:
the embodiment provides a method for manufacturing an additive of a metal pattern on the surface of an insulating substrate, which comprises the following steps:
(1) Preparing a modified solution: firstly, adding 10g of propylene glycol methyl ether and 1g of thiourea into a closed container, magnetically stirring at the speed of 200rpm at room temperature for 15min to obtain a colorless transparent solution, then adding 10g of bisphenol A diglycidyl ether into the obtained colorless transparent solution, continuously magnetically stirring until the diglycidyl ether is completely dissolved, and then adding 0.724g of silver nitrate into the reaction solution, and continuously magnetically stirring to obtain a light yellow transparent solution;
(2) Pretreatment of the surface of a PET base material: immersing the PET film into a beaker filled with absolute ethyl alcohol, and cleaning the PET film at room temperature by using an ultrasonic cleaner; washing the PET film cleaned by the ethanol bath with deionized water, removing residual ethanol on the surface of the PET, then putting the PET film into a drying oven, and drying to obtain a clean PET film;
(3) Surface modification of PET film: adding 2g of epoxy resin curing agent 593 into the light yellow transparent solution obtained in the step (1) at room temperature, magnetically stirring for 30min, uniformly coating the solution on the PET film obtained in the step (2), and curing the coated solution to obtain a modified PET film;
(4) Surface activation of the PET film: the activator comprises a resin microetching agent glycol and a reducing agent sodium borohydride solution; firstly, placing the modified PET film in a resin micro-etching agent glycol at 80 ℃ for treatment for 120min, then washing the surface of the modified PET film with deionized water, and then placing the modified PET film in a 0.2mol/L sodium borohydride solution at 75 ℃ for 60min to obtain the PET film with a black silver simple substance attached to the surface; the resin micro-etching agent of the activator is used for etching the epoxy resin formed by polymerizing the bisphenol A diglycidyl ether to expose the catalytic metal ions embedded in the epoxy resin; the reducing agent is used for reducing the exposed catalytic metal ions into a metal simple substance through strong reducibility and is used as a catalyst in chemical plating.
(5) Depositing copper on the surface of the PET film: and (3) placing the PET film activated in the step (4) into chemical plating solution for depositing copper, wherein the formula of the chemical plating solution is as follows: 32g/L of potassium sodium tartrate tetrahydrate, 2.5g/L of disodium ethylene diamine tetraacetate dihydrate,12.5g/L of copper sulfate pentahydrate, 3.5g/L of nickel sulfate hexahydrate, 10mg/L of 2,2' -bipyridine, 23mg/L of potassium ferrocyanide trihydrate, 10g/L of sodium hydroxide and 12ml/L of formaldehyde solution. And in the chemical plating process, introducing air into the plating solution to improve the stability of the plating solution, and finally obtaining the PET substrate product with the copper layer deposited on the surface. Air is blown into the plating solution in the electroless copper plating process, and the air flow is preferably 5cm 3 The temperature of the plating solution is controlled at 36 ℃, and the chemical plating time is controlled at 60min. And obtaining the PET substrate product with the copper layer deposited on the surface.
The metal pattern on the surface of the insulating base material obtained in the embodiment is shown in fig. 2, and sequentially includes a printed circuit flexible substrate 101, a modified activation layer 102, and a deposition metal layer 104 from bottom to top, where the modified activation layer 102 has metal particles 103 thereon.
Example 3:
the embodiment provides a method for manufacturing an additive of a metal pattern on the surface of an insulating substrate, which comprises the following steps:
(1) Preparing a modified solution: firstly, adding 10g of propylene glycol methyl ether and 1g of thiourea into a closed container, magnetically stirring at the speed of 200rpm at room temperature for 15min to obtain a colorless transparent solution, then adding 10g of bisphenol A diglycidyl ether into the obtained colorless transparent solution, continuously magnetically stirring until the diglycidyl ether is completely dissolved, and then adding 0.724g of silver nitrate into the reaction solution, and continuously magnetically stirring to obtain a light yellow transparent solution;
(2) Pretreatment of the surface of a PET base material: soaking PET film (80 mm × 30 mm) in a beaker filled with anhydrous ethanol, and cleaning with an ultrasonic cleaner at room temperature for 5min; washing the PET film cleaned by the ethanol bath with deionized water to remove residual ethanol on the surface of the PET, then placing the PET film into a drying oven, and drying the PET film for 30min at 80 ℃ to obtain a clean PET film;
(3) Surface modification of PET film: adding 2g of epoxy resin curing agent 593 into the light yellow transparent solution obtained in the step (1) at room temperature, uniformly coating the solution on the PET film obtained in the step (2) after magnetic stirring for 30min, and obtaining a modified PET film after the coated solution is cured;
(4) Surface activation of the PET film: the activating agent comprises resin microetching agent acetone and reducing agent sodium borohydride solution; firstly, placing the modified PET film in resin micro-etching agent acetone at 60 ℃ for treatment for 60min, then washing the surface of the PET film with deionized water, and then placing the PET film in 1mol/L sodium borohydride solution at 55 ℃ for 30min to obtain the PET film with black silver simple substance attached to the surface; the resin microetching agent of the activator is used for etching the epoxy resin formed by polymerization of bisphenol A diglycidyl ether to expose catalytic metal ions embedded in the epoxy resin; the reducing agent is used for reducing the exposed catalytic metal ions into a metal simple substance through strong reducibility and is used as a catalyst in chemical plating.
(5) And (3) depositing copper on the surface of the PET film: and (3) placing the PET film activated in the step (4) into chemical plating solution for depositing copper, wherein the formula of the chemical plating solution is as follows: 32g/L of potassium sodium tartrate tetrahydrate, 2.5g/L of disodium ethylene diamine tetraacetate dihydrate, 12.5g/L of copper sulfate pentahydrate, 3.5g/L of nickel sulfate hexahydrate, 10mg/L of 2,2' -bipyridine, 23mg/L of potassium ferrocyanide trihydrate, 10g/L of sodium hydroxide and 12ml/L of formaldehyde solution. And in the chemical plating process, introducing air into the plating solution to improve the stability of the plating solution, and finally obtaining the PET substrate product with the copper layer deposited on the surface. Blowing air into the plating solution during the chemical copper plating process, wherein the air flow is preferably 3cm 3 The temperature of the plating solution is controlled at 40 ℃, and the chemical plating time is controlled at 45min. And obtaining the PET substrate product with the copper layer deposited on the surface.
The metal pattern on the surface of the insulating base material obtained in the embodiment is shown in fig. 2, and sequentially includes a printed circuit flexible substrate 101, a modified activation layer 102, and a deposition metal layer 104 from bottom to top, where metal particles 103 are respectively disposed on the modified activation layer 102.
The examples are merely illustrative of the principles of the present invention and its efficacy, and are not to be construed as limiting the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (9)
1. A method for manufacturing an additive of a metal pattern on the surface of an insulating substrate is characterized by comprising the following steps:
(1) Preparing a modification solution: firstly, adding 10g of propylene glycol methyl ether and 1g of thiourea into a closed container, carrying out magnetic stirring at room temperature to obtain a colorless transparent solution, then adding 10g of bisphenol A diglycidyl ether into the obtained colorless transparent solution, continuing to carry out magnetic stirring until the diglycidyl ether is completely dissolved, and then adding 0.724g of silver nitrate into the reaction solution, and continuing to carry out magnetic stirring to obtain a light yellow transparent solution;
(2) Pretreatment of the surface of a PET base material: immersing the PET film into a beaker filled with absolute ethyl alcohol, and cleaning the PET film at room temperature by using an ultrasonic cleaner; washing the PET film cleaned by the ethanol bath with deionized water to remove residual ethanol on the surface of the PET, then putting the PET film into a drying oven, and drying to obtain a clean PET film;
(3) Surface modification of PET film: adding an epoxy resin curing agent into the light yellow transparent solution obtained in the step (1) at room temperature, magnetically stirring for 30min, uniformly coating the solution on the PET film obtained in the step (2), and curing the coated solution to obtain a modified PET film;
(4) Surface activation of the PET film: the activator comprises a resin microetching agent and a reducing agent; firstly, placing the modified PET film in a resin micro-etching agent at 50-80 ℃ for treatment for 30-120 min, then washing the surface of the PET film with deionized water, and then placing the PET film in a reducing agent solution at 40-75 ℃ for 10-60 min to obtain the PET film with black silver simple substance attached to the surface;
(5) Depositing copper on the surface of the PET film: and (5) placing the PET film activated in the step (4) in chemical plating solution to deposit copper, and introducing air into the plating solution to improve the stability of the plating solution in the chemical plating process, thereby finally obtaining the PET substrate product with the surface deposited with the copper layer.
2. The method for additive manufacturing of a metal pattern on a surface of an insulating substrate according to claim 1, wherein: the resin microetching agent of the activating agent in the step (4) is used for etching the epoxy resin formed by polymerization of the bisphenol A diglycidyl ether, and catalytic metal ions embedded in the epoxy resin are exposed; the reducing agent is used for reducing the exposed catalytic metal ions into a metal simple substance through strong reduction, and is used as a catalyst in chemical plating.
3. The method for additive manufacturing of a metal pattern on a surface of an insulating substrate according to claim 1, wherein: and (4) the resin microetching agent in the activating agent in the step (4) is any one of acetone and glycol.
4. The method for additive manufacturing of a metal pattern on a surface of an insulating substrate according to claim 1, wherein: the reducing agent in the activating agent in the step (4) is sodium borohydride solution, and the molar concentration is preferably 0.2-1.0 mol/L.
5. The method for additive manufacturing of a metal pattern on a surface of an insulating substrate according to claim 1, wherein:
in the step (1), 10g of propylene glycol methyl ether and 1g of thiourea are added into a closed container, and stirred magnetically at the speed of 200rpm at room temperature for 15min to obtain a colorless transparent solution.
6. The method for additive manufacturing of a metal pattern on a surface of an insulating substrate according to claim 1, wherein: step (3) 2 grams of epoxy curing agent 593 was added.
7. The method for additive manufacturing of a metal pattern on a surface of an insulating substrate according to claim 1, wherein: the chemical plating solution in the step (5) has the following formula: 32g/L of potassium sodium tartrate tetrahydrate, 2.5g/L of disodium ethylene diamine tetraacetate dihydrate, 12.5g/L of copper sulfate pentahydrate, 3.5g/L of nickel sulfate hexahydrate, 10mg/L of 2,2' -bipyridine, 23mg/L of potassium ferrocyanide trihydrate, 10g/L of sodium hydroxide and 12ml/L of formaldehyde solution.
8. The method for additive manufacturing of a metal pattern on a surface of an insulating substrate according to claim 1, wherein: blowing air into the plating solution in the electroless copper plating process in the step (5), wherein the air flow is preferably 2.5-5 cm 3 Min, controlling the temperature of the plating solution between 36 and 45 ℃,the chemical plating time is controlled to be 30-60 min.
9. An insulating substrate surface metal pattern obtainable by the process of any one of claims 1 to 8.
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