WO2022141064A1 - Method for electroplating metal on insulating substrate surface - Google Patents

Method for electroplating metal on insulating substrate surface Download PDF

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WO2022141064A1
WO2022141064A1 PCT/CN2020/140888 CN2020140888W WO2022141064A1 WO 2022141064 A1 WO2022141064 A1 WO 2022141064A1 CN 2020140888 W CN2020140888 W CN 2020140888W WO 2022141064 A1 WO2022141064 A1 WO 2022141064A1
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resin
electroplating
coating
insulating substrate
conductive
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PCT/CN2020/140888
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French (fr)
Chinese (zh)
Inventor
赖志强
梁先文
赵涛
刘丹
孙蓉
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深圳先进电子材料国际创新研究院
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Priority to PCT/CN2020/140888 priority Critical patent/WO2022141064A1/en
Publication of WO2022141064A1 publication Critical patent/WO2022141064A1/en

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/54—Electroplating of non-metallic surfaces
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal

Definitions

  • the invention belongs to the technical field of electroplating, and particularly relates to a method for electroplating metal on the surface of an insulating base material.
  • the second method is to use electrodeposition, that is, electroplating.
  • electroplating has the advantages of less influence on size, good adhesion and controllable thickness. widely used.
  • the surface of the insulating substrate needs to be treated to have a certain conductivity.
  • Electroless plating is the most traditional method. Although this process is relatively mature, it has many shortcomings that are difficult to overcome.
  • the reducing agent used is usually toxic formaldehyde, which poses a threat to the life and health of production personnel.
  • the plating solution process is complicated. The plating solution is unstable, which increases the difficulty and cost of management and control. There are also a large number of complexing agents in the plating solution. These complexing agents cause serious environmental pollution, which also increases the difficulty and cost of processing.
  • the researchers carried out A large number of process researches to replace electroless plating. Physical/chemical vapor deposition can effectively avoid the environmental problems caused by electroless plating, and can deposit dense metal layers.
  • the conductive material is attached to the insulating substrate through surface treatment and forms a uniform film.
  • the common material used to form the conductive film is carbon.
  • Black, graphene and organic conductive polymers, carbon black and graphene have strong hydrophobicity because they are non-polar substances, and at the same time, they are easy to agglomerate due to their small particle size, so they must be uniformly dispersed in water. A large amount of dispersant needs to be added, but this will inevitably reduce the conductivity and the stability of the plating solution.
  • CN107723764A both use metal ion-activated organic conductive polymer films to achieve
  • the main disadvantage of the method of direct electroplating on insulating substrates is that the process is cumbersome, and steps such as adjustment, neutralization and activation are required, the copper deposition rate is low, and copper foil is required for induced deposition.
  • the purpose of the present invention is to address the defects of the background technology and the challenges of the current technology, especially for the metallization of the insulating base material with low dielectric constant, the present invention provides a brand-new method for coating conductive substances on the resin coating.
  • the method is used to form a conductive film on the surface of the insulating substrate, and the formed conductive film is evenly distributed on the insulating substrate and has good conductivity. Due to the existence of the resin, the conductive film has an excellent bond on most insulating substrates. force.
  • the technical scheme of the present invention is:
  • a method for electroplating metal on the surface of an insulating base material comprising the steps of:
  • Plating process parameters and current types are not limited and can be any type of plating parameters.
  • the resin coating includes the following components by mass percentage: resin: 10%-50%, solvent: 10%-50%, curing agent: 1%-10%, solid Filler: 10-60%;
  • step S1 the resin is mixed with the solvent, and fully dispersed to obtain a resin solution
  • the solid filler is fully mixed with the solvent, and fully dispersed to obtain a solid filler solution
  • the resin solution and the solid filler solution are mixed and fully dispersed, and then added curing agent, and fully dispersed to obtain resin coating;
  • step S1 the resin, solid filler and solvent are fully dispersed to obtain a mixed solution, and then a curing agent is added and fully dispersed to obtain a resin coating.
  • the resin is selected from polyethylene, polypropylene, polyvinyl chloride, polystyrene, ABS resin, polyester, polycarbonate, polyurethane, polyamide, polyimide, acrylic One or more of resin, epoxy resin, phenolic resin, UV resin, PTFE resin, polyarylene ether nitrile resin; preferably polyurethane, polyester and UV resin.
  • the solvent is selected from water, ethanol, isopropanol, diethyl ether, toluene, pentane, cyclohexane, acetone, methyl ethyl ketone, ethyl ester, ethyl acetate, N,N- One or more of dimethylformamide, N-methylpyrrolidone, tetrahydrofuran, etc.; preferably ethyl acetate and butanone.
  • the curing agent is selected from one or more of polyisocyanates, acid anhydrides, organic amines, polyurethanes and imidazole curing agents; preferably polyisocyanates and imidazole curing agents.
  • the solid filler is selected from silicon dioxide, graphite, graphene, titanium dioxide, aluminum hydroxide, magnesium hydroxide, magnesium oxide, aluminum oxide, boron nitride, ammonium phosphate, One or more of urea, triphenyl, triphenylphosphine, melamine, melamine derivatives, ammonium polyphosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate and phosphinate, the diameter of the solid filler is 0.1 -100 ⁇ m; preferably melamine and ammonium polyphosphate, 1-10 ⁇ m in diameter.
  • the insulating base material is a plane base material or a special-shaped base material of different materials
  • the insulating base material is selected from epoxy resin reinforced glass fiber cloth, non-woven fabric, glass fiber cloth, ceramics, silicon, wood base material, and organic polymer film;
  • the organic polymer film includes polyethylene, polypropylene, polyimide, polyurethane, polyester, and polycarbonate.
  • the coating process includes one or more of blade coating, spin coating, dip coating, spray coating, microgravure printing, slit extrusion and screen printing, and the drying temperature
  • the temperature is 60°C-300°C, and the thickness of the resin coating is 0.5-20 ⁇ m.
  • the coated conductive substances include silver paste, copper paste, silver-coated copper paste, silver nanowire conductive ink, copper nanowire conductive ink, silver-coated copper nanowire conductive ink, and gold nanowire conductive ink , One or more of organic conductive polymer conductive inks; preferably silver paste and silver nanowire conductive inks.
  • the present invention also protects a method for preparing a printed circuit board, including the above-mentioned method for electroplating metal on the surface of an insulating base material.
  • a resin coating is firstly coated on the insulating base material, a resin with good compatibility with the insulating base material is selected, and after curing, a uniform resin coating with a tiny gap structure is formed on the surface of the insulating base material.
  • the layer has good adhesion on the insulating substrate, and then select the appropriate solid filler according to the selected resin, and then coat the conductive material on the resin coating, the conductive material is filled into the gap structure, and the metal is plated in the gap structure through electroplating.
  • These conductive substances are grown to fill the entire gap structure, so the electroplating layer has excellent adhesion on the insulating substrate.
  • the present invention completely avoids harmful substances used in chemical plating, avoids damage to human body and pollution to the environment, and is environmentally friendly.
  • resin is used as the intermediate layer of the conductive layer formed by the insulating base material and the conductive substance, and the electroplated metal layer with excellent adhesion on the base material can be obtained by growing and filling the metal in the tiny gap of the resin coating, Therefore, the types of insulating substrates used can be expanded to achieve wide application.
  • the method of direct electroplating on the surface of insulating substrates provided by the present invention can realize the metallization of most insulating substrates, and the electroplating layer on the insulating substrates has Excellent adhesion can effectively solve the current 5G technology requirements for low dielectric constant materials as conductive circuit substrates.
  • the present invention can select and use different resins according to different electroplating environments, such as resins with high temperature resistance, acid and alkali resistance, and low dielectric, so the operation range is wider, the weather resistance is stronger, and a wide range of applications can be realized.
  • FIG. 1 is a schematic diagram of a method for electroplating metal on the surface of an insulating substrate according to the present invention.
  • FIG. 2 is a SEM image of the resin coating on PET in Example 1.
  • FIG. 2 is a SEM image of the resin coating on PET in Example 1.
  • FIG. 3 is a SEM image of the silver nanowire conductive ink coated on the resin coating of PET in Example 1.
  • FIG. 4 is a topography diagram of the copper electroplating layer on PET in Example 1.
  • FIG. 4 is a topography diagram of the copper electroplating layer on PET in Example 1.
  • FIG. 5 is the XRD pattern of the copper electroplating layer on PET in Example 1.
  • FIG. 6 is a SEM image of a copper electroplating layer on PET in Example 1.
  • FIG. 7 is an adhesion test diagram of the copper electroplating layer on PET in Example 1.
  • FIG. 8 is a graph of the adhesion test of the electroplated copper layer on PTFE in Example 4.
  • FIG. 9 is a SEM image of the resin coating on PI in Example 7.
  • FIG. 9 is a SEM image of the resin coating on PI in Example 7.
  • FIG. 10 is a SEM image of the conductive silver paste coated on the resin coating of PI in Example 7.
  • FIG. 10 is a SEM image of the conductive silver paste coated on the resin coating of PI in Example 7.
  • FIG. 11 is an adhesion test chart of the electroplated copper layer on FR4 in Example 8.
  • FIG. 11 is an adhesion test chart of the electroplated copper layer on FR4 in Example 8.
  • FIG. 12 is an adhesion test diagram of the electroplated copper layer on the ceramic substrate in Example 10.
  • a schematic diagram of a method for electroplating metal on the surface of an insulating substrate as shown in FIG. 1 , the method for electroplating metal on the surface of an insulating substrate specifically includes the following steps:
  • the resin, the solvent, the curing agent and the solid filler are mixed uniformly in a certain proportion to prepare a resin coating; wherein, the resin coating includes the following components by mass percentage: resin: 10%-50%, solvent: 10%-50% , curing agent: 1%-10%, solid filler: 10-60%.
  • S3 Coat the conductive substance on the surface of the resin coating of S2.
  • the addition of the solid filler creates a gap between the resin molecules or between the resin molecule and the filler.
  • the conductive substance can penetrate into the gap structure on the surface of the coating.
  • a conductive film is formed on the surface of the resin coating, and the conductive substances in the conductive film are used as active sites for subsequent electroplating;
  • the silver nanowire conductive ink was purchased from Zhongke Smart Materials Co., Ltd.
  • the conductive silver paste was purchased from Dongguan Dongji Electronic Paste Co., Ltd.
  • a method for electroplating metal on a PET surface comprising the steps:
  • S1 Mix 20% polyurethane and 28% butanone, and stir at a rate of 1000 r/min under ultrasonic conditions, while mixing 20% ammonium polyphosphate and 28% butanone, and under ultrasonic conditions Stir at a rate of 1000 r/min. After 10 minutes, the two solutions are mixed and stirred at a rate of 1000 r/min under ultrasonic conditions. After the solution is fully dispersed, add 4% imidazole curing agent, and at 1500 r/min. Ultrasonic stirring was carried out at a speed of 100 °C, and the resin coating was obtained after fully dispersing.
  • S3 Use a 30# stainless steel wire rod to scrape the silver nanowire conductive ink on the resin coating in S2, place it in an oven at 150°C for 10 min, take it out, obtain a conductive film, and measure the surface square resistance with a four-probe instrument.
  • FIG. 2 is the SEM image of Example 1 after the resin coating is applied on the PET. It can be clearly seen from the SEM image that there are a large number of solid particles in the resin coating, and there are certain gaps between these particles.
  • Fig. 3 is the SEM image of the silver nanowire conductive ink coated on the resin coating of PET in Example 1. It can be clearly seen from the SEM image that the distribution of silver nanowires is relatively uniform, and most of the silver nanowires are embedded in the solid filler. in the gap between.
  • FIG. 4 is a topography diagram of the copper electroplating layer on PET obtained in step S4 of Example 1. It can be seen from the figure that the copper plating layer can evenly cover the PET surface and the plating layer is smooth and meticulous.
  • FIG. 4 is a topography diagram of the copper electroplating layer on PET obtained in step S4 of Example 1. It can be seen from the figure that the copper plating layer can evenly cover the PET surface and the plating layer is smooth and meticulous.
  • FIG. 5 is the XRD pattern of the copper electroplating layer on PET obtained in step S4 of Example 1. It can be seen from the XRD that the dominant crystal plane of the copper plating layer is the Cu(111) plane.
  • FIG. 6 is a SEM image of the copper electroplating layer on PET obtained in step S4 of Example 1. From the SEM image, it can be seen that the copper plating layer is fine and relatively flat, which fully illustrates the practicability of the present invention.
  • Fig. 7 is the adhesion test diagram of the electroplated copper layer on the PET obtained in step S4 of Example 1, that is, the apparent morphology after the 100-grid method test. It can be seen from the figure that after the 100-grid method test, there is no copper The coating was sticked off by 3M tape, which fully shows that the copper coating has good adhesion.
  • a method for electroplating metal on PI surface, the process steps of electroplating metal are the same as those in Example 1, that is, the resin coating formulation and process used in Example 2, coating process and electroplating formulation and process are the same as those in Example 1, except that S2 Among them, the insulating substrate used in Example 2 is PI.
  • a method of electroplating metal on the surface of FR4 the process steps of electroplating metal are the same as in Example 1, that is, the used coating formula and process, coating process and electroplating formula and process in Example 3 are the same as in Example 1, and the difference is that in S2. , the insulating base material used in Example 3 is FR4.
  • a method for electroplating metal on PTFE surface, the process steps of electroplating metal are the same as in Example 1, that is, the used coating formulation and process, coating process and electroplating formulation and process in Example 4 are the same as in Example 1, except that in S2 , the insulating substrate used in Example 4 is PTFE.
  • Figure 8 shows the appearance of the copper electroplating layer on PTFE in Example 4 after the 100-grid test. It can be seen from the figure that after the 100-grid test, a little of the copper coating was sticked off by the 3M tape, indicating that The copper coating still has some adhesion on the very low surface energy PTFE.
  • a method for electroplating metal on the surface of a ceramic substrate the process steps of electroplating metal are the same as those in Example 1, that is, the coating formulation and process, coating process and electroplating formulation and process used in Example 5 are the same as those in Example 1, except that S2 Among them, the insulating substrate used in Example 5 was a ceramic substrate.
  • Table 1 shows the test results of the surface resistance of the conductive film in step S3 of Examples 1-5 and the adhesion test and surface condition of the electroplated copper layer in step S4.
  • the adhesion test is divided into five grades: very good, good, general, poor, and poor. It can be obtained from the results in Table 1.
  • the technical means of the present invention can effectively realize the metallization of various insulating materials.
  • the conductive film with lower square resistance can be obtained by the layered layer, which can achieve rapid plating, and at the same time, the metal plating layer with excellent adhesion can be obtained by metal deposition and growth in the gap structure.
  • S3 Scratch the conductive silver paste on the resin coating in S2 with a 30-gauge stainless steel wire rod, place it in an oven at 150°C for 10 minutes, and take it out to obtain a conductive film, and measure the surface resistance with a four-probe instrument.
  • a method for electroplating metal on the PI surface, the process steps of electroplating metal are the same as in Example 6, that is, the used coating formula and process, coating process and electroplating formula and process in Example 7 are the same as in Example 6, except that in S2 , the insulating substrate used in Example 7 is PI.
  • FIG. 9 is the SEM image of the resin coating on PI in Example 7. It can be clearly seen from the SEM image that there are a large number of solid particles in the resin coating, and there are certain gaps between these particles.
  • Figure 10 is the SEM image of the conductive silver paste coated on the resin coating of PI in Example 7. It can be clearly seen from the SEM image that the distribution of the silver paste is relatively uniform, and the silver paste enters the gap between the fillers.
  • a method for electroplating metal on the surface of FR4 the process steps of electroplating metal are the same as in Example 6, that is, the used coating formula and process, coating process and electroplating formula and process in Example 8 are the same as in Example 6, and the difference is that in S2. , the insulating base material used in Example 8 is FR4.
  • Figure 11 is the adhesion test diagram of the electroplated copper layer on FR4 of Example 8, that is, the apparent morphology after the 100-grid method test. It can be seen from the figure that after the 100-grid method test, no copper plating layer is 3M The tape sticks off, which fully shows that the copper plating has good adhesion.
  • a method for electroplating metal on PTFE surface, the process steps of electroplating metal are the same as in Example 6, that is, the used coating formula and process, coating process and electroplating formula and process in Example 9 are the same as in Example 6, and the difference is that in S2.
  • the insulating substrate used in Example 9 is PTFE.
  • a method for electroplating metal on the surface of a ceramic substrate the process steps of electroplating metal are the same as those in Example 6, that is, the coating formulation and process, coating process, and electroplating formulation and process used in Example 10 are the same as those in Example 6, except that S2 Among them, the insulating substrate used in Example 10 was a ceramic substrate.
  • Figure 12 shows the appearance of the electroplated copper layer on the ceramic substrate of Example 10 after the 100-grid test. It can be seen from the figure that after the 100-grid test, only a small amount of the copper plating layer is stuck off by the 3M tape. It fully shows that the copper coating has good adhesion.
  • the adhesion test is divided into five grades: very good, good, general, poor, and poor. It can be obtained from the results in Table 2. If different resin coatings are selected, the technical means of the present invention can still effectively realize the metal of various insulating materials. By forming the coating of the gap structure, a conductive film with lower square resistance can be obtained, and rapid plating can be achieved, and at the same time, a metal coating with excellent adhesion can be obtained by depositing and growing metal in the gap structure.

Abstract

The present invention belongs to the technical field of electroplating, and a method for electroplating metal on an insulating substrate surface is disclosed. The method comprises the following steps: S1, mixing a resin, a solvent, a solid filler and a curing agent to prepare a coating paint; S2, coating the resin coating paint on an insulating substrate surface; after the insulating substrate is cured, forming a coating layer having fine gaps; S3, coating a conductive substance on the resin coating layer of S2, the conductive substance permeating into the gapped structure of the resin coating layer, then drying to form a conductive film; S4: placing the insulating substrate containing the conductive film of S3 in an electroplating solution for direct electroplating. In the present invention, a resin is used as an intermediate layer between an insulating substrate and a conductive layer formed by a conductive substance, and metal is grown and filled in fine gaps of the resin coating layer to obtain an electroplated metal layer that adheres well to the substrate. This expands the types of the insulating substrate that may be used, and thus allows for wide application.

Description

一种绝缘基材表面电镀金属的方法A kind of method for electroplating metal on the surface of insulating substrate 技术领域technical field
本发明属于电镀技术领域，具体涉及一种绝缘基材表面电镀金属的方法。The invention belongs to the technical field of electroplating, and particularly relates to a method for electroplating metal on the surface of an insulating base material.
背景技术Background technique
随着电子信息技术的快速发展，尤其是集成电路的工业化发展已成为衡量一个国家工业能力的重要参考，而在电子产品的制造过程中，需要使用到大量的绝缘材料，例如用作芯片的硅材料，印制电路板的环氧树脂增强玻璃纤维布和聚酰亚胺材料，这些绝缘基材大多起承载导电图形的作用，因此需要对这些绝缘基材进行金属化处理使其具有优秀的电气性能。目前使绝缘基材金属化的方法主要有两种，一种是采用压合的方式，即通过粘接剂将绝缘基材和金属在高温下压合，由于受到粘接强度和样品尺寸的限制，该方法的使用受到了很大的局限性；第二种方法是采用电沉积，即电镀，相比于直接压合，电镀具有受尺寸影响小，附着力佳及厚度可控等优势而得到广泛应用。但是，在电镀之前，需对绝缘基材表面进行处理使其具有一定的导电性。With the rapid development of electronic information technology, especially the industrialization of integrated circuits, it has become an important reference for measuring a country's industrial capacity. In the manufacturing process of electronic products, a large amount of insulating materials, such as silicon used for chips, need to be used. Materials, epoxy resin reinforced glass fiber cloth and polyimide materials for printed circuit boards, these insulating substrates mostly play the role of carrying conductive patterns, so these insulating substrates need to be metallized to make them have excellent electrical properties. performance. At present, there are two main methods for metallizing the insulating substrate. One is the pressing method, that is, the insulating substrate and the metal are pressed together at high temperature through an adhesive. Due to the limitation of the bonding strength and the size of the sample , the use of this method has been greatly limited; the second method is to use electrodeposition, that is, electroplating. Compared with direct pressing, electroplating has the advantages of less influence on size, good adhesion and controllable thickness. widely used. However, before electroplating, the surface of the insulating substrate needs to be treated to have a certain conductivity.
化学镀是最为传统的方法，虽然此种工艺较为成熟，但存在着许多难以克服的缺点，比如使用的还原剂通常为有毒的甲醛，对生产人员的生命健康造成威胁，另外镀液工艺复杂，镀液不稳定，增加了管控难度和成本，还有镀液中存在大量的络合剂，这些络合剂对环境污染较为严重，因此也增加了处理难度和处理成本，基于以上，研究人员进行了大量的取代化学镀的工艺研究。物理/化学气相沉积可以有效地避免化学镀所带来的环境问题，并且可以沉积上致密的金属层，是很有潜力取代化学镀的工艺，但是其高昂的设备造价及巨大的能耗问题让许多企业望而却步，另外沉积过程的非选择性也会对靶材造成较大的浪费。例如中国专利《一种半干法处理塑胶直接电镀真空镀膜***》(公开 号CN109402597A)中描述该镀膜设备所使用的辉光电源电压高达2500V，使用的溅射电源功率高达60kW，且不说设备成本，如此之大的能耗也会带来较大的附加成本。导电膜工艺是目前研究较多的用以取代化学镀的直接电镀工艺，通过表面处理将导电物质附着于绝缘基材上并形成一层均匀的薄膜，常见的用于形成导电膜的物质有碳黑、石墨烯以及有机导电高分子聚合物，碳黑与石墨烯由于是非极性物质，具有很强的憎水性，同时由于粒径较小也易于团聚，因此要保证能均匀地分散在水中，则需要加入大量的分散剂，但这样势必会降低导电性以及镀液的稳定性。中国专利《一种基于石墨烯成膜直接电镀线路板的方法》(公开号CN110351956A)和《一种直接电镀导电液及其制备方法》(公开号CN103103950A)中都描述了需要对溶液进行超声处理并且需要加入一定量的分散剂，这些处理不仅增加了工序同时存在电镀效率低的缺陷。有机导电聚合物作为导电膜的一般工艺是首先采用无机氧化物对绝缘基材进行处理，使之带上电荷，通过电荷吸附导电高分子使其成膜，此工艺一般都要求绝缘基材的一端有金属层(铜箔)，并且电镀的过程中必须要保证铜箔与镀液接触，使金属由铜箔处开始生长，如若不然，无论施加多大的电压都无法沉积金属，另外，由于有机导电聚合物的电阻都较大，会使金属的上镀速率较慢，极大地限制生产效率。例如中国专利《绝缘基材表面电镀金属的方法》(公开号CN108977862A)和《一种在绝缘基材上直接电镀的方法》(公开号CN107723764A)都采用了金属离子活化有机导电聚合物膜实现在绝缘基材上直接电镀的方法，其主要是缺陷是工序较为繁琐，需要调整、中和和活化等步骤，上铜速率较低并且都需要使用铜箔进行诱导沉积。Electroless plating is the most traditional method. Although this process is relatively mature, it has many shortcomings that are difficult to overcome. For example, the reducing agent used is usually toxic formaldehyde, which poses a threat to the life and health of production personnel. In addition, the plating solution process is complicated. The plating solution is unstable, which increases the difficulty and cost of management and control. There are also a large number of complexing agents in the plating solution. These complexing agents cause serious environmental pollution, which also increases the difficulty and cost of processing. Based on the above, the researchers carried out A large number of process researches to replace electroless plating. Physical/chemical vapor deposition can effectively avoid the environmental problems caused by electroless plating, and can deposit dense metal layers. It is a potential replacement for electroless plating, but its high equipment cost and huge energy consumption problems make Many companies are discouraged, and the non-selectivity of the deposition process will also cause a large waste of targets. For example, the Chinese patent "A Semi-dry Processing Plastic Direct Electroplating Vacuum Coating System" (Publication No. CN109402597A) describes that the voltage of the glow power supply used by the coating equipment is as high as 2500V, and the power of the sputtering power supply used is as high as 60kW, not to mention the equipment Cost, such a large energy consumption will also bring a large additional cost. The conductive film process is a direct electroplating process that has been widely studied to replace electroless plating. The conductive material is attached to the insulating substrate through surface treatment and forms a uniform film. The common material used to form the conductive film is carbon. Black, graphene and organic conductive polymers, carbon black and graphene have strong hydrophobicity because they are non-polar substances, and at the same time, they are easy to agglomerate due to their small particle size, so they must be uniformly dispersed in water. A large amount of dispersant needs to be added, but this will inevitably reduce the conductivity and the stability of the plating solution. Chinese patents "a method for direct electroplating circuit boards based on graphene film formation" (publication number CN110351956A) and "a direct electroplating conductive solution and its preparation method" (publication number CN103103950A) both describe the need for ultrasonic treatment of the solution And need to add a certain amount of dispersant, these treatments not only increase the process but also have the defect of low electroplating efficiency. The general process of organic conductive polymers as conductive films is to first use inorganic oxides to treat the insulating substrate to make it charged, and then adsorb the conductive polymer to form a film through the charge. This process generally requires one end of the insulating substrate. There is a metal layer (copper foil), and the copper foil must be in contact with the plating solution during the electroplating process, so that the metal starts to grow from the copper foil. Otherwise, no matter how much voltage is applied, the metal cannot be deposited. In addition, due to the organic conductivity Polymers have high electrical resistance, which will slow down the plating rate of metals and greatly limit production efficiency. For example, the Chinese patents "Method for Electroplating Metal on the Surface of Insulating Substrate" (Publication No. CN108977862A) and "A Method for Direct Electroplating on Insulating Substrate" (Publication No. CN107723764A) both use metal ion-activated organic conductive polymer films to achieve The main disadvantage of the method of direct electroplating on insulating substrates is that the process is cumbersome, and steps such as adjustment, neutralization and activation are required, the copper deposition rate is low, and copper foil is required for induced deposition.
另外，随着5G技术的实际应用，由于高频电磁波所携带的信号损失而带来的信号完整性问题也愈发严重，因此要求所使用低介电常数的绝缘基材，例如聚四氟乙烯(PTFE)，陶瓷基板等，但是这些材料具有极低的表面能，在其表面形成稳定、附着力佳和导电性好的导电层仍然是具有挑战性的难题。In addition, with the practical application of 5G technology, the signal integrity problem caused by the loss of signals carried by high-frequency electromagnetic waves is becoming more and more serious, so it is required to use low dielectric constant insulating substrates, such as PTFE. (PTFE), ceramic substrates, etc., but these materials have extremely low surface energy, and it is still a challenging problem to form a stable conductive layer with good adhesion and good conductivity on their surface.
发明内容SUMMARY OF THE INVENTION
本发明的目的在于针对背景技术存在的缺陷以及目前技术存在的挑战，尤其是对于低介电常数的绝缘基材金属化，本发明提供了一种全新的在树脂涂层上涂覆导电物质的方法，用于在绝缘基材表面形成导电膜，并且所形成的导电膜在绝缘基材上分布均匀，导电性佳，由于树脂的存在，导电膜在多数绝缘基材上都有着极佳的结合力。The purpose of the present invention is to address the defects of the background technology and the challenges of the current technology, especially for the metallization of the insulating base material with low dielectric constant, the present invention provides a brand-new method for coating conductive substances on the resin coating. The method is used to form a conductive film on the surface of the insulating substrate, and the formed conductive film is evenly distributed on the insulating substrate and has good conductivity. Due to the existence of the resin, the conductive film has an excellent bond on most insulating substrates. force.
为实现上述技术问题，本发明的技术方案是：For realizing the above-mentioned technical problems, the technical scheme of the present invention is:
一种用于绝缘基材表面电镀金属的方法，其特征在于，包括如下步骤：A method for electroplating metal on the surface of an insulating base material, comprising the steps of:
S1、将树脂、溶剂、固体填料、固化剂按一定比例混合均匀，配制得到树脂涂料；S1. Mix the resin, solvent, solid filler and curing agent uniformly in a certain proportion to prepare a resin coating;
S2、将S1中的树脂涂料涂覆于绝缘基材表面，固化后在绝缘基材表面形成均匀并且表面带有微小缝隙结构的树脂涂层；涂层表面的缝隙结构为树脂分子与树脂分子之间的缝隙结构、树脂分子与填料分子之间的缝隙结构。S2. Coat the resin coating in S1 on the surface of the insulating substrate, and after curing, form a uniform resin coating with a tiny gap structure on the surface of the insulating substrate; the gap structure on the surface of the coating is the difference between the resin molecules and the resin molecules. The gap structure between resin molecules and filler molecules.
S3、将导电物质涂覆于S2中的树脂涂层上，烘干后在树脂涂层表面形成均匀的导电膜，导电膜中的导电物质作为后续电镀的活性位点；S3, coating the conductive material on the resin coating in S2, and after drying, a uniform conductive film is formed on the surface of the resin coating, and the conductive material in the conductive film is used as the active site of subsequent electroplating;
S4、将经过S3处理后的覆有导电膜的绝缘基材置于电镀液中进行直接电镀。电镀工艺参数和电流类型不受限制，可以是任何类型的电镀参数。S4, placing the insulating substrate covered with the conductive film after being processed in S3 in an electroplating solution for direct electroplating. Plating process parameters and current types are not limited and can be any type of plating parameters.
在本发明的技术方案中，步骤S1中，树脂涂料中按质量百分数含量包括如下组分：树脂：10％-50％，溶剂：10％-50％，固化剂：1％-10％，固体填料：10-60％；In the technical solution of the present invention, in step S1, the resin coating includes the following components by mass percentage: resin: 10%-50%, solvent: 10%-50%, curing agent: 1%-10%, solid Filler: 10-60%;
优选的，步骤S1中，将树脂与溶剂混合，并充分分散得到树脂溶液，将固体填料与溶剂充分混合，并充分分散得到固体填料溶液；将树脂溶液和固体填料溶液混合并充分分散，然后加入固化剂，并充分分散，得到树脂涂料；Preferably, in step S1, the resin is mixed with the solvent, and fully dispersed to obtain a resin solution, the solid filler is fully mixed with the solvent, and fully dispersed to obtain a solid filler solution; the resin solution and the solid filler solution are mixed and fully dispersed, and then added curing agent, and fully dispersed to obtain resin coating;
优选的，步骤S1中，将树脂、固体填料与溶剂充分分散后得到混合溶液然后加入固化剂并充分分散得到树脂涂料。Preferably, in step S1, the resin, solid filler and solvent are fully dispersed to obtain a mixed solution, and then a curing agent is added and fully dispersed to obtain a resin coating.
在本发明的技术方案中，步骤S1中，树脂选自聚乙烯、聚丙烯、聚氯乙烯、聚苯乙烯、ABS树脂、聚酯、聚碳酸酯、聚氨酯、聚酰胺、聚酰亚胺、丙烯酸树脂、环氧树脂、酚醛树脂、UV树脂、PTFE树脂、聚芳醚腈树脂中的一种或几种；优选为聚氨酯、聚酯和UV树脂。In the technical solution of the present invention, in step S1, the resin is selected from polyethylene, polypropylene, polyvinyl chloride, polystyrene, ABS resin, polyester, polycarbonate, polyurethane, polyamide, polyimide, acrylic One or more of resin, epoxy resin, phenolic resin, UV resin, PTFE resin, polyarylene ether nitrile resin; preferably polyurethane, polyester and UV resin.
在本发明的技术方案中，步骤S1中，溶剂选自水、乙醇、异丙醇、***、甲苯、戊烷、环己烷、丙酮、丁酮、乙酯、乙酸乙酯、N,N-二甲基甲酰胺、N-甲基吡咯烷酮、四氢呋喃等中的一种或几种；优选为乙酸乙酯和丁酮。In the technical solution of the present invention, in step S1, the solvent is selected from water, ethanol, isopropanol, diethyl ether, toluene, pentane, cyclohexane, acetone, methyl ethyl ketone, ethyl ester, ethyl acetate, N,N- One or more of dimethylformamide, N-methylpyrrolidone, tetrahydrofuran, etc.; preferably ethyl acetate and butanone.
在本发明的技术方案中，步骤S1中，固化剂选自多异氰酸酯、酸酐、有机胺、聚氨酯和咪唑类固化剂中的一种或几种；优选为多异氰酸酯和咪唑类固化剂。In the technical solution of the present invention, in step S1, the curing agent is selected from one or more of polyisocyanates, acid anhydrides, organic amines, polyurethanes and imidazole curing agents; preferably polyisocyanates and imidazole curing agents.
在本发明的技术方案中，步骤S1中，固体填料选自二氧化硅、石墨、石墨烯、二氧化钛、氢氧化铝、氢氧化镁、氧化镁、三氧化二铝、氮化硼、磷酸铵、尿素、三苯、三苯基膦、三聚氰胺、三聚氰胺衍生物、聚磷酸铵、磷酸二氢铵、磷酸氢二铵和次膦酸盐中的一种或几种，所述固体填料的直径为0.1-100μm；优选为三聚氰胺和聚磷酸铵，直径为1-10μm。In the technical solution of the present invention, in step S1, the solid filler is selected from silicon dioxide, graphite, graphene, titanium dioxide, aluminum hydroxide, magnesium hydroxide, magnesium oxide, aluminum oxide, boron nitride, ammonium phosphate, One or more of urea, triphenyl, triphenylphosphine, melamine, melamine derivatives, ammonium polyphosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate and phosphinate, the diameter of the solid filler is 0.1 -100 μm; preferably melamine and ammonium polyphosphate, 1-10 μm in diameter.
在本发明的技术方案中，步骤S2中，绝缘基材为不同材料的平面基材或异形基材；In the technical solution of the present invention, in step S2, the insulating base material is a plane base material or a special-shaped base material of different materials;
优选的，所述绝缘基材选自环氧树脂增强玻璃纤维布、无纺布、玻璃纤维布、陶瓷、硅、木制基材、有机聚合物薄膜中的一种；Preferably, the insulating base material is selected from epoxy resin reinforced glass fiber cloth, non-woven fabric, glass fiber cloth, ceramics, silicon, wood base material, and organic polymer film;
优选的，所述有机聚合物薄膜包括聚乙烯，聚丙烯，聚酰亚胺，聚氨酯，聚酯，聚碳酸酯。Preferably, the organic polymer film includes polyethylene, polypropylene, polyimide, polyurethane, polyester, and polycarbonate.
在本发明的技术方案中，步骤S3中，涂覆工艺包括刮涂、旋涂、浸涂、喷涂、微凹版印刷、狭缝挤压和丝网印刷中的一种或几种，烘干温度为60℃-300℃，树脂涂层厚度为0.5-20μm。In the technical solution of the present invention, in step S3, the coating process includes one or more of blade coating, spin coating, dip coating, spray coating, microgravure printing, slit extrusion and screen printing, and the drying temperature The temperature is 60℃-300℃, and the thickness of the resin coating is 0.5-20μm.
在本发明的技术方案中，涂覆的导电物质包括银浆、铜浆、银包铜浆、银 纳米线导电油墨、铜纳米线导电油墨、银包铜纳米线导电油墨、金纳米线导电油墨、有机导电高分子导电油墨中的一种或几种；优选为银浆和银纳米线导电油墨。In the technical solution of the present invention, the coated conductive substances include silver paste, copper paste, silver-coated copper paste, silver nanowire conductive ink, copper nanowire conductive ink, silver-coated copper nanowire conductive ink, and gold nanowire conductive ink , One or more of organic conductive polymer conductive inks; preferably silver paste and silver nanowire conductive inks.
本发明还保护一种印制线路板的制备方法，包括上述的绝缘基材表面电镀金属的方法。The present invention also protects a method for preparing a printed circuit board, including the above-mentioned method for electroplating metal on the surface of an insulating base material.
本发明绝缘基材表面电镀金属的方法的发明构思如下：The inventive concept of the method for electroplating metal on the surface of an insulating substrate of the present invention is as follows:
本发明首先在绝缘基材上涂覆树脂涂料，选择与绝缘基材相容性很好的树脂，固化后在绝缘基材表面形成均匀并且表面带有微小缝隙结构的树脂涂层，该树脂涂层在绝缘基材上有很好的附着力，再根据所选用的树脂选择恰当的固体填料，再将导电物质涂覆于树脂涂层上，导电物质填入缝隙结构中，通过电镀使金属在这些导电物质上生长从而填满整个缝隙结构，因此电镀层在绝缘基材上具有极佳的附着力。In the present invention, a resin coating is firstly coated on the insulating base material, a resin with good compatibility with the insulating base material is selected, and after curing, a uniform resin coating with a tiny gap structure is formed on the surface of the insulating base material. The layer has good adhesion on the insulating substrate, and then select the appropriate solid filler according to the selected resin, and then coat the conductive material on the resin coating, the conductive material is filled into the gap structure, and the metal is plated in the gap structure through electroplating. These conductive substances are grown to fill the entire gap structure, so the electroplating layer has excellent adhesion on the insulating substrate.
与现有技术相比，本发明的有益效果为：Compared with the prior art, the beneficial effects of the present invention are:
1、本发明完全避免了化学镀中使用的有害物质，避免了对人体的伤害和对环境的污染，绿色环保。1. The present invention completely avoids harmful substances used in chemical plating, avoids damage to human body and pollution to the environment, and is environmentally friendly.
2、本发明使用树脂作为绝缘基材和导电物质形成的导电层的中间层，并且通过在树脂涂层微小缝隙中生长并填满金属可以得到在基材上附着力极佳的电镀金属层，因此可扩展所使用的绝缘基材种类，实现广泛应用，本发明所提供的在绝缘基材表面直接电镀的方法可实现绝大多数绝缘基材的金属化，并且电镀层在绝缘基材上有着极佳的附着力，能有效解决目前5G技术对低介电常数材料作为导电线路基材的要求。2. In the present invention, resin is used as the intermediate layer of the conductive layer formed by the insulating base material and the conductive substance, and the electroplated metal layer with excellent adhesion on the base material can be obtained by growing and filling the metal in the tiny gap of the resin coating, Therefore, the types of insulating substrates used can be expanded to achieve wide application. The method of direct electroplating on the surface of insulating substrates provided by the present invention can realize the metallization of most insulating substrates, and the electroplating layer on the insulating substrates has Excellent adhesion can effectively solve the current 5G technology requirements for low dielectric constant materials as conductive circuit substrates.
3、本发明可根据不同的电镀环境选择使用不同的树脂，例如耐高温，耐酸碱，低介电的树脂，因此操作范围更广，耐候性更强，可实现广泛应用。3. The present invention can select and use different resins according to different electroplating environments, such as resins with high temperature resistance, acid and alkali resistance, and low dielectric, so the operation range is wider, the weather resistance is stronger, and a wide range of applications can be realized.
附图说明Description of drawings
图1为本发明绝缘基材表面电镀金属的方法的示意图。FIG. 1 is a schematic diagram of a method for electroplating metal on the surface of an insulating substrate according to the present invention.
图2为实施例1在PET上涂覆树脂涂层的SEM图。FIG. 2 is a SEM image of the resin coating on PET in Example 1. FIG.
图3为实施例1在PET的树脂涂层上涂覆银纳米线导电油墨的SEM图。FIG. 3 is a SEM image of the silver nanowire conductive ink coated on the resin coating of PET in Example 1. FIG.
图4为实施例1在PET上电镀铜层的表观形貌图。FIG. 4 is a topography diagram of the copper electroplating layer on PET in Example 1. FIG.
图5为实施例1在PET上电镀铜层的XRD图。FIG. 5 is the XRD pattern of the copper electroplating layer on PET in Example 1. FIG.
图6为实施例1在PET上电镀铜层的SEM图。FIG. 6 is a SEM image of a copper electroplating layer on PET in Example 1. FIG.
图7为实施例1在PET上电镀铜层的附着力测试图。FIG. 7 is an adhesion test diagram of the copper electroplating layer on PET in Example 1. FIG.
图8为实施例4在PTFE上电镀铜层的附着力测试图。FIG. 8 is a graph of the adhesion test of the electroplated copper layer on PTFE in Example 4. FIG.
图9为实施例7在PI上涂覆树脂涂层的SEM图。FIG. 9 is a SEM image of the resin coating on PI in Example 7. FIG.
图10为实施例7在PI的树脂涂层上涂覆导电银浆的SEM图。FIG. 10 is a SEM image of the conductive silver paste coated on the resin coating of PI in Example 7. FIG.
图11为实施例8在FR4上电镀铜层的附着力测试图。FIG. 11 is an adhesion test chart of the electroplated copper layer on FR4 in Example 8. FIG.
图12为实施例10在陶瓷基板上电镀铜层的附着力测试图。FIG. 12 is an adhesion test diagram of the electroplated copper layer on the ceramic substrate in Example 10. FIG.
具体实施方式Detailed ways
下面结合实施例，对本发明作进一步地详细说明，但本发明的实施方式不限于此。The present invention will be further described in detail below with reference to the examples, but the embodiments of the present invention are not limited thereto.
需要说明的是以下实施案例的目的在于让此领域内的人士能够了解本发明的内容并据以实施，并不能以此限制本发明的保护范围，凡根据本发明精神实质所作的等效变化或修饰，都应涵盖在本发明的保护范围之内。It should be noted that the purpose of the following implementation cases is to allow those in the field to understand the content of the present invention and implement it accordingly, and cannot limit the protection scope of the present invention by this. Any equivalent changes made according to the spirit of the present invention or Modifications should be included within the protection scope of the present invention.
下述实施例中，绝缘基材表面电镀金属的方法的示意图，如图1所示，绝缘基材表面电镀金属的方法，具体包括如下步骤：In the following embodiments, a schematic diagram of a method for electroplating metal on the surface of an insulating substrate, as shown in FIG. 1 , the method for electroplating metal on the surface of an insulating substrate specifically includes the following steps:
S1：树脂涂料的配制：S1: Formulation of resin coating:
将树脂、溶剂、固化剂、固体填料按一定比例混合均匀，配制得到树脂涂料；其中，树脂涂料中按质量百分数含量包括如下组分：树脂：10％-50％，溶剂：10％-50％，固化剂：1％-10％，固体填料：10-60％。The resin, the solvent, the curing agent and the solid filler are mixed uniformly in a certain proportion to prepare a resin coating; wherein, the resin coating includes the following components by mass percentage: resin: 10%-50%, solvent: 10%-50% , curing agent: 1%-10%, solid filler: 10-60%.
S2：将S1中的树脂涂料覆于绝缘基材表面，固化后在绝缘基材表面形成 均匀并且表面带有微小缝隙的树脂涂层；S2: The resin coating in S1 is coated on the surface of the insulating substrate, and after curing, a uniform resin coating with tiny gaps on the surface is formed on the surface of the insulating substrate;
S3：将导电物质涂覆于S2的树脂涂层表面，固体填料的加入使树脂分子之间或者树脂分子与填料之间产生缝隙，导电物质可渗入涂层表面的缝隙结构中，烘干后在树脂涂层表面形成导电膜，导电膜中的导电物质作为后续电镀的活性位点；S3: Coat the conductive substance on the surface of the resin coating of S2. The addition of the solid filler creates a gap between the resin molecules or between the resin molecule and the filler. The conductive substance can penetrate into the gap structure on the surface of the coating. A conductive film is formed on the surface of the resin coating, and the conductive substances in the conductive film are used as active sites for subsequent electroplating;
S4：将S3得到的覆有导电膜的绝缘基材置于电镀液中进行直接电镀形成电镀层。S4: placing the insulating base material covered with the conductive film obtained in S3 in an electroplating solution for direct electroplating to form an electroplating layer.
下面结合附图和实施例，详述本发明的技术方案。The technical solutions of the present invention will be described in detail below with reference to the accompanying drawings and embodiments.
下述实施例中，银纳米线导电油墨购买于中科思莫特材料有限公司，导电银浆购买于东莞市东济电子浆料有限公司。In the following examples, the silver nanowire conductive ink was purchased from Zhongke Smart Materials Co., Ltd., and the conductive silver paste was purchased from Dongguan Dongji Electronic Paste Co., Ltd.
实施例1：Example 1:
一种PET表面电镀金属的方法，包括如下步骤：A method for electroplating metal on a PET surface, comprising the steps:
S1：将20％的聚氨酯和28％的丁酮混合，并在超声条件下以1000r/min的速率进行搅拌，同时将20％的聚磷酸铵与28％的丁酮混合，并在超声条件下以1000r/min的速率进行搅拌，10min后将这两种溶液混合并在超声条件下以1000r/min的速率进行搅拌，待溶液充分分散后加入4％的咪唑类固化剂，并以1500r/min的速率进行超声搅拌，充分分散后得到树脂涂料。S1: Mix 20% polyurethane and 28% butanone, and stir at a rate of 1000 r/min under ultrasonic conditions, while mixing 20% ammonium polyphosphate and 28% butanone, and under ultrasonic conditions Stir at a rate of 1000 r/min. After 10 minutes, the two solutions are mixed and stirred at a rate of 1000 r/min under ultrasonic conditions. After the solution is fully dispersed, add 4% imidazole curing agent, and at 1500 r/min. Ultrasonic stirring was carried out at a speed of 100 °C, and the resin coating was obtained after fully dispersing.
S2：采用90号不锈钢线棒将S1中的树脂涂料刮涂于整洁的A4样PET表面，置于150℃的烘箱中10min后取出，得到树脂涂层，采用扫描电子显微镜观测涂层形貌。S2: The resin coating in S1 was scraped on the clean A4-like PET surface with a 90-gauge stainless steel wire rod, placed in an oven at 150 °C for 10 min, and then taken out to obtain the resin coating, and the morphology of the coating was observed with a scanning electron microscope.
S3：采用30号不锈钢线棒将银纳米线导电油墨刮涂于S2中的树脂涂层上，置于150℃的烘箱中10min后取出，得到导电膜，采用四探针仪测量表面方阻。S3: Use a 30# stainless steel wire rod to scrape the silver nanowire conductive ink on the resin coating in S2, place it in an oven at 150°C for 10 min, take it out, obtain a conductive film, and measure the surface square resistance with a four-probe instrument.
S4：把S3中经过处理的PET裁取为15cm×5cm的尺寸，然后直接置于电镀铜镀液中进行直接电镀。具体过程为PET直接连上直流电源的阴极，阳极 为磷铜板，电镀液总体积为1.5L，电镀槽体为电镀专用哈林槽，电镀液的配方为130g/LCuSO 4·5H 2O+60g/LH 2SO 4，电镀条件为室温，电镀参数为2A/dm 2电镀10min，电镀结束后取出PET用清水冲洗后吹干，得到铜镀层，另外，为了测试镀层在绝缘基材上的附着力，采用百格法(3M胶带)进行粘贴实验。 S4: Cut the PET treated in S3 into a size of 15cm×5cm, and then directly place it in an electroplating copper plating solution for direct electroplating. The specific process is that the PET is directly connected to the cathode of the DC power supply, the anode is a phosphor copper plate, the total volume of the electroplating solution is 1.5L, the electroplating tank is a special Harlem tank for electroplating, and the formula of the electroplating solution is 130g/LCuSO 4 ·5H 2 O+60g /LH 2 SO 4 , the electroplating condition is room temperature, the electroplating parameter is 2A/dm 2 electroplating for 10min, after the electroplating, take out the PET, rinse it with clean water and blow it dry to obtain the copper coating. In addition, in order to test the adhesion of the coating on the insulating substrate , using the 100 grid method (3M tape) to carry out the sticking experiment.
图2为实施例1在PET上涂覆树脂涂层后的的SEM图，从SEM图中可以明显看到树脂涂层中存在大量的固体颗粒，并且这些颗粒之间存在一定的间隙。图3为实施例1中在PET的树脂涂层上涂覆银纳米线导电油墨的SEM图，从SEM图中可以明显看到银纳米线的分布较为均匀，并且多数银纳米线入到固体填料之间的缝隙中。图4为实施例1步骤S4得到的在PET上电镀铜层的表观形貌图，从图中可以看出铜镀层可均匀覆盖PET表面并且镀层平整细致。图5为实施例1步骤S4得到的在PET上电镀铜层的XRD图，从XRD看出镀铜层的优势晶面为Cu(111)面。图6为实施例1步骤S4得到的在PET上电镀铜层的SEM图，从SEM图可以看出镀铜层细致并且较为平整，充分说明了本发明的可实施性。图7为实施例1步骤S4得到的在PET上的电镀铜层附着力测试图，即经过百格法测试后的表观形貌，从图中可以看出经过百格法测试后，没有铜镀层被3M胶带粘掉，充分说明了铜镀层有很好的附着力。FIG. 2 is the SEM image of Example 1 after the resin coating is applied on the PET. It can be clearly seen from the SEM image that there are a large number of solid particles in the resin coating, and there are certain gaps between these particles. Fig. 3 is the SEM image of the silver nanowire conductive ink coated on the resin coating of PET in Example 1. It can be clearly seen from the SEM image that the distribution of silver nanowires is relatively uniform, and most of the silver nanowires are embedded in the solid filler. in the gap between. FIG. 4 is a topography diagram of the copper electroplating layer on PET obtained in step S4 of Example 1. It can be seen from the figure that the copper plating layer can evenly cover the PET surface and the plating layer is smooth and meticulous. FIG. 5 is the XRD pattern of the copper electroplating layer on PET obtained in step S4 of Example 1. It can be seen from the XRD that the dominant crystal plane of the copper plating layer is the Cu(111) plane. FIG. 6 is a SEM image of the copper electroplating layer on PET obtained in step S4 of Example 1. From the SEM image, it can be seen that the copper plating layer is fine and relatively flat, which fully illustrates the practicability of the present invention. Fig. 7 is the adhesion test diagram of the electroplated copper layer on the PET obtained in step S4 of Example 1, that is, the apparent morphology after the 100-grid method test. It can be seen from the figure that after the 100-grid method test, there is no copper The coating was sticked off by 3M tape, which fully shows that the copper coating has good adhesion.
实施例2：Example 2:
一种PI表面电镀金属的方法，电镀金属的工艺步骤和实施例1相同，即实施例2所用的树脂涂料配方及工艺、涂覆工艺以及电镀配方与工艺与实施例1相同，不同的是S2中，实施例2所用的绝缘基材是PI。A method for electroplating metal on PI surface, the process steps of electroplating metal are the same as those in Example 1, that is, the resin coating formulation and process used in Example 2, coating process and electroplating formulation and process are the same as those in Example 1, except that S2 Among them, the insulating substrate used in Example 2 is PI.
实施例3：Example 3:
一种FR4表面电镀金属的方法，电镀金属的工艺步骤和实施例1相同，即实施例3所用的涂料配方及工艺、涂覆工艺以及电镀配方与工艺与实施例1相同，不同的是S2中，实施例3所用的绝缘基材是FR4。A method of electroplating metal on the surface of FR4, the process steps of electroplating metal are the same as in Example 1, that is, the used coating formula and process, coating process and electroplating formula and process in Example 3 are the same as in Example 1, and the difference is that in S2. , the insulating base material used in Example 3 is FR4.
实施例4：Example 4:
一种PTFE表面电镀金属的方法，电镀金属的工艺步骤和实施例1相同，即实施例4所用的涂料配方及工艺、涂覆工艺以及电镀配方与工艺与实施例1相同，不同的是S2中，实施例4所用的绝缘基材是PTFE。A method for electroplating metal on PTFE surface, the process steps of electroplating metal are the same as in Example 1, that is, the used coating formulation and process, coating process and electroplating formulation and process in Example 4 are the same as in Example 1, except that in S2 , the insulating substrate used in Example 4 is PTFE.
图8为实施例4在PTFE上的电镀铜层经过百格法测试后的表观形貌，从图中可以看出经过百格法测试后，有少许铜镀层被3M胶带粘掉，说明了铜镀层在极低表面能的PTFE上仍有一定的附着力。Figure 8 shows the appearance of the copper electroplating layer on PTFE in Example 4 after the 100-grid test. It can be seen from the figure that after the 100-grid test, a little of the copper coating was sticked off by the 3M tape, indicating that The copper coating still has some adhesion on the very low surface energy PTFE.
实施例5：Example 5:
一种陶瓷基板表面电镀金属的方法，电镀金属的工艺步骤和实施例1相同，即实施例5所用的涂料配方及工艺、涂覆工艺以及电镀配方与工艺与实施例1相同，不同的是S2中，实施例5所用的绝缘基材是陶瓷基板。A method for electroplating metal on the surface of a ceramic substrate, the process steps of electroplating metal are the same as those in Example 1, that is, the coating formulation and process, coating process and electroplating formulation and process used in Example 5 are the same as those in Example 1, except that S2 Among them, the insulating substrate used in Example 5 was a ceramic substrate.
实施例1-5步骤S3中的导电膜表面方阻测试结果及步骤S4中电镀铜层的附着力测试及表面情况见表1。Table 1 shows the test results of the surface resistance of the conductive film in step S3 of Examples 1-5 and the adhesion test and surface condition of the electroplated copper layer in step S4.
表1 实施例1-5导电膜表面方阻、电镀铜层表面情况及附着力测试Table 1 Example 1-5 Conductive film surface resistance, surface condition of electroplated copper layer and adhesion test
Figure PCTCN2020140888-appb-000001
Figure PCTCN2020140888-appb-000001
附着力测试分为很好、好、一般、较差、差5个等级，从表1的结果可以得到，采用本发明技术手段能够有效实现各种绝缘材料的金属化，采用具有缝隙结构的涂层能够得到较低方阻的导电膜，实现快速上镀，同时通过金属在缝隙结构中沉积并生长获得附着力极佳的金属镀层。The adhesion test is divided into five grades: very good, good, general, poor, and poor. It can be obtained from the results in Table 1. The technical means of the present invention can effectively realize the metallization of various insulating materials. The conductive film with lower square resistance can be obtained by the layered layer, which can achieve rapid plating, and at the same time, the metal plating layer with excellent adhesion can be obtained by metal deposition and growth in the gap structure.
实施例6：Example 6:
S1：将30％的聚酯和10％的乙酸乙酯混合，并在超声条件下以1000r/min的速率进行搅拌，同时将20％的三聚氰胺、28％的乙酸乙酯混、10％的UV树脂混合，并在超声条件下以1500r/min的速率进行搅拌，10min后将这两种溶液混合并在超声条件下以1000r/min的速率进行搅拌，待溶液充分分散后加入2％的多异氰酸酯，并以1500r/min的速率进行超声搅拌，充分分散后得到树脂涂料。S1: Mix 30% polyester and 10% ethyl acetate, and stir at a rate of 1000 r/min under ultrasonic conditions, while mixing 20% melamine, 28% ethyl acetate, 10% UV The resin was mixed and stirred at a rate of 1500r/min under ultrasonic conditions. After 10 minutes, the two solutions were mixed and stirred at a rate of 1000r/min under ultrasonic conditions. After the solution was fully dispersed, 2% polyisocyanate was added. , and ultrasonically stirred at a rate of 1500 r/min to obtain a resin coating after fully dispersing.
S2：采用60号不锈钢线棒将S1中的树脂涂料刮涂于整洁的A4样PET表面，置于150℃的紫外烘箱中10min后取出，得到树脂涂层，采用扫描电子显微镜观测涂层形貌。S2: The resin coating in S1 was scraped on the clean A4-like PET surface with a 60-gauge stainless steel wire rod, placed in a UV oven at 150 °C for 10 min, and then taken out to obtain the resin coating, and the coating morphology was observed by scanning electron microscope. .
S3：采用30号不锈钢线棒将导电银浆刮涂于S2中的树脂涂层上，置于150℃的烘箱中10min后取出，得到导电膜，采用四探针仪测量表面方阻。S3: Scratch the conductive silver paste on the resin coating in S2 with a 30-gauge stainless steel wire rod, place it in an oven at 150°C for 10 minutes, and take it out to obtain a conductive film, and measure the surface resistance with a four-probe instrument.
S4：把S3中经过处理的PET裁取为15cm×5cm的尺寸，然后直接置于电镀铜镀液中进行直接电镀。具体过程为PET直接连上直流电源的阴极，阳极为磷铜板，电镀液总体积为1.5L，电镀槽体为电镀专用哈林槽，电镀液的配方为130g/LCuSO 4·5H 2O+60g/LH 2SO 4，电镀条件为室温，电镀参数为2A/dm 2电镀10min，电镀结束后取出PET用清水冲洗后吹干，得到铜镀层，另外，为了测试镀层在绝缘基材上的附着力，采用百格法(3M胶带)进行粘贴实验。 S4: Cut the PET treated in S3 into a size of 15cm×5cm, and then directly place it in an electroplating copper plating solution for direct electroplating. The specific process is that the PET is directly connected to the cathode of the DC power supply, the anode is a phosphor copper plate, the total volume of the electroplating solution is 1.5L, the electroplating tank is a special Harlem tank for electroplating, and the formula of the electroplating solution is 130g/LCuSO 4 ·5H 2 O+60g /LH 2 SO 4 , the electroplating condition is room temperature, the electroplating parameter is 2A/dm 2 electroplating for 10min, after the electroplating, take out the PET, rinse it with clean water and blow it dry to obtain the copper coating. In addition, in order to test the adhesion of the coating on the insulating substrate , using the 100 grid method (3M tape) to carry out the sticking experiment.
实施例7：Example 7:
一种PI表面电镀金属的方法，电镀金属的工艺步骤和实施例6相同，即实施例7所用的涂料配方及工艺、涂覆工艺以及电镀配方与工艺与实施例6相同，不同的是S2中，实施例7所用的绝缘基材是PI。A method for electroplating metal on the PI surface, the process steps of electroplating metal are the same as in Example 6, that is, the used coating formula and process, coating process and electroplating formula and process in Example 7 are the same as in Example 6, except that in S2 , the insulating substrate used in Example 7 is PI.
图9为实施例7在PI上涂覆树脂涂层的SEM图，从SEM图中可以明显看到树脂涂层中存在大量的固体颗粒，并且这些颗粒之间存在一定的间隙。图 10为实施例7中在PI的树脂涂层上涂覆导电银浆的SEM图，从SEM图中可以明显看到银浆的分布较为均匀，并且银浆入到填料之间的缝隙中。FIG. 9 is the SEM image of the resin coating on PI in Example 7. It can be clearly seen from the SEM image that there are a large number of solid particles in the resin coating, and there are certain gaps between these particles. Figure 10 is the SEM image of the conductive silver paste coated on the resin coating of PI in Example 7. It can be clearly seen from the SEM image that the distribution of the silver paste is relatively uniform, and the silver paste enters the gap between the fillers.
实施例8：Example 8:
一种FR4表面电镀金属的方法，电镀金属的工艺步骤和实施例6相同，即实施例8所用的涂料配方及工艺、涂覆工艺以及电镀配方与工艺与实施例6相同，不同的是S2中，实施例8所用的绝缘基材是FR4。A method for electroplating metal on the surface of FR4, the process steps of electroplating metal are the same as in Example 6, that is, the used coating formula and process, coating process and electroplating formula and process in Example 8 are the same as in Example 6, and the difference is that in S2. , the insulating base material used in Example 8 is FR4.
图11为实施例8在FR4上的电镀铜层的附着力测试图，即经过百格法测试后的表观形貌，从图中可以看出经过百格法测试后，没有铜镀层被3M胶带粘掉，充分说明了铜镀层有很好的附着力。Figure 11 is the adhesion test diagram of the electroplated copper layer on FR4 of Example 8, that is, the apparent morphology after the 100-grid method test. It can be seen from the figure that after the 100-grid method test, no copper plating layer is 3M The tape sticks off, which fully shows that the copper plating has good adhesion.
实施例9：Example 9:
一种PTFE表面电镀金属的方法，电镀金属的工艺步骤和实施例6相同，即实施例9所用的涂料配方及工艺、涂覆工艺以及电镀配方与工艺与实施例6相同，不同的是S2中，实施例9所用的绝缘基材是PTFE。A method for electroplating metal on PTFE surface, the process steps of electroplating metal are the same as in Example 6, that is, the used coating formula and process, coating process and electroplating formula and process in Example 9 are the same as in Example 6, and the difference is that in S2. , the insulating substrate used in Example 9 is PTFE.
实施例10：Example 10:
一种陶瓷基板表面电镀金属的方法，电镀金属的工艺步骤和实施例6相同，即实施例10所用的涂料配方及工艺、涂覆工艺以及电镀配方与工艺与实施例6相同，不同的是S2中，实施例10所用的绝缘基材是陶瓷基板。A method for electroplating metal on the surface of a ceramic substrate, the process steps of electroplating metal are the same as those in Example 6, that is, the coating formulation and process, coating process, and electroplating formulation and process used in Example 10 are the same as those in Example 6, except that S2 Among them, the insulating substrate used in Example 10 was a ceramic substrate.
图12为实施例10在陶瓷基板上的电镀铜层经过百格法测试后的表观形貌，从图中可以看出经过百格法测试后，仅有少量铜镀层被3M胶带粘掉，充分说明了铜镀层有很好的附着力。Figure 12 shows the appearance of the electroplated copper layer on the ceramic substrate of Example 10 after the 100-grid test. It can be seen from the figure that after the 100-grid test, only a small amount of the copper plating layer is stuck off by the 3M tape. It fully shows that the copper coating has good adhesion.
实施例6-10步骤S3中的导电膜表面方阻测试结果及S4中电镀铜层的附着力测试及表面情况见表1。Examples 6-10 The results of the square resistance test on the surface of the conductive film in step S3 and the adhesion test and surface condition of the electroplated copper layer in S4 are shown in Table 1.
表2 实施例6-10导电膜表面方阻、电镀铜层表面情况及附着力测试Table 2 Example 6-10 Conductive film surface resistance, surface condition of electroplated copper layer and adhesion test
Figure PCTCN2020140888-appb-000002
Figure PCTCN2020140888-appb-000002
Figure PCTCN2020140888-appb-000003
Figure PCTCN2020140888-appb-000003
附着力测试分为很好、好、一般、较差、差5个等级，从表2的结果可以得到，选择不同的树脂涂层，采用本发明技术手段仍然能够有效实现各种绝缘材料的金属化，通过形成缝隙结构的涂层能够得到较低方阻的导电膜，实现快速上镀，同时通过金属在缝隙结构中沉积并生长获得附着力极佳的金属镀层。The adhesion test is divided into five grades: very good, good, general, poor, and poor. It can be obtained from the results in Table 2. If different resin coatings are selected, the technical means of the present invention can still effectively realize the metal of various insulating materials. By forming the coating of the gap structure, a conductive film with lower square resistance can be obtained, and rapid plating can be achieved, and at the same time, a metal coating with excellent adhesion can be obtained by depositing and growing metal in the gap structure.
表1和表2的结果充分说明了本技术方案的可行性以及广阔的实用性，能有效解决目前电镀领域的关键卡脖子难题。另外，上述实施例只为说明本发明的技术构思和特点，其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施，并不能以此限制本发明的保护范围，凡根据本发明精神实质所作的等效变化或修饰，都应涵盖在本发明的保护范围之内。The results in Tables 1 and 2 fully demonstrate the feasibility and broad practicability of this technical solution, which can effectively solve the key problem of neck-stuck in the current electroplating field. In addition, the above-mentioned embodiments are only intended to illustrate the technical concept and characteristics of the present invention, and their purpose is to enable those who are familiar with the art to understand the content of the present invention and implement it accordingly, and cannot limit the protection scope of the present invention by this. Equivalent changes or modifications made in the spirit of the present invention should be included within the protection scope of the present invention.
上述实施例只为说明本发明的技术构思和特点，其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施，并不能以此限制本发明的保护范围，凡根据本发明精神实质所作的等效变化或修饰，都应涵盖在本发明的保护范围之内。The above-mentioned embodiments are only to illustrate the technical concept and characteristics of the present invention, and their purpose is to enable those who are familiar with the art to understand the content of the present invention and implement it accordingly, and cannot limit the scope of protection of the present invention with this. Equivalent changes or modifications made in the spirit and spirit should all be included within the protection scope of the present invention.
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受所述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。The above-mentioned embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited by the described embodiments, and any other changes, modifications, substitutions, and combinations made without departing from the spirit and principle of the present invention , simplification, all should be equivalent replacement modes, and are all included in the protection scope of the present invention.

Claims (10)

  1. 一种绝缘基材表面电镀金属的方法，其特征在于，包括如下步骤：A method for electroplating metal on the surface of an insulating base material, comprising the following steps:
    S1、将树脂、溶剂、固体填料、固化剂按一定比例混合均匀，配制得到树脂涂料；S1. Mix the resin, solvent, solid filler and curing agent uniformly in a certain proportion to prepare a resin coating;
    S2、将S1中的树脂涂料涂覆于绝缘基材表面，固化后在绝缘基材表面形成均匀并且表面带有微小缝隙结构的树脂涂层；S2. Coat the resin coating in S1 on the surface of the insulating substrate, and after curing, form a uniform resin coating with a tiny gap structure on the surface of the insulating substrate;
    S3、将导电物质涂覆于S2中的树脂涂层上，烘干后在树脂涂层表面形成均匀的导电膜，导电膜中的导电物质作为后续电镀的活性位点；S3, coating the conductive material on the resin coating in S2, and after drying, a uniform conductive film is formed on the surface of the resin coating, and the conductive material in the conductive film is used as the active site of subsequent electroplating;
    S4、将经过S3处理后的覆有导电膜的绝缘基材置于电镀液中进行直接电镀。S4, placing the insulating substrate covered with the conductive film after being processed in S3 in an electroplating solution for direct electroplating.
  2. 根据权利要求1所述的绝缘基材表面电镀金属的方法，其特征在于，步骤S1中，树脂涂料中按质量百分数含量包括如下组分：树脂：10％-50％，溶剂：10％-50％，固化剂：1％-10％，固体填料：10-60％。The method for electroplating metal on the surface of an insulating base material according to claim 1, wherein in step S1, the resin coating comprises the following components by mass percentage: resin: 10%-50%, solvent: 10%-50% %, curing agent: 1%-10%, solid filler: 10-60%.
  3. 根据权利要求1所述的绝缘基材表面金属化的方法，其特征在于，步骤S1中，树脂选自聚乙烯、聚丙烯、聚氯乙烯、聚苯乙烯、ABS树脂、聚酯、聚碳酸酯、聚氨酯、聚酰胺、聚酰亚胺、丙烯酸树脂、环氧树脂、酚醛树脂、UV树脂、PTFE树脂、聚芳醚腈树脂中的一种或几种；优选为聚氨酯、聚酯和UV树脂。The method for metallizing the surface of an insulating substrate according to claim 1, wherein in step S1, the resin is selected from polyethylene, polypropylene, polyvinyl chloride, polystyrene, ABS resin, polyester, polycarbonate , polyurethane, polyamide, polyimide, acrylic resin, epoxy resin, phenolic resin, UV resin, PTFE resin, polyarylene ether nitrile resin, one or more of them; preferably polyurethane, polyester and UV resin.
  4. 根据权利要求1所述的绝缘基材表面电镀金属的方法，其特征在于，步骤S1中，溶剂选自水、乙醇、异丙醇、***、甲苯、戊烷、环己烷、丙酮、丁酮、乙酯、乙酸乙酯、N,N-二甲基甲酰胺、N-甲基吡咯烷酮、四氢呋喃中的一种或几种；优选为乙酸乙酯和丁酮。The method for electroplating metal on the surface of an insulating substrate according to claim 1, wherein in step S1, the solvent is selected from the group consisting of water, ethanol, isopropanol, ether, toluene, pentane, cyclohexane, acetone, butanone , one or more of ethyl ester, ethyl acetate, N,N-dimethylformamide, N-methylpyrrolidone, tetrahydrofuran; preferably ethyl acetate and butanone.
  5. 根据权利要求1所述的绝缘基材表面电镀金属的方法，其特征在于， 步骤S1中，固化剂选自多异氰酸酯、酸酐、有机胺、聚氨酯和咪唑类固化剂中的一种或几种；优选为多异氰酸酯和咪唑类固化剂。The method for electroplating metal on the surface of an insulating substrate according to claim 1, wherein in step S1, the curing agent is selected from one or more of polyisocyanates, acid anhydrides, organic amines, polyurethanes and imidazole curing agents; Preferred are polyisocyanate and imidazole curing agents.
  6. 根据权利要求1所述的绝缘基材表面电镀金属的方法，其特征在于，步骤S1中，固体填料选自二氧化硅、石墨、石墨烯、二氧化钛、氢氧化铝、氢氧化镁、氧化镁、三氧化二铝、氮化硼、磷酸铵、尿素、三苯、三苯基膦、三聚氰胺、三聚氰胺衍生物、聚磷酸铵、磷酸二氢铵、磷酸氢二铵和次膦酸盐中的一种或几种，所述固体填料的直径为0.1-100μm；优选为三聚氰胺和聚磷酸铵，直径为1-10μm。The method for electroplating metal on the surface of an insulating substrate according to claim 1, wherein in step S1, the solid filler is selected from the group consisting of silicon dioxide, graphite, graphene, titanium dioxide, aluminum hydroxide, magnesium hydroxide, magnesium oxide, One of aluminum oxide, boron nitride, ammonium phosphate, urea, triphenyl, triphenylphosphine, melamine, melamine derivatives, ammonium polyphosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate and phosphinate Or several, the diameter of the solid filler is 0.1-100 μm; preferably melamine and ammonium polyphosphate, the diameter is 1-10 μm.
  7. 根据权利要求1所述的绝缘基材表面电镀金属的方法，其特征在于，步骤S2中，绝缘基材为不同材料的平面基材或异形基材；The method for electroplating metal on the surface of an insulating base material according to claim 1, wherein in step S2, the insulating base material is a flat base material or a special-shaped base material of different materials;
    优选的，所述绝缘基材选自环氧树脂增强玻璃纤维布、无纺布、玻璃纤维布、陶瓷、硅、木制基材、有机聚合物薄膜中的一种；Preferably, the insulating base material is selected from epoxy resin reinforced glass fiber cloth, non-woven fabric, glass fiber cloth, ceramics, silicon, wood base material, and organic polymer film;
    优选的，所述有机聚合物薄膜包括聚乙烯，聚丙烯，聚酰亚胺，聚氨酯，聚酯，聚碳酸酯。Preferably, the organic polymer film includes polyethylene, polypropylene, polyimide, polyurethane, polyester, and polycarbonate.
  8. 根据权利要求1所述的绝缘基材表面电镀金属的方法，其特征在于，步骤S3中，涂覆工艺包括刮涂、旋涂、浸涂、喷涂、微凹版印刷、狭缝挤压和丝网印刷中的一种或几种，烘干温度为60℃-300℃，树脂涂层厚度为0.5-20μm。The method for electroplating metal on the surface of an insulating substrate according to claim 1, characterized in that, in step S3, the coating process includes blade coating, spin coating, dip coating, spray coating, microgravure printing, slit extrusion and screen mesh One or several kinds of printing, the drying temperature is 60℃-300℃, and the thickness of the resin coating is 0.5-20μm.
  9. 根据权利要求1所述的绝缘基材表面电镀金属的方法，其特征在于，步骤S3中，涂覆的导电物质包括银浆、铜浆、银包铜浆、银纳米线导电油墨、铜纳米线导电油墨、银包铜纳米线导电油墨、金纳米线导电油墨、有机导电高分子导电油墨中的一种或几种；优选为银浆和银纳米线导电油墨。The method for electroplating metal on the surface of an insulating base material according to claim 1, wherein in step S3, the coated conductive substances include silver paste, copper paste, silver-coated copper paste, silver nanowire conductive ink, and copper nanowires One or more of conductive ink, silver-coated copper nanowire conductive ink, gold nanowire conductive ink, and organic conductive polymer conductive ink; preferably silver paste and silver nanowire conductive ink.
  10. 一种印制线路板的制备方法，其特征在于，包括权利要求1-9任一项 所述的绝缘基材表面电镀金属的方法。A method for preparing a printed circuit board, characterized in that it comprises the method for electroplating metal on the surface of an insulating substrate according to any one of claims 1-9.
PCT/CN2020/140888 2020-12-29 2020-12-29 Method for electroplating metal on insulating substrate surface WO2022141064A1 (en)

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