CN111826643A - Method for improving coating binding force by activating copper plating on modified metal surface - Google Patents
Method for improving coating binding force by activating copper plating on modified metal surface Download PDFInfo
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- CN111826643A CN111826643A CN202010672309.0A CN202010672309A CN111826643A CN 111826643 A CN111826643 A CN 111826643A CN 202010672309 A CN202010672309 A CN 202010672309A CN 111826643 A CN111826643 A CN 111826643A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
- C23C18/405—Formaldehyde
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
- B22F1/145—Chemical treatment, e.g. passivation or decarburisation
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
- C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
- C23C18/2053—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment only one step pretreatment
- C23C18/206—Use of metal other than noble metals and tin, e.g. activation, sensitisation with metals
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/28—Sensitising or activating
- C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C24/00—Coating starting from inorganic powder
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
- C23C24/082—Coating starting from inorganic powder by application of heat or pressure and heat without intermediate formation of a liquid in the layer
- C23C24/085—Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides
- C23C24/087—Coating with metal alloys or metal elements only
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- 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
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
- H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating
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- 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
- H05K3/381—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the substrate
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- 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
- H05K3/389—Improvement of the adhesion between the insulating substrate and the metal by the use of a coupling agent, e.g. silane
Abstract
The invention discloses a method for improving the binding force of a coating by activating copper plating on the surface of modified metal, which comprises the following steps: placing the metal modified epoxy resin composite base material or the alkali washed metal modified epoxy resin composite base material in an alkaline reduction plating solution, wherein the plating temperature is 55-65 ℃, and the plating time is 3-5 h; ultrasonic cleaning is carried out for 5-60 min, and the metal/epoxy resin composite material containing the copper plating layer is obtained; the method is simple and efficient, has controllable conditions, and is easy to realize industrial production. The invention can obtain compact copper plating with high conductivity and strong binding force.
Description
Technical Field
The invention belongs to the technical field of chemical plating and printed circuit preparation, and particularly relates to a method for improving the binding force of a plating layer by activating copper plating on the surface of modified metal.
Background
Printed Circuit Boards (PCBs) are important components in the electronic information industry as carriers of electronic components, serving to support and realize electrical connections. The traditional PCB is prepared by an etching subtractive method, and has the defects of more production processes, large material consumption, high waste liquid discharge and heavy environmental protection pressure. The most potential method for solving the problems is to print conductive paste or conductive ink on an insulating substrate by using a screen printing or ink-jet printing technology, and then cure or sinter the conductive paste or the conductive ink at high temperature to form a circuit, but the conductivity of the obtained circuit is low. The Journal of functional polymers (volume 31(6) page 609 of 2018) reports that metal particles are used as a catalyst for chemical deposition of copper, high conductivity lines can be obtained, and the process can be applied to the manufacture of printed wiring boards, but the process has the disadvantage of poor bonding force between a plating layer and a substrate. In summary, how to obtain a copper plating layer with high bonding force on the surface of a PCB substrate (mainly epoxy resin and alumina ceramic) is a great technical problem that needs to be solved urgently in the PCB industry.
Disclosure of Invention
The invention aims to provide a method for improving the binding force of a plating layer by activating copper plating on the surface of modified metal, which can obtain a compact copper plating layer with high conductivity and strong binding force.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides a method for improving the binding force of a plating layer by activating copper plating on a modified metal surface, which comprises the following steps: placing the metal modified epoxy resin composite base material or the alkali washed metal modified epoxy resin composite base material in an alkaline reduction plating solution, wherein the plating temperature is 55-65 ℃, and the plating time is 3-5 h; ultrasonic cleaning is carried out for 5-60 min, and the metal/epoxy resin composite material containing the copper plating layer is obtained;
the preparation method of the alkaline reduction plating solution comprises the following steps: 0.3-0.5 g of CuSO4·5H2Dissolving O and 7-8 g of EDTA-2Na in 50mL of deionized water, dropwise adding a NaOH solution to adjust the pH value to 11-13, adding 1-2 mL of formaldehyde solution, and uniformly stirring and mixing to obtain the alkaline reduction plating solution;
the preparation method of the metal modified epoxy resin composite base material comprises the following steps:
uniformly mixing the epoxy resin, the methyl tetrahydrophthalic anhydride and the triethanolamine according to the mass ratio of (19-21): (15.2-16.8): 0.09-0.11), and precuring for 30-60 min at the temperature of 130-160 ℃ to obtain precured epoxy resin;
preparing modified metal powder into metal-ethanol dispersion, uniformly coating the metal-ethanol dispersion on the surface of pre-cured epoxy resin, drying at low temperature, curing at high temperature, and ultrasonically cleaning to obtain the metal-modified epoxy resin composite substrate;
the preparation method of the modified metal powder comprises the following steps:
dissolving a silane coupling agent in a mixed solution of ethanol and deionized water, wherein the concentration of the silane coupling agent is 0.001-3 g/mL, uniformly mixing, and adjusting the pH value to 2-5 by using acetic acid;
mixing the silane coupling agent solution and the metal-ethanol dispersion liquid for ultrasonic dispersion, wherein the amount of the silane coupling agent is 1-7% of the mass of the metal powder, centrifuging to remove supernatant, dehydrating for 1-12 hours in a nitrogen atmosphere at the temperature of 140-160 ℃, taking out, respectively ultrasonically cleaning with excessive boiling water and absolute ethyl alcohol, and dehydrating for 1-48 hours in a nitrogen atmosphere at the temperature of 60-100 ℃ to obtain modified metal;
the metal is silver powder or copper powder, and the diameter of the metal is 0.07-10 mu m;
the preparation method of the alkali-washed metal-modified epoxy resin composite base material comprises the following steps:
and (3) placing the metal modified epoxy resin composite base material in a sodium hydroxide aqueous solution with the pH value of 11-13, carrying out alkali washing for 20-40 min at the temperature of 50-80 ℃, and then carrying out ultrasonic washing for three times by using deionized water for 1-10 min each time to obtain the alkali-washed metal modified epoxy resin composite base material.
The metal modified epoxy resin composite base material is placed in alkaline reduction plating solution, and the area of the metal modified epoxy resin composite base material is 7.5cm2The metal modified epoxy resin composite base material is placed in 30-50 mL of alkaline reduction plating solution.
The concentration of the NaOH solution is 3-5 mol/L.
The concentration of the formaldehyde solution is 30-40%.
The concentration of the metal-ethanol dispersion liquid is 10-15%.
The low-temperature drying temperature is 30-45 ℃, and the time is 20-40 min.
The high-temperature curing temperature is 140-160 ℃, and preferably 150 ℃; the time is 130-160 min, preferably 140 min.
The ultrasonic cleaning time is 20-30 min.
The metal modified epoxy resin composite base material after alkaline cleaning is placed in alkaline reduction plating solution, and the area of the metal modified epoxy resin composite base material is 7.5cm2The metal modified epoxy resin composite base material after alkaline cleaning is placed in 30-50 mL of alkaline reduction plating solution.
The epoxy resin is epoxy resin E-51.
Due to the adoption of the technical scheme, the invention has the following advantages and beneficial effects:
the invention provides a method for activating copper plating of a silane coupling agent modified metal powder-epoxy resin composite substrate, which is characterized in that silane coupling agent KH-560 modified silver powder or copper powder with an epoxy group is selected, and the modified metal powder is coated on the surface of a pre-cured epoxy resin substrate. One end of KH-560 is dehydrated through the silicon hydroxyl generated by hydrolysis and the hydroxyl on the surface of the silver powder or copper powder to form a chemical bond; the epoxy group at the other end can participate in the curing reaction of the epoxy resin to form chemical bond combination, so that the binding force between the metal powder and the resin is improved. On the basis, the problem of poor bonding force between the coating and the base material is solved by utilizing the metal powder to catalyze electroless copper plating. Meanwhile, the obtained plating layer is uniform and compact, has good conductivity, and can meet the application requirements in the field of printed circuits.
The preparation method is simple and efficient, has controllable conditions, and is easy to realize industrial production. The invention can obtain compact copper plating with high conductivity and strong binding force. When the dosage of KH-560 is 4% of the metal powder, the maximum binding force between the coating and the resin is 2.27MPa, which is 25.4% higher than that of the coating without KH-560 modified metal powder. The conductivity of the copper plating is about 3.15 multiplied by 107S/m, has huge application prospect in the PCB industry.
Drawings
FIG. 1 is a Fourier transform infrared spectrum of a silane coupling agent KH-560 modified silver powder prepared in example 1.
FIG. 2 is a scanning electron micrograph and an elemental analysis of a cross section of the plating layer prepared in example 1.
FIG. 3 is a graph showing the variation of the bonding force between the plating layer and the resin according to the amount of KH-560.
FIG. 4 is a flow chart of the process of activated copper plating on the surface of modified metal.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
Example 1
FIG. 4 is a flow chart of the process of activated copper plating on the surface of modified metal.
Firstly, the preparation method of the silane coupling agent modified silver powder comprises the following steps:
2.0g of silane coupling agent KH-560 was dissolved in a mixed solution of 95mL of ethanol and 5mL of deionized water, and the pH was adjusted to 4 with acetic acid. Adding 5mL of the newly prepared silane coupling agent KH-560 solution into 25mL of silver powder-ethanol dispersion liquid (the diameter of the silver powder is 1 micron, the mass of the silver powder is 10 percent of the mass of ethanol), performing ultrasonic dispersion for 2h to ensure that the silane coupling agent KH-560 is fully adsorbed on the surface of the silver powder, centrifuging to remove supernatant, placing the solid in a nitrogen atmosphere oven at the temperature of 150 ℃ for dehydration for 2h, taking out, respectively performing ultrasonic cleaning for 30min by using excessive boiling water and absolute ethanol, placing the cleaned silver powder in the nitrogen atmosphere oven at the temperature of 80 ℃ for drying for 24h to obtain the silane coupling agent modified silver powder.
To demonstrate that the silane coupling agent KH-560 can modify silver powder, the silane coupling agent KH-560, the silver powder modified by the silane coupling agent KH-560, and the silver powder modified by the silane coupling agent KH-560 were hydrolyzed in an aqueous alkali (sodium hydroxide) solution having a pH of 12 at 60 ℃ for 30min in a water bath, and the unmodified silver powder were characterized by using a Fourier transform infrared spectrum, and the results are shown in FIG. 1, in which FIG. 1 is a Fourier transform infrared spectrum of the silane coupling agent KH-560 modified silver powder prepared in example 1. From the figure, it can be seen that KH-560 successfully modified silver powder and can be removed by alkaline hydrolysis.
Secondly, the preparation method of the silane coupling agent modified silver powder-epoxy resin composite base material comprises the following steps:
20g of epoxy resin E-51, 16g of methyl tetrahydrophthalic anhydride and 0.1g of triethanolamine are uniformly mixed and spin-coated to form a film (the area is 7.5 cm)2) And placing the epoxy resin in an oven with the temperature of 150 ℃ for precuring for 40min to obtain the precured epoxy resin.
Preparing the silane coupling agent modified silver powder prepared in the first step into silver powder-ethanol dispersion liquid with the concentration of 12.5%, uniformly coating the silver powder-ethanol dispersion liquid on the surface of the pre-cured epoxy resin, heating and drying the silver powder-ethanol dispersion liquid in a drying oven at the temperature of 35 ℃ for 30min, then placing the mixture in the drying oven at the temperature of 150 ℃ for continuously curing for 140min, cooling the mixture at room temperature, and ultrasonically cleaning the mixture for 20min to obtain the silane coupling agent modified silver powder-epoxy resin composite base material.
Step three, activating and plating copper on the silane coupling agent modified silver powder-epoxy resin composite base material:
the preparation method of the alkaline reduction plating solution comprises the following steps: 0.4g of CuSO4·5H2Dissolving O and 7.5g of EDTA-2Na in 50mL of deionized water, dropwise adding a 5mol/L NaOH solution to adjust the pH value to 13, adding 1.5mL of a 37% formaldehyde solution, and uniformly stirring and mixing to obtain the alkaline reduction plating solution.
And (2) placing the silane coupling agent modified silver powder-epoxy resin composite base material prepared in the second step into 30mL of alkaline reduction plating solution, plating for 4h under the condition of water bath at the temperature of 65 ℃, then ultrasonically washing the base material with deionized water for three times for 10min each time to obtain the silane coupling agent modified silver powder-epoxy resin composite material with the copper plating layer on the surface, and performing section characterization on the prepared silane coupling agent modified silver powder-epoxy resin composite material with the copper plating layer on the surface by using SEM (scanning electron microscope), as shown in figure 2, figure 2 is an SEM picture and an element analysis picture of the silane coupling agent modified silver powder-epoxy resin composite material with the copper plating layer on the surface prepared in example 1, figure 2a is an SEM picture of the cross section of a plating layer, figure 2b is an element analysis picture of the plating layer, and the modified silver powder can be obtained by analysis, wherein the thickness of the copper plating layer is about 20 mu m.
A series of silver powders modified by silane coupling agent KH-560 were prepared by changing the mass ratio of the silane coupling agent KH-560 to the silver powders from 0% to 7% (0%, 1%, 2%, 3%, 4%, 5%, 6%, 7%), the influence of the amount of the silane coupling agent KH-560 on the binding force of the plating layer was studied, and then copper plating was performed according to the second and third steps, the pull-off strength of the silver powder-epoxy resin composite modified by silane coupling agent having a copper plating layer on the surface was as shown in FIG. 3, the pull-off strength was tested according to the national Standard GB-5270-. When the dosage of KH-560 is 4% of the silver powder, the maximum binding force between the plating layer and the resin is 2.27MPa, which is 25.4% higher than that of the plating layer without KH-560 modified silver powder. The conductivity of the copper plating is about 3.15 multiplied by 107S/m, has great application prospect in the field of printed circuits.
Example 2
The preparation method of the modified copper powder-epoxy resin composite base material comprises the following steps:
2.0g of silane coupling agent KH-560 was dissolved in a mixed solution of 95mL of ethanol and 5mL of deionized water, and the pH was adjusted to 4 with acetic acid. Adding 5mL of the newly prepared silane coupling agent KH-560 solution into 25mL of copper powder-ethanol dispersion liquid (the diameter of the copper powder is 3 micrometers, and the mass of the copper powder is 10 percent of the mass of ethanol), wherein the dosage of the silane coupling agent is 4 percent of the mass of the metal, performing ultrasonic dispersion for 2h to ensure that the silane coupling agent KH-560 is fully adsorbed on the surface of the copper powder, centrifuging to remove supernatant, placing the solid in a nitrogen atmosphere oven for dehydration for 2h at the temperature of 150 ℃, taking out the solid, performing ultrasonic cleaning for 30min by using excessive boiling water and absolute ethanol respectively, placing the cleaned copper powder in the nitrogen atmosphere oven for drying for 24h at the temperature of 80 ℃, and obtaining the silane coupling agent modified copper powder.
20g of epoxy resin E-51, 16g of methyl tetrahydrophthalic anhydride and 0.1g of triethanolamine are uniformly mixed and spin-coated to form a film (the area is 7.5 cm)2) And placing the epoxy resin in an oven at the temperature of 150 ℃ for pre-curing for 40min to obtain the pre-cured epoxy resin.
Preparing the modified copper powder into a copper powder-ethanol dispersion liquid with the concentration of 12.5%, uniformly coating the copper powder-ethanol dispersion liquid on the surface of the pre-cured epoxy resin, heating and drying the copper powder-ethanol dispersion liquid in an oven with the temperature of 35 ℃ for 30min, then placing the pre-cured epoxy resin in the oven with the temperature of 150 ℃ for continuously curing for 140min, cooling the pre-cured epoxy resin at room temperature, and then ultrasonically cleaning the pre-cured epoxy resin for 20min to obtain the modified copper powder-epoxy resin composite base material.
And (3) placing the modified copper powder-epoxy resin composite base material into 100mL of sodium hydroxide solution with the pH value of 12, carrying out alkali washing for 30min at the temperature of 60 ℃, then carrying out ultrasonic washing for three times by using deionized water, wherein each time is 5min, and thus obtaining the alkali-washed copper powder-epoxy resin composite base material.
Activating and coppering the copper powder-epoxy resin composite base material after alkali washing:
the preparation method of the alkaline reduction plating solution comprises the following steps: 0.35g of CuSO4·5H2Dissolving O and 7.0g of EDTA-2Na in 50mL of deionized water, dropwise adding a 5mol/L NaOH solution to adjust the pH value to 12, adding 1.0mL of a 37% formaldehyde solution, and uniformly mixing to obtain the alkaline reduction plating solution.
And (3) placing the copper powder-epoxy resin composite base material subjected to alkali washing in 30mL of alkaline reduction plating solution, plating for 4h under the water bath condition at the temperature of 60 ℃, and then ultrasonically washing for three times by using deionized water for 10min each time to obtain the copper powder-epoxy resin composite material subjected to alkali washing and provided with a copper plating layer on the surface. The copper plating thickness was about 20 μm. The pull-off strength was 2.10 MPa.
Comparative example 1
Activation of copper plating without KH-560 modified silver powder:
the preparation method of the alkaline reduction plating solution comprises the following steps: 0.35g of CuSO4·5H2Dissolving O and 7.0g of EDTA-2Na in 50mL of deionized water, dropwise adding a 5mol/L NaOH solution to adjust the pH value to 12, adding 1.0mL of a 37% formaldehyde solution, and uniformly mixing to obtain the alkaline reduction plating solution.
Placing the silver powder-epoxy resin composite base material prepared by using unmodified silver powder (the diameter is 1 mu m) into 30mL of alkaline reduction plating solution, plating for 4h under the condition of water bath at the temperature of 60 ℃, and then ultrasonically washing for three times by using deionized water for 10min each time to obtain the silver foil composite material with a copper-plated layer on the surface. The copper plating thickness was about 15 μm. The pull-off strength was 1.82 MPa.
Example 3
Firstly, the preparation method of the silane coupling agent modified silver powder comprises the following steps:
2.0g of silane coupling agent KH-560 was dissolved in a mixed solution of 95mL of ethanol and 5mL of deionized water, and the pH was adjusted to 3 with acetic acid. Adding 1.3mL of the newly prepared silane coupling agent KH-560 solution into 25mL of silver powder-ethanol dispersion liquid (the diameter of the silver powder is 0.07 mu m, the mass of the silver powder is 10 percent of the mass of ethanol), wherein the dosage of the silane coupling agent is 1 percent of the mass of metal, performing ultrasonic dispersion for 2h to ensure that the silane coupling agent KH-560 is fully adsorbed to the surface of the silver powder, centrifuging to remove supernatant, placing the solid in a nitrogen atmosphere oven for dewatering for 2h at the temperature of 150 ℃, taking out, respectively performing ultrasonic cleaning for 30min by using excessive boiling water and absolute ethanol, placing the cleaned silver powder in the nitrogen atmosphere oven for drying for 24h at the temperature of 80 ℃, and obtaining the silane coupling agent modified silver powder.
Secondly, the preparation method of the silane coupling agent modified silver powder-epoxy resin composite base material comprises the following steps:
20.5g of epoxy resin E-51, 15.5g of methyl tetrahydrophthalic anhydride and 0.09g of triethanolamine are uniformly mixed and spin-coated to form a film (the area is 7.5 cm)2) And placing the epoxy resin in an oven with the temperature of 150 ℃ for precuring for 50min to obtain the precured epoxy resin.
Preparing the silane coupling agent modified silver powder prepared in the first step into a silver powder-ethanol dispersion liquid with the concentration of 10%, uniformly coating the silver powder-ethanol dispersion liquid on the surface of the pre-cured epoxy resin, heating and drying the silver powder-ethanol dispersion liquid in a drying oven at the temperature of 45 ℃ for 20min, then placing the dried silver powder-ethanol dispersion liquid in the drying oven at the temperature of 150 ℃ for continuously curing for 150min, cooling the silver powder-ethanol dispersion liquid at room temperature, and ultrasonically cleaning the silver powder-ethanol dispersion liquid for 20min to obtain the silane coupling agent modified silver powder-epoxy.
Step three, activating and plating copper on the silane coupling agent modified silver powder-epoxy resin composite base material:
the preparation method of the alkaline reduction plating solution comprises the following steps: 0.3g of CuSO4·5H2Dissolving O and 7g of EDTA-2Na in 50mL of deionized water, dropwise adding a 5mol/L NaOH solution to adjust the pH value to 12, adding 2mL of a 37% formaldehyde solution, and uniformly stirring and mixing to obtain the alkaline reduction plating solution.
And (3) placing the silane coupling agent modified silver powder-epoxy resin composite base material prepared in the second step into 30mL of alkaline reduction plating solution, plating for 4h under the water bath condition at the temperature of 65 ℃, and then ultrasonically washing with deionized water for three times, wherein each time lasts for 10min, so as to obtain the silane coupling agent modified silver powder-epoxy resin composite material with the copper-plated layer on the surface. The copper plating thickness was about 18.5 μm. The pull-off strength was 1.92 MPa.
Example 4
Firstly, the preparation method of the silane coupling agent modified silver powder comprises the following steps:
1.9g of silane coupling agent KH-560 was dissolved in a mixed solution of 95mL of ethanol and 5mL of deionized water, and the pH was adjusted to 3 with acetic acid. Adding 4mL of the newly prepared silane coupling agent KH-560 solution into 25mL of silver powder-ethanol dispersion liquid (the diameter of the silver powder is 2 micrometers, the mass of the silver powder is 10 percent of the mass of ethanol), performing ultrasonic dispersion for 2h to ensure that the silane coupling agent KH-560 is fully adsorbed on the surface of the silver powder, centrifuging to remove supernatant, placing the solid in a nitrogen atmosphere oven at the temperature of 150 ℃ for dehydration for 2h, taking out, respectively performing ultrasonic cleaning for 30min by using excessive boiling water and absolute ethanol, placing the cleaned silver powder in the nitrogen atmosphere oven at the temperature of 80 ℃ for drying for 24h to obtain the silane coupling agent modified silver powder.
Secondly, the preparation method of the silane coupling agent modified silver powder-epoxy resin composite base material comprises the following steps:
19g of epoxy resin E-51, 16g of methyl tetrahydrophthalic anhydride and 0.1g of triethanolamine are uniformly mixed and spin-coated to form a film (the area is 7.5 cm)2) And placing the epoxy resin in an oven with the temperature of 150 ℃ for precuring for 30min to obtain the precured epoxy resin.
Preparing the silane coupling agent modified silver powder prepared in the first step into a silver powder-ethanol dispersion liquid with the concentration of 10%, uniformly coating the silver powder-ethanol dispersion liquid on the surface of the pre-cured epoxy resin, heating and drying the silver powder-ethanol dispersion liquid in a drying oven at the temperature of 40 ℃ for 20min, then placing the mixture in the drying oven at the temperature of 150 ℃ for continuously curing for 130min, cooling the mixture at room temperature, and ultrasonically cleaning the mixture for 20min to obtain the silane coupling agent modified silver powder-epoxy resin composite base material.
Step three, activating and plating copper on the silane coupling agent modified silver powder-epoxy resin composite base material:
the preparation method of the alkaline reduction plating solution comprises the following steps: 0.3g of CuSO4·5H2Dissolving O and 8g of EDTA-2Na in 50mL of deionized water, dropwise adding a 5mol/L NaOH solution to adjust the pH value to 13, adding 1mL of a 37% formaldehyde solution, and uniformly stirring and mixing to obtain the alkaline reduction plating solution.
And (3) placing the silane coupling agent modified silver powder-epoxy resin composite base material prepared in the second step into 30mL of alkaline reduction plating solution, plating for 5h under the water bath condition at the temperature of 60 ℃, and then ultrasonically washing with deionized water for three times, wherein each time lasts for 10min, so as to obtain the silane coupling agent modified silver powder-epoxy resin composite material with the copper-plated layer on the surface. The copper plating thickness was about 19 μm. The pull-off strength was 2.20 MPa.
Example 5
Firstly, the preparation method of the silane coupling agent modified silver powder comprises the following steps:
2.1g of silane coupling agent KH-560 was dissolved in a mixed solution of 90mL of ethanol and 5mL of deionized water, and the pH was adjusted to 5 with acetic acid. Adding 7mL of the newly prepared silane coupling agent KH-560 solution into 25mL of silver powder-ethanol dispersion liquid (the diameter of the silver powder is 5 micrometers, and the mass of the silver powder is 10 percent of the mass of ethanol), wherein the dosage of the silane coupling agent is 6 percent of the mass of the metal, performing ultrasonic dispersion for 2h to ensure that the silane coupling agent KH-560 is fully adsorbed on the surface of the silver powder, centrifuging to remove supernatant, placing the solid in a nitrogen atmosphere oven for dehydration for 2h at the temperature of 150 ℃, taking out the solid, performing ultrasonic cleaning for 30min by using excessive boiling water and absolute ethanol respectively, placing the cleaned silver powder in the nitrogen atmosphere oven for drying for 24h at the temperature of 80 ℃, and obtaining the silane coupling agent modified silver powder.
Secondly, the preparation method of the silane coupling agent modified silver powder-epoxy resin composite base material comprises the following steps:
21g of epoxy resin E-51, 15.5g of methyl tetrahydrophthalic anhydride and 0.1g of triethanolamine are uniformly mixed and spin-coated to form a film (the area is 7.5 cm)2) And placing the epoxy resin in an oven with the temperature of 150 ℃ for precuring for 30min to obtain the precured epoxy resin.
Preparing the silane coupling agent modified silver powder prepared in the first step into a silver powder-ethanol dispersion liquid with the concentration of 10%, uniformly coating the silver powder-ethanol dispersion liquid on the surface of the pre-cured epoxy resin, heating and drying the silver powder-ethanol dispersion liquid in a drying oven at the temperature of 40 ℃ for 30min, then placing the mixture in the drying oven at the temperature of 160 ℃ for continuously curing for 130min, cooling the mixture at room temperature, and ultrasonically cleaning the mixture for 25min to obtain the silane coupling agent modified silver powder-epoxy resin composite base material.
Step three, activating and plating copper on the silane coupling agent modified silver powder-epoxy resin composite base material:
the preparation method of the alkaline reduction plating solution comprises the following steps: 0.5g of CuSO4·5H2Dissolving O and 8g of EDTA-2Na in 50mL of deionized water, dropwise adding a 5mol/L NaOH solution to adjust the pH value to 12, adding 2mL of a 37% formaldehyde solution, and uniformly stirring and mixing to obtain the alkaline reduction plating solution.
And (3) placing the silane coupling agent modified silver powder-epoxy resin composite base material prepared in the second step into 30mL of alkaline reduction plating solution, plating for 4h under the water bath condition at the temperature of 65 ℃, and then ultrasonically washing with deionized water for three times, wherein each time lasts for 10min, so as to obtain the silane coupling agent modified silver powder-epoxy resin composite material with the copper-plated layer on the surface. The copper plating thickness was about 19 μm. The pull-off strength was 2.21 MPa.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (9)
1. A method for improving the binding force of a plating layer by activating copper plating on the surface of modified metal is characterized by comprising the following steps: placing the metal modified epoxy resin composite base material or the alkali washed metal modified epoxy resin composite base material in an alkaline reduction plating solution, wherein the plating temperature is 55-65 ℃, and the plating time is 3-5 h; ultrasonic cleaning is carried out for 5-60 min, and the metal/epoxy resin composite material containing the copper plating layer is obtained;
the preparation method of the alkaline reduction plating solution comprises the following steps: 0.3-0.5 g of CuSO4·5H2Dissolving O and 7-8 g of EDTA-2Na in 50mL of deionized water, dropwise adding a NaOH solution to adjust the pH value to 11-13, adding 1-2 mL of formaldehyde solution, and uniformly stirring and mixing to obtain the alkaline reduction plating solution;
the preparation method of the metal modified epoxy resin composite base material comprises the following steps:
uniformly mixing the epoxy resin, the methyl tetrahydrophthalic anhydride and the triethanolamine according to the mass ratio of (19-21): (15.2-16.8): 0.09-0.11), and precuring for 30-60 min at the temperature of 130-160 ℃ to obtain precured epoxy resin;
preparing modified metal powder into metal-ethanol dispersion, uniformly coating the metal-ethanol dispersion on the surface of pre-cured epoxy resin, drying at low temperature, curing at high temperature, and ultrasonically cleaning to obtain the metal-modified epoxy resin composite substrate;
the preparation method of the modified metal powder comprises the following steps:
dissolving a silane coupling agent in a mixed solution of ethanol and deionized water, wherein the concentration of the silane coupling agent is 0.001-3 g/mL, uniformly mixing, and adjusting the pH value to 2-5 by using acetic acid;
mixing the silane coupling agent solution and the metal-ethanol dispersion liquid for ultrasonic dispersion, wherein the amount of the silane coupling agent is 1-7% of the mass of the metal powder, centrifuging to remove supernatant, dehydrating for 1-12 hours in a nitrogen atmosphere at the temperature of 140-160 ℃, taking out, respectively ultrasonically cleaning with excessive boiling water and absolute ethyl alcohol, and dehydrating for 1-48 hours in a nitrogen atmosphere at the temperature of 60-100 ℃ to obtain modified metal;
the metal is silver powder or copper powder, and the diameter of the metal is 0.07-10 mu m;
the preparation method of the alkali-washed metal-modified epoxy resin composite base material comprises the following steps:
and (3) placing the metal modified epoxy resin composite base material in a sodium hydroxide aqueous solution with the pH value of 11-13, carrying out alkali washing for 20-40 min at the temperature of 50-80 ℃, and then carrying out ultrasonic washing for three times by using deionized water for 1-10 min each time to obtain the alkali-washed metal modified epoxy resin composite base material.
2. The method for improving the binding force of the coating by activating copper plating on the surface of the modified metal according to claim 1, wherein the step of placing the metal modified epoxy resin composite substrate in the alkaline reduction plating solution is to place the metal modified epoxy resin composite substrate in the alkaline reduction plating solution with the area of 7.5cm2The metal modified epoxy resin composite base material is placed in 30-50 mL of alkaline reduction plating solution.
3. The method for improving the binding force of the coating by activating copper plating on the surface of the modified metal according to claim 1, wherein the concentration of the NaOH solution is 3-5 mol/L.
4. The method for improving the coating binding force of the modified metal surface through activating the copper plating according to claim 1, wherein the concentration of the formaldehyde solution is 30-40%.
5. The method for improving the binding force of the coating by activating the copper plating on the surface of the modified metal according to claim 1, wherein the concentration of the metal-ethanol dispersion liquid is 10-15%.
6. The method for improving the binding force of the coating by activating the copper plating on the surface of the modified metal according to claim 1, wherein the low-temperature drying temperature is 30-45 ℃ and the time is 20-40 min.
7. The method for improving the binding force of the coating by activating the copper plating on the surface of the modified metal according to claim 1, wherein the high-temperature curing temperature is 140-160 ℃ and the time is 130-160 min.
8. The method for improving the bonding force of the coating by activating the copper plating on the surface of the modified metal according to claim 1, wherein the ultrasonic cleaning time is 20-30 min.
9. The method for improving the binding force of the coating by activating copper plating on the surface of the modified metal according to claim 1, wherein the step of placing the metal modified epoxy resin composite substrate subjected to alkali washing in an alkali reduction plating solution is to place the metal modified epoxy resin composite substrate with the area of 7.5cm2The metal modified epoxy resin composite base material after alkaline cleaning is placed in 30-50 mL of alkaline reduction plating solution.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115491667A (en) * | 2021-06-18 | 2022-12-20 | 东莞市德施普技术有限公司 | Magnesium surface treatment method for combination of polymer and magnesium |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1068291A (en) * | 1991-09-05 | 1993-01-27 | 南京大学 | The method of plastic surface copper plating raising and resin and Bond Strength |
| CN1262711A (en) * | 1998-07-07 | 2000-08-09 | 株式会社日本能源 | Pretreating agent for metal plating, and method for metal plating using same |
| CN1406288A (en) * | 2000-04-25 | 2003-03-26 | 株式会社日矿材料 | Pretreating agent for plating and method for metal plating using the same |
| CN1420944A (en) * | 2000-01-07 | 2003-05-28 | 株式会社日矿材料 | Method for metal plating, pretreating agent, and semiconductor wafer and semiconductor device using same |
| US20060233963A1 (en) * | 2003-06-09 | 2006-10-19 | Toru Imori | Method for electroless plating and metal-plated article |
| US20080138629A1 (en) * | 2005-03-10 | 2008-06-12 | Toshifumi Kawamura | Resin Substrate Material, Electronic Component Substrate Material Manufactured by Electroless Plating on the Same, and Method for Manufacturing Electronic Component Substrate Material |
| CN101492814A (en) * | 2009-02-26 | 2009-07-29 | 复旦大学 | Process for producing double-layer flexible cover copper plate |
| CN103866299A (en) * | 2014-03-24 | 2014-06-18 | 大连理工大学 | Pretreatment process of surface chemical plating of resin matrix composite material |
| JP2017017111A (en) * | 2015-06-29 | 2017-01-19 | 公立大学法人兵庫県立大学 | Composite material, and method and device for producing the same |
| CN108754461A (en) * | 2018-05-24 | 2018-11-06 | 合肥学院 | A kind of method of surface of polymer substrates selective chemical plating |
-
2020
- 2020-07-14 CN CN202010672309.0A patent/CN111826643B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1068291A (en) * | 1991-09-05 | 1993-01-27 | 南京大学 | The method of plastic surface copper plating raising and resin and Bond Strength |
| CN1262711A (en) * | 1998-07-07 | 2000-08-09 | 株式会社日本能源 | Pretreating agent for metal plating, and method for metal plating using same |
| CN1420944A (en) * | 2000-01-07 | 2003-05-28 | 株式会社日矿材料 | Method for metal plating, pretreating agent, and semiconductor wafer and semiconductor device using same |
| CN1406288A (en) * | 2000-04-25 | 2003-03-26 | 株式会社日矿材料 | Pretreating agent for plating and method for metal plating using the same |
| US20060233963A1 (en) * | 2003-06-09 | 2006-10-19 | Toru Imori | Method for electroless plating and metal-plated article |
| US20080138629A1 (en) * | 2005-03-10 | 2008-06-12 | Toshifumi Kawamura | Resin Substrate Material, Electronic Component Substrate Material Manufactured by Electroless Plating on the Same, and Method for Manufacturing Electronic Component Substrate Material |
| CN101492814A (en) * | 2009-02-26 | 2009-07-29 | 复旦大学 | Process for producing double-layer flexible cover copper plate |
| CN103866299A (en) * | 2014-03-24 | 2014-06-18 | 大连理工大学 | Pretreatment process of surface chemical plating of resin matrix composite material |
| JP2017017111A (en) * | 2015-06-29 | 2017-01-19 | 公立大学法人兵庫県立大学 | Composite material, and method and device for producing the same |
| CN108754461A (en) * | 2018-05-24 | 2018-11-06 | 合肥学院 | A kind of method of surface of polymer substrates selective chemical plating |
Non-Patent Citations (1)
| Title |
|---|
| 聂旭坤等: "丙烯酸树脂活化银胶的制备 结构与性能", 《功能高分子学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115491667A (en) * | 2021-06-18 | 2022-12-20 | 东莞市德施普技术有限公司 | Magnesium surface treatment method for combination of polymer and magnesium |
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