CN111826643B - Method for improving binding force of plating layer by activating copper plating on surface of modified metal - Google Patents
Method for improving binding force of plating layer by activating copper plating on surface of modified metal Download PDFInfo
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- CN111826643B CN111826643B CN202010672309.0A CN202010672309A CN111826643B CN 111826643 B CN111826643 B CN 111826643B CN 202010672309 A CN202010672309 A CN 202010672309A CN 111826643 B CN111826643 B CN 111826643B
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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
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Abstract
The invention discloses a method for improving the binding force of a plating layer by activating copper plating on the surface of a modified metal, which comprises the following steps: placing the metal modified epoxy resin composite substrate or the metal modified epoxy resin composite substrate subjected to alkali washing into an alkaline reduction plating solution, wherein the plating temperature is 55-65 ℃, and the plating time is 3-5 h; ultrasonic cleaning for 5-60 min to obtain a metal/epoxy resin composite material containing a copper plating layer; the method is simple and efficient, has controllable conditions, and is easy to realize industrial production. The invention can obtain the copper plating layer with compact structure, 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 a modified metal.
Background
The printed circuit board (Printed Circuit Board, PCB) serves as a carrier for the electronic components, and serves to support and electrically connect, which is an important component in the electronic information industry. The traditional PCB is prepared by an etching reduction method, and has the defects of more production procedures, high material consumption, high waste liquid discharge and heavy environmental protection pressure. The most potential method for solving the above problems is to print conductive paste or ink on an insulating substrate by screen printing or ink jet printing, and then cure or sinter the printed paste or ink at high temperature to form a circuit, but the conductivity of the obtained circuit is low. The functional polymer journal (Journal of Functional Polymers,2018, 31 (6) volume 609) reports that a high-conductivity circuit can be obtained by using metal particles as a catalyst for electroless deposition of copper and can be applied to the manufacture of printed wiring boards, but the process has the defect 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 serious technical problem that needs to be solved 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 above purpose, the technical scheme adopted by the invention is as follows:
the first aspect of the invention provides a method for improving the binding force of a plating layer by activating copper plating on the surface of a modified metal, which comprises the following steps: placing the metal modified epoxy resin composite substrate or the metal modified epoxy resin composite substrate subjected to alkali washing into an alkaline reduction plating solution, wherein the plating temperature is 55-65 ℃, and the plating time is 3-5 h; ultrasonic cleaning for 5-60 min to obtain a metal/epoxy resin composite material containing a copper plating layer;
the preparation method of the alkaline reduction plating solution comprises the following steps: 0.3 to 0.5g of CuSO 4 ·5H 2 O and 7-8 g of EDTA-2Na are dissolved in 50mL of deionized water, naOH solution is added dropwise to adjust the pH value to 11-13, 1-2 mL of formaldehyde solution is added and stirred and mixed uniformly, and the alkaline reduction plating solution is obtained;
the preparation method of the metal modified epoxy resin composite substrate comprises the following steps:
uniformly mixing epoxy resin, methyl tetrahydrophthalic anhydride and triethanolamine with the mass ratio of (19-21) (15.2-16.8) (0.09-0.11), and pre-curing for 30-60 min at the temperature of 130-160 ℃ to obtain pre-cured epoxy resin;
preparing modified metal powder into metal-ethanol dispersion liquid, uniformly coating the metal-ethanol dispersion liquid on the surface of the 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, uniformly mixing the mixture, wherein the concentration of the silane coupling agent is 0.001-3 g/mL, and regulating the pH value to be 2-5 by using acetic acid;
mixing the silane coupling agent solution with the metal-ethanol dispersion liquid for ultrasonic dispersion, centrifugally removing supernatant, dehydrating for 1-12 hours in nitrogen atmosphere at the temperature of 140-160 ℃, taking out and respectively ultrasonically cleaning with excessive boiling water and absolute ethanol, dehydrating for 1-48 hours in nitrogen atmosphere at the temperature of 60-100 ℃ to obtain modified metal;
the metal is silver powder or copper powder, and the diameter is 0.07-10 mu m;
the preparation method of the alkali-washed metal modified epoxy resin composite substrate comprises the following steps:
and (3) placing the metal modified epoxy resin composite substrate in a sodium hydroxide aqueous solution with the pH value of 11-13, performing alkaline washing for 20-40 min at the temperature of 50-80 ℃, and performing ultrasonic washing with deionized water for three times, wherein each time is 1-10 min, so as to obtain the metal modified epoxy resin composite substrate after alkaline washing.
The metal modified epoxy resin composite substrate is placed in alkaline reduction plating solution, and the area of the metal modified epoxy resin composite substrate is 7.5cm 2 The metal modified epoxy resin composite substrate 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 ℃, preferably 150 ℃; the time is 130 to 160min, preferably 140min.
The ultrasonic cleaning time is 20-30 min.
The method comprises placing the alkali-washed metal modified epoxy resin composite substrate in an alkaline reduction plating solution with an area of 7.5cm 2 After alkali washing, the metal modified epoxy resin composite substrate is placed in 30-50 mL of alkaline reduction plating solution.
The epoxy resin is epoxy resin E-51.
By adopting 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 to select silane coupling agent KH-560 modified silver powder or copper powder with epoxy groups and coat the modified metal powder on the surface of a pre-cured epoxy resin substrate. One end of KH-560 is dehydrated with silicon hydroxyl generated by hydrolysis and hydroxyl on the surface of 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 bonding force between the metal powder and the resin is improved. On the basis, the metal powder is used for catalyzing chemical copper plating so as to solve the problem of poor bonding force between a plating layer and a base material. Meanwhile, the obtained coating is uniform and compact, has good conductivity, and can meet the application requirements of the field of printed circuits.
The preparation method provided by the invention is simple and efficient, has controllable conditions, and is easy to realize industrial production. The invention can obtain the copper plating layer with compact structure, high conductivity and strong binding force. When the consumption of KH-560 is 4% of the mass of the metal powder, the binding force between the coating and the resin is 2.27MPa at maximum, which is improved by 25.4% compared with the binding force of the coating when the KH-560 is not used for modifying the metal powder. The conductivity of the copper plating layer is about 3.15 multiplied by 10 7 S/m has great application prospect in the PCB industry.
Drawings
FIG. 1 is a Fourier transform infrared spectrum of the silane coupling agent KH-560 modified silver powder prepared in example 1.
FIG. 2 is a scanning electron microscope image and an elemental analysis image of a cross section of the plating layer prepared in example 1.
FIG. 3 is a graph showing the change of the bonding force between the coating and the resin with the KH-560 dosage.
FIG. 4 is a flow chart of modified metal surface activation copper plating.
Detailed Description
In order to more clearly illustrate the present invention, the present invention will be further described with reference to preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and that this invention is not limited to the details given herein.
Example 1
FIG. 4 is a flow chart of modified metal surface activation copper plating.
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 newly prepared solution of the silane coupling agent KH-560 into 25mL of silver powder-ethanol dispersion liquid (the diameter of the silver powder is 1 mu m, the mass of the silver powder is 10% of the mass of ethanol), performing ultrasonic dispersion for 2h, enabling the silane coupling agent KH-560 to be fully adsorbed on the surface of the silver powder, centrifuging to remove supernatant, placing the solid in a nitrogen atmosphere oven at 150 ℃ for dehydration for 2h, taking out the solid, respectively performing ultrasonic cleaning with excessive boiling water and absolute ethyl alcohol for 30min, and placing the cleaned silver powder in a nitrogen atmosphere oven at 80 ℃ for drying for 24h to obtain the silane coupling agent modified silver powder.
To prove that the silane coupling agent KH-560 can modify silver powder, the Fourier transform infrared spectrogram is utilized to characterize the silane coupling agent KH-560, the silver powder modified by the silane coupling agent KH-560 in a water bath with the pH=12 alkali (sodium hydroxide) solution and the temperature of 60 ℃ for 30min, and the unmodified silver powder, the result is shown in figure 1, and figure 1 is the Fourier transform infrared spectrogram of the silane coupling agent KH-560 modified silver powder prepared in example 1. From the figure, it was possible to obtain a silver powder that was successfully modified by KH-560, and that could be removed by alkaline hydrolysis.
The second step, the preparation method of the silane coupling agent modified silver powder-epoxy resin composite substrate comprises the following steps:
uniformly mixing 20g of epoxy resin E-51, 16g of methyl tetrahydrophthalic anhydride and 0.1g of triethanolamine, and spin-coating to form a film (with an area of 7.5 cm) 2 ) The mixture was placed in an oven at 150℃for 40min to obtain a pre-cured epoxy resin.
Preparing silver powder-ethanol dispersion liquid with the concentration of 12.5% from the silane coupling agent modified silver powder prepared in the first step, 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 an oven with the temperature of 35 ℃ for 30min, then placing the silver powder-ethanol dispersion liquid in the oven with the temperature of 150 ℃ for continuous curing for 140min, cooling the silver powder-ethanol dispersion liquid at room temperature, and performing ultrasonic cleaning for 20min to obtain the silane coupling agent modified silver powder-epoxy resin composite substrate.
Thirdly, activating and plating copper on the silver powder-epoxy resin composite substrate modified by the silane coupling agent:
the preparation method of the alkaline reduction plating solution comprises the following steps: 0.4g CuSO 4 ·5H 2 O and 7.5g of EDTA-2Na are dissolved in 50mL of deionized water, the pH is regulated to 13 by dropwise adding of 5mol/L NaOH solution, and 1.5mL of 37% formaldehyde solution is added and stirred uniformly to obtain the alkaline reduction plating solution.
Placing the silane coupling agent modified silver powder-epoxy resin composite substrate prepared in the second step into 30mL of alkaline reduction plating solution, plating for 4h under the water bath condition with the temperature of 65 ℃, then ultrasonically washing with deionized water for 10min each time to obtain the silane coupling agent modified silver powder-epoxy resin composite material with copper plating layers on the surface, and carrying out section characterization on the prepared silane coupling agent modified silver powder-epoxy resin composite material with copper plating layers on the surface by using SEM (scanning electron microscope), wherein as shown in FIG. 2, FIG. 2 is an SEM image and an element analysis image of the silane coupling agent modified silver powder-epoxy resin composite material with copper plating layers on the surface, which are prepared in example 1, FIG. 2a is an SEM image of the cross section of a plating layer, FIG. 2b is an element analysis image of the plating layer, and the analysis can obtain the modified silver powder for catalytic copper plating, wherein the thickness of a copper plating layer is about 20 mu m, and the pull-out strength is 2.27MPa.
Changing the mass ratio of the silane coupling agent KH-560 to the silver powder from 0% to 7% (0%, 1%, 2%, 3%, 4%, 5%, 6%, 7%) to prepare a series of silane coupling agent modified silver powder, and researching siliconThe influence of the dosage of the alkane coupling agent KH-560 on the binding force of the plating layer is achieved, copper plating is carried out according to the second step and the third step, the pull-off strength of the silane coupling agent modified silver powder-epoxy resin composite material with the copper plating layer on the surface is shown in figure 3, the pull-off strength is tested according to national standard GB-5270-1985, and as the dosage of the KH-560 is increased, the binding force between the plating layer and the resin is increased and then reduced as shown in figure 3. When the use level of KH-560 is 4% of the mass of silver powder, the binding force between the plating layer and the resin is 2.27MPa at maximum, which is improved by 25.4% compared with the binding force of the plating layer when the silver powder is not modified by KH-560. The conductivity of the copper plating layer is about 3.15 multiplied by 10 7 S/m has great application prospect in the field of printed circuits.
Example 2
The preparation method of the modified copper powder-epoxy resin composite substrate 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 solution of the silane coupling agent KH-560 into 25mL of copper powder-ethanol dispersion liquid (the diameter of copper powder is 3 mu m, the mass of copper powder is 10% of the mass of ethanol), performing ultrasonic dispersion for 2h, enabling the silane coupling agent KH-560 to be fully adsorbed on the surface of copper powder, centrifuging to remove supernatant, placing the solid in a nitrogen atmosphere oven at 150 ℃ for dehydration for 2h, taking out the solid, respectively performing ultrasonic cleaning with excessive boiling water and absolute ethyl alcohol for 30min, and placing the cleaned copper powder in a nitrogen atmosphere oven at 80 ℃ for drying for 24h to obtain the silane coupling agent modified copper powder.
Uniformly mixing 20g of epoxy resin E-51, 16g of methyl tetrahydrophthalic anhydride and 0.1g of triethanolamine, and spin-coating to form a film (with an area of 7.5 cm) 2 ) The mixture was placed in an oven at a temperature of 150℃and pre-cured for 40min to obtain a pre-cured epoxy resin.
Preparing copper powder-ethanol dispersion liquid with the concentration of 12.5% from the modified copper powder, uniformly coating the copper powder-ethanol dispersion liquid on the surface of the pre-cured epoxy resin, heating and drying the copper powder in a baking oven with the temperature of 35 ℃ for 30min, then placing the copper powder-ethanol dispersion liquid in the baking oven with the temperature of 150 ℃ for continuous curing for 140min, cooling the copper powder-ethanol dispersion liquid at room temperature, and performing ultrasonic cleaning for 20min to obtain the modified copper powder-epoxy resin composite substrate.
And (3) placing the modified copper powder-epoxy resin composite substrate in 100mL of sodium hydroxide solution with the pH value of 12, performing alkaline washing for 30min at the temperature of 60 ℃, and then performing ultrasonic washing with deionized water for three times, each time for 5min, so as to obtain the copper powder-epoxy resin composite substrate after alkaline washing.
Activating copper plating on the copper powder-epoxy resin composite substrate after alkaline washing:
the preparation method of the alkaline reduction plating solution comprises the following steps: 0.35g of CuSO 4 ·5H 2 O and 7.0g of EDTA-2Na are dissolved in 50mL of deionized water, the pH is regulated to 12 by dropwise adding of NaOH solution with the concentration of 5mol/L, and 1.0mL of formaldehyde solution with the concentration of 37% is added for uniform mixing, so that the alkaline reduction plating solution is obtained.
And (3) placing the alkaline washed copper powder-epoxy resin composite substrate in 30mL of alkaline reduction plating solution, plating for 4h under the water bath condition of 60 ℃, and then ultrasonically washing with deionized water for three times, wherein each time is 10min, so as to obtain the alkaline washed copper powder-epoxy resin composite material with a copper plating layer on the surface. The copper plating thickness was about 20 μm. The pull-off strength is 2.10MPa.
Comparative example 1
Activating copper plating without KH-560 modified silver powder:
the preparation method of the alkaline reduction plating solution comprises the following steps: 0.35g of CuSO 4 ·5H 2 O and 7.0g of EDTA-2Na are dissolved in 50mL of deionized water, the pH is regulated to 12 by dropwise adding of NaOH solution with the concentration of 5mol/L, and 1.0mL of formaldehyde solution with the concentration of 37% is added for uniform mixing, so that the alkaline reduction plating solution is obtained.
The silver powder-epoxy resin composite substrate prepared by using unmodified silver powder (with the diameter of 1 μm) is placed in 30mL of alkaline reduction plating solution, plating is carried out for 4 hours under the water bath condition with the temperature of 60 ℃, and then ultrasonic washing is carried out for three times by using deionized water for 10 minutes each time, so as to obtain the silver foil composite material with the copper plating layer on the surface. The copper plating thickness was about 15 μm. The pull-off strength was 1.82MPa.
Example 3
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 solution of the silane coupling agent KH-560 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% of the mass of ethanol), performing ultrasonic dispersion for 2h, enabling the silane coupling agent KH-560 to be fully adsorbed on the surface of the silver powder, centrifuging to remove supernatant, placing the solid in a nitrogen oven at 150 ℃ for dehydration for 2h, taking out the solid, respectively performing ultrasonic cleaning with excessive boiling water and absolute ethyl alcohol for 30min, and placing the cleaned silver powder in a nitrogen oven at 80 ℃ for drying for 24h to obtain the silane coupling agent modified silver powder.
The second step, the preparation method of the silane coupling agent modified silver powder-epoxy resin composite substrate comprises the following steps:
uniformly mixing 20.5g of epoxy resin E-51, 15.5g of methyltetrahydrophthalic anhydride and 0.09g of triethanolamine, and spin-coating to form a film (with an area of 7.5 cm) 2 ) The mixture was placed in an oven at 150℃for 50 minutes to obtain a pre-cured epoxy resin.
Preparing silver powder-ethanol dispersion liquid with the concentration of 10% from the silane coupling agent modified silver powder prepared in the first step, 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 an oven with the temperature of 45 ℃ for 20min, then placing the silver powder-ethanol dispersion liquid in the oven with the temperature of 150 ℃ for continuous curing for 150min, cooling the silver powder-ethanol dispersion liquid at room temperature, and performing ultrasonic cleaning for 20min to obtain the silane coupling agent modified silver powder-epoxy resin composite substrate.
Thirdly, activating and plating copper on the silver powder-epoxy resin composite substrate modified by the silane coupling agent:
the preparation method of the alkaline reduction plating solution comprises the following steps: 0.3g of CuSO 4 ·5H 2 O and 7g of EDTA-2Na are dissolved in 50mL of deionized water, the pH is regulated to 12 by dropwise adding NaOH solution with the concentration of 5mol/L, 2mL of formaldehyde solution with the concentration of 37% is added, and the alkaline reduction plating solution is obtained by stirring and mixing uniformly.
And (3) placing the silane coupling agent modified silver powder-epoxy resin composite substrate prepared in the second step into 30mL of alkaline reduction plating solution, plating for 4 hours under the water bath condition of 65 ℃, and then ultrasonically washing with deionized water for three times, wherein each time is 10 minutes, so as to obtain the silane coupling agent modified silver powder-epoxy resin composite material with a copper plating layer on the surface. The copper plating thickness was about 18.5 μm. The pull-off strength was 1.92MPa.
Example 4
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 solution of the silane coupling agent KH-560 into 25mL of silver powder-ethanol dispersion liquid (the diameter of the silver powder is 2 mu m, the mass of the silver powder is 10% of the mass of ethanol), performing ultrasonic dispersion for 2h, enabling the silane coupling agent KH-560 to be fully adsorbed on the surface of the silver powder, centrifuging to remove supernatant, placing the solid in a nitrogen atmosphere oven at 150 ℃ for dehydration for 2h, taking out the solid, respectively performing ultrasonic cleaning with excessive boiling water and absolute ethyl alcohol for 30min, and placing the cleaned silver powder in a nitrogen atmosphere oven at 80 ℃ for drying for 24h to obtain the silane coupling agent modified silver powder.
The second step, the preparation method of the silane coupling agent modified silver powder-epoxy resin composite substrate 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 (area of 7.5 cm) 2 ) The mixture was placed in an oven at 150℃for 30 minutes to obtain a pre-cured epoxy resin.
Preparing silver powder-ethanol dispersion liquid with the concentration of 10% from the silane coupling agent modified silver powder prepared in the first step, 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 an oven with the temperature of 40 ℃ for 20min, then placing the silver powder-ethanol dispersion liquid in the oven with the temperature of 150 ℃ for continuous curing for 130min, cooling the silver powder-ethanol dispersion liquid at room temperature, and performing ultrasonic cleaning for 20min to obtain the silane coupling agent modified silver powder-epoxy resin composite substrate.
Thirdly, activating and plating copper on the silver powder-epoxy resin composite substrate modified by the silane coupling agent:
the preparation method of the alkaline reduction plating solution comprises the following steps: 0.3g of CuSO 4 ·5H 2 O, 8g EDTA-2Na was dissolved in 50And (3) dropwise adding NaOH solution with the concentration of 5mol/L into the deionized water, regulating the pH to 13, adding 1mL formaldehyde solution with the concentration of 37%, 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 substrate prepared in the second step into 30mL of alkaline reduction plating solution, plating for 5h under the water bath condition of 60 ℃, and then ultrasonically washing with deionized water for three times, wherein each time is 10min, so as to obtain the silane coupling agent modified silver powder-epoxy resin composite material with a copper plating layer on the surface. The copper plating thickness was about 19 μm. The pull-off strength is 2.20MPa.
Example 5
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 solution of the silane coupling agent KH-560 into 25mL of silver powder-ethanol dispersion liquid (the diameter of the silver powder is 5 mu m, the mass of the silver powder is 10% of the mass of ethanol), performing ultrasonic dispersion for 2h, enabling the silane coupling agent KH-560 to be fully adsorbed on the surface of the silver powder, centrifuging to remove supernatant, placing the solid in a nitrogen atmosphere oven at 150 ℃ for dehydration for 2h, taking out the solid, respectively performing ultrasonic cleaning with excessive boiling water and absolute ethyl alcohol for 30min, and placing the cleaned silver powder in a nitrogen atmosphere oven at 80 ℃ for drying for 24h to obtain the silane coupling agent modified silver powder.
The second step, the preparation method of the silane coupling agent modified silver powder-epoxy resin composite substrate comprises the following steps:
21g of epoxy resin E-51, 15.5g of methyltetrahydrophthalic anhydride and 0.1g of triethanolamine are uniformly mixed, and spin-coated to form a film (the area is 7.5 cm) 2 ) The mixture was placed in an oven at 150℃for 30 minutes to obtain a pre-cured epoxy resin.
Preparing silver powder-ethanol dispersion liquid with the concentration of 10% from the silane coupling agent modified silver powder prepared in the first step, 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 an oven with the temperature of 40 ℃ for 30min, then placing the silver powder-ethanol dispersion liquid in the oven with the temperature of 160 ℃ for continuous curing for 130min, cooling the silver powder-ethanol dispersion liquid at room temperature, and performing ultrasonic cleaning for 25min to obtain the silane coupling agent modified silver powder-epoxy resin composite substrate.
Thirdly, activating and plating copper on the silver powder-epoxy resin composite substrate modified by the silane coupling agent:
the preparation method of the alkaline reduction plating solution comprises the following steps: 0.5g CuSO 4 ·5H 2 O and 8g of EDTA-2Na are dissolved in 50mL of deionized water, the pH is regulated to 12 by dropwise adding NaOH solution with the concentration of 5mol/L, 2mL of formaldehyde solution with the concentration of 37% is added, and the alkaline reduction plating solution is obtained by stirring and mixing uniformly.
And (3) placing the silane coupling agent modified silver powder-epoxy resin composite substrate prepared in the second step into 30mL of alkaline reduction plating solution, plating for 4 hours under the water bath condition of 65 ℃, and then ultrasonically washing with deionized water for three times, wherein each time is 10 minutes, so as to obtain the silane coupling agent modified silver powder-epoxy resin composite material with a copper plating layer on the surface. The copper plating thickness was about 19 μm. The pull-off strength was 2.21MPa.
The foregoing description is only illustrative of the preferred embodiment of the present invention, and is not to be construed as limiting the invention, but is to be construed as limiting the invention to any and all simple modifications, equivalent variations and adaptations of the embodiments described above, which are within the scope of the invention, may be made by those skilled in the art without departing from the scope of the invention.
Claims (6)
1. A method for improving the binding force of a plating layer by activating copper plating on the surface of a modified metal is characterized by comprising the following steps: placing the metal modified epoxy resin composite substrate or the metal modified epoxy resin composite substrate subjected to alkali washing in an alkaline reduction plating solution, wherein the plating temperature is 55-65 ℃, and the plating time is 3-5 hours; ultrasonic cleaning is carried out for 5-60 min, and a metal/epoxy resin composite material containing a copper plating layer is obtained;
the preparation method of the alkaline reduction plating solution comprises the following steps ofThe method comprises the following steps: 0.3-0.5 g CuSO 4 ·5H 2 Dissolving O and 7-8 g of EDTA-2Na in 50mL deionized water, dropwise adding a NaOH solution to adjust the pH to 11-13, adding 1-2 mL of formaldehyde solution, and stirring and mixing uniformly to obtain the alkaline reduction plating solution;
the preparation method of the metal modified epoxy resin composite substrate comprises the following steps:
uniformly mixing epoxy resin, methyl tetrahydrophthalic anhydride and triethanolamine with the mass ratio of (19-21): (15.2-16.8): (0.09-0.11), and pre-curing for 30-60 min at the temperature of 130-160 ℃ to obtain pre-cured epoxy resin;
preparing modified metal powder into metal-ethanol dispersion liquid, uniformly coating the metal-ethanol dispersion liquid on the surface of the 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, uniformly mixing the solution with the concentration of the silane coupling agent of 0.001-3 g/mL, and regulating the pH value to 2-5 by using acetic acid;
mixing the silane coupling agent solution with the metal-ethanol dispersion liquid, performing ultrasonic dispersion, centrifugally removing supernatant, dehydrating for 1-12 hours in nitrogen atmosphere at the temperature of 140-160 ℃, taking out, respectively performing ultrasonic cleaning with excessive boiling water and absolute ethanol, and dehydrating for 1-48 hours in nitrogen atmosphere at the temperature of 60-100 ℃ to obtain modified metal powder;
the metal powder is silver powder or copper powder, and the diameter of the metal powder is 0.07-10 mu m;
the preparation method of the alkali-washed metal modified epoxy resin composite substrate comprises the following steps:
and (3) placing the metal modified epoxy resin composite substrate in a sodium hydroxide aqueous solution with the pH value of 11-13, performing alkaline washing for 20-40 min at the temperature of 50-80 ℃, and performing ultrasonic washing with deionized water for three times, wherein each time is 1-10 min, so as to obtain the metal modified epoxy resin composite substrate after alkaline washing.
2. The method for improving the bonding force of a plating layer by activating copper plating on a surface of a modified metal according to claim 1, wherein the concentration of the metal-ethanol dispersion is 10-15%.
3. The method for improving the binding force of a plating layer by activating copper plating on the surface of a modified metal according to claim 1, wherein the low-temperature drying temperature is 30-45 ℃ and the time is 20-40 min.
4. The method for improving the binding force of a plating layer by activating copper plating on the surface of a modified metal according to claim 1, wherein the high-temperature curing temperature is 140-160 ℃ and the time is 130-160 min.
5. The method for improving the binding force of a plating layer by activating copper plating on the surface of a modified metal according to claim 1, wherein the ultrasonic cleaning time is 20-30 min.
6. The method for improving the bonding force of a plating layer by activating copper plating on a surface of a modified metal according to claim 1, wherein the step of placing the alkali-washed metal modified epoxy resin composite substrate in an alkaline reduction plating solution is characterized in that the area of the metal modified epoxy resin composite substrate is 7.5cm 2 After alkali washing, the metal modified epoxy resin composite substrate is placed in 30-50 mL of alkaline reduction plating solution.
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| 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 |
| 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 |
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| WO2000001862A1 (en) * | 1998-07-07 | 2000-01-13 | Japan Energy Corporation | Pretreating agent for metal plating, and method for metal plating using the same |
| CN1174118C (en) * | 2000-01-07 | 2004-11-03 | 株式会社日矿材料 | Method for metal plating, pretreating agent, and semiconductor wafer and semiconductor device using same |
| US6780467B2 (en) * | 2000-04-25 | 2004-08-24 | Nikko Materials Co., Ltd. | Plating pretreatment agent and metal plating method using the same |
| WO2004108986A1 (en) * | 2003-06-09 | 2004-12-16 | Nikko Materials Co., Ltd. | Method for electroless plating and metal-plated article |
| KR101106845B1 (en) * | 2005-03-10 | 2012-01-19 | 닛코킨조쿠 가부시키가이샤 | Resin substrate |
| CN101492814B (en) * | 2009-02-26 | 2010-11-17 | 复旦大学 | Process for producing double-layer flexible cover copper plate |
| CN103866299B (en) * | 2014-03-24 | 2016-08-24 | 大连理工大学 | The pre-treating technology of epoxy resin-base composite material surface chemical plating |
| CN108754461A (en) * | 2018-05-24 | 2018-11-06 | 合肥学院 | A kind of method of surface of polymer substrates selective chemical plating |
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| 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 |
| 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 |
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