Detailed Description
The following further describes the embodiments of the present invention. It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1:
a surface treatment process of rolled copper foil comprises the following steps:
s1, cleaning: soaking the rolled copper foil in a cleaning solution for cleaning, taking out the rolled copper foil, cleaning the rolled copper foil for three times by using hot water at 50 ℃, and airing for later use; when the rolled copper foil is just rolled, the surface of the rolled copper foil is smooth, so that oil stains and an oxidation layer on the surface of the rolled copper foil need to be removed, the surface of the rolled copper foil is enabled to recover activity, in order to ensure that the surface of the rolled copper foil is cleaned, the rolled copper foil is soaked in a cleaning solution for three times for cleaning, the soaking time is 1min, and the cleaning time is three times after each soaking;
in order to effectively remove the greasy dirt and the oxidation layer on the surface of the rolled copper foil, the cleaning solution is optimized in the embodiment, and comprises the following components in percentage by weight:
15% of sodium dodecyl benzene sulfonate, 10% of fatty alcohol-polyoxyethylene ether, 8% of sulfuric acid, 1% of ethanol, 1% of potassium pyrophosphate and 65% of pure water;
the cleaning solution reasonably combines an anionic surfactant, a nonionic surfactant, sulfuric acid and the like, so that the cleaning solution can simultaneously remove oil stains and oxidation layers on the surface of the rolled copper foil, and has high cleaning efficiency;
s2, first coarsening: adding a roughening solution into the electroplating rectifier at a current density of 15A/dm2Electroplating 18S on the rolled copper foil at the temperature of 30 ℃;
coarsening is to generate copper nodules on the surface of the rolled copper foil, improve the surface area of the combination of the rolled copper foil and the substrate, further strengthen the binding force between the rolled copper foil and the substrate, and in order to improve the coarsening effect, the embodiment optimizes a coarsening solution, wherein the coarsening solution comprises 15g/L copper sulfate, 60g/L sulfuric acid, 3g/L ferrous sulfate and 1g/L nickel sulfate, and during preparation, the copper sulfate, the sulfuric acid, the ferrous sulfate and the nickel sulfate are sequentially added into pure water according to the proportion and are uniformly stirred;
s3, first curing: adding a curing liquid into the electroplating rectifier at a current density of 15A/dm2Electroplating 15S on the rolled copper foil at the temperature of 45 ℃;
the solidification has a reinforcing effect on the coarsened structure, a firm foundation is provided for subsequent treatment, and in order to improve the solidification effect, the solidification solution is optimized in the embodiment and comprises 60g/L copper sulfate, 90g/L sulfuric acid and 2g/L lecithin, and during preparation, the copper sulfate, the sulfuric acid and the lecithin are sequentially added into pure water according to the proportion and are uniformly stirred;
s4, secondary coarsening: adding the roughening solution in the first roughening step into the electroplating rectifier, and controlling the current density to be 8A/dm2Electroplating 10S on the rolled copper foil at the temperature of 20 ℃, and performing secondary roughening to improve the roughening effect of the rolled copper foil and greatly improve the binding force between the rolled copper foil and the substrate;
s5, secondary curing: adding the curing liquid in the first curing step into the electroplating rectifier, and controlling the current density to be 12A/dm2Electroplating 10S on the rolled copper foil at the temperature of 35 ℃, and performing secondary curing to reinforce the secondary coarsened structure;
s6, nickel-lanthanum alloy plating: adding a nickel-lanthanum alloy plating solution into an electroplating rectifier at a current density of 10A/dm2Electroplating 50S on the rolled copper foil at the temperature of 50 ℃, and forming a nickel-lanthanum alloy heat-resistant layer on the surface of the rolled copper foil through induced codeposition of nickel and lanthanum, so that the heat resistance and the high-temperature peeling strength of the copper foil are improved;
in order to improve the heat resistance of the copper foil, the heat-resistant plating layer is optimized in the embodiment, the nickel-lanthanum alloy plating solution comprises 35g/L nickel sulfamate, 20g/L lanthanum chloride, 3g/L urea and 2g/L sodium pyrophosphate, and during preparation, the nickel sulfamate, the lanthanum chloride, the urea and the sodium pyrophosphate are sequentially added into pure water according to the proportion, stirred and uniformly mixed, and then the pH value of the plating solution is adjusted to 3 by using citric acid;
s7, tungsten-zinc alloy plating: adding tungsten-zinc alloy plating solution into the electroplating rectifier at a current density of 5A/dm2Electroplating 25S on the rolled copper foil at the temperature of 40 ℃, forming a second heat-resistant layer, namely a tungsten-plated heat-resistant layer, on the surface of the rolled copper foil by taking sodium tungstate as a main salt and zinc nitrate as an auxiliary salt, and further improving the heat resistance and the high-temperature peeling strength of the copper foil;
in order to improve the heat resistance of the copper foil, the second heat-resistant plating layer is optimized in this embodiment, the tungsten-zinc alloy plating solution includes 20g/L sodium tungstate, 10g/L zinc nitrate, 1g/L sodium dodecyl sulfate, and 2g/L sodium citrate, and during the preparation, the sodium tungstate, the zinc nitrate, the sodium dodecyl sulfate, and the sodium citrate are sequentially added to pure water according to the above ratio, and are stirred and mixed uniformly, and then the PH is adjusted to 3 with a boric acid solution;
s8, passivation: in order to remove the redundant heat-resistant coating on the surface of the rolled copper foil and avoid the influence of the redundant heat-resistant coating on the subsequent treatment process, the rolled copper foil plated with the tungsten-zinc alloy is immersed in warm water at 45 ℃ for three times before passivation, then the passivation solution is heated to 40 ℃, and finally the rolled copper foil is immersed in the passivation solution for passivation for 35 s;
in the passivation, a layer of compact antioxidant film is formed on the surface of the rolled copper foil, so that the rolled copper foil is not in direct contact with air, the corrosion resistance of the rolled copper foil is improved, and in order to improve the oxidation resistance of the rolled copper foil, the embodiment optimizes a passivation solution, wherein the passivation solution comprises 6g/L titanium trichloride, 8g/L phytic acid, 8mL/L hydrogen peroxide and 10g/L sodium hexametaphosphate, and during preparation, the titanium trichloride, the phytic acid, the hydrogen peroxide and the sodium hexametaphosphate are sequentially added into pure water according to the proportion and uniformly stirred, and then the pH of the passivation solution is adjusted to 1 by using nitric acid;
s9, drying: placing the passivated rolled copper foil in a 50 ℃ drying oven to be dried for 10 hours;
s10, silane coupling agent treatment: firstly, preparing 3% of silane coupling agent alcohol solution by using absolute ethyl alcohol, wherein the silane coupling agent adopts silane coupling agent kh550, then soaking the dried rolled aluminum foil into the silane coupling agent alcohol solution, taking out the aluminum foil after 15s, and finally curing the aluminum foil for 3h at 70 ℃, so that the surface treatment work of the rolled copper foil can be completed, and the corrosion resistance of the rolled copper foil can be further improved by the silane coupling agent treatment process.
Example 2:
a surface treatment process of rolled copper foil comprises the following steps:
s1, cleaning: soaking the rolled copper foil in a cleaning solution for cleaning, taking out the rolled copper foil, cleaning the rolled copper foil for three times by using hot water at 65 ℃, and airing for later use; when the rolled copper foil is just rolled, the surface of the rolled copper foil is smooth, so that oil stains and an oxidation layer on the surface of the rolled copper foil need to be removed, the surface of the rolled copper foil is enabled to recover activity, in order to ensure that the surface of the rolled copper foil is cleaned, the rolled copper foil is soaked in a cleaning solution for three times for cleaning, the soaking time is 1.5min, and the rolled copper foil needs to be cleaned for three times by hot water at 65 ℃ after each soaking time;
in order to effectively remove the greasy dirt and the oxidation layer on the surface of the rolled copper foil, the cleaning solution is optimized in the embodiment, and comprises the following components in percentage by weight:
18% of sodium dodecyl benzene sulfonate, 12.5% of fatty alcohol-polyoxyethylene ether, 10% of sulfuric acid, 2% of ethanol, 2% of potassium pyrophosphate and 55.5% of pure water;
the cleaning solution reasonably combines an anionic surfactant, a nonionic surfactant, sulfuric acid and the like, so that the cleaning solution can simultaneously remove oil stains and oxidation layers on the surface of the rolled copper foil, and has high cleaning efficiency;
s2, first coarsening: adding a roughening solution into the electroplating rectifier at a current density of 18A/dm2Electroplating 15S on the rolled copper foil at the temperature of 35 ℃;
coarsening is to generate copper nodules on the surface of the rolled copper foil, improve the surface area of the combination of the rolled copper foil and the substrate, further strengthen the binding force between the rolled copper foil and the substrate, and in order to improve the coarsening effect, the embodiment optimizes a coarsening solution, wherein the coarsening solution comprises 20g/L copper sulfate, 70g/L sulfuric acid, 4g/L ferrous sulfate and 2g/L nickel sulfate, and during preparation, the copper sulfate, the sulfuric acid, the ferrous sulfate and the nickel sulfate are sequentially added into pure water according to the proportion and are uniformly stirred;
s3, firstPrimary curing: adding a curing liquid into the electroplating rectifier at a current density of 18A/dm2Electroplating 12S on the rolled copper foil at the temperature of 50 ℃;
the solidification has a reinforcing effect on the coarsened structure, a firm foundation is provided for subsequent treatment, and in order to improve the solidification effect, the solidification solution is optimized in the embodiment and comprises 65g/L copper sulfate, 95g/L sulfuric acid and 2.5g/L lecithin, and during preparation, the copper sulfate, the sulfuric acid and the lecithin are sequentially added into pure water according to the proportion and are uniformly stirred;
s4, secondary coarsening: adding the roughening solution in the first roughening step into a plating rectifier at a current density of 10A/dm2Electroplating the rolled copper foil for 8.5S at the temperature of 25 ℃, and performing secondary roughening to improve the roughening effect of the rolled copper foil and greatly improve the bonding force between the rolled copper foil and the substrate;
s5, secondary curing: adding the curing liquid in the first curing step into a plating rectifier at a current density of 13.5A/dm2Electroplating the rolled copper foil for 7.5 seconds at the temperature of 38 ℃, and performing secondary curing to reinforce the secondary coarsened structure;
s6, nickel-lanthanum alloy plating: adding a nickel-lanthanum alloy plating solution into an electroplating rectifier at a current density of 15A/dm2Electroplating 40S on the rolled copper foil at the temperature of 58 ℃, and forming a nickel-lanthanum alloy heat-resistant layer on the surface of the rolled copper foil through induced codeposition of nickel and lanthanum, so that the heat resistance and the high-temperature peeling strength of the copper foil are improved;
in order to improve the heat resistance of the copper foil, the heat-resistant plating layer is optimized in the embodiment, the nickel-lanthanum alloy plating solution comprises 40g/L nickel sulfamate, 25g/L lanthanum chloride, 4g/L urea and 2.5g/L sodium pyrophosphate, and during preparation, the nickel sulfamate, the lanthanum chloride, the urea and the sodium pyrophosphate are sequentially added into pure water according to the proportion, stirred and mixed uniformly, and then the pH value of the plating solution is adjusted to 4.5 by using citric acid;
s7, tungsten-zinc alloy plating: adding tungsten-zinc alloy plating solution into the electroplating rectifier at a current density of 8A/dm2Electroplating rolled copper foil for 20S at 45 ℃ with sodium tungstate as main saltZinc nitrate is used as auxiliary salt, and a second heat-resistant layer, namely a tungsten-plated heat-resistant layer, is formed on the surface of the rolled copper foil, so that the heat resistance and the high-temperature peeling strength of the copper foil are further improved;
in order to improve the heat resistance of the copper foil, the second heat-resistant plating layer is optimized in this embodiment, the tungsten-zinc alloy plating solution includes 25g/L sodium tungstate, 12.5g/L zinc nitrate, 1.5g/L sodium dodecyl sulfate, and 2.5g/L sodium citrate, and during the preparation, the sodium tungstate, the zinc nitrate, the sodium dodecyl sulfate, and the sodium citrate are sequentially added to pure water according to the above ratio, and are uniformly stirred, and then the PH is adjusted to 4 by using a boric acid solution;
s8, passivation: in order to remove the redundant heat-resistant coating on the surface of the rolled copper foil and avoid the influence of the redundant heat-resistant coating on the subsequent treatment process, the rolled copper foil plated with the tungsten-zinc alloy is immersed in warm water at 50 ℃ for three times before passivation, then the passivation solution is heated to 45 ℃, and finally the rolled copper foil is immersed in the passivation solution for passivation for 30 seconds;
in the passivation, a layer of compact antioxidant film is formed on the surface of the rolled copper foil, so that the rolled copper foil is not in direct contact with air, the corrosion resistance of the rolled copper foil is improved, and in order to improve the oxidation resistance of the rolled copper foil, the embodiment optimizes a passivation solution, wherein the passivation solution comprises 8g/L titanium trichloride, 10g/L phytic acid, 12mL/L hydrogen peroxide and 14g/L sodium hexametaphosphate, and during preparation, the titanium trichloride, the phytic acid, the hydrogen peroxide and the sodium hexametaphosphate are sequentially added into pure water according to the proportion and uniformly stirred, and then the pH of the passivation solution is adjusted to 2 by using nitric acid;
s9, drying: placing the passivated rolled copper foil in an oven at 55 ℃ for drying for 9 hours;
s10, silane coupling agent treatment: firstly, preparing a 4% silane coupling agent alcohol solution by using absolute ethyl alcohol, wherein the silane coupling agent adopts a silane coupling agent kh550, then soaking the dried rolled aluminum foil into the silane coupling agent alcohol solution, taking out the rolled aluminum foil after 12 seconds, and finally curing the rolled aluminum foil for 2 hours at 75 ℃ to finish the surface treatment work of the rolled copper foil, wherein the corrosion resistance of the rolled copper foil can be further improved by the silane coupling agent treatment process.
Example 3:
a surface treatment process of rolled copper foil comprises the following steps:
s1, cleaning: soaking the rolled copper foil in a cleaning solution for cleaning, taking out the rolled copper foil, cleaning the rolled copper foil for three times by using hot water at the temperature of 80 ℃, and airing the rolled copper foil for later use; when the rolled copper foil is just rolled, the surface of the rolled copper foil is smooth, so that oil stains and an oxidation layer on the surface of the rolled copper foil need to be removed, the surface of the rolled copper foil is enabled to recover activity, in order to ensure that the surface of the rolled copper foil is cleaned, the rolled copper foil is soaked in a cleaning solution for three times for cleaning, each soaking time is 2min, and after each soaking time, the rolled copper foil needs to be cleaned for three times by hot water at 80 ℃;
in order to effectively remove the greasy dirt and the oxidation layer on the surface of the rolled copper foil, the cleaning solution is optimized in the embodiment, and comprises the following components in percentage by weight:
20% of sodium dodecyl benzene sulfonate, 15% of fatty alcohol-polyoxyethylene ether, 12% of sulfuric acid, 3% of ethanol, 3% of potassium pyrophosphate and 47% of pure water;
the cleaning solution reasonably combines an anionic surfactant, a nonionic surfactant, sulfuric acid and the like, so that the cleaning solution can simultaneously remove oil stains and oxidation layers on the surface of the rolled copper foil, and has high cleaning efficiency;
s2, first coarsening: adding a roughening solution into the electroplating rectifier at a current density of 20A/dm2Electroplating 12S on the rolled copper foil at the temperature of 40 ℃;
coarsening is to generate copper nodules on the surface of the rolled copper foil, improve the surface area of the combination of the rolled copper foil and the substrate, further strengthen the binding force between the rolled copper foil and the substrate, and in order to improve the coarsening effect, the embodiment optimizes a coarsening solution, wherein the coarsening solution comprises 25g/L copper sulfate, 80g/L sulfuric acid, 5g/L ferrous sulfate and 3g/L nickel sulfate, and during preparation, the copper sulfate, the sulfuric acid, the ferrous sulfate and the nickel sulfate are sequentially added into pure water according to the proportion and are uniformly stirred;
s3, first curing: adding a curing liquid into the electroplating rectifier at a current density of 20A/dm2Electroplating the rolled copper foil for 8S at the temperature of 55 ℃;
the solidification has a reinforcing effect on the coarsened structure, a firm foundation is provided for subsequent treatment, and in order to improve the solidification effect, the solidification solution is optimized in the embodiment and comprises 70g/L copper sulfate, 100g/L sulfuric acid and 3g/L lecithin, and during preparation, the copper sulfate, the sulfuric acid and the lecithin are sequentially added into pure water according to the proportion and are uniformly stirred;
s4, secondary coarsening: adding the roughening solution in the first roughening step into a plating rectifier at a current density of 12A/dm2Electroplating 7S on the rolled copper foil at the temperature of 30 ℃, and performing secondary roughening to improve the roughening effect of the rolled copper foil and greatly improve the binding force between the rolled copper foil and the substrate;
s5, secondary curing: adding the curing liquid in the first curing step into the electroplating rectifier, and controlling the current density to be 15A/dm2Electroplating the rolled copper foil for 5 seconds at the temperature of 40 ℃, and performing secondary curing to reinforce the secondary coarsened structure;
s6, nickel-lanthanum alloy plating: adding a nickel-lanthanum alloy plating solution into an electroplating rectifier at a current density of 20A/dm2Electroplating 30S on the rolled copper foil at the temperature of 65 ℃, and forming a nickel-lanthanum alloy heat-resistant layer on the surface of the rolled copper foil through induced codeposition of nickel and lanthanum, so that the heat resistance and the high-temperature peeling strength of the copper foil are improved;
in order to improve the heat resistance of the copper foil, the heat-resistant plating layer is optimized in the embodiment, the nickel-lanthanum alloy plating solution comprises 45g/L nickel sulfamate, 30g/L lanthanum chloride, 5g/L urea and 3g/L sodium pyrophosphate, and during preparation, the nickel sulfamate, the lanthanum chloride, the urea and the sodium pyrophosphate are sequentially added into pure water according to the proportion, stirred and uniformly mixed, and then the pH value of the plating solution is adjusted to 6 by using citric acid;
s7, tungsten-zinc alloy plating: adding tungsten-zinc alloy plating solution into the electroplating rectifier at a current density of 10A/dm2Electroplating 25S on the rolled copper foil at the temperature of 50 ℃, forming a second heat-resistant layer, namely a tungsten-plated heat-resistant layer, on the surface of the rolled copper foil by taking sodium tungstate as a main salt and zinc nitrate as an auxiliary salt, and further improving the heat resistance and the high-temperature peeling strength of the copper foil;
in order to improve the heat resistance of the copper foil, the second heat-resistant plating layer is optimized in this embodiment, the tungsten-zinc alloy plating solution includes 30g/L sodium tungstate, 15g/L zinc nitrate, 2g/L sodium dodecyl sulfate, and 3g/L sodium citrate, and during the preparation, the sodium tungstate, the zinc nitrate, the sodium dodecyl sulfate, and the sodium citrate are sequentially added to pure water according to the above ratio, and are stirred and mixed uniformly, and then the PH is adjusted to 5 with a boric acid solution;
s8, passivation: in order to remove the redundant heat-resistant coating on the surface of the rolled copper foil and avoid the influence of the redundant heat-resistant coating on the subsequent treatment process, the rolled copper foil plated with the tungsten-zinc alloy is immersed in warm water at 55 ℃ for three times before passivation, then the passivation solution is heated to 50 ℃, and finally the rolled copper foil is immersed in the passivation solution for passivation for 25 s;
in the passivation, a layer of compact antioxidant film is formed on the surface of the rolled copper foil, so that the rolled copper foil is not in direct contact with air, the corrosion resistance of the rolled copper foil is improved, and in order to improve the oxidation resistance of the rolled copper foil, the embodiment optimizes a passivation solution, wherein the passivation solution comprises 10g/L of titanium trichloride, 12g/L of phytic acid, 15mL/L of hydrogen peroxide and 18g/L of sodium hexametaphosphate, and during preparation, the titanium trichloride, the phytic acid, the hydrogen peroxide and the sodium hexametaphosphate are sequentially added into pure water according to the proportion and uniformly stirred, and then the pH of the passivation solution is adjusted to 3 by using nitric acid;
s9, drying: placing the passivated rolled copper foil in a 60 ℃ drying oven to be dried for 8 hours;
s10, silane coupling agent treatment: firstly, preparing a 5% silane coupling agent alcohol solution by using absolute ethyl alcohol, wherein the silane coupling agent adopts a silane coupling agent kh550, then soaking the dried rolled aluminum foil into the silane coupling agent alcohol solution, taking out the aluminum foil after 10 seconds, and finally curing the aluminum foil for 1 hour at 80 ℃, so that the surface treatment work of the rolled copper foil can be completed, and the corrosion resistance of the rolled copper foil can be further improved by the silane coupling agent treatment process.
Example 4:
a surface treatment process of rolled copper foil comprises the following steps:
s1, cleaning: soaking the rolled copper foil in a cleaning solution for cleaning, taking out the rolled copper foil, cleaning the rolled copper foil for three times by using hot water at 65 ℃, and airing for later use; when the rolled copper foil is just rolled, the surface of the rolled copper foil is smooth, so that oil stains and an oxidation layer on the surface of the rolled copper foil need to be removed, the surface of the rolled copper foil is enabled to recover activity, in order to ensure that the surface of the rolled copper foil is cleaned, the rolled copper foil is soaked in a cleaning solution for three times for cleaning, the soaking time is 1.5min, and the rolled copper foil needs to be cleaned for three times by hot water at 65 ℃ after each soaking time;
in order to effectively remove the greasy dirt and the oxidation layer on the surface of the rolled copper foil, the cleaning solution is optimized in the embodiment, and comprises the following components in percentage by weight:
18% sodium stearate, 12.5% coconut diethanolamide, 10% sulfuric acid, 2% isopropanol, 2% sodium nitrite and 55.5% pure water;
the cleaning solution reasonably combines an anionic surfactant, a nonionic surfactant, sulfuric acid and the like, so that the cleaning solution can simultaneously remove oil stains and oxidation layers on the surface of the rolled copper foil, and has high cleaning efficiency;
s2, first coarsening: adding a roughening solution into the electroplating rectifier at a current density of 18A/dm2Electroplating 15S on the rolled copper foil at the temperature of 35 ℃;
coarsening is to generate copper nodules on the surface of the rolled copper foil, improve the surface area of the combination of the rolled copper foil and the substrate, further strengthen the binding force between the rolled copper foil and the substrate, and in order to improve the coarsening effect, the embodiment optimizes a coarsening solution, wherein the coarsening solution comprises 20g/L copper sulfate, 70g/L sulfuric acid, 4g/L ferrous sulfate and 2g/L nickel sulfate, and during preparation, the copper sulfate, the sulfuric acid, the ferrous sulfate and the nickel sulfate are sequentially added into pure water according to the proportion and are uniformly stirred;
s3, first curing: adding a curing liquid into the electroplating rectifier at a current density of 18A/dm2Electroplating 12S on the rolled copper foil at the temperature of 50 ℃;
the solidification has a reinforcing effect on the coarsened structure, a firm foundation is provided for subsequent treatment, and in order to improve the solidification effect, the solidification solution is optimized in the embodiment and comprises 65g/L copper sulfate, 95g/L sulfuric acid and 2.5g/L lecithin, and during preparation, the copper sulfate, the sulfuric acid and the lecithin are sequentially added into pure water according to the proportion and are uniformly stirred;
s4, twiceCoarsening: adding the roughening solution in the first roughening step into a plating rectifier at a current density of 10A/dm2Electroplating the rolled copper foil for 8.5S at the temperature of 25 ℃, and performing secondary roughening to improve the roughening effect of the rolled copper foil and greatly improve the bonding force between the rolled copper foil and the substrate;
s5, secondary curing: adding the curing liquid in the first curing step into a plating rectifier at a current density of 13.5A/dm2Electroplating the rolled copper foil for 7.5 seconds at the temperature of 38 ℃, and performing secondary curing to reinforce the secondary coarsened structure;
s6, nickel-lanthanum alloy plating: adding a nickel-lanthanum alloy plating solution into an electroplating rectifier at a current density of 15A/dm2Electroplating 40S on the rolled copper foil at the temperature of 58 ℃, and forming a nickel-lanthanum alloy heat-resistant layer on the surface of the rolled copper foil through induced codeposition of nickel and lanthanum, so that the heat resistance and the high-temperature peeling strength of the copper foil are improved;
in order to improve the heat resistance of the copper foil, the heat-resistant plating layer is optimized in the embodiment, the nickel-lanthanum alloy plating solution comprises 40g/L nickel sulfamate, 25g/L lanthanum chloride, 4g/L urea and 2.5g/L sodium pyrophosphate, and during preparation, the nickel sulfamate, the lanthanum chloride, the urea and the sodium pyrophosphate are sequentially added into pure water according to the proportion, stirred and mixed uniformly, and then the pH value of the plating solution is adjusted to 4.5 by using citric acid;
s7, tungsten-zinc alloy plating: adding tungsten-zinc alloy plating solution into the electroplating rectifier at a current density of 8A/dm2Electroplating 20S on the rolled copper foil at the temperature of 45 ℃, forming a second heat-resistant layer, namely a tungsten-plated heat-resistant layer, on the surface of the rolled copper foil by taking sodium tungstate as a main salt and zinc nitrate as an auxiliary salt, and further improving the heat resistance and the high-temperature peeling strength of the copper foil;
in order to improve the heat resistance of the copper foil, the second heat-resistant plating layer is optimized in this embodiment, the tungsten-zinc alloy plating solution includes 25g/L sodium tungstate, 12.5g/L zinc nitrate, 1.5g/L sodium dodecyl sulfate, and 2.5g/L sodium citrate, and during the preparation, the sodium tungstate, the zinc nitrate, the sodium dodecyl sulfate, and the sodium citrate are sequentially added to pure water according to the above ratio, and are uniformly stirred, and then the PH is adjusted to 4 by using a boric acid solution;
s8, passivation: in order to remove the redundant heat-resistant coating on the surface of the rolled copper foil and avoid the influence of the redundant heat-resistant coating on the subsequent treatment process, the rolled copper foil plated with the tungsten-zinc alloy is immersed in warm water at 50 ℃ for three times before passivation, then the passivation solution is heated to 45 ℃, and finally the rolled copper foil is immersed in the passivation solution for passivation for 30 seconds;
in the passivation, a layer of compact antioxidant film is formed on the surface of the rolled copper foil, so that the rolled copper foil is not in direct contact with air, the corrosion resistance of the rolled copper foil is improved, and in order to improve the oxidation resistance of the rolled copper foil, the embodiment optimizes a passivation solution, wherein the passivation solution comprises 8g/L titanium trichloride, 10g/L phytic acid, 12mL/L hydrogen peroxide and 14g/L sodium hexametaphosphate, and during preparation, the titanium trichloride, the phytic acid, the hydrogen peroxide and the sodium hexametaphosphate are sequentially added into pure water according to the proportion and uniformly stirred, and then the pH of the passivation solution is adjusted to 2 by using nitric acid;
s9, drying: placing the passivated rolled copper foil in an oven at 55 ℃ for drying for 9 hours;
s10, silane coupling agent treatment: firstly, preparing a 4% silane coupling agent alcohol solution by using absolute ethyl alcohol, wherein the silane coupling agent adopts a silane coupling agent kh550, then soaking the dried rolled aluminum foil into the silane coupling agent alcohol solution, taking out the rolled aluminum foil after 12 seconds, and finally curing the rolled aluminum foil for 2 hours at 75 ℃ to finish the surface treatment work of the rolled copper foil, wherein the corrosion resistance of the rolled copper foil can be further improved by the silane coupling agent treatment process.
Example 5:
a surface treatment process of rolled copper foil comprises the following steps:
s1, cleaning: soaking the rolled copper foil in a cleaning solution for cleaning, taking out the rolled copper foil, cleaning the rolled copper foil for three times by using hot water at 65 ℃, and airing for later use; when the rolled copper foil is just rolled, the surface of the rolled copper foil is smooth, so that oil stains and an oxidation layer on the surface of the rolled copper foil need to be removed, the surface of the rolled copper foil is enabled to recover activity, in order to ensure that the surface of the rolled copper foil is cleaned, the rolled copper foil is soaked in a cleaning solution for three times for cleaning, the soaking time is 1.5min, and the rolled copper foil needs to be cleaned for three times by hot water at 65 ℃ after each soaking time;
in order to effectively remove the greasy dirt and the oxidation layer on the surface of the rolled copper foil, the cleaning solution is optimized in the embodiment, and comprises the following components in percentage by weight:
18% of lauryl alcohol, 12.5% of alkylphenol polyoxyethylene, 10% of sulfuric acid, 2% of butanol, 2% of sodium benzoate and 55.5% of pure water;
the cleaning solution reasonably combines an anionic surfactant, a nonionic surfactant, sulfuric acid and the like, so that the cleaning solution can simultaneously remove oil stains and oxidation layers on the surface of the rolled copper foil, and has high cleaning efficiency;
s2, first coarsening: adding a roughening solution into the electroplating rectifier at a current density of 18A/dm2Electroplating 15S on the rolled copper foil at the temperature of 35 ℃;
coarsening is to generate copper nodules on the surface of the rolled copper foil, improve the surface area of the combination of the rolled copper foil and the substrate, further strengthen the binding force between the rolled copper foil and the substrate, and in order to improve the coarsening effect, the embodiment optimizes a coarsening solution, wherein the coarsening solution comprises 20g/L copper sulfate, 70g/L sulfuric acid, 4g/L ferrous sulfate and 2g/L nickel sulfate, and during preparation, the copper sulfate, the sulfuric acid, the ferrous sulfate and the nickel sulfate are sequentially added into pure water according to the proportion and are uniformly stirred;
s3, first curing: adding a curing liquid into the electroplating rectifier at a current density of 18A/dm2Electroplating 12S on the rolled copper foil at the temperature of 50 ℃;
the solidification has a reinforcing effect on the coarsened structure, a firm foundation is provided for subsequent treatment, and in order to improve the solidification effect, the solidification solution is optimized in the embodiment and comprises 65g/L copper sulfate, 95g/L sulfuric acid and 2.5g/L lecithin, and during preparation, the copper sulfate, the sulfuric acid and the lecithin are sequentially added into pure water according to the proportion and are uniformly stirred;
s4, secondary coarsening: adding the roughening solution in the first roughening step into a plating rectifier at a current density of 10A/dm2Electroplating the rolled copper foil for 8.5S at the temperature of 25 ℃, and performing secondary roughening to improve the roughening effect of the rolled copper foil and greatly improve the bonding force between the rolled copper foil and the substrate;
s5, secondary curing: adding the curing liquid in the first curing step into a plating rectifier at a current density of 13.5A/dm2Electroplating the rolled copper foil for 7.5 seconds at the temperature of 38 ℃, and performing secondary curing to reinforce the secondary coarsened structure;
s6, nickel-lanthanum alloy plating: adding a nickel-lanthanum alloy plating solution into an electroplating rectifier at a current density of 15A/dm2Electroplating 40S on the rolled copper foil at the temperature of 58 ℃, and forming a nickel-lanthanum alloy heat-resistant layer on the surface of the rolled copper foil through induced codeposition of nickel and lanthanum, so that the heat resistance and the high-temperature peeling strength of the copper foil are improved;
in order to improve the heat resistance of the copper foil, the heat-resistant plating layer is optimized in the embodiment, the nickel-lanthanum alloy plating solution comprises 40g/L nickel sulfamate, 25g/L lanthanum chloride, 4g/L urea and 2.5g/L sodium pyrophosphate, and during preparation, the nickel sulfamate, the lanthanum chloride, the urea and the sodium pyrophosphate are sequentially added into pure water according to the proportion, stirred and mixed uniformly, and then the pH value of the plating solution is adjusted to 4.5 by using citric acid;
s7, tungsten-zinc alloy plating: adding tungsten-zinc alloy plating solution into the electroplating rectifier at a current density of 8A/dm2Electroplating 20S on the rolled copper foil at the temperature of 45 ℃, forming a second heat-resistant layer, namely a tungsten-plated heat-resistant layer, on the surface of the rolled copper foil by taking sodium tungstate as a main salt and zinc nitrate as an auxiliary salt, and further improving the heat resistance and the high-temperature peeling strength of the copper foil;
in order to improve the heat resistance of the copper foil, the second heat-resistant plating layer is optimized in this embodiment, the tungsten-zinc alloy plating solution includes 25g/L sodium tungstate, 12.5g/L zinc nitrate, 1.5g/L sodium dodecyl sulfate, and 2.5g/L sodium citrate, and during the preparation, the sodium tungstate, the zinc nitrate, the sodium dodecyl sulfate, and the sodium citrate are sequentially added to pure water according to the above ratio, and are uniformly stirred, and then the PH is adjusted to 4 by using a boric acid solution;
s8, passivation: in order to remove the redundant heat-resistant coating on the surface of the rolled copper foil and avoid the influence of the redundant heat-resistant coating on the subsequent treatment process, the rolled copper foil plated with the tungsten-zinc alloy is immersed in warm water at 50 ℃ for three times before passivation, then the passivation solution is heated to 45 ℃, and finally the rolled copper foil is immersed in the passivation solution for passivation for 30 seconds;
in the passivation, a layer of compact antioxidant film is formed on the surface of the rolled copper foil, so that the rolled copper foil is not in direct contact with air, the corrosion resistance of the rolled copper foil is improved, and in order to improve the oxidation resistance of the rolled copper foil, the embodiment optimizes a passivation solution, wherein the passivation solution comprises 8g/L titanium trichloride, 10g/L phytic acid, 12mL/L hydrogen peroxide and 14g/L sodium hexametaphosphate, and during preparation, the titanium trichloride, the phytic acid, the hydrogen peroxide and the sodium hexametaphosphate are sequentially added into pure water according to the proportion and uniformly stirred, and then the pH of the passivation solution is adjusted to 2 by using nitric acid;
s9, drying: placing the passivated rolled copper foil in an oven at 55 ℃ for drying for 9 hours;
s10, silane coupling agent treatment: firstly, preparing a 4% silane coupling agent alcohol solution by using absolute ethyl alcohol, wherein the silane coupling agent adopts a silane coupling agent kh550, then soaking the dried rolled aluminum foil into the silane coupling agent alcohol solution, taking out the rolled aluminum foil after 12 seconds, and finally curing the rolled aluminum foil for 2 hours at 75 ℃ to finish the surface treatment work of the rolled copper foil, wherein the corrosion resistance of the rolled copper foil can be further improved by the silane coupling agent treatment process.
Example 6:
a surface treatment process of rolled copper foil comprises the following steps:
s1, cleaning: soaking the rolled copper foil in a cleaning solution for cleaning, taking out the rolled copper foil, cleaning the rolled copper foil for three times by using hot water at 65 ℃, and airing for later use; when the rolled copper foil is just rolled, the surface of the rolled copper foil is smooth, so that oil stains and an oxidation layer on the surface of the rolled copper foil need to be removed, the surface of the rolled copper foil is enabled to recover activity, in order to ensure that the surface of the rolled copper foil is cleaned, the rolled copper foil is soaked in a cleaning solution for three times for cleaning, the soaking time is 1.5min, and the rolled copper foil needs to be cleaned for three times by hot water at 65 ℃ after each soaking time;
in order to effectively remove the greasy dirt and the oxidation layer on the surface of the rolled copper foil, the cleaning solution is optimized in the embodiment, and comprises the following components in percentage by weight:
18% vinyl ether, 12.5% polyoxyethylene fatty acid ester, 10% sulfuric acid, 2% ethanol, 2% sodium sulfate and 55.5% pure water;
the cleaning solution reasonably combines an anionic surfactant, a nonionic surfactant, sulfuric acid and the like, so that the cleaning solution can simultaneously remove oil stains and oxidation layers on the surface of the rolled copper foil, and has high cleaning efficiency;
s2, first coarsening: adding a roughening solution into the electroplating rectifier at a current density of 18A/dm2Electroplating 15S on the rolled copper foil at the temperature of 35 ℃;
coarsening is to generate copper nodules on the surface of the rolled copper foil, improve the surface area of the combination of the rolled copper foil and the substrate, further strengthen the binding force between the rolled copper foil and the substrate, and in order to improve the coarsening effect, the embodiment optimizes a coarsening solution, wherein the coarsening solution comprises 20g/L copper sulfate, 70g/L sulfuric acid, 4g/L ferrous sulfate and 2g/L nickel sulfate, and during preparation, the copper sulfate, the sulfuric acid, the ferrous sulfate and the nickel sulfate are sequentially added into pure water according to the proportion and are uniformly stirred;
s3, first curing: adding a curing liquid into the electroplating rectifier at a current density of 18A/dm2Electroplating 12S on the rolled copper foil at the temperature of 50 ℃;
the solidification has a reinforcing effect on the coarsened structure, a firm foundation is provided for subsequent treatment, and in order to improve the solidification effect, the solidification solution is optimized in the embodiment and comprises 65g/L copper sulfate, 95g/L sulfuric acid and 2.5g/L lecithin, and during preparation, the copper sulfate, the sulfuric acid and the lecithin are sequentially added into pure water according to the proportion and are uniformly stirred;
s4, secondary coarsening: adding the roughening solution in the first roughening step into a plating rectifier at a current density of 10A/dm2Electroplating the rolled copper foil for 8.5S at the temperature of 25 ℃, and performing secondary roughening to improve the roughening effect of the rolled copper foil and greatly improve the bonding force between the rolled copper foil and the substrate;
s5, secondary curing: adding the curing liquid in the first curing step into a plating rectifier at a current density of 13.5A/dm2Electroplating the rolled copper foil for 7.5 seconds at the temperature of 38 ℃, and performing secondary curing to reinforce the secondary coarsened structure;
s6, nickel-lanthanum alloy plating: adding a nickel-lanthanum alloy plating solution into an electroplating rectifier at a current density of 15A/dm2Electroplating 40S on the rolled copper foil at the temperature of 58 ℃, and forming a nickel-lanthanum alloy heat-resistant layer on the surface of the rolled copper foil through induced codeposition of nickel and lanthanum, so that the heat resistance and the high-temperature peeling strength of the copper foil are improved;
in order to improve the heat resistance of the copper foil, the heat-resistant plating layer is optimized in the embodiment, the nickel-lanthanum alloy plating solution comprises 40g/L nickel sulfamate, 25g/L lanthanum chloride, 4g/L urea and 2.5g/L sodium pyrophosphate, and during preparation, the nickel sulfamate, the lanthanum chloride, the urea and the sodium pyrophosphate are sequentially added into pure water according to the proportion, stirred and mixed uniformly, and then the pH value of the plating solution is adjusted to 4.5 by using citric acid;
s7, tungsten-zinc alloy plating: adding tungsten-zinc alloy plating solution into the electroplating rectifier at a current density of 8A/dm2Electroplating 20S on the rolled copper foil at the temperature of 45 ℃, forming a second heat-resistant layer, namely a tungsten-plated heat-resistant layer, on the surface of the rolled copper foil by taking sodium tungstate as a main salt and zinc nitrate as an auxiliary salt, and further improving the heat resistance and the high-temperature peeling strength of the copper foil;
in order to improve the heat resistance of the copper foil, the second heat-resistant plating layer is optimized in this embodiment, the tungsten-zinc alloy plating solution includes 25g/L sodium tungstate, 12.5g/L zinc nitrate, 1.5g/L sodium dodecyl sulfate, and 2.5g/L sodium citrate, and during the preparation, the sodium tungstate, the zinc nitrate, the sodium dodecyl sulfate, and the sodium citrate are sequentially added to pure water according to the above ratio, and are uniformly stirred, and then the PH is adjusted to 4 by using a boric acid solution;
s8, passivation: in order to remove the redundant heat-resistant coating on the surface of the rolled copper foil and avoid the influence of the redundant heat-resistant coating on the subsequent treatment process, the rolled copper foil plated with the tungsten-zinc alloy is immersed in warm water at 50 ℃ for three times before passivation, then the passivation solution is heated to 45 ℃, and finally the rolled copper foil is immersed in the passivation solution for passivation for 30 seconds;
in the passivation, a layer of compact antioxidant film is formed on the surface of the rolled copper foil, so that the rolled copper foil is not in direct contact with air, the corrosion resistance of the rolled copper foil is improved, and in order to improve the oxidation resistance of the rolled copper foil, the embodiment optimizes a passivation solution, wherein the passivation solution comprises 8g/L titanium trichloride, 10g/L phytic acid, 12mL/L hydrogen peroxide and 14g/L sodium hexametaphosphate, and during preparation, the titanium trichloride, the phytic acid, the hydrogen peroxide and the sodium hexametaphosphate are sequentially added into pure water according to the proportion and uniformly stirred, and then the pH of the passivation solution is adjusted to 2 by using nitric acid;
s9, drying: placing the passivated rolled copper foil in an oven at 55 ℃ for drying for 9 hours;
s10, silane coupling agent treatment: firstly, preparing a 4% silane coupling agent alcohol solution by using absolute ethyl alcohol, wherein the silane coupling agent adopts a silane coupling agent kh550, then soaking the dried rolled aluminum foil into the silane coupling agent alcohol solution, taking out the rolled aluminum foil after 12 seconds, and finally curing the rolled aluminum foil for 2 hours at 75 ℃ to finish the surface treatment work of the rolled copper foil, wherein the corrosion resistance of the rolled copper foil can be further improved by the silane coupling agent treatment process.
Example 7:
a surface treatment process of rolled copper foil comprises the following steps:
s1, cleaning: soaking the rolled copper foil in a cleaning solution for cleaning, taking out the rolled copper foil, cleaning the rolled copper foil for three times by using hot water at 65 ℃, and airing for later use; when the rolled copper foil is just rolled, the surface of the rolled copper foil is smooth, so that oil stains and an oxidation layer on the surface of the rolled copper foil need to be removed, the surface of the rolled copper foil is enabled to recover activity, in order to ensure that the surface of the rolled copper foil is cleaned, the rolled copper foil is soaked in a cleaning solution for three times for cleaning, the soaking time is 1.5min, and the rolled copper foil needs to be cleaned for three times by hot water at 65 ℃ after each soaking time;
in order to effectively remove the greasy dirt and the oxidation layer on the surface of the rolled copper foil, the cleaning solution is optimized in the embodiment, and comprises the following components in percentage by weight:
18% of glyceride, 12.5% of fatty alcohol-polyoxyethylene ether, 10% of sulfuric acid, 2% of ethanol, 2% of potassium pyrophosphate and 55.5% of pure water;
the cleaning solution reasonably combines an anionic surfactant, a nonionic surfactant, sulfuric acid and the like, so that the cleaning solution can simultaneously remove oil stains and oxidation layers on the surface of the rolled copper foil, and has high cleaning efficiency;
s2, first coarsening: adding a roughening solution into the electroplating rectifier at a current density of 18A/dm2Electroplating 15S on the rolled copper foil at the temperature of 35 ℃;
coarsening is to generate copper nodules on the surface of the rolled copper foil, improve the surface area of the combination of the rolled copper foil and the substrate, further strengthen the binding force between the rolled copper foil and the substrate, and in order to improve the coarsening effect, the embodiment optimizes a coarsening solution, wherein the coarsening solution comprises 20g/L copper sulfate, 70g/L sulfuric acid, 4g/L ferrous sulfate and 2g/L nickel sulfate, and during preparation, the copper sulfate, the sulfuric acid, the ferrous sulfate and the nickel sulfate are sequentially added into pure water according to the proportion and are uniformly stirred;
s3, first curing: adding a curing liquid into the electroplating rectifier at a current density of 18A/dm2Electroplating 12S on the rolled copper foil at the temperature of 50 ℃;
the solidification has a reinforcing effect on the coarsened structure, a firm foundation is provided for subsequent treatment, and in order to improve the solidification effect, the solidification solution is optimized in the embodiment and comprises 65g/L copper sulfate, 95g/L sulfuric acid and 2.5g/L lecithin, and during preparation, the copper sulfate, the sulfuric acid and the lecithin are sequentially added into pure water according to the proportion and are uniformly stirred;
s4, secondary coarsening: adding the roughening solution in the first roughening step into a plating rectifier at a current density of 10A/dm2Electroplating the rolled copper foil for 8.5S at the temperature of 25 ℃, and performing secondary roughening to improve the roughening effect of the rolled copper foil and greatly improve the bonding force between the rolled copper foil and the substrate;
s5, secondary curing: adding the curing liquid in the first curing step into a plating rectifier at a current density of 13.5A/dm2Electroplating the rolled copper foil for 7.5 seconds at the temperature of 38 ℃, and performing secondary curing to reinforce the secondary coarsened structure;
s6, nickel-lanthanum alloy plating: adding a nickel-lanthanum alloy plating solution into an electroplating rectifier at a current density of 15A/dm2Electroplating 40S on the rolled copper foil at the temperature of 58 ℃, and performing induced codeposition on nickel and lanthanum on the surface of the rolled copper foil to form a nickel-lanthanum alloy heat-resistant layerThe heat resistance and the high-temperature peeling strength of the copper foil are improved;
in order to improve the heat resistance of the copper foil, the heat-resistant plating layer is optimized in the embodiment, the nickel-lanthanum alloy plating solution comprises 40g/L nickel sulfamate, 25g/L lanthanum chloride, 4g/L urea and 2.5g/L sodium pyrophosphate, and during preparation, the nickel sulfamate, the lanthanum chloride, the urea and the sodium pyrophosphate are sequentially added into pure water according to the proportion, stirred and mixed uniformly, and then the pH value of the plating solution is adjusted to 4.5 by using citric acid;
s7, tungsten-zinc alloy plating: adding tungsten-zinc alloy plating solution into the electroplating rectifier at a current density of 8A/dm2Electroplating 20S on the rolled copper foil at the temperature of 45 ℃, forming a second heat-resistant layer, namely a tungsten-plated heat-resistant layer, on the surface of the rolled copper foil by taking sodium tungstate as a main salt and zinc nitrate as an auxiliary salt, and further improving the heat resistance and the high-temperature peeling strength of the copper foil;
in order to improve the heat resistance of the copper foil, the second heat-resistant plating layer is optimized in this embodiment, the tungsten-zinc alloy plating solution includes 25g/L sodium tungstate, 12.5g/L zinc nitrate, 1.5g/L sodium dodecyl sulfate, and 2.5g/L sodium citrate, and during the preparation, the sodium tungstate, the zinc nitrate, the sodium dodecyl sulfate, and the sodium citrate are sequentially added to pure water according to the above ratio, and are uniformly stirred, and then the PH is adjusted to 4 by using a boric acid solution;
s8, passivation: in order to remove the redundant heat-resistant coating on the surface of the rolled copper foil and avoid the influence of the redundant heat-resistant coating on the subsequent treatment process, the rolled copper foil plated with the tungsten-zinc alloy is immersed in warm water at 50 ℃ for three times before passivation, then the passivation solution is heated to 45 ℃, and finally the rolled copper foil is immersed in the passivation solution for passivation for 30 seconds;
in the passivation, a layer of compact antioxidant film is formed on the surface of the rolled copper foil, so that the rolled copper foil is not in direct contact with air, the corrosion resistance of the rolled copper foil is improved, and in order to improve the oxidation resistance of the rolled copper foil, the embodiment optimizes a passivation solution, wherein the passivation solution comprises 8g/L titanium trichloride, 10g/L phytic acid, 12mL/L hydrogen peroxide and 14g/L sodium hexametaphosphate, and during preparation, the titanium trichloride, the phytic acid, the hydrogen peroxide and the sodium hexametaphosphate are sequentially added into pure water according to the proportion and uniformly stirred, and then the pH of the passivation solution is adjusted to 2 by using nitric acid;
s9, drying: placing the passivated rolled copper foil in an oven at 55 ℃ for drying for 9 hours;
s10, silane coupling agent treatment: firstly, preparing a 4% silane coupling agent alcohol solution by using absolute ethyl alcohol, wherein the silane coupling agent adopts a silane coupling agent kh550, then soaking the dried rolled aluminum foil into the silane coupling agent alcohol solution, taking out the rolled aluminum foil after 12 seconds, and finally curing the rolled aluminum foil for 2 hours at 75 ℃ to finish the surface treatment work of the rolled copper foil, wherein the corrosion resistance of the rolled copper foil can be further improved by the silane coupling agent treatment process.
Comparative example:
the comparative example is a common surface treatment process of rolled copper foil, and specifically comprises the following steps:
(1) and oil removal: soaking the rolled copper foil in 15% sodium hydroxide solution for 3min, and then cleaning with clear water for three times;
(2) acid washing: soaking the rolled copper foil in 10% sulfuric acid solution for 3min, and then cleaning with clear water for three times;
(3) and coarsening: adding a roughening solution into the electroplating bath at a current density of 40A/dm2Electroplating the rolled copper foil for 5S at the temperature of 30 ℃;
the coarsening liquid comprises 30g/L copper sulfate, 90g/L sulfuric acid, 4g/L gelatin and 1g/L gallium arsenide;
(4) and curing: adding a roughening solution into the electroplating bath at a current density of 30A/dm2Electroplating the rolled copper foil for 8S at the temperature of 50 ℃;
the curing liquid comprises 60g/L copper sulfate and 105g/L sulfuric acid;
(5) and zinc-nickel alloy plating: adding a zinc-nickel alloy plating solution into the plating bath at a current density of 20A/dm2Electroplating 45S on the rolled copper foil at the temperature of 50 ℃;
the zinc-nickel alloy plating solution comprises 60g/L of zinc sulfate, 40g/L of nickel sulfate, 40g/L of sodium acetate and 40g/L of sodium sulfate, and the PH of the plating solution is adjusted to 4 by using dilute sulfuric acid;
(6) and passivating: firstly, heating the passivation solution to 65 ℃, and then soaking the rolled copper foil plated with the zinc-nickel alloy in the passivation solution for passivation for 3 min;
the passivation solution comprises 50g/L of chromium chloride, 125g/L of sodium nitrate and 50g/L of sodium fluoride, and the pH of the plating solution is adjusted to 2 by nitric acid;
(7) and (3) treating by using a silane coupling agent: and (3) soaking the passivated rolled aluminum foil into 10% silane coupling agent alcohol solution, wherein the silane coupling agent is mainly silane coupling agent KH560, taking out after 1min, and finally drying by using hot air at 150 ℃.
And (3) performance testing:
firstly, measuring the peel strength:
experiment design:
the rolled copper foils prepared in examples 1 to 7 and comparative examples were press-fitted with a resin substrate by a laminator to prepare copper clad laminates using examples 1 to 7 and comparative examples as experimental groups, then the peel strength (N/mm) between the rolled copper foils and the resin substrate in examples and comparative examples was tested by a tensile tester, the minimum load (Lm, N) value and the tested sample width (Ws, mm) were recorded, 3 repetitions of measurement were conducted for each experimental group, and the average minimum load (Lm, N) value and the average tested sample width (Ws, mm) were taken as final results.
The peel strength (N/mm) was calculated as follows:
peel strength (N/mm) minimum load (Lm)/width of specimen to be tested (Ws)
The experimental results are as follows:
as can be seen from the results of the peel strength test of the rolled copper foils of examples 1 to 7 and comparative example, the peel strength (N/mm) of the rolled copper foils of examples 1 to 7 was 2.09 to 2.23, while the peel strength (N/mm) of the rolled copper foils of comparative example was 1.57, indicating that the rolled copper foils obtained using the present invention had better peel strength and better adhesion to the substrate.
Table for measuring peel strength of rolled copper foils in examples 1 to 7 and comparative example
Group of
|
Peel strength (N/mm)
|
Example 1
|
2.15
|
Example 2
|
2.23
|
Example 3
|
2.09
|
Example 4
|
2.17
|
Example 5
|
2.22
|
Example 6
|
2.19
|
Example 7
|
2.17
|
Comparative example
|
1.57 |
(II) corrosion resistance test (salt spray test):
experiment design:
the rolled copper foils prepared in examples 1-7 and comparative examples are used as experimental groups respectively, corrosion resistance tests are carried out on the rolled copper foils of the experimental groups by using a circulating corrosion test box, each experimental group is tested for three times, a 5% sodium chloride solution is adopted for carrying out a spraying experiment under the conditions that the temperature is 33-37 ℃ and the pH value is 6.5-7.2, the experiment is carried out for 1 time every 3 hours, whether the corrosion phenomenon occurs in a sample is checked, if the corrosion phenomenon is observed, the experiment is stopped immediately, and the corrosion time is recorded.
The experimental results are as follows:
it was found by the corrosion resistance test experiments that the rolled copper foil of the comparative example showed slight corrosion and small and irregular white rust on the copper foil at 119h, whereas the rolled copper foils of examples 1 to 7 showed no corrosion, and thus the rolled copper foil obtained by the present invention had better corrosion resistance.
(III) testing heat resistance:
experiment design:
the rolled copper foils prepared in examples 1 to 7 and comparative example were used as test groups, and the copper foils of each test group were immersed in solder solutions at 288 ℃, 300 ℃ and 350 ℃ for 1min, and after being taken out, the test samples were observed to see if blistering was observed, and the test was repeated three times for each test group.
The experimental results are as follows:
through a heat resistance test experiment, the rolled copper foils prepared in examples 1-7 and comparative example have no bubble phenomenon after being soaked in the soldering tin liquid at 288 ℃ and 300 ℃ for 1 min; however, after soaking in the solder solution at 350 ℃ for 1min, the rolled copper foil in the comparative example generates obvious bubbling, while the rolled copper foils in examples 1-7 do not generate bubbling, so that the rolled copper foil obtained by the invention has better heat resistance which is far higher than the market standard (288 ℃).
(IV) surface roughness measurement:
experiment design:
the surface roughness (Ra) of the rolled copper foil is an arithmetic mean value of absolute distances between the top peak and the bottom valley of the surface of a sample to be measured, and is an important parameter for reflecting the surface profile characteristics of the sample, and the lower the surface roughness is, the more favorable the circuit with low dielectric loss is manufactured. In this experiment, rolled copper foils prepared in examples 1 to 7 and comparative example were used as test groups, and surface roughness measurements were performed on rolled copper foil samples of each test group using a surface roughness measuring instrument, 5 points were randomly selected on the surface of the copper foil sample for measurement, and the height values of the top and bottom of the peak at each point were recorded, and the surface roughness (R) of the copper foil was obtained by calculating the average of the 5 measurements.
The experimental results are as follows:
as can be seen from the results of measuring the surface roughness (Ra) of the rolled copper foils of examples 1 to 7 and comparative example, the surface roughness (Ra) of the rolled copper foils of examples 1 to 7 was 0.96 to 1.11, while the surface roughness (Ra) of the rolled copper foils of comparative example was 1.57, which indicates that the rolled copper foils obtained by the present invention had lower surface roughness and could satisfy the signal transmission requirements of high-end high-frequency printed circuits.
Measurement Table of surface roughness (Ra) of rolled copper foils in examples 1 to 7 and comparative example
Group of
|
Surface roughness (Ra)
|
Example 1
|
1.11
|
Example 2
|
0.96
|
Example 3
|
1.07
|
Example 4
|
1.04
|
Example 5
|
1.03
|
Example 6
|
1.09
|
Example 7
|
1.07
|
Comparative example
|
1.57 |
The embodiments of the present invention have been described in detail, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, and the scope of protection is still within the scope of the invention.