Water electroplating processing technology for base material

Abstract

The invention discloses a water electroplating processing technology for a base material, and belongs to the technical field of base material surface processing treatment, and the water electroplating processing technology comprises the following steps: step 1) oil and rust removal: a flexible metal base material is subjected to oil and rust removal treatment through oil removal liquid and rust removal liquid in sequence; (2) acid etching is conducted, specifically, the flexible metal base material is put into an acid etching solution to be subjected to acid etching; (3) spraying is conducted, specifically, the flexible metal base material is placed in an automatic spraying machine, the face to be plated is bent outwards to be subjected to spraying, and a first metal plating layer is formed; (4) water electroplating is conducted, specifically, water electroplating is conducted on the flexible metal base material subjected to spraying, the face to be plated is bent outwards to be subjected to water electroplating, and a second metal plating layer is formed outside the first metal plating layer; and (5) vacuum plating is conducted, specifically, vacuum plating is conducted on the flexible metal base material subjected to water electroplating, the face to be plated is bent outwards to be subjected to vacuum plating, and a third metal plating is formed outside the second metal plating. According to the application, the conductive resistance is reduced, and meanwhile, the binding force of the plating is improved.

Description

Technical Field

[0001] The invention relates to the technical field of substrate surface treatment, and in particular to a water electroplating process for a substrate. Background Art

[0002] Flexible metal substrates combine the bendability of flexible materials and the excellent properties of metal coatings, bringing more possibilities to multiple fields such as electronic products and the automotive industry. In particular, flexible metal substrates play an important role in the field of flexible electronics. They can be used to manufacture flexible electronic products such as flexible displays, flexible batteries, and flexible circuit boards. These products have the advantages of being light, flexible, and easy to carry, bringing more convenience to people's lives.

[0003] However, when the existing flexible metal substrates are directly used, most of them have the problem of insufficient conductivity. Therefore, in the prior art, the flexible metal substrate can be electroplated to improve the conductivity of the flexible metal substrate. However, as the number of plating layers of the metal substrate increases, the bonding strength between the plating layers will be affected, resulting in easy peeling. In particular, when the flexible metal material is bent, gaps in the plating layer are often generated or the plating layer falls off.

[0004] Therefore, the present application provides a water electroplating process for a substrate. How to improve the bonding strength of the coating while reducing the conductive resistance by improving the traditional processing technology is a technical problem that needs to be urgently solved by technical personnel in this field. Summary of the invention

[0005] To this end, the present invention provides a water electroplating process for a substrate to solve the related technical problems existing in the prior art.

[0006] In order to achieve the above object, the present invention provides the following technical solutions: According to a first aspect of the present application, a water electroplating process for a substrate is provided, comprising the following steps: Step 1), degreasing and rust removal, the flexible metal substrate is sequentially passed through a degreasing liquid and a rust removing liquid for degreasing and rust removal; Step 2), acid etching, placing the flexible metal substrate into an acid etching solution for acid etching; Step 3), spraying, placing the flexible metal substrate into an automatic spraying machine, bending the side to be plated outward for spraying, and forming a first metal coating; Step 4), water electroplating, water electroplating the flexible metal substrate after spraying, bending the side to be plated outward for water electroplating, and forming a second metal plating layer outside the first metal plating layer; Step 5), vacuum plating, vacuum plating the flexible metal substrate after water electroplating, bending the side to be plated outward for vacuum plating, and forming a third metal plating layer outside the second metal plating layer.

[0007] Furthermore, an ultrasonic cleaning step is included between step 1) and step 2), between step 2) and step 3), between step 3) and step 4), and between step 4) and step 5).

[0008] Further, in step 2), acid etching, placing the flexible metal substrate into an acid etching solution for acid etching, specifically includes: The acid etching solution includes: concentrated sulfuric acid 75-100mL / L, sodium chloride 200-500g / L, KC corrosion inhibitor 3-5g / L, glycine 3-5g / L and sodium dodecyl sulfate 10-50g / L; The flexible metal substrate to be etched is placed in the etching solution at a temperature of 30-62°C and an etching time of 1.5-3.0 minutes.

[0009] Furthermore, before step 3), a grid layer processing step is also included: Step 203), spraying the prepared grid layer liquid onto the surface of the flexible metal substrate, drying at a temperature of 230-350°C for 1.5-2.0 hours; In step 213 , the flexible metal substrate is placed in a ball mill for 0.5-1.5 min.

[0010] Furthermore, the grid layer liquid preparation method is: Add 0.1-0.5 parts of carboxylated carbon nanotubes, 5-30 parts of copper chloride, and 2-25 parts of nickel chloride to deionized water, mix and stir, adjust the pH to neutral with sodium hydroxide solution, microwave heat to 50-80° C., and react for 1-2 hours; The precipitate was obtained by centrifugal filtration, washed twice with deionized water, and prepared into a grid layer liquid with a mass fraction of 5%.

[0011] Further, in step 3), spraying, placing the flexible metal substrate into an automatic spraying machine, bending the side to be plated outward for spraying, and forming a first metal coating, comprising: The bending curvature of the flexible metal substrate is: The bending curvature of the flexible metal substrate is: ; in, It is the curvature of the flexible metal substrate during spraying. is the thickness of the flexible metal substrate, is the expected thickness of the first metal coating, is the adjustment factor for the thickness of the flexible metal substrate, is the adjustment factor for the expected thickness of the metal coating.

[0012] Further, in step 4), water electroplating is performed on the flexible metal substrate after spraying, and the side to be plated is bent outward for water electroplating to form a second metal plating layer outside the first metal plating layer, including: The bending curvature of the flexible metal substrate is: ; in, It is the curvature of the flexible metal substrate during water electroplating. is the thickness of the flexible metal substrate, is the expected thickness of the first metal coating, is the expected thickness of the second metal coating, is the adjustment factor for the thickness of the flexible metal substrate, is the adjustment factor for the expected thickness of the metal coating.

[0013] Further, in step 5), vacuum plating is performed on the flexible metal substrate after water electroplating, and the side to be plated is bent outward for vacuum plating to form a third metal plating layer outside the second metal plating layer, including: The bending curvature of the flexible metal substrate is: ; in, It is the curvature of the flexible metal substrate during water electroplating. is the thickness of the flexible metal substrate, is the expected thickness of the first metal coating, is the expected thickness of the second metal coating, is the expected thickness of the third metal coating, is the adjustment factor for the thickness of the flexible metal substrate, is the adjustment factor for the expected thickness of the metal coating.

[0014] Furthermore, the flexible metal substrate is a stainless steel sheet, a copper alloy sheet or a nickel alloy sheet.

[0015] According to a second aspect of the present application, a low-resistance conductive material is provided, comprising a flexible metal substrate prepared by the above-mentioned water electroplating process for substrates.

[0016] The present invention has the following advantages: The present application improves the flexible metal substrate electroplating process in the prior art. On the one hand, after acid etching, a grid layer liquid is sprayed on the surface of the flexible metal substrate so that the grid layer liquid can penetrate into the rough surface of the flexible metal substrate. At the same time, the grid layer liquid can form a grid layer structure on the surface of the flexible metal substrate, which is beneficial to the adhesion and bonding of subsequent coatings. On the other hand, in the three steps of spraying, water electroplating and vacuum plating, the flexible metal substrate is bent to expose the grid layer, thereby improving the bonding degree of subsequent coatings while ensuring low resistance. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] In order to more clearly illustrate the implementation methods of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for the implementation methods or the description of the prior art. Obviously, the drawings in the following description are only exemplary, and for ordinary technicians in this field, other implementation drawings can be derived from the provided drawings without creative work.

[0018] The structures, proportions, sizes, etc. illustrated in this specification are only used to match the contents disclosed in the specification so as to facilitate understanding and reading by persons familiar with the technology. They are not used to limit the conditions under which the present invention can be implemented, and therefore have no substantial technical significance. Any structural modification, change in proportion or adjustment of size shall still fall within the scope of the technical contents disclosed in the present invention without affecting the effects and purposes that can be achieved by the present invention.

[0019] Figure 1 The present invention provides a flow chart of the steps of the water electroplating process for a substrate. DETAILED DESCRIPTION

[0020] The following is a description of the implementation of the present invention by specific embodiments. People familiar with the art can easily understand other advantages and effects of the present invention from the contents disclosed in this specification. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0021] In order to solve the relevant technical problems existing in the prior art, the present application improves the traditional flexible metal substrate plating process, in order to achieve the premise of reducing the resistance of the flexible metal and improving the bonding strength of the coating, thereby improving the application scope and performance of the flexible metal substrate.

[0022] According to the first aspect of the present application, Figure 1 As shown, a water electroplating process for a substrate is provided, comprising the following steps: Step 1), degreasing and rust removal, the flexible metal substrate is sequentially passed through a degreasing liquid and a rust removing liquid for degreasing and rust removal; Step 2), acid etching, placing the flexible metal substrate into an acid etching solution for acid etching; Step 3), spraying, placing the flexible metal substrate into an automatic spraying machine, bending the side to be plated outward for spraying, and forming a first metal coating; Step 4), water electroplating, water electroplating the flexible metal substrate after spraying, bending the side to be plated outward for water electroplating, and forming a second metal plating layer outside the first metal plating layer; Step 5), vacuum plating, vacuum plating the flexible metal substrate after water electroplating, bending the side to be plated outward for vacuum plating, and forming a third metal plating layer outside the second metal plating layer.

[0023] Furthermore, an ultrasonic cleaning step is included between step 1) and step 2), between step 2) and step 3), between step 3) and step 4), and between step 4) and step 5).

[0024] Further, in step 2), acid etching, placing the flexible metal substrate into an acid etching solution for acid etching, specifically includes: The acid etching solution includes: concentrated sulfuric acid 75-100mL / L, sodium chloride 200-500g / L, KC corrosion inhibitor 3-5g / L, glycine 3-5g / L and sodium dodecyl sulfate 10-50g / L; The flexible metal substrate to be etched is placed in the etching solution at a temperature of 30-62°C and an etching time of 1.5-3.0 minutes.

[0025] Furthermore, before step 3), a grid layer processing step is also included: Step 203), spraying the prepared grid layer liquid onto the surface of the flexible metal substrate, drying at a temperature of 230-350°C for 1.5-2.0 hours; In step 213 , the flexible metal substrate is placed in a ball mill for 0.5-1.5 min.

[0026] Furthermore, the grid layer liquid preparation method is: Add 0.1-0.5 parts of carboxylated carbon nanotubes, 5-30 parts of copper chloride, and 2-25 parts of nickel chloride to deionized water, mix and stir, adjust the pH to neutral with sodium hydroxide solution, microwave heat to 50-80° C., and react for 1-2 hours; The precipitate was obtained by centrifugal filtration, washed twice with deionized water, and prepared into a grid layer liquid with a mass fraction of 5%.

[0027] Further, in step 3), spraying, placing the flexible metal substrate into an automatic spraying machine, bending the side to be plated outward for spraying, and forming a first metal coating, comprising: The bending curvature of the flexible metal substrate is: ; in, It is the curvature of the flexible metal substrate during spraying. is the thickness of the flexible metal substrate, is the expected thickness of the first metal coating, is the adjustment factor for the thickness of the flexible metal substrate, is the adjustment factor for the expected thickness of the metal coating.

[0028] Further, in step 4), water electroplating is performed on the flexible metal substrate after spraying, and the side to be plated is bent outward for water electroplating to form a second metal plating layer outside the first metal plating layer, including: The bending curvature of the flexible metal substrate is: ; in, It is the curvature of the flexible metal substrate during water electroplating. is the thickness of the flexible metal substrate, is the expected thickness of the first metal coating, is the expected thickness of the second metal coating, is the adjustment factor for the thickness of the flexible metal substrate, is the adjustment factor for the expected thickness of the metal coating.

[0029] Further, in step 5), vacuum plating is performed on the flexible metal substrate after water electroplating, and the side to be plated is bent outward for vacuum plating to form a third metal plating layer outside the second metal plating layer, including: The bending curvature of the flexible metal substrate is: ; in, It is the curvature of the flexible metal substrate during water electroplating. is the thickness of the flexible metal substrate, is the expected thickness of the first metal coating, is the expected thickness of the second metal coating, is the expected thickness of the third metal coating, is the adjustment factor for the thickness of the flexible metal substrate, is the adjustment factor for the expected thickness of the metal coating.

[0030] Furthermore, the flexible metal substrate is a stainless steel sheet, a copper alloy sheet or a nickel alloy sheet.

[0031] According to a second aspect of the present application, a low-resistance conductive material is provided, comprising a flexible metal substrate prepared by the above-mentioned water electroplating process for substrates.

[0032] In order to better illustrate the technical effect of the processing technology provided by the present application, the present application provides the following embodiments and comparative examples. The flexible metal substrate selected is a stainless steel sheet with a thickness of 200 μm, the first metal coating is a copper coating with a thickness of 300 nm, the second metal coating is a copper coating with a thickness of 500 nm, and the third metal coating is a copper coating with a thickness of 400 nm. In the processing, when the flexible metal substrate is bent, the adjustment coefficient is between 0.0001 and 0.0001, which can be selected according to the selected materials and needs. The specific embodiments are as follows:

[0033] Example 1 Embodiment 1 provides a water electroplating process for a substrate, comprising the following steps: Step 1) degreasing and rust removal: the flexible metal substrate is sequentially passed through a degreasing liquid and a rust removing liquid for degreasing and rust removal.

[0034] In this embodiment, the degreasing liquid formula used is as follows: Sodium hydroxide 15g / L, sodium bicarbonate 10g / L, sodium phosphate 35g / L, alkylphenol polyoxyethylene ether 0.8g / L. Oil removal treatment temperature 28-32℃, treatment time 2-3min.

[0035] In this embodiment, the rust removal liquid formula used is as follows: Sulfuric acid 160g / L, hexamethylenetetramine 3g / L, triethanolamine 2g / L, sodium dodecyl sulfonate 10g / L, sodium chloride 150g / L. Rust removal temperature 15-25℃, treatment time 2-3min.

[0036] Ultrasonic water washing is used between the above treatment processes to ensure that no residual liquid is generated during the treatment process, thereby ensuring the stability of subsequent treatments.

[0037] Step 2), acid etching, placing the flexible metal substrate into an acid etching solution for acid etching; wherein the formula and treatment scheme of the acid etching solution are as follows: The etching solution includes: 75 mL / L concentrated sulfuric acid, 450 g / L sodium chloride, 4 g / L KC corrosion inhibitor, 4 g / L glycine and 35 g / L sodium dodecyl sulfate; the flexible metal substrate to be etched is placed in the etching solution, the temperature is 35° C., and the etching time is 2.5 min.

[0038] It also includes the mesh layer processing steps: Step 203), add 0.1 parts of carboxylated carbon nanotubes, 28 parts of copper chloride, and 22 parts of nickel chloride to deionized water, mix and stir, adjust the pH to neutral with sodium hydroxide solution, microwave heat to 55°C, and react for 1.5 hours; centrifuge to obtain a precipitate, wash it twice with deionized water, and prepare a grid layer liquid with a mass fraction of 5%. Spray the prepared grid layer liquid onto the surface of the flexible metal substrate, dry it at a temperature of 350°C, and dry it for 2.0 hours; In step 213 , the flexible metal substrate is placed in a ball mill for 0.5 min.

[0039] Step 3), spraying, placing the flexible metal substrate into an automatic spraying machine, bending the side to be plated outward for spraying, and forming a first metal coating; The bending curvature of the flexible metal substrate is: ; in, It is the curvature of the flexible metal substrate during spraying. is the thickness of the flexible metal substrate, is the expected thickness of the first metal coating, is the adjustment factor for the thickness of the flexible metal substrate, is the adjustment factor for the expected thickness of the metal coating.

[0040] Step 4), water electroplating, water electroplating the flexible metal substrate after spraying, bending the side to be plated outward for water electroplating, and forming a second metal plating layer outside the first metal plating layer; The bending curvature of the flexible metal substrate is: ; in, It is the curvature of the flexible metal substrate during water electroplating. is the thickness of the flexible metal substrate, is the expected thickness of the first metal coating, is the expected thickness of the second metal coating, is the adjustment factor for the thickness of the flexible metal substrate, is the adjustment factor for the expected thickness of the metal coating.

[0041] Step 5), vacuum plating, vacuum plating the flexible metal substrate after water electroplating, bending the side to be plated outward for vacuum plating, and forming a third metal plating layer outside the second metal plating layer.

[0042] The bending curvature of the flexible metal substrate is: ; in, It is the curvature of the flexible metal substrate during water electroplating. is the thickness of the flexible metal substrate, is the expected thickness of the first metal coating, is the expected thickness of the second metal coating, is the expected thickness of the third metal coating, is the adjustment factor for the thickness of the flexible metal substrate, is the adjustment factor for the expected thickness of the metal coating.

[0043] Among them, in the above steps, an ultrasonic cleaning step is included between step 1) and step 2), between step 2) and step 3), between step 3) and step 4), and between step 4) and step 5), the purpose of which is to prevent the influence on the subsequent steps by sufficient rinsing and cleaning between the previous and next steps.

[0044] The resistance and bonding strength of the plated flexible metal substrate were tested, as shown in Table 1.

[0045] Example 2 Embodiment 2 provides a water electroplating process for a substrate, comprising the following steps: Step 1) degreasing and rust removal: the flexible metal substrate is sequentially passed through a degreasing liquid and a rust removing liquid for degreasing and rust removal.

[0046] In this embodiment, the degreasing liquid formula used is as follows: Sodium hydroxide 15g / L, sodium bicarbonate 10g / L, sodium phosphate 35g / L, alkylphenol polyoxyethylene ether 0.8g / L. Oil removal treatment temperature 28-32℃, treatment time 2-3min.

[0047] In this embodiment, the rust removal liquid formula used is as follows: Sulfuric acid 160g / L, hexamethylenetetramine 3g / L, triethanolamine 2g / L, sodium dodecyl sulfonate 10g / L, sodium chloride 150g / L. Rust removal temperature 15-25℃, treatment time 2-3min.

[0048] Ultrasonic water washing is used between the above treatment processes to ensure that no residual liquid is generated during the treatment process, thereby ensuring the stability of subsequent treatments.

[0049] Step 2), acid etching, placing the flexible metal substrate into an acid etching solution for acid etching; wherein the formula and treatment scheme of the acid etching solution are as follows: The etching solution includes: 92 mL / L concentrated sulfuric acid, 350 g / L sodium chloride, 3 g / L KC corrosion inhibitor, 5 g / L glycine and 44 g / L sodium dodecyl sulfate; the flexible metal substrate to be etched is placed in the etching solution at a temperature of 42° C. and an etching time of 2.0 min.

[0050] It also includes the mesh layer processing steps: Step 203), add 0.3 parts of carboxylated carbon nanotubes, 25 parts of copper chloride, and 23 parts of nickel chloride to deionized water, mix and stir, adjust the pH to neutral with sodium hydroxide solution, microwave heat to 60°C, and react for 1.3 hours; centrifuge to obtain a precipitate, wash it twice with deionized water, and prepare a grid layer liquid with a mass fraction of 5%. Spray the prepared grid layer liquid onto the surface of the flexible metal substrate, dry it at a temperature of 250°C, and dry it for 1.5 hours; In step 213 , the flexible metal substrate is placed in a ball mill for 1 minute.

[0051] Step 3), spraying, placing the flexible metal substrate into an automatic spraying machine, bending the side to be plated outward for spraying, and forming a first metal coating; The bending curvature of the flexible metal substrate is: ; in, It is the curvature of the flexible metal substrate during spraying. is the thickness of the flexible metal substrate, is the expected thickness of the first metal coating, is the adjustment factor for the thickness of the flexible metal substrate, is the adjustment factor for the expected thickness of the metal coating.

[0052] Step 4), water electroplating, water electroplating the flexible metal substrate after spraying, bending the side to be plated outward for water electroplating, and forming a second metal plating layer outside the first metal plating layer; The bending curvature of the flexible metal substrate is: ; in, It is the curvature of the flexible metal substrate during water electroplating. is the thickness of the flexible metal substrate, is the expected thickness of the first metal coating, is the expected thickness of the second metal coating, is the adjustment factor for the thickness of the flexible metal substrate, is the adjustment factor for the expected thickness of the metal coating.

[0053] Step 5), vacuum plating, vacuum plating the flexible metal substrate after water electroplating, bending the side to be plated outward for vacuum plating, and forming a third metal plating layer outside the second metal plating layer.

[0054] The bending curvature of the flexible metal substrate is: ; in, It is the curvature of the flexible metal substrate during water electroplating. is the thickness of the flexible metal substrate, is the expected thickness of the first metal coating, is the expected thickness of the second metal coating, is the expected thickness of the third metal coating, is the adjustment factor for the thickness of the flexible metal substrate, is the adjustment factor for the expected thickness of the metal coating.

[0055] Among them, in the above steps, an ultrasonic cleaning step is included between step 1) and step 2), between step 2) and step 3), between step 3) and step 4), and between step 4) and step 5), the purpose of which is to prevent the influence on the subsequent steps by sufficient rinsing and cleaning between the previous and next steps.

[0056] The resistance and bonding strength of the plated flexible metal substrate were tested, as shown in Table 1.

[0057] Example 3 Embodiment 3 provides a water electroplating process for a substrate, comprising the following steps: Step 1) degreasing and rust removal: the flexible metal substrate is sequentially passed through a degreasing liquid and a rust removing liquid for degreasing and rust removal.

[0058] In this embodiment, the degreasing liquid formula used is as follows: Sodium hydroxide 15g / L, sodium bicarbonate 10g / L, sodium phosphate 35g / L, alkylphenol polyoxyethylene ether 0.8g / L. Oil removal treatment temperature 28-32℃, treatment time 2-3min.

[0059] In this embodiment, the rust removal liquid formula used is as follows: Sulfuric acid 160g / L, hexamethylenetetramine 3g / L, triethanolamine 2g / L, sodium dodecyl sulfonate 10g / L, sodium chloride 150g / L. Rust removal temperature 15-25℃, treatment time 2-3min.

[0060] Ultrasonic water washing is used between the above treatment processes to ensure that no residual liquid is generated during the treatment process, thereby ensuring the stability of subsequent treatments.

[0061] Step 2), acid etching, placing the flexible metal substrate into an acid etching solution for acid etching; wherein the formula and treatment scheme of the acid etching solution are as follows: The etching solution includes: 100 mL / L concentrated sulfuric acid, 250 g / L sodium chloride, 5 g / L KC corrosion inhibitor, 4 g / L glycine and 50 g / L sodium dodecyl sulfate; the flexible metal substrate to be etched is placed in the etching solution, the temperature is 30° C., and the etching time is 3 minutes.

[0062] It also includes the mesh layer processing steps: Step 203), add 0.4 parts of carboxylated carbon nanotubes, 21 parts of copper chloride, and 18 parts of nickel chloride to deionized water, mix and stir, adjust the pH to neutral with sodium hydroxide solution, microwave heat to 75°C, and react for 1.1h; centrifuge to obtain a precipitate, wash it twice with deionized water, and prepare a grid layer liquid with a mass fraction of 5%. Spray the prepared grid layer liquid onto the surface of the flexible metal substrate, dry it at 280°C, and dry it for 1.8h; In step 213 , the flexible metal substrate is placed in a ball mill for 1.2 minutes.

[0063] Step 3), spraying, placing the flexible metal substrate into an automatic spraying machine, bending the side to be plated outward for spraying, and forming a first metal coating; The bending curvature of the flexible metal substrate is: ; in, It is the curvature of the flexible metal substrate during spraying. is the thickness of the flexible metal substrate, is the expected thickness of the first metal coating, is the adjustment factor for the thickness of the flexible metal substrate, is the adjustment factor for the expected thickness of the metal coating.

[0064] Step 4), water electroplating, water electroplating the flexible metal substrate after spraying, bending the side to be plated outward for water electroplating, and forming a second metal plating layer outside the first metal plating layer; The bending curvature of the flexible metal substrate is: ; in, It is the curvature of the flexible metal substrate during water electroplating. is the thickness of the flexible metal substrate, is the expected thickness of the first metal coating, is the expected thickness of the second metal coating, is the adjustment factor for the thickness of the flexible metal substrate, is the adjustment factor for the expected thickness of the metal coating.

[0065] Step 5), vacuum plating, vacuum plating the flexible metal substrate after water electroplating, bending the side to be plated outward for vacuum plating, and forming a third metal plating layer outside the second metal plating layer.

[0066] The bending curvature of the flexible metal substrate is: ; in, It is the curvature of the flexible metal substrate during water electroplating. is the thickness of the flexible metal substrate, is the expected thickness of the first metal coating, is the expected thickness of the second metal coating, is the expected thickness of the third metal coating, is the adjustment factor for the thickness of the flexible metal substrate, is the adjustment factor for the expected thickness of the metal coating.

[0067] Among them, in the above steps, an ultrasonic cleaning step is included between step 1) and step 2), between step 2) and step 3), between step 3) and step 4), and between step 4) and step 5), the purpose of which is to prevent the influence on the subsequent steps by sufficient rinsing and cleaning between the previous and next steps.

[0068] The resistance and bonding strength of the plated flexible metal substrate were tested, as shown in Table 1.

[0069] Example 4 Embodiment 4 provides a water electroplating process for a substrate, comprising the following steps: Step 1) degreasing and rust removal: the flexible metal substrate is sequentially passed through a degreasing liquid and a rust removing liquid for degreasing and rust removal.

[0070] In this embodiment, the degreasing liquid formula used is as follows: Sodium hydroxide 15g / L, sodium bicarbonate 10g / L, sodium phosphate 35g / L, alkylphenol polyoxyethylene ether 0.8g / L. Oil removal treatment temperature 28-32℃, treatment time 2-3min.

[0071] In this embodiment, the rust removal liquid formula used is as follows: Sulfuric acid 160g / L, hexamethylenetetramine 3g / L, triethanolamine 2g / L, sodium dodecyl sulfonate 10g / L, sodium chloride 150g / L. Rust removal temperature 15-25℃, treatment time 2-3min.

[0072] Ultrasonic water washing is used between the above treatment processes to ensure that no residual liquid is generated during the treatment process, thereby ensuring the stability of subsequent treatments.

[0073] Step 2), acid etching, placing the flexible metal substrate into an acid etching solution for acid etching; wherein the formula and treatment scheme of the acid etching solution are as follows: The etching solution includes: 81 mL / L concentrated sulfuric acid, 400 g / L sodium chloride, 5 g / L KC corrosion inhibitor, 3 g / L glycine and 30 g / L sodium dodecyl sulfate; the flexible metal substrate to be etched is placed in the etching solution at a temperature of 55° C. and an etching time of 1.8 min.

[0074] It also includes the mesh layer processing steps: Step 203), add 0.2 parts of carboxylated carbon nanotubes, 15 parts of copper chloride, and 20 parts of nickel chloride to deionized water, mix and stir, adjust the pH to neutral with sodium hydroxide solution, microwave heat to 80°C, and react for 2 hours; centrifuge to obtain a precipitate, wash it twice with deionized water, and prepare it into a grid layer liquid with a mass fraction of 5%. Spray the prepared grid layer liquid onto the surface of the flexible metal substrate, dry it at 320°C, and dry it for 2.0 hours; In step 213 , the flexible metal substrate is placed in a ball mill for 1.5 minutes.

[0075] Step 3), spraying, placing the flexible metal substrate into an automatic spraying machine, bending the side to be plated outward for spraying, and forming a first metal coating; The bending curvature of the flexible metal substrate is: ; in, It is the curvature of the flexible metal substrate during spraying. is the thickness of the flexible metal substrate, is the expected thickness of the first metal coating, is the adjustment factor for the thickness of the flexible metal substrate, is the adjustment factor for the expected thickness of the metal coating.

[0076] Step 4), water electroplating, water electroplating the flexible metal substrate after spraying, bending the side to be plated outward for water electroplating, and forming a second metal plating layer outside the first metal plating layer; The bending curvature of the flexible metal substrate is: ; in, It is the curvature of the flexible metal substrate during water electroplating. is the thickness of the flexible metal substrate, is the expected thickness of the first metal coating, is the expected thickness of the second metal coating, is the adjustment factor for the thickness of the flexible metal substrate, is the adjustment factor for the expected thickness of the metal coating.

[0077] Step 5), vacuum plating, vacuum plating the flexible metal substrate after water electroplating, bending the side to be plated outward for vacuum plating, and forming a third metal plating layer outside the second metal plating layer.

[0078] The bending curvature of the flexible metal substrate is: ; in, It is the curvature of the flexible metal substrate during water electroplating. is the thickness of the flexible metal substrate, is the expected thickness of the first metal coating, is the expected thickness of the second metal coating, is the expected thickness of the third metal coating, is the adjustment factor for the thickness of the flexible metal substrate, is the adjustment factor for the expected thickness of the metal coating.

[0079] Among them, in the above steps, an ultrasonic cleaning step is included between step 1) and step 2), between step 2) and step 3), between step 3) and step 4), and between step 4) and step 5), the purpose of which is to prevent the influence on the subsequent steps by sufficient rinsing and cleaning between the previous and next steps.

[0080] The resistance and bonding strength of the plated flexible metal substrate were tested, as shown in Table 1.

[0081] Example 5 Embodiment 5 provides a water electroplating process for a substrate, comprising the following steps: Step 1) degreasing and rust removal: the flexible metal substrate is sequentially passed through a degreasing liquid and a rust removing liquid for degreasing and rust removal.

[0082] In this embodiment, the degreasing liquid formula used is as follows: Sodium hydroxide 15g / L, sodium bicarbonate 10g / L, sodium phosphate 35g / L, alkylphenol polyoxyethylene ether 0.8g / L. Oil removal treatment temperature 28-32℃, treatment time 2-3min.

[0083] In this embodiment, the rust removal liquid formula used is as follows: Sulfuric acid 160g / L, hexamethylenetetramine 3g / L, triethanolamine 2g / L, sodium dodecyl sulfonate 10g / L, sodium chloride 150g / L. Rust removal temperature 15-25℃, treatment time 2-3min.

[0084] Ultrasonic water washing is used between the above treatment processes to ensure that no residual liquid is generated during the treatment process, thereby ensuring the stability of subsequent treatments.

[0085] Step 2), acid etching, placing the flexible metal substrate into an acid etching solution for acid etching; wherein the formula and treatment scheme of the acid etching solution are as follows: The etching solution includes: 85 mL / L concentrated sulfuric acid, 300 g / L sodium chloride, 4 g / L KC corrosion inhibitor, 3 g / L glycine and 25 g / L sodium dodecyl sulfate; the flexible metal substrate to be etched is placed in the etching solution, the temperature is 60° C., and the etching time is 1.5 min.

[0086] It also includes the mesh layer processing steps: Step 203), add 0.5 parts of carboxylated carbon nanotubes, 30 parts of copper chloride, and 15 parts of nickel chloride to deionized water, mix and stir, adjust the pH to neutral with sodium hydroxide solution, microwave heat to 68°C, and react for 1.8 hours; centrifuge to obtain a precipitate, wash it twice with deionized water, and prepare a grid layer liquid with a mass fraction of 5%. Spray the prepared grid layer liquid onto the surface of the flexible metal substrate, dry it at 300°C, and dry it for 1.5 hours; In step 213 , the flexible metal substrate is placed in a ball mill for 0.8 min.

[0087] Step 3), spraying, placing the flexible metal substrate into an automatic spraying machine, bending the side to be plated outward for spraying, and forming a first metal coating; The bending curvature of the flexible metal substrate is: ; in, It is the curvature of the flexible metal substrate during spraying. is the thickness of the flexible metal substrate, is the expected thickness of the first metal coating, is the adjustment factor for the thickness of the flexible metal substrate, is the adjustment factor for the expected thickness of the metal coating.

[0088] Step 4), water electroplating, water electroplating the flexible metal substrate after spraying, bending the side to be plated outward for water electroplating, and forming a second metal plating layer outside the first metal plating layer; The bending curvature of the flexible metal substrate is: ; in, It is the curvature of the flexible metal substrate during water electroplating. is the thickness of the flexible metal substrate, is the expected thickness of the first metal coating, is the expected thickness of the second metal coating, is the adjustment factor for the thickness of the flexible metal substrate, is the adjustment factor for the expected thickness of the metal coating.

[0089] Step 5), vacuum plating, vacuum plating the flexible metal substrate after water electroplating, bending the side to be plated outward for vacuum plating, and forming a third metal plating layer outside the second metal plating layer.

[0090] The bending curvature of the flexible metal substrate is: ; in, It is the curvature of the flexible metal substrate during water electroplating. is the thickness of the flexible metal substrate, is the expected thickness of the first metal coating, is the expected thickness of the second metal coating, is the expected thickness of the third metal coating, is the adjustment factor for the thickness of the flexible metal substrate, is the adjustment factor for the expected thickness of the metal coating.

[0091] Among them, in the above steps, an ultrasonic cleaning step is included between step 1) and step 2), between step 2) and step 3), between step 3) and step 4), and between step 4) and step 5), the purpose of which is to prevent the influence on the subsequent steps by sufficient rinsing and cleaning between the previous and next steps.

[0092] The resistance and bonding strength of the plated flexible metal substrate were tested, as shown in Table 1.

[0093] Comparative Example 1 The solution of this comparative example 1 is the same as that of the embodiment 1, but the mesh layer processing step is omitted.

[0094] The resistance and bonding strength of the plated flexible metal substrate were tested, as shown in Table 1.

[0095] Comparative Example 2 The scheme of this comparative example 2 follows that of example 1, but the bending process of the flexible metal substrate in the plating step is omitted.

[0096] The resistance and bonding strength of the plated flexible metal substrate were tested, as shown in Table 1.

[0097] Table 1: Test results of resistance and bonding strength of flexible metal substrates Square resistance (mΩ) Binding force (N / cm) Example 1 25.7 11.2 Example 2 23.4 12.5 Example 3 22.1 13.8 Example 4 24.2 13.1 Example 5 25.1 11.6 Comparative Example 1 46.8 7.5 Comparative Example 2 55.3 8.2 From the above experimental results, it can be seen that for the detection of square resistance, in Examples 1-5, the technical solution of the present application can significantly reduce the square resistance. At the same time, the square resistance of Example 3 reaches the lowest level, which is significantly different from the comparative example. For the detection of bonding strength, compared with Comparative Examples 1 and 2, Examples 1-5 significantly improve the bonding strength of the coating on the flexible metal substrate through the combination of the above-mentioned spraying grid layer liquid processing steps and plating processing parameters.

[0098] The present application improves the flexible metal substrate electroplating process in the prior art. On the one hand, after acid etching, a grid layer liquid is sprayed on the surface of the flexible metal substrate so that the grid layer liquid can penetrate into the rough surface of the flexible metal substrate. At the same time, the grid layer liquid can form a grid layer structure on the surface of the flexible metal substrate, which is beneficial to the adhesion and bonding of subsequent coatings. On the other hand, in the three steps of spraying, water electroplating and vacuum plating, the flexible metal substrate is bent to expose the grid layer, thereby improving the bonding degree of subsequent coatings while ensuring low resistance.

[0099] Although the present invention has been described in detail above by general description and specific embodiments, it is obvious to those skilled in the art that some modifications or improvements can be made to the present invention. Therefore, these modifications or improvements made without departing from the spirit of the present invention all belong to the scope of protection claimed by the present invention.

Claims

1. A water electroplating process for a substrate, characterized in that: The steps include: Step 1), degreasing and derusting, the flexible metal substrate is sequentially passed through a degreasing liquid and a derusting liquid to perform degreasing and derusting treatment; Step 2), acid etching, placing the flexible metal substrate into an acid etching solution for acid etching; Step 3), spraying, placing the flexible metal substrate into an automatic spraying machine, bending the side to be plated outward for spraying, and forming a first metal coating; Step 4), water electroplating, water electroplating the flexible metal substrate after spraying, bending the side to be plated outward for water electroplating, and forming a second metal plating layer outside the first metal plating layer; Step 5), vacuum plating, vacuum plating the flexible metal substrate after water electroplating, bending the side to be plated outward for vacuum plating, and forming a third metal plating layer outside the second metal plating layer.

2. The water electroplating process for a substrate according to claim 1, characterized in that: An ultrasonic cleaning step is included between step 1) and step 2), between step 2) and step 3), between step 3) and step 4), and between step 4) and step 5).

3. The water electroplating process for a substrate according to claim 1, characterized in that: in, Step 2), acid etching, placing the flexible metal substrate into an acid etching solution for acid etching, specifically comprising: The acid etching solution includes: concentrated sulfuric acid 75-100mL / L, sodium chloride 200-500g / L, KC corrosion inhibitor 3-5g / L, glycine 3-5g / L and sodium dodecyl sulfate 10-50g / L; The flexible metal substrate to be etched is placed in the etching solution at a temperature of 30-62°C and an etching time of 1.5-3.0 minutes.

4. The water electroplating process for a substrate according to claim 1, characterized in that: in, Before step 3), the grid layer processing step is also included: Step 203), spraying the prepared grid layer liquid onto the surface of the flexible metal substrate, drying at a temperature of 230-350°C for 1.5-2.0 hours; In step 213 , the flexible metal substrate is placed in a ball mill for 0.5-1.5 min.

5. The water electroplating process for a substrate as claimed in claim 4, characterized in that: in, The grid layer liquid preparation method is: Add 0.1-0.5 parts of carboxylated carbon nanotubes, 5-30 parts of copper chloride, and 2-25 parts of nickel chloride to deionized water, mix and stir, adjust the pH to neutral with sodium hydroxide solution, microwave heat to 50-80° C., and react for 1-2 hours; The precipitate was obtained by centrifugal filtration, washed twice with deionized water, and prepared into a grid layer liquid with a mass fraction of 5%.

6. The water electroplating process for a substrate according to claim 1, characterized in that: in, Step 3), spraying, placing the flexible metal substrate into an automatic spraying machine, bending the side to be plated outward for spraying, and forming a first metal coating, including: The bending curvature of the flexible metal substrate is: ； in, It is the curvature of the flexible metal substrate during spraying. is the thickness of the flexible metal substrate, is the expected thickness of the first metal coating, is the adjustment factor for the thickness of the flexible metal substrate, is the adjustment factor for the expected thickness of the metal coating.

7. The water electroplating process for a substrate according to claim 6, characterized in that: in, Step 4), water electroplating, water electroplating the flexible metal substrate after spraying, bending the side to be plated outward for water electroplating, and forming a second metal plating layer outside the first metal plating layer, including: The bending curvature of the flexible metal substrate is: ； in, It is the curvature of the flexible metal substrate during water electroplating. is the thickness of the flexible metal substrate, is the expected thickness of the first metal coating, is the expected thickness of the second metal coating, is the adjustment factor for the thickness of the flexible metal substrate, is the adjustment factor for the expected thickness of the metal coating.

8. The water electroplating process for a substrate as claimed in claim 7, characterized in that: in, Step 5), vacuum plating, vacuum plating the flexible metal substrate after water electroplating, bending the side to be plated outward for vacuum plating, and forming a third metal plating layer outside the second metal plating layer, including: The bending curvature of the flexible metal substrate is: ； in, It is the curvature of the flexible metal substrate during water electroplating. is the thickness of the flexible metal substrate, is the expected thickness of the first metal coating, is the expected thickness of the second metal coating, is the expected thickness of the third metal coating, is the adjustment factor for the thickness of the flexible metal substrate, is the adjustment factor for the expected thickness of the metal coating.

9. The water electroplating process for a substrate according to claim 1, characterized in that: The flexible metal substrate is a stainless steel sheet, a copper alloy sheet or a nickel alloy sheet.

10. A low resistance conductive material, characterized in that: It comprises a flexible metal substrate prepared by using the water electroplating process for substrates as described in claim 1.

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