Copper surface treatment method for a combination of polymer and copper

Abstract

The present invention provides a copper surface treatment method for manufacturing a metal combination of a polymer and copper with excellent bonding strength. The present invention specifically discloses a method for treating the copper surface for bonding coupling of a polymer and copper, and the copper surface treatment method includes: (a) an etching step of electro-etching the copper surface, (b) a first anodization step of anodizing the copper surface, and (c) a second anodization step of anodizing the copper that has been subjected to the first anodization treatment again. After ultrasonic treatment of the copper that has been subjected to the second anodization treatment, the copper is oxidized again.

Description

Technical Field

[0001] The present invention relates to a method for treating a copper surface of an assembly for the binding coupling of a polymer and copper. More specifically, the present invention relates to a method for treating a copper surface of an assembly for a polymer and copper, by performing a first anodic oxidation treatment and a second anodic oxidation treatment on the copper surface to maximize the binding of the assembly of the polymer and the copper surface. Background Art

[0002] Assemblies of polymers and copper have been applied in various ways to lithium-ion batteries in automobiles, smartphones, or electronic devices, which require waterproof characteristics. However, the bonding strength between the polymer and copper has been pointed out to have potential problems due to its low reliability.

[0003] Therefore, during its manufacturing process, by performing an anodic oxidation treatment on copper, the activity and friction of the copper surface are increased, so that the copper and the polymer are more firmly bonded. However, even after the first anodic oxidation treatment, sufficient adhesion and shielding properties with the polymer cannot be obtained.

[0004] Prior Art

[0005] Patent Application

[0006]

Patent Application 1

[0007] Technical Problem to be Solved by the Invention

[0008] The present invention provides a method for treating a copper surface to solve the above technical problems. The object of the present invention is to provide a method for treating a copper surface to manufacture a metal assembly of a polymer and copper having excellent bonding strength and shielding properties.

[0009] Means for Solving the Technical Problem

[0010] The object of the present invention is to provide a method for treating a copper surface for the binding coupling of a mixture of a polymer and copper, which has the following characteristics:

[0011] (a) An etching step of electro-etching the copper surface,

[0012] (b) A first anodic oxidation step of anodizing the copper surface, and

[0013] (c) A second anodic oxidation step of anodizing the copper that has been subjected to the first anodic oxidation treatment again.

[0014] In step (b), in a mixed solvent of 0.01 - 0.05 wt% NaNO2, 0.1 - 1 wt% NH4F as an auxiliary agent, and 0.01 - 0.1 wt% C2H4(OH)2 as an additive, using a 500 ms pulsed rectifier, at a temperature of 30 - 90 °C, with a current density of 0.01 - 5 A / dm 2 for 1 - 15 minutes.

[0015] In step (c), for the second anodic oxidation treatment, a mixed solvent of 0.1 - 2 wt% C2K2O4, 0.1 - 0.5 wt% Na2O3Si as an auxiliary agent, 0.01 - 0.1 wt% C3H8O3 as an auxiliary agent, and 0.001 - 0.01 wt% C 20 H 24 Na2O 10 S2 is used, and using a 500 ms pulsed rectifier, at a temperature of 30 - 70 °C, with a current density of 0.01 - 1 A / dm 2 for 1 - 10 minutes.

[0016] In step (c), 0.01 - 1 wt% of a silane coupling agent is used as an additive to the mixed solvent.

[0017] In step (c), the silane coupling agent as an additive can be selected from one of the following: (RO)3Si-(CH2)3-NH2, (RO)3Si-(CH2)2-Si(OC2H5)3, (RO)3Si-(CH2)3-SH, (RO)3Si-CH=CH2, (RO)3Si-(CH3)3-OOC(CH3)C=CH2, (RO)3Si-(CH3)3-O-CHCH2O, and (RO)3Si-(CH2) 15 CH3.

[0018] After step (c), the copper after the second anodic oxidation treatment is subjected to ultrasonic treatment.

[0019] In a 0.001 - 0.01 wt% H2SO4 solvent with the addition of 0.001 - 0.01 wt% C2H4(OH)2 as an additive, at a temperature of 30 - 60 °C, ultrasonic treatment is carried out at 400 W and 24 - 100 kHz for 1 - 3 minutes.

[0020] After ultrasonic treatment, the copper is subjected to oxidation treatment.

[0021] The oxidation treatment is carried out in a 0.1 - 3 wt% H2O2 solvent with the addition of 0.001 - 0.01 wt% Na2S2O3 as an additive, at a temperature of 30 - 60 °C for 10 seconds - 5 minutes.

[0022] After the oxidation treatment, the copper is dried at a temperature of 70 to 80 °C for 5 to 10 minutes.

[0023] Advantages of the Invention

[0024] According to the present invention, the copper surface treatment in the present invention has the effect of maximizing the bonding strength between the polymer and copper by generating protrusions on the copper surface during the first anodic oxidation treatment, generating protrusions on the needle-like oxide film during the second anodic oxidation process to maximize the contact area, adding a silane coupling agent during the second anodic oxidation process, and producing a polymer on the protrusions of the needle-like oxide film.

[0025] In addition, by performing ultrasonic treatment after the second anodic oxidation treatment, microcracks are generated on the needle-like oxide film, and then visible protrusions are generated on the fine oxide film on the oxidized microcracks, thereby having the effect of maximizing the bonding strength between the polymer and copper. Description of the Drawings

[0026] Figure 1 Shows the changes in the oxide film during each process after the copper surface treatment.

[0027] Figure 2 Shows Figure 1 A detailed view of the final oxide film.

[0028] Figure 3 Shows the apparatus and conditions for the first anodic oxidation treatment and the second anodic oxidation treatment.

[0029] Figure 4 Shows the ultrasonic apparatus.

[0030] Figure 5 Shows the reaction structure of the silane coupling agent between the polymer and copper.

[0031] Figure 6 (A) is a surface photograph of the oxide film of copper for each process, and (B) is a cross-sectional view of the copper oxide film for each process.

[0032] Figure 7 Shows the T-bend test method for the existing product, the present invention, and their fracture surfaces after the temperature and humidity test.

[0033] Figure 8 Shows the experimental method for the tensile strength after each temperature and humidity test after adding additives and the first and second anodic oxidation treatments.

[0034] Figure 9 Shows the test results of the tensile strength after each temperature and humidity test after adding additives and the first and second anodic oxidation treatments.

[0035] Figure 10 It is a photograph showing the fracture surface after the tensile strength test was conducted after the temperature and humidity test, additives were added, and the first and second anodization treatments were performed.

[0036] Figure 11 It is a comparison graph showing the change in tensile strength over time after the first and second anodization treatments and the addition of additives.

[0037] Figure 12 It shows the measuring device for the temperature and humidity test and its specimen.

[0038] Figure 13 It is a comparison graph of the sealing after the temperature and humidity test was conducted after the first and second anodization treatments and the addition of additives. Detailed implementation mode

[0039] Referring to the following schematic diagram, it illustrates how to use the present invention to manufacture the combination of polymer and copper.

[0040] The present invention is a method for treating the copper surface to maximize the bonding coupling of the mixture of polymer and copper, in the following manner:

[0041] (a) An etching step of electro-etching the copper surface,

[0042] (b) A step of the first anodization treatment of anodizing the copper surface, and

[0043] (c) A second anodization step of anodizing the copper again after the first anodization treatment.

[0044] In step (a), a mixed solution of 5 wt% H2SO2, 10 wt% HNO3, 0.1 wt% of other surfactants, etc. is used on the copper surface, and at 30 - 70 °C, a 500 ms pulse rectifier is used at 1 - 10 A / dm 2 for 5 - 15 minutes of electro-etching treatment.

[0045] This electro-etching treatment leaves an irregular etching pattern on the copper surface.

[0046] In step (b), in a mixed solvent of 0.01 - 0.05 wt% NaNO2, 0.1 - 1 wt% NH4F as an auxiliary agent, 0.01 - 0.1 wt% C2H4(OH)2 as an additive, a pulse rectifier is used at a temperature of 30 - 90 °C at a current density of 0.01 - 5 A / dm 2 for 1 - 15 minutes of treatment.

[0047] The first anodic oxidation treatment oxidizes the etched copper surface and forms a copper oxide film with fine protrusions on its surface.

[0048] In step (c), the second anodic oxidation treatment uses a mixed solvent of 0.1 - 2 wt% of C2K2O4, 0.1 - 0.5 wt% of Na2O3Si as an additive, 0.01 - 0.1 wt% of C3H8O3 as an additive, and 0.001 - 0.01 wt% of C 20 H 24 Na2O 10 S2, and uses a pulsed rectifier of 500 ms to treat at a current density of 0.01 - 1 A / dm at a temperature of 30 - 70 °C for 1 - 10 minutes. 2 for 1 - 10 minutes.

[0049] In step (c), the electrolyte used can be one of the following: C2K2O4, NaHCO3, NaOH, Na2CO3, Na2SO4, K2SO3, Na2SO3, NaNO2, KNO2, NaNO3, NaClO4, CH3COONa, Na2B2O7, NaH2PO2, (NaPO3)6, Na2MoO4, Na3SiO3, and Na2HPO3.

[0050] In step (c), through the second anodic oxidation treatment, during the first anodic oxidation treatment on the copper surface, the protrusions generated by the first anodic oxidation treatment will form sharp protrusions that look like cactus spines between the thin oxide films, which will produce a thin and rough complex of the oxide film, maximizing the contact area, and thus maximizing the bonding strength between the polymer and copper.

[0051] In step (c), 0.01 - 1 wt% of a silane coupling agent is added as an additive to the mixed solution to maximize the bonding strength between the copper after the second anodic oxidation treatment and the polymer.

[0052] Due to the superposition of the van der Waals forces between the polymer and the additives remaining in the copper oxide film after the second anodic oxidation, an additional bonding strength is generated.

[0053] In step (c), the silane coupling agent as an additive can be one of the following: (RO)3Si-(CH2)3-NH2, (RO)3Si-(CH2)2-Si(OC2H5)3, (RO)3Si-(CH2)3-SH, (RO)3Si-CH=CH2, (RO)3Si-(CH3)3-OOC(CH3)C=CH2, (RO)3Si-(CH3)3-O-CHCH2O, and (RO)3Si-(CH2) 15 CH3.

[0054] After step (c), after the second anodization treatment of copper, a solvent of 0.001 - 0.01 wt% H2SO4 with 0.001 - 0.01 wt% C2H4(OH)2 added as an additive is used, and ultrasonic treatment is carried out at 30 - 60 °C for 1 - 3 minutes at 400 W and 24 - 100 kHz.

[0055] Through the first and second anodization treatments, starting from the ultrasonic treatment, fine microcracks are formed on the raised oxidation film on the copper surface. It will further roughen the surface to maximize the contact area, thereby maximizing the bonding strength between the polymer and copper.

[0056] Finally, for the copper after ultrasonic treatment, a 0.1 - 3 wt% H2O2 solvent with 0.001 - 0.01 wt% Na2S2O3 added as an additive is used, and oxidation treatment is carried out at a temperature of 30 - 60 °C for 10 seconds to 5 minutes.

[0057] In the final oxidation treatment, the fine microcracks formed on the raised oxidation film on the copper surface after ultrasonic treatment will be oxidized, and fine protrusions on the oxidation film will be additionally generated on the microcracks. In this way, the contact area with the copper surface is maximized, and thus the bonding strength between copper and the polymer is also maximized.

[0058] Figure 1 Shows the changes in the oxidation film in each process after treating the copper surface.

[0059] Figure 2 Shows the specific shape of the oxidation film generated in each process.

[0060] Hereinafter, specific examples and drawings will be described.

[0061] Example 1

[0062] In step (a), the copper surface is treated with a mixed solution of 5 wt% H2SO2, 10 wt% HNO3, 0.1 wt% additional additive (surfactant), etc., and using a 500 ms pulse rectifier at 30 - 70 °C with a current density of 1 - 10 A / dm 2 for 5 - 15 minutes of electroetching.

[0063] In step (b), the sample is only subjected to the first anodization treatment. It is placed in a mixed solvent containing 0.01 - 0.05 wt% NaNO2, 0.1 - 1 wt% NH4F as an auxiliary agent, and 0.01 - 0.1 wt% C2H4(OH)2 as an additive, and using a pulse rectifier at 0.01 - 5 A / dm 2The current density is placed for 1 - 15 minutes at a temperature of 30 - 90°C.

[0064] Example 2

[0065] After the etching treatment using the electro - etching in step (a),

[0066] After the first anodization treatment in step (b),

[0067] In step (c), a mixed solvent of 0.1 - 2 wt% C2K2O4, 0.1 - 0.5 wt% Na2O3Si as an auxiliary agent, 0.01 - 0.1 wt% C3H8O3 as an auxiliary agent, and 0.001 - 0.01 wt% C 20 H 24 Na2O 10 S2 is used. A second anodization treatment is carried out on the copper after the first anodization treatment for 1 - 10 minutes at a temperature of 30 - 70°C with a current density of 0.01 - 1 A / dm 2 to produce a specimen.

[0068] Example 3

[0069] After the etching treatment using the electro - etching in step (a),

[0070] After the first anodization treatment in step (b),

[0071] 0.01 - 1 wt% silane coupling agent is added as an additive to the mixed solvent used in the second anodization treatment in step (c) to produce a specimen.

[0072] Example 4

[0073] After the etching treatment using the electro - etching in step (a),

[0074] After the first anodization treatment in step (b),

[0075] After adding 0.01 - 1 wt% silane coupling agent as an additive to the mixed solvent used in the second anodization treatment in step (c),

[0076] A 0.001 - 0.01 wt% H2SO4 solvent added with 0.001 - 0.01 wt% C2H4(OH)2 is used. At a temperature of 30 - 60°C, ultrasonic treatment is carried out on the copper after the second anodization treatment for 1 - 3 minutes at 400 W, 24 - 100 kHz to produce a specimen.

[0077] Example 5

[0078] After the etching treatment using the electro-etching in step (a),

[0079] After the first anodization treatment in step (b),

[0080] During the second anodization treatment in step (c)2, after adding 0.01 - 1 wt% of a silane coupling agent as an additive to the mixed solvent for the second anodization,

[0081] After subjecting the copper after the second anodization treatment to ultrasonic treatment,

[0082] By using a 0.1 - 3 wt% H2O2 solvent with 0.001 - 0.01 wt% of Na2S2O3 added as an additive, at a temperature of 30 - 60 °C, the copper after ultrasonic treatment was subjected to an oxidation treatment for 10 seconds to 5 minutes to prepare a specimen.

[0083] The specimens prepared in Examples 1 - 5 were subjected to a resistance test, a T-bend test, a tensile strength test, and a standing time test to measure the bonding strength and the sealing quality. The following are the results.

[0084] Test 1

[0085] Using the specimens of Examples 1 - 5, the resistance was measured and the current-carrying ability was confirmed. The results are shown in Table 1.

[0086] Table 1

[0087]

[0088] Test 2

[0089] Using the specimens of Examples 1 - 5, after a 1000-hour temperature and humidity test, a T-bend test was performed to measure the bonding strength. The results are shown in Table 2.

[0090] Table 2

[0091] Test piece Example 1 Example 2 Example 3 Example 4 Example 5 T-bend test Defective Good Good Good Good

[0092] As shown in Table 2, compared with the specimens subjected to the first anodization treatment in Example 1, the specimens subjected to the second anodization treatment in Examples 2 - 5 showed more excellent characteristics in terms of the bonding strength.

[0093] Figure 7 a is a specimen prepared for the T-bend test, which has a polymer covering the copper specimens of each example.

[0094] Figure 7 b shows the test results of "good" quality in the T-bend test and a schematic diagram of how to perform such a test.

[0095] Figure 7 c shows a schematic diagram of the test results of "poor" quality in the T-bending test and how to conduct such a test.

[0096] Test 3

[0097] Using the specimens of Examples 1 to 5, after 1000 hours of temperature and humidity testing, a T-bending test was conducted to measure the bonding strength, and the results are shown in Figure 9 .

[0098] As Figure 9 shown in the chart in, compared with the specimen of Example 1, the specimen of Example 2 showed excellent tensile strength before and after the temperature and humidity test.

[0099] In addition, compared with the specimen of Example 2, the specimen of Example 3 showed excellent tensile strength before and after the temperature and humidity test.

[0100] Compared with the specimen of Example 3, the specimen of Example 4 showed excellent tensile strength before and after the temperature and humidity test.

[0101] Finally, compared with the specimen of Example 4, the specimen of Example 5 showed excellent tensile strength before and after the temperature and humidity test.

[0102] Figure 8 A shows the specimens made for the tensile strength test, on which polymers are covered on the copper specimens of each example.

[0103] Figure 8 B is a diagram of the experimental method for the tensile strength test.

[0104] Figure 10 are photos of the polymer residue amounts on the separated copper surfaces after the tensile strength experiments were conducted on the specimens of Examples 1 to 5 after the temperature and humidity test.

[0105] Figure 10 A is a photo of the separated side of the specimen of Example 1, showing that it has been conveniently separated and there is almost no polymer on the copper surface.

[0106] Figure 10 B is a photo of the separated side of the specimen of Example 2, showing that 20% of the polymer is retained on the copper surface due to the separation.

[0107] Figure 10 C is a photo of the separated side of the specimen of Example 3, showing that 40% of the polymer is retained on the copper surface due to the separation.

[0108] Figure 10 D is a photo of the separated side of the specimen of Example 4, showing that 60% of the polymer is retained on the copper surface due to the separation.

[0109] Figure 10 E is a photograph of the separation side of the specimen of Example 5, showing that 80% of the polymer is retained on the copper surface due to separation.

[0110] Figure 11 The graph in shows the test results of the tensile strength of the specimens in each example 1 to 12 months after the polymer was coated on the specimens.

[0111] Similarly, compared with the specimen of Example 1, the specimen of Example 2 showed better quality in terms of the decrease in tensile strength over time.

[0112] In addition, compared with the specimen of Example 2, the specimen of Example 3 showed a greater decrease in tensile strength over time.

[0113] Compared with the specimen of Example 3, the specimen of Example 4 showed a greater decrease in tensile strength over time.

[0114] Finally, compared with the specimen of Example 4, the specimen of Example 5 showed a greater decrease in tensile strength over time.

[0115] Test 4

[0116] Using the specimens of Examples 1 to 5, a temperature and humidity test was conducted to measure the sealing between copper and the polymer, and the results are as Figure 13 shown.

[0117] As Figure 13 shown in the graph in, compared with the specimen of Example 1, the specimen of Example 2 showed better sealing quality.

[0118] In addition, compared with the specimen of Example 2, the specimen of Example 3 showed better sealing quality.

[0119] In addition, compared with the specimen of Example 3, the specimen of Example 4 showed better sealing quality.

[0120] Finally, compared with the specimen of Example 4, the specimen of Example 5 showed the best sealing quality.

[0121] Figure 12 A is a photograph of the specimen for the temperature and humidity test.

[0122] Figure 12 B is a picture of the device for conducting the temperature and humidity test.

[0123] Feasibility of industrial application

[0124] The present invention relates to a method for manufacturing a combination of a polymer and copper, which enhances the bonding strength between the polymer and copper by treating the copper surface, improves the sealing quality of components, makes them lighter, and saves the funds consumed by these components.

Claims

1. A copper surface treatment method for coupling a mixture of polymer and copper, characterized in that, Comprising: (a) An etching step of electrochemically etching the copper surface; (b) A first anodizing step of anodizing the copper surface; And (c) A step of second anodizing the copper after the first anodizing treatment; Among them, in step (b), it includes: in a mixed solvent of 0.01 to 0.05 wt% of NaNO2, 0.1 to 1 wt% of NH4F as an auxiliary agent, and 0.01 to 0.1 wt% of C2H4(OH)2 as an additive, using a pulse rectifier to treat at a temperature of 30 to 90 °C with a current density of 0.01 to 5 A / dm 2 for 1 to 15 minutes; and In step (c), the second anodization treatment uses a mixed solvent of 0.1 to 2 wt% of C2K2O4, 0.1 to 0.5 wt% of Na2O3Si as an auxiliary agent, 0.01 to 0.1 wt% of C3H8O3 as an auxiliary agent, and 0.001 to 0.01 wt% of C 20 H 24 Na2O 10 S2, and uses a pulse rectifier of 500 ms to treat at a temperature of 30 to 70 °C for 1 to 10 minutes at a current density of 0.01 to 1 A / dm 2 ; In step (c), 0.01 - 1 wt% of a silane coupling agent is added, and this silane coupling agent is an additive in the mixed solvent.

2. The copper surface treatment method according to claim 1, characterized in that: In step (c), the silane coupling agent used as an additive can be one of the following: (RO)3Si-(CH2)3-NH2, (RO)3Si-(CH2)2-Si(OC2H5)3, (RO)3Si-(CH2)3-SH, (RO)3Si-CH=CH2, and (RO)3Si-(CH2) 15 CH3.

3. The copper surface treatment method according to claim 1, characterized in that: Ultrasonic treatment is performed after the second anodizing step (c).

4. The copper surface treatment method according to claim 3, characterized in that: Using a solvent of 0.001 - 0.01 wt% of H2SO4 with 0.001 - 0.01 wt% of C2H4(OH)2 added as an additive, ultrasonic treatment is performed at a temperature of 30 - 60 °C for 1 - 3 minutes at 400 W, 24 - 100 kHz.

5. The copper surface treatment method according to claim 3, characterized in that: Oxidation treatment is performed after ultrasonic treatment.

6. The copper surface treatment method according to claim 5, characterized in that: Using a solvent of 0.1 - 3 wt% of H2O2 with 0.001 - 0.01 wt% of Na2S2O3 added as an additive, oxidation treatment is performed at a temperature of 30 - 60 °C for 10 seconds - 5 minutes.

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