A kind of non-profile electrolytic copper foil for PTFE ultra-high frequency board and its production process

Abstract

The present invention provides a profile-free electrolytic copper foil for PTFE ultra-high frequency boards and a production process thereof, and relates to the technical field of electrolytic copper foil. The present invention adds an additive A to a copper sulfate electrolyte, and then obtains a profile-free surface raw foil by electroplating. In the surface treatment process, an ultra-fine, uniform, non-magnetic copper nodular layer is generated by electroplating, and then treated with a nano-scale heat-resistant layer, an anti-oxidation layer and an organic layer, so that the rough surface roughness Rz of the finally obtained profile-free electrolytic copper foil is less than 1.0 μm. After the profile-free electrolytic copper foil is pressed with PTFE, the bonding force of the 18 μm copper foil is ≥1.0 kgf / cm, and the bonding force of the 35 μm copper foil is ≥1.5 kgf / cm; the signal transmission loss of the manufactured circuit is tested under 16 GHz conditions, and the Transmission Loss is less than 0.9 db / in, which can be better suitable for the manufacture of PTFE ultra-high frequency boards.

Description

Technical Field

[0001] The invention relates to the technical field of electrolytic copper foil, and in particular to a profile-free electrolytic copper foil for a PTFE ultra-high frequency board and a production process thereof. Background Art

[0002] With the development of the Internet of Things, Internet of Vehicles, cloud computing / servers and smart phones, human life has entered an era of "speedy communications". High-frequency copper clad laminates are one of the core raw materials for the construction of TD-LTE, FDD-LTE base stations, NB-IoT (Internet of Everything) networks and 5G base stations in the current mobile communications field. They are important emerging materials required for the upgrading of technologies such as unmanned millimeter-wave radar and high-precision satellite navigation. They are also key basic materials urgently needed by industries such as communication equipment, aerospace and military. High-frequency copper clad laminates are the research focus of the "high-speed era". Copper foil, resin and glass fiber cloth are the three major raw materials of copper clad laminates, and their quality directly affects PCB signal transmission. There are many resin materials suitable for the production of high-frequency copper clad laminates, such as polytetrafluoroethylene (PTFE), polyphenylene ether (PPO / PPE), cyanate ester (CE), polyimide (PI), liquid crystal polymer (LCP), etc. The corresponding dielectric properties are as follows: the dielectric constant Dk of polytetrafluoroethylene (PTFE) is 2.1, and the dielectric loss Df is 0.0005; the dielectric constant Dk of polyphenylene ether (PPO / PPE) is 2.5, and the dielectric loss Df is 0.0007; the dielectric constant Dk of cyanate ester (CE) is 2.9, and the dielectric loss Df is 0.0030; the dielectric constant Dk of polyimide (PI) is 3.1, and the dielectric loss Df is 0.0028; the dielectric constant Dk of liquid crystal polymer (LCP) is 3.3, and the dielectric loss Df is 0.0020. According to the dielectric properties of each material, it can be seen that PTFE resin has excellent dielectric properties and is most suitable for ultra-high frequency copper clad laminates.

[0003] Electronic copper foil is one of the indispensable basic materials for copper-clad laminates and is also the conductive material in printed circuit boards (PCBs). The characteristics of copper foil have a significant impact on PCB performance, especially when used in high-frequency circuit boards. The surface roughness of copper foil has a significant impact on PCB signal transmission loss. When PTFE resin is used as the raw material for ultra-high frequency boards, if traditional ordinary copper foil (STD or THE copper foil) is pressed into copper-clad laminates and then used to make circuit boards, the signal transmission loss is relatively large due to its uneven microscopic surface morphology; if ordinary HVLP copper foil (very low peak copper foil) is used to make circuit boards with PTFE, the signal transmission loss is improved to a certain extent, but due to its adenoma treatment, the particles are still relatively large, and the general HVLP copper foil contains nickel, a magnetic element, so it is difficult to meet the requirements of low signal transmission loss of ultra-high frequency boards.

[0004] For example, Chinese patent application 202110582011.5 discloses an additive for double-sided photoelectrolytic copper foil, which includes 10-60 parts by weight of nonylphenol polyoxyethylene ether, 2-10 parts by weight of fatty amine ethoxy sulfonate, 1-30 parts by weight of polydisulfide dipropane sulfonate sodium, 0.1-1 parts by weight of 2-mercaptobenzimidazole and 0.1-0.3 parts by weight of hydroxyethyl cellulose. The invention also discloses a method for preparing the double-sided photoelectrolytic copper foil, which uses an electrolytic device to prepare the copper foil and adds the additive to the electrolyte. The additive can be used to prepare an electrolytic copper foil with a rough surface roughness Ra less than 0.3μm and Rz less than 2μm at a high current density, and the tensile strength of the electrolytic copper foil can be made to reach more than 600MPa, but the additive disclosed in the application cannot meet the requirements of low signal transmission loss of ultra-high frequency boards.

[0005] Therefore, it is necessary to develop an electrolytic copper foil suitable for PTFE ultra-high frequency boards, wherein the electrolytic copper foil has almost no profile, thereby achieving the lowest possible signal transmission loss. Summary of the invention

[0006] Based on the defects and shortcomings in the prior art, the present invention aims to provide a profile-free electrolytic copper foil for PTFE ultra-high frequency boards and a production process of the electrolytic copper foil. The roughness of the rough surface of the prepared profile-free electrolytic copper foil is Rz<1.0μm. After pressing with PTFE, the bonding force of the 18μm copper foil is ≥1.0kgf / cm, and the bonding force of the 35μm copper foil is ≥1.5kgf / cm. The signal transmission loss of the circuit made after pressing with PTFE is tested under 16GHz conditions. Transmission Loss<0.9db / in.

[0007] In order to achieve the above object, the present invention is implemented by the following technical solutions:

[0008] A production process of a contour-free electrolytic copper foil for PTFE ultra-high frequency boards, the production process flow comprising: (1) manufacturing contour-free raw foil - (2) anode treatment of non-magnetic material - (3) nano-scale heat-resistant layer treatment - (4) nano-scale anti-oxidation layer treatment - (5) nano-scale organic layer treatment, to obtain the contour-free electrolytic copper foil.

[0009] The (1) process for manufacturing the profile-free raw foil is as follows: adding additive A to a copper sulfate electrolyte, and then obtaining a profile-free surface (roughness Rz≤0.7 μm) of the raw foil having a mirror effect by electrodeposition.

[0010] The copper sulfate electrolyte includes the following components: CuSO4 160-400g / L, H2SO4 80-200g / L, Cl - 30-120mg / L;

[0011] Preferably, the copper sulfate electrolyte comprises the following components in concentrations: CuSO4 250-350 g / L, H2SO4 110-130 g / L, Cl - 50-70mg / L.

[0012] The additive A is selected from at least two of sodium alcoholthiopropane sulfonate, sodium N,N-dimethyldithioformamide propane sulfonate, sodium mercaptoimidazole propane sulfonate, hexylbenzylamine salt, polyethyleneimine salt and fatty amine polyoxyethylene ether;

[0013] Preferably, the additive A is a combination of sodium thiopropane sulfonate and sodium mercaptoimidazolepropane sulfonate;

[0014] Or, the additive A is a combination of sodium N,N-dimethyldithioformamide propane sulfonate and polyethyleneimine salt;

[0015] Or, the additive A is a combination of sodium N,N-dimethyldithiocarboxamide propane sulfonate, hexylbenzylamine salt and fatty amine polyoxyethylene ether.

[0016] The total concentration of the additive A is 0.001-0.1 g / L.

[0017] Preferably, the additive A is a combination of sodium thiopropane sulfonate and sodium mercaptoimidazolepropane sulfonate, with a total concentration of 0.005-0.05 g / L;

[0018] Or, the additive A is a combination of sodium N,N-dimethyldithiocarboxamide propane sulfonate and polyethyleneimine salt, with a total concentration of 0.008-0.08 g / L;

[0019] Or, the additive A is a combination of sodium N,N-dimethyldithiocarboxamide propane sulfonate, hexylbenzylamine salt and fatty amine polyoxyethylene ether, with a total concentration of 0.01-0.08 g / L.

[0020] The electrodeposition current density is 30-100A / dm 2 ; preferably 40-80A / dm 2 .

[0021] The (2) non-magnetic material nodularization process comprises: using a copper sulfate plating solution of a non-magnetic material to perform nodularization on the contourless raw foil obtained in step (1) to obtain an electrolytic copper foil after nodularization;

[0022] The copper sulfate plating solution of the non-magnetic material comprises the following components in concentration: CuSO4 20-100g / L, H2SO4 80-200g / L, sodium molybdate 0.1-2g / L, glucose 1-10g / L;

[0023] Preferably, the copper sulfate plating solution of the non-magnetic material comprises the following components in concentration: CuSO4 50-80 g / L, H2SO4 90-130 g / L, sodium molybdate 0.2-1 g / L, glucose 2-8 g / L;

[0024] The current density of the non-magnetic material anode treatment process is 10-40A / dm 2 ; preferably 15-25A / dm 2 .

[0025] The (3) nanoscale heat-resistant layer treatment process is as follows: using a zinc-indium alloy plating solution to perform nanoscale heat-resistant layer treatment on the electrolytic copper foil after the anode treatment obtained in step (2), thereby obtaining the electrolytic copper foil after the nanoscale heat-resistant layer treatment;

[0026] The plating solution includes the following components in concentrations: ZnSO4 40-50 g / L, indium sulfate 0.1-2 g / L, potassium sodium tartrate 50-100 g / L;

[0027] Preferably, the plating solution comprises the following components in concentrations: ZnSO4 40-50 g / L, indium sulfate 0.5-1.5 g / L, potassium sodium tartrate 60-90 g / L;

[0028] The current density of the nanoscale heat-resistant layer treatment process is 0.1-1A / dm 2 ; preferably 0.2-8A / dm 2 ;

[0029] The (4) nano-scale anti-oxidation layer treatment process is as follows: using a chromium plating solution to perform nano-scale anti-oxidation layer treatment on the electrolytic copper foil treated with the nano-scale heat-resistant layer obtained in step (3), thereby obtaining the electrolytic copper foil treated with the nano-scale anti-oxidation layer;

[0030] The plating solution includes the following components in concentration: Cr 6+ 1-10g / L, pH 2-6; Preferably, the plating solution includes the following components: Cr 6+ 3-6g / L, pH 3-5;

[0031] The current density of the nano-scale anti-oxidation layer treatment process is 1-5A / dm 2 ; preferably 1-3A / dm 2 The (5) nano-scale organic layer treatment process is as follows: spraying a silane coupling agent onto the electrolytic copper foil treated with the nano-scale anti-oxidation layer prepared in step (4); the mass fraction of the silane coupling agent is 0.3%-1%, preferably 0.4%-0.8%.

[0032] The silane coupling agent is selected from one or more aqueous solutions of N-2 (aminoethyl) 3-aminopropyl triethoxysilane, 3-aminopropyl trimethylethyl silane and 3-isobutylallyl triethoxysilane.

[0033] The present invention also provides a profile-free electrolytic copper foil prepared by the above production process.

[0034] The invention also provides application of the electrolytic copper foil in preparing a PTFE ultra-high frequency board.

[0035] In the implementation process of the present invention, a mixed additive A is added to a copper sulfate electrolyte, and a raw foil with a non-profile surface having a mirror effect is obtained after electrodeposition, and then an ultra-fine, uniform, non-magnetic copper nodular layer is generated by electrodeposition, and then the copper foil is treated with a nano-scale heat-resistant layer, an anti-oxidation layer and an organic layer, so that the microscopic specific surface area of ​​the copper foil is increased to a certain extent, and the heat resistance and anti-oxidation ability are enhanced, so that the roughness Rz of the rough surface of the finally obtained non-profile electrolytic copper foil is less than 1.0 μm. After the non-profile electrolytic copper foil obtained by the present invention is pressed with PTFE, the bonding force of the 18 μm copper foil is ≥1.0 kgf / cm, and the bonding force of the 35 μm copper foil is ≥1.5 kgf / cm. The circuit made by pressing the non-profile electrolytic copper foil obtained by the present invention with PTFE has a signal transmission loss of less than 0.9 db / in under 16 GHz conditions. The non-profile electrolytic copper foil obtained by the present invention is suitable for the manufacture of PTFE ultra-high frequency boards.

[0036] Compared with the prior art, the present invention has the following beneficial effects:

[0037] (1) The present invention adds additive A to the electrolyte and controls the ratio and concentration of the additive to avoid the problem that the raw foil produced has a concave-convex microscopic surface and high roughness;

[0038] (2) The present invention adopts non-magnetic materials and ultra-fine agglomeration treatment, thereby reducing signal transmission loss and improving anti-peel strength;

[0039] (3) The present invention uses a nano-scale heat-resistant layer, an anti-oxidation layer, and an organic coating for treatment, so that the heat resistance, corrosion resistance, and peeling strength of the produced copper foil are significantly improved.

[0040] (4) The present invention realizes the preparation of profile-free electrolytic copper foil, the roughness of the raw foil's matte surface Rz≤0.7μm, and the roughness of the obtained profile-free electrolytic copper foil's matte surface Rz<1.0μm; after the profile-free electrolytic copper foil obtained by the present invention is pressed with PTFE, the bonding force of the 18μm copper foil is ≥1.0kgf / cm, and the bonding force of the 35μm copper foil is ≥1.5kgf / cm; the circuit made by pressing the profile-free electrolytic copper foil with PTFE has a signal transmission loss of <0.9db / in under 16GHz conditions, so that the prepared profile-free electrolytic copper foil is suitable for the manufacture of PTFE ultra-high frequency boards. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] Figure 1 This is a production flow chart of the contour-free electrolytic copper foil of the present invention;

[0042] Figure 2 This is the common HTE copper foil electron microscope of comparative example 1 of the present invention;

[0043] Figure 3 This is the ordinary HVLP copper foil electron microscope of comparative example 2 of the present invention;

[0044] Figure 4 This is an electron microscope image of the contour-free raw foil manufactured in Example 1 of the present invention;

[0045] Figure 5 This is an electron microscope image of the electrolytic copper foil suitable for PTFE ultra-high frequency board manufactured in Example 1 of the present invention. DETAILED DESCRIPTION

[0046] The present invention will be further described below in conjunction with specific embodiments, and the advantages and features of the present invention will become clearer as the description proceeds. However, these embodiments are exemplary only and do not constitute any limitation to the scope of the present invention. It should be understood by those skilled in the art that the details and forms of the technical solution of the present invention may be modified or replaced without departing from the spirit and scope of the present invention, but these modifications and replacements all fall within the scope of protection of the present invention.

[0047] Example 1 A production process of 35 μm non-profile electrolytic copper foil for PTFE ultra-high frequency board

[0048] The following steps are involved:

[0049] (1) Production of 35 μm raw foil without profile: copper raw material is placed in sulfuric acid and heated to dissolve to prepare copper sulfate electrolyte, wherein the copper sulfate electrolyte comprises CuSO4 260 g / L, H2SO4 110 g / L, Cl -50mg / L; and adding additive A to the copper sulfate electrolyte, the additive A is: 0.01g / L of sodium N,N-dimethyldithiocarboxamide propane sulfonate and 0.03g / L of polyethyleneimine salt combination, at a current density of 50A / dm 2 Electrodeposition was carried out under the following conditions to obtain a 35μ raw foil without outline (see Appendix 4), the roughness of which was Rz0.60μm.

[0050] (2) Nodularization of non-magnetic materials: The non-profile raw foil obtained in step (1) is subjected to nodularization treatment using a copper sulfate plating solution of non-magnetic materials to obtain an electrolytic copper foil after nodularization treatment; the copper sulfate plating solution of non-magnetic materials comprises 50 g / L CuSO4, 120 g / L H2SO4, 0.5 g / L sodium molybdate, and 5 g / L glucose; the current density is 20 A / dm 2 ;

[0051] (3) Nano-scale heat-resistant layer treatment: The electrolytic copper foil after the anode treatment obtained in step (2) is subjected to nano-scale heat-resistant layer treatment using a zinc-indium alloy plating solution to obtain an electrolytic copper foil after the nano-scale heat-resistant layer treatment; the plating solution is 45 g / L ZnSO4, 0.6 g / L indium sulfate, and 70 g / L potassium sodium tartrate; the current density is 1 A / dm 2 ;

[0052] (4) Nano-scale anti-oxidation treatment: using a chromium plating solution to treat the electrolytic copper foil treated with the nano-scale heat-resistant layer obtained in step (3) with a nano-scale anti-oxidation layer to obtain an electrolytic copper foil treated with the nano-scale anti-oxidation layer; the plating solution is Cr 6+ 4g / L, pH 4; current density 2A / dm 2 ;

[0053] (5) Nano-scale organic layer treatment: spraying a 0.5% aqueous solution of N-2 (aminoethyl) 3-aminopropyltriethoxysilane onto the electrolytic copper foil treated with the nano-scale anti-oxidation layer prepared in step (4) to obtain the profile-free electrolytic copper foil.

[0054] The 35μm non-profile electrolytic copper foil suitable for the manufacture of PTFE ultra-high frequency boards is obtained by treating the non-magnetic material agglomeration, nano-scale heat-resistant layer, anti-oxidation layer, and organic coating (see attached). Figure 5 The roughness of the rough surface of the non-profile electrolytic copper foil is Rz0.81μm, and the bonding force after pressing with PTFE is 1.7kgf / cm. The signal transmission loss of the circuit made after pressing with PTFE is tested at 16GHz and the transmission loss is 0.84db / in.

[0055] Example 2 A production process of 18 μm non-profile electrolytic copper foil for PTFE ultra-high frequency board

[0056] The following steps are involved:

[0057] (1) Production of 18 μm raw foil without profile: copper raw material is placed in sulfuric acid and heated to dissolve to prepare copper sulfate electrolyte, wherein the copper sulfate electrolyte comprises CuSO4 270 g / L, H2SO4 120 g / L, Cl - 55mg / L; and adding additive A to the copper sulfate electrolyte, the additive A is: 0.02g / L sodium thiopropane sulfonate and 0.01g / L sodium mercaptoimidazole propane sulfonate, at a current density of 60A / dm 2 Electrodeposition was carried out under the following conditions to obtain a contour-free 18μ raw foil with a rough surface of Rz0.65μm.

[0058] (2) Nodularization of non-magnetic materials: The non-profile raw foil obtained in step (1) is subjected to nodularization treatment using a copper sulfate plating solution of non-magnetic materials to obtain an electrolytic copper foil after nodularization treatment; the copper sulfate plating solution of non-magnetic materials comprises 60 g / L CuSO4, 125 g / L H2SO4, 0.4 g / L sodium molybdate, and 6 g / L glucose; the current density is 25 A / dm 2 ;

[0059] (3) Nano-scale heat-resistant layer treatment: The electrolytic copper foil after the anode treatment obtained in step (2) is subjected to nano-scale heat-resistant layer treatment using a zinc-indium alloy plating solution to obtain an electrolytic copper foil after the nano-scale heat-resistant layer treatment; the plating solution is 50 g / L ZnSO4, 0.5 g / L indium sulfate, and 80 g / L potassium sodium tartrate; the current density is 1.2 A / dm 2 ;

[0060] (4) Nano-scale anti-oxidation treatment: using a chromium plating solution to treat the electrolytic copper foil treated with the nano-scale heat-resistant layer obtained in step (3) with a nano-scale anti-oxidation layer to obtain an electrolytic copper foil treated with the nano-scale anti-oxidation layer; the plating solution is Cr 6+ 5g / L, pH 4.5; current density 1.5A / dm 2 ;

[0061] (5) Nano-scale organic layer treatment: spraying a 0.45% aqueous solution of 3-isobutylallyltriethoxysilane onto the electrolytic copper foil treated with the nano-scale anti-oxidation layer prepared in step (4) to obtain the profile-free electrolytic copper foil.

[0062] The 18μm non-profile electrolytic copper foil suitable for the manufacture of PTFE ultra-high frequency boards is obtained by treating the non-magnetic material agglomeration, nano-scale heat-resistant layer, anti-oxidation layer, and organic coating. The roughness of the rough surface of the non-profile electrolytic copper foil is Rz0.9μm, and the bonding force after pressing with PTFE is 1.3kgf / cm. The signal transmission loss of the circuit made after pressing with PTFE is tested at 16GHz. Transmission Loss0.86db / in.

[0063] Example 3 Production process of 35 μm non-profile electrolytic copper foil for PTFE ultra-high frequency board

[0064] The following steps are involved:

[0065] Production of 35μm raw foil without profile: copper raw material is placed in sulfuric acid and heated to dissolve to prepare copper sulfate electrolyte, wherein the copper sulfate electrolyte includes CuSO4 280g / L, H2SO4 120g / L, Cl - 60mg / L; and adding additive A to the copper sulfate electrolyte, the additive A is: 0.015g / L of sodium N,N-dimethyldithiocarboxamide propane sulfonate, 0.01g / L of hexylbenzylamine salt and 0.01g / L of fatty amine polyoxyethylene ether.

[0066] At a current density of 70A / dm 2 Electrodeposition was carried out under the conditions to obtain a 35μ raw foil without profile, and its rough surface roughness Rz0.62μm;

[0067] Steps (2)-(5) are consistent with Example 1. The roughness of the rough surface of the 35μm contourless electrolytic copper foil obtained is Rz0.85μm. The bonding force after pressing with PTFE is 1.8kgf / cm. The signal transmission loss of the circuit made after pressing with PTFE is tested at 16GHz and the transmission loss is 0.85db / in.

[0068] Comparative Example 1

[0069] Production of 35μm raw foil: copper raw material is placed in sulfuric acid and heated to dissolve to obtain copper sulfate electrolyte, wherein the copper sulfate electrolyte includes CuSO4 260g / L, H2SO4 110g / L, Cl - 30mg / L; and add 0.01g / L thiourea to the copper sulfate electrolyte, at a current density of 50A / dm 2 Electrodeposition was carried out under the conditions to obtain a common 35μHTE green foil;

[0070] (2) Nodularization treatment: The HTE 35μ raw foil obtained in step (1) was subjected to nodularization treatment using a copper sulfate plating solution containing 50 g / L CuSO4 and 120 g / L H2SO4; the current density was 30 A / dm 2 ;

[0071] Steps (3) to (5) are consistent with Example 1. The microscopic surface of the 35μ copper foil obtained is uneven, and the nodular particles are relatively large (see Appendix Figure 2 ), the roughness of the matte surface is Rz5.85μm, the bonding force after pressing with PTFE is 2.0kgf / cm, and the circuit made after pressing with PTFE is tested for signal transmission loss of 1.30db / in under 16GHz conditions.

[0072] Comparative Example 2

[0073] Step (1) is the same as in Example 1, and a 35μ raw foil without outline is prepared;

[0074] Step (2) Nodularization: The contourless raw foil obtained in step (1) is subjected to nodularization treatment using a copper sulfate plating solution containing iron to obtain an electrolytic copper foil after nodularization treatment; the copper sulfate plating solution contains 50 g / L CuSO4, 120 g / L H2SO4, and 5 g / L ferrous sulfate; the current density is 30 A / dm 2 ;

[0075] Steps (3) to (5) are consistent with Example 1. The microscopic surface nodular particles of the 35μ copper foil obtained are relatively large (see Appendix Figure 3 ), the roughness of the matte surface is Rz1.5μm, the bonding force after pressing with PTFE is 1.6kgf / cm, and the circuit made after pressing with PTFE is tested for signal transmission loss of 0.95db / in under 16GHz conditions.

[0076] The properties of the copper foils prepared in the above Example 1, Example 2, Example 3, Comparative Example 1 and Comparative Example 2 are compared, and the specific results are shown in Table 1 below.

[0077] Table 1 Comparison of copper foil properties

[0078]

[0079] According to the results in Table 1 above: the roughness Rz of the rough surface of the contourless copper foil provided in Examples 1-3 of the present invention is <1.0μm, the bonding force of the 18μm copper foil after pressing with PTFE is ≥1.0kgf / cm, and the bonding force of the 35μm copper foil is ≥1.5kgf / cm. The signal transmission loss of the circuit made after pressing with PTFE is tested under 16GHz conditions. Transmission Loss<0.9db / in, which is lower than that of other comparison examples, meeting the requirements of low roughness and low signal transmission loss for the manufacture of PTFE ultra-high frequency boards.

[0080] The technical means disclosed in the scheme of the present invention are not limited to the technical means disclosed in the above technical means, but also include technical schemes composed of any combination of the above technical features. The above is a specific implementation of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications are also regarded as the protection scope of the present invention.

Claims

1. A production process of profile-free electrolytic copper foil for PTFE ultra-high frequency board, characterized in that: The production process is as follows: (1) manufacturing of profile-free raw foil - (2) anode treatment of non-magnetic material - (3) nano-scale heat-resistant layer treatment - (4) nano-scale anti-oxidation layer treatment - (5) nano-scale organic layer treatment to obtain the profile-free electrolytic copper foil; The manufacturing process of the profile-free raw foil in step (1) is as follows: adding additive A to a copper sulfate electrolyte, and then obtaining a profile-free raw foil with a mirror effect by electrodeposition; The additive A is 0.01 g / L sodium N,N-dimethyldithioformamide propane sulfonate and 0.03 g / L polyethyleneimine salt; The nodularization process of the non-magnetic material in step (2) is as follows: the non-magnetic raw foil obtained in step (1) is subjected to nodularization treatment using a copper sulfate plating solution of a non-magnetic material to obtain an electrolytic copper foil after nodularization treatment; The copper sulfate plating solution of the non-magnetic material is composed of the following components: Composition: CuSO4 20-100g / L, H2SO4 80-200g / L, sodium molybdate 0.1-2g / L, glucose 1-10g / L; current density 10-40A / dm 2 .

2. The production process according to claim 1, characterized in that: The copper sulfate electrolyte comprises the following components: CuSO4 160-400g / L, H2SO4 80-200g / L, Cl - 30-120mg / L.

3. The production process according to claim 1, characterized in that: The electrodeposition current density is 30-100A / dm 2 .

4. The production process according to claim 1, characterized in that: The nanoscale heat-resistant layer treatment process described in step (3) is: using a zinc-indium alloy plating solution to perform nanoscale heat-resistant layer treatment on the electrolytic copper foil after the anode treatment obtained in step (2), so as to obtain the electrolytic copper foil after the nanoscale heat-resistant layer treatment; The plating solution includes the following components: ZnSO4 40-50g / L, indium sulfate 0.1-2g / L, potassium sodium tartrate 50-100g / L; the current density is 0.1-1A / dm 2 .

5. The production process according to claim 1, characterized in that: The nano-scale anti-oxidation layer treatment process described in step (4) is: using a chromium plating solution to perform nano-scale anti-oxidation layer treatment on the electrolytic copper foil treated with the nano-scale heat-resistant layer obtained in step (3), thereby obtaining the electrolytic copper foil treated with the nano-scale anti-oxidation layer; The plating solution includes the following components in concentration: Cr 6+ 1-10g / L, pH 2-6; Current density is 1-5A / dm 2 .

6. The production process according to claim 1, characterized in that: The nanoscale organic layer treatment process described in step (5) is: spraying a silane coupling agent onto the electrolytic copper foil treated with the nanoscale anti-oxidation layer prepared in step (4); the mass fraction of the silane coupling agent is 0.3%-1%.

7. The profile-free electrolytic copper foil prepared according to the production process according to any one of claims 1 to 6.

8. Use of the contourless electrolytic copper foil according to claim 7 in the preparation of PTFE ultra-high frequency boards.

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