CN106011965A - Fine roughing treatment technology for surface of electrolytic copper foil - Google Patents
Fine roughing treatment technology for surface of electrolytic copper foil Download PDFInfo
- Publication number
- CN106011965A CN106011965A CN201610421834.9A CN201610421834A CN106011965A CN 106011965 A CN106011965 A CN 106011965A CN 201610421834 A CN201610421834 A CN 201610421834A CN 106011965 A CN106011965 A CN 106011965A
- Authority
- CN
- China
- Prior art keywords
- copper foil
- roughening
- grades
- electrolytic copper
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
The invention relates to a fine roughing treatment technology for the surface of electrolytic copper foil. The fine roughing treatment technology includes the following processes of primary roughing, secondary roughing, primary curing, secondary curing, third-level roughing, zinc and nickel alloy plating, oxidization preventing, silane coupling agent treating and drying. The copper foil produced through the technology has relatively low surface roughness, meanwhile has very high stripping resisting strength, especially shows excellent bonding strength on plates of Tg 170 or above and is very suitable for low-loss and ultra-low-loss high-speed circuit boards. Key technology indexes of the copper foil produced through the technology reach the level of the same kind of products of advanced copper foil manufacturers such as Mitsui Mining and Smelting (MHT), Furukawa Electric (MP) and JX Nippon Oil (JTC-LC), replaces imported copper foil of the same kind and is applied to high multi-layer high-end plates, HDI high-end plates, halogen-free high-end plates and other high-end plates in China or Euramerican countries.
Description
Technical field
The present invention relates to the process of surface treatment of a kind of Copper Foil, particularly relate to the roughening treatment technique of a kind of electrolytic copper foil surface, belong to high-precision electronics Copper Foil technical field of producing.
Background technology
Electronics Copper Foil is one of primary base material of printed circuit board, is widely used in electric product.China is electronics Copper Foil big producing country, but also has bigger gap in production technology compared with developed countries, and the most high-end Copper Foil product (for high multilamellar, high density interconnection etc.) always Japan and American-European enterprise specially enjoy.High multilamellar (generally higher than 26 layers), high density interconnection (HD I) printed circuit electronics Copper Foil, except requiring internal performance (tensile strength under room temperature, high temperature and the ductility with excellence, antioxidation, corrosion-resistant, resistance etc.) and environmental friendliness outside, limited by its manufacturing process and use environment, also requiring that Copper Foil has relatively low surface roughness, so when high-speed transfer, the dielectric loss of circuit can reduce.On the other hand, there is the Copper Foil of relatively low rugosity for printed circuit, be conducive to making finer circuit.But, for Copper Foil producer, improving the peel strength adhesion strength of resin (i.e. with) of Copper Foil while reducing the roughness of Copper Foil again, particularly on the low-loss sheet material of Tg170～Tg230 (vitrification point), technical difficulty is the biggest.The product of this most domestic Copper Foil manufacturer, is difficult to meet the one of the main reasons of American-European high-end printed circuit.The present inventor, technical characterstic according to American-European high-end printed circuit Copper Foil, on the premise of the technology such as room temperature, the tensile strength of high temperature and the ductility the general high temperature high ductibility Copper Foil (HTE) of holding require, invent special surface and processed the low roughness Copper Foil of technique, it is adaptable to the low-loss of more than Tg170, ultra-low loss, high multilamellar, HD I, Halogen contour end plate material.
Summary of the invention
Technical problem solved by the invention, is to fill up the technological gap of existing domestic Copper Foil industry, it is provided that the fine roughening treatment technique of a kind of electrolytic copper foil surface.
The technical scheme is that
A kind of fine roughening treatment technique of electrolytic copper foil surface, including following technological process: one-level is roughened-two grades of roughening-one-level solidification-three grades of roughening-zinc-nickel alloys of-two grades of solidifications-anti-oxidation-silane coupler and processes-be dried, it is characterized in that, the process conditions of the roughening of described one-level, two grades of roughening and three grades of roughening are: CuSO4·5H2O 40～100g/L, H2SO460～220g/L, Na3PO4·12MO30.1～2.0g/L, temperature 15～40 DEG C.
On the basis of technique scheme, the present invention can also do following improvement.
Further, the roughening of described one-level, two grades of roughening and three grades of roughening be by cathode copper in the sulphuric acid of 40～80 DEG C, be passed through air stirring and dissolve, form the mixed liquor of copper sulfate and sulphuric acid, the electric current density of one-level roughening is 15～25A/dm2, 2～4s, the electric current density of described two grades of roughening is 20～25A/dm2, 2～4s, the electric current density of described three grades of roughening is 5～15A/dm2, 1～3s.
Further, the process conditions of described one-level roughening, two grades of roughening and three grades of roughening are: CuSO4·5H2O 45～80g/L, H2SO480～200g/L, Na3PO4·12MO30.2～1.8g/L, temperature 20～38 DEG C.
Further, the process conditions of described one-level roughening, two grades of roughening and three grades of roughening are: CuSO4·5H2O 50～60g/L, H2SO4140～180g/L, Na3PO4·12MO30.4～1.5g/L, temperature 25～35 DEG C.
The numbered 1313-30-0 of CAS of the sodium phosphomolybdate that the present invention uses, structural formula is as follows:
The effect of one-level roughening and two grades of roughening is the surface at Copper Foil, forms dendritic small crystallization, increases the specific surface area of Copper Foil in order to improve the adhesion strength of Copper Foil and resin material.The roughening treatment step of the present invention, uses sodium phosphomolybdate to do additive, changes the electro-deposition structure (as shown in Figure 3) of copper foil surface.Obviously, the Copper Foil of the present invention is compared with the Copper Foil (Fig. 4) that common roughening treatment obtains, there is more excellent nodular texture, the nodular texture of common Copper Foil roughened layer it is in place of its excellence, focus primarily upon the top on " mountain peak ", and present invention process processes the roughened layer of the Copper Foil obtained, " mountain peak " and " mountain valley " all has uniform nodular texture (as shown in Figure 5).Three grades of roughening, are on the nodular texture surface formed, and form more small point-like crystallization (SEM, 20,000 times, 20-150 nanometer), increase specific surface area further, to improve and the adhesion strength of resin material.
Further, also include acid pickling step before the roughening of described one-level, after described three grades of roughening and anti-oxidation step, also include water-washing step.
Further, described one-level solidification and two grades of solidifications be by cathode copper in the sulphuric acid of 40～90 DEG C, be passed through air stirring and dissolve, form the mixed liquor of copper sulfate and sulphuric acid, pumping into roughening groove to electroplate, one-level solidification solidifies concrete process conditions with two grades and is: CuSO4·5H2O 150～300g/L, H2SO480～180g/L, temperature 35～55 DEG C, electric current density is 15～35A/dm2, 4～10s.
Further, described zinc-nickel alloy refers to potassium pyrophosphate, zinc sulfate, nickel sulfate respectively with water dissolution, lower joining in potassium pyrophosphate solution by zinc sulfate, nickel sulfate solution being stirred continuously, pump in coating bath and electroplate after stirring, concrete technology condition is: ZnSO4·7H2O 0.5～10g/L, NiSO4·6H2O 4～20g/L, K4P2O7·3H2O 150～300g/L, pH 8～11, temperature 30～50 DEG C, electric current density 1～5A/dm2, 2～6s.
Further, described anti-oxidation step refers to, by sodium dichromate water dissolution, use H2SO4Being added thereto to zinc sulfate after regulation pH value dissolve, pump into coating bath and electroplate after stirring, concrete process conditions are: Na2Cr2O7: 5～10g/L, ZnSO4·7H2O:0.1～1.0g/L, pH 2～4, temperature 30～50 DEG C, electric current density 0.5～3.0A/dm2, 1～4s.
Further, it is by γ-glycidyl ether oxygen propyl trimethoxy silicane aqueous solution that concentration is 0.05～0.5wt% that described silane coupler processes step, it is sprayed at copper foil surface under room temperature state, after in the baking oven of 200～400 DEG C toast 4～8s, described γ-glycidyl ether oxygen propyl trimethoxy silicane, CAS numbering is 2530-83-8, and molecular formula is C9H20O5Si。
Further, the HTE Copper Foil that described electrolytic copper foil uses thickness to be 9～140 μm is former paper tinsel, and its working condition is as follows: use the arc Ni-Ti anode of coated with nano iridium dioxide and drum type to rotate Ti cathode, in CuSO4·5H2O 300g/L,H2SO4 140g/L,Cl-30mg/L, temperature 57 DEG C, electric current density 69A/dm2, along with copper-stripping is obtained electrolytic copper foil by the lasting rotation of negative electrode.
The principle of present invention process roughening treatment process is as follows:
Sodium phosphomolybdate is added as additive in coarsening process, change the structure of electro-deposition, its electrochemical mechanism is that sodium phosphomolybdate defines heteropolyacid salt with copper ion complexation in an acidic solution, changing the electrochemistry deposition potential of copper ion, it is mobile that the copper molybdenum alloy of formation receives Inhibition backward " mountain valley " in " mountain peak " deposition.By controlling concentration and the electrodeposition condition of additive sodium phosphomolybdate, finally give the most highly uniform nodular surface structure.The Copper Foil of this uniform nodular texture, sheet material at Tg175, by peel strength from about the 1.15N/mm (with reference to comparative example 2) of common Copper Foil, bring up to more than 1.6N/mm (reference example 1-5), reached the level of Copper Foil producer leading in the world like product.
The invention has the beneficial effects as follows:
1) Copper Foil that present invention process produces, there is relatively low surface roughness, there is again the highest peel strength, particularly on the sheet material of more than Tg170 simultaneously, show the adhesion strength of excellence, be very suitable for the high speed circuit board of low-loss, ultra-low loss；
2) Copper Foil that present invention process produces, has the anti-room temperature of excellence, high temperature oxidation stability.In temperature less than 40 DEG C, under conditions of humidity is less than 60%, deposits 1 year and do not aoxidize；In the high temperature of 210 DEG C, it is passed through air stirring do not aoxidize for 1 hour；Being 85 DEG C in temperature, humidity is within 48 hours, not aoxidize under conditions of 90%.
3) Copper Foil that present invention process produces, has the plating resist layer diffusion of excellence, occurs without the color change that the diffusion of obvious coating causes under room temperature (25 DEG C, 3 months), high temperature (210 DEG C, 1 hour)；There is chemical proofing and the etching of excellence, be suitable for very fine circuit；There is the highest peel strength and high temperature resistance conversion performance, be adapted to the Pb-free coating of PCB；There is the bright finish microetch characteristic of excellence, be adapted to the thin base production requirement that high multilayer printed circuit needs.
4) present invention does not use the compound of the elements such as arsenic, antimony, lead, hydrargyrum, cadmium, it is achieved that production process and the environmental protection of product.
The Copper Foil that present invention process produces, key technical index has reached the like product level of the advanced Copper Foil producer such as Mitsui metal (MHT), Furukawa (MP), JX day Shi ore deposit metal (JTC-LC).Substitute similar import Copper Foil, be applied to domestic or American-European high multilamellar, HDI, Halogen contour end plate material.
Accompanying drawing explanation
Fig. 1 is the process chart of the present invention；
Fig. 2 is the SEM picture of the former paper tinsel of 35 μm；
Fig. 3 is the SEM picture of 35 μm electrolytic copper foils after present invention process processes；
Fig. 4 is the SEM picture of the 35 μm Copper Foils that comparative example 2 obtains；
Fig. 5 is that present invention process processes, with common process, the Copper Foil tangent plane schematic diagram obtained.
Detailed description of the invention
Being described principle and the feature of the present invention below in conjunction with example, example is served only for explaining the present invention, is not intended to limit the scope of the present invention.
Embodiment 1:
The fine roughening treatment technique of a kind of electrolytic copper foil surface, comprises the technical steps that:
1) it is former paper tinsel by the HTE Copper Foil of 35 μm, uses the arc Ni-Ti anode of coated with nano iridium dioxide and diameter 2700mm drum type to rotate Ti cathode, in CuSO4·5H2O 300g/L,H2SO4140g/L,Cl-30mg/L, temperature 57 DEG C, electric current density 69A/dm2Under the conditions of, along with copper-stripping is obtained electrolytic copper foil by the lasting rotation of negative electrode；
2) step 1) gained Copper Foil enter 10wt% dilute sulfuric acid in carry out pickling, time 3s；
3) one-level roughening and two grades of roughening: by step 2) processed after Copper Foil entrance following process conditions under carry out one-level roughening: CuSO4·5H2O 60g/L, H2SO4180g/L, Na3PO4·12MO30.5g/L, temperature 28 DEG C, electric current density 18A/dm2, 2.6s, the Copper Foil after one-level roughening enters two grades of roughening, and the process conditions of two grades of roughening are as follows: CuSO4·5H2O 70g/L, H2SO4140g/L, Na3PO4·12MO30.6g/L, temperature 25 DEG C, electric current density 24A/dm2,4s；
4) one-level solidification and two grades of solidifications: step 3) processed after Copper Foil entrance following process conditions under carry out one-level solidification: CuSO4·5H2O 220g/L, H2SO4100g/L, temperature 50 C, electric current density is 22A/dm2, 6s, the Copper Foil after one-level solidification enters two grades of solidifications, and the process conditions of two grades of solidifications are as follows: CuSO4·5H2O 150g/L, H2SO480g/L, temperature 35 DEG C, electric current density 25A/dm2,8s；
5) three grades of roughening: step 4) in Copper Foil after two grades of solidifications enter under following process conditions and carry out three grades of roughening: CuSO4·5H2O 40g/L, H2SO460g/L, Na3PO4·12MO30.1g/L, temperature 15 DEG C, electric current density 7.5A/dm2, 1.5s, the Copper Foil after having processed enters in rinsing bowl and washes；
6) nickel and zinc alloy: step 5) in has processed after Copper Foil enter contain potassium pyrophosphate, zinc sulfate, nickel sulfate coating bath in electroplate, design parameter is as follows: ZnSO4·7H2O 5.8g/L,NiSO4·6H2O 4.2g/L,K4P2O7·3H2O 200g/L, pH 10.5, temperature 35 DEG C, electric current density 2.5A/dm2,3.2s；Copper Foil after having processed enters in rinsing bowl and washes；
7) anti-oxidation: step 6) in has processed after Copper Foil enter contain zinc sulfate coating bath in electroplate, design parameter is as follows: Na2Cr2O7:8.0g/L,ZnSO4·7H2O:0.85g/L, pH 3.2, temperature 42 DEG C, electric current density 2.2A/dm2,3.2s；
8) silane coupler process: by γ-glycidyl ether oxygen propyl trimethoxy silicane aqueous solution that concentration is 0.15wt%, under room temperature state, be sprayed at copper foil surface, after in the baking oven of 320 DEG C toast 4.5s obtain product.
Embodiment 2:
The fine roughening treatment technique of a kind of electrolytic copper foil surface, comprises the technical steps that:
1) it is former paper tinsel by the HTE Copper Foil of 70 μm, uses the arc Ni-Ti anode of coated with nano iridium dioxide and diameter 2700mm drum type to rotate Ti cathode, in CuSO4·5H2O 300g/L,H2SO4 140g/L,Cl-30mg/L, temperature 57 DEG C, electric current density 69A/dm2, along with copper-stripping is obtained electrolytic copper foil by the lasting rotation of negative electrode；2) step 1) gained Copper Foil enter 10wt% dilute sulfuric acid in soak carry out pickling, time 5s；
3) one-level roughening and two grades of roughening: by step 2) processed after Copper Foil entrance following process conditions under carry out one-level roughening: CuSO4·5H2O 60g/L, H2SO4180g/L, Na3PO4·12MO31.0g/L, temperature 35 DEG C, electric current density 25A/dm2, 2s, the Copper Foil after one-level roughening enters two grades of roughening, and the process conditions of two grades of roughening are as follows: CuSO4·5H2O 100g/L, H2SO4220g/L, Na3PO4·12MO31.0g/L, temperature 25 DEG C, electric current density 20A/dm2,2s；
4) one-level solidification and two grades of solidifications: step 3) processed after Copper Foil entrance following process conditions under carry out one-level solidification: CuSO4·5H2O 150g/L, H2SO480g/L, temperature 35 DEG C, electric current density is 15A/dm2, 4s, the Copper Foil after one-level solidification enters two grades of solidifications, and the process conditions of two grades of solidifications are as follows: CuSO4·5H2O 200g/L, H2SO4120g/L, temperature 45 C, electric current density 25A/dm2,4.5s；
5) three grades of roughening: step 4) in Copper Foil after two grades of solidifications enter under following process conditions and carry out three grades of roughening: CuSO4·5H2O 60g/L, H2SO4180g/L, Na3PO4·12MO31.0g/L, temperature 35 DEG C, electric current density 15A/dm2, 3s, the Copper Foil after having processed enters in rinsing bowl and washes；
6) nickel and zinc alloy: step 5) in has processed after Copper Foil enter contain potassium pyrophosphate, zinc sulfate, nickel sulfate coating bath in electroplate, design parameter is as follows: ZnSO4·7H2O 10g/L,NiSO4·6H2O 20g/L,K4P2O7·3H2O 300g/L, pH 10, temperature 30 DEG C, electric current density 5.0A/dm2,3s；Copper Foil after having processed enters in rinsing bowl and washes；
7) anti-oxidation: step 6) in has processed after Copper Foil enter contain zinc sulfate coating bath in electroplate, design parameter is as follows: Na2Cr2O7:5g/L,ZnSO4·7H2O:0.1g/L, pH 2～4, temperature 40 DEG C, electric current density 2.0A/dm2,2.5s；
8) silane coupler process: by γ-glycidyl ether oxygen propyl trimethoxy silicane aqueous solution that concentration is 0.05wt%, under room temperature state, be sprayed at copper foil surface, after in the baking oven of 320 DEG C toast 4.5s obtain product.
Embodiment 3:
The fine roughening treatment technique of a kind of electrolytic copper foil surface, comprises the technical steps that:
1) it is former paper tinsel by the HTE Copper Foil of 100 μm, uses the arc Ni-Ti anode of coated with nano iridium dioxide and diameter 2700mm drum type to rotate Ti cathode, in CuSO4·5H2O 300g/L,H2SO4 140g/L,C l-30mg/L, temperature 57 DEG C, electric current density 69A/dm2, along with copper-stripping is obtained electrolytic copper foil by the lasting rotation of negative electrode；
2) step 1) gained Copper Foil enter 10wt% dilute sulfuric acid in soak carry out pickling, time 3s；
3) one-level roughening and two grades of roughening: by step 2) processed after Copper Foil entrance following process conditions under carry out one-level roughening: CuSO4·5H2O 100g/L, H2SO4220g/L, Na3PO4·12MO31.5g/L, temperature 30 DEG C, electric current density 15A/dm2, 3s, the Copper Foil after one-level roughening enters two grades of roughening, and the process conditions of two grades of roughening are as follows: CuSO4·5H2O 40g/L, H2SO460g/L, Na3PO4·12MO30.1g/L, temperature 20 DEG C, electric current density 20A/dm2,3s。
4) one-level solidification and two grades of solidifications: step 3) processed after Copper Foil entrance following process conditions under carry out one-level solidification: CuSO4·5H2O 150g/L, H2SO480g/L, temperature 45 C, electric current density is 15A/dm2, 4s, the Copper Foil after one-level solidification enters two grades of solidifications, and the process conditions of two grades of solidifications are as follows: CuSO4·5H2O 200g/L, H2SO4150g/L, temperature 45 C, electric current density 25A/dm2,6s；
5) three grades of roughening: step 4) in Copper Foil after two grades of solidifications enter under following process conditions and carry out three grades of roughening: CuSO4·5H2O 60g/L, H2SO4180g/L, Na3PO4·12MO31.5g/L, temperature 40 DEG C, electric current density 15A/dm2, 1～3s, the Copper Foil after having processed enters in rinsing bowl and washes；
6) nickel and zinc alloy: step 5) in has processed after Copper Foil enter contain potassium pyrophosphate, zinc sulfate, nickel sulfate coating bath in electroplate, design parameter is as follows: ZnSO4·7H2O 5g/L,NiSO4·6H2O 10g/L,K4P2O7·3H2O 200g/L, pH 8, temperature 30 DEG C, electric current density 2A/dm2,2s；Copper Foil after having processed enters in rinsing bowl and washes；
7) anti-oxidation: step 6) in has processed after Copper Foil enter contain zinc sulfate coating bath in electroplate, design parameter is as follows: Na2Cr2O7:6g/L,ZnSO4·7H2O:0.5g/L, pH 2～3, temperature 40 DEG C, electric current density 2.0A/dm2,4s；
8) silane coupler process: by γ-glycidyl ether oxygen propyl trimethoxy silicane aqueous solution that concentration is 0.25wt%, under room temperature state, be sprayed at copper foil surface, after in the baking oven of 320 DEG C toast 4.5s obtain product.
Embodiment 4:
The fine roughening treatment technique of a kind of electrolytic copper foil surface, comprises the technical steps that:
1) it is former paper tinsel by the HTE Copper Foil of 35 μm, uses the arc Ni-Ti anode of coated with nano iridium dioxide and diameter 2700mm drum type to rotate Ti cathode, in CuSO4·5H2O 300g/L,H2SO4140g/L,Cl-30mg/L, temperature 57 DEG C, electric current density 69A/dm2, along with copper-stripping is obtained electrolytic copper foil by the lasting rotation of negative electrode；
2) step 1) gained Copper Foil enter 15wt% dilute sulfuric acid in soak carry out pickling, time 5s；
3) one-level roughening and two grades of roughening: by step 2) processed after Copper Foil entrance following process conditions under carry out one-level roughening: CuSO4·5H2O 40g/L, H2SO460g/L, Na3PO4·12MO31.8g/L, temperature 15 DEG C, electric current density 15A/dm2, 4s, the Copper Foil after one-level roughening enters two grades of roughening, and the process conditions of two grades of roughening are as follows: CuSO4·5H2O 70g/L, H2SO4140g/L, Na3PO4·12MO31.8g/L, temperature 25 DEG C, electric current density 25A/dm2,2s；
4) one-level solidification and two grades of solidifications: step 3) processed after Copper Foil entrance following process conditions under carry out one-level solidification: CuSO4·5H2O 300g/L, H2SO4180g/L, temperature 35 DEG C, electric current density is 35A/dm2, 6s, the Copper Foil after one-level solidification enters two grades of solidifications, and the process conditions of two grades of solidifications are as follows: CuSO4·5H2O 200g/L, H2SO4150g/L, temperature 45 C, electric current density 25A/dm2, 4～10s；
5) three grades of roughening: step 4) in Copper Foil after two grades of solidifications enter under following process conditions and carry out three grades of roughening: CuSO4·5H2O 60g/L, H2SO4140g/L, Na3PO4·12MO32.0g/L, temperature 40 DEG C, electric current density 5A/dm2, 3s, the Copper Foil after having processed enters in rinsing bowl and washes；
6) nickel and zinc alloy: step 5) in has processed after Copper Foil enter contain potassium pyrophosphate, zinc sulfate, nickel sulfate coating bath in electroplate, design parameter is as follows: ZnSO4·7H2O 0.5g/L,NiSO4·6H2O 4g/L,K4P2O7·3H2O 150g/L, pH 10, temperature 30 DEG C, electric current density 1A/dm2,3s；Copper Foil after having processed enters in rinsing bowl and washes；
7) anti-oxidation: step 6) in has processed after Copper Foil enter contain zinc sulfate coating bath in electroplate, design parameter is as follows: Na2Cr2O7:10g/L,ZnSO4·7H2O:1.0g/L, pH 2～4, temperature 40 DEG C, electric current density 3.0A/dm2,3s；
8) silane coupler process: by γ-glycidyl ether oxygen propyl trimethoxy silicane aqueous solution that concentration is 0.5wt%, under room temperature state, be sprayed at copper foil surface, after in the baking oven of 320 DEG C toast 4.5s obtain product.
Embodiment 5:
The fine roughening treatment technique of a kind of electrolytic copper foil surface, comprises the technical steps that:
1) it is former paper tinsel by the HTE Copper Foil of 9 μm, uses the arc Ni-Ti anode of coated with nano iridium dioxide and diameter 2700mm drum type to rotate Ti cathode, in CuSO4·5H2O 300g/L,H2SO4 140g/L,Cl-30mg/L, temperature 57 DEG C, electric current density 69A/dm2, along with copper-stripping is obtained electrolytic copper foil by the lasting rotation of negative electrode；
2) step 1) gained Copper Foil enter 10～15wt% dilute sulfuric acid in soak carry out pickling, time 5～10s；
3) one-level roughening and two grades of roughening: by step 2) processed after Copper Foil entrance following process conditions under carry out one-level roughening: CuSO4·5H2O 60g/L, H2SO4180g/L, Na3PO4·12MO30.2g/L, temperature 35 DEG C, electric current density 25A/dm2, 2s, the Copper Foil after one-level roughening enters two grades of roughening, and the process conditions of two grades of roughening are as follows: CuSO4·5H2O 100g/L, H2SO4220g/L, Na3PO4·12MO30.2g/L, temperature 25 DEG C, electric current density 20A/dm2,2s；
4) one-level solidification and two grades of solidifications: step 3) processed after Copper Foil entrance following process conditions under carry out one-level solidification: CuSO4·5H2O 150g/L, H2SO480g/L, temperature 35 DEG C, electric current density is 15A/dm2, 4s, the Copper Foil after one-level solidification enters two grades of solidifications, and the process conditions of two grades of solidifications are as follows: CuSO4·5H2O 200g/L, H2SO4120g/L, temperature 45 C, electric current density 25A/dm2,4.5s；
5) three grades of roughening: step 4) in Copper Foil after two grades of solidifications enter under following process conditions and carry out three grades of roughening: CuSO4·5H2O 60g/L, H2SO4180g/L, Na3PO4·12MO30.2g/L, temperature 35 DEG C, electric current density 15A/dm2, 2s, the Copper Foil after having processed enters in rinsing bowl and washes；
6) nickel and zinc alloy: step 5) in has processed after Copper Foil enter contain potassium pyrophosphate, zinc sulfate, nickel sulfate coating bath in electroplate, design parameter is as follows: ZnSO4·7H2O 10g/L,NiSO4·6H2O 20g/L,K4P2O7·3H2O 300g/L, pH 10, temperature 30 DEG C, electric current density 5.0A/dm2,3s；Copper Foil after having processed enters in rinsing bowl and washes；
Use the following comparative example of roughening treatment process implementing of CN 103124810A2013.05.29 (WO2012/039285JP2012.03.29) patent disclosure of JX Shi Nippon Mining and Metals Co., Ltd of Japan:
Comparative example 1:
(1) roughening:
Cu2+: 15g/L (adds with the form of copper sulphate pentahydrate)
H2SO4: 100g/L
W (tungsten): 3mg/L (adding with the form of sodium tungstate)
As (arsenic): 1000mg/L is (with H3AsO3Form add)
Sodium lauryl sulphate: 10mg/L
Temperature: 40 DEG C
Electrodeposition condition: electric current density 50A/dm2,4s.
(2) solidification
Cu2+: 50g/L (adds with the form of copper sulphate pentahydrate)
H2SO4: 100g/L
Temperature: 40 DEG C
Electrodeposition condition: electric current density 20A/dm2,10s.
According still further to admiro same as in Example 1, anti-oxidation process, and the post-drying of silane coating coupling agent.
Comparative example 2
(1) roughening
Cu2+: 14g/L (adds with the form of copper sulphate pentahydrate)
H2SO4: 100g/L
Temperature: 25 DEG C
Electrodeposition condition: electric current density 30A/dm2,5s.
(2) solidification
Cu2+: 65g/L (adds with the form of copper sulphate pentahydrate)
H2SO4: 90g/L
Temperature: 45 DEG C
Electrodeposition condition: electric current density 20A/dm2,10s.
According still further to admiro same as in Example 1, anti-oxidation process, and the post-drying of silane coating coupling agent.
Process the performance of Copper Foil for more clearly describing present invention process, the method for testing relating to performance indications in the present invention be described below:
Roughness Rz: use the probe-type surface roughness method of testing that JISB0651-2001 specifies, tests by Marl, Germany M2 type surface roughness.
Peel strength: by 4 grand core Electron Ring epoxy resins semi-solid preparation material (GA-170B-LL, Tg175), uses vacuum press to be hot pressed into copper coated foil plate, is etched into 1mm lines on etching machine, and the method specified according to IPC-TM-650 is tested.
Resistance to hydrochloric acid deterioration rate: 1mm circuit sample etching obtained, in the hydrochloric acid solution of mass percent concentration 18%, after soaking 30 minutes under room temperature condition, tests peel strength value.Peel strength decay percent after soak with hydrochloric acid, is resistance to hydrochloric acid deterioration rate.
Lateral erosion: through the circuit of soak with hydrochloric acid, after testing resistance to hydrochloric acid deterioration rate, the width of measurement circuitry edge reddened area under super depth-of-field microscope (Japan, KEYENCE, VHX-1000), 0-0.1mm is without lateral erosion, more than 0.1mm then for there being lateral erosion.
Bright finish microetch: Copper Foil is toasted 30 minutes at 200 DEG C, in 10Wt%H2SO4,5%H2O2, temperature 35 DEG C, react 30 seconds, clean up and dry, then the surface that detects by an unaided eye is abnormal with or without striped, point etc..
The molybdenum content of copper foil surface and roughening, solidification deposition: use plasma emission spectrometer (ICP-AES, USA, Thermo Electron Corporation) test.
Copper powder: Copper Foil (20cm*20cm) is placed on horizontal stand, take quality be 200g, the rustless steel cylinder of diameter 30mm, alternating floor neutrality Medium speed filter paper is also uprightly put on Copper Foil, horizontal direction applies external force to rustless steel cylinder and moves it 120mm, takes off filter paper (500 times) on microscope and observes with or without copper powder.
Moisture absorption processes deterioration rate: 1mm circuit etching obtained, and boils 120 minutes in distilled water, after cooling down, drying up, and test peel strength percentage of decay after water boil.
Heat treated deterioration rate: 1mm circuit etching obtained, toasts 48 hours at 180 DEG C, cooling, the peel strength percentage of decay after test heating.
The Copper Foil of embodiment of the present invention 1-5 and comparative example 1-2 gained is carried out performance test, and result is as shown in table 1, table 2:
The performance test data of Copper Foil after table 1 surface treated
The performance test data of Copper Foil after table 2 surface treated
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all within the spirit and principles in the present invention, any modification, equivalent substitution and improvement etc. made, should be included within the scope of the present invention.
Claims (10)
1. a fine roughening treatment technique for electrolytic copper foil surface, including following technological process: one-level
It is roughened-two grades of roughening-one-level and solidifies-three grades of roughening-zinc-nickel alloys of-two grades of solidifications-anti-oxidation-silane occasionally
Connection agent processes-is dried, it is characterised in that the roughening of described one-level, two grades of roughening and the technique of three grades of roughening
Condition is: CuSO4·5H2O 40～100g/L, H2SO460～220g/L, Na3PO4·12MO30.1～
2.0g/L, temperature 15～40 DEG C.
The fine roughening treatment technique of electrolytic copper foil surface the most according to claim 1, its feature
Being, the electric current density of described one-level roughening is 15～25A/dm2, 2～4s, the electric current of described two grades of roughening
Density is 20～25A/dm2, 2～4s, the electric current density of described three grades of roughening is 5～15A/dm2, 1～3s.
The fine roughening treatment technique of electrolytic copper foil surface the most according to claim 1 and 2, its
Being characterised by, the process conditions of the roughening of described one-level, two grades of roughening and three grades of roughening are: CuSO4·5H2O
45～80g/L, H2SO480～200g/L, Na3PO4·12MO30.2～1.8g/L, temperature 20～38 DEG C.
The fine roughening treatment technique of electrolytic copper foil surface the most according to claim 3, its feature
Being, the process conditions of the roughening of described one-level, two grades of roughening and three grades of roughening are: CuSO4·5H2O 50～
60g/L, H2SO4140～180g/L, Na3PO4·12MO30.4～1.5g/L, temperature 25～35 DEG C.
The fine roughening treatment technique of electrolytic copper foil surface the most according to claim 1 and 2, its
It is characterised by, also includes acid pickling step before the roughening of described one-level, after described three grades of roughening and anti-oxidation step
Also include water-washing step.
The fine roughening treatment technique of electrolytic copper foil surface the most according to claim 1 and 2, its
Being characterised by, described one-level solidification solidifies concrete process conditions with two grades and is: CuSO4·5H2O
150～300g/L, H2SO480～180g/L, temperature 35～55 DEG C, electric current density be 15～
35A/dm2, 4～10s.
The fine roughening treatment technique of electrolytic copper foil surface the most according to claim 1 and 2, its
Being characterised by, the concrete technology condition of described zinc-nickel alloy is: ZnSO4·7H2O 0.5～
10g/L,NiSO4·6H2O 4～20g/L, K4P2O7·3H2O 150～300g/L, pH 8～11, temperature 30～
50 DEG C, electric current density 1～5A/dm2, 2～6s.
The fine roughening treatment technique of electrolytic copper foil surface the most according to claim 1 and 2, its
Being characterised by, the process conditions that described anti-oxidation step is concrete are: Na2Cr2O7: 5～10g/L, ZnSO4·
7H2O:0.1～1.0g/L, pH 2～4, temperature 30～50 DEG C, electric current density 0.5～3.0A/dm2, 1～4s.
The fine roughening treatment technique of electrolytic copper foil surface the most according to claim 1 and 2, its
Being characterised by, it is by γ-shrink that concentration is 0.05～0.5wt% that described silane coupler processes step
Glycerin ether oxygen propyl trimethoxy silicane aqueous solution, is sprayed at copper foil surface under room temperature state, after
The baking oven of 200～400 DEG C toasts 4～8s.
10. at the fine roughening according to the electrolytic copper foil surface according to any one of claim 1,2,4
Science and engineering skill, it is characterised in that the HTE Copper Foil that described electrolytic copper foil uses thickness to be 9～140 μm is former
Paper tinsel, its working condition is as follows: use the arc Ni-Ti anode of coated with nano iridium dioxide and drum type to rotate titanium the moon
Pole, in CuSO4·5H2O 300g/L,H2SO4140g/L,Cl-30mg/L, temperature 57 DEG C, electric current density
69A/dm2, along with copper-stripping is obtained electrolytic copper foil by the lasting rotation of negative electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610421834.9A CN106011965B (en) | 2016-06-13 | 2016-06-13 | A kind of fine roughening treatment technique of electrolytic copper foil surface |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610421834.9A CN106011965B (en) | 2016-06-13 | 2016-06-13 | A kind of fine roughening treatment technique of electrolytic copper foil surface |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106011965A true CN106011965A (en) | 2016-10-12 |
| CN106011965B CN106011965B (en) | 2018-08-14 |
Family
ID=57088579
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610421834.9A Active CN106011965B (en) | 2016-06-13 | 2016-06-13 | A kind of fine roughening treatment technique of electrolytic copper foil surface |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106011965B (en) |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106757245A (en) * | 2016-11-16 | 2017-05-31 | 山东金宝电子股份有限公司 | A kind of process of surface treatment of melanism Copper Foil |
| CN108505081A (en) * | 2017-02-24 | 2018-09-07 | 南亚塑胶工业股份有限公司 | Method for manufacturing electrolytic copper foil with approximate villiform copper nodules and circuit board assembly |
| CN108505075A (en) * | 2017-02-24 | 2018-09-07 | 南亚塑胶工业股份有限公司 | Method for manufacturing electrolytic copper foil with approximately rugby-shaped copper nodules and circuit board assembly |
| CN108677225A (en) * | 2018-08-14 | 2018-10-19 | 山东金宝电子股份有限公司 | A kind of processing method reducing electrolytic copper foil warpage |
| CN109137013A (en) * | 2018-07-13 | 2019-01-04 | 铜陵市华创新材料有限公司 | A kind of electrolytic copper foil surface electro-deposition ZN-NI-P-LA alloying technology |
| CN109881221A (en) * | 2019-03-04 | 2019-06-14 | 深圳市汇美新科技有限公司 | A kind of ultrathin film electroplating technology of high fracture elongation |
| CN110205656A (en) * | 2019-06-06 | 2019-09-06 | 贵州中鼎高精铜箔制造有限公司 | A kind of fine roughening treatment technique of electrolytic copper foil surface |
| CN110396684A (en) * | 2018-10-31 | 2019-11-01 | 惠州联合铜箔电子材料有限公司 | A kind of 420-500 microns of super thick electrolytic copper foil technique |
| CN110777379A (en) * | 2020-01-03 | 2020-02-11 | 苏师大半导体材料与设备研究院(邳州)有限公司 | Coarsening treatment device for copper foil of circuit board |
| CN110952117A (en) * | 2018-09-27 | 2020-04-03 | 金居开发股份有限公司 | Micro-rough electrolytic copper foil and copper foil substrate |
| CN112011810A (en) * | 2020-08-26 | 2020-12-01 | 九江德福科技股份有限公司 | Production method of high-heat-resistance electrolytic copper foil |
| US11053602B2 (en) | 2018-09-17 | 2021-07-06 | Co-Tech Development Corp. | Micro-roughened electrodeposited copper foil and copper foil substrate |
| CN113176188A (en) * | 2021-04-08 | 2021-07-27 | 九江德福科技股份有限公司 | Method for measuring specific surface area of electrolytic copper foil |
| CN113594048A (en) * | 2021-06-25 | 2021-11-02 | 广东华智芯电子科技有限公司 | Copper lead frame and surface treatment method thereof, package and preparation method thereof |
| CN113718307A (en) * | 2021-06-16 | 2021-11-30 | 惠州合正电子科技有限公司 | Surface treatment process for high-peeling-resistance copper foil |
| CN114990654A (en) * | 2022-06-02 | 2022-09-02 | 山东金宝电子股份有限公司 | Electrolytic copper foil surface treatment process, HVLP copper foil product and application thereof |
| CN115044947A (en) * | 2022-06-17 | 2022-09-13 | 山东金宝电子股份有限公司 | Surface treatment method for improving adhesive force of copper foil and resin |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101935856A (en) * | 2010-08-03 | 2011-01-05 | 山东金宝电子股份有限公司 | Back face treatment process of electrolytic copper foil |
| CN102586831A (en) * | 2012-03-12 | 2012-07-18 | 山东金宝电子股份有限公司 | Surface treatment process for reducing roughness of electrolytic copper foil |
| CN103052278A (en) * | 2012-12-27 | 2013-04-17 | 建滔（连州）铜箔有限公司 | Additive for roughening surface of copper foil |
| CN103173812A (en) * | 2013-03-21 | 2013-06-26 | 山东金宝电子股份有限公司 | Mixed additive for removing internal stress of electrolytic copper foil and method for producing low-stress copper foil |
| CN104928740A (en) * | 2015-07-07 | 2015-09-23 | 安徽铜冠铜箔有限公司 | Surface treatment method for reducing copper powder on rough surface of copper foil |
| CN104962965A (en) * | 2015-05-29 | 2015-10-07 | 灵宝金源朝辉铜业有限公司 | Environmental protection ashing treatment process of calendaring copper foil |
| CN105002496A (en) * | 2015-07-28 | 2015-10-28 | 灵宝华鑫铜箔有限责任公司 | Black surface treatment method for electrolytic copper foil |
-
2016
- 2016-06-13 CN CN201610421834.9A patent/CN106011965B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101935856A (en) * | 2010-08-03 | 2011-01-05 | 山东金宝电子股份有限公司 | Back face treatment process of electrolytic copper foil |
| CN102586831A (en) * | 2012-03-12 | 2012-07-18 | 山东金宝电子股份有限公司 | Surface treatment process for reducing roughness of electrolytic copper foil |
| CN103052278A (en) * | 2012-12-27 | 2013-04-17 | 建滔（连州）铜箔有限公司 | Additive for roughening surface of copper foil |
| CN103173812A (en) * | 2013-03-21 | 2013-06-26 | 山东金宝电子股份有限公司 | Mixed additive for removing internal stress of electrolytic copper foil and method for producing low-stress copper foil |
| CN104962965A (en) * | 2015-05-29 | 2015-10-07 | 灵宝金源朝辉铜业有限公司 | Environmental protection ashing treatment process of calendaring copper foil |
| CN104928740A (en) * | 2015-07-07 | 2015-09-23 | 安徽铜冠铜箔有限公司 | Surface treatment method for reducing copper powder on rough surface of copper foil |
| CN105002496A (en) * | 2015-07-28 | 2015-10-28 | 灵宝华鑫铜箔有限责任公司 | Black surface treatment method for electrolytic copper foil |
Cited By (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106757245B (en) * | 2016-11-16 | 2019-05-21 | 山东金宝电子股份有限公司 | A kind of process of surface treatment of melanism copper foil |
| CN106757245A (en) * | 2016-11-16 | 2017-05-31 | 山东金宝电子股份有限公司 | A kind of process of surface treatment of melanism Copper Foil |
| CN108505081A (en) * | 2017-02-24 | 2018-09-07 | 南亚塑胶工业股份有限公司 | Method for manufacturing electrolytic copper foil with approximate villiform copper nodules and circuit board assembly |
| CN108505075A (en) * | 2017-02-24 | 2018-09-07 | 南亚塑胶工业股份有限公司 | Method for manufacturing electrolytic copper foil with approximately rugby-shaped copper nodules and circuit board assembly |
| CN109137013A (en) * | 2018-07-13 | 2019-01-04 | 铜陵市华创新材料有限公司 | A kind of electrolytic copper foil surface electro-deposition ZN-NI-P-LA alloying technology |
| CN108677225A (en) * | 2018-08-14 | 2018-10-19 | 山东金宝电子股份有限公司 | A kind of processing method reducing electrolytic copper foil warpage |
| US11053602B2 (en) | 2018-09-17 | 2021-07-06 | Co-Tech Development Corp. | Micro-roughened electrodeposited copper foil and copper foil substrate |
| CN110952117B (en) * | 2018-09-27 | 2021-03-12 | 金居开发股份有限公司 | Micro-rough electrolytic copper foil and copper foil substrate |
| CN110952117A (en) * | 2018-09-27 | 2020-04-03 | 金居开发股份有限公司 | Micro-rough electrolytic copper foil and copper foil substrate |
| CN110396684B (en) * | 2018-10-31 | 2020-08-28 | 惠州联合铜箔电子材料有限公司 | Process for 420-doped 500-micron ultra-thick electrolytic copper foil |
| CN110396684A (en) * | 2018-10-31 | 2019-11-01 | 惠州联合铜箔电子材料有限公司 | A kind of 420-500 microns of super thick electrolytic copper foil technique |
| CN109881221A (en) * | 2019-03-04 | 2019-06-14 | 深圳市汇美新科技有限公司 | A kind of ultrathin film electroplating technology of high fracture elongation |
| CN110205656A (en) * | 2019-06-06 | 2019-09-06 | 贵州中鼎高精铜箔制造有限公司 | A kind of fine roughening treatment technique of electrolytic copper foil surface |
| CN110777379A (en) * | 2020-01-03 | 2020-02-11 | 苏师大半导体材料与设备研究院(邳州)有限公司 | Coarsening treatment device for copper foil of circuit board |
| CN112011810A (en) * | 2020-08-26 | 2020-12-01 | 九江德福科技股份有限公司 | Production method of high-heat-resistance electrolytic copper foil |
| WO2022041533A1 (en) * | 2020-08-26 | 2022-03-03 | 九江德福科技股份有限公司 | Production method for high heat-resistant electrodeposited copper foil |
| CN113176188A (en) * | 2021-04-08 | 2021-07-27 | 九江德福科技股份有限公司 | Method for measuring specific surface area of electrolytic copper foil |
| CN113718307A (en) * | 2021-06-16 | 2021-11-30 | 惠州合正电子科技有限公司 | Surface treatment process for high-peeling-resistance copper foil |
| CN113718307B (en) * | 2021-06-16 | 2023-09-15 | 惠州合正电子科技有限公司 | Surface treatment process for high-peel-resistance copper foil |
| CN113594048A (en) * | 2021-06-25 | 2021-11-02 | 广东华智芯电子科技有限公司 | Copper lead frame and surface treatment method thereof, package and preparation method thereof |
| CN113594048B (en) * | 2021-06-25 | 2022-03-11 | 广东华智芯电子科技有限公司 | Copper lead frame and surface treatment method thereof, package and preparation method thereof |
| CN114990654A (en) * | 2022-06-02 | 2022-09-02 | 山东金宝电子股份有限公司 | Electrolytic copper foil surface treatment process, HVLP copper foil product and application thereof |
| CN114990654B (en) * | 2022-06-02 | 2024-04-26 | 山东金宝电子有限公司 | Electrolytic copper foil surface treatment process, HVLP copper foil product and application thereof |
| CN115044947A (en) * | 2022-06-17 | 2022-09-13 | 山东金宝电子股份有限公司 | Surface treatment method for improving adhesive force of copper foil and resin |
| CN115044947B (en) * | 2022-06-17 | 2023-09-29 | 山东金宝电子有限公司 | Surface treatment method for improving adhesion of copper foil and resin |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106011965B (en) | 2018-08-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106011965A (en) | Fine roughing treatment technology for surface of electrolytic copper foil | |
| CN102618902B (en) | Surface treatment process of copper foil for flexible copper-clad plate | |
| CN101935856B (en) | Back face treatment process of electrolytic copper foil | |
| CN102277605B (en) | Process for manufacturing smooth surface roughened electrolytic copper foil | |
| CN110438531B (en) | Preparation method and system of ultrathin copper foil applied to lithium battery | |
| CN100567572C (en) | The gray surface treatment process of electrolytic copper foil | |
| JP5885054B2 (en) | A treated copper foil for a copper clad laminate, a copper clad laminate obtained by bonding the treated copper foil to an insulating resin substrate, and a printed wiring board using the copper clad laminate. | |
| CN101935836B (en) | Surface treatment process of reddened copper foil for high-grade FR-4 copper-clad plate | |
| CN104962965B (en) | The environment-friendly type ashing handling process of rolled copper foil | |
| CN105408525A (en) | Treated surface copper foil, copper foil with carrier, substrate, resin substrate, printed circuit board, copper clad laminate, and printed circuit board manufacturing method | |
| CN102586831A (en) | Surface treatment process for reducing roughness of electrolytic copper foil | |
| CN105408524A (en) | Surface-treated copper foil, copper foil with carrier, substrate, resin substrate, printed circuit board, copper-clad laminate, and method for manufacturing printed circuit board | |
| CN112226790B (en) | Production method of ultrathin high-strength electronic copper foil | |
| CN105603480A (en) | Black surface treatment method for rolled copper foil | |
| CN104694939A (en) | Surface treatment technology for ultralow-surface-roughness copper foil | |
| CN106319585A (en) | Surface treatment method of high-precision blackened rolled copper foil | |
| CN103469267A (en) | Process method for carrying out surface treatment on electrolysis copper foil, and cooper foil treated by using the same | |
| JP7019876B1 (en) | Surface-treated copper foil for printed wiring boards, and copper-clad laminates and printed wiring boards for printed wiring boards using this | |
| CN105209252A (en) | Copper foil with attached carrier, copper-clad laminate using same, printed circuit board, electronic device, and method for manufacturing printed circuit board | |
| CN110344105A (en) | A kind of two-sided surface treatment method of rolled copper foil | |
| CN103334147A (en) | Method for preparing nickel-coated aluminum powder composite coating by utilizing pulse plating | |
| CN104780710A (en) | PCB (Printed circuit board) and manufacturing method thereof | |
| KR20230129209A (en) | Electrodeposited copper foil with its surfaceprepared, process for producing the same and usethereof | |
| CN105874891A (en) | Copper foil, and electrical component and battery including same | |
| JP2022120813A (en) | Ultrathin copper foil, and method of producing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: 265400 No.268, Guoda Road, Zhaoyuan City, Yantai City, Shandong Province Patentee after: Shandong Jinbao Electronics Co.,Ltd. Address before: No. 128, Wenquan Road, Zhaoyuan, Yantai, Shandong 265200 Patentee before: SHANDONG JINBAO ELECTRONICS Co.,Ltd. |