CN106011965B - A kind of fine roughening treatment technique of electrolytic copper foil surface - Google Patents

A kind of fine roughening treatment technique of electrolytic copper foil surface Download PDF

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CN106011965B
CN106011965B CN201610421834.9A CN201610421834A CN106011965B CN 106011965 B CN106011965 B CN 106011965B CN 201610421834 A CN201610421834 A CN 201610421834A CN 106011965 B CN106011965 B CN 106011965B
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copper foil
roughening
temperature
electrolytic copper
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CN106011965A (en
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杨祥魁
徐树民
王维河
徐策
王学江
薛伟
孙云飞
徐好强
宋吉昌
王其伶
宋淑平
谢峰
冯秋兴
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SHANDONG JINBAO ELECTRONICS CO Ltd
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SHANDONG JINBAO ELECTRONIC CO Ltd
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    • 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

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  • 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 present invention relates to a kind of fine roughening treatment techniques of electrolytic copper foil surface, including following technological process：Level-one is roughened the anti-oxidation silane coupling agent of two level roughening level-one solidification two level solidification three-level roughening zinc-nickel alloy and handles drying, the copper foil of present invention process production, with lower surface roughness, there is very high peel strength again simultaneously, especially on the plank of Tg170 or more, show excellent adhesion strength, be very suitable for low-loss, ultra-low loss high speed circuit board；The copper foil of present invention process production, the similar product that key technical index has reached the advanced copper foil producers such as Mitsui metal (MHT), Furukawa (MP), JX days stone days mine metal (JTC LC) is horizontal, similar import copper foil has been substituted, the high end plate materials such as domestic or American-European high multilayer, HDI, Halogen are applied to.

Description

A kind of fine roughening treatment technique of electrolytic copper foil surface
Technical field
The present invention relates to the roughening treatment works of a kind of process of surface treatment of copper foil more particularly to a kind of electrolytic copper foil surface Skill belongs 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 producer, but also have larger gap compared with developed countries in production technology, especially high-end copper foil product (is used for High multilayer, high density interconnection etc.) it is always specially enjoying for Japanese and American-European enterprise.High multilayer (generally higher than 26 layers), high density are mutual Join (HDI) printed circuit electronics copper foil, in addition to require excellent internal performance (tensile strength under room temperature, high temperature with Ductility, anti-oxidant, corrosion-resistant, resistance etc.) and it is environmental-friendly except, limited by its manufacturing process and use environment, also wanted Ask copper foil that there is lower surface roughness, the dielectric loss of circuit can reduce when being used for high-speed transfer in this way.On the other hand, have There is the copper foil of relatively low rugosity to be used for printed circuit, is conducive to make finer circuit.But for copper foil producer, The peel strength (i.e. with the adhesion strength of resin) for improving copper foil while the roughness for reducing copper foil again, especially exists On the low-loss plank of Tg170~Tg230 (glass transition temperature), technical difficulty is quite big.This is also exactly domestic copper foil factory The product of family, it is difficult to one of the main reason for meeting American-European high-end printed circuit.The present inventor, according to American-European high-end print The technical characterstic of circuit copper foil processed, keep the room temperature of general high temperature high ductibility copper foil (HTE), the tensile strength of high temperature and Under the premise of the technologies such as ductility require, the low roughness copper foil of special surface treatment process has been invented, has been suitable for Tg170 or more The high end plate material such as low-loss, ultra-low loss, high multilayer, HDI, Halogen.
Invention content
Technical problem solved by the invention is to fill up the technological gap of existing domestic copper foil industry, provides a kind of electricity Solve the fine roughening treatment technique of copper foil surface.
The technical solution that the present invention solves above-mentioned technical problem is as follows：
A kind of fine roughening treatment technique of electrolytic copper foil surface, including following technological process：Level-one roughening-two level is thick Change-level-one solidification-two level solidification-three-level roughening-zinc-nickel alloy-is anti-oxidation-silane coupling agent processing-drying, feature exists In the process conditions of the level-one roughening, two level roughening and three-level roughening are：CuSO4·5H2O 40~100g/L, H2SO460 ~220g/L, Mo12Na3O400.1~2.0g/L of P, 15~40 DEG C of temperature.
Based on the above technical solution, the utility model can also do following improvement.
Further, the level-one roughening, two level roughening and three-level roughening are led to by cathode copper in 40~80 DEG C of sulfuric acid Enter air stirring dissolving, forms the mixed liquor of copper sulphate and sulfuric acid, the current density of level-one roughening is 15~25A/dm2, 2~ The current density of 4s, the two level roughening are 20~25A/dm2, the current density of 2~4s, the three-level roughening are 5~15A/ dm2, 1~3s.
Further, the process conditions of the level-one roughening, two level roughening and three-level roughening are：CuSO4·5H2O 45~ 80g/L, H2SO480~200g/L, Mo12Na3O400.2~1.8g/L of P, 20~38 DEG C of temperature.
Further, the process conditions of the level-one roughening, two level roughening and three-level roughening are：CuSO4·5H2O 50~ 60g/L, H2SO4140~180g/L, Mo12Na3O400.4~1.5g/L of P, 25~35 DEG C of temperature.
The CAS numbers for the sodium phosphomolybdate that the present invention uses are 1313-30-0, and structural formula is as follows：
Level-one is roughened and the effect of two level roughening is to form dendritic small crystallization on the surface of copper foil, increase copper foil Specific surface area, in order to improve the adhesion strength of copper foil and resin material.The roughening treatment step of the present invention, uses phosphorus molybdenum Sour sodium does additive, changes the electro-deposition structure (as shown in Figure 3) of copper foil surface.It is clear that the present invention copper foil with it is general The copper foil (Fig. 4) that logical roughening treatment obtains is compared, and there is more excellent nodular texture, excellent place to be that common copper foil is thick The nodular texture for changing layer, focuses primarily upon the top on " mountain peak ", and the roughened layer for the copper foil that present invention process is handled, " mountain Peak " and " mountain valley " all have uniform nodular texture (as shown in Figure 5).Three-level is roughened, and is in the nodular texture surface of formation, shape At more small dotted crystallization (SEM, 20,000 times, 20-150 nanometers), specific surface area is further increased, with raising and resin material Adhesion strength.
Further, further include acid pickling step before the level-one roughening, further include after the three-level roughening and anti-oxidation step Water-washing step.
Further, the described level-one solidification and two level solidification be by cathode copper in 40~90 DEG C of sulfuric acid, be passed through air Stirring and dissolving forms the mixed liquor of copper sulphate and sulfuric acid, is pumped into roughening slot and is electroplated, and level-one solidification and two level solidification are specific Process conditions are：CuSO4·5H2O 150~300g/L, H2SO480~180g/L, 35~55 DEG C of temperature, current density be 15~ 35A/dm2, 4~10s.
Further, the zinc-nickel alloy refers to that potassium pyrophosphate, zinc sulfate, nickel sulfate are used water dissolution respectively, not Zinc sulfate, nickel sulfate solution are added in potassium pyrophosphate solution under disconnected stirring, is pumped into coating bath and is electroplated after stirring evenly, Concrete technology condition is：ZnSO4·7H2O 0.5~10g/L, NiSO4·6H2O 4~20g/L, K4P2O7·3H2O 150~ 300g/L, pH 8~11,30~50 DEG C of temperature, 1~5A/dm of current density2, 2~6s.
Further, the anti-oxidation step refers to that H is used in sodium dichromate water dissolution2SO4After adjusting pH value thereto Zinc sulfate dissolving is added, is pumped into coating bath after stirring evenly and is electroplated, specific process conditions are：Na2Cr2O7:5~10g/L, ZnSO4·7H2O:0.1~1.0g/L, pH 2~4,30~50 DEG C of temperature, 0.5~3.0A/dm of current density2, 1~4s.
Further, the silane coupling agent processing step is by γ-glycidol ether of a concentration of 0.05~0.5wt% Oxygen propyl trimethoxy silicane aqueous solution is sprayed at copper foil surface under room temperature state, after dried in 200~400 DEG C of baking oven Roasting 4~8s, the γ-glycidyl ether oxygen propyl trimethoxy silicane, CAS numbers are 2530-83-8, and molecular formula is C9H20O5Si。
Further, it for 9~140 μm of HTE copper foils is former foil that the electrolytic copper foil, which uses thickness, and working condition is as follows： Ti cathode is rotated using the arc Ni―Ti anode and drum type of coated with nano iridium dioxide, in CuSO4·5H2O 300g/L, H2SO4140g/L, Cl-30mg/L, 57 DEG C of temperature, current density 69A/dm2, copper-stripping is obtained with the lasting rotation of cathode Electrolytic copper foil.
The principle of present invention process roughening treatment process is as follows：
Sodium phosphomolybdate is added in coarsening process as additive, changes the structure of electro-deposition, electrochemical mechanism It is that sodium phosphomolybdate forms heteropolyacid salt with copper ion complexing in an acidic solution, electricity is precipitated in the electrochemistry for changing copper ion The copper molybdenum alloy of position, formation receives Inhibition backward " mountain valley " movement in " mountain peak " deposition.By controlling additive phosphorus molybdenum The concentration and electrodeposition condition of sour sodium have finally obtained highly uniform nodular surface structure as shown in Figure 3.This uniform warty The copper foil of structure is carried in the plank of Tg175 by peel strength from 1.15N/mm of common copper foil or so (referring to comparative example 2) Height has arrived 1.6N/mm or more (reference implementation example 1-5), has reached the level of copper foil producer leading in the world similar product.
The beneficial effects of the invention are as follows：
1) copper foil of present invention process production has lower surface roughness, while having very high antistripping strong again Degree, especially on the plank of Tg170 or more, shows excellent adhesion strength, is very suitable for low-loss, ultra-low loss High speed circuit board；
2) copper foil of present invention process production, has excellent anti-room temperature, high temperature oxidation stability.It is wet in temperature less than 40 DEG C Degree is less than under conditions of 60%, and storage does not aoxidize for 1 year；Air stirring is passed through in 210 DEG C of high temperature not aoxidize within 1 hour；In temperature Degree is 85 DEG C, and humidity does not aoxidize for 48 hours under conditions of being 90%.
3) copper foil of present invention process production, has excellent plating resist layer diffusion, room temperature (25 DEG C, 3 months), high temperature Do not occur color change caused by apparent coating diffusion under (210 DEG C, 1 hour)；With excellent chemical resistance and erosion Quarter property, is suitable for very fine circuit；With very high peel strength and high temperature resistance conversion performance, it is adapted to the Pb-free coating of PCB； With excellent smooth surface microetch characteristic, it is adapted to the thin base production requirement that high multilayer printed circuit needs.
4) present invention realizes the ring of production process and product without using the compound of the elements such as arsenic, antimony, lead, mercury, cadmium It protects.
The copper foil of present invention process production, key technical index have reached Mitsui metal (MHT), Furukawa (MP), the similar product of the advanced copper foil producer such as JX days stone days mine metal (JTC-LC) is horizontal.Similar import copper foil has been substituted, Applied to high end plate materials such as domestic or American-European high multilayer, HDI, Halogens.
Description of the drawings
Fig. 1 is the process flow chart of the present invention；
The SEM pictures for the former foil that Fig. 2 is 35 μm；
Fig. 3 is the SEM pictures through present invention process treated 35 μm of electrolytic copper foils；
Fig. 4 is the SEM pictures for 35 μm of copper foils that comparative example 2 obtains；
Fig. 5 is the copper foil section schematic diagram that present invention process is handled with common process.
Specific implementation mode
Principles and features of the present invention are described below in conjunction with example, the given examples are served only to explain the present invention, and It is non-to be used to limit the scope of the present invention.
Embodiment 1：
A kind of fine roughening treatment technique of electrolytic copper foil surface, comprises the technical steps that：
1) it is former foil by 35 μm of HTE copper foils, using the arc Ni―Ti anode and diameter 2700mm of coated with nano iridium dioxide Drum type rotates Ti cathode, in CuSO4·5H2O 300g/L, H2SO4140g/L, Cl-30mg/L, 57 DEG C of temperature, current density 69A/ dm2Under the conditions of, copper-stripping is obtained into electrolytic copper foil with the lasting rotation of cathode；
2) copper foil obtained by step 1), which enters in the dilute sulfuric acid of 10wt%, carries out pickling, time 3s；
3) level-one roughening and two level roughening：Copper foil after the completion of step 2) processing is entered under following process conditions and carries out one Grade roughening：CuSO4·5H2O 60g/L, H2SO4180g/L, Mo12Na3O40P 0.5g/L, 28 DEG C of temperature, current density 18A/ dm2, 2.6s, level-one roughening after copper foil enter two level roughening, two level roughening process conditions it is as follows：CuSO4·5H2O 70g/ L, H2SO4140g/L, Mo12Na3O40P0.6g/L, 25 DEG C of temperature, current density 24A/dm2, 4s；
4) level-one solidification and two level solidification：Copper foil after the completion of step 3) processing, which enters under following process conditions, carries out level-one Solidification：CuSO4·5H2O 220g/L, H2SO4100g/L, temperature 50 C, current density 22A/dm2, 6s, after level-one solidification Copper foil enters two level solidification, and the cured process conditions of two level are as follows：CuSO4·5H2O 150g/L, H2SO480g/L, temperature 35 DEG C, current density 25A/dm2, 8s；
5) three-level is roughened：Copper foil in step 4) after two level solidification, which enters, carries out three-level roughening under following process conditions： CuSO4·5H2O 40g/L, H2SO460g/L, Mo12Na3O40P 0.1g/L, 15 DEG C of temperature, current density 7.5A/dm2, 1.5s, Copper foil after the completion of processing, which enters in rinsing bowl, to be washed；
6) nickel plating kirsite：Copper foil in step 5) after the completion of processing enters the plating containing potassium pyrophosphate, zinc sulfate, nickel sulfate It is electroplated in slot, design parameter is as follows：ZnSO4·7H2O 5.8g/L, NiSO4·6H2O 4.2g/L, K4P2O7·3H2O 200g/L, pH 10.5,35 DEG C of temperature, current density 2.5A/dm2, 3.2s；Copper foil after the completion of processing enters water in rinsing bowl It washes；
7) anti-oxidation：Copper foil in step 6) after the completion of processing, which enters in the coating bath containing zinc sulfate, to be electroplated, specifically Parameter is as follows：Na2Cr2O7:8.0g/L, ZnSO4·7H2O:0.85g/L, pH 3.2,42 DEG C of temperature, current density 2.2A/dm2, 3.2s；
8) silane coupling agent is handled：By the γ of a concentration of 0.15wt%-glycidyl ether oxygen propyl trimethoxy silicane water Solution is sprayed at copper foil surface under room temperature state, after in 320 DEG C of baking oven toast 4.5s obtain product.
Embodiment 2：
A kind of fine roughening treatment technique of electrolytic copper foil surface, comprises the technical steps that：
1) it is former foil by 70 μm of HTE copper foils, using the arc Ni―Ti anode and diameter 2700mm of coated with nano iridium dioxide Drum type rotates Ti cathode, in CuSO4·5H2O 300g/L, H2SO4140g/L, Cl-30mg/L, 57 DEG C of temperature, current density 69A/ dm2, copper-stripping is obtained into electrolytic copper foil with the lasting rotation of cathode；
2) copper foil obtained by step 1), which enters in the dilute sulfuric acid of 10wt% to impregnate, carries out pickling, time 5s；
3) level-one roughening and two level roughening：Copper foil after the completion of step 2) processing is entered under following process conditions and carries out one Grade roughening：CuSO4·5H2O 60g/L, H2SO4180g/L, Mo12Na3O40P 1.0g/L, 35 DEG C of temperature, current density 25A/ dm2, 2s, level-one roughening after copper foil enter two level roughening, two level roughening process conditions it is as follows：CuSO4·5H2O 100g/L, H2SO4220g/L, Mo12Na3O40P1.0g/L, 25 DEG C of temperature, current density 20A/dm2, 2s；
4) level-one solidification and two level solidification：Copper foil after the completion of step 3) processing, which enters under following process conditions, carries out level-one Solidification：CuSO4·5H2O 150g/L, H2SO480g/L, 35 DEG C of temperature, current density 15A/dm2, 4s, the copper after level-one solidification Foil enters two level solidification, and the cured process conditions of two level are as follows：CuSO4·5H2O 200g/L, H2SO4120g/L, temperature 45 C, Current density 25A/dm2, 4.5s；
5) three-level is roughened：Copper foil in step 4) after two level solidification, which enters, carries out three-level roughening under following process conditions： CuSO4·5H2O 60g/L, H2SO4180g/L, Mo12Na3O40P 1.0g/L, 35 DEG C of temperature, current density 15A/dm2, 3s, place Copper foil after the completion of reason, which enters in rinsing bowl, to be washed；
6) nickel plating kirsite：Copper foil in step 5) after the completion of processing enters the plating containing potassium pyrophosphate, zinc sulfate, nickel sulfate It is electroplated in slot, design parameter is as follows：ZnSO4·7H2O 10g/L, NiSO4·6H2O 20g/L, K4P2O7·3H2O 300g/ L, pH 10,30 DEG C of temperature, current density 5.0A/dm2, 3s；Copper foil after the completion of processing, which enters in rinsing bowl, to be washed；
7) anti-oxidation：Copper foil in step 6) after the completion of processing, which enters in the coating bath containing zinc sulfate, to be electroplated, specifically Parameter is as follows：Na2Cr2O7:5g/L, ZnSO4·7H2O:0.1g/L, pH 2~4,40 DEG C of temperature, current density 2.0A/dm2, 2.5s；
8) silane coupling agent is handled：By the γ of a concentration of 0.05wt%-glycidyl ether oxygen propyl trimethoxy silicane water Solution is sprayed at copper foil surface under room temperature state, after in 320 DEG C of baking oven toast 4.5s obtain product.
Embodiment 3：
A kind of fine roughening treatment technique of electrolytic copper foil surface, comprises the technical steps that：
1) it is former foil by 100 μm of HTE copper foils, using the arc Ni―Ti anode and diameter 2700mm of coated with nano iridium dioxide Drum type rotates Ti cathode, in CuSO4·5H2O 300g/L, H2SO4140g/L, Cl-30mg/L, 57 DEG C of temperature, current density 69A/ dm2, copper-stripping is obtained into electrolytic copper foil with the lasting rotation of cathode；
2) copper foil obtained by step 1), which enters in the dilute sulfuric acid of 10wt% to impregnate, carries out pickling, time 3s；
3) level-one roughening and two level roughening：Copper foil after the completion of step 2) processing is entered under following process conditions and carries out one Grade roughening：CuSO4·5H2O 100g/L, H2SO4220g/L, Mo12Na3O40P 1.5g/L, 30 DEG C of temperature, current density 15A/ dm2, 3s, level-one roughening after copper foil enter two level roughening, two level roughening process conditions it is as follows：CuSO4·5H2O 40g/L, H2SO460g/L, Mo12Na3O40P0.1g/L, 20 DEG C of temperature, current density 20A/dm2, 3s.
4) level-one solidification and two level solidification：Copper foil after the completion of step 3) processing, which enters under following process conditions, carries out level-one Solidification：CuSO4·5H2O 150g/L, H2SO480g/L, temperature 45 C, current density 15A/dm2, 4s, the copper after level-one solidification Foil enters two level solidification, and the cured process conditions of two level are as follows：CuSO4·5H2O 200g/L, H2SO4150g/L, temperature 45 C, Current density 25A/dm2, 6s；
5) three-level is roughened：Copper foil in step 4) after two level solidification, which enters, carries out three-level roughening under following process conditions： CuSO4·5H2O 60g/L, H2SO4180g/L, Mo12Na3O40P 1.5g/L, 40 DEG C of temperature, current density 15A/dm2, 1~3s, Copper foil after the completion of processing, which enters in rinsing bowl, to be washed；
6) nickel plating kirsite：Copper foil in step 5) after the completion of processing enters the plating containing potassium pyrophosphate, zinc sulfate, nickel sulfate It is electroplated in slot, design parameter is as follows：ZnSO4·7H2O 5g/L, NiSO4·6H2O 10g/L, K4P2O7·3H2O 200g/ L, pH 8,30 DEG C of temperature, current density 2A/dm2, 2s；Copper foil after the completion of processing, which enters in rinsing bowl, to be washed；
7) anti-oxidation：Copper foil in step 6) after the completion of processing, which enters in the coating bath containing zinc sulfate, to be electroplated, specifically Parameter is as follows：Na2Cr2O7:6g/L, ZnSO4·7H2O:0.5g/L, pH 2~3,40 DEG C of temperature, current density 2.0A/dm2, 4s；
8) silane coupling agent is handled：By the γ of a concentration of 0.25wt%-glycidyl ether oxygen propyl trimethoxy silicane water Solution is sprayed at copper foil surface under room temperature state, after in 320 DEG C of baking oven toast 4.5s obtain product.
Embodiment 4：
A kind of fine roughening treatment technique of electrolytic copper foil surface, comprises the technical steps that：
1) it is former foil by 35 μm of HTE copper foils, using the arc Ni―Ti anode and diameter 2700mm of coated with nano iridium dioxide Drum type rotates Ti cathode, in CuSO4·5H2O 300g/L, H2SO4140g/L, Cl-30mg/L, 57 DEG C of temperature, current density 69A/ dm2, copper-stripping is obtained into electrolytic copper foil with the lasting rotation of cathode；
2) copper foil obtained by step 1), which enters in the dilute sulfuric acid of 15wt% to impregnate, carries out pickling, time 5s；
3) level-one roughening and two level roughening：Copper foil after the completion of step 2) processing is entered under following process conditions and carries out one Grade roughening：CuSO4·5H2O 40g/L, H2SO460g/L, Mo12Na3O40P 1.8g/L, 15 DEG C of temperature, current density 15A/dm2, 4s, the copper foil after level-one roughening enter two level roughening, and the process conditions of two level roughening are as follows：CuSO4·5H2O 70g/L, H2SO4140g/L, Mo12Na3O40P 1.8g/L, 25 DEG C of temperature, current density 25A/dm2, 2s；
4) level-one solidification and two level solidification：Copper foil after the completion of step 3) processing, which enters under following process conditions, carries out level-one Solidification：CuSO4·5H2O 300g/L, H2SO4180g/L, 35 DEG C of temperature, current density 35A/dm2, 6s, after level-one solidification Copper foil enters two level solidification, and the cured process conditions of two level are as follows：CuSO4·5H2O 200g/L, H2SO4150g/L, temperature 45 DEG C, current density 25A/dm2, 4~10s；
5) three-level is roughened：Copper foil in step 4) after two level solidification, which enters, carries out three-level roughening under following process conditions： CuSO4·5H2O 60g/L, H2SO4140g/L, Mo12Na3O40P 2.0g/L, 40 DEG C of temperature, current density 5A/dm2, 3s, processing Copper foil after the completion, which enters in rinsing bowl, to be washed；
6) nickel plating kirsite：Copper foil in step 5) after the completion of processing enters the plating containing potassium pyrophosphate, zinc sulfate, nickel sulfate It is electroplated in slot, design parameter is as follows：ZnSO4·7H2O 0.5g/L, NiSO4·6H2O 4g/L, K4P2O7·3H2O 150g/ L, pH 10,30 DEG C of temperature, current density 1A/dm2, 3s；Copper foil after the completion of processing, which enters in rinsing bowl, to be washed；
7) anti-oxidation：Copper foil in step 6) after the completion of processing, which enters in the coating bath containing zinc sulfate, to be electroplated, specifically Parameter is as follows：Na2Cr2O7:10g/L, ZnSO4·7H2O:1.0g/L, pH 2~4,40 DEG C of temperature, current density 3.0A/dm2, 3s；
8) silane coupling agent is handled：γ-glycidyl ether oxygen propyl trimethoxy silicane of a concentration of 0.5wt% is water-soluble Liquid is sprayed at copper foil surface under room temperature state, after in 320 DEG C of baking oven toast 4.5s obtain product.
Embodiment 5：
A kind of fine roughening treatment technique of electrolytic copper foil surface, comprises the technical steps that：
1) it is former foil by 9 μm of HTE copper foils, using the arc Ni―Ti anode and diameter 2700mm drums of coated with nano iridium dioxide Shape rotates Ti cathode, in CuSO4·5H2O 300g/L, H2SO4140g/L, Cl-30mg/L, 57 DEG C of temperature, current density 69A/ dm2, copper-stripping is obtained into electrolytic copper foil with the lasting rotation of cathode；
2) copper foil obtained by step 1) carries out pickling, 5~10s of time into immersion in the dilute sulfuric acid of 10~15wt%；
3) level-one roughening and two level roughening：Copper foil after the completion of step 2) processing is entered under following process conditions and carries out one Grade roughening：CuSO4·5H2O 60g/L, H2SO4180g/L, Mo12Na3O40P 0.2g/L, 35 DEG C of temperature, current density 25A/ dm2, 2s, level-one roughening after copper foil enter two level roughening, two level roughening process conditions it is as follows：CuSO4·5H2O 100g/L, H2SO4220g/L, Mo12Na3O40P0.2g/L, 25 DEG C of temperature, current density 20A/dm2, 2s；
4) level-one solidification and two level solidification：Copper foil after the completion of step 3) processing, which enters under following process conditions, carries out level-one Solidification：CuSO4·5H2O 150g/L, H2SO480g/L, 35 DEG C of temperature, current density 15A/dm2, 4s, the copper after level-one solidification Foil enters two level solidification, and the cured process conditions of two level are as follows：CuSO4·5H2O 200g/L, H2SO4120g/L, temperature 45 C, Current density 25A/dm2, 4.5s；
5) three-level is roughened：Copper foil in step 4) after two level solidification, which enters, carries out three-level roughening under following process conditions： CuSO4·5H2O 60g/L, H2SO4180g/L, Mo12Na3O40P 0.2g/L, 35 DEG C of temperature, current density 15A/dm2, 2s, place Copper foil after the completion of reason, which enters in rinsing bowl, to be washed；
6) nickel plating kirsite：Copper foil in step 5) after the completion of processing enters the plating containing potassium pyrophosphate, zinc sulfate, nickel sulfate It is electroplated in slot, design parameter is as follows：ZnSO4·7H2O 10g/L, NiSO4·6H2O 20g/L, K4P2O7·3H2O 300g/ L, pH 10,30 DEG C of temperature, current density 5.0A/dm2, 3s；Copper foil after the completion of processing, which enters in rinsing bowl, to be washed；
Using the 103124810 A2013.05.29 (WO2012/ of CN of Japanese JX Shi Nippon Mining and Metals Co., Ltd 039285JP2012.03.29) the following comparative example of the roughening treatment process implementing of patent disclosure：
Comparative example 1：
(1) it is roughened：
Cu2+：15g/L (is added) in the form of cupric sulfate pentahydrate
H2SO4：100g/L
W (tungsten)：3mg/L (is added) in the form of sodium tungstate
As (arsenic)：1000mg/L is (with H3AsO3Form addition)
Lauryl sodium sulfate：10mg/L
Temperature：40℃
Electrodeposition condition：Current density 50A/dm2, 4s.
(2) cure
Cu2+：50g/L (is added) in the form of cupric sulfate pentahydrate
H2SO4：100g/L
Temperature：40℃
Electrodeposition condition：Current density 20A/dm2, 10s.
It is dried according still further to after admiro same as Example 1, anti-oxidation processing, and silane coating coupling agent.
Comparative example 2
(1) it is roughened
Cu2+：14g/L (is added) in the form of cupric sulfate pentahydrate
H2SO4：100g/L
Temperature：25℃
Electrodeposition condition：Current density 30A/dm2, 5s.
(2) cure
Cu2+：65g/L (is added) in the form of cupric sulfate pentahydrate
H2SO4：90g/L
Temperature：45℃
Electrodeposition condition：Current density 20A/dm2, 10s.
It is dried according still further to after admiro same as Example 1, anti-oxidation processing, and silane coating coupling agent.
More clearly to describe the performance that present invention process handles copper foil, by the test side of performance indicator involved in the present invention Method is described below：
Roughness Rz：Using probe-type surface roughness test method as defined in JISB0651-2001, with Marl, Germany M2 Type surface roughness is tested.
Peel strength：By 4 macro benevolence electronics epoxy resin semi-solid preparation material (GA-170B-LL, Tg175), using vacuum pressure Machine is hot pressed into copper coated foil plate, and 1mm lines are etched on etching machine, are tested according to method as defined in IPC-TM-650.
Resistance to hydrochloric acid deterioration rate：The 1mm circuit samples that etching is obtained, in the hydrochloric acid solution of mass percent concentration 18% In, after impregnating 30 minutes under room temperature, test peel strength value.Peel strength decaying percentage after salt acid soak, As resistance to hydrochloric acid deterioration rate.
Lateral erosion：Circuit through salt acid soak, test resistance to hydrochloric acid deterioration rate after, super depth-of-field microscope (Japan, KEYENCE, VHX-1000) under measure the width of line edges reddened area, 0-0.1mm be no lateral erosion, more than 0.1mm then to have Lateral erosion.
Smooth surface microetch：Copper foil is toasted 30 minutes at 200 DEG C, in 10Wt%H2SO4, 5%H2O2In, 35 DEG C of temperature, instead It answers 30 seconds, cleans up and dry, then whether there is or not the exceptions such as striped, point on the surface that detects by an unaided eye.
The molybdenum content of copper foil surface and roughening, solidification deposition：Using plasma emission spectrometer (ICP-AES, USA, Thermo Electron Corporation) test.
Copper powder：Copper foil (20cm*20cm) is placed on horizontal platform, it is the stainless steel cylinder of 200g, diameter 30mm to take quality Body, alternating floor neutrality Medium speed filter paper are simultaneously uprightly put on copper foil, and horizontal direction applies external force to stainless steel cylinder and moves it 120mm, removing filter paper, whether there is or not copper powders for (500 times) observations on microscope.
Moisture absorption handles deterioration rate：The 1mm circuits that etching is obtained, boil 120 minutes in distilled water, after cooling, drying, Test the peel strength percentage of decay after being boiled through boiling.
Heat deterioration rate：The 1mm circuits that etching is obtained, are toasted 48 hours at 180 DEG C, cooling, test heating Peel strength percentage of decay later.
Copper foil obtained by 1-5 of the embodiment of the present invention and comparative example 1-2 is tested for the property, as a result as shown in table 1, table 2：
The performance test data of copper foil after 1 surface treated of table
The performance test data of copper foil after 2 surface treated of table
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all the present invention spirit and Within principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention.

Claims (10)

1. a kind of fine roughening treatment technique of electrolytic copper foil surface, including following technological process：Level-one roughening-two level roughening- Level-one solidification-two level solidification-three-level roughening-zinc-nickel alloy-is anti-oxidation-silane coupling agent processing-drying, which is characterized in that The level-one roughening, two level are roughened and the process conditions of three-level roughening are：CuSO4·5H2O 40~100g/L, H2SO460~ 220g/L, Mo12Na3O401.5~2.0g/L of P, 15~40 DEG C of temperature.
2. the fine roughening treatment technique of electrolytic copper foil surface according to claim 1, which is characterized in that the level-one is thick The current density of change is 15~25A/dm2, the current density of 2~4s, the two level roughening are 20~25A/dm2, 2~4s is described The current density of three-level roughening is 5~15A/dm2, 1~3s.
3. the fine roughening treatment technique of electrolytic copper foil surface according to claim 1 or 2, which is characterized in that described one Grade roughening, two level are roughened and the process conditions of three-level roughening are：CuSO4·5H2O 45~80g/L, H2SO480~200g/L, Mo12Na3O401.5~1.8g/L of P, 20~38 DEG C of temperature.
4. the fine roughening treatment technique of electrolytic copper foil surface according to claim 3, which is characterized in that the level-one is thick Change, two level is roughened and the process conditions of three-level roughening are：CuSO4·5H2O 50~60g/L, H2SO4140~180g/L, Mo12Na3O40P 1.5g/L, 25~35 DEG C of temperature.
5. the fine roughening treatment technique of electrolytic copper foil surface according to claim 1 or 2, which is characterized in that described one Further include acid pickling step before grade roughening, further includes water-washing step after the three-level roughening and anti-oxidation step.
6. the fine roughening treatment technique of electrolytic copper foil surface according to claim 1 or 2, which is characterized in that described Level-one cures and the specific process conditions of two level solidification are：CuSO4·5H2O 150~300g/L, H2SO480~180g/L, temperature 35~55 DEG C of degree, current density are 15~35A/dm2, 4~10s.
7. the fine roughening treatment technique of electrolytic copper foil surface according to claim 1 or 2, which is characterized in that described The concrete technology condition of zinc-nickel alloy is：ZnSO4·7H2O 0.5~10g/L, NiSO4·6H2O 4~20g/L, K4P2O7· 3H2O 150~300g/L, pH 8~11,30~50 DEG C of temperature, 1~5A/dm of current density2, 2~6s.
8. the fine roughening treatment technique of electrolytic copper foil surface according to claim 1 or 2, which is characterized in that described The anti-oxidation specific process conditions of step are：Na2Cr2O7:5~10g/L, ZnSO4 ·7H2O:0.1~1.0g/L, pH 2~4, 30~50 DEG C of temperature, 0.5~3.0A/dm of current density2, 1~4s.
9. the fine roughening treatment technique of electrolytic copper foil surface according to claim 1 or 2, which is characterized in that described Silane coupling agent processing step is by the γ of a concentration of 0.05~0.5wt%-glycidyl ether oxygen propyl trimethoxy silicane water Solution is sprayed at copper foil surface under room temperature state, after in 200~400 DEG C of baking oven toast 4~8s.
10. the fine roughening treatment technique of the electrolytic copper foil surface according to claim 1,2, any one of 4, feature exist It for 9~140 μm of HTE copper foils is former foil to use thickness in, the electrolytic copper foil, and working condition is as follows：Using coated with nano The arc Ni―Ti anode and drum type of iridium dioxide rotate Ti cathode, in CuSO4·5H2O 300g/L, H2SO4140g/L, Cl-30mg/ L, 57 DEG C of temperature, current density 69A/dm2, copper-stripping is obtained into electrolytic copper foil with the lasting rotation of cathode.
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