CN103397342A - High heat-resisting electrolytic copper foil and preparation method thereof - Google Patents
High heat-resisting electrolytic copper foil and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high heat-resisting electrolytic copper foil and a preparation method thereof. The copper foil is characterized in that: the high heat-resisting electrolytic copper foil meets the requirements of the high-speed, high-frequency and high heat-resisting CCL and PCB sheet materials of LOW DK/DF, and the crystal grains in the rough surface of the copper foil are in layered crystallization. The preparation method comprises following steps: preparing an electrolytic copper foil by adopting the direct current electro-deposition technology, and then subjecting the surface of the electrolytic copper foil to following processes: acid washing treatment, low-coarsing process, curing process, oxide treatment, water washing, anti-oxidation process, hot-water washing, silane treatment and drying through adopting different electrolytic liquid combinations and electro-deposition technology parameters in different phases in the electrolytic equipment.
Description
Technical field
The present invention relates to a kind of high heat-resisting electrolytic copper foil and preparation method thereof, particularly a kind of heat-resisting electrolytic copper foil of height that is suitable for the high-speed high frequency of LOW DK/Df, high heat-resisting CCL and pcb board material demand and preparation method thereof.
Background technology
Along with the develop rapidly of electronic information PCB technology, the PCB industry also promotes the future development of CCL towards slimming, densification.At present, this area is more and more higher to the quality parameter requirement of sheet material, and main manifestations is: thickness of dielectric layers is more and more thinner, and deviation is little; Specific inductivity more and more less (Dk); Dielectric loss more and more less (Df); Second-order transition temperature high (TG); CET coefficient of expansion coupling is strict; High tenacity (dimensional stability).
And the thickness done of copper coated foil plate high-end product is more and more thinner now, this just requires also more and more higher to thermotolerance and the electrical property aspect of material, for Copper Foil, want to adapt to making fine rule road, and the Copper Foil of multi-layered board need have high ductility and cementability, simultaneously low roughness, homogeneity, densification must be arranged.
Summary of the invention
The object of the invention is to, a kind of high heat-resisting electrolytic copper foil and preparation method thereof is provided.Electrolytic copper foil of the present invention is suitable for the high-speed high frequency of LOW DK/Df, high heat-resisting CCL and the demand of pcb board material on performance.
Technical scheme of the present invention: a kind of high heat-resisting electrolytic copper foil is characterized in: it is the electrolytic copper foil of the high-speed high frequency that is suitable for LOW DK/Df, high heat-resisting CCL and pcb board material demand, and its hair side crystal grain is laminated crystalline.
In the heat-resisting electrolytic copper foil of above-mentioned height, described electrolytic copper foil thickness is 18um, hair side roughness Rz≤2.5um, FR4 sheet material peel strength >=1.45kg/cm, tensile strength >=380Mpa, unit elongation >=6%.
In the heat-resisting electrolytic copper foil of aforesaid height, described electrolytic copper foil thickness is 35um, hair side roughness Rz≤4.5um, FR4 sheet material peel strength >=2.00kg/cm, tensile strength >=330Mpa, unit elongation >=8%.。
The preparation method of the heat-resisting electrolytic copper foil of aforesaid height, be characterized in, after adopting DC electrodeposition technique to make electrolytic copper foil, speed with 16-18m/min is moved in electrolyzer, by a plurality of stages, in electrolyzer, take the cooperation processing of different electrolyte combination and electro-deposition process parameter, cleanup acid treatment, low roughening treatment, solidification treatment, Darkening process, washing, anti-oxidation processing, hot water wash, silane treatment and baking operation are carried out in the surface of electrolytic copper foil, and its technical process is as follows:
The pickling stage: in electrolytic solution, Cu
2+Concentration≤10g/L, H
2SO
4Concentration 100~200g/L, 20~40 ℃ of temperature;
The alligatoring copper stage: in electrolytic solution, Cu
2+Concentration 8~16g/L, H
2SO
4Concentration 100~220g/L, 20~25 ℃ of temperature, current density 1200~3500A/m
2
Solidify the copper stage: in electrolytic solution, Cu
2+Concentration 20~60g/L, H
2SO
4Concentration 100~200g/L, 40~60 ℃ of temperature, current density 1500~2500A/m
2
Melanism copper one-phase: in electrolytic solution, Cu
2+Concentration 1~10g/L, H
2SO
4Concentration 50~100g/L, 20~25 ℃ of temperature, current density 500~1000A/m
2
The melanism copper two-stage: in electrolytic solution, Cu
2+Concentration 1~2g/L, Ni
2+Concentration 0.1~1g/L, Na
3(C
6H
5O
7): 2H
2O concentration 50~100g/L, (NH
4)
2SO
4Concentration 50~100g/L, 20~25 ℃ of temperature, pH3~5, current density 200~500A/m
2
The zinc-plated stage: in electrolytic solution, Zn
2+Concentration 1~5g/L, Ni
2+Concentration 1~5g/L, K
4P
2O
7Concentration 30~100g/L, 20~50 ℃ of temperature, pH8~10, current density 50~100A/m
2
The passivation stage: in electrolytic solution, Cr
3+Concentration 1~2g/L, 30~60 ℃ of temperature, K
4P
2O
7Concentration 30~100g/L, pH8~10, current density 10~20A/m
2
Hot water wash: 40~60 ℃ of temperature, P0.2~0.3Mpa; (P refers to hydraulic pressure)
Silane treatment stage: γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane concentration 0.2~0.4%(refers to the concentration of solution of silane), pH6-8;
Oven dry: 200~300 ℃ of temperature.
In the preparation method of the heat-resisting electrolytic copper foil of aforesaid height, the described alligatoring copper stage, Copper Foil hair side current density divide four sections given, given current density is respectively 2800~3500,1200,2800~3500 and 1200A/m
2.Namely adopt two electrolyzers, four positive plates to realize, preset time is identical.
In the preparation method of the heat-resisting electrolytic copper foil of aforesaid height, the described curing copper stage, Copper Foil hair side current density divide two sections given, given current density is respectively 1500~2500A/m
2With 1500~2500A/m
2.Namely adopt two electrolyzers, two positive plates to realize, be all identical preset time, and two sections of current densities are not quite identical.
In the preparation method of the heat-resisting electrolytic copper foil of aforesaid height, described melanism copper one-phase, Copper Foil hair side current density divide one section given, current density is 1500~2500A/m
2.Namely adopt an electrolyzer, a positive plate is realized.
In the preparation method of the heat-resisting electrolytic copper foil of aforesaid height, the described melanism copper two-stage, Copper Foil hair side current density divide one section given, current density is 500~1000A/m
2.Namely adopt an electrolyzer, a positive plate is realized.
In the preparation method of the heat-resisting electrolytic copper foil of aforesaid height, the described zinc-plated stage, light face, hair side current density divide two sections given, light face, the current density that hair side is given are respectively 50~100A/m
2With 50~100A/m
2.Zinc-plated stage light splitting surface, two sections given different current densities of hair side, the time is all identical.
In the preparation method of the heat-resisting electrolytic copper foil of aforesaid height, the described passivation stage, light face, hair side current density divide two sections given, light face, the current density density that hair side is given are respectively 10~20A/m
2With 10~20A/m
2.Passivation stage light splitting surface, two sections given different current densities of hair side, the time is all identical.
In the preparation method of the heat-resisting electrolytic copper foil of aforesaid height, the concrete grammar that described DC electrodeposition technique makes electrolytic copper foil is, adopt DC electrodeposition technique that electrolytic solution is formed with electro-deposition process parameter and carries out reasonable coordination, and in electrolytic process, add organic blending additive, its technical process is as follows: adopt electrolytic solution Cu2+ concentration 70~80g/L, H2SO4 concentration 80~120g/L, the parameter of CL-concentration 20 ± 5ppm coordinates 50~60 ℃ of temperature, flow 40~50m3/h, current density 5000~6000A/m2 carries out galvanic deposit; Described organic additive is Mierocrystalline cellulose and gelatin.
In the preparation method of the heat-resisting electrolytic copper foil of aforesaid height, the addition of described Mierocrystalline cellulose and gelatin is 0.01~0.05mg/L.Molecular weight cellulose 250,000; 80-125cps.(25 degree), gelatine molecular weight 10000~30000.
Compared with prior art, electrolytic copper foil of the present invention is suitable for the high-speed high frequency of LOW DK/Df, high heat-resisting CCL, pcb board material demand, and its Copper Foil hair side crystal grain is laminated crystalline, and it has utmost point low profile, the high performance of extending of high temperature.Its obvious characteristic is 18um hair side roughness Rz≤2.5um, unit elongation >=6%, gives birth to paper tinsel organic additive amount and is nano level, in surface treatment process, does not add any poisonous additive, meets the European Union environmental protection requirement.And in preparation method of the present invention by electrolytic copper foil surface is processed, can enlarge the Copper Foil grain surface long-pending, increase the peel strength of Copper Foil hair side, meet CCL High Tg, the high antistripping of Halogen-free, high heat resistance can requirement.And whole process is taked DC electrodeposition technique, electrolyte combination and electro-deposition process parameter are carried out to reasonable disposition, after surface treatment of the present invention, the hair side surfaceness Rz of 18um electrolytic copper foil≤2.5 μ m, its peel strength >=1.45kg/cm, High Tg, Halogen-free, thickness >=0.5mm sheet material peel strength >=1.20kg/cm; And after the technology of the present invention means are processed, 260 ℃ of high temperature, non-oxidation phenomenon under the 30min condition (international standard is 200 ℃ of 0.5h non-oxidation phenomenons), general electrolytic copper foil high temperature oxidation destructive test is 225 ℃, 30min.In addition because the present invention does not adopt poisonous additive, in whole surface treatment process, not there will be the toxic substances such as arsenic, selenium, cadmium, antimony, sexavalent chrome, lead, realized the process environments of asepsis environment-protecting, so not only reduced cost, also helped and realize Sustainable development.The present invention has mainly adopted DC electrodeposition technique, is simple and easy to realize.
Utilize preparation method of the present invention to make electrolytic copper foil, adopt GB/T5121.1-2008 copper and copper alloy chemical analysis method to measure the content of copper >=99.93%(Cu+Ag), apparently higher than GB/T5230, IPC-4562 Copper Foil chemical composition standard >=99.8%(Cu+Ag).Adopt in addition the organic compound content of the methods detections such as ICP-OES, GC-MS, UV-VIS/EDX all<0.001% or 0%.
The accompanying drawing explanation
Fig. 1 is the 18um electrolytic copper foil SEM picture that does not use the inventive method to process;
Fig. 2 uses the inventive method to process 18um electrolytic copper foil SEM picture afterwards.
Embodiment
The present invention is further illustrated below in conjunction with drawings and Examples, but not as the foundation to the present invention's restriction.
Embodiment.A kind of high heat-resisting electrolytic copper foil, it is the electrolytic copper foil of the high-speed high frequency that is suitable for LOW DK/Df, high heat-resisting CCL and pcb board material demand, its hair side crystal grain is laminated crystalline.Thickness is the electrolytic copper foil of 18um, hair side roughness Rz≤2.5um, FR4 sheet material peel strength >=1.45kg/cm, unit elongation >=6%, tensile strength >=380Mpa; Thickness is the electrolytic copper foil of 35um, hair side roughness Rz≤4.5um, FR4 sheet material peel strength >=2.00kg/cm, tensile strength >=330Mpa, unit elongation >=8%.
The preparation method of the heat-resisting electrolytic copper foil of aforesaid height is: after adopting DC electrodeposition technique to make electrolytic copper foil, (speed of 16-18m/min is moved in electrolyzer), by a plurality of stages, in electrolyzer, take the cooperation processing of different electrolyte combination and electro-deposition process parameter, cleanup acid treatment, low roughening treatment, solidification treatment, Darkening process, washing, anti-oxidation processing, hot water wash, silane treatment and baking operation are carried out in the surface of electrolytic copper foil, and its technical process is as follows:
The pickling stage: in electrolytic solution, Cu
2+Concentration≤10g/L, H
2SO
4Concentration 100~200g/L, 20~40 ℃ of temperature;
The alligatoring copper stage: in electrolytic solution, Cu
2+Concentration 8~16g/L, H
2SO
4Concentration 100~220g/L, 20~25 ℃ of temperature, current density 1200~3500A/m
2
Solidify the copper stage: in electrolytic solution, Cu
2+Concentration 20~60g/L, H
2SO
4Concentration 100~200g/L, 40~60 ℃ of temperature, current density 1500~2500A/m
2
Melanism copper one-phase: in electrolytic solution, Cu
2+Concentration 1~10g/L, H
2SO
4Concentration 50~100g/L, 20~25 ℃ of temperature, current density 500~1000A/m
2
The melanism copper two-stage: in electrolytic solution, Cu
2+Concentration 1~2g/L, Ni
2+Concentration 0.1~1g/L, Na
3(C
6H
5O
7): 2H
2O concentration 50~100g/L, (NH
4)
2SO
4Concentration 50~100g/L, 20~25 ℃ of temperature, pH3~5, current density 200~500A/m
2
The zinc-plated stage: in electrolytic solution, Zn
2+Concentration 1~5g/L, Ni
2+Concentration 1~5g/L, K
4P
2O
7Concentration 30~100g/L, 20~50 ℃ of temperature, pH8~10, current density 50~100A/m
2
The passivation stage: in electrolytic solution, Cr
3+Concentration 1~2g/L, 30~60 ℃ of temperature, K
4P
2O
7Concentration 30~100g/L, pH8~10, current density 10~20A/m
2
Hot water wash: 40~60 ℃ of temperature, P0.2~0.3Mpa;
Silane treatment stage: γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane concentration 0.2~0.4%, pH6-8;
Oven dry: 200~300 ℃ of temperature.
The described alligatoring copper stage, Copper Foil hair side current density divide four sections given, given current density is respectively 2800~3500,1200,2800~3500 and 1200A/m
2.
The described curing copper stage, Copper Foil hair side current density divide two sections given, given current density is respectively 1500~2500A/m
2With 1500~2500A/m
2.
Described melanism copper one-phase, Copper Foil hair side current density divide one section given, current density is 500~1000A/m
2.
The described melanism copper two-stage, Copper Foil hair side current density divide one section given, current density is 200~500A/m
2.
The described zinc-plated stage, light face, hair side current density divide two sections given, light face, the current density that hair side is given are respectively 50~100A/m
2With 50~100A/m
2.
The described passivation stage, light face, hair side current density divide two sections given, light face, the current density density that hair side is given are respectively 10~20A/m
2With 10~20A/m
2.
Silane treatment stage: γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane concentration 0.2~0.4% spray treatment.
The concrete grammar that described DC electrodeposition technique makes electrolytic copper foil is, adopt DC electrodeposition technique that electrolytic solution is formed with electro-deposition process parameter and carries out reasonable coordination, and in electrolytic process, add organic blending additive, its technical process is as follows: adopt electrolytic solution Cu2+ concentration 70~80g/L, H2SO4 concentration 80~120g/L, the parameter of CL-concentration 20 ± 5ppm coordinates 50~60 ℃ of temperature, flow 40~50m3/h, and current density 5000~6000A/m2 carries out galvanic deposit; Described organic additive is Mierocrystalline cellulose and gelatin.The addition of described Mierocrystalline cellulose and gelatin is 0.01~0.05mg/L.
The preparation method embodiment 1 of electrolytic copper foil.
Adopt electrolytic solution Cu
2+70~80g/L, H
2SO
480~120g/L, CL
-20 ± 5ppm, T55 ℃, Q:40m
3/ h, current density 6000A/m
2Parameter coordinate and to carry out galvanic deposit, and add organic blending additive in electrolyzer.Described mixed additive consists of: Mierocrystalline cellulose 0.05mg/L, gelatin 0.05mg/L.
By low profile high ductibility energy electrolytic copper foil prepared by embodiment, its hair side crystal grain is stratiform, 18um hair side Rz≤2.5um, unit elongation >=6%, hair side peel strength >=0.4kg/cm, tensile strength >=365Mpa;
The preparation method embodiment 2 of electrolytic copper foil.
Adopt electrolytic solution Cu
2+70~80g/L, H
2SO
480~120g/L, CL
-20 ± 5ppmT50 ℃, Q:50m
3/ h, current density 5000A/m
2Parameter coordinate and to carry out galvanic deposit, and add organic blending additive in electrolyzer.Described mixed additive consists of: Mierocrystalline cellulose 0.01mg/L, gelatin 0.02mg/L.
By low profile high ductibility energy electrolytic copper foil prepared by embodiment, its hair side crystal grain is stratiform, 18um hair side Rz≤2.5um, unit elongation >=8%, hair side peel strength >=0.376kg/cm, tensile strength >=336.8Mpa;
The surface treatment embodiment 1 of electrolytic copper foil.
The pickling stage: Cu
2+≤ 10g/L, H
2SO
4100~200g/L, T20~40 ℃;
The alligatoring copper stage: Cu
2+8~10g/L, H
2SO
4220g/L, T20~25 ℃, current density 2800,1200,2800,1200A/m
2
Solidify copper stage: Cu
2+40g/L, H
2SO
4100g/L, T40~60 ℃, current density 1500A/m
2
Melanism copper one-phase: Cu
2+5g/L, H
2SO
4100g/L, T20~25 ℃, current density 500A/m
2
The melanism copper two-stage: Cu
2+1g/L, Ni
2+1g/L, Na
3(C
6H
5O
7): 2H
2O is 50g/L, (NH
4)
2SO
4For 50g/L, T20~25 ℃, pH3~5, current density 200A/m
2
The zinc-plated stage: Zn
2+4g/L, Ni
2+1g/L, K
4P
2O
7100g/L, T20~50 ℃, pH8~10, light hair side current density 50A/m
2
The passivation stage: Cr
3+1~2g/L, T30~60 ℃, K
4P
2O
7100g/L, pH8~10, light hair side current density 20A/m
2
Hot water wash: T40~60 ℃, P0.2~0.3Mpa;
Silane treatment stage: γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane concentration 0.2~0.4%, pH6-8;
Oven dry: 200~300 ℃ of temperature.
Hair side surfaceness Rz by embodiment 1 scheme 18um electrolytic copper foil≤2.5 μ m, its peel strength >=1.35kg/cm, High Tg, Halogen-free, thickness >=0.5mm sheet material peel strength >=1.10kg/cm.
The surface treatment embodiment 2 of electrolytic copper foil.
The pickling stage: Cu
2+≤ 10g/L H
2SO
4100~200g/L, T20~40 ℃
The alligatoring copper stage: Cu
2+12g/L, H
2SO
4100g/L, T20~25 ℃, current density 3500,1200,3500,1200A/m
2
Solidify copper stage: Cu
2+50g/L, H
2SO
4100g/L, T40~60 ℃, current density 2500A/m
2
Melanism copper one-phase: Cu
2+5g/L, H
2SO
4100g/L, T20~25 ℃, current density 1000A/m
2
The melanism copper two-stage: Cu
2+1g/L, Ni
2+0.5g/L, Na
3(C
6H
5O
7): 2H
2O is 100g/L, (NH
4)
2SO
4For 100g/L, T20~25 ℃, pH3~5, current density 500A/m
2
The zinc-plated stage: Zn
2+2g/L, Ni
2+1g/L, K
4P
2O
750g/L, T20~50 ℃, pH8~10, light hair side current density 100A/m
2
The passivation stage: Cr
3+1g/L T30~60 ℃, K
4P
2O
7100g/L, pH8~10 smooth hair side current density 10A/m
2
Hot water wash: T40~60 ℃, P0.2~0.3Mpa;
Silane treatment stage: γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane concentration 0.2~0.4%, pH6-8;
Oven dry: 200~300 ℃ of temperature.
Hair side surfaceness Rz by embodiment 2 scheme 18um electrolytic copper foils≤2.5 μ m, its peel strength >=1.45kg/cm, High Tg, Halogen-free, thickness >=0.5mm sheet material peel strength >=1.20kg/cm.
Adopt method of the present invention to electrolytic copper foil carry out before and after surface treatment effect as depicted in figs. 1 and 2.After method of the present invention was processed, the electrolytic copper foil surface roughness obviously reduced.
Claims (10)
1. one kind high heat-resisting electrolytic copper foil, it is characterized in that: it is the electrolytic copper foil of the high-speed high frequency that is suitable for LOW DK/Df, high heat-resisting CCL and pcb board material demand, and its hair side crystal grain is laminated crystalline.
2. the heat-resisting electrolytic copper foil of height according to claim 1, it is characterized in that: described electrolytic copper foil thickness is 18um, hair side roughness Rz≤2.5um, FR4 sheet material peel strength >=1.45kg/cm, tensile strength >=380Mpa, unit elongation >=6%.
3. the heat-resisting electrolytic copper foil of height according to claim 1, it is characterized in that: described electrolytic copper foil thickness is 35um, hair side roughness Rz≤4.5um, FR4 sheet material peel strength >=2.00kg/cm, tensile strength >=330Mpa, unit elongation >=8%.
4. the preparation method of the heat-resisting electrolytic copper foil of the described height of arbitrary claim of according to claim 1 to 3, it is characterized in that, after adopting DC electrodeposition technique to make electrolytic copper foil, speed with 16-18m/min is moved in electrolyzer, by a plurality of stages, in electrolyzer, take the cooperation processing of different electrolyte combination and electro-deposition process parameter, cleanup acid treatment, low roughening treatment, solidification treatment, Darkening process, washing, anti-oxidation processing, hot water wash, silane treatment and baking operation are carried out in the surface of electrolytic copper foil, and its technical process is as follows:
The pickling stage: in electrolytic solution, Cu
2+Concentration≤10g/L, H
2SO
4Concentration 100~200g/L, 20~40 ℃ of temperature;
The alligatoring copper stage: in electrolytic solution, Cu
2+Concentration 8~16g/L, H
2SO
4Concentration 100~220g/L, 20~25 ℃ of temperature, current density 1200~3500A/m
2
Solidify the copper stage: in electrolytic solution, Cu
2+Concentration 20~60g/L, H
2SO
4Concentration 100~200g/L, 40~60 ℃ of temperature, current density 1500~2500A/m
2
Melanism copper one-phase: in electrolytic solution, Cu
2+Concentration 1~10g/L, H
2SO
4Concentration 50~100g/L, 20~25 ℃ of temperature, current density 500~1000A/m
2
The melanism copper two-stage: in electrolytic solution, Cu
2+Concentration 1~2g/L, Ni
2+Concentration 0.1~1g/L, Na
3(C
6H
5O
7): 2H
2O concentration 50~100g/L, (NH
4)
2SO
4Concentration 50~100g/L, 20~25 ℃ of temperature, pH3~5, current density 200~500A/m
2
The zinc-plated stage: in electrolytic solution, Zn
2+Concentration 1~5g/L, Ni
2+Concentration 1~5g/L, K
4P
2O
7Concentration 30~100g/L, 20~50 ℃ of temperature, pH8~10, current density 50~100A/m
2
The passivation stage: in electrolytic solution, Cr
3+Concentration 1~2g/L, 30~60 ℃ of temperature, K
4P
2O
7Concentration 30~100g/L, pH8~10, current density 10~20A/m
2
Hot water wash: 40~60 ℃ of temperature, P0.2~0.3Mpa;
Silane treatment stage: γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane concentration 0.2~0.4%, pH6-8;
Oven dry: 200~300 ℃ of temperature.
5. the preparation method of the heat-resisting electrolytic copper foil of height according to claim 4 is characterized in that: the described alligatoring copper stage, current density divide four sections given, given current density is respectively 2800~3500,1200,2800~3500 and 1200A/m
2.
6. the preparation method of the heat-resisting electrolytic copper foil of height according to claim 4 is characterized in that: the described curing copper stage, current density divide two sections given, given current density is respectively 1500~2500A/m
2With 1500~2500A/m
2.
7. the preparation method of the heat-resisting electrolytic copper foil of height according to claim 4 is characterized in that: the described zinc-plated stage, current density divide two sections given, given current density is respectively 50~100A/m
2With 50~100A/m
2.
8. the preparation method of the heat-resisting electrolytic copper foil of height according to claim 4 is characterized in that: the described passivation stage, current density divide two sections given, given current density density is respectively 10~20A/m
2With 10~20A/m
2.
9. the preparation method of the heat-resisting electrolytic copper foil of height according to claim 4, it is characterized in that, the concrete grammar that described DC electrodeposition technique makes electrolytic copper foil is, adopt DC electrodeposition technique that electrolytic solution is formed with electro-deposition process parameter and carries out reasonable coordination, and in electrolytic process, add organic blending additive, its technical process is as follows: adopt electrolytic solution Cu2+ concentration 70~80g/L, H2SO4 concentration 80~120g/L, the parameter of CL-concentration 20 ± 5ppm coordinates 50~60 ℃ of temperature, flow 40~50m3/h, current density 5000~6000A/m2 carries out galvanic deposit, described organic additive is Mierocrystalline cellulose and gelatin.
10. the preparation method of the heat-resisting electrolytic copper foil of height according to claim 9, it is characterized in that: the addition of described Mierocrystalline cellulose and gelatin is 0.01~0.05mg/L; Viscosity when described cellulosic molecular weight is 250000,25 ℃ is 80-125cps.; The molecular weight of described gelatin is 10000~30000.
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CN104372384A (en) * | 2014-11-18 | 2015-02-25 | 安徽铜冠铜箔有限公司 | Method for manufacturing ultra-thick electronic copper foil |
CN104651885A (en) * | 2015-02-12 | 2015-05-27 | 安徽铜冠铜箔有限公司 | Preparation method of electronic copper foil |
CN106558678A (en) * | 2015-09-24 | 2017-04-05 | Ls美创有限公司 | The strong electrolytic copper foil of superelevation, including its electrode and secondary cell and its manufacture method |
CN108179460A (en) * | 2017-12-28 | 2018-06-19 | 湖北中科铜箔科技有限公司 | A kind of high roughness electrolytic copper foil and preparation method thereof |
CN109097751A (en) * | 2017-12-15 | 2018-12-28 | 深圳科诺桥科技股份有限公司 | The preparation method of flexibility coat copper plate |
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CN114457389A (en) * | 2022-01-27 | 2022-05-10 | 九江德福科技股份有限公司 | Method for reducing copper powder falling of electrolytic copper foil in surface treatment process |
WO2022141709A1 (en) * | 2020-12-30 | 2022-07-07 | 广东嘉元科技股份有限公司 | Electrolytic copper foil for high-frequency high-speed printed circuit board, and preparation method therefor |
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CN104372384A (en) * | 2014-11-18 | 2015-02-25 | 安徽铜冠铜箔有限公司 | Method for manufacturing ultra-thick electronic copper foil |
CN104372384B (en) * | 2014-11-18 | 2016-08-17 | 安徽铜冠铜箔有限公司 | A kind of manufacture method of super thick electronics Copper Foil |
CN104651885A (en) * | 2015-02-12 | 2015-05-27 | 安徽铜冠铜箔有限公司 | Preparation method of electronic copper foil |
CN106558678A (en) * | 2015-09-24 | 2017-04-05 | Ls美创有限公司 | The strong electrolytic copper foil of superelevation, including its electrode and secondary cell and its manufacture method |
CN109097751A (en) * | 2017-12-15 | 2018-12-28 | 深圳科诺桥科技股份有限公司 | The preparation method of flexibility coat copper plate |
CN109097748A (en) * | 2017-12-15 | 2018-12-28 | 深圳科诺桥科技股份有限公司 | The preparation method of flexibility coat copper plate |
CN108179460A (en) * | 2017-12-28 | 2018-06-19 | 湖北中科铜箔科技有限公司 | A kind of high roughness electrolytic copper foil and preparation method thereof |
CN111910223A (en) * | 2020-08-24 | 2020-11-10 | 九江德福科技股份有限公司 | Additive for electrolytic copper foil suitable for HDI board and electrolytic copper foil production process |
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 |
WO2022141709A1 (en) * | 2020-12-30 | 2022-07-07 | 广东嘉元科技股份有限公司 | Electrolytic copper foil for high-frequency high-speed printed circuit board, and preparation method therefor |
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CN114457389A (en) * | 2022-01-27 | 2022-05-10 | 九江德福科技股份有限公司 | Method for reducing copper powder falling of electrolytic copper foil in surface treatment process |
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