CN103397342B - A kind of high heat-resisting electrolytic copper foil and preparation method thereof - Google Patents
A kind of high heat-resisting electrolytic copper foil and preparation method thereof Download PDFInfo
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- CN103397342B CN103397342B CN201310360643.2A CN201310360643A CN103397342B CN 103397342 B CN103397342 B CN 103397342B CN 201310360643 A CN201310360643 A CN 201310360643A CN 103397342 B CN103397342 B CN 103397342B
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Abstract
The invention discloses a kind of high heat-resisting electrolytic copper foil and preparation method thereof, it is characterized in that: the heat-resisting electrolytic copper foil of height of the present invention is suitable for LOW? the electrolytic copper foil of the high-speed high frequency of DK/Df, high heat-resisting CCL and pcb board material demand, its hair side crystal grain is laminated crystalline.Preparation method of the present invention is after adopting DC electrodeposition technique to obtain electrolytic copper foil, in electrolyzer, taked the cooperation process of different electrolyte combination and electro-deposition process parameter by multiple stage, cleanup acid treatment, low roughening treatment, solidification treatment, Darkening process, washing, anti-oxidation process, hot water wash, silane treatment and baking operation are carried out to the surface of electrolytic copper foil.
Description
Technical field
The present invention relates to a kind of high heat-resisting electrolytic copper foil and preparation method thereof, be particularly a kind ofly suitable for heat-resisting electrolytic copper foil of height of the high-speed high frequency of LOWDK/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, PCB industry also promotes the future development of CCL towards slimming, densification.At present, this area requires more and more higher to the quality parameter 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 requires strict; High tenacity (dimensional stability).
And the thickness that does of copper coated foil plate high-end product is more and more thinner now, this just requires also more and more higher to the thermotolerance of material and electrical property aspect, for Copper Foil, want adapt to make fine rule road, and the Copper Foil of multi-layered board need have high ductility and cementability, low roughness, homogeneity, densification must be had simultaneously.
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 LOWDK/Df, high heat-resisting CCL and the demand of pcb board material in 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 being suitable for the high-speed high frequency of LOWDK/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 18 μm, hair side roughness Rz≤2.5 μm, 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 35 μm, hair side roughness Rz≤4.5 μm, 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 obtain electrolytic copper foil, run in electrolyzer with the speed of 16-18m/min, in electrolyzer, the cooperation process of different electrolyte combination and electro-deposition process parameter is taked by multiple stage, carry out cleanup acid treatment, low roughening treatment, solidification treatment, Darkening process, washing, anti-oxidation process, hot water wash, silane treatment and baking operation to the surface of electrolytic copper foil, its technical process is as follows:
Pickling stages: in electrolytic solution, Cu
2+concentration≤10g/L, H
2sO
4concentration 100 ~ 200g/L, temperature 20 ~ 40 DEG C;
The alligatoring copper stage: in electrolytic solution, Cu
2+concentration 8 ~ 16g/L, H
2sO
4concentration 100 ~ 220g/L, temperature 20 ~ 25 DEG C, current density 1200 ~ 3500A/m
2;
The solidification copper stage: in electrolytic solution, Cu
2+concentration 20 ~ 60g/L, H
2sO
4concentration 100 ~ 200g/L, temperature 40 ~ 60 DEG C, 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, temperature 20 ~ 25 DEG C, 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, temperature 20 ~ 25 DEG C, 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, temperature 20 ~ 50 DEG C, pH8 ~ 10, current density 50 ~ 100A/m
2;
The passivation stage: in electrolytic solution, Cr
3+concentration 1 ~ 2g/L, temperature 30 ~ 60 DEG C, K
4p
2o
7concentration 30 ~ 100g/L, pH8 ~ 10, current density 10 ~ 20A/m
2;
Hot water wash: temperature 40 ~ 60 DEG C, P0.2 ~ 0.3Mpa; (P refers to hydraulic pressure)
Silane treatment stage: γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane concentration 0.2 ~ 0.4%(refers to the concentration of solution of silane), pH6-8;
Dry: temperature 200 ~ 300 DEG C.
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 pieces of positive plates to realize, preset time is identical.
In the preparation method of the heat-resisting electrolytic copper foil of aforesaid height, the described solidification 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 pieces of positive plates realize, preset time is all identical, and current density two sections is 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, one piece of positive plate realizes.
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, one piece of positive plate realizes.
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, the given different current density of hair side two sections, 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, the given different current density of hair side two sections, 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 obtains electrolytic copper foil is, adopt DC electrodeposition technique that electrolytic solution composition is carried out reasonable coordination with electro-deposition process parameter, and organic blending additive is added in electrolytic process, its technical process is as follows: adopt electrolytic solution Cu
2+concentration 70 ~ 80g/L, H
2sO
4concentration 80 ~ 120g/L, Cl
-the parameter coordination temperature of concentration 20 ± 5ppm 50 ~ 60 DEG C, flow 40 ~ 50m
3/ h, current density 5000 ~ 6000A/m
2carry 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 LOWDK/Df, high heat-resisting CCL, pcb board material demand, and its Copper Foil hair side crystal grain is laminated crystalline, the performance that it has pole low profile, high temperature height extends.Its obvious characteristic is 18 μm of hair side roughness Rz≤2.5 μm, unit elongation >=6%, and raw paper tinsel organic additive amount is nano level, does not add any poisonous additive, meet European Union environmental protection requirement in surface treatment process.And by processing electrolytic copper foil surface in preparation method of the present invention, Copper Foil grain surface can be expanded and amass, increase the peel strength of Copper Foil hair side, meet the requirement of CCLHighTg, Halogen-free height antistripping, high heat resistance energy.And whole process takes DC electrodeposition technique, reasonable disposition is carried out to electrolyte combination and electro-deposition process parameter, after surface treatment of the present invention, hair side surfaceness Rz≤2.5 μm of 18 μm of electrolytic copper foils, its peel strength >=1.45kg/cm, HighTg, Halogen-free, thickness >=0.5mm sheet material peel strength >=1.20kg/cm; And after technical measure process, high temperature 260 DEG C, non-oxidation phenomenon (international standard is 200 DEG C of 0.5h non-oxidation phenomenons) under 30min condition, general electrolytic copper foil high temperature oxidation destructive test is 225 DEG C, 30min.In addition because the present invention does not adopt poisonous additive, in whole surface treatment process, there will not be the toxic substances such as arsenic, selenium, cadmium, antimony, sexavalent chrome, lead, achieve the process environments of asepsis environment-protecting, not only reduce cost like this, also help and realize Sustainable development.The present invention mainly have employed DC electrodeposition technique, is simple and easy to realize.
Preparation method of the present invention is utilized to obtain electrolytic copper foil, GB/T5121.1-2008 Copper and its alloy chemical analysis method is adopted to measure the content >=99.93%(Cu+Ag of copper), apparently higher than GB/T5230, IPC-4562 Copper Foil chemical composition standard >=99.8%(Cu+Ag).Adopt the equal < 0.001% or 0% of organic compound content that the methods such as ICP-OES, GC-MS, UV-VIS/EDX detect in addition.
Accompanying drawing explanation
Fig. 1 is the 18 μm of electrolytic copper foil SEM pictures not using the inventive method process;
Fig. 2 be use the inventive method process after 18 μm of electrolytic copper foil SEM pictures.
Embodiment
Below in conjunction with drawings and Examples, the present invention is further illustrated, but not as the foundation limited the present invention.
Embodiment.A kind of high heat-resisting electrolytic copper foil, it is the electrolytic copper foil being suitable for the high-speed high frequency of LOWDK/Df, high heat-resisting CCL and pcb board material demand, and its hair side crystal grain is laminated crystalline.Thickness is the electrolytic copper foil of 18 μm, hair side roughness Rz≤2.5 μm, FR4 sheet material peel strength >=1.45kg/cm, unit elongation >=6%, tensile strength >=380Mpa; Thickness is the electrolytic copper foil of 35 μm, hair side roughness Rz≤4.5 μm, 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 obtain electrolytic copper foil, (speed of 16-18m/min is run in electrolyzer), in electrolyzer, the cooperation process of different electrolyte combination and electro-deposition process parameter is taked by multiple stage, carry out cleanup acid treatment, low roughening treatment, solidification treatment, Darkening process, washing, anti-oxidation process, hot water wash, silane treatment and baking operation to the surface of electrolytic copper foil, its technical process is as follows:
Pickling stages: in electrolytic solution, Cu
2+concentration≤10g/L, H
2sO
4concentration 100 ~ 200g/L, temperature 20 ~ 40 DEG C;
The alligatoring copper stage: in electrolytic solution, Cu
2+concentration 8 ~ 16g/L, H
2sO
4concentration 100 ~ 220g/L, temperature 20 ~ 25 DEG C, current density 1200 ~ 3500A/m
2;
The solidification copper stage: in electrolytic solution, Cu
2+concentration 20 ~ 60g/L, H
2sO
4concentration 100 ~ 200g/L, temperature 40 ~ 60 DEG C, 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, temperature 20 ~ 25 DEG C, 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, temperature 20 ~ 25 DEG C, 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, temperature 20 ~ 50 DEG C, pH8 ~ 10, current density 50 ~ 100A/m
2;
The passivation stage: in electrolytic solution, Cr
3+concentration 1 ~ 2g/L, temperature 30 ~ 60 DEG C, K
4p
2o
7concentration 30 ~ 100g/L, pH8 ~ 10, current density 10 ~ 20A/m
2;
Hot water wash: temperature 40 ~ 60 DEG C, P0.2 ~ 0.3Mpa;
Silane treatment stage: γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane concentration 0.2 ~ 0.4%, pH6-8;
Dry: temperature 200 ~ 300 DEG C.
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 solidification 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 third oxygen) propyl trimethoxy silicane concentration 0.2 ~ 0.4% spray treatment.
The concrete grammar that described DC electrodeposition technique obtains electrolytic copper foil is, adopt DC electrodeposition technique that electrolytic solution composition is carried out reasonable coordination with electro-deposition process parameter, and organic blending additive is added in electrolytic process, its technical process is as follows: adopt electrolytic solution Cu
2+concentration 70 ~ 80g/L, H
2sO
4concentration 80 ~ 120g/L, Cl
-the parameter coordination temperature of concentration 20 ± 5ppm 50 ~ 60 DEG C, flow 40 ~ 50m
3/ h, current density 5000 ~ 6000A/m
2carry 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.
Preparation method's embodiment 1 of electrolytic copper foil.
Adopt electrolytic solution Cu
2+70 ~ 80g/L, H
2sO
480 ~ 120g/L, Cl
-20 ± 5ppm, T55 DEG C, Q:40m
3/ h, current density 6000A/m
2parameter coordination 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.
The low profile high ductibility energy electrolytic copper foil prepared by embodiment, its hair side crystal grain is stratiform, 18 μm of hair side Rz≤2.5 μm, unit elongation >=6%, hair side peel strength >=0.4kg/cm, tensile strength >=365Mpa;
Preparation method's embodiment 2 of electrolytic copper foil.
Adopt electrolytic solution Cu
2+70 ~ 80g/L, H
2sO
480 ~ 120g/L, Cl
-20 ± 5ppmT50 DEG C, Q:50m
3/ h, current density 5000A/m
2parameter coordination 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.
The low profile high ductibility energy electrolytic copper foil prepared by embodiment, its hair side crystal grain is stratiform, 18 μm of hair side Rz≤2.5 μm, unit elongation >=8%, hair side peel strength >=0.376kg/cm, tensile strength >=336.8Mpa;
The surface treatment embodiment 1 of electrolytic copper foil.
Pickling stages: Cu
2+≤ 10g/L, H
2sO
4100 ~ 200g/L, T20 ~ 40 DEG C;
The alligatoring copper stage: Cu
2+8 ~ 10g/L, H
2sO
4220g/L, T20 ~ 25 DEG C, current density 2800,1200,2800,1200A/m
2;
Solidification copper stage: Cu
2+40g/L, H
2sO
4100g/L, T40 ~ 60 DEG C, current density 1500A/m
2;
Melanism copper one-phase: Cu
2+5g/L, H
2sO
4100g/L, T20 ~ 25 DEG C, 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 DEG C, 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 DEG C, pH8 ~ 10, light hair side current density 50A/m
2;
The passivation stage: Cr
3+1 ~ 2g/L, T30 ~ 60 DEG C, K
4p
2o
7100g/L, pH8 ~ 10, light hair side current density 20A/m
2;
Hot water wash: T40 ~ 60 DEG C, P0.2 ~ 0.3Mpa;
Silane treatment stage: γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane concentration 0.2 ~ 0.4%, pH6-8;
Dry: temperature 200 ~ 300 DEG C.
By hair side surfaceness Rz≤2.5 μm of embodiment 1 scheme 18 μm of electrolytic copper foils, its peel strength >=1.35kg/cm, HighTg, Halogen-free, thickness >=0.5mm sheet material peel strength >=1.10kg/cm.
The surface treatment embodiment 2 of electrolytic copper foil.
Pickling stages: Cu
2+≤ 10g/LH
2sO
4100 ~ 200g/L, T20 ~ 40 DEG C
The alligatoring copper stage: Cu
2+12g/L, H
2sO
4100g/L, T20 ~ 25 DEG C, current density 3500,1200,3500,1200A/m
2;
Solidification copper stage: Cu
2+50g/L, H
2sO
4100g/L, T40 ~ 60 DEG C, current density 2500A/m
2;
Melanism copper one-phase: Cu
2+5g/L, H
2sO
4100g/L, T20 ~ 25 DEG C, 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 DEG C, 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 DEG C, pH8 ~ 10, light hair side current density 100A/m
2;
The passivation stage: Cr
3+1g/LT30 ~ 60 DEG C, K
4p
2o
7the smooth hair side current density 10A/m in 100g/L, pH8 ~ 10
2;
Hot water wash: T40 ~ 60 DEG C, P0.2 ~ 0.3Mpa;
Silane treatment stage: γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane concentration 0.2 ~ 0.4%, pH6-8;
Dry: temperature 200 ~ 300 DEG C.
By hair side surfaceness Rz≤2.5 μm of embodiment 2 scheme 18 μm of electrolytic copper foils, its peel strength >=1.45kg/cm, HighTg, Halogen-free, thickness >=0.5mm sheet material peel strength >=1.20kg/cm.
Method of the present invention is adopted to carry out effect before and after surface treatment as depicted in figs. 1 and 2 to electrolytic copper foil.After method process of the present invention, electrolytic copper foil surface roughness obviously reduces.
Claims (8)
1. a high heat-resisting electrolytic copper foil, is characterized in that: it is the electrolytic copper foil being suitable for the high-speed high frequency of LOWDk/Df, high heat-resisting CCL and pcb board material demand, and its hair side crystal grain is laminated crystalline; Described electrolytic copper foil thickness is 18 μm, hair side roughness Rz≤2.5 μm, FR4 sheet material peel strength >=1.45kg/cm, tensile strength >=380MPa, unit elongation >=6%; Or described electrolytic copper foil thickness is 35 μm, hair side roughness Rz≤4.5 μm, FR4 sheet material peel strength >=2.00kg/cm, tensile strength >=330MPa, unit elongation >=8%.
2. prepare the method for the heat-resisting electrolytic copper foil of height according to claim 1 for one kind, it is characterized in that, after adopting DC electrodeposition technique to obtain electrolytic copper foil, run in electrolyzer with the speed of 16 ~ 18m/min, in electrolyzer, the cooperation process of different electrolyte combination and DC electrodeposition processing parameter is taked by multiple stage, carry out cleanup acid treatment, low roughening treatment, solidification treatment, Darkening process, washing, anti-oxidation process, hot water wash, silane treatment and baking operation to the surface of electrolytic copper foil, its technical process is as follows:
Pickling stages: in electrolytic solution, Cu
2+concentration≤10g/L, H
2sO
4concentration 100 ~ 200g/L, temperature 20 ~ 40 DEG C;
The alligatoring copper stage: in electrolytic solution, Cu
2+concentration 8 ~ 16g/L, H
2sO
4concentration 100 ~ 220g/L, temperature 20 ~ 25 DEG C, current density 1200 ~ 3500A/m
2;
The solidification copper stage: in electrolytic solution, Cu
2+concentration 20 ~ 60g/L, H
2sO
4concentration 100 ~ 200g/L, temperature 40 ~ 60 DEG C, 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, temperature 20 ~ 25 DEG C, 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, C
6h
5na
3o
72H
2o concentration 50 ~ 100g/L, (NH
4)
2sO
4concentration 50 ~ 100g/L, temperature 20 ~ 25 DEG C, pH3 ~ 5, current density 200 ~ 500A/m
2;
Washing;
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, temperature 20 ~ 50 DEG C, pH8 ~ 10, current density 50 ~ 100A/m
2;
The passivation stage: in electrolytic solution, Cr
3+concentration 1 ~ 2g/L, temperature 30 ~ 60 DEG C, K
4p
2o
7concentration 30 ~ 100g/L, pH8 ~ 10, current density 10 ~ 20A/m
2;
Hot water wash: temperature 40 ~ 60 DEG C, pressure 0.2 ~ 0.3MPa;
Silane treatment stage: γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane mass percent concentration is 0.2 ~ 0.4%, pH6-8;
Dry: temperature 200 ~ 300 DEG C.
3. the preparation method of the heat-resisting electrolytic copper foil of height according to claim 2, 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.
4. the preparation method of the heat-resisting electrolytic copper foil of height according to claim 2, is characterized in that: the described solidification copper stage, current density divide two sections given, given current density is respectively 1500 ~ 2500A/m
2with 1500 ~ 2500A/m
2.
5. the preparation method of the heat-resisting electrolytic copper foil of height according to claim 2, 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.
6. the preparation method of the heat-resisting electrolytic copper foil of height according to claim 2, 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.
7. the preparation method of the heat-resisting electrolytic copper foil of height according to claim 2, it is characterized in that, the concrete grammar that described DC electrodeposition technique obtains electrolytic copper foil is, adopt DC electrodeposition technique that electrolytic solution composition is carried out reasonable coordination with DC electrodeposition processing parameter, and organic blending additive is added in electrolytic process, its technical process is as follows: adopt electrolytic solution Cu
2+concentration 70 ~ 80g/L, H
2sO
4concentration 80 ~ 120g/L, Cl
-the parameter coordination temperature of concentration 20 ± 5ppm 50 ~ 60 DEG C, flow 40 ~ 50m
3/ h, current density 5000 ~ 6000A/m
2carry out DC electrodeposition; Described organic additive is Mierocrystalline cellulose and gelatin.
8. the preparation method of the heat-resisting electrolytic copper foil of height according to claim 7, 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 DEG C is 80 ~ 125CPS; The molecular weight of described gelatin is 10000 ~ 30000.
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|---|---|---|---|
| CN201310360643.2A CN103397342B (en) | 2013-08-19 | 2013-08-19 | A kind of high heat-resisting electrolytic copper foil and preparation method thereof |
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|---|---|---|---|
| CN201310360643.2A CN103397342B (en) | 2013-08-19 | 2013-08-19 | A kind of high heat-resisting electrolytic copper foil and preparation method thereof |
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| CN103397342A CN103397342A (en) | 2013-11-20 |
| CN103397342B true CN103397342B (en) | 2016-03-30 |
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| 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 |
| CN104651885B (en) * | 2015-02-12 | 2017-02-01 | 安徽铜冠铜箔有限公司 | Preparation method of electronic copper foil |
| KR20170036262A (en) * | 2015-09-24 | 2017-04-03 | 엘에스엠트론 주식회사 | Electrolytic Copper Foil, Electrode Comprising The Same, Secondary Battery Comprising The Same, and Method for Manufacturing The Same |
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| 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 |
| 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 |
| CN111910223B (en) * | 2020-08-24 | 2022-04-22 | 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 |
| 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 |
| CN112839436B (en) * | 2020-12-30 | 2022-08-05 | 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 thereof |
| 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 |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004263296A (en) * | 2003-02-12 | 2004-09-24 | Furukawa Techno Research Kk | Copper foil for fine pattern printed circuit and manufacturing method therefor |
| JP2005307270A (en) * | 2004-04-21 | 2005-11-04 | Mitsui Mining & Smelting Co Ltd | Carrier foil-fitted electrolytic copper foil and method for producing the carrier foil-fitted electrolytic copper foil |
| CN1958864A (en) * | 2005-11-04 | 2007-05-09 | 苏西（中国）铜箔有限公司 | Organic blending additive in use for producing ultrathin two-faced bright electrolytic copper foil |
| CN101067210A (en) * | 2007-01-26 | 2007-11-07 | 湖北中科铜箔科技有限公司 | Electrolytic copper foil with low-contour and high property and producing method thereof |
| CN101532149A (en) * | 2009-03-06 | 2009-09-16 | 汪汉平 | A two-sided light high performance electrolytic copper foil and its preparation method |
| CN101962789A (en) * | 2010-09-30 | 2011-02-02 | 湖北中科铜箔科技有限公司 | Electrolytic copper foil for high-power LED flexible circuit board and preparation method thereof |
| CN102277597A (en) * | 2011-08-12 | 2011-12-14 | 合肥铜冠国轩铜材有限公司 | Preparation of double-sided photoelectrolytic copper foil for special lithium battery |
| CN103132110A (en) * | 2013-03-20 | 2013-06-05 | 清新县联鑫科技铜箔有限公司 | Preparation method of high-performance electrolytic copper foil |
-
2013
- 2013-08-19 CN CN201310360643.2A patent/CN103397342B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004263296A (en) * | 2003-02-12 | 2004-09-24 | Furukawa Techno Research Kk | Copper foil for fine pattern printed circuit and manufacturing method therefor |
| JP2005307270A (en) * | 2004-04-21 | 2005-11-04 | Mitsui Mining & Smelting Co Ltd | Carrier foil-fitted electrolytic copper foil and method for producing the carrier foil-fitted electrolytic copper foil |
| CN1958864A (en) * | 2005-11-04 | 2007-05-09 | 苏西（中国）铜箔有限公司 | Organic blending additive in use for producing ultrathin two-faced bright electrolytic copper foil |
| CN101067210A (en) * | 2007-01-26 | 2007-11-07 | 湖北中科铜箔科技有限公司 | Electrolytic copper foil with low-contour and high property and producing method thereof |
| CN101532149A (en) * | 2009-03-06 | 2009-09-16 | 汪汉平 | A two-sided light high performance electrolytic copper foil and its preparation method |
| CN101962789A (en) * | 2010-09-30 | 2011-02-02 | 湖北中科铜箔科技有限公司 | Electrolytic copper foil for high-power LED flexible circuit board and preparation method thereof |
| CN102277597A (en) * | 2011-08-12 | 2011-12-14 | 合肥铜冠国轩铜材有限公司 | Preparation of double-sided photoelectrolytic copper foil for special lithium battery |
| CN103132110A (en) * | 2013-03-20 | 2013-06-05 | 清新县联鑫科技铜箔有限公司 | Preparation method of high-performance electrolytic copper foil |
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