CN106191980A - The surface Darkening process method of rolled copper foil - Google Patents
The surface Darkening process method of rolled copper foil Download PDFInfo
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- CN106191980A CN106191980A CN201610600469.8A CN201610600469A CN106191980A CN 106191980 A CN106191980 A CN 106191980A CN 201610600469 A CN201610600469 A CN 201610600469A CN 106191980 A CN106191980 A CN 106191980A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F1/00—Electrolytic cleaning, degreasing, pickling or descaling
- C25F1/02—Pickling; Descaling
- C25F1/04—Pickling; Descaling in solution
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
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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
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/38—Chromatising
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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
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/22—Electroplating: Baths therefor from solutions of zinc
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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
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
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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
- 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
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F3/00—Electrolytic etching or polishing
- C25F3/02—Etching
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/20—Use of solutions containing silanes
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- Inorganic Chemistry (AREA)
- Mechanical Engineering (AREA)
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Abstract
The invention discloses a kind of surface Darkening process method of rolled copper foil, in turn include the following steps: (1) electrochemical degreasing, (2) roughening treatment, (3) cured, the process of (4) nickel plating cobalt, (5) zinc-plated process, (6) passivation, (7) are coated with silane coupling agent and process and (8) drying and processing, obtain product, step (1)~step (6), all alive.The rolled copper foil melanism process for treating surface of the present invention, its advantageous is after each road electroplating work procedure, and the Copper Foil appearance of black obtained meets FPC requirement.After measured, copper foil surface color blackness value is below 30;Surface roughness Ra≤1.0 μm, Rz≤2.0 μm;Peel strength reaches more than 1.4N/mm;More than folding MIT800;There is good acid resistance, alkali resistance, soldering resistance, and etching.Blackness value RAL7016, has good photoextinction.
Description
Technical field
The present invention relates to the surface treatment method of a kind of rolled copper foil, be specifically related to the surface melanism method of rolled copper foil.
Background technology
Copper Foil is one of primary raw material of FCCL (the processing base material of flexible print wiring board), different according to production method,
Copper Foil can be divided into two big classes, is rolled copper foil and electrolytic copper foil respectively.
Described rolled copper foil is to utilize plastic working principle, by the repeat-rolling-annealing process of copper ingot is formed, its
Internal organizational structure is flaky crystal tissue, and rolled copper foil product has good ductility, shoulders flexibility, low roughness and height
Folding resistance, it has also become the basic material of flexible printed-circuit board.Present stage, rolled copper foil is mainly used in flexible electric circuit board and high frequency
In circuit board.
Recently, PDP is big with its screen, and brightness is high, and color reducibility is good, and gray scale is enriched, to change rapidly
Picture fast response time, the advantage such as ultra-thin, applied rapidly in various display devices.The work process of PDP panel is profit
Produce the principle of plasma discharge by mixed gas such as neon-xenons through high pressure effect, control the luminescence of each point to realize Dynamic Graph
As, in its drive circuit, therefore there is bigger pulse current, its circuit and panel inevitably have part frequency electromagnetic waves
Produce, environment is had certain electromagnetic pollution.This just requires to increase by one layer of electromagnetism wave screen before the PDP panel of current all productions
Cover film, realize the shielding to harmful frequency electromagnetic waves, and the effect of PDP presentation of displayed picture can be had a certain upgrade.
Electromagnetic shielding film conduction silk screen is transitted towards conductive mesh from metalized fibers fabric, wherein uses metal forming
Etching and processing and the electromagnetic wave shielding obtained conduction silk screen become main flow.As shielding panel basis Copper Foil owing to having gold
Belong to gloss, it is possible to reflection, from the light outside plate, produces light in making the degradation in contrast of screen, and reflective viewing screen, makes light
Absorbance declines, and the visibility of display screen declines.Therefore, let out to effectively shield the line-spectra of electromagnetic wave and near infrared region
Leakage, promotes PDP Display panel graphical effects, needs copper foil shielding layer is carried out Darkening process, to obtaining the pressure of appearance of black
Prolong Copper Foil.
Owing to the structure of rolled copper foil is different with electrolytic copper foil with purposes, the requirement processing its surface is higher.Due to copper
Paper tinsel blank has Residual oil, so the oil removing of rolled copper foil seems increasingly important.In order to increase and the binding ability of printed board substrate, with
Sample needs to carry out the dendritic copper facing in surface on its Copper Foil faying face, and resolidification, to increase the surface roughness of faying face.In order to full
Foot trip thermostability and the requirement such as corrosion resistance and solderability, it is necessary on the basis of roughening, plate layer of metal or alloy as resistance
Barrier, the barrier layer of rolled copper foil typically uses two kinds of processing modes, i.e. Darkening process (copper-cobalt-nickel or copper-nickel coating) and red
Change processes (fine copper coating).
The zinc-nickel coating the most also developed, finally does passivation and processes with organic membrane.It is main that its surface processes
Technological process includes successively:
Electrochemical deoiling, washing, pickling, washing, roughening treatment (copper coating), washing, cured (plating of surface essence), water
Wash, galvanized alloy or admiro, wash, be passivated, wash → be coated with silane coupling agent and drying.
Reddening (copper facing) or ashing (zinc-plated) process rolled copper foil and are substantially the processing method indiscriminately imitating electrolytic copper foil, with this kind
The FCCL that the rolled copper foil that surface processes is made, its appearance color, anti-stripping, etching, solderability all cannot meet the system of PDP
It is required.
Summary of the invention
It is an object of the invention to provide a kind of surface Darkening process method of rolled copper foil, to overcome prior art to exist
Drawbacks described above, meets the needs of association area application.
The method of the present invention, in turn includes the following steps:
(1) electrochemical degreasing, (2) roughening treatment, (3) cured, the process of (4) nickel plating cobalt, (5) zinc-plated process, (6) are blunt
Change, (7) are coated with silane coupling agent and process and (8) drying and processing, it is thus achieved that product;
Step (1)~step (6), all alive;
Between each step of step (2)~step (7), also include water-washing step;
Between step (1) and step (2), include washing, pickling and water-washing step the most successively;
Preferably, the electrochemical degreasing of step (1) includes 2~4 times, also includes water-washing step between adjacent twice;
Preferably, the roughening treatment of step (2) includes 2~4 times, preferably 2 times, also includes washing step between adjacent twice
Suddenly;
Preferably, the cured of step (3) includes 2~4 times, preferably 2 times, also includes washing step between adjacent twice
Suddenly;
Further, in described electrochemical degreasing step (1), oil removing solution is sodium hydrate aqueous solution, wherein OH-Concentration
Being 30~40g/L, room temperature, electric current density is 2.5~3.5A/dm2;
Further, in described roughening treatment step (2), the concentration of roughening solution used is:
Cu2+20-40g/L, H2SO4100-150g/L, temperature is 20-40 DEG C, and electric current density is 15-50A/dm2;
Preferably, when using the roughening treatment process of 2~4 times, first roughening solution contains the component of following concentration:
Cu2+20-30g/L, H2SO4100-150g/L, temperature is 20-40 DEG C, and electric current density is 15-20A/dm2;During process
Between be 4~6s;
Second to the 4th time, roughening solution contains the component of following concentration of component:
Cu2+30-40g/L, H2SO4120-150g/L, temperature is 20-40 DEG C, and electric current density is 35-50A/dm2;
Further, in described cured step (3), curing solution used contains the component of following concentration:
Cu2+30-50g/L, H2SO480-110g/L, temperature is 40-50 DEG C, and electric current density is 8-20A/dm2;
Preferably, when using the cured step of 2~4 times, curing solution used by primary curing process step contains
The component of following concentration:
Cu2+30-40g/L, H2SO480-110g/L, temperature is 40-50 DEG C, and electric current density is 15-20A/dm2;Remaining
In cured step, curing solution contains the component of following concentration: Cu2+40-50g/L, H2SO480-110g/L, temperature is
40-50 DEG C, electric current density is 8-12A/dm2;
Further, described nickel plating cobalt processes in (step 4), and nickel plating cobalt liquor used contains the component of following concentration:
Ni2+40-60g/L, Co2+1-5g/L, NH4 +20-50g/L, chelating agent 22-28g/L, buffer agent 20-40g/L, melanism
Agent 5-100g/L;
Described chelating agent is selected from citric acid or sodium citrate;
Described buffer agent is selected from boric acid;
Described black agent is selected from NH4 +、K+、SCN-、NH2 +、CS2-One in compound, preferred compound be KSCN,
NH4SCN or SC (NH2)2;
Electric current density 16-24A/dm2, temperature is 0-50 DEG C, pH2-6;
Further, in described zinc-plated process step (5), galvanizing solution used contains the component of following concentration: Zn2+20-
30g/L;
Electric current density 0.3-0.5A/dm2, temperature is 20-30 DEG C;
Further, in described passivation step (6), passivating dip used is the CrO containing following component3 -1-5g/L is molten
Liquid, electric current density 0.2-0.4A/dm2, temperature is 20-30 DEG C;
Further, described spraying silane coupling agent processes in step (7), spraying be weight concentration be 3%~7%
Silane coupler aqueous solution, the spraying weight of the silane coupling agent of butt is 0.1-0.7 gram/cm2;
Term " butt ", refers to water-free silane coupling agent;
Described silane coupling coupling agent can use Guangzhou Kang Ou double trade Co., Ltds trade mark to be the product of KH-550, its
Chemical name is gamma-aminopropyl-triethoxy-silane;
Further, described drying and processing step (8), drying temperature is 150~200 DEG C;
Further, described Acidwash solution is sulphuric acid, wherein H+Concentration is 30-50g/L, temperature room temperature;
Preferably, above-mentioned step (1) is to step (8), and the Copper Foil speed of service is 20-30m/min, in the range of, Mei Gexu
In the time of staying be 4-6s;
The definition of term " electrochemical degreasing, roughening treatment, cured, nickel plating cobalt process, zinc-plated process and passivation " and
Relevant operating process, can be found in calender copper foil of printing circuit board process of surface treatment and the report of coating performance Research Literature
Road, the present invention repeats no more.Those skilled in the art, if it is desired, can be directly refering to plating handbook.
The black surface processing procedure of rolled copper foil of the present invention is made up of above-mentioned step, can thoroughly remove surface trace
Residual oil;Pickling washing trough pickling, removes surface small amounts thing and makes the fresh cleaning of copper foil surface;In order to increase and printed board substrate
Binding ability, the present invention uses repeatedly roughening and cured;Want with corrosion resistance and solderability etc. to meet Copper Foil thermostability
Ask, use nickel plating cobalt to obtain the Copper Foil of appearance of black;In order to prevent Copper Foil oxidation when using or store, Copper Foil plates one layer of chromium
Hydrochlorate is passivated processing;Finally, for making rolled copper foil and pi thin film have good adhesion, also need to cover one layer of silicon of painting
Alkane.The selection of silane is relevant with film material, and target is to obtain optimal cohesive force.
Invention effect
The rolled copper foil melanism process for treating surface of the present invention, its advantageous, after each road electroplating work procedure, obtains
To Copper Foil appearance of black meet FPC requirement.After measured, copper foil surface color blackness value is below 30;Surface roughness Ra≤
1.0 μm, Rz≤2.0 μm;Peel strength reaches more than 1.4N/mm;More than folding MIT800;There is good acid resistance, alkali resistance,
Soldering resistance, and etching.Blackness value RAL7016, has good photoextinction.
Detailed description of the invention
Specific embodiments of the present invention are presented herein below, further illustrate the technical solution of the present invention, but the present invention
Embodiment is not limited to embodiment in detail below.
Embodiment 1
The black surface treatment process of rolled copper foil, in turn includes the following steps:
Electrochemical degreasing, washing, electrochemical degreasing, washing, electrochemical degreasing, washing, pickling, washing, roughening treatment, water
Wash, secondary roughening treatment, washing, cured, washing, secondary cured, washing, nickel plating cobalt, washing, zinc-plated, washing, blunt
Change, wash, be coated with silane coupling agent, drying, rolling are rolled off the production line.
Wherein:
Electrochemical degreasing solution used is sodium hydrate aqueous solution, wherein OH-Concentration is 35g/L, temperature room temperature, electrochemistry
The electric current density of oil removing is 3A/dm2;
Acidwash solution used is sulphuric acid, wherein H+Concentration is 30g/L, temperature room temperature;
First roughening solution used, wherein Cu2+22g/L, H2SO4115g/L, temperature is 30 DEG C, and electric current density is 15A/
dm2;
Secondary roughening solution used, wherein Cu2+32g/L, H2SO4125g/L, temperature is 30 DEG C, and electric current density is 35A/
dm2;
Primary curing solution used, wherein Cu2+32g/L, H2SO485g/L, temperature is 40 DEG C, and electric current density is 15A/
dm2;
Secondary curing solution used, wherein Cu2+42g/L, H2SO485g/L, temperature is 40 DEG C, and electric current density is 8A/dm2;
Nickel plating solution used, wherein Ni2+40g/L, Co2+1g/L, NH4 +20g/L, chelating agent 22g/L, buffer agent 20g/L,
Black agent 15g/L, wherein:
Chelating agent is citric acid, and buffer agent is boric acid, and black agent is KSCN, electric current density 16A/dm2, temperature is 40 DEG C,
PH3;
Galvanizing solution used, Zn2+20g/L, electric current density 0.3A/dm2, temperature is 30 DEG C;
Passivating dip used, wherein: CrO3 -1g/L, electric current density 0.2A/dm2, temperature is 30 DEG C;
Spraying silane coupler used is the silane coupler aqueous solution of weight concentration 3%, uses the double trade of Guangzhou Kang Ou
Company limited's chemical name is the product of gamma-aminopropyl-triethoxy-silane, and the spraying weight of the silane coupling agent of butt is 0.3
Gram/cm2;
Drying temperature is 150 DEG C;
The Copper Foil speed of service is 20m/min, and the time of staying in each sequence is 6s,
The copper foil surface color blackness value obtained through above-mentioned process is RAL7016, surface roughness Ra=0.72 μm, Rz
=1.41 μm;Peel strength reaches more than 1.5N/mm;Folding MIT815;There is good acid resistance, alkali resistance, soldering resistance, and erosion
Quarter property.
Embodiment 2
The present embodiment compared with Example 1, distinguish with:
Electrochemical degreasing solution used is sodium hydrate aqueous solution, wherein OH-Concentration is 40g/L, temperature room temperature, electrochemistry
The electric current density of oil removing is 4A/dm2;
Acidwash solution used by is sulphuric acid, wherein H+Concentration is 35g/L, temperature room temperature;
First roughening solution used, wherein Cu2+26g/L, H2SO4125g/L, temperature is 30 DEG C, and electric current density is 18A/
dm2;
Secondary roughening solution used, wherein Cu2+36g/L, H2SO4135g/L, temperature is 30 DEG C, and electric current density is 38A/
dm2;
Primary curing solution used, wherein Cu2+36g/L, H2SO495g/L, temperature is 40 DEG C, and electric current density is 17A/
dm2;
Secondary curing solution used, wherein Cu2+40g/L, H2SO495g/L, temperature is 40 DEG C, and electric current density is 10A/
dm2;
Nickel plating solution used, wherein Ni2+44g/L, Co2+3g/L, NH4 +30g/L, chelating agent 26g/L, buffer agent 26g/L,
Black agent 15g/L.Its complexing agent selects citric acid, and boric acid selected by buffer agent, and black agent is selected from NH4SCN;Electric current density 19A/
dm2, temperature is 40 DEG C, PH3;
Galvanizing solution used, wherein Zn2+24g/L, electric current density 0.3A/dm2, temperature is 30 DEG C;
Passivating dip used, wherein CrO3 -1g/L, electric current density 0.2A/dm2, temperature is 30 DEG C
Spraying silane coupler used is the silane coupler aqueous solution of weight concentration 5%, the silane coupling agent of butt
Spraying weight is 0.3 gram/cm2;Silane coupler uses Guangzhou Kang Ou double trade Co., Ltds chemical name to be γ-aminopropyl three
The product of Ethoxysilane;
Drying temperature is 160 DEG C;
The Copper Foil speed of service is 30m/min, and the time of staying in each sequence is 4s;
The copper foil surface color blackness value obtained through above-mentioned process is RAL7016, surface roughness Ra=0.18 μm, Rz
=1.93 μm;Peel strength reaches 1.4N/mm;Folding MIT850;There is good acid resistance, alkali resistance, soldering resistance, and etching
Property.
Embodiment 3
The present embodiment compared with Example 2, distinguish with:
Oil removing solution used is sodium hydrate aqueous solution, wherein OH-Concentration is 45g/L, temperature room temperature, electrochemical degreasing
Electric current density is 5A/dm2;
Acidwash solution used is sulphuric acid, wherein H+Concentration is 40g/L, temperature room temperature;
First roughening solution used, wherein Cu2+26g/L, H2SO4120g/L, temperature is 30 DEG C, and electric current density is 16A/
dm2;
Secondary roughening solution used, wherein Cu2+34g/L, H2SO4130g/L, temperature is 30 DEG C, and electric current density is 37A/
dm2;
Primary curing solution used, wherein Cu2+40g/L, H2SO490g/L, temperature is 40 DEG C, and electric current density is 16.2A/
dm2;
Secondary curing solution used, wherein Cu2+35g/L, H2SO490g/L, temperature is 40 DEG C, and electric current density is 9.4A/
dm2;
Nickel plating solution used, wherein Ni2+42g/L, Co2+4g/L, NH4 +25g/L, chelating agent 24g/L, buffer agent 24g/L,
Black agent 8g/L.Its complexing agent selects sodium citrate, and boric acid selected by buffer agent, and black agent selects SC (NH2)2;Electric current density 18A/
dm2, temperature is 40 DEG C, PH3;
Galvanizing solution used, wherein Zn2+22g/L, electric current density 0.3A/dm2, temperature is 30 DEG C;
Passivating dip used, wherein CrO3 -1g/L, electric current density 0.2A/dm2, temperature is 30 DEG C
Spraying silane coupler used is silane coupler aqueous solution.
Spraying silane coupler used is the silane coupler aqueous solution of weight concentration 7%, the silane coupling agent of butt
Spraying weight is 0.5 gram/cm2;Silane coupler uses Guangzhou Kang Ou double trade Co., Ltds chemical name to be γ-aminopropyl three
The product of Ethoxysilane;
Drying temperature is 170 DEG C;
The Copper Foil speed of service is 30m/min, and the time of staying in each sequence is 4s.
The copper foil surface color blackness value obtained through above-mentioned process is RAL7021, surface roughness Ra=0.23 μm, Rz
=1.99 μm;Peel strength reaches 1.6N/mm;Folding MIT815;There is good acid resistance, alkali resistance, soldering resistance, and etching
Property.
Embodiment 4
Compared with Example 3, difference is the present embodiment:
Oil removing solution used is sodium hydrate aqueous solution, wherein OH-Concentration is 50g/L, temperature room temperature, electrochemical degreasing
Electric current density is 6A/dm2;
Acidwash solution used is sulphuric acid, wherein H+Concentration is 50g/L, temperature room temperature;
First roughening solution used, wherein Cu2+30g/L, H2SO4130g/L, temperature is 30 DEG C, and electric current density is 18A/
dm2;
Secondary roughening solution used, wherein Cu2+28g/L, H2SO4130g/L, temperature is 30 DEG C, and electric current density is 39A/
dm2;
Primary curing solution used, wherein Cu2+50g/L, H2SO4110g/L, temperature is 40 DEG C, and electric current density is 20A/
dm2;
Secondary curing solution used, wherein Cu2+45g/L, H2SO4105g/L, temperature is 40 DEG C, and electric current density is 12A/
dm2;
Nickel plating solution used, wherein Ni2+45g/L, Co2+5g/L, NH4 +35g/L, chelating agent 30g/L, buffer agent 28g/L,
Black agent 5g/L.Its complexing agent selects citric acid, and boric acid selected by buffer agent, and black agent selects SC (NH2)2;Electric current density 22A/
dm2, temperature is 40 DEG C, PH4;
Galvanizing solution used, wherein Zn2+26g/L, electric current density 0.4A/dm2, temperature is 30 DEG C;
Passivating dip used, wherein CrO3 -1g/L, electric current density 0.2A/dm2, temperature is 30 DEG C;
Spraying silane coupler used is silane coupler aqueous solution.
Spraying silane coupler used is silane coupler aqueous solution.Spraying silane coupler used is weight concentration?3%
Silane coupler aqueous solution, the spraying weight of the silane coupling agent of butt is 0.7 gram/cm2;Silane coupler uses Guang Zhoukang
Ou Shuan trade Co., Ltd chemical name is the product of gamma-aminopropyl-triethoxy-silane;
Drying temperature is 180 DEG C;
The copper foil surface color blackness value obtained through above-mentioned process is RAL7022, surface roughness Ra=0.26 μm, Rz
=1.53 μm;Peel strength reaches 2.0N/mm;Folding MIT875;There is good acid resistance, alkali resistance, soldering resistance, and etching
Property.
Claims (17)
1. the surface Darkening process method of rolled copper foil, it is characterised in that in turn include the following steps:
(1) electrochemical degreasing, (2) roughening treatment, (3) cured, the process of (4) nickel plating cobalt, (5) zinc-plated process, (6) passivation,
(7) it is coated with silane coupling agent to process and (8) drying and processing, it is thus achieved that product;
In the either step of step (1)~step (6), all alive.
Method the most according to claim 1, it is characterised in that between each step of step (2)~step (7), also
Including water-washing step;Between step (1) and step (2), include washing, pickling and water-washing step the most successively.
Method the most according to claim 1, it is characterised in that the electrochemical degreasing of step (1) includes 2~4 times, adjacent
Water-washing step is also included between twice.
Method the most according to claim 1, it is characterised in that the roughening treatment of step (2) includes 2~4 times, adjacent two
Water-washing step is also included between secondary.
Method the most according to claim 1, it is characterised in that the cured of step (3) includes 2~4 times, adjacent two
Water-washing step is also included between secondary.
Method the most according to claim 1, it is characterised in that in described electrochemical degreasing step (1), oil removing solution is
Sodium hydrate aqueous solution, wherein OH-Concentration is 30~40g/L, room temperature, and electric current density is 2.5~3.5A/dm2。
Method the most according to claim 1, it is characterised in that in described roughening treatment step (2), roughening solution used
Concentration be:
Cu2+20-40g/L, H2SO4100-150g/L, temperature is 20-40 DEG C, and electric current density is 15-50A/dm2。
Method the most according to claim 7, it is characterised in that when using the roughening treatment process of 2~4 times, the most slightly
Change solution and contain the component of following concentration:
Cu2+20-30g/L, H2SO4100-150g/L, temperature is 20-40 DEG C, and electric current density is 15-20A/dm2;The process time is 4
~6s;
Second to the 4th time, roughening solution contains the component of following concentration of component:
Cu2+30-40g/L, H2SO4120-150g/L, temperature is 20-40 DEG C, and electric current density is 35-50A/dm2。
Method the most according to claim 1, it is characterised in that in described cured step (3), curing solution used
Component containing following concentration:
Cu2+30-50g/L, H2SO480-110g/L, temperature is 40-50 DEG C, and electric current density is 8-20A/dm2。
Method the most according to claim 9, it is characterised in that when using the cured step of 2~4 times, solid for the first time
Change processes the component that curing solution used by step contains following concentration:
Cu2+30-40g/L, H2SO480-110g/L, temperature is 40-50 DEG C, and electric current density is 15-20A/dm2;At remaining solidification
In reason step, curing solution contains the component of following concentration: Cu2+40-50g/L, H2SO480-110g/L, temperature is 40-50 DEG C,
Electric current density is 8-12A/dm2。
11. methods according to claim 1, it is characterised in that described nickel plating cobalt processes in step (4), nickel plating used
Cobalt liquor contains the component of following concentration:
Ni2+40-60g/L, Co2+1-5g/L, NH4 +20-50g/L, chelating agent 22-28g/L, buffer agent 20-40g/L, black agent 5-
100g/L;
Described chelating agent is selected from citric acid or sodium citrate;
Described buffer agent is selected from boric acid;
Described black agent is selected from NH4 +、K+、SCN-、NH2 +、CS2-One in compound;
Electric current density 16-24A/dm2, temperature is 0-50 DEG C, pH2-6.
12. methods according to claim 1, it is characterised in that in described zinc-plated process step (5), used zinc-plated molten
Liquid contains the component of following concentration: Zn2+20-30g/L;Electric current density 0.3-0.5A/dm2, temperature is 20-30 DEG C.
13. methods according to claim 1, it is characterised in that in described passivation step (6), passivating dip used is
CrO containing following component3 -1-5g/L solution, electric current density 0.2-0.4A/dm2, temperature is 20-30 DEG C.
14. methods according to claim 1, it is characterised in that described spraying silane coupling agent processes in step (7),
Spraying be weight concentration be the silane coupler aqueous solution of 3%~7%, the spraying weight of the silane coupling agent of butt is 0.1-
0.7 gram/cm2。
15. methods according to claim 1, it is characterised in that described Acidwash solution is sulphuric acid, wherein H+Concentration is 30-
50g/L。
16. methods according to claim 11, it is characterised in that described black agent is selected from KSCN, NH4SCN or SC
(NH2)2。
17. according to the method described in any one of claim 1~16, it is characterised in that step (1) to step (8), and Copper Foil runs
Speed is 20-30m/min, and the time of staying of each operation is 4-6s.
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