CN109097750A - The preparation method of flexibility coat copper plate - Google Patents
The preparation method of flexibility coat copper plate Download PDFInfo
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- CN109097750A CN109097750A CN201711350693.7A CN201711350693A CN109097750A CN 109097750 A CN109097750 A CN 109097750A CN 201711350693 A CN201711350693 A CN 201711350693A CN 109097750 A CN109097750 A CN 109097750A
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- copper
- copper foil
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
- C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/021—Cleaning or etching treatments
- C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/20—Metallic material, boron or silicon on organic substrates
- C23C14/205—Metallic material, boron or silicon on organic substrates by cathodic sputtering
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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
- 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
- C23C28/02—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 only coatings only including layers of metallic material
- C23C28/021—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 only coatings only including layers of metallic material including 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
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
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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
Abstract
The present invention provides a kind of preparation methods of flexibility coat copper plate, the flexibility coat copper plate includes substrate film layer, the sputtering layer on a substrate film layer at least surface is arranged in, with the copper foil for conduction being arranged on the surface of the sputtering layer, and surface of the sputtering layer far from the substrate film layer, and the preparation method of the flexibility coat copper plate is arranged in the copper foil, comprising the following steps: provides substrate film layer, sided corona treatment is carried out to the surface of the substrate film layer, obtains surface modified substrates film layer；Copper is sunk in the surface modified substrates film surface magnetron sputtering method for sputtering layer；In the heavy copper of the sputtering layer electroplating surface, copper foil is prepared, wherein the method for the electroless Plating Copper are as follows: after forming the first electro copper foil on sputtering layer using the alkali copper precipitation method, form the second electro copper foil on first electro copper foil using the sour copper precipitation method.
Description
Technical field
The invention belongs to wiring board technology field more particularly to a kind of preparation methods of flexibility coat copper plate.
Background technique
Flexible print wiring board is that the design and production of line pattern are carried out on flexible substrate in a manner of printing
Product.As the special function unit for being applied to electronic interconnection, due to lightweight, ultra-thin, small in size, flexible good, especially
It is that flexible, curling and folding outstanding advantages, flexible print wiring board have obtained widely in modern electronics industry
Using.Especially in recent years, the continuous improvement with people to electronic apparatus micromation, lightweight and integrated requirement, it is flexible
Circuit board has become one of essential component in all kinds of high-tech electronic product manufacturings, is widely used in notebook electricity
Brain, digital camera, foldable mobile phone, LCD TV and satellite positioning-terminal etc..In this context, as the flexible print of production and processing
The basic material of printed circuit board, the manufacture and application of flexibility coat copper plate have similarly obtained development at full speed.
Flexibility coat copper plate refers to that the single or double in flexible insulating substrate is combined with the copper-clad plate of copper foil, has electrically
The characteristics of energy, hot property, excellent heat resistance.Currently, in the method that insulating substrate surface combines copper foil, there are mainly two types of.First
Kind method is that copper foil is bonded in insulating substrate surface by adhesive to prepare flexibility coat copper plate, and second method is directly exhausted
Edge substrate surface sinks copper as being electrolysed heavy copper for copper foil layer.Compared to first method, copper directly is prepared on insulating substrate surface
Layers of foil can not only reduce production cost, but also obtained flexible copper-clad plate thickness is lower, and most thin copper foil layer thickness can be controlled
System is at 6 μm or so.However, peel strength is too low between copper foil and substrate, can not prepare in insulating substrate surface directly heavy copper
The lower copper foil of thickness.However, with the Highgrade integration and ultra-thin micro of current line plate, ultra high density wiring and ultra-fine
Conduction has become development trend, and this kind of wiring board is higher and higher to the thickness requirement of flexibility coat copper plate, and client is to flexible copper-clad
The requirement that plate proposes 3-5 μm, is even less than 3 μm.In order to which flexibility coat copper plate meets customer requirement, generally require to obtained copper
Foil surface is etched to adapt it to the thickness requirements of product, and is thus greatly wasted copper foil material, increased life
Cost of manufacture is produced, and the performance uniformity of obtained flexibility coat copper plate is poor.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods of flexibility coat copper plate, it is intended to solve existing flexibility coat copper plate
In preparation method, directly when substrate surface sinks copper for copper foil, peel strength is low between copper foil and substrate, causes directly to be electroplated
Heavy copper can not produce the problem of copper foil of the thickness less than 3 μm.
For achieving the above object, The technical solution adopted by the invention is as follows:
One aspect of the present invention provides a kind of preparation method of flexibility coat copper plate, and the flexibility coat copper plate includes substrate film layer,
The sputtering layer on a substrate film layer at least surface, and the copper for conduction being arranged on the surface of the sputtering layer are set
Foil, and surface of the sputtering layer far from the substrate film layer, and the preparation side of the flexibility coat copper plate is arranged in the copper foil
Method, comprising the following steps:
Substrate film layer is provided, sided corona treatment is carried out to the surface of the substrate film layer, obtains surface modified substrates film layer；
Copper is sunk in the surface modified substrates film surface magnetron sputtering method for sputtering layer；
In the heavy copper of the sputtering layer electroplating surface, copper foil is prepared, wherein the method for the electroless Plating Copper are as follows: use alkali copper
After the precipitation method form the first electro copper foil on sputtering layer, second is formed on first electro copper foil using the sour copper precipitation method
Electro copper foil.
Preferably, include: for the step of sputtering layer in the heavy copper of the surface modified substrates film surface magnetron sputtering method
Under vacuum conditions, using nickel, copper as target, source parameters is set are as follows: 1000-4000W, 0.1-0.25A, the inlet air flow of argon gas
Amount is 180-230sccm, throughput is 30-50sccm out, sputters heavy copper, obtains sputtering layer.
Preferably, after forming the first electro copper foil on sputtering layer using the alkali copper precipitation method, using the sour copper precipitation method in institute
Stating the method that the second electro copper foil is formed on the first electro copper foil includes:
Alkaline Bath will be placed in the substrate film layer workpiece that at least a surface is prepared with sputtering layer, walking speed be 20Hz,
Alkali copper electroplating processes are carried out under conditions of electric current is 32.1A, voltage is 3.1, obtain the first copper foil；
Workpiece through alkali copper electroplating processes is placed in roughening electroplate liquid, carries out surface roughening treatment；
Workpiece after surface roughening treatment is placed in solidification electroplate liquid, curing process is carried out；
By in cured treated workpiece is placed in passivation electroplate liquid, surface passivating treatment is carried out, copper foil is obtained,
Wherein, the technological parameter of the surface roughening treatment, curing process, Passivation Treatment are as follows: walking speed 30Hz, electric current are
19+30+30+0.8A, voltage 4.3+3.2+3.0+2.2V.
Preferably, five water that the copper sulphate and concentration that the roughening electroplate liquid is 80-120g/L by concentration are 50-100g/L
Copper sulphate mixes.
It is preferably, described that solidify copper sulphate and concentration that electroplate liquid is 60-110g/L by concentration be the five of 100-200g/L
Brochanite mixes.
Preferably, the five water sulfuric acid that the zinc sulfate and concentration that the passivation electroplate liquid is 2-10g/L by concentration are 1-3g/L
Nickel mixes, and the pH of the roughening electroplate liquid is 3-5.
Preferably, the cupric pyrophosphate and concentration that the alkaline Bath is 30-100g/L by concentration are 200-400g/L's
Potassium pyrophosphate mixes, and the pH of the alkaline Bath is 8-10.
Preferably, in the step of substrate film layer is provided, carries out sided corona treatment to the surface of the substrate film layer, comprising: with
The power of 2.5-4kw carries out sided corona treatment to an at least surface for the substrate film layer, obtains surface modified substrates film layer.
Preferably, the copper foil layer with a thickness of 1 μm~3 μm.
Preferably, the sputtering layer with a thickness of 20nm~300nm.
Preferably, the substrate film layer with a thickness of 40 μm~60 μm.
The preparation method of flexibility coat copper plate provided by the invention, on the one hand, corona is carried out to the surface of the substrate film layer
It handles to increase the adhesive force on the surface of substrate film layer, to play the work of binding force between enhancing sputtering layer and substrate film layer
With；On the other hand, copper is sunk for sputtering layer in the surface modified substrates film surface magnetron sputtering method, further increase copper foil
Binding force between layer and substrate film layer, so can be improved the peel strength of entire flexibility coat copper plate.Therefore, by substrate
The surface of film layer carries out sided corona treatment and the substrate film surface spatter film forming in sided corona treatment, and flexibility coat copper plate has been effectively ensured
Peel strength, so as to by the thinner of the thickness design of copper foil layer so that the thickness of copper foil layer can be fabricated to it is small
In 3 μm of thickness.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of flexibility coat copper plate provided in an embodiment of the present invention.
Specific embodiment
In order to which technical problems, technical solutions and advantageous effects to be solved by the present invention are more clearly understood, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used to explain
The present invention is not intended to limit the present invention.
In the description of the present invention, it is to be understood that, term " first ", " second " are used for description purposes only, and cannot
It is interpreted as indication or suggestion relative importance or implicitly indicates the quantity of indicated technical characteristic.Define as a result, " the
One ", the feature of " second " can explicitly or implicitly include one or more of the features.In the description of the present invention,
The meaning of " plurality " is two or more, unless otherwise specifically defined.
The embodiment of the invention provides a kind of preparation methods of flexibility coat copper plate, comprising the following steps:
S01., substrate film layer is provided, sided corona treatment is carried out to the surface of the substrate film layer, obtains surface modified substrates film
Layer；
S02. copper is sunk for sputtering layer in the surface modified substrates film surface magnetron sputtering method；
S03. in the heavy copper of the sputtering layer electroplating surface, copper foil is prepared, wherein the electroless Plating Copper is using the sour copper precipitation method
It realizes.
The preparation method of flexibility coat copper plate provided in an embodiment of the present invention, on the one hand, to the surface of the substrate film layer into
Row sided corona treatment increases the adhesive force on the surface of substrate film layer, to play binding force between enhancing sputtering layer and substrate film layer
Effect；On the other hand, copper is sunk for sputtering layer in the surface modified substrates film surface magnetron sputtering method, further increase
Binding force between copper foil layer and substrate film layer, and then the peel strength of entire flexibility coat copper plate can be improved.Therefore, by right
The surface of substrate film layer carries out sided corona treatment and the substrate film surface spatter film forming in sided corona treatment, and flexibility has been effectively ensured and has covered
The peel strength of copper sheet, so as to by the thinner of the thickness design of copper foil layer, so that the thickness of copper foil layer can make
At the thickness less than 3 μm.
It should be noted that " ultra-thin " of ultra-thin flexible copper-clad plate provided in an embodiment of the present invention refers to the thickness of its copper foil layer
Degree can be made smaller than 3 μm of flexibility coat copper plate.
Specifically, providing substrate film layer in above-mentioned steps S01, the substrate film layer can select traditional polyimides
The other materials that film or other insulation performances that can satisfy ultra-thin flexible copper-clad plate require.Preferably, the base material film
Layer choosing polyethylene naphthalate film.Due to polyethylene naphthalate physical mechanical property with higher, change
Learn the performance of stability, heat resistance, UV resistant and radiation hardness etc..Therefore, made using polyethylene naphthalate film
It for substrate, can make the ultra-thin flexible copper-clad plate of the embodiment of the present invention on the basis of guaranteeing insulation effect, can have preferably
Physicochemical property extends the service life of product；Meanwhile the polyethylene naphthalate film can also be processed into it is transparent
Film can so enable the ultra-thin flexible copper-clad plate of the embodiment of the present invention to be processed into transparent ultra-thin flexible copper-clad plate,
When product requires ultra-thin flexible copper-clad plate transparency, then it can satisfy its requirement.
Further, sided corona treatment is carried out to the surface of the substrate film layer, obtains surface modified substrates film layer.Specifically
, sided corona treatment is a kind of shock treatment, it can make the surface of material have higher adhesion, and therefore, the present invention is implemented
The ultra-thin flexible copper-clad plate that example provides carries out sided corona treatment by the surface to the substrate film layer, to effectively increase the substrate
The surface adhesion force of film layer, so as to improve the binding force between the film layer and the substrate film layer that subsequent sputtering is formed.
Preferably, in the step of carrying out sided corona treatment to the surface of the substrate film layer, comprising: with the power of 2.5-4kw,
Sided corona treatment is carried out to an at least surface for the substrate film layer, obtains surface modified substrates film layer.In the present embodiment, to described
The power that substrate film layer carries out sided corona treatment is specifically as follows 2.5kw, 3.0kw, 3.5kw, 4.0kw etc..If the function of sided corona treatment
Rate is excessively high, then is easy the breakdown substrate film layer；If the power of sided corona treatment is too low, it is difficult to effectively improve the substrate film layer
Surface adhesion force, be unfavorable for it is subsequent sputtering formed film layer and the substrate film layer between binding force.
Sided corona treatment is carried out to the surface of the substrate film layer, is at least carried out on a surface of the substrate film layer.Specifically
, as an implementation, modified surface is formed on a surface of the substrate film layer, and then in the next steps, successively
Sputtering layer and copper foil are formed in modified surface, obtains single side ultra-thin flexible copper-clad plate.As another embodiment, in the base
Two surfaces of material film layer are respectively formed modified surface, and then in the next steps, successively form sputtering layer and copper in modified surface
Foil obtains double-side ultrathin flexibility coat copper plate.
Flexibility coat copper plate, copper foil are for conductive critical function layer.In the traditional preparation methods of flexibility coat copper plate, usually
Directly copper foil is prepared in substrate film surface.But directly in the heavy copper of electroplating surface of the substrate film layer through sided corona treatment
Standby copper foil, tends to the problem that peel strength is too low between copper foil layer and substrate thin layer and copper foil table is easy to oxidize occur.
In view of this, the embodiment of the present invention forms transition zone before preparing copper foil, in substrate film surface, for improving flexible copper-clad
The peel strength of plate, and then improve product working performance and service life.
In above-mentioned steps S02, copper is sunk for sputtering layer in the surface modified substrates film surface magnetron sputtering method.Pass through
Magnetron sputtering forms sputtering layer in copper-depositing on surface ion of the substrate film layer through sided corona treatment, the sputtering layer with it is described
The corona modified surface of substrate film layer is used in combination, to increase the binding force between copper foil layer and substrate film layer, and then can be with
Improve the peel strength of entire flexibility coat copper plate.Preferably, in the heavy copper of the surface modified substrates film surface magnetron sputtering method
The step of preparing sputtering layer includes: under vacuum conditions, using nickel, copper as target, source parameters to be arranged are as follows: 1000-4000W,
0.1-0.25A, the charge flow rate of argon gas is 180-230sccm, throughput is 30-50sccm out, sputters heavy copper, is sputtered
Layer.
When the embodiment of the present invention prepares sputtering layer, using nickel, copper as target, the ion deposition through bombardment changes on surface
Property substrate film surface, formed nickel-copper alloy layer.The nickel-copper alloy layer can not only increase between copper foil and substrate film layer
Binding force proposes the peel strength of flexibility coat copper plate；Moreover, because containing certain density nickel element in sputtering layer, can also disappear
It destatics, improves the working performance of flexibility coat copper plate.Substrate film layer after increasing sputtering layer can be higher than 6 μ with firm attachment thickness
The copper foil of m, it is not easily to fall off.Further, the electric current of nickel target is 2.5-4A, and the electric current of copper target material is 3-5A, and copper target material
Electric current is higher than the electric current of nickel target, and thus obtained monel sputtering layer has suitable ambrose alloy ratio, not only can more have
Effect ground improves adhesive force of the copper foil in substrate film layer, prepares for following plating steps；Meanwhile thus obtained monel
With better static elasticity eliminating effect.
Above-mentioned magnetron sputtering method sinks copper in the parameter of sputtering layer, in suitable electric current (0.1-0.25A), power
Under the conditions of (1000-4000W), target can be effectively bombarded, palladium ion is promoted to be incorporated in the substrate film layer through sided corona treatment
Surface forms the suitable sputtering layer of thickness.If the electric current is too low (power is too low), it is limited to bombard dynamics, it is difficult to be formed equal
Even sputtering layer, or even sputtering layer cannot be formed；If the electric current is excessively high (power is excessively high), the sputtering layer thickness of formation is blocked up,
Then violate the original intention that obtain ultra-thin flexible copper-clad plate originally, it is often more important that, blocked up sputtering layer, the property of will affect copper-clad plate
Service performance.
Further, in magnetron sputtering process, the charge flow rate that argon gas is arranged is 180-230sccm, throughput is 30- out
50sccm obtains the suitable sputtering layer of thickness to guarantee suitable bombardment dynamics.Specifically, if the charge flow rate mistake of argon gas
Height not only results in waste of resources, but also can reduce the vacuum degree in sputtering chamber, so as to cause vacuum sputtering effect variation, even
Sputtering layer can not be formed.
In above-mentioned steps S03, in the heavy copper of the sputtering layer electroplating surface, copper foil is prepared.It replaces passing using electroless Plating Copper method
The electrolysis of system sinks copper method and rolling process to make copper foil, can also equally play the work for increasing peeling force between copper foil and sputtering layer
With the thickness for diminution copper foil provides further guarantee, efficiently solves copper in conjunction with the setting of sided corona treatment and sputtering layer
Foil thickness has to accomplish 6 μm or more of technical bottleneck, improves the product qualification rate of ultra-thin flexible copper-clad plate；It also avoids simultaneously
Harsh technique is used to etch the problem of thicker copper foil is to obtain relatively thin copper foil.
As the first embodiment, electro-coppering that the electroless Plating Copper is formed on sputtering layer using the sour copper precipitation method
Foil.
Preferably, include: using the method that the sour copper precipitation method prepare copper foil
S031 will be placed in roughening electroplate liquid in the substrate film layer workpiece that at least a surface is prepared with sputtering layer, and it is thick to carry out surface
Change processing.
In the step, the workpiece of heavy copper to be electroplated is set in the substrate film layer workpiece that at least a surface is prepared with sputtering layer
Copper ion is promoted more efficiently to tie by composition, concentration and the electroplating parameter of regulation roughening electroplate liquid in roughening electroplate liquid
It closes in sputtering layer surface, in sputtering layer surface rapid precipitation copper ion, improves heavy copper speed, but the layers of copper that roughening treatment obtains is brilliant
Lattice are not close.Preferably, the copper sulphate and concentration that the roughening electroplate liquid is 80-120g/L by concentration are the five of 50-100g/L
Brochanite mixes.The embodiment of the present invention selects the copper sulphate of certain concentration, cupric sulfate pentahydrate as electroplate liquid system, benefit
In the fast enriching of copper ion.
Workpiece after surface roughening treatment is placed in solidification electroplate liquid by S032, carries out curing process.
In the step, the workpiece after surface roughening treatment is immersed in the solidification electroplate liquid, is solidified by regulation
Composition, concentration and the electroplating parameter of electroplate liquid, the not close layers of copper after surface roughening treatment carries out solidification stabilization, and is formed
The copper foil of dense uniform, to guarantee the service performance of copper foil.In the step, in order to adjust the solidification effect and deposition of copper ion
Uniformity needs to be adjusted the ion concentration in electrolyte, it is preferred that the solidification electroplate liquid is 60-110g/ by concentration
The copper sulphate and concentration of L is that the cupric sulfate pentahydrate of 100-200g/L mixes.The embodiment of the present invention selects copper sulphate, five water sulphur
Sour copper can effectively improve the deposition of copper ion as electroplate liquid system.And above-mentioned solidification electroplate liquid has suitable deposition ring
Border and copper ion concentration fill up not fine and close copper so as to which treated that layers of copper uniformly deposits copper ion being roughened
The gap of layer forms fine and close, copper foil in homogeneous thickness.
S033 carries out in cured treated workpiece is placed in passivation electroplate liquid surface passivating treatment, obtains copper foil.
The copper foil that cured processing obtains, the layers of copper activity on surface is higher, is easy to happen oxidation and influences its performance, such as drops
Low electric conductivity energy.In the step, treated that workpiece is placed in the passivation electroplate liquid by cured, passes through regulation passivation plating
Composition, concentration and the electroplating parameter of liquid carry out ion doping to the copper foil surface of formation, specifically, doping zinc ion and nickel
Ion prevents it to be oxidized to reduce the activity of surface layers of copper；Simultaneously as the copper foil that cured processing obtains, surface are thick
Rugosity is relatively high, by surface passivating treatment, zinc ion, nickel ion can be filled in coarse surface pits, to copper foil table
Face carries out polishing passivation, to obtain the flexibility coat copper plate of copper foil surface relative smooth.Preferably, the passivation electroplate liquid is by dense
The five water nickel sulfates that the zinc sulfate and concentration that degree is 2-10g/L are 1-3g/L mix, and the pH of the roughening electroplate liquid is
3-5.Zinc ion, the nickel ion concentration of suitable passivation electroplate liquid, are conducive to the doping for adjusting the zinc, nickel ion on copper foil surface layer
Amount, to prevent excessive zinc, nickel ion doping from leading to copper foil surface layer while realization prevents copper foil oxidation, surface passivation
Material change occurs for metallographic, and then influences the performance of copper foil itself.
In the step of sour copper precipitation method prepare copper foil, the surface roughening treatment, curing process, the technique of Passivation Treatment ginseng
Number are as follows: walking speed 30Hz, electric current 19+30+30+0.8A, voltage 4.3+3.2+3.0+2.2V.By controlling suitable electric current
Size can effectively control the deposition effect and deposition velocity of ion.Herein, electric current is that the understanding of 19+30+30+0.8A can be with
Electric current for surface roughening treatment is 19A, and curing process uses double-current, and electric current is 30A, and the electric current of Passivation Treatment is
0.8A；Double-current can also be used with surface roughening treatment, electric current is respectively 19A, 30A, and the electric current of curing process is 30A, passivation
The electric current of processing is 0.8A；Voltage is that four voltage datas in 4.3+3.2+3.0+2.2V respectively correspond aforementioned four electric currents
Value.
As second of embodiment, the electroless Plating Copper uses the electro-coppering that is formed on sputtering layer of the alkali copper precipitation method
Foil, thus obtains that copper thickness is thinner, the higher flexibility coat copper plate of surface brightness, and ultra-thin flexible is covered to meet client
The requirement of copper plate thickness, so that its copper thickness is less than 3 μm, even less than 2 μm.
Preferably, include: using the method that the alkali copper precipitation method prepare copper foil
Alkaline Bath will be placed in the substrate film layer workpiece that at least a surface is prepared with sputtering layer, walking speed be 20Hz,
Electroless Plating Copper under conditions of electric current is 32.1A, voltage is 3.1.Suitable electroless Plating Copper condition, can reduce boundary defect, mentions
Height sputtering layer surface heavy work in copper degree, be conducive to copper ion uniformly, be deposited on sputtering layer surface in an orderly manner, finally obtain consistency
Extra thin copper foil high, surface is uniform and smooth.With this condition, the copper thickness being prepared through the alkali copper precipitation method, can be down to 1
μm.The embodiment of the present invention passes through composition, concentration and the electroplating parameter of regulation alkaline Bath, in the workpiece for being prepared with sputtering layer
Surface uniform deposition copper ion, and form extra thin copper foil.It is further preferred that the alkaline Bath is 30-100g/ by concentration
The cupric pyrophosphate and concentration of L is that the potassium pyrophosphate of 200-400g/L mixes, and the pH of the alkaline Bath is 8-10.This
Inventive embodiments select cupric pyrophosphate, potassium pyrophosphate as electroplate liquid system, on the one hand, can provide plating by cupric pyrophosphate
The copper ion, on the other hand, cupric pyrophosphate, potassium pyrophosphate can effectively make the pH of electroplate liquid as a pair of of buffer solution
It is maintained in the range of 8-10, to promote copper ion in sputtering layer surface compact, uniform deposition, forms fine and close bright copper
Foil.
As the third embodiment, the electroless Plating Copper uses the plating that is formed on sputtering layer of the two hypo acid copper precipitation method
Copper foil.It is precipitated by two hypo acid copper, on the one hand, the flexibility that thin flexible copper-clad plate thickness selection can be improved can sputter
Layer surface deposits the relatively thick copper foil of a thickness, and (setting of sputtering layer allows substrate film surface to bear thickness higher than 6 μ
The copper foil layer of m, and have and be well bonded), meet requirement of the client to flexible copper-clad plate thickness；It is precipitated by two hypo acid copper
Obtained copper foil when client reinforcement solutions, can increase the pulling force between copper foil and reinforcement film, increase client supporting material
Peel strength.
Preferably, include: using the method that the sour copper precipitation method prepare copper foil
S031 will be placed in roughening electroplate liquid in the substrate film layer workpiece that at least a surface is prepared with sputtering layer, carry out the first table
Face roughening treatment.
In the step, the workpiece of heavy copper to be electroplated is set in the substrate film layer workpiece that at least a surface is prepared with sputtering layer
Copper ion is promoted more efficiently to tie by composition, concentration and the electroplating parameter of regulation roughening electroplate liquid in roughening electroplate liquid
It closes in sputtering layer surface, in sputtering layer surface rapid precipitation copper ion, improves heavy copper speed, but the layers of copper that roughening treatment obtains is brilliant
Lattice are not close.Preferably, the copper sulphate and concentration that the roughening electroplate liquid is 80-120g/L by concentration are the five of 50-100g/L
Brochanite mixes.The embodiment of the present invention selects the copper sulphate of certain concentration, cupric sulfate pentahydrate as electroplate liquid system, benefit
In the fast enriching of copper ion.Workpiece after first surface roughening treatment is placed in the solidification electroplate liquid by S032, is carried out
First curing process.
In the step, the workpiece after surface roughening treatment is immersed in the solidification electroplate liquid, is solidified by regulation
Not fine and close layers of copper after surface roughening treatment is carried out solidification stabilization, and is formed by composition, concentration and the electroplating parameter of electroplate liquid
Copper foil fine and close, in homogeneous thickness, to guarantee the service performance of copper foil.In the step, in order to adjust the solidification effect of copper ion
And deposition uniformity, it needs to be adjusted the ion concentration in electrolyte, it is preferred that the solidification electroplate liquid is by concentration
The copper sulphate and concentration of 60-110g/L is that the cupric sulfate pentahydrate of 100-200g/L mixes.The embodiment of the present invention selects sulfuric acid
Copper, cupric sulfate pentahydrate can effectively improve the deposition of copper ion as electroplate liquid system.And above-mentioned solidification electroplate liquid has properly
Depositional environment and copper ion concentration, so as in the sputtering layer surface very rapidly and uniformly enriching Cu that is roughened that treated
Ion forms uniform first copper foil.
Workpiece Jing Guo the first curing process is placed in roughening electroplate liquid by S033, carries out second surface roughening treatment.
In the step, the workpiece Jing Guo the first curing process is placed in roughening electroplate liquid, passes through regulation roughening electroplate liquid
Composition, concentration and electroplating parameter promote copper ion to be more efficiently combined within the in sputtering layer surface rapid precipitation copper ion
One copper foil surface improves heavy copper speed, but the layers of copper lattice that roughening treatment obtains is not close.Preferably, the roughening electroplate liquid
The cupric sulfate pentahydrate that the copper sulphate and concentration for being 80-120g/L by concentration are 50-100g/L mixes.Choosing of the embodiment of the present invention
The copper sulphate of selecting certain concentration, cupric sulfate pentahydrate are as electroplate liquid system, conducive to the uniform enrichment of copper ion.
Workpiece after second surface roughening treatment is placed in the solidification electroplate liquid by S034, is carried out at the second solidification
Reason.
In the step, the workpiece after second surface roughening treatment is immersed in the solidification electroplate liquid, regulation is passed through
Composition, concentration and the electroplating parameter for solidifying electroplate liquid carry out solidification stabilization to the not fine and close layers of copper after surface roughening treatment, and
Fine and close, copper foil in homogeneous thickness is formed, to guarantee the service performance of copper foil.In the step, in order to adjust the solidification of copper ion
Effect and deposition uniformity need to be adjusted the ion concentration in electrolyte, it is preferred that the solidification electroplate liquid is by concentration
The cupric sulfate pentahydrate that copper sulphate and concentration for 60-110g/L are 100-200g/L mixes.The embodiment of the present invention selects sulphur
Sour copper, cupric sulfate pentahydrate can effectively improve the deposition of copper ion as electroplate liquid system.And above-mentioned solidification electroplate liquid has conjunction
Suitable depositional environment and copper ion concentration, so as to be roughened treated sputtering layer surface be very rapidly and uniformly enriched with
Copper ion forms uniform copper foil.
Workpiece after the second curing process is placed in the passivation electroplate liquid by S035, is carried out surface passivating treatment, is obtained
To copper foil.
The copper foil that cured processing obtains, the layers of copper activity on surface is higher, is easy to happen oxidation and influences its performance, such as drops
Low electric conductivity energy.In the step, the workpiece after the second curing process is placed in the passivation electroplate liquid, is passivated by regulation
Composition, concentration and the electroplating parameter of electroplate liquid carry out ion doping to the copper foil surface of formation, specifically, doping zinc ion
And nickel ion prevents it to be oxidized to reduce the activity of surface layers of copper；Simultaneously as the copper foil that cured processing obtains, table
Surface roughness is relatively high, by surface passivating treatment, zinc ion, nickel ion can be filled in coarse surface pits, to copper
Foil surface carries out polishing passivation, to obtain the flexibility coat copper plate of copper foil surface relative smooth.Preferably, the passivation electroplate liquid
The five water nickel sulfates that the zinc sulfate and concentration for being 2-10g/L by concentration are 1-3g/L mix, and the roughening electroplate liquid
PH is 3-5.Zinc ion, the nickel ion concentration of suitable passivation electroplate liquid are conducive to adjust the zinc on copper foil surface layer, nickel ion is mixed
Miscellaneous amount, to prevent excessive zinc, nickel ion doping from leading to copper foil table while realization prevents copper foil oxidation, surface passivation
Material change occurs for layer metallographic, and then influences the performance of copper foil itself.
In the step of sour copper precipitation method prepare copper foil, by controlling suitable size of current, ion can be effectively controlled
Deposition effect and deposition velocity.Specifically, the technological parameter of the first surface roughening treatment, the first curing process are as follows: walking speed
For 30Hz, electric current 19+30+30A, voltage 4.3+3.2+3.0V.The second surface roughening treatment, the second curing process,
The technological parameter of Passivation Treatment is that walking speed is 30Hz, electric current 19+30+30+0.8A, voltage 4.3+3.2+3.0+2.2V.This
Place, the understanding that electric current is 19+30+30+0.8A can be that the electric current of second surface roughening treatment is 19A, and the second curing process is adopted
With double-current, electric current is 30A, and the electric current of the second Passivation Treatment is 0.8A；It can also be with second surface roughening treatment using double electricity
Stream, electric current are respectively 19A, 30A, and the electric current of the second curing process is 30A, and the electric current of the second Passivation Treatment is 0.8A；Voltage is
Four voltage datas in 4.3+3.2+3.0+2.2V respectively correspond aforementioned four current values.
It is further preferred that further including one-time surface Passivation Treatment after above-mentioned steps S02, before step S03.Tool
Body, the first copper foil obtained through the first curing process is placed in the passivation electroplate liquid.Preferably, the passivation electroplate liquid
The five water nickel sulfates that the zinc sulfate and concentration for being 2-10g/L by concentration are 1-3g/L mix, and the roughening electroplate liquid
PH is 3-5.
As the 4th kind of embodiment, the electroless Plating Copper is using the plating that the alkali copper precipitation method are formed on sputtering layer twice
Copper foil.By continuous alkali copper precipitation process twice, it can make to arrange even closer, copper foil appearance more light between copper ion
It is bright, meanwhile, continuous alkali copper precipitation process, keeps the mechanical performance of copper foil more prominent, covers to meet client to flexibility twice
The requirement for having both brightness and mechanical performance that copper sheet proposes.
Preferably, include: using the method that the alkali copper precipitation method prepare copper foil
S031. it will be placed in alkaline Bath in the substrate film layer workpiece that at least a surface is prepared with sputtering layer, is in walking speed
20Hz, electric current 32.1A, voltage carry out the first alkali copper electroplating processes under conditions of being 3.1；
S032. the workpiece of the first alkali copper electroplating processes will be placed in alkaline Bath, walking speed is 20Hz, electric current is
32.1A, voltage carry out the second alkali copper electroplating processes under conditions of being 3.1.
Under above-mentioned first alkali copper plating conditions, boundary defect can be reduced, the heavy work in copper degree of sputtering layer surface is improved, has
Conducive to copper ion uniformly, be deposited on sputtering layer surface in an orderly manner, finally obtain the copper foil that consistency is high, surface is uniform and smooth.Into
One step, suitable second alkali copper electroplating processes are carried out continuously, can not only guarantee that copper ion uniformly, in an orderly manner deposits, be caused
The copper foil that density is high, surface is uniform and smooth, and keep the mechanical performance of copper foil more prominent, to meet client to flexible copper-clad
The requirement for having both brightness and mechanical performance that plate proposes.The embodiment of the present invention passes through the composition of regulation alkaline Bath, concentration
And electroplating parameter, the workpiece surface after surface roughening treatment deposits rapidly copper ion, and forms copper foil.Further preferably
, the alkaline Bath used in alkali copper electroplating processes is identical twice, by concentration is the cupric pyrophosphate of 30-100g/L and dense
Degree is that the potassium pyrophosphate of 200-400g/L mixes, and the pH of the alkaline Bath is 8-10.Selection of the embodiment of the present invention
Cupric pyrophosphate, potassium pyrophosphate are as electroplate liquid system, on the one hand, and it can provide plating the copper ion by cupric pyrophosphate,
On the other hand, cupric pyrophosphate, potassium pyrophosphate can effectively make the pH of electroplate liquid be maintained at the model of 8-10 as a pair of of buffer solution
In enclosing, to promote copper ion in sputtering layer surface compact, uniform deposition, fine and close bright copper foil is formed.
As the 5th kind of embodiment, the electroless Plating Copper forms the first electro-coppering using the sour copper precipitation method on sputtering layer
After foil, the second electro copper foil is formed on first electro copper foil using the alkali copper precipitation method.It, can be with by sour copper precipitation process
Obtain the relatively thick layers of copper of thickness, but the surface of layers of copper that sour copper precipitates is relatively rough；Further, it is precipitated in sour copper
After and then carry out alkali copper precipitation process, the high copper of surface brightness can be obtained under the premise of guaranteeing suitable thickness
Foil.
Preferably, after forming the first electro copper foil on sputtering layer using the sour copper precipitation method, using the alkali copper precipitation method in institute
Stating the method that the second electro copper foil is formed on the first electro copper foil includes:
S031 will be placed in roughening electroplate liquid in the substrate film layer workpiece that at least a surface is prepared with sputtering layer, and it is thick to carry out surface
Change processing.
In the step, the workpiece of heavy copper to be electroplated is set in the substrate film layer workpiece that at least a surface is prepared with sputtering layer
Copper ion is promoted more efficiently to tie by composition, concentration and the electroplating parameter of regulation roughening electroplate liquid in roughening electroplate liquid
It closes in sputtering layer surface, in sputtering layer surface rapid precipitation copper ion, improves heavy copper speed, but the layers of copper that roughening treatment obtains is brilliant
Lattice are not close.Preferably, the copper sulphate and concentration that the roughening electroplate liquid is 80-120g/L by concentration are the five of 50-100g/L
Brochanite mixes.The embodiment of the present invention selects the copper sulphate of certain concentration, cupric sulfate pentahydrate as electroplate liquid system, benefit
In the fast enriching of copper ion.
Workpiece after surface roughening treatment is placed in solidification electroplate liquid by S032, carries out curing process.
In the step, the workpiece after surface roughening treatment is immersed in the solidification electroplate liquid, is solidified by regulation
Composition, concentration and the electroplating parameter of electroplate liquid carry out solidification stabilization to the not fine and close layers of copper after surface roughening treatment, and are formed
Copper foil fine and close, in homogeneous thickness, to guarantee the service performance of copper foil.In the step, in order to adjust the solidification effect of copper ion
And deposition uniformity, it needs to be adjusted the ion concentration in electrolyte, it is preferred that the solidification electroplate liquid is by concentration
The copper sulphate and concentration of 60-110g/L is that the cupric sulfate pentahydrate of 100-200g/L mixes.The embodiment of the present invention selects sulfuric acid
Copper, cupric sulfate pentahydrate can effectively improve the deposition of copper ion as electroplate liquid system.And above-mentioned solidification electroplate liquid has properly
Depositional environment and copper ion concentration, so as in the sputtering layer surface very rapidly and uniformly enriching Cu that is roughened that treated
Ion forms uniform copper foil.
S033 carries out in cured treated workpiece is placed in passivation electroplate liquid surface passivating treatment, obtains the first electricity
Plate copper foil.
The copper foil that cured processing obtains, the layers of copper activity on surface is higher, is easy to happen oxidation and influences its performance, such as drops
Low electric conductivity energy.In the step, treated that workpiece is placed in the passivation electroplate liquid by cured, passes through regulation passivation plating
Composition, concentration and the electroplating parameter of liquid carry out ion doping to the copper foil surface of formation, specifically, doping zinc ion and nickel
Ion prevents it to be oxidized to reduce the activity of surface layers of copper；Simultaneously as the copper foil that cured processing obtains, surface are thick
Rugosity is relatively high, by surface passivating treatment, zinc ion, nickel ion can be filled in coarse surface pits, to copper foil table
Face carries out polishing passivation, to obtain the flexibility coat copper plate of copper foil surface relative smooth.Preferably, the passivation electroplate liquid is by dense
The five water nickel sulfates that the zinc sulfate and concentration that degree is 2-10g/L are 1-3g/L mix, and the pH of the roughening electroplate liquid is
3-5.Zinc ion, the nickel ion concentration of suitable passivation electroplate liquid, are conducive to the doping for adjusting the zinc, nickel ion on copper foil surface layer
Amount, to prevent excessive zinc, nickel ion doping from leading to copper foil surface layer while realization prevents copper foil oxidation, surface passivation
Material change occurs for metallographic, and then influences the performance of copper foil itself.
In the step of sour copper precipitation method prepare copper foil, the surface roughening treatment, curing process, the technique of Passivation Treatment ginseng
Number are as follows: walking speed 30Hz, electric current 19+30+30+0.8A, voltage 4.3+3.2+3.0+2.2V.By controlling suitable electric current
Size can effectively control the deposition effect and deposition velocity of ion.Herein, electric current is that the understanding of 19+30+30+0.8A can be with
Electric current for surface roughening treatment is 19A, and curing process uses double-current, and electric current is 30A, and the electric current of Passivation Treatment is
0.8A；Double-current can also be used with surface roughening treatment, electric current is respectively 19A, 30A, and the electric current of curing process is 30A, passivation
The electric current of processing is 0.8A；Voltage is that four voltage datas in 4.3+3.2+3.0+2.2V respectively correspond aforementioned four electric currents
Value.
The workpiece of passivated processing is placed in alkaline Bath by S034, walking speed is 20Hz, electric current 32.1A, voltage are
Alkali copper electroplating processes are carried out under conditions of 3.1, obtain the second electro copper foil.
Suitable electroless Plating Copper condition is conducive to copper ion and uniformly, in an orderly manner deposits, and finally obtains consistency height, surface
The second uniform and smooth electro copper foil.
In the step, the workpiece of passivated processing is placed in alkaline Bath, by the composition, dense for regulating and controlling alkaline Bath
Degree and electroplating parameter, the workpiece surface uniform deposition copper ion after Passivation Treatment, and form copper foil.It is further preferred that
The mixing of potassium pyrophosphate that the cupric pyrophosphate and concentration that the alkaline Bath is 30-100g/L by concentration are 200-400g/L and
At, and the pH of the alkaline Bath is 8-10.The embodiment of the present invention selects cupric pyrophosphate, potassium pyrophosphate as electro-plating liquid
System, on the one hand, it can provide plating the copper ion by cupric pyrophosphate, on the other hand, cupric pyrophosphate, potassium pyrophosphate conduct
A pair of of buffer solution can effectively be such that the pH of electroplate liquid is maintained in the range of 8-10, to promote copper ion in sputtering layer table
Face densification, uniform deposition form fine and close bright copper foil.
As the 6th kind of embodiment, the electroless Plating Copper forms the first electro-coppering using the alkali copper precipitation method on sputtering layer
After foil, the second electro copper foil is formed on first electro copper foil using the sour copper precipitation method.It, can be with by alkali copper precipitation process
Increase copper foil and the peel strength between substrate；On this basis, further progress acid copper precipitation process, can be without thick
Under the premise of change processing (carrying out pretreatment modification to sputtering layer), the deposition efficiency of copper ion is quicklyd increase, production efficiency is improved.
In addition, the copper foil precipitated through alkali copper precipitating-acid copper, has suitable surface roughness, can increase client reinforcing material
The peel strength of material.
Preferably, after forming the first electro copper foil on sputtering layer using the alkali copper precipitation method, using the sour copper precipitation method in institute
Stating the method that the second electro copper foil is formed on the first electro copper foil includes:
S031 will be placed in alkaline Bath in the substrate film layer workpiece that at least a surface is prepared with sputtering layer, be in walking speed
20Hz, electric current 32.1A, voltage carry out alkali copper electroplating processes under conditions of being 3.1, obtain the first copper foil.Suitable plating is heavy
Copper bar part can reduce boundary defect, improve the heavy work in copper degree of sputtering layer surface, is conducive to copper ion and uniformly, in an orderly manner deposits
In sputtering layer surface, the first electro copper foil that consistency is high, surface is uniform and smooth is finally obtained.
In the step, the workpiece of heavy copper to be electroplated is set in the substrate film layer workpiece that at least a surface is prepared with sputtering layer
In being placed in alkaline Bath, by regulating and controlling composition, concentration and the electroplating parameter of alkaline Bath, in the work for being prepared with sputtering layer
The uniform copper ion in part surface, and form the first electro copper foil.It is further preferred that the alkaline Bath is 30- by concentration
The cupric pyrophosphate and concentration of 100g/L is that the potassium pyrophosphate of 200-400g/L mixes, and the pH of the alkaline Bath is 8-
10.The embodiment of the present invention selects cupric pyrophosphate, potassium pyrophosphate as electroplate liquid system, on the one hand, can be mentioned by cupric pyrophosphate
For the copper ion is electroplated, on the other hand, cupric pyrophosphate, potassium pyrophosphate can effectively make to be electroplated as a pair of of buffer solution
The pH of liquid is maintained in the range of 8-10, to promote copper ion in sputtering layer surface compact, uniform deposition, is formed fine and close bright
Copper foil.
The first electro copper foil is formed on sputtering layer using the alkali copper precipitation method, can improve sputtering layer surface nature, thus
Promote in subsequent curing step copper ion more efficiently, be incorporated evenly among sputtering layer surface, improve heavy copper speed and copper foil
The uniformity；Meanwhile after by the alkali copper precipitation method forming the first electro copper foil on sputtering layer, sour copper precipitation process is directly carried out,
Copper foil and the peel strength between substrate can be increased.Workpiece through alkali copper electroplating processes is placed in roughening electroplate liquid by S032,
Carry out surface roughening treatment.
In the step, the workpiece through alkali copper electroplating processes is placed in roughening electroplate liquid, passes through the group of regulation roughening electroplate liquid
Heavy copper speed is improved in the first copper foil surface rapid precipitation copper ion at, concentration and electroplating parameter, but roughening treatment obtains
Layers of copper lattice it is not close.Preferably, the copper sulphate and concentration that the roughening electroplate liquid is 80-120g/L by concentration are 50-
The cupric sulfate pentahydrate of 100g/L mixes.The embodiment of the present invention selects the copper sulphate of certain concentration, cupric sulfate pentahydrate as electricity
Bath system, conducive to the uniform enrichment of copper ion.
Workpiece after surface roughening treatment is placed in solidification electroplate liquid by S033, carries out curing process.
In the step, the workpiece after surface roughening treatment is immersed in the solidification electroplate liquid, is solidified by regulation
Composition, concentration and the electroplating parameter of electroplate liquid carry out solidification stabilization, and shape for the not fine and close layers of copper after surface roughening treatment
At fine and close, copper foil in homogeneous thickness, to guarantee the service performance of copper foil.In the step, in order to adjust the solidification effect of copper ion
Fruit and deposition uniformity need to be adjusted the ion concentration in electrolyte, it is preferred that the solidification electroplate liquid is by concentration
The copper sulphate and concentration of 60-110g/L is that the cupric sulfate pentahydrate of 100-200g/L mixes.The embodiment of the present invention selects sulfuric acid
Copper, cupric sulfate pentahydrate can effectively improve the deposition of copper ion as electroplate liquid system.And above-mentioned solidification electroplate liquid has properly
Depositional environment and copper ion concentration, so as in the sputtering layer surface very rapidly and uniformly enriching Cu that is roughened that treated
Ion forms uniform copper foil.
S034 carries out in cured treated workpiece is placed in passivation electroplate liquid surface passivating treatment, obtains the second bronze medal
Foil.
The copper foil that cured processing obtains, the layers of copper activity on surface is higher, is easy to happen oxidation and influences its performance, such as drops
Low electric conductivity energy.In the step, treated that workpiece is placed in the passivation electroplate liquid by cured, passes through regulation passivation plating
Composition, concentration and the electroplating parameter of liquid carry out ion doping to the copper foil surface of formation, specifically, doping zinc ion and nickel
Ion prevents it to be oxidized to reduce the activity of surface layers of copper；Simultaneously as the copper foil that cured processing obtains, surface are thick
Rugosity is relatively high, by surface passivating treatment, zinc ion, nickel ion can be filled in coarse surface pits, to copper foil table
Face carries out polishing passivation, to obtain the flexibility coat copper plate of copper foil surface relative smooth.Preferably, the passivation electroplate liquid is by dense
The five water nickel sulfates that the zinc sulfate and concentration that degree is 2-10g/L are 1-3g/L mix, and the pH of the roughening electroplate liquid is
3-5.Zinc ion, the nickel ion concentration of suitable passivation electroplate liquid, are conducive to the doping for adjusting the zinc, nickel ion on copper foil surface layer
Amount, to prevent excessive zinc, nickel ion doping from leading to copper foil surface layer while realization prevents copper foil oxidation, surface passivation
Material change occurs for metallographic, and then influences the performance of copper foil itself.
The step of above-mentioned steps S032 to S034 is the sour copper precipitation method, the step of preparing the second copper foil using the sour copper precipitation method
In, the technological parameter of the surface roughening treatment, curing process, Passivation Treatment are as follows: walking speed 30Hz, electric current 19+30+30+
0.8A, voltage 4.3+3.2+3.0+2.2V.By controlling suitable size of current, the deposition effect of ion can be effectively controlled
And deposition velocity.Herein, the understanding that electric current is 19+30+30+0.8A can be that the electric current of surface roughening treatment is 19A, at solidification
Reason uses double-current, and electric current is 30A, and the electric current of Passivation Treatment is 0.8A；Double-current, electricity can also be used with surface roughening treatment
Stream is respectively 19A, 30A, and the electric current of curing process is 30A, and the electric current of Passivation Treatment is 0.8A；Voltage is 4.3+3.2+3.0+
Four voltage datas in 2.2V respectively correspond aforementioned four current values.
When preparing flexibility coat copper plate using the above method of the embodiment of the present invention, can electroless Plating Copper directly as needed obtain
The copper thickness met the requirements, it is no longer necessary to the copper foil on ultra-thin flexible copper-clad plate surface is etched to reduce flexibility coat copper plate
Thickness, raw material not only can be saved, while also can be omitted harsh etch process, greatly reduce flexibility circuit
Plate manufactures cost.
In conjunction with Fig. 1, the flexibility coat copper plate of the above method of embodiment of the present invention preparation includes substrate film layer 1, is arranged in substrate
The sputtering layer 2 on at least surface of film layer 1, and the copper foil 3 for conduction being arranged on the surface of sputtering layer 2, and the setting of copper foil 3 exists
Surface of the sputtering layer 2 far from substrate film layer 1.
Specifically, substrate film layer 1 with a thickness of 40 μm~60 μm, be specifically as follows 40 μm, 42 μm, 45 μm, 48 μm, 50 μ
M, 52 μm, 55 μm, 58 μm and 60 μm etc..The surface that substrate film layer 1 is contacted with sputtering layer 2 forms corona by sided corona treatment
Layer is conducive to improve substrate film layer 1 and the removing of copper foil 3 is strong to be conducive to sputter copper ion in the deposition of substrate film layer 1
Degree.
Sputtering layer 2 with a thickness of 20nm~300nm, be specifically as follows 20nm, 50nm, 100nm, 150nm, 200nm,
250nm and 300nm etc..Its specific thickness can be adjusted according to the thickness of copper foil 3, when the thinner thickness of copper foil 3, be
The peel strength for increasing entire ultra-thin flexible copper-clad plate then needs to increase accordingly the thickness of sputtering layer 2, increases ultra-thin flexible and covers
The peel strength of copper sheet, to meet ultra-thin flexible copper-clad plate when in use to the requirement of peel strength；Conversely, working as the thickness of copper foil 3
When spending thicker, then the thickness of sputtering layer 2 can be reduced accordingly.
Its copper foil 3 with a thickness of 1 μm~3 μm, be specifically as follows 1.0 μm, 1.2 μm, 1.5 μm, 1.8 μm, 2.0 μm, 2.2 μ
M, 2.4 μm, 2.6 μm, 2.8 μm and 3.0 μm etc., specific thickness can according to using its product demand to do specific adjustment, with
Meet the requirement of product as far as possible, reduces the etching to 3 surface of copper foil, the purpose for having reached and saving material, reduce cost.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. a kind of preparation method of flexibility coat copper plate, which is characterized in that the flexibility coat copper plate includes substrate film layer, is arranged in institute
The sputtering layer on a substrate film layer at least surface, and the copper foil for conduction being arranged on the surface of the sputtering layer are stated, and described
Copper foil is arranged in surface of the sputtering layer far from the substrate film layer, and the preparation method of the flexibility coat copper plate, including with
Lower step:
Substrate film layer is provided, sided corona treatment is carried out to the surface of the substrate film layer, obtains surface modified substrates film layer；
Copper is sunk in the surface modified substrates film surface magnetron sputtering method for sputtering layer；
In the heavy copper of the sputtering layer electroplating surface, copper foil is prepared, wherein the method for the electroless Plating Copper are as follows: precipitate using alkali copper
After method forms the first electro copper foil on sputtering layer, the second plating is formed on first electro copper foil using the sour copper precipitation method
Copper foil.
2. the preparation method of flexibility coat copper plate as described in claim 1, which is characterized in that in the surface modified substrates film layer
The heavy copper of surface magnetic control sputtering method includes: under vacuum conditions, using nickel, copper as target, ion source to be arranged for the step of sputtering layer
Parameter are as follows: 1000-4000W, 0.1-0.25A, the charge flow rate of argon gas is 180-230sccm, throughput is 30-50sccm out,
Heavy copper is sputtered, sputtering layer is obtained.
3. the preparation method of flexibility coat copper plate as described in claim 1, which is characterized in that using the alkali copper precipitation method in sputtering layer
After the first electro copper foil of upper formation, the method for the second electro copper foil is formed on first electro copper foil using the sour copper precipitation method
Include:
It will be placed in alkaline Bath in the substrate film layer workpiece that at least a surface is prepared with sputtering layer, is 20Hz, electric current in walking speed
Alkali copper electroplating processes are carried out under conditions of being 3.1 for 32.1A, voltage, obtain the first copper foil；
Workpiece through alkali copper electroplating processes is placed in roughening electroplate liquid, carries out surface roughening treatment；
Workpiece after surface roughening treatment is placed in solidification electroplate liquid, curing process is carried out；
By in cured treated workpiece is placed in passivation electroplate liquid, surface passivating treatment is carried out, copper foil is obtained,
Wherein, the technological parameter of the surface roughening treatment, curing process, Passivation Treatment are as follows: walking speed 30Hz, electric current 19+
30+30+0.8A, voltage 4.3+3.2+3.0+2.2V.
4. the preparation method of flexibility coat copper plate as claimed in claim 3, which is characterized in that the roughening electroplate liquid is by concentration
The copper sulphate and concentration of 80-120g/L is that the cupric sulfate pentahydrate of 50-100g/L mixes；And/or
It is described to solidify the cupric sulfate pentahydrate mixing that copper sulphate and concentration that electroplate liquid is 60-110g/L by concentration are 100-200g/L
It forms.
5. the preparation method of flexibility coat copper plate as claimed in claim 4, which is characterized in that the passivation electroplate liquid is by concentration
The zinc sulfate and concentration of 2-10g/L is that the five water nickel sulfates of 1-3g/L mix, and the pH of the roughening electroplate liquid is 3-5.
6. the preparation method of flexibility coat copper plate as described in any one in claim 1-5, which is characterized in that the alkaline Bath
The potassium pyrophosphate that the cupric pyrophosphate and concentration for being 30-100g/L by concentration are 200-400g/L mixes, and the alkaline electro
The pH of plating solution is 8-10.
7. the preparation method of flexibility coat copper plate as described in any one in claim 1-5, which is characterized in that substrate film layer is provided,
In the step of carrying out sided corona treatment to the surface of the substrate film layer, comprising: with the power of 2.5-4kw, to the substrate film layer
An at least surface carry out sided corona treatment, obtain surface modified substrates film layer.
8. the preparation method of flexibility coat copper plate as described in any one in claim 1-5, which is characterized in that the thickness of the copper foil layer
Degree is 1 μm~3 μm.
9. the preparation method of flexibility coat copper plate as described in any one in claim 1-5, which is characterized in that the thickness of the sputtering layer
Degree is 20nm~300nm.
10. the preparation method of flexibility coat copper plate as described in any one in claim 1-5, which is characterized in that the substrate film layer
With a thickness of 40 μm~60 μm.
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Application publication date: 20181228 |