CN108505081A - Method for manufacturing electrolytic copper foil with approximate villiform copper nodules and circuit board assembly - Google Patents
Method for manufacturing electrolytic copper foil with approximate villiform copper nodules and circuit board assembly Download PDFInfo
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- CN108505081A CN108505081A CN201710160563.0A CN201710160563A CN108505081A CN 108505081 A CN108505081 A CN 108505081A CN 201710160563 A CN201710160563 A CN 201710160563A CN 108505081 A CN108505081 A CN 108505081A
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- villiform
- copper foil
- copper
- tumor
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 260
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 128
- 239000010949 copper Substances 0.000 title claims abstract description 128
- 239000011889 copper foil Substances 0.000 title claims abstract description 128
- 238000000034 method Methods 0.000 title claims abstract description 66
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 44
- 239000010410 layer Substances 0.000 claims abstract description 86
- 239000011888 foil Substances 0.000 claims abstract description 50
- 239000002344 surface layer Substances 0.000 claims abstract description 10
- 239000002335 surface treatment layer Substances 0.000 claims abstract 3
- 206010028980 Neoplasm Diseases 0.000 claims description 94
- 238000007747 plating Methods 0.000 claims description 78
- 238000007788 roughening Methods 0.000 claims description 62
- 239000000758 substrate Substances 0.000 claims description 47
- 239000011347 resin Substances 0.000 claims description 37
- 229920005989 resin Polymers 0.000 claims description 37
- 238000012545 processing Methods 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 23
- 239000003792 electrolyte Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- JRIGVWDKYXCHMG-UHFFFAOYSA-N (5-arsoroso-2-hydroxyphenyl)azanium;chloride Chemical compound Cl.NC1=CC([As]=O)=CC=C1O JRIGVWDKYXCHMG-UHFFFAOYSA-N 0.000 claims description 9
- 229910000413 arsenic oxide Inorganic materials 0.000 claims description 9
- 229960002594 arsenic trioxide Drugs 0.000 claims description 9
- KTTMEOWBIWLMSE-UHFFFAOYSA-N diarsenic trioxide Chemical compound O1[As](O2)O[As]3O[As]1O[As]2O3 KTTMEOWBIWLMSE-UHFFFAOYSA-N 0.000 claims description 9
- 230000005611 electricity Effects 0.000 claims description 9
- 229950008475 oxophenarsine Drugs 0.000 claims description 9
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 7
- 239000003963 antioxidant agent Substances 0.000 claims description 7
- 230000003078 antioxidant effect Effects 0.000 claims description 7
- 235000006708 antioxidants Nutrition 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 230000008878 coupling Effects 0.000 claims description 6
- 238000010168 coupling process Methods 0.000 claims description 6
- 238000005859 coupling reaction Methods 0.000 claims description 6
- 239000003292 glue Substances 0.000 claims description 6
- 229910000077 silane Inorganic materials 0.000 claims description 6
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 5
- 229920000106 Liquid crystal polymer Polymers 0.000 claims description 4
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 230000003064 anti-oxidating effect Effects 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 2
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 230000003746 surface roughness Effects 0.000 description 17
- 239000002245 particle Substances 0.000 description 14
- 230000005540 biological transmission Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000007711 solidification Methods 0.000 description 7
- 230000008023 solidification Effects 0.000 description 7
- 238000004381 surface treatment Methods 0.000 description 6
- 238000010884 ion-beam technique Methods 0.000 description 4
- 239000011241 protective layer Substances 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000002500 effect on skin Effects 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- -1 polyoxy Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004425 Makrolon Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
- H05K3/384—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by plating
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/0058—Laminating printed circuit boards onto other substrates, e.g. metallic substrates
- H05K3/0064—Laminating printed circuit boards onto other substrates, e.g. metallic substrates onto a polymeric substrate
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electroplating Methods And Accessories (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Manufacturing Of Printed Wiring (AREA)
Abstract
the invention discloses a method for manufacturing an electrolytic copper foil with approximate villiform copper nodules and a circuit board assembly, wherein the method for manufacturing the electrolytic copper foil with the approximate villiform copper nodules comprises the steps of forming a raw foil layer by an electrolytic method, wherein the raw foil layer is provided with a preset surface, then forming a surface treatment layer on the preset surface of the raw foil layer to form the electrolytic copper foil with a villiform structure on the surface layer, wherein the surface treatment layer comprises a plurality of villiform copper nodules, and a villiform containing space is formed between every two adjacent villiform copper nodules.
Description
Technical field
The present invention relates to the manufacturing methods of a kind of electrolytic copper foil and circuit board module, have more particularly to a kind of surface layer
The manufacturing method of the electrolytic copper foil of fluff structures and a kind of circuit board group using electrolytic copper foil of the surface layer with fluff structures
The manufacturing method of part.
Background technology
The existing copper foil applied to printed circuit board can form former foil, using back segment by being electroplated in cathode wheel
It handles processing procedure and forms final product.Back segment processing includes executing roughening treatment to the rough surface of former foil, in the thick of former foil
Matte forms multiple copper tumors, to increase the Bonding strength between copper foil and circuit board, that is, increase copper foil stripping it is strong
Degree.
However, electronic product tends to high-frequency high-speed in recent years, when transmitting high-frequency signal, will produce it is so-called become skin effect
It answers (skin effect).In patent document 1 (Japanese Patent Laid the 5116943rd), a kind of high-frequency circuit copper foil is provided
And its manufacturing method, illustrate that the shape of copper foil surface has a great impact to transmission loss, the big copper foil of roughness, signal
Propagation distance is elongated, the problem of just will produce signal decaying and postpone.In other words, the surface of copper foil the smooth, and signal is being led
The loss transmitted in body is smaller.Therefore, the planarization of copper foil surface just plays the part of very important role.If copper foil surface roughness
It is higher, then the easier loss when transmitting high-frequency signal.
Referring to FIG. 1, it shows the partial cutaway schematic of copper foil in the prior art.As shown in Figure 1, in the prior art
The surface of middle copper foil F1 is formed by multiple copper tumor F10 and is generally spherical, and major part spherical shape copper tumor F10 is in level side
To full-size can be more than full-size in vertical direction.In this way, although the roughness of copper foil can be made to maintain one
Default value, but copper foil can be caused when being engaged with high frequency substrate, the peel strength of copper foil is insufficient.
But if attempt to reduce high frequency signal transmission loss to reduce the roughness of copper foil surface, and copper foil can be reduced
With the peel strength of circuit board pressing.Therefore, how when promoting the peel strength of copper foil, and copper foil surface can be kept simultaneously
Planarization be current industry personnel research and development a big project.
Invention content
Technical problem to be solved by the present invention lies in provide a kind of electrolytic copper foil and line in view of the deficiencies of the prior art
The manufacturing method of road board group part.
In order to solve the above technical problems, it is approximate to be to provide a kind of tool for a wherein technical solution of the present invention
The manufacturing method of the electrolytic copper foil of villiform copper tumor.The manufacturing method of the electrolytic copper foil of the approximate villiform copper tumor of tool includes passing through electricity
Solution method is to form foil layer, and foil layer has a predetermined surface.Then, it is formed at a surface in the predetermined surface of foil layer
Layer is managed, there is the electrolytic copper foil of approximate fluff structures to form surface layer.Surface-treated layer includes the villous copper tumor of multiple approximations,
And an approximate villous accommodating space is formed between each two adjacent villous copper tumor of approximation.Form surface-treated layer
Step still further comprises：It executes a plating roughening treatment for the first time and executes first time plating curing process, wherein the
Contain 3 to 40g/L copper in one first electroplate liquid used in primary plating roughening treatment, 100 to 120g/L sulfuric acid, be no more than
The arsenic oxide arsenoxide of 20ppm and 5 to 20ppm tungstate ion.
Preferably, when executing the first plating roughening treatment, used current density is 15 to 40A/dm2, and institute
It is rough surface or shiny surface to state predetermined surface.
Preferably, the step of forming the surface-treated layer still further comprises：Execute second of plating roughening treatment
And second of plating curing process is executed, parameter and the first time plating of second of plating roughening treatment are roughened
The parameter of processing is identical, and the parameter phase of curing process is electroplated with the first time for the parameter of second of plating curing process
Together.
Preferably, the step of forming the surface-treated layer is sequentially to execute first time plating roughening treatment, described
Plating curing process, second of plating roughening treatment and second of plating curing process for the first time.
Preferably, the step of forming the surface-treated layer is sequentially to execute first time plating roughening treatment, described
Second of plating roughening treatment, first time plating curing process and second of plating curing process.
Preferably, contain 50 to 70g/ in used one second electroplate liquid when executing the first time plating curing process
The copper of L, 70 to 100g/L sulfuric acid and arsenic oxide arsenoxide less than 30ppm, and when executing the first time curing process being electroplated
Used current density is 2 to 9A/dm2。
Preferably, primary antibody heat treatment is executed, to form a kirsite heat shield on the surface-treated layer, wherein
It includes 1 to 4g/L zinc and 0.3 to 2.0g/L nickel to execute used electrolyte composition when the heat resistanceheat resistant processing, and is being held
Used current density is 0.4 to 2.5A/dm when the capable heat resistanceheat resistant processing2。
Preferably, an anti-oxidant treatment is executed, to form an anti oxidation layer on the surface-treated layer, wherein holding
Used electrolyte composition includes 1 to 4g/L chromium oxide and 5 to 20g/L hydroxide when the row anti-oxidant treatment
Sodium, and used current density is 0.3 to 3.0A/dm when executing the heat resistanceheat resistant processing2。
Preferably, a silane coupling processing is executed, to form a silane coupling agent process layer on the surface-treated layer,
Wherein, 0.3 to 1.5% weight silane coupling agent is used when executing the silane coupling processing.
Preferably, multiple villous copper tumors of the approximation have a maximum major diameter and a maximum short axle straight
Diameter, maximum major diameter is between 0.5 μm to 1.5 μm, and maximum minor axis diameter is between 0.1 μm to 1.0 μm, and most
Ratio between big minor axis diameter and maximum major diameter is 0.2 to 0.7.
Preferably, the distribution density of multiple villous copper tumors of the approximation is often square micron 2 to 5, and each two
Spacing between the adjacent villous copper tumor of the approximation is between 0.1 to 0.4 μm.
A wherein technical solution of the present invention is to provide a kind of manufacturing method of circuit board module comprising carries
For being formed by the electrolytic copper foil of the approximate villiform copper tumor of tool by the manufacturing method；And the electricity that will have approximate villiform copper tumor
Solution copper foil presses face-to-face with a resin substrate, to form a circuit board module, wherein surface-treated layer faces resin substrate.
Preferably, the peel strength of the electrolytic copper foil of the approximate villiform copper tumor of the tool is at least more than 3lb/in.
Preferably, the electrolytic copper foil of the approximate villiform copper tumor of the tool is combined with the resin substrate by an adhesion glue,
And a part for the adhesion glue is inserted in the villous accommodating space of approximation.
Preferably, the resin substrate is semi-solid preparation substrate or liquid crystal polymer substrate, and when the approximate villiform of the tool
When the electrolytic copper foil of copper tumor is pressed with the resin substrate, a part for the resin substrate inserts the villous appearance of approximation
In emptying.
The beneficial effects of the present invention are by the above-mentioned manufacture method, can be such that the surface-treated layer of electrolytic copper foil has
Multiple villiform copper tumors or approximate villous copper tumor.That is, the width of villiform copper tumor or approximate villous copper tumor
The width of spherical shape copper tumor than in the prior art is small.Therefore, when surface layer has the electrolytic copper foil and resin of approximate fluff structures
Substrate then when, compared to the prior art in for the electrolytic copper foil with spherical shape copper tumor, surface layer has approximate fluff structures
Electrolytic copper foil and resin substrate between with bigger contact area, so as to higher peel strength.
For the enabled feature and technology contents for being further understood that the present invention, please refer to below in connection with the present invention specifically
Bright and attached drawing, however the attached drawing provided is only for reference and description, the person of being not intended to limit the present invention.
Description of the drawings
Fig. 1 is the partial cutaway schematic of electrolytic copper foil in the prior art.
Fig. 2 is the flow chart of the manufacturing method of the electrolytic copper foil of the approximate villiform copper tumor of tool of the embodiment of the present invention.
Fig. 3 is the schematic diagram of the system of the manufacturing method of the electrolytic copper foil to execute the approximate villiform copper tumor of the tool of Fig. 2.
Fig. 4 is the partial cutaway schematic of the electrolytic copper foil of the approximate villiform copper tumor of tool of the embodiment of the present invention.
Close-up schematic view of the electrolytic copper foil for the approximate villiform copper tumor of tool that Fig. 5 is Fig. 4 in region V.
Fig. 6 is the electrolytic copper foil of the approximate villiform copper tumor of tool of the embodiment of the present invention at scanning electron microscope (SEM)
Photo.
Fig. 7 is photo of the electrolytic copper foil in scanning electron microscope (SEM) of comparative example.
Fig. 8 is focused ion beam (FIB) photo of the electrolytic copper foil of the approximate villiform copper tumor of tool of the embodiment of the present invention.
Fig. 9 is the diagrammatic cross-section of the circuit board module of the embodiment of the present invention.
Partial enlarged view of the circuit board module in region X that Figure 10 is Fig. 9.
Figure 11 is the diagrammatic cross-section of the circuit board module of another embodiment of the present invention.
Specific implementation mode
Be below illustrated by particular specific embodiment it is presently disclosed in relation to the " electricity of the approximate villiform copper tumor of tool
The embodiment of the manufacturing method of electrolytic copper foil and circuit board module ".The manufacturing method that the embodiment of the present invention is provided can obtain
The electrolytic copper foil that must have approximate villiform copper tumor, with low rugosity and high-peeling strength.In addition, manufactured by manner described above
The electrolytic copper foil and resin substrate of the approximate villiform copper tumor of tool, which are interconnected, to be formed by circuit board module and can be applied to high frequency letter
Number transmission.Please refer to Fig. 2 and Fig. 3.Fig. 2 shows the manufacturer of the electrolytic copper foil of the approximate villiform copper tumor of the tool of the embodiment of the present invention
The flow chart of method, Fig. 3 are the equipment signal of the manufacturing method of the electrolytic copper foil to execute the approximate villiform copper tumor of the tool of Fig. 2
Figure.
First, as shown in Fig. 2, in the step s 100, by an electrolytic method to form all one's life layers of foil, wherein the foil
Layer has a predetermined surface.
Referring to FIG. 3, the step of forming foil layer by electrolytic method includes providing a foil device 1, and foil device 1
Including at least an electrolytic cell 10, an anode plate 11, a cathode wheel 12 and a roller 13.
From the above, electrolytic cell 10 is containing electrolyte L0.Anode plate 11 is arranged in electrolytic cell 10, and is electrically connected
To the cathode output end of a power supply device 2.Anode plate 11 is to be coated in titanium plate by iridium or its oxide and formed.It is cloudy
Pole wheel 12 then corresponds to electrolytic cell 10 and is arranged, and positioned at 11 top of anode plate.In addition, cathode wheel 12 is electrically connected to power supply confession
Answer the cathode output end of device 2.In embodiments of the present invention, cathode wheel 12 is titanium roller.
In addition, in the present embodiment, foil device 1 further includes the diversion pipe 14 of one and the fluid communication of electrolytic cell 10.It is aforementioned
Electrolyte L0 be by diversion pipe 14 inject electrolytic cell 10 in, flood anode plate 11, and part cathode wheel 12 is made to be immersed in electricity
It solves in liquid L0.
Then, as shown in figure 3, power supply device E1 exports direct current to anode plate 11 and cathode wheel 12, to electricity
It solves liquid L0 and applies electric current, the copper ion in electrolyte L0 is made to be precipitated in the surface of cathode wheel 12, and form foil layer 30.
In addition, when electrolyte L0 forms foil layer 30, can continue in supply electrolyte L0 to electrolytic cell 10.Specifically
For, electrolyte L0 can be flowed by diversion pipe 14 in electrolytic cell 10, with maintain the copper of the electrolyte L0 in electrolytic cell 10 from
Sub- concentration.Referring again to Fig. 3, the foil layer 30 for being formed in 12 surface of cathode wheel can be by the sur-face peeling of cathode wheel 12, and passes through
Roller 13, to carry out follow-up process.
More specifically, foil layer 30 has a rough surface 30a and shiny surface 30b opposite with aforementioned rough surface 30a,
Wherein shiny surface 30b is the surface of foil layer 30 and the contact of cathode wheel 12 in electrolytic process, therefore shiny surface 30b's is coarse
It spends relatively fixed.Rough surface 30a is then the surface for contacting electrolyte L0.The rough surface 30a or shiny surface 30b of foil layer 30 are usual
There can be multiple graininess protrusions.In one embodiment, 10 mean roughness of the rough surface 30a of foil layer 30 are no more than 2 μ
M, such as between 0.9 μm to 1.9 μm.
Then, referring again to Fig. 2, in step s 200, a surface-treated layer is formed in the predetermined surface of foil layer, with
Forming a surface layer has the electrolytic copper foil of approximate fluff structures, wherein and surface-treated layer includes the villous copper tumor of multiple approximations,
And an approximate villous accommodating space is formed between each two adjacent copper tumor.
From the above, formed surface-treated layer step S200 still further comprise execution roughening treatment is electroplated at least once
With curing process is electroplated at least once.In embodiments of the present invention, foil layer can pass through is electroplated roughening treatment and twice electricity twice
Plate curing process, with the predetermined surface of foil layer formed surface-treated layer, wherein predetermined surface can refer to rough surface or
One at least in shiny surface.
Specifically, it is sequentially to execute electricity for the first time after step sloo as shown in Fig. 2, in a wherein embodiment
Plate roughening treatment (step S201), for the first time plating curing process (step S203), second of plating roughening treatment (step
S202) and second is electroplated curing process (step S204).
In another embodiment, after step sloo, it is sequentially to execute plating roughening treatment (step for the first time
S201), second of plating roughening treatment (step S202), first time plating curing process (step S203) and second are electroplated
Curing process (step S204).
More specifically, as plating roughening treatment and the number of plating curing process are more, cathode copper can be increased
The Bonding strength of foil and resin substrate, but the surface roughness of electrolytic copper foil can also increased, and be unfavorable for applying and believe in high frequency
Number transmission.Therefore, plating roughening treatment and number and tune that curing process is electroplated can be increased and decreased according to the needs of practical processing procedure
Whole sequence.
Please refer to Fig. 3.Sequentially to execute plating roughening treatment for the first time, first time plating curing process, be electroplated for second
It is illustrated for roughening treatment and second of plating curing process.
As shown in figure 3, the surface processing device 2 for executing step S201~S204 includes that configuration is online in a production
Multiple transmission units 20, at least one roughening unit 21 (two are painted in Fig. 3), at least one solidified cell 22 (are painted in Fig. 3
Two) and multiple rinse baths 23, wherein the quantity of roughening unit 21, solidified cell 22 and rinse bath 23 according to actual demand and
Setting.Multiple transmission units 20 according to acquiescence processing flow by foil layer 30 be sent to roughening unit 21, rinse bath 23 and
Solidified cell 22 is handled.
Roughening unit 21 includes carrying the roughening slot 210 of the first electroplate liquid L1 and being set in roughening slot 210
One group of roughening anode plate 211.As shown in figure 3, when executing plating roughening treatment for the first time, foil layer 30 can be put into and load
In the roughening slot 210 of first electroplate liquid L1.First electroplate liquid L1 used in the embodiment of the present invention contain 3 to 40g/L copper, 100
To 120g/L sulfuric acid, it is no more than the arsenic oxide arsenoxide (As of 20ppm2O3) and 5 to 20ppm tungstate ion (WO4 2-)。
When executing plating roughening treatment for the first time, roughening anode plate 211 is applied in a positive voltage respectively with foil layer 30
With a negative voltage, so that the copper ion in the first electroplate liquid L1 restores, and multiple wartys are formed in the rough surface 30a of foil layer 30
Copper particle.
It should be noted that the first electroplate liquid L1 used in the embodiment of the present invention has special composition, that is, contain
The copper of low concentration can limit the crystalline growth direction of warty copper particle.In addition, arsenic oxide arsenoxide concentration and tungstate ion it is dense
Degree is no more than 20ppm.If the excessive concentration of arsenic oxide arsenoxide, size spheroidal copper tumor bigger than normal may be formed, and relatively is difficult to be formed
Approximate villiform or villous copper tumor.
Furthermore, when executing plating roughening treatment for the first time, since the copper concentration in the first electroplate liquid L1 is relatively low,
Copper atom can only be limited in compared with the crystallization direction of preference (i.e. longitudinal) storehouse.In other words, warty copper particle compared with preference towards one
It is approximately perpendicular to the direction growth of the rough surface 30a of foil layer 30, and is less easily roughly parallel to the thick of foil layer 30 towards one
Grow up in the direction of matte 30a.Therefore, it after roughening treatment being electroplated by first time, is formed on the rough surface 30a of foil layer 30
Most of warty copper particle size in the horizontal direction can be less than the size in longitudinal direction, can also make each two adjacent warty
Spacing between copper particle is wider.
In addition, in one embodiment, when executing plating roughening treatment for the first time, the current density of foil layer 30 be between
15 to 40A/dm2, the smaller warty copper particle of size can be formed.Current density is less than 15A/dm2, electrolytic copper foil may be caused
Peel strength it is insufficient, current density is higher than 40A/dm2, it is possible to create fall copper powder.In addition, executing at plating roughening for the first time
When reason, the temperature of the first electroplate liquid substantially maintains 20 to 40 degree Celsius.
After completing plating roughening treatment for the first time, plating curing process for the first time is executed, to form a covering warty copper
The copper protective layer of particle so that warty copper particle is tightly fastened rough surface 30a or shiny surface 30b in foil layer 30, and is prevented
Only " lose powder " phenomenon.
As shown in figure 3, plating curing process is executed by solidified cell 22 for the first time.Solidified cell 22 includes a use
To carry the solidification slot 220 of the second electroplate liquid L2 and be set to one group of solidification anode plate 221 of solidification slot 220.
In the present embodiment, foil layer 30 first passes through transmission unit after roughening slot 210 completes plating roughening treatment for the first time
After 20 are transferred into the cleaning of rinse bath 23, it is resent to solidification slot 220, to execute plating curing process for the first time.
When executing plating curing process for the first time, solidification anode plate 221 is applied in a positive voltage respectively with foil layer 30
With a negative voltage, so that the copper ion in the second electroplate liquid L2 restores, and covering warty copper particle is formed on foil layer 30
Copper protective layer.
When executing plating curing process for the first time, used second electroplate liquid L2 contains 50 to 70g/L copper, 70 to
The sulfuric acid of 100g/L, and the arsenic oxide arsenoxide less than 30ppm, and the temperature of the second electroplate liquid L2 substantially maintains Celsius 50 to 70
Degree.
It should be noted that the height of the warty copper particle formed in first time plating roughening treatment is not high.If
For the first time when plating curing process, although the probability that picking phenomenon occurs can be reduced by forming thicker copper protective layer, and reduce
The roughness of electrolytic copper foil surface, being but possible to reduction electrolytic copper foil can shell with the surface area of resin substrate then to reduce
From intensity.Therefore, when executing plating curing process for the first time, the more existing used current density of current density is relatively low, with
Form the relatively thin and deep plating preferable copper protective layer of effect.Accordingly, can be in the case where preventing picking, and be not to reduce cathode copper
Foil can be with the surface area of resin substrate then.In one embodiment, in executing plating curing process for the first time, current density is
2 to 9A/dm2。
In one embodiment, after executing plating roughening treatment for the first time and plating curing process for the first time, you can shape
There is the electrolytic copper foil of approximate fluff structures at surface layer.Detailed construction about surface-treated layer will be in hereinafter furtherly
It is bright.
Then, by transmission unit 20, the foil layer 30 for having been subjected to the first plating curing process is first passed by solidification slot 220
It send to rinse bath 23 after cleaning, is resent in next roughening slot 210, to carry out second of plating roughening treatment.
In the present embodiment, the parameter phase of roughening treatment is substantially electroplated in the parameter of second of plating roughening treatment with first time
Together.In second of plating roughening treatment, it can make to have been formed over multiple wartys on the rough surface 30a of foil layer 30 originally
Copper particle continues to grow up.In addition, being that roughening treatment identical first is electroplated using with first time when second of plating roughening treatment
Electroplate liquid L1.Therefore, the growth direction of warty copper particle still can be limited in the rough surface 30a for being approximately perpendicular to foil layer 30
Direction on.In this way, the bonding area of final electrolytic copper foil and resin substrate can be further increased.
Then, it by transmission unit 20, will be transmitted by roughening slot 210 by the foil layer 30 of second of plating roughening treatment
It after being cleaned to another rinse bath 23, is resent in another solidification slot 220, to carry out second of plating curing process.Second
The composition of the second electroplate liquid L2 in curing process is electroplated, it can be with the group of the second electroplate liquid L2 of first time plating curing process
At identical.In addition, the current density for executing second of plating curing process can also be with electricity when first time plating curing process
Current density is close, ranges approximately from 2 to 9A/dm2.By executing second of plating curing process, copper protection can be further provided
Layer, in order to avoid cause to lose powder.
Please refer to Fig. 4 and Fig. 5.Fig. 4 is the partial cutaway schematic of the electrolytic copper foil of the embodiment of the present invention.Fig. 5 is Fig. 4's
Close-up schematic view of the electrolytic copper foil in region V.
3 surface layer of electrolytic copper foil manufactured by manufacturing method via above-mentioned electrolytic copper foil has down-like structure, and can increase
Sum it up the area of resin substrate then.Specifically, the electrolytic copper foil 3 of the embodiment of the present invention includes all one's life layers of foil 30 and is located at
Surface-treated layer 31 on foil layer 30.
Surface-treated layer 31 is located on the rough surface 30a or shiny surface 30b of foil layer 30.In one embodiment, cathode copper
The overall thickness T of foil 3 is determined depending on practical application request between 6 to 400 μm.
As shown in figure 5, in embodiments of the present invention, surface-treated layer 31 includes multiple villiforms or approximate villous copper
Tumor 310, and each villiform or approximate villous copper tumor 310 are along not parallel with rough surface 30a or shiny surface 30b
Long axis direction extends.
In addition, each villiform or approximate villous copper tumor 310 have a maximum major diameter D1 and one most
Big minor axis diameter D2.In one embodiment, maximum major diameter D1 is described maximum short between 0.5 μm to 1.5 μm
Shaft diameter D2 is between 0.1 μm to 1.0 μm.In addition, forming an approximate villous appearance between each two adjacent copper tumor 310
Empty a S1.
It please compare Fig. 1 and Fig. 5, size of the spherical shape copper tumor in the prior art on short-axis direction can be more than long axis side
Upward size, and it is distributed comparatively dense.In comparison, multiple villiforms of the electrolytic copper foil 3 of the embodiment of the present invention or approximate suede
The copper tumor 310 of hairy is on short-axis direction (direction for being namely parallel to the rough surface 30a or shiny surface 30b of foil layer 30)
Diameter can be also smaller than the diameter on long axis direction.In a preferred embodiment, the maximum minor axis diameter of villiform copper tumor 310
The ratio of D2 and maximum major diameter D1 are between 0.2 to 0.7.
In the embodiment of the present invention, there is no big by the maximum major diameter D1 of villiform or approximate villous copper tumor 310
In the diameter of existing spherical shape copper tumor.Therefore, the surface roughness of the electrolytic copper foil 3 in the embodiment of the present invention there is no because
The shape of copper tumor changes and is significantly increased.In one embodiment, the thickness t of surface-treated layer 31 be about between 0.1 to 4 μm it
Between, and 10 average surface roughness (Rz) of surface-treated layer 31 are about between 1 to 4 μm.Accordingly, the present invention is implemented
The electrolytic copper foil 3 of example is still applicable to cooperation high frequency substrate, to transmit high-frequency signal.
On the other hand, in the electrolytic copper foil of the embodiment of the present invention 3, each two adjacent villiform or approximate villous
Spacing P1 between copper tumor 310 is also wider.In other words, the villiform of the embodiment of the present invention or approximate villous copper tumor 310
Also there is lower density.In one embodiment, between each two adjacent villiform or approximate villous copper tumor 310
It is between 0.1 to 0.4 μm away from P1, and the distribution density of these villiforms or approximate villous copper tumor 310 is every square
Micron 2 to 5.
Please refer to Fig. 6 and Fig. 7.Scanning electron microscope captured by electrolytic copper foils of the Fig. 6 to the embodiment of the present invention
(SEM) photo, Fig. 7 show the scanning electron microscope photo captured by the electrolytic copper foil to a comparative example.
First illustrate, in the electrolytic copper foil of comparison example, is executing parameter and Ben Fa when roughening treatment is electroplated
Bright embodiment is roughly the same, but execute roughening treatment is electroplated when used electroplate liquid composition in containing concentration be more than 40g/
The copper of L.
Compare the photo of Fig. 6 and Fig. 7 it can be found that the embodiment of the present invention by adjusting the first electroplate liquid composition, it is made
The copper tumor particle size for the electrolytic copper foil produced is smaller, and shape is more elongated.The copper tumor shape of the comparative example electrolytic copper foil of Fig. 7 is in
Spherical shape, and it is coarseer.
Fig. 8 is please referred to, display is electrolysed by focused ion beam and the embodiment of the present invention captured by electron beam microscopic system
The photo of the focused ion beam (FIB) of copper foil.Fig. 8 and show the embodiment of the present invention electrolytic copper foil partial cross-section (cross
Section it) shows up.
By the photo of Fig. 6 and Fig. 8 it can be proved that the electrolytic copper foil of the embodiment of the present invention is after passing through surface treatment, meeting
Form multiple villiform copper tumors rather than spherical shape copper tumor.In addition, by focused ion beam and electron beam microscopic system to the present invention
The electrolytic copper foil 3 of embodiment is analyzed, the copper crystalline particle of electrolytic copper foil long axis direction size be between 2.5 to 6.0 μm,
It is between 0.2 to 2.0 μm in short-axis direction size.
Then, referring again to Fig. 2, in embodiments of the present invention, in step S300, a surface treatment is executed.It is above-mentioned
Surface treatment can be heat resistanceheat resistant processing, anti-oxidant treatment, silane coupling agent processing at least one of.
It is to form a kirsite heat resistanceheat resistant on surface-treated layer by electrolytic method when surface treatment is heat resistanceheat resistant processing
Layer, and increase the heat resistance of electrolytic copper foil.In one embodiment, used electrolyte composition includes when executing heat resistanceheat resistant processing
1 to 4g/L zinc and 0.3 to 2.0g/L nickel, and execute heat resistanceheat resistant processing when used current density be 0.4 to
2.5A/dm2。
It is to form an anti oxidation layer on surface-treated layer by electrolytic method when surface treatment is anti-oxidant treatment,
To increase the inoxidizability of electrolytic copper foil.When executing anti-oxidant treatment, used electrolyte composition includes 1 to 4g/L oxygen
Change chromium and 5 to 20g/L sodium hydroxide, and used current density is 0.3 to 3.0A/dm when executing heat resistanceheat resistant processing2。
When surface treatment is silane coupling processing, a silane coupling agent process layer can be formed on surface-treated layer,
In, 0.3 to 1.5% weight silane coupling agent is used when executing in silane coupling processing.
Please refer to Fig. 9 and Figure 10.Fig. 9 shows that the diagrammatic cross-section of the circuit board module of the embodiment of the present invention, Figure 10 are shown
Partial enlarged view of the circuit board module of Fig. 9 in region X.The electrolytic copper foil of the embodiment of the present invention can be applied to different wiring boards
Component, such as rigid printed circuit board (PCB), flexible printed wiring board (FPC) and its homologue.
In the embodiment in fig. 9, circuit board module M1 faces face pressure by a resin substrate 4 and above-mentioned electrolytic copper foil 3
It closes and is formed, and the surface-treated layer 31 of electrolytic copper foil 3 can face resin substrate 4.
Resin substrate 4 can be high frequency substrate, such as：Epoxy resin base plate, polyoxy xylene resin substrate (PPO) or fluorine system
Resin substrate, or by polyimides, ethylene terephthalate, makrolon, liquid crystal polymer or polytetrafluoroethylene (PTFE) etc.
The substrate that material is constituted.
In the embodiment of Fig. 9 and Figure 10, resin substrate 4 is semi-solid preparation substrate or liquid crystal polymer substrate.It can by Figure 10
To find out, since the spacing between the villiform copper tumor 310 of the embodiment of the present invention is wider, pressed in electrolytic copper foil 3 and resin substrate 4
When conjunction, resin substrate 4 can coat and contact the most surfaces of villiform or approximate villous copper tumor 310, and can be deeply close
Like in villous accommodating space S1.In this way, the Bonding strength between electrolytic copper foil 3 and resin substrate 4 is made to enhance.
Figure 11 is please referred to, shows the diagrammatic cross-section of the circuit board module of another embodiment of the present invention.In the present embodiment,
Resin substrate 4 with electrolytic copper foil 3 be combined by adhesion glue 5, and a part for adhesion glue 5 can insert it is approximate villous accommodating
In space.
The electrolytic copper foil 3 of the embodiment of the present invention is tested after being pressed with resin substrate 4, and peel strength can all be more than 3lb/
in.Specifically, in an experimental example, resin substrate 4 is glass mat (FR4), and by glass mat (FR4) and this hair
The electrolytic copper foil of bright embodiment is pressed, and laminated plates test film is formed.Then, it is measured using peel strength puller system.
Test result shows the peel strength of electrolytic copper foil at least more than 3.5lb/in.
In addition, the manufacturing method of the circuit board module of the embodiment of the present invention can also further comprise in pressing electrolytic copper foil 3
After resin substrate 4, electrolytic copper foil 3 is patterned by etching mode, and forms a line layer.
In conclusion the beneficial effects of the present invention are in the manufacturing method of the electrolytic copper foil using the embodiment of the present invention
The concentration of copper can be made to reduce and make arsenic oxide arsenoxide and tungstate radicle by adjusting the composition of the first electroplate liquid L1 in plating roughening treatment
The content of ion be no more than 20ppm, therefore can limit copper tumor crystallization direction and growth direction, to form villiform or approximation
Villous copper tumor 310.
The lateral dimension of spherical shape copper tumor F10 in compared to the prior art, villiform or approximate villous copper tumor 310
It is smaller, the then surface area between electrolytic copper foil 3 and resin substrate 4 can be increased.In addition, two adjacent villiforms or approximate suede
There is relatively wide distance between the copper tumor 310 of hairy, when resin substrate 4 and electrolytic copper foil 3 then when, resin substrate 4 can wrap
The surface of entire copper tumor is covered, and gos deep into the space between two villiforms or approximate villous copper tumor 310, to increase electrolysis
Degree of sticking together between copper foil 3 and resin substrate 4 or adhesion layer 5.
Due to the electrolytic copper foil 3 of the embodiment of the present invention villiform or approximate villous copper tumor 310 in vertical direction
Size be not greater than the sizes of spherical shape copper tumor F10 in the prior art in vertical direction, therefore, the table of electrolytic copper foil 3
Surface roughness is lower compared to the surface roughness of existing copper foil.But the peel strength of the electrolytic copper foil 3 of the embodiment of the present invention
It does not decline to a great extent because surface roughness reduces, and meets the demand of practical application.
The following table 1 is please referred to, shows surface roughness (Roughness), the peel strength of the embodiment of the present invention and comparative example
The ratio (P/R ratio) of (Peel Strength) and peel strength and surface roughness, wherein surface roughness are 10 points
Mean roughness (Rz).Embodiment is the electrolytic copper foil for having villiform or approximate villiform copper tumor, and comparative example is that have circle
The electrolytic copper foil of spherical copper tumor.
Table 1
| Comparative example | Embodiment | |
| Surface roughness (μm) | 3.42 | 1.16 |
| Peel strength (lb/in) | 4.99 | 3.94 |
| Peel strength/surface roughness | 1.46 | 3.40 |
As can be seen from Table 1, the surface roughness of the electrolytic copper foil of the embodiment of the present invention (has ruler compared to comparative example
Very little larger spherical shape copper tumor) surface roughness it is lower, therefore the electrolytic copper foil of the embodiment of the present invention is kept pouring in applied to height
When defeated, the loss of signal can be further decreased.
In addition it is noted that the ratio of peel strength and surface roughness is bigger, the peel strength of copper foil is thick by surface
The influence of rugosity is smaller, and the performance capabilities of peel strength is better.Compared to comparative example it can be seen from upper table, the present invention is real
Apply the peel strength of the electrolytic copper foil of example and the ratio bigger of surface roughness.Therefore, the electrolytic copper foil of the embodiment of the present invention
There is no the losses excessive because of low surface roughness for peel strength.
The foregoing is merely the preferable possible embodiments of the present invention, the protection model of non-therefore the limitation present invention claim
The equivalence techniques variation enclosed, therefore description of the invention and accompanying drawing content is used to be done such as, the right for being both contained in the present invention are wanted
In the protection domain asked.
Claims (15)
1. a kind of manufacturing method of the electrolytic copper foil of tool approximation villiform copper tumor, which is characterized in that the approximate villiform copper of the tool
The manufacturing method of the electrolytic copper foil of tumor includes：
By an electrolytic method to form all one's life layers of foil, wherein the foil layer has a predetermined surface；And
A surface-treated layer is formed in the predetermined surface of the foil layer, there are approximate fluff structures to form a surface layer
Electrolytic copper foil, wherein the surface-treated layer includes the villous copper tumor of multiple approximations, and each two adjacent approximate suede
An approximate villous accommodating space is formed between the copper tumor of hairy；
Wherein, the step of forming the surface-treated layer still further comprises：It executes a plating roughening treatment for the first time and holds
Curing process is electroplated in row one for the first time, wherein in one first electroplate liquid used in first time plating roughening treatment containing 3 to
The copper of 40g/L, 100 to 120g/L sulfuric acid, the arsenic oxide arsenoxide no more than 20ppm and 5 to 20ppm tungstate ion.
2. the manufacturing method of the electrolytic copper foil of tool approximation villiform copper tumor as described in claim 1, which is characterized in that executing
Used current density is 15 to 40A/dm when the first plating roughening treatment2, and the predetermined surface be rough surface or
Person's shiny surface.
3. the manufacturing method of the electrolytic copper foil of tool approximation villiform copper tumor as claimed in claim 2, which is characterized in that form institute
The step of stating surface-treated layer still further comprises：It executes second of plating roughening treatment and executes second of plating admittedly
Change is handled, and the parameter and the first time plating parameter of roughening treatment of second of plating roughening treatment are identical and described
The parameter of second of plating curing process is identical as the first time plating parameter of curing process.
4. the manufacturing method of the electrolytic copper foil of tool approximation villiform copper tumor as claimed in claim 3, which is characterized in that form institute
The step of stating surface-treated layer is sequentially to execute the first time plating roughening treatment, first time plating curing process, institute
State second of plating roughening treatment and second of plating curing process.
5. the manufacturing method of the electrolytic copper foil of tool approximation villiform copper tumor as claimed in claim 3, which is characterized in that form institute
The step of stating surface-treated layer is sequentially to execute the first time plating roughening treatment, second of plating roughening treatment, institute
State plating curing process for the first time and second of plating curing process.
6. the manufacturing method of the electrolytic copper foil of tool approximation villiform copper tumor as described in claim 1, which is characterized in that executing
Containing 50 to 70g/L copper, 70 to 100g/L sulphur in used one second electroplate liquid when the first time plating curing process
Acid and the arsenic oxide arsenoxide less than 30ppm, and execute first time curing process is electroplated when used current density be 2 to
9A/dm2。
7. the manufacturing method of the electrolytic copper foil of tool approximation villiform copper tumor as described in claim 1, which is characterized in that described
The manufacturing method of the electrolytic copper foil of the approximate villiform copper tumor of tool still further comprises：Primary antibody heat treatment is executed, on the surface
A kirsite heat shield is formed in process layer, wherein when executing heat resistanceheat resistant processing used electrolyte composition include 1 to
The zinc of 4g/L and 0.3 to 2.0g/L nickel, and when executing heat resistanceheat resistant processing used current density be 0.4 to
2.5A/dm2。
8. the manufacturing method of the electrolytic copper foil of tool approximation villiform copper tumor as described in claim 1, which is characterized in that described
The manufacturing method of the electrolytic copper foil of the approximate villiform copper tumor of tool still further comprises：An anti-oxidant treatment is executed, in the table
An anti oxidation layer is formed on surface treatment layer, wherein when executing the anti-oxidant treatment used electrolyte composition include 1 to
The chromium oxide of 4g/L and 5 to 20g/L sodium hydroxide, and used current density is when executing heat resistanceheat resistant processing
0.3 to 3.0A/dm2。
9. the manufacturing method of the electrolytic copper foil of tool approximation villiform copper tumor as described in claim 1, which is characterized in that described
The manufacturing method of the electrolytic copper foil of the approximate villiform copper tumor of tool still further comprises：A silane coupling processing is executed, with described
A silane coupling agent process layer is formed on surface-treated layer, wherein when executing the silane coupling processing using 0.3 to
1.5% weight silane coupling agent.
10. the manufacturing method of the electrolytic copper foil of tool approximation villiform copper tumor as described in claim 1, which is characterized in that multiple
There is the villous copper tumor of approximation a maximum major diameter and a maximum minor axis diameter, maximum major diameter to be situated between
Between 0.5 μm to 1.5 μm, maximum minor axis diameter between 0.1 μm to 1.0 μm, and maximum minor axis diameter with most greatly enhance
Ratio between shaft diameter is 0.2 to 0.7.
11. the manufacturing method of the electrolytic copper foil of tool approximation villiform copper tumor as described in claim 1, which is characterized in that multiple
The distribution density of the villous copper tumor of approximation is often square micron 2 to 5, and each two adjacent approximate villiform
Copper tumor between spacing be between 0.1 to 0.4 μm.
12. a kind of manufacturing method of circuit board module, which is characterized in that the manufacturing method of the circuit board module includes：
The electricity for having approximate villiform copper tumor as described in being formed by such as the manufacturing method of one of claim 1 to 11 is provided
Solve copper foil；And
The electrolytic copper foil of the approximate villiform copper tumor of the tool is pressed face-to-face with a resin substrate, to form a circuit board group
Part, wherein the surface-treated layer faces the resin substrate.
13. the manufacturing method of circuit board module as claimed in claim 12, which is characterized in that the approximate villiform copper tumor of the tool
Electrolytic copper foil peel strength at least more than 3lb/in.
14. the manufacturing method of circuit board module as claimed in claim 12, which is characterized in that the approximate villiform copper tumor of the tool
Electrolytic copper foil combined by an adhesion glue with the resin substrate, and the part filling approximate villus of the adhesion glue
In the accommodating space of shape.
15. the manufacturing method of circuit board module as claimed in claim 12, which is characterized in that the resin substrate is semi-solid preparation
Substrate or liquid crystal polymer substrate, and when the electrolytic copper foil of the approximate villiform copper tumor of the tool is pressed with the resin substrate,
A part for the resin substrate is inserted in the villous accommodating space of approximation.
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| WO2022176648A1 (en) * | 2021-02-19 | 2022-08-25 | 日本電解株式会社 | Surface-treated copper foil |
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| CN112118669A (en) * | 2019-06-19 | 2020-12-22 | 金居开发股份有限公司 | Advanced reverse electrolytic copper foil and copper foil substrate using same |
| CN111304700A (en) * | 2020-03-26 | 2020-06-19 | 深圳市惟华电子科技有限公司 | Preparation method of reverse copper foil |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2018141228A (en) | 2018-09-13 |
| JP6894811B2 (en) | 2021-06-30 |
| TW201831733A (en) | 2018-09-01 |
| TWI619851B (en) | 2018-04-01 |
| CN117641764A (en) | 2024-03-01 |
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