CN111394765A - Electrolytic copper foil surface treatment process - Google Patents
Electrolytic copper foil surface treatment process Download PDFInfo
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- CN111394765A CN111394765A CN202010253516.2A CN202010253516A CN111394765A CN 111394765 A CN111394765 A CN 111394765A CN 202010253516 A CN202010253516 A CN 202010253516A CN 111394765 A CN111394765 A CN 111394765A
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 134
- 239000011889 copper foil Substances 0.000 title claims abstract description 121
- 238000000034 method Methods 0.000 title claims abstract description 40
- 230000008569 process Effects 0.000 title claims abstract description 37
- 238000004381 surface treatment Methods 0.000 title claims abstract description 24
- 238000009713 electroplating Methods 0.000 claims abstract description 31
- 238000011282 treatment Methods 0.000 claims abstract description 27
- 238000007788 roughening Methods 0.000 claims abstract description 17
- 230000003064 anti-oxidating effect Effects 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 13
- 239000011888 foil Substances 0.000 claims abstract description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052802 copper Inorganic materials 0.000 claims abstract description 12
- 239000010949 copper Substances 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 9
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 7
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 7
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 7
- 229940117975 chromium trioxide Drugs 0.000 claims abstract description 7
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims abstract description 7
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 7
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 7
- 239000008103 glucose Substances 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 239000011261 inert gas Substances 0.000 claims abstract description 6
- 239000011248 coating agent Substances 0.000 claims abstract description 5
- 238000000576 coating method Methods 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims abstract description 5
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 claims abstract description 5
- 229910000375 tin(II) sulfate Inorganic materials 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001369 Brass Inorganic materials 0.000 claims abstract description 4
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 4
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 4
- 239000012298 atmosphere Substances 0.000 claims abstract description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims abstract description 4
- 239000010951 brass Substances 0.000 claims abstract description 4
- 238000000151 deposition Methods 0.000 claims abstract description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 4
- 238000005507 spraying Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 33
- 239000000758 substrate Substances 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- -1 mercapto compounds Chemical class 0.000 claims description 3
- 238000004804 winding Methods 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims 1
- 238000011161 development Methods 0.000 abstract description 5
- 239000000654 additive Substances 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 230000000996 additive effect Effects 0.000 abstract description 3
- 238000002791 soaking Methods 0.000 abstract description 2
- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical compound [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 230000008054 signal transmission Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007888 film coating Substances 0.000 description 2
- 238000009501 film coating Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- IKWTVSLWAPBBKU-UHFFFAOYSA-N a1010_sial Chemical compound O=[As]O[As]=O IKWTVSLWAPBBKU-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910000413 arsenic oxide Inorganic materials 0.000 description 1
- 229960002594 arsenic trioxide Drugs 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 238000001978 electrochemical passivation Methods 0.000 description 1
- 239000002659 electrodeposit Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Images
Classifications
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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
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
-
- 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
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
-
- 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
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
-
- 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
- C25D5/48—After-treatment of electroplated surfaces
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F1/00—Electrolytic cleaning, degreasing, pickling or descaling
- C25F1/02—Pickling; Descaling
- C25F1/04—Pickling; Descaling in solution
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
The invention discloses an electrolytic copper foil surface treatment process, which comprises the following steps: pre-treating; coarsening: roughening the pretreated original foil in a solution containing copper sulfate, sulfuric acid, sodium silicate and stannous sulfate; and (3) curing: depositing a layer of compact metal copper in the gaps of the nodular particles of the roughened copper foil; electroplating dissimilar metal: heating the copper foil in an inert gas atmosphere to form a brass layer, and then performing an oxidation resistance treatment: dissolving chromium trioxide and glucose solution in water to prepare antioxidant liquid; soaking the prepared copper foil in the antioxidant liquid for 1-4 s; coating: carrying out anti-oxidation treatment on a copper foil, spraying a silane coupling agent on the surface of the copper foil, and drying the surface of the copper foil; and (5) drying. According to the invention, the tin sulfate is added in the dissimilar metal electroplating process, the traditional process adopting Kun as an additive is replaced, the environment is protected, and the green development concept is met.
Description
Technical Field
The invention relates to the technical field of electrolytic copper foil treatment processes, in particular to an electrolytic copper foil surface treatment process.
Background
Copper foil is an extremely thin material of copper, and copper alloy sheets and tapes having a thickness of 100um or less are conventionally called copper foils. The electrolytic copper foil is an important material of a printed circuit board and is mainly used in the fields of electronic computers, industrial control, aerospace and all electrical appliances. In recent years, the domestic electronic information industry has been rapidly developed, and the demand of copper foil for printed circuit boards and upstream products thereof has increased. In recent years, with the continuous development of economy and great improvement of scientific and technical strength in China, China has become a large export country of printed circuit boards. The importance of the electrolytic copper foil in the industrial and national defense modernization construction is more and more obvious, the basic performance of electronic and electric products is directly influenced, and particularly the production technology of the high-grade electrolytic copper foil used on high-precision instruments reflects the advanced level of national industrial products to a certain extent. With the development of electronic products towards miniaturization and multi-functionalization, the requirements on the quality of copper foil products are higher and higher, for example, a thinned copper foil used in a fine circuit is required to have higher peel strength and can effectively reduce or avoid the phenomenon of 'side etching' generated during circuit etching, and a copper foil in a high-frequency circuit is required to have better ion migration resistance. The surface treatment process is an important step in the production process of the copper foil, namely, the specific surface area of the copper foil is increased through a series of roughening and curing treatments, so that the bonding force of a pressing plate is improved, and the roughening and curing treatments of the copper foil need to be carried out in a copper sulfate solution with a certain concentration and continuous electroplating under the action of direct current. At present, surface treatment process flows and process parameters adopted by various copper foil production enterprises in China are different, but generally comprise three treatment processes of coarsening, heat resistance and oxidation resistance, and the common process of electrolytic copper foil surface treatment can be summarized as original foil- > pretreatment- > coarsening- > curing- > electroplating of dissimilar metals (alloy plating) - > oxidation resistance- > silane treatment- > drying. In recent years, domestic copper foil production enterprises have greatly improved copper foil production process flow and product quality, but have a considerable gap compared with international advanced copper foil production enterprises, China exports a large amount of low-grade copper foils, and the copper foils for the inner layer of a high-density interconnection board and the copper foils for a flexible circuit board with high technical content and added value are almost imported from Japan, Korea, Taiwan and the like. At present, when domestic enterprises carry out surface treatment on electrolytic copper foils, a zinc coating is mainly adopted for treating a barrier layer, the copper foil prepared by the method can generate a side corrosion phenomenon when being used for a circuit corrosion process of a printed circuit, so that the bonding force between the copper foil and an insulator matrix is reduced, the copper foil even falls off from the insulator matrix when the copper foil is serious, and the zinc-coated copper foil is easy to oxidize when being stored at normal temperature, which are important reasons for the large difference between the electrolytic copper foil of domestic enterprises and the performance of foreign high-grade electrolytic copper foils. Therefore, an improved surface treatment process of the electrolytic copper foil is urgently needed to expand the application range of the electrolytic copper foil in China.
Disclosure of Invention
The invention aims to provide an electrolytic copper foil surface treatment process, which is used for solving the problems in the prior art, is environment-friendly, solves the problem of side etching in the subsequent processing of the copper foil subjected to surface treatment in the traditional process and improves the quality of the prepared copper foil. In order to achieve the purpose, the invention provides an electrolytic copper foil surface treatment process, which comprises the following specific contents:
s1, pretreatment: cleaning the surface of the original foil by using a solution;
s2, coarsening, namely coarsening the pretreated original foil in a solution with copper sulfate concentration of 25-45 g/L, sulfuric acid of 60-105 ml/L, current density of 12A/d square meter, sodium silicate concentration of 0.07-0.15 g/L and stannous sulfate of 0.7 g/L;
s3, curing: depositing a layer of compact metal copper in the gaps of the nodular particles of the roughened copper foil;
s4, electroplating of dissimilar metals: heating the copper foil in an inert gas atmosphere to form a brass layer, cooling to normal temperature, and then putting the copper foil into an electroplating solution containing nickel sulfate for electrochemical electroplating;
s5, performing anti-oxidation treatment, namely melting chromium trioxide and glucose solution into water to prepare anti-oxidation liquid, wherein the concentration of the chromium trioxide is 0.4-0.8 g/L, and the concentration of the glucose is 2.4-6.0 g/L;
s6, coating: carrying out anti-oxidation treatment on a copper foil, spraying a silane coupling agent on the surface of the copper foil, and then drying the surface of the copper foil;
s7, drying: and drying and winding the coated copper foil.
Preferably, the solution used in step S1 is sulfuric acid, hydrogen peroxide, or a mixed aqueous solution thereof.
Preferably, step S2 includes first roughening and second roughening to increase the bonding strength of the copper foil to the joint edge substrate.
Preferably, chloride ions and mercapto compounds should be added in step S2 when preparing the copper sulfate solution.
Preferably, in the step S4, the inert gas is argon, the heating temperature is 120-; a sodium sulfate solution is also added into the electroplating solution to increase the conductivity of the electroplating solution;
preferably, in step S5, the antioxidant solution is further stirred with a stirring rod inserted therein so that the antioxidant solution continuously flows over the surface of the copper foil.
The invention discloses the following technical effects: the invention discloses an electrolytic copper foil surface treatment process, which adopts a treatment mode of matching chemical plating and electroplating, can form a very compact protective film on the surface of a copper foil, and an antioxidant liquid is easy to separate from the surface of the copper foil. The tin sulfate is added in the dissimilar metal electroplating process, the traditional process adopting Kun as an additive is replaced, the pollution to the environment can be reduced, and the requirement of green development of the electrolytic aluminum industry is met.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without inventive exercise.
FIG. 1 is a flow chart of the surface treatment process of the electrolytic copper foil of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in further detail below.
Referring to fig. 1, the invention provides an electrolytic copper foil surface treatment process, which comprises the following specific contents:
s1, pretreating acid liquor
The raw foil is put into a pickling tank for pretreatment (for removing oxidized parts on the surface of the copper foil and cleaning the surface of the foil for stains), and the process conditions are controlled such that the acid concentration is 76 g/L and the flow rate is 5m3/h。
S2, coarsening, namely coarsening the pretreated original foil in a solution with copper sulfate concentration of 25-45 g/L, sulfuric acid of 60-105 ml/L, current density of 12A/d square meter, sodium silicate concentration of 0.07-0.15 g/L and stannous sulfate of 0.7 g/L.
The quality of the coarsening quality of the copper foil seriously affects the quality of the printed circuit board, the coarsening layer treatment is an indispensable process for improving the bonding strength of the copper foil and a substrate material, and the surface of the produced raw foil needs to be subjected to the coarsening layer treatment in order to ensure that the copper foil has stronger adhesive force with a base material. In the course of the roughening treatment, strong granular and dendritic crystals are formed on the surface of the copper foil by cathodic electrodeposition, and a rough surface with high opening degree is formed to form a high specific surface area, which enhances the adhesive bonding force of resin (resin on a substrate or copper foil adhesive resin) penetration, and also increases the affinity with the resin.
Meanwhile, as copper foils are increasingly used in the production of electronic products, a skin effect exists in a high-frequency circuit (that is, as the signal transmission frequency increases, the current in the circuit almost concentrates on the surface of a circuit to flow), if the copper foils are roughened by using the traditional surface treatment technology, although the bonding strength of the copper foils and a substrate is ensured, the surface roughness of the copper foils is relatively large, the signal transmission distance is lengthened, the signal transmission delay, attenuation and other problems are caused, and the signal deformation and distortion are seriously caused, so that the copper foils with low surface roughness must be used, but the problem that the bonding force between the copper foils and the substrate is not firm exists when the copper foils with low roughness are used. In order to solve the problem, in the embodiment, when the surface of the electrolytic copper foil is treated, a certain concentration of sulfhydryl compound and chloride ion component are added into the plating solution containing copper ions to treat the surface of the electrolytic copper foil, so that the problem of weak bonding force between the copper foil and the substrate can be well solved, and the surface effect and the signal delay can be reduced when the finally obtained finished product is used for manufacturing a high-frequency circuit.
In this embodiment, the roughening includes two times, i.e., a first roughening process and a second roughening process. The first roughening is to electrodeposit spherical copper on the surface of the copper foil, so that the spherical copper can also generate a fastening effect with thermosetting resin while increasing the surface area in a joint surface, but because the spherical copper with a crystal structure plated on the rough surface is loose and fragile, copper powder is easy to fall off, and in order to prevent the situation, the second roughening treatment is carried out, namely a layer of compact copper layer is plated to seal the loose structure. In this embodiment, the bonding strength between the copper foil subjected to the secondary roughening treatment and the joint edge substrate is greatly improved, and on the basis of the invention, a person skilled in the art can perform the third roughening treatment or even the fourth roughening treatment according to the requirement on the performance of the copper foil to further improve the service performance of the copper foil, so as to enhance the bonding strength between the copper foil and the insulating substrate and improve the service performance of the insulating substrate.
The method comprises the steps of using a nickel plating solution, wherein the concentration of nickel sulfate in the electroplating solution is 200 g/L, the concentration of boric acid buffer is 20 g/L, sodium sulfate is added to enhance the conductivity of the electroplating solution, the concentration of sodium sulfate is 30 g/L, electroplating is carried out under the pH value, the current density for electroplating is 200A/300A, the electroplating temperature is 20-40 ℃, the electroplating time is 10-30s, the current density for electroplating can be increased in consideration of the working efficiency, the current density for electroplating can be increased, the electric potential of nickel is higher than that of zinc, the electroplating temperature can be effectively prevented from being higher than that of zinc, the electroplating temperature is 20-40 ℃, the electroplating time is not higher than that of nickel, the electroplating solution has a better chemical corrosion resistance, and the electrochemical corrosion resistance of the copper foil can be kept low, and the chemical corrosion resistance of the copper foil can be improved.
Importantly, sodium tungstate and stannous sulfate are used as additives in the embodiment, the successful substitution of the Kun additive in the coarsening process in the prior art is realized, and the treated product is more environment-friendly and meets the requirement of green development of the electrolytic aluminum industry.
S3, curing: and depositing a layer of compact metal copper in the gaps of the nodular particles of the roughened copper foil.
The solidification treatment is to deposit a layer of compact metal copper in the gaps of the nodular particles of the roughened layer of the copper foil processed in the step S2, increase the contact surface of the roughened layer and the rough foil substrate and reduce the roughness of the surface of the roughened layer. After the copper foil subjected to the roughening treatment in step S2 is treated, the foil surface is uneven and has great undulations, and the surface of the copper foil subjected to the curing treatment is relatively flat. After the solidification treatment, although the roughness is reduced, the contact surface of the coarsened layer and the rough foil is increased, so that the bonding strength of the treatment layer and the insulating substrate material is improved, and the phenomenon of delamination of the treatment layer and the rough foil is fundamentally eliminated.
S4, electroplating of dissimilar metals: heating the copper foil in an inert gas atmosphere to form a brass layer, cooling to normal temperature, and then placing the copper foil in an electroplating solution containing nickel sulfate for electrochemical electroplating.
S5, performing anti-oxidation treatment, namely melting chromium trioxide and glucose solution in water to prepare anti-oxidation liquid, wherein the concentration of the chromium trioxide is 0.4-0.8 g/L, and the concentration of the glucose is 2.4-6.0 g/L, soaking the copper foil prepared in the step S4 in the anti-oxidation liquid for 1-4S, and then performing electrolytic passivation treatment to form a chromized anti-oxidation film on the surface of the electrolytic copper foil, so that air is in contact with the chromized film but not in contact with the copper foil, and the finished copper foil can be prevented from being oxidized in the subsequent storage, transportation and downstream processing production processes to achieve the anti-oxidation purpose.
In the transportation, storage and production operation of copper clad laminate, the copper foil often encounters the pollution of water vapor, dust fall, oxidation and even fingerprints brought by the external environment, so that the surface of the copper foil generates color-changing spots and the like. Meanwhile, after the high temperature is applied to the high-temperature pressing of the board and the processing of the printed circuit board, the surface of the copper foil is locally discolored to form spots of copper oxide and the like. It affects solderability of the copper side, ink affinity, and resistance increase on the circuit, thus requiring passivation on both sides of the copper foil.
S6, coating: and (3) carrying out anti-oxidation treatment on the copper foil, spraying a silane coupling agent on the surface of the copper foil, and then drying the surface of the copper foil.
S7, drying: drying and winding the coated copper foil
The copper foil after the film coating process is dried and wound, in this embodiment, the copper foil after the film coating process is preferably dried by a hot air drying method, so that the surface stress of the copper foil can be removed at the same time, and a person skilled in the art can also use other reasonable drying processes, which are not limited herein.
The electrolytic copper foil treated by the process avoids the harm of arsenic oxide used by the traditional surface treatment process to the environment, simultaneously solves the problem of color change when the electrolytic copper foil subjected to the galvanized surface treatment is stored at normal temperature, and simultaneously, in the actual production, enterprises can purchase batch electrolytic copper foils in advance as raw materials for subsequent production.
In the description of the present invention, it is to be understood that the terms "longitudinal", "lateral", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", and the like, indicate orientations or positional relationships based on those shown in the drawings, are merely for convenience of description of the present invention, and do not indicate or imply that the referenced devices or elements must have a particular orientation, be constructed and operated in a particular orientation, and thus, are not to be construed as limiting the present invention.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (6)
1. The surface treatment process of the electrolytic copper foil is characterized by comprising the following steps:
s1, pretreatment: cleaning the surface of the original foil by using a solution;
s2, coarsening, namely coarsening the pretreated original foil in a solution with copper sulfate concentration of 25-45 g/L, sulfuric acid of 60-105 ml/L, current density of 12A/d square meter, sodium silicate concentration of 0.07-0.15 g/L and stannous sulfate of 0.7 g/L;
s3, curing: depositing a layer of compact metal copper in the gaps of the nodular particles of the roughened copper foil;
s4, electroplating of dissimilar metals: heating the copper foil in an inert gas atmosphere to form a brass layer, cooling to normal temperature, and then putting the copper foil into an electroplating solution containing nickel sulfate for electrochemical electroplating;
s5, performing anti-oxidation treatment, namely melting chromium trioxide and glucose solution into water to prepare anti-oxidation liquid, wherein the concentration of the chromium trioxide is 0.4-0.8 g/L, and the concentration of the glucose is 2.4-6.0 g/L;
s6, coating: carrying out anti-oxidation treatment on the copper foil, spraying a silane coupling agent on the surface of the copper foil, and then drying the surface of the copper foil;
s7, drying: and drying and winding the coated copper foil.
2. The electrolytic copper foil surface treatment process according to claim 1, wherein the solution used in step S1 is sulfuric acid, hydrogen peroxide, or a mixed aqueous solution thereof.
3. The electrolytic copper foil surface treatment process of claim 1, wherein the step S2 includes first roughening and second roughening to increase the bonding strength of the copper foil to the joint edge substrate.
4. The electrolytic copper foil surface treatment process of claim 1, wherein chloride ions and mercapto compounds are further added in the step S2 during the preparation of the copper sulfate solution.
5. The electrolytic copper foil surface treatment process as claimed in claim 1, wherein the inert gas in step S4 is argon, the heating temperature is 120-; and a sodium sulfate solution is also added into the electroplating solution to increase the conductivity of the electroplating solution.
6. The electrolytic copper foil surface treatment process according to claim 1, wherein in step S5, the antioxidant liquid is stirred by inserting a stirring rod so that the antioxidant liquid flows continuously over the surface of the copper foil.
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