CN1701137B - Surface-treated copper foil having blackening-treated surface, process for producing the surface-treated copper foil and, using the surface-treated copper foil, electromagnetic wave shielding conducti - Google Patents
Surface-treated copper foil having blackening-treated surface, process for producing the surface-treated copper foil and, using the surface-treated copper foil, electromagnetic wave shielding conducti Download PDFInfo
- Publication number
- CN1701137B CN1701137B CN2004800010169A CN200480001016A CN1701137B CN 1701137 B CN1701137 B CN 1701137B CN 2004800010169 A CN2004800010169 A CN 2004800010169A CN 200480001016 A CN200480001016 A CN 200480001016A CN 1701137 B CN1701137 B CN 1701137B
- Authority
- CN
- China
- Prior art keywords
- copper foil
- surface treatment
- black
- treated side
- rose vitriol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 257
- 239000011889 copper foil Substances 0.000 title claims abstract description 232
- 238000000034 method Methods 0.000 title claims abstract description 108
- QUQFTIVBFKLPCL-UHFFFAOYSA-L copper;2-amino-3-[(2-amino-2-carboxylatoethyl)disulfanyl]propanoate Chemical compound [Cu+2].[O-]C(=O)C(N)CSSCC(N)C([O-])=O QUQFTIVBFKLPCL-UHFFFAOYSA-L 0.000 title 1
- 238000004519 manufacturing process Methods 0.000 claims abstract description 78
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 26
- 238000001035 drying Methods 0.000 claims abstract description 21
- 238000007747 plating Methods 0.000 claims abstract description 20
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims abstract description 4
- 229940044175 cobalt sulfate Drugs 0.000 claims abstract description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims abstract description 4
- 238000004381 surface treatment Methods 0.000 claims description 143
- 241000220317 Rosa Species 0.000 claims description 106
- 239000011248 coating agent Substances 0.000 claims description 84
- 238000000576 coating method Methods 0.000 claims description 84
- 238000012545 processing Methods 0.000 claims description 76
- 239000007788 liquid Substances 0.000 claims description 48
- 238000010586 diagram Methods 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 4
- 238000005530 etching Methods 0.000 abstract description 74
- 238000005406 washing Methods 0.000 abstract description 34
- 229910017052 cobalt Inorganic materials 0.000 abstract description 25
- 239000010941 cobalt Substances 0.000 abstract description 25
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 25
- 229910052802 copper Inorganic materials 0.000 abstract description 24
- 239000010949 copper Substances 0.000 abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 21
- DAYYOITXWWUZCV-UHFFFAOYSA-L cobalt(2+);sulfate;hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-]S([O-])(=O)=O DAYYOITXWWUZCV-UHFFFAOYSA-L 0.000 abstract 1
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 111
- 239000000243 solution Substances 0.000 description 43
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 20
- HSSJULAPNNGXFW-UHFFFAOYSA-N [Co].[Zn] Chemical compound [Co].[Zn] HSSJULAPNNGXFW-UHFFFAOYSA-N 0.000 description 19
- 230000015572 biosynthetic process Effects 0.000 description 18
- 239000000843 powder Substances 0.000 description 18
- 229910000531 Co alloy Inorganic materials 0.000 description 17
- 238000009713 electroplating Methods 0.000 description 16
- 229910000990 Ni alloy Inorganic materials 0.000 description 15
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 15
- 238000012360 testing method Methods 0.000 description 14
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 13
- 239000002390 adhesive tape Substances 0.000 description 11
- 239000007921 spray Substances 0.000 description 10
- 238000007788 roughening Methods 0.000 description 9
- 230000003278 mimic effect Effects 0.000 description 8
- 229910001429 cobalt ion Inorganic materials 0.000 description 7
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 7
- RFYUQSQGLHNNOY-UHFFFAOYSA-N cobalt;sulfuric acid Chemical compound [Co].OS(O)(=O)=O RFYUQSQGLHNNOY-UHFFFAOYSA-N 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 241000784732 Lycaena phlaeas Species 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- OMSYGYSPFZQFFP-UHFFFAOYSA-J zinc pyrophosphate Chemical compound [Zn+2].[Zn+2].[O-]P([O-])(=O)OP([O-])([O-])=O OMSYGYSPFZQFFP-UHFFFAOYSA-J 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- 238000006424 Flood reaction Methods 0.000 description 3
- 208000003351 Melanosis Diseases 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000012797 qualification Methods 0.000 description 3
- 238000004088 simulation Methods 0.000 description 3
- 230000003746 surface roughness Effects 0.000 description 3
- MTRFEWTWIPAXLG-UHFFFAOYSA-N 9-phenylacridine Chemical compound C1=CC=CC=C1C1=C(C=CC=C2)C2=NC2=CC=CC=C12 MTRFEWTWIPAXLG-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 241000555268 Dendroides Species 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000003287 bathing Methods 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- 239000010951 brass Substances 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 229960004643 cupric oxide Drugs 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- HIRWGWMTAVZIPF-UHFFFAOYSA-N nickel;sulfuric acid Chemical compound [Ni].OS(O)(=O)=O HIRWGWMTAVZIPF-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 229910000563 Arsenical copper Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- XEMZLVDIUVCKGL-UHFFFAOYSA-N hydrogen peroxide;sulfuric acid Chemical compound OO.OS(O)(=O)=O XEMZLVDIUVCKGL-UHFFFAOYSA-N 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- LVIYYTJTOKJJOC-UHFFFAOYSA-N nickel phthalocyanine Chemical compound [Ni+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 LVIYYTJTOKJJOC-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Images
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
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0094—Shielding materials being light-transmitting, e.g. transparent, translucent
- H05K9/0096—Shielding materials being light-transmitting, e.g. transparent, translucent for television displays, e.g. plasma display panel
-
- 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
- C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
-
- 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
- C25D5/48—After-treatment of electroplated surfaces
-
- 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
-
- 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
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
- H05K9/0084—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising a single continuous metallic layer on an electrically insulating supporting structure, e.g. metal foil, film, plating coating, electro-deposition, vapour-deposition
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/38—Chromatising
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Plasma & Fusion (AREA)
- Electromagnetism (AREA)
- Electroplating Methods And Accessories (AREA)
- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
- Laminated Bodies (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
A surface-treated copper foil exhibiting excellent black color which can be worked by the customary copper etching process; and a conductive mesh for PDP produced from such a surface-treated copper foil. In particular, use is made of, for example, a surface-treated copper foil having a blackening-treated surface on a glossy surface side, characterized in that a cobalt sulfate plating layer is disposed on a glossy surface and a rustproof treated layer disposed thereon. For the production of this surface-treated copper foil, there is employed, for example, a process comprising subjecting a glossy surface of copper foil to electrolysis in a black cobalt plating solution containing cobalt sulfate (hexahydrate) at a current density of 2 A/dm<2> or higher so as to form a rustproof treatedlayer and thereafter carrying out water washing and drying.
Description
Technical field
The present invention relates to have the surface-treated copper foil of black treated side, the manufacture method of this surface-treated copper foil and the front panel hertzian wave shielded metal silk screen that adopts the plasma display of this surface-treated copper foil.
Background technology
The shielding of plasm display panel in the process of development, fades to conduction silk screen from the metalized fibers fabric with the conduction silk screen.In the manufacturing of this conduction silk screen, defined several method.One of its method is, the surface treatment copper foil lamination, stick on the PET film, adopts Fotoform process to make.Two of its method is that surface treatment copper foil after supporting substrate adopts Fotoform process to carry out etching, is peeled off the monomeric conduction silk screen of surface treatment copper foil of supporting substrate.
In addition, considered from power saving in recent years, reduce to the level of 50V from 200V with plasma body generation signal voltage and to develop as target, attempt be accompanied by the decline of this voltage and make brightness reduce, make the conduction silk screen the circuit width graph thinning, the lining rate of the front glass plate by the conduction silk screen is reduced.Therefore, the thickness attenuation of conduction silk screen, thus etching and processing is carried out easily.One of them is to carry out on the PET film by the sputter vapour deposition method, forms as galvanized a kind of lamella, then, adopts copper electroplating etc. to form thin copper layer, makes the manufacturing of the conduction silk screen of silk screen live width granular by Fotoform process.
Adopt any of these methods all can make the conduction silk screen, conduction silk screen body is installed in the front panel, can observe from the surface by front glass, so, be processed into a face of the surface-treated copper foil of this conduction silk screen, be processed into black and make and more strengthen through the brightness of light.Before this, in this processing, use the melanism processing etc. of the formation copper oxide that carries out in order to improve the binding property between multilayer printed wiring board and the internal layer circuit resin layer.
The technology trend Hitachi of non-patent literature 1:PDP material changes into テ Network ニ カ Le レ No. the 33rd, one ト of Port (1999-7)
Patent documentation 1: the spy opens flat 11-186785 communique
Patent documentation 2: the spy opens the 2000-31588 communique
Summary of the invention
Problem to be solved by this invention
Yet above-mentioned melanism is handled and is had great problem.That is,, can obtain the very strong extraordinary black surface of black effectively when when copper foil surface adheres to the black oxide of copper in a large number.But, the black oxide of the copper that forms at copper foil surface, adhesion amount the more, from coming off more easily of black surface, so-called powder obscission causes more easily.
When the powder obscission took place, the black oxide that comes off was sneaked into useless place, when being used for handling with the incorporate transparence of the face glass of front, was dispersed to transparent adhesive layer, became the major reason that transparency is worsened.
On the other hand, do not come off as the powder that melanism is handled, can form the black processing of good black side, general black nickel plating, nickelous sulfide plating, cobalt plating etc. are inquired into, but the problem that exists is to adopt common copper etching work procedure to carry out etching and processing from black treated side side.
, relate to the problem points of electronickelling here, the applicant is willing to disclose solution in 2003-045669 number the spy.But, having the surface treatment copper foil that adopts the galvanized black treated side of cobalt, still can't deal with problems.Particularly, the Copper Foil of tunicle is electroplated by the black system with cobalt of market circulation now, exists the etching reagent that adopts copper to be difficult to the cobalt layer is carried out the problem of etching and processing.
Therefore, wait in expectation on the market black processing layer with good black and adopt common copper etching work procedure can be easy to carry out the surface treatment copper foil of electroplating the cobalt tunicle that has of etching and processing and the conduction silk screen that adopts this surface treatment copper foil to make.
Solve the means of problem
What this part contriver etc. concentrated one's attention on to study found that, by adopting following surface treatment copper foil, even have black is the surface treatment copper foil of cobalt electrolytic coating, can easily carry out etching and processing, obtain the electromagnetic wave shielding conduction silk screen that the front panel of high-quality plasma display is used with copper etchant.
＜have a surface treatment copper foil of black treated side 〉
The surface treatment copper foil with black treated side that the present invention relates to comprises two kinds of situations that do not have antirust processing layer and have antirust processing layer.Therefore, antirust processing layer not necessarily but must have antirust processing layer in order to ensure the prolonged preservation of surface treatment copper foil.Below, the surface treatment copper foil that invention relates to this part is illustrated.
The 1st surface treatment copper foil: the surface treatment copper foil that this part invention relates to (below be called the 1st surface treatment copper foil) is that " surface treatment copper foil that has the black treated side on glossy surface wherein, is provided with gravimetric thickness 200mg/m on 1 face of copper foil layer
2～400mg/m
2The rose vitriol electrolytic coating, and the profile height of this black treated side is that 200nm or its are following ".The sectional layer structural simulation of this surface treatment copper foil 1a be shown in Fig. 1.
Shown in this Fig. 1, translate on the face at the light of electrolytic copper foil 7 and to form rose vitriol electrolytic coating 4, (when be electrolytic copper foil, be equivalent to asperities) on its opposite with trickle shot copper 3 and implemented the routine mimic diagram of one of surface treatment copper foil 1a under the roughening treatment state.Yet the opposite of the Copper Foil that use this moment both can have been carried out roughening treatment and also can not carried out roughening treatment.Shown in this Fig. 2, the mimic diagram of one of surface treatment copper foil 1b when having omitted back side roughening treatment example.The roughening treatment layer 2 that constitutes with trickle shot copper 3 for the fusible purpose of improving with base material etc. forms, also can be provided with as required.Form the method for this roughening treatment layer 2, can adopt above-mentioned formation method of adhering to trickle shot copper, make method that trickle cupric oxide adheres to etc., coarsing processing method is not particularly limited.Also have, to copper foil layer 7, the main rolled copper foil that adopts the electrolytic copper foil that obtains by electrolytic process, obtains by rolling process.
And, on the level and smooth glossy surface of this copper foil layer 7, rose vitriol electrolytic coating 4 is set.Here said rose vitriol electrolytic coating 4 means the layer that adopts cobalt sulfate solution to form with electrochemical plating.This rose vitriol electrolytic coating 4 is that the gravimetric thickness that adopts following manufacture method to form reaches 200mg/m
2～400mg/m
2Layer, its solvability to copper etchant solution is good, and can reach sufficient blackization.Have the black system that adopts original cobalt layer and electroplate the cobalt layer of the Copper Foil of tunicle, its gravimetric thickness reaches 1000mg/m
2About, very thick, quality differences such as the solvability of electrolytic coating.The result is that because thick, slack-off with the dissolution rate of copper etchant solution, simultaneously, this accumulates into high density cobalt element in copper etchant solution, becomes the major reason that the etching solution reactive force descends.Also have, the converted weight in the invention of this part is the value that is converted into weight of cobalt.Converted weight is that surface treatment copper foil is dissolved in the acid solution, obtains unit surface cobalt amount with luminescence of plasma spectrum analysis method etc., is converted into the every 1m of surface treatment copper foil
2Weight.
In addition, whether the cobalt electrolytic coating becomes is dissolved in copper etchant solution easily, known carry out cobalt when electroplating the plating condition have a significant impact.That is, resulting cobalt electroplating film has the best etching characteristic when adopting following surface treatment copper foil manufacture method of the present invention.
The 2nd characteristic that the surface treatment copper foil that the present invention relates to has is that the surface shape of this black treated side is not only extremely thick, and the profile height that this black treated side has is at 200nm or below the 200nm.That is, form dead smooth and have certain glossy black treated side.But, do not illustrate that in order not lead to misunderstanding it is certain having deviation in common manufacturing process's scope, needn't whole locational profile heights all below 200nm, in reflection manufacturing process extent of deviation, it is certain having the profile height that surpasses 200nm sometimes.For the profile height of the rose vitriol electrolytic coating 4 of measuring the surface treatment copper foil 1 that the present invention relates to, the FIB that adopts the FIB analytical equipment to observe section observes image and is shown in Fig. 3.The black treated side that on the electrolytic copper foil glossy surface, is forming shown in this Fig. 3.Also have, it is observed from the direction that observed surface is had 60 ° of angles that this FIB observes image.
As can be seen from Figure 3, the section of black treated side obviously exists certain concavo-convex, general employing contact pin type surface roughness meter when monitoring should be concavo-convex.The result is shown in the scale of Fig. 3, to it is believed that it is adopt the impossible correct mensuration level of surface roughness meter concavo-convex.In the present invention, as corresponding to the value that adopts the periodic Rmax of surface roughness instrumentation, the mountain portion in the field of view that FIB is observed and the maximum difference of paddy portion are as " profile height ".Position with " d " expression among this Fig. 3 is the profile height of Fig. 3, can judge to be about 100nm.Yet, in Fig. 3, rose vitriol electrolytic coating 4 forms with the shape of utmost point homogeneous thickness along copper foil surface, with the complete bonding state of copper foil surface maintenance of substrate, do not find unfavorable places such as rose vitriol electrolytic coating 4 projectioies, do not find the place that powder may fall yet.
Relatively therewith, the black treated side that on original copper foil surface, forms,, can obtain Fig. 4 and result shown in Figure 5 when carrying out FIB when observing from section equally with above-mentioned.That is, the shape that constitutes the black treated side is grown into dendroid.Form quite outstanding state from the substrate Copper Foil.Therefore, when measuring the profile height (d) of this moment, the occasion of Fig. 4 is about 480nm, and the occasion of Fig. 5 is about 270nm, can be regarded as and forms quite coarse surface.Yet, having this dendritic black treated side, easy bending, the surface that is vulnerable to damage can be thought by its dendroid portion, yet, if crooked part comes off, to produce dust releasing certainly, the inhomogenous reason of form and aspect takes place in the time of can thinking visual observation black treated side.
The surface treatment copper foil that the invention described above relates to is observed image from the FIB section of Fig. 3 and be can be understood as the surface with dead smooth.But, though be to have the processing of glossy black, be not to have the black treated side the gloss of the irreflexive degree of light that is subjected to, and, even the glossy surface to electrolytic copper foil and rolled copper foil is implemented the black processing, the L value reaches more than 27 or 27 in the Lab chromaticity diagram.Here, as more than 27 or 27 of record, the expression upper limit is not particularly limited, but on experience, the upper limit can reach about 41.
For preferably adopting glossiness, the gloss intensity of representing the black treated side replaces the Lab chromaticity diagram.The glossiness of the black treated side that the present invention relates to, the result who forms this black treated side at the glossy surface of electrolytic copper foil or rolled copper foil is that glossiness [Gs (60 °)] is to be preferred below 30 or 30.When glossiness reaches 30 or 30 when above, become the state of so-called black glossy, it is very showy that metalluster becomes.Here, the lower value of glossiness is uncertain, but empirical value is about 18.
The 2nd surface treatment copper foil: this surface treatment copper foil is, in order to ensure form in the lip-deep prolonged preservation of above-mentioned the 1st surface treatment copper foil antirust processing layer.The two sides of Fig. 6 is had antirust processing layer 5 surface treatment copper foil 1c the sectional layer structural simulation illustrate.Yet, the surface treatment copper foil 1d when the uneven surface side has been omitted roughening treatment shown in Figure 7.Only limit to antirust purpose as Copper Foil, can extensively adopt the inorganic inhibitor of zinc alloys such as organic corrosion inhibitors such as imidazoles, benzotriazole, the general zinc that uses or brass.In addition, on single face, form the antirust processing layer of rose vitriol electrolytic coating, must be located at the back side that surface treatment copper foil of the present invention is provided with the rose vitriol electrolytic coating at least, also do not have fault but be located at the two sides.
But when its two sides was provided with antirust processing layer 5, the effect of these antirust processing layers was to prevent that the trickle shot copper 3 of roughening treatment layer 2 from coming off and as the protective layer of rose vitriol layer 4, simultaneously, the outward appearance of surface treatment copper foil was had the effect that keeps for a long time.At this antirust processing layer 5, it is particularly preferred that zinc-nickel alloy layer or zinc-cobalt layer is set.These antirust processing layers 5 are used in combination with rose vitriol electrolytic coating 4, can be used as rose vitriol electrolytic coating 4 thus and carry out the dissoluting cocatalyst in etching when dissolving and play a role.That is, compare during with rose vitriol electrolytic coating 4 Individual existences, have zinc-nickel alloy layer or zinc-cobalt layer person, the dissolving of rose vitriol electrolytic coating 4 takes place rapidly.
In addition, the sectional layer of two sides with surface treatment copper foil 1c of antirust processing layer 5 and chromic salt gloss finish layer 6 is shown in Fig. 8 and Fig. 9 with constituting simulation.Comparison diagram 6 and Fig. 8, Fig. 7 and Fig. 9 are only have chromic salt gloss finish layer 6 with the surface treatment copper foil difference with antirust processing layer 5 as can be known respectively, and other constitute same.
After the antirust processing layer 5 that is made of zinc-nickel alloy or zinc-cobalt alloy etc. formed, this chromic salt gloss finish layer 6 formed on single face or two sides.In addition, because this chromic salt gloss finish layer 6 exists, the oxidation resistent susceptibility of surface treatment copper foil significantly improves, and can effectively prevent decoration corrosion (コ ス メ テ イ Star Network コ ロ one ジ ヨ Application) effects such as oxidation stain.
＜have a surface treatment copper foil manufacture method of black treated side 〉
The manufacture method of (manufacture method of the 1st surface treatment copper foil) above-mentioned the 1st surface treatment copper foil preferably adopts the manufacture method that contains following operation.This manufacture method can be subdivided into adopt to stir bathes and does not have and stir the situation of bathing, and is divided into " the manufacture method A of the 1st surface treatment copper foil ", " the manufacture method B of the 1st surface treatment copper foil " is illustrated:
The manufacture method A of the 1st surface treatment copper foil: here, the manufacture method of the black treatment process when employing is not had the stirring bath is illustrated.
Whether the Copper Foil that uses in the manufacture method of surface treatment copper foil of the present invention was no matter carried out roughened to the opposite that forms above-mentioned rose vitriol electrolytic coating.Here put down in writing, but the condition when implementing roughened is not particularly limited, for example, when forming this superfine little shot copper, generally can uses arsenical copper electrolyte in order to make provision against emergencies.For example, copper sulfate is solution, and the condition of employing is: copper concentration 5～10g/L, sulfuric acid concentration 100～120g/L, cl concn 20～30ppm, 9-phenylacridine 50～300mg/L, 30～40 ℃ of liquid temperature, current density 5～20A/dm
2Deng.
In a) operation, on the glossy surface of above-mentioned Copper Foil, form the rose vitriol electrolytic coating.This rose vitriol electrolytic coating adopts the rose vitriol electroplate liquid of sulfur acid cobalt (7 hydrate) 8g/L～10g/L, pH4.0 or 4.0 above scopes not bathe as having to stir, and adopts 2A/dm
2Or 2A/dm
2Above current density is carried out electrolysis, forms the rose vitriol electrolytic coating of black system.That is, it is the rose vitriol plating condition when not carrying out solution stirring.Here, the rose vitriol in the rose vitriol electroplate liquid (7 hydrate) is when being lower than 8g/L, and the electrodeposition rate of the rose vitriol electrolytic coating of formation is slack-off, and the thickness of sulfuric acid nickel dam has the uneven tendency that becomes strongly.In contrast, when rose vitriol (7 hydrate) when being higher than 10g/L, the tone that forms the rose vitriol electrolytic coating does not reach good black state.
In addition, to be adjusted to 4.5～5.5 target zone be preferred to the pH value of solution of Ci Shi rose vitriol electroplate liquid.In this scope, qualification rate is good, can obtain good black cobalt electrolytic coating.When carrying out this pH when adjusting, preferably do not add the ionogen beyond sodium hydroxide or the potassium hydroxide etc.The black of cobalt electrolytic coating becomes metallic color easily.
Therefore, by the solution metal ionic concn is kept certain, the result is that the pH of solution can be stabilized in more than 4.0 or 4.0.In order to make in this solution concentration of cobalt ions stable, adopt the solvability cobalt electrode, the dissolving of galvanic deposit cobalt ion composition is supplied with, or the continuous monitoring concentration of metal ions, suitably add with cobaltous hydroxide, it is preferred making the stable method of concentration of cobalt ions.
Yet the current density when carrying out electrolysis adopts 2A/dm
2Or 2A/dm
2Above electric current.Above-mentioned rose vitriol electroplate liquid flows through excessive Faradaic current, even form trickle concavo-convex plating face to a certain degree, also can not produce the powder obscission thus.Therefore, the current density upper limit needn't be set especially, can consider that the production efficiency arbitrary decision of operation gets final product according to general technology general knowledge.
At b) in the operation, the Copper Foil through above-mentioned operation wash, drying, can obtain the surface-treated copper foil of rose vitriol electrolytic coating as the black treated side.Here, method for washing, drying means are not particularly limited, can adopt the mode of common consideration.
The manufacture method B of the 1st surface treatment copper foil: here, the manufacture method of the black treatment process when stirring bath to adopting is illustrated.
In the manufacture method of surface treatment copper foil of the present invention, what form the rose vitriol electrolytic coating is the Copper Foil glossy surface, by adopting following condition, with same with the rose vitriol electrolytic coating that does not have the rose vitriol plating bath formation of stirring, forms fine and close black treated side.
At this moment, in a) operation, on the glossy surface of above-mentioned Copper Foil, adopt sulfur acid cobalt (7 hydrate) 10g/L～40g/L, pH4.0 or 4.0 above, the rose vitriol electroplate liquid of liquid temperature below 30 ℃ or 30 ℃ to bathe, adopt 4A/dm as stirring
2Or 4A/dm
2Following current density is carried out electrolysis, forms the rose vitriol electrolytic coating of black system.Promptly here, with the manufacture method A fundamental difference of the 1st surface treatment copper foil be to stir above-mentioned rose vitriol electroplate liquid limit and carry out electrolysis in the limit when electroplating carrying out rose vitriol.This cobalt sulfate concentration is lower, more can obtain good black state.But the rose vitriol in the rose vitriol electroplate liquid (7 hydrate) adopt the electrodeposition rate that stirs the rose vitriol electrolytic coating of bathing formation slack-off, and the thickness of sulfuric acid nickel dam has the uneven tendency that becomes strongly, becomes industrial obstacle when being lower than 10g/L.In contrast, when rose vitriol (7 hydrate) when being higher than 40g/L, the rose vitriol electrolytic coating of formation is difficult to form fine and close concavo-convex, and the result is the black state that does not reach good.
In addition, when the pH value of solution of rose vitriol electroplate liquid of this moment more than 4.0 or 4.0, it is preferred particularly being adjusted to 4.5～5.5 target zone.In this scope, qualification rate is good, can be stable obtain black cobalt electrolytic coating.When carrying out this pH when adjusting, preferably do not add the ionogen beyond sodium hydroxide or the potassium hydroxide etc.As mentioned above, the black of cobalt electrolytic coating becomes metallic color easily.Therefore, by the solution metal ionic concn is kept certain, the result is with above-mentioned same, and is stable in the scope more than 4.0 or 4.0.
Yet, the rose vitriol electroplate liquid of this moment, its liquid temperature is preferred using below 30 ℃ or 30 ℃.The liquid temperature of this moment is lower, and the tendency that can obtain good black treated side is more arranged.As the liquid temperature is set in below 30 ℃ or 30 ℃, adopt the manufacture method A of the 1st surface treatment copper foil, on the copper foil surface of roughened not, carry out above-mentioned black processing, can obtain good black treated side.
And, be used to carry out electrolytic current density, can adopt 4A/dm
2Or its following electric current.In this scope, even copper foil surface does not carry out roughened, also can form binding property with organic materials good, have a trickle concavo-convex rose vitriol electrolytic coating.Usually, be plate surface in order to obtain having concavo-convex black, can adopt the method for burning plating area (ヤ ケ メ Star キ) feeding Faradaic current to surplus.Yet here, it is littler to be used for electrolytic current density, and the tendency of the black processing that obtains having good stability is more arranged.Therefore, preferably adopt the little current density of trying one's best, but if consider that from industrial productivity the lower value of current density is decided to be 0.5A/dm
2On the other hand, when current density greater than 4A/dm
2The time, adopt the manufacture method A of above-mentioned the 1st surface treatment copper foil, can form and the copper foil surface that does not carry out roughened is carried out the black treated side of the same level of black processing, and needn't adopt manufacture method B.Yet the black treated side that forms in above-mentioned current density range can not produce the dust releasing phenomenon thus yet.
At b) in the operation, the Copper Foil through above-mentioned operation wash, drying, can obtain the surface-treated copper foil of rose vitriol electrolytic coating as the black treated side.Here, method for washing, drying means are not particularly limited, can adopt the mode of common consideration.
(manufacture method of the 2nd surface treatment copper foil)
When being the 2nd surface treatment copper foil, same with the manufacture method of above-mentioned the 1st surface treatment copper foil, make with the surface-treated copper foil of rose vitriol electrolytic coating as the black treated side, then, form antirust processing layer.Therefore, manufacturing process is for " a) forming black on the glossy surface of Copper Foil is the rose vitriol electrolytic coating; B) form antirust processing layer having formed on Copper Foil two sides that black is the rose vitriol electrolytic coating or the single face; C) then, wash, drying ".That is, in the manufacture method (manufacture method A and manufacture method B) of the 1st surface treatment copper foil, increase antirust processing layer and form operation.
Therefore, only antirust processing layer being formed operation here is illustrated.Form antirust processing layer having formed on Copper Foil two sides that black is the rose vitriol electrolytic coating or the single face.For adopting organic corrosion inhibitors such as original known imidazoles, benzotriazole, generally adopting the inorganic inhibitor of zinc alloys such as zinc or brass, do special explanation and adopt well-established law to get final product, so in this detailed.
Below, carry out electroplating processes to adopting zinc nickel alloy electroplating liquid or zinc-cobalt alloy electroplate liquid, the occasion that forms antirust processing layer is illustrated.At first, zinc nickel alloy electroplating is described.Here, the zinc nickel alloy electroplating liquid that adopts is not particularly limited, lift 1 for example down, the condition of employing is: the nickel concentration of used single nickel salt is that the zinc concentration of 1～2.5g/L, zinc pyrophosphate is that 0.1～1g/L, potassium pyrophosphate are 50～500g/L, 20～50 ℃ of liquid temperature, pH8～11, current density 0.3～10A/dm
2
Secondly, plating describes to zinc-cobalt alloy.Here used zinc-cobalt alloy electroplate liquid is not particularly limited, lift 1 for example down, the condition of employing is: the cobalt concentration of used rose vitriol is that the zinc concentration of 1～2.5g/L, zinc pyrophosphate is that 0.1～1g/L, potassium pyrophosphate are 50～500g/L, 20～50 ℃ of liquid temperature, pH8～11, current density 0.3～10A/dm
2Deng.The antirust processing layer that this zinc-cobalt alloy is electroplated and following chromate treating makes up shows excellent especially corrosion resistance nature.
When being the 2nd surface treatment copper foil, after copper foil surface forms zinc-nickel alloy layer or zinc-cobalt alloy layer etc.,, can obtain more excellent erosion resistance if form chromate coating.That is, after forming above-mentioned antirust processing layer the chromate treating operation being set also can.In this chromate treating operation, chromatedsolution is contacted with this copper foil surface carry out replacement Treatment, in chromatedsolution, carry out electrolysis, any method that forms the electrolytic chromate processing of chromic salt tunicle all can adopt.In addition, used here chromatedsolution can use the scope of common method.Then, by washing, drying, obtain having the surface treatment copper foil of black treated side.
＜electromagnetic wave shielding conduction silk screen〉have the surface treatment copper foil of the invention described above black treated side, do not fall powder and have good black from the black treated side, this black treated side can adopt common copper etch process to carry out etching and remove.Therefore, adopt the method for making printing distributing board, can easily be processed into arbitrary shape.Under the circumstances, it is suitable for using as electromagnetic wave shielding conduction silk screen in the front panel of plasm display panel most.
The effect of invention
Surface treatment copper foil with black treated side of the present invention, its rose vitriol electrolytic coating is not only extremely thin, and present can be anti-in the front panel of plasm display panel as the good black of the purposes of electromagnetic wave shielding conduction silk screen.And because cobalt contents is few, etching characteristic is good, and the reactive force of the copper etchant solution of common iron(ic) chloride, sulfuric acid-hydrogen peroxide system does not descend, and the solution life-span can keep for a long time.
In addition, surface treatment copper foil manufacture method of the present invention, upper surface are handled Copper Foil and can be made with good qualification rate, adopt above-mentioned the creating conditions can the most effective formation rose vitriol electrolytic coating, are dissolved in the copper etchant solution.
Description of drawings
Fig. 1 is the mimic diagram of sectional layer structure with surface treatment copper foil of black treated side.
Fig. 2 is the mimic diagram of sectional layer structure with surface treatment copper foil of black treated side.
Fig. 3 is that the FIB of sectional layer structure with surface treatment copper foil of black treated side observes image.
Fig. 4 is that the FIB of sectional layer structure with surface treatment copper foil of black treated side observes image.
Fig. 5 is that the FIB of sectional layer structure with surface treatment copper foil of black treated side observes image.
Fig. 6 is the mimic diagram of sectional layer structure with surface treatment copper foil of black treated side.
Fig. 7 is the mimic diagram of sectional layer structure with surface treatment copper foil of black treated side.
Fig. 8 is the mimic diagram of sectional layer structure with surface treatment copper foil of black treated side.
Fig. 9 is the mimic diagram of sectional layer structure with surface treatment copper foil of black treated side.
Figure 10 is the scanning electron microscope image through the copper foil surface of roughened.
Figure 11 is a scanning electron microscope image of observing the rose vitriol electrolytic coating.
Figure 12 is the scanning electron microscope image of etching test pattern.
Figure 13 is the scanning electron microscope image that does not pass through the rose vitriol electrolytic coating of roughened.
Figure 14 is the scanning electron microscope image that does not pass through the rose vitriol electrolytic coating of roughened.
Embodiment
Illustrate below and make above-mentioned surface treatment copper foil, adopt copper etchant solution to make the result of electromagnetic wave shielding conduction silk screen with black treated side.
The 1st surface treatment copper foil 1a in the present embodiment shown in the shop drawings 1 with the shape of etching method trial-production electromagnetic wave shielding conduction silk screen, confirms etching performance.
In the present embodiment, the Copper Foil of the nominal thickness 15 μ m that the electrolysis of employing copper-bath obtains.Then, adopt the dilution heat of sulfuric acid of 30 ℃ of sulfuric acid concentration 150g/L, liquid temperature, Copper Foil was flooded for 30 seconds in this solution, carry out surface cleaning.
Then, the asperities to the electrolytic copper foil of nominal thickness 15 μ m carries out roughened.The roughened of this moment, be to make this trickle shot copper 3 on the single face of Copper Foil B, adhere to the processing of formation, for copper sulfate is solution, adopting concentration is the solution of copper 10g/L, sulfuric acid 100g/L, chlorine 25ppm, 9-phenylacridine 140mg/L, 38 ℃ of liquid temperature, current density 15A/dm
2, 2 seconds electrolytic condition of electrolysis time.The copper foil surface of this roughening treatment is shown in Figure 10.
As a) operation, on the glossy surface of this electrolytic copper foil, form rose vitriol electrolytic coating 4.The formation of rose vitriol electrolytic coating 4 is, as do not have stir bathe adopt that rose vitriol (7 hydrate) 10g/L, pH transfer to 5.0, the rose vitriol electroplate liquid of 30 ℃ of liquid temperature, use 2A/dm
28 seconds of current density electrolysis, use it as black sulfuric acid cobalt electrolytic coating (thickness conversion: 320mg/m
2) form.At this moment, the concentration of cobalt ions in the solution is not adjusted especially.Because the short period of time electrolysis is so concentration of metal ions needn't be adjusted.The rose vitriol electrolytic coating that forms is shown in Figure 11.
As b) operation, carry out spray washing with competent pure water, in atmosphere temperature degree being heated to 150 ℃ drying oven with electricradiator, be detained for 4 seconds, remove moisture, obtain having the surface treatment copper foil 1a of the black treated side of very good tone.Also have, be provided with in principle at above-mentioned each inter process and adopt 15 seconds washing step of pure water washing, prevent that the solution of pretreatment procedure from entering.
The rerum natura of＜surface treatment copper foil 〉
The result that the surface treatment copper foil section with black treated side that the above-mentioned operation of process obtains is observed with the FIB device, obtain section shown in Figure 3, the profile height of this black treated side (d) is 100nm, the L value of this black treated side in the Lab chromaticity diagram is 30, and glossiness [Gs (60 °)] is 19.In addition, on the black treated side, paste self adhesive tape, do not find that test tape comes off by having peeled off powder.
＜plasma display the manufacturing of hertzian wave shielding conductive silk screen 〉
On the two sides of the above-mentioned surface treatment copper foil that obtains, paste the dry film that becomes etching protective film.Then, only overlapping with mask electromagnetic wave shielding conduction silk screen on the dry film of black treated side side as test, 45 ° of the offset angles of silk screen pitch 200 μ m, silk screen live width 10 μ m, net, to around have a silk screen electrode part the conductive mesh pattern carry out ultraviolet exposure.At this moment, the etch protection layer at whole back sides is also carried out ultraviolet exposure, can not remove by the development of back.Develop with alkaline solution then, form etched pattern.
In addition, the iron(ic) chloride etching solution with copper etchant solution carries out the copper etching from black treated side side, then, by the release etch protective layer, makes electromagnetic wave shielding conduction silk screen.The result is that no etch residue has carried out very good etching.Figure 12 illustrates the etching state of the test pattern (the wide 13 μ m of circuit) that is used to estimate etching.The beautiful circuit of as shown in Figure 12, obtain not having etch residue, etching coefficient is extremely good.
Embodiment 2
In the present embodiment, as shown in Figure 6, make the 2nd surface treatment copper foil 1c that has as the zinc-nickel alloy layer of antirust processing layer,, confirm etching with etching method trial-production electromagnetic wave shielding conduction silk screen.Therefore, before forming the black processing layer with the rose vitriol electrolytic coating similarly to Example 1, so only antirust treatment condition are illustrated.Also have, the rose vitriol thickness of plating layer of black converts similarly to Example 1, reaches 320mg/m
2
The single face of embodiment 1 has been formed the Copper Foil two sides of black sulfuric acid cobalt electrolytic coating here, carried out electroplating processes, formed the zinc-nickel alloy layer on the two sides with zinc nickel alloy electroplating liquid.The zinc-nickel alloy layer, the condition of employing is: the nickel concentration of used single nickel salt is that the zinc concentration of 2.0g/L, zinc pyrophosphate is that 0.5g/L, potassium pyrophosphate are 250g/L, 35 ℃ of liquid temperature, pH10, current density 5A/dm
2, in 5 seconds of electrolysis, separate out evenly level and smooth electrolytic coating in the two sides electrolysis
In addition, similarly to Example 1, carry out spray washing, in atmosphere temperature degree being heated to 150 ℃ drying oven with electricradiator, be detained for 4 seconds, remove moisture, obtain having the surface treatment copper foil 1c of the black treated side of very good tone with competent pure water.Also have, be provided with in principle at above-mentioned each inter process and adopt 15 seconds washing step of pure water washing, prevent that the solution of pretreatment procedure from entering.
The rerum natura of＜surface treatment copper foil 〉
The result that the surface treatment copper foil section with black treated side that the above-mentioned operation of process obtains is observed with the FIB device, obtain section shown in Figure 3, the profile height of this black treated side is 115nm, this black treated side L value in the Lab chromaticity diagram is 28, and glossiness [Gs (60 °)] is 21.In addition, on the black treated side, paste self adhesive tape, do not find that test tape comes off by having peeled off powder.
＜plasma display the manufacturing of hertzian wave shielding conductive silk screen 〉
Similarly to Example 1, adopt the conduction silk screen of the surface treatment copper foil trial-production shielding electromagnetic wave that obtains.The result is, even it is also harmless to exist antirust processing layer to carry out etching, very good etching is carried out in the etching noresidue.
Embodiment 3
In the present embodiment, as shown in Figure 8, manufacturing has as the zinc-nickel alloy layer of antirust processing layer and the 2nd surface treatment copper foil 1e of chromic salt gloss finish layer, with etching method trial-production electromagnetic wave shielding conduction silk screen, confirms etching.Therefore, before forming the black processing layer with the rose vitriol electrolytic coating, similarly to Example 1, so only antirust treatment condition are illustrated.Also have, the rose vitriol thickness of plating layer of black converts similarly to Example 1, reaches 320mg/m
2
The formation of antirust processing layer, zinc nickel alloy electroplating liquid is used in operation similarly to Example 2, after the two sides forms the zinc-nickel alloy layer, carries out the chromic salt gloss finish on the two sides.Adopt the electrolytic chromate gloss finish here, electrolytic condition is: chromic acid is 5.0g/L, pH11.5,35 ℃ of liquid temperature, current density 8A/dm
2, 5 seconds of electrolysis time.
In addition, after forming chromate coating, carry out spray washing with competent pure water, 4 seconds of delay in atmosphere temperature degree being heated to 150 ℃ drying oven with electricradiator, remove moisture, obtain having the surface treatment copper foil 1e of the black treated side of very good tone.Also have, be provided with in principle at above-mentioned each inter process and adopt 15 seconds washing step of pure water washing, prevent that the solution of pretreatment procedure from entering.
The rerum natura of＜surface treatment copper foil 〉
The result that the surface treatment copper foil section with black treated side that the above-mentioned operation of process obtains is observed with the FIB device, obtain section shown in Figure 3, the profile height of this black treated side is 121nm, this black treated side L value in the Lab chromaticity diagram is 27, and glossiness [Gs (60 °)] is 23.In addition, on the black treated side, paste self adhesive tape, do not find that test tape comes off by having peeled off powder.
＜plasma display the manufacturing of hertzian wave shielding conductive silk screen 〉
Similarly to Example 1, adopt the surface treatment copper foil trial-production electromagnetic wave shielding conduction silk screen that obtains.The result is, even it is also harmless to exist antirust processing layer to carry out etching, very good etching is carried out in the etching noresidue.
Embodiment 4
In the present embodiment, as shown in Figure 6, make the 2nd surface treatment copper foil 1c that has as the zinc-cobalt alloy layer of antirust processing layer,, confirm etching with etching method trial-production electromagnetic wave shielding conduction silk screen.Therefore, arrive with till the rose vitriol electrolytic coating formation black processing layer, similarly to Example 1, so only antirust treatment condition are illustrated.Also have, the rose vitriol thickness of plating layer of black converts similarly to Example 1, reaches 320mg/m
2
The glossy surface of embodiment 1 has been formed the Copper Foil two sides of black sulfuric acid cobalt electrolytic coating here, carried out electroplating processes, formed the zinc-cobalt alloy layer on the two sides with the zinc-cobalt alloy electroplate liquid.The zinc-nickel alloy layer, the condition of employing is: the cobalt concentration of used rose vitriol is that the zinc concentration of 2.0g/L, zinc pyrophosphate is that 0.5g/L, potassium pyrophosphate are 250g/L, 35 ℃ of liquid temperature, pH10, current density 5A/dm
2, in 5 seconds of electrolysis, separate out evenly level and smooth electrolytic coating in the two sides electrolysis
In addition, similarly to Example 1, carry out spray washing, in atmosphere temperature degree being heated to 150 ℃ drying oven with electricradiator, be detained for 4 seconds, remove moisture, obtain having the surface treatment copper foil 1c of the black treated side of very good tone with competent pure water.Also have, be provided with in principle at above-mentioned each inter process and adopt 15 seconds washing step of pure water washing, prevent that the solution of pretreatment procedure from entering.
The rerum natura of＜surface treatment copper foil 〉
The result that the surface treatment copper foil section with black treated side that the above-mentioned operation of process obtains is observed with the FIB device, obtain section shown in Figure 3, the profile height of this black treated side is 128nm, this black treated side L value in the Lab chromaticity diagram is 28, and glossiness [Gs (60 °)] is 20.In addition, on the black treated side, paste self adhesive tape, do not find that test tape comes off by having peeled off powder.
＜plasma display the manufacturing of hertzian wave shielding conductive silk screen 〉
Similarly to Example 1, adopt the surface treatment copper foil trial-production electromagnetic wave shielding conduction silk screen that obtains.The result is that even it is also harmless to exist antirust processing layer to carry out etching, etching is noresidue still, carries out very good etching.
Embodiment 5
In the present embodiment, as shown in Figure 8, manufacturing has as the zinc-cobalt alloy layer of antirust processing layer and the 2nd surface treatment copper foil 1e of chromate treating layer, with etching method trial-production electromagnetic wave shielding conduction silk screen, confirms etching.Therefore, arrive with till the rose vitriol electrolytic coating formation black processing layer, similarly to Example 1, so only antirust treatment condition are illustrated.Also have, the rose vitriol thickness of plating layer of black converts similarly to Example 1, reaches 320mg/m
2
The formation of antirust processing layer similarly to Example 4, is used the zinc-cobalt alloy electroplate liquid, after the two sides forms the zinc-cobalt alloy layer, carries out the chromic salt gloss finish on the two sides.Adopt the electrolytic chromate gloss finish here, electrolytic condition is: chromic acid is 5.0g/L, pH11.5,35 ℃ of liquid temperature, current density 8A/dm
2, 5 seconds of electrolysis.
In addition, after forming chromate coating, carry out spray washing with competent pure water, 4 seconds of delay in atmosphere temperature degree being heated to 150 ℃ drying oven with electricradiator, remove moisture, obtain having the surface treatment copper foil 1e of the black treated side of very good tone.Also have, be provided with in principle at above-mentioned each inter process and adopt 15 seconds washing step of pure water washing, prevent that the solution of pretreatment procedure from entering.
The rerum natura of＜surface treatment copper foil 〉
The result that the surface treatment copper foil section with black treated side that the above-mentioned operation of process obtains is observed with the FIB device, obtain section shown in Figure 3, the profile height of this black treated side is 120nm, this black treated side L value in the Lab chromaticity diagram is 29, and glossiness [Gs (60 °)] is 22.In addition, on the black treated side, paste self adhesive tape, do not find that test tape comes off by having peeled off powder.
＜plasma display the manufacturing of hertzian wave shielding conductive silk screen 〉
Similarly to Example 1, adopt the surface treatment copper foil trial-production electromagnetic wave shielding conduction silk screen that obtains.The result is that even it is also harmless to exist antirust processing layer to carry out etching, etching is noresidue still, carries out very good etching.
Embodiment 6
Present embodiment is different with embodiment 1, the asperities of electrolytic copper foil does not carry out roughened, below operation similarly to Example 1, glossy surface side at electrolytic copper foil forms the black processing layer with the rose vitriol electrolytic coating, as shown in Figure 2, make the 2nd surface treatment copper foil 1b, estimate similarly to Example 1.Therefore, because the explanation of operation and embodiment 1 repetition, so omit herein.Also have, the rose vitriol thickness of plating layer of black converts and reaches 310mg/m
2The black face of the surface treatment copper foil that obtains here (rose vitriol electrolytic coating) is shown in Figure 13.
The rerum natura of＜surface treatment copper foil 〉
The result that the surface treatment copper foil section with black treated side that the above-mentioned operation of process obtains is observed with the FIB device, obtain section shown in Figure 3, the profile height of this black treated side is 116nm, this black treated side L value in the Lab chromaticity diagram is 27, and glossiness [Gs (60 °)] is 23.In addition, on the black treated side, paste self adhesive tape, do not find that test tape comes off by having peeled off powder.
＜plasma display the manufacturing of hertzian wave shielding conductive silk screen 〉
Similarly to Example 1, adopt the surface treatment copper foil trial-production electromagnetic wave shielding conduction silk screen that obtains.The result is that even it is also harmless to exist antirust processing layer to carry out etching, etching is noresidue still, carries out very good etching.
Embodiment 7
In the present embodiment, asperities to electrolytic copper foil does not carry out roughened similarly to Example 6, employing is carried out the black processing without the Copper Foil of roughened, make the 1st surface treatment copper foil 1b as shown in Figure 2, adopt the shape of etching method trial-production electromagnetic wave shielding conduction silk screen, confirm etching performance.
In the present embodiment, adopt the Copper Foil of electroplating the nominal thickness 15 μ m that obtain by copper-bath.And the dilution heat of sulfuric acid with 30 ℃ of sulfuric acid concentration 150g/L, liquid temperature floods Copper Foil 30 seconds in this solution, carries out surface cleaning.
Then, passing through a) on this Copper Foil glossy surface, operation forms the rose vitriol electrolytic coating.The formation of rose vitriol electrolytic coating adopts that rose vitriol (7 hydrate) 20g/L, pH transfer to 5.5, the rose vitriol electroplate liquid of 27 ℃ of liquid temperature is as stirring bath, uses 1A/dm
215 seconds of current density electrolysis, form black sulfuric acid cobalt electrolytic coating (thickness conversion: 334mg/m whereby
2).At this moment, the concentration of cobalt ions in the solution is not adjusted especially.Because the short period of time electrolysis is so concentration of metal ions needn't be adjusted.The rose vitriol electrolytic coating that forms is shown in Figure 14.
As b) operation, carry out spray washing with competent pure water, in atmosphere temperature degree being heated to 150 ℃ drying oven with electricradiator, be detained for 4 seconds, remove moisture, obtain having the surface treatment copper foil 1 of the black treated side of very good tone.Also have, be provided with in principle at above-mentioned each inter process and adopt 15 seconds washing step of pure water washing, prevent that the solution of pretreatment procedure from entering.
The rerum natura of＜surface treatment copper foil 〉
The result that the surface treatment copper foil section with black treated side that the above-mentioned operation of process obtains is observed with the FIB device, obtain section shown in Figure 3, the profile height of this black treated side is 131nm, this black treated side L value in the Lab chromaticity diagram is 31, and glossiness [Gs (60 °)] is 24.In addition, on the black treated side, paste self adhesive tape, do not find that test tape comes off by having peeled off powder.
＜plasma display the manufacturing of hertzian wave shielding conductive silk screen 〉
Similarly to Example 1, adopt the surface treatment copper foil trial-production electromagnetic wave shielding conduction silk screen that obtains.The result is that even it is also harmless to exist antirust processing layer to carry out etching, etching is noresidue still, carries out very good etching.
Embodiment 8
In the present embodiment, asperities to electrolytic copper foil does not carry out roughened similarly to Example 6, employing is carried out the black processing without the Copper Foil of roughened, make the 1st surface treatment copper foil 1b as shown in Figure 2, adopt the shape of etching method trial-production electromagnetic wave shielding conduction silk screen, confirm etching performance.
In the present embodiment, adopt the Copper Foil of electroplating the nominal thickness 15 μ m that obtain by copper-bath.And the dilution heat of sulfuric acid with 30 ℃ of sulfuric acid concentration 150g/L, liquid temperature floods Copper Foil 30 seconds in this solution, carries out surface cleaning.
Then, passing through a) on this Copper Foil glossy surface, operation forms the rose vitriol electrolytic coating.The formation of rose vitriol electrolytic coating adopts that rose vitriol (7 hydrate) 20g/L, pH transfer to 5.5, the rose vitriol electroplate liquid of 27 ℃ of liquid temperature is as stirring bath, uses 2A/dm
27 seconds of current density electrolysis, form black sulfuric acid cobalt electrolytic coating (thickness conversion: 330mg/m whereby
2).At this moment, the concentration of cobalt ions in the solution is not adjusted especially.Because the short period of time electrolysis is so concentration of metal ions needn't be adjusted.The rose vitriol electrolytic coating that forms is shown in Figure 14.
As b) operation, carry out spray washing with competent pure water, in atmosphere temperature degree being heated to 150 ℃ drying oven with electricradiator, be detained for 4 seconds, remove moisture, obtain having the surface treatment copper foil 1 of the black treated side of very good tone.Also have, be provided with in principle at above-mentioned each inter process and adopt 15 seconds washing step of pure water washing, prevent that the solution of pretreatment procedure from entering.
The rerum natura of＜surface treatment copper foil 〉
The result that the surface treatment copper foil section with black treated side that the above-mentioned operation of process obtains is observed with the FIB device, obtain section shown in Figure 3, the profile height of this black treated side is 124nm, this black treated side L value in the Lab chromaticity diagram is 33, and glossiness [Gs (60 °)] is 20.In addition, on the black treated side, paste self adhesive tape, do not find that test tape comes off by having peeled off powder.
＜plasma display the manufacturing of hertzian wave shielding conductive silk screen 〉
Similarly to Example 1, adopt the surface treatment copper foil trial-production electromagnetic wave shielding conductive filament net that obtains.The result is that even it is also harmless to exist antirust processing layer to carry out etching, etching is noresidue still, carries out very good etching.
Embodiment 9
In the present embodiment, asperities to electrolytic copper foil does not carry out roughened similarly to Example 6, employing is carried out the black processing without the Copper Foil of roughened, make the 1st surface treatment copper foil 1b as shown in Figure 2, adopt the shape of etching method trial-production electromagnetic wave shielding conduction silk screen, confirm etching performance.
In the present embodiment, adopt the Copper Foil of electroplating the nominal thickness 15 μ m that obtain by copper-bath.And the dilution heat of sulfuric acid with 30 ℃ of sulfuric acid concentration 150g/L, liquid temperature floods Copper Foil 30 seconds in this solution, carries out surface cleaning.
Then, passing through a) on this Copper Foil glossy surface, operation forms the rose vitriol electrolytic coating.The formation of rose vitriol electrolytic coating adopts that rose vitriol (7 hydrate) 40g/L, pH transfer to 5.5, the rose vitriol electroplate liquid of 27 ℃ of liquid temperature is as stirring bath, uses 1A/dm
215 seconds of current density electrolysis, form black sulfuric acid cobalt electrolytic coating (thickness conversion: 338mg/m whereby
2).At this moment, the concentration of cobalt ions in the solution is not adjusted especially.Because the short period of time electrolysis is so concentration of metal ions needn't be adjusted.The rose vitriol electrolytic coating that forms is shown in Figure 14.
As b) operation, carry out spray washing with competent pure water, in atmosphere temperature degree being heated to 150 ℃ drying oven with electricradiator, be detained for 4 seconds, remove moisture, obtain having the surface treatment copper foil 1b of the black treated side of very good tone.Also have, be provided with in principle at above-mentioned each inter process and adopt 15 seconds washing step of pure water washing, prevent that the solution of pretreatment procedure from entering.
The rerum natura of＜surface treatment copper foil 〉
The result that the surface treatment copper foil section with black treated side that the above-mentioned operation of process obtains is observed with the FIB device, obtain section shown in Figure 3, the profile height of this black treated side is 134nm, this black treated side L value in the Lab chromaticity diagram is 34, and glossiness [Gs (60 °)] is 21.In addition, on the black treated side, paste self adhesive tape, do not find that test tape comes off by having peeled off powder.
＜plasma display the manufacturing of hertzian wave shielding conductive silk screen 〉
Similarly to Example 1, adopt the surface treatment copper foil trial-production electromagnetic wave shielding conduction silk screen that obtains.The result is that even it is also harmless to exist antirust processing layer to carry out etching, etching is noresidue still, carries out very good etching.
Embodiment 10
In the present embodiment, as shown in Figure 7, make the 2nd surface treatment copper foil 1d that has as the zinc-cobalt alloy layer of antirust processing layer,, confirm etching with etching method trial-production electromagnetic wave shielding conduction silk screen.Therefore, arrive with till the rose vitriol electrolytic coating formation black processing layer, similarly to Example 1, so only antirust treatment condition are illustrated.Also have, the rose vitriol thickness of plating layer of black converts similarly to Example 7, reaches 334mg/m
2
, on the Copper Foil two sides that has formed black sulfuric acid cobalt electrolytic coating on the single face of embodiment 7, adopt condition similarly to Example 4 here, form the zinc-cobalt alloy layer on the two sides.In addition, similarly to Example 1, carry out spray washing, in atmosphere temperature degree being heated to 150 ℃ drying oven with electricradiator, be detained for 4 seconds, remove moisture, obtain having the surface treatment copper foil 1d of the black treated side of very good tone with competent pure water.Also have, be provided with in principle at above-mentioned each inter process and adopt 15 seconds washing step of pure water washing, prevent that the solution of pretreatment procedure from entering.
The rerum natura of＜surface treatment copper foil 〉
The result that the surface treatment copper foil section with black treated side that the above-mentioned operation of process obtains is observed with the FIB device, obtain section shown in Figure 3, the profile height of this black treated side is 128nm, this black treated side L value in the Lab chromaticity diagram is 28, and glossiness [Gs (60 °)] is 30.In addition, on the black treated side, paste self adhesive tape, do not find that test tape comes off by having peeled off powder.
＜plasma display the manufacturing of hertzian wave shielding conductive silk screen 〉
Similarly to Example 1, adopt the surface treatment copper foil trial-production electromagnetic wave shielding conduction silk screen that obtains.The result is that even it is also harmless to exist antirust processing layer to carry out etching, etching is noresidue still, carries out very good etching.
Embodiment 11
In the present embodiment, as shown in Figure 9, manufacturing has as the zinc-cobalt alloy layer of antirust processing layer and the 2nd surface treatment copper foil 1f of chromate treating layer, with etching method trial-production electromagnetic wave shielding conduction silk screen, confirms etching.Therefore, to form black processing layer position with the rose vitriol electrolytic coating, similarly to Example 7, so only antirust treatment condition are illustrated.Also have, the rose vitriol thickness of plating layer of black converts similarly to Example 7, reaches 334mg/m
2
The formation of antirust processing layer similarly to Example 4, is adopted the zinc-cobalt alloy electroplate liquid, after the two sides forms the zinc-cobalt alloy layer, similarly to Example 5 chromate treating is carried out on the two sides.
When chromate coating forms termination, carry out spray washing with competent pure water, in atmosphere temperature degree being heated to 150 ℃ drying oven with electricradiator, be detained for 4 seconds, remove moisture, obtain having the surface treatment copper foil 1f of the black treated side of very good tone.Also have, be provided with in principle at above-mentioned each inter process and adopt 15 seconds washing step of pure water washing, prevent that the solution of pretreatment procedure from entering.
The rerum natura of＜surface treatment copper foil 〉
The result that the surface treatment copper foil section with black treated side that the above-mentioned operation of process obtains is observed with the FIB device, obtain section shown in Figure 3, the profile height of this black treated side is 115nm, this black treated side L value in the Lab chromaticity diagram is 29, and glossiness [Gs (60 °)] is 22.In addition, on the black treated side, paste self adhesive tape, do not find that test tape comes off by having peeled off powder.
＜plasma display the manufacturing of hertzian wave shielding conductive silk screen 〉
Similarly to Example 1, adopt the surface treatment copper foil trial-production electromagnetic wave shielding conduction silk screen that obtains.The result is that even it is also harmless to exist antirust processing layer to carry out etching, etching is noresidue still, carries out very good etching.
The possibility of utilizing on the industry
The surface treatment copper foil with black treated side that the present invention relates to, no powder comes off from the black treated side, and, can adopt common copper etchant solution to carry out etching and processing, the electromagnetic wave shielding conduction silk screen of the front panel by being used for the plasma scope plate can form high-quality black masks. In addition, as supplying with, then can omit the black treatment process in the front panel manufacturing process as the surface treatment copper foil with black treated side. In addition, have the surface treatment copper foil of black treated side, by adopting above-mentioned manufacture method, can adopt existing copper foil surface treatment process and need not new manufacturing equipment. Therefore, because the good high-quality goods of manufacturing of productive rate, so, produce instinct and reduce.
Claims (16)
1. surface treatment copper foil, it has the black treated side on glossy surface, it is characterized in that, and the gravimetric thickness that this black treated side is provided in a side of on the copper foil layer single face is 200mg/m
2～400mg/m
2The rose vitriol electrolytic coating that forms by electrochemical plating of use cobalt sulfate solution, and the profile height of this black treated side is 200nm or below the 200nm.
2. according to the described surface treatment copper foil of claim 1, wherein, the L value of described black treated side in the Lab chromaticity diagram is more than 27 or 27.
3. according to the described surface treatment copper foil of claim 1, wherein, described black treated side has antirust processing layer.
4. according to the described surface treatment copper foil of claim 3, wherein, antirust processing layer is the antirust processing layer that adopts zinc or zinc alloy.
5. according to the described surface treatment copper foil of claim 3, wherein, antirust processing layer is made of the layer and the chromic salt gloss finish layer that adopt zinc or zinc alloy to form.
6. according to the described surface treatment copper foil of claim 1, wherein, described black treated side is formed in the black treated side on the glossy surface of electrolytic copper foil or rolled copper foil, and glossiness Gs60 ° is below 30 or 30.
7. the manufacture method with surface treatment copper foil of black treated side is characterized in that, have following a) and b) operation:
A) on the glossy surface of Copper Foil, adopt and contain rose vitriol 7 hydrate 8g/L～10g/L, the nothing of the rose vitriol electroplate liquid of pH4.0 or the above scope of pH4.0 stirs bathes, and uses 2A/dm
2Or 2A/dm
2Above current density is carried out electrolysis, forms the rose vitriol electrolytic coating of black system;
B) then, wash, drying.
8. the manufacture method with surface treatment copper foil of black treated side is characterized in that, have following a) and b) operation:
A) on the glossy surface of Copper Foil, adopt and contain rose vitriol 7 hydrate 10g/L～40g/L, pH4.0 or pH4.0 are above, the stirring of the rose vitriol electroplate liquid of liquid temperature below 30 ℃ or 30 ℃ is bathed, and use 4A/dm
2Or 4A/dm
2Following current density is carried out electrolysis, forms the rose vitriol electrolytic coating of black system;
B) then, wash, drying.
9. the manufacture method with surface treatment copper foil of black treated side is the manufacture method with surface treatment copper foil of antirust processing layer and black treated side, it is characterized in that, has following operation a)～c):
A) on the glossy surface of Copper Foil, adopt and contain rose vitriol 7 hydrate 8g/L～10g/L, the nothing of the rose vitriol electroplate liquid of pH4.0 or the above scope of pH4.0 stirs bathes, and uses 2A/dm
2Or 2A/dm
2Above current density is carried out electrolysis, forms the rose vitriol electrolytic coating of black system;
B) on the two sides of the Copper Foil of the rose vitriol electrolytic coating that has formed black or single face, form antirust processing layer;
C) then, wash, drying.
10. the surface treatment copper foil manufacture method with black treated side is the manufacture method with surface treatment copper foil of antirust processing layer and black treated side, it is characterized in that, has following operation a)～c):
A) on the glossy surface of Copper Foil, adopt and contain rose vitriol 7 hydrate 10g/L～40g/L, pH4.0 or pH4.0 are above, the stirring of the rose vitriol electroplate liquid of liquid temperature below 30 ℃ or 30 ℃ is bathed, and use 4A/dm
2Or 4A/dm
2Following current density is carried out electrolysis, forms the rose vitriol electrolytic coating of black system;
B) on the two sides of the Copper Foil of the rose vitriol electrolytic coating that has formed black or single face, form antirust processing layer;
C) then, wash, drying.
11. the electromagnetic wave shielding that the front panel of a plasma display is used conduction silk screen, it adopts the described surface treatment copper foil of claim 1 and forms.
12. the electromagnetic wave shielding that the front panel of a plasma display is used conduction silk screen, it adopts the described surface treatment copper foil of claim 2 and forms.
13. the electromagnetic wave shielding that the front panel of a plasma display is used conduction silk screen, it adopts the described surface treatment copper foil of claim 3 and forms.
14. the electromagnetic wave shielding that the front panel of a plasma display is used conduction silk screen, it adopts the described surface treatment copper foil of claim 4 and forms.
15. the electromagnetic wave shielding that the front panel of a plasma display is used conduction silk screen, it adopts the described surface treatment copper foil of claim 5 and forms.
16. the electromagnetic wave shielding that the front panel of a plasma display is used conduction silk screen, it adopts the described surface treatment copper foil of claim 6 and forms.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP281288/2003 | 2003-07-28 | ||
| JP2003281288 | 2003-07-28 | ||
| JP2003353198 | 2003-10-14 | ||
| JP353198/2003 | 2003-10-14 | ||
| JP027706/2004 | 2004-02-04 | ||
| JP2004027706A JP4458519B2 (en) | 2003-07-28 | 2004-02-04 | Surface-treated copper foil having a blackened surface, a method for producing the surface-treated copper foil, and an electromagnetic shielding conductive mesh for a front panel of a plasma display using the surface-treated copper foil |
| PCT/JP2004/010100 WO2005010241A1 (en) | 2003-07-28 | 2004-07-15 | Surface-treated copper foil having blackening-treated surface, process for producing the surface-treated copper foil and, using the surface-treated copper foil, electromagnetic wave shielding conductive mesh for front panel of plasma display |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1701137A CN1701137A (en) | 2005-11-23 |
| CN1701137B true CN1701137B (en) | 2010-04-21 |
Family
ID=34108578
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2004800010169A Expired - Fee Related CN1701137B (en) | 2003-07-28 | 2004-07-15 | Surface-treated copper foil having blackening-treated surface, process for producing the surface-treated copper foil and, using the surface-treated copper foil, electromagnetic wave shielding conducti |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP4458519B2 (en) |
| KR (1) | KR100686789B1 (en) |
| CN (1) | CN1701137B (en) |
| TW (1) | TW200504148A (en) |
| WO (1) | WO2005010241A1 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4575719B2 (en) * | 2003-11-13 | 2010-11-04 | 三井金属鉱業株式会社 | Surface-treated copper foil having a browned surface, a method for producing the surface-treated copper foil, and an electromagnetic shielding conductive mesh for a front panel of a plasma display using the surface-treated copper foil |
| TW200718347A (en) * | 2005-07-14 | 2007-05-01 | Mitsui Mining & Smelting Co | Blackening surface treated copper foil and electromagnetic wave shielding conductive mesh for front panel of plasma display using the blackening surface treated copper foil |
| US8673428B2 (en) | 2006-12-27 | 2014-03-18 | Hitachi Chemical Company, Ltd. | Engraved plate and substrate with conductor layer pattern using the same |
| JP2009021412A (en) * | 2007-07-12 | 2009-01-29 | Hitachi Chem Co Ltd | Method of manufacturing surface blackened copper metal, method of manufacturing base material with conductor layer pattern, base material with conductor pattern, and electromagnetic wave shielding member using the base material |
| JP2009152285A (en) * | 2007-12-19 | 2009-07-09 | Hitachi Chem Co Ltd | Method for manufacturing metal pattern and base material having conductive layer pattern, and base material having conductive layer pattern and electromagnetic wave shielding member using the same |
| JP2009158842A (en) * | 2007-12-27 | 2009-07-16 | Hitachi Chem Co Ltd | Manufacturing method for surface-blackening copper metal, manufacturing method for base material with conductor-layer pattern, base material with conductor-layer pattern and electromagnetic-wave shielding member using base material |
| CN101906630B (en) * | 2010-08-03 | 2011-08-10 | 山东金宝电子股份有限公司 | Black surface treatment process of electrolytic copper foil |
| CN102660695B (en) * | 2012-04-17 | 2015-07-29 | 重庆材料研究院 | A kind of copper wire and prepare shielding copper mesh method |
| JP7476791B2 (en) | 2018-03-09 | 2024-05-01 | 大日本印刷株式会社 | Conductive film, sensor, touch panel, and image display device |
| CN109680307A (en) * | 2019-01-21 | 2019-04-26 | 苏州宝士杰塑料科技有限公司 | It is a kind of dicoration mono-salt without nickel rifle color electroplating technology |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003201597A (en) * | 2002-01-09 | 2003-07-18 | Nippon Denkai Kk | Copper foil, production method therefor and electromagnetic wave shield body obtained by using the copper foil |
| CN1525492A (en) * | 2003-02-27 | 2004-09-01 | �źӵ�·ͭ����ʽ���� | Electromagnetic shielding copper foil, method of production thereof and electromagnetic shield |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5585689A (en) * | 1978-12-25 | 1980-06-27 | Seiko Instr & Electronics Ltd | Black color plating bath |
| JPS6191385A (en) * | 1984-10-12 | 1986-05-09 | Nippon Kagaku Sangyo Kk | Black electroplating bath |
| JPH0654831B2 (en) * | 1990-08-14 | 1994-07-20 | 株式会社ジャパンエナジー | Method of treating copper foil for printed circuits |
| JP2717910B2 (en) * | 1992-11-19 | 1998-02-25 | 日鉱グールド・フォイル株式会社 | Copper foil for printed circuit and manufacturing method thereof |
| US6224991B1 (en) * | 1999-09-13 | 2001-05-01 | Yates Foil Usa, Inc. | Process for electrodeposition of barrier layer over copper foil bonding treatment, products thereof and electrolyte useful in such process |
| JP3330925B2 (en) * | 2000-04-05 | 2002-10-07 | 株式会社日鉱マテリアルズ | Copper foil for laser drilling |
| JP3998975B2 (en) * | 2001-12-28 | 2007-10-31 | 大日本印刷株式会社 | Electromagnetic wave shielding sheet |
| JP2004119961A (en) * | 2002-09-02 | 2004-04-15 | Furukawa Techno Research Kk | Copper foil for chip-on film, plasma display panel, and high-frequency printed wiring board |
| JP4573254B2 (en) * | 2002-10-25 | 2010-11-04 | Ｊｘ日鉱日石金属株式会社 | Copper foil for plasma display panel and method for producing the same |
| JP2004162143A (en) * | 2002-11-15 | 2004-06-10 | Nippon Denkai Kk | Method for manufacturing copper foil for printed circuit board |
| JP2004172343A (en) * | 2002-11-20 | 2004-06-17 | Nikko Materials Co Ltd | Copper foil for laser drilling and manufacturing method thereof |
-
2004
- 2004-02-04 JP JP2004027706A patent/JP4458519B2/en not_active Expired - Fee Related
- 2004-06-28 TW TW093118760A patent/TW200504148A/en unknown
- 2004-07-15 WO PCT/JP2004/010100 patent/WO2005010241A1/en active Application Filing
- 2004-07-15 CN CN2004800010169A patent/CN1701137B/en not_active Expired - Fee Related
- 2004-07-15 KR KR1020057006660A patent/KR100686789B1/en active IP Right Grant
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003201597A (en) * | 2002-01-09 | 2003-07-18 | Nippon Denkai Kk | Copper foil, production method therefor and electromagnetic wave shield body obtained by using the copper foil |
| CN1525492A (en) * | 2003-02-27 | 2004-09-01 | �źӵ�·ͭ����ʽ���� | Electromagnetic shielding copper foil, method of production thereof and electromagnetic shield |
Also Published As
| Publication number | Publication date |
|---|---|
| TW200504148A (en) | 2005-02-01 |
| JP2005139544A (en) | 2005-06-02 |
| KR20050063784A (en) | 2005-06-28 |
| WO2005010241A1 (en) | 2005-02-03 |
| KR100686789B1 (en) | 2007-02-26 |
| JP4458519B2 (en) | 2010-04-28 |
| TWI296636B (en) | 2008-05-11 |
| CN1701137A (en) | 2005-11-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100407732B1 (en) | Composite foil containing nodular copper / nickel alloy coating, printed circuit board containing it and method of electrodeposition of nodular copper / nickel alloy coating | |
| CN1861842B (en) | Immersion method | |
| CN101223839A (en) | Blackening surface treated copper foil and electromagnetic wave shielding conductive mesh for front panel of plasma display using the blackening surface treated copper foil | |
| US3654099A (en) | Cathodic activation of stainless steel | |
| CN1701137B (en) | Surface-treated copper foil having blackening-treated surface, process for producing the surface-treated copper foil and, using the surface-treated copper foil, electromagnetic wave shielding conducti | |
| TW201002165A (en) | Copper foil for printed circuit board and copper clad laminate plate for printed circuit board | |
| KR20190049818A (en) | Copper foil and copper-clad laminate having the copper foil | |
| JPS6255714B2 (en) | ||
| JP4309817B2 (en) | Method for producing blackened surface-treated copper foil for electromagnetic wave shielding | |
| JPH0441696A (en) | Surface treatment of copper foil for printed circuit | |
| CN1934293B (en) | Surface-treated copper foil having grayed surface, process for producing the same and electromagnetic wave shielding conductive mesh for front panel of plasma display using the surface-treated copper | |
| CN100567584C (en) | Brown surface treatment copper foil and manufacture method, with the electromagnetic wave shielding conductive mesh for front panel of plasma display of this Copper Foil | |
| JP2004256832A (en) | Surface treated copper foil provided with blackening treated face, and magnetic shielding conductive mesh for front panel of plasma display obtained by using the surface treated copper foil | |
| JP2008166655A (en) | Copper foil for electromagnetic shielding material | |
| US5304428A (en) | Copper foil for printed circuit boards | |
| KR20050088409A (en) | Peel strength enhancement of copper laminates | |
| KR100604964B1 (en) | Method for manufacturing black surface-treated copper foil for EMI Shield | |
| JP2772684B2 (en) | Copper foil surface treatment method | |
| JPH0259639B2 (en) | ||
| JP4136496B2 (en) | Method for producing electrolytic copper foil | |
| JP2005139546A (en) | Blacking surface-treated copper foil, process for producing the blackening surface-treated copper foil and, using the blacking surface-treated copper foil, electromagnetic wave shielding conductive mesh | |
| KR100603428B1 (en) | Method for manufacturing black surface-treated copper foil for EMI Shield | |
| JPH07321458A (en) | Surface treatment method of copper foil for printed circuit | |
| JP4575719B2 (en) | Surface-treated copper foil having a browned surface, a method for producing the surface-treated copper foil, and an electromagnetic shielding conductive mesh for a front panel of a plasma display using the surface-treated copper foil | |
| JPS5815950B2 (en) | Surface treatment method for copper foil for printed circuits |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100421 Termination date: 20120715 |