CN101223839A - Blackening surface treated copper foil and electromagnetic wave shielding conductive mesh for front panel of plasma display using the blackening surface treated copper foil - Google Patents
Blackening surface treated copper foil and electromagnetic wave shielding conductive mesh for front panel of plasma display using the blackening surface treated copper foil Download PDFInfo
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- CN101223839A CN101223839A CNA200680025669XA CN200680025669A CN101223839A CN 101223839 A CN101223839 A CN 101223839A CN A200680025669X A CNA200680025669X A CN A200680025669XA CN 200680025669 A CN200680025669 A CN 200680025669A CN 101223839 A CN101223839 A CN 101223839A
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- copper foil
- black
- surface treatment
- untreated
- treated side
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 254
- 239000011889 copper foil Substances 0.000 title claims abstract description 218
- 230000003746 surface roughness Effects 0.000 claims abstract description 26
- 238000004381 surface treatment Methods 0.000 claims description 86
- 238000012545 processing Methods 0.000 claims description 33
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 22
- 229910017052 cobalt Inorganic materials 0.000 claims description 17
- 239000010941 cobalt Substances 0.000 claims description 17
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 16
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 238000005259 measurement Methods 0.000 claims description 7
- 238000005530 etching Methods 0.000 abstract description 40
- 238000004458 analytical method Methods 0.000 abstract description 31
- 239000012790 adhesive layer Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 53
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 50
- 238000004519 manufacturing process Methods 0.000 description 46
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 45
- 239000007788 liquid Substances 0.000 description 42
- 229910052802 copper Inorganic materials 0.000 description 37
- 239000010949 copper Substances 0.000 description 37
- 238000012360 testing method Methods 0.000 description 35
- 238000004879 turbidimetry Methods 0.000 description 29
- 238000000576 coating method Methods 0.000 description 28
- 239000011248 coating agent Substances 0.000 description 27
- 238000005868 electrolysis reaction Methods 0.000 description 26
- 239000000243 solution Substances 0.000 description 24
- 239000003792 electrolyte Substances 0.000 description 23
- 229920000642 polymer Polymers 0.000 description 20
- 239000003795 chemical substances by application Substances 0.000 description 17
- 235000013495 cobalt Nutrition 0.000 description 17
- 229920005989 resin Polymers 0.000 description 17
- 239000011347 resin Substances 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 15
- 239000002390 adhesive tape Substances 0.000 description 14
- 239000003595 mist Substances 0.000 description 14
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 13
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 13
- 238000003672 processing method Methods 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000010408 film Substances 0.000 description 11
- 238000007747 plating Methods 0.000 description 11
- 238000010023 transfer printing Methods 0.000 description 11
- 229910000990 Ni alloy Inorganic materials 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 238000009713 electroplating Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 9
- HIRWGWMTAVZIPF-UHFFFAOYSA-N nickel;sulfuric acid Chemical compound [Ni].OS(O)(=O)=O HIRWGWMTAVZIPF-UHFFFAOYSA-N 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 8
- 239000010936 titanium Substances 0.000 description 8
- 229910052719 titanium Inorganic materials 0.000 description 8
- 238000005554 pickling Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- UGWKCNDTYUOTQZ-UHFFFAOYSA-N copper;sulfuric acid Chemical compound [Cu].OS(O)(=O)=O UGWKCNDTYUOTQZ-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- 229910000531 Co alloy Inorganic materials 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 5
- HSSJULAPNNGXFW-UHFFFAOYSA-N [Co].[Zn] Chemical compound [Co].[Zn] HSSJULAPNNGXFW-UHFFFAOYSA-N 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 229910001429 cobalt ion Inorganic materials 0.000 description 5
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 238000004070 electrodeposition Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 239000002966 varnish Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- OBDVFOBWBHMJDG-UHFFFAOYSA-N 3-mercapto-1-propanesulfonic acid Chemical compound OS(=O)(=O)CCCS OBDVFOBWBHMJDG-UHFFFAOYSA-N 0.000 description 3
- 229920002799 BoPET Polymers 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000004088 simulation Methods 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 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 3
- 238000011282 treatment Methods 0.000 description 3
- 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 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 2
- 241000784732 Lycaena phlaeas Species 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 210000003484 anatomy Anatomy 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- 239000010951 brass Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 2
- 229940044175 cobalt sulfate Drugs 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-methyl phenol Natural products CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 150000002898 organic sulfur compounds Chemical class 0.000 description 2
- 239000006174 pH buffer Substances 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 230000003405 preventing effect Effects 0.000 description 2
- 238000012797 qualification Methods 0.000 description 2
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 238000003287 bathing Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- 238000011284 combination treatment Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000012217 deletion Methods 0.000 description 1
- 230000037430 deletion Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- FTCLAXOKVVLHEG-UHFFFAOYSA-N sodium;3-sulfanylpropane-1-sulfonic acid Chemical compound [Na].OS(=O)(=O)CCCS FTCLAXOKVVLHEG-UHFFFAOYSA-N 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000012546 transfer Methods 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
- C25D5/48—After-treatment of electroplated surfaces
-
- 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
- H05K3/385—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by conversion of the surface of the metal, e.g. by oxidation, whether or not followed by reaction or removal of the converted layer
-
- 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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/03—Conductive materials
- H05K2201/0332—Structure of the conductor
- H05K2201/0335—Layered conductors or foils
- H05K2201/0355—Metal 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
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/03—Metal processing
- H05K2203/0307—Providing micro- or nanometer scale roughness on a metal surface, e.g. by plating of nodules or dendrites
-
- 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
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/03—Metal processing
- H05K2203/0315—Oxidising metal
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Metallurgy (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Plasma & Fusion (AREA)
- Manufacturing & Machinery (AREA)
- Electroplating Methods And Accessories (AREA)
- Electromagnetism (AREA)
- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
- Laminated Bodies (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
Abstract
A blackening surface treated copper foil capable of improving a phenomenon of causing clouding of the surface of an adhesive layer exposed between mesh circuits on completion of etching of a conductive mesh used for shielding a plasma display panel against an electromagnetic wave. The blackening surface treated copper foil is used which is a surface treated copper foil having a blackening treated surface provided on the surface of an untreated electrolytic copper foil, characterized in that the untreated electrolytic copper foil has a surface of which surface roughness Ra is up to 45 nm as measured with a three-dimensional surface structure analysis microscope, and the surface is provided with a blackening treated surface. The surface of the untreated electrolytic copper foil provided with a blackening treated surface more preferably has a surface roughness Rz of up to 850 nm as measured with a three-dimensional surface structure analysis microscope.
Description
Technical field
A kind of black surface treatment copper foil and the electromagnetic wave shielding conductive mesh for front panel that has used the plasma display of this black surface treatment copper foil.
Background technology
The shielding conductive mesh of Plasmia indicating panel is transitted towards conductive mesh from the metalized fibers fabric.And, in recent years, also adopted on the surface of glass or plastic base version, used the good nesa coatings of the transparency such as silver or ITO to replace the technology of conductive mesh, but these transparent conductivity tunicles at the electromagnetic wave shielding of high-frequency region than conductive mesh difference.Therefore, adopt the metal forming etching and processing and the electromagnetic wave shielding conductive mesh that obtains still becomes main flow.
The method of using metal forming to make electromagnetic wave shielding conductive mesh has several.Wherein the most representative manufacture method is described.That is, shown in Fig. 5 a, prepare PET film 4,, become the state shown in Fig. 5 b by adhering agent layer 5 is set in its surface.Then, shown in Fig. 5 c, on adhering agent layer 5, will have the black surface treatment copper foil 2 of black treated side 3, carry out bonding with the mode that above-mentioned adhering agent layer 5 contacts with this black treated side 3.So shown in Fig. 5 d, black surface treatment copper foil 2 is set at the surface.
And, on this black surface treatment copper foil 2, shown in Fig. 5 e, form resist layer 6, on this resist layer 6, shown in Fig. 6 f, exposure conductive mesh pattern 7 develops shown in Fig. 6 g, form the resist pattern form,, become the state shown in Fig. 6 h by etching.At this moment, by peeling off resist layer 6, become the state shown in Fig. 6 i.
Then, shown in Fig. 7 j, push, shown in Fig. 7 k, conductive mesh 8 is pressed in the adhering agent layer 5, and carries out transparence and handle by the first transparent base version 9a and conductive mesh 8 butts that will constitute front filter.Then, shown in Fig. 7 l, peel PET film 4.At last, shown in Fig. 7 m, the bonding adhering agent layer 5 and the second transparent base version 9b, thus finish front filter 1.
The technology trend Hitachi forming technology of non-patent literature 1:PDP material is reported No. 33 (1999-7)
Patent documentation 1:JP spy opens flat 11-186785 communique
Patent documentation 2:JP spy opens the 2000-315889 communique
Patent documentation 3:JP spy opens the 2004-35918 communique
Patent documentation 4:JP spy opens the 2004-162144 communique
Patent documentation 5:JP spy opens the 2004-107786 communique
Patent documentation 6:JP spy opens the 2004-137588 communique
Summary of the invention
The problem that invention will solve
But, because energy-conservationization requirement in recent years, just carrying out plasma generation signal voltage is dropped to the exploitation that the 50V degree is a target from 200V, and in order to compensate the minimizing of the brightness that the reduction that is accompanied by this voltage causes, towards the graph thinning of conductive mesh circuit width, reduce the direction progress of the coverage rate of the front glass panel that causes because of conductive mesh thus.
On the one hand, because conductive mesh self is assembled in the header board, and can be visually observed from the surface by front glass, so for the single face of the surface treatment copper foil that will be processed to this conductive mesh is made good black film, be necessary it is processed into the dark-coloured state of black from dark brown, improve the brightness that sees through light.
In addition, consider future, the surface wave of prediction TV transmits electric wave and can realize digitlization, and the transfer rate of picture intelligence is high speed also, and requires to become more meticulous corresponding to the height of the image of Hi-vision.
Consider above present situation,, then have following problem if pass gloss between the silk screen circuit of electromagnetic wave shielding conductive mesh with light time of distinctness and high brightness more.That is, shown in Fig. 7 i, when the etching of conductive filament mesh-shaped finished, the surface configuration that is exposed to the adhering agent layer 5 between circuit became the transfer printing shape of the black treated side 3 of black surface treatment copper foil 2.This transfer printing shape is according to the difference of the constituent that constitutes adhering agent layer and difference, but after the transparence of having implemented Fig. 8 i～Fig. 8 k is handled, also can not disappear, remain in sometimes and the first transparent base edition 9a between the interface on.
At this moment,, become obstacle thus,, can't obtain distinct image so reduce the brightness of passing the light between the silk screen circuit because this transfer printing shape produces mist.If because such physical cause can't improve the quality of image, then calculate first-class in any case and handle pictorial data, to carry out the light emitting control of pixel thus and eliminate simulation profile obstacle, also limited.
As mentioned above, when the etching of conductive filament mesh-shaped finished, the surface configuration that is exposed to the adhering agent layer between circuit had the phenomenon that produces mist, therefore, seeks to have the Copper Foil of the black treated side that does not cause this problem always.In order to address this problem, attempted adopting above-mentioned patent documentation 3～6 disclosed technology etc., the surface that makes the Copper Foil that is untreated that forms the black treated side is the Copper Foil of low profileization more.Below, patent documentation 3～above-mentioned patent documentation 6 disclosed technology are simply described.
A kind of manufacture method of electrolytic copper foil has been proposed in patent documentation 3, in the manufacture method of the electrolytic copper foil that has used the sulfuric acid copper plating bath, it is characterized in that, use contains the sulfuric acid copper plating bath of the copolymer of poly (dially dialkyl) based quaternary ammonium salt and sulfur dioxide, and record in this sulfuric acid copper plating bath, preferably contain polyethylene glycol, chlorine and 3-sulfydryl-1-sulfonic acid.And, when adopt and insulating substrate between the roughness (separating out surface roughness) of bonding plane little, and thickness is when being the electrolytic copper foil of 10 μ m, obtained being measured as low profile (roughness) about Rz=1.0 ± 0.5 μ m with the contact pin type roughmeter.
In patent documentation 4, the manufacture method of the electrolytic copper foil that the surface roughness as the face of separating out is little, percentage elongation is good, proposed in manufacture method, to use and contain polyethylene glycol, chlorine and 3-sulfydryl-1-sulfonic acid sulfuric acid copper plating bath as feature according to the electrolytic copper foil of the electrolysis of sulfuric acid copper plating bath.And, when adopt and insulating substrate between the roughness (separating out surface roughness) of bonding plane little, thickness is under the situation of electrolytic copper foil of 10 μ m, has obtained being measured as low profile (roughness) about Rz=1.5 ± 0.5 μ m with the contact pin type roughmeter.
In patent documentation 5, disclose and will be used for the manufacturing of electrolytic copper foil as the copper electrolyte that additive contains amines and organosulfur compound, described amines contains the particular anatomy that makes the compound that has an above epoxy radicals in a part and amines carry out addition reaction and obtain.And, describing as embodiment, the surface roughness Rz of the electrolytic copper foil of measuring with the contact pin type roughmeter that is obtained by this manufacture method is in the scope of 0.90～1.20 μ m.
In patent documentation 6, disclose and to be used for the manufacturing of electrolytic copper foil as the copper electrolyte that additive contains quaternary ammonium compound and organosulfur compound, described quaternary ammonium compound contain make the compound that has an above epoxy radicals in a part and amines carry out addition reaction after, the particular anatomy that the nitrogen level Fourization is obtained.And, describing as embodiment, the surface roughness Rz of the electrolytic copper foil of measuring with the contact pin type roughmeter that is obtained by this manufacture method is in the scope of 0.94～1.23 μ m.
Therefore, if use these manufacture methods to make electrolytic copper foil, formed good low profile really and separated out face, and demonstrated extremely good character as the low profile electrolytic copper foil.But even use these low profile Copper Foils, the quality deviation is big, and after the etching of conductive filament mesh-shaped finished, the surface configuration that is exposed to the adhering agent layer between circuit had the phenomenon that produces mist, does not address the above problem.
Be used to solve the method for problem
So the result that the inventor etc. concentrate one's attention on research has expected having by use the surface treatment copper foil of black treated side shown below solving above-mentioned problem.
In order to solve above-mentioned problem, adopt a kind of black surface treatment copper foil, this black surface treatment copper foil has the black treated side on the surface of the electrolytic copper foil that is untreated, it is characterized in that, the above-mentioned electrolytic copper foil that is untreated has that surface roughness Ra is the following surface of 45nm when measuring with three-dimensional surface structure elucidation microscope, and is provided with the black treated side on this surface.
And when measuring with three-dimensional surface structure elucidation microscope, the surface roughness Rz of the face that the black treated side is set of the preferred above-mentioned electrolytic copper foil that is untreated is below the 850nm.
In addition, when measuring with JIS B 0601, the surface roughness (Rzjis) of the face that the black treated side is set of the preferred above-mentioned electrolytic copper foil that is untreated is the low profile of less than 0.8 μ m, and glossiness (Gs (60 °)) is more than 400.
Preferred above-mentioned black treated side has antirust processing layer.
The glossiness of preferred above-mentioned black treated side [Gs (60 °)] is below 35.
And preferably this black treated side use nickel is that black treated side or cobalt are any one in the black treated side.
By using above-described black surface treatment copper foil, can provide high-quality plasma display electromagnetic wave shielding conductive mesh for front panel.
The invention effect
Black surface treatment copper foil of the present invention, its surperficial flatness is good, use this black surface treatment copper foil to make conductive mesh, and when finishing etching, it is low to be exposed to the degree that produces mist on the surface of the adhering agent layer between circuit, so can not worsen the brightness of Plasmia indicating panel, help very much the elimination of the simulation profile obstacle that the light emitting control by pixel causes.
In addition, the black treated side of black surface treatment copper foil of the present invention, preferred employing nickel is that black treated side or cobalt are any one in the black treated side, the black processing that forms under certain rated condition does not have the dry linting phenomenon, and bring into play good black, this black processing layer can be removed by common copper etching work procedure etching.Therefore, can use the operation of making printed wiring board, the electromagnetic wave shielding conductive mesh of high-quality Plasmia indicating panel is provided.
The best mode that is used to carry out an invention
Surface treatment copper foil with black treated side of the present invention has mode shown below.Promptly, adopt a kind of black surface treatment copper foil, this black surface treatment copper foil is for having the surface treatment copper foil of black treated side on the surface of the electrolytic copper foil that is untreated, it is characterized in that the surface roughness Ra that the above-mentioned electrolytic copper foil that is untreated has when measuring with three-dimensional surface structure elucidation microscope is that 45nm following surface and this surface are provided with the black treated side.
Copper Foil is untreated: the Copper Foil that is untreated at first is described.Be meant at this said Copper Foil that is untreated and on the main body Copper Foil, do not implement any antirust surface-treated Copper Foil that waits, can use in electrolytic copper foil or the rolled copper foil any one.But, consider from the cost aspect, preferably use electrolytic copper foil.This electrolytic copper foil obtains in such a way, promptly be between the anode etc. at the rotating cathode of cylinder shape with along the lead of the shape subtend configuration of this rotating cathode, flowing into copper sulphate is solution, utilize cell reaction, copper is separated out on the cylinder surface of rotating cathode, this copper of separating out just becomes the paper tinsel state, peels off continuously and reel from rotating cathode to form.The Copper Foil in this stage is the Copper Foil that is untreated.
This Copper Foil that is untreated from being shaped as of the face that strips down with the rotating cathode state of contact by the transfer printing shape on the accurately machined rotating cathode of minute surface surface, be commonly referred to glassy surface.If the roughness on this rotating cathode surface is too smooth, the copper of then separating out falls from the rotating cathode sur-face peeling at once, can't obtain good electrolytic copper foil.With respect to this,,, be referred to as matsurface (separating out face) so separate out the concaveconvex shape that the surface configuration of the Copper Foil that is untreated of side shows chevron usually because the crystal growth rate of the copper of being separated out is different and different according to crystal plane.But,, obtain the face of separating out of the concaveconvex shape lower sometimes than glassy surface when making under the situation of electrolytic copper foil under certain rated condition.
In such electrolytic copper foil, surface roughness Ra if be untreated during the useful three-dimensional surface structure elucidation of the mask that the black treated side the is set measurement microscope of electrolytic copper foil is the following surface of 45nm, then as mentioned above, the etching that is assembled into the conductive filament mesh-shaped in the header board of Plasmia indicating panel finishes, and the surface configuration that is exposed to the adhering agent layer between the silk screen circuit can not produce mist.As hereinafter described, as the method for leading to a phenomenon that can replace estimating this mist, the black treated side of surface treatment copper foil of the present invention is coated the epoxies sticker in employing, and make it dry, remove this surface treatment copper foil by comprehensive etching, become the state of sticker sheet, measure the method for its turbidity (mist) with nephelometer (the Japanese electric look system nephelometer NDH2000 of Industrial Co., Ltd).Below, this test is called the turbidimetric analysis turbidimetry test.In an embodiment, show turbidity value.
As mentioned above, the etching that is assembled into the conductive filament mesh-shaped in the header board of Plasmia indicating panel finishes, and the surface configuration that is exposed to the adhering agent layer between the silk screen circuit produces mist, reduces the phenomenon that sees through brightness and is all pointed out all the time.At this moment, these those skilled in the art relation between the roughness of black treated side of Copper Foil and surface treatment copper foil of always considering to be untreated.And, its surface made as Fig. 1 and the high magnification of usefulness more than 1500 times shown in Figure 2 carry out can being viewed as smooth surface when SEM observes, and monitor roughness with the contact pin type roughmeter.In Fig. 1 and Fig. 2,, do not find big difference though the turbidity value of turbidimetric analysis turbidimetry test is obviously different.
But, the result that this case inventor etc. has carried out concentrated research, the phenomenon that has obtained being solved by above-mentioned viewpoint this generation mist is impossible conclusion.At this, in Fig. 3 and Fig. 4, shown with the low range of 500 multiplying powers the image of SEM when observing carried out on the surface of the surface treatment copper foil that does not have difference of Fig. 1 and Fig. 2.In the image of this Fig. 3 and Fig. 4, found difference really.That is, in the roughness when narrow zone when high magnification and the short distance scanning measured with the contact pin type roughmeter, there not be the relation between discovery and the turbidity value.At this, use can carry out the three-dimensional surface structure elucidation microscope of sector scanning, by adopting the roughness value in 144 μ m * 108 μ m zones, with the flatness on the being seen surface of micron order as problem.
In addition, if surface roughness with this Copper Foil that is untreated, when representing with the surface roughness Rz that adopts three-dimensional surface structure elucidation measurement microscope, if have the following surface of 850nm, then as mentioned above, the etching that is assembled into the conductive filament mesh-shaped in the header board of Plasmia indicating panel finishes, and the surface configuration that is exposed to the adhering agent layer between the silk screen circuit just can not produce mist.
At this, illustrate and adopt the microscopical roughness of three-dimensional surface structure elucidation to measure.In the present invention, the NewView5032 that adopts Zygo society to make, with 100 times to object lens, carried out concave-convex surface mensuration with laser.And be that high spatial frequency composition and wavelength 3 μ ms below be the mode of low spatial frequency composition 10 μ ms more than to discharge wavelength this moment, setting threshold, and obtain Ra and Rz according to measurement result.Therefore, not the roughness of obtaining with the contact pin type roughmeter at this said Ra and Rz.
To discharge wavelength is the mode setting threshold of the high spatial frequency composition below the 3 μ m, be because in the zone below wavelength is 3 μ m, in the turbidity test of having adopted the untreated foil of carrying out before and after the black processing and surface treatment paper tinsel, the degree of mist has difference even detect by an unaided eye, it is poor also to be difficult to catch sensitively it, on turbidity value, can not create a difference thus, so be judged as the scope that is not to be applicable to turbidity test.On the other hand, be the mode setting threshold of the above low spatial frequency composition of 10 μ m with the deletion wavelength, in case be because wavelength is more than the 10 μ m, then produce excessive concavo-convexly, and as mentioned above, it doesn't matter in the generation of excessive concavo-convex and mist, even the mensuration turbidity value does not have any meaning yet.
In addition, the surface that can observe the above-mentioned electrolytic copper foil that is untreated that the black treated side is set has the low profile of surface roughness (Rzjis) the less than 0.8 μ m when measuring with the contact pin type roughmeter of JIS B 0601 regulation.And on the basis of this surface roughness, preferably its glossiness (Gs (60 °)) is more than 400.Usually, as the be untreated index of flatness of electrolytic copper foil of expression, adopt the value of Rzjis all the time.But, only can only obtain the information of concavo-convex short transverse with Rzjis, can't obtain concavo-convex " cycle " or information such as " waveforms ".Therefore, employing comprises the glossiness notion of parameter of " cycle " or " waveform " information of the concave-convex surface of the electrolytic copper foil that is untreated, by with the combination of itself and surface roughness, can clearly catch and low profile electrolytic copper foil in the past separate out difference between the face.
And the surface of this electrolytic copper foil that is untreated is smooth, helps the formation of the smooth black treated side of black surface treatment copper foil more.Usually, when making electrolytic copper foil according to above-mentioned patent documentation 3～patent documentation 6 disclosed manufacture methods, the value of separating out the roughness (Rzjis) of face side is the degree that surpasses 0.8 μ m.With respect to this, the surface roughness of the Copper Foil that is untreated used in the present invention, if adopt manufacture method described later, then can access the surface roughness (Rzjis) of separating out the face side is the following low profile of 0.6 μ m.At this, be not particularly limited the lower limit of surface roughness, but the following of roughness is limited to about 0.1 μ m from experience.This shows that in the formation of the black treated side of black surface treatment copper foil of the present invention, the surface roughness (Rzjis) of preferably separating out the face side is below the 0.6 μ m, and its glossiness (Gs (60 °)) is more than 600.In addition, in the practical measurement of the above surface roughness, obviously certain deviation is arranged on this measured value, think that the following of measured value that can guarantee is limited to about 0.2 μ m.
The mensuration of glossiness used in the present invention, it is length direction (MD direction) along electrolytic copper foil, measure light with 60 ° of incidence angles to this copper foil surface irradiation, mensuration is carried out with 60 ° of intensity of light reflected of angle of reflection, be the Grossmeters VG-2000 type that adopts Japanese electric look Industrial Co., Ltd system, measure according to the assay method JIS Z 8741-1997 of glossiness.Its result when according to above-mentioned patent documentation 3～patent documentation 6 disclosed manufacture methods, makes the thick electrolytic copper foil of 18 μ m, and when measuring its glossiness of separating out face [Gs (60 °)], is about 250～380 scope.With respect to this, the glossiness of electrolytic copper foil of the present invention [Gs (60 °)] surpasses 400, has more smooth surface as can be known.Further, as shown in the Examples, by optimal conditions, glossiness [Gs (60 °)] also can reach more than 700.In addition, at this, also do not stipulate the higher limit of glossiness, but from experience, about 780 is the upper limit.
The surface of the Copper Foil that is untreated of the black treated side of aforesaid formation surface treatment copper foil of the present invention is not the glassy surface of above-mentioned electrolytic copper foil but separates out face.This is because of the flatness that realizes this degree on the surface that is difficult in rotating cathode, the cause that the copper of being separated out falls from the rotating cathode sur-face peeling in electrolysis easily.
In the manufacturing of the aforesaid Copper Foil that is untreated, creating conditions below preferred the use.That is the preferred sulfuric acid based copper electrolyte that uses at least a, the QAS polymer that added in 3-sulfydryl-1-propane sulfonic acid (hereinafter referred to as [MPS]) or two (the 3-sulfonic acid propyl group) disulphide (hereinafter referred to as [SPS]) and chlorine and obtain, with circulus.By using the sulfuric acid based copper electrolyte of this composition, can make the Copper Foil that is untreated with above-mentioned quality.Three kinds of compositions of MPS or the SPS that comprises in the sulfuric acid based copper electrolyte, the QAS polymer with circulus, chlorine are neccessary compositions as used herein.In addition, sulfuric acid based copper electrolyte of the present invention is that copper concentration is that 50g/l～120g/l, free sulfuric acid concentration are the solution about 60g/l～250g/l.
MPS in this sulfuric acid based copper electrolyte or the total concentration of SPS are preferably 0.5ppm～100ppm, more preferably 0.5ppm～50ppm, more preferably 1ppm～30ppm.When the not enough 0.5ppm of the total concentration of this MPS or SPS, the face of the separating out chap of electrolytic copper foil is difficult to obtain the low profile electrolytic copper foil.On the other hand,, then can not improve the level and smooth effect of the face of separating out of resulting electrolytic copper foil, only can cause the cost of liquid waste processing to increase if the total concentration of MPS or SPS surpasses 100ppm.In addition, comprise MPS salt and SPS salt at this said MPS or SPS, the record value of concentration is 3-sulfydryl-1-propane sulfonic acid sodium (hereinafter referred to as [the MPS-Na]) scaled value as sodium salt.
And this MPS has the situation of dimerization in sulfuric acid based copper electrolyte of the present invention, becomes the SPS structure this moment.Therefore, the total concentration of MPS or SPS is meant except salts such as 3-sulfydryl-1-propane sulfonic acid monomer or MPS-Na, also contains material that adds as SPS and the concentration of adding the modifier of party such as back and SPS in the electrolyte as MPS to.Below, represent the structural formula of MPS with Chemical formula 1, represent the structural formula of SPS with Chemical formula 2.
[Chemical formula 1]
[Chemical formula 2]
And the concentration of the QAS polymer in the sulfuric acid based copper electrolyte that uses in the manufacture method of electrolytic copper foil of the present invention is preferably 1ppm～150ppm, more preferably 10ppm～120ppm, more preferably 15ppm～40ppm.At this, as QAS polymer, can use all materials, but consider that forming low profile separates out the effect of face, most preferably uses diallyldimethylammonium chloride (hereinafter referred to as [DDAC]) polymer with circulus.DDAC is the material that becomes circulus when forming polymer architecture, and the part of circulus is made of the nitrogen-atoms of quaternary ammonium.And, owing to think that the above-mentioned circulus of this DDAC polymer is the mixture of any one or they in four-membered ring～heptatomic ring, so,, and represent as representative at this compound that has five-membered ring structure in these polymer with chemical formula 3.From this chemical formula 3 as can be known, the DDAC polymer is meant that DDAC has the polymer of the above polymer structure of dimer.
[chemical formula 3]
And when the deficiency of the DDAC polymer concentration in this sulfuric acid based copper electrolyte 1ppm, in any case improve the total concentration of MPS or SPS, the also roughening of the face of separating out of electrolytic copper foil is difficult to obtain the low profile electrolytic copper foil.On the other hand, if the concentration of the DDAC polymer in the sulfuric acid based copper electrolyte surpasses 150ppm, then the precipitation state of copper becomes unstable, is difficult to obtain the low profile electrolytic copper foil.
Further, the cl concn of above-mentioned sulfuric acid based copper electrolyte is preferably 5ppm～60ppm.If the not enough 5ppm of this cl concn, the face of separating out of electrolytic copper foil becomes coarse, can't keep low profile.On the other hand, if cl concn surpasses 60ppm, then the matsurface of electrolytic copper foil becomes coarse, and it is unstable that the electrolysis state becomes, and can't form the face of separating out of low profile.
As mentioned above, the one-tenth balance-dividing between MPS in the above-mentioned sulfuric acid based copper electrolyte and/or SPS, DDAC polymer and the chlorine is the most important, if the balance of this tittle has broken away from above-mentioned scope, its result can't obtain the Copper Foil that is untreated of above-mentioned quality.
And, when using the manufacturing of above-mentioned sulfuric acid based copper electrolyte to be untreated Copper Foil, be 20 ℃～60 ℃, more preferably 40 ℃～55 ℃ in the liquid temperature, current density is 15A/dm
2～90A/dm
2, 50A/dm more preferably
2～70A/dm
2Condition under carry out electrolysis.When 20 ℃ of liquid temperature less thaies, speed of separating out reduces, and it is big that the error of the mechanical-physical character of elongation and hot strength etc. becomes.On the other hand, if the liquid temperature surpasses 60 ℃, then the evaporation water component increases, and the change of solution concentration is accelerated, and the face of separating out of resulting electrolytic copper foil is difficult to keep good flatness.In addition, as the not enough 15A/dm of current density
2The time, the speed of separating out of copper diminishes, and industrial production is poor.On the other hand, surpass 90A/dm when current density
2The time, it is big that the roughness of the face of separating out of the resulting Copper Foil that is untreated becomes, and can't keep low profile.
In addition, preferred above-mentioned black treated side has antirust processing layer.This is because can guarantee the long preservation of surface treatment copper foil of the present invention.This antirust processing layer only otherwise can cause the variable color of black treated side and is got final product by the copper etchant solution dissolving easily, can use any one of organic rust preventing etc. of inorganic antirust, the BTA, imidazoles etc. of zinc, brass etc.
The black surface treatment copper foil: on the surface of the above-mentioned Copper Foil that is untreated the black treated side is set, the glossiness of this black treated side [Gs (60 °)] is preferably below 35.If glossiness surpasses 35, then become so-called black light state, metallic luster is very obvious.
And the formation of this black treated side can be adopted the various manufacture methods of the following stated.
[nickel is the black processing method]
From the viewpoint that becomes good black processing and can remove by copper etchant solution, nickel is that the black processing method preferably adopts the following stated black processing method.
Separating out on the face of the above-mentioned Copper Foil that is untreated, form the sulfuric acid nickel dam.This sulfuric acid nickel dam is to use the nickelous sulfate (5 hydrate) that contains 10g/l～300g/l, with the alkali hydroxide slaine pH value is adjusted into the nickelous sulfate electroplate liquid of 5.5～6.0 scopes, by using 1A/dm
2Above current density electrolysis, thereby the nickel coating of formation black.At this, if the not enough 10g/l of nickelous sulfate (5 hydrate) in the nickelous sulfate electroplate liquid, the electrodeposition rate of then formed sulfuric acid nickel dam is slack-off, and the thickness of the sulfuric acid nickel dam uneven tendency grow that becomes.With respect to this, if nickelous sulfate (5 hydrate) surpasses 300g/l, the tone of then formed sulfuric acid nickel dam can't become good black state.This nickelous sulfate electroplate liquid is characterised in that and does not contain the pH buffer.
In addition, the pH value of solution value of Ci Shi nickelous sulfate electroplate liquid is adjusted at 5.5～6.0 scope.If, then can't obtain good black not in this scope.The adjustment of this pH value has been used the alkali hydroxide slaine of NaOH or potassium hydroxide etc.
And the current density when carrying out electrolysis adopts 1A/dm
2Above electric current.Even above-mentioned nickelous sulfate electroplate liquid flows through superfluous Faradaic current, also can guarantee the flatness of formed plating face.Therefore, in the present invention,, actively utilized near the rising of the pH value the negative terminal surface when electrolysis by not using the pH buffer of common employing to carry out electroplating processes intentionally.That is,, on the sulfuric acid nickel dam, comprise nickel oxide etc., thereby form the plating tunicle of black by under strong alkali environment, carrying out electrolysis in fact.Therefore, there is no need specially to be provided with the upper limit of current density, set arbitrarily as long as consider the productivity in the operation.
And, when being under the situation of black processing for nickel, particularly preferably in as antirust processing layer the zinc-nickel alloy layer being set on the black treated side.This is to be that the copper electrolyte of black processing layer carries out the dissolution accelerator that etching is removed because can become according to nickel.Narrations in the back such as formation to this zinc-nickel alloy layer.
Through above operation, by wash, drying, obtain the black surface treatment copper foil.To at this said method for washing, there is no particular limitation for drying means, can adopt the mode of common consideration.
[cobalt is the black processing method]
At cobalt is in the black processing method, and from becoming the viewpoint that good black processing and the enough copper etchant solutions of energy are removed, two kinds of cobalts that preferably adopt the following stated are that black processing method A and cobalt are any one among the black processing method B.
Cobalt is black processing method A: this cobalt is the black processing method that the black processing method is to use not to be had when stirring bath.Separating out on the face of the above-mentioned Copper Foil that is untreated, form the cobaltous sulfate electrodeposited coating.This cobaltous sulfate electrodeposited coating is to adopt the cobaltous sulfate (7 hydrate), the pH value that contain 8g/l～10g/l not to bathe as having to stir at the cobaltous sulfate electroplate liquid of 4.0 above scopes, uses 2A/dm
2Above current density is carried out electrolysis, thereby forms the cobaltous sulfate electrodeposited coating of black system.It promptly is the cobaltous sulfate plating condition when not carrying out the solution stirring.At this, if the not enough 8g/l of cobaltous sulfate (7 hydrate) in the cobaltous sulfate electroplate liquid, the electrodeposition rate of then formed cobaltous sulfate electrodeposited coating is slack-off, and the thickness of cobaltous sulfate layer becomes uneven the tendency grow.With respect to this, if cobaltous sulfate (7 hydrate) surpasses 10g/l, the tone of formed cobaltous sulfate electrodeposited coating can't become good black state.
In addition, the pH value of solution value of Ci Shi cobaltous sulfate electroplate liquid is that target is adjusted with 4.5～5.5 scope preferably.Qualification rate is good in this scope, can access good black cobalt electrodeposited coating.The adjustment of this pH value is not preferably added other electrolyte such as NaOH or potassium hydroxide.This is because the black of cobalt electrodeposited coating becomes metallochrome easily.
Therefore, the pH value of solution value is by the solution metal ion concentration is maintained necessarily, thus with this pH value stabilization in the scope more than 4.0.For the concentration of cobalt ions in the aforesaid stabilizing solution, the following method of preferred employing, promptly adopt deliquescent cobalt electrode, with the dissolving of the cobalt ions composition of electro-deposition and the method for supplying with or by the continuous monitoring concentration of metal ions, stablize the method for concentration of cobalt ions etc. by suitable interpolation cobalt hydroxide.
And the current density when carrying out electrolysis adopts 2A/dm
2Above electric current.Form even above-mentioned cobaltous sulfate electroplate liquid flows through superfluous Faradaic current and to have trickle to a certain degree concavo-convex plating face, but seldom cause the dry linting phenomenon.Therefore, need not to set especially the upper limit of current density, but reference technique general knowledge is considered the productivity in the operation and is set arbitrarily and get final product.
Through above operation,, obtain the black surface treatment copper foil of cobaltous sulfate electrodeposited coating as the black treated side by washing, drying.There is no particular limitation to method for washing, drying means at this moment, can adopt the mode of common consideration.
Cobalt is black processing method B: at this, illustrate and used the black processing method that stirs when bathing.By adopting following condition, form and the same fine and close black treated side of the formed cobaltous sulfate electrodeposited coating of cobaltous sulfate electroplating bath that stirs by nothing.
To contain 10g/l～40g/l cobaltous sulfate (7 hydrate) and pH value and be more than 4.0, the liquid temperature is that cobaltous sulfate electroplate liquid below 30 ℃ is bathed as stirring, and uses 4A/dm
2Following current density is carried out electrolysis, thereby forms the cobaltous sulfate electrodeposited coating that black is on the face separating out of the above-mentioned Copper Foil that is untreated.That is be that black processing method A compares basic difference and is to carry out electrolysis to carrying out when the above-mentioned cobaltous sulfate electroplate liquid of cobaltous sulfate when electroplating stirs, at this and cobalt.This cobalt sulfate concentration has the low more tendency that might produce good black state more of cobalt sulfate concentration.But if the not enough 10g/l of cobaltous sulfate (7 hydrate) in the cobaltous sulfate electroplate liquid, the electrodeposition rate of the cobaltous sulfate electrodeposited coating that then adopt to stir bathe forms is slack-off, and the thickness of cobaltous sulfate layer becomes uneven the tendency grow, causes the result of industrial production difference.With respect to this, if the cobaltous sulfate (7 hydrate) in the cobaltous sulfate electroplate liquid surpasses 40g/l, then formed cobaltous sulfate electrodeposited coating is difficult to form the concavo-convex of densification, and its result can't become good black state.
In addition, the Ph value of the cobaltous sulfate electroplate liquid solution of this moment is preferably more than 4.0, and especially preferred scope with 4.5～5.5 is that target is adjusted.In this scope, qualification rate is good, can stably obtain good black cobalt electrodeposited coating.In adjusting, this pH value preferably do not add other electrolyte such as NaOH or potassium hydroxide.This is because the black of cobalt electrodeposited coating becomes the cause of metallochrome easily as mentioned above.And also as described above, the pH value of solution value can be by keeping certain solution metal ion concentration, with this pH value stabilization in the scope more than 4.0.
And the cobaltous sulfate electroplate liquid of this moment preferably is adjusted into its liquid temperature below 30 ℃ and uses.Has the low more tendency that can access good black treated side more of liquid temperature this moment.If the liquid temperature is set in below 30 ℃, then can access better black treated side.
And the current density when carrying out electrolysis adopts 4A/dm
2Following electric current.In this scope,, also can form tack cobaltous sulfate electrodeposited coating good, that have good micro concavo-convex with organic material etc. even do not carry out the roughened of copper foil surface.Usually, if expect that having concavo-convex black is plate surface, then adopt and flow through the method that the Faradaic current in plating zone is burnt in superfluous belonging to.But it is more little then to have the employed current density of electrolysis at this, the possible more tendency that stably obtains good black processing.Therefore, preferably adopt little current density as far as possible, if but consider industrial production, the lower limit that then can judge current density is 0.5A/dm
2On the other hand, if current density surpasses 4A/dm
2, then become and handle no roughened among the manufacture method A of Copper Foil with above-mentioned first surface and the black treated side of same levels when on copper foil surface, implementing the black processing, lost the meaning of employing manufacture method B.And the black treated side that forms in above-mentioned current density range can not cause the dry linting phenomenon.
Through above operation,, obtain the surface treatment copper foil of cobaltous sulfate electrodeposited coating as the black treated side by washing, drying.To at this said method for washing, there is no particular limitation for drying means, can adopt the mode of common consideration.
Antirust processing: preferably implement antirust processing on the surface of the black surface treatment copper foil that so obtains.At this formation operation of antirust processing layer is described.About adopting organic rust preventings such as known in the past imidazoles, BTA, inorganic antirust etc. the situation of the kirsite of common zinc or brass etc. need not special explanation, abides by usual way get final product, in the detailed explanation of this omission.
Below, illustrate and carry out electroplating processes with zinc nickel alloy electroplating liquid or zinc-cobalt alloy electroplate liquid and form the situation of antirust processing layer.Zinc nickel alloy electroplating at first is described.To there is no particular limitation at this employed zinc nickel alloy electroplating liquid, but if the words of giving an example, can adopt following condition, that is, using the nickel concentration of nickelous sulfate is that 1～2.5g/l, the zinc concentration that uses zinc pyrophosphate are that 0.1～1g/l, potassium pyrophosphate 50～500g/l, 20～50 ℃ of liquid temperature, pH value are 8～11, current density is 0.3～10A/dm
2Condition etc.
Then, plating describes about zinc-cobalt alloy.There is no particular limitation to zinc-cobalt alloy electroplate liquid as used herein, but if the words of giving an example, can adopt following condition, promptly, using the cobalt concentration of cobaltous sulfate is 1～2.5g/l, using the zinc concentration of zinc pyrophosphate is 0.1～1g/l, and potassium pyrophosphate is that 50～500g/l, liquid temperature are that 20～50 ℃, pH value are 8～11, current density is 0.3～10A/dm
2Condition etc.The antirust processing layer that this zinc-cobalt alloy is electroplated and chromate treatment combination described later forms demonstrates outstanding especially corrosion resisting property.
Further,, after forming zinc-nickel alloy layer or zinc-cobalt alloy layer etc. on the surface at Copper Foil, form chromate coating again, then can access more outstanding corrosion resisting property as antirust processing.That is, after forming above-mentioned antirust processing layer, the chromate treatment process is set gets final product.In this chromate treatment process, can adopt replacement that chromatedsolution is contacted with this copper foil surface to handle, perhaps in chromatedsolution, carry out electrolysis and the electrolytic chromate that forms the chromate tunicle any one method in handling.In addition, the chromatedsolution of Shi Yonging also can use the material in the usual method institute scope of application herein.By washing, drying, obtain the better black surface treatment copper foil of corrosion resistance then.
＜electromagnetic wave shielding conductive mesh〉above-described black surface treatment copper foil of the present invention, its surperficial flatness is good, use this black surface treatment copper foil to make conductive mesh, and etching is when finishing, be exposed on the surface of the adhering agent layer between circuit and can not produce mist, so can not worsen the brightness of Plasmia indicating panel, help very much to eliminate the simulation profile obstacle that the light emitting control because of pixel causes.
And the black processing that is used for the formation of black treated side among the present invention can not produce the dry linting phenomenon, and brings into play good black, and this black processing layer can be removed with common copper etching work procedure etching.Therefore, can use the operation of making printed wiring board, easily be processed into shape arbitrarily.If consider these, we can say in the purposes that is best suited for the electromagnetic wave shielding conductive mesh in the header board that is assembled into Plasmia indicating panel.
Narrate embodiment below, but at first the relation of the roughness that adopted contact pin type roughmeter and three-dimensional surface structure elucidation measurement microscope is described.Contact pin type roughmeter and three-dimensional surface structure elucidation microscope all are to use for the identical index of the so-called roughness that obtains same target, so it has been generally acknowledged that these values are consistent.But the contact pin type roughness depends on its contact pilotage radius of curvature, and three-dimensional surface structure elucidation microscope then depends on surveys the light optical path, owing to measure the precision difference, measured value is also different usually.In general, when on measuring the surface, having to a certain degree concavo-convex, have adopt the contact pin type roughmeter the roughness measured value than adopting the big tendency of the microscopical roughness measured value of three-dimensional surface structure elucidation.On the other hand, have that to measure the surface level and smooth and do not have a low profile surface of waveform, with the roughness measured value of contact pin type roughmeter than adopting the little tendency of the microscopical roughness measured value of three-dimensional surface structure elucidation.
Below, explanation manufacturing, etching test result, the result of turbidimetric analysis turbidimetry test of manufacturing, black processing Copper Foil of Copper Foil that be untreated successively.
The be untreated manufacturing of Copper Foil: as the sulfuric acid based copper electrolyte, use copper concentration to be 5ppm as 140g/l as copper-bath, MPS concentration as 80g/l and free sulfuric acid concentration, DDAC polymer (use SENKA (strain) system UNISENSE FPA100L) 3ppm, cl concn are 50 ℃ solution as 10ppm, liquid temperature, and at current density 60A/dm
2Under carry out electrolysis, obtain the thick Copper Foil that is untreated of 18 μ m.The transfer printing of this Copper Foil that is untreated Rzjis (contact pin type roughmeter)=1.02 μ m of glassy surface of surface configuration of titanium system electrode, the roughness of the face of separating out of another side side and glossiness are Ra (three-dimensional surface structure elucidation microscope)=29.2nm, Rz (three-dimensional surface structure elucidation microscope)=200nm, Ra (contact pin type roughmeter)=0.12 μ m, Rzjis (contact pin type roughmeter)=0.47 μ m, glossiness [Gs (60 °)]=699.
The manufacturing of black surface treatment copper foil: then, the above-mentioned Copper Foil that is untreated is carried out pickling processes, thereby make it to purify.It is that 100g/l, liquid temperature are 30 ℃ dilution heat of sulfuric acid that this pickling processes condition is to use concentration, and dip time was 30 seconds.
Then, after pickling processes finishes,, form the sulfuric acid nickel dam separating out on the face of the above-mentioned Copper Foil that is untreated.The formation of sulfuric acid nickel dam be adopt nickelous sulfate (5 hydrate) for 100g/l, with NaOH with the pH value be adjusted into 6.0, the liquid temperature is 30 ℃ nickelous sulfate electroplate liquid, at 1A/dm
2Current density under carry out electrolysis, formed the nickelous sulfate electrodeposited coating of black thus.
Further,, on the two sides of the Copper Foil of the formation of the black sulfuric acid nickel electrodeposited coating that is through with, adopt zinc nickel alloy electroplating liquid to carry out electroplating processes, form the zinc-nickel alloy layer thus on the two sides as antirust processing.Being is 2.0g/l at the nickel concentration that adopts nickelous sulfate, to adopt the zinc concentration of zinc pyrophosphate be 0.5g/l, and potassium pyrophosphate is that 250g/l, liquid temperature are that 35 ℃, pH value are 10, current density is 5A/dm
2Condition under 5 seconds of electrolysis, on the two sides evenly and smoothly electro-deposition the zinc-nickel alloy layer.
After the formation of above-mentioned zinc-nickel alloy layer finishes, abundant spray pure water and washing, and in ambient temperature being maintained 150 ℃ drying oven by electric heater, stopped for 4 seconds, remove moisture, thereby obtained having the surface treatment copper foil of the black treated side of very good tone.The glossiness of the black treated side of this black surface treatment copper foil [Gs (60 °)] is 27.In addition, by on this black treated side, pasting in the adhesive tape test of peeling off behind the adherence adhesive tape, do not find dry linting yet.
Etching test: on the two sides of the black surface treatment copper foil that obtains as mentioned above, paste the dry film that becomes etchant resist.Then, only on the dry film of black treated side side, the overlapping test mask that is used to manufacture experimently electromagnetic wave shielding conductive mesh is that 200 μ m, silk screen live width are that 10 μ m, silk screen drift angle are 45 ° with ultraviolet photoetching silk screen spacing, and has the conductive mesh pattern of silk screen electrode part on every side.At this moment, simultaneously on whole of the rete against corrosion of opposing face, also carry out ultraviolet exposure, be difficult to thus be removed by the development of back.Then, use aqueous slkali to develop, form the etchant resist pattern.
Then, use copper chloride etching solution, carry out the copper etching, then, peel off rete against corrosion, made electromagnetic wave shielding conductive mesh thus from black treated side side as copper etchant solution.Its result, no etch residue, the very good etching of having carried out.
Turbidimetric analysis turbidimetry test: on the black treated side of above-mentioned black surface treatment copper foil, formed resin thin film layer as described below.At first, as raw material, adopted o-cresol phenolic epoxy varnish (Toto Kasei KK makes, YDCN-704), dissolve in solvent the aromatic polyamide resin polymer, with as the mixing varnish of cyclopentanone of solvent and the BJJP3225-50P of commercially available Nippon Kayaku K. K's system.Then, mix in the varnish at this, interpolation is as the VH-4170 phenolic resins of big Japanese ink Co., Ltd. system of curing agent and as the 2E4MZ of Shikoku Chem's system of curing accelerator, the resin compound that obtains having cooperation ratio shown below.
Resin compound: o-cresol phenolic epoxy varnish 38 weight portions
Aromatic polyamide resin polymer 50 weight portions
Phenolic resins 18 weight portions
Curing accelerator 0.1 weight portion
By further using methylethylketone, this resin compound is adjusted into the resin solid composition reaches 30 weight %, thereby obtain resin solution.With the resin solution of making as mentioned above, coat with the intaglio plate coating machine on the black treated side of above-mentioned black surface treatment copper foil.Then, carry out five minutes air-dry, dried three minutes in 140 ℃ heating environment then, obtaining resin layer thickness is the tape tree fat Copper Foil of 40 μ m.Then, from this state, comprehensive etching black surface treatment copper foil is as independent resin film, used as the turbidimetric analysis turbidimetry sample.The result who carries out the turbidimetric analysis turbidimetry of this sample is 5.8%.
Embodiment 2
Below, explanation manufacturing, etching test result, the result of turbidimetric analysis turbidimetry test of manufacturing, black surface treatment copper foil of Copper Foil that be untreated successively.
The be untreated manufacturing of Copper Foil: the Copper Foil that is untreated that has used the method manufacturing identical with embodiment 1.Therefore, the transfer printing of this Copper Foil that is untreated Rzjis, the roughness and the glossiness that opposite side is separated out face of glassy surface of surface configuration of titanium system electrode identical with embodiment 1.
The manufacturing of black surface treatment copper foil: then, in the same manner the above-mentioned Copper Foil that is untreated is carried out pickling processes, thereby make it to purify with embodiment 1.
And, after pickling processes finishes, at the face of the separating out formation cobaltous sulfate electrodeposited coating of the above-mentioned Copper Foil that is untreated.The formation of cobaltous sulfate electrodeposited coating be with cobaltous sulfate (7 hydrate) be adjusted into that 10g/l, pH value are adjusted into 5.0, the liquid temperature is adjusted into 30 ℃ cobaltous sulfate electroplate liquid and do not bathe as having to stir, and at 2A/dm
2Current density under 8 seconds of electrolysis, (conversion thickness is 320mg/m to form the cobaltous sulfate electrodeposited coating of black thus
2).At this moment, expressly do not carry out the adjustment of concentration of cobalt ions in the solution.This is because consider it is the short time electrolysis, so think the adjustment that need not concentration of metal ions.And, in this embodiment, do not carry out special antirust processing.
Through after the above operation, abundant spray pure water and washing, and in ambient temperature being maintained 150 ℃ drying oven by electric heater, stopped for 4 seconds, remove moisture, thereby obtained having the black surface treatment copper foil of the black treated side of very good tone.The glossiness of the black treated side of this black surface treatment copper foil [Gs (60 °)] is 25.In addition, by on this black treated side, pasting in the adhesive tape test of peeling off behind the adherence adhesive tape, do not find dry linting.
Etching test: use the black surface treatment copper foil that obtains as mentioned above, made electromagnetic wave shielding conductive mesh in the same manner with embodiment 1.Its result, no etch residue has carried out very good etching.
Turbidimetric analysis turbidimetry test: use the method identical, make the state of the Copper Foil of tape tree fat, and from this state, etching black processing Copper Foil obtains independent resin film comprehensively with the foregoing description 1, and with its sample of using as turbidimetric analysis turbidimetry.The result who carries out the turbidimetric analysis turbidimetry of this sample is 5.5%.
Below, explanation manufacturing, etching test result, the result of turbidimetric analysis turbidimetry test of manufacturing, black surface treatment copper foil of Copper Foil that be untreated successively.
The be untreated manufacturing of Copper Foil: the Copper Foil that is untreated that has used the method manufacturing identical with embodiment 1.Therefore, the transfer printing of this Copper Foil that is untreated Rzjis, the roughness and the glossiness that opposite side is separated out face of glassy surface of surface configuration of titanium system electrode identical with embodiment 1.
The manufacturing of black surface treatment copper foil: then, in the same manner the above-mentioned Copper Foil that is untreated is carried out pickling processes, thereby make it to purify with embodiment 1.
And, after pickling processes finishes, at the face of the separating out formation cobaltous sulfate electrodeposited coating of the above-mentioned Copper Foil that is untreated.Sulfuric acid thus the formation of electrodeposited coating be with cobaltous sulfate (7 hydrate) be adjusted into that 20g/l, pH value are adjusted into 5.5, the liquid temperature is adjusted into 27 ℃ cobaltous sulfate electroplate liquid with mixing bath, and at 1A/dm
2Current density under 15 seconds of electrolysis, (conversion thickness is 334mg/m to form the cobaltous sulfate electrodeposited coating of black thus
2).At this moment, expressly do not carry out the adjustment of concentration of cobalt ions in the solution.This is because consider it is the short time electrolysis, so think the adjustment that need not concentration of metal ions.And, in this embodiment, do not carry out special antirust processing.
After above operation, abundant spray pure water and washing, and in ambient temperature being maintained 150 ℃ drying oven by electric heater, stopped for 4 seconds, remove moisture, thereby obtained having the black surface treatment copper foil of the black treated side of very good tone.The glossiness of the black treated side of this black surface treatment copper foil [Gs (60 °)] is 26.In addition, after on this black treated side, pasting the adherence adhesive tape, peel off in the adhesive tape test that carries out, do not find dry linting.
Etching test: use the black surface treatment copper foil that obtains as mentioned above, made electromagnetic wave shielding conductive mesh in the same manner with embodiment 1.Its result does not have no etch residue, has carried out very good etching.
Turbidimetric analysis turbidimetry test: use the method identical, make the state of the Copper Foil of tape tree fat, and, obtain independent resin film from the comprehensive etching black of this state processing Copper Foil with the foregoing description 1, and with its sample of using as turbidimetric analysis turbidimetry.The result who carries out the turbidimetric analysis turbidimetry of this sample is 5.4%.
Below, explanation manufacturing, etching test result, the result of turbidimetric analysis turbidimetry test of manufacturing, black surface treatment copper foil of Copper Foil that be untreated successively.
The be untreated manufacturing of Copper Foil: as the sulfuric acid based copper electrolyte, use copper concentration 80g/l and free sulfuric acid concentration to be 10ppm as copper-bath, the SPS concentration of 140g/l, DDAC polymer (use SENKA (strain) system UNISENSE FPA100L) concentration is 50 ℃ solution as 20ppm, cl concn as 22ppm, liquid temperature, and is 60A/dm in current density
2Condition under carry out electrolysis, obtain the thick Copper Foil that is untreated of 18 μ m.The transfer printing of this Copper Foil that is untreated Rzjis (contact pin type roughmeter)=1.02 μ m of glassy surface of titanium system electrode surface shape, the roughness of the face of separating out of another side side and glossiness are respectively Ra (three-dimensional surface structure elucidation microscope)=26nm, Rz (three-dimensional surface structure elucidation microscope)=180nm, Ra (contact pin type roughmeter)=0.10 μ m, Rzjis (contact pin type roughmeter)=0.30 μ m, glossiness [Gs (60 °)]=735.
Below, obtained the black surface treatment copper foil in the same manner with embodiment 3.The glossiness of the black treated side of this black surface treatment copper foil [Gs (60 °)] is 26.In addition, after on this black treated side, pasting the adherence adhesive tape, peel off in the adhesive tape test that carries out, do not find dry linting.
Etching test: use the black surface treatment copper foil that obtains as mentioned above, made electromagnetic wave shielding conductive mesh in the same manner with embodiment 1.Its result, no etch residue has carried out very good etching.
Turbidimetric analysis turbidimetry test: use the method identical, make the Copper Foil state of tape tree fat, from the comprehensive etching black of this state surface treatment copper foil, obtain independent resin film, with its sample of using as turbidimetric analysis turbidimetry with the foregoing description 1.The result who carries out the turbidimetric analysis turbidimetry of this sample is 5.2%.
Comparative example
In comparative example, produce the Copper Foil that is untreated with following described manufacture method, implement the black surface treatment of the foregoing description 2, and show the result who it is carried out the turbidimetric analysis turbidimetry test.Therefore, the result of the manufacturing and the turbidimetric analysis turbidimetry test of the Copper Foil that is untreated only is described.Other condition is identical with embodiment 2.
[comparative example 1]
The be untreated manufacturing of Copper Foil: as the tracking test of patent documentation 3 disclosed embodiment 1, copper sulphate (reagent) and sulfuric acid (reagent) are dissolved in the pure water, being adjusted into copper sulphate (conversion of 5 hydrates) is 280g/l, free sulfuric acid concentration is 90g/l, and copolymer (Nitto Boseki Co. Ltd's system of adding poly (dially dialkyl) based quaternary ammonium salt and sulfur dioxide, trade name PAS-A-5, weight average molecular weight 4000:4ppm), polyethylene glycol (mean molecule quantity 1000:10ppm), 3-sulfydryl-1-propane sulfonic acid (1ppm), further use sodium chloride that cl concn is adjusted into 20ppm, thereby prepared the sulfuric acid copper electroplating liquid.
Then, use the titanium plate electrode, its surface is ground with No. 2000 pouncing papers as negative electrode.Surface roughness is adjusted into Ra=0.20 μ m.Then, anode uses stereotype, is that 40 ℃, current density are 50A/dm in the liquid temperature
2Condition under the above-mentioned electrolyte of electrolysis, thereby obtain the thick Copper Foil that is untreated of 18 μ m.The roughness and the glossiness of this Copper Foil that is untreated are: transfer printing Rzjis (contact pin type roughmeter)=1.02 μ m, roughness and the glossiness that the another side side is separated out face of glassy surface of titanium system electrode surface shape be respectively Ra (three-dimensional surface structure elucidation microscope)=124.5nm, Rz (three-dimensional surface structure elucidation microscope)=1532nm, Ra (contact pin type roughmeter)=0.18 μ m, Rzjis (contact pin type roughmeter)=0.88 μ m, glossiness [Gs (60 °)]=283.
Then, obtained the black surface treatment copper foil in the same manner with embodiment 2.The glossiness of the black treated side of this black surface treatment copper foil [Gs (60 °)] is 22.In addition, after on this black treated side, pasting the adherence adhesive tape, peel off in the adhesive tape test that carries out, do not find dry linting.
Turbidimetric analysis turbidimetry test: use the method identical, make the Copper Foil state of tape tree fat, from the comprehensive etching black of this state surface treatment copper foil, obtain independent resin film, with its sample of using as turbidimetric analysis turbidimetry with the foregoing description 1.The result who carries out the turbidimetric analysis turbidimetry of this sample is 12.3%.
[comparative example 2]
The be untreated manufacturing of Copper Foil: as the sulfuric acid based copper electrolyte, using copper concentration is 50 ℃ solution as the copper-bath of 140g/l, DDAC polymer (using SENKA (strain) system UNISENSE FPA100L), cl concn as 15ppm, liquid temperature as 80g/l and free sulfuric acid concentration, is 60A/dm in current density
2Under carry out electrolysis, thereby obtain the thick Copper Foil that is untreated of 18 μ m.The roughness and the glossiness of this Copper Foil that is untreated are respectively: transfer printing Rzjis (contact pin type roughmeter)=1.02 μ m of glassy surface of titanium system electrode surface shape, the roughness of the face of separating out of another side side and glossiness are respectively Ra (three-dimensional surface structure elucidation microscope)=422nm, Rz (three-dimensional surface structure elucidation microscope)=5240nm, Ra (contact pin type roughmeter)=0.57 μ m, Rzjis (contact pin type roughmeter)=3.80 μ m, glossiness [Gs (60 °)]=0.7.
Then, obtained the black surface treatment copper foil in the same manner with embodiment 2.The glossiness of the black treated side of this black surface treatment copper foil [Gs (60 °)] is 0.5.In addition, after on this black treated side, pasting the adherence adhesive tape, peel off in the adhesive tape test that carries out, do not find dry linting.
Turbidimetric analysis turbidimetry test: use the method identical, make the Copper Foil state of tape tree fat,, obtain independent resin film from the comprehensive etching black of this state surface treatment copper foil with the foregoing description 1, and with its sample of using as turbidimetric analysis turbidimetry.The result who carries out the turbidimetric analysis turbidimetry of this sample is 42.0%.
[comparative example 3]
The be untreated manufacturing of Copper Foil: as the sulfuric acid based copper electrolyte, use copper concentration to be 80g/l, free sulfuric acid concentration is that copper-bath, the DDAC polymer concentration of 140g/l be 4ppm (use SENKA (strain) system UNISENSE FPA100L), low-molecular-weight glue (number-average molecular weight 1560:6ppm), cl concn as 15ppm, liquid temperature is 50 ℃ solution, and is 60A/dm in current density
2Under carry out electrolysis, obtain the thick Copper Foil that is untreated of 18 μ m.The roughness and the glossiness of this Copper Foil that is untreated are respectively: transfer printing Rzjis (contact pin type roughmeter)=1.02 μ m of glassy surface of titanium system electrode surface shape, the roughness of the face of separating out of another side side and glossiness are respectively Ra (three-dimensional surface structure elucidation microscope)=360nm, Rz (three-dimensional surface structure elucidation microscope)=4530nm, Ra (contact pin type roughmeter)=0.42 μ m, Rzjis (contact pin type roughmeter)=3.89 μ m, glossiness [Gs (60 °)]=1.1.
Then, obtained the black surface treatment copper foil in the same manner with embodiment 2.The glossiness of the black treated side of this black surface treatment copper foil [Gs (60 °)] is 0.5.In addition, after on this black treated side, pasting the adherence adhesive tape, peel off in the adhesive tape test that carries out, do not find dry linting.
Turbidimetric analysis turbidimetry test: use the method identical, make the Copper Foil state of tape tree fat,, obtain independent resin film from the comprehensive etching black of this state surface treatment copper foil with the foregoing description 1, and with its sample of using as turbidimetric analysis turbidimetry.The result who carries out the turbidimetric analysis turbidimetry of this sample is 45.0%.
Utilizability on the industry
Black surface treatment copper foil of the present invention, the flatness of its black treatment surface is good, makes Make conductive mesh with this black surface treatment copper foil, and after the etching end, be exposed between circuit The degree that produces mist on the surface of adhering agent layer is low, thus can not worsen the brightness of Plasmia indicating panel, Help very much to eliminate the profile obstacle that the light emitting control because of pixel causes.
In addition, if the black treated side of black surface treatment copper foil of the present invention as at certain bar The nickel that forms under the part is that black treated side or cobalt are the black treated side, the processing of employing black Words do not have the dry linting phenomenon, and can bring into play good black, and this black processing layer can be usually The copper etching work procedure in remove. Therefore, need not special equipment investment, use manufacturing printed wiring board Operation can provide the electromagnetic wave of the Plasmia indicating panel of high-quality black film to appraise through comparison conductive mesh.
Description of drawings
Fig. 1 is the observation image of the black surface treatment copper foil when carrying out the SEM observation with 10000 times of high magnifications.
Fig. 2 is the observation image of the black surface treatment copper foil when carrying out the SEM observation with 10000 times of high magnifications.
Fig. 3 is the observation image of the black surface treatment copper foil when carrying out the SEM observation with 500 times of low ranges pair surface identical with Fig. 1.
Fig. 4 is the observation image of the black surface treatment copper foil when carrying out the SEM observation with 500 times of low ranges pair surface identical with Fig. 2.
Fig. 5 is the cross-section model of manufacturing process that is used to show the electromagnetic wave shielding conductive mesh of Plasmia indicating panel.
Fig. 6 is the cross-section model of manufacturing process that is used to show the electromagnetic wave shielding conductive mesh of Plasmia indicating panel.
Fig. 7 is the cross-section model of manufacturing process that is used to show the electromagnetic wave shielding conductive mesh of Plasmia indicating panel.
Wherein, description of reference numerals is as follows:
1. header board
2. black surface treatment copper foil
3. black treated side
4.PET film
5. adhering agent layer
6. resist layer
7. conductive mesh pattern
8. conductive mesh (electromagnetic wave shielding conductive mesh)
9a. first transparency carrier
9b. second transparency carrier
Claims (7)
1. black surface treatment copper foil, this black surface treatment copper foil is the surface treatment copper foil that has the black treated side on the surface of the electrolytic copper foil that is untreated, it is characterized in that, the surface roughness Ra that the above-mentioned electrolytic copper foil that is untreated has with three-dimensional surface structure elucidation measurement microscope is the following surface of 45nm, and is provided with the black treated side on this surface.
2. black surface treatment copper foil according to claim 1, wherein, the face that the black treated side is set of the above-mentioned electrolytic copper foil that is untreated is below the 850nm with the surface roughness Rz of three-dimensional surface structure elucidation measurement microscope.
3. black surface treatment copper foil according to claim 1 and 2, wherein, the face that the black treated side is set of the above-mentioned electrolytic copper foil that is untreated is the low profile of surface roughness (Rzjis) the less than 0.8 μ m when using JIS B 0601 to measure, and glossiness (Gs (60 °)) is more than 400.
4. according to any described black surface treatment copper foil in the claim 1 to 3, wherein, above-mentioned black treated side has antirust processing layer.
5. according to any described black surface treatment copper foil in the claim 1 to 4, wherein, the glossiness of above-mentioned black treated side [Gs (60 °)] is below 35.
6. according to any described black surface treatment copper foil in the claim 1 to 5, wherein, above-mentioned black treated side is that nickel is that black treated side or cobalt are the black treated side.
7. the electromagnetic wave shielding conductive mesh for front panel of a plasma display, it has used any described black surface treatment copper foil in the claim 1 to 6.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005205445 | 2005-07-14 | ||
| JP205445/2005 | 2005-07-14 |
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|---|---|
| CN101223839A true CN101223839A (en) | 2008-07-16 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA200680025669XA Pending CN101223839A (en) | 2005-07-14 | 2006-07-14 | Blackening surface treated copper foil and electromagnetic wave shielding conductive mesh for front panel of plasma display using the blackening surface treated copper foil |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPWO2007007870A1 (en) |
| KR (1) | KR20080025143A (en) |
| CN (1) | CN101223839A (en) |
| TW (1) | TW200718347A (en) |
| WO (1) | WO2007007870A1 (en) |
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| CN104040036A (en) * | 2012-01-18 | 2014-09-10 | Jx日矿日石金属株式会社 | Surface-treated copper foil for copper-clad laminate and copper-clad laminate using same |
| CN107636209A (en) * | 2015-06-26 | 2018-01-26 | 住友金属矿山股份有限公司 | Conductive board |
| CN112118669A (en) * | 2019-06-19 | 2020-12-22 | 金居开发股份有限公司 | Advanced reverse electrolytic copper foil and copper foil substrate using same |
| TWI776943B (en) * | 2018-01-10 | 2022-09-11 | 日商拓自達電線股份有限公司 | Electromagnetic wave shielding film |
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| CN102618902B (en) * | 2012-04-24 | 2015-04-01 | 山东金宝电子股份有限公司 | Surface treatment process of copper foil for flexible copper-clad plate |
| JP5816230B2 (en) * | 2012-05-11 | 2015-11-18 | Jx日鉱日石金属株式会社 | Surface-treated copper foil and laminate using the same, copper foil, printed wiring board, electronic device, and method for manufacturing printed wiring board |
| TWI462662B (en) | 2013-02-06 | 2014-11-21 | Nanya Plastics Corp | Composite double-side blackening foil and manufacturing method thereof |
| TWI539032B (en) * | 2013-08-01 | 2016-06-21 | Chang Chun Petrochemical Co | Electrolytic copper foil, cleaning fluid composition and cleaning copper foil method |
| JP5862916B1 (en) * | 2014-06-24 | 2016-02-16 | 奥野製薬工業株式会社 | Composition for blackening treatment of copper metal or silver metal |
| CN106687623B (en) | 2014-09-02 | 2019-07-16 | 三井金属矿业株式会社 | Melanism surface treatment copper foil and copper foil with carrier foils |
| WO2016093109A1 (en) * | 2014-12-08 | 2016-06-16 | 三井金属鉱業株式会社 | Method of manufacturing printed wiring board |
| JP6555341B2 (en) * | 2015-04-28 | 2019-08-07 | 住友金属鉱山株式会社 | Conductive substrate |
| JP7392996B2 (en) * | 2019-06-19 | 2023-12-06 | 金居開發股▲分▼有限公司 | Advanced electrolytic copper foil and copper-clad laminates using it |
| CN212648273U (en) | 2020-07-29 | 2021-03-02 | 隆达电子股份有限公司 | Light emitting diode device |
| US11610875B2 (en) | 2020-09-18 | 2023-03-21 | Lextar Electronics Corporation | Light emitting array structure and display |
| US12094861B2 (en) | 2020-09-18 | 2024-09-17 | Lextar Electronics Corporation | Light emitting array structure and display |
| CN115050308A (en) | 2021-03-08 | 2022-09-13 | 隆达电子股份有限公司 | Display device |
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| JP3782250B2 (en) * | 1999-03-31 | 2006-06-07 | 共同印刷株式会社 | Method for manufacturing electromagnetic shielding base material |
| 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 |
| JP3756852B2 (en) * | 2002-07-01 | 2006-03-15 | 日本電解株式会社 | Method for producing electrolytic copper foil |
| 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 |
| JP4120806B2 (en) * | 2002-10-25 | 2008-07-16 | 福田金属箔粉工業株式会社 | Low rough surface electrolytic copper foil and method for producing the same |
| KR100389061B1 (en) * | 2002-11-14 | 2003-06-25 | 일진소재산업주식회사 | Electrolytic copper foil and process producing the same |
| JP4458519B2 (en) * | 2003-07-28 | 2010-04-28 | 三井金属鉱業株式会社 | 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 |
-
2006
- 2006-07-13 TW TW095125642A patent/TW200718347A/en unknown
- 2006-07-14 JP JP2007524718A patent/JPWO2007007870A1/en active Pending
- 2006-07-14 WO PCT/JP2006/314031 patent/WO2007007870A1/en active Application Filing
- 2006-07-14 KR KR1020087000944A patent/KR20080025143A/en not_active Application Discontinuation
- 2006-07-14 CN CNA200680025669XA patent/CN101223839A/en active Pending
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|---|---|---|---|---|
| CN104040036A (en) * | 2012-01-18 | 2014-09-10 | Jx日矿日石金属株式会社 | Surface-treated copper foil for copper-clad laminate and copper-clad laminate using same |
| CN107636209A (en) * | 2015-06-26 | 2018-01-26 | 住友金属矿山股份有限公司 | Conductive board |
| TWI776943B (en) * | 2018-01-10 | 2022-09-11 | 日商拓自達電線股份有限公司 | Electromagnetic wave shielding film |
| CN112118669A (en) * | 2019-06-19 | 2020-12-22 | 金居开发股份有限公司 | Advanced reverse electrolytic copper foil and copper foil substrate using same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2007007870A1 (en) | 2009-01-29 |
| KR20080025143A (en) | 2008-03-19 |
| TW200718347A (en) | 2007-05-01 |
| WO2007007870A1 (en) | 2007-01-18 |
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