WO2022244826A1 - Roughened copper foil, copper foil with carrier, copper-cladded laminate board, and printed wiring board - Google Patents
Roughened copper foil, copper foil with carrier, copper-cladded laminate board, and printed wiring board Download PDFInfo
- Publication number
- WO2022244826A1 WO2022244826A1 PCT/JP2022/020747 JP2022020747W WO2022244826A1 WO 2022244826 A1 WO2022244826 A1 WO 2022244826A1 JP 2022020747 W JP2022020747 W JP 2022020747W WO 2022244826 A1 WO2022244826 A1 WO 2022244826A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- copper foil
- roughened
- peaks
- valleys
- carrier
- Prior art date
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 227
- 239000011889 copper foil Substances 0.000 title claims abstract description 193
- 238000004458 analytical method Methods 0.000 claims abstract description 38
- 238000010191 image analysis Methods 0.000 claims abstract description 17
- 229910052802 copper Inorganic materials 0.000 claims description 38
- 239000010949 copper Substances 0.000 claims description 38
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 21
- 230000005540 biological transmission Effects 0.000 abstract description 40
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- 238000012545 processing Methods 0.000 abstract description 6
- 239000010410 layer Substances 0.000 description 91
- 238000011282 treatment Methods 0.000 description 54
- 239000011347 resin Substances 0.000 description 37
- 229920005989 resin Polymers 0.000 description 37
- 238000007788 roughening Methods 0.000 description 33
- 238000000034 method Methods 0.000 description 30
- 238000007747 plating Methods 0.000 description 29
- 239000000243 solution Substances 0.000 description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 21
- 238000011156 evaluation Methods 0.000 description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- 239000000758 substrate Substances 0.000 description 13
- 239000011888 foil Substances 0.000 description 12
- 239000002245 particle Substances 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 238000005259 measurement Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 239000011701 zinc Substances 0.000 description 9
- 229910000365 copper sulfate Inorganic materials 0.000 description 8
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 8
- 238000000151 deposition Methods 0.000 description 8
- 230000000007 visual effect Effects 0.000 description 8
- 229910052725 zinc Inorganic materials 0.000 description 8
- 229910000990 Ni alloy Inorganic materials 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 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
- 230000008021 deposition Effects 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- -1 nitrogen-containing organic compounds Chemical class 0.000 description 5
- MTRFEWTWIPAXLG-UHFFFAOYSA-N 9-phenylacridine Chemical compound C1=CC=CC=C1C1=C(C=CC=C2)C2=NC2=CC=CC=C12 MTRFEWTWIPAXLG-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000004070 electrodeposition Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- KFJDQPJLANOOOB-UHFFFAOYSA-N 2h-benzotriazole-4-carboxylic acid Chemical compound OC(=O)C1=CC=CC2=NNN=C12 KFJDQPJLANOOOB-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 238000009499 grossing Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 230000003746 surface roughness Effects 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 229910001297 Zn alloy Inorganic materials 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- BQJTUDIVKSVBDU-UHFFFAOYSA-L copper;sulfuric acid;sulfate Chemical compound [Cu+2].OS(O)(=O)=O.[O-]S([O-])(=O)=O BQJTUDIVKSVBDU-UHFFFAOYSA-L 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000002500 effect on skin Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000002346 layers by function Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- AZUHEGMJQWJCFQ-UHFFFAOYSA-N 1,1-bis(2h-benzotriazol-4-ylmethyl)urea Chemical compound C1=CC2=NNN=C2C(CN(CC=2C3=NNN=C3C=CC=2)C(=O)N)=C1 AZUHEGMJQWJCFQ-UHFFFAOYSA-N 0.000 description 1
- FYADHXFMURLYQI-UHFFFAOYSA-N 1,2,4-triazine Chemical compound C1=CN=NC=N1 FYADHXFMURLYQI-UHFFFAOYSA-N 0.000 description 1
- WZRRRFSJFQTGGB-UHFFFAOYSA-N 1,3,5-triazinane-2,4,6-trithione Chemical compound S=C1NC(=S)NC(=S)N1 WZRRRFSJFQTGGB-UHFFFAOYSA-N 0.000 description 1
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- ZDDUSDYMEXVQNJ-UHFFFAOYSA-N 1H-imidazole silane Chemical compound [SiH4].N1C=NC=C1 ZDDUSDYMEXVQNJ-UHFFFAOYSA-N 0.000 description 1
- ZOTOAABENXTRMA-UHFFFAOYSA-N 3-[4-[3-(3-trimethoxysilylpropylamino)propoxy]butoxy]propan-1-amine Chemical compound CO[Si](OC)(OC)CCCNCCCOCCCCOCCCN ZOTOAABENXTRMA-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 1
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- PPTYNCJKYCGKEA-UHFFFAOYSA-N dimethoxy-phenyl-prop-2-enoxysilane Chemical compound C=CCO[Si](OC)(OC)C1=CC=CC=C1 PPTYNCJKYCGKEA-UHFFFAOYSA-N 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- XEMZLVDIUVCKGL-UHFFFAOYSA-N hydrogen peroxide;sulfuric acid Chemical compound OO.OS(O)(=O)=O XEMZLVDIUVCKGL-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 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 1
- 229910052718 tin Inorganic materials 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- VMYXFDVIMUEKNP-UHFFFAOYSA-N trimethoxy-[5-(oxiran-2-yl)pentyl]silane Chemical compound CO[Si](OC)(OC)CCCCCC1CO1 VMYXFDVIMUEKNP-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/04—Wires; Strips; Foils
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- 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
- C25D5/16—Electroplating with layers of varying thickness
-
- 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
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
-
- 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
-
- 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
- H05K3/46—Manufacturing multilayer circuits
Definitions
- the present invention relates to a roughened copper foil, a copper foil with a carrier, a copper-clad laminate, and a printed wiring board.
- the MSAP method is a technique suitable for forming extremely fine circuits, and is carried out using a copper foil with a carrier in order to take advantage of its characteristics. For example, as shown in FIGS. 1 and 2, an ultra-thin copper foil (roughened copper foil 10) is placed on an insulating resin substrate 11 having a lower layer circuit 11b on a base substrate 11a, and a prepreg 12 and a primer layer 13 are formed thereon. (step (a)), peel off the carrier (not shown), and then form via holes 14 by laser drilling as necessary (step (b)).
- step (c) After applying chemical copper plating 15 (step (c)), a predetermined pattern is masked by exposure and development using dry film 16 (step (d)), and electrolytic copper plating 17 is applied (step (e )).
- step (e ) After the dry film 16 is removed to form the wiring portion 17a (step (f)), the unnecessary ultra-thin copper foil or the like between the mutually adjacent wiring portions 17a and 17a is removed by etching over the entire thickness thereof ( Step (g)), wiring 18 formed in a predetermined pattern is obtained.
- Patent Document 1 International Publication No. 2016/117587
- the average distance between surface peaks on the side of the release layer is 20 ⁇ m or less
- the maximum height difference of the undulations on the side opposite to the release layer is A carrier-attached copper foil comprising an ultra-thin copper foil having a thickness of 1.0 ⁇ m or less
- Patent Document 2 Japanese Patent Application Laid-Open No.
- a carrier-attached copper foil having a ratio Sp/Spk to Spk of 3.271 or more and 10.739 or less is disclosed.
- shear strength is one of the physical adhesion indices between a circuit and a substrate, and in order to effectively avoid the above-mentioned circuit peeling, a roughened copper foil suitable for improving the shear strength has been proposed. ing.
- Patent Document 3 International Publication No.
- a treated copper foil is disclosed. According to such a roughened copper foil, it is believed that both excellent etching properties and high shear strength can be achieved in the processing of copper-clad laminates or the manufacture of printed wiring boards.
- a printed wiring board is provided with a copper foil processed into a wiring pattern and an insulating resin base material. Transmission loss consists of conductor loss caused by the copper foil and dielectric loss caused by the insulating resin base material.
- Patent Document 4 Japanese Patent No. 6462961 describes a surface-treated copper foil in which a roughening treatment layer, an anti-corrosion treatment layer and a silane coupling layer are laminated in this order on at least one side of the copper foil.
- the interface developed area ratio Sdr measured from the surface of the coupling layer is 8% or more and 140% or less, the root mean square surface gradient Sdq is 25° or more and 70° or less, and the surface texture aspect ratio Str is 0.25 or more and 0. 0.79 or less. It is said that such a surface-treated copper foil makes it possible to manufacture a printed wiring board with little transmission loss of high-frequency electrical signals and excellent adhesion during reflow soldering.
- copper foil with low transmission loss that is, copper foil with excellent high-frequency characteristics
- transmission loss can be suppressed by smoothing the copper foil and miniaturizing the roughened particles, the physical adhesion (particularly shear strength) between the copper foil and the substrate resin will decrease. .
- the present inventors have now found that in the roughened copper foil, the sum of the heights of the peaks and valleys calculated as the sum of the volume of the peaks and the volume of the valleys, and the average height of the peaks and the average height of the valleys Excellent transmission characteristics and high shear strength in the processing of copper-clad laminates or the manufacture of printed wiring boards by providing a surface profile in which the average height of peaks and valleys calculated as the sum is controlled within a predetermined range. I got the knowledge that it can be compatible with.
- an object of the present invention is to provide a roughened copper foil that can achieve both excellent transmission characteristics and high shear strength in the processing of copper-clad laminates or the manufacture of printed wiring boards.
- a roughened copper foil having a roughened surface on at least one side, wherein the roughened surface has a plurality of peaks that are convex with respect to a reference surface and a plurality of valleys that are concave with respect to the reference surface.
- the mountain and the valley calculated as the sum of the volume of the mountain and the volume of the valley in an analysis area of 2000 nm ⁇ 2000 nm
- the sum of the heights of the valleys is 1.4 ⁇ 10 8 nm 3 or more and 3.5 ⁇ 10 8 nm 3 or less
- Aspect 7 The roughened copper foil according to aspect 6, wherein the surface voxel ratio is 0.25 or more and 0.35 or less.
- Aspect 8 The roughened copper foil according to any one of aspects 1 to 7, further comprising an antirust layer and/or a silane coupling agent layer on the roughened surface.
- a copper clad laminate comprising the roughened copper foil according to any one of aspects 1 to 8.
- a printed wiring board comprising the roughened copper foil according to any one of aspects 1 to 8.
- FIG. 2 is a flow chart of the steps for explaining the MSAP method, showing the first half of the steps (steps (a) to (d)).
- FIG. 2 is a flow chart of the steps for explaining the MSAP method, showing the latter half of the steps (steps (e) to (g)).
- FIG. 3 is a schematic cross-sectional view for explaining the reference surface of the roughened surface and the sum of the heights of peaks and valleys in the roughened copper foil.
- FIG. 4 is a schematic cross-sectional view for explaining the reference plane of the roughened surface and the average height of peaks and valleys in the roughened copper foil.
- FIG. 4 is a diagram in which mountains present on the roughened surface of the roughened copper foil are virtually partitioned by voxels.
- FIG. 4 is a diagram showing regions where laser light cannot enter when a roughened surface is measured with a laser microscope.
- 3 is a diagram showing x-, y-, and z-axes in 3D-SEM observation, and a slice plane S in relation to a roughened copper foil.
- FIG. FIG. 4 is a diagram showing the relationship between each axis after rotating the x-axis, y-axis, and z-axis and the roughened copper foil in 3D-SEM image analysis.
- image obtained using FIB-SEM on the roughened surface refers to cross-sectional processing by FIB (focused ion beam) on the roughened surface of the roughened copper foil. It means an aggregate of cross-sectional images acquired through cross-sectional observation by a SEM (scanning electron microscope), and constitutes three-dimensional shape data as a whole. Specifically, as shown in FIG. 7, the x-axis and z-axis are defined as the in-plane directions of the roughened copper foil 10, and the y-axis is defined as the thickness direction of the roughened copper foil 10.
- a cross-sectional image including the roughened surface of the roughened copper foil 10 on the slice plane S parallel to the xy plane is acquired, and this slice plane is translated by a predetermined interval (for example, 10 nm) in the z-axis direction. It is a collection of cross-sectional images (for example, 1000 sheets in total) acquired in a predetermined analysis area (for example, 2000 nm ⁇ 2000 nm) while moving.
- the “mountain” of the roughened surface is, as schematically shown in FIGS. It means the part that is convex with respect to .
- the “valley” of the roughened surface is, as schematically shown in FIGS. It means a portion that is concave with respect to the surface R.
- the "reference plane" of the roughened surface can be identified by three-dimensional image analysis of an image obtained using FIB-SEM for the roughened surface.
- a median value (reference point) of the height (y direction) of the roughened surface in a predetermined matrix size (for example, 99) in the xz plane centered on the pixel of interest is obtained.
- the matrix size is 99, it means obtaining the median value from the height of the roughened surface in each of 99 ⁇ 99 pixels centering on the pixel of interest.
- This operation is performed for all the pixels in the xz plane that constitute the image of the concave-convex structure (each of them as a target pixel), and the median height of the roughened surface in each target pixel ( reference point). Then, a plane passing through all the reference points in each pixel of interest obtained in this manner can be created and used as a reference plane.
- the three-dimensional image analysis described above can be automatically performed using commercially available software, and a median filter specifying a matrix size (for example, 99) is applied to the uneven structure of the roughened copper foil.
- the reference plane can be determined systematically (that is, there is no item in commercially available software that allows arbitrary setting of conditions other than the matrix size for setting the reference plane).
- the total height of peaks and valleys is a parameter representing the sum of the volume of peaks and the volume of valleys in an analysis area of 2000 nm x 2000 nm (size when viewed from above). That is, as schematically shown in FIG. 3, the total volume Ap of peaks with respect to the reference plane R (total volume of all peaks in the analysis region) and the total volume Av of valleys with respect to the reference plane R (in the analysis region The total volume of all valleys) corresponds to the sum of the heights of peaks and valleys.
- the “sum of heights of peaks and valleys” may be referred to as "sum of volumes of peaks and valleys". Since it is a value calculated by accumulating the numerical value referred to by the name "height”, the expression “total height of peaks and valleys" is daringly used in this specification so that those skilled in the art can easily carry out the measurement. I am using
- the “average height of peaks and valleys” is a parameter that represents the sum of the average height of peaks and the average height of valleys in an analysis area of 2000 nm ⁇ 2000 nm (size when viewed in plan). . That is, as schematically shown in FIG. 4, the average peak height Hp with respect to the reference plane R (the average height of all peaks in the analysis region) and the average valley height Hv with respect to the reference plane R ( The average height H of all valleys in the analysis area) corresponds to the average height H of peaks and valleys.
- total volume of mountains per unit area of 1 nm2 means dividing the total volume of all mountains in an analysis area of 2000 nm x 2000 nm (size when viewed from above) by the area of the analysis area. It is a parameter calculated by
- the sum of the heights of the peaks and valleys, the average height of the peaks and valleys, and the total volume of the peaks per unit area of 1 nm2 are the three-dimensional images of the roughened surface obtained using FIB-SEM. It can be identified by analysis. Such three-dimensional image analysis can be performed using commercially available software. For example, three-dimensional alignment software "ExFact Slice Aligner (version 2.0)” (Nippon Visual Science Co., Ltd. ) and three-dimensional image analysis software “ExFact VR (version 2.2)” and “foil Analysis (version 1.0)” (both manufactured by Nippon Visual Science Co., Ltd.), described in the examples of this specification. Image analysis can be performed according to the conditions specified. Also, a method for obtaining a cross-sectional image obtained by using the FIB-SEM will be described in Examples below.
- the term “surface voxel ratio” refers to, when the peaks of the roughened surface are divided into a plurality of voxels, all voxels that constitute the peaks in an analysis area of 2000 nm ⁇ 2000 nm (size when viewed in plan) means the ratio of the total volume of voxels that make up the surface of the mountain (surface voxels) to the total volume of .
- the surface voxel ratio can be specified by three-dimensional image analysis of an image obtained using FIB-SEM for the roughened surface. Specifically, as schematically shown in FIG. 5, an image obtained using an FIB-SEM of the roughened surface is shown in FIG.
- electrode surface of the carrier refers to the surface that was in contact with the cathode when the carrier was manufactured.
- the "deposition surface" of the carrier refers to the surface on which electrolytic copper is deposited during carrier production, that is, the surface that is not in contact with the cathode.
- the copper foil according to the present invention is a roughened copper foil.
- This roughened copper foil has a roughened surface on at least one side.
- This roughened surface has a plurality of peaks that are convex with respect to the reference plane and a plurality of valleys that are concave with respect to the reference plane. Then, when the image obtained using FIB-SEM on the roughened surface is subjected to three-dimensional image analysis, the peaks and valleys calculated as the sum of the volume of the peaks and the volume of the valleys in the analysis area of 2000 nm ⁇ 2000 nm is 1.4 ⁇ 10 8 nm 3 or more and 3.5 ⁇ 10 8 nm 3 or less.
- the average height of peaks and valleys calculated as the sum of the average height of peaks and the average height of valleys in an analysis area of 2000 nm ⁇ 2000 nm is 40 nm or more and 90 nm or less.
- the copper clad laminate can be processed or processed. In the production of printed wiring boards, it is possible to achieve both excellent transmission characteristics (especially excellent high-frequency characteristics) and high shear strength (and thus high circuit adhesion in terms of shear strength).
- the sum of the heights of the peaks and valleys represents the total volume of the peaks and valleys with respect to the reference plane R, which is the portion in contact with the substrate (the portion that bites into the substrate). roughly corresponds to the volume of Therefore, the greater the sum of the heights of the peaks and valleys, the greater the volume of the portion in contact with the substrate, leading to an increase in shear strength. Also, as described above with reference to FIG. In other words, the smaller the average height of peaks and valleys, the smaller the unevenness of the surface.
- the unevenness of the surface is small, even if the skin depth is reduced due to the increase in frequency, the current path is less likely to be affected by the unevenness of the surface, leading to a reduction in transmission loss. Therefore, by controlling both the total height of the peaks and valleys on the roughened surface and the average height of the peaks and valleys within a predetermined range, when used in a copper-clad laminate or a printed wiring board, It is possible to realize excellent transmission characteristics and high shear strength in a well-balanced manner.
- FIG. 6 schematically shows an example of measurement of the roughened surface using a laser microscope.
- a laser beam is irradiated from above the roughened surface.
- the roughened copper foil has a total height of peaks and valleys on the roughened surface of 1.4 ⁇ 10 8 nm 3 or more and 3.5 ⁇ 10 8 nm 3 or less. , preferably 2.0 ⁇ 10 8 nm 3 or more and 3.5 ⁇ 10 8 nm 3 or less from the viewpoint of further improving shear strength, or 1.4 ⁇ 10 8 nm 3 from the viewpoint of further improving transmission characteristics. 1.8 ⁇ 10 8 nm 3 or less.
- the roughened copper foil has an average height of peaks and valleys on the roughened surface of 40 nm or more and 90 nm or less, preferably 40 nm or more and 80 nm or less, and more preferably transmission characteristics. From the viewpoint of further improving the shear strength, it is 40 nm or more and 50 nm or less, or from the viewpoint of further improving the shear strength, it is 70 nm or more and 80 nm or less.
- the roughened copper foil preferably has a total volume of ridges per unit area of 1 nm 2 on the roughened surface of 7.0 nm 3 or more and 50.0 nm 3 or less, more preferably 30.0 nm 3 or more and 50.0 nm. 3 or less. By doing so, even higher shear strength can be achieved when used in a copper-clad laminate or a printed wiring board.
- the roughened copper foil preferably has a surface voxel ratio of 0.25 or more and 0.60 or less on the roughened surface, and more preferably, to further improve the shear strength. It is 0.25 or more and 0.35 or less from a viewpoint, or 0.40 or more and 0.60 or less from a viewpoint of further improvement of transmission characteristics.
- FIG. 5 schematically shows an example in which the peaks (P 1 , P 2 , P 3 ) present on the roughened surface of the roughened copper foil 10 are virtually partitioned by voxels B.
- the peaks P 1 , P 2 and P 3 shown in FIG. 5 have the same total volume and therefore the same number of voxels B (20) that define each of these peaks.
- the number of surface voxels Bs (voxels located at the outermost surface portion in contact with the resin) constituting the surface of the mountain is 20, 14 and 10, respectively.
- the shear strength by the surface voxel ratio. Also, from the viewpoint of achieving excellent transmission characteristics, it is desirable to control the surface voxel ratio within the above range in consideration of the average height of peaks and valleys.
- the thickness of the roughened copper foil is not particularly limited, it is preferably 0.1 ⁇ m or more and 35 ⁇ m or less, more preferably 0.5 ⁇ m or more and 5.0 ⁇ m or less, and still more preferably 1.0 ⁇ m or more and 3.0 ⁇ m or less.
- the roughened copper foil is not limited to a general copper foil whose surface has been roughened, and may be a carrier-attached copper foil whose copper foil surface has been roughened.
- the thickness of the roughened copper foil is the thickness not including the height of the roughened particles formed on the surface of the roughened surface (thickness of the copper foil itself constituting the roughened copper foil). is.
- a copper foil having a thickness within the above range is sometimes called an ultra-thin copper foil.
- the roughened copper foil has a roughened surface on at least one side. That is, the roughened copper foil may have roughened surfaces on both sides, or may have a roughened surface only on one side.
- the roughened surface is typically provided with a plurality of roughening particles (nobs), and each of these roughening particles preferably consists of copper particles.
- the copper particles may consist of metallic copper, or may consist of a copper alloy.
- the roughening treatment for forming the roughened surface can be preferably carried out by forming roughening particles with copper or a copper alloy on the copper foil.
- This roughening treatment is preferably carried out according to a plating technique involving three stages of plating processes.
- a copper sulfate solution having a copper concentration of 5 g/L or more and 15 g/L or less and a sulfuric acid concentration of 200 g/L or more and 250 g/L or less is used, and the liquid temperature is 25° C. or more and 45° C. or less.
- Electrodeposition is preferably carried out under the plating conditions of a current density of 2 A/dm 2 or more and 4 A/dm 2 or less.
- the first-stage plating process is preferably performed twice in total using two tanks.
- a copper sulfate solution with a copper concentration of 60 g/L or more and 80 g/L or less and a sulfuric acid concentration of 200 g/L or more and 260 g/L or less was used, and the liquid temperature was 45 ° C. or more and 55 ° C. or less, and the current density was 10 A. /dm 2 or more and 15 A/dm 2 or less.
- the copper concentration is 5 g/L or more and 20 g/L or less
- the sulfuric acid concentration is 60 g/L or more and 90 g/L or less
- the chlorine concentration is 20 mg/L or more and 40 mg/L or less
- the 9-phenylacridine (9PA) concentration is preferably performed using a copper sulfate solution of 100 mg/L or more and 200 mg/L or less under plating conditions of a liquid temperature of 25° C. or more and 35° C. or less and a current density of 30 A/dm 2 or more and 60 A/dm 2 or less.
- Each of the second and third plating steps may be performed twice in total using two baths, but is preferably completed in one time. Through such a plating process, it becomes easier to form bumps on the treated surface that are convenient for satisfying the surface parameters described above.
- the roughened copper foil may be subjected to antirust treatment and may have an antirust treatment layer formed thereon.
- the antirust treatment preferably includes plating with zinc.
- the plating treatment using zinc may be either zinc plating treatment or zinc alloy plating treatment, and the zinc alloy plating treatment is particularly preferably zinc-nickel alloy treatment.
- the zinc-nickel alloy treatment may be a plating treatment containing at least Ni and Zn, and may further contain other elements such as Sn, Cr, Co and Mo.
- the Ni/Zn adhesion ratio in the zinc-nickel alloy plating is preferably 1.2 to 10, more preferably 2 to 7, and still more preferably 2.7 to 4 in mass ratio.
- the rust prevention treatment preferably further includes chromate treatment, and this chromate treatment is more preferably performed on the surface of the plating containing zinc after the plating treatment using zinc.
- a particularly preferred antirust treatment is a combination of zinc-nickel alloy plating treatment and subsequent chromate treatment.
- the surface of the roughened copper foil may be treated with a silane coupling agent to form a silane coupling agent layer.
- a silane coupling agent layer can be formed by appropriately diluting the silane coupling agent, coating it, and drying it.
- silane coupling agents include epoxy-functional silane coupling agents such as 4-glycidylbutyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, or 3-aminopropyltrimethoxysilane, N-(2- aminoethyl)-3-aminopropyltrimethoxysilane, N-3-(4-(3-aminopropoxy)butoxy)propyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, etc.
- epoxy-functional silane coupling agents such as 4-glycidylbutyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, or 3-aminopropyltrimethoxysilane, N-(2- aminoethyl)-3-aminopropyltrimethoxysilane, N-3-(4-(3-aminopropoxy)but
- amino-functional silane coupling agents or mercapto-functional silane coupling agents such as 3-mercaptopropyltrimethoxysilane or olefin-functional silane coupling agents such as vinyltrimethoxysilane, vinylphenyltrimethoxysilane, or 3-methacrylic Acrylic functional silane coupling agents such as roxypropyltrimethoxysilane, or imidazole functional silane coupling agents such as imidazole silane, or triazine functional silane coupling agents such as triazine silane, and the like.
- the roughened copper foil preferably further comprises an antirust treatment layer and/or a silane coupling agent layer on the roughened surface, more preferably the antirust treatment layer and the silane coupling agent layer.
- the antirust layer and the silane coupling agent layer may be formed not only on the roughened surface side of the roughened copper foil, but also on the side where the roughened surface is not formed.
- the roughened copper foil of the present invention may be provided in the form of a carrier-attached copper foil.
- a carrier By adopting the form of a copper foil with a carrier, it is possible to realize excellent laser workability and fine line circuit formability. That is, according to a preferred embodiment of the present invention, a carrier, a release layer provided on the carrier, and the roughened copper foil provided on the release layer with the roughened surface facing outward, A copper foil with carrier is provided.
- a known layer structure can be employed, except for using the roughened copper foil of the present invention.
- a carrier is a support for supporting the roughened copper foil to improve its handling properties
- a typical carrier includes a metal layer.
- Examples of such a carrier include aluminum foil, copper foil, stainless steel (SUS) foil, resin film or glass whose surface is metal-coated with copper or the like, and copper foil is preferred.
- the copper foil may be a rolled copper foil or an electrolytic copper foil, preferably an electrolytic copper foil.
- the thickness of the carrier is typically 250 ⁇ m or less, preferably 7 ⁇ m or more and 200 ⁇ m or less.
- the surface of the carrier on the release layer side is preferably smooth. That is, in the manufacturing process of the carrier-attached copper foil, an ultra-thin copper foil (before roughening treatment) is formed on the release layer side surface of the carrier.
- the roughened copper foil of the present invention is used in the form of a carrier-attached copper foil, the roughened copper foil can be obtained by roughening such an ultra-thin copper foil. Therefore, by smoothing the surface of the carrier on the release layer side, the outer surface of the ultra-thin copper foil can also be smoothed. It becomes easy to realize a roughened surface having the sum of the heights of peaks and valleys and the average height of peaks and valleys within the predetermined range.
- the surface of the carrier on the release layer side can be smoothed, for example, by polishing the surface of the cathode used in electrolytic foil production of the carrier with a buff of a predetermined number to adjust the surface roughness. That is, the surface profile of the cathode adjusted in this way is transferred to the electrode surface of the carrier, and an ultra-thin copper foil is formed on the electrode surface of the carrier with a release layer interposed therebetween. It is possible to impart a smooth surface condition that facilitates the realization of the roughened surface described above.
- the buff number is preferably #2000 or more and #3000 or less, more preferably #2000 or more and #2500 or less.
- the electrode surface of the carrier obtained by using the cathode polished with a buff of #2000 or more and #2500 or less has a slight undulation compared to the smooth foil deposition surface, so it is possible to ensure adhesion and smoothness. , it is possible to achieve a good balance between high adhesion and excellent transmission characteristics.
- electrolytic foil manufacturing was performed using an electrolytic solution containing additives.
- the carrier deposition surface side may be the surface of the carrier on the peeling layer side.
- the release layer is a layer that has the function of weakening the peeling strength of the carrier, ensuring the stability of the strength, and suppressing interdiffusion that may occur between the carrier and the copper foil during press molding at high temperatures. .
- the release layer is generally formed on one side of the carrier, but may be formed on both sides.
- the release layer may be either an organic release layer or an inorganic release layer.
- organic components used in the organic release layer include nitrogen-containing organic compounds, sulfur-containing organic compounds, carboxylic acids, and the like.
- Examples of the nitrogen-containing organic compound include triazole compounds, imidazole compounds, etc. Among them, triazole compounds are preferable in terms of easily stabilizing peelability.
- triazole compounds examples include 1,2,3-benzotriazole, carboxybenzotriazole, N',N'-bis(benzotriazolylmethyl)urea, 1H-1,2,4-triazole and 3-amino- 1H-1,2,4-triazole and the like.
- sulfur-containing organic compounds examples include mercaptobenzothiazole, thiocyanuric acid, 2-benzimidazolethiol, and the like.
- carboxylic acids include monocarboxylic acids, dicarboxylic acids, and the like.
- examples of inorganic components used for the inorganic release layer include Ni, Mo, Co, Cr, Fe, Ti, W, P, Zn, chromate treatment films, and the like.
- the release layer may be formed by contacting at least one surface of the carrier with a release layer component-containing solution to fix the release layer component on the surface of the carrier.
- this contact may be performed by immersion in the release layer component-containing solution, spraying the release layer component-containing solution, or flowing the release layer component-containing solution.
- Fixing of the release layer component to the carrier surface may be carried out by adsorption or drying of the release layer component-containing solution, electrodeposition of the release layer component in the release layer component-containing solution, or the like.
- the thickness of the release layer is typically 1 nm or more and 1 ⁇ m or less, preferably 5 nm or more and 500 nm or less.
- another functional layer may be provided between the release layer and the carrier and/or the roughened copper foil.
- auxiliary metal layers include auxiliary metal layers.
- the auxiliary metal layer preferably consists of nickel and/or cobalt. By forming such an auxiliary metal layer on the surface side of the carrier and/or on the surface side of the roughened copper foil, during hot press molding at high temperature or for a long time, it may occur between the carrier and the roughened copper foil. Mutual diffusion can be suppressed and the stability of carrier peeling strength can be ensured.
- the thickness of the auxiliary metal layer is preferably 0.001 ⁇ m or more and 3 ⁇ m or less.
- the roughened copper foil of the present invention is preferably used for producing a copper-clad laminate for printed wiring boards. That is, according to a preferred aspect of the present invention, there is provided a copper-clad laminate comprising the roughened copper foil.
- This copper-clad laminate comprises the roughened copper foil of the present invention and a resin layer provided in close contact with the roughened surface of the roughened copper foil.
- the roughened copper foil may be provided on one side of the resin layer, or may be provided on both sides.
- the resin layer comprises resin, preferably insulating resin.
- the resin layer is preferably prepreg and/or resin sheet.
- Prepreg is a general term for composite materials in which synthetic resin is impregnated into a base material such as a synthetic resin plate, a glass plate, a glass woven fabric, a glass non-woven fabric, or paper.
- insulating resins include epoxy resins, cyanate resins, bismaleimide triazine resins (BT resins), polyphenylene ether resins, and phenol resins.
- the insulating resin forming the resin sheet include insulating resins such as epoxy resins, polyimide resins, and polyester resins.
- the resin layer may contain filler particles made of various inorganic particles such as silica and alumina from the viewpoint of improving insulation.
- the thickness of the resin layer is not particularly limited, it is preferably 1 ⁇ m or more and 1000 ⁇ m or less, more preferably 2 ⁇ m or more and 400 ⁇ m or less, and still more preferably 3 ⁇ m or more and 200 ⁇ m or less.
- the resin layer may be composed of multiple layers.
- a resin layer such as a prepreg and/or a resin sheet may be provided on the roughened copper foil in advance via a primer resin layer that is applied to the surface of the copper foil.
- the roughened copper foil of the present invention is preferably used for producing a printed wiring board. That is, according to a preferred aspect of the present invention, there is provided a printed wiring board comprising the roughened copper foil.
- the printed wiring board according to this aspect includes a layer structure in which a resin layer and a copper layer are laminated.
- the copper layer is a layer derived from the roughened copper foil of the present invention.
- the resin layer is as described above for the copper-clad laminate.
- the printed wiring board can employ a known layer structure except for using the roughened copper foil of the present invention.
- printed wiring boards include a single-sided or double-sided printed wiring board formed by bonding the roughened copper foil of the present invention to one or both sides of a prepreg to form a cured laminate, and then forming a circuit on the printed wiring board.
- a multilayer printed wiring board etc. are mentioned.
- other specific examples include flexible printed wiring boards, COF, TAB tapes, etc., in which the roughened copper foil of the present invention is formed on a resin film to form a circuit.
- a resin-coated copper foil (RCC) is formed by applying the above resin layer to the roughened copper foil of the present invention, and the resin layer is used as an insulating adhesive layer and laminated on the above printed circuit board.
- the roughened copper foil is used as all or part of the wiring layer, and the circuit is formed by the modified semi-additive (MSAP) method, the subtractive method, etc.
- the build-up wiring board and the roughened copper foil are removed.
- an electronic material for glass, an electromagnetic wave shielding film obtained by applying a conductive adhesive to the roughened copper foil of the present invention, and the like are also included.
- the printed wiring board provided with the roughened copper foil of the present invention is used in applications such as automobile antennas, mobile phone base station antennas, high-performance servers, collision prevention radars, etc., which are used in high frequency bands with signal frequencies of 10 GHz or higher. It is suitably used as a high-frequency substrate to be used.
- the roughened copper foil of the present invention is suitable for the MSAP method. For example, when the circuit is formed by the MSAP method, the configurations shown in FIGS. 1 and 2 can be adopted.
- Examples 1, 2 and 4 A copper foil with a carrier provided with a roughened copper foil was produced as follows.
- the carrier on which the organic release layer was formed was immersed in a solution containing nickel concentration of 20 g/L prepared using nickel sulfate, and the liquid temperature was 45° C., pH 3, current density 5 A/L. Under conditions of dm 2 , a deposition amount of nickel equivalent to a thickness of 0.001 ⁇ m was deposited onto the organic release layer. Thus, a nickel layer was formed as an auxiliary metal layer on the organic release layer.
- the surface of the ultra-thin copper foil thus formed was subjected to a roughening treatment to form a roughened copper foil, thereby obtaining a carrier-attached copper foil.
- a roughening treatment in Examples 1 and 2, the following three stages of roughening treatment were performed.
- the roughening treatment in the first step was carried out in two steps. Specifically, using an acidic copper sulfate solution having the copper concentration and sulfuric acid concentration shown in Table 1, the roughening treatment was performed twice at the current density and liquid temperature shown in Table 1.
- the acid copper sulfate solution having the copper concentration and sulfuric acid concentration shown in Table 1 was used, and the roughening treatment was performed at the current density and liquid temperature shown in Table 1.
- the third stage roughening treatment uses an acidic copper sulfate solution with the copper concentration, sulfuric acid concentration, chlorine concentration and 9-phenylacridine (9PA) concentration shown in Table 1, and the current density and liquid temperature shown in Table 1 was subjected to roughening treatment.
- Example 4 two stages of roughening treatment were performed.
- This two-stage roughening treatment consists of a baking plating process for depositing fine copper grains on an ultra-thin copper foil and a covering plating process for preventing the fine copper grains from falling off.
- carboxybenzotriazole (CBTA) was added to an acidic copper sulfate solution with a copper concentration of 10 g / L and a sulfuric acid concentration of 200 g / L so that the concentration shown in Table 1 was obtained, and the current density shown in Table 1 was obtained.
- the roughening treatment was performed at liquid temperature.
- electrodeposition was performed under smooth plating conditions of a liquid temperature of 52° C. and a current density shown in Table 1 using an acidic copper sulfate solution with a copper concentration of 70 g/L and a sulfuric acid concentration of 240 g/L.
- the roughened surface of the obtained copper foil with carrier was subjected to antirust treatment comprising zinc-nickel alloy plating treatment and chromate treatment.
- antirust treatment comprising zinc-nickel alloy plating treatment and chromate treatment.
- the roughening treatment layer and the carrier A zinc-nickel alloy plating treatment was performed on the surface of the Next, the zinc-nickel alloy plated surface was subjected to chromate treatment using an aqueous solution containing 1 g/L of chromic acid under the conditions of pH 12 and current density 1 A/dm 2 .
- Silane coupling agent treatment An aqueous solution containing a commercially available silane coupling agent is adsorbed on the surface of the roughened copper foil side of the carrier-attached copper foil, and the water is evaporated with an electric heater to perform the silane coupling agent treatment. did At this time, the carrier side was not treated with the silane coupling agent.
- Example 3 A roughened copper foil was produced in the same manner as in Example 1 except for the following a) and b). a) Instead of the carrier-attached copper foil, the deposition surface of the following electrolytic copper foil was subjected to a roughening treatment. b) The roughening treatment conditions were changed as shown in Table 1.
- Example 5 (Comparison) Roughening was performed in the same manner as in Example 3, except that in the roughening treatment step, the first and second roughening treatments were not performed, and the third-stage roughening treatment conditions were changed as shown in Table 1. A heat treated copper foil was produced.
- the roughened copper foils or carrier-attached copper foils produced in Evaluation Examples 1 to 5 were subjected to various evaluations shown below.
- ⁇ SEM conditions> - acceleration voltage: 1.0 kV -Working distance: 5mm -Tilt: 54° (with SEM image tilt correction) -Detector: InLens detector -Column Mode: High Resolution - Number of pixels: 2048 (x direction) ⁇ FIB conditions> - acceleration voltage: 30 kV - Slice thickness: 10 nm (interval between slice planes S) - Voxel size setting: Determine the voxel size you want to set, such as (x, y, z) (5 nm, 5 nm, 10 nm).
- the slice thickness is set to 10 nm when z is desired to be 10 nm. Note that the observation magnification can be appropriately changed by the device (model, software, etc.) so as to obtain the determined voxel size.
- Peaks and valleys were labeled separately, and the average height of peaks and valleys in the analysis area, the sum of the heights of peaks and valleys, the surface voxel ratio, and the total volume of peaks per unit area of 1 nm2 were calculated as follows: .
- voxels forming the surface of each labeled mountain were defined as surface voxels Bs.
- volume_voxels_sum calculated in the "voidsSummary_kobu” Excel data generated by the three-dimensional image analysis software "foil Analysis (version 1.0)" is the total volume of all the voxels that make up the mountain. (voxel value)
- surface_voxels_sum is the total volume (voxel value) of the surface voxels Bs.
- the surface voxel ratio in the analysis region was calculated by dividing the total volume of the surface voxels Bs by the total volume of all the voxels forming the mountain.
- a laminate for evaluation was produced. That is, on the surface of the inner layer substrate, a carrier-attached copper foil or a roughened copper foil is laminated via a prepreg (Mitsubishi Gas Chemical Co., Ltd., GHPL-830NSF, thickness 30 ⁇ m) so that the roughened surface is in contact. and thermocompression bonded at a pressure of 4.0 MPa and a temperature of 220° C. for 90 minutes. After that, in the case of the carrier-attached copper foil, the carrier was peeled off to obtain a laminate for evaluation.
- a prepreg Mitsubishi Gas Chemical Co., Ltd., GHPL-830NSF, thickness 30 ⁇ m
- a dry film was attached to the laminate for evaluation described above, and exposure and development were performed. After depositing a copper layer by pattern plating on the laminate masked with the developed dry film, the dry film was peeled off. The exposed copper portion was etched with a sulfuric acid-hydrogen peroxide-based etchant to prepare a sample for shear strength measurement having a height of 15 ⁇ m, a width of 14 ⁇ m, and a length of 150 ⁇ m. Using a bonding strength tester (4000Plus Bondtester manufactured by Nordson DAGE), the shear strength when the sample for shear strength measurement was pushed down from the side was measured.
- a bonding strength tester 4000Plus Bondtester manufactured by Nordson DAGE
- the test type was a destructive test, and the measurement was performed under the conditions of a test height of 5 ⁇ m, a descending speed of 0.05 mm/s, a test speed of 200 ⁇ m/s, a tool movement of 0.03 mm, and a rupture recognition point of 10%.
- the obtained shear strength was rated and evaluated according to the following criteria, and evaluations A and B were judged to be acceptable. The results were as shown in Table 2.
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Abstract
Description
[態様1]
少なくとも一方の側に粗化処理面を有する粗化処理銅箔であって、前記粗化処理面が基準面に対して凸となる複数の山と前記基準面に対して凹となる複数の谷とを有しており、
前記粗化処理面に対してFIB-SEMを用いて得られる画像を三次元画像解析した場合に、2000nm×2000nmの解析領域における前記山の体積及び前記谷の体積の和として算出される山及び谷の高さの総和が1.4×108nm3以上3.5×108nm3以下であり、かつ、前記山の平均高さ及び前記谷の平均高さの和として算出される山及び谷の平均高さが40nm以上90nm以下である、粗化処理銅箔。
[態様2]
前記山及び谷の高さの総和が2.0×108nm3以上3.5×108nm3以下である、態様1に記載の粗化処理銅箔。
[態様3]
前記山及び谷の平均高さが40nm以上80nm以下である、態様1又は2に記載の粗化処理銅箔。
[態様4]
前記粗化処理面に対してFIB-SEMを用いて得られる画像を三次元画像解析した場合に、単位面積1nm2当たりの前記山の総体積が7.0nm3以上50.0nm3以下である、態様1~3のいずれか一つに記載の粗化処理銅箔。
[態様5]
単位面積1nm2当たりの前記山の総体積が30.0nm3以上50.0nm3以下である、態様4に記載の粗化処理銅箔。
[態様6]
前記粗化処理面に対してFIB-SEMを用いて得られる画像を三次元画像解析して前記山を複数のボクセルに分割した場合に、2000nm×2000nmの解析領域における前記山を構成する全ボクセルの総体積に対する、前記山の表面を構成するボクセルの総体積の比である表面ボクセル比が0.25以上0.60以下である、態様1~5のいずれか一つに記載の粗化処理銅箔。
[態様7]
前記表面ボクセル比が0.25以上0.35以下である、態様6に記載の粗化処理銅箔。
[態様8]
前記粗化処理面に防錆処理層及び/又はシランカップリング剤層をさらに備えた、態様1~7のいずれか一つに記載の粗化処理銅箔。
[態様9]
キャリアと、該キャリア上に設けられた剥離層と、該剥離層上に前記粗化処理面を外側にして設けられた態様1~8のいずれか一つに記載の粗化処理銅箔とを備えた、キャリア付銅箔。
[態様10]
態様1~8のいずれか一つに記載の粗化処理銅箔を備えた、銅張積層板。
[態様11]
態様1~8のいずれか一つに記載の粗化処理銅箔を備えた、プリント配線板。 According to the present invention, the following aspects are provided.
[Aspect 1]
A roughened copper foil having a roughened surface on at least one side, wherein the roughened surface has a plurality of peaks that are convex with respect to a reference surface and a plurality of valleys that are concave with respect to the reference surface. and
When the image obtained using FIB-SEM for the roughened surface is subjected to three-dimensional image analysis, the mountain and the valley calculated as the sum of the volume of the mountain and the volume of the valley in an analysis area of 2000 nm × 2000 nm The sum of the heights of the valleys is 1.4×10 8 nm 3 or more and 3.5×10 8 nm 3 or less, and the peaks calculated as the sum of the average height of the peaks and the average height of the valleys and a roughened copper foil having an average valley height of 40 nm or more and 90 nm or less.
[Aspect 2]
The roughened copper foil according to aspect 1, wherein the sum of heights of the peaks and valleys is 2.0×10 8 nm 3 or more and 3.5×10 8 nm 3 or less.
[Aspect 3]
The roughened copper foil according to aspect 1 or 2, wherein the average height of the peaks and valleys is 40 nm or more and 80 nm or less.
[Aspect 4]
When the image obtained using FIB-SEM on the roughened surface is subjected to three-dimensional image analysis, the total volume of the mountains per unit area of 1 nm2 is 7.0 nm3 or more and 50.0 nm3 or less. , The roughened copper foil according to any one of aspects 1 to 3.
[Aspect 5]
The roughened copper foil according to aspect 4, wherein the total volume of the mountains per unit area of 1 nm 2 is 30.0 nm 3 or more and 50.0 nm 3 or less.
[Aspect 6]
When the image obtained using FIB-SEM on the roughened surface is three-dimensional image analyzed and the mountain is divided into a plurality of voxels, all voxels that constitute the mountain in the analysis area of 2000 nm × 2000 nm The roughening treatment according to any one of aspects 1 to 5, wherein the surface voxel ratio, which is the ratio of the total volume of voxels constituting the surface of the mountain to the total volume of the mountain, is 0.25 or more and 0.60 or less. Copper foil.
[Aspect 7]
The roughened copper foil according to aspect 6, wherein the surface voxel ratio is 0.25 or more and 0.35 or less.
[Aspect 8]
The roughened copper foil according to any one of aspects 1 to 7, further comprising an antirust layer and/or a silane coupling agent layer on the roughened surface.
[Aspect 9]
A carrier, a release layer provided on the carrier, and the roughened copper foil according to any one of aspects 1 to 8 provided on the release layer with the roughened surface facing outward. copper foil with carrier.
[Aspect 10]
A copper clad laminate comprising the roughened copper foil according to any one of aspects 1 to 8.
[Aspect 11]
A printed wiring board comprising the roughened copper foil according to any one of aspects 1 to 8.
本発明を特定するために用いられる用語ないしパラメータの定義を以下に示す。 DEFINITIONS Definitions of terms or parameters used to define the present invention are provided below.
本発明による銅箔は粗化処理銅箔である。この粗化処理銅箔は、少なくとも一方の側に粗化処理面を有する。この粗化処理面は、基準面に対して凸となる複数の山と基準面に対して凹となる複数の谷とを有する。そして、粗化処理面に対してFIB-SEMを用いて得られる画像を三次元画像解析した場合に、2000nm×2000nmの解析領域における山の体積及び谷の体積の和として算出される山及び谷の高さの総和が1.4×108nm3以上3.5×108nm3以下である。また、2000nm×2000nmの解析領域における山の平均高さ及び谷の平均高さの和として算出される山及び谷の平均高さが40nm以上90nm以下である。このように粗化処理銅箔において、山及び谷の高さの総和、並びに山及び谷の平均高さをそれぞれ所定の範囲に制御した表面プロファイルを付与することにより、銅張積層板の加工ないしプリント配線板の製造において、優れた伝送特性(とりわけ優れた高周波特性)と高いシェア強度(ひいてはシェア強度という観点での高い回路密着性)とを両立することができる。 Roughened Copper Foil The copper foil according to the present invention is a roughened copper foil. This roughened copper foil has a roughened surface on at least one side. This roughened surface has a plurality of peaks that are convex with respect to the reference plane and a plurality of valleys that are concave with respect to the reference plane. Then, when the image obtained using FIB-SEM on the roughened surface is subjected to three-dimensional image analysis, the peaks and valleys calculated as the sum of the volume of the peaks and the volume of the valleys in the analysis area of 2000 nm × 2000 nm is 1.4×10 8 nm 3 or more and 3.5×10 8 nm 3 or less. Further, the average height of peaks and valleys calculated as the sum of the average height of peaks and the average height of valleys in an analysis area of 2000 nm×2000 nm is 40 nm or more and 90 nm or less. In this way, in the roughened copper foil, by giving a surface profile in which the total height of the peaks and valleys and the average height of the peaks and valleys are respectively controlled within a predetermined range, the copper clad laminate can be processed or processed. In the production of printed wiring boards, it is possible to achieve both excellent transmission characteristics (especially excellent high-frequency characteristics) and high shear strength (and thus high circuit adhesion in terms of shear strength).
上述したように、本発明の粗化処理銅箔はキャリア付銅箔の形態で提供されてもよい。キャリア付銅箔の形態とすることで、優れたレーザー加工性及び細線回路形成性を実現することができる。すなわち、本発明の好ましい態様によれば、キャリアと、キャリア上に設けられた剥離層と、剥離層上に粗化処理面を外側にして設けられた上記粗化処理銅箔とを備えた、キャリア付銅箔が提供される。もっとも、キャリア付銅箔は、本発明の粗化処理銅箔を用いること以外は、公知の層構成が採用可能である。 Carrier-attached copper foil As described above, the roughened copper foil of the present invention may be provided in the form of a carrier-attached copper foil. By adopting the form of a copper foil with a carrier, it is possible to realize excellent laser workability and fine line circuit formability. That is, according to a preferred embodiment of the present invention, a carrier, a release layer provided on the carrier, and the roughened copper foil provided on the release layer with the roughened surface facing outward, A copper foil with carrier is provided. However, for the carrier-attached copper foil, a known layer structure can be employed, except for using the roughened copper foil of the present invention.
本発明の粗化処理銅箔はプリント配線板用銅張積層板の作製に用いられるのが好ましい。すなわち、本発明の好ましい態様によれば、上記粗化処理銅箔を備えた銅張積層板が提供される。本発明の粗化処理銅箔を用いることで、銅張積層板の加工において、優れた伝送特性と高いシェア強度とを両立することができる。この銅張積層板は、本発明の粗化処理銅箔と、粗化処理銅箔の粗化処理面に密着して設けられる樹脂層とを備えてなる。粗化処理銅箔は樹脂層の片面に設けられてもよいし、両面に設けられてもよい。樹脂層は、樹脂、好ましくは絶縁性樹脂を含んでなる。樹脂層はプリプレグ及び/又は樹脂シートであるのが好ましい。プリプレグとは、合成樹脂板、ガラス板、ガラス織布、ガラス不織布、紙等の基材に合成樹脂を含浸させた複合材料の総称である。絶縁性樹脂の好ましい例としては、エポキシ樹脂、シアネート樹脂、ビスマレイミドトリアジン樹脂(BT樹脂)、ポリフェニレンエーテル樹脂、フェノール樹脂等が挙げられる。また、樹脂シートを構成する絶縁性樹脂の例としては、エポキシ樹脂、ポリイミド樹脂、ポリエステル樹脂等の絶縁樹脂が挙げられる。また、樹脂層には絶縁性を向上する等の観点からシリカ、アルミナ等の各種無機粒子からなるフィラー粒子等が含有されていてもよい。樹脂層の厚さは特に限定されないが、1μm以上1000μm以下が好ましく、より好ましくは2μm以上400μm以下であり、さらに好ましくは3μm以上200μm以下である。樹脂層は複数の層で構成されていてよい。プリプレグ及び/又は樹脂シート等の樹脂層は予め銅箔表面に塗布されるプライマー樹脂層を介して粗化処理銅箔に設けられていてもよい。 Copper- Clad Laminate The roughened copper foil of the present invention is preferably used for producing a copper-clad laminate for printed wiring boards. That is, according to a preferred aspect of the present invention, there is provided a copper-clad laminate comprising the roughened copper foil. By using the roughened copper foil of the present invention, it is possible to achieve both excellent transmission characteristics and high shear strength in the processing of copper-clad laminates. This copper-clad laminate comprises the roughened copper foil of the present invention and a resin layer provided in close contact with the roughened surface of the roughened copper foil. The roughened copper foil may be provided on one side of the resin layer, or may be provided on both sides. The resin layer comprises resin, preferably insulating resin. The resin layer is preferably prepreg and/or resin sheet. Prepreg is a general term for composite materials in which synthetic resin is impregnated into a base material such as a synthetic resin plate, a glass plate, a glass woven fabric, a glass non-woven fabric, or paper. Preferred examples of insulating resins include epoxy resins, cyanate resins, bismaleimide triazine resins (BT resins), polyphenylene ether resins, and phenol resins. Examples of the insulating resin forming the resin sheet include insulating resins such as epoxy resins, polyimide resins, and polyester resins. In addition, the resin layer may contain filler particles made of various inorganic particles such as silica and alumina from the viewpoint of improving insulation. Although the thickness of the resin layer is not particularly limited, it is preferably 1 μm or more and 1000 μm or less, more preferably 2 μm or more and 400 μm or less, and still more preferably 3 μm or more and 200 μm or less. The resin layer may be composed of multiple layers. A resin layer such as a prepreg and/or a resin sheet may be provided on the roughened copper foil in advance via a primer resin layer that is applied to the surface of the copper foil.
本発明の粗化処理銅箔はプリント配線板の作製に用いられるのが好ましい。すなわち、本発明の好ましい態様によれば、上記粗化処理銅箔を備えたプリント配線板が提供される。本発明の粗化処理銅箔を用いることで、プリント配線板の製造において、優れた伝送特性と高いシェア強度とを両立することができる。本態様によるプリント配線板は、樹脂層と、銅層とが積層された層構成を含んでなる。銅層は本発明の粗化処理銅箔に由来する層である。また、樹脂層については銅張積層板に関して上述したとおりである。いずれにしても、プリント配線板は、本発明の粗化処理銅箔を用いること以外は、公知の層構成が採用可能である。プリント配線板に関する具体例としては、プリプレグの片面又は両面に本発明の粗化処理銅箔を接着させ硬化した積層体とした上で回路形成した片面又は両面プリント配線板や、これらを多層化した多層プリント配線板等が挙げられる。また、他の具体例としては、樹脂フィルム上に本発明の粗化処理銅箔を形成して回路を形成するフレキシブルプリント配線板、COF、TABテープ等も挙げられる。さらに他の具体例としては、本発明の粗化処理銅箔に上述の樹脂層を塗布した樹脂付銅箔(RCC)を形成し、樹脂層を絶縁接着材層として上述のプリント基板に積層した後、粗化処理銅箔を配線層の全部又は一部としてモディファイド・セミ・アディティブ(MSAP)法、サブトラクティブ法等の手法で回路を形成したビルドアップ配線板や、粗化処理銅箔を除去してセミアディティブ法で回路を形成したビルドアップ配線板、半導体集積回路上へ樹脂付銅箔の積層と回路形成を交互に繰りかえすダイレクト・ビルドアップ・オン・ウェハー等が挙げられる。より発展的な具体例として、上記樹脂付銅箔を基材に積層し回路形成したアンテナ素子、接着剤層を介してガラスや樹脂フィルムに積層しパターンを形成したパネル・ディスプレイ用電子材料や窓ガラス用電子材料、本発明の粗化処理銅箔に導電性接着剤を塗布した電磁波シールド・フィルム等も挙げられる。とりわけ、本発明の粗化処理銅箔を備えたプリント配線板は、信号周波数10GHz以上の高周波帯域で用いられる自動車用アンテナ、携帯電話基地局アンテナ、高性能サーバー、衝突防止用レーダー等の用途で用いられる高周波基板として好適に用いられる。特に、本発明の粗化処理銅箔はMSAP法に適している。例えば、MSAP法により回路形成した場合には図1及び2に示されるような構成が採用可能である。 Printed Wiring Board The roughened copper foil of the present invention is preferably used for producing a printed wiring board. That is, according to a preferred aspect of the present invention, there is provided a printed wiring board comprising the roughened copper foil. By using the roughened copper foil of the present invention, both excellent transmission characteristics and high shear strength can be achieved in the production of printed wiring boards. The printed wiring board according to this aspect includes a layer structure in which a resin layer and a copper layer are laminated. The copper layer is a layer derived from the roughened copper foil of the present invention. Also, the resin layer is as described above for the copper-clad laminate. In any case, the printed wiring board can employ a known layer structure except for using the roughened copper foil of the present invention. Specific examples of printed wiring boards include a single-sided or double-sided printed wiring board formed by bonding the roughened copper foil of the present invention to one or both sides of a prepreg to form a cured laminate, and then forming a circuit on the printed wiring board. A multilayer printed wiring board etc. are mentioned. Further, other specific examples include flexible printed wiring boards, COF, TAB tapes, etc., in which the roughened copper foil of the present invention is formed on a resin film to form a circuit. As another specific example, a resin-coated copper foil (RCC) is formed by applying the above resin layer to the roughened copper foil of the present invention, and the resin layer is used as an insulating adhesive layer and laminated on the above printed circuit board. After that, the roughened copper foil is used as all or part of the wiring layer, and the circuit is formed by the modified semi-additive (MSAP) method, the subtractive method, etc. The build-up wiring board and the roughened copper foil are removed. A build-up wiring board in which a circuit is formed by a semi-additive method, and a direct build-up on wafer in which lamination of resin-coated copper foil on a semiconductor integrated circuit and circuit formation are alternately repeated. More advanced specific examples include antenna elements in which the resin-coated copper foil is laminated on a base material to form a circuit, and electronic materials and windows for panels and displays in which a pattern is formed by laminating the resin-coated copper foil on glass or a resin film via an adhesive layer. An electronic material for glass, an electromagnetic wave shielding film obtained by applying a conductive adhesive to the roughened copper foil of the present invention, and the like are also included. In particular, the printed wiring board provided with the roughened copper foil of the present invention is used in applications such as automobile antennas, mobile phone base station antennas, high-performance servers, collision prevention radars, etc., which are used in high frequency bands with signal frequencies of 10 GHz or higher. It is suitably used as a high-frequency substrate to be used. In particular, the roughened copper foil of the present invention is suitable for the MSAP method. For example, when the circuit is formed by the MSAP method, the configurations shown in FIGS. 1 and 2 can be adopted.
粗化処理銅箔を備えたキャリア付銅箔を以下のようにして作製した。 Examples 1, 2 and 4
A copper foil with a carrier provided with a roughened copper foil was produced as follows.
以下に示される組成の銅電解液と、陰極と、陽極としてのDSA(寸法安定性陽極)とを用いて、溶液温度50℃、電流密度70A/dm2で電解し、厚さ18μmの電解銅箔をキャリアとして作製した。このとき、陰極として、表面を#2000のバフで研磨して表面粗さを整えた電極を用いた。
<銅電解液の組成>
‐ 銅濃度:80g/L
‐ 硫酸濃度:300g/L
‐ 塩素濃度:30mg/L
‐ 膠濃度:5mg/L (1) Preparation of carrier Electrolysis is performed at a solution temperature of 50 ° C. and a current density of 70 A / dm 2 using a copper electrolyte solution having the composition shown below, a cathode, and a DSA (dimensionally stable anode) as an anode, An electrolytic copper foil having a thickness of 18 μm was produced as a carrier. At this time, an electrode whose surface was polished with a #2000 buff to adjust the surface roughness was used as the cathode.
<Composition of Copper Electrolyte>
- Copper concentration: 80g/L
- Sulfuric acid concentration: 300g/L
- Chlorine concentration: 30 mg / L
- Glue concentration: 5mg/L
酸洗処理されたキャリアの電極面を、カルボキシベンゾトリアゾール(CBTA)濃度1g/L、硫酸濃度150g/L及び銅濃度10g/Lを含むCBTA水溶液に、液温30℃で30秒間浸漬し、CBTA成分をキャリアの電極面に吸着させた。こうして、キャリアの電極面にCBTA層を有機剥離層として形成した。 (2) Formation of release layer The electrode surface of the pickled carrier was immersed in a CBTA aqueous solution containing 1 g/L of carboxybenzotriazole (CBTA), 150 g/L of sulfuric acid and 10 g/L of copper at a liquid temperature of 30°C. for 30 seconds to adsorb the CBTA component onto the electrode surface of the carrier. Thus, a CBTA layer was formed as an organic release layer on the electrode surface of the carrier.
有機剥離層が形成されたキャリアを、硫酸ニッケルを用いて作製されたニッケル濃度20g/Lを含む溶液に浸漬して、液温45℃、pH3、電流密度5A/dm2の条件で、厚さ0.001μm相当の付着量のニッケルを有機剥離層上に付着させた。こうして、有機剥離層上にニッケル層を補助金属層として形成した。 (3) Formation of Auxiliary Metal Layer The carrier on which the organic release layer was formed was immersed in a solution containing nickel concentration of 20 g/L prepared using nickel sulfate, and the liquid temperature was 45° C., pH 3, current density 5 A/L. Under conditions of dm 2 , a deposition amount of nickel equivalent to a thickness of 0.001 μm was deposited onto the organic release layer. Thus, a nickel layer was formed as an auxiliary metal layer on the organic release layer.
補助金属層が形成されたキャリアを、以下に示される組成の銅溶液に浸漬して、溶液温度50℃、電流密度5A/dm2以上30A/dm2以下で電解し、厚さ1.5μmの極薄銅箔を補助金属層上に形成した。
<溶液の組成>
‐ 銅濃度:60g/L
‐ 硫酸濃度:200g/L (4) Formation of ultra-thin copper foil The carrier on which the auxiliary metal layer is formed is immersed in a copper solution having the composition shown below, and the solution temperature is 50 ° C. and the current density is 5 A/dm 2 or more and 30 A/dm 2 or less. Electrolysis was performed to form an ultra-thin copper foil having a thickness of 1.5 μm on the auxiliary metal layer.
<Solution composition>
- Copper concentration: 60g/L
- Sulfuric acid concentration: 200 g / L
こうして形成された極薄銅箔の表面に粗化処理を行うことで粗化処理銅箔を形成し、これによりキャリア付銅箔を得た。この粗化処理は、例1及び2については、以下に示される3段階の粗化処理を行った。
‐ 1段階目の粗化処理は2回に分けて行った。具体的には、表1に示される銅濃度及び硫酸濃度の酸性硫酸銅溶液を用い、表1に示される電流密度及び液温で粗化処理を2回行った。
‐ 2段階目の粗化処理は、表1に示される銅濃度及び硫酸濃度の酸性硫酸銅溶液を用い、表1に示される電流密度及び液温で粗化処理を行った。
‐ 3段階目の粗化処理は、表1に示される銅濃度、硫酸濃度、塩素濃度及び9-フェニルアクリジン(9PA)濃度の酸性硫酸銅溶液を用い、表1に示される電流密度及び液温で粗化処理を行った。 (5) Roughening Treatment The surface of the ultra-thin copper foil thus formed was subjected to a roughening treatment to form a roughened copper foil, thereby obtaining a carrier-attached copper foil. As for this roughening treatment, in Examples 1 and 2, the following three stages of roughening treatment were performed.
- The roughening treatment in the first step was carried out in two steps. Specifically, using an acidic copper sulfate solution having the copper concentration and sulfuric acid concentration shown in Table 1, the roughening treatment was performed twice at the current density and liquid temperature shown in Table 1.
- For the second-stage roughening treatment, the acid copper sulfate solution having the copper concentration and sulfuric acid concentration shown in Table 1 was used, and the roughening treatment was performed at the current density and liquid temperature shown in Table 1.
- The third stage roughening treatment uses an acidic copper sulfate solution with the copper concentration, sulfuric acid concentration, chlorine concentration and 9-phenylacridine (9PA) concentration shown in Table 1, and the current density and liquid temperature shown in Table 1 was subjected to roughening treatment.
得られたキャリア付銅箔の粗化処理表面に、亜鉛-ニッケル合金めっき処理及びクロメート処理からなる防錆処理を行った。まず、亜鉛濃度1g/L、ニッケル濃度2g/L及びピロリン酸カリウム濃度80g/Lを含む溶液を用い、液温40℃、電流密度0.5A/dm2の条件で、粗化処理層及びキャリアの表面に亜鉛-ニッケル合金めっき処理を行った。次いで、クロム酸1g/Lを含む水溶液を用い、pH12、電流密度1A/dm2の条件で、亜鉛-ニッケル合金めっき処理を行った表面にクロメート処理を行った。 (6) Antirust Treatment The roughened surface of the obtained copper foil with carrier was subjected to antirust treatment comprising zinc-nickel alloy plating treatment and chromate treatment. First, using a solution containing a zinc concentration of 1 g / L, a nickel concentration of 2 g / L, and a potassium pyrophosphate concentration of 80 g / L, under the conditions of a liquid temperature of 40 ° C. and a current density of 0.5 A / dm 2 , the roughening treatment layer and the carrier A zinc-nickel alloy plating treatment was performed on the surface of the Next, the zinc-nickel alloy plated surface was subjected to chromate treatment using an aqueous solution containing 1 g/L of chromic acid under the conditions of
市販のシランカップリング剤を含む水溶液をキャリア付銅箔の粗化処理銅箔側の表面に吸着させ、電熱器により水分を蒸発させることにより、シランカップリング剤処理を行った。このとき、シランカップリング剤処理はキャリア側には行わなかった。 (7) Silane coupling agent treatment An aqueous solution containing a commercially available silane coupling agent is adsorbed on the surface of the roughened copper foil side of the carrier-attached copper foil, and the water is evaporated with an electric heater to perform the silane coupling agent treatment. did At this time, the carrier side was not treated with the silane coupling agent.
下記a)及びb)以外は例1と同様にして粗化処理銅箔の作製を行った。
a)キャリア付銅箔に代えて、以下の電解銅箔の析出面に粗化処理を行ったこと。
b)表1に示されるように粗化処理条件を変更したこと。 Example 3
A roughened copper foil was produced in the same manner as in Example 1 except for the following a) and b).
a) Instead of the carrier-attached copper foil, the deposition surface of the following electrolytic copper foil was subjected to a roughening treatment.
b) The roughening treatment conditions were changed as shown in Table 1.
銅電解液として以下に示される組成の硫酸酸性硫酸銅溶液を用い、陰極に表面粗さRaが0.20μmのチタン製の電極を用い、陽極にはDSA(寸法安定性陽極)を用いて、溶液温度45℃、電流密度55A/dm2で電解し、厚さ12μmの電解銅箔を得た。
<硫酸酸性硫酸銅溶液の組成>
‐ 銅濃度:80g/L
‐ 硫酸濃度:260g/L
‐ ビス(3-スルホプロピル)ジスルフィド濃度:30mg/L
‐ ジアリルジメチルアンモニウムクロライド重合体濃度:50mg/L
‐ 塩素濃度:40mg/L (Preparation of electrolytic copper foil)
Using a sulfuric acid copper sulfate solution having the composition shown below as the copper electrolyte, using a titanium electrode having a surface roughness Ra of 0.20 μm as the cathode, and using DSA (dimensionally stable anode) as the anode, Electrolysis was performed at a solution temperature of 45° C. and a current density of 55 A/dm 2 to obtain an electrolytic copper foil with a thickness of 12 μm.
<Composition of sulfuric acid copper sulfate solution>
- Copper concentration: 80g/L
- Sulfuric acid concentration: 260g/L
- Bis (3-sulfopropyl) disulfide concentration: 30 mg / L
- Diallyldimethylammonium chloride polymer concentration: 50 mg/L
- Chlorine concentration: 40 mg / L
粗化処理工程において、1段階目及び2段階目の粗化処理を行わず、表1に示されるように3段階目の粗化処理条件を変更したこと以外は、例3と同様にして粗化処理銅箔の作製を行った。 Example 5 (Comparison)
Roughening was performed in the same manner as in Example 3, except that in the roughening treatment step, the first and second roughening treatments were not performed, and the third-stage roughening treatment conditions were changed as shown in Table 1. A heat treated copper foil was produced.
例1~5で作製された粗化処理銅箔又はキャリア付銅箔について、以下に示される各種評価を行った。 The roughened copper foils or carrier-attached copper foils produced in Evaluation Examples 1 to 5 were subjected to various evaluations shown below.
粗化処理銅箔又はキャリア付銅箔に対して、粗化処理面の三次元画像解析を行うことにより、山及び谷の平均高さ、山及び谷の高さの総和、表面ボクセル比、並びに単位面積1nm2当たりの山の総体積をそれぞれ算出した。具体的な手順は以下のとおりである。 (a) Three-dimensional image analysis parameters of roughened surface By performing three-dimensional image analysis of the roughened surface of the roughened copper foil or the carrier-attached copper foil, and the sum of valley heights, the surface voxel ratio, and the total volume of peaks per unit area of 1 nm2 were calculated, respectively. The specific procedure is as follows.
FIB-SEM装置(カールツァイス社製Crossbeam540、SEM制御:SmartSEM Version 6.06 with Service Pack 8、FIB制御:SmartFIB v1.11.0)を用いて、粗化処理面の10240nm×7680nmの領域に対して、下記測定条件にて三次元形状データの取得を行った。この三次元形状データの取得は、図7に示されるように、x軸及びz軸を粗化処理銅箔10の面内方向とし、かつ、y軸を粗化処理銅箔10の厚さ方向と規定した上で、x-y面と平行なスライス面Sでの粗化処理銅箔10の断面画像を取得し、このスライス面をz軸方向に10nmずつ平行移動させながら、上記解析領域において合計1000枚の断面画像を取得することにより行った。なお、今回は下記条件で観察したが、観察条件は装置の状態(機種等)により適宜選択ないし変更できる。 (a-1) 3D-SEM observation FIB-SEM device (Carl Zeiss Crossbeam 540, SEM control: SmartSEM Version 6.06 with Service Pack 8, FIB control: SmartFIB v1.11.0), roughening treatment Three-dimensional shape data was obtained for a region of 10240 nm×7680 nm on the surface under the following measurement conditions. As shown in FIG. 7 , this three-dimensional shape data is acquired with the x-axis and z-axis being the in-plane directions of the roughened
‐加速電圧:1.0kV
‐Working distance:5mm
‐Tilt:54°(SEM像のTilt補正あり)
‐検出器:InLens検出器
‐Column Mode:High Resolution
‐画素数:2048(x方向)
<FIB条件>
‐加速電圧:30kV
‐スライス厚:10nm(スライス面Sの間隔)
‐ボクセルサイズの設定:
(x、y、z)=(5nm、5nm、10nm)のように、設定したいボクセルサイズを決定する。x、yの画素サイズは、FIB-SEM条件により設定することができ、FIB-SEMの画素数にx、yの画素サイズを掛け合わせた数値がFIB-SEMのスケールサイズとなるよう倍率を調整することで、設定を行う。画素数が2048、x、yの画素サイズが5nm、5nmの場合であれば、2048×5nm=10240nmがFIB-SEMのx軸のスケールサイズとなるように倍率を調整する。x軸のスケールサイズが決まれば、y軸のスケールサイズも決まる。zのボクセルサイズは、スライス厚(スライス面Sの間隔)の数値によって決定されるため、zを10nmとしたい場合は、スライス厚を10nmとする。なお、決定したボクセルサイズになるように、装置(機種やソフトウェア等)で観察倍率を適宜変更することができる。 <SEM conditions>
- acceleration voltage: 1.0 kV
-Working distance: 5mm
-Tilt: 54° (with SEM image tilt correction)
-Detector: InLens detector -Column Mode: High Resolution
- Number of pixels: 2048 (x direction)
<FIB conditions>
- acceleration voltage: 30 kV
- Slice thickness: 10 nm (interval between slice planes S)
- Voxel size setting:
Determine the voxel size you want to set, such as (x, y, z)=(5 nm, 5 nm, 10 nm). The pixel size of x and y can be set according to the FIB-SEM conditions, and the magnification is adjusted so that the number of pixels of FIB-SEM multiplied by the pixel size of x and y becomes the scale size of FIB-SEM. to configure the settings. If the number of pixels is 2048 and the pixel sizes of x and y are 5 nm and 5 nm, the magnification is adjusted so that 2048×5 nm=10240 nm is the scale size of the FIB-SEM x axis. Once the x-axis scale size is determined, the y-axis scale size is also determined. Since the voxel size of z is determined by the numerical value of the slice thickness (interval between slice planes S), the slice thickness is set to 10 nm when z is desired to be 10 nm. Note that the observation magnification can be appropriately changed by the device (model, software, etc.) so as to obtain the determined voxel size.
3D-SEMで得られた粗化処理銅箔の三次元形状データのスライス画像から三次元位置合わせソフト「ExFact Slice Aligner(バージョン2.0)」(日本ビジュアルサイエンス株式会社製)でz軸の観察長さが2μm以上となるようにドリフトの補正を行った。ドリフト補正後のスライス画像について、三次元画像解析ソフトウェア「ExFact VR(バージョン2.2)」(日本ビジュアルサイエンス株式会社製)を用いて三次元再構築した。このとき、解析領域は2000nm×1000nm×2000nm(粗化処理銅箔10を平面視した場合は2000nm×2000nm)とし、1ボクセル当たりの大きさは(x、y、z)=(5nm、5nm、10nm)とした。その後、図8に示すように粗化処理面がx-y面となるように軸を回転させた後、「foil Analysis(バージョン1.0)」(日本ビジュアルサイエンス株式会社製)により画像解析することにより、粗化処理面に関する各種データを以下のとおり取得した。 (a-2) 3D-SEM image analysis Three-dimensional alignment software "ExFact Slice Aligner (version 2.0)" (Nippon Visual Science Co., Ltd.) was used to correct the drift so that the observation length of the z-axis was 2 μm or more. The slice images after drift correction were three-dimensionally reconstructed using three-dimensional image analysis software "ExFact VR (version 2.2)" (manufactured by Nippon Visual Science Co., Ltd.). At this time, the analysis area is 2000 nm × 1000 nm × 2000 nm (2000 nm × 2000 nm when the roughened
三次元再構築データに対して大津の二値化にて二値化処理を行い、空気と粗化処理銅箔とを分離した。得られた二値データについて、粗化処理銅箔中の空隙、及び3D-SEM画像取得時におけるデポジションの割れ等に起因するノイズを除去し、粗化処理銅箔の凹凸構造を解析した。得られた粗化処理銅箔の凹凸構造に対して中央値フィルタをかけ、粗化処理面の凹凸の基準面を作成した。このとき、中央値フィルタのマトリクスサイズは99とした。そして、基準面に対して凸となる部分を山、基準面に対して凹となる部分を谷とそれぞれ定義した。山及び谷は個別にラベリングし、解析領域における山及び谷の平均高さ、山及び谷の高さの総和、表面ボクセル比、並びに単位面積1nm2当たりの山の総体積を以下のとおり算出した。 <Preliminary analysis: determination of peaks and valleys>
Otsu's binarization was applied to the three-dimensional reconstructed data, and the air and the roughened copper foil were separated. From the obtained binary data, noise caused by voids in the roughened copper foil and cracks in the deposition during acquisition of 3D-SEM images were removed, and the uneven structure of the roughened copper foil was analyzed. A median filter was applied to the uneven structure of the obtained roughened copper foil to prepare a reference plane for the unevenness of the roughened surface. At this time, the matrix size of the median filter was set to 99. A portion that is convex with respect to the reference plane is defined as a peak, and a portion that is concave with respect to the reference plane is defined as a valley. Peaks and valleys were labeled separately, and the average height of peaks and valleys in the analysis area, the sum of the heights of peaks and valleys, the surface voxel ratio, and the total volume of peaks per unit area of 1 nm2 were calculated as follows: .
三次元画像解析ソフト「foil Analysis(バージョン1.0)」にて算出される「plusMean」と「minusMean」との和を山及び谷の平均高さ(ボクセル値)とした。ここで、「plusMean」は山の高さの平均値(ボクセル値)を表し、「minusMean」は谷の高さの平均値(ボクセル値)を表す。得られた山及び谷の平均高さ(ボクセル値)に1ボクセル当たりの高さ(すなわち5nm)を掛け合わせることで、解析領域における山及び谷の平均高さ(nm)を算出した。結果は表2に示されるとおりであった。 <Average height of peaks and valleys in analysis area>
The sum of "plusMean" and "minusMean" calculated by the three-dimensional image analysis software "foil Analysis (version 1.0)" was defined as the average height (voxel value) of peaks and valleys. Here, "plusMean" represents the mean value (voxel value) of the peak heights, and "minusMean" represents the mean value (voxel value) of the valley heights. By multiplying the obtained average height (voxel value) of peaks and valleys by the height per voxel (that is, 5 nm), the average height (nm) of peaks and valleys in the analysis region was calculated. The results were as shown in Table 2.
三次元画像解析ソフト「foil Analysis(バージョン1.0)」にて算出される「plusSum」と「minusSum」との和を山及び谷の高さの総和(ボクセル値)とした。ここで、「plusSum」は山でのカウント画素(ボクセル)の総和を表し、「minusSum」は谷でのカウント画素(ボクセル)の総和を表す。山及び谷の高さの総和(ボクセル値)に1ボクセル当たりの体積(すなわち5nm×5nm×10nm)を掛け合わせることで、解析領域における山及び谷の高さの総和(nm3)を算出した。結果は表2に示されるとおりであった。 <Total height of peaks and valleys>
The sum of "plusSum" and "minusSum" calculated by the three-dimensional image analysis software "foil Analysis (version 1.0)" was defined as the sum of the heights of peaks and valleys (voxel value). Here, "plusSum" represents the sum of count pixels (voxels) at peaks, and "minusSum" represents the sum of count pixels (voxels) at valleys. The sum of peak and valley heights (voxel value) was multiplied by the volume per voxel (i.e., 5 nm x 5 nm x 10 nm) to calculate the sum of peak and valley heights (nm 3 ) in the analysis area. . The results were as shown in Table 2.
図5に示されるように、ラベリングしたそれぞれの山の表面(大気と接する面)を構成するボクセルを表面ボクセルBsとした。具体的には、三次元画像解析ソフト「foil Analysis(バージョン1.0)」による解析によって生成される「voidsSummary_kobu」エクセルデータにて算出される「volume_voxels_sum」を、山を構成する全ボクセルの総体積(ボクセル値)とし、「surface_voxels_sum」を表面ボクセルBsの総体積(ボクセル値)とした。表面ボクセルBsの総体積を、山を構成する全ボクセルの総体積で割ることで、解析領域における表面ボクセル比を算出した。 <Surface voxel ratio>
As shown in FIG. 5, the voxels forming the surface of each labeled mountain (the surface in contact with the atmosphere) were defined as surface voxels Bs. Specifically, the "volume_voxels_sum" calculated in the "voidsSummary_kobu" Excel data generated by the three-dimensional image analysis software "foil Analysis (version 1.0)" is the total volume of all the voxels that make up the mountain. (voxel value), and "surface_voxels_sum" is the total volume (voxel value) of the surface voxels Bs. The surface voxel ratio in the analysis region was calculated by dividing the total volume of the surface voxels Bs by the total volume of all the voxels forming the mountain.
三次元画像解析ソフト「foil Analysis(バージョン1.0)」による解析によって生成される「voidsSummary_kobu」エクセルデータにて算出される「volume_voxels_sum」を山の総体積(ボクセル値)とした。山の総体積(ボクセル値)に1ボクセル当たりの体積(すなわち5nm×5nm×10nm)を掛け合わせることで、山の総体積(nm3)を求め、これを解析領域(2000nm×2000nm)の面積で割ることで単位面積1nm2当たりの山の総体積(nm3)を算出した。結果は表2に示されるとおりであった。 <Total volume of mountains per unit area of 1 nm2>
"Volume_voxels_sum" calculated from "voidsSummary_kobu" Excel data generated by analysis using the three-dimensional image analysis software "foil Analysis (version 1.0)" was used as the total volume (voxel value) of the mountains. By multiplying the total volume (voxel value) of the mountains by the volume per voxel (that is, 5 nm × 5 nm × 10 nm), the total volume (nm 3 ) of the mountains is obtained, which is the area of the analysis region (2000 nm × 2000 nm). The total volume of mountains (nm 3 ) per unit area of 1 nm 2 was calculated by dividing by . The results were as shown in Table 2.
得られた粗化処理銅箔ないしキャリア付銅箔を用いて評価用積層体を作製した。すなわち、内層基板の表面に、プリプレグ(三菱ガス化学株式会社製、GHPL-830NSF、厚さ30μm)を介して、粗化処理面が当接するようにキャリア付銅箔又は粗化処理銅箔を積層し、圧力4.0MPa、温度220℃で90分間熱圧着した。その後、キャリア付銅箔の場合にはキャリアを剥離し、評価用積層体を得た。 (b) Shear Strength Using the obtained roughened copper foil or carrier-attached copper foil, a laminate for evaluation was produced. That is, on the surface of the inner layer substrate, a carrier-attached copper foil or a roughened copper foil is laminated via a prepreg (Mitsubishi Gas Chemical Co., Ltd., GHPL-830NSF, thickness 30 μm) so that the roughened surface is in contact. and thermocompression bonded at a pressure of 4.0 MPa and a temperature of 220° C. for 90 minutes. After that, in the case of the carrier-attached copper foil, the carrier was peeled off to obtain a laminate for evaluation.
<シェア強度評価基準>
‐評価A:シェア強度が21.3gf/cm以上
‐評価B:シェア強度が19.9gf/cmを超え21.3gf/cm未満
‐評価C:シェア強度が19.9gf/cm以下 A dry film was attached to the laminate for evaluation described above, and exposure and development were performed. After depositing a copper layer by pattern plating on the laminate masked with the developed dry film, the dry film was peeled off. The exposed copper portion was etched with a sulfuric acid-hydrogen peroxide-based etchant to prepare a sample for shear strength measurement having a height of 15 μm, a width of 14 μm, and a length of 150 μm. Using a bonding strength tester (4000Plus Bondtester manufactured by Nordson DAGE), the shear strength when the sample for shear strength measurement was pushed down from the side was measured. At this time, the test type was a destructive test, and the measurement was performed under the conditions of a test height of 5 μm, a descending speed of 0.05 mm/s, a test speed of 200 μm/s, a tool movement of 0.03 mm, and a rupture recognition point of 10%. The obtained shear strength was rated and evaluated according to the following criteria, and evaluations A and B were judged to be acceptable. The results were as shown in Table 2.
<Share strength evaluation criteria>
-Evaluation A: Shear strength of 21.3 gf/cm or more -Evaluation B: Shear strength of more than 19.9 gf/cm and less than 21.3 gf/cm -Evaluation C: Shear strength of 19.9 gf/cm or less
2枚のプリプレグ(パナソニック株式会社製、MEGTRON6、実厚さ68μm)を重ね、その両面にキャリア付銅箔又は粗化処理銅箔の粗化処理面を当接し、真空プレス機を使用して温度190℃で90分間熱圧着した。その後、キャリア付銅箔の場合はキャリアを剥離し銅張積層板を得た。この銅張積層板の銅厚さが18μmとなるように銅めっきを行い、サブトラクティブ法により、マイクロストリップ回路を形成した伝送特性測定用基板を得た。 (c) Transmission characteristics Two sheets of prepreg (manufactured by Panasonic Corporation, MEGTRON6, actual thickness 68 μm) are stacked, and the roughened surfaces of the copper foil with a carrier or the roughened copper foil are brought into contact with both surfaces, and the vacuum press machine is used. was used to perform thermocompression bonding at a temperature of 190° C. for 90 minutes. After that, in the case of a copper foil with a carrier, the carrier was peeled off to obtain a copper-clad laminate. This copper clad laminate was plated with copper so as to have a copper thickness of 18 μm, and by a subtractive method, a substrate for measuring transmission characteristics on which a microstrip circuit was formed was obtained.
<伝送特性評価基準>
‐評価A:伝送損失量の絶対値が0.455dB/cm以下
‐評価B:伝送損失量の絶対値が0.455dB/cmを超え0.465dB/cm未満
‐評価C:伝送損失量の絶対値が0.465dB/cm以上 Using a network analyzer (Agilent, PNA-X N5245A) for the obtained substrate for transmission characteristic measurement, a pattern with a characteristic impedance of the circuit of 50Ω was selected, and the transmission loss S21 (dB/cm) up to 50 GHz was measured. was measured. The average transmission loss amount obtained at 45 to 50 GHz was calculated, and the absolute value was rated and evaluated according to the following criteria. Then, when the transmission characteristic evaluation was A or B, it was determined to be acceptable. The results were as shown in Table 2.
<Transmission Characteristic Evaluation Criteria>
-Evaluation A: The absolute value of the transmission loss amount is 0.455 dB/cm or less -Evaluation B: The absolute value of the transmission loss amount is more than 0.455 dB/cm and less than 0.465 dB/cm -Evaluation C: Absolute transmission loss amount A value of 0.465 dB/cm or more
Claims (11)
- 少なくとも一方の側に粗化処理面を有する粗化処理銅箔であって、前記粗化処理面が基準面に対して凸となる複数の山と前記基準面に対して凹となる複数の谷とを有しており、
前記粗化処理面に対してFIB-SEMを用いて得られる画像を三次元画像解析した場合に、2000nm×2000nmの解析領域における前記山の体積及び前記谷の体積の和として算出される山及び谷の高さの総和が1.4×108nm3以上3.5×108nm3以下であり、かつ、前記山の平均高さ及び前記谷の平均高さの和として算出される山及び谷の平均高さが40nm以上90nm以下である、粗化処理銅箔。 A roughened copper foil having a roughened surface on at least one side, wherein the roughened surface has a plurality of peaks that are convex with respect to a reference surface and a plurality of valleys that are concave with respect to the reference surface. and
When the image obtained using FIB-SEM for the roughened surface is subjected to three-dimensional image analysis, the mountain and the valley calculated as the sum of the volume of the mountain and the volume of the valley in an analysis area of 2000 nm × 2000 nm The sum of the heights of the valleys is 1.4×10 8 nm 3 or more and 3.5×10 8 nm 3 or less, and the peaks calculated as the sum of the average height of the peaks and the average height of the valleys and a roughened copper foil having an average valley height of 40 nm or more and 90 nm or less. - 前記山及び谷の高さの総和が2.0×108nm3以上3.5×108nm3以下である、請求項1に記載の粗化処理銅箔。 The roughened copper foil according to claim 1, wherein the sum of heights of the peaks and valleys is 2.0 x 108 nm3 or more and 3.5 x 108 nm3 or less.
- 前記山及び谷の平均高さが40nm以上80nm以下である、請求項1又は2に記載の粗化処理銅箔。 The roughened copper foil according to claim 1 or 2, wherein the average height of the peaks and valleys is 40 nm or more and 80 nm or less.
- 前記粗化処理面に対してFIB-SEMを用いて得られる画像を三次元画像解析した場合に、単位面積1nm2当たりの前記山の総体積が7.0nm3以上50.0nm3以下である、請求項1又は2に記載の粗化処理銅箔。 When the image obtained using FIB-SEM on the roughened surface is subjected to three-dimensional image analysis, the total volume of the mountains per unit area of 1 nm2 is 7.0 nm3 or more and 50.0 nm3 or less. , The roughened copper foil according to claim 1 or 2.
- 単位面積1nm2当たりの前記山の総体積が30.0nm3以上50.0nm3以下である、請求項4に記載の粗化処理銅箔。 The roughened copper foil according to claim 4, wherein the total volume of the mountains per unit area of 1 nm2 is 30.0 nm3 or more and 50.0 nm3 or less.
- 前記粗化処理面に対してFIB-SEMを用いて得られる画像を三次元画像解析して前記山を複数のボクセルに分割した場合に、2000nm×2000nmの解析領域における前記山を構成する全ボクセルの総体積に対する、前記山の表面を構成するボクセルの総体積の比である表面ボクセル比が0.25以上0.60以下である、請求項1又は2に記載の粗化処理銅箔。 When the image obtained using FIB-SEM on the roughened surface is three-dimensional image analyzed and the mountain is divided into a plurality of voxels, all voxels that constitute the mountain in the analysis area of 2000 nm × 2000 nm The roughened copper foil according to claim 1 or 2, wherein a surface voxel ratio, which is a ratio of the total volume of voxels forming the surface of the mountain to the total volume of the mountain, is 0.25 or more and 0.60 or less.
- 前記表面ボクセル比が0.25以上0.35以下である、請求項6に記載の粗化処理銅箔。 The roughened copper foil according to claim 6, wherein the surface voxel ratio is 0.25 or more and 0.35 or less.
- 前記粗化処理面に防錆処理層及び/又はシランカップリング剤層をさらに備えた、請求項1又は2に記載の粗化処理銅箔。 The roughened copper foil according to claim 1 or 2, further comprising an anticorrosive layer and/or a silane coupling agent layer on the roughened surface.
- キャリアと、該キャリア上に設けられた剥離層と、該剥離層上に前記粗化処理面を外側にして設けられた請求項1又は2に記載の粗化処理銅箔とを備えた、キャリア付銅箔。 A carrier comprising a carrier, a release layer provided on the carrier, and the roughened copper foil according to claim 1 or 2 provided on the release layer with the roughened surface facing outward. with copper foil.
- 請求項1又は2に記載の粗化処理銅箔を備えた、銅張積層板。 A copper clad laminate comprising the roughened copper foil according to claim 1 or 2.
- 請求項1又は2に記載の粗化処理銅箔を備えた、プリント配線板。
A printed wiring board comprising the roughened copper foil according to claim 1 or 2.
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KR1020237038900A KR20240009403A (en) | 2021-05-20 | 2022-05-18 | Roughened copper foil, copper foil with carrier, copper clad laminate and printed wiring board |
CN202280035616.5A CN117321253A (en) | 2021-05-20 | 2022-05-18 | Roughened copper foil, copper foil with carrier, copper-clad laminate, and printed wiring board |
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JP2016089192A (en) * | 2014-10-30 | 2016-05-23 | 株式会社Shカッパープロダクツ | Surface treated copper foil and laminate |
WO2017099094A1 (en) * | 2015-12-09 | 2017-06-15 | 古河電気工業株式会社 | Surface-treated copper foil for printed circuit board, copper-clad laminate for printed circuit board, and printed circuit board |
WO2018211951A1 (en) * | 2017-05-19 | 2018-11-22 | 三井金属鉱業株式会社 | Roughened copper foil, carrier-attached copper foil, copper clad laminate, and printed wiring board |
WO2019093494A1 (en) * | 2017-11-10 | 2019-05-16 | ナミックス株式会社 | Composite copper foil |
JP2020143362A (en) * | 2019-02-01 | 2020-09-10 | 長春石油化學股▲分▼有限公司 | Low transmission loss electrolytic copper foil for printed circuit board |
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JP5242710B2 (en) * | 2010-01-22 | 2013-07-24 | 古河電気工業株式会社 | Roughening copper foil, copper clad laminate and printed wiring board |
JP5204908B1 (en) * | 2012-03-26 | 2013-06-05 | Jx日鉱日石金属株式会社 | Copper foil with carrier, method for producing copper foil with carrier, copper foil with carrier for printed wiring board and printed wiring board |
JP5481577B1 (en) * | 2012-09-11 | 2014-04-23 | Jx日鉱日石金属株式会社 | Copper foil with carrier |
TW201504038A (en) * | 2013-06-04 | 2015-02-01 | Jx Nippon Mining & Metals Corp | Copper foil with carrier, copper-clad laminate, printed wiring board, electric appliance, resin layer, production method for copper foil with carrier, and production method for printed wiring board |
WO2016117587A1 (en) | 2015-01-22 | 2016-07-28 | 三井金属鉱業株式会社 | Ultrathin copper foil with carrier and method for manufacturing same |
WO2016174998A1 (en) * | 2015-04-28 | 2016-11-03 | 三井金属鉱業株式会社 | Roughened copper foil and printed wiring board |
JP6200042B2 (en) * | 2015-08-06 | 2017-09-20 | Jx金属株式会社 | Copper foil with carrier, laminate, printed wiring board manufacturing method and electronic device manufacturing method |
JP6905157B2 (en) | 2018-08-10 | 2021-07-21 | 三井金属鉱業株式会社 | Roughened copper foil, copper foil with carrier, copper-clad laminate and printed wiring board |
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JP2016089192A (en) * | 2014-10-30 | 2016-05-23 | 株式会社Shカッパープロダクツ | Surface treated copper foil and laminate |
WO2017099094A1 (en) * | 2015-12-09 | 2017-06-15 | 古河電気工業株式会社 | Surface-treated copper foil for printed circuit board, copper-clad laminate for printed circuit board, and printed circuit board |
WO2018211951A1 (en) * | 2017-05-19 | 2018-11-22 | 三井金属鉱業株式会社 | Roughened copper foil, carrier-attached copper foil, copper clad laminate, and printed wiring board |
WO2019093494A1 (en) * | 2017-11-10 | 2019-05-16 | ナミックス株式会社 | Composite copper foil |
JP2020143362A (en) * | 2019-02-01 | 2020-09-10 | 長春石油化學股▲分▼有限公司 | Low transmission loss electrolytic copper foil for printed circuit board |
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CN117321253A (en) | 2023-12-29 |
TW202302914A (en) | 2023-01-16 |
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KR20240009403A (en) | 2024-01-22 |
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