WO2022244828A1 - Roughened copper foil, copper foil with carrier, copper-clad laminate, and printed wiring board - Google Patents
Roughened copper foil, copper foil with carrier, copper-clad laminate, and printed wiring board Download PDFInfo
- Publication number
- WO2022244828A1 WO2022244828A1 PCT/JP2022/020749 JP2022020749W WO2022244828A1 WO 2022244828 A1 WO2022244828 A1 WO 2022244828A1 JP 2022020749 W JP2022020749 W JP 2022020749W WO 2022244828 A1 WO2022244828 A1 WO 2022244828A1
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- WIPO (PCT)
- Prior art keywords
- roughened
- copper foil
- particles
- carrier
- axis
- Prior art date
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 224
- 239000011889 copper foil Substances 0.000 title claims abstract description 188
- 239000002245 particle Substances 0.000 claims abstract description 107
- 239000012798 spherical particle Substances 0.000 claims abstract description 34
- 238000010191 image analysis Methods 0.000 claims abstract description 19
- 229910052802 copper Inorganic materials 0.000 claims description 40
- 239000010949 copper Substances 0.000 claims description 40
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 23
- 239000011888 foil Substances 0.000 claims description 10
- 238000007788 roughening Methods 0.000 abstract description 56
- 230000005540 biological transmission Effects 0.000 abstract description 34
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- 238000012545 processing Methods 0.000 abstract description 7
- 239000010410 layer Substances 0.000 description 95
- 239000011347 resin Substances 0.000 description 41
- 229920005989 resin Polymers 0.000 description 41
- 238000000034 method Methods 0.000 description 29
- 238000007747 plating Methods 0.000 description 29
- 238000011156 evaluation Methods 0.000 description 24
- 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
- 238000005530 etching Methods 0.000 description 17
- 238000004458 analytical method Methods 0.000 description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- 239000000758 substrate Substances 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- 238000005259 measurement Methods 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 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
- 229910052725 zinc Inorganic materials 0.000 description 8
- 229910000990 Ni alloy Inorganic materials 0.000 description 7
- 238000000151 deposition Methods 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
- 239000011521 glass Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- -1 nitrogen-containing organic compounds Chemical class 0.000 description 5
- 230000000007 visual effect Effects 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
- 238000004364 calculation method Methods 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 238000004070 electrodeposition Methods 0.000 description 4
- 230000003287 optical effect Effects 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
- 238000001878 scanning electron micrograph Methods 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
- 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
- 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
- XEMZLVDIUVCKGL-UHFFFAOYSA-N hydrogen peroxide;sulfuric acid Chemical compound OO.OS(O)(=O)=O XEMZLVDIUVCKGL-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
- 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
- 230000000694 effects Effects 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
- 239000010419 fine particle 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
- 230000005484 gravity Effects 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000007654 immersion Methods 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
- 239000011159 matrix material Substances 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
- 230000035515 penetration Effects 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
- 230000009467 reduction Effects 0.000 description 1
- 238000004683 secondary electrospray ionisation mass spectroscopy Methods 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 recently found that in a roughened copper foil, by giving a surface profile in which the average height of roughened particles and the proportion of spherical particles in the roughened particles are controlled within predetermined ranges, The present inventors have found that both excellent transmission characteristics and high shear strength can be achieved in the processing of copper-clad laminates or the manufacture of printed wiring boards.
- 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.
- the average height of the roughened particles is 70 nm or less, and the plurality of roughened particles occupy The proportion of the spherical particles is 30% or more
- the spherical particles have a long axis, a middle axis and a short axis that are orthogonal to each other with respect to the roughened particles, and when the length L of the long axis is 1.0, the length M of the middle axis is A roughened copper foil, which is a particle that satisfies 0.3 ⁇ M ⁇ 1.0 and the minor axis length S satisfies 0.3 ⁇ S ⁇ 1.0.
- the base area ratio is the ratio of the projected area to the base area of each roughened particle, and the base area is defined as the xy plane area value of the voxel that constitutes the bottom surface of each roughened particle, and the projected The roughening treatment according to any one of aspects 1 to 3, wherein the area is defined as the product of the x value of the maximum voxel in the x-axis direction and the y value of the maximum voxel in the y-axis direction in each roughening particle.
- Copper foil [Aspect 5] The roughened copper foil according to aspect 4, wherein the average value of the bottom area ratio is 2.0 or more and 3.0 or less.
- Aspect 6 The roughened copper foil according to any one of aspects 1 to 5, further comprising an anticorrosive 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 6 or the carrier-attached copper foil according to aspect 7.
- a printed wiring board comprising the roughened copper foil according to any one of aspects 1 to 6 or the carrier-attached copper foil according to aspect 7.
- 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. 4 is a schematic diagram of a roughening particle divided into a plurality of voxels, and is a diagram for explaining a projected area and a bottom area;
- 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. 5, 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, 5 nm) in the z-axis direction. It is an aggregate of cross-sectional images obtained in a predetermined analysis area (for example, an area of 2400 nm ⁇ 2400 nm when the roughened surface is viewed from above) while the surface is being processed.
- the “average height of roughened particles” means the average height of roughened particles present in a predetermined analysis area (for example, an area of 2400 nm ⁇ 2400 nm when the roughened surface is viewed in plan). means value.
- the average height of the roughened particles can be specified by three-dimensional image analysis of the image obtained using FIB-SEM for the roughened surface. In the three-dimensional image analysis, the underlying shape of the copper foil before roughening may be determined as roughening particles (convex portions). Even if they are not formed by
- the term “spherical particles” refers to roughened particles having a long axis, a middle axis, and a short axis that are perpendicular to each other, and when the length L of the long axis is 1.0, the length of the middle axis It means a particle in which the length M satisfies 0.3 ⁇ M ⁇ 1.0 and the minor axis length S satisfies 0.3 ⁇ S ⁇ 1.0.
- the term “flat particles” means that the length M of the middle axis satisfies 0.3 ⁇ M ⁇ 1.0 when the length L of the long axis is 1.0, and the It means a particle having a short axis length S satisfying S ⁇ 0.3.
- the term “elongated particles” means that the length M of the middle axis satisfies M ⁇ 0.3 when the length L of the long axis is 1.0, and the length of the short axis We mean particles whose height S satisfies S ⁇ 0.3.
- the term “proportion of spherical particles” means the ratio of spherical particles to the roughened particles present in a predetermined analysis area (for example, an area of 2400 nm ⁇ 2400 nm when the roughened surface is viewed from above). do.
- the number NS of spherical particles divided by the sum of the numbers of each particle (that is, the sum of the number NS of spherical particles, the number NF of flat particles, and the number NE of elongated particles) is multiplied by 100.
- Classification of spherical particles, flat particles and elongated particles can be performed by three-dimensional image analysis of images obtained using FIB-SEM on the roughened surface.
- the “average value of the bottom area ratio” means the average of the bottom area ratios of the roughened particles present in a predetermined analysis area (for example, a region of 2400 nm ⁇ 2400 nm when the roughened surface is viewed from above).
- value, and “base area ratio” means the ratio of the projected area to the base area for each roughening particle.
- the base area and projected area can be determined by dividing the roughening particle into voxels. Specifically, as shown in FIG.
- the projected area P is defined as the product of the x value of the maximum voxel in the x-axis direction and the y value of the maximum voxel in the y-axis direction of the roughening particles 10a.
- the bottom area B is defined as the xy plane area value of the voxels forming the bottom surface of the roughening particle 10a.
- the average height of roughened particles, the ratio of spherical particles, and the average value of the base area ratio are obtained by three-dimensional image analysis of the image obtained using FIB-SEM for the roughened surface.
- Such three-dimensional image analysis can be performed using commercially available software.
- the three-dimensional alignment software "ExFact Slice Aligner (version 2.0)" (manufactured by Nippon Visual Science Co., Ltd.
- electrode surface of the carrier refers to the surface that was in contact with the cathode when the carrier was produced.
- 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.
- the roughened surface has a plurality of roughened particles including spherical particles. Then, when an image obtained by using an FIB-SEM on the roughened surface is subjected to three-dimensional image analysis, the average height of the roughened particles is 70 nm or less. Moreover, the ratio of the spherical particles to the plurality of roughened particles is 30% or more.
- the copper clad laminate in the roughened copper foil, by imparting a surface profile in which the average height of the roughened particles and the proportion of spherical particles in the roughened particles are controlled within a predetermined range, the copper clad laminate can be obtained.
- the roughened copper foil of the present invention unexpectedly makes it possible to achieve both.
- the mechanism is not necessarily clear, one of the factors is as follows. First, by reducing the average height of the roughened particles to 70 nm or less, it is possible to reduce the transmission loss by miniaturizing the roughened particles. As the roughened particles become finer, there is concern that the shear strength will decrease. By increasing the proportion of spherical particles in the roughened particles to 30% or more, the anchor effect based on the constricted shape of the spherical particles is exhibited. It is considered that the fine particles can achieve excellent adhesion to the resin.
- FIG. 4 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 average height of the roughened particles is 70 nm or less, preferably 20 nm or more and 70 nm or less, more preferably 30 nm or more and 70 nm or less, even more preferably 50 nm or more and 70 nm or less, and particularly preferably 60 nm or more and 70 nm or less. By doing so, it is possible to achieve excellent transmission characteristics while maintaining high shear strength.
- the proportion of spherical particles in the roughened particles is 30% or more, preferably 30% or more and 90% or less, more preferably 30% or more and 70% or less, still more preferably 30% or more and 50% or less, particularly preferably 35%. 45% or less. By doing so, it is possible to achieve high shear strength while having excellent transmission characteristics.
- the average value of the bottom area ratio of the roughened particles is preferably 3.0 or less, more preferably 2.0 or more and 3.0 or less.
- the mechanism by which the etchability is improved by controlling the average value of the bottom area ratio is not necessarily clear, one of the factors is as follows. That is, when forming a circuit on a copper-clad laminate or the like by etching, it is necessary to remove not only the copper foil on the surface but also the roughened particles that have penetrated into the substrate resin. At this time, since the constricted portion of the roughening particles is too thin, it becomes difficult for the etchant to penetrate into the portion of the resin substrate in which the roughening particles have been bitten, and a large amount of etching is required to eliminate the residual copper. things can happen.
- the roughened particles will have a constricted shape that is convenient for the penetration of the etchant, and the amount of etching required to remove the roughened particles will be reduced. can be reduced.
- 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. It is preferable that the roughened surface comprises a plurality of roughening particles, and each of the plurality of roughening particles 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.
- 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 numerical value means a numerical value obtained by measuring and analyzing the roughened copper foil after the antirust treatment layer and/or the silane coupling agent treatment layer has been formed.
- 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 an average height of roughened particles within the above-described 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, 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 or the carrier-attached copper foil.
- a copper-clad laminate comprising the roughened copper foil or the carrier-attached 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.
- 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.
- 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 or the carrier-attached copper foil.
- a printed wiring board comprising the roughened copper foil or the carrier-attached 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.
- 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.
- 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 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.
- MSAP modified semi-additive
- the build-up wiring board and the roughened copper foil are removed.
- 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.
- 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 1-3 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 3 a two-step roughening treatment was 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 4 (Comparison) 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) A carrier-attached copper foil was produced in the same manner as in Example 1, except that the ultra-thin copper foil was not subjected to roughening treatment.
- the roughened copper foils or carrier-attached copper foils produced in Evaluation Examples 1 to 5 were subjected to various evaluations shown below.
- each convex part is a spherical particle , flat particles, and elongated particles. Convex portions whose shape cannot be determined (calculation of S, M, and L) due to reasons such as a small number of pixels are excluded from the calculation as noise.
- the results were as shown in Table 3.
- ⁇ Average value of bottom area ratio The numerical value of “surface_voxels (voxels)” in each convex portion was defined as the xy plane area value (that is, the bottom area) of the voxels forming the bottom surface of each roughening particle. Also, the numerical value of "size_X (voxels)" in each convex portion is the x value of the maximum voxel in the x-axis direction for each roughening particle, and the numerical value of "size_Y (voxels)” is the y value of the maximum voxel in the y-axis direction. did. Then, the product of the x value and the y value was defined as the projected area of each roughening particle. The ratio of the projected area to the bottom area of each roughening particle was determined as the bottom area ratio, and the average value was calculated. The results were as shown in Table 3.
- 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.
- circuit formability evaluation of etching property
- a laminate for evaluation was produced in the same procedure as for the shear strength. This laminate for evaluation was etched with a sulfuric acid-hydrogen peroxide-based etchant by 0.2 ⁇ m. Measurements were made by checking with an optical microscope (500x) after each etching. When the etching progresses and the laminate for evaluation is observed with an optical microscope, the starting point is when the base resin begins to be observed, and the end point is when the copper (including roughening particles) on the surface is completely removed. did. The etching amount (depth) required from the start point to the end point was defined as the etching amount of the roughening particles.
- the etching amount of the roughened particles is 0.4 ⁇ m
- the etching amount of the obtained roughening particles was graded and evaluated according to the following criteria. The results were as shown in Table 3.
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- Electroplating Methods And Accessories (AREA)
- Parts Printed On Printed Circuit Boards (AREA)
- Laminated Bodies (AREA)
Abstract
Provided is a roughened copper foil capable of achieving both excellent transmission characteristics and a high shear strength in the processing of a copper-clad laminate or in the production of a printed wiring board. This roughened copper foil has a roughened surface on at least one side. This roughened surface has multiple roughening particles, including spherical particles, wherein when a three-dimensional image analysis of a roughened surface image obtained using an FIB-SEM is carried out, the roughening particles have an average height of 70 nm or less, and the occupancy ratio of the spherical particles in the multiple roughening particles is 30% or greater. When a long axis, intermediate axis, and short axis that are orthogonal to each other are set for the of the roughening particles and the length L of the long axis is expressed by 1.0, the spherical particles satisfy the following: the length M of the intermediate axis satisfies 0.3 ≤ M ≤ 1.0, and the length S of the short axis satisfies 0.3 ≤ S ≤ 1.0.
Description
本発明は、粗化処理銅箔、キャリア付銅箔、銅張積層板及びプリント配線板に関する。
The present invention relates to a roughened copper foil, a copper foil with a carrier, a copper-clad laminate, and a printed wiring board.
近年、回路の微細化に適したプリント配線板の製造工法として、ＭＳＡＰ（モディファイド・セミ・アディティブ・プロセス）法が広く採用されている。ＭＳＡＰ法は、極めて微細な回路を形成するのに適した手法であり、その特徴を活かすため、キャリア付銅箔を用いて行われている。例えば、図１及び２に示されるように、極薄銅箔（粗化処理銅箔１０）を、下地基材１１ａ上に下層回路１１ｂを備えた絶縁樹脂基板１１上にプリプレグ１２とプライマー層１３を介してプレスして密着させ（工程（ａ））、キャリア（図示せず）を引き剥がした後、必要に応じてレーザー穿孔によりビアホール１４を形成する（工程（ｂ））。次いで、化学銅めっき１５を施した（工程（ｃ））後に、ドライフィルム１６を用いた露光及び現像により所定のパターンでマスキングし（工程（ｄ））、電気銅めっき１７を施す（工程（ｅ））。ドライフィルム１６を除去して配線部分１７ａを形成した後（工程（ｆ））、互いに隣り合う配線部分１７ａと１７ａ間の不要な極薄銅箔等をそれらの厚み全体にわたってエッチングにより除去して（工程（ｇ））、所定のパターンで形成された配線１８を得る。ここで、回路－基板間の物理的密着性を向上すべく、極薄銅箔の表面に粗化処理を行うことが一般的に行われている。
In recent years, the MSAP (Modified Semi-Additive Process) method has been widely adopted as a manufacturing method for printed wiring boards suitable for miniaturization of circuits. 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)). Next, 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 )). 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. Here, in order to improve the physical adhesion between the circuit and the substrate, it is common practice to roughen the surface of the ultra-thin copper foil.
実際、ＭＳＡＰ法等による微細回路形成性に優れたキャリア付銅箔が幾つか提案されている。例えば、特許文献１（国際公開第２０１６／１１７５８７号）には、剥離層側の面の表面ピーク間平均距離が２０μｍ以下であり、かつ、剥離層と反対側の面のうねりの最大高低差が１．０μｍ以下である極薄銅箔を備えたキャリア付銅箔が開示されており、かかる態様によれば微細回路形成性とレーザー加工性とを両立できるとされている。また、特許文献２（特開２０１８－２６５９０号公報）には、微細回路形成性を向上することを目的として、極薄銅層側表面のＩＳＯ２５１７８に準拠した最大山高さＳｐと突出山部高さＳｐｋとの比Ｓｐ／Ｓｐｋが３．２７１以上１０．７３９以下であるキャリア付銅箔が開示されている。
In fact, several carrier-attached copper foils with excellent fine circuit formability have been proposed by the MSAP method or the like. For example, in Patent Document 1 (International Publication No. 2016/117587), the average distance between surface peaks on the side of the release layer is 20 μm or less, and 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 μm or less is disclosed, and according to this aspect, it is said that both fine circuit formability and laser processability can be achieved. In addition, in Patent Document 2 (Japanese Patent Application Laid-Open No. 2018-26590), for the purpose of improving fine circuit formability, the maximum peak height Sp and the protruding peak height Sp according to ISO25178 on the surface of the ultra-thin copper layer side A carrier-attached copper foil having a ratio Sp/Spk to Spk of 3.271 or more and 10.739 or less is disclosed.
一方、回路の細線化が進むにつれて、プリント配線板の実装工程において、回路に横方向からの物理的な応力（すなわちシェア応力）が加わることで回路が剥がれやすくなり、歩留まりが低下するという課題が顕在化している。この点、回路と基板の物理密着指標の一つにシェア強度（せん断強度）があり、上述の回路剥がれを効果的に回避すべく、シェア強度の向上に適した粗化処理銅箔が提案されている。例えば、特許文献３（国際公開第２０２０／０３１７２１号）には、ＩＳＯ２５１７８に規定される最大高さＳｚ、界面の展開面積比Ｓｄｒ及び山の頂点密度Ｓｐｄがそれぞれ所定の範囲に制御された粗化処理銅箔が開示されている。かかる粗化処理銅箔によれば、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、優れたエッチング性と高いシェア強度とを両立できるとされている。
On the other hand, as circuits become finer, there is a problem that in the mounting process of printed wiring boards, physical stress (i.e., shear stress) is applied to the circuit from the lateral direction, making the circuit easier to peel off and lowering the yield. It is manifesting. In this regard, shear strength (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. For example, in Patent Document 3 (International Publication No. 2020/031721), the maximum height Sz defined in ISO25178, the expansion area ratio Sdr of the interface, and the peak density Spd of the mountain are each controlled to a predetermined range. 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.
ところで、近年の携帯用電子機器等の高機能化に伴い、大量の情報の高速処理をすべく信号の高周波化が進んでおり、とりわけ第５世代移動通信システム（５Ｇ）や第６世代移動通信システム（６Ｇ）等の高周波用途に適したプリント配線板が求められている。このような高周波用プリント配線板には、高周波信号を品質低下させずに伝送可能とするために、伝送損失の低減が望まれる。プリント配線板は配線パターンに加工された銅箔と絶縁樹脂基材とを備えたものであるが、伝送損失は、銅箔に起因する導体損失と、絶縁樹脂基材に起因する誘電体損失とから主としてなる。
By the way, along with recent advances in functionality of portable electronic devices and the like, signals are becoming higher in frequency in order to process a large amount of information at high speed. There is a demand for printed wiring boards suitable for high frequency applications such as systems (6G). For such high-frequency printed wiring boards, reduction in transmission loss is desired in order to enable transmission of high-frequency signals without degrading the quality thereof. 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. Mainly from
導体損失は、高周波になるほど顕著に現れる銅箔の表皮効果によって増大しうる。したがって、高周波用途における伝送損失を抑制するには、銅箔の表皮効果を低減すべく銅箔の平滑化及び粗化粒子の微細化が求められる。この点、伝送損失の低減を目的とした粗化処理銅箔が知られている。例えば、特許文献４（特許第６４６２９６１号公報）には、銅箔の少なくとも片面に、粗化処理層、防錆処理層及びシランカップリング層がこの順で積層された表面処理銅箔に関して、シランカップリング層の表面から測定された界面の展開面積比Ｓｄｒが８％以上１４０％以下、二乗平均平方根表面勾配Ｓｄｑが２５°以上７０°以下、及び表面性状のアスペクト比Ｓｔｒが０．２５以上０．７９以下であることが開示されている。かかる表面処理銅箔によれば、高周波電気信号の伝送損失が少なく、かつリフローはんだ付けの際の優れた密着性を有するプリント配線板の製造が可能になるとされている。
Conductor loss can increase due to the skin effect of the copper foil, which becomes more pronounced at higher frequencies. Therefore, in order to suppress the transmission loss in high-frequency applications, smoothing of the copper foil and miniaturization of roughened particles are required in order to reduce the skin effect of the copper foil. In this respect, a roughened copper foil is known for the purpose of reducing transmission loss. For example, 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.
上述のとおり、高周波伝送の観点から、信号を流す回路配線を形成する材料として伝送損失の少ない銅箔（すなわち高周波特性に優れる銅箔）が求められている。銅箔の平滑化及び粗化粒子の微小化により、伝送損失を抑制することができると考えられるものの、銅箔と基板樹脂等との物理的密着力（とりわけシェア強度）は低下することになる。このように、優れた伝送特性と高い回路密着性とを両立することは容易なことではない。
As described above, from the perspective of high-frequency transmission, copper foil with low transmission loss (that is, copper foil with excellent high-frequency characteristics) is required as a material for forming circuit wiring that carries signals. Although it is thought that 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. . Thus, it is not easy to achieve both excellent transmission characteristics and high circuit adhesion.
本発明者らは、今般、粗化処理銅箔において、粗化粒子の平均高さ、及び粗化粒子に占める球状粒子の割合をそれぞれ所定の範囲内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、優れた伝送特性と高いシェア強度とを両立できるとの知見を得た。
The present inventors have recently found that in a roughened copper foil, by giving a surface profile in which the average height of roughened particles and the proportion of spherical particles in the roughened particles are controlled within predetermined ranges, The present inventors have found that both excellent transmission characteristics and high shear strength can be achieved in the processing of copper-clad laminates or the manufacture of printed wiring boards.
したがって、本発明の目的は、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、優れた伝送特性と高いシェア強度とを両立可能な、粗化処理銅箔を提供することにある。
Therefore, 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.
本発明によれば、以下の態様が提供される。
［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、前記粗化処理面が球状粒子を含む複数の粗化粒子を有しており、
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、前記粗化粒子の平均高さが７０ｎｍ以下であり、かつ、前記複数の粗化粒子に占める前記球状粒子の割合が３０％以上であり、
前記球状粒子は、前記粗化粒子に対して、互いに直行する長軸、中軸及び短軸を設定し、前記長軸の長さＬを１．０とした場合に、前記中軸の長さＭが０．３≦Ｍ≦１．０を満たし、かつ、前記短軸の長さＳが０．３≦Ｓ≦１．０を満たす粒子である、粗化処理銅箔。
［態様２］
前記平均高さが２０ｎｍ以上７０ｎｍ以下である、態様１に記載の粗化処理銅箔。
［態様３］
前記球状粒子の割合が３０％以上９０％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、ｚ軸が前記粗化処理面に対して垂直になり、かつ、ｘ－ｙ面が前記粗化処理面と平行になるようにｘ軸、ｙ軸及びｚ軸を割り当てて三次元画像解析して前記粗化粒子を複数のボクセルに分割した場合に、前記複数の粗化粒子は、底面積比の平均値が３．０以下であり、
前記底面積比は、各粗化粒子における底面積に対する投射面積の比であり、前記底面積は、前記各粗化粒子の底面を構成するボクセルのｘ－ｙ平面積値として定義され、前記投射面積は、前記各粗化粒子におけるｘ軸方向の最大ボクセルのｘ値及びｙ軸方向の最大ボクセルのｙ値の積として定義される、態様１～３のいずれか一つに記載の粗化処理銅箔。
［態様５］
前記底面積比の平均値が２．０以上３．０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１～５のいずれか一つに記載の粗化処理銅箔。
［態様７］
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１～６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８］
態様１～６のいずれか一つに記載の粗化処理銅箔又は態様７に記載のキャリア付銅箔を備えた、銅張積層板。
［態様９］
態様１～６のいずれか一つに記載の粗化処理銅箔又は態様７に記載のキャリア付銅箔を備えた、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, the roughened surface having a plurality of roughened particles including spherical particles,
When the image obtained using FIB-SEM on the roughened surface is subjected to three-dimensional image analysis, the average height of the roughened particles is 70 nm or less, and the plurality of roughened particles occupy The proportion of the spherical particles is 30% or more,
The spherical particles have a long axis, a middle axis and a short axis that are orthogonal to each other with respect to the roughened particles, and when the length L of the long axis is 1.0, the length M of the middle axis is A roughened copper foil, which is a particle that satisfies 0.3≦M≦1.0 and the minor axis length S satisfies 0.3≦S≦1.0.
[Aspect 2]
The roughened copper foil according to aspect 1, wherein the average height is 20 nm or more and 70 nm or less.
[Aspect 3]
The roughened copper foil according to aspect 1 or 2, wherein the proportion of the spherical particles is 30% or more and 90% or less.
[Aspect 4]
An image obtained using a FIB-SEM of the roughened surface is taken so that the z-axis is perpendicular to the roughened surface and the xy plane is parallel to the roughened surface. When the roughened particles are divided into a plurality of voxels by three-dimensional image analysis with the x-axis, y-axis, and z-axis assigned as above, the average value of the bottom area ratio of the plurality of roughened particles is 3. is 0 or less,
The base area ratio is the ratio of the projected area to the base area of each roughened particle, and the base area is defined as the xy plane area value of the voxel that constitutes the bottom surface of each roughened particle, and the projected The roughening treatment according to any one of aspects 1 to 3, wherein the area is defined as the product of the x value of the maximum voxel in the x-axis direction and the y value of the maximum voxel in the y-axis direction in each roughening particle. Copper foil.
[Aspect 5]
The roughened copper foil according to aspect 4, wherein the average value of the bottom area ratio is 2.0 or more and 3.0 or less.
[Aspect 6]
The roughened copper foil according to any one of aspects 1 to 5, further comprising an anticorrosive layer and/or a silane coupling agent layer on the roughened surface.
[Aspect 7]
A carrier, a release layer provided on the carrier, and the roughened copper foil according to any one of aspects 1 to 6 provided on the release layer with the roughened surface facing outward. copper foil with carrier.
[Aspect 8]
A copper clad laminate comprising the roughened copper foil according to any one of aspects 1 to 6 or the carrier-attached copper foil according to aspect 7.
[Aspect 9]
A printed wiring board comprising the roughened copper foil according to any one of aspects 1 to 6 or the carrier-attached copper foil according to aspect 7.
［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、前記粗化処理面が球状粒子を含む複数の粗化粒子を有しており、
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、前記粗化粒子の平均高さが７０ｎｍ以下であり、かつ、前記複数の粗化粒子に占める前記球状粒子の割合が３０％以上であり、
前記球状粒子は、前記粗化粒子に対して、互いに直行する長軸、中軸及び短軸を設定し、前記長軸の長さＬを１．０とした場合に、前記中軸の長さＭが０．３≦Ｍ≦１．０を満たし、かつ、前記短軸の長さＳが０．３≦Ｓ≦１．０を満たす粒子である、粗化処理銅箔。
［態様２］
前記平均高さが２０ｎｍ以上７０ｎｍ以下である、態様１に記載の粗化処理銅箔。
［態様３］
前記球状粒子の割合が３０％以上９０％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、ｚ軸が前記粗化処理面に対して垂直になり、かつ、ｘ－ｙ面が前記粗化処理面と平行になるようにｘ軸、ｙ軸及びｚ軸を割り当てて三次元画像解析して前記粗化粒子を複数のボクセルに分割した場合に、前記複数の粗化粒子は、底面積比の平均値が３．０以下であり、
前記底面積比は、各粗化粒子における底面積に対する投射面積の比であり、前記底面積は、前記各粗化粒子の底面を構成するボクセルのｘ－ｙ平面積値として定義され、前記投射面積は、前記各粗化粒子におけるｘ軸方向の最大ボクセルのｘ値及びｙ軸方向の最大ボクセルのｙ値の積として定義される、態様１～３のいずれか一つに記載の粗化処理銅箔。
［態様５］
前記底面積比の平均値が２．０以上３．０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１～５のいずれか一つに記載の粗化処理銅箔。
［態様７］
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１～６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８］
態様１～６のいずれか一つに記載の粗化処理銅箔又は態様７に記載のキャリア付銅箔を備えた、銅張積層板。
［態様９］
態様１～６のいずれか一つに記載の粗化処理銅箔又は態様７に記載のキャリア付銅箔を備えた、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, the roughened surface having a plurality of roughened particles including spherical particles,
When the image obtained using FIB-SEM on the roughened surface is subjected to three-dimensional image analysis, the average height of the roughened particles is 70 nm or less, and the plurality of roughened particles occupy The proportion of the spherical particles is 30% or more,
The spherical particles have a long axis, a middle axis and a short axis that are orthogonal to each other with respect to the roughened particles, and when the length L of the long axis is 1.0, the length M of the middle axis is A roughened copper foil, which is a particle that satisfies 0.3≦M≦1.0 and the minor axis length S satisfies 0.3≦S≦1.0.
[Aspect 2]
The roughened copper foil according to aspect 1, wherein the average height is 20 nm or more and 70 nm or less.
[Aspect 3]
The roughened copper foil according to aspect 1 or 2, wherein the proportion of the spherical particles is 30% or more and 90% or less.
[Aspect 4]
An image obtained using a FIB-SEM of the roughened surface is taken so that the z-axis is perpendicular to the roughened surface and the xy plane is parallel to the roughened surface. When the roughened particles are divided into a plurality of voxels by three-dimensional image analysis with the x-axis, y-axis, and z-axis assigned as above, the average value of the bottom area ratio of the plurality of roughened particles is 3. is 0 or less,
The base area ratio is the ratio of the projected area to the base area of each roughened particle, and the base area is defined as the xy plane area value of the voxel that constitutes the bottom surface of each roughened particle, and the projected The roughening treatment according to any one of aspects 1 to 3, wherein the area is defined as the product of the x value of the maximum voxel in the x-axis direction and the y value of the maximum voxel in the y-axis direction in each roughening particle. Copper foil.
[Aspect 5]
The roughened copper foil according to aspect 4, wherein the average value of the bottom area ratio is 2.0 or more and 3.0 or less.
[Aspect 6]
The roughened copper foil according to any one of aspects 1 to 5, further comprising an anticorrosive layer and/or a silane coupling agent layer on the roughened surface.
[Aspect 7]
A carrier, a release layer provided on the carrier, and the roughened copper foil according to any one of aspects 1 to 6 provided on the release layer with the roughened surface facing outward. copper foil with carrier.
[Aspect 8]
A copper clad laminate comprising the roughened copper foil according to any one of aspects 1 to 6 or the carrier-attached copper foil according to aspect 7.
[Aspect 9]
A printed wiring board comprising the roughened copper foil according to any one of aspects 1 to 6 or the carrier-attached copper foil according to aspect 7.
定義
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.
本明細書において、「粗化処理面に対してＦＩＢ－ＳＥＭを用いて得られる画像」とは、粗化処理銅箔の粗化処理面に対して、ＦＩＢ（集束イオンビーム）による断面加工とＳＥＭ（走査電子顕微鏡）による断面観察を経て取得される断面画像の集合体を意味し、全体として三次元形状データを構成する。具体的には、図５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の粗化処理面を含む断面画像を取得し、このスライス面をｚ軸方向に所定間隔（例えば５ｎｍ）ずつ平行移動させながら、所定の解析領域（例えば粗化処理面を平面視した場合に２４００ｎｍ×２４００ｎｍの領域）において取得される断面画像の集合体である。
In this specification, the term "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. 5, 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. Then, 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, 5 nm) in the z-axis direction. It is an aggregate of cross-sectional images obtained in a predetermined analysis area (for example, an area of 2400 nm×2400 nm when the roughened surface is viewed from above) while the surface is being processed.
本明細書において、「粗化粒子の平均高さ」とは、所定の解析領域（例えば粗化処理面を平面視した場合に２４００ｎｍ×２４００ｎｍの領域）に存在する粗化粒子の高さの平均値を意味する。粗化粒子の平均高さは、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することにより、特定することができる。なお、三次元画像解析の際に、粗化処理前の銅箔の下地形状等が粗化粒子（凸部）と判断されることがあるが、このように判断された部分は、粗化処理によって形成されたものでなくても粗化粒子とみなして、各種パラメータの計算に算入するものとする。
In the present specification, the “average height of roughened particles” means the average height of roughened particles present in a predetermined analysis area (for example, an area of 2400 nm × 2400 nm when the roughened surface is viewed in plan). means value. The average height of the roughened particles can be specified by three-dimensional image analysis of the image obtained using FIB-SEM for the roughened surface. In the three-dimensional image analysis, the underlying shape of the copper foil before roughening may be determined as roughening particles (convex portions). Even if they are not formed by
本明細書において、「球状粒子」とは、粗化粒子に対して、互いに直行する長軸、中軸及び短軸を設定し、長軸の長さＬを１．０とした場合に、中軸の長さＭが０．３≦Ｍ≦１．０を満たし、かつ、短軸の長さＳが０．３≦Ｓ≦１．０を満たす粒子を意味する。本明細書において、「平たい粒子」とは、上記長軸の長さＬを１．０とした場合に、上記中軸の長さＭが０．３＜Ｍ≦１．０を満たし、かつ、上記短軸の長さＳがＳ＜０．３を満たす粒子を意味する。本明細書において、「細長い粒子」とは、上記長軸の長さＬを１．０とした場合に、上記中軸の長さＭがＭ≦０．３を満たし、かつ、上記短軸の長さＳがＳ＜０．３を満たす粒子を意味する。本明細書において「球状粒子の割合」とは、所定の解析領域（例えば粗化処理面を平面視した場合に２４００ｎｍ×２４００ｎｍの領域）に存在する粗化粒子に占める、球状粒子の割合を意味する。すなわち、球状粒子の個数ＮＳを、各粒子の個数の和（つまり球状粒子の個数ＮＳ、平たい粒子の個数ＮＦ及び細長い粒子の個数ＮＥの和）で割った値に、１００を乗じることにより（＝１００×ＮＳ／（ＮＳ＋ＮＦ＋ＮＥ））、球状粒子の割合を算出することができる。球状粒子、平たい粒子及び細長い粒子の分類は、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することにより行うことができる。
As used herein, the term “spherical particles” refers to roughened particles having a long axis, a middle axis, and a short axis that are perpendicular to each other, and when the length L of the long axis is 1.0, the length of the middle axis It means a particle in which the length M satisfies 0.3≦M≦1.0 and the minor axis length S satisfies 0.3≦S≦1.0. In this specification, the term “flat particles” means that the length M of the middle axis satisfies 0.3<M≦1.0 when the length L of the long axis is 1.0, and the It means a particle having a short axis length S satisfying S<0.3. As used herein, the term “elongated particles” means that the length M of the middle axis satisfies M≦0.3 when the length L of the long axis is 1.0, and the length of the short axis We mean particles whose height S satisfies S<0.3. As used herein, the term "proportion of spherical particles" means the ratio of spherical particles to the roughened particles present in a predetermined analysis area (for example, an area of 2400 nm × 2400 nm when the roughened surface is viewed from above). do. That is, the number NS of spherical particles divided by the sum of the numbers of each particle (that is, the sum of the number NS of spherical particles, the number NF of flat particles, and the number NE of elongated particles) is multiplied by 100. Thus, (=100×N S /(N S +N F +N E )), the percentage of spherical particles can be calculated. Classification of spherical particles, flat particles and elongated particles can be performed by three-dimensional image analysis of images obtained using FIB-SEM on the roughened surface.
本明細書において、「ボクセル」とは、三次元画像データにおける体積の要素であり、二次元画像データの画素に対応する概念である。ボクセルは、立方体や直方体等で表現することができ、例えば１ボクセル毎に（縦、横、高さ）＝（１ｎｍ、１ｎｍ、１ｎｍ）のような大きさを持つため、ＳＩ単位に換算することが可能である。
In this specification, a "voxel" is a volume element in three-dimensional image data, and is a concept corresponding to a pixel in two-dimensional image data. Voxels can be represented by cubes, rectangular parallelepipeds, etc. For example, since each voxel has a size such as (length, width, height) = (1 nm, 1 nm, 1 nm), it is necessary to convert to SI units. is possible.
本明細書において、「底面積比の平均値」とは、所定の解析領域（例えば粗化処理面を平面視した場合に２４００ｎｍ×２４００ｎｍの領域）に存在する粗化粒子の底面積比の平均値を意味し、「底面積比」とは、各粗化粒子における底面積に対する投射面積の比を意味する。底面積及び投射面積は、粗化粒子を複数のボクセルに分割することにより、特定することができる。具体的には、粗化処理面に対してＦＩＢ－ＳＥＭを用いて得られる画像を、図６に示されるように、ｚ軸が粗化処理面に対して垂直になり、かつ、ｘ－ｙ面が粗化処理面と平行になるようにｘ軸、ｙ軸及びｚ軸を割り当てて三次元画像解析して粗化粒子を複数のボクセルに分割する。このとき、図３に示されるように、投射面積Ｐは、粗化粒子１０ａにおけるｘ軸方向の最大ボクセルのｘ値及びｙ軸方向の最大ボクセルのｙ値の積として定義される。また、図３に示されるように、底面積Ｂは、粗化粒子１０ａの底面を構成するボクセルのｘ－ｙ平面積値として定義される。
In the present specification, the “average value of the bottom area ratio” means the average of the bottom area ratios of the roughened particles present in a predetermined analysis area (for example, a region of 2400 nm × 2400 nm when the roughened surface is viewed from above). value, and "base area ratio" means the ratio of the projected area to the base area for each roughening particle. The base area and projected area can be determined by dividing the roughening particle into voxels. Specifically, as shown in FIG. 6, an image obtained using a FIB-SEM for the roughened surface is taken so that the z-axis is perpendicular to the roughened surface and the xy The x-, y-, and z-axes are assigned such that the surface is parallel to the roughened surface, and three-dimensional image analysis is performed to divide the roughened particles into a plurality of voxels. At this time, as shown in FIG. 3, the projected area P is defined as the product of the x value of the maximum voxel in the x-axis direction and the y value of the maximum voxel in the y-axis direction of the roughening particles 10a. Further, as shown in FIG. 3, the bottom area B is defined as the xy plane area value of the voxels forming the bottom surface of the roughening particle 10a.
上述したとおり、粗化粒子の平均高さ、球状粒子の割合、及び底面積比の平均値は、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することにより、特定することができる。このような三次元画像解析は、市販のソフトウェアを用いて行うことができる。例えば、粗化処理面の画像（粗化処理銅箔の三次元形状データのスライス画像）に対して、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）並びに三次元画像解析ソフト「ＥｘＦａｃｔ ＶＲ（バージョン２．２）」及び「ｆｏｉｌ Ａｎａｌｙｓｉｓ（バージョン１．０）」（いずれも日本ビジュアルサイエンス株式会社製）を用い、本明細書の実施例に記載される諸条件に従って画像解析を行うことができる。また、ＦＩＢ－ＳＥＭを用いて得られる断面画像の取得方法については後述の実施例に示すものとする。
As described above, the average height of roughened particles, the ratio of spherical particles, and the average value of the base area ratio are obtained by three-dimensional image analysis of the image obtained using FIB-SEM for the roughened surface. , can be specified. Such three-dimensional image analysis can be performed using commercially available software. For example, for the image of the roughened surface (sliced image of the three-dimensional shape data of the roughened copper foil), the three-dimensional alignment software "ExFact Slice Aligner (version 2.0)" (manufactured by 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 various conditions. Also, a method for obtaining a cross-sectional image obtained by using the FIB-SEM will be described in Examples below.
本明細書において、キャリアの「電極面」とは、キャリア作製時に陰極と接していた側の面を指す。
In this specification, the "electrode surface" of the carrier refers to the surface that was in contact with the cathode when the carrier was produced.
本明細書において、キャリアの「析出面」とは、キャリア作製時に電解銅が析出されていく側の面、すなわち陰極と接していない側の面を指す。
In this specification, 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.
粗化処理銅箔
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、球状粒子を含む複数の粗化粒子を有する。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、粗化粒子の平均高さが７０ｎｍ以下である。また、複数の粗化粒子に占める球状粒子の割合が３０％以上である。このように粗化処理銅箔において、粗化粒子の平均高さ、及び粗化粒子に占める球状粒子の割合をそれぞれ所定の範囲内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. The roughened surface has a plurality of roughened particles including spherical particles. Then, when an image obtained by using an FIB-SEM on the roughened surface is subjected to three-dimensional image analysis, the average height of the roughened particles is 70 nm or less. Moreover, the ratio of the spherical particles to the plurality of roughened particles is 30% or more. In this way, in the roughened copper foil, by imparting a surface profile in which the average height of the roughened particles and the proportion of spherical particles in the roughened particles are controlled within a predetermined range, the copper clad laminate can be obtained. In processing or manufacturing 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 from the viewpoint of shear strength).
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、球状粒子を含む複数の粗化粒子を有する。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、粗化粒子の平均高さが７０ｎｍ以下である。また、複数の粗化粒子に占める球状粒子の割合が３０％以上である。このように粗化処理銅箔において、粗化粒子の平均高さ、及び粗化粒子に占める球状粒子の割合をそれぞれ所定の範囲内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. The roughened surface has a plurality of roughened particles including spherical particles. Then, when an image obtained by using an FIB-SEM on the roughened surface is subjected to three-dimensional image analysis, the average height of the roughened particles is 70 nm or less. Moreover, the ratio of the spherical particles to the plurality of roughened particles is 30% or more. In this way, in the roughened copper foil, by imparting a surface profile in which the average height of the roughened particles and the proportion of spherical particles in the roughened particles are controlled within a predetermined range, the copper clad laminate can be obtained. In processing or manufacturing 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 from the viewpoint of shear strength).
上述したとおり、優れた伝送特性と高いシェア強度とは本来的には両立し難いものであるが、本発明の粗化処理銅箔によればこれらを予想外にも両立することが可能となる。そのメカニズムは必ずしも定かではないが、要因の一つとして以下のようなものが挙げられる。まず、粗化粒子の平均高さを７０ｎｍ以下と小さくすることで、粗化粒子の微細化による伝送損失の低減を実現することができる。そして、粗化粒子の微細化に伴いシェア強度の低下が懸念されるところ、粗化粒子に占める球状粒子の割合を３０％以上と大きくすることで、球状粒子のくびれ形状に基づくアンカー効果を発揮させることができ、微細粒子でありながらも樹脂との優れた密着性を実現できるものと考えられる。
As described above, excellent transmission characteristics and high shear strength are inherently difficult to achieve at the same time, but the roughened copper foil of the present invention unexpectedly makes it possible to achieve both. . Although the mechanism is not necessarily clear, one of the factors is as follows. First, by reducing the average height of the roughened particles to 70 nm or less, it is possible to reduce the transmission loss by miniaturizing the roughened particles. As the roughened particles become finer, there is concern that the shear strength will decrease. By increasing the proportion of spherical particles in the roughened particles to 30% or more, the anchor effect based on the constricted shape of the spherical particles is exhibited. It is considered that the fine particles can achieve excellent adhesion to the resin.
一方、従来技術においては、レーザー顕微鏡を用いて粗化形状を評価していたが、かかる手法では微小な粗化形状の特徴を正しく評価するのに限界がある。ここで、レーザー顕微鏡による粗化処理面の測定の一例を図４に模式的に示す。図４に示されるように、レーザー顕微鏡による測定では、粗化処理面の上からレーザー光が照射される。このとき、粗化粒子１０ａに遮られることによってレーザー光が入射できない領域Ｎが存在する。この領域Ｎに起因して、レーザー顕微鏡を用いた粗化処理面の測定では、粗化粒子１０ａのくびれ形状等の特徴を正しく評価することが困難となりうる。この問題は、優れた伝送特性と高い回路密着性とを両立する微小な粗化形状を追求する場合に顕著となる。また、従来技術において、三次元的にサンプルを評価する手法も検討されているが、優れた伝送特性と高いシェア強度とを両立可能な評価手法として十分なものとはいえない。これに対して、本発明では、粗化粒子の平均高さ、及び球状粒子の割合に着目し、粗化処理銅箔を三次元的に評価してこれらをそれぞれ適切な範囲に制御することで、銅張積層板又はプリント配線板に用いられた場合に、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。
On the other hand, in the conventional technology, a laser microscope was used to evaluate the roughened shape, but this method has limitations in correctly evaluating the characteristics of minute roughened shapes. FIG. 4 schematically shows an example of measurement of the roughened surface using a laser microscope. As shown in FIG. 4, in the measurement with a laser microscope, a laser beam is irradiated from above the roughened surface. At this time, there is a region N where the laser beam cannot enter because it is blocked by the roughening particles 10a. Due to this region N, it may be difficult to correctly evaluate the features such as the constricted shape of the roughened particles 10a in the measurement of the roughened surface using a laser microscope. This problem becomes significant when pursuing a fine roughened shape that achieves both excellent transmission characteristics and high circuit adhesion. In addition, in the prior art, a method of three-dimensionally evaluating a sample has been studied, but it cannot be said to be sufficient as an evaluation method capable of achieving both excellent transmission characteristics and high shear strength. On the other hand, in the present invention, by focusing on the average height of roughened particles and the proportion of spherical particles, the roughened copper foil is evaluated three-dimensionally and these are controlled within appropriate ranges. When used in copper-clad laminates or printed wiring boards, it can achieve both excellent transmission characteristics and high shear strength.
粗化粒子の平均高さは７０ｎｍ以下であり、好ましくは２０ｎｍ以上７０ｎｍ以下、より好ましくは３０ｎｍ以上７０ｎｍ以下、さらに好ましくは５０ｎｍ以上７０ｎｍ以下、特に好ましくは６０ｎｍ以上７０ｎｍ以下である。こうすることで、高いシェア強度でありながらも、優れた伝送特性を実現することができる。
The average height of the roughened particles is 70 nm or less, preferably 20 nm or more and 70 nm or less, more preferably 30 nm or more and 70 nm or less, even more preferably 50 nm or more and 70 nm or less, and particularly preferably 60 nm or more and 70 nm or less. By doing so, it is possible to achieve excellent transmission characteristics while maintaining high shear strength.
粗化粒子に占める球状粒子の割合は３０％以上であり、好ましくは３０％以上９０％以下、より好ましくは３０％以上７０％以下、さらに好ましくは３０％以上５０％以下、特に好ましくは３５％以上４５％以下である。こうすることで、優れた伝送特性でありながらも、高いシェア強度を実現することができる。
The proportion of spherical particles in the roughened particles is 30% or more, preferably 30% or more and 90% or less, more preferably 30% or more and 70% or less, still more preferably 30% or more and 50% or less, particularly preferably 35%. 45% or less. By doing so, it is possible to achieve high shear strength while having excellent transmission characteristics.
粗化粒子における底面積比の平均値は３．０以下であるのが好ましく、より好ましくは２．０以上３．０以下である。近年、電子機器端末等の軽薄短小化に伴い、回路には更なる細線化も求められているところ、粗化粒子における底面積比の平均値を上記範囲内とすることで、銅箔のエッチング性を向上することができ、細線回路の形成に有利なものとなる。
The average value of the bottom area ratio of the roughened particles is preferably 3.0 or less, more preferably 2.0 or more and 3.0 or less. In recent years, as electronic device terminals have become lighter, thinner, and smaller, circuits are required to have even finer wires. It is possible to improve the properties, which is advantageous for the formation of fine line circuits.
底面積比の平均値を制御することでエッチング性が向上するメカニズムは必ずしも定かではないが、要因の一つとして以下のようなものが挙げられる。すなわち、銅張積層板等に対してエッチングにより回路形成を行う際には、表面の銅箔のみならず基板樹脂に食い込ませた粗化粒子も除去する必要がある。この際、粗化粒子のくびれ部分が細すぎることで、樹脂基板の粗化粒子を食い込ませた部分にエッチング液が浸入しにくくなり、残留銅を無くすために多くのエッチング量を要してしまうことが起こりうる。この点、粗化粒子における底面積比の平均値が上記範囲内であると、エッチング液が浸入するのに好都合なくびれ形状を有するものとなり、粗化粒子を除去する際に必要なエッチング量を低減することができると考えられる。
Although the mechanism by which the etchability is improved by controlling the average value of the bottom area ratio is not necessarily clear, one of the factors is as follows. That is, when forming a circuit on a copper-clad laminate or the like by etching, it is necessary to remove not only the copper foil on the surface but also the roughened particles that have penetrated into the substrate resin. At this time, since the constricted portion of the roughening particles is too thin, it becomes difficult for the etchant to penetrate into the portion of the resin substrate in which the roughening particles have been bitten, and a large amount of etching is required to eliminate the residual copper. things can happen. In this regard, if the average value of the bottom area ratio of the roughened particles is within the above range, the roughened particles will have a constricted shape that is convenient for the penetration of the etchant, and the amount of etching required to remove the roughened particles will be reduced. can be reduced.
粗化処理銅箔の厚さは特に限定されないが、０．１μｍ以上３５μｍ以下が好ましく、より好ましくは０．５μｍ以上５．０μｍ以下、さらに好ましくは１．０μｍ以上３．０μｍ以下である。なお、粗化処理銅箔は、通常の銅箔の表面に粗化処理を行ったものに限らず、キャリア付銅箔の銅箔表面に粗化処理を行ったものであってもよい。ここで、粗化処理銅箔の厚さは、粗化処理面の表面に形成された粗化粒子の高さを含まない厚さ（粗化処理銅箔を構成する銅箔自体の厚さ）である。上記範囲の厚さを有する銅箔のことを、極薄銅箔ということがある。
Although the thickness of the roughened copper foil is not particularly limited, it is preferably 0.1 μm or more and 35 μm or less, more preferably 0.5 μm or more and 5.0 μm or less, and still more preferably 1.0 μm or more and 3.0 μm 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. Here, 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.
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。すなわち、粗化処理銅箔は両側に粗化処理面を有するものであってもよいし、一方の側にのみ粗化処理面を有するものであってもよい。粗化処理面は、複数の粗化粒子を備えてなり、これら複数の粗化粒子はそれぞれ銅粒子からなるのが好ましい。銅粒子は金属銅からなるものであってもよいし、銅合金からなるものであってもよい。
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. It is preferable that the roughened surface comprises a plurality of roughening particles, and each of the plurality of roughening particles consists of copper particles. The copper particles may consist of metallic copper, or may consist of a copper alloy.
粗化処理面を形成するための粗化処理は、銅箔の上に銅又は銅合金で粗化粒子を形成することにより好ましく行うことができる。この粗化処理は、３段階のめっき工程を経るめっき手法に従って行われるのが好ましい。この場合、１段階目のめっき工程では、銅濃度５ｇ／Ｌ以上１５ｇ／Ｌ以下、及び硫酸濃度２００ｇ／Ｌ以上２５０ｇ／Ｌ以下の硫酸銅溶液を用いて、液温２５℃以上４５℃以下、電流密度２Ａ／ｄｍ２以上４Ａ／ｄｍ２以下のめっき条件で電着を行うのが好ましい。特に、１段階目のめっき工程は、２つの槽を用いて合計２回行うのが好ましい。２段階目のめっき工程では、銅濃度６０ｇ／Ｌ以上８０ｇ／Ｌ以下、及び硫酸濃度２００ｇ／Ｌ以上２６０ｇ／Ｌ以下の硫酸銅溶液を用いて、液温４５℃以上５５℃以下、電流密度１０Ａ／ｄｍ２以上１５Ａ／ｄｍ２以下のめっき条件で電着を行うのが好ましい。３段階目のめっき工程では、銅濃度５ｇ／Ｌ以上２０ｇ／Ｌ以下、硫酸濃度６０ｇ／Ｌ以上９０ｇ／Ｌ以下、塩素濃度２０ｍｇ／Ｌ以上４０ｍｇ／Ｌ以下、及び９－フェニルアクリジン（９ＰＡ）濃度１００ｍｇ／Ｌ以上２００ｍｇ／Ｌ以下の硫酸銅溶液を用いて、液温２５℃以上３５℃以下、電流密度３０Ａ／ｄｍ２以上６０Ａ／ｄｍ２以下のめっき条件で電着を行うのが好ましい。２段階目及び３段階目の各めっき工程は、２つの槽を用いて合計２回行ってもよいが、合計１回で完了させるのが好ましい。このようなめっき工程を経ることで、上述した表面パラメータを満足するのに好都合なコブを処理表面に形成しやすくなる。
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. In this case, in the first plating step, 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. In particular, the first-stage plating process is preferably performed twice in total using two tanks. In the second plating step, 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. In the third-stage plating process, 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, and the 9-phenylacridine (9PA) concentration. Electrodeposition 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.
所望により、粗化処理銅箔は防錆処理が施され、防錆処理層が形成されたものであってもよい。防錆処理は、亜鉛を用いためっき処理を含むのが好ましい。亜鉛を用いためっき処理は、亜鉛めっき処理及び亜鉛合金めっき処理のいずれであってもよく、亜鉛合金めっき処理は亜鉛－ニッケル合金処理が特に好ましい。亜鉛－ニッケル合金処理は少なくともＮｉ及びＺｎを含むめっき処理であればよく、Ｓｎ、Ｃｒ、Ｃｏ、Ｍｏ等の他の元素をさらに含んでいてもよい。亜鉛－ニッケル合金めっきにおけるＮｉ／Ｚｎ付着比率は、質量比で、１．２以上１０以下が好ましく、より好ましくは２以上７以下、さらに好ましくは２．７以上４以下である。また、防錆処理はクロメート処理をさらに含むのが好ましく、このクロメート処理は亜鉛を用いためっき処理の後に、亜鉛を含むめっきの表面に行われるのがより好ましい。こうすることで防錆性をさらに向上させることができる。特に好ましい防錆処理は、亜鉛－ニッケル合金めっき処理とその後のクロメート処理との組合せである。
If desired, 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. In addition, 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. By doing so, the rust resistance can be further improved. A particularly preferred antirust treatment is a combination of zinc-nickel alloy plating treatment and subsequent chromate treatment.
所望により、粗化処理銅箔は表面にシランカップリング剤処理が施され、シランカップリング剤層が形成されたものであってもよい。これにより耐湿性、耐薬品性及び接着剤等との密着性等を向上することができる。シランカップリング剤層は、シランカップリング剤を適宜希釈して塗布し、乾燥させることにより形成することができる。シランカップリング剤の例としては、４－グリシジルブチルトリメトキシシラン、３－グリシドキシプロピルトリメトキシシラン等のエポキシ官能性シランカップリング剤、又は３－アミノプロピルトリメトキシシラン、Ｎ－（２－アミノエチル）－３－アミノプロピルトリメトキシシラン、Ｎ－３－（４－（３－アミノプロポキシ）ブトキシ）プロピル－３－アミノプロピルトリメトキシシラン、Ｎ－フェニル－３－アミノプロピルトリメトキシシラン等のアミノ官能性シランカップリング剤、又は３－メルカプトプロピルトリメトキシシラン等のメルカプト官能性シランカップリング剤又はビニルトリメトキシシラン、ビニルフェニルトリメトキシシラン等のオレフィン官能性シランカップリング剤、又は３－メタクリロキシプロピルトリメトキシシラン等のアクリル官能性シランカップリング剤、又はイミダゾールシラン等のイミダゾール官能性シランカップリング剤、又はトリアジンシラン等のトリアジン官能性シランカップリング剤等が挙げられる。
If desired, the surface of the roughened copper foil may be treated with a silane coupling agent to form a silane coupling agent layer. As a result, moisture resistance, chemical resistance, adhesion to adhesives and the like can be improved. The silane coupling agent layer can be formed by appropriately diluting the silane coupling agent, coating it, and drying it. Examples of 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. 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.
上述した理由から、粗化処理銅箔は、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ることが好ましく、より好ましくは防錆処理層及びシランカップリング剤層の両方を備える。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が形成されている場合、本明細書における粗化粒子の平均高さ、球状粒子の割合、及び底面積比の平均値の各数値は、防錆処理層及び／又はシランカップリング剤処理層が形成された後の粗化処理銅箔を測定及び解析して得られる数値を意味するものとする。防錆処理層及びシランカップリング剤層は、粗化処理銅箔の粗化処理面側のみならず、粗化処理面が形成されていない側に形成されてもよい。
For the reasons described above, 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. Have both. When the roughened surface is provided with an antirust treatment layer and/or a silane coupling agent layer, each of the average height of roughened particles, the proportion of spherical particles, and the average base area ratio in the present specification The numerical value means a numerical value obtained by measuring and analyzing the roughened copper foil after the antirust treatment layer and/or the silane coupling agent treatment layer has been formed. 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.
キャリア付銅箔
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.
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.
キャリアは、粗化処理銅箔を支持してそのハンドリング性を向上させるための支持体であり、典型的なキャリアは金属層を含む。このようなキャリアの例としては、アルミニウム箔、銅箔、ステンレス（ＳＵＳ）箔、表面を銅等でメタルコーティングした樹脂フィルムやガラス等が挙げられ、好ましくは、銅箔である。銅箔は圧延銅箔及び電解銅箔のいずれであってもよいが、好ましくは電解銅箔である。キャリアの厚さは典型的には２５０μｍ以下であり、好ましくは７μｍ以上２００μｍ以下である。
A carrier is a support for supporting the roughened copper foil to improve its handling properties, and 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 μm or less, preferably 7 μm or more and 200 μm or less.
キャリアの剥離層側の面は平滑であるのが好ましい。すなわち、キャリア付銅箔の製造プロセスにおいて、キャリアの剥離層側の面には（粗化処理を行う前の）極薄銅箔が形成されることになる。本発明の粗化処理銅箔をキャリア付銅箔の形態で用いる場合、粗化処理銅箔は、このような極薄銅箔に対して粗化処理を施すことにより得ることができる。したがって、キャリアの剥離層側の面を平滑にしておくことで、極薄銅箔の外側の面も平滑にすることができ、この極薄銅箔の平滑面に粗化処理を施すことで、上記所定範囲内の粗化粒子の平均高さ等を有する粗化処理面を実現しやすくなる。キャリアの剥離層側の面を平滑にするには、例えばキャリアを電解製箔する際に用いる陰極の表面を所定の番手のバフで研磨して表面粗さを調整することにより行うことができる。すなわち、こうして調整された陰極の表面プロファイルがキャリアの電極面に転写され、このキャリアの電極面上に剥離層を介して極薄銅箔を形成することで、極薄銅箔の外側の面に上述した粗化処理面を実現しやすい平滑な表面状態を付与することができる。好ましいバフの番手は＃２０００以上＃３０００以下であり、より好ましくは＃２０００以上＃２５００以下である。＃２０００以上＃２５００以下の番手のバフで研磨した陰極を用いて得られるキャリアの電極面は、平滑箔析出面に比べ、軽度なうねりがあるため密着性の確保ができるとともに平滑性も確保でき、高い密着性と優れた伝送特性とをよりバランスよく実現することが可能となる。また、極薄銅箔をより平滑なものとし、得られる粗化処理銅箔の各種表面パラメータを上記範囲により制御しやすくなるという観点より、添加剤を含有した電解液を用いて電解製箔したキャリアの析出面側をキャリアの剥離層側の面としてもよい。
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. When 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 an average height of roughened particles within the above-described 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. In addition, from the viewpoint of making the ultra-thin copper foil smoother and making it easier to control various surface parameters of the resulting roughened copper foil within the above range, 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.
剥離層は、キャリアの引き剥がし強度を弱くし、該強度の安定性を担保し、さらには高温でのプレス成形時にキャリアと銅箔の間で起こりうる相互拡散を抑制する機能を有する層である。剥離層は、キャリアの一方の面に形成されるのが一般的であるが、両面に形成されてもよい。剥離層は、有機剥離層及び無機剥離層のいずれであってもよい。有機剥離層に用いられる有機成分の例としては、窒素含有有機化合物、硫黄含有有機化合物、カルボン酸等が挙げられる。窒素含有有機化合物の例としては、トリアゾール化合物、イミダゾール化合物等が挙げられ、中でもトリアゾール化合物は剥離性が安定し易い点で好ましい。トリアゾール化合物の例としては、１，２，３－ベンゾトリアゾール、カルボキシベンゾトリアゾール、Ｎ’，Ｎ’－ビス（ベンゾトリアゾリルメチル）ユリア、１Ｈ－１，２，４－トリアゾール、３－アミノ－１Ｈ－１，２，４－トリアゾール等が挙げられる。硫黄含有有機化合物の例としては、メルカプトベンゾチアゾール、チオシアヌル酸、２－ベンズイミダゾールチオール等が挙げられる。カルボン酸の例としては、モノカルボン酸、ジカルボン酸等が挙げられる。一方、無機剥離層に用いられる無機成分の例としては、Ｎｉ、Ｍｏ、Ｃｏ、Ｃｒ、Ｆｅ、Ｔｉ、Ｗ、Ｐ、Ｚｎ、クロメート処理膜等が挙げられる。なお、剥離層の形成はキャリアの少なくとも一方の表面に剥離層成分含有溶液を接触させ、剥離層成分をキャリアの表面に固定させること等により行えばよい。キャリアを剥離層成分含有溶液に接触させる場合、この接触は、剥離層成分含有溶液への浸漬、剥離層成分含有溶液の噴霧、剥離層成分含有溶液の流下等により行えばよい。その他、蒸着やスパッタリング等による気相法で剥離層成分を被膜形成する方法も採用可能である。また、剥離層成分のキャリア表面への固定は、剥離層成分含有溶液の吸着や乾燥、剥離層成分含有溶液中の剥離層成分の電着等により行えばよい。剥離層の厚さは、典型的には１ｎｍ以上１μｍ以下であり、好ましくは５ｎｍ以上５００ｎｍ以下である。
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. Examples of 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. Examples of triazole compounds include 1,2,3-benzotriazole, carboxybenzotriazole, N',N'-bis(benzotriazolylmethyl)urea, 1H-1,2,4-triazole, 3-amino- 1H-1,2,4-triazole and the like. Examples of sulfur-containing organic compounds include mercaptobenzothiazole, thiocyanuric acid, 2-benzimidazolethiol, and the like. Examples of carboxylic acids include monocarboxylic acids, dicarboxylic acids, and the like. On the other hand, 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. When the carrier is brought into contact with the release layer component-containing solution, 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. In addition, it is also possible to adopt a method of forming a coating of the peeling layer component by a vapor phase method such as vapor deposition or sputtering. 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 μm or less, preferably 5 nm or more and 500 nm or less.
所望により、剥離層とキャリア及び／又は粗化処理銅箔の間に他の機能層を設けてもよい。そのような他の機能層の例としては補助金属層が挙げられる。補助金属層はニッケル及び／又はコバルトからなるのが好ましい。このような補助金属層をキャリアの表面側及び／又は粗化処理銅箔の表面側に形成することで、高温又は長時間の熱間プレス成形時にキャリアと粗化処理銅箔の間で起こりうる相互拡散を抑制し、キャリアの引き剥がし強度の安定性を担保することができる。補助金属層の厚さは、０．００１μｍ以上３μｍ以下とするのが好ましい。
If desired, another functional layer may be provided between the release layer and the carrier and/or the roughened copper foil. Examples of such other functional 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 μm or more and 3 μm or less.
銅張積層板
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、上記粗化処理銅箔又は上記キャリア付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又はキャリア付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 or the carrier-attached copper foil. By using the roughened copper foil or the carrier-attached copper foil of the present invention, both excellent transmission characteristics and high shear strength can be achieved in the processing of a copper-clad laminate. 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、上記粗化処理銅箔又は上記キャリア付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又はキャリア付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 or the carrier-attached copper foil. By using the roughened copper foil or the carrier-attached copper foil of the present invention, both excellent transmission characteristics and high shear strength can be achieved in the processing of a copper-clad laminate. 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.
プリント配線板
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、上記粗化処理銅箔又は上記キャリア付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又はキャリア付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 or the carrier-attached copper foil. By using the roughened copper foil or the carrier-attached 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.
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、上記粗化処理銅箔又は上記キャリア付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又はキャリア付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 or the carrier-attached copper foil. By using the roughened copper foil or the carrier-attached 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.
本発明を以下の例によってさらに具体的に説明する。
The present invention will be explained more specifically by the following examples.
例１～３
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 1-3
A copper foil with a carrier provided with a roughened copper foil was produced as follows.
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 1-3
A copper foil with a carrier provided with a roughened copper foil was produced as follows.
（１）キャリアの準備
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
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
（２）剥離層の形成
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.
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.
（３）補助金属層の形成
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.
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.
（４）極薄銅箔の形成
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
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
（５）粗化処理
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.
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.
一方、例３については２段階の粗化処理を行った。この２段階の粗化処理は、極薄銅箔の上に微細銅粒を析出付着させる焼けめっき工程と、この微細銅粒の脱落を防止するための被せめっき工程とから構成される。焼けめっき工程では、銅濃度１０ｇ／Ｌ及び硫酸濃度２００ｇ／Ｌの酸性硫酸銅溶液に、表１に示される濃度となるようにカルボキシベンゾトリアゾール（ＣＢＴＡ）を添加し、表１に示される電流密度及び液温で粗化処理を行った。その後の被せめっき工程では、銅濃度７０ｇ／Ｌ及び硫酸濃度２４０ｇ／Ｌの酸性硫酸銅溶液を用いて、液温５２℃及び表１に示される電流密度の平滑めっき条件で電着を行った。
On the other hand, for Example 3, a two-step roughening treatment was 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. In the burnt plating step, 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. And the roughening treatment was performed at liquid temperature. In the subsequent overplating step, 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.
（６）防錆処理
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 ofpH 12 and current density 1 A/dm 2 .
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
（７）シランカップリング剤処理
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.
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.
例４（比較）
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 4 (Comparison)
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.
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 4 (Comparison)
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.
（電解銅箔の準備）
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
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
例５（比較）
極薄銅箔に対して粗化処理を行わなかったこと以外は、例１と同様にしてキャリア付銅箔の作製を行った。 Example 5 (Comparison)
A carrier-attached copper foil was produced in the same manner as in Example 1, except that the ultra-thin copper foil was not subjected to roughening treatment.
極薄銅箔に対して粗化処理を行わなかったこと以外は、例１と同様にしてキャリア付銅箔の作製を行った。 Example 5 (Comparison)
A carrier-attached copper foil was produced in the same manner as in Example 1, except that the ultra-thin copper foil was not subjected to roughening treatment.
評価
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.
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.
（ａ）粗化処理面の三次元画像解析パラメータ
粗化処理銅箔又はキャリア付銅箔の粗化処理面（例５については極薄銅箔側の表面）に対して、三次元画像解析を行うことにより、粗化粒子の平均高さ、球状粒子の割合、及び底面積比の平均値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 Three-dimensional image analysis is performed on the roughened surface of the roughened copper foil or the copper foil with a carrier (for example 5, the surface on the ultra-thin copper foil side). By doing so, the average height of the roughening particles, the ratio of spherical particles, and the average value of the ratio of the base area were calculated. The specific procedure is as follows.
粗化処理銅箔又はキャリア付銅箔の粗化処理面（例５については極薄銅箔側の表面）に対して、三次元画像解析を行うことにより、粗化粒子の平均高さ、球状粒子の割合、及び底面積比の平均値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 Three-dimensional image analysis is performed on the roughened surface of the roughened copper foil or the copper foil with a carrier (for example 5, the surface on the ultra-thin copper foil side). By doing so, the average height of the roughening particles, the ratio of spherical particles, and the average value of the ratio of the base area were calculated. The specific procedure is as follows.
（ａ－１）３Ｄ－ＳＥＭ観察
ＦＩＢ－ＳＥＭ装置（カールツァイス社製、Ｃｒｏｓｓｂｅａｍ５４０、ＳＥＭ及びＦＩＢ同時制御：Ａｔｌａｓ Ｅｎｇｉｎｅ ｖ５．５．３）を用いて、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５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５ｎｍずつ平行移動させながら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 Using a FIB-SEM device (manufactured by Carl Zeiss, Crossbeam540, SEM and FIB simultaneous control: Atlas Engine v5.5.3), three-dimensional shape data is obtained under the following measurement conditions. did As shown in FIG. 5 , this three-dimensional shape data is acquired with the x-axis and z-axis being the in-plane directions of the roughenedcopper foil 10 and the y-axis being the thickness direction of the roughened copper foil 10. After defining, acquire a cross-sectional image of the roughened copper foil 10 on a slice plane S parallel to the xy plane, and acquire a cross-sectional image while translating this slice plane by 5 nm in the z-axis direction. I went by. In addition, although observation was performed under the following conditions this time, the observation conditions can be appropriately selected or changed depending on the state of the apparatus (model, etc.).
ＦＩＢ－ＳＥＭ装置（カールツァイス社製、Ｃｒｏｓｓｂｅａｍ５４０、ＳＥＭ及びＦＩＢ同時制御：Ａｔｌａｓ Ｅｎｇｉｎｅ ｖ５．５．３）を用いて、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５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５ｎｍずつ平行移動させながら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 Using a FIB-SEM device (manufactured by Carl Zeiss, Crossbeam540, SEM and FIB simultaneous control: Atlas Engine v5.5.3), three-dimensional shape data is obtained under the following measurement conditions. did As shown in FIG. 5 , this three-dimensional shape data is acquired with the x-axis and z-axis being the in-plane directions of the roughened
＜ＳＥＭ条件＞
‐加速電圧：１．０ｋＶ
‐Ｗｏｒｋｉｎｇ ｄｉｓｔａｎｃｅ：５ｍｍ
‐Ｔｉｌｔ：５４°（ＳＥＭ像のＴｉｌｔ補正あり）
‐検出器：ＳＥＳＩ検出器
‐Ｃｏｌｕｍｎ ｍｏｄｅ：Ｈｉｇｈ ｒｅｓｏｌｕｔｉｏｎ
‐Ｆｉｅｌｄ ｏｆ ｖｉｅｗ：ｘ＝３．２μｍ（ｙは任意に設定）
＜ＦＩＢ条件＞
‐加速電圧：３０ｋＶ
‐スライス厚：５ｎｍ（スライス面Ｓの間隔）
‐ボクセルサイズの設定：
ＦＩＢ－ＳＥＭ装置の測定条件に設定したいボクセルサイズ（ｘ、ｙ、ｚ）＝（３ｎｍ、３ｎｍ、５ｎｍ）を入力してボクセルサイズを設定した。このとき、ｘ、ｙは、画素サイズとして３ｎｍを入力した。また、ｚはスライス厚に５ｎｍを入力した。 <SEM conditions>
- acceleration voltage: 1.0 kV
-Working distance: 5mm
-Tilt: 54° (with SEM image tilt correction)
-Detector: SESI detector -Column mode: High resolution
-Field of view: x = 3.2 μm (y is set arbitrarily)
<FIB conditions>
- acceleration voltage: 30 kV
- Slice thickness: 5 nm (interval between slice planes S)
- Voxel size setting:
The voxel size was set by inputting the voxel size (x, y, z)=(3 nm, 3 nm, 5 nm) to be set in the measurement conditions of the FIB-SEM device. At this time, 3 nm was input as the pixel size for x and y. For z, 5 nm was input as the slice thickness.
‐加速電圧：１．０ｋＶ
‐Ｗｏｒｋｉｎｇ ｄｉｓｔａｎｃｅ：５ｍｍ
‐Ｔｉｌｔ：５４°（ＳＥＭ像のＴｉｌｔ補正あり）
‐検出器：ＳＥＳＩ検出器
‐Ｃｏｌｕｍｎ ｍｏｄｅ：Ｈｉｇｈ ｒｅｓｏｌｕｔｉｏｎ
‐Ｆｉｅｌｄ ｏｆ ｖｉｅｗ：ｘ＝３．２μｍ（ｙは任意に設定）
＜ＦＩＢ条件＞
‐加速電圧：３０ｋＶ
‐スライス厚：５ｎｍ（スライス面Ｓの間隔）
‐ボクセルサイズの設定：
ＦＩＢ－ＳＥＭ装置の測定条件に設定したいボクセルサイズ（ｘ、ｙ、ｚ）＝（３ｎｍ、３ｎｍ、５ｎｍ）を入力してボクセルサイズを設定した。このとき、ｘ、ｙは、画素サイズとして３ｎｍを入力した。また、ｚはスライス厚に５ｎｍを入力した。 <SEM conditions>
- acceleration voltage: 1.0 kV
-Working distance: 5mm
-Tilt: 54° (with SEM image tilt correction)
-Detector: SESI detector -Column mode: High resolution
-Field of view: x = 3.2 μm (y is set arbitrarily)
<FIB conditions>
- acceleration voltage: 30 kV
- Slice thickness: 5 nm (interval between slice planes S)
- Voxel size setting:
The voxel size was set by inputting the voxel size (x, y, z)=(3 nm, 3 nm, 5 nm) to be set in the measurement conditions of the FIB-SEM device. At this time, 3 nm was input as the pixel size for x and y. For z, 5 nm was input as the slice thickness.
（ａ－２）３Ｄ－ＳＥＭ画像解析
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軸の解析長さが２４００ｎｍ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、解析領域は粗化処理銅箔１０を平面視した場合のｘ－ｚ面の大きさを２４００ｎｍ×２４００ｎｍとし、ｙ方向の長さは粗化処理の解析が可能な任意の長さとした。さらに、図６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.), the drift was corrected so that the analysis length of the z-axis was 2400 nm or more. The slice image after drift correction is three-dimensionally reconstructed using the three-dimensional image analysis software "ExFact VR (version 2.2)" (manufactured by Japan Visual Science Co., Ltd.), and the analysis area is the roughenedcopper foil 10. The size of the xz plane in plan view was set to 2400 nm×2400 nm, and the length in the y direction was set to an arbitrary length that allows analysis of the roughening treatment. Furthermore, as shown in FIG. 6, after rotating the axis so that the roughened surface becomes the xy plane, image analysis is performed by "foil Analysis (version 1.0)" (manufactured by Nippon Visual Science Co., Ltd.). As a result, various data on the roughened surface were obtained as follows.
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軸の解析長さが２４００ｎｍ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、解析領域は粗化処理銅箔１０を平面視した場合のｘ－ｚ面の大きさを２４００ｎｍ×２４００ｎｍとし、ｙ方向の長さは粗化処理の解析が可能な任意の長さとした。さらに、図６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.), the drift was corrected so that the analysis length of the z-axis was 2400 nm or more. The slice image after drift correction is three-dimensionally reconstructed using the three-dimensional image analysis software "ExFact VR (version 2.2)" (manufactured by Japan Visual Science Co., Ltd.), and the analysis area is the roughened
三次元画像解析ソフトウェア「ｆｏｉｌ Ａｎａｌｙｓｉｓ（バージョン１.０）」による画像解析では、マトリクスサイズを７７と設定した。そして、解析によって生成される「ｉｃｈｉｊｉＢｇ」フォルダ内のエクセルデータを用いて、下記に示す各種三次元画像解析パラメータの計算を行った。なお、上記解析ソフトウェアでは輝度値によって粒子や空隙等を分類しているため、エクセルデータにおける「ａｖｅｒａｇｅ＿ｂｒｉｇｈｔｎｅｓｓ」が１５０である凸部を粗化粒子とみなして計算対象とした。また、ノイズ除去のため、エクセルデータにおける「ｖｏｌｕｍｅ（ｖｏｘｅｌｓ）」が１０より大きいデータのみを使用することで、体積の小さい凸部を計算から除外した。
In the image analysis using the three-dimensional image analysis software "foil Analysis (version 1.0)", the matrix size was set to 77. Then, using the Excel data in the "ichijiBg" folder generated by the analysis, various three-dimensional image analysis parameters shown below were calculated. In addition, since the analysis software classifies particles, voids, and the like according to the brightness value, convex portions with an "average_brightness" of 150 in the Excel data are regarded as roughened particles and used as calculation targets. In order to remove noise, only data with "volume (voxels)" greater than 10 in the Excel data were used, thereby excluding convex portions with small volumes from the calculation.
＜粗化粒子の平均高さ＞
各凸部の「ｓｉｚｅ＿Ｚ（ｖｏｘｅｌｓ）」の数値を各粗化粒子の高さ（ボクセル数）とした。この数値にボクセルサイズの高さ（５ｎｍ）を掛け合わせることで、各粗化粒子の高さを算出し、その平均値を粗化粒子の平均高さとした。結果は表３に示されるとおりであった。 <Average height of roughening particles>
The numerical value of "size_Z (voxels)" of each convex part was made into the height (voxel number) of each roughening particle. By multiplying this numerical value by the height of the voxel size (5 nm), the height of each roughened particle was calculated, and the average value was taken as the average height of the roughened particles. The results were as shown in Table 3.
各凸部の「ｓｉｚｅ＿Ｚ（ｖｏｘｅｌｓ）」の数値を各粗化粒子の高さ（ボクセル数）とした。この数値にボクセルサイズの高さ（５ｎｍ）を掛け合わせることで、各粗化粒子の高さを算出し、その平均値を粗化粒子の平均高さとした。結果は表３に示されるとおりであった。 <Average height of roughening particles>
The numerical value of "size_Z (voxels)" of each convex part was made into the height (voxel number) of each roughening particle. By multiplying this numerical value by the height of the voxel size (5 nm), the height of each roughened particle was calculated, and the average value was taken as the average height of the roughened particles. The results were as shown in Table 3.
＜球状粒子の割合＞
各凸部における、長軸の長さＬを１．０としたときの短軸の長さＳ及び中軸の長さＭの各数値から、表２に示される基準に従って、各凸部が球状粒子、平たい粒子、及び細長い粒子の３種類の粒子のうち、いずれの粒子に相当するか分類を行った。なお、画素数が少ない等の理由で形状の判定（Ｓ、Ｍ、Ｌの算出）が不可能な凸部については、ノイズとして計算から除外した。 <Percentage of spherical particles>
From each numerical value of the length S of the short axis and the length M of the middle axis when the length L of the long axis is 1.0 in each convex part, according to the criteria shown in Table 2, each convex part is a spherical particle , flat particles, and elongated particles. Convex portions whose shape cannot be determined (calculation of S, M, and L) due to reasons such as a small number of pixels are excluded from the calculation as noise.
各凸部における、長軸の長さＬを１．０としたときの短軸の長さＳ及び中軸の長さＭの各数値から、表２に示される基準に従って、各凸部が球状粒子、平たい粒子、及び細長い粒子の３種類の粒子のうち、いずれの粒子に相当するか分類を行った。なお、画素数が少ない等の理由で形状の判定（Ｓ、Ｍ、Ｌの算出）が不可能な凸部については、ノイズとして計算から除外した。 <Percentage of spherical particles>
From each numerical value of the length S of the short axis and the length M of the middle axis when the length L of the long axis is 1.0 in each convex part, according to the criteria shown in Table 2, each convex part is a spherical particle , flat particles, and elongated particles. Convex portions whose shape cannot be determined (calculation of S, M, and L) due to reasons such as a small number of pixels are excluded from the calculation as noise.
分類された粒子のうち、球状粒子の個数ＮＳを、各粒子の個数の和（つまり球状粒子の個数ＮＳ、平たい粒子の個数ＮＦ及び細長い粒子の個数ＮＥの和）で割った値に、１００を乗じることにより（＝１００×ＮＳ／（ＮＳ＋ＮＦ＋ＮＥ））、球状粒子の割合を算出した。結果は表３に示されるとおりであった。
A value obtained by dividing the number of spherical particles N S among the classified particles by the sum of the numbers of each particle (that is, the sum of the number of spherical particles N S , the number of flat particles N F and the number of elongated particles N E ) was multiplied by 100 (=100× NS /( NS+NF+NE ) ) to calculate the percentage of spherical particles. The results were as shown in Table 3.
なお、三次元画像解析ソフトウェア「ｆｏｉｌ Ａｎａｌｙｓｉｓ（バージョン１.０）」による画像解析では、各凸部に対して、互いに直行する慣性主軸が設定され、それぞれの重心モーメントＳ、Ｍ、Ｌ（ただし、Ｓ≦Ｍ≦Ｌである）が算出される。そして、重心モーメントＬを１．０とした場合の重心モーメントＳの数値（比率）及び重心モーメントＭの数値（比率）がエクセルデータに表示される。つまり、重心モーメントＳ、Ｍ、Ｌがそれぞれ、短軸の長さＳ、中軸の長さＭ、長軸の長さＬに対応する。
In the image analysis using the three-dimensional image analysis software "foil Analysis (version 1.0)", the main axes of inertia that are perpendicular to each other are set for each convex part, and the respective center-of-gravity moments S, M, L (however, S≦M≦L) is calculated. Then, the numerical value (ratio) of the center-of-gravity moment S and the numerical value (ratio) of the center-of-gravity moment M when the center-of-gravity moment L is 1.0 are displayed in the Excel data. That is, the moments of gravity S, M, and L correspond to the length S of the short axis, the length M of the middle axis, and the length L of the long axis, respectively.
＜底面積比の平均値＞
各凸部における「ｓｕｒｆａｃｅ＿ｖｏｘｅｌｓ（ｖｏｘｅｌｓ）」の数値を各粗化粒子の底面を構成するボクセルのｘ－ｙ平面積値（すなわち底面積）とした。また、各凸部における「ｓｉｚｅ＿Ｘ（ｖｏｘｅｌｓ）」の数値を各粗化粒子におけるｘ軸方向の最大ボクセルのｘ値とし、「ｓｉｚｅ＿Ｙ（ｖｏｘｅｌｓ）」の数値をｙ軸方向の最大ボクセルのｙ値とした。そして、当該ｘ値及びｙ値の積を各粗化粒子の投射面積とした。各粗化粒子における底面積に対する投射面積の比を底面積比として求め、その平均値を算出した。結果は表３に示されるとおりであった。 <Average value of bottom area ratio>
The numerical value of “surface_voxels (voxels)” in each convex portion was defined as the xy plane area value (that is, the bottom area) of the voxels forming the bottom surface of each roughening particle. Also, the numerical value of "size_X (voxels)" in each convex portion is the x value of the maximum voxel in the x-axis direction for each roughening particle, and the numerical value of "size_Y (voxels)" is the y value of the maximum voxel in the y-axis direction. did. Then, the product of the x value and the y value was defined as the projected area of each roughening particle. The ratio of the projected area to the bottom area of each roughening particle was determined as the bottom area ratio, and the average value was calculated. The results were as shown in Table 3.
各凸部における「ｓｕｒｆａｃｅ＿ｖｏｘｅｌｓ（ｖｏｘｅｌｓ）」の数値を各粗化粒子の底面を構成するボクセルのｘ－ｙ平面積値（すなわち底面積）とした。また、各凸部における「ｓｉｚｅ＿Ｘ（ｖｏｘｅｌｓ）」の数値を各粗化粒子におけるｘ軸方向の最大ボクセルのｘ値とし、「ｓｉｚｅ＿Ｙ（ｖｏｘｅｌｓ）」の数値をｙ軸方向の最大ボクセルのｙ値とした。そして、当該ｘ値及びｙ値の積を各粗化粒子の投射面積とした。各粗化粒子における底面積に対する投射面積の比を底面積比として求め、その平均値を算出した。結果は表３に示されるとおりであった。 <Average value of bottom area ratio>
The numerical value of “surface_voxels (voxels)” in each convex portion was defined as the xy plane area value (that is, the bottom area) of the voxels forming the bottom surface of each roughening particle. Also, the numerical value of "size_X (voxels)" in each convex portion is the x value of the maximum voxel in the x-axis direction for each roughening particle, and the numerical value of "size_Y (voxels)" is the y value of the maximum voxel in the y-axis direction. did. Then, the product of the x value and the y value was defined as the projected area of each roughening particle. The ratio of the projected area to the bottom area of each roughening particle was determined as the bottom area ratio, and the average value was calculated. The results were as shown in Table 3.
（ｂ）シェア強度
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（例５については極薄銅箔側の表面）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, the roughened surface (the surface on the ultrathin copper foil side in Example 5) is in contact with the surface of the inner layer substrate via a prepreg (GHPL-830NSF, manufactured by Mitsubishi Gas Chemical Co., Ltd., thickness 30 μm). A carrier-attached copper foil or a roughened copper foil was laminated on the substrate 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.
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（例５については極薄銅箔側の表面）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, the roughened surface (the surface on the ultrathin copper foil side in Example 5) is in contact with the surface of the inner layer substrate via a prepreg (GHPL-830NSF, manufactured by Mitsubishi Gas Chemical Co., Ltd., thickness 30 μm). A carrier-attached copper foil or a roughened copper foil was laminated on the substrate 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.
上述の評価用積層体にドライフィルムを張り合わせ、露光及び現像を行った。現像されたドライフィルムでマスキングされた積層体にパターンめっきで銅層を析出させた後、ドライフィルムを剥離した。硫酸－過酸化水素系エッチング液で表出している銅部分をエッチングし、高さ１５μｍ、幅１４μｍ、長さ１５０μｍのシェア強度測定用サンプルを作製した。接合強度試験機（Ｎｏｒｄｓｏｎ ＤＡＧＥ社製 ４０００Ｐｌｕｓ Ｂｏｎｄｔｅｓｔｅｒ）を用い、シェア強度測定用サンプルを横から押し倒した際のシェア強度を測定した。このとき、テスト種類は破壊試験とし、テスト高さ５μｍ、降下スピード０．０５ｍｍ／ｓ、テストスピード２００μｍ／ｓ、ツール移動量０．０３ｍｍ、破壊認識点１０％の条件で測定を行った。得られたシェア強度を以下の基準で格付け評価し、評価Ａ及びＢを合格と判定した。結果は表２に示されるとおりであった。
＜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
＜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
（ｃ）伝送特性
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（例５については極薄銅箔側の表面）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 superimposed, and on both sides are roughened surfaces of carrier-attached copper foil or roughened copper foil (for example 5, ultra-thin The surface of the copper foil side) was brought into contact, and thermocompression bonding was performed at a temperature of 190° C. for 90 minutes using a vacuum press. 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.
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（例５については極薄銅箔側の表面）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 superimposed, and on both sides are roughened surfaces of carrier-attached copper foil or roughened copper foil (for example 5, ultra-thin The surface of the copper foil side) was brought into contact, and thermocompression bonding was performed at a temperature of 190° C. for 90 minutes using a vacuum press. 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.
得られた伝送特性測定用基板について、ネットワークアナライザー（Ａｇｉｌｅｎｔ社製、ＰＮＡ－Ｘ Ｎ５２４５Ａ）を用いて、回路の特性インピーダンスが５０Ωとなるパターンを選定し、５０ＧＨｚまでの伝送損失Ｓ２１（ｄＢ／ｃｍ）を測定した。得られた４５～５０ＧＨｚにおける伝送損失量の平均を算出し、その絶対値を以下の基準で格付け評価した。そして、伝送特性評価がＡ又はＢである場合に合格と判定した。結果は表２に示されるとおりであった。
＜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
＜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
（ｄ）回路形成性（エッチング性評価）
上記シェア強度と同様の手順で評価用積層体を作製した。この評価用積層体に対して硫酸－過酸化水素系エッチング液で０．２μｍずつエッチングを行った。計測は各エッチング後に光学顕微鏡（５００倍）で確認することにより行った。エッチングが進行し、評価用積層体を光学顕微鏡で観察した際に、基材樹脂が観察され始めたときを始点とし、表面の銅（粗化粒子を含む）が完全になくなったときを終点とした。そして、始点から終点までに要したエッチング量（深さ）を、粗化粒子のエッチング量とした。例えば、粗化粒子のエッチング量が０．４μｍということは、光学顕微鏡で基材樹脂が初めて観察された後、更に０．２μｍのエッチングを２回行ったところで、光学顕微鏡で残存銅が検出されなくなったことを意味する（すなわち０．２μｍ×２回＝０．４μｍ）。すなわち、この値が小さいほど少ない回数のエッチングで粗化粒子を除去できることを意味し、エッチング性が良好であることを意味する。得られた粗化粒子のエッチング量を以下の基準で格付け評価した。結果は表３に示されるとおりであった。
＜エッチング性評価基準＞
‐評価Ａ：粗化粒子のエッチング量が０．２μｍ以下
‐評価Ｂ：粗化粒子のエッチング量が０．２μｍを超え０．４μｍ以下
‐評価Ｃ：粗化粒子のエッチング量が０．４μｍ超 (d) circuit formability (evaluation of etching property)
A laminate for evaluation was produced in the same procedure as for the shear strength. This laminate for evaluation was etched with a sulfuric acid-hydrogen peroxide-based etchant by 0.2 μm. Measurements were made by checking with an optical microscope (500x) after each etching. When the etching progresses and the laminate for evaluation is observed with an optical microscope, the starting point is when the base resin begins to be observed, and the end point is when the copper (including roughening particles) on the surface is completely removed. did. The etching amount (depth) required from the start point to the end point was defined as the etching amount of the roughening particles. For example, if the etching amount of the roughened particles is 0.4 μm, after the base resin is first observed with an optical microscope, the remaining copper is detected with an optical microscope after 0.2 μm etching is performed twice. (ie 0.2 μm×2 times=0.4 μm). That is, a smaller value means that the roughening particles can be removed with a smaller number of etchings, and that the etchability is better. The etching amount of the obtained roughening particles was graded and evaluated according to the following criteria. The results were as shown in Table 3.
<Etching Evaluation Criteria>
-Evaluation A: Etched amount of roughening particles is 0.2 μm or less -Evaluation B: Etching amount of roughening particles is more than 0.2 μm and 0.4 μm or less -Evaluation C: Etching amount of roughening particles is more than 0.4 μm
上記シェア強度と同様の手順で評価用積層体を作製した。この評価用積層体に対して硫酸－過酸化水素系エッチング液で０．２μｍずつエッチングを行った。計測は各エッチング後に光学顕微鏡（５００倍）で確認することにより行った。エッチングが進行し、評価用積層体を光学顕微鏡で観察した際に、基材樹脂が観察され始めたときを始点とし、表面の銅（粗化粒子を含む）が完全になくなったときを終点とした。そして、始点から終点までに要したエッチング量（深さ）を、粗化粒子のエッチング量とした。例えば、粗化粒子のエッチング量が０．４μｍということは、光学顕微鏡で基材樹脂が初めて観察された後、更に０．２μｍのエッチングを２回行ったところで、光学顕微鏡で残存銅が検出されなくなったことを意味する（すなわち０．２μｍ×２回＝０．４μｍ）。すなわち、この値が小さいほど少ない回数のエッチングで粗化粒子を除去できることを意味し、エッチング性が良好であることを意味する。得られた粗化粒子のエッチング量を以下の基準で格付け評価した。結果は表３に示されるとおりであった。
＜エッチング性評価基準＞
‐評価Ａ：粗化粒子のエッチング量が０．２μｍ以下
‐評価Ｂ：粗化粒子のエッチング量が０．２μｍを超え０．４μｍ以下
‐評価Ｃ：粗化粒子のエッチング量が０．４μｍ超 (d) circuit formability (evaluation of etching property)
A laminate for evaluation was produced in the same procedure as for the shear strength. This laminate for evaluation was etched with a sulfuric acid-hydrogen peroxide-based etchant by 0.2 μm. Measurements were made by checking with an optical microscope (500x) after each etching. When the etching progresses and the laminate for evaluation is observed with an optical microscope, the starting point is when the base resin begins to be observed, and the end point is when the copper (including roughening particles) on the surface is completely removed. did. The etching amount (depth) required from the start point to the end point was defined as the etching amount of the roughening particles. For example, if the etching amount of the roughened particles is 0.4 μm, after the base resin is first observed with an optical microscope, the remaining copper is detected with an optical microscope after 0.2 μm etching is performed twice. (ie 0.2 μm×2 times=0.4 μm). That is, a smaller value means that the roughening particles can be removed with a smaller number of etchings, and that the etchability is better. The etching amount of the obtained roughening particles was graded and evaluated according to the following criteria. The results were as shown in Table 3.
<Etching Evaluation Criteria>
-Evaluation A: Etched amount of roughening particles is 0.2 μm or less -Evaluation B: Etching amount of roughening particles is more than 0.2 μm and 0.4 μm or less -Evaluation C: Etching amount of roughening particles is more than 0.4 μm
Claims (9)
- 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、前記粗化処理面が球状粒子を含む複数の粗化粒子を有しており、
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、前記粗化粒子の平均高さが７０ｎｍ以下であり、かつ、前記複数の粗化粒子に占める前記球状粒子の割合が３０％以上であり、
前記球状粒子は、前記粗化粒子に対して、互いに直行する長軸、中軸及び短軸を設定し、前記長軸の長さＬを１．０とした場合に、前記中軸の長さＭが０．３≦Ｍ≦１．０を満たし、かつ、前記短軸の長さＳが０．３≦Ｓ≦１．０を満たす粒子である、粗化処理銅箔。 A roughened copper foil having a roughened surface on at least one side, the roughened surface having a plurality of roughened particles including spherical particles,
When the image obtained using FIB-SEM on the roughened surface is subjected to three-dimensional image analysis, the average height of the roughened particles is 70 nm or less, and the plurality of roughened particles occupy The proportion of the spherical particles is 30% or more,
The spherical particles have a long axis, a middle axis and a short axis that are orthogonal to each other with respect to the roughened particles, and when the length L of the long axis is 1.0, the length M of the middle axis is A roughened copper foil, which is a particle that satisfies 0.3≦M≦1.0 and the minor axis length S satisfies 0.3≦S≦1.0. - 前記平均高さが２０ｎｍ以上７０ｎｍ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 average height is 20 nm or more and 70 nm or less.
- 前記球状粒子の割合が３０％以上９０％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 proportion of said spherical particles is 30% or more and 90% 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、ｚ軸が前記粗化処理面に対して垂直になり、かつ、ｘ－ｙ面が前記粗化処理面と平行になるようにｘ軸、ｙ軸及びｚ軸を割り当てて三次元画像解析して前記粗化粒子を複数のボクセルに分割した場合に、前記複数の粗化粒子は、底面積比の平均値が３．０以下であり、
前記底面積比は、各粗化粒子における底面積に対する投射面積の比であり、前記底面積は、前記各粗化粒子の底面を構成するボクセルのｘ－ｙ平面積値として定義され、前記投射面積は、前記各粗化粒子におけるｘ軸方向の最大ボクセルのｘ値及びｙ軸方向の最大ボクセルのｙ値の積として定義される、請求項１又は２に記載の粗化処理銅箔。 An image obtained using a FIB-SEM of the roughened surface is taken so that the z-axis is perpendicular to the roughened surface and the xy plane is parallel to the roughened surface. When the roughened particles are divided into a plurality of voxels by three-dimensional image analysis with the x-axis, y-axis, and z-axis assigned as above, the average value of the bottom area ratio of the plurality of roughened particles is 3. is 0 or less,
The base area ratio is the ratio of the projected area to the base area of each roughened particle, and the base area is defined as the xy plane area value of the voxel that constitutes the bottom surface of each roughened particle, and the projected 3. The roughened copper foil according to claim 1 or 2, wherein the area is defined as the product of the x-value of the largest voxel in the x-axis direction and the y-value of the largest voxel in the y-axis direction in each roughened particle. - 前記底面積比の平均値が２．０以上３．０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 average value of the bottom area ratio is 2.0 or more and 3.0 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に記載の粗化処理銅箔とを備えた、キャリア付銅箔。 A carrier-attached copper comprising a carrier, a release layer provided on the carrier, and the roughened copper foil according to claim 1 provided on the release layer with the roughened surface facing outward. foil.
- 請求項１又は２に記載の粗化処理銅箔又は請求項７に記載のキャリア付銅箔を備えた、銅張積層板。 A copper-clad laminate comprising the roughened copper foil according to claim 1 or 2 or the carrier-attached copper foil according to claim 7.
- 請求項１又は２に記載の粗化処理銅箔又は請求項７に記載のキャリア付銅箔を備えた、プリント配線板。
A printed wiring board comprising the roughened copper foil according to claim 1 or 2 or the carrier-attached copper foil according to claim 7.
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| CN202280036136.0A CN117337344A (en) | 2021-05-20 | 2022-05-18 | Roughened copper foil, copper foil with carrier, copper-clad laminate, and printed wiring board |
| KR1020237038695A KR20240009937A (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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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2014152352A (en) * | 2013-02-06 | 2014-08-25 | Sh Copper Products Corp | Composite copper foil and production method thereof |
| 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 |
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| CN107002265B (en) | 2015-01-22 | 2019-04-26 | 三井金属矿业株式会社 | Ultrathin copper foil and its manufacturing method with carrier |
| CN107429417B (en) * | 2015-03-31 | 2019-11-22 | 三井金属矿业株式会社 | Roughening treatment copper foil, band carrier copper foil, copper-clad laminated board and printed circuit 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 |
| CN112424399B (en) | 2018-08-10 | 2023-07-25 | 三井金属矿业株式会社 | Roughened copper foil, copper foil with carrier, copper-clad laminate, and printed wiring board |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014152352A (en) * | 2013-02-06 | 2014-08-25 | Sh Copper Products Corp | Composite copper foil and production method thereof |
| 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 |
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| KR20240009937A (en) | 2024-01-23 |
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