TW202302914A - Roughened copper foil, copper foil with carrier, copper-cladded laminate board, and printed wiring board - Google Patents
Roughened copper foil, copper foil with carrier, copper-cladded laminate board, and printed wiring board Download PDFInfo
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- TW202302914A TW202302914A TW111118883A TW111118883A TW202302914A TW 202302914 A TW202302914 A TW 202302914A TW 111118883 A TW111118883 A TW 111118883A TW 111118883 A TW111118883 A TW 111118883A TW 202302914 A TW202302914 A TW 202302914A
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- copper foil
- roughened
- peaks
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 245
- 239000011889 copper foil Substances 0.000 title claims abstract description 209
- 238000004458 analytical method Methods 0.000 claims abstract description 34
- 238000010191 image analysis Methods 0.000 claims abstract description 17
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 20
- 230000005540 biological transmission Effects 0.000 abstract description 38
- 238000004519 manufacturing process Methods 0.000 abstract description 14
- 238000012545 processing Methods 0.000 abstract description 8
- 239000010410 layer Substances 0.000 description 92
- 229910052802 copper Inorganic materials 0.000 description 38
- 239000010949 copper Substances 0.000 description 38
- 238000000034 method Methods 0.000 description 35
- 239000011347 resin Substances 0.000 description 35
- 229920005989 resin Polymers 0.000 description 35
- 238000007747 plating Methods 0.000 description 33
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 29
- 238000007788 roughening Methods 0.000 description 29
- 239000000243 solution Substances 0.000 description 24
- 238000011156 evaluation Methods 0.000 description 17
- 239000002245 particle Substances 0.000 description 15
- 239000000758 substrate Substances 0.000 description 15
- 230000008569 process Effects 0.000 description 14
- 239000007788 liquid Substances 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- 239000011888 foil Substances 0.000 description 12
- 238000005520 cutting process Methods 0.000 description 11
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- 239000002184 metal Substances 0.000 description 10
- 229910000365 copper sulfate Inorganic materials 0.000 description 9
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
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- 229910000990 Ni alloy Inorganic materials 0.000 description 7
- 239000000463 material Substances 0.000 description 7
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- 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
- 230000002378 acidificating effect Effects 0.000 description 6
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 230000006872 improvement Effects 0.000 description 6
- 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 5
- 239000000654 additive Substances 0.000 description 5
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
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- 238000001878 scanning electron micrograph Methods 0.000 description 4
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- KFJDQPJLANOOOB-UHFFFAOYSA-N 2h-benzotriazole-4-carboxylic acid Chemical compound OC(=O)C1=CC=CC2=NNN=C12 KFJDQPJLANOOOB-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
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- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
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- 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
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-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
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- 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
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- 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
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-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
- 241001391944 Commicarpus scandens Species 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 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
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
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- 229910017052 cobalt Inorganic materials 0.000 description 1
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 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 1
- 238000005260 corrosion Methods 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
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- 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
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- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
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- 239000000945 filler Substances 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- XEMZLVDIUVCKGL-UHFFFAOYSA-N hydrogen peroxide;sulfuric acid Chemical compound OO.OS(O)(=O)=O XEMZLVDIUVCKGL-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
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- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 238000000465 moulding Methods 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
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 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
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 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
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 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
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- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Laminated Bodies (AREA)
- Parts Printed On Printed Circuit Boards (AREA)
Abstract
Description
本發明係關於一種粗化處理銅箔、附載體銅箔、銅箔積層板及印刷配線板。The invention relates to a roughened copper foil, a copper foil with a carrier, a copper foil laminate and a printed wiring board.
近年來,作為適合於電路之細微化之印刷配線板之製造工法,廣泛採用MSAP(Modified Semi-Additive Process,改良型半加成製程)法。MSAP法為適合於形成極細微之電路之方法,為了活用其特徵,而使用附載體銅箔進行。例如,如圖1及2所示般,使極薄銅箔(粗化處理銅箔10)隔著預浸體12與底塗層13壓按而密接於在基底基材11a上具備下層電路11b之絕緣樹脂基板11上(步驟(a)),在揭下載體(未圖示)後,根據需要藉由雷射穿孔而形成導通孔14(步驟(b))。繼而,在實施化學銅鍍覆15(步驟(c))後,藉由使用乾膜16之曝光及顯影而以特定之圖案遮罩(步驟(d)),實施電鍍銅17(步驟(e))。在去除乾膜16而形成配線部分17a後(步驟(f)),將彼此相鄰之配線部分17a與17a間之不必要之極薄銅箔等藉由遍及該等之厚度整體進行蝕刻而去除(步驟(g)),而獲得以特定之圖案形成之配線18。此處,為了提高電路-基板間之實體密接性,一般而言進行在極薄銅箔之表面進行粗化處理之操作。In recent years, MSAP (Modified Semi-Additive Process, Modified Semi-Additive Process) method has been widely used as a manufacturing method for printed wiring boards suitable for miniaturization of circuits. The MSAP method is a method suitable for forming extremely fine circuits, and it is performed using copper foil with a carrier in order to make full use of its characteristics. For example, as shown in FIGS. 1 and 2 , an ultra-thin copper foil (roughened copper foil 10 ) is pressed through a
實際上,提議若干種在藉由MSAP法等進行之細微電路形成性上優異之附載體銅箔。例如,於專利文獻1(國際公開第2016/117587號)中,揭示具備如下之極薄銅箔之附載體銅箔,該極薄銅箔之剝離層側之面之表面峰間平均距離為20 μm以下、且剝離層與相反側之面之起伏之最大高低差為1.0 μm以下,根據所述態樣,可兼顧細微電路形成性與雷射加工性。又,於專利文獻2(特開2018-26590號公報)中,揭示如下之附載體銅箔,出於提高細微電路形成性之目的,極薄銅層側表面之基於ISO25178最大峰高度Sp與突出峰部高度Spk之比Sp/Spk為3.271以上10.739以下。Actually, several types of copper foil with a carrier excellent in fine circuit formability by MSAP method etc. are proposed. For example, Patent Document 1 (International Publication No. 2016/117587) discloses a copper foil with a carrier having an ultra-thin copper foil having an average distance between surface peaks of the surface on the release layer side of 20 µm or less, and the maximum height difference between the peeling layer and the surface on the opposite side is 1.0 µm or less. According to this aspect, both fine circuit formability and laser processability can be achieved. In addition, in Patent Document 2 (JP-A-2018-26590), the following copper foil with a carrier is disclosed. For the purpose of improving the formability of fine circuits, the maximum peak height Sp and protrusion of the side surface of the ultra-thin copper layer based on ISO25178 are disclosed. The ratio Sp/Spk of the peak height Spk is 3.271 or more and 10.739 or less.
另一方面,隨著推進電路之細線化,在印刷配線板之安裝步驟中,因來自橫向之實體性之應力(亦即剪應力) 施加於電路而電路容易剝離,而成品率下降之課題明顯化。關於此點,在電路與基板之物理密接指標之一上有抗剪強度(剪切強度),為了有效果地避免上述之電路剝離,而提議適合於抗剪強度之提高之粗化處理銅箔。例如,於專利文獻3(國際公開第2020/031721號)中,揭示將ISO25178規定之最大高度Sz、界面之擴展面積比Sdr及峰之頂點密度Spd分別控制於特定之範圍之粗化處理銅箔。根據如此之粗化處理銅箔,於銅箔積層板之加工或印刷配線板之製造中,可兼顧優異之蝕刻性與高抗剪強度。On the other hand, as the circuit becomes thinner, in the process of mounting the printed wiring board, the circuit is easily peeled off due to the physical stress (that is, shear stress) from the lateral direction applied to the circuit, and the problem of the decline in the yield is obvious. change. Regarding this point, there is shear strength (shear strength) as one of the physical adhesion indicators between the circuit and the substrate. In order to effectively avoid the above-mentioned circuit peeling, a roughened copper foil suitable for improving the shear strength is proposed. . For example, Patent Document 3 (International Publication No. 2020/031721) discloses a roughened copper foil in which the maximum height Sz specified in ISO25178, the expansion area ratio Sdr of the interface, and the peak apex density Spd are respectively controlled within specific ranges. According to such a roughened copper foil, both excellent etching properties and high shear strength can be achieved in the processing of copper foil laminates or in the manufacture of printed wiring boards.
且說,伴隨著近年來之行動用電子機器等之高功能化,為了進行大量資訊之高速處理而推進信號之高頻化,特別是追求適合於第5代移動通信系統(5G)或第6代移動通信系統(6G)等之高頻用途之印刷配線板。對於如此之高頻用印刷配線板,為了能夠將高頻信號在不降低品質下進行傳送,而期望傳送損失之減少。印刷配線板具備加工成配線圖案之銅箔、及絕緣樹脂基材,傳送損失主要為起因於銅箔之導體損失、及起因於絕緣樹脂基材之介電損失。In addition, with the high-performance of mobile electronic devices in recent years, in order to perform high-speed processing of a large amount of information, the frequency of signals is promoted, and in particular, it is suitable for the 5th generation mobile communication system (5G) or the 6th generation. Printed wiring boards for high-frequency applications such as mobile communication systems (6G). In such a high-frequency printed wiring board, reduction of transmission loss is desired in order to transmit a high-frequency signal without lowering the quality. A printed wiring board has copper foil processed into a wiring pattern and an insulating resin base material, and the transmission loss is mainly the conductor loss caused by the copper foil and the dielectric loss caused by the insulating resin base material.
導體損失可能因愈為高頻則愈顯著地顯現之銅箔之集膚效應而增大。因此,為了抑制高頻用途下之傳送損失,而追求銅箔之平滑化及粗化粒子之細微化以減少銅箔之集膚效應。關於此點,已知出於傳送損失之減少之目的之粗化處理銅箔。例如,於專利文獻4(專利第6462961號公報)中揭示:關於如下之表面處理銅箔,即:在銅箔之至少一個面,將粗化處理層、防鏽處理層及矽烷偶合層依此順序積層而成者,自矽烷偶合層之表面測定到之界面之擴展面積比Sdr為8%以上140%以下,均方根表面梯度Sdq為25°以上70°以下,及表面性狀之縱橫比Str為0.25以上0.79以下。根據所述之表面處理銅箔,可進行高頻電信號之傳送損失少、且具有回流銲焊接時之優異之密接性之印刷配線板之製造。 [先前技術文獻] [專利文獻] Conductor losses may increase due to the skin effect of copper foil, which appears more prominently at higher frequencies. Therefore, in order to suppress transmission loss in high-frequency applications, the smoothing of copper foil and the miniaturization of roughened particles are pursued to reduce the skin effect of copper foil. In this regard, roughened copper foil for the purpose of reducing transmission loss is known. For example, it is disclosed in Patent Document 4 (Patent No. 6462961): Regarding the following surface-treated copper foil, that is, on at least one surface of the copper foil, a roughening treatment layer, an anti-rust treatment layer, and a silane coupling layer are formed accordingly For those formed by sequential lamination, the expansion area ratio Sdr of the interface measured from the surface of the silane coupling layer is 8% to 140%, the root mean square surface gradient Sdq is 25° to 70°, and the aspect ratio Str of the surface texture It is not less than 0.25 and not more than 0.79. According to the said surface-treated copper foil, the transmission loss of a high-frequency electric signal is small, and it can manufacture the printed wiring board which has excellent adhesiveness at the time of reflow soldering. [Prior Art Literature] [Patent Document]
[專利文獻1] 國際公開第2016/117587號 [專利文獻2] 日本特開2018-26590號公報 [專利文獻3] 國際公開第2020/031721號 [專利文獻4] 日本專利第6462961號公報 [Patent Document 1] International Publication No. 2016/117587 [Patent Document 2] Japanese Patent Laid-Open No. 2018-26590 [Patent Document 3] International Publication No. 2020/031721 [Patent Document 4] Japanese Patent No. 6462961
如上述般,基於高頻傳送之觀點,作為供形成傳送信號之電路配線之材料而追求傳送損失少之銅箔(亦即在高頻特性上優異之銅箔)。雖然考量藉由銅箔之平滑化及粗化粒子之微小化,而可抑制傳送損失,但銅箔與基板樹脂等之實體密接力(特別是抗剪強度)下降。如此般,兼顧優異之傳送特性與高電路密接性並非易事。As described above, from the viewpoint of high-frequency transmission, copper foil with less transmission loss (that is, copper foil excellent in high-frequency characteristics) is required as a material for forming circuit wiring for transmitting signals. Although it is considered that the transmission loss can be suppressed by smoothing the copper foil and miniaturizing the roughened particles, the physical adhesion between the copper foil and the substrate resin (especially the shear strength) decreases. In this way, it is not easy to balance excellent transmission characteristics and high circuit adhesion.
本發明人等此次獲得如下之見解:於粗化處理銅箔中,藉由賦予將作為峰之體積及谷之體積之和而算出之峰及谷之高度之總和、以及作為峰之平均高度及谷之平均高度之和而算出之峰及谷之平均高度分別控制於特定之範圍之表面輪廓,而在銅箔積層板之加工或印刷配線板之製造中,可兼顧優異之傳送特性與高抗剪強度。The inventors of the present invention have obtained the following knowledge: in roughened copper foil, by giving the sum of the heights of the peaks and valleys calculated as the sum of the volumes of the peaks and the volumes of the valleys, and the average height of the peaks and the valleys The average heights of the peaks and valleys calculated by the sum of the average heights are respectively controlled in a specific range of the surface profile, and in the processing of copper foil laminates or the manufacture of printed wiring boards, excellent transmission characteristics and high shear resistance can be taken into account strength.
因此,本發明之目的在於提供一種在銅箔積層板之加工或印刷配線板之製造中,可兼顧優異之傳送特性與高抗剪強度之粗化處理銅箔。Therefore, an object of the present invention is to provide a roughened copper foil capable of achieving both excellent transmission characteristics and high shear strength in the processing of copper-clad laminates or the manufacture of printed wiring boards.
根據本發明,而提供以下之態樣。 [態樣1] 一種粗化處理銅箔,其在至少一側具有粗化處理面,前述粗化處理面具有相對於基準面成為凸部之複數個峰及相對於前述基準面成為凹部之複數個谷, 在將使用FIB-SEM針對前述粗化處理面獲得之圖像進行三維圖像解析時,作為2000 nm×2000 nm之解析區域內之前述峰之體積及前述谷之體積之和而算出之峰及谷之高度之總和為1.4×10 8nm 3以上3.5×10 8nm 3以下、且作為前述峰之平均高度及前述谷之平均高度之和而算出之峰及谷之平均高度為40 nm以上90 nm以下。 [態樣2] 如態樣1之粗化處理銅箔,其中前述峰及谷之高度之總和為2.0×10 8nm 3以上3.5×10 8nm 3以下。 [態樣3] 如態樣1或2之粗化處理銅箔,其中前述峰及谷之平均高度為40 nm以上80 nm以下。 [態樣4] 如態樣1至3中任一項之粗化處理銅箔,其中在將使用FIB-SEM針對前述粗化處理面獲得之圖像進行三維圖像解析時,每1 nm 2單位面積之前述峰之總體積為7.0 nm 3以上50.0 nm 3以下。 [態樣5] 如態樣4之粗化處理銅箔,其中每1 nm 2單位面積之前述峰之總體積為30.0 nm 3以上50.0 nm 3以下。 [態樣6] 如態樣1~5中任一項之粗化處理銅箔,其中在將使用FIB-SEM針對前述粗化處理面獲得之圖像進行三維圖像解析且將前述峰分割成複數個體元時,2000 nm×2000 nm之解析區域內之構成前述峰之表面之體元之總體積相對於構成前述峰之所有體元之總體積之比,即表面體元比為0.25以上0.60以下。 [態樣7] 如態樣6之粗化處理銅箔,其中前述表面體元比為0.25以上0.35以下。 [態樣8] 如態樣1至7中任一項之粗化處理銅箔,其中在前述粗化處理面進一步具備防鏽處理層及/或矽烷偶合劑層。 [態樣9] 一種附載體銅箔,其具備:載體;剝離層,其設置於該載體上;及態樣1至8中任一項之粗化處理銅箔,其以前述粗化處理面為外側設置於該剝離層上。 [態樣10] 一種銅箔積層板,其具備如態樣1至8中任一項之粗化處理銅箔。 [態樣11] 一種印刷配線板,其具備如態樣1至8中任一項之粗化處理銅箔。 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 peaks that are convex with respect to a reference plane and a plurality of concaves with respect to the reference plane The valley is calculated as the sum of the volume of the peak and the volume of the valley in the analysis area of 2000 nm×2000 nm when analyzing the three-dimensional image of the image obtained by using FIB-SEM on the roughened surface The sum of the heights of the peaks and valleys is 1.4×10 8 nm 3 or more and 3.5×10 8 nm 3 or less, and the average height of the peaks and valleys calculated as the sum of the average height of the peaks and the average height of the valleys is 40 nm or more Below 90nm. [Aspect 2] The roughened copper foil according to Aspect 1, wherein the sum of the heights of the aforementioned peaks and valleys is not less than 2.0×10 8 nm 3 and not more than 3.5×10 8 nm 3 . [Aspect 3] The roughened copper foil according to Aspect 1 or 2, wherein the average height of the aforementioned peaks and valleys is not less than 40 nm and not more than 80 nm. [Aspect 4] The roughened copper foil according to any one of Aspects 1 to 3, wherein when the image obtained by using FIB-SEM on the aforementioned roughened surface is subjected to three-dimensional image analysis, every 1 nm 2 The total volume of the aforementioned peaks per unit area is not less than 7.0 nm 3 and not more than 50.0 nm 3 . [Aspect 5] The roughened copper foil according to Aspect 4, wherein the total volume of the aforementioned peaks per unit area of 1 nm 2 is not less than 30.0 nm 3 and not more than 50.0 nm 3 . [Aspect 6] The roughened copper foil according to any one of Aspects 1 to 5, wherein three-dimensional image analysis is performed on the image obtained on the roughened surface using FIB-SEM and the peak is divided into When there are multiple voxels, the ratio of the total volume of the voxels constituting the surface of the aforementioned peak to the total volume of all voxels constituting the aforementioned peak within the analytical region of 2000 nm×2000 nm, that is, the surface voxel ratio is not less than 0.25 and not more than 0.60. [Aspect 7] The roughened copper foil according to Aspect 6, wherein the surface voxel ratio is not less than 0.25 and not more than 0.35. [Aspect 8] The roughened copper foil according to any one of Aspects 1 to 7, further comprising an antirust treatment layer and/or a silane coupling agent layer on the roughened surface. [Aspect 9] A copper foil with a carrier, which includes: a carrier; a release layer provided on the carrier; and the roughened copper foil according to any one of Aspects 1 to 8, which has a It is arranged on the peeling layer for the outside. [Aspect 10] A copper foil laminate including the roughened copper foil according to any one of Aspects 1 to 8. [Aspect 11] A printed wiring board including the roughened copper foil according to any one of Aspects 1 to 8.
定義以下表示為了特定本發明而使用之用語或參數之定義。 Definitions The definitions of the terms or parameters used to specify the present invention are shown below.
於本說明書中,所謂「使用FIB-SEM針對粗化處理面獲得之圖像」,意指針對粗化處理銅箔之粗化處理面,經由利用FIB(聚焦離子束)進行之剖面加工及利用SEM(掃描電子顯微鏡)進行之剖面觀察而取得之剖面圖像之集合體,整體構成三維形狀資料。具體而言,如圖7所示般在將x軸及z軸設為粗化處理銅箔10之面內方向、且將y軸規定為粗化處理銅箔10之厚度方向後,取得與x-y面平行之切割面S處之粗化處理銅箔10之包含粗化處理面之剖面圖像,使該切割面沿z軸方向逐次平行移動特定間隔(例如10 nm),且在特定之解析區域(例如2000 nm×2000 nm)內取得之(例如合計1000張之)剖面圖像之集合體。In this specification, the so-called "image obtained on the roughened surface using FIB-SEM" refers to the roughened surface of the roughened copper foil, which is processed by FIB (focused ion beam) and utilized. The aggregate of cross-sectional images obtained through cross-sectional observation by SEM (Scanning Electron Microscope) constitutes three-dimensional shape data as a whole. Specifically, as shown in FIG. 7 , when the x-axis and the z-axis are defined as the in-plane direction of the roughened
於本說明書中,所謂粗化處理面之「峰」如圖3及4示意性地顯示般,意指粗化處理銅箔10之粗化處理面具有之凹凸構造中之相對於基準面R成為凸部之部分。又,於本說明書中,所謂粗化處理面之「谷」,如圖3及4示意性地顯示般,意指粗化處理銅箔10之粗化處理面具有之凹凸構造中之相對於基準面R成為凹部之部分。粗化處理面之「基準面」可藉由對使用FIB-SEM針對粗化處理面獲得之圖像進行三維圖像解析而特定。具體而言,首先,於2000 nm×2000 nm之解析區域(俯視時之尺寸)內,對於構成凹凸構造之圖像之x-z面內之1個像素(以下稱為關注像素),求得以該關注像素為中心之x-z面內之特定之矩陣尺寸(例如99)中之粗化處理面之高度(y方向)之中央值(基準點)。例如,於矩陣尺寸為99時,意指自以關注像素為中心之99像素×99像素各者之粗化處理面之高度獲得中央值。對於構成凹凸構造之圖像之x-z面內之所有像素(以各個像素為關注像素)分別進行該操作,求得各個關注像素之粗化處理面之高度之中央值(基準點)。然後,可製作通過藉由如此般求得之各個關注像素之所有基準點之面,並設為基準面。上述之三維圖像解析,可使用市售之軟體自動進行,藉由對粗化處理銅箔之凹凸構造應用指定矩陣尺寸(例如99)之中值濾波器而可唯一地決定基準面(亦即在市售之軟體中關於基準面之設定除了矩陣尺寸以外無可任意設定條件之項目)。例如,對於粗化處理面之圖像(粗化處理銅箔之三維形狀資料之切割圖像),可使用三維定位軟體「ExFact Slice Aligner(版本2.0)」(日本VISUAL SCIENCE株式會社製)以及三維圖像解析軟體「ExFact VR(版本2.2)」及「foil Analysis(版本1.0)」(皆為日本VISUAL SCIENCE株式會社製),依照本說明書之實施例中記載之諸個條件進行圖像解析。又,後述之實施例中顯示關於使用FIB-SEM獲得之剖面圖像之取得方法。In this specification, the so-called "peak" of the roughened surface, as shown schematically in FIGS. convex part. In addition, in this specification, the so-called "valley" of the roughened surface, as shown schematically in FIGS. Surface R becomes part of the recess. The "reference plane" of the roughened surface can be specified by performing three-dimensional image analysis on the image obtained for the roughened surface using FIB-SEM. Specifically, first, within the analysis area (size when viewed from above) of 2000 nm×2000 nm, for one pixel in the x-z plane of the image constituting the concave-convex structure (hereinafter referred to as the pixel of interest), obtain the The pixel is the central value (reference point) of the height (y direction) of the roughened surface in a specific matrix size (for example, 99) in the x-z plane of the center. For example, when the matrix size is 99, it means that the median value is obtained from the height of each roughened surface of 99 pixels×99 pixels centered on the pixel of interest. This operation is performed on all pixels in the x-z plane of the image forming the concave-convex structure (each pixel is the pixel of interest), and the median (reference point) of the height of the roughened surface of each pixel of interest is obtained. Then, a plane passing through all the reference points of each pixel of interest obtained in this way can be created and set as a reference plane. The above-mentioned three-dimensional image analysis can be carried out automatically using commercially available software, and the reference plane (ie, In the setting of the reference plane in the commercially available software, there are no items that can be set arbitrarily except for the matrix size). For example, for the image of the roughened surface (the cut image of the 3D shape data of the roughened copper foil), the 3D positioning software "ExFact Slice Aligner (version 2.0)" (manufactured by VISUAL SCIENCE Co., Ltd., Japan) and the 3D The image analysis software "ExFact VR (Version 2.2)" and "foil Analysis (Version 1.0)" (both manufactured by VISUAL SCIENCE Co., Ltd., Japan) performed image analysis in accordance with the conditions described in the Examples of this specification. In addition, the method for obtaining cross-sectional images obtained using FIB-SEM will be shown in Examples described later.
於本說明書中,所謂「峰及谷之高度之總和」,為表示2000 nm×2000 nm之解析區域(俯視時之尺寸)內之峰之體積及谷之體積之和之參數。亦即,如圖3中示意性地顯示般,將相對於基準面R之峰之體積Ap之合計(解析區域內之所有峰之總體積)、與相對於基準面R之谷之體積Av之合計(解析區域內之所有谷之總體積)相加而得者,相當於峰及谷之高度之總和。再者,「峰及谷之高度之總和」亦可稱為「峰及谷之體積之總和」,因在市售之圖像解析軟體之說明書中為藉由將以「峰之高度」及「谷之高度」之名義言及之數值進行積算而算出之值,故在本說明書中,有意使用「峰及谷之高度之總和」之表現以便熟悉此項技術者容易實施測定。In this specification, the "sum of the heights of peaks and valleys" is a parameter representing the sum of the volumes of peaks and valleys within an analysis region (dimensions when viewed from above) of 2000 nm×2000 nm. That is, as schematically shown in FIG. 3, the sum of the peak volumes Ap with respect to the reference plane R (the total volume of all peaks in the analysis region) and the sum of the volumes Av of the valleys with respect to the reference plane R ( The sum of the total volume of all valleys in the analytical area) is equivalent to the sum of the heights of peaks and valleys. Furthermore, "the sum of the heights of peaks and valleys" can also be referred to as "the sum of the volumes of peaks and valleys", because in the manuals of commercially available image analysis software, the terms "height of peaks" and "valleys" are used. Therefore, in this specification, the expression of "the sum of the heights of peaks and valleys" is intentionally used so that those familiar with this technology can easily carry out the measurement.
於本說明書中,所謂「峰及谷之平均高度」,為表示2000 nm×2000 nm之解析區域(俯視時之尺寸)內之峰之平均高度及谷之平均高度之和之參數。亦即,如圖4中示意性地顯示般,將相對於基準面R之峰之高度Hp之平均(解析區域之所有峰之平均高度)、與相對於基準面R之谷之高度Hv之平均(解析區域之所有谷之平均高度)相加而得者,相當於峰及谷之平均高度H。In this specification, the "average height of peaks and valleys" is a parameter representing the sum of the average height of peaks and the average height of valleys within an analysis area (dimensions in plan view) of 2000 nm×2000 nm. That is, as shown schematically in FIG. 4 , the average of the heights Hp of peaks relative to the reference plane R (the average height of all peaks in the analysis region) and the average of the heights Hv of valleys relative to the reference plane R (analysis The average height of all valleys in the area) is equivalent to the average height H of peaks and valleys.
於本說明書中,所謂「每1 nm 2單位面積之峰之總體積」,為藉由將2000 nm×2000 nm之解析區域(俯視時之尺寸)內之所有峰之總體積,以解析區域之面積相除而算出之參數。 In this specification, the so-called "total volume of peaks per unit area of 1 nm" is calculated by comparing the total volume of all peaks in the analysis region (dimensions when viewed from above) of 2000 nm×2000 nm to the area of the analysis region The parameters calculated by division.
峰及谷之高度之總和、峰及谷之平均高度、亦即每1 nm 2單位面積之峰之總體積,可藉由對使用FIB-SEM針對粗化處理面獲得之圖像進行三維圖像解析而特定。如此之三維圖像解析可使用市售之軟體進行。例如,對於粗化處理面之剖面圖像(粗化處理銅箔之三維形狀資料之切割圖像),可使用三維定位軟體「ExFact Slice Aligner(版本2.0)」(日本VISUAL SCIENCE株式會社製)以及三維圖像解析軟體「ExFact VR(版本2.2)」及「foil Analysis(版本1.0)」(皆為日本VISUAL SCIENCE株式會社製),依照本說明書之實施例中記載之諸個條件進行圖像解析。又,後述之實施例中顯示關於使用FIB-SEM獲得之剖面圖像之取得方法。 The sum of the heights of peaks and valleys, the average height of peaks and valleys, that is, the total volume of peaks per 1 nm2 unit area, can be analyzed by performing three-dimensional image analysis on the image obtained for the roughened surface using FIB-SEM rather specific. Such three-dimensional image analysis can be performed using commercially available software. For example, for the cross-sectional image of the roughened surface (the cutting image of the 3D shape data of the roughened copper foil), the 3D positioning software "ExFact Slice Aligner (version 2.0)" (manufactured by VISUAL SCIENCE Co., Ltd., Japan) and The three-dimensional image analysis software "ExFact VR (version 2.2)" and "foil Analysis (version 1.0)" (both manufactured by Japan Visual Science Co., Ltd.) perform image analysis in accordance with the conditions described in the examples of this manual. In addition, the method for obtaining cross-sectional images obtained using FIB-SEM will be shown in Examples described later.
於本說明書中,所謂「體元」,為三維圖像資料中之體積之要素,且為與二維圖像資料之像素對應之概念。體元可以立方體或長方體等表現,例如就每一體元具有如(縱、橫、高度)=(1 nm、1 nm、1 nm)之大小,故可換算成SI單位。In this specification, the so-called "voxel" is an element of volume in three-dimensional image data, and is a concept corresponding to a pixel of two-dimensional image data. Voxels can be represented by cubes or cuboids. For example, each voxel has a size such as (vertical, horizontal, height) = (1 nm, 1 nm, 1 nm), so it can be converted into SI units.
於本說明書中,所謂「表面體元比」,意指在將粗化處理面之峰分割成複數個體元時,2000 nm×2000 nm之解析區域(俯視時之尺寸)之構成峰之表面之體元(表面體元)之總體積、相對於構成峰之所有體元之總體積之比。表面體元比可藉由對使用FIB-SEM針對粗化處理面獲得之圖像進行三維圖像解析而特定。具體而言,如圖5中示意性地顯示般,對使用FIB-SEM針對粗化處理面獲得之圖像,藉由如圖8所示般,以z軸相對於粗化處理面為垂直、且x-y面與粗化處理面為平行之方式分配x軸、y軸及z軸,並進行三維圖像解析,而將存在於粗化處理面之峰(P 1、P 2、P 3)藉由體元B而假想性地區劃(標籤化)。此時,將構成峰之體元B中之構成峰之表面(與大氣接觸之面)之體元定義為「表面體元Bs」,藉此可算出表面體元比。如此之三維圖像解析可使用市售之軟體進行。例如,對於粗化處理面之圖像(粗化處理銅箔之三維形狀資料之切割圖像),可使用三維定位軟體「ExFact Slice Aligner(版本2.0)」(日本VISUAL SCIENCE株式會社製)以及三維圖像解析軟體「ExFact VR(版本2.2)」及「foil Analysis(版本1.0)」(皆為日本VISUAL SCIENCE株式會社製),依照本說明書之實施例中記載之諸個條件進行圖像解析。又,後述之實施例中顯示關於使用FIB-SEM獲得之剖面圖像之取得方法。 In this specification, the so-called "surface voxel ratio" refers to the volume of the surface constituting the peak in the analysis area (size when viewed from above) of 2000 nm×2000 nm when the peak of the roughened surface is divided into plural voxels The ratio of the total volume of the element (surface voxel) to the total volume of all voxels making up the peak. The surface voxel ratio can be specified by three-dimensional image analysis of the image obtained for the roughened surface using FIB-SEM. Specifically, as shown schematically in FIG. 5 , for the image obtained for the roughened surface using FIB-SEM, as shown in FIG. 8 , the z-axis is perpendicular to the roughened surface, And the x-axis, y-axis, and z-axis are assigned in such a way that the xy plane and the roughened surface are parallel, and the three-dimensional image analysis is performed, and the peaks (P 1 , P 2 , P 3 ) existing on the roughened surface are borrowed The voxel B is hypothetically partitioned (labelled). In this case, the voxel constituting the surface of the peak (the surface in contact with the atmosphere) among the voxels constituting the peak is defined as "surface voxel Bs", thereby calculating the surface voxel ratio. Such three-dimensional image analysis can be performed using commercially available software. For example, for the image of the roughened surface (the cut image of the 3D shape data of the roughened copper foil), the 3D positioning software "ExFact Slice Aligner (version 2.0)" (manufactured by VISUAL SCIENCE Co., Ltd., Japan) and the 3D The image analysis software "ExFact VR (Version 2.2)" and "foil Analysis (Version 1.0)" (both manufactured by VISUAL SCIENCE Co., Ltd., Japan) performed image analysis in accordance with the conditions described in the Examples of this specification. In addition, the method for obtaining cross-sectional images obtained using FIB-SEM will be shown in Examples described later.
於本說明書中,所謂載體之「電極面」係指在載體製作時與陰極接觸之側之面。In this specification, the "electrode surface" of the carrier refers to the surface on the side that contacts the cathode when the carrier is fabricated.
於本說明書中,所謂載體之「析出面」係指在載體製作時電解銅不斷析出之側之面、亦即不與陰極接觸之側之面。In this specification, the so-called "precipitation surface" of the carrier refers to the surface on which the electrolytic copper is continuously deposited during the production of the carrier, that is, the surface on the side that is not in contact with the cathode.
粗化處理銅箔本發明之銅箔為粗化處理銅箔。該粗化處理銅箔於至少一側具有粗化處理面。該粗化處理面具有相對於基準面成為凸部之複數個峰及相對於基準面成為凹部之複數個谷。而且,在將使用FIB-SEM針對粗化處理面獲得之圖像進行三維圖像解析時,作為2000 nm×2000 nm之解析區域內之峰之體積及谷之體積之和而算出之峰及谷之高度之總和為1.4×10 8nm 3以上3.5×10 8nm 3以下。又,作為2000 nm×2000 nm之解析區域內之峰之平均高度及谷之平均高度之和而算出之峰及谷之平均高度為40 nm以上90 nm以下。如此般於粗化處理銅箔中,藉由賦予將峰及谷之高度之總和、以及峰及谷之平均高度分別控制於特定之範圍之表面輪廓,而在銅箔積層板之加工或印刷配線板之製造中,可兼顧優異之傳送特性(特別是優異之高頻特性)與高抗剪強度(進而基於抗剪強度之觀點下之高電路密接性)。 Roughening treatment copper foil The copper foil of this invention is a roughening treatment copper foil. The roughened copper foil has a roughened surface on at least one side. The roughened surface has a plurality of peaks that are convex with respect to the reference plane and a plurality of valleys that are concave with respect to the reference plane. Furthermore, when a three-dimensional image analysis is performed on an image obtained on a roughened surface using FIB-SEM, the sum of the volume of the peak and the volume of the valley calculated as the sum of the volume of the peak and the volume of the valley in the analysis area of 2000 nm × 2000 nm The sum of the heights is not less than 1.4×10 8 nm 3 and not more than 3.5×10 8 nm 3 . Also, the average height of peaks and valleys calculated as the sum of the average height of peaks and the average height of valleys in the analysis region of 2000 nm×2000 nm is not less than 40 nm and not more than 90 nm. In this way, in the roughened copper foil, by giving the surface profile that controls the sum of the heights of the peaks and valleys, and the average height of the peaks and valleys to specific ranges, it can be used in the processing or printing of copper foil laminates. In the manufacture of boards, excellent transmission characteristics (especially excellent high-frequency characteristics) and high shear strength (and thus high circuit adhesion from the perspective of shear strength) can be taken into account.
優異之傳送特性與高抗剪強度原本難以兼顧。此乃因為如上述般,為了獲得優異之傳送特性,一般而言追求銅箔之平滑化及粗化粒子之微小化,但另一方面為了提高電路之抗剪強度,一般而言追求加大粗化粒子之故。關於此點,本發明人等在研究之後發現:藉由將粗化處理銅箔進行三維評估而控制粗化形狀,而雖為在傳送損失之減少上有利之微小之凹凸構造,但可理想地保持銅箔-基材間之密接性。而且,發現如此之凹凸構造可藉由將峰及谷之高度之總和、以及峰及谷之平均高度分別控制於特定範圍而實現。It is difficult to balance the excellent transmission characteristics and high shear strength. This is because, as mentioned above, in order to obtain excellent transmission characteristics, the smoothness of copper foil and the miniaturization of roughened particles are generally pursued, but on the other hand, in order to improve the shear strength of the circuit, generally large rough Because of the particles. Regarding this point, the inventors of the present invention found after research that the roughened shape can be controlled by three-dimensionally evaluating the roughened copper foil, and although it is a fine uneven structure that is advantageous in reducing transmission loss, it can be ideally Maintain the adhesion between copper foil and substrate. Furthermore, it was found that such a concavo-convex structure can be realized by controlling the sum of the heights of the peaks and valleys, and the average height of the peaks and valleys, respectively, within specific ranges.
該機制雖不一定為明確,但可考量如以下之內容。亦即,如一面參照圖3而如上述般,峰及谷之高度之總和表示相對於基準面R之峰及谷之合計體積,此大致相當於與基材接觸之部分(咬入基材之部分)之體積。因此,峰及谷之高度之總和愈大,則與基材接觸之部分之體積愈大,故與抗剪強度之增加相關聯。又,如一面參照圖4而如上述般,峰及谷之平均高度表示相對於基準面R之峰高度平均及谷高度平均之合計。即,峰及谷之平均高度愈小,則表面之凹凸愈小。而且,若表面之凹凸小,則即便在因高頻化而趨膚深度變小時,電流路徑亦不易受表面之凹凸影響,而與傳送損失之減少相關聯。因此,藉由將粗化處理面內之峰及谷之高度之總和、以及峰及谷之平均高度之兩者控制於特定範圍,而在使用於銅箔積層板或印刷配線板時,可均衡性良好地實現優異之傳送特性與高抗剪強度。Although the mechanism is not necessarily clear, the following contents can be considered. That is, as mentioned above with reference to FIG. 3 , the sum of the heights of the peaks and valleys represents the total volume of the peaks and valleys with respect to the reference plane R, which roughly corresponds to the portion in contact with the substrate (the portion that bites into the substrate) part) volume. Therefore, the greater the sum of the heights of the peaks and valleys, the greater the volume of the portion in contact with the substrate, and thus correlates with an increase in shear strength. In addition, as mentioned above while referring to FIG. 4 , the average height of peaks and valleys represents the sum of the average peak height and the average valley height with respect to the reference plane R. That is, the smaller the average height of the peaks and valleys, the smaller the unevenness of the surface. Furthermore, if the surface irregularities are small, even if the skin depth becomes smaller due to high frequency, the current path will not be easily affected by the surface irregularities, leading to a reduction in transmission loss. Therefore, by controlling both the sum of the heights of the peaks and valleys and the average heights of the peaks and valleys in the roughened surface within specific ranges, when used in copper foil laminates or printed wiring boards, it is possible to balance It can achieve excellent transmission characteristics and high shear strength with good performance.
另一方面,於先前技術中,使用雷射顯微鏡對粗化形狀進行了評估,但在所述方法中,在準確地評估微小之粗化形狀之特徵上存在界限。此處,圖6示意性地顯示藉由雷射顯微鏡對粗化處理面之測定之一例。如圖6所示般,於雷射顯微鏡之測定中,自粗化處理面之上方照射雷射光。此時,存在因被粗化粒子10a遮擋而雷射光無法入射之區域N。起因於該區域N,在使用雷射顯微鏡之粗化處理面之測定中,可能難以準確地評估峰及谷之表面積或體積等之特徵。該問題在追求兼顧優異之傳送特性與高電路密接性之微小之粗化形狀時變得顯著。又,於先前技術中,亦研究三維地評估樣品之方法,但作為可兼顧優異之傳送特性與高抗剪強度之評估方法不可謂為充分者。相對於此,於本發明中,著眼於峰及谷之高度之總和、以及峰及谷之平均高度,藉由將該等分別控制於適切之範圍,而在使用於銅箔積層板或印刷配線板時,可兼顧優異之傳送特性與高抗剪強度。On the other hand, in the prior art, the roughened shape was evaluated using a laser microscope, but in this method, there is a limit to accurately evaluating the characteristics of the minute roughened shape. Here, FIG. 6 schematically shows an example of measurement of a roughened surface with a laser microscope. As shown in FIG. 6 , in the measurement with a laser microscope, laser light is irradiated from above the roughened surface. At this time, there is a region N where laser light cannot enter due to being blocked by the
基於實現高抗剪強度之觀點,粗化處理銅箔之粗化處理面之峰及谷之高度之總和為1.4×10 8nm 3以上3.5×10 8nm 3以下,較佳的是,基於抗剪強度之進一步提高之觀點為2.0×10 8nm 3以上3.5×10 8nm 3以下,或者基於傳送特性之進一步提高之觀點為1.4×10 8nm 3以上1.8×10 8nm 3以下。 Based on the viewpoint of achieving high shear strength, the sum of the heights of the peaks and valleys on the roughened surface of the roughened copper foil is 1.4×10 8 nm 3 or more and 3.5×10 8 nm 3 or less. The point of view of further improvement of shear strength is 2.0×10 8 nm 3 to 3.5×10 8 nm 3 , or the point of view of further improvement of transmission characteristics is 1.4×10 8 nm 3 to 1.8×10 8 nm 3 .
基於實現優異之傳送特性之觀點,粗化處理銅箔之粗化處理面內之峰及谷之平均高度為40 nm以上90 nm以下,較佳為40 nm以上80 nm以下,更佳的是,基於傳送特性之進一步提高之觀點為40 nm以上50 nm以下,或者基於抗剪強度之進一步提高之觀點為70 nm以上80 nm以下。Based on the viewpoint of achieving excellent transmission characteristics, the average height of the peaks and valleys in the roughened surface of the roughened copper foil is not less than 40 nm and not more than 90 nm, preferably not less than 40 nm and not more than 80 nm, and more preferably, From the point of view of further improvement of transmission characteristics, it is 40 nm to 50 nm, or from the point of view of further improvement of shear strength, it is 70 nm to 80 nm.
粗化處理銅箔之粗化處理面內之每1 nm 2單位面積之峰之總體積為7.0 nm 3以上50.0 nm 3以下為較佳,更佳為30.0 nm 3以上50.0 nm 3以下。藉此,在使用於銅箔積層板或印刷配線板時,可實現更進一步高之抗剪強度。 The total volume of peaks per 1 nm 2 unit area of the roughened copper foil is preferably 7.0 nm 3 to 50.0 nm 3 , more preferably 30.0 nm 3 to 50.0 nm 3 . Thereby, when it is used for a copper-clad laminated board or a printed wiring board, a further higher shear strength can be realized.
基於實現高抗剪強度之觀點,粗化處理銅箔之粗化處理面內之表面體元比為0.25以上0.60以下為較佳,更佳的是,基於抗剪強度之進一步提高之觀點為0.25以上0.35以下,或者基於傳送特性之進一步提高之觀點為0.40以上0.60以下。From the point of view of achieving high shear strength, the surface voxel ratio in the roughened surface of the roughened copper foil is preferably 0.25 to 0.60, more preferably 0.25 from the point of view of further improvement of the shear strength The above is 0.35 or less, or it is 0.40 or more and 0.60 or less from the viewpoint of further improvement of transmission characteristics.
藉由控制表面體元比而可提高抗剪強度之機制雖不一定為明確,但可考量如以下之內容。此處,圖5示意性地顯示將存在於粗化處理銅箔10之粗化處理面之峰(P
1、P
2、P
3)藉由體元B而假想性地區劃之例。圖5所示之峰P
1、峰P
2及峰P
3之總體積相同,因此,分別區劃該等峰之體元B之個數亦為相同(20個)。另一方面,於峰P
1、峰P
2及峰P
3中,構成峰之表面之表面體元Bs(位於與樹脂接觸之最表面部分之體元)分別為20個、14個、10個,故表面體元比(表面體元之總體積相對於所有體元之總體積之比)分別為1.0(=20/20)、0.7(=14/20)、0.5(=10/20)而不同。而且,因依照峰P
3、峰P
2、峰P
1之順序在橫向(以圖5之箭頭所示之方向)上所佔之體積之比例(除了表面體元之外之體積之比例)大,故可依照該順序耐受來自橫向之更大之力(亦即,抗剪強度依照峰P
3、峰P
2、峰P
1之順序為大)。即,在峰之總體積相同時,可謂表面體元比愈小則抗剪強度愈大。考量為僅由表面體元構成之部分脆、容易折斷,故對於抗剪強度之影響小。若僅表示粗化處理面之峰之寬度,則亦包含僅由對於抗剪強度之影響小之表面體元構成之部分,故在與抗剪強度建立對應關係時不充分。因此,抗剪強度較佳的是藉由表面體元比表示。又,基於謀求優異之傳送特性之兼顧之觀點,理想的是在取得與峰及谷之平均高度之平衡下,將表面體元比控制於上述範圍。
Although the mechanism of increasing the shear strength by controlling the surface volume ratio is not necessarily clear, the following contents can be considered. Here, FIG. 5 schematically shows an example in which the peaks (P 1 , P 2 , P 3 ) existing on the roughened surface of the roughened
粗化處理銅箔之厚度並無特別限定,較佳為0.1 μm以上35 μm以下,更佳為0.5 μm以上5.0 μm以下,尤佳為1.0 μm以上3.0 μm以下。再者,粗化處理銅箔並不限於對通常之銅箔之表面進行粗化處理者,亦可為對附載體銅箔之銅箔表面進行粗化處理者。此處,粗化處理銅箔之厚度為不包含形成於處理面之表面之粗化粒子之高度之厚度(構成粗化處理銅箔之銅箔本身之厚度)。有時將具有上述範圍之厚度之銅箔稱為極薄銅箔。The thickness of the roughened copper foil is not particularly limited, but it is preferably from 0.1 μm to 35 μm, more preferably from 0.5 μm to 5.0 μm, especially preferably from 1.0 μm to 3.0 μm. In addition, the roughening process copper foil is not limited to the thing which roughened the surface of the normal copper foil, The thing which roughened the copper foil surface of the copper foil with a carrier may be sufficient. Here, the thickness of the roughened copper foil is a thickness not including the height of the roughened particles formed on the surface of the treated surface (thickness of the copper foil itself constituting the roughened copper foil). Copper foil having a thickness in the above range may be called ultra-thin copper foil.
粗化處理銅箔於至少一側具有粗化處理面。亦即,粗化處理銅箔可於兩側具有粗化處理面,亦可僅於一側具有粗化處理面。粗化處理面典型而言具備複數個粗化粒子(***),該等複數個粗化粒子較佳的是各自包含銅粒子。銅粒子可為包含金屬銅者,亦可為包含銅合金者。The roughened copper foil has a roughened surface on at least one side. That is, the roughened copper foil may have a roughened surface on both sides, or may have a roughened surface only on one side. Typically, the roughened surface has a plurality of roughened particles (protrusions), and each of the plurality of roughened particles preferably contains copper particles. Copper particles may contain metallic copper or may contain a copper alloy.
用於形成粗化處理面之粗化處理可藉由在銅箔之上利用銅或銅合金形成粗化粒子而較佳地進行。該粗化處理較佳的是依照經由3階段之鍍敷步驟之鍍敷方法進行。該情形下,在第1階段之鍍敷步驟中,較佳的是使用銅濃度5 g/L以上15 g/L以下、及硫酸濃度200 g/L以上250 g/L以下之硫酸銅溶液,在液溫25℃以上45℃以下、電流密度2 A/dm 2以上4 A/dm 2以下之鍍敷條件下進行電沈積。特別是,第1階段之鍍敷步驟較佳的是使用2個槽合計進行2次。在第2階段之鍍敷步驟中,較佳的是使用銅濃度60 g/L以上80 g/L以下、及硫酸濃度200 g/L以上260 g/L以下之硫酸銅溶液,在液溫45℃以上55℃以下、電流密度10 A/dm 2以上15 A/dm 2以下之鍍敷條件下進行電沈積。在第3階段之鍍敷步驟中,較佳的是使用銅濃度5 g/L以上20 g/L以下、硫酸濃度60 g/L以上90 g/L以下、氯濃度20 mg/L以上40 mg/L以下、及9-苯基吖啶(9PA)濃度100 mg/L以上200 mg/L以下之硫酸銅溶液,在液溫25℃以上35℃以下、電流密度30 A/dm 2以上60 A/dm 2以下之鍍敷條件下進行電沈積。第2階段及第3階段之各鍍敷步驟可使用2個槽合計進行2次,較佳的是合計以1次完成。藉由經由如此之鍍敷步驟,易於在處理表面形成便於滿足上述之表面參數之較合適之***。 Roughening treatment for forming a roughened surface can be preferably performed by forming roughening particles using copper or a copper alloy on copper foil. The roughening treatment is preferably performed according to a plating method through three-stage plating steps. In this case, in the plating step of the first stage, it is preferable to use a copper sulfate solution with a copper concentration of 5 g/L to 15 g/L and a sulfuric acid concentration of 200 g/L to 250 g/L. Electrodeposition is carried out under the plating conditions of a liquid temperature of 25°C to 45°C and a current density of 2 A/dm 2 to 4 A/dm 2 . In particular, it is preferable to perform the plating step of the first stage twice in total using two tanks. In the plating step of the second stage, it is preferable to use a copper sulfate solution with a copper concentration of 60 g/L to 80 g/L and a sulfuric acid concentration of 200 g/L to 260 g/L. Electrodeposition is carried out under the plating conditions of above 55°C and current density of 10 A/dm 2 to 15 A/dm 2 . In the plating step of the third stage, it is preferable to use a copper concentration of 5 g/L to 20 g/L, a sulfuric acid concentration of 60 g/L to 90 g/L, and a chlorine concentration of 20 mg/L to 40 mg. Copper sulfate solution with a concentration of 9-phenylacridine (9PA) of 100 mg/L or more and 200 mg/L or less, with 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 Electrodeposition is carried out under the plating conditions below /dm 2 . Each plating step of the second stage and the third stage can be performed twice in total using two tanks, and it is preferable to complete it once in total. By going through such a plating step, it is easy to form more suitable protrusions on the treated surface to satisfy the above-mentioned surface parameters.
亦可根據期望對粗化處理銅箔施加防鏽處理,而形成有防鏽處理層。防鏽處理較佳的是包含使用鋅之鍍敷處理。使用鋅之鍍敷處理可為鋅鍍敷處理及鋅合金鍍敷處理之任一者,尤佳為鋅合金鍍敷處理之鋅-鎳合金處理。鋅-鎳合金處理只要為至少包含Ni及Zn之鍍敷處理即可,亦可進一步包含Sn、Cr、Co、Mo等其他元素。鋅-鎳合金鍍敷中之Ni/Zn附著比率在質量比下較佳為1.2以上10以下,更佳為2以上7以下,尤佳為2.7以上4以下。又,防鏽處理較佳的是進一步包含鉻酸鹽處理,更佳的是在使用鋅之鍍敷處理之後,對包含鋅之鍍敷之表面進行該鉻酸鹽處理。藉此可進一步提高防鏽性。尤佳之防鏽處理為鋅-鎳合金鍍敷處理與其後之鉻酸鹽處理之組合。If desired, antirust treatment may be given to the roughened copper foil to form an antirust treatment layer. The antirust treatment preferably includes plating treatment using zinc. The plating treatment using zinc may be any one of zinc plating treatment and zinc alloy plating treatment, especially zinc-nickel alloy treatment of zinc alloy plating treatment. The zinc-nickel alloy treatment may be a plating treatment including at least Ni and Zn, and other elements such as Sn, Cr, Co, and Mo may be further included. The Ni/Zn adhesion ratio in the zinc-nickel alloy plating is preferably from 1.2 to 10 in mass ratio, more preferably from 2 to 7, and especially preferably from 2.7 to 4. In addition, it is preferable that the antirust treatment further includes chromate treatment, and it is more preferable that the chromate treatment is performed on the surface of the plating including zinc after the plating treatment using zinc. Thereby, rust resistance can be further improved. A particularly preferred antirust treatment is a combination of zinc-nickel alloy plating followed by chromate treatment.
亦可根據期望對粗化處理銅箔之表面施加矽烷偶合劑處理,而形成有矽烷偶合劑層。藉此,可提高耐濕性、耐藥品性及與接著劑等之密接性等。矽烷偶合劑層可藉由將矽烷偶合劑適當稀釋後塗佈、並乾燥而形成。作為矽烷偶合劑之例,可舉出:4-縮水甘油基丁基三甲氧基矽烷、3-縮水甘油氧基三甲氧基矽烷等之環氧官能性矽烷偶合劑、或3-胺基丙基三甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷、N-3-(4-(3-胺基丙氧基)丁氧基)丙基-3-胺基丙基三甲氧基矽烷、N-苯基-3-胺基丙基三甲氧基矽烷等之胺基官能性矽烷偶合劑、或3-巰基丙基三甲氧基矽烷等之巰基官能性矽烷偶合劑或乙烯三甲氧基矽烷、乙烯苯基三甲氧基矽烷等之烯烴官能性矽烷偶合劑、或3-甲基丙烯醯氧基丙基三甲氧基矽烷等之丙烯酸官能性矽烷偶合劑、或咪唑矽烷等之咪唑官能性矽烷偶合劑、或三嗪矽烷等之三嗪官能性矽烷偶合劑等。A silane coupling agent treatment may also be applied to the surface of the roughened copper foil as desired to form a silane coupling agent layer. Thereby, moisture resistance, chemical resistance, adhesiveness with an adhesive, etc. can be improved. The silane coupling agent layer can be formed by appropriately diluting the silane coupling agent, applying it, and drying it. Examples of silane coupling agents include epoxy-functional silane coupling agents such as 4-glycidylbutyltrimethoxysilane and 3-glycidyloxytrimethoxysilane, or 3-aminopropyl Trimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-3-(4-(3-aminopropoxy)butoxy)propyl- Amino-functional silane coupling agents such as 3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, etc., or mercapto-functional silanes such as 3-mercaptopropyltrimethoxysilane Olefin-functional silane coupling agents such as vinyltrimethoxysilane and vinylphenyltrimethoxysilane, or acrylic-functional silane coupling agents such as 3-methacryloxypropyltrimethoxysilane , or imidazole functional silane coupling agents such as imidazole silane, or triazine functional silane coupling agents such as triazine silane, etc.
基於上述之理由,粗化處理銅箔較佳的是於粗化處理面進一步具備防鏽處理層及/或矽烷偶合劑層,更佳的是具備防鏽處理層及矽烷偶合劑層之兩者。防鏽處理層及矽烷偶合劑層可不僅形成於粗化處理銅箔之粗化處理面側,亦可形成於未形成有粗化處理面之側。Based on the above reasons, the roughened copper foil is preferably further equipped with an anti-rust treatment layer and/or a silane coupling agent layer on the roughened surface, and more preferably has both an anti-rust treatment layer and a silane coupling agent layer. . The antirust treatment 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.
附載體銅箔如上述般,本發明之粗化處理銅箔可以附載體銅箔之形態而提供。藉由設為附載體銅箔之形態,可實現優異之雷射加工性及細線電路形成性。亦即,根據本發明之較佳之態樣,提供一種附載體銅箔,其具備:載體;剝離層,其設置於載體上;及上述粗化處理銅箔,其以粗化處理面為外側設置於剝離層上。不過,附載體銅箔除了使用本發明之粗化處理銅箔以外,亦可採用周知之層構成。 Copper foil with carrier As mentioned above, the roughened copper foil of this invention can be provided in the form of copper foil with a carrier. By adopting the form of copper foil with a carrier, excellent laser processability and fine line circuit formability can be realized. That is, according to a preferred aspect of the present invention, there is provided a copper foil with a carrier, which includes: a carrier; a release layer provided on the carrier; and the above-mentioned roughened copper foil, which is provided with the roughened surface as the outer side. on the release layer. However, the copper foil with a carrier may employ a known layer configuration other than the roughened copper foil of the present invention.
載體係用於支持粗化處理銅箔而提高其操作性之支持體,典型之載體包含金屬層。作為如此之載體之例,可舉出鋁箔、銅箔、不鏽鋼(SUS)箔、將表面以銅等金屬塗佈之樹脂膜或玻璃等,較佳為銅箔。銅箔可為壓延銅箔及電解銅箔之任一者,較佳為電解銅箔。載體之厚度典型而言為250 μm以下,較佳為7 μm以上200 μm以下。The support system is used to support the roughened copper foil to improve its handling. The typical support includes a metal layer. Examples of such a carrier include aluminum foil, copper foil, stainless steel (SUS) foil, a resin film or glass whose surface is coated with a metal such as copper, and copper foil is preferred. The copper foil may be any one of rolled copper foil and electrolytic copper foil, preferably electrolytic copper foil. The thickness of the carrier is typically not more than 250 μm, preferably not less than 7 μm and not more than 200 μm.
載體之剝離層側之面較佳為平滑。亦即,於附載體銅箔之製造製程中,於載體之剝離層側之面形成(進行粗化處理之前之)極薄銅箔。在以附載體銅箔之形態使用本發明之粗化處理銅箔時,粗化處理銅箔可藉由對如此之極薄銅箔實施粗化處理而獲得。因此,藉由將載體之剝離層側之面預先平滑化,而亦可將極薄銅箔之外側之面平滑化,藉由對該極薄銅箔之平滑面實施粗化處理,而容易實現具有上述特定範圍內之峰及谷之高度之總和、以及峰及谷之平均高度之粗化處理面。為了將載體之剝離層側之面平滑化,例如可藉由對在將載體進行電解製箔時使用之陰極之表面以特定類型之拋光機進行研磨而調整表面粗糙度而進行。亦即,將經如此般調整之陰極之表面輪廓轉印於載體之電極面,藉由在該載體之電極面上隔著剝離層形成極薄銅箔,而可對極薄銅箔之外側之面賦予容易實現上述之粗化處理面之平滑之表面狀態。較佳之拋光之類型為#2000以上#3000以下,更佳為#2000以上#2500以下。使用以#2000以上#2500以下之類型之拋光機研磨之陰極所得之載體之電極面與平滑箔析出面相比,因具有輕度之起伏故可確保密接性且亦可確保平滑性,而可更加均衡性良好地實現高密接性與優異之傳送特性。又,基於將極薄銅箔設為更平滑、而將獲得之粗化處理銅箔之各種表面參數更加容易地控制於上述範圍之觀點,可將使用含有添加劑之電解液進行電解製箔之載體之析出面側作為載體之剝離層側之面。The surface of the carrier on the release layer side is preferably smooth. That is, in the manufacturing process of copper foil with carrier, an ultra-thin copper foil (before roughening treatment) is formed on the surface of the carrier on the release layer side. When the roughened copper foil of the present invention is used in the form of copper foil with a carrier, 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 side of the peeling layer in advance, the surface of the outer side of the ultra-thin copper foil can also be smoothed, and it can be easily realized by roughening the smooth surface of the ultra-thin copper foil. A roughened surface having the sum of the heights of the peaks and valleys and the average height of the peaks and valleys within the above specified range. In order to smoothen the surface of the release layer side of the carrier, for example, it is possible to adjust the surface roughness by polishing the surface of the cathode used in the electrolytic foiling of the carrier with a specific type of polisher. 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 through a release layer, and the outer surface of the ultra-thin copper foil can be processed. The surface provides a smooth surface state that facilitates the above-mentioned roughened surface. The preferred type of polishing is above #2000 and below #3000, more preferably above #2000 and below #2500. Compared with the smooth foil deposition surface, the electrode surface of the carrier obtained by using a cathode polished by a polishing machine of the type above #2000 and below #2500 can ensure adhesion and smoothness due to slight fluctuations, and can be more smooth. Well-balanced to achieve high adhesion and excellent transmission characteristics. In addition, based on the viewpoint of making the ultra-thin copper foil smoother and controlling various surface parameters of the obtained roughened copper foil more easily within the above range, it is possible to use an electrolyte solution containing additives for electrolytic foil production. The side of the precipitation side is used as the side of the release layer of the carrier.
剝離層為具有如下功能之圖:弱化載體之剝離強度,保證該強度之穩定性,進而抑制在高溫下之壓製成形時可能在載體與銅箔之間產生之相互擴散。剝離層一般形成於載體之一個面,亦可形成於兩面。剝離層可為有機剝離層及無機剝離層之任一者。作為使用於有機剝離層之有機成分之例,可舉出含氮有機化合物、含硫有機化合物、羧酸等。作為含氮有機化合物之例,可舉出***化合物、咪唑化合物等,其中***化合物基於剝離性容易穩定之點而為較佳。作為***化合物之例,可舉出1,2,3-苯并***、羧基苯并***、N',N'-雙(苯并***基甲基)脲、1H-1,2,4-***及3-胺基-1H-1,2,4-***等。作為含硫有機化合物之例,可舉出巰基苯并噻唑、硫氰尿酸、2-苯并咪唑硫醇等。作為羧酸之例,可舉出單羧酸、二羧酸等。另一方面,作為使用於無機剝離層之無機成分之例,可舉出Ni、Mo、Co、Cr、Fe、Ti、W、P、Zn、鉻酸鹽處理膜等。再者,剝離層之形成可藉由使剝離層成分含有溶液與載體之至少一個表面接觸,使剝離層成分固定於載體之表面等而進行。在使載體與剝離層成分含有溶液接觸時,可藉由浸漬於剝離層成分含有溶液、噴霧剝離層成分含有溶液、流下剝離層成分含有溶液等而進行該接觸。另外,亦可採用藉由蒸鍍或濺鍍等進行之氣相法而被膜形成剝離層成分之方法。又,剝離層成分之向載體表面之固定可藉由剝離層成分含有溶液之吸附或乾燥、剝離層成分含有溶液中之剝離層成分之電沈積等進行。剝離層之厚度典型而言為1 nm以上1 μm以下,較佳為5 nm以上500 nm以下。The peeling layer is a map that has the following functions: weakening the peeling strength of the carrier, ensuring the stability of the strength, and inhibiting the interdiffusion that may occur between the carrier and the copper foil during press molding at high temperature. The release layer is generally formed on one side of the carrier, and may be formed on both sides. The peeling layer may be any one of an organic peeling layer and an inorganic peeling layer. Examples of the organic component used in the organic release layer include nitrogen-containing organic compounds, sulfur-containing organic compounds, and carboxylic acids. Examples of nitrogen-containing organic compounds include triazole compounds, imidazole compounds, and the like, and among them, triazole compounds are preferable because the detachability is easily stabilized. Examples of triazole compounds include 1,2,3-benzotriazole, carboxybenzotriazole, N',N'-bis(benzotriazolylmethyl)urea, 1H-1,2 , 4-triazole and 3-amino-1H-1,2,4-triazole, etc. Examples of sulfur-containing organic compounds include mercaptobenzothiazole, thiocyanuric acid, and 2-benzimidazolethiol. As an example of a carboxylic acid, a monocarboxylic acid, a dicarboxylic acid, etc. are mentioned. On the other hand, Ni, Mo, Co, Cr, Fe, Ti, W, P, Zn, chromate treatment film, etc. are mentioned as an example of the inorganic component used for an inorganic peeling layer. Furthermore, the formation of the release layer can be carried out by bringing a solution containing the release layer components into contact with at least one surface of the carrier to fix the release layer components on the surface of the carrier, or the like. When the carrier is brought into contact with the solution containing the components of the release layer, the contact can be performed by immersing the solution containing the components of the release layer, spraying the solution containing the components of the release layer, or pouring the solution containing the components of the release layer. In addition, a method of forming a peeling layer component on a film by a gas phase method such as vapor deposition or sputtering can also be used. Also, the release layer components can be fixed to the carrier surface by adsorption or drying of the solution containing the release layer components, electrodeposition of the release layer components in the solution containing the release layer components, or the like. The thickness of the release layer is typically not less than 1 nm and not more than 1 μm, preferably not less than 5 nm and not more than 500 nm.
亦可根據期望,在剝離層與載體及/或粗化處理銅箔之間設置其他功能層。作為如此之其他功能層之例可舉出輔助金屬層。輔助金屬層較佳為包含鎳及/或鈷。藉由將如此之輔助金屬層形成於載體之表面側及/或粗化處理銅箔之表面側,而可抑制在高溫或長時間之熱壓成形時可能在載體與粗化處理銅箔之間產生之相互擴散,而保證載體之剝離強度之穩定性。輔助金屬層之厚度較佳的是設為0.001 μm以上3 μm以下。Other functional layers can also be provided between the release layer and the carrier and/or the roughened copper foil as desired. An example of such another functional layer is an auxiliary metal layer. The auxiliary metal layer preferably includes nickel and/or cobalt. By forming such an auxiliary metal layer on the surface side of the carrier and/or the surface side of the roughened copper foil, it is possible to suppress the possibility of a gap between the carrier and the roughened copper foil during high-temperature or long-term thermocompression forming. The resulting interdiffusion ensures the stability of the peel strength of the carrier. The thickness of the auxiliary metal layer is preferably set to not less than 0.001 μm and not more than 3 μm.
銅箔積層板本發明之粗化處理銅箔較佳的是使用於印刷配線板用銅箔積層板之製作。亦即,根據本發明之較佳之態樣,提供具備上述粗化處理銅箔之銅箔積層板。藉由使用本發明之粗化處理銅箔,於銅箔積層板之加工中,可兼顧優異之傳送特性與高抗剪強度。該銅箔積層板具備本發明之粗化處理銅箔、及與粗化處理銅箔之粗化處理面密接而設置之樹脂層。粗化處理銅箔可設置於樹脂層之一面,亦可設置於兩面。樹脂層包含樹脂、較佳的是包含絕緣性樹脂而成。樹脂層較佳為預浸體及/或樹脂片材。所謂預浸體,為使合成樹脂板、玻璃板、玻璃織布、玻璃不織布、紙等之基材含浸於合成樹脂而得之複合材料之總稱。作為絕緣性樹脂之較佳之例,可舉出環氧樹脂、氰酸酯樹脂、雙馬來亞醯胺三嗪樹脂(BT樹脂)、聚苯醚樹脂、酚樹脂等。又,作為構成樹脂片材之絕緣性樹脂之例,可舉出環氧樹脂、聚醯亞胺樹脂、聚酯樹脂等之絕緣樹脂。又,基於提高絕緣性等之觀點,樹脂層亦可含有包含氧化矽、氧化鋁等之各種無機粒子之填料粒子等。樹脂層之厚度並無特別限定,較佳為1 μm以上1000 μm以下,更佳為2 μm以上400 μm以下,尤佳為3 μm以上200 μm以下。樹脂層可由複數個層構成。預浸體及/或樹脂片材等之樹脂層可隔著預先塗佈於銅箔表面之底塗樹脂層設置於粗化處理銅箔。 Copper Foil Laminated Board The roughened copper foil of the present invention is preferably used in the production of copper foil laminated boards for printed wiring boards. That is, according to a preferable aspect of this invention, the copper foil laminated board provided with the said roughening process copper foil is provided. By using the roughened copper foil of the present invention, both excellent transmission characteristics and high shear strength can be achieved in the processing of copper foil laminates. This copper foil laminate is equipped with the roughening process copper foil of this invention, and the resin layer provided in close contact with the roughening process surface of the roughening process copper foil. The roughened copper foil can be provided on one side of the resin layer or on both sides. The resin layer contains resin, preferably insulating resin. The resin layer is preferably a prepreg and/or a resin sheet. The so-called prepreg is a general term for composite materials obtained by impregnating base materials such as synthetic resin plates, glass plates, glass woven fabrics, glass non-woven fabrics, and paper with synthetic resins. Preferable examples of insulating resins include epoxy resins, cyanate resins, bismaleimide triazine resins (BT resins), polyphenylene ether resins, and phenol resins. Moreover, examples of the insulating resin constituting the resin sheet include insulating resins such as epoxy resins, polyimide resins, and polyester resins. In addition, from the viewpoint of improving insulation and the like, the resin layer may contain filler particles including various inorganic particles such as silicon oxide and aluminum oxide. The thickness of the resin layer is not particularly limited, but it is preferably from 1 μm to 1000 μm, more preferably from 2 μm to 400 μm, and most preferably from 3 μm to 200 μm. The resin layer may consist of a plurality of layers. The resin layer of the prepreg and/or the resin sheet can be provided on the roughened copper foil through the primer resin layer coated on the surface of the copper foil in advance.
印刷配線板本發明之粗化處理銅箔較佳的是使用於印刷配線板之製作。亦即,根據本發明之較佳之態樣,提供具備上述粗化處理銅箔之印刷配線板。藉由使用本發明之粗化處理銅箔,在印刷配線板之製造中,可兼顧優異之傳送特性與高抗剪強度。本態樣之印刷配線板包含將樹脂層與銅層積層而成之層構成。銅層為由來於本發明之粗化處理銅箔之層。又,樹脂層為如對於銅箔積層板而於上述般。總之,印刷配線板除了使用本發明之粗化處理銅箔以外,亦可採用周知之層構成。作為與印刷配線板相關之具體例,可舉出在使本發明之粗化處理銅箔接著於預浸體之一面或兩面並硬化而形成積層體後進行電路形成之一面或兩面印刷配線板、或將該等多層化之多層印刷配線板等。又,作為又一具體例,可舉出在樹脂膜上形成本發明之粗化處理銅箔後形成電路之撓性印刷配線板、COF、TAB帶等。進而,作為再一具體例,可舉出向在本發明之粗化處理銅箔塗佈上述之樹脂層而形成附樹脂銅箔(RCC)、在以樹脂層為絕緣接著材層積層於上述之印刷基板之後、將粗化處理銅箔作為配線層之全部或一部分利用改良型半加成(MSAP)法、移除法等之方法形成電路之增層配線板,或向去除粗化處理銅箔利用半加成法形成電路之增層配線板,向半導體集積電路上交替地重複附樹脂銅箔之積層與電路形成的直接增層於晶圓(Direct build-up on wafer)等。作為更發展性之具體例,可舉出將上述附樹脂銅箔積層於基材進行電路形成之天線元件、經由接著劑層積層於玻璃或樹脂膜而形成圖案之面板、顯示器用電子材料或窗玻璃用電子材料、在本發明之粗化處理銅箔塗佈導電性接著劑而成之電磁波屏蔽膜等。特別是,具備本發明之粗化處理銅箔之印刷配線板較佳地用作於在信號頻率10 GHz以上之高頻帶中使用之汽車用天線、行動電話基地台天線、高性能伺服器、防碰撞用雷達等之用途下使用之高頻基板。特別是,本發明之粗化處理銅箔適合於MSAP法。例如,在藉由MSAP法進行電路形成時可採用如圖1及2所示之構成。 [實施例] Printed Wiring Board The roughened copper foil of the present invention is preferably used in the manufacture of printed wiring boards. That is, according to a preferable aspect of this invention, the printed wiring board provided with the said roughening process copper foil is provided. By using the roughened copper foil of the present invention, both excellent transmission characteristics and high shear strength can be achieved in the manufacture of printed wiring boards. The printed wiring board of this aspect includes the layer structure which laminated|stacked the resin layer and the copper layer. The copper layer is a layer derived from the roughened copper foil of the present invention. In addition, the resin layer is as above-mentioned about the copper foil laminated board. In short, a well-known layer structure can also be used for a printed wiring board other than using the roughened copper foil of this invention. Specific examples related to printed wiring boards include printed wiring boards on one or both sides of which a circuit is formed after the roughened copper foil of the present invention is adhered to one or both sides of a prepreg and hardened to form a laminate, Or a multilayer printed wiring board made of these multilayers. Moreover, as still another specific example, the roughened copper foil of this invention was formed on the resin film, and the flexible printed wiring board which formed the circuit, COF, TAB tape, etc. are mentioned. Furthermore, as yet another specific example, the above-mentioned resin layer is applied to the roughened copper foil of the present invention to form a resin-attached copper foil (RCC), and the resin layer is used as an insulating adhesive material to be laminated on the above-mentioned After printing the substrate, use the roughened copper foil as all or part of the wiring layer to form a build-up wiring board using the modified semi-additive (MSAP) method, removal method, etc., or to remove the roughened copper foil A build-up wiring board that uses a semi-additive method to form a circuit, alternately repeating the build-up of resin-coated copper foil and the direct build-up on wafer (Direct build-up on wafer) formed by the circuit on the semiconductor integrated circuit. Specific examples of further development include antenna elements in which the above-mentioned resin-attached copper foil is laminated on a substrate to form a circuit, a panel in which a pattern is formed by laminating on glass or a resin film via an adhesive, electronic materials for displays, or windows. Electronic material for glass, electromagnetic wave shielding film formed by coating conductive adhesive on roughened copper foil of the present invention, etc. In particular, the printed wiring board provided with the roughened copper foil of the present invention is preferably used in automotive antennas, mobile phone base station antennas, high-performance servers, anti-corrosion High-frequency substrates used in applications such as collision radar. In particular, the roughened copper foil of the present invention is suitable for the MSAP method. For example, the configurations shown in FIGS. 1 and 2 can be used when forming a circuit by the MSAP method. [Example]
藉由以下之例更具體地說明本發明。The present invention is described more specifically by the following examples.
例 1 、 2 及 4如以下般製作具備粗化處理銅箔之附載體銅箔。 Examples 1 , 2 , and 4 produced copper foil with a carrier having a roughened copper foil as follows.
(1)載體之準備 使用以下所示之組成之銅電解液、陰極、作為陽極之DSA(尺寸穩定性陽極),在溶液溫度50℃、電流密度70 A/dm 2下進行電解,將厚度18 μm之電解銅箔製作為載體。此時,作為陰極,使用將表面以#2000之拋光機研磨而調整了表面粗糙度之電極。 <銅電解液之組成> ‐ 銅濃度:80 g/L ‐ 硫酸濃度:300 g/L ‐ 氯濃度:30 mg/L ‐ 膠濃度:5 mg/L (1) Preparation of the carrier Use the copper electrolyte, cathode, and DSA (dimensionally stable anode) as the anode to perform electrolysis at a solution temperature of 50°C and a current density of 70 A/dm 2 , with a thickness of 18 μm electrolytic copper foil is used as the carrier. At this time, as a cathode, an electrode whose surface was polished with a #2000 polisher and whose surface roughness was adjusted was used. <Composition of Copper Electrolyte> - Copper concentration: 80 g/L - Sulfuric acid concentration: 300 g/L - Chlorine concentration: 30 mg/L - Glue concentration: 5 mg/L
(2)剝離層之形成 將經酸洗處理之載體之電極面在含有羧基苯并***(CBTA)濃度1 g/L、硫酸濃度150 g/L及銅濃度10 g/L之CBTA水溶液中,在液溫30℃下浸漬30秒鐘,使CBTA成分吸附於載體之電極面。如此般,在載體之電極面將CBTA層形成為有機剝離層。 (2) Formation of peeling layer Put the electrode surface of the acid-washed carrier in a CBTA aqueous solution containing carboxybenzotriazole (CBTA) concentration of 1 g/L, sulfuric acid concentration of 150 g/L and copper concentration of 10 g/L, at a liquid temperature of 30°C Immerse for 30 seconds to make the CBTA component adsorb on the electrode surface of the carrier. In this way, the CBTA layer was formed as an organic release layer on the electrode surface of the carrier.
(3)輔助金屬層之形成 將形成有機剝離層之載體浸漬於使用硫酸鎳製作之含有鎳濃度20 g/L之溶液中,在液溫45℃、pH3、電流密度5 A/dm 2之條件下,使相當於厚度0.001 μm之附著量之鎳附著於有機剝離層上。如此般,在有機剝離層上將鎳層形成為輔助金屬層。 (3) Formation of the auxiliary metal layer Immerse the carrier forming the organic release layer in a solution containing nickel concentration of 20 g/L made of nickel sulfate, under the conditions of liquid temperature 45°C, pH 3, and current density 5 A/dm 2 Next, nickel was deposited on the organic release layer in an amount corresponding to a thickness of 0.001 μm. In this way, the nickel layer was formed as the auxiliary metal layer on the organic release layer.
(4)極薄銅箔之形成 將形成有輔助金屬層之載體浸漬於以下所示之組成之銅溶液,在溶液溫度50℃、電流密度5 A/dm 2以上30 A/dm 2以下進行電解,而將厚度1.5 μm之極薄銅箔形成於輔助金屬層上。 <溶液之組成> ‐ 銅濃度:60 g/L ‐ 硫酸濃度:200 g/L (4) Formation of ultra-thin copper foil Immerse the carrier with the auxiliary metal layer in the copper solution of the composition shown below, and perform electrolysis at a solution temperature of 50°C and a current density of 5 A/ dm2 to 30 A/ dm2 , and an ultra-thin copper foil with a thickness of 1.5 μm is formed on the auxiliary metal layer. <Solution composition> - Copper concentration: 60 g/L - Sulfuric acid concentration: 200 g/L
(5)粗化處理 藉由在如此般形成之極薄銅箔之表面進行粗化處理而形成粗化處理銅箔,藉此獲得附載體銅箔。該粗化處理對於例1及2,進行以下所示之3階段之粗化處理。 ‐ 第1階段之粗化處理分成2次進行。具體而言,使用表1所示之銅濃度及硫酸濃度之酸性硫酸銅溶液,在表1所示之電流密度及液溫下進行2次粗化處理。 ‐ 第2階段之粗化處理使用表1所示之銅濃度及硫酸濃度之酸性硫酸銅溶液,在表1所示之電流密度及液溫下進行粗化處理。 ‐ 第3階段之粗化處理使用表1所示之銅濃度、硫酸濃度、氯濃度及9-苯基吖啶(9PA)濃度之酸性硫酸銅溶液,在表1所示之電流密度及液溫下進行粗化處理。 (5) Coarsening treatment Copper foil with a carrier is obtained by forming a roughened copper foil by roughening the surface of the ultra-thin copper foil thus formed. In this roughening process, with respect to Examples 1 and 2, three steps of roughening process shown below were performed. - The coarsening treatment of the first stage is divided into 2 times. Specifically, using the 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 roughening treatment of the second stage uses the acidic copper sulfate solution with the copper concentration and sulfuric acid concentration shown in Table 1, and performs the roughening treatment at the current density and liquid temperature shown in Table 1. ‐ The coarsening treatment of the third stage uses the 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 Coarse processing is performed below.
另一方面,對於例4進行2階段之粗化處理。該2階段之粗化處理包含在極薄銅箔之上使細微銅粒析出附著之燒鍍步驟、及防止該細微銅粒之脫落之外覆鍍敷步驟。於燒鍍步驟中,於銅濃度10 g/L及硫酸濃度200 g/L之酸性硫酸銅溶液中,以成為表1所示之濃度之方式添加羧基苯并***(CBTA),在表1所示之電流密度及液溫下進行粗化處理。於其後之外覆鍍敷步驟中,使用銅濃度70 g/L及硫酸濃度240 g/L之酸性硫酸銅溶液,在液溫52℃及表1所示之電流密度之平滑鍍敷條件下進行電沈積。On the other hand, for Example 4, two stages of roughening treatment were performed. The two-stage roughening process includes a firing plating step for depositing and attaching fine copper particles on the ultra-thin copper foil, and an overcoating plating step for preventing the fine copper particles from falling off. In the firing plating step, carboxybenzotriazole (CBTA) was added to the acidic copper sulfate solution having a copper concentration of 10 g/L and a sulfuric acid concentration of 200 g/L so as to have the concentration shown in Table 1. Coarsening was performed at the indicated current densities and liquid temperatures. In the subsequent outer plating step, use an acidic copper sulfate solution with a copper concentration of 70 g/L and a sulfuric acid concentration of 240 g/L, under smooth plating conditions with a liquid temperature of 52°C and a current density shown in Table 1. Conduct electrodeposition.
(6)防鏽處理
對獲得之附載體銅箔之粗化處理表面,進行包含鋅-鎳合金鍍敷處理及鉻酸鹽處理之防鏽處理。首先,使用含有鋅濃度1 g/L、鎳濃度2 g/L及焦磷酸鉀濃度80 g/L之溶液,在液溫40℃、電流密度0.5 A/dm
2之條件下對粗化處理層及載體之表面進行鋅-鎳合金鍍敷處理。接著,使用含有鉻酸1 g/L之水溶液,在pH12、電流密度1 A/dm
2之條件下,對經進行鋅-鎳合金鍍敷處理之表面進行鉻酸鹽處理。
(6) Antirust treatment The roughened surface of the obtained copper foil with a carrier was subjected to antirust treatment including zinc-nickel alloy plating treatment and chromate treatment. First, use 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 to roughen the layer at a liquid temperature of 40°C and a current density of 0.5 A/ dm2 . And the surface of the carrier is treated with zinc-nickel alloy plating. Then, using an aqueous solution containing 1 g/L of chromic acid, under the conditions of
(7)矽烷偶合劑處理 使含有市售之矽烷偶合劑之水溶液吸附於附載體銅箔之粗化處理銅箔側之表面,藉由利用電熱器使水分蒸發,而進行矽烷偶合劑處理。此時,矽烷偶合劑處理不在載體側進行。 (7) Silane coupling agent treatment The aqueous solution containing a commercially available silane coupling agent is adsorbed on the surface of the copper foil with a carrier on the roughened copper foil side, and the silane coupling agent treatment is performed by evaporating water with an electric heater. At this time, the silane coupling agent treatment is not performed on the carrier side.
例 3除了下述a)及b)以外,與例1同樣地進行粗化處理銅箔之製作。 a)取代附載體銅箔,對以下之電解銅箔之析出面進行粗化處理。 b)如表1所示般變更粗化處理條件。 Example 3 Except the following a) and b), it carried out similarly to Example 1, and produced the roughening process copper foil. a) Instead of the copper foil with a carrier, roughen the deposition surface of the following electrolytic copper foil. b) The roughening treatment conditions were changed as shown in Table 1.
(電解銅箔之準備) 作為銅電解液使用以下所示之組成之硫酸酸性硫酸銅溶液,陰極使用表面粗糙度Ra為0.20 μm之鈦製之電極,陽極使用DSA(尺寸穩定性陽極),在溶液溫度45℃、電流密度55 A/dm 2下進行電解,而獲得厚度12 μm之電解銅箔。 <硫酸酸性硫酸銅溶液之組成> ‐ 銅濃度:80 g/L ‐ 硫酸濃度:260 g/L ‐ 雙(3-磺丙基)二硫化物濃度:30 mg/L ‐二烯丙基二甲基氯化銨共聚物濃度:50 mg/L ‐ 氯濃度:40 mg/L (Preparation of Electrolytic Copper Foil) As the copper electrolyte, a sulfuric acid copper sulfate solution with the composition shown below was used, a titanium electrode with a surface roughness Ra of 0.20 μm was used for the cathode, and DSA (dimensionally stable anode) was used for 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 acidic copper sulfate solution> - Copper concentration: 80 g/L - Sulfuric acid concentration: 260 g/L - Bis(3-sulfopropyl) disulfide concentration: 30 mg/L - Diallyl dimethyl Ammonium chloride copolymer concentration: 50 mg/L ‐ Chlorine concentration: 40 mg/L
例 5(比較) 於粗化處理步驟中,不進行第1階段及第2階段之粗化處理,除了如表1所示般變更第3階段之粗化處理條件以外,與例3同樣地進行粗化處理銅箔之製作。 Example 5 (Comparison) In the roughening process, the roughening treatment of the first and second stages was not performed, and the roughening treatment conditions of the third stage were changed as shown in Table 1, and it was carried out in the same manner as in Example 3. Production of roughened copper foil.
[表1]
表1
評估對於在例1~5中製作之粗化處理銅箔或附載體銅箔,進行如以下所示之各種評估。 Evaluation Various evaluations shown below were performed on the roughened copper foil or the copper foil with a carrier produced in Examples 1-5.
(a)粗化處理面之三維圖像解析參數 藉由對於粗化處理銅箔或附載體銅箔進行粗化處理面之三維圖像解析,而分別算出峰及谷之平均高度、峰及谷之高度之總和、表面體元比、以及每1 nm 2單位面積之峰之總體積。具體之程序如以下所述般。 (a) Three-dimensional image analysis parameters of the roughened surface By analyzing the three-dimensional image of the roughened copper foil or the copper foil with a carrier, the average height of the peaks and valleys, and the peaks and valleys are calculated. The sum of the heights, the surface voxel ratio, and the total volume of the peak per 1 nm 2 unit area. The specific procedures are as follows.
(a-1)3D-SEM觀察
使用FIB-SEM裝置(Carl Zeiss公司製Crossbeam540,SEM控制:附服務軟體組8之SmartSEM 版本 6.06,FIB控制:SmartFIB v1.11.0),對於粗化處理面之10240 nm×7680 nm之區域,在下述測定條件下進行三維形狀資料之取得。該三維形狀資料之取得如圖7所示般在將x軸及z軸設為粗化處理銅箔10之面內方向、且將y軸規定為粗化處理銅箔10之厚度方向後,取得與x-y面平行之切割面S處之粗化處理銅箔10之剖面圖像,使該切割面沿z軸方向逐次平行移動10 nm,且在上述解析區域內取得合計1000張之剖面圖像。再者,此次在下述條件下觀察,但觀察條件可根據裝置之狀態(機型等)而適當選擇或變更。
(a-1) 3D-SEM observation
Using a FIB-SEM device (Crossbeam540 manufactured by Carl Zeiss, SEM control: SmartSEM version 6.06 with service software group 8, FIB control: SmartFIB v1.11.0), for the area of 10240 nm×7680 nm on the roughened surface, in the following Acquisition of 3D shape data under measurement conditions. The three-dimensional shape data is acquired after setting the x-axis and z-axis as the in-plane direction of the roughened
<SEM條件> ‐加速電壓:1.0 kV ‐工作距離(Working distance):5mm ‐傾斜(Tilt):54°(有SEM像之傾斜修正) ‐檢測器:InLens檢測器 ‐行模式(Column Mode):高解析度(High Resolution) ‐像素數:2048(x方向) <FIB條件> ‐加速電壓:30 kV ‐切割厚度:10 nm(切割面S之間隔) ‐體元尺寸之設定: 如(x、y、z)=(5 nm、5 nm、10 nm)般決定欲設定之體元尺寸。x、y之像素尺寸可藉由FIB-SEM條件而設定,藉由以FIB-SEM之像素數乘以x、y之像素尺寸而得之數值成為FIB-SEM之縮尺之方式調整倍率,而進行設定。若像素數為2048,x、y之像素尺寸為5 nm、5 nm時,則以2048×5 nm=10240 nm成為FIB-SEM之x軸之縮尺之方式調整倍率。若x軸之縮尺決定,則y軸之縮尺亦決定。因z之體元尺寸係由切割厚度(切割面S之間隔)之數值決定,故在欲將z設為10 nm時,將切割厚度設為10 nm。再者,亦可以成為經決定之體元尺寸之方式,藉由裝置(機種或軟體等)適當變更觀察倍率。 <SEM conditions> ‐Acceleration voltage: 1.0 kV ‐Working distance: 5mm ‐Tilt: 54° (with SEM image tilt correction) ‐Detector: InLens detector ‐Column Mode: High Resolution - Number of pixels: 2048 (x direction) <FIB conditions> ‐Acceleration voltage: 30 kV ‐Cutting thickness: 10 nm (interval between cutting surfaces S) ‐Voxel size setting: Such as (x, y, z) = (5 nm, 5 nm, 10 nm) to determine the voxel size to be set. The pixel size of x and y can be set by the FIB-SEM conditions, and the magnification is adjusted by multiplying the pixel number of FIB-SEM by the pixel size of x and y to become the scale of FIB-SEM. set up. If the number of pixels is 2048, and the x and y pixel sizes are 5 nm and 5 nm, adjust the magnification in such a way that 2048×5 nm=10240 nm becomes the scale of the x-axis of FIB-SEM. If the scale of the x-axis is determined, the scale of the y-axis is also determined. Since the voxel size of z is determined by the value of the cutting thickness (interval between cutting planes S), when z is set to be 10 nm, the cutting thickness is set to 10 nm. Furthermore, the determined voxel size can also be used to appropriately change the observation magnification through the device (model or software, etc.).
(a-2)3D-SEM圖像解析
自藉由3D-SEM獲得之粗化處理銅箔之三維形狀資料之切割圖像利用三維定位軟體「ExFact Slice Aligner(版本2.0)」(日本VISUAL SCIENCE株式會社製)以z軸之觀察長度成為2 μm以上之方式進行漂移之修正。對於漂移修正後之切割圖像,使用三維圖像解析軟體「ExFact VR(版本2.2)」(日本VISUAL SCIENCE株式會社製)進行三維再構建。此時,解析區域設為2000 nm×1000 nm×2000 nm(在俯視粗化處理銅箔10時為2000 nm×2000 nm),每1體元之大小設為(x、y、z)=(5 nm、5 nm、10 nm)。其後,在如圖8所示般以粗化處理面成為x-y面之方式使軸旋轉後,藉由利用「foil Analysis(版本1.0)」(日本VISUAL SCIENCE株式會社製)進行圖像解析,而如下述般取得與粗化處理面相關之各種資料。
(a-2) 3D-SEM image analysis
The cutting image obtained from the three-dimensional shape data of the roughened copper foil obtained by 3D-SEM uses the three-dimensional positioning software "ExFact Slice Aligner (version 2.0)" (manufactured by Japan Visual Science Co., Ltd.) to make the observation length of the z-axis 2 Correct the drift in the way of μm or more. For the cut image after drift correction, three-dimensional reconstruction was carried out using the three-dimensional image analysis software "ExFact VR (version 2.2)" (manufactured by Japan Visual Science Co., Ltd.). At this time, the analysis area is set to 2000 nm×1000 nm×2000 nm (2000 nm×2000 nm when the roughened
<預先解析:峰及谷之決定> 對於三維再構建資料以大津二值化進行二值化處理,將空氣與粗化處理銅箔予以分離。對於獲得之二值資料,去除起因於粗化處理銅箔中之空隙、及3D-SEM圖像取得時之沈積之破裂等之雜訊,解析粗化處理銅箔之凹凸構造。對於獲得之粗化處理銅箔之凹凸構造應用中值濾波器,而製作粗化處理面之凹凸之基準面。此時,中值濾波器之矩陣尺寸設為99。然後,分別將相對於基準面成為凸部之部分定義為峰,將相對於基準面成為凹部之部分定義為谷。將峰及谷個別地標籤化,如以下所述般算出解析區域內之峰及谷之平均高度、峰及谷之高度之總和、表面體元比、以及每1 nm 2單位面積之峰之總體積。 <Pre-analysis: Determination of peaks and valleys> For the three-dimensional reconstruction data, Otsu binarization is used to perform binarization, and the air and the roughened copper foil are separated. For the obtained binary data, the noise caused by the voids in the roughened copper foil and the cracks of the deposition when the 3D-SEM image was obtained was removed, and the uneven structure of the roughened copper foil was analyzed. A median filter was applied to the uneven structure of the obtained roughened copper foil, and a reference plane for the unevenness of the roughened surface was created. At this time, the matrix size of the median filter is set to 99. Then, a portion that becomes a convex portion with respect to the reference plane is defined as a peak, and a portion that becomes a concave portion with respect to the reference plane is defined as a valley. Label the peaks and valleys individually, and calculate the average height of the peaks and valleys, the sum of the heights of the peaks and valleys, the surface voxel ratio, and the total volume of the peaks per 1 nm2 unit area in the analysis region as follows .
<解析區域之峰及谷之平均高度> 將藉由三維圖像解析軟體「foil Analysis(版本1.0)」算出之「plusMean」與「minusMean」之和作為峰及谷之平均高度(體元值)。此處,「plusMean」表示峰之高度之平均值(體元值),「minusMean」表示谷之高度之平均值(體元值)。藉由將獲得之峰及谷之平均高度(體元值)乘以每1體元之高度(亦即5 nm),而算出解析區域內之峰及谷之平均高度(nm)。結果如表2所示般。 <Average height of peaks and valleys in the analysis area> The sum of "plusMean" and "minusMean" calculated by the three-dimensional image analysis software "foil Analysis (version 1.0)" was used as the average height (voxel value) of peaks and valleys. Here, "plusMean" represents the mean value (voxel value) of the peak height, and "minusMean" represents the mean value (voxel value) of the valley height. The average height (nm) of peaks and valleys within the analysis region was calculated by multiplying the obtained average heights (voxel value) of peaks and valleys by the height per 1 voxel (ie, 5 nm). The results are as shown in Table 2.
<峰及谷之高度之總和> 將藉由三維圖像解析軟體「foil Analysis(版本1.0)」算出之「plusSum」與「minusSum」之和作為峰及谷之高度之總和(體元值)。此處,「plusSum」表示峰之計數像素(體元)之總和,「minusSum」表示谷之計數像素(體元)之總和。藉由將峰及谷之高度之總和(體元值)乘以每1體元之體積(亦即5 nm×5 nm×10 nm),而算出解析區域內之峰及谷之高度之總和( nm 3)。結果如表2所示般。 <The sum of peak and valley heights> The sum of "plusSum" and "minusSum" calculated by the 3D image analysis software "foil Analysis (version 1.0)" was used as the sum of peak and valley heights (voxel value). Here, "plusSum" represents the sum of counted pixels (voxels) of peaks, and "minusSum" represents the sum of counted pixels (voxels) of valleys. The sum of the heights of the peaks and valleys in the analytical region ( nm 3 ). The results are as shown in Table 2.
<表面體元比> 如圖5所示般,將構成經標籤化之各個峰之表面(與大氣接觸之面)之體元作為表面體元Bs。具體而言,將利用藉由三維圖像解析軟體「foil Analysis(版本1.0)」之解析而產生之「voidsSummary_kobu」Excel 資料而算出之「volume_voxels_sum」作為構成峰之所有體元之總體積(體元值),將「surface_voxels_sum」作為表面體元Bs之總體積(體元值)。藉由將表面體元Bs之總體積以構成峰之所有體元之總體積相除,而算出解析區域內之表面體元比。 <Surface Voxel Ratio> As shown in FIG. 5 , a voxel constituting the surface (surface in contact with the atmosphere) of each tagged peak is referred to as a surface voxel Bs. Specifically, the "volume_voxels_sum" calculated using the "voidsSummary_kobu" Excel data generated by the analysis of the three-dimensional image analysis software "foil Analysis (version 1.0)" was used as the total volume of all voxels constituting the peak (voxel value ), use "surface_voxels_sum" as the total volume (voxel value) of the surface voxels Bs. The ratio of surface voxels in the resolved region was calculated by dividing the total volume of surface voxels Bs by the total volume of all voxels constituting the peak.
<每1 nm 2單位面積之峰之總體積> 將利用藉由三維圖像解析軟體「foil Analysis(版本1.0)」之解析而產生之「voidsSummary_kobu」Excel 資料而算出之「volume_voxels_sum」作為峰之總體積(體元值)。藉由將峰之總體積(體元值)乘以每1體元之體積(亦即5 nm×5 nm×10 nm),而求得峰之總體積(nm 3),藉由將其以解析區域(2000 nm×2000 nm)之面積相除而算出每1 nm 2單位面積之峰之總體積(nm 3)。結果如表2所示般。 <Total volume of the peak per 1 nm2 unit area> The "volume_voxels_sum" calculated using the "voidsSummary_kobu" Excel data generated by the analysis of the three-dimensional image analysis software "foil Analysis (version 1.0)" was used as the total volume of the peak ( voxel value). The total volume of the peak (nm 3 ) was obtained by multiplying the total volume of the peak (voxel value) by the volume per 1 voxel (ie, 5 nm×5 nm×10 nm), and by dividing it into the resolution area (2000 nm×2000 nm) areas were divided to calculate the total volume (nm 3 ) of the peak per unit area of 1 nm 2 . The results are as shown in Table 2.
(b)抗剪強度 使用獲得之粗化處理銅箔或附載體銅箔製作評估用積層體。亦即,在內層基板之表面,隔著預浸體(三菱瓦斯化學株式會社製、GHPL-830NSF、厚度30 μm)以抵接粗化處理面之方式積層附載體銅箔或粗化處理銅箔,在壓力4.0 MPa、溫度220℃下熱壓接90分鐘。其後,若為附載體銅箔則剝離載體,而獲得評估用積層體。 (b) Shear strength Use the obtained roughened copper foil or copper foil with a carrier to make a laminate for evaluation. That is, on the surface of the inner substrate, the copper foil with a carrier or the roughened copper layer is laminated so as to be in contact with the roughened surface through a prepreg (manufactured by Mitsubishi Gas Chemical Co., Ltd., GHPL-830NSF, thickness 30 μm). The foil was bonded by thermocompression at a pressure of 4.0 MPa and a temperature of 220° C. for 90 minutes. Then, if it is copper foil with a carrier, a carrier is peeled off, and the laminated body for evaluation is obtained.
在上述之評估用積層體貼合乾膜,進行曝光及顯影。在使由經顯影之乾膜遮罩之積層體藉由圖案鍍敷而析出銅層後,剝離乾膜。對藉由硫酸-過氧化氫系蝕刻液而露出之銅部分進行蝕刻,製作高度15 μm、寬度14 μm、長度150 μm之抗剪強度測定用樣品。使用接合強度試驗機(Nordson DAGE公司製 4000Plus Bond tester),測定將抗剪強度測定用樣品自橫向推倒時之抗剪強度。此時,測試種類設為破壞試驗,在測試高度5 μm、下降速度0.05 mm/s、測試速度200 μm/s、工具移動量0.03 mm、破壞辨識點10%之條件下進行測定。對獲得之抗剪強度按照以下之基準進行分等級評估,將評估A及B判定為合格。結果如表2所示般。 <抗剪強度評估基準> ‐評估A:抗剪強度為21.3 gf/cm以上 ‐評估B:抗剪強度超過19.9 gf/cm、未達21.3 gf/cm ‐評估C:抗剪強度為19.9 gf/cm以下 A dry film was attached to the above-mentioned laminated body for evaluation, and exposure and development were performed. After the layered body masked by the developed dry film was deposited by pattern plating to deposit a copper layer, the dry film was peeled off. Etch the copper part exposed by the sulfuric acid-hydrogen peroxide-based etchant, and prepare a sample for measuring shear strength with a height of 15 μm, a width of 14 μm, and a length of 150 μm. Using a bond strength tester (4000Plus Bond tester manufactured by Nordson DAGE), the shear strength when the sample for shear strength measurement was pushed down from the lateral direction was measured. At this time, the test type is set as a destruction test, and the measurement is carried out under the conditions of a test height of 5 μm, a falling speed of 0.05 mm/s, a test speed of 200 μm/s, a tool movement of 0.03 mm, and a failure identification point of 10%. The obtained shear strength was graded and evaluated according to the following criteria, and the evaluations A and B were judged to be acceptable. The results are as shown in Table 2. <Shear Strength Evaluation Standard> ‐Evaluation A: The shear strength is 21.3 gf/cm or more ‐Assessment B: The shear strength exceeds 19.9 gf/cm but falls short of 21.3 gf/cm ‐Evaluation C: The shear strength is 19.9 gf/cm or less
(c)傳送特性 重疊2個預浸體(Panasonic株式會社製、MEGTRON6、實際厚度68 μm),將附載體銅箔或粗化處理銅箔之粗化處理面抵接於其兩面,使用真空壓製機在溫度190℃下熱壓接90分鐘。其後,若為附載體銅箔則剝離載體而獲得銅箔積層板。以該銅箔積層板之銅厚度成為18 μm之方式進行銅鍍覆,藉由移除法,獲得形成有微帶電路之傳送特性測定用基板。 (c) Transmission characteristics Two prepregs (Panasonic Co., Ltd., MEGTRON6, actual thickness 68 μm) are stacked, and the roughened surface of the copper foil with the carrier or the roughened copper foil is abutted on both sides, and the temperature is 190 ℃ using a vacuum press machine. Under thermocompression bonding for 90 minutes. Then, if it is copper foil with a carrier, the carrier is peeled off and the copper foil laminated board is obtained. Copper plating was performed so that the copper thickness of this copper-clad laminated board became 18 μm, and a substrate for measurement of transmission characteristics on which a microstrip circuit was formed was obtained by a removal method.
對於獲得之傳送特性測定用基板,使用網路分析器(Agilent公司製、PNA-X N5245A),選定電路之特性阻抗為50 Ω之圖案,測定直至50 GHz之傳送損失S21(dB/cm)。算出獲得之45~50 GHz下之傳送損失量之平均,對於其絕對值按照以下之基準進行分等級評估。而且在傳送特性評估為A或B時判定為合格。結果如表2所示般。 <傳送特性評估基準> ‐評估A:傳送損失量之絕對值為0.455 dB/cm以下 ‐評估B:傳送損失量之絕對值超過0.455 dB/cm、未達0.465 dB/cm ‐評估C:傳送損失量之絕對值為0.465 dB/cm以上 For the obtained substrate for measurement of transmission characteristics, using a network analyzer (manufactured by Agilent, PNA-X N5245A), a pattern with a characteristic impedance of the circuit of 50 Ω was selected, and the transmission loss S21 (dB/cm) up to 50 GHz was measured. Calculate the average of the obtained transmission loss at 45-50 GHz, and evaluate the absolute value according to the following criteria. Furthermore, when the transfer characteristic evaluation was A or B, it was judged as pass. The results are as shown in Table 2. <Evaluation criteria for transmission characteristics> ‐Evaluation A: The absolute value of transmission loss is 0.455 dB/cm or less ‐Evaluation B: The absolute value of the transmission loss exceeds 0.455 dB/cm but falls below 0.465 dB/cm ‐Evaluation C: The absolute value of transmission loss is 0.465 dB/cm or more
[表2]
表2
10:粗化處理銅箔
10a:粗化粒子
11:絕緣樹脂基板
11a:基底基材
11b:下層電路
12:預浸體
13:底塗層
14:導通孔
15:化學銅鍍覆
16:乾膜
17:電鍍銅
17a:配線部分
18:配線
Ap:相對於基準面之峰之體積
Av:相對於基準面之谷之體積
B:體元
Bs:表面體元
H:峰及谷之平均高度
Hp:相對於基準面之峰之高度
Hv:相對於基準面之谷之高度
N:區域
P
1,P
2,P
3:峰
R:基準面
S:切割面
x,y,z:軸
10: roughened
圖1(a)~(d)係用於說明MSAP法之步驟流程圖,係顯示前半部分之步驟(步驟(a)~(d))之圖。 圖2(e)~(g)係用於說明MSAP法之步驟流程圖,係顯示後半之部分步驟(步驟(e)~(g))之圖。 圖3係用於說明粗化處理銅箔之粗化處理面之基準面、以及峰及谷之高度之總和之示意剖面圖。 圖4係用於說明粗化處理銅箔之粗化處理面之基準面、以及峰及谷之平均高度之示意剖面圖。 圖5係將粗化處理銅箔內之存在於粗化處理面之峰藉由體元而假想性地區劃之圖。 圖6係顯示在藉由雷射顯微鏡測定粗化處理面時的雷射光無法入射之區域之圖。 圖7係將3D-SEM觀察下之x軸、y軸及z軸、以及切割面S在與粗化處理銅箔之關係下顯示之圖。 圖8係顯示3D-SEM圖像解析中之使x軸、y軸及z軸旋轉後之各軸與粗化處理銅箔之關係之圖。 Fig. 1(a)-(d) is a flowchart for explaining the steps of the MSAP method, and is a diagram showing the first half of the steps (steps (a)-(d)). Fig. 2(e)-(g) is a flowchart for explaining the steps of the MSAP method, and is a diagram showing some steps (steps (e)-(g)) in the second half. Fig. 3 is a schematic cross-sectional view illustrating a reference plane of a roughened surface of a roughened copper foil, and a sum of heights of peaks and valleys. Fig. 4 is a schematic cross-sectional view illustrating the reference plane of the roughened surface of the roughened copper foil and the average height of peaks and valleys. FIG. 5 is a diagram in which the peaks existing on the roughened surface in the roughened copper foil are hypothetically divided by voxels. Fig. 6 is a diagram showing a region where laser light does not enter when a roughened surface is measured with a laser microscope. Fig. 7 is a diagram showing the x-axis, y-axis and z-axis under 3D-SEM observation, and the cut surface S in relation to the roughened copper foil. Fig. 8 is a diagram showing the relationship between each axis and the roughened copper foil after rotating the x-axis, y-axis, and z-axis in 3D-SEM image analysis.
10:粗化處理銅箔 10: Coarse treatment of copper foil
Ap:相對於基準面之峰之體積 Ap: The volume of the peak relative to the reference plane
Av:相對於基準面之谷之體積 Av: the volume of the valley relative to the datum
R:基準面 R: reference plane
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WO (1) | WO2022244826A1 (en) |
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JP5242710B2 (en) * | 2010-01-22 | 2013-07-24 | 古河電気工業株式会社 | Roughening copper foil, copper clad laminate and printed wiring board |
JP5204908B1 (en) * | 2012-03-26 | 2013-06-05 | Jx日鉱日石金属株式会社 | Copper foil with carrier, method for producing copper foil with carrier, copper foil with carrier for printed wiring board and printed wiring board |
JP5481577B1 (en) * | 2012-09-11 | 2014-04-23 | Jx日鉱日石金属株式会社 | Copper foil with carrier |
JP6591893B2 (en) * | 2013-06-04 | 2019-10-16 | Jx金属株式会社 | Copper foil with carrier, copper clad laminate, printed wiring board, electronic device, resin layer, method for producing copper foil with carrier, and method for producing printed wiring board |
JP6373166B2 (en) * | 2014-10-30 | 2018-08-15 | Jx金属株式会社 | Surface-treated copper foil and laminate |
KR102031065B1 (en) | 2015-01-22 | 2019-10-11 | 미쓰이금속광업주식회사 | Ultrathin copper foil with carrier and method for manufacturing same, copper-clad laminate, and method for manufacturing printed-wiring board |
CN107532322B (en) * | 2015-04-28 | 2019-07-16 | 三井金属矿业株式会社 | Roughening treatment copper foil 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 |
JP6182584B2 (en) * | 2015-12-09 | 2017-08-16 | 古河電気工業株式会社 | Surface-treated copper foil for printed wiring board, copper-clad laminate for printed wiring board, and printed wiring board |
JP6430092B1 (en) * | 2017-05-19 | 2018-11-28 | 三井金属鉱業株式会社 | Roughened copper foil, copper foil with carrier, copper clad laminate and printed wiring board |
CN111344435A (en) * | 2017-11-10 | 2020-06-26 | 纳美仕有限公司 | Composite copper foil |
KR102480377B1 (en) | 2018-08-10 | 2022-12-23 | 미쓰이금속광업주식회사 | Roughened copper foil, copper foil with carrier, copper-clad laminate and printed wiring board |
US10581081B1 (en) * | 2019-02-01 | 2020-03-03 | Chang Chun Petrochemical Co., Ltd. | Copper foil for negative electrode current collector of lithium ion secondary battery |
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- 2022-05-18 JP JP2023522710A patent/JPWO2022244826A1/ja active Pending
- 2022-05-18 KR KR1020237038900A patent/KR20240009403A/en unknown
- 2022-05-18 WO PCT/JP2022/020747 patent/WO2022244826A1/en active Application Filing
- 2022-05-18 CN CN202280035616.5A patent/CN117321253A/en active Pending
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WO2022244826A1 (en) | 2022-11-24 |
KR20240009403A (en) | 2024-01-22 |
CN117321253A (en) | 2023-12-29 |
TWI804323B (en) | 2023-06-01 |
JPWO2022244826A1 (en) | 2022-11-24 |
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