WO2022255420A1 - 粗化処理銅箔、銅張積層板及びプリント配線板 - Google Patents
粗化処理銅箔、銅張積層板及びプリント配線板 Download PDFInfo
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- WO2022255420A1 WO2022255420A1 PCT/JP2022/022386 JP2022022386W WO2022255420A1 WO 2022255420 A1 WO2022255420 A1 WO 2022255420A1 JP 2022022386 W JP2022022386 W JP 2022022386W WO 2022255420 A1 WO2022255420 A1 WO 2022255420A1
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- Prior art keywords
- copper foil
- roughened
- less
- vmc
- vmp
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 186
- 239000011889 copper foil Substances 0.000 title claims abstract description 164
- 239000002245 particle Substances 0.000 claims abstract description 44
- 238000007788 roughening Methods 0.000 claims description 38
- 239000010949 copper Substances 0.000 claims description 26
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 25
- 229910052802 copper Inorganic materials 0.000 claims description 24
- 238000005520 cutting process Methods 0.000 claims description 14
- 230000008021 deposition Effects 0.000 claims description 10
- 230000005540 biological transmission Effects 0.000 abstract description 45
- 239000000463 material Substances 0.000 abstract description 8
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- 238000000034 method Methods 0.000 description 12
- 238000007747 plating Methods 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 238000005259 measurement Methods 0.000 description 10
- 239000011701 zinc Substances 0.000 description 10
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 9
- 238000010586 diagram Methods 0.000 description 9
- 229910052725 zinc Inorganic materials 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 6
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- 239000000203 mixture Substances 0.000 description 6
- 239000002800 charge carrier Substances 0.000 description 5
- 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 5
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 5
- 229910000990 Ni alloy Inorganic materials 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
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- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910001297 Zn alloy Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
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- 229910052801 chlorine Inorganic materials 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 2
- 235000011180 diphosphates Nutrition 0.000 description 2
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- 239000003822 epoxy resin Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 229920003192 poly(bis maleimide) Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920001955 polyphenylene ether Polymers 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
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- 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 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-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
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- ZDDUSDYMEXVQNJ-UHFFFAOYSA-N 1H-imidazole silane Chemical compound [SiH4].N1C=NC=C1 ZDDUSDYMEXVQNJ-UHFFFAOYSA-N 0.000 description 1
- ZOTOAABENXTRMA-UHFFFAOYSA-N 3-[4-[3-(3-trimethoxysilylpropylamino)propoxy]butoxy]propan-1-amine Chemical compound CO[Si](OC)(OC)CCCNCCCOCCCCOCCCN ZOTOAABENXTRMA-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 101001134276 Homo sapiens S-methyl-5'-thioadenosine phosphorylase Proteins 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 102100022050 Protein canopy homolog 2 Human genes 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
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- 229910001431 copper ion Inorganic materials 0.000 description 1
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- 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
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
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- 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
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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
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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
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
-
- 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
- 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
- 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
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
Definitions
- the present invention relates to roughened copper foils, copper clad laminates and printed wiring boards.
- copper foil is widely used in the form of copper-clad laminates laminated with insulating resin substrates.
- the copper foil and the insulating resin base material have high adhesive strength in order to prevent the wiring from being peeled off during the production of the printed wiring board. Therefore, in ordinary copper foils for manufacturing printed wiring boards, the bonding surface of the copper foil is roughened to form unevenness made of fine copper particles, and the unevenness is pressed into the insulating resin base material. Adhesion is improved by exerting an anchor effect.
- Patent Document 1 Japanese Patent Application Laid-Open No. 2018-172785
- Patent Document 1 Japanese Patent Application Laid-Open No. 2018-172785
- a surface-treated copper foil having an arithmetic mean roughness Ra of 0.08 ⁇ m or more and 0.20 ⁇ m or less on the roughened layer side surface and a TD (width direction) gloss of the roughened layer side surface of 70% or less. disclosed.
- a printed wiring board comprises a copper foil processed into a wiring pattern and an insulating base material. losses.
- Patent Document 2 Japanese Patent Application Laid-Open No. 2015-148011 describes a technique for providing a surface-treated copper foil with low signal transmission loss and a laminated board using the same, and the copper foil surface is improved by surface treatment. It discloses that the skewness Rsk based on JIS B0601-2001 is controlled within a predetermined range of -0.35 or more and 0.53 or less.
- the present inventors have recently investigated the volume of fine tip particles calculated based on the actual volume Vmp of the protruding peaks, the actual volume Vmc of the core portions, and the peak density Spd of the peaks, and the cutting level on the surface of the roughened copper foil.
- the present inventors have found that by controlling the difference Rdc within a predetermined range, it is possible to achieve both excellent transmission characteristics and high peel strength in a copper-clad laminate or printed wiring board manufactured using this.
- an object of the present invention is to provide a roughened copper foil that can achieve both excellent transmission characteristics and high peel strength when used in copper-clad laminates or printed wiring boards.
- a roughened copper foil having a roughened surface on at least one side has an actual volume Vmp ( ⁇ m 3 / ⁇ m 2 ) of the protruding ridges per unit area, an actual volume Vmc ( ⁇ m 3 / ⁇ m 2 ) of the core portions per unit area, and ridges per unit area.
- the fine tip particle volume is 1.300 ⁇ m 3 / piece or less
- the cutting level difference Rdc is 0.95 ⁇ m, calculated by the formula (Vmp + Vmc) / Spd and
- the Vmp, Vmc and Spd are values measured in accordance with ISO 25178 under the conditions of a magnification of 200 times, a cutoff wavelength of 0.3 ⁇ m by an S filter and a cutoff wavelength of 5 ⁇ m by an L filter,
- the Rdc is measured in accordance with JIS B0601-2013 under the conditions of a magnification of 20 times and a cutoff wavelength of 320 ⁇ m with a cutoff value ⁇ c without cutoff with a cutoff value ⁇ s.
- Roughened copper foil which is the value obtained as the difference in cut level c in the height direction (c (Rmr1) - c (Rmr2)) at a thickness ratio (Rmr1) of 20% and a load length ratio (Rmr2) of 80% .
- the roughened copper foil according to aspect 1 wherein the roughened surface has the cutting level difference Rdc of 1.10 ⁇ m or more and 20.00 ⁇ m or less.
- the roughened copper foil according to aspect 1 or 2 wherein the roughened surface has a substantial volume Vmc of the core portion per unit area of 0.360 ⁇ m 3 / ⁇ m 2 or less.
- the roughened surface has a core portion level difference Sk of 1.50 ⁇ m or more, and the Sk is a cutoff wavelength by an L filter, without a magnification of 20 times and cutoff by an S filter, in accordance with ISO25178.
- the roughened surface has a pole height Sxp of 1.10 ⁇ m or more, and the Sxp is 20 times the magnification in accordance with ISO 25178, cutoff by an S filter is not performed, and cutoff wavelength is 320 ⁇ m by an L filter.
- FIG. 4 is a diagram for explaining a load curve of a roughness curve determined according to JIS B0601-2013;
- FIG. 4 is a diagram for explaining a load length ratio Rmr(c) determined according to JIS B0601-2013;
- FIG. 4 is a diagram for explaining a cutting level difference Rdc determined in compliance with JIS B0601-2013;
- FIG. 4 is a diagram for explaining a surface load curve and a load area ratio Smr(c) determined in accordance with ISO25178;
- FIG. 10 is a diagram for explaining a load area ratio Smr1 for separating the protruding peak portion and the core portion, a load area ratio Smr2 for separating the protruding valley portion and the core portion, and a level difference Sk between the core portions, which are determined in accordance with ISO25178; be.
- FIG. 10 is a diagram for explaining the actual volume Vmp of the protruding peak portion and the actual volume Vmc of the core portion determined in accordance with ISO25178; It is a figure for demonstrating pole height Sxp determined based on ISO25178.
- FIG. 4 is a diagram for explaining that the surface unevenness of the roughening-treated copper foil is composed of roughening particle components and waviness components.
- FIG. 4 is a schematic cross-sectional view of a roughened particle, and is a diagram for explaining the volume of fine tip particles.
- BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram which shows an example of the roughening process copper foil of this invention.
- the "load curve of the roughness curve” refers to the substantial part that appears when the roughness curve is cut at cutting level c, determined in accordance with JIS B0601-2013, as shown in FIG. is a curve representing the ratio of as a function of c. That is, the load curve of the roughness curve can also be said to be a curve representing the height at which the load length ratio Rmr(c) is from 0% to 100%.
- the load length ratio Rmr(c) is the ratio of the load length of the roughness curve element at the cutting level c to the evaluation length, determined in accordance with JIS B0601-2013, as shown in FIG. is a parameter that represents
- cutting level difference Rdc refers to two load lengths in the load curve of the roughness curve measured in accordance with JIS B0601-2013, as shown in FIG. This is a parameter representing the difference (c(Rmr1)-c(Rmr2)) in cutting level c in the height direction at ratios Rmr1 and Rmr2 (where Rmr1 ⁇ Rmr2). Assume herein that Rdc is calculated by specifying Rmr1 as 20% and Rmr2 as 80%.
- the "surface load curve” refers to a curve that represents the height at which the load area ratio is from 0% to 100%, determined in accordance with ISO25178.
- the load area ratio is a parameter representing the area of a region having a certain height c or higher, as shown in FIG.
- the load area ratio at height c corresponds to Smr(c) in FIG.
- the secant line of the load curve drawn from the load area ratio of 0% along the load curve with the difference in the load area ratio of 40% is moved from the load area ratio of 0% to the secant line.
- the point where the slope of A straight line that minimizes the sum of squares of deviations in the direction of the vertical axis with respect to the central portion is called an equivalent straight line.
- a portion included in the height range of 0% to 100% of the load area ratio of the equivalent straight line is called a core portion.
- a portion higher than the core portion is called a protruding peak portion, and a portion lower than the core portion is called a protruding valley portion.
- the "load area ratio Smr1 separating the protruding peak portion and the core portion” is a load curve of the height of the upper portion of the core portion and the surface determined in accordance with ISO 25178, as shown in FIG. is a parameter representing the load area ratio at the intersection of (that is, the load area ratio dividing the core portion and the protruding peak portion).
- the "load area ratio Smr2 separating the protruding valley and the core” is the intersection of the height of the lower part of the core and the load curve, which is determined in accordance with ISO 25178, as shown in FIG. It is a parameter that represents the load area ratio (that is, the load area ratio that divides the core portion and the protruding valley portion) in the .
- the “core portion level difference Sk” or “Sk” is the value obtained by subtracting the minimum height from the maximum height of the core portion measured in accordance with ISO 25178, and is shown in FIG. It is a parameter calculated from the difference in the height of the equivalent straight line between the load area ratio of 0% and 100%.
- the term “substantial volume Vmp of the protruding peak” or “Vmp” is a parameter representing the volume of the protruding peak measured in compliance with ISO25178, as shown in FIG.
- the term “substantial volume Vmc of the core portion” or “Vmc” is a parameter representing the volume of the core portion, which is measured according to ISO25178, as shown in FIG.
- Vmp and Vmc are calculated by specifying 10% as the load area ratio Smr1 separating the core portion and the protruding peak portion and as 80% as the load area ratio Smr2 separating the core portion and the protruding valley portion.
- mountain peak density Spd is a parameter representing the number of peaks per unit area, measured according to ISO25178.
- Spd can be calculated by dividing the number of peaks included in the contour curved surface by the projected area of the contour curved surface. In this specification, Spd is calculated by counting only peaks larger than 5% of the maximum amplitude on the profile curved surface.
- fine tip particle volume refers to the actual volume Vmp ( ⁇ m 3 / ⁇ m 2 ) of the projecting peak per unit area, the actual volume Vmc ( ⁇ m 3 / ⁇ m 2 ) of the core portion per unit area, and a parameter calculated by the formula (Vmp+Vmc)/Spd based on the peak density Spd (pieces/ ⁇ m 2 ) of peaks per unit area.
- Vmp+Vmc means the sum of the actual volume Vmp ( ⁇ m 3 / ⁇ m 2 ) of the protruding peak portion per unit area and the actual volume Vmc ( ⁇ m 3 / ⁇ m 2 ) of the core portion per unit area.
- pole height Sxp refers to the difference in height between the load area ratio p% and the load area ratio q%, measured in accordance with ISO 25178 as shown in FIG. is a parameter that represents Sxp represents the difference between the average plane of the surface and the height of the surface after removing particularly high peaks in the surface.
- Sxp is calculated by specifying a load area ratio p of 2.5% and a load area ratio q of 50%.
- the term “developed area ratio Sdr of the interface” or “Sdr” refers to how much the developed area (surface area) of the defined region increases with respect to the area of the defined region, which is measured in accordance with ISO25178. It is a parameter that expresses whether or not The smaller this value, the more nearly flat the surface shape is, and the Sdr of a completely flat surface is 0%. On the other hand, the larger this value, the more uneven the surface shape.
- Rdc can be calculated by measuring the surface profile of a predetermined measurement length on the roughened surface with a commercially available laser microscope.
- Vmp, Vmc, Spd, Sdr, Sk and Sxp can be calculated by measuring the surface profile of a predetermined measurement area on the roughened surface with a commercially available laser microscope.
- Vmp, Vmc, Spd and Sdr are measured under the conditions of a magnification of 200, an S filter cutoff wavelength of 0.3 ⁇ m, and an L filter cutoff wavelength of 5 ⁇ m.
- Rdc shall be measured under the conditions of a cutoff wavelength of 320 ⁇ m with a cutoff value ⁇ c without performing a cutoff with a magnification of 20 times and a cutoff value ⁇ s. Measurement shall be performed under the condition of a cutoff wavelength of 320 ⁇ m by an L filter without cutoff.
- preferable measurement conditions and analysis conditions for the surface profile by the laser microscope will be shown in Examples described later.
- the "electrode surface” of the electrolytic copper foil refers to the surface that was in contact with the cathode when the electrolytic copper foil was manufactured.
- the "deposition surface" of the electrolytic copper foil refers to the surface on which electrolytic copper is deposited during the production of the electrolytic copper foil, that is, the surface that is not in contact with the cathode.
- the copper foil of the present invention is a roughened copper foil.
- This roughened copper foil has a roughened surface on at least one side.
- This roughened surface has an actual volume Vmp ( ⁇ m 3 / ⁇ m 2 ) of the protruding ridges per unit area, an actual volume Vmc ( ⁇ m 3 / ⁇ m 2 ) of the core portions per unit area, and ridges per unit area.
- the volume of fine tip particles is 1.300 ⁇ m 3 /piece or less, which is calculated by the formula (Vmp+Vmc)/Spd based on the vertex density Spd (pieces/ ⁇ m 2 ) of .
- the roughened surface has a cutting level difference Rdc of 0.95 ⁇ m or more.
- the copper-clad laminate or printed wiring board manufactured using the roughened copper foil is excellent. Both transmission characteristics (high-frequency characteristics) and high peel strength (for example, normal peel strength and moisture-resistant peel strength) can be achieved.
- the unevenness on the surface of the roughened copper foil consists of a "roughening particle component” and a “waviness component” having a longer period than the roughening particle component.
- the surface of a copper foil with small undulations (for example, the surface of a double-sided smooth foil or the electrode surface of an electrolytic copper foil) is subjected to a fine roughening treatment to remove small roughened particles.
- a copper-clad laminate or a printed wiring board is produced using such a roughened copper foil, the peel strength between the copper foil and the substrate is generally low.
- the present inventors investigated the effects of roughening particles and waviness on the surface of the copper foil on transmission characteristics and peel strength. As a result, it was found that, contrary to expectations, the waviness component of the copper foil had little effect on the transmission characteristics, and that the size of the roughening particles mainly affected the transmission characteristics. Then, the present inventors made the bumps (roughened particles) finer in order to improve the transmission characteristics, and compensated for the insufficient adhesion by undulating the copper foil, which has a small effect on the transmission characteristics. , it was found that both excellent transmission characteristics and adhesion reliability due to high peel strength can be achieved.
- the inventors have found that excellent transmission characteristics can be achieved by setting the volume of fine tip particles to 1.300 ⁇ m 3 /piece or less with respect to the volume of minute bumps (roughened particles) that affect transmission characteristics. Furthermore, by setting the cutting level difference Rdc under measurement conditions that reflect the height of the roughened surface in a wide range to 0.95 ⁇ m or more, even small roughened particles that are originally difficult to secure peel strength, It was also found that high peel strength between the copper foil and the substrate can be achieved by utilizing the waviness of the copper foil.
- FIG. 9 shows a schematic cross-sectional view of a bump (roughened particle) in which the boundary between the core portion and the protruding valley portion is divided.
- the volume per unit area of the sum of the core portion of the hump and the protruding peak portion corresponds to Vmp+Vmc.
- the peak density Spd represents the number of bumps per unit area, as shown in FIG. Corresponds to tip particle volume.
- the roughening particle component and undulation component on the copper foil surface that affect the transmission characteristics or peel strength can be distinguished by properly using the measurement magnification in the laser microscope, the S filter and L filter, or the cutoff values ⁇ s and ⁇ c. can. Specifically, by measuring the roughened surface at a high magnification of 200 times, it is possible to accurately evaluate the fine irregularities of the roughened surface that affect the transmission characteristics. Then, by measuring under conditions of a cutoff wavelength of 0.3 ⁇ m by the S filter and a cutoff wavelength of 5 ⁇ m by the L filter, it is possible to obtain parameters of the roughened particle component from which the influence of the waviness component is cut.
- the fine tip particle volume, Vmp, Vmc, Vmp+Vmc, Spd, and Sdr in the present invention accurately reflect the parameters of the roughened particles on the copper foil surface, and the transmission characteristics can be obtained by using these indices. can be evaluated accurately.
- the roughened surface by measuring the roughened surface at a low magnification of 20 times, it is possible to extensively evaluate the height (undulation) of the entire roughened surface that affects the adhesion reliability.
- Rdc, Sk, and Sxp in the present invention are parameters that reflect not only the roughening particle component on the copper foil surface but also the waviness component, and the peel strength can be accurately evaluated by using these indices. can.
- the roughened surface of the roughened copper foil has a cutting level difference Rdc of 0.95 ⁇ m or more, preferably 1.10 ⁇ m or more and 20.00 ⁇ m or less, more preferably 1.15 ⁇ m or more and 12.00 ⁇ m or less, further preferably 1.20 ⁇ m or more and 6.00 ⁇ m or less, particularly preferably 1.25 ⁇ m or more and 4.00 ⁇ m or less.
- Rdc cutting level difference
- the roughened surface of the roughened copper foil has a fine tip particle volume of 1.300 ⁇ m 3 or less, preferably 0.300 ⁇ m 3 or more and 1.300 ⁇ m 3 or less, more preferably 0.400 ⁇ m. 3 / pieces to 1.300 ⁇ m 3 / pieces, more preferably 0.500 ⁇ m 3 / pieces to 1.300 ⁇ m 3 / pieces, particularly preferably 0.500 ⁇ m 3 / pieces to 1.200 ⁇ m 3 / pieces.
- the fine tip particle volume within the above range, it is possible to achieve excellent transmission characteristics while maintaining high peel strength.
- the roughened surface of the roughened copper foil preferably has a core volume per unit area Vmc of 0.360 ⁇ m 3 / ⁇ m 2 or less, more preferably 0.040 ⁇ m 3 / ⁇ m 2 or more.
- Vmc core volume per unit area
- Vmp+Vmc which is the sum of the substantial volume Vmp of the protruding peaks and the substantial volume Vmc of the core, is preferably 0.380 ⁇ m 3 / ⁇ m 2 or less, more preferably 0. 0.050 ⁇ m 3 / ⁇ m 2 or more and 0.340 ⁇ m 3 / ⁇ m 2 or less, more preferably 0.090 ⁇ m 3 / ⁇ m 2 or more and 0.310 ⁇ m 3 / ⁇ m 2 or less, particularly preferably 0.130 ⁇ m 3 / ⁇ m 2 or more and 0.280 ⁇ m 3 / ⁇ m 2 or less, most preferably 0.140 ⁇ m 3 / ⁇ m 2 or more and 0.250 ⁇ m 3 / ⁇ m 2 or less.
- Vmp+Vmc is within the above range, it becomes easier to control the volume of the fine tip particles within the above range, and even better transmission characteristics can be achieved while maintaining high peel strength.
- the roughened surface of the roughened copper foil preferably has a crest density Spd per unit area of 0.12/ ⁇ m 2 or more and 0.46/ ⁇ m 2 or less, more preferably 0.13. pieces/ ⁇ m 2 or more and 0.44 pieces/ ⁇ m 2 or less, more preferably 0.14 pieces/ ⁇ m 2 or more and 0.37 pieces/ ⁇ m 2 or less, particularly preferably 0.15 pieces/ ⁇ m 2 or more and 0.31 pieces/ ⁇ m 2 or less, most preferably 0.16 or more/ ⁇ m 2 or more and 0.28 or less/ ⁇ m 2 or less.
- the Spd is within the above range, it becomes easier to control the volume of the fine tip particles within the above range, and even better transmission characteristics can be achieved while maintaining high peel strength.
- the roughened surface of the roughened copper foil preferably has an interface expansion area ratio Sdr of 70% or less, more preferably 5% or more and 65% or less, still more preferably 10% or more and 60% or less, and particularly preferably. is 15% or more and 55% or less, most preferably 20% or more and 50% or less.
- Sdr interface expansion area ratio
- the roughened surface of the roughened copper foil preferably has a core level difference Sk of 1.50 ⁇ m or more, more preferably 1.58 ⁇ m or more and 20.00 ⁇ m or less, still more preferably 1.65 ⁇ m or more12. 00 ⁇ m or less, particularly preferably 1.70 ⁇ m or more and 8.00 ⁇ m or less, most preferably 2.00 ⁇ m or more and 6.00 ⁇ m or less.
- Sk is within the above range, the anchor effect is effectively exhibited while the transmission characteristics are excellent, and a higher peel strength can be realized.
- the roughened surface of the roughened copper foil preferably has a pole height Sxp of 1.10 ⁇ m or more, more preferably 1.20 ⁇ m or more and 20.00 ⁇ m or less, and still more preferably 1.30 ⁇ m or more and 12.00 ⁇ m or less. , particularly preferably 1.40 ⁇ m or more and 8.00 ⁇ m or less, most preferably 1.70 ⁇ m or more and 6.00 ⁇ m or less.
- pole point height Sxp is within the above range, the anchor effect is effectively exhibited while the transmission characteristics are excellent, and a higher peel strength can be realized.
- the thickness of the roughened copper foil is not particularly limited, it is preferably 0.1 ⁇ m or more and 210 ⁇ m or less, more preferably 0.3 ⁇ m or more and 105 ⁇ m or less.
- the roughened copper foil of the present invention is not limited to the ordinary copper foil whose surface has been roughened, but the copper foil surface of the carrier-attached copper foil has been roughened or finely roughened. can be anything.
- the roughened copper foil of the present invention is obtained by subjecting a copper foil surface having predetermined undulations (for example, a deposition surface of an electrolytic copper foil) to a roughening treatment under desired low-roughening conditions. It can be produced preferably by carrying out to form fine roughened particles. Therefore, according to a preferred aspect of the present invention, the roughened copper foil is an electrolytic copper foil, and the roughened surface is present on the deposition surface side of the electrolytic copper foil.
- the roughened copper foil may have roughened surfaces on both sides, or may have a roughened surface only on one side.
- the roughened surface is typically provided with a plurality of roughened particles, and preferably each of these roughened particles is made of copper particles.
- the copper particles may consist of metallic copper, or may consist of a copper alloy.
- the roughening treatment for forming the roughened surface can be preferably carried out by forming roughening particles with copper or a copper alloy on the copper foil.
- the copper foil before the roughening treatment may be a non-roughened copper foil or a pre-roughened copper foil.
- the surface of the copper foil to be roughened preferably has a ten-point average roughness Rz measured in accordance with JIS B0601-1994 of 1.50 ⁇ m or more and 20.00 ⁇ m or less, more preferably It is 2.00 ⁇ m or more and 10.00 ⁇ m or less. Within the above range, it becomes easier to impart the surface profile required for the roughened copper foil of the present invention to the roughened surface.
- the roughening treatment is performed, for example, in a copper sulfate solution containing a copper concentration of 7 g/L or more and 17 g/L or less and a sulfuric acid concentration of 50 g/L or more and 200 g/L or less at a temperature of 20 ° C. or more and 40 ° C. or less at 10 A / dm 2 or more and 50 A. /dm 2 or less.
- This electrolytic deposition is preferably carried out for 0.5 to 30 seconds, more preferably 1 to 30 seconds, and even more preferably 1 to 3 seconds.
- the roughened copper foil according to the present invention is not limited to the method described above, and may be manufactured by any method.
- R L L/D C (Wherein, R L is the liquid resistance index (mm L/mol), L is the distance between the electrodes (anode-cathode) (mm), and D C is the charge carrier density (mol/L).)
- the liquid resistance index RL defined by is preferably 9.0 mm L / mol or more and 20.0 mm L / mol or less, and 11.0 mm L / mol or more and 17.0 mm L / mol or less is more preferred.
- the bumps can be preferably formed in a shape suitable for imparting the surface profile required for the roughened copper foil of the present invention.
- the charge carrier density Dc can be calculated by totaling the product of each ion concentration and valence for all ions present in the plating solution.
- the liquid resistance index is an index that correlates with the resistance of the solution.
- the roughened copper foil may be subjected to antirust treatment and may have an antirust treatment layer formed thereon.
- the antirust treatment preferably includes plating with zinc.
- the plating treatment using zinc may be either zinc plating treatment or zinc alloy plating treatment, and the zinc alloy plating treatment is particularly preferably zinc-nickel alloy treatment.
- the zinc-nickel alloy treatment may be a plating treatment containing at least Ni and Zn, and may further contain other elements such as Sn, Cr, Co and Mo.
- the antirust treatment layer further contains Mo in addition to Ni and Zn, so that the treated surface of the roughened copper foil has excellent adhesion to resin, chemical resistance, and heat resistance, and etching residue is removed. It becomes difficult to remain.
- the Ni/Zn adhesion ratio in the zinc-nickel alloy plating is preferably 1.2 to 10, more preferably 2 to 7, and still more preferably 2.7 to 4 in mass ratio.
- the rust prevention treatment preferably further includes chromate treatment, and this chromate treatment is more preferably performed on the surface of the plating containing zinc after the plating treatment using zinc. By doing so, the rust resistance can be further improved.
- a particularly preferred antirust treatment is a combination of zinc-nickel alloy plating treatment and subsequent chromate treatment.
- the surface of the roughened copper foil may be treated with a silane coupling agent to form a silane coupling agent-treated layer.
- a silane coupling agent-treated layer can be formed by appropriately diluting a silane coupling agent, coating it, and drying it.
- silane coupling agents include epoxy-functional silane coupling agents such as 4-glycidylbutyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, or 3-aminopropyltriethoxysilane, N-(2- aminoethyl)-3-aminopropyltrimethoxysilane, N-3-(4-(3-aminopropoxy)butoxy)propyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, etc.
- epoxy-functional silane coupling agents such as 4-glycidylbutyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, or 3-aminopropyltriethoxysilane, N-(2- aminoethyl)-3-aminopropyltrimethoxysilane, N-3-(4-(3-aminopropoxy)but
- amino-functional silane coupling agents or mercapto-functional silane coupling agents such as 3-mercaptopropyltrimethoxysilane or olefin-functional silane coupling agents such as vinyltrimethoxysilane, vinylphenyltrimethoxysilane, or 3-methacrylic acrylic functional silane coupling agents such as roxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, or imidazole functional silane coupling agents such as imidazole silane, or triazine functional silane coupling agents such as triazine silane, and the like. is mentioned.
- the roughened copper foil preferably further comprises an antirust treatment layer and/or a silane coupling agent treatment layer on the roughened surface, more preferably the antirust treatment layer and the silane coupling agent treatment. It has both layers.
- the anticorrosion treatment layer and the silane coupling agent treatment 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.
- Prepreg is a general term for composite materials in which synthetic resin is impregnated into a base material such as a synthetic resin plate, a glass plate, a glass woven fabric, a glass non-woven fabric, or paper.
- insulating resins include epoxy resins, cyanate resins, bismaleimide triazine resins (BT resins), polyphenylene ether resins, and phenol resins.
- the insulating resin forming the resin sheet include insulating resins such as epoxy resins, polyimide resins, and polyester resins.
- the resin layer may contain filler particles made of various inorganic particles such as silica and alumina from the viewpoint of improving insulation.
- the thickness of the resin layer is not particularly limited, it is preferably 1 ⁇ m or more and 1000 ⁇ m or less, more preferably 2 ⁇ m or more and 400 ⁇ m or less, and still more preferably 3 ⁇ m or more and 200 ⁇ m or less.
- the resin layer may be composed of multiple layers.
- a resin layer such as a prepreg and/or a resin sheet may be provided on the roughened copper foil in advance via a primer resin layer that is applied to the surface of the copper foil.
- the roughened copper foil of the present invention is preferably used for manufacturing printed wiring boards. That is, according to a preferred aspect of the present invention, there is provided a printed wiring board comprising the roughened copper foil.
- the printed wiring board according to this aspect includes a layer structure in which a resin layer and a copper layer are laminated.
- the copper layer is a layer derived from the roughened copper foil of the present invention.
- the resin layer is as described above for the copper-clad laminate. In any case, a known layer structure can be adopted for the printed wiring board.
- printed wiring boards include a single-sided or double-sided printed wiring board formed by bonding the roughened copper foil of the present invention to one or both sides of a prepreg to form a cured laminate, and then forming a circuit on the printed wiring board.
- a multilayer printed wiring board etc. are mentioned.
- other specific examples include flexible printed wiring boards, COF, TAB tapes, etc., in which the roughened copper foil of the present invention is formed on a resin film to form a circuit.
- a resin-coated copper foil (RCC) is formed by applying the above resin layer to the roughened copper foil of the present invention, and the resin layer is used as an insulating adhesive layer and laminated on the above printed circuit board.
- the roughened copper foil is used as all or part of the wiring layer, and the circuit is formed by the modified semi-additive method (MSAP), the subtractive method, etc., and the roughened copper foil is removed.
- MSAP modified semi-additive method
- Examples 1-15 The roughened copper foil of the present invention was manufactured as follows.
- Example 10 an electrolytic copper foil B having a thickness shown in Table 1 was obtained using a sulfuric acid copper sulfate solution having the composition shown below as the copper electrolyte. At this time, conditions other than the composition of the sulfuric acid copper sulfate solution were the same as those for the electrolytic copper foil A.
- Examples 1 to 6, 10, and 12 to 15 are on the deposition surface side
- Examples 7 to 9 and 11 are on the electrode surface. Roughening treatment was performed on the side.
- the deposition surface of the electrolytic copper foils used in Examples 1 to 6, 10 and 12 to 15, and the electrode surface of the electrolytic copper foils used in Examples 7 to 9 and 11 were measured using a contact-type surface roughness meter, and JIS The ten-point average roughness Rz measured according to B0601-1994 was as shown in Table 1.
- first roughening treatment For Examples 1 to 8, the following roughening treatment (first roughening treatment) was performed. This roughening treatment is performed in a copper electrolytic solution for roughening treatment (copper concentration: 7 g / L or more and 17 g / L or less, sulfuric acid concentration: 50 g / L or more and 200 g / L or less, liquid temperature: 30 ° C.) for each example Electrolysis was carried out under the conditions of liquid resistance index, current density and time shown in Table 1, followed by washing with water.
- first roughening treatment For Examples 9 to 15, the following first roughening treatment, second roughening treatment and third roughening treatment were performed in this order.
- the first roughening treatment is performed in a copper electrolytic solution for roughening treatment (copper concentration: 7 g / L or more and 17 g / L or less, sulfuric acid concentration: 50 g / L or more and 200 g / L or less, liquid temperature: 30 ° C.)
- the second roughening treatment is performed by electrolysis under the conditions of liquid resistance index, current density and time shown in Table 1 in a copper electrolytic solution for roughening treatment having the same composition as the first roughening treatment, and washing with water. gone.
- the third roughening treatment is performed in a copper electrolytic solution for roughening treatment (copper concentration: 65 g / L or more and 80 g / L or less, sulfuric acid concentration: 50 g / L or more and 200 g / L or less, liquid temperature: 45 ° C.)
- Table 1 Electrolysis was carried out under the liquid resistance index, current density and time conditions shown in , followed by washing with water.
- the antirust treatment shown in Table 1 was performed on the electrolytic copper foil after the roughening treatment.
- a pyrophosphate bath was used on the roughened surface of the electrolytic copper foil, with a potassium pyrophosphate concentration of 100 g / L and a zinc concentration of 1 g / L. , a nickel concentration of 2 g/L, a molybdenum concentration of 1 g/L, a liquid temperature of 40° C., and a current density of 0.5 A/dm 2 .
- a pyrophosphate bath was applied to the surface of the electrodeposited copper foil that had not been roughened, and the concentration of potassium pyrophosphate was 80 g/L, the concentration of zinc was 0.2 g/L, the concentration of nickel was 2 g/L, the liquid temperature was 40°C.
- a zinc-nickel antirust treatment was performed at a current density of 0.5 A/dm 2 .
- both sides of the electrolytic copper foil were subjected to the same conditions as the surface of the electrolytic copper foil that was not roughened in Examples 1 to 5, 7 and 8. Rust treated.
- Chromate treatment was performed on both surfaces of the antirust-treated electrolytic copper foil to form a chromate layer on the antirust treatment layer. This chromate treatment was performed under the conditions of a chromic acid concentration of 1 g/L, a pH of 11, a liquid temperature of 25° C. and a current density of 1 A/dm 2 .
- Silane Coupling Agent Treatment The chromate-treated copper foil was washed with water and then immediately treated with a silane coupling agent to adsorb the silane coupling agent onto the chromate layer on the roughened surface.
- This silane coupling agent treatment was carried out by spraying a solution of a silane coupling agent using pure water as a solvent onto the roughened surface by showering for adsorption treatment.
- the silane coupling agent 3-aminopropyltrimethoxysilane was used in Examples 1 and 3-8, and 3-glycidoxypropyltrimethoxysilane was used in Examples 2 and 9-15.
- the concentration of the silane coupling agent was 3 g/L in each case. After adsorption of the silane coupling agent, water was finally evaporated by an electric heater to obtain a roughened copper foil with a predetermined thickness.
- Example 1 the surface of the copper-clad laminate on the copper foil side was plated with copper until the thickness of the copper foil reached 18 ⁇ m before forming the circuit.
- Example 4 to 6, 14 and 15 the surface of the copper-clad laminate on the copper foil side was etched until the copper foil had a thickness of 18 ⁇ m before forming the circuit.
- the linear circuit thus obtained was peeled off from the insulating substrate according to JIS C 5016-1994 A method (90° peeling), and the normal peel strength (kgf/cm) was measured.
- the quality of the normal peel strength obtained was evaluated according to the following criteria. The results were as shown in Table 4.
- a base material for high frequency (MEGTRON6N manufactured by Panasonic) was prepared as an insulating resin base material.
- a roughened copper foil is laminated on both sides of this insulating resin substrate so that the roughened surface is in contact with the insulating resin substrate, and a vacuum press is used at a temperature of 190 ° C. for a pressing time of 120 minutes. to obtain a copper-clad laminate having an insulation thickness of 136 ⁇ m.
- the copper-clad laminate was subjected to an etching process to obtain a transmission loss measuring board on which microstrip lines were formed so as to have a characteristic impedance of 50 ⁇ .
- the transmission loss (dB/cm) at 28 GHz was measured on the obtained transmission loss measuring board using a network analyzer (N5225B manufactured by Keysight Technologies). The quality of the obtained transmission loss was evaluated according to the following criteria. The results were as shown in Table 4. ⁇ Transmission loss evaluation criteria> -Good: Transmission loss is -0.33 dB/cm or more -Bad: Transmission loss is less than -0.33 dB/cm
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Abstract
Description
[態様1]
少なくとも一方の側に粗化処理面を有する粗化処理銅箔であって、
前記粗化処理面は、単位面積当たりの突出山部の実体体積Vmp(μm3/μm2)、単位面積当たりのコア部の実体体積Vmc(μm3/μm2)、及び単位面積当たりの山の頂点密度Spd(個/μm2)に基づき、(Vmp+Vmc)/Spdの式により算出される、微小先端粒子体積が1.300μm3/個以下であり、かつ、切断レベル差Rdcが0.95μm以上であり、
前記Vmp、Vmc及びSpdは、ISO25178に準拠して、倍率200倍、Sフィルターによるカットオフ波長0.3μm及びLフィルターによるカットオフ波長5μmの条件で測定される値であり、
前記Rdcは、JIS B0601-2013に準拠して、倍率20倍、カットオフ値λsによるカットオフを行わず、カットオフ値λcによるカットオフ波長320μmの条件で測定される粗さ曲線における、負荷長さ率(Rmr1)20%及び負荷長さ率(Rmr2)80%における高さ方向の切断レベルcの差(c(Rmr1)-c(Rmr2))として得られる値である、粗化処理銅箔。
[態様2]
前記粗化処理面は、前記切断レベル差Rdcが1.10μm以上20.00μm以下である、態様1に記載の粗化処理銅箔。
[態様3]
前記粗化処理面は、単位面積当たりの前記コア部の実体体積Vmcが0.360μm3/μm2以下である、態様1又は2に記載の粗化処理銅箔。
[態様4]
前記粗化処理面は、前記突出山部の実体体積Vmp及び前記コア部の実体体積Vmcの和であるVmp+Vmcが0.380μm3/μm2以下である、態様1~3のいずれか一つに記載の粗化処理銅箔。
[態様5]
前記粗化処理面は、界面の展開面積比Sdrが70%以下であり、前記Sdrは、ISO25178に準拠して、倍率200倍、Sフィルターによるカットオフ波長0.3μm及びLフィルターによるカットオフ波長5μmの条件で測定される値である、態様1~4のいずれか一つに記載の粗化処理銅箔。
[態様6]
前記粗化処理面は、コア部のレベル差Skが1.50μm以上であり、前記Skは、ISO25178に準拠して、倍率20倍、Sフィルターによるカットオフを行わず、Lフィルターによるカットオフ波長320μmの条件で測定される値である、態様1~5のいずれか一つに記載の粗化処理銅箔。
[態様7]
前記粗化処理面は、極点高さSxpが1.10μm以上であり、前記Sxpは、ISO25178に準拠して、倍率20倍、Sフィルターによるカットオフを行わず、Lフィルターによるカットオフ波長320μmの条件で測定される値である、態様1~6のいずれか一つに記載の粗化処理銅箔。
[態様8]
前記粗化処理面は、単位面積当たりの前記山の頂点密度Spdが0.12個/μm2以上0.46個/μm2以下である、態様1~7のいずれか一つに記載の粗化処理銅箔。
[態様9]
前記粗化処理面に防錆処理層及び/又はシランカップリング剤処理層をさらに備えた、態様1~8のいずれか一つに記載の粗化処理銅箔。
[態様10]
前記粗化処理銅箔が電解銅箔であり、前記粗化処理面が電解銅箔の析出面側に存在する、態様1~9のいずれか一つに記載の粗化処理銅箔。
[態様11]
態様1~10のいずれか一つに記載の粗化処理銅箔を備えた、銅張積層板。
[態様12]
態様1~10のいずれか一つに記載の粗化処理銅箔を備えた、プリント配線板。
本発明を特定するために用いられる用語ないしパラメータの定義を以下に示す。
本発明の銅箔は粗化処理銅箔である。この粗化処理銅箔は少なくとも一方の側に粗化処理面を有する。この粗化処理面は、単位面積当たりの突出山部の実体体積Vmp(μm3/μm2)、単位面積当たりのコア部の実体体積Vmc(μm3/μm2)、及び単位面積当たりの山の頂点密度Spd(個/μm2)に基づき、(Vmp+Vmc)/Spdの式により算出される、微小先端粒子体積が1.300μm3/個以下である。また、粗化処理面は、切断レベル差Rdcが0.95μm以上である。このように粗化処理銅箔の表面において、微小先端粒子体積及び切断レベル差Rdcを所定の範囲に制御することにより、これを用いて製造された銅張積層板ないしプリント配線板において、優れた伝送特性(高周波特性)と、高い剥離強度(例えば常態剥離強度及び耐湿剥離強度)とを両立することができる。
RL=L/DC
(式中、RLは液抵抗指数(mm・L/mol)、Lは極間(陽極-陰極間)距離(mm)、DCは電荷担体密度(mol/L)である)
により定義される液抵抗指数RLを9.0mm・L/mol以上20.0mm・L/mol以下とするのが好ましく、11.0mm・L/mol以上17.0mm・L/mol以下とするのがより好ましい。このように液抵抗指数RLを大きくすることで系全体における電圧が大きくなり、コブ形成反応時の電圧も大きくなる。これがコブ形状に影響を及ぼす結果、本発明の粗化処理銅箔に要求される表面プロファイルを付与するのに適した形状のコブを好ましく形成することができる。なお、電荷担体密度DCは、めっき液中に存在する全てのイオンについて、各々のイオン濃度及び価数の積を合計することにより算出することができる。例えば、めっき液として硫酸銅溶液を用いる場合、電荷担体密度DCは、下記式:
Dc=[H+]×1+[Cu2+]×2+[SO4 2-]×2
(式中、[H+]は溶液中の水素イオン濃度(mol/L)、[Cu2+]は溶液中の銅イオン濃度(mol/L)、[SO4 2-]は溶液中の硫酸イオン濃度(mol/L)である)
により算出される。
V=ρ×L×I/S
(式中、Vは電圧、ρは比抵抗、Lは極間距離、Iは電流、Sは極間の断面積である)
が導出される。すなわち、電圧Vは、比抵抗ρ、極間距離L、及び電流密度(=I/S)に比例する。そして、比抵抗ρは上述した電荷担体密度DCに反比例する。このため、電流密度が一定の場合、(極間距離Lに比例し、電荷担体密度DCに反比例する)液抵抗指数を大きくすることで電圧も大きくなる。したがって、液抵抗指数は溶液の抵抗と相関のある指標といえる。
本発明の粗化処理銅箔はプリント配線板用銅張積層板の製造に用いられるのが好ましい。すなわち、本発明の好ましい態様によれば、上記粗化処理銅箔を備えた銅張積層板が提供される。本発明の粗化処理銅箔を用いることで、銅張積層板において、優れた伝送特性と高い剥離強度とを両立することができる。この銅張積層板は、本発明の粗化処理銅箔と、この粗化処理銅箔の粗化処理面に密着して設けられる樹脂層とを備えてなる。粗化処理銅箔は樹脂層の片面に設けられてもよいし、両面に設けられてもよい。樹脂層は、樹脂、好ましくは絶縁性樹脂を含んでなる。樹脂層はプリプレグ及び/又は樹脂シートであるのが好ましい。プリプレグとは、合成樹脂板、ガラス板、ガラス織布、ガラス不織布、紙等の基材に合成樹脂を含浸させた複合材料の総称である。絶縁性樹脂の好ましい例としては、エポキシ樹脂、シアネート樹脂、ビスマレイミドトリアジン樹脂(BT樹脂)、ポリフェニレンエーテル樹脂、フェノール樹脂等が挙げられる。また、樹脂シートを構成する絶縁性樹脂の例としては、エポキシ樹脂、ポリイミド樹脂、ポリエステル樹脂等の絶縁樹脂が挙げられる。また、樹脂層には絶縁性を向上する等の観点からシリカ、アルミナ等の各種無機粒子からなるフィラー粒子等が含有されていてもよい。樹脂層の厚さは特に限定されないが、1μm以上1000μm以下が好ましく、より好ましくは2μm以上400μm以下であり、さらに好ましくは3μm以上200μm以下である。樹脂層は複数の層で構成されていてよい。プリプレグ及び/又は樹脂シート等の樹脂層は予め銅箔表面に塗布されるプライマー樹脂層を介して粗化処理銅箔に設けられていてもよい。
本発明の粗化処理銅箔はプリント配線板の製造に用いられるのが好ましい。すなわち、本発明の好ましい態様によれば、上記粗化処理銅箔を備えたプリント配線板が提供される。本発明の粗化処理銅箔を用いることで、プリント配線板において、優れた伝送特性と高い剥離強度とを両立することができる。本態様によるプリント配線板は、樹脂層と、銅層とが積層された層構成を含んでなる。銅層は本発明の粗化処理銅箔に由来する層である。また、樹脂層については銅張積層板に関して上述したとおりである。いずれにしても、プリント配線板は公知の層構成が採用可能である。プリント配線板に関する具体例としては、プリプレグの片面又は両面に本発明の粗化処理銅箔を接着させ硬化した積層体とした上で回路形成した片面又は両面プリント配線板や、これらを多層化した多層プリント配線板等が挙げられる。また、他の具体例としては、樹脂フィルム上に本発明の粗化処理銅箔を形成して回路を形成するフレキシブルプリント配線板、COF、TABテープ等も挙げられる。さらに他の具体例としては、本発明の粗化処理銅箔に上述の樹脂層を塗布した樹脂付銅箔(RCC)を形成し、樹脂層を絶縁接着材層として上述のプリント基板に積層した後、粗化処理銅箔を配線層の全部又は一部としてモディファイド・セミ・アディティブ法(MSAP)、サブトラクティブ法等の手法で回路を形成したビルドアップ配線板や、粗化処理銅箔を除去してセミアディティブ法(SAP)で回路を形成したビルドアップ配線板、半導体集積回路上へ樹脂付銅箔の積層と回路形成を交互に繰りかえすダイレクト・ビルドアップ・オン・ウェハー等が挙げられる。
本発明の粗化処理銅箔の製造を以下のようにして行った。
例1~9及び11~15について、銅電解液として以下に示される組成の硫酸酸性硫酸銅溶液を用い、陰極にチタン製の電極を用い、陽極にはDSA(寸法安定性陽極)を用いて、溶液温度45℃、電流密度55A/dm2で電解し、表1に示した厚さの電解銅箔Aを得た。このとき、陰極として、表面を#1000のバフで研磨して表面粗さを調整した電極を用いた。
<硫酸酸性硫酸銅溶液の組成>
‐ 銅濃度:80g/L
‐ 硫酸濃度:300g/L
‐ ニカワ濃度:5mg/L
‐ 塩素濃度:30mg/L
<硫酸酸性硫酸銅溶液の組成>
‐ 銅濃度:80g/L
‐ 硫酸濃度:260g/L
‐ ビス(3-スルホプロピル)ジスルフィド濃度:30mg/L
‐ ジアリルジメチルアンモニウムクロライド重合体濃度:50mg/L
‐ 塩素濃度:40mg/L
上述の電解銅箔が備える電極面及び析出面の内、例1~6、10及び12~15については析出面側に対して、例7~9及び11については電極面側に対して、粗化処理を行った。なお、例1~6、10及び12~15に用いた電解銅箔の析出面、並びに例7~9及び11に用いた電解銅箔の電極面における、接触式表面粗さ計を用いてJIS B0601-1994に準拠して測定される十点平均粗さRzは表1に示されるとおりであった。
‐ 第一粗化処理は、粗化処理用銅電解溶液(銅濃度:7g/L以上17g/L以下、硫酸濃度:50g/L以上200g/L以下、液温:30℃)中、表1に示した液抵抗指数、電流密度及び時間の条件にて電解し、水洗することにより行った。
‐ 第二粗化処理は、第一粗化処理と同じ組成の粗化処理用銅電解溶液中、表1に示した液抵抗指数、電流密度及び時間の条件にて電解し、水洗することにより行った。
‐ 第三粗化処理は、粗化処理用銅電解溶液(銅濃度:65g/L以上80g/L以下、硫酸濃度:50g/L以上200g/L以下、液温:45℃)中、表1に示した液抵抗指数、電流密度及び時間の条件にて電解し、水洗することにより行った。
粗化処理後の電解銅箔に表1に示した防錆処理を行った。この防錆処理として、例1~5、7及び8については、電解銅箔の粗化処理を行った面に対し、ピロリン酸浴を用い、ピロリン酸カリウム濃度100g/L、亜鉛濃度1g/L、ニッケル濃度2g/L、モリブデン濃度1g/L、液温40℃、電流密度0.5A/dm2で亜鉛-ニッケル-モリブデン系防錆処理を行った。また、電解銅箔の粗化処理を行っていない面に対し、ピロリン酸浴を用い、ピロリン酸カリウム濃度80g/L、亜鉛濃度0.2g/L、ニッケル濃度2g/L、液温40℃、電流密度0.5A/dm2として亜鉛-ニッケル系防錆処理を行った。一方、例6及び9~15については、電解銅箔の両面に対し、例1~5、7及び8における電解銅箔の粗化処理を行っていない面と同様の条件で亜鉛-ニッケル系防錆処理を行った。
上記防錆処理を行った電解銅箔の両面に対して、クロメート処理を行い、防錆処理層の上にクロメート層を形成した。このクロメート処理は、クロム酸濃度1g/L、pH11、液温25℃及び電流密度1A/dm2の条件で行った。
上記クロメート処理が施された銅箔を水洗し、その後直ちにシランカップリング剤処理を行い、粗化処理面のクロメート層上にシランカップリング剤を吸着させた。このシランカップリング剤処理は、純水を溶媒とするシランカップリング剤の溶液をシャワーリングにて粗化処理面に吹き付けて吸着処理することにより行った。シランカップリング剤として、例1及び3~8では3-アミノプロピルトリメトキシシラン、例2及び9~15では3-グリシドキシプロピルトリメトキシシランを用いた。シランカップリング剤の濃度はいずれも3g/Lとした。シランカップリング剤の吸着後、最終的に電熱器により水分を蒸発させ、所定厚さの粗化処理銅箔を得た。
製造された粗化処理銅箔について、以下に示される各種評価を行った。
レーザー顕微鏡(オリンパス株式会社製、OLS-5000)を用いた表面粗さ解析により、粗化処理銅箔の粗化処理面の測定をISO25178又はJIS B0601-2013に準拠して行った。このとき、Spd、Vmp、Vmc及びSdrについては表2に示されるとおり測定倍率を200倍(対物レンズ倍率100倍×光学ズーム2倍)とし、Rdc、Sk及びSxpについては表3に示されるとおり測定倍率を20倍(対物レンズ倍率20倍)として測定を行った。その他の具体的な測定条件は表2及び3に示されるとおりとした。得られた粗化処理面の表面プロファイルに対して、表2及び3に示される条件に従って解析を行い、Spd、Vmp、Vmc、Sdr、Rdc、Sk及びSxpを算出した。また、得られたSpd、Vmp及びVmcの値に基づいて、Vmp+Vmc及び微小先端粒子体積(=(Vmp+Vmc)/Spd)を算出した。結果は表4に示されるとおりであった。
常温及び多湿環境下における粗化処理銅箔について、絶縁基材との密着性を評価するために、常態剥離強度及び耐湿剥離強度の測定を以下のとおり行った。
絶縁基材として、ポリフェニレンエーテルとトリアリルイソシアヌレートとビスマレイミド樹脂とを主成分とするプリプレグ(厚さ100μm)2枚を用意して、積み重ねた。この積み重ねたプリプレグに、製造した表面処理銅箔をその粗化処理面がプリプレグと当接するように積層し、32kgf/cm2、205℃で120分間のプレスを行って銅張積層板を製造した。次に、この銅張積層板にエッチング法により回路形成を行い、3mm幅の直線回路を備えた試験基板を製造した。なお、例1、2及び12については、回路形成前に、銅箔の厚さが18μmとなるまで銅張積層板の銅箔側表面に対して銅めっきを行った。また、例4~6、14及び15については、回路形成前に、銅箔の厚さが18μmとなるまで銅張積層板の銅箔側表面に対してエッチングを行った。こうして得られた直線回路を、JIS C 5016-1994のA法(90°剥離)に準拠して絶縁基材から引き剥がして常態剥離強度(kgf/cm)を測定した。得られた常態剥離強度の良否を以下の基準に従って評価した。結果は表4に示されるとおりであった。
<常態剥離強度評価基準>
‐良好:常態剥離強度が0.40kgf/cm以上
‐不良:常態剥離強度が0.40kgf/cm未満
剥離強度の測定に先立ち、直線回路を備えた試験基板を沸騰水中に2時間浸漬したこと以外は、上述した常態剥離強度と同様の手順により、耐湿剥離強度(kgf/cm)を測定した。得られた耐湿剥離強度の良否を以下の基準に従って評価した。結果は表4に示されるとおりであった。
<耐湿剥離強度評価基準>
‐良好:耐湿剥離強度が0.40kgf/cm以上
‐不良:耐湿剥離強度が0.40kgf/cm未満
絶縁樹脂基材として高周波用基材(パナソニック製、MEGTRON6N)を用意した。この絶縁樹脂基材の両面に粗化処理銅箔をその粗化処理面が絶縁樹脂基材と当接するように積層し、真空プレス機を使用して、温度190℃、プレス時間120分の条件で積層し、絶縁厚さ136μmの銅張積層板を得た。その後、当該銅張積層板にエッチング加工を施し、特性インピーダンスが50Ωになるようマイクロストリップラインを形成した伝送損失測定用基板を得た。得られた伝送損失測定用基板に対して、ネットワークアナライザー(キーサイトテクノロジー製、N5225B)を用いて、28GHzの伝送損失(dB/cm)を測定した。得られた伝送損失の良否を以下の基準に従って評価した。結果は表4に示されるとおりであった。
<伝送損失評価基準>
‐良好:伝送損失が-0.33dB/cm以上
‐不良:伝送損失が-0.33dB/cm未満
Claims (12)
- 少なくとも一方の側に粗化処理面を有する粗化処理銅箔であって、
前記粗化処理面は、単位面積当たりの突出山部の実体体積Vmp(μm3/μm2)、単位面積当たりのコア部の実体体積Vmc(μm3/μm2)、及び単位面積当たりの山の頂点密度Spd(個/μm2)に基づき、(Vmp+Vmc)/Spdの式により算出される、微小先端粒子体積が1.300μm3/個以下であり、かつ、切断レベル差Rdcが0.95μm以上であり、
前記Vmp、Vmc及びSpdは、ISO25178に準拠して、倍率200倍、Sフィルターによるカットオフ波長0.3μm及びLフィルターによるカットオフ波長5μmの条件で測定される値であり、
前記Rdcは、JIS B0601-2013に準拠して、倍率20倍、カットオフ値λsによるカットオフを行わず、カットオフ値λcによるカットオフ波長320μmの条件で測定される粗さ曲線における、負荷長さ率(Rmr1)20%及び負荷長さ率(Rmr2)80%における高さ方向の切断レベルcの差(c(Rmr1)-c(Rmr2))として得られる値である、粗化処理銅箔。 - 前記粗化処理面は、前記切断レベル差Rdcが1.10μm以上20.00μm以下である、請求項1に記載の粗化処理銅箔。
- 前記粗化処理面は、単位面積当たりの前記コア部の実体体積Vmcが0.360μm3/μm2以下である、請求項1又は2に記載の粗化処理銅箔。
- 前記粗化処理面は、前記突出山部の実体体積Vmp及び前記コア部の実体体積Vmcの和であるVmp+Vmcが0.380μm3/μm2以下である、請求項1又は2に記載の粗化処理銅箔。
- 前記粗化処理面は、界面の展開面積比Sdrが70%以下であり、前記Sdrは、ISO25178に準拠して、倍率200倍、Sフィルターによるカットオフ波長0.3μm及びLフィルターによるカットオフ波長5μmの条件で測定される値である、請求項1又は2に記載の粗化処理銅箔。
- 前記粗化処理面は、コア部のレベル差Skが1.50μm以上であり、前記Skは、ISO25178に準拠して、倍率20倍、Sフィルターによるカットオフを行わず、Lフィルターによるカットオフ波長320μmの条件で測定される値である、請求項1又は2に記載の粗化処理銅箔。
- 前記粗化処理面は、極点高さSxpが1.10μm以上であり、前記Sxpは、ISO25178に準拠して、倍率20倍、Sフィルターによるカットオフを行わず、Lフィルターによるカットオフ波長320μmの条件で測定される値である、請求項1又は2に記載の粗化処理銅箔。
- 前記粗化処理面は、単位面積当たりの前記山の頂点密度Spdが0.12個/μm2以上0.46個/μm2以下である、請求項1又は2に記載の粗化処理銅箔。
- 前記粗化処理面に防錆処理層及び/又はシランカップリング剤処理層をさらに備えた、請求項1又は2に記載の粗化処理銅箔。
- 前記粗化処理銅箔が電解銅箔であり、前記粗化処理面が電解銅箔の析出面側に存在する、請求項1又は2に記載の粗化処理銅箔。
- 請求項1又は2に記載の粗化処理銅箔を備えた、銅張積層板。
- 請求項1又は2に記載の粗化処理銅箔を備えた、プリント配線板。
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2023182177A1 (ja) * | 2022-03-24 | 2023-09-28 | 三井金属鉱業株式会社 | 粗化処理銅箔、キャリア付銅箔、銅張積層板及びプリント配線板 |
WO2023182174A1 (ja) * | 2022-03-24 | 2023-09-28 | 三井金属鉱業株式会社 | 粗化処理銅箔、キャリア付銅箔、銅張積層板及びプリント配線板 |
WO2023182176A1 (ja) * | 2022-03-24 | 2023-09-28 | 三井金属鉱業株式会社 | 粗化処理銅箔、キャリア付銅箔、銅張積層板及びプリント配線板 |
WO2023182175A1 (ja) * | 2022-03-24 | 2023-09-28 | 三井金属鉱業株式会社 | 粗化処理銅箔、キャリア付銅箔、銅張積層板及びプリント配線板 |
WO2024070245A1 (ja) * | 2022-09-28 | 2024-04-04 | Jx金属株式会社 | 表面処理銅箔、銅張積層板及びプリント配線板 |
WO2024070247A1 (ja) * | 2022-09-28 | 2024-04-04 | Jx金属株式会社 | 表面処理銅箔、銅張積層板及びプリント配線板 |
WO2024070248A1 (ja) * | 2022-09-28 | 2024-04-04 | Jx金属株式会社 | 表面処理銅箔、銅張積層板及びプリント配線板 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017179416A1 (ja) * | 2016-04-14 | 2017-10-19 | 三井金属鉱業株式会社 | 表面処理銅箔、キャリア付銅箔、並びにそれらを用いた銅張積層板及びプリント配線板の製造方法 |
WO2020105289A1 (ja) * | 2018-11-19 | 2020-05-28 | 三井金属鉱業株式会社 | 表面処理銅箔、キャリア付銅箔、銅張積層板及びプリント配線板 |
JP2020122190A (ja) * | 2019-01-30 | 2020-08-13 | Jx金属株式会社 | 表面処理銅箔、銅張積層板及びプリント配線板 |
JP2020122189A (ja) * | 2019-01-30 | 2020-08-13 | Jx金属株式会社 | 表面処理銅箔、銅張積層板及びプリント配線板 |
JP2020128589A (ja) * | 2019-02-01 | 2020-08-27 | 長春石油化學股▲分▼有限公司 | 表面処理銅箔 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5758035B2 (ja) | 2013-08-20 | 2015-08-05 | Jx日鉱日石金属株式会社 | 表面処理銅箔及びそれを用いた積層板、プリント配線板、電子機器、並びに、プリント配線板の製造方法 |
JP7356209B2 (ja) | 2017-03-31 | 2023-10-04 | Jx金属株式会社 | 表面処理銅箔、樹脂層付き表面処理銅箔、キャリア付銅箔、積層体、プリント配線板の製造方法及び電子機器の製造方法 |
-
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017179416A1 (ja) * | 2016-04-14 | 2017-10-19 | 三井金属鉱業株式会社 | 表面処理銅箔、キャリア付銅箔、並びにそれらを用いた銅張積層板及びプリント配線板の製造方法 |
WO2020105289A1 (ja) * | 2018-11-19 | 2020-05-28 | 三井金属鉱業株式会社 | 表面処理銅箔、キャリア付銅箔、銅張積層板及びプリント配線板 |
JP2020122190A (ja) * | 2019-01-30 | 2020-08-13 | Jx金属株式会社 | 表面処理銅箔、銅張積層板及びプリント配線板 |
JP2020122189A (ja) * | 2019-01-30 | 2020-08-13 | Jx金属株式会社 | 表面処理銅箔、銅張積層板及びプリント配線板 |
JP2020128589A (ja) * | 2019-02-01 | 2020-08-27 | 長春石油化學股▲分▼有限公司 | 表面処理銅箔 |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2023182177A1 (ja) * | 2022-03-24 | 2023-09-28 | 三井金属鉱業株式会社 | 粗化処理銅箔、キャリア付銅箔、銅張積層板及びプリント配線板 |
WO2023182179A1 (ja) * | 2022-03-24 | 2023-09-28 | 三井金属鉱業株式会社 | 粗化処理銅箔、キャリア付銅箔、銅張積層板及びプリント配線板 |
WO2023182174A1 (ja) * | 2022-03-24 | 2023-09-28 | 三井金属鉱業株式会社 | 粗化処理銅箔、キャリア付銅箔、銅張積層板及びプリント配線板 |
WO2023182176A1 (ja) * | 2022-03-24 | 2023-09-28 | 三井金属鉱業株式会社 | 粗化処理銅箔、キャリア付銅箔、銅張積層板及びプリント配線板 |
WO2023182175A1 (ja) * | 2022-03-24 | 2023-09-28 | 三井金属鉱業株式会社 | 粗化処理銅箔、キャリア付銅箔、銅張積層板及びプリント配線板 |
WO2023182178A1 (ja) * | 2022-03-24 | 2023-09-28 | 三井金属鉱業株式会社 | 粗化処理銅箔、キャリア付銅箔、銅張積層板及びプリント配線板 |
WO2024070245A1 (ja) * | 2022-09-28 | 2024-04-04 | Jx金属株式会社 | 表面処理銅箔、銅張積層板及びプリント配線板 |
WO2024070247A1 (ja) * | 2022-09-28 | 2024-04-04 | Jx金属株式会社 | 表面処理銅箔、銅張積層板及びプリント配線板 |
WO2024070248A1 (ja) * | 2022-09-28 | 2024-04-04 | Jx金属株式会社 | 表面処理銅箔、銅張積層板及びプリント配線板 |
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