CN117337344A - Roughened copper foil, copper foil with carrier, copper-clad laminate, and printed wiring board - Google Patents
Roughened copper foil, copper foil with carrier, copper-clad laminate, and printed wiring board Download PDFInfo
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- CN117337344A CN117337344A CN202280036136.0A CN202280036136A CN117337344A CN 117337344 A CN117337344 A CN 117337344A CN 202280036136 A CN202280036136 A CN 202280036136A CN 117337344 A CN117337344 A CN 117337344A
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- Prior art keywords
- roughened
- copper foil
- particles
- axis
- copper
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 233
- 239000011889 copper foil Substances 0.000 title claims abstract description 197
- 239000002245 particle Substances 0.000 claims abstract description 114
- 239000012798 spherical particle Substances 0.000 claims abstract description 35
- 238000010191 image analysis Methods 0.000 claims abstract description 18
- 238000011282 treatment Methods 0.000 claims description 52
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 23
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 11
- 230000005540 biological transmission Effects 0.000 abstract description 27
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 238000012545 processing Methods 0.000 abstract description 7
- 239000010410 layer Substances 0.000 description 96
- 239000011347 resin Substances 0.000 description 41
- 229920005989 resin Polymers 0.000 description 41
- 229910052802 copper Inorganic materials 0.000 description 36
- 239000010949 copper Substances 0.000 description 36
- 238000000034 method Methods 0.000 description 29
- 238000007747 plating Methods 0.000 description 29
- 239000000243 solution Substances 0.000 description 29
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 26
- 238000005530 etching Methods 0.000 description 25
- 238000011156 evaluation Methods 0.000 description 24
- 238000007788 roughening Methods 0.000 description 23
- 239000000758 substrate Substances 0.000 description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- 238000004458 analytical method Methods 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- 229910000365 copper sulfate Inorganic materials 0.000 description 10
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 239000011888 foil Substances 0.000 description 9
- -1 and the like Chemical compound 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 239000011701 zinc Substances 0.000 description 8
- 229910000990 Ni alloy Inorganic materials 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 7
- 238000005498 polishing Methods 0.000 description 7
- 229910052725 zinc Inorganic materials 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
- 238000000151 deposition Methods 0.000 description 6
- 230000002401 inhibitory effect Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 238000004070 electrodeposition Methods 0.000 description 5
- 230000005484 gravity Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000000007 visual effect Effects 0.000 description 5
- MTRFEWTWIPAXLG-UHFFFAOYSA-N 9-phenylacridine Chemical compound C1=CC=CC=C1C1=C(C=CC=C2)C2=NC2=CC=CC=C12 MTRFEWTWIPAXLG-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- KFJDQPJLANOOOB-UHFFFAOYSA-N 2h-benzotriazole-4-carboxylic acid Chemical compound OC(=O)C1=CC=CC2=NNN=C12 KFJDQPJLANOOOB-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 238000009499 grossing Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 230000003746 surface roughness Effects 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 229910001297 Zn alloy Inorganic materials 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000002500 effect on skin Effects 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- XEMZLVDIUVCKGL-UHFFFAOYSA-N hydrogen peroxide;sulfuric acid Chemical compound OO.OS(O)(=O)=O XEMZLVDIUVCKGL-UHFFFAOYSA-N 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 239000002346 layers by function Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000010295 mobile communication Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 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
- 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
- UYWWLYCGNNCLKE-UHFFFAOYSA-N 2-pyridin-4-yl-1h-benzimidazole Chemical compound N=1C2=CC=CC=C2NC=1C1=CC=NC=C1 UYWWLYCGNNCLKE-UHFFFAOYSA-N 0.000 description 1
- NNRAOBUKHNZQFX-UHFFFAOYSA-N 2H-benzotriazole-4-thiol Chemical compound SC1=CC=CC2=C1NN=N2 NNRAOBUKHNZQFX-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
- 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
- 239000004593 Epoxy Substances 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 description 1
- DUYKOAQJUCADEC-UHFFFAOYSA-N [SiH4].N1=NN=CC=C1 Chemical compound [SiH4].N1=NN=CC=C1 DUYKOAQJUCADEC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- BQJTUDIVKSVBDU-UHFFFAOYSA-L copper;sulfuric acid;sulfate Chemical group [Cu+2].OS(O)(=O)=O.[O-]S([O-])(=O)=O BQJTUDIVKSVBDU-UHFFFAOYSA-L 0.000 description 1
- 239000013310 covalent-organic framework Substances 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- PPTYNCJKYCGKEA-UHFFFAOYSA-N dimethoxy-phenyl-prop-2-enoxysilane Chemical compound C=CCO[Si](OC)(OC)C1=CC=CC=C1 PPTYNCJKYCGKEA-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 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
- 238000001704 evaporation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 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
- 229920000642 polymer Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 238000004683 secondary electrospray ionisation mass spectroscopy Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 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
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- VMYXFDVIMUEKNP-UHFFFAOYSA-N trimethoxy-[5-(oxiran-2-yl)pentyl]silane Chemical compound CO[Si](OC)(OC)CCCCCC1CO1 VMYXFDVIMUEKNP-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
Abstract
Provided is a roughened copper foil which can achieve both excellent transmission characteristics and high shear strength in the processing of a copper-clad laminate to the production of a printed wiring board. The roughened copper foil has a roughened surface on at least one side. The roughened surface has a plurality of roughened particles containing spherical particles, and when three-dimensional image analysis is performed on an image obtained by using a FIB-SEM for the roughened surface, the average height of the roughened particles is 70nm or less, and the proportion of the spherical particles in the plurality of roughened particles is 30% or more. The spherical particles are the following: in the case where the major axis, the center axis, and the minor axis orthogonal to each other are set with respect to the roughened particles, and the length L of the major axis is set to 1.0, the length M of the center axis is 0.3.ltoreq.M.ltoreq.1.0, and the length S of the minor axis is 0.3.ltoreq.S.ltoreq.1.0.
Description
Technical Field
The present invention relates to a roughened copper foil, a copper foil with a carrier, a copper-clad laminate, and a printed circuit board.
Background
In recent years, MSAP (modified semi-additive process) method has been widely used as a method for manufacturing printed circuit boards suitable for circuit miniaturization. The MSAP method is a method suitable for forming an extremely fine circuit, and is performed using a copper foil with a carrier in order to use the characteristics thereof. For example, as shown in fig. 1 and 2, an extra thin copper foil (roughened copper foil 10) is pressed against an insulating resin substrate 11 with a prepreg 12 and a primer layer 13 interposed therebetween to be in close contact with each other, the insulating resin substrate 11 is provided with a lower layer circuit 11b on a base substrate 11a (step (a)), a carrier (not shown) is peeled off, and then a via hole 14 is formed by laser perforation as needed (step (b)). Next, after electroless copper plating 15 is performed (step (c)), exposure and development using a dry film 16 are performed to mask the film in a predetermined pattern (step (d)), and copper plating 17 is performed (step (e)). After the dry film 16 is removed to form the wiring portion 17a (step (f)), unnecessary extra thin copper foil or the like between the wiring portions 17a and 17a adjacent to each other is removed by etching over the entire thickness thereof (step (g)), and the wiring 18 formed in a predetermined pattern is obtained. Here, in order to improve the physical adhesion between the circuit and the substrate, the surface of the extra thin copper foil is generally roughened.
In practice, several carrier-attached copper foils excellent in fine circuit formability based on the MSAP method or the like have been proposed. For example, patent document 1 (international publication No. 2016/117587) discloses a carrier-equipped copper foil comprising an extra thin copper foil having an average surface peak-to-peak distance of 20 μm or less on the release layer side surface and a maximum level difference of 1.0 μm or less on the opposite side surface of the release layer, and it is considered that this system can achieve both fine circuit formation and laser processability. Patent document 2 (japanese patent application laid-open No. 2018-26590) discloses a copper foil with a carrier, in which the ratio Sp/Spk of the maximum peak height Sp to the protruding peak height Spk of the surface of the ultra-thin copper layer according to ISO25178 is 3.271 to 10.739.
On the other hand, as the miniaturization of circuits progresses, physical stress (i.e., shear stress) from the lateral direction is applied to the circuits in the mounting process of printed circuit boards, which causes the circuits to be easily peeled off, and the yield is remarkably lowered. In this regard, as one of the physical adhesion indexes of the circuit and the substrate, there is shear strength (shear strength), and in order to effectively avoid the peeling of the circuit, a roughened copper foil suitable for improving the shear strength has been proposed. For example, patent document 3 (international publication No. 2020/031721) discloses a roughened copper foil in which the maximum height Sz, the interface expansion area ratio Sdr, and the peak top density Spd defined in ISO25178 are controlled to be within predetermined ranges. According to the roughened copper foil, excellent etching properties and high shear strength can be achieved at the same time in the processing of the copper-clad laminate to the production of a printed wiring board.
On the other hand, with recent high-functionality of portable electronic devices and the like, in order to process a large amount of information at high speed, a high frequency signal has been developed, and a printed circuit board particularly suitable for high frequency applications such as a fifth generation mobile communication system (5G) and a sixth generation mobile communication system (6G) has been demanded. In order to transmit a high-frequency signal without deteriorating the quality of the high-frequency signal, a reduction in transmission loss is desired for such a high-frequency printed circuit board. The printed circuit board includes a copper foil processed into a wiring pattern and an insulating resin base material, and the transmission loss is mainly composed of a conductor loss due to the copper foil and a dielectric loss due to the insulating resin base material.
Conductor loss may increase due to the skin effect of the copper foil which becomes more pronounced with higher frequencies. Therefore, in order to suppress transmission loss in high frequency applications, smoothing of the copper foil and miniaturization of the roughened particles are required to reduce the skin effect of the copper foil. In this regard, roughened copper foil is known for the purpose of reducing transmission loss. For example, patent document 4 (japanese patent No. 6462961) relates to a surface-treated copper foil in which a roughened layer, an anti-rust treatment layer, and a silane coupling layer are laminated in this order on at least one surface of the copper foil, and discloses that the interface expansion area ratio Sdr measured from the surface of the silane coupling layer is 8% or more and 140% or less, the root mean square slope Sdq is 25 ° or more and 70 ° or less, and the aspect ratio Str of the surface properties is 0.25 or more and 0.79 or less. According to the surface-treated copper foil, a printed wiring board having less transmission loss of high-frequency electric signals and excellent adhesion at the time of reflow soldering can be produced.
Prior art literature
Patent literature
Patent document 1: international publication No. 2016/117587
Patent document 2: japanese patent laid-open publication No. 2018-26590
Patent document 3: international publication No. 2020/031721
Patent document 4: japanese patent No. 6462961
Disclosure of Invention
As described above, from the viewpoint of high frequency transmission, a copper foil with low transmission loss (i.e., a copper foil excellent in high frequency characteristics) is required as a material for forming a circuit wiring for a flow signal. Although transmission loss can be suppressed by smoothing of the copper foil and miniaturization of the roughened particles, the physical bonding force (in particular, shear strength) of the copper foil and the substrate resin or the like is lowered. Therefore, it is not easy to achieve both excellent transfer characteristics and high circuit adhesion.
The inventors have found the following findings at this time: in the roughened copper foil, the surface profile is given so that the average height of the roughened particles and the ratio of the spherical particles to the roughened particles are controlled within a predetermined range, whereby excellent transfer characteristics and high shear strength can be achieved at the same time in the processing of the copper-clad laminate to the production of the printed wiring board.
Accordingly, an object of the present invention is to provide a roughened copper foil which can achieve both excellent transfer characteristics and high shear strength in the processing of a copper-clad laminate to the production of a printed wiring board.
According to the present invention, the following manner is provided.
Mode 1
A roughened copper foil having a roughened surface on at least one side, the roughened surface having a plurality of roughened particles comprising spherical particles,
when three-dimensional image analysis is performed on an image obtained by using a FIB-SEM for the roughened surface, the average height of the roughened particles is 70nm or less, and the proportion of the spherical particles in the plurality of roughened particles is 30% or more,
the spherical particles are the following particles: when the long axis, the middle axis and the short axis orthogonal to each other are set with respect to the roughened particles, and the length L of the long axis is set to 1.0, the length M of the middle axis is 0.3.ltoreq.M.ltoreq.1.0, and the length S of the short axis is 0.3.ltoreq.S.ltoreq.1.0.
Mode 2
The roughened copper foil according to embodiment 1, wherein the average height is 20nm or more and 70nm or less.
Mode 3
The roughened copper foil according to embodiment 1 or 2, wherein the proportion of the spherical particles is 30% or more and 90% or less.
Mode 4
The roughened copper foil according to any one of the aspects 1 to 3, wherein,
When three-dimensional image analysis is performed on an image obtained by FIB-SEM for the roughened surface by assigning x-axis, y-axis and z-axis so that the z-axis is perpendicular to the roughened surface and the x-y plane is parallel to the roughened surface and dividing the roughened particle into a plurality of voxels, the average value of the bottom area ratio of the plurality of roughened particles is 3.0 or less,
the bottom area ratio is a ratio of a projected area in each of the roughened particles to a bottom area, the bottom area is defined as an x-y plane area value of voxels constituting a bottom surface of each of the roughened particles, and the projected area is defined as a product of an x value of a maximum voxel in an x-axis direction and a y value of a maximum voxel in a y-axis direction in each of the roughened particles.
Mode 5
The roughened copper foil according to embodiment 4, wherein the average value of the bottom area ratio is 2.0 or more and 3.0 or less.
Mode 6
The roughened copper foil according to any one of aspects 1 to 5, wherein the roughened surface further comprises a rust-preventive treatment layer and/or a silane coupling agent layer.
Mode 7
A copper foil with a carrier, comprising: the roughened copper foil according to any one of aspects 1 to 6, wherein the roughened copper foil is provided on the release layer so that the roughened surface is on the outside.
Mode 8
A copper-clad laminate comprising the roughened copper foil according to any one of aspects 1 to 6 or the copper foil with carrier according to aspect 7.
Mode 9
A printed wiring board comprising the roughened copper foil according to any one of aspects 1 to 6 or the copper foil with carrier according to aspect 7.
Drawings
Fig. 1 is a process flow chart for explaining the MSAP method, and is a diagram showing the first half steps (a) to (d)).
Fig. 2 is a process flow chart for explaining the MSAP method, and is a diagram showing the second half of the process (steps (e) to (g)).
Fig. 3 is a schematic view of a roughened particle divided into a plurality of voxels, which is a diagram for explaining a projected area and a bottom area.
Fig. 4 is a view showing a region where laser light is not incident when the roughened surface is measured by a laser microscope.
Fig. 5 is a graph showing the relationship between the x-axis, y-axis and z-axis, and the sliced surface S and the roughened copper foil in 3D-SEM observation.
Fig. 6 is a graph showing the relationship between each axis after rotation of the x-axis, y-axis and z-axis and the roughened copper foil in 3D-SEM image analysis.
Detailed Description
Definition of the definition
The following illustrates definitions of terms and/or parameters used to define the invention.
In the present specification, "an image obtained by using FIB-SEM for the roughened surface" means: the roughened surface of the roughened copper foil is an aggregate of cross-sectional images obtained by cross-sectional processing by FIB (focused ion beam) and cross-sectional observation by SEM (scanning electron microscope), and the aggregate as a whole constitutes three-dimensional shape data. Specifically, as shown in fig. 5, the x-axis and the z-axis are defined as the in-plane direction of the roughened copper foil 10, and the y-axis is defined as the thickness direction of the roughened copper foil 10, and then, a cross-sectional image of the roughened surface including the roughened copper foil 10 in a slice plane S parallel to the x-y plane is acquired, and the slice plane is moved in parallel at predetermined intervals (for example, 5 nm) in the z-axis direction, and at the same time, an aggregate of cross-sectional images acquired in a predetermined analysis area (for example, 2400nm×2400nm area when the roughened surface is viewed in plan view) is acquired.
In the present specification, "average height of roughened particles" means: the average height of the roughened particles present in a predetermined analysis region (for example, a region of 2400nm×2400nm when the roughened surface is viewed from above). The average height of the roughened particles can be determined by three-dimensional image analysis of an image obtained using FIB-SEM for the roughened surface. In the case of three-dimensional image analysis, the base shape of the copper foil before roughening treatment may be determined as roughened particles (protrusions), and the portion thus determined may be considered as roughened particles to be calculated as various parameters, even if it is not formed by roughening treatment.
In the present specification, "spherical particles" refer to particles as follows: when the major axis, the middle axis and the minor axis orthogonal to each other are set with respect to the roughened particles, and the length L of the major axis is set to 1.0, the length M of the middle axis is 0.3.ltoreq.M.ltoreq.1.0, and the length S of the minor axis is 0.3.ltoreq.S.ltoreq.1.0. In the present specification, "flat particles" refer to particles as follows: when the length L of the long axis is 1.0, the length M of the center axis is 0.3 < M.ltoreq.1.0, and the length S of the short axis is S < 0.3. In the present specification, "elongated particles" refer to particles of: when the length L of the long axis is 1.0, the length M of the middle axis is M.ltoreq.0.3, and the length S of the short axis is S.ltoreq.0.3. In the present specification, "proportion of spherical particles" means: the proportion of spherical particles in the roughened particles present in a predetermined analysis region (for example, a region of 2400nm×2400nm in plan view of the roughened surface). That is, by setting the number N of spherical particles S Divided by the sum of the numbers of the individual particles (i.e. the number N of spherical particles S Number N of flat particles F And number N of elongated particles E Sum) and multiplied by 100 (=100×n) S /(N S +N F +N E ) The ratio of the spherical particles can be calculated. Spherical particles and flat particles can be obtained by three-dimensional image analysis of an image obtained by using FIB-SEM for a roughened surfaceAnd classification of elongated particles.
In the present specification, "voxel" refers to an element of a 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, cuboids, or the like, and for example, each 1 voxel has a size of (length, width, height) = (1 nm ), and thus can be converted into SI units.
In the present specification, "average value of bottom area ratio" means: the average value of the bottom area ratio of the roughened particles present in a predetermined analysis region (for example, a region of 2400nm×2400nm in a plan view of the roughened surface), and the "bottom area ratio" means the ratio of the projected area to the bottom area in each roughened particle. The bottom surface area and the projected area can be determined by dividing the roughened particle into a plurality of voxels. Specifically, as shown in fig. 6, the x-axis, the y-axis, and the z-axis are distributed so that the z-axis is perpendicular to the roughening surface and the x-y plane is parallel to the roughening surface, and a three-dimensional image analysis is performed on an image obtained by using the FIB-SEM for the roughening surface, whereby the roughened particles are divided into a plurality of voxels. At this time, as shown in fig. 3, the projection area P is defined as a product of the x value of the maximum voxel in the x-axis direction and the y value of the maximum voxel in the y-axis direction in the roughened particle 10 a. In addition, as shown in fig. 3, the bottom area B is defined in the form of an x-y plane area value of voxels constituting the bottom surface of the roughened particle 10 a.
As described above, the average height of the roughened particles, the ratio of the spherical particles, and the average value of the bottom area ratio can be determined by performing three-dimensional image analysis on an image obtained by using FIB-SEM for the roughened surface. Such three-dimensional image analysis can be performed using commercially available software. For example, for an image of the roughened surface (a slice image of three-dimensional shape data of the roughened copper foil), three-dimensional position alignment software "ExFact Slice Aligner (version 2.0)" (Nihon Visual Science, manufactured by inc.) and three-dimensional image Analysis software "extract VR (version 2.2)", and "foil Analysis (version 1.0)" (both Nihon Visual Science, manufactured by inc.) may be used to perform image Analysis according to the conditions described in the examples of the present specification. The method for acquiring a cross-sectional image obtained by using the FIB-SEM is as shown in examples described later.
In the present specification, the "electrode surface" of the support means a surface on a side that contacts the cathode when the support is fabricated.
In the present specification, the "deposition surface" of the support means a surface on the electrolytic copper deposition side, that is, a surface on the side not in contact with the cathode when the support is produced.
Roughened copper foil
The copper foil according to the present invention is a roughened copper foil. The roughened copper foil has a roughened surface on at least one side. The roughened surface has a plurality of roughened particles including spherical particles. When a three-dimensional image analysis is performed on an image obtained by using a FIB-SEM for the roughened surface, the average height of the roughened particles is 70nm or less. The proportion of the spherical particles in the plurality of roughened particles is 30% or more. In such a roughened copper foil, by providing a surface profile in which the average height of the roughened particles and the proportion of the spherical particles in the roughened particles are controlled within predetermined ranges, excellent transmission characteristics (particularly excellent high-frequency characteristics) and high shear strength (further, high circuit adhesion in terms of shear strength) can be simultaneously achieved in the process of processing a copper-clad laminate to manufacturing a printed wiring board.
As described above, although it is originally difficult to achieve both excellent transmission characteristics and high shear strength, the roughened copper foil according to the present invention is unexpectedly compatible. The mechanism is not clear, but the following can be listed as a main reason. First, by reducing the average height of the roughened particles to 70nm or less, reduction of transmission loss due to the micronization of the roughened particles can be achieved. Further, although there is a concern that the shear strength may decrease with the micronization of the roughened particles, it is considered that by increasing the proportion of the spherical particles in the roughened particles to 30% or more, an anchoring effect due to the contracted shape of the spherical particles can be exerted, and excellent adhesion to the resin can be achieved while being fine particles.
On the other hand, in the prior art, the roughened shape is evaluated using a laser microscope, but there is a limit in correctly evaluating the characteristics of a minute roughened shape by this method. Fig. 4 schematically shows an example of measurement of the roughened surface by a laser microscope. As shown in fig. 4, in the measurement by the laser microscope, laser light is irradiated from above the roughened surface. At this time, there is a region N where laser light cannot be incident due to shielding by the roughened particles 10 a. Because of this region N, it may be difficult to accurately evaluate the characteristics such as the shrinkage shape of the roughened particles 10a in the measurement of the roughened surface using a laser microscope. This problem is remarkable when a minute roughened shape is required that combines excellent transfer characteristics and high circuit adhesion. In addition, in the prior art, a method of three-dimensional evaluation of a sample has been studied, but it is not sufficient as an evaluation method that can achieve both excellent transmission characteristics and high shear strength. In contrast, in the present invention, the roughened copper foil is three-dimensionally evaluated and controlled to a proper range by focusing on the average height of the roughened particles and the ratio of the spherical particles, and when used in a copper-clad laminate or a printed circuit board, both excellent transmission characteristics and high shear strength can be achieved.
The average height of the roughened particles is 70nm or less, preferably 20nm or more and 70nm or less, more preferably 30nm or more and 70nm or less, still more preferably 50nm or more and 70nm or less, and particularly preferably 60nm or more and 70nm or less. This enables to realize excellent transmission characteristics even with high shear strength.
The proportion of the spherical particles in the roughened particles is 30% or more, preferably 30% or more and 90% or less, more preferably 30% or more and 70% or less, still more preferably 30% or more and 50% or less, and particularly preferably 35% or more and 45% or less. This can realize high shear strength while having excellent transmission characteristics.
The average value of the basal area ratio in the roughened particles is preferably 3.0 or less, more preferably 2.0 or more and 3.0 or less. In recent years, along with the miniaturization of electronic equipment terminals and the like, further miniaturization is demanded in terms of circuits, and by setting the average value of the bottom area ratio in the roughened particles to be within the above-described range, the etching property of the copper foil can be improved, which is advantageous for the formation of fine line circuits.
The mechanism of improving etching property by controlling the average value of the bottom area ratio is not clear, but one of the main causes is as follows. That is, when a circuit is formed on a copper-clad laminate or the like by etching, it is necessary to remove not only the copper foil on the surface but also the roughened particles that have entered the substrate resin. At this time, too small a contracted portion of the roughened particles may cause difficulty in the etching liquid to penetrate into the portion of the resin substrate where the roughened particles have entered, and there is a possibility that a large etching amount is required to eliminate residual copper. In this regard, it is considered that when the average value of the bottom area ratio in the roughened particles is within the above range, the roughened particles become particles having a shrink shape that is just suitable for immersion of the etching liquid, and the amount of etching required for removing the roughened particles can be reduced.
The thickness of the roughened copper foil is not particularly limited, but is preferably 0.1 μm or more and 35 μm or less, more preferably 0.5 μm or more and 5.0 μm or less, and still more preferably 1.0 μm or more and 3.0 μm or less. The roughened copper foil is not limited to the copper foil roughened on the surface of a conventional copper foil, and may be a copper foil roughened on the surface of a copper foil with a carrier. The roughened copper foil has a thickness (thickness of the copper foil itself constituting the roughened copper foil) of a height not including the roughened particles formed on the surface of the roughened surface. A copper foil having a thickness in the above range is sometimes referred to as an extra thin copper foil.
The roughened copper foil has a roughened surface on at least one side. That is, the roughened copper foil may have roughened surfaces on both sides, or may have roughened surfaces on only one side. The roughened surface is provided with a plurality of roughened particles, and the plurality of roughened particles are preferably each formed of copper particles. The copper particles may be formed of metallic copper or a copper alloy.
The roughening treatment for forming the roughened surface may be more preferably performed by forming roughened particles from copper or a copper alloy on top of the copper foil. The roughening treatment is preferably performed according to a plating method that goes through a plating process of 3 stages. In this case, it is preferable to use a copper sulfate solution having a copper concentration of 5g/L or more and 15g/L or less and a sulfuric acid concentration of 200g/L or more and 250g/L or less in the plating step of the 1 st stage, and to use a copper sulfate solution having a liquid temperature of 25 ℃ or more and 45 ℃ or less and a current density of 2A/dm 2 Above and 4A/dm 2 Electrodeposition was performed under the following plating conditions. In particular, it is preferable that the plating step in the 1 st stage is performed twice in total using two tanks. Preferably, in the plating step of the 2 nd stage, a copper sulfate solution having a copper concentration of 60g/L to 80g/L and a sulfuric acid concentration of 200g/L to 260g/L is used, and the solution temperature is 45 ℃ to 55 ℃ inclusive and the current density is 10A/dm 2 Above and 15A/dm 2 Electrodeposition was performed under the following plating conditions. Preferably, in the plating step of the 3 rd stage, a copper sulfate solution having a copper concentration of 5g/L to 20g/L, a sulfuric acid concentration of 60g/L to 90g/L, a chlorine concentration of 20mg/L to 40mg/L, and a 9-phenylacridine (9 PA) concentration of 100mg/L to 200mg/L is used, and the solution has a current density of 30A/dm at a liquid temperature of 25 ℃ to 35 ℃ inclusive 2 Above and 60A/dm 2 Electrodeposition was performed under the following plating conditions. The plating steps in the 2 nd and 3 rd stages may be performed twice in total using two tanks, but the total is preferably completed 1 time. By undergoing such a plating process, it becomes easy to form protrusions on the treated surface that are suitable for satisfying the surface parameters described above.
The roughened copper foil may be subjected to an anti-rust treatment to form an anti-rust treated layer, as desired. The rust inhibitive treatment preferably includes a plating treatment using zinc. The plating treatment using zinc may be any of a zinc plating treatment and a zinc alloy plating treatment, and the zinc alloy plating treatment is particularly preferably a 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, mo. The Ni/Zn attachment ratio in the zinc-nickel alloy plating is preferably 1.2 to 10, more preferably 2 to 7, still more preferably 2.7 to 4 in terms of mass ratio. In addition, the rust inhibitive treatment further preferably includes a chromate treatment, which is more preferably performed on the surface of the zinc-containing plating layer after the plating treatment with zinc. This can further improve rust resistance. Particularly preferred rust inhibitive treatments are a combination of zinc-nickel alloy plating treatments followed by chromate treatments.
If desired, a silane coupling agent treatment may be performed on the surface of the roughened copper foil to form a silane coupling agent layer. This can improve moisture resistance, chemical resistance, adhesion to adhesives, and the like. The silane coupling agent layer may be formed by appropriately diluting and coating the silane coupling agent and drying it. Examples of the silane coupling agent include: epoxy functional silane coupling agents such as 4-glycidyl butyl trimethoxysilane and 3-glycidoxypropyl trimethoxysilane; or amino-functional silane coupling agents such as 3-aminopropyl trimethoxysilane, N- (2-aminoethyl) -3-aminopropyl trimethoxysilane, N-3- (4- (3-aminopropoxy) butoxy) propyl-3-aminopropyl trimethoxysilane, and N-phenyl-3-aminopropyl trimethoxysilane; or 3-mercaptopropyl trimethoxy silane and other mercapto functional silane coupling agents; or an olefin functional silane coupling agent such as vinyltrimethoxysilane or vinylphenyltrimethoxysilane; or an acrylic functional silane coupling agent such as 3-methacryloxypropyl trimethoxysilane; or imidazole functional silane coupling agents such as imidazole silane; or a triazine functional silane coupling agent such as a triazine silane.
For the above reasons, the roughened copper foil is preferably further provided with a rust-preventive treatment layer and/or a silane coupling agent layer on the roughened surface, and more preferably with both the rust-preventive treatment layer and the silane coupling agent layer. In the case where the rust inhibitive treated layer and/or the silane coupling agent layer are formed on the roughened surface, each numerical value of the average height of the roughened particles, the ratio of the spherical particles, and the average value of the basal area ratio in the present specification refers to a numerical value obtained by measuring and analyzing the roughened copper foil after the formation of the rust inhibitive treated layer and/or the silane coupling agent treated layer. The rust inhibitive 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 on which the roughened surface is not formed.
Copper foil with carrier
As described above, the roughened copper foil of the present invention may be provided in the form of a copper foil with a carrier. By adopting the copper foil with carrier, excellent laser processability and fine line circuit formability can be achieved. That is, according to a preferred embodiment of the present invention, there is provided a copper foil with a carrier, comprising: the copper foil is provided with a support, a release layer provided on the support, and the roughened copper foil provided on the release layer so that the roughened surface is outside. Of course, the copper foil with carrier may have a known layer structure in addition to the roughened copper foil of the present invention.
The carrier is a support for supporting the roughened copper foil so as to improve its handling properties, and typically the carrier comprises a metal layer. Examples of such a carrier include aluminum foil, copper foil, stainless steel (SUS) foil, resin film having a surface coated with metal such as copper, glass, and the like, and copper foil is preferable. The copper foil may be either a rolled copper foil or an electrolytic copper foil, and is preferably an electrolytic copper foil. The thickness of the support is typically 250 μm or less, preferably 7 μm or more and 200 μm or less.
The release layer side surface of the support is preferably smooth. That is, in the process for producing a copper foil with a carrier, an extra thin copper foil is formed on the release layer side surface of the carrier (before the roughening treatment). When the roughened copper foil of the present invention is used as a copper foil with a carrier, the roughened copper foil can be obtained by roughening such an extra thin copper foil. Therefore, by smoothing the surface of the carrier on the release layer side in advance, the surface of the outer side of the extra thin copper foil can be smoothed, and by roughening the smooth surface of the extra thin copper foil, it becomes easy to realize a roughened surface having an average height of roughened particles or the like within the above-mentioned predetermined range. In order to smooth the surface of the carrier on the release layer side, the surface roughness of the cathode used for electrolytic foil forming of the carrier may be adjusted by polishing the surface of the cathode with a polishing wheel of a predetermined model, for example. That is, the surface profile of the cathode thus adjusted is transferred to the electrode surface of the support, and the extra thin copper foil is formed on the electrode surface of the support via the peeling layer, whereby a smooth surface state that can easily achieve the above-described roughened surface can be imparted to the surface on the outer side of the extra thin copper foil. The polishing wheel is preferably a polishing wheel having a model number of #2000 or more and #3000 or less, more preferably #2000 or more and #2500 or less. The electrode surface of the support obtained by using the cathode polished by the polishing wheel of #2000 or more and #2500 or less has slight waviness compared with the smooth foil deposition surface, and thus can ensure adhesion and smoothness, and can realize high adhesion and excellent transfer characteristics with a more balanced property. In addition, from the viewpoint of making the extra thin copper foil smoother and the various surface parameters of the resulting roughened copper foil easier to control in the above-described ranges, the deposition surface side of the carrier obtained by electrolytic foil production using the electrolyte containing the additive may be used as the release layer side surface of the carrier.
The release layer is a layer having the following functions: the peeling strength of the carrier is reduced, the stability of the strength is ensured, and further, the inter-diffusion possibly occurring between the carrier and the copper foil is suppressed at the time of press molding at high temperature. The release layer is typically formed on one side of the carrier, but may be formed on both sides. The release layer may be any one of an organic release layer and an inorganic release layer. Examples of the organic component used in the organic release layer include nitrogen-containing organic compounds, sulfur-containing organic compounds, carboxylic acids, and the like. Examples of the nitrogen-containing organic compound include triazole compounds and imidazole compounds, and among them, triazole compounds are preferable from the viewpoint of easy and stable peeling property. Examples of the triazole compound include 1,2, 3-benzotriazole, carboxybenzotriazole, N' -bis (benzotriazolomethyl) urea, 1H-1,2, 4-triazole, 3-amino-1H-1, 2, 4-triazole, and the like. Examples of the sulfur-containing organic compound include mercaptobenzotriazole, thiocyanuric acid, and 2-benzimidazole mercaptan. Examples of carboxylic acids include monocarboxylic acids and dicarboxylic acids. Examples of the inorganic component used for the inorganic release layer include Ni, mo, co, cr, fe, ti, W, P, zn and a chromate treatment film. The formation of the release layer may be performed by bringing a solution containing the release layer component into contact with at least one surface of the support, fixing the release layer component to the surface of the support, or the like. In the case of bringing the support into contact with the release layer-containing component solution, the contact may be performed by immersing in the release layer-containing component solution, spraying the release layer-containing component solution, flowing down the release layer-containing component solution, or the like. Further, a method of forming a film of a release layer component by a vapor phase method such as vapor deposition or sputtering may be used. The fixation of the release layer component to the surface of the support may be performed by adsorption and drying of a solution containing the release layer component, electrodeposition of the release layer component in the solution containing the release layer component, or the like. The thickness of the release layer is typically 1nm to 1 μm, preferably 5nm to 500 nm.
Other functional layers may be provided between the release layer and the carrier and/or roughened copper foil, as desired. As examples of such other functional layers, an auxiliary metal layer may be cited. The auxiliary metal layer is preferably formed of 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 interdiffusion which may occur between the carrier and the roughened copper foil during hot press molding at high temperature or for a long time, and to ensure the stability of the peel strength of the carrier. The thickness of the auxiliary metal layer is preferably set to 0.001 μm or more and 3 μm or less.
Copper-clad laminate
The roughened copper foil of the present invention is preferably used for producing a copper-clad laminate for a printed wiring board. That is, according to a preferred embodiment of the present invention, there is provided a copper-clad laminate comprising the roughened copper foil or the copper foil with carrier. The use of the roughened copper foil or the copper foil with carrier according to the present invention can achieve both excellent transfer characteristics and high shear strength in the processing of copper-clad laminates. The copper-clad laminate is provided with the roughened copper foil of the present invention, and a resin layer provided in close contact with the roughened surface of the roughened copper foil. The roughened copper foil may be provided on one side or both sides of the resin layer. The resin layer is made of a resin, preferably an insulating resin. The resin layer is preferably a prepreg and/or a resin sheet. The prepreg is a generic term for a composite material obtained by impregnating a synthetic resin into a base material such as a synthetic resin sheet, a glass woven fabric, a glass nonwoven fabric, or paper. Preferable examples of the insulating resin include epoxy resin, cyanate resin, bismaleimide triazine resin (BT resin), polyphenylene ether resin, and phenol resin. Examples of the insulating resin constituting the resin sheet include insulating resins such as epoxy resin, polyimide resin, and polyester resin. In addition, filler particles formed of various inorganic particles such as silica and alumina may be contained in the resin layer from the viewpoint of improving insulation properties and the like. The thickness of the resin layer is not particularly limited, but is preferably 1 μm or more and 1000 μm or less, more preferably 2 μm or more and 400 μm or less, and still more preferably 3 μm or more and 200 μm or less. The resin layer may be composed of a plurality of layers. The resin layer such as prepreg and/or resin sheet may be provided on the roughened copper foil with a primer resin layer previously applied to the surface of the copper foil.
Printed circuit board with improved heat dissipation
The roughened copper foil of the present invention is preferably used for the production of printed circuit boards. That is, according to a preferred embodiment of the present invention, there is provided a printed wiring board comprising the roughened copper foil or the copper foil with carrier. The use of the roughened copper foil or the copper foil with carrier according to the present invention can achieve both excellent transmission characteristics and high shear strength in the production of printed wiring boards. The printed circuit board of the present embodiment 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. In addition, the resin layer is as described above for the copper-clad laminate. In any case, the printed circuit board may employ a known layer structure in addition to the roughened copper foil of the present invention. Specific examples of the printed wiring board include a single-sided or double-sided printed wiring board obtained by bonding the roughened copper foil of the present invention to one or both sides of a prepreg, curing the bonded copper foil to form a laminate, and then forming a circuit, and a multilayer printed wiring board obtained by layering the laminate and the double-sided printed wiring board. Further, as other specific examples, there are flexible printed circuit boards, COFs, TAB tapes, and the like in which the roughened copper foil of the present invention is formed on a resin film to form a circuit. As other specific examples, there may be mentioned: forming a resin-coated copper foil (RCC) having the resin layer applied to the roughened copper foil of the present invention, laminating the resin layer as an insulating adhesive material layer on the printed circuit board, and forming a build-up wiring board of a circuit by a modified semi-addition (MSAP) method, an subtractive method or the like using the roughened copper foil as all or a part of the wiring layer; removing the roughened copper foil and forming a laminated circuit board of a circuit by a semi-additive method; a direct lamination wafer (direct build up on wafer) and the like are alternately laminated with resin-coated copper foil and circuit formed on a semiconductor integrated circuit. As a specific example of further extension, there may be mentioned: an antenna element formed by laminating the resin-coated copper foil on a substrate to form a circuit; an electronic material for a panel/display and an electronic material for a window glass, which are laminated on glass or a resin film via an adhesive layer and formed with a pattern; an electromagnetic wave shielding film or the like obtained by applying a conductive adhesive to the roughened copper foil of the present invention. In particular, a printed circuit board provided with the roughened copper foil of the present invention is suitable for use as a high-frequency substrate for use in applications such as an automobile antenna, a mobile phone base station antenna, a high-performance server, and an anti-collision radar, which are used in a high frequency band of 10GHz or more in signal frequency. In particular, the roughened copper foil of the present invention is suitable for the MSAP method. For example, when the circuit is formed by the MSAP method, the configuration shown in fig. 1 and 2 can be adopted.
Examples
The present invention will be described more specifically by the following examples.
Examples 1 to 3
The copper foil with carrier having the roughened copper foil was produced as follows.
(1) Preparation of the Carrier
A copper electrolyte, a cathode and DSA (dimensionally stable anode) as an anode were used in the compositions shown below, and the current density was 70A/dm at a solution temperature of 50 DEG C 2 Next, electrolysis was performed to prepare an electrolytic copper foil having a thickness of 18. Mu.m, as a carrier. At this time, as the cathode, an electrode whose surface roughness was adjusted by polishing the surface with a polishing wheel #2000 was used.
Composition of copper electrolyte
Copper concentration: 80g/L
Sulfuric acid concentration: 300g/L
Chlorine concentration: 30mg/L
-gum concentration: 5mg/L
(2) Formation of a release layer
In a CBTA aqueous solution containing Carboxybenzotriazole (CBTA) at a concentration of 1g/L, sulfuric acid at a concentration of 150g/L and copper at a concentration of 10g/L, the electrode surface of the support subjected to acid washing was immersed at a liquid temperature of 30℃for 30 seconds, whereby the CBTA component was adsorbed on the electrode surface of the support. Thus, a CBTA layer was formed as an organic peeling layer on the electrode surface of the support.
(3) Formation of auxiliary metal layer
Immersing the carrier with the organic stripping layer in a solution containing nickel with concentration of 20g/L prepared from nickel sulfate, and heating at 45deg.C, pH3 and current density of 5A/dm 2 Under the conditions of (2) the organic release layer was adhered with nickel in an adhering amount corresponding to a thickness of 0.001. Mu.m. Thereby, a nickel layer is formed as an auxiliary metal layer on the organic peeling layer.
(4) Formation of extra thin copper foil
Immersing the support on which the auxiliary metal layer was formed in a copper solution having the composition shown below at a solution temperature of 50℃and a current density of 5A/dm 2 Above and 30A/dm 2 An extra thin copper foil having a thickness of 1.5 μm was formed on the auxiliary metal layer by electrolysis.
< composition of solution >
Copper concentration: 60g/L
Sulfuric acid concentration: 200g/L
(5) Roughening treatment
The surface of the thus formed extra thin copper foil is roughened to form a roughened copper foil, thereby obtaining a carrier-attached copper foil. Regarding this roughening treatment, the following 3-stage roughening treatments were performed for examples 1 and 2.
The roughening treatment in stage 1 is carried out in two steps. Specifically, an acidic copper sulfate solution having copper concentration and sulfuric acid concentration shown in table 1 was used, and roughening treatment was performed 2 times at the current density and the liquid temperature shown in table 1.
The roughening treatment in stage 2 was performed using an acidic copper sulfate solution having copper concentration and sulfuric acid concentration shown in table 1, at a current density and a liquid temperature shown in table 1.
Stage 3 roughening treatment the roughening treatment was carried out at the current density and liquid temperature shown in table 1 using an acidic copper sulfate solution of copper concentration, sulfuric acid concentration, chlorine concentration and 9-phenylacridine (9 PA) concentration shown in table 1.
On the other hand, the two-stage roughening treatment was performed for example 3. The two-stage roughening treatment includes the following steps: a firing step of depositing and adhering fine copper particles on the extra thin copper foil; and a coating step for preventing the fine copper particles from falling off. In the baking step, carboxybenzotriazole (CBTA) was added to an acidic copper sulfate solution having a copper concentration of 10g/L and a sulfuric acid concentration of 200g/L to give the concentrations shown in Table 1, and roughening treatment was performed at the current densities and liquid temperatures shown in Table 1. In the subsequent coating step, electrodeposition was carried out under a smooth plating condition of a liquid temperature of 52℃and a current density as shown in Table 1 using an acidic copper sulfate solution having a copper concentration of 70g/L and a sulfuric acid concentration of 240 g/L.
(6) Rust-proof treatment
The roughened surface of the obtained copper foil with carrier was subjected to rust-proofing treatment comprising zinc-nickel alloy plating treatment and chromate treatment. First, a solution containing 1g/L of zinc, 2g/L of nickel and 80g/L of potassium pyrophosphate was used, and the current density was 0.5A/dm at a liquid temperature of 40 DEG C 2 Is to under the condition ofThe surface of the roughened layer and the carrier is subjected to zinc-nickel alloy plating treatment. Next, an aqueous solution containing 1g/L of chromic acid was used at a pH of 12 and a current density of 1A/dm 2 The surface subjected to the zinc-nickel alloy plating treatment is subjected to chromate treatment.
(7) Silane coupling agent treatment
The silane coupling agent treatment was performed by adsorbing an aqueous solution containing a commercially available silane coupling agent to the surface of the copper foil with carrier on the roughened copper foil side and evaporating water by an electric heater. At this time, the silane coupling agent treatment was not performed on the carrier side.
Example 4(comparison)
A roughened copper foil was produced in the same manner as in example 1, except for the following a) and b).
a) The following electrolytic copper foil was roughened on the deposition surface to replace the copper foil with carrier.
b) The roughening treatment conditions shown in table 1 were changed.
(preparation of electrolytic copper foil)
An acidic copper sulfate solution of sulfuric acid having the composition shown below was used as a copper electrolyte, an electrode made of titanium having a surface roughness Ra of 0.20 μm was used as a cathode, DSA (dimensionally stable anode) was used as an anode, and the solution temperature was 45℃and the current density was 55A/dm 2 The electrolytic copper foil having a thickness of 12 μm was obtained by electrolysis.
< composition of sulfuric acid copper sulfate solution >
Copper concentration: 80g/L
Sulfuric acid concentration: 260g/L
-bis (3-sulfopropyl) disulfide concentration: 30mg/L
Diallyl dimethyl ammonium chloride polymer concentration: 50mg/L
Chlorine concentration: 40mg/L
Example 5(comparison)
The carrier-equipped copper foil was produced in the same manner as in example 1, except that the extra thin copper foil was not roughened.
TABLE 1
Evaluation
The roughened copper foil or the copper foil with carrier produced in examples 1 to 5 were subjected to various evaluations shown below.
(a) Three-dimensional image analysis parameters of roughened surface
The average height of the roughened particles, the ratio of spherical particles, and the average value of the bottom area ratio were calculated by three-dimensional image analysis of the roughened surface (surface on the side of the extra thin copper foil in example 5) of the roughened copper foil or the copper foil with carrier. The specific steps are as follows.
(a-1) 3D-SEM observation
Three-dimensional shape data were obtained under the following measurement conditions using a FIB-SEM apparatus (manufactured by CarlZeiss Co., ltd., cross beam540, SEM and FIB control: atlas Engine v 5.5.3). The three-dimensional shape data is acquired by: as shown in fig. 5, the cross-sectional image of the roughened copper foil 10 on the dicing surface S parallel to the x-y surface was obtained, and the dicing surface was moved in parallel with each 5nm in the z-axis direction, while setting the x-axis and the z-axis as the in-plane direction of the roughened copper foil 10 and setting the y-axis as the thickness direction of the roughened copper foil 10. Although the observation is performed under the following conditions, the observation conditions may be appropriately selected and/or changed according to the state (model, etc.) of the apparatus.
< SEM Condition >
Acceleration voltage: 1.0kV
-Working distance：5mm
-tin: 54 ° (Tilt correction with SEM image)
-a detector: SESI detector
-Column mode：High resolution
-Field of view: x=3.2 μm (y arbitrarily set)
< FIB Condition >)
Acceleration voltage: 30kV
Slice thickness: 5nm (spacing of slice surfaces S)
-setting of voxel size:
voxel sizes (x, y, z) = (3 nm, 5 nm) to be set are inputted to measurement conditions of the FIB-SEM apparatus, and the voxel sizes are set. At this time, as for x and y, 3nm is input as a pixel size. In addition, z is 5nm into the slice thickness.
(a-2) 3D-SEM image analysis
Based on the slice image of the three-dimensional shape data of the roughened copper foil obtained by the 3D-SEM, correction of drift was performed by three-dimensional alignment software "ExFact Slice Aligner (version 2.0)" (Nihon Visual Science, manufactured by inc.) so that the analysis length of the z-axis became 2400nm or more. The three-dimensional reconstruction was performed on the drift-corrected slice image using three-dimensional image analysis software "extract VR (version 2.2)" (manufactured by Nihon Visual Science, inc.) and the size of the x-z plane in the case of the roughened copper foil 10 was 2400nm×2400nm in plan view, and the length in the y direction was an arbitrary length that could be analyzed by the roughening treatment. Further, after the shaft was rotated so that the roughened surface was an x-y surface as shown in fig. 6, image Analysis was performed by "foil Analysis (version 1.0)" (manufactured by Nihon Visual Science, inc.) to obtain various data on the roughened surface as described below.
In the image Analysis based on the three-dimensional image Analysis software "foil Analysis (version 1.0)", the matrix size was set to 77. The Excel data in the "ichijiBg" folder generated by the analysis is used to calculate various three-dimensional image analysis parameters shown below. In the analysis software described above, particles, voids, and the like are classified according to the luminance value, and therefore, a convex portion having "average_weight" of 150 in Excel data is regarded as a calculation target as a roughened particle. In addition, in order to remove noise, by using only data in which "volume (voxels)" is larger than 10 in Excel data, a small-sized convex portion can be excluded from calculation.
< average height of roughened particles >)
The value of "size_z (voxels)" of each convex portion is taken as the height (voxel number) of each roughened particle. The height of each roughened particle was calculated by multiplying this value by the height of the voxel size (5 nm), and the average value was used as the average height of the roughened particles. The results are shown in Table 3.
< proportion of spherical particles >
From the values of the length S of the minor axis and the length M of the central axis when the length L of the major axis of each convex portion was set to 1.0, the respective convex portions were classified into three types of particles, that is, spherical particles, flat particles, and elongated particles, based on the criteria shown in table 2. The convex portion where the shape determination (calculation of S, M, L) cannot be performed due to the small number of pixels or the like is excluded from the calculation as noise.
TABLE 2
TABLE 2
| Classification | Conditions (conditions) |
| Spherical particles | 0.3≤M≤1.0、0.3≦S≤1.0 |
| Flat particles | 0.3＜M≦1.0、S＜0.3 |
| Elongated particles | M≦0.3、S＜0.3 |
In the classified particles, the number N of the spherical particles S Divided by the individual particlesThe sum of the numbers (i.e. the number N of spherical particles) S Number N of flat particles F And number N of elongated particles E Sum) multiplied by 100 (=100×n) S /(N S +N F +N E ) The proportion of spherical particles was calculated. The results are shown in Table 3.
In the image Analysis by the three-dimensional image Analysis software "foil Analysis (version 1.0)", principal axes of inertia orthogonal to each other are set for each convex portion, and gravity moments S, M, L (s.ltoreq.m.ltoreq.l) of each convex portion are calculated. Next, in Excel data, the value (ratio) of the gravity center moment S and the value (ratio) of the gravity center moment M when the gravity center moment L is set to 1.0 are shown. That is, the gravity moment S, M, L corresponds to the length S of the minor axis, the length M of the center axis, and the length L of the major axis, respectively.
< average value of bottom area ratio >
The value of "surface_ voxels (voxels)" in each convex portion is taken as the x-y plane area value (i.e., bottom area) of the voxels constituting the bottom surface of each roughened particle. The value of "size_x (voxels)" in each convex portion is set as the X value of the largest voxel in the X-axis direction in each roughened particle, and the value of "size_y (voxels)" is set as the Y value of the largest voxel in the Y-axis direction. Then, the product of the x value and the y value is used as the projection area of each roughened particle. The ratio of the projected area to the bottom area in each roughened particle was obtained as the bottom area ratio, and the average value was calculated. The results are shown in Table 3.
(b) Shear strength
Using the obtained roughened copper foil to a carrier-attached copper foil, a laminate for evaluation was produced. Specifically, a copper foil with a carrier or a roughened copper foil was laminated on the surface of the inner layer substrate via a prepreg (GHPL-830 NSF, 30 μm thick, manufactured by Mitsubishi gas chemical Co., ltd.) so as to be in contact with the roughened surface (the surface on the side of the extra thin copper foil in the case of example 5), and was thermally pressed for 90 minutes at a pressure of 4.0MPa and a temperature of 220 ℃. Then, in the case of the copper foil with carrier, the carrier was peeled off to obtain a laminate for evaluation.
A dry film was adhered to the above laminate for evaluation, and the laminate was exposed to light and developed. Copper was chromatographed by pattern plating on the laminate masked with the developed dry film, and then the dry film was peeled off. The exposed copper portion was etched using a sulfuric acid-hydrogen peroxide etching solution to prepare a sample for measuring shear strength having a height of 15 μm, a width of 14 μm and a length of 150 μm. The shear strength of the sample for measuring shear strength was measured by using a bond strength tester (4000 Plus bond tester, manufactured by Nordson DAGE Co.). In this case, the test type was a fracture test, and the measurement was performed under conditions of a test height of 5 μm, a descent speed of 0.05mm/s, a test speed of 200 μm/s, a tool movement amount of 0.03mm, and a fracture recognition point of 10%. The obtained shear strength was evaluated in a step manner according to the following criteria, and the evaluation a and B were judged to be acceptable. The results are shown in Table 2.
< shear Strength evaluation criterion >)
-evaluation a: shear strength of 21.3gf/cm or more
-evaluation B: shear strength exceeding 19.9gf/cm and less than 21.3gf/cm
-evaluation C: shear strength of 19.9gf/cm or less
(c) Transmission characteristics
Two prepregs (megron 6, manufactured by Panasonic corporation, actual thickness 68 μm) were stacked, and a carrier-attached copper foil or a roughened surface of the roughened copper foil (surface on the side of the extra thin copper foil in the case of example 5) was abutted against both surfaces thereof, and hot-pressed at 190 ℃ for 90 minutes using a vacuum press. Then, the carrier was peeled off in the case of the copper foil with carrier, to obtain a copper-clad laminate. Copper plating was performed so that the copper thickness of the copper-clad laminate was 18 μm, and a substrate for measuring transmission characteristics on which a microstrip circuit was formed was obtained by a subtractive method.
The obtained substrate for measuring transmission characteristics was subjected to measurement of transmission loss S21 (dB/cm) up to 50GHz by using a network analyzer (PNA-X N5245A, manufactured by Agilent corporation) and selecting a pattern having a characteristic impedance of 50Ω. The average value of the transmission loss amounts in the 45 to 50GHz values was calculated, and the absolute values thereof were evaluated in a stepwise manner according to the following criteria. Then, the transmission characteristics were evaluated as a or B, and the result was judged as acceptable. The results are shown in Table 2.
< Transmission characteristic evaluation criterion >)
-evaluation a: the absolute value of the transmission loss is less than 0.455dB/cm
-evaluation B: the absolute value of the transmission loss exceeds 0.455dB/cm and is less than 0.465dB/cm
-evaluation C: the absolute value of the transmission loss is more than 0.465dB/cm
(d) Circuit Forming Property (evaluation of etching Property)
A laminate for evaluation was produced in the same manner as the shear strength. The laminate for evaluation was etched with a sulfuric acid-hydrogen peroxide etching solution at a rate of 0.2. Mu.m. The measurement was performed by confirming with an optical microscope (500 times) after each etching. Etching proceeds from the start point when the base resin is observed to the end point when the surface copper (including roughened particles) is completely absent when the evaluation laminate is observed with an optical microscope. The etching amount (depth) required from the start point to the end point is defined as the etching amount of the roughened particles. For example, an etching amount of the roughened particles of 0.4 μm means: after the substrate resin was first observed by an optical microscope, when etching was further performed twice by 0.2 μm, no residual copper was detected by an optical microscope (i.e., 0.2 μm×2 times=0.4 μm). That is, a smaller value indicates that the roughened particles can be removed by etching a smaller number of times, indicating that the etching performance is better. The etching amount of the obtained roughened particles was evaluated in a graded manner according to the following criteria. The results are shown in Table 3.
< etching evaluation criterion >)
-evaluation a: the etching amount of the roughened particles is 0.2 μm or less
-evaluation B: the etching amount of the roughened particles exceeds 0.2 μm and is 0.4 μm or less
-evaluation C: the etching amount of the roughened particles exceeds 0.4 μm
TABLE 3
Claims (9)
1. A roughened copper foil having a roughened surface on at least one side, the roughened surface having a plurality of roughened particles comprising spherical particles,
in the case of performing three-dimensional image analysis on an image obtained by using a FIB-SEM for the roughened surface, the average height of the roughened particles is 70nm or less, and the proportion of the spherical particles in the plurality of roughened particles is 30% or more,
the spherical particles are the following particles: when the long axis, the middle axis and the short axis which are orthogonal to each other are set to the roughened particles and the length L of the long axis is set to 1.0, the length M of the middle axis is 0.3.ltoreq.M.ltoreq.1.0, and the length S of the short axis is 0.3.ltoreq.S.ltoreq.1.0.
2. The roughened copper foil according to claim 1, wherein the average height is 20nm or more and 70nm or less.
3. The roughened copper foil according to claim 1 or 2, wherein the proportion of the spherical particles is 30% or more and 90% or less.
4. The roughened copper foil according to claim 1 or 2, wherein,
in the case where an image obtained by using a FIB-SEM for the roughened surface is three-dimensionally analyzed by assigning x-axis, y-axis and z-axis such that the z-axis is perpendicular to the roughened surface and the x-y plane is parallel to the roughened surface and dividing the roughened particles into a plurality of voxels, the average value of the bottom area ratio of the plurality of roughened particles is 3.0 or less,
the bottom area ratio is a ratio of a projected area in each of the roughened particles, the bottom area being defined in terms of an x-y plane area value of voxels constituting a bottom surface of each of the roughened particles, and the projected area being defined in terms of a product of an x value of a maximum voxel in an x-axis direction and a y value of a maximum voxel in a y-axis direction in each of the roughened particles.
5. The roughened copper foil according to claim 4, wherein the average value of the bottom area ratio is 2.0 or more and 3.0 or less.
6. The roughened copper foil according to claim 1 or 2, further comprising an anti-rust treatment layer and/or a silane coupling agent layer on the roughened surface.
7. A copper foil with a carrier, comprising: the roughened copper foil of claim 1, wherein the roughened copper foil is provided on the release layer so that the roughened surface is on the outside.
8. A copper-clad laminate comprising the roughened copper foil according to claim 1 or 2 or the copper foil with carrier according to claim 7.
9. A printed circuit board provided with the roughened copper foil according to claim 1 or 2 or the copper foil with carrier according to claim 7.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2021-085489 | 2021-05-20 | ||
| JP2021-085490 | 2021-05-20 | ||
| JP2022041749 | 2022-03-16 | ||
| JP2022-041749 | 2022-03-16 | ||
| PCT/JP2022/020749 WO2022244828A1 (en) | 2021-05-20 | 2022-05-18 | Roughened copper foil, copper foil with carrier, copper-clad laminate, and printed wiring board |
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| CN117337344A true CN117337344A (en) | 2024-01-02 |
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| Application Number | Title | Priority Date | Filing Date |
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Country Status (1)
| Country | Link |
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