CN116745468A - Surface-treated copper foil, copper-clad laminate, and printed wiring board - Google Patents
Surface-treated copper foil, copper-clad laminate, and printed wiring board Download PDFInfo
- Publication number
- CN116745468A CN116745468A CN202280008414.1A CN202280008414A CN116745468A CN 116745468 A CN116745468 A CN 116745468A CN 202280008414 A CN202280008414 A CN 202280008414A CN 116745468 A CN116745468 A CN 116745468A
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- China
- Prior art keywords
- copper foil
- layer
- treated
- conditions
- vmc
- Prior art date
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 169
- 239000011889 copper foil Substances 0.000 title claims abstract description 157
- 239000010410 layer Substances 0.000 claims abstract description 137
- 239000002335 surface treatment layer Substances 0.000 claims abstract description 53
- 230000008859 change Effects 0.000 claims abstract description 20
- 239000011347 resin Substances 0.000 claims description 65
- 229920005989 resin Polymers 0.000 claims description 65
- 239000000758 substrate Substances 0.000 claims description 26
- 238000005530 etching Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 description 75
- 239000000463 material Substances 0.000 description 50
- 238000011282 treatment Methods 0.000 description 45
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 36
- 239000000243 solution Substances 0.000 description 36
- 238000009713 electroplating Methods 0.000 description 33
- 238000007747 plating Methods 0.000 description 33
- 238000005259 measurement Methods 0.000 description 30
- 239000010949 copper Substances 0.000 description 19
- 238000009826 distribution Methods 0.000 description 18
- 238000000034 method Methods 0.000 description 18
- 239000006087 Silane Coupling Agent Substances 0.000 description 15
- 239000007787 solid Substances 0.000 description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 13
- 230000008878 coupling Effects 0.000 description 13
- 238000010168 coupling process Methods 0.000 description 13
- 238000005859 coupling reaction Methods 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 229910000077 silane Inorganic materials 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 229910052802 copper Inorganic materials 0.000 description 12
- 239000011701 zinc Substances 0.000 description 11
- 229910018605 Ni—Zn Inorganic materials 0.000 description 10
- 239000011247 coating layer Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 238000007788 roughening Methods 0.000 description 9
- 239000004020 conductor Substances 0.000 description 8
- 239000003921 oil Substances 0.000 description 7
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- 239000011651 chromium Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229920001721 polyimide Polymers 0.000 description 6
- 230000003746 surface roughness Effects 0.000 description 6
- 150000003658 tungsten compounds Chemical class 0.000 description 6
- 229910000881 Cu alloy Inorganic materials 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 239000003822 epoxy resin Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 5
- 229910052721 tungsten Inorganic materials 0.000 description 5
- 239000010937 tungsten Substances 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000011362 coarse particle Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- 239000009719 polyimide resin Substances 0.000 description 4
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 4
- 229920000106 Liquid crystal polymer Polymers 0.000 description 3
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 208000012868 Overgrowth Diseases 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 229910052785 arsenic Inorganic materials 0.000 description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 238000012937 correction Methods 0.000 description 3
- 230000002500 effect on skin Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 238000003908 quality control method Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- QWMFKVNJIYNWII-UHFFFAOYSA-N 5-bromo-2-(2,5-dimethylpyrrol-1-yl)pyridine Chemical compound CC1=CC=C(C)N1C1=CC=C(Br)C=N1 QWMFKVNJIYNWII-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000002238 attenuated effect Effects 0.000 description 2
- 238000004532 chromating Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000010731 rolling oil Substances 0.000 description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- ZDDUSDYMEXVQNJ-UHFFFAOYSA-N 1H-imidazole silane Chemical compound [SiH4].N1C=NC=C1 ZDDUSDYMEXVQNJ-UHFFFAOYSA-N 0.000 description 1
- NLSFWPFWEPGCJJ-UHFFFAOYSA-N 2-methylprop-2-enoyloxysilicon Chemical compound CC(=C)C(=O)O[Si] NLSFWPFWEPGCJJ-UHFFFAOYSA-N 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- 229910001200 Ferrotitanium Inorganic materials 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 206010019909 Hernia Diseases 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
- 239000000654 additive Substances 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000010485 coping Effects 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 239000006059 cover glass Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- CMMUKUYEPRGBFB-UHFFFAOYSA-L dichromic acid Chemical compound O[Cr](=O)(=O)O[Cr](O)(=O)=O CMMUKUYEPRGBFB-UHFFFAOYSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 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
- 238000005286 illumination Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/52—Treatment of copper or alloys based thereon
-
- 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
- C25D5/10—Electroplating with more than one layer of the same or of different metals
-
- 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
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
-
- 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
- C25D5/48—After-treatment of electroplated surfaces
-
- 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
- C25D5/48—After-treatment of electroplated surfaces
- C25D5/50—After-treatment of electroplated surfaces by heat-treatment
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
-
- 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
-
- 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
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Electrochemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Electroplating Methods And Accessories (AREA)
- Manufacturing Of Printed Wiring (AREA)
- Laminated Bodies (AREA)
Abstract
A surface-treated copper foil comprising a copper foil and a surface-treated layer formed on at least one surface of the copper foil. The rate of change of Vmc of the surface treatment layer expressed by the following formula (1) is 23.00 to 40.00%. In the expression of Vmc change rate= (P2-P1)/p2×100 … (1), P1 is Vmc calculated by applying a λs filter having a cutoff value λs of 2 μm, and P2 is Vmc calculated by not applying the λs filter.
Description
Technical Field
The present invention relates to a surface-treated copper foil, a copper-clad laminate, and a printed wiring board.
Background
Copper-clad laminates are widely used for various applications such as flexible printed wiring boards. The flexible printed wiring board is manufactured by forming a conductor pattern (also referred to as a "wiring pattern") by etching a copper foil of a copper-clad laminate, and then connecting and mounting electronic components to the conductor pattern by solder.
In recent years, with the increase in communication speed and capacity in electronic devices such as personal computers and mobile terminals, there has been a demand for flexible printed wiring boards capable of coping with higher frequencies of electric signals. In particular, the higher the frequency of the electric signal, the greater the loss (attenuation) of the signal power, and the more easily the data cannot be read out, and therefore, the reduction of the loss of the signal power is required.
The reasons for the signal power loss (transmission loss) in electronic circuits can be largely divided into two types. One is conductor loss, i.e., loss caused by copper foil, and the other is dielectric loss, i.e., loss caused by resin base material.
The conductor loss has a characteristic that a skin effect exists in a high frequency band and a current flows on the surface of the conductor, so that if the surface of the copper foil is roughened, the current flows along a complicated path. Therefore, in order to reduce the conductor loss of the high-frequency signal, it is desirable to reduce the surface roughness of the copper foil. Hereinafter, in the present specification, the terms "transmission loss" and "conductor loss" will be mainly used to refer to "transmission loss of a high-frequency signal" and "conductor loss of a high-frequency signal".
On the other hand, since dielectric loss depends on the kind of resin base material, it is desirable to use a resin base material made of a low dielectric material (e.g., a liquid crystal polymer or a low dielectric polyimide) for a circuit board in which a high frequency signal flows. Further, dielectric loss is also affected by the adhesive between the adhesive copper foil and the resin base material, so that it is preferable that the adhesive is not used between the adhesive copper foil and the resin base material.
In order to bond the copper foil to the resin base material without using an adhesive, it is proposed to form a surface-treated layer on at least one surface of the copper foil. For example, patent document 1 proposes the following method: a roughened layer formed of roughened particles is provided on the copper foil, and a silane coupling layer is formed on the outermost layer.
Prior art literature
Patent literature
Japanese patent document 1, jp 2012-112009 a
Disclosure of Invention
Problems to be solved by the invention
In general, minute irregularities are present on the surface of the copper foil on which the surface treatment layer is formed. For example, in the case of rolling a copper foil, oil pits formed by rolling oil during rolling are formed on the surface in the form of minute concave-convex portions. In the case of an electrolytic copper foil, polishing streaks of a rotary drum formed during polishing cause precipitation of minute uneven portions formed on the rotary drum side surface of the electrolytic copper foil on the rotary drum.
If there are minute irregularities on the copper foil surface, for example, when forming the roughened layer, current is concentrated at the convex portions on the copper foil surface, and the roughened particles excessively grow, while current is not sufficiently supplied to the concave portions on the copper foil surface and the periphery thereof, and it is difficult to grow the roughened particles. As a result, coarse roughening particles are formed on the convex portions on the copper foil surface, while the roughening particles in the concave portions on the copper foil surface and the concave portions around the concave portions are too small, and in particular, the adhesion of the roughening particles near the ends of the oil pits is insufficient, that is, the roughening particles on the copper foil surface are not uniformly formed. When a force is applied to the surface treated copper foil to peel the surface treated copper foil after the surface treated copper foil is bonded to the resin base material, the surface treated copper foil containing a large number of coarse roughened particles may be easily broken due to concentration of stress in the coarse roughened particles, and as a result, the adhesion to the resin base material may be reduced. Further, in the surface-treated copper foil having insufficient size of roughened particles, anchor effect due to the roughened particles may be reduced, and adhesiveness between the copper foil and the resin base material may not be sufficiently obtained.
In particular, since resin substrates made of low dielectric materials such as liquid crystal polymers and low dielectric polyimides are less likely to adhere to copper foil than conventional resin substrates, development of a method for improving adhesion between copper foil and resin substrates is desired.
The silane coupling treatment layer has an effect of improving adhesion between the copper foil and the resin base material, but the effect of improving adhesion may be insufficient depending on the kind thereof.
The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a surface-treated copper foil capable of improving adhesion to a resin substrate, particularly a resin substrate suitable for high-frequency applications.
In another embodiment, the present invention is directed to a copper-clad laminate excellent in adhesion between a resin base material, particularly a resin base material suitable for high-frequency applications, and a surface-treated copper foil.
In another embodiment, the present invention is directed to a printed wiring board excellent in adhesion between a resin base material, particularly a resin base material suitable for high-frequency applications, and a circuit pattern.
Technical proposal for solving the problems
The inventors of the present invention have made intensive studies on a surface-treated copper foil to solve the above problems, and as a result, have found that: by adding a minute amount of tungsten compound to the plating solution for forming the roughened layer, the overgrowth of the roughened particles of the convex portion formed on the copper foil surface is suppressed, and the roughened particles are easily formed around the concave portion on the copper foil surface. Then, the inventors of the present invention analyzed the surface shape of the surface-treated copper foil thus obtained, and found that the rate of change in Vmc of the surface-treated layer was closely related to the surface shape thereof, thereby completing the embodiment of the present invention.
That is, in one embodiment, the present invention relates to a surface-treated copper foil comprising a copper foil and a surface-treated layer formed on at least one surface of the copper foil, wherein the rate of change of Vmc represented by the above formula (1) is 23.00 to 40.00%.
Rate of change of vmc= (P2-P1)/p2x100· (1)
Where P1 is Vmc calculated by applying a λs filter having a cutoff value λs of 2 μm, and P2 is Vmc calculated by not applying the λs filter.
In another embodiment, the present invention relates to a copper-clad laminate comprising the surface-treated copper foil and a resin substrate bonded to the surface-treated layer of the surface-treated copper foil.
In another embodiment, the present invention relates to a printed wiring board including a circuit pattern formed by etching the surface-treated copper foil of the copper-clad laminate.
ADVANTAGEOUS EFFECTS OF INVENTION
According to an embodiment of the present invention, a surface-treated copper foil capable of improving adhesion to a resin substrate, particularly a resin substrate suitable for high-frequency applications, can be provided.
In another embodiment, the present invention provides a copper-clad laminate excellent in adhesion between a resin base material, particularly a resin base material suitable for high-frequency applications, and a surface-treated copper foil.
Further, according to an embodiment of the present invention, in another embodiment, a printed wiring board excellent in adhesion between a resin base material, particularly, a resin base material suitable for high-frequency use, and a circuit pattern can be provided.
Drawings
FIG. 1 is a typical load curve of a surface treatment layer.
FIG. 2 is a schematic view for explaining roughened particles and Vmc constituting the surface-treated layer.
FIG. 3 is a schematic enlarged sectional view of a surface-treated copper foil having a roughened layer on one side of the copper foil.
Description of the reference numerals
10 copper foil
11 convex part
12 concave portion
20 coarsening particle
30, coating.
Detailed Description
The preferred embodiments of the present invention will be specifically described below, but the present invention should not be construed as being limited thereto, and various changes, modifications and the like may be made based on the knowledge of those skilled in the art without departing from the gist of the present invention. The plurality of constituent elements disclosed in the following embodiments may be appropriately combined to form various inventions. For example, some of the constituent elements may be deleted from all the constituent elements shown in the following embodiments, or constituent elements of different embodiments may be appropriately combined.
The surface treated copper foil of the embodiment of the present invention has a copper foil and a surface treated layer formed on at least one surface of the copper foil.
The surface treatment layer may be formed on only one side of the copper foil, or may be formed on both sides of the copper foil. When the surface treatment layers are formed on both surfaces of the copper foil, the types of the surface treatment layers may be the same or different.
The surface shape of the surface treatment layer may be specified using surface texture parameters by following ISO 25178-2:2012, and analyzing a load curve calculated from the measurement data.
In describing the load curve, the load area ratio will be described first.
The load area ratio is a ratio obtained by dividing a region corresponding to a cross section of a three-dimensional object to be measured when the object is cut at a certain height by the area of the measurement view. In the present invention, a copper foil, a surface-treated layer of a surface-treated copper foil, or the like is set as a measurement object. The load curve is a curve representing the load area ratio at each height. The vicinity of the load area ratio 0% represents the height of the highest portion of the object to be measured, and the vicinity of the load area ratio 100% represents the height of the lowest portion of the object to be measured.
Next, fig. 1 shows a typical load curve of the surface treatment layer. The loading curve can be used to represent the solid and space volumes of the surface treatment layer. The solid volume corresponds to the volume of the portion of the measurement target object in the measurement view, and the space volume corresponds to the volume of the space between the solid portions in the measurement view. In the load curve described in the present invention, the load area ratio is divided into a valley portion, a core portion, and a mountain portion by dividing the load area ratio into 10% and 80%. When the surface treatment layer according to the embodiment of the present invention is described with reference to fig. 1, vvv is the volume of the space at the valley of the surface treatment layer, vvc is the volume of the space at the core of the surface treatment layer, vmp is the volume of the solid at the mountain of the surface treatment layer, and Vmc is the volume of the solid at the core of the surface treatment layer.
The mountain portion is a portion of the object to be measured having a high height. The valley portion is a portion of the object to be measured having a low height. The core portion is a portion of the object to be measured other than the mountain portion and the valley portion, that is, a portion close to the average height.
The solid portion volume Vmp at the mountain portion is the volume of the solid portion at the mountain portion, that is, the portion where the height of the object to be measured is high, and the solid portion volume at the portion where the height of the surface treatment layer is particularly high. The solid portion at a portion of the surface-treated layer having a particularly high height is explained as a portion caused by excessively grown particles (particularly roughened particles) among the particles.
The solid portion volume Vmc at the core portion is the volume of the solid portion at the core portion, that is, at a portion of the object to be measured close to the average height, and is the volume of the solid portion at the portion of the average height of the surface treatment layer. Here, the solid portion at the portion of the average height of the surface treatment layer may be interpreted as a portion due to average-sized particles (particularly roughened particles) formed at a relatively smooth portion of the copper foil surface.
In summary, the present inventors have found that, as a result of the analysis in the above manner, the following findings are obtained: in the surface treated copper foil of the embodiment of the present invention, vmp is related to the solid volume of the overgrown large particles, and Vmc is related to the solid volume of the average size particles. In the following, the case where the coarsened particles are used as particles will be described as an example, but it should be noted that the particles are not limited to coarsened particles.
The measurement data for measuring the surface properties of the surface treated copper foil according to the embodiment of the present invention can be obtained by using a laser microscope such as a confocal laser microscope. The measurement data can be separated into waveforms having various periods and amplitudes by performing fourier transform on the measurement data. The inventors considered that the surface texture parameters to be noted can be calculated from the measurement data by applying a filter for attenuating the amplitudes of the waveforms of the frequencies in the specific range to the separated waveforms, and then synthesizing all the waveforms again and analyzing the synthesized data.
In analyzing the measurement data of the surface roughness, the present inventors have found that: by combining the surface texture parameter calculated by applying the λs filter having the cutoff value λs of 2 μm and the surface texture parameter calculated by not applying the λs filter, detailed information of the characteristic surface shape (particularly, the adhesion state of roughened particles constituting the surface treatment layer) of the surface treatment layer according to the embodiment of the present invention can be obtained.
Here, the λs filter is a contour filter that greatly attenuates the amplitude of a waveform having a wavelength smaller than the cutoff value λs. The λs filter corresponds to ISO 25178-2:2012, S filters in 2012. The magnitude of the amplitude attenuation by the λs filter varies depending on the wavelength of the waveform. The amplitude is attenuated to 50% of the original value at the wavelength of the cutoff value λs, and the amplitude is attenuated more greatly at the waveform having the smaller wavelength.
The cutoff value λs of 2 μm is a size between the size of the roughened particles constituting the surface-treated layer and the size of the oil pits. The measurement data obtained by setting the cutoff value λs to 2 μm is derived from a waveform having a shorter period than the cutoff value λs, and thus can be understood as data obtained by removing the data derived from coarsened particles. Based on this, it is possible to eliminate the difference between the surface property parameter calculated by applying the λs filter having the cutoff value λs of 2 μm and the surface property parameter calculated by applying the λs filter, and to remove the information of the oil pit, that is, the information of the roughened particles constituting the surface treated layer.
Based on the findings described above, the inventors of the present invention have found that the rate of change in Vmc of the surface treated layer expressed by the following formula (1) is closely related to the amount of attached roughened particles constituting the average size of the surface treated layer, after analyzing various surface property parameters obtained from the load curve.
Rate of change of vmc= (P2-P1)/p2x100· (1)
Where P1 is Vmc calculated by applying a λs filter having a cutoff value λs of 2 μm, and P2 is Vmc calculated by not applying the λs filter.
Here, fig. 2 shows a schematic overview for explaining roughened particles and Vmc constituting the surface treatment layer. As shown in fig. 2, the surface-treated layer includes coarsened particles a of an average size and coarsened particles B that overgrow. As described above, it is considered that Vmc corresponds to the volume of the average size roughening particles a formed in the relatively smooth portion of the copper foil surface, and is related to the amount of the average size roughening particles a attached. Vmc is not affected much by macroscopic shapes such as pits, and the macroscopic shapes need to be removed in order to read information of the surface treatment layer more accurately. P1 can be interpreted as the Vmc value after removing the information from the coarsening particle, in other words, the Vmc value for retaining the information from the oil pit or the like. Taking the difference between P2 and P1 means removing the information from macroscopic shapes such as oil pits contained in Vmc. As a result, information on the amount of adhesion of coarsened particles a of the average size can be extracted with high accuracy.
The average size of the roughened particles a formed on the relatively smooth portion of the copper foil surface is considered to be greatly related to the adhesion between the resin base material and the surface-treated layer. It is thought that overgrown (coarse) coarsened particles B cause coarsening fracture, whereas too small coarsened particles do not embed into the resin substrate at all. Therefore, the surface treated copper foil is formed so that the rate of change in Vmc of the surface treated layer in relation to the average amount of adhesion of the roughened particles a is controlled within an appropriate range, whereby the adhesion to the resin base material can be improved.
From this point of view, the surface treated copper foil of the embodiment of the present invention having a change rate of Vmc of 23.00 to 40.00% exhibits sufficient adhesion to the resin base material. From the viewpoint of stably obtaining this effect, the rate of change in Vmc is preferably 23.00 to 32.00%, more preferably 23.00 to 31.00%.
In the surface treatment layer, sku (kurtosis) calculated without applying the λs filter is preferably 2.50 to 4.50.
Sku is a parameter indicating how sharp the histogram is (sharpness) when the histogram of the height is created based on the average height. For example, in the case of sku=3.00, this means that the height distribution is a normal distribution. In the case of Sku >3.00, the larger the numerical value is, the more concentrated the height distribution is. Conversely, in the case of Sku <3.00, the smaller the value, the more dispersed the height distribution.
The surface-treated copper foil of the embodiment of the present invention has irregularities on the surface for improving adhesion of the copper foil to a resin base material. Sku of the surface treatment layer serves as an index for evaluating the height distribution of the irregularities.
The Sku of the surface-treated layer is 2.50 to 4.50, which means that the height distribution is a normal distribution or a distribution close to this. On the other hand, when Sku of the surface treatment layer is less than 2.50, the low-height portion (height from the copper foil surface) of the surface treatment layer is variously interlaced with the high-height portion, and as a result, the height distribution is not biased. The Sku of the surface treatment layer being greater than 4.50 means a highly distributed distribution state, that is, a state in which the surface of the surface treatment layer is a portion of a certain height to occupy a plurality of places prominently.
The height distribution of the surface treatment layer is a normal distribution or a distribution close to the normal distribution, which means that, for example, when the roughened layer is formed on the copper foil surface, particles that excessively grow on the convex portions on the copper foil surface, that is, coarse particles, or the number of portions where no particles are formed in the periphery of the concave portions (the ends of the convex portions) on the copper foil surface is small. Therefore, the Sku of the surface-treated layer is 2.50 to 4.50, which means that the overgrowth of particles of the convex portion formed on the copper foil surface is suppressed, and roughened particles are also formed around the concave portion on the copper foil surface.
The surface treated copper foil having a large number of coarse particles and the surface treated copper foil having a portion where no particles are formed are not preferable from the viewpoint of adhesion to a resin base material. For example, in a surface treated copper foil having a large number of coarse particles, it is considered that when a force for peeling the surface treated copper foil is applied after bonding to a resin base material, stress concentrates on the coarse particles and is likely to break, and as a result, adhesion to the resin base material is rather lowered. In addition, in the surface-treated copper foil having a portion where particles are not formed, it is considered that the following may be the case: the anchoring effect due to the particles cannot be sufficiently ensured, and the adhesion between the surface-treated copper foil and the resin base material is reduced.
Therefore, from the viewpoint of stably obtaining the adhesion to the resin substrate, the lower limit value of Sku of the surface treatment layer is preferably 2.90, and the upper limit value is preferably 4.10.
Furthermore, sku of the surface treatment layer may be according to ISO 25178-2:2012, and analyzing a contour curve calculated from the measurement data, thereby specifying the surface roughness.
The Sq (root mean square height) calculated by the surface treatment layer without applying the λs filter is preferably 0.20 to 0.60 μm. Sq is defined by ISO 25178-2:2012, the parameter in the height direction, which indicates the variation in the height of the convex portion on the surface of the surface treatment layer.
The large Sq of the surface treatment layer means that the variation in height of the convex portion on the surface of the surface treatment layer is large. If Sq is too large (the variation in the height of the convex portion is too large), there is a problem from the viewpoint of quality control of industrial products. Therefore, by setting the Sq of the surface-treated layer to the above range, it is possible to ensure productivity by slightly allowing the variation in the height of the convex portion, and to perform appropriate quality control. From the viewpoint of stably obtaining such an effect, the lower limit value of the Sq of the surface treatment layer is preferably 0.26 μm, more preferably 0.30 μm, still more preferably 0.34 μm, and the upper limit value is preferably 0.53 μm, more preferably 0.48 μm, still more preferably 0.43 μm.
Furthermore, sq of the surface treatment layer may be in accordance with ISO 25178-2:2012, and analyzing a contour curve calculated from the measurement data, thereby specifying the surface roughness.
The Sa (arithmetic mean height) calculated by the surface treatment layer without applying the λs filter is preferably 0.20 to 0.40 μm. Sa is defined by ISO 25178-2:2012, the parameter in the height direction represents the average of the height differences from the average surface.
If Sa of the surface treatment layer is large, the surface of the surface treatment layer becomes rough, and therefore, when the surface treatment copper foil is bonded to the resin base material, the anchor effect is easily exerted. On the other hand, if Sa of the surface treatment layer is too large, when a circuit board is manufactured by processing a copper-clad laminate obtained by bonding a surface-treated copper foil and a resin base material, transmission loss increases due to the skin effect of the surface-treated copper foil. Therefore, by setting Sa of the surface treatment layer to the above range, it is possible to ensure a balance between ensuring adhesion of the surface treated copper foil to the resin base material and suppressing transmission loss. From the viewpoint of stably obtaining such an effect, the lower limit value of Sa of the surface treatment layer is preferably 0.23 μm, more preferably 0.24 μm, and the upper limit value is preferably 0.35 μm.
In the case where suppression of transmission loss due to skin effect and easiness of quality control of industrial products are important, the surface treatment layer preferably has a Sa of 0.20 to 0.32 μm and a Sq of 0.26 to 0.40 μm.
Furthermore, sa of the surface treatment layer may be according to ISO 25178-2:2012, and analyzing a contour curve calculated from the measurement data, thereby specifying the surface roughness.
Ssk (distortion) calculated by the surface treatment layer without applying the λs filter is preferably-1.10 to 0.60.
Ssk is a parameter representing the degree of skew (skew) of a histogram of height when the histogram is created based on the average height. For example, in the case of ssk=0.00, this means that the height distribution is symmetrical with respect to the mean line. In the case where Ssk >0.00, the larger the value is, the more downward the height distribution is with respect to the average line. Conversely, in the case of Ssk <0.00, the smaller the value, the more upward the height distribution is to be inclined with respect to the average line. Therefore, ssk of the surface treatment layer is the same as Sku, and is an index for evaluating the height distribution of the irregularities of the surface treatment layer.
For example, when a roughened layer is formed on the copper foil surface, ssk of-1.10 to 0.60 means that coarse roughening particles, which are roughening particles excessively grown on the convex portions on the copper foil surface, or that few sites are formed around the concave portions (ends of the convex portions) on the copper foil surface where no roughening particles are formed. On the other hand, if the number of the roughened particles is less than-1.10, the roughened particles are not formed around the recessed portion on the copper foil surface. If Ssk exceeds 0.60, the number of roughened particles excessively grown on the convex portions on the copper foil surface is increased.
From the viewpoint of stably obtaining adhesion to the resin substrate, the upper limit value of Ssk of the surface treatment layer is preferably 0.40, and the lower limit value is preferably-0.80.
Furthermore, ssk of the surface treatment layer may be in accordance with ISO 25178-2:2012, and analyzing a contour curve calculated from the measurement data, thereby specifying the surface roughness.
The type of the surface treatment layer is not particularly limited, and various surface treatment layers known in the art can be used.
Examples of the surface-treated layer include a roughened layer, a heat-resistant layer, an anti-rust layer, a chromate layer, a silane coupling layer, and the like. The layers may be used singly or in combination of 2 or more. Among them, the surface-treated layer preferably contains a roughened layer from the viewpoint of adhesion to the resin base material.
In the case where the surface-treated layer contains 1 or more kinds of layers selected from the group consisting of a heat-resistant treated layer, a rust-preventive treated layer, a chromate treated layer and a silane coupling treated layer, the layers are preferably provided on the roughened layer.
Here, fig. 3 is a schematic enlarged cross-sectional view of a surface-treated copper foil having a roughened layer on one surface of the copper foil as an example.
As shown in fig. 3, the roughened layer formed on one surface of the copper foil 10 includes roughened particles 20 and a coating layer 30 coating at least a part of the roughened particles 20. The roughened particles 20 are formed not only near the center of the convex portion 11 on the surface of the copper foil 10 but also around the concave portion 12 (end portions of the convex portion 11). Further, since a minute amount of tungsten compound is added to the plating solution, overgrowth of the roughened particles 20 of the protrusions 11 formed on the surface of the copper foil 10 is suppressed. Therefore, the coarsened particles 20 have a complex shape that grows in all directions without overgrowing into particles having a large particle diameter. It is considered that such a structure can be obtained by controlling the rate of change of Vmc of the surface treatment layer to the above range.
The coarsening particles 20 are not particularly limited, and may be formed of a single element selected from the group consisting of copper, nickel, cobalt, phosphorus, tungsten, arsenic, molybdenum, chromium, and zinc, or an alloy containing 2 or more of these elements. Among them, the coarsening particles 20 are preferably formed of copper or copper alloy, particularly copper.
The coating layer 30 is not particularly limited, and may be formed of copper, silver, gold, nickel, cobalt, zinc, or the like.
The roughened layer may be formed by electroplating. In particular, the roughened particles 20 may be formed by electroplating using a plating solution to which a trace amount of tungsten compound is added.
The tungsten compound is not particularly limited, and sodium tungstate (Na 2 WO 4 ) Etc.
The content of the tungsten compound in the plating solution is preferably 1ppm or more. If the content is such, the coarsening particles 20 formed on the convex portion 11 are prevented from overgrowing, and the coarsening particles 20 are easily formed around the concave portion 12. The upper limit of the content of the tungsten compound is not particularly limited, but is preferably 20ppm from the viewpoint of suppressing an increase in resistance.
The plating conditions for forming the roughened layer may be adjusted according to the plating apparatus or the like used, and are not particularly limited, and typical conditions are as follows. Furthermore, each plating may be performed 1 time or a plurality of times.
(conditions for Forming coarsened particles 20)
Plating solution composition: 5-15 g/L Cu, 40-100 g/L sulfuric acid, 1-6 ppm sodium tungstate
Plating solution temperature: 20-50 DEG C
Electroplating conditions: current density30～90A/dm 2 For 0.1 to 8 seconds
(conditions for forming coating layer 30)
Plating solution composition: 10-30 g/L Cu, 70-130 g/L sulfuric acid
Plating solution temperature: 30-60 DEG C
Electroplating conditions: the current density is 4.8-15A/dm 2 For 0.1 to 8 seconds
The heat-resistant treatment layer and the rust-preventive treatment layer are not particularly limited, and may be formed of materials known in the art. Further, the heat-resistant layer may also function as a rust-preventive layer, and thus 1 layer having functions of both the heat-resistant layer and the rust-preventive layer may be formed as the heat-resistant layer and the rust-preventive layer.
The heat-resistant treatment layer and/or the rust-preventive treatment layer may be formed as a layer containing 1 or more elements (any form of metal, alloy, oxide, nitride, sulfide, or the like) selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, iron, and tantalum. Among them, the heat-resistant treatment layer and/or the rust-preventive treatment layer is preferably a Ni-Zn layer.
The heat-resistant treatment layer and the rust-preventive treatment layer may be formed by electroplating. The conditions may be adjusted according to the plating apparatus used, and are not particularly limited, and the conditions when a heat treatment resistant layer (ni—zn layer) is formed using a general plating apparatus are as follows. Furthermore, the plating may be performed 1 time or more times.
Plating solution composition: 1-30 g/L Ni, 1-30 g/L Zn
Plating solution pH value: 2 to 5
Plating solution temperature: 30-50 DEG C
Electroplating conditions: the current density is 0.1-10A/dm 2 For 0.1 to 5 seconds
The chromate treatment layer is not particularly limited, and may be formed of a material known in the art.
Here, the "chromate treatment layer" in the present specification refers to a layer formed of a liquid containing chromic anhydride, chromic acid, dichromic acid, chromate or dichromate. The chromate treatment layer may be a layer containing elements (any form of metal, alloy, oxide, nitride, sulfide, etc.) such as cobalt, iron, nickel, molybdenum, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic, titanium, etc. Examples of the chromate treatment layer include a chromate treatment layer treated with an aqueous solution of chromic anhydride or potassium dichromate, a chromate treatment layer treated with a treatment solution containing chromic anhydride or potassium dichromate and zinc, and the like.
The chromate treatment layer may be formed by a known method such as immersion chromate treatment or electrolytic chromate treatment. The conditions for forming a general chromate treatment layer are not particularly limited, and the conditions for forming a general chromate treatment layer are as follows. Furthermore, the chromate treatment may be performed 1 time or a plurality of times.
Chromate solution composition: k of 1-10 g/L 2 Cr 2 O 7 Zn in 0.01-10 g/L
pH value of chromate solution: 2 to 5
Chromate solution temperature: 30-55 DEG C
Electrolytic conditions: the current density is 0.1-10A/dm 2 For 0.1 to 5 seconds (in the case of electrolytic chromate treatment)
The silane coupling treatment layer is not particularly limited and may be formed of a material known in the art.
Herein, the term "silane coupling agent layer" as used herein refers to a layer formed of a silane coupling agent.
The silane coupling agent is not particularly limited, and those known in the art can be used. Examples of the silane coupling agent include an amino silane coupling agent, an epoxy silane coupling agent, a mercapto silane coupling agent, a methacryloxy silane coupling agent, a vinyl silane coupling agent, an imidazole silane coupling agent, and a triazine silane coupling agent. Among these, amino silane coupling agents and epoxy silane coupling agents are preferable. The silane coupling agent may be used alone or in combination of 2 or more.
Typical methods for forming the silane coupling layer include a method of forming the silane coupling layer by coating a 1 to 3 vol% aqueous solution of the silane coupling agent and drying the coating.
The copper foil 10 is not particularly limited, and may be either an electrolytic copper foil or a rolled copper foil.
The electrolytic copper foil is generally produced by electrolytic deposition of copper from a copper sulfate plating bath onto a drum of titanium or stainless steel, and has a flat S surface (polished surface) formed on the side of the rotating drum and an M surface (polished surface) formed on the opposite side of the S surface. The M-plane of the electrolytic copper foil generally has minute concave-convex portions. The S-surface of the electrolytic copper foil has minute uneven portions because of the transfer of the polishing stripes of the rotary drum formed during polishing.
Further, the rolled copper foil has minute uneven portions on the surface because oil pits are formed by rolling oil during rolling.
The material of the copper foil 10 is not particularly limited, and when the copper foil 10 is a rolled copper foil, high purity copper such as fine copper (JIS H3100 alloy No. C1100) and oxygen-free copper (JIS H3100 alloy No. C1020 or JIS H3510 alloy No. C1011) which are generally used as a circuit pattern of a printed wiring board can be used. For example, sn-doped copper, ag-doped copper, copper alloys containing Cr, zr, mg, or the like, and copper alloys containing a casson-based copper alloy containing Ni, si, or the like may be used. In the present specification, "copper foil 10" is also a concept including copper alloy foil.
The thickness of the copper foil 10 is not particularly limited, and may be set to 1 to 1000 μm, or 1 to 500 μm, or 1 to 300 μm, or 3 to 100 μm, or 5 to 70 μm, or 6 to 35 μm, or 9 to 18 μm, for example.
The surface-treated copper foil having the above-described structure can be produced by a method known in the art. Here, the parameters such as the rate of change of Vmc of the surface-treated layer can be controlled by adjusting the conditions for forming the surface-treated layer, in particular, the conditions for forming the roughened layer.
The surface-treated copper foil according to the embodiment of the present invention can improve adhesion to a resin base material, particularly a resin base material suitable for high-frequency applications, by controlling the rate of change in Vmc of the surface-treated layer to 23.00 to 40.00%.
The copper-clad laminate according to the embodiment of the present invention comprises the surface-treated copper foil and a resin substrate bonded to the surface-treated layer of the surface-treated copper foil.
The copper-clad laminate can be produced by bonding a resin substrate to the surface-treated layer of the surface-treated copper foil.
The resin base material is not particularly limited, and those known in the art can be used. Examples of the resin substrate include paper substrate phenol resin, paper substrate epoxy resin, synthetic fiber cloth substrate epoxy resin, glass cloth-paper composite substrate epoxy resin, glass cloth-glass non-woven cloth composite substrate epoxy resin, glass cloth substrate epoxy resin, polyester film, polyimide resin, liquid crystal polymer, fluorine resin, and the like. Of these, the resin base material is preferably polyimide resin.
The method for bonding the surface-treated copper foil to the resin base material is not particularly limited, and may be performed according to a method known in the art. For example, the surface treated copper foil may be laminated with a resin-based material and thermocompression bonded.
The copper-clad laminate manufactured in the above manner can be used for manufacturing a printed wiring board.
The copper-clad laminate according to the embodiment of the present invention can improve adhesion to a resin substrate, particularly a resin substrate suitable for high-frequency applications, by using the surface-treated copper foil.
The printed wiring board according to the embodiment of the present invention includes a circuit pattern formed by etching the surface-treated copper foil of the copper-clad laminate.
The printed wiring board can be manufactured by etching the surface-treated copper foil of the copper-clad laminate to form a circuit pattern. The method for forming the circuit pattern is not particularly limited, and known methods such as a subtractive method and a semi-additive method can be used. Among them, the formation method of the circuit pattern is preferably a subtractive method.
In the case of manufacturing a printed wiring board by the subtractive process, it is preferable to perform the following process. First, a resist is coated on the surface of a surface-treated copper foil of a copper-clad laminate, and exposure and development are performed to form a specific resist pattern. Next, the surface-treated copper foil of the portion (excess portion) where the resist pattern is not formed is removed by etching to form a circuit pattern. Finally, the resist pattern on the surface-treated copper foil is removed.
The conditions in the reduction method are not particularly limited, and may be performed according to conditions well known in the art.
Since the copper-clad laminate is used in the printed wiring board according to the embodiment of the present invention, the adhesion between the resin base material, particularly, a resin base material suitable for high-frequency applications, and the circuit pattern is excellent.
Examples (example)
Hereinafter, embodiments of the present invention will be described more specifically by way of examples, but the present invention is not limited to the examples.
Example 1
A rolled copper foil (HA-V2 foil manufactured by JX Metal Co., ltd.) having a thickness of 12 μm was prepared, and after degreasing and pickling one surface, a roughened layer, a heat-resistant layer (Ni-Zn layer), a chromate layer and a silane coupling layer were sequentially formed as surface-treated layers, thereby obtaining a surface-treated copper foil. The formation conditions of the respective treatment layers are as follows.
(1) Coarsening treatment layer
< conditions for Forming coarsened particles >
Plating solution composition: 11g/L Cu,50g/L sulfuric acid, 5ppm tungsten (from sodium tungstate dihydrate)
Plating solution temperature: 27 DEG C
Electroplating conditions: the current density was 80.0A/dm 2 Time 0.51 seconds
Number of electroplating treatments: 2 times
< conditions for Forming coating layer >
Plating solution composition: 20g/L Cu,100g/L sulfuric acid
Plating solution temperature: 50 DEG C
Electroplating conditions: current density 12.6A/dm 2 Time 0.96 seconds
Number of electroplating treatments: 2 times
(2) Heat treatment resistant layer
< conditions for Forming Ni-Zn layer >
Plating solution composition: 23.5g/L Ni,4.5g/L Zn
Plating solution pH value: 3.6
Plating solution temperature: 40 DEG C
Electroplating conditions: current density 0.83A/dm 2 Time 0.49 seconds
Number of electroplating treatments: 1 time
(3) Chromating layer
< conditions for Forming electrolytic chromate treatment layer >
Chromate solution composition: k3 g/L 2 Cr 2 O 7 Zn in an amount of 0.33g/L
pH value of chromate solution: 3.7
Chromate solution temperature: 55 DEG C
Electrolytic conditions: current density 2.20A/dm 2 Time 0.49 seconds
Number of chromate treatments: 2 times
(4) Silane coupling treatment layer
A 1.2 vol% aqueous solution of N-2- (aminoethyl) -3-aminopropyl trimethoxysilane was coated and dried, thereby forming a silane coupling treated layer.
Example 2
A surface-treated copper foil was obtained in the same conditions as in example 1, except that the following conditions were changed.
< conditions for Forming coarsened particles >
Electroplating conditions: current density 46.8A/dm 2 For 1.01 seconds
< conditions for Forming coating layer >
Electroplating conditions: current density 9.6A/dm 2 Time 1.44 seconds
< conditions for Forming Ni-Zn layer >
Electroplating conditions: the current density was 0.88A/dm 2 Time 0.73 seconds
< conditions for Forming electrolytic chromate treatment layer >
Electrolytic conditions: current density 1.42A/dm 2 Time 0.73 seconds
Example 3
A surface-treated copper foil was obtained in the same conditions as in example 1, except that the following conditions were changed.
< conditions for Forming coarsened particles >
Electroplating conditions: current density 41.3A/dm 2 For 1.15 seconds
< conditions for Forming coating layer >
Electroplating conditions: current density 8.2A/dm 2 Time 1.44 seconds
< conditions for Forming Ni-Zn layer >
Electroplating conditions: current density 0.73A/dm 2 Time 0.73 seconds
< conditions for Forming electrolytic chromate treatment layer >
Electrolytic conditions: the current density was 1.51A/dm 2 Time 0.73 seconds
Example 4
A surface-treated copper foil was obtained in the same conditions as in example 1, except that the following conditions were changed.
< conditions for Forming coarsened particles >
Electroplating conditions: current density 54.8A/dm 2 For 0.90 seconds
< conditions for Forming coating layer >
Electroplating conditions: current density 8.2A/dm 2 Time 1.44 seconds
< conditions for Forming Ni-Zn layer >
Electroplating conditions: current density 0.73A/dm 2 Time 0.73 seconds
< conditions for Forming electrolytic chromate treatment layer >
Electrolytic conditions: the current density was 1.51A/dm 2 Time 0.73 seconds
Example 5
A surface-treated copper foil was obtained in the same conditions as in example 1, except that the following conditions were changed.
< conditions for Forming coarsened particles >
Electroplating conditions: current density 46.8A/dm 2 For 1.01 seconds
< conditions for Forming coating layer >
Electroplating conditions: current density 9.6A/dm 2 Time 1.44 seconds
< conditions for Forming Ni-Zn layer >
Electroplating conditions: the current density was 0.88A/dm 2 Time 0.73 seconds
< conditions for Forming electrolytic chromate treatment layer >
Electrolytic conditions: current density 1.42A/dm 2 Time 0.73 seconds
Example 6
A rolled copper foil (HG foil manufactured by JX Metal Co., ltd.) having a thickness of 12 μm was prepared, and after degreasing and acid cleaning of one surface, a roughened layer, a heat-resistant layer (Ni-Zn layer), a chromate layer and a silane coupling layer were sequentially formed as surface-treated layers, thereby obtaining a surface-treated copper foil. The formation conditions of the respective treatment layers are as follows.
(1) Coarsening treatment layer
< conditions for Forming coarsened particles >
Plating solution composition: 12g/L Cu,50g/L sulfuric acid, 5ppm tungsten (from sodium tungstate dihydrate)
Plating solution temperature: 27 DEG C
Electroplating conditions: current density 48.3A/dm 2 Time 0.81 seconds
Number of electroplating treatments: 2 times
< conditions for Forming coating layer >
Plating solution composition: 20g/L Cu,100g/L sulfuric acid
Plating solution temperature: 50 DEG C
Electroplating conditions: current density 11.9A/dm 2 For 1.15 seconds
Number of electroplating treatments: 2 times
(2) Heat treatment resistant layer
< conditions for Forming Ni-Zn layer >
Plating solution composition: 23.5g/L Ni,4.5g/L Zn
Plating solution pH value: 3.6
Plating solution temperature: 40 DEG C
Electroplating conditions: current density 1.07A/dm 2 Time 0.59 seconds
Number of electroplating treatments: 1 time
(3) Chromating layer
< conditions for Forming electrolytic chromate treatment layer >
Chromate solution composition: k3 g/L 2 Cr 2 O 7 Zn in an amount of 0.33g/L
pH value of chromate solution: 3.65
Chromate solution temperature: 55 DEG C
Electrolytic conditions: current density 1.91A/dm 2 Time 0.59 seconds
Number of chromate treatments: 2 times
(4) Silane coupling treatment layer
A 1.2 vol% aqueous solution of N-2- (aminoethyl) -3-aminopropyl trimethoxysilane was coated and dried, thereby forming a silane coupling treated layer.
Comparative example 1
The rolled copper foil (copper foil without surface treatment) used in example 1 was used as a comparison.
Comparative example 2
A surface-treated copper foil was obtained in the same conditions as in example 1, except that the following conditions were changed.
< conditions for Forming coarsened particles >
Plating solution composition: 11g/L Cu,50g/L sulfuric acid
Electroplating conditions: current density 38.8A/dm 2 For 1.27 seconds
< conditions for Forming coating layer >
Electroplating conditions: current density 8.2A/dm 2 Time 1.44 seconds
< conditions for Forming Ni-Zn layer >
Electroplating conditions: current density 0.59A/dm 2 Time 0.73 seconds
< conditions for Forming electrolytic chromate treatment layer >
Electrolytic conditions: current density 1.42A/dm 2 Time 0.73 seconds
The surface-treated copper foil or copper foil obtained in the above examples and comparative examples was subjected to the following characteristic evaluation.
< Vmc, sku, sq, sa and Ssk >
According to ISO 25178-2:2012, measurement (image capturing) was performed using a laser microscope (LEXT OLS 4000) manufactured by olympus corporation. Analysis of the captured image was performed using analysis software of a laser microscope (LEXT OLS 4100) manufactured by olympus corporation. As a result, an average value of the values measured and analyzed at any 5 points was used. The temperature at the time of measurement was set to 23 to 25 ℃. The main setting conditions of the laser microscope and analysis software are as follows.
An objective lens: MPLAPON50XLEX (magnification: 50 times, numerical aperture: 0.95, type of immersion in liquid: air, mechanical barrel length: infinity, cover glass thickness: 0, number of views: FN 18)
Optical zoom magnification: 1 time of
Scanning mode: XYZ high precision (high resolution: 60nm, number of pixels of the fetched data: 1024X 1024)
Taking in the image size [ number of pixels ]: transverse 257 μm X258 μm [ 1024X 1024] longitudinal
(since it is measured in the transverse direction, the estimated length is 257. Mu.m)
DIC: closing
Multilayers: closing
Laser intensity: 100
And (3) compensation: 0
Confocal stage: 0
Beam diameter diaphragm: closing
Image averaging: 1 time
Noise reduction: opening up
Brightness unevenness correction: opening up
An optical noise filter: opening up
And (3) cut-off: in measurement of P1 (Vmc), λc=200 μm and λs=2 μm were applied, and λf was not applied. When P2 (Vmc), sku, sq, sa and Ssk were measured, λc=200 μm was applied, and λs and λf were not applied.
And (3) a filter: gaussian filter
Noise removal: pretreatment for measurement
Surface (slope) correction: implementation of the embodiments
Brightness: adjusted to be in the range of 30 to 50
The brightness is a value to be appropriately set according to the hue of the measurement object. The above-mentioned settings are suitable values when the surface of the surface-treated copper foil having L < x > -69 to-10, a < x > -2 to 32 and b < x > -221 is measured.
Further, for Vmc, the change rate of Vmc is calculated according to the above formula (1).
Furthermore, the λc filter corresponds to ISO 25178-2:2012, L filters in 2012.
< measurement of color tone of measurement object >
MiniScan (registered trademark) EZ Model 4000L manufactured by HunterLab corporation was used as a measuring instrument in accordance with JIS Z8730:2009 to conduct the measurement of L, a and b of CIE L, a and b color systems. Specifically, the surface to be measured of the surface-treated copper foil or the copper foil obtained in the examples and comparative examples was pressed against the photosensitive part of the measuring instrument, and the measurement was performed without light entering from the outside. The measurement of L, a and b is based on JIS Z8722:2009, geometry C. The main conditions of the measuring instrument are as follows.
An optical system: d/8 °, integrating sphere size: 63.5mm, observation light source: d65 (D65)
The measurement method comprises the following steps: reflection of
Illumination diameter: 25.4mm
Diameter measurement: 20.0mm
Measuring wavelength, interval: 400-700 nm and 10nm
Light source: pulse hernia lamp 1-time luminescence/measurement
Traceability criteria: american standard technical institute (NIST) standard correction based on CIE 44 and ASTM E259
Standard observer: 10 degree
The following object colors were used for white tiles serving as measurement standards.
The values in the CIE XYZ color system, measured at D65/10 DEG, are X:81.90, Y:87.02, Z:93.76
< peel Strength >
After the surface-treated copper foil was bonded to the polyimide resin base material, a circuit having a width of 3mm was formed in the MD direction (the longitudinal direction of the rolled copper foil). The formation of the circuit is carried out according to a usual method. Next, according to JIS C6471:1995, measured the strength (MD 90 ° peel strength) when a circuit (surface-treated copper foil) was peeled off from the surface of a resin substrate in the 90 ° direction at a speed of 50 mm/min, i.e., vertically upward from the surface of the resin substrate. The measurement was performed 3 times, and the average value was used as a result of peel strength. When the peel strength is 0.50kgf/cm or more, it can be said that the adhesion between the circuit (surface-treated copper foil) and the resin substrate is good.
Further, the copper foil of comparative example 1 was not bonded to the polyimide resin base material, and thus the evaluation was not performed.
The results of the above-described characteristic evaluation are shown in table 1.
TABLE 1
As shown in table 1, the surface treated copper foils of examples 1 to 6, in which the rate of change in Vmc of the surface treated layer was in the range of 23.00 to 40.00%, were high in peel strength.
On the other hand, the surface treated copper foil of comparative example 2 in which the rate of change in Vmc of the surface treated layer was outside the specific range was low in peel strength.
With reference to the above results and examination of the embodiments of the present invention described so far, according to the embodiments of the present invention, it is possible to provide a surface-treated copper foil capable of improving adhesion to a resin base material, particularly a resin base material suitable for high-frequency applications. Further, according to the embodiment of the present invention, a copper-clad laminate excellent in adhesion between a resin base material, particularly a resin base material suitable for high-frequency use, and a surface-treated copper foil can be provided. Further, according to the embodiment of the present invention, a printed wiring board excellent in adhesion between a resin base material, particularly a resin base material suitable for high-frequency use, and a circuit pattern can be provided.
Claims (10)
1. A surface-treated copper foil comprising a copper foil and a surface-treated layer formed on at least one surface of the copper foil,
the rate of change of vm c represented by the following formula (1) in the surface treatment layer is 23.00-40.00%,
rate of change of vmc= (P2-P1)/p2x100· (1)
Where P1 is Vmc calculated by applying a λs filter having a cutoff value λs of 2 μm, and P2 is Vmc calculated by not applying the λs filter.
2. The surface-treated copper foil according to claim 1, wherein the rate of change of Vmc is 23.00 to 32.00%.
3. The surface-treated copper foil according to claim 1, wherein the rate of change of Vmc is 23.00 to 31.00%.
4. The surface-treated copper foil according to any one of claims 1 to 3, wherein the Sku calculated by the surface-treated layer without applying the λs filter is 2.50 to 4.50.
5. The surface-treated copper foil according to claim 4, wherein Sku is 2.90 to 4.10.
6. The surface treated copper foil according to any one of claims 1 to 5, wherein the Sq of the surface treated layer calculated without applying the λs filter is 0.20 to 0.60 μm.
7. The surface treated copper foil according to any one of claims 1 to 6, wherein Sa of the surface treated layer calculated without applying the λs filter is 0.20 to 0.40 μm.
8. The surface-treated copper foil according to any one of claims 1 to 7, wherein the surface-treated layer contains a roughened layer.
9. A copper-clad laminate comprising the surface-treated copper foil according to any one of claims 1 to 8 and a resin substrate attached to the surface-treated layer of the surface-treated copper foil.
10. A printed wiring board comprising a circuit pattern formed by etching the surface-treated copper foil of the copper-clad laminate according to claim 9.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2021-114581 | 2021-07-09 | ||
| JP2021114581 | 2021-07-09 | ||
| PCT/JP2022/001217 WO2023281774A1 (en) | 2021-07-09 | 2022-01-14 | Surface-treated copper foil, copper-clad laminate and printed wiring board |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116745468A true CN116745468A (en) | 2023-09-12 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202280008414.1A Pending CN116745468A (en) | 2021-07-09 | 2022-01-14 | Surface-treated copper foil, copper-clad laminate, and printed wiring board |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPWO2023281774A1 (en) |
| KR (1) | KR20230110591A (en) |
| CN (1) | CN116745468A (en) |
| TW (1) | TW202302918A (en) |
| WO (1) | WO2023281774A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MY150825A (en) * | 2008-11-25 | 2014-02-28 | Jx Nippon Mining & Metals Corp | Copper foil for printed circuit |
| WO2011138876A1 (en) * | 2010-05-07 | 2011-11-10 | Jx日鉱日石金属株式会社 | Copper foil for printed circuit |
| JP2012112009A (en) | 2010-11-26 | 2012-06-14 | Hitachi Cable Ltd | Copper foil, and method for producing copper foil |
| JP2014152352A (en) * | 2013-02-06 | 2014-08-25 | Sh Copper Products Corp | Composite copper foil and production method thereof |
| WO2017006739A1 (en) * | 2015-07-03 | 2017-01-12 | 三井金属鉱業株式会社 | Roughened copper foil, copper-clad laminate and printed wiring board |
| JP6200042B2 (en) * | 2015-08-06 | 2017-09-20 | Ｊｘ金属株式会社 | Copper foil with carrier, laminate, printed wiring board manufacturing method and electronic device manufacturing method |
| US10581081B1 (en) * | 2019-02-01 | 2020-03-03 | Chang Chun Petrochemical Co., Ltd. | Copper foil for negative electrode current collector of lithium ion secondary battery |
| JP6816193B2 (en) * | 2019-03-26 | 2021-01-20 | 古河電気工業株式会社 | Surface-treated copper foil, and copper-clad laminates and printed wiring boards using this |
| JP2021095596A (en) * | 2019-12-13 | 2021-06-24 | Ｊｘ金属株式会社 | Surface-treated copper foil, copper-clad laminate, and printed wiring board |
-
2022
- 2022-01-14 JP JP2023533043A patent/JPWO2023281774A1/ja active Pending
- 2022-01-14 WO PCT/JP2022/001217 patent/WO2023281774A1/en active Application Filing
- 2022-01-14 TW TW111101710A patent/TW202302918A/en unknown
- 2022-01-14 CN CN202280008414.1A patent/CN116745468A/en active Pending
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|---|---|
| WO2023281774A1 (en) | 2023-01-12 |
| TW202302918A (en) | 2023-01-16 |
| KR20230110591A (en) | 2023-07-24 |
| JPWO2023281774A1 (en) | 2023-01-12 |
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