US20040154930A1 - Copper foil for high frequency circuit and method of production of same - Google Patents

Copper foil for high frequency circuit and method of production of same Download PDF

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Publication number
US20040154930A1
US20040154930A1 US10/775,075 US77507504A US2004154930A1 US 20040154930 A1 US20040154930 A1 US 20040154930A1 US 77507504 A US77507504 A US 77507504A US 2004154930 A1 US2004154930 A1 US 2004154930A1
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Prior art keywords
copper foil
plating
roughening
electrodeposited copper
foil
Prior art date
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Abandoned
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US10/775,075
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English (en)
Inventor
Kensaku Shinozaki
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Furukawa Electric Co Ltd
Original Assignee
Furukawa Circuit Foil Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Furukawa Circuit Foil Co Ltd filed Critical Furukawa Circuit Foil Co Ltd
Assigned to FURUKAWA CIRCUIT FOIL CO., LTD. reassignment FURUKAWA CIRCUIT FOIL CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: SHINOZAKI, KENSAKU
Publication of US20040154930A1 publication Critical patent/US20040154930A1/en
Assigned to THE FURUKAWA ELECTRIC CO., LTD. reassignment THE FURUKAWA ELECTRIC CO., LTD. MERGER (SEE DOCUMENT FOR DETAILS). Assignors: FURUKAWA CIRCUIT FOIL CO., LTD.
Abandoned legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60Electroplating characterised by the structure or texture of the layers
    • C25D5/605Surface topography of the layers, e.g. rough, dendritic or nodular layers
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/38Chromatising
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00Electroforming
    • C25D1/04Wires; Strips; Foils
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00Electroplating: Baths therefor
    • C25D3/02Electroplating: Baths therefor from solutions
    • C25D3/38Electroplating: Baths therefor from solutions of copper
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10Electroplating with more than one layer of the same or of different metals
    • C25D5/12Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/34Pretreatment of metallic surfaces to be electroplated
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48After-treatment of electroplated surfaces
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/627Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00Electroplating characterised by the article coated
    • C25D7/06Wires; Strips; Foils
    • C25D7/0614Strips or foils
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/38Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/382Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
    • H05K3/384Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by plating
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/03Conductive materials
    • H05K2201/0332Structure of the conductor
    • H05K2201/0335Layered conductors or foils
    • H05K2201/0355Metal foils
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/03Metal processing
    • H05K2203/0307Providing micro- or nanometer scale roughness on a metal surface, e.g. by plating of nodules or dendrites
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/07Treatments involving liquids, e.g. plating, rinsing
    • H05K2203/0703Plating
    • H05K2203/0723Electroplating, e.g. finish plating
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/12All metal or with adjacent metals
    • Y10T428/12993Surface feature [e.g., rough, mirror]

Definitions

  • the present invention relates to a copper foil having a small surface roughness of the matte side particularly suitable for a conductive material of printed circuits for high frequency applications and a method of production of the copper foil.
  • the main use of the present invention is a conductive material of printed circuits for high frequency applications
  • the electrodeposited copper foil of the present invention is not limited to that use.
  • Electrodeposited copper foil used for conductive material for a printed circuit has to give the peel strength, electric characteristic, etching characteristics, heat resistance, etc. required for the surface bonded with a resin substrate (hereinafter called the “matte side”).
  • the matte side a resin substrate
  • various methods of treatment for roughening the matte side and improving its chemical properties have been proposed and put practical in use.
  • the method is proposed of performing electrolysis in an acidic copper electroforming bath using the copper foil as the cathode near the limit current density for burnt plating to obtain a rough surface (see for example Japanese Examined Patent Publication (Kokoku) No. 40-15327). Further, the method is proposed of covering the burnt plating surface of the rough surface by smooth copper plating to bind the plurality of the projections stably by the copper foil surface (see for example specification of U.S. Pat. No. 3,293,109).
  • Table 1 shows the transmission loss when transmitting a high frequency signal of 3 GHz to copper foils having various surface roughnesses of the matte side. Table 1 demonstrates that the roughness of the matte side has an extremely small influence on the transmission loss.
  • Roughening treating conditions Roughness (roughening current Roughness after 3 GHZ divided by of roughening Peel transmission roughening speed untreated treating strength loss (A ⁇ min/m) foil ( ⁇ m) ( ⁇ m) (kN/m) (dB/m) 400 1.70 1.99 0.74 3.97 400 1.12 1.33 0.61 3.98 1000 1.60 3.77 1.00 4.03 1000 1.20 1.72 0.74 4.01 300 4.74 5.14 0.92 3.92
  • the inventors engaged in further study about factors causing transmission loss and as a result found that the strength of the roughening (here, “strength of roughening treating” defined as roughening current divided by roughening speed, that is, A ⁇ min/m) for causing deposition of copper particles on the matte side has a large influence.
  • the roughening treating needed to be strong (roughing current large or roughening time long) to obtain a sufficient peel strength. Doing that made the transmission loss worse.
  • the value of the transmission loss is influenced largely by the measurement environment.
  • the transmission loss was measured under the same environment to compare the measured values. Therefore, the values in Table 1, Table 2, and other values can be compared.
  • An invention for producing a copper foil using an electrolyte of copper added with a compound having a mercapto group, at least one kind of other organic compounds and chloride ion see Japanese Patent Publication No. 3313277.
  • the copper foil produced in this invention has a shiny and very smooth surface at the matte side too. By burnt plating or otherwise treating this copper foil, a copper foil that has a matte side having a very low roughness and is suitable for fine patterns can be produced.
  • An object of the present invention is to provide electrodeposited copper foil having a high enough peel strength to meet the demands for recent printed circuit boards and an excellent high frequency transmission characteristic and a method of production of the same.
  • Another object of the present invention is to provide a copper foil having a high peel strength, capable of being applied to a fine pattern-compatible copper foil having small roughness of the matte side, and able to be used to give an excellent printed circuit board with fine patterns improved in high frequency transmission loss.
  • an electrodeposited copper foil wherein part of its surface comprises a rough surface having knob-like projections and a. surface roughness of 2 to 4 ⁇ m.
  • the rough surface having the knob-like projections and the surface roughness of 2 to 4 ⁇ m is a surface of an untreated copper foil for bonding with a resin substrate and is further roughening treated by running a predetermined current through the foil for a predetermined time in an electroforming bath.
  • the electroforming bath is an acidic electroforming bath containing at least one of molybdenum, cobalt, nickel, iron, tungsten and arsenic.
  • the rough surface is further formed with a copper plating layer.
  • the rough surface is further formed with a copper plating layer, at least one layer of nickel plating, zinc plating, cobalt plating, plating of an alloy of the same and a chromate treatment on that, and a coupling agent treatment layer according to need on that.
  • the rough surface having the knob-like projections and the surface roughness of 2 to 4 ⁇ m is a surface of an untreated copper foil for bonding with a resin substrate and is further is further formed with a copper plating layer, at least one layer of nickel plating, zinc plating, cobalt plating, plating of an alloy of the same and a chromate treatment on that, and a coupling agent treatment layer according to need on that.
  • a method of producing an electrodeposited copper foil comprising electrolysis using an electrolyte containing copper as a main component and a compound having mercapto groups, at least one type of another organic compound, and chloride ions to form a copper foil wherein part of its surface comprises a rough surface having knob-like projections and a surface roughness of 2 to 4 ⁇ m.
  • an electroforming bath for a roughening treatment is an acidic electroforming bath containing at least one of molybdenum, cobalt, nickel, iron, tungsten and arsenic.
  • a method of producing an electrodeposited copper foil comprising producing an electrodeposited copper foil having a matte side having a surface roughness of 2 to 4 ⁇ m using an electrolyte containing a compound having mercapto groups, at least one type of another organic compound, and chloride ions and roughening treating the matte side of the electrodeposited copper foil by running a predetermined current through it for a predetermined time in an electroforming bath.
  • FIG. 1 is an electron micrograph of the surface of a copper foil of one example of the present invention
  • FIG. 2 is an electron micrograph of the surface of a copper foil of another example of the present invention.
  • FIG. 3 is an electron micrograph of the surface of a copper foil of a further example of the present invention.
  • the electrodeposited copper foil according to the preset embodiment is characterized in that part of its surface is a rough surface having knob-like projections and having a surface roughness of 2 to 4 ⁇ m.
  • Such an electrodeposited copper foil is produced by electrolysis using an electrolyte containing a compound having mercapto groups, at least one type of another organic compound, and chloride ions.
  • the thus prepared surface to be bonded to a resin substrate (bonding surface) is finished to a smooth surface of a surface roughness of 2 to 4 ⁇ m, has knob-like projections formed on part of the smooth matte side, and can provide copper foil superior in high frequency transmission loss.
  • the above electrodeposited copper foil lacks peel strength. Stronger peel strength is demanded according to the application.
  • the electrodeposited copper foil is run through by a predetermined current as untreated copper foil for a predetermined time in an electroforming bath to roughen the matte side.
  • the roughening treating performed on the untreated copper foil is performed under weaker treatment conditions than the conventional roughening treating. Due to the weak roughening treating, an electrodeposited copper foil has a peel strength equal to or stronger than a conventional one (namely, the roughness of the matte side is large but the roughening treating is weak) and is superior in high frequency transmission loss.
  • an acidic electroforming bath containing at least one of molybdenum, cobalt, nickel, iron, tungsten, and arsenic can be used as the roughening electroforming bath for the roughening treating. Note that by performing the roughening treated copper foil by at least one of nickel plating, zinc plating, cobalt plating, plating of an alloy of the same, treating it by chromate treatment and a coupling agent treatment, the heat resistance, resistance to HC1, stain proofing, and peel strength can be improved.
  • the untreated copper foil by at least on of nickel plating, zinc plating, cobalt plating, plating of an alloy of the same, chromate treatment and a coupling agent treatment, a copper foil having a surface roughness smaller than a roughening treated copper foil and having a high peel strength to a certain type of substrate can be produced. Further, by plating and treating by a coupling agent, the heat resistance, resistance to HC1, and stain proofing can be further improved.
  • Electrodeposited copper foils were produced under the electrolyte composition and the electrolysis conditions shown in A to C of Table 3 (hereinafter, referred as Examples A to C) as the electrodeposited foil-making conditions of the present invention. Further, untreated copper foil was produced under the electrolyte composition and the electrolysis conditions as shown in D of Table 3 as a comparative example. TABLE 3 Conditions for producing copper foils and solution compositions Sulfuric Current Solution Copper acid MPS HEC Glue Cl density temp.
  • FIG. 1 shows the surface state of foil produced under the foil-making conditions A. The knob-like projections are dispersed evenly.
  • FIG. 2 shows the surface state of foil produced under the foil-making conditions B. The knob-like projections are closely concentrated.
  • FIG. 3 shows the surface state of foil produced under the foil-making conditions C. The knob-like projections are small and dispersed evenly with longer distances between them than in FIG. 1.
  • Treatment time 2 to 15 seconds
  • the roughening current density (5 to 30 A/dm 2 ) is lower than the roughening current density used conventionally. Note that the reason the treatment time is made 2 to 15 seconds is the sizes of the anodes were changed for treatment. The line speed was the same for the solution compositions.
  • the roughening treating and the encapsulation plating treatment may be performed several times in the present invention.
  • Example A was roughening treated.
  • the roughening treating for Example B was omitted.
  • plating the plated surface of the copper foil by one of nickel, zinc, cobalt, or an alloy of the same or treating it by chromate or a coupling agent the heat resistance, resistance to HCl, stain proofing, and peel strength can be improved.
  • Example C and Comparative Example D of the present invention were measured for high frequency transmission loss and peel strength while changing the roughening current divided by roughening speed. The results are shown in Table 8. TABLE 8 Roughening current Comparative Comparative Comparative divided by Example C Example C Example C Example D Example D Example D roughening surface peel transmission surface peel transmission speed roughness strength loss roughness strength loss 2600 7.20 1.57 4.45 2.40 1.07 4.38 900 3.95 1.42 3.79 1.25 0.77 3.77 400 2.90 1.22 3.7 0.90 0.60 3.71 200 2.55 1.21 3.62 0.90 0.59 3.64
  • the untreated copper foil of Comparative Example D cannot be used due to the decline of the peel strength when the roughening current divided by the roughening speed becomes small.
  • the copper foil of Example C of the present invention has a high peel strength even when the roughening current divided by the roughening speed becomes small and further has a transmission loss characteristic that is equal to untreated copper foil D.
  • Example D As described above, in Comparative Example D, a clear decline of the peel strength was observed due to the weakening of the roughening treating. In Example C of the present invention, a slight decline of the peel strength was observed due to the weakening of the roughening treating, but the peel strength was sufficient compared with Comparative Example D. Further, the transmission loss is almost the same as Comparative Example D. Therefore, copper foil with excellent transmission loss and further high peel strength and a method for producing the same are available according to the present invention. Needless to say, the copper foil produced in the present invention has a small surface roughness and high peel strength, so is suitable for copper foil for a printed circuit other than for high frequency applications as well.
  • Untreated copper foils were produced having thicknesses of 35 ⁇ m according to the untreated copper foil-making conditions and solution compositions of Example C and Comparative Example D of Example 1 and treated on their surfaces as shown in Table 9. TABLE 9 Condition no. Ni Zn Cr Co Si 1 0.30 0.02 0.03 0 0.005 2 0.30 0.20 0.03 0.2 0.005 3 0.05 0.02 0.03 0 0.005 4 0.05 0.25 0.03 0 0.005 5 0.10 0.04 0.03 0 0.005 6 0.25 0.03 0.03 0.15 0.005 7 0.10 0.03 0.03 0 0 0

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Laminated Bodies (AREA)
  • Manufacturing Of Printed Wiring (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
US10/775,075 2003-02-12 2004-02-11 Copper foil for high frequency circuit and method of production of same Abandoned US20040154930A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2003-033159 2003-02-12
JP2003033159A JP2004244656A (ja) 2003-02-12 2003-02-12 高周波用途対応可能銅箔とその製造方法

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US (1) US20040154930A1 (fr)
EP (1) EP1455005A3 (fr)
JP (1) JP2004244656A (fr)
KR (1) KR20040073387A (fr)
CN (1) CN1530469B (fr)
TW (1) TW200415012A (fr)

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US8668994B2 (en) 2008-12-26 2014-03-11 Jx Nippon Mining & Metals Corporation Rolled copper foil or electrolytic copper foil for electronic circuit, and method of forming electronic circuit using same
US9707738B1 (en) 2016-01-14 2017-07-18 Chang Chun Petrochemical Co., Ltd. Copper foil and methods of use
US9890463B2 (en) 2011-07-29 2018-02-13 Furukawa Electric Co., Ltd. Electrolysis copper-alloy foil, method of the same, electrolytic-solution using the production, negative electrode aggregation used the same, secondary battery, and electrode of the same
US10448507B2 (en) 2016-01-15 2019-10-15 Jx Nippon Mining & Metals Corporation Copper foil, copper-clad laminate board, method for producing printed wiring board, method for producing electronic apparatus, method for producing transmission channel, and method for producing antenna
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US10820414B2 (en) 2016-12-05 2020-10-27 Jx Nippon Mining & Metals Corporation Surface treated copper foil, copper foil with carrier, laminate, method for manufacturing printed wiring board, and method for manufacturing electronic device
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US11528801B2 (en) 2018-12-13 2022-12-13 Lg Innotek Co., Ltd. Printed circuit board
USRE49929E1 (en) 2017-08-08 2024-04-16 Sumitomo Electric Industries, Ltd. Substrate for high-frequency printed wiring board

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US20170208680A1 (en) 2016-01-15 2017-07-20 Jx Nippon Mining & Metals Corporation Copper Foil, Copper-Clad Laminate Board, Method For Producing Printed Wiring Board, Method For Producing Electronic Apparauts, Method For Producing Transmission Channel, And Method For Producing Antenna
JP2017193778A (ja) 2016-04-15 2017-10-26 Jx金属株式会社 銅箔、高周波回路用銅箔、キャリア付銅箔、高周波回路用キャリア付銅箔、積層体、プリント配線板の製造方法及び電子機器の製造方法
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WO2018212285A1 (fr) * 2017-05-18 2018-11-22 Agc株式会社 Film et stratifié de résine d'hydrocarbure fluoré, et procédé de production d'un stratifié thermiquement pressé
CN112708909A (zh) * 2020-12-18 2021-04-27 江西省江铜耶兹铜箔有限公司 一种复合电镀液及高频pcb用低轮廓电解铜箔的制备方法
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EP4391734A1 (fr) 2022-12-21 2024-06-26 JX Metals Corporation Feuille de cuivre, stratifié et carte de circuit imprimé flexible

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CN1530469B (zh) 2011-01-26
CN1530469A (zh) 2004-09-22
TW200415012A (en) 2004-08-16
KR20040073387A (ko) 2004-08-19
EP1455005A2 (fr) 2004-09-08
EP1455005A3 (fr) 2006-08-02
TWI371368B (fr) 2012-09-01

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