WO2015033917A1 - Surface-processed copper foil, copper clad laminate obtained using such surface-processed copper foil, and printed wiring board - Google Patents

Surface-processed copper foil, copper clad laminate obtained using such surface-processed copper foil, and printed wiring board Download PDF

Info

Publication number
WO2015033917A1
WO2015033917A1 PCT/JP2014/073026 JP2014073026W WO2015033917A1 WO 2015033917 A1 WO2015033917 A1 WO 2015033917A1 JP 2014073026 W JP2014073026 W JP 2014073026W WO 2015033917 A1 WO2015033917 A1 WO 2015033917A1
Authority
WO
WIPO (PCT)
Prior art keywords
copper foil
treated copper
wiring board
printed wiring
treated
Prior art date
Application number
PCT/JP2014/073026
Other languages
French (fr)
Japanese (ja)
Inventor
小畠　真一
慎哉 平岡
Original Assignee
三井金属鉱業株式会社
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 三井金属鉱業株式会社 filed Critical 三井金属鉱業株式会社
Priority to JP2015515307A priority Critical patent/JP6722452B2/en
Publication of WO2015033917A1 publication Critical patent/WO2015033917A1/en

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • C—CHEMISTRY; METALLURGY
    • 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
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • 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
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
    • C25D5/611—Smooth 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
    • C25D7/0614—Strips or foils
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/04—Electrolytic coating other than with metals with inorganic materials
    • C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
    • 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
    • H05K1/0213—Electrical arrangements not otherwise provided for
    • H05K1/0237—High frequency adaptations
    • H05K1/0242—Structural details of individual signal conductors, e.g. related to the skin effect
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
    • H05K3/384—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by plating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/565—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of zinc
    • 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
    • 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
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/03—Conductive materials
    • H05K2201/0332—Structure of the conductor
    • H05K2201/0335—Layered conductors or foils
    • H05K2201/0355—Metal 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
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
    • H05K2203/0703—Plating
    • H05K2203/0726—Electroforming, i.e. electroplating on a metallic carrier thereby forming a self-supporting structure
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
    • H05K3/025—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates by transfer of thin metal foil formed on a temporary carrier, e.g. peel-apart copper
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/389—Improvement of the adhesion between the insulating substrate and the metal by the use of a coupling agent, e.g. silane

Definitions

  • the present application relates to a surface-treated copper foil and a copper-clad laminate obtained using the surface-treated copper foil.
  • the present invention relates to a surface-treated copper foil in which a roughening treatment is performed on the electrode surface side of the electrolytic copper foil.
  • Patent Document 1 for the purpose of providing a surface-treated copper foil having excellent etching characteristics, adhesion, chemical resistance, and moisture absorption resistance, “a bonding surface region having a two-dimensional surface area of 6550 ⁇ m 2 was measured by a laser method.
  • the surface-treated copper foil has a surface area ratio (B) of 1.2 to 2.5, which is a value of the ratio [(A) / (6550)] of the three-dimensional surface area (A) ⁇ m 2 to the two-dimensional surface area, More preferably, when the surface roughness (Rzjis) of the untreated copper foil before roughening is less than 1.0 ⁇ m, the surface having a two-dimensional surface area of 6550 ⁇ m 2 is measured by a laser method.
  • the ratio [(A) / (a)] of the three-dimensional surface area (a) ⁇ m 2 before the roughening treatment to the three-dimensional surface area (A) ⁇ m 2 after the roughening treatment is 1.15 to 2.50. "Surface-treated copper foil.”
  • Patent Document 2 the adhesion between the base resin surface exposed to a printed wiring board on which an electronic component is mounted using an anisotropic conductive film and the anisotropic conductive film is good, and the formation of fine wiring is easy.
  • surface area when measuring a two-dimensional region with a surface roughness (Rzjis) of 2.5 ⁇ m or less and a surface area of 6550 ⁇ m 2 by a laser method.
  • the value of the surface area ratio (B) calculated by the ratio [(A) / (6550)] of the (three-dimensional area: A ⁇ m 2 ) to the two-dimensional area is 1.25 to 2.50, the unit of the two-dimensional area
  • the surface-treated copper foil and the insulating resin base material constituting the printed wiring board are good and the variation is extremely high by adopting the surface-treated copper foil shown below. It was conceived that excellent adhesion with a small stability could be secured. Furthermore, it was found that the surface-treated copper foil according to the present application can ensure good high-frequency characteristics and can form a fine pitch circuit. Hereinafter, the surface-treated copper foil according to the present application will be described.
  • the surface-treated copper foil according to the present application is a surface-treated copper foil that has been subjected to a roughening treatment on the electrode surface side of the electrolytic copper foil, and the roughening-treated surface that satisfies the requirements shown in Equation 1 below It is characterized by providing.
  • the surface-treated copper foil according to the present application preferably has a surface area ratio of the roughened surface of 1.7 to 2.4.
  • the surface-treated copper foil according to the present application is subjected to a rust prevention treatment, a silane coupling agent treatment, or the like, if necessary, on the roughened surface.
  • Copper-clad laminate The copper-clad laminate according to the present application is obtained using a surface-treated copper foil having the above-mentioned roughened surface.
  • the printed wiring board according to the present application is obtained by using the copper-clad laminate according to the present application, which is obtained by using the surface-treated copper foil having the roughened surface.
  • the surface-treated copper foil subjected to the roughening treatment on the electrode surface side according to the present application satisfies the above-described conditions, and the surface-treated copper foil and the insulating resin base material constituting the printed wiring board are good, and Adhesion with excellent stability with very little variation can be secured. In addition, good high frequency characteristics can be ensured, and a fine pitch circuit can be formed. As a result, the quality stability of the printed wiring board can be improved and the life of the printed wiring board can be extended. Therefore, the copper clad laminate obtained using the surface-treated copper foil according to the present application is suitable for producing a high-quality printed wiring board.
  • the surface-treated copper foil according to the present application is a surface-treated copper foil that has been subjected to a roughening treatment on the electrode surface side of the electrolytic copper foil, and the roughening treatment that satisfies the requirement shown in the above-mentioned formula 1 A surface is provided.
  • the surface treatment copper foil 1 which concerns on this application can understand the layer structure easily with sectional drawing of the surface treatment copper foil typically shown in FIG. As can be understood from FIG. 1, generally, the deposition surface side 3 of the electrolytic copper foil 2 has an uneven shape.
  • the surface roughness (Rz) of the roughened surface of the surface-treated copper foil according to the present application is 2.5 ⁇ m to 4.0 ⁇ m.
  • This surface roughness (Rz) is a 10-point average roughness defined in JIS standards (JIS B 0601: 1982).
  • the surface roughness (Rz) is less than 2.5 ⁇ m, a good anchor effect for the insulating resin substrate cannot be obtained, and stable adhesion cannot be obtained.
  • the surface roughness (Rz) exceeds 4.0 ⁇ m, when attempting to adhere and form the roughened particles using the electrolytic method, current concentrates on the precipitated particles and the roughened particles overlap each other. Therefore, the peel strength of the formed circuit, the high frequency characteristics of the obtained printed wiring board, and the ability to form a fine pitch circuit tend to vary.
  • the value calculated as [Rmax ⁇ Ra] in addition to the surface roughness (Rz) described above, the value calculated as [Rmax ⁇ Ra] must be 3.5 ⁇ m or less.
  • This index [Rmax ⁇ Ra] has the highest correlation in considering the adhesion stability between the roughened surface of the surface-treated copper foil and the insulating resin substrate.
  • peel strength variation when the value calculated as [Rmax ⁇ Ra] of this surface-treated copper foil exceeds 3.5 ⁇ m, even if it is a peel strength sample produced using the same surface-treated copper foil, This is not preferable because the variation in the measured peel strength of the sample becomes large (hereinafter, this phenomenon is simply referred to as “peeling strength variation”).
  • the lower limit value of [Rmax-Ra] of the roughened surface of the surface-treated copper foil is not particularly defined, but [Rmax-Ra] of the roughened surface of the surface-treated copper foil is not limited. About 2.2 ⁇ m.
  • the surface-treated copper foil according to the present application has a surface area ratio of 1.7 to 2 on the roughened surface. .4 is preferable. This surface area ratio is calculated by comparing the surface area (three-dimensional surface area: A ⁇ m 2 ) when measuring the two-dimensional region corresponding to 6550 ⁇ m 2 of the roughened surface of the surface-treated copper foil with the laser method and the “two-dimensional region area”. It is the value of the surface area ratio calculated by the ratio [(A) / (6550)]. This surface area ratio is an alternative index of the contact area between the surface-treated copper foil and the insulating resin base material.
  • the surface area ratio is less than 1.7, it is difficult to obtain high adhesion between the roughened surface of the surface-treated copper foil and the insulating resin base material.
  • the surface area ratio exceeds 2.4, the adhesion between the roughened surface of the surface-treated copper foil and the insulating resin base material is increased, but the variation in the peel strength tends to increase, which is not preferable. .
  • this surface area ratio exceeds 2.4, since the high frequency characteristic of the obtained printed wiring board tends to fall, it is not preferable.
  • the surface area ratio exceeds 2.4, the particle size variation of the roughened particles at this time also increases, and the ability to form a fine pitch circuit when forming a wiring by etching is not preferable.
  • the transmission loss of high-frequency signals is small, and the transmission Loss variation also decreases.
  • the transmission loss of the high-frequency signal needs to consider the skin effect, and in the microstrip line, the high-frequency signal propagates mainly on the insulating resin base material side. Therefore, the transmission loss in the microstrip line is greatly affected by the “roughened shape of the roughened surface, which is a surface bonded to the insulating resin layer of the surface-treated copper foil” and “linearity of the wiring circuit edge”.
  • the surface-treated copper foil according to the present application is bonded to an insulating resin base material (FR-4 base material) and outputs a signal having a frequency of 10 GHz to a microcircuit having a wiring circuit width of 220 ⁇ m. Transmission loss when transmitting via the stripline can be reduced to 4.0 dB / 10 cm or less.
  • the electrolytic solution has a copper concentration of 5 g / L to 20 g / L, a free sulfuric acid concentration of 50 g / L to 200 g / L, and other additives as necessary (for example, ⁇ -naphthoquinoline, dextrin, glue, It is preferable to use a copper electrolyte containing 15 to 40 ° C. containing thiourea or the like.
  • “cover plating” is immediately performed using smooth plating conditions.
  • this covering plating if smooth copper plating is possible, there is no special limitation regarding plating conditions.
  • the copper concentration is 50 g / L to 80 g / L
  • the free sulfuric acid concentration is 50 g / L to 150 g / L
  • the liquid temperature is 40 ° C. to 50 ° C.
  • the current density is 10 A / dm 2. It is preferable to employ a condition of ⁇ 50 A / dm 2 . As described above, the roughening process is completed.
  • the target surface of the electrolytic copper foil subjected to the roughening treatment is the electrode surface side provided with the replica shape of the electrode surface at the time of producing the electrolytic copper foil. This is because the surface roughness does not change depending on the above.
  • the surface-treated copper foil according to the present application is subjected to a rust prevention treatment, a silane coupling agent treatment, or the like, if necessary, on the roughened surface.
  • a rust prevention treatment inorganic rust prevention or organic rust prevention can be used.
  • inorganic rust prevention zinc rust prevention, brass rust prevention, zinc-nickel alloy rust prevention, zinc-cobalt alloy rust prevention, chromate treatment, etc. can be used.
  • organic rust prevention imidazoles, triazoles and the like can be used.
  • silane coupling agent process which plays the role of an auxiliary agent for improving the adhesion between the insulating resin base material and the surface-treated copper foil improves the wettability between the surface of the surface-treated copper foil and the insulating resin base material.
  • various materials such as a general epoxy functional silane coupling agent, an olefin functional silane coupling agent, and an acrylic functional silane coupling agent can be used.
  • Form of copper-clad laminate The copper-clad laminate according to the present application is obtained by using a surface-treated copper foil having the above-mentioned roughened surface. If the copper clad laminate at this time is obtained using the surface-treated copper foil according to the present application, there are no particular limitations regarding the constituent components, thickness, lamination method, etc. of the insulating resin substrate used. No. Moreover, the copper clad laminated board which concerns on this application contains the concept of both a rigid type and a flexible type.
  • a printed wiring board according to the present application is obtained by using a surface-treated copper foil provided with the above-mentioned roughened surface, and this copper-clad laminated board is used. On the other hand, it is obtained by performing various processes necessary for manufacturing a printed wiring board, such as a known etching process, via-hole process, and plating process. Therefore, the printed wiring board according to the present application includes a rigid type printed wiring board, a flexible type printed wiring board, a rigid-flex type printed wiring board, and the like, and there is no limitation on the type of the printed wiring board.
  • the layer configuration of the printed wiring board according to the present application also includes the concept of all layer configurations of a single-sided printed wiring board, a double-sided printed wiring board, and a multilayer printed wiring board having three or more layers. Therefore, in the case of the printed wiring board according to the present application, it is clearly stated that there is no limitation on the type of insulating layer constituent material and the thickness of the insulating layer.
  • the electrolytic copper foil is immersed in a copper electrolytic solution having a copper concentration of 8 g / L, a free sulfuric acid concentration of 150 g / L, and an additive (Nikawa) containing 25 ° C., and an electric quantity of 200 C / dm 2 is used. Then, electricity was applied for 10 seconds to deposit fine copper particles on the electrode side surface. Thereafter, “cover plating” was performed using the following smooth plating conditions to fix the fine copper particles on the electrode surface. In this covering plating, the conditions of a copper concentration of 70 g / L, a free sulfuric acid concentration of 120 g / L, a liquid temperature of 45 ° C., and a current density of 25 A / dm 2 were adopted.
  • rust prevention treatment was performed on both surfaces of the electrolytic copper foil. Specifically, it is immersed in a solution having a potassium pyrophosphate concentration of 80 g / L, a zinc concentration of 0.2 g / L, a nickel concentration of 2 g / L, and a liquid temperature of 40 ° C. SUS plates were placed on both sides of the electrolytic copper foil and electrolyzed at a current density of 0.5 A / dm 2 to form a zinc-nickel alloy layer on both sides of the electrolytic copper foil.
  • a chromate layer was formed by an electrolytic method. Specifically, it is immersed in a solution having a chromic acid concentration of 1 g / L, a pH of 11, and a liquid temperature of 25 ° C., and the electrolytic copper foil is used as a cathode and the SUS plate is used as an anode on both sides of the electrolytic copper foil. Electrolysis was performed at a current density of 1 A / dm 2 , and a chromate layer was formed on the surface of the zinc-nickel alloy layer to obtain a rust-proofing layer.
  • the rust-proofing layer When the formation of the rust-proofing layer was completed, it was washed with water and immediately subjected to a silane coupling agent treatment on the surface of the rust-proofing layer on the roughened surface. Specifically, ⁇ -glycidoxypropyltrimethoxysilane is dissolved in ion-exchanged water to prepare an aqueous solution having a concentration of 3 g / L, and this aqueous solution is showered over the entire surface of the rust-proofing layer on the roughened surface. Then, it was brought into contact with a roll to make the liquid film thickness uniform.
  • Example 1 When the silane coupling agent treatment was completed, the surface-treated copper foil according to Example 1 was obtained by dispersing the moisture in a drying furnace set to an atmosphere where the copper foil temperature was 150 ° C. for 4 seconds. A scanning electron microscope observation image of the surface-treated copper foil obtained in Example 1 is shown as Example 1 in FIG.
  • Example 2 Under the conditions of the roughening treatment of Example 1, a liquid temperature of 25 ° C. containing a copper concentration of 12 g / L, a free sulfuric acid concentration of 150 g / L, and an additive (Nikawa) A surface-treated copper foil was produced in the same manner as in Example 1 except that the copper electrolyte solution was used, and a surface-treated copper foil according to Example 2 was obtained.
  • Example 3 Under the conditions of the roughening treatment in Example 1, a liquid temperature of 25 ° C. containing a copper concentration of 6 g / L, a free sulfuric acid concentration of 150 g / L, and an additive (Nika) A surface-treated copper foil according to Example 3 was obtained by producing a surface-treated copper foil in the same manner as in Example 1 except that the copper electrolyte solution was used.
  • Evaluation of the three-dimensional surface area Two-dimensional surface roughening of the surface-treated copper foil using an ultra-deep color 3D shape measuring microscope VK-9500 (used laser: violet laser with a visible light limit wavelength of 408 nm) manufactured by Keyence Corporation A three-dimensional surface area was measured for a region having a region area of 6550 ⁇ m 2 .
  • Peel strength The roughened surface of the surface-treated copper foil was overlaid with a FR-4 prepreg having a thickness of about 1.0 mm and heated at 20 kgf / cm 2 (1.96 MPa) at 185 ° C. for 60 minutes.
  • a single-sided copper clad laminate was produced by pressure forming. Then, the surface of the electrolytic copper foil of this single-sided copper clad laminate is leveled, and the dry film method is used to provide a linear wiring circuit having a width of 0.2 mm for measuring the peeling strength. A measurement sample "was obtained. Then, using this “peeling strength measurement sample”, the peeling strength was measured according to JIS C 6481.
  • the high-frequency characteristic here is a vector network analyzer (VNA) 37200B series (model number: 37247C) manufactured by Anritsu Corporation, using a high-frequency signal of 10 GHz, a substrate thickness of 60 ⁇ m, and a wiring circuit width of 220 ⁇ m.
  • VNA vector network analyzer
  • the transmission loss when transmitting via the line was evaluated. And the quality was judged by whether the transmission loss at this time became 4.0 dB / 10 cm or less. When the transmission loss was 4.0 dB / 10 cm or less, it was evaluated as “ ⁇ ”, and when the transmission loss exceeded 4.0 dB / 10 cm, it was evaluated as “x”.
  • Comparative Example 1 Production of surface-treated copper foil: In Comparative Example 1, a surface-treated copper foil was produced in the same manner as in Example 1 except that the amount of electricity was 50 C / dm 2 under the roughening treatment conditions in Example 1. A surface-treated copper foil according to Example 1 was obtained. A scanning electron microscope observation image of the surface-treated copper foil obtained in Comparative Example 1 is shown as Comparative Example 1 in FIG.
  • Comparative Example 2 Production of surface-treated copper foil: In Comparative Example 2, a surface-treated copper foil was produced in the same manner as in Example 1 except that the amount of electricity was 300 C / dm 2 under the conditions of the roughening treatment in Example 1. A surface-treated copper foil according to Comparative Example 2 was obtained. A scanning electron microscope observation image of the surface-treated copper foil obtained in Comparative Example 2 is shown as Comparative Example 2 in FIG.
  • Comparative Example 3 In Comparative Example 3, using the roughening treatment conditions employed in the example of Patent Document 2, the same electrolytic copper foil as Example 1 of the present application was subjected to the roughening treatment. That is, it is as follows.
  • the electrolytic copper foil is immersed in a copper electrolyte at a liquid temperature of 30 ° C. containing a copper concentration of 10 g / L and a free sulfuric acid concentration of 100 g / L, and an electric quantity of 250 C / dm 2 is used. Then, electricity was applied for 10 seconds to deposit fine copper particles on the electrode side surface. Thereafter, “cover plating” was performed using the following smooth plating conditions to fix the fine copper particles on the electrode surface. In this covering plating, the conditions of a copper concentration of 70 g / L, a free sulfuric acid concentration of 150 g / L, a liquid temperature of 45 ° C., and a current density of 60 A / dm 2 were adopted.
  • inorganic rust prevention treatment was performed. Specifically, it is immersed in a solution having a potassium pyrophosphate concentration of 80 g / L, a zinc concentration of 0.2 g / L, a nickel concentration of 2 g / L, and a liquid temperature of 40 ° C., and the electrolytic copper foil is polarized to the cathode. Thus, a zinc-nickel alloy layer was formed on the roughened surface of the electrolytic copper foil. Further, a chromate layer was formed on the surface of the zinc-nickel alloy layer by an electrolytic method.
  • Examples 1 to 3 the values of the surface roughness (Rz), [Rmax ⁇ Ra], and the surface area ratio are all within the appropriate ranges in the present application, and the peel strength is also It can be seen that 1.40 kgf / cm or more is a good value. In addition, it can be said that Examples 1 to 3 have excellent signal transmission characteristics and excellent high frequency characteristics.
  • Comparative Example 1 the surface roughness (Rz) is within the appropriate range in the present application, but [Rmax-Ra] is not within the appropriate range in the present application. Moreover, since the roughening process is inadequate in the comparative example 1, the surface area ratio of the roughening process surface is a low value, and is outside the range considered appropriate in this application. This can be understood from the microscopic observation image of FIG. Although Comparative Example 1 has good high frequency characteristics, the peel strength is as low as 1.28 kgf / cm.
  • Comparative Example 2 since the roughening treatment is excessive, the particle diameter of the fine copper particles is large as can be understood from FIG. Further, the values of the surface roughness (Rz) and [Rmax ⁇ Ra] are out of the proper ranges in the present application. In Comparative Example 2, the surface area ratio is also lower than that in Example 1 or Example 2. As a result, although Comparative Example 2 shows a high peel strength of 1.53 kgf / cm due to the anchor effect of fine copper particles having a large particle size, the signal transmission characteristics are poor and good It cannot be said that it has a high frequency characteristic.
  • Comparative Example 3 As can be understood from FIG. 2, it seems that the particle diameter of the fine copper particles is only slightly larger than that in Example 1.
  • the surface roughness (Rz) is also within the appropriate range in the present application.
  • the value of [Rmax ⁇ Ra] is a higher value than Comparative Example 1 that is outside the appropriate range in the present application, and the surface area ratio is slightly lower than the appropriate range in the present application. It has become.
  • the peel strength is slightly low at 1.36 kgf / cm, the signal transmission characteristics are also deteriorated, and it cannot be said that the high frequency characteristics are provided.
  • the surface roughness (Rz) and [Rmax ⁇ Ra], and further, the roughened surface having a surface area ratio within the appropriate range in the present application has sufficient peel strength.
  • the value can be secured, the signal transmission characteristics are good, and the high frequency characteristics are excellent.
  • the surface-treated copper foil according to the present application has the surface roughness (Rz) and [Rmax-Ra] of the roughened surface, and the surface area ratio is within a predetermined range. It is possible to form a “circuit having a good signal transmission characteristic”, which is a characteristic contrary to the adhesiveness.
  • the surface-treated copper foil according to the present application described above has very little variation in adhesion with the insulating resin base material, the circuit forming excellent in high frequency characteristics can be achieved with “good adhesion with the insulating resin base material”. It is a product that has an excellent balance of conflicting characteristics. Therefore, when a copper clad laminate produced using the surface-treated copper foil according to the present application is used as a basic material of a printed wiring board, it is equipped with a fine pitch circuit having good adhesion to an insulating resin substrate, and a high frequency signal Therefore, it is possible to provide a printed wiring board having a characteristic impedance equivalent to the design quality.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Laminated Bodies (AREA)
  • Parts Printed On Printed Circuit Boards (AREA)

Abstract

The purpose of the present invention is to provide a surface-processed copper foil with which there is very little variation in the adherence of the surface-processed copper foil and an insulating resin substrate which constitute a printed wiring board. To achieve this purpose, provided is a surface-processed copper foil on which roughening has been carried out on the electrode surface side of an electrolytic copper foil, wherein the surface-processed copper foil is characterized by having a roughened surface which satisfies the conditions indicated by a formula 1. Also provided are a copper clad laminate characterized by being obtained by using the surface-processed copper foil, and a printed wiring board characterized by being obtained by using the copper clad laminate.

Description

表面処理銅箔、その表面処理銅箔を用いて得られる銅張積層板及びプリント配線板Surface-treated copper foil, copper-clad laminate and printed wiring board obtained using the surface-treated copper foil
　本件出願は、表面処理銅箔及びその表面処理銅箔を用いて得られる銅張積層板に関する。特に、電解銅箔の電極面側に粗化処理を施した表面処理銅箔に関する。 The present application relates to a surface-treated copper foil and a copper-clad laminate obtained using the surface-treated copper foil. In particular, the present invention relates to a surface-treated copper foil in which a roughening treatment is performed on the electrode surface side of the electrolytic copper foil.
　近年のプリント配線板製造用の表面処理銅箔には、絶縁樹脂基材との良好な密着性を備えることを前提として、ファインピッチ回路の形成に適した良好なエッチング特性、ＧＨｚ帯の高周波信号の伝送損失や特性インピーダンスなどの良好な高周波特性等が求められている。これらの諸特性は、表面処理銅箔に施される粗化処理に依存するものであることから、均一な粗化処理が施され、粗化処理後の表面粗さが過剰に大きくならないことが求められてきた。このような表面処理銅箔として、本件出願人等は、以下に述べる特許文献１及び特許文献２に開示の表面処理銅箔を提唱してきた。 Surface treated copper foil for printed wiring board production in recent years has good etching characteristics suitable for the formation of fine pitch circuits and high frequency signals in the GHz band on the premise that it has good adhesion to insulating resin base materials. Good high-frequency characteristics such as transmission loss and characteristic impedance are required. Since these characteristics depend on the roughening treatment applied to the surface-treated copper foil, a uniform roughening treatment is performed, and the surface roughness after the roughening treatment may not be excessively increased. It has been sought. As such surface-treated copper foil, the present applicants have proposed the surface-treated copper foil disclosed in Patent Document 1 and Patent Document 2 described below.
　特許文献１では、エッチング特性、密着性、耐薬品性、耐吸湿性に優れた表面処理銅箔を提供することを目的として、「２次元表面積が６５５０μｍ２の接着表面領域をレーザー法で測定したときの３次元表面積（Ａ）μｍ２と２次元表面積との比［（Ａ）／（６５５０）］の値である表面積比（Ｂ）が１．２～２．５の表面処理銅箔とし、より好ましくは、未処理銅箔の粗化処理前の表面粗さ（Ｒｚｊｉｓ）が１．０μｍ未満の表面を粗化処理し、２次元表面積が６５５０μｍ２の領域をレーザー法で測定したときの、粗化処理前の３次元表面積（ａ）μｍ２と粗化処理後の３次元表面積（Ａ）μｍ２との比［（Ａ）／（ａ）］の値が１．１５～２．５０の表面処理銅箔。」を採用している。 In Patent Document 1, for the purpose of providing a surface-treated copper foil having excellent etching characteristics, adhesion, chemical resistance, and moisture absorption resistance, “a bonding surface region having a two-dimensional surface area of 6550 μm 2 was measured by a laser method. When the surface-treated copper foil has a surface area ratio (B) of 1.2 to 2.5, which is a value of the ratio [(A) / (6550)] of the three-dimensional surface area (A) μm 2 to the two-dimensional surface area, More preferably, when the surface roughness (Rzjis) of the untreated copper foil before roughening is less than 1.0 μm, the surface having a two-dimensional surface area of 6550 μm 2 is measured by a laser method. The ratio [(A) / (a)] of the three-dimensional surface area (a) μm 2 before the roughening treatment to the three-dimensional surface area (A) μm 2 after the roughening treatment is 1.15 to 2.50. "Surface-treated copper foil."
　特許文献２では、異方性導電膜を用いて電子部品を実装するプリント配線板に露出した基材樹脂表面と異方性導電膜との密着力が良好で、微細配線の形成が容易な２層ポリイミド銅張積層板用の表面処理銅箔を提供することを目的として、「表面粗さ（Ｒｚｊｉｓ）が２．５μｍ以下、表面積が６５５０μｍ２の二次元領域をレーザー法で測定したときの表面積（三次元面積：Ａμｍ２）と二次元領域面積との比［（Ａ）／（６５５０）］で算出される表面積比（Ｂ）の値が１．２５～２．５０、二次元領域の単位面積あたりのクロムの量が２．０ｍｇ／ｍ２以上である絶縁樹脂基材との接着面を備えることを特徴とした表面処理銅箔。」を採用している。 In Patent Document 2, the adhesion between the base resin surface exposed to a printed wiring board on which an electronic component is mounted using an anisotropic conductive film and the anisotropic conductive film is good, and the formation of fine wiring is easy. In order to provide a surface-treated copper foil for a multilayer polyimide copper-clad laminate, “surface area when measuring a two-dimensional region with a surface roughness (Rzjis) of 2.5 μm or less and a surface area of 6550 μm 2 by a laser method. The value of the surface area ratio (B) calculated by the ratio [(A) / (6550)] of the (three-dimensional area: A μm 2 ) to the two-dimensional area is 1.25 to 2.50, the unit of the two-dimensional area A surface-treated copper foil characterized by having an adhesive surface with an insulating resin base material in which the amount of chromium per area is 2.0 mg / m 2 or more is employed.
特開２００８－２８５７５１号公報JP 2008-285751 A 特開２００９－１０５２８６号公報JP 2009-105286 A
　しかしながら、上述の特許文献１及び特許文献２に開示の表面処理銅箔の場合、表面処理銅箔と絶縁樹脂基材との密着性という観点において、一定のレベルでバラツキが生じる。従って、プリント配線板の品質の安定性を更に向上させて、プリント配線板の長寿命化を図るため、プリント配線板を構成する表面処理銅箔と絶縁樹脂基材との密着性を、更にバラツキの無いものとすることが望まれてきた。 However, in the case of the surface-treated copper foils disclosed in Patent Document 1 and Patent Document 2 described above, variations occur at a certain level in terms of adhesion between the surface-treated copper foil and the insulating resin base material. Therefore, in order to further improve the stability of the quality of the printed wiring board and extend the life of the printed wiring board, the adhesiveness between the surface-treated copper foil constituting the printed wiring board and the insulating resin substrate is further varied. It has been desired that there be no.
　そこで、本件発明者等の鋭意研究の結果、以下に示す表面処理銅箔を採用することで、プリント配線板を構成する表面処理銅箔と絶縁樹脂基材とが良好で、且つ、バラツキが極めて少ない安定性に優れた密着性が確保できることに想到した。さらに、本件出願に係る表面処理銅箔は、良好な高周波特性の確保が可能となり、ファインピッチ回路の形成が可能となることが分かった。以下、本件出願に係る表面処理銅箔について説明する。 Therefore, as a result of diligent research by the inventors, the surface-treated copper foil and the insulating resin base material constituting the printed wiring board are good and the variation is extremely high by adopting the surface-treated copper foil shown below. It was conceived that excellent adhesion with a small stability could be secured. Furthermore, it was found that the surface-treated copper foil according to the present application can ensure good high-frequency characteristics and can form a fine pitch circuit. Hereinafter, the surface-treated copper foil according to the present application will be described.
表面処理銅箔：　本件出願に係る表面処理銅箔は、電解銅箔の電極面側に粗化処理を施した表面処理銅箔であって、以下の数１に示す要件を満たす粗化処理表面を備えることを特徴とする。 Surface-treated copper foil: The surface-treated copper foil according to the present application is a surface-treated copper foil that has been subjected to a roughening treatment on the electrode surface side of the electrolytic copper foil, and the roughening-treated surface that satisfies the requirements shown in Equation 1 below It is characterized by providing.
Figure JPOXMLDOC01-appb-M000002
Figure JPOXMLDOC01-appb-M000002
　そして、本件出願に係る表面処理銅箔は、前記粗化処理表面の表面積比が１．７～２．４であることが好ましい。 The surface-treated copper foil according to the present application preferably has a surface area ratio of the roughened surface of 1.7 to 2.4.
　また、本件出願に係る表面処理銅箔は、粗化処理を施した表面に対して、必要に応じて防錆処理、シランカップリング剤処理等を施すことも好ましい。 Moreover, it is also preferable that the surface-treated copper foil according to the present application is subjected to a rust prevention treatment, a silane coupling agent treatment, or the like, if necessary, on the roughened surface.
銅張積層板：　本件出願に係る銅張積層板は、上述の粗化処理表面を備える表面処理銅箔を用いて得られることを特徴とする。 Copper-clad laminate: The copper-clad laminate according to the present application is obtained using a surface-treated copper foil having the above-mentioned roughened surface.
プリント配線板：　本件出願に係るプリント配線板は、上述の粗化処理表面を備える表面処理銅箔を用いて得られることを特徴とする本件出願に係る銅張積層板を用いて得られることを特徴とする。 Printed wiring board: The printed wiring board according to the present application is obtained by using the copper-clad laminate according to the present application, which is obtained by using the surface-treated copper foil having the roughened surface. Features.
　本件出願に係る電極面側に粗化処理を施した表面処理銅箔は、上述の条件を満たすことにより、プリント配線板を構成する表面処理銅箔と絶縁樹脂基材とが良好で、且つ、バラツキが極めて少ない安定性に優れた密着性を確保することができる。また、良好な高周波特性の確保も可能となり、ファインピッチ回路の形成が可能となる。その結果、プリント配線板の品質安定性を向上させ、プリント配線板の長寿命化が図れることになる。従って、本件出願に係る表面処理銅箔を用いて得られる銅張積層板は、高品質のプリント配線板製造に好適なものである。 The surface-treated copper foil subjected to the roughening treatment on the electrode surface side according to the present application satisfies the above-described conditions, and the surface-treated copper foil and the insulating resin base material constituting the printed wiring board are good, and Adhesion with excellent stability with very little variation can be secured. In addition, good high frequency characteristics can be ensured, and a fine pitch circuit can be formed. As a result, the quality stability of the printed wiring board can be improved and the life of the printed wiring board can be extended. Therefore, the copper clad laminate obtained using the surface-treated copper foil according to the present application is suitable for producing a high-quality printed wiring board.
本件出願に係る表面処理銅箔の粗化処理の形態を説明するための模式図である。It is a schematic diagram for demonstrating the form of the roughening process of the surface treatment copper foil which concerns on this application. 実施例及び比較例で得られた表面処理銅箔の粗化処理の状態を対比するための走査型電子顕微鏡観察像である。It is a scanning electron microscope observation image for contrasting the state of the roughening process of the surface treatment copper foil obtained by the Example and the comparative example.
　以下、本件出願に係る「表面処理銅箔の形態」、「銅張積層板の形態」及び「プリント配線板の形態」に関して説明する。 Hereinafter, the “form of surface-treated copper foil”, “form of copper-clad laminate” and “form of printed wiring board” according to the present application will be described.
表面処理銅箔の形態：　本件出願に係る表面処理銅箔は、電解銅箔の電極面側に粗化処理を施した表面処理銅箔であり、上述の数１に示す要件を満たす粗化処理表面を備えることを特徴とする。本件出願に係る表面処理銅箔１は、図１に模式的に示した表面処理銅箔の断面図をもって、その層構成を容易に理解できる。図１において理解できるように、一般的に、電解銅箔２の析出面側３は、凹凸のある形状を備えている。これに対して、電解銅箔２の電極面側４は、電極表面のレプリカ形状であり、Ｒａ＝０．０５μｍ～０．２５μｍ、Ｒｚ＝０．１μｍ～１．８μｍの範囲の滑らかで光沢を備えた表面である。そして、本件出願に係る表面処理銅箔の場合、当該電解銅箔２の電極面側４に粗化処理を施して、粗化処理表面としている（図１の場合、微細銅粒子５を用いた粗化処理を模式化して示している。）。なお、念のために述べておくが、電解銅箔の両面を平滑化した銅箔を使用する場合には、電解銅箔２の析出面側３も滑らかで光沢を備えた表面となる。 Form of surface-treated copper foil: The surface-treated copper foil according to the present application is a surface-treated copper foil that has been subjected to a roughening treatment on the electrode surface side of the electrolytic copper foil, and the roughening treatment that satisfies the requirement shown in the above-mentioned formula 1 A surface is provided. The surface treatment copper foil 1 which concerns on this application can understand the layer structure easily with sectional drawing of the surface treatment copper foil typically shown in FIG. As can be understood from FIG. 1, generally, the deposition surface side 3 of the electrolytic copper foil 2 has an uneven shape. On the other hand, the electrode surface side 4 of the electrolytic copper foil 2 has a replica shape of the electrode surface, and has a smooth and glossy range of Ra = 0.05 μm to 0.25 μm and Rz = 0.1 μm to 1.8 μm. It is a provided surface. And in the case of the surface-treated copper foil which concerns on this application, it roughens to the electrode surface side 4 of the said electrolytic copper foil 2, and is used as the roughened surface (in the case of FIG. 1, the fine copper particle 5 was used. The roughening treatment is shown schematically.) In addition, as just in case, when using the copper foil which smoothed both surfaces of the electrolytic copper foil, the deposition surface side 3 of the electrolytic copper foil 2 also has a smooth and glossy surface.
　本件出願に係る表面処理銅箔の粗化処理表面の表面粗さ（Ｒｚ）は、２．５μｍ～４．０μｍとしている。この表面粗さ（Ｒｚ）とは、ＪＩＳ規格（ＪＩＳ　Ｂ　０６０１：１９８２）に定める１０点平均粗さである。この表面粗さ（Ｒｚ）が２．５μｍ未満の場合には、絶縁樹脂基材に対する良好なアンカー効果を得ることが出来ず、安定した密着性が得られない。一方、表面粗さ（Ｒｚ）が４．０μｍを超える場合には、電解法を用いて粗化粒子を付着形成しようとすると、析出した粒子に電流が集中して、粗化処理粒子同士が重なり合うように析出するため、形成した回路の引き剥がし強さ、得られるプリント配線板の高周波特性、ファインピッチ回路の形成能にバラツキが生じやすくなる。 The surface roughness (Rz) of the roughened surface of the surface-treated copper foil according to the present application is 2.5 μm to 4.0 μm. This surface roughness (Rz) is a 10-point average roughness defined in JIS standards (JIS B 0601: 1982). When the surface roughness (Rz) is less than 2.5 μm, a good anchor effect for the insulating resin substrate cannot be obtained, and stable adhesion cannot be obtained. On the other hand, when the surface roughness (Rz) exceeds 4.0 μm, when attempting to adhere and form the roughened particles using the electrolytic method, current concentrates on the precipitated particles and the roughened particles overlap each other. Therefore, the peel strength of the formed circuit, the high frequency characteristics of the obtained printed wiring board, and the ability to form a fine pitch circuit tend to vary.
　そして、本件出願に係る表面処理銅箔の場合、上述の表面粗さ（Ｒｚ）に加えて、［Ｒｍａｘ－Ｒａ］として算出される値が、３．５μｍ以下でなければならない。この［Ｒｍａｘ－Ｒａ］という指標が、表面処理銅箔の粗化処理表面と絶縁樹脂基材との密着安定性を考える上で、最も相関性が高いものである。そして、この表面処理銅箔の［Ｒｍａｘ－Ｒａ］として算出される値が３．５μｍを超えると、同一の表面処理銅箔を用いて作製した引き剥がし強さ試料であっても、複数個の試料の引き剥がし強さの測定値のバラツキが大きくなるため好ましくない（以下、この現象を、単に「引き剥がし強さのバラツキ」と称する。）。なお、本件出願では、特に、表面処理銅箔の粗化処理表面の［Ｒｍａｘ－Ｒａ］の下限値を規定していないが、当該表面処理銅箔の粗化処理表面の［Ｒｍａｘ－Ｒａ］は、２．２μｍ程度である。 In the case of the surface-treated copper foil according to the present application, in addition to the surface roughness (Rz) described above, the value calculated as [Rmax−Ra] must be 3.5 μm or less. This index [Rmax−Ra] has the highest correlation in considering the adhesion stability between the roughened surface of the surface-treated copper foil and the insulating resin substrate. When the value calculated as [Rmax−Ra] of this surface-treated copper foil exceeds 3.5 μm, even if it is a peel strength sample produced using the same surface-treated copper foil, This is not preferable because the variation in the measured peel strength of the sample becomes large (hereinafter, this phenomenon is simply referred to as “peeling strength variation”). In the present application, the lower limit value of [Rmax-Ra] of the roughened surface of the surface-treated copper foil is not particularly defined, but [Rmax-Ra] of the roughened surface of the surface-treated copper foil is not limited. About 2.2 μm.
　本件出願に係る表面処理銅箔は、以上に述べた「表面粗さ（Ｒｚ）」、「指標［Ｒｍａｘ－Ｒａ］」に加えて、前記粗化処理表面の表面積比が、１．７～２．４の範囲であることが好ましい。この表面積比は、「レーザー法で表面処理銅箔の粗化処理面の６５５０μｍ２相当の二次元領域を測定したときの表面積（三次元表面積：Ａμｍ２）」と「二次元領域面積」との比［（Ａ）／（６５５０）］で算出される表面積比の値である。この表面積比は、表面処理銅箔と絶縁樹脂基材との接触面積の代替指標である。この表面積比が１．７未満の場合、表面処理銅箔の粗化処理表面と絶縁樹脂基材との間で高い密着性が得られ難くなるため好ましくない。一方、この表面積比が２．４を超えると、表面処理銅箔の粗化処理表面と絶縁樹脂基材との密着性は高くなるが、引き剥がし強さのバラツキが大きくなりやすいため、好ましくない。また、この表面積比が２．４を超えると、得られたプリント配線板の高周波特性も低下する傾向があるため、好ましくない。更に、この表面積比が２．４を超えると、このときの粗化粒子の粒径バラツキも大きくなり、エッチングにより配線を形成する際のファインピッチ回路の形成能が低下するため、好ましくない。 In addition to the “surface roughness (Rz)” and “index [Rmax−Ra]” described above, the surface-treated copper foil according to the present application has a surface area ratio of 1.7 to 2 on the roughened surface. .4 is preferable. This surface area ratio is calculated by comparing the surface area (three-dimensional surface area: Aμm 2 ) when measuring the two-dimensional region corresponding to 6550 μm 2 of the roughened surface of the surface-treated copper foil with the laser method and the “two-dimensional region area”. It is the value of the surface area ratio calculated by the ratio [(A) / (6550)]. This surface area ratio is an alternative index of the contact area between the surface-treated copper foil and the insulating resin base material. When the surface area ratio is less than 1.7, it is difficult to obtain high adhesion between the roughened surface of the surface-treated copper foil and the insulating resin base material. On the other hand, if the surface area ratio exceeds 2.4, the adhesion between the roughened surface of the surface-treated copper foil and the insulating resin base material is increased, but the variation in the peel strength tends to increase, which is not preferable. . Moreover, when this surface area ratio exceeds 2.4, since the high frequency characteristic of the obtained printed wiring board tends to fall, it is not preferable. Further, when the surface area ratio exceeds 2.4, the particle size variation of the roughened particles at this time also increases, and the ability to form a fine pitch circuit when forming a wiring by etching is not preferable.
　また、表面処理銅箔の粗化処理表面が、上述した表面粗さ（Ｒｚ）、［Ｒｍａｘ－Ｒａ］、上述した表面積比を満たす粗化形状を備えると、高周波信号の伝送損失が小さく、伝送損失のバラツキも減少する。高周波信号の伝送損失は、表皮効果を考慮する必要があり、マイクロストリップラインでは、高周波信号は絶縁樹脂基材側を主に伝播する。従って、マイクロストリップラインにおける伝送損失は、「表面処理銅箔の絶縁樹脂層との張り合わせ面である粗化処理表面の粗化形状」及び「配線回路エッジの直線性」の影響が大きい。これに対し、本件出願に係る表面処理銅箔は、後述の実施例に示すように、絶縁樹脂基材（ＦＲ－４基材）と接着すると、周波数が１０ＧＨｚの信号を配線回路幅２２０μｍのマイクロストリップライン経由で伝送する際の伝送損失を、４．０ｄＢ／１０ｃｍ以下にできる。 Further, when the roughened surface of the surface-treated copper foil has a roughened shape that satisfies the above-described surface roughness (Rz), [Rmax−Ra], and the above-mentioned surface area ratio, the transmission loss of high-frequency signals is small, and the transmission Loss variation also decreases. The transmission loss of the high-frequency signal needs to consider the skin effect, and in the microstrip line, the high-frequency signal propagates mainly on the insulating resin base material side. Therefore, the transmission loss in the microstrip line is greatly affected by the “roughened shape of the roughened surface, which is a surface bonded to the insulating resin layer of the surface-treated copper foil” and “linearity of the wiring circuit edge”. On the other hand, the surface-treated copper foil according to the present application, as shown in an example described later, is bonded to an insulating resin base material (FR-4 base material) and outputs a signal having a frequency of 10 GHz to a microcircuit having a wiring circuit width of 220 μm. Transmission loss when transmitting via the stripline can be reduced to 4.0 dB / 10 cm or less.
　ここに述べてきた本件出願に係る表面処理銅箔の粗化処理に電解法を用いる場合には、銅電解液をヤケめっき条件で６０Ｃ／ｄｍ２～２５０Ｃ／ｄｍ２の電気量を用いて、電解銅箔表面に微細銅粒子を析出させる方法を採用することができる。なお、このときの電解液は、銅濃度が５ｇ／Ｌ～２０ｇ／Ｌ、フリー硫酸濃度が５０ｇ／Ｌ～２００ｇ／Ｌ、その他必要に応じた添加剤（例えば、α－ナフトキノリン、デキストリン、ニカワ、チオ尿素等）を含有する液温１５℃～４０℃の銅電解液を用いることが好ましい。 In the case of using an electrolytic method roughening treatment of the surface treated copper foil according to the present application it has been described herein, using an electric quantity of 60C / dm 2 ~ 250C / dm 2 of copper electrolyte in burnt plating conditions, A method of depositing fine copper particles on the surface of the electrolytic copper foil can be employed. In this case, the electrolytic solution has a copper concentration of 5 g / L to 20 g / L, a free sulfuric acid concentration of 50 g / L to 200 g / L, and other additives as necessary (for example, α-naphthoquinoline, dextrin, glue, It is preferable to use a copper electrolyte containing 15 to 40 ° C. containing thiourea or the like.
　そして、当該微細銅粒子が電解銅箔表面から脱落することを防止するため、直ちに、平滑めっき条件を用いて「被せめっき」を行う。この被せめっきでは、平滑な銅めっきができれば、めっき条件に関する特段の限定は無い。例えば、硫酸銅系溶液を用いる場合は、銅濃度が５０ｇ／Ｌ～８０ｇ／Ｌ、フリー硫酸濃度が５０ｇ／Ｌ～１５０ｇ／Ｌ、液温が４０℃～５０℃、電流密度が１０Ａ／ｄｍ２～５０Ａ／ｄｍ２の条件を採用することが好ましい。以上のようにして粗化処理が完了する。 Then, in order to prevent the fine copper particles from falling off the surface of the electrolytic copper foil, “cover plating” is immediately performed using smooth plating conditions. In this covering plating, if smooth copper plating is possible, there is no special limitation regarding plating conditions. For example, when a copper sulfate-based solution is used, the copper concentration is 50 g / L to 80 g / L, the free sulfuric acid concentration is 50 g / L to 150 g / L, the liquid temperature is 40 ° C. to 50 ° C., and the current density is 10 A / dm 2. It is preferable to employ a condition of ˜50 A / dm 2 . As described above, the roughening process is completed.
　以上に述べてきた表面処理銅箔において、使用する電解銅箔２の厚さに関して、特段の限定は無い。本件出願に係る表面処理銅箔において、粗化処理を施す電解銅箔の対象表面は、電解銅箔製造時の電極表面のレプリカ形状を備える電極面側であるため、電解銅箔の厚さに依存して表面粗さが変化するものでは無いからである。 In the surface-treated copper foil described above, there is no particular limitation regarding the thickness of the electrolytic copper foil 2 to be used. In the surface-treated copper foil according to the present application, the target surface of the electrolytic copper foil subjected to the roughening treatment is the electrode surface side provided with the replica shape of the electrode surface at the time of producing the electrolytic copper foil. This is because the surface roughness does not change depending on the above.
　また、本件出願に係る表面処理銅箔は、粗化処理を施した表面に対して、必要に応じて防錆処理、シランカップリング剤処理等を施すことも好ましい。防錆処理としては、無機防錆又は有機防錆を使用することが可能である。無機防錆としては、亜鉛防錆、真鍮防錆、亜鉛－ニッケル合金防錆、亜鉛－コバルト合金防錆、クロメート処理等の使用が可能である。有機防錆としては、イミダゾール類、トリアゾール類等の使用が可能である。そして、絶縁樹脂基材と表面処理銅箔との密着性を向上させるための助剤としての役割を果たすシランカップリング剤処理は、表面処理銅箔の表面と絶縁樹脂基材との濡れ性を改善する。このシランカップリング剤処理には、一般的なエポキシ官能性シランカップリング剤を始めオレフィン官能性シランカップリング剤、アクリル官能性シランカップリング剤等種々のものを用いることができる。 Moreover, it is also preferable that the surface-treated copper foil according to the present application is subjected to a rust prevention treatment, a silane coupling agent treatment, or the like, if necessary, on the roughened surface. As the rust prevention treatment, inorganic rust prevention or organic rust prevention can be used. As inorganic rust prevention, zinc rust prevention, brass rust prevention, zinc-nickel alloy rust prevention, zinc-cobalt alloy rust prevention, chromate treatment, etc. can be used. As organic rust prevention, imidazoles, triazoles and the like can be used. And the silane coupling agent process which plays the role of an auxiliary agent for improving the adhesion between the insulating resin base material and the surface-treated copper foil improves the wettability between the surface of the surface-treated copper foil and the insulating resin base material. Improve. For this silane coupling agent treatment, various materials such as a general epoxy functional silane coupling agent, an olefin functional silane coupling agent, and an acrylic functional silane coupling agent can be used.
銅張積層板の形態：　本件出願に係る銅張積層板は、上述の粗化処理表面を備える表面処理銅箔を用いて得られることを特徴とする。このときの銅張積層板は、本件出願に係る表面処理銅箔を使用して得られるものであれば、使用した絶縁樹脂基材の構成成分、厚さ、積層方法等に関して、特段の限定は無い。また、本件出願に係る銅張積層板は、リジッドタイプ、フレキシブルタイプの双方の概念を含むものである。 Form of copper-clad laminate: The copper-clad laminate according to the present application is obtained by using a surface-treated copper foil having the above-mentioned roughened surface. If the copper clad laminate at this time is obtained using the surface-treated copper foil according to the present application, there are no particular limitations regarding the constituent components, thickness, lamination method, etc. of the insulating resin substrate used. No. Moreover, the copper clad laminated board which concerns on this application contains the concept of both a rigid type and a flexible type.
プリント配線板の形態：　本件出願に係るプリント配線板は、上述の粗化処理表面を備える表面処理銅箔を用いて得られることを特徴とする銅張積層板を用いて、この銅張積層板に対して、公知のエッチング加工、バイアホール加工、めっき加工等のプリント配線板製造に必要な各種加工を施して得られるものである。従って、本件出願に係るプリント配線板には、リジッドタイプのプリント配線板、フレキシブルタイプのプリント配線板、リジッド－フレキタイプのプリント配線板等が含まれ、プリント配線板の種類に関する限定は無い。また、本件出願に係るプリント配線板の層構成に関しても、片面プリント配線板、両面プリント配線板、３層以上の多層プリント配線板の全ての層構成の概念を含むものである。従って、本件出願に係るプリント配線板の場合、絶縁層構成材の種類、絶縁層の厚さに関する限定もないことを明記しておく。 Form of printed wiring board: A printed wiring board according to the present application is obtained by using a surface-treated copper foil provided with the above-mentioned roughened surface, and this copper-clad laminated board is used. On the other hand, it is obtained by performing various processes necessary for manufacturing a printed wiring board, such as a known etching process, via-hole process, and plating process. Therefore, the printed wiring board according to the present application includes a rigid type printed wiring board, a flexible type printed wiring board, a rigid-flex type printed wiring board, and the like, and there is no limitation on the type of the printed wiring board. Further, the layer configuration of the printed wiring board according to the present application also includes the concept of all layer configurations of a single-sided printed wiring board, a double-sided printed wiring board, and a multilayer printed wiring board having three or more layers. Therefore, in the case of the printed wiring board according to the present application, it is clearly stated that there is no limitation on the type of insulating layer constituent material and the thickness of the insulating layer.
表面処理銅箔の製造：　実施例１では、厚さ３５μｍ、電極面側の表面粗さがＲａ＝０．２１μｍ、Ｒｍａｘ＝２．４μｍ、Ｒｚ＝１．４μｍの電解銅箔を用いて、以下の条件で当該電極面側に微細銅粒子を付着形成して、粗化処理を行った。 Production of surface-treated copper foil: In Example 1, an electrolytic copper foil having a thickness of 35 μm and surface roughness on the electrode surface side Ra = 0.21 μm, Rmax = 2.4 μm, Rz = 1.4 μm was used, and the following. Under the conditions, fine copper particles were adhered and formed on the electrode surface side, and roughening treatment was performed.
　電解銅箔を、銅濃度が８ｇ／Ｌ、フリー硫酸濃度が１５０ｇ／Ｌ、添加剤（ニカワ）を含有する液温が２５℃の銅電解液に浸漬し、２００Ｃ／ｄｍ２の電気量を用いて、１０秒間通電し、電極面側の表面に微細銅粒子を析出付着させた。その後、以下の平滑めっき条件を用いて「被せめっき」を行い、微細銅粒子を当該電極面に定着させた。この被せめっきでは、銅濃度が７０ｇ／Ｌ、フリー硫酸濃度が１２０ｇ／Ｌ、液温が４５℃、電流密度が２５Ａ／ｄｍ２の条件を採用した。 The electrolytic copper foil is immersed in a copper electrolytic solution having a copper concentration of 8 g / L, a free sulfuric acid concentration of 150 g / L, and an additive (Nikawa) containing 25 ° C., and an electric quantity of 200 C / dm 2 is used. Then, electricity was applied for 10 seconds to deposit fine copper particles on the electrode side surface. Thereafter, “cover plating” was performed using the following smooth plating conditions to fix the fine copper particles on the electrode surface. In this covering plating, the conditions of a copper concentration of 70 g / L, a free sulfuric acid concentration of 120 g / L, a liquid temperature of 45 ° C., and a current density of 25 A / dm 2 were adopted.
　粗化処理が終了した後、電解銅箔の両面に防錆処理を施した。具体的には、ピロリン酸カリウム濃度が８０ｇ／Ｌ、亜鉛濃度が０．２ｇ／Ｌ、ニッケル濃度が２ｇ／Ｌ、液温が４０℃の溶液に浸漬し、電解銅箔を陰極として、陽極のＳＵＳ板を当該電解銅箔の両側に配置し、電流密度０．５Ａ／ｄｍ２で電解し、電解銅箔の両面に亜鉛－ニッケル合金層を形成した。 After the roughening treatment was completed, rust prevention treatment was performed on both surfaces of the electrolytic copper foil. Specifically, it is immersed in a solution having a potassium pyrophosphate concentration of 80 g / L, a zinc concentration of 0.2 g / L, a nickel concentration of 2 g / L, and a liquid temperature of 40 ° C. SUS plates were placed on both sides of the electrolytic copper foil and electrolyzed at a current density of 0.5 A / dm 2 to form a zinc-nickel alloy layer on both sides of the electrolytic copper foil.
　更に、電解法でクロメート層を形成した。具体的には、クロム酸濃度が１ｇ／Ｌ、ｐＨが１１、液温が２５℃の溶液に浸漬し、電解銅箔を陰極として、ＳＵＳ板を陽極として当該電解銅箔の両側に配置し、電流密度１Ａ／ｄｍ２で電解し、亜鉛－ニッケル合金層の表面にクロメート層を形成し、防錆処理層とした。 Further, a chromate layer was formed by an electrolytic method. Specifically, it is immersed in a solution having a chromic acid concentration of 1 g / L, a pH of 11, and a liquid temperature of 25 ° C., and the electrolytic copper foil is used as a cathode and the SUS plate is used as an anode on both sides of the electrolytic copper foil. Electrolysis was performed at a current density of 1 A / dm 2 , and a chromate layer was formed on the surface of the zinc-nickel alloy layer to obtain a rust-proofing layer.
　当該防錆処理層の形成が完了すると、水洗し、直ちに粗化処理表面の防錆処理層の表面にシランカップリング剤処理を施した。具体的には、γ－グリシドキシプロピルトリメトキシシランをイオン交換水に溶解して濃度が３ｇ／Ｌの水溶液を調製し、この水溶液を粗化処理表面の防錆処理層の全面にシャワーリングし、その後ロールと接触させて液膜厚さを均一にした。 When the formation of the rust-proofing layer was completed, it was washed with water and immediately subjected to a silane coupling agent treatment on the surface of the rust-proofing layer on the roughened surface. Specifically, γ-glycidoxypropyltrimethoxysilane is dissolved in ion-exchanged water to prepare an aqueous solution having a concentration of 3 g / L, and this aqueous solution is showered over the entire surface of the rust-proofing layer on the roughened surface. Then, it was brought into contact with a roll to make the liquid film thickness uniform.
　シランカップリング剤処理が終了すると、銅箔温度が１５０℃になる雰囲気に設定した乾燥炉内に４秒間保持して水分を気散させ、実施例１に係る表面処理銅箔を得た。実施例１で得られた表面処理銅箔の走査型電子顕微鏡観察像を図２に実施例１として示す。 When the silane coupling agent treatment was completed, the surface-treated copper foil according to Example 1 was obtained by dispersing the moisture in a drying furnace set to an atmosphere where the copper foil temperature was 150 ° C. for 4 seconds. A scanning electron microscope observation image of the surface-treated copper foil obtained in Example 1 is shown as Example 1 in FIG.
粗化処理表面の表面粗さ：　得られた実施例１の表面処理銅箔は、粗化処理表面の表面粗さがＲａ＝０．５１μｍ、Ｒｍａｘ＝３．７μｍ、Ｒｚ＝３．０μｍであった。 Surface roughness of roughened surface: The surface-treated copper foil of Example 1 obtained had surface roughness Ra = 0.51 μm, Rmax = 3.7 μm, and Rz = 3.0 μm. It was.
表面処理銅箔の製造：　実施例２では、実施例１の粗化処理の条件において、銅濃度が１２ｇ／Ｌ、フリー硫酸濃度が１５０ｇ／Ｌ、添加剤（ニカワ）を含有する液温２５℃の銅電解液を採用した以外は、実施例１と同様にして表面処理銅箔を製造し、実施例２に係る表面処理銅箔を得た。 Production of surface-treated copper foil: In Example 2, under the conditions of the roughening treatment of Example 1, a liquid temperature of 25 ° C. containing a copper concentration of 12 g / L, a free sulfuric acid concentration of 150 g / L, and an additive (Nikawa) A surface-treated copper foil was produced in the same manner as in Example 1 except that the copper electrolyte solution was used, and a surface-treated copper foil according to Example 2 was obtained.
粗化処理表面の表面粗さ：　得られた実施例２の表面処理銅箔は、粗化処理表面の表面粗さがＲａ＝０．４０μｍ、Ｒｍａｘ＝３．４μｍ、Ｒｚ＝３．０μｍであった。 Surface roughness of roughened surface: The surface-treated copper foil of Example 2 obtained had surface roughness Ra = 0.40 μm, Rmax = 3.4 μm, and Rz = 3.0 μm. It was.
表面処理銅箔の製造：　実施例３では、実施例１の粗化処理の条件において、銅濃度が６ｇ／Ｌ、フリー硫酸濃度が１５０ｇ／Ｌ、添加剤（ニカワ）を含有する液温２５℃の銅電解液を採用した以外は、実施例１と同様にして表面処理銅箔を製造し、実施例３に係る表面処理銅箔を得た。 Production of surface-treated copper foil: In Example 3, under the conditions of the roughening treatment in Example 1, a liquid temperature of 25 ° C. containing a copper concentration of 6 g / L, a free sulfuric acid concentration of 150 g / L, and an additive (Nika) A surface-treated copper foil according to Example 3 was obtained by producing a surface-treated copper foil in the same manner as in Example 1 except that the copper electrolyte solution was used.
粗化処理表面の表面粗さ：　得られた実施例３の表面処理銅箔は、粗化処理表面の表面粗さがＲａ＝０．４８μｍ、Ｒｍａｘ＝３．２μｍ、Ｒｚ＝３．１μｍであった。 Surface roughness of the roughened surface: The surface-treated copper foil of Example 3 obtained had surface roughness Ra = 0.48 μm, Rmax = 3.2 μm, and Rz = 3.1 μm. It was.
［測定方法］
表面粗さ（Ｒｚ）の評価： 上述の粗化処理前の電解銅箔及び表面処理銅箔の粗化処理表面の表面粗さ（Ｒａ、Ｒｍａｘ、Ｒｚ）は、先端のｒが２μｍのダイヤモンドスタイラスを備える触針式の表面粗さ計（（株）小坂研究所製、商品名：ＳＥＦ－３０Ｄ）を用い、ＪＩＳ　Ｂ　０６０１：１９８２に準拠して測定した。 [Measuring method]
Evaluation of surface roughness (Rz): The surface roughness (Ra, Rmax, Rz) of the roughened surface of the electrolytic copper foil and the surface-treated copper foil before the above-mentioned roughening treatment is a diamond stylus whose tip r is 2 μm. Was measured using a stylus type surface roughness meter (trade name: SEF-30D, manufactured by Kosaka Laboratory Ltd.) according to JIS B 0601: 1982.
三次元表面積の評価： 株式会社キーエンス製の超深度カラー３Ｄ形状測定顕微鏡ＶＫ－９５００（使用レーザー：可視光限界波長４０８ｎｍのバイオレットレーザー）を用いて、表面処理銅箔の粗化処理表面の二次元領域面積が６５５０μｍ２の領域について、三次元表面積を測定した。 Evaluation of the three-dimensional surface area: Two-dimensional surface roughening of the surface-treated copper foil using an ultra-deep color 3D shape measuring microscope VK-9500 (used laser: violet laser with a visible light limit wavelength of 408 nm) manufactured by Keyence Corporation A three-dimensional surface area was measured for a region having a region area of 6550 μm 2 .
引き剥がし強さ：　表面処理銅箔の粗化処理表面に、厚さ約１．０ｍｍのＦＲ－４プリプレグを重ね合わせて、２０ｋｇｆ／ｃｍ２（１．９６ＭＰａ）、１８５℃×６０分間の加熱加圧成形を行い片面銅張積層板を作製した。そして、この片面銅張積層板の電解銅箔の表面を整面し、ドライフィルム法を用いて、引き剥がし強さ測定用の幅０．２ｍｍの直線状の配線回路を備える「引き剥がし強さ測定試料」を得た。そして、この「引き剥がし強さ測定試料」を用いて、ＪＩＳ Ｃ ６４８１に準拠して、引き剥がし強さを測定した。 Peel strength: The roughened surface of the surface-treated copper foil was overlaid with a FR-4 prepreg having a thickness of about 1.0 mm and heated at 20 kgf / cm 2 (1.96 MPa) at 185 ° C. for 60 minutes. A single-sided copper clad laminate was produced by pressure forming. Then, the surface of the electrolytic copper foil of this single-sided copper clad laminate is leveled, and the dry film method is used to provide a linear wiring circuit having a width of 0.2 mm for measuring the peeling strength. A measurement sample "was obtained. Then, using this “peeling strength measurement sample”, the peeling strength was measured according to JIS C 6481.
高周波特性：　ここでの高周波特性は、アンリツ株式会社製　ベクトルネットワークアナライザー（ＶＮＡ）　３７２００Ｂシリーズ（型番：３７２４７Ｃ）で、１０ＧＨｚの高周波信号を用いて、基材厚さ６０μｍ、配線回路幅２２０μｍのマイクロストリップライン経由で伝送する際の伝送損失を評価した。そして、このときの伝送損失が４．０ｄＢ／１０ｃｍ以下になるか否かで良否を判断した。伝送損失が４．０ｄＢ／１０ｃｍ以下の場合に「○」と評価し、伝送損失が４．０ｄＢ／１０ｃｍを超える場合に「×」と評価した。 High-frequency characteristic: The high-frequency characteristic here is a vector network analyzer (VNA) 37200B series (model number: 37247C) manufactured by Anritsu Corporation, using a high-frequency signal of 10 GHz, a substrate thickness of 60 μm, and a wiring circuit width of 220 μm. The transmission loss when transmitting via the line was evaluated. And the quality was judged by whether the transmission loss at this time became 4.0 dB / 10 cm or less. When the transmission loss was 4.0 dB / 10 cm or less, it was evaluated as “◯”, and when the transmission loss exceeded 4.0 dB / 10 cm, it was evaluated as “x”.
比較例Comparative example
［比較例１］
表面処理銅箔の製造：　比較例１では、実施例１の粗化処理条件において、電気量を５０Ｃ／ｄｍ２とした以外は、実施例１と同様にして表面処理銅箔を製造し、比較例１に係る表面処理銅箔を得た。比較例１で得られた表面処理銅箔の走査型電子顕微鏡観察像を図２に比較例１として示す。 [Comparative Example 1]
Production of surface-treated copper foil: In Comparative Example 1, a surface-treated copper foil was produced in the same manner as in Example 1 except that the amount of electricity was 50 C / dm 2 under the roughening treatment conditions in Example 1. A surface-treated copper foil according to Example 1 was obtained. A scanning electron microscope observation image of the surface-treated copper foil obtained in Comparative Example 1 is shown as Comparative Example 1 in FIG.
粗化処理表面の表面粗さ：　得られた比較例１の表面処理銅箔は、粗化処理表面の表面粗さがＲａ＝０．４４μｍ、Ｒｍａｘ＝４．０μｍ、Ｒｚ＝３．６μｍであった。 Surface roughness of roughened surface: The surface-treated copper foil of Comparative Example 1 obtained had surface roughness Ra = 0.44 μm, Rmax = 4.0 μm, Rz = 3.6 μm. It was.
［比較例２］
表面処理銅箔の製造：　比較例２では、実施例１の粗化処理の条件において、電気量を３００Ｃ／ｄｍ２とした以外は、実施例１と同様にして表面処理銅箔を製造し、比較例２に係る表面処理銅箔を得た。比較例２で得られた表面処理銅箔の走査型電子顕微鏡観察像を図２に比較例２として示す。 [Comparative Example 2]
Production of surface-treated copper foil: In Comparative Example 2, a surface-treated copper foil was produced in the same manner as in Example 1 except that the amount of electricity was 300 C / dm 2 under the conditions of the roughening treatment in Example 1. A surface-treated copper foil according to Comparative Example 2 was obtained. A scanning electron microscope observation image of the surface-treated copper foil obtained in Comparative Example 2 is shown as Comparative Example 2 in FIG.
粗化処理表面の表面粗さ：　得られた比較例２の表面処理銅箔は、粗化処理表面の表面粗さがＲａ＝０．８９μｍ、Ｒｍａｘ＝６．５μｍ、Ｒｚ＝５．１μｍであった。 Surface roughness of the roughened surface: The surface-treated copper foil of Comparative Example 2 obtained had surface roughness Ra = 0.89 μm, Rmax = 6.5 μm, Rz = 5.1 μm. It was.
［比較例３］
　比較例３では、特許文献２の実施例で採用した粗化処理条件を使用して、本件出願の実施例１と同様の電解銅箔に粗化処理を施した。即ち、以下のとおりである。 [Comparative Example 3]
In Comparative Example 3, using the roughening treatment conditions employed in the example of Patent Document 2, the same electrolytic copper foil as Example 1 of the present application was subjected to the roughening treatment. That is, it is as follows.
表面処理銅箔の製造： 電解銅箔を、銅濃度が１０ｇ／Ｌ、フリー硫酸濃度が１００ｇ／Ｌを含有する液温３０℃の銅電解液に浸漬し、２５０Ｃ／ｄｍ２の電気量を用いて、１０秒間通電し、電極面側の表面に微細銅粒子を析出付着させた。その後、以下の平滑めっき条件を用いて「被せめっき」を行い、微細銅粒子を当該電極面に定着させた。この被せめっきでは、銅濃度が７０ｇ／Ｌ、フリー硫酸濃度が１５０ｇ／Ｌ、液温が４５℃、電流密度が６０Ａ／ｄｍ２の条件を採用した。 Production of surface-treated copper foil: The electrolytic copper foil is immersed in a copper electrolyte at a liquid temperature of 30 ° C. containing a copper concentration of 10 g / L and a free sulfuric acid concentration of 100 g / L, and an electric quantity of 250 C / dm 2 is used. Then, electricity was applied for 10 seconds to deposit fine copper particles on the electrode side surface. Thereafter, “cover plating” was performed using the following smooth plating conditions to fix the fine copper particles on the electrode surface. In this covering plating, the conditions of a copper concentration of 70 g / L, a free sulfuric acid concentration of 150 g / L, a liquid temperature of 45 ° C., and a current density of 60 A / dm 2 were adopted.
　粗化処理が終了すると、無機防錆処理を施した。具体的には、ピロリン酸カリウム濃度が８０ｇ／Ｌ、亜鉛濃度が０．２ｇ／Ｌ、ニッケル濃度が２ｇ／Ｌ、液温が４０℃の溶液に浸漬し、電解銅箔を陰極に分極することにより、当該電解銅箔の粗化処理面に亜鉛－ニッケル合金層を形成した。更に、この亜鉛－ニッケル合金層の表面に、電解法でクロメート層を形成した。具体的には、クロム酸濃度が１ｇ／Ｌ、ｐＨが１１、液温が２５℃の溶液に浸漬し、電解銅箔を陰極に分極して、粗化処理面にクロメート層を形成し、防錆処理層とした。 When the roughening treatment was completed, inorganic rust prevention treatment was performed. Specifically, it is immersed in a solution having a potassium pyrophosphate concentration of 80 g / L, a zinc concentration of 0.2 g / L, a nickel concentration of 2 g / L, and a liquid temperature of 40 ° C., and the electrolytic copper foil is polarized to the cathode. Thus, a zinc-nickel alloy layer was formed on the roughened surface of the electrolytic copper foil. Further, a chromate layer was formed on the surface of the zinc-nickel alloy layer by an electrolytic method. Specifically, it is immersed in a solution having a chromic acid concentration of 1 g / L, a pH of 11, and a liquid temperature of 25 ° C., and the electrolytic copper foil is polarized to the cathode to form a chromate layer on the roughened surface. A rust-treated layer was obtained.
　当該防錆処理層の形成が完了すると、水洗し、直ちに粗化処理表面の防錆処理層の表面に、シランカップリング剤処理を施した。具体的には、γ－グリシドキシプロピルトリメトキシシランをイオン交換水に溶解して濃度が３ｇ／Ｌの水溶液を調製し、この水溶液を粗化処理表面の全面が濡れるようにシャワーリングし、銅箔温度が１５０℃になる雰囲気に設定した乾燥炉内に４秒間保持して水分を気散させて、比較例３に係る表面処理銅箔を得た。比較例３で得られた表面処理銅箔の走査型電子顕微鏡観察像を図２に比較例３として示す。 When the formation of the rust-proofing layer was completed, it was washed with water and immediately subjected to a silane coupling agent treatment on the surface of the rust-proofing layer on the roughened surface. Specifically, γ-glycidoxypropyltrimethoxysilane was dissolved in ion-exchanged water to prepare an aqueous solution having a concentration of 3 g / L, and this aqueous solution was showered so that the entire surface of the roughened surface was wetted, The surface-treated copper foil which concerns on the comparative example 3 was obtained by hold | maintaining for 4 second in the drying furnace set to the atmosphere which set copper foil temperature to 150 degreeC, and disperse | distributing a water | moisture content. A scanning electron microscope observation image of the surface-treated copper foil obtained in Comparative Example 3 is shown as Comparative Example 3 in FIG.
粗化処理表面の表面粗さ：　得られた比較例３の表面処理銅箔は、粗化処理表面の表面粗さがＲａ＝０．５０μｍ、Ｒｍａｘ＝４．４μｍ、Ｒｚ＝４．０μｍであった。 Surface roughness of roughened surface: The surface-treated copper foil of Comparative Example 3 obtained had surface roughness Ra = 0.50 μm, Rmax = 4.4 μm, and Rz = 4.0 μm. It was.
［実施例と比較例との対比］
　以下、実施例と比較例との対比を行うにあたり、以下の表１に実施例と比較例との評価結果を纏めて列挙する。 [Contrast between Example and Comparative Example]
Hereinafter, in comparing the examples and the comparative examples, the evaluation results of the examples and the comparative examples are listed in Table 1 below.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　実施例１～実施例３をみると、表面粗さ（Ｒｚ）、［Ｒｍａｘ－Ｒａ］、表面積比のそれぞれの値が、いずれも本件出願において適正とする範囲に入っており、引き剥がし強さも１．４０ｋｇｆ／ｃｍ以上と良好な値を示していることがわかる。また、これら実施例１～実施例３は、信号の伝送特性が良好であり、高周波特性に優れるといえる。 Looking at Examples 1 to 3, the values of the surface roughness (Rz), [Rmax−Ra], and the surface area ratio are all within the appropriate ranges in the present application, and the peel strength is also It can be seen that 1.40 kgf / cm or more is a good value. In addition, it can be said that Examples 1 to 3 have excellent signal transmission characteristics and excellent high frequency characteristics.
　これに対し、比較例１は、表面粗さ（Ｒｚ）が本件出願において適正とする範囲に入っているものの、［Ｒｍａｘ－Ｒａ］は本件出願において適正とする範囲から外れている。また、比較例１は、粗化処理が不十分なため、粗化処理面の表面積比が低い値になっており、本件出願において適正とする範囲から外れている。このことは、図２の顕微鏡観察像からも理解できる。比較例１は、高周波特性は良好であっても、引き剥がし強さが１．２８ｋｇｆ／ｃｍと低い。 In contrast, in Comparative Example 1, the surface roughness (Rz) is within the appropriate range in the present application, but [Rmax-Ra] is not within the appropriate range in the present application. Moreover, since the roughening process is inadequate in the comparative example 1, the surface area ratio of the roughening process surface is a low value, and is outside the range considered appropriate in this application. This can be understood from the microscopic observation image of FIG. Although Comparative Example 1 has good high frequency characteristics, the peel strength is as low as 1.28 kgf / cm.
　比較例２では、粗化処理が過剰なため、図２から理解できるように、微細銅粒子の粒径が大きくなっている。そして、表面粗さ（Ｒｚ）及び［Ｒｍａｘ－Ｒａ］の値が、本件出願において適正とする範囲から外れている。また、比較例２は、表面積比に関しても、実施例１や実施例２に比べ低い値になっている。その結果、比較例２は、粒径の大きな微細銅粒子のアンカー効果により、引き剥がし強さが１．５３ｋｇｆ／ｃｍと高い値を示しているものの、信号の伝送特性が低下しており、良好な高周波特性を備えているとはいえない。 In Comparative Example 2, since the roughening treatment is excessive, the particle diameter of the fine copper particles is large as can be understood from FIG. Further, the values of the surface roughness (Rz) and [Rmax−Ra] are out of the proper ranges in the present application. In Comparative Example 2, the surface area ratio is also lower than that in Example 1 or Example 2. As a result, although Comparative Example 2 shows a high peel strength of 1.53 kgf / cm due to the anchor effect of fine copper particles having a large particle size, the signal transmission characteristics are poor and good It cannot be said that it has a high frequency characteristic.
　比較例３では、図２から理解できるように、実施例１に比べて微細銅粒子の粒径が、僅かに大きくなっているに過ぎないように思われる。表面粗さ（Ｒｚ）も本件出願において適正とする範囲に入っている。しかしながら、［Ｒｍａｘ－Ｒａ］の値は、本件出願において適正とする範囲から外れている比較例１よりもさらに高い値となっており、表面積比は、本件出願において適正とする範囲からやや低い値となっている。その結果、引き剥がし強さが１．３６ｋｇｆ／ｃｍとやや低く、信号の伝送特性も低下しており、良好な高周波特性を備えているとはいえない。 In Comparative Example 3, as can be understood from FIG. 2, it seems that the particle diameter of the fine copper particles is only slightly larger than that in Example 1. The surface roughness (Rz) is also within the appropriate range in the present application. However, the value of [Rmax−Ra] is a higher value than Comparative Example 1 that is outside the appropriate range in the present application, and the surface area ratio is slightly lower than the appropriate range in the present application. It has become. As a result, the peel strength is slightly low at 1.36 kgf / cm, the signal transmission characteristics are also deteriorated, and it cannot be said that the high frequency characteristics are provided.
　以上のことから理解できるように、表面粗さ（Ｒｚ）及び［Ｒｍａｘ－Ｒａ］、さらには、表面積比が本件出願において適正とする範囲内である粗化処理表面は、引き剥がし強さも十分な値を確保することができると共に、信号の伝送特性も良好で、高周波特性に優れたものとなっている。 As can be understood from the above, the surface roughness (Rz) and [Rmax−Ra], and further, the roughened surface having a surface area ratio within the appropriate range in the present application has sufficient peel strength. The value can be secured, the signal transmission characteristics are good, and the high frequency characteristics are excellent.
　よって、本件出願に係る表面処理銅箔は、粗化処理表面の表面粗さ（Ｒｚ）及び［Ｒｍａｘ－Ｒａ］、さらには、表面積比が所定の範囲以内であるため、絶縁樹脂基材との密着性のバラツキが極めて少なく、良好な密着性を実現できると同時に、本来であれば、密着性とは相反する特性である「良好な信号の伝送特性を備える回路」の形成が可能となる。 Therefore, the surface-treated copper foil according to the present application has the surface roughness (Rz) and [Rmax-Ra] of the roughened surface, and the surface area ratio is within a predetermined range. It is possible to form a “circuit having a good signal transmission characteristic”, which is a characteristic contrary to the adhesiveness.
　以上に述べた本件出願に係る表面処理銅箔は、絶縁樹脂基材との密着性のバラツキが極めて少ないため、「絶縁樹脂基材との良好な密着性」及び「高周波特性に優れる回路形成が可能」という相反する特性のバランスに優れる製品である。従って、本件出願に係る表面処理銅箔を用いて製造した銅張積層板を、プリント配線板の基礎材料として用いると、絶縁樹脂基材に対する良好な密着性を備えるファインピッチ回路を備え、高周波信号の伝送損失が少なく、設計品質通りの特性インピーダンスを備えるプリント配線板の提供が可能となる。 Since the surface-treated copper foil according to the present application described above has very little variation in adhesion with the insulating resin base material, the circuit forming excellent in high frequency characteristics can be achieved with “good adhesion with the insulating resin base material”. It is a product that has an excellent balance of conflicting characteristics. Therefore, when a copper clad laminate produced using the surface-treated copper foil according to the present application is used as a basic material of a printed wiring board, it is equipped with a fine pitch circuit having good adhesion to an insulating resin substrate, and a high frequency signal Therefore, it is possible to provide a printed wiring board having a characteristic impedance equivalent to the design quality.

Claims (5)

  1. 電解銅箔の電極面側に粗化処理を施した表面処理銅箔であって、以下の数１に示す要件を満たす粗化処理表面を備えることを特徴とする表面処理銅箔。
    Figure JPOXMLDOC01-appb-M000001
         A surface-treated copper foil, which is a surface-treated copper foil that has been subjected to a roughening treatment on the electrode surface side of the electrolytic copper foil, the surface-treated copper foil satisfying the requirements shown in the following formula 1.
    Figure JPOXMLDOC01-appb-M000001
  2. 前記粗化処理表面の表面積比が１．７～２．４である請求項１に記載の表面処理銅箔。 The surface-treated copper foil according to claim 1, wherein a surface area ratio of the roughened surface is 1.7 to 2.4.
  3. 前記粗化処理を施した表面に対して、必要に応じて防錆処理、シランカップリング剤処理等を施した請求項１又は請求項２に記載の表面処理銅箔。 The surface-treated copper foil of Claim 1 or Claim 2 which performed the antirust process, the silane coupling agent process, etc. with respect to the surface which gave the said roughening process as needed.
  4. 請求項１～請求項３のいずれか１項に記載の表面処理銅箔を用いて得られることを特徴とする銅張積層板。 A copper-clad laminate obtained by using the surface-treated copper foil according to any one of claims 1 to 3.
  5. 請求項４に記載の銅張積層板を用いて得られることを特徴とするプリント配線板。 A printed wiring board obtained by using the copper-clad laminate according to claim 4.
PCT/JP2014/073026 2013-09-05 2014-09-02 Surface-processed copper foil, copper clad laminate obtained using such surface-processed copper foil, and printed wiring board WO2015033917A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2015515307A JP6722452B2 (en) 2013-09-05 2014-09-02 Surface-treated copper foil, copper-clad laminate obtained by using the surface-treated copper foil, and printed wiring board

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013-184092 2013-09-05
JP2013184092 2013-09-05

Publications (1)

Publication Number Publication Date
WO2015033917A1 true WO2015033917A1 (en) 2015-03-12

Family

ID=52628391

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2014/073026 WO2015033917A1 (en) 2013-09-05 2014-09-02 Surface-processed copper foil, copper clad laminate obtained using such surface-processed copper foil, and printed wiring board

Country Status (3)

Country Link
JP (2) JP6722452B2 (en)
TW (1) TWI515342B (en)
WO (1) WO2015033917A1 (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20170137932A (en) 2015-07-03 2017-12-13 미쓰이금속광업주식회사 Roughened copper foil, copper clad laminate and printed wiring board
WO2019131092A1 (en) * 2017-12-26 2019-07-04 Ｊｘ金属株式会社 Copper foil for heat dissapation and heat disspating member
JP2020076151A (en) * 2018-11-05 2020-05-21 金居開發股▲分▼有限公司 Microroughened electrolytic copper foil and copper-clad substrate with the same
WO2020105289A1 (en) * 2018-11-19 2020-05-28 三井金属鉱業株式会社 Surface-treated copper foil, carrier-attached copper foil, copper-clad laminate, and printed wiring board
KR20220044746A (en) 2020-06-11 2022-04-11 미쓰이금속광업주식회사 Double-sided copper clad laminate
CN114929944A (en) * 2019-12-24 2022-08-19 日本电解株式会社 Surface-treated copper foil and method for producing same

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20230161954A (en) * 2021-03-29 2023-11-28 미쓰이금속광업주식회사 Roughened copper foil, copper clad laminate and printed wiring board

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08158100A (en) * 1994-10-06 1996-06-18 Furukawa Circuit Foil Kk Roughening of copper foil surface
JPH10330983A (en) * 1997-05-30 1998-12-15 Fukuda Metal Foil & Powder Co Ltd Electrolytic copper foil and its production
JPH11340595A (en) * 1998-05-21 1999-12-10 Furukawa Electric Co Ltd:The Copper foil for printed circuit board and copper foil attached with resin
JPH11340596A (en) * 1998-05-21 1999-12-10 Furukawa Electric Co Ltd:The Copper foil for printed circuit board and copper foil attached with resin
WO2003102277A1 (en) * 2002-06-04 2003-12-11 Mitsui Mining & Smelting Co.,Ltd. Surface treatment copper foil for low dielectric substrate, copper clad laminate including the same and printed wiring board
JP2004152904A (en) * 2002-10-29 2004-05-27 Kyocera Corp Electrolytic copper foil, film and multilayer wiring substrate therewith, and method of manufacturing the same
JP2004256910A (en) * 2003-02-04 2004-09-16 Furukawa Techno Research Kk Copper foil for high-frequency circuit, manufacturing method therefor, manufacturing facility therefor, and high-frequency circuit using the copper foil
JP2008226800A (en) * 2007-03-16 2008-09-25 Fukuda Metal Foil & Powder Co Ltd Copper foil for lithium secondary battery negative electrode collector and its manufacturing method
WO2013002279A1 (en) * 2011-06-30 2013-01-03 古河電気工業株式会社 Electrolytic copper foil, method for producing electrolytic copper foil, and lithium ion secondary cell using electrolytic copper foil as collector
JP2013091825A (en) * 2011-10-25 2013-05-16 Furukawa Electric Co Ltd:The Electrolytic copper foil for lithium ion secondary battery and production method thereof
JP2013133514A (en) * 2011-12-27 2013-07-08 Furukawa Electric Co Ltd:The Copper foil, electrode for secondary battery, secondary battery, and printed circuit board

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2563118B2 (en) * 1987-12-26 1996-12-11 日鉱金属株式会社 Copper or copper alloy material for flexible printed circuit board and manufacturing method thereof
JPH07273458A (en) * 1994-03-31 1995-10-20 Hitachi Chem Co Ltd Manufacturing method of multilayer-wiring board
JP3281783B2 (en) * 1995-12-06 2002-05-13 三井金属鉱業株式会社 Copper foil for printed wiring board, method for producing the same, and electrolytic apparatus
JPH10212365A (en) * 1996-11-29 1998-08-11 Mitsui Chem Inc Resin molding and its production
JP2005154815A (en) * 2003-11-21 2005-06-16 Mitsui Mining & Smelting Co Ltd Copper electrolytic solution in manufacturing electrolytic copper foil, and method for manufacturing electrolytic copper foil
JP5129642B2 (en) * 2007-04-19 2013-01-30 三井金属鉱業株式会社 Surface treated copper foil, copper clad laminate obtained using the surface treated copper foil, and printed wiring board obtained using the copper clad laminate
JP5391366B2 (en) * 2011-06-28 2014-01-15 古河電気工業株式会社 Electrolytic copper foil, wiring board using the electrolytic copper foil, and flexible wiring board
KR20140054435A (en) * 2011-09-30 2014-05-08 제이엑스 닛코 닛세키 킨조쿠 가부시키가이샤 Copper foil excellent in adhesion with resin, method for manufacturing same, and printed wiring board or battery negative electrode material using electrolytic copper foil

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08158100A (en) * 1994-10-06 1996-06-18 Furukawa Circuit Foil Kk Roughening of copper foil surface
JPH10330983A (en) * 1997-05-30 1998-12-15 Fukuda Metal Foil & Powder Co Ltd Electrolytic copper foil and its production
JPH11340595A (en) * 1998-05-21 1999-12-10 Furukawa Electric Co Ltd:The Copper foil for printed circuit board and copper foil attached with resin
JPH11340596A (en) * 1998-05-21 1999-12-10 Furukawa Electric Co Ltd:The Copper foil for printed circuit board and copper foil attached with resin
WO2003102277A1 (en) * 2002-06-04 2003-12-11 Mitsui Mining & Smelting Co.,Ltd. Surface treatment copper foil for low dielectric substrate, copper clad laminate including the same and printed wiring board
JP2004152904A (en) * 2002-10-29 2004-05-27 Kyocera Corp Electrolytic copper foil, film and multilayer wiring substrate therewith, and method of manufacturing the same
JP2004256910A (en) * 2003-02-04 2004-09-16 Furukawa Techno Research Kk Copper foil for high-frequency circuit, manufacturing method therefor, manufacturing facility therefor, and high-frequency circuit using the copper foil
JP2008226800A (en) * 2007-03-16 2008-09-25 Fukuda Metal Foil & Powder Co Ltd Copper foil for lithium secondary battery negative electrode collector and its manufacturing method
WO2013002279A1 (en) * 2011-06-30 2013-01-03 古河電気工業株式会社 Electrolytic copper foil, method for producing electrolytic copper foil, and lithium ion secondary cell using electrolytic copper foil as collector
JP2013091825A (en) * 2011-10-25 2013-05-16 Furukawa Electric Co Ltd:The Electrolytic copper foil for lithium ion secondary battery and production method thereof
JP2013133514A (en) * 2011-12-27 2013-07-08 Furukawa Electric Co Ltd:The Copper foil, electrode for secondary battery, secondary battery, and printed circuit board

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20170137932A (en) 2015-07-03 2017-12-13 미쓰이금속광업주식회사 Roughened copper foil, copper clad laminate and printed wiring board
JP7068341B2 (en) 2017-12-26 2022-05-16 Ｊｘ金属株式会社 Heat-dissipating copper foil and heat-dissipating members
WO2019131092A1 (en) * 2017-12-26 2019-07-04 Ｊｘ金属株式会社 Copper foil for heat dissapation and heat disspating member
KR20200090207A (en) * 2017-12-26 2020-07-28 제이엑스금속주식회사 Copper foil for heat dissipation and heat dissipation member
JPWO2019131092A1 (en) * 2017-12-26 2020-12-03 Ｊｘ金属株式会社 Copper foil for heat dissipation and heat dissipation member
KR102461590B1 (en) * 2017-12-26 2022-11-01 제이엑스금속주식회사 Copper foil for heat dissipation and heat dissipation member
JP2020076151A (en) * 2018-11-05 2020-05-21 金居開發股▲分▼有限公司 Microroughened electrolytic copper foil and copper-clad substrate with the same
US11186918B2 (en) 2018-11-05 2021-11-30 Co-Tech Development Corp. Micro-roughened electrodeposited copper foil and copper clad laminate using the same
WO2020105289A1 (en) * 2018-11-19 2020-05-28 三井金属鉱業株式会社 Surface-treated copper foil, carrier-attached copper foil, copper-clad laminate, and printed wiring board
JP7453154B2 (en) 2018-11-19 2024-03-19 三井金属鉱業株式会社 Surface treated copper foil, copper foil with carrier, copper clad laminates and printed wiring boards
CN114929944A (en) * 2019-12-24 2022-08-19 日本电解株式会社 Surface-treated copper foil and method for producing same
EP4083272A4 (en) * 2019-12-24 2023-01-11 Nippon Denkai, Ltd. Surface-treated copper foil and method for manufacturing same
US11952675B2 (en) 2019-12-24 2024-04-09 Nippon Denkai, Ltd. Surface-treated copper foil and method for manufacturing same
KR20220044746A (en) 2020-06-11 2022-04-11 미쓰이금속광업주식회사 Double-sided copper clad laminate
US11670455B2 (en) 2020-06-11 2023-06-06 Mitsui Mining & Smelting Co., Ltd. Double-sided copper-clad laminate

Also Published As

Publication number Publication date
JP2020109216A (en) 2020-07-16
TW201512468A (en) 2015-04-01
JPWO2015033917A1 (en) 2017-03-02
TWI515342B (en) 2016-01-01
JP6893572B2 (en) 2021-06-23
JP6722452B2 (en) 2020-07-15

Similar Documents

Publication Publication Date Title
JP6893572B2 (en) Surface-treated copper foil manufacturing method
TWI619409B (en) Method for manufacturing surface-treated copper foil, laminated board, printed wiring board, electronic device, copper foil with carrier and printed wiring board
JP6682516B2 (en) Roughened copper foil and printed wiring board
JP5129642B2 (en) Surface treated copper foil, copper clad laminate obtained using the surface treated copper foil, and printed wiring board obtained using the copper clad laminate
CN1657279B (en) Treated copper foil and circuit board
JP5871426B2 (en) Surface treated copper foil for high frequency transmission, laminated plate for high frequency transmission and printed wiring board for high frequency transmission
JP6487704B2 (en) Treated copper foil, copper-clad laminate using the treated copper foil, and printed wiring board
KR102274906B1 (en) Copper foil and copper clad laminate having the same
TWI627307B (en) Surface-treated copper foil for printed wiring board, copper-clad laminate for printed wiring board, and printed wiring board
JP2006103189A (en) Surface-treated copper foil and circuit board
JP7374298B2 (en) Roughened copper foil, copper clad laminates and printed wiring boards
JP2007186797A (en) Method for producing ultrathin copper foil with carrier, ultrathin copper foil produced by the production method, and printed circuit board, multilayer printed circuit board and wiring board for chip on film using the ultrathin copper foil
JP2017106069A (en) Surface treated copper foil for printed wiring board, copper clad laminate for printed wiring board and printed wiring board
JP2015124426A (en) Surface-treated copper foil and laminate
JP5576514B2 (en) Surface-treated copper foil, laminated board, printed wiring board and printed circuit board
JP6687409B2 (en) High chroma treated copper foil, copper clad laminate using the treated copper foil, and method for producing the treated copper foil
TW202030379A (en) Surface-treated copper foil, copper-cladded laminate plate, and printed wiring board
JP2015105440A (en) Surface treated copper foil, laminate, printed wiring board, printed circuit board and electronic apparatus
JP4615226B2 (en) Composite material for substrate and circuit board using the same
JP2016141823A (en) Surface-treated copper foil and laminate sheet
WO2020246467A1 (en) Surface-treated copper foil, copper-clad laminate plate, and printed wiring board
TW202302920A (en) Surface-treated copper foil
JP2005159239A (en) High frequency copper foil and copper clad laminate using the same
WO2022255422A1 (en) Roughened copper foil, copper-clad laminate board, and printed circuit board
WO2022209990A1 (en) Roughened copper foil, copper-clad laminate and printed wiring board

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2015515307

Country of ref document: JP

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14841735

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14841735

Country of ref document: EP

Kind code of ref document: A1