WO2013108415A1 - 銅張積層板用表面処理銅箔及びそれを用いた銅張積層板 - Google Patents
銅張積層板用表面処理銅箔及びそれを用いた銅張積層板 Download PDFInfo
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- WO2013108415A1 WO2013108415A1 PCT/JP2012/055594 JP2012055594W WO2013108415A1 WO 2013108415 A1 WO2013108415 A1 WO 2013108415A1 JP 2012055594 W JP2012055594 W JP 2012055594W WO 2013108415 A1 WO2013108415 A1 WO 2013108415A1
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- roughening
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- 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
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- 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
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- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
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- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/04—Wires; Strips; Foils
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- 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
- C25D3/22—Electroplating: Baths therefor from solutions of zinc
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- 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
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- 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
- C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper
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- 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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
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- 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
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- 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
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- 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
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- 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
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- 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
- B32B2250/00—Layers arrangement
- B32B2250/03—3 layers
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- 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
- B32B2250/00—Layers arrangement
- B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
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- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/412—Transparent
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- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/538—Roughness
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- 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
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- 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
- H05K2201/01—Dielectrics
- H05K2201/0104—Properties and characteristics in general
- H05K2201/0108—Transparent
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- 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
Definitions
- the present invention relates to a surface-treated copper foil for a copper-clad laminate and a copper-clad laminate using the same, and in particular, a copper-clad laminate suitable for a field where transparency of the remaining resin after etching the copper foil is required.
- the present invention relates to a surface-treated copper foil for plates and a copper-clad laminate using the same.
- FPCs flexible printed wiring boards
- the signal transmission speed has been increased, and impedance matching has become an important factor in FPC.
- a resin insulation layer for example, polyimide
- the FPC is processed such as bonding to a liquid crystal substrate and mounting of an IC chip. The alignment at this time is visible through the resin insulation layer remaining after etching the copper foil of the copper clad laminate. Therefore, the visibility of the resin insulating layer is important.
- a copper clad laminated board can also be manufactured even if it uses the rolled copper foil by which the roughening plating was given to the surface.
- This rolled copper foil usually uses tough pitch copper (oxygen content of 100 to 500 ppm by weight) or oxygen free copper (oxygen content of 10 ppm by weight or less) as a raw material, and after hot rolling these ingots, It is manufactured by repeating cold rolling and annealing to a thickness.
- Patent Document 1 proposes to use a low-roughness electrolytic foil having a high surface glossiness as a conductor layer.
- Patent Document 2 proposes a rolled copper foil having an oil pit depth of 2.0 ⁇ m or less on the surface formed by a cold rolling process under conditions such as oil film control as a copper foil having excellent flexibility. ing.
- Patent Document 1 a low-roughness copper foil obtained by improving adhesion with an organic treatment agent after blackening treatment or plating treatment is broken due to fatigue in applications where flexibility is required for a copper-clad laminate. May be inferior in resin transparency. Further, even if a rolled copper foil having an oil pit state as described in Patent Document 2 is used, sufficient transparency of the resin cannot be obtained. Thus, in the prior art, the resin transparency after removing the rolled copper foil by etching was low, and the chip alignment could not be performed smoothly.
- the present invention provides a copper foil for a copper-clad laminate, which adheres well to a resin and is excellent in resin transparency after the copper foil is removed by etching.
- a surface-treated copper foil in which roughened particles are formed on the surface of the copper foil by a roughening treatment, and the surface of the roughened surface has a particle size of 0.
- Coarse particles having a particle size of 0 to 42 particles / ⁇ m 2 and a particle size of 0.10 ⁇ m or more but less than 0.30 ⁇ m are 0 to 25 particles / ⁇ m 2 and a particle size of 0.30 ⁇ m or more and less than 1.0 ⁇ m.
- a surface-treated copper foil for copper-clad laminate in which roughened particles having a particle size of 0 to 10 particles / ⁇ m 2 and roughened particles having a particle diameter of 1.0 ⁇ m or more are formed in an amount of 0 to 0.1 particles / ⁇ m 2 .
- the roughened surface has 10 to 42 roughened particles having a particle size of less than 0.10 ⁇ m / ⁇ m 2 and a particle size of 0.1 ⁇ m. 10 ⁇ m or 0.30 .mu.m less roughening particles 0 to 10 / [mu] m 2, with roughening particles of less than a particle size 0.30 .mu.m 1.0 .mu.m is 0-5 / [mu] m 2, the particle size 1.0 .mu.m or more It is formed without roughening particles.
- the roughened surface has 15 to 42 roughened particles having a particle size of less than 0.10 ⁇ m / ⁇ m 2 and a particle size of 0. more .10Myuemu 0.30 .mu.m less roughening particles are 0-2 / [mu] m 2, with roughening particles of less than a particle size 0.30 .mu.m 1.0 .mu.m is 0-2 / [mu] m 2, the particle size 1.0 .mu.m or more It is formed without roughening particles.
- the roughened surface has 0 to 42 rough particles having a particle size of less than 0.10 ⁇ m / ⁇ m 2 and a particle size of 10-25 particles / ⁇ m 2 of coarse particles of 0.10 ⁇ m or more but less than 0.30 ⁇ m, 0-2 particles / ⁇ m 2 of coarse particles of 0.30 ⁇ m or more and less than 1.0 ⁇ m, and particle size of 1.0 ⁇ m It is formed without the above roughening particles.
- 0 to 30 particles / ⁇ m 2 of roughened particles having a particle size of less than 0.10 ⁇ m are formed on the roughened surface.
- roughening particles of less than a particle size 0.30 .mu.m 1.0 .mu.m is 3 to 7 / [mu] m 2
- the particle size 1.0 .mu.m It is formed without the above roughening particles.
- the roughened surface has 15 to 42 roughened particles having a particle size of less than 0.10 ⁇ m / ⁇ m 2 , a particle size of 0-3 particles / ⁇ m 2 of 0.10 ⁇ m or more and less than 0.30 ⁇ m, no coarse particles of particle size of 0.30 ⁇ m or more and less than 1.0 ⁇ m, no rough particles of particle size of 1.0 ⁇ m or more Is formed.
- the surface area A of the roughened particles and the area obtained when the roughened particles are viewed in plan from the copper foil surface side.
- the ratio A / B with B is 2.00 to 2.45.
- the A / B is 2.00 to 2.30.
- the A / B is 2.00 to 2.15.
- the light transmittance of the resin substrate becomes 30% or more.
- the present invention is a copper clad laminate comprising the surface-treated copper foil and a resin substrate laminated.
- a surface-treated copper foil for a copper clad laminated substrate that is excellently bonded to a resin and excellent in transparency of the resin after the copper foil is removed by etching.
- the copper foil used in the present invention may be either an electrolytic copper foil or a rolled copper foil.
- the surface of the copper foil that adheres to the resin base material, that is, the roughened surface has a fist-like shape on the surface of the copper foil after degreasing for the purpose of improving the peel strength of the copper foil after lamination.
- a roughening process for electrodeposition is performed.
- the electrolytic copper foil has irregularities at the time of manufacture, the irregularities are further increased by enhancing the convex portions of the electrolytic copper foil by roughening treatment. In the present invention, this roughening treatment can be performed by copper-cobalt-nickel alloy plating.
- Ordinary copper plating or the like may be performed as a pretreatment before roughening, and ordinary copper plating or the like may be performed as a finishing treatment after roughening in order to prevent electrodeposits from dropping off.
- the content of treatment may be somewhat different between the rolled copper foil and the electrolytic copper foil.
- known treatments related to copper foil roughening are included as necessary, and are collectively referred to as roughening treatment.
- the ternary alloy layer can be formed as follows. If the amount of deposited Co is less than 100 ⁇ g / dm 2 , the heat resistance may deteriorate and the etching property may deteriorate.
- the amount of Co deposition exceeds 3000 ⁇ g / dm 2 , it is not preferable when the influence of magnetism must be taken into account, etching spots may occur, and acid resistance and chemical resistance may deteriorate. If the Ni adhesion amount is less than 100 ⁇ g / dm 2 , the heat resistance may deteriorate. On the other hand, when the Ni adhesion amount exceeds 900 ⁇ g / dm 2 , the etching residue increases.
- a preferable Co adhesion amount is 1000 to 2000 ⁇ g / dm 2 , and a preferable nickel adhesion amount is 200 to 400 ⁇ g / dm 2 .
- the etching stain means that Co remains without being dissolved when etched with copper chloride
- the etching residue means that Ni remains without being dissolved when alkaline etching is performed with ammonium chloride. It means that.
- Plating bath composition Cu 10-20 g / L, Co 1-10 g / L, Ni 1-10 g / L pH: 1 to 4 Temperature: 40-50 ° C Current density D k : 20 to 30 A / dm 2 Plating time: 1-5 seconds
- cobalt nickel cobalt -100 ⁇ 700 ⁇ g / dm 2 weight deposited on the roughened surface is 200 ⁇ 3000 ⁇ g / dm 2 - can form a nickel alloy plating layer.
- This treatment can be regarded as a kind of rust prevention treatment in a broad sense.
- This cobalt-nickel alloy plating layer needs to be performed to such an extent that the adhesive strength between the copper foil and the substrate is not substantially lowered. If the amount of cobalt adhesion is less than 200 ⁇ g / dm 2 , the heat-resistant peel strength is lowered, and the oxidation resistance and chemical resistance may be deteriorated.
- the treated surface becomes reddish, which is not preferable.
- the amount of cobalt deposition exceeds 3000 ⁇ g / dm 2 , it is not preferable when the influence of magnetism must be taken into account, etching spots occur, and deterioration of acid resistance and chemical resistance is considered.
- a preferable cobalt adhesion amount is 500 to 3000 ⁇ g / dm 2 .
- the nickel adhesion amount is less than 100 ⁇ g / dm 2 , the heat-resistant peel strength is lowered and the oxidation resistance and chemical resistance are deteriorated.
- nickel exceeds 700 ⁇ g / dm 2 the alkali etching property is deteriorated.
- a preferable nickel adhesion amount is 200 to 600 ⁇ g / dm 2 .
- Plating bath composition Co 1-20 g / L, Ni 1-20 g / L pH: 1.5-3.5 Temperature: 30-80 ° C Current density D k : 1.0 to 20.0 A / dm 2 Plating time: 0.5-4 seconds
- a zinc plating layer having an adhesion amount of 10 to 80 ⁇ g / dm 2 is further formed on the cobalt-nickel alloy plating. If the zinc adhesion amount is less than 10 ⁇ g / dm 2 , the heat deterioration rate improving effect may be lost. On the other hand, when the zinc adhesion amount exceeds 80 ⁇ g / dm 2 , the hydrochloric acid resistance deterioration rate may be extremely deteriorated.
- the zinc adhesion amount is 20 to 60 ⁇ g / dm 2 , more preferably 30 to 50 ⁇ g / dm 2 .
- Plating bath composition Zn 100 to 300 g / L pH: 3-4 Temperature: 50-60 ° C Current density D k : 0.1 to 0.5 A / dm 2 Plating time: 1 to 3 seconds
- a zinc alloy plating layer such as zinc-nickel alloy plating may be formed in place of the zinc plating layer, and a rust prevention layer may be formed on the outermost surface by chromate treatment or application of a silane coupling agent. Good.
- the surface-treated copper foil of the present invention is a ternary composed of copper, cobalt, and nickel on the primary particle layer after forming a primary particle layer of copper on the surface of the copper foil in advance as a roughening treatment.
- an example of plating conditions for the primary particles of copper is as follows: Plating bath composition: Cu 10-25 g / L, sulfuric acid 50-100 g / L Temperature: 25-50 ° C Current density D k : 10 to 70 A / dm 2 Plating time: 5 to 25 seconds Coulomb amount 50 to 500 As / dm 2
- Secondary particle plating conditions is as follows: Plating bath composition: Cu 10-20 g / L, nickel 5-15 g / L, cobalt 5-15 g / L pH: 2-3 Temperature: 30-50 ° C Current density D k : 20 to 60 A / dm 2 Plating time: 1-5 seconds Coulomb amount 30-70 As / dm 2
- the surface-treated copper foil of the present invention is a surface-treated copper foil in which roughened particles are formed on the surface of the copper foil by a roughening treatment, and the particle size of the surface-treated copper foil is less than 0.10 ⁇ m.
- the surface-treated copper foil of the present invention has high peel strength and adheres favorably to the resin, and the light transmittance of the resin after the copper foil is removed by etching is good.
- the number of roughened particles having a particle diameter of less than 0.10 ⁇ m is 10 to 42 particles / ⁇ m 2
- the number of roughened particles having a particle diameter of 0.10 ⁇ m to less than 0.30 ⁇ m is 0 to 10 particles / ⁇ m 2 .
- [mu] m 2 with roughening particles of less than a particle size 0.30 .mu.m 1.0 .mu.m is 0-5 / [mu] m 2, preferably a particle size 1.0 .mu.m or more roughening particles are not present.
- roughening particles of size less than 0.10 ⁇ m 15 to 42 amino / [mu] m 2 are 0-2 / [mu] m 2
- the particle size 0.30 ⁇ m or more More preferably, the number of coarse particles less than 1.0 ⁇ m is 0 to 2 particles / ⁇ m 2 , and there are no coarse particles having a particle size of 1.0 ⁇ m or more.
- the roughening treated surface roughening particles of size less than 0.10 ⁇ m 0 to 42 amino / [mu] m 2 roughening particles of size less than 0.10 ⁇ m or 0.30 ⁇ m 10 to 25 / [mu] m 2
- the rough particles having a particle size of 0.30 ⁇ m or more and less than 1.0 ⁇ m may be formed at 0 to 2 particles / ⁇ m 2 without any rough particles having a particle size of 1.0 ⁇ m or more.
- the roughened surface has 0-30 particles / ⁇ m 2 of roughened particles having a particle size of less than 0.10 ⁇ m, 0-25 particles / ⁇ m 2 of roughened particles having a particle size of 0.10 ⁇ m or more but less than 0.30 ⁇ m,
- the number of roughened particles having a particle size of 0.30 ⁇ m or more and less than 1.0 ⁇ m may be 3 to 7 particles / ⁇ m 2 and there may be no roughened particles having a particle size of 1.0 ⁇ m or more.
- the roughening treated surface roughening particles of size less than 0.10 ⁇ m 15 to 42 amino / [mu] m 2 roughening particles of size less than 0.10 ⁇ m or 0.30 ⁇ m is 0-3 / [mu] m 2
- the surface-treated copper foil of the present invention has a light transmittance of the resin substrate in a portion where the copper foil is removed after being bonded to the resin substrate. Becomes better. Specifically, when the surface-treated copper foil of the present invention is bonded to both surfaces of a 50 ⁇ m thick resin substrate from the surface of the roughened surface, the light transmittance of the resin substrate is removed when the copper foil is removed by etching. May be 30% or more, preferably 50% or more.
- the ratio A / B between the surface area A of the roughened particles and the area B obtained when the roughened particles are viewed in plan from the copper foil surface side greatly affects the light transmittance of the resin. That is, the smaller the ratio A / B, the better the resin transmittance described above. Therefore, in the surface-treated copper foil of the present invention, the ratio A / B is preferably 2.00 to 2.45, more preferably 2.00 to 2.30, and 2.00 to 2 Even more preferably, .15.
- the morphology and formation density of the particles are determined, and the number density of particles having the above particle diameters and the area ratio A / B of the particles can be controlled.
- the copper-clad laminate can be manufactured by bonding the surface-treated copper foil of the present invention to the resin substrate from the roughened surface side.
- the resin substrate is not particularly limited as long as it has characteristics applicable to a printed wiring board or the like.
- a paper base phenol resin, a paper base epoxy resin, a synthetic fiber cloth base epoxy resin for rigid PWB Glass cloth / paper composite base material epoxy resin, glass cloth / glass nonwoven fabric composite base material epoxy resin, glass cloth base material epoxy resin, etc. can be used, and polyester film, polyimide film, etc. can be used for FPC.
- a prepreg in which a base material such as glass cloth is impregnated with a resin and the resin is cured to a semi-cured state is prepared. It can be carried out by superposing a copper foil on the prepreg from the opposite surface of the coating layer and heating and pressing.
- the copper-clad laminate of the present invention can be used for various printed wiring boards (PWB), and is not particularly limited. It can be applied to (three or more layers), and can be applied to rigid PWB, flexible PWB (FPC), and rigid flex PWB from the viewpoint of the type of insulating substrate material.
- PWB printed wiring boards
- Examples 1 to 13 and Comparative Examples 1 to 5 a copper foil was prepared, and one surface was plated under the conditions described in Tables 1 to 4 as a roughening treatment.
- rolled copper foil of tough pitch copper (JIS H3100 C1100R) manufactured by JX Nippon Mining & Metals was used.
- electrolytic copper foil HLPLC foil manufactured by JX Nippon Mining & Metals was used as copper foils of Examples 9 to 13 and Comparative Examples 1 and 4
- the copper foil was bonded to both surfaces of a polyimide film with a thermosetting adhesive for lamination (thickness 50 ⁇ m), and the copper foil was removed by etching (ferric chloride aqueous solution) to prepare a sample film.
- the light transmittance of the obtained resin layer was measured using a spectrophotometer V-660 manufactured by JASCO Corporation with a slit of 10 mm and a wavelength of 620 nm.
- the copper foil was bonded to both surfaces of a polyimide film with a thermosetting adhesive for lamination (thickness 50 ⁇ m), and the copper foil was removed by etching (ferric chloride aqueous solution) to prepare a sample film.
- the printed material was attached to one surface of the obtained resin layer, and the visibility of the printed material was judged from the opposite surface through the resin layer.
- the printed product with a clear outline was evaluated as “ ⁇ ” (passed), and the printed outline was evaluated as “x” (failed).
- Peel strength (adhesive strength);
- the normal peel strength was measured with a tensile tester Autograph 100 and the peel strength measured in a normal state after being placed in an oven at 150 ° C. for 1 week, and the normal peel strength was 0.7 N. / Mm or more can be used for copper clad laminated substrate applications. Table 5 shows the conditions and evaluation of each test.
- Examples 1 to 13 all had good transmittance, visibility, and peel strength.
- the number of roughened particles having a particle size of 1.0 ⁇ m or more exceeded 0.1 particles / ⁇ m 2 , and thus the transmittance was poor.
- the number of roughened particles having a particle size of 0.30 ⁇ m or more and less than 1.0 ⁇ m was more than 10 particles / ⁇ m 2 , and thus the transmittance was poor.
- the number of roughened particles having a particle size of 0.10 ⁇ m or more and less than 0.30 ⁇ m was more than 25 particles / ⁇ m 2 , and thus the transmittance was poor.
- FIG. 1 shows the printed matter of (a) Comparative Example 1, (b) Example 1, (c) Example 2, (d) Example 3, and (e) Example 4 in the above-described visibility evaluation. Each photo is shown.
- FIG. 2 shows (a) Comparative Example 1, (b) Example 1, (c) Example 2, (d) Example 10, and (e) Example 4 in the evaluation of the number density of the roughened particles. The SEM observation photograph of each is shown.
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Abstract
Description
一方、特許文献2では屈曲性に優れる銅箔として、油膜制御等の条件下の冷間圧延工程で形成された表面上のオイルピットの深さが2.0μm以下である圧延銅箔が提案されている。
本発明は、樹脂と良好に接着し、且つ、銅箔をエッチングで除去した後の樹脂の透明性に優れた銅張積層基板用銅箔を提供する。
本発明において使用する銅箔は、電解銅箔或いは圧延銅箔いずれでも良い。通常、銅箔の、樹脂基材と接着する面、即ち粗化面には積層後の銅箔の引き剥し強さを向上させることを目的として、脱脂後の銅箔の表面にふしこぶ状の電着を行う粗化処理が施される。電解銅箔は製造時点で凹凸を有しているが、粗化処理により電解銅箔の凸部を増強して凹凸を一層大きくする。本発明においては、この粗化処理は銅-コバルト-ニッケル合金めっきにより行うことができる。粗化前の前処理として通常の銅めっき等が行われることがあり、粗化後の仕上げ処理として電着物の脱落を防止するために通常の銅めっき等が行なわれることもある。圧延銅箔と電解銅箔とでは処理の内容を幾分異にすることもある。本発明においては、こうした前処理及び仕上げ処理をも含め、銅箔粗化と関連する公知の処理を必要に応じて含め、総称して粗化処理と云うものとする。
めっき浴組成:Cu10~20g/L、Co1~10g/L、Ni1~10g/L
pH:1~4
温度:40~50℃
電流密度Dk:20~30A/dm2
めっき時間:1~5秒
めっき浴組成:Co1~20g/L、Ni1~20g/L
pH:1.5~3.5
温度:30~80℃
電流密度Dk:1.0~20.0A/dm2
めっき時間:0.5~4秒
めっき浴組成:Zn100~300g/L
pH:3~4
温度:50~60℃
電流密度Dk:0.1~0.5A/dm2
めっき時間:1~3秒
めっき浴組成:Cu10~25g/L、硫酸50~100g/L
温度:25~50℃
電流密度Dk:10~70A/dm2
めっき時間:5~25秒
クーロン量50~500As/dm2
めっき浴組成:Cu10~20g/L、ニッケル5~15g/L、コバルト5~15g/L
pH:2~3
温度:30~50℃
電流密度Dk:20~60A/dm2
めっき時間:1~5秒
クーロン量30~70As/dm2
銅箔と樹脂基板とを積層すると、銅箔表面の粗化粒子は樹脂に埋め込まれる。続いて、銅箔層をエッチング除去した際、銅箔表面の粗化粒子の形態が樹脂にレプリカとして残る。この樹脂のレプリカが小さいほうが、すなわち、銅箔表面の粗化粒子が微細なほうが、透過の際に光の散乱が小さくなるため、視認性に優れることになる。このような観点から、本発明の表面処理銅箔は、銅箔表面に粗化処理により粗化粒子が形成された表面処理銅箔であり、粗化処理表面に、粒径0.10μm未満の粗化粒子が0~42個/μm2、粒径0.10μm以上0.30μm未満の粗化粒子が0~25個/μm2、粒径0.30μm以上1.0μm未満の粗化粒子が0~10個/μm2、粒径1.0μm以上の粗化粒子が0~0.1個/μm2で形成されている。本発明の表面処理銅箔は、上記構成により、ピール強度が高くなって樹脂と良好に接着し、且つ、銅箔をエッチングで除去した後の樹脂の光透過性が良好となる。その結果、当該樹脂を透過して視認される位置決めパターンを介して行うICチップ搭載時の位置合わせ等が容易となる。
このような粗化粒子の個数密度について、粒径0.10μm未満の粗化粒子が10~42個/μm2、粒径0.10μm以上0.30μm未満の粗化粒子が0~10個/μm2、粒径0.30μm以上1.0μm未満の粗化粒子が0~5個/μm2で、粒径1.0μm以上の粗化粒子が存在しないのが好ましい。また、粒径0.10μm未満の粗化粒子が15~42個/μm2、粒径0.10μm以上0.30μm未満の粗化粒子が0~2個/μm2、粒径0.30μm以上1.0μm未満の粗化粒子が0~2個/μm2で、粒径1.0μm以上の粗化粒子が存在しないのがより好ましい。
また、粗化処理表面に、粒径0.10μm未満の粗化粒子が0~42個/μm2、粒径0.10μm以上0.30μm未満の粗化粒子が10~25個/μm2、粒径0.30μm以上1.0μm未満の粗化粒子が0~2個/μm2で、粒径1.0μm以上の粗化粒子がなく形成されていてもよい。さらに、粗化処理表面に、粒径0.10μm未満の粗化粒子が0~30個/μm2、粒径0.10μm以上0.30μm未満の粗化粒子が0~25個/μm2、粒径0.30μm以上1.0μm未満の粗化粒子が3~7個/μm2で、粒径1.0μm以上の粗化粒子がなく形成されていてもよい。さらに、粗化処理表面に、粒径0.10μm未満の粗化粒子が15~42個/μm2、粒径0.10μm以上0.30μm未満の粗化粒子が0~3個/μm2、粒径0.30μm以上1.0μm未満の粗化粒子がなく、粒径1.0μm以上の粗化粒子がなく形成されていてもよい。
本発明の表面処理銅箔は、上述のように粗化処理表面の平均粗さRzが制御されているため、樹脂基板に貼り合わせた後、銅箔を除去した部分の樹脂基板の光透過率が良好となる。具体的には、本発明の表面処理銅箔は、粗化処理表面側から厚さ50μmの樹脂基板の両面に貼り合わせた後、エッチングで当該銅箔を除去したとき、樹脂基板の光透過率が30%以上、好ましくは50%以上であってもよい。
粗化粒子の表面積Aと、粗化粒子を銅箔表面側から平面視したときに得られる面積Bとの比A/Bは、上述の樹脂の光透過率に大いに影響を及ぼす。すなわち、比A/Bが小さい銅箔ほど、上述の樹脂の透過率が良好となる。このため、本発明の表面処理銅箔は、当該比A/Bが2.00~2.45であるのが好ましく、2.00~2.30であるのがより好ましく、2.00~2.15であるのがさらにより好ましい。
(1)粗化粒子の個数密度測定;
銅箔の粗化面の3万倍の走査型電子顕微鏡写真(面積4.3μm×3.1μm)から粒径サイズ毎に粒子個数をカウントした。なお、走査型電子顕微鏡写真の粒子の上に直線を引いた場合に、粒子を横切る直線の長さが最も長い部分の粒子の長さをその粒子の粒径とした。
粗化粒子の表面積はレーザー顕微鏡による測定法を使用した。株式会社キーエンス製レーザーマイクロスコープVK8500を用いて粗化処理面の100×100μm相当面積(実データでは9924.4μm2)における三次元表面積Aを測定して、三次元表面積A÷二次元表面積B=面積比(A/B)とする手法により設定を行った。
銅箔をラミネート用熱硬化性接着剤付きポリイミドフィルム(厚み50μm)の両面に貼り合せ、銅箔をエッチング(塩化第二鉄水溶液)で除去してサンプルフィルムを作成した。得られた樹脂層に対し、日本分光株式会社製分光光度計V-660を用いて、スリット10mmで、波長620nmの設定により光透過率を測定した。
銅箔をラミネート用熱硬化性接着剤付きポリイミドフィルム(厚み50μm)の両面に貼り合わせ、銅箔をエッチング(塩化第二鉄水溶液)で除去してサンプルフィルムを作成した。得られた樹脂層の一面に印刷物を貼り付け、反対面から樹脂層越しに印刷物の視認性を判定した。印刷物の輪郭がはっきりしたものを「○」(合格)、輪郭が崩れたものを「×」(不合格)と評価した。
PC-TM-650に準拠し、引張り試験機オートグラフ100で常態ピール強度と150℃のオーブン中で1週間置いた後の常態で測定したピール強度を測定し、上記常態ピール強度が0.7N/mm以上を銅張積層基板用途に使用できるものとした。
上記各試験の条件及び評価を表5に示す。
実施例1~13は、いずれも透過率、視認性及びピール強度が良好であった。
比較例1、2は、粒径1.0μm以上の粗化粒子が0.1個/μm2超であったため、透過率が不良であった。
比較例3は、粒径0.30μm以上1.0μm未満の粗化粒子が10個/μm2超であったため、透過率が不良であった。
比較例4は、粒径0.10μm以上0.30μm未満の粗化粒子が25個/μm2超であったため、透過率が不良であった。
比較例5は、粒径0.10μm未満の粗化粒子が42個/μm2超であったため、透過率が不良であった。
図1に、上記視認性評価の際の、(a)比較例1、(b)実施例1、(c)実施例2、(d)実施例3、(e)実施例4の印刷物の観察写真をそれぞれ示す。
図2に、上記粗化粒子の個数密度評価の際の、(a)比較例1、(b)実施例1、(c)実施例2、(d)実施例10、(e)実施例4のSEM観察写真をそれぞれ示す。
Claims (11)
- 銅箔表面に粗化処理により粗化粒子が形成された表面処理銅箔であって、
前記粗化処理表面に、粒径0.10μm未満の粗化粒子が0~42個/μm2、粒径0.10μm以上0.30μm未満の粗化粒子が0~25個/μm2、粒径0.30μm以上1.0μm未満の粗化粒子が0~10個/μm2、粒径1.0μm以上の粗化粒子が0~0.1個/μm2で形成されている銅張積層板用表面処理銅箔。 - 前記粗化処理表面に、粒径0.10μm未満の粗化粒子が10~42個/μm2、粒径0.10μm以上0.30μm未満の粗化粒子が0~10個/μm2、粒径0.30μm以上1.0μm未満の粗化粒子が0~5個/μm2で、粒径1.0μm以上の粗化粒子がなく形成されている請求項1に記載の銅張積層板用表面処理銅箔。
- 前記粗化処理表面に、粒径0.10μm未満の粗化粒子が15~42個/μm2、粒径0.10μm以上0.30μm未満の粗化粒子が0~2個/μm2、粒径0.30μm以上1.0μm未満の粗化粒子が0~2個/μm2で、粒径1.0μm以上の粗化粒子がなく形成されている請求項2に記載の銅張積層板用表面処理銅箔。
- 前記粗化処理表面に、粒径0.10μm未満の粗化粒子が0~42個/μm2、粒径0.10μm以上0.30μm未満の粗化粒子が10~25個/μm2、粒径0.30μm以上1.0μm未満の粗化粒子が0~2個/μm2で、粒径1.0μm以上の粗化粒子がなく形成されている請求項1に記載の銅張積層板用表面処理銅箔。
- 前記粗化処理表面に、粒径0.10μm未満の粗化粒子が0~30個/μm2、粒径0.10μm以上0.30μm未満の粗化粒子が0~25個/μm2、粒径0.30μm以上1.0μm未満の粗化粒子が3~7個/μm2で、粒径1.0μm以上の粗化粒子がなく形成されている請求項1に記載の銅張積層板用表面処理銅箔。
- 前記粗化処理表面に、粒径0.10μm未満の粗化粒子が15~42個/μm2、粒径0.10μm以上0.30μm未満の粗化粒子が0~3個/μm2、粒径0.30μm以上1.0μm未満の粗化粒子がなく、粒径1.0μm以上の粗化粒子がなく形成されている請求項1に記載の銅張積層板用表面処理銅箔。
- 前記粗化粒子の表面積Aと、前記粗化粒子を前記銅箔表面側から平面視したときに得られる面積Bとの比A/Bが2.00~2.45である請求項1~3に記載の銅張積層板用表面処理銅箔。
- 前記A/Bが2.00~2.30である請求項4に記載の銅張積層板用表面処理銅箔。
- 前記A/Bが2.00~2.15である請求項5に記載の銅張積層板用表面処理銅箔。
- 前記銅箔を、粗化処理表面側から厚さ50μmの樹脂基板の両面に貼り合わせた後、エッチングで前記銅箔を除去したとき、前記樹脂基板の光透過率が30%以上となる請求項1~6のいずれかに記載の銅張積層板用表面処理銅箔。
- 請求項1~7のいずれかに記載の表面処理銅箔と樹脂基板とを積層して構成した銅張積層板。
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JP2015024515A (ja) * | 2013-07-24 | 2015-02-05 | Jx日鉱日石金属株式会社 | キャリア付銅箔及びそれを用いた銅張積層板 |
WO2015012376A1 (ja) * | 2013-07-24 | 2015-01-29 | Jx日鉱日石金属株式会社 | 表面処理銅箔、キャリア付銅箔、基材、樹脂基材、プリント配線板、銅張積層板及びプリント配線板の製造方法 |
US10257938B2 (en) | 2013-07-24 | 2019-04-09 | Jx Nippon Mining & Metals Corporation | Surface-treated copper foil, copper foil with carrier, substrate, resin substrate, printed wiring board, copper clad laminate and method for producing printed wiring board |
CN104349582B (zh) * | 2013-07-30 | 2018-11-13 | 古河电气工业株式会社 | 线路板用铜箔及线路板 |
CN104349582A (zh) * | 2013-07-30 | 2015-02-11 | 古河电气工业株式会社 | 线路板用铜箔及线路板 |
JP5706026B1 (ja) * | 2013-07-30 | 2015-04-22 | 古河電気工業株式会社 | 配線板用銅箔及び配線板 |
JP2015061939A (ja) * | 2013-08-20 | 2015-04-02 | Jx日鉱日石金属株式会社 | 表面処理銅箔及びそれを用いたキャリア付銅箔、積層板、プリント配線板、電子機器、並びに、プリント配線板の製造方法 |
JP2015061756A (ja) * | 2013-08-21 | 2015-04-02 | Jx日鉱日石金属株式会社 | キャリア付銅箔及びそれを用いた積層板、プリント配線板、電子機器、並びに、プリント配線板の製造方法 |
JP2015147978A (ja) * | 2014-02-06 | 2015-08-20 | 古河電気工業株式会社 | 高周波回路用銅箔、銅張積層板及びプリント配線板 |
CN104359833A (zh) * | 2014-11-07 | 2015-02-18 | 广州兴森快捷电路科技有限公司 | 覆铜板剥离强度的测试方法 |
CN105835478A (zh) * | 2015-01-29 | 2016-08-10 | Jx金属株式会社 | 表面处理铜箔、及关于它的制品 |
CN105835478B (zh) * | 2015-01-29 | 2019-08-09 | Jx 金属株式会社 | 表面处理铜箔、及关于它的制品 |
JP2016145390A (ja) * | 2015-02-07 | 2016-08-12 | Jx金属株式会社 | キャリア付銅箔、積層体、プリント配線板、及び、プリント配線板の製造方法 |
Also Published As
Publication number | Publication date |
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TW201341175A (zh) | 2013-10-16 |
KR20150074219A (ko) | 2015-07-01 |
KR20140088911A (ko) | 2014-07-11 |
JP5919303B2 (ja) | 2016-05-18 |
CN104053825A (zh) | 2014-09-17 |
TWI569957B (zh) | 2017-02-11 |
CN104053825B (zh) | 2016-12-07 |
KR102066314B1 (ko) | 2020-01-14 |
JPWO2013108415A1 (ja) | 2015-05-11 |
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