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WO2013118416A1 - Feuille de cuivre comportant un support, procédé de fabrication de feuille de cuivre comportant un support, carte de câblage imprimé, carte de circuit imprimé et stratifié plaqué de cuivre - Google Patents

Feuille de cuivre comportant un support, procédé de fabrication de feuille de cuivre comportant un support, carte de câblage imprimé, carte de circuit imprimé et stratifié plaqué de cuivre Download PDF

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Publication number
WO2013118416A1
WO2013118416A1 PCT/JP2012/083722 JP2012083722W WO2013118416A1 WO 2013118416 A1 WO2013118416 A1 WO 2013118416A1 JP 2012083722 W JP2012083722 W JP 2012083722W WO 2013118416 A1 WO2013118416 A1 WO 2013118416A1
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WIPO (PCT)
Prior art keywords
layer
carrier
copper
copper foil
intermediate layer
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Ceased
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PCT/JP2012/083722
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English (en)
Japanese (ja)
Inventor
美里 中願寺
友太 永浦
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JX Nippon Mining and Metals Corp
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JX Nippon Mining and Metals Corp
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Priority to JP2013557388A priority Critical patent/JP5903446B2/ja
Publication of WO2013118416A1 publication Critical patent/WO2013118416A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C25D5/14—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex layers
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/123—Spraying molten metal
    • 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
    • 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
    • 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
    • H05K1/09—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
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/388—Improvement of the adhesion between the insulating substrate and the metal by the use of a metallic or inorganic thin film adhesion layer

Definitions

  • the present invention relates to a copper foil with a carrier, a method for producing a copper foil with a carrier, a printed wiring board, a printed circuit board, and a copper clad laminate. More specifically, the present invention relates to a copper foil with a carrier used as a material for a printed wiring board for fine patterns, a method for producing the copper foil with a carrier, a printed wiring board, a printed circuit board, and a copper clad laminate.
  • a printed wiring board is manufactured as a copper clad laminate in which an insulating substrate mainly composed of a copper foil and a glass epoxy substrate, a BT resin, a polyimide film or the like is bonded. Bonding is performed by laminating an insulating substrate and a copper foil and applying heat and pressure (laminating method), or by applying a varnish that is a precursor of an insulating substrate material to a surface having a coating layer of copper foil, A heating / curing method (casting method) is used.
  • the thickness of the copper foil used for the copper clad laminate is 9 ⁇ m, and further the thickness is becoming 5 ⁇ m or less.
  • the handleability when forming a copper clad laminate by the above-described lamination method or casting method is extremely deteriorated. Therefore, a copper foil with a carrier has appeared, in which a thick metal foil is used as a carrier, and an ultrathin copper layer is formed on the metal foil via a release layer.
  • a general method of using a copper foil with a carrier is to peel the carrier through a release layer after the surface of the ultrathin copper layer is bonded to an insulating substrate and thermocompression bonded.
  • a diffusion prevention layer, a release layer, and an electrolytic copper plating are formed in this order on the surface of a carrier, and a Cr or Cr hydrated oxide layer is formed as a release layer.
  • a method for maintaining good peelability after hot pressing by using a simple substance or an alloy of Ni, Co, Fe, Cr, Mo, Ta, Cu, Al, P as a diffusion preventing layer is disclosed.
  • the release layer is formed of Cr, Ni, Co, Fe, Mo, Ti, W, P, alloys thereof or hydrates thereof. Furthermore, Patent Documents 2 and 3 describe that it is effective to provide Ni, Fe or an alloy layer thereof as a base of the release layer in order to stabilize the peelability in a high temperature use environment such as a hot press. Has been.
  • an object of the present invention is to provide a copper foil with a carrier that can be peeled off after a lamination process on an insulating substrate, while the ultrathin copper layer does not peel off from the carrier before the lamination process on the insulating substrate.
  • Another object of the present invention is to provide a carrier-attached copper foil in which the generation of pinholes on the ultrathin copper layer side surface is suppressed.
  • the present inventor conducted extensive research and used copper foil as a carrier, formed an intermediate layer between the ultrathin copper layer and the carrier, and formed this intermediate layer on the copper foil carrier.
  • Consist of nickel and chromate in order, control the amount of nickel and chromium deposited, and control the chromium and nickel atom concentration on the intermediate layer surface when peeled between the intermediate layer and ultrathin copper layer has been found to be extremely effective. It is also extremely effective to control the chromium and nickel atom concentration on the surface of the intermediate layer when the insulating substrate is thermocompression bonded to the ultrathin copper layer and the carrier is peeled off from the ultrathin copper layer. I found.
  • the present invention has been completed on the basis of the above knowledge, and in one aspect, includes a copper foil carrier, an intermediate layer laminated on the copper foil carrier, and an ultrathin copper layer laminated on the intermediate layer.
  • a copper foil with a carrier, The intermediate layer is configured by laminating nickel and chromate in this order on the copper foil carrier, Adhesion amount 100 ⁇ 40000 ⁇ g / dm 2 of nickel, the adhesion amount of chromium is 5 ⁇ 100 ⁇ g / dm 2,
  • the atomic concentration (%) of chromium in the depth direction (x: unit nm) obtained from the depth direction analysis from the surface by XPS is defined as f (x).
  • ⁇ f (x) dx / ( ⁇ f (x) dx + ⁇ g (x) dx + ⁇ h (x) dx + ⁇ i (x) dx + ⁇ j (x) dx + ⁇ k (x) dx) is 1-30%
  • ⁇ g (x) dx / ( ⁇ f (x) dx + ⁇ g (x) dx + ⁇ h (x) dx + ⁇ i (x) dx + ⁇ j (x) dx + ⁇ k (x) dx) is 1 to 50%, and [1.0, 4.0], ⁇
  • the section [1.0, 4.0], ⁇ h (x) dx / ( ⁇ f (x) dx + ⁇ g (x) dx + ⁇ h (x) dx + ⁇ i (x) dx + ⁇ j (x) dx + ⁇ k (x) dx) satisfies 1 to 30.
  • the binding energy of the 2P3 / 2 orbit of chromium detected by XPS of the intermediate layer is in the range of 576 to 580 eV.
  • the ultrathin copper layer is thermocompression-bonded under the conditions of an insulating substrate in the atmosphere, pressure: 20 kgf / cm 2 , 220 ° C. ⁇ 2 hours,
  • the atomic concentration (%) of chromium in the depth direction (x: unit nm) obtained from the depth direction analysis from the surface by XPS is defined as f (x).
  • ⁇ f (x) dx / ( ⁇ f (x) dx + ⁇ g (x) dx + ⁇ h (x) dx + ⁇ i (x) dx + ⁇ j (x) dx + ⁇ k (x) dx) is 0.5-30%
  • ⁇ g (x) dx / ( ⁇ f (x) dx + ⁇ g (x) dx + ⁇ h (x) dx + ⁇ i (x) dx + ⁇ j (x) dx + ⁇ k (x) dx) is 1 to 50% and [1.0, 4.0], ⁇
  • the ultrathin copper layer is thermocompression-bonded under the conditions of an insulating substrate in the atmosphere, pressure: 20 kgf / cm 2 , 220 ° C. ⁇ 2 hours,
  • ⁇ f (x) dx / ( ⁇ f (x) in the section [0, 1.0] in the depth direction analysis from the intermediate layer surface by XPS dx + ⁇ g (x) dx + ⁇ h (x) dx + ⁇ i (x) dx + ⁇ j (x) dx + ⁇ k (x) dx) satisfies 1 to 25%.
  • the ultrathin copper layer is thermocompression-bonded under the conditions of an insulating substrate in the atmosphere, pressure: 20 kgf / cm 2 , 220 ° C. ⁇ 2 hours,
  • ⁇ h (x) dx / ( ⁇ f ( x) dx + ⁇ g (x) dx + ⁇ h (x) dx + ⁇ i (x) dx + ⁇ j (x) dx + ⁇ k (x) dx) satisfies 2 to 40%.
  • the copper foil carrier is formed of an electrolytic copper foil or a rolled copper foil.
  • the surface of the ultrathin copper layer has a roughening treatment layer.
  • the roughening treatment layer is any one selected from the group consisting of copper, nickel, cobalt and zinc, or any one or more. It is a layer made of an alloy containing.
  • one or more types selected from the group consisting of a rust prevention layer, a chromate treatment layer and a silane coupling treatment layer on the surface of the roughening treatment layer has a layer of.
  • a nickel plating is formed on a copper foil carrier, and then an intermediate layer is formed by forming a chromate layer by electrolytic chromate, and an extremely thin layer is formed by electrolytic plating on the intermediate layer. And a step of forming a copper layer.
  • a nickel plating is formed on a copper foil carrier and then an intermediate layer is formed by forming a chromate layer by electrolytic chromate, and an electrode is formed on the intermediate layer by electrolytic plating. It is a manufacturing method of copper foil with a carrier including the process of forming a thin copper layer, and the process of forming a roughening process layer on the said ultra-thin copper layer.
  • the present invention is a printed wiring board manufactured using the carrier-attached copper foil of the present invention.
  • the present invention is a printed circuit board manufactured using the carrier-attached copper foil of the present invention.
  • the present invention is a copper clad laminate manufactured using the carrier-attached copper foil of the present invention.
  • the copper foil with a carrier according to the present invention has high adhesion between the carrier and the ultrathin copper layer before the lamination process to the insulating substrate, while the carrier and the ultrathin copper layer after the lamination process to the insulation substrate. Adhesiveness is lowered, it can be easily peeled off at the carrier / ultra-thin copper layer interface, and the occurrence of pinholes on the surface of the ultra-thin copper layer can be well suppressed.
  • FIG. 2 It is a XPS depth profile of the depth direction of the intermediate
  • FIG. 2 It is an XPS depth profile of the depth direction of the intermediate
  • FIG. It is the XPS depth profile of the depth direction of the ultra-thin copper layer surface before board
  • a copper foil is used as a carrier that can be used in the present invention.
  • the carrier is typically provided in the form of rolled copper foil or electrolytic copper foil.
  • the electrolytic copper foil is produced by electrolytic deposition of copper from a copper sulfate plating bath onto a drum of titanium or stainless steel, and the rolled copper foil is produced by repeating plastic working and heat treatment with a rolling roll.
  • the copper foil material is, for example, Sn-containing copper, Ag-containing copper, copper alloy added with Cr, Zr, Mg, etc., and Corson-based added with Ni and Si Copper alloys such as copper alloys can also be used.
  • a copper alloy foil is also included.
  • the thickness of the carrier that can be used in the present invention is not particularly limited, but may be appropriately adjusted to a thickness suitable for serving as a carrier, for example, 12 ⁇ m or more. However, if it is too thick, the production cost becomes high, so generally it is preferably 35 ⁇ m or less. Accordingly, the thickness of the carrier is typically 12-70 ⁇ m, more typically 18-35 ⁇ m.
  • Intermediate layer An intermediate layer is provided on the copper foil carrier.
  • the intermediate layer is formed by laminating nickel and chromate in this order on a copper foil carrier. Since the adhesive strength between nickel and copper is higher than the adhesive strength between chromium and copper, when the ultrathin copper layer is peeled off, it peels at the interface between the ultrathin copper layer and chromate. Further, the nickel of the intermediate layer is expected to have a barrier effect that prevents the copper component from diffusing from the carrier into the ultrathin copper layer. Also, chromate is formed on the intermediate layer instead of chrome plating.
  • chromium plating forms a dense chromium oxide layer on the surface, when an ultrathin copper foil is formed by electroplating, the electrical resistance increases and pinholes are likely to occur. Since the chromium oxide layer that is not as dense as chromium plating is formed on the surface on which the chromate is formed, it is difficult to become resistance when forming an ultrathin copper foil by electroplating, and pinholes can be reduced. When using electrolytic copper foil as a carrier, it is preferable to provide an intermediate layer on the shiny surface from the viewpoint of reducing pinholes.
  • the chromate layer is thin at the interface of the ultrathin copper layer, while the ultrathin copper layer does not peel from the carrier before the lamination process to the insulating substrate, while the carrier after the lamination process to the insulating substrate From the viewpoint of obtaining the property that the ultrathin copper layer can be peeled off.
  • the chromate layer is present at the boundary between the carrier and the ultrathin copper layer without providing the nickel layer, the peelability is hardly improved, and when there is no chromate layer and the nickel layer and the ultrathin copper layer are laminated directly, nickel Depending on the amount of nickel in the layer, the peel strength is too strong or too weak to obtain an appropriate peel strength.
  • the intermediate layer is also peeled along with the peeling of the ultrathin copper layer, that is, peeling occurs between the carrier and the intermediate layer.
  • peeling occurs between the carrier and the intermediate layer.
  • the adhesion between the chromium and copper interface is weak and easy to peel off. Further, when the nickel amount in the intermediate layer is insufficient, there is only a very small amount of chromium between the carrier and the ultrathin copper layer, so that they are in close contact with each other and are difficult to peel off.
  • the nickel of the intermediate layer can be formed by wet plating such as electroplating, electroless plating and immersion plating, or dry plating such as sputtering, CVD and PDV. Electroplating is preferable from the viewpoint of cost. Also, chromate can be formed with, for example, electrolytic chromate, immersion chromate, etc., but the chromium concentration can be increased, and the peel strength of the ultrathin copper layer from the copper foil carrier is improved. Preferably formed.
  • the adhesion amount of nickel is 100 to 40000 ⁇ g / dm 2
  • the adhesion amount of chromium is 5 to 100 ⁇ g / dm 2
  • the nickel adhesion amount is preferably 300 to 10,000 ⁇ g / dm 2, and preferably 500 to 3000 ⁇ g / dm 2.
  • the chromium adhesion amount is preferably 10 to 50 ⁇ g / dm 2 , more preferably 12 to 30 ⁇ g / dm 2 .
  • Strike plating An ultrathin copper layer is provided on the intermediate layer. Before that, strike plating with a copper-phosphorus alloy may be performed to reduce pinholes in the ultrathin copper layer. Examples of the strike plating include a copper pyrophosphate plating solution.
  • Ultra-thin copper layer An ultrathin copper layer is provided on the intermediate layer.
  • the ultra-thin copper layer can be formed by electroplating using an electrolytic bath such as copper sulfate, copper pyrophosphate, copper sulfamate, copper cyanide, etc., and is used in general electrolytic copper foil with high current density. Since a copper foil can be formed, a copper sulfate bath is preferable.
  • the thickness of the ultrathin copper layer is not particularly limited, but is generally thinner than the carrier, for example, 12 ⁇ m or less. Typically 0.5 to 12 ⁇ m, more typically 2 to 5 ⁇ m.
  • a roughening treatment layer may be provided on the surface of the ultrathin copper layer by performing a roughening treatment, for example, in order to improve the adhesion to the insulating substrate.
  • the roughening treatment can be performed, for example, by forming roughened particles with copper or a copper alloy.
  • the roughening process may be fine.
  • the roughening treatment layer may be a single layer selected from the group consisting of copper, nickel, cobalt and zinc, or a layer made of an alloy containing one or more of them.
  • secondary particles, tertiary particles and / or rust preventive layers are formed of nickel, cobalt, copper, zinc alone or an alloy, and further on the surface.
  • Treatments such as chromate treatment and silane coupling treatment may be applied. That is, on the surface of the roughening treatment layer, one or more layers selected from the group consisting of a rust prevention layer, a chromate treatment layer and a silane coupling treatment layer may be formed, and on the surface of the ultrathin copper layer, You may form 1 or more types of layers selected from the group which consists of a rust prevention layer, a chromate treatment layer, and a silane coupling treatment layer.
  • middle layer is manufactured.
  • the surface of the ultra-thin copper layer is made of paper base phenol resin, paper base epoxy resin, synthetic fiber cloth base epoxy resin, glass cloth / paper composite.
  • a copper-clad laminate can be obtained by bonding to an insulating substrate such as a base epoxy resin, glass cloth / glass nonwoven fabric composite base epoxy resin and glass cloth base epoxy resin, polyester film, polyimide film, etc., and peeling the carrier after thermocompression bonding.
  • an ultrathin copper layer bonded to the insulating substrate of the copper-clad laminate can be etched into a target conductor pattern, and finally a printed wiring board or a printed circuit board can be manufactured.
  • the peeled portion is mainly the interface between the intermediate layer and the ultrathin copper layer.
  • the atomic concentration of chromium in the depth direction (x: unit nm) obtained from the depth direction analysis from the surface by XPS ( %) Is f (x), nickel atomic concentration (%) is g (x), copper atomic concentration (%) is h (x), and oxygen total atomic concentration (%) is i (x).
  • ⁇ f (x ) dx / ( ⁇ f (x) dx + ⁇ g (x) dx + ⁇ h (x) dx + ⁇ i (x) dx + ⁇ j (x) dx + ⁇ k (x) dx) is 2-25% It is preferable to satisfy.
  • the copper foil with a carrier of the present invention is obtained by thermocompression bonding an insulating substrate to an ultrathin copper layer under the conditions of pressure: 20 kgf / cm 2 , 220 ° C. ⁇ 2 hours between the intermediate layer and the ultrathin copper layer.
  • the atomic concentration (%) of chromium in the depth direction (x: unit nm) obtained from XPS depth direction analysis is defined as f (x)
  • the atomic concentration (%) of nickel is g (x), copper atomic concentration (%) as h (x), oxygen total atomic concentration (%) as i (x), carbon atomic concentration (%) as j (x), etc.
  • ⁇ f (x) dx / ( ⁇ f (x) dx + ⁇ g (x) dx + ⁇ h (x) dx + ⁇ i (x) dx + ⁇ j (x) dx + ⁇ k (x) dx) is 0.5-30%
  • ⁇ g (x) dx / ( ⁇ f (x) dx + ⁇ g (x) dx + ⁇ h (x) dx + ⁇ i (x) dx + ⁇ j (x) dx + ⁇ k (x) dx) is 1 to 50%, and [1.
  • the copper foil with a carrier of the present invention is obtained by thermocompression bonding an insulating substrate to an ultrathin copper layer under the conditions of pressure: 20 kgf / cm 2 and 220 ° C. ⁇ 2 hours between the intermediate layer and the ultrathin copper layer.
  • ⁇ f (x) dx / ( ⁇ f (x) dx + ⁇ g (x) dx + ⁇ in the section [0, 1.0] in the depth direction analysis from the intermediate layer surface by XPS h (x) dx +) i (x) dx + ⁇ j (x) dx + ⁇ k (x) dx) preferably satisfies 1 to 25%.
  • chromium is present in a certain amount or more on the outermost surface of the intermediate layer when peeled between the intermediate layer / ultra-thin copper layer, and nickel is present inside the outermost surface. The concentration is high.
  • the copper foil with carrier of the present invention is peeled between the intermediate layer / ultra-thin copper layer, in the section [1.0, 4.0] of the depth direction analysis from the intermediate layer surface by XPS, ⁇ h (x ) dx / ( ⁇ f (x) dx + ⁇ g (x) dx + ⁇ h (x) dx + ⁇ i (x) dx + ⁇ j (x) dx + ⁇ k (x) dx) is 1-30% It is preferable to satisfy.
  • the copper foil with a carrier of the present invention is obtained by thermocompression bonding an insulating substrate to an ultrathin copper layer under the conditions of pressure: 20 kgf / cm 2 , 220 ° C.
  • copper is present in a certain amount or more inside the intermediate layer when peeled between the intermediate layer / ultra thin copper layer.
  • the peel strength can be controlled by controlling the copper concentration in nickel.
  • copper exists in a certain amount or more inside the intermediate layer when the copper foil carrier is peeled from the ultrathin copper layer. For this reason, there exists an effect that the fall of the extreme peeling strength after thermocompression-bonding can be prevented.
  • the higher the nickel current density is set to increase the electrodeposition rate per unit time, and the higher the transport speed of the carrier copper foil, the lower the density of the nickel layer.
  • the concentration of copper in the nickel can be controlled. Further, when the current density in the chromate treatment is increased and the conveying speed of the carrier copper foil is decreased, the chromium concentration increases and the chromium concentration can be controlled.
  • the binding energy of the 2P3 / 2 orbit of chromium detected by XPS in the intermediate layer is in the range of 576 to 580 eV. According to such a configuration, chromium present in the intermediate layer becomes not chromium metal but chromium oxide, and the generation of pinholes on the surface of the ultrathin copper layer can be suppressed more favorably.
  • Nickel sulfate 250-300 g / L Nickel chloride: 35 to 45 g / L Nickel acetate: 10-20g / L Trisodium citrate: 15-30 g / L Brightener: Saccharin, butynediol, etc.
  • Sodium dodecyl sulfate 30 to 100 ppm pH: 4-6 Bath temperature: 50-70 ° C Current density: 3 to 15 A / dm 2
  • -Cr plating solution composition chromic anhydride 200-400 g / L, sulfuric acid 1.5-4 g / L pH: 1 to 4 Liquid temperature: 45-60 ° C Current density: 10 to 40 A / dm 2
  • Electrolytic chromate treatment Liquid composition (1) Potassium dichromate 1-10 g / L, Zinc 0-5 g / L
  • a / dm 2 Coulomb amount: 0.5-30 As / dm 2
  • an ultrathin copper layer having a thickness of 35 ⁇ m was formed on the intermediate layer on the roll-to-roll-type continuous plating line by electroplating under the following conditions to produce a copper foil with a carrier.
  • a copper foil with a carrier For Examples 1 to 3, 5, 7, 11, and 13 to 15, copper foils with a carrier having ultrathin copper layers with thicknesses of 1, 2, 3, 5, and 12 ⁇ m were also produced.
  • Current density 10 to 100 A / dm 2
  • the amount of nickel deposited is measured by ICP emission analysis after dissolving the sample in nitric acid with a concentration of 20% by mass.
  • the amount of chromium deposited is quantitatively analyzed by atomic absorption spectrometry after dissolving the sample in 7% by mass of hydrochloric acid. Measured with
  • XPS measuring device (ULVAC-PHI, Model 5600MC) ⁇ Achieved vacuum: 3.8 ⁇ 10 ⁇ 7 Pa
  • X-ray Monochromatic AlK ⁇ or non-monochromatic MgK ⁇ , X-ray output 300 W, detection area 800 ⁇ m ⁇ , angle between sample and detector 45 °
  • Ion beam ion species Ar + , acceleration voltage 3 kV, sweep area 3 mm ⁇ 3 mm, sputtering rate 2.8 nm / min (in terms of SiO 2 )
  • the copper foil carrier was peeled off from the ultra-thin copper layer, the XPS measurement was performed for the exposed copper foil carrier surface, and the depth profile was created.
  • FIG. 1 and FIG. 2 show XPS depth profiles in the depth direction of the surface of the intermediate layer before bonding the substrates of Example 2 and Comparative Example 3, respectively.
  • FIG. 3 shows an XPS depth profile in the depth direction of the surface of the ultrathin copper layer before bonding the substrates in Example 2.

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Electrochemistry (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Parts Printed On Printed Circuit Boards (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Laminated Bodies (AREA)
PCT/JP2012/083722 2012-02-06 2012-12-26 Feuille de cuivre comportant un support, procédé de fabrication de feuille de cuivre comportant un support, carte de câblage imprimé, carte de circuit imprimé et stratifié plaqué de cuivre Ceased WO2013118416A1 (fr)

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JP2013557388A JP5903446B2 (ja) 2012-02-06 2012-12-26 キャリア付銅箔、キャリア付銅箔の製造方法、プリント配線板の製造方法、プリント回路板の製造方法、銅張積層板の製造方法及び電子機器の製造方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013166995A (ja) * 2012-02-15 2013-08-29 Jx Nippon Mining & Metals Corp キャリア付銅箔及びその製造方法
JP2015047795A (ja) * 2013-09-02 2015-03-16 Jx日鉱日石金属株式会社 キャリア付銅箔、プリント配線板、プリント回路板、銅張積層板、及びプリント配線板の製造方法
JP2016050364A (ja) * 2014-08-29 2016-04-11 Ｊｘ金属株式会社 キャリア付銅箔、銅張積層板、プリント配線板、電子機器、積層体、キャリア付銅箔の製造方法、銅張積層板の製造方法及びプリント配線板の製造方法
JP2017088971A (ja) * 2015-11-12 2017-05-25 Ｊｘ金属株式会社 キャリア付銅箔、キャリア付銅箔の製造方法、積層体、プリント配線板の製造方法及び電子機器の製造方法

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US454381A (en) * 1891-06-16 Alexander gael seinfeld
JPS5720347A (en) * 1980-07-14 1982-02-02 Nippon Denkai Kk Synthetic foil for printed wiring and its manufacture
JP2002292788A (ja) * 2001-03-30 2002-10-09 Nippon Denkai Kk 複合銅箔及び該複合銅箔の製造方法
JP2004169181A (ja) * 2002-10-31 2004-06-17 Furukawa Techno Research Kk キャリア付き極薄銅箔、及びその製造方法、キャリア付き極薄銅箔を用いたプリント配線基板
JP2005076091A (ja) * 2003-09-01 2005-03-24 Furukawa Circuit Foil Kk キャリア付き極薄銅箔の製造方法、及びその製造方法で製造されたキャリア付き極薄銅箔
WO2013031913A1 (fr) * 2011-08-31 2013-03-07 Jx日鉱日石金属株式会社 Feuille de cuivre pourvue d'un support

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Publication number Priority date Publication date Assignee Title
US7026059B2 (en) * 2000-09-22 2006-04-11 Circuit Foil Japan Co., Ltd. Copper foil for high-density ultrafine printed wiring boad
TW200420208A (en) * 2002-10-31 2004-10-01 Furukawa Circuit Foil Ultra-thin copper foil with carrier, method of production of the same, and printed circuit board using ultra-thin copper foil with carrier

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US454381A (en) * 1891-06-16 Alexander gael seinfeld
JPS5720347A (en) * 1980-07-14 1982-02-02 Nippon Denkai Kk Synthetic foil for printed wiring and its manufacture
JP2002292788A (ja) * 2001-03-30 2002-10-09 Nippon Denkai Kk 複合銅箔及び該複合銅箔の製造方法
JP2004169181A (ja) * 2002-10-31 2004-06-17 Furukawa Techno Research Kk キャリア付き極薄銅箔、及びその製造方法、キャリア付き極薄銅箔を用いたプリント配線基板
JP2005076091A (ja) * 2003-09-01 2005-03-24 Furukawa Circuit Foil Kk キャリア付き極薄銅箔の製造方法、及びその製造方法で製造されたキャリア付き極薄銅箔
WO2013031913A1 (fr) * 2011-08-31 2013-03-07 Jx日鉱日石金属株式会社 Feuille de cuivre pourvue d'un support

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013166995A (ja) * 2012-02-15 2013-08-29 Jx Nippon Mining & Metals Corp キャリア付銅箔及びその製造方法
JP2015047795A (ja) * 2013-09-02 2015-03-16 Jx日鉱日石金属株式会社 キャリア付銅箔、プリント配線板、プリント回路板、銅張積層板、及びプリント配線板の製造方法
JP2016050364A (ja) * 2014-08-29 2016-04-11 Ｊｘ金属株式会社 キャリア付銅箔、銅張積層板、プリント配線板、電子機器、積層体、キャリア付銅箔の製造方法、銅張積層板の製造方法及びプリント配線板の製造方法
JP2017088971A (ja) * 2015-11-12 2017-05-25 Ｊｘ金属株式会社 キャリア付銅箔、キャリア付銅箔の製造方法、積層体、プリント配線板の製造方法及び電子機器の製造方法

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TW201341600A (zh) 2013-10-16
JPWO2013118416A1 (ja) 2015-05-11
JP5903446B2 (ja) 2016-04-13

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