WO2015040998A1 - 銅箔、キャリア箔付銅箔及び銅張積層板 - Google Patents

銅箔、キャリア箔付銅箔及び銅張積層板 Download PDF

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WO2015040998A1
WO2015040998A1 PCT/JP2014/071798 JP2014071798W WO2015040998A1 WO 2015040998 A1 WO2015040998 A1 WO 2015040998A1 JP 2014071798 W JP2014071798 W JP 2014071798W WO 2015040998 A1 WO2015040998 A1 WO 2015040998A1
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Prior art keywords
copper foil
copper
layer
foil
roughened
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PCT/JP2014/071798
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English (en)
French (fr)
Japanese (ja)
Inventor
裕昭 津吉
眞 細川
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三井金属鉱業株式会社
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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 CN201480051363.6A priority Critical patent/CN105556004B/zh
Priority to JP2015515306A priority patent/JP6283664B2/ja
Priority to MYPI2016700973A priority patent/MY182166A/en
Priority to KR1020167007204A priority patent/KR101920976B1/ko
Publication of WO2015040998A1 publication Critical patent/WO2015040998A1/ja

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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
    • C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/52—Treatment of copper or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
    • C23C22/63—Treatment of copper or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/82—After-treatment
    • C23C22/83—Chemical after-treatment
    • 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
    • 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
    • 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
    • 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
    • C25D5/615—Microstructure of the layers, e.g. mixed structure
    • C25D5/617—Crystalline 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
    • 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
    • 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
    • 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
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/20—Use of solutions containing silanes
    • 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
    • C25D3/12—Electroplating: Baths therefor from solutions of 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
    • C25D3/38—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
    • 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
    • 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

Definitions

  • the present application relates to a copper foil, a copper foil with a carrier foil, and a copper-clad laminate obtained using these copper foils.
  • the present invention relates to a copper foil provided with a roughening treatment layer having a finer concavo-convex structure on the surface of the copper foil than conventional.
  • the copper foil for this application is often provided with a shape that exhibits an anchor effect on the surface of the copper foil that serves as an adhesive surface.
  • adhesion of fine copper particles as disclosed in Patent Document 1, etc.
  • “unevenness formation by etching” as disclosed in Patent Document 2, etc. Has been performed on the surface of the copper foil.
  • Patent Document 3 in order to provide a copper-clad laminate for a printed circuit in which a copper foil and a laminated base material are firmly bonded with a tough and reactive adhesive,
  • a copper clad laminate in which copper foil is laminated and bonded on both sides a.
  • a general formula QRSiXYZ ... [1] (wherein Q is a functional group that reacts with the following resin composition, R is Q Or a silane coupling agent represented by the general formula T (SH) n ⁇ , a bonding group that links Si atom to each other, X, Y, and Z represent a hydrolyzable group or hydroxyl group bonded to Si atom.
  • T is an aromatic ring, an aliphatic ring, a heterocyclic ring, an aliphatic chain, and n is an integer of 2 or more
  • T is an aromatic ring, an aliphatic ring, a heterocyclic ring, an aliphatic chain, and n is an integer of 2 or more
  • Acrylic monomer, methacrylic monomer, polymer thereof or olefin (2) Diallyl phthalate, epoxy acrylate or epoxy methacrylate and their oligomer peroxide curable resin composition, (3) ethylene butylene copolymer and styrene copolymer in the molecule A thermoplastic elastomer peroxide curable resin composition, (4) an olefin copolymer resin composition containing a glycidyl group, and (5) a polyvinyl butyral resin resin composition having a side chain containing an unsaturated group.
  • an adhesive composed of a polyvinyl butyral resin and a resin composition of an amino resin having a spiroacetal ring and an epoxy resin, or an adhesive of the resin composition. It is possible to adopt a copper-clad laminate for printed circuits, which is directly bonded to the laminated substrate. It is.
  • Patent Document 4 provides a copper foil that does not contain chromium in the surface treatment layer and is excellent in the peel strength of the circuit after being processed into a printed wiring board, the chemical resistance deterioration rate of the peel strength, and the like.
  • a copper foil provided with a surface treatment layer on a bonding surface of a copper foil used when producing a copper clad laminate by bonding with an insulating resin base material, the surface treatment layer being a bonding surface of the copper foil It is disclosed to employ a copper foil characterized in that it is obtained by adhering a zinc component, a high melting point metal component having a melting point of 1400 ° C. or higher, and further a carbon component. It is disclosed that “the bonding surface of the copper foil is preferably one having a surface roughness (Rzjis) of 2.0 ⁇ m or less without being subjected to a roughening treatment”.
  • Such a non-roughened copper foil does not have a concavo-convex shape formed by a roughening treatment on the surface bonded to the insulating resin base material. For this reason, when performing circuit formation by etching the copper foil, it is not necessary to provide an over-etching time for removing the anchor shape (uneven shape) embedded in the insulating resin substrate side. Therefore, if non-roughened copper foil is used, a fine pitch circuit having a good etching factor can be formed.
  • this non-roughened copper foil does not have an anchor shape (uneven shape) embedded in the insulating resin substrate side, the adhesion of the non-roughened copper foil to the insulating resin substrate is roughened. It tends to be lower than that of the copper foil subjected to.
  • the copper foil according to the present application includes a roughening treatment layer having a fine concavo-convex structure formed from needle-like or plate-like convex portions having a maximum length of 500 nm or less made of a copper composite compound, and The surface of the roughening treatment layer is provided with a silane coupling agent treatment layer on at least one surface.
  • Copper foil with carrier foil The copper foil with carrier foil according to the present application is characterized in that a carrier foil is provided on one side of the copper foil described above via a bonding interface layer.
  • Copper-clad laminate The copper-clad laminate according to the present application is obtained by using a copper foil or a copper foil with a carrier foil provided with the above-mentioned roughening treatment layer and silane coupling layer.
  • the copper foil or copper foil with carrier foil according to the present application is “a roughened layer having a fine concavo-convex structure formed by needle-like or plate-like convex portions having a maximum length of 500 nm or less made of a copper composite compound”. It has. For this reason, the surface provided with the roughening treatment layer is used as an adhesive surface with the insulating resin base material, so that the insulating resin base of the non-roughened copper foil can be obtained by the nano-anchor effect by the convex portions forming the fine uneven structure. Good adhesion can be ensured compared to the adhesion to the material.
  • the fine concavo-convex structure is formed by extremely short needle-like or plate-like convex portions having a maximum length of 500 nm or less, a slight over-etching time is required when forming a circuit by etching.
  • the convex part of the state embedded in the insulating resin base material side can be dissolved and removed. Therefore, good etching performance equivalent to that of the non-roughened copper foil can be realized, and a fine pitch circuit having a good etching factor can be formed.
  • a silane coupling agent treatment layer on the surface of the roughening treatment layer, it is possible to realize moisture absorption deterioration resistance equivalent to that of a conventional roughening copper foil.
  • Form of copper foil The copper foil according to the present application was formed on at least one surface of the copper foil from needle-like or plate-like convex portions having a maximum length of 500 nm or less made of a copper composite compound.
  • a roughening treatment layer having a fine concavo-convex structure and a silane coupling agent treatment layer on the surface of the roughening treatment layer are provided.
  • the copper foil which concerns on this application should just be equipped with the said roughening process layer in "at least one surface of copper foil", and the double-sided roughening process copper which provided the roughening process layer on both surfaces of copper foil Any of the single side
  • surface roughening process copper foil provided with the roughening process layer only in one side of foil and copper foil may be sufficient.
  • the copper foil according to the present application the copper foil may be an electrolytic copper foil or a rolled copper foil.
  • the thickness of the copper foil at this time is not particularly limited, and it is generally sufficient to recognize the copper foil as having a thickness of 200 ⁇ m or less.
  • the surface of the copper foil on which the roughening treatment layer and the silane coupling agent layer are provided may be referred to as a roughening treatment surface.
  • the roughened layer has a fine concavo-convex structure formed from needle-like or plate-like convex portions having a maximum length of 500 nm or less made of a copper composite compound.
  • a scanning electron microscope observation image showing the surface of the roughened layer when the roughened layer referred to in the present application is provided on the double-side smooth electrolytic copper foil is shown in FIG. Shown in a). As shown in FIG.
  • FIG. 1 (b) is a further enlarged view of the surface of the roughened layer shown in FIG. 1 (a), and is a scanning electron microscope observation image at a magnification of 50000 times.
  • the “convex portion” means a protruding portion extending in a needle shape or a plate shape from the surface of the copper foil when the cross section of the copper foil is observed.
  • the projecting portion is composed of a single crystal of a copper composite compound or an aggregate of a plurality of crystals, and the convex portions are densely provided on the surface of the copper foil as shown in FIGS. 1 (a) and 1 (b). It has been.
  • FIG. 2 shows an electrode surface and a deposition surface of a general electrolytic copper foil, and observation images of the respective surfaces when the roughening treatment layer is provided on each surface.
  • the surface shape of each surface of the electrolytic copper foil is finer along the surface shape of each surface before the roughening treatment. It can be confirmed that the concavo-convex structure is formed and the macroscopic surface shape of each surface before the roughening treatment is maintained after the roughening treatment.
  • the roughening treatment layer is formed so that the needle-like or plate-like convex portion of the nm order covers the surface of the copper foil thinly along the surface shape of the copper foil. Since it is densely provided on the surface of the foil, it is considered that the macroscopic surface shape of the copper foil before the roughening treatment can be maintained.
  • the roughening treatment layer referred to in the present application has a fine concavo-convex structure formed by convex portions on the order of nm, and the maximum length of the convex portions is extremely small as 500 nm or less as described above. It is possible to suppress a change in the surface roughness on the roughening treatment surface side before and after the treatment. In other words, by providing the roughened layer on the copper foil having a smooth surface, the surface having the smooth surface before the roughened layer is maintained, and the surface with nano-structures having the fine concavo-convex structure is maintained. An anchor effect can be expressed.
  • FIG. 3 is a scanning electron microscope observation image showing a cross section of the copper foil according to the present application.
  • a portion observed in a thin line shape is a convex portion.
  • the surface of the copper foil is covered with innumerable convex portions densely packed with each other, and each convex portion is provided so as to protrude from the surface of the copper foil along the surface shape of the copper foil. Is done.
  • the “maximum length of the convex portion” means that when the length from the base end to the tip end of each convex portion observed in the shape of the line (line segment) in the cross section of the copper foil is measured.
  • the maximum length of the convex portion is preferably 400 nm or less, and more preferably 300 nm or less. As the maximum length of the convex portion becomes shorter, a fine uneven structure can be imparted to the surface of the copper foil, and the surface shape of the copper foil before the roughening treatment can be maintained. The change in height can be suppressed.
  • a fine pitch circuit can be formed.
  • the “thickness of the roughening treatment layer” corresponds to the thickness of the fine uneven structure provided on the surface layer portion of the copper foil.
  • the length and the protruding direction of each convex part forming the fine concavo-convex structure are not constant, and the protruding direction of each convex part is not parallel to the thickness direction of the copper foil. Therefore, the length of the convex portion and the height of the convex portion in the thickness direction of the copper foil do not match, and the maximum length of the convex portion and the maximum thickness of the roughening treatment layer also match. Without having a relationship of (thickness of the roughened layer) ⁇ (maximum length of the convex portion).
  • the thickness of the roughening treatment layer varies.
  • the average thickness of the roughened layer is 400 nm.
  • the maximum length of the convex portion is 500 nm or less, and when the average thickness of the roughened layer is 100 nm or more, the maximum length of the convex portion is 100 nm or more.
  • the average thickness of the roughened layer is preferably 100 nm or more, and the average thickness of the roughened layer is within the range of 100 nm to 350 nm. In some cases, it has been determined that it is possible to combine “good adhesion more than the non-roughened copper foil to the insulating resin base material” and “good etching performance equivalent to the non-roughened copper foil”. In FIG. 3, the roughened layer has an average thickness of 250 nm.
  • the length of the tip portion that can be separately observed from other convex portions is preferably 250 nm or less.
  • “the length of the tip portion that can be separately observed from other convex portions refers to the length shown below.
  • the surface of the roughened layer is observed with a scanning electron microscope as described above, the roughened layer is separated from the surface of the copper foil as described above with reference to FIGS.
  • the convex part protrudes in the shape of a needle or a plate, and the convex part is provided densely on the surface of the copper foil, the base end part of the convex part from the surface of the copper foil, that is, a copper composite compound
  • the interface between the convex portion and the copper foil cannot be observed. Therefore, when the copper foil is observed in a plane as described above, it is separated from other convex portions among the convex portions adjacent to each other while being densely packed, and exists independently as one convex portion.
  • the portion that can be observed when it is obtained is referred to as the “tip portion that can be observed separately from other convex portions”, and the length of the tip portion refers to the tip of the convex portion (ie, the tip of the tip portion). The length up to the position on the most proximal side that can be separated and observed from other convex portions.
  • the maximum length of the convex portion is approximately 500 nm or less, and as described above, due to the nanoanchor effect due to the fine uneven structure of the roughened layer.
  • the length of the tip portion that can be separately observed from other convex portions is 250 nm or less, there is no convex portion that protrudes long from the surface of the copper foil, and the surface of the roughening treatment layer has another surface.
  • the length of the tip portion of the convex portion is preferably 200 nm or less, and more preferably 100 nm or less. Moreover, when obtaining favorable adhesiveness with an insulating resin base material, the length of the tip portion of the convex portion is preferably 30 nm or more, and more preferably 50 nm or more.
  • the length of the tip portion of the convex portion is 1 ⁇ 2 or less with respect to the maximum length of the convex portion.
  • the ratio is 1 ⁇ 2 or less, while separating from other convex portions, the tip portion of the convex portion protrudes from the surface of the copper foil, so that the nano anchor effect can be exhibited, Since the convex portions adjacent to each other on the base end side of the convex portions are densely packed on the copper foil surface while being in contact with each other, the copper foil surface can be densely covered with the fine concavo-convex structure.
  • the silane coupling agent treatment layer provided on the roughened surface is composed of olefin functional silane, epoxy functional silane, vinyl functional silane, acrylic functional silane, amino functional silane and mercapto functional silane as a silane coupling agent. Either can be used to form.
  • silane coupling agents are represented by the general formula R—Si (OR ′) n (where R: an organic functional group typified by an amino group or vinyl group, OR ′: a methoxy group or an ethoxy group) And the like, n: 2 or 3.
  • silane coupling agent said here is shown more specifically, vinyltrimethoxysilane, vinylphenyltrimethoxylane, mainly using the same coupling agent as used for a glass cloth of a prepreg for a printed wiring board, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, 4-glycidylbutyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, N- ⁇ (aminoethyl) ⁇ -aminopropyltrimethoxysilane, Use N-3- (4- (3-aminopropoxy) ptoxy) propyl-3-aminopropyltrimethoxysilane, imidazolesilane, triazinesilane, 3-acryloxypropylmethoxysilane, ⁇ -mercaptopropyltrimethoxysilane, etc. Is possible .
  • silane coupling agents listed here do not adversely affect the subsequent etching process and the characteristics after becoming a printed wiring board even when used on the adhesive surface of the copper foil with the insulating resin substrate.
  • Which type is used in the silane coupling agent can be appropriately selected according to the type of the insulating resin base material, the method of using the copper foil, and the like.
  • the silane coupling agent described above contains water as a main solvent, the silane coupling agent component is contained in a concentration range of 0.5 g / L to 10 g / L, and the silane coupling agent has a room temperature level. It is preferable to use an agent treatment liquid.
  • concentration of the silane coupling agent in the silane coupling agent treatment liquid is less than 0.5 g / L, the adsorption rate of the silane coupling agent is slow, which is not suitable for general commercial profit, and the adsorption is not uniform. It becomes.
  • the concentration of the silane cup agent exceeds 10 g / L, the adsorption rate is not particularly high, and the performance quality such as moisture absorption resistance is not particularly improved. .
  • the adsorption method of the silane coupling agent to the copper foil surface using this silane coupling agent treatment liquid can employ an immersion method, a showering method, a spraying method, etc., and is not particularly limited. That is, any method can be used as long as the copper foil and the silane coupling agent treatment solution can be brought into contact with each other and adsorbed in accordance with the process design.
  • the silane coupling agent After the silane coupling agent is adsorbed on the surface of the roughening treatment layer, it is sufficiently dried to perform a condensation reaction between the —OH group on the surface of the roughening treatment layer and the adsorbed silane coupling agent. Promote and completely evaporate the water resulting from the condensation.
  • the drying method at this time For example, even if an electric heater is used or a blast method that blows warm air is not particularly limited, a drying method and drying conditions corresponding to the production line may be employed.
  • the roughening treatment layer functions as a light absorbing layer that absorbs light, and the surface of the roughening treatment surface is darkened to blackening, browning, or the like as compared to before the roughening treatment.
  • the roughened surface of the copper foil according to the present application has a special color tone, and the lightness L * value of the L * a * b * color system is 25 or less.
  • the maximum length of the convex portion constituting the roughening treatment layer may exceed 500 nm, which is not preferable.
  • the value of L * exceeds 25 even if the maximum length of the convex portion is 500 nm or less, the convex portion may not be provided sufficiently densely on the surface of the copper foil. .
  • the value of the lightness L * exceeds 25 it is considered that the roughening treatment is insufficient or the state of the roughening treatment is uneven.
  • the value of the lightness L * may be used as an indicator of the "surface state of the roughened surface", as the value of the lightness L * is less than 25, no relative "insulating resin substrate Arakado It can be considered that the surface state is better in obtaining “adhesiveness better than that of foil”, and if the value of the lightness L * is 20 or less, the reliability with respect to the adhesiveness with the insulating resin substrate is high. This is preferable because it improves dramatically.
  • the lightness L * in the present application was measured using a spectral color difference meter SE2000 manufactured by Nippon Denshoku Industries Co., Ltd., and the whiteness plate attached to the measuring device was used for lightness calibration in accordance with JIS Z8722: 2000. . And the measurement of 3 times is performed regarding the same site
  • the convex part which forms the fine concavo-convex structure in the roughening process layer of the copper foil which concerns on this application consists of a copper complex compound.
  • the copper composite compound preferably contains copper oxide and cuprous oxide.
  • the high frequency signal does not flow through the roughened layer. That is, if the copper foil which concerns on this application is used, the high frequency characteristic equivalent to the non-roughened copper foil which is not provided with the roughening process layer will be shown regarding the transmission loss of a high frequency signal.
  • the roughened layer has good adhesion to a low dielectric constant and low dielectric loss tangent insulating resin substrate used for a high frequency substrate. Therefore, the copper foil which concerns on this application is very suitable as a high frequency circuit formation material by providing the said roughening process layer with respect to the untreated copper foil which was excellent in the following high frequency characteristics, for example.
  • a copper foil suitable for a high-frequency circuit forming material can be obtained by providing the roughening layer on an untreated copper foil having the following characteristics.
  • the copper foil according to the present application can be suitably used for manufacturing a microstrip line or a strip line by providing the roughening treatment layer for an untreated copper foil having the following characteristics. it can.
  • the surface roughness (Rz) and glossiness (Gs60 °) of the surface in close contact with the insulating resin substrate are within the following ranges, respectively.
  • the insulating resin base material is in close contact with both surfaces, and therefore the surface characteristics of both surfaces are preferably within the following range.
  • Cu obtained when the constituent elements of the roughened layer are analyzed by X-ray photoelectron spectroscopy hereinafter referred to as “XPS”.
  • the ratio of the peak area of Cu (I) (hereinafter referred to as the occupied area ratio) to the total area of the peak area of I) and the peak area of Cu (II) is preferably 50% or more.
  • each peak of Cu (I) and Cu (II) can be separated and detected.
  • the Cu (0) peak may be observed overlapping the shoulder portion of the large Cu (I) peak.
  • the peak of Cu (0) is observed overlappingly, it shall be considered as a Cu (I) peak including this shoulder part.
  • the constituent elements of the copper composite compound forming the fine concavo-convex structure layer are analyzed using XPS, and Cu (I) and 934 appearing at 932.4 eV corresponding to the binding energy of Cu 2p 3/2.
  • Each peak obtained by detecting photoelectrons of Cu (II) appearing at .3 eV is separated into waveforms, and the occupied area ratio of the Cu (I) peak is specified from the peak area of each component.
  • Quantum 2000 (beam condition: 40 W, 200 ⁇ m diameter) manufactured by ULVAC-PHI Co., Ltd. is used as an XPS analyzer
  • “MultiPack ver. 6.1A” is used as analysis software to perform state / semi-quantitative narrow measurement. be able to.
  • the Cu (I) peak obtained as described above is considered to be derived from monovalent copper constituting cuprous oxide (cuprous oxide: Cu 2 O). And it is thought that a Cu (II) peak originates in the bivalent copper which comprises copper oxide (cupric oxide: CuO). Furthermore, it is considered that the Cu (0) peak is derived from zero-valent copper constituting metallic copper. Therefore, when the occupation area ratio of the Cu (I) peak is less than 50%, the proportion of cuprous oxide in the copper composite compound constituting the roughened layer is smaller than the proportion of copper oxide. Copper oxide has higher solubility in acids such as an etchant than cuprous oxide.
  • the occupied area ratio of the Cu (I) peak is less than 50%, when the roughened surface side of the copper foil is bonded to the insulating resin substrate and the circuit is formed by the etching method, A roughening process layer becomes easy to melt
  • the occupied area ratio of the Cu (I) peak is 70% or more and 80% or more when the constituent elements of the copper composite compound that forms the roughened layer by XPS are analyzed. More preferably it is.
  • the component ratio of cuprous oxide having higher acid solubility resistance to the etching solution or the like becomes higher than that of copper oxide.
  • the acid solubility resistance of the roughened layer to the etching solution is improved, and it becomes possible to reduce the insertion of the etching solution during circuit formation, thereby forming a copper wiring having good adhesion to the insulating resin substrate. be able to.
  • the upper limit value of the occupied area ratio of the Cu (I) peak is not particularly limited, but is 99% or less. As the occupied area ratio of the Cu (I) peak decreases, the adhesiveness between the two surfaces when the roughened surface side of the copper foil is bonded to the insulating resin base material tends to be improved.
  • the exclusive area ratio of the Cu (I) peak is preferably 98% or less, and more preferably 95% or less.
  • the occupied area ratio of the Cu (I) peak is calculated by a calculation formula of Cu (I) / ⁇ Cu (I) + Cu (II) ⁇ ⁇ 100 (%).
  • the specific surface area (hereinafter simply referred to as “specific surface area”) measured by adsorbing krypton on the surface of the roughened layer is preferably 0.035 m 2 / g or more.
  • the specific surface area measured in this way is 0.035 m 2 / g or more
  • the average thickness of the roughened layer becomes 200 nm or more
  • the roughened surface provided with the roughened layer is insulated.
  • good adhesion can be ensured.
  • the upper limit value of the specific surface area is not particularly limited, the fine concavo-convex structure is formed by densely forming needle-like or plate-like convex portions having a maximum length of 500 nm or less.
  • the upper limit value of the specific surface area is calculated to be about 0.3 m 2 / g, and actually about 0.2 m 2 / g is the upper limit value.
  • the specific surface area is measured by using a specific surface area / pore distribution measuring device 3Flex manufactured by Micromeritics Co., Ltd. as a pretreatment by heating the sample at 300 ° C. for 2 hours. The above measurement can be performed by using krypton (Kr).
  • the roughening treatment layer according to the present application described above can be formed, for example, by subjecting the surface of the copper foil to a roughening treatment by the following wet method.
  • a copper compound containing copper oxide (cupric oxide) is formed on the surface of the copper foil by oxidizing the surface of the copper foil by a wet method using a solution.
  • the copper compound is reduced, and a part of the copper oxide is converted into cuprous oxide (cuprous oxide), thereby forming a “needle or plate comprising a copper composite compound containing copper oxide and cuprous oxide.
  • the fine concavo-convex structure formed from the convex portions can be formed on the surface of the copper foil.
  • the “fine concavo-convex structure” itself referred to in the present application is formed of a copper compound containing copper oxide at the stage where the surface of the copper foil is oxidized by a wet method. And when the said copper compound is reduce
  • a small amount of metallic copper may be contained in a copper composite compound containing copper oxide and cuprous oxide as main components.
  • an alkaline solution such as a sodium hydroxide solution when the wet roughening treatment is performed.
  • an alkaline solution such as a sodium hydroxide solution
  • a convex portion made of a copper compound containing needle-like or plate-like copper oxide can be formed on the surface of the copper foil.
  • the convex portion grows long, and the maximum length may exceed 500 nm, forming the fine concavo-convex structure referred to in the present application. It becomes difficult. Therefore, in order to form the fine concavo-convex structure, it is preferable to use an alkaline solution containing an oxidation inhibitor capable of finely suppressing oxidation on the copper foil surface.
  • Examples of such an oxidation inhibitor include an amino silane coupling agent. If the copper foil surface is oxidized using an alkaline solution containing an amino silane coupling agent, the amino silane coupling agent in the alkaline solution is adsorbed on the surface of the copper foil, and the copper foil surface by the alkaline solution Can be finely suppressed. As a result, the growth of copper oxide needle-like crystals can be suppressed, and the roughened layer referred to in the present application having an extremely fine concavo-convex structure on the order of nm can be formed.
  • amino-based silane coupling agent examples include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3- Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, etc. may be used. It can. All of these are dissolved in an alkaline solution and are stably held in the alkaline solution, and also exhibit the effect of finely suppressing the oxidation of the copper foil surface described above.
  • the fine concavo-convex structure formed by subjecting the surface of the copper foil to an oxidation treatment with an alkaline solution containing an amino-based silane coupling agent is substantially maintained even after the reduction treatment.
  • a roughening treatment layer having a fine concavo-convex structure on the order of nm formed by needle-like or plate-like convex portions having a maximum length of 500 nm or less, comprising copper oxide and cuprous oxide, and having a maximum length of 500 nm or less. can be obtained.
  • the roughening treatment layer is formed on both sides of the copper foil by a method such as immersing the copper foil in the treatment solution. It can be formed easily. Therefore, when this wet method is used, it becomes possible to easily obtain a double-sided roughened copper foil suitable for forming an inner layer circuit of a multilayer printed wiring board, and both the inner layer circuit and the interlayer insulating layer and the like are good. Adhesion can be ensured.
  • the roughened layer according to the present application is less likely to cause so-called powder falling during handling and the like, and can maintain a fine uneven structure on the surface. Accordingly, handling can be facilitated even when a double-side roughened copper foil is used.
  • Form of copper foil with carrier foil In the case of copper foil with carrier foil according to the present application, it is possible to apply all of the concepts applied to the copper foil described above. Therefore, only different parts will be described in detail.
  • the copper foil with carrier foil according to the present application is a copper foil with carrier foil having a layer configuration of carrier foil / bonding interface layer / copper foil layer, and the outer surface of the carrier foil and the outer surface of the copper foil layer.
  • a silane coupling agent treatment layer is provided on the surface of the roughening treatment layer.
  • the surface on which the roughening treatment layer is provided is referred to as a roughening treatment surface.
  • the copper foil with carrier foil includes “when both the outer surface of the carrier foil and the outer surface of the copper foil layer are roughened surfaces”.
  • the outer surface of the carrier foil is a surface exposed on the surface of the carrier foil constituting the copper foil with the carrier foil, and “the outer surface of the copper foil layer”. "Is the surface exposed on the surface of the copper foil layer constituting the copper foil with carrier foil.
  • the material for the carrier foil referred to here.
  • a carrier foil copper foil (here, a concept including rolled copper foil, electrolytic copper foil, etc., regardless of its production method), and copper components such as resin foil coated with copper on the surface are present on the surface.
  • copper foil here, a concept including rolled copper foil, electrolytic copper foil, etc., regardless of its production method
  • copper components such as resin foil coated with copper on the surface are present on the surface.
  • it can be used. Judging from the viewpoint of cost, it is preferable to use copper foil.
  • the thickness as carrier foil there is no limitation in particular also about the thickness as carrier foil. From the industrial point of view, the concept as a foil generally refers to a foil having a thickness of 200 ⁇ m or less, and it is sufficient to use this concept.
  • the bonding interface layer there is no particular limitation as long as it can be a peelable type product from which the carrier foil can be peeled off, as long as the characteristics required for the bonding interface layer are satisfied.
  • Either an inorganic bonding interface layer composed of an agent or an organic bonding interface layer composed of an organic agent can be used.
  • an inorganic agent which comprises an inorganic joining interface layer 1 type, or 2 or more types chosen from chromium, nickel, molybdenum, a tantalum, vanadium, tungsten, cobalt, and these oxides can be mixed and used, for example.
  • an organic joining interface layer comprised from an organic agent what consists of 1 type (s) or 2 or more types selected from a nitrogen containing organic compound, a sulfur containing organic compound, and carboxylic acid can be used.
  • the nitrogen-containing organic compound include 1,2,3-benzotriazole, carboxybenzotriazole, N ′, N′-bis (benzotriazolylmethyl) urea, which are triazole compounds having a substituent, and 1H. It is preferable to use -1,2,4-triazole, 3-amino-1H-1,2,4-triazole and the like.
  • the sulfur-containing organic compound it is preferable to use mercaptobenzothiazole, thiocyanuric acid, 2-benzimidazolethiol, and the like.
  • the carboxylic acid it is particularly preferable to use a monocarboxylic acid, and it is particularly preferable to use oleic acid, linoleic acid, linolenic acid, or the like.
  • both of the inorganic bonding interface layer and the organic bonding interface layer can be preferably used.
  • the carrier foil has an appropriate peeling strength. From the viewpoint of ensuring the thickness stably, it is more preferable to use an organic bonding interface layer.
  • the method for forming the bonding interface layer with this organic agent is to dissolve the above-mentioned organic agent in a solvent and immerse the carrier foil in the solution, or to perform showering, spraying, dripping on the surface on which the bonding interface layer is to be formed.
  • concentration of the organic agent in the solvent is preferably in the range of 0.01 g / L to 10 g / L and the liquid temperature of 20 to 60 ° C. in all the organic agents described above.
  • an auxiliary metal layer such as Ni or Co may be formed on the surface of the organic bonding interface layer in order to improve the heat resistance of the bonding interface layer.
  • the copper foil layer is described as including not only a copper foil called an ultrathin copper foil of 12 ⁇ m or less but also a layer formed of a copper foil thicker than 12 ⁇ m. This is because in the case of a copper foil layer having a thickness of 12 ⁇ m or more, the carrier foil may be used to prevent surface contamination.
  • the carrier foil according to the present application is provided with the roughening treatment layer and the silane coupling agent treatment layer described in the description of the copper foil on the surface of the copper foil layer of the copper foil with carrier foil described above. It is a copper foil. That is, the copper foil with carrier foil according to the present application is obtained by subjecting the surface of the copper foil layer to roughening treatment (oxidation treatment and reduction treatment) and silane coupling agent treatment. Therefore, the duplicate description here is omitted.
  • Form of copper-clad laminate The copper-clad laminate according to the present application is obtained using a copper foil or a copper foil with a carrier foil provided with the above-mentioned roughening treatment layer. If the copper clad laminate at this time is obtained using a copper foil or a copper foil with a carrier foil according to the present application, the constituent components of the used insulating resin base material, the thickness, the laminating method, etc. There is no special limitation. Moreover, the copper clad laminated board here contains both a rigid type and a flexible type.
  • a copper clad laminate as a printed wiring board manufacturing material is obtained by removing the carrier foil after the copper foil with a carrier foil and an insulating resin base material are bonded together. Is obtained.
  • Example 1 a copper electrolyte solution having the composition described in the following is used, DSA is used as an anode, and a cathode (a titanium plate electrode whose surface is polished with No. 2000 polishing paper), a liquid temperature is 50 ° C., and a current density is 60 A / dm 2.
  • the electrolytic copper foil having a thickness of 18 ⁇ m was obtained.
  • the surface roughness (Rz) of the deposited surface of the obtained electrolytic copper foil was 0.2 ⁇ m, and the glossiness (Gs60 °) was 600.
  • the measurement of glossiness and the measurement of surface roughness are as follows.
  • Copper electrolyte composition Copper concentration: 80 g / L Free sulfuric acid concentration: 140 g / L Bis (3-sulfopropyl) disulfide concentration: 5 mg / L Diallyldimethylammonium chloride polymer concentration: 30 mg / L Chlorine concentration: 25mg / L
  • Glossiness was measured using a gloss meter PG-1M manufactured by Nippon Denshoku Industries Co., Ltd. according to JIS Z 8741-1997, which is a glossiness measurement method.
  • Pretreatment The electrolytic copper foil produced as described above was immersed in an aqueous sodium hydroxide solution, subjected to alkaline degreasing treatment, and washed with water. And after immersing the electrolytic copper foil which this alkali degreasing process complete
  • the copper foil that had been subjected to the preliminary treatment was subjected to an oxidation treatment.
  • the electrolytic copper foil is treated with sodium hydroxide containing a liquid temperature of 70 ° C., pH 12, chlorous acid concentration of 150 g / L, and N-2- (aminoethyl) -3-aminopropyltrimethoxysilane concentration of 10 g / L. It was immersed in the solution for 2 minutes to form a fine concavo-convex structure made of a copper compound on the surface of the electrolytic copper foil.
  • the main component of the copper compound at this time is considered to be copper oxide.
  • a reduction treatment was performed on the electrolytic copper foil that had been subjected to the oxidation treatment.
  • a roughening treatment having a fine concavo-convex structure made of a copper composite compound containing copper oxide and cuprous oxide is obtained by reducing a part of the copper oxide to cuprous oxide on the surface of the electrolytic copper foil. A layer was formed.
  • Silane coupling agent treatment When the reduction treatment is completed, after washing with water, a silane coupling agent treatment solution (an aqueous solution containing 5 g / L of ⁇ -glycidoxypropyltrimethoxysilane using ion-exchanged water as a solvent) It sprayed on the roughening surface of the electrolytic copper foil after the said roughening process by the showering method, and adsorption
  • the adsorption of the silane coupling When the adsorption of the silane coupling is completed, the moisture on the surface is evaporated in an atmosphere at 120 ° C. using an electric heater, and the —OH group and the silane coupling agent on the roughened surface are The condensation reaction was promoted to obtain a copper foil according to the present application having a silane coupling agent treatment layer on the surface of the roughening treatment layer.
  • Lightness L * of the roughened surface The value of lightness L * of the copper foil obtained in this example was 10.
  • Hygroscopic deterioration performance evaluation results Using the copper foil of Example 1 and a 100 ⁇ m thick insulating resin substrate (MEGTRON4 manufactured by Panasonic Corporation), using a vacuum press machine, the pressing pressure is 2.9 MPa, the temperature Bonding was performed under the conditions of 190 ° C. and a press time of 90 minutes to produce a copper clad laminate. Next, using this copper-clad laminate, a test substrate having a 3.0 mm width peel strength measuring linear circuit was produced by an etching method. And using this test board
  • Example 2 a copper foil with a carrier foil using the electrolytic copper foil (untreated copper foil) produced in Example 1 as a carrier foil was produced according to the following procedure.
  • an organic agent layer was formed as a bonding interface layer on the deposition surface side of the carrier foil.
  • the carrier foil was immersed for 30 seconds in an organic material-containing dilute sulfuric acid aqueous solution having a sulfuric acid concentration of 150 g / L, a copper concentration of 10 g / L, a CBTA concentration of 800 ppm, and a liquid temperature of 30 ° C.
  • the contaminating component adhering to the surface of the carrier foil was acid-washed, and CBTA was adsorbed on the surface of the carrier foil to form an organic agent layer mainly composed of CBTA.
  • a nickel layer was formed as a refractory metal layer on the bonding interface layer.
  • a Watts bath having a nickel sulfate (NiSO 4 ⁇ 6H 2 O) concentration of 330 g / L, a nickel chloride (NiCl 2 ⁇ 6H 2 O) concentration of 45 g / L, a boric acid concentration of 35 g / L, and a pH of 3
  • Electrolysis was performed under electrolytic conditions of a liquid temperature of 45 ° C. and a current density of 2.5 A / dm 2 to form a nickel layer having a converted thickness of 0.01 ⁇ m on the bonding interface layer.
  • the electrolytic copper foil layer was formed on the said heat-resistant metal layer. Specifically, using a copper electrolytic solution having a copper concentration of 65 g / L and a sulfuric acid concentration of 150 g / L, electrolysis is performed under electrolytic conditions of a liquid temperature of 45 ° C. and a current density of 15 A / dm 2 , and the thickness is formed on the heat-resistant metal layer. A 2 ⁇ m electrolytic copper foil layer was formed. At this time, the surface roughness (Rz) on the deposition surface side of this electrolytic copper foil layer was 0.2 ⁇ m, and the glossiness [Gs (60 °)] was 600. The surface treatment was performed in the following procedure on the surface of the electrolytic copper foil layer of the electrolytic copper foil with carrier foil formed as described above.
  • Pretreatment The copper foil with carrier foil was subjected to alkali degreasing treatment and sulfuric acid treatment in the same manner as in Example 1 and washed with water.
  • the surface of the electrolytic copper foil layer is made of a copper compound by oxidizing the surface of the electrolytic copper foil layer of the copper foil with carrier foil after the preliminary treatment in the same manner as in Example 1. A fine relief structure was formed. Next, the surface on which the copper composite compound of the electrolytic copper foil layer of the copper foil with carrier foil after the oxidation treatment was formed was subjected to reduction treatment in the same manner as in Example 1, and the surface of the electrolytic copper foil layer was subjected to copper oxide and suboxide. A roughening treatment layer having a fine concavo-convex structure made of a copper composite compound containing copper oxide was formed.
  • Silane coupling agent treatment When the above reduction treatment was completed, a silane coupling agent treatment was performed in the same manner as in Example 1 to obtain a copper foil with a carrier foil according to the present application.
  • Lightness L * of roughened surface The value of lightness L * of the roughened surface of the electrolytic copper foil layer of the copper foil with carrier foil obtained in Example 2 was 18.
  • Moisture absorption degradation performance evaluation results The roughened surface of the electrolytic copper foil layer of the copper foil with carrier foil of Example 2 and an insulating resin base material (GHPL-830NS, manufactured by Mitsubishi Gas Chemical Co., Ltd.) having a thickness of 100 ⁇ m, Using a vacuum press machine, a copper-clad laminate was manufactured by bonding together under the conditions of a pressing pressure of 3.9 MPa, a temperature of 220 ° C., and a pressing time of 90 minutes. Then, the carrier foil on the surface of the copper-clad laminate is removed, and the exposed electrolytic copper foil layer is subjected to electrolytic copper plating so as to have a thickness of 18 ⁇ m, and an etching method is used to measure the peel strength.
  • GHPL-830NS insulating resin base material
  • a test substrate with a 4 mm wide linear circuit was produced. Then, using this test substrate, the normal peel strength and the peel strength after the PCT moisture absorption treatment were measured. However, the PCT moisture absorption treatment was performed by holding the test substrate for 24 hours (PCT test) in a high-temperature and high-pressure steam atmosphere of 121 ° C. ⁇ 2 atm. Further, the peel strength of the dried test substrate after the PCT treatment was measured, and the value at this time was defined as the peel strength after the PCT moisture absorption treatment.
  • [PCT moisture absorption deterioration rate (%)] 100 ⁇ ⁇ [normal peel strength] ⁇ [peel strength after PCT moisture absorption] ⁇ / [normal peel strength]
  • the anti-PCT moisture absorption deterioration rate was calculated according to the calculation formula.
  • [normal peel strength] 0.75 kgf / cm
  • [peel strength after moisture absorption treatment] 0.68 kgf / cm
  • [moisture resistance deterioration rate (%)] of the electrolytic copper foil of Example 1 ] 9.3%.
  • Example 2 Using the electrolytic copper foil (untreated electrolytic copper foil) produced in Example 1, surface treatment was performed in the following procedure.
  • the oxidation treatment (oxidation treatment time: 2 minutes) performed in the preliminary treatment and the roughening treatment and the silane coupling agent treatment after the roughening treatment are the same as those in Example 1.
  • the pH and dimethylamine borane concentration of the aqueous solution used for the reduction treatment were changed as follows, and these effects were verified.
  • the copper foil which concerns on this application was obtained by immersing for 1 minute in each of nine types of aqueous solution (room temperature) which combined these three levels, performing a reduction process, washing with water, and drying.
  • the copper foils obtained when the aqueous solution used for the reduction treatment had a pH of 12 were designated as “Execution Sample 12-a, Implementation Sample 12-b, and Implementation Sample 12-c”.
  • the “ ⁇ a” display when indicating each of the samples is when the dimethylamine borane concentration in the aqueous solution used for the reduction treatment is 5 g / L.
  • the “ ⁇ b” display is when the dimethylamine borane concentration in the aqueous solution used for the reduction treatment is 10 g / L.
  • “ ⁇ c” is indicated when the dimethylamine borane concentration in the aqueous solution used for the reduction treatment is 20 g / L.
  • Example 3 The scanning electron microscope observation images of all the working samples obtained in Example 3 were in the same form as shown in FIG. Then, when the state of the “fine irregularities made of a copper composite compound” on the surface of the roughened layer of each of the implementation samples is analyzed using XPS, the presence of “copper oxide” and “cuprous oxide” is clearly confirmed. Table 3 shows the occupation area ratio of the peak of Cu (I) with respect to the total area of the peak area of Cu (I) and the peak area of Cu (II). Further, as a result of this qualitative analysis, the presence of “—COO group” was clearly confirmed on the roughened surface. Further, in the same manner as in Example 1, a test substrate was produced using each sample. Then, using this test substrate, the normal peel strength and the peel strength after moisture absorption treatment were measured in the same manner as in Example 1. These results are shown together in Table 3.
  • Comparative Example 1 The copper foil of Comparative Example 1 is obtained by omitting the silane coupling agent treatment in the copper foil of Example 1. In contrast to the copper foil described in Example 1, the presence or absence of the silane coupling agent treatment is It is for confirming the influence which it has on moisture absorption degradation performance. Therefore, except for the silane coupling agent treatment, other manufacturing conditions are the same as those in the example, and therefore, a duplicate description is omitted and only the evaluation results are described below.
  • Lightness L * of the roughened surface The value of the lightness L * of the copper foil obtained in Comparative Example 1 was 10.
  • Comparative Example 2 The copper foil with carrier foil of Comparative Example 2 is obtained by subjecting the copper foil with carrier foil used in Example 2 to roughening treatment, rust prevention treatment, and silane coupling agent treatment according to the following procedure.
  • the copper foil with carrier foil described in Example 2 it is for confirming the influence of the difference in the roughening treatment layer on the PCT moisture absorption deterioration rate. Therefore, regarding the manufacturing conditions, portions different from those in the second embodiment will be described, and redundant description will be omitted.
  • Roughening treatment In the roughening treatment step, fine copper particles were deposited on the surface of the electrolytic copper foil layer of the copper foil with carrier foil. At this time, a burn plating condition in which a copper sulfate solution (sulfuric acid concentration 100 g / L, copper concentration 18 g / L), liquid temperature 25 ° C., current density 10 A / dm 2 , and energization time 10 seconds was adopted.
  • a copper sulfate solution sulfuric acid concentration 100 g / L, copper concentration 18 g / L
  • liquid temperature 25 ° C. current density 10 A / dm 2
  • energization time 10 seconds was adopted.
  • a copper sulfate solution (sulfuric acid concentration 150 g / L, copper concentration 65 g / L), liquid temperature 45 ° C., current density 15 A / dm 2 , energization time 20
  • a copper sulfate solution sulfuric acid concentration 150 g / L, copper concentration 65 g / L
  • liquid temperature 45 ° C. current density 15 A / dm 2
  • energization time 20 By adopting second smooth plating conditions, fine copper particles were fixed on the surface of the electrolytic copper foil layer.
  • Rust prevention treatment Here, the surface of the electrolytic copper foil layer of the carrier foil-attached copper foil having been subjected to the roughening treatment was subjected to a rust prevention treatment using zinc as a rust prevention element.
  • the rust prevention treatment layer uses a zinc sulfate bath, uses a zinc sulfate solution having a sulfuric acid concentration of 70 g / L and a zinc concentration of 20 g / L, a liquid temperature of 40 ° C., a current density of 15 A / dm 2 , and an energization time of 20
  • the zinc anticorrosive treatment layer was formed using the second condition.
  • Example 2 similarly to Example 2, the silane coupling agent treatment and drying were performed to obtain a copper foil with a carrier foil of Comparative Example 2.
  • Lightness L * of roughened surface The value of lightness L * of the copper foil obtained in Comparative Example 2 was 46.
  • Comparative Example 3 In Comparative Example 3, the same pretreatment as in Example 1 was performed using the same electrolytic copper foil as in Example 1, and instead of the roughening process in Example, blackening treatment and reduction treatment were performed to obtain Comparative Sample 3. It was. Hereinafter, the blackening process and the reduction process will be described.
  • Blackening treatment 10% by volume of “PRO BOND 80A OXIDE SOLUTION”, which is an oxidation treatment solution manufactured by Rohm & Haas Electronic Materials Co., Ltd.
  • a general blackening treatment was formed on the surface by immersing in an aqueous solution containing 20 vol% and having a liquid temperature of 85 ° C. for 5 minutes.
  • Reduction treatment The oxidized copper foil after the oxidation treatment is reduced to 6.7 vol% for “CIRCUPOSIT PB OXIDE CONVERTER 60C”, which is a reduction treatment solution manufactured by Rohm & Haas Electronic Materials Co., Ltd. 5% immersion in an aqueous solution having a liquid temperature of 35 ° C., washed with water, and dried to obtain a comparative sample having a reduction blackening treatment layer shown in FIG.
  • the state of the surface of the roughened layer of the surface-treated copper foil (comparative sample) obtained in this comparative example was analyzed using XPS, and the presence of “Cu (0)” was confirmed.
  • the presence of “Cu (II)” and “Cu (I)” was also confirmed, and the peak of Cu (I) relative to the total area of the peak area of Cu (I) and the peak area of Cu (II) was confirmed.
  • the occupied area ratio is as shown in Table 3.
  • the presence of “—COO group” was not confirmed on the roughened surface.
  • Example 1 Comparison between Example 1 and Comparative Example 1 The comparison between Example 1 and Comparative Example 1 is for confirming the effect of the silane coupling agent treatment.
  • the evaluation results of Example 1 and Comparative Example 1 are shown in Table 1 below.
  • Example 2 and Comparative Example 2 The comparison between Example 2 and Comparative Example 2 is that the copper foil with carrier foil according to the present application is a copper foil with carrier foil subjected to conventional roughening treatment, etc. On the other hand, it is for confirming what superiority is exhibited.
  • the evaluation results of Example 2 and Comparative Example 2 are shown in Table 2 below.
  • the copper foil with carrier foil of Comparative Example 2 is different from the copper foil with carrier foil of Example 2 in the roughening treatment method.
  • the “roughening surface shape” is Different.
  • the components which comprise a roughening process layer differ. Specifically, “copper oxide”, “cuprous oxide”, and “—COO group” were detected by XPS from the roughened surface of the copper foil with carrier foil of Example 2. These components are hardly detected from the roughened surface, and the roughened layer of the comparative example is composed of fine copper grains electrodeposited on the surface of the copper foil, so that the main component is mainly “copper” or “ Copper alloy ".
  • the needle-shaped or plate-shaped convex which consists of a copper complex compound It can be seen that the concavo-convex structure formed by the shaped portions is finer than the concavo-convex structure formed by the fine copper particles attached to the surface of the copper foil in the roughening treatment layer of Comparative Example 2.
  • Example 2 As a result, the moisture resistance deterioration rate of Example 2 is 9.3%, while the humidity resistance deterioration rate of Comparative Example 2 is reduced to 22.0%. Therefore, it is clear that the copper foil with carrier foil of Comparative Example 2 is not suitable for manufacturing printed wiring boards that are exposed to much water or various aqueous solutions as compared with the copper foil with carrier foil of Example 2.
  • Example 3 and Comparative Example 3 Comparison between Example 3 and Comparative Example 3: Next, referring to Table 3 below, Example 3 and Comparative Example 3 are compared.
  • the occupied area ratio of the Cu (I) peak is 83%. Therefore, in the occupied area ratio of the Cu (I) peak, it can be seen that there is no difference between Example 3 and Comparative Example 3.
  • the state analysis by XPS described above the detected components are different. The presence of “—COO group” was not confirmed on the roughened surface of the sample.
  • planar observation of the roughened surface of the comparative sample 3 is performed, a long and thick needle-like convex portion is observed, and the shape of the convex portion formed by the blackening treatment is an oxidation treatment performed on the implementation sample. Unlike the shape of the convex part formed later, the tip part is sharply pointed.
  • the thickness of the concavo-convex structure layer formed by the blackening treatment was 700 nm.
  • the tip of the convex part was rounded, and the uneven shape of the surface was greatly changed by the reduction process.
  • the cross section after the reduction treatment was observed for the comparative sample 3
  • the surface shape of the fine concavo-convex structure formed by the oxidation treatment was maintained after the reduction treatment. That is, it can be predicted that the convex portion formed in the comparative sample is very fragile as compared with the working sample, and a so-called problem of powder falling occurs.
  • the peel strength of the surface-treated copper foil obtained in Example 3 and Comparative Example 3 will be compared.
  • the peel strength of the working sample is 0.69 kgf / cm to 0.81 kgf / cm.
  • the peeling strength of the comparative sample was 0.33 kgf / cm, which was confirmed to be lower than the working sample.
  • the copper foil or carrier foil-attached copper foil according to the present application described above is “a roughened layer having a fine concavo-convex structure formed by needle-like or plate-like convex portions having a maximum length of 500 nm or less”. I have. For this reason, the surface provided with the roughening treatment layer is used as an adhesive surface with the insulating resin base material, so that the insulating resin base of the non-roughened copper foil can be obtained by the nano-anchor effect by the convex portions forming the fine uneven structure. Good adhesion can be ensured compared to the adhesion to the material.
  • the fine concavo-convex structure is formed by extremely short needle-like or plate-like convex portions having a maximum length of 500 nm or less, a slight over-etching time is required when forming a circuit by etching.
  • the convex part of the state embedded in the insulating resin base material side can be dissolved and removed. Therefore, good etching performance equivalent to that of the non-roughened copper foil can be realized, and a fine pitch circuit having a good etching factor can be formed.
  • a silane coupling agent treatment layer on the surface of the roughening treatment layer, it is possible to realize moisture absorption deterioration resistance equivalent to that of a conventional roughening copper foil.
  • the copper foil according to the present application can be provided with a roughening treatment layer on both sides of the copper foil, and powder formation is suppressed, so that the inner layer circuit formation of the multilayer printed wiring board is achieved. It can be set as the double-side roughening copper foil suitable for.

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Manufacturing Of Printed Wiring (AREA)
  • Parts Printed On Printed Circuit Boards (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
PCT/JP2014/071798 2013-09-20 2014-08-20 銅箔、キャリア箔付銅箔及び銅張積層板 WO2015040998A1 (ja)

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MYPI2016700973A MY182166A (en) 2013-09-20 2014-08-20 Copper foil, copper foil with carrier foil, and copper-clad laminate
KR1020167007204A KR101920976B1 (ko) 2013-09-20 2014-08-20 구리박, 캐리어박 부착 구리박, 및 구리 피복 적층판

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WO2022202921A1 (ja) * 2021-03-25 2022-09-29 ナミックス株式会社 積層体の製造方法
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WO2022202540A1 (ja) * 2021-03-26 2022-09-29 三井金属鉱業株式会社 粗化処理銅箔、キャリア付銅箔、銅張積層板及びプリント配線板
WO2022224684A1 (ja) * 2021-04-20 2022-10-27 ナミックス株式会社 銅部材

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MY182166A (en) 2021-01-18
TW201524279A (zh) 2015-06-16
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