CN107614753A - 覆铜层叠板的制造方法 - Google Patents

覆铜层叠板的制造方法 Download PDF

Info

Publication number
CN107614753A
CN107614753A CN201780001695.7A CN201780001695A CN107614753A CN 107614753 A CN107614753 A CN 107614753A CN 201780001695 A CN201780001695 A CN 201780001695A CN 107614753 A CN107614753 A CN 107614753A
Authority
CN
China
Prior art keywords
copper
copper foil
thermoplastic resin
laminated board
roughening
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201780001695.7A
Other languages
English (en)
Other versions
CN107614753B (zh
Inventor
立冈步
细川真
川口彰太
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Namics Corp
Original Assignee
Mitsui Mining and Smelting Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsui Mining and Smelting Co Ltd filed Critical Mitsui Mining and Smelting Co Ltd
Publication of CN107614753A publication Critical patent/CN107614753A/zh
Application granted granted Critical
Publication of CN107614753B publication Critical patent/CN107614753B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/09—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/12—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/061—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/285—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyethers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/286—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysulphones; polysulfides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/288—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyketones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/322—Layered products comprising a layer of synthetic resin comprising polyolefins comprising halogenated polyolefins, e.g. PTFE
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/325—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polycycloolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/144—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers using layers with different mechanical or chemical conditions or properties, e.g. layers with different thermal shrinkage, layers under tension during bonding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0012—Mechanical treatment, e.g. roughening, deforming, stretching
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/022—Non-woven fabric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/024—Woven fabric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • 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
    • 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
    • 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
    • H05K3/385—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by conversion of the surface of the metal, e.g. by oxidation, whether or not followed by reaction or removal of the converted layer
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/40—General aspects of joining substantially flat articles, e.g. plates, sheets or web-like materials; Making flat seams in tubular or hollow articles; Joining single elements to substantially flat surfaces
    • B29C66/41—Joining substantially flat articles ; Making flat seams in tubular or hollow articles
    • B29C66/45—Joining of substantially the whole surface of the articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/40—General aspects of joining substantially flat articles, e.g. plates, sheets or web-like materials; Making flat seams in tubular or hollow articles; Joining single elements to substantially flat surfaces
    • B29C66/47—Joining single elements to sheets, plates or other substantially flat surfaces
    • B29C66/472—Joining single elements to sheets, plates or other substantially flat surfaces said single elements being substantially flat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/73—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/735—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the extensive physical properties of the parts to be joined
    • B29C66/7352—Thickness, e.g. very thin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/73—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/739—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/7392—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of at least one of the parts being a thermoplastic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/06—Coating on the layer surface on metal layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/24—Organic non-macromolecular coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/028—Paper layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/102—Oxide or hydroxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/204—Di-electric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7246—Water vapor barrier
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
    • B32B2309/08—Dimensions, e.g. volume
    • B32B2309/10—Dimensions, e.g. volume linear, e.g. length, distance, width
    • B32B2309/105—Thickness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2327/00—Polyvinylhalogenides
    • B32B2327/12—Polyvinylhalogenides containing fluorine
    • B32B2327/18—PTFE, i.e. polytetrafluoroethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2398/00—Unspecified macromolecular compounds
    • B32B2398/20—Thermoplastics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • B32B2605/18—Aircraft
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/03—Metal processing
    • H05K2203/0307—Providing micro- or nanometer scale roughness on a metal surface, e.g. by plating of nodules or dendrites

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Textile Engineering (AREA)
  • Laminated Bodies (AREA)
  • Manufacturing Of Printed Wiring (AREA)

Abstract

本发明提供一种即使使用低介电常数的热塑性树脂也能够以较高的密合力将铜箔和树脂接合的覆铜层叠板的制造方法。该方法的特征在于，包括以下工序：准备在至少一侧具有粗糙化处理表面的粗糙化处理铜箔，该粗糙化处理表面具有由含有氧化铜和氧化亚铜的针状结晶构成的微细凹凸；以及在粗糙化处理铜箔的粗糙化处理表面粘贴片状的热塑性树脂而得到覆铜层叠板。在将要粘贴热塑性树脂时，粗糙化处理表面的根据连续电化学还原分析(SERA)确定的氧化铜厚度为1nm～20nm、且根据连续电化学还原分析(SERA)确定的氧化亚铜厚度为15nm～70nm。

Description

覆铜层叠板的制造方法
技术领域
本发明涉及一种覆铜层叠板的制造方法。
背景技术
作为适用于形成细间距电路的印刷电路板铜箔，提案有一种粗糙化处理铜箔，其具有经过氧化处理和还原处理(以下，有时统称为氧化还原处理)而形成的微细凹凸来作为粗糙化处理表面。
例如，在专利文献1(国际公开第2014/126193号)中公开有一种表面处理铜箔，该表面处理铜箔在表面具有粗糙化处理层，该粗糙化处理层是由最大长度在500nm以下的包括铜复合化合物的针状的微细凹凸形成的。另外，在专利文献2(国际公开第2015/040998号)中公开有一种铜箔，该铜箔在至少一面具有粗糙化处理层，该粗糙化处理层具有由包括铜复合化合物且最大长度在500nm以下的尺寸的针状的凸状部形成的微细凹凸，且在该粗糙化处理层的表面具有硅烷偶联剂处理层。根据这些文献中的粗糙化处理铜箔，能够利用由粗糙化处理层的微细凹凸产生的锚固效果得到与绝缘树脂基材之间的良好的密合性，并且，能够形成具有良好的蚀刻因子的细间距电路。专利文献1、2所公开的具有微细凹凸的粗糙化处理层均通过在进行碱脱脂等预处理之后经过氧化还原处理而形成。这样形成的微细凹凸具有由铜复合化合物的针状结晶构成的特有的形状，具有该微细凹凸的粗糙化处理表面一般比通过附着微细铜粒而形成的粗糙化处理表面、通过蚀刻赋予凹凸而成的粗糙化处理表面微细。
现有技术文献
专利文献
专利文献1：国际公开第2014/126193号
专利文献2：国际公开第2015/040998号
发明内容
发明要解决的问题
然而，随着近年的便携式电子设备等的高功能化，为了高速处理大量的信息而逐渐推进信号的高频化，并谋求适用于高频用途的印刷电路板。对于这样的高频用印刷电路板而言，为了能够不使品质降低地传输高频信号，期望降低传输损耗。印刷电路板包括被加工成布线图案的铜箔和绝缘树脂基材，传输损耗主要包括由铜箔引起的导体损耗和由绝缘树脂基材引起的介质损耗。因而，为了降低由绝缘树脂基材引起的介质损耗，若能够使用低介电常数的热塑性树脂，则非常理想。然而，与热固化树脂不同，以聚四氟乙烯(PTFE)等氟树脂、液晶聚合物(LCP)树脂为代表的低介电常数的热塑性树脂的化学活性较低，因而与铜箔之间的密合力较低。因此，为了使用热塑性树脂和铜箔制作覆铜层叠板，对要与热塑性树脂接合的铜箔的表面实施使其具有一定程度上较大的表面粗糙度的粗糙化处理，从而提高与树脂之间的密合性。然而，从降低导体损耗的观点来看，期望表面平滑的铜箔，因此，期望在使用低粗糙度的铜箔的同时实现提高铜箔与热塑性树脂之间的密合性的方法。
本发明人此次得到了以下的见解：在具有包括由针状结晶构成的微细凹凸在内的粗糙化处理表面的粗糙化处理铜箔的情况下，通过将根据连续电化学还原分析(SERA)以厚度换算而确定的氧化铜的量和氧化亚铜的量分别控制在预定的范围内，能够实现相对于低介电常数的热塑性树脂的较高的密合性。其结果，得到了以下的见解：即使使用低介电常数的热塑性树脂，也能够制造铜箔和树脂以较高的密合力接合而成的覆铜层叠板。
因而，本发明的目的在于：即使使用低介电常数的热塑性树脂，也能够制造铜箔和树脂以较高的密合力接合而成的覆铜层叠板。
用于解决问题的方案
根据本发明的一技术方案，提供一种覆铜层叠板的制造方法，其特征在于，
该覆铜层叠板的制造方法包含以下工序：
准备在至少一侧具有粗糙化处理表面的粗糙化处理铜箔，该粗糙化处理表面包括由含有氧化铜和氧化亚铜的针状结晶构成的微细凹凸；以及
在所述粗糙化处理铜箔的所述粗糙化处理表面粘贴片状的热塑性树脂并得到覆铜层叠板，
在将要粘贴所述热塑性树脂时，所述粗糙化处理表面的根据连续电化学还原分析(SERA)确定的氧化铜厚度为1nm～20nm、且根据连续电化学还原分析(SERA)确定的氧化亚铜厚度为15nm～70nm。
具体实施方式
覆铜层叠板的制造方法
本发明涉及一种覆铜层叠板的制造方法。本发明的方法包括：(1)准备粗糙化处理铜箔的工序；(2)在粗糙化处理铜箔的粗糙化处理表面粘贴片状的热塑性树脂的工序。粗糙化处理铜箔为在至少一侧具有粗糙化处理表面的铜箔，该粗糙化处理表面包括由含有氧化铜(CuO)和氧化亚铜(Cu2O)的针状结晶构成的微细凹凸。而且，该粗糙化处理表面的特征在于，在粘贴热塑性树脂时，根据连续电化学还原分析(SERA)确定的氧化铜厚度为1nm～20nm，且根据连续电化学还原分析(SERA)确定的氧化亚铜厚度为15nm～70nm。如此，在具有包括由针状结晶构成的微细凹凸在内的粗糙化处理表面的粗糙化处理铜箔的情况下，通过将根据连续电化学还原分析(SERA)以厚度换算而确定的氧化铜的量和氧化亚铜的量分别控制在上述预定的范围内，能够实现相对于低介电常数的热塑性树脂的较高的密合性。即，如上所述，与热固化树脂不同，以聚四氟乙烯(PTFE)等氟树脂、液晶聚合物(LCP)树脂为代表的低介电常数的热塑性树脂的化学活性较低，因而原本与铜箔之间的密合力较低。其原因被认为是，由含有氧化铜和氧化亚铜的针状结晶构成的微细凹凸的表面容易存在OH基，因此呈亲水性，然而，热塑性树脂为疏水性，因此，两者之间缺乏亲和性。关于这一点，根据本发明的方法，预先将根据SERA以厚度换算而确定的氧化铜的量和氧化亚铜的量分别控制在上述预定的范围内从而形成为特有的氧化状态，在该氧化状态下的粗糙化处理表面粘贴热塑性树脂。由此，能够提高粗糙化处理铜箔的粗糙化处理表面与热塑性树脂之间的亲和性，其结果，能够实现较高的密合性、即较高的剥离强度。其结果，即使使用低介电常数的热塑性树脂，也能够制造铜箔和树脂以较高的密合力接合而成的覆铜层叠板。
(1)准备粗糙化处理铜箔
本发明的方法所使用的铜箔为粗糙化处理铜箔。该粗糙化处理铜箔在至少一侧具有粗糙化处理表面。粗糙化处理表面包括由含有氧化铜和氧化亚铜的针状结晶构成的微细凹凸。而且，对于该粗糙化处理表面而言，在粘贴热塑性树脂时，根据连续电化学还原分析(SERA)确定的氧化铜厚度为1nm～20nm，优选为1nm～18nm，更优选为2nm～15nm，并且，根据连续电化学还原分析(SERA)确定的氧化亚铜厚度为15nm～70nm，优选为20nm～65nm，更优选为25nm～40nm。在该SERA分析中，能够使用市售的SERA分析装置(例如ECI Technology公司制的QC-100)，并按照例如以下的顺序进行分析。首先，为了分析，将粗糙化处理铜箔的8.0mm2的区域利用O型密封垫片隔离，注入硼酸缓冲液，用氮使其饱和。对上述区域施加30μA/cm2的电流密度Id，计量在-0.40V～-0.60V时发生的Cu2O还原反应所花费的时间，且计量在-0.60V～-0.85V时发生的CuO还原反应所花费的时间，并分别设为t1和t2，其中，t1和t2的单位为秒。使用基于法拉第定律求出的常数K，根据T＝K·Id·t的公式计算出CuO和Cu2O各自的厚度T，其中，T的单位为nm。另外，与CuO相关的常数K的值为6.53×10-5(cm3/A·sec)，与Cu2O相关的K的值为2.45×10-4(cm3/A·sec)。
微细凹凸能够经过氧化还原处理形成，典型的情况下，观察到呈针状结晶向相对于铜箔面大致垂直和/或倾斜的方向繁茂生长的形状(例如草坪状)。针状结晶的高度(即从针状结晶的根部起沿垂直方向测量的高度)优选为50nm～400nm，更优选为100nm～400nm，进一步优选为120nm～350nm。若是上述这样的范围内的针状结晶高度，则更适合于形成细间距电路、高频用途。特别是，若是这样的低粗糙度，则能够降低在高频信号传输中成为问题的铜箔的集肤效应，而降低由铜箔引起的导体损耗，由此，能够有意地降低高频信号的传输损耗。
本发明的粗糙化处理铜箔的厚度没有特殊限定，优选为0.1μm～70μm，更优选为0.5μm～18μm。另外，本发明的粗糙化处理铜箔并不限定于在通常的铜箔的表面进行粗糙化处理而成，还可以是在带载体的铜箔的铜箔表面进行粗糙化处理而成。
根据本发明的优选的实施方式，粗糙化处理铜箔在粗糙化处理表面具有有机防锈层。有机防锈层没有特殊限定，优选含有三唑化合物和硅烷偶联剂的至少任一种。作为三唑化合物的例子，可列举苯并三唑、羧基苯并三唑、甲基苯并三唑、氨基三唑、硝基苯并三唑、羟基苯并三唑、氯苯并三唑、乙基苯并三唑、萘三唑。作为硅烷偶联剂的例子，可列举3-环氧丙氧基丙基三甲氧基硅烷、3-环氧丙氧基丙基甲基二甲氧基硅烷等环氧官能性硅烷偶联剂、或3-氨基丙基三乙氧基硅烷、3-氨基丙基三甲氧基硅烷、N-2(氨基乙基)3-氨基丙基三甲氧基硅烷、N-苯基-3-氨基丙基三甲氧基硅烷等氨基官能性硅烷偶联剂、或3-巯基丙基三氧基硅烷等巯基官能性硅烷偶联剂、或乙烯基三甲氧基硅烷、乙烯基苯基三甲氧基硅烷等乙烯基官能性硅烷偶联剂、或3-甲基丙烯酰氧基丙基三甲氧基硅烷等甲基丙烯酰基官能性硅烷偶联剂、或3-丙烯酰氧丙基三甲氧基硅烷等丙烯酰基官能性硅烷偶联剂、或咪唑硅烷等咪唑官能性硅烷偶联剂、或三嗪硅烷等三嗪官能性硅烷偶联剂等。有机防锈层更优选含有三唑化合物，作为三唑化合物的优选的例子，可列举有苯并三唑(BTA)和羧基苯并三唑(CBTA)。在热塑性树脂为氟树脂的情况下，特别优选含有BTA、CBTA等的三唑化合物的有机防锈层。更优选三唑化合物的理由可列举以下的方面。通过三唑化合物和粗糙化处理表面的氧化亚铜形成铜络合物，从而与形成于通常的铜箔的情况相比，成分在表面更致密地附着，因而能够发挥优异的防锈功能。因此，能够容易地将长期保管粗糙化处理铜箔时的氧化铜厚度和氧化亚铜厚度维持在上述的预定的范围内。另外，在暴露于高温等严酷的环境的情况下，通过利用含有三唑化合物的有机防锈层来维持表面的微细凹凸，因此，能够维持较高的可靠性。
(2)粘贴热塑性树脂
在粗糙化处理铜箔的粗糙化处理表面粘贴片状的热塑性树脂而得到覆铜层叠板。该热塑性树脂的相对于粗糙化处理铜箔的粘贴按照公知的覆铜层叠板的制造步骤进行粘贴即可，没有特殊限定。另外，还能够采用在内层基板隔着热塑性树脂粘贴铜箔的方法，在该情况下按照所谓的积层法等公知的方法进行粘贴即可。无论何种情况，都根据本发明的方法，预先将利用SERA以厚度换算而确定的氧化铜的量和氧化亚铜的量分别控制在上述预定的范围内从而形成为特有的氧化状态，在该氧化状态下的粗糙化处理表面粘贴热塑性树脂。由此，能够提高粗糙化处理铜箔的粗糙化处理表面与热塑性树脂之间的亲和性，其结果，能够实现较高的密合性、即较高的剥离强度。其结果，即使使用低介电常数的热塑性树脂，也能够制造铜箔和树脂以较高的密合力接合而成的覆铜层叠板。热塑性树脂的相对于粗糙化处理铜箔的粘贴优选通过一边加热一边压制的方式进行，由此，能够使热塑性树脂软化而使粗糙化处理表面的微细凹凸进入。其结果，能够利用由微细凹凸(特别是针状结晶)相对于树脂的咬合而产生的锚固效果来确保铜箔与树脂之间的密合性。压制时的温度根据所使用的热塑性树脂的特性来适当确定即可，没有特殊限定，优选为150℃～500℃，更优选为180℃～400℃。压制压力也没有特殊限定，优选为1MPa～10MPa，更优选为2MPa～5MPa。
片状的热塑性树脂既可以是剪切而成的片，也可以是自辊抽出的长片，其形态没有特殊限定。作为热塑性树脂的优选的例子，可列举聚砜(PSF)、聚醚砜(PES)、非晶态聚芳酯(PAR)、液晶聚合物(LCP)、聚醚醚酮(PEEK)、热塑性聚酰亚胺(PI)、聚酰胺酰亚胺(PAI)、氟树脂、聚酰胺(PA)、尼龙、聚缩醛(POM)、改性聚苯醚(m-PPE)、聚对苯二甲酸乙二醇酯(PET)、玻璃纤维强化聚对苯二甲酸乙二醇酯(GF-PET)、环烯烃(COP)以及它们的任意的组合。从期望的介质损耗角正切和优异的耐热性的观点来看，作为热塑性树脂的更优选的例子，可列举聚砜(PSF)、聚醚砜(PES)、非晶态聚芳酯(PAR)、液晶聚合物(LCP)、聚醚醚酮(PEEK)、热塑性聚酰亚胺(PI)、聚酰胺酰亚胺(PAI)、氟树脂以及它们的任意的组合。从低介电常数的观点来看，特别优选的热塑性树脂为氟树脂。作为氟树脂的优选的例子，可列举聚四氟乙烯(PTFE)、四氟乙烯-全氟烷基乙烯基醚共聚物(PFA)、四氟乙烯-六氟丙烯共聚物(FEP)、乙烯-四氟乙烯共聚物(ETFE)以及它们的任意的组合。
粗糙化处理铜箔既可以设于片状的热塑性树脂的单面，也可以设于热塑性树脂的双面。片状的热塑性树脂含有热塑性树脂即可，也可以还含有其他的材料。因而，片状的热塑性树脂也可以是预浸料。预浸料为使合成树脂浸渍于合成树脂板、玻璃板、玻璃织布、玻璃无纺布、纸等基材而成的复合材料的总称。另外，从提高绝缘性等观点来看，热塑性树脂还可以含有包括二氧化硅、氧化铝等的各种无机颗粒的填料颗粒等。片状的热塑性树脂的厚度没有特殊限定，优选为1μm～1000μm，更优选为2μm～400μm，进一步优选为3μm～200μm。树脂层可以由多层构成。
制造方法
本发明的粗糙化处理铜箔可以利用所有的方法制造而成，但优选经过氧化还原处理制造而成。以下，说明本发明的粗糙化处理铜箔的优选的制造方法的一个例子。该优选的制造方法包括：准备铜箔的工序；以及对上述表面依次进行预处理、氧化处理以及还原处理的粗糙化工序(氧化还原处理)。
(1)准备铜箔
作为制造粗糙化处理铜箔所使用的铜箔，能够使用电解铜箔和压延铜箔这两者，更优选使用电解铜箔。另外，铜箔既可以是非粗糙化的铜箔，也可以是实施了预粗糙化的铜箔。铜箔的厚度没有特殊限定，优选为0.1μm～70μm，更优选为0.5μm～18μm。在以带载体的铜箔的形态准备铜箔的情况下，铜箔可以是利用无电解镀铜法和电解镀铜法等湿式成膜法、溅射和化学蒸镀等干式成膜法、或它们的组合而形成的铜箔。
对于要进行粗糙化处理的铜箔的表面而言，按照ISO25178的标准测量的最大高度Sz优选在1.5μm以下，更优选在1.2μm以下，进一步优选在1.0μm以下。在上述范围内时，容易在粗糙化处理表面实现本发明的粗糙化处理铜箔所要求的表面轮廓、特别是1.5μm以下的最大高度Sz。Sz的下限值没有特殊限定，但Sz优选在0.1μm以上，更优选在0.2μm以上，进一步优选在0.3μm以上。
(2)粗糙化处理(氧化还原处理)
优选的是，对如此地被赋予了上述较低的Sz的铜箔的表面实施依次进行预处理、氧化处理以及还原处理的湿式的粗糙化工序。特别是，通过利用使用了溶液的湿式法对铜箔的表面实施氧化处理，从而在铜箔表面形成含有氧化铜(CuO)的铜化合物。然后，通过对该铜化合物进行还原处理而使氧化铜的一部分转化为氧化亚铜(Cu2O)，从而能够在铜箔的表面形成由针状结晶构成的微细凹凸，该针状结晶包括含有氧化铜和氧化亚铜的铜复合化合物。在此，在利用湿式法对铜箔的表面进行了氧化处理的阶段，利用以氧化铜为主要成分的铜化合物形成微细凹凸。然后，在对该铜化合物进行了还原处理时，在大致维持了利用该铜化合物形成的微细凹凸的形状的状态下，将氧化铜的一部分转化为氧化亚铜，而成为包括含有氧化铜和氧化亚铜的铜复合化合物的微细凹凸。在这样地利用湿式法对铜箔的表面实施了适当的氧化处理之后，实施还原处理，从而能够形成nm等级的微细凹凸。
(2a)预处理
在氧化处理之前，优选对电解铜箔实施脱脂等预处理。对于该预处理，优选的是，在将电解铜箔浸渍于氢氧化钠水溶液而进行碱脱脂处理之后，进行水洗。另外，优选在将被实施了碱脱脂处理的电解铜箔浸渍于硫酸类水溶液之后，进行水洗。硫酸类水溶液的硫酸浓度没有特殊限定，但优选为1质量％～20质量％。另外，电解铜箔相对于硫酸类水溶液的浸渍时间没有特殊限定，但优选为2秒～2分钟。
(2b)氧化处理
使用氢氧化钠溶液等碱性溶液对被实施了上述预处理的铜箔进行氧化处理。通过利用碱性溶液对铜箔的表面进行氧化，而能够在铜箔的表面形成由针状结晶构成的微细凹凸，该针状结晶包括以氧化铜为主要成分的铜复合化合物。此时，碱性溶液的温度优选为60℃～85℃，碱性溶液的pH优选为10～14。另外，从氧化的观点来看，碱性溶液优选含有氯酸盐、亚氯酸盐、次氯酸盐、高氯酸盐，其浓度优选为100g/L～500g/L。优选通过将电解铜箔浸渍于碱性溶液来进行氧化处理，该浸渍时间(即氧化时间)优选为10秒～20分钟，更优选为30秒～10分钟。
优选氧化处理所使用的碱性溶液还含有氧化抑制剂。即，在利用碱性溶液对铜箔的表面实施了氧化处理的情况下，存在该凸状部过度生长而超过所期望的长度的情况，难以形成期望的微细凹凸。于是，为了形成上述微细凹凸，优选使用含有可抑制铜箔表面的氧化的氧化抑制剂的碱性溶液。作为优选的氧化抑制剂的例子，可列举氨基类硅烷偶联剂。通过使用含有氨基类硅烷偶联剂的碱性溶液对铜箔表面实施氧化处理，从而使该碱性溶液中的氨基类硅烷偶联剂吸附于铜箔的表面，能够抑制碱性溶液对铜箔表面的氧化。其结果，能够抑制氧化铜的针状结晶的生长，能够形成包括极微细的凹凸的期望的粗糙化处理表面。作为氨基类硅烷偶联剂的具体例子，可列举N-2-(氨基乙基)-3-氨基丙基甲基二甲氧基硅烷、N-2-(氨基乙基)-3-氨基丙基三甲氧基硅烷、3-氨基丙基三甲氧基硅烷、3-氨基丙基三乙氧基硅烷、3-三乙氧基甲硅烷基-N-(1,3-二甲基-亚丁基)丙胺、N-苯基-3-氨基丙基三甲氧基硅烷等，特别优选N-2-(氨基乙基)-3-氨基丙基三甲氧基硅烷。这些氨基类硅烷偶联剂均溶解于碱性溶液，并在碱性溶液中被稳定地保持，并且，发挥上述的抑制铜箔表面氧化的效果。碱性溶液中的氨基类硅烷偶联剂(例如N-2-(氨基乙基)-3-氨基丙基三甲氧基硅烷)的优选浓度为0.01g/L～20g/L，更优选为0.02g/L～20g/L。
(2c)还原处理
使用还原处理液对被实施了上述氧化处理的铜箔(以下称作氧化处理铜箔)进行还原处理。通过利用还原处理使氧化铜的一部分转化为氧化亚铜(Cu2O)，能够在铜箔的表面形成由针状结晶构成的微细凹凸，该针状结晶包括含有氧化铜和氧化亚铜的铜复合化合物。该还原处理通过使还原处理液与氧化处理铜箔接触来进行即可，优选利用在还原处理液中浸渍氧化处理铜箔的方法、以喷淋的方式向氧化处理铜箔施加还原处理液的方法来进行处理，该处理时间优选为2秒～60秒，更优选为5秒～30秒。另外，优选的还原处理液为二甲胺硼烷水溶液，该水溶液优选含有浓度为10g/L～40g/L的二甲胺硼烷。另外，优选使用碳酸钠和氢氧化钠将二甲胺硼烷水溶液调整为pH12～pH14。此时的水溶液的温度没有特殊限定，为室温即可。优选对这样地进行了还原处理的铜箔进行水洗，并进行干燥。
(3)防锈处理
也可以根据期望，利用有机防锈剂对铜箔实施防锈处理，形成有机防锈层。由此，在粗糙化处理铜箔的粗糙化处理表面，能够在尽可能长的时间内维持特有的氧化状态，该特有的氧化状态是将根据SERA以厚度换算而确定的氧化铜的量和氧化亚铜的量分别控制在预定的范围内而成的，在该被维持的氧化状态下容易在粗糙化处理表面粘贴热塑性树脂。另外，还能够提高耐湿性、耐化学药品性以及与粘接剂等之间的密合性等。有机防锈层没有特殊限定，优选含有三唑化合物和硅烷偶联剂的至少任一者。作为三唑化合物的例子，可列举苯并三唑、羧基苯并三唑、甲基苯并三唑、氨基三唑、硝基苯并三唑、羟基苯并三唑、氯苯并三唑、乙基苯并三唑以及萘三唑，特别优选为苯并三唑。作为硅烷偶联剂的例子，可列举有3-环氧丙氧基丙基三甲氧基硅烷、3-环氧丙氧基丙基甲基二甲氧基硅烷等环氧官能性硅烷偶联剂、或3-氨基丙基三乙氧基硅烷、3-氨基丙基三甲氧基硅烷、N-2(氨基乙基)3-氨基丙基三甲氧基硅烷、N-苯基-3-氨基丙基三甲氧基硅烷等氨基官能性硅烷偶联剂、或3-巯基丙基三甲氧基硅烷等巯基官能性硅烷偶联剂、或乙烯基三甲氧基硅烷、乙烯基苯基三甲氧基硅烷等乙烯基官能性硅烷偶联剂、或3-甲基丙烯酰氧基丙基三甲氧基硅烷等甲基丙烯酰基官能性硅烷偶联剂、或3-丙烯酰氧丙基三甲氧基硅烷等丙烯酰基官能性硅烷偶联剂、或咪唑硅烷等咪唑官能性硅烷偶联剂、或三嗪硅烷等三嗪官能性硅烷偶联剂等。能够通过将三唑化合物、硅烷偶联剂等有机防锈剂适当稀释后进行涂布并使其干燥来形成有机防锈层。
印刷电路板
本发明的覆铜层叠板优选用于制作印刷电路板。即，根据本发明的优选的方式，能够提供使用上述覆铜层叠板而得到的印刷电路板。作为与印刷电路板相关的具体例，可列举在本发明的覆铜层叠板形成电路而成的单面或双面的印刷电路板、将该单面或双面的印刷电路板多层化而成的多层印刷电路板等。多层印刷电路板既可以是通过在内层基板隔着热塑性树脂层粘贴铜箔而成的多层覆铜层叠板上形成电路而成的多层印刷电路板，也可以是形成积层层而成的多层印刷电路板。另外，电路形成方法既可以是消减法(日文：サブトラクティブ法)，也可以是改性半添加法(日文：モディファイド·セミアディティブ)(MSAP法)。使用本发明的覆铜层叠板制作的印刷电路板优选用作在信号频率10GHz以上的高频带中使用的汽车用天线、移动电话基站天线、高性能服务器、防撞雷达等用途中所使用的高频基板。
实施例
利用以下的例子进一步具体地说明本发明。
例1～例8
(1)制作粗糙化处理铜箔
(1a)制作电解铜箔
使用以下所示的组成的硫酸酸性硫酸铜溶液作为铜电解液，阴极使用钛制的旋转电极，阳极使用DSA(尺寸稳定性阳极)，并以45℃的溶液温度、55A/dm2的电流密度进行电解，得到了厚度为18μm的电解铜箔。在按照ISO25178标准并使用激光显微镜(株式会社基恩士(KEYENCE)制造的VK-X100)测量了该电解铜箔的析出面和电极面的最大高度Sz时，析出面的Sz为0.8μm，电极面的Sz为1.2μm。
＜硫酸酸性硫酸铜溶液的组成＞
‐铜浓度：80g/L
‐硫酸浓度：260g/L
‐双(3-磺丙基)二硫化物浓度：30mg/L
‐二烯丙基二甲基氯化铵聚合物浓度：50mg/L
‐氯浓度：40mg/L
(1b)粗糙化处理(氧化还原处理)
利用以下所示的三阶段的工艺对上述得到的电解铜箔的析出面侧进行粗糙化处理(氧化还原处理)。即，依次进行以下所示的预处理、氧化处理以及还原处理。
＜预处理＞
将由上述(1)得到的电解铜箔在40g/L的氢氧化钠水溶液中以40℃浸渍30秒，进行碱脱脂处理，之后，进行水洗。在将实施了该碱脱脂处理的电解铜箔在硫酸浓度为10体积％的硫酸水溶液中以40℃浸渍30秒之后，进行水洗。
＜氧化处理＞
对实施了上述预处理的电解铜箔进行氧化处理。通过使该电解铜箔在液温为75℃、pH＝12、亚氯酸浓度为100g/L～500g/L、N-2-(氨基乙基)-3-氨基丙基三甲氧基硅烷浓度为10g/L的氢氧化钠溶液中浸渍3分钟(例1～例6以及例8)或7分钟(例7)来进行该氧化处理。如此，在电解铜箔的两表面形成由包括铜复合化合物的针状结晶构成的微细凹凸。
＜还原处理＞
对实施了上述氧化处理的试样进行还原处理。通过将利用上述氧化处理而形成有微细凹凸的试样在使用碳酸钠和氢氧化钠而调整为pH＝13的二甲胺硼烷浓度为10g/L～40g/L的水溶液中浸渍1分钟来进行该还原处理。此时的水溶液的温度设为室温。对如此进行了还原处理的试样进行水洗，并进行干燥。利用这些工序，将电解铜箔的两表面的氧化铜的一部分还原成为氧化亚铜，而形成了具有微细凹凸的粗糙化处理表面，该微细凹凸包括含有氧化铜和氧化亚铜的铜复合化合物。如此，得到在至少一侧具有粗糙化处理表面的粗糙化处理铜箔，该粗糙化处理表面包括由针状结晶构成的微细凹凸。
(1c)形成有机防锈层
对上述粗糙化处理铜箔进行有机防锈层的形成。该有机防锈的形成通过以下方式进行：在将粗糙化处理铜箔在含有浓度为6g/L的苯并三唑(例1、6、7)、3-氨基丙基三甲氧基硅烷(例2～例5)或羧基苯并三唑(例8)作为有机防锈剂的水溶液中、以液温25℃浸渍30秒之后，以表1所示的条件使其干燥。
表1
表1
*表示比较例。
(2)粗糙化处理铜箔的评价
对在例1～例5中制作成的粗糙化处理铜箔进行以下所示的各种评价。
<SERA测量>
根据连续电化学还原分析(SERA)对粗糙化处理铜箔的粗糙化处理表面测量了氧化铜(CuO)厚度和氧化亚铜(Cu2O)厚度。在该SERA分析中，作为测量装置而使用了ECITechnology公司制的QC-100。步骤如以下所示。首先，为了分析，利用O型密封垫片将粗糙化处理铜箔的8.0mm2的区域隔离，注入硼酸缓冲液，利用氮使其饱和。对上述区域施加30μA/cm2的电流密度Id，计量在-0.40V～-0.60V时发生的Cu2O还原反应以及在-0.60V～-0.85V时发生的CuO还原反应所需的时间，并分别设为t1和t2，其中，t1和t2的单位为秒。使用由法拉第定律求出的常数K并根据T＝K·Id·t的公式计算出CuO和Cu2O的各自的厚度T，其中，T的单位为nm。另外，与CuO相关的K的值为6.53×10-5(cm3/A·sec)，与Cu2O相关的常数K的值为2.45×10-4(cm3/A·sec)。根据K＝M/(z·F·ρ)(在公式中，M为分子量，z为电荷量，F为法拉第常数，ρ为密度)的公式计算出上述常数K。
即，通过在K＝M/(z·F·ρ)的公式中输入以下的值而计算出与CuO相关的常数K(＝6.53×10-5(cm3/A·sec))。
M(分子量)＝79.545(g/mol)
z(电荷量)＝2(CuO+H2O+2e-→Cu+2OH-)
F(法拉第常数)＝96494(C/mol)＝96500(A·sec/mol)
ρ(密度)＝6.31(g/cm3)
另外，通过在K＝M/(z·F·ρ)的公式中输入以下的值而计算出与Cu2O相关的常数K(＝2.45×10-4(cm3/A·sec))。
M(分子量)＝143.09(g/mol)
z(电荷量)＝1(Cu2O+H2O+2e-→2Cu+2OH-)
F(法拉第常数)＝96494(C/mol)＝96500(A·sec/mol)
ρ(密度)＝6.04(g/cm3)
＜观察粗糙化处理表面(微细凹凸)＞
在利用剖面SEM观察构成粗糙化处理铜箔的粗糙化处理表面的微细凹凸(析出面侧)时，可确认在例1～例5的任一例子中粗糙化处理表面均包括由无数的针状结晶构成的微细凹凸。另外，利用透射电子显微镜(TEM)(日本电子株式会社制的JEM-ARM200F)观察微细凹凸(特别是针状结晶)的剖面，根据所获得的STEM-HAADF图像测量针状结晶的高度(相对于箔垂直的方向上的长度)。此时，将在1μm×1μm的区域内对十个部位进行测量而得到的值的平均值设为各样品的针状结晶高度。结果如表1所示。
＜相对于热塑性树脂(PTFE)的常态剥离强度＞
作为热塑性树脂基材，准备PTFE基材(RO3003 Bondply、ROGERS Corporation制，厚度为125μm)。将刚刚进行了上述SERA测量的粗糙化处理铜箔(厚度为18μm)以使其粗糙化处理表面与该基材抵接的方式层叠在该PTFE基材上，使用真空压制机，在压制压力为2.4MPa、温度为370℃、压制时间为30分钟的条件下进行压制并制作覆铜层叠板。接着，制作利用蚀刻法而在该覆铜层叠板设有0.4mm宽的剥离强度测量用线性电路的试验基板。按照JISC5016-1994的A方法(90°剥离)的标准将这样形成的线性电路自PTFE基材剥离，并测量常态剥离强度(kgf/cm)。使用台式材料试验机(STA-1150、株式会社Orientec社制)进行该测量。结果如表1所示。
＜相对于热塑性树脂(PTFE)的耐热剥离强度＞
将具有0.4mm宽的剥离强度测量用线性电路的试验基板放入烘箱并以150℃加热4小时，在288℃的焊锡槽中悬浮10秒，除此之外，利用与上述的相对于PTFE的常态剥离强度相同的步骤，测量相对于PTFE的耐热剥离强度(kgf/cm)。结果如表1所示。另外，测量耐热剥离强度的技术性的意义如下所示。使用了热塑性树脂的印刷电路板有时会暴露于高温等严酷的环境下，期望即使在暴露于这样的严酷的环境下之后也具有铜箔与树脂之间的较高的密合可靠性。实际上，使用了PTFE的印刷电路板有时在航空、宇宙用等方面使用，从该观点来看，也期望进一步改善耐热剥离强度。当然，在未暴露于高温等严酷的环境下的用途的情况下，只要常态剥离强度较高即可满足，而耐热剥离强度可以不一定较高。
＜相对于热塑性树脂(液晶聚合物)的常态剥离强度＞
作为热塑性树脂基材，准备厚度为50μm的LCP(液晶聚合物)薄膜(CT-Z、株式会社Kuraray制)。在该LCP薄膜以使粗糙化处理表面与该薄膜抵接的方式层叠粗糙化处理铜箔，使用真空压制机，并在压制压力为4MPa、温度为320℃、压制时间为10分钟的条件下进行压制而制作覆铜层叠板。接着，制作利用蚀刻法而在覆铜层叠板具备0.4mm宽的剥离强度测量用线性电路的试验基板。按照JISC5016-1994的A法(90°剥离)的标准将如此形成的线性电路自绝缘树脂基材剥离，并测量常态剥离强度(kgf/cm)。结果如表1所示。
<相对于热固化树脂(R1551)的剥离强度>
作为绝缘树脂基材准备了预浸料(Panasonic株式会社制，R-1551，厚度为200μm)。在该预浸料以使粗糙化处理表面与预浸料抵接的方式层叠粗糙化处理铜箔，使用真空压制机，在压制压力为2.9MPa、温度为190℃、压制时间为90分钟的条件下进行压制而制作覆铜层叠板，接着，制作利用蚀刻法而在该覆铜层叠板设有0.4mm宽度的剥离强度测量用线性电路的试验基板。按照JISC6481-1996的标准将如此形成的线性电路自绝缘树脂基材剥离，并测量常态剥离强度(kgf/cm)。结果如表1所示。
表2
表2
*表示比较例。
根据表2所示的结果可明确，通过使用具有根据SERA确定的CuO厚度为1nm～20nm、且根据SERA确定的Cu2O厚度为15nm～70nm的粗糙化处理表面的粗糙化处理铜箔，能够对热塑性树脂实现0.70kgf/cm以上的较高的常态剥离强度。与此相对照地，在热固化树脂的情况下，CuO厚度和Cu2O厚度在上述范围内和上述范围外均完全未看到在热塑性树脂中看到的那样的常态剥离强度的改善，因此，可以说在热塑性树脂中实现的上述效果是无法由热固化树脂预测到的显著的效果。通常，粗糙化处理表面因存在CuO和Cu2O而具有微细凹凸，但这些表面容易存在OH基，而带有亲水性，结果使得与热塑性树脂之间的密合性下降。这一方面，根据本发明的粗糙化处理铜箔，通过控制CuO厚度和Cu2O厚度，能够期望地使粗糙化处理表面的亲水性降低，而能够提高与热塑性树脂之间的密合性。

Claims (8)

1.一种覆铜层叠板的制造方法，其特征在于，
该覆铜层叠板的制造方法包括以下工序：
准备在至少一侧具有粗糙化处理表面的粗糙化处理铜箔，该粗糙化处理表面包括由含有氧化铜和氧化亚铜的针状结晶构成的微细凹凸；以及
在所述粗糙化处理铜箔的所述粗糙化处理表面粘贴片状的热塑性树脂而得到覆铜层叠板，
在将要粘贴所述热塑性树脂时，所述粗糙化处理表面的根据连续电化学还原分析(SERA)确定的氧化铜厚度为1nm～20nm、且根据连续电化学还原分析(SERA)确定的氧化亚铜厚度为15nm～70nm。
2.根据权利要求1所述的覆铜层叠板的制造方法，其中，
所述针状结晶的高度为50nm～400nm。
3.根据权利要求1或2所述的覆铜层叠板的制造方法，其中，
所述热塑性树脂为从包括聚砜、聚醚砜、非晶态聚芳酯、液晶聚合物、聚醚醚酮、热塑性聚酰亚胺、聚酰胺酰亚胺、氟树脂、聚酰胺、尼龙、聚缩醛、改性聚苯醚、聚对苯二甲酸乙二醇酯、玻璃纤维强化聚对苯二甲酸乙二醇酯、环烯烃的组中选择的至少一种。
4.根据权利要求1或2所述的覆铜层叠板的制造方法，其中，
所述热塑性树脂为从包括聚砜、聚醚砜、非晶态聚芳酯、液晶聚合物、聚醚醚酮、热塑性聚酰亚胺、聚酰胺酰亚胺以及氟树脂的组中选择的至少一种。
5.根据权利要求1或2所述的覆铜层叠板的制造方法，其中，
所述热塑性树脂为氟树脂，该氟树脂为从包括聚四氟乙烯、四氟乙烯-全氟烷基乙烯基醚共聚物、四氟乙烯-六氟丙烯共聚物以及乙烯-四氟乙烯共聚物的组中选择的至少一种。
6.根据权利要求1～5中任一项所述的覆铜层叠板的制造方法，其中，
所述粗糙化处理铜箔在所述粗糙化处理表面具有有机防锈层。
7.根据权利要求6所述的覆铜层叠板的制造方法，其中，
所述有机防锈层含有三唑化合物和硅烷偶联剂的至少任一者。
8.根据权利要求6所述的覆铜层叠板的制造方法，其中，
所述有机防锈层含有三唑化合物。
CN201780001695.7A 2016-03-03 2017-01-31 覆铜层叠板的制造方法 Active CN107614753B (zh)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
JP2016-040795 2016-03-03
JP2016040795 2016-03-03
JP2016082658 2016-11-02
JPPCT/JP2016/082658 2016-11-02
PCT/JP2017/003344 WO2017150043A1 (ja) 2016-03-03 2017-01-31 銅張積層板の製造方法

Publications (2)

Publication Number Publication Date
CN107614753A true CN107614753A (zh) 2018-01-19
CN107614753B CN107614753B (zh) 2018-09-28

Family

ID=59742754

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201780001695.7A Active CN107614753B (zh) 2016-03-03 2017-01-31 覆铜层叠板的制造方法

Country Status (5)

Country Link
US (1) US10244635B2 (zh)
KR (1) KR101846141B1 (zh)
CN (1) CN107614753B (zh)
SG (1) SG11201708903SA (zh)
WO (1) WO2017150043A1 (zh)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111029590A (zh) * 2019-12-25 2020-04-17 苏州清陶新能源科技有限公司 一种电池极片基体、其制备方法和用途
CN112004610A (zh) * 2018-04-26 2020-11-27 Ａｇｃ株式会社 层叠体的制造方法及层叠体
CN112204171A (zh) * 2018-06-20 2021-01-08 纳美仕有限公司 粗化处理铜箔、贴铜叠层板和印刷电路板

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7013003B2 (ja) * 2017-11-10 2022-01-31 ナミックス株式会社 粗面化処理された銅表面を有する物体
WO2019131093A1 (ja) * 2017-12-26 2019-07-04 Ｊｘ金属株式会社 放熱用銅箔及び放熱部材
DE102018200758A1 (de) * 2018-01-18 2019-07-18 Robert Bosch Gmbh Antennenelement und Antennenarray
WO2020095988A1 (ja) * 2018-11-08 2020-05-14 株式会社クラレ 熱可塑性液晶ポリマーフィルムおよびそれを用いた回路基板
JP2020152855A (ja) * 2019-03-22 2020-09-24 横浜ゴム株式会社 熱硬化性樹脂組成物及び熱硬化性樹脂
US20230276579A1 (en) 2020-07-16 2023-08-31 Mitsui Mining & Smelting Co., Ltd. Manufacturing methods for copper-clad laminate and printed wiring board
US20230276571A1 (en) 2020-07-16 2023-08-31 Mitsui Mining & Smelting Co., Ltd. Copper-clad laminate plate and printed wiring board

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005310621A (ja) * 2004-04-23 2005-11-04 Matsushita Electric Ind Co Ltd 非水電解液二次電池
JP2011162860A (ja) * 2010-02-12 2011-08-25 Furukawa Electric Co Ltd:The 表面粗化銅箔とその製造方法及び銅張積層板
WO2015040998A1 (ja) * 2013-09-20 2015-03-26 三井金属鉱業株式会社 銅箔、キャリア箔付銅箔及び銅張積層板
WO2015111756A1 (ja) * 2014-01-27 2015-07-30 三井金属鉱業株式会社 粗化処理銅箔、銅張積層板及びプリント配線板

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2955974A (en) * 1957-06-10 1960-10-11 Int Resistance Co Metal to plastic laminated article and the method of making the same
JPS61176192A (ja) * 1985-01-31 1986-08-07 株式会社日立製作所 銅と樹脂との接着方法
JPH06104543A (ja) 1992-09-22 1994-04-15 Nippon Steel Corp 放熱性の優れたプリント配線板用銅張積層板およびその製造方法
TW374802B (en) * 1996-07-29 1999-11-21 Ebara Densan Ltd Etching composition, method for roughening copper surface and method for producing printed wiring board
EP2100323A4 (en) * 2006-12-12 2011-12-07 Interplex Qlp Inc ELECTRONIC PLASTIC COMPONENT CAPSULATION
MY154259A (en) * 2007-10-22 2015-05-29 Hitachi Chemical Co Ltd Method for forming a copper wiring pattern, and copper oxide particle dispersed slurry used therein
US8518281B2 (en) * 2008-06-03 2013-08-27 Kesheng Feng Acid-resistance promoting composition
CN107881505A (zh) 2013-02-14 2018-04-06 三井金属矿业株式会社 表面处理铜箔及用表面处理铜箔得到的覆铜层压板
KR101856302B1 (ko) * 2013-03-26 2018-05-09 후루카와 덴키 고교 가부시키가이샤 전고체 이차 전지
JP6060854B2 (ja) 2013-08-21 2017-01-18 住友金属鉱山株式会社 樹脂フィルムの表面処理方法及びこれを含んだ銅張積層板の製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005310621A (ja) * 2004-04-23 2005-11-04 Matsushita Electric Ind Co Ltd 非水電解液二次電池
JP2011162860A (ja) * 2010-02-12 2011-08-25 Furukawa Electric Co Ltd:The 表面粗化銅箔とその製造方法及び銅張積層板
WO2015040998A1 (ja) * 2013-09-20 2015-03-26 三井金属鉱業株式会社 銅箔、キャリア箔付銅箔及び銅張積層板
WO2015111756A1 (ja) * 2014-01-27 2015-07-30 三井金属鉱業株式会社 粗化処理銅箔、銅張積層板及びプリント配線板

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112004610A (zh) * 2018-04-26 2020-11-27 Ａｇｃ株式会社 层叠体的制造方法及层叠体
CN112204171A (zh) * 2018-06-20 2021-01-08 纳美仕有限公司 粗化处理铜箔、贴铜叠层板和印刷电路板
TWI808183B (zh) * 2018-06-20 2023-07-11 日商納美仕有限公司 粗化處理銅箔、貼銅層合板及印刷佈線板
CN112204171B (zh) * 2018-06-20 2023-09-29 纳美仕有限公司 粗化处理铜箔、贴铜叠层板和印刷电路板
CN111029590A (zh) * 2019-12-25 2020-04-17 苏州清陶新能源科技有限公司 一种电池极片基体、其制备方法和用途

Also Published As

Publication number Publication date
US10244635B2 (en) 2019-03-26
WO2017150043A1 (ja) 2017-09-08
KR20170127039A (ko) 2017-11-20
CN107614753B (zh) 2018-09-28
US20180139848A1 (en) 2018-05-17
SG11201708903SA (en) 2017-11-29
KR101846141B1 (ko) 2018-04-05

Similar Documents

Publication Publication Date Title
CN107614753B (zh) 覆铜层叠板的制造方法
JP6913188B2 (ja) 表面処理銅箔及び当該銅箔を含むラミネート板並びに装置
CN112204171B (zh) 粗化处理铜箔、贴铜叠层板和印刷电路板
CN105556004B (zh) 铜箔、带有载体箔的铜箔及覆铜层压板
CN107923047B (zh) 粗糙化处理铜箔、覆铜层叠板及印刷电路板
CN110087405B (zh) 带有粘合剂层的铜箔、覆铜层压板及印刷布线板
TWI645073B (zh) Copper foil and semiconductor package substrate
US20080261020A1 (en) Adhesive layer for resin and a method of producing a laminate including the adhesive layer
WO2007040196A1 (ja) 表面処理銅箔及びその表面処理銅箔の製造方法並びにその表面処理銅箔を用いた銅張積層板
KR101695236B1 (ko) 동박, 이를 포함하는 전기부품 및 전지
JP6687409B2 (ja) 高彩度処理銅箔及び該処理銅箔を用いた銅張積層板並びに該処理銅箔の製造方法
TWI616336B (zh) Method for manufacturing copper-clad laminate
JP2022019630A (ja) 複合材料及びそれから製造される銅被覆ラミネート
JP6178035B1 (ja) 銅張積層板の製造方法
CN102548202B (zh) 经粗化处理的铜箔及其制造方法
WO2019188837A1 (ja) 表面処理銅箔、銅張積層板、及びプリント配線板の製造方法
TWI819511B (zh) 表面處理銅箔及使用該表面處理銅箔的覆銅層壓板以及印刷線路板
JP7325000B2 (ja) 表面処理銅箔、並びに、それを用いた銅張積層板、樹脂付銅箔および回路基板
KR20230161954A (ko) 조화 처리 구리박, 동장 적층판 및 프린트 배선판
KR20230141859A (ko) 조화 처리 구리박, 동장 적층판 및 프린트 배선판
WO2022014647A1 (ja) 銅張積層板及びプリント配線板の製造方法
JP5135573B2 (ja) 接着性複合体組成物の接着方法、その方法を用いた積層板の製造方法並びに反応性皮膜形成材

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
TR01 Transfer of patent right

Effective date of registration: 20190529

Address after: Niigata Prefecture, Japan

Patentee after: Namics Corp.

Address before: Tokyo, Japan, Japan

Patentee before: Mitsui Mining & Smelting Co.

TR01 Transfer of patent right