TW201940709A - Copper foil with carrier, copper-clad laminate and printed wiring board - Google Patents
Copper foil with carrier, copper-clad laminate and printed wiring board Download PDFInfo
- Publication number
- TW201940709A TW201940709A TW108102636A TW108102636A TW201940709A TW 201940709 A TW201940709 A TW 201940709A TW 108102636 A TW108102636 A TW 108102636A TW 108102636 A TW108102636 A TW 108102636A TW 201940709 A TW201940709 A TW 201940709A
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- TW
- Taiwan
- Prior art keywords
- copper foil
- carrier
- layer
- wiring board
- printed wiring
- Prior art date
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
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- 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
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
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- 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
- B32B15/092—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 epoxy resins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/12—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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/0007—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding involving treatment or provisions in order to avoid deformation or air inclusion, e.g. to improve surface quality
- B32B37/003—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding involving treatment or provisions in order to avoid deformation or air inclusion, e.g. to improve surface quality to avoid air inclusion
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- 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
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- 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
- B32B7/06—Interconnection of layers permitting easy separation
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- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1646—Characteristics of the product obtained
- C23C18/165—Multilayered product
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- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1646—Characteristics of the product obtained
- C23C18/165—Multilayered product
- C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
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- 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
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
- H05K3/025—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates by transfer of thin metal foil formed on a temporary carrier, e.g. peel-apart copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/732—Dimensional properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
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- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/04—Wires; Strips; Foils
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/565—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of zinc
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
- H05K3/384—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by plating
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- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Electrochemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Quality & Reliability (AREA)
- Manufacturing & Machinery (AREA)
- Laminated Bodies (AREA)
- Parts Printed On Printed Circuit Boards (AREA)
- Manufacturing Of Printed Wiring (AREA)
Abstract
Description
本發明有關附有載體之銅箔、銅層積板及印刷配線板。The present invention relates to a copper foil with a carrier, a copper laminate, and a printed wiring board.
作為用以製造印刷配線板之材料已廣泛使用附有載體之銅箔。附有載體之銅箔係將玻璃-環氧基材、酚基材、聚醯亞胺等之絕緣樹脂基材藉由熱加壓而貼合作成銅層積板,使用於製造印刷配線板。As a material for manufacturing a printed wiring board, a copper foil with a carrier has been widely used. The copper foil with a carrier is an insulating resin substrate such as a glass-epoxy substrate, a phenol substrate, or polyimide, which is bonded to a copper laminate by heat and pressure, and is used to produce a printed wiring board.
附有載體之銅箔已提案有典型上具有依序具備載體、剝離層及極薄銅箔之構成,使用含有機化合物之有機剝離層作為該剝離層。例如專利文獻1(日本特開2003-328178號公報)中,揭示附有載體之銅箔之製造方法,其包含使用含有50ppm~2000ppm有機劑之酸洗溶液,將載體表面酸洗溶解,同時藉由吸附有機劑而形成酸洗吸附有機被膜作為有機剝離層,亦揭示使用羧基苯并***(CBTA)作為該有機劑。且,專利文獻2(日本專利第5842077號公報)中,亦揭示使用羧基苯并***(CBTA)作為有機剝離層之附有載體之銅箔。The copper foil with a carrier is proposed to have a structure which typically has a carrier, a release layer, and an ultra-thin copper foil in this order, and an organic release layer containing an organic compound is used as the release layer. For example, Patent Document 1 (Japanese Patent Application Laid-Open No. 2003-328178) discloses a method for manufacturing a copper foil with a carrier, which comprises using an acid pickling solution containing an organic agent at 50 ppm to 2000 ppm to pickle and dissolve the surface of the carrier, while borrowing The formation of an acid-washed and adsorbed organic film by adsorbing an organic agent as an organic release layer has also been disclosed using carboxybenzotriazole (CBTA) as the organic agent. Furthermore, Patent Document 2 (Japanese Patent No. 5842077) also discloses a copper foil with a carrier using carboxybenzotriazole (CBTA) as an organic release layer.
然而,將附有載體之銅箔藉熱加壓貼合於樹脂基材時,於極薄銅箔與載體之間會發生凹坑(blister)(氣泡)。由於凹坑對電路形成造成不良影響,故導致製品良率降低。為了對該問題採取對策,提案有減低剝離層中水分量之技術。例如於專利文獻3(日本特開2015-199355號公報)中,揭示以30℃/分鐘加熱至500℃時所發生之水分量為160ppm/g以下之附有載體之銅箔,藉由設為水分發生受抑制之附有載體之銅箔,而可良好地抑制凹坑之發生。
[先前技術文獻]
[專利文獻]However, when a copper foil with a carrier is bonded to a resin substrate by heat and pressure, a blister (bubble) occurs between the ultra-thin copper foil and the carrier. Since the pits adversely affect the circuit formation, the yield of the product is reduced. In order to take countermeasures against this problem, a technique has been proposed to reduce the moisture content in the peeling layer. For example, Patent Document 3 (Japanese Laid-Open Patent Publication No. 2015-199355) discloses that a copper foil with a carrier having a moisture content of 160 ppm / g or less generated when heated to 500 ° C at 30 ° C / min is set as The occurrence of moisture can be suppressed and the copper foil with a carrier can suppress the occurrence of pits.
[Prior technical literature]
[Patent Literature]
[專利文獻1] 日本特開2003-328178號公報
[專利文獻2] 日本專利第5842077號公報
[專利文獻3] 日本特開2015-199355號公報[Patent Document 1] Japanese Patent Laid-Open No. 2003-328178
[Patent Document 2] Japanese Patent No. 5842077
[Patent Document 3] Japanese Patent Laid-Open No. 2015-199355
然而,如專利文獻3所揭示之先前技術,關於因凹坑發生所致之良率降低問題尚未滿足地解決,而期望進一步改善。However, as in the prior art disclosed in Patent Document 3, the problem of yield reduction due to the occurrence of pits has not been satisfactorily resolved, and further improvements are expected.
本發明人等如今得到如下見解:於具備含羧基之化合物及其衍生物之剝離層之附有載體之銅箔中,藉由將H2 O分子及CO2 分子之個數密度減低為特定值以下,可顯著抑制隨著對樹脂基材之熱加壓積層而發生之凹坑。The present inventors have now found that, in a copper foil with a carrier having a release layer of a carboxyl-containing compound and a derivative thereof, the number density of H 2 O molecules and CO 2 molecules is reduced to a specific value In the following, the occurrence of pits caused by thermally pressing the resin substrate can be significantly suppressed.
因此,本發明之目的在於提供可顯著抑制隨著對樹脂基材之熱加壓積層而發生之凹坑的附有載體之銅箔。Therefore, an object of the present invention is to provide a copper foil with a carrier that significantly suppresses the occurrence of pits caused by thermally pressing the resin substrate.
依據本發明之一態樣,提供一種附有載體之銅箔,其係依序具有載體、剝離層及極薄銅箔之附有載體之銅箔,
前述剝離層包含含羧基之化合物及其衍生物,
前述附有載體之銅箔之每單位面積之H2
O分子的個數為3.44×1016
個/cm2
以下,且前述附有載體之銅箔之每單位面積之CO2
分子的個數為1.39×1016
個/cm2
以下。According to one aspect of the present invention, there is provided a copper foil with a carrier, which is a copper foil with a carrier having a carrier, a release layer, and an ultra-thin copper foil in order,
The release layer includes a carboxyl-containing compound and a derivative thereof,
The number of H 2 O molecules per unit area of the aforementioned copper foil with a carrier is 3.44 × 10 16 pieces / cm 2 or less, and the number of CO 2 molecules per unit area of the aforementioned copper foil with a carrier is 1.39 × 10 16 pieces / cm 2 or less.
依據本發明其他一態樣,提供一種具備前述附有載體之銅箔的銅層積板。According to another aspect of the present invention, a copper laminate provided with the aforementioned copper foil with a carrier is provided.
依據本發明其他一態樣,提供一種具備前述附有載體之銅箔的印刷配線板。According to another aspect of the present invention, there is provided a printed wiring board including the aforementioned copper foil with a carrier.
依據本發明其他一態樣,提供一種印刷配線板之製造方法,其特徵係使用上述附有載體之銅箔,製造印刷配線板。According to another aspect of the present invention, a method for manufacturing a printed wiring board is provided, which is characterized by using the above-mentioned copper foil with a carrier to manufacture a printed wiring board.
附有載體之銅箔
本發明之附有載體之銅箔係依序具有載體、剝離層及極薄銅箔者。剝離層包含含羧基之化合物(典型上為具有羧基之有機化合物)及其衍生物。附有載體之銅箔之每單位面積之H2
O分子的個數為3.44×1016
個/cm2
以下。且附有載體之銅箔之每單位面積之CO2
分子的個數為1.39×1016
個/cm2
以下。如此,於具備包含含羧基之化合物及其衍生物之剝離層的附有載體之銅箔中,藉由將H2
O分子及CO2
分子之個數密度減低至特定值以下,可顯著抑制伴隨對樹脂基材之熱加壓積層而發生之凹坑。由於凹坑對電路形成造成不良影響,故藉由減低凹坑可實現製品良率之提高。Copper foil with carrier The copper foil with carrier of the present invention has a carrier, a release layer, and an ultra-thin copper foil in this order. The release layer contains a carboxyl group-containing compound (typically an organic compound having a carboxyl group) and a derivative thereof. The number of H 2 O molecules per unit area of the copper foil with a carrier is 3.44 × 10 16 pieces / cm 2 or less. In addition, the number of CO 2 molecules per unit area of the copper foil with a carrier is 1.39 × 10 16 pieces / cm 2 or less. As described above, in a copper foil with a carrier having a release layer containing a carboxyl group-containing compound and a derivative thereof, by reducing the number density of H 2 O molecules and CO 2 molecules to a specific value or less, the accompanying A pit generated by heat-pressing a resin substrate. Since the pits adversely affect the circuit formation, the yield of the product can be improved by reducing the pits.
發生凹坑之機制雖尚未明確,但可認為係如下。圖2顯示含羧基之化合物的一種即亞油酸之升溫脫離輪廓之圖。圖2所示之升溫脫離輪廓係顯示將試料(亞油酸)以特定速度升溫時於各溫度下自試料表面脫離之H2 O分子及CO2 分子之個數。如圖2所示,與水的脫離有關之主要波峰存在三點,該等自低溫起依序為i)起因於吸附於試料表面之水的脫離(吸附水之脫離)之波峰,ii)起因於與羧基共振之水的脫離(共振水之脫離)之波峰,及iii)起因於水伴隨相鄰亞油酸彼此之脫水縮合反應(酯化反應)而脫離之波峰。另一方面,與二氧化碳之脫離有關之主要波峰於180℃附近存在1點,其係起因於二氧化碳自亞油酸之羧基脫離之脫碳酸反應的波峰。引起該脫碳酸反應之溫度雖隨有機化合物之種類而異,但一般為150℃以上。如此,即使於比發生吸附水自含羧基之有機化合物脫離之溫度(例如90℃左右)更高之溫度(例如110~200℃),亦大量發生水及二氧化碳。因此,具備包含含羧基化合物之剝離層的附有載體之銅箔藉熱加壓貼合於樹脂基材時,經加熱之剝離層中引起上述反應,大量發生水及二氧化碳。其結果,認為於極薄銅箔與載體之間發生起因於水及二氧化碳氣體之凹坑。此點,依據本發明,藉由事先將附有載體之銅箔中之H2 O分子及CO2 分子之個數密度減低至特定值以下,認為可有效防止對樹脂基材之熱加壓積層時自剝離層大量產生水及二氧化碳,而可顯著抑制凹坑發生者。Although the mechanism of the occurrence of pits is not clear, it can be considered as follows. Figure 2 shows a graph of escaping temperature rise profile of linoleic acid, a carboxyl-containing compound. The temperature rise and drop profile shown in FIG. 2 shows the number of H 2 O molecules and CO 2 molecules that are detached from the sample surface at each temperature when the sample (linoleic acid) is heated at a specific rate. As shown in Figure 2, there are three main peaks related to the detachment of water. These are, in order from low temperature, i) the peaks caused by the detachment of water adsorbed on the sample surface (the detachment of adsorbed water), and ii) the cause. The peaks due to the detachment of water that resonates with the carboxyl group (the detachment of the resonant water), and iii) the peaks due to the detachment of water accompanying the dehydration condensation reaction (esterification reaction) of adjacent linoleic acid with each other. On the other hand, the main peak related to the release of carbon dioxide exists at around 180 ° C, which is a peak resulting from the decarbonation reaction of carbon dioxide from the carboxyl group of linoleic acid. Although the temperature at which the decarbonation reaction is caused varies depending on the type of the organic compound, it is generally 150 ° C or higher. In this way, even at a temperature (for example, 110 to 200 ° C) higher than the temperature (for example, about 90 ° C) at which adsorption water is detached from the carboxyl-containing organic compound, a large amount of water and carbon dioxide occur. Therefore, when a copper foil with a carrier including a release layer containing a carboxyl compound is bonded to a resin substrate by heat and pressure, the above-mentioned reaction occurs in the heated release layer, and a large amount of water and carbon dioxide occur. As a result, it is thought that pits caused by water and carbon dioxide gas occurred between the ultra-thin copper foil and the carrier. At this point, according to the present invention, by reducing the number density of H 2 O molecules and CO 2 molecules in the copper foil with a carrier to a specific value or less in advance, it is considered that the thermal pressure lamination of the resin substrate can be effectively prevented When the self-stripping layer generates a large amount of water and carbon dioxide, the occurrence of pits can be significantly suppressed.
因此,附有載體之銅箔中每單位面積之H2 O分子的個數較好為3.44×1016 個/cm2 以下,更好為3.38×1016 個/cm2 以下,又更好為3.30×1016 個/cm2 以下。每單位面積之H2 O分子的個數之下限值並未特別限定,但典型上為1.00×1015 個/cm2 以上,更典型為1.50×1015 個/cm2 以上,再更典型為1.04×1016 個/cm2 以上。又,附有載體之銅箔中每單位面積之CO2 分子的個數為1.39×1016 個/cm2 以下,較好為1.34×1016 個/cm2 以下,又更好為1.32×1016 個/cm2 以下。每單位面積之CO2 分子的個數之下限值並未特別限定,但典型上為1.00×1015 個/cm2 以上,更典型為1.50×1015 個/cm2 以上,再更典型為9.17×1015 個/cm2 以上。附有載體之銅箔中H2 O分子及CO2 分子的個數,如後述實施例所言,可藉由升溫脫離法(TDS:Thermal Desorption Spectrometry)較好地測定。Therefore, the number of H 2 O molecules per unit area in the copper foil with a carrier is preferably 3.44 × 10 16 pieces / cm 2 or less, more preferably 3.38 × 10 16 pieces / cm 2 or less, and more preferably 3.30 × 10 16 pieces / cm 2 or less. The lower limit of the number of H 2 O molecules per unit area is not particularly limited, but is typically 1.00 × 10 15 / cm 2 or more, more typically 1.50 × 10 15 / cm 2 or more, and more typically It is 1.04 × 10 16 pieces / cm 2 or more. The number of CO 2 molecules per unit area in the copper foil with a carrier is 1.39 × 10 16 pieces / cm 2 or less, preferably 1.34 × 10 16 pieces / cm 2 or less, and more preferably 1.32 × 10 16 pieces / cm 2 or less. The lower limit of the number of CO 2 molecules per unit area is not particularly limited, but it is typically 1.00 × 10 15 / cm 2 or more, more typically 1.50 × 10 15 / cm 2 or more, and even more typically 9.17 × 10 15 pieces / cm 2 or more. The number of H 2 O molecules and CO 2 molecules in the copper foil with a carrier can be better measured by a thermal desorption spectroscopy (TDS: Thermal Desorption Spectrometry) as described in the examples described later.
剝離層係具有使載體與極薄銅箔間之剝離強度較弱,擔保該強度安定性,進而抑制熱加壓成形時於載體與銅箔間引起之相互擴散的功能。剝離層一般係形成於載體之一面,但亦可形成於兩面。剝離層包含含羧基化合物及其衍生物。因此,剝離層典型上為有機剝離層,但亦可為有機剝離層與無機剝離層之複合剝離層,或包含有機剝離劑及無機剝離劑之混合剝離層。此處,所謂含羧基化合物之衍生物包含含羧基化合物之分子內的一部分藉由脫離反應或取代反應等而變化之化合物,或藉由加成反應等而於含羧基化合物之分子內之一部分加成原子團之化合物等。作為此等衍生物之例,舉例為含羧基化合物藉由脫水縮合反應而成為酸酐(典型上為二聚物)之化合物、藉由脫碳酸反應而自羧基脫離CO2 分子之化合物、對含羧基化合物附加甲基等之取代基之化合物等。因此,剝離層只要為自層形成之初包含含羧基化合物及其衍生物即可,但較好為因後述之加熱處理而於事後不可避免地使含羧基化合物之一部分變化為衍生物。亦即,亦可係剝離層最初包含含羧基化合物而不伴隨其衍生物,之後,施以後述之加熱處理而使一部分之含羧基化合物反應(例如脫水縮合反應或脫碳酸反應),而成為包含含羧基化合物及其衍生物之剝離層。The peeling layer has a function of making the peeling strength between the carrier and the ultra-thin copper foil weak, ensuring the stability of the strength, and further suppressing the interdiffusion caused between the carrier and the copper foil during hot press molding. The release layer is generally formed on one side of the carrier, but may be formed on both sides. The release layer contains a carboxyl-containing compound and a derivative thereof. Therefore, the release layer is typically an organic release layer, but may be a composite release layer of an organic release layer and an inorganic release layer, or a mixed release layer containing an organic release agent and an inorganic release agent. Here, the so-called carboxyl-containing compound derivative includes a compound in which a part of the molecule of the carboxyl compound is changed by a dissociation reaction or a substitution reaction, or is added to a part of the molecule of the carboxyl compound by an addition reaction or the like. Atom-forming compounds, etc. As examples of these derivatives, compounds containing a carboxyl group to form an acid anhydride (typically a dimer) by dehydration condensation reaction, compounds that desorb CO 2 molecules from a carboxyl group by decarbonation reaction, and Compounds in which a substituent such as a methyl group is added. Therefore, the release layer may include a carboxyl group-containing compound and a derivative thereof at the beginning of formation of the layer, but it is preferable that a part of the carboxyl group-containing compound is inevitably changed to a derivative after the heat treatment described later. That is, the peeling layer may include a carboxyl group-containing compound initially without accompanying a derivative thereof, and thereafter, a part of the carboxyl group-containing compound may be reacted (for example, a dehydration condensation reaction or a decarbonation reaction) by applying a heat treatment to be described later, and then include Release layer of carboxyl-containing compound and its derivative.
含羧基化合物較好為羧基苯并***(CBTA)。或者,含羧基化合物亦可為單羧酸及/或二羧酸。作為單羧酸之較佳例舉例為亞油酸、油酸、亞麻酸、硫代乙醇酸、3-巰基-2-吡啶羧酸等。作為二羧酸之較佳例舉例為硫代蘋果酸、偶氮二羧酸異丙酯、偶氮二羧酸二乙酯等。藉由剝離層包含上述含羧基化合物,即使於施加熱加壓成形(例如250℃以上)或長時間之烘烤處理(例如於200℃8小時)等之情況下,亦可更進一步維持容易使載體剝離去除之狀態。The carboxyl-containing compound is preferably a carboxybenzotriazole (CBTA). Alternatively, the carboxyl-containing compound may be a monocarboxylic acid and / or a dicarboxylic acid. Preferred examples of the monocarboxylic acid include linoleic acid, oleic acid, linolenic acid, thioglycolic acid, 3-mercapto-2-pyridinecarboxylic acid, and the like. Preferred examples of the dicarboxylic acid include thiomalic acid, isopropyl azodicarboxylate, and diethyl azodicarboxylate. By including the carboxyl-containing compound in the release layer, it is possible to further maintain the easy-to-use condition even when hot press molding (for example, 250 ° C or higher) or long-term baking treatment (for example, 200 hours for 8 hours) is applied. The carrier is peeled and removed.
載體係用以支持極薄銅箔提高其處理性之支持體,典型之載體包含金屬層。作為此等載體之例,舉例為鋁箔、銅箔、不鏽鋼(SUS)箔、表面以銅等金屬塗佈之樹脂膜或玻璃等,較好為銅箔。銅箔可為壓延銅箔及電解銅箔之任一者。載體厚度典型上為250μm以下,較好為9~200μm。The carrier is a support for supporting ultra-thin copper foil to improve its handleability. A typical carrier includes a metal layer. Examples of such carriers include aluminum foil, copper foil, stainless steel (SUS) foil, resin film or glass coated with a metal such as copper on the surface, and copper foil is preferred. The copper foil may be either a rolled copper foil or an electrolytic copper foil. The thickness of the carrier is typically 250 μm or less, preferably 9 to 200 μm.
極薄銅箔可為附有載體之極薄銅箔中採用之習知構成而未特別限定。例如極薄銅箔可為利用無電解銅鍍敷法及電解銅鍍敷法等之濕式成膜法、濺鍍及化學蒸鍍等之乾式成膜法、或該等之組合而形成者。極薄銅箔之較佳厚度為0.1~7.0μm,更好為0.5~5.0μm,又更好為1.0~3.0μm。The ultra-thin copper foil may have a conventional structure used in an ultra-thin copper foil with a carrier, and is not particularly limited. For example, the ultra-thin copper foil may be formed by a wet film formation method such as electroless copper plating method and electrolytic copper plating method, a dry film formation method such as sputtering and chemical vapor deposition, or a combination thereof. The preferred thickness of the ultra-thin copper foil is 0.1 to 7.0 μm, more preferably 0.5 to 5.0 μm, and still more preferably 1.0 to 3.0 μm.
極薄銅箔之最外面(亦即遠離剝離層之側的面)較好為粗化面。亦即,較好於極薄銅箔之一面進行粗化處理。如此,可提高銅層積板或印刷配線板製造時之與樹脂層的密著性。該粗化處理較好依據經過包含如下步驟之至少2種步驟的習知鍍敷方法進行:於極薄銅箔上析出附著微細銅粒並燒結鍍敷之步驟,及用以防止該微細銅粒脫落之外覆鍍敷步驟。The outermost surface of the ultra-thin copper foil (that is, the surface away from the release layer side) is preferably a roughened surface. That is, it is preferable to perform roughening treatment on one side of the ultra-thin copper foil. In this way, the adhesiveness with the resin layer at the time of manufacture of a copper laminated board or a printed wiring board can be improved. The roughening treatment is preferably performed according to a conventional plating method including at least two steps including the steps of depositing fine copper particles on an ultra-thin copper foil and sintering the plating, and preventing the fine copper particles. Outside the plating step.
於剝離層與載體及/或極薄銅箔之間亦可設置其他功能層。作為此等其他功能層之例舉例為輔助金屬層。輔助金屬層較好由鎳及/或鈷所成。藉由於載體表面側及/或極薄銅箔表面側形成此輔助金屬層,可進一步抑制高溫或長時間熱加壓成形時於載體及極薄銅箔之間引起之相互擴散,可擔保載體之剝離強度之安定性。輔助金屬層厚度較好為0.001~3μm。Other functional layers may be provided between the release layer and the carrier and / or the ultra-thin copper foil. An example of such other functional layers is an auxiliary metal layer. The auxiliary metal layer is preferably made of nickel and / or cobalt. By forming the auxiliary metal layer on the surface side of the carrier and / or the surface side of the ultra-thin copper foil, the mutual diffusion caused between the carrier and the ultra-thin copper foil during high-temperature or long-time heat-press forming can be further suppressed, and the carrier can be guaranteed. Stability of peel strength. The thickness of the auxiliary metal layer is preferably 0.001 to 3 μm.
依據期望,亦可對極薄銅箔實施防鏽處理。防鏽處理較好包含使用鋅之鍍敷處理。使用鋅之鍍敷處理可為鋅鍍敷處理及鋅合金鍍敷處理之任一者,鋅合金鍍敷處理特佳為鋅-鎳合金處理。鋅-鎳合金處理若為包含Ni及Zn之鍍敷處理即可,亦可進而包含Sn、Cr、Co等之其他元素。鋅-鎳合金鍍敷中Ni/Zn附著比例,以質量比計,較好為1.2~10,更好為2~7,又更好為2.7~4。又,防鏽處理較好進而包含鉻酸鹽處理。此鉻酸鹽處理更好係於使用鋅之鍍敷處理後,對包含鋅之鍍敷表面進行。若如此則可進而提高防鏽性。特佳之防鏽處理係鋅-鎳合金鍍敷處理與其後之鉻酸鹽處理之組合。Depending on expectations, anti-rust treatment can also be applied to very thin copper foil. The antirust treatment preferably includes a plating treatment using zinc. The plating treatment using zinc may be any one of a zinc plating treatment and a zinc alloy plating treatment, and the zinc alloy plating treatment is particularly preferably a zinc-nickel alloy treatment. The zinc-nickel alloy treatment may be a plating treatment including Ni and Zn, and may further include other elements such as Sn, Cr, and Co. The Ni / Zn adhesion ratio in zinc-nickel alloy plating is preferably 1.2 to 10, more preferably 2 to 7, and even more preferably 2.7 to 4 in terms of mass ratio. The rust prevention treatment preferably further includes a chromate treatment. This chromate treatment is more preferably performed on a plating surface containing zinc after a plating treatment using zinc. If so, the rust prevention property can be further improved. A particularly good antirust treatment is a combination of zinc-nickel alloy plating treatment and subsequent chromate treatment.
依據期望,亦可於極薄銅箔表面實施矽烷偶合劑處理,形成矽烷偶合劑層。藉此可提高耐濕性、耐藥品性及與接著劑等之密著性等。矽烷偶合劑層可藉由適當稀釋矽烷偶合劑並塗佈、乾燥而形成。作為矽烷偶合劑之例舉例為4-縮水甘油基丁基三甲氧基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷等之環氧官能性矽烷偶合劑,或3-胺基丙基三甲氧基矽烷、N-2(胺基乙基)3-胺基丙基三甲氧基矽烷、N-3-(4-(3-胺基丙氧基)丁氧基)丙基-3-胺基丙基三甲氧基矽烷、N-苯基-3-胺基丙基三甲氧基矽烷等之胺基官能性矽烷偶合劑,或3-巰基丙基三甲氧基矽烷等之巰基官能性矽烷偶合劑,或乙烯基三甲氧基矽烷、乙烯基苯基三甲氧基矽烷等之烯烴官能性矽烷偶合劑,或3-甲基丙烯醯氧基丙基三甲氧基矽烷等之丙烯酸官能性矽烷偶合劑,或咪唑基矽烷等之咪唑官能性矽烷偶合劑,或三嗪矽烷等之三嗪官能性矽烷偶合劑等。According to expectations, the surface of the ultra-thin copper foil may also be treated with a silane coupling agent to form a silane coupling agent layer. This can improve moisture resistance, chemical resistance, adhesion to adhesives, and the like. The silane coupling agent layer can be formed by appropriately diluting the silane coupling agent, coating, and drying. Examples of the silane coupling agent include epoxy-functional silane coupling agents such as 4-glycidylbutyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-aminopropyltrimethyl Oxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-3- (4- (3-aminopropyloxy) butoxy) propyl-3-amine Amine-functional silane coupling agents such as propyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and thiol-functional silane coupling agents such as 3-mercaptopropyltrimethoxysilane Mixture, or olefin-functional silane coupling agents such as vinyltrimethoxysilane, vinylphenyltrimethoxysilane, etc., or acrylic functional silane coupling agents such as 3-methacryloxypropyltrimethoxysilane Or an imidazole-functional silane coupling agent such as imidazolyl silane or a triazine-functional silane coupling agent such as triazine silane.
附有載體之銅箔之製造方法
本發明之附有載體之銅箔可依據習知方法藉由於載體上依序形成剝離層、極薄銅箔等之各層製作附有載體之銅箔後,實施以下所述之2階段加熱處理步驟,促進自剝離層之水及二氧化碳產生及排出而較好地製造。Manufacturing method of copper foil with a carrier The copper foil with a carrier of the present invention can be implemented by forming a copper foil with a carrier by sequentially forming layers such as a peeling layer and an ultra-thin copper foil on the carrier according to a conventional method. The two-stage heat treatment step described below promotes the production and discharge of water and carbon dioxide from the peeling layer, and enables better production.
第1階段之加熱處理步驟係藉由高溫處理上述發生水及二氧化碳之反應而進行之步驟。較佳之加熱處理條件係隨附有載體之銅箔的尺寸或形狀、所用之烘烤爐種類等而變動。因此,只要對應於該等變動要素,適當設定充分發生水及二氧化碳之加熱處理條件即可,亦即適當設定不僅使吸附水脫離,而且使共振水自剝離層所含之含羧基化合物脫離以及伴隨脫水縮合反應及脫碳酸反應而產生水及二氧化碳之脫離的加熱處理條件即可。典型上,第1階段之加熱處理溫度為超過180℃之溫度,較好為200~280℃,更好為220~250℃。又,第1階段之加熱處理時間典型上為0.5~40小時,較好為1~30小時,更好為2~24小時。若如此,可邊有效地防止銅箔之劣化或根據期望設定之矽烷偶合劑層的剝落等,邊可較好地自附有載體之銅箔(典型上為剝離層)發生水及二氧化碳。尤其,於接近用以貼合於樹脂基材之熱加壓的溫度進行第1階段之加熱處理,有助於有效抑制伴隨熱加壓積層之凹坑發生。又,典型上,藉由第1階段之高溫加熱處理,可將剝離層中所含之含羧基化合物之一部分變化為其衍生物(例如二聚物或CO2 分子經脫離之化合物)。The heat treatment step in the first stage is a step carried out by high-temperature treatment of the above-mentioned reaction of water and carbon dioxide. Preferred heat treatment conditions vary depending on the size or shape of the copper foil with a carrier, the type of baking furnace used, and the like. Therefore, it is sufficient to appropriately set the heat treatment conditions that sufficiently generate water and carbon dioxide in accordance with these changing factors, that is, to appropriately set not only the adsorption water but also the resonance water from the carboxyl-containing compound contained in the release layer and the accompanying The heat treatment conditions for the dehydration condensation reaction and decarbonation reaction to generate water and carbon dioxide detachment may be sufficient. Typically, the heat treatment temperature in the first stage is a temperature exceeding 180 ° C, preferably 200 to 280 ° C, and more preferably 220 to 250 ° C. The heat treatment time in the first stage is typically 0.5 to 40 hours, preferably 1 to 30 hours, and more preferably 2 to 24 hours. In this case, water and carbon dioxide can be generated from the copper foil (typically a peeling layer) with a carrier, while effectively preventing deterioration of the copper foil or peeling of the silane coupling agent layer that is set as desired. In particular, performing the heat treatment in the first stage at a temperature close to the heat pressure applied to the resin substrate can effectively suppress the occurrence of pits accompanying the heat pressure build-up. In addition, typically, a part of the carboxyl-containing compound contained in the peeling layer can be changed to a derivative thereof (for example, a dimer or a compound in which CO 2 molecules are detached) by a high-temperature heat treatment in the first stage.
第2階段之加熱處理步驟係將因第1階段之加熱處理步驟所產生之水及二氧化碳藉由比較低溫且長時間之加熱處理而自附有載體之銅箔排出之步驟。亦即,由於藉由第1階段之加熱處理而自附有載體之銅箔發生之水及二氧化碳典型上係源自包含含羧基化合物之剝離層者,故該水及二氧化碳駐留於附有載體之銅箔中(例如載體與極薄銅箔之間),而成為凹坑之要因。因此,期望藉由第2階段之加熱處理,將駐留於附有載體之銅箔中之水及二氧化碳迫出系外。其結果,可將附有載體之銅箔(尤其是剝離層)改質至每單位面積之H2 O分子的個數為3.44×1016 個/cm2 以下,且每單位面積之CO2 分子的個數為1.39×1016 個/cm2 以下者。此時,基於進而防止自剝離層發生水及二氧化碳之觀點,第2階段之加熱處理溫度較好低於第1階段之加熱處理溫度。典型上,第2階段之加熱處理溫度為180℃以下,較好為90~180℃,更好為100~180℃。且第2階段之加熱處理時間典型上為3~40小時,較好為5~35小時,更好為5~30小時。若如此,則可將於第1階段之加熱處理所發生之水及二氧化碳有效地自附有載體之銅箔排出。又,與第1階段之加熱處理條件同樣,第2階段之較佳加熱處理條件亦根據附有載體之銅箔的尺寸或形狀、所用之烘烤爐種類等而變動。The heat treatment step in the second stage is a step of discharging water and carbon dioxide generated by the heat treatment step in the first stage from a copper foil with a carrier by a relatively low temperature and long time heat treatment. That is, since water and carbon dioxide generated from the copper foil with a carrier by the heat treatment in the first stage are typically derived from a peeling layer containing a carboxyl-containing compound, the water and carbon dioxide reside in the carrier with the carrier. The copper foil (for example, between the carrier and the ultra-thin copper foil) becomes the cause of the pits. Therefore, it is expected that the water and carbon dioxide residing in the copper foil with a carrier are forced out of the system by the heat treatment in the second stage. As a result, the copper foil with a carrier (especially the release layer) can be modified to a number of H 2 O molecules per unit area of 3.44 × 10 16 units / cm 2 or less, and CO 2 molecules per unit area. The number is 1.39 × 10 16 pieces / cm 2 or less. At this time, from the viewpoint of further preventing the occurrence of water and carbon dioxide from the peeling layer, the heat treatment temperature in the second stage is preferably lower than the heat treatment temperature in the first stage. Typically, the heat treatment temperature in the second stage is 180 ° C or lower, preferably 90 to 180 ° C, and more preferably 100 to 180 ° C. The heat treatment time in the second stage is typically 3 to 40 hours, preferably 5 to 35 hours, and more preferably 5 to 30 hours. If so, the water and carbon dioxide generated in the first-stage heat treatment can be effectively discharged from the copper foil with a carrier. Also, similar to the heat treatment conditions in the first stage, the preferred heat treatment conditions in the second stage vary depending on the size or shape of the copper foil with a carrier, the type of baking furnace used, and the like.
銅層積板
本發明之附有載體之銅箔較好使用於製作印刷配線板之銅層積板。亦即依據本發明之較佳態樣,提供具備上述附載體之銅箔的銅層積板。該銅層積板具備本發明之附有載體之銅箔與密著於該附有載體之銅箔而設置之樹脂層。附有載體之銅箔可設於樹脂層之單面,亦可設於兩面。樹脂層包含樹脂較好包含絕緣性樹脂而成。樹脂層較好為預浸片及/或樹脂薄片。所謂預浸片係於合成樹脂板、玻璃板、玻璃織布、玻璃不織布、紙等之基材中含浸合成樹脂之複合材料的總稱。作為絕緣性樹脂之較佳例舉例為環氧樹脂、氰酸酯樹脂、雙馬來醯亞胺三嗪樹脂(BT樹脂)、聚苯醚樹脂、酚樹脂等。且,作為構成樹脂薄片之絕緣性樹脂舉例為環氧樹脂、聚醯亞胺樹脂、聚酯樹脂等之絕緣樹脂。又,基於對樹脂層提高絕緣性等之觀點,亦可含有由氧化矽、氧化鋁等之各種無機粒子而成之填料粒子等。樹脂層的厚度並未特別限定,但較好為1~1000μm,更好為2~400μm,再更好為3~200μm。樹脂層亦可以複數層構成。預浸片及/或樹脂薄片等之樹脂層亦可經由預先塗佈於極薄銅箔表面之底塗樹脂層而設於附有載體之銅箔上。Copper laminated board The copper foil with a carrier of the present invention is preferably used for a copper laminated board for producing a printed wiring board. That is, according to a preferred aspect of the present invention, a copper laminated board provided with the above-mentioned copper foil with a carrier is provided. The copper laminated board includes the copper foil with a carrier of the present invention and a resin layer provided in close contact with the copper foil with a carrier. The copper foil with a carrier can be provided on one side of the resin layer or on both sides. The resin layer containing resin preferably contains an insulating resin. The resin layer is preferably a prepreg and / or a resin sheet. The so-called prepreg is a general term for a composite material impregnated with a synthetic resin in a substrate such as a synthetic resin plate, a glass plate, a glass woven fabric, a glass nonwoven fabric, or paper. Preferred examples of the insulating resin include epoxy resin, cyanate resin, bismaleimide triazine resin (BT resin), polyphenylene ether resin, and phenol resin. Examples of the insulating resin constituting the resin sheet include insulating resins such as epoxy resin, polyimide resin, and polyester resin. In addition, from the viewpoint of improving the insulation properties of the resin layer, filler particles and the like made of various inorganic particles such as silicon oxide and aluminum oxide may be contained. The thickness of the resin layer is not particularly limited, but is preferably 1 to 1000 μm, more preferably 2 to 400 μm, and even more preferably 3 to 200 μm. The resin layer may be composed of a plurality of layers. The resin layer such as a prepreg sheet and / or a resin sheet may be provided on a copper foil with a carrier through a primer resin layer previously applied on the surface of an ultra-thin copper foil.
印刷配線板
本發明之附有載體之銅箔較好使用於製作印刷配線板。亦即依據本發明之較佳態樣,提供具備上述附有載體之銅箔之印刷配線板或其製造方法。本態樣之印刷配線板包含樹脂層與銅層依此順序積層而成之層構成。又,針對樹脂層係如關於銅層積板有關之上述。總之,印刷配線板可採用習知之層構成。關於印刷配線板之具體例,舉例為於預浸片之單面或雙面接著本發明之極薄銅箔並硬化作成積層體之後,形成電路之單面或雙面印刷配線板或使該等多層化之多層印刷配線板等。又,作為其他具體例亦舉例有於樹脂膜上形成本發明之極薄銅箔並形成電路之可撓性印刷配線板、COF、TAB帶等。作為進而其他具體例舉例為形成於本發明之極薄銅箔上塗佈有上述樹脂層之附樹脂銅箔(RCC),將該樹脂層作為絕緣接著材層積層於上述印刷配線板後,將極薄銅箔作為配線層之全部或一部分而藉改良・半加成(MSAP)法、減去法等之方法形成電路之增層配線板、或去除極薄銅箔並藉半加成法(SAP)形成電路之增層配線板、重複對半導體積體電路上積層附樹脂銅箔與電路形成之晶圓上直接增層(Direct Buildup On Wafer)等。本發明之附有載體之銅箔亦可較好地使用於利用未使用所謂之芯基板,而使絕緣樹脂層與導體層交替積層之無芯增層法之製造方法。
[實施例]Printed wiring board The copper foil with a carrier of the present invention is preferably used for manufacturing a printed wiring board. That is, according to a preferred aspect of the present invention, a printed wiring board provided with the above-mentioned copper foil with a carrier or a manufacturing method thereof is provided. The printed wiring board of this aspect includes a layer formed by laminating a resin layer and a copper layer in this order. The resin layer is as described above for the copper laminate. In short, the printed wiring board can be constructed using a conventional layer. Specific examples of the printed wiring board include, for example, one side or both sides of the prepreg, followed by the ultra-thin copper foil of the present invention and hardened to form a laminated body, and then a single-sided or double-sided printed wiring board of a circuit is formed or the like. Multi-layered multilayer printed wiring boards, etc. In addition, as other specific examples, a flexible printed wiring board, a COF, a TAB tape, etc., in which the ultra-thin copper foil of the present invention is formed on a resin film to form a circuit are also exemplified. As another specific example, the resin-coated copper foil (RCC) formed by coating the resin layer on the ultra-thin copper foil of the present invention is used as an example, and the resin layer is laminated on the printed wiring board as an insulating adhesive, and then The ultra-thin copper foil is used as the whole or a part of the wiring layer to form a circuit-added wiring board by a method such as the improved and semi-additive (MSAP) method or the subtractive method, or the ultra-thin copper foil is removed and the semi-additive method is used ( (SAP) forming a circuit build-up wiring board, repeating direct buildup on wafers formed by laminating resin copper foil and circuits formed on a semiconductor integrated circuit. The copper foil with a carrier of the present invention can also be suitably used for a manufacturing method of a coreless build-up method in which an insulating resin layer and a conductor layer are alternately laminated without using a so-called core substrate.
[Example]
本發明藉由以下之例進一步具體說明。The present invention is further specifically described by the following examples.
例1、2及4~8
如以下般來進行附有載體之銅箔之製作及評價。Examples 1, 2 and 4 to 8
Production and evaluation of the copper foil with a carrier were performed as follows.
(1)載體之準備
準備以IPC規格分類為等級3之厚度18μm之電解銅箔作為載體。作為該載體之電解銅箔係經電解製箔之狀態的銅箔(所謂生箔),未施以防鏽處理、粗化處理等之表面處理者。進行酸洗處理以將附著於載體表面之油脂成分或表面氧化被膜去除。(1) Preparation of the carrier An electrolytic copper foil having a thickness of 18 μm, which is classified by the IPC standard as Class 3, is prepared as a carrier. The electrolytic copper foil used as the carrier is a copper foil (so-called green foil) in a state of being electrolytically produced, and has not been subjected to a surface treatment such as rust prevention treatment or roughening treatment. A pickling process is performed to remove the grease components or the surface oxide film attached to the surface of the carrier.
(2)剝離層之形成
經酸洗處理之載體的電極面側於CBTA(羧基苯并***)濃度1g/L、硫酸濃度150g/L及銅濃度10g/L之CBTA水溶液中於液溫30℃浸漬30秒,將CBTA成分吸附於載體之電極面。如此,於載體之電極面表面形成CBTA層作為剝離層。(2) Formation of the peeling layer The electrode surface of the pickled carrier is placed in a CBTA (carboxybenzobenzotriazole) concentration of 1 g / L, a sulfuric acid concentration of 150 g / L, and a copper concentration of 10 g / L in an aqueous solution of CBTA at a liquid temperature of 30 Immerse at 30 ° C for 30 seconds to adsorb the CBTA component to the electrode surface of the carrier. In this way, a CBTA layer is formed on the surface of the electrode surface of the carrier as a release layer.
(3)輔助金屬層之形成
形成有剝離層之載體浸漬於使用硫酸鎳製作之鎳濃度20g/L之溶液中,於液溫45℃、pH3、電流密度5A/dm2
之條件,於剝離層上附著相當於厚度0.001μm之附著量的鎳。如此,於剝離層上形成鎳層作為輔助金屬層。(3) Auxiliary metal layer formation The carrier with the release layer is immersed in a solution of nickel concentration of 20 g / L made of nickel sulfate, and the release layer is formed at a temperature of 45 ° C, a pH of 3, and a current density of 5 A / dm 2 . Nickel was deposited on the substrate in an amount corresponding to a thickness of 0.001 μm. In this way, a nickel layer is formed on the release layer as an auxiliary metal layer.
(4)極薄銅箔之形成
將形成輔助金屬層之載體浸漬於銅濃度60g/L及硫酸濃度200g/L的硫酸銅溶液中,以液溫50℃、電流密度5~30A/dm2
電解,於輔助金屬層上形成厚度1.5μm之極薄銅箔。(4) Formation of ultra-thin copper foil The carrier forming the auxiliary metal layer is immersed in a copper sulfate solution having a copper concentration of 60 g / L and a sulfuric acid concentration of 200 g / L, and is electrolyzed at a liquid temperature of 50 ° C and a current density of 5 to 30 A / dm 2 An extremely thin copper foil having a thickness of 1.5 μm is formed on the auxiliary metal layer.
(5)粗化處理
對極薄銅箔表面進行粗化處理。該粗化處理藉由以下2階段鍍敷進行。第1階段鍍敷步驟係使用包含銅10g/L及硫酸120g/L之酸性硫酸銅溶液,於液溫40℃、電流密度30A/dm2
之鍍敷條件進行電鍍。第2階段鍍敷步驟係使用包含銅70g/L及硫酸120g/L之酸性硫酸銅溶液,於液溫40℃、電流密度30A/dm2
之鍍敷條件進行電鍍。(5) Roughening treatment Roughening the surface of the ultra-thin copper foil. This roughening process is performed by the following two-stage plating. The first-stage plating step is electroplating using an acidic copper sulfate solution containing copper 10 g / L and sulfuric acid 120 g / L under plating conditions at a liquid temperature of 40 ° C and a current density of 30 A / dm 2 . The second-stage plating step was performed by using an acidic copper sulfate solution containing copper 70 g / L and sulfuric acid 120 g / L under plating conditions of a liquid temperature of 40 ° C. and a current density of 30 A / dm 2 .
(6)防鏽處理
對粗化處理後之附有載體之銅箔兩面進行由無機防鏽處理及鉻酸鹽處理而成之防鏽處理。作為無機防鏽處理,係使用焦磷酸浴,以焦磷酸鉀濃度80g/L、鋅濃度0.2g/L、鎳濃度2g/L、液溫40℃、電流密度0.5A/dm2
進行鋅-鎳合金防鏽處理。其次,作為鉻酸鹽處理,係於鋅-鎳合金防鏽處理之後,進而形成鉻酸鹽層。該鉻酸鹽處理係以鉻酸濃度1g/L、pH11、液溫25℃、電流密度1A/dm2
進行。(6) Anti-rust treatment Both sides of the copper foil with a carrier after roughening treatment are subjected to anti-rust treatment by inorganic anti-rust treatment and chromate treatment. As an inorganic antirust treatment, zinc-nickel was performed using a pyrophosphate bath at a potassium pyrophosphate concentration of 80 g / L, a zinc concentration of 0.2 g / L, a nickel concentration of 2 g / L, a liquid temperature of 40 ° C, and a current density of 0.5 A / dm 2 . Alloy antirust treatment. Next, as a chromate treatment, a chromate layer was formed after the zinc-nickel alloy antirust treatment. This chromate treatment was performed at a chromic acid concentration of 1 g / L, a pH of 11, a liquid temperature of 25 ° C, and a current density of 1 A / dm 2 .
(7)矽烷偶合劑處理
將施以上述防鏽處理之銅箔進行水洗,隨後立即進行矽烷偶合劑處理,於粗化處理面之防鏽處理層上吸附矽烷偶合劑。該矽烷偶合劑處理係藉由使用以純水作為溶劑,3-胺基丙基三甲氧基矽烷濃度為3g/L之溶液,利用淋洗環將該溶液吹附至粗化處理面進行吸附處理而進行。矽烷偶合劑吸附後,最終藉由電熱器使水分蒸散,獲得具備厚度1.5μm之粗化處理銅箔之附有載體之銅箔。(7) Silane coupling agent treatment The copper foil to which the rust prevention treatment has been applied is washed with water, and then the silane coupling agent treatment is immediately performed to adsorb the silane coupling agent on the rust prevention treatment layer of the roughened surface. This silane coupling agent treatment is performed by using pure water as a solvent and a solution of 3-aminopropyltrimethoxysilane with a concentration of 3 g / L, and blowing the solution onto the roughened surface using an eluent ring for adsorption treatment. And proceed. After the silane coupling agent was adsorbed, water was finally evaporated by an electric heater to obtain a copper foil with a carrier having a roughened copper foil having a thickness of 1.5 μm and a carrier.
(8)加熱處理
對於如此所得之附有載體之銅箔,於大氣氛圍中,以烘箱於表1所示之條件下進行1階段或2階段之加熱處理。此時,將例1、2及4~8之各例中之加熱條件如表1所示般適當變化,而製作剝離層中之水分含量及二氧化碳含量不同之各種樣品。又,加熱處理條件係根據樣品之尺寸或烘烤爐種類等而異,當然本發明絕不因該等條件而受到限制。(8) Heat treatment The copper foil with a carrier thus obtained was subjected to a one-stage or two-stage heat treatment in an atmosphere in an oven under the conditions shown in Table 1. At this time, the heating conditions in each of Examples 1, 2, and 4 to 8 were appropriately changed as shown in Table 1, and various samples having different moisture content and carbon dioxide content in the peeling layer were prepared. In addition, the heat treatment conditions vary depending on the size of the sample, the type of the baking oven, and the like, of course, the present invention is not limited by these conditions.
(9)附有載體之銅箔評價
針對所得附有載體之銅箔進行以下評價。(9) Evaluation of copper foil with carrier The following evaluations were performed on the obtained copper foil with carrier.
<評價1:水分及二氧化碳之測定>
藉由升溫脫離法(TDS:Thermal Desorption
Spectrometry)如以下般進行所得附有載體之銅箔(尤其剝離層)中所含之水分及二氧化碳之測定。首先,為了去除上述(8)中施以加熱處理之附有載體之銅箔表面吸附之水分,而以真空定溫乾燥器,於50℃、對於大氣壓為-0.1 MPa之條件進行7天真空乾燥。其次,將已進行真空乾燥之附有載體之銅箔以衝壓機衝打成直徑1cm的大小,作成試驗片,快速測定該試驗片之重量。將試驗片以載體與極薄銅箔分離之狀態(亦即剝離層露出之狀態)設定於升溫脫離分析裝置(電子科學股份有限公司製,TDS1200II)之腔室中,流通氮氣3分鐘後,進行5分鐘抽真空。隨後,對試驗片照射燈光,利用光吸收以30℃/分鐘之升溫速度使試驗片升溫至400℃,針對其間自試驗片產生之氣體,藉由質量分析計進行定性及定量。此時,將m/z=18作為H2
O氣體,將m/z=44作為CO2
氣體進行解析,分別獲得附有載體之銅箔中直徑1cm的圓內所佔之H2
O分子及CO2
分子之各個數。藉由將如此獲得之值除以直徑1cm的圓面積(0.785cm2
),算出每單位面積之H2
O分子及CO2
分子之各個數。結果彙總示於表1及圖1。又,表1中,為了參考,亦一併示出藉由將H2
O及CO2
之各重量(自分子個數換算者)除以試驗片重量而算出之附有載體的銅箔之H2
O及CO2
之各重量比例(ppm)。<Evaluation 1: Measurement of moisture and carbon dioxide>
Thermal Desorption (TDS: Thermal Desorption
Spectrometry) The moisture and carbon dioxide contained in the obtained copper foil with a carrier (particularly a release layer) were measured as follows. First, in order to remove the moisture adsorbed on the surface of the copper foil with a carrier subjected to heat treatment in the above (8), a vacuum constant temperature dryer was used to perform vacuum drying at 50 ° C for 7 days under atmospheric pressure of -0.1 MPa. . Next, the copper foil with a carrier that has been vacuum-dried was punched into a size of 1 cm in diameter by a punch to make a test piece, and the weight of the test piece was quickly measured. The test piece was set in a state where the carrier was separated from the ultra-thin copper foil (that is, the state where the peeling layer was exposed) in a chamber of a temperature rising separation analysis device (manufactured by Electronic Science Co., Ltd., TDS1200II). Evacuate for 5 minutes. Subsequently, the test piece was irradiated with light, and the test piece was heated to 400 ° C at a temperature increase rate of 30 ° C / min by light absorption, and the gas generated from the test piece was qualitatively and quantitatively analyzed by a mass spectrometer. At this time, m / z = 18 was used as the H 2 O gas, and m / z = 44 was used as the CO 2 gas. The H 2 O molecules and the 1 cm diameter circle in the copper foil with the carrier were obtained. Each number of CO 2 molecules. By dividing the value thus obtained by a circle area (0.785 cm 2 ) with a diameter of 1 cm, the respective numbers of H 2 O molecules and CO 2 molecules per unit area were calculated. The results are summarized in Table 1 and FIG. 1. In Table 1, for reference, the H of the copper foil with a carrier calculated by dividing each weight of H 2 O and CO 2 (converted from the number of molecules) by the weight of the test piece is also shown. The respective weight ratios (ppm) of 2 O and CO 2 .
<評價2:凹坑之測定>
準備厚度100μm之預浸片(三菱瓦斯化學股份有限公司製,GHPL-830NSF)作為樹脂基材。對該樹脂基材將上述(8)中施以加熱處理之附有載體之銅箔以其極薄銅箔側與樹脂基材抵接之方式進行積層,以壓力2.4MPa及溫度250℃進行90分鐘熱加壓成形後,進一步以烘烤爐於溫度200℃進行8小時烘烤處理,獲得銅層積板樣品。自該銅層積板樣品剝離載體後,使用光學顯微鏡(KYENCE股份有限公司製,VHX-5000),以倍率20倍及測定視野18mm×13.5mm之條件,計算於極薄銅箔表面形成之凹陷數,將不同3視野之平均值作為凹坑數。亦即由於於載體剝離後之銅層積板樣品表面(亦即極薄銅箔表面)形成凹陷作為起因於載體與極薄銅箔之間發生之凹坑的痕跡,故該凹陷數視為所發生之凹坑數。結果彙總示於表1。<Evaluation 2: Measurement of pits>
A 100 μm-thick prepreg (GHPL-830NSF, manufactured by Mitsubishi Gas Chemical Co., Ltd.) was prepared as a resin substrate. The copper foil with a carrier subjected to the heat treatment in the above (8) was laminated on the resin substrate so that the ultra-thin copper foil side was in contact with the resin substrate, and the temperature was 90 at a pressure of 2.4 MPa and a temperature of 250 ° C. After the one-minute hot press molding, a baking furnace was further subjected to a baking treatment at a temperature of 200 ° C. for 8 hours to obtain a copper laminate sample. After removing the carrier from the copper laminate sample, the depression formed on the surface of the ultra-thin copper foil was calculated using an optical microscope (VHX-5000, manufactured by KYENCE Co., Ltd.) at a magnification of 20 times and a measuring field of view of 18 mm × 13.5 mm. The number of pits is the average value of the three fields of view. That is to say, since the depression formed on the surface of the copper laminate sample (that is, the surface of the ultra-thin copper foil) after the carrier is peeled off is a trace caused by the pits occurring between the carrier and the ultra-thin copper foil, the number of depressions is considered The number of pits that occurred. The results are summarized in Table 1.
例3(比較)
除了不對附有載體之銅箔施以加熱處理水以外,與例1同樣進行附有載體之銅箔的製作及評價。結果彙總示於表1及圖1。Example 3 (comparative)
A copper foil with a carrier was produced and evaluated in the same manner as in Example 1 except that the copper foil with a carrier was not subjected to heat-treated water. The results are summarized in Table 1 and FIG. 1.
例9(比較)
除了於剝離層之形成步驟中,替代CBTA水溶液,而使用亞油酸濃度1000重量ppm之亞油酸水溶液以外,與例2同樣進行附有載體之銅箔的製作及評價。結果彙總示於表1及圖1。Example 9 (comparative)
Except that in the step of forming the release layer, instead of the CBTA aqueous solution, a linoleic acid aqueous solution having a linoleic acid concentration of 1,000 ppm by weight was used, and a carrier-made copper foil was produced and evaluated in the same manner as in Example 2. The results are summarized in Table 1 and FIG. 1.
圖1係對例1~9之附有載體之銅箔之每單位面積之H2 O分子及CO2 分子的各個數作圖之圖。FIG. 1 is a graph plotting the respective numbers of H 2 O molecules and CO 2 molecules per unit area of the copper foil with a carrier of Examples 1 to 9. FIG.
圖2係顯示亞油酸之升溫脫離輪廓之圖。 Fig. 2 is a graph showing the temperature rise off profile of linoleic acid.
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