WO2017130721A1 - 表面改質ポリエステル系樹脂を含む銅または銅合金物品および製造方法 - Google Patents
表面改質ポリエステル系樹脂を含む銅または銅合金物品および製造方法 Download PDFInfo
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- WO2017130721A1 WO2017130721A1 PCT/JP2017/000855 JP2017000855W WO2017130721A1 WO 2017130721 A1 WO2017130721 A1 WO 2017130721A1 JP 2017000855 W JP2017000855 W JP 2017000855W WO 2017130721 A1 WO2017130721 A1 WO 2017130721A1
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- compound
- copper alloy
- polyester resin
- copper
- compound 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
- 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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- 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
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- 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
- B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
- B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
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- 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
- B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
- B29C65/48—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
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- 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
- B29C66/01—General aspects dealing with the joint area or with the area to be joined
- B29C66/02—Preparation of the material, in the area to be joined, prior to joining or welding
- B29C66/026—Chemical pre-treatments
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- 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
- B29C66/01—General aspects dealing with the joint area or with the area to be joined
- B29C66/05—Particular design of joint configurations
- B29C66/10—Particular design of joint configurations particular design of the joint cross-sections
- B29C66/11—Joint cross-sections comprising a single joint-segment, i.e. one of the parts to be joined comprising a single joint-segment in the joint cross-section
- B29C66/112—Single lapped joints
- B29C66/1122—Single lap to lap joints, i.e. overlap joints
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- 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
- B29C66/71—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 composition of the plastics material of the parts to be joined
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- 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
- B29C66/74—Joining plastics material to non-plastics material
- B29C66/742—Joining plastics material to non-plastics material to metals or their alloys
- B29C66/7428—Transition metals or their alloys
- B29C66/74281—Copper or alloys of copper
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- 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
- B29C66/90—Measuring or controlling the joining process
- B29C66/91—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux
- B29C66/919—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges
- B29C66/9192—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams
- B29C66/91921—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams in explicit relation to another temperature, e.g. to the softening temperature or softening point, to the thermal degradation temperature or to the ambient temperature
- B29C66/91931—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams in explicit relation to another temperature, e.g. to the softening temperature or softening point, to the thermal degradation temperature or to the ambient temperature in explicit relation to the fusion temperature or melting point of the material of one of the parts to be joined
- B29C66/91935—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams in explicit relation to another temperature, e.g. to the softening temperature or softening point, to the thermal degradation temperature or to the ambient temperature in explicit relation to the fusion temperature or melting point of the material of one of the parts to be joined lower than said fusion temperature
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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
- 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
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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
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
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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
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J139/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Adhesives based on derivatives of such polymers
- C09J139/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
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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
- 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
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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
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
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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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/10—Other heavy metals
- C23G1/103—Other heavy metals copper or alloys of copper
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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
- H05K1/03—Use of materials for the substrate
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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
- H05K1/03—Use of materials for the substrate
- H05K1/05—Insulated conductive substrates, e.g. insulated metal substrate
- H05K1/056—Insulated conductive substrates, e.g. insulated metal substrate the metal substrate being covered by an organic insulating layer
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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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- 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
- B29C66/90—Measuring or controlling the joining process
- B29C66/92—Measuring or controlling the joining process by measuring or controlling the pressure, the force, the mechanical power or the displacement of the joining tools
- B29C66/929—Measuring or controlling the joining process by measuring or controlling the pressure, the force, the mechanical power or the displacement of the joining tools characterized by specific pressure, force, mechanical power or displacement values or ranges
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- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
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- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/12—Using specific substances
- H05K2203/122—Organic non-polymeric compounds, e.g. oil, wax, thiol
- H05K2203/124—Heterocyclic organic compounds, e.g. azole, furan
Definitions
- the present disclosure relates to a copper alloy article including a copper alloy in which a polyester resin member is bonded to at least a part of a surface, a polyester resin member suitable for manufacturing a copper alloy article, and a method for manufacturing the same.
- a copper alloy is an indispensable material as a wiring material, and an electronic circuit board (printed wiring board) in which a copper wiring and an insulating layer mainly made of a resin are combined is used in an electronic device.
- an electronic circuit board printed wiring board
- Rigid printed wiring boards that use non-flexible materials such as epoxy resin impregnated into glass fiber and hardened on the printed wiring board, and thin and flexible materials such as polyimide film and polyester film
- FPC flexible printed wiring board
- FCCL Flexible Copper Clad Laminate
- FCCL Flexible Copper Clad Laminate
- a method anchor effect
- the surface of the copper foil is roughened and the adhesive or heated resin surface is brought into close contact with the rough surface.
- Patent Document 1 discloses a copper oxide layer present on the surface of a copper wiring layer in order to obtain high adhesion between a copper wiring layer having a smooth surface and an insulating layer in a circuit board having a cured resin as an insulating layer.
- -Based silane cups having silanol groups which are substituted or coated with oxides and / or hydroxides of other metals such as tin, zinc, chromium, cobalt and aluminum and covalently bonded to the oxide and hydroxide layers
- a layer of a ring agent or a mixture thereof is provided, and a vinyl-based silane coupling agent layer having a carbon-carbon unsaturated double bond is further formed thereon to form a vinyl group contained in the resin cured product of the insulating layer.
- a circuit board (multilayer wiring board) in which a covalent bond is formed therebetween is disclosed.
- a circuit board manufacturing method a copper oxide layer on a copper surface is replaced or covered with a metal oxide and / or hydroxide layer such as tin, zinc, chromium, cobalt and aluminum by plating, sputtering or vapor deposition.
- the metal oxide and hydroxide layers increase the adhesion between the silane coupling agent and the metal layer
- the residual silanol groups in the amine silane coupling agent layer and the silanol groups in the vinyl silane coupling agent layer cause a covalent bond
- the carbon-carbon unsaturated double bond of the vinyl silane coupling agent forms a covalent bond with the vinyl compound in the insulating layer
- pressurizes and heats the resin cured product of the insulating layer What includes curing is disclosed.
- This circuit board has a complicated configuration and a complicated manufacturing process.
- Patent Document 2 discloses a flexible laminate in which a silane coupling agent is interposed between a base film of polyethylene naphthalate (PEN), which is a polyester resin, and a conductive layer such as copper. It is described that the hydrolysis functional group of the silane coupling agent reacts with water to form a silanol group and binds to a metal such as copper, and the organic functional group binds to PEN by reaction. Further, a laminating process is disclosed in which a copper alloy is laminated on a base film coated with a silane coupling agent by a sputtering method, and further, copper plating is performed to form a conductive layer.
- PEN polyethylene naphthalate
- Patent Documents 3 to 6 a copper or aluminum metal material whose surface is not roughened, or a plating material obtained by plating the metal material with silver, nickel, or chromate is coated with a silane or titanium coupling agent.
- a treated surface treated metal material is disclosed.
- a method for producing a composite in which a liquid crystal polymer (hereinafter referred to as LCP) film having a polyester structure is thermocompression bonded to the surface-treated metal material, or a polymer is injection-molded and joined.
- LCP liquid crystal polymer
- a coupling agent for the surface treatment of a metal or its plating material a coupling agent having a functional group containing nitrogen, that is, an amine-based silane or titanium coupling agent is preferable, and adheres well to the metal and peel strength. It is described that (peel strength) is high and effective.
- Patent Document 7 Since the novel compound disclosed in Patent Document 7 has an amino group and an alkoxysilane group introduced into a triazine ring, when a surface treatment agent containing the compound is used, a metal and a resin are more effective than an existing silane coupling agent. The chemical bonding property that connects is increased. However, there is a need for a method that can provide higher bonding strength.
- an object of the present disclosure is to provide a copper alloy article in which a polyester resin main body and a copper alloy substrate are joined, in which they are joined with sufficiently high joining strength, and a method for manufacturing the same.
- Aspect 1 of the present invention includes a base made of a copper alloy, a polyester resin body, and a compound layer that joins the base and the polyester resin body.
- Aspect 2 of the present invention is the copper alloy article according to Aspect 1, wherein the functional group containing nitrogen has a cyclic structure of five or more members containing nitrogen.
- Aspect 3 of the present invention is the copper alloy article according to Aspect 2, wherein the cyclic structure having five or more members is a triazole or triazine structure.
- Aspect 4 of the present invention is the copper alloy article according to any one of Aspects 1 to 3, wherein the substrate has a surface roughness Ra of 0.1 ⁇ m or less.
- the polyester resin main body is made of a polyester resin selected from the group consisting of polyethylene terephthalate, polymethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and a liquid crystal polymer. 5.
- Aspect 6 of the present invention is the copper alloy article according to any one of Aspects 1 to 7, wherein an oxide layer and a rust preventive layer are not present on the surface of the substrate.
- Aspect 7 of the present invention is a polyester resin member including a polyester resin main body and a compound layer provided on the surface of the polyester resin main body,
- the compound layer contains a compound having a functional group containing nitrogen and a silanol group, and an alkane-type amine silane coupling agent.
- Aspect 8 of the present invention is the polyester resin member according to Aspect 7, wherein the functional group containing nitrogen has a cyclic structure of five or more members containing nitrogen.
- Aspect 9 of the present invention is the polyester resin member according to Aspect 8, wherein the cyclic structure having 5 or more members is a triazole or triazine structure.
- a tenth aspect of the present invention is that the polyester resin body is made of a polyester resin selected from the group consisting of polyethylene terephthalate, polymethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and a liquid crystal polymer. 10.
- the polyester resin member according to any one of features 7 to 9, which is characterized.
- Aspect 11 of the present invention is a copper alloy member including a base made of a copper alloy and a compound layer provided on the surface of the base,
- the compound layer includes a compound having a functional group containing nitrogen and a silanol group, and an alkane-type amine-based silane coupling agent.
- Aspect 12 of the present invention is the copper alloy member according to Aspect 11, wherein the functional group containing nitrogen has a cyclic structure of five or more members containing nitrogen.
- Aspect 13 of the present invention is the copper alloy member according to Aspect 12, wherein the five-membered or higher ring structure is a triazole or triazine structure.
- Aspect 14 of the present invention is a method for producing a polyester resin member comprising a polyester resin main body and a compound layer provided on the surface of the polyester resin main body, In the manufacturing method characterized by contacting the surface of the polyester-based resin main body with a solution containing a functional group containing nitrogen and a silanol group and an alkane-type amine-based silane coupling agent, followed by heat treatment is there.
- Aspect 15 of the present invention is a method for producing a copper alloy article comprising a base made of a copper alloy, a polyester resin main body, and a compound layer that joins the base and the polyester resin main body.
- Aspect 16 of the present invention is a method for producing a copper alloy member including a base made of a copper alloy and a compound layer provided on the surface of the base, Washing the substrate with an aqueous acid solution;
- the surface of the substrate is contacted with a solution containing a functional group containing nitrogen and a silanol group and an alkane-type amine-based silane coupling agent, and then heat-treated.
- Aspect 17 of the present invention is a method for producing a copper alloy article comprising a base made of a copper alloy, a polyester resin main body, and a compound layer that joins the base and the polyester resin main body.
- a step of obtaining a copper alloy member by the production method according to aspect 16 Joining the base and the polyester resin main body by bonding the compound layer and the polyester resin main body.
- Aspect 18 of the present invention is such that the molar concentration ratio of the compound having a functional group containing nitrogen and a silanol group and the alkane-type amine-based silane coupling agent in the solution is 1: 0.5 to 1:15. 18.
- the polyester resin main body and the copper alloy substrate can be bonded with sufficient bonding strength through the compound layer containing two kinds of compounds.
- FIG. 1 is a schematic cross-sectional view of a copper alloy article according to Embodiment 1 of the present invention.
- FIG. 2 is an XPS spectrum of the surface of the LCP film coated with ImS.
- FIG. 3 is an XPS spectrum of the surface of the LCP film coated with AAS.
- FIG. 4 is an XPS spectrum of a mixture of AAS and the surface of the LCP film coated with ImS.
- 5 (a) and 5 (b) are schematic cross-sectional views for explaining a first method for producing a copper alloy article according to Embodiment 1.
- FIG. 6 (a) and 6 (b) are schematic cross-sectional views for explaining a second method for producing a copper alloy article according to the first embodiment.
- FIG. 1 is a schematic cross-sectional view of a copper alloy article according to Embodiment 1 of the present invention.
- FIG. 2 is an XPS spectrum of the surface of the LCP film coated with ImS.
- FIG. 3 is an XPS spectrum of
- FIG. 7 is an XPS spectrum of the surface of a copper foil piece coated with AST.
- FIG. 8 is an XPS spectrum of the surface of a copper foil piece coated with AAS.
- FIG. 9 is an XPS spectrum of the surface of a copper foil piece coated with a mixed aqueous solution of AST and AAS.
- FIG. 10 is an XPS spectrum of the surface of a copper foil piece coated with a mixed aqueous solution of AST and AAS.
- FIG. 11 is an XPS spectrum of the surface of a copper foil piece coated with a mixed aqueous solution of AST and AAS.
- FIG. 12 is an XPS spectrum of the surface of a copper foil piece coated with a mixed aqueous solution of AST and AAS.
- FIG. 13 is an FT-IR chart of an LPC test piece prepared from Comparative Example 4 copper-clad laminate.
- FIG. 14 is an FT-IR chart of an LPC test piece prepared from the copper-clad laminate of Comparative Example 5.
- FIG. 15 is an FT-IR chart of an LPC test piece prepared from the copper-clad laminate of Example 6.
- the compound layer for bonding the copper alloy substrate and the polyester-based resin main body contains two types of compounds, so that the bonding strength is higher than when only one of the compounds is included.
- the present inventors have found that the copper alloy article according to the present disclosure can be completed.
- a compound having both a functional group containing nitrogen and a silanol group is used as the first compound.
- an alkane type amine silane coupling agent is used as the second compound.
- the copper alloy base and the polyester-based resin main body include the first compound having a functional group containing nitrogen and a silanol group and the second compound that is an alkane-type amine-based silane coupling agent.
- the present invention relates to a copper alloy article joined through a compound layer. Embodiments according to the present invention will be described below.
- FIG. 1 is a schematic cross-sectional view of a copper alloy article 3 according to Embodiment 1, and includes a copper alloy base 10, a polyester-based resin main body 40, and a compound layer 20 disposed therebetween.
- the copper alloy base 10 and the polyester resin main body 40 are joined via the compound layer 20.
- the copper alloy base 10 is made of pure copper or various copper alloys, and any copper alloy used in industry can be used as the copper alloy.
- a copper foil such as an electrolytic copper foil or a rolled copper foil can be applied.
- a rolled copper foil having high flexibility is suitable for FPC.
- the polyester resin body 40 is made of a polyester resin.
- An example of the polyester resin is a polycondensate of polyvalent carboxylic acid (dicarboxylic acid) and polyalcohol (diol).
- Polyethylene terephthalate (PET) polymethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and liquid crystal polymer (LCP) are preferred.
- a polyester resin film, a polyester resin plate, or the like can be used for the polyester resin main body 40.
- the LCP film has a material characteristic of a low relative dielectric constant and a low dielectric loss tangent, there is an advantage that transmission loss of a high-frequency signal line is particularly reduced when applied to FPC.
- the LCP film has a very low water absorption, the dimensional stability is good even under high humidity.
- a copper alloy article using a rolled copper foil as the copper alloy substrate 10 and an LCP film as the polyester resin body will be described in detail.
- the copper alloy article 3 using the copper alloy substrate 10 and the polyester resin main body 40 in other forms can be similarly configured and manufactured.
- the surface of the copper alloy base 10 is flat, for example, the surface roughness Ra Is preferably 0.1 ⁇ m or less.
- the copper alloy is exposed on the surface of the copper alloy base 10. Therefore, a method for selecting the copper alloy substrate 10 suitable for any of the embodiments will be examined.
- Copper foil A is used in the existing FPC, but when XPS measurement was performed, zinc was detected. That is, it was found that the copper foil A was galvanized.
- the copper foil suitable for the second embodiment one having no plating layer is preferable, and therefore the copper foil A is excluded.
- the surface roughness Ra was measured with a laser microscope. Copper foil B had an R a of 0.05 ⁇ m, and copper foil C had an R a of 0.15 ⁇ m. When the surface wrinkle-like dent (oil spot) was confirmed by SEM observation, the copper foil B had fewer oil spots than the copper foil C. From these results, the copper foil B was judged to have higher surface smoothness, and the copper foil B was used for the copper alloy substrate 10.
- a commercially available copper foil is coated with a rust inhibitor.
- an oxide layer can be formed over time on the surface of the copper foil.
- the rust inhibitor and the oxide layer are removed from the surface of the copper foil, It is desirable to expose copper. For this purpose, it is necessary to perform cleaning (acid cleaning) for removing the rust inhibitor and the oxide layer before using the copper foil. For this reason, the condition of acid cleaning was examined using the copper foil B as a sample.
- the cleaning solution 15% sulfuric acid and 1% hydrochloric acid at room temperature were used.
- the sample was immersed in a cleaning solution at an immersion time of 0 minutes (not cleaned), 1 minute, and 5 minutes, then removed from the cleaning solution, sufficiently washed with ion-exchanged water, and dried. Thereafter, the surface of the sample was analyzed by XPS to determine the cleaning level.
- the cleaning level of the copper foil surface after acid cleaning was determined by whether or not the rust inhibitor remained on the surface.
- the copper foil surface after washing is measured by XPS, and qualitatively determined by the presence or absence of a nitrogen (N) peak derived from a rust inhibitor (a peak of nitrogen N1s orbital near a binding energy of 400 eV). went. In the XPS spectrum, “Yes” was given when a peak due to nitrogen (N) could be confirmed, and “None” was given when no peak could be confirmed.
- the measurement results are shown in Table 2.
- the oxide layer can also be used as a criterion for cleaning level.
- the oxide layer can be completely removed from the surface of the copper foil by acid cleaning, the copper on the surface of the copper foil reacts with oxygen in the atmosphere at the moment when the copper foil is taken out of the cleaning solution, and a trace amount of oxide is formed. Generated. In the surface analysis by XPS, this trace amount of oxide is also detected, so it is difficult to accurately determine the cleaning level.
- the peak derived from the N1s orbital and the peak derived from the Cu ⁇ ⁇ ⁇ 2p orbital by confirming the peak derived from the N1s orbital and the peak derived from the Cu ⁇ ⁇ ⁇ 2p orbital by XPS analysis of the surface of the copper foil peeled from the copper alloy article, It can be seen that acid-washed copper foil was used.
- the absence of a rust inhibitor can be confirmed by the absence of a peak derived from the N 1s orbital.
- the peak derived from the Cu 2p orbit is very small (for example, the peak intensity of 1/10 or less, particularly the peak intensity of 1/20 or less of the peak intensity derived from Cu-O existing near 935 eV). It can be confirmed that there is no oxide layer.
- the compound layer 20 contains two types of compounds, a first compound having a functional group containing nitrogen and a silanol group, and a second compound which is an alkane-type amine-based silane coupling agent. Any of these can be used alone as a silane coupling agent, but in the present disclosure, by using a bulky first compound and a linear second compound in combination, they can be used alone. It has been found that the bond strength can be increased.
- the functional group containing nitrogen is effective in increasing the bond strength to the copper alloy substrate 10 because of its high chemical adsorption to copper.
- the silanol group is effective in increasing the bond strength to the polyester resin main body 40 because of its high chemical adsorption to the ester structure of the polyester resin. Therefore, the compound (first compound) having a functional group containing nitrogen and a silanol group is suitable for bonding the copper alloy substrate 10 and the polyester resin main body 40.
- the present inventors allow a linear silane coupling agent (second compound) to coexist so that the copper alloy substrate 10 and the polyester resin main body 40 We found for the first time that the bond strength can be increased.
- the reason why such an effect can be obtained is not clear, but is considered to be due to the following mechanism.
- the second compound which is an alkane-type amine silane coupling agent, has a relatively low bulk structure (for example, a linear structure).
- the first compound having a functional group containing nitrogen and a silanol group has a bulky structure as compared with the linear second compound. Therefore, in the situation where only the first compound exists, the first compounds are unlikely to be close to each other. Since the second compound can enter between the bulky first compounds, the density of the compound in the compound layer 20 can be increased. Thereby, when the polyester resin main body 40 and the copper alloy substrate 10 are bonded via the compound layer 20, the bonding strength can be increased. Therefore, the copper alloy substrate 10 and the polyester are bonded when the first compound part and the second compound are bonded together in comparison with the case where only the first compound or only the second compound is bonded. The joint strength of the resin body 40 can be improved.
- the surfaces of the copper alloy base 10 and the polyester resin body 40 are not roughened, and a metal oxide layer is not formed on the surface of the copper alloy base.
- the copper alloy base 10 and the polyester-based resin main body 40 can be firmly bonded.
- the “functional group containing nitrogen” of the first compound preferably has a cyclic structure having a nitrogen or more 5-membered ring.
- the cyclic structure having five or more members including nitrogen can be, for example, a triazole or triazine structure. Since the structure of the first compound becomes particularly bulky when it has a five-membered ring structure or more, the first compounds are more difficult to come close to each other. Therefore, the bond strength is improved by mixing the second compound. The effect is even more remarkable.
- the compound layer contains the first compound and the second compound.
- analytical methods such as XPS analysis
- the peak attributed to the nitrogen atom bonded by a double bond the peak attributed to the nitrogen atom bonded by a double bond
- the nitrogen atom of the primary amino group And the peak attributed to the nitrogen atom of the secondary amino group.
- Those peaks can be identified by the analysis spectrum of the XPS spectrum.
- the nitrogen atoms contained in the first compound and the nitrogen atoms contained in the second compound are in different bonding states, the peaks of the XPS spectrum attributed to those nitrogen atoms can be identified. . Thereby, it can be specified that the first compound and the second compound are contained in the compound layer.
- N nitrogen atoms
- a peak indicating chemisorption between copper (Cu) and N atoms did not appear.
- ET-coated LCP and PET there is no peak chemical shift indicating chemisorption with epoxy groups. From these results, it was shown that ET was not physically adsorbed on the surface of copper foil, LCP, or PET but only physically adsorbed.
- the compound AST is a compound having a functional group containing nitrogen and a silanol group (that is, the first compound), and the compound AST is composed of one alkoxysilane group and 2 in a triazine 6-membered ring containing three nitrogen atoms. Has an amino group.
- the compound AST is composed of one alkoxysilane group and 2 in a triazine 6-membered ring containing three nitrogen atoms.
- the copper foil coated with AST when the Cu 2p orbital peak of copper was observed, a peak indicating a bond of Cu and N was confirmed.
- Compound ImS is a compound having a functional group containing nitrogen and a silanol group (that is, a first compound), and has a structure in which a 5-membered imidazole ring and one alkoxysilane group are connected.
- a peak indicating a bond of Cu and N indicating that the imidazole group was chemisorbed on copper.
- there was a Cu (zero-valent) peak indicating that there was a portion where no ImS was present on the copper surface.
- AST no Cu (zero valence) peak was observed, indicating that AST chemisorbs more densely on the copper surface than ImS.
- the compounds AAS and AS are alkane-type amine-based silane coupling agents (that is, the second compound), and are typical compounds widely applied to bonding copper and resin in the prior art documents.
- the Cu 2p orbital peak of copper has a Cu (zero valence) peak as in ImS, and there is a portion where AAS and AS are not adsorbed on the copper surface. It was shown that there is. That is, until now, in many literatures, silanol groups have been chemically adsorbed on the surface of copper, but on the surface of copper that has been sufficiently acid-washed, unlike the literature, the chemical adsorption properties of these compounds are low. It became clear that it fell.
- substituent of the cyclic compound containing nitrogen in addition to the amino group of AST, a ureido group, an isocyanate group, and the like may be used.
- FIG. 2 shows the N1s peak of the XPS spectrum of the ImS film, which is separated into two spectra by XPS spectrum analysis software.
- the second peak appearing at the position of the binding energy of 398.99 eV is attributed to the amino nitrogen atom (labeled with “> N-” in FIG. 2) contained in the 5-membered imidazole ring.
- the intensity of the second peak is substantially the same as the intensity of the first peak.
- FIG. 3 shows the N1s peak of the XPS spectrum of the AAS film, which is separated into three spectra by analysis software.
- the peak appearing at the position of binding energy 399.98 eV is attributed to the nitrogen atom of the primary amino group (labeled with “—NH 2 ” in FIG. 3).
- the peak appearing at the position of binding energy 399.12 eV is attributed to the nitrogen atom of the secondary amino group (labeled with “-NH” in FIG. 3).
- FIG. 4 shows the N1s peak of the XPS spectrum of the compound film containing ImS and AAS, which is separated into two spectra by analysis software.
- the second peak appearing at the position of binding energy 399.44 eV is the peak attributed to the amino nitrogen atom (labeled with “> N-” in FIG.
- the intensity of the second peak is about 2.5 times that of the first peak.
- the intensity of the second peak relative to the first peak is remarkably increased, so that in addition to ImS, a compound containing an amino group (AAS in this example) is included.
- a solution containing a first compound having a functional group containing nitrogen and a silanol group and a second compound that is an alkane-type amine-based silane coupling agent is brought into contact with the surface of the polyester-based resin main body 40.
- the solution can be brought into contact with the surface of the polyester resin main body 40 by a known method such as coating or spraying.
- the compound layer 20 can be formed on the surface of the polyester-based resin main body 40 by heat treatment (FIG. 5A). Thereby, the polyester resin member 47 including the polyester resin main body 40 and the compound layer 20 is obtained.
- the first solution containing the first compound and the second solution containing the second compound may be prepared separately instead of the solution containing the first compound and the second compound.
- the first solution and the second solution are sequentially brought into contact with the surface of the polyester-based resin main body 40, whereby the first compound and the second compound can be mixed and adsorbed on the surface of the polyester-based resin main body 40. it can.
- the second solution may be contacted after the first solution is contacted, or the second solution may be contacted after the second solution is contacted.
- the functional group containing nitrogen preferably has a cyclic structure having a 5-membered ring or more containing nitrogen.
- the cyclic structure having five or more members is a triazole or triazine structure.
- Specific examples of compounds include AST, ImS, AST-like compounds obtained by substituting some functional groups of AST described in Table 5 with other functional groups, imidazole silane coupling agents, and the like.
- AST-like compounds include compounds in which the triethoxy group of AST is a trimethoxy group, and the amino substituent of 4,6-di (2-aminoethyl) amino group of AST is N-2- (aminoethyl)- 3-aminopropyl group, 3-aminopropyl group, N- (1,3-dimethyl-methylidene) propylamino group, N-phenyl-3-aminopropyl group, N- (vinylbenzyl) -2-aminoethyl-3
- Examples include compounds having a -aminopropyl group or a 3-ureidopropyl group.
- imidazole silane coupling agent examples include tris- (trimethoxysilylpropyl) isocyanurate, 1-imidazolyl group, 3-imidazolyl group, and 4-imidazolyl group, trimethoxy group, and triethoxy group. What has a trialkoxysilyl group together is mentioned.
- alkane type amine silane coupling agent a linear alkane type amine silane coupling agent is preferable.
- specific compounds include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane , 3-aminopropyltriethoxysilane and the like.
- the surface of the copper alloy substrate 10 is cleaned with an acid aqueous solution. Thereby, the oxide layer and rust preventive agent which exist on the surface of the copper alloy base 10 can be removed.
- the acid aqueous solution for example, sulfuric acid, hydrochloric acid, a mixed solution of sulfuric acid and chromic acid, a mixed solution of sulfuric acid and hydrochloric acid, a mixed solution of sulfuric acid and nitric acid, and the like can be used.
- an aqueous sulfuric acid solution or an aqueous hydrochloric acid solution is preferred.
- Cleaning can be performed by immersing the copper alloy substrate 10 in an acid aqueous solution for a predetermined time.
- the immersion time may be a range in which the surface oxide layer and the rust preventive agent can be removed and the copper alloy substrate 10 is not significantly eroded.
- 1% hydrochloric acid when 1% hydrochloric acid is used, it can be immersed for 30 seconds to 10 minutes (for example, 1 minute). When 15% sulfuric acid is used, it may be immersed for 1 to 20 minutes (for example, 5 minutes).
- the compound layer 20 may be formed on the surface of the copper alloy substrate 10. A modification will be described with reference to FIGS. 6 (a) and 6 (b).
- Step 1-1 Formation of Chemical Layer 20>
- a solution containing a compound having a functional group containing nitrogen and a silanol group is brought into contact with the cleaned surface of the copper alloy substrate 10. Thereafter, the compound layer 20 can be formed on the surface of the copper alloy substrate 10 by heat treatment (FIG. 6A). Thereby, the copper alloy member 15 including the copper alloy substrate 10 and the compound layer 20 is obtained. Details of the compound layer 20 are described in Step 1-1. It is the same.
- Step 1-2 of Embodiment 1 the surface of the copper alloy substrate 10 is washed with an acid aqueous solution, and the oxide layer and the rust inhibitor present on the surface of the copper alloy substrate 10 are removed.
- polyester-type resin member 47 (FIG. 5 (a)) containing the compound layer 20 and the copper alloy member 15 (FIG. 6 (a)) containing the compound layer 20 are prepared, and those compound layers 20 are made to contact. By applying pressure, a copper alloy article 3 as shown in FIG. 1 can be obtained.
- the compound layer of the polyester-based resin member 47 is formed from a first solution containing a first compound having a functional group containing nitrogen and a silanol group, and the compound layer of the copper alloy member 15 is replaced with an alkane-type amine-based silane cup. You may form from the 2nd solution containing the 2nd compound which is a ring agent.
- the compound layer of the polyester-based resin member 47 and the compound layer of the copper alloy member 15 are brought into contact with each other at the time of bonding, the first compound contained in one compound layer and the second compound contained in the other compound layer When both of the compounds are chemisorbed, the compound layer 20 including the first compound and the second compound can be formed.
- the first compound contained in one compound layer and the second compound contained in the other compound layer are not sufficiently chemically adsorbed, the effect of improving the bonding strength may not be sufficiently exhibited. Therefore, it is preferable to appropriately select a method for forming the compound layer depending on the compound to be used.
- LCP film pieces were prepared by cutting a 50- ⁇ m-thick LCP film CT-Z (manufactured by Kuraray) into a square with a side of 150 mm.
- One of four types of compound aqueous solutions (ET aqueous solution, AAS aqueous solution, ImS aqueous solution, and AST aqueous solution) was applied to both surfaces of the test piece of the LCP film using a JSP dip coater. The concentration of each aqueous solution was 0.1%.
- Copper foil B (manufactured by UACJ, thickness 18 ⁇ m) was washed with 1% hydrochloric acid for 1 minute, sufficiently washed with ion-exchanged water, and dried. Thereafter, eight test pieces (copper foil pieces) obtained by cutting the copper foil B into a square having a side of 150 mm were also prepared. And either of the above-mentioned four types of compound aqueous solution was apply
- Copper foil pieces were placed on both sides of the LCP film piece on which the compound layer was formed, heated at 270 ° C. while being pressed at a surface thickness of 4 MPa with a vacuum press machine manufactured by Kitagawa Seiki, held for 20 minutes, and further 10 ° C. at 290 ° C. Holding for two minutes, a double-sided copper-clad laminate was produced. In this double-sided copper-clad laminate, a compound layer is placed between the LCP film and the copper foil.
- the compound aqueous solution was applied to both the LCP film and the copper foil, but even if applied to either one, a compound layer can be formed between the LCP film and the copper foil. That is, the surface to be applied can be appropriately determined depending on the wettability of the compound solution, the ease of forming the compound layer, the amount of the required compound, and the like.
- a double-sided copper-clad laminate was prepared in the same manner using a test piece in which the compound aqueous solution was not applied to either the LCP film or the copper foil.
- a test piece was cut out from a double-sided copper-clad laminate, and the entire surface of the copper foil on the back surface was removed by etching according to JIS C 6471 section 8.1 “Peeling strength of copper foil”.
- a 10 mm pattern was left by etching, and a peeled test piece was produced. Peel off to the reinforcing plate and fix the LCP film side on the back of the test piece with double-sided tape, use Shimadzu Autograph AGS-5kNX, peel off the copper foil in 180 ° direction at a peeling speed of 50 mm / min, Three peel strengths were measured under each condition. The minimum and maximum values were read from the peel test chart. The results are shown in Table 6.
- the LCP film and the copper foil were not bonded, and were peeled off at the interface between the copper foil and the LCP film.
- the minimum and maximum peel strength values were 0.16 kN / m and 0.20 kN / m, respectively.
- the white LCP film remained thin (thinly cohesive peeling) when the peeling interface of the copper foil after the peeling test was observed.
- the minimum and maximum peel strength values were 0.32 kN / m and 0.37 kN / m, respectively.
- the compound AAS is considered to have a relatively low peel strength because both the copper foil and the LCP film have low chemical adsorption.
- the LCP film and the copper foil were joined by the compound layer containing Compound ImS, the LCP film remained white (cohesive peeling) when the peeling interface of the copper foil after the peeling test was observed.
- the minimum and maximum peel strengths were 0.39 kN / m and 0.44 kN / m, respectively.
- the LCP film remained white (cohesive peeling) when the peeling interface of the copper foil after the peeling test was observed.
- the minimum and maximum peel strength values were 0.59 kN / m and 0.68 kN / m, respectively.
- Example 1 The effect of adding a compound having a cyclic molecular structure containing a nitrogen atom (first compound) and an alkane-type amine-based silane coupling agent (second compound) was examined.
- a 50 ⁇ m-thick LCP film CT-Z (manufactured by Kuraray) was cut into a square with a side of 150 mm to prepare a test piece (LCP film piece). Four pieces of LCP film were prepared.
- One of the compound aqueous solutions containing the compounds shown in Table 7 was applied to both surfaces of the LCP film piece using a JSP dip coater. Specifically, in Example 1, the compound layer was formed using a mixed aqueous solution containing 0.1% by weight of ImS and 1% by weight of AAS. In Comparative Example 2, an aqueous solution containing 0.1% by weight of ImS was used, and in Comparative Example 2, an aqueous solution containing 0.1% by weight of AAS was used.
- Copper foil B (made by UACJ, thickness 18 ⁇ m) shown in Table 1 was washed with 1% hydrochloric acid for 1 minute, then sufficiently washed with ion-exchanged water, and dried. Thereafter, the copper foil B was cut into a square having a side of 150 mm to prepare a test piece (copper foil piece). Eight copper foil pieces were prepared. And either of the above-mentioned four types of compound aqueous solution was apply
- Example 1 when the LCP film and the copper foil were joined together by a compound layer containing both compound ImS (first compound) and compound AAS (second compound), The minimum and maximum peel strengths were 0.44 kN / m and 0.68 kN / m, respectively.
- Example 1 When compared with the maximum peel strength, Example 1 had a peel strength of about 1.55 times (0.68 / 0.44) of Comparative Example 1 and about 1.84 times (0.68 / 0.37) of Comparative Example 2. That is, it was found that by simply mixing the compound ImS and the compound AAS as in Example 1, the peel strength can be improved by 1.5 times or more compared to the case where each of them is used alone. By comparing the maximum values, it is possible to know how much the maximum value of the bonding strength that can be realized by the compound layer as in Example 1 can be improved.
- Example 2 In Example 2, a test piece (“double-sided copper-clad laminate in which an LCP film piece and a copper foil piece were laminated)” was prepared in the same manner as in Example 1 using a compound aqueous solution containing the compounds in Table 8. A peel test was performed. Specifically, in Example 2, the compound layer was formed using a mixed aqueous solution containing 0.1% by weight of AST and 1% by weight of AAS. In Comparative Example 3, an aqueous solution containing 0.1% by weight of AST was used. The results of the peel test are shown in Table 8.
- Example 2 when the LCP film and the copper foil were joined by a compound layer containing both the compound AST (first compound) and the compound AAS (second compound), The minimum and maximum peel strength were 0.68 kN / m and 0.77 kN / m, respectively.
- Example 2 When compared with the maximum peel strength, Example 2 had a peel strength of about 2.08 times (0.77 / 0.37) of Comparative Example 2 and about 1.13 times (0.77 / 0.68) of Comparative Example 3. That is, it was found that by simply mixing the compound AST and the compound AAS as in Example 2, it was possible to realize an improvement in the peel strength of 1.13 times or more compared to the case where each was used alone.
- the bonding strength by using AST alone is sufficiently high among conventional silane coupling agents, but according to the embodiment of the present invention, it can be further improved.
- the first compound having a cyclic molecular structure including a nitrogen atom (for example, the compounds ImS and AST) has a large molecular structure, and therefore a gap is generated between the molecules when chemisorbed.
- a second compound having a low molecular weight and a chain structure (eg, compound AAS) may have an effect of entering and closing the gap between the molecules of the first compound ImS and AST.
- Examples 3 to 7 In Examples 3 to 7, (A) peeling test, (B) XPS analysis and (C) FT-IR test were performed.
- the minimum and maximum peel strengths were 0.60 kN / m and 0.65 kN / m, respectively.
- the peel strength tends to be improved.
- the minimum value of the peel strength is 0.63 to 0.70 kN / m
- the maximum value is 0.67 to 0.73 kN / m.
- the maximum value of the peel strength was about 1.12 times (0.73 / 0.65) as compared with Comparative Example 4.
- Example 7 The minimum and maximum peel strengths of Example 7 were 0.55 kN / m and 0.61 kN / m, respectively, which were lower than Comparative Example 4, but Comparative Example 5 (using an aqueous solution containing only AAS) ) Peel strength (minimum value is 0.42 kN / m, maximum value is 0.47 kN / m).
- the molar ratio of the first compound (AST) to the second compound (AAS) is preferably 1: 1 to 1:10 (Examples 4 to 6)
- the maximum tensile strength is It becomes 0.70 kN / m or more which could not be achieved with the compound, and extremely strong bond strength can be achieved.
- the XPS spectrum was analyzed around the Cu 2p orbital peak of the XPS spectrum.
- a Cu—N bond peak, a Cu—O bond peak, and a Cu (zero-valent) peak are mainly observed.
- the Cu—N bond peak is labeled “Cu—N”
- the Cu—O bond peak is labeled “Cu—O”
- the Cu (zero valence) peak is labeled “Cu (0)”.
- Each peak is interpreted as follows.
- the Cu—N bond peak indicates that the triazine ring and the amino group (both derived from AST) in the compound layer are chemically adsorbed on the copper foil surface.
- the Cu—O bond peak indicates that the silanol group (derived from AST) in the compound layer is chemically adsorbed on the copper foil surface.
- the Cu (zero-valent) peak indicates that there is a copper foil surface that does not chemisorb the compound.
- FIG. 7 is an XPS spectrum of a copper foil piece in which a compound layer is formed from an AST aqueous solution (see Table 9) used in Comparative Example 4.
- a compound layer is formed from an AST aqueous solution (see Table 9) used in Comparative Example 4.
- Table 5 the main Cu—N bond peak
- the Cu (zero-valent) peak was not observed hidden behind the noise.
- the silanol group indicated by the Cu—O bond peak is a functional group that contributes to chemisorption with an ester structure contained in LCP, PET, and the like.
- the ratio of silanol groups chemically adsorbed on the copper foil surface is small. Conceivable. That is, it is preferable that no Cu—O bond peak is observed in the XPS spectrum (or the peak is as small as possible).
- FIG. 8 is an XPS spectrum of a copper foil piece in which a compound layer is formed using the AAS aqueous solution (see Table 9) used in Comparative Example 5.
- AAS aqueous solution see Table 9 used in Comparative Example 5.
- FIGS. 9 to 11 are XPS spectra of copper foil pieces in which a compound layer is formed from a mixed aqueous solution of AST and AAS (see Table 9) used in Examples 3 to 5.
- the molar ratio of AST and AAS in the mixed aqueous solution used is 1: 0.5
- the molar ratio is 1: 1
- the molar ratio is 1: 2.
- a main Cu—N bond peak, a Cu—O bond peak, and a Cu (zero-valent) peak were observed. Compared with FIGS.
- those XPS spectra have large peak intensities of the Cu—O bond peak and Cu (zero-valent) peak, and are close to the peak intensity of the Cu—N bond peak.
- a Cu (zero-valent) peak that was not observed in Fig. 7 (AST alone) can be observed, and the peak intensity of the Cu-O bond peak is Cu-N bond. It became as large as the peak.
- FIG. 12 is an XPS spectrum of a copper foil piece having a compound layer formed of a mixed aqueous solution of AST and AAS used in Example 6 (see Table 9).
- the molar ratio of AST and AAS in the mixed aqueous solution used is 1:10.
- the peak intensities of Cu—O and Cu (zero valence) are significantly lower than the Cu—N bond peak, and the peak of Cu (zero valence) has almost disappeared. Since the Cu (zero-valent) peak almost disappeared, it is judged that the compound layer on the surface of the copper foil almost completely covered the copper surface.
- FT-IR analysis is measured by the attenuated total reflection (ATR) method using a Fourier transform infrared spectrophotometer FT / IR680 Plus with JASCO's ATR500 / M multi-total reflection measurement device manufactured by JASCO. Went.
- the multiple total reflection measurement apparatus used a Ge prism, and the measurement was performed with an incident angle of 45 ° and the number of reflections of 5 times.
- FT-IR charts of each LPC test piece are shown in FIGS.
- FIG. 13 is an FT-IR chart of an LPC test piece prepared from the copper-clad laminate of Comparative Example 4.
- FIG. 15 is an FT-IR chart of an LPC test piece prepared from the copper-clad laminate of Example 6.
- the FT-IR chart of FIG. 15 is significantly different from FIGS. Peak of CN group AST triazine rings of 3295cm -1, and the peak of the CH 2 groups of 2966cm -1 and 2926cm -1 is stronger than 13 and 14.
- the C ⁇ O group of the ester group of the LCP film of 1735 cm ⁇ 1 is weaker than in FIGS.
- a Si—OH group peak was detected at 920 cm ⁇ 1 .
- Example 6 a sufficient bond (high-density bond) was formed between the compound and the ester structure of the LCP film by using a mixed aqueous solution of AST and AAS. Therefore, the compound was not removed when the copper foil was wet etched. That is, the LPC test piece was covered with the compound layer. As a result, in the FT-IR chart of FIG. 15, the peak of the C ⁇ O group of the ester group of the LCP film of 1735 cm ⁇ 1 was reduced. Further, the peak of the C ⁇ N group of the triazine ring of AST of 1715 cm ⁇ 1 appeared clearly (this peak does not appear in Comparative Example 4 (FIG. 13) using AST).
- a copper metal substrate and a polyester resin member could be firmly joined by adding an alkane amine silane coupling agent to a compound having a cyclic molecular structure containing a nitrogen atom. .
- Copper Alloy Article 10 Copper Alloy Base 15 Copper Alloy Member 20 Compound Layer 40 Polyester Resin Body 47 Polyester Resin Member 50 Hydrogen Peroxide Water
Abstract
Description
回路基板の製造方法としては、銅表面の酸化銅層を、メッキ、スパッタまたは蒸着などにより、錫、亜鉛、クロム、コバルトおよびアルミなどの金属酸化物および/または水酸化物層で置換または被覆すること、この金属酸化物および水酸化物層がシランカップリング剤と金属層間の接着力を高めること、アミン系シランカップリング剤層中の残存シラノール基とビニル系シランカップリング剤層のシラノール基とが共有結合を生じること、更にビニル系シランカップリング剤の炭素-炭素不飽和二重結合が絶縁層中のビニル化合物と共有結合を生じること、絶縁層の樹脂硬化物を加圧、加熱下で硬化させることを含むものが開示されている。
この回路基板は、構成が複雑であり、また製造工程が煩雑である。
本発明の態様1は、銅合金よりなる基体と、ポリエステル系樹脂本体と、前記基体と前記ポリエステル系樹脂本体とを接合する化合物層とを含み、
前記化合物層が、窒素を含む官能基とシラノール基とを有する化合物と、アルカン型アミン系シランカップリング剤と、を含有することを特徴とする銅合金物品である。
前記化合物層が、窒素を含む官能基とシラノール基とを有する化合物と、アルカン型アミン系シランカップリング剤と、を含有することを特徴とするポリエステル系樹脂部材である。
前記化合物層が、窒素を含む官能基とシラノール基とを有する化合物と、アルカン型アミン系シランカップリング剤と、を含有することを特徴とする銅合金部材である。
ポリエステル系樹脂本体の表面に、窒素を含む官能基とシラノール基を有する化合物と、アルカン型アミン系シランカップリング剤とを含有する溶液を接触させた後に、熱処理することを特徴とする製造方法である。
態様14に記載の製造方法により、ポリエステル系樹脂部材を得る工程と、
前記基体の表面を酸水溶液で洗浄する工程と、
前記化合物層と、洗浄した前記基体の表面とを接合することにより、前記基体と前記ポリエステル系樹脂本体とを接合する工程と、を含むことを特徴とする製造方法である。
前記基体を酸水溶液で洗浄する工程と、
前記基体の表面に、窒素を含む官能基とシラノール基を有する化合物と、アルカン型アミン系シランカップリング剤とを含有する溶液を接触させた後に、熱処理することを特徴とする製造方法である。
態様16に記載の製造方法により、銅合金部材を得る工程と、
前記化合物層と前記ポリエステル系樹脂本体とを接合することにより、前記基体と前記ポリエステル系樹脂本体とを接合する工程と、を含むことを特徴とする製造方法である。
具体的には、第1の化合物としては、窒素を含む官能基とシラノール基とを共に有する化合物を使用する。第2の化合物としては、アルカン型アミン系シランカップリング剤を使用する。すなわち、本開示は、銅合金基体と、ポリエステル系樹脂本体とが、窒素を含む官能基とシラノール基とを有する第1の化合物およびアルカン型アミン系シランカップリング剤である第2の化合物を含有する化合物層を介して接合された銅合金物品に係るものである。
以下、本発明に係る実施の形態について説明する。
図1は、実施の形態1に係る銅合金物品3の概略断面図であり、銅合金基体10と、ポリエステル系樹脂本体40と、それらの間に配置された化合物層20とを含んでいる。銅合金基体10とポリエステル系樹脂本体40は、化合物層20を介して接合されている。
銅合金基体10には、例えば電解銅箔、圧延銅箔等の銅箔を適用できる。特に、屈曲性の高い圧延銅箔は、FPCに好適である。
実施の形態1および2において、プリント基板における高周波信号の伝送損失を低減するためには、銅合金基体10の表面が平坦であるのが好ましく、例えば表面粗さRaが0.1μm以下であるのが好ましい。また、後述する実施の形態2では、銅合金基体10の表面に銅合金が露出しているのが好ましい。そこで、いずれの実施の形態にも適した銅合金基体10の選択方法について検討する。
次に、これらの銅箔B、Cについては、表面粗さの測定と、表面の電子顕微鏡(SEM)分析を行った。
SEM観察により、表面のしわ状のへこみ(オイルスポット)を確認したところ、銅箔Bのほうが、銅箔Cよりもオイルスポットが少なかった。
これらの結果から、銅箔Bの方が表面の平滑性が高いと判断し、銅合金基体10には、銅箔Bを用いることした。
市販の銅箔には、防錆剤の塗布が塗布されている。また、銅箔の表面には、時間の経過による酸化物層が生成され得る。FCP等の銅合金物品の場合には、銅箔の特性、例えば電気伝導性を最大限発揮するには、銅箔の表面から防錆剤および酸化物層を除去して、銅箔の表面に銅を露出させるのが望ましい。そのためには、銅箔を使用する前に、防錆剤および酸化物層を除去するための洗浄(酸洗浄)を行う必要がある。このため、銅箔Bをサンプルとして用いて、酸洗浄の条件について検討した。
酸洗浄後の銅箔表面の洗浄レベルは、表面に防錆剤が残存するか否かにより判定した。具体的には、洗浄後の銅箔表面をXPSにより測定し、防錆剤に由来する窒素(N)のピーク(結合エネルギー400eV付近の窒素N1s軌道のピーク)の有無により、定性的に判定を行った。XPSスペクトルに、窒素(N)に起因するピークが確認できたときを「あり」とし、ピークが確認できないときは「なし」とした。測定結果を表2に示す。
化合物層20には、窒素を含む官能基とシラノール基とを有する第1の化合物と、アルカン型アミン系シランカップリング剤である第2の化合物の2種類の化合物を含む。いずれも単独でシランカップリング剤として使用することができるが、本開示では、嵩高い第1の化合物と、直鎖状の第2の化合物とを併用することにより、それらを単独使用するよりも結合強度を高めることができることを見いだした。
そのため、第1の化合物のみ、または第2の化合物のみで接合したときに比べて、第1の化合部物と第2の化合物とを共存させて接合したときのほうが、銅合金基板10とポリエステル系樹脂本体40の接合強度を向上させることができる。
5員環以上の環状構造を有すると第1の化合物の構造が特に嵩高くなるため、第1の化合物同士がさらに近接しにくくなることから、第2の化合物を混合することによる結合強度の向上効果が一層顕著である。
ここで、第1の化合物に含まれる窒素原子と、第2の化合物に含まれる窒素原子とが異なる結合状態にあることにより、それらの窒素原子に帰属されるXPSスペクトルのピークは識別可能である。これにより、化合物層中に第1の化合物と第2の化合物とが含まれていることを特定することができる。
以下に、種々の化合物と銅合金基体との接合強度について比較した。
化合物は、表3に示した5種類を選んだ(以下、各化合物は、表3に記載した記号で呼ぶ)。化合物の化学名が開示されているものについては、それを記載したが、詳細が開示されていない化合物ImSについては、開示されている基本構造を記載した。これらの化合物の持つ主要官能基を、表4に示した。アルコキシシラン基は、水溶液ではシラノール基になることが知られている。この中で、化合物ETだけは、アルコキシシラン基をもっておらず、シランカップリング剤ではない。
化合物ETは、窒素を含む官能基とシラノール基とを有する化合物(つまり、第1の化合物)であり、化合物ETは、窒素原子(N)3個を含むトリアジン6員環に3個のエポキシ基と3個のオキソ基(C=O)をもつ。ETコーティングした銅箔では、銅(Cu)とN原子間の化学吸着を示すピークが現れなかった。ETコーティングしたLCPおよびPETでは、エポキシ基との化学吸着を示すピークの化学シフトが生じない。これらのことから、ETは、銅箔、LCP、PETのいずれの表面にも化学吸着せず、物理的に吸着されるのみであることが示された。
化合物ASTは、窒素を含む官能基とシラノール基とを有する化合物(つまり、第1の化合物)であり、化合物ASTは、窒素原子3個を含むトリアジン6員環に1個のアルコキシシラン基と2個のアミノ基を持っている。ASTコーティングした銅箔では、銅のCu 2p軌道ピークをみると、CuとNの結合を示すピークが確認された。また、ASTコーティングしたLCPおよびPETでは、C1s軌道ピークの286~288eVにC-O、C=Oの結合を示すピークが現れ、いずれのピークも元のフィルムのピーク位置からシフトしている。これらのことから、ASTは、トリアジン6員環とアミノ基のNが銅に、シラノール基がLCP、PETのエステル構造に化学吸着することが示された。
化合物ImSは、窒素を含む官能基とシラノール基とを有する化合物(つまり、第1の化合物)であり、イミダゾール5員環と1個のアルコキシシラン基がつながった構造である。ImSコーティングした銅箔では、銅のCu 2p軌道ピークをみると、CuとNの結合を示すピークがあり、イミダゾール基が銅に化学吸着することが示された。同時にCu(0価)のピークもあり、銅の表面にImSが存在しない部分が存在することが示された。ASTでは、Cu(0価)のピークは観測されなかったことから、ASTの方がImSよりも銅表面に高密度で化学吸着することを示している。
化合物AASとASは、アルカン型アミン系シランカップリング剤(つまり、第2の化合物)であり、先行技術文献において、広く銅と樹脂の接着に適用されている典型的な化合物である。しかし、それらの化合物でコーティングした銅箔では、銅のCu 2p軌道ピークをみると、ImSと同様にCu(0価)のピークがあり、銅の表面にAASやASが吸着していない部分があることが示された。すなわち、これまで、多くの文献において、シラノール基が銅の表面と化学的に吸着するとされてきたが、十分酸洗浄された銅表面においては文献とは異なり、これらの化合物の化学的吸着性が低下することが明らかとなった。
AAS、ASコーティングしたLCPにおいては、289eVに未反応のエステル基のピークがあり、LCPに対する化学吸着性も低いと判断される。
第1の化合物としてImS、第2の化合物としてAASを用いて、各化合物とXPSスペクトルとの関係を調べた。
所定の化合物を含む水溶液をLCPフィルムに塗布し、次いで100℃で5分間熱処理した。LCPフィルム表面に形成された化合物の膜について、XPS分析を行った。
結合エネルギー400.87eVの位置に現れる第1のピークは、イミダゾール5員環に含まれる二重結合で結合された窒素原子(図2で"-C=N-C-"でラベリングされている)に帰属される。
結合エネルギー398.99eVの位置に現れる第2のピークは、イミダゾール5員環に含まれるアミノ型の窒素原子(図2で">N-"でラベリングされている)に帰属される。
第2のピークの強度は、第1のピークの強度とほぼ同じである。
結合エネルギー399.98eVの位置に現れるピークは、第一級アミノ基の窒素原子(図3で"-NH2"でラベリングされている)に帰属される。
結合エネルギー399.12eVの位置に現れるピークは、第二級アミノ基の窒素原子(図3で"-NH"でラベリングされている)に帰属される。
結合エネルギー400.97eVの位置に現れる第1のピークは、イミダゾール5員環に含まれる二重結合で結合された窒素原子(図4で"-C=N-C-"でラベリングされている)に帰属される。このピークが存在することから、測定した化合物の膜にImSが含まれていることが分かる。
結合エネルギー399.44eVの位置に現れる第2のピークは、アミノ型の窒素原子(図4で">N-"でラベリングされている)に帰属されるピークと、第一級アミノ基の窒素原子("-NH2"でラベリングされている)に帰属されるピークと、第二級アミノ基の窒素原子("-NH"でラベリングされている)に帰属されるピークとが重なり合っている。第2のピークの強度は、第1のピークの約2.5倍である。図2に示すImSのXPSスペクトルと比べると、第1のピークに対する第2のピークの強度が著しく大きくなっていることから、ImSの他に、アミノ基を含む化合物(この例ではAAS)が含まれていることがわかる。
ポリエステル系樹脂本体40の表面に、窒素を含む官能基とシラノール基とを有する第1の化合物と、アルカン型アミン系シランカップリング剤である第2の化合物とを含有する溶液を接触させる。溶液は、例えば塗布、スプレー等の公知の方法により、ポリエステル系樹脂本体40の表面に接触させることができる。その後に、熱処理することにより、ポリエステル系樹脂本体40の表面に化合物層20を形成することができる(図5(a))。これにより、ポリエステル系樹脂本体40および化合物層20を含むポリエステル系樹脂部材47が得られる。
銅合金基体10の表面を酸水溶液で洗浄する。これにより、銅合金基体10の表面に存在する酸化物層および防錆剤を除去することができる。
酸水溶液としては、例えば、硫酸、塩酸、硫酸とクロム酸の混合液、硫酸と塩酸の混合液、硫酸と硝酸の混合液等の酸溶液の水溶液が利用できる。特に、硫酸水溶液または塩酸水溶液が好ましい。
洗浄は、酸水溶液に銅合金基体10を所定時間浸漬して行うことができる。浸漬する時間は、表面の酸化物層および防錆剤を除去でき、かつ銅合金基体10を大幅に浸食しない範囲であればよい。例えば、1%塩酸を使用する場合には、30秒~10分(例えば1分)浸漬することができる。また、15%硫酸を使用する場合には、1~20分(例えば5分)浸漬してもよい。
図5(b)に示すように、ポリエステル系樹脂部材47の化合物層20と、洗浄した銅合金基体10とを接触させて加圧することにより、ポリエステル系樹脂部材47と銅合金基体10とを接合して、図1に示すような銅合金物品3を得ることができる。これは、ポリエステル系樹脂部材47のポリエステル樹脂本体40と銅合金基体10とを、化合物層20を介して接合する、とみなすこともできる。
加圧する前または加圧中に、銅合金基体10とポリエステル系樹脂部材47を加熱すると、接合しやすくなるので好ましい。なお、加熱温度は、ポリエステル系樹脂部材47のポリエステル系樹脂本体10が溶融しない温度にする。加圧は、面圧1MPa~8MPa、例えば4MPaにすることができる。
洗浄した銅合金基体10の表面に、窒素を含む官能基とシラノール基とを有する化合物を含有する溶液を接触させる。その後に、熱処理することにより、銅合金基体10の表面に化合物層20を形成することができる(図6(a))。これにより、銅合金基体10および化合物層20を含む銅合金部材15が得られる。
化合物層20の詳細は、工程1-1.と同様である。
実施の形態1の工程1-2.と同様の工程により、銅合金基体10の表面を酸水溶液で洗浄して、銅合金基体10の表面に存在する酸化物層および防錆剤を除去する。
図6(b)に示すように、ポリエステル系樹脂本体40と、銅合金部材15の化合物層20とを接触させて加圧することにより、ポリエステル系樹脂本体40と銅合金部材15とを接合して、図1に示すような銅合金物品3を得ることができる。
加圧接合の詳細については、実施の形態1と同様である。
ただし、一方の化合物層に含まれる第1の化合物と、他方の化合物層に含まれる第2の化合物とが十分に化学吸着されない場合には、接合強度の向上効果が十分に発揮されないおそれがあるため、使用する化合物によって、化合物層の形成方法を適宜選択するのが好ましい。
厚さ50μmのLCPフィルムCT-Z(クラレ製)を、一辺150mmの正方形に切断した試験片(LCPフィルム片)を4枚準備した。LCPフィルムの試験片の両面に、JSP製ディップコーターを使用して、4種類の化合物水溶液(ET水溶液、AAS水溶液、ImS水溶液、およびAST水溶液)のいずれかを塗布した。各水溶液の濃度は0.1%とした。
その後、水溶液を塗布したLCPフィルム片と銅箔片を、100℃で5分間熱処理した。これにより、LCPフィルム片の両面と、銅箔片の両面に、化合物層を形成した。
化合物ASTを含む化合物層によりLCPフィルムと銅箔とを接合した場合、剥離試験後の銅箔の剥離界面を観察すると、LCPフィルムが白く残っていた(凝集剥離)。引き剥がし強度の最小値と最大値はそれぞれ0.59kN/m、0.68kN/mであった。
窒素原子を含む環状分子構造を持つ化合物(第1の化合物)と、アルカン型アミン系シランカップリング剤(第2の化合物)とを複合添加したときの効果について調べた。
その後、水溶液を塗布したLCPフィルム片と銅箔片を、100℃で5分間熱処理した。これにより、LCPフィルム片の両面と、銅箔片の両面に、化合物層を形成した。
引き剥がし試験の結果を表7に示す。
比較例2のように、化合物AAS(第2の化合物)のみを含む化合物層によりLCPフィルムと銅箔とを接合した場合、引き剥がし強度の最小値と最大値はそれぞれ0.32kN/m、0.37kN/mであった。
これに対して、実施例1のように、化合物ImS(第1の化合物)と化合物AAS(第2の化合物)とを共に含む化合物層によりLCPフィルムと銅箔とを接合した場合には、引き剥がし強度の最小値と最大値はそれぞれ0.44kN/m、0.68kN/mであった。
実施例2では、表8の化合物を含む化合物水溶液を使用して、実施例1と同様にして試験片(LCPフィルム片と銅箔片を積層した「両面銅張り積層板」)を作製し、引き剥がし試験を行った。具体的には、実施例2では、ASTを0.1重量%、AASを1重量%含有する混合水溶液を使用して、化合物層を形成した。比較例3では、ASTを0.1重量%含有する水溶液を使用した。
引き剥がし試験の結果を表8に示す。
比較例3のように、化合物AST(第1の化合物)のみを含む化合物層によりLCPフィルムと銅箔とを接合した場合、引き剥がし強度の最小値と最大値はそれぞれ0.59kN/m、0.68kN/mであった。
これに対して、実施例2のように、化合物AST(第1の化合物)と化合物AAS(第2の化合物)とを共に含む化合物層によりLCPフィルムと銅箔とを接合した場合には、引き剥がし強度の最小値と最大値はそれぞれ0.68kN/m、0.77kN/mであった。
実施例3~7では、(A)引き剥がし試験、(B) XPS分析および(C)FT-IR試験を行った。
実施例2で使用した化合物AST、AASの混合比と結合強度との関係を調べた。
第1の化合物(化合物AST)と、第2の化合物(AAS)とを含む混合水溶液において、ASTとAASのモル濃度の合計を48mmol/Lに固定し、ASTとAASの濃度をモル比で1:0から1:15まで(重量%比で2:0からおよそ0.1:1.0まで)の間で変更した。ここで、モル濃度を一定にしたのは、溶液中の分子の数で比較することにより、化合物の特性を正しく比較できるためである。つまり、モル濃度で規定することにより、各分子の化学吸着性と接合強度との関係を正しく対比することができる。
引き剥がし試験に使用する試験片(両面銅張り積層板)は、実施例1と同様に形成した。
複合添加の詳細と引き剥がし強度の測定結果を、表9に示した。
実施例7の引き剥がし強度の最小値と最大値はそれぞれ0.55kN/m、0.61kN/mであり、比較例4よりは低い値となったが、比較例5(AASのみを含む水溶液を使用)の引き剥がし強度(最小値が0.42kN/m、最大値が0.47kN/m)よりは高い値となった。
第1の化合物(AST)と第2の化合物(AAS)の混合比と、銅箔表面における化合物の化学吸着の状態との関係を調べた。
銅箔片の表面に、第1の化合物(化合物AST)と、第2の化合物(AAS)とを含む混合水溶液を塗布した。使用する混合水溶液は、実施例3~6および比較例4、5で使用したものと同じである(表9参照)。
銅箔片の表面(両面)に、JSP製ディップコーターを使用して、いずれかの水溶液を塗布する。その後に銅箔片を100℃で5分間熱処理して、銅箔片の表面に化合物層を形成し、化合物層で被覆された銅箔片の表面をXPS分析した。各銅箔片のXPSスペクトルを図7~12に示す。
各ピークは以下のように解釈される。
(i) Cu-N結合ピークは、化合物層中のトリアジン環およびアミノ基(いずれもAST由来)が、銅箔表面に化学吸着していることを示す。
(ii)Cu-O結合ピークは、化合物層中のシラノール基(AST由来)が、銅箔表面に化学吸着していることを示す。
(iii)Cu(0価)ピークは、化合物を化学吸着していない銅箔表面が存在していることを示す。
Cu-O結合ピークで示されるシラノール基は、LCP、PET等に含まれるエステル構造との化学吸着に寄与する官能基である。よって、銅箔と、エステル構造を持つ樹脂フィルムとの引き剥がし強度を向上するには、銅箔表面に化学吸着するシラノール基(つまり、消費されるシラノール基)の割合が小さいことが好ましい、と考えられる。すなわち、XPSスペクトルにおいて、Cu-O結合ピークが観察されない(又はピークができるだけ小さい)ことが好ましい。
図9では、使用した混合水溶液中のASTとAASのモル比が1:0.5であり、図10では、モル比が1:1であり、図11では、モル比が1:2である。図9~11のXPSスペクトルには、主要なCu-N結合ピーク、Cu-O結合ピークおよびCu(0価)のピークが観察された。それらのXPSスペクトルは、図7および8と比べると、Cu-O結合ピークおよびCu(0価)ピークのピーク強度が大きく、Cu-N結合ピークのピーク強度に近くなっている。つまり、ASTにAASを混合することにより、図7(AST単独)では観察されなかったCu(0価)ピークが観察されるようになり、さらにCu-O結合ピークのピーク強度がCu-N結合ピークと同等まで大きくなった。
・Cu(0価)ピークのピーク強度が大きくなっていることから、銅箔表面上における化合物の化学吸着の密度が低下している。
・Cu-O結合ピークのピーク強度が大きくなっていることから、シラノール基が銅箔表面に多く化学吸着して、ここで多く消費されていると考えられる。上述した通り、シラノール基は樹脂フィルムのエステル構造に化学吸着するため、銅箔表面で消費されるのは好ましくない。
これらの結果は、銅箔表面上における化合物の化学吸着という観点からみると、ASTにAASを添加する効果が十分発揮されていない状態と見ることができる。
図12では、Cu-OとCu(0価)のピーク強度が、Cu-N結合ピークよりも著しく低くなり、Cu(0価)のピークがほぼ消滅した。Cu(0価)のピークがほぼ消滅したことから、銅箔表面の化合物層が銅表面をほぼ覆い尽くしていると判断される。また、Cu-O結合ピークが著しく低くなったことから、銅箔表面に化学吸着しないシラノール基の割合が高いことがわかる。つまり、樹脂フィルムのエステル構造に化学吸着できるシラノール基が多く残されている。
このように、嵩高い環状構造の第1の化合物と直鎖構造の第2の化合物を混合することにより、接合強度の高い化合物層を形成できることが確認された。さらに、それらの化合物の混合比率を適切に調整することにより、嵩高い環状構造の化合物と直鎖の化合物の立体構造の違いを特に有効に利用することが可能となり、銅箔と、エステル構造を持つ樹脂フィルムとに対する化合物の化学吸着の密度および構造を最適化できることが確認された。
言い換えれば、本開示に係る発明の効果を最大限に発揮するためには、広く利用されている直鎖型のシランカップリング剤を複数混合すること、および/または嵩高い化合物を複数混合するだけではなく、化合物の選択と、その混合比率を適切に調節することが重要である。
化合物層とLCPフィルム表面との結合状態を調べた。
上記の「(A)引き剥がし試験」と同様に、比較例4、5と実施例6の試験片(両面銅張り積層板)を作成した。得られた銅張り積層板を温度60℃の30~35%塩化第二鉄水溶液に5~6分浸漬し、銅箔を溶解除去(ウェットエッチング)した。これにより、銅箔とLPCフィルム片の間に形成された化合物層を、露出させた。その後、イオン交換水で洗浄し、80℃のオーブン中で30分間乾燥してFT-IR分析用のLPC試験片(化合物層で被覆されたLPCフィルム片)とした。
図13は、比較例4の銅張り積層板から作成したLPC試験片のFT-IRチャートである。3383cm-1にASTのトリアジン環のC-N基のピーク(弱くブロードな)、2962cm-1と2926cm-1にCH2基のピーク(弱い)、1735cm-1にLCPフィルムのエステル基のC=O基のピーク、および914cm-1にASTのSi-OH基のピークが検出された。
2926cm-1にAASのCH2基のピーク(弱い)、1735cm-1にLCPフィルムのエステル基のC=O基にピーク、および914cm-1にAASのSi-OH基のピークが検出された。
発明者らは、FT-IRの結果を以下のように解釈することにより、銅張り積層板の引き剥がし試験の結果(表9参照)と整合することを見いだした。つまり、下記のように解釈すれば、比較例に比べて、実施例の引き剥がし強度が高いことを論理的に説明することができる。なお、下記の解釈が実際の現象と一致していない場合であっても、本開示に係る発明の効果が否定されるものではないことに留意されたい。
10 銅合金基体
15 銅合金部材
20 化合物層
40 ポリエステル系樹脂本体
47 ポリエステル系樹脂部材
50 過酸化水素水
Claims (18)
- 銅合金よりなる基体と、ポリエステル系樹脂本体と、前記基体と前記ポリエステル系樹脂本体とを接合する化合物層とを含み、
前記化合物層が、窒素を含む官能基とシラノール基とを有する化合物と、アルカン型アミン系シランカップリング剤と、を含有することを特徴とする銅合金物品。 - 前記窒素を含む官能基が、窒素を含む5員環以上の環状構造を有することを特徴とする請求項1に記載の銅合金物品。
- 前記5員環以上の環状構造が、トリアゾールまたはトリアジン構造であることを特徴とする請求項2に記載の銅合金物品。
- 前記基体の表面粗さRaが0.1μm以下であることを特徴とする請求項1~3のいずれか1項に記載の銅合金物品。
- 前記ポリエステル系樹脂本体が、ポリエチレンテレフタレート、ポリメチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート、ポリブチレンナフタレートおよび液晶ポリマーから成る群から選択されるポリエステル系樹脂から成ることを特徴とする請求項1~4のいずれか1項に記載の銅合金物品。
- 前記基体の表面に、酸化物層および防錆剤層が存在しないことを特徴とする請求項1~5のいずれか1項に記載の銅合金物品。
- ポリエステル系樹脂本体と、当該ポリエステル系樹脂本体の表面に設けられた化合物層とを含むポリエステル系樹脂部材であって、
前記化合物層が、窒素を含む官能基とシラノール基とを有する化合物と、アルカン型アミン系シランカップリング剤と、を含有することを特徴とするポリエステル系樹脂部材。 - 前記窒素を含む官能基が、窒素を含む5員環以上の環状構造を有することを特徴とする請求項7に記載のポリエステル系樹脂部材。
- 前記5員環以上の環状構造が、トリアゾールまたはトリアジン構造であることを特徴とする請求項8に記載のポリエステル系樹脂部材。
- 前記ポリエステル系樹脂本体が、ポリエチレンテレフタレート、ポリメチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート、ポリブチレンナフタレートおよび液晶ポリマーから成る群から選択されるポリエステル系樹脂から成ることを特徴とする請求項7~9のいずれか1項に記載のポリエステル系樹脂部材。
- 銅合金よりなる基体と、当該基体の表面に設けられた化合物層とを含む銅合金部材であって、
前記化合物層が、窒素を含む官能基とシラノール基とを有する化合物と、アルカン型アミン系シランカップリング剤と、を含有することを特徴とする銅合金部材。 - 前記窒素を含む官能基が、窒素を含む5員環以上の環状構造を有することを特徴とする請求項11に記載の銅合金部材。
- 前記5員環以上の環状構造が、トリアゾールまたはトリアジン構造であることを特徴とする請求項12に記載の銅合金部材。
- ポリエステル系樹脂本体と、当該ポリエステル系樹脂本体の表面に設けられた化合物層とを含むポリエステル系樹脂部材を製造する方法であって、
ポリエステル系樹脂本体の表面に、窒素を含む官能基とシラノール基を有する化合物と、アルカン型アミン系シランカップリング剤とを含有する溶液を接触させた後に、熱処理することを特徴とする製造方法。 - 銅合金よりなる基体と、ポリエステル系樹脂本体と、前記基体と前記ポリエステル系樹脂本体とを接合する化合物層とを含む銅合金物品の製造方法であって、
請求項14に記載の製造方法により、ポリエステル系樹脂部材を得る工程と、
前記基体の表面を酸水溶液で洗浄する工程と、
前記化合物層と、洗浄した前記基体の表面とを接合することにより、前記基体と前記ポリエステル系樹脂本体とを接合する工程と、を含むことを特徴とする製造方法。 - 銅合金よりなる基体と、当該基体の表面に設けられた化合物層とを含む銅合金部材を製造する方法であって、
前記基体を酸水溶液で洗浄する工程と、
前記基体の表面に、窒素を含む官能基とシラノール基を有する化合物と、アルカン型アミン系シランカップリング剤とを含有する溶液を接触させた後に、熱処理することを特徴とする製造方法。 - 銅合金よりなる基体と、ポリエステル系樹脂本体と、前記基体と前記ポリエステル系樹脂本体とを接合する化合物層とを含む銅合金物品の製造方法であって、
請求項16に記載の製造方法により、銅合金部材を得る工程と、
前記化合物層と前記ポリエステル系樹脂本体とを接合することにより、前記基体と前記ポリエステル系樹脂本体とを接合する工程と、を含むことを特徴とする製造方法。 - 前記溶液中における、窒素を含む官能基とシラノール基とを有する化合物と、アルカン型アミン系シランカップリング剤とのモル濃度比が、1:0.5~1:15であることを特徴とする請求項14~17のいずれか1項に記載の製造方法。
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CN (1) | CN108431298B (ja) |
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WO2019026382A1 (ja) * | 2017-08-02 | 2019-02-07 | 株式会社新技術研究所 | 金属と樹脂の複合材 |
JP2019048392A (ja) * | 2017-09-07 | 2019-03-28 | 小島プレス工業株式会社 | 金属被覆樹脂基材の製造方法 |
WO2022176914A1 (ja) * | 2021-02-18 | 2022-08-25 | 富士フイルム株式会社 | 液晶ポリマーフィルム、ポリマーフィルム、及び積層体 |
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US11053593B2 (en) | 2016-01-27 | 2021-07-06 | Advanced Technologies, Inc. | Copper or copper alloy article comprising surface-modified polyester-based resin and manufacturing method |
DE102019217123A1 (de) * | 2019-11-06 | 2021-05-06 | Robert Bosch Gmbh | Verfahren zur Herstellung eines Bauteil-Kunststoff-Verbundes |
JPWO2021187214A1 (ja) | 2020-03-18 | 2021-09-23 |
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- 2017-01-12 WO PCT/JP2017/000855 patent/WO2017130721A1/ja active Application Filing
- 2017-01-12 DE DE112017000516.7T patent/DE112017000516B4/de not_active Expired - Fee Related
- 2017-01-12 JP JP2017506437A patent/JP6268370B2/ja not_active Expired - Fee Related
- 2017-01-12 GB GB1812224.2A patent/GB2561137B/en not_active Expired - Fee Related
- 2017-01-12 KR KR1020187016941A patent/KR101910332B1/ko active IP Right Grant
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GB201812224D0 (en) | 2018-09-12 |
JPWO2017130721A1 (ja) | 2018-02-01 |
US20190078213A1 (en) | 2019-03-14 |
CN108431298A (zh) | 2018-08-21 |
GB2561137B (en) | 2019-08-07 |
US11053593B2 (en) | 2021-07-06 |
JP6268370B2 (ja) | 2018-01-31 |
TW201741134A (zh) | 2017-12-01 |
TWI647097B (zh) | 2019-01-11 |
US20210285108A1 (en) | 2021-09-16 |
KR20180074795A (ko) | 2018-07-03 |
DE112017000516T5 (de) | 2018-10-11 |
DE112017000516B4 (de) | 2020-08-20 |
CN108431298B (zh) | 2019-06-21 |
GB2561137A (en) | 2018-10-03 |
KR101910332B1 (ko) | 2018-10-19 |
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