WO2023144974A1 - 金属部材、金属樹脂接合体及び金属樹脂接合体の製造方法 - Google Patents

金属部材、金属樹脂接合体及び金属樹脂接合体の製造方法 Download PDF

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Publication number
WO2023144974A1
WO2023144974A1 PCT/JP2022/003176 JP2022003176W WO2023144974A1 WO 2023144974 A1 WO2023144974 A1 WO 2023144974A1 JP 2022003176 W JP2022003176 W JP 2022003176W WO 2023144974 A1 WO2023144974 A1 WO 2023144974A1
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WO
WIPO (PCT)
Prior art keywords
metal
resin
anchor portion
joint surface
aggregate
Prior art date
Application number
PCT/JP2022/003176
Other languages
English (en)
French (fr)
Inventor
聖一 斎
Original Assignee
睦月電機株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 睦月電機株式会社 filed Critical 睦月電機株式会社
Priority to PCT/JP2022/003176 priority Critical patent/WO2023144974A1/ja
Priority to CN202280003502.2A priority patent/CN116829346A/zh
Priority to JP2022535844A priority patent/JPWO2023144974A1/ja
Priority to EP22740272.4A priority patent/EP4245522A4/en
Publication of WO2023144974A1 publication Critical patent/WO2023144974A1/ja

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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/02—Positioning or observing the workpiece, e.g. with respect to the point of impact; Aligning, aiming or focusing the laser beam
    • B23K26/06—Shaping the laser beam, e.g. by masks or multi-focusing
    • B23K26/062—Shaping the laser beam, e.g. by masks or multi-focusing by direct control of the laser beam
    • B23K26/0622—Shaping the laser beam, e.g. by masks or multi-focusing by direct control of the laser beam by shaping pulses
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/36—Removing material
    • B23K26/362—Laser etching
    • B23K26/364—Laser etching for making a groove or trench, e.g. for scribing a break initiation groove
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/36—Removing material
    • B23K26/40—Removing material taking account of the properties of the material involved
    • 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
    • B29C65/14—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
    • B29C65/16—Laser beams
    • 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
    • B29C65/34—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using heated elements which remain in the joint, e.g. "verlorenes Schweisselement"
    • B29C65/3472—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using heated elements which remain in the joint, e.g. "verlorenes Schweisselement" characterised by the composition of the heated elements which remain in the joint
    • B29C65/3476—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using heated elements which remain in the joint, e.g. "verlorenes Schweisselement" characterised by the composition of the heated elements which remain in the joint being metallic
    • 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
    • B29C65/34—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using heated elements which remain in the joint, e.g. "verlorenes Schweisselement"
    • B29C65/36—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using heated elements which remain in the joint, e.g. "verlorenes Schweisselement" heated by induction
    • B29C65/3604—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using heated elements which remain in the joint, e.g. "verlorenes Schweisselement" heated by induction characterised by the type of elements heated by induction which remain in the joint
    • B29C65/3656—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using heated elements which remain in the joint, e.g. "verlorenes Schweisselement" heated by induction characterised by the type of elements heated by induction which remain in the joint being a layer of a multilayer part to be joined, e.g. for joining plastic-metal laminates
    • 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
    • B29C65/34—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using heated elements which remain in the joint, e.g. "verlorenes Schweisselement"
    • B29C65/36—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using heated elements which remain in the joint, e.g. "verlorenes Schweisselement" heated by induction
    • B29C65/3672—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using heated elements which remain in the joint, e.g. "verlorenes Schweisselement" heated by induction characterised by the composition of the elements heated by induction which remain in the joint
    • B29C65/3676—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using heated elements which remain in the joint, e.g. "verlorenes Schweisselement" heated by induction characterised by the composition of the elements heated by induction which remain in the joint being metallic
    • 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
    • B29C65/44—Joining a heated non plastics element to a plastics element
    • 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
    • B29C65/44—Joining a heated non plastics element to a plastics element
    • B29C65/46—Joining a heated non plastics element to a plastics element heated by induction
    • 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
    • B29C65/82—Testing the joint
    • B29C65/8253—Testing the joint by the use of waves or particle radiation, e.g. visual examination, scanning electron microscopy, or X-rays
    • 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
    • B29C66/024—Thermal pre-treatments
    • B29C66/0246—Cutting or perforating, e.g. burning away by using a laser or using hot air
    • 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
    • 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
    • B29C66/303—Particular design of joint configurations the joint involving an anchoring effect
    • B29C66/3032—Particular design of joint configurations the joint involving an anchoring effect making use of protrusions or cavities belonging to at least one of the parts to be joined
    • B29C66/30321—Particular design of joint configurations the joint involving an anchoring effect making use of protrusions or cavities belonging to at least one of the parts to be joined making use of protrusions belonging to at least one of the parts to be joined
    • 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
    • B29C66/303—Particular design of joint configurations the joint involving an anchoring effect
    • B29C66/3032—Particular design of joint configurations the joint involving an anchoring effect making use of protrusions or cavities belonging to at least one of the parts to be joined
    • B29C66/30325—Particular design of joint configurations the joint involving an anchoring effect making use of protrusions or cavities belonging to at least one of the parts to be joined making use of cavities belonging to at least one of the parts to be joined
    • 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
    • B29C66/303—Particular design of joint configurations the joint involving an anchoring effect
    • B29C66/3032—Particular design of joint configurations the joint involving an anchoring effect making use of protrusions or cavities belonging to at least one of the parts to be joined
    • B29C66/30325—Particular design of joint configurations the joint involving an anchoring effect making use of protrusions or cavities belonging to at least one of the parts to be joined making use of cavities belonging to at least one of the parts to be joined
    • B29C66/30326—Particular design of joint configurations the joint involving an anchoring effect making use of protrusions or cavities belonging to at least one of the parts to be joined making use of cavities belonging to at least one of the parts to be joined in the form of porosity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/40—General aspects of joining substantially flat articles, e.g. plates, sheets or web-like materials; Making flat seams in tubular or hollow articles; Joining single elements to substantially flat surfaces
    • B29C66/41—Joining substantially flat articles ; Making flat seams in tubular or hollow articles
    • B29C66/45—Joining of substantially the whole surface of the articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—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
    • B29C66/72—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 structure of the material of the parts to be joined
    • B29C66/721—Fibre-reinforced materials
    • B29C66/7212—Fibre-reinforced materials characterised by the composition of the fibres
    • 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
    • B29C66/72—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 structure of the material of the parts to be joined
    • B29C66/721—Fibre-reinforced materials
    • B29C66/7214—Fibre-reinforced materials characterised by the length of the fibres
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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
    • B29C66/73—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/739—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/7392—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of at least one of the parts being a thermoplastic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
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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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    • B29C66/70—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
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C66/80—General aspects of machine operations or constructions and parts thereof
    • B29C66/83—General aspects of machine operations or constructions and parts thereof characterised by the movement of the joining or pressing tools
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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
    • B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/286—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysulphones; polysulfides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K2103/00—Materials to be soldered, welded or cut
    • B23K2103/02—Iron or ferrous alloys
    • B23K2103/04—Steel or steel alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K2103/00—Materials to be soldered, welded or cut
    • B23K2103/08—Non-ferrous metals or alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K2103/00—Materials to be soldered, welded or cut
    • B23K2103/08—Non-ferrous metals or alloys
    • B23K2103/10—Aluminium or alloys thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/105—Metal
    • B32B2264/1052—Aluminum
    • 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
    • B32B2307/748—Releasability
    • 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
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B32B3/30—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer formed with recesses or projections, e.g. hollows, grooves, protuberances, ribs

Definitions

  • the present invention relates to a metal member, a metal-resin bonded body, and a method for manufacturing a metal-resin bonded body.
  • a metal-resin joined body in which a metal member made of metal and a resin member made of synthetic resin are joined.
  • an anchor portion may be formed on the surface (metal bonding surface) of the metal member to which the resin member is bonded.
  • Patent Document 1 an open hole having an opening on the metal bonding surface side of a metal member, an internal space having no opening on the metal bonding surface side, an open hole and an internal space, and open holes It has been proposed to form an anchor portion having a tunnel connection path for connecting the metal member to the metal joint surface of the metal member.
  • Patent Document 2 an uneven layer having an uneven shape and a metal porous layer formed on the uneven layer are provided, and a plurality of pores opening to the outermost surface of the metal porous layer are formed in the metal porous layer. It has been proposed to form an anchor portion having a thickness of 0.2 mm on a metal joint surface of a metal member.
  • Patent Document 1 since the open hole, the internal space, and the tunnel connection path that constitute the anchor portion are provided in a recessed portion from the metal joint surface, even if the resin member is joined to the metal joint surface, the open hole and the inner space will be removed. It is difficult for the resin member to enter the space or the tunnel connecting path, and the anchor effect is not sufficiently exhibited.
  • Patent Document 2 since the metal porous layer is provided with elongated pores having an opening diameter (width dimension) of 100 nm or less that opens to the outermost surface of the metal porous layer, a resin member is formed on the metal bonding surface. Even if the resin member is joined, it is difficult for the resin member to enter the elongated holes, and the anchor effect is not sufficiently exhibited.
  • Patent No. 5998303 Japanese Patent Application Laid-Open No. 2018-80360
  • the present invention has been made in view of the above points, and an object of the present invention is to improve the bonding strength of a metal-resin bonded body in which a metal member and a resin member are bonded by forming an anchor portion that easily exhibits an anchor effect. do.
  • a metal member made of metal comprising a metal bonding surface and an anchor portion protruding from the metal bonding surface, wherein the anchor portion is disposed between an aggregate of a plurality of metal particles and between the plurality of metal particles.
  • a metal member comprising a plurality of voids formed therein, wherein the plurality of voids are connected inside the anchor portion and extend from the surface of the anchor portion to the inside.
  • a metal-resin joined body comprising a metal member made of a metal and a resin member made of a thermoplastic resin, wherein the metal member has a metal bonding surface and a resin bonding surface of the resin member is bonded to the metal bonding surface of the metal member.
  • a metal-resin joined body that is connected to the inside of the anchor portion and connected from the surface of the anchor portion to the inside.
  • a method for manufacturing a metal-resin joined body in which a resin member made of a thermoplastic resin is joined to a metal joint surface of a metal member, an anchor portion protruding from the metal joint surface is attached to the metal member. and after the anchor forming step, the resin member is pressurized while being in contact with the anchor portion, and the anchor portion is inserted into the resin member to bring the metal joint surface into contact with the resin joint surface.
  • the anchor forming step by irradiating the metal bonding surface with a pulsed laser beam, an aggregate of a plurality of metal particles is formed, and the anchor portion is formed between the plurality of metal particles.
  • an anchor portion having a shape that facilitates the anchor effect, and to improve the joint strength of a metal-resin joined body in which a metal member and a resin member are joined.
  • FIG. 1 is a cross-sectional view showing a schematic configuration of a metal-resin bonded body according to an embodiment of the present invention
  • FIG. 2 is a plan view showing a schematic configuration of a metal joint surface of a metal member constituting the metal-resin joined body of FIG. 1
  • 1 is a diagram showing a first step of a method for manufacturing a metal-resin bonded body according to an embodiment of the present invention
  • FIG. 4 is a diagram showing the second step of the method for manufacturing a metal-resin bonded body according to one embodiment of the present invention; SEM photograph of the metal joint surface of the metal member of Example 1 SEM photograph of a cross section perpendicular to the laser scanning direction of the metal member of Example 1 SEM photograph of a cross section cut parallel to the laser scanning direction of the anchor portion of the metal member of Example 1 SEM photograph of a cross section perpendicular to the laser scanning direction of the metal member of Comparative Example 1 SEM photograph of the cross section of the metal-resin joined body of Example 1 Component analysis image showing the distribution of aluminum in the cross section of FIG. Component analysis image showing the distribution of sulfur in the cross section of FIG. Component analysis image showing the distribution of silicon in the cross section of FIG.
  • a metal-resin joined body 10 includes a resin member 20 made of thermoplastic resin and a metal member 30 made of metal. ) 22 and a surface 32 of the metal member 30 (hereinafter, this surface may be referred to as a “metal bonding surface”) 32 .
  • the resin member 20 is a member obtained by molding a thermoplastic resin into a predetermined shape such as a block, plate, or line. Further, the resin member 20 may be a thermoplastic resin coating film or an adhesive layer made of a thermoplastic resin adhesive.
  • thermoplastic resin forming the resin member 20 examples include polypropylene resin (PP resin), polyacetal resin (POM resin), polyphenylene sulfide resin (PPS resin), polyetheretherketone resin (PEEK), acrylonitrile/ Butadiene/styrene resin (ABS resin), polyethylene resin (PE resin), polybutylene terephthalate resin (PBT resin), polyamide resin (PA resin) such as nylon 66 (PA66), epoxy resin, liquid crystal polymer (LCP resin), modification Polyphenylene ether resin (modified PPE), reactor type soft polypropylene resin (metallocene reactor type TPO resin), and the like.
  • PP resin polypropylene resin
  • POM resin polyacetal resin
  • PPS resin polyphenylene sulfide resin
  • PEEK polyetheretherketone resin
  • ABS resin acrylonitrile/ Butadiene/styrene resin
  • PES resin polyethylene resin
  • PBT resin polybutylene terephthalate resin
  • the resin member 20 may be a carbon fiber reinforced thermoplastic resin (CFRTP) in which carbon fiber is blended with the thermoplastic resin as described above, a reinforcing material such as glass fiber or talc in the thermoplastic resin as described above, or a hard material. Combustion materials, anti-deterioration agents, elastomer components, and the like may be blended therein.
  • CFRTP carbon fiber reinforced thermoplastic resin
  • Metal member 30 is a member obtained by molding metal into a predetermined shape such as a block, plate, or line.
  • Metals constituting the metal member 30 include copper (Cu), iron (Fe), aluminum (Al), zinc (Zn), magnesium (Mg), tin (Sn), titanium (Ti), nickel (Ni), chromium.
  • Various metals such as (Cr) can be used without particular limitation.
  • the metal member 30 is an alloy made of two or more metals such as a copper alloy, an iron alloy (steel material), an aluminum alloy, a stainless steel, a titanium alloy, a nickel alloy, a chromium alloy, a zinc alloy, a magnesium alloy, or a silicon alloy.
  • the metal member 30 is made of aluminum, zinc, magnesium, tin, Fe—Si alloys, Cu—Sn alloys, Mg—Al alloys, etc., which have a melt viscosity of 5 mPa ⁇ s or less at the melting point, in that the anchor portions 34 to be described later can be easily formed. is preferably a metal or alloy.
  • the shape of the metal member 30 can be a desired shape depending on the application.
  • An arbitrary method can be applied to the forming method of the metal member 30. Casting in which a molten metal or the like is poured into a mold of a desired shape, cutting using a machine tool or the like, punching using a press machine or the like is used. may
  • the metal joint surface 32 of the metal member 30 is roughened and provided with an anchor portion 34 .
  • the metal member 30 may have an oxide film (metal oxide) formed on the metal joint surface 32 and the anchor portion 34 .
  • the oxide film may be a native oxide film naturally formed on the surface of the metal.
  • the oxide film may be formed on the surface of the metal member 30 by surface treatment with an oxidizing agent, electrolytic treatment by anodization, plasma oxidation treatment, heat oxidation treatment in an oxygen-containing gas, or the like.
  • the oxide film may be formed on the surface of the metal member 30 by rapidly heating the surface of the metal member 30 in an oxygen-containing gas atmosphere such as air. It is preferable that the temperature rise of the surface of the metal member 30 per minute during rapid heating is equal to or higher than the melting point temperature of the metal forming the metal member 30 . By rapidly heating the surface of the metal member 30 in this manner, a dense oxide film can be formed on the surface of the metal member 30 . Moreover, by rapidly heating the surface of the metal member 30, microcracks are generated on the surface of the oxide film, and the bonding area with the resin member 20 increases.
  • the surface of the metal member 30 can be rapidly heated by various methods such as laser heating, induction heating, or resistance heating. It is preferable to form an oxide film by heating the surface of the metal member 30 by the irradiation of .
  • the anchor portion 34 includes an aggregate 38 of a plurality of metal particles 36 and a plurality of voids 40 formed between the plurality of metal particles 36. provided to protrude.
  • the anchor portion 34 is provided along a predetermined direction (hereinafter referred to as the first direction) X. As shown in FIG.
  • the aggregate 38 is three-dimensionally arranged such that the plurality of metal particles 36 are in contact with each other while providing gaps 40 between the plurality of metal particles 36. is fused.
  • a plurality of gaps 40 provided in the anchor portion 34 are opened in various directions on the surface of the anchor portion 34 and are connected inside the anchor portion 34 to connect from the surface of the anchor portion 34 to the inside.
  • the plurality of metal particles 36 forming the aggregate 38 are made of the same metal as the metal forming the metal member 30 .
  • the particle diameter of the metal particles 36 is not particularly limited.
  • the average particle size of the metal particles 36 may be 5-50 ⁇ m.
  • the average particle diameter of the metal particles 36 is obtained by obtaining an image by microscopic observation, and using this image, the major axis and minor axis of the metal particles 36 (when the major axis and minor axis are the same, the length in a certain axial direction) and the length in the axial direction perpendicular thereto) are measured for 10 randomly selected particles, and the average value is calculated.
  • the aggregate 38 preferably includes a plurality of columnar metal particles 36 protruding so that one end adheres to the metal joint surface 32 and the other end protrudes away from the metal joint surface 32 . More preferably, the tip of the columnar metal particle 36 is rounded.
  • the columnar metal particles 36 are metal particles formed by resolidifying the metal melted by irradiating the metal joint surface 32 of the metal member 30 with a laser as described later without scattering from the metal joint surface 32. 36.
  • the aggregate 38 also includes substantially spherical metal particles 36 formed by redepositing the molten metal scattered from the metal joint surface 32 by laser irradiation onto the metal joint surface 32. may contain. Preferably, 60% or more of the metal particles 36 constituting the aggregate 38 are columnar metal particles 36 .
  • the columnar metal particles 36 mean metal particles 36 whose length in the longitudinal direction is at least twice the maximum diameter dimension of the metal particles 36 .
  • the maximum diameter dimension means the maximum dimension of cross-sectional diameters in a cross section perpendicular to the longitudinal direction of the metal particles 36 .
  • the length in the longitudinal direction and the maximum diameter dimension of the metal particles 36 can be measured using an image obtained by microscopic observation.
  • the longitudinal length and maximum diameter dimension of 10 randomly selected metal particles 36 are measured, and the respective average values are taken as the average longitudinal length and average maximum diameter dimension, the longitudinal direction of the metal particles 36
  • the average length of the metal particles 36 may be 5-50 ⁇ m, and the average maximum diameter dimension of the metal particles 36 may be 5-25 ⁇ m.
  • the ratio of the columnar metal particles 36 to the metal particles 36 constituting the aggregate 38 was determined by randomly selecting 100 metal particles 36 from the image acquired by microscopic observation, It is calculated from the number of columnar metal particles 36 included.
  • the minimum diameter of the opening of the void 40 is preferably 0.1 ⁇ m or more, more preferably 1 ⁇ m or more. When the minimum diameter of the opening of the gap 40 is 0.1 ⁇ m or more, the resin member 20 easily enters the gap 40 .
  • aggregates 38 of a plurality of metal particles 36 may be provided inside recesses 42 recessed from metal joint surface 32, as shown in FIG.
  • the concave portion 42 may be a concave groove extending along the first direction X with a depth of 5 to 200 ⁇ m from the metal joint surface 32 and a width of 5 to 200 ⁇ m at the position of the metal joint surface 32 .
  • three anchor portions 34 are provided on the metal joint surface 32 at intervals in a direction Y perpendicular to the first direction X (hereinafter, this direction is the second direction).
  • one anchor portion 34 may be provided on the metal joint surface 32, or any number of anchor portions 34 may be provided on the metal joint surface 32 at intervals in the second direction Y.
  • one anchor portion 34 may be provided parallel to the other anchor portions 34 as shown in FIG. good too.
  • the resin member 20 and the metal member 30 molded into a predetermined shape are prepared. Then, an anchor forming step is performed to form the anchor portion 34 on the metal joint surface 32 of the metal member 30 . After that, a bonding step is performed to bond the resin bonding surface 22 of the resin member 20 to the metal bonding surface 32 on which the anchor portion 34 is formed. As a result, the metal-resin bonded body 10 in which the resin member 20 is bonded to the metal bonding surface 32 of the metal member 30 is obtained.
  • the anchor forming process and the bonding process will be described in detail below.
  • the metal bonding surface 32 of the metal member 30 to which the resin member 20 is bonded has a coefficient A represented by the following formula (1) of 0.1 or more and 1.0. It is preferable to irradiate while moving (scanning) in the first direction X a pulsed laser beam that satisfies the following.
  • A LF/(1 ⁇ C) Formula (1)
  • L is the laser beam spot diameter (mm)
  • F is the laser beam fluence (J/mm 2 )
  • C is the overlap ratio between scanning laser beam spots.
  • the metal joint surface 32 is irradiated with a pulsed laser beam having a coefficient A of 0.1 or more and 1.0 or less, the metal at the position irradiated with the laser beam is melted to form a concave portion 42 and melted.
  • the resulting metal particles are deposited in the recesses 42 to form aggregates 38 of the metal particles 36 .
  • the anchor portions 34 are formed by irradiating the laser beam in the oxygen-containing gas as described above, metal oxides are formed on the surfaces of the metal particles 36 forming the anchor portions 34 .
  • the metal joint surface is scanned in the first direction X with pulsed laser light at positions at predetermined intervals in the second direction Y. 32 is irradiated.
  • a portion of the metal joint surface 32 where the anchor portion 34 is to be formed is irradiated with a laser beam to form the metal joint.
  • a pretreatment for removing impurities adhering to the surface 32 may be performed.
  • (5-2) Joining Step In the joining step, the metal member 30 and the resin member 20 are heated and brought into contact with the metal joining surface 32 while the resin joining surface 22 is pressed. As a result, the resin member 20 is joined to the metal joining surface 32 of the metal member 30 to obtain the metal-resin joined body 10 .
  • the metal-resin bonded body 10 is manufactured by performing the first step and the second step using the bonding apparatus 50 as shown in FIGS.
  • the joining device 50 includes a stage 51 on which the metal member 30 is placed, a heating device 52 that induction-heats the metal member 30 placed on the stage 51, and a press device that pressure-bonds the resin member 20 to the metal member 30. 53.
  • the metal member 30 is placed on the stage 51 so that the metal bonding surface 32 provided with the anchor portion 34 faces the resin member 20 .
  • the heating device 52 includes an induction heating coil connected to a power supply (not shown), and when drive power is input from the power supply, the induction heating coil generates a magnetic field to heat the metal member 30 placed on the stage 51 .
  • the metal joint surface 32 of is induction-heated.
  • the pressing device 53 includes a rod 54 made of an insulating material such as ceramics, and a pressing portion 55 that moves the rod 54 to press the resin member 20 against the metal joint surface 32 of the metal member 30 .
  • the rod 54 may be inserted into the hollow portion of the induction heating coil of the heating device 52 and arranged to face the resin member 20 .
  • the pressurizing unit 55 includes a pneumatic cylinder controlled by an electropneumatic regulator, a spring pressurizer, or the like, and determines the speed at which the resin member 20 is moved together with the rod 54 and the time when the resin member 20 is pressed against the metal member 30. It is preferable to be able to control the pressure.
  • the metal bonding surface 32 provided with the anchor portion 34 faces the resin member 20 to be set later.
  • a metal member 30 is placed on the stage 51 .
  • the resin member 20 is arranged so that the resin bonding surface 22 faces the metal bonding surface 32 of the metal member 30 placed on the stage 51 with a gap therebetween.
  • the distance between the metal joint surface 32 of the metal member 30 and the resin joint surface 22 of the resin member 20 is set to 0.001 mm to 10 mm, for example.
  • the heating device 52 is arranged so as to face the metal bonding surface 32 of the metal member 30 with the resin member 20 interposed therebetween.
  • the heating device 52 is arranged above the resin member 20 and the resin member 20 is arranged between the heating device 52 and the metal member 30 .
  • a driving power source is supplied to the heating device 52 to generate a magnetic field from an induction heating coil provided in the heating device 52 to heat the metal joint surface 32 of the metal member 30 .
  • the driving power supplied to the heating device 52, the position of the induction heating coil provided in the heating device 52, and the like are adjusted so that the metal joint surface 32 of the metal member 30 reaches the first temperature T1.
  • the gas between the metal member 30 and the resin member 20 is heated to the first temperature T1.
  • the resin bonding surface 22 of the resin member 20 facing the metal bonding surface 32 of the metal member 30 is exposed to the gas heated to the first temperature T1, and the resin bonding surface 22 reaches the first temperature T1.
  • the heating device 52 heats the metal joint surface 32 of the metal member 30 for a predetermined time S1 (for example, 1 to 10 seconds) to perform the first step as described above. Move to the process.
  • the heating device 52 stops heating the metal member 30 or reduces the amount of heat to continue to perform the second step.
  • the temperature of the gas between the member 30 and the resin member 20) is lowered (cooled) until it reaches the second temperature T2. Then, the resin member 20 and the metal member 30 are joined together at the second temperature T2.
  • the press device 53 moves the resin member 20 at a predetermined speed V to collide with the metal member 30 at a temperature lower than the first temperature T1 (second temperature T2).
  • the resin member 20 is strongly pressed against the metal joint surface 32 of the metal member 30 while the position corresponding to the tip of the rod 54 is in contact with the anchor portion 34 , and is pressed against the metal member 30 with a predetermined pressure P.
  • the anchor portion 34 enters the resin member 20
  • the thermoplastic resin forming the resin member 20 enters the gap 40 provided in the anchor portion 34 .
  • the anchor portion 34 is embedded in the resin member 20 while the void 40 is filled with the thermoplastic resin, and the resin bonding surface 22 of the resin member 20 and the metal bonding surface 32 of the metal member 30 are locally (spotted). A joined metal-resin joined body 10 is obtained. Then, the second step ends.
  • the first temperature T1 can be a temperature equal to or higher than the load deflection temperature Tf of the thermoplastic resin forming the resin member 20 when a load of 1.8 MPa is applied.
  • the resin member 20 is made of a thermoplastic resin mixed with a reinforcing material such as carbon fiber, glass fiber, or talc
  • the load deflection temperature Tf is the load deflection temperature Tf when a load of 1.8 MPa is applied to a thermoplastic resin containing no reinforcing material.
  • the upper limit of the first temperature T1 can be set to a temperature lower than the decomposition temperature of the thermoplastic resin forming the resin member 20, that is, lower than the temperature at which the thermoplastic resin begins to vaporize.
  • the upper limit of the first temperature T1 may be 1000.degree.
  • the upper limit of the first temperature T1 can be set to a temperature 20° C. higher than the melting point Tm of the thermoplastic resin forming the resin member 20 .
  • the second temperature T2 may be lower than the first temperature T1, but is equal to or higher than the load deflection temperature Tf of the thermoplastic resin forming the resin member 20 when a load of 1.8 MPa is applied. is preferred.
  • the second temperature T ⁇ b>2 is preferably lower than the melting point Tm of the thermoplastic resin forming the resin member 20 .
  • a temperature difference between the first temperature T1 and the second temperature T2 is preferably 1° C. or more and 20° C. or less.
  • the melting point Tm of a thermoplastic resin is a value measured using a differential scanning calorimeter at a heating rate of 10°C per minute according to JIS K7121.
  • the melting points of typical thermoplastic resins are 168°C for polypropylene resin, 265°C for nylon 66, 232 to 267°C for polybutylene terephthalate resin, and 280°C for polyphenylene sulfide resin.
  • the deflection temperature under load Tf of the thermoplastic resin is the deflection temperature under load when a load of 1.8 MPa is applied, measured according to JIS K7191.
  • the load deflection temperature Tf of typical thermoplastic resins when a load of 1.8 MPa is applied is given.
  • Sulfide resin is 105°C.
  • the first step is preferably performed in an oxygen-containing gas such as air. That is, the metal bonding surface 32 and the resin bonding surface 22 are heated to the first temperature T1 in an oxygen-containing gas atmosphere, and the metal bonding surface 32 and the resin bonding surface 22 are heated to the first temperature T1 in the oxygen-containing gas. Exposure is preferred.
  • the resin bonding surface 22 of the resin member 20 reacts with oxygen contained in the oxygen-containing gas, thereby neutralizing basic or amphoteric oxides. As a result, functional groups that can be chemically bonded are generated on the resin bonding surface 22 of the resin member 20 .
  • the surface of the metal member 30 is oxidized and covered with an oxide film made of a metal oxide. and van der Waals forces and hydrogen bonds.
  • the functional group of the resin bonding surface 22 forms a covalent bond with the metal oxide of the metal member 30 through a neutralization reaction (dehydration condensation). Form.
  • Examples of functional groups generated on the resin bonding surface 22 include carboxyl groups (—COOH), carbonyl groups (—CO—), and hydroxy groups ( —OH).
  • functional groups possessed by the resin bonding surface 22 include carboxyl groups, carbonyl groups, and hydroxy groups.
  • R is the main chain of the thermoplastic resin forming the resin member 20 and Me is the metal forming the metal member 30 .
  • the second temperature T2 is the same as the functional group of the resin bonding surface 22 of the resin member 20 and the metal formed on the metal bonding surface 32 of the metal member 30. It is preferably a temperature at which a covalent bond can be formed by a neutralization reaction with an oxide. Moreover, the second temperature T2 is preferably a temperature at which water generated by the neutralization reaction is removed from the reaction system. The second temperature T2 varies depending on the types of functional groups and metal oxides, so it is difficult to define unconditionally. more preferred.
  • the metal member 30 and the resin member 20 may be heated so that the entire metal member 30 and the resin member 20 reach the first temperature T1, but at least the metal bonding surface 32 and the resin bonding surface 22 may be heated to the first temperature T1.
  • the pressure P when pressing the resin member 20 against the metal member 30 is preferably a pressure equal to or higher than the compressive yield stress of the thermoplastic resin forming the resin member 20 . Since this pressure P varies depending on the thermoplastic resin that constitutes the resin member 20, it is difficult to define it unconditionally, but it is preferably 10 to 100 MPa.
  • the planar shape of the joint may be any shape such as a point shape, a linear shape, or a planar shape.
  • the temperatures of the resin member 20, the metal member 30 and their surroundings may be maintained at the second temperature T2.
  • the resin member 20 may be kept in contact with the metal member 30 under pressure until the temperatures of the resin member 20, the metal member 30 and their surroundings are cooled to a predetermined temperature or less.
  • the resin member 20 is pressed against the metal member 30 until the temperatures of the resin member 20, the metal member 30 and their surroundings are cooled below the glass transition temperature Tg of the thermoplastic resin forming the resin member 20. Contact is preferred.
  • the bonding process the case where the resin member 20 molded in advance into a predetermined shape is heated and pressed against the metal member 30 has been described.
  • the resin member 20 may be joined to the metal member 30 by inserting the resin member 20 into the metal member 30 and injecting the melted synthetic resin material toward the metal joining surface 32 in the injection mold.
  • thermoplastic resin forming the resin member 20 enters the gap 40, thereby exhibiting a high anchoring effect.
  • the bonding strength between the resin member 20 and the metal member 30 can be increased.
  • the anchor portion 34 protrudes from the metal bonding surface 32 and a plurality of voids 40 are formed between the plurality of metal particles 36 arranged three-dimensionally. Relatively large openings open in various directions. Therefore, in the present embodiment, the thermoplastic resin forming the resin member 20 can easily enter the void 40, and the bonding strength can be improved. In particular, even when the resin member 20 and the metal member 30 are joined at the second temperature T2 lower than the melting point Tm of the thermoplastic resin forming the resin member 20, the thermoplastic resin forming the resin member 20 is formed into a void. 40, and the joint strength can be improved while suppressing the shape deformation of the resin member 20. As shown in FIG.
  • the anchor portion 34 when at least a portion of the plurality of metal particles 36 constituting the anchor portion 34 are columnar metal particles 36 having one end attached to the metal joint surface 32 and the other end protruding away from the metal joint surface 32, The metal particles 36 are more likely to bite into the interior of the resin member 20 . Therefore, the anchor portion 34 exhibits a high anchoring effect, and the bonding strength can be improved.
  • the gap 40 can be extended deep into the anchor portion 34, thereby improving the joint strength. can do.
  • Examples 1 to 3 and Comparative Examples 1 to 3 a single-mode laser with a laser wavelength of 1064 nm and a pulse width of 0.2 ⁇ sec was irradiated to the metal joint surface of the metal member made of aluminum (Al1050) to form a 18 mm long Anchor portions were formed at a pitch of 0.2 mm. Then, a resin member was joined to the metal joint surface on which the anchor portion was formed. Examples 1 to 3 were irradiated with a laser having a coefficient A of 0.53 J/mm, and Comparative Examples 1 to 3 were irradiated with a laser having a coefficient A of 0.08 J/mm.
  • the details of the resin members used in Examples 1 to 3 and Comparative Examples 1 to 3, the dimensions of the metal members, the dimensions of the resin members, and the bonding area (overlap area) between the resin members and the metal members are as follows. is.
  • the resin members of Example 1 and Comparative Example 1 contain glass fiber as a reinforcing material.
  • ⁇ PPS resin Susteel (registered trademark) SGX120 ⁇ Modified 6T nylon resin: Arlen (registered trademark) A350 ⁇ PP resin: Novatec (registered trademark) HG30U ⁇ Dimensions of metal members: 18 mm x 45 mm x 1.6 mm ⁇ Dimensions of resin member: 10 mm x 40 mm x 3.0 mm ⁇ Joint area between metal member and resin member: 10mm x 5mm
  • the evaluation method is as follows.
  • FIG. 5 is a SEM photograph of the metal joint surface of the metal member of Example 1
  • FIG. 6 is a SEM photograph of a cross section perpendicular to the laser scanning direction (longitudinal direction of the anchor portion) of the metal member of Example 1
  • FIG. 8 shows a SEM photograph of a cross section of the metal member of Example 1 cut parallel to the laser scanning direction
  • FIG. 8 shows a SEM photograph of a cross section of the metal member of Comparative Example 1 perpendicular to the laser scanning direction.

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Abstract

接合強度の高い金属樹脂接合体を得る。　本発明の金属樹脂接合体は、金属からなる金属部材３０と熱可塑性樹脂からなる樹脂部材２０とを備え、金属部材３０の金属接合面３２に樹脂部材２０の樹脂接合面２２を接合した金属樹脂接合体１０である。金属部材３０は金属接合面３２から突出するアンカ部３４を備える。アンカ部３４は、複数の金属粒子３６の集合体３８と、複数の金属粒子３６の間に形成された複数の空隙４０を備える。複数の空隙４０は、アンカ部３４の内部で連結されアンカ部３４の表面から内部へ繋がっている。

Description

金属部材、金属樹脂接合体及び金属樹脂接合体の製造方法
　本発明は、金属部材、金属樹脂接合体及び金属樹脂接合体の製造方法に関する。
　金属からなる金属部材と合成樹脂からなる樹脂部材とを接合した金属樹脂接合体が知られている。金属樹脂接合体では、金属部材と樹脂部材との接合強度を高めるため、樹脂部材を接合する金属部材の表面（金属接合面）にアンカ部を形成することがある。
　例えば、下記特許文献１には、金属部材の金属接合面側に開口部を有する開放孔と、金属接合面側に開口部を有していない内部空間と、開放孔及び内部空間や開放孔同士を接続するトンネル接続路とを有するアンカ部を、金属部材の金属接合面に形成することが提案されている。
　また、下記特許文献２には、凹凸形状の凹凸層と、凹凸層上に形成された金属多孔層とを備え、金属多孔層の最表面に開口する複数個の空孔が金属多孔層に形成されたアンカ部を、金属部材の金属接合面に形成することが提案されている。
　しかしながら、特許文献１では、アンカ部を構成する開放孔や内部空間やトンネル接続路が金属接合面より凹んだところ設けられているため、金属接合面に樹脂部材を接合させても開放孔や内部空間やトンネル接続路に樹脂部材が入り込みにくく、アンカ効果が十分に発揮されない。
　また、特許文献２では、金属多孔質層の最表面に開口する開口部の口径（幅寸法）が１００ｎｍ以下の細長い空孔が金属多孔質層に設けられているため、金属接合面に樹脂部材を接合させても細長い空孔に樹脂部材が入り込みにくく、アンカ効果が十分に発揮されない。
特許第５９９８３０３号 特開２０１８－８０３６０号公報
　本発明は、以上の点に鑑みてなされたものであり、アンカ効果を発揮しやすいアンカ部を形成し、金属部材と樹脂部材を接合した金属樹脂接合体の接合強度を向上することを目的とする。
　本実施形態によれば、下記［１］～［７］の態様が提供される。
　［１］金属からなる金属部材において、金属接合面と、前記金属接合面から突出するアンカ部とを備え、前記アンカ部は、複数の金属粒子の集合体と、前記複数の金属粒子の間に形成された複数の空隙を備え、前記複数の空隙は、前記アンカ部の内部で連結され前記アンカ部の表面から内部へ繋がっている金属部材。
　［２］前記集合体は、一端が前記金属接合面に付着し他端が前記金属接合面から離れるように突出する柱状の金属粒子を含む上記［１］に記載の金属部材。
　［３］前記金属接合面から陥没する凹部を備え、前記集合体の一部が前記金属接合面から突出するように、前記集合体が前記凹部内に設けられている上記［１］又は［２］に記載の金属部材。
　［４］前記アンカ部は、前記金属接合面上に所定の方向に沿って設けられている上記［１］～［３］のいずれか１つに記載の金属部材。
　［５］金属からなる金属部材と熱可塑性樹脂からなる樹脂部材とを備え、前記金属部材の金属接合面に前記樹脂部材の樹脂接合面を接合した金属樹脂接合体において、前記金属部材は前記金属接合面から突出するアンカ部を備え、前記アンカ部は、複数の金属粒子の集合体と、前記複数の金属粒子の間に形成された複数の空隙を備え、前記複数の空隙は、前記アンカ部の内部で連結され前記アンカ部の表面から内部へ繋がっている金属樹脂接合体。
　［６］前記集合体は、一端が前記金属接合面に付着し他端が前記金属接合面から離れるように突出する柱状の金属粒子である上記［５］に記載の金属樹脂接合体。
　［７］前記金属部材は、前記金属接合面から陥没する凹部を備え、前記集合体の一部が前記金属接合面から突出するように、前記集合体が前記凹部内に設けられている上記［５］又は［６］に記載の金属樹脂接合体。
　［８］前記アンカ部は、前記金属接合面上に所定の方向に沿って設けられている上記［５］～［７］いずれか１つに記載の金属樹脂接合体。
　［９］金属からなる金属部材の金属接合面に熱可塑性樹脂からなる樹脂部材の樹脂接合面を接合した金属樹脂接合体の製造方法において、前記金属接合面から突出するアンカ部を前記金属部材に形成するアンカ形成工程と、前記アンカ形成工程後、前記樹脂部材を前記アンカ部に接触させながら加圧して、前記アンカ部を前記樹脂部材に入り込ませて前記金属接合面を前記樹脂接合面に接触させる接合工程とを備え、前記アンカ形成工程は、前記金属接合面に対してパルスレーザ光を照射することで、複数の金属粒子の集合体からなり、前記複数の金属粒子の間に前記アンカ部の表面から内部へ繋がる複数の空隙を有する前記アンカ部を形成する金属樹脂接合体の製造方法。
　［１０］前記集合体は、一端が前記金属接合面に付着し他端が前記金属接合面から離れるように突出する柱状の金属粒子である上記［９］に記載の金属樹脂接合体の製造方法。
　アンカ効果を発揮しやすい形状を有するアンカ部を形成することができ、金属部材と樹脂部材を接合した金属樹脂接合体の接合強度を向上することができる。
本発明の一実施形態に係る金属樹脂接合体の概略構成を示す断面図 図１の金属樹脂接合体を構成する金属部材の金属接合面の概略構成を示す平面図 本発明の一実施形態に係る金属樹脂接合体の製造方法の第１工程を示す図 本発明の一実施形態に係る金属樹脂接合体の製造方法の第２工程を示す図 実施例１の金属部材の金属接合面のＳＥＭ写真 実施例１の金属部材のレーザ走査方向に対して垂直な断面のＳＥＭ写真 実施例１の金属部材のアンカ部をレーザ走査方向に平行に切断した断面のＳＥＭ写真 比較例１の金属部材のレーザ走査方向に対して垂直な断面のＳＥＭ写真 実施例１の金属樹脂接合体の断面のＳＥＭ写真 図９の断面におけるアルミニウムの分布を示す成分分析像 図９の断面における硫黄の分布を示す成分分析像 図９の断面におけるケイ素の分布を示す成分分析像
　本発明は下記実施形態に限定されない。下記実施形態は、例として提示したものであり、発明の範囲を限定することは意図していない。新規な実施形態は、その他の様々な形態で実施されることが可能であり、発明の要旨を逸脱しない範囲で、種々の省略、置き換え、変更を行うことができる。なお、以下、本発明の実施形態について図面を参照して説明する。図面では、説明のために部材の大きさなどが誇張されて書かれている場合がある。
　（１）金属樹脂接合体１０
　まず、本実施形態の金属樹脂接合体１０について説明する。図１に示すように、金属樹脂接合体１０は、熱可塑性樹脂からなる樹脂部材２０と、金属からなる金属部材３０とを備え、樹脂部材２０の表面（以下、この表面を「樹脂接合面」ということがある）２２と、金属部材３０の表面（以下、この表面を「金属接合面」ということがある）３２とを接合したものである。
　（２）樹脂部材２０
　樹脂部材２０は、熱可塑性樹脂をブロック状、板状、又は線状等の所定形状に成形した部材である。また、樹脂部材２０は、熱可塑性樹脂の塗膜や、熱可塑性樹脂製の接着剤からなる接着層であってもよい。樹脂部材２０を構成する熱可塑性樹脂として、具体例を挙げると、ポリプロピレン樹脂（ＰＰ樹脂）、ポリアセタール樹脂（ＰＯＭ樹脂）、ポリフェニレンサルファイド樹脂（ＰＰＳ樹脂）、ポリエーテルエーテルケトン樹脂（ＰＥＥＫ）、アクリロニトリル／ブタジエン／スチレン樹脂（ＡＢＳ樹脂）、ポリエチレン樹脂（ＰＥ樹脂）、ポリブチレンテレフタレート樹脂（ＰＢＴ樹脂）、ナイロン６６等（ＰＡ６６）のポリアミド樹脂（ＰＡ樹脂）、エポキシ樹脂、液晶ポリマー（ＬＣＰ樹脂）、変性ポリフェニレンエーテル樹脂（変性ＰＰＥ）、リアクター型軟質ポリプロピレン系樹脂（メタロセン系リアクター型ＴＰＯ樹脂）などである。また、樹脂部材２０は、上記のような熱可塑性樹脂に炭素繊維が配合された炭素繊維強化熱可塑性樹脂（ＣＦＲＴＰ）や、上記のような熱可塑性樹脂にガラス繊維、タルクなどの補強材や難燃化材や劣化防止剤やエラストマー成分などが配合されたものでもよい。
　（３）金属部材３０
　金属部材３０は、金属をブロック状、板状、又は線状等の所定形状に成形した部材である。金属部材３０を構成する金属としては、銅（Ｃｕ）、鉄（Ｆｅ）、アルミニウム（Ａｌ）、亜鉛（Ｚｎ）、マグネシウム（Ｍｇ）、錫（Ｓｎ）、チタン（Ｔｉ）ニッケル（Ｎｉ）、クロム（Ｃｒ）等、特に限定されず種々の金属を用いることができる。また、金属部材３０は、銅合金、鉄合金（鉄鋼材）、アルミニウム合金、ステンレス、チタン合金、ニッケル合金、クロム合金、亜鉛合金、マグネシウム合金等の２種以上の金属からなる合金、あるいはケイ素や炭素など非金属と上記した金属との合金から構成されてもよい。金属部材３０は、後述するアンカ部３４を形成しやすい点で、アルミニウム、亜鉛、マグネシウム、錫やＦｅ－Ｓｉ合金、Ｃｕ－Ｓｎ合金、Ｍｇ－Ａｌ合金等、融点における溶融粘度が５ｍＰａ・ｓ以下である金属や合金であることが好ましい。
　金属部材３０の形状は、用途等に応じて所望の形状とすることができる。金属部材３０の成形方法は、任意の方法を適用することができ、所望の形状の型に溶融した金属等を流し込む鋳造や、工作機械等による切削加工や、プレス機械等による打ち抜き加工等を用いてもよい。
　金属部材３０の金属接合面３２には、粗面化処理が施され、アンカ部３４が設けられている。
　また、金属部材３０は、金属接合面３２やアンカ部３４に酸化膜（金属酸化物）が形成されていてもよい。酸化膜は、金属の表面に自然に形成された自然酸化膜であってもよい。また、酸化膜は、酸化剤による表面処理、陽極酸化による電解処理、プラズマ酸化処理、酸素含有気体中での加熱酸化処理等により金属部材３０の表面に形成されたものであってもよい。
　好ましい態様として、酸化膜は、空気中などの酸素含有気体の雰囲気下において、金属部材３０の表面を急速に加熱して金属部材３０の表面に形成されたものであってもよい。急速に加熱する際の１分間あたりの金属部材３０の表面の上昇温度は、金属部材３０を構成する金属の融点温度以上であることが好ましい。このように金属部材３０の表面を急速に加熱することで、金属部材３０の表面に緻密な酸化膜を形成することができる。しかも、金属部材３０の表面を急速に加熱することで、酸化膜の表面にマイクロクラックが発生し、樹脂部材２０との接合面積が大きくなる。
　なお、レーザ加熱、誘導加熱又は抵抗加熱など種々の方法によって金属部材３０の表面を急速に加熱することができるが、加熱時の昇温速度が速く、温度制御が容易であることから、レーザ光の照射によって金属部材３０の表面を加熱して酸化膜を形成することが好ましい。
　（４）アンカ部３４
　アンカ部３４は、図１及び図２に示すように、複数の金属粒子３６の集合体３８と、複数の金属粒子３６の間に形成された複数の空隙４０とを備え、金属接合面３２から突出するように設けられている。アンカ部３４は、所定方向（以下、この方向を第１方向）Ｘに沿って設けられている。
　集合体３８は、複数の金属粒子３６との間に空隙４０を設けつつ複数の金属粒子３６が互いに接触するように三次元的に配置されたものであり、複数の金属粒子３６は接触する部分が融着している。アンカ部３４に設けられた複数の空隙４０は、アンカ部３４の表面に種々の方向に向けて開口するとともにアンカ部３４の内部で連結され、アンカ部３４の表面から内部へ繋がっている。
　集合体３８を構成する複数の金属粒子３６は、金属部材３０を構成する金属と同一の金属からなる。金属粒子３６の粒子径は、特に限定されない。例えば、金属粒子３６の平均粒径は５～５０μｍでもよい。ここで、金属粒子３６の平均粒径は、顕微鏡観察により画像を得て、この画像を用いて、金属粒子３６の長径と短径（長径と短径が同じ場合には、ある軸方向の長さとこれに直交する軸方向の長さ）を無作為に選んだ１０個の粒子について測定し、その平均値を算出することで求められる。
　集合体３８は、一端が金属接合面３２に付着し他端が金属接合面３２から離れるように突出する柱状の金属粒子３６を複数含んでいることが好ましい。柱状の金属粒子３６の先端は丸みを帯びていることがより好ましい。
　この柱状の金属粒子３６は、金属部材３０の金属接合面３２へ後述するようなレーザを照射することで溶融した金属が、金属接合面３２から飛散すること無く再凝固して形成された金属粒子３６である。
　なお、集合体３８は、このような柱状の金属粒子３６とともに、レーザ照射によって金属接合面３２から飛散した溶融金属が金属接合面３２に再付着することで形成された略球状の金属粒子３６を含んでいてもよい。集合体３８は、集合体３８を構成する金属粒子３６の６０％以上が柱状の金属粒子３６であることが好ましい。
　ここで柱状の金属粒子３６とは、金属粒子３６の長手方向の長さが金属粒子３６の最大径寸法の２倍以上である金属粒子３６を意味する。最大径寸法とは、金属粒子３６の長手方向に垂直な断面における断面径のうち最大の寸法を意味する。
　金属粒子３６の長手方向の長さ及び最大径寸法は、顕微鏡観察により取得した画像を用いて測定することができる。無作為に選んだ１０個の金属粒子３６について長手方向の長さ及び最大径寸法を測定し、それぞれの平均値を長手方向の平均長さ及び平均最大径寸法とすると、金属粒子３６の長手方向の平均長さは５～５０μｍでもよく、金属粒子３６の平均最大径寸法は５～２５μｍでもよい。
　また、集合体３８を構成する金属粒子３６に占める柱状の金属粒子３６の割合は、顕微鏡観察により取得した画像から１００個の金属粒子３６を無作為に選び、選んだ１００個の金属粒子３６に含まれる柱状の金属粒子３６の個数から算出する。
　空隙４０は、開口部の最小径が０．１μｍ以上であることが好ましく、１μｍ以上であることがより好ましい。空隙４０の開口部の最小径が、０．１μｍ以上であると空隙４０の内部に樹脂部材２０が入り込みやすくなり、１μｍ以上であると空隙４０の内部に樹脂部材２０が更に入り込みやすくなる。
　好ましい態様として、複数の金属粒子３６の集合体３８は、図１に示すように、金属接合面３２から陥没する凹部４２の内部に設けられてもよい。凹部４２は金属接合面３２からの深さが５～２００μｍ、金属接合面３２の位置における幅が５～２００μｍの第１方向Ｘに沿って延びる凹溝であってもよい。集合体３８が凹部４２の内部に設けられている場合、集合体３８の一部が金属接合面３２より突出するように、集合体３８が凹部４２の内部に設けられている。
　なお、本実施形態では、図２に示すように、金属接合面３２に３つのアンカ部３４が第１方向Ｘに垂直な方向（以下、この方向を第２方向）Ｙに間隔をあけて設けられているが、金属接合面３２に１つのアンカ部３４を設けてもよく、金属接合面３２に任意の数のアンカ部３４を第２方向Ｙに間隔をあけて設けてもよい。また、金属接合面３２に複数のアンカ部３４を設ける場合、図２に示すように一のアンカ部３４が、他のアンカ部３４と平行に設けられてもよく、傾斜するように設けられてもよい。
　（５）金属樹脂接合体１０の製造方法
　次に、金属樹脂接合体１０の製造方法について説明する。
　まず、所定形状に成形した樹脂部材２０と金属部材３０を準備する。そして、金属部材３０の金属接合面３２にアンカ部３４を形成するアンカ形成工程を実行する。その後、アンカ部３４を形成した金属接合面３２に、樹脂部材２０の樹脂接合面２２を接合する接合工程を行う。これにより、金属部材３０の金属接合面３２に樹脂部材２０が接合された金属樹脂接合体１０が得られる。以下、アンカ形成工程及び接合工程について詳述する。
　（５－１）アンカ形成工程
　アンカ形成工程では、金属部材３０のうち樹脂部材２０が接合される金属接合面３２に、下記式（１）で表される係数Ａが０．１以上１．０以下を満たすパルス状のレーザ光を第１方向Ｘへ移動（走査）させながら照射することが好ましい。
Ａ＝ＬＦ／（１―Ｃ）　式（１）
　式（１）中、Ｌはレーザ光のスポット直径（ｍｍ）、Ｆはレーザ光のフルエンス（Ｊ／ｍｍ２）、Ｃは走査するレーザ光のスポット間のオーバーラップ率を表す。なお、オーバーラップ率Ｃは、レーザ光のスポット間隔（隣接するレーザスポットの中心間の距離）をｄ（ｍｍ）とすると、Ｃ＝（Ｌ－ｄ）／Ｌで表される。
　上記の係数Ａが０．１以上１．０以下のパルス状のレーザ光を金属接合面３２に照射すると、レーザ光を照射した位置にある金属は溶融して凹部４２が形成されるとともに、溶融した金属が粒子状になって凹部４２内に堆積して金属粒子３６の集合体３８が形成される。
　なお、酸素含有気体中において上記のようにレーザ光を照射してアンカ部３４を形成すると、アンカ部３４を構成する金属粒子３６の表面に金属酸化物が形成される。
　また、複数のアンカ部３４を第２方向Ｙに間隔をあけて形成する場合、第２方向Ｙに所定間隔をあけた位置においてパルス状のレーザ光を第１方向Ｘへ走査させながら金属接合面３２に照射する。
　なお、金属部材３０の金属接合面３２にパルス状のレーザ光を照射してアンカ部３４を形成する前に、金属接合面３２においてアンカ部３４を形成する箇所にレーザ光を照射し、金属接合面３２に付着する不純物を除去する前処理を行ってもよい。
　（５－２）接合工程
　接合工程では、金属部材３０及び樹脂部材２０を加熱した状態で、金属接合面３２に樹脂接合面２２を加圧しながら接触させる。これにより、金属部材３０の金属接合面３２に樹脂部材２０が接合され金属樹脂接合体１０が得られる。本実施形態では、図３及び図４に示すような接合装置５０を用いて第１工程及び第２工程を行い、金属樹脂接合体１０を製造する。
　接合装置５０は、金属部材３０が載置されるステージ５１と、ステージ５１に載置された金属部材３０を誘導加熱する加熱装置５２と、樹脂部材２０を金属部材３０に加圧接合するプレス装置５３とを備える。
　ステージ５１には、アンカ部３４を設けた金属接合面３２が樹脂部材２０と対向するように金属部材３０が載置される。
　加熱装置５２は、電源装置（不図示）に接続された誘導加熱コイルを備え、電源装置から駆動電源が入力されると誘導加熱コイルから磁界を発生させてステージ５１に載置された金属部材３０の金属接合面３２を誘導加熱する。
　プレス装置５３は、セラミックス等の絶縁体で形成されたロッド５４と、ロッド５４を移動させて樹脂部材２０を金属部材３０の金属接合面３２に押し当てる加圧部５５とを備える。ロッド５４は、図３に示すように、加熱装置５２が有する誘導加熱コイルの中空部分に挿入され、樹脂部材２０と対向するように配置されていてもよい。加圧部５５は、電空レギュレータにより制御された空圧式シリンダや、スプリング式加圧器などを備え、ロッド５４とともに樹脂部材２０を移動させる速度と、樹脂部材２０を金属部材３０に押し当てる時の圧力を制御できることが好ましい。
　接合装置５０を用いて金属樹脂接合体１０を製造するには、まず、気体が存在する雰囲気において、アンカ部３４を設けた金属接合面３２がこの後にセッティングする樹脂部材２０と対向するように、ステージ５１の上に金属部材３０を載置する。
　次いで、樹脂接合面２２がステージ５１に載置した金属部材３０の金属接合面３２と間隔をあけて対向するように樹脂部材２０を配置する。金属部材３０の金属接合面３２と樹脂部材２０の樹脂接合面２２との間隔は、例えば、０．００１ｍｍ～１０ｍｍに設定される。
　次いで、樹脂部材２０を挟んで金属部材３０の金属接合面３２に対向するように加熱装置５２を配置する。図３に示す場合では、加熱装置５２を樹脂部材２０の上方に配置し、加熱装置５２と金属部材３０との間に樹脂部材２０を配置する。
　次いで、樹脂部材２０の樹脂接合面２２を第１の温度Ｔ１に加熱した気体に曝す第１工程を実行する。
　具体的には、加熱装置５２に駆動電源を供給して、加熱装置５２に設けられた誘導加熱コイルから磁界を発生させて金属部材３０の金属接合面３２を加熱する。その際、金属部材３０の金属接合面３２が第１の温度Ｔ１になるように、加熱装置５２に供給する駆動電源や加熱装置５２に設けられた誘導加熱コイルの位置等を調整する。
　上記のような金属部材３０の加熱に伴って、金属部材３０と樹脂部材２０との間にある気体が第１の温度Ｔ１に加熱される。これにより、金属部材３０の金属接合面３２に対向する樹脂部材２０の樹脂接合面２２が、第１の温度Ｔ１に加熱された気体に曝され、樹脂接合面２２が第１の温度Ｔ１になる。加熱装置５２は、金属部材３０の金属接合面３２を所定時間Ｓ１（例えば、１～１０秒間）加熱して上記のような第１工程を実行し、その後、第１工程を終了して第２工程へ移行する。
　第１工程が終了すると、引き続き第２工程を実行するため、加熱装置５２は、金属部材３０の加熱を停止又は加熱量を低減して、樹脂接合面２２、金属接合面３２及びその周囲（金属部材３０と樹脂部材２０との間の気体）の温度が第２の温度Ｔ２になるまで降温（冷却）する。そして、第２の温度Ｔ２で樹脂部材２０と金属部材３０とを接合する。
　つまり、第２工程では、第１の温度Ｔ１より低い温度（第２の温度Ｔ２）において、プレス装置５３が、樹脂部材２０を所定の速度Ｖで移動させて金属部材３０に衝突させる。このとき、樹脂部材２０は、ロッド５４の先端に対応した位置がアンカ部３４に接触しながら金属部材３０の金属接合面３２に強く押し付けられ、所定の圧力Ｐで金属部材３０に押し付けられる。これにより、アンカ部３４が樹脂部材２０に入り込み、アンカ部３４に設けられた空隙４０に樹脂部材２０を構成する熱可塑性樹脂が進入する。その結果、空隙４０に熱可塑性樹脂が充填されつつアンカ部３４が樹脂部材２０に埋設され、樹脂部材２０の樹脂接合面２２と金属部材３０の金属接合面３２とが局所的（スポット的）に接合された金属樹脂接合体１０が得られる。そして、第２工程を終了する。
　ここで、第１の温度Ｔ１とは、樹脂部材２０を構成する熱可塑性樹脂の１．８ＭＰａの荷重を加えたときの荷重たわみ温度Ｔｆ以上の温度とすることができる。なお、樹脂部材２０が、熱可塑性樹脂に炭素繊維やガラス繊維やタルク等の補強材が配合された樹脂からなる場合、樹脂部材２０を構成する熱可塑性樹脂の１．８ＭＰａの荷重を加えたときの荷重たわみ温度Ｔｆとは、補強材を含まない熱可塑性樹脂の１．８ＭＰａの荷重を加えたときの荷重たわみ温度Ｔｆである。
　第１の温度Ｔ１の上限値は、樹脂部材２０を構成する熱可塑性樹脂の分解温度以下、つまり、熱可塑性樹脂が気化し始める温度より低い温度とすることができる。一例を挙げると、第１の温度Ｔ１の上限値を１０００℃としてもよい。好ましくは、樹脂部材２０を構成する熱可塑性樹脂の融点Ｔｍより２０℃高い温度に第１の温度Ｔ１の上限値を設定することができる。
　また、第２の温度Ｔ２は、第１の温度Ｔ１より低い温度であればよいが、樹脂部材２０を構成する熱可塑性樹脂の１．８ＭＰａの荷重を加えたときの荷重たわみ温度Ｔｆ以上であることが好ましい。第２の温度Ｔ２は、樹脂部材２０を構成する熱可塑性樹脂の融点Ｔｍより低い温度であることが好ましい。第１の温度Ｔ１と第２の温度Ｔ２との温度差は１℃以上２０℃以下であることが好ましい。樹脂部材２０を構成する熱可塑性樹脂の融点Ｔｍより低い温度で樹脂部材２０と金属部材３０とを接合することで、樹脂部材２０の形状の変形を抑えつつ樹脂部材２０を金属部材３０に接合することができる。
　なお、本明細書において、熱可塑性樹脂の融点Ｔｍは、ＪＩＳ　Ｋ７１２１に準じて、示差走査熱量測定器を用いて、昇温速度毎分１０℃で測定した値である。代表的な熱可塑性樹脂の融点を挙げると、ポリプロピレン樹脂は１６８℃、ナイロン６６は２６５℃、ポリブチレンテレフタレート樹脂は２３２～２６７℃、ポリフェニレンサルファイド樹脂は２８０℃である。
　また、熱可塑性樹脂の荷重たわみ温度Ｔｆは、ＪＩＳ　Ｋ７１９１に準じた方法で測定した１．８ＭＰａの荷重を加えたときの荷重たわみ温度である。代表的な熱可塑性樹脂の１．８ＭＰａの荷重を加えたときの荷重たわみ温度Ｔｆを挙げると、ポリプロピレン樹脂は５７～６５℃、ナイロン６６は６６～６８℃、ポリブチレンテレフタレート樹脂は５８℃、ポリフェニレンサルファイド樹脂は１０５℃である。
　なお、第１工程は、空気などの酸素含有気体中で実行されることが好ましい。つまり、酸素含有気体の雰囲気において金属接合面３２及び樹脂接合面２２を第１の温度Ｔ１に加熱し、金属接合面３２及び樹脂接合面２２を第１の温度Ｔ１に加熱された酸素含有気体に曝すことが好ましい。
　酸素含有気体の雰囲気で第１工程を実行すれば、樹脂部材２０の樹脂接合面２２が、酸素含有気体に含まれている酸素と反応することで、塩基性または両性の酸化物と中和反応して化学的に結合しうる官能基が樹脂部材２０の樹脂接合面２２に生成される。
　通常、金属部材３０の表面は、酸化され金属酸化物からなる酸化膜に被覆されているため、樹脂接合面２２に生成された官能基が金属部材３０の金属接合面３２に存在する金属酸化物とファンデルワールス力や水素結合によって接合する。加えて、樹脂部材２０と金属部材３０とを加熱及び加圧状態で接合することで、樹脂接合面２２の官能基が金属部材３０の金属酸化物と中和反応（脱水縮合）による共有結合を形成する。
　樹脂接合面２２に生成される官能基の一例を挙げると、樹脂部材２０を構成する熱可塑性樹脂の酸化分解により生成されたカルボキシル基（－ＣＯＯＨ）、カルボニル基（－ＣＯ－）、ヒドロキシ基（－ＯＨ）の少なくともいずれか１つを有している。樹脂部材２０を構成する熱可塑性樹脂がポリフェニレンサルファイド樹脂（ＰＰＳ）のようなイオウ原子（ヘテロ原子）を含む樹脂では、樹脂接合面２２が有する官能基としてはカルボキシル基、カルボニル基、ヒドロキシ基に加えて、スルホン基（－ＳＯ３Ｈ）、スルホニル基（－ＳＯ２－ ）、スルファニル基（－ＳＨ）、ジスルフィド基（－ＳＳ－）等のようなヘテロ原子を含む官能基を含んでもよい。
　金属部材３０と樹脂部材２０の接合により生じる中和反応の一例を挙げると、樹脂接合面２２が官能基としてカルボキシル基（Ｒ－ＣＯＯＨ）を有しており、金属部材３０が２価の金属から構成されている場合、下記式（２）のような中和反応が生じる。
２（Ｒ－ＣＯＯＨ）＋ＭｅＯ＝２（Ｒ－ＣＯＯ）－Ｍｅ＋Ｈ２Ｏ↑・・・（２）
　なお、式（２）中、Ｒは樹脂部材２０を構成する熱可塑性樹脂の主鎖、Ｍｅは金属部材３０を構成する金属である。
　また、酸素含有気体の雰囲気で第１工程を実行する場合、第２の温度Ｔ２は、樹脂部材２０の樹脂接合面２２が有する官能基と、金属部材３０の金属接合面３２に形成された金属酸化物とが中和反応による共有結合を形成しうる温度であることが好ましい。また、第２の温度Ｔ２は、中和反応により発生した水が反応系から除去される温度であることが好ましい。第２の温度Ｔ２は、官能基及び金属酸化物の種類により変わるため、一概に規定することが困難であるが、中和反応により発生した水が除去されやすいことから１００℃以上であることがより好ましい。
　また、第１工程において、金属部材３０及び樹脂部材２０の全体が第１の温度Ｔ１になるように金属部材３０及び樹脂部材２０を加熱してもよいが、少なくとも金属接合面３２及び樹脂接合面２２が第１の温度Ｔ１になるように金属部材３０及び樹脂部材２０を加熱してもよい。
　また、第２工程において、樹脂部材２０を金属部材３０に押し当てる時の圧力Ｐは、樹脂部材２０を構成する熱可塑性樹脂の圧縮降伏応力以上の圧力であることが好ましい。この圧力Ｐは、樹脂部材２０を構成する熱可塑性樹脂により変わるため、一概に規定することが困難であるが、１０～１００ＭＰａであることが好ましい。
　また、本実施形態では、プレス装置５３が金属部材３０へ向けて樹脂部材２０を移動する場合について説明したが、金属部材３０を樹脂部材２０へ向けて移動させてもよい。
　また、本実施形態のように金属部材３０と樹脂部材２０を局所的に接合する場合、接合箇所の平面形状は点状、線状、面状など任意の形状であってもよい。
　また、本実施形態では、金属部材３０と樹脂部材２０を局所的に加圧して接合する場合について説明したが、樹脂接合面２２や金属接合面３２の全面を加圧するなど樹脂部材２０と金属部材３０とを広い範囲にわたって接合してもよい。
　また、本実施形態において、樹脂部材２０を金属部材３０に押し付けている間、樹脂部材２０、金属部材３０及びその周囲の温度を第２の温度Ｔ２に保持してもよい。あるいはまた、樹脂部材２０、金属部材３０及びその周囲の温度が所定温度以下に冷却されるまで、樹脂部材２０を金属部材３０に加圧状態で接触させ続けても良い。その場合、樹脂部材２０、金属部材３０及びその周囲の温度が、樹脂部材２０を構成する熱可塑性樹脂のガラス転移温度Ｔｇ以下に冷却されるまで、樹脂部材２０を金属部材３０に加圧状態で接触させることが好ましい。
　また、本実施形態では、接合工程として、予め所定形状に成形した樹脂部材２０を加熱しながら金属部材３０に圧着する場合について説明したが、アンカ部３４が形成された金属部材３０を射出成形型内にインサートし、溶融した合成樹脂材料を射出成形型内で金属接合面３２へ向けて射出することで、金属部材３０に樹脂部材２０を接合してもよい。
　（６）効果
　本実施形態の金属樹脂接合体１０では、樹脂部材２０を金属部材３０に接合する際に、樹脂部材２０を構成する熱可塑性樹脂が空隙４０に進入するため、高いアンカ効果を発揮することができ、樹脂部材２０と金属部材３０との接合強度を高めることができる。
　本実施形態では、アンカ部３４が金属接合面３２から突出するとともに、三次元的に配置された複数の金属粒子３６の間に複数の空隙４０が形成されているため、アンカ部３４の表面に比較的大きな開口部が種々の方向に向けて開口する。そのため、本実施形態では、樹脂部材２０を構成する熱可塑性樹脂が空隙４０に進入しやすく、接合強度を向上することができる。特に、樹脂部材２０を構成する熱可塑性樹脂の融点Ｔｍより低い第２の温度Ｔ２で樹脂部材２０と金属部材３０とを接合する場合であっても、樹脂部材２０を構成する熱可塑性樹脂を空隙４０に進入させることができ、樹脂部材２０の形状変形を抑えつつ、接合強度を向上することができる。
　しかも、アンカ部３４を構成する複数の金属粒子３６の少なくとも一部が、一端が金属接合面３２に付着し他端が金属接合面３２から離れるように突出する柱状の金属粒子３６である場合、樹脂部材２０の内部へ金属粒子３６が食い込みやすくなる。そのため、アンカ部３４によって高いアンカ効果が発揮され、接合強度を向上することができる。
　本実施形態のように金属接合面３２から陥没する凹部４２にアンカ部３４を構成する集合体３８が設けられている場合、空隙４０をアンカ部３４の奥深くまで延ばすことができ、接合強度を向上することができる。
　本実施形態において、アンカ部３４の表面に金属酸化物が形成されている場合、樹脂部材２０の樹脂接合面２２が有する官能基が、アンカ部３４の金属酸化物と双極子相互作用によって接合する。加えて、樹脂接合面２２の官能基が金属酸化物と中和反応（脱水縮合）による共有結合を形成する。そのため、金属樹脂接合体１０の接合強度高めることができる。
（実施例）
　以下、本発明の実施例１～３及び比較例１～３を説明する。なお、本発明は実施例１～３に限定されるものではない。
　実施例１～３及び比較例１～３において、レーザ波長が１０６４ｎｍ、パルス幅が０．２μ秒のシングルモードレーザを照射してアルミニウム（Ａｌ１０５０）からなる金属部材の金属接合面に長さ１８ｍｍのアンカ部を０．２ｍｍピッチで形成した。そして、アンカ部を形成した金属接合面に樹脂部材を接合した。実施例１～３は上記係数Ａが０．５３Ｊ／ｍｍのレーザを照射し、比較例１～３は上記係数Ａが０．０８Ｊ／ｍｍのレーザを照射した。
　また、実施例１～３及び比較例１～３に使用した樹脂部材の詳細、金属部材の寸法、樹脂部材の寸法、樹脂部材と金属部材との接合面積（オーバラップ面積）は、以下の通りである。なお、実施例１及び比較例１の樹脂部材には、補強材としてガラス繊維が配合されている。
　・ＰＰＳ樹脂：サスティール（登録商標）ＳＧＸ１２０
　・変成６Ｔナイロン樹脂：アーレン（登録商標）　Ａ３５０
　・ＰＰ樹脂：ノバテック（登録商標）　ＨＧ３０Ｕ
　・金属部材の寸法：１８ｍｍ×４５ｍｍ×１．６ｍｍ
　・樹脂部材の寸法：１０ｍｍ×４０ｍｍ×３．０ｍｍ
　・金属部材と樹脂部材との接合面積：１０ｍｍ×５ｍｍ
　評価方法は次の通りである。
　（ａ）アンカ部のＳＥＭ観察
　金属接合面にアンカ部を形成した実施例１及び比較例１の金属部材について、樹脂部材２０を接合していない状態でアンカ部のＳＥＭ観察を行った。複数の金属粒子の集合体と、複数の金属粒子の間に形成された複数の空隙とを備えたアンカ部が金属接合面から突出するように形成されている場合、良好なアンカ部であると評価して「〇」で表し、このようなアンカ部が形成されていない場合、不良なアンカ部であると評価して「×」で表した。
　結果は表１、図５～図８に示すとおりである。図５は実施例１の金属部材の金属接合面のＳＥＭ写真、図６は実施例１の金属部材のレーザ走査方向（アンカ部の長手方向）に対して垂直な断面のＳＥＭ写真、図７は実施例１の金属部材のアンカ部をレーザ走査方向に平行に切断した断面のＳＥＭ写真、図８は比較例１の金属部材のレーザ走査方向に対して垂直な断面のＳＥＭ写真を示す。
　図５～図７に示すように、実施例１の金属部材では、一端が金属接合面に付着し他端が金属接合面から離れるように突出する柱状の金属粒子からなる金属粒子が複数集まった集合体と、複数の金属粒子の間に形成された複数の空隙と、を備えたアンカ部が金属接合面から突出するように形成されていた。一方、比較例１の金属部材では、図８に示すように、金属接合面から陥没する凹部が形成されていたが、複数の金属粒子の集合体と複数の金属粒子の間に形成された複数の空隙とを備えたアンカ部が形成されていなかった。
　（ｂ）接合強度
　ＪＩＳ　Ｋ　６８５０に規定された試験方法のうち、金属部材の寸法、樹脂部材の寸法、樹脂部材と金属部材との接合面積を上記の通りに変更し、その他の条件を同規格に準じて、引張試験機（島津製作所、オートグラフ　ＡＧＸ－Ｖ）を用い、引張速度１０ｍｍ／ｍｉｎ、測定温度２５℃で測定した。なお、実施例１～３及び比較例１～３の試験片をそれぞれ４個ずつ作製し、４個の測定値の平均値をそれぞれの接合強度とした。
Figure JPOXMLDOC01-appb-T000001
  
　結果は、表１に示すとおりである。ＰＰＳ樹脂、変成６Ｔナイロン樹脂及びＰＰ樹脂において、比較例１～３に比べて実施例１～３において接合強度が向上したことが確認できた。
　（ｃ）ＥＤＳ（エネルギー分散型Ｘ線分光法）による元素分析
　実施例１の金属樹脂接合体について、日本電子社製ＪＳＭ－６３９０Ａを用いて断面を撮像するとともにＥＤＳによる元素分析を行った。
　結果は、図９～図１２に示すとおりである。なお、図９において樹脂部材（図９の上部の暗い領域）に存在する明るい箇所は樹脂部材が含有するガラス繊維を示している。図１０において白色に見える領域にアルミニウムが存在することを示している。図１１において白色に見える領域にＰＰＳに含まれる硫黄が存在することを示している。図１２において白色に見える領域にガラス繊維に含まれるケイ素が存在することを示している。
　図９～図１２から分かるように、アンカ部を構成するアルミニウム粒子の突起形状を壊すことなくアルミニウム粒子の集合体の空隙部分に硫黄が存在していた。このことからアルミニウム粒子が樹脂部材の内部へ食い込みアンカ効果を発揮するとともに、空隙部分へ進入したＰＰＳ樹脂によってアンカ効果を発揮していることが確認できた。
１０…金属樹脂接合体
２０…樹脂部材
２２…樹脂接合面
３０…金属部材
３２…金属接合面
３４…アンカ部
３６…金属粒子
３８…集合体
４０…空隙
４２…凹部

Claims (10)

  1. 　金属からなる金属部材において、
    　金属接合面と、前記金属接合面から突出するアンカ部とを備え、
    　前記アンカ部は、複数の金属粒子の集合体と、前記複数の金属粒子の間に形成された複数の空隙を備え、
    　前記複数の空隙は、前記アンカ部の内部で連結され前記アンカ部の表面から内部へ繋がっている金属部材。
  2. 　前記集合体は、一端が前記金属接合面に付着し他端が前記金属接合面から離れるように突出する柱状の金属粒子を含む請求項１に記載の金属部材。
  3. 　前記金属接合面から陥没する凹部を備え、
    　前記集合体の一部が前記金属接合面から突出するように、前記集合体が前記凹部内に設けられている請求項１又は２に記載の金属部材。
  4. 　前記アンカ部は、前記金属接合面上に所定の方向に沿って設けられている請求項１～３のいずれか１項に記載の金属部材。
  5. 　金属からなる金属部材と熱可塑性樹脂からなる樹脂部材とを備え、前記金属部材の金属接合面に前記樹脂部材の樹脂接合面を接合した金属樹脂接合体において、
    　前記金属部材は前記金属接合面から突出するアンカ部を備え、
    　前記アンカ部は、複数の金属粒子の集合体と、前記複数の金属粒子の間に形成された複数の空隙を備え、
    　前記複数の空隙は、前記アンカ部の内部で連結され前記アンカ部の表面から内部へ繋がっている金属樹脂接合体。
  6. 　前記集合体は、一端が前記金属接合面に付着し他端が前記金属接合面から離れるように突出する柱状の金属粒子を含む請求項５に記載の金属樹脂接合体。
  7. 　前記金属部材は、前記金属接合面から陥没する凹部を備え、
    　前記集合体の一部が前記金属接合面から突出するように、前記集合体が前記凹部内に設けられている請求項５又は６に記載の金属樹脂接合体。
  8. 　前記アンカ部は、前記金属接合面上に所定の方向に沿って設けられている請求項５～７のいずれか１項に記載の金属樹脂接合体。
  9. 　金属からなる金属部材の金属接合面に熱可塑性樹脂からなる樹脂部材の樹脂接合面を接合した金属樹脂接合体の製造方法において、
    　前記金属接合面から突出するアンカ部を前記金属部材に形成するアンカ形成工程と、
    　前記アンカ形成工程後、前記樹脂部材を前記アンカ部に接触させながら加圧して、前記アンカ部を前記樹脂部材に入り込ませて前記金属接合面を前記樹脂接合面に接触させる接合工程とを備え、
    　前記アンカ形成工程は、前記金属接合面に対してパルスレーザ光を照射することで、複数の金属粒子の集合体からなり、前記複数の金属粒子の間に前記アンカ部の表面から内部へ繋がる複数の空隙を有する前記アンカ部を形成する金属樹脂接合体の製造方法。
  10. 　前記集合体は、一端が前記金属接合面に付着し他端が前記金属接合面から離れるように突出する柱状の金属粒子を含む請求項９に記載の金属樹脂接合体の製造方法。
     
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