WO2022044740A1 - 金属と樹脂の接合方法及びその接合体 - Google Patents

金属と樹脂の接合方法及びその接合体 Download PDF

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Publication number
WO2022044740A1
WO2022044740A1 PCT/JP2021/028939 JP2021028939W WO2022044740A1 WO 2022044740 A1 WO2022044740 A1 WO 2022044740A1 JP 2021028939 W JP2021028939 W JP 2021028939W WO 2022044740 A1 WO2022044740 A1 WO 2022044740A1
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Prior art keywords
metal
resin
compound
group
treatment
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Ceased
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PCT/JP2021/028939
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English (en)
French (fr)
Japanese (ja)
Inventor
和男 大谷
信行 高橋
良太 新林
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Resonac Holdings Corp
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Showa Denko KK
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Application filed by Showa Denko KK filed Critical Showa Denko KK
Priority to JP2022545601A priority Critical patent/JPWO2022044740A1/ja
Priority to CN202180052776.6A priority patent/CN116113536A/zh
Priority to US18/042,492 priority patent/US20230330946A1/en
Publication of WO2022044740A1 publication Critical patent/WO2022044740A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • B29C65/56—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using mechanical means or mechanical connections, e.g. form-fits
    • B29C65/64—Joining a non-plastics element to a plastics element, e.g. by force
    • 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
    • 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
    • B29C65/18—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using heated tools
    • B29C65/24—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using heated tools characterised by the means for heating the tool
    • B29C65/30—Electrical means
    • B29C65/32—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
    • B29C65/02—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
    • B29C65/48—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
    • B29C65/4805—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding characterised by the type of adhesives
    • B29C65/481—Non-reactive adhesives, e.g. physically hardening adhesives
    • B29C65/4815—Hot melt adhesives, e.g. thermoplastic adhesives
    • 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
    • B29C65/4805—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding characterised by the type of adhesives
    • B29C65/483—Reactive adhesives, e.g. chemically curing adhesives
    • B29C65/4835—Heat curing adhesives
    • 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
    • B29C65/50—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding using adhesive tape, e.g. thermoplastic tape; using threads or the like
    • B29C65/5007—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding using adhesive tape, e.g. thermoplastic tape; using threads or the like characterised by the structure of said adhesive tape, threads or the like
    • B29C65/5021—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding using adhesive tape, e.g. thermoplastic tape; using threads or the like characterised by the structure of said adhesive tape, threads or the like being multi-layered
    • 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
    • B29C65/50—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding using adhesive tape, e.g. thermoplastic tape; using threads or the like
    • B29C65/5057—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding using adhesive tape, e.g. thermoplastic tape; using threads or the like positioned between the surfaces 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
    • 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
    • B29C65/52—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding characterised by the way of applying the adhesive
    • B29C65/54—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding characterised by the way of applying the adhesive between pre-assembled parts
    • 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
    • B29C65/8207—Testing the joint by mechanical methods
    • B29C65/8215—Tensile tests
    • 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
    • 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
    • B29C66/028—Non-mechanical surface pre-treatments, i.e. by flame treatment, electric discharge treatment, plasma treatment, wave energy or particle radiation
    • 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
    • B29C66/40—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
    • B29C66/43—Joining a relatively small portion of the surface of said 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
    • B29C66/71—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
    • 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
    • B29C66/73—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
    • 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
    • B29C66/7422—Aluminium or alloys of aluminium
    • 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
    • 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
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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
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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

Definitions

  • the present invention relates to a metal-resin bonding method and a bonded body thereof, which are bonded by high-frequency induction welding.
  • Multi-materialization is the combination of materials with different functions and properties (hereinafter, also referred to as dissimilar materials) such as high tensile strength steel sheets (HITEN), aluminum, and resins such as carbon fiber reinforced plastics (CFRP). This is a method for reducing the weight and increasing the strength of the material. Joining technology for dissimilar materials is indispensable for realizing multi-materialization.
  • dissimilar materials such as high tensile strength steel sheets (HITEN), aluminum, and resins such as carbon fiber reinforced plastics (CFRP).
  • Patent Documents 1 and 2 disclose a manufacturing method in which a coated metal molding material containing an organic resin layer having a thickness of 0.2 ⁇ m or more and a thermoplastic resin are heated by electromagnetic induction and welded. Specifically, a method for producing a composite by joining a metal provided with a polypropylene-based organic material layer and a molded product of a polypropylene-based composition is disclosed.
  • thermoplastic composite molded body in which a thermoplastic elastomer resin composition is interposed between a member made of a magnetic material and / or a conductor and a thermoplastic resin and integrated by welding by electromagnetic induction heating is used. It has been disclosed. Specifically, a thermoplastic elastomer resin composition containing a hard segment composed of a crystalline aromatic polyester unit and a soft segment composed of an aliphatic polyether unit and / or an aliphatic polyester is interposed between the metal and the polyester. A method of integrating block copolymers by welding by electromagnetic induction heating is disclosed.
  • Patent Document 1 and Patent Document 2 can solve the problems of fastening with rivets and bonding with an adhesive, but bonding using a metal and a resin as different materials is sufficient. It had a problem that it was difficult to obtain strength.
  • the present invention has been made in view of such a technical background, and provides a metal-resin bonding method and a bonded body thereof capable of bonding a metal and a resin with sufficient bonding strength by high-frequency induction welding. The purpose is.
  • a metal-resin bonding method in which a metal and a resin are bonded by high-frequency induction welding via an intermediate resin layer that causes a chemical reaction by high-frequency induction welding.
  • the intermediate resin layer is a primer layer laminated on the metal.
  • the intermediate resin layer includes a thermoplastic resin layer obtained by subjecting an in-situ polymerization type composition to at least one reaction selected from a polyaddition reaction and a radical polymerization reaction, and a thermosetting resin layer in a B stage state.
  • the method for joining a metal and a resin according to [1] which is a multilayer structure film.
  • thermosetting resin layer in the B stage state is one of [4], [8], and [9], wherein the unsaturated group is radically polymerized or the epoxy group is ring-opened polymerized.
  • the functional group imparting treatment is a treatment of reacting a compound corresponding to at least one selected from the following (i) to (iii) to impart a functional group to the surface of the metal.
  • the method for joining a metal and a resin according to. (Ii) Alkoxysilane compound (ii) A compound having at least one functional group selected from an amino group, an epoxy group, a mercapto group, and an isocyanato group (iii) A compound having a radical reactive group [13] [1] to [ A metal-resin bonding body obtained by the metal-resin bonding method according to any one of 12].
  • the metal and resin can be bonded with sufficient bonding strength by high-frequency induction welding. Therefore, according to the present invention, it is possible to provide a bonded body in which a metal and a resin are bonded with sufficient bonding strength by high-frequency induction welding.
  • the bonding method of the present embodiment is a metal-resin bonding method in which a metal and a resin are bonded by high-frequency induction welding via an intermediate resin layer that causes a chemical reaction by high-frequency induction welding.
  • the chemical reaction means changing to another substance by the reaction, and means changing by synthesis, cyclization, decomposition, condensation, polymerization, oxidation, reduction, rearrangement, addition and the like.
  • High-frequency induction welding is a method of melting and welding a material from the inside by dielectric heating with high frequency.
  • the metal and the resin can be bonded with sufficient bonding strength by bonding by high frequency induction welding.
  • the metal and the resin can be joined in a relatively short time. Further, it is possible to provide a bonded body in which a metal and a resin are bonded with sufficient bonding strength.
  • the metal, the intermediate resin layer and the resin may be joined at once, the metal and the intermediate resin layer may be joined and then the resin may be joined, or the resin and the intermediate resin layer may be joined. After joining, the metal may be joined. From the viewpoint of productivity, it is preferable to join the metal, the intermediate resin layer, and the resin at once.
  • the metal is not particularly limited, and examples thereof include iron, copper, aluminum, magnesium, and titanium.
  • the word "iron” is used to include iron and its alloys. Examples of the iron alloy include steel and the like.
  • copper, aluminum, magnesium, titanium and the like are also used in the sense of including these simple substances and their alloys.
  • aluminum is preferable from the viewpoint of weight reduction, ease of processing, and the like, and from the viewpoint of multi-material material applications used in automobiles and the like.
  • ⁇ surface treatment From the viewpoint of improving the adhesiveness between the metal and the intermediate resin layer and improving the bonding strength between the metal and the resin, it is preferable to apply a surface treatment to the bonding surface of the metal with the resin.
  • the bonding strength between the metal and the resin is improved by removing contaminants on the metal surface by surface treatment, roughening the metal surface for the purpose of anchoring effect, and imparting functional groups to the metal surface.
  • the surface treatment includes, for example, cleaning with a solvent, degreasing treatment, blasting treatment, polishing treatment (sanding treatment), plasma treatment, corona discharge treatment, laser treatment, UV ozone treatment, etching treatment, chemical conversion treatment, and functional group addition treatment. Etc., and are appropriately selected depending on the metal.
  • the surface treatment may be performed by only one type or by combining two or more types. Among these, degreasing treatment, polishing treatment, plasma treatment, corona discharge treatment, UV ozone treatment, etching treatment, and functional group addition treatment are preferable, and plasma treatment, etching treatment, and functional group addition treatment are preferable. As the surface treatment limited to aluminum, degreasing treatment, etching treatment, and functional group addition treatment are more preferable, and as the surface treatment of all metals, degreasing treatment, plasma treatment, etching treatment, and functional group addition treatment are more preferable. As a specific method of the surface treatment, a known method can be applied.
  • Examples of the cleaning with the solvent and the like and the degreasing treatment include a method of dissolving and removing stains such as oils and fats on the surface of a metal with an organic solvent such as acetone and toluene. It is preferable to carry out the cleaning with the solvent and the like and the degreasing treatment before performing other surface treatments.
  • blasting process examples include a shot blasting process, a sandblasting process, a wet blasting process, and the like.
  • polishing treatment examples include buffing using a polishing cloth, roll polishing using polishing paper (sandpaper), electrolytic polishing, and the like.
  • the plasma treatment uses a plasma treatment high-pressure power source to hit a metal surface with a plasma beam emitted from a rod, first cleans a foreign matter oil film existing on the surface, and then applies gas energy to excite surface molecules.
  • the method Specific examples thereof include an atmospheric pressure plasma treatment method capable of imparting a hydroxyl group or a polar group to a metal surface.
  • a metal is sandwiched between a pair of electrodes under the atmospheric pressure discharged from the electrodes, and a high AC voltage is applied between the two electrodes to excite the corona discharge, and the surface of the metal becomes a corona discharge. It is an exposure process.
  • the corona generated gas include helium, argon, nitrogen, carbon monoxide, carbon dioxide, oxygen, and the like, and a mixed gas thereof can also be used.
  • the laser treatment is a technique for rapidly heating and cooling only the metal surface layer by laser irradiation to improve the characteristics of the metal surface, and the metal surface can be roughened.
  • a known laser treatment technique can be used for the laser treatment.
  • the UV ozone treatment is a method of cleaning or reforming the surface by the energy of short-wavelength ultraviolet rays emitted from a low-pressure mercury lamp and the power of ozone ( O3) generated by the energy.
  • a cleaning surface reforming device using a low-pressure mercury lamp is called a "UV ozone cleaner", a “UV cleaning device”, an “ultraviolet surface modifying device” or the like.
  • the etching treatment includes, for example, a chemical etching treatment such as an alkali method, a phosphoric acid-sulfuric acid method, a fluoride method, a chromic acid-sulfuric acid method, and a salt iron method, and an electrochemical etching treatment such as an electrolytic etching method.
  • a chemical etching treatment such as an alkali method, a phosphoric acid-sulfuric acid method, a fluoride method, a chromic acid-sulfuric acid method, and a salt iron method
  • an electrochemical etching treatment such as an electrolytic etching method.
  • aluminum is used as the metal, the caustic soda method using an aqueous solution of sodium hydroxide or an aqueous solution of potassium hydroxide is preferable, and the caustic soda method using an aqueous solution of sodium hydroxide is more preferable.
  • a metal is immersed in an aqueous solution of sodium hydroxide or potassium hydroxide having a concentration of 3 to 20% by mass at 20 to 70 ° C. for 1 to 15 minutes, and after the immersion, 1 to 20% by mass of nitrate is used. It is preferable to neutralize (de-smut) with an aqueous solution or the like, wash with water, and dry.
  • a chelating agent, an oxidizing agent, a phosphate or the like may be added.
  • the chemical conversion treatment is to form a chemical conversion film on the surface of a metal.
  • Examples of the chemical conversion treatment include boehmite treatment and zirconium treatment.
  • As the boehmite treatment a known boehmite treatment or the like can be used.
  • the boehmite treatment is, for example, a treatment in which aluminum is treated with hot water to form a boehmite film on the surface.
  • Ammonia, triethanolamine, or the like may be added to water as a reaction accelerator.
  • the zirconium treatment is a treatment for forming a zirconium salt film on the surface of aluminum using, for example, a zirconium compound such as zirconium phosphate or a zirconium salt.
  • a zirconium compound such as zirconium phosphate or a zirconium salt.
  • aluminum is immersed in a chemical agent for zirconium treatment such as "Palcoat 3762" and "Palcoat 3796" (all manufactured by Nihon Parkerizing Co., Ltd.) at 45 to 70 ° C. for 0.5 to 3 minutes. Is preferable.
  • the zirconium treatment is preferably performed after the etching treatment by the caustic soda method.
  • the functional group imparting treatment is a treatment for imparting a functional group to the surface of a metal.
  • the functional group imparting treatment as shown in FIGS. 2, 4, and 6, the functional group of one layer or a plurality of layers laminated between the metal and the intermediate resin layer in contact with the metal and the intermediate resin layer.
  • the group-containing layer 4 can be formed.
  • the functional groups of the functional group-containing layer 4 are the functional groups of the metal surface and the functional groups of the resin constituting the intermediate resin layer, respectively.
  • the chemical bond formed by the reaction has the effect of improving the adhesiveness between the metal and the intermediate resin layer. In addition, the effect of improving the bonding strength between the metal and the resin can also be obtained.
  • the functional group-imparting treatment includes cleaning, degreasing, blasting, polishing, plasma treatment, laser treatment, UV ozone treatment, etching treatment, chemical conversion treatment, and the like, such as cleaning and anchoring effect, on the metal surface. It is preferable to carry out the surface treatment for the purpose of the above. In particular, when the intermediate resin layer is a thermoplastic resin film or a multilayer structure film described later, it is preferable to perform a functional group imparting treatment from the viewpoint of obtaining sufficient bonding strength.
  • the functional group imparting treatment corresponds to a functional group such as a hydroxyl group that originally exists on the metal surface or is newly generated by the surface treatment, and at least one selected from the following (i) to (iii). It is preferable that the treatment is such that the compound is reacted to impart a functional group derived from the compound to the surface of the metal.
  • Alkoxysilane compound (ii) Compound having at least one functional group selected from amino group, epoxy group, mercapto group, and isocyanato group (iii) Compound having radical reactive group
  • alkoxysilane compound A specific example of the alkoxysilane compound is a silane coupling agent, which preferably has a functional group such as an amino group, an epoxy group, a mercapto group, a styryl group, a (meth) acryloyl group, and an isocyanato group.
  • a silane coupling agent include vinyltrimethoxysilane having a vinyl group, vinyltriethoxysilane, 2- (3,4-epyloxycyclohexyl) ethyltrimethoxysilane having an epoxy group, and 3-glyci having a glycidyl group.
  • the method for imparting a functional group with the silane coupling agent is not particularly limited, and examples thereof include a spray coating method and a dipping method.
  • a low-concentration aqueous solution of a silane coupling agent or a low-concentration organic solvent solution of a silane coupling agent is brought into contact with the surface of the metal, so that the hydroxyl group or the like existing on the surface of the metal reacts with the silane coupling agent. Then, a silanol group is generated, and the oligomerized silanol group is bonded to the surface of the metal.
  • a diluted solution obtained by diluting a silane coupling agent with an organic solvent to a concentration of about 0.5% by mass to 50% by mass is heated to room temperature to 100 ° C., and the material is contained in this diluted solution. Is immersed for 1 minute to 5 days to introduce a functional group chemically bonded to the surface of the metal.
  • the silane coupling agent itself or the silane coupling agent diluted with an organic solvent is sprayed on the surface of the metal, and the drying treatment is performed at room temperature to 100 ° C. for 1 minute to 5 hours. After a drying treatment, a strong chemical bond is formed, and a functional group chemically bonded to the surface of the metal can be introduced.
  • the method of imparting a functional group with the silane coupling agent it is preferable to wash the surface into which the functional group is introduced by the silane coupling agent with an organic solvent, alcohol, water or the like.
  • an organic solvent, alcohol, water or the like By removing the silane coupling agent and the compound derived from the silane coupling agent remaining on the functional group introduced by the chemical bond with a weak adsorption force by washing, the bonding strength between the metal and the resin can be improved. ..
  • the compound having an amino group include an amino compound having a (meth) acryloyl group and an amino compound having two or more amino groups.
  • the amino compound is not particularly limited, but for example, (meth) acrylamide, ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 1,4-diaminobutane, hexamethylenediamine, 2 , 5-Dimethyl-2,5-hexanediamine, 2,2,4-trimethylhexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, 4-aminomethyloctamethylenediamine, 3,3' -Iminobis (propylamine), 3,3'-methylimiminobis (propylamine), bis (3-aminopropyl) ether, 1,2-bis (3-aminopropyloxy) ethane, mensendiamine, isophoronediamine, Bis
  • the method for treating with the compound having an amino group is not particularly limited, and examples thereof include a spray coating method and a dipping method. Specifically, for example, a diluted solution obtained by diluting a compound having an amino group with an organic solvent to a concentration of about 5% by mass to 50% by mass is heated to room temperature to 100 ° C., and the material is contained in this diluted solution. For 1 minute to 5 days, the material is taken out and dried at room temperature to 100 ° C. for 1 minute to 5 hours.
  • the compound having an epoxy group include an epoxy compound having a (meth) acryloyl group, an epoxy compound having an alkenyl group, and a bifunctional or higher functional epoxy compound.
  • examples thereof include glycidyl (meth) acrylate, allyl glycidyl ether, 1,6-hexanediol diglycidyl ether, and epoxy resins having two or more epoxy groups in the molecule.
  • 3,4-epoxycyclohexylmethylmethacrylate for example, "Cyclomer M100" (manufactured by Daicel Co., Ltd.)
  • 1,2-epoxy-4-vinylcyclohexane for example, "Seroxide 2000”
  • the method for imparting a functional group with the compound having an epoxy group is not particularly limited, and examples thereof include a spray coating method and a dipping method.
  • a compound having an epoxy group and a low-concentration organic solvent solution of an amine-based or phosphorus-based catalyst are brought into contact with the surface of the metal, so that the hydroxyl group or the like existing on the surface of the metal reacts with the epoxy group to make it functional.
  • a group can be added.
  • a diluted solution obtained by diluting a compound having an epoxy group containing 0.5 to 5% by mass of a catalyst with an organic solvent to a concentration of about 0.5% by mass to 50% by mass is prepared at room temperature.
  • a functional group chemically bonded to the surface of the metal By immersing the material in this diluted solution at 100 ° C. for 1 minute to 5 days, a functional group chemically bonded to the surface of the metal can be introduced.
  • a diluted solution obtained by diluting the compound having an epoxy group containing 0.5 to 5% by mass on the surface of the metal with an organic solvent to a concentration of about 0.5% by mass to 50% by mass is used.
  • the amine-based catalyst is not particularly limited, but for example, triethylenediamine, tetramethylguanidine, N, N, N', N'-tetramethylhexane-1,6-diamine, dimethyl etheramine, N, Examples thereof include N, N', N'', N''-pentamethyldipropylene-triamine, N-methylmorpholin, bis (2-dimethylaminoethyl) ether, dimethylaminoethoxyethanol, triethylamine and the like.
  • the phosphorus-based catalyst is not particularly limited, and examples thereof include triphenylphosphine, benzyltriphenylphosphonium chloride, n-butyltriphenylphosphonium bromide, and the like.
  • Compound having a mercapto group Specific examples of the compound having a mercapto group are a bifunctional or higher functional thiol compound, a thiol compound having an alkenyl group, and the like.
  • a trifunctional or higher functional thiol compound or a compound having an alkenyl group other than the mercapto group is preferable.
  • the thiol compound is not particularly limited, but for example, pentaerythritol tetrakis (3-mercaptopropionate) (for example, "QX40" (manufactured by Mitsubishi Chemical Corporation), "QE-340M” (Toray.
  • the method for treating with the thiol compound is not particularly limited, and examples thereof include a spray coating method and a dipping method. Specifically, for example, a diluted solution obtained by diluting a thiol compound with an organic solvent to a concentration of about 5% by mass to 50% by mass is heated to room temperature to 100 ° C., and the material is placed in this diluted solution for 1 minute. Examples thereof include a method in which the material is taken out after being soaked for about 5 days and then dried at room temperature to 100 ° C. for 1 minute to 5 hours. Amines may be contained as a catalyst in the diluted solution of the thiol compound.
  • the bonding strength between the metal and the resin can be improved.
  • Compound having an isocyanato group Specific examples of the compound having an isocyanato group are an isocyanato compound having a (meth) acryloyl group, a bifunctional or higher functional isocyanato compound, and the like.
  • the isocyanate compound is not particularly limited, but is, for example, 2-isocyanatoethyl methacrylate (for example, "Carens MOI” (registered trademark)) (Showa Denko Co., Ltd.), which is an isocyanate compound having a (meth) acryloyl group.
  • 2-Isocyanatoethyl acrylate eg, "Karenzu AOI” (registered trademark) (manufactured by Showa Denko Co., Ltd.)
  • 1,1- (bisacryloyloxyethyl) ethyl isocyanate eg, "Karenzu BEI (registered)
  • MDI diphenylmethane diisocyanate
  • HDI hexamethylene diisocyanate
  • TDI tolylene diisocyanate
  • IPDI isophorone diisocyanate
  • the method for treating with the isocyanate compound is not particularly limited, and examples thereof include a spray coating method and a dipping method. Specifically, for example, a diluted solution obtained by diluting an isocyanate compound with an organic solvent to a concentration of about 5% by mass to 50% by mass is heated to room temperature to 100 ° C., and the material is placed in this diluted solution for 1 minute. Examples thereof include a method in which the material is taken out after being soaked for about 5 days and then dried at room temperature to 100 ° C. for 1 minute to 5 hours.
  • the bonding strength between the metal and the resin can be improved.
  • radical reactive group means a functional group that reacts with a radical, and a functional group having an ethylenic carbon-carbon double bond is preferable.
  • the radical reaction group include, but are not limited to, a methacryloyl group, an acryloyl group, a vinyl group, an alkenyl group and the like.
  • the compound having a radical reactive group include a compound having a hydroxyl group, a carboxy group, an isocyanato group, a styryl group and the like, and having a (meth) acryloyl group and an alkenyl group.
  • the method for treating with the compound having a radical reactive group is not particularly limited, and examples thereof include a spray coating method and a dipping method. Specifically, for example, a diluted solution obtained by diluting a compound having a radical reactive group with an organic solvent to a concentration of about 5% by mass to 50% by mass is heated to room temperature to 100 ° C. and contained in this diluted solution. Examples thereof include a method in which the material is immersed for 1 minute to 5 days, then the material is taken out and dried at room temperature to 100 ° C. for 1 minute to 5 hours.
  • the method of treating with the compound having a radical reactive group it is preferable to wash the surface into which the functional group is introduced by the compound having the radical reactive group with an organic solvent or the like.
  • the bonding strength between the metal and the resin is improved by removing the compound having a radical reactive group or the compound derived from the compound having a radical reactive group remaining on the functional group introduced by a chemical bond with a weak adsorptive force by washing. Can be made to.
  • the compound used for imparting a functional group is preferably a compound corresponding to (i) and (ii), and is preferably an alkoxysilane compound, a compound having a mercapto group, and an isocyanato group. It is more preferable that the compound has the above, and it is further preferable that it is an alkoxysilane compound.
  • the resin is not particularly limited, but is preferably a thermoplastic resin.
  • the thermoplastic resin may be a general synthetic resin, for example, a general-purpose resin such as polypropylene (PP), polyethylene (PE), polystyrene (PS), polymethylmethacrylate (PMMA), polyvinyl chloride (PVC); Polyester resin such as polycarbonate (PC), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyamide resin such as polyamide 6 (PA6), polyamide 66 (PA66), polyacetal (POM), modified polyphenylene ether (m-PPE).
  • PP polypropylene
  • PE polyethylene
  • PS polystyrene
  • PMMA polymethylmethacrylate
  • PVC polyvinyl chloride
  • Polyester resin such as polycarbonate (PC), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyamide resin such as polyamide 6 (PA6), polyamide 66 (PA66
  • thermoplastic resin is not particularly limited, but PP, PC, PBT, PA6, PA66, and PPS are preferable from the viewpoint of obtaining a bonded body in which the metal and the resin are bonded with sufficient bonding strength.
  • the resin may be composed of only the resin, or may be a fiber reinforced plastic (FRP) reinforced with glass fiber or carbon fiber.
  • the resin is preferably a preformed molded product, or may be formed as a coating film. Examples of the form of the resin include bulk, film, sheet, FRP molded product and the like. It may be one kind selected from these, or it may be a complex of two or more kinds.
  • the method for producing the resin and the molding method of the above-mentioned embodiment are not particularly limited, and in the present embodiment, the resin obtained by a known method can be applied.
  • the resin may contain, for example, a colorant such as a pigment, a filler, an antioxidant, an additive such as an ultraviolet inhibitor, and the like.
  • the intermediate resin layer in the present embodiment is a layer that causes a chemical reaction by high-frequency induction welding, and refers to a layer that is interposed between the metal and the resin to be bonded and the metal and the resin are bonded.
  • the chemical reaction is preferably a polyaddition reaction, a radical polymerization reaction, and a crosslinking reaction from the viewpoint of obtaining sufficient bonding strength and the strength of the intermediate resin layer.
  • the intermediate resin layer also forms a chemical bond with the functional group existing on the metal surface, and the metal and the intermediate resin layer have strong adhesiveness.
  • the intermediate resin layer may be one layer or a plurality of layers.
  • the intermediate resin layer is a primer layer laminated on the metal, and at least the outermost layer of the primer layer polymerizes the in-situ polymerization type composition on the metal. It is preferably an in-situ polymerization type polymer layer.
  • the intermediate resin layer comprises reacting the in-situ polymerization type composition with at least one reaction selected from a polyaddition reaction and a radical polymerization reaction, and further described by the high frequency induction welding. It is preferably a thermoplastic resin film that causes a reaction.
  • the intermediate resin layer is in a B-stage state with a thermoplastic resin layer obtained by subjecting a field-polymerized composition to at least one reaction selected from a polyaddition reaction and a radical polymerization reaction.
  • a multilayer structure film containing a thermosetting resin layer is preferable.
  • the in-situ polymerization type composition in the present embodiment means that a composition containing a reactive bifunctional compound in a predetermined combination is subjected to a double addition reaction on the site, that is, on various materials, or radically polymerizable.
  • a composition containing a monofunctional monomer is subjected to a radical polymerization reaction to form a thermoplastic structure, that is, a linear polymer structure.
  • the in-situ polymerization type composition is a polymerizable composition having thermoplasticity without forming a three-dimensional network having a crosslinked structure, unlike a thermosetting resin having a three-dimensional network having a crosslinked structure.
  • the thermoplastic resin film and the multilayer structure film it is not always necessary to carry out all the reactions in the field, but since they have common components, they are included in the "field polymerization type composition". do.
  • the in-situ polymerization type composition preferably contains at least one selected from the following (a) to (g).
  • (A) Combination of bifunctional isocyanate compound and compound having bifunctional hydroxyl group (b) Combination of bifunctional isocyanate compound and compound having bifunctional amino group (c) Combination of bifunctional isocyanate compound and bifunctional thiol compound Combination (d) Combination of bifunctional epoxy compound and compound having bifunctional hydroxyl group (e) Combination of bifunctional epoxy compound and bifunctional carboxy compound (f) Combination of bifunctional epoxy compound and bifunctional thiol compound (f) g) Radical polymerizable monofunctional monomer
  • the compounding ratio of the two bifunctional compounds in (a) to (g) can be set in consideration of the reactivity of the double addition reaction of both compounds.
  • the bifunctional isocyanate compound The molar equivalent ratio of the isocyanate group to the hydroxyl group of the compound having a bifunctional hydroxyl group, that is, the molar ratio of the bifunctional isocyanate compound to the compound having a bifunctional hydroxyl group is preferably 0.7 to 1.5. , More preferably 0.8 to 1.4, still more preferably 0.9 to 1.3.
  • the in-situ polymerization type composition contains at least one selected from the above (a) to (g), as a catalyst for the polyaddition reaction, for example, triethylamine, 2,4,6-tris (dimethylamino).
  • a tertiary amine such as methyl) phenol-a phosphorus compound such as triphenylphosphine is preferably used.
  • the polymerization initiator for the radical polymerization reaction for example, known organic peroxides, photoinitiators and the like are preferably used.
  • a room temperature radical polymerization initiator in which a cobalt metal salt or amines are combined with an organic peroxide may be used.
  • the organic peroxide include those classified into ketone peroxide, peroxyketal, hydroperoxide, diallyl peroxide, diacyl peroxide, peroxyester, and peroxydicarbonate.
  • the photopolymerization initiator is preferably one capable of initiating radical polymerization by irradiation with light in the wavelength range of ultraviolet rays to visible light. These may be used alone or in combination of two or more. Of these, organic peroxides are preferred.
  • the bifunctional isocyanate compound is a compound having two isocyanato groups, for example, hexamethylene diisocyanate, tetramethylene diisocyanate, dimerate diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI) or a mixture thereof.
  • TDI hexamethylene diisocyanate
  • tetramethylene diisocyanate dimerate diisocyanate
  • TDI 2,4- or 2,6-tolylene diisocyanate
  • P-Phenylylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate (MDI) and the like are preferable from the viewpoint of the strength of the intermediate resin layer.
  • the compound having a bifunctional hydroxyl group is a compound having two hydroxyl groups, and is, for example, an aliphatic glycol compound such as ethylene glycol, propylene glycol, diethylene glycol, and 1,6-hexanediol; bisphenol A, bisphenol F, and bisphenol S.
  • Examples thereof include bifunctional phenol compounds such as. These may be used alone or in combination of two or more. Of these, propylene glycol, diethylene glycol and the like are preferable from the viewpoint of the toughness of the intermediate resin layer.
  • a bifunctional phenol compound is preferable, bisphenols are more preferable, and bisphenol A and bisphenol S are further preferable.
  • the bifunctional amino compound is a compound having two amino groups, and is, for example, ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 1,4-diaminobutane, 1,6-hexamethylenediamine, and the like.
  • the bifunctional thiol compound is a compound having two mercapto groups, for example, 1,4-bis (3-mercaptobutylyloxy) butane which is a bifunctional secondary thiol compound (for example, "Carens MT (registered)”. Trademark) BD1 ”(manufactured by Showa Denko KK)) and the like.
  • the bifunctional thiol compound may be used alone or in combination of two or more.
  • the bifunctional epoxy compound is a compound having two epoxy groups, and is, for example, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a biphenol type epoxy resin, a naphthalene type bifunctional epoxy resin, or the like.
  • Aromatic epoxy resins examples thereof include aliphatic epoxy compounds such as 1,6-hexanediol diglycidyl ether. These may be used alone or in combination of two or more.
  • bisphenol A type epoxy resin is preferable from the viewpoint of the strength of the intermediate resin layer. Specific products include "jER (registered trademark) 828, 834, 1001, 1004, 1007, YX-4000" (all manufactured by Mitsubishi Chemical Corporation).
  • an epoxy compound having a special structure can be used as long as it is bifunctional.
  • the bifunctional carboxy compound is a compound having two carboxy groups, and examples thereof include succinic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, isophthalic acid, and terephthalic acid. These may be used alone or in combination of two or more. Of these, isophthalic acid, terephthalic acid, adipic acid and the like are preferable from the viewpoint of the strength and toughness of the intermediate resin layer.
  • the radically polymerizable monofunctional monomer is a monomer having one ethylenically unsaturated bond.
  • styrene monomers styrene-based monomers such as ⁇ -, o-, m-, p-alkyl, nitro, cyano, amide, ester derivatives, chlorstyrene, vinyltoluene, divinylbenzene, etc.
  • the radically polymerizable monofunctional monomer is the main component among the components other than the solvent of the in-situ polymerization type composition.
  • the main component means that the content of the radically polymerizable monofunctional monomer is 50 to 100% by mass.
  • the content is preferably 60% by mass or more, more preferably 80% by mass or more.
  • the in-situ polymerization type composition preferably contains (d), and more preferably contains a bifunctional phenol compound and a bifunctional epoxy resin, from the viewpoint of bonding the metal and the resin with more sufficient bonding strength. It is more preferable to contain bisphenol A and bisphenol A type epoxy resin, or bisphenol S and bisphenol A type epoxy resin, and even more preferably to contain bisphenol S and bisphenol A type epoxy resin.
  • the in-situ polymerization type composition is a polymer capable of imparting toughness such as a rubber component such as a carboxy group-terminated butadiene nitrile rubber, an aromatic polyetherketone, a silicon elastomer, and an acrylic resin. It is preferable to include.
  • a rubber component such as a carboxy group-terminated butadiene nitrile rubber, an aromatic polyetherketone, a silicon elastomer, and an acrylic resin.
  • the aromatic polyetherketone include polyetheretherketone (PEEK) and the like.
  • the silicon elastomer include "DOWNSIL EP-2600" (manufactured by The Dow Chemical Company) and "DOWNSIL EP-2601" (manufactured by The Dow Chemical Company).
  • acrylic resin examples include methyl methacrylate-butadiene styrene-styrene copolymer (MBS) such as "BTA-730" (manufactured by The Dow Chemical Company), polymethyl methacrylate (PMMA) and the like.
  • MFS methyl methacrylate-butadiene styrene-styrene copolymer
  • PMMA polymethyl methacrylate
  • the in-situ polymerization type composition may contain maleic anhydride-modified polyolefin in addition to the above (a) to (g).
  • Maleic anhydride-modified polypropylene is polypropylene graft-modified with maleic anhydride.
  • Specific products include "Kayabrid 002PP”, “002PP-NW”, “003PP”, “003PP-NW” (all manufactured by Akzo Nobel), and "Modic (registered trademark)” series (manufactured by Mitsubishi Chemical Corporation). And so on.
  • the polypropylene additive functionalized with maleic anhydride "SCONA TPPP2112GA”, “TPPP8112GA”, and “TPPP9212GA” (all manufactured by BYK) may be used in combination.
  • the in-situ polymerization type composition preferably contains a maleic anhydride-modified polyolefin.
  • the in-situ polymerization type composition may contain a solvent and any additive such as a colorant and an antioxidant, if necessary. If the in-situ polymerization type composition is liquid, it is not necessary to use a solvent.
  • the solvent include methyl ethyl ketone, methyl isobutyl ketone, acetone, ethyl acetate, toluene, xylene, tetrahydrofuran, water and the like.
  • the thermoplastic resin film in the present embodiment is a film that is interposed between the resins to be bonded to the metal and can bond the metal to the resin by high frequency induction welding. Then, the in-situ polymerization type composition is subjected to at least one reaction selected from a polyaddition reaction and a radical polymerization reaction, and the reaction is further caused by the high frequency induced welding. That is, the film is in the middle of the reaction (the reaction is not completed).
  • the primer layer in the present embodiment is a layer laminated on a metal, which is interposed between the resins to be bonded to the metal, and is a layer capable of bonding the metal and the resin by high frequency induction welding. ..
  • the primer layer is composed of one layer or a plurality of layers, and at least the outermost layer is a field-polymerized polymer layer obtained by polymerizing a field-polymerized composition on the metal.
  • the "outermost layer” refers to the surface on the opposite side to the metal, and is the surface that comes into direct contact with the resin at the time of joining.
  • the primer layer undergoes a chemical reaction by high-frequency induction welding.
  • 1 and 2 show schematic cross-sectional views of a bonded body in which a metal and a resin are bonded, wherein the intermediate resin layer according to one embodiment of the present embodiment is a primer layer.
  • the primer layer 3 is preferably laminated in direct contact with the metal 1 as shown in FIG.
  • the functional group layer 4 is a layer formed by the functional group imparting treatment.
  • the primer layer may be composed of a plurality of layers including the in-situ polymerization type polymer layer.
  • the primer layer may include one or a plurality of thermosetting resin layers in addition to the in-situ polymerization type polymer layer.
  • thermosetting resin constituting the thermosetting resin layer include urethane resin, epoxy resin, vinyl ester resin, and unsaturated polyester resin. These may be used alone or in combination of two or more.
  • the thickness of the primer layer depends on the type of metal and resin materials, the contact area of the bonded portion, etc., but is due to the difference in the coefficient of thermal expansion between the metal and the resin in order to obtain sufficient bonding strength. From the viewpoint of suppressing thermal deformation of the obtained bonded body, it is preferably 1 ⁇ m to 10 mm, more preferably 10 ⁇ m to 8 mm, still more preferably 50 ⁇ m to 5 mm.
  • the thickness of the primer layer shall be the total value of the thickness of each layer.
  • Each layer of the primer layer may contain any additive such as a colorant and an antioxidant, if necessary, within a range in which sufficient bonding strength obtained by high-frequency induction welding of the primer layer can be obtained. good.
  • a solution containing the field-polymerized composition and a solvent is applied onto the metal or functional group-containing layer, and the field-polymerized composition is subjected to a double addition reaction. It can be obtained by polymerizing by at least one reaction selected from radical polymerization reactions, that is, by causing a chemical reaction.
  • the coating method for forming the in-situ polymerization type polymer layer contained in the primer layer is not particularly limited, and for example, a dipping method, a spray coating method, or the like can be used.
  • the concentration of the in-situ polymerization type composition is about 0.5 to 50% by mass, and the metal is immersed in a solution at room temperature to 100 ° C. for 1 minute to 5 days, and then at room temperature to
  • the in-situ polymerization type polymer layer is formed by drying at a temperature within the range of 100 ° C. for 1 minute to 5 hours, then heating to a temperature within the range of room temperature to 200 ° C. and leaving it for 5 to 120 minutes. Can be done.
  • the metal immersed in the solution for 1 minute to 5 days is irradiated with ultraviolet rays or visible light at a temperature within the range of room temperature to 100 ° C. for 10 seconds to 60 minutes. By doing so, the in-situ polymerization type polymer layer can be formed.
  • the spray method for example, a solution having a concentration of about 0.5 to 50% by mass of the in-situ polymerization type composition is sprayed on the metal 1 at a temperature in the range of room temperature to 100 ° C. for 1 minute to 5 hours. After drying, the in-situ polymerization type polymer layer can be formed by leaving it at a temperature in the range of room temperature to 200 ° C. for 5 to 120 minutes.
  • the primer layer is formed by photocuring
  • the in-situ polymerization type polymer layer can be formed by irradiating with ultraviolet rays or visible light at a temperature in the range of room temperature to 100 ° C. for 10 seconds to 60 minutes.
  • the method for forming the layer is not particularly limited, and the same method as the field-polymerized polymer layer can be used. ..
  • thermoplastic resin film in the present embodiment is a film that is interposed between the resins to be bonded to the metal and can bond the metal to the resin by high frequency induction welding. Then, the in-situ polymerization type composition is subjected to at least one reaction selected from a polyaddition reaction and a radical polymerization reaction, and the reaction is further caused by the high frequency induced welding. That is, the film is in the middle of the reaction (the reaction is not completed).
  • 3 and 4 show schematic cross-sectional views of a bonded body in which a metal and a resin are bonded, wherein the intermediate resin layer according to another aspect of the present embodiment is a thermoplastic resin film.
  • thermoplastic resin film 5 is preferably placed in direct contact with the metal 1 as shown in FIG. 3 or via a functional group-containing layer 4 which is a part of the metal 1 as shown in FIG.
  • the method for producing the thermoplastic resin film is not particularly limited, but for example, a solution obtained by dissolving the in-situ polymerization type composition in a solvent is applied onto the release film, and the environment is at room temperature to 40 ° C. It can be produced by allowing the solvent to volatilize by leaving it underneath for 1 minute to 5 hours and then leaving it at room temperature to 200 ° C. for 1 to 60 minutes to allow the reaction to proceed halfway.
  • the thickness of the thermoplastic resin film depends on the type of metal and resin, the contact area of the bonded portion, etc., but is due to the difference in the thermal expansion coefficient between the metal and the resin in order to obtain sufficient bonding strength.
  • the size is preferably 1 ⁇ m to 5 mm, more preferably 5 ⁇ m to 2 mm, still more preferably 10 ⁇ m to 1 mm.
  • the crushed thermoplastic resin film is emulsified in water or the like using an emulsifier to form the emulsion, which is applied onto the metal 1 in the form of an emulsion and subjected to heavy addition.
  • the intermediate resin layer can also be formed by advancing at least one reaction selected from the reaction and the radical polymerization reaction.
  • the multilayer structure film in the present embodiment is a film that is interposed between the resin to be bonded to the metal and can bond the metal to the resin by high frequency induction welding. Then, it contains a thermoplastic resin layer obtained by subjecting the in-situ polymerization type composition to at least one reaction selected from a polyaddition reaction and a radical polymerization reaction, and a thermosetting resin layer in a B stage state (semi-curing state). Further, the thermosetting resin layer in the B stage state is one in which a cross-linking reaction (curing reaction occurs) from the B stage state (semi-curing state) due to high frequency induction welding, that is, a chemical reaction occurs.
  • the multilayer structure film 6 in FIGS. 5 and 6 is a film containing a thermosetting resin layer in a B-stage state (semi-cured state) before the metal and the resin are bonded by high-frequency induction welding, and is high-frequency induction welding. This is a film after a cross-linking reaction, that is, a chemical reaction has occurred.
  • the multilayer structure film 6 is preferably arranged in direct contact with the metal 1 as shown in FIG. 5 or via a functional group-containing layer 4 which is a part of the metal 1 as shown in FIG.
  • the multilayer structure film may include a layer other than the thermoplastic resin layer and the thermosetting resin layer in the B stage state.
  • thermoplastic resin layer contained in the multilayer structure film is not completed even if at least one reaction selected from the polyaddition reaction and the radical polymerization reaction of the in-situ polymerization type composition is completed. May be in the middle.
  • thermosetting resin layer in the B stage state is preferably one in which the unsaturated group contained in the thermoplastic resin layer is radically polymerized or the epoxy group is ring-opened polymerized by high frequency induction welding.
  • the production of the multilayer structure film is not particularly limited, but is, for example, produced by forming the thermoplastic resin layer and then providing a B-stage thermosetting resin layer on the thermoplastic resin layer. be able to. Specifically, a solution obtained by dissolving the in-situ polymerization type composition in a solvent is applied onto a release film and left at room temperature to 40 ° C. for 1 minute to 5 hours to volatilize the solvent. At least one reaction selected from the double addition reaction and the radical polymerization reaction is carried out at room temperature to 200 ° C. for 60 to 120 minutes to form the thermoplastic resin layer. In this case, the temperature may be changed rather than constant, and the reaction may be completed or may be in progress.
  • thermosetting resin layer in the B stage state on the thermoplastic resin layer by at least one method selected from the following (1) to (4) to produce the multilayer structure film. ..
  • a peroxide catalyst for high temperature curing that functions as a catalyst at 80 to 150 ° C. and an epoxy curing agent for normal temperature curing that functions as a curing agent at room temperature to 40 ° C. are added to a resin having an unsaturated group and an epoxy group. After mixing to obtain a resin composition, the resin composition was applied onto the thermoplastic resin layer, and then left at room temperature to 40 ° C. for 1 minute to 10 hours to proceed with ring-opening polymerization of the epoxy group. Manufactures multi-layered films.
  • a resin having an unsaturated group and an epoxy group is mixed with a photoinitiator for the purpose of radical polymerization of the unsaturated group and an epoxy curing agent for high temperature curing that functions as a curing agent at 80 to 200 ° C.
  • a composition is obtained, the resin composition is applied onto the thermoplastic resin layer, and then light irradiation is performed for 0.1 to 5 minutes to proceed with radical polymerization of unsaturated groups to produce the multilayer structure film.
  • a resin composition is obtained by adding and mixing a polyisocyanate compound and a peroxide catalyst for high temperature curing that functions as a catalyst at 80 to 150 ° C. to a vinyl ester resin, and the resin composition is used as the thermoplastic resin.
  • the reaction between the hydroxyl group of the vinyl ester resin skeleton and the isocyanate compound is promoted by leaving it at room temperature to 40 ° C. for 1 to 60 minutes to produce the multilayer structure film.
  • a resin composition is obtained by adding and mixing a peroxide catalyst for high-temperature curing that functions as a catalyst at 80 to 150 ° C. and a near-infrared radical polymerization catalyst to a vinyl ester resin, and the resin composition is subjected to the thermoplasticity.
  • the vinyl ester resin is subjected to radical polymerization by irradiating it with near infrared rays for 0.5 to 5 minutes to produce the multilayer structure film.
  • the multilayer structure film can be produced by the methods (1) and (3) from the viewpoint of the adhesiveness between the thermoplastic resin and the thermosetting resin layer in the B stage state. (3) is preferable, and (3) is more preferable.
  • the multilayer structure film preferably directly bonds the thermosetting resin layer in the B stage state to the metal, and directly bonds the thermoplastic resin layer to the resin. Is preferable.
  • the multilayer structure film contains a layer other than the thermoplastic resin layer and the thermosetting resin layer in the B stage state, the other layer is the thermosetting resin and the thermosetting in the B stage state. It is preferably a layer interposed between the sex resin layer.
  • the thickness of the multilayer structure film depends on the type of metal and resin, the contact area of the bonded portion, and the like, but in order to obtain sufficient bonding strength and due to the difference in the coefficient of thermal expansion between the metal and the resin. From the viewpoint of suppressing the occurrence of thermal deformation of the obtained bonded body, it is preferably 1 ⁇ m to 10 mm, more preferably 10 ⁇ m to 5 mm, and further preferably 20 ⁇ m to 1 mm.
  • high-frequency induction welding refers to a method of melting and welding a material from the inside by dielectric heating with high frequency.
  • the high-frequency induction welding in the present embodiment is performed by arranging the metal and the resin so as to be bonded via the intermediate resin layer. According to this embodiment, the metal and the resin can be bonded with sufficient bonding strength.
  • Examples of the device used in the high-frequency induction welding include a high-frequency heating device having a power supply unit and a heating coil unit (high-frequency bar) that generates a strong high-frequency electric field.
  • a high-frequency induction welding device is a device that generates a magnetic field whose direction and strength change when an alternating current is passed through the conductor of the heating coil, and a current flows through the metal installed in the generated magnetic field. It generates heat due to Joule heat generated by the electrical resistance of the metal.
  • the high frequency welding device a known one can be used.
  • the electromagnetic induction welders “UH-2.5K”, “UH-5K”, “UHT-1002F”, “UHT-1500”, “UHT-5002”, “UHT-5002” manufactured by Seidensha Electronics Co., Ltd.
  • Examples include “UHT-15002”, “UHT-502”, “UHT-1002”, and a high frequency welder “PLASEST-8 x XD” manufactured by Yamamoto Vinita Co., Ltd.
  • the oscillation frequency in the high frequency induction welding may be in the range of 1 to 1500 kHz.
  • the oscillation frequency may be adjusted to an appropriate level according to the size and type of the metal and the resin, and the components of the intermediate resin layer.
  • the output in the high frequency induction welding is in the range of 0.1 to 2000 W.
  • the oscillation time in the high-frequency induction welding may be adjusted according to the size and type of the metal and the resin, and the components of the intermediate resin layer, and is, for example, preferably 1.0 to 10.0 seconds, more preferably. Is 1.5 to 8.0 seconds.
  • the bonded body in the present embodiment is formed by bonding a metal and a resin via an intermediate resin layer that causes a chemical reaction by high-frequency induction welding, and is the present embodiment. It is a metal-resin junction obtained by the metal-resin bonding method of.
  • the bonded body is a primer layer in which an intermediate resin layer is laminated on the metal, and at least the outermost layer of the primer layer is a field-polymerized composition on the metal. It is preferable that the in-situ polymerization type polymer layer is polymerized with.
  • the intermediate resin layer is formed by subjecting the in-situ polymerization type composition to at least one reaction selected from a polyaddition reaction and a radical polymerization reaction, and the high frequency welding is performed. It is preferable that the thermoplastic resin film further causes the above reaction.
  • the bonded body is a thermoplastic resin layer obtained by subjecting the intermediate resin layer to at least one reaction selected from a polyaddition reaction and a radical polymerization reaction of the in-situ polymerization type composition. A multilayer structure film containing a thermosetting resin layer in a B-stage state is preferable.
  • Table 1 shows the details of the metal used for producing the metal test piece in the following Examples and Comparative Examples.
  • the metal made of each of the following materials had a size of 18 mm ⁇ 45 mm.
  • each resin test piece 10 mm ⁇ 45 mm ⁇ 3 mm
  • each resin test piece was injection-molded by an injection molding machine "SE100V" (manufactured by Sumitomo Heavy Industries, Ltd.) under each condition shown in Table 2 below to obtain a size of 10 mm ⁇ 45 mm ⁇ 3 mm.
  • SE100V injection molding machine
  • Plasma treatment was performed on the surface of the metal test piece using the atmospheric pressure plasma processing device "Openair-Plasma (registered trademark) generator FG5001" (manufactured by Plasmatreat) under the conditions of an irradiation distance of 15 mm and a feed rate of 5 m / min. ..
  • ⁇ In-situ polymerization type composition 2 5 g of maleic anhydride-modified polypropylene "Modic (registered trademark) ER321P" (manufactured by Mitsubishi Chemical Corporation) and 95 g of xylene were mixed and heated to 125 ° C. with stirring to dissolve the maleic anhydride-modified polypropylene. Subsequently, 1.01 g of the bifunctional epoxy resin "jER (registered trademark) 1001" (bisphenol A type epoxy resin manufactured by Mitsubishi Chemical Corporation, molecular weight of about 900), 0.24 g of bisphenol A, and 0.006 g of triphenylphosphine were added and dissolved. , Cooled to room temperature to obtain an in-situ polymerization type composition 2.
  • jER registered trademark
  • triphenylphosphine triphenylphosphine
  • a metal test piece with a primer layer was obtained by the same method except that the field-polymerized composition 2 was used instead of the field-polymerized composition 1 in the metal test piece 1 with a primer layer.
  • TEC7785--12 manufactured by Nagase ChemteX Corporation
  • the adhesive 1 was evenly applied with a rod in a 180 ° C. dryer using a 20 ⁇ m spacer so that the thickness was 20 ⁇ m, and a metal test piece with a primer layer was obtained.
  • ⁇ Metal test piece with primer layer using adhesive 2> As a pretreatment, an acrylic hot melt adhesive "UX801" (adhesive manufactured by Nagase ChemteX Corporation) melted at 180 ° C. on the surface of one side of a metal test piece subjected to plasma treatment only or plasma treatment and functional group addition treatment 1. 2) was evenly applied with a rod using a 20 ⁇ m spacer in a 180 ° C. dryer so as to have a thickness of 20 ⁇ m, and a metal test piece with a primer layer was obtained.
  • UX801 acrylic hot melt adhesive manufactured by Nagase ChemteX Corporation
  • thermoplastic resin film 1 [Preparation of in-situ polymerization type thermoplastic resin film] ⁇ In-situ polymerization type thermoplastic resin film 1>
  • the in-situ polymerization type composition 1 is applied by a spray method on a PTFE film, which is a release film, so that the thickness after drying is 30 ⁇ m, and the solvent is volatilized by leaving it in the air at room temperature for 30 minutes.
  • the heavy addition reaction was slightly advanced in a furnace at a temperature of 100 ° C. for 5 minutes, then allowed to cool to room temperature, and then peeled off from the release film, leaving room for the polymerization reaction (in a semi-cured state). An in-situ polymerization type thermoplastic resin film 1 was obtained.
  • thermoplastic resin film 2 The in-situ polymerization type thermoplastic resin film 2 which left room for the polymerization reaction by the same method as the production of the in-situ polymerization type thermoplastic resin film 1 except that the double addition reaction was carried out in the furnace at a temperature of 150 ° C. for 5 minutes. Was produced.
  • thermoplastic resin film 1 Preparation of polymerization-completed thermoplastic resin film.
  • the in-situ polymerization type composition 1 is applied by a spray method on a PTFE film which is a release film so that the thickness after drying is 30 ⁇ m, and the solvent is volatilized by leaving it in the air at room temperature for 30 minutes.
  • the heavy addition reaction was carried out in a furnace at a temperature of 160 ° C. for 2 hours, then allowed to cool to room temperature, then peeled off from the release film and completely polymerized (the heavy addition reaction was completed). A thermoplastic resin film was obtained.
  • thermosetting resin composition 1 was prepared. Subsequently, the in-situ polymerization type composition 1 was sprayed onto a PTFE film, which is a release film, so that the thickness after drying was 30 ⁇ m, and left in the air at room temperature for 30 minutes. After volatilizing the solvent, the heavy addition reaction was carried out for 10 minutes in a furnace at a temperature of 150 ° C.
  • thermosetting resin composition 1 is applied onto the obtained thermoplastic resin film i so that the thickness after drying is 30 ⁇ m, and the epoxy group is cured at room temperature by leaving it at room temperature for 3 hours, and then PTFE is obtained.
  • the film was peeled off to obtain a two-layer structure film 1 (radical polymerizable type) having a thermoplastic resin layer and a thermosetting resin layer in a B-stage state.
  • thermosetting resin composition 2 was applied onto the thermoplastic resin film i produced in the same manner as described above so that the thickness after drying was 20 ⁇ m, and the thermosetting resin composition 2 was left at room temperature for 3 hours to form a methacryloyl group. Was cured at room temperature, and then the PTFE film was peeled off to obtain a two-layer structure film 2 (epoxy-curable type) having a thermoplastic resin layer and a thermosetting resin layer in a B-stage state.
  • thermosetting resin composition 3 Vinyl ester resin "Lipoxy (registered trademark) R-806" (manufactured by Showa Denko KK) 100 g, diphenylmethane diisocyanate “Millionate MR-100" (manufactured by Tosoh Corporation) 3.0 g, and peroxide catalyst "Perbutyl Z” (Manufactured by Nichiyu Co., Ltd.) 1.0 g was mixed to obtain a thermosetting resin composition 3. Subsequently, the thermosetting resin composition 3 was applied onto the thermoplastic resin film i so that the thickness after drying was 20 ⁇ m, and the mixture was allowed to stand at 40 ° C.
  • a two-layer structure film 3 (radical polymerization type) having a thermoplastic resin layer and a thermosetting resin layer in a B stage state.
  • thermosetting resin composition 3 is applied onto the thermoplastic resin film so that the thickness after drying is 20 ⁇ m, left at 40 ° C. for 3 hours to react the isocyanato group with the hydroxyl group, and then further.
  • Example 1-1 (Welding) The surface of the metal test piece with the primer layer on which the metal material is aluminum, the surface treatment is the etching treatment and the functional group addition treatment 1, and the in-situ polymerization type composition 1 is used as the primer layer.
  • Electromagnetic induction welder "UHT-1002F” (manufactured by Seidensha Electronics Co., Ltd.) with one surface of the resin test piece using PA6 as the resin overlapped so that the joint portion is 1 cm x 0.5 cm.
  • the oscillator "UH-2.5K” manufactured by Seidensha Electronics Co., Ltd.
  • high-frequency electromagnetic induction welding is performed at the oscillation frequency of 900 kHz, the output adjustment tap 4, the pressing force of 150 N, and the oscillation time shown in Table 3. This was performed to prepare a test piece P1-1 of a metal-resin bonded body.
  • the joint portion means a portion where the metal test piece and the resin test piece are overlapped with each other.
  • Example 1-1 test pieces P1-2 to P1-6 of a metal-resin junction were prepared by the same method except that the combination of the metal, the primer layer, and the resin shown in Table 3 and the oscillation time were used. did. Further, in Example 1-1, a tensile shear test was performed by the same method except that the obtained test pieces P1-2 to P1-6 were used instead of the test pieces P1-1. The measurement results are shown in Table 3.
  • Example 1-1 (Welding)
  • the metal material is aluminum, and instead of the metal test piece with a primer layer subjected to the etching treatment and the functional group addition treatment 1 as the surface treatment, the metal material is aluminum, and the surface treatment is as follows. High-frequency induction welding was attempted by the same method except that a metal test piece (without primer layer) that had been subjected to only etching treatment was used, but bonding was not possible.
  • Example 1-1 test pieces Q1-2 and Q1-5 of a metal-resin junction were prepared by the same method except that the combination of the metal, the primer layer, and the resin shown in Table 3 and the oscillation time were used. did. Further, in Example 1-1, a tensile shear test was performed by the same method except that the obtained test pieces Q1-2 and Q1-5 were used instead of the test pieces P1-1. The measurement results are shown in Table 3.
  • Comparative Examples 1-3, 1-4, 1-6 In Comparative Example 1-1, high-frequency induction welding was attempted by the same method except for the combination of the metal and the resin shown in Table 3 and the oscillation time, but the bonding could not be performed without the primer layer.
  • Example 1-1 instead of a metal test piece with a primer layer, the metal material is aluminum, an etching treatment and a functional group addition treatment 1 are performed as surface treatments, and an in-situ polymerization type composition 1 is used as a primer layer.
  • the metal material is aluminum, and the metal test piece (without primer layer) that has been subjected to the etching treatment and the functional group addition treatment 1 as the surface treatment is used.
  • Q2-1 was prepared.
  • Example 1-1 (Tensile shear strength) In Example 1-1, a tensile shear test was performed by the same method except that the test piece Q2-1 was used instead of the test piece P1-1. The measurement results are shown in Table 3.
  • Example 1-1 test pieces Q2-2 and Q2-5 of a metal-resin junction were prepared by the same method except that the combination of the metal, the primer layer, and the resin shown in Table 3 and the oscillation time were used. did. Further, in Example 1-1, a tensile shear test was performed by the same method except that the obtained test pieces Q2-2 and Q2-5 were used instead of the test pieces P1-1. The measurement results are shown in Table 3.
  • Comparative Examples 2-3, 2-4, 2-6 In Comparative Example 2-1 high frequency induction welding was attempted by the same method except that the combination of the metal and the resin shown in Table 3 and the oscillation time were set. As a result, without the primer layer, it was possible to bond when PC was used as the resin, and the test piece Q2-4 of the metal-resin bonded body could be obtained, but when PPS and PP were used. Can not be joined.
  • a tensile shear test was performed by the same method except that the test piece Q2-4 was used instead of the test piece P1-1 in Example 1-1. The measurement results are shown in Table 3.
  • Example 2-1 (Welding) In-situ polymerization type thermoplastic resin film on one side of a metal test piece that was subjected to etching treatment and functional group addition treatment 1 using aluminum as a metal and one side of a resin test piece that used PA6 as a resin. High-frequency electromagnetic induction welding was performed in the same manner as in Example 1-1 with 1 sandwiched between them and the joints were overlapped so as to have a size of 1 cm ⁇ 0.5 cm. -1 was prepared.
  • Example 1-1 (Tensile shear strength) In Example 1-1, a tensile shear test was performed by the same method except that the test piece F2-1 was used instead of the test piece P1-1. The measurement results are shown in Table 4.
  • Example 2-1 the test pieces F2-2 to F2-5 of the metal-resin bonded body were prepared by the same method except that the combination of the metal and the resin shown in Table 4 and the oscillation time were set. Further, in Example 1-1, a tensile shear test was performed by the same method except that the test pieces F2-2 to F2-5 were used instead of the test piece P1-1. The measurement results are shown in Table 4.
  • Example 3-1 (Welding) A metal-resin bonded test piece F3-1 was produced by the same method except that the field-polymerized thermoplastic resin film 2 was used instead of the field-polymerized thermoplastic resin film 1 in Example 2-1. ..
  • Example 1-1 (Tensile shear strength) In Example 1-1, a tensile shear test was performed by the same method except that the test piece F3-1 was used instead of the test piece P1-1. The measurement results are shown in Table 4.
  • Example 3-1 the test pieces F3-2 to F3-5 of the metal-resin bonded body were prepared by the same method except that the combination of the metal and the resin shown in Table 5 and the oscillation time were set. Further, in Example 1-1, a tensile shear test was performed by the same method except that the test pieces F3-2 to F3-5 were used instead of the test piece P1-1. The measurement results are shown in Table 4.
  • Example 4-1 (Welding) In Example 2-1, aluminum was used as the metal, and instead of the metal test piece subjected to the etching treatment and the functional group addition treatment 1, aluminum was used as the metal, and the etching treatment and the functional group addition treatment 2 were performed. A metal test piece is used, and a two-layer structure film 1 is used instead of the field-polymerized thermoplastic resin film 1, and one surface of the metal test piece is thermoset in the B stage state of the two-layer structure film 1. A metal-resin bonded test piece F4-1 was produced by the same method except that the sex resin layers were overlapped so as to be in contact with each other.
  • Test piece F4-1 a tensile shear strength test was carried out by the same method except that the test piece F4-1 was used instead of the test piece P1-1 in Example 1-1. The measurement results are shown in Table 5.
  • Example 4-1 test pieces F4-2 to F4-5 were prepared by the same method except for the combination of the metal and the resin shown in Table 6 and the oscillation time. Further, in Example 1-1, the tensile shear strength test was carried out by the same method except that the test pieces F4-2 to F4-5 were used instead of the test pieces P1-1. The measurement results are shown in Table 5.
  • Example 5-1 (Welding) In Example 4-1 aluminum was used as the metal, and instead of the metal test piece subjected to the etching treatment and the functional group addition treatment 2, aluminum was used as the metal, and the etching treatment and the functional group addition treatment 1 were performed. A metal test piece is used, and a two-layer structure film 2 is used instead of the two-layer structure film 1, and one surface of the metal test piece is a heat-curable resin layer in the B stage state of the two-layer structure film 2. A metal-resin bonded test piece F5-1 was prepared by the same method except that they were overlapped so as to be in contact with each other.
  • Test piece F5-1 a tensile shear strength test was carried out by the same method except that the test piece F5-1 was used instead of the test piece P1-1 in Example 1-1. The measurement results are shown in Table 5.
  • Example 5-1 test pieces F5-2 to F5-5 of the metal-resin bonded body were prepared by the same method except that the combination of the metal and the resin shown in Table 5 and the oscillation time were set. Further, in Example 1-1, a tensile shear test was performed by the same method except that the test pieces F5-2 to F5-5 were used instead of the test pieces P1-1. The measurement results are shown in Table 5.
  • Example 6-1 (Welding) In Example 4-1 the two-layer structure film 3 is used instead of the two-layer structure film 1, and one surface of the metal test piece is in contact with the thermosetting resin layer in the B stage state of the two-layer structure film 3.
  • a metal-resin bonded test piece F6-1 was produced by the same method except that the films were overlapped with each other.
  • Test piece F6-1 (Tensile shear strength) With respect to the test piece F6-1, a tensile shear strength test was carried out by the same method except that the test piece F6-1 was used instead of the test piece P1-1 in Example 1-1. The measurement results are shown in Table 5.
  • Example 6-1 the test pieces F6-2 to F6-5 were prepared by the same method except for the combination of the metal and the resin shown in Table 5 and the oscillation time. Further, in Example 1-1, a tensile shear test was performed by the same method except that the test pieces F6-2 to F6-5 were used instead of the test piece P1-1. The measurement results are shown in Table 5.
  • Example 1-1 (Tensile shear strength) In Example 1-1, a tensile shear test was performed by the same method except that the test pieces Q3-1 and Q3-2 were used instead of the test pieces P1-1. The measurement results are shown in Table 6.
  • Example 2-1 the test pieces Q3-3 and Q3-4 of the metal-resin bonded body were prepared by the same method except that the combination of the metal, the film and the resin shown in Table 6 and the oscillation time were set. Further, in Example 1-1, a tensile shear test was performed by the same method except that the test pieces Q3-3 and Q3-4 were used instead of the test pieces P1-1. The measurement results are shown in Table 6.
  • Example 5-5 In Example 5-5, the bonding was attempted by the same method except that the combination of the metal, the film and the resin shown in Table 6 and the oscillation time were set, but the bonding could not be performed.
  • the application of the bonded body using the metal-resin bonding method according to the present invention is not particularly limited, but for example, a door side panel, a bonnet roof, a tailgate, a steering hanger, an A pillar, a B pillar, and a C pillar. , D-pillar, crash box, power control unit (PCU) housing, electric compressor member (inner wall part, suction port part, exhaust control valve (ECV) insertion part, mount boss part, etc.), lithium ion battery (LIB) spacer, battery It can be applied to automobile parts such as cases and LED head lamps, smartphones, notebook computers, tablet computers, smart watches, large liquid crystal televisions (LCD-TVs), outdoor LED lighting structures, and the like.
  • PCU power control unit
  • ECV exhaust control valve
  • LIB lithium ion battery
  • the bonded body in which CFRP and metal are bonded can be suitably applied to applications of multi-material materials such as automobiles.
  • the bonded body obtained by joining FRP and copper foil is also suitable for use as an electronic material substrate.

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