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WO2023054278A1 - Stratifié - Google Patents

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Publication number
WO2023054278A1
WO2023054278A1 PCT/JP2022/035771 JP2022035771W WO2023054278A1 WO 2023054278 A1 WO2023054278 A1 WO 2023054278A1 JP 2022035771 W JP2022035771 W JP 2022035771W WO 2023054278 A1 WO2023054278 A1 WO 2023054278A1
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WO
WIPO (PCT)
Prior art keywords
primer layer
laminate
layer
resin
metal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2022/035771
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English (en)
Japanese (ja)
Inventor
佳世 下川
明日香 遠藤
涼平 大幡
研一 岡田
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.)
Nitto Denko Corp
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Nitto Denko Corp
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Filing date
Publication date
Application filed by Nitto Denko Corp filed Critical Nitto Denko Corp
Publication of WO2023054278A1 publication Critical patent/WO2023054278A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/022—Mechanical properties

Definitions

  • the present invention relates to laminates.
  • Metals are sometimes used in parts of sporting goods, transportation equipment, electronic equipment, housing equipment, etc.
  • Various techniques are used to achieve strong adhesion between metals and dissimilar materials such as resins.
  • Patent Document 1 by introducing phosphate ions into an oxide film formed on the surface of aluminum, a layer in which phosphate ions are bonded to the oxide film is formed, producing surface-treated aluminum with excellent adhesiveness.
  • Patent Document 2 discloses a surface treatment method for increasing affinity with adhesives and achieving high adhesion durability by forming an oxide film containing inorganic materials such as Ti and Zr on the surface of a Mg-containing aluminum alloy.
  • Patent Document 3 proposes a technique to improve adhesion reliability with an adhesive by applying a mixed primer of a silane compound and an amino-silane coupling agent to a metal surface as an alternative technique for metal welding.
  • US Pat. No. 5,200,005 comprises at least one first layer of at least one first metal and at least one further layer of a polyamide composition (PC), said polyamide composition (PC) comprising: a copolyamide prepared by polymerization of the components (A) caprolactam, (B) at least one C4-C40-dioic acid, and (C) at least one C4-C20-diamine, said copolyamide being an amide Laminates are disclosed having amide functional group concentrations ranging from 3.5 to 7 groups/1000 g/mole.
  • Japanese Patent Application Laid-Open No. 2011-122220 Japanese Patent Application Laid-Open No. 2021-105209 Japanese Patent Application Laid-Open No. 2017-043845 Japanese special table 2020-514139
  • Patent Documents 1 and 2 require electrolytic treatment, chemical conversion treatment, etc., and many chemical solutions and cleaning/sintering equipment must be used, and the process is complicated and has a high environmental impact.
  • Patent Document 4 requires a crimping process at a high temperature of about 240°C, which is expected to impose a high process load and lack environmental consideration.
  • the present invention has been made in view of the above-mentioned conventional circumstances, and provides a laminate that has a strong adhesive force between a primer layer and a metal layer and that can be easily produced at a low pressure bonding temperature (for example, 170° C. or less). are issues to be resolved.
  • the present invention relates to the following ⁇ 1> to ⁇ 9>.
  • ⁇ 1> A laminate in which a primer layer is laminated on at least a part of a metal layer,
  • the primer layer contains a polymer component containing a polyamide resin as a main component,
  • G'1/G'0>1.0 (1) In formula (1), G'1 is an arbitrary point when the laminate is viewed in the thickness direction when the primer layer and the metal layer are thermocompressed at a temperature of 150 ° C., from the interface between the primer layer and the metal layer.
  • ⁇ 4> A resin bonded body in which a resin material is laminated on at least a part of the laminate according to any one of ⁇ 1> to ⁇ 3>.
  • ⁇ 5> A metal bonded body in which a metal material is laminated on at least part of the laminate according to any one of ⁇ 1> to ⁇ 3>.
  • ⁇ 6> An adhesive joined body in which an adhesive layer is laminated on at least a part of the laminate according to any one of ⁇ 1> to ⁇ 3>.
  • ⁇ 7> At least part of the laminate according to any one of ⁇ 1> to ⁇ 3> is provided with a coating film, painted object.
  • ⁇ 8> The method for producing a laminate according to ⁇ 1>, including the step of thermally transferring the primer layer to the metal layer at a temperature equal to or higher than the melting point of the primer layer.
  • ⁇ 9> The method for producing a laminate according to ⁇ 8>, further comprising the step of providing the primer layer on at least one side of the release sheet.
  • the laminate of the present invention has a strong adhesion between the primer layer and the metal layer, and can be easily manufactured at a low crimping temperature.
  • the metal layer is less likely to peel off.
  • FIG. 1 is a schematic cross-sectional view showing an example of the laminate of the present application.
  • the laminate of the present invention is a laminate in which a primer layer is laminated on at least a part of a metal layer,
  • the primer layer contains a polymer component containing a polyamide resin as a main component,
  • the following formula (1) is satisfied.
  • G'1/G'0>1.0 (1) In formula (1), G'1 is an arbitrary point when the laminate is viewed in the thickness direction when the primer layer and the metal layer are thermocompressed at a temperature of 150 ° C., from the interface between the primer layer and the metal layer.
  • G'0 is an arbitrary point when the laminate is viewed in the thickness direction when the primer layer and the metal layer are thermocompressed at a temperature of 150 ° C., from the interface between the primer layer and the metal layer. It is the elastic modulus of the primer layer in the range from a point 0.3 ⁇ m away from the primer layer to the center of the primer layer.
  • the primer layer firmly adheres to the surface of the metal layer, thereby increasing the bonding strength of the joined body.
  • G'1/G'0 is preferably greater than 1.1 from the viewpoint of improving the adhesion between the primer layer and the metal layer.
  • G'1 and G'0 can be specifically measured by the method described in Examples.
  • the primer layer contains a polymer component containing a polyamide resin as a main component.
  • the content of the polymer component in the primer layer is preferably 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, still more preferably 90% by mass to 100% by mass, particularly It is preferably 92% to 100% by weight, most preferably 95% to 100% by weight.
  • the main component of the polymer component is polyamide resin.
  • the main component means a component contained in an amount of 50% by mass or more.
  • the content of the polyamide resin in the polymer component is preferably 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, still more preferably 90% by mass to 100% by mass, especially It is preferably 92% to 100% by weight, most preferably 95% to 100% by weight.
  • polyamide resin Any appropriate polyamide resin can be selected as the polyamide resin as long as it does not impair the effects of the present invention.
  • polyamide resins include aliphatic polyamide resins, alicyclic polyamide resins, aromatic polyamide resins, and fatty acid-modified polyamide resins. Only one type of polyamide resin may be used, or two or more types may be used in combination.
  • Polyamide resins are obtained, for example, by condensation polymerization of dicarboxylic acids such as adipic acid and dimer acid and diamines such as ethylenediamine and hexamethylenediamine.
  • polyamide resins suitable for the present invention include methoxymethyl group-containing polyamide resins and polyamide copolymer resins.
  • a commercially available product may be employed as the methoxymethyl group-containing polyamide resin.
  • Examples of such commercially available products include the "Fine Resin” (registered trademark) series (manufactured by Narimichi Co., Ltd.). Only one type of methoxymethyl group-containing polyamide resin may be used, or two or more types may be used.
  • the methoxymethyl group-containing polyamide resin has a weight average molecular weight (Mw) of preferably 1,000 to 1,000,000, more preferably 3,000 to 500,000, and still more preferably 5,000, in that the effects of the present invention can be more expressed. ⁇ 100000.
  • the polystyrene equivalent molecular weight in GPC measurement is used as the weight average molecular weight (Mw).
  • a commercially available product may be used as the polyamide copolymer resin.
  • Examples of such commercial products include "Amilan CM8000" (manufactured by Toray Industries, Inc.). Only one kind of polyamide copolymer resin may be used, or two or more kinds thereof may be used.
  • the polyamide copolymer resin has a weight average molecular weight (Mw) of preferably 1,000 to 1,000,000, more preferably 3,000 to 500,000, and still more preferably 5,000 to 200,000, in that the effects of the present invention can be further expressed. , particularly preferably 10,000 to 100,000, and most preferably 20,000 to 70,000.
  • the primer layer may further contain a cross-linking agent as an additive in addition to the polymer component.
  • the cross-linking agent may be contained in the primer layer in a form after cross-linking reaction, a form before cross-linking reaction, a form in which partial cross-linking reaction has occurred, an intermediate or composite form thereof, and the like.
  • cross-linking agents examples include organic acid-based cross-linking agents and organic peroxide-based cross-linking agents.
  • cross-linking agent Only one type of cross-linking agent may be used in the primer layer, or two or more types may be used.
  • the content of the cross-linking agent that can be contained in the primer layer is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, relative to 100 parts by mass of the polymer component, from the viewpoint of increasing elasticity. . From the viewpoint of imparting high surface tension, the amount is preferably 20 parts by mass or less, more preferably 10 parts by mass or less.
  • the type, combination, content, etc. of the cross-linking agent that can be contained in the primer layer can be appropriately set according to the purpose and desired properties.
  • the primer layer may further contain fine particles as an additive.
  • the fine particles may be inorganic fine particles or organic fine particles.
  • inorganic fine particles examples include silicon oxide fine particles (e.g., fumed silica, colloidal silica, precipitated silica, silica gel, silica airgel, quartz glass, glass fiber, etc.), titanium oxide fine particles, aluminum oxide fine particles, zinc oxide fine particles, and tin oxide. fine particles, calcium carbonate fine particles, barium sulfate fine particles, talc fine particles, kaolin fine particles, calcium sulfate fine particles, and the like.
  • silicon oxide fine particles e.g., fumed silica, colloidal silica, precipitated silica, silica gel, silica airgel, quartz glass, glass fiber, etc.
  • titanium oxide fine particles aluminum oxide fine particles, zinc oxide fine particles, and tin oxide.
  • fine particles calcium carbonate fine particles, barium sulfate fine particles, talc fine particles, kaolin fine particles, calcium sulfate fine particles, and the like.
  • organic fine particles examples include polymethyl methacrylate resin powder (PMMA fine particles), silicone resin powder, polystyrene resin powder, polycarbonate resin powder, acrylic styrene resin powder, benzoguanamine resin powder, melamine resin powder, polyolefin resin powder, and polyester resin powder. , polyamide resin powder, polyimide resin powder, polyethylene fluoride resin powder, carbon fiber, cellulose fiber, and the like.
  • Fine particles may be surface-treated as necessary. Only one type of fine particles may be used, or two or more types may be used for the fine particles that may be contained in the primer layer.
  • the content of the fine particles that can be contained in the primer layer is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and further preferably 5 parts by mass or more with respect to 100 parts by mass of the polymer component. preferable. From the viewpoint of film-forming properties, the content is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and even more preferably 30 parts by mass or less.
  • the type, combination, content, etc. of fine particles that can be contained in the primer layer can be appropriately set according to the purpose and desired properties.
  • the melting point of the primer layer is preferably 80°C to 170°C. When the melting point of the primer layer is within the above range, the compression temperature during the production of the laminate can be lowered.
  • the melting point of the primer layer is preferably 80°C to 170°C, more preferably 100°C to 150°C.
  • the melting point of the primer layer can be specifically measured by the method described in Examples.
  • the thickness of the primer layer is preferably 1 ⁇ m to 2000 ⁇ m, more preferably 5 ⁇ m to 1000 ⁇ m. Shape followability improves that thickness of a primer layer is in the above-mentioned range.
  • the primer layer can be manufactured by any suitable method. For example, a method of dipping a release sheet in a solution (primer composition) containing a primer layer material and a solvent and then drying the release sheet as necessary; A method of drying as necessary after applying with a brush, a method of applying a solution containing a primer layer material and a solvent to the surface of the release sheet with various coaters and then drying as necessary, and a method of drying as necessary on the surface of the release sheet. A method of spray coating a solution containing the material of the primer layer and a solvent, followed by drying as necessary. The release sheet will be described later.
  • Examples of the primer composition include a solution obtained by dissolving the material of the primer layer in a solvent.
  • solvents include water; alcohols such as methanol, ethanol and isopropyl alcohol (IPA); ketones such as methyl ethyl ketone; esters; aliphatic, alicyclic and aromatic hydrocarbons; halogenated hydrocarbons; amides such as dimethyl sulfoxide; ethers such as dimethyl ether and tetrahydrofuran; Only one kind of solvent may be used, or two or more kinds thereof may be used.
  • solvents include water; alcohols such as methanol, ethanol and isopropyl alcohol (IPA); ketones such as methyl ethyl ketone; esters; aliphatic, alicyclic and aromatic hydrocarbons; halogenated hydrocarbons; amides such as dimethyl sulfoxide; ethers such as dimethyl ether and tetrahydrofuran; Only one kind of solvent may be used, or
  • the solid content concentration in the primer composition can be appropriately set according to the purpose. From the viewpoint of thickness accuracy of the primer layer, the solid content concentration is preferably 1% by mass to 40% by mass, more preferably 10% by mass to 35% by mass, and still more preferably 15% by mass to 30% by mass. be.
  • the primer composition may contain pH adjusters, cross-linking agents, viscosity adjusters (thickeners, etc.), leveling agents, release adjusters, plasticizers, softeners, fillers, colorants (pigments, dyes etc.), surfactants, antistatic agents, preservatives, anti-aging agents, UV absorbers, antioxidants, light stabilizers, and other additives.
  • a coloring agent makes the primer layer visible, making it easier to determine whether the surface of the resin member has already been modified, which is advantageous in terms of process control.
  • Colorants include, for example, dyes and pigments. Further, the colorant may be a fluorescent material that can be visually recognized under black light.
  • the release sheet is not particularly limited, but preferably has a heat resistance of 100° C. or higher and a tensile elastic modulus at 100° C. of 1 GPa or lower.
  • it may be a non-silicone resin sheet or a silicone resin sheet, but it is preferably a non-silicone resin sheet.
  • polyester-based resin sheet manufactured by Nitoflon
  • polymethylpentene-based resin sheet manufactured by Mitsui Chemicals Tohcello, Opulan (registered trademark)
  • polystyrene-based resin sheet manufactured by Kurabo Industries, Oidis (registered trademark)
  • polyamide-based A resin sheet a polyolefin-based resin sheet, and the like are included.
  • the release sheet that can be used for the primer layer includes, for example, unstretched polyamide 6, unstretched polyamide 66, biaxially stretched polyamide 6, biaxially stretched polyamide 66, biaxially stretched polypropylene, biaxially stretched polyethylene terephthalate, Biaxially oriented polybutylene terephthalate, easily molded polyethylene terephthalate, cutting molded polytetrafluoroethylene (PTFE), cast molded polytetrafluoroethylene, undrawn extruded tetrafluoroethylene-ethylene copolymer (ETFE), undrawn extruded tetrafluoroethylene Examples include fluoroethylene-perfluoroalkoxyethylene copolymer (PFA), unstretched extruded tetrafluoroethylene-hexafluoropropylene joint (FEP), and laminates having these as main layers.
  • PFA fluoroethylene-perfluoroalkoxyethylene copolymer
  • FEP unstretched
  • the thickness of the release sheet is preferably 1 ⁇ m to 1000 ⁇ m, more preferably 5 ⁇ m to 500 ⁇ m, still more preferably 10 ⁇ m to 300 ⁇ m, and particularly preferably 20 ⁇ m to 100 ⁇ m, from the viewpoint of conformability.
  • the surface of the release sheet on the primer layer side or both surfaces may be subjected to a release treatment with an appropriate release agent such as silicone.
  • Metal layer examples include metal foils such as rolled metal foils and electrolytic metal foils, metal deposition films, metal plating films, and the like.
  • the metal layer may be a single layer or multiple layers.
  • the metal layer may be composed of only one kind of metal, or may be composed of two or more kinds of metals.
  • metals forming the metal layer include gold, silver, copper, aluminum, iron, titanium, and alloys containing one or more of these. Among these, copper, aluminum and titanium are preferred.
  • the thickness of the metal layer is preferably 0.01 mm to 10 mm, more preferably 0.1 mm to 5 mm.
  • the manufacturing method of the laminate of the present invention has a step of heat-transferring onto the metal layer at a temperature equal to or higher than the melting point of the primer layer. Further, in the method for producing a laminate of the present invention, a primer layer may be provided on at least one side of the release sheet.
  • the laminate of the present invention is produced, for example, by placing the primer layer side of the primer layer with a release sheet on at least a portion of the metal layer and performing thermal transfer.
  • At least part of the metal layer means at least part of all the surfaces of the metal layer.
  • the metal layer is plate-like, sheet-like, or film-like, it means part of at least one surface, or the whole of at least one surface.
  • the temperature of thermal transfer is equal to or higher than the melting point of the primer layer, preferably 80°C to 170°C, more preferably 100°C to 150°C.
  • the heat transfer method includes, for example, oven heating, infrared heating, high-frequency heating, and heat press, preferably heat press (press molding).
  • the time for thermal transfer is preferably 1 to 10 minutes.
  • a primer layer is placed on at least a part of the metal layer in a molding machine (e.g., press machine, etc.), and molding is performed with heating (e.g., integral molding by hot press). It is a mode. According to this aspect, since the metal layer can be molded at the same time, high productivity and low cost can be provided.
  • a molding machine e.g., press machine, etc.
  • Molding means processing a material into a predetermined shape regardless of whether a mold is used, and “molding” means processing a material into a predetermined shape using a mold.
  • the pressure in the heating press is preferably 0.1 MPa to 20 MPa, more preferably 1 MPa to 10 MPa.
  • the release sheet is preferably removed.
  • the method for removing the release sheet is not particularly limited, and may be manual removal, removal using dedicated peeling equipment, or the like.
  • the primer layer 20 is provided on the surface of the metal layer 10 to obtain the laminate 100, as shown in FIG.
  • the coated article of the present invention is obtained by laminating a coating film on at least a part of the laminate of the present invention.
  • the coating film is preferably laminated on the surface of the primer layer.
  • the coating film is not particularly limited, and examples thereof include epoxy-based, polyester-melamine-based, alkyd-melamine-based, acrylic-melamine-based, acrylic-urethane-based, and acrylic-polyacid curing agent-based coatings. .
  • the thickness of the coating film is not particularly limited, and is usually 0.01 ⁇ m to 2000 ⁇ m, more preferably 0.1 ⁇ m to 1000 ⁇ m, still more preferably 0.5 ⁇ m to 500 ⁇ m, particularly preferably 1 ⁇ m to 200 ⁇ m. .
  • the coating method of the coating film there are no particular restrictions on the coating method of the coating film, and general methods such as brush coating, roller coating, spray coating, and various coater coatings can be used, and the coating amount is not particularly limited.
  • the time and temperature for heating the coating film can be appropriately determined depending on the coating material to be used, the coating amount, and the like.
  • the resin bonded body of the present invention is obtained by laminating a resin material on at least a part of the laminate of the present invention.
  • the resin contained in the resin material may be a thermoplastic resin or a thermosetting resin, and is preferably a carbon fiber reinforced resin (CFRP).
  • thermoplastic resins include PP (polypropylene), PA (polyamide), PPE (polyphenylene ether), PPS (polyphenylene sulfide), PET (polyethylene terephthalate), PBT (polybutylene terephthalate), POM (polyacetal), PEEK ( polyether ether ketone), PC (polycarbonate), PES (polyether sulfide), EP (epoxy), and the like.
  • PP polypropylene
  • PA polyamide
  • PPE polyphenylene ether
  • PPS polyphenylene sulfide
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • POM polyacetal
  • PEEK polyether ether ketone
  • PC polycarbonate
  • PES polyether sulfide
  • EP
  • thermoplastic resins that can advantageously exhibit the effects of the present invention.
  • a fiber reinforced thermoplastic may be employed as the thermoplastic.
  • Fiber reinforced thermoplastic resins include, for example, carbon fiber reinforced thermoplastic resins (CFRTP) and glass fiber reinforced thermoplastic resins (GFRTP).
  • Carbon fiber reinforced thermoplastic resins include, for example, PPS carbon fiber reinforced thermoplastic resins, PA carbon fiber reinforced thermoplastic resins, PES carbon fiber reinforced thermoplastic resins, EP carbon fiber reinforced thermoplastic resins, A PP-based carbon fiber reinforced thermoplastic resin and the like are included.
  • Glass fiber reinforced thermoplastic resins include, for example, PPS glass fiber reinforced thermoplastic resins, PA glass fiber reinforced thermoplastic resins, PP glass fiber reinforced thermoplastic resins, and the like.
  • thermosetting resins examples include unsaturated polyester resins, vinyl ester resins, epoxy resins, melamine resins, phenol resins, urethane resins, polyisocyanate resins, polyisocyanurate resins, and polyimide resins.
  • Examples of the shape of the resin material include a plate shape having a flat surface, a plate shape having a curved surface, a sheet shape, a film shape, and the like.
  • the thickness of the resin material is, for example, 0.001 mm to 10 mm.
  • Examples of methods for laminating resin materials include hot pressing.
  • the conditions at that time can be appropriately determined according to the type of the resin material and the primer layer.
  • the metal bonded body of the present invention is obtained by laminating a metal material on at least a part of the laminate of the present invention.
  • metal materials include gold, silver, copper, aluminum, iron, titanium, and alloys containing one or more of these. Among these, copper, aluminum and titanium are preferred.
  • the thickness of the metal material is, for example, 0.01 mm to 10 mm.
  • Examples of methods for laminating metal materials include hot pressing.
  • the conditions at that time can be appropriately determined according to the type of the metal material and the primer layer.
  • the adhesive bonded article of the present invention is obtained by laminating an adhesive layer on at least a part of the laminate of the present invention.
  • the adhesive contained in the adhesive layer includes, for example, an acrylic resin-based adhesive, an epoxy resin-based adhesive, an amino resin-based adhesive, a vinyl resin (vinyl acetate-based polymer, etc.)-based adhesive, and a curable acrylic resin. system adhesives, silicone resin-based adhesives, and the like can be used.
  • the thickness of the adhesive layer is, for example, 0.01 mm to 2 mm.
  • Examples of methods for laminating adhesive layers include application of adhesive, transfer of adhesive layers, and heat press. The conditions at that time can be appropriately determined according to the types of the adhesive layer and the primer layer.
  • the primer layer contains a polymer component containing a polyamide resin as a main component,
  • G'1/G'0>1.0 (1) (In formula (1), G'1 is an arbitrary point when the laminate is viewed in the thickness direction when the primer layer and the metal layer are thermocompressed at a temperature of 150 ° C., from the interface between the primer layer and the metal layer.
  • a coated article comprising a coating film on at least a part of the laminate according to any one of [1] to [3].
  • the method for producing a laminate according to [1] which includes the step of thermally transferring the primer layer to the metal layer at a temperature equal to or higher than the melting point of the primer layer.
  • the resulting primer composition was applied to the release layer side of a PET release sheet (Mitsubishi Chemical DANFOIL MRF38) and dried at 100°C for 2 minutes to obtain a 10 ⁇ m-thick primer layer with a release sheet.
  • a PET release sheet Mitsubishi Chemical DANFOIL MRF38
  • ⁇ Melting point of primer layer> A primer layer was laminated to a thickness of 500 ⁇ m and cut to a diameter of 25 mm to obtain a test piece. Using a jig, a viscoelasticity apparatus ARES-G2 manufactured by TA Instruments Co., Ltd. was used to measure the temperature dispersion of the test piece at 25 to 200°C. The temperature at which the storage modulus (G') decreased due to liquefaction was defined as the melting point of the primer layer.
  • a strong adhesive tape was provided as a guide on the metal layer of the resulting joined body.
  • the metal layer side was peeled off at a rate of 300 mm/min in the direction of 180°, and the peel force (N/10 mm) was measured.
  • the width of the test piece was fixed at 10 mm.
  • the bonded body obtained above was cut with an ultramicrotome to prepare a cross section, fixed on a predetermined sample table, and an AFM force curve measurement of the interface between the metal layer and the primer layer was performed.
  • the elastic modulus G'1 of the primer layer was measured in a range from the interface to a point 0.2 ⁇ m away from the primer layer. The measurement was performed at arbitrary five points, and the average value was taken as G'1.
  • the elastic modulus G'0 of the primer layer was measured in the range from a point 0.3 ⁇ m away from the interface toward the primer layer to the center of the primer layer. The measurement was performed at arbitrary five points, and the average value was taken as G'0.
  • the conditions for measuring the elastic modulus of the primer layer were as follows. Equipment: Oxford Instruments MFP-30-SA Measurement mode: AFM force curve method Probe: Si Measurement range: 1.2 ⁇ m (128 x 128 points) Measurement atmosphere: Atmosphere Measurement temperature: Room temperature
  • Example 2 A laminate was produced and evaluated in the same manner as in Example 1 except that a 60 ⁇ m aluminum foil was used instead of the 30 ⁇ m copper foil.
  • Example 3 A laminate was prepared and evaluated in the same manner as in Example 1 except that 2 parts by mass of an acrylic resin (Alphon UC-3000 manufactured by Toa Gosei Co., Ltd.) was added to the primer composition with respect to 100 parts by mass of the modified nylon resin. gone.
  • an acrylic resin Alphon UC-3000 manufactured by Toa Gosei Co., Ltd.
  • Example 4 A laminate was produced and evaluated in the same manner as in Example 3 except that a 60 ⁇ m aluminum foil was used instead of the 30 ⁇ m copper foil.
  • Example 5 A laminate was produced and evaluated in the same manner as in Example 1, except that copolymerized nylon (Amilan CM-8000 manufactured by Toray Industries, Inc.) was used instead of the modified nylon resin.
  • copolymerized nylon Amilan CM-8000 manufactured by Toray Industries, Inc.
  • Example 6 A laminate was produced and evaluated in the same manner as in Example 5 except that a 60 ⁇ m aluminum foil was used instead of the 30 ⁇ m copper foil.
  • Example 1 A laminate was produced and evaluated in the same manner as in Example 1, except that the primer layer was not provided.
  • Comparative Example 2 A laminate was produced and evaluated in the same manner as in Comparative Example 1 except that a 60 ⁇ m aluminum foil was used instead of the 30 ⁇ m copper foil.
  • Table 1 shows the evaluation results of Examples and Comparative Examples.
  • the laminate of the present invention has a strong adhesion between the primer layer and the metal layer, and can be easily produced at a low pressure bonding temperature.

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  • Laminated Bodies (AREA)

Abstract

L'objectif de la présente invention est de fournir un stratifié qui présente une force d'adhérence élevée entre une couche d'apprêt et une couche métallique, et qui peut être fabriqué de façon pratique à de basses températures de sertissage.　La présente invention se rapporte à un stratifié obtenu par stratification d'une couche d'apprêt sur au moins une partie d'une couche métallique. La couche d'apprêt contient un constituant polymère ayant une résine polyamide en tant que principal constituant, et satisfait l'expression (1) ci-dessous.　(1) : G'(1)/G'(0) > 1. (0) (les définitions de G'(1) et G'(0) dans l'expression (1) sont telles que définies dans la description. )
PCT/JP2022/035771 2021-09-29 2022-09-26 Stratifié Ceased WO2023054278A1 (fr)

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WO2025069962A1 (fr) * 2023-09-29 2025-04-03 日東電工株式会社 Composition adhésive, feuille adhésive, stratifié pourvu d'une feuille adhésive, stratifié pourvu d'une feuille durcie, et procédé pour produire un stratifié pourvu d'une feuille durcie

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JPH06218875A (ja) * 1993-01-28 1994-08-09 Toray Ind Inc ポリアミド被覆成形体およびそれに用いるポリアミドフィルム
JP2005144674A (ja) * 2003-11-11 2005-06-09 Toray Ind Inc 金属または木質系材料と熱可塑性樹脂の一体成形体およびその製造方法
JP2020514139A (ja) * 2017-03-20 2020-05-21 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 金属及びポリアミド組成物を含有する積層体
JP2020163831A (ja) * 2019-03-29 2020-10-08 日東電工株式会社 積層体の製造方法、塗装物の製造方法、接合構造体の製造方法、熱転写シート、及び積層体

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06218875A (ja) * 1993-01-28 1994-08-09 Toray Ind Inc ポリアミド被覆成形体およびそれに用いるポリアミドフィルム
JP2005144674A (ja) * 2003-11-11 2005-06-09 Toray Ind Inc 金属または木質系材料と熱可塑性樹脂の一体成形体およびその製造方法
JP2020514139A (ja) * 2017-03-20 2020-05-21 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 金属及びポリアミド組成物を含有する積層体
JP2020163831A (ja) * 2019-03-29 2020-10-08 日東電工株式会社 積層体の製造方法、塗装物の製造方法、接合構造体の製造方法、熱転写シート、及び積層体

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025069962A1 (fr) * 2023-09-29 2025-04-03 日東電工株式会社 Composition adhésive, feuille adhésive, stratifié pourvu d'une feuille adhésive, stratifié pourvu d'une feuille durcie, et procédé pour produire un stratifié pourvu d'une feuille durcie

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