WO2023054278A1

WO2023054278A1 - Laminate

Info

Publication number: WO2023054278A1
Application number: PCT/JP2022/035771
Authority: WO
Inventors: 佳世下川; 明日香遠藤; 涼平大幡; 研一岡田
Original assignee: 日東電工株式会社
Priority date: 2021-09-29
Filing date: 2022-09-26
Publication date: 2023-04-06
Also published as: TW202321019A

Abstract

The purpose of the present invention is to provide a laminate which has strong adhesive strength between a primer layer and a metal layer, and which can be manufactured conveniently at low crimping temperatures.　The present invention relates to a laminate obtained by laminating a primer layer onto at least a portion of a metal layer. The primer layer contains a polymer component having a polyamide resin as a main component thereof, and satisfies expression (1) below.　(1): G'(1)/G'(0) > 1.(0) (The definitions of G'(1) and G'(0) in expression (1) are as stated in the description.)

Description

laminate

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. there is

For example, in 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. there is

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

However, the techniques described in 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.

In addition, in the technique described in Patent Document 3, although the surface treatment method by applying a primer is simple, the process is limited because the primer itself has an active life.

Furthermore, the technology described in 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.

As a result of extensive studies aimed at achieving the above object, the present inventors have found that the following laminate can solve the above problems, and have completed the present invention.

That is, 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,
A laminate that satisfies the following formula (1).
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. is the elastic modulus of the primer layer up to a point 0.2 μm away toward the primer 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 μm away from the primer layer to the center of the primer layer. )
<2> The laminate according to <1>, wherein the primer layer has a melting point of 80°C to 170°C.
<3> The laminate according to <1>, wherein the primer layer has a thickness of 1 μm to 2000 μm.
<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. In addition, in a joined body obtained by laminating another material on the laminate of the present invention, 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.

Although the present invention will be described in detail below, these are examples of preferred embodiments, and the present invention is not limited to these contents.

[Laminate]
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. is the elastic modulus of the primer layer up to a point 0.2 μm away toward the primer 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 μm away from the primer layer to the center of the primer layer. )

In the laminate of the present invention, polar groups having a large dipole moment (C=O, CN, SH, NH, etc.) in the primer layer are oriented on the surface of the metal layer. As a result, it is thought that the glass transition temperature at the interface between the primer layer and the metal layer is locally increased, and the adhesion between the primer layer and the metal layer is strengthened.

Further, when the above formula (1) is satisfied, the primer layer firmly adheres to the surface of the metal layer, thereby increasing the bonding strength of the joined body.

The value of 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.

<Primer layer>
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. Here, 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.

Any appropriate polyamide resin can be selected as the polyamide resin as long as it does not impair the effects of the present invention. Examples of 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.

Examples of 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.

In addition, in the present invention, 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.

Examples of cross-linking agents include organic acid-based cross-linking agents and organic peroxide-based cross-linking agents.

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.

Examples of inorganic fine particles 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.

Examples of organic fine particles 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.

Also, 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 μm to 2000 μm, more preferably 5 μm to 1000 μm. Shape followability improves that thickness of a primer layer is in the above-mentioned range.

[Method for producing primer layer]
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.
Examples of 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.

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.

If necessary, 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.

For example, the addition of 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.

[Release sheet]
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. In addition, it may be a non-silicone resin sheet or a silicone resin sheet, but it is preferably a non-silicone resin sheet. manufactured by Nitoflon), polyester-based resin sheet, 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.

More specifically, 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.

The thickness of the release sheet is preferably 1 μm to 1000 μm, more preferably 5 μm to 500 μm, still more preferably 10 μm to 300 μm, and particularly preferably 20 μm to 100 μm, from the viewpoint of conformability.
If necessary, 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 of the metal layer 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. Moreover, the metal layer may be composed of only one kind of metal, or may be composed of two or more kinds of metals.

Examples of 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.

[Laminate production method]
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.

That is, 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.

Thermal transfer bonds the polymer component contained in the primer layer to the metal layer.
Thermal transfer may be performed simultaneously with placing the primer layer, or may be performed after placing the primer layer.

"At least part of the metal layer" means at least part of all the surfaces of the metal layer. For example, when 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. By setting the thermal transfer temperature to the melting point of the primer layer or higher, the adhesion between the primer layer and the metal layer is strengthened.

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.

As the heat press, for example, 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.

"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. means

The pressure in the heating press is preferably 0.1 MPa to 20 MPa, more preferably 1 MPa to 10 MPa.

Also, after thermal transfer, 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.

By the above manufacturing method, the primer layer 20 is provided on the surface of the metal layer 10 to obtain the laminate 100, as shown in FIG.

[Painted object]
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 μm to 2000 μm, more preferably 0.1 μm to 1000 μm, still more preferably 0.5 μm to 500 μm, particularly preferably 1 μm to 200 μm. .

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. In addition, 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.

[Joint]
<Resin joined body>
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).
Examples of 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. Among these resins, PPS (polyphenylene sulfide), PA (polyamide), PES (polyether sulfide), and EP (epoxy) are exemplified as thermoplastic resins that can advantageously exhibit the effects of the present invention.

A fiber reinforced thermoplastic (FRTP) may be employed as the thermoplastic.
Fiber reinforced thermoplastic resins (FRTP) include, for example, carbon fiber reinforced thermoplastic resins (CFRTP) and glass fiber reinforced thermoplastic resins (GFRTP).
Carbon fiber reinforced thermoplastic resins (CFRTP) 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 (GFRTP) include, for example, PPS glass fiber reinforced thermoplastic resins, PA glass fiber reinforced thermoplastic resins, PP glass fiber reinforced thermoplastic resins, and the like.

Examples of thermosetting resins 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.

<Metal joined body>
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.

Examples of 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.

<Adhesive joined body>
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.

As described above, this specification discloses the following matters.
[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,
A laminate that satisfies the following formula (1).
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. is the elastic modulus of the primer layer up to a point 0.2 μm away toward the primer 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 μm away from the primer layer to the center of the primer layer. )
[2] The laminate according to [1], wherein the primer layer has a melting point of 80°C to 170°C.
[3] The laminate according to [1] or [2], wherein the primer layer has a thickness of 1 μm to 2000 μm.
[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 joined body in which a metal material is laminated on at least a 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] A coated article comprising a coating film on at least a part of the laminate according to any one of [1] to [3].
[8] 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.
[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 present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

[Example 1]
<Production of primer layer>
Dissolve 100 parts by mass of modified nylon resin (Fine Resin FR-105 manufactured by Narimichi Co., Ltd.) in a mixed solvent of ethanol / water / isopropyl alcohol = 68% by mass / 12% by mass / 20% by mass at 60 ° C. Solid content 20 A primer composition of % by mass was prepared.

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 µm-thick primer layer with a release sheet.

<Production of laminate>
The primer layer side of the obtained primer layer with a release sheet is placed on a 30 μm copper foil, transferred with a thermal laminator under conditions of 150 ° C. and 0.1 MPa, and the copper foil (metal layer) and the primer layer are laminated. got a body

<Melting point of primer layer>
A primer layer was laminated to a thickness of 500 μm 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.

<180° peel test>
The release sheet of the obtained laminate was peeled off, and the primer layer side was placed on the CFRP epoxy resin prepreg. With a layer structure of metal layer/primer layer/CFRP prepreg, thermocompression bonding was performed under conditions of 150° C.×1 MPa×3 min to obtain a joined body.

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.

<Measurement of elastic modulus>
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 μm away from the primer layer. The measurement was performed at arbitrary five points, and the average value was taken as G'1.

In addition, the elastic modulus G'0 of the primer layer was measured in the range from a point 0.3 μm 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.

Then, the value of G'1/G'0 was obtained.

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 μm (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 μm aluminum foil was used instead of the 30 μm 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.

[Example 4]
A laminate was produced and evaluated in the same manner as in Example 3 except that a 60 μm aluminum foil was used instead of the 30 μm 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.

[Example 6]
A laminate was produced and evaluated in the same manner as in Example 5 except that a 60 μm aluminum foil was used instead of the 30 μm copper foil.

[Comparative 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 μm aluminum foil was used instead of the 30 μm copper foil.

Table 1 shows the evaluation results of Examples and Comparative Examples.

From the results in Table 1, it was found that 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.

Various embodiments have been described above with reference to the drawings, but it goes without saying that the present invention is not limited to such examples. It is obvious that a person skilled in the art can conceive of various modifications or modifications within the scope described in the claims, and these also belong to the technical scope of the present invention. Understood. Moreover, each component in the above embodiments may be combined arbitrarily without departing from the gist of the invention.

This application is based on a Japanese patent application (Japanese Patent Application No. 2021-159959) filed on September 29, 2021, the content of which is incorporated herein by reference.

10 metal layer 20 primer layer 100 laminate

Claims

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,
A laminate that satisfies the following formula (1).
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. is the elastic modulus of the primer layer up to a point 0.2 μm away toward the primer 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 μm away from the primer layer to the center of the primer layer. )
The laminate according to claim 1, wherein the primer layer has a melting point of 80°C to 170°C.
The laminate according to claim 1, wherein the primer layer has a thickness of 1 μm to 2000 μm.
A resin bonded body in which a resin material is laminated on at least a part of the laminate according to any one of claims 1 to 3.
A metal bonded body in which a metal material is laminated on at least a part of the laminate according to any one of claims 1 to 3.
An adhesive bonded body in which an adhesive layer is laminated on at least a part of the laminate according to any one of claims 1 to 3.
A coated article comprising a coating film on at least a part of the laminate according to any one of claims 1 to 3.
The method for manufacturing a laminate according to claim 1, comprising a 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 method for producing a laminate according to claim 8, further comprising the step of providing the primer layer on at least one side of the release sheet.