Metal composite material and method for producing the same

Abstract

SOLUTION: The present invention provides a metal composite material having a metal material joined thereto, a method for producing the same, and a joint material for the metal composite material.SELECTED DRAWING: None

Description

Technical Field

[0001] This specification relates to a metal composite material, a method for manufacturing the same, and a joining material therefor.

Background Art

[0002] Generally, joining of metal materials to each other or joining of a metal material to another inorganic or organic material includes joining by a welding method and joining by an adhesive. However, in the case of joining by an adhesive, surface treatment or the like is often required for the metal material (Patent Document 1).

[0003] In addition, it is known that fullerene can be carburized on the surface of various metal materials, thereby improving the hardness and the like of the metal material surface (Patent Document 2).

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, even when metal materials or dissimilar materials are joined after performing surface treatment, it has still been difficult to obtain a composite material integrated with high joining strength.

[0006] This specification provides a metal composite material including a structure in which metal materials are joined, a method for manufacturing the same, and a joining material for the metal composite material.

Means for Solving the Problems

[0007] When the inventors were studying various behaviors of fullerenes on the surface of a metallic material regarding bonding on the surface of the metallic material, they found that when heating fullerenes on the surface of the metallic material and when a curable resin composition coexists, the bondability of the cured product layer derived from the curable resin composition to the surface of the metallic material is improved. Based on these findings, the present specification provides the following means.

[0008] [1] A metal composite material, comprising: a metallic material; a cured product layer provided on the surface of the metallic material and containing a resin cured product; and a material containing at least a decomposition product of fullerenes or a compound derived from this decomposition product in the cured product layer and / or the surface layer of the metallic material in contact with the cured product layer of the metallic material. [2] The material according to [1], wherein the surface layer further has the resin cured product or a part thereof. [3] The material according to [1] or [2], wherein the resin cured product is a cured product of a resin curable composition containing an active hydrogen compound. [4] The material according to any one of [1] to [3], wherein the metallic material is one or more selected from Fe-based materials and Al-based materials. [5] The material according to any one of [1] to [4], wherein one or more of the metallic materials are integrated via one or more of the cured product layers. [6] The material according to any one of [1] to [5], wherein the resin cured product is an epoxy resin cured product. [7] A method for producing a metal composite material, comprising: a step of supplying fullerenes to the surface of a metallic material; a step of supplying a curable resin composition to the fullerenes; a step of curing the resin curable composition to obtain a resin cured product; and [8] The method according to [7], further comprising a step of cleaving at least a part of the carbon-carbon bonds in the fullerenes on the surface of the metallic material. [9] The step of cleaving the carbon-carbon bond includes heating the fullerene in an acidic atmosphere, the method according to [8].

[10] The step of obtaining the cured resin is a step involving heating or a step of curing the resin curable composition containing an active hydrogen compound, the method according to any one of [7] to [9].

[11] A joining kit for obtaining a metal composite material, a first agent containing fullerene, a second agent containing a curable resin composition, and a kit comprising.

[12] A metal material for composite formation with a cured resin, having at least fullerene or its decomposition product on the surface.

[13] A method for manufacturing a metal material for composite formation with a cured resin, a step of supplying fullerene to the surface of the metal material, a step of cleaving at least a part of the carbon-carbon bonds in the fullerene on the surface of the metal material, and a method comprising.

Brief Description of the Drawings

[0009]

Figure 1

Figure 2

Figure 3A

Figure 3B

Figure 4A

Figure 4B

Figure 5A

Figure 5B

Mode for Carrying Out the Invention

[0010] The disclosure of this specification relates to metal composite materials, methods for manufacturing the same, bonding kits for metal composite materials, metal materials for composite formation, and the like.

[0011] According to the metal composite material (hereinafter also referred to as the composite material) disclosed in this specification, a cured product layer of a resin curable composition is bonded to the surface of a metal material, and the composite material is such that the cured product layer and the metal material are well integrated. Since the metal material is integrated by the cured product layer, the characteristics of the cured product layer can be easily imparted to the metal material. Further, by using the cured product layer as a bonding layer, even metal materials and dissimilar materials can be integrated, and thus various forms of metal composite materials such as metal composite materials in composite forms that were conventionally difficult can be provided.

[0012] According to the method for manufacturing a metal composite material (hereinafter also referred to as the manufacturing method) disclosed in this specification, by supplying fullerene to the surface of a metal material and curing a curable resin composition, a metal composite material in which the cured product layer is well integrated can be manufactured. Further, when curing the curable resin composition, by supplying a material having an affinity for the curable resin composition to the curable resin composition, the material can also be integrated into the cured product layer.

[0013] According to the bonding kit for obtaining the metal composite material disclosed in this specification, since it includes fullerene and a curable resin composition, a cured product layer having good bonding properties with a metal material, a dissimilar material, etc. can be imparted to the surface of the metal material.

[0014] The metal materials for composite formation disclosed in this specification can have a bonding surface on their surface that facilitates integration with metal materials, dissimilar materials, etc. through the curing of a curable resin composition.

[0015] Hereinafter, the disclosure of this specification will be described in detail with reference to the drawings as appropriate. FIG. 1 is a diagram showing an example of the structure of a composite material, and FIG. 2 is a diagram showing an example of the flow of a manufacturing method.

[0016] (Metal composite material) As shown in FIG. 1, the composite material 2 includes a metal material 10 and a cured product layer 20 which is a layer provided on the surface of the metal material 10 and contains a resin cured product. Further, at least a decomposition product of fullerene can be contained in the cured product layer 20 and / or the surface layer 30 in contact with the cured product layer 20 of the metal material 10.

[0017] (Metal material) The metal constituting the metal material 10 is not particularly limited, and examples include metal base materials such as single metals and alloys. Examples of the metal include iron (Fe), aluminum (Al), copper (Cu), or alloys containing these. Typically, an Fe-based material which is Fe or an alloy thereof, and an Al-based material which is Al or an alloy thereof can be mentioned. The metal material 10 in this specification may be a material entirely composed of such a metal, or a metal material provided on the surface of a base material of a dissimilar material in the form of a film such as a metal foil or a layer.

[0018] The form of the metal material 10 is not particularly limited and can have various three-dimensional shapes. It may itself have a specific three-dimensional form such as a flat plate shape or a spherical shape, or it may be a three-dimensional form that covers the surface of another base material (including the outer surface and the inner surface).

[0019] (Cured product layer) The cured product layer 20 containing a resin cured product is provided on the surface of the metal material 10. The cured product layer 20 only needs to be provided on at least a part of the surface of the metal material 10, and its thickness and the like are not particularly limited.

[0020] The cured material layer 20 contains a resin cured product. The resin cured product is not particularly limited and may be a cured product of a thermosetting resin or a cured product of a thermoplastic resin. The resin cured product can be a monomer, an oligomer resin having a polymerizable component that can react with activated carbon species or activated carbon generated by the decomposition of fullerene, or a resin that can generate a decomposition product capable of reacting with activated carbon species or activated carbon during polymerization. Such resins include, for example, epoxy resins, melamine resins, urea resins, unsaturated polyester resins, urethane resins, alkyd resins, etc. Further, examples of the thermosetting resin include epoxy resins, urethane resins, etc., and examples of the thermoplastic resin include acrylic resins, methacrylic resins, styrene resins, propylene resins, polyamide resins, polyethylene terephthalate, etc.

[0021] For example, the epoxy resin is not particularly limited, and a conventionally known epoxy resin can be appropriately selected according to the use of the composite material. Examples of the epoxy resin include bifunctional epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol A / F type epoxy resin; Novolak type epoxy resins such as phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin; Polyfunctional epoxy resins such as trisphenol methane type epoxy resin; Glycidylamine type epoxy resin; Diglycidyl ether compounds of polyfunctional phenols, diglycidyl ether compounds of polyfunctional alcohols, and halides thereof; Heterocyclic ring-containing epoxy resins such as triglycidyl isocyanurate, and alicyclic epoxy resins such as hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, etc.

[0022] As the epoxy resin, among the above, it is preferable to use an epoxy resin having a bifunctional or higher epoxy group. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, alicyclic epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, diglycidyl ether compounds of polyfunctional phenols, diglycidyl ether compounds of polyfunctional alcohols, halides thereof, hydrogenated products thereof, etc. are available, and several types can be used in combination. From the viewpoint of heat resistance, alicyclic epoxy resin can be preferably used. By using these epoxy resins, a cured product layer excellent in heat resistance may be obtained.

[0023] The cured product of the epoxy resin is obtained by curing various epoxy resins with a curing agent as required. Although it may be suitable to use a curing agent, as the curing agent, a conventionally known curing agent can be appropriately selected and used. As the curing agent, for example, aliphatic amine-based such as dicyandiamide and diaminophenylmethane, aromatic amine-based such as diaminophenylsulfone, amine-based curing agents such as dicyandiamide; phthalic anhydride, pyromellitic anhydride, polyfunctional phenols such as phenol novolac and cresol novolac can be used, and several types of these can also be used in combination. As the curing agent, a curing agent that requires a curing reaction accompanied by heating or a curing agent that is an active hydrogen compound can be used. By using such a curing agent, fullerene may be activated in situ when obtaining the resin cured product. The blending amount of the curing agent may be appropriately determined according to the type and blending amount of the thermosetting resin used in the resin composition of the present invention, and is not particularly limited.

[0024] Also, as the acrylic resin, a polymer of a monomer having a (meth)acryloyl group such as a known (meth)acrylic acid, (meth)acrylate, etc., a copolymer of two or more of the above monomers, or a copolymer containing different monomers can be appropriately selected and used without particular limitation. Further, as the urethane resin, various known urethane resins can be appropriately used.

[0025] The cured product layer 20 can be obtained by preparing a curable resin composition containing, in addition to the cured resin, known curing accelerators, inorganic fillers, colorants, etc. as appropriate, and supplying and curing the composition onto the surface of a metal material (more specifically, the surface on which fullerene or its decomposition product has been previously supplied). Based on the composition of the curable resin composition, the cured product layer 20 can contain, in addition to the cured resin, unreacted epoxy resin, crosslinking agent, and further decomposition products thereof. The cured product layer 20 can further contain decomposition products of fullerene, which will be described in detail later.

[0026] (Fullerene) Fullerene is a carbon cluster in which carbon atoms form a hollow closed-shell structure, and the number of carbon atoms forming the closed-shell structure is usually an even number from 60 to 130. Specific examples of fullerenes include C60, C70, C76, C78, C82, C84, C90, C94, C96, and higher-order carbon clusters having more carbon atoms than these. Each of these fullerenes and mixtures of the above fullerenes can be used as appropriate, and the number of carbon atoms is not particularly limited. From the viewpoint of easy production, etc., fullerenes C60, C70, and mixtures thereof can be used. In addition to the above fullerenes, fullerene may be a fullerene derivative in which other molecules or functional groups are chemically modified on the fullerene molecule.

[0027] In the cured product layer 20 of the composite material 2 and the surface layer 30 in contact with the cured product layer 20 of the metal material 10, there is contained a decomposition product of fullerene or a compound derived from a decomposition product of fullerene (hereinafter, these are collectively referred to as decomposition products, etc.). The decomposition product of fullerene is not particularly limited, but is a compound obtained as a result of partial cleavage of the carbon-carbon bonds constituting fullerene, and oxides obtained by the reaction of the compound with oxygen, etc. Here, the decomposition product of fullerene can be obtained by decomposing fullerene in an oxidizing atmosphere such as air or oxygen, for example, at 250°C or higher, and for example, at 300°C or higher, and for example, at 350°C or higher. Also, for example, at 360°C or higher, and for example, at 370°C or higher, and for example, at 380°C or higher, and for example, at 390°C or higher. Further, the heating temperature can be set in consideration of sublimation of fullerene, etc., and is, for example, 600°C or lower, and for example, 550°C or lower, and for example, 500°C or lower, and for example, 450°C or lower, and for example, 400°C or lower, and for example, 390°C or lower, and for example, 380°C or lower, and for example, 370°C or lower. From the above, suitable heating temperatures are, for example, 350°C or higher and 450°C or lower, and for example, 350°C or higher and 400°C or lower, and for example, 350°C or higher and 390°C or lower, and for example, 350°C or higher and 380°C or lower, and for example, 350°C or higher and 370°C or lower.

[0028] Examples of the compound derived from the decomposition product of fullerene include reaction products of various fullerene decomposition products with an epoxy resin or its curing agent (crosslinking material), reaction products of reaction products of a fullerene decomposition product with an epoxy resin and a curing agent, and the like. Such reaction compounds vary depending on the type of epoxy resin and curing agent used.

[0029] Based on the composition of the curable resin composition, the cured product layer 20 can contain a resin cured product, unreacted epoxy resin, crosslinking agent, and further decomposition products and unreacted substances thereof, etc., and further can contain the above-mentioned decomposition products, etc. Among the cured product layer 20, the range mainly containing decomposition products, etc. refers to the range from the interface between the cured product layer 20 and the metal material 10 to, for example, a vertical distance of 200 μm, or for example, 100 μm, or for example, 50 μm, or for example, 30 μm.

[0030] The surface layer 30 of the metal material 10 can also contain decomposition products, etc. The surface layer 30 in contact with the cured product layer 20 refers to the range from the interface with the cured product layer 20 to a vertical distance of, for example, 200 μm, or for example, 100 μm, or for example, 50 μm, or for example, 30 μm. When the surface layer 30 contains decomposition products, etc., the integrality with the cured product layer may be more excellent. Also, for example, when decomposition products, etc. are contained at a higher concentration on the surface layer 30 side between the surface layer 30 and the cured product layer 20, the integrality with the cured product layer 20 may be more excellent than in the case where it is not so. Note that a high concentration of decomposition products, etc. on the surface layer 30 side can be determined by comparing the content of at least one type of decomposition product, etc. in the range of an equal vertical distance, for example, 1 nm or less, from the interface between the metal material 10 and the cured product layer 20.

[0031] The detection and content comparison of decomposition products, etc. in the cured product layer 20 and the surface layer 30 can be carried out, for example, by obtaining a cross-sectional region (for example, 100 μm × 100 μm) including the interface of the composite material 2 and performing TOF-SIMS (Time-of-Flight Secondary Ion Mass Spectrometry) on the cross-section.

[0032] In order to make the surface layer 30 contain decomposition products, etc. or make the surface layer 30 contain decomposition products, etc. at a higher concentration, it is preferable that the fullerene applied to the surface of the metal material 10 is decomposed by heat treatment, etc. prior to the formation of the cured product layer 20 to generate fullerene decomposition products.

[0033] The surface layer 30 of the metal material 10 can further contain a cured resin or a part thereof. By containing a cured resin or a part thereof in the surface layer 30 of the metal material 10, the cured product layer 20 and the metal material 10 are well integrated. Examples of a part of the cured resin contained in the surface layer 30 include the resin and the curing agent before curing of the cured resin. Further, examples of the part include decomposition products of the cured resin. The presence or absence of the cured resin or a part thereof in the surface layer 30 of the metal material 10 can be detected by TOF-SIMS as described above.

[0034] As described above, by including decomposition products and the like in the cured product layer 20 and / or the surface layer 30 on the cured product layer side of the metal material, the cured product layer 20 and the metal material 10 can exhibit good integrality. Thereby, various properties based on the cured product layer 20 can be exhibited with respect to the metal material 10. For example, surface layers for various applications such as a protective film, an antifouling film, a corrosion prevention film, a coating film, and a decorative film can be provided on the surface of the metal material by the cured product layer 20.

[0035] Furthermore, the cured product layer 20 can be used as a bonding layer to form a composite material including another material via the cured product layer 20. The other material may be any material that can be bonded by curing of the curable resin composition and is not particularly limited. When the other material is the same or different metal material, it is preferable to supply fullerene or a decomposition product thereof previously applied to the metal material 10 to the surface of the other material. This is because the integrality of the cured product layer 20 with respect to the surface of the other material is improved.

[0036] (Method for manufacturing a metal composite material) The manufacturing method disclosed in this specification can include a step of supplying fullerene to the surface of a metallic material (fullerene supply step), a step of supplying a curable resin composition to the fullerene (curable composition supply step), and a step of curing the curable resin composition to obtain a cured product layer including a resin cured product (cured product layer formation step). According to the manufacturing method, a cured product layer excellent in integrality can be provided on the surface of the metallic material, and characteristics based on the cured product layer can be imparted to the metallic material. Further, in order to improve the integrality of the cured product layer with the metallic material, a step of cleaving carbon-carbon bonds in the fullerene (fullerene activation step) can be included.

[0037] Hereinafter, with reference to FIG. 2, the fullerene supply step, the fullerene activation step, the curable composition supply step, and the cured product layer formation step will be described.

[0038] (Fullerene supply step) The step of supplying fullerene to the surface of the metallic material 10 is not particularly limited as long as fullerene can be supplied to the surface of the metallic material 10. The fullerene that can be used in this step is as described above. Fullerene powder may be supplied to the surface of the metallic material 10, the metallic material 10 may be hermetically embedded in the fullerene powder, the compression-molded fullerene molded body may be rubbed on the surface of the base material, the fullerene dispersed or dissolved in water or an organic solvent may be appropriately supplied to the surface of the metallic material 10, or a fullerene film may be formed on the surface of the base material by vacuum deposition. Briefly, a fullerene solution can be prepared with a suitable solvent such as xylene, and the fullerene solution can be supplied to the surface of the metallic material 10. When the fullerene solution or dispersion is supplied to the surface of the metallic material 10, it is preferable to dry the solvent.

[0039] (Fullerene activation step) The fullerene activation step is a step of cleaving a part of at least some of the carbon-carbon bonds in the fullerene on the surface of the metal material 10 to produce fullerene decomposition products and their oxides. According to the inventors, it has been found that due to the generation and presence of such fullerene decomposition products, when the composite material 2 is finally obtained, a large amount of decomposition products and the like can be contained in the surface layer 30 of the metal material 10 to improve the integrity. Therefore, the step of producing the fullerene decomposition products is referred to as the fullerene activation step.

[0040] The fullerene activation step can be carried out by heating the metal material supplied with fullerene. Such heat treatment can be carried out in an oxidizing atmosphere such as oxygen or air.

[0041] In the fullerene activation step, within the temperature range already described, it may be treated for a time such that the fullerene is sufficiently decomposed. The treatment time varies depending on the heating temperature and is not particularly limited. For example, it can be 30 minutes or more, or for example, 1 hour or more, or for example, 2 hours or more, or for example, 3 hours or more, or for example, 4 hours or more, etc. Also, for example, it can be 6 hours or less, or for example, 5 hours or less, or for example, 4 hours or less, etc.

[0042] The subsequent composition supply step can be carried out without performing the fullerene activation step. Even if the fullerene activation step is not performed, there may be cases where the surface layer 30 of the metal material 10 contains fullerene decomposition products or compounds derived from such decomposition products, and as a result, good bonding may be obtained. For example, in the process of curing a curable resin composition containing an active hydrogen compound such as an amine curing agent (for example, when the cured product is a polymer of an active hydrogen compound and an epoxy group or glycidyl group), fullerene decomposes along with the curing reaction of the resin, and the surface layer 30 of the metal material 10 can contain fullerene decomposition products or compounds derived from such decomposition products. Further, in the case where the cured product layer forming step involves heating at about 150°C to 200°C and fullerene decomposition products are generated in situ in the cured product layer forming step, the surface layer 30 of the metal material 10 can contain fullerene decomposition products or compounds derived from such decomposition products.

[0043] (Composition supply step) The composition supply step is a step of supplying the curable resin composition to unactivated fullerene or activated fullerene on the surface of the metal material 10. The curable resin composition is as described above. The method of supplying the curable resin composition to the surface of the metal material provided with fullerene (unactivated or activated) is not particularly limited, and a known method of supplying a resin composition or the like can be appropriately adopted. As the curable resin composition, the various embodiments described above can be applied.

[0044] (Cured product layer forming step) The cured product layer forming step is a step of supplying the curable resin composition to the fullerene of the metal material 10 and curing it. The operation for curing is defined by the epoxy resin and curing agent used in the curable resin composition, and the necessary time and temperature are provided so that the required curing conditions are satisfied. For example, it is at room temperature to 300°C, 40°C to 300°C, 60°C to 250°C for about 1 hour or more and 24 hours or less.

[0045] In forming the cured product layer 20, appropriate pressure can also be applied to the metal material 10 provided with the curable resin composition. When the cured product layer 20 is used as a bonding layer, appropriate pressure can be applied to the metal material 10, the composition, and other materials to be bonded.

[0046] When the fullerene activation step is performed during the formation of the cured product layer 20, the surface layer 30 of the metal material 10 tends to contain compounds derived from fullerene decomposition products, or reaction products of fullerene decomposition products with resin cured products or parts thereof, such as resin cured products or parts thereof. For this reason, the cured product layer 20 is well integrated with the surface of the metal material 10. Also, the resin cured product or part thereof itself also tends to be contained in the surface layer 30. Even when the cured product layer 20 is formed without going through the fullerene activation step, due to heating in the cured product formation step or the presence of an active hydrogen compound, the cured product layer 20 tends to contain decomposition products and the like, and the surface layer 30 may also contain decomposition products and the like. Therefore, even without going through the fullerene activation step, the cured product layer 20 is well integrated with the surface of the metal material 10.

[0047] Through the above steps, the composite material 2 can be obtained by forming the cured product layer 20 on the surface of the metal material 10. The manufacturing method can be variously modified, and those skilled in the art can appropriately obtain various forms of composite materials already described.

[0048] For example, when the cured product layer 20 is used as a bonding layer, prior to the cured product layer formation step, another metal material having activated or unactivated fullerene on its surface is brought into contact with the surface of the composition of the metal material that has undergone the composition supply step, and the cured product formation step is carried out to obtain a composite material 2 in which the metal material 10 and another metal material are bonded via the cured product layer 20. Also, for example, when the metal material 10 and a non-metal material are bonded via a cured product layer, the surface of the non-metal material does not necessarily need to be supplied with fullerene.

[0049] (Metal material for composite with resin cured product layer, its manufacturing method, and surface treatment method of metal material,) According to the method for manufacturing the composite material 2 described above, a cured product layer 20 with excellent integrality can be imparted to the metal material 10. According to the above disclosure, a metal material for composite formation suitable for imparting such a cured product layer 20 and a manufacturing method thereof are also provided. That is, a metal material for composite formation with a resin cured product layer having a fullerene decomposition product on its surface, a step of supplying fullerene to the surface of the metal material, and a step of cleaving carbon-carbon bonds in the fullerene are also provided. According to this metal material and its manufacturing method, a metal material capable of joining the cured product layer 20 with good integrality can be provided. This manufacturing method can also be implemented as a surface treatment method for the metal material. The metal material, fullerene, fullerene decomposition product, and the step of cleaving some of the carbon-carbon bonds in the fullerene can include various aspects as already described.

[0050] (Bonding Kit for Obtaining a Metal Composite Material) The bonding kit for obtaining a metal composite material disclosed in this specification can include a first agent containing fullerene and a second agent containing a curable resin composition. As described so far, by interposing fullerene on the surface of the metal material 10, when the curable resin composition is supplied and cured, a composite material 2 including the well-integrated metal material 10 and the cured product layer 20 can be obtained. Therefore, by preparing a kit in which the first agent contains fullerene and the second agent contains a curable resin composition, the composite material 2 can be easily obtained. The fullerene and the curable resin composition can include various aspects as already described.

Examples

[0051] Hereinafter, examples embodying the disclosure of this specification will be described. However, the following examples further specifically explain the disclosure of this specification and do not limit the disclosure of this specification.

Examples

[0052] (Bonding of a Metal Material with a Resin Cured Product Layer) In this example, DENATITE XNR6813 (resin) and XNH6813 (hardener) (manufactured by Nagase Sangyo Co., Ltd.), which are two-component heat-resistant curable resin compositions, or Araldite 2012 (manufactured by HUNTSDMAN Co., Ltd.), a structural curable resin composition, and fullerene (Nano Mix manufactured by Frontier Carbon Corporation, composed of 50 - 65% C60, 15 - 25% C70, and other higher-order fullerenes) were used. As the Fe-based material, cold-rolled steel SPC270 was used, and as the Al-based material, ADC12, an aluminum die-cast alloy, was joined, and the joining strength was analyzed.

[0053] (Preparation of Bonded Body Example 1) For each metal material, test pieces of 25 mm × 100 mm were prepared and the surfaces were degreased by wiping with acetone. For these test pieces, the 25 mm × 30 mm portion at the ends of the test pieces was used as the mutual bonding region. First, the following operations were performed on the bonding regions of the Fe-based material and the Al-based material to prepare Bonded Body Example 1.

[0054] A fullerene saturated solution (solvent: xylene, 8.7 mg / ml) was prepared, and 0.5 ml of the fullerene saturated solution was dropped onto each bonding region of the Fe-based test piece and the Al-based test piece and dried. These test pieces were heated at 350 °C for 2 hours in an air atmosphere to activate the fullerene. Each test piece was left to cool to room temperature. Then, 0.5 ml of the above heat-resistant curable resin composition (liquid) was dropped onto the bonding region of the Fe-based test piece, and immediately, the bonding region of the Al-based test piece was overlapped on this bonding region, a weight of 380 g was loaded, preheated at 80 °C for 2 hours, and then heated at 180 °C for 2 hours to prepare a bonded body.

[0055] (Preparation of Bonded Body Example 2) Except for not performing the heat treatment of fullerene, the operation was the same as that of Bonded Body Example 1 to cure the curable resin composition without undergoing the heat treatment of fullerene and prepare a bonded body.

[0056] (Preparation of Bonded Body Example 3) Except for using the above-described structural curable resin composition as the curable resin composition, the operation was the same as in Bonded Body Example 1 to cure the curable resin composition and produce a bonded body.

[0057] (Production of Bonded Body Example 4) Except for using the structural curable resin composition as the curable resin composition and not performing the heat treatment of fullerene, the operation was the same as in Bonded Body Example 1 to cure the curable resin composition without undergoing the heat treatment of fullerene and produce a bonded body.

[0058] (Production of Bonded Body Comparative Example 1) Except for dropping the saturated solution of fullerene and not performing the heat treatment of fullerene, the operation was the same as in Bonded Body Example 1 to cure the curable resin composition without interposing fullerene and produce a bonded body.

[0059] (Production of Bonded Body Comparative Example 2) Except for dropping the saturated solution of fullerene and not performing the heat treatment of fullerene, the operation was the same as in Bonded Body Example 3 to cure the curable resin composition without interposing fullerene and produce a bonded body.

[0060] Tensile tests were conducted on these Bonded Body Examples 1 to 4 and Bonded Body Comparative Example 1, and the bonding strength was evaluated. The results are shown below. The tensile test was performed by attaching both ends of the fabricated bonded body to a tensile compression testing machine and pulling to measure the strength at the time of fracture. The tensile compression testing machine used was Autograph AG-Xplus 50KN manufactured by Shimadzu Corporation, and the tensile speed was 1 mm / min.

[0061]

Table 1

[0062] As shown in Table 1, although the bonded body Examples 1 and 3 involving heat treatment of fullerene were bonded with high strength, the bonded body Examples 2 and 4 without heat treatment of fullerene were also bonded with significantly higher strength compared to the bonded body Comparative Examples 1 and 2 without using fullerene. Also, in the bonded body Examples 1 and 3, the cured product layer itself was broken, but in the bonded body Example 2, the cured product layer peeled off on the surface of the Fe-based test piece, and in the bonded body Example 4, it peeled off on both the Fe-based side and the Al-based side. In the bonded body Comparative Example 2, only the Fe-based side peeled off and broke.

[0063] From the above, it was found that by interposing fullerene, high bonding strength can be obtained without performing heat treatment, and even higher bonding strength can be obtained when heat treatment is performed. Also, in the bonding with heat treatment of fullerene, since the cured product layer itself was broken, it was found that it was firmly bonded to the metal base side.

Example

[0064] In this example, in order to confirm the distribution of fullerene decomposition products and the like in the vicinity of the bonding interface of the bonded body produced in Example 1, a test body for evaluation was produced according to Example 1, and the detection of molecular species was performed by TOF-SIMS.

[0065] The test bodies were prepared with SPC270 (Fe-based material, cold-rolled steel) with and without fullerene coated and activated, and ADC12 (Al-based material, aluminum die-cast alloy) with and without fullerene coated and activated in the same way. The heat-resistant curable resin composition used in Example 1 was applied to each of them, and immediately heated at 80 °C for 2 hours and then at 180 °C for 2 hours to bond them. After air cooling, the bonded body was cut so as to include the bonding interface, and the molecular species were detected by TOF-SIMS for the analysis target region of 100 μm × 100 μm of the cut surface. In this TOF-SIMS, elements or molecular species existing at a depth of 1 nm or less from the surface can be detected. The results are shown in FIGS. 3 to 5.

[0066] Figures 3 to 4 respectively show the evaluation results of the bonding interfaces between the cured epoxy resin and Fe(SPC270) and between the cured epoxy resin and Al(ADC12). Note that the left side of each figure shows the results for the bonded body without fullerene activation treatment, and the right side shows the results for the bonded body with fullerene activation treatment. Also, at both ends of each figure, the Fe analysis results and Al analysis results of each bonded body are shown to indicate the interfaces. In addition, the molecular species whose composition formulas were identified were identified as fullerene decomposition products and reaction products of fullerene decomposition products and epoxy resin based on their compositions and the like.

[0067] Figures 3A and 3B show the evaluation results at the Fe-side bonding interface of the test specimens. As shown in these figures, it was found that fullerene and fullerene decomposition products penetrated more into the Fe surface layer (in the range of a vertical distance of at least 30 μm from the bonding interface to the deep side) in the activated bonded body. Also, the reaction products of the epoxy resin and the crosslinking agent and the epoxy resin decomposition products penetrated more into the Fe surface layer in the activated bonded body. The reaction products of the fullerene decomposition products and the epoxy resin and the reaction products of the fullerene decomposition products, the epoxy resin, and the crosslinking agent penetrated into the Fe surface layer regardless of activation.

[0068] Figures 4A and 4B show the evaluation results at the Al-side bonding interface of the test specimens. As shown in these figures, it was found that fullerene and fullerene decomposition products penetrated more into the Al surface layer (in the range of a vertical distance of at least 30 μm from the bonding interface to the deep side) in the activated bonded body. Also, the reaction products of the epoxy resin and the crosslinking agent penetrated more into the Al surface layer in the activated bonded body. The epoxy resin decomposition products, the reaction products of the fullerene decomposition products and the epoxy resin, and the reaction products of the fullerene decomposition products, the epoxy resin, and the crosslinking agent penetrated into the Fe surface layer regardless of activation.

[0069] In addition, FIGS. 5A and 5B further show the evaluation results for other molecular species with respect to the Fe-side bonding interface and the Al-side bonding interface of the test piece, together with the evaluation results of the bonded body coated with only the epoxy resin and cured. As shown in FIGS. 5A and 5B, it was found that the fullerene decomposition products, crosslinking agents, epoxy resins, and reaction products of the epoxy resin and the crosslinking agent all penetrated into the Fe surface layer and the Al surface layer (both in the range of a vertical distance of at least 30 μm from the bonding interface to the deep side).

[0070] In addition, from FIGS. 3 to 5, it was found that although the fullerene was almost decomposed by the activation treatment, both the fullerene and its decomposition products penetrated into the metal group side by the activation.

[0071] From the above, it was found that by accompanying fullerene activation, the fullerene and the fullerene decomposition products were maintained in a state of penetrating into the metal group surface layer (in the range of a vertical distance of at least 30 μm from the bonding interface to the deep side), and were present less on the resin side. It was found that the penetration of such fullerene decomposition products to the surface layer side of the metal group contributed to the improvement of the bonding strength.

Claims

1. A metal composite material comprising: a metal material; a cured product layer provided on the surface of the metal material and containing a cured product of a heat-resistant thermosetting resin composition; and a material in which at least the surface layer of the cured product layer and the metal material in contact with the cured product layer contains a fullerene decomposition product in which at least a part of the carbon-carbon bonds of fullerene is cleaved and the cured product of the heat-resistant thermosetting resin composition or a part thereof.

2. The material according to claim 1, wherein the cured product is a cured product of the heat-resistant thermosetting resin composition containing an active hydrogen compound.

3. The material according to claim 1 or 2, wherein the metal material is one or more selected from Fe-based materials and Al-based materials.

4. The material according to any one of claims 1 to 3, wherein one or more of the metal materials are integrated via one or more of the cured product layers.

5. The material according to any one of claims 1 to 4, wherein the cured product contains a cured product of an epoxy resin.

6. A method for manufacturing a metal composite material, comprising: a step of supplying fullerene to the surface of a metal material; a step of supplying a curable resin composition to the fullerene; and a step of curing the curable resin composition to obtain a resin cured product.

7. The method according to claim 6, further comprising a step of cleaving at least a part of the carbon-carbon bonds in the fullerene on the surface of the metal material.

8. The method according to claim 7, wherein the step of cleaving the carbon-carbon bonds includes heating the fullerene in an oxidizing atmosphere.

9. The method according to any one of claims 6 to 8, wherein the step of obtaining the resin cured product is a step involving heating or a step of curing the curable resin composition containing an active hydrogen compound.

10. A joining kit for obtaining a metal composite material, comprising: a first agent containing fullerene; a second agent containing a curable resin composition; and

11. A metal material for composite formation with a resin cured product, having at least fullerene or a decomposition product thereof on the surface.

12. A method for manufacturing a metal material for composite formation with a resin cured product, comprising: a step of supplying fullerene to the surface of the metal material; and a step of cleaving at least a part of the carbon-carbon bonds in the fullerene on the surface of the metal material. ​ ​

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