Title of invention: Metal-fiber reinforced resin material composite
Technical field
[0001]
　The present invention relates to a metal-fiber reinforced resin material composite body in which a metal member and a fiber reinforced resin material are laminated and integrated.
Background technology
[0002]
　Fiber Reinforced Plastics (FRP), which is a composite of reinforced fibers (for example, glass fibers, carbon fibers, etc.) contained in a matrix resin, is lightweight and excellent in tensile strength and workability. Therefore, it is widely used from consumer fields to industrial applications. In the automobile industry as well, in order to meet the needs for vehicle body weight reduction leading to improvement in fuel efficiency and other performances, application of FRP to automobile members is being considered, focusing on the lightness, tensile strength, workability, etc. of FRP. ..
[0003]
　When the FRP itself is used as an automobile member, there are various problems as described below. First, when painting or bending, existing equipment such as a painting line provided for a metal member such as steel or a bending die cannot be used as it is for FRP. Secondly, since FRP has low compressive strength, it is difficult to use FRP as it is for automobile parts that require high compressive strength. Thirdly, the matrix resin of FRP is brittle because it is generally a thermosetting resin such as an epoxy resin, and therefore, there is a possibility of brittle fracture when deformed. Fourth, FRP (Carbon Fiber Reinforced Plastics (CFRP)), which uses carbon fibers as reinforcing fibers, is expensive, which causes a cost increase of automobile parts. Fifth, as described above, since the thermosetting resin is used as the matrix resin, the curing time is long and the takt time is long, which is not suitable for manufacturing an automobile member requiring a short takt time. Sixth, FRP using a thermosetting resin as a matrix resin does not undergo plastic deformation, so once it is cured, it cannot be bent.
[0004]
　In order to solve these problems, recently, a metal member-FRP composite material in which a metal member and FRP are laminated and integrated (composite) has been studied. Regarding the first problem, in the metal member-FRP composite material, a metal member such as steel material can be positioned on the surface of the composite material, so that a coating line or a mold provided for the metal material such as steel material can be provided. Etc. can be used as they are. Regarding the second problem described above, the compressive strength of the composite material can be increased by combining the metal member having high compressive strength and FRP. With respect to the third problem described above, by combining with a metal member such as a steel material having ductility, brittleness is reduced and the composite material can be deformed. Regarding the fourth problem, by combining a low-priced metal member and FRP, it is possible to reduce the amount of FRP used, so that the cost of automobile members can be reduced.
[0005]
　In order to combine the metal member and the FRP, it is necessary to bond or bond the metal member and the FRP. As a bonding method, generally, a method using an epoxy resin-based thermosetting adhesive is used. Are known.
[0006]
　Further, in order to solve the problems when the above FRP is used for automobile members, it has been studied in recent years to use a thermoplastic resin as a matrix resin of the FRP instead of a thermosetting resin such as an epoxy resin. Regarding the third problem, since the thermoplastic resin is used as the matrix resin, the FRP can be plastically deformed and brittleness can be reduced. With respect to the fifth problem, by using a thermoplastic resin as the matrix resin, solidification and softening are ready, so that the tact time can be shortened. Regarding the sixth problem, as described above, since it becomes possible to plastically deform the FRP, bending work becomes easy.
[0007]
　As described above, by compounding the FRP using the thermoplastic resin as the matrix resin with the metal member, it is possible to solve the problems when the FRP is used as the automobile member.
[0008]
　Here, regarding the joining or adhering means of the fiber reinforced resin material such as FRP and the metal member, technical development is actively conducted mainly from the viewpoint of strengthening the joining force between the metal member and the adhering or adhering means. It is being appreciated.
[0009]
　For example, in Patent Document 1 and Patent Document 2, a hard and highly crystalline thermoplastic resin is injection-molded on the adhesive surface of a metal member by injection-molding, or an adhesive layer of an epoxy resin is provided on the metal member. There has been proposed a technique for improving the adhesion strength between the metal member and CFRP.
[0010]
　In Patent Document 3, a composite of a reinforcing fiber base material and a metal, in which a bonding surface of a carbon fiber base material with a metal member is impregnated with an adhesive resin such as an epoxy resin and the other surface is impregnated with a thermoplastic resin to form a prepreg. The body is proposed.
[0011]
　Patent Document 4 proposes a method of manufacturing a sandwich structure with a steel plate using a CFRP molding material using a polyurethane resin matrix. The material of this document utilizes the good moldability of the thermoplastic polyurethane resin, and at the same time, is made to be a thermosetting resin by causing a crosslinking reaction to the polyurethane resin by after-cure, thereby enhancing the strength.
[0012]
　In Patent Document 5, powder of a phenoxy resin or a resin composition in which a crystalline epoxy resin and an acid anhydride as a cross-linking agent are mixed with a phenoxy resin is applied to a reinforced fiber base material by a powder coating method to prepare a prepreg. It has been proposed to prepare the above and mold and cure it by hot pressing to obtain CFRP.
[0013]
　In Patent Document 6, a composite material composed of a flat plate-shaped carrier material composed of a metal and a fiber-reinforced thermoplastic material and a supporting material composed of a thermoplastic material is heated to form a rib structure on the supporting material. In addition, there has been proposed a method for manufacturing a structural part for vehicle body, in which a carrier material is molded into a three-dimensional part.
[0014]
　In Patent Document 7, a fiber-reinforced resin intermediate material used by being heated and pressed in a laminated state, in which a reinforcing fiber base material has voids opened to the outer surface, and a resin in powder form is in a semi-impregnated state. Have been proposed.
Prior art documents
Patent literature
[0015]
Patent Document 1: International Publication No. 2009/116484
Patent Document 2: Japanese Patent Laid-Open No. 2011-240620
Patent Document 3: Japanese Patent Laid-Open No. 2016-3257
Patent Document 4: Japanese Patent Laid-Open No. 2015-212085
Patent Document 5: International Publication No. 2016/152856
Patent Document 6: Japanese Patent Publication No. 2015-536850
Patent Document 7: Patent No. 5999721
Non-patent literature
[0016]
Non-Patent Document 1: Takeyuki Tanaka, Journal of Coloring Materials, Vol. 63, No. 10, 622-632, 1990.
Summary of the invention
Problems to be Solved by the Invention
[0017]
　By the way, in designing a composite material in which a metal member and a fiber-reinforced resin material such as FRP are composited, when designing a high-strength material, generally, the thickness of the metal member is increased or the strength of the fiber is high. It is necessary to increase the amount of the reinforced resin material used to thicken the layer containing the fiber reinforced resin material. In addition, in order to bond the thick metal member and the layer containing the fiber reinforced resin material, it may be necessary to increase the thickness of the adhesive layer.
[0018]
　However, if the thickness of the metal member is increased, the weight is increased, and the need for weight reduction may not be satisfied. Further, if the layer containing the fiber reinforced resin material is made thicker, the workability is lowered, and the cost is increased due to the increase in the amount of the fiber reinforced resin material used. As described above, in a composite material in which a metal member and a fiber-reinforced resin material such as FRP are composited, there is a trade-off relationship between high strength and light weight, and further technical innovation is required.
[0019]
　Therefore, the present invention has been made in view of the above problems, by firmly joining the metal member and the fiber reinforced resin material, while improving the strength, is lightweight and excellent in workability, and further, the fiber reinforced resin material. It is an object of the present invention to provide a metal-fiber reinforced resin material composite capable of reducing the amount of used.
Means for solving the problems
[0020]
　As a result of earnest studies, the present inventors have joined a metal member and a fiber-reinforced resin material by a cured product of an adhesive resin composition containing a predetermined amount of a phenoxy resin (A) to be integrated (composite). It was found that the above problems can be solved by doing so, and the present invention has been completed.
[0021]
　That is, according to an aspect of the present invention, a metal member, a matrix resin, and a first fiber-reinforced resin material having a reinforcing fiber material contained in the matrix resin, the metal member and the The first fiber reinforced resin material is a metal-fiber reinforced resin material composite compounded via an adhesive resin layer, wherein the adhesive resin layer is a phenoxy resin (A Metal-fiber, which contains a cured product of an adhesive resin composition containing 50 parts by mass or more of ), and exhibits a superaddition rule in which the maximum load of the metal-fiber reinforced resin material composite exceeds a law of addition (law of mixture). A reinforced resin material composite is provided.
[0022]
　As described above, by including the phenoxy resin in the adhesive resin composition, the metal member and the first fiber-reinforced resin material can be firmly bonded. As a result, the metal-fiber reinforced resin material composite can exhibit excellent strength against a tensile load even if the metal member, the fiber reinforced resin material and the adhesive resin layer are thin.
[0023]
　Here, the superaddition rule means that the following expression (2-2) is established.
　C>A2+B (2-2) In the
　formula (2-2), the load A2 indicates the tensile load of the metal member alone when the metal-fiber reinforced resin material composite is broken, and the load B is the first load. Shows the maximum load of the fiber-reinforced resin material alone, and the load C is the maximum load of the metal-fiber-reinforced resin material composite.
[0024]
　Here, the superaddition rule degree, which is the ratio of the load C to the total load of the load A2 and the load B, may be 1.01 or more, and the superaddition rule degree is 1.05 or more. It may be.
[0025]
　In addition, the total thickness T1 of the metal member and the elastic coefficient E1 of the metal member, the total thickness T2 of the first fiber reinforced resin material and the adhesive resin layer, the first fiber reinforced resin material and the The elastic modulus E2 of the adhesive resin layer may satisfy the relationship of the following expression (1).
　(T1×E1)/(T2×E2)>0.3...Equation (1)
[0026]
　In the metal-fiber reinforced resin material composite, the adhesive resin layer is a second fiber reinforced resin material having the cured product as a matrix resin and a reinforced fiber material contained in the matrix resin. May be.
[0027]
　In the metal-fiber reinforced resin material composite, the adhesive resin composition is in the range of 5 parts by mass or more and 85 parts by mass or less with respect to 100 parts by mass of the phenoxy resin (A), and the crosslinkable resin (B). A crosslinkable adhesive resin composition further comprising: and the cured product may be a crosslinked cured product.
[0028]
　In the metal-fiber reinforced resin material composite, the thickness of the adhesive resin layer is preferably more than 20 μm.
[0029]
　In the metal-fiber reinforced resin material composite, the material of the metal member may be a steel material, an iron-based alloy, titanium or aluminum. The steel material may be a hot dip galvanized steel sheet, an electrogalvanized steel sheet, or an aluminized steel sheet.
Effect of the invention
[0030]
　As described above, according to the present invention, by containing a phenoxy resin in the adhesive resin composition, it becomes possible to firmly bond the metal member and the first fiber reinforced resin material. As a result, the metal-fiber reinforced resin material composite exhibits excellent strength against tensile load exceeding the additive law even if the thickness of the metal member, the fiber reinforced resin material and the adhesive resin layer is reduced. it can. Therefore, it is possible to improve the strength of the metal-fiber reinforced resin material composite, to reduce the weight and the workability, and to reduce the amount of the fiber reinforced resin material used.
Brief description of the drawings
[0031]
FIG. 1 is a schematic view showing a cross-sectional structure of a metal-fiber reinforced resin material composite body according to a first embodiment of the present invention.
FIG. 2 is a schematic view showing a cross-sectional structure of another mode of the metal-fiber reinforced resin material composite according to the same embodiment.
FIG. 3 is an explanatory diagram for explaining a method for measuring the content of a phenoxy resin.
FIG. 4 is an explanatory diagram for explaining a thickness measuring method.
FIG. 5 is an explanatory view showing an example of a manufacturing process of the metal-fiber reinforced resin material composite according to the same embodiment.
FIG. 6 is an explanatory view showing an example of a manufacturing process of another aspect of the metal-fiber reinforced resin material composite according to the same embodiment.
FIG. 7 is a schematic diagram showing a cross-sectional structure of a metal-fiber reinforced resin material composite body according to a second embodiment of the present invention.
FIG. 8 is a schematic view showing a sectional structure of another mode of the metal-fiber reinforced resin material composite according to the same embodiment.
FIG. 9 is an explanatory view showing an example of a manufacturing process of the metal-fiber reinforced resin material composite according to the same embodiment.
FIG. 10 is an explanatory diagram showing a structure of a sample of a metal-FRP composite for tensile test in Examples and Comparative Examples.
FIG. 11 is a graph schematically showing the result of a tensile test of each test piece.
FIG. 12 is a graph schematically showing a preferred range of (T1×E1)/(T2×E2).
MODE FOR CARRYING OUT THE INVENTION
[0032]
　Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. In this specification and the drawings, components having substantially the same functional configuration are designated by the same reference numerals, and duplicate description will be omitted.
[0033]
First Embodiment
[Configuration of Metal-Fiber Reinforced Resin Material Composite]
　First, referring to FIGS. 1 and 2, a metal-fiber reinforced resin material composite according to a first embodiment of the present invention will be described. The configuration will be described. 1 and 2 are schematic views showing a cross-sectional structure in the stacking direction of a metal-FRP composite 1 as an example of the metal-fiber reinforced resin material composite according to the present embodiment.
[0034]
　As shown in FIG. 1, the metal-FRP composite 1 includes a metal member 11, an FRP layer 12 as an example of the first fiber-reinforced resin material according to the present embodiment, and an adhesive resin layer 13. The metal member 11 and the FRP layer 12 are compounded via the adhesive resin layer 13. Here, “composite” means that the metal member 11 and the FRP layer 12 (first fiber reinforced resin material) are joined (bonded) via the adhesive resin layer 13 and are integrated. To do. Further, “integrated” means that the metal member 11, the FRP layer 12 (first fiber-reinforced resin material), and the adhesive resin layer 13 move integrally during processing or deformation.
[0035]
　In the metal-FRP composite 1, the adhesive resin layer 13 is a solidified product or a cured product of an adhesive resin composition containing 50 parts by mass or more of the phenoxy resin (A) with respect to 100 parts by mass of the resin component, as described later. .. The term "solidified product" simply means that the resin component itself is solidified, and the term "cured product" means that the resin component is hardened by containing various curing agents. .. The curing agent that can be contained in the cured product also includes a crosslinking agent as described below, and the above-mentioned "cured product" includes a crosslinked cured product.
[0036]
　In the present embodiment, the adhesive resin layer 13 is provided so as to contact at least one surface of the metal member 11, and firmly adheres the metal member 11 and the FRP layer 12 to each other. However, the adhesive resin layer 13 and the FRP layer 12 may be provided not only on one surface of the metal member 11 but also on both surfaces thereof. Alternatively, a laminate including the adhesive resin layer 13 and the FRP layer 12 may be sandwiched between the two metal members 11.
[0037]
　Further, in the metal-FRP composite 1, the total thickness T1 of the metal member 11 and the elastic modulus E1 of the metal member 11, the total thickness T2 of the FRP layer 12 and the adhesive resin layer 13, the FRP layer 12 and the adhesive resin. The elastic modulus E2 of the layer 13 preferably satisfies the relationship of the following expression (1). The elastic modulus in the present embodiment means the tensile elastic modulus (Young's modulus) at room temperature (25° C.). Details of this relationship will be described later.
　(T1×E1)/(T2×E2)>0.3...Equation (1)
[0038]
　Hereinafter, each component of the metal-FRP composite 1 and other configurations will be described in detail.
[0039]
(Metal Member 11)
　The material, shape, thickness and the like of the metal member 11 are not particularly limited as long as they can be molded by pressing or the like, but the shape is preferably a thin plate. Examples of the material of the metal member 11 include iron, titanium, aluminum, magnesium and alloys thereof. Here, examples of the alloy include iron-based alloys (including stainless steel), Ti-based alloys, Al-based alloys, Mg alloys, and the like. The material of the metal member 11 is preferably a steel material, an iron-based alloy, titanium and aluminum, and more preferably a steel material having a higher elastic modulus than other metal species. Examples of such iron and steel materials include cold-rolled steel sheets for general use, drawing or ultra-deep drawing, which are standardized in the Japanese Industrial Standards (JIS) as thin steel plates used for automobiles, and workability for automobiles. There are steel materials such as cold-rolled high-tensile steel sheet, hot-rolled steel sheet for general use and processing, hot-rolled steel sheet for automobile structure, hot-rolled high-strength steel sheet for automobiles, and for general structures and machinery. Carbon steel, alloy steel, high-strength steel, etc. used for structural purposes can also be mentioned as steel materials not limited to thin plates.
[0040]
　The steel material may be subjected to any surface treatment. Here, the surface treatment is, for example, various plating treatments such as zinc plating (hot dip galvanized steel sheet, electrogalvanizing etc.) and aluminum plating, chemical conversion treatments such as chromate treatment and non-chromate treatment, and physical treatment such as sandblasting. Examples of the surface roughening treatment include chemical surface roughening treatments such as chemical or chemical etching, but are not limited thereto. Further, alloying of plating and surface treatment of plural kinds may be performed. As the surface treatment, it is preferable that at least a treatment for the purpose of imparting antirust property is performed.
[0041]
　In order to improve the adhesiveness with the FRP layer 12, it is preferable to treat the surface of the metal member 11 with a primer. As the primer used in this treatment, for example, a silane coupling agent or a triazine thiol derivative is preferable. Examples of the silane coupling agent include epoxy type silane coupling agents, amino type silane coupling agents, and imidazole silane compounds. Examples of the triazinethiol derivative include 6-diallylamino-2,4-dithiol-1,3,5-triazine, 6-methoxy-2,4-dithiol-1,3,5-triazine monosodium, and 6-propyl-2. , 4-dithiolamino-1,3,5-triazine monosodium and 2,4,6-trithiol-1,3,5-triazine are exemplified.
[0042]
　Here, depending on the material of the metal member 11, an oil film may be formed on the surface of the metal member 11 from the viewpoint of rust prevention and the like. For example, when the metal member 11 is a steel material, particularly a hot dip galvanized steel plate, an electrogalvanized steel plate, an aluminum plated steel plate, or the like, an oil film of rust-preventing oil is often formed on the surface of the metal member 11. When it is difficult to bond the FRP and the metal member 11 with sufficient bonding strength even if the FRP and the metal member 11 are bonded with the adhesive resin layer 13 while such an oil film is formed on the surface of the metal member 11. There is. That is, it may be difficult to manufacture the metal-FRP composite 1 having the superaddition rule. Therefore, when an oil film is formed on the surface of the metal member 11, it is preferable to perform a degreasing treatment before joining with the FRP. As a result, the FRP and the metal member 11 can be bonded with sufficient bonding strength, and the metal-FRP composite 1 can easily obtain strength exceeding the additive rule described later. Regarding the necessity of degreasing, the target metal member 11 is joined in advance to the target FRP by the target adhesive resin composition without the degreasing step to be integrated, and the superaddition rule is actually applied. You can make a judgment by checking whether or not occurs. Additive rules and super-additive rules will be described later.
[0043]
(FRP Layer 12) The
　FRP layer 12 has a matrix resin 101 and a composite reinforced fiber material 102 contained in the matrix resin 101.
[0044]
　As the matrix resin 101 used in the FRP layer 12, either a thermosetting resin or a thermoplastic resin can be used. Examples of the thermosetting resin include epoxy resin and vinyl ester resin. Examples of the thermoplastic resin include phenoxy resin, polyolefin and acid modified products thereof, polystyrene, polymethylmethacrylate, AS resin, ABS resin, polyester such as polyethylene terephthalate and polybutylene terephthalate, vinyl chloride, acrylic, polycarbonate, polyamide, polyether sulfone. , Polyphenylene ether and its modified products, polyimide, polyamide imide, polyether imide, polyether ether ketone, super engineering plastics such as polyphenylene sulfide, polyoxymethylene, polyarylate, polyether ketone, polyether ketone ketone, and nylon etc. One or more types can be used.
[0045]
　Among the above-mentioned resins, it is preferable to form the matrix resin 101 from a resin composition having good adhesion with the phenoxy resin (A) contained in the adhesive resin composition of the adhesive resin layer 13. Examples of the resin having good adhesion to the phenoxy resin (A) include epoxy resin, phenoxy resin, polyolefin resin acid-modified with maleic anhydride, polycarbonate, polyarylate, polyimide, polyamide, polyether sulfone. .. Some of these resins have low adhesiveness to the metal member 11, but they can be indirectly bonded to the metal member 11 by interposing the adhesive resin layer 13.
[0046]
　Here, when a thermosetting resin is used as the matrix resin 101, as described above, there are problems that the FRP layer 12 is brittle, has a long tact time, and cannot be bent. From the viewpoint of eliminating such problems, it is preferable to use a thermoplastic resin as the matrix resin 101. However, since the thermoplastic resin usually has a high viscosity when melted, and cannot be impregnated into the reinforcing fiber material 102 in a low viscosity state like a thermosetting resin such as an epoxy resin before thermosetting, The impregnation property for the reinforcing fiber material 102 is poor. Therefore, unlike the case where the thermosetting resin is used as the matrix resin 101, the reinforcing fiber density (VF: Volume Fraction) in the FRP layer 12 cannot be increased. Taking carbon fiber reinforced plastic (CFRP) using carbon fiber as the reinforcing fiber material 102, for example, when epoxy resin is used as the matrix resin 101, VF can be about 60%, but polypropylene or When a thermoplastic resin such as nylon is used as the matrix resin 101, the VF is about 50%. Here, in order for FRP to exhibit excellent tensile strength, the matrix resin 101 is impregnated into the reinforcing fiber material 102 in a state in which each fiber constituting the reinforcing fiber material 102 is strongly drawn in the same direction at a high density. There is a need. The reinforced fiber material 102 in such a state is hard to be impregnated with the matrix resin 101. If the reinforcing fiber material 102 is not sufficiently impregnated with the matrix resin 101 and defects such as voids occur in the FRP, not only the FRP does not exhibit a desired tensile strength, but also the FRP is brittle and fractures from the origin. there's a possibility that. Therefore, the impregnation property is very important. Further, when a thermoplastic resin such as polypropylene or nylon is used, the FRP layer 12 cannot have high heat resistance as in the case of using a thermosetting resin such as an epoxy resin.
[0047]
　In order to solve the problem when using such a thermoplastic resin, it is preferable to use a phenoxy resin as the matrix resin 101. Since the phenoxy resin has a molecular structure very similar to that of the epoxy resin, it has the same heat resistance as that of the epoxy resin and also has good adhesiveness to the adhesive resin layer 13 and the metal member 11. Further, a so-called partially curable resin can be obtained by adding a curing component such as an epoxy resin and copolymerizing the phenoxy resin. By using such a partially curable resin as the matrix resin 101, it is possible to obtain a matrix resin having excellent impregnation properties into the reinforcing fiber material 102. Further, by thermally curing the curing component in the partially curable resin, it is possible to prevent the matrix resin 101 in the FRP layer 12 from being melted or softened when exposed to a high temperature like a normal thermoplastic resin. it can. The addition amount of the curing component to the phenoxy resin may be appropriately determined in consideration of the impregnation property into the reinforcing fiber material 102, the brittleness of the FRP layer 12, the tact time, the processability, and the like. As described above, by using the phenoxy resin as the matrix resin 101, it is possible to add and control the curing component with a high degree of freedom.
[0048]
　Note that, for example, when carbon fiber is used as the reinforcing fiber material 102, the surface of the carbon fiber is often provided with a sizing agent that is compatible with the epoxy resin. Since the phenoxy resin has a structure very similar to that of the epoxy resin, by using the phenoxy resin as the matrix resin 101, the sizing agent for the epoxy resin can be used as it is. Therefore, cost competitiveness can be improved.
[0049]
　In the metal-FRP composite 1, the matrix resin 101 of the FRP layer 12 and the resin forming the adhesive resin layer 13 (details will be described later) may be the same resin or different resins. Good. However, from the viewpoint of sufficiently securing the adhesiveness between the FRP layer 12 and the adhesive resin layer 13, as the matrix resin 101, the same or the same resin as the resin forming the resin forming the adhesive resin layer 13 or a polymer It is preferable to select a resin type having a similar ratio of polar groups contained in the above. Here, the "same resin" means that they are composed of the same components and have the same composition ratio, and the "resin of the same kind" has different composition ratios if the main components are the same. Means good. The "same resin" includes "same resin". Further, the "main component" means a component contained in 50 parts by mass or more out of 100 parts by mass of all the resin components. The “resin component” includes a thermoplastic resin and a thermosetting resin, but does not include a non-resin component such as a crosslinking agent.
[0050]
　The reinforcing fiber material 102 is not particularly limited, but for example, carbon fiber, boron fiber, silicon carbide fiber, glass fiber, aramid fiber and the like are preferable, and carbon fiber is more preferable. As for the type of carbon fiber, for example, either PAN type or pitch type can be used, and it may be selected according to the purpose and application. As the reinforcing fiber material 102, one kind of the above-mentioned fibers may be used alone, or a plurality of kinds may be used in combination.
[0051]
　In the FRP used in the FRP layer 12, examples of the reinforcing fiber base material that serves as the base material of the reinforcing fiber material 102 include, for example, a nonwoven fabric base material using chopped fibers, a cloth material using continuous fibers, and a unidirectional reinforcing fiber base material. (UD material) or the like can be used. From the viewpoint of the reinforcing effect, it is preferable to use a cloth material or a UD material as the reinforcing fiber base material.
[0052]
　In the metal-FRP composite 1, the FRP layer 12 is formed by using at least one FRP molding prepreg. The FRP layer 12 is not limited to one layer, and may be two or more layers as shown in FIG. 2, for example. The thickness of the FRP layer 12 and the number n of the FRP layers 12 when the FRP layer 12 has a plurality of layers may be appropriately set according to the purpose of use. When there are a plurality of FRP layers 12, each layer may have the same structure or different layers. That is, the resin type of the matrix resin 101 forming the FRP layer 12, the type and content ratio of the reinforcing fiber material 102, and the like may be different for each layer.
[0053]
(Adhesive Resin Layer 13) The
　adhesive resin layer 13 joins the metal member 11 of the metal-FRP composite 1 and the FRP layer 12 together.
[0054]
Adhesive Resin Composition The
　adhesive resin layer 13 is composed of a solidified product or a cured product of an adhesive resin composition containing 50 parts by mass or more of the phenoxy resin (A) with respect to 100 parts by mass of the resin component. That is, 50 parts by mass or more of 100 parts by mass of the resin component is composed of the phenoxy resin (A). By using such an adhesive resin composition, it becomes possible to firmly bond the metal member 11 and the FRP layer 12. The adhesive resin composition preferably contains 55 parts by mass or more of the phenoxy resin (A) in 100 parts by mass of the resin component. The form of the adhesive resin composition can be, for example, powder, liquid such as varnish, or solid such as film.
[0055]
　The content of the phenoxy resin (A) can be measured using infrared spectroscopy (IR: InfraRed spectroscopy) as follows, and the content ratio of the phenoxy resin from the resin composition targeted by IR can be determined. In the case of analysis, it can be measured according to the method disclosed in Non-Patent Document 1 above. Specifically, it can be measured by using a general method of IR analysis such as a transmission method or an ATR reflection method. Although the following method is an analysis method for the resin composition in the FRP layer 12, the same analysis method can be applied to the adhesive resin layer 13.
[0056]
　The FRP layer 12 is scraped off with a sharp blade or the like, the fibers are removed as much as possible with tweezers, and the resin composition to be analyzed is sampled from the FRP layer 12. In the case of the transmission method, KBr powder and the powder of the resin composition to be analyzed are crushed while being uniformly mixed in a mortar or the like to prepare a thin film, which is used as a sample. In the case of the ATR reflection method, a tablet may be prepared by crushing while uniformly mixing powder in a mortar as in the transmission method to prepare a sample, or a single crystal KBr tablet (for example, diameter 2 mm×thickness 1. The surface of 8 mm) may be scratched with a file or the like, and the powder of the resin composition to be analyzed may be sprinkled and adhered to form a sample. In any method, it is important to measure the background of KBr alone before mixing with the resin to be analyzed. As the IR measuring device, a general commercially available one can be used, but as for the accuracy, the absorption (Absorbance) is in 1% unit, and the wave number (Wavenumber) is in 1 cm −1 unit. An apparatus is preferable, and examples thereof include FT/IR-6300 manufactured by JASCO Corporation.
[0057]
　When investigating the content of the phenoxy resin (A), the absorption peak of the phenoxy resin is as shown in FIGS. 2, 3, 4, 6, and 7 of Non-Patent Document 1. When only the absorption peaks disclosed in Non-Patent Document 1 above are observed in the measured IR spectrum, it is determined that the IR spectrum is composed of only the phenoxy resin.
[0058]
　On the other hand, when a peak other than the absorption peak disclosed in Non-Patent Document 1 is detected, it is determined that another resin composition is contained, and the content is estimated as follows. The powder of the resin composition to be analyzed and the powder of the phenoxy resin composition (for example, Phenothote YP-50S manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) were mixed at a mass ratio of 100:0, 90:10, A mixture of 80:20, 70:30, 60:40, 50:50, 40:60, 30:70, 20:80, 10:90 and 0:100 was mixed and IR-analyzed to obtain a phenoxy resin. derived peak (e.g. ~ 1480 cm 1450 -1 , 1500 cm -1 vicinity, 1600 cm -1 vicinity, etc.) to record the change in the intensity of. A calibration curve as shown in FIG. 3 is created based on the obtained change in intensity. By using the obtained calibration curve, the phenoxy resin content of a sample whose phenoxy resin content is unknown can be determined.
[0059]
　Specifically, when the phenoxy content of the resin composition to be analyzed is X%, X% can be estimated from the strength change when the phenoxy resin is shaken from X% to 100%. That is, when measured with the above-mentioned mixing ratio, the content of the phenoxy resin changes to X, 0.9X+10, 0.8X+20, 0.7X+30... 0.2X+80, 0.1X+90, 100%. It is possible to draw a straight line connecting each point by taking the content rate on the horizontal axis and the absorption peak intensity on the vertical axis, the intensity when the content is 100% is I 100 , and the intensity when the content is X% is I X , When the content is 0%, that is, when the Y intercept of the graph is I 0 , (I X −I 0 )/(I 100 −I 0 )×100 becomes X%, which can be specified. The reason why the mixing ratio was finely shaken in steps of 10% is to improve the measurement accuracy.
[0060]
　The "phenoxy resin" is a linear polymer obtained from a condensation reaction between a dihydric phenol compound and epihalohydrin or a polyaddition reaction between a dihydric phenol compound and a difunctional epoxy resin, and is an amorphous thermoplastic resin. Is. The phenoxy resin (A) can be obtained by a conventionally known method in a solution or without a solvent, and can be used in any form of powder, varnish and film. The weight average molecular weight (Mw) of the phenoxy resin (A) is, for example, in the range of 10,000 or more and 200,000 or less, preferably in the range of 20,000 or more and 100,000 or less. , And more preferably in the range of 30,000 or more and 80,000 or less. By setting the Mw of the phenoxy resin (A) in the range of 10,000 or more, the strength of the molded article can be increased, and the effect is to set the Mw to 20,000 or more, further 30,000 or more. And it gets even higher. On the other hand, by setting the Mw of the phenoxy resin (A) to 200,000 or less, the workability and processability can be made excellent, and this effect is that the Mw is 100,000 or less, further 80,000 or less. By doing so, it will be even higher.
[0061]
　Further, the average molecular weight of the adhesive resin (phenoxy resin (A) and other resin components) forming the adhesive resin layer 13 is preferably larger than the average molecular weight of the matrix resin 101 of the FRP layer 12. The matrix resin 101 for the FRP layer 12 preferably has a low viscosity when melted in order to enhance the impregnation property into the reinforcing fiber material. Therefore, it is preferable that the matrix resin 101 has a small molecular weight.
[0062]
　The Mw in the present specification is a value measured by gel permeation chromatography (GPC) and converted using a standard polystyrene calibration curve.
[0063]
　The hydroxyl group equivalent (g/eq) of the phenoxy resin (A) used in the present embodiment is, for example, in the range of 50 or more and 1000 or less, preferably in the range of 50 or more and 750 or less, and more preferably 50 or more. It is within the range of 500 or less. When the hydroxyl group equivalent of the phenoxy resin (A) is 50 or more, the hydroxyl group is reduced and the water absorption is lowered, so that the mechanical properties of the cured product can be improved. On the other hand, by setting the hydroxyl equivalent of the phenoxy resin (A) to 1000 or less, it is possible to suppress the decrease of the hydroxyl groups, so that the affinity with the adherend is improved and the mechanical properties of the metal-FRP composite 1 are improved. Can be made. This effect is further enhanced by setting the hydroxyl equivalent to 750 or less, further 500 or less.
[0064]
　The glass transition temperature (Tg) of the phenoxy resin (A) is suitably in the range of 65°C or higher and 150°C or lower, for example, but preferably in the range of 70°C or higher and 150°C or lower. When Tg is 65° C. or higher, the moldability can be ensured and the fluidity of the resin can be prevented from becoming too large, so that the thickness of the adhesive resin layer 13 can be sufficiently secured. On the other hand, when Tg is 150° C. or lower, the melt viscosity becomes low, so that it becomes easy to impregnate the reinforcing fiber base material without defects such as voids, and a lower temperature bonding process can be performed. The Tg of the phenoxy resin (A) in the present specification was measured using a differential scanning calorimeter at a temperature within the range of 20 to 280° C. under a temperature rising condition of 10° C./min, and the second scan peak. It is a numerical value calculated from the value.
[0065]
　The phenoxy resin (A) is not particularly limited as long as it satisfies the above physical properties, but as a preferable one, a bisphenol A type phenoxy resin (for example, Phenotote YP-50 and Phenotote YP manufactured by Nippon Steel & Sumitomo Metal Corporation) is used. -50S, available as Phenotote YP-55U), bisphenol F type phenoxy resin (for example, available as Nippon Steel & Sumikin Chemical Co., Ltd. Phenotote FX-316), copolymerized phenoxy resin of bisphenol A and bisphenol F (for example, , Available as Nippon Steel & Sumikin Chemical Co., Ltd. YP-70), special phenoxy resins such as brominated phenoxy resins other than the above-mentioned phenoxy resins, phosphorus-containing phenoxy resins, sulfone group-containing phenoxy resins (for example, Nippon Steel & Sumikin Chemical Co., Ltd. Fenotooth YPB-43C, available from Fenotooth FX293, YPS-007, etc.). These resins may be used alone or in combination of two or more.
[0066]
　The adhesive resin composition may contain a thermoplastic resin or a thermosetting resin other than the phenoxy resin (A). The type of thermoplastic resin is not particularly limited, and examples thereof include phenoxy resin, polyolefin and acid-modified products thereof, polystyrene, polymethylmethacrylate, AS resin, ABS resin, polyester such as polyethylene terephthalate and polybutylene terephthalate, vinyl chloride, and acrylic. , Super engineering plastics such as polycarbonate, polyamide, polyether sulfone, polyphenylene ether and its modified products, polyimide, polyamide imide, polyether imide, polyether ether ketone, polyphenylene sulfide, polyoxymethylene, polyarylate, polyether ketone, polyether One or more selected from ketone ketone, nylon and the like can be used. As the thermosetting resin, for example, one or more selected from epoxy resin, vinyl ester resin, phenol resin, and urethane resin can be used.
[0067]
　The adhesive resin composition preferably has a melt viscosity of 3,000 Pa·s or less in any temperature range of 160 to 250° C., and within a range of 90 Pa·s or more and 2,900 Pa·s or less. Those having a melt viscosity are more preferable, and those having a melt viscosity in the range of 100 Pa·s or more and 2,800 Pa·s or less are further preferable. When the melt viscosity in the temperature range of 160 to 250° C. is 3,000 Pa·s or less, the fluidity at the time of melting is improved, and defects such as voids are less likely to occur in the adhesive resin layer 13. On the other hand, when the melt viscosity is 90 Pa·s or less, the molecular weight of the resin composition is too small, and when the molecular weight is too small, the resin composition becomes brittle and the mechanical strength of the metal-FRP composite 1 is reduced.
[0068]
◇Crosslinkable adhesive resin composition
　By adding, for example, an acid anhydride, an isocyanate, or caprolactam as a crosslinking agent to the adhesive resin composition containing the phenoxy resin (A), the crosslinkable adhesive resin composition (that is, the adhesive A cured product of the resin composition) can also be used. In the crosslinkable adhesive resin composition, the secondary hydroxyl group contained in the phenoxy resin (A) is used to cause a crosslinking reaction to improve the heat resistance of the adhesive resin composition. It is advantageous for application to. For cross-linking using the secondary hydroxyl group of the phenoxy resin (A), it is preferable to use a cross-linkable adhesive resin composition containing a cross-linking curable resin (B) and a cross-linking agent (C). As the crosslinkable resin (B), for example, an epoxy resin or the like can be used, but it is not particularly limited. By using such a crosslinkable adhesive resin composition, a cured product (crosslinked cured product) in the second cured state in which Tg of the adhesive resin composition is greatly improved as compared with the case of using the phenoxy resin (A) alone is obtained. .. The Tg of the crosslinked cured product of the crosslinkable adhesive resin composition is, for example, 160° C. or higher, preferably 170° C. or higher and 220° C. or lower.
[0069]
　In the crosslinkable adhesive resin composition, the crosslinkable curable resin (B) blended with the phenoxy resin (A) is preferably a bifunctional or higher functional epoxy resin. Examples of the bifunctional or higher epoxy resin include bisphenol A type epoxy resin (for example, available as Epototo YD-011, Epototo YD-7011, and Epototo YD-900 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) and bisphenol F type epoxy resin (for example, , Available as Nippon Steel & Sumikin Chemical Co., Ltd. Epotote YDF-2001), diphenyl ether type epoxy resin (for example, Nippon Steel & Sumikin Chemical Co., Ltd. YSLV-80DE), tetramethylbisphenol F type epoxy resin (for example, Nippon Steel & Sumikin Chemical Co., Ltd.) (Available as YSLV-80XY manufactured by Nippon Steel Co., Ltd.), bisphenol sulfide type epoxy resin (for example, available as YSLV-120TE manufactured by Nippon Steel Sumikin Chemical Co., Ltd.), hydroquinone type epoxy resin (for example Epototo YDC-1312 manufactured by Nippon Steel Sumikin Chemical Co., Ltd.) , And phenol novolac type epoxy resin (available, for example, as Nippon Steel & Sumikin Chemical Co., Ltd. Epototo YDPN-638), orthocresol novolac type epoxy resin (for example, Nippon Steel & Sumitomo Metal Chemical Co., Ltd. Epototo YDCN-701, Epototo) YDCN-702, Epotote YDCN-703, Epotote YDCN-704), aralkylnaphthalene diol novolac type epoxy resin (for example, ESN-355 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), triphenylmethane type epoxy resin (for example, , Available as EPPN-502H manufactured by Nippon Kayaku Co., Ltd.) and the like, but the invention is not limited thereto. Moreover, these epoxy resins may be used individually by 1 type, and may be used in mixture of 2 or more types.
[0070]
　The cross-linking curable resin (B) is not particularly limited, but a crystalline epoxy resin is preferable, and the melting viscosity at 150° C. is 2.0 Pa. A crystalline epoxy resin having s or less is more preferable. By using a crystalline epoxy resin having such melting characteristics, the melt viscosity of the crosslinkable adhesive resin composition as the adhesive resin composition can be reduced, and the adhesiveness of the adhesive resin layer 13 can be improved. You can When the melt viscosity exceeds 2.0 Pa·s, the moldability of the crosslinkable adhesive resin composition may be deteriorated and the homogeneity of the metal-FRP composite 1 may be deteriorated.
[0071]
　Examples of the crystalline epoxy resin suitable as the crosslinking curable resin (B) include Epotote YSLV-80XY, YSLV-70XY, YSLV-120TE, YDC-1312 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., and YX-4000 manufactured by Mitsubishi Chemical Corporation. , YX-4000H, YX-8800, YL-6121H, YL-6640 and the like, HP-4032, HP-4032D, HP-4700 and the like manufactured by DIC Corporation, NC-3000 and the like manufactured by Nippon Kayaku Co., Ltd.
[0072]
　The crosslinking agent (C) crosslinks the phenoxy resin (A) three-dimensionally by forming an ester bond with the secondary hydroxyl group of the phenoxy resin (A). Therefore, unlike strong crosslinking such as curing of a thermosetting resin, the crosslinking can be released by a hydrolysis reaction, so that the metal member 11 and the FRP layer 12 can be easily separated. Therefore, the metal member 11 and the FRP layer 12 can be recycled respectively.
[0073]
　An acid anhydride is preferable as the crosslinking agent (C). The acid anhydride is not particularly limited as long as it is a solid at room temperature and has little sublimation property. Aromatic acid anhydrides having two or more acid anhydrides that react with the hydroxyl group of A) are preferable. In particular, an aromatic compound having two acid anhydride groups such as pyromellitic anhydride has a higher crosslink density and a higher heat resistance than a combination of trimellitic anhydride and a hydroxyl group, and thus is preferably used. To be done. Aromatic dianhydrides such as phenoxy resins such as 4,4'-oxydiphthalic acid, ethylene glycol bisanhydrotrimellitate, and 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride Also, aromatic acid dianhydrides having compatibility with the epoxy resin are more preferable because they have a large effect of improving Tg. In particular, an aromatic acid dianhydride having two acid anhydride groups such as pyromellitic acid anhydride has a higher crosslinking density than phthalic anhydride having only one acid anhydride group, It is preferably used because it has improved heat resistance. That is, since the aromatic acid dianhydride has two acid anhydride groups, it has good reactivity, and a crosslinked cured product having sufficient strength for demolding can be obtained in a short molding time, and the phenoxy resin (A) can be obtained. The final crosslink density can be increased because four carboxyl groups are generated by the esterification reaction with the secondary hydroxyl group therein.
[0074]
　The reaction of the phenoxy resin (A), the epoxy resin as the crosslinking curable resin (B), and the crosslinking agent (C) is performed by reacting the secondary hydroxyl group in the phenoxy resin (A) with the acid anhydride group of the crosslinking agent (C). Is crosslinked and cured by the esterification reaction of ##STR3## and the reaction between the carboxyl group generated by this esterification reaction and the epoxy group of the epoxy resin. Although a phenoxy resin crosslinked product can be obtained by the reaction of the phenoxy resin (A) and the crosslinking agent (C), the coexistence of the epoxy resin can reduce the melt viscosity of the adhesive resin composition, and thus the adherend ( It exhibits excellent properties such as improved impregnation with the metal member 11 and the FRP layer 12), promotion of crosslinking reaction, improvement of crosslinking density, and improvement of mechanical strength.
[0075]
　In the crosslinkable adhesive resin composition, an epoxy resin as a crosslinkable curable resin (B) coexists, but it contains a phenoxy resin (A) which is a thermoplastic resin as a main component, and its secondary hydroxyl group. It is considered that the esterification reaction between the acid anhydride group of the crosslinking agent (C) and the acid anhydride group has priority. That is, since the reaction between the acid anhydride used as the cross-linking agent (C) and the epoxy resin used as the cross-linking curable resin (B) takes time (reaction rate is slow), The reaction with the secondary hydroxyl group of the phenoxy resin (A) occurs first, and then the crosslinking agent (C) remaining in the previous reaction and the residual carboxyl group derived from the crosslinking agent (C) react with the epoxy resin. This further increases the crosslink density. Therefore, unlike a resin composition containing an epoxy resin, which is a thermosetting resin, as a main component, the crosslinked cured product obtained from the crosslinkable adhesive resin composition is a thermoplastic resin and has excellent storage stability.
[0076]
　In the crosslinkable adhesive resin composition utilizing the crosslinking of the phenoxy resin (A), the crosslinking curable resin (B) is in the range of 5 parts by mass or more and 85 parts by mass or less with respect to 100 parts by mass of the phenoxy resin (A). It is preferable that it is contained so that The content of the crosslinkable resin (B) with respect to 100 parts by mass of the phenoxy resin (A) is more preferably in the range of 9 parts by mass or more and 83 parts by mass or less, and further preferably 10 parts by mass or more and 80 parts by mass or less. It is within the range. By setting the content of the cross-linking curable resin (B) to 85 parts by mass or less, the curing time of the cross-linking curable resin (B) can be shortened, so that the strength required for demolding can be easily obtained in a short time. The recyclability of the FRP layer 12 is improved. This effect is further enhanced by setting the content of the crosslinkable curable resin (B) to 83 parts by mass or less, and further 80 parts by mass or less. On the other hand, by setting the content of the crosslinkable curable resin (B) to 5 parts by mass or more, it becomes easy to obtain the effect of improving the crosslink density by the addition of the crosslinkable curable resin (B), and thus the crosslinkable adhesive resin composition is crosslinked. The cured product easily develops Tg of 160° C. or higher, and the fluidity becomes good. The content of the cross-linking curable resin (B) is determined by measuring the peak derived from the epoxy resin in the same manner by the method using IR as described above, thereby measuring the content of the cross-linking curable resin (B). it can.
[0077]
　The amount of the cross-linking agent (C) to be added is usually in the range of 0.6 mol or more and 1.3 mol or less of an acid anhydride group with respect to 1 mol of the secondary hydroxyl group of the phenoxy resin (A), preferably The amount is in the range of 0.7 to 1.3 mol, and more preferably in the range of 1.1 to 1.3 mol. When the amount of the acid anhydride group is 0.6 mol or more, the crosslink density becomes high, so that the mechanical properties and heat resistance are excellent. This effect is further enhanced by setting the amount of the acid anhydride group to 0.7 mol or more, further 1.1 mol or more. When the amount of the acid anhydride group is 1.3 mol or less, it is possible to suppress the unreacted acid anhydride and the carboxyl group from adversely affecting the curing characteristics and the crosslinking density. Therefore, it is preferable to adjust the compounding amount of the crosslinkable resin (B) according to the compounding amount of the crosslinking agent (C). Specifically, for example, an epoxy resin used as the crosslinkable curable resin (B) reacts a carboxyl group generated by the reaction between the secondary hydroxyl group of the phenoxy resin (A) and the acid anhydride group of the crosslinker (C). For that purpose, the compounding amount of the epoxy resin may be in the range of 0.5 mol or more and 1.2 mol or less in terms of an equivalent ratio with the crosslinking agent (C). Preferably, the equivalent ratio of the cross-linking agent (C) to the epoxy resin is in the range of 0.7 mol or more and 1.0 mol or less.
[0078]
　When the cross-linking agent (C) is blended with the phenoxy resin (A) and the cross-linking curable resin (B), a cross-linkable adhesive resin composition can be obtained, but it is promoted as a catalyst so that the cross-linking reaction is surely performed. The agent (D) may be further added. The accelerator (D) is not particularly limited as long as it is a solid at room temperature and has no sublimation property, and examples thereof include tertiary amines such as triethylenediamine, 2-methylimidazole, 2-phenylimidazole, Examples thereof include imidazoles such as 2-phenyl-4-methylimidazole, organic phosphines such as triphenylphosphine, and tetraphenylboron salts such as tetraphenylphosphonium tetraphenylborate. These accelerators (D) may be used alone or in combination of two or more. When the accelerator (D) is used, the content of the accelerator (D) is 0 with respect to 100 parts by mass of the total amount of the phenoxy resin (A), the crosslinkable curable resin (B) and the crosslinker (C). It is preferably in the range of 1 part by weight or more and 5 parts by weight or less.
[0079]
　The crosslinkable adhesive resin composition is a solid at room temperature, and its melt viscosity is such that the minimum melt viscosity, which is the lower limit value of the melt viscosity in the temperature range of 160 to 250° C., is 3,000 Pa·s or less. Is preferable, it is more preferably 2,900 Pa·s or less, still more preferably 2,800 Pa·s or less. When the minimum melt viscosity in the temperature range of 160 to 250° C. is 3,000 Pa·s or less, the adherend can be sufficiently impregnated with the crosslinkable adhesive resin composition during thermocompression bonding such as hot pressing. Since it is possible to suppress the occurrence of defects such as voids in the adhesive resin layer 13, the mechanical properties of the metal-FRP composite 1 are improved. This effect is further enhanced by setting the minimum melt viscosity in the temperature range of 160 to 250° C. to be 2,900 Pa·s or less, and further 2,800 Pa·s or less.
[0080]
　The above-mentioned adhesive resin composition (including a crosslinkable adhesive resin composition) includes, for example, natural rubber, synthetic rubber, elastomers, various inorganic fillers, solvents, and constitutions as long as its adhesiveness and physical properties are not impaired. You may mix|blend other additives, such as a pigment, a colorant, an antioxidant, a UV inhibitor, a flame retardant, and a flame retardant auxiliary.
[0081]
　As described above, an oil film may be formed on the surface of the metal member 11. When it is difficult to bond the FRP and the metal member 11 with sufficient bonding strength even if the FRP and the metal member 11 are bonded with the adhesive resin layer 13 while such an oil film is formed on the surface of the metal member 11. There is. That is, it may be difficult to bond the adhesive resin layer 13 and the metal member 11 with sufficient bonding strength. As one of the measures against such a problem, there is a method of degreasing the surface of the metal member 11 as described above. Another method is a method of adding an oil surface adhesive to the adhesive resin composition.
[0082]
　Here, the oil surface adhesive agent is an adhesive agent that exhibits adhesiveness to an adherend on which an oil film is formed. The oil surface adhesive is also called an oil absorbing adhesive or the like, and contains a component having a high affinity with oil. That is, when the oil surface adhesive is applied to the adherend, the oil adhesive adheres to the adherend while absorbing the oil content on the surface of the adherend. Various types of oil surface adhesives are commercially available, and they can be used in this embodiment without particular limitation. That is, when the metal member 11 on which the oil film is formed and the FRP are joined by the adhesive resin layer 13 containing a certain adhesive, when the metal-FRP composite 1 exhibiting the superaddition rule can be produced, It can be said that the adhesive is an oil surface adhesive suitable for this embodiment. Examples of the oil surface adhesive include Alpha Tech 370 (epoxy oil surface adhesive) manufactured by Alpha Industry Co., Ltd. and Devcon PW1 (methacrylate oil surface adhesive) manufactured by Devcon Corporation. Only one type of oil surface adhesive may be used, or a plurality of types of oil surface adhesive may be mixed and used.
[0083]
　The compounding amount of the oil surface adhesive may be adjusted so that the metal-FRP composite 1 exhibits the superaddition rule. May be
[0084]
　Note that an oil surface adhesive may be applied to the interface between the adhesive resin layer 13 and the metal member 11 to adhere them. That is, an oil surface adhesive may be applied to the surface of at least one of the adhesive resin layer 13 and the metal member 11 to adhere them. The specific coating amount may be adjusted so that the metal-FRP composite 1 exhibits the superaddition rule. As an example, the applied amount may be 10-500 μm thick. The coating method is not particularly limited, and examples thereof include roll coating, bar coating, spraying, dipping, and coating using a brush.
[0085]
　As described above, as a countermeasure when the oil film is formed on the surface of the metal member 11, a method of performing degreasing treatment, a method of adding an oil surface adhesive to the adhesive resin composition, a metal member 11 and an adhesive resin layer There may be mentioned a method of applying an oil surface adhesive to the interface with 13. Any one of these may be used, or two or more thereof may be used in combination. As described above, when the metal member 11 is a hot dip galvanized steel sheet, an electrogalvanized steel sheet, or an aluminum plated steel sheet, an oil film is often formed on the surface of the metal member 11. Therefore, when the metal member 11 is made of these steel plates, it is preferable to consider taking the above oil film countermeasure.
[0086]
(Thickness of Adhesive Resin Layer 13) In the
　metal-FRP composite 1 according to the present embodiment , the thickness of the adhesive resin layer 13 is more than 20 μm from the viewpoint of ensuring sufficient adhesiveness between the metal member 11 and the FRP layer 12. Is preferable, and more preferably 30 μm or more. By setting the thickness of the adhesive resin layer 13 to more than 20 μm, the adhesiveness between the metal member 11 and the FRP layer 12 can be sufficiently enhanced, and the metal-FRP composite 1 can have sufficient workability. On the other hand, from the viewpoint of sufficiently securing the mechanical characteristics of the metal-FRP composite 1, the thickness of the adhesive resin layer 13 is preferably 500 μm or less, more preferably 200 μm or less. This is because if the adhesive resin layer 13 is too thick, the meaning of the resin whose strength is increased by the fibers becomes weak.
[0087]
(Regarding Super Addition Rule)
　The maximum load of the metal-FRP composite 1 according to the present embodiment exhibits excellent strength exceeding the addition rule, that is, the super addition rule. Here, the superaddition rule in the present embodiment will be described based on FIG. 11. FIG. 11 is a graph schematically showing the results of measuring the tensile load of the metal member 11 alone, the tensile load of the FRP alone, and the tensile load of the metal-FRP composite 1. Here, the measurement of tensile load shall be performed by the method shown in the Example mentioned later. The horizontal axis of FIG. 11 represents the amount of deformation of the test piece, and the vertical axis represents the tensile load. The graph L1 shows the correlation between the deformation amount and the tensile load of the metal member 11 alone, and the load A1 shows the maximum load (the maximum value of the tensile load) of the metal member 11 alone. The load A2 indicates a tensile load of the metal member 11 at a deformation amount D described later. The X mark in the graph L1 indicates the amount of deformation and the tensile load when the metal member 11 breaks.
[0088]
　The graph L2 shows the correlation between the deformation amount and the tensile load of the FRP alone, and the load B shows the maximum load (the maximum value of the tensile load) of the FRP alone. The mark X in the graph L2 indicates that the FRP was broken. The graph L3 shows the correlation between the deformation amount of the metal-FRP composite 1 and the tensile load, and the load C shows the maximum load (the maximum value of the tensile load) of the metal-FRP composite 1. The mark X in the graph L3 indicates that the metal-FRP composite 1 was broken, and the deformation amount D indicates the deformation amount (elongation) of the metal-FRP composite 1 when the metal-FRP composite 1 was broken.
[0089]
　The super-addition rule in the present embodiment means that the expression (2-2) among the following expressions (2-1) and (2-2) considered as the super-addition rule is satisfied.
　C>A1+B (2-1)
　C>A2+B (2-2)
　That is, in the determination of the success or failure of the superadditive rule, it may be determined whether or not the equation (2-2) is satisfied. Here, since the load A1 is larger than the load A2, if the expression (2-1) is satisfied, the expression (2-2) is inevitably satisfied. Therefore, when the expression (2-1) is satisfied, However, it may be determined that the super-additive rule holds.
[0090]
　In the case of a metal of A1>>A2 such as high-tensile steel, the formula (2-2) is satisfied, but the formula (2-1) is often not satisfied. However, it is possible to determine whether the superaddition rule is satisfied, but in the case of a metal in which the load A1 and the load A2 are close to each other (for example, in the case of A1/A2<1.1, ( In FIG. 11 is one example), the load A1 may be easier to measure, and in that case, it is easier to determine the superaddition rule based on the equation (2-1). At that time, even if the equation (2-1) is not satisfied, if the equation (2-2) is satisfied, it is determined that the super-addition rule is satisfied.
[0091]
　If the load C is about the same as the total load of the load A1 and the load B, A1>A2, and the super-addition rule is established. As shown in a comparative example described later, in the metal-FRP composite that does not satisfy the requirements of the present embodiment, the load C may be less than the total load of the load A2 and the load B.
[0092]
　Here, the ratio of the load C to the total load of the load A2 and the load B (=C/(A2+B)) is defined as the degree of superaddition rule. In this embodiment, the degree of superaddition rule exceeds 1.00. The superaddition rule degree is preferably 1.01 or more, and more preferably 1.05 or more. Here, in the determination of establishment of the above-mentioned super-addition rule, in the case of a metal such as soft steel in which the load A1 and the load A2 are close to each other, it can be easily determined by using the formula (2-1). However, it is preferable that the degree of superaddition rule is calculated by C/(A2+B).
[0093]
In order for the
　metal-FRP composite 1 to express the superaddition rule (for the formula (1)) , for example, the metal member 11, the FRP layer 12, and the adhesive resin layer 13 have the above-described configurations, and It suffices if Expression (1) is satisfied.
　　(T1×E1)/(T2×E2)>0.3...Equation (1)
[0094]
　In the formula (1), T1 is the total thickness of the metal member 11, E1 is the elastic coefficient of the metal member 11, T2 is the total thickness of the FRP layer 12 and the adhesive resin layer 13, and E2 is the FRP. It is the elastic modulus of the layer 12 and the adhesive resin layer 13. Therefore, T1 and E1 are parameters related to the metal member 11, and T2 and E2 are parameters related to the FRP layer 12 and the adhesive resin layer 13. T1 is defined as "the total thickness of the metal member 11" when the metal-FRP composite 1 is produced by using a plurality of metal members 11 such as sandwiching the FRP layer 12 with a plurality of metal members 11. Because there is. Further, the elastic coefficient E2 may be calculated according to the addition rule. For example, assuming that the FRP layer 12 is A and the adhesive resin layer 13 is B, the elastic modulus E2 is (elastic modulus of A×thickness of A/total thickness T2 of FRP layer 12 and adhesive resin layer 13)+(elasticity of B) It is calculated by the coefficient×thickness B/total thickness T2) of the FRP layer 12 and the adhesive resin layer 13. Here, it is not necessary to consider the elastic coefficient of the adhesive resin layer 13 in the elastic coefficient E2. This is because the tensile strengths of the FRP layer 12 and the adhesive resin layer 13 substantially depend on the FRP layer 12, more specifically, the reinforcing fiber material 102 in the FRP layer 12. Further, the adhesive resin layer 13 may be very thin with respect to the thickness of the FRP layer 12. In this case, T2 may be only the thickness of the FRP layer 12. That is, the thickness of the adhesive resin layer 13 may be ignored. For example, when the thickness of the adhesive resin layer 13 is 5 μm or less with respect to the thickness of the FRP layer 12, the thickness of the adhesive resin layer 13 may be ignored. When a plurality of types of metal members 11 are stacked, E1 is calculated according to the additive rule. For example, when the metal member 11 is composed of A, B,..., E1 is (elastic coefficient of A×thickness of A/total thickness T1 of a plurality of metal members)+(elastic coefficient of B×B) Thickness/total thickness T1) of the plurality of metal members is calculated. Similarly, when a plurality of types of FRP layers 12 are laminated, E2 is calculated according to the addition rule. For example, if the plurality of FRP layers 12 are A, B, C,... The coefficient is calculated as follows: sex coefficient×A thickness/total thickness T2 of a plurality of FRP layers+(elastic coefficient B×thickness B/total thickness T2 of a plurality of FRP layers). The elastic coefficient of the FRP layer 12 may be the elastic coefficient of the reinforcing fiber material 102 forming the FRP layer 12.
[0095]
　The maximum load of the metal-FRP composite 1 satisfying the formula (1) exhibits excellent strength and superaddition rule exceeding the addition rule. The reason is presumed as follows. The metal-FRP composite 1 has a metal member 11, an FRP layer 12, and an adhesive resin layer 13 interposed therebetween. Although the FRP layer 12 is brittle, the metal member 11 is ductile and has a large elastic coefficient E1. At this time, since the adhesive resin layer 13 contains the phenoxy resin (A) having excellent adhesiveness to the metal member 11, the metal member 11 and the FRP layer 12 are firmly adhered by the adhesive resin layer 13. Therefore, when the metal-FRP composite 1 is subjected to a large tensile load, the FRP layer 12 (having brittleness) is broken, and the metal member 11 (having ductility and a large elastic coefficient E1). ) Acts to suppress. Therefore, it is considered that the metal-FRP composite 1 shows a higher strength as compared with the metal member 11 alone or the FRP layer 12 alone when the total thickness is compared under the same conditions.
[0096]
　Further, the coefficient of thermal expansion differs between the metal member 11 and the adhesive resin forming the adhesive resin layer 13, and the amount of change due to heat is larger in the metal member 11. Therefore, when the metal-FRP composite 1 is molded at a high temperature and then cooled in the manufacturing process, the FRP layer 12 and the adhesive resin layer 13 follow the metal member 11 having large expansion and contraction to some extent from the beginning. It is fixed with compressive force (internal stress) applied. When a tensile load is applied to the metal-FRP composite 1, the FRP layer 12 and the adhesive resin layer 13 in the compressed state have a larger elongation margin than in the non-compressed state, and the fracture is delayed by that amount. As a result, it is considered that the entire metal-FRP composite 1 can exhibit high tensile strength. Such an effect is more effectively obtained as the elastic coefficient E1 of the metal member 11 increases. That is, the larger the elastic modulus E1 of the metal member 11, the larger the tensile load per unit elongation of the metal-FRP composite 1. Then, as described above, the expansion margin is increased due to the internal stress. Therefore, the larger the elastic modulus E1 of the metal member 11 is, the larger the tensile load corresponding to this margin (the tensile load necessary to extend the metal-FRP composite 1 by the above-mentioned margin) becomes, and therefore the metal-FRP composite is increased. The body 1 can withstand higher tensile loads.
[0097]
　Here, the above equation (1) is derived by the following experiment.
　That is, whether or not the strength exceeding the additive rule was obtained for a large number of samples in which the thickness and elastic coefficient of the metal member and the FRP thickness and elastic coefficient were changed was verified by experiments, and then the thickness of the FRP was changed laterally. Along the axis, the verification result (whether or not strength exceeding the addition rule was obtained) of each sample was plotted on the coordinate plane with the thickness of the metal member as the vertical axis. Then, it is derived from the result of expressing the straight line representing the boundary of the region where the intensity exceeding the addition rule is obtained as an approximated curve by a known statistical analysis process. According to the above equation (1), for example, when the elastic coefficient E2 of the FRP layer 12 is fixed and the elastic coefficient E1 of the metal member 11 is high, the addition is performed even if the total thickness T1 of the metal member 11 is reduced. Excellent strength exceeding the law can be realized. On the contrary, if the elastic coefficient E1 of the metal member 11 is low, the total thickness T1 of the metal member 11 is increased in order to realize excellent strength exceeding the addition rule.
[0098]
　For the above reasons, it is preferable that the metal-FRP composite 1 satisfying the above formula (1) is made of iron (steel material, iron-based alloy, etc.) as the material of the metal member 11. Since iron has a large elastic coefficient E1 of about 200 GPa and has toughness, excellent strength can be maintained even if the thickness T1 is reduced. Further, as the material of the metal member 11, titanium (about 105 GPa), aluminum (about 70 GPa) or the like having a large elastic coefficient E1 is preferably used, though not so much as iron.
[0099]
　The thicknesses of the metal member 11, the FRP layer 12, and the adhesive resin layer 13 can be measured in accordance with the cross section method of the optical method of JIS K 5600-1-7, 5.4 as follows. it can. That is, a room temperature curable resin that can be embedded without any harmful effect on the sample is used, and a low viscosity Epomount 27-777 manufactured by Refinetech Co., Ltd. is used as a main agent and 27-772 is used as a curing agent. Embed. At a place to be observed with a cutting machine, the sample is cut so as to be parallel to the thickness direction and a cross-section is taken out. A observing surface is prepared by polishing with a (counter). If an abrasive is used, it is polished with an appropriate grade of diamond paste or similar paste to create the viewing surface. If necessary, buffing may be carried out so that the surface of the sample is smoothed to the condition that it can be observed.
[0100]
　Use a microscope equipped with an appropriate illumination system to give the optimum image contrast, and use a microscope capable of measuring with an accuracy of 1 μm (for example, BX51 manufactured by Olympus Co., Ltd.) so that the size of the visual field is 300 μm. select. The size of the visual field may be changed so that each thickness can be confirmed (for example, if the thickness of the FRP layer 12 is 1 mm, the size of the visual field can be changed). For example, when measuring the thickness of the adhesive resin layer 13, the observation visual field is equally divided into four as shown in FIG. 4, and the thickness of the adhesive resin layer 13 is measured at the center portion in the width direction of each separation point. Let the average thickness be the thickness in the said visual field. This observation visual field is performed by selecting 5 different places, and each observation visual field is divided into four equal parts, the thickness is measured in each fraction, and the average value is calculated. Adjacent observation fields of view are preferably separated by 3 cm or more. The value obtained by further averaging the average values ​​at the five points may be used as the thickness of the adhesive resin layer 13. The thickness of the metal member 11 and the FRP layer 12 may be measured in the same manner as the thickness of the adhesive resin layer 13.
[0101]
　When the boundary surfaces of the metal member 11, the FRP layer 12, and the adhesive resin layer 13 are relatively clear, the thickness of the adhesive resin layer 13 can be measured by the above method. However, the boundary surface between the FRP layer 12 and the adhesive resin layer 13 is not always clear. When the boundary surface is unclear, the boundary surface may be specified by the following method. That is, the metal-FRP composite 1 is scraped off from the metal member 11 side by using a grinder or the like to which a diamond grindstone is attached. Then, the cut surface is observed with the microscope to measure the area ratio of the fiber portions forming the reinforcing fiber material 102 (the area ratio of the fiber portions to the total area of ​​the observation visual field). The area ratio may be measured in a plurality of observation visual fields, and the arithmetic mean value thereof may be used as the area ratio of the fiber portion. Then, the cut surface when the area ratio of the fiber portion exceeds 10% may be the boundary surface between the FRP layer 12 and the adhesive resin layer 13.
[0102]
(Regarding the preferable range of (T1×E1)/(T2×E2))
　As described above, the degree of superaddition rule is preferably 1.01 or more, and more preferably 1.05 or more. In other words, it can be said that the larger the degree of superadditive rule, the more preferable. Then, the present inventor examined in detail the results of Examples described later (Examples in which the metal-FRP composite 1 was produced under various manufacturing conditions and the characteristics thereof were evaluated). As a result, (T1×E1)/ It was revealed that there is a correlation between (T2×E2) and the degree of superaddition rule. Since the manufacturing conditions of each example are various, it is not possible to simply compare the degree of superaddition rule of each example. Therefore, the present inventor estimates the degree of superaddition rule when the manufacturing conditions are leveled, and the result shows the results of (T1×E1)/(T2×E2) on the horizontal axis and the superaddition rule on the vertical axis. When plotted on a plane having a certain degree, a graph L4 shown in FIG. 12 was obtained. According to this graph L4, when (T1×E1)/(T2×E2) becomes 0.3, the degree of superaddition rule becomes 1.00, and (T1×E1)/(T2×E2) becomes When it is larger than 0.3 (that is, when Expression (1) is satisfied), the degree of superaddition rule exceeds 1.00. Further, the degree of superaddition rule takes a maximum value within the range of (T1×E1)/(T2×E2) of 1.7 to 6.0. Therefore, it is understood that the preferable lower limit value of (T1×E1)/(T2×E2) is 1.7 or more and the preferable upper limit value thereof is 6.0 or less. When (T1×E1)/(T2×E2) takes a value within this range, the degree of superaddition rule becomes 1.01 or more, and further 1.05 or more. A more preferable lower limit is 2.5 or more, and a more preferable upper limit is 3.0 or less. This is because, when (T1×E1)/(T2×E2) is 2.5 or more and 3.0 or less, the degree of superaddition rule becomes the maximum value or becomes a value closer to the maximum value. The maximum value is greater than 1.05 and may be, for example, about 1.3.
[0103]
[Method for Producing
　Metal-Fiber Reinforced Resin Material Composite] The configuration of the metal-FRP composite 1 as the metal-fiber reinforced resin material composite according to the present embodiment has been described in detail above. A method of manufacturing the metal-FRP composite 1 according to this embodiment will be described with reference to FIGS. 5 and 6 are explanatory views showing an example of a manufacturing process of the metal-FRP composite 1.
[0104]
　In the metal-FRP composite 1, the FRP (or the FRP molding prepreg which is a precursor thereof) processed into a desired shape and the metal member 11 are provided with an adhesive resin composition (including a crosslinkable adhesive resin composition). And the adhesive resin composition is solidified (in the case of a crosslinkable adhesive resin composition, cured). The adhered FRP becomes the FRP layer 12, and the solidified or cured product of the adhesive resin composition becomes the adhesive resin layer 13. As a method of forming a composite by adhering the metal member 11 and FRP with an adhesive resin composition and joining them, for example, the following method 1 or method 2 can be performed, but the method 1 is more preferable.
[0105]
(Method 1) In
　Method 1, after a coating film (which will become the adhesive resin layer 13) made of the adhesive resin composition is formed on the surface of the metal member 11, an FRP or FRP forming prepreg (the first prepreg which becomes the FRP layer 12 is formed. Prepregs) are laminated and thermocompression bonded.
[0106]
　In this method 1, for example, as shown in FIG. 5A, a powdery or liquid adhesive resin composition is applied to at least one surface of the metal member 11 to form a coating film 20. In the method 1, the coating film 20 may be formed not on the metal member 11 side but on the FRP side that becomes the FRP layer 12 or the FRP molding prepreg (first prepreg) side, but here, the metal member 11 is formed. The case where the coating film 20 is formed on the side will be described as an example.
[0107]
　Next, as shown in FIG. 5( b ), the FRP molding prepreg 21 that will become the FRP layer 12 is placed on the side of the metal member 11 on which the coating film 20 is formed, and the metal member 11 and the coating film 20 are arranged. And the FRP molding prepreg 21 are laminated in this order to form a laminated body. In addition, in FIG. 5B, FRP may be laminated instead of the FRP molding prepreg 21. At this time, the bonding surface of the FRP may be roughened by blasting, plasma treatment, corona treatment, or the like. It is preferable that the activation is performed by such as. Next, by heating and pressurizing this laminated body, a metal-FRP composite 1 is obtained as shown in FIG. 5(c).
[0108]
　In Method 1, as a method of forming the coating film 20 to be the adhesive resin layer 13, a method of powder coating the powder of the adhesive resin composition on the surface of the metal member 11 is preferable. The adhesive resin layer 13 formed by powder coating is easily melted because the adhesive resin composition is fine particles, and voids are easily removed because the coating film 20 has appropriate voids. Moreover, since the adhesive resin composition wets the surface of the metal member 11 well when the FRP or the FRP molding prepreg 21 is heat-pressed, a degassing step such as varnish coating is not necessary, and as seen in a film. Defects due to lack of wettability such as generation of voids are unlikely to occur.
[0109]
　In the method 1, the coating film 20 is formed on both surfaces of the metal member 11 in FIG. 5A, and the FRP molding prepreg 21 (or FRP) is formed on each of the coating films 20 in FIG. 5B. You may laminate. Further, the FRP molding prepreg 21 (or FRP) that becomes the FRP layer 12 is not limited to one layer, and may be a plurality of layers (see FIG. 2 ). Further, two or more metal members 11 may be used and the FRP molding prepreg 21 (or FRP) to be the FRP layer 12 may be laminated so as to be sandwiched.
[0110]
(Method 2) In
　Method 2, the adhesive resin composition formed into a film and the FRP or FRP molding prepreg (first prepreg) to be the FRP layer 12 are laminated on the metal member 11 and thermocompression bonded.
[0111]
　In this method 2, as shown in FIG. 6A, for example, on at least one surface of the metal member 11, an adhesive sheet 20A in which the adhesive resin composition is formed into a film, and an FRP molding prepreg 21 which becomes the FRP layer 12 are formed. Are stacked and arranged to form a laminated body in which the metal member 11, the adhesive sheet 20A, and the prepreg 21 for FRP molding are laminated in this order. Note that, in FIG. 6A, FRP may be laminated instead of the FRP molding prepreg 21, but at this time, the bonding surface of the FRP is roughened by blasting or the like, plasma-treated, corona-treated, or the like. It is preferable that the activation is performed by such as. Next, by heating and pressurizing this laminated body, the metal-FRP composite 1 is obtained as shown in FIG. 6(b).
[0112]
　In Method 2, in FIG. 6A, the adhesive sheet 20A and the FRP molding prepreg 21 (or FRP) may be laminated on both surfaces of the metal member 11, respectively. Further, the FRP molding prepreg 21 (or FRP) serving as the FRP layer 12 is not limited to one layer and may be a plurality of layers (see FIG. 2 ). In addition, two or more metal members 11 may be used and the adhesive sheet 20A and the FRP molding prepreg 21 (or FRP) that becomes the FRP layer 12 may be laminated so as to be sandwiched.
[0113]
(Compounding with
　Metal Member ) It is preferable to carry out the compounding of the metal member 11 and the FRP as follows, for example.
　i) In the above method 1, the adhesive resin composition is applied as powder or varnish at a predetermined position on the adhesive surface of the metal member 11 to form the coating film 20 to be the adhesive resin layer 13. Next, the laminated body in which the FRP molding prepreg 21 to be the FRP layer 12 is laminated is placed in a pressure molding machine and pressure-molded to form the adhesive resin layer 13.
　ii) In the above method 2, the adhesive sheet 20A to be the adhesive resin layer 13 is arranged at a predetermined position on the adhesive surface of the metal member 11. Next, the laminated body in which the FRP molding prepreg 21 to be the FRP layer 12 is laminated is placed on a pressure molding machine and pressure-molded to form the adhesive resin layer 13.
[0114]
(Heat compression bonding conditions) In the
　above methods 1 and 2, the heat compression bonding conditions for compounding the metal member 11, the adhesive sheet 20A, and the FRP molding prepreg 21 (or FRP) that becomes the FRP layer 12 are: It is as follows.
[0115]
　The thermocompression bonding temperature is not particularly limited, but is, for example, in the range of 100°C or higher and 400°C or lower, preferably 150°C or higher and 300°C or lower, more preferably 160°C or higher and 270°C or lower, and further preferably 180°C or higher. It is within the range of 250°C or lower. Within such a temperature range, the temperature above the melting point is more preferable for a crystalline resin, and the temperature above Tg+150° C. is more preferable for an amorphous resin. If the temperature exceeds the upper limit, excessive heat may be applied, resulting in decomposition of the resin.If the temperature is lower than the lower limit, the melt viscosity of the resin is high. Impregnation into the material becomes poor.
[0116]
　The pressure at the time of thermocompression bonding is, for example, preferably 3 MPa or more, more preferably 3 MPa or more and 5 MPa or less. If the pressure exceeds the upper limit, excessive pressure is applied, which may cause deformation or damage. If the pressure is lower than the lower limit, impregnability into the reinforcing fiber base material deteriorates.
[0117]
　As for the thermocompression bonding time, if it is at least 3 minutes or more, the thermocompression bonding can be sufficiently performed, and it is preferably within the range of 5 minutes or more and 20 minutes or less.
[0118]
　In the thermocompression bonding step, a composite batch molding of the metal member 11, the adhesive sheet 20A, and the FRP molding prepreg 21 (or FRP) that becomes the FRP layer 12 may be performed by a pressure molding machine. The composite collective molding is preferably performed by hot pressing, but it is also possible to quickly install the material preheated to a predetermined temperature in a low-temperature pressure molding machine for processing. By performing the thermocompression bonding process as described above, the FRP layer 12 can be bonded to the metal member 11 in a state in which a compressive force (internal stress) is applied to the FRP layer 12 and the adhesive resin layer 13, and thus the above-mentioned super The additive rule can be expressed.
[0119]
(Additional heating step) In the
　methods 1 and 2, as the adhesive resin composition for forming the adhesive resin layer 13 and the raw material resin for forming the matrix resin 101, a phenoxy resin (A) and a crosslinkable curable resin ( When the crosslinkable adhesive resin composition containing B) and the crosslinking agent (C) is used, an additional heating step may be further included.
[0120]
　When the crosslinkable adhesive resin composition is used, the adhesive resin layer 13 is formed by the first cured product (solidified product) in the thermosetting process, which is solidified but not crosslinked (cured). Can be formed. Further, when the same or similar kind as the crosslinkable adhesive resin composition is used as the raw material resin of the matrix resin of the FRP molding prepreg 21 which becomes the FRP layer 12, a cured product (solidified product) in the first cured state The FRP layer 12 including the matrix resin 101 made of can be formed.
[0121]
　In this way, through the thermocompression bonding process, the metal member 11, the adhesive resin layer 13 of the first cured product (solidified product), and the FRP layer 12 are laminated and integrated into a metal- An intermediate (preform) of FRP composite 1 can be produced. In this intermediate body, if necessary, the FRP layer 12 may be one in which the matrix resin 101 is a cured product (solidified product) in the first cured state. Then, by performing an additional heating step on the intermediate body after the thermocompression bonding step, post-curing is performed on at least the adhesive resin layer 13 made of the cured product (solidified product) in the first cured state. The resin can be cross-linked and cured to be a cured product in the second cured state (cross-linked cured product). Preferably, the FRP layer 12 is also post-cured to cross-link and harden the matrix resin 101 made of a cured product (solidified product) in the first cured state to obtain a cured product in the second cured state (cross-linked cured product). Can be changed to.
[0122]
　The additional heating step for post-curing is preferably performed at a temperature in the range of 200° C. or higher and 250° C. or lower for about 30 minutes to 60 minutes. It should be noted that instead of post-cure, heat history in a post-process such as painting may be used.
[0123]
　As described above, when the crosslinkable adhesive resin composition is used, Tg after crosslinking and curing is significantly improved as compared with the phenoxy resin (A) alone. Therefore, before and after the additional heating step is performed on the above-described intermediate, that is, the resin changes from the first cured state cured product (solidified product) to the second cured state cured product (crosslinked cured product). In the process, Tg changes. Specifically, the Tg of the resin before cross-linking in the intermediate is, for example, 150° C. or lower, whereas the Tg of the cross-linked resin after the additional heating step is, for example, 160° C. or higher, preferably 170° C. Since the temperature is improved within the range of 220° C. or less, heat resistance can be significantly increased.
[0124]
(Pretreatment Step) When the
　metal-FRP composite 1 is manufactured, it is preferable to degrease the metal member 11 as a pretreatment step of joining the metal member 11 and the FRP with the adhesive resin composition, and releasing the metal member 11 from the mold. It is more preferable to perform the mold treatment and the removal of the deposits (dust removal) on the surface of the metal member 11. Except for a steel plate having very high adhesion such as TFS (Tin Free Steel), the metal member 11 such as a steel plate to which rust-preventing oil or the like is normally attached must be degreased to recover the adhesion, as described above. It is difficult to obtain strength exceeding the additive rule. Therefore, by performing the above-mentioned pretreatment on the metal member 11, it becomes easy for the metal-FRP composite 1 to obtain strength exceeding the additive rule. Regarding the necessity of degreasing, whether the target metal member is joined in advance to the target FRP by the target adhesive resin composition without the degreasing step and integrated so that the superaddition rule actually occurs. You can make a decision by checking. The determination of whether the super-additive rule occurs will be described later in [Confirmation of existence of super-additive rule]. As described above, the oil surface adhesive may be added to the adhesive resin composition together with the degreasing treatment or instead of the degreasing treatment, or the oil surface adhesive may be adhered to the interface between the adhesive resin layer 13 and the metal member 11. A hydrophilic adhesive may be applied.
[0125]
(Post-process) In the post-process for the
　metal-FRP composite 1, in addition to painting, mechanical bonding with other members such as bolts and riveting, drilling, application of adhesive for adhesive bonding, etc. Is done.
[0126]
Second Embodiment
[Configuration of Metal-Fiber Reinforced Resin Material Composite]
　Next, referring to FIGS. 7 and 8, a metal-fiber reinforced resin material composite according to a second embodiment of the present invention. The configuration of will be described. 7 and 8 are schematic views showing a cross-sectional structure in the stacking direction of the metal-FRP composite 2 as an example of the metal-fiber reinforced resin material composite according to the present embodiment.
[0127]
　As shown in FIG. 7, the metal-FRP composite 2 includes a metal member 11, an FRP layer 12 as an example of the first fiber-reinforced resin material according to this embodiment, and an adhesive resin layer 13A. The metal member 11 and the FRP layer 12 are compounded via the adhesive resin layer 13A. In the present embodiment, the above description is that the adhesive resin layer 13A is the second fiber-reinforced resin material that includes the matrix resin 103 and the reinforced fiber material 104 that is contained in the matrix resin 103 and is composited. It is different from the adhesive resin layer 13 according to the first embodiment. As will be described later, the matrix resin 103 is a solidified product or a cured product of an adhesive resin composition containing 50 parts by mass or more of the phenoxy resin (A) with respect to 100 parts by mass of the resin component.
[0128]
　Here, the configuration of the FRP layer 12 is similar to that of the first embodiment described above. Further, in the present embodiment, the adhesive resin layer 13A is provided so as to contact at least one surface of the metal member 11, and firmly adheres the metal member 11 and the FRP layer 12 to each other. However, the adhesive resin layer 13A and the FRP layer 12 may be provided not only on one side of the metal member 11 but also on both sides thereof. Alternatively, a laminate including the adhesive resin layer 13A and the FRP layer 12 may be sandwiched between the two metal members 11.
[0129]
　Also in the metal-FRP composite 2, as in the metal-FRP composite 1, the FRP layer 12 is composed of at least one FRP molding prepreg, and the FRP layer 12 is The number of layers is not limited to one and may be two or more as shown in FIG. 8, for example. The number n of layers of the FRP layer 12 when the FRP layer 12 is composed of a plurality of layers may be appropriately set according to the purpose of use. When there are a plurality of FRP layers 12, each layer may have the same structure or different layers. That is, the resin type of the matrix resin 101 forming the FRP layer 12, the type and content ratio of the reinforcing fiber material 102, and the like may be different for each layer.
[0130]
　Further, the maximum load of the metal-FRP composite 2 exhibits excellent strength exceeding the addition rule, that is, the super-addition rule, similarly to the metal-FRP composite 1 according to the first embodiment. Furthermore, the total thickness T1 of the metal member 11 and the elastic coefficient E1 of the metal member 11, the total thickness T2 of the FRP layer 12 and the adhesive resin layer 13, and the elastic coefficient E2 of the FRP layer 12 are expressed by the above formula (1). To satisfy the relationship. The preferable range of (T1×E1)/(T2×E2) is also the same as in the first embodiment. Since the elastic modulus of the adhesive resin layer 13A is large in the second embodiment, E2 is preferably the elastic modulus of the laminate of the FRP layer 12 and the adhesive resin layer 13.
[0131]
　Hereinafter, each component of the metal-FRP composite 2 and other configurations will be described in detail, but the description common to the metal-FRP composite 1 according to the first embodiment will be appropriately omitted, and the adhesive resin layer 13A will be bonded. The description will focus on the parts different from the resin layer 13.
[0132]
(Adhesive Resin Layer 13A) The
　adhesive resin layer 13A joins the metal member 11 of the metal-FRP composite 2 and the FRP layer 12 together.
[0133]
Adhesive resin composition The
　matrix resin 103, which is the adhesive resin constituting the adhesive resin layer 13A, is a solidified product or a cured product of the adhesive resin composition containing 50 parts by mass or more of the phenoxy resin (A) with respect to 100 parts by mass of the resin component. Is. By using such an adhesive resin composition, it becomes possible to firmly bond the metal member 11 and the FRP layer 12.
[0134]
　Here, from the viewpoint of sufficiently securing the adhesiveness between the FRP layer 12 and the adhesive resin layer 13A, the FRP is made of the same or the same resin as the resin forming the matrix resin 103 which is the adhesive resin forming the adhesive resin layer 13A. It is preferable to form the matrix resin 101 of the layer 12.
[0135]
　When the metal-FRP composite 2 has a plurality of FRP layers 12, the resin species forming the matrix resin 103 of the adhesive resin layer 13A and the FRP layer 12 closest to the adhesive resin layer 13A in contact with the adhesive resin layer 13A. The resin species of the matrix resin 101 may be the same or different. From the viewpoint of securing the adhesiveness between the adhesive resin layer 13A and the FRP layer 12 in contact with the adhesive resin layer 13A, as the resin species of the matrix resin 103 and the matrix resin 101, the same or the same type of resin, or the ratio of polar groups contained in the polymer It is preferable to select a combination of resin types having similar values.
[0136]
◇Crosslinkable Adhesive Resin Composition
　Similar to the adhesive resin layer 13 according to the first embodiment, an adhesive resin composition containing a phenoxy resin (A) as the matrix resin 103 of the adhesive resin layer 13A is, for example, acid anhydride. It is also possible to use a crosslinkable adhesive resin composition (that is, a cured product of the adhesive resin composition) by blending a compound, isocyanate, caprolactam or the like as a crosslinking agent. In the crosslinkable adhesive resin composition, the secondary hydroxyl group contained in the phenoxy resin (A) is used to cause a crosslinking reaction to improve the heat resistance of the adhesive resin composition. It is advantageous for application to. For cross-linking using the secondary hydroxyl group of the phenoxy resin (A), it is preferable to use a cross-linkable adhesive resin composition containing a cross-linking curable resin (B) and a cross-linking agent (C).
[0137]
　Further, as in the first embodiment, when a crosslinkable adhesive resin composition utilizing crosslinking of the phenoxy resin (A) is used as the matrix resin 103, 100 parts by mass of the phenoxy resin (A) is crosslinked and cured. It is preferable that the functional resin (B) is contained in the range of 5 parts by mass or more and 85 parts by mass or less. The content of the crosslinkable resin (B) with respect to 100 parts by mass of the phenoxy resin (A) is more preferably in the range of 9 parts by mass or more and 83 parts by mass or less, and further preferably 10 parts by mass or more and 80 parts by mass or less. It is within the range.
[0138]
　Furthermore, if a cross-linking agent (C) is blended with the phenoxy resin (A) and the cross-linking curable resin (B), a cross-linkable adhesive resin composition can be obtained, but as a catalyst to ensure the cross-linking reaction, The accelerator (D) may be further added. The accelerator (D) is the same as that described in the first embodiment. When the matrix resin 103 is formed by using the crosslinkable adhesive resin composition as a fine powder and adhering to the reinforcing fiber base material by a powder coating method using an electrostatic field, the catalyst activation temperature is set as the promoter (D). It is preferable to use an imidazole-based latent catalyst that is solid at room temperature and has a temperature of 130° C. or higher.
[0139]
　In addition, the matrix resin 103 is the same as the adhesive resin forming the adhesive resin layer 13 according to the first embodiment described above. In addition, what is not described above regarding the adhesive resin layer 13A is the same as the adhesive resin layer 13 according to the first embodiment. For example, the above-mentioned oil surface adhesive agent may be added to the adhesive resin composition. Further, an oil surface adhesive may be applied to the interface between the metal member 11 and the adhesive resin layer 13A.
[0140]
[Method for Producing
　Metal-Fiber Reinforced Resin Material Composite] The configuration of the metal-FRP composite 2 as the metal-fiber reinforced resin material composite according to this embodiment has been described above. Next, refer to FIG. However, a method for manufacturing the metal-FRP composite 2 according to this embodiment will be described. FIG. 9 is an explanatory diagram showing an example of a manufacturing process of the metal-FRP composite 2.
[0141]
　The metal-FRP composite 2 comprises an adhesive resin composition (crosslinkable adhesive resin composition) which becomes the matrix resin 103 of the FRP (or its precursor, FRP molding prepreg) processed into a desired shape and the metal member 11. And the reinforcing fiber material 104 are adhered to each other, and the adhesive resin composition is solidified (in the case of a crosslinkable adhesive resin composition, cured). The adhered FRP becomes the FRP layer 12, and the adhesive sheet containing the solidified or cured product of the adhesive resin composition becomes the adhesive resin layer 13A. As a method of forming a composite by adhering the metal member 11 and the FRP with the above-mentioned adhesive sheet and joining them, for example, the following method 3 can be used.
[0142]
(Method 3) In
　Method 3, an adhesive sheet (second prepreg) containing an adhesive resin composition that becomes the matrix resin 103 and the reinforcing fiber material 104, and an FRP or FRP molding prepreg (the first prepreg that becomes the FRP layer 12 (first Prepreg) is laminated on the metal member 11 and thermocompression bonded.
[0143]
　In this method 3, as shown in, for example, FIG. 9A, an adhesive sheet 20B containing an adhesive resin composition serving as a matrix resin 103 and a reinforcing fiber material 104 on at least one surface of the metal member 11, and an FRP. The prepreg 21 for FRP molding which becomes the layer 12 is arrange|positioned in piles, and the metal member 11, the adhesive sheet 20B, and the prepreg 21 for FRP molding are laminated|stacked in this order, and the laminated body is formed. Here, the adhesive sheet 20B is a sheet-like prepreg for adhering the metal member 11 and the FRP layer 12. Note that, in FIG. 9A, FRP may be laminated instead of the FRP molding prepreg 21, but the bonding surface of the FRP at this time is, for example, roughened by blasting, plasma treatment, corona treatment, or the like. It is preferable that the activation is performed by such as. Next, by heating and pressurizing this laminated body, a metal-FRP composite 2 is obtained as shown in FIG. 9(b).
[0144]
　In the method 3, the FRP molding prepreg 21 (or FRP) is joined to the metal member 11 by the adhesive sheet 20B containing the reinforcing fiber material 104. In this case, the resin component derived from the adhesive resin composition impregnated in the reinforcing fiber material 104 (portion to be the matrix resin 103) functions as an adhesive resin.
[0145]
　In Method 3, in FIG. 9A, the adhesive sheet 20B and the FRP molding prepreg 21 (or FRP) may be laminated on both surfaces of the metal member 11, respectively. Further, the FRP molding prepreg 21 (or FRP) serving as the FRP layer 12 is not limited to one layer and may be a plurality of layers (see FIG. 8 ). Alternatively, two or more metal members 11 may be used and laminated so that the adhesive sheet 20B and the FRP molding prepreg 21 (or FRP) that becomes the FRP layer 12 are sandwiched in a sandwich shape.
[0146]
(Compounding with
　Metal Member ) The compounding of the metal member 11 and the FRP is preferably performed as follows, for example.
[0147]
　An adhesive sheet 20B to be the adhesive resin layer 13A is arranged at a predetermined position on the adhesive surface of the metal member 11. Next, the laminated body in which the FRP molding prepreg 21 to be the FRP layer 12 is laminated is placed in a pressure molding machine and pressure-molded to form the adhesive resin layer 13A.
[0148]
In the
　above method 3, the thermo-compression bonding conditions for compounding the metal member 11, the adhesive sheet 20B, and the prepreg 21 (or FRP) for FRP forming the FRP layer 12 are as follows. Is. The thermocompression bonding temperature, the pressure for pressure bonding, and the thermocompression bonding time are the same as those in Method 2 described above.
[0149]
　In the thermocompression bonding step, a composite batch molding of the metal member 11, the adhesive sheet 20B, and the FRP molding prepreg 21 (or FRP) that becomes the FRP layer 12 may be performed by a pressure molding machine.
[0150]
(Additional heating step) In the
　method 3, as the adhesive resin composition for forming the adhesive resin layer 13A or the raw material resin for forming the matrix resin 101, a phenoxy resin (A) and a crosslinkable curable resin (B) are used. When using a crosslinkable adhesive resin composition containing a crosslinking agent (C) and a crosslinking agent (C), as in the methods 1 and 2, an additional heating step can be further included. The details of the additional heating step are the same as those in the first embodiment ("adhesive resin layer 13" is "adhesive resin layer 13A", "metal-FRP composite 1" is "metal-FRP composite 2". Should be read separately).
[0151]
(Pre-treatment step and post-step) The
　pre-treatment step and post-step are the same as those in the above-described first embodiment.
[0152]
(Method of Manufacturing Adhesive Sheet)
　Here, a method of manufacturing the adhesive sheet 20B (second prepreg) used when forming the adhesive resin layer 13A will be described. Even when the FRP layer 12 is formed of the same resin as the matrix resin 103 of the adhesive resin layer 13A, it can be manufactured by the following method.
[0153]
　In the adhesive sheet 20B forming the adhesive resin layer 13A, the reinforcing fiber base material to be the reinforcing fiber material 104 is similar to the FRP layer 12, for example, a non-woven fabric base material using chopped fibers or a cloth material using continuous fibers, Although a unidirectional reinforcing fiber base material (UD material) or the like can be used, it is preferable to use a cloth material or a UD material from the viewpoint of the reinforcing effect.
[0154]
　As the adhesive sheet 20B, it is preferable to use a prepreg prepared by a powder coating method, rather than a prepreg prepared by a conventionally known method such as a wet melt method or a film stack method. The prepreg prepared by the powder coating method has good drapeability because the resin is impregnated in the reinforcing fiber base material in the state of fine particles, and it can follow even if the adherend has a complicated shape. Because it is possible, it is suitable for batch forming hot press.
[0155]
　The main methods of powder coating methods include, for example, electrostatic coating method, fluidized bed method, suspension method, etc., and either method may be appropriately selected depending on the reinforcing fiber base material type and the matrix resin type. .. Of these, the electrostatic coating method and the fluidized bed method are preferable methods because they are suitable for thermoplastic resins, have simple steps, and have good productivity. In particular, the electrostatic coating method is the most suitable method because it is excellent in the uniformity of adhesion of the adhesive resin composition to the reinforcing fiber base material.
[0156]
　When powder-coating the adhesive resin composition that becomes the matrix resin 103 when forming the adhesive sheet 20B, the adhesive resin composition containing the phenoxy resin (A) is used as a fine powder, and the fine powder is used. It is preferable to obtain the prepreg by attaching it to the reinforcing fiber base material by powder coating.
[0157]
　For pulverizing the adhesive resin composition containing the phenoxy resin (A), for example, a pulverizing and mixing machine such as a low temperature dry pulverizing machine (Centry dry mill) can be used, but the pulverizing and mixing machine is not limited thereto. When the adhesive resin composition for the matrix resin 103 is pulverized, the components of the adhesive resin composition may be pulverized and then mixed, or the components may be mixed in advance and then pulverized. In this case, it is preferable to set the crushing conditions so that each fine powder has an average particle diameter described later. The fine powder thus obtained has an average particle size of 10 μm or more and 100 μm or less, preferably 40 μm or more and 80 μm or less, and more preferably 40 μm or more and 50 μm or less. By setting the average particle diameter to 100 μm or less, the energy when the adhesive resin composition collides with the fiber in powder coating in an electrostatic field can be reduced, and the adhesion rate to the reinforcing fiber base material can be increased. Further, by setting the average particle diameter to 10 μm or more, it is possible to prevent the particles from being scattered by the entrained airflow and suppress the deterioration of the adhesion efficiency, and to prevent the resin fine powder floating in the air from deteriorating the working environment. it can.
[0158]
　When powder coating of a crosslinkable adhesive resin composition obtained by mixing a phenoxy resin (A) with a crosslinkable curable resin (B) and a crosslinking agent (C) as an adhesive resin composition for forming the adhesive sheet 20B, The average particle size of the fine powder of the phenoxy resin (A) and the fine powder of the crosslinkable curable resin (B) is in the range of 1 to 1.5 times the average particle size of the fine powder of the crosslinking agent (C). It is preferable. By setting the particle size of the fine powder of the cross-linking agent (C) to be equal to or smaller than the particle size of the fine powder of the phenoxy resin (A) and the cross-linking curable resin (B), the cross-linking agent (C) even inside the reinforcing fiber base material. Enter and adhere to the reinforcing fiber material. Moreover, since the crosslinking agent (C) is evenly present around the particles of the phenoxy resin (A) and the particles of the crosslinkable resin (B), the crosslinking reaction can be reliably advanced.
[0159]
　In the powder coating for forming the adhesive sheet 20B, the adhesion amount (resin ratio: RC) of the adhesive resin composition serving as the matrix resin 103 to the reinforcing fiber base material is within the range of 20% or more and 50% or less, for example. It is preferable to apply the coating so that RC is more preferably in the range of 25% or more and 45% or less, and further preferably in the range of 25% or more and 40% or less. By setting RC to 50% or less, deterioration of mechanical properties such as tensile and flexural modulus of FRP can be prevented. Further, by setting RC to 20% or more, a necessary amount of resin can be secured, so that the matrix resin 103 is sufficiently impregnated into the inside of the reinforcing fiber base material, and the thermophysical properties and mechanical properties can be improved.
[0160]
　The fine powder of the powder-coated adhesive resin composition (which becomes the matrix resin 103) is fixed to the reinforcing fiber base material by heating and melting. In this case, the powder may be applied to the reinforcing fiber base material and then heat-sealed, or by applying powder to the reinforcing fiber base material which has been heated in advance, the reinforcing fiber of fine powder of the adhesive resin composition may be obtained. It may be fused at the same time as the coating on the substrate. As described above, by heating and melting the fine powder of the adhesive resin composition on the surface of the reinforcing fiber base material, the adhesion to the reinforcing fiber base material is enhanced, and the fine powder of the coated adhesive resin composition can be prevented from falling off. .. However, at this stage, the adhesive resin composition which becomes the matrix resin 103 is concentrated on the surface of the reinforcing fiber base material, and does not reach the inside of the reinforcing fiber base material like the molded body after the heat and pressure molding. .. The heating time for fusing the adhesive resin composition after powder coating is not particularly limited, but is usually 1 to 2 minutes. The melting temperature is in the range of 150 to 240°C, preferably in the range of 160 to 220°C, more preferably in the range of 180 to 200°C. If the melting temperature exceeds the upper limit, the curing reaction may proceed, and if the melting temperature falls below the lower limit, heat fusion becomes insufficient, and during handling work, fine powder of the adhesive resin composition falls off or falls off. May occur. Here, an oil surface adhesive may be added to the adhesive resin composition. The specific addition method is not particularly limited, but the following methods may be mentioned, for example. When the oil surface adhesive is liquid, the adhesive resin composition is finely cut and crushed, mixed with the oil surface adhesive, and the same steps as the above-described manufacturing method are performed using this as a raw material. Good. As the method of cutting and crushing, the above-mentioned finely pulverizing method may be used. When the oil surface adhesive is solid, the oil surface adhesive is dissolved in an organic solvent, the solution is mixed with the adhesive resin composition, and the organic solvent is volatilized and dried. You may perform the process similar to the manufacturing method mentioned above. In addition, the oil surface adhesive and the adhesive resin composition are physically cut with a stirrer or the like, pulverized, and mixed to obtain a mixture as described above, which is used as a raw material.
[0161]
　Regarding the FRP molding prepreg 21 used for forming the FRP layer 12, it is preferable to use the prepreg manufactured by the above powder coating method at least for those adjacent to the adhesive resin layers 13 and 13A. Since the adhesive resin layers 13 and 13A and the prepreg 21 for FRP molding are both manufactured by the powder coating method, the interfaces of the both are mixed in a rough state at the time of thermocompression bonding and become mixed and integrated. By the anchor effect, the adhesive strength between the adhesive resin layers 13 and 13A and the FRP layer 12 can be improved.
[0162]

　According to the above-described first and second embodiments, a metal in which the metal member 11 and the FRP layer 12 are firmly joined via the adhesive resin layers 13 and 13A. -FRP complexes 1, 2 are provided. These metal-FRP composites 1 and 2 are lightweight, have excellent workability, and can be manufactured by a simple method. For example, even if the metal member 11 is a steel material that has been subjected to anticorrosion treatment, the metal member 11 and the FRP layer 12 have high adhesive strength without performing a special surface roughening treatment. In addition, when the metal member 11 and the FRP to be the FRP layer 12 are combined, the manufacturing cost can be reduced because the metal member 11 and the FRP layer 12 can be collectively processed at the same time when the metal member 11 is formed by hot pressing. Therefore, the metal-FRP composites 1 and 2 of the above-described embodiments are used as a lightweight and high-strength material as a structural member for applications such as automobile members and aircraft members as well as casings for electric and electronic devices. It can be used preferably. Furthermore, since the metal-FRP composites 1 and 2 can solve all the above-mentioned six problems when using FRP for automobile members, they can be used particularly suitably as automobile members.
Example
[0163]
　Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. The tests and measuring methods for various physical properties in this example are as follows.
[0164]
[Average particle size (D50)] The
　average particle size is measured by a laser diffraction/scattering particle size distribution measuring device (Microtrac MT3300EX, manufactured by Nikkiso Co., Ltd.) when the cumulative volume is 50% on a volume basis. did.
[0165]
[Melt Viscosity] A
　rheometer (manufactured by Anton Paar) was used to sandwich a sample size of 4.3 cm 3 between parallel plates, and the temperature was raised at 20° C./min while the frequency was 1 Hz and the load strain was 5%. The melt viscosity at 180° C. was measured.
[0166]
[Resin ratio (RC:%)]
　It was calculated using the following formula from the weight (W1) of the reinforcing fiber base material before adhesion of the matrix resin and the weight (W2) of the FRP molding material after adhesion of the resin.
　Resin ratio (RC:%)=(W2-W1)/W2×100
　　　W1: Weight of reinforcing fiber base material before resin adhesion
　　　W2: Weight of FRP molding material after resin adhesion
[0167]
[Measurement of Thickness of
　Adhesive Resin Layer ] The thickness of the adhesive resin layer was measured by the method mentioned above.
[0168]
[Measurement of Tensile Load and Tensile Elastic Modulus (Elastic Modulus)]
　Mechanical properties (tensile strength) of metal-FRP composite materials obtained in accordance with JIS K 7164:2005 isotropic and orthotropic fiber reinforced plastic test conditions. Strength and tensile modulus) were measured. The tensile load is the product of the tensile strength and the cross-sectional area of ​​the test piece (tensile strength (N/mm 2 )=tensile load (N)÷cross-sectional area of ​​the test piece (mm 2 )). The dimensions of the test piece were 200 mm×25 mm.
[0169]
　Here, as schematically shown in FIG. 10, the metal members 11 are arranged on both sides of the FRP laminated body in which the FRP layer 12 and the adhesive resin layer 13 (or the adhesive resin layer 13A) are laminated. A metal-FRP composite sample for a tensile test was obtained by heating and pressing under the conditions shown in the comparative example. The arrow direction in FIG. 10 indicates the load application direction.
[0170]
[Confirmation of Presence or Absence of
　Super Additive Rule ] Whether or not the super additive rule was expressed was confirmed as follows. The metal member 11 and the FRP layer 12 (here, the prepreg before the FRP layer 12 is integrated with the metal member 11) are individually subjected to a tensile test by the above-described measurement method, and each maximum load (load A1 , B) is measured. Then, the metal-FRP composite in which the metal member 11 and the FRP layer 12 are composited is also subjected to the tensile test by the above-described measuring method to measure the maximum load (load C). Further, based on the deformation amount D (deformation amount at break of the metal-FRP composite) when the load C is measured and the result of the tensile test of the metal member 11, the tension of the metal member 11 at the deformation amount D is calculated. The load (load A2) is calculated. Then, the success or failure of the equations (2-1) and (2-2) is determined, and when at least the equation (2-2) is satisfied, it is determined that the super-addition rule is expressed. In this embodiment, the equation (2-1) is the "reference 1" and the equation (2-2) is the "reference 2". The degree of super-additive rule is calculated by C/(A2+B), but when the criterion 1 is also satisfied, the degree of super-additive rule corresponding to the criterion 1 is calculated as C/(A1+B). The superaddition rule degree is preferably 1.01 or more, and more preferably 1.05 or more. For example, when the formula (2-1) is satisfied, the maximum load of the composite is preferably 1% or more, and more preferably 5% or more, compared to the total load of each alone. That is, the degree of superaddition rule is preferably 1.01 or more, and more preferably 1.05 or more. At this time, in the test piece, it is preferable that the size of the test piece of the metal member and the FRP alone is the same as the size of the metal member and the FRP layer of the test piece of the composite. This method can also be used to confirm the presence or absence of the superaddition rule in advance in determining the necessity of degreasing in the above (pretreatment step).
[0171]
　If the individual materials of the metal member 11 and the FRP layer 12 are not available and only the metal-FRP composite is available, the metal member 11 is peeled from the FRP layer 12 to obtain individual members. If peeling is difficult, use a grinder or the like with a diamond grindstone attached to create a metal-FRP composite in which only the metal member 11 and the FRP layer 12 have been removed, respectively. By carrying out the test, each tensile load is measured.
[0172]
　Specifically, three test pieces are cut out from the metal-FRP composite. The size of each test piece may be determined according to the size of the obtained metal-FRP composite and the like, but as an example, a strip shape having a width of 25 mm and a length of 200 mm may be used. In addition, even if a tab made of glass epoxy, which is generally specified by the standard such as JIS K 7164:2005, is attached to the test piece so that the test piece is not damaged by a test piece holding mechanism such as a chuck of a tensile tester. Good. These are designated as first to third test pieces. Then, by observing the cross section of one of the test pieces in accordance with the cross section method of the optical method of JIS K 5600-1-7, Section 5.4, the metal member 11, the FRP layer 12, and the adhesive resin layer are observed. The thickness of 13 is measured. Then, the maximum load of the metal-FRP composite is measured by performing the above-described tensile test on the first test piece. That is, the first test piece is used as the metal-FRP composite metal member 11.
[0173]
　On the other hand, the FRP layer 12 and the adhesive resin layer 13 are removed from the second test piece. The removal method is as described above. That is, the second test piece is used as the metal member 11. When the FRP layer 12 and the adhesive resin layer 13 are scraped off, about 5 to 10% of the measured thickness of the metal member 11 may be scraped off. This is due to the error in the measured thickness. On the other hand, there is no problem if the adhesive resin layer 13 remains on the metal member 11 to some extent. This is because the maximum load of the adhesive resin layer 13 is negligibly smaller than the maximum load of the metal member 11. Next, the maximum load (load A1) of the metal member 11 is measured by performing the above-described tensile test on the second test piece. Further, the tensile load (load A2) of the metal member 11 at the deformation amount D is obtained based on the deformation amount D when the load C is measured and the result of the tensile test of the metal member 11.
[0174]
　On the other hand, the metal member 11 and the adhesive resin layer 13 are removed from the third test piece. The removal method is as described above. That is, the third test piece is used as the FRP layer 12. When the metal member 11 and the adhesive resin layer 13 are scraped off, about 5 to 10% of the measured thickness of the FRP layer 12 may be scraped off. This is due to the error in the measured thickness. On the other hand, there is no problem even if the adhesive resin layer 13 remains on the FRP layer 12 to some extent. This is because the maximum load of the adhesive resin layer 13 is negligibly smaller than the maximum load of the FRP layer 12. Next, the maximum load of the FRP layer 12 is measured by performing the above-mentioned tensile test on the third test piece. Then, based on each measured value and the equations (2-1) and (2-2) (preferably the equation (2-2)), it may be determined whether or not the super-addition rule is satisfied. The method of measuring the tensile load of the metal member, the FRP, and the respective materials in the composite material when the metal member is surface-treated can be carried out in the same manner as above. The method of measuring the tensile load of the metal member, the FRP, and the respective materials in the composite material when the metal member is surface-treated can be carried out in the same manner as above. Further, in the tensile test, when the sample broke, the sample was peeled from the metal-FRP composite, that is, peeled: × (with peeling), and when not peeled, peeled: ○ (without peeling) evaluated.
[0175]
[FRP prepreg]
Polyamide CFRP prepreg
　Sakai Obex BHH-100GWODPT1/PA, Vf (fiber volume content): 47%
Polycarbonate CFRP prepreg
　Sakai Obex BHH-100GWODPT1/PC, Vf (fiber volume content): 47%
polypropylene CFRP prepreg
　Sakai Obex BHH-100GWODPT1/PP, Vf (fiber volume content): 47%
[0176]
[Phenoxy resin (A)]
　(A-1): Phenothote YP-50S (bisphenol A type manufactured by Nippon Steel & Sumitomo Metal Corporation, Mw=40,000, hydroxyl equivalent=284 g/eq), melt viscosity at 250° C.=90 Pa・S, Tg=83℃
[0177]
[Crosslinking curable resin (B)]
　Epoxy resin
　YSLV-80XY (Tetramethylbisphenol F type, manufactured by Nippon Steel & Sumitomo Metal Corporation, epoxy equivalent=192 g/eq, melting point=72° C.)
[0178]
[Crosslinking agent (C)]
　Ethylene glycol bisanhydrotrimellitate: TMEG
　(acid anhydride equivalent: 207, melting point: 160°C)
[0179]
[Preparation Example 1] [Preparation of
phenoxy resin CFRP prepreg A] As a
　phenoxy resin (A), a powder obtained by crushing and classifying A-1 and having an average particle diameter D50 of 80 μm was used as a reinforced fiber base material ( A cloth material: IMS 60) manufactured by Toho Tenax Co., Ltd. was subjected to powder coating in an electrostatic field under the conditions of an electric charge of 70 kV and a blowing air pressure of 0.32 MPa. Then, the resin is heat-melted by heating and melting in an oven at 170° C. for 1 minute to obtain a phenoxy resin having a thickness of 0.21 mm, an elastic modulus of 75 [GPa], a maximum load of 5100 [N], and a Vf (fiber volume content) of 60%. Resin CFRP prepreg A was prepared.
[0180]
[Preparation Example 2] [Preparation of
phenoxy resin CFRP prepreg B] As a
　phenoxy resin (A), a powder obtained by crushing and classifying A-1 and having an average particle diameter D50 of 80 μm was used as a reinforced fiber base material ( A cloth material: IMS 60) manufactured by Toho Tenax Co., Ltd. was subjected to powder coating in an electrostatic field under the conditions of an electric charge of 70 kV and a blowing air pressure of 0.32 MPa. After that, the resin is heat-melted at 170° C. for 1 minute in an oven to heat-bond the resin, and phenoxy having a thickness of 0.65 mm, an elastic modulus of 75 [GPa], a maximum load of 13500 [N], and Vf (fiber volume content rate) of 60%. Resin CFRP prepreg B was prepared.
[0181]
[Preparation Example 3] [Preparation of
phenoxy resin GFRP prepreg] As a
　phenoxy resin (A), a plain weave reinforced fiber base material made of glass fiber is a powder obtained by crushing and classifying A-1 and having a mean particle diameter D50 of 80 μm. (Cloth material: WEA 116E 106S 136 manufactured by Nitto Boseki Co., Ltd.) was subjected to powder coating in an electrostatic field under the conditions of an electric charge of 70 kV and a blowing air pressure of 0.32 MPa. After that, the resin is heat-melted at 170° C. for 1 minute in an oven to heat-bond the resin, and phenoxy having a thickness of 0.161 mm, an elastic modulus of 20 [GPa], a maximum load of 1470 [N], and a Vf (fiber volume content) of 50%. A resin GFRP prepreg was prepared.
[0182]
[Preparation Example 4] [Preparation of
phenoxy resin CFRP prepreg C] As the
　phenoxy resin (A), a powder obtained by crushing and classifying A-1 and having an average particle diameter D50 of 80 μm was used as a reinforced fiber base material ( UD material: IMS 60) manufactured by Toho Tenax Co., Ltd. was subjected to powder coating in an electrostatic field under the conditions of an electric charge of 70 kV and a blowing air pressure of 0.32 MPa. Thereafter, the resin is heat-melted at 170° C. for 1 minute in an oven to heat-bond the resin, and a phenoxy resin having a thickness of 0.3 mm, an elastic modulus of 110 [GPa], a maximum load of 13000 [N], and a Vf (fiber volume content) of 46%. Resin CFRP prepreg C was prepared.
[0183]
[Preparation Example 5] [Preparation of
crosslinked phenoxy resin CFRP prepreg A] As
　phenoxy resin (A), 100 parts by mass of A-1, 30 parts by mass of crosslinkable curable resin (B), and 73 parts by mass of crosslinking agent (C). The powder was prepared, pulverized and classified to obtain powder having an average particle diameter D50 of 80 μm, which was dry blended with a dry powder mixer (a rocking mixer manufactured by Aichi Denki Co., Ltd.). The obtained crosslinkable phenoxy resin composition was applied to a plain weave reinforced fiber base material (cloth material: Sakai Obex Co., SA-3203) made of carbon fiber in an electrostatic field at a charge of 70 kV and a blowing air pressure of 0.32 MPa. Powder coating was performed under the conditions. After that, the resin is heat-melted at 170° C. for 1 minute in an oven to thermally fuse the resin, and a crosslinked phenoxy having a thickness of 0.65 mm, an elastic modulus of 75 [GPa], a maximum load of 17,000 [N], and a resin ratio (RC) of 48%. Resin CFRP prepreg A was prepared.
[0184]
　The melt viscosity of the crosslinkable phenoxy resin composition at 250°C was 250 Pa·s. Regarding the Tg of the phenoxy resin after cross-linking and curing, a plurality of prepared prepregs were laminated and pressed with a press machine heated to 200° C. for 3 MPa for 3 minutes to prepare a CFRP laminate having a thickness of 2 mm, and at 170° C. After performing post-curing for 30 minutes, a test piece having a width of 10 mm and a length of 10 mm was cut out with a diamond cutter, and a temperature increasing condition of 5° C./minute was measured using a dynamic viscoelasticity measuring device (DMA 7e manufactured by Perkin Elmer). , And the maximum peak of tan δ obtained was taken as Tg.
[0185]
　[Preparation Example 6] [Preparation of
crosslinked phenoxy resin CFRP prepreg B]
　100 parts by mass of A-1 as the phenoxy resin (A), 30 parts by mass of the crosslinkable curable resin (B), and 73 parts by mass of the crosslinking agent (C). As a nylon resin, 120 parts by mass of Aldrich's CAS No. 25038-54-4 Product No. 181110 was prepared, and each was pulverized and classified to obtain a powder having an average particle diameter D50 of 80 μm. It was dry blended by a machine (a rocking mixer manufactured by Aichi Electric Co., Ltd.). The obtained crosslinkable phenoxy resin composition was applied to a plain weave reinforced fiber base material (cloth material: Sakai Obex Co., SA-3203) made of carbon fiber in an electrostatic field at a charge of 70 kV and a blowing air pressure of 0.32 MPa. Powder coating was performed under the conditions. After that, the resin is heat-melted at 170° C. for 1 minute in an oven to heat-bond the resin, and a crosslinked phenoxy having a thickness of 0.65 mm, an elastic modulus of 75 [GPa], a maximum load of 18500 [N], and a resin ratio (RC) of 48%. Resin CFRP prepreg B was prepared.
[0186]
　[Preparation Example 7] [Preparation of
phenoxy resin film]
　A-1 was used as the phenoxy resin (A) and pressed at 3° C. for 3 minutes with a press machine heated to 200° C. to prepare a phenoxy resin film having a thickness of 20 μm. did.
[0187]
　[Production Example 8] [Production of
polypropylene and phenoxy resin film]
　20 parts by mass of A-1 as the phenoxy resin (A) and 80 parts by mass of CAS No. 9003-07-0 product number 427861 manufactured by Aldrich as the polypropylene resin. The prepared and pulverized and classified powders having an average particle diameter D50 of 80 μm were pressed with a press machine heated to 200° C. for 3 MPa for 3 minutes, and a 20 μm-thick polypropylene and phenoxy resin film. It was created.
[0188]
　[Preparation Example 9] [Preparation of
phenoxy resin film containing oil surface adhesive agent]
　50 parts by mass of A-1 as a phenoxy resin (A), and a main agent of Alpha Industrial Co., Ltd. Alpha Tech 370 as an oil surface adhesive agent Prepare 50 parts by mass of a mixture of curing agents in a weight ratio of 100:30, press these mixtures with a press machine heated to 200° C. for 3 MPa for 3 minutes to obtain an oil surface adhesive having a thickness of 200 μm. A filled phenoxy resin film was prepared.
[0189]
[Preparation Example 10] [Preparation of
phenoxy resin CFRP prepreg D] As a
　phenoxy resin (A), a powder obtained by crushing and classifying A-1 and having an average particle diameter D50 of 80 μm was used as a reinforced fiber base material ( A cloth material: IMS 60) manufactured by Toho Tenax Co., Ltd. was subjected to powder coating in an electrostatic field under the conditions of an electric charge of 70 kV and a blowing air pressure of 0.32 MPa. After that, the resin is heat-melted in an oven at 170° C. for 1 minute to heat-bond the resin, and a phenoxy resin having a thickness of 1.00 mm, an elastic modulus of 75 [GPa], a maximum load of 19000 [N], and a Vf (fiber volume content rate) of 60%. Resin CFRP prepreg D was prepared.
[0190]
[Preparation Example 11] [Preparation of
phenoxy resin CFRP prepreg E] As a
　phenoxy resin (A), a powder obtained by pulverizing and classifying A-1 and having an average particle diameter D50 of 80 μm was used as a reinforced fiber substrate ( A cloth material: IMS 60) manufactured by Toho Tenax Co., Ltd. was subjected to powder coating in an electrostatic field under the conditions of an electric charge of 70 kV and a blowing air pressure of 0.32 MPa. Then, the resin is heat-melted by heating and melting in an oven at 170° C. for 1 minute to obtain a phenoxy resin having a thickness of 0.18 mm, an elastic modulus of 75 [GPa], a maximum load of 2800 [N], and a Vf (fiber volume content) of 60%. Resin CFRP prepreg E was prepared.
[0191]
[Metal member]
Metal member (M-1):
　Tin-free steel plate manufactured by Nippon Steel & Sumikin Co., Ltd., thickness 0.21 mm
Metal member (M-2):
　Commercially available aluminum alloy A5052 plate, thickness 0.6 mm
metal member ( M-3):
　Niraco pure titanium plate, thickness 0.1 mm
metal member (M-4):
　Niraco pure aluminum plate, thickness 0.1 mm
metal member (M-5):
　Nippon Metal Co. magnesium alloy AZ31B Plate, thickness 0.1 mm
metal member (M-6):
　Nippon Steel & Sumikin Co., Ltd. hot dip galvanized steel sheet, 0.8 mm thickness
metal member (M-7):
　Nippon Steel & Sumikin Co., Ltd. hot dip galvanized high strength steel plate , Thickness 0.42mm
[0192]
[Example 1]
　M-1 that was sufficiently degreased with acetone was used as the metal member 11, the phenoxy resin CFRP prepreg A of Production Example 1 was used as the FRP layer 12, and the phenoxy resin film of Production Example 7 was used as the adhesive resin layer 13. A sample of the metal-CFRP composite for tensile test having the structure shown in FIG. 10 was used and was pressed by a pressing machine heated to 250° C. for 3 minutes at 3 MPa. The thickness of the adhesive resin layer 13 was 20 μm. A tensile test was conducted on the obtained sample after cooling. The results are shown in Table 1.
[0193]
　The metal member (M-1) was a steel plate with high adhesion without rust-preventive oil or the like adhering to the surface. The same result as in the case of Example 1 in which expression was performed and degreasing was performed was obtained.
[0194]
[Example 2] A
　metal-CFRP composite sample was prepared in the same manner as in Example 1 except that the phenoxy resin CFRP prepreg B of Preparation Example 2 was used as the FRP layer 12. The thickness of the adhesive resin layer 13 was 20 μm. A tensile test was conducted on the obtained sample after cooling. The results are shown in Table 1.
[0195]
Example 3 A
　metal-CFRP composite sample was prepared in the same manner as in Example 2 except that M-2 that had been sufficiently degreased with acetone was used as the metal member 11. The thickness of the adhesive resin layer 13 was 20 μm. A tensile test was conducted on the obtained sample after cooling. The results are shown in Table 1.
[0196]
[Example 4] A
　metal-CFRP composite sample was prepared in the same manner as in Example 1 except that the phenoxy resin GFRP prepreg of Preparation Example 3 was used as the FRP layer 12. The thickness of the adhesive resin layer 13 was 20 μm. A tensile test was conducted on the obtained sample after cooling. The results are shown in Table 1.
[0197]
Example 5 A
　metal-CFRP composite sample was prepared in the same manner as in Example 1 except that the phenoxy resin CFRP prepreg C of Preparation Example 4 was used as the FRP layer 12. The thickness of the adhesive resin layer 13 was 20 μm. A tensile test was conducted on the obtained sample after cooling. The results are shown in Table 1.
[0198]
Example 6
　A sample of the metal-CFRP composite was prepared in the same manner as in Example 1 except that the polyamide CFRP prepreg of the FRP prepreg was used as the FRP layer 12. The thickness of the adhesive resin layer 13 was 20 μm. A tensile test was conducted on the obtained sample after cooling. The results are shown in Table 1.
[0199]
Example 7 A
　metal-CFRP composite sample was produced in the same manner as in Example 1 except that a polycarbonate CFRP prepreg of FRP prepreg was used as the FRP layer 12. The thickness of the adhesive resin layer 13 was 20 μm. A tensile test was conducted on the obtained sample after cooling. The results are shown in Table 1.
[0200]
Example 8 A
　metal-CFRP composite sample was prepared in the same manner as in Example 1 except that polypropylene FRP prepreg polypropylene CFRP prepreg was used as the FRP layer 12. The thickness of the adhesive resin layer 13 was 20 μm. A tensile test was conducted on the obtained sample after cooling. The results are shown in Table 1.
[0201]
Example 9 A
　metal-CFRP composite sample was prepared in the same manner as in Example 2 except that M-3 that had been sufficiently degreased with acetone was used as the metal member 11. The thickness of the adhesive resin layer 13 was 20 μm. A tensile test was conducted on the obtained sample after cooling. The results are shown in Table 1.
[0202]
[Example 10]
　The crosslinked phenoxy resin CFRP prepreg A of Preparation Example 5 was used as the FRP layer 12. The resin film obtained in the following steps was used as the adhesive resin layer 13. That is, 100 parts by mass of A-1 as the phenoxy resin (A), 30 parts by mass of the cross-linking curable resin (B), and 73 parts by mass of the cross-linking agent (C) were prepared, respectively pulverized and classified to obtain an average particle diameter D50. The powder having a particle size of 80 μm was dry blended with a dry powder mixer (a rocking mixer manufactured by Aichi Electric Co., Ltd.). The obtained crosslinkable phenoxy resin composition was pressed with a press machine heated to 200° C. for 3 MPa for 3 minutes to prepare a resin film having a thickness of 20 μm, which was used as the adhesive resin layer 13. A metal-CFRP composite sample was prepared in the same manner as in Example 1 except for the above. The thickness of the adhesive resin layer 13 was 20 μm. A tensile test was conducted on the obtained sample after cooling. The results are shown in Table 1.
[0203]
Example 11 As the
　FRP layer 12, the crosslinked phenoxy resin CFRP prepreg B of Preparation Example 6 was used. The resin film obtained in the following steps was used as the adhesive resin layer 13. That is, 100 parts by mass of A-1 as the phenoxy resin (A), 30 parts by mass of the crosslinkable curable resin (B), 73 parts by mass of the crosslinking agent (C), and a nylon resin of CAS No. 25038-54 manufactured by Aldrich. -4 Prepare 120 parts by mass of product number 181110, pulverize and classify each into powder having an average particle diameter D50 of 80 μm, and dry blend with a dry powder mixer (a rocking mixer manufactured by Aichi Electric Co., Ltd.). did. The obtained crosslinkable phenoxy resin composition was pressed at 200° C. with a pressing machine at 3 MPa for 3 minutes to prepare a resin film having a thickness of 20 μm, which was used as an adhesive resin layer. A metal-CFRP composite sample was prepared in the same manner as in Example 1 except for the above. The thickness of the adhesive resin layer 13 was 20 μm. A tensile test was conducted on the obtained sample after cooling. The results are shown in Table 1.
[0204]
[Example 12] The
　metal member 11 was M-7 sufficiently degreased with acetone, the FRP layer 12 was the phenoxy resin CFRP prepreg D of Preparation Example 10, and the adhesive resin layer 13 was the phenoxy resin film of Preparation Example 7. A metal-CFRP composite sample was prepared in the same manner as in Example 1 except that it was used. The thickness of the adhesive resin layer 13 was 20 μm. A tensile test was conducted on the obtained sample after cooling. The results are shown in Table 1.
[0205]
Example 13 The
　metal member 11 was M-7 sufficiently degreased with acetone, the FRP layer 12 was the phenoxy resin CFRP prepreg E of Preparation Example 11, and the adhesive resin layer 13 was the phenoxy resin film of Preparation Example 7. A metal-CFRP composite sample was prepared in the same manner as in Example 1 except that the sample was used. The thickness of the adhesive resin layer 13 was 20 μm. A tensile test was conducted on the obtained sample after cooling. The results are shown in Table 1.
[0206]
[Example 14]
　After sufficiently degreasing the metal member 11 with acetone, in order to quantitatively attach the oil component to the surface, cup grease type 1 No. 3 manufactured by JX Nikko Nisseki Co., Ltd. of 5 g/m 2 was used. A metal was prepared in the same manner as in Example 13 except that M-7 applied in an amount of 3 g/m 2 was used, and an oil surface adhesive, Alpha Tech 370, manufactured by Alpha Industry Co., Ltd. was applied thereon. A sample of -CFRP complex was prepared. The thickness of the adhesive resin layer 13 was 22 μm. A tensile test was conducted on the obtained sample after cooling. The results are shown in Table 1.
[0207]
[Example 15]
　After thoroughly degreasing the metal member 11 with acetone, in order to quantitatively attach the oil component to the surface, cup grease type 1 No. 3 manufactured by JX Nikko Nisseki Co., Ltd. of 5 g/m 2 was used. A metal-CFRP composite sample was prepared in the same manner as in Example 13 except that the phenoxy resin film containing the oil surface adhesive of Preparation Example 9 was used as the adhesive resin layer 13 with M-7 applied in an amount. did. The thickness of the adhesive resin layer 13 was 200 μm. A tensile test was conducted on the obtained sample after cooling. The results are shown in Table 1.
[0208]
[Comparative Example 1]
　M-1 as the metal member 11 was thinned by cutting and polishing to a thickness of 0.032 mm (32 μm) and then sufficiently degreased with acetone, and the FRP layer 12 was prepared. A sample of the metal-CFRP composite for tensile test having the structure shown in FIG. 10 using the phenoxy resin CFRP prepreg C of Example 4 and the phenoxy resin film of Preparation Example 7 as the adhesive resin layer 13 was heated to 250° C. It was produced by pressing at 3 MPa for 3 minutes with the above press machine. The thickness of the adhesive resin layer 13 was 20 μm. A tensile test was conducted on the obtained sample after cooling. The results are shown in Table 2.
[0209]
[Comparative Example 2]
　M-4 that was sufficiently degreased with acetone as the metal member 11, the phenoxy resin CFRP prepreg B of Preparation Example 1 as the FRP layer 12, and the phenoxy resin film of Preparation Example 7 as the adhesive resin layer 13. Was prepared by pressing a sample of the metal-CFRP composite for tensile test having the structure shown in FIG. 10, using a press machine heated to 250° C. at 3 MPa for 3 minutes. The thickness of the adhesive resin layer 13 was 20 μm. A tensile test was conducted on the obtained sample after cooling. The results are shown in Table 2.
[0210]
[Comparative Example 3] A
　metal-CFRP composite sample was prepared in the same manner as in Comparative Example 2 except that M-5 that had been sufficiently degreased with acetone was used as the metal member 11. The thickness of the adhesive resin layer 13 was 20 μm. A tensile test was conducted on the obtained sample after cooling. The results are shown in Table 2.
[0211]
[Comparative Example 4]
　M-1 that was sufficiently degreased with acetone as the metal member 11, the phenoxy resin CFRP prepreg B of Preparation Example 1 as the FRP layer 12, and the polypropylene and phenoxy of Preparation Example 8 as the adhesive resin layer 13. A sample of the metal-CFRP composite for tensile test having a structure shown in FIG. 10 using a resin film was produced by pressing the sample at 3 MPa for 3 minutes with a press machine heated to 250° C. The thickness of the adhesive resin layer 13 was 20 μm. A tensile test was conducted on the obtained sample after cooling. The results are shown in Table 2.
[0212]
[Comparative Example 5]
　After sufficiently degreasing the metal member 11 with acetone, in order to quantitatively attach an oil component to the surface, a cup grease No. 1 No. 3 manufactured by JX Nikko Nisseki Co., Ltd. of 5 g/m 2 was used. A metal-CFRP composite sample was prepared in the same manner as in Example 13 except that the amount of M-7 applied was used. The thickness of the adhesive resin layer 13 was 20 μm. A tensile test was conducted on the obtained sample after cooling. The results are shown in Table 2.
[0213]
[Reference Example] A
　metal-CFRP composite sample was prepared in the same manner as in Comparative Example 2 except that M-2 that had not been degreased was used as the metal member 11. The thickness of the adhesive resin layer 13 was 20 μm. A tensile test was conducted on the obtained sample after cooling. The results are shown in Table 2.
[0214]
[table 1]

[0215]
[Table 2]

[0216]
　As can be seen from Tables 1 and 2, a cured product of an adhesive resin composition containing 50 parts by mass or more of a phenoxy resin (A) with respect to 100 parts by mass of a resin component is provided as an adhesive resin layer to prevent oil film (degreasing or oil interviewing). Examples 1 to 15 which are treated with an adhesive adhesive) and satisfy the condition of the formula (1) are those of Comparative Examples 1 to 3 and the phenoxy resin (A) which do not satisfy the condition of the formula (1). Excellent in mechanical strength as compared with Comparative Example 4 in which an adhesive resin layer having a content of less than 50 parts by mass is provided, and Comparative Example 5 in which degreasing is not performed and adhesion of a metal member surface is remarkably poor and Reference Example. Was there. The elastic modulus E2 of the equation (1) was calculated based on the additive rule, with the elastic modulus of the adhesive resin layer being 2 GPa. Further, with respect to metal peeling, although all Comparative Examples have occurred, it has been confirmed that metal peeling occurs regardless of the type of oil used in Comparative Examples.
[0217]
　The preferred embodiments of the present invention have been described above in detail with reference to the accompanying drawings, but the present invention is not limited to these examples. It is obvious that a person having ordinary knowledge in the technical field to which the present invention pertains can come up with various changes or modifications within the scope of the technical idea described in the claims. Of course, it is understood that these also belong to the technical scope of the present invention.
Explanation of symbols
[0218]
　　　1, 2 Metal-FRP composite
　　11 Metal member
　　12 FRP layer
　　13, 13A Adhesive resin layer
　　20 Coating film
　　20A, 20B Adhesive sheet
　　21 FRP molding prepreg
　101 Matrix resin
　102 Reinforcement fiber material
　103 Matrix resin
　104 Reinforcement fiber material
The scope of the claims
[Claim 1]
　A
　first fiber-reinforced resin material having a metal member, a matrix resin, and a reinforcing fiber material contained in the matrix resin
,
　wherein the metal member and the first fiber-reinforced resin material are bonded to each other. A metal-fiber reinforced resin material composite compounded through a resin layer,
　wherein the adhesive resin layer contains 50 parts by mass or more of a phenoxy resin (A) with respect to 100 parts by mass of a resin component. A
　metal-fiber reinforced resin material composite containing a solidified product or a cured product of 1. , wherein the maximum load of the metal-fiber reinforced resin material composite shows a superaddition rule.
[Claim 2]
　The metal-fiber reinforced resin material composite according to claim 1, wherein the superaddition rule is that the following expression (2-2) is established.
　C>A2+B (2-2) In the
　formula (2-2), the load A2 indicates the tensile load of the metal member alone when the metal-fiber reinforced resin material composite is broken, and the load B is the first load. Shows the maximum load of the fiber-reinforced resin material alone, and the load C is the maximum load of the metal-fiber-reinforced resin material composite.
[Claim 3]
　The metal-fiber reinforced resin material composite according to claim 2, wherein a superaddition rule degree, which is a ratio of the load C to a total load of the load A2 and the load B, is 1.01 or more.
[Claim 4]
　The metal-fiber reinforced resin material composite according to claim 3, wherein the degree of superaddition rule is 1.05 or more.
[Claim 5]
　The total thickness T1 of the metal member and the elastic coefficient E1 of the metal member, the total thickness T2 of the first fiber reinforced resin material and the adhesive resin layer, the first fiber reinforced resin material and the adhesive resin. The metal-fiber reinforced resin material composite according to any one of claims 1 to 4, wherein the elastic modulus E2 of the layer satisfies the relationship of the following formula (1).
　(T1×E1)/(T2×E2)>0.3...Equation (1)
[Claim 6]
　The adhesive resin layer is a second fiber-reinforced resin material having the solidified or cured product as a matrix resin and a reinforcing fiber material contained in the matrix resin. The metal-fiber reinforced resin material composite according to item 1.
[Claim 7]
　The adhesive resin composition is a crosslinkable adhesive resin composition further containing a crosslinkable curable resin (B) in a range of 5 parts by mass to 85 parts by mass with respect to 100 parts by mass of the phenoxy resin (A).
　The metal-fiber reinforced resin material composite according to any one of claims 1 to 6 , wherein the cured product is a crosslinked cured product.
[Claim 8]
　8. The metal-fiber reinforced resin material composite according to claim 1, wherein the adhesive resin layer has a thickness of more than 20 μm.
[Claim 9]
　The metal-fiber reinforced resin material composite according to any one of claims 1 to 8, wherein the material of the metal member is a steel material, an iron-based alloy, titanium or aluminum.
[Claim 10]
　The metal-fiber reinforced resin material composite according to claim 9, wherein the steel material is a hot dip galvanized steel sheet, an electrogalvanized steel sheet, or an aluminum plated steel sheet.