Title of invention: Metal-fiber reinforced resin material composite and method for producing the same
Technical field
[0001]
　The present invention relates to a metal-fiber reinforced resin material composite in which a metal member and a fiber reinforced resin material are laminated and integrated, and a method for producing the same.
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 components is being considered, focusing on lightness, tensile strength, workability, etc. of FRP. ..
[0003]
　There are various problems when the FRP itself is used as an automobile member. First, when painting or bending, existing equipment such as a painting line or a metal mold for bending provided for metal members such as steel cannot be used as it is for FRP. Secondly, since FRP has low compressive strength, it is difficult to use it as it is for automobile parts that require high compressive strength. Thirdly, since the matrix resin of FRP is generally a thermosetting resin such as an epoxy resin and has brittleness, there is a risk 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, so that it is not suitable for manufacturing an automobile member requiring a short takt time. Sixth, since FRP using a thermosetting resin as a matrix resin does not undergo plastic deformation, it cannot be bent once it has been cured.
[0004]
　In order to solve these problems, a metal member-FRP composite material in which a metal member and FRP are laminated and integrated (composite) has been studied recently. Regarding the first problem described above, in the metal member-FRP composite material, since the metal member such as steel material can be positioned on the surface of the composite material, the coating line and the mold provided for the metal material such as steel material. Etc. can be used as they are. With respect to the second problem described above, the compressive strength of the composite material can be increased by combining the metal member having a high compressive strength with the FRP. With respect to the third problem described above, by combining with a metal member such as a steel material having ductility, the brittleness is reduced and the composite material can be deformed. With respect to the fourth problem, by combining a low-priced metal member and FRP, the amount of FRP used can be reduced, so that the cost of the automobile member 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, and as a bonding method, a method using an epoxy resin thermosetting adhesive is generally used. Are known.
[0006]
　Further, in order to solve the problems when the above FRP is used for an automobile member, 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, and thus the tact time can be shortened. Regarding the sixth problem, as described above, since it becomes possible to plastically deform the FRP, the bending process 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 by performing a surface roughening treatment on an adhesive surface of a metal member, or an adhesive layer of an epoxy resin is provided on the metal member. There has been proposed a technique for improving the adhesive strength between the metal member and CFRP.
[0010]
　In Patent Document 3, a composite of a reinforcing fiber base material and a metal which is a prepreg obtained by impregnating a bonding surface of a carbon fiber base material with a metal member with an adhesive resin such as an epoxy resin and impregnating the other surface with a thermoplastic resin. 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 is made to be a thermosetting resin by causing a cross-linking reaction in 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 in 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 made of a metal and a fiber-reinforced thermoplastic material and a support material made of a thermoplastic material is heated to form a rib structure on the support 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]
　However, even the techniques proposed in Patent Documents 1 to 7 have not been sufficient in terms of shear strength between the fiber reinforced resin material such as FRP and the metal member.
[0018]
　Therefore, the present invention has been made in view of the above problems, and improves the shear strength between the metal member and the fiber reinforced material by more firmly joining the metal member and the fiber reinforced resin material, and It is an object of the present invention to provide a metal-fiber reinforced resin material composite which is light in weight and excellent in workability while improving.
Means for solving the problem
[0019]
　As a result of intensive studies, the present inventors have constructed a fiber reinforced resin material with a matrix resin containing a specific thermoplastic resin and a reinforced fiber material contained in the matrix resin, and have a reinforced fiber material. The present invention has been completed by finding that the shear strength between the metal member and the fiber-reinforced resin material can be improved by interposing a resin layer made of the same kind of resin as the matrix resin between the metal member and the metal member.
[0020]
　That is, according to one aspect of the present invention, there is provided a method for producing a metal-fiber reinforced resin material composite including a metal member and a fiber reinforced resin material laminated on at least one surface of the metal member. A reinforcing fiber base material made of a reinforcing fiber material, a first cured matrix resin impregnated in the reinforcing fiber base material and containing a thermoplastic resin, between the metal member and the reinforcing fiber material. And a first cured resin layer formed of the matrix resin of the same kind as the matrix resin and impregnated into the reinforcing fiber base material leaching on the surface of the metal member. Is produced, and the matrix resin and the resin constituting the resin layer are heated to change the matrix resin and the resin forming the resin layer from the first cured state to the second cured state. Manufacture of a metal-fiber reinforced resin material composite in which the glass transition temperature of the resin forming the resin layer is changed so that the shear strength between the heated metal member and the fiber reinforced resin material is 0.8 MPa or more. A method is provided.
[0021]
　As described above, by leaching the matrix resin impregnated into the reinforcing fiber base material onto the surface of the metal member, a resin layer made of the same kind of resin as the matrix resin is formed between the metal member and the reinforcing fiber material. can do. Furthermore, changing the glass transition temperature of the matrix resin and the resin forming the resin layer before and after the heating of the resin forming the matrix resin and the resin forming the resin layer from the first cured state to the second cured state. Thus, the metal member after heating and the fiber-reinforced resin material can be bonded more firmly. Therefore, the shear strength between the metal member and the fiber-reinforced resin material after heating can be 0.8 MPa or more. Here, the shear strength is measured by a “shear test” described later. Therefore, 0.8 MPa corresponds to 40 N/5 mm.
[0022]
　Here, the matrix resin in the first cured state is, as the thermoplastic resin, a phenoxy resin (A), a polyolefin and an acid-modified product thereof, polycarbonate, polyamide, polyester, polystyrene, vinyl chloride, acryl, and further polyether. It may contain one or more selected from the group consisting of super engineering plastics such as ether ketone and polyphenylene sulfide.
[0023]
　In the method for producing a metal-fiber reinforced resin material composite, the first cured matrix resin may include 50 parts by mass or more of the phenoxy resin (A) with respect to 100 parts by mass of the resin component.
[0024]
　In the method for producing a metal-fiber reinforced resin material composite, the matrix resin in the first cured state is in a 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). A crosslinkable resin composition further containing a crosslinkable resin (B), wherein the first cured state is a solidified product of the resin forming the matrix resin and the resin layer, and the second cured state. However, a crosslinked cured product of the matrix resin and the resin forming the resin layer may be used.
[0025]
　In the method for producing a metal-fiber reinforced resin material composite, the first cured resin layer is a layer in which the content of fibers detached from the reinforced fiber material is 5% by mass or less, May have a thickness of 20 μm or less.
[0026]
　According to another aspect of the present invention, a metal-fiber reinforced resin material composite including a metal member and a fiber reinforced resin material that is laminated on at least one surface of the metal member to form a composite with the metal member. The fiber-reinforced resin material is a matrix resin containing a thermoplastic resin, a reinforcing fiber material contained in the matrix resin, and interposed between the reinforcing fiber material and the metal member, There is provided a metal-fiber reinforced resin material composite having a matrix resin and a resin layer made of the same kind of resin, and having a shear strength of 0.8 MPa or more between the metal member and the fiber reinforced resin material.
[0027]
　As described above, a matrix resin containing a thermoplastic resin and a reinforcing fiber material contained in the matrix resin constitute a fiber-reinforced resin material, and a matrix resin is provided between the reinforcing fiber material and the metal member. The metal member and the fiber reinforced resin material can be more firmly joined by interposing the resin layer made of the same kind of resin. Therefore, the shear strength between the metal member and the fiber reinforced resin material can be 0.8 MPa or more.
[0028]
　Here, a superaddition rule may be shown in which the maximum load of the metal-fiber reinforced resin material composite exceeds a law of addition (law of mix).
[0029]
　Further, the matrix resin in the first cured state is, as the thermoplastic resin, a phenoxy resin (A), a polyolefin and an acid modified product thereof, polycarbonate, polyamide, polyester, polystyrene, vinyl chloride, acryl, and further polyether ether. It may contain any one or more selected from the group consisting of super engineering plastics such as ketones and polyphenylene sulfide.
[0030]
　In the metal-fiber reinforced resin material composite, it is preferable that the matrix resin contains 50 parts by mass or more of the phenoxy resin (A) with respect to 100 parts by mass of the resin component.
[0031]
　In the metal-fiber reinforced resin material composite, it is preferable that the resin constituting the resin layer is a crosslinked cured product, and the glass transition temperature of the crosslinked cured product is 160° C. or higher.
[0032]
　In the metal-fiber reinforced resin material composite, the resin layer is a layer in which the content of fibers desorbed from the reinforced fiber material is 5% by mass or less, and the thickness of the layer is 20 μm or less. preferable.
[0033]
　In the metal-fiber reinforced resin material composite, the total thickness T1 of the metal member and the elastic coefficient E1 of the metal member, the total thickness T2 of the fiber reinforced resin material and the elastic coefficient E2 of the fiber reinforced resin material, However, you may make it satisfy|fill the relationship of following formula (1).
　T1×E1>0.3×T2×E2 ・・・Equation (1)
　(T1×E1)/(T2×E2)>0.3 ・・・Equation (1)
[0034]
　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.
[0035]
　The steel material may be a galvanized steel sheet, an electrogalvanized steel sheet, or an aluminized steel sheet.
[0036]
　Further, according to another aspect of the present invention, a metal-fiber reinforced resin material comprising a metal member and a fiber reinforced resin material laminated on at least one surface of the metal member and compounded with the metal member. In the composite, the fiber-reinforced resin material is a matrix resin containing a thermoplastic resin, a reinforcing fiber material contained in the matrix resin, and interposed between the reinforcing fiber material and the metal member. And a resin layer made of the same kind of resin as the matrix resin, wherein the matrix resin is 50 parts by mass or more with respect to 100 parts by mass of the resin component, and the phenoxy resin (A) 100. A metal-fiber reinforced resin material composite, which is a crosslinked cured product of a crosslinkable resin composition containing 5 parts by mass or more and 85 parts by mass or less of the crosslinking curable resin (B) with respect to parts by mass. Provided.
[0037]
　As described above, a matrix resin containing a thermoplastic resin and a reinforcing fiber material contained in the matrix resin constitute a fiber-reinforced resin material, and a matrix resin is provided between the reinforcing fiber material and the metal member. By interposing a resin layer made of the same type of resin as described above and further containing a phenoxy resin (A) and a crosslinkable curable resin (B) as matrix resins at a predetermined ratio, the metal member and the fiber reinforced resin material are combined. Can be joined more firmly. Therefore, the shear strength between the metal member and the fiber-reinforced resin material can be greatly improved.
[0038]
　Here, the maximum load of the metal-fiber reinforced resin material composite may exhibit a superaddition law.
[0039]
　In the metal-fiber reinforced resin material composite, the shear strength between the metal member and the fiber reinforced resin material is preferably 0.8 MPa or more.
[0040]
　In the metal-fiber reinforced resin material composite, the matrix resin and the resin forming the resin layer change from a solidified product in the first cured state to a crosslinked cured product in the second cured state by heating. Before and after, the glass transition temperature may change, and the shear strength between the metal member and the fiber-reinforced resin material after the heating may be 0.8 MPa or more.
[0041]
　In the metal-fiber reinforced resin material composite, the resin layer is a layer in which the content of fibers desorbed from the reinforced fiber material is 5% by mass or less, and the thickness of the layer is 20 μm or less. preferable.
[0042]
　In the metal-fiber reinforced resin material composite, the total thickness T1 of the metal member and the elastic coefficient E1 of the metal member, the total thickness T2 of the fiber reinforced resin material and the elastic coefficient E2 of the fiber reinforced resin material, However, you may make it satisfy|fill the relationship of following formula (1).
　(T1×E1)/(T2×E2)>0.3 Formula (1)
[0043]
　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.
[0044]
　The steel material may be a galvanized steel sheet, an electrogalvanized steel sheet, or an aluminized steel sheet.
Effect of the invention
[0045]
　As described above, according to the present invention, since the metal member and the fiber reinforced resin material can be bonded more firmly, the shear strength between the metal member and the fiber reinforced material can be improved and the strength can be improved. At the same time, it is possible to provide a metal-fiber reinforced resin material composite which is lightweight and has excellent workability, and a method for producing the same.
Brief description of the drawings
[0046]
FIG. 1 is a schematic diagram showing a cross-sectional structure of a metal-fiber reinforced resin material composite according to a preferred 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 the manufacturing process following FIG. 5.
FIG. 7 is a schematic diagram showing a cross-section in which an X portion of FIG. 6 is enlarged.
FIG. 8 is an explanatory view showing another example of the manufacturing process of the metal-fiber reinforced resin material composite according to the same embodiment.
FIG. 9 is an explanatory view showing still another example of the manufacturing process of the metal-fiber reinforced resin material composite according to the same embodiment.
FIG. 10 is an explanatory diagram showing a configuration of a sample of the metal-FRP composite for tensile test in Examples and Comparative Examples.
FIG. 11 is an explanatory diagram showing a configuration of a sample of a metal-FRP composite for bending test in Examples and Comparative Examples.
FIG. 12 is an explanatory diagram showing a structure of a sample of the metal-FRP composite for shear test in Examples and Comparative Examples.
FIG. 13 is a graph schematically showing the result of the tensile test of each test piece.
FIG. 14 is a graph schematically showing a preferable range of (T1×E1)/(T2×E2).
MODE FOR CARRYING OUT THE INVENTION
[0047]
　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.
[0048]
[Configuration of Metal-Fiber Reinforced Resin Material Composite]
　First, the configuration of the metal-fiber reinforced resin material composite resin material composite according to a preferred embodiment of the present invention will be described with reference to FIGS. 1 and 2. . 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.
[0049]
　As shown in FIG. 1, the metal-FRP composite 1 includes a metal member 11 and an FRP layer 12 as an example of the fiber reinforced resin material according to the present embodiment. The metal member 11 and the FRP layer 12 are compounded via the resin layer 101 which is a part of the FRP layer 12. Here, “composite” means that the metal member 11 and the FRP layer 12 (fiber reinforced resin material) are joined (bonded) via the resin layer 101 and are integrated. In addition, “integrated” means that the metal member 11 and the FRP layer 12 (fiber reinforced resin material) move as a unit during processing or deformation.
[0050]
　In the metal-FRP composite 1, the FRP layer 12 constitutes a part or all of the fiber reinforced resin material according to this embodiment. The resin layer 101, which is a part of the FRP layer 12, is interposed between the reinforcing fiber material 103 and the metal member 11 and is made of the same resin as the matrix resin 102 of the FRP layer 12, as described later.
[0051]
　In the present embodiment, the resin layer 101 is provided so as to be in contact with 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 resin layer 101 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 resin layer 101 and the FRP layer 12 may be sandwiched between the two metal members 11.
[0052]
　Hereinafter, each component of the metal-FRP composite 1 and other configurations will be described in detail.
[0053]
(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 a thin plate shape is preferable. 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 general-purpose cold-rolled steel sheets for drawing, ultra-deep drawing, and automobiles, which are standardized by the Japanese Industrial Standard (JIS) as thin steel sheets used 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, and workable hot-rolled high-strength steel sheet for automobiles. Carbon steel, alloy steel, high-strength steel, etc. used for structural purposes can also be mentioned as steel materials not limited to thin plates.
[0054]
　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. The surface roughening treatment may be, but is not limited to, a chemical surface roughening treatment such as static or chemical etching. Moreover, 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.
[0055]
　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 silane coupling agents, amino 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. And 4-dithiolamino-1,3,5-triazine monosodium and 2,4,6-trithiol-1,3,5-triazine.
[0056]
　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 preventive oil is often formed on the surface of the metal member 11. Even if it is attempted to bond the FRP and the metal member 11 with such an oil film formed on the surface of the metal member 11, it may be difficult to bond the FRP and the metal member 11 with sufficient bonding strength. That is, it may be difficult to produce the metal-FRP composite 1 exhibiting the superaddition rule. Therefore, when an oil film is formed on the surface of the metal member 11, it is preferable to perform degreasing treatment before joining with the FRP. This makes it possible to bond the FRP and the metal member 11 with a sufficient bonding strength, and it becomes easier for the metal-FRP composite 1 to obtain strength exceeding the additive rule described later. Regarding the necessity of degreasing, the target metal member 11 is joined to the target FRP by the target adhesive resin composition in advance without the degreasing step, 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.
[0057]
(FRP layer 12) The
　FRP layer 12 is a matrix resin 102, a reinforced fiber material 103 contained in the matrix resin 102 and compounded, and a resin layer located between the reinforced fiber material 103 and the metal member 11. 101 and. The resin layer 101 may be provided on at least one side of the FRP layer 12, and may be provided on both sides. That is, when the metal members 11 are arranged on both sides of the FRP layer 12, the resin layers 101 are provided between the metal members 11 on both sides of the reinforcing fiber material 103.
[0058]
　Further, as shown in FIG. 2, the FRP layer 12 may be laminated with at least one or more other FRP layers 13 to form a fiber reinforced resin material. In this case, the FRP layer 13 may be one layer or two or more layers. When the FRP layer 13 is laminated, at least the FRP layer 12 in contact with the metal member 11 has the resin layer 101. The other FRP layer 13 may have the same structure as the FRP layer 12, or may have a different structure. The thickness of the FRP layers 12 and 13 and the total number n of the FRP layers 12 and 13 when one or more FRP layers 13 are arranged may be appropriately set according to the purpose of use. When the FRP layer 13 is arranged, the FRP layers 12 and 13 may have the same configuration or may have different configurations. That is, the type of resin forming the matrix resin 102 of the FRP layer 12 and the matrix resin of the FRP layer 13, the type and content ratio of the reinforcing fiber material 103, and the like may be different for each layer. From the viewpoint of ensuring the adhesiveness between the FRP layer 12 and the FRP layer 13, the FRP layer 12 and one or more FRP layers 13 are the same or the same kind of resin, or the ratio of polar groups contained in the polymer. It is preferable to select a resin type having similar properties. 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 of 100 parts by mass of all 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.
[0059]
　Hereinafter, the reinforcing fiber material 103, the matrix resin 102, and the resin layer 101 in the FRP layer 12 will be sequentially described.
[0060]
The
　reinforcing fiber material 103 is not particularly limited, but for example, carbon fiber, boron fiber, silicon carbide fiber, glass fiber, aramid fiber, etc. 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 103, one kind of the above-mentioned fibers may be used alone, or a plurality of kinds may be used in combination. As the reinforcing fiber material in the FRP layer 13, the same material as above can be used.
[0061]
The
　matrix resin 102 is made of a resin composition containing a thermoplastic resin.
[0062]
◇Resin composition The resin composition
　constituting the matrix resin 102 can contain a thermosetting resin as a resin component in addition to the thermoplastic resin, but it is preferable to contain the thermoplastic resin as a main component. The type of thermoplastic resin that can be used as the matrix resin 102 is not particularly limited, and examples thereof include phenoxy resin, polyolefin and acid modified products thereof, polystyrene, polymethylmethacrylate, AS resin, ABS resin, polyethylene terephthalate and polybutylene terephthalate. Polyester such as 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, poly One or more selected from arylate, polyetherketone, polyetherketoneketone, nylon and the like can be used. The "thermoplastic resin" also includes a resin that can be a cross-linked cured product in a second cured state described later. Further, as the thermosetting resin that can be used for the matrix resin 102, for example, one or more selected from an epoxy resin, a vinyl ester resin, a phenol resin, and a urethane resin can be used.
[0063]
　Here, in the metal-FRP composite 1, a resin composition containing a thermoplastic resin (preferably containing a thermoplastic resin as a main component) is used as the matrix resin 102. As described above, since the matrix resin 102 contains the thermoplastic resin, a problem when the thermosetting resin is used as the matrix resin of the FRP described above, that is, the FRP layer 12 has brittleness, and the takt time is reduced. Problems such as long length and inability to bend can be solved.
[0064]
　Here, as will be described in detail later, in the process of forming the matrix resin 102 of the FRP layer 12, the matrix resin 102 leaches onto the surface of the metal member 11 (in other words, the interface between the metal member 11 and the reinforcing fiber material 103). There are cases. Then, the resin layer 101 may be formed by the matrix resin 102 leached on the surface of the metal member 11. When the resin layer 101 is formed by such leaching of the matrix resin 102, the thermoplastic resin forming the matrix resin 102 is a phenoxy resin, a polyolefin and an acid-modified product thereof, polycarbonate, polyamide, polyester, polystyrene, vinyl chloride. , Acrylic, and further preferably one or more selected from the group consisting of super engineering plastics such as polyether ether ketone and polyphenylene sulfide. In these thermoplastic resins, the molecules flow with a viscosity according to the temperature and the molecular weight during heating and melting, and under the conditions where they flow appropriately, they can sufficiently flow between the fiber bundles in the FRP and escape. Can be leached on the surface of the metal member 11 in the formation process of. Further, when the thermoplastic resin flowing with an appropriate viscosity comes into contact with the surface of the metal material, good adhesion is obtained when the surface of the metal material and the molecules of the thermoplastic resin interact favorably, and Since the material flows more easily into the unevenness, an anchor effect is easily obtained, and a more suitable adhesion state can be obtained. The conditions under which the viscosity is appropriate (temperature during heating, molecular weight) differ depending on the resin, but if the superaddition rule described below is satisfied, it can be determined that the viscosity is appropriate.
[0065]
　However, the thermoplastic resin usually has a high viscosity when melted, and cannot be impregnated into the reinforcing fiber material 103 in a low viscosity state like a thermosetting resin such as an epoxy resin before thermosetting, The impregnation property for the reinforcing fiber material 103 is poor. Therefore, unlike the case where the thermosetting resin is used as the matrix resin 102, the reinforcing fiber density (VF: Volume Fraction) in the FRP layer 12 cannot be increased. Taking carbon fiber reinforced plastic (CFRP) that uses carbon fiber as the reinforcing fiber material 103, for example, when epoxy resin is used as the matrix resin 102, VF can be about 60%, but polypropylene or When a thermoplastic resin such as nylon is used as the matrix resin 102, the VF is about 50%. Here, in order for the FRP to exhibit excellent tensile strength, the matrix resin 102 is impregnated into the reinforcing fiber material 103 in a state in which each fiber constituting the reinforcing fiber material 103 is strongly stretched in the same direction at a high density. There is a need. It is difficult for the matrix resin 102 to impregnate the reinforcing fiber material 103 in such a state. If the reinforcing fiber material 103 is not sufficiently impregnated with the matrix resin 102 and a defect such as a void occurs in the FRP, not only the FRP does not exhibit a desired tensile strength, but also the FRP starts brittle fracture from the defect. there's a possibility that. Therefore, the impregnation property is very important. Moreover, 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.
[0066]
　In order to solve the problem when using such a thermoplastic resin, it is preferable to use a phenoxy resin as the matrix resin 102. Since the phenoxy resin has a molecular structure very similar to that of the epoxy resin, it has the same heat resistance as the epoxy resin, and also has good adhesiveness to the metal member 11 and the reinforcing fiber material 103. Further, a so-called partially curable resin can be obtained by adding a curing component such as an epoxy resin to the phenoxy resin and copolymerizing the resin. By using such a partially curable resin as the matrix resin 102, it is possible to obtain a matrix resin having excellent impregnation properties into the reinforcing fiber material 103. Further, by thermally curing the curing component in the partially curable resin, it is possible to prevent the matrix resin 102 in the FRP layer 12 from being melted or softened when exposed to a high temperature like a normal thermoplastic resin. it can. The amount of the hardening component added to the phenoxy resin may be appropriately determined in consideration of the impregnating property into the reinforcing fiber material 103, 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 102, it is possible to add and control the curing component with a high degree of freedom.
[0067]
　Note that, for example, when carbon fiber is used as the reinforcing fiber material 103, the surface of the carbon fiber is often provided with a sizing agent that is well 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 102, the sizing agent for the epoxy resin can be used as it is. Therefore, cost competitiveness can be improved.
[0068]
　In addition, among the thermoplastic resins, the phenoxy resin has good moldability and is excellent in adhesiveness with the reinforcing fiber material 103 and the metal member 11, and by using an acid anhydride, an isocyanate compound, caprolactam or the like as a cross-linking agent. After molding, it is possible to give the same properties as the thermosetting resin having high heat resistance. Therefore, in the present embodiment, as the resin component of the matrix resin 102, 50 parts by mass or more of the phenoxy resin (A) is contained 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 phenoxy resin). It is preferable to use a solidified product or a cured product of a resin composition (composed of the resin (A)). Here, the term "solidified product" simply means a solidified resin component itself (first cured state), and the term "cured product" means that the resin component contains various curing agents. Means a second cured state. 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 formed by crosslinking. By using such a resin composition, it becomes possible to firmly bond the metal member 11 and the FRP layer 12. The 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.
[0069]
　The content of the phenoxy resin (A) can be measured by infrared spectroscopy (IR: InfraRed spectroscopy) as described below, and the content ratio of the phenoxy resin from the resin composition targeted by IR can be measured. 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.
[0070]
　The FRP layer 12 is cut off with a sharp blade or the like, 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. IR measuring device, can be used ones manner generally commercially available, absorbed as precision (Absorbance) in 1% increments, wavenumber (Wavenumber) is 1 cm -1 with analytical accuracy that can distinguish units An apparatus is preferable, and examples thereof include FT/IR-6300 manufactured by JASCO Corporation.
[0071]
　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 described above are observed in the measured IR spectrum, it is determined that the IR spectrum is composed of only the phenoxy resin.
[0072]
　On the other hand, when a peak other than the absorption peak disclosed in Non-Patent Document 1 is detected, it is determined that the resin composition contains another resin composition, and the content is estimated as follows. The powder of the resin composition to be analyzed and the powder of the phenoxy resin composition (eg, 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. Based on the obtained change in intensity, a calibration curve as shown in FIG. 3 is created. By using the obtained calibration curve, the phenoxy resin content of a sample whose phenoxy resin content is unknown can be determined.
[0073]
　Specifically, when the phenoxy content of the resin composition to be analyzed is X%, X% can be estimated from the change in strength when the phenoxy resin is shaken from X% to 100%. That is, when measured with the above-mentioned compounding 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 , the intensity when X% is the content is I X , If the content is 0%, that is, 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.
[0074]
　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) within 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 the effect is that the Mw is 100,000 or less, further 80,000 or less. By doing so, it will be even higher. The Mw in the present specification is a value measured by gel permeation chromatography (GPC) and converted using a standard polystyrene calibration curve.
[0075]
　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.
[0076]
　Further, the glass transition temperature (Tg) of the phenoxy resin (A) is suitably in the range of, for example, 65° C. or higher and 150° C. or lower, but is 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 resin layer 101 can have a sufficient thickness. On the other hand, when Tg is 150° C. or less, 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 at a temperature within the range of 20 to 280° C. under a temperature rising condition of 10° C./min using a differential scanning calorimeter, and the second scan peak was obtained. It is a numerical value calculated from the value.
[0077]
　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 Phenototo YP-55U), bisphenol F-type phenoxy resin (for example, available as Nippon Steel & Sumikin Chemical Co., Ltd. Phenototo 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.
[0078]
　The thermoplastic resin used as the resin component of the matrix resin 102 preferably has a melt viscosity of 3,000 Pa·s or less in any of the temperature ranges of 160 to 250° C., and 90 Pa·s or more and 2,900 Pa. It is more preferable that the melt viscosity is in the range of s or less, and it is further preferable that the melt viscosity is in the range of 100 Pa·s or more and 2,800 Pa·s or less. 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 resin layer 101. On the other hand, if the melt viscosity is 90 Pa·s or less, the molecular weight of the resin composition is too small, and if the molecular weight is too small, the resin composition becomes brittle and the mechanical strength of the metal-FRP composite 1 decreases.
[0079]
◇Crosslinkable resin composition
　A resin composition containing a phenoxy resin (A) is mixed with, for example, an acid anhydride, an isocyanate, or caprolactam as a crosslinking agent to give a crosslinkable resin composition (that is, a resin composition It can also be a cured product). The crosslinkable resin composition improves the heat resistance of the resin composition by utilizing a secondary hydroxyl group contained in the phenoxy resin (A) to cause a crosslinking reaction, so that it can be applied to a member used in a higher temperature environment. It is advantageous for application. For the cross-link formation using the secondary hydroxyl group of the phenoxy resin (A), it is preferable to use a cross-linkable 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 resin composition, a cured product (crosslinked cured product) in the second cured state in which Tg of the 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 resin composition is, for example, 160° C. or higher, preferably 170° C. or higher and 220° C. or lower.
[0080]
　In the crosslinkable resin composition, the crosslinkable 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 resins (for example, available as Nippon Steel & Sumitomo Metal Corporation Epotote YD-011, Epotote YD-7011, Epotote YD-900), bisphenol F type epoxy resins (eg, , Available as Epototo YDF-2001 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., diphenyl ether type epoxy resin (for example, available as YSLV-80DE manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), tetramethylbisphenol F type epoxy resin (for example, Nippon Steel & Sumikin Chemical Co., Ltd.) Available as YSLV-80XY manufactured by K.K.), 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 Epototo YDPN-638 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), orthocresol novolac type epoxy resin (for example, Epototo YDCN-701, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., Epototo) YDCN-702, Epotote YDCN-703, Epotote YDCN-704), aralkylnaphthalenediol 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 not limited thereto. These epoxy resins may be used alone or in combination of two or more.
[0081]
　The cross-linking curable resin (B) is not particularly limited, but a crystalline epoxy resin is preferable, and the melting point at a melting point of 70° C. to 145° C. and the melt viscosity at 150° C. is 2.0 Pa. A crystalline epoxy resin having s or less is more preferable. By using the crystalline epoxy resin having such a melting property, the melt viscosity of the crosslinkable resin composition as the resin composition can be reduced, and the adhesiveness of the resin layer 101 can be improved. When the melt viscosity exceeds 2.0 Pa·s, the moldability of the crosslinkable resin composition may be deteriorated and the homogeneity of the metal-FRP composite 1 may be deteriorated.
[0082]
　Examples of the crystalline epoxy resin suitable as the cross-linking 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.
[0083]
　The cross-linking agent (C) three-dimensionally cross-links the phenoxy resin (A) 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.
[0084]
　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, but from the viewpoint of imparting heat resistance to the metal-FRP composite 1 and reactivity, a phenoxy resin ( Aromatic acid anhydrides having two or more acid anhydrides that react with the hydroxyl group of A) are preferable. Particularly, 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 anhydride has a higher crosslink 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 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.
[0085]
　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 cross-linked and cured by the esterification reaction of (1) and the reaction of the carboxyl group generated by this esterification reaction with 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 resin composition, so that the adherend (metal It exhibits excellent properties such as improved impregnation with the member 11 and the FRP layer 12), accelerated crosslinking reaction, increased crosslink density, and improved mechanical strength.
[0086]
　In the crosslinkable 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 with the acid anhydride group of the crosslinking agent (C) 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 or the residual carboxyl group derived from the crosslinking agent (C) reacts 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 resin composition is a thermoplastic resin and has excellent storage stability.
[0087]
　In the crosslinkable resin composition utilizing the crosslinking of the phenoxy resin (A), the crosslinkable 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 as follows. The content of the crosslinkable resin (B) with respect to 100 parts by mass of the phenoxy resin (A) is more preferably 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 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 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 resin (B), and thus the crosslink curing of the crosslinkable resin composition. The product easily develops Tg of 160° C. or higher, and the fluidity becomes good. The content of the crosslinkable resin (B) is measured by the same method as described above for the peak derived from the epoxy resin by the method using IR as described above to measure the content of the crosslinkable resin (B). it can.
[0088]
　The compounding amount of the cross-linking agent (C) 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), and preferably The amount is in the range of 0.7 mol or more and 1.3 mol or less, more preferably 1.1 mol or more and 1.3 mol or less. 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 blending amount of the crosslinkable curable resin (B) according to the blending 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 crosslinking agent (C). For that purpose, the compounding amount of the epoxy resin is preferably 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 crosslinking agent (C) to the epoxy resin is in the range of 0.7 mol or more and 1.0 mol or less.
[0089]
　When the cross-linking agent (C) is blended with the phenoxy resin (A) and the cross-linking curable resin (B), a cross-linkable resin composition can be obtained, but an accelerator as a catalyst so that the cross-linking reaction is surely performed. (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 crosslinkable resin composition is formed into a fine powder and is attached to the reinforcing fiber base material by a powder coating method using an electrostatic field to form the matrix resin 102, the catalyst activation temperature is set as the accelerator (D). It is preferable to use an imidazole-based latent catalyst that is solid at room temperature that is 130° C. or higher. When the accelerator (D) is used, the compounding amount 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.
[0090]
　The crosslinkable resin composition is solid at room temperature, and its melt viscosity is such that the minimum melt viscosity, which is the lower limit of melt viscosity in the temperature range of 160 to 250° C., is 3,000 Pa·s or less. It is preferably 2,900 Pa·s or less, 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 crosslinkable resin composition can be sufficiently impregnated into the adherend during thermocompression bonding such as hot pressing. Since it is possible to suppress the occurrence of defects such as voids in the resin layer 101, 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.
[0091]
　The resin composition (including the crosslinkable resin composition) for forming the matrix resin 102 includes, for example, natural rubber, synthetic rubber, elastomer, and various inorganic fillers as long as the adhesiveness and physical properties thereof are not impaired. Other additives such as a solvent, an extender pigment, a colorant, an antioxidant, a UV inhibitor, a flame retardant, and a flame retardant auxiliary may be blended.
[0092]
　As described above, an oil film may be formed on the surface of the metal member 11. Even if it is attempted to bond the FRP and the metal member 11 with such an oil film formed on the surface of the metal member 11, it may be difficult to bond the FRP and the metal member 11 with sufficient bonding strength. As one of measures against such a problem, there is a method of degreasing the surface of the metal member 11 as described above.
[0093]
　On the other hand, when the resin layer 101 is formed by leaching the matrix resin 102, an oil surface adhesive may be added to the resin composition for forming the matrix resin 102. At least a part of the oil surface adhesive which is added to the resin composition is leached onto the surface of the metal member 11 and contained in the resin layer 101. The resin layer 101 containing the oil surface adhesive is firmly bonded to the metal member 11 even when an oil film is formed on the surface of the metal member 11.
[0094]
　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-FRP composite 1 showing the superaddition rule can be produced as a result of joining the metal member 11 on which the oil film is formed and the FRP to which the oil surface adhesive is added, 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., Devcon PW1 (methacrylate oil surface adhesive) manufactured by Devcon Corporation, and the like. Only one type of oil surface adhesive may be used, or a plurality of types of oil surface adhesive may be mixed and used.
[0095]
　The blending amount of the oil surface adhesive in the matrix resin 102 may be adjusted so that the metal-FRP composite 1 exhibits the superaddition rule. As an example, 50 parts by mass with respect to 100 parts by mass of the resin component. It may be included in a large amount, and may be about several parts by mass as long as the effects of the present embodiment (superaddition rule, etc.) are exhibited.
[0096]
　When the fiber-reinforced resin material is a laminated body in which one layer or two or more layers of the FRP layer 13 are laminated on the FRP layer 12, the matrix resin in the FRP layer 13 is not particularly limited, and even a thermoplastic resin may be thermoset. Resin may be used. Examples of the thermoplastic resin include phenoxy resin, polyolefin and acid-modified products thereof, polystyrene, polymethyl methacrylate, AS resin, ABS resin, thermoplastic aromatic polyester such as polyethylene terephthalate and polybutylene terephthalate, vinyl chloride, acryl, polycarbonate. , Polyimide, polyamide, polyamide imide, polyether imide, polyether sulfone, polyphenylene ether and its modified products, polyether ether ketone, polyphenylene sulfide, super engineering plastics, polyoxymethylene, polyarylate, polyether ketone, polyether ketone ketone , And one or more selected from nylon and the like can be used. As the thermosetting resin, for example, epoxy resin, vinyl ester resin or the like can be used. When a phenoxy resin is used as the matrix resin 102 of the FRP layer 12, it is preferable to form the matrix resin of the FRP layer 13 with a resin composition having good adhesion to the phenoxy resin. Here, as the resin having good adhesion to the phenoxy resin, for example, epoxy resin, phenoxy resin, polyolefin resin acid-modified with maleic anhydride, polycarbonate, polyarylate, polyimide, polyamide, polyether sulfone and the like. To be However, the matrix resin in the FRP layer 13 is preferably a resin composition containing a thermoplastic resin as in the FRP layer 12, and the same or the same resin composition as the matrix resin 102 in the FRP layer 12. Is more preferable.
[0097]
The
　resin layer 101 is interposed between the metal member 11 and the FRP layer 12 of the metal-FRP composite 1 to bond the metal member 11 and the FRP layer 12 together. The resin layer 101 is formed between the surface of the metal member 11 and the reinforcing fiber material 103 closest to the surface. More specifically, the reinforcing fiber material 103 is the matrix resin 102 impregnated into the sheet-shaped reinforcing fiber base material 104 made of the reinforcing fiber material 103 when the metal member 11 and the FRP layer 12 are joined by thermocompression bonding. Melts. The reinforcing fiber material 103 flowing out together with the molten matrix resin 102 forms fine irregularities due to the reinforcing fiber material 103 on the surface of the reinforcing fiber base material 104. The resin layer 101 is formed between the metal member 11 and a portion of the reinforcing fiber material 103 located on the surface of the reinforcing fiber base material 104 having the fine irregularities, which is closest to the surface of the metal member 11. Further, when the matrix resin 102 is melted as described above, some of the fibers forming the reinforcing fiber material 103 may be desorbed and mixed into the resin layer 101. In other words, the possibility that fibers that were fluff from the reinforcing fiber material 103 may be mixed in the resin layer 101 cannot be excluded. However, the amount of fibers mixed in the resin layer 101 is at most 5 mass% or less with respect to the total mass of the resin layer 101, and is not enough to strengthen the resin forming the resin layer 101. That is, the resin layer 101 does not contain fibers from the viewpoint of reinforcing the resin. Specifically, the resin layer 101 is a layer in which the content of fibers detached from the reinforcing fiber material 103 is 5% by mass or less, and is preferably made of only a resin composition containing no thermoplastic resin containing a thermoplastic resin. It is a layer. Therefore, the resin layer 101 is a portion where the reinforcing effect by the fibers is not exerted, and the mechanical strength such as the bending strength and the bending elastic modulus of the resin layer 101 is the mechanical strength peculiar to the solidified or cured product of the resin. Is the same as.
[0098]
　Further, the resin layer 101 needs to be formed of a resin composition made of the same resin as the matrix resin 102 of the FRP layer 12, and is preferably made of a resin composition made of the same resin. Since the matrix resin of the FRP layer 12 and the resin layer 101 are formed of a resin composition composed of at least the same type of resin, the adhesion between the metal member 11 and the FRP layer 12 via the resin layer 101 is strong. Therefore, the mechanical strength of the entire metal-FRP composite 1 can be increased. Since the type and physical properties of the resin forming the resin layer 101 are the same as those of the matrix resin 102 described above, detailed description thereof will be omitted. As described above, an oil surface adhesive may be added to the resin layer 101.
[0099]
　As will be described later, the resin layer 101 may be formed of resin leached at the interface with the metal member 11 in the process of forming the matrix resin 102 of the FRP layer 12, or the FRP layer. It may be formed by disposing a resin sheet or applying a resin composition between the precursor of 12 and the metal member 11. In this case, an oil surface adhesive may be added to the resin sheet or the coating liquid. The compounding amount of the oil surface adhesive may be determined by the same method as described above.
[0100]
　An oil surface adhesive may be applied to the interface between the resin layer 101 and the metal member 11 to bond them. For example, when the resin layer 101 is formed by leaching the matrix resin 102, an oil surface adhesive may be applied to at least one surface of the FRP (or prepreg) and the metal member 11 to adhere them. .. The coating method is not particularly limited, and examples thereof include roll coating, bar coating, spraying, dipping, and coating using a brush. When the resin layer 101 is formed of a resin sheet, an oil surface adhesive may be applied to the surface of the resin sheet on the metal member 11 side or the surface of the metal member 11 to adhere them. Further, when the resin layer 101 is formed by applying the resin composition, an oil surface adhesive is applied to the surface of the metal member 11 and the FRP (or prepreg) on ​​the side where the resin composition is not applied, and these are applied. You may join. 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.
[0101]
　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 a resin composition for forming the matrix resin 102, A method of applying an oil surface adhesive to the interface between the metal member 11 and the adhesive resin layer 13 can be used. 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.
[0102]
◇ Thickness of the
　resin layer 101 The resin layer 101 is formed with a substantially uniform thickness between the metal member 11 and the reinforcing fiber material 103 of the FRP layer 12, and since there are no voids, the metal member 11 and the FRP layer. The adhesiveness with 12 can be further strengthened. On the other hand, since the resin layer 101 is a layer made of only resin that is not fiber-reinforced, its mechanical strength is inferior to that of the portion of the FRP layer 12 in which the matrix resin 102 impregnates the reinforcing fiber material 103. Therefore, if the thickness of the resin layer 101 is too large, the mechanical strength and durability of the metal-FRP composite 1 may decrease. Further, in order to directly transmit the influence of the strength of the FRP layer 12 having large mechanical strength such as tensile strength to the metal member 11, it is preferable that the resin layer 101 has a small thickness to some extent.
[0103]
　For the above reasons, the thickness of the resin layer 101 is, for example, preferably 50 μm or less, more preferably 40 μm or less, further preferably 20 μm or less, and particularly preferably 10 μm or less. In particular, when the resin layer 101 is derived from the raw material resin composition of the matrix resin 102 of the FRP layer 12 (that is, the matrix resin 102 is formed at the interface between the FRP layer 12 and the metal member 11 in the process of forming the matrix resin 102). In the case where the raw material resin composition is formed of resin that has leached out), the thickness of the resin layer 101 is preferably 20 μm or less, and more preferably 10 μm or less. When the thickness of the resin layer 101 exceeds 50 μm, the effect of reinforcing the resin with fibers becomes weak, and the mechanical strength and durability of the metal-FRP composite 1 may be reduced, and the strength of the FRP layer 12 may be reduced. This is not preferable because it becomes difficult to directly transmit the influence of 1 to the metal member 11.
[0104]
　Further, from the viewpoint of sufficiently securing the adhesiveness between the metal member 11 and the FRP layer 12, the thickness of the resin layer 101 is preferably 1 μm or more. When the resin layer 101 is formed by a method such as stacking resin sheets or coating a raw material resin composition, the thickness of the resin layer 101 is preferably 20 μm or more.
[0105]
(Shear Strength) In the
　metal-FRP composite 1 having the above configuration, the shear strength between the metal member 11 and the fiber reinforced resin material including the FRP layer 12 (in some cases, the FRP layer 13) is 0.8 MPa or more. Preferably, it is more preferably 1.0 MPa or more. By setting the shear strength to 0.8 MPa or more, sufficient mechanical strength of the metal-FRP composite 1 can be ensured and excellent durability can be obtained. The shear strength in the present embodiment is a value measured by a shear test described later. Therefore, 0.8 MPa corresponds to 4.0 N/5 mm and 1.0 MPa corresponds to 50 N/5 mm.
[0106]
　The shear strength within the above range is from that of the solidified product in the first cured state of the resin composition (including the crosslinked resin composition) forming the matrix resin 102 and the resin layer 101 to the second by heating. The glass transition temperature changes before and after the change to the crosslinked cured product in the cured state. For example, the Tg of the first cured resin composition is 150° C. or lower, while the Tg of the second cured resin composition is 160° C. or higher. Thereby, the shear strength between the metal member 11 and the FRP layer 12 after the heating can be more surely set to 0.8 MPa or more.
[0107]
(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. 13. FIG. 13 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 below-mentioned Example. The horizontal axis of FIG. 13 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 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 deformation amount and the tensile load when the metal member 11 is broken.
[0108]
　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 X mark 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 (maximum 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.
[0109]
　The super-addition rule in the present embodiment means that the expression (2-2) is established among the following expressions (2-1) and (2-2) considered as the super-addition rule.
　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 Expression (2-2) is satisfied. Here, since the load A1 is larger than the load A2, the formula (2-1) is inevitably satisfied if the formula (2-1) is satisfied. Therefore, when the formula (2-1) is satisfied, However, it may be determined that the super-additive rule holds.
[0110]
　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. In that case, it is easier to determine the superaddition rule based on the equation (2-1). At this 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.
[0111]
　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 satisfied. 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.
[0112]
　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 a 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).
[0113]
In order for the
　metal-FRP composite 1 to express the superaddition rule (for the formula (1)) , for example, the metal member 11 and the FRP layer 12 (when the FRP layer 13 is present, the FRP layers 12 and 13) are used. It suffices to have the configuration described above and to satisfy the following expression (1).
　　(T1×E1)/(T2×E2)>0.3 Formula (1)
[0114]
　In the formula (1), T1 is the total thickness of the metal member 11, E1 is the elastic coefficient of the metal member 11, and T2 is the total thickness of the FRP layer 12 (that is, between the reinforcing fiber material 103 and the resin layer 101). The total thickness, which is the total thickness of the FRP layers 12 and 13 when the FRP layer 13 is present, and E2 is the elastic modulus of the FRP layer 12 (the FRP layers 12 and 13 when the FRP layer 13 is present). Is. The elastic modulus in the present embodiment means the tensile elastic modulus (Young's modulus) at room temperature (25° C.). Therefore, T1 and E1 are parameters related to the metal member 11, and T2 and E2 are parameters related to the FRP layer 12 (FRP layers 12 and 13 when the FRP layer 13 is present). 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. The FRP layer 12 is composed of a resin layer 101 and a layer made of a reinforcing fiber material 103 and a matrix resin 102. The elastic coefficient E2 of the FRP layer 12 is calculated by adding the elastic coefficients of these layers according to the addition rule. For example, when the layer composed of the reinforcing fiber material 103 and the matrix resin 102 is A and the resin layer 101 is B, the elastic modulus E2 is (elastic modulus of A×thickness of A/total thickness T2 of FRP layer 12)+(B Is calculated by the following formula: elastic coefficient x thickness of B/total thickness of FRP layer 12 T2).
[0115]
　Further, the resin layer 101 may be very thin with respect to the thickness of the reinforcing fiber material 103. In this case, T2 may be only the thickness of the reinforcing fiber material 103. That is, the thickness of the adhesive resin layer 13 may be ignored. For example, when the thickness of the resin layer 101 is less than 5 μm with respect to the thickness of the reinforcing fiber material 103, the thickness of the resin layer 101 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 a plurality of metal members is calculated. Similarly, when one or more FRP layers 13 are stacked on the FRP layer 12, E2 is calculated according to the additive rule. For example, assuming that the FRP layers 12 and 13 are A, B, C,... Of thickness/total thickness T2 of a plurality of FRP layers). The elastic coefficients of the FRP layers 12 and 13 may be the elastic coefficients of the reinforcing fiber material 103 that constitutes them.
[0116]
　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 a resin layer 101 interposed therebetween. The FRP layer 12 is brittle, but the metal member 11 is ductile and has a large elastic modulus E1. At this time, since the resin layer 101 contains the phenoxy resin (A) or the like having excellent adhesiveness to the metal member 11, the metal member 11 and the FRP layer 12 are firmly adhered by the resin layer 101. 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 has a higher brittle fracture and a higher strength than the metal member 11 alone or the FRP layer 12 alone when the total thickness is the same.
[0117]
　The metal member 11 and the adhesive resin forming the resin layer 101 have different coefficients of thermal expansion, and the metal member 11 has a larger amount of change due to heat. Therefore, in the manufacturing process, when the metal-FRP composite 1 is molded at a high temperature and then cooled, the metal member 11 having a large expansion and contraction follows the metal member 11, and the FRP layer 12 and the resin layer 101 are compressed to some extent from the beginning. It is fixed with force (internal stress) applied. When a tensile load is applied to the metal-FRP composite 1, the FRP layer 12 and the resin layer 101 in the compressed state have a larger elongation margin than in the uncompressed state, and the fracture is delayed by that amount. 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, as the elastic coefficient E1 of the metal member 11 is larger, the tensile load per unit elongation amount of the metal-FRP composite 1 is larger. 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. The body 1 can withstand higher tensile loads.
[0118]
　Here, the above formula (1) is derived by the following experiment.
　That is, whether or not the strength exceeding the additive law was obtained for a large number of samples in which the thickness and elastic coefficient of the metal member and the thickness and elastic coefficient of the FRP were changed was tested, and then the thickness of the FRP was changed horizontally. With respect to the axis, the verification result (whether strength exceeding the addition rule was obtained) of each sample was plotted on a coordinate plane with the thickness of the metal member taken as the vertical axis. Then, it is derived from the result of expressing the straight line representing the boundary of the region in which the intensity exceeding the addition rule is obtained as an approximate curve by a known statistical analysis process. According to the above formula (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.
[0119]
　From 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, although it is not as good as iron.
[0120]
　The thicknesses of the metal member 11, the FRP layer 12, and the resin layer 101 can be measured according to the cross-section method of the optical method of JIS K 5600-1-7, 5.4 as follows. .. That is, using a room temperature curing resin that can be embedded without any harmful effect on the sample, using a low viscosity Epomount 27-777 made by Refinetech Co., Ltd. as a main agent and 27-772 as a curing agent, Embed. At a place to be observed with a cutting machine, a sample is cut so as to be parallel to the thickness direction to obtain a cross section, and a count of abrasive paper specified in JIS R 6252 or 6253 (for example, 280 count, 400 count or 600 count) is used. 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 a condition that can withstand observation.
[0121]
　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 field of view 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 resin layer 101, the observation visual field is divided into four equal parts as shown in FIG. 4, and the thickness of the resin layer 101 is measured at the center portion in the width direction of each separation point, and the average thereof is measured. Is the thickness in the field of view. This observation visual field is performed by selecting 5 different portions, and each observation visual field is divided into four equal parts, the thickness of each fraction is measured, and the average value is calculated. Adjacent observation fields of view should be selected at a distance of 3 cm or more. The value obtained by further averaging the average values ​​at these five points may be used as the thickness of the resin layer 101. The thickness of the metal member 11 and the FRP layer 12 may be measured in the same manner as the thickness of the resin layer 101.
[0122]
　When the boundary surfaces of the metal member 11, the resin layer 101, and the reinforcing fiber material 103 are relatively clear, the thickness of the resin layer 101 can be measured by the above method. However, the boundary surface between the resin layer 101 and the reinforcing fiber material 103 is not always clear. For example, when the resin layer 101 is formed by seeping the matrix resin 102, the boundary surface is often unclear. In such a case, the boundary line 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 above-mentioned microscope, and the area ratio of the fiber portions forming the reinforcing fiber material 103 (the area ratio of the fiber portions to the total area of ​​the observation visual field) is measured. 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. The cutting surface when the area ratio of the fiber portion exceeds 10% may be the boundary surface between the resin layer 101 and the reinforcing fiber material 103.
[0123]
(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. That is, it can be said that the larger the degree of superaddition rule, the more preferable. Then, the present inventor examined the results of Examples (Examples in which the metal-FRP composite 1 was produced under various manufacturing conditions and evaluated the characteristics thereof) described later in detail, and the result was (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 super-addition rule when the manufacturing conditions are leveled, and the result shows the results of (T1×E1)/(T2×E2) on the horizontal axis and the super-addition rule on the vertical axis. When plotted on a plane having a certain degree, a graph L4 shown in FIG. 14 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 becomes 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 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 can be, for example, about 2.7.
[0124]
[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 to 9 are explanatory views showing an example of a manufacturing process of the metal-FRP composite 1.
[0125]
　In the method for producing the metal-FRP composite 1 according to this embodiment, the step (1) of producing the FRP layer 12 and the step (2) of setting the shear strength between the metal member 11 and the FRP layer 12 to 0.8 MPa or more. And, including. In step (1), the FRP layer 12 having the reinforcing fiber base material 104, the matrix resin 102 in the first cured state impregnated in the reinforcing fiber base material 104, and the resin layer 101 in the first cured state is produced. To do. In the step (2), the glass transition temperature of the resin composition is changed before and after the resin composition forming the matrix resin 102 and the resin layer 101 is changed from the first cured state to the second cured state by heating. By this, the shear strength between the metal member 11 and the FRP layer 12 after heating is set to 0.8 MPa or more.
[0126]
　In the step (1), the first cured resin layer 101 is preferably formed by leaching the matrix resin 102 with which the reinforcing fiber base material 104 is impregnated onto the surface of the metal member 11.
[0127]
　In the step (1), it is preferable that the matrix resin 102 in the first cured state contains 50 parts by mass or more of the phenoxy resin (A) with respect to 100 parts by mass of the resin component.
[0128]
　In the step (1), the matrix resin 102 in the first cured state 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) (B). It is preferable that the crosslinkable resin composition further contains In this case, the first cured state is a solidified product of the resin composition for forming the matrix resin 102 and the resin layer 101, and the second cured state is for forming the matrix resin 102 and the resin layer 101. It is a crosslinked cured product of a resin composition.
[0129]
　As a more specific method for producing the metal-FRP composite 1 as described above, for example, the following production methods 1 to 3 can be mentioned.
[0130]
[Manufacturing Method 1]
　First, the flow of Manufacturing Method 1 will be described with reference to FIGS. The manufacturing method 1 includes, for example, step A and step B.
[0131]

　Step A is a step of forming a prepreg 106 in which the partially fused structure 105A of the raw material resin composition containing a thermoplastic resin is formed on at least one surface of the reinforcing fiber base material 104. As a method of carrying out this step A, there are, for example, the following method A1 or method A2.
[0132]
(Method A1) The
　method A1 may further include the following step a and step b.
　Step a: In the
　step a, as shown in FIGS. 5A and 5B, at least one surface of the sheet-shaped reinforcing fiber base material 104 made of the reinforcing fiber material 103 is coated with a fine amount of the raw material resin composition which is solid at room temperature. The powder 105 is attached to form the resin-attached fiber base material 104A. As a method for attaching the fine powder 105 to the reinforcing fiber base material 104, for example, a powder coating method can be used. Here, the above-mentioned oil surface adhesive may be added to the raw material resin composition. According to the powder coating method, since the raw material resin composition is fine particles, it is easily melted, and since the coating film after coating has appropriate voids, it serves as an escape path for air and voids are less likely to occur. When thermocompressing the prepreg 106 and the metal member 11 in step B described later, the resin melted on the surface of the prepreg first spreads quickly on the surface of the metal member 11 and then impregnates inside the reinforcing fiber base material 104. .. Therefore, as compared with the conventionally used melt impregnation method, defects due to insufficient wettability of the molten resin on the surface of the metal member 11 are less likely to occur. That is, in the melt impregnation method in which the resin extruded from the reinforcing fiber base material 104 adheres to the metal member 11, the wettability of the molten resin on the surface of the metal member 11 tends to be insufficient in the prepared prepreg. The painting method solves this problem.
[0133]
　The powder coating method includes, for example, electrostatic coating method, fluidized bed method, and suspension method as main construction methods. Among them, electrostatic coating method and fluidized bed method are suitable methods for thermoplastic resin. It is preferable because the process is simple and the productivity is good. In particular, the electrostatic coating method is the most preferable because the adhesion of the fine powder 105 of the raw material resin composition to the reinforcing fiber base material 104 is excellent in uniformity.
[0134]
　Although FIG. 5B shows a state in which the fine powder 105 of the raw material resin composition is attached to one surface of the resin-attached fiber base material 104A, the fine powder 105 is attached to both sides of the resin-attached fiber base material 104A. The powder 105 may be attached.
[0135]
(Coating Conditions by Powder Coating Method)
　The average particle size of the fine powder 105 of the raw material resin composition used in the powder coating method is, for example, preferably in the range of 10 μm or more and 100 μm or less, and in the range of 40 μm or more and 80 μm or less. More preferably, it is more preferably in the range of 40 μm or more and 50 μm or less. By setting the average particle size of the fine powder 105 to 100 μm or less, the energy when the fine powder 105 collides with the fibers in powder coating in an electrostatic field can be reduced, and the adhesion rate to the reinforcing fiber base material 104 can be increased. You can Further, by setting the average particle size to 10 μm or less, it is possible to suppress a decrease in the adhesion efficiency due to the particles being scattered by the accompanying air flow, and the working environment is deteriorated by the fine powder 105 of the raw material resin composition floating in the air. It can be prevented from being caused. As a method for making the raw material resin composition finely divided, it is preferable to use a crushing and mixing machine such as a low temperature dry crushing machine (Centry dry mill), but the method is not limited thereto. When the raw material resin composition is pulverized, a plurality of raw material components may be pulverized and then mixed, or a plurality of components may be mixed in advance and then pulverized.
[0136]
　In the powder coating, the fine powder 105 of the raw material composition may be applied so that the amount of adhesion (resin ratio: RC) of the fine powder 105 to the reinforcing fiber base material 104 falls within the range of 20% or more and 50% or less. preferable. 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 bending elastic modulus of FRP can be prevented. Further, by setting RC to 20% or more, the necessary amount of resin can be secured, so that the matrix resin 106 can be sufficiently impregnated into the inside of the reinforcing fiber base material, and the thermophysical properties and mechanical properties can be improved.
[0137]
(Conditions Regarding Reinforcing Fiber Base Material)
　Examples of the reinforcing fiber base material 104, which is a sheet-like base material made of the reinforcing fiber material 103, include, for example, a non-woven fabric base material using chopped fibers, a cross material using continuous fibers, and a unidirectional material. A 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. Regarding the type of the reinforcing fiber material 103, for example, any of PAN type and pitch type may be used, and one of these may be used alone depending on the purpose and application, Alternatively, two or more kinds may be used in combination.
[0138]
　When a carbon fiber cloth material or a UD material is used as the reinforcing fiber base material 104, it is preferable that the carbon fiber material is subjected to an opening treatment (referred to as a filament). In general, carbon fibers are fiber bundles composed of a large number of short fibers such as 1,000 to tens of thousands, and the cross section thereof is circular or slightly flat elliptical. Therefore, it is difficult to reliably impregnate the inside of the fiber bundle with the resin. The fiber-spreading process is a process in which the carbon fiber bundle is widened and thinned in the width direction by a known mechanical method. Since the resin-impregnating property is greatly improved by the opening process as compared with the non-opened product, the physical properties of the molded product are also improved. The basis weight of the reinforcing fiber base material 104 is preferably in the range of 40 g/m 2 or more and 250 g/m 2 or less. When the basis weight is 40 g/m 2 or more, the number of reinforcing fibers in the molded product can be increased, and thus desired mechanical properties can be obtained. Further, when the basis weight is 250 g/m 2 or less, it becomes easy to sufficiently impregnate the inside of the reinforcing fiber base material 104 with the resin.
[0139]
　Step b: In
　Step b, as shown in FIGS. 5B and 5C, the resin-attached fiber base material 104A is subjected to heat treatment to incompletely melt the fine powder 105 of the raw material resin composition, By solidifying, the prepreg 106 having the partially fused structure 105A of the raw material resin composition is formed. Here, “incompletely melting” does not mean that all of the fine powder 105 of the raw material resin composition is made into droplets and flows, but a part of the fine powder 105 is completely made into droplets, Most of the fine powder 105 means that only the surface is formed into droplets, and the central portion is melted only to a state where it remains solid. Further, the “partial fusion bonding structure 105A” has a mesh-like structure in which the fine powder 105 is partially melted by the heat treatment in the vicinity of the surface layer portion of the reinforcing fiber base material 104, and the adjacent fine powder 105 is fused and melted. It is solidified in cooperation with. The partial fusion bonding structure 105A enhances the adhesion to the reinforcing fiber base material 104, prevents the fine powder 105 from falling off, and secures a certain air permeability in the thickness direction of the reinforcing fiber base material 104. Therefore, in the heating/pressurizing process of the step B described later, an escape path for air in the reinforcing fiber base material 104 is secured, and generation of voids can be avoided. The partially fused structure 105A is preferably formed uniformly on the entire surface of the prepreg 106, but may be microscopically unevenly distributed.
[0140]
　Although FIG. 5C shows a state in which the partial fusion bonding structure 105A is formed on one surface of the prepreg 106, even if the partial fusion bonding structure 105A is formed on both surfaces of the prepreg 106. Good.
[0141]
(Heat Treatment Conditions) The
　heat treatment depends on the melting point or Tg of the raw material resin composition used, because the fine powder 105 of the raw material resin composition is incompletely melted to enable formation of the partially fused structure 105A. It is preferable to carry out at a temperature in the range of about 100 to 400°C. Further, when the raw material resin composition is a crystalline resin, it is more preferable to perform the treatment at a temperature equal to or lower than the melting point. If the heat treatment temperature exceeds approximately 400° C., the thermal melting of the fine powder 105 proceeds too much, the partially fused structure 105A is not formed, and the air permeability may be impaired. Further, if the heat treatment temperature is lower than about 100° C., the partial fusion structure 105A is not formed, and the heat fusion to the reinforcing fiber base material 104 becomes insufficient, and the powder of the fine powder 105 is handled during the handling work of the prepreg 106. Drops and dropouts may occur.
[0142]
　The heat treatment time is not particularly limited as long as the fine powder 105 of the raw material resin composition attached to the reinforcing fiber base material 104 can be fixed to the reinforcing fiber base material 104, but for example, 1 to 5 minutes is preferable. That is, by performing heat treatment in a much shorter time than during molding, the resin can be fixed to the reinforcing fiber base material 104 in the state of the partially fused structure 105A, and powder falling can be prevented.
[0143]
　At the stage of the prepreg 106 after the heat treatment, the raw material resin composition (the one having the partially fused structure 105A and the fine powder 105 as it is) is concentrated near the surface of the reinforcing fiber base material 104, and is heated by the step B described later. It does not reach the inside of the reinforcing fiber base material 104 like the pressed body. The heat treatment may be performed with the resin-attached fiber base material 104A and the metal member 11 in contact with each other.
[0144]
(Method A2) The
　method A2 is a method in which the steps a and b in the method A1 are collectively performed. That is, although not shown, the fine powder 105 of the raw material resin composition which is solid at room temperature is adhered to at least one surface of the sheet-shaped reinforcing fiber base material 104 heated to a predetermined temperature by the powder coating method to form the fine powder 105. Is melted incompletely and then solidified to form the prepreg 106 in which the partially fused structure 105A is formed. In the method A1, the powder-coated fine powder 105 was fixed to the reinforcing fiber base material 104 by heat treatment, but in the method A2, the fine powder 105 was powder-coated on the preheated reinforcing fiber base material 104. The difference is that the partial fusion-bonding structure 105A is formed by fusion-bonding the reinforcing fiber base material 104 at the same time as coating.
[0145]
　Since various processing conditions in the method A2 are the same as those in the method A1, the detailed description is omitted.
[0146]
(Thickness of prepreg) The
　prepreg 106 obtained in the step A preferably has a thickness of 40 μm or more and 200 μm or less, and more preferably 50 μm or more and 150 μm or less. By setting the thickness of the prepreg 106 to 40 μm or more, it is possible to improve the handling property and avoid impregnation failure due to insufficient resin. By setting the thickness of the prepreg 106 to 200 μm or less, the reinforcing fiber base material 104 can be sufficiently impregnated with the molten resin in the step B described later, and the mechanical strength can be improved.
[0147]
(Air Permeability of Prepreg) The air permeability of the
　prepreg 106 in the thickness direction when the thickness is 40 to 200 μm is preferably in the range of 500 cc/cm 2 /sec or more and 1000 cc/cm 2 /sec or less, and 700 cc/cm. More preferably, it is in the range of 2 /sec or more and 900 cc/cm 2 /sec or less. By setting the air permeability to 500 cc/cm 2 /sec or more, in the heating and pressurizing process of the step B described later, the escape paths of air in the prepreg 106 increase, and voids are less likely to occur. That is, in bonding with the dense metal member 11, it is important that the air existing in the prepreg 106 escapes in the thickness direction to the side opposite to the bonding surface, so that the air permeability is 500 cc/cm 2 /sec. By controlling as described above, degassing from the prepreg 106 can be facilitated. On the other hand, when the air permeability is 1000 cc/cm 2 /sec or less, the fine powder 105 of the raw material resin composition is less likely to fall off, and the handling property can be improved.
[0148]
　The surface roughness of the prepreg 106 is preferably in the range of 0.010 mm or more and 0.100 mm or less as the surface roughness, and in the range of 0.015 mm or more and 0.075 mm or less. More preferably. When Ra is in the above range, the air in the prepreg 106 can escape from the side surface in the heating and pressurizing process of the step B described later. Therefore, even when the prepreg 106 is sandwiched between the dense metal members 11, the prepreg 106 and the metal member 11 are firmly bonded, and the metal-FRP composite 1 having excellent mechanical strength can be obtained. When Ra is less than 0.010 mm, the prepregs 106 or the prepregs 106 and other prepregs are easily fused by the heating and pressurizing treatment, which causes the escape of air and causes voids. If Ra exceeds 0.100 mm, voids may be left out, which is not preferable.
[0149]
(Resin Concentration Gradient in Prepreg) In
　the prepreg 106 in which the partially fused structure 105A of the raw material resin composition is formed, with respect to the thickness of the reinforced fiber base material 104 with respect to the end face of the original reinforced fiber base material 104, Then, 10% by mass or more of the raw material resin composition is preferably adhered within a range of 0 to 50% in the thickness direction, and more preferably 10% by mass or more and 40% by mass or less is adhered. By providing a gradient in the adhesion concentration of the raw material resin composition in this way, in the next step B, when the surface of the prepreg 106 on which the partially fused structure 105A is formed is brought into contact with the metal member 11 for heating and pressurization. The molten resin can be sufficiently spread on the boundary between the prepreg 106 and the metal member 11. That is, by utilizing the property of the metal member 11 having a high thermal conductivity and being easily heated, and contacting the surface thereof with a high-concentration solid raw material resin composition containing the partially fused structure 105A, the resin is melted. And a large amount of molten resin can be supplied to the adhesion boundary. Therefore, even with respect to the raw material resin composition having a relatively large melt viscosity, the resin layer 101 can be formed in addition to being able to penetrate the entire prepreg 106 in a short time. In addition, by forming the partial fusion bonding structure 105A to increase the resin concentration on the surface side to be bonded to the metal member 11, the air permeability is controlled within the above range, so that the prepreg 106 exists in the process B. Since air can escape to the side opposite to the adhesive surface in the thickness direction of the prepreg 106, the occurrence of voids is avoided.
[0150]
In
　step B, as shown in FIGS. 6A and 6B, the surface of the prepreg 106 on which the partially fused structure 105A is formed is brought into contact with the surface of the metal member 11. The metal member 11 and the prepreg 106 are thermocompression-bonded by performing the heating and pressurizing treatment in the state. By the heat and pressure treatment, the raw material resin composition attached to the prepreg 106 is completely melted and wetted (leaked) on the surface of the metal member 11, and at the same time, the reinforcing fiber base material 104 is impregnated. By solidifying or curing the impregnated raw material resin composition, the matrix resin 102 is formed, the FRP layer 12 as the fiber reinforced resin material is formed, and the FRP layer 12 is bonded to the metal member 11. .. In step B, the partially fused structure 105A of the raw material resin composition in the prepreg 106 comes into contact with the metal member 11 in the heat and pressure treatment and spreads in a thin film, so that the reinforcing fiber material 103 hardly exists. (Only 5% by mass or less is present), so that the resin layer 101 can be formed almost entirely of resin. In this way, the metal-FRP composite body 1 in which the FRP layer 12 and the metal member 11 are firmly joined is formed.
[0151]
　In the thermocompression bonding step of step B, the raw material resin composition is completely melted into a liquid by heating, and permeates into the prepreg 106 by pressurization. In the prepreg 106 controlled to have a predetermined air permeability, an escape path for air is secured, so the molten resin permeates while expelling the air, and impregnation is completed in a short time even at a relatively low pressure, resulting in void formation. Occurrence can be avoided.
[0152]
　The thermocompression bonding temperature depends on the melting point or Tg of the raw material resin composition used, because the fine powder 105 of the raw material resin composition and the partially fused structure 105A are completely melted and impregnated into the entire reinforcing fiber base material 104. It can be set appropriately. The thermocompression bonding conditions such as temperature will be described later.
[0153]
　In the step B, the metal member 11 and the prepreg 106 may be formed into an arbitrary three-dimensional shape at the same time as the thermocompression bonding. In this case, it is preferable that the pressure when the metal member 11 and the prepreg 106 are pressure-bonded to each other is formed on the basis of the pressure required for press-forming the metal member 11. In the manufacturing method 1, it is preferable to form the composite having a three-dimensional shape by collectively molding the metal member 11 and the prepreg 106. However, in the step B, the metal member 11 previously formed into an arbitrary three-dimensional shape is formed. It is also suitable for a method of crimping the prepreg 106.
[0154]
　The composite collective molding of the metal member 11 and the FRP layer 12 by the pressure molding machine is preferably performed by hot pressing, but the material preheated to a predetermined temperature is quickly installed in the low temperature pressure molding machine and processed. You may. The metal member 11 and the prepreg 106 may be temporarily fixed in advance when the members are installed in the heat molding machine. The temporary fixing condition is not particularly limited as long as the partially fused structure 105A of the prepreg 106 is maintained and the air permeability is secured.
[0155]
　As shown in FIG. 6B, the obtained metal-FRP composite 1 is provided with the metal member 11 and the FRP layer 12 as the fiber reinforced resin material. Further, as shown in FIGS. 6B and 7, the FRP layer 12 includes a matrix resin 102 and a reinforcing fiber material 103 which is a composite reinforcing fiber contained in the matrix resin 102. doing. Further, the FRP layer 12 has a resin layer 101, which is a part thereof, between the surface of the metal member 11 and the reinforcing fiber material 103 closest to the surface. In the resin layer 101, the fine powder 105 of the raw material resin composition adhered to the surface of the prepreg 106 on the side where the partially fused structure 105A is formed is brought into contact with the metal member 11 in the thermocompression bonding in the step B to form a thin film. It is formed by being solidified or hardened. The resin layer 101 is a layer that is almost entirely made of resin, in which the reinforcing fiber material 103 hardly exists. In other words, the resin layer 101 does not contain fibers in an amount sufficient to reinforce the resin, although it is undeniable that fibers detached from the reinforcing fiber material 103 may be mixed.
[0156]
　In addition, in the said manufacturing method 1, you may add an oily surface adhesive to a 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 raw material resin composition is finely cut and crushed, mixed with the oil surface adhesive, and the same process as in the above-described production method 1 is 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 raw material resin composition, and the organic solvent is volatilized and dried. You may perform the process similar to the manufacturing method 1 mentioned above. Further, the steps similar to those in the above-mentioned production method 1 may be carried out using a mixture obtained by physically cutting, pulverizing and mixing the oil surface adhesive and the raw material resin composition with a stirrer.
[0157]
[Manufacturing Method 2]
　Next, the manufacturing method 2 will be described with reference to FIG. In the manufacturing method 2, after the coating film 20 (which becomes the resin layer 101) made of the raw material resin composition is formed on the surface of the metal member 11, the FRP that becomes the FRP layer 12 or FRP molding processed into a desired shape is formed. The metal-FRP composite 1 is manufactured by laminating the prepregs 21 and thermocompression bonding. The FRP molding prepreg 21 is a precursor of FRP. In the manufacturing method 2, the coating film 20 may be formed on the FRP side that becomes the FRP layer 12 or the FRP molding prepreg 21 side instead of the metal member 11 side. However, hereinafter, the coating film 20 on the metal member 11 side. An example will be described where the above is formed.
[0158]
　First, as shown in FIG. 8A, a powdery or liquid raw material resin composition is applied to at least one surface of the metal member 11 to form a coating film 20. The above-mentioned oil surface adhesive may be added to the raw material resin composition. The addition method may be the same as the method described in the manufacturing method 1.
[0159]
　Next, as shown in FIG. 8( b ), on the side on which the coating film 20 is formed, the FRP molding prepreg 21 that becomes the FRP layer 12 is placed in an overlapping manner, and the metal member 11, the coating film 20, and the FRP molding prepreg 21 are arranged. The prepreg 21 and the prepreg 21 form a laminated body laminated in this order. Note that, in FIG. 8B, FRP may be laminated instead of the FRP molding prepreg 21. In this case, it is preferable that the bonding surface of the FRP is roughened by, for example, blast treatment, activated by plasma treatment, corona treatment, or the like.
[0160]
　Next, by heating and pressurizing the formed laminated body, the metal-FRP composite 1 is obtained as shown in FIG. 8(c).
[0161]
　In the manufacturing method 2, as a method of forming the coating film 20 to be the resin layer 101, a method of powder coating the powder of the raw material resin composition on the surface of the metal member 11 is preferable. The resin layer 101 formed by powder coating is easily melted because the raw material resin composition is fine particles, and voids are easily removed because the coating film 20 has appropriate voids. Therefore, when the FRP or the prepreg 21 for FRP molding is heated and pressure-bonded, the raw material resin composition wets the surface of the metal member 11 well, so that a deaeration step such as varnish coating is not necessary, and a void as seen in the film is obtained. Defects due to lack of wettability such as occurrence of are unlikely to occur.
[0162]
　In the manufacturing method 2, the coating film 20 is formed on both surfaces of the metal member 11 in FIG. 8A, and the FRP molding prepreg 21 (or FRP) is formed on each of the coating films 20 in FIG. 8B. May be laminated. Alternatively, two or more metal members 11 may be used and the fiber-reinforced resin material including the FRP layer 12 may be laminated so as to be sandwiched. Further, a prepreg (or FRP) for FRP molding which becomes the FRP layer 13 may be laminated.
[0163]
[Manufacturing Method 3]
　Next, the manufacturing method 3 will be described with reference to FIG. In the production method 3, the metal-FRP composite 1 is produced by laminating the film-formed raw material resin composition and the FRP or FRP molding prepreg 21 which becomes the FRP layer 12 on the metal member 11 and thermocompression bonding.
[0164]
　In this manufacturing method 3, for example, as shown in FIG. 9A, a resin sheet 20A formed by film-forming the raw material resin composition on at least one surface of the metal member 11 and a prepreg for FRP molding which becomes the FRP layer 12. 21 are arranged in an overlapping manner to form a laminated body in which the metal member 11, the resin sheet 20A and the FRP molding prepreg 21 are laminated in this order. The above-mentioned oil surface adhesive agent may be added to the resin sheet 20A. Note that, in FIG. 9A, FRP can 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.
[0165]
　Next, by heating and pressurizing this laminated body, the metal-FRP composite 1 is obtained as shown in FIG. 9(b).
[0166]
　In the manufacturing method 3, in FIG. 9A, the resin sheet 20A and the FRP molding prepreg 21 (or FRP) may be laminated on both surfaces of the metal member 11, respectively. Alternatively, two or more metal members 11 may be used and the fiber-reinforced resin material including the FRP layer 12 may be laminated so as to be sandwiched. Furthermore, you may laminate|stack the prepreg (or FRP) for FRP molding used as the FRP layer 13.
[0167]
(Heat-bonding conditions) In the
　above-described manufacturing methods 1 to 3, the heat-bonding conditions for compounding the metal member 11, the resin sheet 20A, and the FRP molding prepreg 21 (or FRP) that becomes the FRP layer 12 are as follows. , As follows.
[0168]
　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, the resin may be decomposed because excessive heat is applied, and if the temperature is lower than the lower limit, the melt viscosity of the resin is high. Impregnation into the material becomes poor.
[0169]
　The pressure at the time of thermocompression bonding is, for example, preferably 3 MPa or more, and 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 less than the lower limit, impregnation into the reinforcing fiber base material is deteriorated.
[0170]
　As for the thermocompression bonding time, if the thermocompression bonding time is at least 3 minutes or more, the thermocompression bonding can be sufficiently performed, and it is preferably in the range of 5 minutes or more and 20 minutes or less. However, in the production method 1, the impregnation time can be shortened as compared with, for example, the film stack method of the production method 3 by controlling the partial fusion bonding structure 105A, the resin concentration gradient, and the air permeability. Thermocompression bonding is possible, and the thermocompression bonding time is preferably within the range of 1 to 10 minutes.
[0171]
　In the thermocompression bonding step, a composite batch molding of the metal member 11, the resin 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 thus the above-mentioned superaddition rule is expressed. can do.
[0172]
　Here, when the metal member 11 and the FRP molding prepreg 21 (or FRP) to be the FRP layer 12 are heated and pressure-composited to form a composite, the temperature of the metal member 11 side is set to the temperature of the FRP molding prepreg 21 (or FRP). It is preferable to set it higher than. Specifically, for example, the metal member 11 may be preheated and installed in a pressure molding machine together with the FRP molding prepreg 21 (or FRP) that has not been preheated for processing. In this way, by setting the temperature of the metal member 11 side higher than the temperature of the FRP molding prepreg 21 (or FRP), the matrix resin 102 from the FRP layer 12 can be more surely leached. At the same time, the metal member 11 and the FRP layer 12 can be bonded more firmly.
[0173]
(Additional heating step) In
　Manufacturing Method 1 to Manufacturing Method 3, a phenoxy resin (A) and a crosslinkable cured resin are used as a resin composition for forming the resin layer 101 and a raw material resin for forming the matrix resin 102. When using the crosslinkable resin composition containing (B) and the crosslinking agent (C), an additional heating step may be further included.
[0174]
　When the crosslinkable resin composition is used, the FRP layer 12 including the first cured resin layer 101 and the matrix resin 102 which has been solidified but has not been crosslinked (cured) in the thermocompression bonding step. Can be formed. That is, the metal-FRP composite in which the metal member 11 and the FRP layer 12 including the resin layer 101 made of the cured product (solidified product) in the first cured state are laminated and integrated through the thermocompression bonding process. The intermediate body (preform) of 1 can be produced. Then, after the thermocompression bonding step, an additional heating step is performed on this intermediate body to perform post cure on at least the resin layer 101 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).
[0175]
　In addition to the FRP layer 12, the above-mentioned intermediate may include another FRP layer 13 laminated on the FRP layer 12. In this case, the matrix resin of the FRP layer 13 may be in the first cured state formed by using the crosslinkable resin composition as a raw material. In this case, the matrix resin of the FRP layer 13 can also be cross-linked and cured by post cure to obtain a cross-linked cured product in the second cured state.
[0176]
　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. Instead of post cure, heat history in a post process such as painting may be used.
[0177]
　As described above, when the crosslinkable 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 body, that is, the resin changes from the cured product (solidified product) in the first cured state to the cured product (crosslinked cured product) in the second cured state. 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 to 220° C. or less, heat resistance can be significantly increased.
[0178]
(Pretreatment Step) When the
　metal-FRP composite 1 is manufactured, it is preferable to degrease the metal member 11 as a pretreatment step of compounding the metal member 11 and the FRP molding prepreg 21 (or FRP). It is more preferable to perform mold release treatment on the mold or remove adhered matter (dust removal) on the surface of the metal member 11. Except for steel plates with very high adhesion such as TFS (Tin Free Steel), metal members 11 such as steel plates to which rust-preventing oil or the like is normally attached must be degreased to restore the adhesion. It is difficult to obtain strength exceeding the additive rule. Therefore, by performing the above-mentioned pretreatment on the metal member 11, the metal-FRP composite 1 can easily 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, and the super-addition rule actually occurs? You can make a decision by checking whether or not it is correct. 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 raw material resin composition together with the degreasing treatment or in place of the degreasing treatment, and the oil surface adhesiveness may be added to the interface between the FRP layer 12 and the metal member 11. An adhesive may be applied.
[0179]
(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.
[0180]

　According to the above-described embodiment, the metal-FRP in which the metal member 11 and the fiber-reinforced resin material including the FRP layer 12 are firmly joined by the resin layer 101 forming a part of the FRP layer 12. A complex 1 is provided. The metal-FRP composite 1 is lightweight and excellent in workability and can be manufactured by a simple method. For example, even if the metal member 11 is a steel material subjected to anticorrosion treatment, the metal member 11 and the fiber-reinforced resin material including the FRP layer 12 have high adhesive strength without performing a special surface roughening treatment. have. Further, when the metal member 11 and the fiber-reinforced resin material including the FRP layer 12 are composited, the metal member 11 can be processed at the same time by hot pressing, so that the manufacturing cost can be reduced. Therefore, the metal-FRP composite 1 of the above-described embodiment is suitable as a lightweight and high-strength material not only as a casing for electric/electronic devices, but also as a structural member for applications such as automobile members and aircraft members. Can be used. Furthermore, since the metal-FRP composite 1 can solve all the above-mentioned six problems when the FRP is used for an automobile member, it can be used particularly preferably as an automobile member.
Example
[0181]
　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 measurement methods for various physical properties in this example are as follows.
[0182]
[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.
[0183]
[Melt Viscosity] Using a
　rheometer (manufactured by Anton Paar), a sample size of 4.3 cm 3 was sandwiched 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.
[0184]
[Resin ratio (RC:%)]
　It was calculated 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 using the following formula.
　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
[0185]
[Measurement of Thickness of
　Resin Layer ] The thickness of the resin layer was measured by the method mentioned above.
[0186]
[Measurement of Tensile Load and Tensile Elastic Modulus (Elastic Modulus)]
　Mechanical properties of a metal-FRP composite material (tensile 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 size of the test piece was 200 mm×25 mm.
[0187]
　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 resin layer 13 are laminated, and thermocompression bonding is performed under the conditions shown in the examples and comparative examples. Thus, a metal-FRP composite sample for tensile test was obtained. The arrow direction in FIG. 10 indicates the load application direction.
[0188]
[Confirmation of Presence or Absence of
　Super Addition Rule ] Whether or not the super addition 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. Next, 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 tensile force of the metal member 11 at the deformation amount D is determined. The load (load A2) is calculated. Then, the success or failure of the expressions (2-1) and (2-2) is determined, and if at least the expression (2-2) is satisfied, it is determined that the super-addition rule is expressed. In the present embodiment, the equation (2-1) is the "reference 1" and the equation (2-2) is the "reference 2". The degree of superadditional rule is calculated by C/(A2+B), but when the criterion 1 is also satisfied, the degree of superadditional rule corresponding to the criterion 1 is calculated as C/(A1+B). The degree of superaddition rule 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, than the total load of each alone. At this time, in the test piece, the size of the test piece of the metal member and the FRP alone may be matched with the size of the metal member and the FRP layer of the composite test piece. In the above-mentioned (pretreatment step) in determining the necessity of degreasing, the presence or absence of the super-addition rule in advance can also be confirmed by this method.
[0189]
　If a single material for the metal member 11 and the FRP layer 12 is 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 are removed, respectively, and then pulled. By performing the test, the individual tensile loads may be measured.
[0190]
　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 generally specified in 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, the thickness of the metal member 11 and the FRP layer 12 is measured 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. .. Then, the above-mentioned tensile test is performed on the first test piece to measure the maximum load (load C) of the metal-FRP composite. That is, the first test piece is used as the metal-FRP composite 1.
[0191]
　On the other hand, the FRP layer 12 is 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 is 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 even if the resin layer 101 remains on the metal member 11 to some extent. This is because the maximum load of the resin layer 101 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.
[0192]
　On the other hand, the metal member 11 is 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 is 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. Next, the maximum load (load B) of the FRP layer 12 is measured by performing the above-described tensile test on the third test piece. Then, based on each measured value and the equations (2-1) and (2-2) (preferably equation (2-2)), it may be determined whether or not the super-addition rule is satisfied. The tensile load of the metal member 11 and the FRP layer 12 in the composite material when the metal member 11 is surface-treated can be measured by the same measurement method as above.
[0193]
[Bending Test]
　The mechanical properties (presence or absence of peeling between the metal member 11 and the FRP layer 12 due to bending) of the metal-FRP composite material obtained according to the bending test method of fiber reinforced plastics according to JIS K 7074:1988 were measured. As shown in FIG. 11, FRP laminated bodies (those in which the FRP layer 12 and the FRP layer 13 are laminated) are arranged on both sides of the metal member 11, respectively, and thermocompression bonding is performed under the conditions shown in the respective examples and comparative examples. To obtain a metal-FRP composite sample for bending test. The white arrow in FIG. 11 indicates the direction of load application. When the mechanical strength was measured, when the sample was broken, the metal plate peeled from the FRP laminate was evaluated as peeling: x (with peeling), and when not peeled, peeling: ○ (no peeling) was evaluated.
[0194]
[Shear Test] The
　measurement was carried out with reference to the tensile shear adhesive strength test method of JIS K 6850:1999 adhesive. As shown in FIG. 12, two metal members 11 processed into a size of width 5 mm×length 60 mm are prepared, and portions of 10 mm from the end portions of each metal member 11 are separated into an FRP laminate (FRP layer 12). (/FRP layer 13/FRP layer 12 laminated in this order) was placed, and thermocompression bonding was performed under the conditions shown in each Example and Comparative Example to prepare a sample of the metal-FRP composite for shear test. That is, in the sample of the metal-FRP composite for shear test, the FRP laminate is sandwiched between the upper and lower ends of the two metal members 11 and heat-pressed under the conditions shown in each Example and Comparative Example. Made by. The two white arrows in FIG. 12 indicate the direction in which the tensile load is applied.
[0195]
[FRP prepreg]
Polyamide CFRP prepreg
　BHH-100GWODPT1/PA manufactured by Sakai Obex Co., Vf (fiber volume content): 47%
Polycarbonate CFRP prepreg
　Sakai Obex manufactured BHH-100GWODPT1/PC, Vf (fiber volume content): 47%
polypropylene CFRP prepreg
　Sakai Obex BHH-100GWODPT1/PP, Vf (fiber volume content): 47%
[0196]
[Phenoxy resin (A)]
　(A-1): Phenothote YP-50S (bisphenol A type manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., Mw=40,000, hydroxyl equivalent=284 g/eq), melt viscosity at 250° C.=200 Pa・S, Tg=83℃
[0197]
[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.)
[0198]
[Crosslinking Agent (C)]
　Ethylene glycol bisanhydrotrimellitate: TMEG
　(acid anhydride equivalent: 207, melting point: 160° C.)
[0199]
[Preparation Example 1] [Preparation of
phenoxy resin CFRP prepreg A] As the
　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 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 0.65 mm, an elastic modulus of 75 [GPa], a maximum load of 13500 [N], and a Vf (fiber volume content) of 60%. Resin CFRP prepreg A was prepared.
[0200]
[Preparation Example 2] [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 an average 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. Thereafter, 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 0.161 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.
[0201]
[Preparation Example 3] [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 prepared powder was pulverized and classified, and powder having an average particle diameter D50 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 applied to a plain-woven reinforcing fiber base material (cloth material: SA-3203, manufactured by Sakai Obex Co., Ltd., 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. Then, 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 17,000 [N], and a resin ratio (RC) of 48%. Resin CFRP prepreg A was prepared.
[0202]
　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 laminated body having a thickness of 2 mm, and at 170°C. After 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 dynamic viscoelasticity measuring device (DMA 7e manufactured by Perkin Elmer) was used to raise the temperature by 5° C./min. , And the maximum peak of tan δ obtained was measured as Tg.
[0203]
[Preparation Example 4] [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-woven reinforcing fiber base material (cloth material: SA-3203, manufactured by Sakai Obex Co., Ltd., 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.
[0204]
[Production Example 5] [Production of
polypropylene film] As a
polypropylene resin, pellets of Novatec PP EA9 manufactured by Nippon Polypro Co., Ltd. were pressed with a press machine heated to 200°C for 3 MPa for 3 minutes to form a polypropylene resin film having a thickness of 50 µm. It was created.
[0205]
[Production Example 6] [Production of
phenoxy resin CFRP prepreg C] As the
　phenoxy resin (A), A-1 was pressed at 3OMPa for 3 minutes with a press machine heated to 200°C to prepare a phenoxy resin sheet having a thickness of 200 µm. , A plain weave reinforced fiber substrate made of carbon fiber (cloth material: SA-3203, manufactured by Sakai Obex Co., Ltd.) are alternately laminated, and the laminated body is pressed at 3 MPa for 3 minutes with a press machine heated to 250° C. A phenoxy resin CFRP prepreg C having a thickness of 0.6 mm, an elastic modulus of 75 [GPa], a tensile load of 12000 [N], and a Vf (fiber volume content) of 60% was prepared.
[0206]
[Production Example 7] [Production of
phenoxy resin CFRP prepreg D] 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 ( 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 was heat-melted at 170° C. for 1 minute in an oven to heat-bond the resin, and a phenoxy resin having a thickness of 1.0 mm, an elastic modulus of 75 [GPa], a maximum load of 19000 [N], and a Vf (fiber volume content) of 60%. Resin CFRP prepreg D was prepared.
[0207]
[Preparation Example 8] [Preparation of
phenoxy resin CFRP prepreg E] 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 ( 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 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.
[0208]
[Preparation Example 9] [Preparation of
phenoxy resin CFRP prepreg F] As the
　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 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. On the surface of this, a mixture of a main agent of Alpha Industrial Co., Ltd. Alpha Tech 370 and a curing agent at a weight ratio of 100:30 was applied in an amount of 3 g/m 2 , and then heated and melted in an oven at 170° C. for 1 minute. Then, the resin was heat-sealed to prepare a phenoxy resin CFRP prepreg F having a thickness of 0.2 mm, an elastic modulus of 68 [GPa], a maximum load of 3000 [N], and a Vf (fiber volume content) of 54%.
[0209]
[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):
　Tin-free steel plate manufactured by Nippon Steel & Sumikin Co., Ltd., thickness 0.12 mm
Metal member (M-3):
　Niraco pure aluminum plate, thickness 0.1 mm
Metal member (M-4):　
　Niraco pure titanium plate, thickness 0.1 mm
Metal member (M-5):
　Nippon Metal Co., Ltd. AZ31B alloy plate, thickness 0.1 mm
metal member (M-6):
　commercially available A5052 alloy plate, thickness 0.6 mm
metal member (M-7):
　Nippon Steel & Sumikin Co., Ltd. hot dip galvanized high strength steel plate, thickness 0. 4 mm
[0210]
[Example 1]
　M-1 was used as the metal member 11 and the phenoxy resin CFRP prepreg A of Preparation Example 1 was used as the FRP layer 12, and the structure shown in FIGS. A sample of the metal-CFRP composite for the test was produced by pressing the sample at 3 MPa for 3 minutes with a press machine heated to 250°C. The thickness of the resin layer 101 was about 10 μm. After cooling, the obtained sample was subjected to a tensile test, a bending test and a shearing test. The results are shown in Table 1.
[0211]
Example 2 A
　metal-CFRP composite sample was prepared in the same manner as in Example 1 except that M-2 was used as the metal member 11. The thickness of the resin layer 101 was about 10 μm. After cooling, the obtained sample was subjected to a tensile test, a bending test and a shearing test. The results are shown in Table 1.
[0212]
Example 3 A
　metal-CFRP composite sample was prepared in the same manner as in Example 1 except that M-3 which had been sufficiently degreased with acetone was used as the metal member 11. The thickness of the resin layer 101 was about 10 μm. After cooling, the obtained sample was subjected to a tensile test, a bending test and a shearing test. The results are shown in Table 1.
[0213]
Example 4 A
　metal-CFRP composite sample was prepared in the same manner as in Example 1 except that M-4 that had been sufficiently degreased with acetone was used as the metal member 11. The thickness of the resin layer 101 was about 10 μm. After cooling, the obtained sample was subjected to a tensile test, a bending test and a shearing test. The results are shown in Table 1.
[0214]
Example 5 A
　metal-CFRP composite sample was prepared in the same manner as in Example 1 except that M-5 which had been sufficiently degreased with acetone was used as the metal member 11. The thickness of the resin layer 101 was about 10 μm. After cooling, the obtained sample was subjected to a tensile test, a bending test and a shearing test. The results are shown in Table 1.
[0215]
Example 6 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 2 was used as the FRP layer 12. The thickness of the resin layer 101 was about 10 μm. After cooling, the obtained sample was subjected to a tensile test, a bending test and a shearing test. The results are shown in Table 1.
[0216]
Example 7 A
　metal-CFRP composite sample was prepared in the same manner as in Example 1 except that a polyamide CFRP prepreg of FRP prepreg was used as the FRP layer 12. The thickness of the resin layer 101 was about 10 μm. After cooling, the obtained sample was subjected to a tensile test, a bending test and a shearing test. The results are shown in Table 1.
[0217]
Example 8 A
　metal-CFRP composite sample was prepared in the same manner as in Example 1 except that the FRP prepreg polycarbonate CFRP prepreg was used as the FRP layer 12. The thickness of the resin layer 101 was about 10 μm. After cooling, the obtained sample was subjected to a tensile test, a bending test and a shearing test. The results are shown in Table 1.
[0218]
[Example 9] A
　metal-CFRP composite sample was produced 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 resin layer 101 was about 10 μm. After cooling, the obtained sample was subjected to a tensile test, a bending test and a shearing test. The results are shown in Table 1.
[0219]
Example 10
　A metal-CFRP composite sample was prepared in the same manner as in Example 1 except that the crosslinked phenoxy resin CFRP prepreg A of Preparation Example 3 was used as the FRP layer 12. The thickness of the resin layer 101 was about 10 μm. After cooling, the obtained sample was subjected to a tensile test, a bending test and a shearing test. The results are shown in Table 1.
[0220]
[Example 11] A
　metal-CFRP composite sample was prepared in the same manner as in Example 1 except that the crosslinked phenoxy resin CFRP prepreg B of Preparation Example 4 was used as the FRP layer 12. The thickness of the resin layer 101 was about 10 μm. After cooling, the obtained sample was subjected to a tensile test, a bending test and a shearing test. The results are shown in Table 1.
[0221]
[Example 12] In the same
　manner as in Example 1 except that M-7 sufficiently degreased with acetone was used as the metal member 11 and the phenoxy resin CFRP prepreg D of Preparation Example 7 was used as the FRP layer 12, A sample of metal-CFRP composite was made. The thickness of the resin layer 101 was about 10 μm. After cooling, the obtained sample was subjected to a tensile test, a bending test and a shearing test. The results are shown in Table 1.
[0222]
[Example 13] In the same
　manner as in Example 1 except that M-7 sufficiently degreased with acetone was used as the metal member 11 and the phenoxy resin CFRP prepreg E of Preparation Example 8 was used as the FRP layer 12, A sample of metal-CFRP composite was prepared. The thickness of the resin layer 101 was about 10 μm. After cooling, the obtained sample was subjected to a tensile test, a bending test and a shearing test. The results are shown in Table 1.
[0223]
[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. M-7 applied in an amount of 3 to 3 g/m 2 of an oil surface adhesive, Alpha Tech 370, manufactured by Alpha Industry Co., was applied on the surface of the phenoxy resin of Preparation Example 8 as an FRP layer 12. A metal-CFRP composite sample was prepared in the same manner as in Example 1 except that CFRP prepreg E was used. The thickness of the resin layer 101 was about 20 μm. After cooling, the obtained sample was subjected to a tensile test, a bending test and a shearing test. The results are shown in Table 1.
[0224]
[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 1 except that the amount of M-7 applied was used and the FRP layer 12 was the phenoxy resin CFRP prepreg F of Preparation Example 9. The thickness of the resin layer 101 was about 20 μm. After cooling, the obtained sample was subjected to a tensile test, a bending test and a shearing test. The results are shown in Table 1.
[0225]
[Comparative Example 1]
　Toraycap prepreg F6343B-05P (impregnated with a thermosetting epoxy resin in a plain weave of PAN-based carbon fiber having an elastic modulus of 230 GPa impregnated with a thermosetting epoxy resin) manufactured by Toray Industries, Inc. was heated and pressed in an autoclave to prepare CFRP. 10, 11 and 12 were used as the FRP layer 12, M-1 was used as the metal member 11, and a two-liquid mixed epoxy resin adhesive Araldite Standard manufactured by Nichiban Co., Ltd. was used as the resin layer 101. Samples of the metal-CFRP composite for the tensile test, the bending test, and the shear test of the structure shown in (1) were prepared. The thickness of the resin layer 101 was about 15 μm. After cooling, the obtained sample was subjected to a tensile test, a bending test and a shearing test. The results are shown in Table 2.
[0226]
Comparative Example 2 Using
　M-1 as the metal member 11, the phenoxy resin CFRP prepreg C of Preparation Example 6 as the FRP layer 12, and the polypropylene film prepared in Preparation Example 5 as the resin layer 101, FIG. Samples of the metal-CFRP composites for the tensile test, bending test, and shear test of the structures shown in Nos. 11 and 12 were manufactured by pressing at 3 MPa for 3 minutes with a press machine heated to 200°C. That is, in Comparative Example 2, the resin layer 101 was not formed by leaching the resin from the FRP layer 12, but was formed by a polypropylene film prepared separately. The thickness of the resin layer 101 was about 40 μm. After cooling, the obtained sample was subjected to a tensile test, a bending test and a shearing test. The results are shown in Table 2.
[0227]
[Comparative Example 3]
　M-1 was used as the metal member 11 and the phenoxy resin CFRP prepreg A of Preparation Example 1 was used as the FRP layer 12, and the structure shown in FIGS. A metal-CFRP composite sample for a test was produced by pressing it at 3 MPa for 3 minutes with a press machine heated to 150°C. Almost no resin layer 101 could be confirmed. After cooling, the obtained sample was subjected to a tensile test, a bending test and a shearing test. The results are shown in Table 2.
[0228]
[Comparative Example 4]
After sufficiently degreasing the metal member 11 with acetone, in order to quantitatively attach the oil component to the surface, a 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 amount of M-7 applied was used. The thickness of the resin layer 101 was about 10 μm. After cooling, the obtained sample was subjected to a tensile test, a bending test and a shearing test. The results are shown in Table 1.
[0229]
[table 1]

[0230]
[Table 2]

[0231]
　As can be seen from Table 1 and Table 2, the resin layer 101 is provided by the same kind of resin as the matrix resin 102 of the thermoplastic resin of the FRP layer 12, and an oil film countermeasure (degreasing or treatment using an oil surface adhesive) is performed. In Examples 1 to 15, Comparative Example 1 in which the matrix resin 102 and the resin layer 101 are thermosetting resins, Comparative Example 2 in which the matrix resin 102 and the resin layer 101 are not the same kind of resin, and the resin layer 101 can hardly be confirmed. Compared with Comparative Example 3 and Comparative Example 4 in which the oil component adheres to the surface of the metal member 11 and there is no countermeasure against the oil film, metal peeling does not occur, and the metal member 11 and the FRP layer 12 are well adhered and integrated. And has excellent workability and mechanical properties. 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. The elastic modulus E2 of the equation (1) was calculated based on the additive rule with the elastic modulus of the resin layer being 2 GPa. However, in Comparative Examples 1 to 3, the elastic modulus of the resin layer was 0.
[0232]
　The preferred embodiments of the present invention have been described in detail above 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
[0233]
　　　DESCRIPTION OF SYMBOLS 1 Metal-FRP composite
　　11 Metal member
　　12, 13 FRP layer
　　20 Coating film
　　20A Resin sheet
　　21 FRP molding prepreg
　101 Resin layer
　102 Matrix resin
　103 Reinforcing fiber material
　104 Reinforcing fiber base material
　104A Resin adhesion fiber base material
　105 Fine powder
　105A Partial fusion structure
　106 prepreg
The scope of the claims
[Claim 1]
　What is claimed is: 1. A method for producing a metal-fiber reinforced resin material composite, comprising: a metal member; and a fiber reinforced resin material laminated on at least one surface of the metal member, comprising
　a reinforced fiber base material made of a reinforced fiber material. A 　resin of the same type as the matrix resin,
　which is impregnated in the reinforcing fiber base material and
is interposed between the first cured state matrix resin containing a thermoplastic resin and the metal member and the reinforcing fiber material. from it, the resin layer of the first cured state formed by the matrix resin impregnated into the reinforcing fiber base is oozed on the surface of the metal member
to produce the fiber-reinforced resin material having ,
　The glass transition temperature of the resin forming the matrix resin and the resin layer before and after the heating to change the resin forming the matrix resin and the resin layer from the first cured state to the second cured state is varied,
　the shear strength of the metallic member after heating and the fiber-reinforced resin material to the 0.8MPa or more, the metal - method for producing a fiber reinforced resin material composite.
[Claim 2]
　The matrix resin in the first cured state, as the thermoplastic resin, is a phenoxy resin (A), a polyolefin and an acid modified product thereof, polycarbonate, polyamide, polyester, polystyrene, vinyl chloride, acryl, polyether ether ketone, and polyphenylene. The method for producing a metal-fiber reinforced resin material composite according to claim 1, containing at least one selected from the group consisting of sulfide.
[Claim 3]
　The method for producing a metal-fiber reinforced resin material composite according to claim 2, wherein the matrix resin in the first cured state contains 50 parts by mass or more of the phenoxy resin (A) with respect to 100 parts by mass of the resin component.
[Claim 4]
　A crosslinkable resin in which the first cured matrix resin further contains 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). A composition,
　wherein the first cured state is a solidified product of a resin that forms the matrix resin and the resin layer, and
　the second cured state is a resin that forms the matrix resin and the resin layer. The method for producing a metal-fiber reinforced resin material composite according to claim 3, which is a crosslinked cured product.
[Claim 5]
　5. The resin layer in the first cured state is a layer in which the content of fibers desorbed from the reinforcing fiber material is 5% by mass or less, and the thickness of the layer is 20 μm or less. 7. The method for producing a metal-fiber reinforced resin material composite according to any one of items.
[Claim 6]
　A metal-fiber reinforced resin material composite comprising a metal member and a fiber reinforced resin material laminated on at least one surface of the metal member and composited with the metal member,
　wherein the fiber reinforced resin material is ,
　and a matrix resin containing a thermoplastic resin,
　a reinforcing fiber material which is contained in the matrix resin,
　and interposed between the metallic member and the reinforcing fiber material, a resin layer made of the matrix resin of the same kind as the resin If,
have,
　shear strength between the fiber reinforced resin material and the metal member is not less than 0.8 MPa, the metal - fiber reinforced resin material composite.
[Claim 7]
　The metal-fiber reinforced resin material composite according to claim 6, wherein the maximum load of the metal-fiber reinforced resin material composite exhibits a superaddition rule.
[Claim 8]
　The matrix resin is selected from the group consisting of a phenoxy resin (A), a polyolefin and an acid modified product thereof, a polycarbonate, a polyamide, a polyester, a polystyrene, a vinyl chloride, an acryl, a polyether ether ketone, and a polyphenylene sulfide as the thermoplastic resin. The metal-fiber reinforced resin material composite according to claim 6 or 7, containing any one or more of the following.
[Claim 9]
　The metal-fiber reinforced resin material composite according to claim 8, wherein the matrix resin contains 50 parts by mass or more of the phenoxy resin (A) with respect to 100 parts by mass of the resin component.
[Claim 10]
　The metal-fiber reinforced resin material composite according to any one of claims 6 to 9, wherein the resin constituting the resin layer is a crosslinked cured product, and the crosslinked cured product has a glass transition temperature of 160°C or higher. body.
[Claim 11]
　11. The resin layer according to claim 6, wherein the content of fibers desorbed from the reinforcing fiber material is 5% by mass or less, and the thickness of the layer is 20 μm or less. Metal-fiber reinforced resin material composite.
[Claim 12]
　The total thickness T1 of the metal member and the elastic coefficient E1 of the metal member, and the total thickness T2 of the fiber reinforced resin material and the elastic coefficient E2 of the fiber reinforced resin material satisfy the relationship of the following formula (1). The metal-fiber reinforced resin material composite according to any one of claims 6 to 11.
　(T1×E1)/(T2×E2)>0.3 Formula (1)
[Claim 13]
　The metal-fiber reinforced resin material composite according to any one of claims 6 to 12, wherein the material of the metal member is a steel material, an iron-based alloy, titanium or aluminum.
[Claim 14]
　The metal-fiber reinforced resin material composite according to claim 13, wherein the steel material is a hot dip galvanized steel sheet, an electrogalvanized steel sheet, or an aluminum plated steel sheet.
[Claim 15]
　A metal-fiber reinforced resin material composite comprising a metal member and a fiber reinforced resin material laminated on at least one surface of the metal member and composited with the metal member,
　wherein the fiber reinforced resin material comprises: ,
　and a matrix resin containing a thermoplastic resin,
　a reinforcing fiber material which is contained in the matrix resin,
　and interposed between the metallic member and the reinforcing fiber material, a resin layer made of the matrix resin of the same kind as the resin If,
has,
　the matrix resin, 50 parts by mass or more of the phenoxy resin (a) with respect to 100 parts by mass of the resin component, the phenoxy resin (a) 85 parts by 5 parts by mass or more with respect to 100 parts by weight A metal-fiber reinforced resin material composite, which is a crosslinked cured product of a crosslinkable resin composition containing the crosslinkable curable resin (B) within the following range.
[Claim 16]
　The metal-fiber reinforced resin material composite according to claim 15, wherein the maximum load of the metal-fiber reinforced resin material composite exhibits a superaddition rule.
[Claim 17]
　The metal-fiber reinforced resin material composite according to claim 15 or 16, wherein the shear strength between the metal member and the fiber reinforced resin material is 0.8 MPa or more.
[Claim 18]
　By the heating, the glass transition temperature is changed before and after the matrix resin and the resin forming the resin layer are changed from the solidified product in the first cured state to the crosslinked cured product in the second cured state, The metal-fiber reinforced resin material composite according to claim 17, wherein the shear strength between the metal member and the fiber reinforced resin material after the heating is 0.8 MPa or more.
[Claim 19]
　19. The resin layer according to claim 15, wherein the content of the fibers detached from the reinforcing fiber material is 5% by mass or less, and the thickness of the layer is 20 μm or less. Metal-fiber reinforced resin material composite.
[Claim 20]
　The total thickness T1 of the metal member and the elastic coefficient E1 of the metal member, and the total thickness T2 of the fiber reinforced resin material and the elastic coefficient E2 of the fiber reinforced resin material satisfy the relationship of the following expression (1). The metal-fiber reinforced resin material composite according to any one of claims 15 to 19.
　(T1×E1)/(T2×E2)>0.3 Formula (1)
[Claim 21]
　The metal-fiber reinforced resin material composite according to any one of claims 15 to 20, wherein the material of the metal member is a steel material, an iron-based alloy, titanium or aluminum.
[Claim 22]
　22. The metal-fiber reinforced resin material composite according to claim 21, wherein the steel material is a hot dip galvanized steel sheet, an electrogalvanized steel sheet, or an aluminum plated steel sheet.