WO2020202460A1

WO2020202460A1 - Metal/carbon-fiber-reinforced resin material composite and production method for metal/carbon-fiber-reinforced resin material composite

Info

Publication number: WO2020202460A1
Application number: PCT/JP2019/014606
Authority: WO
Inventors: 植田　浩平; 保明河村; 真純郡; 雅晴茨木
Original assignee: 日本製鉄株式会社
Priority date: 2019-04-02
Filing date: 2019-04-02
Publication date: 2020-10-08
Also published as: JPWO2020202460A1; JP7147964B2

Abstract

[Problem] To provide: a metal/carbon-fiber-reinforced resin material composite that suppresses corrosion of a metal member, and, in particular, corrosion from contact with other materials, and achieves excellent adhesion between the metal member and a carbon-fiber-reinforced resin material; and a production method for the metal/carbon-fiber-reinforced resin material composite. [Solution] This metal/carbon-fiber-reinforced resin material composite includes a metal member, a resin coating layer that is provided on at least a portion of the surface of the metal member, and a carbon-fiber-reinforced resin material that is provided on the resin coating layer and includes a matrix resin and a carbon fiber material that is in the matrix resin. The resin coating layer includes: inorganic salt particles that have a powder resistivity of greater than 7.0×10⁷ Ωcm at 23°C–27°C, are rust resistant, and comprise an inorganic salt of at least one element selected from among Cr, P, and V; and a binder resin. The inorganic salt particles are 5.0%–40.0% of the volume of the resin coating layer.

Description

Method for manufacturing metal-carbon fiber reinforced resin material composite and metal-carbon fiber reinforced resin material composite

The present invention relates to a method for producing a metal-carbon fiber reinforced resin material composite and a metal-carbon fiber reinforced resin material composite.

Fiber reinforced plastic (FRP: Fiber Reinforced Plastics), which is a composite of reinforced fibers (for example, glass fiber, carbon fiber, etc.) contained in a matrix resin, is lightweight and has excellent tensile strength and workability. Therefore, it is widely used from the consumer field to industrial applications. In the automobile industry as well, in order to meet the needs for weight reduction of vehicle bodies that lead to improvements in fuel efficiency and other performance, the application of FRP to automobile parts is being considered, focusing on the lightness, tensile strength, workability, etc. of FRP. ..

Among them, carbon fiber reinforced plastic (CFRP: Carbon Fiber Reinforced Plastics), which uses carbon fiber as a reinforcing fiber, is particularly lightweight due to the strength of the carbon fiber and is particularly excellent in tensile strength. It is a promising material for various uses.

On the other hand, CFRP matrix resin is generally a thermosetting resin such as an epoxy resin and therefore has brittleness, so that it may break brittlely when deformed. Further, since CFRP using a thermosetting resin as a matrix resin does not undergo plastic deformation, it cannot be bent once it is cured. Further, CFRP is generally expensive and causes an increase in cost of various members such as automobile members.

On the other hand, in order to solve these problems while maintaining the above-mentioned advantages of CFRP, recently, a metal member-CFRP composite material in which a metal member and CFRP are laminated and integrated (composite). Is being considered. Since the metal member has ductility, the brittleness is reduced by combining with such a metal member, and the composite material can be deformed and processed. Further, by combining the low-priced metal member and CFRP, the amount of CFRP used can be reduced, so that the cost of the automobile member can be reduced.

By the way, the carbon fiber in CFRP is a good conductor. Therefore, a phenomenon in which a metal member in contact with CFRP becomes electrically conductive and corrodes due to electrolytic corrosion (contact corrosion of dissimilar materials) may occur. Several proposals have been made to prevent such contact corrosion of dissimilar materials.

Patent Document 1 proposes a carbon fiber reinforced resin molded product in which a particulate or oily silicone compound is dispersed in a matrix resin of a carbon fiber reinforced resin molded product, which is used in contact with a metal part. ..

Patent Document 2 proposes a fiber-reinforced resin member in which a non-conductive sleeve and a non-conductive sheet such as a glass fiber reinforced resin are arranged between a metal fastening member and a CFRP laminated plate. Patent Document 3 proposes a fastening structure of a carbon fiber reinforced resin material in which a carbon fiber reinforced resin material and a contact portion of a metal collar are bonded to each other via an insulating adhesive.

Japanese Unexamined Patent Publication No. 2014-162848 International Publication No. 2016/021259 International Publication No. 2016/117062

However, the molded product described in Patent Document 1 is obtained by imparting water repellency to the surface of the carbon fiber reinforced resin molded product with silicone, and does not prevent conduction between the carbon fiber and the metal part. Therefore, it is difficult to sufficiently suppress contact corrosion of dissimilar materials. Further, the techniques according to Patent Documents 2 and 3 are only related to joining a metal member and a carbon fiber reinforced resin material, and cannot be simply applied to a metal-carbon fiber reinforced resin material composite. For example, the bonded portion between the metal of the metal-carbon fiber reinforced resin material composite and the carbon fiber reinforced resin material needs to be bonded by a relatively thin resin layer in order to maintain the integrity of the composite. Therefore, it is difficult to arrange a relatively thick glass fiber reinforced resin as described in Patent Document 2 in the composite. Further, it is not clear whether the contact corrosion of different materials can be sufficiently suppressed when the insulating resin layer as described in Patent Document 3 is arranged relatively thinly.

Furthermore, when the metal member and the carbon fiber reinforced resin material are used in an integrated manner, it is necessary to ensure excellent adhesion between them.

Therefore, the present invention has been made in view of the above problems, and corrosion of the metal member, particularly contact corrosion of different materials, is suppressed, and the adhesion between the metal member and the carbon fiber reinforced resin material is excellent. It is an object of the present invention to provide a new and improved method for producing a metal-carbon fiber reinforced resin material composite and a metal-carbon fiber reinforced resin material composite.

As a result of diligent studies to solve the above problems, the present inventors have an insulating property and a rust preventive property in the resin film layer arranged between the metal member and the carbon fiber reinforced resin material. By blending the inorganic salt particles containing a predetermined inorganic salt, it is possible to prevent the carbon fibers contained in the carbon fiber reinforced resin material from penetrating the resin film layer and coming into contact with the metal member, and in a corrosive environment. It was found that the rust-preventive inorganic salt particles were eluted to greatly improve the corrosion resistance. This is because the metal ions eluted from the particles in a corrosive environment are deposited not only on the metal but also on the carbon fiber to form an insulating film between the two, so that contact between different materials is avoided and the corrosion resistance is improved. Guess.

The present invention has been made based on such findings, and the gist thereof is as follows.
(1) Metal members and
A resin film layer arranged on at least a part of the surface of the metal member,
It has a matrix resin and a carbon fiber reinforced resin material containing a carbon fiber material existing in the matrix resin, which is arranged on the resin film layer.
The resin film layer, a powder resistivity at 23 ~ 27 ° C. is the 7.0 × 10 ⁷ Ωcm greater, and has a rust function, Cr, one or more elements selected from P and V It contains inorganic salt particles composed of inorganic salts, and further contains a binder resin.
A metal-carbon fiber reinforced resin material composite in which the volume fraction of the inorganic salt particles in the resin film layer is 5.0% or more and 40.0% or less.
(2) The inorganic salt includes chromate ion, dichromate ion, phosphate ion, hydrogen phosphate ion, dihydrogen phosphate ion, diphosphate ion, triphosphate ion, orthovanadate ion, and metavanadate ion. The metal-carbon fiber reinforced resin material composite according to (1), which comprises a salt of one or more ions selected from the group consisting of.
(3) The inorganic salt comprises one or more selected from the group consisting of aluminum dihydrogen tripolyphosphate, strontium chromate, potassium chromate, calcium chromate, magnesium vanadate, potassium vanadate, and calcium vanadate. , (1) or (2). The metal-carbon fiber reinforced resin material composite.
(4) The metal-carbon fiber reinforced resin material composite according to any one of (1) to (3), wherein the resin film layer has an average thickness of 5.0 μm or more.
(5) The metal-carbon fiber reinforcement according to any one of (1) to (4), wherein the average particle size of the oxide and / or inorganic salt particles is 0.2 μm or more and 50.0 μm or less. Resin material composite.
(6) The metal-carbon fiber reinforced resin material composite according to any one of (1) to (5), wherein the glass transition temperature of the resin film layer is 100 ° C. or lower.
(7) The metal-carbon fiber reinforced resin material composite according to any one of (1) to (6), wherein the matrix resin contains a thermoplastic resin.
(8) The metal-carbon fiber reinforced resin material composite according to any one of (1) to (7), wherein the matrix resin contains a phenoxy resin.
(9) The item according to any one of (1) to (8), wherein the binder resin contains one or more selected from the group consisting of urethane resin, epoxy resin, polyester resin and melamine resin. Metal-carbon fiber reinforced resin material composite.
(10) The metal-carbon fiber reinforced resin material composite according to any one of (1) to (8), wherein the metal member is a steel material or a plated steel material.
(11) A step of thermocompression bonding a metal member provided with a resin film layer on at least a part of the surface and a carbon fiber reinforced resin material via the resin film layer is provided.
The carbon fiber reinforced resin material includes a matrix resin and a carbon fiber material present in the matrix resin.
The resin film layer, a powder resistivity at 23 ~ 27 ° C. is the 7.0 × 10 ⁷ Ωcm greater, and has a rust function, Cr, one or more elements selected from P and V Contains inorganic salt particles composed of inorganic salts, and further contains a binder resin.
A method for producing a metal-carbon fiber reinforced resin material composite, wherein the volume fraction of the inorganic salt particles in the resin film layer is 5.0% or more and 40.0% or less.
(12) The method for producing a metal-carbon fiber reinforced resin material composite according to (11), further comprising a step of molding the metal member before the thermocompression bonding step.
(13) The metal-carbon fiber reinforced resin material composite according to (11), further comprising a step of forming a laminate in which the metal member and the carbon fiber reinforced resin material are laminated after the thermocompression bonding step. Manufacturing method.

As described above, according to the present invention, a new and improved metal that suppresses corrosion of metal members, particularly contact corrosion of dissimilar materials, and has excellent adhesion between metal members and carbon fiber reinforced resin materials. -A method for producing a carbon fiber reinforced resin material composite and a metal-carbon fiber reinforced resin material composite can be provided.

It is sectional drawing in the stacking direction of the metal-carbon fiber reinforced resin material composite which concerns on one Embodiment of this invention. It is sectional drawing in the stacking direction of the metal-carbon fiber reinforced resin material composite which concerns on one modification of this invention. It is sectional drawing in the stacking direction of the metal-carbon fiber reinforced resin material composite which concerns on other modification of this invention. It is sectional drawing in the stacking direction of the metal-carbon fiber reinforced resin material composite which concerns on other modification of this invention. It is a schematic diagram explaining the manufacturing method of the metal-CFRP composite which concerns on 1st Embodiment of this invention. It is a schematic diagram explaining the manufacturing method of the metal-CFRP composite which concerns on 1st Embodiment of this invention. It is a schematic diagram explaining the manufacturing method of the metal-CFRP composite which concerns on 2nd Embodiment of this invention. It is a schematic diagram explaining the manufacturing method of the metal-CFRP composite which concerns on 2nd Embodiment of this invention.

A preferred embodiment of the present invention will be described in detail with reference to the accompanying drawings below. In the present specification and the drawings, components having substantially the same functional configuration are designated by the same reference numerals to omit duplicate description.

Also, similar components of different embodiments are distinguished by adding different alphabets after the same code. However, if it is not necessary to distinguish each of a plurality of components having substantially the same functional configuration, only the same reference numerals are given. In addition, each figure is appropriately enlarged or reduced for ease of explanation, and the figure does not show the actual size and ratio of each part.

<1. Metal-Carbon Fiber Reinforced Resin Material Composite>
[1.1. Composition of metal-carbon fiber reinforced resin material composite]
First, the configuration of the metal-carbon fiber reinforced resin material composite according to the embodiment of the present invention will be described with reference to FIG. FIG. 1 is a schematic view showing a cross-sectional structure of a metal-carbon fiber reinforced resin material composite 1 as an example of the metal-carbon fiber reinforced resin material composite according to the present embodiment in the stacking direction.

As shown in FIG. 1, the metal-carbon fiber reinforced resin material (CFRP) composite 1 includes a metal member 11, a carbon fiber reinforced resin material (CFRP layer) 12, and a resin film layer 13. The metal member 11 and the CFRP layer 12 are composited via the resin film layer 13. Here, "composite" means that the metal member 11 and the CFRP layer 12 are bonded (bonded) to each other via the resin film layer 13 and integrated. Further, "integration" means that the metal member 11, the CFRP layer 12, and the resin film layer 13 move as one when processed or deformed.

In the present embodiment, the resin film layer 13, the powder resistivity at 23 ~ 27 ° C. is 7.0 × 10 ⁷ Ωcm than has the anti-corrosion function, Cr, is selected from P and V It contains inorganic salt particles 131 composed of inorganic salts of one or more elements (hereinafter, also simply referred to as “inorganic salt particles 131”), and the volume resistivity of the inorganic salt particles 131 is 100, which is the total volume of the resin film layer 13. When it is%, it is 5.0% or more and 40.0% or less. As a result, the corrosion resistance of the metal-CFRP composite 1 is improved, particularly with respect to contact corrosion of different materials. When the volume ratio of the inorganic salt particles 131 is 5.0% or more, the inorganic salt particles 131 can surely prevent the contact corrosion between the metal member 11 and the carbon fiber material 121. Further, when the volume fraction of the inorganic salt particles 131 is 40.0% or less, the cohesive failure of the resin film layer 13 is prevented, and the adhesion between the resin film layer 13 and the CFRP layer 12 is sufficiently excellent. ..

The volume fraction of the inorganic salt particles 131 in the resin film layer 13 is the specific gravity of the film resin by determining the solid content mass ratio of the inorganic salt particles 131 added when the resin film layer 13 is produced in the resin film layer 13. And the volume fraction can be calculated from the specific gravity of the particles. Further, the volume ratio of the inorganic salt particles 131 in the resin film layer 13 is analyzed by analyzing an arbitrary cross section with an electrolytic emission type electron probe microanalyzer (FE-EPMA: Electron Probe Micro Analyzer), and the surface of the metal component contained in the particles. The area ratio obtained by image analysis using the distribution photograph can be used as the volume ratio of the particles in the resin film layer. As a result of diligent studies by the inventors, it was found that the volume fraction in the film and the area fraction of the metal component contained in the particles measured by FE-EPMA in terms of cross section are strictly different but close to each other. , In the present invention, it can also be obtained as described above.

Hereinafter, each configuration of the metal-CFRP composite 1 will be described in detail.
(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 a press or the like, but the shape is preferably a thin plate. Examples of the material of the metal member 11 include iron, titanium, aluminum, magnesium, and alloys thereof. Here, examples of alloys 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 tensile strength than other metal types. Examples of such steel materials include cold-rolled steel sheets for general use, drawing or ultra-deep drawing, which are standardized by the Japan Industrial Standards (JIS) as thin plate-shaped steel sheets used for automobiles, and workability for automobiles. There are steel materials such as cold-rolled high-tensile steel sheets, hot-rolled steel sheets for general use and processing, hot-rolled steel sheets for automobile structures, and workable hot-rolled high-tensile steel sheets for automobiles, for general structures and machinery. Carbon steel, alloy steel, high tension steel and the like used for structural purposes can also be mentioned as steel materials not limited to thin plates.

Any surface treatment may be applied to the steel material. Here, the surface treatment refers to, for example, various plating treatments such as zinc plating and aluminum plating, chemical conversion treatments such as chromate treatment and non-chromate treatment, and chemical surfaces such as physical or chemical etching such as sandblasting. Roughing treatment can be mentioned, but is not limited to these. Further, the plating may be alloyed or a plurality of types of surface treatments may be applied. As the surface treatment, it is preferable that at least a treatment for the purpose of imparting rust prevention is performed.

Among the steel materials, the plated steel material that has been plated is preferable because it has excellent corrosion resistance. Particularly preferable plated steel materials as the metal member 11 include hot-dip galvanized steel sheets, galvanized galvanized steel sheets, alloyed hot-dip galvanized steel sheets obtained by heat-treating these and alloying them by diffusing Fe during zinc plating, and electrogalvanized steel sheets. Hot-dip Zn-Al alloy-plated steel sheets represented by steel sheets, electric Zn-Ni plated steel sheets, hot-dip Zn-5% Al alloy-plated steel sheets and hot-dip 55% Al-Zn alloy-plated steel sheets, hot-dip Zn-1 to 12% Al-1 Hot-dip Zn-Al-Mg alloy-plated steel sheet represented by ~ 4% Mg alloy-plated steel sheet, hot-dip 55% Al-Zn-0.1 ~ 3% Mg alloy-plated steel sheet, Ni-plated steel sheet, or heat-treated and Ni-plated. Examples thereof include alloyed Ni-plated steel sheets, Al-plated steel sheets, tin-plated steel sheets, and chrome-plated steel sheets that are alloyed by diffusing Fe. The galvanized steel sheet has excellent corrosion resistance and is suitable. Further, the Zn—Al—Mg alloy plated steel sheet is more suitable because it has further excellent corrosion resistance.

It is preferable that the surface of the metal member 11 is treated with a primer in order to enhance the adhesiveness with the CFRP layer 12. As the primer used in this treatment, for example, a silane coupling agent or a triazine thiol derivative is preferable. Generally known silane coupling agents as silane coupling agents, for example, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-amino Ethyl) Aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropylmethyldiethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxy Propylmethyldimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane, N-β- ( N-Vinylbenzylaminoethyl) -γ-aminopropylmethyldimethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl)- γ-Aminopropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-Mercaptopropyltrimethoxysilane, γ-Mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldiethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxy Silane, vinyl triacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropylmethyldiethoxysilane, hexamethyldisilazane, γ-anilinopropyl Trimethoxysilane, γ-anilinopropylmethyldimethoxysilane, γ-anilinopropyltriethoxysilane, γ-anilinopropylmethyldiethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyltriethoxysilane, vinylmethyldi Ethoxysilane, octadecyldimethyl [3- (trimethoxysilyl) propyl] ammonium chloride, octadecyldimethyl [3- (methyldimethoxysilyl) propyl] Ammonium chloride, octadecyldimethyl [3- (triethoxysilyl) propyl] ammonium chloride, octadecyldimethyl [3- (methyldiethoxysilyl) propyl] ammonium chloride, γ-chloropropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, Examples thereof include methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, etc., and silane coupling agents having a glycidyl ether group, for example, γ-glycidoxypropyltrimethoxysilane and γ-glycidoxy having a glycidyl ether group. The use of propyltriethoxysilane particularly improves the process adhesion of the coating. Further, when a triethoxy type silane coupling agent is used, the storage stability of the surface treatment agent (primer) can be improved. It is considered that this is because triethoxysilane is relatively stable in an aqueous solution and the polymerization rate is slow. The silane coupling agent may be used alone or in combination of two or more. Examples of triazine thiol derivatives include 6-diallylamino-2,4-dithiol-1,3,5-triazine, 6-methoxy-2,4-dithiol-1,3,5-triazine monosodium and 6-propyl-2. , 4-Dithiolamino-1,3,5-triazine monosodium and 2,4,6-trithiol-1,3,5-triazine and the like are exemplified.

(CFRP layer 12)
The CFRP layer 12 has a matrix resin 123 and a carbon fiber material 121 contained in the matrix resin 123 and compounded.

The carbon fiber material 121 is not particularly limited, but for example, either a PAN type or a pitch type can be used and may be selected according to the purpose and application. Further, as the carbon fiber material 121, the above-mentioned fibers may be used alone or in combination of two or more.

In the CFRP used for the CFRP layer 12, the reinforcing fiber base material used as the base material of the carbon fiber material 121 includes, for example, a non-woven fabric base material using chopped fiber, a cloth material using continuous fiber, and a unidirectional reinforcing fiber base material. (UD material) or the like can be used. From the viewpoint of the reinforcing effect, it is preferable to use a cloth material or a UD material as the reinforcing fiber base material.

The matrix resin 123 can be a solidified product or a cured product of the resin composition. Here, the term "solidified" simply means that the resin component itself is solidified, and the term "cured product" means that the resin component is cured by containing various curing agents. To do. The curing agent that can be contained in the cured product also includes a cross-linking agent as described later, and the above-mentioned "cured product" includes a cross-linked cured product formed by cross-linking.

◇ Resin composition As the resin composition constituting the matrix resin 123, either a thermosetting resin or a thermoplastic resin can be used, but it is preferable that the resin composition contains the thermoplastic resin as a main component. The type of thermoplastic resin that can be used for the matrix resin 123 is not particularly limited, and for example, phenoxy resin, polyolefin and its acid-modified product, polystyrene, polymethylmethacrylate, AS resin, ABS resin, polyethylene terephthalate and polybutylene terephthalate. Thermoplastic aromatic polyesters such as polyester, polycarbonate, polyimide, polyamide, polyamideimide, polyetherimide, polyethersulfone, polyphenylene ether and its modifications, polyphenylene sulfide, polyoxymethylene, polyarylate, polyetherketone, polyetheretherketone , Polyetherketone Ketone, and one or more selected from nylon and the like can be used. The "thermoplastic resin" also includes a resin that can be a crosslinked cured product in the second cured state described later. Further, as the thermosetting resin that can be used for the matrix resin 123, for example, one or more selected from epoxy resin, vinyl ester resin, phenol resin, and urethane resin can be used.

Here, when the matrix resin 123 contains a thermoplastic resin, there are problems when a thermosetting resin is used as the CFRP matrix resin described above, that is, the CFRP layer 12 has brittleness and the tact time is long. , Problems such as not being able to bend can be solved. However, since the thermoplastic resin usually has a high viscosity when melted and cannot be impregnated into the carbon fiber material 121 in a low viscosity state like a thermosetting resin such as an epoxy resin before thermosetting, it cannot be impregnated. Poor impregnation property with respect to the carbon fiber material 121. Therefore, it is not possible to increase the reinforcing fiber density (VF: Volume Fraction) in the CFRP layer 12 as in the case where the thermosetting resin is used as the matrix resin 123. For example, when an epoxy resin is used as the matrix resin 123, the VF can be about 60%, but when a thermoplastic resin such as polypropylene or nylon is used as the matrix resin 123, the VF is 50%. It will be about. Further, when a thermoplastic resin such as polypropylene or nylon is used, the CFRP layer 12 cannot have high heat resistance as in the case where a thermosetting resin such as an epoxy resin is used.

In order to solve the problem when such a thermoplastic resin is used, it is preferable to use a phenoxy resin as the matrix resin 123. 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 has good adhesiveness to the metal member 11 and the carbon fiber material 121. Further, by adding a curing component such as an epoxy resin to the phenoxy resin and copolymerizing it, a so-called partially cured resin can be obtained. By using such a partially curable resin as the matrix resin 123, it is possible to obtain a matrix resin having excellent impregnation property into the carbon fiber material 121. Furthermore, by thermosetting the cured component in this partially curable resin, it is possible to prevent the matrix resin 123 in the CFRP layer 12 from melting or softening when exposed to a high temperature, unlike a normal thermoplastic resin. it can. The amount of the curing component added to the phenoxy resin may be appropriately determined in consideration of the impregnation property of the carbon fiber material 121, the brittleness of the CFRP layer 12, the tact time, the processability, and the like. As described above, by using the phenoxy resin as the matrix resin 123, it is possible to add and control the curing component with a high degree of freedom.

For example, the surface of the carbon fiber material 121 is often coated with a sizing agent that is familiar with the epoxy resin. Since the phenoxy resin has a structure very similar to that of the epoxy resin, the sizing agent for the epoxy resin can be used as it is by using the phenoxy resin as the matrix resin 123. Therefore, cost competitiveness can be enhanced.

Among the thermoplastic resins, the phenoxy resin has good moldability and is excellent in adhesion to the carbon fiber material 121 and the metal member 11, and by using an acid anhydride, an isocyanate compound, caprolactam, etc. as a cross-linking agent. After molding, it can have the same properties as a highly heat-resistant thermosetting resin. Therefore, in the present embodiment, as the resin component of the matrix resin 123, it is preferable to use a solidified or cured product of a resin composition containing 50 parts by mass or more of phenoxy resin with respect to 100 parts by mass of the resin component. By using such a resin composition, the metal member 11 and the CFRP layer 12 can be firmly bonded to each other. It is more preferable that the resin composition contains 55 parts by mass or more of the phenoxy resin out of 100 parts by mass of the resin component. The form of the adhesive resin composition can be, for example, a powder, a liquid such as varnish, or a solid such as a film.

The content of the phenoxy resin can be measured by infrared spectroscopy (IR: Infrared spectroscopy) as described below, and when the content ratio of the phenoxy resin is analyzed from the target resin composition by IR. , It can be measured by using a general method of IR analysis such as transmission method and ATR reflection method.

The CFRP layer 12 is carved out with a sharp blade or the like, fibers are removed as much as possible with tweezers or the like, and the resin composition to be analyzed is sampled from the CFRP layer 12. In the case of the permeation method, a thin film is prepared by crushing the KBr powder and the powder of the resin composition to be analyzed while uniformly mixing them in a mortar or pestle to prepare a sample. In the case of the ATR reflection method, a tablet may be prepared by crushing the powder while uniformly mixing it in a mortar as in the transmission method, or a single crystal KBr tablet (for example, diameter 2 mm × thickness 1. The surface of 8 mm) may be scratched with a pestle or the like, and the powder of the resin composition to be analyzed may be sprinkled and adhered as a sample. In either method, it is important to measure the background of KBr alone before mixing with the resin to be analyzed. As the IR measuring device, a general commercially available one can be used, but the accuracy is such that the absorption (Absorbance) is in units of 1% and the wave number (Wavenumber) is in units of 1 cm- ^1. The apparatus is preferable, and examples thereof include FT / IR-6300 manufactured by JASCO Corporation.

When investigating the content of the phenoxy resin, the absorption peak of the phenoxy resin, for example, ¹⁴⁵⁰ ~ ^1480cm ^-1, 1500cm -1 vicinity, since there like 1600 cm ^-1 vicinity, based on the intensity of the absorption peak, containing It is possible to calculate the quantity.

The "phenoxy resin" is a linear polymer obtained from a condensation reaction between a divalent phenol compound and epihalohydrin or a double addition reaction between a divalent phenol compound and a bifunctional epoxy resin, and is an amorphous thermoplastic resin. Is. The phenoxy resin can be obtained in a solution or in a solvent-free manner by a conventionally known method, and can be used in any form of powder, varnish and film. The average molecular weight of the phenoxy resin 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 mass average molecular weight (Mw). Is in the range of 30,000 or more and 80,000 or less. By setting the Mw of the phenoxy resin (A) to the range of 10,000 or more, the strength of the molded product can be increased, and this effect is to set the Mw to 20,000 or more, further to 30,000 or more. And it will be even higher. On the other hand, by setting the Mw of the phenoxy resin to 200,000 or less, the workability and workability can be improved, and this effect is to set the Mw to 100,000 or less, further to 80,000 or less. And it will be even higher. In addition, Mw in this specification is a value measured by gel permeation chromatography (GPC) and converted using a standard polystyrene calibration curve.

The hydroxyl group equivalent (g / eq) of the phenoxy resin 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 and 500 or less. It is within the range. By setting the hydroxyl group equivalent of the phenoxy resin to 50 or more, the water absorption rate is lowered by reducing the hydroxyl groups, so that the mechanical properties of the cured product can be improved. On the other hand, by setting the hydroxyl group equivalent of the phenoxy resin to 1,000 or less, it is possible to suppress the decrease in hydroxyl groups, so that the affinity with the adherend is improved and the mechanical properties of the metal-CFRP composite 1 are improved. be able to. This effect is further enhanced by setting the hydroxyl group equivalent to 750 or less, and further to 500 or less.

Further, the glass transition temperature (Tg) of the phenoxy resin is preferably in the range of 65 ° C. or higher and 150 ° C. or lower, but preferably in the range of 70 ° C. or higher and 150 ° C. or lower. When the Tg is 65 ° C. or higher, it is possible to prevent the resin from becoming too fluid while ensuring moldability, so that the thickness of the resin film layer 13 can be sufficiently ensured. On the other hand, when the Tg is 150 ° C. or lower, the melt viscosity becomes low, so that the carbon-reinforced fiber base material can be easily impregnated without defects such as voids, and a lower temperature bonding process can be performed. The Tg of the resin in the present specification is measured at a temperature in the range of 20 to 280 ° C. using a differential scanning calorimetry device under a heating condition of 10 ° C./min, and is calculated from the peak value of the second scan. It is a numerical value.

The phenoxy resin is not particularly limited as long as it satisfies the above physical properties, but preferred ones are bisphenol A type phenoxy resins (for example, Phenototo YP-50 and Phenotote YP-50S manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.). Phenotote YP-55U available), bisphenol F type phenoxy resin (for example, available as Phenotote FX-316 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), bisphenol A and bisphenol F copolymerized phenoxy resin (for example, Nippon Steel & Sumikin) Special phenoxy resins such as brominated phenoxy resins other than the phenoxy resins listed above, phosphorus-containing phenoxy resins, and sulfone group-containing phenoxy resins (for example, phenoxy resins manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.) (Available as Thoth YPB-43C, Phenotote FX293, YPS-007, etc.) and the like. These resins can be used alone or in admixture of two or more.

The thermoplastic resin used as the resin component of the matrix resin 123 is preferably one having a melt viscosity of 3,000 Pa · s or less in any of the temperature ranges of 160 to 250 ° C., and is 90 Pa · s or more and 2,900 Pa · s or more. The melt viscosity in the range of s or less is more preferable, and the melt viscosity in the range of 100 Pa · s or more and 2,800 Pa · s or less is further preferable. By setting the melt viscosity in the temperature range of 160 to 250 ° C. to 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 CFRP layer 12. On the other hand, when the melt viscosity is 90 Pa · s or more, the molecular weight of the resin composition can be made appropriate, and embrittlement and the accompanying decrease in mechanical strength of the metal-CFRP composite 1 can be suppressed. Can be done.

Further, the resin composition constituting the matrix resin 123 may be a crosslinkable resin composition in which a crosslinking agent is blended with the above-mentioned resin composition. For example, a crosslinkable resin composition is obtained by blending, for example, an acid anhydride, isocyanate, caprolactam or the like as a crosslinker with a resin composition containing a phenoxy resin (hereinafter, also referred to as “phenoxy resin (A)”). It can also be. The crosslinkable resin composition is subjected to a crosslink reaction using a secondary hydroxyl group contained in the phenoxy resin (A) to improve the heat resistance of the resin composition, so that the member can be used in a higher temperature environment. It is advantageous for application. For cross-linking using the secondary hydroxyl group of the phenoxy resin (A), it is preferable to use a cross-linking resin composition containing a cross-linking curable resin (B) and a cross-linking agent (C). As the crosslinkable curable resin (B), for example, an epoxy resin or the like can be used, but the method is not particularly limited. By using such a crosslinkable resin composition, a cured product (crosslinked cured product) in a second cured state in which the Tg of the resin composition is significantly improved as compared with the case of the phenoxy resin (A) alone can be 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.

In the crosslinkable resin composition, as the crosslinkable curable resin (B) to be blended with the phenoxy resin (A), an epoxy resin having bifunctionality or higher is preferable. Examples of the bifunctional or higher functional epoxy resin include bisphenol A type epoxy resin (for example, available as Epototo YD-011, Epototo YD-7011, and Epototo YD-900 manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.) and bisphenol F type epoxy resin (for example). , Nippon Steel & Sumikin Chemical Co., Ltd. Epototo YDF-2001), Diphenyl ether type epoxy resin (for example, Nippon Steel & Sumitomo Metal Chemical Co., Ltd. YSLV-80DE), Tetramethylbisphenol F type epoxy resin (for example, Nippon Steel & Sumitomo Metal Chemical Co., Ltd.) YSLV-80XY manufactured by Nippon Steel & Sumitomo Metal Corporation (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.) (Available as), phenol novolac type epoxy resin (for example, available 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, Epototo YDCN-703, Epototo YDCN-704 available), Aralquilnaphthalenediol novolac type epoxy resin (for example, available as ESN-355 manufactured by Nippon Steel & Sumitomo Metal Corporation), Triphenylmethane type epoxy resin (for example) , Available as EPPN-502H manufactured by Nippon Kayaku Co., Ltd.), but is not limited thereto. Further, one of these epoxy resins may be used alone, or two or more of these epoxy resins may be mixed and used.

The crosslinkable curable resin (B) is not particularly limited, but a crystalline epoxy resin is preferable, and the melt viscosity at 150 ° C. is 2.0 Pa · in the melting point range of 70 ° C. or higher and 145 ° C. or lower. A crystalline epoxy resin having an s or less is more preferable. By using a crystalline epoxy resin exhibiting such melt characteristics, the melt viscosity of the crosslinkable resin composition as the resin composition can be lowered, and the adhesiveness of the CFRP layer 12 can be improved. Further, when the melt viscosity is 2.0 Pa · s or less, the moldability of the crosslinkable resin composition can be made sufficiently excellent, and the homogeneity of the metal-CFRP composite 1 can be improved. it can.

Examples of the crystalline epoxy resin suitable as the crosslinkable curable resin (B) include Epototo YSLV-80XY, YSLV-70XY, YSLV-120TE, YDC-1312, and Mitsubishi Chemical Corporation YX-4000 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. , YX-4000H, YX-8800, YL-6121H, YL-6640, etc., HP-4032, HP-4032D, HP-4700, etc. manufactured by DIC Corporation, NC-3000 manufactured by Nippon Kayaku Co., Ltd., etc.

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 the strong cross-linking such as curing of a thermosetting resin, the cross-linking can be broken by a hydrolysis reaction, so that the metal member 11 and the CFRP layer 12 can be easily peeled off. Therefore, the metal member 11 can be recycled.

Acid anhydride is preferable as the cross-linking agent (C). The acid anhydride is not particularly limited as long as it is solid at room temperature and does not have much sublimation property, but it is a phenoxy resin (from the viewpoint of imparting heat resistance to the metal-CFRP complex 1 and reactivity. Aromatic acid anhydrides having two or more acid anhydrides that react with the hydroxyl group of A) are preferable. In particular, aromatic compounds having two acid anhydride groups, such as pyromellitic anhydride, are preferably used because they have a higher crosslink density and improved heat resistance than a combination of trimellitic anhydride and a hydroxyl group. Will be done. Aromatic acid dianhydrides are also phenoxy resins such as 4,4'-oxydiphthalic acid, ethylene glycol bisuanhydrotrimerite, and 4,4'-(4,4'-isopropyridenediphenoxy) diphthalic anhydride. Aromatic acid dianhydride having compatibility with the epoxy resin has a large effect of improving Tg and is more preferable. In particular, aromatic acid dianhydrides having two acid anhydride groups, such as pyromellitic anhydride, have improved cross-linking densities as compared to, for example, phthalic anhydride having only one acid anhydride group. It is preferably used because it improves heat resistance. That is, the aromatic acid dianhydride has two acid anhydride groups, so that 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). Since four carboxyl groups are generated by the esterification reaction with the secondary hydroxyl group inside, the final crosslink density can be increased.

The reaction of the phenoxy resin (A), the epoxy resin as the crosslinkable resin (B), and the crosslinker (C) is carried out with the secondary hydroxyl group in the phenoxy resin (A) and the acid anhydride group of the crosslinker (C). Is crosslinked and cured by the esterification reaction of the above, and further, the reaction of the carboxyl group generated by this esterification reaction with the epoxy group of the epoxy resin. A phenoxy resin crosslinked product can be obtained by the reaction of the phenoxy resin (A) and the cross-linking agent (C), but since the melt viscosity of the resin composition can be lowered by the coexistence of the epoxy resin, the adherend (resin). It exhibits excellent properties such as improvement of impregnation property with the film layer 13), promotion of cross-linking reaction, improvement of cross-linking density, and improvement of mechanical strength.

In the crosslinkable resin composition, the epoxy resin as the crosslinkable curable resin (B) coexists, but the phenoxy resin (A), which is a thermoplastic resin, is the main component, and the secondary hydroxyl group is used. It is considered that the esterification reaction of the cross-linking agent (C) with the acid anhydride group is prioritized. 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 (the reaction rate is slow), the cross-linking agent (C) is used. The reaction of the phenoxy resin (A) with the secondary hydroxyl group occurs first, and then the cross-linking agent (C) remaining in the previous reaction and the residual carboxyl group derived from the cross-linking agent (C) react with the epoxy resin. As a result, the crosslink density is further increased. Therefore, unlike the resin composition containing an epoxy resin which is a thermosetting resin as a main component, the crosslinked cured product obtained by the crosslinkable resin composition is a thermoplastic resin and is excellent in storage stability.

In the crosslinkable resin composition utilizing cross-linking of the phenoxy resin (A), the cross-linking curable resin (B) is in the range of 5 parts by mass or more and 85 parts by mass or less with respect to 100 parts by mass of the phenoxy resin (A). It is preferable that it is contained so as to become. The content of the crosslinkable curable resin (B) with respect to 100 parts by mass of the phenoxy resin (A) is more preferably in the range of 9 parts by mass or more and 83 parts by mass or less, and further preferably 10 parts by mass or more and 80 parts by mass or less. It is within the range. By setting the content of the crosslinkable resin (B) to 85 parts by mass or less, the curing time of the crosslinkable resin (B) can be shortened, so that the strength required for demolding can be easily obtained in a short time. The recyclability of the CFRP layer 12 is improved. This effect is further enhanced by setting the content of the crosslink curable resin (B) to 83 parts by mass or less, further to 80 parts by mass or less. On the other hand, when the content of the crosslinkable resin (B) is 5 parts by mass or more, it becomes easy to obtain the effect of improving the crosslink density by adding the crosslinkable resin (B), and the crosslinkable resin composition can be crosslinked and cured. The substance easily expresses Tg at 160 ° C. or higher, and the fluidity becomes good. The content of the crosslinkable resin (B) is measured in the same manner 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.

The blending 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 the acid anhydride group with respect to 1 mol of the secondary hydroxyl group of the phenoxy resin (A), and is preferable. The amount is in the range of 0.7 mol or more and 1.3 mol or less, and 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 that the unreacted acid anhydride and the carboxyl group adversely affect the curing characteristics and the cross-linking density. Therefore, it is preferable to adjust the blending amount of the crosslink curable resin (B) according to the blending amount of the crosslinking agent (C). Specifically, for example, the epoxy resin used as the crosslinkable curable resin (B) is used to react the carboxyl group generated by the reaction between the secondary hydroxyl group of the phenoxy resin (A) and the acid anhydride group of the crosslinker (C). For this purpose, the blending amount of the epoxy resin may be set within the range of 0.5 mol or more and 1.2 mol or less in terms of the equivalent ratio with the cross-linking agent (C). Preferably, the equivalent ratio of the cross-linking agent (C) to the epoxy resin is in the range of 0.7 mol or more and 1.0 mol or less.

When the cross-linking agent (C) is blended together with the phenoxy resin (A) and the cross-linking curable resin (B), a cross-linking resin composition can be obtained, but an accelerator as a catalyst is used to ensure that the cross-linking reaction is carried out. (D) may be further added. The accelerator (D) is not particularly limited as long as it is solid at room temperature and does not have sublimation properties. For example, a tertiary amine such as triethylenediamine, 2-methylimidazole, 2-phenylimidazole, etc. Examples thereof include imidazoles such as 2-phenyl-4-methylimidazole, organic phosphins such as triphenylphosphine, and tetraphenylborone salts such as tetraphenylphosphonium tetraphenylborate. One type of these accelerators (D) may be used alone, or two or more types may be used in combination. When the crosslinkable resin composition is made into a fine powder and adhered to the reinforcing fiber base material by a powder coating method using an electrostatic field to form the matrix resin 123, the catalytic activity temperature is set as the accelerator (D). It is preferable to use an imidazole-based latent catalyst that is solid at room temperature of 130 ° C. or higher. When the accelerator (D) is used, the blending 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 resin (B) and the crosslinker (C). It is preferably in the range of 1 part by mass or more and 5 parts by weight or less.

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 the melt viscosity in the temperature range of 160 to 250 ° C., is 3,000 Pa · s or less. It is more preferably 2,900 Pa · s or less, and even more preferably 2,800 Pa · s or less. By setting the minimum melt viscosity in the temperature range of 160 to 250 ° C. to 3,000 Pa · s or less, the crosslinkable resin composition can be sufficiently impregnated into the adherend during heat pressure bonding by a hot press or the like. Since it is possible to suppress the occurrence of defects such as voids in the CFRP layer 12, the mechanical properties of the metal-CFRP 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 2,900 Pa · s or less, and further to 2,800 Pa · s or less.

The resin composition (including the crosslinkable resin composition) for forming the matrix resin 123 includes, for example, natural rubber, synthetic rubber, elastomer, and various inorganic fillers as long as the adhesiveness and physical properties are not impaired. , Solvent, extender pigment, colorant, antioxidant, ultraviolet inhibitor, flame retardant, flame retardant aid and other additives may be blended.

However, the matrix resin 123 preferably has a content of inorganic salt particles, which will be described later, of less than 5.0% by volume. When the boundary between the CFRP layer 12 and the resin film layer 13 cannot be determined depending on the composition of the resin or the like, the boundary between the CFRP layer 12 and the resin film layer 13 can be determined based on the content of the inorganic salt particles. ..

Further, the impedance of the CFRP layer 12 is preferably less than 1 × 10 ⁹ Ω. When the impedance of the CFRP layer 12 is less than 1 × 10 ⁹ Ω, an electrodeposition coating film is likely to be formed on the CFRP layer 12 during electrodeposition coating. Therefore, on the side surface of the metal-CFRP composite 1 (the surface along the stacking direction), the electrodeposition coating film is sufficiently easily formed from the CFRP layer 12 to the metal member 11. This makes it possible to suppress contact corrosion of dissimilar materials on the side surface of the metal-CFRP composite 1. Further, on the side surface of the metal-CFRP composite 1, conduction due to a corrosion factor such as water or salt water can be suppressed, and corrosion of the metal member 11 due to this corrosion factor can be suppressed.

In the metal-CFRP composite 1, the matrix resin 123 of the CFRP layer 12 and the resin constituting the resin film layer 13 may be the same resin or different resins. However, from the viewpoint of sufficiently ensuring the adhesiveness between the CFRP layer 12 and the resin film layer 13, the matrix resin 123 is contained in a resin or polymer of the same or the same type as the resin forming the resin constituting the resin film layer 13. It is preferable to select a resin type having an approximate ratio of polar groups contained in. Here, "the same resin" means that it is composed of the same components and has the same composition ratio, and if the main components are the same, the composition ratio is different from that of "the same type of resin". It means that it is also good. The "same type of resin" includes the "same resin". Further, the "main component" means a component contained in an amount of 50 parts by mass or more out of 100 parts by mass of the total resin component. The "resin component" includes a thermoplastic resin and a thermosetting resin, but does not include a non-resin component such as a cross-linking agent.

In the metal-CFRP composite 1, the CFRP layer 12 is formed by using at least one CFRP molding prepreg. The number of CFRP forming prepregs to be laminated can be selected according to the desired thickness of the CFRP layer 12.

(Resin film layer 13)
The resin film layer 13 is arranged between the metal member 11 of the metal-CFRP composite 1 and the CFRP layer 12 and joins them. Further, the resin film layer 13 has an insulating property in a corrosive environment, and insulates between the metal member 11 and the CFRP layer 12. Specific examples of the corrosive environment include an environment in which water adheres and / or exists around the metal-CFRP composite 1 when the metal-CFRP composite 1 is wet or after it is wet.

Then, the resin film layer 13, at least, the powder resistivity at 23 ~ 27 ° C. is the 7.0 × 10 ⁷ Ωcm greater, and has a rust function, Cr, 1 kind selected from P and V It contains inorganic salt particles 131 composed of inorganic salts of the above elements, and further contains binder resin 133.

The volume fraction of the inorganic salt particles 131 in the resin film layer 13 is 5.0% or more and 40.0% or less. This makes it possible to prevent corrosion of the metal member 11, particularly contact corrosion of different materials.

To explain in detail, in general, the CFRP layer and the metal member are joined by thermocompression bonding via a resin film layer. At this time, some of the carbon fiber materials in the CFRP layer are pressed by the pressure during thermocompression bonding and protrude from the surface of the CFRP layer. Then, the protruding carbon fiber material penetrates the resin film layer, so that the carbon fiber material and the metal member come into contact with each other, and corrosion occurs due to electrolytic corrosion.

On the other hand, in the present embodiment, in the metal-CFRP composite 1, the inorganic salt particles 131 having a relatively low conductivity are made of resin so that the carbon fiber material 121 protruding from the surface of the CFRP layer 12 does not come into contact with the metal member 11. It is contained in the film layer 13. That is, the inorganic salt particles 131 having relatively low conductivity act as a spacer between the carbon fiber material 121 and the metal member 11, and can insulate between the carbon fiber material 121 and the metal member 11. Since the volume ratio of the inorganic salt particles 131 in the resin film layer 13 is 5.0% or more and 40.0% or less, the inorganic salt particles 131 existing in the resin film layer 13 are appropriately bonded even during thermocompression bonding. It is fixed and can prevent the film layer 13 of the carbon fiber material 121 protruding from the CFRP layer 12 from penetrating. Therefore, contact between the carbon fiber material 121 and the metal member 11 is prevented, and contact corrosion of different materials is prevented. Furthermore, the present inventors have determined that by making the inorganic salt particles 131 have a rust preventive function, the components of the inorganic salt particles 131 having rust preventive properties are eluted in a corrosive environment, and the corrosion resistance is greatly improved. I found out. This is because the metal or inorganic ions eluted from the inorganic salt in a corrosive environment are deposited not only on the metal member 11 but also on the carbon fiber (carbon fiber material 121) to form an insulating film between them, so that different materials are used. It is presumed that contact is avoided and corrosion resistance is improved. As a result, the peeling of the resin film layer 13 and the CFRP layer 12 prevents the invasion of corrosion factors, and the corrosion is prevented.

If the volume fraction of the inorganic salt particles 131 in the resin film layer 13 is less than 5.0%, the volume concentration of the inorganic salt in the film becomes low, and the inorganic salt particles 131 easily move during thermocompression bonding. Then, the carbon fiber material 121 protruding from the CFRP layer 12 presses and moves the inorganic salt particles 131, and as a result, the carbon fiber material 121 easily penetrates the resin film layer 13. As a result, contact corrosion of dissimilar materials cannot be sufficiently prevented. Further, if the inorganic salt does not have a rust preventive function, the metal or inorganic ions do not dissolve or become difficult to dissolve in a corrosive environment, and the action of depositing on the surface of the carbon fiber material 121 or the surface of the metal member 11 acts. descend. The volume fraction of the inorganic salt particles 131 in the resin film layer 13 is preferably 10.0% or more, more preferably 20.0% or more.

Further, when the volume fraction of the inorganic salt particles 131 in the resin film layer 13 exceeds 40.0%, the resin film layer 13 is likely to be aggregated and broken, and the adhesion between the resin film layer 13 and the CFRP layer 12 is sufficient. It doesn't become a plastic. The volume fraction of the inorganic salt particles 131 in the resin film layer 13 is preferably 35.0% or less, more preferably 30.0% or less.

It is conceivable to form an inorganic salt layer or a metal oxide layer having low conductivity instead of the resin film layer 13 containing the inorganic salt particles 131. In this case, the insulation between the metal member and the carbon fiber material is considered. While the properties can be guaranteed, the workability of the metal-CFRP composite itself is reduced and it becomes difficult to guarantee the adhesion. Therefore, the advantage of combining the metal member and the CFRP layer is sufficiently obtained. I can't.

Also, the powder resistivity at 23 ~ 27 ° C. of the inorganic salt particles 131 are 7.0 × 10 ⁷ Ωcm than as described above. Since the conductivity of the inorganic salt particles 131 is relatively small as described above, the inorganic salt particles 131 function as a spacer having an insulating property between the carbon fiber material 121 and the metal member 11. In contrast, the powder resistivity at 23 ~ 27 ° C. of the inorganic salt particles 131 is less than 7.0 × 10 ⁷ Ωcm and a carbon fiber material 121 and the metal member 11 has been conducted through the inorganic salt particles 131 I can't control the electrolytic corrosion. The powder resistance of the inorganic salt particles 131 at 23 to 27 ° C. is 10 MPa using a commercially available powder resistance measuring machine, for example, "Powder resistance measuring system MCP-PD51 type" manufactured by Mitsubishi Chemical Analytech. It can be obtained by measuring the resistance of the powder particles compressed with. Further, in general, the powder resistivity can be regarded as equivalent to the volume resistivity of the material itself of the conductive particles 131 to be measured.

The inorganic salt particles 131 in the resin film layer 13 have the powder resistivity and rust preventive function as described above, and may be composed of an inorganic salt of one or more elements selected from Cr, P and V. There is no particular limitation. When Cr, P and V are dissolved as ions in a corrosive environment, they are likely to be deposited on the surface of the metal member 11 as the anode and the carbon fiber material 121 as the cathode, which is effective in improving the corrosion resistance.

As the inorganic salt constituting the inorganic salt particles 131 having a rust preventive function according to the present embodiment, for example, the above-mentioned inorganic salt of oxo acid containing a metal atom or element can be used. The inorganic salt containing Cr, chromate ions _(CrO ^{4 2-),} and salts of dichromate ion _(Cr ^{₂ O 7 2-)} of Cr such oxoacid ions. Examples of the inorganic salt containing P, phosphoric acid ion _(PO ^{4 3-),} hydrogen phosphate ions _(HPO ^{4 2-),} dihydrogen phosphate ion _(H 2 PO ₄ ^-), diphosphate ions (P ₂ O ₇ ^4-), triphosphate ions _(P _{3 O} ^{10 5-,} salts "tripolyphosphate") of P such oxoacid ions. Examples of the inorganic salt containing V, orthovanadate ion _(VO ^{4 3-),} and salts of metavanadate (VO ^3-) of V such oxoacid ions.
The inorganic salt particles 131 may be one kind of salt of each of the above-mentioned oxoacid ions, or may be a plurality of kinds of salts.

Among the above, the inorganic particles 131 are formed from the viewpoint of the barrier effect against the corrosion factors of the oxide when the inorganic salt fine particles are eluted and ionized in a wet corrosive environment and deposited as an oxide on the surface of a metal plate or carbon fiber. inorganic salts include, chromate ion _(CrO ^{4 2-),} phosphate ion _(PO ^{4 3-),} triphosphate ions _(P _{3 O} ^{10 5-,} "tripolyphosphate"), orthovanadate ion (VO It is preferably one or more salts selected from the group consisting of ₄ ^3- ) and metavanadic acid (VO ^3- ).

Examples of the counterion of each of the above oxoacid ions include cations of elements such as alkali metals, alkaline earth metals, Be, Mg, and Al, and one of them may be used alone or in combination of two or more. Can be used.

Among the above, the inorganic salt contained in the inorganic particles 131 is selected from the group consisting of Ca, Na, K, Sr, Mg, and Al as counterions from the viewpoint of elution of fine particles in the resin matrix in a corrosive environment. It is preferably a cation of one or more elements to be formed.

More specifically, examples of the inorganic salt include chromate such as potassium chromate, calcium chromate, and strontium chromate, zinc phosphate, aluminum phosphate, aluminum dihydrogen tripolyphosphate, sodium phosphate, and magnesium phosphate. Phosphates such as trimagnesium phosphate and vanadates such as sodium metavanadate, calcium vanadate and magnesium vanadate can be mentioned.

Among the above, from the viewpoint of elution of fine particles in the resin matrix in a corrosive environment, the conductive particles 131 are inorganic salts such as aluminum dihydrogen tripolyphosphate, strontium chromate, calcium chromate, potassium chromate, and vanadic acid. It preferably consists of one or more selected from the group consisting of magnesium, potassium vanadate, and calcium vanadate.

The average particle size r of the inorganic salt particles 131 is not particularly limited, but is, for example, 0.2 μm or more and 50.0 μm or less, preferably 0.2 μm or more and 10.0 μm or less. When the average particle size r of the inorganic salt particles 131 is 0.2 μm or more, the function as a spacer between the carbon fiber material 121 and the metal member 11 is fully exhibited. When the average particle size r of the inorganic salt particles 131 is 50.0 μm or less, the inorganic salt particles 131 are more suppressed from protruding onto the surface of the resin film layer 13, and the surface area of all the particles in the film is further suppressed. Since the inorganic salt particles 131 are easily eluted in a corrosive environment, it is also effective in further improving the corrosion resistance.

The average particle size of the inorganic salt particles 131 in the resin film layer 13 is measured by a generally known particle distribution measuring device, for example, a laser diffraction / scattering type particle size distribution measuring device (Microtrack MT3300EX, manufactured by Nikkiso Co., Ltd.). The particle size (D50) when the cumulative volume becomes 50% as a reference can be measured. Further, when it is desired to confirm the average particle size of the particles added in the resin film layer 13 in a mixed state, an arbitrary cross section of the resin film layer 13 is analyzed by FE-EPMA and has the rust preventive function. It can be obtained by the average value of the particle radii measured by the surface distribution photograph of the components contained in the inorganic salt.

Further, the resin film layer 13 contains the binder resin 133. The binder resin 133 functions as a binder for the inorganic salt particles 131 and contributes to the improvement of the insulating property of the resin film layer 13. The binder resin 133 is not particularly limited, and either a thermosetting resin or a thermoplastic resin can be used. Examples of the thermosetting resin include urethane resin, epoxy resin, melamine resin, vinyl ester resin and the like. Thermoplastic resins include phenoxy resins, polyolefins (polypropylene, etc.) and their acid modified products, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polycarbonate, polyimide, polyamide, polyamideimide, polyetherimide, polyethersulfone, and polyphenylene ether. And modified products thereof, polyarylate, polyetherketone, polyetheretherketone, polyetherketoneketone, nylon and the like. Examples of the phenoxy resin include those similar to those that can be used for the matrix resin 123 in the CFRP layer 12 described above.

Among the above, the binder resin 133 preferably contains one or more selected from the group consisting of urethane resin, epoxy resin, polyester resin and melamine resin. These resins are suitable because they easily flow at room temperature or are easily dissolved in a solvent or the like and applied, although they depend on the molecular weight and the glass transition temperature.

The glass transition temperature Tg of the binder resin 133 is, for example, 100 ° C. or lower, preferably 10 ° C. or higher and 60 ° C. or lower, and more preferably 10 ° C. or higher and 35 ° C. or lower. As a result, the carbon fiber reinforced resin is less likely to be peeled off even if the molding process is performed after the CFRP is attached.

The resin film layer 13 includes, for example, natural rubber, synthetic rubber, elastomer, and various inorganic fillers, solvents, extender pigments, colorants, antioxidants, and ultraviolet antioxidants, as long as the adhesiveness and physical properties are not impaired. Other additives such as a flame retardant and a flame retardant aid may be blended.

The average thickness T of the resin film layer 13 is not particularly limited, but is, for example, 5.0 μm or more, preferably 5.0 μm or more and less than 200.0 μm. When the average thickness T of the resin film layer 13 is 5.0 μm or more, it is possible to more reliably perform insulation and prevent contact corrosion of different materials of the metal member. Further, when the average thickness T of the resin film layer 13 is less than 200.0 μm, the cohesive failure of the resin film layer 13 is prevented, and the adhesion between the resin film layer 13 and the CFRP layer 12 is sufficiently excellent. Become.
Each configuration of the metal-CFRP composite 1 has been described above.

The glass transition temperature of the resin film layer 13 is, for example, 100 ° C. or lower, preferably 10 ° C. or higher and 60 ° C. or lower, and more preferably 10 ° C. or higher and 35 ° C. or lower. As a result, the carbon fiber reinforced resin is less likely to be peeled off even if the molding process is performed after the CFRP is attached.

The glass transition temperature of the resin film layer 13 can be measured by thermomechanical analysis (TMA). The thermomechanical analyzer can be a commercially available device, for example, the "TMA7000 series" manufactured by Hitachi High-Tech Science.

The thicknesses of the metal member 11, the CFRP layer 12, and the resin film layer 13 can be measured in accordance with the cross-sectional method of the optical method of JIS K 560-1-7, 5.4 as follows. it can. That is, using a room temperature curing resin that can be embedded without any harmful effect on the sample, using the low-viscosity Epomount 27-777 manufactured by Refine Tech Co., Ltd. as the main agent and 27-772 as the curing agent, the sample is used. Embed. At the point to be observed with a cutting machine, the sample is cut so as to be parallel to the thickness direction to obtain a cross section, and a polishing paper having a count specified in JIS R 6252 or 6253 (for example, 280 count, 400 count or 600 count). Polish with a count) to prepare an observation surface. If an abrasive is used, it is polished with an appropriate grade diamond paste or similar paste to create an observation surface. Further, if necessary, buffing may be performed to smooth the surface of the sample to a state where it can withstand observation.

Use a microscope equipped with an appropriate lighting 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 Corporation) so that the field of view is 300 μm. select. The size of the visual field may be changed so that the thickness of each can be confirmed (for example, if the thickness of the CFRP layer 12 is 1 mm, the size of the visual field may be changed so that the thickness can be confirmed). For example, when measuring the thickness of the resin film layer 13, the observation field of view is divided into four equal parts, the thickness of the resin film layer 13 is measured at the center of each fraction in the width direction, and the average thickness is measured. The thickness in the field of view. This observation field of view is performed by selecting 5 different places, dividing into 4 equal parts within each observation field of view, measuring the thickness in each fraction, and calculating the average value. Adjacent observation fields should be selected at least 3 cm apart. The thickness of the resin film layer 13 may be obtained by further averaging the average values at these five locations. Further, the thickness of the metal member 11 and the CFRP layer 12 may be measured in the same manner as the measurement of the thickness of the resin film layer 13.

[1.2. Modification example]
Next, a modified example of the metal-carbon fiber reinforced resin material composite 1 according to the above-described embodiment will be described. In addition, each modification described below may be applied alone to the said embodiment of the present invention, or may be applied in combination to the said embodiment of the present invention. Further, each modification may be applied in place of the configuration described in the above embodiment of the present invention, or may be additionally applied to the configuration described in the above embodiment of the present invention. 2 to 4 are schematic cross-sectional views for explaining the metal-carbon fiber reinforced resin material composite according to the modified example of the present invention, respectively.

(First modification)
In the above-described embodiment, the metal-CFRP composite 1 has been described as being composed of the metal member 11, the CFRP layer 12, and the resin film layer 13, but the present invention is not limited thereto. In the metal-CFRP composite 1 according to the present invention, additional layers may be arranged between layers or surfaces of each of these configurations. For example, as shown in FIG. 2, in the metal-CFRP composite 1A according to the modified example, a chemical conversion treatment layer 14 is arranged between the resin film layer 13 and the metal member 11. By arranging such a chemical conversion treatment layer 14 between the metal member 11 and the resin film layer 13, the corrosion resistance of the metal member 11 is improved, and the metal member 11 and the resin film layer of the metal-CFRP composite 1A are improved. Adhesion with 13 is improved.

The chemical conversion treatment layer 14 is not particularly limited, but is preferably a chemical conversion treatment layer containing Cr, P, Si and / or Zr. As a result, the above-mentioned effect of improving corrosion resistance and adhesion can be obtained more remarkably.

Such a chemical conversion treatment layer 14 may be an inorganic type or an inorganic-organic mixed type in which Cr, P, Si and / or Zr are polymerized via C or CO to form a network, or may be contained in a binder such as a resin. A type in which a film to which a compound composed of Cr, P, Si and / or Zr is added is applied and dried may be used. If necessary, other generally known rust preventive components, such as V-acid type, Ti-acid type, and P-acid type, may be added during the chemical conversion treatment. These chemical conversion treatments may be of a reaction type in which a film is precipitated by reacting with a metal on the surface of a metal material when treated, or of a type in which a wet treatment liquid is applied and dried and cured. It can be selected as needed.

In this case, the chemical conversion treatment layer 14 can contain Cr, P, Si and / or Zr in total, for example, 10 mg / m ² or more and 500 mg / m ² or less, preferably 30 g / m ² or more and 300 g / m ² or less. .. As a result, the adhesion between the metal member 11 and the resin film layer 13 can be made sufficiently excellent while further improving the corrosion resistance.

(Second modification)
Further, in the above-described embodiment, the CFRP layer 12 and the resin film layer 13 have been described as being arranged on one side of the metal member 11, but the present invention is not limited thereto. For example, as in the metal-CFRP composite 1B shown in FIG. The CFRP layer 12 and the resin film layer 13 may be arranged on both sides of the metal member 11. Further, in this case, the configurations of the CFRP layer 12 and the resin film layer 13 may be different from each other or may be the same.

(Third variant)
Further, the CFRP layer is not limited to the above-described embodiment, and may be a plurality of layers. For example, as in the metal-CFRP composite 1C shown in FIG. 4, the CFRP layer 12A is not limited to one layer, and may be two or more layers. When the CFRP layer 12A is a plurality of layers, the number n of the CFRP layer 12A may be appropriately set according to the purpose of use. When there are a plurality of CFRP layers 12A, each layer may have the same configuration or may be different. That is, the resin type of the matrix resin 123 constituting the CFRP layer 12A, the type and the content ratio of the carbon fiber material 121, and the like may be different for each layer.

(Fourth modification)
In the above-described embodiment, the case where the metal-CFRP composite 1 is plate-shaped has been schematically described, but the present invention is not limited to this, and naturally, the metal-CFRP composite according to the present invention is molded. You may be.

<2. Method for manufacturing metal-carbon fiber reinforced resin material composite>
Next, a method for producing the metal-carbon fiber reinforced resin material composite according to the embodiment of the present invention will be described. The method for producing a metal-carbon fiber reinforced resin material composite according to an embodiment of the present invention is a method of producing a metal member and a carbon fiber reinforced resin provided on at least a part of the surface of a resin film layer containing inorganic salt particles and a binder resin. It has a step of heat-bonding the material to the material through the resin film layer. Further, before and after the thermocompression bonding step, there may be a step of forming a metal member or a laminate in which the metal member and a carbon fiber reinforced resin material are laminated. Hereinafter, the method for producing the metal-carbon fiber reinforced resin material composite according to the embodiment of the present invention will be described in detail on the premise that molding is performed, but it goes without saying that molding may be omitted. ..
[2.1. First Embodiment]
5 and 6 are schematic views illustrating a method for producing a metal-CFRP composite according to the first embodiment of the present invention. The method for producing the metal-CFRP composite 1D according to the first embodiment includes a metal member 11A in which the resin film layer 13A is provided on at least a part of the surface and a carbon fiber reinforced resin material (CFRP or CFRP forming prepreg). At least has a thermocompression bonding step A for obtaining the laminate 100 by thermocompression bonding the resin film layer 13A. Further, the method for producing the metal-CFRP composite 1D according to the present embodiment includes the laminate 100 with the molding step A.
Further, the present embodiment may include, if necessary, a resin film layer forming step, a pretreatment step, and / or a post-step of forming the resin film layer 13A on at least a part of the surface of the metal member 11A. Hereinafter, each step will be described.

(Pretreatment process)
First, the metal member 11A is prepared (FIG. 5A). It is preferable that the metal member 11 is degreased, which is generally known, if necessary. As the degreasing method, generally known methods such as wiping with a solvent, washing with water, washing with an aqueous solution containing a surfactant or a detergent, a method of heating to volatilize an oil component, and alkaline degreasing can also be used. Alkaline degreasing is industrially common and is suitable because it has a high degreasing effect. Further, it is more preferable to perform a mold release treatment on the mold to be used and removal of deposits (dust removal) on the surface of the metal member 11A. By these pretreatments, the adhesion between the metal member 11A and the resin film layer 13A is improved.

(Film formation process)
Next, the resin film layer 13A is formed on the surface of the metal member 11A (FIG. 5 (b)). The resin film layer 13A is formed by applying a film layer material composition containing the material of the resin film layer 13A to the surface of the metal member 11A, drying and baking. The resin film layer material composition may be in the form of a liquid or slurry, or may be in the form of powder. A sheet as a resin film layer material composition molded in advance into a plate shape may be attached by thermocompression bonding or the like.

Further, the coating method is not particularly limited, and in the case of a sheet type, the pasting method can be a generally known method such as a human or a robot. In the case of a viscous liquid, it can be applied by a generally known method such as coating by a discharge method from a slit nozzle or a circular nozzle, brush coating, plate coating, spatula coating and the like. For those dissolved in a solvent, generally known coating methods such as brush coating, spray coating, bar coater, ejection coating from nozzles of various shapes, die coater coating, curtain coater coating, roll coater coating, screen printing, inkjet Coating or the like can be used. When the resin film layer material composition is in the form of powder, a known method such as powder coating can be adopted. In particular, in the resin film layer 13A formed by powder coating, since the resin film layer material composition is fine particles, the resin component is easily melted, and since the resin film layer 13A has appropriate voids, voids are removed. Cheap. Further, when the CFRP or the prepreg for CFRP molding is thermocompression-bonded, the resin component constituting the resin film layer 13A wets the surface of the metal member 11A well, so that a degassing step such as varnish coating is not required. The resin film layer 13A may be applied to the entire surface of the metal member 11A, or may be partially applied only to the portion to which the carbon fiber reinforced resin material (CFRP) is attached.

A chemical conversion treatment layer 14 may be provided on the metal member 11A before the resin film layer 13A is applied. As a method for providing the chemical conversion treatment layer 14, a generally known treatment method, for example, an immersion drying method, an immersion / water washing / drying method, a spray / water washing / drying method, a coating / drying method, a coating / drying curing method, or the like is used. Can be done. The coating method can be a generally known method such as dipping, brush coating, spraying, roll coater, bar coater, and blade coater.

Further, drying and baking can be performed by, for example, heat treatment. The heating conditions are not particularly limited, and can be, for example, 10 seconds or more and 30 minutes or less under the conditions of 100 ° C. or higher and 250 ° C. or lower. The resin film layer material composition may be a room temperature curing type. In this case, the resin film layer material composition may be a one-component type in which the main resin and the curing agent are mixed. It may be a two-component curing type in which the main resin and the curing agent are separated and mixed immediately before the coating, or a three-component or more type in which the main resin, the curing agent, and other additives are separated and mixed immediately before the coating. good.

The resin film layer 13A is coated or affixed when the CFRP forming prepreg or CFRP to be the CFRP layer 12B and the metal member 11A are placed on top of each other, and these laminated bodies are cured when they are thermally pressure-bonded, which will be described later. Alternatively, the CFRP forming prepreg or CFRP is placed on top of the resin film layer 13A laminated and cured by coating or pasting on the metal member 11A in advance, and then heat-bonded, which will be described later. Is also good.

(Thermocompression bonding step A)
Next, the metal member 11A and the carbon fiber reinforced resin material (CFRP or CFRP forming prepreg) are thermocompression bonded via the resin film layer 13A to obtain a metal-CFRP composite 1 (FIG. 5 (c)). Specifically, a laminate in which a CFRP molding prepreg (or CFRP) to be a CFRP layer 12B is laminated on a resin film layer 13A is installed in a pressurizing machine, and pressurization is performed while heating. As a result, the laminated body 100 in which the metal member 11A, the resin film layer 13A, and the CFRP layer 12B are laminated in this order is manufactured.

Specifically, first, the metal member 11A and the CFRP molding prepreg or CFRP are placed on top of each other via the resin film layer 13A to obtain a laminated body. When CFRP is used, it is preferable that the adhesive surface of CFRP is roughened by, for example, blasting treatment, or activated by plasma treatment, corona treatment, or the like. Next, the laminate 100 is obtained by heating and pressurizing (thermocompression bonding) the laminate.

Here, the thermocompression bonding conditions in this step are as follows.
The thermocompression bonding temperature is not particularly limited, but is, for example, 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, a crystalline resin is more preferably at a temperature equal to or higher than the melting point, and a non-crystalline resin is more preferably at a temperature of Tg + 150 ° C. or higher. When the temperature is equal to or lower than the upper limit temperature, it is possible to suppress excessive heat application and prevent the resin from being decomposed. Further, when the temperature is at least the above lower limit temperature, the melt viscosity of the resin can be made appropriate, and the adhesiveness to CFRP and the impregnation property to the CFRP base material can be made excellent.

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. When the pressure is 5 MPa or less, it is possible to prevent excessive pressure from being applied, and more reliably prevent deformation and damage from occurring. Further, when the pressure is 3 MPa or more, the impregnation property into the CFRP base material can be improved.

Regarding the thermocompression bonding time, at least 3 minutes or more is sufficient for thermocompression bonding, and it is preferably within the range of 5 minutes or more and 20 minutes or less.

(Additional heating process)
As an adhesive resin composition for forming the film layer 13A and a raw material resin for forming the matrix resin 123, the phenoxy resin (A) contains a crosslinkable curable resin (B) and a crosslinkable agent (C). If the adhesive resin composition is used, an additional heating step may be further included.

When a crosslinkable adhesive resin composition is used, the resin film layer 13A is formed by a cured product (solidified product) in the first cured state, which is solidified but not crosslinked (cured) in the thermocompression bonding step. Can be formed. Further, when the same or the same type as the crosslinkable adhesive resin composition is used as the raw material resin for the matrix resin of the CFRP molding prepreg to be the CFRP layer 12B, the cured product (solidified product) in the first cured state is used. The CFRP layer 12 containing the matrix resin 123 can be formed.

As described above, the intermediate body (preform) of the metal-CFRP composite 1A in which the metal member 11A, the uncured resin film layer 13A, and the CFRP layer 12B are laminated and integrated through the thermocompression bonding step. ) Can be produced. In this intermediate, if necessary, a CFRP layer 12B in which the matrix resin 123 is a cured product (solidified product) in the first cured state can be used. Then, the intermediate is post-cured to at least the resin film layer 13 made of the cured product (solidified material) in the first cured state by further performing an additional heating step after the heat bonding step. , The resin can be cross-linked and cured to change into a cured product (cross-linked cured product) in a second cured state. Preferably, the CFRP layer 12B is also post-cured to crosslink and cure the matrix resin 123 composed of the cured product (solidified product) in the first cured state, and the cured product (crosslinked cured product) in the second cured state. Can be changed to.

The additional heating step for post-cure is preferably performed at a temperature in the range of 200 ° C. or higher and 250 ° C. or lower over a period of about 30 to 60 minutes. Instead of post-cure, the heat history in a post-process such as painting may be used.

As described above, when the crosslinkable adhesive resin composition is used, the Tg after crosslink curing is greatly improved as compared with the phenoxy resin (A) alone. Therefore, before and after performing an additional heating step on the above-mentioned intermediate, that is, the resin changes from a cured product (solidified product) in the first cured state to a 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. or lower. Since the temperature is improved within the range of 220 ° C. or lower, the heat resistance can be significantly improved.

If molding of the laminate 100 is unnecessary, the following molding step A may be omitted, and the laminate 100 itself may be obtained as a metal-CFRP composite.

(Molding step A)
Next, the laminate 100 is molded (FIG. 6 (d)) to obtain a metal-CFRP composite 1D. The molding method of the laminated body 100 is not particularly limited, and various press workings such as shearing, bending, drawing, and forging can be adopted.

These presses may be performed at room temperature, but hot presses are suitable because CFRP does not easily come off from metal members during processing. The temperature of the hot press is preferably the same as that of the thermocompression bonding step described above.

In this embodiment, the thermocompression bonding step A and the molding step A (molding of the metal-CFRP composite 1D) may be performed at the same time. That is, in the pressure molding machine, the metal member 11A and the carbon fiber reinforced resin material (CFRP or CFRP forming prepreg) may be thermocompression bonded via the resin film layer 13A and may be molded at the same time.

(Post-process)
In the post-process for the metal-CFRP composite 1D, if necessary, in addition to painting, for mechanical joining with other members such as bolts and rivets, drilling and application of adhesive for adhesive joining. And so on.

[2.2. Second Embodiment]
7 and 8 are schematic views illustrating a method for producing a metal-CFRP composite according to a second embodiment of the present invention. The method for producing the metal-CFRP composite 1E according to the second embodiment includes a molding step B for molding a metal member 11B provided on at least a part of the surface of the resin film layer 13B, a metal member 11B, and carbon fibers. It has a heat-bonding step B in which the reinforced resin material is heat-bonded via the resin film layer 13B to obtain a metal-CFRP composite 1E.

That is, the second embodiment is different from the first embodiment in that the laminated body of the metal member 11B and the resin film layer 13B is molded before the CFRP layer 12C is formed. In the case of the first embodiment, depending on the matrix resin of CFRP, there is a risk that the resin may be cracked or peeled off from the metal member 11A. In addition, a warm press is required to prevent these. Further, in the first embodiment, when the CFRP is thick, it is necessary to devise a press die after the CFRP is attached. By forming the metal member 11B before forming the CFRP layer 12C in this way, the problems that may occur in the first embodiment described above can be eliminated, and the normally used press die can be diverted.

Since each condition used in the second embodiment is basically the same as that in the first embodiment, the description thereof will be omitted.

Specifically, the metal member 11B is prepared (FIG. 7 (a)), and the resin film layer 13B is formed on the surface of the metal member 11B (FIG. 7 (b)). Then, the metal member 11B on which the resin film layer 13B is formed is molded (FIG. 7 (c)). Finally, the carbon fiber reinforced resin material is thermocompression-bonded to the molded metal member 11B via the resin film layer 13B to obtain a metal-CFRP composite 1E (FIGS. 8 (d) and 8 (e)).

The method for producing the metal-CFRP composite according to the present embodiment has been described above. The method for producing the metal-CFRP composite according to the present invention is not limited to the above-described embodiment.

Hereinafter, the present invention will be described in more detail by way of examples. The examples described below are merely examples of the present invention, and do not limit the present invention.

<1. Manufacture of metal-CFRP composite>
(Preparation of metal plate)
The components are C: 0.131% by mass, Si: 1.19% by mass, Mn: 1.92%, P: 0.009% by mass, S: 0.0025% by mass, Al: 0.027% by mass, N : A steel having 0.0032% by mass and a balance of Fe was hot-rolled, pickled, and then cold-rolled to obtain a cold-rolled steel sheet having a thickness of 1.0 mm. Next, the produced cold-rolled steel sheet was annealed with a continuous annealing device under the condition that the maximum reached plate temperature was 820 ° C. The gas atmosphere in the annealing furnace in the annealing step was an N ₂ atmosphere containing 1.0% by volume of H ₂ . The produced cold-rolled steel sheet is called "CR".

Further, a cold-dip galvanized steel sheet prepared was prepared by annealing the produced cold-rolled steel sheet under the condition that the maximum temperature reached at 820 ° C. in the annealing step of a continuous hot-dip galvanizing apparatus having an annealing step, and then hot-dip galvanizing in the plating step. The gas atmosphere in the annealing furnace in the annealing step was an N ₂ atmosphere containing 1.0% by volume of H ₂ . The components of the plating bath in the plating process are Zn-0.2% Al (referred to as "GI"), Zn-0.09% Al (referred to as "GA"), Zn-1.5% Al-1.5. Four kinds of% Mg (referred to as "Zn-Al-Mg") and Zn-11% Al-3% Mg-0.2% Mg (referred to as "Zn-Al-Mg-Si") were used. Incidentally, those using hot-dip plating bath of Zn-0.09% Al plating (GA) is by dipping the steel sheet in a molten coating bath, while pulling the steel plate from the plating bath, by blowing N ₂ gas from the slit nozzle gas After wiping and adjusting the adhesion amount, alloying was performed by heating at a plate temperature of 480 ° C. with an induction heater to diffuse Fe in the steel plate into the plating layer.

When the tensile strength of the produced metal plate was measured, it was 980 MPa in each case.
The amount of plating on the plated steel sheet was 45 g / m ² for GA and 60 g / m ^{2 for} plating other than GA. In addition to the above, aluminum plates (hereinafter referred to as "Al plates") and magnesium alloy plates (hereinafter referred to as "Mg alloy plates") were also prepared as metal plates other than steel plates.

(Pretreatment process)
The prepared metal plate was degreased with an alkaline degreasing agent "Fine Cleaner E6404" manufactured by Nihon Parkerizing Co., Ltd.
(Chemical conversion processing process)
2.5 g / L of γ-aminopropyltriethoxysilane, 1 g / L of water-dispersed silica (Nissan Chemical Co., Ltd. "Snowtech N", water-soluble acrylic resin (reagent polyacrylic acid)) on a defatted metal plate An aqueous solution to which 3 g / L was added was applied with a bar coater and dried in a hot air oven under the condition that the reaching plate temperature was 150 ° C. Further, a 3 g / L aqueous solution of zirconium carbonate aqueous solution and a chromate treatment solution manufactured by Nippon Parkering Co., Ltd. Similarly, "ZM-1300AN" was also applied with a bar coater and dried in a hot air oven under the condition that the reaching plate temperature was 150 ° C. After that, the product coated with an aqueous solution containing aqueous dispersion silica was treated with "Si-based treatment". (Or simply "Si-based"), "Zr-based treatment" (or simply "Zr-based") coated with an aqueous solution of zirconium carbonate, "Cr-based treatment" (or simply "Cr-based") treated with a chromate treatment solution. It is called "Cr system").

The adhesion amount of each treatment was 30 mg / m ² . The wet coating amount before drying, which is applied to the entire surface of the metal plate, is calculated by [mass of the metal plate after coating]-[mass of the metal plate before coating], and Cr and Si included in the wet coating amount. , Zr, respectively, were calculated and divided by the area of the metal plate. Further, while calculating the adhesion amount by the above-mentioned method, chemical conversion-treated metal plates (dried) having five different adhesion amounts were prepared, and these were measured using fluorescent X-rays, and the obtained detection intensity was calculated. It is also possible to draw a calibration curve from the relationship with the amount of adhesion and obtain the amount of adhesion using this.

(Resin film layer forming process)
Epoxy resin "jER ^(R) 828" manufactured by Mitsubishi Chemical Co., Ltd., urethane-modified epoxy resin "Epokey ^(R) 802-30CX" manufactured by Mitsui Chemicals Co., Ltd., and polyester resin "Byron ^(R) 300" manufactured by Toyobo Co., Ltd. were prepared as binder resins. .. In addition, as a curing agent, Mitsubishi Gas Chemical Company's amine "MXDA (methoxylendiamine)", Ube Kosan Co., Ltd. "1,12-dodecamethylenediamine", Mitsui Chemical Company's melamine "Uban ^(R) 20SB", Daiichi Kogyo A water-based urethane resin "Superflex ^(R) 150" manufactured by Pharmaceutical Co., Ltd. and a melamine resin "Simel ^(R) 325" manufactured by Cytec Co., Ltd. were prepared.

Next, the following film resin samples were prepared by mixing these resins with a curing agent.
-Epoxy resin-A: "jER ^(R) 828" manufactured by Mitsubishi Chemical Corporation was added to 100 parts by mass and 30 parts by mass of "1,12-dodecamethylenediamine" manufactured by Ube Industries, Ltd. was added and mixed.
-Epoxy resin-B: "jER ^(R) 828" manufactured by Mitsubishi Chemical Corporation was added to 100 parts by mass and 30 parts by mass of "MXDA (methxylylenediamine)" manufactured by Mitsubishi Gas Chemical Company was added and mixed.

-Epoxy resin-C: Add 20 parts by mass of "Uban ^(R) 20SB" manufactured by Mitsui Chemicals to 100 parts by mass of solid content of "Epokey ^(R) 802-30CX" manufactured by Mitsui Chemicals, and mix. did.
-Polyester / melamine resin: Toyobo's "Byron ^(R) 300" dissolved in cyclohexanone as a solvent in an amount of 30% by mass, and Mitsui Chemicals' melamine resin "Uban ^(R) 20SB" was added to 100 parts by mass of solid content. 20 parts by mass of solid content was added and mixed.
-Urethane / melamine resin: 80 parts by mass of solid content of water-based urethane resin "Superflex ^(R) 150" manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., and 20 parts by mass of solid content of melamine resin "Simel ^(R) 325" manufactured by Cytec Co., Ltd. Added.

Further, a resin film coating liquid was prepared by mixing the following particles with the prepared resin. The amount of particles added is shown in Table 1 by obtaining the mass ratio of the solid content in the film of the particles to be added to the resin film coating liquid, calculating the volume fraction from the specific gravity of the film resin solid content and the specific gravity of the particles. The volume fraction was adjusted to be the same. For the specific gravity, the catalog value or the literature value of each substance was used.

-Aluminum dihydrogen tripolyphosphate: "K-WHITE # 105" manufactured by TAYCA Corporation, with an average particle size of 1.6 μm (catalog value) was used. Hereinafter, it will be referred to as "Al P acid".

-Strontium chromate: The reagent was rubbed with a mortar and then classified using a sieve to have an average particle size of 3 μm. Hereinafter referred to as "Cr acid Sr".
-Magnesium vanadate: The reagent was rubbed with a mortar and then classified using a sieve to have an average particle size of 3.0 μm, 11.0 μm, 48.0 μm, and 100.0 μm. Hereinafter referred to as "Mg V acid".
-Potassium chromate: A reagent was rubbed with a mortar and then classified using a sieve to have an average particle size of 3.0 μm. Hereinafter referred to as "Cr acid K".
-Calcium chromate: The reagent was rubbed with a mortar and then classified using a sieve to have an average particle size of 3.0 μm. Hereinafter referred to as "Ca acid Cr".
-Potassium dichromate: The reagent was rubbed with a mortar and then classified using a sieve to have an average particle size of 3.0 μm. Hereinafter referred to as "diCr acid K".
-Sodium phosphate: The reagent was rubbed with a mortar and then classified using a sieve to have an average particle size of 3.0 μm. Hereinafter referred to as "Na Pate".
-Calcium hydrogen phosphate: A reagent was rubbed with a mortar and then classified using a sieve to have an average particle size of 3.0 μm. Hereinafter referred to as "Ca Pate".
-Ammonium dihydrogen phosphate: The reagent was rubbed with a mortar and then classified using a sieve to have an average particle size of 3.0 μm. Hereinafter referred to as "P acid NH4".
-Sodium hydrogen pyrophosphate hydrate: The reagent was rubbed with a mortar and then classified using a sieve to have an average particle size of 3.0 μm. Hereinafter referred to as "Na pyropate".
-Calcium vanadate: The reagent was rubbed with a mortar and then classified using a sieve to have an average particle size of 3.0 μm. Hereinafter referred to as "Ca V acid".
-Potassium metavanadate: The reagent was rubbed in a mortar and then classified using a sieve to have an average particle size of 3.0 μm. Hereinafter referred to as "V acid K".

-Alumina: Fine-grained alumina "A-42-2" manufactured by Showa Denko KK used an average particle size (particle size distribution center diameter) of 4.7 μm (catalog value). Hereinafter referred to as "alumina".

-Titanium oxide: "Typake ^(R) CR-95" manufactured by Ishihara Sangyo Co., Ltd., with an average particle size of 0.3 μm (catalog value) was used. Hereinafter referred to as "Ti oxide".
-Conductive titanium oxide: Sn-doped titanium oxide "ET-500W" manufactured by Ishihara Sangyo Co., Ltd. had an average particle size of 2.0 to 3.0 μm (catalog value). Hereinafter referred to as "conductive Ti".
-Talc: A general-purpose talc "P-6" manufactured by Nippon Talc Co., Ltd. was used with an average particle size of 3.3 μm (catalog value). Hereinafter referred to as "talc".
-Kaolin ray: A wet kaolin ray "kaolin ray 5M" manufactured by Takehara Chemical Industry Co., Ltd. was classified using a sieve to have an average particle size of 3.0 μm. Hereinafter referred to as "crate".
-Silica: "AEROSIL ^(R) 50" manufactured by Nippon Aerosil Co., Ltd. was used. When the average particle size was measured with a laser diffraction type particle size distribution measuring device "SALD-2300" manufactured by Shimadzu Corporation, it was less than 0.2 μm.
The above-mentioned alumina, titanium oxide, and silica are oxide particles, which are different from the inorganic salt particles having a rust preventive function. Also, talc and kaolin clay are not inorganic salt particles having a rust preventive function.

Table 1 shows the prepared resin film coating liquids, which are distinguished by the labels "Film-1" to "Film-30". The powder resistivity of the particles in Table 1 is the resistance value when each powder is compressed by 10 MPa at 25 ° C. using the powder resistance measurement system MCP-PD51 manufactured by Mitsubishi Chemical Analytech. The glass transition point was measured by drying and curing these resin film coating liquids in an oven at 200 ° C. for 20 minutes with an automatic differential scanning calorimeter “DSC-60A” manufactured by Shimadzu Corporation.

The prepared resin film coating liquid is partially coated on a metal plate cut to the size required for evaluation with a blade coater on only one side and only the part to which CFRP is attached, and the reaching plate temperature reaches 230 ° C. in 60 seconds. It was dried and cured under the conditions. Partial application is performed by masking the part other than the part to which CFRP is attached in advance with masking tape (using "Nitto Denko ^(R) tape" manufactured by Nitto Denko Corporation ⁾ , applying a resin film layer, and peeling off the masking tape after drying and baking. went.

The film layer thickness was determined by observing the vertical cross section with a microscope using a sample embedded in resin and polished so that the vertical cross section could be observed in advance, and measuring the film layer thickness.

(Thermocompression bonding process)
Crushed bisphenol A type phenoxy resin "Phenototo YP-50S" (Mw = 40,000, hydroxyl group equivalent = 284 g / eq, melt viscosity at 250 ° C. = 90 Pa · s, Tg = 83 ° C.) manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. The classified powder having an average particle diameter D50 of 80 μm is applied to a reinforcing fiber base material (cloth material: manufactured by Toho Tenax Co., Ltd., IMS60) made of carbon fiber under the conditions of an electric charge of 70 kV and a sprayed air pressure of 0.32 MPa in an electrostatic field. Powder coating was performed. Then, the resin is heat-sealed by heating and melting at 170 ° C. for 1 minute in an oven to heat-fuse the resin, and phenoxy having a thickness of 0.65 mm, an elastic modulus of 75 [GPa], a tensile load of 13500 [N], and a Vf (fiber volume content) of 60%. A resin CFRP prepreg was prepared. The size of the prepreg was the same as that of the metal plate.

The average particle size of the pulverized and classified phenoxy resin is the particle size when the cumulative volume is 50% on a volume basis by a laser diffraction / scattering type particle size distribution measuring device (Microtrack MT3300EX, manufactured by Nikkiso Co., Ltd.). It was measured.

Next, the prepared prepreg was placed on a metal plate on which a resin film layer was laminated, and pressed at 3 MPa for 3 minutes with a press machine having a flat mold heated to 250 ° C. to form a composite as shown in Tables 2 and 3. A metal-CFRP composite was prepared as a body sample.

<Evaluation>
1. 1. Corrosion resistance Using the prepared composite sample having a width of 70 mm and a length of 150 mm, degreasing, surface adjustment, and zinc phosphate treatment were performed, and then electrodeposition coating was applied. For degreasing, a degreasing agent "Fine Cleaner E6408" manufactured by Nihon Parkerizing Co., Ltd. was used and immersed for 5 minutes at 60 ° C. for degreasing. The degreased sample was immersed for 5 minutes at 40 ° C. using "Preparen X" manufactured by Nihon Parkerizing Co., Ltd. for surface adjustment. Then, zinc phosphate treatment was performed by immersing the zinc phosphate chemical agent "Palbond L3065" manufactured by Nihon Parkerizing Co., Ltd. at 35 ° C. for 3 minutes. After the zinc phosphate treatment, it was washed with water and dried in an oven at 150 ° C. Then, the electrodeposition paint "Power Float 1200" manufactured by Nippon Paint Co., Ltd. was electrodeposited by 15 μm and baked in an oven at 170 ° C. for 20 minutes as a sample. The electrodeposition coating was applied only to the metal part to which CFRP was not attached.

A cycle corrosion test (CCT) was performed using the prepared sample. The CCT mode was performed according to the automobile industry standard JASO-M609. The sample was tested by installing it on a testing machine so that salt water was sprayed on the evaluation surface with the CFRP side as the evaluation surface.
In the test, the appearance of the sample was visually observed every 15 cycles (1 cycle in 8 hours), and the cycle in which red rust occurred was determined. The larger the number of cycles until red rust occurs, the better the corrosion resistance. In addition, since red rust is generated near the edge of the CFRP attached to the metal, we focused on that and observed it. When the metal plates used were an aluminum alloy plate and a magnesium alloy plate, red rust, which is an oxide of iron, does not occur, so the number of cycles in which white rust, which is an oxide of aluminum or magnesium, occurs was determined.

The corrosion resistance differs depending on the metal plate used. Therefore, the evaluation of corrosion resistance was carried out by setting a standard for each type of metal plate. Specifically, when a cold-rolled steel sheet (CR) is used, if red rust occurs in 30 cycles or less, it is a rejected product, and if it is not, it is a passed product.
When a plated steel sheet (GI) is used, if red rust occurs in 60 cycles or less, it is a rejected product, and if it is not, it is a passed product.
When a plated steel sheet (GA) is used, if red rust occurs in 60 cycles or less, it is a rejected product, and if it is not, it is a passed product.
When a plated steel sheet (Zn-Al-Mg) is used, if red rust occurs in 90 cycles or less, it is a rejected product, and if it is not, it is a passed product.
When a plated steel sheet (Zn-Al-Mg-Si) is used, if red rust occurs in 120 cycles or less, it is a rejected product, and if it is not, it is a passed product.
When an aluminum alloy plate (Al plate) is used, if white rust occurs in 120 cycles or less, it is a rejected product, and if it is not, it is a passed product.
When a magnesium alloy plate (Mg alloy plate) was used, the case where white rust occurred in 120 cycles or less was evaluated as a rejected product, and the other cases were evaluated as a passed product.

2.3 Point bending test A composite sample with a width of 30 mm and a length of 100 mm was used for the test. For this sample, CFRP was attached to the entire surface of one side of a metal plate. A three-point bending test was performed by placing the sample on a jig having a distance between fulcrums of 60 mm and applying a load near the center between the fulcrums. The sample was placed on the jig so that the load-applied side was on the CFRP side and tested. In a three-point bending test, the peeling state of the metal plate and CFRP when the sample was bent when a load was applied was observed and evaluated. The peeling state differs depending on the sample, and there are "no peeling", "slightly peeling" of the deformed part, and "large peeling" of CFRP completely peeling from the metal plate. , These were evaluated.

3. 3. Press workability The press workability in hot working in a state where a V-shaped uneven die was heated to 200 ° C. was tested using a composite sample having a width of 50 mm and a length of 50 mm. In this sample, CFRP was attached to the entire surface of one side of a metal plate, and the concave mold side was set to CFRP and the convex mold side was to be a metal material, and the die was pressed. The angle of the V part of the V-shaped die was 90 °, and press working was performed using dies with different R (radius of curvature) of the bent part to determine the limit R at which CFRP does not peel off. .. The smaller the bending R, the better the press formability.

The above evaluation results are shown in Tables 2 to 4 together with the composition of the complex sample.

From this result, when the same kind of metal plate is used, the metal-CFRP composite of the present invention is superior in corrosion resistance to contact corrosion of different materials between carbon fiber and metal as compared with the composite of Comparative Example. Moreover, the CFRP was not easily peeled off even when a bending test or a hot press was performed, which was excellent.

Although the preferred embodiments of the present invention have been described in detail with reference to the accompanying drawings, the present invention is not limited to such examples. It is clear that a person having ordinary knowledge in the field of technology to which the present invention belongs can come up with various modifications or modifications within the scope of the technical ideas described in the claims. , These are also naturally understood to belong to the technical scope of the present invention.

1,1A, 1B, 1C, 1D, 1E Metal-

CFRP composite

11, 11A,

11B Metal member

12, 12A, 12B, 12C CFRP layer 121 Carbon fiber material 123

Matrix resin

13, 13A, 13B Resin film layer 131 Inorganic salt Particle 133 Binder resin 14 Chemical conversion treatment layer

Claims

With metal parts
A resin film layer arranged on at least a part of the surface of the metal member,
It has a matrix resin and a carbon fiber reinforced resin material containing a carbon fiber material existing in the matrix resin, which is arranged on the resin film layer.
The resin film layer, a powder resistivity at 23 ~ 27 ° C. is the 7.0 × 10 7 Ωcm greater, and has a rust function, Cr, one or more elements selected from P and V It contains inorganic salt particles composed of inorganic salts, and further contains a binder resin.
A metal-carbon fiber reinforced resin material composite in which the volume fraction of the inorganic salt particles in the resin film layer is 5.0% or more and 40.0% or less.
The inorganic salt comprises chromate ion, dichromate ion, phosphate ion, hydrogen phosphate ion, dihydrogen phosphate ion, diphosphate ion, triphosphate ion, orthovanadate ion, and metavanadate ion. The metal-carbon fiber reinforced resin material composite according to claim 1, which comprises a salt of one or more ions selected from the group.
Claimed that the inorganic salt comprises one or more selected from the group consisting of aluminum dihydrogen tripolyphosphate, strontium chromate, potassium chromate, calcium chromate, magnesium vanadate, potassium vanadate, and calcium vanadate. The metal-carbon fiber reinforced resin material composite according to 1 or 2.
The metal-carbon fiber reinforced resin material composite according to any one of claims 1 to 3, wherein the average thickness of the resin film layer is 5.0 μm or more.
The metal-carbon fiber reinforced resin material composite according to any one of claims 1 to 4, wherein the average particle size of the inorganic salt particles is 0.2 μm or more and 50.0 μm or less.
The metal-carbon fiber reinforced resin material composite according to any one of claims 1 to 5, wherein the glass transition temperature of the resin film layer is 100 ° C. or lower.
The metal-carbon fiber reinforced resin material composite according to any one of claims 1 to 6, wherein the matrix resin contains a thermoplastic resin.
The metal-carbon fiber reinforced resin material composite according to any one of claims 1 to 7, wherein the matrix resin contains a phenoxy resin.
The metal-carbon fiber reinforced according to any one of claims 1 to 8, wherein the binder resin contains one or more selected from the group consisting of urethane resin, epoxy resin, polyester resin and melamine resin. Resin material composite.
The metal-carbon fiber reinforced resin material composite according to any one of claims 1 to 9, wherein the metal member is a steel material or a plated steel material.
A step of thermocompression bonding a metal member provided with a resin film layer on at least a part of the surface and a carbon fiber reinforced resin material via the resin film layer is provided.
The carbon fiber reinforced resin material includes a matrix resin and a carbon fiber material present in the matrix resin.
The resin film layer, a powder resistivity at 23 ~ 27 ° C. is the 7.0 × 10 7 Ωcm greater, and has a rust function, Cr, one or more elements selected from P and V Contains inorganic salt particles composed of inorganic salts, and further contains a binder resin.
A method for producing a metal-carbon fiber reinforced resin material composite, wherein the volume fraction of the inorganic salt particles in the resin film layer is 5.0% or more and 40.0% or less.
The method for producing a metal-carbon fiber reinforced resin material composite according to claim 11, further comprising a step of molding the metal member before the thermocompression bonding step.
The method for producing a metal-carbon fiber reinforced resin material composite according to claim 11, further comprising a step of forming a laminate in which the metal member and the carbon fiber reinforced resin material are laminated after the thermocompression bonding step. ..