WO2020202462A1

WO2020202462A1 - Composite of metal and carbon-fiber-reinforced resin material and method for manufacturing composite of metal and carbon-fiber-reinforced resin material

Info

Publication number: WO2020202462A1
Application number: PCT/JP2019/014608
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: JPWO2020202462A1; JP7147965B2

Abstract

[Problem] To sufficiently suppress corrosion of metal members, in particular corrosion from contact with dissimilar material. [Solution] This composite of metal and carbon-fiber-reinforced resin material comprises: a metal member; and a carbon-fiber-reinforced resin material that contains a prescribed matrix resin positioned on at least part of the surface of the metal member, carbon fiber material present in the matrix resin, and inorganic salt particles that have a powder resistivity at 23–27°C of more than 7.0 × 10⁷ [Ω·cm], have an anti-corrosion function, and comprise at least one type of element selected from the group consisting of Cr, P, and V.

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 different materials) may occur. In order to prevent such contact corrosion of different materials, some proposals have been made conventionally.

For example, Patent Document 1 below 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. Has been done.

Further, Patent Document 2 below 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. The following 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, in the molded product proposed in Patent Document 1, the surface of the carbon fiber reinforced resin molded product is provided with water repellency by silicone, and the conduction between the carbon fiber and the metal part is not prevented. Therefore, it is difficult to sufficiently suppress contact corrosion of dissimilar materials. Further, the techniques proposed in 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. ..

Therefore, the present invention has been made in view of the above problems, and an object of the present invention is a metal-carbon fiber capable of sufficiently suppressing corrosion of metal members, particularly contact corrosion of dissimilar materials. It is an object of the present invention to provide a method for producing a 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 found a predetermined inorganic salt having high electrical resistance and excellent insulating properties in the carbon fiber reinforced resin material. By directly containing the inorganic salt particles to function as a spacer, it is possible to prevent the carbon fibers contained in the carbon fiber reinforced resin material from coming into contact with the metal member, and the above-mentioned inorganic salt particles can be prevented from coming into contact with the metal member in a corrosive environment. It was found that it is possible to improve the insulating property between the carbon fiber and the metal material and also to improve the corrosion resistance of the carbon fiber reinforced resin material itself by melting and depositing on the carbon fiber, and completed the present invention. It was.
The gist of the present invention completed based on the above findings is as follows.

[1] The metal member, the carbon fiber material located at least a part of the surface of the metal member, the predetermined matrix resin, and the carbon fiber material existing in the matrix resin, and the powder resistance at 23 to 27 ° C. 7.0 × 10 7 a ^[Ω · cm] greater, and has a rust function, Cr, containing P, and the inorganic salt particles made of inorganic salts of one or more elements selected from V, and A metal-carbon fiber reinforced resin material composite comprising a carbon fiber reinforced resin material.
[2] The inorganic salt particles are chromate ion, dichromate ion, phosphate ion, hydrogen phosphate ion, dihydrogen phosphate ion, diphosphate ion, triphosphate ion, orthovanadate ion, metavanadate ion. The metal-carbon fiber reinforced resin material composite according to [1], which comprises an inorganic salt of one or more ions selected from the group consisting of.
[3] The inorganic salt particles are selected from one or more selected from the group consisting of aluminum dihydrogen tripolyphosphate, strontium chromate, potassium chromate, calcium chromate, potassium vanadate, magnesium vanadate, and calcium vanadate. The metal-carbon fiber reinforced resin material composite according to [1] or [2].
[4] When the average thickness of the fiber bundle of the carbon fiber material is D [μm] and the average particle size of the inorganic salt particles is r [μm], the relationship of D / r ≧ 10 is satisfied. The metal-carbon fiber reinforced resin material composite according to any one of [1] to [3].
[5] The metal-carbon fiber reinforced resin material composite according to any one of [1] to [4], wherein the average particle size of the inorganic salt particles is 0.10 μm or more and 10.00 μm or less.
[6] The metal-carbon fiber reinforced resin material according to any one of [1] to [5], wherein the volume ratio of the inorganic salt particles in the carbon fiber reinforced resin material is 5% or more and 30% or less. Complex.
[7] The metal-carbon fiber reinforced according to any one of [1] to [6], wherein the reinforced fiber density (Volume Fraction: VF) of the carbon fiber reinforced resin material is 30% or more and 70% or less. Resin material composite.
[8] The metal-carbon fiber reinforced resin material composite according to any one of [1] to [7], wherein the matrix resin contains a thermoplastic resin.
[9] The metal-carbon fiber reinforced resin material composite according to any one of [1] to [8], wherein the matrix resin contains a phenoxy resin.
[10] The metal-carbon fiber reinforced resin material composite according to any one of [1] to [9], wherein the material of the metal member is a steel material, an iron-based alloy, titanium or aluminum.
[11] The metal-carbon fiber reinforced resin material composite according to [10], wherein the steel material is a plated steel material.
[12] on at least one surface of the metal member, and a matrix resin, and the carbon fiber material, the powder resistivity at 23 ~ 27 ° C. is ^{7.0 × 10 7 [Ω · cm} ] greater, and proof A carbon fiber reinforced resin material containing inorganic salt particles composed of an inorganic salt of one or more elements selected from Cr, P, and V having a rust function, or the matrix resin and the carbon fiber material. After arranging the carbon fiber reinforced resin material prepreg containing the inorganic salt particles, the metal member and the carbon fiber reinforced resin material or the carbon fiber reinforced resin material prepreg are heat-bonded to each other. A method for producing a carbon fiber reinforced resin material composite.
[13] The metal-carbon fiber reinforced according to [12], wherein the metal member is processed into a predetermined shape prior to the arrangement of the carbon fiber reinforced resin material or the carbon fiber reinforced resin material prepreg. A method for producing a resin material composite.
[14] After the metal member and the carbon fiber reinforced resin material or the carbon fiber reinforced resin material prepreg are heat-bonded, the obtained heat-bonded body is processed into a predetermined shape, according to [12]. The method for producing a metal-carbon fiber reinforced resin material composite according to the above method.

As described above, according to the present invention, it is possible to sufficiently suppress corrosion of metal members, particularly contact corrosion of dissimilar materials.

It is a schematic diagram which shows the cross-sectional structure of the metal-fiber reinforced resin material composite which concerns on embodiment of this invention. It is a schematic diagram which shows the cross-sectional structure of another aspect of the metal-fiber reinforced resin material composite which concerns on this embodiment. It is explanatory drawing for demonstrating the thickness measurement method. It is explanatory drawing which shows an example of the manufacturing process of the metal-fiber reinforced resin material composite which concerns on this embodiment.

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.

(Embodiment)
<Structure of metal-carbon fiber reinforced resin material composite>
First, the configuration of the metal-fiber reinforced resin material composite according to the first embodiment of the present invention will be described with reference to FIGS. 1 and 2. 1 and 2 are schematic views showing a cross-sectional structure of the metal-carbon fiber reinforced resin material composite 1 as an example of the metal-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 10 and a carbon fiber reinforced resin material (CFRP layer) 20. The metal member 10 and the CFRP layer 20 are composited with each other. Here, "composite" means that the metal member 10 and the CFRP layer 20 are joined (bonded) to each other and integrated. Further, "integration" means that the metal member 10 and the CFRP layer 20 move as one body during processing or deformation.

In the present embodiment, CFRP layer 20 has a predetermined matrix resin, the carbon fiber material present in the matrix resin, 23-27 powder resistivity at ℃ is 7.0 × 10 ⁷ [Ω · cm ] It contains inorganic salt particles composed of an inorganic salt of one or more elements selected from Cr, P, and V, which are super and have a rust preventive function. As a result, the corrosion resistance of the metal-CFRP composite 1 according to the present embodiment, particularly the corrosion resistance related to contact corrosion of dissimilar materials, is improved.
Hereinafter, each configuration of the metal-CFRP composite 1 will be described in detail.

[About metal member 10]
The material, shape, thickness, and the like of the metal member 10 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 10 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-based alloys, and the like. The material of the metal member 10 is preferably a steel material, an iron-based alloy, titanium and aluminum, and more preferably a steel material having a higher elastic modulus than other metal 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 plating may be applied to the steel material. Here, the plating may be, for example, various platings such as galvanization and aluminum plating, alloying of platings, and a plurality of types of surface treatments, for example, chemical conversion treatments. 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 subjected to the zinc-based plating treatment is particularly preferable because it has excellent corrosion resistance. Particularly preferable plated steel materials as the metal member 10 include, for example, hot-dip galvanized steel sheets, galvanized steel sheets, or alloyed hot-dip zinc alloyed by heat-treating these plated steel sheets and diffusing Fe during zinc plating. Hot-dip Zn-Al alloy-plated steel sheets, hot-dip Zn-1 Hot-dip Zn-Al-Mg alloy-plated steel sheets, Ni-plated steel sheets, represented by ~ 12% Al-1-4% Mg alloy-plated steel sheets and hot-dip 55% Al-Zn-0.1-3% Mg alloy-plated steel sheets 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 heat-treating a plated steel sheet and diffusing Fe during Ni plating. Among these plated steel sheets, galvanized steel sheets are suitable because of their excellent corrosion resistance. Further, the Zn—Al—Mg alloy plated steel sheet is more suitable because it is more excellent in corrosion resistance.

The thickness of the metal member 10 according to the present embodiment is not particularly limited, but is, for example, 0.1 to 10.0 mm depending on the strength required for the metal-CFRP composite 1 and the allowable thickness. It is preferable to set the degree.

Here, in order to improve the adhesiveness between the metal member 10 and the CFRP layer 20, the surface of the metal member 10 is preferably treated by chemical conversion treatment. The film formed on the surface of the metal member 10 by the chemical conversion treatment preferably contains Cr, P, Si and / or Zr. As a result, the corrosion resistance of the metal member 10 is further improved, and the adhesion between the metal member 10 and the CFRP layer 20 is further improved.
As the chemical conversion treatment, what is called chromate treatment or chromate-free treatment is preferable. The chromate treatment is a treatment for forming a film based on chromium oxide, and is suitable because the adhesion to the adhesive is excellent when silica is added. The chromate-free treatment is a treatment for forming a treatment film mainly composed of a resin, a treatment for forming an inorganic film containing a zirconium bond or a siloxane bond, or a treatment for forming an organic / inorganic composite film. In order to obtain a film containing a zirconium bond, it is preferable to treat with a treatment liquid containing zirconate. In order to obtain a film containing a siloxane bond, it is preferable to treat with a silane coupling agent. Further, it may be treated with a triazine thiol derivative. Examples of the silane coupling agent include generally known silane coupling agents such as γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, and γ- (2-aminoethyl). Aminoethyl) Aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropylmethyldiethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacry Loxypropylmethyldimethoxysilane, 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, dimethyldi Ethoxysilane, vinyl triacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropylmethyldiethoxysilane, hexamethyldisilazane, γ-anilino Propyltrimethoxysilane, γ-anilinopropylmethyldimethoxysilane, γ-anilinopropyltriethoxysilane, γ-anilinopropylmethyldiethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyltriethoxysilane, vinylmethyl Diethoxysilane, 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 , Methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane and the like. When a silane coupling agent having a glycidyl ether group (for example, γ-glycidoxypropyltrimethoxysilane and γ-glycidoxypropyltriethoxysilane having a glycidyl ether group) is used, the process adhesion of the coating film is particularly high. improves. Further, when a triethoxy type silane coupling agent is used, the storage stability of the base treatment agent 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.

[About CFRP layer 20]
CFRP layer 20 includes a matrix resin 201, is contained in such a matrix resin 201, a carbon fiber material 203 which is complexed, 23-27 powder resistivity at ℃ is ^{7.0 × 10 7 [Ω · cm} ] It has inorganic salt particles 205 composed of an inorganic salt of one or more elements selected from Cr, P, and V, which are super and have a rust preventive function.

In the CFRP layer 20 according to the present embodiment, the matrix resin 201 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 201, both a thermosetting resin and a thermoplastic resin can be used, but it is preferable that the thermoplastic resin is the main component. The type of thermoplastic resin that can be used for the matrix resin 201 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 polyester, polycarbonate, polyimide, polyamide, polyamideimide, polyetherimide, polyethersulfone, polyphenylene ether and its modifications, polyphenylene sulfide, polyoxymethylene, polyarylate, polyetherketone, polyetheretherketone, etc. , 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 201, 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 201 contains a thermoplastic resin, there are problems when a thermosetting resin is used as the matrix resin of CFRP, that is, the CFRP layer 20 has brittleness, the tact time is long, and bending. Problems such as inability to process can be solved. However, since the thermoplastic resin usually has a high viscosity when melted and cannot be impregnated into the carbon fiber material 203 in a low viscosity state like a thermosetting resin such as an epoxy resin before thermosetting. Poor impregnation property with respect to carbon fiber material 203. Therefore, unlike the case where the thermosetting resin is used as the matrix resin 201, the reinforcing fiber density (VF: Volume Fraction) in the CFRP layer 20 cannot be increased. For example, when an epoxy resin is used as the matrix resin 201, the VF can be about 60%, but when a thermoplastic resin such as polypropylene or nylon is used as the matrix resin 201, the VF is 50%. It will be about. Further, when a thermoplastic resin such as polypropylene or nylon is used, the CFRP layer 20 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 201. 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 10. 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 201, it is possible to obtain a matrix resin having excellent impregnation property into the carbon fiber material 203. Furthermore, by thermosetting the cured component in this partially curable resin, it is possible to prevent the matrix resin 201 in the CFRP layer 20 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 203, the brittleness of the CFRP layer 20, the tact time, the processability, and the like. As described above, by using the phenoxy resin as the matrix resin 201, 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 203 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 201. 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 203 and the metal member 10, 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, 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 as the resin component of the matrix resin 201. By using such a resin composition, the metal member 10 can be firmly joined. 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 using infrared spectroscopy (IR: Infrared spectroscopy) as described below, and the content ratio of the phenoxy resin can be determined from the resin composition targeted by infrared spectroscopy. When analyzing, it can be measured by using a general method of infrared spectroscopic analysis such as a transmission method or an ATR reflection method.

The CFRP layer 20 is carved out with a sharp blade or the like, fibers and granules are removed as much as possible with tweezers or the like, and the resin composition to be analyzed is sampled from the CFRP layer 20. 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 (Wavember) 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 is present in e.g. ¹⁴⁵⁰ ~ ^1480cm ^-1, 1500cm -1 vicinity, 1600 cm ^-1 vicinity like. Therefore, the content of the phenoxy resin is calculated based on the calibration curve prepared in advance showing the relationship between the intensity of the absorption peak and the content of the phenoxy resin and the measured intensity of the absorption peak. It is possible to do.

Here, the "phenoxy resin" is a linear polymer obtained from a condensation reaction between a divalent phenol compound and epihalohydrin or a polyaddition reaction between a divalent phenol compound and a bifunctional epoxy resin, and is amorphous. It is a thermoplastic resin. 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 within the range of 10,000 or more, the strength of the molded product can be increased, and this effect can be further achieved by setting the Mw to 20,000 or more, further 30,000 or more. Increase. On the other hand, by setting the Mw of the phenoxy resin to 200,000 or less, it is possible to improve workability and workability, and this effect is to set the Mw to 100,000 or less, and 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, further 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 CFRP layer 20 can be sufficiently secured. On the other hand, when the Tg is 150 ° C. or lower, the melt viscosity becomes low, so that the reinforcing 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 & Sumitomo Metal Chemical Co., Ltd.), bisphenol A and bisphenol F copolymerized phenoxy resin (for example, Nippon Steel & Sumitomo Metal) 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 201 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 20. On the other hand, when the melt viscosity is 90 Pa · s or more, the resin composition has a molecular weight that does not cause embrittlement, and the mechanical strength of the metal-CFRP composite 1 can be maintained. ..

Further, the resin composition constituting the matrix resin 201 may be a mixture of the above-mentioned resin composition and a crosslinkable resin composition. 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)"). You can also do it. 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 20 can be improved. Further, when the melt viscosity at 150 ° C. is 2.0 Pa · s or less, the moldability of the crosslinkable resin composition can be improved, 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 10 and the CFRP layer 20 can be easily peeled off. Therefore, the metal member 10 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 reacting the phenoxy resin (A) with the cross-linking agent (C), but the coexistence of the epoxy resin can reduce the melt viscosity of the resin composition, so that the resin composition can be combined with the adherend. It exhibits excellent properties such as improved impregnation property, accelerated cross-linking reaction, improved cross-linking density, and improved 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 20 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 determined by similarly measuring the peak derived from the epoxy resin by the method using infrared spectroscopy as described above, thereby containing the crosslinkable resin (B). The amount can be measured.

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 contained. 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 phosphines 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 201, 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 mass 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 20, 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 201 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.

The carbon fiber material 203 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 203, one type of the above-mentioned fibers may be used alone, or a plurality of types may be used in combination.

In the CFRP used for the CFRP layer 20, the reinforcing fiber base material used as the base material of the carbon fiber material 203 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.

CFRP layer 20 according to this embodiment, the powder resistivity at 23 ~ 27 ° C. is ^{7.0 × 10 7 [Ω · cm} ] greater, and has a rust function, Cr, P, and from V It contains an inorganic salt particle 205 composed of an inorganic salt of one or more selected elements. Since the inorganic salt particles 205 having the above-mentioned insulating properties are present in the CFRP layer 20, the corrosion resistance of the CFRP layer 20 itself is also improved. Here, when the average thickness of the fiber bundle of the carbon fiber material 203 is D [μm] and the average particle size of the inorganic salt particles is r [μm], the relationship of D / r ≧ 10 is satisfied. Suitable.

To explain in more detail, in general, the CFRP layer and the metal member are joined by thermocompression bonding. 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 comes into contact with the metal member, 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 205 having a relatively low conductivity are CFRP so that the carbon fiber material 203 protruding from the surface of the CFRP layer 20 does not come into contact with the metal member 10. It is contained in the layer 20. That is, the inorganic salt particles 205 having relatively low conductivity act as a spacer between the carbon fiber material 203 and the metal member 10, and can insulate between the carbon fiber material 203 and the metal member 10. Further, in a corrosive environment, the inorganic salt particles are dissolved and deposited on the carbon fiber material 203 to improve the insulating property between the carbon fiber material 203 and the metal member 10, and the carbon fiber reinforced resin material itself Corrosion resistance can also be improved.

Further, when the average thickness D of the fiber bundle of the carbon fiber material 203 and the average particle size r of the inorganic salt particles 205 satisfy the relationship of D / r ≧ 10, the inorganic salt particles 205 to be blended are formed. It is prevented from protruding from the surface of the CFRP layer 20, and the adhesion between the metal member 10 and the CFRP layer 20 and the adhesion between the matrix resin 201 of the CFRP layer 20 and the carbon fiber material 203 are ensured. On the other hand, the smaller the D / r value, the more effective the adhesion. The upper limit is not particularly specified, but considering the lower limit of the particle size of the inorganic salt particles, it is preferable that 10000> D / r.

Further, the average particle size of the above-mentioned inorganic salt particles is preferably 0.10 μm or more and 10.00 μm or less. When the average particle size is 0.10 μm or more, the effect on corrosion resistance can be improved, and when the average particle size is 10.00 μm or less, the adhesion between the metal member 10 and the CFRP layer 20 and Sufficient adhesion between the matrix resin 201 in the CFRP layer 20 and the carbon fiber material 203 can be ensured. Further, when the average particle size is 10.00 μm or less, the total surface area of the inorganic salt particles 205 contained in the CFRP layer 20 is large enough to elute components that contribute to corrosion suppression in a corrosive environment. Become.

The above average particle size means the particle size at an integrated value of 50% in the particle size distribution obtained by the laser diffraction / scattering method.

The volume fraction of the inorganic salt particles 205 in the CFRP layer 20 is, for example, preferably 5% or more and 30% or less, and more preferably 10% or more and 20% or less. When the volume ratio of the inorganic salt particles 205 is within the above range, the contact corrosion between the metal member 10 and the carbon fiber material 203 is more effectively performed while ensuring the adhesion between the CFRP layer 20 and the metal member 10. It becomes possible to prevent it.

Further, the reinforcing fiber density VF of the CFRP layer 20 is preferably 30% or more and 70% or less, and more preferably 40% or more and 60% or less. When the reinforcing fiber density VF of the CFRP layer 20 is within the above range, the CFRP layer 20 can more reliably realize the desired mechanical strength.

Powder resistivity at 23 ~ 27 ° C. of the inorganic salt particles 205 as described above, as described above, is ^{7.0 × 10 7 [Ω · cm} ] greater. Since the conductivity of the inorganic salt particles 205 is relatively small as described above, the inorganic salt particles 205 function as a spacer having an insulating property between the carbon fiber material 203 and the metal member 10. As a result, electrolytic corrosion is suppressed without conducting conduction between the carbon fiber material 203 and the metal member 10. In contrast, when the powder resistivity at 23 ~ 27 ° C. of the inorganic salt particles 205 is ^{7.0 × 10 7 [Ω · cm} ] or less, a carbon fiber material 203 and the metal member 10 and the inorganic salt particles It becomes easy to conduct through 205, and electrolytic corrosion cannot be suppressed. Here, the upper limit value of the powder resistivity is not particularly specified, and the larger the value of the powder resistivity, the more preferable.

The powder resistivity of the inorganic salt particles 205 at 23 to 27 ° C. was determined by using a commercially available powder resistance measuring machine (for example, "powder resistance measuring system MCP-PD51 type" manufactured by Mitsubishi Chemical Analytech Co., Ltd.). It can be obtained by measuring the resistance of the powder particles compressed at 10 MPa. Further, in general, the powder resistivity can be regarded as equivalent to the volume resistivity of the material itself of the inorganic salt particles to be measured.

The inorganic salt particles 205 in the CFRP layer 20 have the above-mentioned powder resistance and rust preventive function, and are composed of an inorganic salt of one or more elements selected from Cr, P, and V. If there is no particular limitation, it is more preferable to use an inorganic salt composed of an inorganic salt of one or more elements selected from Cr, P, and V, which is effective in corrosion resistance. Cr, P, and V are likely to be deposited on the surfaces of the metal member 10 as the anode and the carbon fiber material 203 as the cathode when dissolved as ions in a corrosive environment, and are effective in corrosion resistance. Since such an inorganic salt functions as an excellent rust preventive material, it is possible to more reliably improve the corrosion resistance of the CFRP layer 20.

As the inorganic salt constituting the inorganic salt particles 205 having the rust preventive function according to the present embodiment, for example, the above-mentioned inorganic salt of oxo acid containing a metal element can be used. The inorganic salt containing Cr, chromate ions _(CrO ^{4 2-),} dichromate ion _(Cr ^{₂ O 7 2-),} and salts of oxo acid ions of Cr and the like. 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-),} pyrovanadates ion _(V ₂ ^{O 7 4-),} metavanadate ion _([VO ^{_3] n n-)}
And the salt of V oxoacid ion.
The inorganic salt particles 205 may be composed of one kind of salt of each of the above-mentioned oxoacid ions, or may be made of a plurality of kinds.

Among the above, the inorganic salt particles are described 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 contained in the 205, chromate ion _(CrO ^{4 2-),} phosphate ion _(PO ^{4 3-),} triphosphate ions _(P _{3 O} ^{10 5-,} "tripolyphosphate"), orthovanadate ion It preferably consists of one or more salts selected from the group consisting of (VO ₄ ^3- ), pyrovanadic acid ion (V ₂ O ₇ ^4- ), 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 salt particles 205 is selected from the group consisting of Ca, 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.

As a specific example of such inorganic salt particles 205, examples of the inorganic salt include chromates such as potassium chromate, calcium chromate, and strontium chromate, zinc phosphate, aluminum phosphate, aluminum tripolyphosphate, and sodium phosphate. Phosphates such as magnesium phosphate and trimagnesium phosphate, molybdates such as potassium molybdate and calcium molybdate, vanadates such as sodium metavanadate, calcium vanadate, magnesium vanadate, calcium tungstate, tungstate Tungstates such as sodium and tungstate can be used.

Among the above, more preferably, the inorganic salt particles 205 are prepared as inorganic salts such as aluminum dihydrogen tripolyphosphate, strontium chromate, and calcium chromate, from the viewpoint of elution of fine particles in the resin matrix in a corrosive environment. It is preferably one or more selected from the group consisting of potassium chromate, magnesium vanadate, potassium vanadate, and calcium vanadate.

Instead of the CFRP layer 20 containing the inorganic salt particles 205, a metal oxide layer having low conductivity may be formed between the metal member and the CFRP layer without including the inorganic salt particles in the CFRP layer 20. Conceivable. However, in this case, while the insulating property between the metal member and the carbon fiber material can be ensured, the processability of the metal-CFRP composite itself is lowered, and the composite between the metal member and the CFRP layer is formed. Not enough benefits.

The configuration of the metal-CFRP composite 1 according to the present embodiment has been described in detail above.

In the above description, the case where the CFRP layer 20 is arranged on one side of the metal member 10 has been given as an example, but the present invention is not limited to this. For example, in the metal-CFRP composite 1, CFRP layers 20 may be arranged on both sides of the metal member 10. Further, in this case, the configurations of the CFRP layers 20 may be different from each other or may be the same.

Further, the CFRP layer 20 is not limited to the example shown in the above description, and may be a plurality of layers. For example, as in the metal-CFRP composite 1 shown in FIG. 2, the CFRP layer 20 is not limited to one layer, and may be two or more layers. When the CFRP layer 20 is a plurality of layers, the number n of the CFRP layer 20 may be appropriately set according to the purpose of use. When there are a plurality of CFRP layers 20, each layer may have the same configuration or may be different. That is, the resin type of the matrix resin 201 constituting the CFRP layer 20, the type and content ratio of the carbon fiber material 203, the type and content ratio of the inorganic salt particles 205, and the like may be different for each layer.

Further, in the above description, the case where the metal-CFRP composite 1 is plate-shaped has been taken up, but the present invention is not limited to this, and of course, the metal-CFRP composite according to the present invention may be molded. ..

(About the method of measuring the thickness of each layer)
A method for measuring the thickness of the metal member 10 and the CFRP layer 20 will be briefly described with reference to FIG. FIG. 3 is an explanatory diagram for explaining a method of measuring the thickness.

The thickness of the metal member 10 and the CFRP layer 20 can be measured, for example, in accordance with the cross-sectional method of the optical method of JIS K 560-1-7, 5.4 as follows. That is, using a room temperature curing resin that can be embedded without any harmful effect on the sample, using 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, when measuring the thickness of the CFRP layer 20, the observation field of view is divided into four equal parts as shown in FIG. 3, the thickness of the CFRP layer 20 is measured at the center of each fraction in the width direction, and the average thereof is measured. Let the thickness of be 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 CFRP layer 20 may be obtained by further averaging the average values at these five locations. Further, the thickness of the metal member 10 may be measured in the same manner as the measurement of the thickness of the CFRP layer 20.

<Manufacturing method of metal-carbon fiber reinforced resin material composite>
Hereinafter, the method for producing the metal-carbon fiber reinforced resin material composite according to the present embodiment will be described in detail with reference to FIG. FIG. 4 is an explanatory diagram showing an example of a manufacturing process of the metal-fiber reinforced resin material composite according to the present embodiment.

The method for producing the metal-CFRP composite 1 according to the present embodiment is as follows: (1) On at least one surface of the metal member, a matrix resin, a carbon fiber material, and a powder resistance at 23 to 27 ° C. are 7. Carbon containing an inorganic salt particle composed of an inorganic salt of one or more elements selected from Cr, P, and V, which is more than 0 × 10 ⁷ [Ω · cm] and has a rust preventive function. A step of arranging a carbon fiber reinforced resin material prepreg containing a fiber reinforced resin material or the matrix resin, the carbon fiber material, and the inorganic salt particles, and (2) a metal member and a carbon fiber reinforced resin. Includes a step of heat-pressing the material or carbon fiber reinforced resin material prepreg. Through this step, the carbon fiber reinforced resin material prepreg becomes a carbon fiber reinforced resin material (CFRP layer 20). As a result, the metal member 10 and the carbon fiber reinforced resin material or the carbon fiber reinforced resin material prepreg are combined with each other to form the metal-CFRP composite 1 according to the present embodiment.

At this time, the metal member may be processed into a predetermined shape prior to the arrangement of the carbon fiber reinforced resin material or the carbon fiber reinforced resin material prepreg. Further, after the metal member and the carbon fiber reinforced resin material or the carbon fiber reinforced resin material prepreg are thermocompression bonded, the obtained thermocompression bonded body may be processed into a predetermined shape.

In the manufacturing method according to the present embodiment, for example, CFRP or CFRP molding prepreg 25 to be the CFRP layer 20 is laminated on the metal member 10 and heat-bonded. Here, the CFRP or CFRP molding prepreg 25 contains the matrix resin 201, the carbon fiber material 203, and the inorganic salt particles 205 having the above-mentioned insulating properties.

In such a manufacturing method, for example, as shown in FIG. 4A, a CFRP molding prepreg 25 is arranged on at least one surface of the metal member 10, and the metal member 10 and the CFRP molding prepreg 25 are laminated in this order. Form the laminated body. In FIG. 4A, CFRP can be laminated instead of the CFRP molding prepreg 25, but at this time, the adhesive surface of CFRP is roughened by, for example, blasting, plasma treatment, corona treatment, or the like. It is preferable that the activation is performed by such as. Next, by heating and pressurizing this laminate, a metal-FRP composite 1 is obtained as shown in FIG. 4 (b). In such a manufacturing method, the matrix resin 201 contained in the CFRP molding prepreg 25 functions as an adhesive resin.

Here, in FIG. 4A, CFRP molding prepregs 25 (or CFRP) may be laminated on both sides of the metal member 10. Further, the CFRP molding prepreg 25 (or CFRP) to be the CFRP layer 20 is not limited to one layer, and may be a plurality of layers. Further, two or more metal members 10 may be used and laminated so as to sandwich the CFRP forming prepreg 25 (or CFRP) in a sandwich shape.

[Compounding with metal member 10]
The composite of the metal member 10 and the CFRP layer 20 is preferably carried out as follows, for example.

The CFRP molding prepreg 25 to be the CFRP layer 20 is arranged at a predetermined position on the adhesive surface of the metal member 10 to form a laminated body. Then, the obtained laminate is installed in a pressure molding machine and pressure-molded to form a CFRP layer 20.

[About heat crimping conditions]
In the manufacturing method as described above, the heat-bonding conditions for combining the metal member 10 and the CFRP molding prepreg 25 (or CFRP) are as follows.

The heat crimping 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, more preferably. Is in the range of 180 ° C. or higher and 250 ° C. or lower. Within such a temperature range, a crystalline resin is more preferably a temperature above the melting point, and a non-crystalline resin is more preferably a temperature of Tg + 150 ° C. or higher. If the temperature is equal to or lower than the upper limit temperature, decomposition of the resin due to excessive heat can be suppressed. Further, when the temperature is at least the lower limit temperature, the melt viscosity of the resin can be set to be sufficiently low to maintain the adhesiveness to the reinforcing fiber material and the impregnation property to the reinforcing fiber base material.

The pressure during heat crimping is, for example, preferably 3 MPa or more, and more preferably 3 MPa or more and 5 MPa or less. When the pressure is not more than the upper limit, deformation and damage due to excessive pressure can be suppressed. Further, if it is at least the lower limit, the impregnation property of the reinforcing fiber base material can be maintained.

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

The batch molding as described above is preferably performed by hot pressing, but it is also possible to quickly install a material preheated to a predetermined temperature in a low temperature pressure molding machine for processing.

[About additional heating process]
In such a production method, when a crosslinkable adhesive resin composition containing a crosslinkable curable resin (B) and a crosslinker (C) in the phenoxy resin (A) is used as the raw material resin for forming the matrix resin 201. In addition, additional heating steps can be included.

When a crosslinkable adhesive resin composition is used, the first cured product (solidified product) in the first cured state is solidified but not crosslinked (cured) in the heat crimping step. The CFRP layer 20 containing the matrix resin 201 made of a cured product (solidified product) in a cured state can be formed.

In this way, through the heat crimping step, the metal member 10 and the CFRP layer 20 made of the cured product (solidified material) in the first cured state are laminated and integrated, and are intermediate between the metal-FRP composite 1. The body (preform) can be made. Then, the intermediate is post-cured by at least the CFRP layer 20 made of the cured product (solidified material) in the first cured state by further performing an additional heating step after the heat crimping step. The resin can be cross-linked and cured to change into a cured product (cross-linked cured product) in a second cured state.

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. In addition, instead of post-cure, the heat history in the 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.

[About pretreatment process]
When producing the metal-CFRP composite 1, it is preferable to degrease the metal member 10 as a pretreatment step, and perform a mold release treatment on the mold and removal of deposits (dust removal) on the surface of the metal member 10. Is more preferable. Except for steel plates having very high adhesion such as TFS (Tin Free Steel), it is usually preferable that the metal member 10 such as a steel plate to which rust preventive oil or the like is attached is degreased to restore the adhesion. Regarding the necessity of degreasing, if the target metal member is joined and integrated with the target CFRP without a degreasing step in advance, it is confirmed whether sufficient adhesiveness can be obtained, and it is judged. Good.
[About chemical conversion processing process]
If necessary, a chemical conversion treatment liquid is applied to the surface of the metal member 10 degreased in the pretreatment step and dried to improve the adhesion between the CFRP layer 20 and the metal member 10, which is preferable. As the chemical conversion treatment liquid, for example, it is preferable to use a treatment liquid containing Cr, P, Si and / or Zr. Specifically, as the chemical conversion treatment liquid, a known chromate treatment liquid, a known phosphoric acid treatment liquid, an aqueous solution containing zirconate, a silane coupling agent, a triazine thiol derivative, or the like can be used. A chemical conversion treatment film can be formed by applying this chemical conversion treatment liquid to the surface of the metal member 10 and drying it. The chemical conversion treatment liquid can be applied by a generally known method such as dipping, roll coating, blade coating, and spray coating. Drying after coating can be performed in a generally known oven such as a hot air oven, an infrared oven, a near infrared oven, or an induction heating oven. The drying temperature is not particularly specified, but the condition that the plate temperature is 50 ° C. to 200 ° C. is preferable.

[Post-process]
In the post-process for the metal-CFRP composite 1, in addition to painting, drilling and application of an adhesive for adhesive bonding are performed for mechanical bonding with other members such as bolts and rivets.

[About the manufacturing method of CFRP or CFRP prepreg]
Here, a method for producing CFRP or CFRP forming prepreg 25 used when forming the CFRP layer 20 will be described.

In the CFRP or CFRP molding prepreg 25 used when forming the CFRP layer 20, the reinforcing fiber base material used as the carbon fiber material 203 is, for example, a non-woven fabric base material using chopped fibers or a cloth material using continuous fibers. A directional reinforcing fiber base material (UD material) or the like can be used, but from the viewpoint of the reinforcing effect, it is preferable to use a cloth material or a UD material.

As the CFRP or CFRP molding prepreg 25, it is preferable to use a prepreg produced by a powder coating method rather than a prepreg produced by a conventionally known method such as a wet melt or a film stack method. The prepreg produced by the powder coating method has good drapeability because the reinforcing fiber base material is impregnated with the resin in the state of fine particles, and can follow even if the adherend has a complicated shape. Suitable for bulk forming hot press because it is possible.

The main methods of the powder coating method include, for example, an electrostatic coating method, a fluidized bed method, a suspension method, etc., and any of these methods may be appropriately selected depending on the reinforcing fiber base material type and the matrix resin type. .. Of these, the electrostatic coating method and the fluidized bed method are suitable methods for thermoplastic resins, and are preferable because the process is simple and the productivity is good. In particular, the electrostatic coating method is the most suitable method because it is excellent in the uniformity of adhesion of the adhesive resin composition to the reinforcing fiber base material.

When powder-coating the adhesive resin composition to be the matrix resin 201 when forming the CFRP or CFRP molding prepreg 25, the adhesive resin composition containing the phenoxy resin (A) described above is made into a fine powder. It is preferable to obtain a prepreg by adhering this fine powder to the reinforcing fiber base material by powder coating.

For finely powdering the adhesive resin composition containing the phenoxy resin (A), for example, a pulverizing mixer such as a low-temperature drying pulverizer (Sentrid Dry Mill) can be used, but the present invention is not limited thereto. Further, when pulverizing the adhesive resin composition for the matrix resin 201, each component of the adhesive resin composition may be pulverized and then mixed, or each component may be mixed in advance and then pulverized. In this case, it is preferable to set the pulverization conditions so that each fine powder has an average particle size described later. The fine powder thus obtained has an average particle diameter in the range of 10 μm or more and 100 μm or less, preferably in the range of 40 μm or more and 80 μm or less, and more preferably in the range of 40 μm or more and 50 μm or less. When the average particle size is 100 μm or less, the energy when the adhesive resin composition collides with the fibers can be reduced in powder coating in an electrostatic field, and the adhesion rate to the reinforcing fiber base material can be increased. In addition, by setting the average particle size to 10 μm or more, it is possible to prevent particles from scattering due to the accompanying airflow and suppress a decrease in adhesion efficiency, and prevent resin fine powder floating in the atmosphere from causing deterioration of the working environment. it can.

As an adhesive resin composition for forming CFRP or CFRP molding prepreg 25, powder coating of a crosslinkable adhesive resin composition in which a crosslinkable resin (B) and a crosslinker (C) are mixed with a phenoxy resin (A). When the above is performed, the average particle size of the fine powder of the phenoxy resin (A) and the fine powder of the crosslinkable resin (B) is 1 to 1.5 times the average particle size of the fine powder of the crosslinker (C). It is preferably within the range. By making the particle size of the fine powder of the cross-linking agent (C) equal to or smaller than the particle size of the fine powder of the phenoxy resin (A) and the cross-linking curable resin (B), the cross-linking agent (C) is even inside the reinforcing fiber base material. Enters and adheres to the reinforcing fiber material. Further, since the cross-linking agent (C) is evenly present around the particles of the phenoxy resin (A) and the particles of the cross-linking curable resin (B), the cross-linking reaction can be reliably advanced.

In powder coating for forming CFRP or CFRP molding prepreg 25, the amount of the adhesive resin composition to be the matrix resin 201 adhered to the reinforcing fiber base material (resin ratio: RC) is, for example, 20% or more and 50%. It is preferable to apply the coating so as to be within the following range. The RC is more preferably in the range of 25% or more and 45% or less, and further preferably in the range of 25% or more and 40% or less. By setting RC to 50% or less, it is possible to prevent deterioration of mechanical properties such as tensile and flexural modulus of CFRP. Further, by setting RC to 20% or more, the required amount of resin adhered can be secured, so that the matrix resin 201 is sufficiently impregnated into the inside of the carbon fiber base material, and the thermal and mechanical properties can be improved.

The fine powder of the powder-coated adhesive resin composition (which becomes the matrix resin 201) is fixed to the reinforcing fiber base material by heating and melting. In this case, the powder may be applied to the reinforcing fiber base material and then heat-fused, or the fine powdered reinforcing fibers of the adhesive resin composition may be coated with the powder on the preheated reinforcing fiber base material. It may be fused at the same time as the coating on the base material. By heating and melting the fine powder of the adhesive resin composition on the surface of the reinforcing fiber base material in this way, the adhesion to the reinforcing fiber base material can be enhanced and the fine powder of the coated adhesive resin composition can be prevented from falling off. .. However, at this stage, the adhesive resin composition to be the matrix resin 201 is concentrated on the surface of the reinforcing fiber base material, and does not reach the inside of the reinforcing fiber base material as in the molded product after heat and pressure molding. .. The heating time for fusing the adhesive resin composition after powder coating is not particularly limited, but is usually 1 to 2 minutes. The melting temperature is in the range of 150 to 240 ° C., preferably in the range of 160 to 220 ° C., and more preferably in the range of 180 to 200 ° C. If the melting temperature is not more than the upper limit, the progress of the curing reaction can be prevented. Further, if it is at least the lower limit, heat fusion is sufficient, and the fine powder of the adhesive resin composition is prevented from falling off or falling off during handling work.

The method for producing the metal-carbon fiber reinforced resin material composite according to the present embodiment has been described in detail above.

The method for producing the metal-carbon fiber reinforced resin material composite and the metal-carbon fiber reinforced resin material composite according to the present invention will be specifically described below with reference to Examples and Comparative Examples. The examples shown below are merely examples of the method for producing the metal-carbon fiber reinforced resin material composite and the metal-carbon fiber reinforced resin material composite according to the present invention, and are merely examples of the metal-carbon fiber according to the present invention. The method for producing the reinforced resin material composite and the metal-carbon fiber reinforced resin material composite is not limited to the following examples.

(Preparation of metal plate)
As a metal plate which is an example of a metal member, 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: 0.0032% by mass, steel consisting of Fe and impurities as the balance is hot-rolled, pickled, and then cold-rolled to a thickness of 1.0 mm. A steel plate was obtained. Next, the obtained cold-rolled steel sheet was annealed by 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 . Hereinafter, the produced cold-rolled steel sheet is referred to as "CR".

In addition, the obtained cold-rolled steel sheet is annealed under the condition that the maximum reached plate temperature is 820 ° C. in the annealing process of a continuous hot-dip plating apparatus having an annealing process, and then hot-dip galvanized in the plating process is also prepared. did. 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 step are Zn-0.2% Al (hereinafter referred to as "GI"), Zn-0.09% Al (hereinafter referred to as "GA"), Zn-1. 5% Al-1.5% Mg (hereinafter referred to as "Zn-Al-Mg"), Zn-11% Al-3% Mg-0.2% Mg (hereinafter referred to as "Zn-Al-Mg-Si") ”) Was used.

Incidentally, those using hot-dip plating bath of Zn-0.09% Al plating (GA) is by immersing 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 After gas 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.

The tensile strength of each of the produced metal plates was measured and found to be 980 MPa. The amount of plating of the plated steel sheet was 45 g / m ² per side for GA and 60 g / m ² per side for plating other than GA.

(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 3 g / L of aqueous solution 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 manufactured by Nippon Parkering Co., Ltd. Similarly, the liquid "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 liquid "Si" was coated with an aqueous solution containing aqueous dispersion silica. It is called "system treatment", the one coated with an aqueous solution of zirconium carbonate is called "Zr-based treatment", and the one treated with a chromate treatment liquid is called "Cr-based treatment".

The adhesion amount of each treatment was 30 mg / m ² per side. 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, which is included in the wet coating amount, The masses of Si and Zr 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 the obtained calibration curve.

(Making CFRP prepreg)
For bisphenol A type phenoxy resin "Phenototo YP-50S" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. (Mw = 40,000, hydroxyl group equivalent = 284 g / eq, melt viscosity at 250 ° C. = 90 Pa · s, Tg = 83 ° C.) The inorganic salt particles or oxide particles shown below were kneaded.

A phenoxy resin kneaded with inorganic salt particles or oxide particles was pulverized and classified to prepare a powder having an average particle diameter D50 of 80 μm. Next, a reinforcing fiber base material made of carbon fiber (cloth material: manufactured by Toho Tenax Co., Ltd., IMS60) was powder-coated under the conditions of an electric charge of 70 kV and a sprayed air pressure of 0.32 MPa in an electrostatic field. 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.

Regarding the produced prepreg, the fiber bundle was measured from a photograph obtained by observing the vertical cross section of the carbon fiber in the length direction with a traveling electron microscope and found to be 200 μm.

<Inorganic salt particles and oxide particles used in this experiment>
-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 μm, 10 μm, and 15 μm. Hereinafter, it will be referred to as "Mg V acid".
-Magnesium vanadate: A powder granulated by a dry powder granulator (generally called a jet mill) was atomized and classified by a classifier to have an average particle size of 0.05 μm. Hereinafter, it will be 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 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 μm. Hereinafter referred to as "Ca acid Cr".
-Potassium nichrome: After rubbing the reagent with a mortar, the reagent was classified using a sieve to have an average particle size of 3 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 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 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 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 μm. Hereinafter referred to as "Na pyropate".
-Calcium vanadate: The reagent was rubbed in a mortar and then classified using a sieve to have an average particle size of 3 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 μm. Hereinafter referred to as "V acid K".
-Zinc oxide: 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 "Zn oxide".
-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 (registered trademark) CR-95" manufactured by Ishihara Sangyo Co., Ltd., with an average particle size of 0.28 μm (catalog value) was used. Hereinafter referred to as "Ti oxide".
-Calcium carbonate: 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 "Ca carbonate".
-Conductive titanium oxide: Sn-doped titanium oxide "ET-500W" manufactured by Ishihara Sangyo Co., Ltd. was classified by sieving with an average particle size of 2 to 3 μm (catalog value) to obtain an average particle size of 2 μm. 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 μm. Hereinafter referred to as "crate".
-Silica: "AEROSIL® 50" manufactured by Aerosil Japan 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 0.1 μm.
-Zinc oxide: Zinc oxide "MZ-300" manufactured by TAYCA Corporation 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 0.1 μm. Hereinafter referred to as "ZnO".

Of the above oxide particles and inorganic salt particles, alumina and Ti oxide are oxide particles, which are different from the inorganic salt particles having a rust preventive function. Also, Ca carbonate is not an inorganic salt particle having a rust preventive function.

The prepared prepregs are summarized in Table 1 below.
The powder resistance of the particles in Table 1 is a resistance value when each powder is compressed by 10 MPa at 25 ° C. using a powder resistance measurement system MCP-PD51 manufactured by Mitsubishi Chemical Analytech. The glass transition point was measured by measuring the produced prepreg with an automatic suggested scanning calorimeter "DSC-60A" manufactured by Shimadzu Corporation.

The prepared film coating liquid is partially applied on a metal plate cut to the size required for evaluation with a blade coater on only one side and only on the part where the CFRP prepreg is attached, and the ultimate plate temperature is maintained at 230 ° C. It was dried and cured under the condition that the time was 60 seconds. For partial application, mask the area other than the part to which the CFRP prepreg is attached in advance with masking tape (using "Nitto Denko (registered trademark) tape" manufactured by Nitto Denko Corporation), apply the film, and remove the masking tape after drying and baking. I went there.

(Thermocompression bonding process)
A metal-CFRP composite material was prepared by stacking the prepared prepregs on a metal plate and pressing them at 3 MPa for 3 minutes with a press machine having a flat die heated to 250 ° C. During the thermocompression bonding treatment, dust and the like were carefully removed from the surface of the flat mold, and the surface of each metal plate was washed in advance with acetone. The total thickness of the CFRP on which the prepreg was stacked was 1.5 mm.

<Evaluation>
[1. Corrosion resistance]
Using the prepared composite material 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. Degreasing was carried out by immersing in a degreasing agent "Fine Cleaner E6408" manufactured by Nihon Parkerizing Co., Ltd. at 60 ° C. for 5 minutes. The surface of the defatted sample was adjusted by immersing it in "Preparen X" manufactured by Nihon Parkerizing Co., Ltd. at 40 ° C. for 5 minutes. Then, zinc phosphate treatment was carried out 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. Electrodeposition coating was performed on metal parts 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 with the CFRP side as the evaluation surface so that salt water was sprayed on 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. Further, since red rust is generated from the vicinity of the end of the CFRP attached to the metal plate, the observation was focused on such a region. 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]
The test was carried out using a composite sample having a width of 30 mm and a length of 100 mm. As this sample, a metal plate having CFRP attached to the entire surface on one side was used. 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 and tested so that the side to which the load was applied was the CFRP side. When a load was applied in a three-point bending test, the peeling state of the metal plate and CFRP when the sample was bent was observed and evaluated.

The peeling state differs depending on the sample, and there are those with "no peeling", those with "slightly peeling" of the deformed part, and those with CFRP completely peeling from the metal plate and "largely peeling". Yes, these were evaluated.

The obtained evaluation results are summarized in Table 2 below.

As is clear from Table 2 above, the sample corresponding to the invention example of the present invention shows excellent corrosion resistance, while the sample corresponding to the comparative example of the present invention has a problem in corrosion resistance.

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 anyone with 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 Metal-carbon fiber reinforced resin material composite 10 Metal member 20 Carbon fiber reinforced resin material (CFRP layer)
25 CFRP molding prepreg 201 matrix resin 203 carbon fiber material 205 inorganic salt particles

Claims

With metal parts
The is located in at least a part of the surface of the metal member, and a predetermined matrix resin, the carbon fiber material present in the matrix resin, 23 to a powder resistivity at 27 ° C. is 7.0 × 10 7 [ A carbon fiber reinforced resin material containing inorganic salt particles composed of an inorganic salt of one or more elements selected from Cr, P, and V, which are more than Ω · cm] and have a rust preventive function. ,
A metal-carbon fiber reinforced resin material composite comprising.
The inorganic salt particles include chromate ion, dichromate ion, phosphate ion, hydrogen phosphate ion, dihydrogen phosphate ion, diphosphate ion, triphosphate ion, orthovanadate ion, pyrovanadate ion, metavanazine. The metal-carbon fiber reinforced resin material composite according to claim 1, which comprises an inorganic salt of one or more ions selected from the group consisting of acid ions.
Claimed that the inorganic salt particles consist of 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.
Claim 1 satisfies the relationship of D / r ≧ 10 when the average thickness of the fiber bundle of the carbon fiber material is D [μm] and the average particle size of the inorganic salt particles is r [μm]. The metal-carbon fiber reinforced resin material composite according to any one of 3 to 3.
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 0.10 μm or more and 10.00 μm or less.
The metal-carbon fiber reinforced resin material composite according to any one of claims 1 to 5, wherein the volume ratio of the inorganic salt particles in the carbon fiber reinforced resin material is 5% or more and 30% or less.
The metal-carbon fiber reinforced resin material composite according to any one of claims 1 to 6, wherein the reinforced fiber density (Volume Fraction: VF) of the carbon fiber reinforced resin material is 30% or more and 70% or less.
The metal-carbon fiber reinforced resin material composite according to any one of claims 1 to 7, wherein the matrix resin contains a thermoplastic resin.
The metal-carbon fiber reinforced resin material composite according to any one of claims 1 to 8, wherein the matrix resin contains a phenoxy resin.
The metal-carbon fiber reinforced resin material composite according to any one of claims 1 to 9, wherein the material of the metal member is a steel material, an iron-based alloy, titanium or aluminum.
The metal-carbon fiber reinforced resin material composite according to claim 10, wherein the steel material is a plated steel material.
On at least one surface of the metal member, and a matrix resin, and the carbon fiber material, the powder resistivity at 23 ~ 27 ° C. is 7.0 × 10 7 [Ω · cm ] greater, and the rust prevention function A carbon fiber reinforced resin material containing inorganic salt particles composed of an inorganic salt of one or more elements selected from Cr, P, and V, or the matrix resin, the carbon fiber material, and the above. After arranging the carbon fiber reinforced resin material prepreg containing the inorganic salt particles, the metal member and the carbon fiber reinforced resin material or the carbon fiber reinforced resin material prepreg are heat-bonded to each other. A method for producing a resin material composite.
The metal-carbon fiber reinforced resin material composite according to claim 12, wherein the metal member is processed into a predetermined shape prior to the arrangement of the carbon fiber reinforced resin material or the carbon fiber reinforced resin material prepreg. How to make the body.
The metal according to claim 12, wherein after the metal member and the carbon fiber reinforced resin material or the carbon fiber reinforced resin material prepreg are heat-bonded, the obtained heat-bonded body is processed into a predetermined shape. -A method for producing a carbon fiber reinforced resin material composite.