JP6419499B2 - Method for producing composite of metal and FRTP - Google Patents

Description

  The present invention relates to a method for producing a composite made of a fiber and a fiber reinforced thermoplastic resin (FRTP) reinforced with fibers such as carbon fibers. More specifically, the present invention relates to a method for producing a composite in which a metal and a fiber reinforced thermoplastic resin obtained by reinforcing a thermoplastic resin as a matrix resin with carbon fibers or aramid fibers are laminated.

  A carbon fiber composite material (CFRP) in which carbon fibers are hardened with a resin is known. Among these, thermosetting carbon fiber composite materials (CFRTS) using a thermosetting resin such as an epoxy resin as a matrix resin have high strength and ultralight properties, such as golf club shafts, tennis rackets, fishing rods and the like. In recent years, it has been used for aircraft main wings, etc., and its demand is rapidly expanding. However, there are few views that CFRTS will become the leading role in the future for automobile structures, which are expected to be the next major application after aircraft. One of the reasons is that an autoclave that creates a vacuum environment is used to remove air existing between prepregs as a curing method of CFRTS. For this reason, the time required for the bonding process is as long as several hours, that is, the production efficiency is low.

  Therefore, instead of thermosetting fiber reinforced plastics, fiber reinforced thermoplastics (FRTP, Fiber Reinforced Thermo) reinforced with carbon fiber, glass fiber, aramid fiber, etc., using a thermoplastic resin that is easy to process as a matrix. Plastics) is expected. As for FRTP, intermediate materials such as isotropic or unidirectional plates have been developed, and in recent years, prototypes obtained by molding them into a desired shape by a hot press method have been made. That is, since the matrix resin is thermoplastic, if the FRTP prepreg, which is an intermediate material, is pressed in a state of being heated to the melting point or higher, an FRTP molded product can be produced, and the molding time is also a short time of 10 to 20 minutes. It is possible with. As the matrix resin, highly crystalline thermoplastic resins such as PA6 (6 nylon), PA66 (66 nylon), PPS (polyphenylene sulfide resin), PEEK (polyetheretherketone resin), and thermoplastic polyimide are used. Yes. Further, CFRTP using carbon fibers as fibers, AFRTP using aramid fibers, and the like are known.

  As the development of CFRTP molding progresses, it has been found that CFRTP can obtain high strength comparable to CFRTS. Therefore, at present, research and development of the connecting structure between parts has become an issue as to how to assemble the obtained CFRTP shaped object and finish it into a desired product, part, etc. such as an automobile. That is, although CFRTP contains a large amount of carbon fiber, the matrix resin is a thermoplastic resin, and its mechanical strength is weak when viewed microscopically. Therefore, a conventional assembling method employing a mechanical connection structure in which a hole is opened and a part and a part are fastened with bolts and nuts, such as a metal mechanical part, is not suitable. For example, in the case of screw connection, excessive tightening of screws will destroy the matrix resin, and even if it is fixed that seems to be tightened by an appropriate torque, it will often loosen due to changes in environmental temperature and changes over time, resulting in a decrease in adhesive strength. .

  In addition, as in the case of metal resistance welding, a heat fusion method using ultrasonic waves between thermoplastic resins, which are the base materials, is also envisaged, but it is possible to reliably and easily melt the thick CFRTP molded products. It is difficult to put on and is not practical. On the other hand, the fixing between the CFRTP moldings and the metal parts with an adhesive does not give a desired fixing strength. Under these circumstances, the present inventors considered the most feasible connection method (adhesion structure or joint structure) to make the end or part of the CFRTP molding to be connected a metal part. Thus, a conventional mechanical connection structure using the metal portion or a fixing method is employed. In order to make this technique successful, the metal part for connection and the CFRTP molded product which is the main structure part are reliably joined (fixed) and integrated.

  Patent Document 1 proposes a technique directly proposed by the present inventors and related to a joining method, that is, a technique for manufacturing an alternately laminated plate by joining a metal thin plate material and a CFRTP thin plate material. Yes. According to Patent Document 1, in order to obtain a strong bonding force between a thin metal plate portion and a thermoplastic resin (PPS), the surface on the metal side is a double-concave surface shape having a period of micron order and a period of several tens of nanometers (this book Formed on the surface of a new NMT (abbreviation of New nano molding tech.) Proposed by the inventor, or surface-treated metal surface shape by NAT (abbreviation of Nano adhesion tech.), And the surface of the metal material This is a method in which a CFRTP prepreg is overlaid and heated to a temperature equal to or higher than the melting point of the resin while removing air in a vacuum environment using a heat press or a vacuum heat press to fix the metal and CFRTP.

  Furthermore, in Patent Document 1, a thermoplastic resin powder of the same type as that used for the matrix resin of CFRTP is applied on a metal material subjected to the same surface treatment (by powder coating), There is a description that this powder-coated metal sheet material and CFRTP sheet material are heat-melted and bonded using a general-purpose hot press machine after being heat-fused under nitrogen. The present inventors conducted an experiment again on the joining method described in Patent Document 1 with respect to PPS and PEEK. That is, as described in Patent Document 1, it is a method in which a metal surface is coated with powder, melted and baked, and CFRTP is bonded thereto using a vacuum hot press. A specific metal was tested using a titanium alloy plate or the like. Titanium alloy “KS6-4” (standard name of Kobe Steel Co., Ltd., head office: Japan) which is 0.4 mm thick “JIS60 type” and “TAB6400” (US standard “ASTM B348 Gr5”) Shinagawa-ku, Tokyo) was used.

  The outer surfaces of both sides were formed with this titanium alloy plate, and a PPS and PEEK matrix resin was used as the intermediate layer, but a 100 mm rectangular laminate plate of CFRTP having a thickness of about 2 mm was produced. Furthermore, in order to observe a cut surface, the outer periphery of the obtained laminated board was cut | disconnected with the high-speed thread saw, and the 90-mm square laminated board was produced. This cut surface had no cavities and the like, and the cross-section of each material appeared, and it was temporarily judged that a satisfactory joining force was obtained. However, the following tests were conducted, and it was found that these PPS and PEEK laminates had fundamental problems. That is, a large number of strips of 90 mm × 15 mm were obtained from the obtained laminated plate with a high-speed yarn saw, and the ends of the titanium thin plate were peeled off from the resin portion with a nipper from the ends of the strips, and the peeled alloy ends were peeled off. A test was conducted by grasping with a nipper and peeling off from the CFRTP part.

  This method is a simple peeling test. Peeling requires a considerable force and the joining force was not low, but there was no adhesion of resin powder (fine particles) to the peeled Ti alloy sheet surface, that is, the resin was biting into the fine recesses on the metal surface It was found that there was no evidence and the maximum strength was not achieved. That is, when a thermoplastic resin is bonded to a new NMT-treated metal under optimum conditions by injection molding, the resin powder (fine particles) always adheres to the metal side when it is peeled off. Then it was not so far. In the case of laminates made by powder coating using PPS powder or PEEK powder, the laminate is similarly cut into strips, the metal alloy thin plate is peeled off, and it is confirmed that there is no resin powder adhering to the peeled thin plate surface. did.

  Unfortunately, these laminates made using the vacuum hot press method and powder coating method do not have enough resin intrusion into the fine recesses on the metal surface. It was an interface fracture in which the resin part fell out of the fine recess, not the fracture of. If there is no strong metal-resin bonding force that causes a material breakage of the resin part, it should not be used as an assembly method for CFRTP material. Judged to seek.

  The inventors of the present invention have (1) the entire surface covered with ultrafine recesses having a diameter of 20 to 50 nm and (2) an amine-based surface as a bonding condition between an aluminum alloy and a crystalline resin such as PBT. It was proposed that the molecule is chemisorbed (see, for example, Patent Documents 2 and 3). Similarly, the conditions imposed on the metal alloy material when using the new NMT are (3) a rough surface with 1-10 μm period irregularities on the surface, and (4) an ultra-long period of 5 to 300 nm on the rough surface. Proposed that it has a fine irregular surface, and (5) its surface is covered with a thin ceramic layer such as metal oxide or metal phosphate (for example, patent References 4 and 5).

JP 2011-240620 A JP 2004-50488 A WO2004 / 041532 WO2009 / 031632 JP 2011-240620 A

The present invention has been invented against the background as described above, and achieves the following objects.
The objective of this invention is providing the manufacturing method of the composite_body | complex of a metal and FRTP with which the adhering strength of a CFRTP material and a metal is strong.
Another object of the present invention is to provide a method for producing a composite of metal and FRTP, which has a high bonding strength between the CFRTP material and the metal and has little variation in the bonding strength even after mass production.
Still another object of the present invention is to provide a composite of metal and FRTP that facilitates a mechanical fastening structure such as a bolt-nut type with another structural member made of a metal material or the like in a composite of a CFRTP material and a metal. It is in providing the manufacturing method of a body.

The present invention adopts the following means in order to solve the above problems.
The method for producing a complex of metal and FRTP of the present invention 1 comprises
An aluminum alloy surface treatment step in which the surface of the aluminum alloy shaped article is covered with an ultrafine recess having a diameter of 20 to 50 nm and the amine-based molecules are chemically adsorbed;
Inserting the aluminum alloy shaped article that has undergone the surface treatment step into an injection mold, and injecting a polyamide resin or a polyphenylene sulfide-based resin composition onto the surface to create an injection bonded product;
A charging step in which the injection-bonded product is loaded into a hot press mold, and the polyamide resin or the polyphenylene sulfide is a matrix resin and the FRTP prepreg or FRTP molded product is stacked and loaded on the injected resin; ,
In the hot press mold, for heating and pressurizing in order to perform both heat fusion of the matrix resin and the injected polyamide resin or the polyphenylene sulfide resin composition , which are the same type, at a time. A hot press process ;
In the hot pressing step, the start of melting of the injected polyamide resin or polyphenylene sulfide resin composition and the matrix resin is detected by the numerical value of the pressurization, and immediately after the decrease of the pressurization is detected, The cooling of the panel is started.

The method for producing a metal-FRTP complex of the present invention 2 comprises:
The surface has a roughness on the order of microns in which the average length (RSm) of the contour curve element is 0.8 to 10 μm and the maximum height (Rz) is 0.2 to 5 μm, and has the roughness. A metal alloy surface treatment step for producing a metal alloy shaped article in which ultrafine irregularities having a period of 10 to 300 nm are present and the surface layer is covered with a thin ceramic layer of metal oxide or metal phosphate,
Inserting the metal alloy shaped article that has undergone the surface treatment step into an injection mold, and injecting a polyamide resin or a polyphenylene sulfide-based resin composition onto the surface layer to create an injection bonded product; and
Loading step of charging the hot-press mold with the injection-bonded product, and charging the injected resin with the FRTP prepreg or FRTP molding using the polyamide resin or the polyphenylene sulfide resin as a matrix resin;
In the hot press mold, for heating and pressurizing in order to perform both heat fusion of the matrix resin and the injected polyamide resin or the polyphenylene sulfide resin composition , which are the same type, at a time. A hot press process ;
In the hot pressing step, the start of melting of the injected polyamide resin or polyphenylene sulfide resin composition and the matrix resin is detected by the numerical value of the pressurization, and immediately after the decrease of the pressurization is detected, The cooling of the panel is started.

The method for producing a composite of a metal and FRTP of the present invention 3 comprises the method for producing a composite of a metal and FRTP of the present invention 1 or 2,
The FRTP is characterized by using CFRTP (carbon fiber reinforced thermoplastic) or AFRTP (aramid fiber reinforced thermoplastic).

  The method for producing a metal and CFRTP of the present invention has strong adhesion between the metal part and the resin part of CFRTP, and can ensure product stability even in mass production. In addition, the composite portion of the metal and CFRTP of the present invention in which the structural portion that maintains strength and shape is made of CFRTP material and the assembly end and the like is made of metal material is not only sturdy and lightweight, but also assembled with other parts. Is easy. Therefore, the composite of the metal and CFRTP of the present invention can be used for parts of mobile machines such as automobiles, building members and the like.

FIG. 1 is a test piece of an injection-bonded product having a shape capable of measuring a bonding force (shearing force) between a metal and a resin. FIG. 2 shows the appearance and dimensions of an iron container for testing the influence of heat by placing an injection joint or the like and leaving it to be covered with a lid. FIG. 3 shows the shape of an injection-joined product composed of a metal plate and a flat resin part, and the position of the pin gate when the flat resin part of the injection-joined product is injection-joined. FIG. 4 shows an example of the shape of a CFRTP molded product (composite) with a thin metal plate obtained from the injection-bonded product and the CFRTP prepreg of FIG. 3 by a hot press method. FIG. 5 is an external view showing another metal thick plate joined to the metal thin plate of the CFRTP molded product with the metal thin plate of FIG. 4 by an adhesive. FIG. 6 shows the composite of FIG. 5 cut into several pieces so that the bonding force (shear breaking force) between the metal part and the CFRTP part in the CFRTP molded product with a metal thin plate (FIG. 4) can be measured. The second-stage cutting process is performed. FIG. 7 is a test piece in which a cut is made in the cut portion of FIG. 6 so that the bonding force (shear breaking force) between the metal portion and the CFRTP portion can be measured by a tensile test. FIG. 8 is a 100,000 times electron micrograph of the A5052 aluminum alloy after the NMT treatment.

Embodiments of the present invention will be described below.
[1. Metal alloy material and its surface treatment]
As the metal used in the present invention, an aluminum alloy, a general steel material, stainless steel, pure titanium, a titanium alloy, a magnesium alloy, an aluminum plated steel plate, or the like can be used. The method for producing a composite of a metal and CFRTP of the present invention and the composite use the injection joining technique of NMT and new NMT referred to in the present invention from the development process described above. Therefore, the metal materials used in this composite are limited to those to which this injection joining technology can be applied. As a result, NMT uses an aluminum alloy, and any metal species can be used in the new NMT. As long as it meets the definitions of NMT and new NMT, the type of metal that can be used in the present invention is not limited.

  The conditions imposed on the aluminum alloy when NMT is used in the present invention are as follows: (1) The entire surface is covered with ultrafine recesses having a diameter of 20 to 50 nm, and (2) amine-based molecules are chemisorbed on the surface. (For example, see Patent Documents 2 and 3). Moreover, the conditions imposed on the metal alloy material of the new NMT are (3) a rough surface with irregularities with a period of 1 to 10 μm on the surface, and (4) an ultrafine irregular surface with a period of 5 to 300 nm on the rough surface. (5) The surface is covered with a thin ceramic layer such as a metal oxide or a metal phosphate. Specific surface treatment methods are described in, for example, Patent Documents 4 and 5 and the like, and are well-known techniques, and detailed descriptions thereof are omitted. However, in the examples of the present invention, the NMT treatment method for the used A5052 aluminum alloy and the new NMT treatment method for the aluminum plated steel sheet and the titanium alloy are described in the examples described later.

[2. Resin composition used for injection joining]
It describes about the resin composition used for injection joining. First, the resin composition to be used in the NMT and the new NMT is not limited to the present invention, and there are two conditions. One is (1) a resin composition mainly composed of a hard thermoplastic resin having high crystallinity. Specifically, polyamide resin, PBT, liquid crystal polymer (fully aromatic polyester resin), PPS, PEEK, etc. are hit, and polyolefins are not included. Further, in addition to the above conditions, (2) the resin component includes a heat-resistant different polymer or organic molecule as a subsidiary component other than the main component resin, and all or a part of the different molecules are melted when the main component polymer and molecule are melted. It is possible to create a resin compound that can be mixed at a level.

  That is, when a resin is injected into a mold from an injection molding machine, the injected molten resin collides with the surface of the metal alloy material in the mold, and the physical impact produces seeds of these resin crystals, resulting in rapid viscosity. In general, it becomes difficult to penetrate into the rough surface formed on the surface of the metal alloy or the fine concave portion of the ultra fine uneven surface. However, when the resin compound shown in the above (2) is used, in both the case of NMT and the case of the new NMT, the crystallization rate at the time of rapid cooling is slowed by including a different polymer other than the main component resin, This makes it easy for the resin to penetrate into the ultrafine recesses on the surface of the metal alloy material, which is effective in securing the injection joining force. Resin types that have been successfully compounded using such different polymers and specific organic molecules and that can be suitably used for injection joining include various polyamide resins, PBT, and PPS resin compositions. It is.

  First, the polyamide resin will be described more specifically. There are many types of polyamide resins, but there is a method in which two types of polyamide resins such as semi-aromatic nylon as the main component in the resin component and PA6 or PA66 as the subcomponent are mixed and used. This is intended to suppress the crystallization rate of the semi-aromatic nylon, which is the main component, by adding the secondary component nylon. There is also a method for suppressing the crystallization rate by finding some crystallization inhibitor in one kind of polyamide resin. Currently, the polyamide resins frequently used by the present inventors are “Amilan CM3501 (manufactured by Toray Industries, Inc. (head office: Chuo-ku, Tokyo, Japan))” and “91G40 (Asahi Kasei Corporation (head office: Chiyoda, Tokyo, Japan). Ward) product) ".

  As for the PBT-based resin, those in which 90 to 80% of the resin content is PBT and 10 to 20% are PET and a modified polyolefin resin can be suitably used. As this PBT resin, a commercially available resin often used by the present inventors is “BD-01 (product name, manufactured by Toray Industries, Inc.)”. Furthermore, regarding PPS resins, 97-70% of the resin content is PPS, 3-30% is a modified polyolefin resin, and some compatibilizing material is added to make these both compatible at the molecular level. Can be suitably used. The present inventors often use a polyphenylene sulfide resin “SGX120 (Tosoh Corporation (head office: Minato-ku, Tokyo, Japan)” containing 20% of short glass fibers, and reinforcing fibers and inorganics. “SGX100 (manufactured by Tosoh Corporation)”, which does not include fillers such as powder, but has the same resin composition as the former.

  Up to this point, an outline of the general theory of injection joining has been described, but the injection joining used in the present invention has the following points to be noted. One is that the injection-bonded product obtained in this step is then housed in a press mold together with the FRTP prepreg and once heated to a temperature higher than the melting point of the matrix resin. Then, the resin part of the injection bonded product is melted and thermally melted with the resin component of the FRTP part and mixed and integrated. In short, these resin compositions used for injection joining serve not as a structural part but as an adhesive with metal. For this reason, it is preferable that the resin having a good flow and the resin melted to the end of the thin cavity be easily distributed, and a resin composition containing no filler is preferably used. In general, when a metal material and a thermoplastic resin are integrated by injection joining or the like, the resin part is large when compared with the linear expansion coefficient of the resin part and the metal part, and as a resin that maintains its joining state even when the environmental temperature changes The glass fiber and the like are compounded in large quantities to reduce the linear expansion coefficient, but this is not necessary in the present invention.

  The other point relates to the resin type. As described above, the resin types studied by each company as CFRTP are PA6, PA66, PPS, PEEK, thermoplastic polyimide, and the like, and do not include PBT. However, as described above, an injection joining phenomenon was found, but the types of resins that are publicly available and marketed as resin compositions for injection joining are only PA6, PA66, other polyamide resin mixtures, PBT, and PPS. . Therefore, only a few species of PA6, PA66, PPS can be specifically used in connection with the present invention. However, the present inventors, including the present inventors, are developing new technologies that enable injection bonding of these resin types to metals so that the present invention can be used for PEEK and thermoplastic polyimide. Therefore, when the injection joining technique for these resin types is obtained, the present invention can also be applied to CFRTP systems using PEEK and thermoplastic polyimide as a matrix resin. Similarly, when CFRTP using PBT is required in the future, the present invention can be used to produce a composite of metal and CFRTP.

[3. Production of injection-joined products]
FIG. 1 shows a composite obtained by injection joining a metal alloy piece treated with NMT or new NMT and various resins, for measuring the joining force (breaking shear stress) between the metal alloy piece and the resin. It is a test piece which is an injection bonded product. The plate-shaped metal alloy piece 1 is 45 mm × 18 mm × (0.4 to 1.6) mm thick. This is inserted into an injection mold. The resin part 2 is injected into the metal alloy piece 1 inserted into the injection mold from a runner 3 for injection molding through a gate. The resin part has a thickness of 45 mm × 10 mm × 3 mm. The area of the joint portion 4 between the metal alloy piece 1 and the resin portion 2 is 50 mm ² . By using an auxiliary jig for measuring the shear breaking force of the composite and applying it to a tensile tester, the joining force (shear breaking force) of the joint portion 4 is measured and used as the joining force.

  On the other hand, what is shown in FIG. 3 is an injection-joined article 10 obtained by injection-bonding a resin portion 12 made of various resins from a runner 13 through a gate to a metal thin plate 11 which is a metal alloy subjected to NMT or new NMT treatment. It is. This injection bonded product 10 is an example of an intermediate product used for manufacturing the composite of the present invention. The injection bonded article 10 of this example is obtained by bonding a thin metal plate 11 having a thickness of 0.4 mm and a thin resin portion 12 having a thickness of about 0.8 mm, and has a total thickness of 1.2 mm. A rectangular plate of 100 mm in length and width. Although the appearance shape of the injection-joined product is different between FIGS. 1 and 3, technically, the metal and the resin are joined by injection molding exactly the same.

  That is, it is prepared by inserting a metal alloy piece or a metal plate piece subjected to NMT or new NMT treatment into an injection mold and injecting the above-mentioned injection joining resin. As described above, the NMT and new NMT processing methods for each metal are known techniques, and the specific processing method differs depending on the metal alloy type, so that it is complicated and omitted in the text. When the shear strength was measured using the test piece that is the injection-bonded product of FIG. 1, a PPS resin not containing reinforcing fibers (in this example, “SGX100 (manufactured by Tosoh Corporation)”) was used. In this case, the pressure is about 47 MPa (23 ° C.), and in the case of “SGX120 (manufactured by Tosoh Corporation)” containing 20% of PPS resin and glass fiber frequently used in normal injection joining, the pressure is about 43 MPa. In short, as a general theory, when an injection bonded product that is a composite of a metal and a resin is made using a resin containing a reinforcing fiber, the bonding force of the bonded portion of the metal and the resin is rather lowered.

[4. FRTP (fiber reinforced thermoplastic resin)]
In the following description, CFRTP using carbon fibers will be described. However, other fibers such as glass fibers and aramid fibers may be used. Therefore, fiber reinforced thermoplastic resin (FRTP) may be used in the present invention. Good, fiber reinforced thermoplastic resins (FRTP) other than CFRTP can also be used. Tape-like products in which carbon fiber bundles are wrapped with nylon 6, nylon 66, PPS, PEEK, etc. are mass-produced by several companies in Japan and are commercially available. The PPS tape obtained by the present inventor had a width of 50 mm and a thickness of about 0.2 mm. It can be cut with scissors and used as a CFRTP prepreg. The CFRTP prepreg can be easily made from a resin film and a carbon fiber cloth if there is a hot press.

  That is, an example of this is to prepare a flat plate-type press die, lay an aluminum foil for peeling on the lower die, and a nylon film in which a number of holes are punched with a sword (needle). Lay PPS film. Further, the carbon fiber cloth was laid thereon, and further, a number of holes were drilled at Kenzan and a resin film was laid thereon, and further, an aluminum foil for peeling was sequentially laminated. The press upper molds are stacked and lightly pressed so that the thickness of the resin amount and the carbon fiber amount is about 1 mm. In this lightly pressurized state, it is heated to about +20 to 30 ° C., which is higher than the melting point of the resin enclosing the carbon fiber bundle. Then, the CFRTP prepreg is completed by peeling off the aluminum foil for peeling on both sides. The reason for explaining this self-made prepreg is that commercially available CFRTP tapes are mostly fiber bundles, and CFRTP prepregs containing plain or twill carbon fiber cloth are difficult to obtain. Therefore, the CFRTP prepreg or the CFRTP molded product as used in the present invention refers to those containing carbon fiber fabrics such as fiber bundle type, plain weave, twill weave and satin weave.

[5. Hot press process]
Both the above-mentioned injection-bonded product made of metal and resin and the above-mentioned CFRTP prepreg (see [4. FRTP (fiber reinforced thermoplastic resin)]) were put into a press mold and hot-pressed to melt all the resin components. Then, it is a process of cooling and integrating in a short time. The hot press operation itself in this hot press process is the essence of the present invention, and therefore holds the key to achieving the present invention. In other words, the resin content in the injection-bonded product composed of the inserted metal and resin is heated to a temperature equal to or higher than the melting point of the resin during this hot press operation. It has been found that the bonding force between the metal and the resin part is drastically reduced even when cooled down. Specific measurement examples of the bonding force are shown in the examples.

  The main chemical reason is that when an injection-joint made of a metal and a resin is placed in a high-temperature environment, the pyrolysis gas is always generated from the resin portion although there is an excessive amount depending on the heating temperature. If this pyrolysis gas is generated in the vicinity of the interface where the metal and the resin are bonded, the bonding force is reduced. Therefore, one of the most important factors is to consider an operation method so as to shorten the time required for the total resin content to exceed the resin melting point as much as possible.

(Hot press hot plate specifications)
If the press machine used in the present invention is not a small press machine with a hot platen but a general press machine, the hot plate is preferably designed and manufactured in advance so as to have the following structure and function. . That is, the upper and lower heating plates are, for example, thicker than 20 mm, with a water cooling circuit to increase the cooling capacity, and a plurality of heaters to be installed and thermocouples for measuring the temperature are arranged, and the temperature of the upper and lower heating plates is What has a structure and a function with a small difference and the temperature difference between the center part of each hot platen and an edge part is preferable. In particular, when using a large press die, a temperature control electronic device is incorporated, and the heating temperature of the heater placed on the upper and lower heating plates is finely controlled, so that the temperature difference between the upper and lower heating plates and the center of each heating plate It is preferable to have a control device and control software for reducing the temperature difference between the part and the end part.

  In this way, the temperature in each part in the upper and lower heating plates is made uniform, and the surroundings of the press die and the heating plate are covered with a thick insulating material, so that the temperature deviation of each part in the press die can be reduced, and as a result, the mold The maximum temperature given to the injection-bonded material in the mold can be kept in a temperature range slightly higher than the resin melting temperature. Making the temperature given to the mold uniform in this mold at the time of hot pressing eventually reduces the amount of pyrolysis gas generated in the resin, and as a result, between the metal part resin parts in the metal CFRTP integrated product which is the final product It leads to securing high joining force.

(Hot press operation)
The temperature control of the heating plate itself is easy if it is designed and manufactured so as to exhibit the specifications and functions as described above, but it is not a direct measurement of the resin temperature in the press mold, but temporarily It is difficult to measure directly. Therefore, although it is indirect, the temperature of the hot platen is set to about the resin melting point + 30 ° C., and the temperature is smoothly raised while the temperature difference of each part of the hot plate is reduced to reach this temperature. However, since the temperature reached by the hot platen is not the temperature of the resin, during this temperature increase, the operator pays attention not to the thermometer of the hot platen but to the size of the press hydraulic pressure being applied. The pressure of the press hydraulic pressure indicates that the resin has melted, and this molten state is determined by observing the pressure value of the hydraulic pressure gauge.

  The pressure decrease due to the melting of the resin can be judged by the sudden decrease in the hydraulic pressure that occurs suddenly. If there is a sudden decrease in hydraulic pressure, the heating power supply is immediately turned off and the maximum amount of cooling water is supplied to the water cooling circuit. At the same time, the heat insulating material surrounding the press die is removed to accelerate the cooling effect. The lowered hydraulic pressure should not be increased immediately at the initially set hydraulic pressure, but should be returned to the original set pressure after a while. That is, according to the operations of the present inventors, resin leakage occurred when the lowered hydraulic pressure was immediately returned to the initial hydraulic pressure (for example, weak hydraulic pressure of about 1 MPa with respect to the press surface), and this resin leakage was not easily cured. . In short, the resin content in the press mold is in a liquid state, and if the seal portions of the upper and lower molds are not cooled to some extent, if the pressurization is continued in a liquid state, it can be said that the press pressure is low and the resin leakage continues.

  Actually, it is correct that the optimum method has not yet been found as a hot press operation for producing CFRTP molded into a desired shape. The fact is that we are struggling to develop the press operation method. In short, the oil pressure should be returned at an early stage, ignoring a certain amount of resin leakage, and the molten resin should be overheated and in the liquid stage, CFRTP should be slightly pressurized to obtain a good product, or the operation to return the oil pressure should not be done quickly. However, it is still not possible to obtain a CFRTP whose performance is slightly inferior to that described above while reducing the resin leakage by returning the hydraulic pressure to the time when the resin surface has cooled and solidified, and further increasing the pressure after cooling. Not done. After returning to about 1 MPa as described above, the present inventors further increased the pressure to about 5 MPa (on the press surface basis) when the hot platen temperature became about 100 ° C. or more lower than the resin melting point, and CFRTP Was tightened.

  Although the resin temperature at this point was not known, it was certain that the resin crystallized and solidified in the vicinity of the seal part, and the amorphous part of the resin was still expected to be highly viscous, It was thought that no resin leakage occurred while gas was released under high pressure. In any case, in order to determine what the best hot press operation method is, it is necessary to observe the finished CFRTP molded product in detail and accurately evaluate its physical properties. At present, it is only known that the pressure control operation itself is related to the amount of resin leakage together with the mechanical properties of the resulting CFRTP. These are the places where CFRTP development engineers are struggling, but from the inventors, the joint force between the metal part and the CFRTP part, which is directly related to the present invention, is based on the sudden drop in hydraulic pressure. Satisfactory results can be obtained with only a hot plate quenching operation, and only this should be clearly implemented.

The present inventors conducted various experiments as shown below. The typical apparatus used in the experiment is shown in (a) to (f).
(A) Electron microscope observation SEM type electron microscopes “S-4800 (manufactured by Hitachi, Ltd. (head office: Tokyo, Japan))” and “JSM-6700F (manufactured by JEOL Ltd. (head office: Tokyo, Japan)) ) "And observed at 1-2 KV.
(B) Measurement of bonding strength of test piece Using a tensile tester “AG-10kNX (manufactured by Shimadzu Corporation, head office: Kyoto, Japan)”, the shear breaking force was measured at a pulling speed of 10 mm / min.
(C) Heat press process The small press machine for laboratories with a heating board "MP-WNH (made by Toyo Seiki Seisakusho Co., Ltd. (head office: Tokyo, Japan))" was used.

Examples of the present invention will be described below as experimental examples.
[Experiment 1] (New NMT treatment of titanium alloy)
A commercially available 0.4 mm thick pure titanium-based titanium alloy “KS40 (manufactured by Kobe Steel, Inc. (head office: Tokyo, Japan))” thin plate was obtained and cut to create a thin plate piece of 100 mm × 100 mm. Water is put into an immersion tank, and a commercially available aluminum alloy degreasing agent “NE-6” (manufactured by Meltex Co., Ltd. (head office: Tokyo, Japan)) is added to the water, and an aqueous solution having a concentration of 7.5% ( 60 ° C.). The thin plate piece was immersed in this for 5 minutes and then washed thoroughly with water. Subsequently, a 1.5% strength aqueous caustic soda solution (40 ° C.) was prepared in another dipping bath, and the above thin plate piece was dipped in this for 1 minute and washed with water.

  Next, an aqueous solution (60 ° C.) containing 2% of an acid activator “KA-3 (manufactured by Metallurgy Engineering Laboratory, Inc. (head office: Tokyo, Japan))”, which is a universal etching agent, is prepared in another immersion tank And after immersing the said thin plate piece in this for 4 minutes, this was washed with water. Subsequently, a 3% concentration aqueous nitric acid solution (40 ° C.) was prepared in another dipping bath, and the above thin plate piece was dipped in this for 3 minutes and then washed with water. Next, in another immersion tank, a heated aqueous solution (70 ° C.) containing 2% potassium permanganate and 3% potassium hydroxide was prepared, and the above-mentioned thin plate pieces were immersed in this for 30 minutes and then washed with water. Next, a warmed aqueous solution (45 ° C.) containing 2% potassium permanganate, 1% acetic acid, and 0.5% hydrated sodium acetate is prepared in another dipping bath, and the above-mentioned thin piece is placed in this for 3 minutes. After soaking, it was washed with water. The thin plate pieces washed with water were placed in a hot air drier at 80 ° C. for 15 minutes and dried. After drying, the thin plate piece was wrapped in aluminum foil, which was then placed in a plastic bag and sealed. These treatment steps are one of the new NMT treatment methods for pure titanium alloy, and the shape and composition of the surface layer of the obtained titanium alloy satisfy the three conditions on the metal side indicated by the above-mentioned new NMT theory. Yes.

[Experiment 2 (Injection joining to titanium alloy)]
The above-mentioned surface-treated titanium alloy piece is inserted into an injection mold, and the above-described non-filler-type PPS resin “SGX100” for NMT is injected to form an injection-joined product having the shape shown in FIG. Obtained. As shown in FIG. 3, the shape of the injection bonded product is a plate-like object 11 having a size of 100 mm × 100 mm × thickness 1.2 mm. In this experiment 2, the thickness of the metal part 0.4 mm and the thickness of the resin part 12 The thickness is 0.8 mm. The injection-joint obtained in this way is deformed when it cools, so a steel flat plate is placed in a hot air dryer, and after several sheets are stacked on it, a further steel flat plate is placed, and a steel weight of about 10 kg is placed on the plate to correct it. Then, the dryer temperature was raised to 170 ° C. and left at this temperature for 1 hour, and then allowed to cool until the next day to produce a flat plate-like composite having a rectangular shape as shown in FIG. .

  Take one piece of this flat plate, forcibly peel off the metal end of the corner with a cutter, peel off the peeled end with a nipper, and see the back side of the titanium alloy sheet, and the resin powder is attached. It was confirmed that the injection joining reached the expected level. In addition, an injection joint which is a shear test piece shown in FIG. 1 is made from a pure titanium-based titanium alloy “KS40” piece and a PPS-based resin “SGX100” having a thickness of 45 mm × 18 mm × 1 mm, and this is used as an auxiliary jig. The bonding force (shear breaking force) between the metal part and the resin part measured by compressive shear fracture was 46 MPa (23 ° C.). Therefore, in the composite body 2 having the shape shown in FIG. 3 described above, it can be estimated that the joining force between the titanium alloy thin plate portion 11 and the PPS resin portion 12 is also at a 46 MPa level in terms of the shear breaking force.

[Experimental example 3] (Titanium alloy and CFRTP joint)
A press die that can be pressed to a thickness of 10 mm with a square of 100 mm × 100 mm is prepared, and the titanium alloy plate 11 having the shape shown in FIG. 3 obtained in Experimental Example 1 and the resin portion 12 that is the PPS resin “SGX100” are used. The flat plate composite 10 was placed on the lower mold of the press mold so that the resin part 12 was on the top. On this resin portion 12, 40 sheets of CFRTP tape (manufactured by Toray Industries, Inc.) using a PPS resin having a width of 50 mm and a thickness of about 0.2 mm as a matrix resin are cut into 100 mm lengths alternately in a 90 degree direction Changed and spread. Flat plate composite 10
The total length of the CFRTP tape pieces charged on the resin part 12 was 4 m and the mass was 66 g. Furthermore, a fluororesin film for peeling cut to 100 mm × 100 mm was laid on the uppermost part of the CFRTP tape piece, and an upper die was placed.

This press mold was placed in the center of the lower plate of a press “MP-WNH (manufactured by Toyo Seiki Seisakusho Co., Ltd.)” with a hot plate and a water-cooled tube, and the temperature was raised by applying a weak minimum pressure of about 1 MPa or less. When both thermometers rise to 200 ° C, a thick insulating futon (heat insulating material) is wrapped around the mold to suppress heat dissipation from the mold, and after that, while taking care not to make a difference in the upper and lower heating plate temperature The temperature was started at a target of 320 ° C. At the start of the temperature increase, a pressure of 1 MPa (about 10 kgf / cm ² ) was applied to a 100 cm ² area of 100 mm square in the calculation, and then the oil pressure gauge was watched. When the hot platen temperature was around 310 ° C, the oil pressure dropped sharply to 1 MPa or less, so the hot platen power was turned off, the tap water was fully fed, and the insulation futon was removed to see if there was resin leakage from the press mold. Watched.

  Since there was a slight resin leak and it seemed that the leak stopped immediately, when the oil pressure was returned to 1 MPa, a resin leak occurred again. Therefore, the oil pressure was reduced again to halve and the resin leak was stopped. Then, about 60 seconds after the start time of turning off the heater and starting water cooling, the hot platen thermometer fell to 200 ° C., so press oil was fed and the press pressure was increased to 5 MPa (5 times the initial pressure). Then, water cooling was continued while maintaining the high pressure, and when the temperature of both the upper and lower hot plates became 150 ° C. or lower, the pressurization by hydraulic pressure was stopped and the press mold was removed from the press machine. The press mold was disassembled to release the CFRTP molded product with metal plate. As a result, a laminated plate-like product 20 in which the titanium alloy plate 11 having the shape shown in FIG. 4 and the CFRTP molded product 14 were integrated was obtained. In this example, the total thickness is 3.5 mm, and the CFRTP part is 3.1 mm thick. Not only the resin but also carbon fiber leaked out more than expected, and the design of the seal part was difficult. I realized. However, it was felt that the obtained laminated plate-like product had a metal sound when hit with a stick and a high strength product equivalent to CFRP was obtained regardless of the front and back.

[Experimental Example 4] (Titanium alloy and CFRTP joint processed)
The hot press product including the titanium alloy plate 11 obtained in Experimental Example 3 was taken, and the entire circumference with burrs was cut using a high-speed yarn saw having a diamond blade, and as shown in FIG. 5, a 90 mm × 90 mm square plate Processed into a shaped laminate. In addition, the laminate was immersed in a degreasing solution in which the commercially available degreasing agent “NE-6 (manufactured by Meltex Co.)” for aluminum alloy used in Experimental Example 1 was placed (liquid temperature 60 ° C. ), After 5 minutes of immersion, washed well with water and then put in a hot air dryer set at 80 ° C. for 15 minutes to dry. Take out the one-component epoxy adhesive “Scotch Weld EW2040 (manufactured by Sumitomo 3M Limited (Head Office: Tokyo))” as a metal within the extent that it feels warm when the finger touches the titanium alloy plate 11 side. A thin coat was applied to the entire surface.

  On the other hand, a plate piece 15 of 90 mm × 90 mm was cut out from the above-mentioned pure titanium-based titanium alloy “KS40” plate material having a thickness of 2 mm, and this was subjected to surface treatment in exactly the same manner as in Experimental Example 1. The titanium alloy plate 15 that had been subjected to the surface treatment and was also dried by the dryer was placed on the laminated plate 20 coated with the adhesive, and placed in a hot air dryer while being placed. The four clips were sandwiched and fixed so as not to deviate from each other, and the temperature of the dryer was raised to 170 ° C., and when the temperature reached 170 ° C., the dryer was turned off for 15 minutes to cool. By this operation, a composite body having the shape shown in FIG. 5, that is, a laminated plate 30 having a titanium alloy part thickness of 2.4 mm was obtained. The laminate 30 shown in FIG. 5 is not an object for making itself, but is a first stage additional process so that the bonding force (shear breaking force) between the metal part and the CFRTP part described later can be measured. is there.

  The laminate 30 having the shape shown in FIG. 5 was cut using a high-speed yarn saw having a diamond blade, and the strip-like laminate pieces 35 (FIG. 6) each having a flat end surface of 90 mm × 15 mm were cut into six pieces. While observing the metal of the laminated plate piece 35 having the shape shown in FIG. 6 and the resin portion in the vicinity of the bonding surface 36 of the CFRTP portion with a magnifying glass with a loupe, the existence of carbon fibers was examined. It was not felt that there was a carbon fiber absent part in a part very close to 36. In short, it seems that the layer of the resin part 12 which is only the resin component without the filler which should have been joined to the injection-joined product with a thickness of 0.8 mm is almost completely mixed with carbon fibers from CFRTP. It was.

[Experimental Example 5] (Further processing of bonded titanium alloy and CFRTP)
The laminated plate having the shape shown in FIG. 6 obtained in Experimental Example 4 was processed into the shape shown in FIG. 7 using a high-speed rotary blade. That is, the shape for measuring the joining force between the original 0.4 mm-thick titanium alloy portion and the CFRTP portion as a numerical value of the shear breaking force can be measured by finally making the shape shown in FIG. It was. The shape of the sample considered that almost correct shearing force acts on the 15 mm × 6 mm = 0.9 cm ² portion left as the joint surface 45 if both ends of the shaped object shown in FIG. It is. Five specimens 40 having the shape shown in FIG. 7 were pulled and broken by a tensile tester, and the area of the fractured joint surface 45 was accurately remeasured. The calculated average shear breaking force was 42.8 MPa. It was high enough. Moreover, black resin powder remained on the fracture surface trace on the metal side, which was a material fracture of the resin part.

[Experimental Example 6] (NMT treatment of aluminum alloy)
A commercially available A5052 aluminum alloy sheet with a thickness of 0.5 mm was obtained and cut to form a 100 mm × 100 mm alloy piece. A commercially available aluminum degreasing agent “NE-6 (manufactured by Meltex Co., Ltd.)” was added to the water in the dipping bath to prepare an aqueous solution (60 ° C.) having a concentration of 7.5%. The alloy piece was immersed in this for 5 minutes and washed thoroughly with water. Subsequently, a 1% hydrochloric acid aqueous solution (40 ° C.) was prepared in another tank, and the alloy pieces were immersed in this for 1 minute and washed with water. Next, a 1.5% strength aqueous caustic soda solution (40 ° C.) was prepared in another immersion tank, and the alloy pieces were immersed in this for 4 minutes, followed by washing with water. Subsequently, a 3% nitric acid aqueous solution (40 ° C.) was prepared in another tank, and the alloy pieces were immersed in this for 3 minutes and then washed with water.

  Next, an aqueous solution (60 ° C.) containing 3.5% monohydric hydrazine is prepared in another soaking tank, and the above alloy piece is soaked for 1 minute in this, and then monohydric hydrazine is placed in another soaking tank. An aqueous solution (33 ° C.) containing 0.5% was prepared, and the alloy piece was immersed in this for 6 minutes and washed with water. Next, the square piece was put in a hot air dryer at 67 ° C. for 15 minutes and dried. After drying, the alloy piece was wrapped in aluminum foil, and then put in a plastic bag and sealed. This is the latest NMT processing method for aluminum alloys. Actually, when the A5052 aluminum alloy piece treated as described above was observed with an electron microscope at a magnification of 100,000, the entire surface was covered with a recess having a diameter of 20 to 30 nm. This electron micrograph is shown in FIG.

[Experimental Example 7] (Aluminum alloy injection joining)
The surface-treated A5052 aluminum alloy piece obtained in Experimental Example 6 was inserted into an injection mold, PPS resin “SGX100” was injected, and each of the injection joints having the shape shown in FIG. I got a lot. The appearance of the injection bonded product obtained in this experimental example was the shape shown in FIG. 3, but the thickness of the resin part was 0.7 mm, unlike the experimental example described above.

[Experimental Example 8] (Joint of aluminum alloy and CFRTP)
A press die that can be pressed to a thickness of 10 mm with a square of 100 mm × 100 mm is prepared, and an aluminum alloy piece having the shape shown in FIG. 3 obtained in Experimental Example 7 and an injection-joined product made of PPS resin “SGX100” The mold was laid so that the resin part 12 was on top. On the resin part 12, 40 sheets of a PPS CFRTP tape (made by Toray Industries, Inc.) having a width of about 0.2 mm and a thickness of about 0.2 mm are cut into 100 mm lengths, and 20 layers are formed while shifting the direction by 90 degrees. Laid down like this. The total CFRTP tape piece charged was 4 m in length and 66 g in mass. A fluororesin film cut to 100 mm × 100 mm was laid on the top, and an upper die was placed.

  In short, the subsequent hot press treatment was performed in exactly the same manner as in Experimental Example 3. As a result, an injection bonded product in which the aluminum alloy having a shape as shown in FIG. 3 and the CFRTP molded product were integrated was obtained. The total thickness was 3.4 mm, the CFRTP portion was 2.9 mm thick, and there were many resin leaks containing carbon fibers that appeared as burrs. Thereafter, the same operation as in Experimental Example 4 was performed. That is, the hot-pressed product containing the aluminum alloy thin plate obtained was processed into a square plate-shaped laminate with a 90 mm x 90 mm end face using a diamond blade high-speed yarn saw and cut into the entire circumference with burrs. And a 90 mm × 90 mm plate piece cut out from a separately prepared A5052 aluminum alloy plate having a thickness of 2 mm, were bonded with a one-component epoxy adhesive “Scotch Weld EW2040 (manufactured by Sumitomo 3M Limited)”. The obtained laminate having the shape shown in FIG. 5 was cut using a high-speed yarn saw with a diamond blade, and processed into six strip-like laminate pieces (the shape shown in FIG. 6) of 90 mm × 15 mm.

[Experimental Example 9] (Measurement of bonding force of bonded aluminum alloy and CFRTP)
The strip-shaped material having the shape shown in FIG. 6 obtained in Experimental Example 8 was processed into the shape of FIG. 7 using a high-speed rotary blade in exactly the same manner as in Experimental Example 5. That is, it is a shape for measuring the joining force between the 0.5 mm-thick aluminum alloy part and the CFRTP part as a numerical value of the shear breaking force. It is a data shape that is considered that if the both ends are pulled and broken, a substantially correct shearing force is applied to the 0.9 cm ² portion left as the joint surface. The average shear breaking force calculated by pulling and breaking five samples with a tensile tester and accurately measuring the area of the fractured surface was 43.3 MPa, which was sufficiently high. Moreover, black resin powder remained on the fracture surface trace on the metal side, which was a material fracture of the resin part.

[Experimental example 10] (New NMT treatment of aluminum plated steel sheet)
A commercially available 0.4 mm thick aluminum-plated steel sheet “ULSTER steel sheet (registered trademark of Nisshin Steel Co., Ltd. (head office: Tokyo, Japan))” was obtained and cut to produce a large number of steel sheet pieces of 100 mm × 100 mm. A commercially available aluminum degreasing agent “NE-6 (manufactured by Meltex Co., Ltd.)” was added to the water in the dipping bath to prepare an aqueous solution (60 ° C.) having a concentration of 7.5%. The steel piece was immersed in this for 5 minutes and washed thoroughly with water. Subsequently, a 1% hydrochloric acid aqueous solution (40 ° C.) was prepared in another tank, and the steel piece was immersed in this for 1 minute and washed with water. Next, a 1.5% strength aqueous caustic soda solution (40 ° C.) was prepared in another tank, and the steel pieces were immersed in this for 4 minutes and washed with water. Subsequently, a 3% nitric acid aqueous solution (40 ° C.) was prepared in another tank, and the steel pieces were immersed in this for 3 minutes and washed with water.

  Next, an aqueous solution (60 ° C.) containing 3.5% monohydric hydrazine is prepared in another tank, and the steel pieces are immersed in this for 2 minutes. An aqueous solution (40 ° C.) containing 5% was prepared, and the steel piece was immersed in this for 1 minute and washed with water. Next, an aqueous solution (45 ° C.) containing 2% potassium permanganate, 1% acetic acid and 0.5% hydrated sodium acetate is prepared in another tank, and the steel piece is immersed in this for 1 minute. Washed with water. The obtained steel piece was put into a hot air dryer set at 80 ° C. for 15 minutes and dried. After drying, the steel piece was wrapped in aluminum foil, and further put in a plastic bag and sealed. This is a new NMT processing method defined by the present inventors for an aluminum plated steel sheet.

[Experimental example 11] (Injection joining of aluminum plated steel sheet)
The 100 mm × 100 mm × 0.4 mm surface-treated aluminum-plated steel plate obtained in Example 10 was inserted into an injection mold, and a PPS resin “SGX100 (manufactured by Tosoh Corporation)” was injected. A large number of injection joints each having the shape shown were obtained. After that, in the same manner as in Experimental Example 3, using a PPS-use CFRTP tape, a laminated plate that is a composite of a metal and CFRTP formed of an aluminum-plated steel plate and CFRTP by a hot press method as shown in FIG. It was created.

  Furthermore, a new NMT type surface treatment was applied to 90 mm × 90 mm × 2 mm thick SPCC (cold rolled steel sheet). That is, it was immersed for 5 minutes in a bath of an aqueous solution (60 ° C.) in which 7.5% of a commercially available aluminum degreasing agent “NE-6” was dissolved, and washed thoroughly with water. Subsequently, a 1.5% strength aqueous caustic soda solution (40 ° C.) was prepared in another tank, and the steel pieces were immersed in this for 1 minute and washed with water. Next, a 10% strength aqueous sulfuric acid solution (60 ° C.) was prepared in another tank, and the steel pieces were immersed in this for 4 minutes and washed with water. Subsequently, 1% ammonia water was prepared in another tank, and the steel pieces were immersed in this for 3 minutes and washed with water. Next, an aqueous solution (45 ° C.) containing 2% potassium permanganate, 1% acetic acid and 0.5% hydrated sodium acetate is prepared in another tank, and the steel slab is immersed in this for 2 minutes, washed with water, 80 Dry at 15 ° C. for 15 minutes.

  Then, this surface-treated SPCC and the laminated plate using the aluminum plated steel plate were bonded to each other using a one-component epoxy adhesive in the same manner as in Experimental Example 4 to obtain a laminated plate having the shape shown in FIG. And it cut | disconnected the magnitude | size of 90 mm x 15 mm, and obtained the strip-shaped thing of the shape shown in FIG. Further, in exactly the same manner as in Experimental Example 5, the strips were cut and the shape shown in FIG. 7 was obtained and subjected to a tensile tester to measure the average bonding force (shear breaking force) of the five pieces. did. As a result, it was 41.8 MPa, and it was also found that the joint was sufficiently strong.

[Experimental Example 12] (Aluminum alloy injection joining / polyamide resin)
The surface-treated A5052 aluminum alloy piece obtained in Experimental Example 6 was inserted into an injection mold, and a polyamide resin “91G40 (Asahi Kasei Co., Ltd. (head office: Chiyoda-ku, Tokyo, Japan))” was injected to conduct an experiment. As in Example 2, an injection-joined product having the shape shown in FIG. The injection bonded product obtained in this experimental example has the shape shown in FIG. 3, but in this example, the thickness of the resin portion is 0.7 mm.

[Experimental Example 13] (Aluminum alloy and polyamide resin CFRTP integrated product)
A press mold capable of press-molding a flat plate of 100 mm × 100 mm was prepared. A 25 μm-thick nylon 66 film “Unilon G100 # 25 (manufactured by Idemitsu Unitech Co., Ltd. (head office: Minato-ku, Tokyo, Japan))” was obtained, and a number of products were prepared by cutting the film into 100 mm × 100 mm. Then, this film was laid on a wooden board, and a number of holes were made by repeatedly piercing it ten times or more with a tool provided with a large number of needles. On the other hand, a twill-woven carbon fiber cloth “CO6347B (manufactured by Toray Industries, Inc.)” having a thickness of 0.22 mm was obtained, and a large number of 100 mm × 100 mm cut products were prepared.

An aluminum foil cut to 100 mm × 100 mm was laid on the lower mold of the press die, and then a film was laid in a set of 6 sheets, and then laid alternately using 5 carbon fiber cloths and 6 sets of films. Since the last film was a single film, an aluminum foil cut into 100 mm × 100 mm was laid on it, and an upper mold was placed thereon. Then, the filled press die was set in a small press “MP-WNH (manufactured by Toyo Seiki Co., Ltd.)” with a hot platen, and the pressure was adjusted to 0.5 t by applying a hydraulic pressure to the press die. This pressure corresponds to a load of 5 kgf / cm ² (0.5 MPa) against the press surface.

  The hot platen temperature was set to 250 ° C., and the temperature of the upper and lower hot plates was raised above this set temperature, and then the target temperature was raised to 280 ° C. while taking care that the temperature of the upper and lower plates matched. When the oil pressure decreased, the press oil pressure was added to keep the oil pressure, but it was found that the oil pressure dropped greatly at around 270 ° C. and the entire resin was melted. Therefore, the hot platen power supply was turned off and water cooling was started, and the heat insulating futon was removed. The press oil was not replenished, and when the temperature of the upper and lower heating plates decreased to 100 ° C., the hydraulic pressure was removed and the mold was taken out from the press. The mold was disassembled to take out the contents, and the aluminum foil was peeled off to obtain a plate-like CFRTP. This operation was repeated to obtain a large number of thin plate-like CFRTP having a thickness of about 1 mm.

[Experimental Example 14] (Aluminum alloy and CFRTP joint / polyamide resin)
A press die that can be pressed to a thickness of 10 mm with a square of 100 mm × 100 mm is prepared, and an injection-joined product of the aluminum alloy piece of FIG. 3 shape and polyamide resin obtained in Experimental Example 12 is placed on the lower die with the resin part on top So laid. On top of that, three CFRTP thin plates made of nylon 66 of 100 mm × 100 mm obtained in Experimental Example 13 were laid. A fluororesin film cut to 100 mm × 100 mm was laid on the uppermost part, and an upper die was placed. The subsequent hot press treatment was performed in the same manner as in Experimental Example 3. However, the hot platen temperature when the press hydraulic pressure began to drop rapidly was about 280 ° C. As a result of this operation, a composite was obtained in which the aluminum alloy having a shape as shown in FIG. 4 and CFRTP using a polyamide resin as a matrix resin were integrated. The total thickness was 3.4 mm, the CFRTP part was 2.9 mm thick, and leakage of resin containing carbon fibers that appeared as burrs was also observed.

  Thereafter, the same operation as in Experimental Example 4 was performed. In other words, the hot-pressed product containing the aluminum alloy thin plate obtained was processed into a composite that is a square plate-shaped laminate with a 90 mm x 90 mm end face using a diamond blade high-speed yarn saw and cutting the entire circumference with burrs. The laminated plate and a 90 mm × 90 mm piece cut out from a separately prepared A5052 aluminum alloy plate having a thickness of 2 mm were bonded with a one-component epoxy adhesive “Scotch Weld EW2040 (manufactured by Sumitomo 3M Limited)”. . The obtained laminate plate having the shape of FIG. 5 was cut using a high-speed yarn saw with a diamond blade, and processed into six strip-like laminate plate pieces (FIG. 6) of 90 mm × 15 mm. The composite shown in FIG. 6 is obtained by cutting the composite shown in FIG. 5 into several pieces, and the joining force (shear breaking force) between the metal part and the CFRTP part in the CFRTP molded product with a metal thin plate (FIG. 4). The second-stage cutting process is performed so that measurement can be performed.

The strip-shaped material having the shape shown in FIG. 6 was processed into the shape of FIG. That is, it is a shape for measuring the joining force between the 0.5 mm-thick aluminum alloy part and the CFRTP part as a numerical value of the shear breaking force. The laminate shown in FIG. 7 is a test in which a cut is made in the cut product and the bonding force (shear breaking force) between the metal part and the CFRTP part can be measured by a tensile test. It is a piece. After all, this is an additional process in the final stage so that the bonding force (shear breaking force) between the metal part and the CFRTP part in the CFRTP molded product with a thin metal plate (FIG. 4) can be measured. Since the metal part is 2.5mm thick and the CFRTP part is 2.9mm thick, if both ends are pulled and fractured as they are, the shape of the material considered to have almost correct shearing force acting on the 0.9cm ² part left as the joint surface It is. Five samples were pulled and ruptured with a tensile tester, and the average shear breaking force obtained by re-measurement of the area of the fractured surface was 42.5 MPa, which was sufficiently high.

[Experimental Example 15] (Heating test of injection bonded product: Reference experiment)
What is shown in FIG. 2 is the appearance and dimensions of an iron container for testing the influence of heat by placing an injection joint or the like and leaving it to cover. The iron container 50 includes a box-shaped main body 53 having an open upper surface and a lid 52 on the upper portion, and includes a thermocouple hole 51 for measuring the temperature in the main body 53. The iron container 50 is a heating box for giving a thermal history to an injection joined product (shaped object shown in FIG. 1) of PPS resin “SGX100 (manufactured by Tosoh Corporation)” and various metals. The lid 52 is opened, and one injection joint having the shape shown in FIG. 1 is placed on the floor portion (not shown) disposed in the container main body 53. A lid 52 is placed on the container body 53, the lid is closed, a thermocouple is inserted into the thermocouple hole 51, and the iron container 50 is placed in a heating furnace, which is a high-temperature hot-air drying furnace. Give the heat history in a form that can be understood.

  A heating furnace in which one injection-jointed product of the shape shown in FIG. 1 of the titanium alloy “KS40” and the PPS resin “SGX100” obtained in Experimental Example 2 is housed in a container body 53 and preheated to 150 ° C. An iron container 50 was put in, and the cord connected to the thermocouple was pulled out of the heating furnace so that the temperature inside the container body 53 could be observed with a thermometer. After that, the temperature setting of the heating furnace was set to 350 ° C. and the temperature increase was started. When the temperature in the container body 53 reaches 300 ° C., immediately turn off the heating power source of the heating furnace, open the heating furnace door, quickly take out the iron container 50 with both hands wearing heat-resistant gloves, place it on the floor, and put the lid 52 on I opened it. The product was allowed to cool for about 5 minutes, and the injection bonded product was taken out from the container body 53. This experiment was a little rough but gave a high temperature history of 300 ° C. × 5 seconds. That is, considering the above operation time, 5 seconds was determined as the heating time.

  Similarly, one injection-jointed product having the shape of FIG. 1 using the titanium alloy “KS40” obtained in Experimental Example 2 is placed in the container body 53 and placed in the heating furnace, and the temperature in the heating furnace is increased. When the temperature reached 300 ° C., the heating power supply of the heating furnace was immediately turned off, and after 10 seconds, the heating furnace door was opened, the box was taken out with both hands with heat-resistant gloves and placed on the floor, and the lid 52 was opened. The product was allowed to cool for about 5 minutes, and the injection bonded product was taken out from the container body 53. In this experiment, it was assumed that a high temperature history of 300 ° C. × 15 seconds was given.

  Further, one injection joint having the shape shown in FIG. 1 using the titanium alloy “KS40” obtained in Experimental Example 2 is placed in an iron box container 50 and placed in a heating furnace, and then the temperature in the heating furnace is increased. When the temperature inside the container body 53 reaches 345 ° C., immediately turn off the heating power of the heating furnace, leave it for 10 seconds, open the heating furnace door, take out the box with both hands wearing heat-resistant gloves and place it on the floor. The lid 52 was opened. The product was allowed to cool for about 5 minutes, and the injection bonded product was taken out from the container body 53. In this experiment, a high temperature history of 345 ° C. × 15 seconds was given. Similarly, an A5052 aluminum alloy obtained in the same manner as in Experimental Example 7 and an injection-joint of “SGX100” shaped as shown in FIG. 1, and an aluminum plated steel sheet “Alster Steel Sheet (manufactured by Nisshin Steel Co., Ltd.)” A thermal history load test similar to the method described above was also performed on the injection bonded product having the shape shown in FIG. 1 of “SGX100”. On the next day after performing these tests, the bonding force was measured. The results are shown in Table 1.

  From Table 1, it was found that even when the melting point or higher was reached, the bonding force could be maintained at a level of 40 MPa if the set time was short. However, it has been found that when the injection-bonded product is placed at a high temperature close to the melting point, the bonding force is clearly reduced after cooling. Moreover, although it may be under normal pressure, the decrease in the bonding force was fast enough to be observed in seconds. Although the temperature was only 15-20 ° C. higher than the melting point, the initial bonding force (46.5 MPa) dropped to nearly 40% from the initial bonding force (46.5 MPa) in a short time of 5 seconds. This indicates that it is most important to smoothly exceed the heating peak time of the hot press at high speed. It also shows that it is not the temperature monitoring but the oil pressure monitoring that affects the hot press operation. This point is different from the point of caution when simply obtaining a CFRTP molded product from a CFRTP prepreg.

DESCRIPTION OF SYMBOLS 1 ... Metal alloy piece 2 ... Resin part 4 ... Joint part 5, 40 ... Shear stress fracture test piece 10 ... Injection-joined article 11 ... Metal thin plate 13 ... Runner 14 ... CFRTP molding 20 ... Composite 30 ... Laminate board 35 ... Lamination Plate piece 45 ... joining surface 50 ... iron container 51 ... thermocouple hole 52 ... lid

Claims (3)

An aluminum alloy surface treatment step in which the surface of the aluminum alloy shaped article is covered with an ultrafine recess having a diameter of 20 to 50 nm and the amine-based molecules are chemically adsorbed;
Inserting the aluminum alloy shaped article that has undergone the surface treatment step into an injection mold, and injecting a polyamide resin or a polyphenylene sulfide-based resin composition onto the surface to create an injection bonded product;
A charging step in which the injection-bonded product is loaded into a hot press mold, and the polyamide resin or the polyphenylene sulfide is a matrix resin and the FRTP prepreg or FRTP molded product is stacked and loaded on the injected resin; ,
In the hot press mold, for heating and pressurizing in order to perform both heat fusion of the matrix resin and the injected polyamide resin or the polyphenylene sulfide resin composition , which are the same type, at a time. A hot press process ;
In the hot pressing step, the start of melting of the injected polyamide resin or polyphenylene sulfide resin composition and the matrix resin is detected by the numerical value of the pressurization, and immediately after the decrease of the pressurization is detected, A method for producing a composite of metal and FRTP, characterized in that cooling of the panel is started. The surface has a roughness on the order of microns in which the average length (RSm) of the contour curve element is 0.8 to 10 μm and the maximum height (Rz) is 0.2 to 5 μm, and has the roughness. A metal alloy surface treatment step for producing a metal alloy shaped article in which ultrafine irregularities having a period of 10 to 300 nm are present and the surface layer is covered with a thin ceramic layer of metal oxide or metal phosphate,
Inserting the metal alloy shaped article that has undergone the surface treatment step into an injection mold, and injecting a polyamide resin or a polyphenylene sulfide-based resin composition onto the surface layer to create an injection bonded product; and
Loading step of charging the hot-press mold with the injection-bonded product, and charging the injected resin with the FRTP prepreg or FRTP molding using the polyamide resin or the polyphenylene sulfide resin as a matrix resin;
In the hot press mold, for heating and pressurizing in order to perform both heat fusion of the matrix resin and the injected polyamide resin or the polyphenylene sulfide resin composition , which are the same type, at a time. A hot press process ;
In the hot pressing step, the start of melting of the injected polyamide resin or polyphenylene sulfide resin composition and the matrix resin is detected by the numerical value of the pressurization, and immediately after the decrease of the pressurization is detected, A method for producing a composite of metal and FRTP, characterized in that cooling of the panel is started. In the manufacturing method of the composite_body | complex of the metal and FRTP of Claim 1 or 2 ,
The FRTP uses CFRTP (carbon fiber reinforced thermoplastic) or AFRTP (aramid fiber reinforced thermoplastic). A method for producing a composite of metal and FRTP.