JPH0335107B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing a metal-fiber-reinforced thermosetting resin composite in which a metal and a fiber-reinforced thermosetting resin are firmly bonded. More specifically, the present invention relates to a method of manufacturing a metal-fiber-reinforced thermosetting resin composite by providing a sprayed metal layer on a metal surface and bonding the metal and fiber-reinforced thermosetting resin via the sprayed layer. .

Traditionally, composites of metal and fiber-reinforced thermosetting resin have been implemented in many fields for the purpose of rust prevention, insulation, and coloring of metals, or for the purpose of reinforcing fiber-reinforced thermosetting resin and making it conductive. has been done. However, the adhesion of fiber-reinforced thermosetting resins to metals is generally poor, and this tends to cause problems in which the metal and fiber-reinforced thermosetting resins peel off.

To improve this, attempts have been made to improve the adhesive strength between metal and fiber-reinforced thermosetting resin by using metal adhesives or primers, or by treating the metal surface to create irregularities. However, it is still not sufficiently effective or requires a lot of effort, so the development of a method for joining metal and fiber-reinforced thermosetting resin that is simple and has sufficient adhesive strength is awaited. The current situation is that

As a result of intensive research in view of the current situation, the present inventors have determined that a thermal sprayed layer of a porous metal that is firmly bonded to the metal and that is porous is provided in advance on the surface of the metal that is to be bonded to the fiber-reinforced thermosetting resin. , then supplying a thermosetting resin and reinforcing fibers to this sprayed layer,
If resin is impregnated into the sprayed layer and reinforcing fibers and then cured, the sprayed material and thermosetting resin become entangled in a complicated manner inside the sprayed layer because the sprayed layer is porous.
The inventors have discovered that it is possible to obtain a metal-fiber-reinforced thermosetting resin composite having strong adhesive strength, leading to the present invention.

That is, in the present invention, when bonding a metal and a fiber-reinforced thermosetting resin to obtain a metal-fiber-reinforced thermosetting resin composite, the metal is coated with a thermal spray coating on the surface to be bonded to the resin in advance. After that, a thermosetting resin and reinforcing fibers are supplied to the thermal sprayed coating, and the thermosetting resin is impregnated into the thermal sprayed coating and the reinforcing fibers at room temperature or under heating, and the reinforcing fibers are impregnated simultaneously with the impregnation or subsequently. The method is characterized in that a metal-fiber reinforced thermosetting resin composite is produced by molding a fiber-reinforced thermosetting resin molded article on the thermal spray coating and then curing the resin.

In carrying out the present invention, first, a thermal spray layer of about 10 to 500 microns is formed by thermal spraying on a metal that has been subjected to pretreatment such as degreasing or blasting as necessary. If the metal sprayed layer is thinner than 10 microns, sufficient adhesion cannot be obtained, and if it is thicker than 500 microns, there is little improvement in adhesion, both of which are undesirable.

Next, thermosetting resin and reinforcing fibers are supplied to the thermal spray layer using heat/pressure molding such as injection, press, and transfer, or methods such as resin injection, hand lay-up, and spray-up. A thermosetting resin is impregnated into the inside of the thermal sprayed coating and the reinforcing fibers at room temperature or under heating, a fiber-reinforced thermosetting resin molded body is formed on the thermal sprayed coating simultaneously or subsequently with the impregnation, and then the resin is cured. By this process, a metal-fiber reinforced thermosetting resin composite can be obtained.

The metals that can be used for the metal-fiber reinforced thermosetting resin composite in the present invention include single metals and alloys such as iron, aluminum, stainless steel, brass, steel, zinc, copper, and cupronickel, and metals that are solid at room temperature. can all be used.

In addition, thermosetting resins that can be used for the metal-fiber reinforced thermosetting resin composite include epoxy resins and unsaturated polyester resins.
Any resin that can change from a liquid state to a solid state by curing that can be impregnated into the porous sprayed surface and the reinforcing fibers can be used. In addition, it is easy to obtain a liquid thermosetting resin with a low viscosity, so that the thermal spray layer and reinforcing fibers are sufficiently impregnated to obtain a metal fiber-reinforced thermosetting resin composite with strong adhesive strength. be able to. In the present invention,
By blending reinforcing fibers into these thermosetting resins,
Used as fiber-reinforced thermosetting resin. It is also possible to mix fillers and colorants into these thermosetting resins. Among these, glass fiber-reinforced thermosetting resins containing glass fibers are preferred because the resulting composite has excellent strength. However, the present invention is not limited to the composition or blending of such fiber-reinforced thermosetting resin.

Thermal spraying used in the present invention refers to a method of spraying metal in a molten or semi-molten state, such as gas spraying, arc spraying, or plasma spraying, to form a porous sprayed layer.The sprayed materials include iron, aluminum, etc. All metal materials commonly used in thermal spraying, such as stainless steel, zinc, and copper, can be used, but appropriate equipment and materials must be selected depending on the intended use of the metal-fiber reinforced thermosetting resin composite. desirable.

Hereinafter, the present invention will be explained in more detail with reference to Examples. Note that all parts in the examples represent parts by weight.

Example 1 One side of a mild steel plate with a thickness of 5 mm and a length and width of 300 mm was heated using steel grid #100 and an air pressure of 5 mm.
After blasting under conditions of Kg/ ^cm2 , the blasted surface of the mild steel plate was coated with 70% aluminum using a gas spraying machine (Top Jet, manufactured by SNMI, France) by a conventional method. Sprayed to micron thickness. Next, a resin composition prepared by mixing 1 part of a 55% solution of methyl ethyl ketone peroxide with 100 parts of an unsaturated polyester resin (manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd., Eporak G-752PTX) was applied to the thermally sprayed aluminum layer by roll brushing. Then, 5 plies of glass mat (manufactured by Nitto Boseki Co., Ltd., MC-450A) were laminated using the above resin composition by hand lay-up method,
It was then cured at room temperature.

The resulting composite with a thickness of 10 mm consisting of a mild steel plate and glass fiber reinforced unsaturated polyester resin was firmly bonded.

After placing this complex in an oven at 100 °C for 60 minutes,
No change was observed even after 20 cycles of cold and hot repeated tests, one cycle of which was immersion in ice water at 0°C for 60 minutes.

Comparative Example 1 After blasting one side of a mild steel plate with a thickness of 5 mm and a length and width of 300 mm under the same conditions as in Example 1, unsaturated polyester resin (manufactured by Nippon Shokubai Chemical Co., Ltd.) was applied to the blasted surface. ,Epolorac G
A resin composition prepared by mixing 1 part of a 55% solution of methyl ethyl ketone peroxide per 100 parts of resin was applied to glass matte (manufactured by Nitto Boseki Co., Ltd., MC-450A) using a roll brush.
Five plies were laminated using the above resin composition by a hand lay-up method, and then cured at room temperature.

When the resulting composite of the mild steel plate and the glass fiber-reinforced unsaturated polyester resin was placed in an oven at 100°C for 60 minutes, the glass fiber-reinforced unsaturated polyester resin layer was completely separated from the mild steel plate.

Example 2 After blasting both sides of a mild steel plate with a thickness of 3 mm, a width of 200 m, and a length of 4 mm under the same conditions as in Example 1, an arc thermal spraying machine (manufactured by TAFA, USA, 375EFS) to a thickness of 100 microns according to known techniques. This thermally sprayed mild steel plate is surrounded by swirl mats (manufactured by Asahi Fiberglass Co., Ltd., M8624).
Furthermore, the outer periphery is made of unsaturated polyester resin (manufactured by Nippon Shokubai Chemical Co., Ltd., Epolack G-151NL).
100 parts, 1 part of benzoyl peroxide, calcium carbonate (manufactured by Nitto Funka Chemical Co., Ltd., NS-100) 50
Glass roving impregnated with a resin composition containing 300% (Nitto Boseki Co., Ltd., PS220RL-510)
The books are lined up in the longitudinal direction, and the outer periphery is surrounded by a swirl mat (same as the swirl mat described above), and then drawn into a mold whose temperature is controlled to 110°C, and passed through the mold at a drawing speed of 50 cm/min. After heating and hardening, a composite body was obtained in which a thermally sprayed mild steel plate was placed in the center and the outer periphery was FRP.

The resulting composite of the mild steel plate and the glass fiber-reinforced unsaturated polyester resin was firmly bonded.

This composite was subjected to 20 cycles of cold and hot repeated tests under the same conditions as in Example 1, but no change was observed.

Example 3 After blasting the outer surface of a steel pipe with an inner thickness of 2.5 mm, an inner diameter of 300 mm, and a length of 4 m under the same conditions as in Example 1, an arc thermal spraying machine (manufactured by TAFA, USA) was applied to the blasted surface. 375EFS) to a thickness of 50 microns according to known techniques.

This thermally sprayed steel pipe was fixed so that it could rotate in the circumferential direction, and 1 part of a 55% solution of methyl ethyl ketone peroxide was added to 100 parts of unsaturated polyester resin (Eporak G-103, manufactured by Nippon Shokubai Chemical Co., Ltd.).
glass roving (manufactured by Nippon Sheet Glass Co., Ltd.).
RER231FW11) was impregnated with unsaturated polyester resin and wound around the steel pipe while rotating in the circumferential direction, and filament winding molding was performed on the outer periphery of the thermally sprayed steel pipe to create a glass roving impregnated with unsaturated polyester resin to a thickness of 5 mm. A layer was formed and then cured at room temperature to obtain a composite of the steel pipe and glass fiber reinforced unsaturated polyester resin.

The obtained composite was strongly bonded, and no change was observed in 20 cycles of cold/heat repeated tests under the same conditions as in Example 1.

Claims (1)

[Scope of Claims] 1. When bonding a metal and a fiber-reinforced thermosetting resin to obtain a metal-fiber-reinforced thermosetting resin composite, the metal is thermally sprayed on the surface to be bonded to the resin in advance. Form a film, then supply a thermosetting resin and reinforcing fibers to the thermal sprayed coating, impregnate the inside of the thermal sprayed coating and the reinforcing fibers with the thermosetting resin at room temperature or under heating, and simultaneously or simultaneously with the impregnation. A method for producing a metal-fiber-reinforced thermosetting resin composite, comprising subsequently molding a fiber-reinforced thermosetting resin molded article on the thermal spray coating, and then curing the resin. 2. The method for producing a metal-fiber reinforced thermosetting resin composite according to claim 1, wherein the thickness of the sprayed coating is in the range of 10 to 500 microns. 3 Thermal spray coating has a void ratio of 1% by volume or more10
The method for producing a metal-fiber reinforced thermosetting resin composite according to claim 1, wherein the amount is less than or equal to the volume percent. 4 Metal-fiber reinforced thermosetting resin composite is metal-
The method for producing a metal-fiber-reinforced thermosetting resin composite according to claim 1, which is a fiber-reinforced thermosetting resin laminate.