JPH06305037A - Preparation of fiber-reinforced resin pipe - Google Patents

Abstract

PURPOSE:To provide a pipe being lightweight, with good surface accuracy and improved durability, to simplify manufacturing process and to reduce manufacturing cost by a method wherein a fluid pressure is acted in an inner pressure holding body and an uncured fiber-reinforced resin layer is brought into tight contact with the inner face of an outer mold on which a metal foil is arranged by the expanding pressure and then, the resin layer is cured. CONSTITUTION:An inner pressure holding body 3 is arranged outside of an inner mold 2 and an uncured fiber-reinforced resin layer 4 is formed on the outside by means of a filament winding method. Then, a metal foil 5 is arranged on the inner face of an outer mold 1 with a cylindrical inner face. Then, the inner mold is arranged inside of the outer mold 1 and the inner pressure holding body 3 is expanded by introducing air pressure into the inner pressure holding body 3. The uncured fiber-reinforced resin layer 4 is brought into tight contact with the outer mold 1 by the expanding pressure. The fiber-reinforced resin layer 4 is cured while this condition is kept to obtain a fiber-reinforced resin pipe with a metal-clad surface.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a fiber reinforced resin (hereinafter referred to as F
(Sometimes referred to as RP).

[0002]

2. Description of the Related Art Since FRP has a characteristic that it has higher specific strength and higher specific rigidity than metal materials, it has started to be used in industrial fields such as FRP pipes. However, the hardness of FRP pipes is lower than that of metals, so they are easily scratched by the objects to be contacted. They have poor wear resistance and thus have a short life. In addition, since they are poor conductors of electricity, static electricity may be generated depending on the usage form. There was a problem that it was easy.

In order to solve these problems, FRP
It has been studied to use the surface of a pipe made of metal by using it. As a method of manufacturing this type of pipe, for example, F
A pipe material pipe made of RP is molded, and a conductive treatment agent layer made of a resin composition containing metal powder is formed on the surface thereof,
A method is known in which a metal tubular body is covered, a copper or nickel plating layer is formed on the surface by electrolytic plating, and the surface is ground or polished to finish.

[0004]

SUMMARY OF THE INVENTION These conventional manufacturing methods involve plating steps for metallizing the surface of pipes and machining steps such as turning, grinding or polishing for precision of the outer surface. Since many are required, the raw material yield is low, the manufacturing cost is high, and there is a problem in economic efficiency. In addition, the FRP pipe obtained by these methods cannot achieve sufficient weight reduction, or the FRP pipe element pipe and the plating layer are not necessarily joined sufficiently, and thus higher performance and lighter weight are desired. There was a problem that it was not suitable for rare uses.

An object of the present invention is to solve the above-mentioned problems. It is lightweight, has excellent dimensional accuracy, has a high yield of raw materials, and reduces the machining process as much as possible to simplify the manufacturing process. FR that can withstand stable use over a long period of time
The purpose is to provide P pipes. INDUSTRIAL APPLICABILITY The method of the present invention is suitable for manufacturing lighter weight FRP rolls, golf clubs, fishing rods and the like.

[0006]

The present invention comprises the following inventions. 1st invention: The manufacturing method of the fiber-reinforced resin pipe with which the surface was coated with the metal characterized by performing the following process in this order. 1. A step of disposing an internal pressure holder on the outside of the inner mold and forming an uncured fiber-reinforced resin layer on the outer side thereof, and a step of disposing a metal foil on the inner surface of the outer mold having a cylindrical cavity. 2. A step of disposing an inner pressure holding body and arranging an inner mold on which an uncured fiber-reinforced resin layer is formed inside the outer mold on which the metal foil is arranged. 3. A step of expanding the internal pressure holder by applying a fluid pressure to the inside of the internal pressure holder, and bringing the uncured fiber-reinforced resin layer into close contact with the inner surface of the outer die on which the metal foil is arranged by the expansion pressure. 4. A step of curing the uncured fiber-reinforced resin layer.

Second invention: A method for manufacturing a fiber-reinforced resin pipe whose surface is coated with a metal, characterized in that the following steps are performed in this order. 1. A step of disposing an internal pressure holder on the outside of the inner mold and forming an uncured fiber-reinforced resin layer on the outside thereof. 2. A step of disposing a metal foil on the outer surface of the uncured fiber-reinforced resin layer formed on the outer side of the inner mold. 3. A step of installing an inner mold in which an uncured fiber-reinforced resin layer is formed and a metal foil is arranged inside an outer mold having a cylindrical cavity. 4. A step of expanding the internal pressure holder by applying a fluid pressure to the inside of the internal pressure holder, and bringing the uncured fiber-reinforced resin layer into close contact with the inner surface of the outer mold via the metal foil by the expansion pressure. 5. A step of curing the uncured fiber-reinforced resin layer. The present invention will be described in detail below. The method of the present invention is characterized by performing the steps as described above, but may include additional additional steps before and after each step.

In the present invention, the reinforcing fiber used for forming the FRP pipe is preferably a fiber having a high elastic modulus and strength because it is necessary to reduce the amount of bending under load. Such fibers include, for example, carbon fibers, glass fibers, aramid fibers, and ceramic fibers. Moreover, you may use these fibers in combination of 2 or more types. Specific strength,
A reinforced fiber having a large specific rigidity is more preferable because the effect of weight reduction is more remarkable, and a fiber having an elastic modulus of 150 GPa or more, preferably 200 GPa or more is preferable. Examples of the fiber having a modulus of elasticity of 150 GPa or more include carbon fiber.

The matrix resin used for molding the FRP pipe is not particularly limited, and includes epoxy resin, unsaturated polyester resin, vinyl ester resin, urethane resin, phenol resin, alkyd resin,
Thermosetting resin such as xylene resin, melamine resin, furan resin, silicone resin, polyethylene resin, polypropylene resin, polyvinyl chloride resin, polymethacrylate resin, ABS resin, fluorine resin, polycarbonate resin,
Polyester resin, polyamide resin (nylon 6,6.
6, 6.10, 6.11, 6.12), a thermoplastic resin such as a polyphenylene sulfide resin, a polysulfone resin, a polyether sulfone resin, a polyether ether ketone resin, and a polyphenylene oxide resin. Of these, epoxy resins, unsaturated polyester resins and vinyl ester resins are preferable from the viewpoint of handleability. These resins and reinforcing fibers may be used in combination of two or more, if necessary.

The inner die used in the present invention is not particularly limited, but it is preferable to use a die having a cylindrical outer surface, for example, a mandrel made of stainless steel.

The internal pressure holder arranged on the outer surface of the inner mold is
It has a function of expanding when a fluid pressure is applied to the inside thereof, for example, by introducing compressed air or the like. Specifically, a cylindrical inner mold is covered with a tube, and both ends of the tube are brought into close contact with the surface of the inner mold to form a seal when a fluid pressure is applied, and a fluid pressure inlet is provided. However, the present invention is not limited to this, but may be, for example, a bag having a fluid pressure introduction port and a bag arranged around the inner mold so as to wrap the inner mold.

The material of the internal pressure holding member is preferably an elastic material, for example, a film made of a thermoplastic synthetic resin such as silicone rubber, natural rubber, polyvinyl chloride, polyamide (nylon), polyester, polypropylene or polyethylene, or Examples thereof include a film in which these are combined and laminated.

Various conventionally known methods can be used to form the uncured fiber-reinforced resin layer on the outside of the internal pressure holder. For example, the fiber tow of the reinforcing fibers can be impregnated with the above-mentioned uncured matrix resin, and then can be produced according to the method of the present invention described below using the filament winding method. Instead of the filament winding method, it is also possible to use a method of winding a sheet-like prepreg in which uncured resin is impregnated around aligned fiber bundles.

The outer mold having a cylindrical cavity used in the present invention is an outer mold having an inner cavity for forming a cylindrical outer surface of an FRP pipe with high accuracy. Steel, aluminum, etc.
It can be manufactured using various conventionally known materials. The outer shape of the outer mold is not particularly limited. To reduce the weight of raw materials, FRP is used as the outer mold.
It is preferable to use a pipe made of. It is preferable that the inner surface of the outer die be accurately finished. By doing so, the accuracy of the finish of the outer surface of the FRP pipe after molding is improved.

An inner pressure holder and an uncured fiber-reinforced resin layer are arranged inside the outer mold prepared as described above,
The formed inner mold is installed, and fluid pressure is applied to the inner pressure holding body. The type of fluid that acts on the internal pressure holder is not particularly limited, but it is preferable because compressed air is easy to handle. The pressure of the fluid to be actuated is FR, which was previously determined by the structural design.
It depends on the wall thickness of P pipe, the laminated structure, the laminated angle and the like and is not necessarily limited, but is preferably at least 0.2 MPa, more preferably 0.3 MPa or more. In addition, before applying the fluid pressure, if the entire inside of the outer mold is sealed and sucked by vacuum, the FRP without the inclusion of voids
This is more preferable because a pipe made of the same can be obtained.

By expanding the internal pressure holder by the action of fluid pressure, the fiber reinforced resin layer is brought into close contact with the inner surface of the outer mold via the metal foil. Then, the fiber reinforced resin layer is heat-cured according to a usual method, and then the outer mold, the inner mold and the inner pressure holding body are removed to obtain an FRP having a good outer surface accuracy.
Get a pipe made.

The metal foil is arranged on the inner surface of the outer mold or on the outer side of the uncured fiber reinforced resin layer, and adheres to the outer surface of the FRP pipe after molding. The material of the metal foil is stainless steel,
Examples include copper, nickel, a nickel / copper two-layer structure, and a nickel / copper / nickel three-layer structure, but these are appropriately selected depending on the application and are not particularly limited.

Examples of the metal foil include electrolytic metal foil, rolled metal foil, and the like, and the form thereof is a quadrangular shape having a size capable of covering the entire surface of the pipe with one layer of foil, a tube shape, or a perforated tube shape. preferable. Further, when the metal foil has a rectangular shape, the metal foils may overlap each other when they are formed on the outer surface of the FRP pipe. In order to obtain high joint strength between the metal foils and the joint surface between the metal foil and the fiber reinforced resin, it is preferable that at least the surface in contact with the fiber reinforced resin layer is roughened. Examples of such a material include electrolytic metal foils having one surface or both surfaces wholly or partially roughened.

Here, roughening means that the surface of the metal foil is made uneven, bumpy or mushroom-shaped. Examples of the roughening method include electrochemical treatment, chemical treatment such as etching, and mechanical treatment such as rubbing with a wire brush.

The thickness of the metal foil is 150 in terms of handleability.
μm or less is preferable. More preferably 20 to 100 μ
m. If it exceeds 150 μm, the weight increases and the rigidity of the metal foil material increases.
It is not preferable because the surface of the RP pipe has irregularities.

The preferred method of arranging the metal foil on the outer mold is to bring it into close contact. Various methods are conceivable as a method for bringing the metal foil into close contact with the outer mold. For example, a square metal foil is rolled so as to fit the inner surface of the outer mold, and the metal foil is placed on the inner surface of the outer mold after an adhesive agent such as a film or liquid is attached to the overlapping metal foils. The inner cylinder made of metal foil is pressed with air pressure or the like through a bag made of polyvinyl chloride, polyethylene or the like to be brought into close contact with the outer mold.

The overlap margin of the overlapping metal foils is
It is preferably about 0.1 to 10 mm. Overlap margin is 0.1m
If it is less than m, strict process control is required to prevent the gap from opening. Further, if it is larger than 10 mm, material loss becomes large, which is not preferable.

As the metal foil, a metal foil tube can be used. When using a metal foil tube, insert the metal foil inside the outer mold and press it with air pressure etc. from the inside of the inner cylinder made of metal foil through a bag of polyvinyl chloride, polyethylene, etc. A metal foil can be adhered to the mold. The method for disposing the metal foil on the outer surface of the uncured fiber-reinforced resin layer formed on the outer side of the inner mold is not particularly limited.

The method for curing the fiber reinforced resin layer is not necessarily limited. It is possible to use a method in which the inner mold and the outer mold are integrated with each other, and the mixture is placed in a heat curing furnace and heated and cured while the fluid pressure is applied to the inner pressure holder.

[0025]

[Examples] Specific examples will be described below.
The invention is not limited by these examples.

As the carbon fiber, Magnamite (registered trademark) IM6 manufactured by Sumika Hercules Co., Ltd. (tensile elastic modulus 27)
6 GPa and tensile strength 4.4 GPa) were used. As the epoxy resin composition, bisphenol A (Sumiepoxy (registered trademark) E manufactured by Sumitomo Chemical Co., Ltd.) is used as an epoxy resin.
LA128), hexahydrophthalic anhydride (HN5500 manufactured by Hitachi Chemical Co., Ltd.) as a curing agent, and 2,4,6-tris (dimethylaminomethyl) phenol (Sumicure manufactured by Sumitomo Chemical Co., Ltd.) as a curing aid. (Registered trademark) DMP30) was used in a stoichiometric amount.

Example 1 A stainless mandrel having an outer diameter of 100 mm and a length of 2,500 mm was mounted on a filament winding apparatus, a mold release agent was applied to the mandrel, and then carbon fiber was impregnated in a liquid epoxy resin composition. It was wrapped around, placed in a heat curing oven, and heated at 150 ° C. for 2 hours to cure. The wrapping of the fiber is 3 mm at an angle of ± 55 ° and 0.
An outer mold made of fiber reinforced resin was made to have a thickness of 5 mm. This outer mold is represented by (1) in FIG.

A 35 μm-thick electrolytic copper foil (CF-T8 manufactured by Fukuda Metal Foil & Powder Co., Ltd.) was cut into a 2200 mm × 315 mm square shape and rounded to fit the inner surface of the outer mold, and the electrolytic copper foils overlap each other. Film adhesive (8) on the part (America Cyanamid Company (America
FM (registered trademark) 123-2) manufactured by n Cyanamid Company is attached as shown in FIG. 2, an electrolytic copper foil is inserted inside the outer mold, and is placed inside an inner cylinder formed of the electrolytic copper foil. 0.1M via a polyvinyl chloride bag
By applying air pressure of Pa for 10 minutes, the electrolytic copper foil was brought into close contact with the outer mold made of fiber reinforced resin. This electrolytic copper foil is represented as a metal foil (5) in FIG.

On the other hand, the inner diameter is 65 mm and the length is 2
A special mandrel (2) made of stainless steel of 000 mm is attached to the filament winding device, and a silicon tube (heat-shrink rubber tube ST-400DG manufactured by Shin-Etsu Chemical Co., Ltd.) is covered as the internal pressure holder (3) on this mandrel, and this silicon is used. A polyester film (manufactured by Toyobo Co., Ltd., trade name E) is used as a seal when the both ends of the tube are closely adhered to the stainless special mandrel and air pressure is applied to the outer side of the silicon tube for release.
-7006) was wrapped. Then, the carbon fiber was impregnated with a liquid epoxy resin composition and wound around the entire outer circumference of the silicon tube around which the polyester film was wound. The winding angle of the fiber was ± 10 °, and the winding thickness was 8.5 mm. The volume ratio of carbon fiber to resin was adjusted so that the amount of resin adhered was 60 ± 2%. In FIG. 1, the uncured fiber-reinforced resin layer is (4)
It is represented by.

A silicon tube and an inner mold wound with a fiber reinforced resin are put inside an outer mold made of a fiber reinforced resin in which an electrolytic copper foil is adhered to the inner surface, and the inside of the outer mold made of the fiber reinforced resin is vacuum-sucked. A vacuum pressure of 30 MPa is applied through the port (6) for 30 minutes, and an air pressure of 0.3 MPa is applied to the void portion formed by the outer surface of the inner mold and the silicon tube through the fluid pressure inlet port (7) while vacuuming. By operating for a minute, the electrolytic copper foil on the inner surface of the outer mold made of the fiber-reinforced resin is brought into close contact by expanding the fiber-reinforced resin wound around the inner mold,
Fiber reinforced resin and electrolytic copper foil are integrated.

The above integrated fiber reinforced resin and electrolytic copper foil were placed in a thermosetting oven with air pressure acting on the outer mold and the inner mold, and heated and cured while rotating at 120 ° C. for 2 hours. After curing, the mold was removed from the outer mold and the inner mold, and unnecessary parts at both ends were cut and removed to obtain a carbon fiber reinforced resin pipe whose surface layer was covered with electrolytic copper foil.

The pipe obtained by the method of the present invention is suitable for production when metalizing the surface of rolls, golf clubs, fishing rods and the like.

[0033]

The FRP pipe manufacturing method of the present invention has a reduced number of machining steps as compared with the conventional methods, the raw material yield is improved, and the manufacturing cost is simplified by simplifying the manufacturing steps. Has been reduced. In addition, the FRP pipe obtained by the method of the present invention is lighter in weight than the conventional FRP pipe, has the same or higher surface performance and static electricity removal performance, and has a joint strength between the FRP tubular body and the metal layer. Is strong and durable.

[Brief description of drawings]

FIG. 1 is a cross-sectional view of an example of an arrangement of an inner die, an outer die, an inner pressure holder, a metal foil, and a fiber reinforced resin layer at the time of molding a FRP tubular body having a metal foil on an outer surface.

FIG. 2 is a partial cross-sectional view showing an example of an arrangement of an outer mold, a metal foil, and a film adhesive, showing details of a portion where metal foils overlap each other.

[Explanation of symbols]

 1: Outer mold 2: Inner mold 3: Inner pressure holder 4: Unhardened fiber reinforced resin layer 5: Metal foil 6: Vacuum suction port 7: Fluid pressure introduction port 8: Film adhesive

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Internal reference number FI Technical display location // B29L 23:00 4F (72) Inventor Koji Yamatatsu 6 Kitahara, Tsukuba, Ibaraki Sumitomo Chemical Co., Ltd. In-house (72) Inventor Yoshiki Matsuoka 6 Kitahara, Tsukuba-shi, Ibaraki Sumitomo Chemical Co., Ltd.

Claims (2)

[Claims] 1. A method for producing a fiber-reinforced resin pipe whose surface is coated with a metal, characterized in that the following steps are performed in this order. 1. A step of disposing an internal pressure holder on the outside of the inner mold and forming an uncured fiber-reinforced resin layer on the outer side thereof, and a step of disposing a metal foil on the inner surface of the outer mold having a cylindrical cavity. 2. A step of disposing an inner pressure holding body and arranging an inner mold on which an uncured fiber-reinforced resin layer is formed, inside the outer mold on which the metal foil is arranged. 3. A step of expanding the internal pressure holder by applying a fluid pressure to the inside of the internal pressure holder, and bringing the uncured fiber-reinforced resin layer into close contact with the inner surface of the outer die on which the metal foil is arranged by the expansion pressure. 4. A step of curing the uncured fiber-reinforced resin layer. 2. A method for producing a fiber-reinforced resin pipe whose surface is coated with a metal, characterized in that the following steps are performed in this order. 1. A step of disposing an internal pressure holder on the outside of the inner mold and forming an uncured fiber-reinforced resin layer on the outside thereof. 2. A step of disposing a metal foil on the outer surface of the uncured fiber-reinforced resin layer formed on the outer side of the inner mold. 3. A step of installing an inner mold in which an uncured fiber-reinforced resin layer is formed and a metal foil is arranged inside an outer mold having a cylindrical cavity. 4. A step of expanding the internal pressure holder by applying a fluid pressure to the inside of the internal pressure holder, and bringing the uncured fiber-reinforced resin layer into close contact with the inner surface of the outer mold via the metal foil by the expansion pressure. 5. A step of curing the uncured fiber-reinforced resin layer.