JPH0570614A - Prepreg - Google Patents

Abstract

PURPOSE:To obtain lightweight prepreg for golf club, etc., having high vibration- damping properties, impact resistance and strength by forming a fiber reinforced composite resin layer having reinforcing fibers impregnated with a matrix resin or a resin layer containing no reinforcing fibers on the surface of metal fiber paper. CONSTITUTION:Reinforcing fibers 2 such as polyacrylonitrile-based carbon fibers having 7.0mum fiber diameter are impregnated with a matrix resin 5 such as epoxy resin to give a fiber reinforced composite resin layer 4, which is superimposed on one side of a metal fiber paper 3 such as stainless steel fiber paper using stainless steel short fibers having 2-12mu fiber diameter and 1-10mm fiber length, pressed by rollers, etc., and bonded to give fiber reinforced prepreg 1. The opposite side of the fiber reinforced composite resin layer 4 of the fiber reinforced prepreg 1 thus obtained is coated with the same resin layer 5' as the matrix resin 5, containing no reinforcing fibers to give the objective prepreg suitable for producing a member having high compression strength, impact strength and torsional rupture strength.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention is light in weight and excellent in mechanical properties, particularly toughness, excellent in vibration damping property and impact resistance property, and further excellent in compressive strength and torsional fracture strength.
For example, golf club shafts or golf club head faces, fishing rods, sports and leisure products such as various racket frames such as tennis rackets or badminton rackets, bicycle frames, and pipe materials for various machine parts, and other members. The present invention relates to a prepreg which can be preferably used for manufacturing a prepreg. Particularly, in the prepreg of the present invention, a fiber-reinforced composite resin layer in which a matrix resin is impregnated in a reinforcing fiber or a resin layer having no reinforcing fiber is arranged on at least one side of a metal fiber paper, and impact strength and A prepreg having excellent torsional fracture strength is provided.

[0002]

2. Description of the Related Art In recent years, prepregs made of carbon fibers and other various reinforcing fibers have been widely used in various technical fields. For example, even when manufacturing sports equipment such as golf club shafts, they are lightweight and have high mechanical strength. It is often used because it is expensive, and has achieved extremely good results.

However, further improvements are desired in terms of strength and elastic modulus or in terms of feel during use, and in order to meet such demands, as a fiber reinforced prepreg, for example, carbon fiber and It is proposed to use a hybrid prepreg that uses different fibers such as boron fiber, titanium fiber, amorphous fiber, stainless steel fiber, glass fiber, various organic fibers and the like different from carbon fiber as a reinforcing fiber, and research for it is proposed. It is being actively conducted (Japanese Patent Application No. 1-234241).

Such hybrid prepregs can be easily manufactured and achieve improved mechanical strength and improved feel.

Recently, further improvement of mechanical properties such as tensile strength, compressive strength and elastic modulus, and tenacity has been desired to prevent breakage and increase flight distance. It is strongly desired that the feel (hit feeling) at the time of use, particularly the feel that a conventional metal shaft has, is desired, and further improvement is desired.

For this purpose, as shown in FIG. 9, a fiber reinforced prepreg in which a metal foil layer 3A is laminated on one side of a fiber reinforced composite resin layer 4 in which a matrix resin 5 is impregnated in a reinforced fiber 2. 1A has been proposed (for example, Japanese Patent Laid-Open No. Sho 6).
(See JP 1-148045).

Such a fiber reinforced prepreg is excellent in compressive strength, impact strength and torsional fracture strength, and in particular, when a golf club shaft is manufactured from these prepregs, the feel of a conventional metal shaft can be achieved. I found out.

[0008]

However, according to the results of the research and experiments conducted by the present inventors, a fiber reinforced prepreg having a metal foil layer was used to manufacture, for example, a golf club shaft or other pipe material. In this case, it has been found that the following problems occur depending on the shape of the pipe material.

FIG. 10 shows a case where the golf club shaft 200 is manufactured.
Usually, it is manufactured by winding a fiber-reinforced prepreg 1A around an elongated slanted mandrel 100. In the golf club shaft 200, as shown in FIG.
00a may be formed, and when the fiber reinforced prepreg 1 is wound around such a step forming portion, the metal foil layer 3A has no flexibility and wrinkles 202 are generated on the step 200a. The same can be said for the case where the step portion 200a is formed in the pipe member 200 having a constant diameter as shown in FIG.

The wrinkles 202 on the pipe material 200 such as the golf club shaft are not only bad in appearance but also have a reduced mechanical strength to obtain desired compression strength, impact strength and torsional fracture strength. It caused a problem that it could not be done.

Furthermore, the fiber reinforced prepreg 1 shown in FIG.
When the metal foil layer 3A is attached to the fiber-reinforced composite resin layer 4 in the production of A, the fiber-reinforced composite resin layer 4 and the metal foil layer 3
Bubbles (voids) may remain on the laminated surface with A.
The presence of such bubbles not only lowers the mechanical strength of the fiber-reinforced prepreg 1A itself, but in some cases, the bubbles are observed from the outside, which is not preferable from an aesthetic viewpoint.

Therefore, an object of the present invention is to form a uniform pipe material without causing wrinkles, even if the pipe material is provided with a stepped portion. Manufacture of sports / leisure products, bicycle frames, and various pipe parts for machine parts and other members that are aesthetically pleasing without deterioration in strength, impact strength and torsional fracture strength. Another object of the present invention is to provide a prepreg that can be suitably used for.

[0013]

The above objects are achieved by the prepreg according to the present invention. In summary, the present invention is characterized in that a fiber-reinforced composite resin layer in which a matrix resin is impregnated in a reinforcing fiber or a resin layer having no reinforcing fiber is arranged on at least one side of a metal fiber paper. It is a prepreg. As metal fiber paper, stainless steel,
A metal fiber sheet produced by using fibers such as nickel, aluminum, brass and iron, preferably having a fiber diameter of 15 μm or less, is preferably used.

[0014]

Next, the prepreg according to the present invention will be described in more detail with reference to the drawings.

FIG. 1 shows a fiber reinforced prepreg which is an embodiment of the present invention. In this embodiment, the fiber-reinforced prepreg 1 has a sheet-shaped metal fiber paper 3 on one side of a fiber-reinforced composite resin layer 4 in which a matrix resin 5 is impregnated in a reinforcing fiber 2.
Are stacked. Total thickness of fiber reinforced prepreg 1 (T)
Is generally 50 to 300 μm. The metal fiber paper 3 will be described in detail later.

The reinforcing fibers 2 are inorganic fibers such as carbon fibers, boron fibers, glass fibers, alumina fibers, silicon carbide fibers and silicon nitride fibers; aramid fibers, polyarylate fibers,
Organic fibers such as polyethylene fibers and polyester fibers;
Or, using one kind selected from metal fibers such as titanium fiber, amorphous fiber, stainless steel fiber, or
As shown in FIG. 2, a plurality of types can be used in the form of a hybrid composed of, for example, two types of reinforcing fibers 2 (2a, 2b). Further, the reinforcing fibers 2 can be arranged in one direction and arranged, or can be used in the state of cloth (woven cloth).

As the matrix resin 5, a thermosetting matrix resin such as epoxy resin, unsaturated polyester resin, polyurethane resin, diallyl phthalate resin or phenol resin can be used. Further, a curing agent and other imparting agents such as flexibility imparting agent are appropriately added so that the curing temperature is 50 to 200 ° C.

As a preferred example, an epoxy resin is preferable as the matrix resin, and examples of usable epoxy resins include (1) glycidyl ether type epoxy resins (bisphenol A, F, S type epoxy resin, novolac type epoxy resin). Resin, brominated bisphenol A epoxy resin); (2) cycloaliphatic epoxy resin;
(3) Glycidyl ester-based epoxy resin; (4) Glycidylamine-based epoxy resin, tetraglycidyldiaminodiphenylmethane, triglycidyl-p-aminophenol, etc .; (5) Heterocyclic epoxy resin; and other various epoxy resins. One kind or a plurality of kinds are used, and bisphenol A, F, S glycidyl amine epoxy resin is particularly preferably used. As the curing agent, an amine-based curing agent such as dicyandiamide (DIC
Y), diaminodiphenylsulfone (DDS), diaminodiphenylmethane (DDM); acid anhydrides such as hexahydrophthalic anhydride (HHPA) and methylhexahydrophthalic anhydride (MHHPA) are used, but especially amine curing Agents are preferably used.

Further, the compounding ratio of the reinforcing fiber and the matrix resin in the fiber-reinforced composite resin layer 4 of the present invention can be arbitrarily adjusted as in the case of a normal prepreg. Therefore, according to the present invention, the thickness (T ₁ ) of the fiber-reinforced composite resin layer 4 will usually be about 30 to 200 μm.

The fiber-reinforced prepreg 1 having such a structure can be manufactured by any method, but generally, as the fiber-reinforced composite resin layer 4, the reinforced fiber 2 is first impregnated with the matrix resin 5 to manufacture the prepreg. , Then the prepreg 4
It is preferable that the metal fiber paper 3 is attached to one side surface by pressing with a roller or the like, for example. Furthermore, if necessary, as shown in FIGS. 3 and 4, a resin layer 5 ′ may be provided with an appropriate thickness on the surface of the metal fiber paper 3 opposite to the prepreg 4 side. As the resin used for the resin layer 5 ′, the same resin as the matrix resin 5 of the fiber reinforced composite resin layer 4 can be used.

In the embodiment shown in FIGS. 1 and 2, the fiber-reinforced composite resin layer 4 is arranged only on one side of the metal fiber paper 3. However, as shown in FIGS. The fiber-reinforced composite resin layer 4 may be disposed on both sides of the layer 3.

7 and 8 show another embodiment of the present invention. In this embodiment, the resin layer 5 ′ having no reinforcing fiber is provided on one side of the metal fiber paper 3 (FIG. 7) or on both sides of the metal fiber paper 3 (FIG. 8) and the fiber-reinforced composite resin layer 4. Shown are prepregs 1 arranged with a similar thickness (T ₁ ).

The resin used for the resin layer 5'in this embodiment can be the same as the matrix resin used in the previous embodiments.

Next, the metal fiber paper 3 used in the present invention
Will be described.

In the present invention, the metal fiber paper 3 has a thickness of 20-8.
A sheet-shaped product having a diameter of 0 μm and having a fiber diameter of 1 to 30 μm, preferably 15 μm or less, manufactured using short fibers such as stainless steel, nickel, aluminum, brass and iron is suitable. Used for.

In particular, the metal fiber paper 3 used for producing the prepreg 1 of the present invention has a fiber diameter of 2 to 12 μm.
m, a stainless steel fiber paper using a stainless steel short fiber having a fiber length of 1 to 10 mm is preferable, and for example, those commercially available as a stainless steel fiber sheet from Tomoegawa Paper Co., Ltd. can be preferably used.

In the manufacturing process of the metal fiber paper 3, an organic or inorganic binder is used, but the binder can be removed in the manufacturing process if necessary. In the present invention, it is possible to use either a high-content paper in which the binder remains in the metal fiber paper or a sintered paper in which the binder is completely removed and 100% metal fiber is used. Usually, as the organic binder, wood pulp, synthetic pulp (PE, PP), aramid pulp, MF
Pulp-like substances such as C; PVA fibers, acrylic fibers, composite fibers (PE / PP), fibrous substances such as low-melting polyester fibers; latexes, polyethyleneimine, CMC,
Liquid materials such as acrylic resins, melamine resins, urea resins, and phenol resins; powder materials such as various starches, PVA, and phenol resins, and inorganic binders are colloidal materials such as silica sol, alumina sol, and zirconia sol. A liquid material such as sodium silicate, sodium phosphate, magnesium phosphate, sodium phosphate, lithium borate is used.

According to the results of the studies and experiments conducted by the present inventors,
The metal fiber paper 3 is a porous body in which a large number of pores are formed regardless of the presence or absence of a binder, and when the metal fiber paper 3 is pressed and attached to the side surface of the fiber-reinforced composite resin layer 4. The matrix resin 5 in the fiber-reinforced composite resin layer 4 penetrates into the pores of the metal fiber paper 3 so that the metal fiber paper 3 and the fiber-reinforced composite resin layer 4 can be completely integrated. Furthermore,
Particularly in the prepreg 1 shown in FIGS. 1 to 4 and 7,
When attaching the metal fiber paper 3 to the fiber-reinforced composite resin layer 4,
The air bubbles (voids) generated on the laminated surface of the metal fiber paper 3 and the fiber-reinforced composite resin layer 4 can escape to the outside through the pores of the metal fiber paper 3, and the air bubbles remain on the laminated surface. , Virtually completely eliminated. Therefore, according to the present invention, the produced fiber reinforced prepreg 1 itself does not have a decrease in mechanical strength due to generation of bubbles, which is preferable from the viewpoint of aesthetics.

Furthermore, the surface of the metal fiber paper 3 can be chemically treated in order to further improve the adhesiveness with the fiber-reinforced composite resin layer 4. Particularly, after degreasing treatment, chromate treatment or phosphate treatment may be performed to form a chromate layer or a chemical conversion treatment film such as zinc phosphate or iron phosphate on the metal fiber surface. it can.

Next, the prepreg 1 of the present invention will be described more specifically with reference to Examples.

Example 1 As the reinforcing fiber 2, PAN-based carbon fiber having a fiber diameter of 7.0 μm (manufactured by Toray Industries, Inc .: trade name “T300”) is used, and the matrix resin 5 is an epoxy resin. ,
A fiber-reinforced composite resin layer 4 having the structure shown in FIG. 1 was produced.
Further, the matrix resin 5 in the fiber-reinforced composite resin layer 4
Content was 35% by weight, FAW was 150 g / m ² , and thickness (T ₁ ) was 150 μm.

Then, the sheet-shaped metal fiber paper 3 was adhered to the fiber-reinforced composite resin layer 4 by pressing it with a roller to produce the fiber-reinforced prepreg 1 of the present invention having the structure shown in FIG.

The metal fiber paper 3 is a stainless steel fiber sheet (stainless steel fiber sheet (high compound paper) manufactured by Tomoegawa Paper Co., Ltd.) using a stainless steel short fiber having a fiber diameter of 8 μm and a fiber length of about 3 mm, and a basis weight of 95 g / m ² , thickness (T ₂ ) 3
7 μm) was used.

Fiber-reinforced prepreg 1 thus obtained
On the side opposite to the fiber-reinforced composite resin layer 4 with a basis weight of 30 g /
The same epoxy resin as the matrix resin 5 was applied at m ² to obtain the fiber reinforced prepreg 1 having the structure shown in FIG. The total thickness of this fiber reinforced prepreg 1 was 187 μm.

Further, a golf club shaft 200 having a shape as shown in FIG. 10 in which such a fiber reinforced prepreg 1 was arranged in the outermost layer was manufactured. Workability is easy, and wrinkles 2 are formed on the step portion 200a of the golf club shaft 200.
02 did not occur, which was also aesthetically pleasing.
Moreover, as a result of measuring the mechanical strength and the like, the impact strength and the torsional fracture strength are shown in FIG. 9, and the prepreg made with the metal foil 3A instead of the metal fiber paper 3 (Comparative Example 1).
Was better than the one used. Also, the feel during use was good.

Comparative Example 1 Instead of the metal fiber paper 3, a stainless foil 3 having a thickness of 30 μm was used.
A fiber reinforced prepreg 1A having the same composition and method as in Example 1 except that A was used.
Was manufactured, and a golf club shaft 200 having a shape as shown in FIG. 10 was manufactured.

In particular, workability was poor and wrinkles 202 were formed on the stepped portion 200a, which was not aesthetically pleasing. As a result of measuring the mechanical strength and the like, the impact strength and the torsional fracture strength were inferior to those of Example 1.

Example 2 As in Example 1, the reinforcing fiber 2 has a fiber diameter of 7.0 μm.
m of PAN-based carbon fiber (trade name “T300” manufactured by Toray Industries, Inc.) is used, and epoxy resin is used as the matrix resin 5 to fabricate the fiber-reinforced composite resin layer 4 having the configuration shown in FIG. did. Further, the content of the matrix resin 5 in the fiber-reinforced composite resin layer 4 is 35% by weight, and the FAW is 15
The thickness (T ₁ ) was 0 g / m ² and 150 μm.

Then, the sheet-shaped metal fiber paper 3 was pressed onto the fiber-reinforced composite resin layer 4 with a roller to bond the fiber-reinforced composite resin layer 4 to produce the fiber-reinforced prepreg 1 of the present invention having the structure shown in FIG.

The metal fiber paper 3 is a stainless steel fiber sheet (stainless steel fiber sheet (sintered paper) manufactured by Tomoegawa Paper Co., Ltd.) using a stainless steel short fiber having a fiber diameter of 8 μm and a fiber length of about 3 mm, and a basis weight of 110 g / m ² , thickness (T ₂ ) 4
3 μm) was used.

Fiber-reinforced prepreg 1 thus obtained
On the side opposite to the fiber-reinforced composite resin layer 4, the basis weight is 35 g /
The same epoxy resin as the matrix resin 5 was applied at m ² to obtain the fiber reinforced prepreg 1 having the structure shown in FIG. The total thickness of this fiber reinforced prepreg 1 was 193 μm.

Further, a golf club shaft 200 having a shape as shown in FIG. 10 in which such a fiber reinforced prepreg 1 was arranged in the outermost layer was manufactured. Workability is easy, and wrinkles 2 are formed on the step portion 200a of the golf club shaft 200.
02 did not occur, which was also aesthetically pleasing.
Moreover, as a result of measuring the mechanical strength and the like, the impact strength and the torsional fracture strength were superior to those using the prepreg shown in Comparative Example 1. Also, the feel during use was good.

[0043]

EFFECT OF THE INVENTION The prepreg according to the present invention configured as described above can form a uniform pipe material without causing wrinkles even if a step portion is formed on the pipe material. In particular, for producing sports and leisure products, bicycle frames, and various pipe parts for machine parts, which do not decrease in compressive strength, impact strength, torsional fracture strength, etc. and are aesthetically superior. It has a feature that it can be suitably used.

[Brief description of drawings]

FIG. 1 is a cross-sectional configuration diagram of an embodiment of a prepreg according to the present invention.

FIG. 2 is a cross-sectional configuration diagram of another embodiment of the prepreg according to the present invention.

FIG. 3 is a cross-sectional configuration diagram of another embodiment of the prepreg according to the present invention.

FIG. 4 is a cross-sectional configuration diagram of another embodiment of the prepreg according to the present invention.

FIG. 5 is a cross-sectional configuration diagram of another embodiment of the prepreg according to the present invention.

FIG. 6 is a cross-sectional configuration diagram of another embodiment of the prepreg according to the present invention.

FIG. 7 is a cross-sectional configuration diagram of another embodiment of the prepreg according to the present invention.

FIG. 8 is a cross-sectional configuration diagram of another embodiment of the prepreg according to the present invention.

FIG. 9 is a cross-sectional configuration diagram of a conventional fiber reinforced prepreg.

FIG. 10 is a front view showing an example of a golf club shaft made of a conventional fiber reinforced prepreg.

FIG. 11 is a front view showing an example of a pipe material made of a conventional fiber reinforced prepreg.

[Explanation of symbols]

 1 prepreg 2 reinforcing fiber 3 metal fiber paper 4 fiber reinforced composite resin layer 5 matrix resin 5'resin layer

Claims (1)

[Claims] 1. A prepreg characterized in that a fiber-reinforced composite resin layer in which a matrix resin is impregnated in a reinforcing fiber or a resin layer having no reinforcing fiber is arranged on at least one side of a metal fiber paper. ..