JPH058224A - Prepreg - Google Patents

Abstract

PURPOSE:To enable molding of a uniform pipe material without generating creases and does not cause lowering of compression strength, shock strength and rupture in torsion strength even if it is a material obtained by forming a stepped part on, for example, the pipe material. CONSTITUTION:A foil-like expanded metallic layer 3 is laminated on one side of a fiber-reinforced composite resin layer 4 impregnated with matrix resin 5 within a reinforced fiber 2, in a fiber-reinforced prepreg 1.

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 face surfaces, fishing rods, sports and leisure equipment such as various racket frames such as tennis rackets or badminton rackets, bicycle frames, and pipe materials for various mechanical parts, and others. The present invention relates to a prepreg that can be preferably used for manufacturing a member. 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 foil-shaped expanded metal layer, A prepreg having excellent strength and 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 Different from carbon fiber such as boron fiber, titanium fiber, amorphous fiber, stainless steel
It has been proposed to use a hybrid prepreg using different kinds of fibers such as glass fiber, glass fiber, and various organic fibers as a reinforcing fiber, and researches therefor have been actively conducted (Japanese Patent Application No. 1-3242441).

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.

To this end, as shown in FIG.
A fiber reinforced prepreg 1A 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 has been proposed (for example, JP-A-61-148045). See the bulletin).

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. 11 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. As shown in FIG. 11, the golf club shaft 200 includes a step portion 2
00a may be formed, and when the fiber reinforced prepreg 1 is wound around such a step forming portion, the metal foil layer 3 has no flexibility and wrinkles 202 are generated at the step 200a. This is as shown in FIG.
The same can be said when the step portion 200a is formed in the pipe material 200 having a constant diameter.

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.

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 step 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.

[0012]

The above objects are achieved by the prepreg according to the present invention. In summary, the present invention provides 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 disposed on at least one side of a foil-shaped expanded metal layer. It is a prepreg characterized by.

[0013]

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 the fiber-reinforced prepreg 1 in this embodiment, a foil-shaped expanded metal layer 3 is laminated on one side of a fiber-reinforced composite resin layer 4 in which a matrix resin 5 is impregnated in a reinforcing fiber 2. The total thickness (T) of the fiber reinforced prepreg 1 is generally 20 to 300 μm. The foil-shaped expanded metal layer 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,
Alternatively, as shown in FIG. 5, a plurality of types, for example, two types of reinforcing fibers 2 (2a, 2b) can be used in the form of a hybrid. 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 an epoxy resin, an unsaturated polyester resin, a polyurethane resin, a diallyl phthalate resin or a 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 constitution can be manufactured by any method. Generally, as the fiber-reinforced composite resin layer 4, first, the reinforced fiber 2 is impregnated with the matrix resin 5 to manufacture the prepreg. , Then the prepreg 4
It is preferable that the expanded metal as the foil-shaped expanded metal layer 3 is attached to one side surface of the substrate by pressing it with, for example, a roller.

In the embodiment shown in FIGS. 1 and 5, the fiber-reinforced composite resin layer 4 is arranged only on one side of the foil-shaped expanded metal layer 3, but as shown in FIGS. The fiber-reinforced composite resin layer 4 may be arranged on both sides of the expanded metal layer 3.

8 and 9 show another embodiment of the present invention. In this example, a prepreg 1 in which a resin layer 5 ′ having no reinforcing fiber is arranged on one side of the foil-shaped expanded metal layer (FIG. 8) or on both sides of the foil-shaped expanded metal layer 3 (FIG. 9). Is exemplified.

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 foil-shaped expanded metal layer 3 used in the present invention will be described.

The foil-shaped expanded metal forming the foil-shaped expanded metal layer 3 according to the present invention is as shown in FIG.
A foil-shaped or thin plate-shaped metal material 3'having a thickness (T ₂ ') of 5 to 100 μm, for example, an aluminum foil with a thickness of 10 to 100 μm manufactured by Showa Aluminum Co., Ltd., or, for example, Takeuchi metal foil powder Using a stainless steel foil, a high-strength steel foil, and a titanium foil having a thickness of 5 to 50 μm manufactured by Kogyo Co., Ltd., a notch (slit) 30 is formed by a normal technique, and a force is applied in a direction orthogonal to the notch 30. It is made by stretching at P (FIG. 4). Other usable metal materials 3 '
Examples thereof include iron, copper, nickel, nichrome, tin, lead, magnesium, gold, silver, platinum, other various metals and alloys thereof. These metal materials 3 ′, that is, the foil-shaped expanded metal 3, has a thickness, that is, a strand 3 _S.
When the plate thickness (T ₂ ') in FIG. 4 is thinner than 5 μm, the compressive strength and torsional fracture strength are insufficient, and when it is thicker than 100 μm, the formability is insufficient.

The foil-shaped expanded metal layer 3 is prepared by using the foil-shaped or thin-plate-shaped metal material 3'having a plate thickness (T ₂ ') of 5 to 100 μm as described above. , It becomes a wavy shape by stretching, and its thickness T ₂ is substantially
Is 30 to 150 μm.

According to the present invention, in the foil-shaped expanded metal 3, the width between the slits 30, that is, the width a of the strand 3 _S is 0.1 to 2.0 mm, and the length of the slit 30 is 0.
The length c between the adjacent slits 30 forming the bond 3 _B (FIG. 4) is 5 to 10 mm and 0.1 to 2.0 mm. Further, the size of the mesh 3a after being stretched is such that the ratio (SW / LW) of the mesh center-to-center distance (SW) to the mesh center-to-center distance (LW) is 1/50 to 50 /.
1, preferably 1/50 to 5/1.

The foil-shaped expanded metal 3, that is, the mesh 3a can be formed in various modes depending on the use for which the prepreg 1 is used. When producing a club shaft, the width a of the strand 3 _S is 0.1 mm, the length of the slit 30 is 0.75 mm, and the length c between the adjacent slits 30 forming the bond 3 _B is 0. The size of the mesh 3a after stretching is set to 2 mm, and the ratio (SW / LW) of the short-side center distance (SW) to the long-side center distance (LW) of the mesh is 3: 7. It

The foil-shaped expanded metal 3 produced in this manner is treated mechanically or chemically on its surface in order to improve the adhesiveness with the fiber-reinforced composite resin layer or resin layer 4. It is possible to In particular, after degreasing treatment, chromate treatment or phosphate treatment is performed to form a chromate layer or a chemical conversion treatment film such as zinc phosphate or iron phosphate on the foil-shaped expanded metal surface. Preferably. Furthermore, surface hardening treatment under a high temperature nitrogen atmosphere is also effective.

Further, in the above embodiment, the stretching direction of the foil-shaped expanded metal 3 is achieved along the arrangement direction of the reinforcing fibers 2, but in some cases, it is orthogonal to the arrangement direction of the reinforcing fibers 2. It is also possible to do in.

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

Example 1 PAN-based carbon fiber having a fiber diameter of 7.0 μm as the reinforcing fiber 2 (manufactured by Toray Industries, Inc .: trade name “T-300”)
And the epoxy resin was used as the matrix resin 5, and the fiber-reinforced composite resin layer 4 having the structure shown in FIG. 1 was produced. The content of the matrix resin 5 in the fiber-reinforced composite resin layer 4 was 35% by weight.

Next, the fiber-reinforced composite resin layer 4 has a thickness (T
₂ ) The foil-shaped expanded metal 3 having a thickness of 70 μm was pressed by a roller and adhered to produce the fiber-reinforced prepreg 1 of the present invention having the structure shown in FIG.

At this time, the foil-shaped expanded metal 3 is
A stainless foil having a thickness (T ₂ ') of 30 μm is used, the width a of the strand 3 _S is 0.1 mm, the length of the slit 30 is 0.75 mm, and the distance between the adjacent slits 30 forming the bond 3 _B is 30 mm. The length c of the mesh 3a is 0.2 mm, and the dimension of the mesh 3a after stretching is the ratio (SW / SW) between the short-side center-to-center distance (SW) of the mesh LW) was 3: 7.

Further, a golf club shaft 200 having a shape as shown in FIG. 11 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.
Further, as a result of measuring the mechanical strength and the like, as for the impact strength and the torsional fracture strength, as shown in FIG. 10, a prepreg (Comparative Example 1) made of the metal foil 3A was used instead of the foil-shaped expanded metal. Was better than the one. Also, the feel during use was good.

Comparative Example 1 A fiber reinforced prepreg having the structure shown in FIG. 10 was made by using the same material and method as in Example 1 except that a 30 μm thick stainless steel foil 3A was used instead of the foil expanded metal 3. 1A was manufactured, and a golf club shaft 200 having a shape shown in FIG. 11 was manufactured.

In particular, the 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.

[0037]

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 plan view of the prepreg of FIG.

FIG. 3 is a plan view of a foil-shaped expanded metal before being stretched.

FIG. 4 is a perspective view of a foil-shaped expanded metal.

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 another embodiment of the prepreg according to the present invention.

FIG. 10 is a cross-sectional configuration diagram of a conventional fiber reinforced prepreg.

FIG. 11 is a front view showing an example of a golf club shaft made of a conventional fiber reinforced prepreg.

FIG. 12 is a front view showing an example of a pipe material made of a conventional fiber reinforced prepreg.

[Explanation of symbols]

1 prepreg 3 foil-shaped expanded metal layer (foil-shaped expanded metal) 3a mesh 4 fiber-reinforced resin layer (resin layer) 5 matrix resin

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location B32B 15/08 105 7148-4F // B29K 105: 06

Claims (1)

Claim: What is claimed is: 1. 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 foil-shaped expanded metal layer. A prepreg that has been characterized.