JPH05255523A - Fiber reinforced prepreg - Google Patents

Abstract

(57) [Abstract] [Purpose] Not only is it aesthetically pleasing, without disturbing the arrangement of the reinforcing fibers, it also eliminates physical variations, and also has toughness, vibration damping and impact resistance characteristics, especially compressive strength and torsion. It can be suitably used for producing sports / leisure products, bicycle frames, and various pipe materials for machine parts, which are excellent in breaking strength. [Structure] The fiber reinforced prepreg 1 uses reinforcing fibers 6 arranged in the same direction at a predetermined interval and having a fiber diameter of 30 to 500 μm as warp threads, and other fibers or the same fibers as weft threads 8. A fiber reinforced resin layer 4 configured by impregnating a matrix resin 3 into a cloth (woven fabric) woven by
The metal foil layer 7 laminated on one side of the fiber reinforced resin layer 4.

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, it can be suitably used for manufacturing golf club shafts, fishing rods, sports and leisure products such as various racket frames such as tennis rackets or badminton rackets, bicycle frames, and various pipe parts for machine parts. The present invention relates to a fiber-reinforced prepreg that can be manufactured. Particularly, the fiber-reinforced prepreg of the present invention has 3
Characteristic in that a metal foil layer is laminated on one side of a fiber reinforced resin layer formed by weaving a reinforcing fiber having a fiber diameter of 0 to 500 μm (including a “converted diameter” described later) into a cloth. Have.

[0002]

2. Description of the Related Art In recent years, prepregs made of carbon fibers and various other reinforcing fibers have been widely used in various technical fields. For example, they are lightweight and have high mechanical strength when manufacturing golf club shafts. It is used for many reasons and has achieved extremely good results.

However, further improvements are desired in terms of strength and elastic modulus, in terms of feel during use, and in terms of fashionability (aesthetics), and in order to meet such demands, The outermost layer of the fiber-reinforced composite resin shaft is shown in FIG.
Impregnated with the matrix resin 3 as shown in FIG.
Various attempts have been made to arrange layers formed of prepreg 4 having reinforcing fibers 6 such as boron fibers, titanium fibers, amorphous fibers, stainless steel fibers, glass fibers, and various organic fibers.

[0004]

Although such a prepreg 4 can be manufactured efficiently and relatively easily by using a drum winder or the like, the mechanical strength and the feel can be improved. In some cases, the reinforcing fibers 6 are disturbed in the arrangement direction during the manufacturing process, or during the process of winding the prepreg 4 around a mandrel or the like after manufacturing and shaping it into a predetermined shape. Disorders of the arrangement of the reinforcing fibers 6 are not only aesthetically unpleasant, but also cause variations in physical properties, which is not preferable in terms of product quality.

In order to eliminate such disorder of the fiber, extremely careful handling of the reinforcing fiber 6 in the manufacturing process or the prepreg 4 after manufacturing is required, and in terms of handling property (workability). There's a problem.

In order to solve this problem, the present inventors have
As shown in FIG. 13, a reinforcing fiber 6 was woven with a weft 8 to form a cloth (woven fabric), and a prepreg 4 impregnated with a matrix resin 3 was produced (Japanese Patent Application No. 2-1381).
03).

With this structure, it is possible to solve the disorder in the arrangement direction of the reinforcing fibers 6 and to eliminate the variation in physical properties. The present invention relates to the improvement of such a prepreg, and is intended to further improve the mechanical properties.

That is, the object of the present invention is to not only disturb the arrangement of the reinforcing fibers and to improve the appearance, but also to eliminate variations in physical properties, and also toughness, vibration damping properties and impact resistance properties, particularly compressive strength. Another object of the present invention is to provide a fiber-reinforced prepreg which is excellent in torsional fracture strength and can be suitably used for producing sports and leisure products, bicycle frames, and various pipe materials for machine parts.

[0009]

The above object is achieved by the fiber reinforced prepreg according to the present invention. In summary, according to the present invention, the diameter of fibers arranged in one direction at predetermined intervals is 30.
A fiber-reinforced resin layer formed by impregnating a matrix resin into a cloth (woven fabric) obtained by weaving a reinforcing fiber having a length of ˜500 μm as a warp yarn, and the same fiber as the reinforcing fiber or another different fiber as a weft yarn; A fiber reinforced prepreg, comprising: a metal foil layer laminated on one side of a reinforced resin layer. Preferably, the metal foil layer is formed of a sheet-shaped or mesh-shaped metal material having a thickness of 5 to 100 μm, and the warp threads are carbon fibers, boron fibers, glass fibers, alumina fibers, and silicon carbide. Fiber, inorganic fiber such as silicon nitride fiber; metal fiber such as titanium fiber, amorphous fiber, stainless steel fiber; and organic fiber such as aramid fiber, polyarylate fiber, polyethylene fiber, and the weft thread is carbon fiber. ,
Inorganic fibers such as boron fibers, glass fibers, alumina fibers, silicon carbide fibers, and silicon nitride fibers having a small fiber diameter; organic fibers such as aramid fibers, polyarylate fibers, and polyethylene fibers; and titanium fibers and amorphous fibers having a small fiber diameter. , Stainless steel fibers and other metal fibers.

[0010]

The fiber-reinforced prepreg according to the present invention will be described in more detail with reference to the drawings. As shown in FIGS. 1 and 2, for example, the fiber-reinforced prepreg 1 of the present invention has reinforcing fibers 6 arranged in the same direction at predetermined intervals and having a fiber diameter of 30 to 500 μm as warp yarns, A fiber reinforced resin layer 4 formed by impregnating a matrix resin 3 into a cloth (woven fabric) 5 woven using another fiber or the same fiber as the weft thread 8, and one side of the fiber reinforced resin layer 4. And a metal foil layer 7 laminated on the. The woven structure, the woven density, etc. of the cloth 5 are appropriately selected as needed, but the wefts 8 may be woven to such an extent as to fix the arrangement of the reinforcing fibers to be the warp 6. According to the present invention, the total thickness (T) of the fiber reinforced prepreg 1 is 20 to 300 μm.

The fiber-reinforced prepreg 1 having such a structure can be manufactured by any method. Generally, as the fiber-reinforced composite resin layer 4, a cloth 5 is first impregnated with the matrix resin 3 to manufacture a prepreg, After that, it is preferable that the metal foil as the metal foil layer 3 is attached to one side surface of the prepreg 4 by pressing it with a roller or the like to manufacture. Therefore, in the following description, although it is described that the fiber-reinforced prepreg 1 of the present invention is manufactured by this method, it is to be understood that the present invention is not limited thereto.

Further, the metal foil forming the metal foil layer 3 does not only mean a so-called "sheet-like" metal material such as a foil or a thin plate in the present invention, but also a net having a large number of holes. Alternatively, it also means a so-called "mesh-like" metallic material that is porous like expanded metal. Such a metal foil 3 has 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, a thickness of 5 to 50 μm manufactured by Takeuchi Metal Foil & Powder Co., Ltd.
Stainless steel foil, high-strength steel foil, and titanium foil are preferably used. Other metal materials that can be used include iron,
Copper, nickel, nichrome, tin, lead, magnesium, gold,
There are silver, platinum and various other metals and alloys thereof.
When the thickness (T ₂ ) of the metal foil 3 is thinner than 5 μm, the compressive strength and the torsional fracture strength are insufficient, and the thickness is 100 μm.
When it is thicker than m, the moldability becomes insufficient.

Further, the metal foil 3 has a fiber-reinforced resin layer 4
In order to improve the adhesiveness with
Alternatively, it can be chemically treated. In particular, it is preferable to perform a degreasing treatment and then a chromium treatment or a phosphoric acid treatment to form a chromium layer or a chemical conversion treatment film such as zinc phosphate or iron phosphate on the surface of the metal foil. Furthermore, surface hardening treatment under a high temperature nitrogen atmosphere is also effective.

Next, a prepreg as the fiber reinforced resin layer 4 which can suitably manufacture the fiber reinforced prepreg 1 of the present invention will be described.

Although the prepreg 4 having such a structure can be manufactured by various methods, as shown in FIG. 3, the prepreg 4 is formed between the warp threads 6 and the weft threads 8 between the release papers 10 coated with the matrix resin 3. It is extremely suitably manufactured by arranging the cloth 5 made of the above and integrating them by pressing and / or heating.

As the reinforcing fiber as the warp yarn 6, inorganic fiber such as boron fiber having a large fiber diameter and metal fiber such as titanium fiber, amorphous fiber and stainless steel fiber are preferably used, and the diameter of such fiber is usually 30. ~ 150 μm
And preferably 50 to 120 μm.

Further, according to the present invention, as the warp yarn 6, carbon fiber, glass fiber, alumina fiber, silicon carbide fiber,
Inorganic fibers such as silicon nitride fibers; organic fibers such as aramid fibers, polyarylate fibers and polyethylene fibers can also be used. However, in general, these fibers have a fiber diameter, that is, a monofilament diameter (d) of 5 to 50 μm.
Since it is small, the warp 6
When used as a fiber 6, as shown in FIG.
It is used in the form of a strand (fiber bundle) 6 in which a large number of a are bundled.

Therefore, even metal fibers having a small fiber diameter can be used as the warp yarns 6 in the form of strands.

In the present specification, the fiber diameter of the warp yarn 6 in the case of such a strand form means a reduced diameter D ₀ represented by the following equation. D ₀ = n ^1/2 · d n: Convergence number d: Fiber diameter

When such a strand is used as the warp yarn 6, the shape of a circular cross section having a reduced diameter D ₀ in the prepreg 4 as shown in FIG. It does not exist and is usually in a flatly deformed state. Therefore, as described above, the fiber reinforced prepreg 1 having the same thickness (T ₁ ) as when the boron fiber, titanium fiber, amorphous fiber, stainless steel fiber or the like having a large fiber diameter is used as the warp yarn 6.
In order to manufacture, the fiber diameter when the strand is used as the warp yarn 6, that is, the converted diameter D ₀ is preferably 500 μm at the maximum.

For example, when 300 organic fibers such as polyarylate fibers having a fiber diameter d of 23 μm are converged, the converted diameter D ₀ becomes 398 μm, and the glass fiber having a fiber diameter d of 13 μm. Is 800, and the converted diameter D ₀ is 368 μm. Both of these strands are also suitably used as the warp yarns 6, and the prepreg 4 as shown in FIG. 5, that is, the fiber-reinforced prepreg 1 of the present invention. Can be manufactured.

The weft thread 8 constituting the cloth 5 may be the same as the warp thread 6, and the fiber diameter is 5 to 30 μm.
m, preferably 6 to 12 μm, such as carbon fibers, boron fibers having a small fiber diameter, glass fibers, alumina fibers, silicon carbide fibers, silicon nitride fibers, and other inorganic fibers; aramid fibers, polyarylate fibers, polyethylene fibers, etc. Organic fibers; or titanium fibers having a small fiber diameter, amorphous fibers, metal fibers such as stainless steel fibers, and the like can be arbitrarily used, and other various fibers can also be used. Generally, it is preferable to use inorganic fibers such as glass fibers and alumina fibers, organic fibers such as polyethylene fibers and polyester fibers. As the weft yarn, a thin fiber, a thin fiber bundle, or a transparent yarn is more preferable. From this point, glass fiber, polyethylene fiber, alumina fiber and the like are particularly preferable.

As the matrix resin 3, 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 usable epoxy resins include, for example, (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), diaminophenyl sulfone (DDS), diaminodiphenylmethane (DDM); acid anhydrides such as hexahydrophthalic anhydride (HHPA) and methylhexahydrophthalic anhydride (MHHPA) are used.
Particularly, amine-based curing agents are preferably used.

The warp threads in the prepreg 4 of the present invention,
The mixing ratio of the matrix resin and the weft yarn can be adjusted arbitrarily, but generally, in weight%, the warp yarn: the matrix resin: the weft yarn =
(20-50) :( 20-60) :( 10-50). Further, according to the present invention, the thickness (T ₁ ) of the prepreg can be made to be about the fiber diameter of the warp yarn 6 to be used, but it will usually be about 50 to 200 μm.

In the above description of the embodiment, the cloth 5 arranged in the prepreg 4 is composed of only the warp threads 6 and the weft threads 8. However, the cloth 5 used in the present invention is as follows. The present invention is not limited to such a woven structure, and for example, FIG.
As shown in FIG. 5, fixing fibers 9 can be further arranged as warp yarns between the warp yarns 6 and can be woven. As the fixing warp yarn 9 used for such a purpose, the same yarn as the weft yarn 8 can be used, and as described above, it may be the same as the reinforcing fiber in the prepreg 4, that is, the warp yarn 6. It is also possible to use various other fibers, but usually,
Inorganic fibers such as carbon fiber, glass fiber, alumina fiber,
It is preferable to use organic fibers such as polyethylene fibers and polyester fibers. Even as the fixing warp 9
Fine fibers, thin fiber bundles, and transparent ones are more preferable. From this point, as with the weft thread 8, especially glass fiber,
Polyethylene fiber, alumina fiber and the like are preferable.

Further, in the above embodiment, the warp yarn, that is, the reinforcing fiber 6 is described as one type, but the present invention is not limited to this, and includes two or more kinds of warp yarns as reinforcing fibers. You can For example, in FIG. 7 and FIG.
A mode in which two kinds of fibers 6a and 6b are woven as the warp yarns 6 in the cloth 5 is shown. In this example, two types of fibers 6a, 6
Although b is woven alternately, it is not limited to this, and any arrangement is possible. Also in this case, as shown in FIG. 9, the fixing fiber 9 can be further arranged as the warp yarn between the warp yarns 6a and 6b and can be woven.

Next, the fiber-reinforced prepreg 1 of the present invention will be described more specifically with reference to examples.

Example 1 A prepreg 4 was manufactured by the method described with reference to FIG. That is, in this embodiment, the release paper 10 having a thickness of 120 μm is used.
The matrix resin 3 having a thickness of 65 μm was applied onto the above. An epoxy resin was used as the matrix resin 3.

Boron fibers and titanium fibers are used as the reinforcing fibers as the warp threads 6, and the weft thread 8 has a fineness of 10 g / 1.
Glass fiber having a length of 000 m was used.

As the boron fiber, fibers having a fiber diameter of 100 μm are used at intervals of 1 mm, and the weft thread 8 is 0.5
The cloth 5 having the structure shown in FIG. Titanium fibers having a fiber diameter of 100 μm were used at intervals of 2 mm, and weft threads 8 were woven at intervals of 0.5 mm to fabricate a cloth 5 having the structure shown in FIG.

The cloth 5 was sandwiched between the two release papers 10 coated with the matrix resin 3 and pressed together and / or heated to be integrated, thereby forming a prepreg 4 as shown in FIG.

A stainless steel foil having a thickness of 30 μm was pressed onto the prepregs 4 with a roller to adhere the prepregs 4 to produce the fiber-reinforced prepreg 1 of the present invention having the structure shown in FIG.

Further, a golf club shaft having such a fiber reinforced prepreg 1 arranged in the outermost layer was manufactured, and the mechanical strength and the like were measured. As a result, the impact strength and the torsional fracture strength are shown in FIG. It was possible to significantly increase it compared to the one using, and the feel during use was also improved.

Furthermore, the fiber-reinforced prepreg 1 according to the present invention has a warp yarn 6 which is formed during the manufacturing process and also when the fiber-reinforced prepreg 1 thus manufactured is wound around a mandrel to form a golf shaft or the like. The arrangement was not disturbed in the length direction of the fiber, the workability was easy, and it was also aesthetically pleasing.

Example 2 In the above-mentioned Example 1, the cloth 5 having the structure shown in FIG. 6 was produced, and the fiber-reinforced prepreg 1 was prepared by using the cloth 5 and using the same materials and conditions as those of the above-mentioned Example 1. Was manufactured.

That is, glass fibers having a fineness of 10 g / 1000 m are used as the weft threads 8 and the fixing warp threads 9, the warp threads 6 such as boron fiber and titanium fiber are arranged at 2 mm intervals, and the fixing warp threads 9 are each warp thread. Three pieces were arranged at intervals of 0.5 mm between 6 and the weft threads 8 were arranged at intervals of 0.5 mm, and were woven as shown in FIG.

Although a golf club shaft having the fiber reinforced prepreg 1 using the cloth 5 arranged in the outermost layer was manufactured, the warp yarns 6 can be fixed at a predetermined pitch, and the dissimilar fibers 6 are arranged in the fiber direction. I was able to almost completely eliminate the disturbance. At the same time, the mechanical properties of the golf club shaft, particularly impact strength and torsional fracture strength, could be significantly increased.

Example 3 In the above Example 1, the cloth 5 was sandwiched between the two release papers 10 coated with the matrix resin, and pressed and / or pressed toward each other.
Alternatively, it is integrated by heating, but in this embodiment, as shown in FIG. 10, the release paper 10 is not simply coated with the matrix resin 3 but carbon fibers as the reinforcing fibers 2. The first and second carbon fiber reinforced prepregs 4A and 4B used were used.

That is, the first and second carbon fiber reinforced prepregs 4A and 4B have the same structure and have a thickness of 120 μm.
It was formed on the m-th release paper 10 with a thickness of 65 μm. As the carbon fiber as the reinforcing fiber 2, a PAN-based carbon fiber having a fiber diameter of 7.0 μm (manufactured by Toray Industries, Inc .: trade name “T-300”) was used, and the matrix resin 3 was an epoxy resin. .. The content of matrix resin in the prepreg was 35% by weight.

First and second carbon fiber reinforced prepreg 4
The reinforced fibers 2 of A and 4B were arranged in one direction so as to be aligned with the warp yarns 6, and otherwise the same as in Example 1 to produce the fiber reinforced prepreg 1 shown in FIG.

A golf club shaft having such a fiber reinforced prepreg 1 arranged in the outermost layer was manufactured, and its mechanical strength and the like were measured. As compared with the shaft of Example 1, the bending fracture strength and the rigidity were further improved. I was able to improve it.

[0043]

The fiber reinforced prepreg according to the present invention configured as described above eliminates the disorder of the arrangement of the reinforcing fibers,
Not only is it aesthetically pleasing, but it also eliminates variations in physical properties and is tough and has excellent impact strength and torsional fracture strength.
Further, it has a feature that it can be preferably used for manufacturing various pipe materials for machine parts.

[Brief description of drawings]

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

FIG. 2 is a perspective view showing an example of a cloth woven with reinforcing fibers used in the present invention.

FIG. 3 is a cross-sectional view illustrating one manufacturing method of the fiber reinforced prepreg according to the present invention.

FIG. 4 is a cross-sectional view of a strand showing one form of a reinforcing fiber used in the present invention.

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

FIG. 6 is a perspective view showing another example of a cloth woven with reinforcing fibers used in the present invention.

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

FIG. 8 is a perspective view showing another example of a cloth woven with reinforcing fibers used in the present invention.

FIG. 9 is a perspective view showing still another example of a cloth woven with reinforcing fibers used in the present invention.

FIG. 10 is a cross-sectional view illustrating another method for manufacturing the fiber reinforced prepreg according to the present invention.

FIG. 11 is a cross-sectional configuration diagram of another embodiment of the fiber reinforced prepreg according to the present invention.

FIG. 12 is a cross-sectional configuration diagram of a conventional fiber reinforced prepreg.

FIG. 13 is a cross-sectional configuration diagram of another conventional fiber-reinforced prepreg.

[Explanation of symbols]

 1 Fiber Reinforced Prepreg 3 Matrix Resin 4 Fiber Reinforced Resin Layer (Prepreg) 5 Cloth 6 Reinforced Fiber (Warp) 7 Metal Foil Layer (Metal Foil) 8 Weft

Claims (1)

[Claims] 1. A cloth obtained by weaving reinforcing fibers arranged in one direction at predetermined intervals and having a fiber diameter of 30 to 500 μm as warp yarns, and weaving the same fibers as the reinforcing fibers or other different fibers as weft yarns. A fiber reinforced prepreg, comprising a fiber reinforced resin layer formed by impregnating a woven fabric) with a matrix resin, and a metal foil layer laminated on one side of the fiber reinforced resin layer.