JPH04348137A - Composite prepreg - Google Patents

Abstract

PURPOSE:To obtain a composite prepreg capable of providing a lightweight fiber-reinforced composite resin material molded product such as a golf club shaft improved in mechanical strength and further in impact resistance. CONSTITUTION:A composite prepreg 1 is constructed by laminating a resin film layer 4 on a fiber-reinforced composite resin layer 3 having reinforcing fiber 2 and further laminating a metallic foil layer 5 thereon. Since the prepreg 1 has the resin film layer 4 and the metallic foil layer 5, the resultant fiber- reinforced composite resin material molded product such as a golf club shaft is improved in torsional breaking strength and impact resistance by using the above-mentioned composite prepreg 1 and a normal prepreg in combination.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention relates to a composite formed by laminating a fiber-reinforced composite resin layer, a resin film layer, and a metal foil layer, each having one or more types of reinforcing fibers such as carbon fiber and different types of fibers. Regarding prepreg.

0002

[Prior Art] In recent years, fiber-reinforced composite resin materials using prepregs containing carbon fibers and various other reinforcing fibers have been widely used in various technical fields, such as golf shafts, fishing rods, tennis rackets, and badminton rackets. In the production of fiber-reinforced composite resin molded products such as various racket frames, it is widely used because it is lightweight and has high mechanical strength, and has achieved very good results.

0003

[Problems to be Solved by the Invention] However, it is desired to further improve the torsional fracture strength and impact resistance of fiber-reinforced composite resin molded articles, and to improve the feel during use.

[0004] When improving the torsional fracture strength of a fiber-reinforced composite resin annular body with a circular or polygonal cross section made using prepreg, the inside or, in some cases, the outside of the annular body has the same cross-sectional shape. However, current pipe manufacturing and processing technology limits the minimum wall thickness of aluminum pipes.
This inevitably results in a significant increase in weight. Therefore, it is not advantageous to employ aluminum pipe reinforcement for small-diameter fiber-reinforced composite resin material annular bodies such as golf shafts and fishing rods, regardless of the case of large-diameter annular bodies.

In view of the above-mentioned current situation, the object of the present invention is to provide a fiber-reinforced composite resin material molding for golf club shafts and the like that is lightweight, has improved mechanical strength such as torsional fracture strength, and also has improved impact resistance. The object of the present invention is to provide a composite prepreg that can be obtained as a high quality product.

[0006]

[Means for Solving the Problems] The above objects are achieved by the composite prepreg according to the present invention. In summary, the present invention:
This is a composite prepreg in which a fiber-reinforced composite resin layer containing one or more types of reinforcing fibers, a resin film layer, and a metal foil layer are laminated. Preferably, the thickness of the resin film layer is 5 to 1
The thickness of the metal foil layer is 5 to 50 μm, and the thickness of the entire composite prepreg is 20 to 300 μm. The lamination order of the fiber-reinforced composite resin layer, the resin film layer, and the metal foil layer is the order of the fiber-reinforced composite resin layer, the resin film layer, and the metal foil layer, or the order of the resin film layer, the fiber-reinforced composite resin layer, and the metal foil layer. , or a fiber-reinforced composite resin layer, a metal foil layer, and a resin film layer in any order.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The composite prepreg according to the present invention will be explained in detail below with reference to the drawings.

FIG. 1 is a sectional view showing an embodiment of the composite prepreg of the present invention. According to the present invention, the composite prepreg 1 includes a fiber-reinforced composite resin layer 3 having one or more types of reinforcing fibers 2, a resin film layer 4, and a metal foil layer 5 laminated in any order. In this embodiment, a resin film layer 4 is laminated on a fiber-reinforced composite resin layer 3 having carbon fibers as reinforcing fibers 2, and a metal foil layer 5 is laminated on the resin film layer 4.

The fiber-reinforced composite resin layer 3 is made by impregnating matrix resin 6 between reinforcing fibers, that is, carbon fibers 2 arranged in one direction. In the present invention, this carbon fiber 2 also means graphite fiber, and graphite fiber can also be used as the carbon fiber 2.

As the matrix resin 6, thermosetting matrix resins such as epoxy resin, unsaturated polyester resin, polyurethane resin, diallyl phthalate resin, and phenol resin can be used. Furthermore, the curing temperature is 5
A curing agent and other imparting agents, such as a flexibility imparting agent, are appropriately added so that the temperature is 0 to 200°C.

To give a preferable example, epoxy resin is preferable as the matrix resin, and usable epoxy resins include, for example, (1) glycidyl ether-based epoxy resin (bisphenol A, F, S-based epoxy resin, Novolak epoxy resin, brominated bisphenol A
(2) Cycloaliphatic epoxy resin; (
3) Glycidyl ester type epoxy resin; (4) Glycidylamine type epoxy resin; (5) Heterocyclic epoxy resin; and one or more types selected from various other epoxy resins, particularly bisphenol A. , F, S glycidylamine-based epoxy resins are preferably used. In addition, as the curing agent, amine-based curing agents such as dicyandiamide (DICY) and diaminophenyl sulfone (D
DS), diaminodiphenylmethane (DDM); acid anhydride systems, such as hexahydrophthalic anhydride (HHPA),
Although methylhexahydrophthalic anhydride (MHHPA) and the like are used, amine-based curing agents are particularly preferably used.

The blending ratio of carbon fibers 2 and matrix resin 6 in the fiber-reinforced composite resin layer 3 can be adjusted as desired, but in general, the ratio by weight of carbon fibers:matrix resin=30 to 80:
A good range is 20 to 70, preferably 40 to 75:25.
~60. If the proportion of carbon fibers 2 is less than 30% by weight, when the matrix resin 6 is cured to form the fiber-reinforced composite resin layer 3 into a fiber-reinforced composite resin material, the strength of the composite resin material due to reinforcement with the carbon fibers 2 will be insufficient. It becomes enough, and on the other hand, it becomes 80
If it exceeds % by weight, the amount of matrix resin 6 will be too small, and there is a possibility that the strength of matrix resin 6 of the composite resin material will not be sufficient.

In the present invention, the resin film layer 4 is provided on the composite prepreg 1 in order to impart impact resistance to a fiber-reinforced composite resin molded product made using the prepreg, such as a golf club shaft. . For this reason, the resin film layer 4 is made to be a relatively flexible layer. For such a resin film layer 4, a thermoplastic resin film such as polyurethane resin, nylon resin, modified nylon resin, polyethylene terephthalate resin, polyvinyl chloride resin, polycarbonate resin, polyvinylidene chloride resin, ethyl cellulose resin, cellulose acetate resin, etc. is used. can be used.

In this case, a thermoplastic resin film that is highly compatible with the matrix resin 6 can be used for the purpose of improving adhesiveness with the fiber-reinforced composite resin layer 3. For example, when an epoxy resin or the like is used for the matrix resin 6, examples thereof include polyurethane resin, modified nylon resin film, and the like.

[0015] The thickness of the resin film layer 4 is 5 to 100 μm.
If the thickness is less than 5 μm, it is too thin and the resulting fiber-reinforced composite resin molded product cannot have sufficient impact resistance, and if it exceeds 100 μm, it is too thick and the fiber-reinforced composite resin material is too thin. The decrease in strength of resin material molded products cannot be ignored.

In the present invention, the metal foil layer 5 is provided on the composite prepreg 1 in order to impart mechanical strength to the resulting fiber-reinforced composite resin molded product, thereby improving the desired torsional fracture strength. can do. For the metal foil layer 5, a foil-like or thin-plate metal sheet, a metal net, or a porous foil-like or thin-plate metal mesh such as expanded metal can be used. The thickness of the metal foil layer 5 is 5 to 50 μm. If the thickness of the metal foil layer 5 is less than 5 μm, it is too thin, and the effect of improving the mechanical strength such as compressive strength and torsional fracture strength of the resulting fiber-reinforced composite resin molded product cannot be sufficiently obtained. On the other hand, if it exceeds 50 μm, it will be too thick, resulting in poor workability during molding and an excessive increase in weight of the resulting fiber-reinforced composite resin material molded product.

Metal materials that can be used for the metal foil layer 5 include aluminum, titanium, iron, copper, nickel, nichrome, tin, lead, magnesium, gold, silver, platinum, and various other metals and alloys thereof. . For example, aluminum foil with a thickness of 20 to 50 μm manufactured by Showa Aluminum Co., Ltd., titanium foil with a thickness of 5 to 30 μm manufactured by Takeuchi Metal Foil & Powder Industry Co., Ltd., stainless steel foil with a thickness of 15 to 50 μm, high strength steel foil, etc. It can be used suitably.

On the surface of this metal foil layer 5, a metal foil layer 5 is laminated on the resin film layer 4 on which it is laminated, or on the fiber reinforced composite resin layer 3, or on the fiber reinforced composite resin layer 3.
When the metal foil layer 5 is laminated between the resin film layer 4 and the resin film layer 4, the metal foil layer 5 is formed by mechanically or physically forming holes, adding lines, or providing unevenness in order to improve the adhesion with these layers. Surface treatments such as roughening can be applied to the surface. Alternatively, the surface of the metal foil layer 5 is treated with a functional group that interacts with the matrix resin 6 of the fiber-reinforced composite resin layer 3 by a chemical method such as potassium dichromate, sodium dichromate, parkerizing, or ACP method. be able to. Metal foil layer 5
When the material is made of aluminum or steel, anodizing is also effective.

[0019] The overall thickness of the composite prepreg 1 is 20 to 3
It is appropriate to set it to 00 μm. If the thickness of the composite prepreg 1 is less than 20 μm, it is too thin, and not only is it difficult to manufacture the prepreg 1, but it is also impractical to use for creating a fiber-reinforced composite resin molded product. Also, the thickness is 30
If it exceeds 0 μm, it will be too thick and it will be difficult to create a fiber-reinforced composite resin molded product with good moldability.

The composite prepreg 1 of this example can be manufactured by any method, but a prepreg in which matrix resin 6 is impregnated between carbon fibers 2 arranged in one direction is used as the fiber-reinforced composite resin layer 3. Then, when producing the prepreg by the hot roll method, the above resin film is attached instead of the cover film to the side opposite to the side to which the release paper is attached to form the resin film layer 4, The metal foil layer 5 can be suitably manufactured by pressing and pasting the above-mentioned metal sheet or mesh onto the resin film layer 4 using, for example, a roller. However, it is not limited to this.

[0021] The present composite prepreg 1 is normally used in combination with a normal prepreg such as a carbon fiber prepreg when producing a fiber-reinforced composite resin molded article. For example, a golf club shaft basically consists of an inner or outer angle layer and an outer or inner straight layer, but the composite prepreg 1 can be used for either the angle layer or the straight layer. It can also be used between straight layers. Generally, it is preferable to wrap one or two layers of the composite prepreg 1 around the straight layer in terms of the performance of the golf club shaft, particularly in terms of impact strength, torsional fracture strength, and feel at impact. Therefore, in the case of a golf club shaft in which the straight layer is located as the outer layer, ordinary prepreg such as carbon fiber prepreg is placed around the mandrel that serves as the mold.
For the angled layer, wrap the fibers the desired number of times with the fiber arrangement direction tilted to the mandrel axis; for the straight layer, wrap the fibers the desired number of times with the fiber arrangement direction parallel to the mandrel axis; 1 to 2 layers of composite prepreg 1 are wound around. Then, the matrix resin is heated and cured while wrapping the pressure tape to prevent deformation of the fiber-reinforced composite resin layer of the normal prepreg and composite prepreg, thereby forming the fiber-reinforced composite resin layer into a fiber-reinforced composite resin material layer. A cured product in the shape of a golf club shaft may be obtained, and then the necessary processing may be performed to finish it into a golf club shaft.

[0022] According to the golf club shaft manufactured by using the composite prepreg 1 of this embodiment in combination, it is not only lightweight, but also has a fiber-reinforced composite resin made of the composite prepreg 1 laminated in a single layer to multiple layers. Since the metal foil layer 5 is provided between the layers of the material, the torsional fracture strength and impact resistance are improved, and the resin film layer 4 is also provided between the layers of the fiber reinforced composite resin material. The impact resistance is further improved, and the feel (hitting feeling) during use is also good.

FIG. 2 is a sectional view showing another embodiment of the composite prepreg of the present invention. Composite prepreg 1 of this example
This differs from the embodiment shown in FIG. 1 in that a fiber-reinforced composite resin layer 3 is laminated on the resin film layer 4, and a metal foil layer 5 is laminated on the fiber-reinforced composite resin layer 3. The configurations of the fiber-reinforced composite resin layer 3, resin film layer 4, and metal foil layer 5 of the composite prepreg 1 of this example are basically the same as those of the example of FIG. 1.

[0024] Also in this example, the obtained fiber-reinforced composite resin molded product such as a golf club shaft has a single layer to
Since the resin film layer 4 and the metal foil layer 5 are provided between the layers of the fiber-reinforced composite resin material laminated in multiple layers, it is lightweight and has high torsional fracture strength as in the previous embodiment. It is high, has good impact resistance, and has a good feel during use (hitting feeling).

FIG. 3 is a sectional view showing still another embodiment of the composite prepreg of the present invention. The composite prepreg 1 of this example differs from the example of FIG. 1 in that a metal foil layer 5 is laminated on the fiber-reinforced composite resin layer 3, and a resin film layer 4 is laminated on the metal foil layer 5. Composite prepreg 1 of this example
The configurations of the fiber-reinforced composite resin layer 3, resin film layer 4, and metal foil layer 5 are basically the same as in the embodiment shown in FIG.

Similarly, according to this example, the obtained fiber-reinforced composite resin material molded product such as a golf shaft has a structure in which a fiber-reinforced composite resin material is laminated in a single layer to a plurality of layers between the layers. Since it is equipped with a resin film layer 4 and a metal foil layer 5, it is lightweight, has high torsional fracture strength, and has good impact resistance.
The feel (hitting feeling) during use is also good.

In all of the above examples, the reinforcing fiber 2
Carbon fiber was used as the material, but boron fiber, glass fiber,
Inorganic fibers such as alumina fibers, silicon carbide fibers, and silicon nitride fibers; organic fibers such as aramid fibers, polyarylate fibers, and polyethylene fibers; or metal fibers such as titanium fibers, amorphous fibers, and stainless steel fibers may be optionally used. Can be done. Further, although the reinforcing fibers 2 are arranged in one direction, the reinforcing fibers 2 may be arranged in two or more directions, or may be arranged in a cross pattern.

FIG. 4 is a sectional view showing still another embodiment of the composite prepreg of the present invention. In the composite prepreg 1 of this example, in the composite prepreg 1 of FIG. 1, in addition to the carbon fiber 2, fibers 7 of a different type are used as reinforcing fibers in the fiber-reinforced composite resin layer 3 to hybridize the reinforcing fibers. It is a characteristic. The other configuration of the composite prepreg 1 of this example is basically the same as the example of FIG. 1.

The above-mentioned different types of fibers 7 are arranged in the matrix resin 6 of the fiber-reinforced composite resin layer 3 in the same direction as the carbon fibers 2 at predetermined intervals. In this example, the fiber diameter is 2 to 30
The carbon fiber 2 has a fiber diameter of 50 μm, whereas the fiber diameter of the different fiber 7 is 50 μm.
Although the above-described diameter is large, the different fibers 7 do not have to have a large diameter. When using the different types of fibers 7 in the form of strands with small fiber diameters, the strand diameter of the different types of fibers 7 is given as the converted diameter D0 = n1/2 × d (n: number of bundled fibers, d: fiber diameter). , the strand diameter is the converted diameter D0
A maximum of 500 μm can be used. Furthermore, as shown in FIG. 4, the different types of fibers 7 are preferably located at the center of the composite prepreg 1, but may be slightly offset above and below the center.

Such a fiber-reinforced composite resin layer 3 can be produced by various methods, but two sheets of prepreg in which carbon fibers 2 are arranged in one direction are used, and different types of fibers 7 are arranged in the same direction as the carbon fibers 2 between them. They can be manufactured very suitably by arranging them at predetermined intervals and integrating them by pressing and/or heating.

In the present composite prepreg 1, as usual, the reinforcing fibers are hybridized with the main purpose of supplementing physical properties or other physical properties that are insufficient with one type of reinforcing fiber, and therefore the different types of fibers 7 are Although it is generally considered to be a material other than carbon fiber, in some cases, carbon fiber may be used as the different type of fiber 7 if the fiber diameter or physical properties are different from that of the other carbon fiber 2. In addition to carbon fibers with different physical properties, the different types of fibers 7 include inorganic fibers such as boron fibers, glass fibers, alumina fibers, silicon carbide fibers, and silicon nitride fibers; organic fibers such as aramid fibers, polyarylate fibers, and polyethylene fibers; Metal fibers such as titanium fibers, amorphous fibers, stainless steel fibers, etc. can be optionally used.

The blending ratio of the carbon fibers 2, different types of fibers 7, and matrix resin 6 in the fiber-reinforced composite resin layer 3 can be set arbitrarily, but in general, the ratio by weight of carbon fibers: different types of fibers: matrix resin is 40 to 80:2. -20: A range of 20-60 is good.

To manufacture a fiber-reinforced composite resin molded product such as a golf club shaft by using the composite prepreg 1 of this example in combination with a normal carbon fiber prepreg, etc., it is sufficient to carry out the process in accordance with the previous example. In addition to the effect of improving physical properties due to the different types of fibers, the obtained fiber-reinforced composite resin molded product also has the effect of layer-to-layer bonding of the fiber-reinforced composite resin material by the composite prepreg 1 laminated in a single layer to multiple layers. The intervening resin film layer 4 and metal foil layer 5 provide excellent effects such as being lightweight, having high torsional fracture strength, good impact resistance, and good feel (hitting feeling) during use.

In this embodiment, the fiber-reinforced composite resin layer 3, which is a hybrid of fiber reinforcement, is placed as the bottom layer, and a resin film layer 4 and a metal foil layer 5 are sequentially formed thereon as in the embodiment shown in FIG. Although the case where they are laminated has been described, the fiber-reinforced composite resin layer 3, resin film layer 4, and metal foil layer 5 can be laminated in the same order as in the embodiment shown in FIG. 2 or 3. Needless to say, similar effects can be obtained. Moreover, instead of two types of reinforcing fibers, three or more types can be used to create a hybrid.

The present invention will be further explained based on specific examples.

[0036] Composite prepreg 1 was prepared according to the present invention,
A golf club shaft was manufactured by using it in combination with ordinary prepreg. The manufacturing method is as follows.

[0037] An angle layer of P with a thickness of 120 μm and a resin content of 32% was applied to a mandrel in the shape of a golf club shaft.
AN-based carbon fiber prepreg (manufactured by Toray Industries, Inc., product name M
-40) is wound at +45° and -45° in total 8 layers, and on top of that, a straight layer with a thickness of 120 μm and a resin amount of 32
% PAN-based carbon fiber prepreg (manufactured by Toray Industries, Inc., trade name T-300) was wound in one layer, and further, as a second straight layer, two layers of composite prepreg 1 of the present invention were wound. Next, one layer of glass fiber unidirectional prepreg with a thickness of 70 μm was wrapped for surface polishing, and finally, E-glass prepreg was wrapped as a reinforcing layer to reinforce the tip, and then taped with polypropylene stretched tape and heated. After curing, a prescribed finishing process such as polishing was performed to prepare a golf club shaft.

The obtained golf club shaft was assembled into a golf club after its mechanical properties such as torsional fracture strength and impact strength were measured, and the feel at impact was tested. For comparison, a composite prepreg was prepared that did not meet the conditions of the present invention, and was used and tested in the manufacture of golf club shafts in the same manner as above. The results obtained are shown in Table 1.

[0039]

[Table 1]

In Table 1, prepreg indicates a fiber-reinforced composite resin layer 3, and foil/prepreg/film indicates a fiber-reinforced composite resin layer 3 laminated on a resin film layer 4, and a metal layer on the fiber-reinforced composite resin layer 3. This shows that the foil layer 5 is laminated. This also applies to other layer configurations. The numerical values after the reinforcing fibers and different types of fibers indicate the blending ratio (wt%) in the fiber-reinforced composite resin layer 3, and the remainder is the amount of matrix resin. Also, the symbol ◎ indicates very good, ◯ indicates good, △ indicates slightly poor, and × indicates poor.

The carbon fibers of the reinforcing fibers in Table 1 have a fiber diameter of 7.
．． 0 μm PAN-based carbon fiber (manufactured by Toray Industries, Inc., trade name T-300) was used. The different types of glass fibers are glass fibers with a fiber diameter of 7.0 μm (manufactured by Asahi Fiberglass Co., Ltd., standard name: E-Glass), and the aramid fibers are aramid fibers with a fiber diameter of 12 μm (manufactured by Teijin Ltd., trade name: Technora). ), the polyarylate fiber has a fiber diameter of 23 μm.
polyarylate fiber (manufactured by Kuraray Co., Ltd., trade name Vectran) was used. Epoxy resin was used as the matrix resin. The stainless steel foil used was made by Takeuchi Metal Foil and Powder Industries Co., Ltd. and had a thickness of 20 μm. The titanium foil used was one manufactured by Takeuchi Metal Foil and Powder Industries Co., Ltd. and having a thickness of 20 μm. Both modified nylon films had a thickness of 20 μm.

As shown in Table 1, in Examples 1 to 7, the composite prepreg used in combination with the ordinary carbon fiber prepreg had a metal foil layer and a resin film layer, so the golf The torsional fracture strength and impact resistance of the club shaft were both improved to better or better, and the feeling of use of the golf club remained better than good. On the other hand, in Comparative Examples 1 and 2, a film layer was not provided on the combined composite prepreg, so the impact resistance was slightly inferior, and in Comparative Example 3, a metal foil layer was not provided on the composite prepreg, so the torsional fracture strength was inferior. At the same time, the usability of the golf club was also inferior.

[0043]

Effects of the Invention As explained above, the composite prepreg of the present invention has a structure in which a fiber-reinforced composite resin layer having one or more types of reinforcing fibers, a metal foil layer, and a resin film layer are laminated. By using this in combination with a normal prepreg, it is possible to obtain a fiber-reinforced composite resin molded product that is lightweight and has improved torsional fracture strength and impact resistance. It is suitable for manufacturing golf shafts, fishing rods, tennis rackets, badminton rackets, etc.

[Brief explanation of the drawing]

FIG. 1 is a sectional view showing one embodiment of the composite prepreg of the present invention.

FIG. 2 is a sectional view showing another embodiment of the composite prepreg of the present invention.

FIG. 3 is a sectional view showing still another embodiment of the composite prepreg of the present invention.

FIG. 4 is a sectional view showing still another embodiment of the composite prepreg of the present invention.

[Explanation of symbols]

1 Composite prepreg 2 Reinforced fiber 3 Fiber reinforced composite resin layer 4 Resin film layer 5 Metal foil layer 6 Matrix resin 7. Different types of fibers

Claims (2)

[Claims] 1. A composite prepreg in which a fiber-reinforced composite resin layer having one or more types of reinforcing fibers, a resin film layer, and a metal foil layer are laminated. [Claim 2] The thickness of the resin film layer is 5 to 100 μm.
m, the thickness of the metal foil layer is 5 to 50 μm, and the total thickness is 2
The composite prepreg according to claim 1, which has a diameter of 0 to 300 μm.