JP3363559B2 - Nickel / titanium superelastic wire composite prepreg - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention reinforces a fiber-reinforced composite resin material molded article such as a golf club shaft or a badminton racket to separate fragments due to breakage during use. The present invention relates to a nickel-titanium superelastic wire composite prepreg suitable for prevention. [0002] In recent years, fiber-reinforced composite resin materials using prepregs having carbon fibers and other various reinforcing fibers have been widely used in various technical fields, such as golf club shafts, badminton rackets, and the like. In a racket frame of a tennis racket, etc., a fiber-reinforced composite resin material molded article is often used because of its light weight and high mechanical strength. [0003] Such a golf club shaft is composed of a plurality of carbon fiber reinforced composite resin material layers and the like.
As shown in FIG. 3, a predetermined number of carbon fiber reinforced prepregs 101 cut into a predetermined shape and size are wound around a mandrel 100 serving as a mold, and the matrix resin of the prepreg 101 is cured to form the prepreg 101 into a carbon fiber reinforced composite. It is formed by using a resin material. At this time, in order to improve the torsional and bending performance, as a carbon fiber reinforced prepreg, as shown in FIG. 4, carbon fibers are alternately arranged with respect to the axis of the mandrel 100 (also the axis of the golf club shaft). Angle in the opposite direction (θ), that is, angle in the clockwise direction (± θ) (usually θ =
A prepreg 101 (angle layer 101 ') arranged so as to be inclined by 35 ° to 45 °) and, as shown in FIG. 5, carbon fibers are parallel to the axis of the golf club shaft (θ = 0 °). The prepregs 102 (straight layers 102 ') are used, and usually, as shown in FIG. 3, the prepregs 101 (angle layers 101') are formed on the inner layer of the golf club shaft, and the prepregs 102 (angled layers 101 ') are formed on the outer layer. A straight layer 102 ') is often used. Normally, the inner layer prepreg 101 (angle layer 101 ') has about 4 to 10 layers, and the outer layer prepreg 1
02 (straight layer 102 ') is laminated about 2 to 5 layers,
The golf club shaft basically has about 4 to 10 angle layers 101 'on the inner carbon fiber reinforced composite resin material layer.
And a straight layer 102 'of about 2 to 5 outer carbon fiber reinforced composite resin layers. [0006] The golf club shaft made of the carbon fiber reinforced composite resin material as described above is lightweight, has high mechanical strength, and generally provides good results. [0007] In a golf club shaft, a badminton racket, and the like, when the golf club shaft is used by vigorously shaking it, when broken, the broken fragments are separated and fly vigorously around. I went there and there was a problem that the surroundings were dangerous. [0008] For this reason, a fiber-reinforced composite material molded product such as a golf club shaft or a badminton racket can be easily reinforced so that even if the molded product is broken during use, the fragments are separated and the surroundings are separated. It is desired to prevent flying in a vigorous manner and to enhance the safety of the surroundings. SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a fiber-reinforced composite resin material molded article such as a golf club shaft or a badminton racket using a prepreg. Even if these molded articles are broken during use, a composite prepreg that eliminates the separation of broken pieces, prevents the pieces from flying vigorously around, and improves the safety of the surroundings. To provide. The above object is achieved by a nickel / titanium superelastic wire composite prepreg according to the present invention. In summary, the present invention comprises two or more types of reinforcing fibers arranged in one direction and a matrix resin impregnated with the reinforcing fibers, wherein one type of the reinforcing fibers is nickel-titanium having an elongation of 10 to 60%. A nickel / titanium superelastic wire composite prepreg characterized by being a superelastic wire. FIG. 1 is a view showing one embodiment of a nickel-titanium superelastic wire composite prepreg of the present invention. FIG. 1 (a) is a sectional view of the composite prepreg, and FIG. 1 (b) is a cover. It is a top view of the composite prepreg in the state where the film was peeled off. The composite prepreg of the present invention is a prepreg having two or more types of reinforcing fibers arranged in one direction. When a fiber-reinforced composite resin material molded article is produced, a carbon fiber or the like is usually used. Used in combination with prepreg. In the present invention, nickel-titanium (Ni.Ti) superelastic wire is used for one of the two or more types of reinforcing fibers in order to impart high elongation to a part of the reinforcing fibers of the composite prepreg. It is a big feature. According to this embodiment, the composite prepreg 1
A carbon fiber 2 as a main reinforcing fiber and a Ni.Ti superelastic wire 3 are arranged in one direction, and the carbon fiber 2 and the superelastic wire 3 are impregnated with a matrix resin 4.
The entire composite prepreg 1 is supported on release paper 5, and a cover film 6 is covered on the surface of the prepreg 1 on the side opposite to the release paper 5. The composite prepreg 1 is used after peeling off the release paper 5 and the cover film 6. The Ni.Ti superelastic wire 3 is made of a high elongation Ni.Ti alloy. This high elongation Ni / Ti alloy is a kind of shape memory alloy, and is configured to memorize the shape by heat treatment.
When the tension is removed after being pulled, it has the property of returning to its original size. Typically, such a high elongation Ni.Ti alloy has an elongation of 15.0% and a composition ratio of Ni / Ti ≒.
Although there is a 50/50 (weight ratio), one having an elongation of 10 to 60% is generally known due to the difference in the composition ratio Ni / Ti. Normally, the elongation of the reinforcing fiber or the reinforcing fiber compounded with the main reinforcing fiber is carbon fiber: 1-1.
5%, SUS fiber: 1.7%, boron fiber: 1.2%,
Glass fiber: 4%, Kevlar fiber (organic fiber): 2.4
% And both are small. Also, Ti fibers have a relatively high elongation, but still break at 10% elongation due to deformation strain. With respect to the elongation of these fibers, the Ni.
The elongation of the Ti alloy wire is extremely large at 10 to 60%. Therefore, in the present invention, in order to give a high elongation to a part of the reinforcing fibers of the composite prepreg 1, the N of the elongation of 10 to 60% is used.
A Ni.Ti superelastic wire 3 made of an i.Ti alloy is used. The outer diameter of the Ni · Ti superelastic wire 3 is preferably 50 to
It is about 200 μm. The composite prepreg 1 obtained by compounding the Ni / Ti superelastic wire 3 is used in combination with a normal prepreg,
When manufacturing fiber reinforced composite resin material molded products such as golf club shafts and badminton rackets, the molded products are:
Even if a break occurs during use, the Ni / Ti superelastic wire 3 stretches greatly without cutting and keeps the broken pieces together, so that the pieces can be prevented from flying vigorously around. become. The mode of compounding the Ni.Ti superelastic wire 3 with the carbon fiber 4 is as follows.
For example, a structure in which the carbon fibers 4 are arranged in one direction around the superelastic wire 3 and between the superelastic wires 3 is provided as an example. As the matrix resin 4, a thermosetting matrix resin such as an epoxy resin, an unsaturated polyester resin, a polyurethane resin, a diallyl phthalate resin and a phenol resin can be used. Further, a curing agent and other imparting agents such as a flexibility imparting agent are appropriately added so that the curing temperature is 50 to 200 ° C. In one preferred example, the matrix resin is preferably an epoxy resin. Examples of usable epoxy resins include (1) glycidyl ether epoxy resins (bisphenol A, F, S epoxy resins, A novolak epoxy resin, a brominated bisphenol A epoxy resin); (2) a cycloaliphatic epoxy resin;
(3) Glycidyl ester-based epoxy resin; (4) Glycidylamine-based epoxy resin; (5) Heterocyclic epoxy resin; One or more kinds selected from various other epoxy resins are used, and in particular, bisphenol A, F, S
Glycidylamine-based epoxy resins are preferably used.
As the curing agent, amine curing agents such as dicyandiamide (DICY) and diaminophenylsulfone (D
DS), diaminodiphenylmethane (DDM); anhydride systems such as hexahydrophthalic anhydride (HHPA),
Methylhexahydrophthalic anhydride (MHHPA) or the like is used, and an amine-based curing agent is particularly preferably used. The mixing ratio of the reinforcing fiber (carbon fiber 2 + superelastic wire 3) and the matrix resin 4 can be arbitrarily adjusted, but generally, the reinforcing fiber: matrix resin = 30 to 8 by weight%.
The range of 0:20 to 70 is good, preferably 40 to 75:
25 to 60. When the proportion of the reinforcing fibers is less than 30% by weight, when the matrix resin 4 is cured to make the composite prepreg 1 a fiber-reinforced composite resin material, the strength of the composite resin material due to the reinforcement with the reinforcing fibers becomes insufficient. If it exceeds 80% by weight, the matrix resin 4 may be too small, and the strength of the matrix resin 4 of the composite resin material may not be sufficient. Carbon fiber 2 was used as the main reinforcing fiber. In addition to carbon fiber, metal fibers such as SUS fiber and titanium fiber, inorganic fibers such as boron fiber, and organic fibers such as glass fiber and Kevlar fiber. One or more species can be used as the main reinforcing fiber. The overall thickness of the composite prepreg 1 is 20 to 3
Suitably, it is set to 00 μm. If the thickness of the prepreg 1 is less than 20 μm, it is too thin to make the prepreg 1 difficult, and is not practical for use in producing a fiber-reinforced composite resin material molded product. Also 300μ thick
If it exceeds m, it will be too thick, and it will be difficult to produce a fiber-reinforced composite resin material molded article with good moldability. The composite prepreg 1 of the present invention can be produced by any method. However, two resin coatings obtained by coating a matrix resin on release paper are used, and the resin of the two resin coated papers is used. By arranging the carbon fiber and the Ni.Ti superelastic wire between them, continuously supplying them between the hot rolls, and heating and pressing with the hot rolls, the prepreg 1 can be suitably manufactured. it can. However, the present composite prepreg 1, which is not limited to this, is used in combination with a normal prepreg such as a carbon fiber prepreg when manufacturing a fiber-reinforced composite resin material molded product such as a golf club shaft or a badminton racket. For example, in the case of a golf club shaft, the carbon fibers have angles (θ) in opposite directions to the axis of the mandrel 100 (also the axis of the golf club shaft),
That is, the angle (± θ) in the clockwise direction (usually θ = 35 ° to 45 °)
°) Prepreg 101 arranged so as to be inclined by
And a prepreg 102 in which carbon fibers are arranged in parallel (θ = 0 °) with respect to the axis of the golf club shaft, as shown in FIG. When the composite prepreg 1 of the present invention is used in combination, for example, as shown in FIG. That is, according to the present invention, the prepreg 10
1 and the prepreg 1
02 and an intermediate, innermost or outermost composite layer 1 ′ of the composite prepreg 1.
Is formed. Usually, the angle layer 101 'is about 4 to 10
And the straight layer 102 'are laminated about 2 to 5 layers, and the composite layer 1' according to the present invention is composed of 1 to 2 layers. Angle layer 1
01 'may be the outer layer and the straight layer 102' may be the inner layer. Further, in order to compensate for insufficient strength at the front and rear ends of the golf club shaft, for example, a reinforcing layer (not shown) can be added at that location. Of course, the angle layer 101 'and the straight layer 102' are formed by using various prepregs known as those skilled in the art using other fibers such as glass fibers other than carbon fibers as reinforcing fibers. It is also possible. According to the fiber-reinforced composite resin material molded article manufactured by combining such a composite prepreg 1, not only is it lightweight, but even if the molded article breaks during use, Ni. Since the Ti superelastic wire 3 extends greatly without being cut and keeps the broken fragments, the fragments can be prevented from flying vigorously to the surroundings, and the safety of the surroundings can be improved. . The present invention will be further described based on specific examples. Example 1 A golf club shaft made of a fiber-reinforced composite material was prepared by using the composite prepreg of the present invention together with a carbon fiber prepreg. As shown in FIG. 5, an angle layer 101 'is placed on a mandrel 100 in the form of a golf club shaft.
Prepreg 101 is a PAN-based carbon fiber prepreg having a thickness of 120 μm and a resin amount of 32% at + 45 °, −4 °
A total of 8 layers are wound at 5 °, two layers of the composite prepreg 1 of the present invention are wound thereon for the composite layer 1 ′, and a carbon fiber prepreg 103 for the straight layer 103 ′ is further formed thereon with a thickness of 130 μm and a resin amount of Four layers of 35% PAN-based carbon fiber prepreg were wound. And one layer of a glass fiber unidirectional prepreg having a thickness of 85 μm for surface polishing,
Finally, a T-glass prepreg is wrapped as a reinforcing layer to reinforce the tip portion, and then taped with a polypropylene stretch tape and heat-cured. Thereafter, a predetermined finish such as polishing is performed to form a golf club shaft. Created. The Ni.Ti superelastic wire 3 used for the composite prepreg 1 has an outer diameter of 100 μm and an elongation of 50%.
The alloy wires were arranged in one direction at an interval of p = 1.0 mm. The carbon fiber 2 of the composite prepreg 1 has an outer diameter of 7 μm,
PAN- based carbon fibers having physical properties of 3.5 GPa in tensile strength, 240 GPa in tensile elasticity and 1.5% elongation, were arranged in one direction at a basis weight of 150 g / m ² . The matrix resin used was an epoxy resin. The dimensions of the obtained golf club shaft were 1075 mm in total length, 8.5 mm in outer diameter at the front end (head side), and 15.3 mm in outer diameter at the rear end (grip side). A notch of 1.0 mm from the surface is placed 150 mm from the tip head side of the golf club shaft, the rear end grip side is set on a golf hitting machine, and the golf club is swung a plurality of times at a speed of 40 mm / sec. The shaft was forcibly broken. As a result, the golf club shaft was broken from the notch at the time of swinging 45 times, but the broken tip fragment was Ni Ni of the intermediate composite layer 1 '.
-The fragments were not separated because they were tied up by the Ti hyperelastic wire, and the fragments could be prevented from flying vigorously around. Example 2 The same composite prepreg 1 as used in Example 1 was used to form a composite layer 1 ′.
Was formed on the outermost layer of the golf club shaft. Otherwise, a golf club shaft was prepared in the same manner as in Example 1. Similarly, a notch was formed in the golf club shaft, and the golf club was swung by a test hitter to forcibly break the shaft. As a result, the golf club shaft breaks from the notch at the time of swinging 41 times, and the broken tip-side fragment is not separated by the Ni.Ti superelastic wire of the outermost composite layer 1 ', and Was able to be prevented from flying fast. As described above, the nickel-titanium superelastic wire composite prepreg of the present invention comprises two or more types of reinforcing fibers arranged in one direction and a matrix resin impregnated with the reinforcing fibers. As one of the two or more types of reinforcing fibers, a superelastic wire made of a nickel-titanium alloy having an elongation of 10 to 60% was used to impart high elongation to a part of the reinforcing fibers. Therefore, when a fiber-reinforced composite resin material molded article such as a golf club shaft or a badminton racket is manufactured by using this in combination with a normal prepreg using carbon fiber or the like, even if breakage occurs during use of these molded articles, the broken fragment Can be kept together without being separated, and the fragments can be prevented from flying vigorously to the surroundings, so that the safety of the surroundings can be improved. Furthermore, due to the superelastic performance of the nickel / titanium superelastic wire, it is possible to absorb the impact at the time of hitting and to repel it strongly, giving excellent shock absorption and rebound to molded products such as golf club shafts. can do.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a view showing one embodiment of a nickel-titanium superelastic wire composite prepreg of the present invention. FIG. 2 is a cross-sectional view showing a golf club shaft provided with a composite layer of the composite prepreg of FIG. FIG. 3 is a sectional view showing a conventional golf club shaft. FIG. 4 is an explanatory view showing a method of manufacturing a golf club shaft. FIG. 5 is a plan view showing a prepreg for manufacturing a golf club shaft. [Description of Signs] 1 Nickel / titanium superelastic wire composite prepreg 1 'composite layer 2 carbon fiber 3 nickel / titanium superelastic wire 4 matrix resin 5 release paper 6 cover film

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁷ , DB name) B29B 11/16 B29B 15/08-15/14 C08J 5/24

Claims (1)

(57) [Claim 1] It is composed of two or more kinds of reinforcing fibers arranged in one direction and a matrix resin impregnated therein, and one kind of the reinforcing fibers has an elongation of 10%. A nickel-titanium superelastic wire composite prepreg, which is a nickel-titanium superelastic wire of about 60%.