JPH07196824A - Prepreg using superelastic nickel-titanium fiber - Google Patents

Abstract

PURPOSE:To obtain a prepreg using superelastic nickel-titanium fiber which can easily reinforce a fiber-reinforced A resin molding (e.g. a golf club shaft) in producing the molding from a normal prepreg, thus prevents fragments of the molding from violently flying when the molding is snapped, and enhances the safety of the surroundings. CONSTITUTION:This prepreg is obtd. by impregnating a matrix resin into two kinds of reinforcing fiber arranged in one direction provided one kind of the fiber is a superelastic fiber made of a nickel-titanium alloy with an elongation of 10-60%. When a molding reinforced with the prepreg is snapped during its use, the superelastic fiber prevents fragments of the molding from separating and violently flying. The superelasticity of the fiber imparts good impact absorbing properties, repulsive properties, etc., to the molding.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a nickel-titanium ultra-powder suitable for strengthening fiber reinforced composite resin material molded products such as golf club shafts and badminton rackets to prevent separation of fragments due to breakage during use. An elastic wire composite prepreg.

[0002]

2. Description of the Related Art In recent years, fiber reinforced composite resin materials using prepregs having carbon fibers and various other reinforcing fibers have been widely used in various technical fields, such as golf club shafts, badminton rackets, and tennis rackets. Also in racket frames and the like, fiber-reinforced composite resin material molded products are often used because they are lightweight and have high mechanical strength.

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 are wound around a mandrel 100 serving as a mold, and the matrix resin of the prepregs 101 is cured to make the prepregs 101 carbon fiber reinforced composite. It is formed by using a resin material.

At this time, in order to improve the twisting and bending performance, in the carbon fiber reinforced prepreg, as shown in FIG. 4, the carbon fibers are aligned with the axis of the mandrel 100 (also the axis of the golf club shaft). To the opposite direction (θ), that is, the angle (± θ) clockwise (usually θ =
As shown in FIG. 5, the prepreg 101 (angle layer 101 ') arranged so as to be inclined by 35 ° to 45 °) and the carbon fibers are parallel to the axis of the golf club shaft (θ = 0 °). And a prepreg 102 (straight layer 102 ') arranged in a row, and generally, as shown in FIG. 3, the prepreg 101 (angle layer 101') is formed on the inner layer of the golf club shaft and the prepreg 102 (is formed on the outer layer thereof. Straight layers 102 ') are often used.

Usually, 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 by about 2 to 5 layers,
The golf club shaft is basically an angle layer 101 'having about 4 to 10 layers of carbon fiber reinforced composite resin material on the inner side.
And a straight layer 102 'of about 2 to 5 carbon fiber reinforced composite resin material layers on the outside.

The golf club shaft made of the carbon fiber reinforced composite resin material as described above is light in weight and high in mechanical strength, and the result is generally good.

[0007]

By the way, in golf club shafts, badminton rackets, etc., they are vigorously shaken for use. Therefore, when they are broken, the broken pieces are separated and fly around vigorously. There was a problem that the surroundings were dangerous.

[0008] From the above, molded products made of fiber reinforced composite materials such as golf club shafts and badminton rackets can be easily reinforced, and even if the molded products are broken during use, fragments of the molded products separate and surround the surroundings. It is hoped that the safety of the surroundings will be improved by preventing the violently flying to the area.

Therefore, it is an object of the present invention to easily reinforce a molded product by using it together with an ordinary prepreg when manufacturing a fiber reinforced composite resin material molded product such as a golf club shaft or badminton racket using the prepreg. Even if breakage occurs in these molded products during use, a composite prepreg that eliminates the separation of broken fragments and prevents the fragments from flying vigorously to the surroundings and enhances the safety of the surroundings Is to provide.

[0010]

The above object can be achieved by the nickel-titanium superelastic wire composite prepreg according to the present invention. In summary, the present invention comprises two or more kinds of reinforcing fibers arranged in one direction and a matrix resin impregnated therein, one of the reinforcing fibers is nickel titanium having an elongation of 10 to 60%. This is a nickel-titanium superelastic wire composite prepreg, which is a superelastic wire.

[0011]

EXAMPLE FIG. 1 is a view showing an example of the 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 film peeling. FIG. 3 is a plan view of the composite prepreg in the completed state.

The composite prepreg of the present invention is a prepreg having two or more kinds of reinforcing fibers arranged in one direction, and carbon fibers or the like are usually used when producing a fiber-reinforced composite resin material molded product. Used in combination with the prepreg. In the present invention, nickel-titanium (Ni.Ti) superelastic wire is used for one of two or more kinds of reinforcing fibers in order to give a part of the reinforcing fibers of the composite prepreg a high elongation. This is a great feature.

According to this embodiment, the composite prepreg 1 is
Carbon fibers 2 as main reinforcing fibers and Ni / Ti superelastic wires 3 are arranged in one direction, and the carbon fibers 2 and the superelastic wires 3 are impregnated with a matrix resin 4.
The entire composite prepreg 1 is supported on the release paper 5, and the surface of the prepreg 1 opposite to the release paper 5 is covered with a cover film 6. The composite prepreg 1 is used by removing the release paper 5 and the cover film 6.

The Ni / Ti superelastic wire 3 is made of a Ni / Ti alloy having a high elongation. This high-elongation Ni / Ti alloy is a kind of shape memory alloy, and is designed to memorize the shape by heat treatment. The heat-treated Ni / Ti alloy wire is
It has the property of returning to its original dimensions when the tension is removed after pulling. As such a Ni / Ti alloy having a high elongation, the elongation is typically 15.0% and the composition ratio Ni / Ti≈.
Although there is 50/50 (weight ratio), it is generally known that the elongation is 10 to 60% due to the difference in composition ratio Ni / Ti.

Usually, the elongation of the reinforcing fiber or the reinforcing fiber compounded with the main reinforcing fiber is as follows: carbon fiber: 1 to 1.
5%, SUS fiber: 1.7%, boron fiber: 1.2%,
Glass fiber: 4%, Kevlar fiber (organic fiber): 2.4
%, Both are small. Although Ti fibers have a relatively high elongation, they still break at 10% elongation due to deformation strain.

For the elongation of these fibers, the above Ni.
The elongation of the Ti alloy wire of 10 to 60% is extremely large. Therefore, in the present invention, in order to give a part of the reinforcing fiber of the composite prepreg 1 a high elongation, 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 in which the Ni / Ti superelastic wire 3 is composited is used in combination with a normal prepreg,
When a fiber reinforced composite resin material molded product such as a golf club shaft or badminton racket is manufactured, the molded product is
Even if breakage occurs during use, the Ni / Ti superelastic wire 3 expands greatly without cutting and holds the broken pieces together, so it is possible to prevent the fragments from flying vigorously to the surrounding area. become.

The Ni / Ti superelastic wire 3 is compounded with the carbon fiber 4 in such a manner that the Ni / Ti superelastic wire 3 is spaced by p = 0.2.
As an example, a structure in which the carbon fibers 4 are arranged in one direction at a distance of up to 2.0 mm and the carbon fibers 4 are arranged in one direction around the superelastic wire 3 and between the superelastic wires 3 can be given.

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 or 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.

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, brominated bisphenol A type epoxy resin); (2) cycloaliphatic epoxy resin;
(3) Glycidyl ester-based epoxy resin; (4) Glycidylamine-based epoxy resin; (5) Heterocyclic epoxy resin; and one or more kinds selected from other various epoxy resins, particularly bisphenol A, F, S
Glycidyl amine epoxy resin is preferably used.
As the curing agent, an amine-based curing agent such as dicyandiamide (DICY) or diaminophenyl sulfone (D
DS), diaminodiphenylmethane (DDM); acid anhydride systems such as hexahydrophthalic anhydride (HHPA),
Methylhexahydrophthalic anhydride (MHHPA) or the like is used, but an amine-based curing agent is particularly preferably used.

The reinforcing fiber (carbon fiber 2 + super elastic wire 3) and the matrix resin 4 may be mixed in any proportion, but generally, the weight ratio of reinforcing fiber: matrix resin = 30 to 8
The range of 0:20 to 70 is good, and preferably 40 to 75:
25-60. 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 into a fiber-reinforced composite resin material, the strength of the composite resin material due to the reinforcement by the reinforcing fibers becomes insufficient, and conversely If it exceeds 80% by weight, the amount of the matrix resin 4 becomes too small, and the strength of the matrix resin 4 of the composite resin material may not be sufficient.

Although carbon fiber 2 was used as the main reinforcing fiber, in addition to carbon fiber, metal fiber such as SUS fiber and titanium fiber, inorganic fiber such as boron fiber, organic fiber such as glass fiber and Kevlar fiber, etc. One or more species can be used as the main reinforcing fiber.

The total thickness of the composite prepreg 1 is 20 to 3
It is suitable to set it 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 to manufacture, and it is not practical to use for producing a fiber-reinforced composite resin material molded article. Also, the thickness is 300μ
If it exceeds m, it is too thick, and it becomes difficult to produce a fiber-reinforced composite resin material molded article with good moldability.

The composite prepreg 1 of the present invention can be manufactured by any method, but two resin coatings in which a matrix resin is coated on release paper are used, and the resin of the two resin coated papers is used. The carbon fiber and the Ni / Ti superelastic wire are arranged between them, and these are continuously supplied between hot rolls, and heated and pressed by the hot rolls, whereby the prepreg 1 can be suitably manufactured. it can. However, the present composite prepreg 1 is not limited to this, and 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 mutually opposite directions with respect to the axis of the mandrel 100 (which is also the axis of the golf club shaft),
That is, an angle (± θ) in the clockwise direction (usually θ = 35 ° to 45 °
Prepreg 101 arranged to be inclined by
And a prepreg 102 in which carbon fibers are arranged in parallel (θ = 0 °) to the axis of the golf club shaft, as shown in FIG. 4, and the prepreg 102 is manufactured by curing. When the composite prepreg 1 of the invention is used in combination, the composite prepreg 1 is manufactured by disposing the composite prepreg 1 in the intermediate layer or in the innermost layer or the outermost layer as shown in FIG. 3, for example.

That is, according to the present invention, the prepreg 10
Angle layer 101 ′ of the inner layer and prepreg 1
02, the outer straight layer 102 ', and the composite prepreg 1, the intermediate layer, the innermost layer, or the outermost composite layer 1'.
And a golf club shaft is formed.

Generally, the angle layer 101 'has about 4-10.
The layers and the straight layers 102 'are laminated in about 2 to 5 layers, and the composite layer 1'according to the present invention is 1 to 2 layers. Angle layer 1
It is also possible to use 01 'as the outer layer and the straight layer 102' as the inner layer. In addition, a reinforcing layer (not shown) may be added to the front and rear ends of the golf club shaft in order to compensate for insufficient strength.

Of course, the angle layer 101 'and the straight layer 102' are formed by using various prepregs known to those skilled in the art, which use other fibers such as glass fibers other than carbon fibers as the reinforcing fibers. It is also possible.

According to the fiber-reinforced composite resin material molded product produced by combining the composite prepreg 1 as described above, not only is it lightweight, but even if the molded product is broken during use, Ni. Since the Ti superelastic wire 3 extends greatly without being cut, and the broken pieces are held together, it is possible to prevent the fragments from flying vigorously to the surroundings, and it is possible to enhance the safety of the surroundings. .

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, the angle layer 101 'is formed on the mandrel 100 of the golf club shaft type.
As a prepreg 101 for use, a PAN-based carbon fiber prepreg having a thickness of 120 μm and a resin amount of 32% is + 45 °, −4.
A total of 8 layers are wound at 5 °, two layers of the composite prepreg 1 of the present invention are wound on the composite layer 1 ′, and then a carbon fiber prepreg 103 for the straight layer 103 ′ is formed thereon, the thickness is 130 μm, and the resin amount is Four layers of 35% PAN-based carbon fiber prepreg were wound. Then, one layer of 85 μm thick glass fiber unidirectional prepreg was wound for surface polishing,
Finally, a prepreg of T-glass is wound as a reinforcing layer to reinforce the tip portion of the tip, and then the polypropylene tape is taped to heat and harden it, and then 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 is made of Ni / Ti having an outer diameter of 100 μm and an elongation of 50%.
Alloy wires were arranged in one direction at intervals of p = 1.0 mm. The carbon fiber 2 of the composite prepreg 1 has an outer diameter of 7 μm,
A PAN diameter carbon fiber having physical properties of a tensile strength of 3.5 GPa, a tensile elastic modulus of 240 GPa and an elongation of 1.5% was arranged in one direction at a fiber basis weight of 150 g / m ² . The matrix resin used was an epoxy resin. The obtained golf club shaft had a total length of 1075 mm, a tip (head side) outer diameter of 8.5 mm, and a rear end (grip side) outer diameter of 15.3 mm.

A notch 1.0 mm from the surface is inserted at 150 mm from the tip head side of this golf club shaft, and the trailing end grip side is set on a golf trial machine and swung multiple times at a speed of 40 mm / sec. , Forcibly broken the shaft. As a result, the golf club shaft was broken from the notch at the time when it was shaken 45 times, but the broken fragment on the tip side was Ni of the intermediate composite layer 1 '.
-The Ti superelastic wire did not separate the pieces because they were joined together, and it was possible to prevent fragments from rushing around.

Example 2 A composite layer 1'using the same composite prepreg 1 as in Example 1
Was formed on the outermost layer of the golf club shaft. A golf club shaft was produced in the same manner as in Example 1 except for the above.

Similarly, a notch was formed in the golf club shaft, and the golf club shaft was shaken by a tester to forcibly break the shaft. As a result, the golf club shaft was broken from the notch when it was shaken 41 times, and the broken tip side fragment was not separated by the Ni / Ti superelastic wire of the outermost composite layer 1 ′, I was able to prevent it from flying fast.

[0037]

As described above, the nickel-titanium superelastic wire composite prepreg of the present invention comprises two or more kinds of reinforcing fibers arranged in one direction and a matrix resin impregnated therein. As one of the above-mentioned reinforcing fibers, a superelastic wire made of a nickel-titanium alloy having an elongation of 10 to 60% was used to impart a high elongation to a part of the reinforcing fibers. Therefore, when a fiber reinforced composite resin material molded product such as a golf club shaft or badminton racket is manufactured by using this together with an ordinary prepreg using carbon fiber or the like, even if breakage occurs during use of these molded products, the broken pieces It is possible to prevent the fragments from rushing to the surroundings and to enhance the safety of the surroundings because the fragments can be connected without being separated. Furthermore, due to the superelasticity of the nickel / titanium superelastic wire, it is possible to satisfactorily absorb impact at the time of impact and strongly repel it, giving excellent impact absorption and repulsion to molded products such as golf club shafts. can do.

[Brief description of drawings]

FIG. 1 is a diagram showing an embodiment of a nickel-titanium superelastic wire composite prepreg of the present invention.

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 diagram showing a method for manufacturing a golf club shaft.

FIG. 5 is a plan view showing a prepreg for manufacturing a golf club shaft.

[Explanation of symbols]

 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

Claims (1)

[Claims] 1. A nickel-titanium superelastic material having two or more kinds of reinforcing fibers arranged in one direction and a matrix resin impregnated therein, one kind of the reinforcing fibers having an elongation of 10 to 60%. A nickel-titanium superelastic wire composite prepreg characterized by being a wire.