JPH11123782A - Tubular form of fiber-reinforced composite material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a tubular form of fiber-reinforced composite material which has outstanding rupture strength in bending, rupture deflection in bending and high impact absorbing energy. SOLUTION: This tubular form contains a high compression breaking strain layer which contains carbon fibers orientated θ±15 deg. with the longitudinal direction of the tubular form. In addition, the modulas of compression elasticity, in a direction in which the carbon fibers are orientated, of the carbon fibers, which is calculated based on the conversion of a compression breaking strain in the high compression breaking strain layer, in the direction in which the carbon fibers are orientated, as 1-5% and the fiber-volume content of the carbon fibers as 60%, is 3-120 GPa.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a tubular body made of a fiber-reinforced composite material.

[0002]

2. Description of the Related Art Tubular bodies made of a reinforced fiber composite material are used in various applications such as golf club shafts and fishing rods.

[0003] With respect to golf club shafts, the trend of weight reduction has been further accelerated in recent years. Since the weight reduction leads to a decrease in the bending rupture strength of the shaft, it has been difficult to produce a lightweight shaft having excellent bending rupture strength.

In a fishing rod, it is required that the tip portion has flexibility. In order to obtain excellent flexibility, there is a method of reducing the wall thickness of the tip part, but at the same time, the bending rupture strength is lowered, so that the superior bending rupture strength and flexibility in the tip part have been achieved so far. It was difficult to produce a compatible fishing rod.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a tubular body made of a fiber-reinforced composite material having an excellent flexural strength, flexural flexure and impact energy. is there.

[0006]

The above object of the present invention is achieved by a tubular body made of a fiber-reinforced composite material as described below.
That is, the present invention provides 0 ° to ±
A high compression rupture strain layer containing carbon fibers oriented at 15 °, wherein the high compression rupture strain layer has a compression rupture strain in the carbon fiber orientation direction of 1 to 5% and a fiber volume content of the carbon fiber of 60% The present invention relates to a tubular body made of a fiber-reinforced composite material, characterized in that the compression elastic modulus in the direction of orientation of the carbon fiber calculated as (3) is 3 to 120 GPa.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The fiber-reinforced composite material tubular body of the present invention has a reinforcement in which the reinforcing fibers are oriented at 0 ° to ± 5 ° which is substantially parallel to the longitudinal direction (axial direction) of the tubular body. It may have a straight layer formed by laminating fiber prepregs.

Here, the number of layers referred to in the present invention means how many specific layers such as straight layers are laminated on average, that is, how many turns are wound around the axis of the tubular body.
Depending on the use of the tubular body, specifically the use of a golf shaft or the like, the tubular body of the present invention is a reinforced fiber prepreg in which the reinforcing fibers are oriented at ± 20 ° to ± 70 ° with respect to the longitudinal direction of the tubular body. May be provided with an oblique layer.

[0009] The oblique layer is usually a positive oblique layer formed by laminating reinforcing fiber prepregs in which reinforcing fibers are oriented at + 20 ° to + 70 ° with respect to the longitudinal direction of the tubular body.
Reinforcing fiber is -20 ° to the longitudinal direction of the tubular body.
There is a positive-negative oblique layer of a negative oblique layer formed by laminating reinforcing fiber prepregs oriented at 70 °.

[0010] The positive oblique layers or the negative oblique layers can be alternately laminated every single layer or every plural layers. Also,
The number of layers of the positive oblique layer and the negative oblique layer may be different from each other.

[0011] Depending on other uses of the tubular body, specifically applications such as fishing rods, the tubular body of the present invention has a reinforcing fiber in which the reinforcing fibers are approximately ± 70 ° at right angles to the longitudinal direction of the tubular body.
It may also have a hoop layer formed by laminating reinforcing fiber prepregs oriented at ~ 90 °.

[0012] Examples of the reinforcing fibers used in these reinforcing fiber prepregs include carbon fibers, glass fibers, aramid fibers, ceramic fibers, boron fibers, metal fibers, etc., but preferably pitch-based carbon fibers or polyacrylonitrile. Based carbon fibers can be used. Examples of the matrix resin used in the reinforcing fiber prepreg include a thermosetting resin or a thermoplastic resin selected from an epoxy resin, an unsaturated polyester resin, a phenol resin, a silicone resin, a polyurethane resin, a urea resin, a melamine resin, and the like. And preferably an epoxy resin.

[0013] The carbon fibers used in these reinforced fiber prepregs have a compression breaking strain in the direction of orientation of the carbon fibers of 0.05% or more and less than 1.0%, and a fiber volume content of the carbon fibers of 60% or less. % Of the compression elastic modulus in the orientation direction of the carbon fiber is 125 GPa to 600 GPa.
Can be used.

According to the present invention, there is provided a tubular body made of a fiber-reinforced composite material having such a structure, wherein a prepreg containing carbon fibers having a compressive breaking strain of 1.0 to 5.0% and a compression modulus of 3 to 120 GPa is laminated. A compression breaking strain layer is formed.

The carbon fibers used in the high compression breaking strain layer have a compression breaking strain of 1 to 5%, preferably 1.5 to 5%, more preferably 1.7 to 5%, and most preferably 2 to 5%. ~ 5% carbon fiber can be used.

The carbon fiber used for the high compression breaking strain layer has a compression modulus of 3 GPa to 120 GPa.
a, preferably 3 GPa to 100 GPa carbon fiber.

Further, as the carbon fibers used in the high compression breaking strain layer, carbon fibers having a density of less than 1.9 g / cm ³ , preferably less than 1.8 g / cm ³ can be used. If the density is higher than 1.9 g / cm ³ , the weight of the tubular body increases, which is not preferable.

Further, as the carbon fibers used in the high compression breaking strain layer, the number of strand filaments is 2
4000 or less, preferably 12000 or less, more preferably 6000 or less, most preferably 3000 or less carbon fibers can be used.

The number of filaments of the strand is 240
If the number is larger than 00, it is not preferable because a prepreg impregnated with a matrix resin is easily produced, especially when a prepreg having a small basis weight of carbon fibers is produced.

As the carbon fiber used for the carbon fiber prepreg used for the high compression strain layer, any of pitch-based carbon fiber and polyacrylonitrile-based carbon fiber can be used, and pitch-based carbon fiber is particularly preferable. The matrix resin used for the carbon fiber prepreg used for the high compression breaking strain layer is a thermosetting resin selected from epoxy resin, unsaturated polyester resin, phenol resin, silicone resin, polyurethane resin, urea resin, melamine resin, etc. A resin or a thermoplastic resin is used, and an epoxy resin is preferable.

In the present invention, the basis weight of the reinforcing fibers in the prepreg is not particularly limited.
/ M ² , preferably in the range of 50 to 200 g / m ² . If the basis weight of the reinforcing fibers is greater than 300 g / m ^{2, the} degree of freedom in designing the tubular body is undesirably limited. The reinforcing fiber weight is 20 g / m2.
^{If it is} smaller than ² , the prepreg is apt to wrinkle during the production of the tubular body, which is not preferable.

The high-compression-rupture strain layer provides a tubular body made of a fiber-reinforced composite material having excellent flexural rupture strength.
°, preferably formed by laminating carbon fiber prepregs oriented at 0 ° to ± 5 ° substantially parallel to the longitudinal direction of the tubular body.

The prepreg for forming the high compression rupture strain layer may be laminated at any position in the thickness direction of the fiber-reinforced composite material tubular body of the present invention. More preferably, it can be laminated so as to be the outermost layer of the tubular body.

Further, as the prepreg for forming the high compression rupture strain layer, two or more prepregs each having the same shape or non-identical shape can be used.

The high compressive rupture strain layer is any one of an oblique layer, a straight layer, and a hoop layer, or
It can be used in combination with more than one species. The ratio of the other layer having a thickness in the radial direction of the tubular body to the high compression rupture strain layer, that is, a layer formed by combining one or more of an oblique layer, a straight layer, and a hoop layer. Can be from 20: 1 to 1:20.

As the reinforcing fiber prepreg in the present invention, a textile prepreg and a unidirectional prepreg can be used, and a unidirectional prepreg is preferably used. The unidirectional prepreg can also loosely pass weft yarns for the purpose of fixing reinforcing fibers.

The Vf of each of the high compression breaking strain layer, the oblique layer, the straight layer, and the hoop layer of the tubular molded article of the present invention is usually 40 to 90 vol%, preferably 50 to 75 vol%.
%.

In the present invention, a tube obtained by laminating a glass fiber cloth on a reinforcing fiber prepreg is wound to form a tubular body, and the crushing strength of the tubular body can be increased. The tubular body made of the fiber-reinforced composite material of the present invention may be a tubular body having a taper or a tubular body having no taper and being parallel to an axis.

[0029]

EXAMPLES Examples will be shown below, but the present invention is not limited by these examples. The three-point bending test in the present invention was performed under the conditions of a distance between supporting points of 300 mm, an indenter diameter R of 75 mm, a supporting point diameter of 12.5 mm, and a test speed of 5 mm / min.

The impact test in the present invention uses a falling weight type impact tester (Model IITM-18) manufactured by Yonekura Seisakusho Co., Ltd., with a distance between supports of 300 mm, an indenter diameter of R75 mm, a fulcrum diameter of 12.5 mm, a falling weight of 766 g, Fall height 1800
mm, and the falling weight speed at the time of collision was 6.0 m / sec.

The compressive modulus and the compressive breaking strain are measured in accordance with the compression test method ASTM D3410 for fiber reinforced composite materials, and the compressive stress calculated from the compressive load and the cross-sectional area of the test specimen and the strain applied to the compressive test specimen The compression modulus was measured from the compression strain obtained from the gauge. In addition, the value of the compression elastic modulus in the present invention is a Vf 60% conversion value. The compression rupture strain is an actually measured value in a composite compression test. The value of the tensile modulus is in accordance with ASTM D303.
This is a value obtained by measuring according to No. 9.

Example 1 A wax was applied as a release agent to a mandrel having a diameter of 6.0 mm and a length of 1200 mm, and then as an oblique layer, P3052S-12 (trade name, polyacrylonitrile-based carbon) manufactured by Toray Industries, Inc. Fiber T700S, tensile modulus 230G
Pa, carbon fiber weight of 125 g / m ² , epoxy resin content of 33 wt%), and cutting each of the prepregs so as to make three rounds on the mandrel, to obtain two positive and negative oblique layer prepregs. After shifting one from the other by a distance corresponding to a half circumference of the mandrel so that the carbon fibers of the positive and negative oblique layer prepregs are oriented at + 45 ° and −45 ° respectively with respect to the longitudinal direction of the mandrel, Wrapped around a mandrel.

As a straight layer, P805 manufactured by Toray Industries, Inc.
5S-12 (trade name, polyacrylonitrile-based carbon fiber M30S, tensile modulus 300 GPa, carbon fiber weight 12
A prepreg (5 g / m ² , epoxy resin content 24 wt%) was used, and the prepreg was cut so that the prepreg wrapped around the oblique layer four times. The prepreg was wrapped around the oblique layer so that the reinforcing fibers were parallel to the longitudinal direction of the mandrel.

Further, as a high compression breaking strain layer, E0526A-10 manufactured by Nippon Graphite Fiber Co., Ltd. (trade name, pitch-based carbon fiber XN-05, tensile modulus of 50 GP)
a, carbon fiber basis weight 100 g / m ² , epoxy resin content 37 wt%, compression rupture strain 2.9%, compression elastic modulus 32
GPa) prepreg, and cutting the prepreg so that the prepreg makes three turns on the straight layer. The prepreg (one sheet) obtained from the high-compression strain layer is reinforced by the reinforcing fiber of the prepreg. It was wound on the straight layer so as to be parallel to the direction. A shrink tape was wound around the laminate obtained by the above lamination (winding), heated to 130 ° C. and deaerated and hardened, and then a mandrel was removed to obtain a pipe. FIG. 1 shows a sectional view of the tubular body before the mandrel is removed. In the figure, 1 is a plan view of a mandrel, 2a is a positive oblique layer prepreg, 2b is a negative oblique layer prepreg, 3 is a straight layer prepreg,
4 shows a plan view of each of the high compression rupture strain layer prepregs. The outer diameter of the pipe was 9.0 mm. Table 1 shows the three-point bending properties and impact properties of the obtained pipe.

As shown in Table 1, the pipe of Example 1 had excellent three-point bending rupture load (bending rupture strength), three-point bending rupture, and impact absorption energy. In this embodiment, the oblique layer and the straight layer are laminated on the mandrel in this order, but the straight layer and the oblique layer may be laminated in this order.

Comparative Example 1 P3052S- manufactured by Toray Industries, Inc.
12 (trade name, polyacrylonitrile-based carbon fiber T70
0S, tensile modulus 230 GPa, carbon fiber basis weight 125 g
/ M ^2, an epoxy resin content of 33 wt% compression strain at break 1.4%, except for using the prepreg of the compression elastic modulus 130 GPa), and a pipe was formed in the same manner as in Example 1.

As shown in Table 1, the pipe of Comparative Example 1 was
The three-point bending rupture load, the three-point bending rupture deflection, and the impact absorption energy were low and inferior.

Comparative Example 2 GE-1 manufactured by Nippon Steel Chemical Co., Ltd.
A prepreg having a 00 (trade name, glass fiber reinforced prepreg, tensile modulus of elasticity 73 GPa, glass fiber basis weight 100 g / m ² , epoxy resin content 35 wt%, compression breaking strain 1.3%, compression elastic modulus 44 GPa) was used. A pipe was formed in the same manner as in Example 1, except that a high compression rupture strain layer prepreg obtained by cutting this prepreg so that the prepreg made four turns on the straight layer was used. As shown in Table 1, the pipe of Comparative Example 2 has low three-point bending load, three-point bending fracture, low impact absorption energy,
Was inferior.

Example 2 Overall length 1200 mm, small diameter 6 mm, large diameter 1
After applying wax as a release agent to a mandrel having a taper of 3.2 mm, P3 manufactured by Toray Industries, Inc. as an oblique layer.
Using a prepreg of 052S-12 (trade name, polyacrylonitrile-based carbon fiber T700S, tensile modulus 230 GPa, carbon fiber basis weight 125 g / m ² , epoxy resin content 33 wt%), each wrap around the mandrel 2.5 times. The prepreg was cut into two positive and negative oblique layer prepregs, and the carbon fibers of the positive and negative oblique layer prepregs were each +45 with respect to the longitudinal direction of the mandrel.
One of them was shifted from the other by a distance corresponding to a half circumference of the mandrel so as to be oriented at an angle of -45 °, and then wound around the mandrel.

As a straight layer, P805 manufactured by Toray Industries, Inc.
5S-12 (trade name, polyacrylonitrile-based carbon fiber M30S, tensile modulus 300 GPa, carbon fiber weight 12
A prepreg (5 g / m ² , epoxy resin content 24 wt%) was used, and the prepreg was cut so that the prepreg wrapped around the oblique layer three times. The prepreg was wound on the oblique layer so that the reinforcing fibers were substantially parallel to the longitudinal direction of the mandrel.

Further, as a high compression breaking strain layer, E1526C-10 manufactured by Nippon Graphite Fiber Co., Ltd. (trade name, pitch-based carbon fiber XN-15, tensile modulus of 150 G)
Pa, carbon fiber basis weight 100 g / m ² , epoxy resin content 33 wt%, compression breaking strain 1.8%, compression modulus 8
Using a prepreg of 5 GPa), the prepreg was cut so that the prepreg would make two rounds on the straight layer to obtain a high compression breaking strain layer prepreg. The high compression breaking strain layer prepreg (one sheet) was wound on the straight layer so that the reinforcing fibers of the prepreg were substantially parallel to the longitudinal direction of the mandrel.

A shrink tape was wound around the laminate obtained by the above-mentioned lamination, heated to 130 ° C. and deaerated and hardened, and then a mandrel was removed to obtain a shaft. FIG. 2 shows a sectional view of the tubular body before the mandrel is removed. In the figure, 1 is a plan view of a mandrel, 2a is a positive oblique layer prepreg, 2b
Represents a plan view of a negative oblique layer prepreg, 3 represents a straight layer prepreg, and e represents a plan view of a high compression fracture strain layer prepreg.

The outer diameter of the shaft at the smaller diameter end is 8.2 m.
m, the outer diameter at the large diameter side end was 15.5 mm. Further, the shaft was cut at 400 mm and 800 mm portions from the end portion on the small diameter side to obtain three types of test specimens having different diameters and a length of 400 mm. The three types of test specimens were classified into a small-diameter part, a central part, and a large-diameter part according to the cutting position from the shaft. Table 2 shows the three-point bending properties of the obtained shaft. As shown in Table 2, the shaft of Example 2 had an excellent three-point bending rupture load in any of the small diameter portion, the central portion, and the large diameter portion.

Comparative Example 3 As a high compression breaking strain layer, P8055S- manufactured by Toray Industries, Inc.
12 (trade name, polyacrylonitrile-based carbon fiber M30
S, tensile modulus 300 GPa, carbon fiber basis weight 125 g /
A shaft was formed in the same manner as in Example 2 except that a prepreg having m2, an epoxy resin content of 24 wt%, a compressive rupture strain of 0.9%, and a compression modulus of 175 GPa) was used.

As shown in Table 2, the shaft of Comparative Example 3 was inferior in the three-point bending load at all of the small diameter portion, the central portion, and the large diameter portion, and was inferior.

[0046]

[Table 1]

[0047]

[Table 2]

[0048]

As described above, according to the present invention, it is possible to obtain a tubular body made of a fiber-reinforced composite material having excellent flexural rupture strength, flexural rupture deflection and impact absorption energy.

[Brief description of the drawings]

FIG. 1 is a plan view of a prepreg used for a mandrel and each layer and a cross-sectional view of a tubular body manufactured in Example 1.

FIG. 2 is a plan view of a prepreg used for a mandrel and each layer and a cross-sectional view of a tubular body manufactured in Example 2.

[Explanation of symbols]

1: Mandrel, 2a: Positive cross layer prepreg, 2b:
Negative oblique layer prepreg, 3: straight layer prepreg,
4: High compression rupture strain layer prepreg.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI B29K 105: 08 B29L 23:00 31:52 (72) Inventor Shinichi Takemura 8 Chidoricho, Naka-ku, Yokohama-shi, Kanagawa Nippon Oil Central Research Laboratory Co., Ltd. (72) Inventor Kiho Hayata 8 Chidori-cho, Naka-ku, Yokohama-shi, Kanagawa Nippon Oil & Oil Co., Ltd. Central Research Laboratory Co., Ltd. (72) Inventor Hideyuki Ohno 3-5-1 Nishishinjuku, Shinjuku-ku, Tokyo Japan Graphite Fiber Co., Ltd. (72) Inventor Mikio Shima 3-5-1 Nishi Shinjuku, Shinjuku-ku, Tokyo Japan Graphite Fiber Co., Ltd. (72) Inventor Yutaka Arai 1 Fujimachi, Hirohata-ku, Himeji-shi, Hyogo Nippon Steel Corporation New Materials Division (72) Inventor Tomohiro Nakanishi 1 Kimitsu, Kimitsu City, Chiba Pref.

Claims (2)

[Claims] 1. The method according to claim 1, wherein the longitudinal direction of the tubular body is 0 ° to ± 15
° high compressive rupture strain layer containing carbon fibers oriented in °, the compressive rupture strain of the high compressive rupture strain layer in the carbon fiber orientation direction is 1 to 5% and the fiber volume content of the carbon fiber is 60%. A tubular body made of a fiber-reinforced composite material, wherein the converted compression modulus in the orientation direction of the carbon fiber is 3 to 120 GPa. 2. The fiber-reinforced composite material tubular body according to claim 1, wherein the tubular body further includes an oblique layer and a straight layer.