CN1131139C - Tubelike body made of fiber-reinforced composite material - Google Patents

Abstract

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. This tubular form contains a high compression breaking strain layer which contains carbon fibers orientated theta plusmn 15 deg. 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

Tubular body made of fiber-reinforced composite material

technical field

The invention relates to tubular bodies made of fiber reinforced composite material.

Background technique

Tubular bodies made of reinforced fiber composite materials are used in various applications such as golf grips and fishing rods.

For golf grips, in recent years, there has been a greater tendency to be lightweight. It has hitherto been difficult to manufacture lightweight grips with good bending breaking strength because light weight results in a reduction in the bending breaking strength of the bar.

For fishing rods, flexibility is required at the front end. In order to obtain good flexibility, the method of reducing the wall thickness of the front end part is adopted, but at the same time, the bending breaking strength will be reduced. Therefore, it is still difficult to manufacture fishing rods with good bending breaking strength and flexibility.

The purpose of the present invention is to solve the above existing problems and provide a tubular body made of fiber reinforced composite material with good bending breaking strength, bending deflection, and impact energy absorption.

Contents of the invention

The above objects of the present invention are achieved by a tubular body made of fiber reinforced composite material as described below.

That is, the present invention relates to a tubular body made of fiber-reinforced composite material, characterized in that it contains a high compression fracture deformation layer comprising a The compression fracture deformation of the carbon fiber in the orientation direction of the high compression fracture deformation layer is 1-5%, and after converting the fiber volume content of the carbon fiber into 60%, the compressive elastic modulus in the orientation direction of the carbon fiber is 3-120GPa.

A brief description of the drawings

1 is a plan view of a mandrel or a prepreg used for each layer and a cross-sectional view of a tubular body produced in Example 1;

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

Specific Embodiments of the Invention

The tubular body made of the fiber-reinforced composite material of the present invention may have a straight layer in which reinforcing fiber prepregs are stacked along the entire length of the shaft, wherein the reinforcing fiber prepreg is longitudinally (axially) relative to the tubular body. ) are oriented approximately in parallel in the range of 0° to ±5°. The number of stacked straight layers is 1 to 20 layers, preferably 1 to 18 layers, and most preferably 1 to 16 layers. The number of stacked straight layers can be kept equal or varied along the longitudinal direction of the tubular body.

Here, the number of layers mentioned in the present invention refers to how many layers are averagely stacked of specific layers such as straight layers, that is, how many times of winding is performed around the axis of the tubular body.

According to the use of the above-mentioned tubular body, specifically, the use of the golf grip, the tubular body of the present invention has a bias ply formed by laminating layers of reinforcing fiber prepreg, wherein the reinforcing fiber prepreg is made of reinforcing fiber It is oriented within the range of ±20°～±70° in the longitudinal direction of the tubular body.

The bias layers are generally positive and negative bias layers, which are formed by laminating reinforcing fiber prepregs oriented in the range of +20° to +70° relative to the longitudinal direction of the above-mentioned tubular body. A bias layer and a negative bias layer formed by laminating reinforcing fiber prepregs in which reinforcing fibers are oriented in the range of -20° to -70° with respect to the longitudinal direction of the tubular body.

Each layer or multiple layers of positive oblique layers or negative oblique layers are stacked alternately. It is also possible to make the number of laminations of positive skew layers and negative skew layers different from each other. The stacking number of the oblique layers of the positive and negative groups is 1 to 12 layers, preferably 1 to 10 layers. That is, when the number of stacked positive bias layers and negative bias layers is the same, the total number of stacked bias layers is 2 to 24 layers, preferably 2 to 20 layers.

According to other uses of the above-mentioned tubular body, specifically, the use as a fishing rod, the tubular body of the present invention may also have an annular layer formed by making the reinforcing fibers approximately at right angles to the longitudinal direction of the aforementioned tubular body at ±70°. The reinforcing fiber prepregs oriented in the range of ±90°, preferably ±80° to ±90° are laminated and formed. The number of laminations of the ring layer is 1 to 10 layers, preferably 1 to 8 layers. The number of laminated layers of the diagonal layer and the annular layer may be equal or variable along the longitudinal direction of the tubular body.

As the reinforcing fiber used for such a reinforcing fiber prepreg, carbon fiber, glass fiber, aramid fiber, ceramic fiber, boron fiber, metal fiber, etc. can be used, but it is preferable to use bituminous carbon fiber or Polyacrylonitrile-based carbon fiber. As the matrix resin used for the aforementioned reinforcing fibers, thermosetting resins or thermoplastic resins selected from epoxy resins, unsaturated polyester resins, phenolic resins, silicone resins, polyurethane resins, urea resins, melamine resins, etc. can be used, most preferably Well it's epoxy.

As the carbon fiber used in the reinforcing fiber prepreg, such carbon fiber can be used, when the fiber volume content of the aforementioned carbon fiber is calculated as 60%, the compressive modulus of elasticity in the direction of carbon fiber orientation is 125 GPa to 600 GPa.

The present invention is a tubular body made of fiber-reinforced composite material, which is characterized in that a high compression fracture deformation layer is formed, and the deformation layer is composed of a material with a compression fracture deformation of 1.0 to 5.0% and a compression elastic modulus of 3GPa to 120GPa. Laminated carbon fiber prepregs.

As the carbon fiber used in the high compression fracture deformation layer, the compression fracture deformation of 1 to 5%, preferably 1.5 to 5%, more preferably 1.7 to 5%, most preferably 2 to 5% carbon fiber .

In addition, as the carbon fiber used for the high compression fracture deformation layer, it is desirable to use a carbon fiber having a compressive elastic modulus of 3 GPa to 120 GPa, preferably 3 GPa to 100 GPa.

In addition, as the carbon fiber used for the high compression fracture deformation layer, a carbon fiber having a density of less than 1.9 g/cm ³ , preferably less than 1.8 g/cm ³ can be used. When the density is greater than 1.9 g/cm ³ , it is not desirable because the weight of the tubular body will be increased.

In addition, as the carbon fiber used for the high compression fracture deformation layer, carbon fibers having a twisted fiber number of 24,000 or less, preferably 12,000 or less, more preferably 6,000 or less, most preferably 3,000 or less can be used.

When the number of stranded fibers exceeds 24,000, it is not preferable because a hole defect is likely to occur when a prepreg is produced by impregnating a matrix resin, especially when a prepreg with a small carbon fiber mesh is produced.

As the carbon fiber used for the carbon fiber prepreg on the above-mentioned high compression fracture layer, any one of resin-based carbon fiber and polyacrylonitrile-based carbon fiber can be used, but pitch-based carbon fiber is preferably used. In addition, as the matrix resin used in the carbon fiber prepreg of the high compression cracking deformation layer, it can be selected from epoxy resin, unsaturated polyester resin, phenolic resin, silicone resin, polyurethane resin, urea resin, melamine resin, etc. available thermosetting or thermoplastic resins, but epoxy resins are preferred.

In the present invention, there is no particular limitation on the weight of the reinforcing fiber of the prepreg, and it is usually in the range of 20 to 300 g/m ² , preferably 50 to 200 g/m ² . When designing a tubular body having a reinforcement fiber content of more than 300 g/m ² , the degree of freedom in design is limited, which is not preferable. In addition, it is not preferable to manufacture a tubular body in which the reinforcement fiber per unit weight is less than 20 g/m ² , since the prepreg tends to wrinkle.

In order to provide a tubular body made of fiber-reinforced composite material with good bending breaking strength, the aforementioned high compression fracture deformation layer is formed in such a way that the carbon fiber is at 0° to ±15° relative to the longitudinal direction of the tubular body, preferably at 0 ° to ±10°, more preferably in the range of 0° to ±5° substantially parallel to the tubular body, and the carbon fiber prepregs oriented in this way are laminated. The above-mentioned high compression fracture deformation layer may be laminated over the entire lengthwise region of the tubular body. In the case where only the above-mentioned high compression fracture deformation layer is laminated in a part of the longitudinal direction of the tubular body, good bending strength and impact resistance can be imparted to the tubular body on the part where the aforementioned high compression fracture deformation layer is laminated, but in It cannot be expected that the bending breaking strength and the impact resistance will be improved on the part where the above-mentioned high compressive cracking deformation layer is not laminated. Therefore, by laminating the high compression fracture deformation layer over the entire longitudinal region of the tubular body, the bending strength and impact resistance of the entire longitudinal direction of the tubular body can be improved. In addition, both the bending breaking strength and the improvement of the impact resistance should be taken into consideration, so as to reduce the weight of the tubular body.

The prepreg forming the above-mentioned high compression fracture layer can be laminated at any position in the wall thickness direction of the tubular body made of the fiber-reinforced composite material of the present invention, and it is better to be laminated on the outer side of the tubular body, It is preferably laminated on the outermost layer of the tubular body.

In addition, as the prepreg forming the high compression fracture deformation layer, when it can be divided into two or more pieces, prepregs of the same shape or different shapes can be used respectively.

The above-mentioned high compression fracture deformation layer can be used in combination with any one or two or more of diagonal layers, straight layers, and annular layers. Compared with the above-mentioned high compression fracture deformation layer with a wall thickness in the radial direction of the tubular body, other layers, that is, any one of oblique layers, straight layers, and annular layers, or a combination of two or more layers is relatively The ratio of the aforementioned deformation layer is 50:1-1:50, preferably 20:1-1:20, most preferably 15:1-1:15.

As the reinforcing fiber prepreg of the present invention, a fabric prepreg and a unidirectional prepreg can be used, but a unidirectional prepreg is preferably used. The unidirectional prepreg can be sparsely passed through the weft threads for the purpose of fixing the reinforcing fibers.

The Vf of each layer of the high compression fracture deformation layer, the bias layer, the straight layer and the annular layer of the tubular molded body of the present invention is usually 40-90v°l%, preferably 50-75v°l%.

In the present invention, the glass fiber fabric is superimposed on the reinforced fiber prepreg and formed into a wound tubular body, which can increase the compressive strength of the tubular body.

The tubular body made of the fiber-reinforced composite material of the present invention may be a tapered tubular body, or a non-tapered tubular body parallel to the axial direction.

The examples described below do not limit the present invention.

The three-point bending test of the present invention is carried out under the following conditions: fulcrum distance 300mm, indenter radius R75mm, fulcrum radius R12.5mm, test speed 5mm/min.

In addition, the impact test of the present invention is carried out under the following conditions: using a drop weight type impact testing machine (IITM-18 type) manufactured by Rice Cang Manufacturing Co., Ltd., the fulcrum distance is 300mm, the indenter radius is R75mm, the fulcrum radius is R12.5mm, the drop weight Weight 766g, drop height 1800mm, drop hammer speed 6.0mm/sec during impact.

Compressive elastic modulus and compression rupture deformation are carried out in accordance with ASTM D3410, a compression test method for fiber-reinforced composite materials, from the compression stress calculated from the compression weight and the cross-sectional area of the test piece, and the compression deformation obtained from the strain gauge attached to the compression test piece. The compressive modulus of elasticity was determined. Furthermore, the value of the compressive modulus of elasticity in the present invention is a Vf60% conversion value. In addition, the compression cracking deformation is the measured value of the hybrid compression test. The value of the tensile modulus of elasticity is a value measured according to ASTM D3039.

The embodiment of making non-tapered tubular body (embodiment 1, comparative example 1, 2)

After coating paraffin wax manufactured by Linley (Co., Ltd.) as a release agent on a mandrel with a diameter of 6.0 mm and a length of 1200 mm, P3052S-12 manufactured by Toray (Co., Ltd.) was used as a bias layer. Prepreg, the positive and negative two diagonal ply prepregs that can be wound on the mandrel for 3 turns and cut, are wound on the mandrel after overlapping one side with the other at a distance equivalent to half a circle of the shaft , wherein the carbon fibers of the positive and negative bias layer prepregs are respectively oriented at +45° and -45° relative to the longitudinal direction of the mandrel.

Using the P8055S-12 prepreg manufactured by Toray Co., Ltd. as the straight layer, the straight layer prepreg (one piece) that can be wound around the bias layer for 4 turns and cut was wound on the bias layer. Cross-ply, where the reinforcing fibers of the prepreg shall be parallel to the longitudinal direction of the shaft.

Then, as the high compression fracture deformation layer, various unidirectional prepregs shown in Table 1, which can be wound on a straight layer for 3 The resulting high compression fracture set ply is wound on a straight ply with the reinforcing fibers of the prepreg parallel to the longitudinal direction of the mandrel. The shrinkable rubber layer was wound on the laminate obtained by the above lamination (winding), and after heating at 130°C for defoaming and hardening, the mandrel was pulled out to obtain a tubular body. Figure 1 shows a cross-sectional view of the tubular body before the mandrel has been pulled out. In the figure, 1 represents the plan view of the mandrel, 2a is the positive bias layer prepreg, 2b is the negative bias layer prepreg, 3 is the straight layer prepreg, 4 is the high compression fracture deformation layer The respective plan views of the prepregs. The outer diameter of the tubular shape is 9.0mm. Table 1 shows the three-point bending resistance physical properties and impact physical properties of the obtained tubular body.

As shown in Table 1, the tubular body of Example 1 had good three-point bending rupture load (bending breaking strength), three-point bending rupture deflection, and impact absorption load. The tubular body of Comparative Example 1 had low three-point bending resistance to rupture load, three-point bending resistance to rupture deflection, and impact absorption energy, and was poor in performance. The tubular body of Comparative Example 2 was also low in three-point bending breaking load, three-point bending breaking deflection, and impact absorbed energy, and was poor in performance.

The embodiment of manufacturing tapered tubular body (embodiment 2, comparative example 3)

Using a tapered mandrel with a total length of 1200mm, a small diameter of 6mm, and a large diameter of 13.2mm, each layer is stacked from the small diameter side to the large diameter side with a certain number of layers as shown in Figure 2(b)～( e) Cutting in the shape shown, the bias layers are positive and negative bias layers, they should use the prepregs obtained by cutting and winding on the mandrel for 2.5 turns respectively, and the bias layers are separated by a distance equivalent to half a cycle of the shaft After interlacing with the other side, it is wound on the shaft, wherein the carbon fibers of the positive and negative bias layer prepregs are respectively oriented at +45° and -45° relative to the longitudinal direction of the mandrel. Straight layers are laminated for 3 weeks, high compression cracked layers are laminated for 2 weeks, and the rest are produced in the same manner as the non-tapered tubular body.

Table 2 shows the prepregs used for each layer. Different types of prepregs were used for the high compression fracture deformation layer of each Example and Comparative Example, and the performance of the shaft was compared.

Figure 2 shows a cross-sectional view of the tapered tubular body before the mandrel has been pulled out. 1 in the figure shows the plan view of the mandrel, 2a is the positive bias layer prepreg, 2b is the negative bias layer prepreg, 3 is the straight layer prepreg, 4 is the high compression cracking deformation layer prepreg The respective plan views of the impregnated blanks.

The outer diameter of the narrow-diameter side end of the tubular body shaft was 8.2 mm, and the outer diameter of the large-diameter side end was 15.5 mm. Then, the shaft was cut into portions of 400 mm and 800 mm from the small-diameter side end to obtain three types of test bodies having different diameters and a length of 400 mm. The shaft sections cut out from the three test bodies are respectively called the thin diameter part, the central part and the thick diameter part. Table 2 shows the three-point bending resistance physical properties of the resulting shafts.

In Example 2 shown in Table 2, any of the small-diameter portion, the central portion, and the large-diameter portion of the shaft has good three-point bending fracture load resistance. In the shaft of Comparative Example 3, the three-point bending fracture resistance of any of the small-diameter portion, the central portion, and the large-diameter portion was low, and the performance was poor.

In this embodiment, layers can be laminated on the mandrel in the order of oblique layers and straight layers, or in the order of straight layers and oblique layers.

The details of the prepreg used in each embodiment and comparative example are as follows:

(1) P3052S-12 manufactured by Toray Co., Ltd.: polyacrylonitrile-based carbon fiber T700S (tensile elastic modulus 230 GPa, compression fracture deformation 1.4%, compressive elastic modulus 130 GPa), carbon fiber mesh weight 125 g/m ² , ring Oxygen resin content 33wt%.

(2) P8055S-12 manufactured by Toray Co., Ltd.: polyacrylonitrile-based carbon fiber M30S (tensile elastic modulus 300 GPa, compression fracture deformation 0.9%, compressive elastic modulus 175 GPa), carbon fiber mesh weight 125 g/m ² , ring Oxygen resin content 24wt%.

(3) E0526A-10 manufactured by Nippon Graphite Fiber Co., Ltd.: pitch-based carbon fiber XN-05 (tensile elastic modulus 50GPa, compression fracture deformation 2.9%, compressive elastic modulus 32GPa), carbon fiber mesh 100g/m ² , Epoxy resin content 37wt%.

(4) GE-100 manufactured by Nippon Steel Chemical Co., Ltd.: glass fiber (tensile elastic modulus 73GPa, compression fracture deformation 1.3%, compressive elastic modulus 44GPa), glass fiber mesh 100g/m ² , epoxy Resin content 35wt%.

(5) E1526C-10 manufactured by Japan Graphite Fiber Co., Ltd.: pitch-based carbon fiber XN-15 (tensile elastic modulus 150GPa, compression fracture deformation 1.8%, compressive elastic modulus 85GPa), carbon fiber mesh 100g/m ² , The content of epoxy resin is 33wt%. Table 1

Physical properties of three-point bending resistance and impact physical properties of non-tapered tubular body Diagonal layer (3 layers × 2) Straight layer (4 layers) High compression fracture deformation layer (3 layers) Three-point bending resistance physical characteristics Shock physical properties Prepreg Reinforcing Fiber Prepreg Reinforcing Fiber Prepreg Reinforcing Fiber Compression fracture deformation*1 Compression modulus of elasticity*2 Three-point bending fracture load resistance Three-point bending resistance to rupture deflection Impact absorption energy Example 1 P3052S-12T700S P8055S-12M30S E0526A-10XN-05 2.9% 32GPa 820N 30mm 9.0J Comparative example 1 ditto ditto P3052S-12T700S 1.4% 130GPa 735N 17mm 5.2J Comparative example 2 ditto ditto GE-100 glass 1.3% 44GPa 720N 23mm 7.1J

*1: Compression fracture deformation is the compression fracture deformation value in the 0° direction when the carbon fiber used in the high compression fracture deformation layer is used as a unidirectional composite material.

*2: Compressive elastic modulus is the compressive elastic modulus value in the 0° direction after converting the volume content of carbon fiber into 60% when the carbon fiber used in the high compression cracking deformation layer is used as a unidirectional composite material.

Table 2

Three-point Bending Resistance Physical Properties of Conical Tubular Body Diagonal layer (2.5 layers × 2) Straight layer (3 layers) High compression fracture deformation layer (2 layers) Three-point bending fracture load resistance Prepreg Reinforcing Fiber Prepreg Reinforcing Fiber Prepreg Reinforcing Fiber Compression fracture deformation*1 Compression modulus of elasticity*2 Front part Tip-400mm Central part 400-800mm Large diameter part 800mm-Butt Example 2 P3052S-12T700S P8055S-12M30S E1526C-10XN-15 1.8% 85GPa 600N 700N 785N Comparative example 3 ditto ditto P8055S-12M30S 0.9% 175GPa 450N 610N 705N

*1: Compression fracture deformation is the compression fracture deformation value in the 0° direction when the carbon fiber used in the high compression fracture deformation layer is used as a unidirectional composite material.

*2: Compressive elastic modulus is the compressive elastic modulus value in the 0° direction after converting the volume content of carbon fiber into 60% when the carbon fiber used in the high compression cracking deformation layer is used as a unidirectional composite material.

As mentioned above, the present invention can obtain a tubular body made of fiber composite material with good bending rupture resistance, bending rupture resistance, and impact energy absorption.

Claims (7)

1. A tubular body made of fiber-reinforced composite material, characterized in that: it contains a high compression fracture deformation layer, and the high compression fracture deformation layer contains oriented in the range of 0°～±15° relative to the longitudinal direction of the tubular body For carbon fibers, the compression fracture deformation relative to the orientation direction of the high compression fracture deformation layer is 1-5%, and after converting the fiber volume content of the carbon fibers into 60%, the compression elastic modulus of the obtained carbon fiber orientation direction is 3-120GPa . 2. The tubular body made of fiber-reinforced composite material according to claim 1, characterized in that: said tubular body further comprises a diagonal layer and a straight layer. 3. The tubular body made of fiber-reinforced composite material according to claim 1 or 2, characterized in that: said tubular body also includes an annular layer. 4. The tubular body made of fiber-reinforced composite material according to claim 1 or 2, characterized in that: the carbon fibers used in the high compression fracture deformation layer are pitch-based carbon fibers or polyacrylonitrile-based carbon fibers. 5. The tubular body made of fiber-reinforced composite material as claimed in claim 4, characterized in that: the reinforcing fibers used in the diagonal layer and the straight layer are from carbon fiber, glass fiber, aramid fiber, pottery Fibers selected from boron fibers, metal fibers. 6. The tubular body made of fiber-reinforced composite material as claimed in claim 5, characterized in that: the oblique layer or the straight layer contains carbon fibers, and after converting the fiber volume content of the carbon fibers by 60%, the obtained The compressive modulus of elasticity in the direction of carbon fiber orientation is 125-600Gpa. 7. The tubular body made of fiber-reinforced composite material as claimed in claim 4, characterized in that: in the radial direction of the tubular body made of fiber-reinforced composite material, the wall thickness of the high compression fracture deformation layer is the same as that of the The ratio of the total wall thickness of other layers outside the high compression fracture deformation layer is 50:1~1:50.