JPH04249137A - Fiber reinforced resin material - Google Patents

Abstract

PURPOSE:To manufacture the above fiber reinforced resin material of high mechanical strength and without generating delamination. CONSTITUTION:A three-dimensional filler provided with projections in the three- dimensional directions like a tetrapod is interposed in a fiber reinforced resin material composed of laminate reinforced fiber layers and impregnated with synthetic resin together with said synthetic resin. Said projections are in the state of biting into the fiber reinforced layer. As the three-dimensional filler, for example, a zinc oxide whisker is used.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fiber-reinforced resin material particularly having excellent strength between reinforcing fiber layers.

0002

BACKGROUND OF THE INVENTION Fiber-reinforced resin materials are composite materials made by laminating multiple layers of reinforcing fibers and impregnating the layers with synthetic resin, and are used in various applications as FRP. For example, as shown in FIG. 8, a cylindrical fiber-reinforced resin material 90 is used for fishing rods, pipes, lightweight structural materials, and the like. The fiber-reinforced resin material 90 is obtained by laminating (winding) glass rovings 9 as reinforcing fiber layers in multiple layers, impregnating a synthetic resin 8 between them, and heat-curing the synthetic resin 8. Note that the fiber reinforced resin material 90 has a circular cavity 93 inside thereof. The mechanical properties of fiber-reinforced resin materials depend mostly on the reinforcing fiber layer.

0003

[Problem to be Solved] However, as shown in FIG. 8, fiber-reinforced resin materials tend to cause delamination 95 between the laminated reinforcing fiber layers, and when this delamination 95 occurs, the fiber-reinforced resin material 90 The strength will drop significantly. As shown in FIG. 8, when the fiber-reinforced resin material 90 is cylindrical, this delamination 95 often occurs in the direction along the circumference. Further, a plate-shaped fiber-reinforced resin material (see FIG. 6 described later) in which cloth-shaped reinforcing fiber layers are laminated in the vertical direction also has the problem of delamination. As described above, fiber-reinforced resin materials are excellent as lightweight and high-strength materials, but they suffer from the serious problem of delamination.

In order to deal with this problem of delamination, a method has been proposed in which short fibers such as glass fibers are three-dimensionally arranged in a jet stream in a direction perpendicular to the longitudinal direction of the reinforcing fiber layer ( (Special Publication No. 2-2986). However, this method requires larger equipment and is difficult to implement for products with complex shapes, cylindrical shapes, and thick fiber-reinforced resin materials. Therefore, the inventors conducted various studies as a countermeasure against delamination and came up with the present invention. In view of these problems, the present invention aims to provide a fiber-reinforced resin material that can prevent delamination and has excellent mechanical strength.

[0005]

[Means for solving the problems] The present invention provides a fiber-reinforced resin material in which reinforcing fiber layers are laminated in a multi-layered manner and a synthetic resin is impregnated between them. A three-dimensional filler having protrusions in three-dimensional directions like a shape is interposed with the above synthetic resin,
The three-dimensional filler is a fiber-reinforced resin material characterized in that its acicular protrusions bite into the reinforcing fiber layer. The most noteworthy thing about this invention is that
The three-dimensional filler is interposed together with the synthetic resin between the laminated reinforcing fiber layers, and the protrusions of the three-dimensional filler are wedged into the reinforcing fiber layers.

[0006] As the three-dimensional filler, a material having protrusions protruding in three or more directions is used. The size of the three-dimensional filler is such that the maximum distance between its needle-like protrusions is 10 μm.
It is preferable to use one of m or more. When the thickness is less than 10 μm, there is little contribution to strength improvement. Examples of the three-dimensional filler include zinc oxide whiskers. As shown in FIG. 3, which will be described later, the whisker has acicular protrusions that protrude in four directions in a tetrapod shape. Further, the three-dimensional filler is preferably used in an amount of 0.05 to 5% (weight ratio) based on the synthetic resin. If it is less than 0.05%, the amount of three-dimensional filler that bites in between the reinforcing fiber layers is small, and the strength improvement is not sufficient. On the other hand, even if it exceeds 5%, it is difficult to obtain a commensurate increase in strength.

[0007]

[Operations and Effects] In the present invention, a three-dimensional filler is interposed together with a synthetic resin between the laminated reinforcing fiber layers, and the protrusions of the three-dimensional filler are wedged into the reinforcing fiber layers. The fiber-reinforced resin material of the present invention has high strength, particularly high bending strength and bending modulus. The reason why such high strength is obtained is not clear, but it is thought to be due to the following reasons. That is, the three-dimensional filler plays a role of connecting between the reinforcing fiber layer and the synthetic resin to improve the strength, and a large number of the three-dimensional filler is also present in the synthetic resin matrix to improve the strength of the matrix itself. It seems that it is possible to do so. In addition, delamination is therefore less likely to occur. As described above, according to the present invention, it is possible to provide a fiber-reinforced resin material that can prevent delamination and has excellent mechanical strength.

[0008]

EXAMPLES Example 1 A fiber-reinforced resin material according to the present invention will be explained with reference to FIGS. 1 to 7. The fiber reinforced resin material 10 of this example is shown in FIG.
As shown in the figure, reinforcing fiber layers 1 are laminated in a multilayered manner, and a synthetic resin 2 is impregnated between them, and a large number of three-dimensional fillers 3 are interposed between the laminated reinforcing fiber layers 1. It becomes. The needle-like protrusions 31 of the three-dimensional filler 3 are in a state of digging into the reinforcing fiber layer 1. As shown in FIG. 3, the three-dimensional filler 3 has acicular protrusions 31 extending in the three-dimensional direction like a tetrapod shape. Note that FIG. 3 shows the S of zinc oxide whiskers, which will be described later.
This is a transcription of an EM photograph (scanning electron micrograph, magnification: 1000x).

The reinforcing fiber layer 1 is a roving made by bundling a large number of reinforcing fibers (for example, glass fibers) 11, as shown in FIG. Then, this roving is shown in Figure 5.
As shown in the figure, the fiber-reinforced resin material is wound and laminated to form the skeleton. As can be seen from this,
FIG. 1 shows a cross section of the laminated portion of the reinforcing fiber layer 1 shown in FIG. Further, in manufacturing the fiber reinforced resin material 10, a synthetic resin bath 25 is prepared in which a three-dimensional filler 3 is added and dispersed in a liquid synthetic resin 2, as shown in FIG. Then, a reinforcing fiber layer (roving) 1 made up of thousands to tens of thousands of reinforcing fibers is pulled out from the bobbin 110, immersed in a synthetic resin bath 25, and a synthetic resin 2 is impregnated around the reinforcing fiber layer 1. let Subsequently, the reinforcing fiber layer 1 is wound in a layered manner using a winding rod 4.

The above-mentioned winding is carried out in the same way as the usual method, as shown in FIG. This is done using the fold-back method of wrapping around the area. After winding, the synthetic resin is heated and hardened, and the winding rod 4 located at the center is pulled out. As a result, as shown in the figure, a cylindrical fiber-reinforced resin material 10 having a cavity 14 is obtained. In addition, the same figure shows a ring 10 made by cutting this fiber-reinforced resin material 10 into rings.
1 was shown. This ring 101 is used for a delamination test, as will be described later.

What is important in the production of the fiber-reinforced resin material 10 is that when the roving-shaped reinforcing fiber layer 1 is immersed in the synthetic resin bath 25 to impregnate it with the synthetic resin 2, The three-dimensional filler 3 is also the reinforcing fiber layer 1
It is attached to the surface of the surface. Then, while the reinforcing fiber layer 1 is being wound, the three-dimensional filler 3 is taken in between the reinforcing fiber layers 1 and bites into the spaces between the reinforcing fiber layers 1. As a result, the fiber-reinforced resin material 10 shown in FIG. 1 is obtained.

As mentioned above, the fiber reinforced resin material 1 of this example
0, as shown in FIG. 1, the three-dimensional filler 3 is interposed between the reinforcing fiber layers 1 together with the synthetic resin 2, and the needle-like protrusions 31 of the three-dimensional filler 3 are biting into the reinforcing fiber layer 1. Therefore, the mechanical strength between the laminated reinforcing fiber layers 1 is improved, and delamination can be prevented. In addition,
In the above description, a fiber-reinforced resin material in which bundle-like rovings are laminated in a cylindrical shape as a reinforcing fiber layer has been described, but as shown in FIG.
Of course, the present invention can also be applied to a plate-shaped fiber-reinforced resin material formed by laminating multiple layers.

Example 2 Fiber-reinforced resin material according to the present invention (sample Nos. 1 and 2)
was created. For comparison, fiber-reinforced resin materials (sample Nos. C1 and C2) without using three-dimensional fillers were also produced. For these, bending strength (kg/mm) and bending elastic modulus (kg/mm2) were measured. The result is
Shown in the table. That is, in Sample 1 according to the present invention, glass roving (ER2310 manufactured by Asahi Fiber Glass Co., Ltd.) was first used as the reinforcing fiber layer. In addition, as synthetic resins, epoxy resins (manufactured by Ciba Geigy, LY5052 and HY5
052 in a ratio of 10:3.8) was used.

[0014] In addition, as a three-dimensional filler, the above-mentioned figure 3
The zinc oxide whiskers shown in (manufactured by Matsushita Industrial Equipment Co., Ltd., Panatetra) were used. This one had needle-like protrusions extending in approximately four directions, and the total length was 30 μm on average. The three-dimensional filler was used in an amount of 1 part by weight (0.2%) based on 500 parts by weight of the synthetic resin. Then, as shown in Example 1 above, the roving was immersed in the mixed bath of the synthetic resin and the three-dimensional filler to impregnate and adhere to it, and then wrapped around an iron pipe having an outer diameter of 50 mm. The winding was performed at a winding angle of 45 degrees and a pitch of 1, as shown in Figure 5 above.
Proceed in the length direction at 50 mm, turn around after 500 mm, and return to the original position. Next, start again from the side section where you ran the first time and go 500mm in the same way and return. Then, when the iron pipe is uniformly covered with roving,
A total of 3 plies were laminated and wrapped.

[0015] Thereafter, heating was performed at 120°C for 60 minutes to heat and harden the synthetic resin. Next, the iron pipe was extracted to obtain a cylindrical fiber-reinforced resin material. Next, in order to measure the strength of this fiber-reinforced resin material, it was cut into rings 101 as shown in the lower part of FIG. Then, as shown in FIG.
It was set between 1.52. In the compression test, the downward speed of the jig 52 was 5 mm/min. Then, a load was applied in the diametrical direction of the ring 101, and the bending strength and bending elastic modulus were calculated from the maximum load when delamination occurred in the fiber-reinforced resin material.

[0016] Also, sample No. Sample No. 2 has a ratio of three-dimensional filler to synthetic resin of 0.1%, and the other samples are Sample No. 2. It is the same as 1. Next, as a comparative example, sample No. C1 does not use a three-dimensional filler, and the others are sample No. It is the same as 1. Also, sample No.
．． C2 is the sample No. In 1, instead of the three-dimensional filler, linear fine short glass fibers (manufactured by Asahi Fiberglass Co., Ltd. M) with a diameter of about 13 μm and an average length of 65 μm
F-T10A). This short fiber was blended at 0.2% (weight ratio) with respect to the synthetic resin. Others are sample No. It is the same as 1.

The measurement results are shown in the table. As can be seen from the table, sample No. according to the present invention. 1 and 2 are comparative sample N
o. Compared to C1 and C2, bending strength is approximately 110 kg/m
m and flexural modulus of about 4800 kg/mm2, both of which are high values. Thus, the fiber reinforced resin material according to the present invention has high mechanical strength.

[0018]

【table】 [Brief explanation of the drawing]

FIG. 1 is an explanatory cross-sectional diagram of a fiber-reinforced resin material in Example 1.

FIG. 2 is a perspective view of a laminated state of reinforcing fiber layers in Example 1.

FIG. 3 is an enlarged view of zinc oxide whiskers as a three-dimensional filler in Example 1.

FIG. 4 is an explanatory diagram of the manufacturing method of the fiber-reinforced resin material in Example 1.

FIG. 5 is a manufacturing process diagram of a cylindrical fiber-reinforced resin material in Example 1.

FIG. 6 is an explanatory diagram of a plate-shaped fiber-reinforced resin material in Example 1.

FIG. 7 is an explanatory diagram of strength measurement in Example 2.

FIG. 8 is a perspective view of a conventional cylindrical fiber-reinforced resin material.

Claims (1)

[Claims] Claim 1: In a fiber-reinforced resin material in which reinforcing fiber layers are laminated in multiple layers and a synthetic resin is impregnated between them, there is a three-dimensional space between the laminated reinforcing fiber layers like a tetrapod shape. A fiber-reinforced resin material characterized in that a three-dimensional filler having projections in the direction is interposed together with the synthetic resin, and the projections of the three-dimensional filler are in a state of digging into the reinforcing fiber layer.