JP3326984B2 - Organic fiber reinforced resin material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic fiber reinforced resin material, and more particularly to an organic fiber reinforced resin material which prevents interlaminar shear fracture in bending / compression deformation, improves bending / compression strength, and impregnates resin. The present invention relates to an organic fiber reinforced resin material having excellent mechanical properties by improving the following.

[0002]

2. Description of the Prior Art As a conventional organic fiber reinforced thermoplastic resin material, an aramid fiber material / thermoplastic resin composite material has been proposed (JP-A-63-87228, JP-A-1-228).
0199, JP-A-2-144901, JP-A-3-76614, JP-A-3-121135, JP-A-3-130118 and JP-A-3-16
No. 1331), and a nylon fiber material or a polyester fiber / thermoplastic resin composite material has been proposed (JP-A-59-207966, JP-A-1-43532).
JP, JP-A-2-124856, JP-A-3-7
6614 and JP-A-3-130118).

[0003] Conventional organic fiber reinforced thermosetting resin materials include aramid fiber material, liquid crystal fiber material, ultra high molecular weight polyethylene fiber material, vinylon fiber material and PPS / PEEK fiber material as unsaturated fiber. It is manufactured as a composite material using a resin or an epoxy resin as a base material. These composite materials are manufactured by laminating a resin-impregnated prepreg in a mold and then curing the resin under pressure and heat.

On the other hand, as a reinforcing fiber treatment method by needle punching, for example, a combination of a glass long fiber and a glass long fiber mat (Japanese Patent Application Laid-Open No. 62-240514) or a glass long fiber and an organic fiber such as polyamide or polypropylene fiber are used. Combination with a mat (Japanese Patent Laid-Open No. 59-71847)
Publication).

[0005]

However, in the above-mentioned conventional organic fiber reinforced resin material, a woven laminate or a nonwoven fabric laminate is usually used as a reinforcing fiber. When subjected to the above, there is a disadvantage that the fiber tension cannot be sufficiently exerted due to the shear fracture between the laminated layers, and the bending / compression strength is significantly reduced. In addition, in the case of a woven fabric laminate, the number of woven fabrics increases when forming a thick material, so that the laminating operation becomes complicated, and because of the filtering effect of the woven fabric at the time of resin impregnation, the resin impregnating property is significantly impaired, and sufficient mechanical There is a drawback that characteristics cannot be obtained. On the other hand, when the nonwoven fabric laminate is used alone, the impregnating property of the resin is good, but there is a drawback that it is extremely difficult to satisfy the high strength required for the material in recent years.

[0006] On the other hand, in the processing of reinforcing fibers by needle punching, conventionally, the purpose is to improve the handling of glass fibers aligned in one direction, and in practice, glass fibers are cut and matted. And has a drawback that the merit of using long fibers is not utilized.

Accordingly, an object of the present invention is to prevent interlaminar shear failure in bending / compression deformation of an organic fiber reinforced resin material,
An object of the present invention is to provide an organic fiber reinforced resin material having excellent mechanical properties by improving bending / compression strength and improving resin impregnation.

[0008]

Means and Action for Solving the Problems The present inventors have
Attention is paid to the fact that the smaller the number of layers during bending / compression deformation, the smaller the number of layers in the same thickness of the laminated material, the smaller the probability of destruction and the greater the breaking strength. Improving the bending / compressive strength of organic fiber reinforced resin by stacking sheets in which fibers are stuck into a woven fiber bundle and tightly integrated, and furthermore, the nonwoven fabrics are entangled with each other and the interlayer between the sheet laminates is apparently eliminated. It was found that, by integrating the organic fiber woven fabric and the organic fiber non-woven fabric, the impregnation of the woven fabric with the resin monomer was reduced as compared to the woven fabric alone, and the void fraction could be significantly reduced. The invention has been reached.

The object of the present invention is to provide a method in which a predetermined number of sheets obtained by needle-punching and unifying an organic fiber nonwoven fabric on both sides or one side of an organic fiber fabric are laminated in a mold and then impregnated with a resin monomer. This is achieved by an organic fiber reinforced resin material in which a resin is reacted and solidified or laminated in a prepreg sheet state in which a resin monomer has been impregnated in advance, and the resin is reacted and solidified.

[0010] It is preferable that the void fraction of the sheet obtained by needle-punching an organic fiber nonwoven fabric on both sides or one side of the organic fiber woven fabric is 5% by volume or less. When the void fraction of the sheet exceeds 5% by volume, the strength is remarkably reduced due to fracture starting from the void.

The basis weight of the organic fiber nonwoven fabric is 20 to 250.
It is preferably in the range of g / m ² . When a weight per unit area of the organic fiber nonwoven fabric is less than 20 g / m ² weak entanglement of fibers between the nonwoven fabric and therefore likely to occur interlaminar shear strength decreases, exceeding 250 g / m ² in the opposite nonwoven fiber voids of And the impregnation of the resin is significantly inhibited, and the strength of the composite material is reduced. Further, the sheet in which the organic fiber woven fabric and the organic fiber non-woven fabric are integrated is 10 to 60% by weight.
Is preferably contained in the range of If the content of the sheet is less than 10% by weight, the sheet is likely to undulate and not sufficiently function as a reinforcing fiber, and conversely 60% by weight.
If it exceeds 300, the nonwoven fabric will be crushed at the time of lamination, the voids between the fibers will be dense, and the resin impregnation will be significantly inhibited.

[0012]

According to the present invention, as shown in FIGS. 1 and 2, the reinforcing fibers are formed by laminating an organic fiber nonwoven fabric on both sides or one surface of an organic fiber woven fabric, and then needle-punching the fibers to form the organic fiber nonwoven fabric. Is strongly integrated so as to pierce the organic fiber woven fiber bundle, thereby preventing delamination between the organic fiber woven fabric and the organic fiber non-woven fabric during bending or compressive deformation, and allowing the organic fiber non-woven fabric to mutually Provided is an organic fiber reinforced resin in which the sheets are united by being entangled to improve the breaking strength, and further, by using an organic fiber nonwoven fabric, the void fraction is significantly reduced as compared with a woven fabric alone laminate. Can be.

[0013]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.
In addition, about the material obtained by the Example and the comparative example, the following measurements were performed.

Bending test It was based on JIS K 7055. A test piece was cut out in parallel with the fiber direction and measured under predetermined conditions.

[0015] Compression test: In accordance with JIS K 7056 B method. A test piece was cut out in parallel with the fiber direction and measured under predetermined conditions.

Interlaminar shear test This was based on JIS K 7057. A test piece was cut out in parallel with the fiber direction and measured under predetermined conditions.

Izod impact test It was based on JIS K 6911. A test piece was cut out in parallel with the fiber direction, and a flat wise impact test was performed under a predetermined condition.

Measurement of Specific Gravity of Reinforcement The weight of organic fiber reinforced resin pieces in air and methanol was calculated by the buoyancy method at room temperature.

Void fraction Calculated according to void fraction (volume%) = 100 × [(theoretical density) − (measured density)].

Examples 1 to 3 Commercially available high-strength vinylon fiber plain fabric (basis weight 180 g /
m ² ), a sheet obtained by integrating a commercially available general-purpose vinylon fiber nonwoven fabric (having a basis weight of 100 g / m ² ) by needle punching on both sides of the commercial acetone was immersed in commercial acetone for 30 minutes, and the acetone was sufficiently removed. Dry for 24 hours. A predetermined number of the obtained sheets are stacked and placed in a mold, and a ring-opening bulk polymerizable thermosetting resin, dicyclopentadiene (D
CP) was injected, and a curing reaction was performed to obtain a plate-shaped sample. The plate thickness was set to 5 mm regardless of the number of reinforcing fibers laminated.

Example 4 Commercially available high-strength vinylon fiber plain fabric (weight per unit area: 360 g /
m ² ), a sheet obtained by integrating a commercially available general-purpose vinylon fiber nonwoven fabric (having a basis weight of 100 g / m ² ) by needle punching on both sides of the commercial acetone was immersed in commercial acetone for 30 minutes, and the acetone was sufficiently removed. Dry for 24 hours. A predetermined number of the obtained sheets are stacked and placed in a mold, and a ring-opening bulk polymerizable thermosetting resin, dicyclopentadiene (D
CP) was injected, and a curing reaction was performed to obtain a plate-shaped sample. The plate thickness was set to 5 mm.

Example 5 Commercially available high-strength vinylon fiber plain fabric (basis weight 180 g /
m ² ), a sheet obtained by integrating a commercially available general-purpose vinylon fiber nonwoven fabric (having a basis weight of 200 g / m ² ) with a needle punch on both sides of the commercial acetone was immersed in commercially available acetone for 30 minutes, and the acetone was sufficiently removed. Dry for 24 hours. A predetermined number of the obtained sheets are stacked and placed in a mold, and a ring-opening bulk polymerizable thermosetting resin, dicyclopentadiene (D
CP) was injected, and a curing reaction was performed to obtain a plate-shaped sample. The plate thickness was set to 5 mm.

Example 6 Commercially available high-strength vinylon fiber plain fabric (basis weight 180 g /
m ² ), a sheet obtained by integrating a commercially available polyester fiber non-woven fabric (having a basis weight of 100 g / m ² ) by needle punching on both sides was immersed in commercially available acetone for 30 minutes, and the acetone was sufficiently removed. Dried for hours. A predetermined number of the obtained sheets are stacked and placed in a mold, and a ring-opening bulk polymerizable thermosetting resin, dicyclopentadiene (D
CP) was injected, and a curing reaction was performed to obtain a plate-shaped sample. The plate thickness was set to 5 mm.

Example 7 Commercially available high-strength vinylon fiber plain fabric (basis weight: 180 g /
m^Two), A commercially available non-woven vinylon fiber nonwoven fabric
Weight 100g / m^Two) By needle punch
Sheet and commercially available high-strength vinylon fiber plain fabric (basis weight
180g / m ^Two) On one side, commercially available general purpose vinylon fiber
Non-woven fabric (basis weight 100g / m^Two) To needle punch
Immerse the more integrated sheet in commercially available acetone for 30 minutes
After thoroughly removing acetone, dry at 60 ° C for 24 hours.
Dried. Arrange the woven surface of the single-sided nonwoven sheet on the outermost surface, and
Place a double-sided nonwoven sheet in the part, stack it and install it in the mold,
Dicyclopentadi, a ring-opening bulk polymerizable thermosetting resin.
Ene (DCP) is injected and cured to obtain a plate-like sample.
Obtained. The plate thickness was set to 5 mm.

Example 8 Commercially available high-strength vinylon fiber plain fabric (basis weight 180 g /
m ² ), a sheet obtained by integrating a commercially available general-purpose vinylon fiber non-woven fabric (having a basis weight of 100 g / m ² ) with a needle punch on both sides was immersed in commercially available acetone for 30 minutes, and the acetone was sufficiently removed. For 24 hours. A predetermined number of prepreg sheets impregnated with a commercially available bisphenol A type epoxy resin were laminated on the obtained sheet, placed in a mold, and cured to obtain a plate-shaped sample. Board thickness is 5
mm.

Example 9 Commercially available high-strength vinylon fiber plain fabric (basis weight: 180 g /
m ² ), a sheet obtained by integrating a commercially available general-purpose vinylon fiber non-woven fabric (having a basis weight of 100 g / m ² ) with a needle punch on both sides was immersed in commercially available acetone for 30 minutes, and the acetone was sufficiently removed. For 24 hours. A predetermined number of prepreg sheets impregnated with a commercially available unsaturated polyester resin were laminated on the obtained sheet, placed in a mold, and allowed to undergo a curing reaction to obtain a plate-shaped sample. The plate thickness was set to 5 mm.

Comparative Example 1 Commercially available high-strength vinylon fiber plain fabric (basis weight 180 g /
m ² ) was immersed in commercially available acetone for 30 minutes to sufficiently remove the acetone, and then dried at 60 ° C. for 24 hours. The obtained 11 sheets are stacked and placed in a mold, and a ring-opening bulk polymerizable thermosetting resin, dicyclopentadiene (DCP)
And a curing reaction was performed to obtain a plate-like sample. Board thickness is 5
mm.

Comparative Example 2 Commercially available high-strength vinylon fiber plain fabric (basis weight 180 g /
m ² ), a sheet obtained by integrating a commercially available general-purpose vinylon fiber non-woven fabric (having a basis weight of 100 g / m ² ) with a needle punch on both sides was immersed in commercially available acetone for 30 minutes, and the acetone was sufficiently removed. For 24 hours. Two sheets obtained and a high-strength vinylon fiber plain fabric (basis weight 180 g / m ² ) in which the fiber is not constrained by a needle punch are arranged and stacked in the center of the sheet, placed in a mold, and opened in a mold. Dicyclopentadiene (DCP), which is a block polymerizable thermosetting resin, was injected and cured to obtain a plate-shaped sample. The plate thickness was set to 5 mm.

Comparative Examples 3 and 4 Commercially available high-strength vinylon fiber plain fabric (basis weight 180 g /
m ² ), a sheet obtained by integrating a commercially available general-purpose vinylon fiber nonwoven fabric (having a basis weight of 100 g / m ² ) with a needle punch on both surfaces of the resultant was immersed in commercially available acetone for 30 minutes, and the acetone was sufficiently removed. For 24 hours. A predetermined number of the obtained sheets were laminated and placed in a mold, and dicyclopentadiene (DCP), which is a thermosetting resin having a ring-opening mass, was injected thereinto to cause a curing reaction. The plate thickness was set to 5 mm regardless of the number of reinforcing fibers laminated. still,
In Comparative Example 4, the impregnating property of the resin was extremely poor, and a sample whose mechanical properties could be measured could not be obtained.

Comparative Example 5 Commercially available high-strength vinylon fiber plain fabric (basis weight 180 g /
m ² ), a sheet obtained by integrating a commercially available general-purpose vinylon fiber non-woven fabric (having a basis weight of 300 g / m ² ) by needle punch on both surfaces of the resultant was immersed in commercially available acetone for 30 minutes, and the acetone was sufficiently removed. For 24 hours. A predetermined number of the obtained sheets were stacked and placed in a mold, and dicyclopentadiene (DCP), which is a thermosetting resin having a ring-opening mass, was injected to cause a curing reaction. Note that Comparative Example 5
With regard to, the impregnating property of the resin was extremely poor, and a sample from which the mechanical properties could be measured could not be obtained.

Comparative Example 6 Commercially available high-strength vinylon fiber plain fabric (basis weight 180 g /
m ² ), a sheet obtained by integrating a commercially available general-purpose vinylon fiber nonwoven fabric (having a basis weight of 10 g / m ² ) by needle punch on both surfaces of the resultant was immersed in commercially available acetone for 30 minutes, and the acetone was sufficiently removed. For 24 hours. A predetermined number of the obtained sheets are stacked and placed in a mold. Dicyclopentadiene (DCP), which is a ring-opening block polymerizable thermosetting resin, is injected and cured to obtain a plate-shaped sample. . The plate thickness was set to 5 mm.

Table 1 shows the test results for Examples 1 to 9 and Comparative Examples 1 to 6.

[0033]

[Table 1]

In this embodiment, dicyclopentadiene, epoxy resin, unsaturated polyester resin and vinylon fiber and polyester fiber have been described as examples of the matrix resin. There are no particular restrictions, and examples of the base resin include ring-opening polymerizable polycarbonate, ε-caprolactam (polyamide), a polyfunctional isocyanate / polyfunctional polyol mixture (urethane resin), and the like. Examples include polyethylene fibers, aramid fibers, and liquid crystal fibers. In addition, about how to weave organic fiber fabric,
The present invention is not limited to the plain weave described in the embodiment, but may be a satin weave, a slant weave, a satin weave, a multiple weave, or the like.

[0035]

As described above, according to the present invention, the reinforcing fiber is constituted by a sheet obtained by needle-punching an organic fiber non-woven fabric on both sides or one side of an organic fiber woven fabric, so that the woven fabric and the non-woven fabric can be combined. Between the woven fabric and the laminate of the woven fabric, by using the organic fiber non-woven fabric to improve the bending / compression strength of the organic fiber reinforced resin. Can be obtained. Moreover, the organic fiber reinforced resin material of the present invention is also useful as an energy absorbing member because it also improves impact strength. Further, as shown in FIG. 3, the organic fiber reinforced resin material of the present invention has a good non-woven fabric portion because the nonwoven fabric portion is compressed by compression molding or the like and follows an arbitrary shape. Used for a wide range of applications such as sports equipment such as canoe, marine transportation equipment parts such as motor boat hulls, transportation equipment such as aircraft fuselage and railways, automobile parts such as side members, bumper beams, fenders, and construction parts such as soundproof panels. be able to.

[Brief description of the drawings]

FIG. 1 is a schematic view showing a cross section of a double-sided nonwoven fabric sheet of the organic fiber reinforced resin material of the present invention.

FIG. 2 is a schematic view showing a cross section of a single-sided nonwoven fabric sheet of the organic fiber reinforced resin material of the present invention.

FIG. 3 is a schematic view showing a cross section during compression molding of the organic fiber reinforced resin material of the present invention.

[Explanation of symbols]

 1 Organic fiber woven fabric 2 Organic fiber non-woven fabric

Claims (2)

(57) [Claims] 1. A predetermined number of sheets obtained by needle-punching an organic fiber nonwoven fabric on both sides or one side of an organic fiber woven fabric are laminated in a mold, and then impregnated with a resin monomer to react and solidify the resin. Or an organic fiber reinforced resin material obtained by laminating in a prepreg sheet state previously impregnated with a resin monomer and allowing the resin to react and solidify. 2. The organic fiber nonwoven fabric has a basis weight of 20 to 25.
^2. The organic fiber reinforced resin material according to claim 1, wherein a sheet in which the organic fiber woven fabric and the organic fiber nonwoven fabric are integrated is contained in an amount of 10 to 60% by weight in a range of 0 g / m ^2. .