JPH0873629A - Resin material reinforced with organic fiber - Google Patents

Abstract

PURPOSE: To obtain the subject material excellent in flexural/compression strength, impact resistance and shapability, reduced in a void fraction, and useful for ski boards, etc., by integrally joining fiber woven fabrics to nonwoven fabrics, laminating the produced sheets to each other, impregnating the laminate with a resin monomer, and subsequently reaction-solidifying the impregnated resin monomer. CONSTITUTION: This material is obtained by integrally joining one or two organic nonwoven fabrics to the surface or both the surfaces of each of organic woven fabrics by a needle-punching method, laminating the thus produced sheets to each other in a mold, impregnating the produced laminate with a resin monomer and subsequently reaction-solidifying the impregnated resin monomer, or laminating prepreg sheets preliminarily impregnated with the resin monomer and subsequently reactionsolidifying the impregnated resin monomer. The organic-nonwoven fabric has a METSUKE weight of 20-250g/m<2> , and the material contains 10-60wt.% of the sheets produced by integrally joining the organic nonwoven fabrics to the organic woven fabrics.

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 prevent interlayer shear fracture during bending / compression deformation of an organic fiber reinforced resin material, improve bending / compression strength, and impregnate resin. The present invention relates to an organic fiber reinforced resin material having excellent mechanical properties by improving

[0002]

2. Description of the Related 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 and JP-A-1-28).
No. 0199, No. 2-144901, No. 3-76614, No. 3-121135, No. 3-130118, and No. 3-16.
1331), and further, a nylon fiber material or a polyester fiber / thermoplastic resin composite material has been proposed (JP-A-59-207966 and JP-A-1-43532).
Japanese Patent Laid-Open Publication No. H2-124956 and Japanese Patent Laid-Open Publication H3-7
6614 and JP-A-3-130118).

As conventional organic fiber reinforced thermosetting resin materials, aramid fiber materials, liquid crystal fiber materials, ultra high molecular weight polyethylene fiber materials, vinylon fiber materials and PPS / PEEK fiber materials are unsaturated polyesters as reinforcing fibers. It is manufactured as a composite material using resin or epoxy resin as a base material. These composite materials are manufactured by laminating a prepreg impregnated with a resin in advance in a mold and then curing the resin under pressure and heating.

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

[0005]

However, in the above-mentioned conventional organic fiber reinforced resin material, a woven fabric laminate or a nonwoven fabric laminate is usually used as the reinforcing fiber. However, in the woven fabric laminate resin material, bending or compression load is applied. However, there is a drawback that the tensile strength of the fiber cannot be sufficiently exerted due to the shear fracture between the laminated layers, and the bending / compressive strength is significantly reduced. Further, in the case of a woven fabric laminate, the number of woven fabrics to be laminated increases when forming a thick product, which complicates the laminating work, and when the resin is impregnated, the filtering effect by the eyes of the woven fabric remarkably impairs the resin impregnation property, resulting in sufficient mechanical strength. There was a drawback that the characteristics could not be obtained. On the other hand, when the non-woven fabric laminate is used alone, the resin impregnation property is good, but in recent years, it is extremely difficult to satisfy the high strength required for the material.

On the other hand, regarding the treatment of the reinforcing fiber by needle punching, the conventional purpose is to improve the handleability in the production of glass fibers aligned in one direction, and in practice, the glass fiber is cut and matted. However, there is a drawback in that the merit of using long fibers is not utilized.

Therefore, an object of the present invention is to prevent interlaminar shear failure during 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 / compressive strength and improving resin impregnation property.

[0008]

Means and Actions for Solving the Problems The present inventors have
Focusing on the fact that in a laminated material of the same thickness, the smaller the number of layers during bending / compression deformation, the smaller the probability of fracture and the greater the fracture strength, needle-punching an organic fiber non-woven fabric into an organic fiber fabric to form a non-woven fabric. Improving the bending / compressive strength of the organic fiber reinforced resin by stacking sheets in which fibers are pierced into a woven fiber bundle and firmly integrated, and the non-woven fabrics are entangled with each other It has been found that, by integrating the organic fiber woven fabric and the organic fiber non-woven fabric together, the impregnation inhibition of the resin monomer by the woven fabric is alleviated as compared with the woven fabric single laminate, and the void fraction can be significantly reduced. The invention was reached.

The above object of the present invention is to laminate a predetermined number of sheets, which are obtained by needle punching and integrating an organic fiber non-woven fabric on both sides or one side of an organic fiber woven fabric, and impregnate the resin monomer, This is achieved by an organic fiber reinforced resin material characterized in that a resin is reacted and solidified or laminated in a prepreg sheet state in which a resin monomer is impregnated in advance, and the resin is reacted and solidified.

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

The weight per unit area 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 Becomes dense and the impregnation of the resin is significantly hindered, and the strength of the composite material decreases. 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.
It is preferable to be contained within the range. If the content of the sheet is less than 10% by weight, the sheet is easily corrugated and cannot sufficiently function as a reinforcing fiber.
If it exceeds, the non-woven fabric is crushed during lamination, the voids between fibers become dense, and the resin impregnation is significantly hindered.

[0012]

The present invention, as shown in FIG. 1 and FIG. 2, is a fiber which constitutes an organic fiber non-woven fabric by needle-punching after the organic fiber non-woven fabric is laminated on both sides or one side of the organic fiber woven fabric with the constitution of the reinforcing fiber. Is a sheet which is firmly integrated so as to be stabbed in the organic fiber woven fiber bundle, prevents delamination between the organic fiber woven fabric and the organic fiber non-woven fabric during bending and compression deformation, and the organic fiber non-woven fabric is mutually To provide an organic fiber reinforced resin in which the breaking strength is improved by entwining and integrating the sheets, and by using an organic fiber nonwoven fabric, the void fraction is remarkably reduced as compared with a woven fabric single laminate. You can

[0013]

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto.
The following measurements were performed on the materials obtained in Examples and Comparative Examples.

Bending test According to JIS K 7055. A test piece was cut out parallel to the fiber direction and measured under predetermined conditions.

Compression test This was based on JIS K 7056 B method. A test piece was cut out parallel to the fiber direction and measured under predetermined conditions.

Interlaminar Shear Test According to JIS K 7057. A test piece was cut out parallel to the fiber direction and measured under predetermined conditions.

Izod impact test According to JIS K 6911. A test piece was cut out parallel to the fiber direction, and a flatwise impact test was performed under predetermined conditions.

Measurement of Specific Gravity of Reinforcing Material The specific gravity of the reinforcing material was calculated by the buoyancy method from the weight of the organic fiber reinforced resin piece in air and in methanol.

Void fraction Void fraction (volume%) = 100 × [(theoretical density) − (measured density)]

Examples 1 to 3 Commercially available high-strength vinylon fiber plain weaves (weight per unit weight 180 g /
m ² ), a sheet in which a commercially available general-purpose vinylon fiber non-woven fabric (weight per unit area 100 g / m ² ) is integrated by needle punching is immersed in commercial acetone for 30 minutes to sufficiently remove the acetone, and then at 60 ° C. It was dried for 24 hours. A predetermined number of the obtained sheets were laminated and placed in a mold, and 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 laminated reinforcing fibers.

Example 4 Commercially available high-strength vinylon fiber plain weave (weight per unit area: 360 g /
m ² ), a sheet in which a commercially available general-purpose vinylon fiber non-woven fabric (weight per unit area 100 g / m ² ) is integrated by needle punching is immersed in commercial acetone for 30 minutes to sufficiently remove the acetone, and then at 60 ° C. It was dried for 24 hours. A predetermined number of the obtained sheets were laminated and placed in a mold, and 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 weave (weight per unit area: 180 g /
m ² ), a sheet in which commercially available general-purpose vinylon fiber non-woven fabric (weight per unit area: 200 g / m ² ) is integrated by needle punching is immersed in commercially available acetone for 30 minutes to sufficiently remove the acetone, and then at 60 ° C. It was dried for 24 hours. A predetermined number of the obtained sheets were laminated and placed in a mold, and 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 weave (weight per unit area: 180 g /
m ² ), a sheet in which a commercially available polyester fiber non-woven fabric (weight per unit area 100 g / m ² ) is integrated by needle punching is soaked in commercially available acetone for 30 minutes to sufficiently remove acetone, and then at 24 ° C. at 24 ° C. Dried for hours. A predetermined number of the obtained sheets were laminated and placed in a mold, and 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 weave (weight per unit area: 180 g /
m²) On both sides of commercially available general-purpose vinylon fiber non-woven fabric
Weight 100g / m²) Is integrated by needle punching
Sheet and commercial high-strength vinylon fiber plain weave (weight per unit area)
180g / m ²) One side has commercial vinylon fiber on the market
Non-woven fabric (weight per unit area 100g / m²) To the needle punch
Immerse the more integrated sheet in commercial acetone for 30 minutes
After removing the acetone thoroughly, dry at 60 ° C for 24 hours.
Dried Place the woven surface of the single-sided non-woven sheet on the outermost surface
Place a double-sided non-woven sheet on the part and stack it in the mold,
Ring-Opening Bulk Polymerizable Thermosetting Resin, Dicyclopentadi
Injecting ene (DCP), curing reaction and plate-shaped sample
Obtained. The plate thickness was set to 5 mm.

Example 8 Commercially available high-strength vinylon fiber plain weave (weight per unit weight: 180 g /
m ² ), a sheet in which a commercially available general-purpose vinylon fiber non-woven fabric (weight per unit area: 100 g / m ² ) is integrated by needle punching is immersed in commercially available acetone for 30 minutes to sufficiently remove the acetone, and then 60 ° C. And dried for 24 hours. A predetermined number of prepreg sheets impregnated with a commercially available bisphenol A type epoxy resin were stacked on the obtained sheet, placed in a mold, and allowed to undergo a curing reaction to obtain a plate-shaped sample. Board thickness is 5
to be mm.

Example 9 Commercially available high-strength vinylon fiber plain weave (weight per unit area: 180 g /
m ² ), a sheet in which a commercially available general-purpose vinylon fiber non-woven fabric (weight per unit area: 100 g / m ² ) is integrated by needle punching is immersed in commercially available acetone for 30 minutes to sufficiently remove the acetone, and then 60 ° C. And dried for 24 hours. A predetermined number of prepreg sheets impregnated with a commercially available unsaturated polyester resin were stacked 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 weave (weight per unit 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. Eleven sheets obtained were laminated and placed in a mold, and dicyclopentadiene (DCP), which is a ring-opening block-like polymerizable thermosetting resin
Was injected and a curing reaction was performed to obtain a plate-shaped sample. Board thickness is 5
to be mm.

Comparative Example 2 Commercially available high-strength vinylon fiber plain woven fabric (weight per unit weight: 180 g /
m ² ), a sheet in which a commercially available general-purpose vinylon fiber non-woven fabric (weight per unit area: 100 g / m ² ) is integrated by needle punching is immersed in commercially available acetone for 30 minutes to sufficiently remove the acetone, and then 60 ° C. And dried for 24 hours. Two sheets obtained and a high-strength vinylon fiber plain weave (weight per unit area: 180 g / m ² ) that does not restrain the fibers by needle punching are placed and laminated in the center of the two sheets and placed in a mold to open the ring. A bulky thermosetting resin, dicyclopentadiene (DCP), was injected and a curing reaction was performed 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 weave (weight per unit area: 180 g /
m ² ), a sheet in which a commercially available general-purpose vinylon fiber non-woven fabric (weight per unit area 100 g / m ² ) is integrated by needle punching is immersed in commercially available acetone for 30 minutes to sufficiently remove the acetone, and then 60 ° C. And dried for 24 hours. A predetermined number of the obtained sheets were laminated and placed in a mold, and dicyclopentadiene (DCP), which is a ring-opened block-polymerizable thermosetting resin, was injected and a curing reaction was performed. The plate thickness was set to 5 mm regardless of the number of laminated reinforcing fibers. still,
In Comparative Example 4, the resin impregnability was extremely poor, and a sample whose mechanical characteristics could be measured could not be obtained.

Comparative Example 5 Commercially available high-strength vinylon fiber plain weave (weight per unit weight: 180 g /
m ² ), a sheet in which a commercially available general-purpose vinylon fiber non-woven fabric (weight per unit area is 300 g / m ² ) is integrated by needle punching is immersed in commercially available acetone for 30 minutes to sufficiently remove the acetone, and then 60 ° C. And dried for 24 hours. A predetermined number of the obtained sheets were laminated and placed in a mold, and dicyclopentadiene (DCP), which is a ring-opened block-polymerizable thermosetting resin, was injected and a curing reaction was performed. Incidentally, this comparative example 5
As for No. 3, the resin impregnability was extremely poor, and a sample whose mechanical characteristics could be measured could not be obtained.

Comparative Example 6 Commercially available high-strength vinylon fiber plain weave (weight per unit weight: 180 g /
m ² ), a sheet in which a commercially available general-purpose vinylon fiber non-woven fabric (weight per unit area 10 g / m ² ) is integrated by needle punching is immersed in commercially available acetone for 30 minutes to sufficiently remove the acetone, and then 60 ° C. And dried for 24 hours. A predetermined number of the obtained sheets were stacked and placed in a mold, and dicyclopentadiene (DCP), which was a ring-opened block-type polymerizable thermosetting resin, was injected and a curing reaction was performed to obtain a plate-shaped sample. . The plate thickness was set to 5 mm.

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

[0033]

[Table 1]

In the present embodiment, the base resin is dicyclopentadiene, epoxy resin, unsaturated polyester resin, and the reinforcing fibers are vinylon fiber and polyester fiber. Is not particularly limited, and examples of the base material resin include ring-opening polymerizable polycarbonate, ε-caprolactam (polyamide), polyfunctional isocyanate / polyfunctional polyol mixture (urethane resin), and the like, and the organic fiber has high strength. Examples thereof include polyethylene fiber, aramid fiber, liquid crystal fiber and the like. Also, regarding the weave of organic fiber fabric,
The weave is not limited to the plain weave described in the embodiments, and satin weave, twill weave, satin weave, multiple weave, and the like can be applied.

[0035]

As described above, according to the present invention, the reinforcing fiber is made into a sheet in which the organic fiber non-woven fabric is needle-punched and integrated on both sides or one side of the organic fiber woven fabric to form a woven fabric and a non-woven fabric. Space between them, and also the layers during sheet lamination are integrated to improve the bending / compressive strength of the organic fiber reinforced resin, and by using an organic fiber non-woven fabric, the void fraction is higher than that of the woven fabric single laminate. It is possible to obtain an organic fiber reinforced resin having a significantly reduced value. Further, the organic fiber reinforced resin material of the present invention also improves impact strength, and is therefore useful as an energy absorbing member. Furthermore, as shown in FIG. 3, the organic fiber reinforced resin material of the present invention has good shapeability because the non-woven fabric part is compressed by compression molding or the like and follows an arbitrary shape, and skis, sailboards, 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 body and railroad, automobile parts such as side members, bumper beams, fenders, building parts such as soundproof panels be able to.

[Brief description of drawings]

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

[Explanation of symbols]

 1 organic fiber woven fabric 2 organic fiber woven fabric

Claims (2)

[Claims] 1. A sheet obtained by needle punching and integrating an organic fiber non-woven fabric on both sides or one side of an organic fiber woven fabric, laminating a predetermined number of the sheets in a mold, impregnating the resin monomer, and reacting and solidifying the resin. Alternatively, an organic fiber reinforced resin material characterized by being laminated in a prepreg sheet state in which a resin monomer has been impregnated in advance, and reacting and solidifying the resin. 2. The weight per unit area of the organic fiber nonwoven fabric is 20 to 25.
The organic fiber reinforced resin material according to claim 1, wherein the amount of the sheet in which the organic fiber woven fabric and the organic fiber nonwoven fabric are integrated is contained in the range of 0 to 60% by weight in the range of 0 g / m ^2. .