WO2004068059A1

WO2004068059A1 - Impact-resistant fiber reinforced composite material

Info

Publication number: WO2004068059A1
Application number: PCT/JP2004/000727
Authority: WO
Inventors: Atsushi Murakami; Kunio Nishi; Masahiro Mitsufuji; Shinkichi Murakami; Toshikazu Takeda; Takaharu Ichiryu; Yukihiro Nomura
Original assignee: Nippon Steel Composite Corporation; Kinboshi Inc.; Toyobo Co.,Ltd.
Priority date: 2003-01-30
Filing date: 2004-01-28
Publication date: 2004-08-12
Also published as: JPWO2004068059A1

Abstract

Impact-resistant fiber reinforced composite material (1) comprising fiber sheet (2), the fiber sheet (2) composed of high strength fibers (f) of 17 cN/dtex or greater tensile strength and 450 cN/dtex or greater tensile elasticity, and matrix resin (3), wherein as the matrix resin (3), an ionomer resin comprising an ethylene/methacrylic acid copolymer whose molecules are crosslinked with each other by metal ions is contained in an amount of 3 to 100 wt.% based on the fiber (f). This impact-resistant fiber reinforced composite material excels in blade-proof performance against cutting tools and bullet-proof performance for protecting human, etc. from high-speed flying objects, such as bullets and fragments. Further, this impact-resistant fiber reinforced composite material can be commendably formed into lightweight clothing and tool materials for protecting part or the entirety of human body from cutting tools and bullets, such as stab-proof vest, bullet-proof vest, bullet-proof helmet and stab-proof gloves, and formed into portable protective tools, such as police baton, nightstick, thrust fork and shield, and protective materials, bullet-proof plates, etc. for use in vehicles, boats, aircrafts, helicopters, etc.

Description

Description Impact resistant fiber reinforced composites Technical field

The present invention generally relates to a composite material, and particularly to a blade material for a cutting tool and an excellent heat resistance for protecting a human body from a high-speed flying object such as a bullet or a shard, a blade-proof vest, a bullet-proof vest, a bullet-proof hermet, Clothing and materials that protect part or the whole of the body from blades, 弹 maru, etc., and portable protective equipment such as batons, sticks, sticks, and shields, as well as vehicles, boats, aircrafts, etc. The present invention relates to an impact-resistant fiber-reinforced composite material that can suitably produce a protective material, a bulletproof plate, and the like used for such applications. Background art

Conventionally, metals such as special steel and titanium have been mainly used as heat-resistant protective materials such as blade-proof vests, water-resistant vests, bullet-proof helmets, and bullet-proof plates. However, metal-based materials are heavy and pose problems in wearability, handling, and operability.

Therefore, fiber-reinforced composite materials are currently receiving attention. For example,

In the publication No. 8-1897977, a fabric having a high strength and high modulus polyethylene fiber having a tensile strength of at least 17 c NZ dtex and a tensile modulus of at least 450 cN / dtex or more is disclosed. A protective material made of resin has been proposed.

The protective material disclosed in Japanese Patent Application Laid-Open No. Hei 8-189977, in particular, uses butadiene / acrylonitrile having a vinyl ester terminal and a side chain in a resin component, using a piper ester resin as a resin. Elastomer of polymer Is added in an amount of 20 to 80% by weight.

The protective material disclosed in the above-mentioned Japanese Patent Application Laid-Open No. 8-189797 has the features that it is lightweight, and has excellent ballistic resistance (heat resistance) and excellent blade resistance.

The present inventors have further conducted a number of research experiments in order to provide an impact-resistant fiber-reinforced composite material which is lightweight and has high durability (high heat resistance) and excellent blade resistance. .

As a result, in particular, as a resin, that is, an ionomer resin in which the molecules of an ethylene-methacrylic acid copolymer are crosslinked with metal ions as a matrix resin impregnated in high-strength fibers, this resin is identified as a specific resin. It has been found that when impregnated into high-strength fibers at a high ratio, the weight, the blade resistance and the heat resistance can be significantly improved.

The present invention is based on such novel findings of the present inventors, and is a further improvement and development of the protective material disclosed in the above-mentioned Japanese Patent Application Laid-Open No. 8-189797. is there.

In other words, an object of the present invention is to provide a blade-proof vest, bullet-proof vest, and bullet-proof helmet that are excellent in blade-resistant performance against a blade and heat-resistant performance for protecting a human body and the like from high-speed flying objects such as bullets and fragments. , Clothing and materials that protect part and all of the body from knives and bullets, such as gloves, and gloves, as well as portable protective equipment such as batons, wands, staples, shields, and vehicles, boats, aircraft, and helicopters. It is an object of the present invention to provide an impact-resistant fiber reinforced composite material that can suitably produce a protective material, a bulletproof plate, and the like used in the evening and the like. Disclosure of the invention

The above objects are achieved by the impact-resistant fiber-reinforced composite material according to the present invention. In summary, the present invention has a tensile strength of 17 cN / dteX or more and a tensile modulus. In a high impact fiber reinforced composite material having a fiber sheet formed of high-strength fibers of 450 cN / dtex or more, and a matrix resin,

An impact-resistant fiber reinforced material comprising, as the matrix resin, an ionomer resin obtained by cross-linking a molecule of an ethylene-methacrylic acid copolymer with metal ions, in an amount of 3 to 100% by weight based on the fiber. It is a composite material.

According to one embodiment of the present invention, the ionomer resin has a specific gravity of 0.93 to 0.97 and a flexural modulus of 100 to 330 MPa.

As a method of impregnating the fiber sheet with the ionomer resin, a method of laminating an ionomer film and heat-pressing, a method of heat-pressing pellets or powder, and a method of diving into an ionomer dispersion can be adopted.

According to another embodiment of the present invention, the fiber sheet is formed by laminating one or more layers of a woven fabric, a knitted fabric or a nonwoven fabric alone or in combination, or has a high strength. It is formed by laminating fiber layers in which fibers are arranged in one direction so that the orientation angles of the fibers are different from each other, or by combining these various fabrics and unidirectionally arranged fiber layers.

According to another embodiment of the present invention, the high-strength fiber is an aramide fiber, a polyarylate fiber, a polyethylene fiber, a polyvinyl alcohol fiber, a benzazole fiber, a carbon fiber, and a high-strength glass fiber alone or A plurality of fibers are used in combination. BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a cross-sectional configuration view of an example of an impact-resistant fiber-reinforced composite material according to the present invention.

FIG. 2 is a perspective view showing one configuration example of the fiber sheet. FIG. 3 is a perspective view showing another configuration example of the fiber sheet. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the impact-resistant fiber-reinforced composite material according to the present invention will be described in more detail. FIG. 1 shows a cross-sectional configuration of an example of an impact-resistant fiber-reinforced composite material according to the present invention. In this embodiment, the impact-resistant fiber-reinforced composite material 1 has a fiber sheet 2 formed of high-strength fibers, and a resin impregnated in the fiber sheet 2, that is, a matrix resin 3.

As shown in FIGS. 2 (A) and 2 (B), the fiber sheet 2 may be a woven or knitted fabric 2a (FIG. 2 (A)) or a non-woven fabric (FIG. 2 (B)). The fabric 2b as shown in FIG. The weight per unit area of the fabrics 2 a and 2 b is not limited, but is usually 30 to 500 gZm ² . In addition, the fiber sheet 2 is formed by laminating one or more layers of such a cloth 2a or 2b, that is, a woven cloth, a knitted cloth, a nonwoven cloth, or the like, or a different kind of cloth. Alternatively, one or more layers can be formed by combining them. Alternatively, as shown in FIGS. 3A and 3B, a fiber formed by arranging high-strength fibers f in one direction can be used. A plurality of layers, for example, a fiber layer laminate (fiber layers 2a, 2b, 2c) in which three or more layers are stacked (FIG. 3 (A)). At this time, each of the fiber layers 2a, 2b, and 2c is preferably formed of a fiber of each of the fiber layers 2a, 2b, and 2c so that a network structure is formed in each of the fiber layer laminates. The orientation angles a, b, and c are different from each other. For example, the orientation angles are aa = + 30 to 65 °, o; b = 0 °, o; c = —30 to 65 °.

Also, as shown in FIG. 3 (B), the fiber layer laminate does not have the three-layer structure described above, but has a fiber layer 2a having an orientation angle aa of 90 ° and an orientation angle b of 0. ° Fiber layer laminate (fiber Weir layers 2a and 2b) can also be used. Further, two or more fiber layer laminates (2a, 2b) composed of these two layers can be used. Furthermore, it is also possible to form by combining various fabrics shown in FIG. 2 with the unidirectionally arranged fiber layers shown in FIG.

According to the present invention, the fiber f forming the fiber sheet 2 has a tensile strength of at least 17 cN Zd tex and a tensile modulus of 450 to ensure blade resistance, heat resistance (ballistic resistance) and lightness. c It must be a high-strength fiber of N / dtex or more.

As such high-strength fibers, polyethylene fibers having a high-strength and high-modulus described in JP-A-8-189797 can be used. In addition, as high-strength fibers, aramide fibers, Use high-strength organic fibers, such as polyarylate fibers, polyvinyl alcohol fibers, and benzazole fibers, and high-strength inorganic fibers, such as carbon fibers and high-strength glass fibers, alone or in combination. be able to.

As the matrix resin 3, an ionomer resin obtained by crosslinking the molecules of an ethylene-methacrylic acid copolymer with metal ions is used.

In other words, the ionomer resin has a structure in which the side chain of a carboxylic acid group is present in the molecular chain of polyethylene, and a part of this carboxylic acid group is crosslinked between molecular chains by a metal cation (Na + or Zn +). It has excellent toughness, elasticity and flexibility, and has extremely good impact resistance.

Usually, the ionomer resin used in the present invention has a specific gravity of 0.93 to 0.97 and a flexural modulus of 100 to 330 MPa.

According to the present invention, such an ionomer resin is contained as a matrix resin 3 in a high-strength fiber 3, that is, in an amount of 3 to 100% by weight based on the fiber sheet 2, so that the blade resistance and the heat resistance are excellent, and the impact resistance is high. The composite fiber-reinforced composite material 1 can be provided. When the amount of the matrix resin exceeds 100% by weight, a composite having excellent blade-resistant and heat-resistant performance as compared with the protective material described in JP-A-8-189977 is mentioned. If the content is less than 3% by weight, the resin 3 is not filled between the fibers of the fiber sheet 2 and the rigidity and shape retention deteriorate rapidly.

The impact-resistant fiber-reinforced composite material 1 of the present embodiment can be produced by any method, but usually, a fiber sheet 2 having the above configuration is impregnated with a matrix resin 3 to produce a pre-preda sheet. Then, a desired number of such pre-preda sheets are laminated, heated and pressed in a mold and shaped into a predetermined shape, whereby a protective product using the impact-resistant fiber-reinforced composite material 1 is obtained.

Other manufacturing methods include laminating the ionomer film and heat-pressing it, or, for example, applying a powdered ionomer resin such as pellets or powder and then melting it by heat-pressing. It is also possible to use a method of impregnating, or a method of preparing a liquid in which an ionomer is dispersed, diving the fiber sheet into the liquid, and subsequently performing a drying step.

In addition, when the required number of the prepred sheets are laminated and sewn, or when the required number of the prepred sheets and the fiber sheets 2 are laminated and sewn, a flexible protective product can be obtained.

That is, the prepreg sheet as the impact-resistant fiber-reinforced composite material 1 can be formed into a plate shape such as a protection plate, or can be formed into a protection helmet or the like. Also, when the required number of prepred sheets are stacked and sewn, or when the required number of prepred sheets and the fiber sheet 2 are stacked and sewn, a flexible blade-proof vest and bulletproof zipper are manufactured. can do.

According to the impact-resistant fiber-reinforced composite material 1 of the present invention, the high-strength fiber f Since the fiber sheet 2 has a structure impregnated with an ionomer resin having excellent toughness, elasticity and flexibility and having extremely good impact resistance, that is, an impregnated structure, the fiber sheet 2 is externally added to the composite material 1. For example, the impact of a high-speed projectile such as a bullet or a fragment is sufficiently absorbed by the ionomer resin 3 and the fiber sheet 2 made of high-strength fiber. It will have blade-resistant performance. Moreover, the impact-resistant fiber-reinforced composite material 1 of the present invention is lightweight, and is excellent in wearability, handleability, and operability.

Regarding the effects of the present invention, the following reasons are considered.

In other words, when the ionomer resin is not impregnated, or when impact is received from a projectile or the like, only the fiber bundle existing at the impact site and the fiber bundle in the vicinity thereof tend to absorb energy. On the other hand, when the ionomer resin is impregnated, the ionomer resin has excellent impact resistance and excellent adhesiveness, so that the fiber bundle is appropriately integrated. Energy absorption including the fiber bundle is possible. Therefore, it is considered that the fiber sheet material composed of the sheet impregnated with the ionomer resin has excellent shock absorbing ability and can prevent appropriate deformation due to impact. In addition, since the ionomer component contains metal ions, it has a high affinity for metal bullets, and therefore has a large interaction with metal bullets when exposed, which makes the head of the metal bullet very difficult. It is considered that the effect of improving the impact resistance and the deformation resistance of the ionomer-impregnated fiber sheet is exhibited.

The ionomer-impregnated fiber sheet also has excellent properties as a fireproof material. An ionomer film having excellent impact resistance and abrasion resistance is a material frequently used in golf pole applications. Therefore, in the case of the ionomer-impregnated fiber sheet, the impact resistance and the abrasion resistance of the ionomer itself are lower than that of cutting tools. It is thought that the ionomer integrates the fiber bundle of the fiber sheet as an adhesive and disperses the stress, and also contributes to the excellent performance as a blade-proof material. .

Next, the impact-resistant fiber-reinforced composite material 1 of the present invention will be further described with reference to examples.

Examples 1, 2, 3

Tensile strength 3 7 c N / dtex, a tensile modulus of elasticity 1 1 5 0 PBO fiber of c N / dtex by using a (Toyobo Co., Ltd., trade name "Zairon"), a plain weave fabric having a basis weight of 1 3 5 g Zm ² It was manufactured and used as a fiber sheet 2. An ionomer resin (Mitsui-Dupont Polychemical Co., Ltd., trade name “Yachiimiran”), in which the molecules of an ethylene-methacrylic acid copolymer are crosslinked with metal ions, is used as the matrix resin 3 in the fiber sheet 2. The reinforced fiber was impregnated with 60% by weight to prepare a prepredder.

Next, 10 sheets of the pre-preda and 40 sheets of the fiber sheet 2 were laminated, and a total of 50 sheets were stitched. Further, 20 sheets of the pre-preda and 30 sheets of the fiber sheet 2 were laminated, and a total of 50 sheets were stitched. Also, 30 sheets of the pre-preda and 20 fiber sheets 2 were laminated, and a total of 50 sheets were stitched to obtain a third embodiment.

Comparative Examples 1, 2, 3, 4

The matrix resin 3 was obtained by dissolving an elastomer of a butadiene Z acrylonitrile copolymer having a vinyl group in a terminal chain which cures at 120 ° (5 minutes, 40% by weight in a vinyl ester resin. Except for the above, Comparative Examples 1, 2, and 3 were molded in the same manner as in Examples 1 to 3 above.

Further, 50 fiber sheets 2 were laminated and sewn to prepare Comparative Example 4. The samples of Examples 1 to 3 and Comparative Examples 1 to 4 were evaluated for blade resistance and impact resistance. (Evaluation of blade performance)

The blade performance was evaluated by placing urethane with a thickness of 40 mm on the back of the material to be tested, applying a load to an ice pick and a butterfly knife, dropping the knife vertically, and evaluating the performance based on the penetration depth of the cutting edge. The ice pick used was a single-pilot, 148 mm long nail series manufactured by Takakusan Co., Ltd. The butterfly knife used was STO Butterfly Series SK-49W manufactured by Seto Die & Hammer Co., Ltd., 70 mm in blade length. The impact energy was generated by the method shown in Table 1 below.

[Table 1] Energy amount Weight of falling object including blade Distance from material under test to blade edge

20 J 2.5 kg 82 cm

30 J 3.0 kg 103 cm

40 J 4.0 kg 103 cm

50 J 5.0 kg 103 cm

Tables 2 and 3 show the results of evaluating the blade resistance performance of each sample. In Tables 2 and 3, the horizontal axis indicates energy, the vertical axis indicates materials to be inspected, and the numbers in the table indicate the penetration depth (mm).

[Table 2] Performance test using an ice pick

20 J 30 J 40 J 50 J

Example Ί 0 0 4 8

Example 2 0 0 0 3

Example 3 0 0 0 0

Comparative Example 1 4 1 9 39> 40

Comparative Example 2 5 1 8 40> 40

Comparative Example 3 2 20 35> 40

Comparative Example 4 4 20 38> 40 Examples 1 to 3 show that the penetration depth is small and the blade resistance to ice picks is high.

[Table 3]

Performance test with butterfly knife

20 J 30 J 40 J 50 J

Example 1 0 0 8 1 2

Example 2 0 0 0 7

Example 3 0 0 0 0

Comparative Example 1 1 2 30> 40> 40

Comparative Example 2 1 0 35> 40> 40

Comparative Example 3 1 4 26> 40> 40

Comparative Example 4 Ί 5 31> 40> 40

Examples 1 to 3 show that the penetration depth is small, and that the blade resistance is high with respect to the butterfly knife.

(Impact resistance evaluation)

To evaluate the impact resistance, place a 100 mm thick clay on the back of the material to be tested, and place a 弹 circle weighing 15.6 g from a 44 caliber launcher at right angles to the above sample from a distance of 5 m from the above sample. After firing, the velocity of the bullet was measured, the amount of energy of impact was calculated, and the amount of dent of the test material in the direction of the clay was measured to evaluate the impact resistance.

Table 4 shows the results of evaluating the impact resistance performance of each sample. [Table 4] Impact resistance test

Energy (J) Depression (mm)

Example 1 520 3 1

Example 2 1 51 0 25

Example 3 1 523 1 3

Comparative Example 1 1 5 1 1 48

Comparative Example 2 1 530 46

Comparative Example 3 1 51 8 49

Comparative Example 4 1 520 46

Examples 1 to 3 show a small amount of dents and high impact resistance.

As described above, the impact-resistant fiber-reinforced composite material of the present invention has a fiber sheet formed of high-strength fibers having a tensile strength of 17 c NZd tex or more and a tensile modulus of 450 c NZd tex or more, An impact-resistant fiber-reinforced composite material having a matrix resin, wherein the matrix resin contains, as a matrix resin, an ionomer resin in which the molecules of an ethylene-methacrylic acid copolymer are cross-linked with metal ions in an amount of 3 to 100% by weight based on the reinforcing fibers. Because of its configuration, it has excellent blade resistance against blades and resistance against high-speed flying objects such as round shards, etc., and is lightweight. Clothing and materials that protect part and all of the body from knives and 丸 such as blade gloves, portable protective equipment such as batons, sticks, sticks, shields, and vehicles and boats Aircraft, armor used in helicopters, can be suitably prepared and bulletproof plate.

Claims

The scope of the claims

1. In an impact-resistant fiber-reinforced composite material having a fiber sheet formed of high-strength fiber having a tensile strength of 17 c NZd tex or more and a tensile modulus of 450 c NZ d tex or more, and a matrix resin,

An impact-resistant fiber-reinforced composite material comprising, as the matrix resin, an ionomer resin obtained by cross-linking a molecule of an ethylene-methacrylic acid copolymer with metal ions in an amount of 3 to 100% by weight based on the fiber. .

2. The impact resistant fiber reinforced composite material according to claim 1, wherein the ionomer resin has a specific gravity of 0.93 to 0.97 and a flexural modulus of 100 to 330 MPa.

3. The fiber sheet is formed by laminating one or more layers of a woven fabric, a knitted fabric or a nonwoven fabric alone or in combination, or a fiber layer in which high-strength fibers are arranged in one direction. 3. The impact resistance according to claim 1, wherein the fibers are formed by laminating so that the orientation angles of the fibers are different from each other, or are formed by combining these various fabrics and unidirectionally arranged fiber layers. Fiber reinforced composite.

4. As the high-strength fiber, use is made of aramid fiber, polyarylate fiber, polyethylene fiber, polyvinyl alcohol fiber, benzazole fiber, carbon fiber, and high-strength glass fiber alone or in combination of plural kinds of fibers. The impact-resistant fiber-reinforced composite material according to claim 1, 2, or 3.