KR20160053312A - Method of manufacturting bulletproof-fiber complex prepreg comprising cnt or graphene and bulletproof articles manufactured by using the same - Google Patents

Abstract

The present invention relates to a producing method of a bulletproof-fiber complex prepreg, comprising the steps of: preparing an impregnation solution by dispersing carbon nanotube(CNT) or graphene particles in a solvent; preparing a bulletproof-fiber complex by impregnating bulletproof fibers in the impregnation solution and drying the bulletproof fibers; preparing a bulletproof-fiber complex layer by processing the bulletproof-fiber complex into layers; and penetrating a thermoplastic resin into at least one side of the bulletproof-fiber complex layer by heat-compressing one thermoplastic resin film into at least one side of the bulletproof-fiber complex layer.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a method for manufacturing a bulletproof fiber composite prepreg comprising carbon nanotubes (CNTs) or graphenes, and a ballistic member manufactured by the method. BACKGROUND ART < RTI ID = 0.0 >

This technology is a technology in the field of bulletproof materials, and is a technique for manufacturing a bulletproof member having a lightweight but excellent shielding performance, less distortion due to various bullets, and improved temperature sensitivity.

Aramid-based fibers, which were developed in the 1970s, which have been used as core materials for today, starting from nylon fibers in the 1950s and which have made a turning point in the development of bulletproof materials, And ultra high molecular weight polyethylene (UHMWPE) based fibers are mainstream.

Although these high strength fibers are manufactured in various forms and used according to the demand for protection performance, the most widely used materials are a fabric type and a fiber yarn which are arranged in a 0 ㅀ direction and coated with a polymer resin, Unidirectional Tape (UD) formed after lamination in the direction of 0 ㅀ and 90 가 is mainstream.

Generally, the fabric is composed of warp and weft, and the weaving is performed by using different denier (1 g per 9000 m) depending on the application. There are many kinds of woven fabrics, but plain weave type having superior impact energy absorption due to high frictional force between yarn and yarn is applied most. In the case of a fabric, when a FSP (Fragment Simulating Projectile) collides, the yarn constituting the fabric is pulled out and absorbs and disperses the energy of the bobbin to stop the yarn. The drawing strength is the friction force between the yarn and the yarn And when the energy of the bullet exceeds the frictional force or the tensile strength of the yarn, the bullet breaks and penetrates the yarn. On the other hand, in the case of ballast, the core of the tanza is made of lead material and the outer surface is covered with copper, so that when the bullet is collided with the bullet material, the shape of the bulge turns into a mushroom, And brings a huge trauma to the rear.

Therefore, in order to prevent the debris from passing through the debris, deformation of the debris does not occur during collision with the debris, and the deformation of the debris is required. On the other hand, A bulletproof material capable of reducing backface signatures (BFS) by transmitting large impact energy is required.

Basically, when a shock is applied to the bulletproof material, the kinetic energy is quickly transmitted to the adjacent fibers or the next layer, and the shock is dispersed to improve the bulletproof performance. Discloses a technique for dispersing kinetic energy by increasing frictional force between fibers by coating expandable dry powders on fibers or applying them to fabrics to disperse impact energy by increasing frictional force between fibers, ), Heavy, and relatively limited flexibility.

In recent years, when a bullet-proof test was carried out at a low speed (250 m / s or less) with a sheathed shot of a shear thickening fluid (STF: Shear Thickening Fluid) containing impregnated nanoparticles in a kevlar fabric, The results showed that the bulletproof resistance was significantly improved. This technology increases the frictional force of yarn between warp and weft to increase the ball protection ability which is the disadvantage of the fabric bulletproof material while maintaining the flexibility and economy related to the wearability in the case of the fragmented bulletproof and bulletproof clothing which is the advantage of the fabric bulletproof material. So as to suppress the deformation of the fabric layer and reduce the rear deformation. However, this technique has the problem of keeping the STF solution from volatilizing for years of use.

On the other hand, the UD material maintains almost the strength of the fiber because the fibers are aligned in a straight line, and has the advantage that the shock wave can be quickly transmitted and the energy can be dispersed. However, in terms of economy, it has disadvantages as high price.

Today, aramid fibers and ultrahigh molecular weight polyether (UHMPE) fibers are the most commonly used materials for bulletproof materials. Aramid fibers are mainly made of fabric type, and UHMPE fibers are used more as UD type than fabric type. Unidirectional tape material manufactured using UHMPE fiber is getting popular as a bulletproof material including personal bulletproof. This is because the density of the material is lower than that of the existing aramid fiber, which can reduce the weight of the bulletproof material. However, since the melting point of this material is low, it can not be used for a long period of time because the protective power is reduced by 30% in an environment of 80 ° C or higher. Further, the UD material is expensive compared to the fabric in terms of economy.

On the other hand, Aramid fiber which is used more as a fabric bulletproofing material has a higher density than UHMPE, but has a disadvantage in weight reduction. However, the melting point reaches 400 ° C and there is no decrease in the protection against temperature environment. In terms of economics, fabrics have a low cost advantage. Therefore, a variety of techniques are being developed to improve the economy of aramid fabrics and their protection.

An object of the present invention is to provide a bulletproof member having excellent bulletproof performance against bullet and bullet bullet, lightweight and economical as well as solving problems such as disadvantages and economical problems of the prior art as described above The present invention also provides a method for producing a ballistic resistant fiber composite prepreg as a basic unit for producing the same.

Another object of the present invention is to provide a ballistic resistant fiber composite prepreg which is manufactured by the above-described method and can be utilized as various laminated forms.

It is still another object of the present invention to provide a bulletproof member having the bulletproof fiber composite envelope prepreg laminated thereon.

A method of manufacturing a ballistic resistant fiber composite prepreg according to an embodiment of the present invention includes: preparing an impregnation solution by dispersing carbon nanotube (CNT) or graphene particles in a solvent; Impregnating the anti-armor fiber with the impregnation solution and drying to prepare a anti-armor fiber composite; Preparing a bulletproof fiber composite material layer by processing the bulletproof fiber composite material into a layer; And thermally bonding at least one thermoplastic resin film to at least one surface of the anti-fogging fiber composite layer to infiltrate the thermoplastic resin on at least one surface of the anti-fogging fiber composite layer.

The anti-armor fiber may be a unit fiber in the form of a yarn, or a fabric. As the bulletproof fiber, aramid fiber, ultrahigh molecular weight polyethylene (UHMPE) fiber, nylon fiber, glass fiber and the like can be used.

The step of preparing the impregnation solution may further include adding a polymer resin to the impregnation solution to promote the bonding of the CNT or graphene particle and the anti-fogging fiber.

The thermoplastic resin film may be a film made of a polypropylene resin, a polyurethane resin, or a polyethylene resin.

The method may further include the step of impregnating the anti-fogging fiber composite with a polymer resin solution that promotes bonding of the CNTs or the graphene fibers to the anti-fogging fibers after the step of preparing the anti-fogging fiber composite.

The protective fabric composite prepreg according to an embodiment of the present invention is characterized in that CNT or graphene is dispersed and attached in a fabric made of a bulletproof fiber and the content of the CNT or graphene in the fabric is 0.1 to 10 wt% %, And a thermocompression resin film layer formed on at least one side of the above-mentioned anti-fogging fiber composite layer and formed by thermally pressing at least one thermoplastic resin film.

The bulletproof member according to an embodiment of the present invention includes the prepreg laminate in which the above-mentioned bulletproof fiber composite prepreg is repeatedly laminated with the thermosetting resin film layer as a bonding layer.

The bulletproof member may include a laminated portion of different types of prepregs containing different anti-tarnish fibers.

According to the manufacturing method of the present invention, it is possible to maximize the bulletproof performance of the conventional bullet-proof fabrics, to improve the sensitivity to temperature, and to produce a lightweight composite of unit materials.

The prepreg as the unit material composite can be applied to various types of industrial products such as bulletproof products by various lamination forms, molding methods and the like.

The carbon material such as CNT or graphene is uniformly dispersed in the prepreg, so that the functionality of the carbon material can be maximized.

Further, the bulletproof member recycled using the prepreg such as a bulletproof plate has excellent bulletproof performance against both fragmented bullet and bullet, and is excellent in puncture resistance and deformation resistance.

1 is a flowchart conceptually showing a method of manufacturing a bulletproof member including a method of manufacturing a bulletproof fiber composite prepreg according to an embodiment of the present invention.
2 is a cross-sectional view illustrating a layered structure of a protective fabric composite prepreg according to an embodiment of the present invention.
3 is a cross-sectional view conceptually showing a laminated structure of a bulletproof member according to an embodiment of the present invention.
4 is an electron micrograph showing a state in which CNT fibers are dispersed in aramid fibers.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a method of manufacturing a bulletproof composite fiber prepreg and a bulletproof member according to the present invention will be described in detail with reference to the accompanying drawings. The prepared ballistic fiber composite prepreg and the ballistic member including it will be described in detail. However, the following description is only an exemplary description of the present invention, and the technical idea of the present invention is not limited by the following description, and the technical idea of the present invention is defined by the claims that follow.

1 is a flowchart conceptually showing a method for manufacturing a bulletproof material according to an embodiment of the present invention.

Referring first to FIG. 1, a method (S100) for manufacturing a ballistic resistant fiber composite prepreg will first start an impregnation solution for impregnating the armored fiber from a preparation step (S110). The impregnation solution may be prepared by mixing and dispersing CNT or graphene particles in an alcohol-based solvent or the like and dissolving them. The dispersion may be dispersed in a container equipped with an ultrasonic generator or the like.

As the CNT, a single-walled nanotube (SWCNT), a multi-walled nanotube (MWCNT) or the like can be used. The impregnation solution may contain CNT and graphene, respectively, or CNT and graphene may be included at the same time. The CNT or the graphene may be contained in the alcoholic solvent at a concentration of 0.01 to 3 wt%.

When the impregnating solution is prepared, the impregnating solution is prepared in the ultrasonic generator, and the CNT or the graphene or the like is attached to the fibers while continuously impregnating the armor-protecting fibers, for example, yarn-shaped unit fibers (S120 ). In the present embodiment, an example of a yarn-shaped unit fiber has been described. Alternatively, an already woven fabric can be used as a bulletproof fiber. In the case of an already-woven fabric armor fiber, in addition to impregnation, CNT or graphene can also be introduced into the fibers by a process which is sufficient for the fabric to be applied.

As the bulletproof fiber, aramid fiber, ultrahigh molecular weight polyethylene (UHMPE) fiber, nylon fiber, glass fiber and the like can be used. The above-mentioned anti-armor fibers may be used alone, but two or more different anti-armor fibers may be used. When two different kinds of anti-armor fibers are used, it is possible to fabricate a bulletproof material having more various required properties through ultimate weaving using two or more different kinds of fiber yarns.

Specifically, the yarn-shaped anti-armor fibers (armor fiber yarns) are wound on a bobbin. While being unwound, the yarn is impregnated while moving through a guide roller or the like into an immersion liquid container equipped with an ultrasonic generator. At this time, it is preferable that tension is applied to the fibers, and CNTs or graphenes in the solution are uniformly dispersed without precipitating due to the generated ultrasonic waves.

The impregnating solution may optionally include a polymer resin for promoting the bonding of CNTs or graphene particles to the anti-fogging fibers. As the polymer resin, a phenol resin, an epoxy resin, a urethane resin, an acrylic resin, a PVA resin phenol polymer, or the like can be used. In the case of a polymer capable of causing agglomeration or aggregation in the impregnation solution, It is preferable not to be included in the solution step.

In the case of the above-mentioned lumps or aggregation-inducing polymers, it is preferable to further carry out the impregnation step in a separate polymer solution after the bulletproof fiber impregnation step (S120). Namely, the anti-armor fiber primarily impregnated into the CNT or the graphene solution is secondarily impregnated into the polymer solution, so that the CNT or the graphene can be firmly bonded to the fiber structure. As described above, the polymer solution may be a phenol resin, an epoxy resin, a urethane resin, an acrylic resin, a PVA resin phenol-based polymer, and the like. These polymers may be used alone or in combination of two or more. As in the present embodiment, a separate impregnation process of the polymer resin is advantageous to prevent aggregation. That is, when some polymers are included in the initial impregnation solution at the same time, aggregation may occur, so that they are not mixed in the primary impregnation solution stage. Therefore, the impregnation of CNT or graphene particles in the fibrous tissue .

As described above, the anti-fogging fiber impregnated in the CNT or the graphene solution and impregnated in the polymer solution is subjected to the drying process, so that the anti-fogging fiber composite can be prepared.

When the armor fiber composite is in the form of fiber yarn, it is processed into a layer through weaving and processing (S130), and is processed into a layer when the fabric is processed in the form of fabric from the beginning of the process. The above processing means that the processing is processed into a plate shape through the tip or the like. However, in the case where the pre-step process has already been performed as a shape already required, it is not necessary to perform a separate layer-forming process (S130).

When the layer is processed to form the anti-fogging fiber composite layer, a thermoplastic resin film is bonded to one side or both sides of the anti-fogging fiber composite layer, followed by thermocompression (S140). Although the method of thermocompression bonding is exemplified in this embodiment, it is possible to employ the thermocompression bonding method in the present invention as long as the hotmelt of the thermoplastic resin is induced and the pressure is applied.

As the thermoplastic resin film, a film containing a polypropylene resin, a polyurethane resin, or a polyethylene resin may be used. As the resin film, a resin film blended with two or more of the resins may be used.

The resin film is formed as a layer on one side of the anti-armor fiber composite by a method such as thermocompression bonding, but a part of the thermoplastic resin is penetrated into the anti-armor fiber composite material, And serves to firmly bind the pin component.

When the thermoplastic resin film is thermally pressed, the ballistic fiber composite prepreg is completed.

2 is a cross-sectional view illustrating a layered structure of a protective fabric composite prepreg according to an embodiment of the present invention.

2, the anti-vandal fiber composite prepreg 100 may include at least one anti-armor fiber composite layer 110 in which CNTs or graphenes are dispersed and uniformly bonded to fibers, and at least one side of the anti-armor fiber composite layer 110 And a thermosetting resin film layer 115 formed by thermocompression of a thermoplastic resin film formed on the thermosetting resin film layer.

One piece of the thermoplastic resin film may be used, but a plurality of sheets may be used, thereby satisfying the physical properties of the required anti-bulletproof fiber composite prepreg 100.

As described above, by using the thermoplastic resin in the form of a film, it is possible to uniformly infiltrate the resin into the bulletproof fiber composite layer 110, and further, by quantifying the thermoplastic resin to be used, the content of the thermoplastic resin can be easily controlled .

The armored fiber composite prepreg 100 can be manufactured and distributed as such. Referring again to FIG. 1, in the step of manufacturing a product, the bulletproof fiber composite prepreg may be used as a specific bulletproof member such as a bulletproof plate by forming a laminate through a lamination step (S150).

The anti-vandal fiber composite prepreg 100 may be preliminarily prepared as described above and may be put into the manufacturing process of the bulletproof member. Alternatively, the anti-vandal fiber composite prepreg 100 may be pre- And may be combined in the manufacturing step of the bulletproof member, that is, the laminating step. That is, each layer can be pressure-bonded integrally in the manufacturing step of the bulletproof member.

3 is a cross-sectional view conceptually showing a laminated structure of a bulletproof member according to an embodiment of the present invention.

Referring to FIG. 3, in the present embodiment, three prepregs 220, 240 and 260 are laminated and pressed so that (a) a plate-shaped bulletproof member 200 can be manufactured.

The pre-presses can be processed as a bullet-proof molded article similar to a complete monolith by pressure. Although only a plate-shaped bulletproof member 20 is described in this embodiment, various types of bulletproof members can be manufactured through various processing designs such as a processing method and a pressurizing method.

In addition, the prepregs 220, 240 and 260 may include the same anti-fogging fibers, but in some cases, the prepregs 220, 240 and 260 may include different anti-fogging fibers, Each of the prepregs 220, 240, and 260 may include a thermocompression resin film layer having different resin components.

Referring again to FIG. 2, the content of CNT or graphene in the anti-armor fiber composite layer 110 is preferably 0.1 to 10% by weight. The content of the CNT or the graphene can be adjusted by adjusting the concentration of the impregnating solution or controlling the impregnation time.

Hereinafter, the production method of the present invention will be described in more detail with reference to concrete examples.

[Example]

Example 1

The aramid fiber used in this example used a high strength cement as the heracron 600 denier aramid from Kolon Industries. The fabric was made of plain weave, and the number of warp and weft yarns was 27 ㅧ 27 or more per inch, and the density was more than 190g / m ² . The carbon nanotubes used in the examples were multiwall nanotubes, CNTs were dispersed in isopropanol, and 0.01 wt% of phenolic resin was added thereto. The CNT content was 0.05 wt%. Dispersion of CNT was treated with ultrasonic. The fabric was impregnated under the prepared solution as described above. After impregnation, the CNTs dispersed on the fiber surface can be seen in the photograph. 3 is an electron micrograph showing a state in which CNT fibers are dispersed in the aramid fiber. The CNT-aramid fabrics thus produced were laminated, and a polyurethane film was placed between the respective fabrics using the bonding means, followed by thermocompression bonding to produce a CNT-aramid laminated material. The thermocompression condition was a temperature of 135 ° C, a molding time of 20 minutes, and a molding pressure of 40 kg / cm ² .

Experiment 1: Draw strength

After the laminate prepared in Example 1 was cut into 100 mm (L) x 50 mm (W), the drawing strength of the yarn was measured using a fixing fixture. When pulling the yarn out of the fabric, the pullout strength increases if there is friction between the yarn and the yarn. This in turn means that if the yarn is impacted, the deformation of the yarn due to the friction of the yarn can be suppressed, ultimately reducing the rear deformation. Therefore, the pulling test of the yarn was carried out in a tensile tester, and the following results were obtained. As shown in Table 1 below, the CNT treated fabric showed a draw strength value 4 to 5 times higher than the pure CNT-free fabric, confirming that the CNT contributed to the frictional force.

Experiment 2: flexural modulus

The three-point bending test was performed using the laminate prepared in Example 1 to measure flexural strength and flexural modulus. As shown in Table 2, the CNT-aramid fabric showed a flexural strength of about 26% and an elastic modulus of about 14% higher than that of the CNT-free fabric. Therefore, CNT-aramid fabric material is resistant to deformation when subjected to external load.

Material Flexural Strength (MPa) Flexural modulus (MPa) Pure aramid fiber 24.0 (+/- 0.97) 3454 (+/- 145) Aramid fiber containing CNT 30.2 (+/- 0.66) 3953 (+ - 172)

As a result of the drawing test of the yarn and the bending test of the fabric, the development of the polyurethane film as a matrix for the lamination of the aramid and the addition of the CNT to the aramid developed by the present invention, It is proving that it will be excellent indirectly.

Experiment 3: Bulletproof performance test

The bulletproof composite material prepared in the above example was subjected to a bulletproof performance test. A 600 denier aramid fabric was cut into 400 x 400 mm for impregnation with the prepared CNT solution. A polyurethane film was placed between the layer and the layer while being laminated, and molding was performed under the same conditions as in Example 1 in a hydraulic press.

The second bullet specimen was designed as a hybrid laminated material mixed with UD material composed of UHMPE fiber. UHMPE UD layer on the front side and CNT-aramid fabric layer on the back side. After lamination of these hybrid materials, molding was carried out under the above-mentioned conditions to produce a fireproof board.

The ballistic performance test was carried out using two types of shotgun and pistol guns. The fracture shot was used with Cal.22 FSP (1.1g, 17grain) and was protected by the Mil-STD-662F (V50 Ballistic Test for Armor) and NATO STD-2920 The limit V50 value was measured. The following tests were performed on 9 mm lean at level IIIA of the NIJ STD-0101.06 standard, and the back face signature (BFS) was measured by the impact of the shot. To measure this, a clay loam (Roma Plastina No. 1) was used. Six shots were fired according to the standard, and the deformation depth of the oil clay was measured after the test. The NIJ specification limits the maximum allowable depth to 44 mm.

Bulletproof performance result

Table 3 shows the result of the bulletproof test. As shown in Table 3, the protective performance against the Cal.22 fragmentary carbon was the best in the case of hybrid hybrid of CNT-aramid fabric and UD. In the case of pure CNT-aramid fabrics, the V50 value is about 8% lower than that of pure UD. This means that the CNT-aramid fabric exhibits a somewhat brittle characteristic as compared with UDd, which means that the penetration of debris can easily occur. That is to say, Brittel properties are the result of addition of CNT.

On the other hand, the CNT-aramid fabric is the most excellent for the rear deformation by 9mm FMJ carbon. This is because, as mentioned above, the CNT causes a large friction of the yarn-yarn at the time of impact to suppress the deformation of the fabric, and this result means that the present invention is superior. This result is more than twice as high as that of UD. In the case of a hybrid, the median value of the above two materials is taken. Therefore, if the system to be protected is mainly made of bolts, it can be designed only with CNT-aramid fabric. In case of a system that satisfies both shatter and ballast, hybrid design combining CNT-aramid and UD can be applied. Particularly, the present invention is characterized in that the material of the present invention is excellent when the HMPE UD type material, which is known as the lightest bulletproof material in the present day, has the same area density, and the CNT-aramid material and the HMPE UD It is superior to pure HMPE UD material when mixed material. This is advantageous not only in terms of protection but also in terms of economy, at least by 20-30% when using CNT-aramid fabrics.

Claims (9)

Dispersing carbon nanotube (CNT) or graphene particles in a solvent to prepare an impregnation solution;
Impregnating the anti-armor fiber with the impregnation solution and drying to prepare a anti-armor fiber composite;
Preparing a bulletproof fiber composite material layer by processing the bulletproof fiber composite material into a layer; And
And thermally bonding at least one thermoplastic resin film to at least one surface of the anti-armor fiber composite material layer to infiltrate the thermoplastic resin on at least one surface of the anti-armor fiber composite material layer .
The method according to claim 1,
Wherein the anti-armor fiber is a unit fiber in the form of a yarn, or a fabric.
The method according to claim 1,
Wherein the anti-armor fiber comprises at least one fiber selected from the group consisting of aramid fiber, ultrahigh molecular weight polyethylene (UHMPE) fiber, nylon fiber and glass fiber.
The method according to claim 1,
Wherein the preparation step of the impregnation solution further comprises adding a polymer resin to the impregnation solution to promote the bonding of the CNT or graphene particles to the anti-fogging fiber.
The method according to claim 1,
Wherein the thermoplastic resin film is made of a polypropylene resin, a polyurethane resin, or a polyethylene resin.
The method according to claim 1,
Further comprising the step of impregnating the ballistic resistant fiber composite with a polymer resin solution which promotes bonding of the CNT or graphene particle and the anti-fogging fiber after the step of preparing the anti-fogging fiber composite. Wherein the CNT or graphene is dispersed and adhered to the fabric by a polymer binder and the content of CNT or graphene in the fabric is 0.1 to 10% by weight; And
And a thermally compression-bonded resin film layer formed on at least one surface of the bulletproof fiber composite layer and formed by thermally pressing at least one thermoplastic resin film.
A bulletproof member comprising the prepreg laminate in which the bulletproof fiber composite prepreg of claim 6 is repeatedly laminated with the thermosetting resin film layer as a bonding layer.
9. The method of claim 8,
Wherein the bulletproof member includes a laminated portion of different types of prepregs including different anti-tarnish fibers.

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