KR910003993B1 - Frp comprex layer which is bulletproop - Google Patents

Frp comprex layer which is bulletproop Download PDF

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Publication number
KR910003993B1
KR910003993B1 KR1019880001922A KR880001922A KR910003993B1 KR 910003993 B1 KR910003993 B1 KR 910003993B1 KR 1019880001922 A KR1019880001922 A KR 1019880001922A KR 880001922 A KR880001922 A KR 880001922A KR 910003993 B1 KR910003993 B1 KR 910003993B1
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South Korea
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woven fabric
heat
minutes
aliphatic polyamide
fiber woven
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KR1019880001922A
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Korean (ko)
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KR890012793A (en
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김병옥
손동근
김철홍
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동양나이론 주식회사
배기은
동양폴리에스터 주식회사
김인환
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/42—Layered products comprising a layer of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/08—Impregnating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness

Abstract

The fiber reinforced plastic complex molding material is prepd. by; soaking each of the aliphatic polyamide fibric textile and the aramide fibric textile in the thermosetting resin compsn liq.; then laminating and heat-, press molding several thereof. In the precess, before soaking, the aliphatic polyamide fibric textile is 1st heat-treated at 130-150 deg.C for 3-5 min become to 0.05-0.3% of oil pick up (OPU) value; 2nd heat-treated at 170-190 deg.C for 4-6 min; and heat-treated at 200-300 deg.C for 5-10 min. become to 0.01-0.1% of OPU value. The obtd. material is useful for the mgg. of the bullet proof clothe, helmet or tankprotector.

Description

방탄력이 우수한 섬유강화 복합성형체의 제조방법Manufacturing method of fiber reinforced composite molded article having excellent ballistic resistance

본 발명은 방탄력(防彈力)과 외관이 우수한 섬유강화 복합성형체의 제조방법에 관한 것으로서, 본 발명으로 제조된 섬유강화 복합성형체로는 방탄복, 헬멧(Helmet) 또는 전차프로텍터(Tankprotector)등이 있다.The present invention relates to a method for producing a fiber-reinforced composite molded article having excellent ballistic resistance and appearance, and the fiber-reinforced composite molded article manufactured by the present invention includes a body armor, a helmet or a tank protector. .

본 발명을 좀더 상세하게 설명하면 지방족 폴리아미드 필라멘트사로 제직된 직물과 아라미드(Aramide)사로 된 직물을 특정의 조건하에서 각각 열처리(Heat Setting)시킨 다음 페놀계 또는 에폭시수지와 폴리비닐부티랄, 메탄올등으로 조성되는 수지용액에 함침시켜 반경화 상태의 프리프레그(prepreg)를 제조한 후 이들을 적당한 크기로 절단하여 상호 적층시키는 것을 특징으로 하는 방탄력과 외관이 우수한 섬유강화 복합성형체의 제조방법에 관한 것이다. 헬멧등에 방탄기능과 내염성을 부여하기 위한 종래의 방법으로는 지방족 폴리아미드섬유 직포와 아라미드섬유 직포를 페놀 또는 에폭시 수지용액에 함침시켜 건조시킨 것을 적정크기로 절단한 후 단독 또는 상호적층한 후 가열 가압하여 제조하였으나(일본특개소 61-17440) 이러한 방법에 의할 경우 직포와 수지간의 낮은 접착력 때문에 성형 후에 수지함침 직포 상호간의 박리현상이 일어나서 인장강력 및 방탄력이 저하되었으며, 가열가압시 수지함침 직포의 수축현상으로 인해 생산효율이 떨어지는 문제점이 있었으며 또 종래의 방법은 단순히 페놀수지 또는 에폭시수지만을 경화제로 사용하였기 때문에 성형체의 표면이 불량하여 최종제품의 품위를 손상시키는 문제점이 있었다.The present invention will be described in more detail by heat-treating each fabric (woven fabric made of aliphatic polyamide filament yarn and fabric made of aramid (Aramide)) under specific conditions, and then phenolic or epoxy resin, polyvinyl butyral, methanol, and the like. The present invention relates to a method for producing a fiber-reinforced composite molded article having excellent ballistic resistance and appearance by impregnating a resin solution prepared in the present invention to produce a prepreg in a semi-cured state, and then cutting them into a suitable size. . Conventional methods for imparting ballistic resistance and flame resistance to helmets include impregnating an aliphatic polyamide fiber fabric and an aramid fiber fabric with a phenol or epoxy resin solution, and cutting the dried to an appropriate size. However, according to this method, the tensile strength and the ballistic resistance of the resin-impregnated woven fabric were reduced after molding due to the low adhesion between the woven fabric and the resin. Due to the shrinkage phenomenon, there was a problem in that the production efficiency was lowered. In addition, the conventional method simply used phenol resin or epoxy resin as a curing agent, so that the surface of the molded product was poor, thereby damaging the quality of the final product.

본 발명은 상술한 바와 같은 종래 기술의 제반 문제점을 해결하기 위하여 안출된 것으로 상술하면 다음과 같다. 지방족 폴리아미드섬유 직포를 O.P.U(Oil Pick Up)값이 0.05-0.3%가 되도록 130-150℃에서 3-5분간 1차로 열처리한 후 이를 다시 2차로 170-190℃에서 4-6분간 열처리하고, 아라미드섬유 직포를 O.P.U값이 0.01-0.1%가 되도록 200-230℃에서 7-10분간 열처리한 다음, 이들의 직포를 페놀 또는 에폭시수지와 폴리비닐부티랄, 메탄올, 카프로락탐 블록 이소시아네이트(Caprolactam blocked isocyanate)로 조성된 수지용액에 침지시킨 다음 수지 용액의 픽업율이 지방족 폴리아마이드섬유 직포의 경우는 20-30중량%, 아라미드섬유 직포의 경우는 10-20중량%가 되게한 다음 열처리하여 반경화 상태의 프리프레그를 제조한 후, 적정크기로 절단한 것을 수매 상호적층시켜 가열가압 및 냉각시키는 것을 특징으로 하는 섬유강화 복합성형체의 제조방법에 관한 것이다.The present invention has been made in order to solve the problems of the prior art as described above as follows. The aliphatic polyamide fiber woven fabric was primarily heat treated at 130-150 ° C. for 3-5 minutes so as to have an OPU (Oil Pick Up) value of 0.05-0.3%, and then secondly heat-treated at 170-190 ° C. for 4-6 minutes, The aramid fiber woven fabric was heat-treated at 200-230 ° C. for 7-10 minutes so that the OPU value was 0.01-0.1%, and then the woven fabric was phenol or epoxy resin, polyvinyl butyral, methanol, and caprolactam blocked isocyanate. Immersed in the resin solution prepared in the following) and then the pickup rate of the resin solution was 20-30% by weight in the case of aliphatic polyamide fiber woven fabric, and 10-20% by weight in the case of aramid fiber woven fabric, followed by heat treatment. The present invention relates to a method for producing a fiber-reinforced composite molded article characterized by preparing a prepreg of the present invention, and then heating and pressing the product, which is cut to a suitable size, by mutual lamination.

본 발명에서 지방족 폴리아미드섬유 직포 및 아라미드섬유 직포를 열처리하는 이유는 섬유직포의 유제함량을 저하시커 직포와 수지용액과의 결합력을 증대시키기 위함이며 이렇게 함으로서 가열 가압하여 성형시켰을 때 직포간의 박리현상을 완전하게 방지할 수 있다. 또한 지방족 폴리아미드 섬유 직포를 2차로 열처리하는 이유는 지방족 폴리아미드 섬유 직포의 건열수축율을 3%이하로 감소시켜 후공정에서 발생되는 수축현상을 사전에 방지하여 생산효율을 증대시키기 위함이다. 그리고 프리프레그의 제조에 있어 수지용액중에 폴리비닐부티랄을 첨가함으로써 프리프레그의 표면외관이 미려해짐은 물론 결합강도가 일층 더 강화되며, 또한 직포와 수지용액과 친화력 및 결합속도의 향상을 위해 촉매로 카프로락탐 블록 이소시아네이트를 첨가하였다.The reason for heat-treating the aliphatic polyamide fiber woven fabric and the aramid fiber woven fabric in the present invention is to reduce the emulsion content of the fiber woven fabric to increase the bonding force between the seeker woven fabric and the resin solution. Can be prevented completely. In addition, the reason for the secondary heat treatment of the aliphatic polyamide fiber woven fabric is to reduce the dry heat shrinkage rate of the aliphatic polyamide fiber woven fabric to 3% or less to prevent the shrinkage occurring in the post process in advance to increase the production efficiency. In the preparation of the prepreg, the addition of polyvinyl butyral to the resin solution not only enhances the surface appearance of the prepreg but also enhances the bonding strength, and also improves the affinity and binding speed of the woven fabric and the resin solution. Was added caprolactam block isocyanate.

한편, 본 발명에 있어서 지방족 폴리아미드섬유 또는 아라미드섬유로 강화된 각각의 프리프레그를 상호적층시켜 가열 가압 및 냉각함에 있어서의 최적 조건은 온도 150-160℃, 압력 100-120Kg/㎠으로 5-15분간 가열가압하고 15-25℃에서 2-7분간 냉각하는 것이다.On the other hand, in the present invention, the optimum conditions for heat pressurization and cooling by mutually stacking each prepreg reinforced with aliphatic polyamide fibers or aramid fibers are 5-15 at a temperature of 150-160 ° C. and a pressure of 100-120 Kg / cm 2. Heat pressurize for minutes and cool for 2-7 minutes at 15-25 ℃.

본 발명으로 제조된 섬유강화 복합성형체인 헬멧, 방탄복, 또는 전차프로텍터등은 종래의 것에 비해 방탄력과 표면 외관이 월등히 우수하였으며 높은 생산성으로 제조할 수 있다.The fiber-reinforced composite molded article produced by the present invention, such as a helmet, a body armor, a tank protector, and the like, have excellent ballistic resistance and surface appearance, and can be manufactured with high productivity.

[실시예]EXAMPLE

(1) 840데니어의 나이론 6섬유를 사용하여 36×36본/인치의 밀도를 가지는 바스켓조직의 직물을 제직하여 O.P.U값이 0.1%가 되도록 130℃에서 5분간 열처리한 후 180℃에서 5분간 재차 열처리를 실시하였다.(1) Using a 840 denier nylon 6 fiber, weaving a basket tissue with a density of 36 × 36 patterns / inch and heat-treating at 130 ° C. for 5 minutes to obtain an OPU value of 0.1%, and then again at 180 ° C. for 5 minutes. Heat treatment was performed.

(2) 1,5000데니어의 아라미드섬유를 이용하여 17×17본/인치의 밀도를 가지는 바스켓조직의 직물을 제직하여 O.P.U값이 0.1%가 되도록 210℃에서 9분간 열처리를 실시하였다.(2) Using a 1,5000 denier aramid fiber, weaving a basket tissue having a density of 17 × 17 patterns / inch was heat-treated at 210 ℃ for 9 minutes so that the O.P.U value is 0.1%.

상기 (1),(2)의 열처리된 직포를 페놀계 수지 25중량%, 폴리비닐부티랄 5중량%, 메탄올 69중량%, 카프로락탐 블록 이소시아네이트 1중량%로 조성된 수지용액에 침지시켜 나이론 6 직포 및 아라미드직포의 수지 함량이 각각 30중량% 및 15중량%가 되도록 픽업한 다음 열처리하여 프리프레그를 제조한 후 이들을 소정의 크기로 절단하였다.The heat treated woven fabric of (1) and (2) was immersed in a resin solution composed of 25% by weight of phenolic resin, 5% by weight of polyvinyl butyral, 69% by weight of methanol, and 1% by weight of caprolactam block isocyanate. The resin contents of the woven fabric and the aramid woven fabric were picked up to 30% by weight and 15% by weight, respectively, and then heat-treated to prepare prepregs, and then they were cut to a predetermined size.

다음에 나이론 6 프리프레그 10, 아라미드 프리프레그 4매를 상호 적층하되 나이론 6 프리프레그를 표면층으로 하고 아라미드 프리프레그를 내층으로 적층한 다음 온도 150℃, 압력110kg/㎠로 10분동안 가열 가압하여 모울딩한 후 20℃의 냉각수를 이용하여 5분간 냉각하여 섬유강화 복합성형체(방탄용 헬멧)을 제조하여 방탄력을 측정하였는 바 그 결과는 (표1)과 같다.Next, 10 nylon 6 prepregs and 4 aramid prepregs were laminated to each other, and the nylon 6 prepreg was used as a surface layer, and the aramid prepreg was laminated as an inner layer, and then heated and pressurized at a temperature of 150 ° C. and a pressure of 110 kg / cm 2 for 10 minutes. After crying, the fiber reinforced composite molded article (ballistic helmet) was manufactured by cooling for 5 minutes using a cooling water at 20 ° C., and the ballistic resistance was measured. The results are shown in Table 1 below.

[비교예 1]Comparative Example 1

(1) 840데니어의 나일론 6 섬유를 사용하여 36×36본/인치의 밀도를 가지는 바스켓조직의 직물을 제직하였다.(1) A woven fabric of basket structure having a density of 36 × 36 patterns / inch was woven using nylon 6 fiber of 840 denier.

(2) 1,500데니어의 아라미드섬유를 사용하여 17×17본/인치의 밀도를 가지는 바스켓조직의 직물을 제직하였다.(2) Using a 1,500 denier aramid fibers, weaving a basket of fabric having a density of 17 × 17 pattern / inch.

상기(1),(2)의 직포를 페놀계 수지 31중량%, 메탄올 69중량%로 조성된 수지용액에 침지시켜 나이론 6직포 및 아라미드 직포의 수지함량이 각각 30중량% 및 15중량%가 되도록 열처리하여 프리프레그를 제조한 후 이들을 소정의 크기로 절단하였다. 다음에 나이론 6 프리프레그 10매, 아라미드 프리프레그 4매를 상호 적층하되 나이론 6 프리프레그를 표면층으로 하고 아라미드 프리프레그를 내층으로 하여 적층한 다음 온도150℃, 압력 110Kg/㎠으로 10분동안 가열, 가압하여 모울딩한 후 20℃의 냉각수를 이용 5분간 냉각하여 섬유강화 복합성형체(방탄용 헬멧)을 제조하여 방탄력을 측정하였다(표 1)참조.The woven fabrics of (1) and (2) were immersed in a resin solution composed of 31% by weight of phenolic resin and 69% by weight of methanol so that the resin contents of nylon 6 and aramid woven fabric were 30% by weight and 15% by weight, respectively. The prepregs were prepared by heat treatment, and then they were cut to a predetermined size. Next, 10 nylon 6 prepregs and 4 aramid prepregs were laminated to each other, and the nylon 6 prepreg was used as a surface layer, and the aramid prepreg was laminated as an inner layer, and then heated at a temperature of 150 ° C. and a pressure of 110 Kg / cm 2 for 10 minutes. After pressing and molding, the mixture was cooled for 5 minutes using a cooling water at 20 ° C. to prepare a fiber-reinforced composite molded body (ballistic helmet) and to measure the ballistic resistance (Table 1).

[비교예 2]Comparative Example 2

840데니어의 나이론 6 섬유를 사용하여 36×36본/인치의 밀도를 가지는 바스켓조직의 직물을 제직한 후, 페놀계 수지 31중량%, 메탄을 69중량%로 조성된 수지용액에 침지시켜 수지함량이 30중량%가 되도록 열처리하여 프리프레그를 제조한 후 소정의 크기로 절단(14매)한 다음 이들을 적층하여 온도 150℃, 압력 110Kg/㎠로 10분동안 가열, 가압하여 모울딩한 후 20℃의 냉각수를 이용 5분간 냉각하여 섬유강화 복합성형체(방탄용 헬멧)을 제조하여 방탄력을 측정하였다(표1)참조.After weaving a basket fabric having a density of 36 × 36 plates / inch using 840 denier nylon 6 fibers, the resin content was immersed in a resin solution composed of 31 wt% phenolic resin and 69 wt% methane. Heat-treated to 30% by weight to prepare a prepreg, cut to a predetermined size (14 sheets), and then laminated them and heated and pressurized for 10 minutes at a temperature of 150 ° C. and a pressure of 110 Kg / cm 2 and then 20 ° C. Cooling water was cooled for 5 minutes to prepare a fiber-reinforced composite molded body (ballistic helmet) to measure the ballistic resistance (Table 1).

[비교예 3]Comparative Example 3

1,500데니어의 아라미드섬유를 사용한 것 외에는 비교예 2와 동일한 방법으로 실시하였다(표1)참조.The same procedure as in Comparative Example 2 was conducted except that 1,500 denier aramid fibers were used (see Table 1).

[표 1]TABLE 1

Figure kpo00001
Figure kpo00001

* 방탄력 측정 : 미국 HP White LAB에서 측정함.* Bulletproof force measurement: measured in the United States HP White LAB.

17grain의 입자 혹은 탄환을 가속시켜 목표물에 수직으로 명중시킨다. 이때의 입자 혹은 탄환의 속도 및 관통여부를 측정하여 V50(Velocity 50)를 산출한다.Accelerate 17grain particles or bullets and hit them vertically. The velocity and penetration of particles or bullets at this time are measured to calculate V50 (Velocity 50).

V50(Velocity 50)이란 50%의 방탄성을 가질때의 탄환 또는 입자의 속도이며, 통상적으로 거리측정, 총구에서의 속도, 목표물 앞에서의 속도, 탄환 또는 입자의 중량을 산정하여 낸 수치이며 방탄력을 표시하는 단위이다.V50 (Velocity 50) is the velocity of a bullet or particle when it has a ballistic resistance of 50%, and is usually a value obtained by calculating a distance, a speed in a muzzle, a velocity in front of a target, a weight of a bullet or particles, and a ballistic force. The unit to display.

Claims (3)

지방족 폴리아미드섬유 직포와 아리미드섬유 직포를 각각 열경화성 수지조성액에 함침시킨 다음, 이들 수매를 상호 적층하여 가열, 가압 성형시킴에 있어서, 수지에 함침시키기 전에 지방족 폴리아미드섬유 직포를 O.P.U(Oil Pick Up)값이 0.05-03%가 되도록 130-150℃에서 3-5분간 1차 열처리한 다음 170-190℃에서 4-6분간 2차 열처리하고, 아라미드섬유 직포를 O.P.U값이 0.01-0.1%가 되도록 200-230℃에서 5-10분간 열처리함을 특징으로 하는 방탄력이 우수한 섬유강화 복합성형체의 제조방법.The aliphatic polyamide fiber woven fabric and the arimid fiber woven fabric are impregnated with the thermosetting resin composition, respectively, and these laminates are mutually laminated and heated and press-molded. The aliphatic polyamide fiber woven fabric is subjected to OPU (Oil Pick Up) before impregnation with the resin. ) First heat treatment at 130-150 ° C. for 3-5 minutes to 0.05-03%, then second heat treatment at 170-190 ° C. for 4-6 minutes, and aramid fiber woven fabric with OPU value of 0.01-0.1%. Method for producing a fiber-reinforced composite molded article having excellent anti-ballistic power characterized in that the heat treatment at 200-230 ℃ 5-10 minutes. 제 1 항에 있어서, 열경화성 수지조성액은 페놀 또는 에폭시 수지와, 폴리비닐부티랄, 메탄올 및 카프로락탐 블록 이소시아네이트로 조성됨을 특징으로 하는 방탄력이 우수한 섬유강화 복합성형체의 제조방법The method of claim 1, wherein the thermosetting resin composition is composed of a phenol or an epoxy resin and polyvinyl butyral, methanol, and caprolactam block isocyanate. 제 1 항에 있어서, 수지함침량을 지방족 폴리아미드섬유 직포의 경우는 20-30중량%, 아라미드섬유 직포의 경우는 10-20중량%가 되도록 하는 방탄력이 우수한 섬유강화 복합성형체의 제조방법.The method for producing a fiber-reinforced composite molded article according to claim 1, wherein the resin impregnation amount is 20-30% by weight for an aliphatic polyamide fiber woven fabric and 10-20% by weight for an aramid fiber woven fabric.
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