KR20230076927A - Electromagnetic wave shielding carbon fiber manufacturing method by conductive spray-dipping coating - Google Patents
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- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/22—Sheathing; Armouring; Screening; Applying other protective layers
- H01B13/225—Screening coaxial cables
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/0016—Apparatus or processes specially adapted for manufacturing conductors or cables for heat treatment
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/30—Drying; Impregnating
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
- H05K9/009—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising electro-conductive fibres, e.g. metal fibres, carbon fibres, metallised textile fibres, electro-conductive mesh, woven, non-woven mat, fleece, cross-linked
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Abstract
본 발명은 탄소섬유에 나노 금속 분말을 코팅하여 탄소섬유의 기본 물성을 향상시키고 전자파 차폐 기능을 부여하는 전자파 차폐 탄소섬유 제조방법에 관한 것이다.
본 발명은 「(a) 탄소섬유에 나노 금속 분말을 분사하여 금속 코팅 탄소섬유를 형성시키는 단계; (b) 상기 금속 코팅 탄소섬유를 열 건조시키는 단계; (c) 열 건조된 금속 코팅 탄소섬유에 금속분말이 분산된 우레탄 수지 수용액을 침액(浸液, Dipping)시키는 단계; 및 (d) 우레탄 수지 피막이 형성된 탄소섬유를 건조처리하는 단계; 를 포함하는 전도성 분사-침액 코팅에 의한 전자파 차폐 탄소섬유 제조방법」을 제공한다.The present invention relates to a method for manufacturing electromagnetic wave shielding carbon fiber, which improves the basic physical properties of carbon fiber and imparts an electromagnetic wave shielding function by coating carbon fiber with nano metal powder.
The present invention comprises the steps of "(a) spraying nano-metal powder on carbon fibers to form metal-coated carbon fibers; (b) heat-drying the metal-coated carbon fibers; (c) dipping an aqueous urethane resin solution in which metal powder is dispersed into the heat-dried metal-coated carbon fiber; and (d) drying the carbon fibers on which the urethane resin film is formed. It provides a method for manufacturing electromagnetic wave shielding carbon fiber by conductive spray-immersion coating comprising a.
Description
본 발명은 탄소섬유에 나노 금속 분말을 코팅하여 탄소섬유의 기본 물성을 향상시키고 전자파 차폐 기능을 부여하는 전자파 차폐 탄소섬유 제조방법에 관한 것이다. The present invention relates to a method for manufacturing electromagnetic wave shielding carbon fiber, which improves the basic physical properties of carbon fiber and imparts an electromagnetic wave shielding function by coating carbon fiber with nano metal powder.
최근 전기 자동차, 자율주행 자동차, 드론, 도심 항공기 등의 수송 수단(이하, '전자기기 운송 수단') 연구 개발 및 제품화가 증가하고 있다. 이러한 전자기기 운송 수단은 많은 편의를 제공하지만 기기로부터 발생하는 전자파는 인체에 악영향을 미쳐 신경 과민, 두통, 어지러움, 생체 리듬의 변화 등 여러 가지 질병들을 유발시킬 수 있다고 보고되고 있다. Recently, research, development, and commercialization of means of transportation (hereinafter, 'electronic means of transportation') such as electric vehicles, self-driving cars, drones, and urban aircraft are increasing. It has been reported that these electronic means of transportation provide a lot of convenience, but electromagnetic waves generated from the devices can adversely affect the human body and cause various diseases such as nervousness, headache, dizziness, and changes in biorhythms.
또한 전자파는 인체뿐만 아니라 특정한 주파수를 통해 작동시키는 기기들의 오작동을 유발하여 예기치 못한 사고 및 상황을 유발시킬 수 있다. 현재 이와 같은 전자파 장애에 대한 위험성을 인식하고, 문제의 해결을 위해 전자파 차폐에 관한 많은 연구가 국내·외적으로 진행되고 있다. In addition, electromagnetic waves may cause malfunctions of devices that operate through a specific frequency as well as the human body, causing unexpected accidents and situations. Currently, many studies on electromagnetic wave shielding are being conducted domestically and internationally to recognize the risk of electromagnetic interference and to solve the problem.
전자파에 의해 인체에 악영향을 주는 현상이나 전자기기로부터 발생하는 불요 전자파가 통신이나 다른 기기에 전자기적 장애를 유발시키는 현상을 전자파 장애(electromagnetic interference, EMI)라 일컬으며, 이러한 EMI의 영향은 전기전자 및 통신 산업에 있어 치명적인 장애 요소로 대두되고 있다. The phenomenon that adversely affects the human body by electromagnetic waves or the phenomenon that unwanted electromagnetic waves generated from electronic devices cause electromagnetic interference to communication or other devices is called electromagnetic interference (EMI). It is emerging as a fatal obstacle in the telecommunications industry.
EMI 방지를 위해서는 전자기기에서 기준치 이상의 전자파가 누설되지 않도록 하는 것이 중요하며, 반대로 전자기기에 불요 전자파가 침입하지 않도록 하는 것도 중요하다. In order to prevent EMI, it is important to prevent electromagnetic waves exceeding a standard value from leaking from electronic devices, and conversely, it is also important to prevent unnecessary electromagnetic waves from entering electronic devices.
일반적으로 전자파 차폐 소재로는 금속계 소재가 주목 받아 왔다. 하지만 각종 경량화 추세 및 에너지 저감적 측면에서 금속 대비 경량인 고분자계 소재를 이용한 방법들에 대한 연구가 이루어지고 있다. 하지만 고분자계 소재는 기본적으로 전자파 차폐의 효과가 없으며, 이러한 소재에 차폐성능을 부여하기 위해, 전이금속인 Cu, Ag, Ni 등을 코팅시켜 전도성을 가지면서 전자기파를 흡수할 수 있는 플라스틱 강화 복합재료를 제조하여 전자파를 차폐시키는 효과를 발휘할 수 있는 재료를 개발하고 있는 추세이다. In general, metal-based materials have received attention as electromagnetic wave shielding materials. However, in terms of various lightweight trends and energy reduction, research is being conducted on methods using polymer-based materials that are lighter than metals. However, polymer-based materials basically do not have the effect of shielding electromagnetic waves, and in order to impart shielding performance to these materials, plastic-reinforced composite materials that can absorb electromagnetic waves while having conductivity by coating transition metals such as Cu, Ag, Ni, etc. It is a trend to develop materials that can exert the effect of shielding electromagnetic waves by manufacturing.
고분자계 소재에 각 전이금속을 도입시켰을 경우 전자파 차폐능을 부여할 수 있으나, Cu는 공기 중에서 쉽게 산화되어 CuxOy로 변성되어 그 특성을 상실하는 경우가 종종 있으며, Ag는 단가가 비싸기 때문에 비용적인 측면에서 불리하다. 반면 Ni는 비용적인 측면에서 유리하며, 표면 산화가 적기 때문에 고분자 기반 전자파 차폐용 소재의 가공용으로 주목 받고 있으나 Ag나 Cu에 비해 전기적 특성이 좋지 못한 한계가 있다.When each transition metal is introduced into a polymer-based material, electromagnetic wave shielding ability can be given, but Cu is easily oxidized in air and denatured into CuxOy, which often loses its properties, and Ag is expensive, so cost aspects disadvantaged in On the other hand, Ni is advantageous in terms of cost and has less surface oxidation, so it is attracting attention for processing of polymer-based electromagnetic wave shielding materials, but has poor electrical properties compared to Ag or Cu.
한편, 고분자계 재료는 대부분의 전자파를 투과시키는 특성을 가지고 있어 충전재를 함께 사용하는 것이 효과적이다. 지금까지 주로 사용된 전자파 차폐용 복합재료는 고분자 기재(基材)에 각종 금속섬유나 세라믹 분말을 첨가하여 만들었다. 복합재료 제작에 사용된 전형적인 기재로는 에폭시 수지, 페놀수지, 실리콘 고무, 폴리에틸렌 등을 예시할 수 있으며, 충전로는 전도성 손실재로서 알루미늄, 은 분말, 은도금 유리구, 흑연 분말 등이 널리 사용되어 왔다. 또한, 자성손실 첨가재로서 각종 페라이트 분말 및 카르보닐 철 분말이 사용되고 있으며, 유전 손실재로 PMN-PT(lead magnesium niobate-PbTiO3) 세라믹 또는 BaTiO3 등이 검토되고 있다.On the other hand, since the polymer-based material has a property of transmitting most of the electromagnetic waves, it is effective to use it together with a filler. Composite materials for shielding electromagnetic waves, which have been mainly used so far, are made by adding various metal fibers or ceramic powders to a polymer substrate. Epoxy resin, phenolic resin, silicone rubber, polyethylene, etc. can be exemplified as typical substrates used in the manufacture of composite materials, and aluminum, silver powder, silver-plated glass spheres, graphite powder, etc. are widely used as conductivity loss materials for filling furnaces. come. In addition, various ferrite powders and carbonyl iron powders are used as magnetic loss additives, and PMN-PT (lead magnesium niobate-PbTiO 3 ) ceramics or BaTiO 3 are being studied as dielectric loss materials.
본 발명은 탄소섬유의 기본 물성을 향상시키고, 표면상태를 개질하며, 편조 케이블 제작을 용이하게 하는 유연성을 갖도록 하고 전자파 차폐 효과가 우수하게 발현되도록 하는 전자파 차폐 탄소섬유 제조 방법을 제공함에 그 목적이 있다. The purpose of the present invention is to provide a method for manufacturing electromagnetic wave shielding carbon fiber that improves the basic physical properties of carbon fiber, modifies the surface state, has flexibility that facilitates braided cable production, and exhibits excellent electromagnetic wave shielding effect. there is.
본 발명은 「(a) 탄소섬유에 나노 금속 분말을 분사하여 금속 코팅 탄소섬유를 형성시키는 단계; (b) 상기 금속 코팅 탄소섬유를 열 건조시키는 단계; (c) 열 건조된 금속 코팅 탄소섬유에 금속분말이 분산된 우레탄 수지 수용액을 침액(浸液, Dipping)시키는 단계; 및 (d) 우레탄 수지 피막이 형성된 탄소섬유를 건조처리하는 단계; 를 포함하는 전도성 분사-침액 코팅에 의한 전자파 차폐 탄소섬유 제조방법」을 제공한다.The present invention comprises the steps of "(a) spraying nano-metal powder on carbon fibers to form metal-coated carbon fibers; (b) heat-drying the metal-coated carbon fibers; (c) dipping an aqueous urethane resin solution in which metal powder is dispersed into the heat-dried metal-coated carbon fiber; and (d) drying the carbon fibers on which the urethane resin film is formed. It provides a method for manufacturing electromagnetic wave shielding carbon fiber by conductive spray-immersion coating comprising a.
상기 (a)단계는 단수 또는 복수 가닥의 탄소섬유를 40~100 T/M 범위의 연수로 약연사(Low twist) 처리하는 가연(加撚, twisting)공정으로 전처리하는 과정을 포함할 수 있으며, 상기 나노 금속 분말로는 직경 50~100 ㎚의 구리 분말을 적용할 수 있다.The step (a) may include pre-treatment of single or multiple strands of carbon fiber with a low twisting process with soft water in the range of 40 to 100 T/M, Copper powder having a diameter of 50 to 100 nm may be used as the nano-metal powder.
또한, 상기 (a)단계에서는 나노 금속 분말이 분산된 콜로이드 수용액을 분사하되, 상기 콜로이드 수용액은, 물 45~55 wt%, 우레탄 수지 40~50 wt%, 경화제 0.3~0.7 wt%, 나노 금속 분말 4.3~4.7 wt% 를 포함하여 점도 200~300 cps가 되도록 조성된 것을 적용할 수 있다.In addition, in the step (a), the colloidal aqueous solution in which the nano-metal powder is dispersed is sprayed, and the colloidal aqueous solution includes 45 to 55 wt% of water, 40 to 50 wt% of a urethane resin, 0.3 to 0.7 wt% of a curing agent, and nano-metal powder It is possible to apply a composition so that the viscosity is 200 to 300 cps, including 4.3 to 4.7 wt%.
또한, 상기 (a)단계는 분사각 13~20°, 분사 높이 5~10 ㎝, 분사 범위 5~8 ㎝, 분사압 38~45 psi 및 공급 유량 0.9~6.1 lpm 범위에서 분사조건을 제어할 수 있다.In addition, the step (a) can control the spray conditions in the range of spray angle 13 ~ 20 °, spray height 5 ~ 10 cm, spray range 5 ~ 8 cm, spray pressure 38 ~ 45 psi, and supply flow rate 0.9 ~ 6.1 lpm there is.
상기 (b)단계는 250~290℃ 온도 조건에서 5~10초간 열 건조를 진행시킬 수 있으며, 상기 (c)단계의 상기 우레탄 수지 수용액은, 물 35~45 wt%, 우레탄 수지 50~60 wt%, 경화제 0.3~0.7 wt%, 나노 금속 분말 4.3~4.7 wt% 를 포함하여 점도 500~700 cps가 되도록 조성된 것을 적용할 수 있다.In step (b), heat drying may be performed for 5 to 10 seconds at a temperature of 250 to 290 ° C., and the aqueous solution of the urethane resin in step (c) includes 35 to 45 wt% of water and 50 to 60 wt% of urethane resin. %, curing agent 0.3 ~ 0.7 wt%, including nano-metal powder 4.3 ~ 4.7 wt% can be applied so that the viscosity is 500 ~ 700 cps.
상기 (d)단계의 건조처리는 오븐 건조 후 우레탄 수지 피막이 형성된 탄소섬유에 15℃ 미만의 냉각수를 분무하고 냉풍 건조를 실시하는 과정으로 진행할 수 있다.The drying treatment in step (d) may proceed to a process of spraying cooling water at less than 15° C. on the carbon fiber on which the urethane resin film is formed after drying in an oven and performing cold air drying.
또한, 상기 (a)단계 내지 (d)단계를 거쳐 나노 금속 분말이 분사-침액 코팅된 탄소섬유 외연에 수지 압출 코팅을 실시하는 (e)단계를 더 포함시킬 수 있다.In addition, a step (e) of performing resin extrusion coating on the outer edge of the carbon fiber on which the nano-metal powder is spray-immersion coated through steps (a) to (d) may be further included.
본 발명에 따르면 아래의 효과를 기대할 수 있다.According to the present invention, the following effects can be expected.
1. 분사-침액 코팅에 의해 인장강도, 전기전도성 등 탄소섬유의 기본 물성이 향상되고 전자파 차폐 기능이 부여된다.1. The basic physical properties of carbon fiber, such as tensile strength and electrical conductivity, are improved by spray-immersion liquid coating, and electromagnetic wave shielding function is given.
2. 탄소섬유를 가연공정으로 전처리하여, 물성 저하를 방지하고 편조 케이블 제작을 용이하게 하는 유연성을 갖는다.2. By pre-treating carbon fiber with a twisting process, it has flexibility to prevent deterioration of physical properties and facilitate the production of braided cables.
3. 섬유 표면에 보플 및 핀(pin) 사 등의 불량 요소가 제거되어 외관이 개선된다.3. Defective elements such as fluff and pin yarn are removed from the surface of the fiber to improve the appearance.
[도 1]은 본 발명 (a)단계에서 이용되는 탄소섬유 연사장치의 구성도이다.
[도 2]는 본 발명 (a)단계에서 이용되는 나노 금속 분말이 포함된 콜로이드 수용액 분사를 위한 분사장치의 구성도이다.
[도 3]은 본 발명 (b)단계에서 이용되는 건조장치의 구성도이다.
[도 4]는 본 발명 (c)단계에서 이용되는 침액장치의 구성도이다.
[도 5]는 본 발명에 의한 전도성 분사-침액 코팅 전·후의 탄소섬유를 편조한 상태를 촬영하여 표면 상태를 비교한 것이다
[도 6]은 본 발명 (e)단계를 거쳐 가공된 전자파 차폐 탄소섬유의 구성도이다.[Figure 1] is a configuration diagram of a carbon fiber yarn yarn used in step (a) of the present invention.
[Figure 2] is a configuration diagram of a spraying device for spraying a colloidal aqueous solution containing nano-metal powder used in step (a) of the present invention.
[Figure 3] is a configuration diagram of a drying device used in step (b) of the present invention.
[Figure 4] is a configuration diagram of an immersion device used in step (c) of the present invention.
[Figure 5] compares the surface conditions by photographing the state of braiding carbon fibers before and after conductive spray-immersion coating according to the present invention.
[Figure 6] is a configuration diagram of the electromagnetic wave shielding carbon fiber processed through the step (e) of the present invention.
본 발명은 전기도전성이 우수한 탄소섬유에 나노 금속 분말을 분사(Spray) 후 건조, 나노 금속 분말이 분산된 우레탄 수지를 침액(dipping)시킨 후 건조하는 공정으로 이루어진다. The present invention consists of a process of spraying nano-metal powder on carbon fibers having excellent electrical conductivity, drying, dipping urethane resin in which nano-metal powder is dispersed, and then drying.
구체적으로 본 발명은 「(a) 탄소섬유에 나노 금속 분말을 분사하여 금속 코팅 탄소섬유를 형성시키는 단계; (b) 상기 금속 코팅 탄소섬유를 열 건조시키는 단계; (c) 열 건조된 금속 코팅 탄소섬유에 금속분말이 분산된 우레탄 수지 수용액을 침액시키는 단계; 및 (d) 우레탄 수지 피막이 형성된 탄소섬유를 건조처리하는 단계; 를 포함하는 전도성 분사-침액 코팅에 의한 전자파 차폐 탄소섬유 제조방법」을 제공한다.Specifically, the present invention comprises the steps of "(a) spraying nano-metal powder on carbon fibers to form metal-coated carbon fibers; (b) heat-drying the metal-coated carbon fibers; (c) immersing the heat-dried metal-coated carbon fiber in an aqueous urethane resin solution in which metal powder is dispersed; and (d) drying the carbon fibers on which the urethane resin film is formed. It provides a method for manufacturing electromagnetic wave shielding carbon fiber by conductive spray-immersion coating comprising a.
이하에서는 본 발명의 각 단계별 공정을 상세히 설명하기로 한다.Hereinafter, each step of the process of the present invention will be described in detail.
1. (a)단계1. Step (a)
(a)단계는 탄소섬유에 나노 금속 분말을 분사하여 금속 코팅 탄소섬유를 형성시키는 단계이다.Step (a) is a step of spraying nano-metal powder on carbon fibers to form metal-coated carbon fibers.
상기 탄소섬유는 가연(加撚, twisting)공정으로 전처리하는 것이 바람직하다. 상기 가연공정은 [도 1]에 도시된 연사장치로 실행할 수 있으며, 단수 또는 복수 가닥의 탄소섬유를 40~100 T/M 범위의 연수로 약연사(Low twist) 처리한 탄소섬유에 나노 금속 분말을 분사한다. 위와 같은 약연사 처리에 따라 케이블 편조용으로 사용하기 용이하게 되고, 편조공정 시 가이더 롤러를 거치는 과정에서 보풀 발생을 방지하여 표면 상태가 개선된다([도 5] 참조). The carbon fiber is preferably pretreated by a twisting process. The false twisting process can be carried out with the twisting device shown in [Fig. 1], and the carbon fiber of single or multiple strands is low twisted with soft water in the range of 40 to 100 T/M Nano metal powder on carbon fiber to inject According to the above weakly twisted yarn treatment, it is easy to use for cable braiding, and the surface condition is improved by preventing the generation of fluff in the process of passing through the guider roller during the braiding process (see [Fig. 5]).
종래의 무전해 도금 등을 위한 탄소섬유의 전처리 방식은 탄소섬유를 계면활성제, 유기 용매 및 비이온 계면활성제를 포함하는 수용액에 통과시켜 탄소섬유를 탈지 및 연화시키는 단계를 거친다. 탄소섬유에 사이징된 에폭시나 우레탄을 제거하는 탈지 작용을 하며, 동시에 섬유 표면을 팽윤(swelling) 및 연화(softening) 시킨다. 이러한 공정을 실시함에 따라 탄소섬유의 고유성질인 인장강도가 약화되며, 벌크(Bulk) 사절이 발생하여 편조(Braiding)된 전선 케이블의 내구성을 저하시킨다. 또한, 무전해 도금공정에서 발생하는 폐수의 처리도 문제가 된다.In a conventional method for pre-treating carbon fibers for electroless plating, the carbon fibers are passed through an aqueous solution containing a surfactant, an organic solvent, and a nonionic surfactant to degrease and soften the carbon fibers. It performs a degreasing action to remove sized epoxy or urethane from carbon fiber, and at the same time, swelling and softening the fiber surface. As this process is carried out, the tensile strength, which is a unique property of carbon fiber, is weakened, and bulk trimming occurs, thereby reducing the durability of the braided wire cable. In addition, the treatment of wastewater generated in the electroless plating process is also a problem.
본 발명은 분사-건조-침액-건조의 연속공정으로 폐수 발생 문제 등을 근본적으로 제거하면서, 분사 및 침액 코팅을 위해 전술한 가연(加撚)공정으로 탄소섬유에 대한 전처리를 수행하여 탄소섬유의 물성 저하가 발생하지 않게 된다.The present invention is a continuous process of spraying-drying-immersion-drying, which fundamentally eliminates the problem of wastewater generation, and pre-treatment of carbon fiber with the above-described false twisting process for spraying and dip coating to obtain carbon fibers. Deterioration of physical properties does not occur.
분사공정을 위해서는 나노 금속 분말이 포함된 콜로이드 수용액을 분사액으로 적용할 수 있고, 직경 50~100 ㎚의 구리 분말로 적용할 수 있다. For the spraying process, a colloidal aqueous solution containing nano metal powder can be applied as a spraying liquid, and copper powder with a diameter of 50 to 100 nm can be applied.
상기 콜로이드 수용액은 물 45~55 wt%, 우레탄 수지 40~50 wt%, 경화제 0.3~0.7 wt%, 나노 금속 분말 4.3~4.7 wt% 로 조성하여, 점도 200~300 cps가 되도록 조정한다. 이러한 낮은 점도의 콜로이드 수용액을 분사함으로써 나노 금속 분말이 탄소섬유 필라멘트 사이 사이에 깊이 스며들 수 있다.The colloidal aqueous solution is composed of 45 to 55 wt% of water, 40 to 50 wt% of a urethane resin, 0.3 to 0.7 wt% of a curing agent, and 4.3 to 4.7 wt% of nano metal powder, and the viscosity is adjusted to 200 to 300 cps. By spraying such a low-viscosity colloidal aqueous solution, the nano-metal powder can be deeply penetrated between the carbon fiber filaments.
분사조건은 분사각 13~20°, 분사 높이 5~10 ㎝, 분사 범위 5~8 ㎝, 분사압 38~45 psi, 공급 유량 0.9~6.1 lpm 범위에서 설정한다. 위의 분사공정은 [도 2]에 도시된 분사장치를 이용하여 실시할 수 있다.The spray conditions are set within the range of spray angle 13~20°, spray height 5~10 cm, spray range 5~8 cm, spray pressure 38~45 psi, supply flow rate 0.9~6.1 lpm. The above injection process can be carried out using the injection device shown in [Fig. 2].
at 20 °C (Ω·m) Resistivity, ρ,
at 20 °C (Ω m)
at 20 °C (S/ m) Conductivity, σ,
at 20 °C (S/m)
coefficient (K) Temperature
coefficient (K)
위 [표 1]은 금속 분말의 전기 저항과 전기전도성을 정리한 것이다. 전기적 성능은 은이 가장 우수하나, 가격을 고려할 때 구리를 적용하는 것이 가장 바람직하다. 일반적인 증착 방식이나 도금방식으로 탄소섬유 표면에 구리 금속 분말을 코팅하는 경우 구리가 공기 중에서 산화되어 그 전기적 특성을 상실하는 경우가 있으나, 본 발명을 적용하여 나노 구리 분말을 콜로이드 수용액에 포함시켜 분사함으로써 구리의 공기 접촉을 방지할 수 있고, 후술할 침액공정에 의해서도 구리가 공기에 직접 접하는 것을 방지할 수 있다.[Table 1] above summarizes the electrical resistance and electrical conductivity of metal powder. Although silver has the best electrical performance, it is most preferable to use copper in consideration of price. When copper metal powder is coated on the surface of carbon fiber by a general deposition or plating method, copper is oxidized in air and loses its electrical properties. Copper can be prevented from coming into contact with air, and direct contact of copper with air can also be prevented by an immersion process to be described later.
2. (b)단계2. Step (b)
(b)단계는 상기 금속 코팅 탄소섬유를 열 건조시키는 단계이다. 본 단계의 열 건조는 250~290℃ 온도 조건에서 5~10초간 진행시킬 수 있으며, [도 3]에 도시된 건조장치를 이용하여 실시할 수 있다. 상기 건조장치는 IR 히터가 내장된 터널형 히팅챔버 내부를 상기 금속 코팅 탄소섬유가 길이방향을 따라 관통하도록 구성할 수 있으며, 최대 건조 온도 400℃ 까지 가열되는 약 3m 길이의 히팅챔버를 250~290℃로 제어하고 상기 금속 코팅 탄소섬유의 이동 속도를 20~30m/min으로 제어함으로써 5~10초간의 열 건조가 진행되도록 할 수 있다.Step (b) is a step of drying the metal-coated carbon fiber by heat. Heat drying in this step can be carried out for 5 to 10 seconds at a temperature of 250 to 290 ° C., and can be carried out using the drying device shown in [Fig. 3]. The drying device may be configured so that the metal-coated carbon fiber penetrates the inside of a tunnel-type heating chamber in which an IR heater is built in along the length direction, and a heating chamber with a length of about 3 m heated to a maximum drying temperature of 400 ° C. By controlling the temperature at ° C. and controlling the moving speed of the metal-coated carbon fiber at 20 to 30 m/min, heat drying for 5 to 10 seconds may be performed.
3. (c)단계3. Step (c)
(c)단계는 열 건조된 금속 코팅 탄소섬유에 금속분말이 분산된 우레탄 수지 수용액을 침액시키는 단계이다.Step (c) is a step of immersing an aqueous urethane resin solution in which metal powder is dispersed into the heat-dried metal-coated carbon fiber.
상기 우레탄 수지 수용액은 물 35~45 wt%, 우레탄 수지 50~60 wt%, 경화제 0.3~0.7 wt%, 나노 금속 분말 4.3~4.7 wt% 로 조성하여, 점도 500~700 cps가 되도록 조정하는 것이 바람직하다.The urethane resin aqueous solution is composed of 35 to 45 wt% of water, 50 to 60 wt% of urethane resin, 0.3 to 0.7 wt% of a curing agent, and 4.3 to 4.7 wt% of nano metal powder, preferably adjusted to a viscosity of 500 to 700 cps do.
침액 방법으로는 [도 4]에 도시된 침액장치를 이용한 키스코팅(Kiss coating) 방식을 적용할 수 있다.As an immersion method, a kiss coating method using the immersion device shown in [Fig. 4] can be applied.
4. (d)단계4. Step (d)
우레탄 수지 피막이 형성된 탄소섬유를 건조처리하는 단계이다. This is a step of drying the carbon fiber on which the urethane resin film is formed.
본 단계에서는 건조 오븐기를 이용하여 우레탄 수지 피막이 형성된 탄소섬유를 완전 건조시킨 후 냉풍팬으로 후속 건조를 진행하는 것이 바람직하다. 건조 오븐기를 이용한 완전 건조 후에도 위의 탄소섬유에 부분적으로 테키(Tacky)가 남게 되므로 보빈에 권취하기 전에 온도 15℃ 미만의 냉각수를 분무하고, 냉풍팬의 바람으로 건조시켜 테키를 없애는 것이다.In this step, it is preferable to completely dry the carbon fiber on which the urethane resin film is formed using a drying oven, and then to perform subsequent drying with a cooling fan. Even after complete drying using a drying oven, tacky remains partially on the carbon fiber, so before winding on the bobbin, coolant with a temperature of less than 15 ° C is sprayed and dried with the wind of a cold fan to remove tacky.
전술한 공정에 따라 나노 금속 분말의 분사(spray)로 탄소섬유 필라멘트(filament) 사이 사이에 피막을 형성시킬 수 있고, 열 건조 후 다시 침액(Dipping) 처리하여 탄소섬유에 나노 금속 분말이 포함된 피막을 고르게 형성시킴으로써 탄소섬유의 높은 인장강도를 유지하며 전자파 차폐 기능을 부여할 수 있다. According to the above-described process, a film can be formed between carbon fiber filaments by spraying the nano-metal powder, and after heat drying, dipping treatment is performed again to form a film containing the nano-metal powder in the carbon fiber. By forming evenly, it is possible to impart electromagnetic wave shielding function while maintaining high tensile strength of carbon fiber.
본 발명에 따라 제조된 전자파 차폐 탄소섬유는 일반적인 증착 방식, 무전핵-도금 방식을 적용하여 제조한 것에 비해 전기전도성이 향상되고, 인장강도가 더욱 향상되며, 표면 상태 개선 및 표면 저항 저감 효과를 보여, 직물로 직조하거나 케이블용 편조용 우수 소재로 적용할 수 있다.The electromagnetic wave shielding carbon fiber manufactured according to the present invention has improved electrical conductivity, further improved tensile strength, improved surface condition, and reduced surface resistance compared to those manufactured by applying a general deposition method or an electronuclear-plating method. , it can be woven into a fabric or applied as an excellent material for cable braiding.
이하에서는 전술한 (a)단계 내지 (d)단계 공정 처리를 "전도성 분사-침액 코팅"이라 칭하기로 한다.Hereinafter, the process of steps (a) to (d) described above will be referred to as "conductive spray-immersion coating".
상기 전도성 분사-침액 코팅 이후에는 수지 압출 코팅으로 코팅층을 1층 더 형성시키는 (e)단계를 더 부가함으로써 전자파 차폐 탄소섬유의 사용 내구성을 향상시킬 수 있다([도 6] 참조). After the conductive spray-immersion liquid coating, the use durability of the electromagnetic wave shielding carbon fiber can be improved by further adding a step (e) of forming one more coating layer by resin extrusion coating (see [FIG. 6]).
수지 압출 코팅층 형성을 위한 수지는 우레탄 수지 기반으로 구리 등의 전도성 금속 분말을 분산시킨 것을 적용하여 전기전도성 및 전자파 차폐 성능 발현에 부 영향을 주지 않도록 할 수 있다.The resin for forming the resin extrusion coating layer is a urethane resin-based dispersion of conductive metal powder such as copper, so that electrical conductivity and electromagnetic wave shielding performance are not adversely affected.
이하 구체적 시험예와 함께 본 발명을 상세히 설명한다. Hereinafter, the present invention will be described in detail with specific test examples.
1. 시험 조건1. Test conditions
탄소섬유에 대한 전도성 분사-침액 코팅 전·후의 물성 비교를 위한 시험예에 적용된 공정별 조건은 다음과 같다.Conditions for each process applied to the test examples for comparing physical properties before and after conductive spray-immersion coating on carbon fibers are as follows.
(1) 탄소섬유 가연(加撚, twisting)공정(1) Carbon fiber twisting process
- 탄소섬유(Toray T700 12000 60E) - Carbon fiber (Toray T700 12000 60E)
- 50 T/M 가연- 50 T/M combustible
(2) 분사 코팅을 위한 분사액(콜로이드 수용액) 조성(2) Composition of spray liquid (aqueous colloidal solution) for spray coating
- 물 : 50 wt% - Water: 50 wt%
- 우레탄 수지(우레탄 30 wt%가 포함된 sol) : 45 wt%- Urethane resin (sol containing 30 wt% of urethane): 45 wt%
- 경화제(폴로이소시아네이트 고형분 90 wt%, 점도 2,000~3,500 cps) : 0.5 wt% - Curing agent (polyisocyanate solid content 90 wt%, viscosity 2,000 ~ 3,500 cps): 0.5 wt%
- 구리 분말(직경 100 nm ) : 4.5 wt%- Copper powder (
- 분사액 점도 : 240 cps- Injection fluid viscosity: 240 cps
(3) 분사장치 제어 조건(3) Injector control conditions
- 분사장치 : UniJet PWMD/PWMM- Injector : UniJet PWMD/PWMM
- 분사각 : 15°- Spray angle: 15°
- 분사 높이 : 7 ㎝- Spray height: 7 cm
- 분사 범위 : 5 ㎝- Spray range: 5 cm
- 분사압 : 40 psi(2.75 bar)- Injection pressure: 40 psi (2.75 bar)
- 공급 유량 : 6 lpm- Supply flow rate: 6 lpm
(4) 분사공정 후 열 건조 조건(4) Heat drying conditions after spraying process
- 건조장치 : 히팅챔버 길이 2,950 ㎜, 히팅챔버 내 IR 히터(1조 90 cm) 좌·우 각 8세트 내장, 최대 온도 400 ℃)- Drying device: Heating chamber length 2,950 mm, built-in IR heater (1 set 90 cm) 8 sets each left and right, maximum temperature 400 ℃)
- 건조 온도 : 260 ℃- Drying temperature: 260 ℃
- 탄소섬유 이동 속도 : 25 m/min (탄소섬유 동일 구간 열 건조 시간 7초)- Carbon fiber movement speed: 25 m/min (7 seconds of heat drying time in the same section of carbon fiber)
(5) 침액코팅을 위한 우레탄 수용액 조성 (5) Composition of aqueous urethane solution for dip coating
- 물 : 40 wt% - Water: 40 wt%
- 우레탄 수지(우레탄 30 wt%가 포함된 sol) : 55 wt%- Urethane resin (sol containing 30 wt% of urethane): 55 wt%
- 경화제(폴로이소시아네이트 고형분 90 wt%, 점도 2,000~3,500 cps) : 0.5 wt% - Curing agent (polyisocyanate solid content 90 wt%, viscosity 2,000 ~ 3,500 cps): 0.5 wt%
- 구리 분말(직경 50~100 nm ) : 4.5 wt%- Copper powder (50-100 nm in diameter): 4.5 wt%
- 우레탄 수용액 점도 : 620 cps- Urethane aqueous solution viscosity: 620 cps
(6) 침액 후 건조 조건(6) Dry conditions after soaking
- 오븐 건조 : 200℃, 20~25초- Oven drying: 200℃, 20~25 seconds
- 냉풍 건조 : 10 ℃ 냉각수 분무 후 냉풍팬 가동- Cold air drying: Cooling fan is operated after spraying 10 ℃ cooling water
2. 시험 결과2. Test results
아래 [표 2]는 탄소섬유(Toray T700 12000 60E)에 대한 전도성 분사-침액 코팅 전·후의 물성 변화를 정리하여 나타낸 것이다. [Table 2] below summarizes the physical property changes before and after the conductive spray-immersion liquid coating for carbon fiber (Toray T700 12000 60E).
[표 2]에 나타난 바와 같이 전도성 분사-침액 코팅 후 인장강도는 90.44 kgf에서 118.24 kgf로 약 30% 향상되었고, 신율은 1.8%에서 2.6%로 상대적으로 44% 이상 증가하였다. 표면저항은 0.0001~0.01% 수준으로 크게 감소하였다.As shown in [Table 2], after conductive spray-immersion coating, the tensile strength increased by about 30% from 90.44 kgf to 118.24 kgf, and the elongation increased by more than 44% from 1.8% to 2.6%. The surface resistance was greatly reduced to the level of 0.0001~0.01%.
첨부된 [도 5]에는 전도성 분사-침액 코팅 전·후의 탄소섬유를 편조한 상태를 촬영하여 표면 상태를 비교한 것이다. 핀(Pin) 사 발생 여부가 육안으로 확연히 구별된다.In the attached [Fig. 5], the state of braiding carbon fibers before and after conductive spray-immersion coating is photographed and the surface state is compared. Whether or not a pin has occurred is clearly distinguished with the naked eye.
본 발명은 위에서 언급한 바와 같이 시험예와 관련하여 설명되었으나, 본 발명의 요지를 벗어남이 없는 범위 내에서 다양한 수정 및 변형이 가능하며, 다양한 분야에서 사용 가능하다. 따라서 본 발명의 청구범위는 이전 발명의 진정한 범위 내에 속하는 수정 및 변형을 포함한다.Although the present invention has been described in relation to the test examples as mentioned above, various modifications and variations are possible within the scope without departing from the gist of the present invention, and can be used in various fields. Accordingly, the claims of the present invention include modifications and variations that fall within the true scope of the foregoing invention.
해당 없음Not applicable
Claims (9)
(b) 상기 금속 코팅 탄소섬유를 열 건조시키는 단계;
(c) 열 건조된 금속 코팅 탄소섬유에 금속분말이 분산된 우레탄 수지 수용액을 침액(浸液, Dipping)시키는 단계; 및
(d) 우레탄 수지 피막이 형성된 탄소섬유를 건조처리하는 단계; 를 포함하는 전도성 분사-침액 코팅에 의한 전자파 차폐 탄소섬유 제조방법.
(a) spraying nano-metal powder on carbon fibers to form metal-coated carbon fibers;
(b) heat-drying the metal-coated carbon fibers;
(c) dipping an aqueous urethane resin solution in which metal powder is dispersed into the heat-dried metal-coated carbon fiber; and
(d) drying the carbon fiber on which the urethane resin film is formed; Electromagnetic wave shielding carbon fiber manufacturing method by conductive spray-immersion coating comprising a.
상기 (a)단계는 단수 또는 복수 가닥의 탄소섬유를 40~100 T/M 범위의 연수로 약연사(Low twist) 처리하는 가연(加撚, twisting)공정으로 전처리하는 것을 특징으로 하는 전도성 분사-침액 코팅에 의한 전자파 차폐 탄소섬유 제조방법.
In paragraph 1,
The step (a) is conductive spraying, characterized in that pre-treatment of single or multiple strands of carbon fiber with a low twisting process with soft water in the range of 40 to 100 T / M Method for manufacturing electromagnetic wave shielding carbon fiber by dip coating.
상기 (a)단계의 나노 금속 분말로는 직경 50~100 ㎚의 구리 분말이 적용된 것을 특징으로 하는 전도성 분사-침액 코팅에 의한 전자파 차폐 탄소섬유 제조방법.
In paragraph 1,
Electromagnetic wave shielding carbon fiber manufacturing method by conductive spray-immersion coating, characterized in that copper powder with a diameter of 50 ~ 100 ㎚ is applied as the nano-metal powder in step (a).
상기 (a)단계는 나노 금속 분말이 분산된 콜로이드 수용액을 분사하되,
상기 콜로이드 수용액은, 물 45~55 wt%, 우레탄 수지 40~50 wt%, 경화제 0.3~0.7 wt%, 나노 금속 분말 4.3~4.7 wt% 를 포함하여 점도 200~300 cps가 되도록 조성된 것을 특징으로 하는 전도성 분사-침액 코팅에 의한 전자파 차폐 탄소섬유 제조방법.
In paragraph 1,
In the step (a), the colloidal aqueous solution in which the nano-metal powder is dispersed is sprayed,
The colloidal aqueous solution is composed of 45 to 55 wt% of water, 40 to 50 wt% of urethane resin, 0.3 to 0.7 wt% of curing agent, and 4.3 to 4.7 wt% of nano metal powder to have a viscosity of 200 to 300 cps. Electromagnetic wave shielding carbon fiber manufacturing method by conductive spray-immersion liquid coating.
상기 (a)단계는 분사각 13~20°, 분사 높이 5~10 ㎝, 분사 범위 5~8 ㎝, 분사압 38~45 psi 및 공급 유량 0.9~6.1 lpm 범위에서 분사조건을 제어하는 것을 특징으로 하는 전도성 분사-침액 코팅에 의한 전자파 차폐 탄소섬유 제조방법.
In paragraph 4,
In the step (a), the injection conditions are controlled in the range of a spray angle of 13 to 20 °, a spray height of 5 to 10 cm, a spray range of 5 to 8 cm, a spray pressure of 38 to 45 psi, and a supply flow rate of 0.9 to 6.1 lpm. Electromagnetic wave shielding carbon fiber manufacturing method by conductive spray-immersion liquid coating.
상기 (b)단계는 250~290℃ 온도 조건에서 5~10초간 열 건조를 진행하는 것을 특징으로 하는 전도성 분사-침액 코팅에 의한 전자파 차폐 탄소섬유 제조방법.
In paragraph 1,
The step (b) is a method for manufacturing electromagnetic wave shielding carbon fiber by conductive spray-immersion coating, characterized in that in the heat drying for 5 to 10 seconds at a temperature condition of 250 ~ 290 ℃.
상기 (c)단계의 상기 우레탄 수지 수용액은, 물 35~45 wt%, 우레탄 수지 50~60 wt%, 경화제 0.3~0.7 wt%, 나노 금속 분말 4.3~4.7 wt% 를 포함하여 점도 500~700 cps가 되도록 조성된 것을 특징으로 하는 전도성 분사-침액 코팅에 의한 전자파 차폐 탄소섬유 제조방법.
In paragraph 1,
The aqueous solution of the urethane resin in the step (c) has a viscosity of 500 to 700 cps, including 35 to 45 wt% of water, 50 to 60 wt% of the urethane resin, 0.3 to 0.7 wt% of the curing agent, and 4.3 to 4.7 wt% of the nano metal powder. Electromagnetic wave shielding carbon fiber manufacturing method by conductive spray-immersion coating, characterized in that the composition to be.
상기 (d)단계의 건조처리는 오븐 건조 후 우레탄 수지 피막이 형성된 탄소섬유에 15℃ 미만의 냉각수를 분무하고 냉풍 건조를 실시하는 과정으로 진행하는 것을 특징으로 하는 전도성 분사-침액 코팅에 의한 전자파 차폐 탄소섬유 제조방법.
In paragraph 1,
The drying treatment in step (d) is performed by spraying cooling water at less than 15 ° C. on the carbon fiber on which the urethane resin film is formed after drying in the oven and performing cold air drying. Electromagnetic wave shielding carbon by conductive spray-immersion coating Fiber manufacturing method.
(e) 상기 (a)단계 내지 (d)단계를 거쳐 나노 금속 분말이 분사-침액 코팅된 탄소섬유 외연에 수지 압출 코팅을 실시하는 단계; 를 더 포함하는 것을 특징으로 하는 전도성 분사-침액 코팅에 의한 전자파 차폐 탄소섬유 제조방법. In any one of claims 1 to 8,
(e) performing resin extrusion coating on the outer edge of the carbon fiber on which the nano-metal powder is spray-dip coated through steps (a) to (d); Electromagnetic wave shielding carbon fiber manufacturing method by conductive spray-immersion coating, characterized in that it further comprises.
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| KR20030021407A (en) * | 2001-09-06 | 2003-03-15 | 영남방직주식회사 | Electromagneticwave -cutting fibre |
| KR20070106453A (en) * | 2006-04-28 | 2007-11-01 | 닛토덴코 가부시키가이샤 | Structure having a characteristic of conducting or absorbing electromagnetic waves |
| KR20100001073U (en) * | 2008-07-23 | 2010-02-02 | 조영선 | Electromagnetic wave Cutting Fiber |
| KR101469683B1 (en) | 2013-05-31 | 2014-12-05 | 주식회사 불스원신소재 | Methods for Preparing of Electromagnetic Shielding Composite Using Copper-Nickel Plated Carbon Fiber Prepared by Electroless-Electronic Continuous Process and Electromagnetic Shielding Material Prepared by the Methods |
| KR102072483B1 (en) | 2019-07-17 | 2020-02-25 | 주식회사 비에스엠신소재 | Method for plating of carbon fiber fabric using continuous process of electroless and electrolysis plating, and fabrics that can shield electromagnetic waves including the carbon fiber fabric plated by the method |
| KR20200039255A (en) | 2018-10-05 | 2020-04-16 | 가온전선 주식회사 | Electromagnetic wave shield cable using carbon fiber |
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2021
- 2021-11-23 KR KR1020210161861A patent/KR102619446B1/en active IP Right Grant
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|---|---|---|---|---|
| JPH08323797A (en) * | 1994-10-17 | 1996-12-10 | Matsushita Electric Ind Co Ltd | Method and apparatus for producing molded product |
| KR20020000012A (en) | 2000-06-20 | 2002-01-04 | 윤종용 | Method for manufacturing chip scale package having slits |
| KR20030021407A (en) * | 2001-09-06 | 2003-03-15 | 영남방직주식회사 | Electromagneticwave -cutting fibre |
| KR20070106453A (en) * | 2006-04-28 | 2007-11-01 | 닛토덴코 가부시키가이샤 | Structure having a characteristic of conducting or absorbing electromagnetic waves |
| KR20100001073U (en) * | 2008-07-23 | 2010-02-02 | 조영선 | Electromagnetic wave Cutting Fiber |
| KR101469683B1 (en) | 2013-05-31 | 2014-12-05 | 주식회사 불스원신소재 | Methods for Preparing of Electromagnetic Shielding Composite Using Copper-Nickel Plated Carbon Fiber Prepared by Electroless-Electronic Continuous Process and Electromagnetic Shielding Material Prepared by the Methods |
| KR20200039255A (en) | 2018-10-05 | 2020-04-16 | 가온전선 주식회사 | Electromagnetic wave shield cable using carbon fiber |
| KR102072483B1 (en) | 2019-07-17 | 2020-02-25 | 주식회사 비에스엠신소재 | Method for plating of carbon fiber fabric using continuous process of electroless and electrolysis plating, and fabrics that can shield electromagnetic waves including the carbon fiber fabric plated by the method |
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