KR20020087290A - A Ni-Fe ALLOY COATING STEEL SHEET FOR SHEILDING ELECTROMAGNETIC WAVE AND A MANUFACTURING METHOD THEREFOR - Google Patents
A Ni-Fe ALLOY COATING STEEL SHEET FOR SHEILDING ELECTROMAGNETIC WAVE AND A MANUFACTURING METHOD THEREFOR Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
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- C25D5/50—After-treatment of electroplated surfaces by heat-treatment
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Abstract
Description
본 발명은 T.V, 컴퓨터, 냉장고, 복사기 등의 가전기기 및 자동차, 통신기기에서 발생되는 전자파를 효과적으로 차단할 수 있는 강판 및 그 제조방법에 관한 것이며, 보다 상세하게는 냉연강판에 Ni-Fe합금 도금을 행한 후 열처리함에 의해 전자파 차폐능이 제공된 차폐강판 및 그 제조방법에 관한 것이다.The present invention relates to a steel sheet that can effectively block electromagnetic waves generated in home appliances such as TVs, computers, refrigerators, copiers, and automobiles and communication devices, and a method of manufacturing the same. The present invention relates to a shielded steel sheet provided with electromagnetic shielding ability by heat treatment after performing the same, and a method of manufacturing the same.
최근 산업기기 및 가전기기의 디지털화가 급속히 진전되면서 각종 전자기기로부터 방출되는 전자기파가 각종 정밀기기의 신호교란, 오동작 및 기능정지 등을 일으키는 장애요인으로 작용하고 있다. 따라서, 전자기파에 의한 폐해를 얼마나 감소시킬 수 있느냐가 관련분야의 관건이 되고 있다.In recent years, as digitalization of industrial devices and home appliances has rapidly progressed, electromagnetic waves emitted from various electronic devices are acting as obstacles causing signal disturbance, malfunction, and malfunction of various precision devices. Therefore, how to reduce the damage caused by electromagnetic waves has become a key in the related field.
이에 관련된 종래기술로서, 유럽특허 제0,186,145호는 고주파영역(1MHz-1GHz)에서 납+아연+니오븀이나 납+아연+탄탈늄, 납+아연+텅스텐으로 된 금속계와 세라믹의 합성 물질로서 차폐능을 향상시키는 기술을 제시하였고, 제0,107,863호에서는 폴리머 물질과 팔라듐이나 니켈 등의 금속물질을 혼합함으로써 주파수 영역에 따른 전자파 차폐 및 흡수능을 향상시키는 기술을 제시하였다. 그러나, 상기 유럽특허 제0,186,145호는 금속계와 세라믹의 혼합에 의한 것으로 경하며, 차폐성능이 떨어지는 문제가 있고, 또한 상기 유럽특허 제0,107,863호의 기술에서는 금속과 폴리머의 혼합시 금속의 입도에 의해 차이가 많으며, 금속성분의 균일 분포가 어려워 차폐성능이 떨어지는 문제가 있었다.As a related art, European Patent No. 0,186,145 has a shielding ability as a composite material of a metal-based and ceramic of lead + zinc + niobium or lead + zinc + tantalum, and lead + zinc + tungsten in the high frequency region (1 MHz-1 GHz). In order to improve the electromagnetic wave shielding and absorption ability according to the frequency domain, a number of the present invention has been proposed, and in No. 0,107,863, a mixture of a polymer material and a metal material such as palladium or nickel is proposed. However, the European Patent No. 0,186,145 is caused by the mixing of metals and ceramics, and there is a problem of poor shielding performance, and the European Patent No. 0,107,863 has a difference due to the particle size of the metal when the metal and the polymer are mixed. Many, there is a problem that the shielding performance is poor because the uniform distribution of the metal component is difficult.
또한, 일본특개소61-163231에서는 알루미늄에 구리, 망간, 니켈, 철 등의 원소를 일정량 혼합함으로써 전자파 차폐능을 향상시키려 하였으나 대부분 차폐성능이 떨어지며 특히 저주파(KHz 영역)에서는 그 효과가 미미하다.In addition, Japanese Patent Application Laid-Open No. 61-163231 attempts to improve electromagnetic wave shielding ability by mixing a certain amount of elements such as copper, manganese, nickel, and iron with aluminum, but most of the shielding performances are inferior, especially in low frequency (KHz region).
일본특개평8-97588은 산화물 초전도성 물질에 의한 자기 차폐능 향상에 대한 것으로 제조공정이 복잡하고 부착성이 떨어지며, 일본 특개평9-116293은 플라스틱제에 전도성 자성재료를 증착도금함으로써 플라스틱과 같은 비전도성 물질에 적용하는 것으로 본 발명과는 근본적으로 다르며, 일본 특허공개 제2000-36419호는 제진강판을 만들어서 차폐능을 향상시키는 기술에 관한 것이지만 제조방법이 복잡하고 비용이 많이 드는 단점이 있다.Japanese Patent Application Laid-Open No. 8-97588 relates to the improvement of magnetic shielding ability by an oxide superconducting material, and the manufacturing process is complicated and inferior in adhesion. It is fundamentally different from the present invention as applied to a conductive material, and Japanese Patent Laid-Open No. 2000-36419 relates to a technique for improving shielding ability by making a damping steel sheet, but has a disadvantage in that the manufacturing method is complicated and expensive.
또한, 일본 특개평7-86788는 강판표면에 레이저 빔을 조사하여 강판 표면을 개질함으로써 전자파 차폐성능을 향상시킨 것으로 레이저빔의 조절이 어려워 활용상에 어려운 단점이 있다.In addition, Japanese Patent Laid-Open No. 7-86788 improves electromagnetic shielding performance by modifying the surface of a steel sheet by irradiating a laser beam on the surface of the steel sheet, which makes it difficult to control the laser beam.
이에, 본 발명의 발명자들은 상기와 같은 문제를 해결하기 위하여 연구 및 실험을 거듭하고 그 결과에 근거하여 본 발명을 제안하게 된 것으로, 본 발명은 냉연강판에 차폐능이 우수한 물질을 코팅하여 물리적 처리를 행함으로써 강판에 차폐능을 부여하는 방법 및 차폐능이 우수한 강판을 제공하고자 하는데, 그 목적이 있다.Accordingly, the inventors of the present invention have repeatedly studied and experimented to solve the above problems, and proposed the present invention based on the results. The present invention provides a physical treatment by coating a material having excellent shielding ability on a cold rolled steel sheet. It is intended to provide a method of imparting shielding ability to a steel sheet and a steel sheet excellent in shielding performance.
도 1은 Ni-Fe합금 도금 및 열처리의 유무에 따른 차폐능을 비교한 그래프1 is a graph comparing the shielding ability with or without Ni-Fe alloy plating and heat treatment
도 2는 Ni-Fe합금 도금 및 650℃에서의 열처리의 유무에 따른 차폐능을 비교한 그래프2 is a graph comparing the shielding ability with or without Ni-Fe alloy plating and heat treatment at 650 ℃
도 3은 Ni-Fe합금 도금 및 750℃에서의 열처리의 유무에 따른 차폐능을 비교한 그래프3 is a graph comparing the shielding ability with or without Ni-Fe alloy plating and heat treatment at 750 ℃
상기한 목적을 달성하기 위한 본 발명은,The present invention for achieving the above object,
냉연강판의 편면 또는 양면에 조성이 Ni: 20~90wt%, Fe:80~10wt%인 Ni-Fe합금 도금층을 1㎛~1mm의 두께로 형성하는 단계;및Forming a Ni-Fe alloy plating layer having a composition of 20: 90 wt% Ni and 80: 10 wt% Fe on one or both sides of the cold rolled steel sheet with a thickness of 1 μm to 1 mm; and
상기 Ni-Fe합금 도금층이 형성된 코팅강판을 750~1100℃에서 1분~300분간 열처리하여 강판에 전자파 차폐능을 부여하는 단계를 포함하여 이루어지는 전자파 차폐용 니켈-철 합금 코팅강판의 제조방법에 관한 것이다.A method of manufacturing a nickel-iron alloy coated steel sheet for electromagnetic wave shielding comprising heat-treating the coated steel sheet having the Ni-Fe alloy plated layer formed at 750 to 1100 ° C. for 1 minute to 300 minutes. will be.
또한, 본 발명은,In addition, the present invention,
그 편면 또는 양면에 조성이 Ni: 20~90wt%, Fe:80~10wt%인 Ni-Fe합금 도금층이 1㎛~1mm의 두께로 형성되어 있고 Ni-Fe합금 자성상(magnetic phase)이 형성되어 있으며, 10~100Hz에서 20dB 이상의 차폐능을 나타내는 전자파 차폐용 니켈-철 합금 코팅강판에 관한 것이다.Ni-Fe alloy plating layers having a composition of 20 to 90 wt% Ni and 80 to 10 wt% Fe are formed on one or both sides thereof with a thickness of 1 μm to 1 mm, and a magnetic phase of Ni-Fe alloy is formed. The present invention relates to a nickel-iron alloy coated steel sheet for shielding electromagnetic waves at 10 to 100 Hz.
이하, 본 발명에 대하여 설명한다.EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated.
Ni-Fe합금은 그 조성에 따라 자기특성이 좌우되고, 결정자기 이방상수 및 자왜정수가 거의 0에 가까운 조성의 경우 dc 투자율이 크게는 수십만을 상회하는 우수한 재료이다. 그러나, 열처리 방법에 따라 그 특성이 크게 좌우될 뿐 아니라, 판매가가 약 3천만원/ton을 호가할 정도로 고가이며, 일부조성은 전량 수입에 의존하고 있어 수급체계에도 문제가 있다. 따라서, 차폐능은 우수하나 차폐재로서는 적합하지 못한 단점이 있다.Ni-Fe alloys are excellent materials whose magnetic properties depend on their composition, and the DC permeability is largely greater than hundreds of thousands in the case of the composition where the crystal anisotropy and magnetostriction constants are nearly zero. However, the characteristics of the heat treatment method greatly depends, and the selling price is about 30 million won / ton, which is expensive, and some of the composition depends on imports, which causes problems in the supply and demand system. Therefore, there is a disadvantage that the shielding performance is excellent but not suitable as a shielding material.
이에, 본 발명자들은, 상기한 Ni-Fe합금의 전자파 차폐능에는 미치지 못하지만, 차폐재로서 사용가능한 우수한 차폐능을 보유한 차폐강판을 값싸게 생산하는 방법에 대하여 연구 및 실험하여 본 발명을 완성시켰다. 즉, 본 발명은 냉연강판 표면상에 Ni-Fe합금을 통상의 전기도금에 의해 코팅하고 이를 열처리함으로써, 통상의 냉연강판에 특히 저주파 영역(수 Hz~100KHz)에서 우수한 전자파 차폐능을 갖도록 한 것이다.Thus, the present inventors have completed the present invention by researching and experimenting with a method of producing a shielded steel sheet having a good shielding ability which can be used as a shielding material, although it does not reach the electromagnetic shielding ability of the Ni-Fe alloy. That is, the present invention is to coat the Ni-Fe alloy on the surface of the cold-rolled steel sheet by conventional electroplating and heat treatment, so that the cold-rolled steel sheet has excellent electromagnetic shielding ability, especially in the low frequency region (several Hz ~ 100KHz). .
이하, 본 발명에 대하여 보다 상세히 설명한다.Hereinafter, the present invention will be described in more detail.
먼저, 냉연강판의 편면 또는 양면에 Ni-Fe합금 도금층을 형성하는데, Ni-Fe합금의 도금은 통상의 전기도금을 이용할 수 있다. 상기 Ni-Fe합금의 조성은 우수한 전자파 차폐능을 발현할 수 있는 조성범위인 Ni: 20~90wt%, Fe: 80~10wt%인 것이 바람직하며, 보다 바람직하게는 Ni이 78~80wt%인 것이다. 또한, 상기 Ni-Fe합금 도금층은 두께가 1㎛~1mm인 것이 바람직한데 그 이유는, 상기 Ni-Fe합금 도금층의 두께가 1㎛ 미만인 경우에는 코팅층에 의해 발현되는 전자파 차폐능이 미미하고, 1mm보다 두꺼워지면 표면에 크랙이 발생하여 오히려 차폐능이 감소하고 코팅층이 박리할 수 있기 때문이다.First, a Ni-Fe alloy plating layer is formed on one side or both sides of a cold rolled steel sheet, and plating of the Ni-Fe alloy may use conventional electroplating. The composition of the Ni-Fe alloy is preferably in the range of 20 to 90 wt% Ni, 80 to 10 wt% Fe, which is capable of expressing excellent electromagnetic shielding ability, and more preferably, Ni is 78 to 80 wt%. . The Ni-Fe alloy plating layer preferably has a thickness of 1 μm to 1 mm. The reason is that when the thickness of the Ni-Fe alloy plating layer is less than 1 μm, the electromagnetic wave shielding ability expressed by the coating layer is insignificant, and the thickness is less than 1 mm. This is because thickening may cause cracks on the surface, thereby reducing the shielding ability and causing the coating layer to peel off.
상기와 같이 Ni-Fe합금 도금층이 형성된 강판은 그 자체로도 차폐능을 발휘하지만, 본 발명은 상기 강판에 열처리를 실시함으로써 보다 우수한 전자파 차폐능을 제공하였다. 즉, 상기 강판에 대하여 750~1100℃에서 1~300분 유지하는 열처리를 실시하면, Ni과 Fe이 결합하여 자구(magnetic domain)를 형성함으로써 차폐능을 발휘하는 것이다. 이 때, 열처리 온도가 750℃ 미만이거나 열처리시간이 1분 미만인 경우에는 자구의 형성이 미약하고, 열처리온도가 1100℃ 이상이거나 열처리시간이 300분 이상인 경우에는 차폐능은 향상할 수 있지만, 비용이 증가하고 강판의 연화현상(softening)을 유발하여 경도를 저하시킬 수 있는 문제가 있다.As described above, the steel sheet on which the Ni-Fe alloy plating layer is formed exhibits a shielding ability in itself, but the present invention provides a better electromagnetic shielding ability by subjecting the steel sheet to heat treatment. That is, when the heat treatment is performed for 1 to 300 minutes at 750 ~ 1100 ℃ for the steel sheet, Ni and Fe combine to form a magnetic domain (magnetic domain) to exhibit the shielding ability. At this time, when the heat treatment temperature is less than 750 ℃ or the heat treatment time is less than 1 minute, the formation of magnetic domains is weak, and when the heat treatment temperature is 1100 ℃ or more or the heat treatment time is 300 minutes or more, the shielding ability can be improved, but the cost is high. There is a problem that can increase the hardness and cause softening (softening) of the steel sheet.
한편, 본 발명에서 기판으로 사용되는 냉연강판은 특히 한정하지 않으며, 통상의 냉연강판을 사용할 수 있다.On the other hand, the cold rolled steel sheet used as a substrate in the present invention is not particularly limited, it can be used a common cold rolled steel sheet.
이하, 실시예를 통하여 본 발명을 보다 상세히 설명한다.Hereinafter, the present invention will be described in more detail with reference to Examples.
(실시예 1)(Example 1)
C: 0.02중량% 이하 함유되고 크기가 200mm x 100mm x 1mm인 냉연강판의 편면에 Ni-Fe합금 전기도금을 행하였다. 전기도금은 약 400ℓ부피의 도금조에 NaCl 30g/ℓ, NiCl26H2O 109g/ℓ, FeSO46H2O 4g/ℓ, 계면활성제 7g/ℓ첨가하고, 45℃에서 PH 2.0~2.5, 전류밀도 5~15A/dm2로 하여 실시하였다. 도금후 도금층의 조성은 Ni: 약 50wt%, Fe: 약 50wt%였으며 도금층의 두께는 약 10㎛이었다.C: Ni-Fe alloy electroplating was performed on one side of a cold rolled steel sheet containing 0.02 wt% or less and having a size of 200 mm x 100 mm x 1 mm. Electroplating is added about 400l volume plating bath with NaCl 30g / l, NiCl 2 6H 2 O 109g / l, FeSO 4 6H 2 O 4g / l, surfactant 7g / l, PH 2.0 ~ 2.5, current density at 45 ℃ It carried out by 5-15A / dm <2> . After plating, the composition of the plating layer was about 50 wt% of Ni and about 50 wt% of Fe, and the thickness of the plating layer was about 10 μm.
상기와 같이 본 발명에 따라 Ni-Fe합금 도금층이 형성된 냉연강판과, Ni-Fe합금 도금을 실시하지 않은 일반 냉연강판에 대하여, 불활성분위기하 1100℃에서 약 60분 유지하는 열처리를 실시한 후 냉각하여 시편을 제작하였는데, 이 때, 도금시편의 경우는 실험의 재현성을 위하여 동일한 도금조건으로 시편을 3개 제작하였다.As described above, the cold rolled steel sheet having the Ni-Fe alloy plated layer formed thereon and the general cold rolled steel sheet not subjected to Ni-Fe alloy plating were subjected to a heat treatment for about 60 minutes at 1100 ° C. under an inert atmosphere, followed by cooling. At this time, in the case of plated specimens, three specimens were prepared under the same plating conditions for the reproducibility of the experiment.
그 다음, 이와 같이 하여 제작된 본 발명의 도금시편들인 발명재(1), 통상의 냉연강판에 도금을 실시하지 않고 본 발명의 열처리만을 실시한 비교재(1), 그리고 통상의 냉연강판인 비교재(2)에 대하여, 차폐능을 측정하고 그 결과를 도 1에 나타내었다. 이 때, 차폐능은 ASTM A698-74에 규정된 시험법에 의거하여 측정하였다.Next, the invention material (1), which is the plating specimens of the present invention produced in this way, the comparative material (1) which performed only the heat treatment of the present invention without plating on a common cold rolled steel sheet, and a comparative cold rolled steel sheet For (2), the shielding ability was measured and the results are shown in FIG. At this time, the shielding ability was measured according to the test method specified in ASTM A698-74.
도1에 나타난 바와 같이, 발명재(1)의 차폐능은 일반 냉연강판인 비교재(2)에 비해 10~100Hz에서 최고 약 8dB정도 증가하였고, 열처리만을 실시한 냉연기판인 비교재(1) 보다는 약 3.5dB 정도 증가한 것을 알 수 있다. 이것으로부터, 열처리는 차폐능 향상에 큰 기여를 하는 것을 추정할 수 있다.As shown in Figure 1, the shielding ability of the invention material (1) is up to about 8dB at 10 ~ 100Hz compared to the comparative material (2), which is a common cold rolled steel sheet, compared to the comparative material (1) which is only a cold-rolled substrate subjected to heat treatment only It can be seen that the increase of about 3.5dB. From this, it can be estimated that heat treatment greatly contributes to the improvement of shielding ability.
한편, 본 발명의 조건으로 제조한 3개의 시편이 거의 유사한 차폐능을 나타내는 것을 도 1을 통해 알 수 있기 때문에, 본 발명의 재현성 또한 입증되었다.On the other hand, since it can be seen from Figure 1 that the three specimens prepared under the conditions of the present invention show almost similar shielding ability, the reproducibility of the present invention was also demonstrated.
(실시예 2)(Example 2)
실시예 1에서 사용한 도금조건으로 Ni-Fe합금이 도금된 냉연강판에 대하여 열처리온도를 650℃, 750℃로 변화시켜 열처리를 실시한 후, 차폐능을 측정하고 그 결과를 각각 도 2 및 도 3에 나타내었다. 이 때, 열처리온도를 650℃로 하여 제작한 시편은 비교재(3), 750℃로 하여 제작한 시편은 발명재(2)로 하였다. 또한, 미도금시편에 대해서도 열처리온도를 650℃, 750℃로 변화시키는 열처리를 실시하였고, 이와 같이 하여 제조된 시편을 각각 비교재(4), 비교재(5)로 하였다. 또한, 도 2 및 도 3에 있어서, 비교재(1)은 실시예 1의 것과 동일한 시편이다.After the heat treatment was performed by changing the heat treatment temperature to 650 ° C and 750 ° C for the cold rolled steel plate plated with Ni-Fe alloy under the plating condition used in Example 1, the shielding ability was measured and the results are shown in FIGS. 2 and 3, respectively. Indicated. At this time, the specimen produced at a heat treatment temperature of 650 ° C. was used as the comparative material (3) and the specimen produced at 750 ° C. was used as the invention material (2). In addition, the unplated specimens were subjected to a heat treatment in which the heat treatment temperatures were changed to 650 ° C. and 750 ° C., and the specimens prepared in this way were used as the comparative material 4 and the comparative material 5, respectively. In addition, in FIG. 2 and FIG. 3, the comparative material 1 is the same specimen as Example 1. FIG.
먼저, 도 2는 열처리 온도를 650℃로 한 경우의 차폐능을 나타낸 그래프로서, 도 2에 나타난 바와 같이, 본 발명의 코팅처리를 실시했지만 열처리 온도를 650℃로 낮게 하여 제작한 비교재(3)의 경우, 미도금시편을 650℃로 열처리한 비교재(4) 또는 통상의 냉연강판인 비교재(2)에 비해서는 차폐능이 우수하나, 70Hz 이상의 주파수에서 차폐능이 비교재(4)보다도 저하하는 것을 알 수 있다. 즉, 열처리온도가 650℃로 낮은 경우에는, Ni-Fe코팅층에서 발현되는 차폐특성의 기여가 거의 없고, 시편에 유기된 응력에 의해 차폐능이 오히려 감소한다.First, FIG. 2 is a graph showing shielding ability when the heat treatment temperature is set at 650 ° C., and as shown in FIG. 2, the comparative material produced by lowering the heat treatment temperature at 650 ° C. although the coating treatment of the present invention was performed (3) ), The shielding performance is superior to that of the comparative material (4) heat-treated at 650 ° C. or the comparative material (2), which is a common cold rolled steel sheet, but the shielding performance is lower than that of the comparative material (4) at a frequency of 70 Hz or higher. I can see that. That is, when the heat treatment temperature is low at 650 ° C., there is little contribution of the shielding property expressed in the Ni—Fe coating layer, and the shielding ability is rather reduced by the stress induced in the specimen.
한편, 열처리를 750℃에서 실시한 경우에 대한 차폐능 측정결과를 나타내는 도 3에 따르면, 발명재(2)는, 통상의 냉연강판인 비교재(2)에 비해서는 우수한 차폐능을 나타내고, 미도금시편을 열처리한 비교재(5)에 비해 비록 차폐능의 개선 정도가 미미하기는 하지만 다소 증가하는 경향을 보이는 것을 알 수 있다. 이것은 열처리온도가 750℃ 이상인 경우, Ni-Fe코팅층이 차폐능 향상에 기여하기 때문인 것으로 생각할 수 있다.On the other hand, according to FIG. 3 which shows the measurement result of the shielding ability at the time of heat processing at 750 degreeC, the invention material 2 shows the shielding ability excellent compared with the comparative material 2 which is a normal cold rolled steel plate, and is unplated. Compared with the comparative material 5 heat-treated the specimen, although the degree of improvement of the shielding performance is insignificant, it can be seen that it tends to increase somewhat. This may be considered to be because the Ni-Fe coating layer contributes to the shielding performance improvement when the heat treatment temperature is 750 ° C or higher.
상기한 바와 같은 본 발명에 의하면, 용이한 제조방법을 이용해 저비용으로 우수한 전자파 차폐능을 제공하는 강판을 제작하고, 이를 가전기기, 자동차, 및 통신기기 등에 적용할 수 있는 효과가 있는 것이다.According to the present invention as described above, by using an easy manufacturing method to produce a steel sheet providing excellent electromagnetic shielding ability at a low cost, there is an effect that can be applied to home appliances, automobiles, and communication equipment.
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