KR20050097571A - Method for manufacturing black surface-treated copper foil for emi shield - Google Patents
Method for manufacturing black surface-treated copper foil for emi shield Download PDFInfo
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- KR20050097571A KR20050097571A KR1020040022642A KR20040022642A KR20050097571A KR 20050097571 A KR20050097571 A KR 20050097571A KR 1020040022642 A KR1020040022642 A KR 1020040022642A KR 20040022642 A KR20040022642 A KR 20040022642A KR 20050097571 A KR20050097571 A KR 20050097571A
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- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0094—Shielding materials being light-transmitting, e.g. transparent, translucent
- H05K9/0096—Shielding materials being light-transmitting, e.g. transparent, translucent for television displays, e.g. plasma display panel
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/34—Anodisation of metals or alloys not provided for in groups C25D11/04 - C25D11/32
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/38—Chromatising
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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
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
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- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
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- 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
- C25D5/48—After-treatment of electroplated surfaces
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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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
- H05K3/384—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by plating
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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
- H05K9/0084—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising a single continuous metallic layer on an electrically insulating supporting structure, e.g. metal foil, film, plating coating, electro-deposition, vapour-deposition
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
- C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
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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
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/0213—Electrical arrangements not otherwise provided for
- H05K1/0216—Reduction of cross-talk, noise or electromagnetic interference
- H05K1/0218—Reduction of cross-talk, noise or electromagnetic interference by printed shielding conductors, ground planes or power plane
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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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/03—Conductive materials
- H05K2201/0332—Structure of the conductor
- H05K2201/0335—Layered conductors or foils
- H05K2201/0355—Metal foils
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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
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
- H05K2203/0703—Plating
- H05K2203/0723—Electroplating, e.g. finish plating
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Abstract
본 발명은 반사율이 낮고 외관에 얼룩이 없으며 잔사(殘渣)가 거의 없는 균일한 외관을 가지는 전자파 차폐용 흑화표면처리 동박의 제조방법 및 그 동박에 관한 것으로서,The present invention relates to a method for producing a blackening surface-treated copper foil for electromagnetic wave shielding and a copper foil having a uniform appearance with low reflectance, no uneven appearance and little residue.
그 제조방법은, Co 또는 Co 를 포함하는 2원계 이상의 전해도금욕에서 도금을 행하여 동박의 표면에 Co을 포함하는 흑화도금층을 형성하는 단계와;The manufacturing method includes the steps of plating in a binary or higher electroplating bath containing Co or Co to form a blackening plating layer containing Co on the surface of the copper foil;
염기성 전해욕에서 상기 동박을 양극으로 배치하여 전기분해함으로써, 상기 흑화도금층의 표면을 산화시키는 단계와;를 포함하는 것을 특징으로 한다.And oxidizing the surface of the blackening plating layer by placing the copper foil as an anode in a basic electrolytic bath and electrolyzing the same.
상기 방법에 의하여 제조된 표면처리동박은, 반사율이 낮은 흑색의 외관을 가지므로, PDP 표시화면의 휘도를 저하시키지 않는다는 장점이 있다.Since the surface-treated copper foil manufactured by the above method has a black appearance with low reflectance, there is an advantage that the luminance of the PDP display screen is not lowered.
또한, 본 발명에 의한 표면처리동박은 흑색의 외관을 가지면서도, 외관에 얼룩 및 잔사(殘渣)가 거의 없는 균일한 외관을 가지므로, 이를 이용하여 제조된 전자파 차폐체용 복합재료의 불량률이 현저히 낮아지며, 상기 복합재료를 사용하여 제조된 PDP 표시화면의 외관이 우수하게 되는 효과가 있다.In addition, since the surface-treated copper foil according to the present invention has a black appearance and a uniform appearance with almost no stains and residues on the appearance, the defective rate of the composite material for electromagnetic wave shields manufactured using the same is significantly lowered. In addition, there is an effect that the appearance of the PDP display screen manufactured using the composite material is excellent.
Description
본 발명은 반사율이 낮고 외관에 얼룩이 없으며 잔사(殘渣)가 거의 없는 균일한 외관을 가지는 전자파 차폐용 흑화표면처리 동박의 제조방법과 그 표면처리동박에 관한 것이다.The present invention relates to a method for producing a blackened surface-treated copper foil for shielding electromagnetic waves and a surface-treated copper foil having a uniform reflectance with low reflectance, no uneven appearance and little residue.
플라즈마 디스플레이 패널(PDP)은 화상 표시면으로부터 인체에 유해한 강력한 전자파를 방사하기 때문에 전자파 차폐체를 설치하여 전자파의 방사를 방지할 필요가 있다. 전자파 차폐체로서는 동(銅)회로를 예컨대 PET 등과 같은 절연성 투명기재에 적층시켜 제조한 복합재료가 사용되고 있는데, 상기 복합재료는 전자파 방사의 방지 능력과 광선 투과성이 우수한 장점이 있다. 구체적으로 상기 복합재료는 소정의 표면조도를 가지는 동박(copper foil)을 상기 투명기재에 적층하고, 에칭에 의하여 불필요한 동박을 제거하여 원하는 동회로를 형성함으로써 제조된다. 동회로의 선폭과 패턴은 필요로 하는 전자파 방사 능력과 광선의 투과성을 근거로 선택된다. Since the plasma display panel (PDP) radiates powerful electromagnetic waves harmful to the human body from the image display surface, it is necessary to provide electromagnetic shielding to prevent radiation of electromagnetic waves. As the electromagnetic shielding body, a composite material manufactured by laminating a copper circuit on an insulating transparent substrate such as PET is used. The composite material has an advantage of preventing electromagnetic radiation and excellent light transmittance. Specifically, the composite material is manufactured by laminating a copper foil having a predetermined surface roughness on the transparent substrate, and removing unnecessary copper foil by etching to form a desired copper circuit. The line width and pattern of the copper circuit are selected based on the required electromagnetic radiation capability and light transmittance.
그런데, 상기 동회로가 외광을 반사하면 표시화면의 휘도(brightness)를 저하시키는 문제가 있다. 따라서, 전자파 차폐용 동박으로서는, 흑색에 가깝도록 표면처리되어 낮은 반사율을 가지는 동박이 선호되고 있다.However, when the copper circuit reflects external light, there is a problem of lowering the brightness of the display screen. Therefore, as an electromagnetic shielding copper foil, the copper foil which has surface treatment so that it is close to black and has a low reflectance is preferable.
하지만, 표면처리된 동박의 표면이 흑색에 가까울수록, 그 외관에 얼룩이 발생하기 쉬워지거나, 표면으로부터 분말이 묻어나오는 등 잔사가 발생하기 쉬워지는 경향이 있다. 동박 표면의 얼룩은 PDP의 화질을 떨어뜨리며, 잔사는 에칭되어 투명기재가 드러나야 할 부분에 떨어져서 광선의 투과성을 떨어뜨리므로, PDP 해상도가 전반적으로 저하되는 단점이 있다.However, the closer the surface of the surface-treated copper foil is to black, the more likely stains are likely to appear on the appearance, or the residue tends to be generated such as powders from the surface. The stain on the surface of the copper foil degrades the quality of the PDP, and the residue is etched and falls on the portion where the transparent substrate is to be exposed, thereby reducing the light transmittance.
이 때문에, 종래에는 동박의 표면을 완전한 흑색으로 하지 않고, 흑색에 가까운 초콜렛색이나 어두운 금속색을 가지도록 표면처리하는 방향으로 주로 연구가 행해지고 있다. 그러나, 상기와 같은 방법으로 제조된 동박의 표면은 완전한 흑색이 아니므로, 전자파 차폐용 동박으로서의 반사율 개선에는 한계가 있었다. For this reason, conventionally, research is mainly performed in the direction which surface-treats so that the surface of copper foil may be made into the chocolate color and dark metal color which are close to black, without making completely black. However, since the surface of the copper foil manufactured by the above method is not completely black, the reflectance improvement as an electromagnetic shielding copper foil had a limit.
본 발명은 흑색의 외관을 가져서 반사율이 낮은 전자파 차폐용 흑화표면처리 동박및 그 제조방법을 제공하는 것을 목적으로 한다.An object of the present invention is to provide a blackening surface-treated copper foil for shielding electromagnetic waves having a black appearance and low reflectance, and a method of manufacturing the same.
또한, 본 발명은 흑색의 외관을 가지면서도, 얼룩 및 잔사(殘渣)가 거의 없는 균일한 외관을 가지는 전자파 차폐용 흑화표면처리 동박 및 그 제조방법을 제공하는 것을 목적으로 한다.Moreover, an object of this invention is to provide the blackening surface-treated copper foil for electromagnetic wave shield which has black external appearance, and has a uniform external appearance with few stains and residues, and its manufacturing method.
또한, 본 발명의 또 다른 목적은, 박리강도(peel strength)가 우수한 전자파 차폐용 흑화표면처리 동박 및 그 제조방법을 제공하는 데에 있다.Further, another object of the present invention is to provide a blackening surface-treated copper foil for shielding electromagnetic waves excellent in peel strength and a method of manufacturing the same.
상기 목적을 달성하기 위한, 본 발명에 따른 전자파 차폐용 흑화표면처리 동박의 제조방법은,The manufacturing method of the blackening surface-treated copper foil for electromagnetic wave shield which concerns on this invention to achieve the said objective,
Co 또는 Co를 포함하는 2원계 이상의 전해도금욕에서 도금을 행하여 동박의 표면에 Co를 포함하는 흑화도금층을 형성하는 단계와;Performing plating in a binary or higher electroplating bath containing Co or Co to form a blackening plating layer containing Co on the surface of the copper foil;
염기성 전해욕에서 상기 동박을 양극으로 배치하여 전기분해함으로써, 상기 흑화도금층의 표면을 산화시키는 단계와;를 포함하는 것을 특징으로 한다.And oxidizing the surface of the blackening plating layer by placing the copper foil as an anode in a basic electrolytic bath and electrolyzing the same.
상기 흑화도금층을 형성하기 전에, 동박의 표면에 미세 동입자층을 석출 형성시키는 단계를 더 포함하는 것이 바람직하다.Before forming the blackening plating layer, it is preferable to further include depositing a fine copper particle layer on the surface of the copper foil.
또한, 상기 산화된 흑화도금층의 표면에 전해 크로메이트층을 형성하는 단계를 더 포함하는 것이 바람직하다.In addition, it is preferable to further include the step of forming an electrolytic chromate layer on the surface of the oxidized blackening plating layer.
한편, 흑화도금층이 형성된 표면의 이면에 Zn 또는 Zn합금으로 구성된 도금 피막층을 형성하는 단계를 더 포함하는 것이 바람직하다.On the other hand, it is preferable to further comprise the step of forming a plated coating layer composed of Zn or Zn alloy on the back surface of the blackened plating layer is formed.
상기 염기성 전해욕의 pH는 10 이상인 것이 바람직하다.It is preferable that pH of the said basic electrolytic bath is 10 or more.
이하에서는, 본 발명에 대하여 자세하게 설명하기로 한다.Hereinafter, the present invention will be described in detail.
본 발명의 대상이 되는 전자파 차폐용 동박은 광폭 생산이 가능한 전해동박으로서 동박의 두께는 1 ~ 35㎛이고, 바람직한 것은 6 ~ 18㎛이다. 표면조도(Rz : DIN)는 0.1 ~ 2.0 ㎛이고, 바람직한 것은 0.5 ~ 1.5 ㎛이다. 표면조도가 0.1 ㎛보다 작은 경우 투명기재와의 접착성이 충분하지 않게 되어 전자파 차폐체의 신뢰성이 저하되고, 2.0 ㎛보다 큰 경우 에칭에 의하여 회로를 형성한 뒤에 동박이 접착되어 있는 투명기재의 표면의 요철이 크게 되어 이로 인하여 표시화면의 흐림이 커지게 됨으로 바람직하지 않다.Electromagnetic shielding copper foil which is the object of this invention is an electrolytic copper foil which can produce wide width, and thickness of copper foil is 1-35 micrometers, and 6-18 micrometers is preferable. Surface roughness (Rz: DIN) is 0.1-2.0 micrometers, and 0.5-1.5 micrometers are preferable. If the surface roughness is less than 0.1 μm, the adhesion with the transparent base material becomes insufficient, and the reliability of the electromagnetic wave shield decreases. If the surface roughness is larger than 2.0 μm, the surface of the transparent base material on which the copper foil is bonded after forming a circuit by etching is formed. It is not preferable that the unevenness becomes large, thereby increasing the blurring of the display screen.
본 발명의 주된 특징은, 흑색표면처리된 동박을 염기성 전해욕에서 산화처리함으로써, 동박 표면을 흑색으로 하면서도 얼룩 또는 잔사가 발생하지 않는 균일한 외관의 흑화표면처리 동박을 얻을 수 있다는데 있다.The main feature of the present invention is that, by oxidizing the black surface-treated copper foil in a basic electrolytic bath, it is possible to obtain a blackened surface-treated copper foil having a uniform appearance in which the copper foil surface is black while no stains or residues are generated.
동박의 흑화처리는, 흑색을 유발하는 금속이 포함된 전해도금욕에서 동박을 음극에 배치하고 상기 음극의 동박표면 상에 상기 금속 도금층을 석출시킴으로써 행해진다. 흑색을 유발한다고 알려진 금속으로는 Cu, Cr, Al, Co 등이 있으나, Cu는 완전한 흑색을 도출할 수 있으나 추후 동박회로패턴 형성시 동박회로 쪽으로 침투하여 회로패턴을 손상시키는 문제가 있고, Cr은 동박회로 형성시의 에칭성에 문제를 일으키기 때문에 본 발명에 적용하기 어렵다. 또한, Al은 그 금속특성상 후술하는 양극산화처리가 가능하지 않다. 따라서, 제품손상방지, 제조공정상의 문제점및 양극산화처리의 효율성 등을 고려하면, Co가 가장 적당한 금속이다. The blackening process of copper foil is performed by arrange | positioning copper foil to a cathode in the electroplating bath containing the metal which causes black, and depositing the said metal plating layer on the copper foil surface of the said cathode. Metals known to cause black include Cu, Cr, Al, and Co, but Cu may lead to complete black, but there is a problem of damaging the circuit pattern by penetrating into the copper foil circuit when forming the copper foil circuit pattern. Since the problem arises in the etching property at the time of copper foil circuit formation, it is difficult to apply to this invention. In addition, Al cannot be anodized as described later due to its metal properties. Therefore, in consideration of product damage prevention, manufacturing process problems, and anodizing efficiency, Co is the most suitable metal.
Co의 흑화도금은 예컨대 Ir 전극을 양극으로 사용하고, 음극을 동박으로 하여 한계전류밀도 이상의 전류에서 도금을 행함으로써 이루어지며, 동박 표면에 형성된 Co 흑화도금층은 Co3O4, CoOOH, CoO와 같은 산화물의 형태로 되어 있다.Blackening of the Co-coated, for example is made by carrying out plating at a current more than the limiting current density using the Ir electrode as an anode and to the cathode of a copper foil, Co blackening the coating layer formed on the copper foil surface, such as Co 3 O 4, CoOOH, CoO It is in the form of an oxide.
전해도금욕에 포함되는 Co의 농도는 1 ~ 80 g/l에서 선택할 수 있으나, 가장 효율좋게 흑화도금층이 형성될 수 있는 농도는 10 ~ 30 g/l이다. 공업적으로 경제적인 도금욕의 전류밀도는 0.1 ~ 60 A/dm2이고, 특히 5 ~ 25 A/dm2의 전류밀도가 바람직하다. 또한, 도금시간은 1 ~ 20초 범위에서 가능하나, 전류밀도, 전해액 농도 등을 고려하여 상기 범위 이외도 가능하다.The concentration of Co included in the electroplating bath may be selected from 1 to 80 g / l, but most efficiently, the concentration of blackening plating layer may be 10 to 30 g / l. The current density of the industrially economical plating bath is 0.1-60 A / dm 2 , particularly preferably 5-25 A / dm 2 . In addition, the plating time may be in the range of 1 to 20 seconds, but may be out of the range in consideration of the current density, the electrolyte concentration, and the like.
한편, 동박의 박리강도 향상이나 동박에 다른 특성을 부가하기 위하여 Co 외의 다른 금속성분도 전해욕에 포함시킬 수 있다. 동박의 특성을 해치지 않고, 박리강도를 향상시키는 원소로서 Ni, Fe가 적당하다. 상기 금속성분과 Co를 합친 전해액 중의 금속성분농도도 1 ~ 80 g/l 범위에 있는 것이 도금 효율성 측면에서 바람직하다.On the other hand, in order to improve the peeling strength of copper foil and to add other characteristics to copper foil, other metal components other than Co can also be included in an electrolytic bath. Ni and Fe are suitable as an element which improves peeling strength, without impairing the characteristic of copper foil. It is preferable from the viewpoint of plating efficiency that the metal component concentration in the electrolyte solution in which the metal component and Co are combined is in the range of 1 to 80 g / l.
흑화도금층이 형성된 동박은 표면에 도금입자층이 노듈(nodule)모양으로 석출된 상태이다. 그런데, 도금입자층이 형성된 동박의 표면조도는 전체적으로는 전자파 차폐용 동박으로 사용가능한 범위 내에 있지만, 미시적으로 그 표면을 살펴보면 동박의 표면조건 또는 도금조건 등에 따라 동박의 표면에 석출되는 노듈입자의 크기나 수가 부분적으로 차이가 있게 된다. 또한, 석출반응에 의하여 음극에서는 수소가 발생하게 되는데, 이러한 수소가 발생하는 부분의 도금두께는 나머지 부분의 두께와 미세한 차이를 보인다.The copper foil in which the blackening plating layer was formed is a state in which the plating particle layer precipitated in the shape of a nodule on the surface. By the way, although the surface roughness of the copper foil in which the plated particle layer is formed is generally within the range that can be used as the electromagnetic shielding copper foil, microscopically looking at the surface thereof, the size of the nodule particles deposited on the surface of the copper foil according to the surface conditions or plating conditions of the copper foil, The number is partially different. In addition, hydrogen is generated in the cathode by the precipitation reaction, and the plating thickness of the hydrogen-producing portion shows a slight difference from the thickness of the remaining portion.
이 때문에 전체 동박표면을 조망하였을 때, 주위부에 비하여 입자크기나 입자수가 상대적으로 차이가 크거나, 수소발생태양이 다른 부분은 얼룩으로 보이게 된다. 또한, 아주 미세한 입자의 경우, 동박의 제조과정 중에 표면으로부터 탈락되어 잔사가 되어 동박 품질을 떨어뜨린다. For this reason, when the entire copper foil surface is viewed, the portion where the particle size and number of particles are relatively different or the hydrogen-generating sun is different from the surrounding portion appear as spots. In addition, in the case of very fine particles, they fall off the surface during the manufacturing process of the copper foil and become a residue, which degrades the copper foil quality.
본 발명은, 이러한 문제를 해결하기 위하여, 흑화도금층이 형성된 동박을 염기성 전해욕에 양극으로 배치하고, 흑화도금층의 표면을 산화(부식)시켜 일정 정도 평탄화함으로써, 얼룩, 잔사의 발생을 극력 저감하고 있다.In order to solve this problem, the present invention is to arrange a copper foil having a blackening plated layer as an anode in a basic electrolytic bath, to oxidize (corrode) the surface of the blackening plated layer to planarize to a certain extent, thereby reducing the occurrence of stains and residues as much as possible. have.
흑화도금층을 양극산화처리하는 경우의 장점은, 흑화도금층 표면을 전해액이 전후좌우방향으로 균일한 플로우(flow)로 흐르면서 그 표면을 고르게 부식시킨다는 점에 있다. An advantage of anodizing the black plating layer is that the surface of the black plating layer is corroded evenly while the electrolyte flows in a uniform flow in the front, rear, left and right directions.
양극산화전해욕은 NaOH, KOH 등과 같은 염기성 용액으로 구성된 염기성 전해용이며, 양극 산화시의 바람직한 전류 밀도는 1 ~ 30 A/dm2, 시간은 1 ~ 20초에서 선택할 수 있다. 상기 전류밀도 및 시간은 전해액의 종류, 조성 및 온도 등에 따라 달라질 수 있다. 양극산화는 예컨대 스테인레스 스틸을 음극으로 사용하고, 양극에 흑화표면처리된 동박을 배치하여 행해진다.The anodic oxidation bath is for basic electrolysis consisting of a basic solution such as NaOH, KOH, etc., and the preferred current density at the time of anodic oxidation can be selected from 1 to 30 A / dm 2 and the time from 1 to 20 seconds. The current density and time may vary depending on the type, composition and temperature of the electrolyte. Anodization is performed by, for example, using stainless steel as a cathode and arranging blackened surface-treated copper foil on the anode.
양극산화처리에 있어서 중요한 점은, 염기성 전해욕의 pH조정이다. 얼룩, 잔사를 효과적으로 제거하기 위해서는, 전해욕의 pH가 적어도 10 이상이어야 하며, 본 출원인의 실험결과에 의하면, pH 13에서 가장 바람직한 결과를 나타내었다.An important point in the anodic oxidation treatment is the pH adjustment of the basic electrolytic bath. In order to effectively remove stains and residues, the pH of the electrolytic bath should be at least 10, and according to the results of the applicant's experiment, the most preferable result was shown at pH 13.
한편, 반사율을 작게 하고 또한 투명기재와의 접착성을 향상시키기 위해 흑화도금을 행하기 전에, 동박의 표면에 미세 동입자층을 석출부착시킬 수 있다. 석출된 동입자는 앵커(anchor)역할을 하여 투명기재에 동박을 적층시킬 때 박리강도를 상승시켜 접착성을 향상시키며, 외광을 난반사시켜 반사율을 떨어뜨린다.On the other hand, the fine copper particle layer can be deposited and deposited on the surface of the copper foil before the blackening is performed in order to reduce the reflectance and improve the adhesion with the transparent substrate. Precipitated copper particles act as anchors to increase the peel strength when laminating copper foil on a transparent substrate, and improve adhesion, and diffuse reflection of external light to reduce reflectance.
미세 동입자층의 형성은 프린트배선판용 동박에 사용되는 조화(粗化)처리를 이용하여 행할 수 있다. 조화처리는 황산동 도금욕에서 행하는 것이 보통이며, 조화처 시의 동입자 부착량은 0.1 ~ 10 g/㎡ 범위가 바람직하다. 상기 범위를 하회(조도 하강)하면 반사율은 낮아지지만 박리강도(접착성)가 떨어지며, 상기 범위를 상회(조도 상승)하면 역으로 박리강도는 높아지지만 반사율이 높아지기 때문이다.Formation of a fine copper particle layer can be performed using the roughening process used for the copper foil for printed wiring boards. The roughening treatment is usually carried out in a copper sulfate plating bath, and the copper particle adhesion amount at the time of roughening is preferably in the range of 0.1 to 10 g / m 2. This is because if the above range is lowered (roughness lowering), the reflectance is lowered but the peeling strength (adhesiveness) is lowered.
미세 동입자층 형성, 흑화도금층 형성 및 양극산화처리 시의 3공정에 걸쳐서 표면조도는 Rz(DIN 규격)로 0.1 ~ 2.0 ㎛이내로 유지되어야 한다. 그 이유는 상술한 바와 같다. 상술한 흑화도금조건, 양극산화조건의 범위 내에서 표면처리할 경우 표면조도를 상기 범위 이내로 유지할 수 있다.The surface roughness should be maintained within 0.1 to 2.0 μm in Rz (DIN standard) throughout the three processes of forming the fine copper particle layer, forming the blackened plating layer, and anodizing. The reason is as described above. When surface treatment is performed within the range of the above blackening plating conditions and anodization conditions, the surface roughness can be maintained within the above range.
한편, 본 발명의 동박에 전해 크로메이트(chromate)처리 등의 방청처리를 할 수 있다. 또한, 흑화 도금을 행하지 않은 쪽의 표면에 Zn 또는 Zn 합금으로 이루어진 도금 피막을 형성하면, 전자파 차폐체 제조를 위한 가열공정에서 가열 변색을 방지할 수 있다.On the other hand, the copper foil of this invention can be subjected to rust prevention treatment such as electrolytic chromate treatment. In addition, when a plating film made of Zn or Zn alloy is formed on the surface of the non-blackened plating surface, heat discoloration can be prevented in the heating step for producing the electromagnetic wave shield.
이하, 본 발명을 실시예를 통하여 구체적으로 설명한다. 그러나, 아래의 실시예는 오로지 본 발명을 설명하기 위한 것으로, 본 발명의 요지에 따라 본 발명의 범위가 아래의 실시예에 국한되지 않는다는 것은 당업계에서 통상의 지식을 가진 자에게 자명할 것이다.Hereinafter, the present invention will be described in detail through examples. However, the following examples are only for illustrating the present invention, and it will be apparent to those skilled in the art that the scope of the present invention is not limited to the following examples according to the gist of the present invention.
실시예Example
실시예 1:Example 1:
표면조도(Rz)가 2 ㎛이하, 두께 10㎛인 전해동박을 100g/l 황산에서 5초동안 침지하고 산세처리 후 순수(純水)로 세척한 후에, 아래의 조건으로 흑화도금처리 및 양극산화처리를 하였다.An electrolytic copper foil having a surface roughness (Rz) of 2 μm or less and a thickness of 10 μm was immersed in 100 g / l sulfuric acid for 5 seconds, washed with pure water after pickling, and then subjected to blackening and anodizing under the following conditions. Was done.
흑화도금처리조건; 전해욕의 Co 금속이온 농도 18 g/l(Co는 황산코발트형태로 도금욕에 첨가됨), 완충액(H3BO3) 농도 30g/l, pH 3.5, 전해액의 온도 30 ℃, 전류밀도 20 A/dm2 , 도금 시간 4 초.Blackening plating treatment conditions; Co metal ion concentration of electrolytic bath 18 g / l (Co is added to the plating bath in the form of cobalt sulfate), buffer (H 3 BO 3 ) concentration 30 g / l, pH 3.5, electrolyte temperature 30 ℃, current density 20 A / dm 2 , plating time 4 seconds.
양극산화처리조건; NaOH 양극산화욕의 pH : 13, 양극산화욕 온도 : 70 ℃, 전류밀도 : 15 A/dm2, 산화처리시간 : 4 초.Anodizing conditions; PH of NaOH anodic oxidation bath: 13, anodic oxidation bath temperature: 70 ℃, current density: 15 A / dm 2 , oxidation time: 4 seconds.
실시예 2:Example 2:
동 부착량을 1.5g/㎡으로 하여 미세 동입자층을 형성하고, 실시예 1과 동일한 조건으로 흑화도금처리 및 양극산화처리를 하였다.The fine copper particle layer was formed with the copper adhesion amount as 1.5 g / m <2>, and blackening plating process and anodizing process were performed on the conditions similar to Example 1.
실시예 3:Example 3:
실시예 1과 동일한 조건으로 동박의 표면을 전처리한 후, 이하의 조건으로 흑화도금처리 및 양극산화처리를 행하였다.After the surface of the copper foil was pretreated under the same conditions as in Example 1, blackening plating treatment and anodizing treatment were performed under the following conditions.
흑화도금처리조건; Co 금속이온의 농도 10 g/l, Ni 금속이온농도 8 g/l,(Ni은 황산니켈형태로 도금욕에 첨가됨), 완충액(H3BO3) 농도 30g/l, pH 3.5, 전해액의 온도 30 ℃, 전류밀도 20 A/dm2 , 도금 시간 4 초.Blackening plating treatment conditions; Co metal ion concentration 10 g / l, Ni metal ion concentration 8 g / l, (Ni is added to the plating bath in the form of nickel sulfate), buffer (H 3 BO 3 ) concentration 30 g / l, pH 3.5, electrolyte Temperature 30 ℃, current density 20 A / dm 2 , plating time 4 seconds.
양극산화처리조건; NaOH 양극산화욕의 pH 13, 양극산화욕 온도 70 ℃, 전류밀도 15 A/dm2, 산화처리시간 4초.Anodizing conditions; PH 13 of the NaOH anodic oxidation bath, anodic oxidation bath temperature 70 ℃, current density 15 A / dm 2 , oxidation time 4 seconds.
실시예 4:Example 4:
실시예 2와 같은 조건으로 미세 동입자층을 형성한 후, 실시예 3과 동일한 조건으로 흑화도금처리 및 양극산화처리를 행하였다.After the fine copper particle layer was formed under the same conditions as in Example 2, blackening plating treatment and anodizing treatment were performed under the same conditions as in Example 3.
실시예 5: Example 5:
실시예 1과 동일한 조건으로 동박의 표면을 전처리한 후, 이하의 조건으로 흑화도금처리 및 양극산화처리를 행하였다.After the surface of the copper foil was pretreated under the same conditions as in Example 1, blackening plating treatment and anodizing treatment were performed under the following conditions.
흑화도금처리조건; Co 금속이온의 농도 10 g/l, Fe 금속이온의 농도 5 g/l(Fe는 황산철 형태로 도금욕에 첨가됨), 완충액(H3BO3) 농도 30g/l, pH 3.5, 전해액의 온도 30 ℃, 전류밀도 20 A/dm2, 도금 시간 4 초.Blackening plating treatment conditions; Co metal ion concentration 10 g / l, Fe metal ion concentration 5 g / l (Fe is added to the plating bath in the form of iron sulfate), buffer (H 3 BO 3 ) concentration 30 g / l, pH 3.5, electrolyte Temperature 30 ℃, current density 20 A / dm 2 , plating time 4 seconds.
양극산화처리조건; NaOH 양극산화욕의 pH 12, 양극산화욕 온도 70 ℃, 전류밀도 15 A/dm2, 산화처리시간 4초.Anodizing conditions; PH of NaOH anodic oxidation bath, anodic oxidation bath temperature 70 ℃, current density 15 A / dm 2 , oxidation time 4 seconds.
실시예 6:Example 6:
실시예 2와 같은 조건으로 미세 동입자층을 형성한 후, 실시예 5와 동일한 조건으로 흑화도금처리 및 양극산화처리를 행하였다.After the fine copper particle layer was formed under the same conditions as in Example 2, blackening plating treatment and anodizing treatment were performed under the same conditions as in Example 5.
비교예 Comparative example
상기 실시예와 동일한 조건으로 전해동박 표면을 전처리한 후, 아래의 조건으로 흑화처리도금을 실시하였다.After pretreatment of the surface of the electrolytic copper foil under the same conditions as in the above example, blackening treatment plating was performed under the following conditions.
Co 금속이온의 농도 20 g/l, pH 3.5, 전해액의 온도 30 ℃, 전류밀도 20 A/dm2, 도금 시간 4 초.Co metal ion concentration 20 g / l, pH 3.5, electrolyte temperature 30 deg. C, current density 20 A / dm 2 , plating time 4 seconds.
이하의 표는 상기 실시예 및 비교예에 따른 표면처리동박의 얼룩발생여부, 문지름에 의한 잔사발생(분락)여부, 박리강도를 측정한 결과를 나타낸 것이다.The following table shows the results of measuring the occurrence of staining of the surface-treated copper foil according to the Examples and Comparative Examples, the occurrence of residue (separation) by rubbing, and the peel strength.
[표][table]
얼룩의 정도 : △ 약간 존재, ▲ 없음Degree of dirt: △ little presence, ▲ no
잔사발생(문지름에 의한 분락) 정도 : ○ 미량, ● 없음Residue (separation due to rubbing) degree: ○ Trace amount, ● None
표에 도시된 바와 같이, 흑화도금처리만을 한 비교예는 표면 상에 얼룩과 잔사가 발생하고 있다. 그러나, 흑화도금처리 후에 양극산화처리를 한 본 발명 실시예는 얼룩 및 잔사가 발생하지 않음을 알 수 있다.As shown in the table, in the comparative example which only performed the blackening plating process, the stain and the residue generate | occur | produce on the surface. However, it can be seen that the embodiment of the present invention subjected to the anodizing treatment after the blackening plating treatment does not generate stains and residues.
또한, 흑화도금처리 전에 미세 동입자층을 형성시킨 실시예 2, 4, 6은, 미세 동입자층을 형성하지 않은 각 대응되는 조건의 실시예 1, 3, 5에 비하여 박리강도가 상승하였음을 알 수 있다. 또, 흑화도금층에 Ni과 Fe가 각각 추가적으로 포함된 실시예 3과 실시예 5가 상기 성분들이 포함되지 않은 실시예 1에 대해 더 높은 박리강도를 가짐을 알 수 있다.In addition, Examples 2, 4, and 6, in which the fine copper particle layer was formed before the blackening plating process, showed that the peeling strength was increased as compared with Examples 1, 3, and 5 in the corresponding conditions in which the fine copper particle layer was not formed. have. In addition, it can be seen that Example 3 and Example 5, in which Ni and Fe are additionally included in the blackened plating layer, have a higher peeling strength than Example 1, in which the above components are not included.
상기한 바와 같은 균일한 외관을 가지는 본 발명의 표면처리동박을 PET와 같은 절연성 투명기재에 적층하여 제조되는 복합재료로 전자파 차폐체를 제조하면, 표시화면의 해상도가 우수한 플라즈마 디스플레이 패널을 제조할 수 있으며, 그 불량률도 현저히 낮출수 있게 된다.When the electromagnetic shielding body is manufactured from a composite material prepared by laminating the surface-treated copper foil of the present invention having the uniform appearance as described above on an insulating transparent substrate such as PET, a plasma display panel having excellent display screen resolution can be manufactured. As a result, the failure rate can be significantly lowered.
이상에서 설명한 바와 같이, 본 발명의 제조방법에 의하여 제조된 표면처리동박은, 반사율이 낮은 흑색의 외관을 가지므로, PDP 표시화면의 휘도를 저하시키지 않는다는 장점이 있다.As described above, the surface-treated copper foil manufactured by the manufacturing method of the present invention has a black appearance with low reflectance, and thus has the advantage of not lowering the luminance of the PDP display screen.
또한, 본 발명에 의한 표면처리동박은 흑색의 외관을 가지면서도, 얼룩 및 잔사(殘渣)가 거의 없는 균일한 외관을 가지므로, 이를 이용하여 제조된 전자파 차폐체용 복합재료의 불량률이 현저히 낮아지며, 상기 복합재료를 사용하여 제조된 PDP 표시화면의 외관이 우수하게 되는 효과가 있다.In addition, since the surface-treated copper foil according to the present invention has a black appearance and has a uniform appearance with little stains and residues, the defective rate of the composite material for electromagnetic wave shields manufactured using the same is significantly lowered. There is an effect that the appearance of the PDP display screen manufactured using the composite material becomes excellent.
Claims (7)
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KR1020040022642A KR100603428B1 (en) | 2004-04-01 | 2004-04-01 | Method for manufacturing black surface-treated copper foil for EMI Shield |
JP2004150277A JP3869433B2 (en) | 2004-04-01 | 2004-05-20 | Method for producing blackened surface-treated copper foil for electromagnetic wave shielding |
PCT/KR2005/000951 WO2006004298A1 (en) | 2004-04-01 | 2005-03-31 | Method for manufacturing black surface-treated copper foil for emi shield |
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US6497806B1 (en) * | 2000-04-25 | 2002-12-24 | Nippon Denkai, Ltd. | Method of producing a roughening-treated copper foil |
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