JP2007531820A - Method for producing blackened surface-treated copper foil for electromagnetic wave shielding - Google Patents

Method for producing blackened surface-treated copper foil for electromagnetic wave shielding Download PDF

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JP2007531820A
JP2007531820A JP2007506086A JP2007506086A JP2007531820A JP 2007531820 A JP2007531820 A JP 2007531820A JP 2007506086 A JP2007506086 A JP 2007506086A JP 2007506086 A JP2007506086 A JP 2007506086A JP 2007531820 A JP2007531820 A JP 2007531820A
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copper foil
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JP4326019B2 (en
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ジョンホ リュ
スンリャン ジョン
サン ボム キム
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イルジン コッパー ホイル カンパニー リミテッド
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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
    • C—CHEMISTRY; METALLURGY
    • 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
    • C—CHEMISTRY; METALLURGY
    • 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
    • C25D11/38—Chromatising
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • H05K9/0094—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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Electroplating Methods And Accessories (AREA)

Abstract

本発明は、反射率が低く外観に斑が無く、残渣が殆ど無い均一な外観を有する電磁波遮蔽用黒化表面処理銅箔の製造方法及びその銅箔に関するものであって、電解メッキ浴に陰極として銅箔を配置し、前記銅薄箔の表面に黒化メッキ層を形成させることにより電磁波遮蔽用表面処理銅箔を製造する方法において、Ｃｏ及び陰極における水素発生を抑制する酸化剤を含む電解メッキ浴を使用して前記銅箔表面に黒色のＣｏ酸化物メッキ層を形成させることを特徴とする。
前記方法によって製造された表面処理銅箔は、反射率が低い黒色の外観を有するので、ＰＤＰ表示画面の輝度を低下させないという長所がある。
さらに、本発明による表面処理銅箔は黒色の外観を有しながらも、外観に斑及び残渣が殆どない均一な外観を有するので、これを利用して製造された電磁波遮蔽用複合材料の不良率が顕著に低くなり、前記複合材料を使用して製造されたＰＤＰ表示画面の外観が優秀になる効果がある。
【選択図】 なしThe present invention relates to a method for producing a blackened surface-treated copper foil for electromagnetic wave shielding having a uniform appearance with low reflectivity, no appearance and almost no residue, and to the copper foil, which is used as a cathode in an electrolytic plating bath. In the method of manufacturing a surface-treated copper foil for shielding electromagnetic waves by forming a copper foil as a surface and forming a blackened plating layer on the surface of the copper thin foil, electrolysis containing an oxidizing agent that suppresses hydrogen generation at Co and the cathode A black Co oxide plating layer is formed on the surface of the copper foil using a plating bath.
Since the surface-treated copper foil manufactured by the above method has a black appearance with a low reflectance, there is an advantage that the brightness of the PDP display screen is not lowered.
Furthermore, since the surface-treated copper foil according to the present invention has a black appearance but has a uniform appearance with few spots and residues on the appearance, the defective rate of the electromagnetic shielding composite material produced using this Is significantly reduced, and the appearance of the PDP display screen manufactured using the composite material is excellent.
[Selection figure] None

Description

この発明は、反射率が低く、外観に斑が無く、残渣が殆どない均一な外観を有する電磁波遮蔽用黒化表面処理銅箔の製造方法とその表面処理銅箔に関する。   The present invention relates to a method for producing a blackened surface-treated copper foil for shielding electromagnetic waves and having a uniform appearance with low reflectance, no appearance and no residue, and the surface-treated copper foil.

プラズマデイスプレーパネル（ＰＤＰ）は画像表示面から人体に有害な強力な電磁波を放射するため電磁波遮蔽体を設置して電磁波の放射を防止する必要がある。電磁波遮蔽体としては、銅回路を、例えば、ＰＥＴ等のような絶縁性透明基材に積層させて製造した複合材料が使用されているが、前記複合材料は電磁波放射防止能力と光線透過性が優れた長所がある。具体的に、前記複合材料は、所定の表面粗度を有する銅箔（copper foil）を前記透明基材に積層し、エッチングによって不必要な銅箔を除去して望む銅回路を形成することにより製造される。
銅回路の線幅とパターンは必要とする電磁波放射能力と光線の透過性を根拠に選択される。
ところが、前記銅回路が外観を反射すると表示画面の輝度（brightness）を低下させる問題がある。従って、電磁波遮蔽用銅箔としては、黒色に近いように表面処理され低い反射率を有する銅箔が選好されている。
しかしながら、表面処理された銅箔の表面が黒色に近いほど、その外観に斑が発生しやすくなるか、表面から粉末が付いて出る等残渣が発生しやすくなる傾向がある。銅箔表面の斑はＰＤＰの画質を劣らせ、残渣はエッチングされ透明基材が表れるべき部分に落ちて光線の透過性を劣らせるので、ＰＤＰ解像度が全般的に低下される短所がある。
このため、従来では銅箔の表面を完全に黒色にしないで、黒色に近いチョコレート色や暗い金属色を有するように表面処理する方向に主に研究が行われている。しかし、前記のような方法で製造された銅箔の表面は完全な黒色でないので、電磁波遮蔽用銅箔としての反射率の改善には限界があった。 Since a plasma display panel (PDP) emits a strong electromagnetic wave harmful to the human body from an image display surface, it is necessary to install an electromagnetic wave shield to prevent the emission of the electromagnetic wave. As the electromagnetic wave shielding body, a composite material produced by laminating a copper circuit on an insulating transparent base material such as PET is used. However, the composite material has an electromagnetic radiation prevention ability and light transmittance. There are excellent advantages. Specifically, the composite material is formed 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. Manufactured.
The line width and pattern of the copper circuit are selected based on the required electromagnetic wave radiation ability and light transmittance.
However, when the copper circuit reflects the appearance, there is a problem that the brightness of the display screen is lowered. Therefore, as an electromagnetic shielding copper foil, a copper foil that is surface-treated so as to be close to black and has a low reflectance is preferred.
However, the closer the surface of the surface-treated copper foil is to black, the easier it is for spots to appear on its appearance or for residues to be generated, such as powder coming out of the surface. The spots on the surface of the copper foil deteriorate the image quality of the PDP, and the residue is etched and falls on the portion where the transparent substrate should appear, resulting in inferior light transmittance. Therefore, the PDP resolution is generally lowered.
For this reason, research has been mainly conducted in the direction of surface treatment so that the surface of the copper foil is not completely black but has a chocolate color or dark metal color close to black. However, since the surface of the copper foil manufactured by the method as described above is not completely black, there is a limit in improving the reflectance as an electromagnetic shielding copper foil.

本発明は、黒色の外観を有するので反射率が低い電磁波遮蔽用黒化表面処理銅箔及びその製造方法を提供することを目的とする。
また、本発明は、黒色の外観を有しながらも、斑及び残渣が殆ど無い均一な外観を有する電磁波遮蔽用黒化表面処理銅箔及びその製造方法を提供することを目的とする。
また、本発明の更に他の目的は、剥離強度（peel strength）が優秀な電磁波遮蔽用黒化表面処理銅箔及びその製造方法を提供することにある。 An object of the present invention is to provide a blackened surface-treated copper foil for electromagnetic wave shielding and a method for producing the same, which has a black appearance and has a low reflectance.
Another object of the present invention is to provide a blackened surface-treated copper foil for electromagnetic wave shielding and a method for producing the same having a uniform appearance with almost no spots and residues while having a black appearance.
Still another object of the present invention is to provide an electromagnetic shielding blackened surface-treated copper foil having excellent peel strength and a method for producing the same.

前記目的を達成するための、本発明の電磁波遮蔽用黒化表面処理銅箔の製造方法は、電解メッキ浴に陰極として銅箔を配置し、前記銅薄箔の表面に黒化メッキ層を形成させることにより電磁波遮蔽用表面処理銅箔を製造する方法において、Ｃｏ及び陰極における水素発生を抑制する酸化剤を含む電解メッキ浴を使用して前記銅箔表面に黒色のＣｏ酸化物メッキ層を形成させることを特徴とする。
前記酸化剤は、ＫＮＯ３、ＮＨ４ＮＯ３、ＨＮＯ３、ＮａＮＯ３、ＮＨ４ＣｌＯ３、ＫＣｌＯ３、ＮａＣｌＯ３及びＫＭＯ４から成る群から選択される少なくとも１種であってもよい
前記酸化剤の濃度は、１〜４０ｇ／ｌであることが好ましい。
更に、前記電解メッキ浴にＮｉ及びＦｅから成る群から選択される少なくとも１種の金属イオンが含まれることが好ましい。
前記電解メッキ浴中Ｃｏ、Ｎｉ及びＦｅの金属成分総濃度が１〜８０ｇ／ｌであることが好ましい。
一方、前記Ｃｏ酸化物メッキ層を形成する前に、更に、銅箔の表面に微細銅粒子層を析出形成させる段階を含むことが好ましい。
更に、前記Ｃｏ酸化物メッキ層の表面に電解クロメート層を形成する段階を含むことが好ましい。
更に、メッキ層が形成された表面の裏面にＺｎ又はＺｎ合金で構成されたメッキ被膜層を形成する段階を含むことが好ましい。 In order to achieve the above object, the method for producing a blackened surface-treated copper foil for electromagnetic wave shielding according to the present invention comprises disposing a copper foil as a cathode in an electrolytic plating bath and forming a blackened plating layer on the surface of the copper thin foil. Forming a black Co oxide plating layer on the surface of the copper foil using an electrolytic plating bath containing an oxidizing agent that suppresses hydrogen generation at Co and the cathode. It is characterized by making it.
The oxidizing agent may be at least one selected from the group consisting of KNO 3 , NH 4 NO 3 , HNO 3 , NaNO 3 , NH 4 ClO 3 , KClO 3 , NaClO 3 and KMO 4. The concentration of is preferably 1 to 40 g / l.
Furthermore, it is preferable that the electrolytic plating bath contains at least one metal ion selected from the group consisting of Ni and Fe.
The total concentration of Co, Ni and Fe metal components in the electrolytic plating bath is preferably 1 to 80 g / l.
On the other hand, before forming the Co oxide plating layer, it is preferable to further include a step of forming a fine copper particle layer on the surface of the copper foil.
Furthermore, it is preferable to include a step of forming an electrolytic chromate layer on the surface of the Co oxide plating layer.
Furthermore, it is preferable to include a step of forming a plating film layer made of Zn or a Zn alloy on the back surface of the surface on which the plating layer is formed.

以下、本発明を詳しく説明する。
本発明の対象となる電磁波遮蔽用銅箔は広幅生産が可能な電解銅箔であって、銅箔の厚さは１〜３５μｍであり、好ましくは６〜１８μｍである。表面粗度（Ｒｚ：ＤＩＮ）は０．１〜２．０μｍであり、好ましくは、０．５〜１．５μｍである。表面粗度が０．１μｍより小さい場合、透明基材との接着性が十分でないようになり、電磁波遮蔽体の信頼性が低下され、２．０μｍより大きい場合、エッチングによって回路を形成した後に、銅箔が接着されている透明基材の表面の凹凸が大きくなり、これに因り表示画面の曇りが大きくなるので好ましくない。
銅箔の黒化表面処理は、黒色を誘発する金属が含まれた電解メッキ浴において銅箔を陰極に配置し、前記陰極の銅箔表面上に前記金属メッキ層を析出させることにより行われる。黒色を誘発すると知られた金属としては、Ｃｕ、Ｃｒ、Ｃｏ等があるが、Ｃｕは完全な黒色を導出できるが、追後銅箔回路パターン形成時銅箔回路側に浸透して回路パターンを損傷させる問題があり、Ｃｒは銅箔回路形成時のエッチング性に問題を起こすため、本発明に適用することが難しい。従って、製品損傷防止、製造工程上の問題点等を考慮すると、Ｃｏが最も適当な金属である。 Hereinafter, the present invention will be described in detail.
The copper foil for electromagnetic wave shielding which is the object of the present invention is an electrolytic copper foil capable of wide production, and the thickness of the copper foil is 1 to 35 μm, preferably 6 to 18 μm. The surface roughness (Rz: DIN) is 0.1 to 2.0 μm, preferably 0.5 to 1.5 μm. If the surface roughness is less than 0.1 μm, the adhesion with the transparent substrate is not sufficient, the reliability of the electromagnetic wave shield is reduced, and if greater than 2.0 μm, after forming the circuit by etching, Unevenness on the surface of the transparent base material to which the copper foil is bonded increases, which is not preferable because cloudiness of the display screen increases.
The blackened surface treatment of the copper foil is performed by placing the copper foil on the cathode in an electrolytic plating bath containing a metal that induces blackness, and depositing the metal plating layer on the copper foil surface of the cathode. There are Cu, Cr, Co, etc. that are known to induce black color, but Cu can derive a complete black color, but it penetrates into the copper foil circuit side at the time of copper foil circuit pattern formation later, and the circuit pattern is There is a problem of damage, and Cr causes a problem in etching property when forming a copper foil circuit, so that it is difficult to apply to the present invention. Accordingly, Co is the most suitable metal in consideration of product damage prevention, manufacturing process problems, and the like.

Ｃｏメッキ層が黒色を呈するためには、限界電流密度辺りで電解メッキして、銅箔表面上にＣｏ３Ｏ４、ＣｏＯＯＨ、ＣｏＯのような酸化物の形態で析出されなければならない。しかし、前述のとおり、このような黒化メッキ層は表面に斑が生じるか、表面から粉末が付いて出る残渣発生の問題がある。黒化メッキ層に斑や残渣が発生する主な理由は、陰極から発生する水素の発生態様が銅箔表面に従って均一でないからであると思われる。即ち、メッキ過程で陰極である銅箔表面ではＣｏが酸化され析出されるとともに、水素（Ｈ２）が発生するようになるが、このような水素が発生する部分のメッキ厚さは残り部分の厚さと微細な差異を見せる。このため、全体の銅箔表面を眺望した時、周囲部に比べて水素が発生しないか水素発生態様が異なる部分は斑に見えるようになる。また、前記のようなメッキの不均一性に因り銅箔の製造過程中に表面から部分的にメッキ粒子が脱落される等残渣が発生するようになる。
従って、メッキ層が形成された銅箔の表面粗度が全体的には電磁波遮蔽用銅箔に使用可能な範囲内にあるとしても、前記のように不均一な外観を有する銅箔は製品不良を招くようになる問題がある。 In order for the Co plating layer to exhibit a black color, it must be electroplated around the limit current density and deposited on the copper foil surface in the form of oxides such as Co 3 O 4 , CoOOH, and CoO. However, as described above, such a blackened plating layer has a problem of generation of residue on the surface, or generation of a residue attached with powder from the surface. It seems that the main reason why spots and residues are generated in the blackened plating layer is that the generation mode of hydrogen generated from the cathode is not uniform according to the copper foil surface. That is, during the plating process, Co is oxidized and deposited on the surface of the copper foil, which is the cathode, and hydrogen (H 2 ) is generated. Shows small differences in thickness. For this reason, when the whole copper foil surface is looked at, the part which hydrogen does not generate | occur | produce compared with the surrounding part, or a hydrogen generating aspect differs will become visible. Further, due to the non-uniformity of plating as described above, residues such as plating particles are partially dropped from the surface during the manufacturing process of the copper foil.
Therefore, even if the surface roughness of the copper foil on which the plating layer is formed is within the range that can be used for the copper foil for electromagnetic wave shielding as a whole, the copper foil having a non-uniform appearance as described above is a defective product. There is a problem that will invite.

本発明は、Ｃｏを含む全体メッキ浴に水素発生抑制剤としての酸化剤を添加して陰極における水素発生を抑制することにより、陰極における水素発生態様を均一化することにより、均一な外観の黒化メッキ層を有する黒化表面処理銅箔を得ることができることにその特徴がある。前記酸化剤は水素の発生を抑制するので水素発生で生成され得る斑を防止するとともに、電解液中のＣｏを酸化させる。
このような酸化剤物質としては、ＫＮＯ３、ＮＨ４ＮＯ３、ＨＮＯ３、ＮａＮＯ３、ＮＨ４ＣｌＯ３、ＫＣｌＯ３、ＮａＣｌＯ３、ＫＭＯ４等があり、この中一つ以上を電解メッキ浴に所定量含ませると均一な外観の黒化表面処理銅箔を得ることができる。
具体的なメッキ過程は、例えば、Ｉｒ電極を陽極に使用し、陰極を銅箔にしてメッキを行うことによりなり、銅箔表面に形成されたＣｏ黒化メッキ層はＣｏ３Ｏ４、ＣｏＯＯＨ、ＣｏＯのような酸化物の形態になっている。電解メッキ浴に含まれるＣｏの濃度は１〜８０ｇ／ｌから選ぶことができるが、最も効率良く黒化メッキ層が形成できる濃度は２０〜６０ｇ／ｌである。酸化剤の濃度は、１〜４０ｇ／ｌが適当であり、最も適切な濃度は１〜１５ｇ／ｌである。酸化剤の濃度が１ｇ／ｌを下回ると、水素発生抑制効果が殆ど無くなるばかりでなく、黒色の酸化メッキ層を得ることができないし、４０ｇ／ｌを超えるとＣｏが度を過ぎて酸化され却ってメッキ層の残渣発生（粉落）が更に甚だしくなるからである。 The present invention adds a oxidant as a hydrogen generation inhibitor to the entire plating bath containing Co to suppress hydrogen generation at the cathode, thereby uniformizing the hydrogen generation mode at the cathode, thereby achieving a uniform black appearance. It is characterized in that a blackened surface-treated copper foil having a plated layer can be obtained. The oxidant suppresses the generation of hydrogen, thereby preventing spots that can be generated by hydrogen generation and oxidizing Co in the electrolyte.
Examples of such an oxidant material include KNO 3 , NH 4 NO 3 , HNO 3 , NaNO 3 , NH 4 ClO 3 , KClO 3 , NaClO 3 , KMO 4, etc., and one or more of them are used as an electrolytic plating bath. When a predetermined amount is included, a blackened surface-treated copper foil having a uniform appearance can be obtained.
The specific plating process includes, for example, plating using an Ir electrode as an anode and a cathode as a copper foil, and the Co blackening plating layer formed on the surface of the copper foil includes Co 3 O 4 , CoOOH, It is in the form of an oxide such as CoO. The concentration of Co contained in the electrolytic plating bath can be selected from 1 to 80 g / l, but the concentration at which the blackened plating layer can be formed most efficiently is 20 to 60 g / l. The concentration of the oxidizing agent is suitably 1 to 40 g / l, and the most suitable concentration is 1 to 15 g / l. When the concentration of the oxidizing agent is less than 1 g / l, not only the effect of suppressing hydrogen generation is almost lost, but also a black oxide plating layer cannot be obtained, and when it exceeds 40 g / l, Co is excessively oxidized and rejected. This is because the generation of residue (powder) in the plating layer becomes more serious.

工業的に経済的なメッキ浴の電流密度は０．１〜６０Ａ／ｄｍ２であり、特に５〜２５Ａ／ｄｍ２の電流密度が好ましい。電流密度が０．１Ａ／ｄｍ２未満であれば望む黒色のメッキ層を得ることができないし、６０Ａ／ｄｍ２以上では黒色メッキ層と銅箔との間の接着強度が劣り剥離現像が発生するからである。
メッキ浴のｐＨは２．５〜５．５範囲であるのが好ましく、特に、３．０〜４．０範囲の ｐＨが好ましい。ｐＨが２．５未満である場合、メッキされた黒化層が溶け出るようになり、ｐＨが５．５以上である場合には黒化表面処理されない反対側面が変色される問題がある。前記ｐＨは硫酸とＫＯＨを添加して調節することができる。
また、メッキ時間は１〜２０秒範囲で可能であるが、電流密度、電解液濃度等を考慮して前記範囲以外も可能である。
一方、銅箔の剥離強度を向上させ透明基材との接着性を向上させるためにＣｏ外の他の金属成分も電解浴に含ませることができる。銅箔の特性を害せず、剥離強度を向上させる元素としては、Ｎｉ、Ｆｅが適当である。前記金属成分とＣｏとを合わせた電解液中の金属成分濃度も１〜８０ｇ／ｌ範囲にあるものがメッキ効率性の側面で好ましい。 Current density industrially economical plating baths are 0.1~60A / dm 2, in particular current density of 5~25A / dm 2 is preferred. If the current density is less than 0.1 A / dm 2 , the desired black plating layer cannot be obtained, and if it is 60 A / dm 2 or more, the adhesive strength between the black plating layer and the copper foil is poor and peeling development occurs. Because.
The pH of the plating bath is preferably in the range of 2.5 to 5.5, and particularly preferably in the range of 3.0 to 4.0. When the pH is less than 2.5, the plated blackened layer starts to melt, and when the pH is 5.5 or more, there is a problem that the opposite side surface that is not treated with the blackened surface is discolored. The pH can be adjusted by adding sulfuric acid and KOH.
The plating time can be in the range of 1 to 20 seconds, but other than the above range is also possible in consideration of the current density, the electrolyte concentration, and the like.
On the other hand, other metal components other than Co can be included in the electrolytic bath in order to improve the peel strength of the copper foil and improve the adhesion to the transparent substrate. Ni and Fe are suitable as elements that improve the peel strength without impairing the properties of the copper foil. The metal component concentration in the electrolyte solution combining the metal component and Co is preferably in the range of 1 to 80 g / l from the viewpoint of plating efficiency.

また、反射率を小さくし、透明基材との接着性を向上させるために黒化メッキを行う前に、銅箔の表面に微細銅粒子層を析出付着させることができる。析出された銅粒子はアンカー（anchor）役割をして透明基材に銅箔を積層させる時、剥離強度を上昇させて接着性を向上させ、外光を乱反射させ反射率を劣らせる。
微細銅粒子層の形成は、プリント配線板用銅箔に使用される粗化処理を利用して行うことができる。粗化処理は硫酸銅メッキ浴で行うことが普通であり、粗化処理時の銅粒子の付着量は０．１〜１０ｇ／ｍ２範囲が好ましく、更に好ましい範囲は０．５〜８ｇ／ｍ２である。
微細銅粒子層形成、黒化メッキ層形成の全ての表面処理工程に亘って表面粗度は前述のとおり、Ｒｚ（ＤＩＮ規格）で０．１〜２．０μｍ以内に保持されるべきである。
上述の微細銅粒子層形成条件、黒化メッキ条件の範囲内で表面処理する場合、表面粗度を前記範囲以内に保持することができる。
一方、本発明の銅箔に電解クロメート（chromate）処理等の防錆処理をすることができる。また、黒化メッキを行わない側の表面にＺｎ又はＺｎ合金からなるメッキ被膜を形成すると、電磁波遮蔽体製造のための加熱工程で加熱変色を防ぐことができる。 In addition, a fine copper particle layer can be deposited on the surface of the copper foil before performing blackening plating in order to reduce the reflectance and improve the adhesion to the transparent substrate. The deposited copper particles act as an anchor, and when the copper foil is laminated on the transparent substrate, the peel strength is increased to improve the adhesion, and the external light is irregularly reflected to deteriorate the reflectance.
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 performed in a copper sulfate plating bath, and the amount of copper particles deposited during the roughening treatment is preferably in the range of 0.1 to 10 g / m 2 , and more preferably in the range of 0.5 to 8 g / m. 2 .
As described above, the surface roughness should be kept within 0.1 to 2.0 μm in Rz (DIN standard) over the entire surface treatment process of forming the fine copper particle layer and blackening plating layer.
When the surface treatment is performed within the range of the above-described fine copper particle layer forming conditions and blackening plating conditions, the surface roughness can be maintained within the above ranges.
On the other hand, the copper foil of the present invention can be subjected to rust prevention treatment such as electrolytic chromate treatment. Further, when a plating film made of Zn or a Zn alloy is formed on the surface not subjected to blackening plating, heating discoloration can be prevented in the heating process for manufacturing the electromagnetic wave shielding body.

以下、本発明を実施例により具体的に説明する。しかし、以下の実施例は専ら本発明を説明するためのものであって、本発明の要旨に基づいて本発明の範囲が以下の実施例に限定されないことは当業者にとって自明である。   Hereinafter, the present invention will be specifically described by way of examples. However, the following examples are only for explaining the present invention, and it is obvious to those skilled in the art that the scope of the present invention is not limited to the following examples based on the gist of the present invention.

実施例１
表面粗度（Ｒｚ）が２μｍ以下、厚さ１０μｍである電解銅箔を１００ｇ／ｌ硫酸において、５秒間浸漬し酸洗処理後純水で洗浄した後に、通常的にｓｈｉｎｙ面と称する銅箔表面に下の条件で黒化メッキ処理を行った。黒化メッキ処理後、黒化処理面にＣｒ防錆処理を行った。電解浴組成；Ｃｏ金属イオン濃度４０ｇ／ｌ（Ｃｏは硫酸コバルト形態でメッキ浴に添加される）、ＫＮＯ３濃度２ｇ／ｌ、緩衝液（Ｈ３ＢＯ３）濃度３０ｇ／ｌ
電解液ｐＨ；３．５、
電解液の温度：２５℃、電流密度；１０Ａ／ｄｍ２、メッキ時間；４秒。 Example 1
An electrolytic copper foil having a surface roughness (Rz) of 2 μm or less and a thickness of 10 μm is immersed in 100 g / l sulfuric acid for 5 seconds, pickled, washed with pure water, and then generally referred to as a shiny surface. The blackening plating process was performed under the following conditions. After the blackening plating treatment, the blackening treatment surface was subjected to Cr rust prevention treatment. Electrolytic bath composition: Co metal ion concentration 40 g / l (Co is added to the plating bath in the form of cobalt sulfate), KNO 3 concentration 2 g / l, buffer solution (H 3 BO 3 ) concentration 30 g / l
Electrolyte pH: 3.5,
Electrolyte temperature: 25 ° C., current density: 10 A / dm 2 , plating time: 4 seconds.

実施例２
実施例１と同一な条件で銅箔の表面を前処理した後、通常的にshiny面と称する銅箔表面に下の条件で黒化メッキ処理を実施した。黒化メッキ処理後、黒化処理面にＣｒ防錆処理を実施した。電解浴組成；Ｃｏ金属イオン濃度４０ｇ／ｌ（Ｃｏは硫酸コバルト形態でメッキ浴に添加される）、ＫＮＯ３濃度２ｇ／ｌ、緩衝液（Ｈ３ＢＯ３）濃度３０ｇ／ｌ
電解液 ｐＨ；３．５，
電解液の温度；２５℃、電流密度；２０Ａ／ｄｍ２、メッキ時間；２．５秒 Example 2
After pretreating the surface of the copper foil under the same conditions as in Example 1, the blackening plating treatment was carried out on the surface of the copper foil, which is usually referred to as a shiny surface, under the following conditions. After the blackening plating treatment, the blackening treatment surface was subjected to Cr rust prevention treatment. Electrolytic bath composition: Co metal ion concentration 40 g / l (Co is added to the plating bath in the form of cobalt sulfate), KNO 3 concentration 2 g / l, buffer solution (H 3 BO 3 ) concentration 30 g / l
Electrolyte pH: 3.5,
Electrolyte temperature: 25 ° C., current density: 20 A / dm 2 , plating time: 2.5 seconds

実施例３
銅付着量を１．５ｇ／ｍ２にして微細銅粒子層を形成し、実施例２と同一な条件で黒化メッキ処理及び防錆処理をした。 Example 3
A fine copper particle layer was formed with a copper adhesion amount of 1.5 g / m 2 , and blackening plating treatment and rust prevention treatment were performed under the same conditions as in Example 2.

実施例４
実施例１と同一な条件で銅箔の表面を前処理した後、通常的にｓｈｉｎｙ面と称する銅箔表面に下の条件で黒化メッキ処理を実施した。黒化メッキ処理後、黒化処理面にＣｒ防錆処理を実施した。電解浴組成；Ｃｏ金属イオン濃度３５ｇ／ｌ（Ｃｏは硫酸コバルト形態でメッキ浴に添加される）、Ｎｉ金属イオン濃度（硫酸ニッケル形態でメッキ浴に添加される）８ｇ／ｌ、ＫＮＯ３濃度２ｇ／ｌ、緩衝液（Ｈ３ＢＯ３）濃度３０ｇ／ｌ
電解液ｐＨ；３．５，
電解液の温度；２５℃、電流密度；１０Ａ／ｄｍ２、メッキ時間；４秒。 Example 4
After pre-treating the surface of the copper foil under the same conditions as in Example 1, a blackening plating process was performed on the copper foil surface, usually referred to as a shiny surface, under the following conditions. After the blackening plating treatment, the blackening treatment surface was subjected to Cr rust prevention treatment. Electrolytic bath composition: Co metal ion concentration 35 g / l (Co is added to the plating bath in the form of cobalt sulfate), Ni metal ion concentration (added to the plating bath in the form of nickel sulfate) 8 g / l, KNO 3 concentration 2 g / L, buffer (H 3 BO 3 ) concentration 30 g / l
Electrolyte pH: 3.5,
Electrolyte temperature: 25 ° C., current density: 10 A / dm 2 , plating time: 4 seconds.

実施例５
Ｎｉイオンの代わりにＦｅイオンを８ｇ／ｌ添加したことの外には実施例４と同一な条件で黒化メッキ処理及び防錆処理を行った。 Example 5
A blackening plating treatment and a rust prevention treatment were performed under the same conditions as in Example 4 except that 8 g / l of Fe ions were added instead of Ni ions.

比較例１
前記実施例と同一な条件で電解銅箔表面を前処理した後、下記の条件で黒化処理メッキを実施した。黒化メッキ処理後、黒化処理面にＣｒ防錆処理を実施した。電解浴組成；Ｃｏ金属イオン濃度４０ｇ／ｌ（Ｃｏは硫酸コバルト形態でメッキ浴に添加される）、緩衝液（Ｈ３ＢＯ３）濃度３０ｇ／ｌ、その他微量元素等。
電解液ｐＨ；３．５、
電解液の温度；２５℃、電流密度；２０Ａ／ｄｍ２、メッキ時間；２．５秒。 Comparative Example 1
After pre-treating the surface of the electrolytic copper foil under the same conditions as in the above example, blackening plating was performed under the following conditions. After the blackening plating treatment, the blackening treatment surface was subjected to Cr rust prevention treatment. Electrolytic bath composition: Co metal ion concentration 40 g / l (Co is added to the plating bath in the form of cobalt sulfate), buffer solution (H 3 BO 3 ) concentration 30 g / l, and other trace elements.
Electrolyte pH: 3.5,
Electrolyte temperature: 25 ° C., current density: 20 A / dm 2 , plating time: 2.5 seconds.

比較例２
前記実施例と同一な条件で電解銅箔表面を前処理した後、下記の条件で黒化処理メッキを実施した。黒化メッキ処理後、黒化処理面にＣｒ防錆処理を実施した。電解浴組成；Ｃｏ金属イオン濃度３０ｇ／ｌ（Ｃｏは硫酸コバルト形態でメッキ浴に添加される）、Ｎｉ金属イオン濃度（硫酸ニッケル形態でメッキ浴に添加される）８ｇ／ｌ、緩衝液（Ｈ３ＢＯ３）濃度３０ｇ／ｌ、その他微量元素等。
電解液ｐＨ；３．５、
電解液の温度；２５℃、電流密度；２０Ａ／ｄｍ２、メッキ時間；４秒。 Comparative Example 2
After pre-treating the surface of the electrolytic copper foil under the same conditions as in the above example, blackening plating was performed under the following conditions. After the blackening plating treatment, the blackening treatment surface was subjected to Cr rust prevention treatment. Electrolytic bath composition: Co metal ion concentration 30 g / l (Co is added to the plating bath in the form of cobalt sulfate), Ni metal ion concentration (added to the plating bath in the form of nickel sulfate) 8 g / l, buffer solution (H 3 BO 3 ) Concentration 30 g / l, other trace elements, etc.
Electrolyte pH: 3.5,
Electrolyte temperature: 25 ° C., current density: 20 A / dm 2 , plating time: 4 seconds.

下記表１は前記実施例及び比較例による表面処理銅箔の斑発生有無、擦ることによる残渣発生（粉落）有無、剥離強度を測定した結果を表したものである。

Figure 2007531820
Table 1 below shows the results of measuring the presence / absence of spots on the surface-treated copper foil according to the examples and comparative examples, the presence / absence of residue generation (dusting) by rubbing, and the peel strength.
Figure 2007531820

表１に示すように、電解メッキ浴に酸化剤が含まれなかった比較例１及び２は表面上に斑と残渣が発生している。しかし、本発明の実施例は斑及び残渣が発生しなかったことを分かる。
また、黒化メッキ処理前に微細銅粒子層を形成させた実施例３は、微細銅粒子層を形成しない各対応される条件の実施例２に比べて剥離強度が上昇したことを分かる。また、黒化メッキ層にＮｉとＦｅとがそれぞれ追加的に含まれた実施例４と実施例５とが前記成分等が含まれない実施例１及び２より更に高い剥離強度を有することを分かる。
前記のような均一な外観を有する本発明の表面処理銅箔をＰＥＴのような絶縁性透明基材に積層して製造される複合材料で電磁波遮蔽体を製造すると、表示画面の解像図が優秀なプラズマデイスプレーパネルを製造することができ、その不良率も顕著に低くすることができるようになる。 As shown in Table 1, in Comparative Examples 1 and 2 in which the oxidant was not contained in the electrolytic plating bath, spots and residues were generated on the surface. However, it can be seen that the examples of the present invention did not produce spots and residues.
In addition, it can be seen that Example 3 in which the fine copper particle layer was formed before the blackening plating treatment increased the peel strength as compared with Example 2 in each of the corresponding conditions in which the fine copper particle layer was not formed. Further, it can be seen that Example 4 and Example 5 in which Ni and Fe are additionally included in the blackened plating layer have higher peel strength than Examples 1 and 2 in which the above components and the like are not included. .
When an electromagnetic wave shielding body is manufactured with a composite material manufactured by laminating the surface-treated copper foil of the present invention having a uniform appearance as described above on an insulating transparent substrate such as PET, a resolution diagram of a display screen is obtained. An excellent plasma display panel can be manufactured, and the defect rate can be significantly reduced.

以上で説明したとおり、本発明の製造方法によって製造された表面処理銅箔は、反射率が低い黒色の外観を有するので、ＰＤＰ表示画面の輝度を低下させないという長所がある。
さらに、本発明による表面処理銅箔は、黒色の外観を有しながらも、斑及び残渣が殆どない均一な外観を有するので、これを利用して製造された電磁波遮蔽体用複合材料の不良率が顕著に低くなり、前記複合材料を使用して製造されたＰＤＰ表示画面の外観が優秀になる効果がある。 As described above, since the surface-treated copper foil manufactured by the manufacturing method of the present invention has a black appearance with low reflectance, there is an advantage that the luminance of the PDP display screen is not lowered.
Furthermore, since the surface-treated copper foil according to the present invention has a black appearance but a uniform appearance with almost no spots and residues, the defect rate of the composite material for electromagnetic wave shields produced using this Is significantly reduced, and the appearance of the PDP display screen manufactured using the composite material is excellent.

Claims (10)

電解メッキ浴に陰極として銅箔を配置し、前記銅薄箔の表面に黒化メッキ層を形成させることにより電磁波遮蔽用表面処理銅箔を製造する方法において、Ｃｏ及び陰極における水素発生を抑制する酸化剤を含む電解メッキ浴を使用して前記銅箔表面に黒色のＣｏ酸化物メッキ層を形成させることを特徴とする電磁波遮蔽用黒化表面処理銅箔の製造方法。 In a method for producing a surface-treated copper foil for electromagnetic wave shielding by disposing copper foil as a cathode in an electrolytic plating bath and forming a blackened plating layer on the surface of the copper thin foil, suppressing hydrogen generation at Co and the cathode A method for producing a blackened surface-treated copper foil for shielding electromagnetic waves, wherein a black Co oxide plating layer is formed on the surface of the copper foil using an electrolytic plating bath containing an oxidizing agent. 前記酸化剤が、ＫＮＯ３、ＮＨ４ＮＯ３、ＨＮＯ３、ＮａＮＯ３、ＮＨ４ＣｌＯ３、ＫＣｌＯ３、ＮａＣｌＯ３及びＫＭＯ４から成る群から選択される少なくとも１種であることを特徴とする請求項１に記載の製造方法。 The oxidizing agent is at least one selected from the group consisting of KNO 3 , NH 4 NO 3 , HNO 3 , NaNO 3 , NH 4 ClO 3 , KClO 3 , NaClO 3 and KMO 4. Item 2. The manufacturing method according to Item 1. 前記酸化剤の濃度が１〜４０ｇ／ｌであることを特徴とする請求項２に記載の製造方法。 The manufacturing method according to claim 2, wherein the concentration of the oxidizing agent is 1 to 40 g / l. 前記電解メッキ浴にＮｉ及びＦｅから成る群から選択される少なくとも１種の金属イオンがさらに含まれることを特徴とする請求項１に記載の製造方法。 The method according to claim 1, wherein the electrolytic plating bath further includes at least one metal ion selected from the group consisting of Ni and Fe. 前記電解メッキ浴中Ｃｏ、Ｎｉ及びＦｅの金属成分総濃度が１〜８０ｇ／ｌであることを特徴とする請求項４に記載の製造方法。 The manufacturing method according to claim 4, wherein the total concentration of Co, Ni and Fe metal components in the electrolytic plating bath is 1 to 80 g / l. 前記Ｃｏ酸化物メッキ層を形成する前に、更に、銅箔の表面に微細銅粒子層を析出形成させる段階を含む請求項１〜５のいずれか一項に記載の製造方法。 The manufacturing method according to any one of claims 1 to 5, further comprising a step of depositing and forming a fine copper particle layer on the surface of the copper foil before forming the Co oxide plating layer. 更に、前記Ｃｏ酸化物メッキ層の表面に電解クロメート層を形成する段階を含む請求項６に記載の製造方法。 The manufacturing method according to claim 6, further comprising a step of forming an electrolytic chromate layer on a surface of the Co oxide plating layer. 更に、メッキ層が形成された表面の裏面にＺｎ又はＺｎ合金で構成されたメッキ被膜層を形成する段階を含む請求項６に記載の製造方法。 Furthermore, the manufacturing method of Claim 6 including the step of forming the plating film layer comprised by Zn or Zn alloy on the back surface of the surface in which the plating layer was formed. 請求項６に記載の製造方法によって製造された電磁波遮蔽用黒化表面処理銅箔。 A blackened surface-treated copper foil for electromagnetic wave shielding produced by the production method according to claim 6. 請求項９に記載の黒化表面処理銅箔を絶縁性透明基材に積層して製造された電磁波遮蔽用複合材料。 An electromagnetic shielding composite material produced by laminating the blackened surface-treated copper foil according to claim 9 on an insulating transparent substrate.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5993984A (en) * 1982-11-17 1984-05-30 Fuji Electric Co Ltd Water encapsulated pump device
WO2013168528A1 (en) * 2012-05-09 2013-11-14 奥野製薬工業株式会社 BLACKENING TREATMENT SOLUTION FOR BLACK Cr-Co ALLOY PLATING FILM
JP2017505385A (en) * 2013-12-30 2017-02-16 イルジン マテリアルズ カンパニー リミテッドＩｌｊｉｎ Ｍａｔｅｒｉａｌｓ Ｃｏ．， Ｌｔｄ． Copper foil, electrical parts including the same, and battery

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007332418A (en) * 2006-06-15 2007-12-27 Fukuda Metal Foil & Powder Co Ltd Surface treated copper foil
WO2017130869A1 (en) * 2016-01-29 2017-08-03 住友金属鉱山株式会社 Blackening plating solution and method for manufacturing conductive substrate

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW230290B (en) * 1991-11-15 1994-09-11 Nikko Guruder Foreer Kk
JP3222002B2 (en) * 1993-12-27 2001-10-22 株式会社日鉱マテリアルズ Copper foil for printed circuit and manufacturing method thereof
US6497806B1 (en) * 2000-04-25 2002-12-24 Nippon Denkai, Ltd. Method of producing a roughening-treated copper foil
JP3374127B2 (en) * 2000-11-27 2003-02-04 古河サーキットフォイル株式会社 Metal foil, laminated board for circuit boards using it

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5993984A (en) * 1982-11-17 1984-05-30 Fuji Electric Co Ltd Water encapsulated pump device
WO2013168528A1 (en) * 2012-05-09 2013-11-14 奥野製薬工業株式会社 BLACKENING TREATMENT SOLUTION FOR BLACK Cr-Co ALLOY PLATING FILM
US9920416B2 (en) 2012-05-09 2018-03-20 Okuno Chemical Industries Co., Ltd. Blackening treatment solution for black Cr—Co alloy plating film
JP2017505385A (en) * 2013-12-30 2017-02-16 イルジン マテリアルズ カンパニー リミテッドＩｌｊｉｎ Ｍａｔｅｒｉａｌｓ Ｃｏ．， Ｌｔｄ． Copper foil, electrical parts including the same, and battery

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