JP2009206514A - Copper foil for printed circuit and surface treating method thereof, and plating apparatus - Google Patents

Copper foil for printed circuit and surface treating method thereof, and plating apparatus Download PDF

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JP2009206514A
JP2009206514A JP2009040973A JP2009040973A JP2009206514A JP 2009206514 A JP2009206514 A JP 2009206514A JP 2009040973 A JP2009040973 A JP 2009040973A JP 2009040973 A JP2009040973 A JP 2009040973A JP 2009206514 A JP2009206514 A JP 2009206514A
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copper foil
copper
plating
printed circuit
molybdenum
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Seung Jun Choi
スン−ジュン チェ，
Sang Gyum Kim
サン−ギュン キム，
Jeong Ik Kim
ジョン−イク キム，
Jong-Ho Lee
ジョン−ホ リ，
Seung Min Kim
スン−ミン キム，
Young Uk Chae
ヨン−ウク チャ，
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LS Mtron Ltd
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LS Mtron Ltd
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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
    • C25D1/00—Electroforming
    • C25D1/12—Electroforming by electrophoresis
    • C25D1/14—Electroforming by electrophoresis of inorganic material
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0614—Strips or foils
    • C25D7/0671—Selective 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
    • 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Electrochemistry (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Molecular Biology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Parts Printed On Printed Circuit Boards (AREA)
  • Laminated Bodies (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To provide a copper foil for a printed circuit which is improved in heat resistance, acid resistance, etc., and a surface treating method thereof. <P>SOLUTION: The copper foil for the printed circuit is surface-treated by the method including a stage of forming a copper nodule layer on a surface of a copper foil after a foil forming stage, and a stage of forming a barrier layer by plating the copper nodule layer with molybdenum (Mo) or Molybdenum (Mo) alloy. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

本発明は、プリント回路用銅箔の表面処理に関し、より詳しくは、フレキシブルプリント回路（ＦＰＣ：Ｆｌｅｘｉｂｌｅ Ｐｒｉｎｔｅｄ Ｃｉｒｃｕｉｔ）などのプリント回路に用いられる銅箔の表面をメッキ処理して耐熱性、耐酸性などを改善したプリント回路用銅箔及びそのための表面処理方法、並びにメッキ装置に関する。   TECHNICAL FIELD The present invention relates to surface treatment of copper foil for printed circuits, and more specifically, heat treatment, acid resistance, etc. by plating the surface of copper foil used for printed circuits such as flexible printed circuits (FPCs). The present invention relates to a copper foil for printed circuit, a surface treatment method therefor, and a plating apparatus.

電子部品用プリント回路に用いられる基礎素材である銅箔は、電気メッキ法で電解銅箔を製造する製箔工程と、原箔に剥離強度などを与えるための後処理工程と、を通じて製造される。   Copper foil, which is a basic material used in printed circuits for electronic components, is manufactured through a foil-making process for producing electrolytic copper foil by electroplating and a post-treatment process for giving peel strength to the original foil. .

通常の製箔工程によって製造された銅箔は、電気メッキするときに陰極板から剥離され、相対的に粗度が低くて光沢のある面（Ｓ面：Ｓｈｉｎｙ Ｓｉｄｅ）と、Ｓ面の他面に位置し、相対的に粗度が高くて光沢のない面（Ｍ面：Ｍａｔｔｅ Ｓｉｄｅ）と、に区分される。   The copper foil produced by the normal foil making process is peeled off from the cathode plate when electroplating, and has a relatively low roughness and glossy surface (S surface: Shiny Side), and the other surface of the S surface. And a surface having a relatively high roughness and no gloss (M surface: Matte Side).

製箔工程で製造された電解銅箔は、後処理工程で銅ノジュールとバリアを形成する表面処理を施すことでプリント回路用に好適な物理的、化学的特性が与えられる。   The electrolytic copper foil produced in the foil-making process is given physical and chemical characteristics suitable for printed circuits by performing a surface treatment that forms a copper nodule and a barrier in the post-treatment process.

すなわち、後処理工程で銅箔は、図１に示されたように第１銅メッキ槽１０、第２銅メッキ槽１１、ニッケルメッキ槽１２、クロムメッキ槽１３などを順次通過することで電気メッキによって表面処理される。図１において、本体銅箔１は複数のガイドロール１４によって各メッキ槽の内部に導かれ、最終的に巻取りロール１５に巻き取られる。各メッキ槽の内部に配置されるガイドロール１４には、電気メッキのためにメッキ液に印加される極性に対応する極性の電極が連結される。第１銅メッキ槽１０には銅箔のＭ面に銅ノジュールの核を生成させるためのメッキ液が満たされ、第２銅メッキ槽１１には銅ノジュールの核を成長させるためのメッキ液が満たされる。   That is, in the post-processing step, the copper foil is electroplated by sequentially passing through the first copper plating tank 10, the second copper plating tank 11, the nickel plating tank 12, the chrome plating tank 13 and the like as shown in FIG. Surface treated by. In FIG. 1, the main body copper foil 1 is guided to the inside of each plating tank by a plurality of guide rolls 14 and finally taken up by a take-up roll 15. An electrode having a polarity corresponding to the polarity applied to the plating solution for electroplating is connected to the guide roll 14 disposed in each plating tank. The first copper plating tank 10 is filled with a plating solution for generating copper nodule nuclei on the M surface of the copper foil, and the second copper plating tank 11 is filled with a plating solution for growing copper nodule nuclei. It is.

後処理工程によってプリント回路用銅箔は、図２に示されたように、本体銅箔１のＭ面上に銅ノジュール層２が設けられた構造を持つ。銅ノジュール層２上には、ニッケル（Ｎｉ）、クロム（Ｃｒ）などのメッキ層であるバリア層３が設けられ、耐熱、耐塩酸性、耐酸化性などが与えられる。図示されてはいないが、バリア層３の上には銅箔に接着される樹脂フィルムとの接着力を向上させるために、シランカップリング剤がさらに塗布される。   As shown in FIG. 2, the printed circuit copper foil has a structure in which the copper nodule layer 2 is provided on the M surface of the main body copper foil 1 by the post-processing step. On the copper nodule layer 2, a barrier layer 3 which is a plating layer of nickel (Ni), chromium (Cr) or the like is provided, and heat resistance, hydrochloric acid resistance, oxidation resistance and the like are given. Although not shown, a silane coupling agent is further applied on the barrier layer 3 in order to improve the adhesive force with the resin film adhered to the copper foil.

しかし、従来の後処理工程では接着力、耐熱、耐酸特性などを増加させることに限界があり、特に銅箔とポリマー樹脂を接着させる高温熱処理工程で耐熱性が脆弱であるため、銅箔と樹脂の遊離現象が生じてエッチング性が良くないという問題がある。   However, the conventional post-treatment process has limitations in increasing adhesive strength, heat resistance, acid resistance, etc., and in particular, the heat resistance is weak in the high-temperature heat treatment process for bonding copper foil and polymer resin, so copper foil and resin This causes a problem that the etching phenomenon is not good.

本発明は、前述したような問題点を解決するために創案されたものであり、バリア層の金属原素の成分改善を通じて耐熱性、耐酸特性などを向上させることで樹脂フィルムとの接着力とエッチング性などに優れるプリント回路用銅箔及びそのための表面処理方法、並びにメッキ装置を提供することを目的とする。   The present invention was devised to solve the above-described problems, and improves the heat resistance, acid resistance characteristics, etc. through improvement of the components of the metal element of the barrier layer, thereby improving the adhesive strength with the resin film. An object of the present invention is to provide a copper foil for printed circuit excellent in etching property, a surface treatment method therefor, and a plating apparatus.

前述したような目的を達成するために、本発明はモリブデン（Ｍｏ）元素を含むバリア層を提供するプリント回路用銅箔の表面処理方法を開示する。   In order to achieve the above-described object, the present invention discloses a surface treatment method for a copper foil for a printed circuit which provides a barrier layer containing a molybdenum (Mo) element.

すなわち、本発明によるプリント回路用銅箔の表面処理方法は製箔工程を経た銅箔の表面に銅ノジュール層を形成する第１段階、及び前記銅ノジュール層上にモリブデン（Ｍｏ）またはモリブデン（Ｍｏ）合金をメッキしてバリア層を形成する第２段階を含む。   That is, the surface treatment method of a copper foil for printed circuit according to the present invention is a first step of forming a copper nodule layer on the surface of the copper foil that has undergone the foil-making process, and molybdenum (Mo) or molybdenum (Mo ) Including a second step of plating the alloy to form a barrier layer.

前記モリブデン（Ｍｏ）のメッキ量は０．５〜１００ｍｇ／ｍ２であることが望ましい。 The plating amount of molybdenum (Mo) is preferably 0.5 to 100 mg / m 2 .

前記第２段階で前記バリア層を形成するとき、亜鉛（Ｚｎ）または亜鉛（Ｚｎ）合金をメッキする処理をさらに施すことができる。   When the barrier layer is formed in the second step, a treatment of plating zinc (Zn) or a zinc (Zn) alloy can be further performed.

前記亜鉛（Ｚｎ）のメッキ量は２０ｍｇ／ｍ２以下であることが望ましい。 The plating amount of zinc (Zn) is desirably 20 mg / m 2 or less.

前記第２段階で前記バリア層を形成するとき、クロム（Ｃｒ）またはクロム（Ｃｒ）合金をメッキする処理をさらに施すことができる。   When the barrier layer is formed in the second stage, a treatment of plating chromium (Cr) or a chromium (Cr) alloy may be further performed.

望ましくは、前記第２段階の後には前記バリア層上にシランカップリング剤を塗布する処理を施すことができる。   Preferably, after the second step, a treatment for applying a silane coupling agent on the barrier layer can be performed.

本発明の他の態様によれば、本体銅箔と、前記本体銅箔の表面に形成された銅ノジュール層と、前記銅ノジュール層上にメッキされ、モリブデン（Ｍｏ）層またはモリブデン（Ｍｏ）合金層を含むバリア層と、を含むプリント回路用銅箔が提供される。   According to another aspect of the present invention, a main body copper foil, a copper nodule layer formed on the surface of the main body copper foil, and a molybdenum (Mo) layer or a molybdenum (Mo) alloy plated on the copper nodule layer And a copper layer for a printed circuit including the barrier layer.

前記バリア層において、前記モリブデン（Ｍｏ）のメッキ量は０．５〜１００ｍｇ／ｍ２であることが望ましい。 In the barrier layer, the molybdenum (Mo) plating amount is preferably 0.5 to 100 mg / m 2 .

前記バリア層には亜鉛（Ｚｎ）層または亜鉛（Ｚｎ）合金層がさらに含まれ得る。   The barrier layer may further include a zinc (Zn) layer or a zinc (Zn) alloy layer.

前記バリア層において、前記亜鉛（Ｚｎ）のメッキ量は２０ｍｇ／ｍ２以下であることが望ましい。 In the barrier layer, the zinc (Zn) plating amount is preferably 20 mg / m 2 or less.

前記バリア層には、クロム（Ｃｒ）層またはクロム（Ｃｒ）合金層がさらに含まれ得る。   The barrier layer may further include a chromium (Cr) layer or a chromium (Cr) alloy layer.

前記バリア層上には、シランカップリング剤層をさらに設けることができる。   A silane coupling agent layer can be further provided on the barrier layer.

本発明のさらに他の態様によれば、製箔工程を経た銅箔の表面を処理するための銅箔メッキ装置において、前記銅箔の表面に銅ノジュールの核を生成できるメッキ液が満たされた第１銅メッキ槽と、前記銅箔の表面に対して銅ノジュールの核を成長できるメッキ液が満たされた第２銅メッキ槽と、前記銅箔の銅ノジュール上にモリブデン（Ｍｏ）またはモリブデン（Ｍｏ）合金をメッキするためのメッキ液が満たされたモリブデンメッキ槽と、を含むことを特徴とするプリント回路用銅箔メッキ装置が提供される。   According to yet another aspect of the present invention, in the copper foil plating apparatus for treating the surface of the copper foil that has undergone the foil-making process, the surface of the copper foil is filled with a plating solution that can generate nuclei of copper nodules. A first copper plating tank; a second copper plating tank filled with a plating solution capable of growing copper nodule nuclei on the surface of the copper foil; and molybdenum (Mo) or molybdenum (on the copper nodule of the copper foil) Mo) Molybdenum plating tank filled with a plating solution for plating an alloy is provided, and a copper foil plating apparatus for printed circuit is provided.

プリント回路用銅箔メッキ装置には、前記銅箔の銅ノジュール上に亜鉛（Ｚｎ）または亜鉛（Ｚｎ）合金をメッキするためのメッキ液が満たされた亜鉛メッキ槽がさらに含まれ得る。   The copper foil plating apparatus for printed circuit may further include a galvanizing tank filled with a plating solution for plating zinc (Zn) or a zinc (Zn) alloy on the copper nodules of the copper foil.

また、プリント回路用銅箔メッキ装置には、前記銅箔の銅ノジュール上にクロム（Ｃｒ）またはクロム（Ｃｒ）合金をメッキするためのメッキ液が満たされたクロムメッキ槽がさらに含まれ得る。   The printed circuit copper foil plating apparatus may further include a chrome plating tank filled with a plating solution for plating chromium (Cr) or a chromium (Cr) alloy on the copper nodules of the copper foil.

本発明によれば、銅箔の銅ノジュール層上にモリブデン（Ｍｏ）またはモリブデン（Ｍｏ）合金を含むバリア層を設けて高温熱処理工程時の耐熱性を高めることで、銅箔と樹脂フィルムとの間の遊離現象を防止することができ、耐酸性、耐腐食性、エッチング性などを改善することができる。   According to the present invention, the barrier layer containing molybdenum (Mo) or molybdenum (Mo) alloy is provided on the copper nodule layer of the copper foil to increase the heat resistance during the high-temperature heat treatment process, thereby The release phenomenon can be prevented, and the acid resistance, corrosion resistance, etching property and the like can be improved.

本明細書に添付される次の図面は、本発明の望ましい実施例を例示するものであり、発明の詳細な説明とともに本発明の技術的な思想をさらに理解させる役割をするため、本発明は図面に記載された事項だけに限定されて解釈されてはならない。
従来技術による後処理工程で用いられるプリント回路用銅箔メッキ装置の構成図である。 図１のプリント回路用銅箔メッキ装置によって表面処理されたプリント回路用銅箔の主要構成を示した断面図である。 本発明の望ましい実施例によるプリント回路用銅箔の表面処理方法が行われる過程を示したフロー図である。 本発明の望ましい実施例によるプリント回路用銅箔メッキ装置の構成図である。 本発明の望ましい実施例によるプリント回路用銅箔メッキ装置によって表面処理されたプリント回路用銅箔の主要構成を示した断面図である。 本発明の実施例によるプリント回路用銅箔の剥離強度特性を従来技術と比べた表である。 The following drawings attached to the specification illustrate preferred embodiments of the present invention, and together with the detailed description, serve to further understand the technical idea of the present invention. It should not be construed as being limited to the matters described in the drawings.
It is a block diagram of the copper foil plating apparatus for printed circuits used in the post-processing process by a prior art. It is sectional drawing which showed the main structures of the copper foil for printed circuits surface-treated by the copper foil plating apparatus for printed circuits of FIG. 1 is a flowchart illustrating a process in which a surface treatment method for a printed circuit copper foil according to a preferred embodiment of the present invention is performed. 1 is a configuration diagram of a copper foil plating apparatus for a printed circuit according to a preferred embodiment of the present invention. 1 is a cross-sectional view illustrating a main configuration of a printed circuit copper foil surface-treated by a printed circuit copper foil plating apparatus according to a preferred embodiment of the present invention. It is the table | surface which compared the peeling strength characteristic of the copper foil for printed circuits by the Example of this invention with the prior art.

以下、添付された図面を参照して本発明の望ましい実施例を詳しく説明する。これに先立ち、本明細書及び請求範囲に使われた用語や単語は通常的や辞書的な意味に限定して解釈されてはならず、発明者自らは発明を最善の方法で説明するために用語の概念を適切に定義できるという原則に則して本発明の技術的な思想に応ずる意味及び概念で解釈されねばならない。したがって、本明細書に記載された実施例及び図面に示された構成は、本発明のもっとも望ましい一実施例に過ぎず、本発明の技術的な思想のすべてを代弁するものではないため、本出願の時点においてこれらに代替できる多様な均等物及び変形例があり得ることを理解せねばならない。   Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. Prior to this, the terms and words used in this specification and claims should not be construed to be limited to ordinary or lexicographic meanings, and the inventor himself should explain the invention in the best possible manner. It must be interpreted with the meaning and concept corresponding to the technical idea of the present invention in accordance with the principle that the term concept can be appropriately defined. Therefore, the configuration described in the embodiments and drawings described in this specification is only the most preferable embodiment of the present invention, and does not represent all of the technical idea of the present invention. It should be understood that there are various equivalents and variations that can be substituted at the time of filing.

図３に示されたように、本発明では、製箔処理を施して銅箔を製造した後（Ｓ１００）、銅箔のＭ面に銅をメッキして多数のノジュール構造を形成するノジュール処理（Ｓ１１０）と、銅ノジュール構造の上にモリブデン（Ｍｏ）成分を含むメッキ層を形成して物理的、化学的特性を強化するバリア層メッキ処理（Ｓ１２０）と、を含む表面処理工程を施す。   As shown in FIG. 3, in the present invention, a copper foil is manufactured by performing a foil manufacturing process (S100), and then copper is plated on the M surface of the copper foil to form a number of nodule structures ( A surface treatment process including S110) and a barrier layer plating process (S120) in which a plating layer containing a molybdenum (Mo) component is formed on the copper nodule structure to enhance physical and chemical characteristics is performed.

図４には、本発明の望ましい実施例による表面処理方法を行うためのプリント回路用銅箔メッキ装置の概略的な構成が示されている。   FIG. 4 shows a schematic configuration of a copper foil plating apparatus for a printed circuit for performing a surface treatment method according to a preferred embodiment of the present invention.

図４を参照すれば、本発明の望ましい実施例によるプリント回路用銅箔メッキ装置は、銅箔上に銅ノジュール構造を形成するための第１銅メッキ槽１００及び第２銅メッキ槽１０１と、銅ノジュール構造の上にバリア層を形成するためのモリブデンメッキ槽１０２と、を含む。   Referring to FIG. 4, a copper foil plating apparatus for a printed circuit according to a preferred embodiment of the present invention includes a first copper plating tank 100 and a second copper plating tank 101 for forming a copper nodule structure on a copper foil, And a molybdenum plating bath 102 for forming a barrier layer on the copper nodule structure.

第１銅メッキ槽１００には銅箔のＭ面に銅ノジュールの核を生成させるためのメッキ液が満たされ、第２銅メッキ槽１０１には銅ノジュールの核を成長させるためのメッキ液が満たされる。   The first copper plating tank 100 is filled with a plating solution for generating copper nodule nuclei on the M surface of the copper foil, and the second copper plating tank 101 is filled with a plating solution for growing copper nodule nuclei. It is.

モリブデンメッキ槽１０２には、耐熱性を始め、耐酸性及び耐腐食性に優れたモリブデン（Ｍｏ）またはモリブデン（Ｍｏ）合金成分を含むメッキ液が満たされる。メッキ液内でイオン状態で存在していたモリブデン（Ｍｏ）は、電解による析出時に金属または合金形態で銅ノジュール上に電着される。   The molybdenum plating tank 102 is filled with a plating solution containing molybdenum (Mo) or a molybdenum (Mo) alloy component having excellent acid resistance and corrosion resistance as well as heat resistance. Molybdenum (Mo) present in an ionic state in the plating solution is electrodeposited on the copper nodules in the form of a metal or an alloy during deposition by electrolysis.

モリブデン（Ｍｏ）成分によって与えられる物理的、化学的特性をより強化するために、プリント回路用銅箔メッキ装置には亜鉛（Ｚｎ）または亜鉛（Ｚｎ）合金成分を含むメッキ液が満たされる亜鉛メッキ槽１０３と、クロム（Ｃｒ）またはクロム（Ｃｒ）合金成分を含むメッキ液が満たされるクロムメッキ槽１０４と、がさらに備えられる。   In order to further enhance the physical and chemical properties given by the molybdenum (Mo) component, the copper foil plating apparatus for printed circuits is filled with a plating solution containing zinc (Zn) or a zinc (Zn) alloy component. A tank 103 and a chromium plating tank 104 filled with a plating solution containing chromium (Cr) or a chromium (Cr) alloy component are further provided.

モリブデンメッキ槽１０２に満たされるメッキ液中のモリブデン（Ｍｏ）含量は、２０ｇ／ｌに設定され得る。一方、モリブデン（Ｍｏ）‐ニッケル（Ｎｉ）合金が使われる場合、メッキ液中のモリブデン（Ｍｏ）含量は１５ｇ／ｌ、ニッケル（Ｎｉ）含量は３０ｇ／ｌに設定され得る。ここで、メッキ液のｐＨは１２、温度は２５℃に保持することが望ましい。   The molybdenum (Mo) content in the plating solution filled in the molybdenum plating tank 102 can be set to 20 g / l. On the other hand, when a molybdenum (Mo) -nickel (Ni) alloy is used, the molybdenum (Mo) content in the plating solution can be set to 15 g / l, and the nickel (Ni) content can be set to 30 g / l. Here, it is desirable to maintain the pH of the plating solution at 12 and the temperature at 25 ° C.

製箔工程によって製造された本体銅箔２００は、第１銅メッキ槽１００、第２銅メッキ槽１０１、モリブデンメッキ槽１０２、亜鉛メッキ槽１０３、及びクロムメッキ槽１０４を順次連続的に通過することで電気メッキによって表面処理される。ここで、本体銅箔２００は複数のガイドロール１０５によって各メッキ槽の内部に導かれ、最終的に巻取りロール１０６に巻き取られる。各メッキ槽の内部に配置されるガイドロール１０５は、電気メッキのために該当メッキ液に印加される極性に対応する極性の電極が連結されて通電される。   The main body copper foil 200 manufactured by the foil making process sequentially passes through the first copper plating tank 100, the second copper plating tank 101, the molybdenum plating tank 102, the galvanizing tank 103, and the chrome plating tank 104 sequentially. Surface treatment is performed by electroplating. Here, the main body copper foil 200 is guided to the inside of each plating tank by a plurality of guide rolls 105 and finally taken up by the take-up roll 106. The guide roll 105 disposed inside each plating tank is energized with an electrode having a polarity corresponding to the polarity applied to the corresponding plating solution for electroplating.

図５には、本発明の望ましい実施例によるプリント回路用銅箔メッキ装置によって製作されたプリント回路用銅箔の構成が示されている。   FIG. 5 shows a structure of a copper foil for a printed circuit manufactured by a copper foil plating apparatus for a printed circuit according to a preferred embodiment of the present invention.

図５に示されたように、プリント回路用銅箔は、本体銅箔２００と、本体銅箔２００のＭ面上に形成される銅ノジュール層２０１と、銅ノジュール層２０１上に設けられ、モリブデン（Ｍｏ）を始め亜鉛（Ｚｎ）、クロム（Ｃｒ）などの成分を含むバリア層２０２と、を含む。   As shown in FIG. 5, the printed circuit copper foil is provided on the main body copper foil 200, the copper nodule layer 201 formed on the M surface of the main body copper foil 200, and the copper nodule layer 201. And a barrier layer 202 containing components such as zinc (Zn) and chromium (Cr).

銅ノジュール層２０１上にメッキされるモリブデン（Ｍｏ）成分は、耐熱性を向上させることでＦＲ（Ｆｌａｍｅ Ｒｅｔａｒｄａｎｔ）−４などの樹脂フィルムに対する接着強度を高め、耐酸性、耐腐食性などを高める作用をする。バリア層２０２において、モリブデン（Ｍｏ）のメッキ量は０．５〜１００ｍｇ／ｍ２であることが効果的である。モリブデン（Ｍｏ）合金がメッキされる場合、モリブデン（Ｍｏ）以外の元素（例えば、ニッケル（Ｎｉ）などの遷移金属）のメッキ量はモリブデン（Ｍｏ）メッキ量の０．１倍〜２倍であることが望ましい。 Molybdenum (Mo) component plated on the copper nodule layer 201 improves the adhesion strength to resin films such as FR (Frame Regentant) -4 by improving heat resistance, and improves acid resistance and corrosion resistance. do. In the barrier layer 202, it is effective that the plating amount of molybdenum (Mo) is 0.5 to 100 mg / m 2 . When molybdenum (Mo) alloy is plated, the plating amount of elements other than molybdenum (Mo) (for example, transition metals such as nickel (Ni)) is 0.1 to 2 times the molybdenum (Mo) plating amount. It is desirable.

亜鉛（Ｚｎ）とクロム（Ｃｒ）成分は、バリア層２０２の耐熱、耐酸性などをより強化させる作用をする。ここで、特に亜鉛（Ｚｎ）のメッキ量は２０ｍｇ／ｍ２以下であることが効果的である。 The zinc (Zn) and chromium (Cr) components act to further strengthen the heat resistance and acid resistance of the barrier layer 202. Here, it is particularly effective that the plating amount of zinc (Zn) is 20 mg / m 2 or less.

バリア層２０２上には、銅箔に接着される樹脂フィルムとの接着力を向上させるためにシランカップリング剤（図示せず）が塗布される。ここで、シランとしてはエポキシ系またはアミン系が望ましい。   A silane coupling agent (not shown) is applied on the barrier layer 202 in order to improve the adhesive force with the resin film adhered to the copper foil. Here, the silane is preferably epoxy or amine.

図６には、本発明の実施例によるプリント回路用銅箔の剥離強度特性を従来技術（比較例）と比べた結果が示されている。   FIG. 6 shows the result of comparing the peel strength characteristics of the copper foil for printed circuit according to the example of the present invention with that of the prior art (comparative example).

図６において、本発明の実施例１は１２μｍ厚と１８μｍ厚の本体銅箔に対して１０ｍｇ／ｍ２ずつのモリブデン（Ｍｏ）と亜鉛（Ｚｎ）をメッキしてバリア層２０２を形成し、樹脂フィルムとしてＦＲ−４樹脂を接着した後、１８０℃で４８時間熱処理して銅箔の剥離強度を測定した結果である。 6, in Example 1 of the present invention, a barrier layer 202 is formed by plating 10 mg / m 2 of molybdenum (Mo) and zinc (Zn) on a main body copper foil having a thickness of 12 μm and a thickness of 18 μm. This is the result of measuring the peel strength of the copper foil after bonding FR-4 resin as a film and then heat-treating at 180 ° C. for 48 hours.

また、本発明の実施例２は１２μｍ厚と１８μｍ厚の本体銅箔に対して５ｍｇ／ｍ２のニッケル（Ｎｉ）と、１０ｍｇ／ｍ２ずつのモリブデン（Ｍｏ）及び亜鉛（Ｚｎ）をメッキしてバリア層２０２を形成し、樹脂フィルムとしてＦＲ−４樹脂を接着した後、１８０℃で４８時間熱処理して銅箔の剥離強度を測定した結果である。 In Example 2 of the present invention, 5 mg / m 2 of nickel (Ni), 10 mg / m 2 of molybdenum (Mo), and zinc (Zn) are plated on a main body copper foil of 12 μm thickness and 18 μm thickness. After forming the barrier layer 202 and bonding the FR-4 resin as a resin film, the result of heat treatment at 180 ° C. for 48 hours and the peel strength of the copper foil was measured.

一方、比較例は１２μｍ厚と１８μｍ厚の本体銅箔に対してニッケル（Ｎｉ）を主成分にしてバリア層を形成した場合であり、樹脂フィルムとしてＦＲ−４樹脂を接着した後、１８０℃で４８時間熱処理して銅箔の剥離強度を測定した結果である。   On the other hand, a comparative example is a case where a barrier layer is formed with nickel (Ni) as a main component on a main body copper foil of 12 μm thickness and 18 μm thickness, and after FR-4 resin is bonded as a resin film, at 180 ° C. It is the result of heat-processing for 48 hours and measuring the peeling strength of copper foil.

図６の表を参照すれば、本発明を適用したとき従来技術に比べて熱処理後の剥離強度特性が改善することが確認できる。   Referring to the table of FIG. 6, it can be confirmed that when the present invention is applied, the peel strength characteristics after heat treatment are improved as compared with the prior art.

以上のように、本発明がたとえ限定された実施例及び図面によって説明されたが、本発明はこれによって限定されるものでなく、本発明が属する技術分野で通常の知識を持つ者によって本発明の技術思想と特許請求の範囲の均等範囲内で多様な修正及び変形が可能であることは言うまでもない。   As described above, the present invention has been described by way of limited embodiments and drawings. However, the present invention is not limited thereto, and the present invention can be obtained by a person having ordinary knowledge in the technical field to which the present invention belongs. It goes without saying that various modifications and variations can be made within the scope of the technical idea and the scope of claims.

１００ 第１銅メッキ槽
１０１ 第２銅メッキ槽
１０２ モリブデンメッキ槽
１０３ 亜鉛メッキ槽
１０４ クロムメッキ槽
１０５ ガイドロール
１０６ 巻取りロール
２００ 本体銅箔
２０１ 銅ノジュール層
２０２ バリア層 DESCRIPTION OF SYMBOLS 100 1st copper plating tank 101 2nd copper plating tank 102 Molybdenum plating tank 103 Zinc plating tank 104 Chromium plating tank 105 Guide roll 106 Winding roll 200 Main body copper foil 201 Copper nodule layer 202 Barrier layer

Claims (17)

製箔工程を経た銅箔の表面に銅ノジュール層を形成する第１段階と、
前記銅ノジュール層上にモリブデン（Ｍｏ）またはモリブデン（Ｍｏ）合金をメッキしてバリア層を形成する第２段階と、を含むプリント回路用銅箔の表面処理方法。 A first step of forming a copper nodule layer on the surface of the copper foil that has undergone the foil-making process;
And a second step of forming a barrier layer by plating molybdenum (Mo) or molybdenum (Mo) alloy on the copper nodule layer. 前記モリブデン（Ｍｏ）のメッキ量が０．５〜１００ｍｇ／ｍ２であることを特徴とする請求項１に記載のプリント回路用銅箔の表面処理方法。 The surface treatment method for a copper foil for a printed circuit according to claim 1, wherein the molybdenum (Mo) plating amount is 0.5 to 100 mg / m 2 . 前記第２段階において、亜鉛（Ｚｎ）または亜鉛（Ｚｎ）合金をさらにメッキすることを特徴とする請求項１に記載のプリント回路用銅箔の表面処理方法。   2. The surface treatment method for a copper foil for a printed circuit according to claim 1, wherein in the second stage, zinc (Zn) or a zinc (Zn) alloy is further plated. 前記亜鉛（Ｚｎ）のメッキ量が２０ｍｇ／ｍ２以下であることを特徴とする請求項３に記載のプリント回路用銅箔の表面処理方法。 The surface treatment method for a copper foil for printed circuit according to claim 3, wherein the zinc (Zn) plating amount is 20 mg / m 2 or less. 前記第２段階において、クロム（Ｃｒ）またはクロム（Ｃｒ）合金をさらにメッキすることを特徴とする請求項１に記載のプリント回路用銅箔の表面処理方法。   2. The surface treatment method for a copper foil for a printed circuit according to claim 1, wherein in the second step, chromium (Cr) or a chromium (Cr) alloy is further plated. 前記第２段階の後に前記バリア層上にシランカップリング剤を塗布することを特徴とする請求項１に記載のプリント回路用銅箔の表面処理方法。   The surface treatment method for a copper foil for a printed circuit according to claim 1, wherein a silane coupling agent is applied on the barrier layer after the second step. 前記第２段階で使われるメッキ液にはイオン状態で存在するモリブデン（Ｍｏ）が含有されることを特徴とする請求項１に記載のプリント回路用銅箔の表面処理方法。   The surface treatment method for a copper foil for a printed circuit according to claim 1, wherein the plating solution used in the second step contains molybdenum (Mo) present in an ionic state. 本体銅箔と、
前記本体銅箔の表面に形成された銅ノジュール層と、
前記銅ノジュール層上にメッキされ、モリブデン（Ｍｏ）層またはモリブデン（Ｍｏ）合金層を含むバリア層と、を含むプリント回路用銅箔。 The body copper foil,
A copper nodule layer formed on the surface of the main body copper foil;
And a barrier layer plated on the copper nodule layer and including a molybdenum (Mo) layer or a molybdenum (Mo) alloy layer. 前記モリブデン（Ｍｏ）のメッキ量が０．５〜１００ｍｇ／ｍ２であることを特徴とする請求項８に記載のプリント回路用銅箔。 The copper foil for printed circuits according to claim 8, wherein the molybdenum (Mo) plating amount is 0.5 to 100 mg / m 2 . 前記バリア層には亜鉛（Ｚｎ）層または亜鉛（Ｚｎ）合金層がさらに含まれることを特徴とする請求項８に記載のプリント回路用銅箔。   The printed circuit copper foil according to claim 8, wherein the barrier layer further includes a zinc (Zn) layer or a zinc (Zn) alloy layer. 前記亜鉛（Ｚｎ）のメッキ量が２０ｍｇ／ｍ２以下であることを特徴とする請求項１０に記載のプリント回路用銅箔。 11. The copper foil for printed circuit according to claim 10, wherein the zinc (Zn) plating amount is 20 mg / m 2 or less. 前記バリア層にはクロム（Ｃｒ）層またはクロム（Ｃｒ）合金層がさらに含まれることを特徴とする請求項８に記載のプリント回路用銅箔。   The printed circuit copper foil according to claim 8, wherein the barrier layer further includes a chromium (Cr) layer or a chromium (Cr) alloy layer. 前記バリア層上にシランカップリング剤層がさらに形成されたことを特徴とする請求項８に記載のプリント回路用銅箔。   The printed circuit copper foil according to claim 8, further comprising a silane coupling agent layer formed on the barrier layer. 前記本体銅箔にはポリイミド（ＰＩ）フィルムが付着されたことを特徴とする請求項８ないし請求項１３のうちいずれか１項に記載のプリント回路用銅箔。   The printed circuit copper foil according to any one of claims 8 to 13, wherein a polyimide (PI) film is attached to the main body copper foil. 製箔工程を経た銅箔の表面を処理するための銅箔メッキ装置において、
前記銅箔の表面に銅ノジュールの核を生成できるメッキ液が満たされた第１銅メッキ槽と、
前記銅箔の表面に対して銅ノジュールの核を成長できるメッキ液が満たされた第２銅メッキ槽と、
前記銅箔の銅ノジュール上にモリブデン（Ｍｏ）またはモリブデン（Ｍｏ）合金をメッキするためのメッキ液が満たされたモリブデンメッキ槽と、を含むことを特徴とするプリント回路用銅箔メッキ装置。 In the copper foil plating apparatus for processing the surface of the copper foil that has undergone the foil making process,
A first copper plating tank filled with a plating solution capable of generating copper nodule nuclei on the surface of the copper foil;
A second copper plating tank filled with a plating solution capable of growing copper nodule nuclei on the surface of the copper foil;
A copper foil plating apparatus for a printed circuit, comprising: a molybdenum plating bath filled with a plating solution for plating molybdenum (Mo) or molybdenum (Mo) alloy on the copper nodules of the copper foil. 前記銅箔の銅ノジュール上に亜鉛（Ｚｎ）または亜鉛（Ｚｎ）合金をメッキするためのメッキ液が満たされた亜鉛メッキ槽をさらに含むことを特徴とする請求項１５に記載のプリント回路用銅箔メッキ装置。   The printed circuit copper according to claim 15, further comprising a zinc plating tank filled with a plating solution for plating zinc (Zn) or a zinc (Zn) alloy on the copper nodules of the copper foil. Foil plating equipment. 前記銅箔の銅ノジュール上にクロム（Ｃｒ）またはクロム（Ｃｒ）合金をメッキするためのメッキ液が満たされたクロムメッキ槽をさらに含むことを特徴とする請求項１５に記載のプリント回路用銅箔メッキ装置。
The printed circuit copper according to claim 15, further comprising a chromium plating bath filled with a plating solution for plating chromium (Cr) or a chromium (Cr) alloy on the copper nodules of the copper foil. Foil plating equipment.
JP2009040973A 2008-02-28 2009-02-24 Copper foil for printed circuit and surface treating method thereof, and plating apparatus Pending JP2009206514A (en)

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JP2005340634A (en) * 2004-05-28 2005-12-08 Hitachi Cable Ltd Copper foil for printed wiring board, and its production process
JP2005340633A (en) * 2004-05-28 2005-12-08 Hitachi Cable Ltd Copper foil for printed wiring board and its production process
JP2005353918A (en) * 2004-06-11 2005-12-22 Hitachi Cable Ltd Copper foil for printed-wiring board and manufacturing method thereof
JP2006319286A (en) * 2005-05-16 2006-11-24 Hitachi Cable Ltd Copper foil for printed circuit board with taking environmental conservation into consideration

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WO2013115382A1 (en) * 2012-02-03 2013-08-08 Jx日鉱日石金属株式会社 Copper foil for printed wiring board, as well as laminate, printed wiring board, and electronic component using same
JP2013161925A (en) * 2012-02-03 2013-08-19 Jx Nippon Mining & Metals Corp Copper foil for printed wiring plate, laminate using the same, printed wiring plate and electronic component
CN104080951A (en) * 2012-02-03 2014-10-01 Jx日矿日石金属株式会社 Copper foil for printed wiring board, as well as laminate, printed wiring board, and electronic component using same
JP2016207794A (en) * 2015-04-21 2016-12-08 京セラ株式会社 Wiring board

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