JP2002368365A - Composite copper foil equipped with copper or copper alloy support and printed board using the same - Google Patents
Composite copper foil equipped with copper or copper alloy support and printed board using the sameInfo
- Publication number
- JP2002368365A JP2002368365A JP2001168090A JP2001168090A JP2002368365A JP 2002368365 A JP2002368365 A JP 2002368365A JP 2001168090 A JP2001168090 A JP 2001168090A JP 2001168090 A JP2001168090 A JP 2001168090A JP 2002368365 A JP2002368365 A JP 2002368365A
- Authority
- JP
- Japan
- Prior art keywords
- copper
- copper foil
- composite
- alloy support
- foil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- 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
- C25D1/04—Wires; Strips; 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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
- H05K3/025—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates by transfer of thin metal foil formed on a temporary carrier, e.g. peel-apart copper
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、極薄銅箔のハンド
リング性を向上させ、銅箔表面にプリプレグシートの樹
脂粉等の汚染物が付着しないようにし、さらに異物によ
る傷、打痕防止に有効な銅又は銅合金の支持体付複合銅
箔及び該複合銅箔を使用したプリント基板に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention improves the handling of ultra-thin copper foil, prevents contaminants such as resin powder of prepreg sheets from adhering to the surface of the copper foil, and prevents scratches and dents due to foreign matter. The present invention relates to an effective copper or copper alloy-supported composite copper foil and a printed circuit board using the composite copper foil.
【０００２】[0002]
【従来の技術】従来、プリント回路基板に使用される銅
張り積層板は、銅箔を紙−フェノール樹脂含浸基材やガ
ラス−エポキシ樹脂含浸基材に積層し、プレス装置を用
いて加熱・加圧して形成されたり、銅箔ロールと樹脂基
材を連続的にラミネート、加熱して形成されている。さ
らにこの銅張り積層板は、エッチング等の処理を経て回
路網を形成し、さらに半導体装置等の素子を搭載するこ
とにより電子機器用のボードが作製されている。一般
に、プレスやラミネート装置を用いて銅箔を加圧する際
に、銅箔の光沢面（Ｓ面）等に銅箔の切断時に発生した
銅の切屑やプリプレグの樹脂粉等の異物が付着している
と、前記光沢面が傷付いたり、異物が接着してしまうと
いう問題があった。また、積層後でも装置から銅張り積
層板を取り出す時や重ね合わせる時などに、光沢面相互
が擦り合わされて傷付く場合もあった。2. Description of the Related Art Conventionally, a copper-clad laminate used for a printed circuit board is formed by laminating a copper foil on a paper-phenol resin-impregnated base material or a glass-epoxy resin-impregnated base material, and heating and heating using a press device. It is formed by pressing or by continuously laminating and heating a copper foil roll and a resin substrate. Further, the copper-clad laminate forms a circuit network through processes such as etching, and further, an element such as a semiconductor device is mounted thereon, thereby manufacturing a board for electronic equipment. In general, when pressing a copper foil using a press or a laminating apparatus, foreign matter such as copper chips or prepreg resin powder generated when cutting the copper foil adheres to the glossy surface (S surface) of the copper foil. In such a case, there is a problem that the glossy surface is damaged or a foreign substance adheres. Further, even after the lamination, when the copper-clad laminates are taken out of the apparatus or when they are overlapped, the glossy surfaces may be rubbed against each other and damaged.
【０００３】近年、電子機器の小型化の要請から回路幅
が著しく小さくなり、それに伴って銅張り積層板に使用
される銅箔の厚さも１２μｍ以下になるなど、厚さを減
少させた銅箔の需要が大きくなってきている。ところ
が、銅箔の厚さが１２μｍ以下に減少するとハンドリン
グ性が極めて悪化する。上記に述べたプレス及びラミネ
ート工程に限らず、通常の切断や梱包さらには運搬中に
傷が付いたり、異物が混入したり、しわ、折れ等が発生
することが多くなり、特に銅箔の光沢面ではその影響を
強く受けやすいという問題がある。このように傷、し
わ、折れ等が発生したものは、特に光沢面側に発生した
場合、回路の断線や短絡の原因となり、それはさらにプ
リント回路基板や電子機器の欠陥につながり大きな問題
となってきている。[0003] In recent years, due to the demand for miniaturization of electronic equipment, the circuit width has been remarkably reduced, and the thickness of the copper foil used for the copper-clad laminate has been reduced to 12 μm or less. Demand is growing. However, when the thickness of the copper foil is reduced to 12 μm or less, the handling property is extremely deteriorated. Not only in the press and lamination processes described above, but also during normal cutting and packing, and even during transportation, scratches, foreign substances are mixed, wrinkles, breaks, etc. often occur, especially the gloss of copper foil On the other hand, there is a problem that it is easily affected by the influence. Such scratches, wrinkles, breaks, and the like, especially when they occur on the glossy side, cause disconnection or short circuit of the circuit, which further leads to defects in printed circuit boards and electronic devices, which is a serious problem. ing.
【０００４】以上のような銅箔表面の傷、しわ、折れ等
を防止し、ハンドリング性を向上させようとして、いく
つかの提案がなされている。その一例を挙げると、例え
ばプレス成形時の加熱温度（約１７０°Ｃ）に耐えるポ
リアミド等の樹脂フイルムを、接着剤を用いて銅箔に接
着しようとする提案がある。しかし、このような樹脂フ
イルムでは相当厚いフイルムを使用しない限り、銅箔の
ハンドリング性を向上させるほどの強度を得ることがで
きないために、しわや折れを効果的に防止できず、また
樹脂や接着剤の熱による膨張・収縮により変形するおそ
れがあり、さらにフイルムの接着に使用する接着剤が銅
箔に残存して汚染の原因になる場合があり、必ずしも良
好な改善策とは言えなかった。また、樹脂フイルムの代
わりにアルミニウム箔を使用し、接着剤を用いて銅箔に
接着しようとする提案もなされている。しかし、使用さ
れるアルミニウム箔は通常圧延で製造されており、その
際使用される圧延油が残留し、接着時に銅箔に転写し
て、プリント基板の作製時に、これが原因でレジストの
密着性が劣化するという問題が発生した。アルミニウム
箔を脱脂したり、高温で焼鈍することで圧延油を除去す
ることは可能だが、コストアップとなる問題がある。ま
た、高温で焼鈍するとアルミニウム箔が軟化し強度が低
下するため、キヤリアとして使用するためには厚みをか
なり厚くする必要があり、コストアップや重量増の問題
が発生する。このような圧延油残留問題以外にも、アル
ミニウム箔には表面のアルミニウム粉がプレス時に銅箔
に転写し、回路の断線や短絡の原因となる問題点があっ
た。さらに、有機系及びニッケルを剥離層とした複合銅
箔の提案もある。しかし、この場合は樹脂との積層プレ
ス時に、剥離層が銅又は銅合金の支持体及び極薄銅箔に
拡散し、銅又は銅合金の支持体との剥離に問題があると
いう欠点があった。Some proposals have been made to prevent the above-mentioned scratches, wrinkles, breaks, and the like on the copper foil surface and to improve the handleability. As an example, there is a proposal to bond a resin film such as polyamide, which withstands a heating temperature (about 170 ° C.) during press molding, to a copper foil using an adhesive. However, unless such a resin film is used, it is not possible to obtain enough strength to improve the handleability of the copper foil unless a considerably thick film is used, so that wrinkles and breaks cannot be effectively prevented. The agent may be deformed due to expansion and contraction due to heat of the agent, and the adhesive used for bonding the film may remain on the copper foil to cause contamination, and this is not necessarily a good improvement measure. It has also been proposed to use an aluminum foil instead of a resin film and to bond the film to a copper foil using an adhesive. However, the aluminum foil used is usually manufactured by rolling, and the rolling oil used at that time remains, which is transferred to the copper foil at the time of bonding, and the adhesiveness of the resist is reduced due to this during the production of the printed circuit board. The problem of deterioration occurred. Although it is possible to remove the rolling oil by degreasing the aluminum foil or annealing at a high temperature, there is a problem that the cost increases. Further, annealing at a high temperature softens the aluminum foil and lowers its strength. Therefore, in order to use it as a carrier, it is necessary to considerably increase its thickness, which causes problems of cost increase and weight increase. In addition to the problem of residual rolling oil, the aluminum foil has a problem that aluminum powder on the surface is transferred to the copper foil at the time of pressing and causes disconnection or short circuit of the circuit. Furthermore, there is a proposal of a composite copper foil using an organic material and nickel as a release layer. However, in this case, at the time of laminating press with resin, there was a disadvantage that the peeling layer diffused into the copper or copper alloy support and the ultra-thin copper foil, and there was a problem in peeling from the copper or copper alloy support. .
【０００５】[0005]
【発明が解決しょうとする課題】本発明は上記のような
問題点に鑑みてなされたものであり、その目的とすると
ころは、極薄銅箔のハンドリング性を向上させ、銅箔表
面にプリプレグシートの樹脂粉等の汚染物が付着しない
ようにし、異物による傷、打痕防止、さらには切断、梱
包、運搬中の傷、しわ、折れ等を効果的に防止できる銅
又は銅合金の支持体（キャリア）を備えた複合銅箔及び
該複合銅箔を使用したプリント基板を得ようとするもの
である。SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to improve the handleability of ultra-thin copper foil and to improve the prepreg on the copper foil surface. A copper or copper alloy support that prevents contaminants such as resin powder on the sheet from adhering and prevents scratches and dents due to foreign matter, and can effectively prevent scratches, wrinkles, and breaks during cutting, packing, and transportation. An object is to obtain a composite copper foil provided with a (carrier) and a printed circuit board using the composite copper foil.
【０００６】[0006]
【課題を解決するための手段】以上から、本発明は １． 銅又は銅合金の支持体と極薄銅箔との間の支持体
側に、酸化膜で覆われたニッケル層を有することを特徴
とする銅又は銅合金の支持体を備えた複合銅箔及び該複
合銅箔を使用したプリント基板。 ２． ０．０５〜５．０μｍのニッケル層を有すること
を特徴とする上記１記載の銅又は銅合金の支持体を備え
た複合銅箔及び該複合銅箔を使用したプリント基板。 ３． ニッケル層の酸化膜の厚さが２５〜５００Åであ
ることを特徴とする上記１又は２記載の銅又は銅合金の
支持体を備えた複合銅箔及び該複合銅箔を使用したプリ
ント基板。 ４． 銅又は銅合金の支持体の厚さが１５〜７０μｍで
あることを特徴とする上記１〜３のそれぞれに記載の銅
又は銅合金の支持体を備えた複合銅箔及び該複合銅箔を
使用したプリント基板。 ５． 銅又は銅合金の支持体が電解銅箔又は圧延銅箔で
あることを特徴とする上記１〜４のそれぞれに記載の銅
又は銅合金の支持体を備えた複合銅箔及び該複合銅箔を
使用したプリント基板。 ６． 銅又は銅合金の支持体に支持される極薄銅箔の厚
さが０．５〜１２μｍであることを特徴とする上記１〜
５のそれぞれに記載の銅又は銅合金の支持体を備えた複
合銅箔及び該複合銅箔を使用したプリント基板。 ７． 極薄銅箔とニッケル層との剥離強度が０．００２
〜０．５ｋｇ／ｃｍであることを特徴とする上記１〜６
のそれぞれに記載の銅又は銅合金の支持体を備えた複合
銅箔及び該複合銅箔を使用したプリント基板。を提供す
る。From the above, the present invention provides: A composite copper foil provided with a copper or copper alloy support, which has a nickel layer covered with an oxide film on the support side between the copper or copper alloy support and the ultra-thin copper foil, Printed circuit board using composite copper foil. 2. 2. A composite copper foil provided with a copper or copper alloy support as described in 1 above, which has a nickel layer of 0.05 to 5.0 μm, and a printed circuit board using the composite copper foil. 3. 3. The composite copper foil provided with the copper or copper alloy support according to the above 1 or 2, wherein the thickness of the oxide film of the nickel layer is 25 to 500 °, and a printed board using the composite copper foil. 4. The composite copper foil provided with the copper or copper alloy support according to any one of the above 1 to 3, wherein the copper or copper alloy support has a thickness of 15 to 70 μm, and the composite copper foil is used. Printed circuit board. 5. The composite copper foil and the composite copper foil provided with the copper or copper alloy support according to any one of the above 1 to 4, wherein the copper or copper alloy support is an electrolytic copper foil or a rolled copper foil Printed circuit board used. 6. Wherein the thickness of the ultra-thin copper foil supported on the copper or copper alloy support is 0.5 to 12 μm.
5. A composite copper foil provided with the copper or copper alloy support according to 5 above, and a printed circuit board using the composite copper foil. 7. 0.002 peel strength between ultra-thin copper foil and nickel layer
1 to 6 characterized by the above-mentioned.
And a printed circuit board using the composite copper foil provided with the copper or copper alloy support described in any one of the above. I will provide a.
【０００７】[0007]
【発明の実施の形態】本発明の銅又は銅合金の支持体を
備えた複合銅箔及び該複合銅箔を使用したプリント基板
は、まず銅又は銅合金の支持体の表面に、０．０５〜
５．０μｍのニッケルめっき層を形成する。このニッケ
ルめっき層を形成する条件の好ましい一例を下記に示
す。ニッケルめっき ニッケル濃度 ：１０〜８０ｇ／Ｌ 電解液温度 ：２０〜８０°Ｃ 電流密度 ：０．１〜２０Ａ／ｄｍ２ ｐＨ ：１．０〜５．０ このニッケル層の表面にさらに酸化膜を形成する。この
酸化膜の厚さは２５〜５００Åであることが望ましい。
酸化膜は極薄銅箔の剥離性を著しく向上させることがで
きる。このニッケル層の上に酸化膜を形成する手段とし
て陽極酸化があり、この酸化膜形成を形成する条件の好
ましい一例を下記に示す。酸化膜形成 ＮａＯＨ濃度 ：０．５〜２０ｇ／Ｌ 電解液温度 ：２０〜５０°Ｃ 電流密度 ：１〜１０Ａ／ｄｍ２ そしてこの酸化膜の上に極薄銅箔を形成する。極薄銅箔
の厚さは０．５〜１２μｍであることが望ましい。極薄
銅箔を形成は電気めっきによって形成するが、その銅め
っきの好ましい条件の一例を下記に示す。銅めっき 銅濃度 ：３０〜１２０ｇ／Ｌ Ｈ２ＳＯ４濃度 ：２０〜１２０ｇ／Ｌ 電解液温度 ：２０〜８０°Ｃ 電流密度 ：１０〜１００Ａ／ｄｍ２ BEST MODE FOR CARRYING OUT THE INVENTION A composite copper foil provided with a copper or copper alloy support of the present invention and a printed circuit board using the composite copper foil are prepared by first placing 0.05% on the surface of a copper or copper alloy support. ~
A nickel plating layer of 5.0 μm is formed. Preferred examples of the conditions for forming the nickel plating layer are shown below. Nickel plating Nickel concentration: 10 to 80 g / L Electrolyte temperature: 20 to 80 ° C Current density: 0.1 to 20 A / dm 2 pH: 1.0 to 5.0 An oxide film is further formed on the surface of this nickel layer I do. The thickness of this oxide film is desirably 25 to 500 °.
The oxide film can significantly improve the peelability of the ultra-thin copper foil. Anodization is a means for forming an oxide film on the nickel layer, and a preferred example of conditions for forming the oxide film is shown below. Oxide film forming NaOH concentration: 0.5 to 20 g / L Electrolyte temperature: 20 to 50 ° C. Current density: 1 to 10 A / dm 2 Then, an ultra-thin copper foil is formed on the oxide film. The thickness of the ultra-thin copper foil is desirably 0.5 to 12 μm. The ultra-thin copper foil is formed by electroplating. An example of preferable conditions for the copper plating is shown below. Copper plating copper concentration: 30 to 120 g / L H 2 SO 4 concentration: 20 to 120 g / L Electrolyte temperature: 20 to 80 ° C. Current density: 10 to 100 A / dm 2
【０００８】これによって、銅又は銅合金の支持体を備
えた複合銅箔が得られる。さらに、この積層された複合
銅箔と樹脂基材をプレス又はラミネートにより積層し
て、銅張積層板が形成されるが、この銅又は銅合金の支
持体を備えた複合銅箔はハンドリング性が極めて良好な
為、しわ、折れ等の発生を効果的に防止でき、また銅又
は銅合金の支持体による覆いにより銅箔の面に直接異物
が付着するのを防止できる。さらに積層後、酸化膜を有
するニッケル層の部分から銅又は銅合金の支持体を剥離
し、エッチング等の処理により回路網が形成されるが、
回路形成の直前まで酸化膜を備えたニッケル層を有する
銅又は銅合金の支持体で保護されているため、銅張積層
板の異物による傷、打痕防止に有効であり、さらには切
断、梱包、運搬中の傷、しわ、折れ等を効果的に防止で
きる。As a result, a composite copper foil provided with a copper or copper alloy support is obtained. Further, the laminated composite copper foil and the resin base material are laminated by pressing or laminating to form a copper-clad laminate. The composite copper foil provided with the copper or copper alloy support has a handleability. Since it is extremely good, it is possible to effectively prevent wrinkles, breaks, and the like from occurring, and to prevent foreign substances from directly adhering to the surface of the copper foil by covering with a copper or copper alloy support. After further lamination, the copper or copper alloy support is peeled from the nickel layer portion having an oxide film, and a circuit network is formed by a process such as etching.
Immediately before circuit formation, it is protected by a copper or copper alloy support having a nickel layer with an oxide film, which is effective in preventing scratches and dents due to foreign matter on the copper-clad laminate, and furthermore, cutting and packing In addition, scratches, wrinkles, breaks, and the like during transportation can be effectively prevented.
【０００９】本発明の銅箔に使用する銅又は銅合金の支
持体は電解銅箔又は圧延銅箔を使用することができる。
その好適な厚さは１５〜７０μｍである。コスト面から
はより薄い電解銅箔又は圧延銅箔を用いるのが望ましい
が、あまり薄いと強度的に支持体（キャリア）として使
用できないため、ある程度以上の厚みは必要である。極
薄銅箔と表面に酸化膜層を形成したニッケル層との剥離
強度が０．００２〜０．５ｋｇ／ｃｍ２であり、容易に
剥離することができる。なお、この場合の剥離強度は、
前記複合銅箔を極薄銅箔側に１５０°Ｃ以上で基材に積
層した場合の値を示す。The copper or copper alloy support used in the copper foil of the present invention may be an electrolytic copper foil or a rolled copper foil.
Its preferred thickness is between 15 and 70 μm. From the viewpoint of cost, it is desirable to use a thinner electrolytic copper foil or rolled copper foil. However, if it is too thin, it cannot be used as a support (carrier) in terms of strength, so a certain thickness or more is required. The peel strength between the ultra-thin copper foil and the nickel layer having an oxide film layer formed on the surface is 0.002 to 0.5 kg / cm 2 , and it can be easily peeled. The peel strength in this case is
The values when the composite copper foil is laminated on the substrate at 150 ° C. or higher on the ultra-thin copper foil side are shown.
【００１０】ニッケル層を形成する銅箔面は光沢面
（Ｓ）面に施すのが良いが、他の面すなわち粗化面（Ｍ
面）に施しても良い。また、他のめっき等の表面処理を
行った銅箔面に施しても良い。例えば、一般にプリント
配線板用銅箔には粗化粒子形成、酸化膜形成、耐熱性膜
の形成、防錆処理等が施されるが、本発明にはこれらの
処理が適用でき、本発明はこれらの全てを包含するもの
である。The copper foil surface on which the nickel layer is formed is preferably applied to the glossy surface (S), but the other surface, that is, the roughened surface (M)
Surface). Moreover, you may give to the copper foil surface which performed surface treatments, such as other plating. For example, copper foil for printed wiring boards is generally subjected to roughening particle formation, oxide film formation, heat-resistant film formation, rust prevention treatment, etc., and these treatments can be applied to the present invention. It encompasses all of these.
【００１１】銅箔の積層工程の例を示すと、例えばプレ
ス圧力を１０〜３０ｋｇ／ｃｍ２程度、プレス温度１７
０°Ｃ前後で６０〜１８０分間、加熱及び圧力を加えて
積層する。これにより、銅箔とプリプレグシートとの接
合が十分に行うことができる。また、銅又は銅合金の支
持体を備えた複合銅箔はハンドリング性が極めて良好な
ので、しわ、折れ等が発生することがなくなる。特に、
極薄銅箔の厚さが１２μｍ以下である場合のハンドリン
グ性の向上が著しい。更に、上記プレス工程に限らず、
通常の切断や梱包、さらには運搬中に傷がついたり、異
物が混入したり、しわ、折れ等が発生することがなくな
るという効果がある。これによって、プリント回路基板
の回路の切断や短絡が減少し、さらに電子機器の欠陥を
抑制でき、製品の歩留まりが向上する効果がある。An example of the copper foil laminating step is as follows. For example, the pressing pressure is set to about 10 to 30 kg / cm 2 and the pressing temperature is set to 17 kg / cm 2.
Lamination is performed by applying heat and pressure at about 0 ° C. for 60 to 180 minutes. Thereby, the joining between the copper foil and the prepreg sheet can be sufficiently performed. Further, the composite copper foil provided with the copper or copper alloy support has extremely good handling properties, so that wrinkling, breakage and the like do not occur. In particular,
When the thickness of the ultra-thin copper foil is 12 μm or less, the handling property is remarkably improved. Furthermore, not limited to the above pressing process,
There is an effect that scratches, foreign substances are mixed, wrinkles, breaks, and the like do not occur during normal cutting, packing, and transport. As a result, the number of cuts and short circuits in the circuit of the printed circuit board is reduced, and furthermore, defects in electronic devices can be suppressed, and the yield of products can be improved.
【００１２】上記積層後、極薄銅箔から酸化膜を備えた
ニッケル層を有する銅又は銅合金の支持体を容易に剥離
除去することができる。キャリア用の銅又は銅合金の支
持体としての箔又はシート（板）はリサイクルすること
ができる。これによって、極薄銅箔のハンドリング性を
向上させ、銅箔表面にプリプレグシートの樹脂粉等の汚
染物を付着させず、異物による傷、打痕防止、さらには
切断、梱包、運搬中の傷、しわ、折れ等を発生させずに
プリント回路基板を容易に得ることができる。After the lamination, the copper or copper alloy support having the nickel layer provided with the oxide film can be easily peeled off from the ultra-thin copper foil. The foil or sheet (plate) as the carrier of copper or copper alloy for the carrier can be recycled. This improves the handling of ultra-thin copper foil, prevents contaminants such as resin powder from the prepreg sheet from adhering to the copper foil surface, prevents scratches and dents due to foreign matter, and also damages during cutting, packing, and transportation. A printed circuit board can be easily obtained without causing wrinkles, breaks, and the like.
【００１３】[0013]
【実施例及び比較例】次に、本発明の実施例及び比較例
について説明する。なお、本実施例はあくまで一例であ
り、本発明はこの例に制限されない。すなわち、本発明
の技術思想の範囲で、本実施例以外の態様あるいは変形
を全て包含するものである。Examples and Comparative Examples Next, examples and comparative examples of the present invention will be described. Note that the present embodiment is merely an example, and the present invention is not limited to this example. That is, all aspects or modifications other than the present embodiment are included within the scope of the technical idea of the present invention.
【００１４】（実施例１）支持体銅金属層として厚さ３
５μｍの電解銅箔Ｓ面に、上記ニッケルめっきの条件で
厚さ０．１μｍのニッケルめっきを行った。そしてこの
ニッケルめっきの表面に、上記条件で陽極酸化により４
５Åの酸化膜を形成した。なお、この陽極酸化の時間は
１０秒であった。酸化皮膜厚の計測はオージェ電子分光
を用いＳｉＯ２換算で計測した（以下、酸化皮膜厚の計
測は同様に行った）。さらに、この支持体銅金属に形成
した酸化膜を有するニッケル被膜の上に、前記銅めっき
の条件で厚さ５μｍの銅を析出させた。次に、この複合
銅箔をプリプレグＦＲ−４に積層し、１７５°Ｃで３０
分、３５ｋｇ／ｃｍ２の条件でプレスを行い、銅張り積
層板を得た。このようにして得た本実施例１の銅又は銅
合金の支持体を備えた複合銅箔のしわ発生の観察及び剥
離強度を調べた結果を表１に示す。表１に示す通り、極
薄銅箔とニッケル被膜を有する銅又は銅合金の支持体と
の剥離性は良好であり、しわの発生がなくハンドリング
性は良好であった。Example 1 A copper metal layer having a thickness of 3
The surface of the 5 μm electrolytic copper foil S was subjected to nickel plating with a thickness of 0.1 μm under the above-described nickel plating conditions. Then, the surface of the nickel plating is subjected to anodization under the above-described conditions by 4%.
An oxide film of 5% was formed. The time of this anodic oxidation was 10 seconds. The oxide film thickness was measured in terms of SiO 2 using Auger electron spectroscopy (hereinafter, the oxide film thickness was measured similarly). Further, on the nickel film having an oxide film formed on the support copper metal, copper having a thickness of 5 μm was deposited under the conditions of the copper plating. Next, this composite copper foil was laminated on prepreg FR-4,
The press was performed under the conditions of 35 kg / cm 2 for a minute to obtain a copper-clad laminate. Table 1 shows the results of observing the occurrence of wrinkling and examining the peel strength of the composite copper foil provided with the copper or copper alloy support of Example 1 thus obtained. As shown in Table 1, the peelability between the ultra-thin copper foil and the copper or copper alloy support having a nickel coating was good, wrinkles did not occur, and the handling property was good.
【００１５】[0015]
【表１】 [Table 1]
【００１６】（実施例２）実施例１と同様に、支持体銅
金属層として厚さ３５μｍの電解銅箔Ｓ面に、上記ニッ
ケルめっきの条件で厚さ０．５μｍのニッケルめっきを
行った。そしてこのニッケルめっきの表面に、上記条件
で陽極酸化により５０Åの酸化膜を形成した。なお、こ
の陽極酸化の時間は３０秒であった。さらに、この支持
体銅金属に形成した酸化膜を有するニッケル被膜の上
に、前記銅めっきの条件で厚さ７μｍの銅を析出させ
た。次に、この複合銅箔を実施例１と同様に、プリプレ
グＦＲ−４に積層し、１７５°Ｃで３０分、３５ｋｇ／
ｃｍ２の条件でプレスを行い、銅張り積層板を得た。こ
のようにして得た本実施例２の銅又は銅合金の支持体を
備えた複合銅箔のしわ発生の観察及び剥離強度を調べた
結果を同様に、表１に示す。表１に示す通り、極薄銅箔
とニッケル被膜を有する銅又は銅合金の支持体との剥離
性は良好であり、しわの発生がなくハンドリング性は良
好であった。Example 2 In the same manner as in Example 1, a surface of the electrolytic copper foil S having a thickness of 35 μm as a support copper metal layer was subjected to nickel plating with a thickness of 0.5 μm under the above-mentioned nickel plating conditions. Then, a 50 ° oxide film was formed on the surface of the nickel plating by anodic oxidation under the above conditions. The time of this anodization was 30 seconds. Further, 7 μm thick copper was deposited on the nickel film having an oxide film formed on the support copper metal under the conditions of the copper plating. Next, this composite copper foil was laminated on a prepreg FR-4 in the same manner as in Example 1, and was baked at 175 ° C. for 30 minutes at 35 kg / kg.
Pressing was performed under the condition of cm 2 to obtain a copper-clad laminate. Table 1 also shows the results of observing the occurrence of wrinkling and examining the peel strength of the composite copper foil provided with the copper or copper alloy support of Example 2 thus obtained. As shown in Table 1, the peelability between the ultra-thin copper foil and the copper or copper alloy support having a nickel coating was good, wrinkles did not occur, and the handling property was good.
【００１７】（実施例３）実施例１と同様に、支持体銅
金属層として厚さ３５μｍの電解銅箔Ｓ面に、上記ニッ
ケルめっきの条件で厚さ０．１μｍのニッケルめっきを
行った。そしてこのニッケルめっきの表面に、上記条件
で陽極酸化により２５Åの酸化膜を形成した。なお、こ
の陽極酸化の時間は１秒であった。さらに、この支持体
銅金属に形成した酸化膜を有するニッケル被膜の上に、
前記銅めっきの条件で厚さ５μｍの銅を析出させた。次
に、この複合銅箔を実施例１と同様に、プリプレグＦＲ
−４に積層し、１７５°Ｃで３０分、３５ｋｇ／ｃｍ２
の条件でプレスを行い、銅張り積層板を得た。このよう
にして得た本実施例３の銅又は銅合金の支持体を備えた
複合銅箔のしわ発生の観察及び剥離強度を調べた結果を
同様に、表１に示す。表１に示す通り、極薄銅箔とニッ
ケル被膜を有する銅又は銅合金の支持体との剥離性は良
好であり、しわの発生がなくハンドリング性は良好であ
った。Example 3 In the same manner as in Example 1, a 35 μm-thick electrolytic copper foil S as a support copper metal layer was nickel-plated with a thickness of 0.1 μm under the above-mentioned nickel plating conditions. Then, a 25 ° oxide film was formed on the surface of the nickel plating by anodic oxidation under the above conditions. The time of this anodic oxidation was 1 second. Further, on the nickel coating having an oxide film formed on the support copper metal,
Under the conditions of the copper plating, copper having a thickness of 5 μm was deposited. Next, in the same manner as in Example 1, the prepreg FR
-4, 35 kg / cm 2 at 175 ° C. for 30 minutes
Was pressed under the conditions described above to obtain a copper-clad laminate. Table 1 also shows the results of observing the occurrence of wrinkling and examining the peel strength of the composite copper foil provided with the copper or copper alloy support of Example 3 thus obtained. As shown in Table 1, the peelability between the ultra-thin copper foil and the copper or copper alloy support having a nickel coating was good, wrinkles did not occur, and the handling property was good.
【００１８】（実施例４）実施例１と同様に、支持体銅
金属層として厚さ３５μｍの電解銅箔Ｓ面に、上記ニッ
ケルめっきの条件で厚さ０．１μｍのニッケルめっきを
行った。そしてこのニッケルめっきの表面に、上記条件
で陽極酸化により４６０Åの酸化膜を形成した。なお、
この陽極酸化の時間は６０秒であった。さらに、この支
持体銅金属に形成した酸化膜を有するニッケル被膜の上
に、前記銅めっきの条件で厚さ５μｍの銅を析出させ
た。次に、この複合銅箔を実施例１と同様に、プリプレ
グＦＲ−４に積層し、１７５°Ｃで３０分、３５ｋｇ／
ｃｍ２の条件でプレスを行い、銅張り積層板を得た。こ
のようにして得た本実施例４の銅又は銅合金の支持体を
備えた複合銅箔のしわ発生の観察及び剥離強度を調べた
結果を同様に、表１に示す。表１に示す通り、極薄銅箔
とニッケル被膜を有する銅又は銅合金の支持体との剥離
性は良好であり、しわの発生がなくハンドリング性は良
好であった。Example 4 In the same manner as in Example 1, a 35 μm-thick electrolytic copper foil S as a support copper metal layer was nickel-plated with a thickness of 0.1 μm under the above-mentioned nickel plating conditions. Then, an oxide film of 460 ° was formed on the surface of the nickel plating by anodic oxidation under the above conditions. In addition,
The time of this anodization was 60 seconds. Further, on the nickel film having an oxide film formed on the support copper metal, copper having a thickness of 5 μm was deposited under the conditions of the copper plating. Next, this composite copper foil was laminated on a prepreg FR-4 in the same manner as in Example 1, and was baked at 175 ° C. for 30 minutes at 35 kg / kg.
Pressing was performed under the condition of cm 2 to obtain a copper-clad laminate. Table 1 also shows the results of observing the occurrence of wrinkling and examining the peel strength of the composite copper foil provided with the copper or copper alloy support of Example 4 thus obtained. As shown in Table 1, the peelability between the ultra-thin copper foil and the copper or copper alloy support having a nickel coating was good, wrinkles did not occur, and the handling property was good.
【００１９】（比較例１）支持体銅金属層として厚さ３
５μｍの電解銅箔Ｓ面に、上記ニッケルめっきの条件で
厚さ０．１μｍのニッケルめっきを行った。そしてこの
ニッケルめっきの表面に陽極酸化を行わずに、前記銅め
っきの条件で厚さ５μｍの銅を析出させた。なお、陽極
酸化を行わない場合のニッケルの酸化皮膜厚は２０Åで
あった。次に、この複合銅箔を実施例１と同様に、プリ
プレグＦＲ−４に積層し、１７５°Ｃで３０分、３５ｋ
ｇ／ｃｍ２の条件でプレスを行い、銅張り積層板を得
た。このようにして得た比較例１の銅又は銅合金の支持
体を備えた複合銅箔のしわ発生の観察及び剥離強度を調
べた結果を同様に表１に示す。(Comparative Example 1) A copper metal layer having a thickness of 3
The surface of the 5 μm electrolytic copper foil S was subjected to nickel plating with a thickness of 0.1 μm under the above-described nickel plating conditions. Then, copper having a thickness of 5 μm was deposited on the surface of the nickel plating under the conditions of the copper plating without performing anodic oxidation. In addition, the thickness of the nickel oxide film when the anodic oxidation was not performed was 20 °. Next, this composite copper foil was laminated on a prepreg FR-4 in the same manner as in Example 1, and was heated at 175 ° C. for 30 minutes for 35 k.
Pressing was performed under the conditions of g / cm 2 to obtain a copper-clad laminate. Table 1 also shows the results of observing the occurrence of wrinkling and examining the peel strength of the composite copper foil provided with the copper or copper alloy support of Comparative Example 1 thus obtained.
【００２０】表１から明らかなように、比較例１はハン
ドリング性良好で、しわの発生は見られないが、粘着テ
ープを貼り付け、これを引き剥がすピーリング（剥離）
テストを行ったところ剥離不能で、悪い結果となった。
以上の比較例の結果に対して、実施例１及び実施例２で
は上記の通り、ハンドリング性が良好でしわの発生がな
く、また実施例１及び実施例２のピール強度はいずれも
０．０２５ｋｇ／ｃｍであり、良好な剥離性を示した。
このように、本発明の銅又は銅合金の支持体の表面にニ
ッケルめっき層を形成し、このニッケル層の表面にさら
に酸化膜を形成した後、この酸化膜の上に極薄の銅箔を
形成した銅又は銅合金の支持体を備えた複合銅箔、及び
この積層された複合銅箔と樹脂基材をプレス又はラミネ
ートにより積層して、銅張積層板（プリント基板）は優
れた特性を有することが分かる。As is clear from Table 1, Comparative Example 1 has good handling properties and no wrinkles are generated, but peeling is performed by sticking an adhesive tape and peeling it off.
When the test was carried out, peeling was not possible, resulting in a bad result.
In contrast to the results of the above comparative examples, in Examples 1 and 2, as described above, the handleability was good and no wrinkles were generated, and the peel strength of Examples 1 and 2 was 0.025 kg. / Cm, and showed good releasability.
Thus, after forming a nickel plating layer on the surface of the copper or copper alloy support of the present invention and further forming an oxide film on the surface of the nickel layer, an ultra-thin copper foil is formed on the oxide film. The copper-clad laminate (printed board) has excellent characteristics by pressing or laminating the composite copper foil provided with the formed copper or copper alloy support, and the laminated composite copper foil and the resin base material by pressing or laminating. It can be seen that it has.
【００２１】[0021]
【発明の効果】銅又は銅合金の支持体を備え、該銅又は
銅合金の支持体と極薄銅箔との間に、酸化膜を備えたニ
ッケル層を有する本発明の複合銅箔及び該複合銅箔を使
用したプリント基板は、極薄銅箔のハンドリング性を向
上させ、銅箔表面にプリプレグシートの樹脂粉等の汚染
物が付着しないようにし、また異物による傷、打痕防止
に有効であり、さらには通常の切断、梱包、運搬中の
傷、異物の混入、しわ、折れ等の発生を防止できるとい
う優れた効果を有する。According to the present invention, there is provided a composite copper foil of the present invention comprising a copper or copper alloy support, and having a nickel layer provided with an oxide film between the copper or copper alloy support and the ultra-thin copper foil. Printed circuit boards using composite copper foil improve the handling of ultra-thin copper foil, prevent contaminants such as prepreg sheet resin powder from adhering to the copper foil surface, and are effective in preventing scratches and dents due to foreign matter Further, the present invention has an excellent effect of preventing the occurrence of scratches, inclusion of foreign matter, wrinkles, breaks, and the like during normal cutting, packing, and transportation.
Claims (7)
の支持体側に、酸化膜で覆われたニッケル層を有するこ
とを特徴とする銅又は銅合金の支持体を備えた複合銅箔
及び該複合銅箔を使用したプリント基板。1. A copper or copper alloy support having a nickel layer covered with an oxide film on a support side between a copper or copper alloy support and an ultra-thin copper foil. A composite copper foil and a printed circuit board using the composite copper foil.
することを特徴とする請求項１記載の銅又は銅合金の支
持体を備えた複合銅箔及び該複合銅箔を使用したプリン
ト基板。2. A composite copper foil provided with a copper or copper alloy support according to claim 1, further comprising a nickel layer having a thickness of 0.05 to 5.0 μm, and a printed circuit board using said composite copper foil. .
０Åであることを特徴とする請求項１又は２記載の銅又
は銅合金の支持体を備えた複合銅箔及び該複合銅箔を使
用したプリント基板。3. The thickness of the oxide film of the nickel layer is 25 to 50.
3. A composite copper foil provided with a copper or copper alloy support according to claim 1 or 2, and a printed circuit board using said composite copper foil.
０μｍであることを特徴とする請求項１〜３のそれぞれ
に記載の銅又は銅合金の支持体を備えた複合銅箔及び該
複合銅箔を使用したプリント基板。4. The support of copper or copper alloy has a thickness of 15 to 7
A composite copper foil provided with the copper or copper alloy support according to any one of claims 1 to 3, and a printed circuit board using the composite copper foil.
延銅箔であることを特徴とする請求項１〜４のそれぞれ
に記載の銅又は銅合金の支持体を備えた複合銅箔及び該
複合銅箔を使用したプリント基板。5. The composite copper foil provided with a copper or copper alloy support according to claim 1, wherein the copper or copper alloy support is an electrolytic copper foil or a rolled copper foil. And a printed circuit board using the composite copper foil.
銅箔の厚さが０．５〜１２μｍであることを特徴とする
請求項１〜５のそれぞれに記載の銅又は銅合金の支持体
を備えた複合銅箔及び該複合銅箔を使用したプリント基
板。6. The copper or copper alloy according to claim 1, wherein the thickness of the ultra-thin copper foil supported on the copper or copper alloy support is 0.5 to 12 μm. And a printed circuit board using the composite copper foil.
０．００２〜０．５ｋｇ／ｃｍであることを特徴とする
請求項１〜６のそれぞれに記載の銅又は銅合金の支持体
を備えた複合銅箔及び該複合銅箔を使用したプリント基
板。7. The copper or copper alloy support according to claim 1, wherein the peel strength between the ultra-thin copper foil and the nickel layer is 0.002 to 0.5 kg / cm. And a printed circuit board using the composite copper foil.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001168090A JP4672907B2 (en) | 2001-06-04 | 2001-06-04 | Composite copper foil provided with copper or copper alloy support and printed circuit board using the composite copper foil |
| PCT/JP2002/005179 WO2002100136A1 (en) | 2001-06-04 | 2002-05-29 | Composite copper foil with copper or copper alloy support body, and printed circuit board using the composite copper foil |
| TW91111530A TW573079B (en) | 2001-06-04 | 2002-05-30 | Composite copper foil with copper or copper alloy support body, and printed circuit board using the composite copper foil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001168090A JP4672907B2 (en) | 2001-06-04 | 2001-06-04 | Composite copper foil provided with copper or copper alloy support and printed circuit board using the composite copper foil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2002368365A true JP2002368365A (en) | 2002-12-20 |
| JP4672907B2 JP4672907B2 (en) | 2011-04-20 |
Family
ID=19010371
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001168090A Expired - Lifetime JP4672907B2 (en) | 2001-06-04 | 2001-06-04 | Composite copper foil provided with copper or copper alloy support and printed circuit board using the composite copper foil |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP4672907B2 (en) |
| TW (1) | TW573079B (en) |
| WO (1) | WO2002100136A1 (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010027052A1 (en) | 2008-09-05 | 2010-03-11 | 古河電気工業株式会社 | Ultrathin copper foil with carrier, and copper laminated board or printed wiring board |
| WO2012132572A1 (en) * | 2011-03-30 | 2012-10-04 | Jx日鉱日石金属株式会社 | Copper foil with copper carrier, method for producing said copper foil, copper foil for electronic circuit, method for producing said copper foil, and method for forming electronic circuit |
| US8530749B2 (en) | 2007-12-28 | 2013-09-10 | Iljin Copper Foil Co., Ltd. | Copper foil attached to the carrier foil, a method for preparing the same and printed circuit board using the same |
| JP5481553B1 (en) * | 2012-11-30 | 2014-04-23 | Ｊｘ日鉱日石金属株式会社 | Copper foil with carrier |
| JP2016191135A (en) * | 2015-03-31 | 2016-11-10 | Ｊｘ金属株式会社 | Copper foil with carrier, laminate, printed wiring board, electronic device, manufacturing method of copper foil with carrier and manufacturing method of printed wiring board |
| 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 |
| JP2018053327A (en) * | 2016-09-29 | 2018-04-05 | Ｊｘ金属株式会社 | Metal foil with carrier, laminate, method for manufacturing laminate, method for manufacturing printed-wiring board, and method for manufacturing electronic equipment |
| KR20180035566A (en) | 2016-09-29 | 2018-04-06 | 제이엑스금속주식회사 | Metal foil with carrier, laminate, method of manufacturing printed wiring board, method of manufacturing electronic device and method of manufacturing metal foil with carrier |
| JP2020183572A (en) * | 2019-05-09 | 2020-11-12 | ナミックス株式会社 | Production method of metallic component having metal layer |
| WO2020226161A1 (en) * | 2019-05-09 | 2020-11-12 | ナミックス株式会社 | Composite copper member |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5318329B2 (en) * | 1973-12-03 | 1978-06-14 | ||
| JP2000269637A (en) * | 1999-03-18 | 2000-09-29 | Furukawa Circuit Foil Kk | Copper foil for high-density ultrafine wiring board |
| JP2002292788A (en) * | 2001-03-30 | 2002-10-09 | Nippon Denkai Kk | Composite copper foil and method for manufacturing the same |
-
2001
- 2001-06-04 JP JP2001168090A patent/JP4672907B2/en not_active Expired - Lifetime
-
2002
- 2002-05-29 WO PCT/JP2002/005179 patent/WO2002100136A1/en active Application Filing
- 2002-05-30 TW TW91111530A patent/TW573079B/en active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5318329B2 (en) * | 1973-12-03 | 1978-06-14 | ||
| JP2000269637A (en) * | 1999-03-18 | 2000-09-29 | Furukawa Circuit Foil Kk | Copper foil for high-density ultrafine wiring board |
| JP2002292788A (en) * | 2001-03-30 | 2002-10-09 | Nippon Denkai Kk | Composite copper foil and method for manufacturing the same |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8530749B2 (en) | 2007-12-28 | 2013-09-10 | Iljin Copper Foil Co., Ltd. | Copper foil attached to the carrier foil, a method for preparing the same and printed circuit board using the same |
| WO2010027052A1 (en) | 2008-09-05 | 2010-03-11 | 古河電気工業株式会社 | Ultrathin copper foil with carrier, and copper laminated board or printed wiring board |
| JPWO2010027052A1 (en) * | 2008-09-05 | 2012-02-02 | 古河電気工業株式会社 | Ultra-thin copper foil with carrier and copper-laminated laminate or printed wiring board |
| US8674229B2 (en) | 2008-09-05 | 2014-03-18 | Furukawa Electric Co., Ltd. | Ultra-thin copper foil with carrier and copper-clad laminate board or printed circuit board substrate |
| JP5959149B2 (en) * | 2008-09-05 | 2016-08-02 | 古河電気工業株式会社 | Ultra-thin copper foil with carrier and copper-laminated laminate or printed wiring board |
| WO2012132572A1 (en) * | 2011-03-30 | 2012-10-04 | Jx日鉱日石金属株式会社 | Copper foil with copper carrier, method for producing said copper foil, copper foil for electronic circuit, method for producing said copper foil, and method for forming electronic circuit |
| JP5481553B1 (en) * | 2012-11-30 | 2014-04-23 | Ｊｘ日鉱日石金属株式会社 | Copper foil with carrier |
| 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 |
| JP2016191135A (en) * | 2015-03-31 | 2016-11-10 | Ｊｘ金属株式会社 | Copper foil with carrier, laminate, printed wiring board, electronic device, manufacturing method of copper foil with carrier and manufacturing method of printed wiring board |
| JP2018053327A (en) * | 2016-09-29 | 2018-04-05 | Ｊｘ金属株式会社 | Metal foil with carrier, laminate, method for manufacturing laminate, method for manufacturing printed-wiring board, and method for manufacturing electronic equipment |
| KR20180035566A (en) | 2016-09-29 | 2018-04-06 | 제이엑스금속주식회사 | Metal foil with carrier, laminate, method of manufacturing printed wiring board, method of manufacturing electronic device and method of manufacturing metal foil with carrier |
| JP2020183572A (en) * | 2019-05-09 | 2020-11-12 | ナミックス株式会社 | Production method of metallic component having metal layer |
| WO2020226159A1 (en) * | 2019-05-09 | 2020-11-12 | ナミックス株式会社 | Method for manufacturing metal member having metal layer |
| WO2020226161A1 (en) * | 2019-05-09 | 2020-11-12 | ナミックス株式会社 | Composite copper member |
| JP2020183573A (en) * | 2019-05-09 | 2020-11-12 | ナミックス株式会社 | Composite copper member |
| CN113661275A (en) * | 2019-05-09 | 2021-11-16 | 纳美仕有限公司 | Composite copper component |
| JP7409602B2 (en) | 2019-05-09 | 2024-01-09 | ナミックス株式会社 | composite copper parts |
| JP7456579B2 (en) | 2019-05-09 | 2024-03-27 | ナミックス株式会社 | Method for manufacturing a metal member having a metal layer |
Also Published As
| Publication number | Publication date |
|---|---|
| TW573079B (en) | 2004-01-21 |
| JP4672907B2 (en) | 2011-04-20 |
| WO2002100136A1 (en) | 2002-12-12 |
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