JP3854207B2 - Composite copper foil provided with copper or copper alloy support and printed circuit board using the composite copper foil - Google Patents
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Description
【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、異物による傷、打痕防止に有効であり、さらに支持体を剥がした後の極薄銅箔の酸化変色を効果的に防止できる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。
【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。
【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。
【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。
（以上については、例えば特許文献１及び特許文献２参照）
【０００５】
【特許文献１】
特開昭５０−８６４３１号公報
【特許文献２】
特開２０００−２６９６３７号公報
【０００６】
【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、打痕を防止し、また切断、梱包、運搬中の傷、しわ、折れ等を効果的に防止でき、さらに支持体を剥がした後も、極薄銅箔の酸化変色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。
【０００７】
【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し、さらにこの酸化膜で覆われたニッケル層と極薄銅箔との間にベンゾトリアゾール被覆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。
【０００８】
【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。
酸化防止剤塗布
ベンゾトリアゾール ：０．００５〜１０ｇ／Ｌ
浸漬時間 ：５〜６０秒
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
【０００９】
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。
【００１０】
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。
【００１１】
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。
【００１２】
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１７０°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。
【００１３】
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。
さらに、ベンゾトリアゾールの被覆層は、酸化防止剤として極めて有効であり、支持体付銅箔及び該銅箔を使用したプリント基板の使用に際し、支持体を剥がした後も、極薄銅箔表面の酸化変色が長期に亘って防止できる著しい効果を有する。
【００１４】
【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。
【００１５】
（実施例１）
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４５Å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）。
この陽極酸化による酸化膜形成後、ベンゾトリアゾール５．０ｇ／Ｌ溶液に３０秒浸漬させた。この後、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、剥離強度、耐食性を調べた結果を、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った。この時の剥離強度は０．０３ｋｇ／ｃｍであった。また、しわの発生がなくハンドリング性は良好であった。
さらに、支持体銅金属層と接していた側の極薄銅箔表面は、１０日経過しても酸化変色の発生が観察されなかった。
【００１６】
【表１】
（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面上に、上記ニッケルめっきの条件で厚さ１．０μｍ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。
この陽極酸化による酸化膜形成後、ベンゾトリアゾール５．０ｇ／Ｌ溶液に３０秒浸漬させた。この後、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、剥離強度、耐食性を調べた結果を、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った。この時の剥離強度は０．０３ｋｇ／ｃｍであった。また、しわの発生がなくハンドリング性は良好であった。
さらに、支持体銅金属層と接していた側の極薄銅箔表面は、１０日経過しても酸化変色の発生が観察されなかった。
【００１８】
（比較例１）
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、実施例１と同条件で陽極酸化を行った。さら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、剥離強度、耐食性を調べた結果を、同様に表１に示す。
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、しわの発生もなく、剥離性も容易であった。しかし、２日後に酸化・変色が観察された。
【００１９】
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０．０３ｋｇ／ｃｍであり、良好な剥離性を示した。さらに、長期に亘って酸化変色がなく、ベンゾトリアゾールの効果が著しいことが確認できた。
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、ベンゾトリアゾールの被膜層を形成し、さら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は、プリント基板の使用に際し、支持体を剥がした後も、極薄銅箔の酸化変色を効果的に防止でき、かつより均一な剥離強度のあるキャリア付銅箔を得ることができた。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。
【００２０】
【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及びベンゾトリアゾール被膜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、さらに効果的に酸化変色を防止できるという優れた効果を有する。[0001]
BACKGROUND OF THE INVENTION
The present invention improves the handling of ultrathin copper foil, prevents contaminants such as resin powder of the prepreg sheet from adhering to the surface of the copper foil, is effective in preventing scratches and dents due to foreign matter, and further supports the support. The present invention relates to a copper or copper alloy-supported composite copper foil that can effectively prevent oxidation discoloration of an ultrathin copper foil after peeling, and a printed circuit board using the composite copper foil.
[0002]
[Prior art]
Conventionally, a copper-clad laminate used for a printed circuit board is formed by laminating a copper foil on a paper-phenolic resin-impregnated base material or a glass-epoxy resin-impregnated base material, and heating and pressurizing using a press device. The copper foil roll and the resin base material are continuously laminated and heated. Furthermore, this copper-clad laminate forms a circuit network through a process such as etching, and a board for an electronic device is manufactured by mounting elements such as a semiconductor device.
In general, when pressurizing a copper foil using a press or laminating apparatus, foreign matters such as copper chips generated during cutting of the copper foil or resin powder of the prepreg adhere to the glossy surface (S surface) of the copper foil. If there is, there is a problem that the glossy surface is damaged or a foreign matter adheres. Further, even when the copper-clad laminate is taken out from the apparatus or laminated after the lamination, the glossy surfaces may be rubbed and damaged.
[0003]
In recent years, there has been a demand for copper foil with reduced thickness, such as the circuit width has been remarkably reduced due to the demand for miniaturization of electronic equipment, and the thickness of copper foil used for copper-clad laminates has become 12 μm or less. It's getting bigger.
However, when the thickness of the copper foil is reduced to 12 μm or less, the handling property is extremely deteriorated. Not only the press and laminating processes described above, but also the usual cutting, packing, and fretting during transportation, foreign matter mixing, wrinkles, breakage, etc., especially the gloss of copper foil There is a problem that it is easily affected by this.
Such scratches, wrinkles, creases, etc., especially on the glossy side, can cause circuit breaks and short circuits, which can lead to defects in printed circuit boards and electronic equipment and become a major problem. ing.
[0004]
Several proposals have been made to prevent scratches, wrinkles, creases, and the like on the surface of the copper foil as described above and to improve handling properties. As an example, there is a proposal to bond a resin film such as polyamide that can withstand the heating temperature (about 170 ° C.) during press molding to a copper foil using an adhesive.
However, such a resin film cannot effectively prevent wrinkles and creases, as long as it does not use a considerably thick film. There is a risk of deformation due to expansion and contraction of the agent due to heat, and the adhesive used for film adhesion may remain on the copper foil and cause contamination, which is not necessarily a good improvement measure.
In addition, proposals have been made to use an aluminum foil instead of a resin film and to adhere 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 and is transferred to the copper foil at the time of bonding. 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. In addition, when annealed at a high temperature, the aluminum foil is softened and the strength is lowered, so that it is necessary to increase the thickness considerably in order to use it as a carrier, which causes problems of cost increase and weight increase. In addition to the problem of remaining rolling oil, the aluminum foil has a problem in that the aluminum powder on the surface is transferred to the copper foil at the time of pressing, causing a circuit disconnection or a short circuit.
Furthermore, there is also a proposal of a composite copper foil having an organic type and nickel as a release layer. However, in this case, at the time of laminating with the resin, the peeling layer diffuses into the copper or copper alloy support and the ultrathin copper foil, and there is a problem that there is a problem in peeling from the copper or copper alloy support. .
(For the above, see, for example, Patent Document 1 and Patent Document 2)
[0005]
[Patent Document 1]
Japanese Patent Laid-Open No. 50-86431 [Patent Document 2]
Japanese Patent Laid-Open No. 2000-269637
[Problems to be solved by the invention]
The present invention has been made in view of the problems as described above, and the object of the present invention is to improve the handleability of ultrathin copper foil, and contaminants such as resin powder of a prepreg sheet are present on the surface of the copper foil. Prevents adhesion, prevents scratches and dents from foreign objects, and effectively prevents cutting, packing, transporting scratches, wrinkles, folds, etc. It is intended to obtain a composite copper foil provided with a copper (copper) support (carrier) that can effectively prevent oxidation discoloration and a printed board using the composite copper foil.
[0007]
[Means for Solving the Problems]
From the above, the present invention is 1. A nickel layer covered with an oxide film is provided on the support side between the copper or copper alloy support and the ultrathin copper foil, and further between the nickel layer covered with this oxide film and the ultrathin copper foil. A composite copper foil provided with a copper or copper alloy support and a printed circuit board using the composite copper foil.
2. The composite copper foil provided with the support body of copper or copper alloy of said 1 characterized by having a nickel layer of 0.05-5.0 micrometers, and a printed circuit board using this composite copper foil.
3. The thickness of the oxide film of a nickel layer is 25-500 mm, The composite copper foil provided with the support body of the copper or copper alloy of said 1 or 2 characterized by the above-mentioned, and the printed circuit board using this composite copper foil.
4). The thickness of the copper or copper alloy support is 15 to 70 μm, and the composite copper foil provided with the copper or copper alloy support according to each of the above 1 to 3 and the composite copper foil are used. Printed circuit board.
5). The composite copper foil provided with the copper or copper alloy support according to each of the above 1 to 4, wherein the copper or copper alloy support is an electrolytic copper foil or a rolled copper foil, and the composite copper foil. Used printed circuit board.
6). The thickness of the ultra-thin copper foil supported by the support body of copper or a copper alloy is 0.5-12 micrometers, It provided with the support body of the copper or copper alloy in each of said 1-5 characterized by the above-mentioned. Composite copper foil and printed circuit board using the composite copper foil.
7). The composite copper foil provided with the copper or copper alloy support according to each of the above 1 to 6, wherein the peel strength between the ultrathin copper foil and the nickel layer is 0.002 to 0.5 kg / cm And a printed circuit board using the composite copper foil.
I will provide a.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
The composite copper foil provided with the copper or copper alloy support of the present invention and the printed circuit board using the composite copper foil are first plated with nickel of 0.05 to 5.0 μm on the surface of the copper or copper alloy support. Form a layer.
A preferable example of conditions for forming the nickel plating layer is shown below.
Nickel plating Nickel concentration: 10-80g / L
Electrolyte temperature: 20-80 ° C
Current density: 0.1 to 20 A / dm 2
pH: 1.0-5.0
An oxide film is further formed on the surface of the nickel layer. The thickness of this oxide film is preferably 25 to 500 mm. The oxide film can remarkably improve the peelability of the ultrathin copper foil. Anodization is a means for forming an oxide film on the nickel layer, and a preferred example of conditions for forming this oxide film is shown below.
Oxide film forming NaOH concentration: 0.5 to 20 g / L
Electrolyte temperature: 20-50 ° C
Current density: 1-10 A / dm 2
Then, an ultrathin copper foil is formed on this oxide film. The thickness of the ultrathin copper foil is preferably 0.5 to 12 μm. An ultrathin copper foil is formed by electroplating. An example of preferable conditions for the copper plating is shown below.
Benzotriazole coated with antioxidant: 0.005 to 10 g / L
Immersion time: 5 to 60 seconds Copper plating Copper concentration: 30 to 120 g / L
H 2 SO 4 concentration: 20 to 120 g / L
Electrolyte temperature: 20-80 ° C
Current density: 10 to 100 A / dm 2
[0009]
Thereby, the composite copper foil provided with the support body of copper or a copper alloy is obtained. Furthermore, the laminated composite copper foil and the resin base material are laminated by pressing or laminating to form a copper-clad laminate, but the composite copper foil provided with the copper or copper alloy support has handling properties. Since it is extremely good, it is possible to effectively prevent the occurrence of wrinkles, creases and the like, and it is possible to prevent foreign matter from directly attaching to the surface of the copper foil by covering with a support of copper or copper alloy.
Further, after the lamination, the copper or copper alloy support is peeled off from the nickel layer portion having the oxide film, and a circuit network is formed by a process such as etching, but the nickel layer provided with the oxide film is formed until immediately before the circuit formation. Because it is protected by a copper or copper alloy support, it is effective in preventing scratches and dents caused by foreign matter on the copper-clad laminate, and it is also effective for scratches, wrinkles, breaks, etc. during cutting, packing, and transportation. Can be prevented.
[0010]
The copper or copper alloy support used in the copper foil of the present invention can be an electrolytic copper foil or a rolled copper foil. The preferred thickness is 15 to 70 μm. From the viewpoint of cost, it is desirable to use a thinner electrolytic copper foil or rolled copper foil, but if it is too thin, it cannot be used as a support (carrier) in strength, so a thickness of a certain level or more is necessary. The peel strength between the ultrathin 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 can be easily peeled off. In addition, the peeling strength in this case shows the value at the time of laminating | stacking the said composite copper foil on a base material at 150 degreeC or more on the ultrathin copper foil side.
[0011]
The copper foil surface on which the nickel layer is formed is preferably applied to the glossy surface (S) surface, but may be applied to another 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, generally, copper foil for printed wiring boards is subjected to roughening particle formation, oxide film formation, heat-resistant film formation, rust prevention treatment, etc., but these treatments can be applied to the present invention. All of these are included.
[0012]
When the example of the lamination process of copper foil is shown, for example, it will laminate | stack by applying a heating and a pressure for 60 to 180 minutes at about 10-30 kg / cm < 2 > press pressure and the press temperature of around 170 degreeC. Thereby, joining of copper foil and a prepreg sheet can fully be performed. Moreover, since the composite copper foil provided with the support body of copper or a copper alloy has very good handling property, wrinkles, creases, etc. do not occur.
In particular, the handling property is remarkably improved when the thickness of the ultrathin copper foil is 12 μm or less. Further, the present invention is not limited to the above pressing process, and there is an effect that normal cutting and packing, and further, there is no damage during transportation, foreign matters are mixed, wrinkles, breakage, etc. are not generated.
As a result, cutting and short-circuiting of the printed circuit board can be reduced, defects in the electronic device can be suppressed, and the yield of the product can be improved.
[0013]
After the above lamination, a copper or copper alloy support having a nickel layer provided with an oxide film can be easily peeled and removed from the ultrathin copper foil. The foil or sheet (plate) as a carrier of copper or copper alloy for the carrier can be recycled.
This improves the handleability of ultra-thin copper foil, prevents prepreg sheet resin powder and other contaminants from adhering to the copper foil surface, prevents scratches caused by foreign matter, prevents dents, and also scratches during cutting, packing, and transportation. Thus, it is possible to easily obtain a printed circuit board without causing wrinkles or creases.
Furthermore, the coating layer of benzotriazole is extremely effective as an antioxidant, and after using the copper foil with a support and a printed circuit board using the copper foil, the surface of the ultrathin copper foil is removed even after the support is removed. It has a remarkable effect that oxidation discoloration can be prevented over a long period of time.
[0014]
[Examples and Comparative Examples]
Next, examples and comparative examples of the present invention will be described. In addition, a present Example is an example to the last, and this invention is not restrict | limited to this example. That is, all aspects or modifications other than the embodiment are included within the scope of the technical idea of the present invention.
[0015]
Example 1
Nickel plating having a thickness of 0.1 μm was performed on the surface of the electrolytic copper foil S having a thickness of 35 μm as a support copper metal layer under the above nickel plating conditions. A 45-mm oxide film was formed on the surface of the nickel plating by anodic oxidation under the above conditions. The anodic oxidation time 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 in the same manner).
After forming the oxide film by this anodic oxidation, it was immersed in a benzotriazole 5.0 g / L solution for 30 seconds. Thereafter, 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, and pressed at 175 ° C. for 30 minutes under the conditions of 35 kg / cm 2 to obtain a copper-clad laminate.
Table 1 shows the results of observation of wrinkle generation, peel strength, and corrosion resistance 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 ultrathin copper foil and the copper or copper alloy support having a nickel coating was good. The peel strength at this time was 0.03 kg / cm. Moreover, there was no generation | occurrence | production of a wrinkle and handling property was favorable.
Furthermore, no oxidation discoloration was observed on the ultrathin copper foil surface on the side in contact with the support copper metal layer even after 10 days.
[0016]
[Table 1]
(Example 2)
As in Example 1, nickel plating having a thickness of 1.0 μm was performed on the surface of the electrolytic copper foil S having a thickness of 35 μm as the support copper metal layer under the above nickel plating conditions. A 50-mm oxide film was formed on the surface of the nickel plating by anodic oxidation under the above conditions. The anodic oxidation time was 30 seconds.
After forming the oxide film by this anodic oxidation, it was immersed in a benzotriazole 5.0 g / L solution for 30 seconds. Thereafter, 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 in the same manner as in Example 1, and pressed at 175 ° C. for 30 minutes at 35 kg / cm 2 to obtain a copper-clad laminate. Table 1 shows the results of the observation of wrinkle generation, peel strength, and corrosion resistance 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 ultrathin copper foil and the copper or copper alloy support having a nickel coating was good. The peel strength at this time was 0.03 kg / cm. Moreover, there was no generation | occurrence | production of a wrinkle and handling property was favorable.
Furthermore, no oxidation discoloration was observed on the ultrathin copper foil surface on the side in contact with the support copper metal layer even after 10 days.
[0018]
(Comparative Example 1)
Nickel plating having a thickness of 0.1 μm was performed on the surface of the electrolytic copper foil S having a thickness of 35 μm as a support copper metal layer under the above nickel plating conditions. The surface of this nickel plating was anodized under the same conditions as in Example 1. Further, copper having a thickness of 5 μm was deposited under the above copper plating conditions.
Next, this composite copper foil was laminated on prepreg FR-4 in the same manner as in Example 1, and pressed at 175 ° C. for 30 minutes at 35 kg / cm 2 to obtain a copper-clad laminate.
Table 1 shows the results of observation of wrinkle generation, peel strength, and corrosion resistance of the composite copper foil provided with the copper or copper alloy support of Comparative Example 1 thus obtained.
As is clear from Table 1, Comparative Example 1 had good handling properties, no wrinkles, and easy peelability. However, oxidation and discoloration were observed after 2 days.
[0019]
In contrast to the results of the comparative examples described above, in Examples 1 and 2, as described above, handling properties are good and wrinkles are not generated, and the peel strengths of Examples 1 and 2 are both 0.03 kg. / Cm, indicating good peelability. Furthermore, it was confirmed that there was no oxidative discoloration over a long period of time and the effect of benzotriazole was remarkable.
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, a coating layer of benzotriazole is formed, and further ultrathin The composite copper foil provided with the copper or copper alloy support formed with the copper foil can effectively prevent oxidation discoloration of the ultrathin copper foil even after the support is peeled off when using the printed circuit board, and A copper foil with a carrier having a more uniform peel strength could be obtained. The laminated composite copper foil and the resin base material are laminated by pressing or laminating, and it can be seen that the copper-clad laminate (printed board) has excellent characteristics.
[0020]
【The invention's effect】
A composite copper foil of the present invention, comprising a copper or copper alloy support, and having a nickel layer and a benzotriazole coating layer provided with an oxide film between the copper or copper alloy support and an ultrathin copper foil, and Printed circuit board using composite copper foil improves handling of ultra-thin copper foil, prevents prepreg sheet resin powder and other contaminants from adhering to the copper foil surface, and is effective in preventing scratches and dents from foreign objects Furthermore, it has an excellent effect that it can prevent the occurrence of normal cutting, packing, flaws during transportation, mixing of foreign substances, wrinkles, folds, etc., and more effectively preventing oxidative discoloration.
Claims (7)
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| TW200804626A (en) * | 2006-05-19 | 2008-01-16 | Mitsui Mining & Smelting Co | Copper foil provided with carrier sheet, method for fabricating copper foil provided with carrier sheet, surface-treated copper foil provided with carrier sheet, and copper-clad laminate using the surface-treated copper foil provided with carrier she |
| JP5481553B1 (en) * | 2012-11-30 | 2014-04-23 | Ｊｘ日鉱日石金属株式会社 | Copper foil with carrier |
| JP6140481B2 (en) * | 2013-03-05 | 2017-05-31 | Ｊｘ金属株式会社 | Copper foil with carrier, method for producing copper foil with carrier, printed wiring board, printed circuit board, copper-clad laminate, and method for producing printed wiring board |
| JP6140480B2 (en) * | 2013-03-05 | 2017-05-31 | Ｊｘ金属株式会社 | Copper foil with carrier, method for producing copper foil with carrier, printed wiring board, printed circuit board, copper-clad laminate, and method for producing printed wiring board |
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