JP4981488B2 - Roughened rolled copper plate and method for producing the same - Google Patents
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Description
本発明は、基板の導体層やメタルコア層に使用される粗化圧延銅板およびその製造方法に関するものである。 The present invention relates to a roughened rolled copper plate used for a conductor layer and a metal core layer of a substrate, and a method for producing the same.
基板の導体層には１０〜７０μｍ厚の電解銅箔が使用されている。電解銅箔は表面粗度が大きいマット面と平滑面であるシャイニー面を有し、このうち積層用樹脂との接着に用いられるのは表面粗度が大きいマット面であるが、このマット面をさらに粗化めっき処理して、樹脂との接着性を高めた粗化電解銅箔が主に使用されている。
ところで、大電流通電基板の導体層やメタルコア基板のメタルコア層には７０μｍ以上の厚みの銅板（箔）が必要とされるが、この厚みの電解銅箔は製造コストが非常に高くなり、またその厚い電解銅箔は機械的特性も不十分になることから、電解銅箔を使用するのは困難であった。
An electrolytic copper foil having a thickness of 10 to 70 μm is used for the conductor layer of the substrate. Electrolytic copper foil has a matte surface with a large surface roughness and a shiny surface that is a smooth surface. Of these, the matte surface with a large surface roughness is used for bonding to the laminating resin. Further, a roughened electrolytic copper foil that has been subjected to roughening plating treatment to improve adhesion with a resin is mainly used.
By the way, a copper plate (foil) having a thickness of 70 μm or more is required for the conductor layer of the large current conducting substrate and the metal core layer of the metal core substrate. However, the manufacturing cost of the electrolytic copper foil of this thickness is very high. Since the thick electrolytic copper foil has insufficient mechanical properties, it has been difficult to use the electrolytic copper foil.
そこで、このような用途では低コストで製造できる圧延銅板が主に使用されている。
しかし、圧延銅板はその表面粗度が電解銅箔のマット面に比較して一般的に一桁低く、樹脂との接着性が電解銅箔に比べて劣っているため、圧延銅板を粗化処理することで電解銅箔並みの樹脂との接着性をもたせる試みが種々行われてきた。
Therefore, rolled copper sheets that can be manufactured at low cost are mainly used in such applications.
However, the surface roughness of the rolled copper sheet is generally an order of magnitude lower than the matte surface of the electrolytic copper foil, and the adhesiveness with the resin is inferior to that of the electrolytic copper foil. By doing so, various attempts have been made to provide adhesion with a resin equivalent to electrolytic copper foil.
圧延銅板（箔）の粗化処理方法は、化学エッチングが一般的であり、各種のエッチング方法、処理液が提供されているが、化学エッチングは処理液自体が高価であり、また多量の廃液を処理しなければならないという問題を有する。
また、特許文献１には、比較的低コストで行える電解エッチング、つまり、圧延銅箔を酸電解液中で直流または交流で陽極電解してエッチング粗化する方法が開示されているが、エッチング処理によって電解液の銅濃度が上昇し、銅エッチング量に応じた銅廃液が発生し、廃液処理が高コストとなるという問題を有する。
The roughening treatment method of the rolled copper plate (foil) is generally chemical etching, and various etching methods and treatment liquids are provided. However, the chemical etching is expensive, and a large amount of waste liquid is removed. Has the problem of having to deal with.
Patent Document 1 discloses electrolytic etching that can be performed at a relatively low cost, that is, a method in which a rolled copper foil is subjected to anodic electrolysis in a direct current or alternating current in an acid electrolytic solution to roughen the etching. As a result, the copper concentration of the electrolytic solution increases, and a copper waste liquid corresponding to the amount of copper etching is generated, resulting in a high cost of waste liquid treatment.
一方、パルス電解を用いた粗化処理方法も幾つか行われている。
例えば、特許文献２には、銅箔に対し銅めっき液中で直流による陰極電解（銅めっき）を行い、銅箔表面に大きな一次起伏を形成し、その後、電流密度の絶対値および通電時間が等しい正負のパルスを交互に印加するＰＲ（Ｐｅｒｉｏｄｉｃ ｒｅｖｅｒｓｅ）電解を行い、引き続き陰極電解（銅めっき）を行い、一次起伏の上に比較的形状の大きな二次起伏を形成し、粗化する方法が開示されている。
しかしながら、この方法はその実施例に示されているとおり、高銅濃度の硫酸銅液を使用し、高温下で非常に高い電流密度の処理が必要であり、高価な整流器が必要となり、設備も高価なものになる。また、ＰＲ電解の前後で直流による銅めっきを行う必要があり、工程数が多く煩雑であった。
On the other hand, some roughening methods using pulse electrolysis are also performed.
For example, Patent Document 2 discloses that cathodic electrolysis (copper plating) is performed on a copper foil in a copper plating solution by direct current to form a large primary undulation on the surface of the copper foil. PR (Periodic reverse) electrolysis that alternately applies equal positive and negative pulses, followed by cathodic electrolysis (copper plating), forming a relatively large secondary undulation on the primary undulation, and roughening It is disclosed.
However, this method uses a copper sulfate solution having a high copper concentration as shown in the examples, requires a very high current density treatment at a high temperature, requires an expensive rectifier, and has facilities. It becomes expensive. Moreover, it is necessary to perform direct current copper plating before and after the PR electrolysis, which is complicated and complicated.
また、特許文献３には、銅箔に対し、硫酸酸性銅めっき液中で電流密度の絶対値および時間が同じくらいの正負のパルスを用いて、正負の電気量の絶対値が等しいぐらい（０．７〜１．３）の正負の交番パルス電解、または交流電解をする活性化処理を行い、活性化・微細化し、続いて限界電流密度付近またはそれ以上の直流による陰極電解（銅めっき）を行い銅の突起物粗化を行い、さらに上記突起物の脱落防止のための銅めっきによる被覆層を形成し、粗化面を生成させる方法が開示されている。
しかしながら、この方法においても交番パルス電解後にさらに直流による銅めっきを行う必要があり、工程数が増え煩雑であった。
Patent Document 3 discloses that the absolute values of positive and negative electric quantities are equal to each other by using positive and negative pulses having the same current density and time in a sulfuric acid copper plating solution as compared with copper foil (0). .7 to 1.3) Activation of positive and negative alternating pulse electrolysis or alternating current electrolysis, activation and miniaturization, followed by cathodic electrolysis (copper plating) near or above the limit current density A method is disclosed in which roughening of the copper protrusions is performed, and a coating layer is formed by copper plating to prevent the protrusions from falling off, thereby generating a roughened surface.
However, even in this method, it is necessary to perform copper plating by direct current after alternating pulse electrolysis, which increases the number of steps and is complicated.
このように、パルス電解を用いた従来の粗化処理方法は、パルス電解はあくまでも直流による陰極電解（銅めっき）で形成する大きな一次起伏や突起物などを二次起伏形成や活性化などで補足するもので、パルス電解単独によるものではなかった。
本発明は、このような事情に照らして、従来のように直流による陰極電解（銅めっき）とパルス電解を組み合わせるのではなく、パルス電解単独により従来の粗化電解銅箔並みの樹脂との接着性を有し、しかも低コストである粗化圧延銅板およびその製造方法を提供することを課題としている。 In light of such circumstances, the present invention does not combine direct current cathodic electrolysis (copper plating) and pulse electrolysis as in the past, but rather adheres to a resin similar to a conventional roughened electrolytic copper foil by pulse electrolysis alone. It is an object of the present invention to provide a roughened rolled copper sheet and a method for producing the same that have high performance and low cost.
本発明者は、上記課題につき鋭意検討したところ、圧延銅板を電解液中にて非対称の正負のパルスでパルス電解するにあたり、電解液中に光沢剤を含ませる一方、正負パルスの電流密度、通電時間および単位面積当たりの積算電流値が、それぞれ、一定の関係を満たすようにしたときに、パルス電解単独により従来の粗化電解銅箔並みの樹脂との接着性を有する粗化圧延銅板が得られることを見出し、本発明を完成するに至った。 The present inventor has diligently studied the above problems, and in performing electrolysis of a rolled copper plate with an asymmetric positive / negative pulse in the electrolytic solution, a brightener is included in the electrolytic solution, while the current density of the positive / negative pulse When the accumulated current values per time and unit area satisfy a certain relationship, a roughened rolled copper sheet having adhesiveness similar to that of a conventional roughened electrolytic copper foil is obtained by pulse electrolysis alone. As a result, the present invention has been completed.
すなわち、本発明は、 電気化学的手法によって粗化された粗化圧延銅板であって、この粗化圧延銅板は光沢剤を含む電解液中にて非対称の正負のパルスでパルス電解されており、上記正パルスの電流密度Ｉａ（Ａ／ｄｍ２）と上記負パルスの電流密度Ｉｃ（Ａ／ｄｍ２）が下記の（１）式を満たし、上記正パルスの通電時間Ｔａ（秒）と上記負パルスの通電時間Ｔｃ（秒）が下記の（２）式を満たし、上記正パルスの単位面積当たりの積算電流値Ｑａ（A・ｓ／ｄｍ２）と上記負パルスの単位面積当たりの積算電流値Ｑｃ（A・ｓ／ｄｍ２）が下記の（３）式を満たすことを特徴とする粗化圧延に係るものである。
｜Ｉａ｜＞｜Ｉｃ｜ … （１）
Ｔａ＜Ｔｃ … （２）
１＜｜Ｑｃ／Ｑａ｜≦４ … （３）
〔ここで、（１），（３）式中の｜｜は、絶対値を表している〕
また、本発明は、光沢剤を含む電解液中にて非対称の正負のパルスで圧延銅板をパルス電解する工程を有し、上記正パルスの電流密度Ｉａ（Ａ／ｄｍ２）と上記負パルスの電流密度Ｉｃ（Ａ／ｄｍ２）が下記の（１）式を満たし、上記正パルスの通電時間Ｔａ（秒）と上記負パルスの通電時間Ｔｃ（秒）が下記の（２）式を満たし、上記正パルスの単位面積当たりの積算電流値Ｑａ（A・ｓ／ｄｍ２）と上記負パルスの単位面積当たりの積算電流値Ｑｃ（A・ｓ／ｄｍ２）が下記の（３）式を満たすことを特徴とする粗化圧延銅板の製造方法に係るものである。
｜Ｉａ｜＞｜Ｉｃ｜ … （１）
Ｔａ＜Ｔｃ … （２）
１＜｜Ｑｃ／Ｑａ｜≦４ … （３）
〔ここで、（１），（３）式中の｜｜は、絶対値を表している〕
That is, the present invention is a rough rolled copper plate roughened by an electrochemical method, the rough rolled copper plate is pulse electrolyzed with asymmetric positive and negative pulses in an electrolyte containing a brightener, The positive pulse current density Ia (A / dm 2 ) and the negative pulse current density Ic (A / dm 2 ) satisfy the following equation (1), and the positive pulse energization time Ta (seconds) and the negative pulse current density Ic (A / dm 2 ) The pulse energization time Tc (seconds) satisfies the following formula (2), and the accumulated current value Qa (A · s / dm 2 ) per unit area of the positive pulse and the accumulated current value per unit area of the negative pulse: Qc (A · s / dm 2 ) relates to roughing rolling characterized by satisfying the following expression (3).
| Ia |> | Ic | (1)
Ta <Tc (2)
1 <| Qc / Qa | ≦ 4 (3)
[Where, || in the expressions (1) and (3) represents an absolute value]
The present invention also includes a step of pulse electrolysis of a rolled copper plate with asymmetric positive and negative pulses in an electrolyte solution containing a brightener, and the current density Ia (A / dm 2 ) of the positive pulse and the negative pulse. The current density Ic (A / dm 2 ) satisfies the following expression (1), the energization time Ta (second) of the positive pulse and the energization time Tc (second) of the negative pulse satisfy the following expression (2), The accumulated current value Qa (A · s / dm 2 ) per unit area of the positive pulse and the accumulated current value Qc (A · s / dm 2 ) per unit area of the negative pulse satisfy the following expression (3). The present invention relates to a method for producing a roughened rolled copper sheet.
| Ia |> | Ic | (1)
Ta <Tc (2)
1 <| Qc / Qa | ≦ 4 (3)
[Where, || in the expressions (1) and (3) represents an absolute value]
本発明は、従来の直流による陰極電解（銅めっき）とパルス電解を組み合わせるのではなく、パルス電解単独で粗化電解銅箔並みの樹脂との接着性を有し、良好なハンダ耐熱性も示す低コストな粗化圧延銅板を得ることができる。
また、本発明では、パルス電解によりめっき、電解を繰り返し行っているので、液中のＣｕイオン濃度の変化が通常の直流電気めっきに比べて少なく、液が長持ちし補充交換を少なくすることができる。さらに、従来の粗化処理のようにパルスめっき後にさらに直流電気めっきを行うような煩雑な作業を必要としない。
The present invention does not combine conventional direct current cathodic electrolysis (copper plating) and pulse electrolysis, but has pulse electrolysis alone and adhesion to a resin similar to a roughened electrolytic copper foil, and also exhibits good solder heat resistance. A low-cost roughened rolled copper sheet can be obtained.
Further, in the present invention, since plating and electrolysis are repeatedly performed by pulse electrolysis, the change in Cu ion concentration in the liquid is less than that of normal DC electroplating, and the liquid lasts longer and replenishment replacement can be reduced. . Furthermore, the complicated operation | work which performs DC electroplating further after pulse plating like the conventional roughening process is not required.
本発明において、電解液には、硫酸銅系、シアン化銅系、ピロリン酸銅系、ホウフッ化銅系などの一般的な銅めっき液に、光沢剤や抑制剤を含ませたものが用いられる。
電解液中の銅イオンの濃度は特に制限するものではないが、好ましくは４０ｇ／ｌ以上であり、より好ましくは４０ｇ／ｌ〜２５０ｇ／ｌである。
また、電解液中の光沢剤や抑制剤の濃度は、光沢剤製造メーカーの使用法に従って適宜に添加量を定めることができる。
電解液の組成などについては上記以外の点については、通常のパルス電解法で用いるものと特に異ならず、同様のものを用いることができる。
光沢剤・抑制剤には、一般的に知られているものを使用できる。例えば、特開２００１−３１９１号公報に開示されているものなどを使用できる。市販品の例としては、Ｒｏｈｍ ａｎｄ Ｈａａｓ社製のカパーグリームシリーズ、日本化学産業株式会社製のクッペライトシリーズ、ピロニッカシリーズなどが挙げられる。
In the present invention, as the electrolytic solution, a general copper plating solution such as a copper sulfate-based, copper cyanide-based, copper pyrophosphate-based, copper borofluoride-based solution containing a brightener or an inhibitor is used. .
The concentration of copper ions in the electrolytic solution is not particularly limited, but is preferably 40 g / l or more, more preferably 40 g / l to 250 g / l.
Further, the concentration of the brightener and the inhibitor in the electrolytic solution can be appropriately determined according to the usage method of the brightener manufacturer.
Regarding the composition of the electrolytic solution and the like, the points other than the above are not particularly different from those used in the normal pulse electrolysis method, and the same ones can be used.
As the brightener / inhibitor, those generally known can be used. For example, those disclosed in JP 2001-3191 A can be used. Examples of commercially available products include the Capper Gream series manufactured by Rohm and Haas, the Cupperite series manufactured by Nippon Kagaku Sangyo Co., Ltd., and the Pironica series.
本発明においては、このような光沢剤を含む電解液中にて、非対称の正負のパルスで、圧延銅板をパルス電解するが、前記のようにその際に、正パルスの電流密度Ｉａと負パルスの電流密度Ｉｃとの関係、正パルスの通電時間Ｔａと負パルスの通電時間Ｔｃとの関係、正パルスの単位面積当たりの積算電流値Ｑａと負パルスの単位面積当たりの積算電流値Ｑｃとの関係が、それぞれ、下記（１）〜（３）式を満たすようにすることが肝要である。
｜Ｉａ｜＞｜Ｉｃ｜ … （１）
Ｔａ＜Ｔｃ … （２）
１＜｜Ｑｃ／Ｑａ｜≦４ … （３）
〔ここで、（１），（３）式中の｜｜は、絶対値を表している〕
好ましい実施態様を述べると上記式において電流密度Ｉａは１０〜３５Ａ／ｄｍ２が好ましく、Ｉｃは２〜１５Ａ／ｄｍ２が好ましい。この値が大きすぎると電流が強すぎて処理板中でのムラが発生やすくなり、小さすぎると粗化量が少なくなり、粗化後のピール強度が不十分となる。
また通電時間（１パルスの通電時間）は正パルスＴａ（電解）では０．５〜２msが好ましく、負パルスＴｃ（めっき）では５〜２０msが好ましい。さらにいえばＴｃ／Ｔａは２０以下が好ましい。この値が大きすぎるとめっきが強すぎて粗化が浅くなる。
また、より好ましくは １．３＜｜Ｑｃ／Ｑａ｜≦３ である。この値が大きすぎるとめっきが強すぎて平滑化されてピール強度の低下を招く事になり、小さすぎるとめっき自体の固着力が低下してピール強度が低下する。
In the present invention, a rolled copper plate is subjected to pulse electrolysis with an asymmetric positive and negative pulse in an electrolytic solution containing such a brightener. At that time, the positive pulse current density Ia and the negative pulse are used as described above. Of the positive pulse energization time Ta and the negative pulse energization time Tc, and the accumulated current value Qa per unit area of the positive pulse and the accumulated current value Qc per unit area of the negative pulse. It is important that the relationships satisfy the following expressions (1) to (3).
| Ia |> | Ic | (1)
Ta <Tc (2)
1 <| Qc / Qa | ≦ 4 (3)
[Where, || in the expressions (1) and (3) represents an absolute value]
Current density Ia is preferably 10~35A / dm 2 in the described preferred embodiments the above formulas, Ic is preferably 2~15A / dm 2. If this value is too large, the current is too strong and unevenness in the treated plate is likely to occur, and if it is too small, the amount of roughening decreases and the peel strength after roughening becomes insufficient.
The energization time (one pulse energization time) is preferably 0.5 to 2 ms for the positive pulse Ta (electrolysis) and 5 to 20 ms for the negative pulse Tc (plating). Furthermore, Tc / Ta is preferably 20 or less. If this value is too large, the plating is too strong and the roughening becomes shallow.
More preferably, 1.3 <| Qc / Qa | ≦ 3. If this value is too large, the plating is too strong and smoothed, resulting in a decrease in peel strength. If it is too small, the adhesion strength of the plating itself is decreased and the peel strength is decreased.
次に本発明の実施態様を図面に従って説明する。
図１は、上記本発明のパルス電解の様子を模式的に示したものである。
図１に示されるように、正パルスの電流密度Ｉａと負パルスの電流密度Ｉｃとの関係が（１）式を満たし、正パルスの通電時間Ｔａと負パルスの通電時間Ｔｃとの関係が（２）式を満たし、正パルスの単位面積当たりの積算電流値Ｑａと負パルスの単位面積当たりの積算電流値Ｑｃとの関係が（３）式を満たすようにしたときに、表面に形成される突起物による粗度が大きくなり、従来の粗化電解銅箔並に高い樹脂との接着性を有する粗化圧延銅板を得ることが可能となる。これに対し、上記いずれかの関係が上記の式を満たさないと表面に形成される突起物による粗度が低くなり、十分な樹脂との接着性が得られなくなる。
Next, embodiments of the present invention will be described with reference to the drawings.
FIG. 1 schematically shows the state of pulse electrolysis according to the present invention.
As shown in FIG. 1, the relationship between the current density Ia of the positive pulse and the current density Ic of the negative pulse satisfies the equation (1), and the relationship between the energization time Ta of the positive pulse and the energization time Tc of the negative pulse is ( 2) When the equation is satisfied and the relationship between the accumulated current value Qa per unit area of the positive pulse and the accumulated current value Qc per unit area of the negative pulse satisfies the equation (3), it is formed on the surface. The roughness due to the protrusions increases, and it becomes possible to obtain a roughened rolled copper sheet having adhesiveness with a resin as high as that of a conventional roughened electrolytic copper foil. On the other hand, if any of the above relationships does not satisfy the above formula, the roughness due to the protrusions formed on the surface is low, and sufficient adhesion to the resin cannot be obtained.
なお、図１では、パルスの通電を負パルスから始めた例を示しているが、負パルス、正パルスのどちらから始めてもよい。いずれから始めても、上記（１）〜（３）式を満たす限り、上記と同様の効果が奏されるものである。
また、本発明における圧延銅板には、市販されているものをいずれも使用できる。その厚みもとくに限定されないが、大電流通電基板の導体層やメタルコア基板のメタルコア層として利用できる７０μｍ以上の厚みの圧延銅板が好ましい。
Although FIG. 1 shows an example in which the energization of a pulse is started from a negative pulse, it may be started from either a negative pulse or a positive pulse. Even if it starts from any, as long as the said Formula (1)-(3) is satisfy | filled, the effect similar to the above is show | played.
Moreover, as the rolled copper plate in the present invention, any commercially available one can be used. Although the thickness is not particularly limited, a rolled copper plate having a thickness of 70 μm or more that can be used as a conductor layer of a large current conducting substrate or a metal core layer of a metal core substrate is preferable.
つぎに、本発明の実施例に基づき、さらに具体的に説明する。ただし、本発明は、これらの実施例に限定されるものではない。 Next, based on the example of the present invention, it explains still more concretely. However, the present invention is not limited to these examples.
実施例１〜１８
３００ｍｍ×３００ｍｍ×０．２ｍｍの圧延銅板（タフピッチ銅）を用い、これに通常の前処理方法（脱脂、酸洗い、水洗）を施したのち、下記の粗化処理液（電解液）中で、電流密度の絶対値および時間が異なる正負のパルスを用いて、正負の単位面積当たりの積算電流値の絶対値が異なる正負のパルス電解を行い（負側：めっき、正側：溶解）、圧延銅板表面を粗化した。粗化処理条件〔正負パルスの電流密度、通電時間、トータル通電（粗化処理）時間〕を、表１（実施例１〜５）、表２（実施例６〜１３）、表４（実施例１４〜１８）のように、設定して、１８種の粗化圧延銅板を製造した。
Examples 1-18
Using a rolled copper plate (tough pitch copper) of 300 mm × 300 mm × 0.2 mm, and after applying a normal pretreatment method (degreasing, pickling, washing with water) to this, in the following roughening treatment liquid (electrolytic solution), Using positive and negative pulses with different absolute values of current density and time, positive and negative pulse electrolysis with different absolute values of accumulated current values per positive and negative unit area (negative side: plating, positive side: melting), rolled copper plate The surface was roughened. Table 1 (Examples 1 to 5), Table 2 (Examples 6 to 13), and Table 4 (Examples) for roughening treatment conditions [current density of positive and negative pulses, energization time, total energization (roughening treatment) time]. 14-18), 18 kinds of roughened rolled copper sheets were produced.
＜粗化処理液＞
硫酸銅五水塩：９０ｇ／Ｌ、
硫酸：１１０ｍＬ／Ｌ、
塩素イオン：７０ｐｐｍ、
光沢剤：カパーグリームＰＰＲ−Ｃ；５ｍＬ／Ｌ
カパーグリームＰＰＲ−Ａコンク；０．２ｍＬ／Ｌ
（光沢剤はＲｏｈｍ ａｎｄ Ｈａａｓ社製）
液温度：２０℃
<Roughening solution>
Copper sulfate pentahydrate: 90 g / L,
Sulfuric acid: 110 mL / L,
Chloride ion: 70 ppm,
Brightener: Capper Gream PPR-C; 5 mL / L
Copper Gree PPR-A Conch; 0.2 mL / L
(Brightener is made by Rohm and Haas)
Liquid temperature: 20 ° C
比較例１
表４に示すように、正負のパルス電解を行わず、直流電流密度５Ａ／ｄｍ2による陰極電解（銅めっき）を２８０ｓ行い、粗化圧延銅板を製造した。
Comparative Example 1
As shown in Table 4, positive and negative pulse electrolysis was not performed, and cathodic electrolysis (copper plating) was performed at a direct current density of 5 A / dm 2 for 280 s to produce a rough rolled copper sheet.
比較例２
表４に示すように、正負パルスの電流密度は（１）式を満たし、正負パルスの通電時間は（２）式を満たすが、正パルスの単位面積当たりの積算電流値Ｑａと負パルスの単位面積当たりの積算電流値Ｑｃとが（３）式を満たさない粗化処理条件で、正負のパルス電解を行い、粗化圧延銅板を製造した。
Comparative Example 2
As shown in Table 4, the current density of the positive and negative pulses satisfies the formula (1) and the energization time of the positive and negative pulses satisfies the formula (2), but the integrated current value Qa per unit area of the positive pulse and the unit of the negative pulse Positive and negative pulse electrolysis was performed under roughening conditions where the integrated current value Qc per area did not satisfy the formula (3) to produce a roughened rolled copper sheet.
比較例３
表４に示すように、実施例３と同じ正負のパルス電解を行ったのち、直流電流密度３Ａ／ｄｍ2による陰極電解（銅めっき）を１８０ｓ行った、すなわち、パルス電解と直流による陰極電解（銅めっき）を組み合わせて、粗化圧延銅板を製造した。
Comparative Example 3
As shown in Table 4, after performing the same positive and negative pulse electrolysis as in Example 3, cathodic electrolysis (copper plating) with a direct current density of 3 A / dm 2 was performed for 180 s, that is, cathodic electrolysis with pulse electrolysis and direct current ( A roughened rolled copper sheet was manufactured by combining copper plating.
上記の実施例１〜１８および比較例１〜３の各粗化圧延銅板を使用し、これをプリプレグと積層して銅張積層板を作製した。この銅張積層板について、ＪＩＳ Ｃ６４８１に基づく引きはがし試験を行い、積層プレス後未加熱品のピール強度を測定した。また、実施例１〜５および実施例１４〜１８の各銅張積層板は、積層プレス後未加熱品だけでなく、２６０℃のハンダで６０秒間加熱処理したものについても測定した。
これらの結果を表１〜表４に併記した。なお、表４には、参考のために、従来の粗化電解銅箔（０．０７ｍｍ厚）を使用して、上記と同様に銅張積層板を作製したものについての結果も併記した。
Using each of the roughened rolled copper plates of Examples 1 to 18 and Comparative Examples 1 to 3 described above, this was laminated with a prepreg to prepare a copper-clad laminate. About this copper clad laminated board, the peeling test based on JISC6481 was done, and the peel strength of the unheated goods was measured after the lamination press. Moreover, each copper clad laminated board of Examples 1-5 and Examples 14-18 measured not only the unheated goods after lamination press but what was heat-processed with 260 degreeC solder | solder for 60 seconds.
These results are also shown in Tables 1 to 4. In Table 4, for reference, the results of using a conventional roughened electrolytic copper foil (0.07 mm thickness) to produce a copper clad laminate in the same manner as described above are also shown.
上記の表１〜表４の結果から明らかなように、本発明の実施例１〜１８の各圧延銅箔は積層プレス後未加熱品で２．１〜３．２ｋＮ／ｍのピール強度を有し、電解銅箔の２．５ｋＮ／ｍと同等であった。これに対し、比較例１〜３の各圧延銅箔は、積層プレス後未加熱品で０．７〜１．４ｋＮ／ｍのピール強度を示し、電解銅箔に比べて著しく劣っていた。
また、本発明の実施例１〜５および実施例１４〜１８の各圧延銅箔は、２６０℃のハンダで６０秒加熱処理したのちでも、１．９〜２．８ｋＮ／ｍと処理前の約９０％のピール力を維持し、ハンダ耐熱性が良好であった。
As is clear from the results in Tables 1 to 4 above, each rolled copper foil of Examples 1 to 18 of the present invention is an unheated product after lamination press and has a peel strength of 2.1 to 3.2 kN / m. It was equivalent to 2.5 kN / m of the electrolytic copper foil. On the other hand, each rolled copper foil of Comparative Examples 1 to 3 was an unheated product after the lamination press and exhibited a peel strength of 0.7 to 1.4 kN / m, which was significantly inferior to the electrolytic copper foil.
In addition, each of the rolled copper foils of Examples 1 to 5 and Examples 14 to 18 of the present invention is 1.9 to 2.8 kN / m, which is about 1.9 to 2.8 kN / m after heat treatment with 260 ° C. solder. The peel strength of 90% was maintained and the solder heat resistance was good.
Claims (4)
｜Ｉａ｜＞｜Ｉｃ｜ … （１）
Ｔａ＜Ｔｃ … （２）
１＜｜Ｑｃ／Ｑａ｜≦４ … （３）
〔ここで、（１），（３）式中の｜｜は、絶対値を表している〕 A rough rolled copper plate roughened by an electrochemical method, the rough rolled copper plate being pulse electrolyzed with asymmetric positive and negative pulses in an electrolyte containing a brightener, and the current density of the positive pulse Ia (A / dm 2 ) and the negative pulse current density Ic (A / dm 2 ) satisfy the following formula (1), and the positive pulse energization time Ta (seconds) and the negative pulse energization time Tc ( Second) satisfies the following equation (2), and the cumulative current value Qa (A · s / dm 2 ) of the positive pulse and the cumulative current value Qc (A · s / dm 2 ) of the negative pulse are the following (3 The roughened rolled copper sheet characterized by satisfying the formula:
| Ia |> | Ic | (1)
Ta <Tc (2)
1 <| Qc / Qa | ≦ 4 (3)
[Where, || in the expressions (1) and (3) represents an absolute value]
｜Ｉａ｜＞｜Ｉｃ｜ … （１）
Ｔａ＜Ｔｃ … （２）
１＜｜Ｑｃ／Ｑａ｜≦４ … （３）
〔ここで、（１），（３）式中の｜｜は、絶対値を表している〕 A step of subjecting the rolled copper plate to pulse electrolysis with an asymmetric positive and negative pulse in an electrolyte containing a brightener, and the positive pulse current density Ia (A / dm 2 ) and the negative pulse current density Ic (A / dm 2 ) satisfies the following equation (1), the energizing time Ta (second) of the positive pulse and the energizing time Tc (second) of the negative pulse satisfy the following equation (2), and the accumulated current of the positive pulse: A method for producing a rough rolled copper sheet, characterized in that a value Qa (A · s / dm 2 ) and an integrated current value Qc (A · s / dm 2 ) of the negative pulse satisfy the following expression (3):
| Ia |> | Ic | (1)
Ta <Tc (2)
1 <| Qc / Qa | ≦ 4 (3)
[Where, || in the expressions (1) and (3) represents an absolute value]
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| JP6093646B2 (en) | 2013-05-14 | 2017-03-08 | 新光電気工業株式会社 | Manufacturing method of plating film |
| CN109468670B (en) * | 2018-11-16 | 2021-03-26 | 中山品高电子材料有限公司 | Method for electroplating copper layer on lead frame |
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| KR102638749B1 (en) * | 2019-06-07 | 2024-02-21 | 후루카와 덴키 고교 가부시키가이샤 | Surface treated copper foil, copper clad laminate and printed wiring board |
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