JP5706026B1 - Copper foil for wiring board and wiring board - Google Patents
Copper foil for wiring board and wiring board Download PDFInfo
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- JP5706026B1 JP5706026B1 JP2014146807A JP2014146807A JP5706026B1 JP 5706026 B1 JP5706026 B1 JP 5706026B1 JP 2014146807 A JP2014146807 A JP 2014146807A JP 2014146807 A JP2014146807 A JP 2014146807A JP 5706026 B1 JP5706026 B1 JP 5706026B1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
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Abstract
【課題】配線板に適用して好適な樹脂密着性と回路パターン形成後の視認性を両立させた配線板用電解銅箔を提供する。【解決手段】電解銅の樹脂を接着する被接着面側表面の波長６００ｎｍにおける拡散反射率（Ｒｄ）が５〜５０％で、彩度（Ｃ＊）が５０以下である配線板用電解銅箔である。本配線板用電解銅箔においては、明度指数（Ｌ＊）を７５以下とすることが好ましく、波長６００ｎｍにおける全光線反射率（Ｒｔ）を１０〜５５％とすることがより好ましい。【選択図】なしDisclosed is an electrolytic copper foil for a wiring board, which is suitable for application to a wiring board and has both good resin adhesion and visibility after circuit pattern formation. An electrolytic copper foil for a wiring board having a diffuse reflectance (Rd) of 5 to 50% at a wavelength of 600 nm and a chroma (C *) of 50 or less on a surface to be bonded to which an electrolytic copper resin is bonded. It is. In this electrolytic copper foil for wiring boards, the lightness index (L *) is preferably 75 or less, and the total light reflectance (Rt) at a wavelength of 600 nm is more preferably 10 to 55%. [Selection figure] None
Description
本発明は、配線板用の銅箔に関するもので、より詳しくは樹脂密着性と回路パターン形成後の樹脂透過視認性を両立させた、配線板に適用して好適な銅箔に関するものである。 The present invention relates to a copper foil for a wiring board, and more particularly relates to a copper foil suitable for application to a wiring board that achieves both resin adhesion and resin permeation visibility after forming a circuit pattern.
各種電子機器類において基板や接続材料として配線板が用いられており、配線板の導電層には銅箔が一般的に使用されている。 In various electronic devices, a wiring board is used as a substrate or a connection material, and a copper foil is generally used for a conductive layer of the wiring board.
上記配線板に採用される銅箔は一般的に圧延銅箔または電解銅箔の形で供給される。
配線板用銅箔に使用する圧延銅箔は、その製造工程で付与される熱履歴における結晶成長を抑制するために金属等の添加物を必須成分として含有する。このため銅箔本来の導電性が低下し、また、製造コストも電解銅箔より劣る場合がある。そのため、配線板用銅箔としては導電性が高く、生産性に優れ、薄層化が容易な電解銅箔が広く用いられる傾向にある。
The copper foil employed for the wiring board is generally supplied in the form of a rolled copper foil or an electrolytic copper foil.
The rolled copper foil used for the copper foil for wiring boards contains an additive such as a metal as an essential component in order to suppress crystal growth in the thermal history imparted in the production process. For this reason, the original electroconductivity of copper foil falls and manufacturing cost may be inferior to electrolytic copper foil. Therefore, as the copper foil for wiring boards, electrolytic copper foil that has high conductivity, excellent productivity, and easy thinning tends to be widely used.
配線板は、一般的には銅箔とポリイミドなどの樹脂フィルムとを貼り合わせ、エッチングで回路パターンを形成する。回路パターンが形成された配線板はその後の実装工程においては、回路パターン形成時に銅箔をエッチングした箇所の樹脂フィルムを透かしてアライメントマーク等をカメラで認識し位置決めを行う場合がある。そのため、この樹脂フィルムを透過した光が拡散せず明瞭にカメラで認識できる樹脂透過視認性状態であることが要求される。
本明細書では以下、この樹脂透過視認性を単に「視認性」と表現する。
The wiring board is generally formed by bonding a copper foil and a resin film such as polyimide, and forming a circuit pattern by etching. In the subsequent mounting process, the wiring board on which the circuit pattern is formed may be positioned by recognizing the alignment mark or the like with a camera through the resin film where the copper foil is etched when forming the circuit pattern. Therefore, it is required that the light transmitted through the resin film is in a resin transmission visibility state that can be clearly recognized by a camera without diffusing.
In the present specification, the resin permeation visibility is hereinafter simply referred to as “visibility”.
樹脂フィルムの視認性は一般的にＨａｚｅ(曇値)で表される。樹脂フィルムの全光線透過率（Ｔｔ）、拡散透過率（Ｔｄ）に対してＨａｚｅは下記式で表される。
（Ｔｄ／Ｔｔ）×１００（％）
値が小さいほど視認性が高い。視認性の評価には一般に波長６００ｎｍのＨａｚｅが採用される。
The visibility of the resin film is generally represented by Haze (cloudiness value). Total light transmittance of resin film (T t ), Diffuse transmittance (T d Haze is expressed by the following formula.
(Td / Tt) × 100 (%)
The smaller the value, the higher the visibility. For evaluation of visibility, Haze having a wavelength of 600 nm is generally employed.
樹脂フィルムの種類が同一であれば、樹脂フィルムのＨａｚｅは表面形状に左右される。表面が荒れていると拡散透過成分が大きくなりＨａｚｅは高くなるため、視認性を高くするには表面を平滑にする必要がある。
また、樹脂フィルムの表面形状は、貼り合せた銅箔の表面形状を転写する。そのため、平滑な樹脂表面を得るためには平滑な銅箔を使用することが必要になる。
If the type of the resin film is the same, the haze of the resin film depends on the surface shape. If the surface is rough, the diffuse transmission component becomes large and the haze increases. Therefore, the surface needs to be smoothed to increase the visibility.
Moreover, the surface shape of the resin film transfers the surface shape of the bonded copper foil. Therefore, in order to obtain a smooth resin surface, it is necessary to use a smooth copper foil.
一方、配線板としての使用に対しては、樹脂フィルムと銅箔の密着性が要求される。密着性向上のためには銅箔表面を粗くして接触表面積の増大およびアンカー効果を利用することが多い。密着性の向上は視認性の低下に繋がり、樹脂密着性と視認性とは、二律背反する関係にある。 On the other hand, for use as a wiring board, adhesion between the resin film and the copper foil is required. In order to improve adhesion, the copper foil surface is often roughened to increase the contact surface area and use the anchor effect. The improvement in adhesion leads to a decrease in visibility, and the resin adhesion and visibility are in a trade-off relationship.
銅箔表面を粗くする方法(粗化処理)としては、銅箔上に粒状の銅めっきを施す（粗化めっき）ことが一般的である。その他にエッチングで表面を粗くする方法、銅以外の金属または合金めっきで粗化めっきを施すといった方法が用いられる。 As a method for roughening the copper foil surface (roughening treatment), it is common to apply granular copper plating (roughening plating) on the copper foil. In addition, a method of roughening the surface by etching or a method of roughening plating by metal or alloy plating other than copper is used.
特許文献１（特開平１１−３４０５９６）は、銅の粗化めっきを２回施すことにより、一次粗化粒子の上により小さい二次粗化粒子を析出させることで樹脂との密着力を高めていることを特徴とする電解銅箔を開示している。しかしこの発明の電解銅箔は表面が粗くなりすぎているために密着性は優れているが視認性が低い。 Patent Document 1 (Japanese Patent Laid-Open No. 11-340596) increases the adhesion with a resin by precipitating smaller secondary roughened particles on the primary roughened particles by performing copper roughening plating twice. An electrolytic copper foil is disclosed. However, since the surface of the electrolytic copper foil of the present invention is too rough, the adhesiveness is excellent, but the visibility is low.
特許文献２（特開２００８−２８５７５１）は、粗化めっきの条件を調整することにより大きな比表面積を持つことを特徴とする電解銅箔を開示している。しかしこの発明の電解銅箔も表面が粗くなりすぎているために密着性は優れているが視認性が低い。 Patent document 2 (Unexamined-Japanese-Patent No. 2008-285751) is disclosing the electrolytic copper foil characterized by having a large specific surface area by adjusting the conditions of roughening plating. However, since the surface of the electrolytic copper foil of the present invention is too rough, the adhesion is excellent but the visibility is low.
特許文献３（特開２０１１−１１９７５９）は、特殊な熱圧着で得られる多層ポリイミドフィルムを、平滑な銅箔に特殊な条件で熱圧着することを特徴とする銅張積層板を開示している。しかしこの発明は樹脂の構成および銅張積層板の製法に制約が多く、ある特定の条件でのみ実現できる内容であるといえる。またこの発明の銅張積層板には平滑な銅箔を用いるため視認性には優れるが密着性は劣る。 Patent Document 3 (Japanese Patent Application Laid-Open No. 2011-119759) discloses a copper clad laminate characterized by thermocompression bonding a multilayer polyimide film obtained by special thermocompression bonding to a smooth copper foil under special conditions. . However, the present invention has many restrictions on the resin structure and the copper clad laminate manufacturing method, and it can be said that the present invention can be realized only under specific conditions. Moreover, since smooth copper foil is used for the copper clad laminated board of this invention, it is excellent in visibility, but adhesiveness is inferior.
特許文献４（特許５０３５２２０）は、熱圧着性多層ポリイミドフィルムを平滑な銅箔に特殊な条件で熱圧着することを特徴とする銅張積層板を開示している。しかしこの発明も樹脂の構成および銅張積層板の製法には制約が多く、ある特定の条件でのみ実現できる内容であるといえる。またこの発明の銅張積層板には平滑な銅箔を用いるため視認性には優れるが密着性は劣る。 Patent Document 4 (Patent 5035220) discloses a copper-clad laminate characterized by thermocompression bonding a thermocompression-bonding multilayer polyimide film to a smooth copper foil under special conditions. However, the present invention also has many restrictions on the resin structure and the method for producing the copper clad laminate, and can be said to be a content that can be realized only under certain specific conditions. Moreover, since smooth copper foil is used for the copper clad laminated board of this invention, it is excellent in visibility, but adhesiveness is inferior.
特許文献５（特許４０９０４６７）は、鏡面光沢度の高い銅箔に対して一定の組成比を持つ（ニッケルー亜鉛）めっきを施したことを特徴とする電解銅箔を開示している。この発明は光透過率で視認性の評価を行っているが、光透過率つまり全光線透過率がある程度以上高いことは高視認性にとって必要条件であって十分条件ではない。高視認性にとっては全光線透過率が高くかつ拡散透過率が低いことが十分条件となるが、この発明は光沢箔を使用するものの（ニッケル−亜鉛）めっきを特殊な条件で行っているために密着性には優れるが拡散透過率が高く、視認性には劣る。 Patent Document 5 (Patent 4090467) discloses an electrolytic copper foil characterized by applying (nickel-zinc) plating having a certain composition ratio to a copper foil having high specular gloss. In this invention, the visibility is evaluated by the light transmittance, but the light transmittance, that is, the total light transmittance, is higher than a certain level, which is a necessary condition for high visibility and not a sufficient condition. A high total light transmittance and a low diffuse transmittance are sufficient conditions for high visibility, but this invention uses a glossy foil, but (nickel-zinc) plating is performed under special conditions. It has excellent adhesion but high diffuse transmittance and poor visibility.
特許文献６（特開平５−３３１９３）は、銅箔表面に酸化物を形成し、その後還元することで銅箔表面に微細構造を形成したことを特徴とする銅箔を開示している。この発明の銅箔は非常に粗い表面を有するために、この箔表面を転写した樹脂フィルムの視認性は低い。 Patent document 6 (Unexamined-Japanese-Patent No. 5-33193) is disclosing the copper foil characterized by forming the oxide on the copper foil surface, and forming the fine structure on the copper foil surface by reducing after that. Since the copper foil of this invention has a very rough surface, the visibility of the resin film which transferred this foil surface is low.
特許文献７（特開２０１０−２３６０５８）は、粗化めっきの粗化粒子先端角を鋭くすることでロープロファイルと樹脂密着性を両立させたことを特徴とする銅箔を開示している。しかしこの発明の銅箔表面は十分に粗いために、この箔表面を転写した樹脂フィルムの視認性は低い。 Patent Document 7 (Japanese Patent Application Laid-Open No. 2010-236058) discloses a copper foil characterized in that both low profile and resin adhesion are achieved by sharpening the tip angle of the roughening particles of roughening plating. However, since the copper foil surface of the present invention is sufficiently rough, the visibility of the resin film to which the foil surface is transferred is low.
特許文献８（特許４４７０９１７）は、粗化めっき後の表面色を制御することでリチウムイオン二次電池のサイクル特性を向上させた電池集電体用銅箔を開示している。この発明の銅箔は電池電極合剤との密着性を高めるために表面が粗化されており、この箔の表面を転写した配線板用樹脂フィルムの視認性は低い。 Patent Document 8 (Patent 4470917) discloses a copper foil for a battery current collector in which the cycle characteristics of a lithium ion secondary battery are improved by controlling the surface color after rough plating. The surface of the copper foil of the present invention is roughened in order to enhance the adhesion to the battery electrode mixture, and the visibility of the resin film for wiring boards to which the surface of this foil is transferred is low.
本発明は、配線板の用途に好適な樹脂密着性と回路パターン形成後の視認性を両立させた配線板用銅箔を提供することにある。 An object of the present invention is to provide a copper foil for a wiring board that achieves both resin adhesion suitable for the use of the wiring board and visibility after forming a circuit pattern.
本発明によれば、実質的に純銅で粗化処理された銅箔の被接着面側表面において、波長６００ｎｍにおける拡散反射率（Ｒd）が５〜５０％の範囲内で、かつ彩度（Ｃ*）が５０以下であることを特徴とする配線板用銅箔が提供される。
According to the present invention, the diffuse reflectance (R d ) at a wavelength of 600 nm is within a range of 5 to 50% on the surface to be bonded of the copper foil that has been substantially roughened with pure copper, and the saturation ( A copper foil for wiring boards is provided, wherein C * ) is 50 or less.
本発明の前記配線板用銅箔は、前記樹脂が積層される銅箔の表面において面の明度指数Ｌ＊（Ｌｉｇｈｔｎｅｓｓ）が７５以下であることが好ましい。 The copper foil for wiring board of the present invention preferably has a surface brightness index L * (Lightness) of 75 or less on the surface of the copper foil on which the resin is laminated.
本発明の前記配線板用銅箔は、前記樹脂が積層される銅箔の表面において、波長６００ｎｍにおける全光線反射率（Ｒｔ）が１０〜５５％の範囲内であることが好ましい。 The copper foil for wiring board of the present invention preferably has a total light reflectance (R t ) within a range of 10 to 55% at a wavelength of 600 nm on the surface of the copper foil on which the resin is laminated.
本発明の前記配線板用銅箔は、前記樹脂が積層される銅箔の表面において、入射角60°における光沢度Ｇｓ（６０°）が５％以上であることが好ましい。 The copper foil for wiring board of the present invention preferably has a gloss Gs (60 °) at an incident angle of 60 ° of 5% or more on the surface of the copper foil on which the resin is laminated.
本発明の前記配線板用銅箔は、樹脂フィルムと積層され、前記電解銅箔をエッチングすることで回路パターンが形成されることを特徴とする。 The copper foil for wiring boards of the present invention is laminated with a resin film, and a circuit pattern is formed by etching the electrolytic copper foil.
本発明の前記配線板用銅箔は、必要に応じて密着性・防錆・耐薬品性等を目的とした各種表面処理を施すことも可能である。
本発明の配線板用銅箔は、電解銅箔であることとすれば特に好ましい。
The copper foil for wiring board of the present invention can be subjected to various surface treatments for the purpose of adhesion, rust prevention, chemical resistance and the like, if necessary.
The copper foil for wiring boards of the present invention is particularly preferable if it is an electrolytic copper foil.
本発明により、樹脂との密着性を確保した上で視認性を損なわない配線板用銅箔を提供することができる。 According to the present invention, it is possible to provide a copper foil for wiring boards that does not impair visibility while ensuring adhesion with a resin.
本発明の配線板用銅箔は、少なくとも一方の面が、例えば、電解銅箔の場合は、Ｍ面（マット面）またはＳ面（シャイニー面）の少なくとも一方の面、圧延銅箔の場合は圧延面の少なくとも一方の面が波長６００ｎｍにおける拡散反射率が５〜５０％の範囲内で、かつ彩度（Ｃ＊）が５０以下であることを特徴とする。
なお、本明細書においては銅箔製造時においてＴｉ板などに代表されるカソードと接触
していた面をＳ（ｓｈｉｎｙ）面、電解液と接触していた面をＭ（ｍａｔｔｅ）面と表記
する。
樹脂フィルムの全光線透過率は樹脂の種類および厚さによっておおよそ定まり、樹脂形状で少しは変化するもののその変化の程度は小さい。そのため、視認性を評価するＨａｚｅは拡散透過率に大きく影響される。樹脂の拡散透過率はその表面形状に大きく影響される。樹脂の表面形状は銅箔の表面形状を転写したものとなる。そのため、銅箔の形状が樹脂の拡散透過率および視認性に大きく影響する。
銅箔表面の拡散反射率が５０％より大きいと、転写された表面形状を持つ樹脂は拡散透過率が上昇し、密着力は優れるが視認性が悪くなる。一方、拡散反射率が５％より小さいと、極めて良好な光沢を持つ銅箔表面となるが、平滑すぎるために視認性は優れるが樹脂との密着性は低下する。
When the copper foil for wiring boards of the present invention has at least one surface, for example, an electrolytic copper foil, at least one surface of an M surface (matt surface) or an S surface (shiny surface), or a rolled copper foil. At least one of the rolled surfaces has a diffuse reflectance of 5 to 50% at a wavelength of 600 nm and a saturation (C * ) of 50 or less.
In the present specification, the surface that is in contact with the cathode typified by a Ti plate at the time of manufacturing the copper foil is referred to as the S (shiny) surface, and the surface that is in contact with the electrolytic solution is referred to as the M (matte) surface. .
The total light transmittance of the resin film is roughly determined by the type and thickness of the resin, and changes slightly depending on the resin shape, but the degree of change is small. Therefore, Haze for evaluating visibility is greatly influenced by the diffuse transmittance. The diffuse transmittance of the resin is greatly influenced by the surface shape. The surface shape of the resin is a transfer of the surface shape of the copper foil. Therefore, the shape of the copper foil greatly affects the diffuse transmittance and visibility of the resin.
When the diffuse reflectance of the copper foil surface is larger than 50%, the resin having the transferred surface shape has an increased diffuse transmittance and excellent adhesion, but the visibility is deteriorated. On the other hand, if the diffuse reflectance is less than 5%, the surface of the copper foil has a very good gloss. However, since the surface is too smooth, the visibility is excellent, but the adhesion with the resin is reduced.
色を、明度指数Ｌ＊とクロマネティクス指数ａ＊、ｂ＊から成る均等色空間上の座標で表わした、
ＣＩＥ Ｌ＊ａ＊ｂ＊表色系において、彩度（Ｃ＊）は数式（１）で算出される。彩度が低いほど灰色な表面になる。彩度が高い表面は反射率が波長によって大きく異なり、反対に彩度が低い表面は分光反射率が平坦である。
〔数式１〕
In the CIE L * a * b * color system, the saturation (C * ) is calculated by Equation (1). The lower the saturation, the grayer the surface. The surface with high saturation varies greatly depending on the wavelength, and the surface with low saturation has a flat spectral reflectance.
[Formula 1]
銅箔表面の色相は、表面処理によって大きく異なる。しかしＨａｚｅは一般的に波長６００ｎｍの値を評価に使用する。
Ｈａｚｅの評価が一般的に波長６００ｎｍの値を採用することに注目した本発明者等は、彩度（Ｃ＊）が５０以下、つまり彩度が低いことでどの色相の表面においても波長６００ｎｍの反射率は一定以上に保たれ、このような表面を有する銅箔は、表面を転写した樹脂フィルムの視認性と密着性の両立が可能であることを見出した。
また銅箔の表面から視認性が決定されるために樹脂の種類、樹脂の製法、配線板の製法等に左右されにくいことを見出した。
The hue of the copper foil surface varies greatly depending on the surface treatment. However, Haze generally uses a value of wavelength 600 nm for evaluation.
The inventors of the present invention who paid attention to the fact that the evaluation of Haze generally adopts a value of a wavelength of 600 nm have a saturation (C * ) of 50 or less, that is, the saturation is low, and the surface of any hue has a wavelength of 600 nm. It has been found that the reflectance is kept above a certain level, and the copper foil having such a surface can achieve both the visibility and adhesion of the resin film having the surface transferred.
Moreover, since visibility was determined from the surface of copper foil, it discovered that it was hard to be influenced by the kind of resin, the manufacturing method of resin, the manufacturing method of a wiring board, etc.
本発明の配線板用銅箔は、明度指数（Ｌ＊）が７５以下であることが好ましい。
銅箔表面は、明度指数（Ｌ＊）が高いほど白く、低いほど黒く見える。本発明者等は、白い表面の銅箔は、箔表面での光の散乱回数が多く散乱光の角度が広く分散するために白く明るく見えることを確認した。一方、同じ拡散反射率を持つ銅箔でも明度の低い箔の場合は、箔表面の光の散乱回数が比較的少なく散乱光の角度は広く分散しないことを確認し、明度指数（Ｌ＊）が７５以下である表面を転写した樹脂フィルムは、明度指数（Ｌ＊）が高い白い箔の表面を転写した樹脂フィルムに比べて視認性が高いことを見出した。
The copper foil for wiring boards of the present invention preferably has a lightness index (L * ) of 75 or less.
The copper foil surface appears whiter as the lightness index (L * ) is higher, and blacker as it is lower. The present inventors have confirmed that a white surface copper foil appears white and bright because the number of light scattering on the foil surface is large and the angle of scattered light is widely dispersed. On the other hand, in the case of a copper foil having the same diffuse reflectance but a low brightness, it is confirmed that the number of light scattering on the foil surface is relatively small and the angle of the scattered light is not widely dispersed, and the brightness index (L * ) is It was found that a resin film having a surface of 75 or less transferred has higher visibility than a resin film having a surface of a white foil having a high lightness index (L * ).
本発明の配線板用銅箔は、波長６００ｎｍにおける全光線反射率が１０〜５５％の範囲内であることが好ましい。全光線反射率が５５％より高いと拡散反射率が高いことが多く視認性が低い。また１０％より低いときには密着力が低下する。 The copper foil for wiring board of the present invention preferably has a total light reflectance at a wavelength of 600 nm in a range of 10 to 55%. When the total light reflectance is higher than 55%, the diffuse reflectance is often high and the visibility is low. On the other hand, when it is lower than 10%, the adhesion is reduced.
本発明の配線板用銅箔は、入射角６０°における光沢度（Ｇｓ（６０°））が５％以上であることが好ましい。光沢度が５％未満のときは視認性が低くなる。
なお、本明細書においては「光沢度（Ｇｓ（６０°））」を単に「光沢度」と表記する。
The copper foil for wiring board of the present invention preferably has a glossiness (Gs (60 °)) of 5% or more at an incident angle of 60 °. When the glossiness is less than 5%, the visibility is low.
In this specification, “glossiness (Gs (60 °))” is simply expressed as “glossiness”.
以下本発明の一実施形態につき詳細に説明する。
使用する銅箔は処理を行う面が、処理前の時点で光沢度が１０％以上であることが好ましい。使用前の未処理銅箔の光沢度は、無光沢箔で０〜３０程度、光沢箔で１００〜５００程度であり、光沢度が１０％未満の表面形状では、粗化処理後に十分な視認性を得ることが難しくなるためである。
上記銅箔の少なくとも片面（電解銅箔の場合は、Ｍ面またはＳ面の少なくとも一方の面、圧延銅箔の場合は圧延面の少なくとも一方の面）に粗化処理を行う。
無粗化の状態の銅箔では、視認性と樹脂密着性を両立することは難しい。以下に述べる後処理で箔表面を適切な状態に調整することが重要となる。
Hereinafter, one embodiment of the present invention will be described in detail.
As for the copper foil to be used, it is preferable that the surface to be processed has a glossiness of 10% or more before the processing. The glossiness of the untreated copper foil before use is about 0 to 30 for matte foil, about 100 to 500 for glossy foil, and the surface shape with a glossiness of less than 10% has sufficient visibility after roughening treatment. This is because it becomes difficult to obtain.
Roughening treatment is performed on at least one surface of the copper foil (in the case of electrolytic copper foil, at least one surface of the M surface or S surface, in the case of rolled copper foil, at least one surface of the rolled surface).
With a copper foil in a non-roughened state, it is difficult to achieve both visibility and resin adhesion. It is important to adjust the foil surface to an appropriate state by post-processing described below.
粗化処理の代表例としてはＣｕ粗化めっきである。Ｃｕ粗化めっきには硫酸銅めっき液を用いる。粗化めっき液の硫酸濃度は５０〜２５０ｇ／Ｌ（リットル）、特に７０〜２００ｇ／Ｌが好ましい。硫酸濃度が５０ｇ／Ｌ未満となると導電率が低く、粗化粒子の電着性が悪くなる。硫酸濃度を２５０ｇ／Ｌより上げると設備の腐食が促進される。
粗化めっき液の銅濃度は６〜１００ｇ／Ｌ、特に１０〜５０ｇ／Ｌが好ましい。銅濃度が６ｇ／Ｌ未満となると粗化粒子の電着性が悪くなる。銅濃度を１００ｇ／Ｌより上げると粒子状にめっきするにはより大電流が必要になり、設備上も現実的でない。
A typical example of the roughening treatment is Cu roughening plating. A copper sulfate plating solution is used for Cu roughening plating. The sulfuric acid concentration of the roughening plating solution is preferably 50 to 250 g / L (liter), particularly 70 to 200 g / L. When the sulfuric acid concentration is less than 50 g / L, the electrical conductivity is low, and the electrodeposition properties of the roughened particles are deteriorated. Increasing the sulfuric acid concentration above 250 g / L promotes equipment corrosion.
The copper concentration of the roughening plating solution is preferably 6 to 100 g / L, particularly preferably 10 to 50 g / L. When the copper concentration is less than 6 g / L, the electrodeposition properties of the roughened particles are deteriorated. When the copper concentration is increased above 100 g / L, a larger current is required for plating in the form of particles, which is not realistic in terms of equipment.
粗化めっき液には有機または無機添加剤を添加しても良い。高分子多糖類を添加すると、拡散限界電流密度を小さくし、より低い電流密度条件でも粗化粒子が発生しやすくなる。
An organic or inorganic additive may be added to the roughening plating solution. When the high molecular polysaccharide is added, the diffusion limit current density is decreased, and roughened particles are easily generated even under a lower current density condition .
粗化めっきする電流密度は５〜１２０Ａ／ｄｍ２、特に３０〜１００Ａ／ｄｍ２が好ましい。電流密度が５Ａ／ｄｍ２未満になると処理に時間を要するために生産性が低い。電流密度を１２０Ａ／ｄｍ２より上げると粗化粒子の電着性が悪くなる。 The current density for rough plating is preferably 5 to 120 A / dm 2 , particularly preferably 30 to 100 A / dm 2 . When the current density is less than 5 A / dm 2 , the process takes time, and the productivity is low. When the current density is increased from 120 A / dm 2 , the electrodeposition property of the roughened particles is deteriorated.
粗化処理をした後に、粗化粒子を覆い粗化粒子と銅箔の密着性を高めるめっき処理を行っても良い。その場合も硫酸銅めっき液が用いられる。この２層めっき処理を更に複数回数重ねることで粗化粒子の均一電着性を高めても良い。 After the roughening treatment, a plating treatment for covering the roughened particles and improving the adhesion between the roughened particles and the copper foil may be performed. In that case, a copper sulfate plating solution is also used. The two-layer plating process may be further repeated a plurality of times to improve the uniform electrodeposition of the roughened particles.
また、粗化めっき以外の手法により粗化処理を行っても良い。例としては、エッチング処理によるもの、酸化剤または雰囲気調整により箔表面を酸化させ表面を粗化させるもの、酸化させた表面を再還元することで表面を粗化させるもの、およびこれらを組み合わせた処理によるものなどが挙げられる。
Moreover, you may perform a roughening process by methods other than roughening plating. Examples include by e etching process, which is roughened surface is oxidized foil surface by an oxidizing agent or atmospheric adjustment, which is roughened surface by re-reduction of the surface was oxidized, and a combination thereof The thing by processing etc. are mentioned.
次に、銅箔の少なくとも粗化処理した方の片面にＰＲパルス電解による処理を行う。ＰＲパルス電解を施すことで粗化粒子の溶解、析出が繰り返され、粗化粒子の小型化、粗化粒子数の増大、粗化粒子表面の平滑化などが行われ、視認性を向上する粗化粒子形状となる。 Next, at least one surface of the copper foil subjected to the roughening treatment is treated by PR pulse electrolysis. By applying PR pulse electrolysis, the dissolution and precipitation of the roughened particles are repeated, the roughened particles are reduced in size, the number of roughened particles is increased, and the surface of the roughened particles is smoothed to improve the visibility. It becomes a particle shape.
ＰＲパルス電解液は硫酸銅めっき液を用いる。硫酸濃度は５０〜１５０ｇ／Ｌが好ましく、銅濃度は２０〜１００ｇ／Ｌが好ましい。これらの濃度範囲を超えると、上述のように設備への負荷が高まる、電着性が悪くなる等の問題が発生する。
ＰＲパルス電解の順電解時間および逆電解時間は５０〜５００ミリ秒の範囲が好ましい。５０ミリ秒未満であると、ＰＲパルス電解の効果が現れにくく、５００ミリ秒より長いと粗化粒子がより粗大化する可能性がある。
ＰＲパルス電解の順電流密度は０．５〜１０Ａ／ｄｍ２が好ましい。０．５Ａ／ｄｍ２未満ではパルス１回あたりの析出量が小さく、表面形状への効果が得られにくい。１０Ａ／ｄｍ２を超えると電着性が悪くなる。
逆電流密度は１〜２０Ａ／ｄｍ２が好ましい。またこの範囲内であっても順電流密度に対して大きく下回る、または上回るような条件は好ましくない。ＰＲパルス電解の条件は、それぞれの項目が密接に影響しあうために総合的に判断して条件を決定する。
A copper sulfate plating solution is used as the PR pulse electrolyte. The sulfuric acid concentration is preferably 50 to 150 g / L, and the copper concentration is preferably 20 to 100 g / L. When these concentration ranges are exceeded, problems such as an increase in the load on the equipment and poor electrodeposition occur as described above.
The forward electrolysis time and reverse electrolysis time of PR pulse electrolysis are preferably in the range of 50 to 500 milliseconds. If it is less than 50 milliseconds, the effect of PR pulse electrolysis is hardly exhibited, and if it is longer than 500 milliseconds, the coarse particles may be coarsened.
Forward current density of the PR pulse electrolysis is preferably 0.5~10A / dm 2. If it is less than 0.5 A / dm 2 , the amount of precipitation per pulse is small, and it is difficult to obtain an effect on the surface shape. When it exceeds 10 A / dm 2 , the electrodeposition property is deteriorated.
Reverse current density is preferably 1 to 20A / dm 2. Further, even within this range, conditions that are greatly below or above the forward current density are not preferable. The conditions of the PR pulse electrolysis are determined by comprehensive judgment because each item has a close influence.
更に必要に応じて、後処理としてアルカリ浸漬処理を行う。製箔用添加剤等の表面汚染物の残渣の除去や粗化粒子表面の平滑化を目的として行う。アルカリ溶液としてはＮａＯＨ水溶液を使用する。ＮａＯＨ濃度は１０〜６０ｇ／Ｌの範囲が好ましい。溶液温度は２０〜５０℃、浸漬時間は５〜５０秒が好ましい。 Further, if necessary, an alkali immersion treatment is performed as a post treatment. It is performed for the purpose of removing residues of surface contaminants such as additives for foil making and smoothing the surface of roughened particles. An NaOH aqueous solution is used as the alkaline solution. The NaOH concentration is preferably in the range of 10 to 60 g / L. The solution temperature is preferably 20 to 50 ° C., and the immersion time is preferably 5 to 50 seconds.
上記銅箔の少なくとも片方の面に、更に表面処理層を設けることも可能である。具体的には密着性・耐熱性・耐薬品性・防錆を目的とした表面処理層が挙げられる。表面処理層の内、金属表面処理層としては、Ｎｉ、Ｚｎ、Ｃｒ、Ｓｉ、Ｃｏ、Ｍｏ、の単体または水和物が挙げられる。合金表面処理層としては、Ｎｉ、Ｓｉ、Ｃｏ、Ｍｏ、の少なくとも１種類の金属または１種類以上の金属を含有する合金を付着させた後、Ｚｎを付着させ、さらにＣｒを付着させる。
金属表面処理層の場合はＮｉまたはＭｏ等エッチング性を悪くする金属については表面処理層の厚さを０．８ｍｇ／ｄｍ２以下とすることが好ましい。なお、ＮｉまたＭｏを合金で析出させる合金表面処理層の場合でもその表面処理層の厚さは、１．５ｍｇ／ｄｍ２以下とすることが好ましい。また、Ｚｎについては付着量が多いとエッチング時に溶けてピール強度の劣化の原因になることがあるため２ｍｇ／ｄｍ２以下であることが好ましい。また、いずれもこの程度の付着量であれば、上記表面処理後の銅箔粗化面の形状および表面色を大きく損なうことはない。
It is also possible to further provide a surface treatment layer on at least one surface of the copper foil. Specific examples include a surface treatment layer for the purpose of adhesion, heat resistance, chemical resistance, and rust prevention. Of the surface treatment layers, examples of the metal surface treatment layer include Ni, Zn, Cr, Si, Co, and Mo alone or hydrates. As the alloy surface treatment layer, after depositing at least one kind of metal of Ni, Si, Co, and Mo or an alloy containing one or more kinds of metals, Zn is adhered, and Cr is further adhered.
In the case of a metal surface treatment layer, the thickness of the surface treatment layer is preferably 0.8 mg / dm 2 or less for a metal such as Ni or Mo that deteriorates etching properties. Even in the case of an alloy surface treatment layer in which Ni or Mo is precipitated as an alloy, the thickness of the surface treatment layer is preferably 1.5 mg / dm 2 or less. In addition, when Zn is attached in a large amount, it may melt during etching and cause deterioration of peel strength, so that it is preferably 2 mg / dm 2 or less. Moreover, if both are adhesion amount of this grade, the shape and surface color of the copper foil roughening surface after the said surface treatment will not be impaired significantly.
上記金属表面処理層、または合金表面処理層を設ける（付着させる）めっき液とめっき条件の一例を下記する。
〔Ｎｉめっき〕
ＮｉＳＯ４・６Ｈ２Ｏ １０〜５００ｇ／Ｌ
Ｈ３ＢＯ３ １〜５０ｇ／Ｌ
電流密度 １〜５０Ａ／ｄｍ２
浴温 １０〜７０℃
処理時間 １秒〜２分
ｐＨ ２．０〜４．０
An example of a plating solution and plating conditions for providing (attaching) the metal surface treatment layer or the alloy surface treatment layer will be described below.
[Ni plating]
NiSO 4 · 6H 2 O 10~500g / L
H 3 BO 3 1-50 g / L
Current density 1-50A / dm 2
Bath temperature 10-70 ° C
Processing time 1 second to 2 minutes
pH 2.0-4.0
〔Ｎｉ−Ｍｏめっき〕
ＮｉＳＯ４・６Ｈ２Ｏ １０〜５００ｇ／Ｌ
Ｎａ２ＭｏＯ４・２Ｈ２Ｏ １〜５０ｇ／Ｌ
クエン酸３ナトリウム２水和物 ３０〜２００ｇ／Ｌ
電流密度 １〜５０Ａ／ｄｍ２
浴温 １０〜７０℃
処理時間 １秒〜２分
ｐＨ １．０〜４．０
[Ni-Mo plating]
NiSO 4 · 6H 2 O 10~500g / L
Na 2 MoO 4 · 2H 2 O 1~50g / L
Trisodium citrate dihydrate 30-200 g / L
Current density 1-50A / dm 2
Bath temperature 10-70 ° C
Processing time 1 second to 2 minutes
pH 1.0-4.0
〔Ｍｏ−Ｃｏめっき〕
Ｎａ2ＭｏＯ4・２Ｈ2Ｏ １〜３０ｇ／Ｌ
ＣｏＳＯ4・７Ｈ2Ｏ １〜５０ｇ／Ｌ
クエン酸３ナトリウム２水和物 ３０〜２００ｇ／Ｌ
電流密度 １〜５０Ａ／ｄｍ2
浴温 １０〜７０℃
処理時間 １秒〜２分
ｐＨ １．０〜４．０
[Mo-Co plating]
Na 2 MoO 4 .2H 2 O 1-30 g / L
CoSO 4 · 7H 2 O 1-50g / L
Trisodium citrate dihydrate 30 to 200 g / L
Current density 1-50A / dm 2
Bath temperature 10-70 ° C
Processing time 1 second to 2 minutes
pH 1.0-4.0
〔Ｚｎめっき〕
酸化亜鉛 ２〜４０ｇ／Ｌ
水酸化ナトリウム １０〜３００ｇ／Ｌ
温度 ５〜６０℃
電流密度 ０．１〜１０Ａ／ｄｍ２
処理時間 １秒〜２分
ｐＨ １．０〜４．０
[Zn plating]
Zinc oxide 2-40g / L
Sodium hydroxide 10-300g / L
Temperature 5-60 ° C
Current density 0.1-10 A / dm 2
Processing time 1 second to 2 minutes
pH 1.0-4.0
〔Ｃｒめっき〕
ＣｒＯ３ ０．５〜４０ｇ／Ｌ
液温 ２０〜７０℃
処理時間 １秒〜２分
電流密度 ０．１〜１０Ａ／ｄｍ２
ｐＨ １．０〜４．０
[Cr plating]
CrO3 0.5-40g / L
Liquid temperature 20-70 ° C
Processing time 1 second to 2 minutes
Current density 0.1-10 A / dm 2
pH 1.0-4.0
これら金属表面処理層上にシランを塗布することが好ましい。塗布するシランについては一般的に使用されているアミノ系、ビニル系、シアノ基系、エポキシ系が挙げられる。 It is preferable to apply silane on these metal surface treatment layers. Examples of the silane to be applied include commonly used amino, vinyl, cyano group, and epoxy systems.
以下に本発明を実施例に基づいて説明するが、これらの実施例は例示であり、本発明はこれらに限定されるものではない。 The present invention will be described below based on examples, but these examples are illustrative and the present invention is not limited thereto.
Ｍ面の光沢度が２３０％、Ｓ面の光沢度が１００％である電解銅箔を使用した。この電解銅箔を脱脂・酸洗した後、下記表１に示す条件にて粗化処理、ＰＲパルス電解、アルカリ浸漬処理を行なった。
An electrolytic copper foil having a glossiness of 230% on the M surface and a glossiness of 100% on the S surface was used. After this electrolytic copper foil was degreased and pickled, it was subjected to roughening treatment, PR pulse electrolysis, and alkali immersion treatment under the conditions shown in Table 1 below.
粗化処理液添加剤 ＰＰＳ：ピリジウムプロピルスルホネイト
ｔｏｎ：パルス順電解時間
ｔｒｅｖ：パルス逆電解時間
ｔｏｆｆ：パルス電解停止時間
Ｉｏｎ：パルス順電流密度
Ｉｒｅｖ：パルス逆電流密度
Roughening solution additive PPS: Pyridium propyl sulfonate
ton: pulse forward electrolysis time trev: pulse reverse electrolysis time toff: pulse electrolysis stop time Ion: pulse forward current density Irev: pulse reverse current density
作製した各実施例、各比較例の電解銅箔を以下の項目において評価した。
（１）反射率の測定
日本分光製、紫外可視分光光度計Ｖ−６６０(積分球ユニット)を使用した。電解銅箔の処理面（Ｍ面又はＳ面）に対して鋭角な入射角で測定光を入射し、全光線反射率（Ｒｔ）（ＪＩＳ Ｋ ７３７５）を測定した。垂直に測定光を入射し拡散反射率（Ｒｄ）を測定した。いずれも波長６００ｎｍのときの値を評価に使用した。結果を表２に記載した。
The produced electrolytic copper foil of each Example and each comparative example was evaluated in the following items.
(1) Measurement of reflectance A UV-visible spectrophotometer V-660 (integrating sphere unit) manufactured by JASCO Corporation was used. Measuring light was incident at an acute incident angle with respect to the treated surface (M surface or S surface) of the electrolytic copper foil, and the total light reflectance (Rt) (JIS K 7375) was measured. Measurement light was incident vertically and diffuse reflectance (Rd) was measured. In all cases, the value at a wavelength of 600 nm was used for evaluation. The results are shown in Table 2.
（２）表面色の測定
日本分光製、紫外可視分光光度計Ｖ−６６０(積分球ユニット)を使用した。波長８７０〜２００ｎｍの間で電解銅箔処理面（Ｍ面又はＳ面）の全光線分光反射率を測定した。そのスペクトルから、測定機付属ソフトウェアによりＬ＊、ａ＊、ｂ＊を算出した。Ｃ＊は数式１によりａ＊とｂ＊から算出した（ＪＩＳ Ｚ ８７２２、ＪＩＳ Ｚ ８７８１−４）。結果を表２に記載した。
(2) Measurement of surface color A UV-visible spectrophotometer V-660 (integrating sphere unit) manufactured by JASCO Corporation was used. The total light spectral reflectance of the electrolytic copper foil treated surface (M surface or S surface) was measured between wavelengths 870 and 200 nm. From the spectrum, L * , a * , and b * were calculated by the software attached to the measuring instrument. C * was calculated from a * and b * according to Formula 1 (JIS Z 8722, JIS Z 8781-4). The results are shown in Table 2.
（３）フィルム視認性評価
上記銅箔の処理面（電解銅箔の場合は、Ｍ面又はＳ面）にポリイミドフィルムを３００℃、１時間の条件で熱プレス圧着し、銅張積層板を作製した。この後に塩化銅エッチングで銅箔を全溶解させ、銅箔表面が転写されたポリイミドフィルムを作製した。
測定には、日本分光製 紫外可視分光光度計Ｖ−６６０(積分球ユニット)を使用した。測定は、ＪＩＳＫ ７３７５およびＪＩＳ Ｋ ７１３６を参考にして行った。銅箔表面が転写されたポリイミドフィルムに対して垂直に測定光を入射し、その透過光が積分球に入るようにした。入射光の光軸と積分球内壁が交差する箇所に積分球内壁と同様の標準反射板を設置したときの透過率が全光線透過率（Ｔｔ）であり、同箇所にトラッピングを設置し垂直に透過してきた光を積分球の外に出し除外した上で測定したときの透過率が拡散透過率（Ｔｄ）である。（Ｔｄ／Ｔｔ）×１００（％）をＨａｚｅとして算出した。
視認性の評価としては、Ｈａｚｅ＜３０（％）のとき「Ａ」、３０≦Ｈａｚｅ＜６０（％）のとき「Ｂ」、６０（％）≦Ｈａｚｅ＜９０（％）のとき「Ｃ」、９０（％）≦Ｈａｚｅのとき「Ｄ」とした。視認性評価Ｄのものは、本発明の銅箔の用途としては適さない程度の視認性であり、視認性評価Ｃのものは本発明の銅箔の用途として適する程度の視認性であるといえる。ＣからＢ、Ａの順に視認性が高くなり、より好ましい評価といえる。結果を表２に記載した。
(3) Film visibility evaluation A polyimide film is hot press-bonded to the treated surface of the copper foil (M surface or S surface in the case of electrolytic copper foil) at 300 ° C. for 1 hour to produce a copper clad laminate. did. Thereafter, the copper foil was completely dissolved by copper chloride etching to produce a polyimide film having the copper foil surface transferred.
For the measurement, an ultraviolet-visible spectrophotometer V-660 (integrating sphere unit) manufactured by JASCO was used. The measurement was performed with reference to JISK 7375 and JIS K7136. Measuring light was incident perpendicularly to the polyimide film onto which the copper foil surface was transferred, so that the transmitted light entered the integrating sphere. The transmittance when a standard reflector similar to the inner wall of the integrating sphere is installed at the location where the optical axis of the incident light intersects with the inner wall of the integrating sphere is the total light transmittance (Tt). The transmittance measured when the transmitted light is removed from the integrating sphere and excluded is the diffuse transmittance (Td). (Td / Tt) × 100 (%) was calculated as Haze.
The evaluation of visibility is “A” when Haze <30 (%), “B” when 30 ≦ Haze <60 (%), “C” when 60 (%) ≦ Haze <90 (%), When 90 (%) ≦ Haze, “D” was set. The thing of visibility evaluation D is a visibility of the grade which is not suitable as a use of the copper foil of this invention, and the thing of visibility evaluation C can be said to be the visibility of a grade suitable for the use of the copper foil of this invention. . The visibility increases in the order of C, B, and A, which can be said to be more preferable evaluation. The results are shown in Table 2.
（４）銅箔表面粗さの測定
銅箔処理面（Ｍ面又はＳ面）の粗さＲｚを接触式表面粗さ計を用いて測定した（ＪＩＳ−Ｂ−０６０１）。基準長さは０．８ｍｍで行った。結果を表２に記載した。
(4) Measurement of copper foil surface roughness The roughness Rz of the copper foil treated surface (M surface or S surface) was measured using a contact surface roughness meter (JIS-B-0601). The reference length was 0.8 mm. The results are shown in Table 2.
（５）銅箔光沢度の測定
銅箔処理面（Ｍ面又はＳ面）の光沢度を光沢度計を用いて測定した（ＪＩＳ−Ｚ―８７４１）。結果を表２に記載した。
(5) Measurement of copper foil glossiness The glossiness of the copper foil treated surface (M surface or S surface) was measured using a gloss meter (JIS-Z-8741). The results are shown in Table 2.
（６）銅箔／樹脂間のピール強度の測定
（３）の処理で作製した銅張積層板を使用して銅箔部を１０ｍｍ巾テープでマスキングし塩化銅エッチングを行った後テープを除去して１０ｍｍ巾のサンプルを作成し、ピール強度を測定した。
ピール強度が０．６Ｎ／ｍｍ以上のとき「○（合格）」とし、０．６Ｎ／ｍｍ未満のとき「×（不合格）」とした。結果を表２に記載した。
(6) Measurement of peel strength between copper foil / resin Using the copper-clad laminate prepared in the process of (3), the copper foil portion was masked with a 10 mm width tape and subjected to copper chloride etching, and then the tape was removed. A 10 mm wide sample was prepared, and the peel strength was measured.
When the peel strength was 0.6 N / mm or more, it was “◯ (passed)”, and when it was less than 0.6 N / mm, it was “x (failed)”. The results are shown in Table 2.
（７）視認性と密着性の総合評価
上記（１）〜（６）の測定の結果から、以下の基準に基づいて総合評価を行った。結果を表２に記載した。
視認性がＤ、または密着性が×のもの ： ×
視認性がＣ、かつ密着性が○のもの ： ○
視認性がＡまたはＢ、かつ密着性が○のもの ： ◎
(7) Comprehensive evaluation of visibility and adhesion From the results of the above measurements (1) to (6), comprehensive evaluation was performed based on the following criteria. The results are shown in Table 2.
Visibility is D or adhesion is x: x
Visibility is C and adhesion is ○: ○
Visibility is A or B, and adhesion is ○: ◎
Ｒｄ：拡散反射率
Ｌ＊：明度指数
Ｃ＊：彩度
Ｔｔ：全光線透過率
Ｔｄ：拡散透過率
Ｈａｚｅ：曇値
実施例１〜１０は表２から明らかなように視認性と密着性が共に優れている。
実施例１１、１２および１３は、それぞれ実施例４、８、および１０と同じ条件の処理を銅箔のＳ面に施した結果である。いずれも視認性および密着性に優れるが、同一条件のＭ面処理とＳ面処理とを比較するとＳ面処理の方が視認性が低くなる傾向にある。実施例１４は、一般的な圧延銅箔(ＴＰＣ)の片面に処理を施した結果である。良い結果が得られた実施例９と同じ条件の処理を用いた。しかし結果は実施例９よりもわずかに視認性が悪い表面が得られている。これは、圧延銅箔表面にはオイルピットなどの表面形状異常が存在するために粗化処理で粒子が均一に形成されにくいことに起因すると考えられる。
As can be seen from Table 2, Examples 1 to 10 are excellent in both visibility and adhesion.
Examples 11, 12, and 13 are the results of applying the same conditions as those of Examples 4, 8, and 10 to the S surface of the copper foil. Both are excellent in visibility and adhesion, but when the M surface treatment and S surface treatment under the same conditions are compared, the visibility of the S surface treatment tends to be lower. Example 14 is the result of processing one side of a general rolled copper foil (TPC). A process under the same conditions as in Example 9 with good results was used. However, as a result, a surface slightly worse in visibility than in Example 9 was obtained. This is presumably because the surface of the rolled copper foil has a surface shape abnormality such as oil pits, so that it is difficult to form particles uniformly by the roughening treatment.
比較例１および２は従来から行われている粗化処理を施した銅箔である。密着性には優れるが視認性に劣る。
比較例３および４は粗化処理等の後処理によって適切な粒子が形成されず、大きな周期でのうねりを伴った比較的平滑な箔である。拡散反射率が低すぎる表面であり、視認性には優れるが密着性に劣る。
比較例５も粗化処理によって適切な粒子が形成されず、高低差の小さい凹凸が形成された箔である。拡散反射率は良好な値を示しており、視認性は良好だが密着性に劣る。
Comparative Examples 1 and 2 are copper foils subjected to a conventional roughening treatment. It has excellent adhesion but poor visibility.
Comparative Examples 3 and 4 are comparatively smooth foils with undulations with a large period in which appropriate particles are not formed by post-treatment such as roughening treatment. The surface has a diffuse reflectance that is too low, and has excellent visibility but poor adhesion.
Comparative Example 5 is also a foil in which appropriate particles are not formed by the roughening treatment and unevenness with a small height difference is formed. The diffuse reflectance shows a good value and the visibility is good but the adhesion is poor.
比較例６および７は、密着性に優れるが、粗化粒子の形状が適切でないために彩度（Ｃ＊）、または彩度（Ｃ＊）と明度指数（Ｌ＊）の両方の値が高い。拡散反射率も良好な値を示すが、表面が転写された樹脂フィルムでは拡散透過が大きくなり、視認性が低い。
比較例８は彩度（Ｃ＊）の値は良好であるが粗化粒子が大きくなったために拡散反射率が高く、視認性は低い。
比較例９は、低密度な粗化粒子層が形成された箔である。拡散反射率は良好な値を示すが、彩度（Ｃ＊）が高く、密着性が悪い。
比較例１０および１１は、それぞれ比較例５および８と同じ条件の処理をＳ面に施した結果である。どちらも視認性と密着性を両立できていない。
Comparative Examples 6 and 7 are excellent in adhesion, but have a high saturation (C * ) or both saturation (C * ) and lightness index (L * ) values because the shape of the roughened particles is not appropriate. . The diffuse reflectance also shows a good value, but the resin film having the surface transferred has a large diffuse transmission and low visibility.
In Comparative Example 8, the value of saturation (C * ) is good, but the roughened particles are large, so that the diffuse reflectance is high and the visibility is low.
Comparative Example 9 is a foil in which a low-density roughened particle layer is formed. The diffuse reflectance shows a good value, but has high chroma (C * ) and poor adhesion.
Comparative Examples 10 and 11 are the results of applying the same conditions to the S surface as Comparative Examples 5 and 8, respectively. Neither has both visibility and adhesion.
本発明は、電解銅箔の場合、未処理銅箔（表面処理前の銅箔）表面を先ず粗化めっきし、次いで粗化めっき表面をＰＲパルス電解し、必要によりアルカリ浸漬処理を施し、その表面に必要により密着性・耐熱性・耐薬品性・防錆を目的とした表面処理層を設けた配線板用電解銅箔である。 In the case of the electrolytic copper foil, the present invention first rough-plats the surface of the untreated copper foil (copper foil before the surface treatment), then PR pulse electrolyzes the rough-plated surface, and if necessary, performs an alkali immersion treatment, It is an electrolytic copper foil for a wiring board provided with a surface treatment layer for the purpose of adhesion, heat resistance, chemical resistance and rust prevention on the surface as necessary.
本発明によって、配線板に適用して好適な樹脂密着性と視認性の両方が優れた配線板用電解銅箔を提供することが可能となる。 By this invention, it becomes possible to provide the electrolytic copper foil for wiring boards excellent in both resin adhesiveness and visibility suitable for a wiring board.
また、本来ならば樹脂密着性および視認性は銅箔の特性のみならず樹脂の特性も大きく影響するところを、本発明は銅箔の表面特性、樹脂の転写表面形状の制御により樹脂密着性および視認性を高い水準にすることを達成している。そのため、樹脂の特性、製法、種類等に影響されにくく、樹脂側の設計自由度が高いため配線板の生産性、安定性に優れる。 In addition, originally, the resin adhesion and visibility are greatly influenced not only by the characteristics of the copper foil but also by the characteristics of the resin. Achieved high visibility. Therefore, it is hardly affected by the characteristics, manufacturing method, type, etc. of the resin, and the design flexibility on the resin side is high, so that the productivity and stability of the wiring board are excellent.
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| JP7492807B2 (en) * | 2016-12-06 | 2024-05-30 | Ｊｘ金属株式会社 | Surface-treated copper foil, carrier-attached copper foil, laminate, method for manufacturing printed wiring board, and method for manufacturing electronic device |
| JP7492808B2 (en) * | 2017-03-31 | 2024-05-30 | Ｊｘ金属株式会社 | Surface-treated copper foil, surface-treated copper foil with resin layer, copper foil with carrier, laminate, method for manufacturing printed wiring board, and method for manufacturing electronic device |
| US10190225B2 (en) * | 2017-04-18 | 2019-01-29 | Chang Chun Petrochemical Co., Ltd. | Electrodeposited copper foil with low repulsive force |
| US10424793B2 (en) * | 2017-11-14 | 2019-09-24 | Chang Chun Petrochemical Co., Ltd. | Electrodeposited copper foil and method for producing the same, and current collector for lithium secondary battery and secondary battery comprising the electrodeposited copper foil |
| US10337115B1 (en) * | 2018-01-05 | 2019-07-02 | Chang Chun Petrochemical Co., Ltd. | Surface treated copper foil for high speed printed circuit board products including the copper foil and methods of making |
| WO2019208522A1 (en) * | 2018-04-27 | 2019-10-31 | Ｊｘ金属株式会社 | Surface-treated copper foil, copper clad laminate, and printed wiring board |
| JP7234743B2 (en) * | 2019-03-29 | 2023-03-08 | 三菱マテリアル株式会社 | Joined body and insulating circuit board |
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| CN104349582B (en) | 2018-11-13 |
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