JPH0320493A - Surface-roughened copper foil for printed circuit and formation of its roughened surface - Google Patents
Surface-roughened copper foil for printed circuit and formation of its roughened surfaceInfo
- Publication number
- JPH0320493A JPH0320493A JP15474189A JP15474189A JPH0320493A JP H0320493 A JPH0320493 A JP H0320493A JP 15474189 A JP15474189 A JP 15474189A JP 15474189 A JP15474189 A JP 15474189A JP H0320493 A JPH0320493 A JP H0320493A
- Authority
- JP
- Japan
- Prior art keywords
- copper
- copper foil
- roughened
- adhesive strength
- foil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 113
- 239000011889 copper foil Substances 0.000 title claims abstract description 63
- 230000015572 biosynthetic process Effects 0.000 title description 2
- 229910052802 copper Inorganic materials 0.000 claims abstract description 50
- 239000010949 copper Substances 0.000 claims abstract description 50
- 238000007747 plating Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 7
- -1 copper pyrophosphate ions Chemical class 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 abstract description 33
- 230000001070 adhesive effect Effects 0.000 abstract description 33
- 239000011347 resin Substances 0.000 abstract description 16
- 229920005989 resin Polymers 0.000 abstract description 16
- 238000004070 electrodeposition Methods 0.000 abstract description 7
- 239000011888 foil Substances 0.000 abstract description 7
- PEVJCYPAFCUXEZ-UHFFFAOYSA-J dicopper;phosphonato phosphate Chemical compound [Cu+2].[Cu+2].[O-]P([O-])(=O)OP([O-])([O-])=O PEVJCYPAFCUXEZ-UHFFFAOYSA-J 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 4
- 239000003513 alkali Substances 0.000 abstract description 2
- 239000002585 base Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000007788 roughening Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000006866 deterioration Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 4
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000005238 degreasing Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 239000002659 electrodeposit Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003287 bathing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 1
- 229960002218 sodium chlorite Drugs 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、プリント回路基板に用いられる銅箔に関し、
更に詳しくは、樹脂基材と積層する銅箔の被接着面が電
解処理により微細粗面化されてい〔従来の技術〕
プリント回路用ｆｌ箔としては主に電解銅箔、圧延銅箔
が用いられている。これらの銅箔はいずれも一般に、樹
脂基材と積層する銅箔の被接着面が何らかの方法によっ
て、より強固な接着強度が得られるように、予め粗面化
処理がなされている。[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to copper foil used for printed circuit boards,
More specifically, the bonded surface of the copper foil laminated to the resin base material is finely roughened by electrolytic treatment [prior art] Electrolytic copper foil and rolled copper foil are mainly used as fl foil for printed circuits. ing. All of these copper foils are generally roughened in advance by some method on the bonded surface of the copper foil to be laminated with the resin base material so as to obtain stronger adhesive strength.
この粗面化手段として適用されている主流は電解銅箔の
粗面化手段にあってはメッキ法である。メッキ法には例
えば、特公昭５３−３９３７６号公報に開示されている
方法がある。これは酸性銅メッキ浴を用いて銅箔を陰極
として、まず限界電流密度前一後の範囲の電流によりい
わゆるコガシメッキによる粒粉状銅電着層を形成させ、
更に該層上に限界電流密度程度又はそれ以下の電流によ
り粒状ではないが表面の凹凸の立体配置が上記銅電着体
の粒状立体配置に等しい実質的には平滑なメッキ銅電着
層を堆積させて前記粒粉状銅をいわゆるコブ状銅に変化
させこれにより接着強度の増強を得ようとするものであ
る。このコブ状銅を形或することにより該箔面は、電解
処理前にくらべて比表面積の増大がはかられるとともに
コブ状銅によるアンカー効果が発揮されて樹脂基材と銅
箔間の接着強度が向上する。このコブ状銅では、その凹
凸の個々の直径は０．２〜２μｍ程度の大きさであり、
その表面は電子顕微鏡で微視的に観察すると（ｘ２０，
０００）比較的平滑な球面である。このことは、より強
固な接着強度を得るために樹脂との濡れ性、密着性を更
に高めようとする場合、必ずしも好ましい粗面を提供し
ているものとはいえず未だ改善の余地を残している．
一方、圧延銅箔にあっては、この銅箔が可撓性に優れて
いることからフレキシブル配線板に多用されている。圧
延銅箔の表面は電解銅箔にくらべて両表面ともに比較的
平滑なことなどに特徴がある。圧延ｗ４箔の表面を粗面
化するにあたっては、電気特性のうちｗ４′４と基材と
の眉間絶縁性の信頼性を高水準に維持しながら強固な接
着強度を得ることが重要な要求特性である。そのために
は、前記するコブ状銅を銅箔面に形成してもよいが、そ
の粗面形成はきわめて小さい表面あらさを有する粗面で
あることの方が有益であり、しかも接着強度の大きいこ
とが望まれている。そこで、このような粗面を形成する
には、例えば化学処理によって銅酸化物の粗面形或を付
与するブラックオキサイド処理が採用されている。しか
し、この方法によれば、得られた銅酸化物層がエッチン
グ工程などに用いられる酸やアルカリ薬剤により腐食さ
れ化学的耐食性の面で実用上の支障を含むものであり、
しかも一般にこの処理方法は処理浴温か高いこと（４５
〜９５℃）、処理時間が長いこと（２分以上）、最適処
理浴組威を安定維持することが困難であることなど品質
の信頼性に悪影響を与える多くの要因を含み、その管理
は複雑である。The main method used to roughen the surface of electrolytic copper foil is plating. An example of the plating method is the method disclosed in Japanese Patent Publication No. 53-39376. This involves using an acidic copper plating bath, using a copper foil as a cathode, and applying a current in the range of before and after the critical current density to form a granular copper electrodeposition layer by so-called Kogashi plating.
Further, on the layer, a plated copper electrodeposited layer is deposited using a current at or below the critical current density, which is not granular but has a substantially smooth plated copper electrodeposit layer in which the three-dimensional arrangement of surface irregularities is equal to the granular three-dimensional arrangement of the copper electrodeposited body. The purpose is to change the granular copper into so-called lump-like copper, thereby increasing the adhesive strength. By forming this copper knob, the specific surface area of the foil surface is increased compared to before electrolytic treatment, and the anchor effect of the copper knob is exerted, increasing the adhesive strength between the resin base material and the copper foil. will improve. In this knob-shaped copper, the diameter of each unevenness is about 0.2 to 2 μm,
When the surface is microscopically observed with an electron microscope (x20,
000) It is a relatively smooth spherical surface. This means that when trying to further improve wettability and adhesion with the resin in order to obtain stronger adhesive strength, it cannot be said that it necessarily provides a desirable rough surface and there is still room for improvement. There is. On the other hand, rolled copper foil is often used in flexible wiring boards because of its excellent flexibility. The surface of rolled copper foil is characterized in that both surfaces are relatively smooth compared to electrolytic copper foil. When roughening the surface of rolled W4 foil, among the electrical properties, it is important to maintain high reliability of glabellar insulation between W4'4 and the base material while maintaining strong adhesive strength. It is. To this end, the above-described copper bumps may be formed on the copper foil surface, but it is more beneficial to form a rough surface with extremely small surface roughness, and also to have high adhesive strength. is desired. Therefore, in order to form such a rough surface, for example, a black oxide treatment is employed in which a rough surface shape is imparted to copper oxide by chemical treatment. However, according to this method, the obtained copper oxide layer is corroded by the acid or alkaline chemicals used in the etching process, which poses a practical problem in terms of chemical corrosion resistance.
Moreover, this treatment method generally requires a high treatment bath temperature (45
There are many factors that adversely affect quality reliability, such as long processing times (more than 2 minutes), difficulty stably maintaining the optimal processing bath composition, and their management is complex. It is.
本発明の目的は、前記する問題点を解消することにある
。即ち、ｍ箔の被接着面を電解処理により微細粒状銅よ
りなる粗面を形成させて、樹脂基材と銅箔間の接着強度
の優れたプリント回路用粗面化銅箔とその粗面形或方法
を提供することにある。An object of the present invention is to solve the above-mentioned problems. That is, by electrolytically treating the bonded surface of m-foil to form a rough surface made of finely granular copper, we have developed a roughened copper foil for printed circuits with excellent adhesive strength between the resin base material and the copper foil, and its rough surface shape. The purpose is to provide a method.
本発明者等は、樹脂基材と積層する銅箔の被接着面の接
着強度を向上させる粗面形成について種々検討した結果
、次の知見を得た。即ち、予め前記するコブ状銅等が電
解処理により形成されている粗面化処理銅箔又は粗面化
処理を施していない比較的平滑な表面を有する銅箔の被
接着面に微細粒状銅を均一に電着被覆することにより本
発明の目的である接着強度の向上が飛躍的に促進される
ことを見出した．本発明はこの知見に基づいてなされた
ものでありその要旨とするところは、銅箔の被接着面に
粒径０。００５〜０．１５μｍの微細粒状銅が電着被覆
されているプリント回路用粗面化銅箔を提供することと
、銅箔の被接着面にピロリン酸銅イオンを含むアルカリ
性銅メッキ浴を用いて限界電流密度付近又はそれ以上の
電流により電解処理を施し、該被接着面上に微細粒状銅
を形成することを特徴とするプリント回路用粗面化銅箔
の粗面形或方法を提供することにある。The present inventors have conducted various studies on the formation of a rough surface to improve the adhesive strength of the bonded surface of the copper foil laminated to the resin base material, and have obtained the following findings. That is, fine granular copper is applied to the bonded surface of a roughened copper foil on which the aforementioned lump-shaped copper etc. have been formed by electrolytic treatment or a copper foil with a relatively smooth surface that has not been subjected to roughening treatment. It has been found that the improvement of adhesive strength, which is the objective of the present invention, is dramatically promoted by applying uniform electrodeposition coating. The present invention was made based on this knowledge, and its gist is that the surface of the copper foil to be bonded is coated with fine granular copper particles having a grain size of 0.005 to 0.15 μm by electrodeposition. Providing a roughened copper foil, and electrolytically treating the surface of the copper foil to be bonded using an alkaline copper plating bath containing copper pyrophosphate ions with a current near or higher than the critical current density; An object of the present invention is to provide a method for forming a roughened copper foil for printed circuits, which is characterized by forming fine grained copper thereon.
以下、本発明を具体的に説明する。本発明に用いられる
銅箔は主に電解銅箔、圧延銅箔に代表されるが、真空蒸
着法、イオンプレーテング法等の乾式法によって例えば
プラスチックフィルム上に銅膜を形成させたものであっ
てもよい。銅箔の表面、即ち樹脂基材と積層する被接着
面は、予め公知の機械的、電気化学的などの手段を用い
て適度な凹凸が形成されている粗面化処理が施されてい
るものであってもよいし、何ら粗面化処理が施されてい
ない例えば鏡面に近い表面であってもよい。The present invention will be explained in detail below. The copper foil used in the present invention is mainly typified by electrolytic copper foil and rolled copper foil, but copper foil may be formed on a plastic film using a dry method such as vacuum evaporation or ion plating. It's okay. The surface of the copper foil, that is, the surface to be bonded to be laminated with the resin base material, has been roughened in advance by using known mechanical, electrochemical, etc. means to form appropriate irregularities. For example, the surface may be a mirror-like surface that has not been subjected to any roughening treatment.
本発明のプリント回路用粗面化銅箔の被接着面には、粒
径０． ０ ０ ５〜０．Ｉ５μｍを有する微細粒状銅
が電着被覆されているが、これは、後述する方法により
簡便に得られる．特に好ましい微細粒状銅の粒径は０．
０１〜０． １ ５ ｔｔ ｍの範囲である．この微細
粒状鋼の粒径がＯ． Ｏ Ｏ ５μｍ未満の場合は、銅
箔と樹脂基材との接着強度の向上効果は小さく、また、
０．１５μｍを超える場合は、微細粒状銅を銅箔面に保
持することが困難となる。微細粒状銅の粒径は、メッキ
浴の組或やその処理条件の設定などに関連するものであ
る。特には過大電流により長時間通電した場合、時とし
て針状銅の析出傾向が認められる。針状銅の析出した粗
面は樹脂基材との接着強度を若干向上させる方向へ導く
ものの、その反面この針状銅が所要のプリント回路を得
るために腐食した後で露出した樹脂基板に残存して電気
特性を悪化させる場合もあり好ましくない。また、この
微細粒状銅の厚みは０．０１〜０．１５μｍで均一に電
着被覆されていることが好ましい．この場合外観色相は
黒かっ色を呈し、その最表面層は主に亜酸化銅であるこ
とがＥＳＣＡ分析によって判明されている．この微細粒
状銅は、比表面積の増大と樹脂基材との濡れ性を好適に
改善することに寄与しているものと考えられ、これによ
り接着強度の向上が図られるものと推測される。The adherend surface of the roughened copper foil for printed circuits of the present invention has a grain size of 0. 0 0 5~0. Fine granular copper having an I of 5 μm is coated by electrodeposition, and this can be easily obtained by the method described below. The particle size of the particularly preferable fine granular copper is 0.
01~0. The range is 1 5 tt m. The grain size of this fine-grained steel is O. When O O is less than 5 μm, the effect of improving the adhesive strength between the copper foil and the resin base material is small, and
If it exceeds 0.15 μm, it becomes difficult to hold fine grained copper on the copper foil surface. The particle size of the fine granular copper is related to the composition of the plating bath and the setting of its processing conditions. In particular, when the current is applied for a long time due to excessive current, a tendency to deposit acicular copper is sometimes observed. The rough surface on which the acicular copper precipitates leads to a slight improvement in the adhesive strength with the resin substrate, but on the other hand, the acicular copper remains on the exposed resin substrate after being corroded to obtain the desired printed circuit. This is not preferable because it may deteriorate the electrical characteristics. Further, it is preferable that the fine granular copper has a thickness of 0.01 to 0.15 μm and is uniformly electrodeposited. In this case, the external appearance is blackish-brown, and ESCA analysis has revealed that the outermost layer is mainly cuprous oxide. It is thought that this fine granular copper contributes to increasing the specific surface area and suitably improving the wettability with the resin base material, and it is presumed that this improves the adhesive strength.
特に、上記の微細粒状銅が電着被覆されている圧延銅箔
をフレキシブル配線板に用いると、従来の方法では得ら
れなかった十分な接着強度を有するフレキシブル配線板
を安定して効率よく得ることができる。In particular, when the rolled copper foil coated with the above-mentioned fine grained copper is used for a flexible wiring board, it is possible to stably and efficiently obtain a flexible wiring board with sufficient adhesive strength that cannot be obtained by conventional methods. I can do it.
次に本発明の粗面形成方法について説明する。Next, the rough surface forming method of the present invention will be explained.
本発明の粗面化銅箔を得るに際しては、前述したように
銅箔の表面（被接着面）は、予め粗面化されている銅箔
であっても、粗面化されていない銅箔であっても特に制
限をうけるものではないが、銅箔の被接着面に微細粒状
銅を好適に電着形成させるには、前段の工程として、脱
脂、酸洗、また場合によっては、実質的に平滑な銅メッ
キ層を形成させるなどの工程を設け、表面の清浄化や活
性化を行う手段を付加することが望ましい。これにより
、微細粒状銅は緻密かつ密着性のよい被膜となって形成
され、本発明の目的である接着強度の向上に大きく貢献
することになる。When obtaining the roughened copper foil of the present invention, as described above, the surface of the copper foil (surface to be bonded) may be a copper foil that has not been roughened, even if it is a copper foil that has been roughened in advance. However, in order to suitably electrodeposit fine granular copper on the surface of the copper foil to be adhered, degreasing, pickling, and in some cases, substantial It is desirable to provide a process such as forming a smooth copper plating layer on the surface and add means for cleaning and activating the surface. As a result, the finely granular copper is formed into a dense and highly adhesive film, which greatly contributes to the improvement of adhesive strength, which is the objective of the present invention.
更に、本発明の粗面形成方法は、ピロリン酸銅イオンを
含むアルカ２性銅メ・・キ浴を用いて電解処理を施して
粗面を形成するが、このメッキ浴の好適な浴組戒および
電解条件は次のような範囲から選択されることが望まし
いが、特にこの範囲に限定するものではない。Furthermore, in the method for forming a rough surface of the present invention, a rough surface is formed by electrolytic treatment using an alkaline copper plating bath containing copper pyrophosphate ions. The electrolytic conditions are preferably selected from the following ranges, but are not particularly limited to this range.
ピロリン酸銅 ５０〜１５０ｇ＃！ピロリン
酸カリウム １５０〜４８０ｇ／Ｉ！アンモニア水（
比重０． ８ ８ ）
１〜１０ＩＩ１１／２
８〜９
３ 〜 １ ０ Ａ／ｄｎ＋”
１〜３０秒
２０〜５０゜Ｃ
銅板
！ｌｉｉ１′４
ＰＨ
電流密度
電解処理時間
浴温
陽極
陰極
ここで、電流密度は限界電流密度付近又はそれ以上とす
る。電流密度が限界電流密度より小さすぎると、目的と
する粒径０． Ｏ Ｏ ５〜０．１５μｍの微細粒状銅
を得ることができない。Copper pyrophosphate 50-150g #! Potassium pyrophosphate 150-480g/I! Ammonia water (
Specific gravity 0. 8 8) 1~10II11/2 8~9 3~10 A/dn+" 1~30 seconds 20~50°C Copper plate!lii1'4 PH Current density Electrolytic treatment time Bath temperature Anode Cathode Here, the current density is at its limit The current density should be close to or higher than the current density.If the current density is too smaller than the critical current density, it is impossible to obtain fine granular copper particles having the target particle size of 0.005 to 0.15 μm.
以上の条件で得られた銅箔は、水洗しクロメート処理等
を施して用いられることが好ましい。The copper foil obtained under the above conditions is preferably used after being washed with water and subjected to chromate treatment.
以下、実施例により詳しく説明する。 Hereinafter, this will be explained in detail with reference to examples.
実施例１
厚み３５μｍの圧延銅箔の表面に公知のアルカリ脱脂処
理、酸洗処理を施して、引き続いて水洗した後、ピロリ
ン酸銅メッキ浴（浴組成；ピロリン酸銅１００ｇ＃！、
ピロリン酸カリウム３００ｇ／ｌ、アンモニア水２ｎｌ
／Ｉｔ，ＰＨ８．５、浴温２５’Ｃ ）を用いて、この
メッキ浴の限界電流密度を超える６＾／ｄａ”の電流に
より、６秒間電解処理して、該箔面に粒径０．０５〜０
．１μｍの微細粒状銅を形成させた。この銅箔の処理面
の色相は均一な黒かっ色を呈していた。Example 1 The surface of a rolled copper foil with a thickness of 35 μm was subjected to a known alkali degreasing treatment and pickling treatment, and then washed with water, followed by a copper pyrophosphate plating bath (bath composition: copper pyrophosphate 100 g #!).
Potassium pyrophosphate 300g/l, ammonia water 2nl
/It, PH 8.5, bath temperature 25'C), electrolytic treatment was carried out for 6 seconds with a current of 6^/da'' which exceeds the limiting current density of this plating bath, and a grain size of 0. 05-0
．． Fine grained copper of 1 μm was formed. The treated surface of this copper foil had a uniform blackish-brown hue.
次にこのｗ４箔を水洗し、公知クロメート処理を施して
水洗、乾燥させた後、接着強度を測定するためガラス・
エポキシ樹脂含浸基材と積層して銅張積層板とし、試験
片を作製した。この試験片の銅箔と樹脂基林間の接着強
度をＪＩＳＣ６４８１に準拠し室温下で測定（銅箔巾１
＋ｎｍ）Ｌたところ、０．８ｋｇ／ｃｍであった。また
、室温下で測定した接着強度をＡ、室温下で６Ｎ塩酸に
１時間浸漬後の接着強度をＢとしたとき（Ａ−Ｂ） ／
ＡＸ １ ０ ０（％）から算出される塩酸による劣化
率は５％（接着強度０． ７ ｅ ｋｇ／ｃｍ ）であ
った。一方、室温下で測定した接着強度をＡ、温度７０
゜Ｃで１０％シアン化カリウム水溶液に３０分浸漬後の
接着強度をＢとしたとき（Ａ−Ｂ） ／ＡＸ １ ０
０ （％）から算出されるシアン化カリウムによる劣化
率は６．２％（接着強度０． ７ ５ ｋｇ／ Ｃｌｌ
）であった．比較例１
本発明の方法を施さなかった他は実施例１と同様の処理
を施して接着強度を測定したところ０．３８ｋｇ／ｃｍ
であった。また、実施例１と同様に塩酸及びシアン化カ
リウムによる劣化率を測定したところ前者が３１．６％
（接着強度０． ２ ６ ｋｇ／ ｅｌｌ ）、後者が
２６．３％（接着強度０． ２ ８ ｋｇ／ ｃｍ ）
であった。Next, this W4 foil was washed with water, subjected to a known chromate treatment, washed with water, and dried.
This was laminated with an epoxy resin-impregnated base material to form a copper-clad laminate, and a test piece was prepared. The adhesive strength between the copper foil and the resin matrix of this test piece was measured at room temperature in accordance with JISC6481 (copper foil width 1
+nm)L was 0.8 kg/cm. In addition, when the adhesive strength measured at room temperature is A, and the adhesive strength after being immersed in 6N hydrochloric acid at room temperature for 1 hour is B, (A-B) /
The deterioration rate due to hydrochloric acid calculated from AX 100 (%) was 5% (adhesive strength 0.7 e kg/cm ). On the other hand, the adhesive strength measured at room temperature is A, and the temperature is 70.
When the adhesive strength after 30 minutes immersion in 10% potassium cyanide aqueous solution at °C is B (A-B) /AX 1 0
The deterioration rate due to potassium cyanide calculated from 0 (%) is 6.2% (adhesive strength 0.75 kg/Cll
)Met. Comparative Example 1 The same treatment as in Example 1 was applied except that the method of the present invention was not applied, and the adhesive strength was measured to be 0.38 kg/cm.
Met. In addition, when the deterioration rate due to hydrochloric acid and potassium cyanide was measured in the same manner as in Example 1, the former was 31.6%.
(adhesion strength 0.26 kg/ell), the latter being 26.3% (adhesion strength 0.28 kg/cm)
Met.
比較例２
実施例１と同様の銅箔を用いて実施例ｌと同様に脱脂、
酸洗、水洗を行った後、公知のブラックオキサイド浴（
浴組戒：亜塩素酸ナトリウム３０ｇｅｌ、水酸化ナトリ
ウム１５ｇ／ｊ！、リン酸ナトリウム１ ２ｇ／Ｌ Ｐ
Ｈ １ ３．４、浴温９５゜Ｃ）を用いて２分間浸漬
処理を施して黒色の酸化銅を形成させた他は実施例１と
同様にして接着強度を測定したところ０．３０ｋｇ／ｃ
ｍであった。また、実施例１と同様に塩酸及びシアン化
カリウムによる劣化率を測定したところ前者、後者いず
れも１００％であった．
実施例１と比較例１とを対比させたとき又は実施例１と
比較例２とを対比させたときの結果から、本発明の方法
により得られた微細粒状銅を電着被覆した銅箔では、顕
著に接着強度の向上が認められた。また化学薬品に対す
る劣化率も小さく耐食性も良好であった。Comparative Example 2 Using the same copper foil as in Example 1, degreasing and
After acid washing and water washing, a known black oxide bath (
Bathing precepts: Sodium chlorite 30gel, sodium hydroxide 15g/j! , Sodium phosphate 12g/L P
Adhesive strength was measured in the same manner as in Example 1, except that black copper oxide was formed by immersion treatment for 2 minutes using H 1 3.4, bath temperature 95 ° C), and the adhesive strength was 0.30 kg/c.
It was m. Further, when the deterioration rate due to hydrochloric acid and potassium cyanide was measured in the same manner as in Example 1, both the former and the latter were 100%. From the results of comparing Example 1 and Comparative Example 1 or comparing Example 1 and Comparative Example 2, it was found that the copper foil coated with fine granular copper obtained by the method of the present invention by electrodeposition , a remarkable improvement in adhesive strength was observed. Furthermore, the rate of deterioration due to chemicals was small and the corrosion resistance was also good.
実施例２
厚み３５μｍの電解銅箔の粗面倒に予め硫酸銅メッキ浴
を用いて公知のいわゆるコガシメッキにより粒粉状銅層
を形成し、該層上に更に平滑銅メッキ層を重畳して直径
０． ２〜２μｍのコブ状銅を有する粗面化処理を施し
た。Example 2 A granular copper layer was formed on the rough surface of an electrolytic copper foil with a thickness of 35 μm by using a copper sulfate plating bath in advance by known so-called Kogashi plating, and a smooth copper plating layer was further superimposed on the layer to give a diameter of 0. ．． A roughening treatment was performed to have copper knobs of 2 to 2 μm.
次にこの銅箔表面に本発明の方法による電解処理を実施
例１と同様のメッキ浴及び処理条件により施して、コブ
状銅を被覆するように粒径０．０５〜０．１μｍの微細
粒状銅を形成した。この得られた粗面化！ｐ！箔を水洗
、クロメート処理した後、実施例１と同様に接着強度を
測定したところ２．２ｋｇ／０であった．
比較例３
本発明の方法を施さなかった他は実施例２と同様の処理
を施して接着強度を測定．したところ１。８ｋｇ／ｃｍ
であった。Next, the surface of this copper foil was subjected to electrolytic treatment according to the method of the present invention using the same plating bath and treatment conditions as in Example 1, so that fine particles with a particle size of 0.05 to 0.1 μm were formed so as to cover the copper knobs. Formed copper. This obtained roughening! p! After washing the foil with water and subjecting it to chromate treatment, the adhesive strength was measured in the same manner as in Example 1 and found to be 2.2 kg/0. Comparative Example 3 The same treatment as in Example 2 was applied, except that the method of the present invention was not applied, and the adhesive strength was measured. As a result, it was 1.8 kg/cm
Met.
実施例３
銅箔が圧延銅箔であったことの他は実施例２と同様に０
． ２〜２μｍのコブ状銅を有する粗面化処理を施し、
次に実施例２と同様のメッキ浴及び処理条件によりコブ
状鋼を被覆するように０．０５〜０．１μｍの微細粒状
銅を形成し、更に実施例２と同様のクロメート処理した
後実施例２と同様に接着強度を測定したところ２．０ｋ
ｇ／ｃＴＩ１であった。Example 3 Same as Example 2 except that the copper foil was rolled copper foil.
．． A roughening treatment with 2 to 2 μm copper bumps is applied,
Next, using the same plating bath and treatment conditions as in Example 2, fine grained copper of 0.05 to 0.1 μm was formed to cover the knob-shaped steel, and the same chromate treatment as in Example 2 was carried out. When the adhesive strength was measured in the same way as 2, it was 2.0k.
g/cTI1.
比較例４
実施例３と同様の銅箔を用いて、本発明の方法を施さな
かった他は実施例３と同様の処理を施して接着強度を測
定したところ１． ８ ｋｇ ／ ｃｍであった。Comparative Example 4 Using the same copper foil as in Example 3, the same treatment as in Example 3 was performed except that the method of the present invention was not applied, and the adhesive strength was measured.1. It was 8 kg/cm.
実施例２と比較例３とを対比させたとき及び実施例３と
比較例４とを対比させたときの結果から、いずれも本発
明の微細粒状銅を電着被覆した銅箔では顕著に接着強度
の向上が認められた。From the results of comparing Example 2 and Comparative Example 3 and comparing Example 3 and Comparative Example 4, it was found that the copper foil coated with the fine granular copper of the present invention by electrodeposition showed remarkable adhesion. An improvement in strength was observed.
本発明の微細粒状銅を電着被覆した粗面化銅箔は、これ
を用いて銅張積層板にしたとき、樹脂基材と銅箔間の接
着強度を向上させるのに有効である。特にフレキシブル
配線板に多用される圧延銅箔へ適用すると、樹脂基材と
銅箔間の接着強度が効果的に向上し、化学薬品による耐
食性も実用上満足することが認められる．The roughened copper foil electrodeposited with finely granular copper of the present invention is effective in improving the adhesive strength between the resin base material and the copper foil when it is used to form a copper-clad laminate. In particular, when applied to rolled copper foil, which is often used in flexible wiring boards, it has been found that the adhesive strength between the resin base material and the copper foil is effectively improved, and the corrosion resistance against chemicals is also satisfactory for practical purposes.
Claims (1)
微細粒状銅が電着被覆されているプリント回路用粗面化
銅箔。 ２、銅箔の被接着面にピロリン酸銅イオンを含むアルカ
リ性銅メッキ浴を用いて限界電流密度付近又はそれ以上
の電流により電解処理を施し、該被接着面上に微細粒状
銅を形成するプリント回路用粗面化銅箔の粗面形成方法
。[Scope of Claims] 1. A roughened copper foil for printed circuits, in which the adhered surface of the copper foil is electrodeposited with fine copper particles having a grain size of 0.005 to 0.15 μm. 2. Printing in which the surface of the copper foil to be bonded is subjected to electrolytic treatment using an alkaline copper plating bath containing copper pyrophosphate ions with a current near or higher than the limiting current density to form fine granular copper on the surface to be bonded. A method for forming a rough surface of roughened copper foil for circuits.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1154741A JP2708130B2 (en) | 1989-06-19 | 1989-06-19 | Rough surface forming method of copper foil for printed circuit |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1154741A JP2708130B2 (en) | 1989-06-19 | 1989-06-19 | Rough surface forming method of copper foil for printed circuit |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0320493A true JPH0320493A (en) | 1991-01-29 |
| JP2708130B2 JP2708130B2 (en) | 1998-02-04 |
Family
ID=15590908
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1154741A Expired - Fee Related JP2708130B2 (en) | 1989-06-19 | 1989-06-19 | Rough surface forming method of copper foil for printed circuit |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2708130B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001226795A (en) * | 1999-12-10 | 2001-08-21 | Nippon Denkai Kk | Roughening treated copper foil and producing method therefor |
| JP2010236058A (en) * | 2009-03-31 | 2010-10-21 | Mitsui Mining & Smelting Co Ltd | Roughening-processed copper foil, method of manufacturing roughening-processed copper foil and copper clad laminate |
| JP4771552B2 (en) * | 2005-10-05 | 2011-09-14 | Ｊｘ日鉱日石金属株式会社 | 2-layer flexible board |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5167234A (en) * | 1974-12-09 | 1976-06-10 | Hitachi Ltd | PIRORINSANDOMETSUKIZEIKAHIMAKUBOSHIHO |
| JPS60133788A (en) * | 1983-12-21 | 1985-07-16 | 富士通株式会社 | Method of plating printed board |
-
1989
- 1989-06-19 JP JP1154741A patent/JP2708130B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5167234A (en) * | 1974-12-09 | 1976-06-10 | Hitachi Ltd | PIRORINSANDOMETSUKIZEIKAHIMAKUBOSHIHO |
| JPS60133788A (en) * | 1983-12-21 | 1985-07-16 | 富士通株式会社 | Method of plating printed board |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001226795A (en) * | 1999-12-10 | 2001-08-21 | Nippon Denkai Kk | Roughening treated copper foil and producing method therefor |
| JP4771552B2 (en) * | 2005-10-05 | 2011-09-14 | Ｊｘ日鉱日石金属株式会社 | 2-layer flexible board |
| JP2010236058A (en) * | 2009-03-31 | 2010-10-21 | Mitsui Mining & Smelting Co Ltd | Roughening-processed copper foil, method of manufacturing roughening-processed copper foil and copper clad laminate |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2708130B2 (en) | 1998-02-04 |
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