JP2708130B2 - Rough surface forming method of copper foil for printed circuit - Google Patents
Rough surface forming method of copper foil for printed circuitInfo
- Publication number
- JP2708130B2 JP2708130B2 JP1154741A JP15474189A JP2708130B2 JP 2708130 B2 JP2708130 B2 JP 2708130B2 JP 1154741 A JP1154741 A JP 1154741A JP 15474189 A JP15474189 A JP 15474189A JP 2708130 B2 JP2708130 B2 JP 2708130B2
- Authority
- JP
- Japan
- Prior art keywords
- copper
- copper foil
- adhesive strength
- rough surface
- fine
- 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.)
- Expired - Fee Related
Links
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
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る樹脂基材との接
着強度に優れるプリント回路用銅箔の粗面形成方法に関
するものである。Description: BACKGROUND OF THE INVENTION The present invention relates to a copper foil used for a printed circuit board, and more particularly, to a copper foil laminated with a resin base material having a finely roughened surface by electrolytic treatment. The present invention relates to a method for forming a rough surface of a copper foil for a printed circuit, which is excellent in adhesive strength to a surfaced resin substrate.
プリント回路用銅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。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を浴を
用いて銅箔を陰極として、まず限界電流密度前後の範囲
の電流によりいわゆるコガシメッキによる粒紛状銅電着
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紛状銅をいわゆる
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。このコブ状銅を形成することにより
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（×20,000）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。As a copper foil for a printed circuit, an electrolytic copper foil and a rolled copper foil are mainly used. In general, any of these copper foils is previously subjected to a surface roughening treatment so that a bonding surface of the copper foil to be laminated on the resin base material can obtain stronger bonding strength by some method. The main method applied as the roughening means is a plating method in the roughening means for electrolytic copper foil. Examples of the plating method include a method disclosed in Japanese Patent Publication No. 53-39376. This is to form a copper powder electrodeposited layer by so-called kogashi plating with a current in the range of about the limiting current density by using a copper foil as a cathode using a bath of acidic copper plating, and further forming a powdered copper electrodeposited layer by so-called kogashi plating on the layer. A substantially smoother plated copper electrodeposition layer, which is not granular due to a current smaller than that but whose surface irregularity is equal to the granular configuration of the copper electrodeposit, is deposited on the powder copper so-called bump. It is intended to change to copper-like copper and thereby obtain an increase in adhesive strength. By forming this bump-shaped copper, the foil surface has an increased specific surface area as compared to before the electrolytic treatment, and at the same time, the anchor effect by the bump-shaped copper is exerted, and the adhesive strength between the resin substrate and the copper foil is increased. improves. In this bump-shaped copper, the diameter of each of the irregularities is about 0.2 to 2 μm, and the surface is a relatively smooth spherical surface when microscopically observed (× 20,000) with an electron microscope. This means
In order to further increase the wettability and adhesion with a resin in order to obtain a stronger adhesive strength, it does not necessarily provide a preferable rough surface, and there is still room for improvement.
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。圧延銅箔の表面を粗面
化するにあたっては、電気特性のうち銅箔と基材との層
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成を付与
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が高いこと（45〜95
℃）、処理時間が長いこと（２分以上）、最適処理浴組
成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。On the other hand, rolled copper foil is widely used for flexible wiring boards because the copper foil has excellent flexibility.
The surface of the rolled copper foil is characterized in that both surfaces are relatively smoother than the electrolytic copper foil. In roughening the surface of rolled copper foil, it is important to obtain a strong adhesive strength while maintaining the reliability of interlayer insulation between the copper foil and the substrate at a high level among the electrical properties. is there. for that purpose,
The bumpy copper may be formed on the copper foil surface, but the rough surface formation is more advantageously a rough surface having a very small surface roughness, and it is desired that the bonding strength is large. I have. Therefore, in order to form such a rough surface, for example, a black oxide treatment for providing a rough surface of copper oxide by a chemical treatment is employed. However, according to this method, the obtained copper oxide layer is corroded by an acid or an alkali agent used in an etching step or the like, and involves a practical problem in terms of chemical corrosion resistance. High processing bath temperature (45-95
° C), a long processing time (2 minutes or more), difficulty in maintaining stable optimum processing bath composition, and many other factors that adversely affect the reliability of quality, and its management is complicated.
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、銅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銅箔の粗面形成方法を提供す
ることにある。An object of the present invention is to solve the above-mentioned problems. That is, a method for forming a rough surface of a copper foil for a printed circuit having excellent adhesion strength between a resin base material and a copper foil by forming a rough surface made of fine-grained copper by electrolytic treatment on a surface to be bonded of the copper foil is provided. It is in.
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
いて電流密度３〜10A/dm2、電解処理時間１〜30秒、浴
温20〜50℃で、限界電流密度以上の電流により電解処理
を施し、該被接着面上に粒径0.005〜0.15μｍの微細粒
状銅を厚みが0.01〜0.15μｍになるように形成すること
を特徴とするプリント回路用銅箔の粗面形成方法を提供
することにある。The present inventors have conducted various studies on the formation of a rough surface for improving the bonding strength of the surface to be bonded of a copper foil to be laminated with a resin substrate, and have obtained the following knowledge. That is, fine-grained copper is applied to the surface to be bonded of the roughened copper foil or the copper foil having a relatively smooth surface that has not been subjected to the roughening treatment, in which the bumpy copper or the like is formed by electrolytic treatment in advance. It has been found that the uniform electrodeposition coating drastically enhances the adhesive strength, which is the object of the present invention. The present invention has been made based on this finding, and the gist of the present invention is to use an alkaline copper plating bath containing copper pyrophosphate ions on the surface to be bonded of a copper foil, to obtain a current density of 3 to 10 A / dm 2 , The treatment time is 1 to 30 seconds, the bath temperature is 20 to 50 ° C., the electrolytic treatment is performed by the current equal to or higher than the limiting current density, and the fine grained copper having a particle diameter of 0.005 to 0.15 μm on the surface to be adhered has a thickness of 0.01 to 0.15 μm. It is an object of the present invention to provide a method for forming a rough surface of a copper foil for a printed circuit, characterized in that the copper foil is formed so that
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、イオンブ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、電気化学的などの主を用い
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。本発明によ
り得られるプリント回路用銅箔の被接着面には、粒径0.
005〜0.15μｍ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0.01〜0.15μｍの範囲で
ある。この微細粒状銅の粒径が0.005μｍ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
浴の組成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、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を
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。Hereinafter, the present invention will be described specifically. The copper foil used in the present invention is mainly represented by an electrolytic copper foil or a rolled copper foil, but is obtained by forming a copper film on a plastic film, for example, by a dry method such as a vacuum evaporation method or an ion-bratting method. You may. The surface of the copper foil, that is, the surface to be adhered to be laminated with the resin base material has been subjected to a surface roughening treatment in which appropriate irregularities are formed using a known mechanical or electrochemical device. Or a surface close to a mirror surface that has not been subjected to any surface roughening treatment. The adhered surface of the copper foil for a printed circuit obtained by the present invention has a particle size of 0.1.
Fine-grained copper having a size of 005 to 0.15 μm is electrodeposited, which can be easily obtained by a method described later. Particularly preferred particle size of the finely divided copper is in the range of 0.01 to 0.15 μm. When the particle size of the fine-grained copper is less than 0.005 μm, the effect of improving the adhesive strength between the copper foil and the resin substrate is small,
On the other hand, when it exceeds 0.15 μm, it becomes difficult to hold fine-grained copper on the copper foil surface. The particle size of the fine-grained copper is related to the composition of the plating bath and the setting of the processing conditions. In particular, when a current is applied for a long time due to an excessive current, a tendency to precipitate acicular copper is sometimes observed. The rough surface on which the acicular copper precipitates leads to a direction that slightly improves the adhesive strength with the resin base material, while the acicular copper remains on the exposed resin substrate after being corroded to obtain a required printed circuit. This may undesirably deteriorate electrical characteristics. Preferably, the fine-grained copper has a thickness of 0.01 to 0.15 μm and is uniformly coated by electrodeposition. In this case, the appearance hue is blackish brown, and it has been found by ESCA analysis that the outermost layer is mainly cuprous oxide. This fine-grained copper is considered to have contributed to the increase in the specific surface area and the improvement in the wettability with the resin substrate, and it is presumed that the bonding strength is thereby improved.
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 a rolled copper foil coated with fine-grained copper as described above is used for a flexible wiring board, it is possible to stably and efficiently obtain a flexible wiring board having a sufficient adhesive strength that could not be obtained by the conventional method. Can be.
次に本発明の粗面形成方法について説明する。本発明
の方法により得られる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覆と
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。Next, the rough surface forming method of the present invention will be described. In obtaining the roughened copper foil obtained by the method of the present invention, as described above, the surface (adhered surface) of the copper foil is roughened even if the copper foil is roughened in advance. It is not particularly limited even if it is not a copper foil, but in order to suitably electrodeposit fine-grained copper on the adhered surface of the copper foil, as a preceding step, degreasing, pickling, and sometimes It is desirable to provide a step of forming a substantially smooth plating layer and to add a means for cleaning and activating the surface.
As a result, the fine-grained copper is formed as a dense and highly adherent coating, which greatly contributes to the improvement of the adhesive strength, which is the object 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
を含むアルカリ性銅メッ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成および
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。Further, the rough surface forming method of the present invention performs electrolytic treatment using an alkaline copper plating bath containing copper pyrophosphate ions to form a rough surface. The preferred bath composition and electrolysis conditions of the plating bath are as follows. It is desirable to select from such a range, but it is 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/ アンモニア水（比重0.88） １〜10ml/ PH ８〜９ 電流密度 ３〜10A/dm2 電解処理時間 １〜30秒 浴温 20〜50℃ 陽極 銅板 陰極 銅箔 ここで、電流密度は限界電流密度以上とする。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.
005〜0.15μｍの微細粒状銅を得ることができない。Copper pyrophosphate 50-150g / Potassium pyrophosphate 150-480g / Ammonia water (specific gravity 0.88) 1-10ml / PH 8-9 Current density 3-10A / dm 2 Electrolysis time 1-30 seconds Bath temperature 20-50 ℃ Anode Copper plate Cathode Copper foil Here, the current density shall be higher than the limit current density. If the current density is too small than the limit current density, the target particle size is 0.
Fine grain copper of 005 to 0.15 μm cannot be obtained.
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 a chromate treatment or the like.
以下、実施例により詳しく説明する。 Hereinafter, an example will be described in detail.
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/、アンモニア水2ml/、PH8.5、
浴温25℃）を用いて、このメッキ浴の限界電流密度を超
える6A/dm2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 A surface of a rolled copper foil having a thickness of 35 μm was subjected to a known alkali degreasing treatment and an acid pickling treatment, and subsequently washed with water. /, Ammonia water 2ml /, PH8.5,
Using a bath temperature of 25 ° C.), a current of 6 A / dm 2 exceeding the limiting current density of the plating bath is subjected to electrolytic treatment for 6 seconds to form fine-grained copper having a grain size of 0.05 to 0.1 μm on the foil surface. Was. The color of the treated surface of the copper foil was uniform blackish brown.
次にこの銅箔を水洗し、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材間の接着強
度をJISC6481に準拠し室温下で測定（銅箔巾1mm）した
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）/A×100（％）から算出され
る塩酸による劣化率は５％（接着強度0.76kg/cm）であ
った。一方、室温下で測定した接着強度をＡ、温度70℃
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）/A×100（％）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
5kg/cm）であった。Next, the copper foil is washed with water, subjected to a known chromate treatment, washed with water, and dried.
A test piece was prepared by laminating with an epoxy resin-impregnated substrate to form a copper-clad laminate. The adhesive strength between the copper foil and the resin substrate of this test piece was measured at room temperature (copper foil width 1 mm) in accordance with JIS C6481, and was 0.8 kg / cm. Further, when the adhesive strength measured at room temperature is A and the adhesive strength after immersion in 6N hydrochloric acid at room temperature for 1 hour is B, the degradation rate due to hydrochloric acid calculated from (AB) / A × 100 (%) Was 5% (adhesive strength 0.76 kg / cm). On the other hand, the adhesive strength measured at room temperature was A, and the temperature was 70 ° C.
Assuming that the adhesive strength after immersion in a 10% aqueous potassium cyanide solution for 30 minutes is B, the degradation rate due to potassium cyanide calculated from (AB) / A × 100 (%) is 6.2% (adhesive strength 0.7
5 kg / cm).
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
0.26％kg/cm）、後者が26.3％（接着強度0.28kg/cm）で
あった。Comparative Example 1 The same treatment as in Example 1 was performed except that the method of the present invention was not performed, and the adhesive strength was measured. The result was 0.38 kg / cm. 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% (adhesive strength).
0.26% kg / cm) and the latter 26.3% (adhesive strength 0.28 kg / cm).
比較例２ 実施例１と同様の銅箔を用いて実施例１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（浴組成：亜塩素酸ナトリウム30g/、水酸化ナトリ
ウム15g/、リン酸ナトリウム12g/、pH13.4、浴温95
℃）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/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、後者いずれも100％であった。Comparative Example 2 After performing degreasing, pickling and water washing in the same manner as in Example 1 using the same copper foil as in Example 1, a known black oxide bath (bath composition: sodium chlorite 30 g /, sodium hydroxide) 15 g /, sodium phosphate 12 g /, pH 13.4, bath temperature 95
° C), and the 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, and found to be 0.30 kg / cm. In addition, when the degradation 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%.
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。When Example 1 and Comparative Example 1 are compared or Example 1
From the results when comparing with Comparative Example 2, the copper foil electrodeposited with fine granular copper obtained by the method of the present invention,
A remarkable improvement in adhesive strength was observed. Also, the rate of deterioration with respect to chemicals was small and the corrosion resistance was good.
実施例２ 厚み35μｍの電解銅箔の粗面側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 powdery copper layer was previously formed on a roughened surface of a 35 μm-thick electrolytic copper foil by a known so-called kogashi plating using a copper sulfate plating bath, and a smooth copper plating layer was further superimposed on the layer to form a diameter.
A roughening treatment having a bumpy copper of 0.2 to 2 μm was performed.
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銅箔を水洗、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/cmであった。Next, the copper foil surface is subjected to electrolytic treatment by the method of the present invention under the same plating bath and processing conditions as in Example 1 to form fine-grained copper having a grain size of 0.05 to 0.1 μm so as to cover the bumpy copper. did. After the obtained roughened copper foil was washed with water and subjected to chromate treatment, the adhesive strength was measured in the same manner as in Example 1 to find that it was 2.2 kg / cm.
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。Comparative Example 3 The same treatment as in Example 2 was performed except that the method of the present invention was not performed, and the adhesive strength was measured. The result was 1.8 kg / cm.
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
銅を被覆するように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2.0kg/cmであっ
た。Example 3 Same as Example 2 except that the copper foil was a rolled copper foil.
A roughening treatment having a copper bump of 0.2 to 2 μm is performed, and then a fine granular copper of 0.05 to 0.1 μm is formed so as to cover the copper bump by the same plating bath and processing conditions as in Example 2. Further, after performing the same chromate treatment as in Example 2, the adhesive strength was measured in the same manner as in Example 2, and it was 2.0 kg / cm.
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1.8kg/cmであった。Comparative Example 4 The same copper foil as in Example 3 was subjected to the same treatment as in Example 3 except that the method of the present invention was not applied, and the adhesive strength was measured. The result was 1.8 kg / cm.
実施例２と比較例３と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 when Example 2 and Comparative Example 3 were compared and when Example 3 and Comparative Example 4 were compared, the adhesive strength was remarkably high in the copper foil electrodeposited with fine-grained copper of the present invention. Improvement was observed.
本発明の方法により得られる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、化学薬品にる耐食性も実用上満足することが認めら
れる。The surface-roughened copper foil electrodeposited with fine-grained copper obtained by the method of the present invention, when used as a copper-clad laminate,
It is effective for improving the adhesive strength between the resin base material and the copper foil. In particular, when applied to a rolled copper foil frequently used for a flexible wiring board, it is recognized that the adhesive strength between the resin base material and the copper foil is effectively improved, and the corrosion resistance to chemicals is practically satisfied.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 美甘 昌宏 茨城県下館市下江連1226番地 日本電解 株式会社下館第二工場内 (72)発明者 山岸 武 茨城県下館市下江連1226番地 日本電解 株式会社下館第二工場内 (56)参考文献 特開 昭60−133788（ＪＰ，Ａ) 特開 昭51−67234（ＪＰ，Ａ) 特開 昭62−216294（ＪＰ，Ａ) 実開 平１−84784（ＪＰ，Ｕ) ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Masahiro Mika 1226 Shimoedashiri, Shimodate-shi, Ibaraki Japan Nippon Electrolysis Co., Ltd. Inside the Shimodate second factory (56) References JP-A-60-133788 (JP, A) JP-A-51-67234 (JP, A) JP-A-62-216294 (JP, A) JP, U)
Claims (1)
むアルカリ性銅メッキ浴を用いて電流密度３〜10A/d
m2、電解処理時間１〜30秒、浴温20〜50℃で、限界電流
密度以上の電流により電解処理を施し、該被接着面上に
粒径0.005〜0.15μｍの微細粒状銅を厚みが0.01〜0.15
μｍになるように形成することを特徴とするプリント回
路用銅箔の粗面形成方法。1. A current density of 3 to 10 A / d using an alkaline copper plating bath containing copper pyrophosphate ions on a surface to be bonded of a copper foil.
m 2 , electrolytic treatment time 1 to 30 seconds, bath temperature 20 ~ 50 ℃, subjected to electrolytic treatment with a current greater than the limiting current density, on the surface to be bonded 0.005 ~ 0.15μm fine-grained copper with a thickness of 0.01-0.15
A method for forming a rough surface of a copper foil for a printed circuit, the method comprising forming the copper foil to have a thickness of μm.
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 JPH0320493A (en) | 1991-01-29 |
| JP2708130B2 true 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) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3949871B2 (en) * | 1999-12-10 | 2007-07-25 | 日本電解株式会社 | Roughening copper foil and method for producing the same |
| JP4771552B2 (en) * | 2005-10-05 | 2011-09-14 | Ｊｘ日鉱日石金属株式会社 | 2-layer flexible board |
| JP5400447B2 (en) * | 2009-03-31 | 2014-01-29 | 三井金属鉱業株式会社 | Roughened copper foil, method for producing roughened copper foil, and copper-clad laminate |
Family Cites Families (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
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0320493A (en) | 1991-01-29 |
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