JPH08236930A - Copper foil for printed circuit and its manufacture - Google Patents

Copper foil for printed circuit and its manufacture

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Publication number
JPH08236930A
JPH08236930A JP5822595A JP5822595A JPH08236930A JP H08236930 A JPH08236930 A JP H08236930A JP 5822595 A JP5822595 A JP 5822595A JP 5822595 A JP5822595 A JP 5822595A JP H08236930 A JPH08236930 A JP H08236930A
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copper
foil
layer
formed
group
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JP5822595A
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Japanese (ja)
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JP2920083B2 (en )
Inventor
Eita Arai
Toshio Kurosawa
英太 新井
俊雄 黒澤
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Nikko Gould Foil Kk
日鉱グールド・フォイル株式会社
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Abstract

PURPOSE: To obtain a sufficiently high bonding strength between copper foil and resin substrate so as to prevent the scattering of powder at the time of etching by providing a roughened layer containing specific kinds of metals on the surface of the copper foil to be bonded.
CONSTITUTION: In order to reinforce the projecting sections of raw foil 1, a roughened layer 3 composed of numerous electrodeposited copper projections containing both one or two kinds of first-group metals selected out of a first- group composed of chromium and tungsten and one or two or more kinds of second-group metals selected out of a second group composed of vanadium, nickel, iron, cobalt, zinc, germanium, and molybdenum is formed on the surface of the foil 1 through roughening treatment. Thereafter, a thin plated-copper layer 4 is formed for preventing the falling off of the copper projections and a treated plated layer 5 is formed so as to give a heat resistance and other characteristics to the layer 4. Finally, a corrosion preventing layer 6 is formed. The surface to be bonded of the copper foil thus treated is bonded to a resin substrate, etc.
COPYRIGHT: (C)1996,JPO

Description

【発明の詳細な説明】 DETAILED DESCRIPTION OF THE INVENTION

【0001】 [0001]

【産業上の利用分野】本発明は、印刷回路用銅箔及びその製造方法に関するものであり、特には銅箔と樹脂基板との接着強度を高めるために銅箔の被接着面にクロム及びタングステンから成る第1群から選ばれた1種或いは2種である第1群金属と、バナジウム、ニッケル、鉄、 BACKGROUND OF THE INVENTION The present invention relates to a copper foil and a method for manufacturing the same printed circuit, chromium and tungsten in particular surface to be adhered of the copper foil in order to increase the adhesive strength between the copper foil and the resin substrate one or first group metal is a 2 species selected from a first group consisting of vanadium, nickel, iron,
コバルト、亜鉛、ゲルマニウム及びモリブデンから成る第2群から選ばれたる1種或いは2種以上である第2群金属との両者を含有する多数の突起状(粒状又は節こぶ状、以下単に突起状と記載する)銅電着物から成る粗化処理層を形成した印刷回路用銅箔及びその製造方法に関する。 Cobalt, zinc, a large number of protruding containing both a second group metal is germanium and the second selected upcoming one or two or more from the group consisting of molybdenum (granular or section knobby, hereinafter simply protruding and according to) about copper for a printed circuit to form a roughened layer made of copper electrodeposits foil and a manufacturing method thereof.

【0002】 [0002]

【従来技術】印刷回路用銅箔は一般に、合成樹脂等の基材に高温高圧下で積層接着され、その後目的とする回路を形成するべくレジストを用いて所定の回路パターンをスクリーン印刷した後、不要部を除去するために塩化第二銅溶液等のエッチング液を使用してエッチング処理が施される。 DESCRIPTION OF THE PRIOR ART copper foil for printed circuits generally is laminated and bonded under high temperature and pressure to a substrate such as a synthetic resin, after then screen printed a predetermined circuit pattern using a resist to form a circuit of interest, etching process is performed using an etchant of the second copper solution and the like chloride to remove unnecessary portions. 最終的に、所要の素子が半田付けされて、エレクトロニクスデバイス用の種々の印刷回路板を形成する。 Finally, the required element is soldered to form various printed circuit board for electronic devices. 印刷配線板用銅箔に対する品質要求は、樹脂基材と接着される被接着面(粗化面)と光沢面とで異なる。 Quality requirements for the copper foil for printed circuit boards differ in the bonding surface to be bonded to the resin base material and (roughened surface) and glossy surface.

【0003】本発明が関与する粗化面に対する要求としては、主として、 基材との引きはがし強さが高温加熱、湿式処理、半田付け、薬品処理等の後でも充分なこと(剥離強度)、 保存時における酸化変色のないこと(防錆性)、 基材との積層、エッチング後に生じる所謂積層汚点のないこと(耐塩酸性) エッチングに際して粉落ちのないこと(粉落ち防止) 等が挙げられる。 [0003] As the demand for the roughened surface with which the invention is concerned, primarily, peeling strength of the base material is a high temperature heat, wet processing, soldering, sufficient that (peel strength) even after the chemical treatment or the like, it no oxidative discoloration during the storage (rust resistance), laminate of a substrate, that there is no dusting when the absence of so-called laminated blemish that occurs after the etching (hydrochloric acid) etching (dusting prevention) and the like. 中でも、充分に高い引きはがし強度を有することは被接着面の最も重要な基本的事項である。 Above all, it has a sufficiently high peel strength is the most important basic matters of the adhesive surface.

【0004】銅箔と樹脂基板との接着強度を高めるために、銅箔の被接着面には、多数の突起状銅電着物から成る粗化処理層が形成されている。 [0004] In order to increase the adhesive strength between the copper foil and the resin substrate, the adherend surface of the copper foil, roughening treatment layer comprising a plurality of protruding copper electrodeposits are formed. 電解銅箔に粗化処理が施される場合には、生箔自体がすでに凸部を有しており、その凸部の頂上部付近に突起状銅電着物が多数電着して凸部を更に増強することになる。 When the roughening treatment in the electrolytic copper foil is subjected has a Namahaku itself already protrusion, the protrusion and a number electrodeposited protruding copper electrodeposit around the top portion of the convex portion It will be further enhanced.

【0005】有効な粗化処理として、特公昭54−38 [0005] as a valid roughening treatment, JP-B-54-38
053号、特公昭53−39327号等に砒素、アンチモン、ビスマス、セレンまたはテルルを含む酸性銅電解浴中で限界電流密度前後で電解することが記載されている。 053, arsenic in Japanese Patent Publication No. 53-39327, etc., antimony, bismuth, it is described that the electrolysis at the limiting current density before and after an acidic copper electrolyte bath containing a selenium or tellurium. 実用的には、砒酸が電解浴に添加されることが多い。 In practice, it is often arsenic acid is added to the electrolytic bath. これにより生箔の凸部に多数の突起状銅電着物が形成され、それにより接着強度が高まり、粗化処理方法として有効である。 Thus a number of the protruding copper electrodeposit on the convex portion of the raw foil is formed, thereby increasing the adhesive strength, it is effective as a roughening method.

【0006】 [0006]

【発明が解決しようとする課題】しかしながら、砒素が関与する場合、電解時に銅電着物中に砒素が数100p [0007] However, if the arsenic is involved, arsenic number 100p in the copper electrodeposit during electrolysis
pm取り込まれるため、銅箔の再生その他の処理時にまたエッチング時に砒素が溶出したエッチング液の処分時に存在する砒素が環境上また健康上重大な問題となる。 Because incorporated pm, arsenic arsenic during or etching during other processing regeneration of the copper foil is present on disposal of the eluted etchant is environmental or health serious problem.
こうした毒性元素を含まない粗化処理法としてベンゾキノリン類を微量添加した浴を使用する方法(特公昭56 How to use a bath benzo quinolines were added in a small amount as a roughening treatment method that does not include such toxic elements (JP-B-56
−41196号)、モリブデン、バナジウム或いは両者を添加した浴での処理(特公昭62−56677号、特公昭62−56678号)、或いはパルスめっきでの粗化処理(特開昭63−17597号、特開昭58−16 -41196 No.), molybdenum, treatment in a bath with the addition of vanadium or both (JP-B-62-56677, JP-B-62-56678), or roughening treatment with pulse plating (JP 63-17597, JP-A-58-16
4797号)等が提唱されているが、剥離強度、粉落ちその他の面でいまだ必ずしも充分ではない。 4797 No.) have been proposed, but not always sufficient yet in peel strength, dusting and other aspects.

【0007】本発明の課題は、印刷回路用銅箔の被接着面について、環境問題を呈さず、しかも樹脂基板との間で充分な接着強度を発現しそしてエッチングに際して粉落ちを生じない粗化処理技術を確立することである。 An object of the present invention, for the bonded surface of the copper foil for printed circuit, not exhibit environmental issues, yet no powder falling upon express sufficient adhesive strength between the resin substrate and etching roughening it is to establish the process technology.

【0008】 [0008]

【課題を解決するための手段】本発明者等は、課題解決に向けての検討の結果、(a)クロム及びタングステンから成る第1群から選ばれた1種或いは2種である第1 The present inventors have SUMMARY OF THE INVENTION As a result of the study towards solving the problem, the first which is one or two species selected from a first group consisting of (a) chromium and tungsten
群金属と(b)バナジウム、ニッケル、鉄、コバルト、 Group metal and (b) vanadium, nickel, iron, cobalt,
亜鉛、ゲルマニウム及びモリブデンから成る第2群から選ばれたる1種或いは2種以上である第2群金属との両者を含有する銅電解浴を用いて銅箔の被接着面に多数の突起状銅電着物から成る粗化処理層を形成すると、デンドライト(樹枝状の結晶)の発生を抑制しそして丸みを帯びた突起が良好に電着し、銅箔と樹脂基板との接着強度を向上しそして粉落ちを回避するのに有用であることを見出すに至った。 Zinc, germanium and multiple protruding copper surface to be adhered of the two copper foils using a copper electrolytic bath containing the second metal group is the second selected upcoming one or two or more from the group consisting of molybdenum When forming a roughened layer made of electrodeposit, suppressing the occurrence of dendrite (dendrite crystal) and projections rounded satisfactorily electrodeposited, to improve the adhesive strength between the copper foil and the resin substrate and and we have found that it is useful to avoid dusting. この知見に基づいて、本発明は、銅箔の被接着面に、(a)クロム及びタングステンから成る第1群から選ばれた1種或いは2種である第1群金属と(b)バナジウム、ニッケル、鉄、コバルト、亜鉛、 Based on this finding, the present invention is to be adhered surface of the copper foil, (a) the first group metal is one or two species selected from a first group consisting of chromium and tungsten and (b) vanadium, nickel, iron, cobalt, zinc,
ゲルマニウム及びモリブデンから成る第2群から選ばれた1種或いは2種以上である第2群金属との両者を含有する多数の突起状銅電着物から成る粗化処理層を有することを特徴とする印刷回路用銅箔を提供する。 Characterized by having a roughened layer consisting of a number of protruding copper electrodeposits containing both with one or the second metal group is two or more species selected from a second group consisting of germanium and molybdenum providing a copper foil for printed circuit.

【0009】この粗化処理層の上に従来通り更にトリート層及び防錆層を形成することができ、この観点から、 [0009] it is possible to form a further Treat layer and anticorrosive layer conventionally on the roughened layer, from this point of view,
本発明は更に、銅箔の被接着面に、(a)クロム及びタングステンから成る第1群から選ばれた1種或いは2種である第1群金属と(b)バナジウム、ニッケル、鉄、 The present invention further relates to the bonding surface of the copper foil, (a) chromium and the first metal group and is one or two species selected from a first group consisting of tungsten (b) vanadium, nickel, iron,
コバルト、亜鉛、ゲルマニウム及びモリブデンから成る第2群から選ばれたる1種或いは2種以上である第2群金属との両者を含有する多数の突起状銅電着物から成る粗化処理層と、前記粗化処理層を被覆する、銅、クロム、ニッケル、鉄、コバルト及び亜鉛から成る群から選択された1種乃至2種以上の金属又は合金から成るトリート層と、該トリート層を被覆する防錆層とを有することを特徴とする印刷回路用銅箔を提供する。 Cobalt, zinc, and the roughened layer composed of a large number of protruding copper electrodeposits containing both a second group metal is germanium and one upcoming selected from the second group consisting of molybdenum, or two or more, the covering the roughened layer, copper, rust covering chromium, nickel, iron, and treats layer consisting of one or more metal or alloy selected from the group consisting of cobalt and zinc, said Treat layer providing a copper foil for printed circuits characterized by having a layer. 突起状銅電着物の脱落を防止する薄い銅めっき層を前記粗化処理層とトリート層との間に形成するのが有益である。 It is advantageous to form the thin copper-plated layer for preventing falling off of the protruding copper electrodeposits between the roughened layer and Treat layer.

【0010】更に、印刷回路用銅箔を製造する方法として、本発明は、酸性銅電解浴において銅箔を陰極として限界電流密度付近で電解して銅箔の被接着面に多数の突起状銅電着物から成る粗化処理層を形成する印刷回路用銅箔及びその製造方法において、電解浴中に(a)クロム及びタングステンから成る第1群から選ばれた1種或いは2種である第1群金属:0.0001〜5g/l Furthermore, as a method for producing a copper foil for printed circuit, the present invention includes a plurality of protruding copper surface to be adhered of the copper foil copper foil electrolytically in critical current density near the cathode in an acidic copper electrolyte bath in printed circuit copper foil, and a manufacturing method thereof for forming a roughened layer made of electrodeposit, first a one or two species selected from a first group consisting of (a) chromium and tungsten in the electrolytic bath group metal: 0.0001~5g / l
と、(b)バナジウム、ニッケル、鉄、コバルト、亜鉛、ゲルマニウム及びモリブデンから成る第2群から選ばれたる1種或いは2種以上である第2群金属:0.0 If, (b) vanadium, nickel, iron, cobalt, zinc, the second group metal is germanium and the second selected upcoming one or two or more from the group consisting of molybdenum: 0.0
01〜50g/l の両者を存在せしめることを特徴とする印刷回路用銅箔の製造方法を提供する。 To provide a manufacturing method of a copper foil for printed circuit, characterized in that made present both 01~50g / l. 更に、粗化処理層上に、好ましくは形成された粗化処理層上に突起状銅電着物の脱落を防止する薄い銅めっき層を電解により形成した後、銅、クロム、ニッケル、鉄、コバルト及び亜鉛から成る群から選択される1種乃至2種以上の金属又は合金から成るトリート層を電解により形成し、更に防錆処理することを特徴とする上記の印刷回路用銅箔の製造方法が提供される。 Furthermore, on the roughened layer, after preferably a thin copper-plated layer for preventing falling off of the protruding copper electrodeposit formed by electrolytic on roughened formed layer, copper, chromium, nickel, iron, cobalt and Treat layer was formed by electrolytic comprised of one or more metal or alloy is selected from the group consisting of zinc, the method of manufacturing the printed circuit copper foil, characterized by further rust It is provided.

【0011】 [0011]

【作用】本発明に従えば、電解浴中に(a)クロム及びタングステンから成る第1群から選ばれた1種或いは2 According to the invention, one selected from the first group consisting of (a) chromium and tungsten in the electrolytic bath or 2
種である第1群金属:0.0001〜5g/l と、 The first metal group are species: and 0.0001~5g / l,
(b)バナジウム、ニッケル、鉄、コバルト、亜鉛、ゲルマニウム及びモリブデンから成る第2群から選ばれたる1種或いは2種以上である第2群金属:0.001〜 (B) vanadium, nickel, iron, cobalt, zinc, the second group metal is germanium and the second selected upcoming one or two or more from the group consisting of molybdenum: 0.001
50g/l の両者を存在せしめて粗化処理層を構成することにより、突起状銅電着物が微量の第1群金属と第2 50 g / l and allowed to exist both by configuring the roughened layer, the first metal group protruding copper electrodeposits are traces of the second
群金属とを併有することになる。 Thus having both the group metal. クロム及び(又は)タングステンの第1群金属成分が存在することにより、銅電着時の核発生を抑制してデンドライトの形成を抑制しまた電着突起状粒子を丸めて、接着強度の向上に有用となり、またエッチング時の粉落ちを防止する。 By chromium and (or) the first group metal component tungsten are present, to suppress the nucleation during copper electrodeposition the dendrite formation by rounding the suppression Shimada electrodeposition protruding particles, to improve the adhesion strength It is useful, also to prevent dusting at the time of etching. クロム又はタングステンイオンが電解浴に存在しないと、限界電流付近で電解すると、銅電着物は樹枝状となり、接着強度を改善するよりむしろ損なうことになる。 When chromium or tungsten ions is not present in the electrolytic bath, the electrolytic near the limiting current, the copper electrodeposit becomes dendritic would impair rather than improve the adhesion strength. 粉落ちが生じると、エッチング処理後銅の微粉が残るため電気的特性を損なう危険がある。 If dusting occurs, there is a risk of deteriorating the electric characteristics due to fine powder remains after the etching process the copper. また、バナジウム、ニッケル、 In addition, vanadium, nickel,
鉄、コバルト、亜鉛、ゲルマニウム及びモリブデンから選ばれる1種或いは2種以上の第2群金属成分の存在は、粗化粒子の異方性成長を促し、接着強度の向上に寄与する。 Iron, cobalt, zinc, presence of one or more of the second metal group component selected from germanium and molybdenum, encourage anisotropic growth of the roughening particles, contributes to the improvement of adhesive strength.

【0012】 [0012]

【発明の具体的な説明】本発明は、圧延銅箔及び電解銅箔いずれをも対象としうるが、特には電解銅箔が対象とされる。 DETAILED DESCRIPTION OF THE INVENTION The present invention is either rolled copper foil and electrolytic copper foil may be of interest, particularly electrolytic copper foils are targeted. 電解銅箔に固有に存在する多数の凸部を個々に更に増強するのに有用である。 It is useful for further enhancing the individual multiple protrusions inherently present in the electrolytic copper foil. 従来のように砒素に代表される有毒元素を含む銅電解浴を使用しての限界電流前後の電解によりこうした粗化処理層が効果的に形成されるが、砒素が数100ppm粗化処理層にとり込まれるために環境及び健康問題を呈したのである。 Although such roughened layer is effectively formed by the limiting current before and after the electrolysis using the electrolytic copper baths containing toxic elements typified by arsenic as in the prior art, taken arsenic number 100ppm roughened layer it was exhibited environmental and health problems due to be written.

【0013】図1は、電解銅箔の被接着面側の処理層の例を概略的に示す。 [0013] Figure 1 shows an example of the bonding surface side of the treated layer of the electrolytic copper foil schematically. 生箔1の被接着面には電解銅箔であるために、その表面全体にわたって凸部2が分布している。 To the adherend surface of the raw foil 1 is an electrolytic copper foil, the convex portion 2 is distributed over its surface. この生箔上に粗化処理が行なわれる。 The roughening treatment on the raw foil is performed. 本発明に従う粗化処理により、凸部2の頂上部付近を主体として(a)クロム及びタングステンから成る第1群から選ばれた1種或いは2種である第1群金属と(b)バナジウム、ニッケル、鉄、コバルト、亜鉛、ゲルマニウム及びモリブデンから成る第2群から選ばれたる1種或いは2 The roughening treatment according to the present invention, the vicinity of the top portion of the convex portion 2 mainly (a) the first group metal and which is one or more of the compounds selected from the first group consisting of chromium and tungsten (b) vanadium, nickel, iron, cobalt, zinc, one upcoming selected from the second group consisting of germanium and molybdenum or 2
種以上である第2群金属とを同時に含有する多数の突起状銅電着物から構成される粗化処理層3が形成され、凸部を増強する。 Numerous protruding copper electrodeposition composed of deposits roughened layer 3 is formed containing a second metal group is seed or simultaneously enhancing protrusions. 圧延銅箔のような平滑な銅箔に粗化処理が施された場合には電着物自体が突起部を構成する。 When the roughening treatment is performed on a smooth copper foil such as rolled copper foil is electrodeposit itself constituting the protrusion. この後、多数の処理態様があるが、例えば突起状銅電着物の脱落を防止するために薄い銅めっき層4が形成され、 Thereafter, there are numerous processing mode, for example, a thin copper plating layer 4 in order to prevent falling off of the protruding copper electrodeposit is formed,
そして後耐熱性その他の特性を付与するためにクロム、 The chromium to impart a rear heat resistance and other properties,
ニッケル、鉄、コバルト及び亜鉛等の金属乃至合金、例えば黄銅等のトリートめっき層5が形成され、最後にクロメート処理等に代表される防錆層6が形成される。 Nickel, iron, metals or alloys such as cobalt and zinc and treat plating layer 5 of, for example, brass or the like is formed, anticorrosive layer 6 as represented by the last chromate treatment or the like is formed. こうして処理された銅箔被接着面が樹脂基板等に接着される。 Thus treated copper foil adherend surface is bonded to a resin substrate or the like. 以下、各工程について詳述する。 Below, it will be described in detail each of the steps.

【0014】本発明に従う粗化処理用銅電解浴のめっき条件は次の通りである: (粗化処理用銅電解浴めっき条件) Cuイオン:5〜50g/l H 2 SO 4 :10〜100g/l 第1群金属(Cr、Wの1種又は2種)イオン:0.0 [0014] Plating Conditions of roughening copper electrolytic bath according to the present invention are as follows: (roughening treatment for a copper electrolytic bath Plating Conditions) Cu ion: 5~50g / l H 2 SO 4 : 10~100g / l group 1 metal (Cr, 1 or 2 or of W) ions: 0.0
001〜5g/l 第2群金属(V、Ni、Fe、Co、Zn、Ge、Mo 001~5g / l the second group metal (V, Ni, Fe, Co, Zn, Ge, Mo
の1種或いは2種以上) イオン:0.001〜50g/l 温 度:室温〜50℃ D k :5〜80A/dm 2時間:1〜30秒 One or two or more) ions: 0.001 to 50 g / l Temperature: room temperature ~50 ℃ D k: 5~80A / dm 2 Time: 1-30 seconds

【0015】銅電解浴中に存在させるクロム又はタングステンの濃度或いは両者の組合せの濃度は0.0001 The concentration of the copper concentration of chromium or tungsten is present in the electrolytic bath or a combination of both 0.0001
〜5g/lが適当であり、好ましくは0.0002〜1 ~5g / l is a suitable, preferably 0.0002 to 1
g/lである。 A g / l. 添加量が0.0001g/l未満では接着強度を増すのに充分な効果はなく、他方5g/lを超えても、その効果に顕著な向上はなくまた経済的負担が増大する。 The amount is not sufficient effect to increase the adhesive strength is less than 0.0001 g / l, even more than the other 5 g / l, the effect on remarkable improvement also not economic burden increases. クロム又はタングステンの供給源として、ナトリウム塩、カリウム塩、酸化物等の使用が可能である。 As a source of chromium or tungsten, sodium salt, potassium salt, it is possible to use such oxides. 例えば、無水クロム酸(VI)やタングステン酸ナトリウム(2水塩)等が使用される。 For example, chromic acid (VI) or sodium tungstate anhydride (dihydrate) or the like is used. また、銅電解浴中に存在させるバナジウム、ニッケル、鉄、コバルト、亜鉛、ゲルマニウム及びモリブデンから選ばれる1種或いは2種以上の組合わせの濃度は、0.001〜50g/ Also, vanadium is present in the electrolytic copper bath, nickel, iron, cobalt, zinc, the concentration of one or more combinations selected from germanium and molybdenum, 0.001 to 50 g /
lが適当であり、好ましくは0.01〜20g/lである。 l are suitable, preferably 0.01~20g / l. 添加量が0.001g/l未満では接着強度を増すべく粗化粒子の異方性成長を促すのに十分な効果はなく、他方50g/lを超えてもその効果に顕著な向上はない。 The amount of addition is not sufficiently effective to promote the anisotropic growth of the roughening particles to increase the adhesion strength is less than 0.001 g / l, is no significant improvement in the effect beyond the other 50 g / l. むしろ、表面の処理ムラが目立つようになる。 Rather, so that processing unevenness of the surface is noticeable. ニッケル、鉄、コバルト及び亜鉛の供給源としては、それらの硫酸塩、酸化物、水酸化物等が使用できる。 Nickel, iron, as a source of cobalt and zinc, their sulfates, oxides, hydroxides and the like can be used. また、 Also,
バナジウムの供給源としては、酸化物、硫酸バナジル、 Sources of vanadium, oxides, vanadyl sulfate,
酸素酸塩のナトリウム塩、カリウム塩、アンモニウム塩等が使用できる。 Sodium salt of an oxygen acid salts, potassium salts, ammonium salts, and the like can be used. ゲルマニウム及びモリブデンの供給源としては、酸化物或いは酸素酸塩のナトリウム塩、カリウム塩、アンモニウム塩等が使用できる。 Sources of germanium and molybdenum, sodium salt of oxide or oxygen acid salts, potassium salts, ammonium salts, and the like can be used.

【0016】上記のような粗化処理後、必要に応じ公知の処理、例えば薄い銅めっき層を形成し、突起状電着物の脱落を防止することが好ましい。 [0016] After the roughening treatment as described above, known treatment necessary, for example, is formed thin copper-plated layer, it is preferable to prevent the falling off of the protruding electrodeposit. この薄い銅層の被覆として、もっとも一般的な、硫酸銅浴を使用した場合の好ましい銅電解条件は下記の通りである。 As the coating of the thin copper layer, the most common, preferred copper electrolysis conditions when using a copper sulfate bath are as follows. (薄い銅めっき層電解条件) Cuイオン:5〜50g/l H 2 SO 4 :10〜100g/l 温度:室温〜50℃ D k :5〜80A/dm 2時間:1〜30秒 (Thin copper-plated layer electrolysis conditions) Cu ion: 5~50g / l H 2 SO 4 : 10~100g / l Temperature: room temperature ~50 ℃ D k: 5~80A / dm 2 Time: 1-30 seconds

【0017】粗化面に、好ましくは上記の薄い銅めっきを施した後、銅、クロム、ニッケル、鉄、コバルト及び亜鉛から成る群から選択される1種乃至2種以上の金属層または合金層を形成するトリート処理を行うことが好ましい。 [0017] roughened surface, preferably after having been subjected to the thin copper-plated, copper, chromium, nickel, iron, one or more metal layers or alloy layers is selected from the group consisting of cobalt and zinc it is preferred to carry out the treat process for forming a. 例えば、銅、クロム、ニッケル、鉄、コバルト或いは亜鉛の金属層、或いは銅−ニッケル、銅−コバルト、銅−ニッケル−コバルト、銅−亜鉛等に代表され得る合金層が形成されうる(例えば、特公昭56−902 For example, copper, chromium, nickel, iron, cobalt or a metal layer of zinc, or copper - nickel, copper - cobalt, copper - nickel - cobalt, copper - alloy layer which may be represented by zinc can be formed (for example, Japanese Publication 56-902
8号、特開昭54−13971号、特開平2−2928 No. 8, JP-A-54-13971, JP-A-2-2928
94号、特開平2−292895号、特公昭51−35 94 Patent, JP-A-2-292895, JP-B-51-35
711号、特公昭54−6701号参照)。 711 No., see JP-B-54-6701). こうしたトリート処理層は銅箔の最終性状を決定するものとしてまた障壁層としての役割を果たす。 Such Treat treatment layer serves as also a barrier layer as to determine the final properties of the copper foil.

【0018】亜鉛被膜を例にとると、亜鉛電気めっきおよび無電解めっきいずれでも行いうるが、粗化面片面にのみ被膜を形成するためには亜鉛電解操作による方が便宜である。 [0018] Taking the zinc layer as an example, but may be carried out either zinc electroplating and electroless plating, to form a film only on the roughened surface one side is conveniently better with zinc electrolysis operation. また、厚さの精確な制御、厚さの一様性、付着層の緻密化等の観点からも電解操作が好ましい。 Furthermore, precise control of the thickness, uniformity of thickness, the electrolytic operation in terms of densification, such as the adhesion layer. 亜鉛電解操作は、硫酸亜鉛めっき浴や塩化亜鉛めっき浴に代表される酸性亜鉛めっき浴、シアン化亜鉛めっき浴のようなアルカリ性亜鉛めっき浴、あるいはピロリン酸亜鉛めっき浴が使用しうるが、もっとも一般的に使用される硫酸亜鉛浴で充分である。 Zinc electrolysis operation, the acidic zinc plating bath represented by zinc sulfate plating bath, zinc chloride plating bath, an alkaline zinc plating baths, such as zinc cyanide plating bath, or is zinc pyrophosphate plating bath can be used, most commonly is sufficient zinc sulfate bath which is used. 硫酸亜鉛浴を使用した場合の好ましい亜鉛電解条件は下記の通りである。 Preferred zinc electrolysis conditions when using a zinc sulfate bath are as follows. (亜鉛トリート処理電解条件) ZnSO 4・7H 2 O:50〜350g/l pH(硫酸):2.5〜4.5 浴温度:40〜60℃ 陰極:銅箔 陽極:亜鉛または不溶性陽極 陰極電流密度:0.05〜0.4A/dm 2時間:10〜30秒 亜鉛被覆量は、15〜1500μg/dm 2とすることが好ましく、特に好ましくは15〜400μg/dm 2 (Zinc Treat process electrolysis conditions) ZnSO 4 · 7H 2 O: 50~350g / l pH ( sulfate): 2.5-4.5 bath temperature: 40 to 60 ° C. Cathode: copper anode: zinc or insoluble anode Cathode current density: 0.05~0.4A / dm 2 Time: 10-30 seconds zinc coating amount is preferably set to 15~1500μg / dm 2, particularly preferably 15~400μg / dm 2
である。 It is. 亜鉛被覆量は、積層時の樹脂基板の種類によって異なる。 Zinc coating amount varies depending on the kind of the resin substrate during lamination. 例えばフェノール樹脂基板用は、15〜60 For example a phenolic resin substrate, 15 and 60
μg/dm 2とし、ガラスエポキシ樹脂基板用は、60 and [mu] g / dm 2, for a glass epoxy resin substrate, 60
〜1500μg/dm 2 、特に好ましくは60〜400 ~1500μg / dm 2, particularly preferably 60 to 400
μg/dm 2とする。 and μg / dm 2.

【0019】合金層の一例としてCu−Znトリート処理の電解液組成及び条件例を挙げておく: (Cu−Znトリート処理電解条件) NaCN:10〜30g/l NaOH:40〜100g/l CuCN:60〜120g/l Zn(CN) 2 :1〜10g/l pH:10〜13 温度:60〜80℃ D k :1〜10A/dm 2 The previously mentioned electrolytic solution composition and conditions Examples of Cu-Zn Treat process as an example of the alloy layer: (Cu-Zn Treat process electrolysis conditions) NaCN: 10~30g / l NaOH: 40~100g / l CuCN: 60~120g / l Zn (CN) 2 : 1~10g / l pH: 10~13 temperature: 60~80 ℃ D k: 1~10A / dm 2

【0020】更に、好ましくは、このトリート処理層表面上に防錆層が形成される。 Furthermore, preferably, anticorrosive layer is formed in the treat-treated layer on the surface. 公知の防錆処理の任意のものが適用可能である。 Any of the possible adaptation of known rust. クロメート処理液は現在使用されている様々の処理液いずれも使用しうるが、好ましいクロメート処理条件例を以下に示す: (クロメート処理条件電解条件) K 2 Cr 27 (或いはNa 2 Cr 27 、CrO 3 ): While chromate treatment solutions may be used either various processing solutions that are currently used, shows a preferred chromate treatment conditions example: (chromate treatment conditions electrolysis conditions) K 2 Cr 2 O 7 (or Na 2 Cr 2 O 7, CrO 3):
0.2〜20g/l 酸:りん酸あるいは硫酸、有機酸 pH:1.0〜3.5 浴温度:20〜40℃ 電流密度:0.1〜0.5A/dm 2時間:10〜60秒 陽極:鉛板、Pt−Ti板、ステンレス鋼板 クロム酸化物付着量はクロム量として50μg/dm 2 0.2 to 20 g / l acid: phosphoric acid, or sulfuric acid, organic acids pH: 1.0 to 3.5 bath temperature: 20 to 40 ° C. Current density: 0.1~0.5A / dm 2 Time: 10 to 60 sec anode: lead plates, Pt-Ti plate, stainless steel plate chromium oxide coating weight 50 [mu] g / dm 2 as the amount of chromium
以下で充分であり、好ましくは15〜30μg/dm 2 A sufficient or less, preferably 15~30μg / dm 2
とされる。 It is. クロム量が30μg/dm 2を超えると防錆力は向上するがエッチング性が低下する。 Rust prevention when the chromium content exceeds 30 [mu] g / dm 2 is improved etching resistance decreases.

【0021】有用な防錆方法として、本件出願人は、電解亜鉛・クロム処理による亜鉛及び/又は酸化亜鉛とクロム酸化物との混合皮膜処理を提唱し(特公昭58−7 [0021] Useful rust method, the applicant of the present invention, proposed a mixed coating treatment of zinc by electrolysis zinc-chromium treatment and / or zinc oxide and chromium oxide (JP-B 58-7
077号)、多くの成果を挙げてきた。 No. 077), has been given a lot of achievements. 更に、特開平2 Further, JP-A-2
−294490号は、長期間高温多湿条件下での黒点発生を防止することを目的として、浸漬クロメート処理によりクロム酸化物皮膜を形成し、続いて電解亜鉛・クロム処理により亜鉛及び/又は酸化亜鉛とクロム酸化物との混合皮膜を形成することを開示する。 No. -294490, for the purpose of long term to prevent black spot occurrence at high temperature and high humidity conditions, the chromium oxide film is formed by dipping chromate treatment, followed by zinc by electrolysis zinc-chromium treatment and / or zinc oxide and It discloses forming a mixed film of chromium oxide.

【0022】最後に、必要に応じ、銅箔と樹脂基板との接着力の改善を主目的として、防錆層上にシランカップリング剤を塗布するシラン処理が施される。 [0022] Finally, if necessary, to improve the adhesion between the copper foil and the resin substrate as a main purpose, silane treatment of applying a silane coupling agent on the anticorrosive layer is applied. 塗布方法は、シランカップリング剤溶液のスプレーによる吹付け、コーターでの塗布、浸漬、流しかけ等いずれでもよい。 The coating method, only spraying with a spray of a silane coupling agent solution, application of a coater, immersion, may be any such over flow. 例えば、特公昭60−15654号は、銅箔の粗面側にクロメート処理を施した後シランカップリング剤処理を行なうことによって銅箔と樹脂基板との接着力を改善することを記載している。 For example, Japanese Patent Publication No. 60-15654 describes to improve the adhesion between the copper foil and the resin substrate by performing silane coupling agent treatment was subjected to chromate treatment to the roughened surface side of the copper foil . 詳細はこれを参照されたい。 For more information see this.

【0023】こうして粗化面を被膜処理された銅箔は、 The copper foil with roughened surface is coating treatment thus,
光沢面を必要に応じ処理した後、粗化面に接着剤を塗布して樹脂基板に加熱圧着することにより印刷回路用銅張り積層板とされ、所定の加工操作を経た後、印刷回路板として使用に供される。 After treatment necessary glossy surface, it is a copper-clad laminate for printed circuit by thermocompression bonding the adhesive to the resin substrate coated on the roughened surface, after a predetermined processing operation, a printed circuit board It is subjected to use. 光沢面の処理方法としては、クロメート処理を含む各種化成処理、銅とのキレート化反応を利用した有機剤処理、銅より卑な金属ないし合金の被覆処理等その面において要求される特定水準に応じて適当なものが選ばれる。 The treatment method of the shiny side, various chemical conversion treatment containing chromate treatment, organic agent processing using the chelation reaction with copper, depending on the particular level which is required in the coating process such that the surface of the base metal or alloy of copper those Te appropriate is chosen.

【0024】この後、必要に応じて、銅箔の延性を改善する目的で焼鈍処理を施すこともある。 [0024] Thereafter, if necessary, also it is subjected to annealing treatment in order to improve the ductility of the copper foil.

【0025】本発明による第1群金属としてクロム又はタングステンイオン或いはその組合せそして第2群金属としてバナジウム、ニッケル、鉄、コバルト、亜鉛、ゲルマニウム及びモリブデンから選ばれる1種或いは2種以上のイオンを含有する銅電解浴で粗化した銅箔は、その処理は均一であり、ムラもなく優秀な基板特性を示した。 The present invention chromium or tungsten ions or as a first metal group by vanadium as a combination thereof and the second metal group, nickel, containing iron, cobalt, zinc, one or more ions selected from germanium and molybdenum copper foil was roughened by electrolytic copper bath, the process is uniform and showed excellent substrate properties without unevenness. 即ち、銅箔とガラス布基材エポキシ樹脂で積層板を作製した場合、良好な接着性及び耐熱性を示し、デンドライトの発達を抑えた丸みのある銅電着物が形成されるので、接着強度は高くまたエッチング後の基板の電気的特性や粉落ちの問題がなく良好な性状を示した。 That is, when producing a laminate with copper foil and glass-cloth-based epoxy resin, it showed a good adhesion and heat resistance, since the copper electrodeposit a rounded with reduced development of dendrites are formed, bonding strength high the electrical characteristics and dusting problems of the substrate after etching showed good properties without.

【0026】 [0026]

【実施例】以下、実施例及び比較例を示す。 EXAMPLES Hereinafter, Examples and Comparative Examples.

【0027】(実施例1)硫酸銅(5水塩)100g/ [0027] (Example 1) of copper sulfate (pentahydrate) 100g /
l、硫酸100g/l、無水クロム酸(VI)1g/ l, sulfuric acid 100 g / l, chromic acid anhydride (VI) 1 g /
l、硫酸ニッケル6水和物13g/l、及び硫酸コバルト7水和物14g/lを含む水溶液を30℃で電解浴として使用し、厚さ70μmの電解銅箔の被接着面に電流密度20A/dm 2で10秒間めっきして突起状銅電着物を形成した後、銅イオン45g/l及び硫酸100g l, the current density 20A surface to be adhered of the electrolytic copper foil of nickel sulfate hexahydrate 13 g / l, and used as an electrolytic bath at 30 ° C. The aqueous solution containing cobalt sulfate heptahydrate 14 g / l, thickness 70μm a / dm 2 at plating for 10 seconds after forming the protruding copper electrodeposit copper ions 45 g / l and sulfuric acid 100g
/lを含む銅電解液(40℃)を用いて、30A/dm / Copper electrolyte containing l using (40 ℃), 30A / dm
2で4秒間銅めっきした。 And 4 seconds copper plating at 2. このようにして得られた銅箔を分析したところ、箔全体に対するクロム、ニッケル及びコバルトの含有量は、クロム:約1ppm、ニッケル:約2ppmそしてコバルト:0.5ppm(突起状銅電着物中のCr、Ni及びCoの含有量は、Cr:約0.01wt%、Ni:約0.02wt%そしてCo: Analysis of the copper foil thus obtained, chromium for the entire foil, the content of nickel and cobalt, chromium: about 1 ppm, nickel: about 2ppm and Cobalt: 0.5 ppm (in the protuberant copper electrodeposits Cr, Ni content and Co, Cr: about 0.01 wt%, Ni: about 0.02 wt% and Co:
約0.005wt%)であった。 It was about 0.005wt%). 得られた銅箔をガラス布基材エポキシ樹脂に加熱・加圧して銅張り積層板を作製し、引きはがし強さ及び粉落ち特性を測定した。 The resulting copper foil heated to a glass fabric based epoxy resin and pressure to prepare a copper-clad laminate was measured peel strength and dusting properties. 結果を表1に示す。 The results are shown in Table 1. 更に、粗化処理層上に亜鉛によるトリート処理層及び防錆層を形成した銅箔は一層良好な耐熱性と耐酸化性を示した。 Further, copper foil to form a treat processing layer and the anti-corrosion layer with zinc on the roughened layer showed better heat resistance and oxidation resistance.

【0028】(実施例2)硫酸銅(5水塩)100g/ [0028] (Example 2) copper sulfate (pentahydrate) 100g /
l、硫酸100g/l、タングステン酸ナトリウム(2 l, sulfuric acid 100 g / l, sodium tungstate (2
水塩)0.02g/l、硫酸ニッケル6水和物13g/ Monohydrate) 0.02 g / l, nickel sulfate hexahydrate 13 g /
l、硫酸コバルト7水和物14g/lを含む水溶液を3 l, an aqueous solution containing cobalt sulfate heptahydrate 14 g / l 3
0℃で電解浴として使用し、厚さ70μmの電解銅箔の被接着面に電流密度10A/dm 2で20秒間めっきして突起状銅電着物を形成した後、銅イオン45g/l、 Use as an electrolytic bath at 0 ° C., after forming a protruding copper electrodeposits was plated at a current density of 10A / dm 2 20 seconds the adhesive surface of the electrolytic copper foil having a thickness of 70 [mu] m, a copper ion 45 g / l,
硫酸100g/lを含む電解液(40℃)を用い、30 Using the electrolytic solution containing sulfuric acid 100g / l (40 ℃), 30
A/dm 2で4秒間めっきした。 It was plated 4 seconds A / dm 2. このようにして得られた銅箔を分析したところ、箔全体に対するタングステン、ニッケル及びコバルトの含有量はそれぞれ約1pp Analysis of the copper foil thus obtained, about each tungsten, the content of nickel and cobalt to total foil 1pp
m、約2ppmそして約0.6ppm(突起状銅電着物中のW、Ni及びCoの含有量は、それぞれ約0.01 m, content of about 2ppm and about 0.6 ppm (W in the protuberant copper electrodeposits, Ni and Co, about each 0.01
wt%、約0.02wt%そして約0.006wt%) wt%, about 0.02wt% and about 0.006wt%)
であった。 Met. 得られた銅箔をガラス布基材エポキシ樹脂に加熱・加圧して銅張り積層板を作製し、引きはがし強さ及び粉落ち特性を測定した。 The resulting copper foil heated to a glass fabric based epoxy resin and pressure to prepare a copper-clad laminate was measured peel strength and dusting properties. 結果を表1に示す。 The results are shown in Table 1. 更に、 In addition,
粗化処理層上に亜鉛によるトリート処理層及び防錆層を形成した銅箔は一層良好な耐熱性と耐酸化性を示した。 Copper foil was formed Treat processing layer and the anti-corrosion layer with zinc on the roughened layer showed better heat resistance and oxidation resistance.

【0029】(実施例3)硫酸銅(5水塩)100g/ [0029] (Example 3) copper sulfate (pentahydrate) 100g /
l、硫酸100g/l、無水クロム酸(VI)0.1g l, sulfuric acid 100 g / l, chromic acid anhydride (VI) 0.1 g
/l、タングステン酸ナトリウム(2水塩)0.01g / L, sodium tungstate (dihydrate) 0.01 g
/l、硫酸ニッケル6水和物13g/l、及び硫酸コバルト7水和物14g/lを含む水溶液を30℃で電解浴として使用し、厚さ70μmの電解銅箔の被接着面に電流密度20A/dm 2で10秒間めっきして突起状銅電着物を形成した後、銅イオン45g/l、硫酸100g / L, the current density surface to be adhered of the electrolytic copper foil of nickel sulfate hexahydrate 13 g / l, and used as an electrolytic bath at 30 ° C. The aqueous solution containing cobalt sulfate heptahydrate 14 g / l, thickness 70μm after 20A / dm 2 in plated 10 seconds to form a protruding copper electrodeposit copper ions 45 g / l, sulfuric acid 100g
/lを含む電解液(40℃)を用い、30A/dm 2で4秒間めっきした。 / L electrolyte containing used (40 ° C.), was plated at 30A / dm 2 4 sec. このようにして得られた銅箔を分析したところ、箔全体に対するクロム及びタングステン、 Analysis of the copper foil thus obtained, chromium and tungsten on the entire foil,
ニッケル及びコバルトの含有量は、クロム:約0.1p The content of nickel and cobalt, chromium: about 0.1p
pm、タングステン:約0.7ppm、ニッケル:約2 pm, tungsten: about 0.7ppm, nickel: about 2
ppmそしてコバルト:約0.6ppm(突起状銅電着物中の含有量は、Cr:約0.001wt%、W:約0.007wt%、Ni:約0.02wt%そしてC ppm and cobalt: about 0.6 ppm (content in the protuberant copper electrodeposits, Cr: about 0.001 wt%, W: about 0.007 wt%, Ni: about 0.02 wt% and C
o:約0.006wt%)であった。 o: it was about 0.006wt%). 得られた銅箔をガラス布基材エポキシ樹脂に加熱・加圧して銅張り積層板を作製し、引きはがし強さ及び粉落ち特性を測定した。 The resulting copper foil heated to a glass fabric based epoxy resin and pressure to prepare a copper-clad laminate was measured peel strength and dusting properties.
結果を表1に示す。 The results are shown in Table 1. 更に、粗化処理層上に亜鉛によるトリート処理層及び防錆層を形成した銅箔は一層良好な耐熱性と耐酸化性を示した。 Further, copper foil to form a treat processing layer and the anti-corrosion layer with zinc on the roughened layer showed better heat resistance and oxidation resistance.

【0030】(実施例4)硫酸銅(5水塩)100g/ [0030] (Example 4) copper sulfate (pentahydrate) 100g /
l、硫酸100g/l、タングステン酸ナトリウム(2 l, sulfuric acid 100 g / l, sodium tungstate (2
水塩)0.01g/l、及び硫酸コバルト7水和物14 Monohydrate) 0.01 g / l, and cobalt sulfate heptahydrate 14
g/lを含む水溶液を30℃で電解浴として使用し、厚さ70μmの電解銅箔の被接着面に電流密度20A/d g / l was used as an electrolytic bath at 30 ° C. The aqueous solution containing the current density surface to be adhered of the electrolytic copper foil with a thickness of 70 [mu] m 20A / d
2で10秒間めっきして突起状銅電着物を形成した後、銅イオン45g/l、硫酸100g/lを含む電解液(40℃)を用い、30A/dm 2で4秒間めっきした。 After forming the protruding copper electrodeposits was plated with m 2 10 seconds, copper ion 45 g / l, electrolytic solution containing sulfuric acid 100 g / l using a (40 ° C.), it was plated at 30A / dm 2 4 sec. このようにして得られた銅箔を分析したところ、箔全体に対するタングステン及びコバルトの含有量は、タングステン:約0.7ppmそしてコバルト:約1pp Analysis of the copper foil thus obtained, the content of tungsten and cobalt to total foil, tungsten: about 0.7ppm and cobalt: about 1pp
m(突起状銅電着物中の含有量は、W:約0.007w m (content in the protuberant copper electrodeposits, W: about 0.007w
t%そしてCo:約0.01wt%)であった。 t% and Co: was about 0.01wt%). 得られた銅箔をガラス布基材エポキシ樹脂に加熱・加圧して銅張り積層板を作製し、引きはがし強さ及び粉落ち特性を測定した。 The resulting copper foil heated to a glass fabric based epoxy resin and pressure to prepare a copper-clad laminate was measured peel strength and dusting properties. 結果を表1に示す。 The results are shown in Table 1. 更に、粗化処理層上に亜鉛によるトリート処理層及び防錆層を形成した銅箔は一層良好な耐熱性と耐酸化性を示した。 Further, copper foil to form a treat processing layer and the anti-corrosion layer with zinc on the roughened layer showed better heat resistance and oxidation resistance.

【0031】(比較例1)添加物を含まない例として、 [0031] Examples containing no (Comparative Example 1) additives,
硫酸銅(5水塩)100g/l及び硫酸100g/lを含む水溶液を30℃で電解浴として使用し、厚さ70μ Use as an electrolytic bath at 30 ° C. The aqueous solution containing copper sulfate (pentahydrate) 100 g / l and sulfuric acid 100 g / l, thickness 70μ
mの電解銅箔の被接着面に電流密度20A/dm 2で1 at a current density of 20A / dm 2 surface to be adhered of the electrolytic copper foil of m 1
0秒間めっきした後、銅イオン45g/l、硫酸100 After plating 0 seconds, copper ion 45 g / l, sulfuric acid 100
g/lを含む電解液(40℃)を用い、30A/dm 2 electrolyte used (40 ° C.) containing g / l, 30A / dm 2
で4秒間めっきした。 It was plated in 4 seconds. 得られた銅箔をガラス布基材エポキシ樹脂に加熱・加圧して銅張り積層板を作製し、引きはがし強さ及び粉落ち特性を測定した。 The resulting copper foil heated to a glass fabric based epoxy resin and pressure to prepare a copper-clad laminate was measured peel strength and dusting properties. 結果を表1に示す。 The results are shown in Table 1.

【0032】(比較例2)従来からの砒素を含む例として、硫酸銅(5水塩)100g/l、硫酸100g/l [0032] Examples containing arsenic from (Comparative Example 2) Conventionally, copper sulfate (pentahydrate) 100 g / l, sulfuric acid 100 g / l
及び砒酸3g/lを含む水溶液を30℃で電解浴として使用し、厚さ70μmの電解銅箔の被接着面に電流密度20A/dm 2で10秒間めっきした後、銅イオン45 And arsenate an aqueous solution containing 3 g / l was used as an electrolytic bath at 30 ° C., after plating at a current density of 20A / dm 2 10 seconds the adhesive surface of the electrolytic copper foil having a thickness of 70 [mu] m, copper ion 45
g/l、硫酸100g/lを含む電解液(40℃)を用い、30A/dm 2で4秒間めっきした。 g / l, using the electrolyte (40 ° C.) containing sulfuric acid 100 g / l, were plated at 30A / dm 2 4 sec. このようにして得られた銅箔を分析したところ、箔全体に対する砒素の含有量は約200ppm(突起状銅電着物中のAsの含有量は、約1.2wt%)であった。 Analysis of the copper foil thus obtained, the content of arsenic to the total foil about 200 ppm (content of As in the protuberant copper electrodeposits, about 1.2 wt%) it was. 得られた銅箔をガラス布基材エポキシ樹脂に加熱・加圧して銅張り積層板を作製し、引きはがし強さ及び粉落ち特性を測定した。 The resulting copper foil heated to a glass fabric based epoxy resin and pressure to prepare a copper-clad laminate was measured peel strength and dusting properties. 結果を表1に示す。 The results are shown in Table 1.

【0033】 [0033]

【表1】 [Table 1]

【0034】 [0034]

【発明の効果】本発明によるクロム又はタングステン或いは両者から成る第1群金属成分と、バナジウム、ニッケル、鉄、コバルト、亜鉛、ゲルマニウム及びモリブデンから選ばれる1種或いは2種以上から成る第2群金属成分とを含有する銅電解浴で粗化した銅箔は、その処理は均一であり、ムラもなく優秀な基板特性を示す。 A first group metal component made of chromium or tungsten or both according to the present invention, vanadium, nickel, iron, cobalt, zinc, one or a second metal group consisting of two or more selected from germanium and molybdenum copper foil roughened copper electrolytic bath containing a component, the processing is uniform, showing excellent substrate properties without unevenness. 銅箔とガラス布基材エポキシ樹脂で積層板を作製した場合、 If to produce a laminate with copper foil and glass-cloth-based epoxy resin,
良好な接着性及び耐熱性を示し、デンドライトの発達を抑えた丸みのある電着物が形成されるので、接着強度は向上しまたエッチング後の基板の電気的特性や粉落ちの問題がない。 Showed good adhesion and heat resistance, since the electrodeposit a rounded with reduced development of dendrites are formed, bonding strength is no electrical characteristics and dusting problems of the substrate after enhanced also etched.

【図面の簡単な説明】 BRIEF DESCRIPTION OF THE DRAWINGS

【図1】電解銅箔の被接着面側の処理層の例を概略的に示す断面図である。 1 is a cross-sectional view schematically showing an example of the bonding surface side of the treated layer of the electrolytic copper foil.

【符号の説明】 DESCRIPTION OF SYMBOLS

1 生箔 2 凸部 3 粗化処理層 4 銅めっき層 5 トリート処理めっき層 6 防錆層 1 raw foil 2 projections 3 roughened layer 4 copper plating layer 5 Treat treated plating layer 6 anticorrosive

Claims (6)

    【特許請求の範囲】 [The claims]
  1. 【請求項1】 銅箔の被接着面に、(a)クロム及びタングステンから成る第1群から選ばれた1種或いは2種である第1群金属と(b)バナジウム、ニッケル、鉄、 To 1. A target bonding surface of the copper foil, (a) chromium and the first metal group and is one or two species selected from a first group consisting of tungsten (b) vanadium, nickel, iron,
    コバルト、亜鉛、ゲルマニウム及びモリブデンから成る第2群から選ばれた1種或いは2種以上である第2群金属との両者を含有する多数の突起状銅電着物から成る粗化処理層を有することを特徴とする印刷回路用銅箔。 Cobalt, zinc, have a roughened layer consisting of a number of protruding copper electrodeposits containing both with one or the second metal group is two or more species selected from a second group consisting of germanium and molybdenum copper foil for printed circuit according to claim.
  2. 【請求項2】 銅箔の被接着面に、(a)クロム及びタングステンから成る第1群から選ばれた1種或いは2種である第1群金属と(b)バナジウム、ニッケル、鉄、 To 2. A target bonding surface of the copper foil, (a) chromium and the first metal group and is one or two species selected from a first group consisting of tungsten (b) vanadium, nickel, iron,
    コバルト、亜鉛、ゲルマニウム及びモリブデンから成る第2群から選ばれた1種或いは2種以上である第2群金属との両者を含有する多数の突起状銅電着物から成る粗化処理層と、前記粗化処理層を被覆する、銅、クロム、 Cobalt, zinc, and the roughened layer composed of a large number of protruding copper electrodeposits containing both a second group metal is one kind or two or more species selected from a second group consisting of germanium and molybdenum, the covering the roughened layer, copper, chromium,
    ニッケル、鉄、コバルト及び亜鉛から成る群から選択された1種乃至2種以上の金属又は合金から成るトリート層と、該トリート層を被覆する防錆層とを有することを特徴とする印刷回路用銅箔。 Nickel, iron, and treats layer consisting of one or more metal or alloy selected from the group consisting of cobalt and zinc, for a printed circuit, characterized in that it comprises a rust-preventive layer covering the Treat layer Copper foil.
  3. 【請求項3】 突起状銅電着物の脱落を防止する薄い銅めっき層を前記粗化処理層とトリート層との間に形成したことを特徴とする請求項2の印刷回路用銅箔。 3. A copper foil for printed circuit according to claim 2, characterized in that formed between the protruding copper electrodeposit the roughened layer and Treat layer a thin copper plating layer for preventing falling off.
  4. 【請求項4】 酸性銅電解浴において銅箔を陰極として限界電流密度付近で電解して銅箔の被接着面に多数の突起状銅電着物から成る粗化処理層を形成する印刷回路用銅箔の製造方法において、電解浴中に(a)クロム及びタングステンから成る第1群から選ばれた1種或いは2 4. A copper for a printed circuit which forms a roughened layer consisting of a number of protruding copper electrodeposits on the bonded surface of the copper foil copper foil by electrolysis at the limiting current density near the cathode in an acidic copper electrolyte bath the method of manufacturing a foil, one or two selected from the first group consisting of (a) chromium and tungsten in the electrolytic bath
    種である第1群金属:0.0001〜5g/l と、 The first metal group are species: and 0.0001~5g / l,
    (b)バナジウム、ニッケル、鉄、コバルト、亜鉛、ゲルマニウム及びモリブデンから成る第2群から選ばれた1種或いは2種以上である第2群金属:0.001〜5 (B) vanadium, nickel, iron, cobalt, zinc, the second group metal is germanium and one or more selected from the second group consisting of molybdenum: 0.001
    0g/l の両者を存在せしめることを特徴とする印刷回路用銅箔の製造方法。 Method of manufacturing a printed circuit copper foil, characterized in that made present both 0 g / l.
  5. 【請求項5】 形成された粗化処理層上に銅、クロム、 5. A copper roughened layer formed, chromium,
    ニッケル、鉄、コバルト及び亜鉛から成る群から選択される1種乃至2種以上の金属又は合金から成るトリート層を電解により形成し、更に防錆処理することを特徴とする請求項4の印刷回路用銅箔の製造方法。 Nickel, iron, a treat layer comprising one or more metal or alloy is selected from the group consisting of cobalt and zinc is formed by electrolytic, printed circuit according to claim 4, further characterized by rust manufacturing method of use copper foil.
  6. 【請求項6】 形成された粗化処理層上に突起状銅電着物の脱落を防止する薄い銅めっき層を電解により形成し、形成された銅めっき層上に銅、クロム、ニッケル、 6. The thin copper-plated layer for preventing falling off of the protruding copper electrodeposit formed on the roughened layer was formed by electrolytic copper in the formed copper plating layer, chrome, nickel,
    鉄、コバルト及び亜鉛から成る群から選択される1種乃至2種以上の金属または合金から成るトリート層を電解により形成し、更に防錆処理することを特徴とする請求項4の印刷回路用銅箔の製造方法。 Iron, one or Treat layer consisting of two or more metals or alloys selected from the group consisting of cobalt and zinc is formed by electrolytic further copper for a printed circuit according to claim 4, characterized in that the rust method of manufacturing the foil.
JP5822595A 1995-02-23 1995-02-23 Copper foil and its manufacturing method for a printed circuit Expired - Fee Related JP2920083B2 (en)

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JP2004238647A (en) * 2003-02-04 2004-08-26 Furukawa Circuit Foil Kk Smoothened copper foil, and production method therefor
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