JPS61253886A - Copper foil for printed circuit and manufacture thereof - Google Patents
Copper foil for printed circuit and manufacture thereofInfo
- Publication number
- JPS61253886A JPS61253886A JP9553985A JP9553985A JPS61253886A JP S61253886 A JPS61253886 A JP S61253886A JP 9553985 A JP9553985 A JP 9553985A JP 9553985 A JP9553985 A JP 9553985A JP S61253886 A JPS61253886 A JP S61253886A
- Authority
- JP
- Japan
- Prior art keywords
- copper foil
- zinc
- printed circuits
- electroplating
- molybdenum
- 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
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
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
-
- 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 Methods And Accessories (AREA)
- Manufacturing Of Printed Wiring (AREA)
- Conductive Materials (AREA)
- Non-Insulated Conductors (AREA)
- Parts Printed On Printed Circuit Boards (AREA)
- Laminated Bodies (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
［発明の技術分野］
本発明はプリント回路用銅箔とその製造方法に関し、更
に詳しくは、基材に銅箔を接着せしめて銅張積層板にし
たとき、高温加熱後にあっても基材との剥離強度が著し
く向上し、かつ、エツチング処理時におけるサイドエツ
チング現象の発生を減少せしめるに有効なプリント回路
用銅箔とその製造方法に関する。[Detailed Description of the Invention] [Technical Field of the Invention] The present invention relates to a copper foil for printed circuits and a method for manufacturing the same, and more specifically, when copper foil is bonded to a base material to form a copper-clad laminate, high temperature heating is performed. The present invention relates to a copper foil for printed circuits and a method for producing the same, which has significantly improved peel strength from a substrate even after etching and is effective in reducing the occurrence of side etching phenomena during etching treatment.
［発明の技術的背景とその問題点］
最近、プリント回路が緻密化していくにつれて、プリン
ト回路に使用する銅箔には、基材との剥離強度、耐半田
性、耐薬品性が優れているという特性の外に、ガラス−
エポキシ樹脂のような接着剤を用いて基材と接着し加熱
加圧して積層し例えば １８０℃で４８時間というよう
な条件下で高温加熱したのちであっても、基材との剥離
強度が依然として良好であるという特性が要求されてい
る。[Technical background of the invention and its problems] Recently, as printed circuits have become more dense, copper foil used for printed circuits has superior peel strength with the base material, solder resistance, and chemical resistance. In addition to this characteristic, glass
Even after adhering to a base material using an adhesive such as epoxy resin, laminating it under heat and pressure, and heating it at a high temperature for 48 hours at 180°C, the peel strength with the base material still remains. Good properties are required.
ところで、特公昭５８−７０７７号公報には、耐熱性の
プリント回路用銅箔が開示されている。ここで開示され
ているプリント回路用銅箔は、銅箔の少なくとも一方の
面に亜鉛若しくは酸化亜鉛とクロム酸化物との混合物の
薄膜を形成したものである。そしてこのプリント回路用
銅箔は、アルカリ性の電鍍浴を用いて上記成分の薄膜を
電着せしめて製造されている。By the way, Japanese Patent Publication No. 58-7077 discloses a heat-resistant copper foil for printed circuits. The copper foil for printed circuits disclosed herein has a thin film of zinc or a mixture of zinc oxide and chromium oxide formed on at least one surface of the copper foil. This copper foil for printed circuits is manufactured by electrodepositing a thin film of the above components using an alkaline electroplating bath.
このプリント回路用銅箔は高温加熱後における耐酸化性
はたしかに向上するものの、しかし一方では、この銅箔
を用いてプリント回路を作成すると、エツチング処理時
にサイドエツチング現象が発生して実用性に欠けるとい
う問題がある。このサイドニー７チングに対する耐性を
高め銅箔に防錆力を付与する方法として、銅箔を六価ク
ロム塩の水溶液に浸漬する処理若しくはその状態で通電
処理して銅箔の表面にクロム薄膜を形成することが知ら
れているが、しかしこのような処理を施した銅箔であっ
ても、得られたプリント回路板は、その使用条件が過酷
な場合、とりわけ高温加熱後における剥離強度が必ずし
も満足のいく状態ではない、しかも、その製造時に使用
する六価クロムは明確な公害源であるため、環境衛生上
からして使用することを避けるべきである。Although this copper foil for printed circuits certainly has improved oxidation resistance after being heated to high temperatures, on the other hand, when making printed circuits using this copper foil, side etching occurs during the etching process, making it impractical. There is a problem. As a method of increasing resistance to side kneeching and imparting anti-rust properties to copper foil, a thin chromium film is formed on the surface of the copper foil by immersing the copper foil in an aqueous solution of hexavalent chromium salt or by applying electricity in that state. However, even with copper foil treated in this way, the resulting printed circuit board may not always have satisfactory peel strength under harsh usage conditions, especially after high-temperature heating. Moreover, the hexavalent chromium used in its production is a clear source of pollution, and its use should be avoided from environmental health considerations.
一般に、プリント回路用銅箔の製造工程は、例えば硫醜
銅電鍍浴を用いて銅箔の表面に樹枝状の銅を電析させる
工程と、この電析銅の表面に亜鉛などの薄層を形成する
工程から成り、これらの工程は通常同じ処理機を用いた
連続工程として構成されている。In general, the manufacturing process for copper foil for printed circuits includes a process of electrodepositing dendritic copper on the surface of the copper foil using, for example, a sulfur-containing copper electroplating bath, and a process of depositing a thin layer of zinc or other material on the surface of the deposited copper. These steps are usually configured as consecutive steps using the same processor.
それゆえ、電析工程の終了後、亜鉛などの薄層をアルカ
リ性浴を用いて形成し、その洗浄液を電析工程の排水と
合流せしめて排水溝に流出した場合、排水溝では水酸化
銅が沈積し易くなり好ましくなく、また、亜鉛などの薄
層を形成した銅箔面の残留アルカリ成分を洗浄除去する
ために大量の水を必要とせざるを得ない。Therefore, if a thin layer of zinc or the like is formed using an alkaline bath after the electrodeposition process, and the cleaning solution is combined with the wastewater from the electrodeposition process and flows into the drain, copper hydroxide will be present in the drain. This is undesirable because it tends to deposit, and a large amount of water is required to wash and remove residual alkali components from the surface of the copper foil on which a thin layer of zinc or the like is formed.
このように、上記先行技術のプリント回路用銅箔は、こ
れを用いて亜鉛などの薄層を形成した銅張積層板の高温
加熱後における剥離強度が必ずしも満足のいくレベルに
はなく、しかも重大なことには、その製造工程において
上記したような種々の不都合を不可避とする。したがっ
て、その改良は強く望まれている。As described above, the copper foil for printed circuits of the prior art described above does not necessarily have a satisfactory peel strength after high-temperature heating of copper-clad laminates in which a thin layer of zinc or the like is formed using the copper foil, and moreover, it has serious problems. In particular, various inconveniences as described above are inevitable in the manufacturing process. Therefore, its improvement is strongly desired.
［発明の目的］
本発明は、基材との剥離強度が前記先行のプリント回路
用銅箔の場合と同等か若しくはそれ以上であり、またサ
イドエツチングの発生がないプリント回路用銅箔と、そ
の製造方法の提供を目的とする。[Object of the Invention] The present invention provides a copper foil for printed circuits which has a peel strength with respect to a base material that is equal to or higher than that of the preceding copper foil for printed circuits, and which does not cause side etching. The purpose is to provide a manufacturing method.
［発明の概要］
本発明のプリント回路用銅箔は、銅箔の少なくとも一方
の面に、亜鉛若しくは亜鉛酸化物を含有するモリブデン
薄膜が形成されていることを特徴とし、その製造方法は
、モリブデン酸イオンを含み、かつ、金属亜鉛若しくは
亜鉛の塩を溶解せしめてなる電鍍浴中に銅箔を浸漬して
電鍍処理を施すことを特徴とする。[Summary of the Invention] The copper foil for printed circuits of the present invention is characterized in that a molybdenum thin film containing zinc or zinc oxide is formed on at least one surface of the copper foil, and the method for producing the copper foil includes a molybdenum thin film containing zinc or zinc oxide. The method is characterized by electroplating by immersing the copper foil in an electroplating bath containing acid ions and dissolving metallic zinc or zinc salt.
本発明のプリント回路用銅箔に用いられる銅箔は、電解
銅箔、圧延銅箔などのいずれであってもよく格別限定さ
れるものではない、また、銅箔の厚みに関しても特に限
定するものではない、基材と接着せしめる面は、予め粗
面化しておき更に例えば硫酸銅電鍍浴を用いてそこに樹
枝状の銅を電析させたものが好適である。The copper foil used for the copper foil for printed circuits of the present invention may be either electrolytic copper foil, rolled copper foil, etc., and is not particularly limited, and there are no particular limitations on the thickness of the copper foil. It is preferable that the surface to be bonded to the base material be roughened in advance and that dendritic copper be electrodeposited thereon using, for example, a copper sulfate electroplating bath.
この銅箔の片面若しくは両面には、後述の電鍍処理によ
って、亜鉛若しくは亜鉛酸化物が含有されているモリブ
デン薄膜が形成される。ここでいう亜鉛若しくは亜鉛酸
化物は、電鍍処理時に該モリブデン薄膜中に混在するも
のであって、具体的には金属亜鉛、酸化亜鉛、水酸化亜
鉛などである。A thin molybdenum film containing zinc or zinc oxide is formed on one or both sides of the copper foil by electroplating, which will be described later. The zinc or zinc oxide mentioned here is mixed in the molybdenum thin film during electroplating, and specifically includes metal zinc, zinc oxide, zinc hydroxide, and the like.
上記モリブデン薄膜は、モリブデンの含有量が１０〜２
５０ ＩＬｇ／ｄｍ２．亜鉛の含有量が１０〜２５０ｇ
ｇ／ｄａ２をもって構成されていることが好ましい。The molybdenum thin film has a molybdenum content of 10 to 2
50 ILg/dm2. Zinc content is 10-250g
g/da2.
モリブデンの含有量が１１Ｌｇ／ｄ１２未満の場合には
サイドエツチング現象が多発し始めて好ましくなく、ま
た、モリブデンの含有量が２５０μｇ／ｄ１１２を超え
る場合には剥離強度に資する効果が減少して好ましくな
い、一方、亜鉛の含有量が１０ ｇ ｇ／ｄｔａ２未満
の場合には、このモリブデン薄膜が基材との剥離強度の
向上に資する効果は減退し、また２５０ ＩＬｇ／ｄ膳
２を超える場合には、サイドエツチング現象が多発しは
じめて好ましくない。If the molybdenum content is less than 11 Lg/d12, side etching phenomenon will occur frequently, which is undesirable, and if the molybdenum content exceeds 250 μg/d12, the effect contributing to peel strength will decrease, which is undesirable. On the other hand, if the zinc content is less than 10 g g/dta2, the effect of this molybdenum thin film on improving the peel strength with the base material decreases, and if it exceeds 250 ILg/dta2, It is not desirable if the side etching phenomenon begins to occur frequently.
とくに、モリブデンの含有量が５０〜１５０ ＪＬｇ／
ｄ膳２゜亜鉛の含有量が５０〜１５０ ＩＬｇｏｄｓ”
の薄膜は好適である。この薄膜においてモリブデン、亜
鉛の上記含有量は、用いる電鍍浴における各成分の濃度
。In particular, the content of molybdenum is 50 to 150 JLg/
d Zen 2゜Zinc content is 50-150 ILgods”
A thin film of is suitable. The above contents of molybdenum and zinc in this thin film are determined by the concentration of each component in the electroplating bath used.
電鍍条件等を適宜に調節することにより容易に制御する
ことができる。It can be easily controlled by appropriately adjusting the plating conditions and the like.
本発明のプリント回路用銅箔は次のようにして製造する
ことができる。The copper foil for printed circuits of the present invention can be manufactured as follows.
まず、電鍍浴を調製する。用いる電鍍浴は、モリブデン
酸イオンを含みかつ亜鉛若しくは亜鉛の塩が溶解せしめ
られた水溶液である。First, prepare an electroplating bath. The electroplating bath used is an aqueous solution containing molybdate ions and in which zinc or zinc salt is dissolved.
モリブデン酸イオンの供給源としては、例えばＮａ２Ｍ
ｏＯ４−２Ｈ２０、Ｋ２ＭｏＯ４、（ＮＨ４）６Ｍｏ７
０２４・４Ｈ２０をあげることができ、また亜鉛の塩の
供給源としては、例えば、Ｚｎ５０４−７Ｈ２０，Ｚｎ
（，１２，Ｚｎ（ＣＨ３（００）２・２Ｈ２０をあげる
ことができる。これらの、各イオン供給源をそれぞれ所
定量水に溶解せしめて電鍍浴が構成されるが、溶解せし
める各イオン供゛給源の量は、銅箔上に電析せしめるモ
リブデン、亜鉛の前記した６量を勘案して決められる０
例えばモリブデン酸イオン供給源としてＮａ２ＭｏＯ４
・２Ｈ２０を用い、亜鉛イオン供給源としてＺｎＳＯ４
・７Ｈ２０を用いた場合、それぞれの溶解量は電鍍浴全
量１文当り、０．５〜１０ｇ。As a source of molybdate ions, for example, Na2M
oO4-2H20, K2MoO4, (NH4)6Mo7
Zn504-7H20, Zn504-7H20, Zn504-7H20, Zn504-7H20, etc.
(,12,Zn(CH3(00)2・2H20).The electroplating bath is constructed by dissolving each of these ion sources in a predetermined amount of water. The amount of 0 is determined by taking into account the above-mentioned six amounts of molybdenum and zinc to be deposited on the copper foil.
For example, Na2MoO4 as a source of molybdate ions.
・Using 2H20 and ZnSO4 as the zinc ion source
- When using 7H20, the amount of each dissolved amount is 0.5 to 10 g per one pot of the total electroplating bath.
０．５〜１０ｇの範囲にあることが好ましい。It is preferably in the range of 0.5 to 10 g.
電鍍浴は硫酸等の酸液を用いてｐＨを３．０〜５．０の
酸性液に調整して用いることが好ましい、 ｐＨが３．
０より低くなると、亜鉛の電析量が増大し、またＰＨが
５．０より高くなると電鍍浴中に水酸化亜鉛の沈澱が生
じはじめるからである。The electroplating bath is preferably used by adjusting the pH to an acidic solution of 3.0 to 5.0 using an acid solution such as sulfuric acid.
This is because when the pH is lower than 0, the amount of zinc deposited increases, and when the pH is higher than 5.0, zinc hydroxide begins to precipitate in the electroplating bath.
つぎに、この電鍍浴に銅箔を浸漬して電鍍処理を施す、
電鍍処理は通常室温下で行なえばよい。Next, the copper foil is immersed in this electroplating bath to perform electroplating treatment.
Electroplating treatment may normally be carried out at room temperature.
電流密度は格別限定されないが０，１〜ＩＯＡ／ｄａ２
が好適である。また電鍍時間は、形成するモリブデン薄
ＤＩの厚みとの関係から １〜１０秒であればよい。The current density is not particularly limited, but is 0.1 to IOA/da2.
is suitable. Further, the electroplating time may be 1 to 10 seconds depending on the thickness of the thin molybdenum DI to be formed.
このような電鍍処理を施した銅箔を電鍍浴から引き出し
たのちただちに水洗して付着電鍍液を除去し、更に例え
ば１００〜１１０℃の温度で大気中乾燥処理を施すこと
により、本発明のプリント回路用銅箔が得られる。After the copper foil subjected to such electroplating treatment is taken out from the electroplating bath, it is immediately washed with water to remove the adhering electroplating solution, and further dried in the atmosphere at a temperature of 100 to 110°C, for example, to produce the print of the present invention. A copper foil for circuits is obtained.
なお、このようにして製造した本発明のプリント回路用
鋼箔のモリブデン−亜鉛薄膜の上にクロメート薄膜を積
層し、更にその上にシランカップリング剤を含有した接
着剤層を形成せしめると、その銅箔は基材との剥離強度
および耐塩酸性が一層向上するので有用である。In addition, when a chromate thin film is laminated on the molybdenum-zinc thin film of the steel foil for printed circuits of the present invention produced in this way, and an adhesive layer containing a silane coupling agent is further formed on top of the molybdenum-zinc thin film, Copper foil is useful because it further improves peel strength with the base material and hydrochloric acid resistance.
［発明の実施例］
実施例ｌ
Ｎａ２ＭｏＯ４−２Ｈ２０の濃度１ｇ／ ｌ 、 Ｚｎ
ＳＯ４・７Ｈ２０（７）濃度２ｇ／ｆＬ、硫酸でｐＨを
４に調整した電鍍浴の中に、厚み１８μの銅箔を浸漬し
、電流密度０．３Ａ／ ｄａ” 。[Examples of the invention] Example 1 Concentration of Na2MoO4-2H20 1 g/l, Zn
A copper foil with a thickness of 18 μm was immersed in an electroplating bath in which the SO4.7H20(7) concentration was 2 g/fL and the pH was adjusted to 4 with sulfuric acid, and the current density was 0.3 A/da”.
通電時間５秒、浴温度室温の条件で電鍍処理を施し、つ
いでただちに銅箔を取り出して充分水洗したのち １０
０〜１１０℃で乾燥した。Electroplating was performed under the conditions of energization time of 5 seconds and bath temperature of room temperature, and then the copper foil was immediately removed and thoroughly washed with water.
Dry at 0-110°C.
得られた銅箔の粗面側に形成された薄膜中のモリブデン
量、亜鉛量を原子吸光光度計を用いて測定しｐ−ｇ／ｄ
ｒｓ２量として算出した。その結果を表に示した。The amount of molybdenum and the amount of zinc in the thin film formed on the rough surface side of the obtained copper foil were measured using an atomic absorption spectrophotometer and determined as p-g/d.
It was calculated as the amount of rs2. The results are shown in the table.
つぎに、銅箔の粗面側にガラスエポキシ樹脂含浸基材を
接着し、温度１８０℃、圧力１００ ｋｇ／ ｃ■２で
４０分間加熱加圧処理して縦２５０■濡横２５０■■厚
み１、Ｅｌｍｍの銅張積層板の試験片を製作した。Next, a glass epoxy resin-impregnated base material is adhered to the rough side of the copper foil, and heated and pressure-treated at a temperature of 180°C and a pressure of 100 kg/cm2 for 40 minutes to give a height of 250 mm, a wet width of 250 mm, and a thickness of 1. , Elmm copper clad laminate test pieces were manufactured.
この試験片につき以下の仕様で剥離強度を測定し、また
サイドエツチング発生の有無を観察した。The peel strength of this test piece was measured according to the following specifications, and the presence or absence of side etching was observed.
剥離強度： ＪＩＳ Ｃ−８４８１に準拠する。Peel strength: Based on JIS C-8481.
以上の試験を室温下で行なった結 果をＡ、試験片を １８０℃の恒温槽 中で４８時間放置したのちの結果を Ｂとして示した。The results of the above tests conducted at room temperature Place the fruit in A and the test piece in a constant temperature bath at 180°C. The results after leaving it inside for 48 hours. Shown as B.
サイドエツチング観察：銅箔の光沢面に市販のエツチン
グレジスト膜を形成し
て配線パターンを印刷し、塩化第
二銅エツチング液でプリント回路
板以外の銅箔を溶解除去して回路
幅１ｍｍの回路板とし、回路と基板
の境界部を顕微鏡観察（倍率１５０）
してサイドエツチング発生の有無
を観察した。Side etching observation: A commercially available etching resist film is formed on the glossy surface of the copper foil, a wiring pattern is printed, and the copper foil other than the printed circuit board is dissolved and removed using cupric chloride etching solution to form a circuit board with a circuit width of 1 mm. The boundary between the circuit and the board was observed under a microscope (magnification: 150) to determine whether side etching occurred.
以上の結果を表に示した。The above results are shown in the table.
実施例２
Ｎａ２ＭｏＯ４−２８２０、ＺｎＳＯ４・７Ｈ２０（１
）濃度がそれぞれ０．５ｇ／見、 ０．５ｇ／ｌであっ
たこと、電流密度が０．１Ａ／ｄ＋＋２であったこと１
通電時間が３秒であったこと、を除いては実施例１と同
様にしてプリント回路用銅箔を製造した。各特性仕様を
表に示した。Example 2 Na2MoO4-2820, ZnSO4・7H20(1
) The concentrations were 0.5 g/l and 0.5 g/l, respectively, and the current density was 0.1 A/d++2.
A copper foil for printed circuits was produced in the same manner as in Example 1, except that the current application time was 3 seconds. Each characteristic specification is shown in the table.
実施例３
Ｎａ２ＭｏＯ４−２Ｈ２０、ＺｎＳＯ４・７Ｈ２０の濃
度がそれぞれ２．０ｇ／見、４゜Ｏｇ／ ｌであったこ
と、ｐＨが４．５であったこと、電流密度がＩＡ／ｄ鳳
２であったこと。Example 3 The concentrations of Na2MoO4-2H20 and ZnSO4.7H20 were 2.0 g/ml and 4°Og/l, respectively, the pH was 4.5, and the current density was IA/d 2. Was it.
を除いては実施例１と同様にしてプリント回路用銅箔を
製造した。各特性仕様を表に示した。A copper foil for printed circuits was produced in the same manner as in Example 1 except for the following. Each characteristic specification is shown in the table.
比較例１
電鍍浴にＮａ２Ｃｒ２Ｏ７・２Ｈ２０５ｇ／ ｌの濃度
でｐＨ５の水溶液を用い、これに実施例１で用いた銅箔
を浸漬して、電流密度０．５Ａ／ ｄｍ２．通電時間５
秒、浴温度室温の条件で電鍍処理を施し、銅箔表面にク
ロメート薄ｎりを形成した。Comparative Example 1 An aqueous solution with a concentration of Na2Cr2O7.2H205 g/l and pH 5 was used in an electroplating bath, and the copper foil used in Example 1 was immersed in the solution at a current density of 0.5 A/dm2. Energization time 5
Electroplating was performed at a bath temperature of room temperature for 2 seconds to form a thin chromate layer on the surface of the copper foil.
この銅箔につき、実施例１と同様の手法で薄膜構成金属
の量、剥離強度、サイドエツチング発生の有無について
調べ、その結果を表に示した。This copper foil was examined for the amount of metal forming the thin film, peel strength, and occurrence of side etching using the same method as in Example 1, and the results are shown in the table.
比較例２
電鍍浴がＺｎＳＯ４・７Ｈ２０５ｇ／ Ｑ トＮａＯＨ
４０ｇ／ ｆＬ カら成るアルカリ性亜鉛電鍍液であっ
たことを除いては、比較例１と同様の条件で電鍍処理を
施し、銅箔表面に亜鉛薄膜を形成した。その特性仕様を
表に示した。Comparative Example 2 Electroplating bath was ZnSO4.7H205g/Q NaOH
Electroplating was performed under the same conditions as in Comparative Example 1, except that the alkaline zinc electroplating solution was 40 g/fL, and a thin zinc film was formed on the surface of the copper foil. Its characteristic specifications are shown in the table.
比較例３
電鍍浴がＺｎＳＯ４・７Ｈ２０５ｇ／ ｌ 、 Ｎａ２
Ｃｒ２Ｏ７・２２Ｈ２Ｏ３／ ｌ 、 ＮａＯＨ４０ｇ
／ ｌから成るアルカリ性亜鉛−クロム電鍍液であった
こと、電流密度が０．３Ａ／ｄａ２であったこと、を除
いては比較例１と同様の条件下で電鍍処理を施し、銅箔
表面に亜鉛−クロムの混合薄膜を形成した。その特性仕
様を表に示した。Comparative example 3 Electroplating bath was ZnSO4.7H205g/l, Na2
Cr2O7・22H2O3/l, NaOH40g
Electroplating was carried out under the same conditions as in Comparative Example 1, except that the electroplating solution was an alkaline zinc-chromium electroplating solution consisting of 0.3 A/l and the current density was 0.3 A/da2, and the surface of the copper foil was electroplated. A zinc-chromium mixed thin film was formed. Its characteristic specifications are shown in the table.
［発明の効果］
以上の説明で明らかなように、本発明方法で製造したプ
リント回路用銅箔は、加熱処理後にあっても基材との剥
離強度は大きく、またエツチング処理時においてはサイ
ドエツチングの発生がない、しかもその製造方法におい
ては、公害源たるクロムを使用することもなく、また電
鍍液がアルカリ性の場合に生じていた不都合も解消され
てその工業的価値は大である。[Effects of the Invention] As is clear from the above explanation, the copper foil for printed circuits manufactured by the method of the present invention has a high peel strength from the base material even after heat treatment, and also shows no side etching during etching treatment. Moreover, the manufacturing method does not use chromium, which is a source of pollution, and eliminates the inconveniences that occur when the electroplating solution is alkaline, making it of great industrial value.
Claims (1)
化物を含有するモリブデン薄膜が形成されていることを
特徴とするプリント回路用銅箔。 ２、亜鉛含有モリブデン薄膜が、モリブデン１０〜２５
０μｇ／ｄｍ＾２、亜鉛１０〜２５０μｇ／ｄｍ＾２で
構成されている特許請求の範囲第１項記載のプリント回
路用銅箔。 ３、モリブデン酸イオンを含み、かつ、金属亜鉛若しく
は亜鉛の塩を溶解せしめてなる電鍍浴中に銅箔を浸漬し
て電鍍処理を施すことを特徴とするプリント回路用銅箔
の製造方法。 ４、電鍍浴が酸性液である特許請求の範囲第３項記載の
プリント回路用銅箔の製造方法。[Claims] 1. A copper foil for printed circuits, characterized in that a molybdenum thin film containing zinc or zinc oxide is formed on at least one surface of the copper foil. 2. The zinc-containing molybdenum thin film contains molybdenum 10 to 25
The copper foil for printed circuits according to claim 1, comprising 0 μg/dm^2 and zinc 10 to 250 μg/dm^2. 3. A method for producing copper foil for printed circuits, which comprises immersing the copper foil in an electroplating bath containing molybdate ions and dissolving metal zinc or zinc salt to perform electroplating treatment. 4. The method for producing copper foil for printed circuits according to claim 3, wherein the electroplating bath is an acidic liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9553985A JPS61253886A (en) | 1985-05-07 | 1985-05-07 | Copper foil for printed circuit and manufacture thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9553985A JPS61253886A (en) | 1985-05-07 | 1985-05-07 | Copper foil for printed circuit and manufacture thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61253886A true JPS61253886A (en) | 1986-11-11 |
| JPH0376798B2 JPH0376798B2 (en) | 1991-12-06 |
Family
ID=14140365
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9553985A Granted JPS61253886A (en) | 1985-05-07 | 1985-05-07 | Copper foil for printed circuit and manufacture thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61253886A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63187684A (en) * | 1987-01-30 | 1988-08-03 | 株式会社東芝 | Circuit board |
| JP2007508448A (en) * | 2003-09-02 | 2007-04-05 | オリン コーポレイション | Chromium-free discoloration prevention / adhesion promoting treatment composition |
| WO2013115382A1 (en) * | 2012-02-03 | 2013-08-08 | Jx日鉱日石金属株式会社 | Copper foil for printed wiring board, as well as laminate, printed wiring board, and electronic component using same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5620718A (en) * | 1979-07-28 | 1981-02-26 | Mitsubishi Heavy Ind Ltd | Air feeder for diesel engine |
-
1985
- 1985-05-07 JP JP9553985A patent/JPS61253886A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5620718A (en) * | 1979-07-28 | 1981-02-26 | Mitsubishi Heavy Ind Ltd | Air feeder for diesel engine |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63187684A (en) * | 1987-01-30 | 1988-08-03 | 株式会社東芝 | Circuit board |
| JP2007508448A (en) * | 2003-09-02 | 2007-04-05 | オリン コーポレイション | Chromium-free discoloration prevention / adhesion promoting treatment composition |
| JP2010111951A (en) * | 2003-09-02 | 2010-05-20 | Olin Corp | Chromium-free antitarnish adhesion-promoting treatment composition |
| WO2013115382A1 (en) * | 2012-02-03 | 2013-08-08 | Jx日鉱日石金属株式会社 | Copper foil for printed wiring board, as well as laminate, printed wiring board, and electronic component using same |
| JP2013161925A (en) * | 2012-02-03 | 2013-08-19 | Jx Nippon Mining & Metals Corp | Copper foil for printed wiring plate, laminate using the same, printed wiring plate and electronic component |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0376798B2 (en) | 1991-12-06 |
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