JPS5925297A - Copper foil for printed circuit - Google Patents
Copper foil for printed circuitInfo
- Publication number
- JPS5925297A JPS5925297A JP13529982A JP13529982A JPS5925297A JP S5925297 A JPS5925297 A JP S5925297A JP 13529982 A JP13529982 A JP 13529982A JP 13529982 A JP13529982 A JP 13529982A JP S5925297 A JPS5925297 A JP S5925297A
- Authority
- JP
- Japan
- Prior art keywords
- copper foil
- layer
- zinc
- foil
- copper
- 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
Landscapes
- Laminated Bodies (AREA)
- Manufacturing Of Printed Wiring (AREA)
- Parts Printed On Printed Circuit Boards (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】
この発明は、銅箔と基材とからの銅張積層板の高温加熱
後の接着特性を顕著に改善した印刷回路用銅箔に関する
ものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a copper foil for printed circuits that has significantly improved adhesive properties after high temperature heating of a copper clad laminate made of a copper foil and a substrate.
最近、印刷回路の緻密化に伴い、使用する銅箔に対して
、基材との剥離強度、耐半田性、耐薬品性以外′に、銅
箔と基材とを積層後、例えばこれに１８０℃で４８時間
という長時間の加熱を行った場合でも、訃］箔と基桐面
との間の剥頗強度の良い制御剤の出現が要望されている
６゜従来、耐熱性の印刷回路用銅箔ケ得るための方法と
して、特公昭５１−３５７１１号公報（アメリカ特許第
３５８５０１０号公報に対応のもの）には、銅箔の片面
に、亜鉛、インジウム、４へ／ｆ１１ηとからなる群か
ら選ばれる金属紙塙被慢を設けたもの、−１だ特公昭５
３−３９３７６号公報（アメリカ特許第３８５７６８１
号に対応するもの）にう′ま、を同箔に少くとも第１お
よび、８２の２ｕｉ頂の粗化処理を施し、２番目の処理
により形成されだ粗面に、亜鉛、真鍮などの薄層を形成
させたものの使用が有効であると開示されている。しか
し、上記従来法は、鋼箔粗面を基材と加熱力１１圧して
銅張積層板となす際に、予じめ銅箔ｖ１１ｉ＃ Ｉｔこ
形成させた亜鉛主体金属薄層が銅箔と合金化し、これに
よって積層板となしだ局舎の７ｊＩｉｌ’Ａｆｆｑと基
材との剥離強度を維持し、かつ銅箔と基拐との接合面に
発生し易い褐色のしみ、いわゆる積層汚点の発生防止を
ねらったものでるる。しかし。Recently, with the densification of printed circuits, the copper foil used has not only the peel strength with the base material, solder resistance, and chemical resistance, but also There is a need for a control agent that has good peeling strength between the foil and the paulownia substrate surface even when heated for a long time of 48 hours at ℃. As a method for obtaining copper foil, Japanese Patent Publication No. 51-35711 (corresponding to U.S. Pat. No. 3,585,010) discloses that one side of the copper foil is coated with zinc, indium, and a metal selected from the group consisting of 4/f11η. The one with the selected metal paper wall, -1.
Publication No. 3-39376 (US Patent No. 3857681)
The same foil is subjected to at least the first and 82 2ui top roughening treatments, and the roughened surface formed by the second treatment is coated with a thin film of zinc, brass, etc. It is disclosed that the use of layered materials is effective. However, in the above conventional method, when forming a copper-clad laminate by heating the rough surface of the steel foil with the base material at 11 pressures, the thin zinc-based metal layer formed in advance on the copper foil is mixed with the copper foil. alloyed, thereby maintaining the peel strength between the laminate and the base material, and preventing the occurrence of brown stains, so-called lamination stains, that tend to occur on the bonding surface between the copper foil and the base material. There are things that are aimed at prevention. but.
上記従来法の第１の欠点は、＠眼精層板の製造に当り、
′祠′？西と暴利との接着力向上のため、予じめ電解処
理によって銅箔粗面に樹枝状銅層整形成させ、その上に
ＩＩＦ鉛などの異種金属を電析により形成させるもので
あり、これにより樹枝軟銅の一部分が曲鉛などの異種金
属の薄層で覆われるだめ、接面と基材とを加熱加圧して
鋼張積層板となす際に、銅箔と暴利との間の剥離強度が
低下するのを回付できないものである。寸だ第２の欠点
は、銅箔面にメッキにより形成した叱鉛層は長間放置中
に、その放置条件により、酸化亜鉛、炭酸亜鉛、塩塙性
亜鉛などに変化し、粉化脱落し易いという欠点があった
。The first drawback of the above conventional method is that when producing the ocular lamina,
'Shrine'? In order to improve the adhesion between the market and the profiteers, a dendritic copper layer is formed on the rough surface of the copper foil by electrolytic treatment in advance, and a dissimilar metal such as IIF lead is deposited on top of this by electrolytic treatment. As a result, a part of the dendrite annealed copper is covered with a thin layer of a dissimilar metal such as curved lead, so when the contact surface and the base material are heated and pressed to form a steel clad laminate, the peel strength between the copper foil and the profiteer is reduced. This is something that cannot be repeated due to a decrease in The second drawback is that the scolding layer formed by plating on the copper foil surface changes into zinc oxide, zinc carbonate, zinc chloride, etc. when left for a long time, depending on the conditions, and powders and falls off. It had the disadvantage of being easy.
この中温１の欠点口、印刷回路の緻密化に伴う銅箔と基
（ぢ而とのμ・１］離強度を増強するだめの犬さな障害
となる。さりとてｉｌｌ ｆｌＵ強度の向上のみを考Ｉ
・←、し、ν１・１１箔ｉｉｔ面に強力な屯屑粗化を施
せば、形成さ町た樹枝軟銅が脱落し易くなり、いわゆる
積層汚点の発生を防止できなくなる。This shortcoming of medium temperature 1 is a serious obstacle to increasing the μ・1 separation strength between the copper foil and the substrate as printed circuits become more dense. I
・←, ν1・11 If strong dust roughening is applied to the iit surface of the foil, the formed dendrite annealed copper will easily fall off, making it impossible to prevent so-called lamination stains.
またｊ’４’、’ ２の欠点は、袢ｉ１箔の長＋１ＪＩ
・保存ないし／ｐ同同量輸出に当って考慮すべき問題
である。Also, the drawback of j'4' and '2 is that the length of the hitsuki i1 foil + 1JI
・This is an issue that should be taken into account when preserving or exporting the same amount.
本発明者等は、銅箔粗面側に、クロメート処理層を設け
、接面を前記一般式ＹＲ８Ｉ Ｘ３（式中のＹは高分子
物と反応する官能基、Ｒ，はＹとケイ素原子とを連結す
る鎖状またけ環状の炭化水素を含む結合基、Ｘはケイ素
原子に結合する有機捷たは無機の加水分解性の基を表わ
す。）で示されるシランカップリング剤溶液で処理後。The present inventors provided a chromate treatment layer on the rough surface side of the copper foil, and the contact surface was formed using the general formula YR8I (X represents an organic or inorganic hydrolyzable group bonded to a silicon atom) after treatment with a silane coupling agent solution.
基材と接着させると該銀箔と基材との接着力を顕著に向
上できることを認め、すでに昭和５５年特許願第１６２
３６７号として特許出願している。It was recognized that the adhesion between the silver foil and the base material could be significantly improved by adhering it to the base material, and patent application No. 162 was filed in 1982.
A patent application has been filed as No. 367.
しかし、その後の研究によると、該出′幀の方法で得だ
鋼張積層板は、現在業界において要求されている１例え
ば１８０℃、４８時間という加熱処理を行った後におい
て、銅箔と暴利との剥離強度を保持させる点においては
未だ欠点があることを認めた。そこで引続き銅箔粗面の
処理条件などについて各種検討を行ってきた。その結果
、銅箔の粗面に直ｆＩ！：または・経度の粗化を行った
後、核部に亜鉛まだは亜鉛合金の薄層を形成し、該層に
公知の方法でクロメート処理層を設け、その上に、前記
一般式の化合物による処理層を形成させだ銅箔を基材と
積層したものは、上記１８０℃、４８時間の加熱処理後
°においても、剥離強度がｐく、その他の特性において
も従来のものとＩｈＪ等であることを多数の実験により
確認できた。本発明は上記実験結果に基づいて、ここに
完成をみたものである。However, subsequent research has shown that the steel-clad laminates obtained by this method cannot be used for commercial purposes after being subjected to the heat treatment currently required in the industry, for example, at 180°C for 48 hours. It was acknowledged that there were still deficiencies in maintaining the peel strength. Therefore, we continued to conduct various studies on processing conditions for the rough surface of copper foil. As a result, direct fI! on the rough surface of the copper foil! : Or - After roughening, a thin layer of zinc or zinc alloy is formed on the core, a chromate treatment layer is provided on the layer by a known method, and a chromate treatment layer is applied on top of the layer by a compound of the above general formula. The copper foil laminated with the base material on which the treated layer has been formed has a peel strength of P even after the heat treatment at 180°C for 48 hours, and has other properties that are comparable to conventional products such as IhJ. This was confirmed through numerous experiments. The present invention has now been completed based on the above experimental results.
本発明の鉋１箔は、シランカップリング剤が、クロメー
ト処理した銅箔と基材との接着力を強くする／ζめ、
ｎｉｌ記特公昭５３−３９３７６号公報に開示のものの
ように４同量面に苛酷になり易い粗化処理の必要なく、
従来の銅箔以上の剥離強度を保持し得る１、従って本発
明全同量粗面を暴利と積層後エツチングにより印刷回路
板としても、絶縁基板中に（も１枝状矩残留物による積
層汚点を生じる恐れはない。まだ本発明の銅（〉＾粗面
側に形成する唾鉛丑たは亜鉛合金層に関しても、該層上
に施すクロメート処理層が、その防蝕性を増すだめ、銅
箔の長期保存が可能となるという利点がある。また出願
中の明細１において、ＪｉｌＪＪ々説明したように、ク
ロメート処哩層上に形成したシランカップリング剤薄膜
がρ四組と暴利とを誤
強桃に接着する作用効果をもつため、 Ａｌｌｌｌ全特
公昭５１５７１１号公報に開示されているように（同量
粗面に、亜鉛とインジウムと面粗とからなる群から選ば
れる少くとも４マイクロインチ（ＯＪμ）以上の電着層
を形成させる必要もな（０，１μ以下の亜鉛または亜鉛
合金層を形成しても、十分その効果を発揮できるもので
ある。従って、この発明は業界に極めて有効な印刷回路
用１１・・１箔を提供する発明であると考える。The plane 1 foil of the present invention has a silane coupling agent that strengthens the adhesive force between the chromate-treated copper foil and the base material.
Unlike the one disclosed in Japanese Patent Publication No. 53-39376, there is no need for harsh roughening treatment on the 4-equivalent surface.
It can maintain peel strength higher than that of conventional copper foil. Therefore, the present invention can also be used as a printed circuit board by profiteering the same amount of rough surface and etching after lamination. There is no risk of causing corrosion.However, regarding the copper foil or zinc alloy layer formed on the rough surface side of the copper foil of the present invention, the chromate treatment layer applied on the layer increases its corrosion resistance. It has the advantage of being able to be stored for a long time.Also, as explained in Jil.J. J. In order to have the effect of adhering to the peach, as disclosed in Allll Zentoku Kokoku No. 515711 (1985), at least 4 microinches of zinc, indium, and surface roughness selected from the group consisting of zinc, indium, and surface roughness are applied to the rough surface by the same amount. There is no need to form an electrodeposited layer with a thickness of 0.1 μm or more (a zinc or zinc alloy layer with a thickness of 0.1 μm or less can sufficiently exhibit its effect. Therefore, this invention is extremely effective for the industry. This invention is considered to provide 11...1 foil for printed circuits.
本発明についての説明を続けると、本発明において銅箔
面に形成する亜鉛合金としては、スズ、ニッケル、銅、
カドミウム、マグネシウムなどの通常メッキで合金とす
ることが【可能な金属であシ、これらの金属は、公知の
ｔｑ ＋ｌｌＩｒ浴を用いれば、銅箔粗面への電析が可
能である。しかし１本発明においては、゛電析にかえて
真空蒸着法、スパッタリング法などの乾式法により形成
することもできる。なお銅箔粗面にＩＩＩ！、鉛層を形
成した場合に較べ、中（鉛合金層を形成させれば？ ｆ
ｊｍ張積層積層板製作１号路板となす場合に、その面ｊ
塩酸性を著しく向上できる。Continuing the explanation of the present invention, in the present invention, the zinc alloy formed on the copper foil surface includes tin, nickel, copper,
Metals such as cadmium and magnesium, which can be made into alloys by ordinary plating, can be electrodeposited onto the rough surface of copper foil using a known tq +llIr bath. However, in the present invention, instead of electrodeposition, it may be formed by a dry method such as a vacuum evaporation method or a sputtering method. In addition, on the copper foil rough surface III! , compared to the case where a lead layer is formed, (if a lead alloy layer is formed? f
jm tension laminated laminate production When making the No. 1 road board, its surface j
Hydrochloric acidity can be significantly improved.
１だ本発明にｋいて、亜鉛１だは亜鉛合金層−Ｆに形成
するクロメートの４ ｉｌＱは、重クロム酸ナトリウム
寸たは三酸化クロムの水溶液を用い、この水溶液中に１
＋＋！鉛または亜鉛合金層を形成させである銅箔をｒｅ
漬するか或いは、この溶液中で該銅箔を陰極として連成
すれば、該金属まだは合金層上に容易に形成することか
り能である。According to the present invention, the 4ilQ of the chromate formed in the zinc alloy layer-F is determined by using an aqueous solution of sodium dichromate or chromium trioxide, and adding 1lQ to the aqueous solution.
++! Copper foil is coated with lead or zinc alloy layer.
The metal layer can be easily formed on the alloy layer by dipping or coupling the copper foil as a cathode in this solution.
引続き本発明において、前記クロム薄膜上に形成させる
７ランカツプリング剤の薄膜の形成について述べると、
使用するシランカップリング剤は１本発明者等が、すで
に出願中の昭和５５年特許願１６２３６７号の明細書に
記載したものが。Continuing with the present invention, the formation of a thin film of a 7-rank coupling agent to be formed on the chromium thin film will be described.
The silane coupling agent used is the one described in the specification of patent application No. 162367 filed in 1982 by the present inventors.
いずれも使用でき１代表的なものを記載するとｒ−アミ
ンブロピルトリエトキンンラン、Ｎ−２−アミノエチル
−３−アミノプロピルトリメトキシシラン、γ−クロロ
プロピルートリメトキシシラン、γ−グリンドオキンプ
ロピルートリメトキン７ランなどである。Any of them can be used. Typical examples include r-amine propyltriethoxysilane, N-2-aminoethyl-3-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, and γ-grindodoquine. Propyltrimethquine 7ran, etc.
また、使用するシランカップリング剤液の処理濃度も前
記出願中の明細書に述べたと同様０．００１〜５％の範
囲のもので良い。以下１本発明を実施例を掲げて、さら
に具体的に説明する。Further, the processing concentration of the silane coupling agent liquid used may be in the range of 0.001 to 5% as described in the above-mentioned specification. Hereinafter, the present invention will be described in more detail with reference to Examples.
実施例（１）
公知の硫酸多量メッキ浴を使用し、チタン製陶極面に電
析形成させた３３μの１間笛を剥ｉ＋ｊｌｆ： ｌ〜、
これを硫酸亜鉛１５０ｇ／看、硫酸アルミニウム３０ピ
≠キ浴中に浸漬し、該銅箔を陰極、鉛板を陽棒として用
い、浴温２５℃、電流密度ＩＡ／ａｍ”において銅箔粗
面にそれぞれ厚さ０．０５１１と０．１２μの亜ｆ［１
薄層を形成した多数の試料を作製した。ついでこの試料
を濃度０．３％の重クロム酸ナトリウム水溶液に浸漬し
、試料のｌｌｊ鉛形成而を面極として浴温２５”Ｃ１市
、流密度０．３Ａ／ｄｍ”において５秒間通電を行い、
亜鉛層上にクロメ−トメＬ７１Ｉ＊を形成イ々、別に訳
製した７ランカツプリング剤であるγ−アミノプロピル
トリエトキンシランの濃度０．０３％、０．３％および
３０％の３種類の液中に常ン、稈て１分間浸漬し取出し
て乾燥後、亜鉛層形成面をガラスクロスを基材としたエ
ポキシ樹脂板に重ね。Example (1) Using a known sulfuric acid copious plating bath, a 33 μm electrode deposited on the surface of a titanium ceramic electrode was peeled off: i + jlf: l ~,
This was immersed in a bath containing 150 g of zinc sulfate and 30 pins of aluminum sulfate, and using the copper foil as a cathode and the lead plate as a positive rod, the rough surface of the copper foil was heated at a bath temperature of 25°C and a current density of IA/am. subf[1 with thicknesses of 0.0511 and 0.12μ, respectively
A number of samples with thin layers were prepared. Next, this sample was immersed in a sodium dichromate aqueous solution with a concentration of 0.3%, and current was applied for 5 seconds at a bath temperature of 25" C1 and a flow density of 0.3 A/dm, using the sample's llj lead formation as a face electrode. ,
After forming chromate L71I* on the zinc layer, three types of γ-aminopropyltriethquin silane, a 7-run coupling agent prepared separately, at concentrations of 0.03%, 0.3% and 30% were applied. The culm was immersed in the solution for 1 minute, taken out and dried, and the zinc layer-formed side was placed on an epoxy resin plate with glass cloth as the base material.
１５５°Ｃ１圧力１００に９／ｃｎＬの条件で３０分間
処理し、２５０＋ｎｒｎＸ２５０ｍｍＸ２ｍｍのΦ同張
積層板を試作した。−ま）ここ・のオＩ千層板の特性と
比較するため、亜鉛層を設けない銅箔のみのもつおよび
亜鉛層とクロメート薄膜イ〔設け、その上にカップリン
グ薄膜（、￥を形成さぜない試料からも銅張積層板を試
作し、これら各試料の１８０°Ｃ１４８時間の加熱処理
ｆｆ１ｉｌ後における暴利と銅箔との間のｇで１１離強
度を測定してみた。結宋は表１の通りである。It was treated at 155° C., pressure 100, and 9/cnL for 30 minutes to fabricate a Φ same tension laminate with dimensions of 250+nrnX250mmX2mm. In order to compare the properties of the 1,000-layer board with the copper foil without the zinc layer, and with the zinc layer and chromate thin film, a coupling thin film (, \) was formed on it. Copper-clad laminates were also trial-produced from samples that did not meet the standards, and the separation strength in g between each sample and the copper foil after heat treatment at 180°C for 148 hours was measured. As per 1.
表１
表から、亜鉛層とクロメート処理１ｑのみを設けた試料
からのものは、カップリング剤処理１１ｑを設けたもの
よりも剥ｉ’ｆｆ１強度が加熱処理前、処理（は０１μ
以下としても、その効果は十分発を軍できることを知り
得だ１゜
実施例（２）
実施例（１）で述べたと同様の銅箔わｌ ｉｆｆを、公
知の硫酸銅メッキ浴を用いて′電解しでぞの表面に樹枝
状階層を形成させた。Table 1 From the table, it can be seen that the peeling i'ff1 strength of the sample with only the zinc layer and chromate treatment 1q was higher than that of the sample with the coupling agent treatment 11q before heat treatment and after treatment (01μ
It can be seen that the effect can be sufficiently achieved even if the following conditions are used.1゜Example (2) A copper foil plate similar to that described in Example (1) was prepared using a known copper sulfate plating bath. A dendritic hierarchy was formed on the surface of the electrolyzed resin.
ついで、これをＩＩＡ酸ｔａ鉛４０ｇ／Ａ−４顎Ｃ俊≧
Ｘ’ｙ−スズ４０ ｇ／−＃、ｌｔ＋ｊｆ ｊｓ２７５
ｇ、／−ｅ、７−ｃ ／ −＃ ７．５ ｇ／１３．
セラテン２ｇ／−ｅからなる亜鉛〜スズ合金メッキ浴に
浸Ｏ“Ｈ〜前記処胛銅箔を陰極、鉛板を陽極に用いて、
浴温２５”Ｇ、電流密度ＩＡ／ｃｉｍ”において、Ｆ’
ｌ枝状の鋼層上に＋１ｐさ０．０５７１と０．１２μの
亜鉛〜スズ師金の、・：り層を設けた試料を形成させた
。Next, this was mixed with 40 g of Ta lead IIA acid/A-4 jaw C-shun≧
X'y-tin 40 g/-#, lt+jf js275
g, /-e, 7-c / -# 7.5 g/13.
Immerse in a zinc-tin alloy plating bath consisting of Ceraten 2g/-e using the treated copper foil as the cathode and the lead plate as the anode,
At bath temperature 25"G and current density IA/cim", F'
A sample was formed in which a layer of zinc to tin master metal of +1p 0.0571 and 0.12μ was provided on a branch-shaped steel layer.
引続き、上記試料を実ｂｌｉ例（１）において述べたと
同様、＠、クロノ、酸すｌ−’Ｊウムの水溶液で処理し
、該試料の推鉛〜スズ合金薄層上にクロメート薄１１悼
を形成体〕、実施例（１）と同一条件でシランカップリ
ング剤溶液で処理し、カップリング剤袖呻を形成後、実
施例（１）と同様の銅眼精１％板を試作した。これとは
別に１合金層を形成させる前の鋼箔および合金層とクロ
メート処理小臭を設けただけの鋼量からも前記と同一の
・銅張積層板を作り、これら試作積層板につき１８０°
Ｃ１４８時間の加熱処理を施す前後において、銅箔と暴
利との間の剥に１強度を測定してみた。結果は表２に示
す〕ｍりである。Subsequently, the above sample was treated with an aqueous solution of @, chlorine, and sodium oxide in the same manner as described in Example (1), and a thin layer of chromate was applied on the thin lead-tin alloy layer of the sample. [formed body] was treated with a silane coupling agent solution under the same conditions as in Example (1) to form a coupling agent sleeve, and then a 1% copper eye sperm board similar to Example (1) was produced as a trial. Separately, the same copper-clad laminates as above were made from the steel foil before forming one alloy layer, the alloy layer, and the amount of steel with a slight chromate treatment.
The peeling strength between the copper foil and the copper foil was measured before and after the heat treatment for 148 hours. The results are shown in Table 2.
表２
表から１通常の樹枝状鋼層を設けた絹ｊ箔をＦ＋１いて
も１本発明処理により、加熱処理イダＣの剥’ｉｌＥ強
度のよい銅張積層板が得られ、従来の亜鉛合釜層のみを
形成した銅箔からの積層板に較べて、その効果は顕著で
あり１本発明のカップリン剤膜を設けることが有効であ
ること（は明らかである。Table 2 From Table 1, even if silk J foil provided with a normal dendritic steel layer is F+1, by the treatment of the present invention, a copper-clad laminate with good peeling strength of heat-treated Ida C can be obtained, and compared to the conventional zinc alloy. The effect is remarkable compared to a laminate made of copper foil with only a pot layer formed thereon, and it is clear that the provision of the coupling agent film of the present invention is effective.
実施例（３）
実施例（２）と同−鋼箔の粗面に、実施例（２）と同様
の僧■枝状銅層を電析形成後、この銅箔を。Example (3) Same as Example (2) - After forming a triangular copper layer similar to Example (2) on the rough surface of the steel foil, this copper foil was deposited.
ンス′ン化銅５０ ｇ／−（Ｌ シアン化亜鉛３０ｇ／
Ａ、ンアン化ナトリウム９０ｇ／ｅ、炭酸すｌ・リウム
３０ｇ／−６、ロッセル塩４ ｓ ｇ／−６からなる１
［ｉ ４！４〜′洞合金メッキ浴に浸漬し、該ｔｌｌ箔
を陰極、鉛板を陽極とし。Copper cyanide 50 g/-(L Zinc cyanide 30 g/-
A, 1 consisting of 90 g/e of sodium anhydride, 30 g/-6 of sl/lium carbonate, and 4 g/-6 of Rossell's salt.
[i4!4~' Immerse in a hollow alloy plating bath, using the tll foil as a cathode and the lead plate as an anode.
浴温４０℃、電がｒ９密度ＩＡ／ｄｍ２において該＊箔
の樹枝状な１ｉｉ１１：Δに、それぞれ０．０５μとＯ
，’１２ｚｌ厚さの亜（（）〜ｒ５１１合金薄１＜ｒｑ
を形成した。ついでこの試料を濃＋ｌｆ０．３％の小り
ロム酸ナトリウム水＠液に常温で！５秒間ｌツ（ｊ’ｊ
シ、前記即鉛〜銅合金層」二に、クロメート蒲１ｉ？、
（を＋Ｗ成芒せ、？に薄ｌ１１４上にプランカップリン
グ削であるＮ−２−アミノエチル−３−アミノブロビル
トリメトキンンランを用い実ＭＭ Ｎ（１）でノホベ／
こと同様の濃度液で処理し、亜鉛〜７（ｏ’ｉ ｆｆ金
、ｊｑ−り０７！ −１−ｉｉＩＬｐ’Ｂ、カッｊ ’
） ：、ｙりＲ１ｒ’Ａり・１１′する制沓′Ｉ盆試作
し、実砲１２１ｉ （１）と同様の基土」と１７ｒ層し
て同一大きさのへ１張積層板を試作した。また比較のた
め合斂層を設けない”？ｌ’ｉ ＞＋’ｉ及び合金層と
クロメート薄１：９を設け、カップリンク剤膜は形成さ
せない鋼箔からも′側張積層板を試作し、これら積層板
の１８０°Ｃ１４８＋１．’ｒ間・鴫υし胛前後におけ
る銅箔と基材とのり・１１）誰強度を測定した。結果は
表３に示す通りである。At a bath temperature of 40°C and an electric current r9 density IA/dm2, 0.05 μ and O
, '12zl thick sub(()~r511 alloy thin 1<rq
was formed. Next, add this sample to a small amount of concentrated + lf0.3% sodium romate solution at room temperature! 5 seconds ltsu (j'j
2. Chromate layer 1i? ,
(Make a +W awn, and use N-2-aminoethyl-3-aminobrobyltrimethquine, which is a plan coupling cut, on a thin l114 plate with a real MM N(1).
Zinc~7 (o'i ff gold, jq-ri07!-1-iiILp'B, kaj'
) :, I made a prototype of a base with 11' and 17r layers of the same base as the actual gun 121i (1) and made a 1-layer laminate of the same size. . For comparison, a side-clad laminate was also prototyped from steel foil without a convergence layer and with an alloy layer and a chromate thin layer of 1:9, but without a coupling agent film. The adhesion strength between the copper foil and the base material before and after the 180° C. 148+1.r period and before and after the sintering of these laminates was measured.The results are shown in Table 3.
表３
表から１刊箔和而に、電析により樹枝状粗層を設けたも
のに対しても１本発明の亜鉛〜調合金層、りｐメート処
理、！Ｉ！膜、カップリング）′４す膜を設け／こ・、
・ｌ箔からの’１ｌｔｊ１１も積層板は、その加熱処理
前ｒ′２にむける剥離強門においてすぐれていることが
わプハっだ、。Table 3 From Table 1, it can be seen that even for those in which a dendritic coarse layer is provided by electrodeposition, the zinc-adjusted alloy layer of the present invention, RP Mate treatment,! I! (membrane, coupling)
It has been found that the laminate made from l foil is superior in terms of peel strength towards r'2 before its heat treatment.
４追Ｊ１１１の１列係
この発明は、原出ヰ：１であろ昭和５５年特許斤（１２
ｒ〜１６２３６７弓の印刷回路用錦１張積ｊ〆板を得る
／ζめに欠く′ことのてきない主要事項である釧ｊ箔の
″（１１而（ｔｉｌｌにクロメート処理膜を、さらにそ
の上に′（＋１宇／ランカ、プリング剤薄膜を形成させ
てなる銅箔に代え、・１．・Ｉ ｉ′？１ｔｌｌ而ｆｌ
’ｌｌ＋に、１ず亜鉛または１１ｉｉ、 ４１Ｂ−１，
合金１−発設け、その上にクロメート処理膜さら（てそ
の」二にＡｉＪ吉己７ランカツブリング剤薄Ｉ（１゛与
をｊヒ１ｉｌｊ ｔ、た！４１ ＋、・用量路用う同；
狛で）す１面１熱４妾着性の点において、よりすぐれた
ｊｉｊ） Ｉ＋−ｊ？ ｉｌ’ｊｆ層板の製浩忙用能と
し／ξもので、ｉα加の９２件をｌ晶するものでろる。4. 1st row clerk of J111
r ~ 162367 To obtain the brocade board for printed circuits of the bow, it is essential to obtain the final board. ni′(+1 u/Lanka, instead of copper foil formed with a thin film of pulling agent, ・1.・I i′?1tll and fl
'll+, 1z zinc or 11ii, 41B-1,
Alloy 1 was applied, and a chromate-treated film was applied on top of it, followed by AiJ Yoshimi 7-run coupling agent thin I (1. ;
Koma de)su 1 side 1 heat 4 superior jij) I+-j? It is the production of the il'jf laminate, and the 92 cases of iα addition will be crystallized.
Claims (1)
クロメート処理層を形成し、さらに該層上に一般弐ＹＲ
８ｉＸ！（ここにＹは高分子物と反応する官能基、Ｒは
Ｙとケイ素原子とを連結する鎖状または環状の炭化水素
を含む結合基、Ｘはケイ素原子に結合する有機または無
機の加水分解性の基を表わすものである。）で示される
シランカップリング剤層を設けたことを特徴とする印刷
回路用銅箔。On a thin layer of zinc or zinc alloy on the rough side of the copper foil,
A chromate treatment layer is formed, and general 2 YR is further applied on the layer.
8iX! (Here, Y is a functional group that reacts with a polymer, R is a bonding group containing a chain or cyclic hydrocarbon that connects Y and a silicon atom, and X is an organic or inorganic hydrolyzable group that is bonded to a silicon atom. A copper foil for printed circuits, characterized in that it is provided with a silane coupling agent layer represented by the following.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13529982A JPS5925297A (en) | 1982-08-03 | 1982-08-03 | Copper foil for printed circuit |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13529982A JPS5925297A (en) | 1982-08-03 | 1982-08-03 | Copper foil for printed circuit |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5925297A true JPS5925297A (en) | 1984-02-09 |
| JPH0219994B2 JPH0219994B2 (en) | 1990-05-07 |
Family
ID=15148453
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13529982A Granted JPS5925297A (en) | 1982-08-03 | 1982-08-03 | Copper foil for printed circuit |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5925297A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5071520A (en) * | 1989-10-30 | 1991-12-10 | Olin Corporation | Method of treating metal foil to improve peel strength |
| US5622782A (en) * | 1993-04-27 | 1997-04-22 | Gould Inc. | Foil with adhesion promoting layer derived from silane mixture |
| WO2009063764A1 (en) * | 2007-11-14 | 2009-05-22 | Nippon Mining & Metals Co., Ltd. | Copper foil including resistive film layer |
| JP2011127226A (en) * | 2005-06-23 | 2011-06-30 | Jx Nippon Mining & Metals Corp | Copper foil for printed wiring board |
| JP2011219789A (en) * | 2010-04-06 | 2011-11-04 | Fukuda Metal Foil & Powder Co Ltd | Treated copper foil for copper-clad laminate, copper-clad laminate obtained by sticking the treated copper foil to insulating resin substrate, and printed wiring board obtained by using the copper-clad laminate |
| KR101111930B1 (en) * | 2008-09-30 | 2012-02-14 | 이비덴 가부시키가이샤 | Multilayer printed wiring board and method for manufacturing multilayer printed wiring board |
| KR101111932B1 (en) * | 2008-09-30 | 2012-03-14 | 이비덴 가부시키가이샤 | Multilayer printed wiring board and method for manufacturing multilayer printed wiring board |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4570070B2 (en) * | 2004-03-16 | 2010-10-27 | 三井金属鉱業株式会社 | Electrolytic copper foil with carrier foil provided with resin layer for forming insulating layer, copper-clad laminate, printed wiring board, method for producing multilayer copper-clad laminate, and method for producing printed wiring board |
-
1982
- 1982-08-03 JP JP13529982A patent/JPS5925297A/en active Granted
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5071520A (en) * | 1989-10-30 | 1991-12-10 | Olin Corporation | Method of treating metal foil to improve peel strength |
| US5622782A (en) * | 1993-04-27 | 1997-04-22 | Gould Inc. | Foil with adhesion promoting layer derived from silane mixture |
| JP2011127226A (en) * | 2005-06-23 | 2011-06-30 | Jx Nippon Mining & Metals Corp | Copper foil for printed wiring board |
| WO2009063764A1 (en) * | 2007-11-14 | 2009-05-22 | Nippon Mining & Metals Co., Ltd. | Copper foil including resistive film layer |
| JP4460026B2 (en) * | 2007-11-14 | 2010-05-12 | 日鉱金属株式会社 | Copper foil with resistive film layer |
| JPWO2009063764A1 (en) * | 2007-11-14 | 2011-03-31 | 日鉱金属株式会社 | Copper foil with resistive film layer |
| US8314340B2 (en) | 2008-09-30 | 2012-11-20 | Ibiden Co., Ltd. | Multilayer printed wiring board and method for manufacturing multilayer printed wiring board |
| KR101111930B1 (en) * | 2008-09-30 | 2012-02-14 | 이비덴 가부시키가이샤 | Multilayer printed wiring board and method for manufacturing multilayer printed wiring board |
| KR101111932B1 (en) * | 2008-09-30 | 2012-03-14 | 이비덴 가부시키가이샤 | Multilayer printed wiring board and method for manufacturing multilayer printed wiring board |
| CN102802344A (en) * | 2008-09-30 | 2012-11-28 | 揖斐电株式会社 | Multilayer printed wiring board and method for manufacturing multilayer printed wiring board |
| US8633400B2 (en) | 2008-09-30 | 2014-01-21 | Ibiden Co., Ltd. | Multilayer printed wiring board and method for manufacturing multilayer printed wiring board |
| US8661665B2 (en) | 2008-09-30 | 2014-03-04 | Ibiden Co., Ltd. | Method for manufacturing multilayer printed wiring board |
| US9038266B2 (en) | 2008-09-30 | 2015-05-26 | Ibiden Co., Ltd. | Multilayer printed wiring board and method for manufacturing multilayer printed wiring board |
| JP2011219789A (en) * | 2010-04-06 | 2011-11-04 | Fukuda Metal Foil & Powder Co Ltd | Treated copper foil for copper-clad laminate, copper-clad laminate obtained by sticking the treated copper foil to insulating resin substrate, and printed wiring board obtained by using the copper-clad laminate |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0219994B2 (en) | 1990-05-07 |
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