JPH0732306B2 - Copper foil for printed circuit and manufacturing method thereof - Google Patents
Copper foil for printed circuit and manufacturing method thereofInfo
- Publication number
- JPH0732306B2 JPH0732306B2 JP3111539A JP11153991A JPH0732306B2 JP H0732306 B2 JPH0732306 B2 JP H0732306B2 JP 3111539 A JP3111539 A JP 3111539A JP 11153991 A JP11153991 A JP 11153991A JP H0732306 B2 JPH0732306 B2 JP H0732306B2
- Authority
- JP
- Japan
- Prior art keywords
- copper foil
- layer
- zinc
- phosphorus
- resistant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
Landscapes
- Parts Printed On Printed Circuit Boards (AREA)
- Electroplating Methods And Accessories (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Manufacturing Of Printed Wiring (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は銅の表面処理被膜に関す
るもので、特に詳しくは、耐熱変色性防錆被膜を有する
印刷回路用銅箔およびその製造方法に関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a copper surface-treated coating, and more particularly to a copper foil for printed circuits having a heat-resistant, discoloration-resistant and rust-proof coating and a method for producing the same.
【０００２】[0002]
【従来の技術】印刷回路板は年々急速に成長しており、
高性能化、高信頼性の要求が高まっており、印刷回路用
銅箔に対してもその要求はますます複雑で厳しいものに
なっている。2. Description of the Related Art Printed circuit boards are growing rapidly year by year,
The demands for higher performance and higher reliability are increasing, and the requirements for copper foil for printed circuits are becoming more and more complicated and demanding.
【０００３】印刷回路板製造の第１段階は、まず銅箔を
合成樹脂含浸基材に積層し、プレスにより高温加熱圧着
して、銅張積層板を得ることである。この場合、民生用
の紙フェノール基材などではプレス温度は 150〜160 ℃
程度であるが、産業用のガラスエポキシ基材となると、
10〜20℃温度が高く、また最近増加しつつある高温耐熱
性樹脂基材やポリイミド樹脂基材などではさらに高温を
必要とする。また、印刷回路板の高密度化や高多層化に
伴って、寸法変化率を縮小するため、プレス後、ポスト
キュア (高温加熱保持) を行う場合が出てきた。そのた
め、銅箔の樹脂との接合面でない光沢面側は通常、高温
での長時間の保持で熱酸化を受けやすく、その面が無処
理であれば、強度に酸化変色が生じ、表面特性的にも、
外観的にも製品の価値が全くないものとなる。The first step in the production of a printed circuit board is to first laminate a copper foil on a synthetic resin-impregnated base material and press-heat it at a high temperature to obtain a copper-clad laminate. In this case, the pressing temperature is 150 to 160 ° C for consumer-use paper phenol substrates.
To some extent, when it comes to industrial glass epoxy substrates,
The temperature is high at 10 to 20 ° C, and the high temperature heat resistant resin base material and the polyimide resin base material which are increasing recently require higher temperature. In addition, post-cure (high-temperature heating and holding) has been performed after pressing in order to reduce the dimensional change rate with the increase in density and multilayer of printed circuit boards. Therefore, the glossy side of the copper foil, which is not the surface to be joined with the resin, is usually susceptible to thermal oxidation when held at high temperature for a long time, and if that surface is not treated, strong oxidative discoloration occurs and the surface characteristic Also,
In terms of appearance, the product has no value.
【０００４】そのため、従来はたとえば特公昭54-29187
には、亜鉛を含むアルカリ性水溶液中に銅を浸漬する
か、あるいは同水溶液中で銅を陽極として通電すること
により被膜を形成する方法や、また、特公昭58-7077に
は亜鉛または酸化亜鉛とクロム酸化物とよりなる混合物
の被覆層を設ける方法、また特公昭58-53079には銅−錫
合金被膜を形成する方法などがある。さらにまた、特開
昭57-152490 には６価クロム化合物と水溶性亜鉛化合
物、および硫酸ナトリウムを加えたｐＨ 6.5以下の浴中
で銅箔を陰極電解する方法がある。Therefore, conventionally, for example, Japanese Examined Patent Publication No. 54-29187
Is a method of forming a coating by immersing copper in an alkaline aqueous solution containing zinc, or by energizing copper in the same aqueous solution as an anode, and in Japanese Patent Publication No. 58-7077, zinc or zinc oxide is used. There is a method of forming a coating layer of a mixture of chromium oxide and a method of forming a copper-tin alloy coating in Japanese Patent Publication No. 58-53079. Further, JP-A-57-152490 discloses a method of cathodic electrolyzing a copper foil in a bath containing a hexavalent chromium compound, a water-soluble zinc compound, and sodium sulfate and having a pH of 6.5 or less.
【０００５】しかし、上記に述べた従来の方法では次の
ような問題点がある。クロム、亜鉛の共析被膜の場合や
銅−錫合金被膜の場合は、これだけでは 200℃１時間と
いった高温長時間に対し、耐熱変色性がないし、樹脂と
の積層プレス後ポストキュアに対する耐熱性が全くな
い。また、積層プレスに至るまでの保存における経時酸
化に対する防錆効果も不十分である。また、亜鉛をメッ
キさせる方法で、その量を増加させれば耐熱変色性が向
上するが、亜鉛を多量に析出させると、外観上灰色を呈
し、積層プレス後でも黄銅色となり、また、半田濡れ性
の障害となるので、商品価値の無いものとなる。However, the conventional method described above has the following problems. Chromium and zinc eutectoid coatings or copper-tin alloy coatings do not have heat discoloration resistance at high temperature and long time such as 200 ° C for 1 hour, and have heat resistance to post cure after lamination press with resin. Not at all. In addition, the rust preventive effect against oxidation over time during storage up to the lamination press is insufficient. In addition, when the amount of zinc is increased by the method of plating with zinc, the heat discoloration resistance is improved, but when a large amount of zinc is deposited, it will appear gray in appearance, and will have a brass color even after lamination pressing, and will also get wet with solder. It becomes a sexual impediment and has no commercial value.
【０００６】[0006]
【発明が解決しようとする課題】本発明者らは前記した
従来の技術の問題点に鑑み、種々研究、検討した結果、
従来の耐熱変色性防錆被膜にシランカップリング剤およ
び、りんまたはりん化合物からなる第２層を加えること
によって、優れた性能をもつ耐熱変色性防錆被膜を有す
る銅箔が得られることを見出し、本発明を完成した。DISCLOSURE OF INVENTION Problems to be Solved by the Invention In view of the problems of the above-mentioned conventional techniques, the present inventors have conducted various researches and studies, and as a result,
It has been found that by adding a silane coupling agent and a second layer made of phosphorus or a phosphorus compound to a conventional heat-resistant tarnish-resistant rust-preventive coating, a copper foil having a heat-resistant tarnish-resistant rust-proof coating having excellent performance can be obtained. The present invention has been completed.
【０００７】[0007]
【問題を解決するための手段】すなわち、本発明は銅箔
の少なくとも光沢面側表面層が、亜鉛または亜鉛を主と
する混合物層、化合物層または合金層である第１層と、
その上にシランカップリング剤および、りんまたはりん
化合物からなる第２層より構成されることを特徴とす
る、耐熱変色性防錆被膜を有する印刷回路用銅箔であ
り、必要に応じて、第１層が亜鉛または酸化亜鉛と、ク
ロム酸化物からなる、混合物または化合物層であること
を特徴する、あるいは、第１層が亜鉛または亜鉛を主と
する合金層と、その表面にクロメート処理されたクロム
酸化物層を有することを特徴とする印刷回路用銅箔であ
る。また、本発明の製造方法は銅箔の少なくとも光沢面
側を亜鉛およびクロムイオンを含むアルカリ浴中で陰極
電解処理し、次いでその処理面上にシランカップリング
剤および、りんまたはりん化合物を含む溶液を塗布して
耐熱変色性防錆被膜を形成する印刷回路用銅箔の製造方
法、または銅箔の少なくとも光沢面側を亜鉛または亜鉛
合金の微量メッキ被膜を設け、次にクロメート処理し、
その上にシランカップリング剤および、りんまたはりん
化合物を含む溶液を塗布して耐熱変色性防錆被膜を形成
する印刷回路用銅箔の製造方法である。That is, the present invention provides a first layer in which at least the gloss surface side surface layer of a copper foil is zinc or a mixture layer mainly containing zinc, a compound layer or an alloy layer,
A copper foil for a printed circuit having a heat-resistant discoloration-resistant rust-preventive coating, characterized in that it comprises a silane coupling agent and a second layer comprising phosphorus or a phosphorus compound thereon. One layer is a mixture or compound layer consisting of zinc or zinc oxide and chromium oxide, or the first layer is zinc or an alloy layer mainly containing zinc and its surface is chromated A copper foil for a printed circuit having a chromium oxide layer. Further, in the production method of the present invention, at least the shiny side of the copper foil is subjected to cathodic electrolysis treatment in an alkaline bath containing zinc and chromium ions, and then a solution containing a silane coupling agent and phosphorus or a phosphorus compound on the treated surface. A method for producing a copper foil for a printed circuit in which a heat-resistant discoloration-resistant rust-preventive coating is formed by applying, or at least a shiny side of the copper foil is provided with a microplating coating of zinc or a zinc alloy, and then chromate-treated,
A method for producing a copper foil for a printed circuit, in which a solution containing a silane coupling agent and phosphorus or a phosphorus compound is applied thereon to form a heat-resistant discoloration-resistant rust-preventive coating.
【０００８】[0008]
【作用】本発明の第２層は非常に薄い被膜であるが、そ
の耐熱効果は著しく、同時にまた半田濡れ性、レジスト
密着性に対し障害とならない。The second layer of the present invention is a very thin film, but its heat resistance effect is remarkable, and at the same time, it does not hinder solder wettability and resist adhesion.
【０００９】シランカップリング剤はＳｉとして好まし
くは0.01〜20mg/m2 、さらに好ましくは 0.1〜10mg/m2
である。りんまたはりん化合物の量はＰとして好ましく
は0.01〜20mg/m2 、さらに好ましくは 0.1〜10mg/m2 で
ある。Ｓｉ，Ｐとも量が少ない場合は本発明の耐熱変色
性の効果が低く、量が多い場合は乾燥ムラやシミが発生
しやすくなるため外観上良いものが得られにくい。この
第２層のコーティング方法は、シランカップリング剤、
りん化合物を含む水溶液、あるいは有機溶剤を銅箔表面
にスプレーコーティングあるいは溶液中浸漬を行い、乾
燥させることで達成される。シランカップリング剤とり
ん化合物とは別々に連続して処理しても良いが、同時処
理の方が工程上有利である。The silane coupling agent is preferably 0.01 to 20 mg / m 2 , more preferably 0.1 to 10 mg / m 2 as Si.
Is. The amount of phosphorus or phosphorus compound as P is preferably 0.01 to 20 mg / m 2 , more preferably 0.1 to 10 mg / m 2 . When the amounts of both Si and P are small, the effect of the heat discoloration resistance of the present invention is low, and when the amounts are large, unevenness in drying and stains are likely to occur, and it is difficult to obtain a good appearance. This second layer is coated with a silane coupling agent,
This can be achieved by spray-coating or dipping an aqueous solution containing a phosphorus compound or an organic solvent on the copper foil surface and then drying. The silane coupling agent and the phosphorus compound may be separately and continuously treated, but simultaneous treatment is advantageous in terms of process.
【００１０】シランカップリング剤は、一般式YRSiX3(
ここでＹは高分子物と反応する官能基、ＲはＹとＳｉと
を結合する炭化水素を含む結合基、ＸはＳｉに結合する
加水分解性基を表す）なるものであり、例えば、γ−ア
ミノプロピルトリエトキシシラン、Ｎ−β−アミノエチ
ル−γ−アミノプロピルトリメトキシシラン、γ−グリ
シドキシトリメトキシシラン、γ−ウレイドプロピルト
リエトキシシランなどを使用する。The silane coupling agent has the general formula YRSiX 3 (
Here, Y represents a functional group that reacts with a polymer, R represents a bonding group containing a hydrocarbon that bonds Y and Si, and X represents a hydrolyzable group that bonds to Si). -Aminopropyltriethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, γ-glycidoxytrimethoxysilane, γ-ureidopropyltriethoxysilane and the like are used.
【００１１】りんの供給剤はりん、またはりん化合物と
して、例えばりん酸、りん酸のアルカリ金属塩、トリポ
リリン酸、トリポリリン酸のアルカリ金属塩、ピロリン
酸、ピロリン酸のアルカリ金属塩、リン酸トリエチル、
リン酸トリメチルなどが上げられる。しかし、ナトリウ
ム塩およびカリウム塩は、耐熱変色性に効果はあるが、
その量が多いと、防錆力が低下するため、その量を少な
くするか、もしくは、使用しない方が良い。リチウム塩
は防錆に効果がある。The phosphorus supply agent is phosphorus or a phosphorus compound such as phosphoric acid, an alkali metal salt of phosphoric acid, tripolyphosphoric acid, an alkali metal salt of tripolyphosphoric acid, pyrophosphoric acid, an alkali metal salt of pyrophosphoric acid, triethyl phosphate, or the like.
Examples include trimethyl phosphate. However, sodium salt and potassium salt are effective in heat discoloration resistance,
If the amount is large, the rust preventive power is lowered, so it is better to reduce the amount or not use it. Lithium salt is effective for rust prevention.
【００１２】りん酸を用いた水溶液を例に取れば、りん
酸(85%) が0.01〜0.5cc/l 、シランカップリング剤は0.
01〜10g/l の範囲が良い。なお、りん化合物とシランカ
ップリング剤の溶液は水溶液の場合、ｐＨが 5.0〜12.
0、さらに好ましくは 6.0〜11.0でなければならない。
このｐＨ範囲以外の場合は、第１層中のＺｎが溶解除去
されてしまうからである。りん化合物とシランカップリ
ング剤のどちらか一方では耐熱効果は低く、両者の存在
で始めて本発明の効果が発揮される。Taking an aqueous solution using phosphoric acid as an example, phosphoric acid (85%) is 0.01 to 0.5 cc / l, and the silane coupling agent is 0.1.
A range of 01-10g / l is good. When the solution of the phosphorus compound and the silane coupling agent is an aqueous solution, the pH is 5.0 to 12.
It should be 0, more preferably 6.0-11.0.
This is because Zn in the first layer will be dissolved and removed if it is outside this pH range. Either one of the phosphorus compound and the silane coupling agent has a low heat resistance effect, and the effect of the present invention is exhibited only when both are present.
【００１３】本発明の第１層は第２層の前に当然処理さ
れるものであり、亜鉛を主とする混合物層、化合物層ま
たは合金層における添加元素としてはＣｒの他にＣｕ，
Ｎｉ，Ｃｏ，Ｓｎ，Ｍｇ，Ａｌ，Ｓｉ，Ｐ，Ｍｏ，Ｗ，
Ｖが上げられ、その一つ以上を選択することができる
が、主体はＺｎであり、添加元素の代表はＣｒである。
第１層の形成方法としては、例えば特公昭58-15950の方
法などによりＺｎ、Ｃｒの化合物層を形成させるが、亜
鉛または亜鉛合金を極く微量にメッキさせても良い。こ
の場合は、この亜鉛または亜鉛合金層表面にクロメート
処理を施す方が耐熱性、防錆性とも向上する。Ｚｎまた
はＺｎ化合物の被覆量はＺｎとして 1〜50mg/m2 、好ま
しくは３〜20mg/m2 が良い。Ｃｒを含む場合は、Ｃｒと
して0.1〜10mg/m2 、好ましくは 0.5〜5mg/m2が良い。
Ｚｎ，Ｃｒともその量が少ない場合は第２層が適当量で
あっても、耐熱効果が低く、多い場合は半田濡れ性の障
害となったり、外観色調の問題となったりする。The first layer of the present invention is naturally treated before the second layer, and as the additive element in the mixture layer, compound layer or alloy layer mainly containing zinc, Cu, Cu,
Ni, Co, Sn, Mg, Al, Si, P, Mo, W,
Although V can be increased and one or more of them can be selected, the main component is Zn and the representative additive element is Cr.
As a method of forming the first layer, a compound layer of Zn and Cr is formed by, for example, the method of Japanese Patent Publication No. 58-15950, but zinc or zinc alloy may be plated in an extremely small amount. In this case, heat treatment and rust prevention are improved by subjecting the surface of the zinc or zinc alloy layer to chromate treatment. The coverage of the Zn or Zn compounds 1 to 50 mg / m 2 as Zn, preferably from 3 to 20 mg / m 2. When Cr is contained, the Cr content is 0.1 to 10 mg / m 2 , preferably 0.5 to 5 mg / m 2 .
When both Zn and Cr are small in amount, the heat resistance effect is low even if the amount of the second layer is appropriate, and when the amount is large, solder wettability is impaired and appearance color tone becomes a problem.
【００１４】[0014]
【実施例】以下、本発明の実施例について述べる。 実施例(1) ３５μm 厚さの電解銅箔の光沢面を なる浴中で2A/dm2 ,10秒間陰極電解し、水洗後、 （Ｂ） γ−アミノプロピルトリエトキシシラン 1.0 cc/l りん酸(85%) 0.13cc/l なる液を吹き付け、乾燥させた。この銅箔の特性試験結
果を表２に示す。また、この耐熱防錆被膜のＺｎ量は7.
0mg/m2、Ｃｒ量は1.8mg/m2、Ｓｉは 4mg/m2 、Ｐは 2mg
/m2 であった。なお、分析はＺｎ，Ｃｒ，ＳｉをＩＣＰ
発光分光分析法、Ｐを吸光光度法により行なった。EXAMPLES Examples of the present invention will be described below. Example (1) A glossy surface of an electrolytic copper foil having a thickness of 35 μm was applied. Consisting 2A / dm 2, 10 sec to cathodic electrolysis in a bath, washed with water, spraying (B) .gamma.-aminopropyltriethoxysilane 1.0 cc / l phosphoric acid (85%) 0.13cc / l becomes liquid, and dried . Table 2 shows the characteristic test results of this copper foil. The Zn content of this heat-resistant and rustproof coating is 7.
0mg / m 2 , Cr content 1.8mg / m 2 , Si 4mg / m 2 , P 2mg
It was / m 2 . In addition, analysis uses Zn, Cr, Si for ICP
Emission spectroscopy, P was performed by absorptiometry.
【００１５】実施例(2) ３５μm 厚さの電解銅箔の光沢面を実施例(1) でのＡ浴
のかわりに下記Ｃ浴を用い、 0.15A/dm2 、 3秒間陰極電解して、亜鉛の微量メッキを
した後、水洗し、 の浴中で0.2A/dm2、３秒間陰極電解した。次いで、水洗
後、実施例(1) と同じ (Ｂ) 液を吹き付け乾燥させた。
この銅箔の特性試験結果を表２に示す。Example (2) The following C bath was used in place of the A bath in Example (1) for the glossy surface of the electrolytic copper foil having a thickness of 35 μm. Cathodic electrolysis for 0.15A / dm 2 for 3 seconds, microplating of zinc, then washing with water, In the bath of 0.2 A / dm 2 , cathodic electrolysis was performed for 3 seconds. Then, after washing with water, the same liquid (B) as in Example (1) was sprayed and dried.
Table 2 shows the characteristic test results of this copper foil.
【００１６】実施例 (3)〜(8) ３５μm 厚さの電解銅箔の光沢面に実施例(1) と同じＡ
浴を用い、2 A/dm2 、10秒間陰極電解し、水洗後、表１
に示すようなシランカップリング剤とりん化合物の組成
の液を吹き付け、乾燥させた。この銅箔の特性試験結果
を表２の実施例(3)〜(8) に示す。Examples (3) to (8) The same A as Example (1) was applied to the glossy surface of an electrolytic copper foil having a thickness of 35 μm.
Using a bath, conduct cathodic electrolysis for 10 seconds at 2 A / dm 2 , wash with water, and then
A liquid having a composition of a silane coupling agent and a phosphorus compound as shown in (3) was sprayed and dried. The characteristic test results of this copper foil are shown in Examples (3) to (8) of Table 2.
【００１７】[0017]
【表１】 [Table 1]
【００１８】比較例 (1) ３５μm 厚さの電解銅箔の光沢面を実施例(1) と同じＡ
浴で2A/dm2 、10秒間陰極電解し、水洗し、乾燥させ
た。この銅箔の特性試験結果を表２に示す。Comparative Example (1) The glossy surface of an electrolytic copper foil having a thickness of 35 μm was the same as in Example (1) A
It was subjected to cathodic electrolysis in a bath at 2 A / dm 2 for 10 seconds, washed with water, and dried. Table 2 shows the characteristic test results of this copper foil.
【００１９】[0019]
【表２】 [Table 2]
【００２０】比較例 (2) ３５μm 厚さの電解銅箔の光沢面を実施例(1) と同じＡ
浴で2A/dm2 、10秒間陰極電解し、水洗し、Ｎ−β−ア
ミノエチル−γ−アミノプロピルトリエトキシシラン0.
5cc/l の水溶液を吹き付け、乾燥させた。この銅箔の特
性試験結果を表２に示す。Comparative Example (2) The glossy surface of an electrolytic copper foil having a thickness of 35 μm was the same as in Example (1) A
Cathodic electrolysis in a bath at 2 A / dm 2 for 10 seconds, washing with water, and N-β-aminoethyl-γ-aminopropyltriethoxysilane.
A 5 cc / l aqueous solution was sprayed and dried. Table 2 shows the characteristic test results of this copper foil.
【００２１】比較例 (3) ３５μm 厚さの電解銅箔の光沢面に実施例(1) と同じＡ
浴で2A/dm2 、10秒間陰極電解し、水洗し、りん酸三ナ
トリウム0.2g/lの水溶液を吹き付け、乾燥させた。この
銅箔の特性試験結果を表２に示す。Comparative Example (3) The same A as in Example (1) was applied to the glossy surface of an electrolytic copper foil having a thickness of 35 μm.
It was subjected to cathodic electrolysis for 10 seconds in a bath at 2 A / dm 2 , washed with water, sprayed with an aqueous solution of trisodium phosphate 0.2 g / l, and dried. Table 2 shows the characteristic test results of this copper foil.
【００２２】なお、表２における「銅箔加熱変色性」は
銅箔単体での熱風循環式オーブン中の加熱酸化変色性
を，「ポストキュア」は銅箔をFR-4グレードの樹脂基材
に積層プレスし、これの銅箔光沢面の同じオーブン中加
熱酸化変色性を見ている。また、その判定は、 ○：全く変色無し □：わずかに変色あり △：やや変色あり ×：全面変色 ××：全面強度に変色 である。また、半田濡れ性はIPC-CF-150E,4-12項目を基
本とし、1/10Ｎ塩酸水溶液中に25℃、10秒間浸漬後、水
洗、乾燥し、ＷＷＧロジンフラックスを塗布後、 235℃
半田中に浸漬し、その濡れ度合いを目視判定した。○は
全面濡れたことを示す。レジスト密着性はFR-4グレード
の樹脂基材にプレス成形後、ＵＶソルダーレジストをス
クリーン印刷し、ＵＶ照射装置で硬化させ、塗膜硬度を
鉛筆硬度法で測定した。○は４Ｈ以上であったことを示
す。防錆テストは銅箔を６０℃, ８５％相対湿度に保っ
た恒温恒湿器中で７２時間保持し、その酸化変色度合い
を目視観察した。良好なものから、○、△、×の順で判
定した。"Copper foil heat discoloration" in Table 2 is the heat oxidative discoloration of a copper foil alone in a hot air circulation type oven, and "Post cure" is the copper foil as a FR-4 grade resin substrate. Laminate press and look at the oxidative discoloration of the copper foil shiny side of this upon heating in the same oven. In addition, the judgment is: ◯: no discoloration at all □: slightly discoloration Δ: slightly discoloration ×: discoloration on entire surface xx: discoloration on entire surface strength Also, solder wettability is basically based on IPC-CF-150E, 4-12 items, soaked in a 1 / 10N hydrochloric acid aqueous solution at 25 ° C for 10 seconds, washed with water, dried, and applied with WWG rosin flux at 235 ° C.
It was dipped in solder and the degree of wetting was visually determined. ○ indicates that the entire surface was wet. The resist adhesion was measured by press molding a FR-4 grade resin substrate, screen-printing a UV solder resist, curing it with a UV irradiation device, and measuring the coating film hardness by the pencil hardness method. ◯ indicates that it was 4H or more. In the rust prevention test, the copper foil was kept for 72 hours in a thermo-hygrostat kept at 60 ° C. and 85% relative humidity, and the degree of oxidative discoloration was visually observed. It was judged in the order of good, good, and bad from the good one.
【００２３】[0023]
【発明の効果】表２に示す通り、本発明の耐熱変色性防
錆被膜は比較例に比べて、格段の耐熱性の向上が認めら
れ、特にポストキュア（積層プレス後加熱）における耐
熱性に優れるものである。また、経時酸化防止の効果も
あり、さらに、半田濡れ性や、レジスト密着性の障害と
はならず、総合的に優れた銅箔を提供できるものであ
る。また、本発明の製造方法は製造工程上、容易に実施
できるものであり、その効果は極めて高い。As shown in Table 2, the heat-resistant discoloration rust-preventive coating of the present invention is remarkably improved in heat resistance as compared with Comparative Examples, and particularly in heat resistance in post cure (heating after lamination press). It is excellent. In addition, it also has an effect of preventing oxidation over time, and further, does not hinder the solder wettability and the resist adhesiveness, and can provide an overall excellent copper foil. Further, the manufacturing method of the present invention can be easily implemented in the manufacturing process, and its effect is extremely high.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特公 平３−14915（ＪＰ，Ｂ２) 特公 昭61−33907（ＪＰ，Ｂ２) ─────────────────────────────────────────────────── ─── Continued Front Page (56) References Japanese Patent Publication No. 3-14915 (JP, B2) Japanese Patent Publication No. 61-33907 (JP, B2)
Claims (5)
鉛または亜鉛を主とする混合物層、化合物層または合金
層である第１層と、その上にシランカップリング剤およ
び、りんまたはりん化合物からなる第２層より構成され
ることを特徴とする、耐熱変色性防錆被膜を有する印刷
回路用銅箔。1. A first layer in which at least the surface layer on the glossy side of a copper foil is zinc or a mixture layer mainly containing zinc, a compound layer or an alloy layer, and a silane coupling agent and phosphorus or phosphorus on the first layer. A copper foil for a printed circuit having a heat-resistant, discoloration-resistant and anticorrosive coating, comprising a second layer made of a compound.
酸化物からなる、混合物または化合物層であることを特
徴とする請求項１の印刷回路用銅箔。2. The copper foil for a printed circuit according to claim 1, wherein the first layer is a mixture or compound layer containing zinc or zinc oxide and chromium oxide.
層と、その表面にクロメート処理されたクロム酸化物を
有することを特徴とする請求項１の印刷回路用銅箔。3. The copper foil for a printed circuit according to claim 1, wherein the first layer has zinc or an alloy layer mainly containing zinc and chromate-treated chromium oxide on the surface thereof.
クロムイオンを含むアルカリ浴中で陰極電解処理し、次
いでその処理面上にシランカップリング剤および、りん
またはりん化合物を含む溶液を塗布して耐熱変色性防錆
被膜を形成する印刷回路用銅箔の製造方法。4. A copper foil is subjected to cathodic electrolysis on at least the shiny side of the copper foil in an alkaline bath containing zinc and chromium ions, and then the treated surface is coated with a solution containing a silane coupling agent and phosphorus or a phosphorus compound. A method for producing a copper foil for printed circuits, which forms a heat-resistant, discoloration-resistant, rustproof coating.
亜鉛合金の微量メッキ被膜を設け、次にクロメート処理
し、その上にシランカップリング剤および、りんまたは
りん化合物を含む溶液を塗布して耐熱変色性防錆被膜を
形成する印刷回路用銅箔の製造方法。5. A copper foil is provided with a zinc or zinc alloy microplating coating on at least the shiny side, then chromate treated, and a solution containing a silane coupling agent and phosphorus or phosphorus compound is applied thereon. A method for producing a copper foil for a printed circuit, which forms a heat-resistant discoloration rustproof film.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3111539A JPH0732306B2 (en) | 1991-05-16 | 1991-05-16 | Copper foil for printed circuit and manufacturing method thereof |
| US07/924,527 US5338619A (en) | 1991-05-16 | 1992-08-04 | Copper foil for printed circuits and method of producing same |
| US08/041,383 US5356528A (en) | 1991-05-16 | 1993-04-01 | Copper foil for printed circuits and method of producing same |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3111539A JPH0732306B2 (en) | 1991-05-16 | 1991-05-16 | Copper foil for printed circuit and manufacturing method thereof |
| US07/924,527 US5338619A (en) | 1991-05-16 | 1992-08-04 | Copper foil for printed circuits and method of producing same |
| US08/041,383 US5356528A (en) | 1991-05-16 | 1993-04-01 | Copper foil for printed circuits and method of producing same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04338694A JPH04338694A (en) | 1992-11-25 |
| JPH0732306B2 true JPH0732306B2 (en) | 1995-04-10 |
Family
ID=27311987
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3111539A Expired - Fee Related JPH0732306B2 (en) | 1991-05-16 | 1991-05-16 | Copper foil for printed circuit and manufacturing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0732306B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3329572B2 (en) * | 1994-04-15 | 2002-09-30 | 福田金属箔粉工業株式会社 | Copper foil for printed circuit and surface treatment method thereof |
| JP2006028597A (en) * | 2004-07-16 | 2006-02-02 | Dipsol Chem Co Ltd | Rust-preventive treatment agent and rust-preventive treatment method |
| JP4660819B2 (en) * | 2005-12-15 | 2011-03-30 | 福田金属箔粉工業株式会社 | Copper foil for flexible printed wiring boards for COF |
| JP2012158828A (en) * | 2011-02-03 | 2012-08-23 | Furukawa Electric Co Ltd:The | Surface-treated copper foil, and method for production thereof |
| JP5919656B2 (en) * | 2011-06-14 | 2016-05-18 | 大日本印刷株式会社 | Conductive substrate for wiring pattern formation of current collector sheet for solar cell |
| TWI536581B (en) | 2011-06-14 | 2016-06-01 | Dainippon Printing Co Ltd | A conductive substrate for forming a wiring pattern for a solar cell collector sheet, and a method for manufacturing a current collector for a solar cell |
-
1991
- 1991-05-16 JP JP3111539A patent/JPH0732306B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04338694A (en) | 1992-11-25 |
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