JP4370074B2 - Copper foil for printed wiring board and manufacturing method thereof - Google Patents
Copper foil for printed wiring board and manufacturing method thereof Download PDFInfo
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- JP4370074B2 JP4370074B2 JP2002026439A JP2002026439A JP4370074B2 JP 4370074 B2 JP4370074 B2 JP 4370074B2 JP 2002026439 A JP2002026439 A JP 2002026439A JP 2002026439 A JP2002026439 A JP 2002026439A JP 4370074 B2 JP4370074 B2 JP 4370074B2
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Description
【０００１】
【産業上の利用分野】
本発明は、プリント配線板用銅箔とその製造方法に関する。
【０００２】
【従来の技術】
電子機器に用いられるプリント配線板は、銅張積層板に対してエッチング加工を行うことで銅箔の不要部分を除去し、回路配線を形成している。銅張積層板は、ガラス繊維布にエポキシ樹脂を含浸させた基材と、銅箔とを、積層成型して製造される。また、無機フィラーを含有するエポキシ樹脂フィルムを銅箔上に形成した樹脂付銅箔を用いることも行われている。樹脂付銅箔に用いられるエポキシ樹脂フィルムの厚さは、回路配線層間の絶縁を確保するために通常１００μｍ程度である。プリント配線板は製造工程において過酷な処理条件にさらされ、また、長期に使用されるため、高度な信頼性が要求され、銅箔と基材間の高い引きはがし強さが特に要求される。このため、銅箔と基材間の引きはがし強さを物理的に向上させることを目的として、酸性銅メッキ浴等による粗化処理が銅箔に対して行われている。また、引きはがし強さを化学的に向上させることを目的として、シランカップリング剤によるカップリング剤処理を行なうことが、特開昭５７−８７３２４号公報に記載されている。また、特開平８−１９３１８８号公報には、粗化処理を行なわない銅箔上に、ゴム変成エポキシ樹脂組成物からなる接着剤層を形成した、接着剤付銅箔が記載されている。この接着剤層の厚さは、特に規定されてはいないが、実施例からみて３０μｍ程度である。
【０００３】
【発明が解決しようとする課題】
プリント配線板は、電子技術の高度化に伴って急速な技術的進歩を遂げており、プリント配線板を構成する銅箔に要求される性能も厳しさを増している。特に電子機器の小型化・高性能化の進展に伴う回路配線の高密度化とデータ転送の高速化に対応するため、表面粗さの小さい銅箔が望まれている。表面粗さの小さい銅箔を用いることでエッチング加工性が向上して微細な回路配線の形成が容易になり、高密度な回路配線を実現することができるとともに、信号波形の乱れの原因となる回路配線表面の凹凸が減少することでデータ転送の高速化を実現できるが、基材との物理的な相互作用が減少して回路配線の引きはがし強さが低下する。また、基材の高耐熱性、高弾性率、低熱膨張率化等の高機能化に対応して、基材中の無機フィラが増加する傾向にある。このため、基材中の樹脂分が減少した結果、塑性変形による応力緩和などが小さくなり、引きはがし強さが低下する傾向にある。引きはがし強さを高くするために樹脂を変性させると、基材の特性が損なわれる恐れがある。
【０００４】
本発明は、回路配線の微細化及び基材の高機能化に対応するため、表面粗さを上げることなく、引きはがし強さに優れるプリント配線板用銅箔とその製造方法を提供するものである。
【０００５】
【課題を解決するための手段】
本発明者らは鋭意検討の結果、重量平均分子量が７０，０００以上のエポキシ重合体からなり、厚さが、重量換算厚さで０．５〜５ｇ／ｍ 2 である接着性付与層を設けることにより、表面粗さの小さい平滑な銅箔を用いても実用上十分な引きはがし強さが得られることを見出し、本発明を完成するに至った。すなわち、本発明は、防錆処理層と、カップリング剤処理層と、重量平均分子量が７０，０００以上のエポキシ樹脂重合体からなり、厚さが、重量換算厚さで０．５〜５ｇ／ｍ 2 である接着性付与層とを有することを特徴とするプリント配線板用銅箔である。カップリング剤としては、エポキシシラン系カップリング剤を用いることにより、引きはがし強さに優れたプリント配線板用銅箔が得られる。
【０００６】
さらに本発明は、重量平均分子量が７０，０００以上のエポキシ樹脂重合体からなる接着性付与層を形成してプリント配線板用銅箔を製造する工程において、エポキシ樹脂重合体を１〜１０％含有する溶液を銅箔に塗工することを特徴とするプリント配線板用銅箔の製造方法である。
【０００７】
【発明の実施の形態】
本発明のプリント配線板用銅箔に用いる銅箔の種類は、電解銅箔、圧延銅箔のいずれでもよく、厚さについては３〜７０μｍが好適であり、特に好ましくは３〜１８μｍがさらに好適である。銅箔が７０μｍよりも厚いとエッチング加工が困難となり、３μｍよりも薄いと取扱いが困難となる。電解銅箔には光沢面と非光沢面の２種類の表面があり、各々表面形状と表面粗さが異なるが、本発明においては接着性付与層をどちらの表面上に設けてもよい。表面粗さは、１０点平均粗さで０．５〜１０μｍが好適であり、特に好ましくは０．５〜３μｍがさらに好適である。表面粗さが０．５μｍよりも小さいと、銅箔自体の製造が困難になる。一方、３μｍよりも大きいと、基材樹脂に埋没した部分が増加してエッチング加工が困難となる。さらに、表面粗さが大きいと高周波信号の波形に乱れが生じやすくなるので、高周波回路に用いる場合には、表面粗さが上記の範囲内で小さいことが好ましい。表面粗さが上記の範囲であれば、粗化処理が行われていない銅箔も使用することができる。粗化処理が行われていない銅箔を用いた鋼張積層板は、基材樹脂に埋没した粗化粒子が存在しないため、特にエッチング加工性に優れる。
【０００８】
また、本発明において、銅箔の被接着面には、防錆処理層、カップリング剤処理層を設ける必要がある。防錆処理層としてはクロメート処理層のほか、亜鉛を含有する亜鉛−クロメート処理層、亜鉛とアルミニウムとからなる複合処理層等があり、これらの防錆処理層は酸素や水分を遮断して、銅ないし上記の金属処理層及び合金処理層の経時劣化を防止する。防錆処理層は、対応する金属イオンまたはその錯イオンを含有する処理浴中で浸漬または電解処理を行なうことにより形成することができる。シランカップリング剤処理層は、各種のカップリング剤の水溶液、水分散液、溶液等を防錆処理層上に塗工、噴霧等の各種の方法により形成することができる。カップリング剤としては、各種のシランカップリング剤を単独あるいは混合して用いることができ、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス（β−メトキシエトキシ）シラン、β−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルメチルジエトキシシラン、γ−グリシドキシプロピルトリエトキシシラン、γ−メタクリロキシプロピルメチルジメトキシシラン、γ−メタクリロキシプロピルトリメトキシシラン、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、γ−アミノプロピルトリメトキシシラン、Ｎ−フェニル−γ−アミノプロピルトリエトキシシラン、γ−クロロプロピルトリメトキシシラン、γ−メルカプトプロピルトリメトキシシラン、γ−メルカプトプロピルメチルジメトキシシラン等を用いることができる。さらには、上記したシランカップリング剤１種以上を混合して使用する。特に好ましくはエポキシシランがさらに好適である。また、必要であれば上記のシランカップリング剤とテトラメトキシシラン、テトラエトキシシラン、テトラプロポキシシラン、テトラブトキシシラン等のテトラアルコキシシランあるいは水ガラス、ケイ酸リチウム、ケイ酸カリウム等のポリケイ酸塩と混合して使用してもよい。カップリング処理剤層を形成することにより、回路配線の引きはがし強さ並びに耐湿性が向上する。また、プリント配線板としての要求特性に応じて防錆処理層の下に金属処理層または合金処理層を形成してもよい。この金属処理層または合金処理層として用いる金属としては、亜鉛、ニッケル、コバルト、モリブデン、インジウム、鉄等があり、必要に応じて単独または合金として用いられ、金属処理層または合金処理層には、これらの金属の一部が酸化物または水酸化物として存在してもよい。
【０００９】
接着性付与層の形成に用いるエポキシ樹脂重合体としては、特開平４−１２０１２４号公報，特開平４−１２０１２５号公報、特開平５−９３０４１号公報、並びに特開平５−９３０４２号公報に記載のビスフェノールＡジグリシジルエーテル等の二官能性エポキシ樹脂、ビスフェノールＡ等の二官能フェノール類及びメラミン、イソシアヌル酸等のトリアジン環若しくはイソシアヌル環を有する化合物との反応によりできるエポキシを用いることができる。このエポキシ樹脂重合体は、フィルム形成性や機械強度に優れることから、溶解度の許容する範囲で高分子量であることが好ましく、重量平均分子量で７０，０００以上、より好ましくは１００，０００以上である。上記のエポキシ樹脂重合体を溶剤に溶解し、濃度が１〜１０％のワニスとして用いる。溶剤としては、ホルムアミド、ジメチルホルムアミド、ジメチルアセトアミド、Ｎ−メチルピロリドン等のアミド化合物類、クロロホルム、塩化メチレン等のハロゲン化炭化水素類、アリルグリシジルエーテル、スチレンオキサイド、フェニルグリシジルエーテル等のエポキシ化合物類、アミド化合物類とベンゼン、ヘキサン、トルエン、キシレン等の炭化水素類、メタノール、エタノール、1一プロパノール、2一プロパノール等のアルコール類、アセトン、２−ブタノン、２−ペンタノン、３−ペンタノン等のケトン類、あるいは、ギ酸メチル、酢酸メチル、酢酸エチル等のエステル類との混合溶剤を用いる。
【００１０】
上記のエポキシ樹脂重合体は熱軟化性であり、熱硬化性を付与する硬化剤を配合したエポキシ樹脂重合体ワニスとして銅箔上に各種の方法で塗工し、乾燥することにより、接着性付与層を形成する。硬化剤としては各種のブロックイソシアネート類等、エポキシ重合体の水酸基と反応して架橋三次元化するものを用いることができる。また、低分子量のエポキシ樹脂とジシアンジアミド等の硬化剤を添加し、エポキシ樹脂硬化物とともに一体化させてもよい。さらには、各種の熱硬化性樹脂の硬化システムを適用することができる。また、本発明のエポキシ樹脂重合体ワニスは難燃剤、レベリング剤、酸化防止剤などの各種添加剤を添加することができ、乾燥後の樹脂組成物層の塗工量は、重量換算厚さで０．５〜５ｇ／ｍ２である。０．５ｇ／ｍ２未満では引きはがし強さが低く、５ｇ／ｍ２より厚いと耐湿性が低下する。接着性付与層は、銅箔の被接着面を完全に被覆している必要はなく、粗面側であれば凸部の頂点が被覆されていなくてもよい。
【００１１】
接着性付与層を銅箔の被接着面に設ける方法としては、上記のエポキシ樹脂重合体ワニスを公知の塗工方式、例えば、転写方式（ローラ、ホイール、ダウバー）、触圧方式（ボールポイント）、噴射方式、自重滴下方式等を用いることができる。これらの中では、噴射方式あるいは自重滴下方式によって実施することが量産性、経済性の点で実用上望ましい。エポキシ樹脂重合体ワニスを塗工した後、加熱乾燥することにより、接着性付与層を半硬化状態とする。完全に硬化した状態ではガラス布エポキシ樹脂基材等の積層基材との積層成型に際して、接着性付与層と基材樹脂との一体化が十分ではなく、信頼性が低下する。一方、硬化が不十分な状態では、塗工品をロール状で保管した場合に接着性付与層が銅箔の他方の面を汚染する。乾燥温度は４５〜３００℃、好ましくは７０〜２００℃、乾燥時間は１０秒〜６０分、好ましくは１〜３０分である。
【００１２】
【実施例】
以下、本発明を実施例に基づいて詳細に説明するが、本発明はこれに限定されるものではない。
【００１３】
（実施例１）重量平均分子量が１２７，０００のビスフェノールＡ系エポキシ樹脂重合体を含有する溶液（固形分３０％、溶剤：ジメチルアセトアミド）１００重量部に、クレゾールノボラック型エポキシ樹脂（エポキシ当量：１９８）１５重量部、フェノールノボラック（水酸基当量：１０６）７重量部、２−エチル−４−メチルイミダゾール１重量部を加え、ジメチルアセドアミド１８７８重量部を加えて攪拌し、エポキシ樹脂重合体ワニスを調製した。このエポキシ樹脂重合体ワニスを、粗化処理層と、ニッケルとモリブデンとコバルトからなる合金処理層と、クロメート処理層と、シランカップリング剤処理層の形成された厚さ１２μｍの電解銅箔の非光沢面側（１０点平均粗さ：Ｒｚ＝５．５μｍ）にスプレー法により５秒間塗布し、直ちに温度７０℃で３０分間乾燥してプリント配線板用銅箔とした。接着性付与層の厚さは、重量換算厚さで４．７ｇ／ｍ２であった。プリント配線板用銅箔を、厚さ０．２ｍｍのガラス布基材エポキシ樹脂プリプレグ（日立化成工業株式会社製、商品名 ＧＥＡ−６７Ｎ及びＧＥＡ−６７９Ｎ）８枚に、樹脂面（即ち、被接着面）がプリプレグに面するように積層し、温度１６８℃、圧力０．３ＭＰａ、時間９０分の条件下で加熱加圧処理して銅張積層板を作製した。この銅張積層板の特性を表に示した。なお、試験法は下記に記載したとおりである。ただし、引きはがし強さ及び耐薬品性劣化率はＦＲ−５グレードのプリプレグ（ＧＥＡ−６７９Ｎ）を用いた銅張積層板における値であり、耐湿性劣化率はＦＲ−４グレードのプリプレグ（ＧＥＡ−６７Ｎ）を用いた銅張積層板における値である。
（実施例２）表面粗さが１０点平均粗さ＝２．３で粗化処理層が形成されていないことを除いては、実施例１と同様にして評価を行なった。結果を合わせて表に示した。
【００１４】
（実施例３）表面粗さが１０点平均粗さ＝１．５で粗化処理層が形成されていないことを除いては、実施例1と同様にして評価を行なった。結果を合わせて表に示した。
【００１５】
（比較例１）カップリング剤処理層が形成されていないことを除いては、実施例1と同様にして評価を行なった。結果を合わせて表に示した。
【００１６】
（比較例２）接着性付与層が重量換算厚さで０．３ｇ／ｍ２であることを除いては、実施例1と同様にして評価を行なった。結果を合わせて表に示した。
【００１７】
（比較例３）接着性付与層が重量換算厚さで１０ｇ／ｍ２であることを除いては、実施例1と同様にして評価を行なった。結果を合わせて表に示した。
【００１８】
（比較例４）接着性付与層を形成しないことを除いては、実施例1と同様にして評価を行なった。結果を合わせて表に示した。
【００１９】
（比較例５）接着性付与層を形成しないことを除いては、実施例２と同様にして評価を行なった。結果を合わせて表に示した。
【００２０】
（比較例６）接着性付与層を形成しないことを除いては、実施例３と同様にして評価を行なった。結果を合わせて表に示した。
【００２１】
【表１】
【発明の効果】
本発明のプリント配線板用銅箔を用いることにより、銅箔と樹脂基材間の引きはがし強さを高く保持する高信頼性のプリント配線板を製造できる。[0001]
[Industrial application fields]
The present invention relates to a copper foil for printed wiring boards and a method for producing the same.
[0002]
[Prior art]
A printed wiring board used in an electronic device forms an circuit wiring by removing unnecessary portions of the copper foil by etching the copper-clad laminate. The copper clad laminate is manufactured by laminating a base material obtained by impregnating a glass fiber cloth with an epoxy resin and a copper foil. Moreover, using the copper foil with resin which formed the epoxy resin film containing an inorganic filler on copper foil is also performed. The thickness of the epoxy resin film used for the copper foil with resin is usually about 100 μm in order to ensure insulation between circuit wiring layers. Since the printed wiring board is exposed to severe processing conditions in the manufacturing process and is used for a long period of time, high reliability is required, and high peeling strength between the copper foil and the substrate is particularly required. For this reason, the roughening process by an acidic copper plating bath etc. is performed with respect to copper foil for the purpose of improving physically the peeling strength between copper foil and a base material. JP-A-57-87324 discloses that a coupling agent treatment with a silane coupling agent is performed for the purpose of chemically improving the peel strength. JP-A-8-193188 discloses a copper foil with an adhesive in which an adhesive layer made of a rubber-modified epoxy resin composition is formed on a copper foil that is not subjected to a roughening treatment. The thickness of the adhesive layer is not particularly specified, but is about 30 μm from the viewpoint of the examples.
[0003]
[Problems to be solved by the invention]
Printed wiring boards have made rapid technological progress with the advancement of electronic technology, and the performance required for the copper foil constituting the printed wiring boards has also increased. In particular, a copper foil having a small surface roughness is desired in order to cope with the high density of circuit wiring and the high speed of data transfer accompanying the progress of miniaturization and high performance of electronic devices. Using copper foil with a small surface roughness improves the etching processability, facilitates the formation of fine circuit wiring, realizes high-density circuit wiring, and causes signal waveform disturbance. Although the data transfer speed can be increased by reducing the irregularities on the surface of the circuit wiring, the physical interaction with the base material is reduced and the peeling strength of the circuit wiring is reduced. In addition, the inorganic filler in the base material tends to increase in response to high functionality such as high heat resistance, high elastic modulus, and low thermal expansion coefficient of the base material. For this reason, as a result of a decrease in the resin content in the base material, stress relaxation due to plastic deformation and the like are reduced, and the peel strength tends to decrease. If the resin is modified to increase the peel strength, the properties of the substrate may be impaired.
[0004]
The present invention provides a copper foil for a printed wiring board having excellent peel strength without increasing the surface roughness and a method for producing the same, in order to cope with miniaturization of circuit wiring and higher functionality of a substrate. is there.
[0005]
[Means for Solving the Problems]
The present inventors have conducted extensive studies results, Ri Do from the weight-average molecular weight of 70,000 or more epoxy polymer, thickness, adhesion-imparting layer 0.5 to 5 g / m Ru 2 der in terms of weight thickness It has been found that even if a smooth copper foil having a small surface roughness is used, a practically sufficient peel strength can be obtained, and the present invention has been completed. That is, the present invention, 0.5 to 5 g and rust-proofing layer, and a coupling agent treatment layer, Ri Do from the weight-average molecular weight of 70,000 or more epoxy resin polymer, a thickness, in terms of weight thickness a copper foil for printed wiring board and having a / m 2 der Ru adhesion-imparting layer. Ca The coupling agent, by using an epoxy silane coupling agent, copper foil for printed wiring boards having excellent strength peeling is obtained.
[0006]
Furthermore, the present invention includes an epoxy resin polymer in an amount of 1 to 10% in a process for producing a copper foil for printed wiring board by forming an adhesion-imparting layer comprising an epoxy resin polymer having a weight average molecular weight of 70,000 or more It is the manufacturing method of the copper foil for printed wiring boards characterized by coating the solution to do on copper foil.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The type of the copper foil used for the copper foil for printed wiring boards of the present invention may be either an electrolytic copper foil or a rolled copper foil. The thickness is preferably 3 to 70 μm, particularly preferably 3 to 18 μm. It is. Etching is difficult when the copper foil is thicker than 70 μm, and handling is difficult when the copper foil is thinner than 3 μm. The electrolytic copper foil has two types of surfaces, a glossy surface and a non-glossy surface, each having a different surface shape and surface roughness, but in the present invention, an adhesion-imparting layer may be provided on either surface. The surface roughness is preferably a 10-point average roughness of 0.5 to 10 μm, particularly preferably 0.5 to 3 μm. If the surface roughness is less than 0.5 μm, it is difficult to produce the copper foil itself. On the other hand, if it is larger than 3 μm, the portion buried in the base resin increases and etching processing becomes difficult. Further, when the surface roughness is large, the waveform of the high-frequency signal is likely to be disturbed. Therefore, when used in a high-frequency circuit, the surface roughness is preferably small within the above range. If the surface roughness is in the above range, a copper foil that has not been roughened can also be used. A steel-clad laminate using a copper foil that has not been subjected to roughening treatment is particularly excellent in etching processability because there are no roughened particles embedded in the base resin.
[0008]
Moreover, in this invention, it is necessary to provide a rust prevention process layer and a coupling agent process layer in the to-be-adhered surface of copper foil. In addition to the chromate treatment layer, the rust prevention treatment layer includes a zinc-chromate treatment layer containing zinc, a composite treatment layer composed of zinc and aluminum, etc., and these rust prevention treatment layers block oxygen and moisture, Prevents deterioration of copper or the above-mentioned metal treatment layer and alloy treatment layer with time. The antirust treatment layer can be formed by dipping or electrolytic treatment in a treatment bath containing the corresponding metal ion or complex ion thereof. The silane coupling agent-treated layer can be formed by applying various aqueous solutions, aqueous dispersions, solutions, and the like of various coupling agents on the rust-proofing layer by various methods such as coating and spraying. As the coupling agent, various silane coupling agents can be used singly or in combination. Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, β- (3,4-epoxy (Cyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacrylic Roxypropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, γ-chloropropyltrimethoxysilane , - mercaptopropyltrimethoxysilane, it is possible to use γ- mercaptopropyl methyl dimethoxy silane. Further, one or more silane coupling agents described above are mixed and used. Particularly preferred is epoxysilane. In addition, if necessary, the above silane coupling agent and tetraalkoxysilane such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, or polysilicate such as water glass, lithium silicate, potassium silicate, and the like You may mix and use. By forming the coupling agent layer, the circuit wiring peeling strength and moisture resistance are improved. Further, a metal treatment layer or an alloy treatment layer may be formed under the rust prevention treatment layer according to the required characteristics as a printed wiring board. The metal used as the metal treatment layer or alloy treatment layer includes zinc, nickel, cobalt, molybdenum, indium, iron, etc., and is used alone or as an alloy as required. Some of these metals may be present as oxides or hydroxides.
[0009]
Examples of the epoxy resin polymer used for forming the adhesion-imparting layer include those described in JP-A-4-120124, JP-A-4-120125, JP-A-5-93041, and JP-A-5-93042. It is possible to use a bifunctional epoxy resin such as bisphenol A diglycidyl ether, a bifunctional phenol such as bisphenol A, and an epoxy produced by a reaction with a compound having a triazine ring or isocyanuric ring such as melamine and isocyanuric acid. Since this epoxy resin polymer is excellent in film formability and mechanical strength, it is preferable to have a high molecular weight within the allowable range of solubility, and a weight average molecular weight of 70,000 or more, more preferably 100,000 or more. . The above epoxy resin polymer is dissolved in a solvent and used as a varnish having a concentration of 1 to 10%. Examples of the solvent include amide compounds such as formamide, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone, halogenated hydrocarbons such as chloroform and methylene chloride, epoxy compounds such as allyl glycidyl ether, styrene oxide, and phenyl glycidyl ether. Amide compounds and hydrocarbons such as benzene, hexane, toluene and xylene, alcohols such as methanol, ethanol, 1-propanol and 2-propanol, and ketones such as acetone, 2-butanone, 2-pentanone and 3-pentanone Alternatively, a mixed solvent with esters such as methyl formate, methyl acetate, and ethyl acetate is used.
[0010]
The above epoxy resin polymer is heat-softening, and it is applied to the copper foil by various methods as an epoxy resin polymer varnish containing a curing agent that imparts thermosetting properties, and then dried to provide adhesion. Form a layer. As the curing agent, it is possible to use various blocked isocyanates and the like which react with the hydroxyl group of the epoxy polymer to form a cross-linked structure. Alternatively, a low molecular weight epoxy resin and a curing agent such as dicyandiamide may be added and integrated with the cured epoxy resin. Furthermore, various thermosetting resin curing systems can be applied. Moreover, the epoxy resin polymer varnish of the present invention can be added with various additives such as a flame retardant, leveling agent, and antioxidant, and the coating amount of the resin composition layer after drying is expressed in terms of weight equivalent thickness. 0.5 to 5 g / m 2 . When it is less than 0.5 g / m 2 , the peel strength is low, and when it is thicker than 5 g / m 2 , the moisture resistance is lowered. The adhesion-imparting layer does not need to completely cover the surface to be bonded of the copper foil, and the vertex of the convex portion may not be covered as long as it is on the rough surface side.
[0011]
As a method of providing an adhesion-imparting layer on the adherend surface of the copper foil, the above-mentioned epoxy resin polymer varnish is applied by a known coating method, for example, a transfer method (roller, wheel, downer), a contact pressure method (ball point) A spraying method, a dead weight dropping method, or the like can be used. Among these, it is practically desirable in terms of mass productivity and economy to carry out by the injection method or the self-weight dropping method. After applying the epoxy resin polymer varnish, the adhesiveness-imparting layer is brought into a semi-cured state by heating and drying. In a completely cured state, when the laminate molding with a laminated base material such as a glass cloth epoxy resin base material is performed, the adhesion-imparting layer and the base material resin are not sufficiently integrated, and the reliability is lowered. On the other hand, in a state where the curing is insufficient, the adhesion imparting layer contaminates the other surface of the copper foil when the coated product is stored in a roll shape. The drying temperature is 45 to 300 ° C, preferably 70 to 200 ° C, and the drying time is 10 seconds to 60 minutes, preferably 1 to 30 minutes.
[0012]
【Example】
EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to this.
[0013]
Example 1 A cresol novolak type epoxy resin (epoxy equivalent: 198) was added to 100 parts by weight of a solution (solid content 30%, solvent: dimethylacetamide) containing a bisphenol A type epoxy resin polymer having a weight average molecular weight of 127,000. ) 15 parts by weight, 7 parts by weight of phenol novolac (hydroxyl equivalent: 106), 1 part by weight of 2-ethyl-4-methylimidazole, 1878 parts by weight of dimethylacedamide and stirred, and the epoxy resin polymer varnish Prepared. This epoxy resin polymer varnish was prepared by using a roughened layer, an alloy-treated layer made of nickel, molybdenum, and cobalt, a chromate-treated layer, and a 12 μm-thick electrolytic copper foil formed with a silane coupling agent-treated layer. The glossy surface (10-point average roughness: Rz = 5.5 μm) was applied by spraying for 5 seconds and immediately dried at a temperature of 70 ° C. for 30 minutes to obtain a copper foil for a printed wiring board. The thickness of the adhesion imparting layer was 4.7 g / m 2 in terms of weight. Copper foil for printed wiring board is bonded to 8 sheets of glass cloth base epoxy resin prepreg (trade name GEA-67N and GEA-679N, manufactured by Hitachi Chemical Co., Ltd.) having a thickness of 0.2 mm on the resin surface (that is, bonded) Layer) so as to face the prepreg, and a heat treatment was performed under the conditions of a temperature of 168 ° C., a pressure of 0.3 MPa, and a time of 90 minutes to prepare a copper-clad laminate. The characteristics of this copper clad laminate are shown in the table. The test method is as described below. However, the peel strength and the chemical resistance deterioration rate are values in a copper clad laminate using FR-5 grade prepreg (GEA-679N), and the moisture resistance deterioration rate is FR-4 grade prepreg (GEA- 67N) is a value in a copper clad laminate.
Example 2 Evaluation was performed in the same manner as in Example 1 except that the surface roughness was 10-point average roughness = 2.3 and no roughened layer was formed. The results are shown in the table together.
[0014]
(Example 3) Evaluation was carried out in the same manner as in Example 1 except that the surface roughness was 10-point average roughness = 1.5 and no roughened layer was formed. The results are shown in the table together.
[0015]
(Comparative Example 1) Evaluation was performed in the same manner as in Example 1 except that the coupling agent-treated layer was not formed. The results are shown in the table together.
[0016]
(Comparative Example 2) Evaluation was performed in the same manner as in Example 1 except that the adhesion-imparting layer was 0.3 g / m 2 in terms of weight. The results are shown in the table together.
[0017]
(Comparative Example 3) Evaluation was performed in the same manner as in Example 1 except that the adhesion-imparting layer was 10 g / m 2 in terms of weight. The results are shown in the table together.
[0018]
(Comparative Example 4) Evaluation was performed in the same manner as in Example 1 except that no adhesion imparting layer was formed. The results are shown in the table together.
[0019]
(Comparative Example 5) Evaluation was performed in the same manner as in Example 2 except that no adhesion imparting layer was formed. The results are shown in the table together.
[0020]
(Comparative Example 6) Evaluation was performed in the same manner as in Example 3 except that no adhesion-imparting layer was formed. The results are shown in the table together.
[0021]
[Table 1]
【The invention's effect】
By using the copper foil for a printed wiring board of the present invention, a highly reliable printed wiring board that keeps the peel strength between the copper foil and the resin base material high can be manufactured.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002026439A JP4370074B2 (en) | 2002-02-04 | 2002-02-04 | Copper foil for printed wiring board and manufacturing method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002026439A JP4370074B2 (en) | 2002-02-04 | 2002-02-04 | Copper foil for printed wiring board and manufacturing method thereof |
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| JP2003229648A JP2003229648A (en) | 2003-08-15 |
| JP4370074B2 true JP4370074B2 (en) | 2009-11-25 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20070074001A (en) | 2002-03-05 | 2007-07-10 | 히다치 가세고교 가부시끼가이샤 | Metal foil with resin and metal-clad laminate, and printed wiring board using the same and method for production thereof |
| JP3949676B2 (en) * | 2003-07-22 | 2007-07-25 | 三井金属鉱業株式会社 | Copper foil with ultrathin adhesive layer and method for producing the copper foil with ultrathin adhesive layer |
| TWI262041B (en) | 2003-11-14 | 2006-09-11 | Hitachi Chemical Co Ltd | Formation method of metal layer on resin layer, printed wiring board, and production method thereof |
| CN100546435C (en) * | 2003-11-14 | 2009-09-30 | 日立化成工业株式会社 | Formation method, printed substrate and the manufacture method thereof of the resin bed of metal level |
| TWI282259B (en) | 2004-01-30 | 2007-06-01 | Hitachi Chemical Co Ltd | Adhesion assisting agent-bearing metal foil, printed wiring board, and production method of printed wiring board |
| WO2006051864A1 (en) * | 2004-11-10 | 2006-05-18 | Hitachi Chemical Co., Ltd. | Metal foil provided with adhesion auxiliary material and printed wiring board using same |
| JP2007137041A (en) * | 2005-10-17 | 2007-06-07 | Hitachi Chem Co Ltd | Copper foil with adhesion assistant, printed wiring board and valuation method for curing degree |
| CN107263959A (en) * | 2009-06-05 | 2017-10-20 | 吉坤日矿日石金属株式会社 | Conductor package substrate copper foil and base plate for encapsulating semiconductor |
| JP6303364B2 (en) * | 2013-09-27 | 2018-04-04 | 凸版印刷株式会社 | Method for forming through hole in core substrate |
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2002
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