JP4273259B2 - Circuit board film - Google Patents
Circuit board film Download PDFInfo
- Publication number
- JP4273259B2 JP4273259B2 JP2003183843A JP2003183843A JP4273259B2 JP 4273259 B2 JP4273259 B2 JP 4273259B2 JP 2003183843 A JP2003183843 A JP 2003183843A JP 2003183843 A JP2003183843 A JP 2003183843A JP 4273259 B2 JP4273259 B2 JP 4273259B2
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- JP
- Japan
- Prior art keywords
- layer
- component
- weight
- film
- resin
- 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
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- 229920001187 thermosetting polymer Polymers 0.000 claims description 101
- 229920005989 resin Polymers 0.000 claims description 90
- 239000011347 resin Substances 0.000 claims description 90
- 238000007747 plating Methods 0.000 claims description 88
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- 239000010949 copper Substances 0.000 claims description 71
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- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
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- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
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- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
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- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 2
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Description
【０００１】
【産業上の利用分野】
本発明は、回路基板、特に携帯電話、ＰＤＡ（パーソナル・デジタル・アシスタント）、ノートパソコンなどの携帯型機器の電子回路等に利用することのできる回路基板用のベースフィルム、特にフレキシブル回路基板用として好適なベースフィルムに関する。
【０００２】
【従来の技術】
ポリイミド樹脂フィルム、液晶ポリマーフィルム、アラミド樹脂フィルム及びポリエーテルエーテルケトンフィルムなどのフィルムは、優れた耐熱性、寸法安定性、耐溶剤性、及び電気的、機械的特性を有していることから、電子機器等の絶縁材料として広く利用されている。特にポリイミドフィルム上に導体層を形成したものは、テープオートメーティッドボンディング（ＴＡＢ）などのフレキシブル回路基板（ＦＰＣ）に多用されている。
【０００３】
従来、ポリイミドフィルム上に導体層を形成する方法としては、ポリイミドフィルムと銅箔を接着剤（熱硬化性樹脂組成物）で貼り合わせるラミネート法が主流であった。しかしながら、該方法で製造される銅箔付きの基板用フィルムは回路形成の際の穴あけ工程が煩雑である。例えば、基板用フィルム両面に形成された回路を接続するためのスルーホール形成をレーザーで行う場合、まず両面の銅箔にエッチングにより穴をあける工程を経た後、更に絶縁層部分にレーザーで穴をあけることが必要になる。また、ラミネート法では、例えば、３５μｍ、１８μｍ、１２μｍなど、ある程度の厚みを有する銅箔が使用されているが、厚みが増すとサブトラクティブ法による微細な回路形成が困難となる一方、厚みを薄くすると高価になるという問題がある。特にスルーホール内壁をメッキする場合、銅箔上にもメッキが形成されることにより厚みが増し微細な回路形成に不都合となる。
【０００４】
このような問題点を解決するために、直接スパッタリング、蒸着等の乾式プロセスでポリイミド樹脂フィルム上に下地となる金属層を形成した後、無電解銅メッキ、更には電気銅メッキにより導体層を形成する方法（特許文献１および特許文献２）やポリイミドフィルム上に直接メッキを施し導体層を形成する方法（特許文献３および特許文献４）が試みられている。前者は、ポリイミド樹脂フィルムと導体層との密着性向上のために、コバルト、ニッケル、クロムといった下地となる金属層をスパッタリング、真空蒸着等の乾式のメタライジング方式により形成する必要があり、工程が複雑となり且つ、ピンホールの発生を防ぐことが難しい。また、後者の場合も、ポリイミド樹脂フィルムの表面の特殊な親水化処理に加え、無電解銅メッキや電気銅メッキ工程に先立ち、無電解ニッケルメッキ等の工程が必要なため、工程が複雑であり、また接着強度においても必ずしも満足のいくレベルではない。
【０００５】
一方、特許文献５には、これらの問題点を解決するため、耐熱樹脂層と酸化剤による粗化が可能な熱硬化物からなる粗化性樹脂硬化物層で構成される回路基板用のフィルムが開示されている。該フィルムは耐熱樹脂層を有していながらメッキにより導体層が形成でき、ファインパターンの形成が可能でメッキの接着強度にも優れた回路基板を製造することが可能である。しかしながら、該フィルムは耐熱樹脂層と硬化物層という物性の異なる２層間の界面おける接着性の問題が生じることが避けられない。また、耐熱樹脂層は可とう性に優れるものの硬化物層は可とう性の点で必ずしも満足いくものではなく、フレキシブル回路基板等の回路基板のベースフィルムとして用いるには更に改善が求められていた。
【０００６】
【特許文献１】
特開２００１−７７４９３号公報
【特許文献２】
特開平７−２４３０４９号公報
【特許文献３】
特開平８−３１８８１号公報
【特許文献４】
特開平７−２３４０４９号公報
【特許文献５】
国際公開ＷＯ０３／００９６５５号パンフレット
【０００７】
【発明が解決しようとする課題】
本発明は、複数の層からなるフィルムに見られるような層間の接着性の問題がなく、メッキ性や可とう性に優れ、微細な回路形成に適した回路基板用のベースフィルムを提供すること、特にフレキシブル回路基板用として好適なベースフィルムを提供することを目的とする。
【０００８】
【課題を解決するための手段】
本発明者等は、前記課題を解決すべく鋭意検討した結果、特定の物理的性質を有しかつ有機溶剤に可溶の耐熱樹脂、熱硬化性樹脂および充填材を特定の割合で配合した熱硬化性樹脂組成物の硬化物がメッキ性や可とう性に優れ、微細な回路形成にも適したフィルムとなることを見出し、本発明を完成させた。
【０００９】
すなわち、本発明は、以下の内容を含むものである。
【００１０】
［１］ 成分（ａ）破断強度が１００ＭＰａ以上、破断伸度が１０％以上、２０〜１５０℃間の熱膨張係数が６０ｐｐｍ以下、及びガラス転移温度が１６０℃以上である有機溶剤に溶解する耐熱樹脂、成分（ｂ）熱硬化性樹脂、（ｃ）充填剤、並びに（ｄ）ポリブタジエン骨格および／またはポリシロキサン骨格を有する樹脂、を含有し、成分（ａ）と成分（ｂ）の割合が重量比で１００：１〜１：１であり、成分（ａ）と成分（ｂ）の合計量と成分（ｃ）の割合が重量比で１００：１〜３：２であり、成分（ｄ）の配合量が成分（ａ）１００重量部に対し０．１〜１５重量部であり、成分（ａ）〜（ｄ）の合計配合量が７０重量％以上である熱硬化性樹脂組成物の熱硬化物からなる厚さ５乃至２０μｍの回路基板用フィルム。
【００１１】
［２］ 下記Ａ層及びＢ層を隣接して有する回路基板用フィルム、
Ａ層：成分（ａ）破断強度が１００ＭＰａ以上、破断伸度が１０％以上、２０〜１５０℃間の熱膨張係数が６０ｐｐｍ以下、及びガラス転移温度が１６０℃以上である有機溶剤に溶解する耐熱樹脂、成分（ｂ）熱硬化性樹脂、（ｃ）充填剤、並びに（ｄ）ポリブタジエン骨格および／またはポリシロキサン骨格を有する樹脂、を含有し、成分（ａ）と成分（ｂ）の割合が重量比で１００：１〜１：１であり、成分（ａ）と成分（ｂ）の合計量と成分（ｃ）の割合が重量比で１００：１〜３：２であり、成分（ｄ）の配合量が成分（ａ）１００重量部に対し０．１〜１５重量部であり、成分（ａ）〜（ｄ）の合計配合量が７０重量％以上である熱硬化性樹脂組成物の熱硬化物からなる厚さ５乃至２０μｍの熱硬化物層、及びＢ層：金属箔。
【００１２】
［３］ 下記Ａ層及びＣ層からなり、Ｃ層、Ａ層及びＣ層の順の層構成を有する回路基板用フィルム、
Ａ層：成分（ａ）破断強度が１００ＭＰａ以上、破断伸度が１０％以上、２０〜１５０℃間の熱膨張係数が６０ｐｐｍ以下、及びガラス転移温度が１６０℃以上である有機溶剤に溶解する耐熱樹脂、成分（ｂ）熱硬化性樹脂、（ｃ）充填剤、並びに（ｄ）ポリブタジエン骨格および／またはポリシロキサン骨格を有する樹脂、を含有し、成分（ａ）と成分（ｂ）の割合が重量比で１００：１〜１：１であり、成分（ａ）と成分（ｂ）の合計量と成分（ｃ）の割合が重量比で１００：１〜３：２であり、成分（ｄ）の配合量が成分（ａ）１００重量部に対し０．１〜１５重量部であり、成分（ａ）〜（ｄ）の合計配合量が７０重量％以上である熱硬化性樹脂組成物の熱硬化物からなる厚さ５乃至２０μｍの熱硬化物層、及びＣ層：無電解銅メッキ層。
【００１３】
［４］ 下記のＡ層Ｃ層及びＤ層からなり、Ｄ層、Ｃ層、Ａ層、Ｃ層及びＤ層の順の層構成を有する回路基板用フィルム、
Ａ層：成分（ａ）破断強度が１００ＭＰａ以上、破断伸度が１０％以上、２０〜１５０℃間の熱膨張係数が６０ｐｐｍ以下、及びガラス転移温度が１６０℃以上である有機溶剤に溶解する耐熱樹脂、成分（ｂ）熱硬化性樹脂、（ｃ）充填剤、並びに（ｄ）ポリブタジエン骨格および／またはポリシロキサン骨格を有する樹脂、を含有し、成分（ａ）と成分（ｂ）の割合が重量比で１００：１〜１：１であり、成分（ａ）と成分（ｂ）の合計量と成分（ｃ）の割合が重量比で１００：１〜３：２であり、成分（ｄ）の配合量が成分（ａ）１００重量部に対し０．１〜１５重量部であり、成分（ａ）〜（ｄ）の合計配合量が７０重量％以上である熱硬化性樹脂組成物の熱硬化物からなる厚さ５乃至２０μｍの熱硬化物層、
Ｃ層：無電解銅メッキ層、及び
Ｄ層：電気銅メッキ層。
【００１４】
［５］ 下記のＡ層、Ｂ層及びＣ層からなり、Ｂ層、Ａ層及びＣ層の順の層構成を有する回路基板用フィルム、
Ａ層：成分（ａ）破断強度が１００ＭＰａ以上、破断伸度が１０％以上、２０〜１５０℃間の熱膨張係数が６０ｐｐｍ以下、及びガラス転移温度が１６０℃以上である有機溶剤に溶解する耐熱樹脂、成分（ｂ）熱硬化性樹脂、（ｃ）充填剤、並びに（ｄ）ポリブタジエン骨格および／またはポリシロキサン骨格を有する樹脂、を含有し、成分（ａ）と成分（ｂ）の割合が重量比で１００：１〜１：１であり、成分（ａ）と成分（ｂ）の合計量と成分（ｃ）の割合が重量比で１００：１〜３：２であり、成分（ｄ）の配合量が成分（ａ）１００重量部に対し０．１〜１５重量部であり、成分（ａ）〜（ｄ）の合計配合量が７０重量％以上である熱硬化性樹脂組成物の熱硬化物からなる厚さ５乃至２０μｍの熱硬化物層、
Ｂ層：金属箔、及び
Ｃ層：無電解銅メッキ層。
【００１５】
［６］ 下記のＡ層、Ｂ層、Ｃ層及びＤ層からなり、Ｂ層、Ａ層、Ｃ層及びＤ層の順の層構成を有する回路基板用フィルム、
Ａ層：成分（ａ）破断強度が１００ＭＰａ以上、破断伸度が１０％以上、２０〜１５０℃間の熱膨張係数が６０ｐｐｍ以下、及びガラス転移温度が１６０℃以上である有機溶剤に溶解する耐熱樹脂、成分（ｂ）熱硬化性樹脂、（ｃ）充填剤、並びに（ｄ）ポリブタジエン骨格および／またはポリシロキサン骨格を有する樹脂、を含有し、成分（ａ）と成分（ｂ）の割合が重量比で１００：１〜１：１であり、成分（ａ）と成分（ｂ）の合計量と成分（ｃ）の割合が重量比で１００：１〜３：２であり、成分（ｄ）の配合量が成分（ａ）１００重量部に対し０．１〜１５重量部であり、成分（ａ）〜（ｄ）の合計配合量が７０重量％以上である熱硬化性樹脂組成物の熱硬化物からなる厚さ５乃至２０μｍの熱硬化物層、
Ｂ層：金属箔、
Ｃ層：無電解銅メッキ層、及び
Ｄ層：電気銅メッキ層。
【００１６】
［７］ 成分（ａ）の耐熱樹脂がポリイミド、ポリアミドイミド、ポリアミドからなる群より選ばれる１種以上の耐熱樹脂である前記［１］乃至［６］記載の回路基板用フィルム。
【００１７】
［８］ 成分（ａ）の耐熱樹脂がポリアミドイミドである前記［１］乃至［６］記載の回路基板用フィルム。
【００１８】
［９］ 成分（ｂ）の熱硬化性樹脂が、エポキシ樹脂、ビスマレイミド化合物とジアミン化合物の重合物、シアネートエステル化合物からなる群より選ばれる１種以上の熱硬化性樹脂である前記［１］乃至［６］記載の回路基板用フィルム。
【００１９】
［１０］ 成分（ｂ）の熱硬化性樹脂が、エポキシ樹脂である前記［１］乃至［６］記載の回路基板用フィルム。
【００２０】
［１１］ 成分（ｃ）の充填材が、アクリルゴム粒子、シリコン粒子、シリカからなる群より選ばれる１種以上の充填材である前記［１］乃至［６］記載の回路基板用フィルム。
【００２１】
［１２］ 前記［１］〜［１１］のいずれかに記載の回路基板用フィルムを使用して製造された回路基板。
【００２２】
［１３］ 前記［１］〜［１１］のいずれかに記載の回路基板用フィルムを使用して製造されたフレキシブル回路基板。
【００２３】
【発明の実施の形態】
以下に本発明を詳細に説明する。
【００２４】
本発明における熱硬化性耐熱樹脂組成物、すなわち、成分（ａ）破断強度が１００ＭＰａ以上、破断伸度が１０％以上、２０〜１５０℃間の熱膨張係数が６０ｐｐｍ以下、及びガラス転移温度が１６０℃以上である有機溶剤に溶解する耐熱樹脂、成分（ｂ）熱硬化性樹脂、（ｃ）充填剤、並びに（ｄ）ポリブタジエン骨格および／またはポリシロキサン骨格を有する樹脂、を含有し、成分（ａ）と成分（ｂ）の割合が重量比で１００：１〜１：１であり、成分（ａ）と成分（ｂ）の合計量と成分（ｃ）の割合が重量比で１００：１〜３：２であり、成分（ｄ）の配合量が成分（ａ）１００重量部に対し０．１〜１５重量部であり、成分（ａ）〜（ｄ）の合計配合量が７０重量％以上である熱硬化性樹脂組成物について説明する。
【００２５】
本発明における成分（ａ）の耐熱樹脂としては、ポリイミド樹脂、ポリアミドイミド樹脂、ポリアミド樹脂、ポリエーテルイミド樹脂、ポリベンゾオキサゾール樹脂、ポリベンゾイミダゾール樹脂、ポリアミック酸又はこれらの樹脂成分の化学構造を有する共重合体等の耐熱樹脂から選択することができる。これら耐熱樹脂の中では、ポリイミド樹脂、ポリアミドイミド樹脂、ポリアミド樹脂が好ましく、特にポリアミドイミドが好ましい。なお、ポリイミドの前駆体であるポリアミック酸を耐熱樹脂として用いた場合、少なくとも３００℃以上のイミド化温度を必要とするため、エポキシ樹脂や有機フィラー、ブタジエンゴムなどのように３００℃以上の耐熱性を持たないものを併用することは困難である。
【００２６】
本発明における耐熱樹脂は、破断強度が１００ＭＰａ以上、破断伸度が１０％以上、熱膨張係数が７０ｐｐｍ以下、及びガラス転移温度が１６０℃以上であることが必要である。本発明の回路基板用フィルムはフレキシブル回路基板等の回路基板用のベースフィルムとして好適に使用することができるが、成分（ａ）の耐熱樹脂がこれらの値を満たさない場合、ベースフィルムとしての必要な強靱さを得ることが困難となる。
【００２７】
破断強度及び破断伸度は、ＪＩＳ（日本工業規格） Ｋ ７１２７に記載の方法に従って決定される。熱膨張係数及びガラス転移温度は、ＪＩＳ Ｋ ７１９７に記載の方法に従って決定される。なお、ガラス転移温度が分解温度よりも高く、実質ガラス転移温度が観測されない場合も本発明に言う「ガラス転移温度が１６０℃以上である」の定義内に含まれる。なお、分解温度とは、ＪＩＳ Ｋ ７１２０に記載の方法に従って測定したときの質量減少率が５％となる温度で定義される。
【００２８】
本発明における耐熱樹脂は、有機溶媒に溶解する特性を有することが必須である。溶剤に溶解することができない耐熱樹脂は、他の成分と混合して組成物を調製することができないため、本発明に用いることができない。有機溶剤は特に限定されないが、本発明の性質上、２０〜３０℃の常温で液体であり、耐熱樹脂を溶解する性質を有するものが用いられる。また、耐熱樹脂や熱硬化樹脂と反応しない有機溶媒であることが必要であり、例えば、フェノール性水酸基を有するクレゾール等は除かれる。
【００２９】
本発明において使用する好ましい有機溶媒としては、例えば、アセトン、メチルエチルケトン、シクロヘキサノン等のケトン類、酢酸エチル、酢酸ブチル、セロソルブアセテート、プロピレングリコールモノメチルエーテルアセテート、カルビトールアセテート等の酢酸エステル類、セロソルブ、ブチルカルビトール等のカルビトール類、トルエン、キシレン等の芳香族炭化水素類、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を挙げることができる。有機溶剤は２種以上を組み合わせて用いてもよい。
【００３０】
成分（ａ）の耐熱樹脂として上市されている好ましい具体例としては、新日本理化（株）社製の可溶性ポリイミド「リカコートＳＮ２０」及び「リカコートＰＮ２０」、日本ＧＥプラスチックス（株）社製のポリエーテルイミド「ウルテム」、東洋紡績（株）社製のポリアミドイミド「バイロマックスＨＲ１１ＮＮ」及び「バイロマックスＨＲ１６ＮＮ」などが挙げられる。
【００３１】
成分（ａ）の耐熱樹脂は各々単独で用いてもよく、２種類以上を組み合わせて用いてもよい。
【００３２】
本発明における成分（ｂ）の熱硬化性樹脂は、プラスチックフィルム製造において通常用いられる熱硬化温度１５０〜３５０℃の範囲で熱硬化するものであれば特に限定されるものではないが、比較的低温である１５０〜２００℃の範囲で硬化するものを選択することがより好ましい。成分（ｂ）の熱硬化性樹脂としては、例えば、１分子中に２以上のエポキシ基を有するエポキシ樹脂、ビスマレイミド化合物とジアミン化合物の重合物、シアネートエステル化合物、ビスマレイミド化合物、ビスアリルナジド樹脂、ベンゾオキサジン化合物等の熱硬化性樹脂を挙げることができる。中でも、１分子中に２以上のエポキシ基を有するエポキシ樹脂、ビスマレイミド化合物とジアミン化合物の重合物、シアネートエステル化合物、またはこれらの混合物が好ましい。また、１分子中に２以上のエポキシ基を有するエポキシ樹脂及びビスマレイミド化合物とジアミン化合物の重合物の混合物、１分子中に２以上のエポキシ基を有するエポキシ樹脂及びシアネートエステル化合物の混合物、１分子中に２以上のエポキシ基を有するエポキシ樹脂がより好ましく、特に１分子中に２以上のエポキシ基を有するエポキシ樹脂が好ましい。
【００３３】
エポキシ樹脂としては、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、フェノールノボラックエポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、アルキルフェノールノボラック型エポキシ樹脂、ビフェノール型エポキシ樹脂、ナフタレン型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、フェノールとフェノール性水酸基を有する芳香族アルデヒドとの縮合物のエポキシ化物、トリグリシジルイソシアヌレート、脂肪環式エポキシ樹脂等などの１分子中に２以上の官能基を有するエポキシ樹脂を挙げることができる。
【００３４】
エポキシ樹脂を使用する場合にはエポキシ硬化剤が必要となる。エポキシ硬化剤としては、アミン系硬化剤、グアニジン系硬化剤、イミダゾール系硬化剤、フェノール系硬化剤、酸無水物系硬化剤、ヒドラジド系硬化剤、カルボン酸系硬化剤、チオール系硬化剤又はこれらのエポキシアダクトやマイクロカプセル化したもの等を挙げることができる。また、トリフェニルホスフィン、ホスホニウムボレート、３−（３，４−ジクロロフェニル）−１，１−ジメチルウレア等の硬化促進剤を併用して用いてもよい。
【００３５】
エポキシ硬化剤の具体例としては、例えば、ジシアンジアミド、２−フェニル−４−メチル−５−ヒドロキシメチルイミダゾール、２，４−ジアミノ−６−（２−メチル−１−イミダゾリルエチル）−１、３、５−トリアジン・イソシアヌル酸付加物、トリアジン構造含有ノボラック樹脂（例えば、フェノライト７０５０シリーズ：大日本インキ化学工業（株）社製）などを挙げることができる。
【００３６】
ビスマレイミド化合物とジアミン化合物の重合物樹脂としては、（株）プリンテック社製の「テクマイトＥ２０２０」などが挙げられる。
シアネートエステル化合物としては、ビスフェノールＡ型シアネートエステルである「プリマセット（Ｐｒｉｍａｓｅｔ） ＢＡ２００」（ロンザ（株）社製）、「プリマセット（Ｐｒｉｍａｓｅｔ） ＢＡ２３０Ｓ」（ロンザ（株）社製）、ビスフェノールＨ型シアネートエステルである「プリマセット（Ｐｒｉｍａｓｅｔ） ＬＥＣＹ」（ロンザ（株）社製）、「アロシー（Ａｒｏｃｙ）Ｌ１０」（バンティコ（株）社製）、ノボラック型シアネートエステルである「プリマセット（Ｐｒｉｍａｓｅｔ） ＰＴ３０」（ロンザ（株）社製）、「アロシー（Ａｒｏｃｙ）ＸＵ−３７１」（バンティコ（株）社製）、ジシクロペンタジエン型シアネートエステルである「アロシー（Ａｒｏｃｙ）ＸＰ７１７８７．０２Ｌ」（バンティコ（株）社製）などが挙げられる。
ビスマレイミド化合物としては、４，４‘−ジフェニルメタンビスマレイミドである「ＢＭＩ−Ｓ」（三井化学（株）社製）、ポリフェニルメタンマレイミドである「ＢＭＩ−Ｍ−２０」（三井化学（株）社製）などが挙げられる。
ビスアリルナジド樹脂としては、ジフェニルメタン−４，４‘−ビスアリルナジックイミドである「ＢＡＮＩ−Ｍ」（丸善石油化学（株）社製）などが挙げられる。
ベンゾオキサジン樹脂としては、四国化成（株）社製「Ｂ−ａ型ベンゾオキサジン」、「Ｂ−ｍ型ベンゾオキサジン」などが挙げられる。
【００３７】
これら成分（ｂ）の熱硬化性樹脂は、各々単独で用いてもよく、２種類以上を組み合わせて用いてもよい。
【００３８】
本発明における成分（ｃ）の充填材は熱硬化性樹脂組成物の熱硬化物表面を酸化剤で粗化する際に、適度な粗化面を形成し、メッキによってピール強度に優れる導体層の形成を可能にするために重要である。充填材は、無機充填材と有機充填材に分類できる。無機充填材は硬化物の熱膨張率を下げる効果もあり、有機充填材は硬化物中の応力を緩和する効果もある。
【００３９】
無機充填材としては、シリカ、アルミナ、硫酸バリウム、タルク、クレー、雲母粉、水酸化アルミニウム、水酸化マグネシウム、炭酸カルシウム、炭酸マグネシウム、酸化マグネシウム、窒化ホウ素、ホウ酸アルミニウム、チタン酸バリウム、チタン酸ストロンチウム、チタン酸カルシウム、チタン酸マグネシウム、チタン酸ビスマス、酸化チタン、ジルコン酸バリウム、ジルコン酸カルシウムなどが挙げられる。特にシリカが好ましい。無機充填材は平均粒径５μｍ以下のものが好ましい。平均粒径が５μｍを超える場合、粗化後メッキにより形成した導体層に回路パターンを形成する際にファインパターンの形成を安定に行うことが困難になる場合がある。また耐湿性を向上させるため、シランカップリング剤等の表面処理剤で表面処理してあるものが好ましい。
【００４０】
有機充填材としては、好ましくはアクリルゴム粒子、シリコン粒子が挙げられる。粗化後に適度な凹凸を形成させる観点から、特に扁平状の有機充填材を用いるのがより好ましい。有機充填材も同様に平均粒径５μｍ以下のものが好ましい。
【００４１】
本発明における成分（ｄ）の「ポリブタジエン骨格及び／又はポリシロキサン骨格を有する樹脂」は、成分（ｃ）と同様に、酸化剤により硬化物表面に好ましい粗化面を形成するために重要である。
【００４２】
ポリブタジエンとしては、ポリブタジエンゴム、エポキシ変性ポリブタジエンゴム、ウレタン変性ポリブタジエンゴム、アクリロニトリル変性ポリブタジエンゴム、メタクリロニトリル変性ポリブタジエンゴム、カルボキシル基を有するアクリロニトリル・ブタジエンゴム、アクリロニトリルゴム分散型エポキシ樹脂等が挙げられ、ポリシロキサン骨格を有する樹脂としては、日立化成工業（株）社製の「ＫＳ９１００」、「ＫＳ９３００」等のシロキサン骨格含有ポリアミドイミドなどが挙げられる。
【００４３】
本発明における熱硬化性樹脂組成物においては、成分（ａ）の耐熱樹脂と成分（ｂ）の熱硬化性樹脂の割合が重量比で１００：１〜１：１の範囲であることを必要とする。より好ましい範囲は成分（ａ）と成分（ｂ）の割合が重量比で１００：１〜５：３である。成分（ａ）の割合が少なすぎると、回路基板用のベースフィルムとして必要な強靱さを得ることが困難となる。また成分（ａ）は酸化剤として汎用されるアルカリ性過マンガン酸溶液に対する耐性が低いため、成分（ａ）の割合が多すぎると粗化後の硬化物物性が低下する場合がある。
【００４４】
本発明における熱硬化性樹脂組成物においては、成分（ａ）と成分（ｂ）の合計量と成分（ｃ）の割合が重量比で１００：１〜３：２の範囲であることを必要とする。より好ましい範囲は１００：３〜２０：１１である。成分（ｃ）の充填材の割合がこの範囲より多いと、本発明の回路基板用フィルムに必要な物性値が得られ難い傾向にあり、少ないと粗化により十分な凹凸面が得られにくい傾向にある。
【００４５】
本発明における熱硬化性樹脂組成物においては、成分（ｄ）の配合量が成分（ａ）１００重量部に対し０．１〜１５重量部の範囲であることを必要とする。より好ましい範囲は成分（ａ）１００重量部に対し、０．１〜１５重量部である。成分（ｄ）の配合量がこの範囲より多いと、硬化物の機械強度が低下する傾向にあり、少ないと酸化剤による粗化により十分な凹凸面が得られにくい傾向にある。
【００４６】
本発明における熱硬化性樹脂組成物の硬化物は、回路基板用のベースフィルムとしての強靱性とメッキによりピール強度に優れた導体層が形成可能な粗化性を併せ持つ。すなわち、該硬化物は、破断強度が１００ＭＰａ以上、破断伸度が５％以上、２０〜１５０℃間の熱膨張係数が７０ｐｐｍ以下、及びガラス転移温度が１５０℃以上の物性値、更に好ましくは、破断強度１１０MＰa以上、破断伸度が１０％以上、２０〜１５０℃間の熱膨張係数が５０ｐｐｍ以下、及びガラス転移温度が２００℃以上の物性値を達成することが可能である。また酸化剤により硬化物表面を粗化しメッキにより導体層を形成することで、０．６ｋｇｆ／ｃｍ（５．９×１０２Ｎ／ｍ）以上、好ましく０．７ｋｇｆ／ｃｍ（６．９×１０２Ｎ／ｍ）以上の導体層のピール強度を達成することが可能である。
【００４７】
本発明における熱硬化性樹脂組成物においては、本発明の効果が十分に発揮される範囲内で、成分（ａ）〜（ｄ）以外の他の成分を配合することもできるが、成分（ａ）〜（ｄ）の合計配合量が７０重量％以上であることを必要とする（すなわち７０重量％〜１００重量％）。より好ましい範囲は７５重量％以上、更に好ましくは８０重量％以上、更に好ましくは８５重量％以上、更に好ましくは９０重量％以上である。成分（ａ）〜（ｄ）の合計配合量が７０重量％未満であると本発明の効果が十分に発揮されない傾向にある。
【００４８】
本発明における熱硬化性樹脂組成物に配合される他の成分としては、例えば、オルベン、ベントン等の増粘剤、シリコーン系、フッ素系、高分子系の消泡剤又はレベリング剤、イミダゾール系、チアゾール系、トリアゾール系、シランカップリング剤等の密着性付与剤、フタロシアニン・ブルー、フタロシアニン・グリーン、アイオジン・グリーン、ジスアゾイエロー、カーボンブラック等の着色剤等の樹脂添加剤や（ａ）、（ｂ）、（ｄ）成分以外の任意の樹脂成分などを挙げることができる。
【００４９】
本発明の回路基板用フィルムは、上記に説明した熱硬化性樹脂組成物の硬化物からなる。該硬化物表面は酸化剤による粗化処理によって、表面に緻密な凹凸を形成することができ、粗化処理後の硬化物表面にメッキにより導体層を形成することが可能である。
【００５０】
本発明の回路基板用フィルムは、例えば熱硬化性樹脂組成物のワニスを平滑かつ離型性のある支持体の表面に塗布し、乾燥後あるいは乾燥途中の適当な段階で支持体より剥離することにより製造することができる。
【００５１】
ワニスを調製するための有機溶剤としては、例えば、アセトン、メチルエチルケトン、シクロヘキサノン等のケトン類、酢酸エチル、酢酸ブチル、セロソルブアセテート、プロピレングリコールモノメチルエーテルアセテート、カルビトールアセテート等の酢酸エステル類、セロソルブ、ブチルカルビトール等のカルビトール類、トルエン、キシレン等の芳香族炭化水素類、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を挙げることができる。有機溶剤は２種以上を組み合わせて用いてもよい。
【００５２】
回路基板用フィルムの具体的な製造方法としては、プラスチックフィルム製造において通常用いられる溶液流延法（キャスティング法）などのように、熱硬化性樹脂組成物のワニスをＴダイから押し出して、ダイの下を走行しているステンレス製のエンドレスベルトに流延し、このベルトの上で適度に溶剤を揮発させてフィルムを得、続いてフィルムをベルトより剥離して最終乾燥と熱硬化を行う方法や、剥離性を有する支持体上に該熱硬化性樹脂組成物のワニスを塗布し、フィルム状になるまで熱硬化性樹脂組成物の乾燥を行ってから、樹脂組成物フィルムを剥離性フィルムより剥離して最終乾燥と熱硬化を行う方法などが挙げられる。乾燥及び熱硬化の条件は特に限定されず、溶剤の沸点の違いや、支持体と樹脂組成物の接着性、熱硬化成分の反応開始温度などを考慮しながら、作業性に応じて適宜決定することができる。フィルム状にするための乾燥条件は、ワニスに含まれる溶媒の種類等によっても異なるが、例えば５０〜２００℃で１分〜３０分程度の範囲から選択することができる。また最終乾燥及び熱硬化を行う工程の条件も特に限定はされず、最終的に熱硬化樹脂組成物が硬化した状態とするために当業者が適宜好ましい条件を設定することができるが、例えば１５０℃〜３５０℃で３０分〜２４時間程度の範囲から選択することができる。
【００５３】
前記のようにして得られる熱硬化性樹脂組成物の硬化物からなる回路基板用フィルムは、当業者に公知の方法、すなわち酸化剤による粗化処理によって表面に緻密な凹凸を形成し、粗化表面にメッキを行う方法により導体層を形成することができる。なお導体層形成後は、１５０〜２００℃で２０〜９０分アニール（aneal）処理することにより、導体層のピール強度をさらに向上、安定化させることができる。
【００５４】
粗化処理に用いる酸化剤としては、アルカリ性過マンガン酸溶液や重クロム酸塩、過酸化水素、硫酸、硝酸等の酸化剤溶液が挙げられるが、特にプリント配線板の製造において広く用いられているアルカリ性過マンガン酸溶液が好ましい。アルカリ性過マンガン酸溶液としては、例えば、水酸化ナトリウムの水溶液に過マンガン酸カリウムや過マンガン酸ナトリウムを溶解した溶液を挙げることができる。
【００５５】
メッキによる導体層形成は、無電解メッキと電解メッキを組み合わせた方法、又は導体層とは逆パターンのメッキレジストを形成し、無電解メッキのみで導体層を形成する方法により行うことができる。
【００５６】
無電解銅メッキは、一般的にプリント配線板のアディティブ法あるいはセミアディティブ法で通常用いられる方法で行うことができる。すなわち、まず、酸化剤で粗化されたフィルム表面に触媒付与を行った後、所定の無電解銅メッキ液に所定の条件の元に浸漬することで実施することができる。粗化表面に付与する触媒としては、通常一般に用いられているパラジウム金属がより好ましい。無電解銅メッキ液は、錯化剤や還元剤等の浴構成成分の違いで種々のものが市販されているが、特に限定されるものではない。無電界銅メッキ層（Ｃ層）の厚みは、通常０．１〜３μｍであり、好ましくは、０．３〜２μｍである。
【００５７】
無電解銅メッキ表面に電解銅メッキを行なう方法も公知の方法に従って行うことができ、電界銅メッキ液についても、浴構成成分の違いで種々のものが使われるが、特に通常一般に用いられている硫酸銅メッキ浴が好ましい。電界銅メッキ層（Ｄ層）の厚みは、通常３〜３５μｍであり、好ましくは、５〜２０μｍである。
【００５８】
導体層に回路形成する方法としては、当業者に公知のサブトラクティブ法やセミアディティブ法などを用いることができる。サブトラクティブ法の場合、無電解銅メッキ層の上に電気メッキ層を形成した後、エッチングレジストを形成し、塩化第二鉄、塩化第二銅等のエッチング液でエッチングすることにより導体パターンを形成した後、エッチングレジストを剥離することにより、回路形成することが出来る。また、セミアディティブ法の場合には、無電界銅メッキ層上にパターンレジストを施し、所望の厚みの電界銅メッキ層（パターンメッキ層）を形成後、パターンレジストを剥離し、無電解銅メッキ層をフラッシュエッチで除去することにより、回路基板を得ることができる。
【００５９】
なお本発明の回路基盤用フィルムにおいては、熱硬化性樹脂組成物よりなるＡ層と、金属箔よりなるＢ層を隣接して有する構成のフィルムとしてもよい。このような回路基板用フィルムにおいては、前述したように硬化物層が酸化剤により粗化でき、さらにその粗化表面に無電界銅メッキを行うことができ、さらには無電界銅メッキ上に電界銅メッキを行うことができる。このようにフィルムの硬化物層表面に粗化処理及びメッキ処理を行うことにより、片面がメッキ、もう片面が金属箔により導体層が形成された両面銅張回路基板を製造することができる。このような回路基板用フィルムは、例えば、硬化物層にレーザーにより穴あけを施し、続いて、メッキ処理に、形成された穴も含めて導体層を形成する際、すでに接着されている金属箔を基点に穴内にビアポストを形成していくことができる利点がある。
【００６０】
このような金属箔つきのフィルムの製造は、一般的には、金属箔（Ｂ層）を支持体とし、
この表面に前記と同様に本発明における熱硬化性樹脂組成物のワニスを塗布・乾燥させて硬化物層（Ａ層）を形成することで得ることができる。金属箔は特に銅箔が好ましく、その銅箔については、圧延銅箔及び電解銅箔のいずれでもよく、その厚さは、２μｍ以上３６μｍ以下であるのが一般的である。銅箔の厚みが薄く作業性が困難な場合は、必要に応じてキャリア付き銅箔を使用しても良い。また、樹脂が塗布される金属箔の面については、樹脂と金属箔の接着力を高くする観点から、マット面であることがより好ましく、必要に応じて、銅箔の塗布面に事前にカップリング剤等の化学処理を施したものを用いてもよい。
【００６１】
本発明における回路基板用フィルムの好ましい層構成としては、以下の層構成例１乃至６を挙げることができる。
【００６２】
層構成例１：熱硬化物層（Ａ層）
層構成例２：熱硬化物層（Ａ層）／金属箔（Ｂ層）
層構成例３：無電界メッキ層（Ｃ層）／熱硬化物層（Ａ層）／無電界メッキ層（Ｃ層）
層構成例４：電界銅メッキ層（Ｄ層）／無電界メッキ層（Ｃ層）／熱硬化物層（Ａ層）／無電界メッキ層（Ｃ層）／電界銅メッキ層（Ｄ層）
層構成例５：無電界メッキ層（Ｃ層）／熱硬化物層（Ａ層）／金属箔（Ｂ層）
層構成例６：電界銅メッキ層（Ｄ層）／無電界メッキ層（Ｃ層）／熱硬化物層（Ａ層）／金属箔（Ｂ層）
【００６３】
なお、本発明の回路基板用フィルムは、ロール状に巻き取って、保存、貯蔵することもできる。
【実施例】
【００６４】
以下、実施例を示して本発明を具体的に説明するが、本発明はこれに限定されるものではない。なお、実施例中、部は重量部を意味する。
【００６５】
＜実施例１＞
ビスフェノールＡ型エポキシ樹脂「エピコート８２８」（エポキシ当量１９０、ジャパンエポキシレジン（株）社製）３０部、トリアジン環含有フェノールノボラック樹脂の２−ブタノン溶液「フェノライトＬＡ７０５２」（不揮発分６０重量％、不揮発分のフェノール水酸基当量１２０、大日本インキ化学工業（株）社製）１３部、扁平形状を有するシリコン樹脂粒子「ＡＧＭ１０１」（竹本油脂（株）社製）１部（平均粒径０．４１μｍ）、球状シリカ３部（平均粒径１μｍ）を混合しロール分散させ、これにポリアミドイミド「ＨＲ１１ＮＮ」（不揮発分１５重量％、破断強度１５０ＭＰａ、破断伸度８０％、熱膨張係数４２ｐｐｍ、ガラス転移温度３００℃、東洋紡績（株）社製）４６０部及びシロキサン変性ポリアミドイミド「ＫＳ９１００」（不揮発分３１重量％、日立化成工業（株）社製）１５部を混合し、熱硬化性樹脂組成物の樹脂ワニスを作成した。
【００６６】
＜実施例２＞
実施例１記載の樹脂ワニスを、厚さ３８μｍのポリエチレンテレフタレートフィルム上に、乾燥後の樹脂厚みが３０μｍとなるように塗布し、８０〜１４０℃（平均１１０℃）で約１６分間乾燥させた。続いて、樹脂組成物フィルムをポリエチレンテレフタレートフィルムより剥離し、金属製の治具に樹脂組成物フィルムを固定してから、１８０℃で３０分間加熱し熱硬化させて、前記層構成例１に相当する回路基板用フィルムを作成した。
【００６７】
熱硬化物層をポリエチレンテレフタレートフィルムより剥がし、更に２００℃で３時間加熱した後、ＪＩＳ Ｋ ７１２７に従い、このフィルムからダンベル状の試験片を切り出した。これら試験片を用いて引張試験を行い、フィルムの破断強度、破断伸度を測定したところ、次のような値を示した。破断強度＝１１０MＰa、破断伸度＝１３％。また、この硬化物フィルムを１８０度で折り曲げた際に、フィルムにはクラックは発生せず、十分な可とう性を示した。
【００６８】
＜実施例３＞
実施例１記載の樹脂ワニスを、厚さ１８μｍの銅箔上に、乾燥後の樹脂厚みが２０μｍとなるように塗布し、８０〜１４０℃（平均１１０℃）で約１６分間乾燥させ、さらに続いて、１８０℃で３０分加熱し熱硬化させて、前記層構成例２に相当する回路基板用フィルムを作成した。
【００６９】
＜実施例４＞
実施例２記載の、構成例（１）に相当する回路基板用フィルムを、「Swelling Dip Securiganth P」（アトテックジャパン（株）社製）を用いた膨潤液に８０℃で５分間浸漬して粗化性樹脂硬化物層表面を膨潤後、続いて、アルカリ性過マンガン酸溶液に８０℃で１０分間浸漬して粗化を行ない、さらに、粗化性樹脂硬化物層表面に残ったマンガンを還元除去した。引続き、無電界銅メッキの触媒付与を行なった後、無電界銅メッキ液に３２℃で３０分間浸漬して、１．５μｍの無電界銅メッキ皮膜を形成させた。これを、１２０℃で３０分間乾燥を行って、前記層構成例３に相当する回路基板用フィルムを得た。また、これをさらに、酸洗浄し、含リン銅板をアノードとし、陰極電流密度２．０Ａ／ｄｍ２で１２分間電気銅メッキを行ない、厚さ５μｍの銅メッキ皮膜を形成させた。最後に、２００℃で３時間アニールを行って、前記層構成例４記載の回路基板用フィルムを得た。メッキの皮膜の接着強度（ピール強度）は０．８ｋｇｆ／ｃｍ（７．８×１０２Ｎ／ｍ）であった。
【００７０】
＜実施例５＞
実施例３記載の、層構成例２に相当する回路基板用フィルムを、「Swelling Dip Securiganth P」（アトテックジャパン（株）社製）を用いた膨潤液に８０℃で５分間浸漬して硬化物層表面を膨潤後、続いてアルカリ性過マンガン酸溶液に８０℃で１０分間浸漬して粗化を行ない、さらに、硬化物層表面に残ったマンガンを還元除去した。引続き、無電界銅メッキの触媒付与を行なった後、無電界銅メッキ液に３２℃で３０分間浸漬して、１．５μｍの無電界銅メッキ皮膜を形成させた。これを、１２０℃で３０分間乾燥を行って、層構成例５記載の回路基板用フィルムを得た。また、これをさらに、酸洗浄し、含リン銅板をアノードとし、陰極電流密度２．０Ａ／ｄｍ２で１２分間電気銅メッキを行ない、厚さ５μｍの銅メッキ皮膜を形成させた。最後に、２００℃で３時間アニールを行って、層構成例６記載の回路基板用フィルムを得た。メッキ皮膜の接着強度（ピール強度）は０．８ｋｇｆ／ｃｍ（７．８×１０２Ｎ／ｍ）であった。
【００７１】
＜実施例６＞
まず、ビスフェノールＡ型エポキシ樹脂「エピコート８２８」（エポキシ当量１９０、ジャパンエポキシレジン（株）社製）１５部、芳香族炭化水素系溶剤「イプゾール１５０」（出光石油化学（株）社製）１０部、末端エポキシ化ポリブタジエンゴム「デナレックスＲ４５ＥＰＴ」（ナガセ化成工業（株）社製）１部、アクリルゴム微粒子「ＡＣ３８３２」（ガンツ化成（株）社製）３部、球状シリカ４０部を混合しロール分散させた。これに、予めビスマレイミドとジアミン化合物の重合物「テクマイトＥ２０２０」（（株）プリンテック社製）３５部をシクロヘキサノン５０部に加熱溶解させ室温まで冷却しておいたもの及び、予め１，８−ジアザビシクロ（５、４、０）ウンデセン０．２部を２−ブタノン２部に加熱溶解させ室温まで冷却しておいたものを添加し、引き続いて、ポリアミドイミド「ＨＲ１１ＮＮ」（不揮発分１５重量％、破断強度１５０ＭＰａ
、破断伸度８０％、熱膨張係数４２ｐｐｍ、ガラス転移温度３００℃、東洋紡績（株）社製）５６０部を添加し、熱硬化性樹脂組成物のワニスを作成した。
【００７２】
＜実施例７＞
実施例６記載の樹脂ワニスを、厚さ３８μｍのポリエチレンテレフタレートフィルム上に、乾燥後の樹脂厚みが３０μｍとなるように塗布し、８０〜１４０℃（平均１１０℃）で約１６分間乾燥させた。続いて、樹脂組成物フィルムをポリエチレンテレフタレートフィルムより剥がし、金属製の治具に樹脂組成物フィルムを固定してから、１８０℃で３０分間加熱し熱硬化させて、層構成例１に相当する回路基板用フィルムを作成した。
【００７３】
熱硬化物層をポリエチレンテレフタレートフィルムより剥がし、更に２００℃で３時間加熱した後、ＪＩＳ Ｋ ７１２７に従い、このフィルムからダンベル状の試験片を切り出した。これら試験片を用いて引張試験を行い、硬化フィルムの破断強度、破断伸度を測定したところ、次のような値を示した。破断強度＝１２０ＭＰａ、破断伸度＝６％。また、この硬化物フィルムを１８０度で折り曲げた際に、フィルムにはクラックは発生しなかった。
【００７４】
＜実施例８＞
実施例７記載の樹脂ワニスを、厚さ１８μｍの銅箔上に、乾燥後の樹脂厚みが２０μｍとなるように塗布し、８０〜１４０℃（平均１１０℃）で約１６分間乾燥させ、続いて、１８０℃で３０分間加熱し熱硬化させて、層構成例２に相当する回路基板用フィルムを作成した。
【００７５】
＜実施例９＞
実施例７記載の、構成例（１）に相当する回路基板用フィルムを、「Swelling Dip Securiganth P」（アトテックジャパン（株）社製）を用いた膨潤液に８０℃で５分間浸漬して粗化性樹脂硬化物層表面を膨潤後、続いて、アルカリ性過マンガン酸溶液に８０℃で１０分間浸漬して粗化を行ない、さらに、粗化性樹脂硬化物層表面に残ったマンガンを還元除去した。引続き、無電界銅メッキの触媒付与を行なった後、無電界銅メッキ液に３２℃で３０分浸漬して、１．５μｍの無電界銅メッキ皮膜を形成させた。これを、１２０℃で３０分間乾燥を行って、構成例（３）記載の回路基板用フィルムを得た。また、これをさらに、酸洗浄し、含リン銅板をアノードとし、陰極電流密度２．０Ａ／ｄｍ２で１２分間電気銅メッキを行ない、厚さ５μｍの銅メッキ皮膜を形成させた。最後に、２００℃で３時間アニールを行って、層構成例４記載の回路基板用フィルムを得た。メッキ皮膜の接着強度は１．０ｋｇｆ／ｃｍ（９．８×１０２Ｎ／ｍ）であった。
【００７６】
＜実施例１０＞
実施例８記載の、構成例（２）に相当する回路基板用フィルムを、「Swelling Dip Securiganth P」（アトテックジャパン（株）社製）を用いた膨潤液に８０℃で５分間浸漬して硬化物層表面を膨潤後、続いて、アルカリ性過マンガン酸溶液に８０℃で１０分間浸漬して粗化を行ない、さらに硬化物層表面に残ったマンガンを還元除去した。
【００７７】
引続き、無電界銅メッキの触媒付与を行なった後、無電界銅メッキ液に３２℃で３０分浸漬して、１．５μｍの無電界銅メッキ皮膜を形成させた。これを、１２０℃で３０分間で乾燥を行って、構成例（５）記載の回路基板用フィルムを得た。また、これをさらに、酸洗浄し、含リン銅板をアノードとし、陰極電流密度２．０Ａ／ｄｍ２で１２分間電気銅メッキを行ない、厚さ５μｍの銅メッキ皮膜を形成させた。最後に、２００℃で３時間アニールを行って、層構成例６記載の回路基板用フィルムを得た。メッキ皮膜の接着強度は１．０ｋｇｆ／ｃｍ（９．８×１０２Ｎ／ｍ）であった。
【００７８】
＜実施例１１＞
まず、ビスフェノールＡ型エポキシ樹脂「エピコート８２８」（エポキシ当量１９０、ジャパンエポキシレジン（株）社製）１５部、芳香族炭化水素系溶剤「イプゾール１５０」（出光石油化学（株）社製）１０部、末端エポキシ化ポリブタジエンゴム「デナレックスＲ４５ＥＰＴ」（ナガセ化成工業（株）社製）１部、アクリルゴム微粒子「ＡＣ３８３２」（ガンツ化成（株）社製）３部、球状シリカ４０部を混合しロール分散させた。さらにこのものに、ビスフェノールＡ型エポキシ樹脂「エピコート８２８」（エポキシ当量１９０、ジャパンエポキシレジン（株）社製）１５部を添加し、さらに、予め１，８−ジアザビシクロ（５、４、０）ウンデセン０．４部を２−ブタノン３．６部に加熱溶解させ室温まで冷却しておいたものを添加し、引き続いて、ポリアミドイミド「ＨＲ１１ＮＮ」（不揮発分１５重量％、破断強度１５０ＭＰａ、破断伸度８０％、熱膨張係数４２ｐｐｍ、ガラス転移温度３００℃、東洋紡績（株）社製）４５０部を添加して、熱硬化性樹脂組成物のワニスを作成した。
【００７９】
＜実施例１２＞
実施例１１記載の樹脂ワニスを、厚さ３８μｍのポリエチレンテレフタレートフィルム上に、乾燥後の樹脂厚みが３０μｍとなるように塗布し、８０〜１４０℃（平均１１０℃）で約１６分間乾燥させた。続いて、樹脂組成物フィルムをポリエチレンテレフタレートフィルムより剥がし、金属製の治具に樹脂組成物フィルムを固定してから、１８０℃で３０分加熱し熱硬化させて、層構成例１に相当する回路基板用フィルムを作成した。
【００８０】
熱硬化物層をポリエチレンテレフタレートフィルムより剥がし、更に２００℃で３時間加熱した後、ＪＩＳ Ｋ ７１２７に従い、このフィルムからダンベル状の試験片を切り出した。これら試験片を用いて引張試験を行い、硬化フィルムの破断強度、破断伸度を測定したところ、次のような値を示した。破断強度＝１１０ＭＰａ、破断伸度＝５．７％。また、この硬化物フィルムを１８０度で折り曲げた際に、フィルムにはクラックは発生しなかった。
【００８１】
＜実施例１３＞
実施例１１記載の樹脂ワニスを、厚さ１８μｍの銅箔上に、乾燥後の樹脂厚みが２０μｍとなるように塗布し、８０〜１４０℃（平均１１０℃）で約１６分間乾燥させ、さらに続いて、１８０℃で３０分加熱し熱硬化させて、層構成例２に相当する回路基板用フィルムを作成した。
【００８２】
＜実施例１４＞
実施例１２記載の、構成例（１）に相当する回路基板用フィルムを、「Swelling Dip Securiganth P」（アトテックジャパン（株）社製）を用いた膨潤液に８０℃で５分浸漬して硬化物層表面を膨潤後、続いて、アルカリ性過マンガン酸溶液に８０℃で１０分間浸漬して粗化を行ない、さらに硬化物層表面に残ったマンガンを還元除去した。引続き、無電界銅メッキの触媒付与を行なった後、無電界銅メッキ液に３２℃で３０分浸漬して、１．５μｍの無電界銅メッキ皮膜を形成させた。これを、２００℃で３時間乾燥を行って、層構成例３記載の回路基板用フィルムを得た。また、これをさらに、酸洗浄し、含リン銅板をアノードとし、陰極電流密度２．０Ａ／ｄｍ２で１２分間電気銅メッキを行ない、厚さ５μｍの銅メッキ皮膜を形成させた。最後に、１７０℃で６０分間アニールを行って、構成例（４）記載の回路基板用フィルムを得た。メッキの皮膜の接着強度は０．９ｋｇｆ／ｃｍであった（８．８×１０２Ｎ／ｍ）。
【００８３】
＜実施例１５＞
実施例１３記載の、層構成例２に相当する回路基板用フィルムを、「Swelling Dip Securiganth P」（アトテックジャパン（株）社製）を用いた膨潤液に８０℃で５分浸漬して硬化物層表面を膨潤後、続いて、アルカリ性過マンガン酸溶液に８０℃で１０分間浸漬して粗化を行ない、さらに硬化物層表面に残ったマンガンを還元除去した。 引続き、無電界銅メッキの触媒付与を行なった後、無電界銅メッキ液に３２℃で３０分浸漬して、１．５μｍの無電界銅メッキ皮膜を形成させた。これを、１２０℃で３０分間乾燥を行って、層構成例５記載の回路基板用フィルムを得た。また、これをさらに、酸洗浄し、含リン銅板をアノードとし、陰極電流密度２．０Ａ／ｄｍ２で１２分間電気銅メッキを行ない、厚さ５μｍの銅メッキ皮膜を形成させた。最後に、２００℃で３時間アニールを行って、構成例（６）記載の回路基板用フィルムを得た。メッキの皮膜の接着強度は０．９ｋｇｆ／ｃｍ（８．８×１０２Ｎ／ｍ）であった。
【００８４】
＜比較例１＞
予めビスフェノールＡ型エポキシ樹脂「エピコート８２８」（エポキシ当量１９０、ジャパンエポキシレジン（株）社製）２０部、及び、クレゾールノボラック型エポキシ樹脂「エピクロンＮ６７３」（エポキシ当量２１５、軟化点７８℃、大日本インキ科学工業（株）社製）３５部を２−ブタノンに加熱溶解させ室温まで冷却しておいたものに、トリアジン環含有フェノールノボラック樹脂の２−ブタノン溶液「フェノライトＬＡ７０５２」（不揮発分６０重量％、不揮発分のフェノール水酸基当量１２０、大日本インキ化学工業（株）社製）４５部、ビキシレノール型エポキシ樹脂「エピコートＹＸ−４０００」（エポキシ当量１８５、ジャパンエポキシレジン（株）社製）とビスフェノールＳからなるフェノキシ樹脂のシクロヘキサノン溶液「ＹＬ−６７４６Ｈ３０」（不揮発分３０重量％、重量平均分子量３００００、ジャパンエポキシレジン（株）社製）７０部、さらに球形シリカ１８部、微粉砕シリカ２部を添加し、ロール分散を行なって熱硬化性樹脂組成物の樹脂ワニスを作成した。
【００８５】
比較例１記載の樹脂ワニスを、離型処理を施した厚さ３８μｍのポリエチレンテレフタレートフィルム上に、乾燥後の樹脂厚みが３０μｍとなるように塗布し、８０〜１４０℃（平均１１０℃）で約１６分間乾燥させ、続いて、１８０℃で３０分加熱し熱硬化させて、回路基板用フィルムを作成した。
【００８６】
熱硬化物層をポリエチレンテレフタレートフィルムより剥がし、更に２００℃で３時間加熱した後、ＪＩＳ Ｋ ７１２７に従い、このフィルムからダンベル状の試験片を切り出した。これら試験片を用いて引張試験を行い、硬化フィルムの破断強度、破断伸度を測定したところ、次のような値を示し、機械特性に優れる硬化物フィルムを得ることができなかった。破断強度＝８５ＭＰａ、破断伸度＝１．８％
また、この硬化物フィルムを１８０度で折り曲げた際、フィルムにはクラックが発生した。
【００８７】
＜比較例２＞
２５μｍのポリイミドフィルム「カプトンＥＮ」上に、Ｎｉシード層をスパッタで形成し、銅メッキ（８μｍ）した市販の「Ｓ‘ＰＥＲＦＬＥＸ」（住友金属鉱山（株）社製）のメッキ皮膜の接着強度は０．５ｋｇｆ／ｃｍ（４．９×１０２Ｎ／ｍ）であった。
【００８８】
【発明の効果】
本発明によれば、メッキにより簡便にピール強度に優れ微細な回路形成が可能な導体層を形成することができ、可とう性やフレキシブル回路基板等のベースフィルムとして要求される緒物性にも優れた回路基板用フィルムを得ることができ、該フィルムはフレキシブル回路基板用のベースフィルムとして特に優れたものとなる。[0001]
[Industrial application fields]
INDUSTRIAL APPLICABILITY The present invention relates to a circuit board, particularly a base film for a circuit board that can be used for an electronic circuit of a portable device such as a cellular phone, a PDA (Personal Digital Assistant), and a notebook personal computer, particularly for a flexible circuit board. It relates to a suitable base film.
[0002]
[Prior art]
Films such as polyimide resin film, liquid crystal polymer film, aramid resin film and polyetheretherketone film have excellent heat resistance, dimensional stability, solvent resistance, and electrical and mechanical properties. Widely used as an insulating material for electronic devices. In particular, a conductor film formed on a polyimide film is often used for flexible circuit boards (FPC) such as tape automated bonding (TAB).
[0003]
Conventionally, as a method for forming a conductor layer on a polyimide film, a laminating method in which a polyimide film and a copper foil are bonded with an adhesive (thermosetting resin composition) has been the mainstream. However, the film for a substrate with a copper foil produced by this method requires a complicated drilling process when forming a circuit. For example, when forming a through-hole to connect circuits formed on both sides of a substrate film with a laser, first through a step of making a hole in the copper foil on both sides by etching, and then further drilling a hole in the insulating layer portion with a laser It is necessary to make it. In the laminating method, for example, a copper foil having a certain thickness such as 35 μm, 18 μm, and 12 μm is used. However, when the thickness increases, it becomes difficult to form a fine circuit by the subtractive method, while the thickness is reduced. Then there is a problem that it becomes expensive. In particular, when the inner wall of the through hole is plated, the plating is also formed on the copper foil, which increases the thickness and is inconvenient for forming a fine circuit.
[0004]
In order to solve such problems, after forming a base metal layer on the polyimide resin film by a dry process such as direct sputtering or vapor deposition, a conductor layer is formed by electroless copper plating and further by electrolytic copper plating. Attempts have been made to perform such a method (Patent Document 1 and Patent Document 2) and a method of directly plating on a polyimide film to form a conductor layer (Patent Document 3 and Patent Document 4). In the former, in order to improve the adhesion between the polyimide resin film and the conductor layer, it is necessary to form a base metal layer such as cobalt, nickel, chromium by a dry metallizing method such as sputtering, vacuum deposition, etc. It becomes complicated and it is difficult to prevent pinholes. In the latter case, the process is complicated because a process such as electroless nickel plating is required prior to the electroless copper plating or electrolytic copper plating process in addition to the special hydrophilization treatment of the surface of the polyimide resin film. Also, the adhesive strength is not always satisfactory.
[0005]
On the other hand, in Patent Document 5, in order to solve these problems, a film for a circuit board composed of a heat-resistant resin layer and a roughened resin cured material layer made of a thermosetting material that can be roughened with an oxidizing agent. Is disclosed. While the film has a heat-resistant resin layer, a conductor layer can be formed by plating, a fine pattern can be formed, and a circuit board having excellent plating adhesive strength can be produced. However, it is inevitable that the film has an adhesive problem at the interface between two layers having different physical properties, that is, a heat-resistant resin layer and a cured product layer. Further, although the heat-resistant resin layer is excellent in flexibility, the cured product layer is not always satisfactory in terms of flexibility, and further improvement has been demanded for use as a base film of a circuit board such as a flexible circuit board. .
[0006]
[Patent Document 1]
JP 2001-77493 A
[Patent Document 2]
Japanese Patent Laid-Open No. 7-243049
[Patent Document 3]
JP-A-8-31881
[Patent Document 4]
Japanese Patent Laid-Open No. 7-234049
[Patent Document 5]
International Publication WO03 / 009655 Pamphlet
[0007]
[Problems to be solved by the invention]
The present invention provides a base film for a circuit board that is free from problems of adhesion between layers as seen in a film composed of a plurality of layers, has excellent plating properties and flexibility, and is suitable for fine circuit formation. In particular, an object is to provide a base film suitable for a flexible circuit board.
[0008]
[Means for Solving the Problems]
As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a heat-resistant resin having a specific physical property and soluble in an organic solvent, a thermosetting resin, and a filler are blended at a specific ratio. The present inventors have found that a cured product of the curable resin composition has excellent plating properties and flexibility and is a film suitable for fine circuit formation, thus completing the present invention.
[0009]
That is, the present invention includes the following contents.
[0010]
[1] Component (a) Heat resistance dissolved in an organic solvent having a breaking strength of 100 MPa or more, a breaking elongation of 10% or more, a thermal expansion coefficient between 20 to 150 ° C. of 60 ppm or less, and a glass transition temperature of 160 ° C. or more. Resin, component (b) thermosetting resin, (c) filler, and (d) resin having polybutadiene skeleton and / or polysiloxane skeleton, and the ratio of component (a) to component (b) is weight The ratio of the total amount of component (a) and component (b) and component (c) is 100: 1 to 3: 2 by weight, and the ratio of component (d) is 100: 1 to 1: 1. Thermosetting of thermosetting resin composition whose blending amount is 0.1 to 15 parts by weight with respect to 100 parts by weight of component (a), and the total blending amount of components (a) to (d) is 70% by weight or more. A film for a circuit board having a thickness of 5 to 20 μm.
[0011]
[2] A film for a circuit board having the following A layer and B layer adjacent to each other,
Layer A: Component (a) Heat resistance that dissolves in an organic solvent having a breaking strength of 100 MPa or more, a breaking elongation of 10% or more, a thermal expansion coefficient between 20 to 150 ° C. of 60 ppm or less, and a glass transition temperature of 160 ° C. or more. Resin, component (b) thermosetting resin, (c) filler, and (d) resin having polybutadiene skeleton and / or polysiloxane skeleton, and the ratio of component (a) to component (b) is weight The ratio of the total amount of component (a) and component (b) and component (c) is 100: 1 to 3: 2 by weight, and the ratio of component (d) is 100: 1 to 1: 1. Thermosetting of thermosetting resin composition whose blending amount is 0.1 to 15 parts by weight with respect to 100 parts by weight of component (a), and the total blending amount of components (a) to (d) is 70% by weight or more. A thermoset layer of 5 to 20 μm in thickness and B layer: metal foil.
[0012]
[3] A film for a circuit board comprising the following A layer and C layer, and having a layer structure in the order of C layer, A layer and C layer,
Layer A: Component (a) Heat resistance that dissolves in an organic solvent having a breaking strength of 100 MPa or more, a breaking elongation of 10% or more, a thermal expansion coefficient between 20 to 150 ° C. of 60 ppm or less, and a glass transition temperature of 160 ° C. or more. Resin, component (b) thermosetting resin, (c) filler, and (d) resin having polybutadiene skeleton and / or polysiloxane skeleton, and the ratio of component (a) to component (b) is weight The ratio of the total amount of component (a) and component (b) and component (c) is 100: 1 to 3: 2 by weight, and the ratio of component (d) is 100: 1 to 1: 1. Thermosetting of thermosetting resin composition whose blending amount is 0.1 to 15 parts by weight with respect to 100 parts by weight of component (a), and the total blending amount of components (a) to (d) is 70% by weight or more. 5 to 20 μm-thick thermoset layer and C layer: electroless copper mesh Layer.
[0013]
[4] A circuit board film comprising the following A layer C layer and D layer, and having a layer structure in the order of D layer, C layer, A layer, C layer and D layer,
Layer A: Component (a) Heat resistance that dissolves in an organic solvent having a breaking strength of 100 MPa or more, a breaking elongation of 10% or more, a thermal expansion coefficient between 20 to 150 ° C. of 60 ppm or less, and a glass transition temperature of 160 ° C. or more. Resin, component (b) thermosetting resin, (c) filler, and (d) resin having polybutadiene skeleton and / or polysiloxane skeleton, and the ratio of component (a) to component (b) is weight The ratio of the total amount of component (a) and component (b) and component (c) is 100: 1 to 3: 2 by weight, and the ratio of component (d) is 100: 1 to 1: 1. Thermosetting of thermosetting resin composition whose blending amount is 0.1 to 15 parts by weight with respect to 100 parts by weight of component (a), and the total blending amount of components (a) to (d) is 70% by weight or more. A thermoset layer having a thickness of 5 to 20 μm,
C layer: electroless copper plating layer, and
D layer: an electrolytic copper plating layer.
[0014]
[5] A circuit board film comprising the following A layer, B layer and C layer, and having a layer structure in the order of B layer, A layer and C layer,
Layer A: Component (a) Heat resistance that dissolves in an organic solvent having a breaking strength of 100 MPa or more, a breaking elongation of 10% or more, a thermal expansion coefficient between 20 to 150 ° C. of 60 ppm or less, and a glass transition temperature of 160 ° C. or more. Resin, component (b) thermosetting resin, (c) filler, and (d) resin having polybutadiene skeleton and / or polysiloxane skeleton, and the ratio of component (a) to component (b) is weight The ratio of the total amount of component (a) and component (b) and component (c) is 100: 1 to 3: 2 by weight, and the ratio of component (d) is 100: 1 to 1: 1. Thermosetting of thermosetting resin composition whose blending amount is 0.1 to 15 parts by weight with respect to 100 parts by weight of component (a), and the total blending amount of components (a) to (d) is 70% by weight or more. A thermoset layer having a thickness of 5 to 20 μm,
B layer: metal foil, and
C layer: electroless copper plating layer.
[0015]
[6] A circuit board film comprising the following A layer, B layer, C layer and D layer, and having a layer structure in the order of B layer, A layer, C layer and D layer,
Layer A: Component (a) Heat resistance that dissolves in an organic solvent having a breaking strength of 100 MPa or more, a breaking elongation of 10% or more, a thermal expansion coefficient between 20 to 150 ° C. of 60 ppm or less, and a glass transition temperature of 160 ° C. or more. Resin, component (b) thermosetting resin, (c) filler, and (d) resin having polybutadiene skeleton and / or polysiloxane skeleton, and the ratio of component (a) to component (b) is weight The ratio of the total amount of component (a) and component (b) and component (c) is 100: 1 to 3: 2 by weight, and the ratio of component (d) is 100: 1 to 1: 1. Thermosetting of thermosetting resin composition whose blending amount is 0.1 to 15 parts by weight with respect to 100 parts by weight of component (a), and the total blending amount of components (a) to (d) is 70% by weight or more. A thermoset layer having a thickness of 5 to 20 μm,
B layer: metal foil,
C layer: electroless copper plating layer, and
D layer: an electrolytic copper plating layer.
[0016]
[7] The circuit board film according to any one of [1] to [6], wherein the heat-resistant resin of component (a) is at least one heat-resistant resin selected from the group consisting of polyimide, polyamideimide, and polyamide.
[0017]
[8] The circuit board film according to any one of [1] to [6], wherein the heat-resistant resin of the component (a) is polyamideimide.
[0018]
[9] The above-mentioned [1], wherein the thermosetting resin of component (b) is one or more thermosetting resins selected from the group consisting of an epoxy resin, a polymer of a bismaleimide compound and a diamine compound, and a cyanate ester compound. The film for circuit boards as described in thru | or [6].
[0019]
[10] The circuit board film according to any one of [1] to [6], wherein the thermosetting resin of the component (b) is an epoxy resin.
[0020]
[11] The circuit board film according to any one of [1] to [6], wherein the filler of component (c) is one or more fillers selected from the group consisting of acrylic rubber particles, silicon particles, and silica.
[0021]
[12] A circuit board manufactured using the circuit board film according to any one of [1] to [11].
[0022]
[13] A flexible circuit board manufactured using the circuit board film according to any one of [1] to [11].
[0023]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is described in detail below.
[0024]
The thermosetting heat-resistant resin composition in the present invention, that is, the component (a) has a breaking strength of 100 MPa or more, a breaking elongation of 10% or more, a thermal expansion coefficient between 20 to 150 ° C. of 60 ppm or less, and a glass transition temperature of 160. A heat-resistant resin that dissolves in an organic solvent at or above ° C, component (b) a thermosetting resin, (c) a filler, and (d) a resin having a polybutadiene skeleton and / or a polysiloxane skeleton. ) And component (b) in a weight ratio of 100: 1 to 1: 1, and the total amount of component (a) and component (b) and the ratio of component (c) are in a weight ratio of 100: 1 to 1-3. 2: The amount of component (d) is 0.1 to 15 parts by weight with respect to 100 parts by weight of component (a), and the total amount of components (a) to (d) is 70% by weight or more. A certain thermosetting resin composition is demonstrated.
[0025]
The heat-resistant resin of component (a) in the present invention has a chemical structure of polyimide resin, polyamideimide resin, polyamide resin, polyetherimide resin, polybenzoxazole resin, polybenzimidazole resin, polyamic acid, or these resin components. It can be selected from heat resistant resins such as copolymers. Among these heat resistant resins, polyimide resins, polyamideimide resins, and polyamide resins are preferable, and polyamideimide is particularly preferable. When polyamic acid, which is a polyimide precursor, is used as a heat-resistant resin, it requires an imidization temperature of at least 300 ° C., so that it has a heat resistance of 300 ° C. or higher such as an epoxy resin, an organic filler, or butadiene rubber. It is difficult to use those that do not have
[0026]
The heat-resistant resin in the present invention needs to have a breaking strength of 100 MPa or more, a breaking elongation of 10% or more, a thermal expansion coefficient of 70 ppm or less, and a glass transition temperature of 160 ° C. or more. The circuit board film of the present invention can be suitably used as a base film for a circuit board such as a flexible circuit board. However, when the heat-resistant resin of the component (a) does not satisfy these values, it is necessary as a base film. It becomes difficult to obtain a strong toughness.
[0027]
The breaking strength and breaking elongation are determined according to the method described in JIS (Japanese Industrial Standard) K7127. The thermal expansion coefficient and glass transition temperature are determined according to the method described in JIS K 7197. The case where the glass transition temperature is higher than the decomposition temperature and no substantial glass transition temperature is observed is also included in the definition of “the glass transition temperature is 160 ° C. or higher” in the present invention. The decomposition temperature is defined as the temperature at which the mass reduction rate is 5% when measured according to the method described in JIS K 7120.
[0028]
It is essential that the heat resistant resin in the present invention has a property of being dissolved in an organic solvent. A heat-resistant resin that cannot be dissolved in a solvent cannot be used in the present invention because it cannot be mixed with other components to prepare a composition. Although the organic solvent is not particularly limited, an organic solvent that is liquid at room temperature of 20 to 30 ° C. and has a property of dissolving the heat-resistant resin is used due to the properties of the present invention. Moreover, it is necessary to be an organic solvent which does not react with a heat-resistant resin or a thermosetting resin, and for example, cresol having a phenolic hydroxyl group is excluded.
[0029]
Preferred organic solvents used in the present invention include, for example, ketones such as acetone, methyl ethyl ketone, cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, cellosolve, butyl. Examples thereof include carbitols such as carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. Two or more organic solvents may be used in combination.
[0030]
Preferable specific examples marketed as the heat-resistant resin of component (a) include soluble polyimides “Rika Coat SN20” and “Lika Coat PN20” manufactured by Shin Nippon Rika Co., Ltd., polys manufactured by Nippon GE Plastics Co., Ltd. Examples include ether imide “Ultem”, polyamide imide “Bilomax HR11NN” and “Vilomax HR16NN” manufactured by Toyobo Co., Ltd.
[0031]
The heat resistant resin of component (a) may be used alone or in combination of two or more.
[0032]
The thermosetting resin of the component (b) in the present invention is not particularly limited as long as it is thermosetting within a range of 150 to 350 ° C. which is usually used in plastic film production, but it is relatively low temperature. It is more preferable to select one that cures in the range of 150 to 200 ° C. Examples of the thermosetting resin of component (b) include an epoxy resin having two or more epoxy groups in one molecule, a polymer of a bismaleimide compound and a diamine compound, a cyanate ester compound, a bismaleimide compound, a bisallyl nazide resin, and a benzoate. A thermosetting resin such as an oxazine compound can be given. Among these, an epoxy resin having two or more epoxy groups in one molecule, a polymer of a bismaleimide compound and a diamine compound, a cyanate ester compound, or a mixture thereof is preferable. Also, a mixture of an epoxy resin having two or more epoxy groups in one molecule and a polymer of a bismaleimide compound and a diamine compound, a mixture of an epoxy resin having two or more epoxy groups in a molecule and a cyanate ester compound, one molecule An epoxy resin having two or more epoxy groups is more preferable, and an epoxy resin having two or more epoxy groups in one molecule is particularly preferable.
[0033]
Epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac epoxy resin, bisphenol S type epoxy resin, alkylphenol novolac type epoxy resin, biphenol type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin. And epoxy resins having two or more functional groups in one molecule such as an epoxidized product of a condensate of phenol and an aromatic aldehyde having a phenolic hydroxyl group, triglycidyl isocyanurate, alicyclic epoxy resin, etc. .
[0034]
When using an epoxy resin, an epoxy curing agent is required. As epoxy curing agent, amine curing agent, guanidine curing agent, imidazole curing agent, phenol curing agent, acid anhydride curing agent, hydrazide curing agent, carboxylic acid curing agent, thiol curing agent or these Epoxy adducts or microencapsulated ones. Further, a curing accelerator such as triphenylphosphine, phosphonium borate, 3- (3,4-dichlorophenyl) -1,1-dimethylurea may be used in combination.
[0035]
Specific examples of the epoxy curing agent include, for example, dicyandiamide, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,4-diamino-6- (2-methyl-1-imidazolylethyl) -1, 3, Examples include 5-triazine / isocyanuric acid adducts, triazine structure-containing novolak resins (for example, Phenolite 7050 series: manufactured by Dainippon Ink and Chemicals, Inc.).
[0036]
Examples of the polymer resin of the bismaleimide compound and the diamine compound include “Techmite E2020” manufactured by Printec Co., Ltd.
Examples of the cyanate ester compounds include “Primaset BA200” (Lonza Co., Ltd.), “Primaset BA230S” (Lonza Co., Ltd.), and bisphenol H type, which are bisphenol A type cyanate esters. “Primaset LECY” which is a cyanate ester (manufactured by Lonza), “Arocy L10” (manufactured by Bantico), “Primaset” PT30 which is a novolak cyanate ester “Arocy XU-371” (manufactured by Bantico Co., Ltd.), “Arocy XP71787.02L” (Bantico Co., Ltd.) which is a dicyclopentadiene-type cyanate ester. (Made by company) Etc.
As bismaleimide compounds, 4,4′-diphenylmethane bismaleimide “BMI-S” (manufactured by Mitsui Chemicals), polyphenylmethane maleimide “BMI-M-20” (Mitsui Chemicals, Inc.) Etc.).
Examples of the bisallylnazide resin include “BANI-M” (manufactured by Maruzen Petrochemical Co., Ltd.) which is diphenylmethane-4,4′-bisallylnadicimide.
Examples of the benzoxazine resin include “Ba type benzoxazine” and “Bm type benzoxazine” manufactured by Shikoku Kasei Co., Ltd.
[0037]
These thermosetting resins of component (b) may be used alone or in combination of two or more.
[0038]
The filler of the component (c) in the present invention is a conductor layer that forms an appropriate roughened surface when the surface of the thermosetting product of the thermosetting resin composition is roughened with an oxidizing agent and is excellent in peel strength by plating. It is important to allow formation. Fillers can be classified into inorganic fillers and organic fillers. The inorganic filler also has an effect of lowering the thermal expansion coefficient of the cured product, and the organic filler has an effect of relieving stress in the cured product.
[0039]
Inorganic fillers include silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate, titanate Examples include strontium, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, and calcium zirconate. Silica is particularly preferable. The inorganic filler preferably has an average particle size of 5 μm or less. When the average particle diameter exceeds 5 μm, it may be difficult to stably form a fine pattern when forming a circuit pattern on a conductor layer formed by plating after roughening. Moreover, in order to improve moisture resistance, what was surface-treated with surface treating agents, such as a silane coupling agent, is preferable.
[0040]
The organic filler is preferably acrylic rubber particles or silicon particles. From the viewpoint of forming appropriate irregularities after roughening, it is more preferable to use a flat organic filler. Similarly, the organic filler preferably has an average particle size of 5 μm or less.
[0041]
The “resin having a polybutadiene skeleton and / or a polysiloxane skeleton” as the component (d) in the present invention is important for forming a preferable roughened surface on the surface of the cured product with an oxidizing agent, as in the case of the component (c). .
[0042]
Examples of polybutadiene include polybutadiene rubber, epoxy-modified polybutadiene rubber, urethane-modified polybutadiene rubber, acrylonitrile-modified polybutadiene rubber, methacrylonitrile-modified polybutadiene rubber, acrylonitrile-butadiene rubber having a carboxyl group, and acrylonitrile rubber-dispersed epoxy resin. Examples of the resin having a siloxane skeleton include siloxane skeleton-containing polyamideimides such as “KS9100” and “KS9300” manufactured by Hitachi Chemical Co., Ltd.
[0043]
In the thermosetting resin composition in the present invention, the ratio of the heat-resistant resin of component (a) and the thermosetting resin of component (b) needs to be in the range of 100: 1 to 1: 1 by weight ratio. To do. A more preferable range is that the ratio of the component (a) to the component (b) is 100: 1 to 5: 3 by weight. If the proportion of component (a) is too small, it will be difficult to obtain the toughness required as a base film for circuit boards. Moreover, since the component (a) has low resistance to an alkaline permanganic acid solution that is widely used as an oxidizing agent, if the proportion of the component (a) is too large, the physical properties of the cured product may be reduced.
[0044]
In the thermosetting resin composition in the present invention, it is necessary that the total amount of the component (a) and the component (b) and the ratio of the component (c) are in the range of 100: 1 to 3: 2 by weight ratio. To do. A more preferable range is 100: 3 to 20:11. When the ratio of the filler of the component (c) is larger than this range, the physical property value necessary for the circuit board film of the present invention tends to be difficult to obtain, and when it is small, sufficient uneven surface tends not to be obtained due to roughening. It is in.
[0045]
In the thermosetting resin composition in this invention, it is required that the compounding quantity of a component (d) is the range of 0.1-15 weight part with respect to 100 weight part of component (a). A more preferred range is 0.1 to 15 parts by weight per 100 parts by weight of component (a). If the amount of component (d) is more than this range, the mechanical strength of the cured product tends to be reduced, and if it is less, sufficient uneven surface tends to be difficult to obtain due to roughening with an oxidizing agent.
[0046]
The cured product of the thermosetting resin composition in the present invention has both toughness as a base film for a circuit board and roughening properties capable of forming a conductor layer having excellent peel strength by plating. That is, the cured product has a breaking strength of 100 MPa or more, a breaking elongation of 5% or more, a thermal expansion coefficient between 20 to 150 ° C. of 70 ppm or less, and a glass transition temperature of 150 ° C. or more, more preferably, It is possible to achieve physical properties with a breaking strength of 110 MPa or more, a breaking elongation of 10% or more, a thermal expansion coefficient between 20 and 150 ° C. of 50 ppm or less, and a glass transition temperature of 200 ° C. or more. Further, the surface of the cured product is roughened with an oxidizer and a conductor layer is formed by plating, so that 0.6 kgf / cm (5.9 × 10 6 2 N / m) or more, preferably 0.7 kgf / cm (6.9 × 10 2 N / m) or higher peel strength of the conductor layer can be achieved.
[0047]
In the thermosetting resin composition in the present invention, components other than the components (a) to (d) can be blended within the range in which the effects of the present invention are sufficiently exhibited. ) To (d) are required to be 70% by weight or more (that is, 70% to 100% by weight). A more preferable range is 75% by weight or more, further preferably 80% by weight or more, further preferably 85% by weight or more, and further preferably 90% by weight or more. When the total amount of components (a) to (d) is less than 70% by weight, the effects of the present invention tend not to be sufficiently exhibited.
[0048]
Examples of other components blended in the thermosetting resin composition of the present invention include thickeners such as olben and benton, silicone-based, fluorine-based, polymer-based antifoaming agents or leveling agents, imidazole-based compounds, Adhesion imparting agents such as thiazole, triazole, and silane coupling agents, resin additives such as phthalocyanine / blue, phthalocyanine / green, iodin / green, disazo yellow, carbon black and other colorants, and (a), (b ), (D) and other optional resin components.
[0049]
The circuit board film of the present invention comprises a cured product of the thermosetting resin composition described above. The surface of the cured product can be formed with fine irregularities on the surface by a roughening treatment with an oxidizing agent, and a conductor layer can be formed on the surface of the cured product after the roughening treatment by plating.
[0050]
The film for a circuit board of the present invention is obtained by, for example, applying a varnish of a thermosetting resin composition to the surface of a smooth and releasable support, and peeling it from the support after drying or at an appropriate stage during drying. Can be manufactured.
[0051]
Examples of organic solvents for preparing varnish include ketones such as acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, acetate esters such as carbitol acetate, cellosolve, butyl Examples thereof include carbitols such as carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. Two or more organic solvents may be used in combination.
[0052]
As a specific method for producing a film for a circuit board, a varnish of a thermosetting resin composition is extruded from a T die such as a solution casting method (casting method) usually used in plastic film production, Cast onto a stainless steel endless belt running underneath, volatilize the solvent properly on this belt to obtain a film, and then peel the film off the belt for final drying and thermosetting Then, a varnish of the thermosetting resin composition is applied onto a support having peelability, and the thermosetting resin composition is dried until a film is formed, and then the resin composition film is peeled from the peelable film. And final drying and heat curing. The conditions for drying and thermosetting are not particularly limited, and are appropriately determined according to workability, taking into account differences in boiling point of the solvent, adhesion between the support and the resin composition, reaction initiation temperature of the thermosetting component, and the like. be able to. The drying conditions for forming a film vary depending on the type of solvent contained in the varnish, but can be selected from a range of about 1 to 30 minutes at 50 to 200 ° C., for example. Moreover, the conditions of the process of performing final drying and thermosetting are not particularly limited, and those skilled in the art can appropriately set preferable conditions for finally setting the thermosetting resin composition to a cured state. It can be selected from a range of about 30 minutes to 24 hours at a temperature of from 350C to 350C.
[0053]
The film for a circuit board made of a cured product of the thermosetting resin composition obtained as described above is roughened by forming dense irregularities on the surface by a method known to those skilled in the art, that is, by a roughening treatment with an oxidizing agent. The conductor layer can be formed by a method of plating on the surface. After forming the conductor layer, the peel strength of the conductor layer can be further improved and stabilized by annealing at 150 to 200 ° C. for 20 to 90 minutes.
[0054]
Examples of the oxidizing agent used for the roughening treatment include alkaline permanganic acid solutions, dichromates, hydrogen peroxide, sulfuric acid, nitric acid and other oxidizing agent solutions, and are particularly widely used in the production of printed wiring boards. Alkaline permanganic acid solutions are preferred. Examples of the alkaline permanganate solution include a solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide.
[0055]
The conductor layer can be formed by plating by a method combining electroless plating and electrolytic plating, or by forming a plating resist having a pattern opposite to that of the conductor layer and forming the conductor layer only by electroless plating.
[0056]
Electroless copper plating can be generally performed by a method usually used in an additive method or a semi-additive method of a printed wiring board. That is, first, the catalyst can be applied to the film surface roughened with an oxidizing agent, and then immersed in a predetermined electroless copper plating solution under predetermined conditions. As the catalyst imparted to the roughened surface, palladium metal which is generally used is more preferable. Various electroless copper plating solutions are commercially available due to differences in bath constituents such as complexing agents and reducing agents, but are not particularly limited. The thickness of the electroless copper plating layer (C layer) is usually 0.1 to 3 μm, and preferably 0.3 to 2 μm.
[0057]
A method of performing electrolytic copper plating on the electroless copper plating surface can also be performed according to a known method, and various types of electrolytic copper plating solutions are used depending on differences in bath constituents, but are generally commonly used. A copper sulfate plating bath is preferred. The thickness of the electrolytic copper plating layer (D layer) is usually 3 to 35 μm, and preferably 5 to 20 μm.
[0058]
As a method of forming a circuit in the conductor layer, a subtractive method or a semi-additive method known to those skilled in the art can be used. In the case of the subtractive method, after forming an electroplating layer on the electroless copper plating layer, an etching resist is formed, and a conductor pattern is formed by etching with an etchant such as ferric chloride or cupric chloride. Then, the circuit can be formed by removing the etching resist. In the case of the semi-additive method, a pattern resist is applied on the electroless copper plating layer, and after forming an electrolytic copper plating layer (pattern plating layer) with a desired thickness, the pattern resist is peeled off and the electroless copper plating layer is formed. Is removed by flash etching, whereby a circuit board can be obtained.
[0059]
In addition, in the film for circuit boards of this invention, it is good also as a film of the structure which has A layer which consists of a thermosetting resin composition, and B layer which consists of metal foil adjacent. In such a film for a circuit board, the cured product layer can be roughened with an oxidizing agent as described above, and further, electroless copper plating can be performed on the roughened surface, and further an electric field can be formed on the electroless copper plating. Copper plating can be performed. Thus, by performing the roughening treatment and the plating treatment on the surface of the cured product layer of the film, it is possible to produce a double-sided copper-clad circuit board in which one side is plated and the other side is formed of a metal foil. Such a film for a circuit board is formed by, for example, applying a metal foil that has already been bonded when forming a conductor layer including a formed hole in a plating process by drilling a cured product layer with a laser. There is an advantage that a via post can be formed in the hole at the base point.
[0060]
Production of such a film with a metal foil is generally a metal foil (B layer) as a support,
It can be obtained by applying and drying the varnish of the thermosetting resin composition in the present invention on this surface to form a cured product layer (A layer) as described above. The metal foil is particularly preferably a copper foil. The copper foil may be either a rolled copper foil or an electrolytic copper foil, and the thickness is generally 2 μm or more and 36 μm or less. When the copper foil is thin and workability is difficult, a copper foil with a carrier may be used as necessary. The surface of the metal foil to which the resin is applied is more preferably a mat surface from the viewpoint of increasing the adhesive force between the resin and the metal foil. You may use what gave chemical processing, such as a ring agent.
[0061]
Examples of the preferable layer structure of the circuit board film in the present invention include the following layer structure examples 1 to 6.
[0062]
Layer configuration example 1: Thermoset layer (A layer)
Layer configuration example 2: thermoset layer (A layer) / metal foil (B layer)
Layer configuration example 3: electroless plating layer (C layer) / thermosetting material layer (A layer) / electroless plating layer (C layer)
Layer configuration example 4: electrolytic copper plating layer (D layer) / electroless plating layer (C layer) / thermosetting material layer (A layer) / electroless plating layer (C layer) / electrolytic copper plating layer (D layer)
Layer configuration example 5: electroless plating layer (C layer) / thermosetting material layer (A layer) / metal foil (B layer)
Layer configuration example 6: electrolytic copper plating layer (D layer) / electroless plating layer (C layer) / thermosetting material layer (A layer) / metal foil (B layer)
[0063]
In addition, the film for circuit boards of this invention can also be wound up in roll shape and preserve | saved and stored.
【Example】
[0064]
EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated concretely, this invention is not limited to this. In the examples, parts means parts by weight.
[0065]
<Example 1>
30 parts of bisphenol A type epoxy resin “Epicoat 828” (epoxy equivalent 190, manufactured by Japan Epoxy Resins Co., Ltd.), 2-butanone solution of phenol novolac resin containing triazine ring “Phenolite LA7052” (nonvolatile content 60 wt%, nonvolatile Phenol hydroxyl group equivalent of 120 parts, manufactured by Dainippon Ink & Chemicals, Inc.) 13 parts, flat silicon resin particle “AGM101” (produced by Takemoto Yushi Co., Ltd.) 1 part (average particle size 0.41 μm) 3 parts of spherical silica (average particle size 1 μm) are mixed and roll-dispersed. Polyamideimide “HR11NN” (non-volatile content 15% by weight, breaking strength 150 MPa, breaking elongation 80%, thermal expansion coefficient 42 ppm, glass transition temperature) 460 parts at 300 ° C., manufactured by Toyobo Co., Ltd.) and siloxane-modified polyamideimide “KS” 9100 "(non-volatile content 31% by weight, manufactured by Hitachi Chemical Co., Ltd.) was mixed to prepare a resin varnish of a thermosetting resin composition.
[0066]
<Example 2>
The resin varnish described in Example 1 was applied onto a polyethylene terephthalate film having a thickness of 38 μm so that the resin thickness after drying was 30 μm, and dried at 80 to 140 ° C. (average 110 ° C.) for about 16 minutes. Subsequently, the resin composition film is peeled off from the polyethylene terephthalate film, and the resin composition film is fixed to a metal jig, and then heated at 180 ° C. for 30 minutes to be thermally cured. A circuit board film was prepared.
[0067]
The thermoset layer was peeled off from the polyethylene terephthalate film and further heated at 200 ° C. for 3 hours, and then a dumbbell-shaped test piece was cut out from this film according to JIS K 7127. A tensile test was performed using these test pieces, and the breaking strength and breaking elongation of the film were measured. The following values were obtained. Breaking strength = 110 MPa, breaking elongation = 13%. Moreover, when this cured | curing material film was bent at 180 degree | times, the film did not generate | occur | produce a crack and showed sufficient flexibility.
[0068]
<Example 3>
The resin varnish described in Example 1 was applied onto a 18 μm thick copper foil so that the resin thickness after drying was 20 μm, dried at 80 to 140 ° C. (average 110 ° C.) for about 16 minutes, and further Then, it was heated at 180 ° C. for 30 minutes and thermally cured to produce a circuit board film corresponding to the layer constitution example 2.
[0069]
<Example 4>
The film for circuit board corresponding to the structural example (1) described in Example 2 was immersed in a swelling solution using “Swelling Dip Securiganth P” (manufactured by Atotech Japan Co., Ltd.) for 5 minutes at 80 ° C. After swelling the surface of the hardened resin layer, it is roughened by immersing it in an alkaline permanganate solution at 80 ° C. for 10 minutes, and the remaining manganese on the surface of the hardened resin layer is reduced and removed. did. Subsequently, a catalyst for electroless copper plating was applied, and then immersed in an electroless copper plating solution at 32 ° C. for 30 minutes to form a 1.5 μm electroless copper plating film. This was dried at 120 ° C. for 30 minutes to obtain a circuit board film corresponding to the layer constitution example 3. Further, this was further washed with an acid, a phosphorous copper plate as an anode, and a cathode current density of 2.0 A / dm. 2 Then, electrolytic copper plating was performed for 12 minutes to form a copper plating film having a thickness of 5 μm. Finally, annealing was performed at 200 ° C. for 3 hours to obtain the circuit board film described in the layer structure example 4. The adhesive strength (peel strength) of the plating film is 0.8 kgf / cm (7.8 × 10 8 2 N / m).
[0070]
<Example 5>
A cured product obtained by immersing the film for circuit board corresponding to the layer configuration example 2 described in Example 3 in a swelling solution using “Swelling Dip Securiganth P” (manufactured by Atotech Japan Co., Ltd.) at 80 ° C. for 5 minutes. After swelling the surface of the layer, it was then roughened by dipping in an alkaline permanganate solution at 80 ° C. for 10 minutes, and further, manganese remaining on the surface of the cured product layer was reduced and removed. Subsequently, a catalyst for electroless copper plating was applied, and then immersed in an electroless copper plating solution at 32 ° C. for 30 minutes to form a 1.5 μm electroless copper plating film. This was dried at 120 ° C. for 30 minutes to obtain a circuit board film described in Layer Construction Example 5. Further, this was further washed with an acid, a phosphorous copper plate as an anode, and a cathode current density of 2.0 A / dm. 2 Then, electrolytic copper plating was performed for 12 minutes to form a copper plating film having a thickness of 5 μm. Finally, annealing was performed at 200 ° C. for 3 hours to obtain a circuit board film described in Layer Structure Example 6. The adhesive strength (peel strength) of the plating film is 0.8 kgf / cm (7.8 × 10 8 2 N / m).
[0071]
<Example 6>
First, 15 parts of bisphenol A type epoxy resin “Epicoat 828” (epoxy equivalent 190, manufactured by Japan Epoxy Resins Co., Ltd.), 10 parts of aromatic hydrocarbon solvent “Ipsol 150” (produced by Idemitsu Petrochemical Co., Ltd.) 1 part of epoxidized polybutadiene rubber “Denalex R45EPT” (manufactured by Nagase Kasei Kogyo Co., Ltd.), 3 parts of acrylic rubber fine particles “AC3832” (manufactured by Ganz Kasei Co., Ltd.) and 40 parts of spherical silica are mixed and roll-dispersed. I let you. To this, 35 parts of a polymer of bismaleimide and a diamine compound "Techmite E2020" (manufactured by Printec Co., Ltd.) was dissolved in 50 parts of cyclohexanone and cooled to room temperature, and 1,8- Diazabicyclo (5,4,0) undecene 0.2 part was added to 2-butanone heated and dissolved and cooled to room temperature, followed by addition of polyamideimide “HR11NN” (non-volatile content 15% by weight, Breaking strength 150 MPa
Then, 560 parts of rupture elongation 80%, thermal expansion coefficient 42 ppm, glass transition temperature 300 ° C., manufactured by Toyobo Co., Ltd.) were added to prepare a varnish of a thermosetting resin composition.
[0072]
<Example 7>
The resin varnish described in Example 6 was applied onto a 38 μm thick polyethylene terephthalate film so that the resin thickness after drying was 30 μm, and dried at 80 to 140 ° C. (average 110 ° C.) for about 16 minutes. Subsequently, the resin composition film is peeled off from the polyethylene terephthalate film, the resin composition film is fixed to a metal jig, and then heated at 180 ° C. for 30 minutes to be thermally cured, and a circuit corresponding to the layer configuration example 1 A film for a substrate was prepared.
[0073]
The thermoset layer was peeled off from the polyethylene terephthalate film and further heated at 200 ° C. for 3 hours, and then a dumbbell-shaped test piece was cut out from this film according to JIS K 7127. A tensile test was performed using these test pieces, and the breaking strength and breaking elongation of the cured film were measured. The following values were obtained. Breaking strength = 120 MPa, breaking elongation = 6%. Further, when this cured product film was bent at 180 degrees, no crack was generated in the film.
[0074]
<Example 8>
The resin varnish described in Example 7 was applied onto a 18 μm thick copper foil so that the resin thickness after drying was 20 μm, dried at 80 to 140 ° C. (average 110 ° C.) for about 16 minutes, and subsequently Then, it was heated at 180 ° C. for 30 minutes to be thermally cured, and a film for a circuit board corresponding to layer constitution example 2 was produced.
[0075]
<Example 9>
The film for circuit board corresponding to the structural example (1) described in Example 7 was immersed in a swelling solution using “Swelling Dip Securiganth P” (manufactured by Atotech Japan Co., Ltd.) for 5 minutes at 80 ° C. After swelling the surface of the hardened resin layer, it is roughened by immersing it in an alkaline permanganate solution at 80 ° C. for 10 minutes, and the remaining manganese on the surface of the hardened resin layer is reduced and removed. did. Subsequently, a catalyst for electroless copper plating was applied, and then immersed in an electroless copper plating solution at 32 ° C. for 30 minutes to form a 1.5 μm electroless copper plating film. This was dried at 120 ° C. for 30 minutes to obtain a film for a circuit board described in Structural Example (3). Further, this was further washed with an acid, a phosphorous copper plate as an anode, and a cathode current density of 2.0 A / dm. 2 Then, electrolytic copper plating was performed for 12 minutes to form a copper plating film having a thickness of 5 μm. Finally, annealing was performed at 200 ° C. for 3 hours to obtain a circuit board film described in Layer Structure Example 4. The adhesive strength of the plating film is 1.0 kgf / cm (9.8 × 10 2 N / m).
[0076]
<Example 10>
The film for circuit board corresponding to the structural example (2) described in Example 8 is cured by being immersed in a swelling solution using “Swelling Dip Securiganth P” (manufactured by Atotech Japan Co., Ltd.) at 80 ° C. for 5 minutes. After swelling the surface of the physical layer, it was then roughened by dipping in an alkaline permanganic acid solution at 80 ° C. for 10 minutes to further reduce and remove manganese remaining on the surface of the cured product layer.
[0077]
Subsequently, a catalyst for electroless copper plating was applied, and then immersed in an electroless copper plating solution at 32 ° C. for 30 minutes to form a 1.5 μm electroless copper plating film. This was dried at 120 ° C. for 30 minutes to obtain a film for a circuit board described in Structural Example (5). Further, this was further washed with an acid, a phosphorous copper plate as an anode, and a cathode current density of 2.0 A / dm. 2 Then, electrolytic copper plating was performed for 12 minutes to form a copper plating film having a thickness of 5 μm. Finally, annealing was performed at 200 ° C. for 3 hours to obtain a circuit board film described in Layer Structure Example 6. The adhesive strength of the plating film is 1.0 kgf / cm (9.8 × 10 2 N / m).
[0078]
<Example 11>
First, 15 parts of bisphenol A type epoxy resin “Epicoat 828” (epoxy equivalent 190, manufactured by Japan Epoxy Resins Co., Ltd.), 10 parts of aromatic hydrocarbon solvent “Ipsol 150” (produced by Idemitsu Petrochemical Co., Ltd.) 1 part of epoxidized polybutadiene rubber “Denalex R45EPT” (manufactured by Nagase Kasei Kogyo Co., Ltd.), 3 parts of acrylic rubber fine particles “AC3832” (manufactured by Ganz Kasei Co., Ltd.), and 40 parts of spherical silica are mixed and dispersed. I let you. Furthermore, 15 parts of bisphenol A type epoxy resin “Epicoat 828” (epoxy equivalent 190, manufactured by Japan Epoxy Resins Co., Ltd.) was added to this product, and 1,8-diazabicyclo (5,4,0) undecene was previously added. 0.4 parts of 2-butanone dissolved in 3.6 parts of heat and cooled to room temperature were added, followed by polyamideimide “HR11NN” (non-volatile content 15% by weight, breaking strength 150 MPa, breaking elongation. A thermosetting resin composition varnish was prepared by adding 450 parts of 80%, thermal expansion coefficient 42 ppm, glass transition temperature 300 ° C., manufactured by Toyobo Co., Ltd.
[0079]
<Example 12>
The resin varnish described in Example 11 was applied on a polyethylene terephthalate film having a thickness of 38 μm so that the resin thickness after drying was 30 μm, and dried at 80 to 140 ° C. (average 110 ° C.) for about 16 minutes. Subsequently, the resin composition film is peeled off from the polyethylene terephthalate film, and the resin composition film is fixed to a metal jig, and then heated at 180 ° C. for 30 minutes to be thermally cured, and a circuit corresponding to the layer configuration example 1 A film for a substrate was prepared.
[0080]
The thermoset layer was peeled off from the polyethylene terephthalate film and further heated at 200 ° C. for 3 hours, and then a dumbbell-shaped test piece was cut out from this film according to JIS K 7127. A tensile test was performed using these test pieces, and the breaking strength and breaking elongation of the cured film were measured. The following values were obtained. Breaking strength = 110 MPa, elongation at break = 5.7%. Further, when this cured product film was bent at 180 degrees, no crack was generated in the film.
[0081]
<Example 13>
The resin varnish described in Example 11 was applied on a copper foil having a thickness of 18 μm so that the resin thickness after drying was 20 μm, dried at 80 to 140 ° C. (average 110 ° C.) for about 16 minutes, and further Then, the film for a circuit board corresponding to the layer configuration example 2 was prepared by heating at 180 ° C. for 30 minutes and thermosetting.
[0082]
<Example 14>
The film for circuit board corresponding to the structural example (1) described in Example 12 is cured by being immersed in a swelling liquid using “Swelling Dip Securiganth P” (manufactured by Atotech Japan Co., Ltd.) at 80 ° C. for 5 minutes. After swelling the surface of the physical layer, it was then roughened by dipping in an alkaline permanganic acid solution at 80 ° C. for 10 minutes to further reduce and remove manganese remaining on the surface of the cured product layer. Subsequently, a catalyst for electroless copper plating was applied, and then immersed in an electroless copper plating solution at 32 ° C. for 30 minutes to form a 1.5 μm electroless copper plating film. This was dried at 200 ° C. for 3 hours to obtain a circuit board film described in Layer Structure Example 3. Further, this was further washed with an acid, a phosphorous copper plate as an anode, and a cathode current density of 2.0 A / dm. 2 Then, electrolytic copper plating was performed for 12 minutes to form a copper plating film having a thickness of 5 μm. Finally, annealing was performed at 170 ° C. for 60 minutes to obtain a circuit board film described in the configuration example (4). The adhesive strength of the plating film was 0.9 kgf / cm (8.8 × 10 8 2 N / m).
[0083]
<Example 15>
A cured product obtained by immersing the film for circuit board corresponding to the layer constitution example 2 described in Example 13 in a swelling solution using “Swelling Dip Securiganth P” (manufactured by Atotech Japan Co., Ltd.) at 80 ° C. for 5 minutes. After swelling the surface of the layer, it was then roughened by immersing it in an alkaline permanganate solution at 80 ° C. for 10 minutes, and further, manganese remaining on the surface of the cured product layer was reduced and removed. Subsequently, a catalyst for electroless copper plating was applied, and then immersed in an electroless copper plating solution at 32 ° C. for 30 minutes to form a 1.5 μm electroless copper plating film. This was dried at 120 ° C. for 30 minutes to obtain a circuit board film described in Layer Construction Example 5. Further, this was further washed with an acid, a phosphorous copper plate as an anode, and a cathode current density of 2.0 A / dm. 2 Then, electrolytic copper plating was performed for 12 minutes to form a copper plating film having a thickness of 5 μm. Finally, annealing was performed at 200 ° C. for 3 hours to obtain a film for circuit board described in Structural Example (6). The adhesive strength of the plating film is 0.9 kgf / cm (8.8 × 10 8 2 N / m).
[0084]
<Comparative Example 1>
20 parts of bisphenol A type epoxy resin “Epicoat 828” (epoxy equivalent 190, manufactured by Japan Epoxy Resins Co., Ltd.) and cresol novolac type epoxy resin “Epicron N673” (epoxy equivalent 215, softening point 78 ° C., Dainippon) Ink Science Industrial Co., Ltd. (35 parts) was dissolved in 2-butanone and cooled to room temperature, and a 2-butanone solution of phenolic novolak resin containing triazine ring “Phenolite LA7052” (non-volatile content 60 wt. %, Nonvolatile phenol equivalent hydroxyl group 120, Dainippon Ink & Chemicals, Inc.) 45 parts, bixylenol type epoxy resin “Epicoat YX-4000” (epoxy equivalent 185, Japan Epoxy Resins Co., Ltd.) and Cyclohexano of phenoxy resin consisting of bisphenol S 70 parts of a solution “YL-6746H30” (non-volatile content 30% by weight, weight average molecular weight 30000, manufactured by Japan Epoxy Resins Co., Ltd.), 18 parts of spherical silica and 2 parts of finely pulverized silica were added, and roll dispersion was performed. A resin varnish of a thermosetting resin composition was prepared.
[0085]
The resin varnish described in Comparative Example 1 was applied on a 38 μm-thick polyethylene terephthalate film that had been subjected to a release treatment so that the resin thickness after drying would be 30 μm, and approximately 80 to 140 ° C. (average 110 ° C.). The film was dried for 16 minutes, and then heated and cured at 180 ° C. for 30 minutes to produce a circuit board film.
[0086]
The thermoset layer was peeled off from the polyethylene terephthalate film and further heated at 200 ° C. for 3 hours, and then a dumbbell-shaped test piece was cut out from this film according to JIS K 7127. A tensile test was performed using these test pieces, and the breaking strength and breaking elongation of the cured film were measured. The following values were obtained, and a cured film having excellent mechanical properties could not be obtained. Breaking strength = 85 MPa, breaking elongation = 1.8%
Moreover, when this cured | curing material film was bent at 180 degree | times, the crack generate | occur | produced in the film.
[0087]
<Comparative example 2>
The adhesion strength of the commercially available “S'PERFLEX” (manufactured by Sumitomo Metal Mining Co., Ltd.) in which a Ni seed layer is formed by sputtering on a 25 μm polyimide film “Kapton EN” and copper plated (8 μm) is 0.5 kgf / cm (4.9 × 10 2 N / m).
[0088]
【The invention's effect】
According to the present invention, it is possible to easily form a conductor layer capable of forming a fine circuit with excellent peel strength by plating, and excellent in properties required for a base film of a flexible circuit board or the like. A circuit board film can be obtained, and the film is particularly excellent as a base film for a flexible circuit board.
Claims (13)
Ａ層：成分（ａ）破断強度が１００ＭＰａ以上、破断伸度が１０％以上、２０〜１５０℃間の熱膨張係数が６０ｐｐｍ以下、及びガラス転移温度が１６０℃以上である有機溶剤に溶解する耐熱樹脂、成分（ｂ）熱硬化性樹脂、（ｃ）充填剤、並びに（ｄ）ポリブタジエン骨格および／またはポリシロキサン骨格を有する樹脂、を含有し、成分（ａ）と成分（ｂ）の割合が重量比で１００：１〜１：１であり、成分（ａ）と成分（ｂ）の合計量と成分（ｃ）の割合が重量比で１００：１〜３：２であり、成分（ｄ）の配合量が成分（ａ）１００重量部に対し０．１〜１５重量部であり、成分（ａ）〜（ｄ）の合計配合量が７０重量％以上である熱硬化性樹脂組成物の熱硬化物からなる厚さ５乃至２０μｍの熱硬化物層、及びＢ層：金属箔。Circuit board film having the following A layer and B layer adjacent to each other,
Layer A: Component (a) Heat resistance that dissolves in an organic solvent having a breaking strength of 100 MPa or more, a breaking elongation of 10% or more, a thermal expansion coefficient between 20 to 150 ° C. of 60 ppm or less, and a glass transition temperature of 160 ° C. or more. Resin, component (b) thermosetting resin, (c) filler, and (d) resin having polybutadiene skeleton and / or polysiloxane skeleton, and the ratio of component (a) to component (b) is weight The ratio of the total amount of component (a) and component (b) and component (c) is 100: 1 to 3: 2 by weight, and the ratio of component (d) is 100: 1 to 1: 1. Thermosetting of thermosetting resin composition whose blending amount is 0.1 to 15 parts by weight with respect to 100 parts by weight of component (a), and the total blending amount of components (a) to (d) is 70% by weight or more. A thermoset layer of 5 to 20 μm in thickness and B layer: metal foil.
Ａ層：成分（ａ）破断強度が１００ＭＰａ以上、破断伸度が１０％以上、２０〜１５０℃間の熱膨張係数が６０ｐｐｍ以下、及びガラス転移温度が１６０℃以上である有機溶剤に溶解する耐熱樹脂、成分（ｂ）熱硬化性樹脂、（ｃ）充填剤、並びに（ｄ）ポリブタジエン骨格および／またはポリシロキサン骨格を有する樹脂、を含有し、成分（ａ）と成分（ｂ）の割合が重量比で１００：１〜１：１であり、成分（ａ）と成分（ｂ）の合計量と成分（ｃ）の割合が重量比で１００：１〜３：２であり、成分（ｄ）の配合量が成分（ａ）１００重量部に対し０．１〜１５重量部であり、成分（ａ）〜（ｄ）の合計配合量が７０重量％以上である熱硬化性樹脂組成物の熱硬化物からなる厚さ５乃至２０μｍの熱硬化物層、及びＣ層：無電解銅メッキ層。A film for a circuit board comprising the following A layer and C layer, and having a layer structure in the order of C layer, A layer and C layer,
Layer A: Component (a) Heat resistance that dissolves in an organic solvent having a breaking strength of 100 MPa or more, a breaking elongation of 10% or more, a thermal expansion coefficient between 20 to 150 ° C. of 60 ppm or less, and a glass transition temperature of 160 ° C. or more. Resin, component (b) thermosetting resin, (c) filler, and (d) resin having polybutadiene skeleton and / or polysiloxane skeleton, and the ratio of component (a) to component (b) is weight The ratio of the total amount of component (a) and component (b) and component (c) is 100: 1 to 3: 2 by weight, and the ratio of component (d) is 100: 1 to 1: 1. Thermosetting of thermosetting resin composition whose blending amount is 0.1 to 15 parts by weight with respect to 100 parts by weight of component (a), and the total blending amount of components (a) to (d) is 70% by weight or more. 5 to 20 μm-thick thermoset layer and C layer: electroless copper mesh Layer.
Ａ層：成分（ａ）破断強度が１００ＭＰａ以上、破断伸度が１０％以上、２０〜１５０℃間の熱膨張係数が６０ｐｐｍ以下、及びガラス転移温度が１６０℃以上である有機溶剤に溶解する耐熱樹脂、成分（ｂ）熱硬化性樹脂、（ｃ）充填剤、並びに（ｄ）ポリブタジエン骨格および／またはポリシロキサン骨格を有する樹脂、を含有し、成分（ａ）と成分（ｂ）の割合が重量比で１００：１〜１：１であり、成分（ａ）と成分（ｂ）の合計量と成分（ｃ）の割合が重量比で１００：１〜３：２であり、成分（ｄ）の配合量が成分（ａ）１００重量部に対し０．１〜１５重量部であり、成分（ａ）〜（ｄ）の合計配合量が７０重量％以上である熱硬化性樹脂組成物の熱硬化物からなる厚さ５乃至２０μｍの熱硬化物層、
Ｃ層：無電解銅メッキ層、及び
Ｄ層：電気銅メッキ層。A film for a circuit board comprising the following A layer C layer and D layer, and having a layer structure in the order of D layer, C layer, A layer, C layer and D layer,
Layer A: Component (a) Heat resistance that dissolves in an organic solvent having a breaking strength of 100 MPa or more, a breaking elongation of 10% or more, a thermal expansion coefficient between 20 to 150 ° C. of 60 ppm or less, and a glass transition temperature of 160 ° C. or more. Resin, component (b) thermosetting resin, (c) filler, and (d) resin having polybutadiene skeleton and / or polysiloxane skeleton, and the ratio of component (a) to component (b) is weight The ratio of the total amount of component (a) and component (b) and component (c) is 100: 1 to 3: 2 by weight, and the ratio of component (d) is 100: 1 to 1: 1. Thermosetting of thermosetting resin composition whose blending amount is 0.1 to 15 parts by weight with respect to 100 parts by weight of component (a), and the total blending amount of components (a) to (d) is 70% by weight or more. A thermoset layer having a thickness of 5 to 20 μm,
C layer: electroless copper plating layer, and D layer: electrolytic copper plating layer.
Ａ層：成分（ａ）破断強度が１００ＭＰａ以上、破断伸度が１０％以上、２０〜１５０℃間の熱膨張係数が６０ｐｐｍ以下、及びガラス転移温度が１６０℃以上である有機溶剤に溶解する耐熱樹脂、成分（ｂ）熱硬化性樹脂、（ｃ）充填剤、並びに（ｄ）ポリブタジエン骨格および／またはポリシロキサン骨格を有する樹脂、を含有し、成分（ａ）と成分（ｂ）の割合が重量比で１００：１〜１：１であり、成分（ａ）と成分（ｂ）の合計量と成分（ｃ）の割合が重量比で１００：１〜３：２であり、成分（ｄ）の配合量が成分（ａ）１００重量部に対し０．１〜１５重量部であり、成分（ａ）〜（ｄ）の合計配合量が７０重量％以上である熱硬化性樹脂組成物の熱硬化物からなる厚さ５乃至２０μｍの熱硬化物層、
Ｂ層：金属箔、及び
Ｃ層：無電解銅メッキ層。A film for a circuit board comprising the following layer A, layer B and layer C, and having a layer structure in the order of layer B, layer A and layer C,
Layer A: Component (a) Heat resistance that dissolves in an organic solvent having a breaking strength of 100 MPa or more, a breaking elongation of 10% or more, a thermal expansion coefficient between 20 to 150 ° C. of 60 ppm or less, and a glass transition temperature of 160 ° C. or more. Resin, component (b) thermosetting resin, (c) filler, and (d) resin having polybutadiene skeleton and / or polysiloxane skeleton, and the ratio of component (a) to component (b) is weight The ratio of the total amount of component (a) and component (b) and component (c) is 100: 1 to 3: 2 by weight, and the ratio of component (d) is 100: 1 to 1: 1. Thermosetting of thermosetting resin composition whose blending amount is 0.1 to 15 parts by weight with respect to 100 parts by weight of component (a), and the total blending amount of components (a) to (d) is 70% by weight or more. A thermoset layer having a thickness of 5 to 20 μm,
B layer: metal foil, and C layer: electroless copper plating layer.
Ａ層：成分（ａ）破断強度が１００ＭＰａ以上、破断伸度が１０％以上、２０〜１５０℃間の熱膨張係数が６０ｐｐｍ以下、及びガラス転移温度が１６０℃以上である有機溶剤に溶解する耐熱樹脂、成分（ｂ）熱硬化性樹脂、（ｃ）充填剤、並びに（ｄ）ポリブタジエン骨格および／またはポリシロキサン骨格を有する樹脂、を含有し、成分（ａ）と成分（ｂ）の割合が重量比で１００：１〜１：１であり、成分（ａ）と成分（ｂ）の合計量と成分（ｃ）の割合が重量比で１００：１〜３：２であり、成分（ｄ）の配合量が成分（ａ）１００重量部に対し０．１〜１５重量部であり、成分（ａ）〜（ｄ）の合計配合量が７０重量％以上である熱硬化性樹脂組成物の熱硬化物からなる厚さ５乃至２０μｍの熱硬化物層、
Ｂ層：金属箔、
Ｃ層：無電解銅メッキ層、及び
Ｄ層：電気銅メッキ層。A film for a circuit board comprising the following A layer, B layer, C layer and D layer, and having a layer structure in the order of B layer, A layer, C layer and D layer,
Layer A: Component (a) Heat resistance that dissolves in an organic solvent having a breaking strength of 100 MPa or more, a breaking elongation of 10% or more, a thermal expansion coefficient between 20 to 150 ° C. of 60 ppm or less, and a glass transition temperature of 160 ° C. or more. Resin, component (b) thermosetting resin, (c) filler, and (d) resin having polybutadiene skeleton and / or polysiloxane skeleton, and the ratio of component (a) to component (b) is weight The ratio of the total amount of component (a) and component (b) and component (c) is 100: 1 to 3: 2 by weight, and the ratio of component (d) is 100: 1 to 1: 1. Thermosetting of thermosetting resin composition whose blending amount is 0.1 to 15 parts by weight with respect to 100 parts by weight of component (a), and the total blending amount of components (a) to (d) is 70% by weight or more. A thermoset layer having a thickness of 5 to 20 μm,
B layer: metal foil,
C layer: electroless copper plating layer, and D layer: electrolytic copper plating layer.
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| JP4774749B2 (en) * | 2005-01-31 | 2011-09-14 | 日立化成工業株式会社 | Conductor-clad laminate, printed wiring board and multilayer wiring board using the same |
| JP4957059B2 (en) * | 2005-04-19 | 2012-06-20 | 宇部興産株式会社 | Polyimide film laminate |
| US8043697B2 (en) | 2005-04-19 | 2011-10-25 | Ube Industries, Ltd. | Polyimide film-laminated body |
| US9201299B2 (en) | 2007-10-01 | 2015-12-01 | San-Ei Kagaku Co., Ltd. | Inorganic filler and organic filler-containing curable resin composition, resist film coated printed wiring board, and method for producing the same |
| DE102008045424B4 (en) * | 2007-10-01 | 2018-03-22 | San-Ei Kagaku Co. Ltd. | A curable synthetic resin mixture containing an inorganic filler and an organic filler and use thereof |
| JP2016088050A (en) * | 2014-11-11 | 2016-05-23 | 住友ベークライト株式会社 | Metal film with resin layer |
| US10544305B2 (en) | 2015-01-16 | 2020-01-28 | Hitachi Chemical Company, Ltd. | Thermosetting resin composition, resin film for interlayer insulation, composite film, printed wiring board, and method for producing same |
| JP6809014B2 (en) * | 2016-04-18 | 2021-01-06 | 昭和電工マテリアルズ株式会社 | Thermosetting resin composition, resin film for interlayer insulation, composite film, printed wiring board and its manufacturing method |
| JP6885000B2 (en) * | 2016-07-19 | 2021-06-09 | 昭和電工マテリアルズ株式会社 | A resin film for forming a semiconductor rewiring layer, a composite film for forming a semiconductor rewiring layer, a semiconductor device using them, and a method for manufacturing the semiconductor device. |
| JP6922167B2 (en) * | 2016-07-20 | 2021-08-18 | 昭和電工マテリアルズ株式会社 | Thermosetting resin composition, resin film for interlayer insulation, composite film, printed wiring board and its manufacturing method |
| CN107033517B (en) * | 2016-11-25 | 2019-07-12 | 苏州生益科技有限公司 | A kind of prepolymer of modified polybutadiene and its preparation method and application |
| JP7087912B2 (en) * | 2018-10-25 | 2022-06-21 | 味の素株式会社 | Resin composition |
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