JP7013444B2 - 樹脂組成物、樹脂付銅箔、誘電体層、銅張積層板、キャパシタ素子及びキャパシタ内蔵プリント配線板 - Google Patents
樹脂組成物、樹脂付銅箔、誘電体層、銅張積層板、キャパシタ素子及びキャパシタ内蔵プリント配線板 Download PDFInfo
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- JP7013444B2 JP7013444B2 JP2019505985A JP2019505985A JP7013444B2 JP 7013444 B2 JP7013444 B2 JP 7013444B2 JP 2019505985 A JP2019505985 A JP 2019505985A JP 2019505985 A JP2019505985 A JP 2019505985A JP 7013444 B2 JP7013444 B2 JP 7013444B2
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Images
Classifications
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Description
前記樹脂成分が、エポキシ樹脂と、活性エステル樹脂と、芳香族ポリアミド樹脂とを含む、樹脂組成物が提供される。
本発明の樹脂組成物は、樹脂成分と、誘電体フィラーとを含む。そして、この樹脂成分は、エポキシ樹脂と、活性エステル樹脂と、芳香族ポリアミド樹脂とを含む。このように、エポキシ樹脂、活性エステル樹脂及び芳香族ポリアミド樹脂を誘電体フィラーと共に含む樹脂組成物を、キャパシタの誘電体層として用いることで、優れた回路密着性を確保しながら、高温高湿下におけるキャパシタンス低下ないし誘電率低下を抑制することができる。すなわち、本発明の樹脂組成物を含む誘電体層は本来的に静電容量が高く、高温高湿下においてもその高い静電容量が低下しにくい。また、本発明の樹脂組成物を含む誘電体層は、高温高湿下においても回路構成成分(典型的にはCu等の金属)のマイグレーションが起こりにくく、それ故、層間絶縁性を長期にわたって保持することができる。したがって、誘電体層は、高温高湿下で誘電率が低下しにくく、それ故、高温高湿下におけるキャパシタンスが低下しにくくなる。そうでありながら、本発明の樹脂組成物を含む誘電体層は回路密着性にも優れており、キャパシタにおける回路剥がれが起こりにくい。
本発明の樹脂組成物は樹脂付銅箔の樹脂として用いられるのが好ましい。樹脂付銅箔における樹脂組成物は、2枚の樹脂付銅箔を樹脂組成物が互いに向かい合うように積層して誘電体層を形成させる観点から、半硬化されているのが好ましい。予め樹脂付銅箔の形態とすることで、樹脂層ないし誘電体層を別途形成することなく、キャパシタ素子やキャパシタ内蔵プリント配線板の製造を効率良く行うことができる。すなわち、本発明の好ましい態様によれば、銅箔と、銅箔の少なくとも一方の面に設けられた樹脂組成物とを含む、樹脂付銅箔が提供される。典型的には、樹脂組成物は樹脂層の形態であって、樹脂組成物を、銅箔に乾燥後の樹脂層の厚さが所定のものとなるようにグラビアコート方式で塗工し乾燥させ、樹脂付銅箔を得る。この塗工の方式については任意であるが、グラビアコート方式の他、ダイコート方式、ナイフコート方式等を採用することができる。その他、ドクターブレードやバーコータ等を使用して塗工することも可能である。
本発明の樹脂組成物は硬化されて誘電体層とされるのが好ましい。すなわち、本発明の好ましい態様によれば、本発明の樹脂組成物が硬化された層である、誘電体層が提供される。樹脂組成物の硬化は公知の手法に基づき行えばよいが、熱間真空プレスにより行うのが好ましい。誘電体層の厚さは、所望の静電容量を確保できる限り特に限定されないが、好ましくは0.2~30μmであり、より好ましくは0.5~20μm、さらに好ましくは1~8μm、最も好ましくは2~6μmである。これらの範囲内の厚さであると、高い静電容量を実現しやすい、樹脂組成物の塗布により樹脂層の形成がしやすい、銅箔との間で十分な密着性を確保しやすいといった利点がある。
本発明の樹脂組成物ないしそれを含む誘電体層は銅張積層板に適用されるのが好ましい。すなわち、本発明の好ましい態様によれば、第一銅箔と、上述した誘電体層と、第二銅箔とを順に備えた、銅張積層板が提供される。銅張積層板の形態とすることで、本発明の樹脂組成物を誘電体層として含むキャパシタ素子やキャパシタ内蔵プリント配線板を望ましく作製することができる。銅張積層板の作製方法は特に限定されないが、例えば、2枚の上述した樹脂付銅箔を樹脂層が互いに向かい合うように積層して高温で真空プレスすることにより銅張積層板を製造することができる。
本発明の樹脂組成物ないしそれを含む誘電体層はキャパシタ素子に組み込まれるのが好ましい。すなわち、本発明の好ましい態様によれば、上述した誘電体層を有する、キャパシタ素子が提供される。キャパシタ素子の構成は特に限定されず、公知の構成が採用可能である。特に好ましい形態は、キャパシタないしその誘電体層がプリント配線板の内層部分として組み込まれた、キャパシタ内蔵プリント配線板である。すなわち、本発明の特に好ましい態様によれば、上述した誘電体層を有する、キャパシタ内蔵プリント配線板が提供される。特に、本発明の樹脂付銅箔を用いることで、キャパシタ素子やキャパシタ内蔵プリント配線板を公知の手法に基づき効率良く製造することができる。
(1)樹脂ワニスの調製
まず、樹脂ワニス用原料成分として、以下に示される樹脂成分、イミダゾール系硬化促進剤及び誘電体フィラーを用意した。
‐ エポキシ樹脂:ビフェニルノボラック型エポキシ樹脂、日本化薬株式会社製、NC-3000
‐ 活性エステル樹脂:DIC株式会社製、HPC-8000-65T
‐ 芳香族ポリアミド樹脂:日本化薬株式会社製、BPAM-155
‐ イミダゾール硬化促進剤:四国化成工業株式会社製、2P4MHZ、添加量1.0wt%(樹脂成分100wt%に対して)
‐ 誘電体フィラー:BaTiO3、日本化学工業株式会社製、AKBT-M
‐ フィラー分散剤:チタネート系カップリング剤、味の素ファインテクノ株式会社製、KR-44
シクロペンタノン、誘電体フィラー及びフィラー分散剤をそれぞれ秤量した。秤量した溶剤、誘電体フィラー及びフィラー分散剤を分散機でスラリー化した。スラリー化を確認した後、樹脂ワニスを秤量し、分散機で誘電体フィラー含有スラリーとともに混練して、樹脂組成物4を得た。
図1に示されるように、得られた樹脂組成物4を、銅箔2(三井金属鉱業株式会社製、厚さ35μm、表面粗さRz=0.5μm)に厚さが1.5μmとなるようにバーコーターを用いて塗工し、その後130℃に加熱したオーブンにて3分間乾燥させ、樹脂を半硬化状態とした。こうして樹脂付銅箔6を得た。
図1に示されるように、2枚の樹脂付銅箔6を樹脂組成物4が互いに向かい合うように積層し、圧力40kgf/cm2、200℃で90分間の真空プレスを行い、樹脂組成物4を硬化状態とした。こうして硬化された樹脂組成物4を誘電体層として含む銅張積層板8を得た。
得られた銅張積層板8の片面又は両面にエッチングを施して各種評価用の回路10を形成し、以下の各種評価を行った。
銅張積層板の片面にエッチングを施して10mm幅の直線状の回路を作製した後、オートグラフにて引き剥がし速度50mm/分で回路を引き剥がし、その剥離強度を測定した。この測定はIPC-TM-650 2.4.8に準拠して行った。測定された剥離強度を以下の基準に従い評価した。結果は表1に示されるとおりであった。
‐評価A:0.8kgf/cm以上(良)
‐評価B:0.4kgf/cm以上でかつ0.8kgf/cm未満(可)
‐評価C:0.4kgf/cm未満(不可)
まず、銅張積層板の片面にエッチングを施して直径0.5インチ(12.6mm)の円形の回路を作製した後、LCRメーター(日置電気株式会社製、LCRハイテスタ3532-50)にて周波数1kHzにおける静電容量を測定した。この測定はIPC-TM-650 2.5.2に準拠して行った。結果は表1に示されるとおりであった。
‐評価AA:2%未満(最良)
‐評価A:2%以上でかつ3%未満(良)
‐評価B:3%以上でかつ6%未満(可)
‐評価C:6%以上(不可)
銅張積層板の両面にエッチングを施して直径0.5インチ(12.6mm)の円形の回路を作製した後、上部電極及び下部電極に配線をはんだ付けし、配線をマイグレーション測定用テスターに接続した。評価回路を85℃及び85%RHの恒温恒湿槽に投入し、印加電圧3Vの負荷をかけ、1×105Ω以上の絶縁抵抗を保持する時間を計測した。計測された層間絶縁性保持時間を以下の基準に従い評価した。結果は表1に示されるとおりであった。
‐評価AA:1000時間以上(最良)
‐評価A:500時間以上でかつ1000時間未満(良)
‐評価B:200時間以上でかつ500時間未満(可)
‐評価C:200時間未満(不可)
評価1~3の評価結果を以下の基準に当てはめることにより、総合評価を決定した。結果は表1に示されるとおりであった。
‐評価AA:全ての評価においてA以上の判定となるもの(最良)
‐評価A:C判定となるものがなく、かつ、B判定となるものが1つあるもの(良)
‐評価B:C判定となるものがなく、かつ、B判定となるものが2つあるもの(可)
‐評価C:C判定が少なくとも1つあるもの(不可)
活性エステル樹脂の代わりにフェノール樹脂(明和化成株式会社製、MEH-7500)20.0重量部を用い、エポキシ樹脂の配合比を40.0重量部に増やしたこと以外は例3と同様にして、樹脂ワニスの調製及び各種評価を行った。結果は表1に示されるとおりであった。
芳香族ポリアミド樹脂の代わりにブチラール樹脂(積水化学工業製、KS-5Z)を用いたこと以外は例2と同様にして、樹脂ワニスの調製及び各種評価を行った。結果は表1に示されるとおりであった。
芳香族ポリアミド樹脂を用いず、エポキシ樹脂の配合比を56.0重量部、活性エステル樹脂の配合比を44.0重量部に増やしたこと以外は例1と同様にして、樹脂ワニスの調製及び各種評価を行った。結果は表1に示されるとおりであった。
Claims (9)
- 樹脂成分と、誘電体フィラーとを含む樹脂組成物であって、
前記樹脂成分が、エポキシ樹脂と、活性エステル樹脂と、芳香族ポリアミド樹脂とを含み、
前記樹脂成分100重量部に対して、前記芳香族ポリアミド樹脂25~85重量部及び前記活性エステル樹脂15~35重量部を含み、
前記樹脂組成物の固形分100重量部に対して、前記誘電体フィラー60~95重量部を含む、樹脂組成物。 - 前記誘電体フィラーが、BaTiO3、SrTiO3、Pb(Zr,Ti)O3、PbLaTiO3、PbLaZrO及びSrBi2Ta2O9からなる群から選択される少なくとも1種を含む、請求項1に記載の樹脂組成物。
- 前記誘電体フィラーが、BaTiO3である、請求項1又は2に記載の樹脂組成物。
- 銅箔と、前記銅箔の少なくとも一方の面に設けられた請求項1~3のいずれか一項に記載の樹脂組成物とを含む、樹脂付銅箔。
- 請求項1~3のいずれか一項に記載の樹脂組成物が硬化された層である、誘電体層。
- 前記誘電体層の厚さが、0.2~30μmである、請求項5に記載の誘電体層。
- 第一銅箔と、請求項5又は6に記載の誘電体層と、第二銅箔とを順に備えた、銅張積層板。
- 請求項5又は6に記載の誘電体層を有する、キャパシタ素子。
- 請求項5又は6に記載の誘電体層を有する、キャパシタ内蔵プリント配線板。
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