JP6928920B2 - 熱硬化性組成物、樹脂シート、樹脂付き金属箔、金属張積層板、及びプリント配線板 - Google Patents
熱硬化性組成物、樹脂シート、樹脂付き金属箔、金属張積層板、及びプリント配線板 Download PDFInfo
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/036—Multilayers with layers of different types
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- C—CHEMISTRY; METALLURGY
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- B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
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- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
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Description
本実施形態に係る熱硬化性組成物(以下、組成物(X)ともいう)は、エチレン−プロピレン−ジエン共重合体(A)と、重合性不飽和結合を有する表面処理剤で表面処理された無機充填材(B)とを含有する。この組成物(X)の硬化物は、低い誘電率、低い誘電正接、高い耐熱性、並びに金属及び樹脂に対する高い密着性を有することができる。このため、組成物(X)は、金属張積層板及びプリント配線板の絶縁層を作製するための材料として好適であり、その場合、組成物(X)は、プリント配線板に良好な高周波特性と良好な信頼性とを付与できる。
組成物(X)の成分について、詳しく説明する。
本実施形態に係る樹脂シートは、組成物(X)の乾燥物又は半硬化物を含む。樹脂シートは、積層板及びプリント配線板作製のための材料に適用できる。すなわち、樹脂シートを用い、樹脂シートの硬化物を含む絶縁層(すなわち、組成物(X)の硬化物を含む絶縁層)を備える積層板、及び樹脂シートの硬化物を含む絶縁層(すなわち、組成物(X)の硬化物を含む絶縁層)を備えるプリント配線板を、作製できる。また、樹脂シートをボンディングシートとして使用することもできる。
本実施形態に係る樹脂付き金属箔1は、金属箔10と、金属箔10に重なる樹脂層20とを備える。樹脂層20は、組成物(X)の乾燥物又は半硬化物を含む。
本実施形態に係る金属張積層板2について説明する。
本実施形態に係るプリント配線板3について説明する。
表1及び表2中の「組成」の欄に示す成分を、トルエンに添加することで、固形分濃度25質量%の組成物を得た。
・共重合体1:エチレン−プロピレン−ジエン共重合体、ムーニー粘度(ML(1+4)100℃)15、エチレン含有量72質量%、ジエン含有量3.6質量%、三井化学株式会社製、品番X−3012P。
・共重合体2:エチレン−プロピレン−ジエン共重合体、ムーニー粘度(ML(1+4)100℃)32、エチレン含有量47質量%、ジエン(5−エチリデン−2−ノルボルネン)含有量9.5質量%、三井化学株式会社製、品番8030M。
・共重合体3:エチレン−プロピレン−ジエン共重合体、ムーニー粘度(ML(1+4)125℃)58、エチレン含有量41質量%、ジエン(5−エチリデン−2−ノルボルネン)含有量14.0質量%、三井化学株式会社製、品番9090M。
・重合性不飽和基を有する有機化合物1:式(2)に示す化合物、四国化成工業株式会社製、品番DD−1。
・重合性不飽和基を有する有機化合物2:ジビニルベンゼン、東京化成工業製。
・重合性不飽和基を有する有機化合物3:トリシクロデカンジメタノールジメタクリレート、新中村化学製、品番DCP。
・重合性不飽和基を有する有機化合物4:長鎖アルキルビスマレイミド、Molecular Design Inc製、品番BMI−689。
・ビスマレイミド:大和化成工業製、品番BMI−1000。
・エポキシ化合物:日本化薬製、品番NC−3000H。
・エラストマー1:クラレ製、品名セプトンV9827。
・エラストマー2:クラレ製、品名ハイブラー7125。
・エラストマー3:クラレ製、品名ハイブラー5127。
・無機充填材1:ビニルシランにより表面処理された球状シリカ、株式会社アドマテックス製、品番0.5μmSV−CT1(25%トルエン含有スラリー)。
・無機充填材2:メタクリルシランにより表面処理された球状シリカ、株式会社アドマテックス製、品番0.5μmSM−CT1(25%トルエン含有スラリー)。
・無機充填材3:フェニルシランにより表面処理された球状シリカ、株式会社アドマテックス製、品番0.5μmSP−CT1(25%トルエン含有スラリー)。
・熱ラジカル重合開始剤:日油株式会社製、品名パーブチルP。
2−1.誘電特性(比誘電率及び誘電正接)
厚み18μmの二つの銅箔を、その光沢面同士が対向するように配置し、二つの銅箔の間に樹脂シートを配置した。これらを200℃、2MPaの条件で1時間加熱プレスすることで、サンプルを作製した。このサンプルにエッチング処理を施すことで両面の銅箔を除去することで、樹脂シートの硬化物からなる試験片を作製した。この試験片の、試験周波数10GHzの場合での比誘電率及び誘電正接を、IPC TM−650 2.5.5.5に基づいて測定した。なお、本実施形態における、「低い誘電率」の判断基準の一つとして、この試験による誘電率が3.0以下であることが挙げられる。また、本実施形態における、「低い誘電正接」の判断基準の一つとして、この試験による誘電正接が0.0025以下であることが挙げられる。
厚み12μmの銅箔と厚み3μmのポリアミドイミド製の絶縁層とを備える基材を二つ用意した。二つの基材を絶縁層同士が対向するように配置し、更に絶縁層の間に樹脂シートを配置した。これらを200℃、2MPaの条件で1時間加熱プレスすることで、サンプルを作製した。このサンプルの、ポリアミドイミド製の絶縁層に対する樹脂シートの硬化物の、90°剥離強度を測定した。なお、本実施形態における、「樹脂に対する高い密着性」の判断基準の一つとして、この試験による剥離強度が0.5N/mm以上であることが挙げられる。
厚み12μmの銅箔と厚み3μmのポリアミドイミド製の絶縁層とを備える基材と、厚み12μmの銅箔とを用意した。基材の絶縁層と銅箔とを対向するように配置し、更に絶縁層と銅箔との間に樹脂シートを配置した。これらを200℃、2MPaの条件で1時間加熱プレスすることで、サンプルを作製した。このサンプルの、銅箔に対する樹脂シートの硬化物の、90°剥離強度を測定した。なお、本実施形態における、「金属に対する高い密着性」の判断基準の一つとして、この試験による剥離強度が0.5N/mm以上であることが挙げられる。
上記の「剥離強度1」の試験の場合と同じ方法で、サンプルを作製した。サンプルから、JIS C6471に基づき試験片を作製した。この試験片を260℃及び300℃のはんだ浴に3分間浮かべてから引き上げた後、試験片の外観を観察した。その結果、はんだ浴の温度が260℃、300℃のいずれの場合でも膨れ、はがれ等の異常が認められない場合を「A」、はんだ浴の温度が260℃では異常が認められないが300℃では異常が認められた場合を「B」、はんだ浴の温度が260℃、300℃のいずれの場合でも異常が認められた場合を「C」と、評価した。なお、本実施形態における「高い耐熱性」の判断基準の一つとして、この試験による評価が「A」又は「B」であることが挙げられる。
上記の「剥離強度2」の試験の場合と同じ方法で、サンプルを作製した。サンプルから、JIS C6471に基づき試験片を作製した。この試験片を260℃及び300℃のはんだ浴に3分間浮かべてから引き上げた後、試験片の外観を観察した。その結果、はんだ浴の温度が260℃、300℃のいずれの場合でも膨れ、はがれ等の異常が認められない場合を「A」、はんだ浴の温度が260℃では異常が認められないが300℃では以上が認められた場合を「B」、はんだ浴の温度が260℃、300℃のいずれの場合でも異常が認められた場合を「C」と、評価した。なお、本実施形態における「高い耐熱性」の判断基準の一つとして、この試験による評価が「A」又は「B」であることが挙げられる。
Claims (9)
- エチレン−プロピレン−ジエン共重合体(A)と、
重合性不飽和結合を有する表面処理剤で表面処理された無機充填材(B)と、
重合性不飽和基を有する有機化合物(C)と、
を含有し、
前記有機化合物(C)の量は、前記エチレン−プロピレン−ジエン共重合体(A)100質量部に対して、1質量部以上100質量部以下である、
金属張積層板又はプリント配線板の、絶縁層を形成するための、
熱硬化性組成物。 - 前記無機充填材(B)の量は、前記エチレン−プロピレン−ジエン共重合体(A)100質量部に対して、30質量部以上500質量部以下である、
請求項1又は2に記載の熱硬化性組成物。 - 請求項1から3のいずれか一項に記載の熱硬化性組成物の乾燥物又は半硬化物を含む、
樹脂シート。 - 金属箔と、前記金属箔に重なる樹脂層とを備え、
前記樹脂層は、請求項1から3のいずれか一項に記載の熱硬化性組成物の乾燥物又は半硬化物を含む、
樹脂付き金属箔。 - 前記樹脂層は、前記金属箔に重なる第一の樹脂層と、前記第一の樹脂層に重なる第二の樹脂層とを含み、
前記第一の樹脂層は、液晶ポリマー、ポリイミド、ポリアミドイミド、フッ素樹脂及びポリフェニレンエーテルからなる群から選択される少なくとも一種の成分を含み、
前記第二の樹脂層は、前記熱硬化性組成物の乾燥物又は半硬化物を含む、
請求項5に記載の樹脂付き金属箔。 - 前記第一の樹脂層の厚みが、1μm以上50μm以下であり、前記第二の樹脂層の厚みが5μm以上200μm以下である、
請求項6に記載の樹脂付き金属箔。 - 絶縁層と金属箔とを備え、
前記絶縁層は、請求項1から3のいずれか一項に記載の熱硬化性組成物の硬化物を含む、金属張積層板。 - 絶縁層と導体配線とを備え、
前記絶縁層は、請求項1から3のいずれか一項に記載の熱硬化性組成物の硬化物を含む、プリント配線板。
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