JPWO2016190278A1 - シールドフィルムおよびシールドプリント配線板 - Google Patents
シールドフィルムおよびシールドプリント配線板 Download PDFInfo
- Publication number
- JPWO2016190278A1 JPWO2016190278A1 JP2017520698A JP2017520698A JPWO2016190278A1 JP WO2016190278 A1 JPWO2016190278 A1 JP WO2016190278A1 JP 2017520698 A JP2017520698 A JP 2017520698A JP 2017520698 A JP2017520698 A JP 2017520698A JP WO2016190278 A1 JPWO2016190278 A1 JP WO2016190278A1
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- JP
- Japan
- Prior art keywords
- shield film
- conductive adhesive
- weight
- parts
- flame retardant
- 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.)
- Granted
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- 239000002184 metal Substances 0.000 claims abstract description 42
- 239000010410 layer Substances 0.000 claims abstract description 37
- 239000003822 epoxy resin Substances 0.000 claims abstract description 36
- 239000003063 flame retardant Substances 0.000 claims abstract description 36
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 36
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- 239000012790 adhesive layer Substances 0.000 claims abstract description 33
- 229920001971 elastomer Polymers 0.000 claims abstract description 25
- 239000000806 elastomer Substances 0.000 claims abstract description 25
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 23
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000011231 conductive filler Substances 0.000 claims abstract description 19
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 19
- 239000011574 phosphorus Substances 0.000 claims abstract description 19
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- 230000001070 adhesive effect Effects 0.000 claims abstract description 16
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- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
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- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
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Abstract
Description
1つの実施形態においては、上記カルボキシル基含有エラストマーは、不飽和カルボン酸で変性されたスチレン−エチレンプロピレン−スチレン共重合体である。
1つの実施形態においては、上記有機リン系難燃剤はホスフィン酸金属塩である。
1つの実施形態においては、上記導電性接着剤層は、VTM−0またはそれより良好な難燃性を有し、かつ、1GHzにおいて2.0〜4.0の比誘電率および0.0015〜0.0040の誘電正接を有する。
本発明の別の局面によれば、シールドプリント配線板が提供される。このシールドプリント配線板は、上記のシールドフィルムを含む。
図1は、本発明の1つの実施形態によるシールドフィルムの概略断面図である。本実施形態のシールドフィルム100は、金属層10と、金属層10の一方の側に配置された導電性接着剤層20と、を備える。シールドフィルム100は、必要に応じて、金属層10の導電性接着剤層20と反対側に配置された保護層30をさらに備えてもよい。実用的には、金属層10(存在する場合には、保護層30)の外側および/または導電性接着剤層20の外側には、離型フィルム(セパレーター)40が剥離可能に仮着され、使用に供されるまでの間シールドフィルムを保護している。
金属層10は、金属の薄膜からなる層である。金属層10は、電磁波シールド層として機能し得る。
導電性接着剤層20は、エポキシ樹脂とカルボキシル基含有エラストマーとの硬化物と、有機リン系難燃剤と、導電性フィラーと、を含む。言い換えれば、導電性接着剤層20は、エポキシ樹脂およびカルボキシル基含有エラストマーを含む樹脂成分と有機リン系難燃剤と導電性フィラーとを含む導電性接着剤組成物を硬化させることにより形成される。
保護層30は、代表的には、任意の適切な樹脂フィルムで構成される。樹脂フィルムを構成する樹脂とは、熱硬化性樹脂であってもよく、熱可塑性樹脂であってもよく、電子線(例えば、可視光線、紫外線)硬化性樹脂であってもよい。樹脂の具体例としては、エポキシ樹脂、フェノール樹脂、アミノ樹脂、アルキッド樹脂、ウレタン樹脂、(メタ)アクリル樹脂、ポリイミド樹脂、ポリアミドイミド樹脂が挙げられる。
本発明の実施形態によるシールドプリント配線板は、プリント配線板と上記A項からC項に記載のシールドフィルムとを含む。プリント配線板は、信号回路が形成されたベースフィルムと、信号回路を覆って当該ベースフィルム上の全面に設けられた絶縁フィルムと、を有する。1つの実施形態においては、プリント配線板は、フレキシブルプリント配線板である。シールドフィルムは、導電性接着剤層を介して、プリント配線板の絶縁フィルム上に積層されている。なお、プリント配線板の構成は当業界で周知であるので、詳細な説明は省略する。
実施例、参考例および比較例において調製した導電性接着剤組成物の硬化物について、PNA−L ネットワークアナライザーN5230A(アジレント社製)を用いて、空洞共振器摂動法(条件:23℃、1GHz)により比誘電率(ε)および誘電正接(tanδ)を測定した。
(2)難燃性
実施例、参考例および比較例において調製した導電性接着剤組成物の硬化物について、UL94規格に準拠したVTM燃焼性試験により難燃性を評価した。
(3)特性インピーダンス
実施例2および参考例1で得られたシールドフィルムの特性インピーダンスについて、オシロスコープとTDRモジュールとTDRプローブとで構成されたシステムを用いて評価した。オシロスコープは、テクトロニクス社製のDSC8200を用いた。TDRモジュールは、テクトロニクス社製の80E04を用いた。TDRプローブは、テクトロニクス社製のP8018(シングル:50Ω)およびP80318(差動:100Ω)を用いた。
(4)アイパターン
実施例2および参考例1で得られたシールドフィルムのアイパターン(伝送波形)について、データジェネレータとオシロスコープとサンプリングモジュールとで構成されたシステムを用いて評価した。オシロスコープは、テクトロニクス社製のDSC8200を用いた。データジェネレータは、アジレント社製の81133Aを用いた。サンプリングモジュールは、テクトロニクス社製の80E03を用いた。ビットレートを0.5Gbps、1.0Gbps、2.0Gbpsおよび3.0Gbpsに変化させて測定を行った。
離型層を形成した剥離性フィルムに、アクリル系樹脂を含む保護層用樹脂組成物をコーティングし、乾燥することで、厚さが5μmの保護層を形成した。次いで、圧延加工により作製した厚み2μmの銅箔を、保護層に貼り合わせた。
次いで、撹拌装置付きの1000mlフラスコに、下記に示す原料を下記に示す割合で添加し、室温下で6時間撹拌して溶解することにより、固形分濃度20%の液状導電性接着剤組成物を調製した。これを銅箔の上にドクターブレイド(板状のヘラ)を用いて塗布し、100℃×3分の条件で乾燥させて導電性接着剤層を形成した。なお、エポキシ樹脂としてクレゾールノボラック型エポキシ樹脂(DIC社製、エピクロン N−655−EXP)を用いた。カルボキシル基含有エラストマーとしてマレイン酸変性スチレン−エチレンプロピレン−スチレンブロック共重合体(クラレ社製、セプトン2007)を用いた。有機リン系難燃剤としてトリスジエチルホスフィン酸アルミニウム(クラリアントジャパン社製、EXOLITE OP−935)を用いた。導電性フィラーとして樹枝状の銀コート銅粉(平均粒子径13μm)を用いた。
エポキシ樹脂:10部
カルボキシル基含有エラストマー:100部
有機リン系難燃剤:30部
導電性フィラー:20部
イミダゾール系硬化促進剤(四国化成社製、キュアゾールC11−Z):0.2重量部
溶媒(トルエン/メチルエチルケトン=90:10質量比):400重量部
このようにして、金属層/導電性接着剤層の構成を有するシールドフィルムを作製した。得られたシールドフィルムを上記(1)〜(2)の評価に供した。結果を表1に示す。
厚みが5.5μmの銅箔を用いたこと以外は実施例1と同様にしてシールドフィルムを得た。得られたシールドフィルムを上記(1)〜(4)の評価に供した。比誘電率、誘電正接および難燃性の結果を表1に示す。特性インピーダンスの結果を参考例1の結果と併せて図2に示す。アイパターンの結果を参考例1および比較例6の結果と併せて図3に示す。
有機リン系難燃剤の添加量を表1のとおりとしたこと以外は実施例2と同様にしてシールドフィルムを得た。得られたシールドフィルムを上記(1)〜(4)の評価に供した。比誘電率、誘電正接、および難燃性の結果を表1に示す。
有機リン系難燃剤の添加量を表1のとおりとしたこと以外は実施例2と同様にしてシールドフィルムを得た。得られたシールドフィルムを上記(1)〜(4)の評価に供した。比誘電率、誘電正接、および難燃性の結果を表1に示す。
有機リン系難燃剤および導電性フィラーの添加量を表1のとおりとしたこと以外は実施例2と同様にしてシールドフィルムを得た。得られたシールドフィルムを上記(1)〜(4)の評価に供した。比誘電率、誘電正接、および難燃性の結果を表1に示す。
難燃剤を用いなかったこと以外は実施例1と同様にしてシールドフィルムを得た。得られたシールドフィルムを上記(1)〜(4)の評価に供した。比誘電率、誘電正接および難燃性の結果を表1に示す。特性インピーダンスの結果を実施例2の結果と併せて図2に示す。アイパターンの結果を実施例2および比較例6の結果と併せて図3に示す。
有機リン系難燃剤30部の代わりに窒素系難燃剤(メラミンシアヌレート、日産化学社製、MC−4500)30部を用いたこと以外は実施例1と同様にしてシールドフィルムを得た。得られたシールドフィルムを上記(1)〜(2)の評価に供した。結果を表1に示す。
樹脂成分として変性エポキシ樹脂(アクリル変性エポキシ樹脂、日本化薬社製、ZCR−1798H)を用いたこと以外は実施例1と同様にしてシールドフィルムを得た。得られたシールドフィルムを上記(1)〜(2)の評価に供した。結果を表1に示す。
銀を蒸着して金属層(厚み0.1μm)を形成したこと、樹脂成分としてリン含有エポキシ樹脂(新日鉄化学社製、FX−305BEK)を用いたこと、導電性接着剤層の厚みを10μmとしたこと、および、窒素系難燃剤を用いたこと以外は実施例1と同様にしてシールドフィルムを得た。得られたシールドフィルムを上記(1)〜(2)の評価に供した。結果を表1に示す。
有機リン系難燃剤の添加量を表1のとおりとしたこと以外は実施例2と同様にしてシールドフィルムを得た。得られたシールドフィルムを上記(1)〜(4)の評価に供した。比誘電率、誘電正接、および難燃性の結果を表1に示す。
有機リン系難燃剤の添加量を表1のとおりとしたこと以外は実施例2と同様にしてシールドフィルムを得た。得られたシールドフィルムを上記(1)〜(4)の評価に供した。比誘電率、誘電正接、および難燃性の結果を表1に示す。
有機リン系難燃剤および導電性フィラーの添加量を表1のとおりとしたこと以外は実施例2と同様にしてシールドフィルムを得た。得られたシールドフィルムを上記(1)〜(4)の評価に供した。比誘電率、誘電正接、および難燃性の結果を表1に示す。アイパターンの結果を実施例2および参考例1の結果と併せて図3に示す。
表1から明らかなように、シールドフィルムの導電性接着剤層において特定の樹脂成分と特定量の有機リン系難燃剤と特定量の導電性フィラーとを組み合わせて用いることにより、優れた難燃性を付与しつつ、非常に低い比誘電率および誘電正接(すなわち、優れた高速伝送特性)を実現できることがわかる。また、図2に示すように、実施例2のシールドフィルムは、参考例1のシールドフィルムに比べてインピーダンス変化が小さいことがわかる。さらに、図3に示すように、実施例2のシールドフィルムは、参考例1および比較例6のシールドフィルムに比べてアイパターンが優れていることがわかる(特に、ビットレートが大きくなるほど顕著である)。すなわち、図2および図3は、シールドフィルムの導電性接着剤層において特定の樹脂成分に有機リン系難燃剤を加えることにより、難燃性のみならず伝送特性も顕著に改善されることを明確に示している。これは、特定の樹脂成分と有機リン系難燃剤との組み合わせによる予期せぬ優れた効果である。
20 導電性接着剤層
30 保護層
40 離型フィルム
100 シールドフィルム
Claims (5)
- 金属層と、該金属層の一方の側に配置された導電性接着剤層と、を備え、
該導電性接着剤層が、エポキシ樹脂とカルボキシル基含有エラストマーとの硬化物と、有機リン系難燃剤と、導電性フィラーと、を含み、
該金属層の厚みが0.3μm〜7μmであり、
該導電性接着剤層を構成する導電性接着剤が、該エポキシ樹脂および該カルボキシル基含有エラストマーの合計100重量部に対して、該有機リン系難燃剤を10重量部〜50重量部および該導電性フィラーを10重量部〜80重量部含む、
シールドフィルム。 - 前記カルボキシル基含有エラストマーが、不飽和カルボン酸で変性されたスチレン−エチレンプロピレン−スチレン共重合体である、請求項1に記載のシールドフィルム。
- 前記有機リン系難燃剤がホスフィン酸金属塩である、請求項1または2に記載のシールドフィルム。
- 前記導電性接着剤層が、VTM−0またはそれより良好な難燃性を有し、かつ、1GHzにおいて2.0〜4.0の比誘電率および0.0015〜0.0040の誘電正接を有する、請求項1から3のいずれかに記載のシールドフィルム。
- 請求項1から4のいずれかに記載のシールドフィルムを含む、シールドプリント配線板。
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WO2016190278A1 (ja) | 2016-12-01 |
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CN107535082A (zh) | 2018-01-02 |
US20180134920A1 (en) | 2018-05-17 |
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KR20170140350A (ko) | 2017-12-20 |
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