JP2017502100A - ノンハロゲン樹脂組成物及びそれを用いて製造されたプリプレグと積層板 - Google Patents
ノンハロゲン樹脂組成物及びそれを用いて製造されたプリプレグと積層板 Download PDFInfo
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- JP2017502100A JP2017502100A JP2016528902A JP2016528902A JP2017502100A JP 2017502100 A JP2017502100 A JP 2017502100A JP 2016528902 A JP2016528902 A JP 2016528902A JP 2016528902 A JP2016528902 A JP 2016528902A JP 2017502100 A JP2017502100 A JP 2017502100A
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- 0 C*Cc(cc1)ccc1N(C1)COc2c1cc(C(C)(C)c1cc(CN(CC3)c4ccc(C[C@](C)[*+])cc4)c3cc1)cc2 Chemical compound C*Cc(cc1)ccc1N(C1)COc2c1cc(C(C)(C)c1cc(CN(CC3)c4ccc(C[C@](C)[*+])cc4)c3cc1)cc2 0.000 description 3
- URLKBWYHVLBVBO-UHFFFAOYSA-N Cc1ccc(C)cc1 Chemical compound Cc1ccc(C)cc1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
ぼしたため基材同士及び基材と銅箔との接着強度を低下させるからである。
であってもよく、好ましくは15〜22部であり、さらに好ましくは15部である。
均分子量が1000〜4000である。
実施例は本発明を理解するためのものに過ぎず、本発明への具体的な制限と見なされるべきではないことを、当業者は了承すべきである。
窒素ガスを保護雰囲気として、撹拌する条件で、単量体である無水マレイン酸と開始剤とを媒体に加えて溶解させて60〜80℃に加熱した際、単量体であるイソプロペニルベンゼンと分子量調整剤とを滴下し、滴下終了後に撹拌し続けて1〜8h反応させて、低分子量のイソプロペニルベンゼン/無水マレイン酸ポリマー粒子の分散系を得た。分散系を遠心分離し乾燥させて、低分子量のイソプロペニルベンゼン/無水マレイン酸交互共重合体を得た。なお、前記開始剤は、有機過酸化物又はアゾ化合物であり、前記媒体は、有機酸アルキルエステルとアルカンとの混合溶液であり、前記分子量調整剤は、ビニルアセテートであり、無水マレイン酸とイソプロペニルベンゼンの使用量のモル比は1:0.90〜0.96であり、反応系における無水マレイン酸とイソプロペニルベンゼン二つの単量体の質量濃度の合計は2.0〜7.5%であり、開始剤の質量濃度は0.05〜0.35%であり、分子量調整剤の質量濃度は0.10〜0.45%であり、有機酸アルキルエステルとアルカンとの混合溶液における有機酸アルキルエステルの体積分率は20〜80%である。
エポキシ樹脂、ベンゾオキサジン、ポリフェニレンエーテル、イソプロペニルベンゼン−無水マレイン酸、ノンハロゲン難燃剤、硬化促進剤、フィラー、及び溶媒等を容器に入れて、均一に混合させるまで撹拌し、接着剤を製造し、溶媒で溶液における固形分の含有量を60%〜70%に調整して接着液を製造し、即ち本発明のノンハロゲン樹脂組成物接着液を得て、2116電子グレードのガラス繊維布を接着液に浸漬し、オーブンで半硬化シートに焼成し、6枚の2116半硬化シートを取り出し、両面に35μm厚みの電解銅箔を被覆し、ホットプレス機で真空積層を行い、190℃で120分硬化させ、銅張積層板を製造する。
A エポキシ樹脂
A−1 ビフェニル型エポキシ樹脂:NC−3000−H(日本化薬製 商品名)
A−2 ジシクロペンタジエン型エポキシ樹脂:HP−7200H(大日本インキ製 商品名)
B ベンゾオキサジン
B−1 脂肪族ベンゾオキサジン:KAH−F5404(韓国Kolon製 商品名)
B−2 フッ素化ベンゾオキサジン:KAH−F5301(韓国Kolon製 商品名)
B−3 ビスフェノールF型ベンゾオキサジン:LZ8280(ハンツマン・アドバンスト・マテリアルズ製)
B−4 ジシクロペンタジエン型ベンゾオキサジン:LZ8260(ハンツマン・アドバンスト・マテリアルズ製)
C−1 低分子量のポリフェニレンエーテル:MX90(SABIC Innovative Plastics 商品名)、数平均分子量1000〜4000
C−2 高分子量のポリフェニレンエーテル:Sabic640−111(SABIC
Innovative Plastics製 商品名)、数平均分子量15000〜20000
D−1 製造例におけるイソプロペニルベンゼン−無水マレイン酸オリゴマー
D−2 スチレン−無水マレイン酸オリゴマー:SMA−EF40(アメリカSartomer社製 商品名)
E ノンハロゲン難燃剤:リン含有フェノール樹脂:XZ92741(DOW化学製 商品名)
F 硬化促進剤:2E4MZ(四国化成製 商品名)
G フィラー:溶融シリカ
示差走査熱量法(DSC)に基づき、IPC−TM−650 2.4.25による指定されるDSC方法に従って測定する。
IPC−TM−650 2.4.8方法における「熱応力後」の実験条件に基づき、金属キャップの剥離強度を測定する。
ストリップライン共振法を用いて、IPC−TM−650 2.5.5.5に基づいて1GHzにおける誘電率(Dk)と誘電正接(Df)を測定する。
UL−94標準に基づいて測定する。
銅張積層板を銅エッチング液に浸漬し、表面銅箔を除去して基板を評価し、基板を圧力鍋の中に放置し、121℃、2atm下で2h処理し、吸水率を測定した後、温度288℃の錫ストーブの中に浸漬し、基材に発泡又はクラックが発生する際に対応する時間を記録する。基材を錫ストーブの中に入れてから5分後にも発泡又はクラックが発生しない場合、評価を終了する。
レイン酸オリゴマーが用いられた比較例1よりも低い誘電率、誘電正接及びPCT吸水率が得られるものである。
Claims (10)
- 前記エポキシ樹脂は、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、ビフェニル型エポキシ樹脂、アルキルノボラック型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、ビスフェノールAノボラック型エポキシ樹脂、o−クレゾールノボラック型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、三官能エポキシ樹脂、四官能エポキシ樹脂、イソシアネート改質エポキシ樹脂、ナフタレン型エポキシ樹脂、又はリン含有エポキシ樹脂から選ばれるいずれか1種又は少なくとも2種の混合物である、ことを特徴とする請求項1に記載のノンハロゲン樹脂組成物。
- 前記ベンゾオキサジンは、フッ素化ベンゾオキサジン樹脂、脂肪族ベンゾオキサジン樹脂、又はジシクロペンタジエン型ベンゾオキサジン樹脂から選ばれるいずれか1種又は少なくとも2種の混合物であり、
前記ベンゾオキサジンは、フッ素化ベンゾオキサジン樹脂、又は脂肪族ベンゾオキサジン樹脂から選ばれるいずれか1種又は少なくとも2種の混合物であることが好ましく、
前記フッ素化ベンゾオキサジン樹脂は、
前記脂肪族ベンゾオキサジン樹脂の化学構造式は、
前記ジシクロペンタジエン型ベンゾオキサジン樹脂の化学構造式は、
- 前記ポリフェニレンエーテルの数平均分子量は、1000〜4000である、ことを特徴とする請求項1に記載のノンハロゲン樹脂組成物。
- 前記ノンハロゲン難燃剤は、ホスファゼン、ポリリン酸アンモニウム、トリス(2−カルボキシエチル)ホスフィン、トリス(2−クロロプロピル)ホスフェート、トリメチルホスフェート、ジメチル−メチルホスフェート、レゾルシノールジキシリルホスフェート、リン窒素系化合物、ポリリン酸メラミン、メラミンシアヌレート、トリヒドロキシエチルイソシアヌレート、9,10−ジヒドロ−9−オキサ−10−ホスファフェナントレン
−10−オキシド、又はDOPO含有フェノール樹脂から選ばれるいずれか1種又は少なくとも2種の混合物である、ことを特徴とする請求項1に記載のノンハロゲン樹脂組成物。 - 前記硬化促進剤は、イミダゾール系促進剤であり、
前記硬化促進剤は、2−メチルイミダゾール、ウンデシルイミダゾール、2−エチル−4−メチルイミダゾール、2−フェニルイミダゾール、又は1−シアノエチル置換イミダゾールから選ばれるいずれか1種又は少なくとも2種の混合物であることが好ましい、ことを特徴とする請求項1に記載のノンハロゲン樹脂組成物。 - 前記フィラーは、無機又は有機フィラーであり、
前記フィラーが無機フィラーである場合、前記無機フィラーは、水酸化アルミニウム、酸化アルミニウム、水酸化マグネシウム、酸化マグネシウム、アルミナ、シリカ、炭酸カルシウム、窒化アルミニウム、窒化ホウ素、炭化ケイ素、二酸化チタン、酸化亜鉛、酸化ジルコニウム、雲母、ベーマイト、焼成タルク、タルカムパウダー、窒化ケイ素、又は焼成カオリンから選ばれるいずれか1種又は少なくとも2種の混合物であることが好ましく、
前記フィラーが有機フィラーである場合、前記有機フィラーは、ポリテトラフルオロエチレン粉末、ポリフェニレンサルファイド、又はポリエーテルスルホン粉末から選ばれるいずれか1種又は少なくとも2種の混合物であることが好ましく、
前記フィラーの粒径は、0.01〜50μmであり、好ましくは1〜15μmであり、さらに好ましくは1〜5μmである、ことを特徴とする請求項1に記載のノンハロゲン樹脂組成物。 - 請求項1〜7のいずれか一項に記載のノンハロゲン樹脂組成物を用いて製造されたプリプレグであって、基材と、浸漬乾燥後に基材に付着したノンハロゲン樹脂組成物とを含み、
前記基材は、ガラス繊維不織布、又はガラス繊維織布であることが好ましい、ことを特徴とするプリプレグ。 - 請求項8に記載のプリプレグを含む、ことを特徴とする積層板。
- 請求項9に記載の積層板を含む、ことを特徴とするプリント回路基板。
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PCT/CN2014/092841 WO2016074290A1 (zh) | 2014-11-11 | 2014-12-02 | 一种无卤树脂组合物及用其制作的预浸料与层压板 |
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AU2014411039A1 (en) | 2016-12-01 |
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TWI555792B (zh) | 2016-11-01 |
CN104448702A (zh) | 2015-03-25 |
CN104448702B (zh) | 2017-05-24 |
US20170198135A1 (en) | 2017-07-13 |
US10144824B2 (en) | 2018-12-04 |
EP3133122B1 (en) | 2019-07-24 |
JP6271008B2 (ja) | 2018-01-31 |
TW201617399A (zh) | 2016-05-16 |
KR101798809B1 (ko) | 2017-11-16 |
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