JP4210875B2 - Heat resistant flame retardant resin composition, adhesive film using the same, and metal foil with adhesive - Google Patents

Description

【０００６】
【化１１】
【０００７】
【化１２】

【０００８】
【化１３】

【０００９】
【化１４】
【００１０】
本発明は、シロキサン変性臭素化ポリアミドイミド樹脂が一般式（１式）で示される臭素化芳香族ジアミンと芳香族環を３個以上有するジアミン及びシロキサンジアミンの混合物と無水トリメリット酸を反応させて得られる一般式（２式）、（５式）及び一般式（３式）で示されるジイミドジカルボン酸を含む混合物と一般式（４式）で示される芳香族ジイソシアネートを反応させて得られるシロキサン変性臭素化ポリアミドイミド樹脂であり熱硬化性樹脂が２個以上のグリシジル基を持つエポキシ樹脂であると好ましい耐熱性難燃樹脂組成物である。また、本発明は、熱硬化性樹脂が、２個以上のグリシジル基を持つエポキシ樹脂とその硬化促進剤または硬化剤を含有すると好ましい耐熱性難燃樹脂組成物である。そして、本発明は、シロキサン変性ポリアミドイミド樹脂が、（ａ）一般式（１式）で示される臭素化芳香族ジアミン及び（ｃ）シロキサンジアミンの混合物と無水トリメリット酸とを（ａ+ｃ）の合計ｍｏｌと無水トリメリット酸のｍｏｌ比が１／２．０５〜１／２．２０で反応させて得られる一般式（２式）及び一般式（３式）で示されるジイミドジカルボン酸を含む混合物と一般式（４式）で示される芳香族ジイソシアネートとを（ａ+ｃ）の合計ｍｏｌと芳香族ジイソシアネートのｍｏｌ比が１／１．０５〜１／１．５０で反応させて得られるシロキサン変性臭素化ポリアミドイミド樹脂であると好ましく、シロキサン変性臭素化ポリアミドイミド樹脂が、（ａ）一般式（１式）で示される臭素化芳香族ジアミンと（ｂ）芳香族環を３個以上有するジアミン及び（ｃ）シロキサンジアミンの混合物と無水トリメリット酸とを（ａ＋ｂ+ｃ）の合計ｍｏｌと無水トリメリット酸のｍｏｌ比をジアミン／無水トリメリット酸＝１／２．０５〜１／２．２０で反応させて得られる一般式（２式）、（５式）及び一般式（３式）で示されるジイミドジカルボン酸を含む混合物と一般式（４式）で示される芳香族ジイソシアネートとを（ａ＋ｂ+ｃ）の合計ｍｏｌと芳香族ジイソシアネートのｍｏｌ比をジアミン／芳香族ジイソシアネート＝１／１．０５〜１／１．５０で反応させて得られるシロキサン変性臭素化ポリアミドイミド樹脂であると好ましい。そして、本発明は、シロキサン変性臭素化ポリアミドイミド樹脂が、（ｄ）臭素化芳香族ジイミドジカルボン酸として２，２−ビス［４−｛４−（５−ヒドロキシカルボニル−１，３−ジオン−イソインドリノ）フェノキシ｝−３，５−ジブロモフェニル］プロパン、（ｅ）芳香族環を３個以上有するジイミドジカルボン酸として２，２−ビス［４−｛４−（５−ヒドロキシカルボニル−１，３−ジオン−イソインドリノ）フェノキシ｝フェニル］プロパンと（ｆ）シロキサンジイミドジカルボン酸としてビス（５−ヒドロキシカルボニル−１，３−ジオン−イソインドリノ）プロピルポリジメチルシロキサンの混合物と芳香族ジイソシアネートとを（ｄ+ｅ＋ｆ）の合計ｍｏｌと芳香族ジイソシアネートのｍｏｌ比をジイミドジカルボン酸／芳香族ジイソシアネート＝１／１．０５〜１／１．５０で反応させて得られるシロキサン変性臭素化ポリアミドイミド樹脂であると好ましい。
更に、本発明は、上記の耐熱性難燃樹脂組成物をワニスとし、支持基材上に塗布させてフィルム状またはシート状にした接着フィルムである。また、本発明は、耐熱性難燃樹脂組成物をワニスとし、金属箔に塗布して得られる接着剤付金属箔である。本発明の耐熱性難燃樹脂組成物は、ワニス溶剤の揮発速度が速く、厚膜でも残存溶剤分を５重量％以下にすることが可能であり、基材との密着性の良好な接着フィルムまたは接着シートを得ることができる。
【００１１】
【発明の実施の形態】
本発明で用いる一般式（１式）で示される臭素化芳香族ジアミンは特開昭５８−８６３９号公報に記載されているようにテトラブロモビスフェノールＡとｐ−クロロニトロベンゼンを炭酸カリウムの存在下、ＮＭＰ中で反応させた
【００１２】
本発明で用いる芳香族環を３個以上有するジアミンとしては、２，２−ビス［４−（４−アミノフェノキシ）フェニル］プロパン（以下、ＢＡＰＰと略す）、ビス［４−（３−アミノフェノキシ）フェニル］スルホン、ビス［４−（４−アミノフェノキシ）フェニル］スルホン、２，２−ビス［４−（４−アミノフェノキシ）フェニル］ヘキサフルオロプロパン、ビス［４−（４−アミノフェノキシ）フェニル］メタン、４，４'−ビス（４−アミノフェノキシ）ビフェニル、ビス［４−（４−アミノフェノキシ）フェニル］エーテル、ビス［４−（４−アミノフェノキシ）フェニル］ケトン、１，３−ビス（４−アミノフェノキシ）ベンゼン、１，４−ビス（４−アミノフェノキシ）ベンゼン等が例示でき、単独でまたはこれらを組み合わせて用いることができる。ＢＡＰＰは、ポリアミドイミド樹脂の特性のバランスとコスト的に他のジアミンより特に好ましい。
【００１３】
本発明で用いるシロキサンジアミンとしては一般式（６式）で表されるものが用いられる。
【００１４】
【化１５】

【００１５】
このようなシロキサンジアミンとしては７式に示すものが挙げられ、これらの中でもシロキサン系両末端アミンであるアミノ変性シリコーンオイルＸ−２２−１６１ＡＳ（アミン当量４５０）、Ｘ−２２−１６１Ａ（アミン当量８４０）、Ｘ−２２−１６１Ｂ（アミン当量１５００）、以上信越化学工業株式会社製商品名、ＢＹ１６−８５３（アミン当量６５０）、ＢＹ１６−８５３Ｂ（アミン当量２２００）以上、東レダウコーニングシリコーン株式会社製商品名などが市販品として挙げられる。
【００１６】
【化１６】

【００１７】
本発明で用いる芳香族ジイソシアネートとして、４，４'−ジフェニルメタンジイソシアネート（以下ＭＤＩと略す）、２，４−トリレンジイソシアネート、２，６−トリレンジイソシアネート、ナフタレン−１，５−ジイソシアネート、２，４−トリレンダイマー等が例示できる。これらは単独でまたは組み合わせて用いることができる。
【００１８】
本発明で用いる熱硬化性樹脂として、エポキシ樹脂、フェノール樹脂、ポリエステル樹脂、ポリイミド樹脂、ビスマレイミドトリアジン樹脂等を使用することができる。接着性、取扱性よりエポキシ樹脂がより好ましい。熱硬化性樹脂は、シロキサン変性臭素化ポリアミドイミド樹脂１００重量部に対し１〜１５０重量部配合する。１重量部未満では、耐溶剤性に劣り、１５０重量部を超えると樹脂が脆くなり可撓性に乏しくなってしまう。熱硬化樹脂は、２個以上のグリシジル基を持つエポキシ樹脂とその硬化剤、もしくは、２個以上のグリシジル基を持つエポキシ樹脂とその硬化促進剤を用いることが好ましい。またグリシジル基は多いほどよく、３個以上であればさらに好ましい。グリシジル基の数により、配合量が異なり、グリシジル基が多いほど配合量が少なくてもよい。また、エポキシ樹脂の硬化剤を併用すればさらに好ましい。
【００１９】
エポキシ樹脂の硬化剤または硬化促進剤は、エポキシ樹脂と反応するもの、または、硬化を促進させるものであればどのようなものでもよく、例えば、アミン類、イミダゾール類、多官能フェノール類、酸無水物類等が使用できる。アミン類としては、ジシアンジアミド、ジアミノジフェニルメタン、グアニル尿素等が使用でき、イミダゾール類としてはアルキル基置換イミダゾール、ベンゾイミダゾール等が使用でき、多官能フェノール類としては、ヒドロキノン、レゾルシノール、ビスフェノールＡ及びこれらのハロゲン化合物、さらに前記多官能フェノール類とホルムアルデヒドとの付加縮合物であるノボラック型フェノール樹脂、レゾール型フェノール樹脂などが使用でき、酸無水物類としては、無水フタル酸、ベンゾフェノンテトラカルボン酸二無水物、メチルハイミック酸等が使用できる。このうち、硬化促進剤としては、イミダゾール類を用いることが好ましい。これらの硬化剤または硬化促進剤の必要な量は、アミン類の場合は、アミンの活性水素の当量とエポキシ樹脂のエポキシ当量がほぼ等しくなる量が好ましい。イミダゾールの場合は、単純に活性水素との当量比とならず、経験的にエポキシ樹脂１００重量部に対して、０．１〜１０重量部必要となる。多官能フェノール類の場合、エポキシ樹脂のエポキシ基１当量に対して、０．６〜１．２水酸基当量が必要である。これらの硬化剤または硬化促進剤の量は、少なければ未硬化のエポキシ樹脂が残り、Ｔｇが低くなり、多すぎると、未反応の硬化剤及び硬化促進剤が残り、絶縁性が低下する。
【００２０】
この他に、配線板に使用する際に、必要に応じてスルーホール内壁等のめっき密着性を上げること、及びアディティブ法で配線板を製造するために、無電解めっき用触媒を加えることもできる。
【００２１】
本発明では、これらの組成物を有機溶媒中で混合して、耐熱性難燃樹脂組成物とする。このような有機溶媒としては、溶解性が得られるものであればどのようなものでもよく、ジメチルアセトアミド、ジメチルホルムアミド、ジメチルスルホキシド、Ｎ−メチル−２−ピロリドン、γ−ブチロラクトン、スルホラン、シクロヘキサノン等が使用できる。
【００２２】
この耐熱性難燃樹脂組成物を、離型処理したポリエチレンテレフタレート（ＰＥＴ）フィルム等に塗布して接着フィルムや接着シートを作製したり、金属箔の片面に塗布して金属箔付接着フィルムや金属箔付接着シートとすることができる。金属箔が銅箔の場合、接着剤付銅箔が得られ、プリント配線板に用いれば、銅箔をエッチング加工して回路形成ができるので好ましい。耐熱性難燃樹脂組成物ワニスを支持基材上に塗布した後は目的に応じた硬化状態に加熱乾燥して使用することができる。
【００２３】
この耐熱性難燃樹脂組成物の配合比はシロキサン変性臭素化ポリアミドイミド樹脂中のシロキサン量、エポキシ樹脂のエポキシ当量によってきめることができる。耐熱性難燃樹脂組成物ワニスの溶剤揮発速度すなわち乾燥速度は組成物中のシロキサン量が多いほど速くなる。シロキサン量の多いシロキサン変性臭素化ポリアミドイミドを使用すればより多くのエポキシ樹脂等の熱硬化性樹脂成分を配合しても高い乾燥速度のワニスを得ることができ、その結果、より穏和な乾燥条件でも残存溶剤の少ない接着フィルム、接着シート、接着剤付金属箔を得ることができる。
【００２４】
またエポキシ樹脂のエポキシ基はシロキサン変性臭素化ポリアミドイミド樹脂のアミド基と反応する。従って熱硬化性樹脂としてエポキシ樹脂単独またはエポキシ樹脂とその硬化促進剤を用いる場合にはシロキサン変性臭素化ポリアミドイミド樹脂のアミド当量とエポキシ樹脂のエポキシ当量の比が１以下となるように配合することが好ましい。エポキシ樹脂の配合量が多くなると未反応のエポキシ樹脂が硬化後接着剤中に残りＴｇが上がらないおそれがある。接着フィルム、接着シート、接着剤付金属箔は加熱によって硬化させることができる。硬化促進剤としてイミダゾール等の塩基性触媒を使用すると硬化温度は１６０℃程度の低温から始めることが可能でありエポキシ樹脂のグリシジル基とシロキサン変性ポリアミドイミド樹脂のアミド基の間で挿入反応が起こり三次元橋かけ樹脂が得られる。
【００２５】
【実施例】
（合成例１）
環流冷却器を連結したコック付き２５ｍｌの水分定量受器、温度計、撹拌器を備えた１リットルのセパラブルフラスコに臭素化芳香族ジアミンとして（２，２−ビス［４−（４−アミノフェノキシ）−３，５−ジブロモフェニル］プロパン）１１６．２ｇ（０．１６ｍｏｌ）、シロキサンジアミンとして反応性シリコンオイルＸ−２２−１６１ＡＳ（信越化学工業株式会社製商品名、アミン当量４１６）３３．３ｇ（０．０４ｍｏｌ）、ＴＭＡ（無水トリメリット酸）８０．７ｇ（０．４２ｍｏｌ）を、非プロトン性極性溶媒としてＮＭＰ（Ｎ−メチル−２−ピロリドン）５６０ｇを仕込み、８０℃で３０分間撹拌した。そして水と共沸可能な芳香族炭化水素としてトルエン１００ｍｌを投入してから温度を上げ約１６０℃で２時間環流させた。水分定量受器に水が約７．２ｍｌ以上たまっていること、水の流出が見られなくなっていることを確認し、水分定量受器にたまっている流出液を除去しながら、約１９０℃まで温度を上げて、トルエンを除去した。その後、溶液を室温に戻し、芳香族ジイソシアネートとしてＭＤＩ（４，４'−ジフェニルメタンジイソシアネート）６０．１ｇ（０．２４ｍｏｌ）を投入し、１９０℃で２時間反応させた。反応終了後、シロキサン変性臭素化ポリアミドイミド樹脂のＮＭＰ溶液を得た。
【００２６】
（合成例２）
環流冷却器を連結したコック付き２５ｍｌの水分定量受器、温度計、撹拌器を備えた１リットルのセパラブルフラスコに臭素化芳香族ジアミンとして（２，２−ビス［４−（４−アミノフェノキシ）−３，５−ジブロモフェニル］プロパン）２９．０ｇ（０．０４ｍｏｌ）、芳香族環を３個以上有するジアミンとして（２，２−ビス［４−（４−アミノフェノキシ）フェニル］プロパン）１６．４ｇ（０．０４ｍｏｌ）、シロキサンジアミンとして反応性シリコンオイルＸ−２２−１６１ＡＳ（信越化学工業株式会社製商品名、アミン当量４１６）１６．７ｇ（０．０２ｍｏｌ）、ＴＭＡ（無水トリメリット酸）４０．３ｇ（０．２１ｍｏｌ）を、非プロトン性極性溶媒としてＮＭＰ（Ｎ−メチル−２−ピロリドン）３１５ｇを仕込み、８０℃で３０分間撹拌した。そして水と共沸可能な芳香族炭化水素としてトルエン１００ｍｌを投入してから温度を上げ約１６０℃で２時間環流させた。水分定量受器に水が約３．６ｍｌ以上たまっていること、水の流出が見られなくなっていることを確認し、水分定量受器にたまっている流出液を除去しながら、約１９０℃まで温度を上げて、トルエンを除去した。その後、溶液を室温に戻し、芳香族ジイソシアネートとしてＭＤＩ（４，４'−ジフェニルメタンジイソシアネート）３０．０ｇ（０．１２ｍｏｌ）を投入し、１９０℃で２時間反応させた。反応終了後、シロキサン変性臭素化ポリアミドイミド樹脂のＮＭＰ溶液を得た。
【００２７】
（合成例３）
環流冷却器を連結したコック付き２５ｍｌの水分定量受器、温度計、撹拌器を備えた１リットルのセパラブルフラスコに臭素化芳香族ジアミンとして（２，２−ビス［４−（４−アミノフェノキシ）−３，５−ジブロモフェニル］プロパン）、２９．１ｇ（０．０４ｍｏｌ）、芳香族環を３個以上有するジアミンとして（２，２−ビス［４−（４−アミノフェノキシ）フェニル］プロパン）、４１．５ｇ（０．１０ｍｏｌ）、シロキサンジアミンとして反応性シリコンオイルＸ−２２−１６１ＡＳ（信越化学工業株式会社製商品名、アミン当量４１６）５０．０ｇ（０．０６ｍｏｌ）、ＴＭＡ（無水トリメリット酸）８０．７ｇ（０．４２ｍｏｌ）、非プロトン性極性溶媒としてＮＭＰ（Ｎ−メチル−２−ピロリドン）５６０ｇを仕込み、８０℃で３０分間撹拌した。そして水と共沸可能な芳香族炭化水素としてトルエン１００ｍｌを投入してから温度を上げ約１６０℃で２時間環流させた。水分定量受器に水が約７．２ｍｌ以上たまっていること、水の流出が見られなくなっていることを確認し、水分定量受器にたまっている流出液を除去しながら、約１９０℃まで温度を上げて、トルエンを除去した。その後、溶液を室温に戻し、芳香族ジイソシアネートとしてＭＤＩ（４，４'−ジフェニルメタンジイソシアネート）６０．０ｇ（０．２４ｍｏｌ）を投入し、１９０℃で２時間反応させた。反応終了後、シロキサン変性臭素化ポリアミドイミド樹脂のＮＭＰ溶液を得た。
【００２８】
（合成例４）
環流冷却器を連結したコック付き２５ｍｌの水分定量受器、温度計、撹拌器を備えた１リットルのセパラブルフラスコに芳香族環を３個以上有するジアミンとして（２，２−ビス［４−（４−アミノフェノキシ）フェニル］プロパン）８２．１ｇ（０．２０ｍｏｌ）、ＴＭＡ（無水トリメリット酸）８０．７ｇ（０．４２ｍｏｌ）、非プロトン性極性溶媒としてＮＭＰ（Ｎ−メチル−２−ピロリドン）５６０ｇを仕込み、８０℃で３０分間撹拌した。そして水と共沸可能な芳香族炭化水素としてトルエン１００ｍｌを投入してから温度を上げ約１６０℃で２時間環流させた。水分定量受器に水が約７．２ｍｌ以上たまっていること、水の流出が見られなくなっていることを確認し、水分定量受器にたまっている流出液を除去しながら、約１９０℃まで温度を上げて、トルエンを除去した。その後、溶液を室温に戻し、芳香族ジイソシアネートとしてＭＤＩ（４，４'−ジフェニルメタンジイソシアネート）６０．０ｇ（０．２４ｍｏｌ）を投入し、１９０℃で２時間反応させた。反応終了後、芳香族ポリアミドイミド樹脂のＮＭＰ溶液を得た。
【００２９】
（実施例１〜１０）
合成例１〜４のシロキサン変性臭素化ポリアミドイミド樹脂または芳香族ポリアミドイミド樹脂とエポキシ樹脂としてＥＳＣＮ１９５（住友化学工業株式会社製商品名、ｏ−クレゾールノボラック型エポキシ樹脂、エポキシ当量１９５ｇ／ｅｑ）、２−エチル−４−メチルイミダゾールを表１に示す配合量で配合し、樹脂が均一になるまで約１時間撹拌した後、脱泡のため２４時間、室温で静置し耐熱性難燃樹脂組成物とした。その樹脂組成物を、離型ＰＥＴフィルム上に乾燥後の膜厚が５０μｍとなるように塗布し、１２０℃、３０分乾燥させＢステージの接着フィルムとした。その後、この接着フィルムを剥がしテフロン製の枠に固定し、１８０℃で６０分間熱処理を行い硬化物フィルムを得た。この硬化物フィルムのガラス転移温度、貯蔵弾性率、難燃性を測定し、結果を表１に示した。なお、ガラス転移点（Ｔｇ）と貯蔵弾性率は、粘弾性測定装置、ＤＶＥ−Ｖ４型（レオロジー社製商品名）を用い、下記の条件で測定した。Ｔｇはｔａｎδの最大値を用いた。
・治具：引張り
・チャック間距離：２０ｍｍ
・測定温度：５０〜３５０℃
・昇温速度：５℃／分
・測定周波数：１０Ｈｚ
・サンプルサイズ；５ｍｍ幅×３０ｍｍ長
【００３０】
またＢステージの接着フィルムの加熱処理前後（１８０℃、１時間）のフィルムの重量変化からＢステージでのフィルム中の残存揮発分を測定し残存揮発分としてその測定結果を表１にあわせて示した。更に、銅箔（古河サーキットフォイル株式会社製商品名、ＴＳＣ−１８）の粗化面側に耐熱性難燃樹脂組成物ワニスを乾燥厚みが５０μｍになるように塗布し、上記と同条件でＢステージの接着剤付銅箔を作製した。この接着剤付銅箔と別の銅箔ＴＳＣ−１８と張り合わせ、温度１８０℃、圧力２０ｋｇｆ/ｃｍ²、１時間プレスし両面銅箔張積層板を得た。得られた両面銅箔張積層板の銅箔／接着剤間の銅箔引き剥がし強さを銅箔接着強度として表１に示した。また、２６０℃のはんだ浴に浸漬し、フクレや剥がれが発生する時間を３分間観察しその結果を表１に示した。さらにフィルムの燃焼試験を行い、その測定結果を表１に示した。
【００３１】
（比較例１）
比較例１として、実施例６の配合でポリアミドイミド樹脂として臭素を含まない樹脂を用いた配合とした。即ち合成例２の臭素化芳香族ジアミン０．０４モルの代わりに芳香族環を３個以上有するジアミンを０．０４モル加え芳香族環を３個以上有するジアミンを合計０．０８モル、シロキサンジアミンを０．０２モルにした以外は合成例２と同様にしてシロキサン含有ポリアミドイミド樹脂のＮＭＰ溶液を合成して用いた。その他は実施例と同じ乾燥条件でＢステージフィルムを作製し、その後１８０℃で１時間硬化してＣステージフィルムとした。そして実施例と同様にして諸特性を測定し結果を表１に示した。
【００３２】
（比較例２）
比較例２として、合成例４の芳香族ポリアミドイミド樹脂のＮＭＰ溶液を用いた。その他は実施例と同じ乾燥条件でＢステージフィルムを作製し、その後１８０℃で１時間硬化してＣステージフィルムとした。そして実施例と同様にして諸特性を測定し結果を表１に示した。
【００３３】
【表１】

【００３４】
本発明の耐熱性難燃樹脂組成物は、合成例１〜４に示したように沸点が２０２℃であるＮ−メチル−２−ピロリドンを使用し、１２０℃で３０分間乾燥させたにも係わらず残存揮発分を少ない値にすることができ、エポキシ樹脂の硬化をほとんど進めることなくＢステージの接着フィルム、シート、接着剤付銅箔を製造することができた。これは、ポリアミドイミド樹脂中にシロキサン成分を含まない比較例２のＢステ−ジの残存揮発分が１３．０重量％と高いことからも明らかなように、ポリアミドイミド樹脂中にシロキサンを含有しているためであり、溶剤乾燥性が良好で、穏和な条件で残存揮発分の少ないＢステージの接着剤を得ることができる。そして、硬化物のＴｇは１９５℃以上と高く、銅箔に対する接着力も高い。また、比較例１の臭素を含まない樹脂に比べて難燃性が高く、ＶＴＭ−０となる。
【００３５】
【発明の効果】
以上に説明したように、本発明によって、難燃性、耐熱性、溶剤乾燥性に優れた耐熱性難燃樹脂組成物とそれを用いた接着フィルム、接着シート及び接着剤付金属箔を提供することができる。金属箔である銅箔との接着性、はんだ耐熱性に優れることから配線板用途に最適である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a heat-resistant flame-retardant resin composition, an adhesive film using the same, and a metal foil with an adhesive.
[0002]
[Prior art]
Polyamideimide resins are mainly used for wire coating materials (heat resistant enameled wires) because they have excellent electrical properties, heat resistance, mechanical properties, and abrasion resistance.
[0003]
[Problems to be solved by the invention]
However, since polyamideimide resin is generally synthesized using a solvent having a high boiling point, there are some problems in processing into a film or sheet. For example, under low-temperature drying conditions of 150 ° C. or lower, drying for a long time is necessary, and the residual volatile content of a film or sheet generally obtained is 10% by weight or more. Further, when a sheet exceeding 100 μm was produced even under high temperature drying conditions of 150 ° C. or higher, it was difficult to make the residual volatile content 5% by weight or less. Further, when a resin composition in which a thermosetting resin is blended with a polyamide-imide resin is formed into a sheet under high-temperature drying conditions, a thermosetting reaction proceeds, making it difficult to produce a so-called B-stage sheet. One application of polyamideimide resin is an interlayer adhesive film for wiring boards. This takes the form which apply | coated the resin composition which mix | blended the polyamideimide resin and the thermosetting resin on base materials, such as a plastic film, and made it the film form or a sheet form, In such a case, in a film or a sheet | seat It is preferable that the residual volatile content of the water is 5% by weight or less, preferably 1% by weight or less. In addition, it is necessary to dry the coating film at a low temperature that does not cause the curing reaction of the thermosetting resin. Furthermore, it is preferable that the remaining volatile content of the sheet can be reduced even for a sheet having a thickness exceeding 100 μm, for example, regardless of the thickness of the sheet. Moreover, it is preferable that the adhesiveness between a base material and a resin composition sheet is high. The present invention does not accelerate the curing reaction even when dried at such a low temperature, has a low residual volatile content, has excellent adhesiveness, and has a flame-retardant and heat-resistant heat-resistant flame-retardant resin composition and its use An object of the present invention is to provide an adhesive film and a metal foil with an adhesive.
[0004]
[Means for Solving the Problems]
The present invention is a heat-resistant flame-retardant resin composition containing 100 parts by weight of the following siloxane-modified brominated polyamideimide resin and 1 to 150 parts by weight of a thermosetting resin. It is preferable that the thermosetting resin is an epoxy resin having two or more glycidyl groups. The siloxane-modified brominated polyamideimide resin used in the present invention is a combination of (a) brominated aromatic diamine (formula 1), (b) diamine having 3 or more aromatic rings, and (c) siloxane diamine as diamine components. Used, and reacted with trimellitic anhydride (a ′) brominated aromatic diimide dicarboxylic acid (formula 2), (b ′) diimide dicarboxylic acid (formula 5) having 3 or more aromatic rings, (c ′ ) A mixture containing siloxane diimide dicarboxylic acid (formula 3) and preferably obtained by reacting these diimide dicarboxylic acid and aromatic diisocyanate (formula 4). There are two types of siloxane-modified brominated polyamideimide resins that are preferred for use in the present invention, depending on the combination of diamines. One is the combination of (a) (a) brominated aromatic diamine (formula 1) and (c) siloxane diamine. (B) The other one is a combination of (a) brominated aromatic diamine (formula 1), (b) diamine having 3 or more aromatic rings, and (c) siloxane diamine. Then, (i) and (b) the reaction molar ratio of diamine and trimellitic anhydride in each case was reacted with diamine / trimellitic anhydride = 1 / 2.05 to 1 / 2.20, and the resulting diimide The reaction is preferably carried out at a molar ratio of diamine / aromatic diisocyanate = 1 / 1.05 to 1 / 1.50 using a molar ratio of the mixture containing the dicarboxylic acid and the aromatic isocyanate.
[0005]
[Chemical Formula 10]

[0006]
Embedded image
[0007]
Embedded image

[0008]
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[0009]
Embedded image
[0010]
In the present invention, a siloxane-modified brominated polyamideimide resin is reacted with a mixture of a brominated aromatic diamine represented by the general formula (formula 1), a diamine having three or more aromatic rings and siloxane diamine, and trimellitic anhydride. Siloxane modification obtained by reacting the resulting mixture containing diimidedicarboxylic acid represented by general formula (2 formula), (5 formula) and general formula (3 formula) with aromatic diisocyanate represented by general formula (4 formula) It is a preferable heat-resistant flame-retardant resin composition when it is a brominated polyamideimide resin and the thermosetting resin is an epoxy resin having two or more glycidyl groups. Moreover, this invention is a preferable heat resistant flame-retardant resin composition, when a thermosetting resin contains the epoxy resin which has a 2 or more glycidyl group, its hardening accelerator, or a hardening | curing agent. In the present invention, the siloxane-modified polyamideimide resin comprises (a) a mixture of a brominated aromatic diamine represented by the general formula (formula 1) and (c) siloxane diamine and trimellitic anhydride (a + c). A diimide dicarboxylic acid represented by the general formula (formula 2) and the general formula (formula 3) obtained by reacting at a molar ratio of total mol of trimellitic anhydride to 1 / 2.05 to 1 / 2.20 Siloxane obtained by reacting a mixture with an aromatic diisocyanate represented by the general formula (formula 4) at a molar ratio of the total mol of (a + c) to the aromatic diisocyanate of 1 / 1.05 to 1 / 1.50 A modified brominated polyamideimide resin is preferred, and the siloxane-modified brominated polyamideimide resin comprises (a) a brominated aromatic diamine represented by the general formula (1 formula) and (b) 3 aromatic rings. A mixture of the diamine and (c) siloxane diamine and trimellitic anhydride having the above total mol of (a + b + c) and the molar ratio of trimellitic anhydride is diamine / trimellitic anhydride = 1 / 2.05-1 / 2. A mixture containing diimidedicarboxylic acid represented by the general formula (formula 2), (formula 5) and general formula (formula 3) obtained by reacting in 2.20 and an aromatic diisocyanate represented by the general formula (formula 4); A siloxane-modified brominated polyamideimide resin obtained by reacting a total mole of (a + b + c) with a molar ratio of aromatic diisocyanate to diamine / aromatic diisocyanate = 1 / 1.05 to 1 / 1.50. preferable. In the present invention, the siloxane-modified brominated polyamideimide resin has 2,2-bis [4- {4- (5-hydroxycarbonyl-1,3-dione-isoindolino) as (d) brominated aromatic diimide dicarboxylic acid. ) Phenoxy} -3,5-dibromophenyl] propane, (e) 2,2-bis [4- {4- (5-hydroxycarbonyl-1,3-dione) as diimidedicarboxylic acid having 3 or more aromatic rings -Isoindolino) phenoxy} phenyl] propane and (f) a mixture of bis (5-hydroxycarbonyl-1,3-dione-isoindolino) propylpolydimethylsiloxane as siloxane diimide dicarboxylic acid and an aromatic diisocyanate of (d + e + f) The molar ratio of total mol to aromatic diisocyanate is diimide dicarboxylic acid / A siloxane-modified brominated polyamideimide resin obtained by reacting with aromatic diisocyanate = 1 / 1.05 to 1 / 1.50 is preferred.
Furthermore, the present invention is an adhesive film in which the above heat-resistant flame retardant resin composition is used as a varnish and is applied onto a supporting substrate to form a film or a sheet. Moreover, this invention is metal foil with an adhesive agent obtained by making a heat resistant flame-retardant resin composition into varnish and apply | coating to metal foil. The heat-resistant flame retardant resin composition of the present invention has a fast volatilization rate of the varnish solvent, and can have a residual solvent content of 5% by weight or less even with a thick film, and has good adhesion to the substrate. Alternatively, an adhesive sheet can be obtained.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
The brominated aromatic diamine represented by the general formula (formula 1) used in the present invention is prepared by combining tetrabromobisphenol A and p-chloronitrobenzene in the presence of potassium carbonate as described in JP-A-58-8639. Reacted in NMP
Examples of the diamine having three or more aromatic rings used in the present invention include 2,2-bis [4- (4-aminophenoxy) phenyl] propane (hereinafter abbreviated as BAPP), bis [4- (3-aminophenoxy). ) Phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, bis [4- (4-aminophenoxy) phenyl ] Methane, 4,4′-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ketone, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene and the like can be exemplified, alone or in combination Can be used. BAPP is particularly preferred over other diamines in terms of the balance of properties of the polyamideimide resin and cost.
[0013]
As the siloxane diamine used in the present invention, those represented by the general formula (formula 6) are used.
[0014]
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[0015]
Examples of such siloxane diamines include those shown in Formula 7, among which amino-modified silicone oils X-22-161AS (amine equivalent 450) and X-22-161A (amine equivalent 840), which are siloxane-based amines at both ends. ), X-22-161B (amine equivalent 1500), trade names manufactured by Shin-Etsu Chemical Co., Ltd., BY16-853 (amine equivalent 650), BY16-853B (amine equivalent 2200) or more, products manufactured by Toray Dow Corning Silicone Co., Ltd. Names are listed as commercial products.
[0016]
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[0017]
As the aromatic diisocyanate used in the present invention, 4,4′-diphenylmethane diisocyanate (hereinafter abbreviated as MDI), 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, 2,4 -Tolylene dimer etc. can be illustrated. These can be used alone or in combination.
[0018]
As the thermosetting resin used in the present invention, an epoxy resin, a phenol resin, a polyester resin, a polyimide resin, a bismaleimide triazine resin, or the like can be used. An epoxy resin is more preferable than adhesiveness and handleability. The thermosetting resin is blended in an amount of 1 to 150 parts by weight based on 100 parts by weight of the siloxane-modified brominated polyamideimide resin. If it is less than 1 part by weight, the solvent resistance is poor, and if it exceeds 150 parts by weight, the resin becomes brittle and the flexibility becomes poor. The thermosetting resin is preferably an epoxy resin having two or more glycidyl groups and its curing agent, or an epoxy resin having two or more glycidyl groups and its curing accelerator. Further, the more glycidyl groups, the better. The blending amount varies depending on the number of glycidyl groups, and the blending amount may be smaller as the glycidyl group is larger. Further, it is more preferable to use an epoxy resin curing agent in combination.
[0019]
The epoxy resin curing agent or curing accelerator may be anything that reacts with the epoxy resin or accelerates curing, such as amines, imidazoles, polyfunctional phenols, acid anhydrides. Things can be used. As the amines, dicyandiamide, diaminodiphenylmethane, guanylurea and the like can be used. As the imidazoles, alkyl group-substituted imidazole, benzimidazole and the like can be used. As the polyfunctional phenols, hydroquinone, resorcinol, bisphenol A and their halogens. Compounds, and further, novolak-type phenol resins and resol-type phenol resins, which are addition condensates of polyfunctional phenols and formaldehyde, can be used as acid anhydrides, such as phthalic anhydride, benzophenone tetracarboxylic dianhydride, Methyl hymic acid can be used. Of these, imidazoles are preferably used as the curing accelerator. In the case of amines, the necessary amount of these curing agents or curing accelerators is preferably such that the active hydrogen equivalent of the amine and the epoxy equivalent of the epoxy resin are approximately equal. In the case of imidazole, it is not simply an equivalent ratio with active hydrogen, and is empirically required to be 0.1 to 10 parts by weight per 100 parts by weight of the epoxy resin. In the case of polyfunctional phenols, 0.6 to 1.2 hydroxyl equivalents are required for 1 equivalent of epoxy groups of the epoxy resin. If the amount of these curing agents or curing accelerators is small, uncured epoxy resin remains, and Tg becomes low. If too large, unreacted curing agents and curing accelerators remain, and the insulating property is lowered.
[0020]
In addition to this, when used for a wiring board, an electroless plating catalyst can be added to increase the plating adhesion of the inner wall of the through-hole, etc., if necessary, and to produce the wiring board by an additive method. .
[0021]
In the present invention, these compositions are mixed in an organic solvent to obtain a heat resistant flame retardant resin composition. As such an organic solvent, any solvent can be used as long as solubility is obtained. Examples thereof include dimethylacetamide, dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, γ-butyrolactone, sulfolane, and cyclohexanone. Can be used.
[0022]
This heat-resistant flame-retardant resin composition is applied to a release-treated polyethylene terephthalate (PET) film or the like to produce an adhesive film or an adhesive sheet, or applied to one side of a metal foil to form an adhesive film with metal foil or a metal It can be set as the adhesive sheet with foil. When the metal foil is a copper foil, an adhesive-attached copper foil is obtained, and if used for a printed wiring board, the copper foil can be etched to form a circuit, which is preferable. After the heat-resistant flame retardant resin composition varnish is applied on the support substrate, it can be used after being dried by heating to a cured state according to the purpose.
[0023]
The blending ratio of the heat resistant flame retardant resin composition can be determined by the amount of siloxane in the siloxane-modified brominated polyamideimide resin and the epoxy equivalent of the epoxy resin. The solvent volatilization rate, that is, the drying rate of the heat resistant flame retardant resin composition varnish increases as the amount of siloxane in the composition increases. If siloxane-modified brominated polyamideimide with a large amount of siloxane is used, a higher drying rate varnish can be obtained even if more thermosetting resin components such as epoxy resins are blended, resulting in milder drying conditions. However, it is possible to obtain an adhesive film, an adhesive sheet, and a metal foil with an adhesive with little residual solvent.
[0024]
The epoxy group of the epoxy resin reacts with the amide group of the siloxane-modified brominated polyamideimide resin. Therefore, when an epoxy resin alone or an epoxy resin and its curing accelerator are used as the thermosetting resin, the ratio of the amide equivalent of the siloxane-modified brominated polyamideimide resin and the epoxy equivalent of the epoxy resin should be 1 or less. Is preferred. When the compounding amount of the epoxy resin is increased, the unreacted epoxy resin may remain in the adhesive after curing and the Tg may not be increased. The adhesive film, adhesive sheet, and metal foil with adhesive can be cured by heating. When a basic catalyst such as imidazole is used as a curing accelerator, the curing temperature can be started from a low temperature of about 160 ° C., and an insertion reaction occurs between the glycidyl group of the epoxy resin and the amide group of the siloxane-modified polyamideimide resin. A former cross-linked resin is obtained.
[0025]
【Example】
(Synthesis Example 1)
A 2-liter separable flask equipped with a water condenser with a cock connected to a reflux condenser, a thermometer, and a stirrer was added as a brominated aromatic diamine (2,2-bis [4- (4-aminophenoxy). ) -3,5-dibromophenyl] propane) 116.2 g (0.16 mol), reactive silicone oil X-22-161AS (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., amine equivalent 416) as siloxane diamine 33.3 g ( 0.04 mol) and 80.7 g (0.42 mol) of TMA (trimellitic anhydride) were charged with 560 g of NMP (N-methyl-2-pyrrolidone) as an aprotic polar solvent, followed by stirring at 80 ° C. for 30 minutes. Then, 100 ml of toluene was added as an aromatic hydrocarbon azeotropic with water, and the temperature was raised and refluxed at about 160 ° C. for 2 hours. Confirm that water has accumulated in the moisture metering receiver about 7.2ml or more and that no water has flowed out, and remove the effluent accumulated in the moisture metering receiver, up to about 190 ° C. The temperature was raised to remove toluene. Thereafter, the solution was returned to room temperature, 60.1 g (0.24 mol) of MDI (4,4′-diphenylmethane diisocyanate) was added as an aromatic diisocyanate, and the mixture was reacted at 190 ° C. for 2 hours. After completion of the reaction, an NMP solution of siloxane-modified brominated polyamideimide resin was obtained.
[0026]
(Synthesis Example 2)
A 2-liter separable flask equipped with a water condenser with a cock connected to a reflux condenser, a thermometer, and a stirrer was added as a brominated aromatic diamine (2,2-bis [4- (4-aminophenoxy). ) -3,5-dibromophenyl] propane) 29.0 g (0.04 mol), (2,2-bis [4- (4-aminophenoxy) phenyl] propane) 16 as a diamine having 3 or more aromatic rings .4 g (0.04 mol), reactive silicon oil X-22-161AS (trade name, amine equivalent 416) manufactured by Shin-Etsu Chemical Co., Ltd. as siloxane diamine, 16.7 g (0.02 mol), TMA (trimellitic anhydride) 40.3 g (0.21 mol) was charged with 315 g of NMP (N-methyl-2-pyrrolidone) as an aprotic polar solvent, and 80 In the mixture was stirred for 30 minutes. Then, 100 ml of toluene was added as an aromatic hydrocarbon azeotropic with water, and the temperature was raised and refluxed at about 160 ° C. for 2 hours. Confirm that water has accumulated about 3.6 ml or more in the moisture determination receiver and that no outflow of water has been observed, and remove the effluent that has accumulated in the moisture determination receiver to about 190 ° C. The temperature was raised to remove toluene. Thereafter, the solution was returned to room temperature, 30.0 g (0.12 mol) of MDI (4,4′-diphenylmethane diisocyanate) was added as an aromatic diisocyanate, and the mixture was reacted at 190 ° C. for 2 hours. After completion of the reaction, an NMP solution of siloxane-modified brominated polyamideimide resin was obtained.
[0027]
(Synthesis Example 3)
A 2-liter separable flask equipped with a water condenser with a cock connected to a reflux condenser, a thermometer, and a stirrer was added as a brominated aromatic diamine (2,2-bis [4- (4-aminophenoxy). ) -3,5-dibromophenyl] propane), 29.1 g (0.04 mol), as a diamine having three or more aromatic rings (2,2-bis [4- (4-aminophenoxy) phenyl] propane) 41.5 g (0.10 mol), reactive silicon oil X-22-161AS (trade name, amine equivalent 416) manufactured by Shin-Etsu Chemical Co., Ltd. as siloxane diamine, 50.0 g (0.06 mol), TMA (anhydrous trimellit) Acid) 80.7 g (0.42 mol), NMP (N-methyl-2-pyrrolidone) 560 g as an aprotic polar solvent was charged, 8 And stirred for 30 min at ° C.. Then, 100 ml of toluene was added as an aromatic hydrocarbon azeotropic with water, and the temperature was raised and refluxed at about 160 ° C. for 2 hours. Confirm that water has accumulated in the moisture metering receiver about 7.2ml or more and that no water has flowed out, and remove the effluent accumulated in the moisture metering receiver, up to about 190 ° C. The temperature was raised to remove toluene. Thereafter, the solution was returned to room temperature, 60.0 g (0.24 mol) of MDI (4,4′-diphenylmethane diisocyanate) was added as an aromatic diisocyanate, and the mixture was reacted at 190 ° C. for 2 hours. After completion of the reaction, an NMP solution of siloxane-modified brominated polyamideimide resin was obtained.
[0028]
(Synthesis Example 4)
As a diamine having 3 or more aromatic rings in a 1-liter separable flask equipped with a 25 ml water meter with a cock connected to a reflux condenser, a thermometer, and a stirrer (2,2-bis [4- ( 4-aminophenoxy) phenyl] propane) 82.1 g (0.20 mol), TMA (trimellitic anhydride) 80.7 g (0.42 mol), NMP (N-methyl-2-pyrrolidone) as an aprotic polar solvent 560 g was charged and stirred at 80 ° C. for 30 minutes. Then, 100 ml of toluene was added as an aromatic hydrocarbon azeotropic with water, and the temperature was raised and refluxed at about 160 ° C. for 2 hours. Confirm that water has accumulated in the moisture metering receiver about 7.2ml or more and that no water has flowed out, and remove the effluent accumulated in the moisture metering receiver, up to about 190 ° C. The temperature was raised to remove toluene. Thereafter, the solution was returned to room temperature, 60.0 g (0.24 mol) of MDI (4,4′-diphenylmethane diisocyanate) was added as an aromatic diisocyanate, and the mixture was reacted at 190 ° C. for 2 hours. After completion of the reaction, an NMP solution of an aromatic polyamideimide resin was obtained.
[0029]
(Examples 1 to 10)
ESCN195 (commercial name, manufactured by Sumitomo Chemical Co., Ltd., o-cresol novolak type epoxy resin, epoxy equivalent 195 g / eq) as an epoxy resin and the siloxane-modified brominated polyamideimide resin or aromatic polyamideimide resin of Synthesis Examples 1-4 -Ethyl-4-methylimidazole was blended in the blending amounts shown in Table 1 and stirred for about 1 hour until the resin became uniform, and then allowed to stand at room temperature for 24 hours for defoaming. It was. The resin composition was applied onto a release PET film so that the film thickness after drying was 50 μm, and dried at 120 ° C. for 30 minutes to obtain a B-stage adhesive film. Thereafter, the adhesive film was peeled off, fixed to a Teflon frame, and heat treated at 180 ° C. for 60 minutes to obtain a cured product film. The glass transition temperature, storage elastic modulus, and flame retardancy of this cured product film were measured, and the results are shown in Table 1. In addition, the glass transition point (Tg) and the storage elastic modulus were measured on condition of the following using the viscoelasticity measuring device and DVE-V4 type (Rheology company make). As the Tg, the maximum value of tan δ was used.
・ Jig: Pulling ・ Distance between chucks: 20 mm
・ Measurement temperature: 50-350 ° C
・ Temperature increase rate: 5 ° C./min ・ Measurement frequency: 10 Hz
・ Sample size: 5mm width x 30mm length
Also, the residual volatile content in the B-stage film was measured from the change in film weight before and after the heat treatment of the B-stage adhesive film (180 ° C., 1 hour), and the measurement results are shown in Table 1 as the residual volatile content. It was. Furthermore, a heat resistant flame retardant resin composition varnish was applied to the roughened surface side of copper foil (Furukawa Circuit Foil Co., Ltd., trade name: TSC-18) so that the dry thickness was 50 μm. A copper foil with an adhesive for the stage was prepared. This copper foil with adhesive and another copper foil TSC-18 were bonded together and pressed at a temperature of 180 ° C. and a pressure of 20 kgf / cm ² for 1 hour to obtain a double-sided copper foil-clad laminate. Table 1 shows the copper foil peeling strength between the copper foil and the adhesive of the obtained double-sided copper foil-clad laminate as the copper foil adhesive strength. Moreover, it immersed in the solder bath of 260 degreeC, the time which a swelling and peeling generate | occur | produce was observed for 3 minutes, and the result was shown in Table 1. Further, a film burning test was performed, and the measurement results are shown in Table 1.
[0031]
(Comparative Example 1)
As comparative example 1, it was set as the mixing | blending which used the resin which does not contain a bromine as a polyamideimide resin by the mixing | blending of Example 6. FIG. That is, in place of 0.04 mol of the brominated aromatic diamine of Synthesis Example 2, 0.04 mol of diamine having 3 or more aromatic rings and 0.08 mol of diamine having 3 or more aromatic rings in total, siloxane diamine A NMP solution of a siloxane-containing polyamideimide resin was synthesized and used in the same manner as in Synthesis Example 2 except that 0.02 mol was used. Otherwise, a B-stage film was produced under the same drying conditions as in Examples, and then cured at 180 ° C. for 1 hour to obtain a C-stage film. Various characteristics were measured in the same manner as in the examples, and the results are shown in Table 1.
[0032]
(Comparative Example 2)
As Comparative Example 2, the NMP solution of the aromatic polyamideimide resin of Synthesis Example 4 was used. Otherwise, a B-stage film was produced under the same drying conditions as in the Examples, and then cured at 180 ° C. for 1 hour to obtain a C-stage film. Various characteristics were measured in the same manner as in the examples, and the results are shown in Table 1.
[0033]
[Table 1]

[0034]
Although the heat-resistant flame-retardant resin composition of the present invention used N-methyl-2-pyrrolidone having a boiling point of 202 ° C. as shown in Synthesis Examples 1 to 4, it was dried at 120 ° C. for 30 minutes. The residual volatile content could be reduced, and the B-stage adhesive film, sheet, and adhesive-attached copper foil could be produced with little progress in curing the epoxy resin. As is clear from the fact that the residual volatile content of the B stage of Comparative Example 2 which does not contain a siloxane component in the polyamideimide resin is as high as 13.0% by weight, the polyamideimide resin contains siloxane. This is because a solvent-drying property is good, and a B-stage adhesive having a small residual volatile content can be obtained under mild conditions. And Tg of hardened | cured material is as high as 195 degreeC or more, and the adhesive force with respect to copper foil is also high. Moreover, compared with the resin which does not contain the bromine of the comparative example 1, flame retardance is high and it becomes VTM-0.
[0035]
【The invention's effect】
As described above, the present invention provides a heat-resistant flame-retardant resin composition excellent in flame retardancy, heat resistance, and solvent drying properties, an adhesive film using the same, an adhesive sheet, and a metal foil with an adhesive. be able to. It is optimal for wiring board applications because of its excellent adhesion to copper foil, which is a metal foil, and solder heat resistance.

Claims (9)

General formula (2 formulas) and general formula (3 formulas) obtained by reacting a mixture of brominated aromatic diamine and siloxane diamine having a siloxane-modified brominated polyamideimide resin represented by general formula (1 formula) with trimellitic anhydride 100 parts by weight of a siloxane-modified brominated polyamideimide resin obtained by reacting a mixture containing a diimide dicarboxylic acid represented by formula (4) with an aromatic diisocyanate represented by the general formula (formula 4) and 1 to 150 parts by weight of a thermosetting resin. A heat-resistant flame-retardant resin composition to be contained.

  The heat-resistant flame-retardant resin composition according to claim 1, wherein the thermosetting resin is an epoxy resin having two or more glycidyl groups. A general formula obtained by reacting a siloxane-modified brominated polyamideimide resin with a mixture of a brominated aromatic diamine represented by the general formula (formula 1), a diamine having three or more aromatic rings and a siloxane diamine, and trimellitic anhydride Siloxane-modified brominated polyamideimide obtained by reacting a mixture containing diimide dicarboxylic acid represented by (formula 2), (formula 5) and general formula (formula 3) with an aromatic diisocyanate represented by general formula (formula 4) A heat-resistant flame-retardant resin composition, which is a resin and the thermosetting resin is an epoxy resin having two or more glycidyl groups.

  The heat-resistant flame retardant resin according to any one of claims 1 to 3, wherein the thermosetting resin contains an epoxy resin having two or more glycidyl groups and a curing accelerator or a curing agent thereof. Composition.   A siloxane-modified brominated polyamideimide resin comprises (a) a mixture of a brominated aromatic diamine represented by the general formula (formula 1) and (c) siloxane diamine and trimellitic anhydride in a total mol of (a + c) A mixture containing diimidedicarboxylic acid represented by the general formula (formula 2) and the general formula (formula 3) obtained by reacting at a molar ratio of trimellitic anhydride of 1 / 2.05 to 1 / 2.20 and the general formula Siloxane-modified brominated polyamide obtained by reacting the aromatic diisocyanate represented by (Formula 4) with a total molar ratio of (a + c) to the molar ratio of aromatic diisocyanate of 1 / 1.05 to 1 / 1.50. The heat-resistant flame-retardant resin composition according to any one of claims 1, 2, and 4, which is an imide resin.   Siloxane-modified brominated polyamideimide resin comprises (a) a brominated aromatic diamine represented by the general formula (formula 1), (b) a diamine having three or more aromatic rings, and (c) a mixture of siloxane diamine and anhydrous tri General formula (formula 2) obtained by reacting merit acid with mol ratio of total mol of (a + b + c) and trimellitic anhydride at diamine / trimellitic anhydride = 1 / 2.05 to 1 / 2.20 ), (5 formula) and a mixture containing diimide dicarboxylic acid represented by the general formula (3 formula) and the aromatic diisocyanate represented by the general formula (4 formula) and the total mol of (a + b + c) and the aromatic diisocyanate A siloxane-modified brominated polyamideimide resin obtained by reacting at a molar ratio of diamine / diisocyanate = 1 / 1.05 to 1 / 1.50. Or heat-resistant flame-retardant resin composition according to claim 4.   Siloxane-modified brominated polyamideimide resin is (d) 2,2-bis [4- {4- (5-hydroxycarbonyl-1,3-dione-isoindolino) phenoxy} -3, as brominated aromatic diimide dicarboxylic acid. 5-dibromophenyl] propane, (e) 2,2-bis [4- {4- (5-hydroxycarbonyl-1,3-dione-isoindolino) phenoxy} phenyl as diimidedicarboxylic acid having 3 or more aromatic rings ] A mixture of propane and (f) bis (5-hydroxycarbonyl-1,3-dione-isoindolino) propylpolydimethylsiloxane as siloxane diimide dicarboxylic acid and an aromatic diisocyanate, and a total mol of (d + e + f) and mol of diisocyanate The ratio is diimide dicarboxylic acid / aromatic diisocyanate = 7. The heat resistance according to claim 3, wherein the heat resistance is a siloxane-modified brominated polyamideimide resin obtained by reacting at 1 / 1.05 to 1 / 1.50. Flame retardant resin composition.   The adhesive film which made the heat-resistant flame-retardant resin composition in any one of Claim 1 thru | or 7 into a film form or a sheet form by making it apply | coat on a support base material.   A metal foil with an adhesive obtained by applying the heat-resistant flame-retardant resin composition according to any one of claims 1 to 7 to a metal foil as a varnish.