JP4442065B2 - Organic insulating film material and organic insulating film - Google Patents

Description

式（１）中、Ｘは式（２）より選ばれる構造を示す。
【０００８】
【化１４】

式（２）中、Ｘ₁は式（３）より選ばれる構造を示し、これらの構造中のベンゼン環上の水素原子は、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔ−ブチル基、フッ素原子、およびトリフルオロメチル基からなる群から選ばれる少なくとも1個の基で置換されていてもよい。
【０００９】
【化１５】

【００１０】
【化１６】

式（４）中、Ｙは式（５）より選ばれる構造を示す。
【００１１】
【化１７】

式（５）中、Ｘ₁は式（３）より選ばれる構造を示す。
【００１２】
【化１８】

式（６）中、Ｚは式（７）より選ばれる構造を示す。
【００１３】
【化１９】

【００１４】
【化２０】

但し、一般式（８）中のｎは２〜１０００までの整数を示す。Ｘは（２）より、及びＹは式（５）よりそれぞれ選ばれる構造を示す。
【００１５】
【化２１】

但し、一般式（９）中のｎは２〜１０００までの整数を示す。Ｘは（２）より、及びＹは式（５）よりそれぞれ選ばれる構造を示す。
【００１６】
すなわち、本発明は、（ａ）〜（ｅ）項に記載の通りである。
【００１７】
（ａ） 一般式（１）で表されるジアミノフェノール化合物と、該化合物のアミノ基と反応しうるｄ価の有機基を有する化合物（ｄは３以上１０以下）とを反応させ、続けて一般式（４）で表されるジカルボン酸化合物とを反応させた後、一般式（６）で表されるカルボン酸化合物と反応させることにより得られる、一般式（８）で表されるポリベンゾオキサゾール樹脂前駆体を主構造とする重合体からなることからなることを特徴とする有機絶縁膜材料。
【００１８】
（ｂ） 一般式（１）で表されるジアミノフェノール化合物（Ｍ）と、一般式（４）で表されるジカルボン酸化合物（Ｎ）とが、反応モル比（Ｎ／Ｍ）を、０．５から０．９９の範囲で反応させたことを特徴とする前記（ａ）項に記載の有機絶縁膜用材料。
【００１９】
（ｃ） 一般式（６）で表されるカルボン酸化合物（Ｌ）と、一般式（１）で表されるジアミノフェノール化合物（Ｍ）とが、反応モル比（Ｌ／２Ｍ）を、０．０１から０．５の範囲で反応させたことを特徴とする前記（ａ）又は（ｂ）項に記載の有機絶縁膜用材料。
【００２０】
（ｄ） ジアミノフェノール化合物のアミノ基と反応しているｄ価の有機基を有する化合物のモル数が、[[(Ｍ−Ｎ)ｘ２−Ｌ]／ｄ]モルであることを特徴とする前記（ａ）〜（ｃ）項のいずれかに記載の有機絶縁膜用材料。（但し、Ｍはジアミノフェノール化合物の反応モル数を、Ｎはジカルボン酸の反応モル数を、Ｌはカルボン酸の反応モル数を示す。）
【００２１】
（ｅ） 前記（ａ）〜（ｄ）項のいずれかに記載の有機絶縁膜用材料を用いて得られた有機絶縁膜であって、縮合反応及び架橋反応を経て調整された一般式（９）で表されるポリベンゾオキサゾール樹脂を主構造とする樹脂層からなることを特徴とする有機絶縁膜。
【００２２】
【発明の実施の形態】
本発明の有機絶縁膜材料は、一般式（１）の構造を有するジアミノフェノール化合物と、該化合物のアミノ基と反応しうるｄ価の有機基を有する化合物（ｄは３以上１０以下）、一般式（４）の構造を有するジカルボン酸化合物と、および一般式（６）の構造を有するアセチレン含有カルボン酸化合物とから、従来の酸クロリド法、活性エステル法、ポリリン酸やジシクロヘキシルカルボジイミド等の脱水縮合剤の存在下での縮合反応により得ることができる。
【００２３】
本発明の有機絶縁膜材料は、一般式（１）で表されるジアミノフェノール化合物（Ｍモル）と一般式（４）で表されるジカルボン酸（Ｎモル）との反応モル比（Ｎ／Ｍ）が、０．５から０．９９の範囲で合成される枝分かれ構造を有する重合体からなることが好ましい。モル比（Ｎ／Ｍ）が０．９９よりも大きいと、ジアミノフェノール化合物と該化合物のアミノ基と反応しうるｄ価の有機基を有する化合物（ｄは３以上１０以下）との反応物の樹脂中における含有率が低くなり、この場合、有機絶縁膜において、密度の低下および誘電率の低下が発現しなくなる恐れがある。モル比（Ｎ／Ｍ）が０．５よりも小さいと、得られる重合体の分子量が上がらず、未反応のジアミノフェノール化合物が残存し、有機絶縁膜の成膜において問題が生じる場合があるか、或いは脆い有機絶縁膜になってしまう恐れがある。
【００２４】
本発明に用いる一般式（１）で表されるジアミノフェノール化合物のアミノ基と反応しうるｄ価の有機基を有する化合物のモル数は、一般式（１）で表されるジアミノフェノール化合物（Ｍモル）と一般式（４）で表されるジカルボン酸（Ｎモル）の反応モル比（Ｎ／Ｍ）と一般式（６）であらわされるカルボン酸（Ｌモル）に対して、[[(Ｍ−Ｎ)ｘ２−Ｌ]／ｄ] モルであることが好ましい。ｄ価の有機基を有する化合物のモル数が [[(Ｍ−Ｎ)ｘ２−Ｌ]／ｄ] モルよりも少ないと、アミノ基と反応するｄ価の有機基を有する化合物の導入量が少なくなり、この場合、得られる化合物において、未反応のアミノ基が残存することにより誘電率の低下が発現しなくなる恐れがある。ｄ価の有機基を有する化合物のモル数が [[(Ｍ−Ｎ)ｘ２−Ｌ]／ｄ] よりも多いと、前駆体の架橋反応が進行することがあり、その際、溶剤不溶となり、均一なワニスが得られず絶縁膜形成において影響を及ぼす恐れがある。
【００２５】
本発明に用いる一般式（６）で表されるカルボン酸（Ｌモル）は、一般式（１）で表されるジアミノフェノール化合物（Ｍモル）に対して、反応モル比（Ｌ／２Ｍ）の値が０．０１から０．５の範囲であることが好ましい。（Ｌ／２Ｍ）の値が０．０１よりも少ないと、アセチレン基の架橋反応が十分進行しないため高耐熱化の効果が得られなくなる恐れがある。また、（Ｌ／２Ｍ）の値が０．５よりも大きい場合には、得られる重合体の分子量が上がらず、未反応のジアミノフェノール化合物が残存し、有機絶縁膜の成膜において問題が生じるか、或いは脆い有機絶縁膜になる恐れがある。
【００２６】
本発明に用いる一般式（１）で表されるジアミノフェノール化合物としては、例えば２,４−ジアミノレゾルシノール、４,６−ジアミノレゾルシノール、２,２−ビス（３−アミノ−４−ヒドロキシフェニル）ヘキサフルオロプロパン、２,２−ビス（４−アミノ−３−ヒドロキシフェニル）ヘキサフルオロプロパン、２,２−ビス（３−アミノ−４−ヒドロキシフェニル）プロパン、２,２−ビス（４−アミノ−３−ヒドロキシフェニル）プロパン、３,３'−ジアミノ−４,４'−ジヒドロキシビフェニルスルフォン、４,４'−ジアミノ−３,３'−ジヒドロキシビフェニルスルフォン、３,３'−ジアミノ−４,４'−ジヒドロキシビフェニル、４,４'−ジアミノ−３,３'−ジヒドロキシビフェニル、９,９−ビス−｛４−（（４−アミノ−３−ヒドロキシ）−フェノキシ）−フェニル｝−フルオレン、９,９−ビス−｛４−（（３−アミノ−４−ヒドロキシ）−フェノキシ）−フェニル｝−フルオレン、３,３'−ジアミノ−４,４'−ジヒドロキシジフェニルエーテル、４,４'−ジアミノ−３,３'−ジヒドロキシジフェニルエーテル、２,２−ビス（３−アミノ−４−ヒドロキシ−２−トリフルオロメチル）プロパン、２,２−ビス（４−アミノ−３−ヒドロキシ−２−トリフルオロメチル）プロパン、２,２−ビス（３−アミノ−４−ヒドロキシ−５−トリフルオロメチル）プロパン、２,２−ビス（４−アミノ−３−ヒドロキシ−５−トリフルオロメチル）プロパン、２,２−ビス（３−アミノ−４−ヒドロキシ−６−トリフルオロメチル）プロパン、２,２−ビス（４−アミノ−３−ヒドロキシ−６−トリフルオロメチル）プロパン、２,２−ビス（３−アミノ−４−ヒドロキシ−２−トリフルオロメチル）ヘキサフルオロプロパン、２,２−ビス（４−アミノ−３−ヒドロキシ−２−トリフルオロメチル）ヘキサフルオロプロパン、２,２−ビス（３−アミノ−４−ヒドロキシ−５−トリフルオロメチル）ヘキサフルオロプロパン、２,２−ビス（４−アミノ−３−ヒドロキシ−５−トリフルオロメチル）ヘキサフルオロプロパン、２,２−ビス（３−アミノ−４−ヒドロキシ−６−トリフルオロメチル）ヘキサフルオロプロパン、２,２−ビス（４−アミノ−３−ヒドロキシ−６−トリフルオロメチル）ヘキサフルオロプロパン、３,３'−ジアミノ−４,４'−ジヒドロキシ−２,２'−トリフルオロメチルビフェニル、４,４'−ジアミノ−３,３'−ジヒドロキシ−２,２'−トリフルオロメチルビフェニル、３,３'−ジアミノ−４,４'−ジヒドロキシ−５,５'−トリフルオロメチルビフェニル、４,４'−ジアミノ−３,３'−ジヒドロキシ−５,５'−トリフルオロメチルビフェニル、３,３'−ジアミノ−４,４'−ジヒドロキシ−６,６'−トリフルオロメチルビフェニル、４,４'−ジアミノ−３,３'−ジヒドロキシ−６,６'−トリフルオロメチルビフェニルなどを挙げることができるが、必ずしもこれらに限られるものではない。また、これら２種以上のジアミノフェノール化合物を組み合わせて使用することも可能である。
【００２７】
本発明に用いる一般式（４）で表されるジカルボン酸としては、例えば、イソフタル酸、テレフタル酸、４,４'−ビフェニルジカルボン酸、１,４−ナフタレンジカルボン酸、２,６−ナフタレンジカルボン酸、４,４'−スルホニルベンゼンジカルボン酸、ビフェニルエーテル−４,４'−ジカルボン酸、４,４'−イソプロピリデンビフェニルジカルボン酸、４,４'−ヘキサフルオロイソプロピリデンビフェニルジカルボン酸、４,４'−ビス｛２,２'−ビス（トリフルオロメチル）フェニル｝ジカルボン酸、３−フルオロイソフタル酸、２−フルオロイソフタル酸、２−フルオロテレフタル酸、２,４,５,６−テトラフルオロイソフタル酸、２,３,５,６−テトラフルオロテレフタル酸、５−トリフルオロメチルイソフタル酸などが挙げられるが、必ずしもこれらに限られるものではない。また、これら２種以上のジカルボン酸を組み合わせて使用することも可能である。
【００２８】
本発明で用いる一般式（１）で表されるジアミノフェノール化合物のアミノ基と反応しうるｄ価の有機基を有する化合物（ｄは３以上１０以下）は、一般的な方法でクロリド化した化合物または活性エステル化した化合物を用いるのが好ましいが、一般式（１）で表されるジアミノフェノール化合物のアミノ基に反応するものであれば良い。例えば、該化合物が、トリメシン酸、トリメリック酸、１，３，５−シクロヘキサントリカルボン酸、５，５’−ビスイソフタル酸、３，３’，４，４’−ビフェニルテトラカルボン酸無水物、ビフェニルエーテル−３，３’，５，５’−テトラカルボン酸、ビフェニルエーテル−３，３’，４，４’−テトラカルボン酸無水物、３，３’，４，４’−（１，１’−ヘキサフルオロイソプロピリデンビフェニル）テトラカルボン酸無水物、１，２，３，４，５，６−ベンゼンヘキサカルボン酸などの酸クロリド化合物や活性エステル化合物等が挙げられる。中でも、トリメシン酸、トリメリック酸、１，３，５−シクロヘキサントリカルボン酸、５，５’−ビスイソフタル酸が、好ましい。これらは、２種以上同時に使用してもかまわない。
【００２９】
本発明で用いる一般式（６）で表されるカルボン酸化合物は、アセチレン含有カルボン酸であり、例えば２−エチニル安息香酸、３−エチニル安息香酸、４−エチニル安息香酸、１,３−ジエチニル安息香酸、２,４−ジエチニル安息香酸、１,３,５−トリエチニル安息香酸、２−エチニル−１−ナフトエ酸、３−エチニル−１−ナフトエ酸、４−エチニル−１−ナフトエ酸、５−エチニル−１−ナフトエ酸、６−エチニル−１−ナフトエ酸、７−エチニル−１−ナフトエ酸、８−エチニル−１−ナフトエ酸、２−エチニル−２−ナフトエ酸、３−エチニル−２−ナフトエ酸、４−エチニル−２−ナフトエ酸、５−エチニル−２−ナフトエ酸、６−エチニル−２−ナフトエ酸、７−エチニル−２−ナフトエ酸、８−エチニル−２−ナフトエ酸、３,５−ジエチニル−１−ナフトエ酸、３,６−ジエチニル−１−ナフトエ酸、３,７−ジエチニル−１−ナフトエ酸、３,８−ジエチニル−１−ナフトエ酸、４,５−ジエチニル−１−ナフトエ酸、４,６−ジエチニル−１−ナフトエ酸、４,７−ジエチニル−１−ナフトエ酸、４,８−ジエチニル−１−ナフトエ酸、３,５−ジエチニル−２−ナフトエ酸、３,６−ジエチニル−２−ナフトエ酸、３,７−ジエチニル−２−ナフトエ酸、３,８−ジエチニル−２−ナフトエ酸、４,５−ジエチニル−２−ナフトエ酸、４,６−ジエチニル−２−ナフトエ酸、４,７−ジエチニル−２−ナフトエ酸、４,８−ジエチニル−２−ナフトエ酸、３,５,６−トリエチニル−１−ナフトエ酸、３,５,７−トリエチニル−１−ナフトエ酸、３,５,８−トリエチニル−１−ナフトエ酸、３,６,７−トリエチニル−１−ナフトエ酸、４,５,７−トリエチニル−２−ナフトエ酸、４,５,８−トリエチニル−２−ナフトエ酸、４,６,８−トリエチニル−２−ナフトエ酸、２−エチニルシクロペンタンカルボン酸、３−エチニルシクロペンタンカルボン酸、２−エチニルシクロヘキサンカルボン酸、３−エチニルシクロヘキサンカルボン酸、４−シクロヘキシニルカルボン酸、２,４−ジエチニルシクロヘキサンカルボン酸、３,５−ジエチニルシクロヘキサンカルボン酸等が挙げられるが、これらに限定されるものではない。また、これら２種類以上のアセチレン含有カルボン酸を組み合わせて使用することも可能である。
【００３０】
本発明の有機絶縁膜材料の製造は、一般式（１）で表されるジアミノフェノール化合物とｄ価（ｄは３以上１０以下）の有機基を有する化合物との反応により得られた化合物と、一般式（４）で表されるジカルボン酸、一般式（６）で表されるカルボン酸との反応により行われるが、前記ジアミノフェノール化合物と、一般式（４）で表されるジカルボン酸とを、活性エステル法により反応させて、有機絶縁膜材料を合成する場合は、ｄ価（ｄは３価以上１０以下）の有機基を有する化合物の活性エステル化合物およびカルボン酸の活性エステル化合物と、酸クロリド法により前駆体を合成する場合は、ｄ価（ｄは３価以上１０以下）の有機基を有する化合物の活性エステル化合物およびカルボン酸の酸クロリド化合物と、該アミノフェノール化合物のアミノ基とを反応させることで、枝分かれ構造を有する重合体からなる絶縁膜用樹脂を得ることができる。
【００３１】
本発明の有機絶縁膜材料の製造方法の中で、例えば、酸クロリド法では、使用する酸クロリドは、まず、Ｎ,Ｎ−ジメチルホルムアミド等の触媒存在下で、一般式（４）で表されるジカルボン酸、例えば、４,４'−ヘキサフルオロイソプロピリデンビフェニルジカルボン酸と過剰量の塩化チオニルとを、室温ないし７５℃で反応させ、過剰の塩化チオニルを加熱及び減圧により留去した後、残渣をヘキサン等の溶媒で再結晶することにより、４,４'−ヘキサフルオロイソプロピリデンビフェニルジカルボン酸クロリドを得ることができる。また、トリメシン酸等の一般式（１）で表されるジアミノフェノール化合物のアミノ基と反応しうるｄ価の有機基を有する化合物や、４−エチニル安息香酸等の一般式（６）で表されるカルボン酸についても、同様にして、それぞれトリメシン酸クロリド、４−エチニル安息香酸クロリド等のクロリド化合物として得ることができる。このようにして製造した酸クロリドの内、まず、一般式（１）で表されるジアミノフェノール化合物のアミノ基と反応しうるｄ価の有機基を有する化合物のクロリド化合物を、ビスアミノフェノール化合物と共に、通常Ｎ−メチル−２−ピロリドン、Ｎ,Ｎ−ジメチルアセトアミド等の極性溶媒に溶解し、ピリジン等の酸受容剤存在下で室温ないし−３０℃で反応させ、次いで、一般式（４）で表されるジカルボン酸のクロリド化合物を反応させ、更に、一般式（６）で表されるカルボン酸のクロリド化合物を加えて反応させることにより、一般式（８）で表されるポリベンゾオキサゾール前駆体を主構造とする重合体からなる有機絶縁膜材料を得ることができる。
【００３２】
また、ジアミノフェノール化合物と、前記酸クロリド化合物の代わりに、ｄ価の有機基を有する化合物（ｄは３以上１０以下）の活性エステル化合物を反応させ、続けて一般式（４）で表されるジカルボン酸化合物と一般式（６）で表されるカルボン酸の活性エステル化合物と反応させることによっても、有機絶縁膜材料を得ることができる。
【００３３】
本発明の有機絶縁膜材料は、通常、これを溶剤に溶解し、ワニス状にして使用するのが好ましい。溶剤としては、 Ｎ−メチル−２−ピロリドン、γ−ブチロラクトン、Ｎ,Ｎ−ジメチルアセトアミド、ジメチルスルホキシド、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールジブチルエーテル、プロピレングリコールモノメチルエーテル、ジプロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、乳酸メチル、乳酸エチル、乳酸ブチル、メチル−１,３−ブチレングリコールアセテート、１,３−ブチレングリコール−３−モノメチルエーテル、ピルビン酸メチル、ピルビン酸エチル、メチル−３−メトキシプロピオネート等を１種、または２種以上混合して用いることが出来る。
【００３４】
本発明の有機絶縁膜材料には、必要により、各種添加剤として、界面活性剤やカップリング剤等を添加し、半導体用層間絶縁膜、保護膜、多層回路の層間絶縁膜、フレキシブル銅張板のカバーコート、ソルダーレジスト膜、液晶配向膜等として用いることができる。
【００３５】
本発明の有機絶縁膜の製造方法としては、まず、本発明の有機絶縁膜材料を、上記溶剤に溶解してワニスとして、適当な支持体、例えば、ガラス、金属、シリコーンウエハーやセラミック基盤等に塗布する。塗布方法としては、スピンナーを用いた回転塗布、スプレーコーターを用いた噴霧塗布、浸漬、印刷、ロールコーティング等が挙げられる。このようにして、塗膜を形成した後、加熱処理をして、縮合反応させてポリベンゾオキサゾール樹脂に変換すると共に、架橋反応させて、一般式（９）で表される構造を主構造とする樹脂層からなる有機絶縁膜を得るのが好ましい。
【００３６】
本発明の有機絶縁膜材料は、感光剤としてのナフトキノンジアジド化合物と一緒に用いることで、感光性樹脂組成物として用いることが可能である。
【００３７】
【実施例】
以下に実施例により本発明を具体的に説明するが、本発明は、実施例の内容になんら限定されるものではない。実施例及び比較例で作成したフィルムを用いて、特性評価のため、誘電率、耐熱性、および密度を測定した。各特性の測定条件は次のとおりとし、その測定結果は表１にまとめて示した。以下、部は重量部を示す。
【００３８】
誘電率：測定周波数１ＭＨｚでヒューレットパッカード社製ＨＰ−４２８４Ａ Ｐｒｅｃｉｓｉｏｎ ＬＣＲメーターを用いて測定を行った。
耐熱性：セイコーインスツルメンツ（株）製ＴＧ／ＤＴＡ２２０を用いて、窒素ガスフロー下、昇温速度１０℃／分の条件により、重量減少５％の時の温度を測定した。
密度：水―よう化ナトリウムによる勾配液を２３℃で１．３８から１．４８の間で調整し、(株)柴山科学機械製作所製密度勾配式比重測定装置Ｂ型を用いて測定を行った。
【００３９】
「実施例１」
２，２−ビス （３− アミノ−４−ヒドロキシフェニル）ヘキサフルオロプロパン３．６６部（１０ｍｍｏｌ）を、乾燥窒素雰囲気下で、乾燥した１０部のＮ−メチル−２−ピロリドンに溶解し、５℃で、１０部のγ−ブチロラクトンに、トリメシン酸トリクロリド０．０８０部（０．３０ｍｍｏｌ）を溶解したものを、３０分かけて滴下した。続いて、室温まで戻し、室温で１時間攪拌した。その後、５℃で、４０部のγ−ブチロラクトンに、４,４'−ヘキサフルオロイソプロピリデンビフェニルジカルボン酸ジクロリド４．０８部（９．５０ｍｍｏｌ）を溶解したものを、３０分かけて滴下し、続いて４−エチニル安息香酸クロリド０．０１６部（０．１ｍｍｏｌ）をγ−ブチロラクトン５ｍＬに溶解したものを滴下し、1時間攪拌した。続いて、室温まで戻し、室温で１時間攪拌した。その後、５℃で、１０部のγ−ブチロラクトンに、ピリジン１．５８部を溶解したものを、３０分かけて滴下した。滴下終了後、室温まで戻し、室温で３時間攪拌して反応させることにより、ポリベンゾオキサゾール前駆体（有機絶縁膜材料）を得た。得られたポリベンゾオキサゾール前駆体を東ソー株式会社製ＧＰＣを用いてポリスチレン換算で数平均分子量（Ｍｎ）を求めたところ、７．０ｘ１０³、重量平均分子量（Ｍｗ）が１．３６ｘ１０⁵であった。
【００４０】
このポリベンゾオキサゾール前駆体１０ｇを、Ｎ−メチル−２−ピロリドンに溶解して２０％の溶液とし、孔径０．２μｍのテフロン（Ｒ）フィルターで濾過し、ワニスを得た。このワニスを、スピンコーターを用いてシリコンウエハー上に塗布した。塗布後、１００℃のホットプレート上で、２４０秒乾燥した後、窒素を流入して、酸素濃度を１００ｐｐｍ以下に制御したオーブンを用いて、１５０℃／３０分、２５０℃／３０分、３５０℃／３０分の順で加熱し、絶縁膜用樹脂フィルムを得た。得られたフィルムを用いて、各種特性の評価を行った。
【００４１】
「実施例２」
実施例１において、４−エチニル安息香酸クロリド０．０１６部（０．１ｍｍｏｌ）を６−エチニル−２−ナフトエ酸クロリド０．０２１部（０．１ｍｍｏｌ）とする以外は、全て実施例１と同様にして、ポリベンゾオキサゾール前駆体（有機絶縁膜材料）の合成を行った。ＧＰＣにより分子量を測定したところ、ポリスチレン換算でＭｎが７．０ｘ１０³、Ｍｗが１．３７ｘ１０⁵であった。その後、実施例１と同様にして、ワニスを得た。ここで得たワニスを用いて、実施例１と同様にして、絶縁膜用樹脂フィルムを作製し、評価を行った。
【００４２】
「実施例３」
実施例１において、トリメシン酸トリクロリド０．０８０部（０．３０ｍｍｏｌ）を０．１５９部（０．６０ｍｍｏｌ）とし、４,４'−ヘキサフルオロイソプロピリデンビフェニルジカルボン酸ジクロリド４．０８部（９．５０ｍｍｏｌ）を３．８６部（９．００ｍｍｏｌ）とし、４−エチニル安息香酸クロリド０．０１６部（０．１０ｍｍｏｌ）を０．０３３部（０．２０ｍｍｏｌ）とする以外は、全て実施例１と同様にして、ポリベンゾオキサゾール前駆体（有機絶縁膜材料）の合成を行った。ＧＰＣにより分子量を測定したところ、ポリスチレン換算でＭｎが６．７ｘ１０³、Ｍｗが９．８ｘ１０⁴であった。その後、実施例１と同様にして、ワニスを得た。ここで得たワニスを用いて、実施例１と同様にして、絶縁膜用樹脂フィルムを作製し、評価を行った
【００４３】
「実施例４」
実施例１において、トリメシン酸トリクロリド０．０８０部（０．３０ｍｍｏｌ）を０．１５９部とし、４,４'−ヘキサフルオロイソプロピリデンビフェニルジカルボン酸ジクロリド４．０８部（９．５０ｍｍｏｌ）を３．８６部（９．００ｍｍｏｌ）とし、４−エチニル安息香酸クロリド０．０１６部（０．１０ｍｍｏｌ）を３−エチニル安息香酸クロリド０．０３３部（０．２０ｍｍｏｌ）とする以外は、全て実施例１と同様にして、ポリベンゾオキサゾール前駆体（有機絶縁膜材料）の合成を行った。ＧＰＣにより分子量を測定したところ、ポリスチレン換算でＭｎが６．７ｘ１０³、Ｍｗが９．５ｘ１０⁴であった。その後、実施例１と同様にして、ワニスを得た。ここで得たワニスを用いて、実施例１と同様にして、絶縁膜用樹脂フィルムを作製し、評価を行った。
【００４４】
「比較例１」
撹拌装置、窒素導入管、滴下漏斗を付けたセパラブルフラスコ中、２，２−ビス（３−アミノ−４−ヒドロキシフェニル）ヘキサフルオロプロパン１４．６５部（４０ｍｍｏｌ）を、乾燥したジメチルアセトアミド２００部に溶解し、ピリジン７．９２部（２００ｍｍｏｌ）を添加後、乾燥窒素導入下、−１５℃で、ジメチルアセトアミド１００ｇに、４,４'−ヘキサフルオロイソプロピリデンビフェニルジカルボン酸ジクロリド１６．９２ｇ（４０ｍｍｏｌ）を溶解したものを、３０分かけて滴下し、沈殿物を回収し、乾燥して、ポリベンゾオキサゾール前駆体（有機絶縁膜材料）の粉末を得た。ＧＰＣにより、前記絶縁膜材料の分子量を測定したところ、スチレン換算でＭｎが３．８ｘ１０⁴、Ｍｗが８．０３ｘ１０⁴であった。その後、実施例１と同様にして、ワニスを得た。ここで得たワニスを用いて、実施例１と同様にして、絶縁膜用樹脂フィルムを作製し、評価を行った。
【００４５】
「比較例２」
２，２−ビス （３− アミノ−４−ヒドロキシフェニル）ヘキサフルオロプロパン３．６６部（１０．００ｍｍｏｌ）を、乾燥窒素雰囲気下で、乾燥した１０部のＮ−メチル−２−ピロリドンに溶解し、５℃で、４０部のγ−ブチロラクトンに、４,４'−ヘキサフルオロイソプロピリデンビフェニルジカルボン酸ジクロリド４．０８部（９．５０ｍｍｏｌ）を溶解したものを、３０分かけて滴下した。続いて、室温まで戻し、室温で１時間攪拌した。その後、５℃で、１０部のγ−ブチロラクトンに、ピリジン１．５８部を溶解したものを、３０分かけて滴下した。滴下終了後、室温まで戻し、室温で３時間攪拌して、ポリベンゾオキサゾール前駆体を得た。その後、５℃で、１０部のγ−ブチロラクトンに、トリメシン酸トリクロリド０．０８０部（０．３０ｍｍｏｌ）を溶解したものを、滴下して反応したところ、分子量が急激に増大し、反応溶液はゲル化した。
【００４６】
「比較例３」
実施例１のポリベンゾオキサゾール前駆体の合成において、４−エチニル安息香酸クロリド０．０１６部（０．１ｍｍｏｌ）を添加しない以外は、全て実施例１と同様にして、ポリベンゾオキサゾール前駆体（有機絶縁膜材料）の合成を行った。ＧＰＣにより分子量を測定したところ、ポリスチレン換算でＭｎが７．０ｘ１０³、Ｍｗが１．３５ｘ１０⁵であった。その後、実施例１と同様にして、ワニスを得た。ここで得たワニスを用いて、実施例１と同様にして、絶縁膜用樹脂フィルムを作製し、評価を行った。
【００４７】
「比較例４」
実施例１のポリベンゾオキサゾール前駆体の合成において、トリメシン酸クロリド０．０８０部（０．０３０ｍｍｏｌ）を添加しない以外は、全て実施例１と同様にして、ポリベンゾオキサゾール前駆体（有機絶縁膜材料）の合成を行った。ＧＰＣにより分子量を測定したところ、ポリスチレン換算でＭｎが９．８ｘ１０³、Ｍｗが１．３ｘ１０⁵であった。その後、実施例１と同様にして、ワニスを得た。ここで得たワニスを用いて、実施例１と同様にして、絶縁膜用樹脂フィルムを作製し、評価を行った。
【００４８】
【表１】

尚、密度低下率は、それぞれ得られたフィルムの密度から、ｄ価の有機基を有する化合物と一般式（６）で表されるカルボン酸化合物とを用いずに合成した比較例１のポリベンゾオキサゾール樹脂からなるフィルムの密度を基準として、算出した。
【００４９】
表１にまとめられた結果から明らかなように、本発明のポリベンゾオキサゾール前駆体を用いて作製した、実施例のポリベンゾオキサゾール樹脂は、いずれも誘電率が２．４３〜２．５と低く、さらに耐熱性が高いという良好な特性を示した。これに対して、比較例では、枝分かれ構造を有したポリベンゾオキサゾール樹脂ではあるものの、比較例１、３においては、アセチレンによる架橋がないため、実施例に比べて高い耐熱性が得られなかった。また、比較例１、４においては、枝分かれ構造を有していないため、実施例に比べて誘電率が高く２．６を下回る値は得られなかった。
【００５０】
【発明の効果】
本発明により、電気特性、熱特性、機械特性及び物理特性に優れた有機絶縁膜用材料及び有機絶縁膜を得ることができる。従って、本発明の有機絶縁膜用材料は、電気特性、熱特性、機械特性及び物理特性が要求される様々な分野、例えば半導体用の層間絶縁膜、保護膜、多層回路の層間絶縁膜、フレキシブル銅張板のカバーコート、ソルダーレジスト膜、液晶配向膜などとして適用できる。[0001]
BACKGROUND OF THE INVENTION
The present invention is excellent in electrical characteristics, thermal characteristics, mechanical characteristics and physical characteristics, and is used for semiconductor interlayer insulation films, protective films, multilayer circuit interlayer insulation films, flexible copper-clad cover coats, solder resist films, and liquid crystal alignment films. The present invention relates to an organic insulating film material and an organic insulating film suitable for applications such as
[0002]
[Prior art]
At present, an inorganic material such as an oxide film (silicon dioxide or the like) produced by a CVD method (chemical vapor deposition method) or the like is mainly used as an interlayer insulating film for a semiconductor. However, an inorganic insulating film such as an oxide film has a high dielectric constant, and application of an organic material is being studied as one candidate for a low dielectric constant insulating film in order to increase the speed and performance of a semiconductor. As organic materials for semiconductor applications, heat-resistant resins excellent in electrical characteristics, mechanical characteristics, physical characteristics, and the like have been proposed.
[0003]
As an organic material for semiconductor use, a polyimide resin excellent in heat resistance, electrical characteristics, mechanical characteristics and the like is used. In recent years, with higher speed, higher functionality, and higher performance of semiconductors, there is a further demand for improvement in heat resistance, electrical properties, hygroscopicity, thermal expansion coefficient, etc., and higher performance resins are required. It is like that.
[0004]
For these reasons, attempts have been made to apply polybenzoxazole resins, which exhibit superior performance in terms of electrical characteristics and water absorption resistance, to insulating materials for semiconductor applications as compared to polyimide resins. The polybenzoxazole resin is easy to satisfy only one of electrical characteristics, thermal characteristics, and physical characteristics, and is composed of, for example, 4,4′-diamino-3,3′-dihydroxybiphenyl and terephthalic acid. There are polybenzoxazole resins, polybenzoxazole resins composed of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and terephthalic acid, and the like. However, demands for further lowering the dielectric constant in recent years are severe, and it has become difficult to satisfy the dielectric constant required for high-density films such as organic resins. For this reason, a method of greatly reducing the dielectric constant as an insulating film by opening a hole in an inorganic film such as an oxide film has been performed, but a method that meets the requirements has not been obtained.
[0005]
[Problems to be solved by the invention]
An object of the present invention is to provide a heat-resistant organic insulating film material and an organic insulating film which are excellent in all of electric characteristics, thermal characteristics and physical characteristics in semiconductor applications, and particularly have a very low dielectric constant.
[0006]
[Means for Solving the Problems]
As a result of intensive studies in view of the above-mentioned conventional problems, the present inventors have found a diaminophenol compound represented by the general formula (1) and a d-valent organic group capable of reacting with the amino group of the compound. A compound having a branched structure by reacting a compound having a compound (d is 3 or more and 10 or less) with a dicarboxylic acid compound represented by the general formula (4), and further acetylene represented by the general formula (6) A material for an organic insulating film composed of a polymer having a structure represented by the general formula (8) synthesized by reacting the contained carboxylic acid as a main structure, and a general formula (9) using the material. The organic insulating film characterized by comprising a polybenzoxazole resin layer having a main structure as a main structure has high heat resistance, and it is possible to obtain high dielectric constant characteristics by reducing the density. Discovered and led to the completion of the present invention
[0007]
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In formula (1), X represents a structure selected from formula (2).
[0008]
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In formula (2), X ₁ Represents a structure selected from Formula (3), and the hydrogen atom on the benzene ring in these structures is a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, or a fluorine atom. , And may be substituted with at least one group selected from the group consisting of trifluoromethyl groups.
[0009]
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[0010]
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In formula (4), Y represents a structure selected from formula (5).
[0011]
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In formula (5), X ₁ Represents a structure selected from the formula (3).
[0012]
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In formula (6), Z represents a structure selected from formula (7).
[0013]
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[0014]
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However, n in General formula (8) shows the integer of 2-1000. X represents a structure selected from (2), and Y represents a structure selected from Formula (5).
[0015]
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However, n in general formula (9) shows the integer of 2-1000. X represents a structure selected from (2), and Y represents a structure selected from Formula (5).
[0016]
That is, the present invention is as described in the items (a) to (e).
[0017]
(A) The diaminophenol compound represented by the general formula (1) is reacted with a compound having a d-valent organic group that can react with the amino group of the compound (d is 3 or more and 10 or less). Polybenzoxazole represented by the general formula (8) obtained by reacting with the dicarboxylic acid compound represented by the formula (4) and then reacting with the carboxylic acid compound represented by the general formula (6) An organic insulating film material comprising a polymer having a resin precursor as a main structure.
[0018]
(B) The diaminophenol compound (M) represented by the general formula (1) and the dicarboxylic acid compound (N) represented by the general formula (4) have a reaction molar ratio (N / M) of 0. The organic insulating film material according to item (a), wherein the reaction is performed in the range of 5 to 0.99.
[0019]
(C) The carboxylic acid compound (L) represented by the general formula (6) and the diaminophenol compound (M) represented by the general formula (1) have a reaction molar ratio (L / 2M) of 0. The organic insulating film material according to item (a) or (b), wherein the reaction is performed in a range of 01 to 0.5.
[0020]
(D) The number of moles of the compound having a d-valent organic group reacting with the amino group of the diaminophenol compound is [[(MN) × 2-L] / d] mole. The material for organic insulating films according to any one of (a) to (c). (However, M represents the reaction mole number of the diaminophenol compound, N represents the reaction mole number of the dicarboxylic acid, and L represents the reaction mole number of the carboxylic acid.)
[0021]
(E) An organic insulating film obtained by using the organic insulating film material according to any one of (a) to (d), wherein the general formula (9) adjusted through a condensation reaction and a crosslinking reaction An organic insulating film comprising a resin layer having a main structure of a polybenzoxazole resin represented by
[0022]
DETAILED DESCRIPTION OF THE INVENTION
The organic insulating film material of the present invention includes a diaminophenol compound having the structure of the general formula (1), a compound having a d-valent organic group that can react with the amino group of the compound (d is 3 or more and 10 or less), From the dicarboxylic acid compound having the structure of the formula (4) and the acetylene-containing carboxylic acid compound having the structure of the general formula (6), the conventional acid chloride method, active ester method, polyphosphoric acid, dicyclohexylcarbodiimide and the like dehydration condensation It can be obtained by a condensation reaction in the presence of an agent.
[0023]
The organic insulating film material of the present invention is a reaction molar ratio (N / M) of a diaminophenol compound (M mol) represented by the general formula (1) and a dicarboxylic acid (N mol) represented by the general formula (4). ) Is preferably made of a polymer having a branched structure synthesized in the range of 0.5 to 0.99. When the molar ratio (N / M) is greater than 0.99, the reaction product of a diaminophenol compound and a compound having a d-valent organic group capable of reacting with the amino group of the compound (d is 3 or more and 10 or less) The content in the resin is lowered, and in this case, there is a risk that the organic insulating film will not exhibit a decrease in density and a decrease in dielectric constant. If the molar ratio (N / M) is less than 0.5, the molecular weight of the resulting polymer will not increase, and unreacted diaminophenol compounds may remain, causing problems in the formation of the organic insulating film. Or, there is a risk of becoming a brittle organic insulating film.
[0024]
The number of moles of the compound having a d-valent organic group that can react with the amino group of the diaminophenol compound represented by the general formula (1) used in the present invention is the diaminophenol compound (M) represented by the general formula (1). Mol) and the reaction molar ratio (N / M) of the dicarboxylic acid (N mole) represented by the general formula (4) and the carboxylic acid (L mole) represented by the general formula (6) [[(M -N) x2-L] / d] mol. When the number of moles of the compound having a d-valent organic group is less than [[(MN) x2-L] / d] mole, the amount of the compound having a d-valent organic group that reacts with an amino group is reduced. Thus, in this case, in the obtained compound, there is a possibility that the decrease in the dielectric constant may not occur due to the remaining unreacted amino group. When the number of moles of the compound having a d-valent organic group is larger than [[(MN) x2-L] / d], the precursor may undergo a crosslinking reaction, and in that case, the solvent becomes insoluble, A uniform varnish cannot be obtained, which may affect the formation of the insulating film.
[0025]
The carboxylic acid (L mol) represented by the general formula (6) used in the present invention has a reaction molar ratio (L / 2M) with respect to the diaminophenol compound (M mol) represented by the general formula (1). The value is preferably in the range of 0.01 to 0.5. If the value of (L / 2M) is less than 0.01, the crosslinking reaction of the acetylene group does not proceed sufficiently, so that the effect of increasing the heat resistance may not be obtained. When the value of (L / 2M) is larger than 0.5, the molecular weight of the obtained polymer does not increase, and unreacted diaminophenol compound remains, which causes a problem in forming an organic insulating film. Or, there is a risk of becoming a fragile organic insulating film.
[0026]
Examples of the diaminophenol compound represented by the general formula (1) used in the present invention include 2,4-diaminoresorcinol, 4,6-diaminoresorcinol, and 2,2-bis (3-amino-4-hydroxyphenyl) hexa. Fluoropropane, 2,2-bis (4-amino-3-hydroxyphenyl) hexafluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 2,2-bis (4-amino-3) -Hydroxyphenyl) propane, 3,3'-diamino-4,4'-dihydroxybiphenylsulfone, 4,4'-diamino-3,3'-dihydroxybiphenylsulfone, 3,3'-diamino-4,4'- Dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, 9,9-bis- {4-((4-amino-3-hydroxy) Phenoxy) -phenyl} -fluorene, 9,9-bis- {4-((3-amino-4-hydroxy) -phenoxy) -phenyl} -fluorene, 3,3′-diamino-4,4′-dihydroxydiphenyl ether 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 2,2-bis (3-amino-4-hydroxy-2-trifluoromethyl) propane, 2,2-bis (4-amino-3- Hydroxy-2-trifluoromethyl) propane, 2,2-bis (3-amino-4-hydroxy-5-trifluoromethyl) propane, 2,2-bis (4-amino-3-hydroxy-5-trifluoro) Methyl) propane, 2,2-bis (3-amino-4-hydroxy-6-trifluoromethyl) propane, 2,2-bis (4-amino-3-hydroxy-6-trifluoro) Fluoromethyl) propane, 2,2-bis (3-amino-4-hydroxy-2-trifluoromethyl) hexafluoropropane, 2,2-bis (4-amino-3-hydroxy-2-trifluoromethyl) hexafluoro Propane, 2,2-bis (3-amino-4-hydroxy-5-trifluoromethyl) hexafluoropropane, 2,2-bis (4-amino-3-hydroxy-5-trifluoromethyl) hexafluoropropane, 2,2-bis (3-amino-4-hydroxy-6-trifluoromethyl) hexafluoropropane, 2,2-bis (4-amino-3-hydroxy-6-trifluoromethyl) hexafluoropropane, 3, 3'-diamino-4,4'-dihydroxy-2,2'-trifluoromethylbiphenyl, 4,4'-diamino-3,3'-dihydroxy Cis-2,2'-trifluoromethylbiphenyl, 3,3'-diamino-4,4'-dihydroxy-5,5'-trifluoromethylbiphenyl, 4,4'-diamino-3,3'-dihydroxy- 5,5′-trifluoromethylbiphenyl, 3,3′-diamino-4,4′-dihydroxy-6,6′-trifluoromethylbiphenyl, 4,4′-diamino-3,3′-dihydroxy-6, Although 6'- trifluoromethyl biphenyl etc. can be mentioned, it is not necessarily restricted to these. It is also possible to use a combination of these two or more diaminophenol compounds.
[0027]
Examples of the dicarboxylic acid represented by the general formula (4) used in the present invention include isophthalic acid, terephthalic acid, 4,4′-biphenyldicarboxylic acid, 1,4-naphthalenedicarboxylic acid, and 2,6-naphthalenedicarboxylic acid. 4,4′-sulfonylbenzenedicarboxylic acid, biphenyl ether-4,4′-dicarboxylic acid, 4,4′-isopropylidenebiphenyldicarboxylic acid, 4,4′-hexafluoroisopropylidenebiphenyldicarboxylic acid, 4,4 ′ -Bis {2,2'-bis (trifluoromethyl) phenyl} dicarboxylic acid, 3-fluoroisophthalic acid, 2-fluoroisophthalic acid, 2-fluoroterephthalic acid, 2,4,5,6-tetrafluoroisophthalic acid, 2,3,5,6-tetrafluoroterephthalic acid, 5-trifluoromethylisophthalic acid, etc. However, it is not limited to these. It is also possible to use a combination of these two or more dicarboxylic acids.
[0028]
The compound having a d-valent organic group that can react with the amino group of the diaminophenol compound represented by the general formula (1) used in the present invention (d is 3 or more and 10 or less) is a compound chlorided by a general method. Alternatively, an active esterified compound is preferably used, but any compound that reacts with the amino group of the diaminophenol compound represented by the general formula (1) may be used. For example, the compound may be trimesic acid, trimeric acid, 1,3,5-cyclohexanetricarboxylic acid, 5,5′-bisisophthalic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic anhydride, biphenyl ether −3,3 ′, 5,5′-tetracarboxylic acid, biphenyl ether-3,3 ′, 4,4′-tetracarboxylic anhydride, 3,3 ′, 4,4 ′-(1,1′- Hexafluoroisopropylidenebiphenyl) tetracarboxylic acid anhydride, acid chloride compounds such as 1,2,3,4,5,6-benzenehexacarboxylic acid, active ester compounds, and the like. Of these, trimesic acid, trimeric acid, 1,3,5-cyclohexanetricarboxylic acid, and 5,5′-bisisophthalic acid are preferable. Two or more of these may be used simultaneously.
[0029]
The carboxylic acid compound represented by the general formula (6) used in the present invention is an acetylene-containing carboxylic acid, for example, 2-ethynylbenzoic acid, 3-ethynylbenzoic acid, 4-ethynylbenzoic acid, 1,3-diethynylbenzoic acid. Acid, 2,4-diethynylbenzoic acid, 1,3,5-triethynylbenzoic acid, 2-ethynyl-1-naphthoic acid, 3-ethynyl-1-naphthoic acid, 4-ethynyl-1-naphthoic acid, 5-ethynyl -1-naphthoic acid, 6-ethynyl-1-naphthoic acid, 7-ethynyl-1-naphthoic acid, 8-ethynyl-1-naphthoic acid, 2-ethynyl-2-naphthoic acid, 3-ethynyl-2-naphthoic acid 4-ethynyl-2-naphthoic acid, 5-ethynyl-2-naphthoic acid, 6-ethynyl-2-naphthoic acid, 7-ethynyl-2-naphthoic acid, 8-ethynyl-2-naphthoic acid, 3 , 5-diethynyl-1-naphthoic acid, 3,6-diethynyl-1-naphthoic acid, 3,7-diethynyl-1-naphthoic acid, 3,8-diethynyl-1-naphthoic acid, 4,5-diethynyl-1 -Naphthoic acid, 4,6-diethynyl-1-naphthoic acid, 4,7-diethynyl-1-naphthoic acid, 4,8-diethynyl-1-naphthoic acid, 3,5-diethynyl-2-naphthoic acid, 3, 6-diethynyl-2-naphthoic acid, 3,7-diethynyl-2-naphthoic acid, 3,8-diethynyl-2-naphthoic acid, 4,5-diethynyl-2-naphthoic acid, 4,6-diethynyl-2- Naphthoic acid, 4,7-diethynyl-2-naphthoic acid, 4,8-diethynyl-2-naphthoic acid, 3,5,6-triethynyl-1-naphthoic acid, 3,5,7-triethynyl-1-naphthoic acid 3,5,8-triethynyl-1-naphtho Acid 3,6,7-triethynyl-1-naphthoic acid, 4,5,7-triethynyl-2-naphthoic acid, 4,5,8-triethynyl-2-naphthoic acid, 4,6,8-triethynyl-2 -Naphthoic acid, 2-ethynylcyclopentanecarboxylic acid, 3-ethynylcyclopentanecarboxylic acid, 2-ethynylcyclohexanecarboxylic acid, 3-ethynylcyclohexanecarboxylic acid, 4-cyclohexylinylcarboxylic acid, 2,4-diethynylcyclohexanecarboxylic acid Examples include 3,5-diethynylcyclohexanecarboxylic acid, but are not limited thereto. It is also possible to use a combination of these two or more acetylene-containing carboxylic acids.
[0030]
The production of the organic insulating film material of the present invention comprises a compound obtained by a reaction between a diaminophenol compound represented by the general formula (1) and a compound having an organic group of d valence (d is 3 or more and 10 or less), The dicarboxylic acid represented by the general formula (4) is reacted with the carboxylic acid represented by the general formula (6). The diaminophenol compound and the dicarboxylic acid represented by the general formula (4) In the case of synthesizing an organic insulating film material by reacting by an active ester method, an active ester compound of a compound having an organic group of d valence (d is from 3 to 10), an active ester compound of carboxylic acid, and an acid In the case of synthesizing a precursor by the chloride method, an active ester compound of a compound having an organic group of d valence (d is 3 or more and 10 or less), an acid chloride compound of a carboxylic acid, and the aminophenol An amino group of the compound is reacted, it is possible to obtain an insulating film for a resin composed of a polymer having a branched structure.
[0031]
In the method for producing an organic insulating film material of the present invention, for example, in the acid chloride method, the acid chloride to be used is first represented by the general formula (4) in the presence of a catalyst such as N, N-dimethylformamide. A dicarboxylic acid such as 4,4′-hexafluoroisopropylidenebiphenyldicarboxylic acid and an excess amount of thionyl chloride are reacted at room temperature to 75 ° C., and the excess thionyl chloride is distilled off by heating and reduced pressure. Can be recrystallized with a solvent such as hexane to obtain 4,4′-hexafluoroisopropylidenebiphenyldicarboxylic acid chloride. In addition, a compound having a d-valent organic group capable of reacting with the amino group of the diaminophenol compound represented by the general formula (1) such as trimesic acid, or a general formula (6) such as 4-ethynylbenzoic acid. Similarly, the carboxylic acids can be obtained as chloride compounds such as trimesic acid chloride and 4-ethynylbenzoic acid chloride. Among the acid chlorides thus produced, first, a chloride compound of a compound having a d-valent organic group capable of reacting with the amino group of the diaminophenol compound represented by the general formula (1) is combined with a bisaminophenol compound. In general, it is dissolved in a polar solvent such as N-methyl-2-pyrrolidone or N, N-dimethylacetamide and reacted at room temperature to −30 ° C. in the presence of an acid acceptor such as pyridine, The polybenzoxazole precursor represented by the general formula (8) is reacted by reacting the dicarboxylic acid chloride compound represented by the general formula (6) and further reacting the carboxylic acid chloride compound represented by the general formula (6). An organic insulating film material made of a polymer having a main structure can be obtained.
[0032]
Further, instead of the diaminophenol compound and the acid chloride compound, an active ester compound of a compound having a d-valent organic group (d is 3 or more and 10 or less) is reacted, and then represented by the general formula (4). The organic insulating film material can also be obtained by reacting the dicarboxylic acid compound with the active ester compound of the carboxylic acid represented by the general formula (6).
[0033]
The organic insulating film material of the present invention is usually preferably used by dissolving it in a solvent and varnishing it. Solvents include N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol Monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3-methoxypropio Nate or the like can be used alone or in combination of two or more.
[0034]
The organic insulating film material of the present invention is optionally added with various additives such as surfactants and coupling agents, and is used for semiconductor interlayer insulating films, protective films, interlayer insulating films for multilayer circuits, flexible copper-clad plates. Cover coat, solder resist film, liquid crystal alignment film, and the like.
[0035]
As a method for producing the organic insulating film of the present invention, first, the organic insulating film material of the present invention is dissolved in the above-mentioned solvent to form a varnish, for example, glass, metal, silicone wafer or ceramic substrate. Apply. Examples of the coating method include spin coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, and the like. Thus, after forming a coating film, it heat-processes, it is made to carry out condensation reaction, it converts into polybenzoxazole resin, and it is made to cross-link, and the structure represented by General formula (9) is made into a main structure. It is preferable to obtain an organic insulating film made of a resin layer.
[0036]
The organic insulating film material of the present invention can be used as a photosensitive resin composition by using it together with a naphthoquinone diazide compound as a photosensitive agent.
[0037]
【Example】
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the contents of the examples. Dielectric constant, heat resistance, and density were measured for property evaluation using the films prepared in Examples and Comparative Examples. The measurement conditions for each characteristic were as follows, and the measurement results are summarized in Table 1. Hereinafter, a part shows a weight part.
[0038]
Dielectric constant: Measured using a HP-4284A Precision LCR meter manufactured by Hewlett-Packard at a measurement frequency of 1 MHz.
Heat resistance: TG / DTA220 manufactured by Seiko Instruments Inc. was used to measure the temperature at a weight loss of 5% under a nitrogen gas flow under a temperature increase rate of 10 ° C./min.
Density: A gradient solution of water-sodium iodide was adjusted at 1.38 to 1.48 at 23 ° C., and measurement was performed using a density gradient type specific gravity measuring device B type manufactured by Shibayama Scientific Machinery Co., Ltd. .
[0039]
Example 1
2.66 parts (10 mmol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was dissolved in 10 parts of dried N-methyl-2-pyrrolidone under a dry nitrogen atmosphere, and 5 What melt | dissolved 0.080 part (0.30 mmol) of trimesic acid trichloride in 10 parts (gamma) -butyrolactone was dripped at 30 degreeC over 30 minutes. Then, it returned to room temperature and stirred at room temperature for 1 hour. Thereafter, at 5 ° C., 4.08 parts (9.50 mmol) of 4,4′-hexafluoroisopropylidenebiphenyldicarboxylic acid dichloride dissolved in 40 parts of γ-butyrolactone was added dropwise over 30 minutes, followed by A solution prepared by dissolving 0.016 part (0.1 mmol) of 4-ethynylbenzoic acid chloride in 5 mL of γ-butyrolactone was added dropwise and stirred for 1 hour. Then, it returned to room temperature and stirred at room temperature for 1 hour. Then, what melt | dissolved 1.58 parts of pyridines in 10 parts (gamma) -butyrolactone at 5 degreeC was dripped over 30 minutes. After completion of dropping, the mixture was returned to room temperature and reacted at room temperature for 3 hours to obtain a polybenzoxazole precursor (organic insulating film material). When the number average molecular weight (Mn) was calculated | required in polystyrene conversion using Tosoh Corporation GPC, the obtained polybenzoxazole precursor was 7.0x10. ^Three The weight average molecular weight (Mw) is 1.36 × 10 ^Five Met.
[0040]
10 g of this polybenzoxazole precursor was dissolved in N-methyl-2-pyrrolidone to form a 20% solution, and filtered through a Teflon (R) filter having a pore size of 0.2 μm to obtain a varnish. This varnish was applied onto a silicon wafer using a spin coater. After coating, after drying for 240 seconds on a 100 ° C. hot plate, 150 ° C./30 minutes, 250 ° C./30 minutes, 350 ° C. using an oven in which nitrogen is introduced and the oxygen concentration is controlled to 100 ppm or less. / In order of 30 minutes, a resin film for insulating film was obtained. Various characteristics were evaluated using the obtained film.
[0041]
"Example 2"
Example 1 Example 1 is the same as Example 1 except that 0.016 part (0.1 mmol) of 4-ethynylbenzoic acid chloride is changed to 0.021 part (0.1 mmol) of 6-ethynyl-2-naphthoic acid chloride. Then, a polybenzoxazole precursor (organic insulating film material) was synthesized. When molecular weight was measured by GPC, Mn was 7.0x10 in terms of polystyrene. ^Three , Mw 1.37x10 ^Five Met. Thereafter, a varnish was obtained in the same manner as in Example 1. Using the varnish obtained here, an insulating film resin film was prepared and evaluated in the same manner as in Example 1.
[0042]
"Example 3"
In Example 1, 0.080 parts (0.30 mmol) of trimesic acid trichloride was changed to 0.159 parts (0.60 mmol), and 4.08 parts (9.50 mmol) of 4,4′-hexafluoroisopropylidenebiphenyldicarboxylic acid dichloride. ) Is 3.86 parts (9.00 mmol) and 4-ethynylbenzoyl chloride is 0.016 parts (0.10 mmol) is 0.033 parts (0.20 mmol). Then, a polybenzoxazole precursor (organic insulating film material) was synthesized. When molecular weight was measured by GPC, Mn was 6.7 x 10 in terms of polystyrene. ^Three , Mw is 9.8x10 ^Four Met. Thereafter, a varnish was obtained in the same manner as in Example 1. Using the varnish obtained here, a resin film for insulating film was prepared and evaluated in the same manner as in Example 1.
[0043]
"Example 4"
In Example 1, 0.080 part (0.30 mmol) of trimesic acid trichloride was used as 0.159 part, and 4.08 part (9.50 mmol) of 4,4′-hexafluoroisopropylidenebiphenyldicarboxylic acid dichloride was used as 3.86. All in the same manner as Example 1 except that 4-ethynylbenzoic acid chloride 0.016 part (0.10 mmol) is 3-ethynylbenzoic acid chloride 0.033 part (0.20 mmol). Then, a polybenzoxazole precursor (organic insulating film material) was synthesized. When molecular weight was measured by GPC, Mn was 6.7 x 10 in terms of polystyrene. ^Three , Mw is 9.5x10 ^Four Met. Thereafter, a varnish was obtained in the same manner as in Example 1. Using the varnish obtained here, an insulating film resin film was prepared and evaluated in the same manner as in Example 1.
[0044]
"Comparative Example 1"
In a separable flask equipped with a stirrer, a nitrogen introducing tube and a dropping funnel, 14.65 parts (40 mmol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was added to 200 parts of dried dimethylacetamide. After the addition of 7.92 parts (200 mmol) of pyridine and introduction of dry nitrogen at −15 ° C., 100 g of dimethylacetamide was added to 16.92 g (40 mmol) of 4,4′-hexafluoroisopropylidenebiphenyldicarboxylic acid dichloride. A solution obtained by dissolving was added dropwise over 30 minutes, and the precipitate was collected and dried to obtain a polybenzoxazole precursor (organic insulating film material) powder. When the molecular weight of the insulating film material was measured by GPC, Mn was 3.8 x 10 in terms of styrene. ^Four , Mw is 8.03x10 ^Four Met. Thereafter, a varnish was obtained in the same manner as in Example 1. Using the varnish obtained here, an insulating film resin film was prepared and evaluated in the same manner as in Example 1.
[0045]
“Comparative Example 2”
2.66 parts (10.00 mmol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was dissolved in 10 parts of dried N-methyl-2-pyrrolidone under a dry nitrogen atmosphere. At 5 ° C., 4.08 parts (9.50 mmol) of 4,4′-hexafluoroisopropylidenebiphenyldicarboxylic acid dichloride dissolved in 40 parts of γ-butyrolactone was added dropwise over 30 minutes. Then, it returned to room temperature and stirred at room temperature for 1 hour. Then, what melt | dissolved 1.58 parts of pyridines in 10 parts (gamma) -butyrolactone at 5 degreeC was dripped over 30 minutes. After completion of dropping, the mixture was returned to room temperature and stirred at room temperature for 3 hours to obtain a polybenzoxazole precursor. Thereafter, at 80C, 10 parts of γ-butyrolactone having 0.080 part (0.30 mmol) of trimesic acid trichloride dissolved therein was dropped to react. As a result, the molecular weight increased rapidly, and the reaction solution was a gel. Turned into.
[0046]
“Comparative Example 3”
In the synthesis of the polybenzoxazole precursor of Example 1, everything was the same as in Example 1 except that 0.016 part (0.1 mmol) of 4-ethynylbenzoic acid chloride was not added. Insulating film material) was synthesized. When molecular weight was measured by GPC, Mn was 7.0x10 in terms of polystyrene. ^Three , Mw 1.35x10 ^Five Met. Thereafter, a varnish was obtained in the same manner as in Example 1. Using the varnish obtained here, an insulating film resin film was prepared and evaluated in the same manner as in Example 1.
[0047]
“Comparative Example 4”
In the synthesis of the polybenzoxazole precursor of Example 1, everything was the same as in Example 1 except that 0.080 part (0.030 mmol) of trimesic acid chloride was not added, and the polybenzoxazole precursor (organic insulating film material) ) Was synthesized. When molecular weight was measured by GPC, Mn was 9.8 × 10 in terms of polystyrene. ^Three , Mw is 1.3x10 ^Five Met. Thereafter, a varnish was obtained in the same manner as in Example 1. Using the varnish obtained here, an insulating film resin film was prepared and evaluated in the same manner as in Example 1.
[0048]
[Table 1]

In addition, the density reduction rate is the polybenzo of Comparative Example 1 synthesized without using the compound having a d-valent organic group and the carboxylic acid compound represented by the general formula (6) from the density of each obtained film. Calculation was performed based on the density of the film made of the oxazole resin.
[0049]
As is clear from the results summarized in Table 1, all of the polybenzoxazole resins of Examples produced using the polybenzoxazole precursor of the present invention have a low dielectric constant of 2.43 to 2.5. In addition, it showed good characteristics of high heat resistance. On the other hand, in the comparative example, although it is a polybenzoxazole resin having a branched structure, in Comparative Examples 1 and 3, since there is no cross-linking by acetylene, high heat resistance was not obtained compared to the examples. . Moreover, in Comparative Examples 1 and 4, since it did not have a branched structure, the dielectric constant was higher than that of the Example, and a value lower than 2.6 was not obtained.
[0050]
【The invention's effect】
According to the present invention, an organic insulating film material and an organic insulating film excellent in electrical characteristics, thermal characteristics, mechanical characteristics, and physical characteristics can be obtained. Therefore, the organic insulating film material of the present invention is used in various fields that require electrical characteristics, thermal characteristics, mechanical characteristics, and physical characteristics, such as interlayer insulating films for semiconductors, protective films, interlayer insulating films for multilayer circuits, and flexible films. It can be applied as a copper clad cover coat, solder resist film, liquid crystal alignment film and the like.

Claims (5)

After reacting the diaminophenol compound represented by the general formula (1) with a compound having a d-valent organic group that can react with the amino group of the compound (d is 3 or more and 10 or less), the general formula A polybenzoxazole resin precursor represented by the general formula (8) obtained by reacting with the dicarboxylic acid compound represented by (4) and further reacting with the carboxylic acid compound represented by the general formula (6) An organic insulating film material characterized by comprising a polymer having a main structure.

(In formula (1), X represents a structure selected from formula (2).)

(In formula (2), X ₁ represents a structure selected from formula (3), and the hydrogen atoms on the benzene ring in these structures are methyl, ethyl, propyl, isopropyl, butyl, isobutyl. And may be substituted with at least one group selected from the group consisting of a group, a t-butyl group, a fluorine atom, and a trifluoromethyl group.)

(In formula (4), Y represents a structure selected from formula (5).)

(In formula (5), X ₁ represents a structure selected from formula (3).)

(In formula (6), Z represents a structure selected from formula (7).)

However, n in General formula (8) shows the integer of 2-1000. X represents a structure selected from (2), and Y represents a structure selected from Formula (5). The diaminophenol compound (M) represented by the general formula (1) and the dicarboxylic acid compound (N) represented by the general formula (4) have a reaction molar ratio (N / M) of 0.5 to 0. The organic insulating film material according to claim 1, which is reacted in a range of .99. The carboxylic acid compound (L) represented by the general formula (6) and the diaminophenol compound (M) represented by the general formula (1) have a reaction molar ratio (L / 2M) of 0.01 to 0. The organic insulating film material according to claim 1, wherein the organic insulating film material is reacted in a range of .5. The number of moles of the compound having a d-valent organic group reacting with the amino group of the diaminophenol compound is [[(MN) x2-L] / d] mole. 4. The organic insulating film material according to any one of 3 above. (However, M represents the reaction mole number of the diaminophenol compound, N represents the reaction mole number of the dicarboxylic acid, and L represents the reaction mole number of the carboxylic acid.) An organic insulating film obtained by using the organic insulating film material according to claim 1, wherein the polybenzo represented by the general formula (9) adjusted through a condensation reaction and a crosslinking reaction An organic insulating film comprising a resin layer having an oxazole resin as a main structure.

However, n in general formula (9) shows the integer of 2-1000. X represents a structure selected from Formula (2), and Y represents a structure selected from Formula (5).

(In Formulas (2) and (5), X ₁ represents a structure selected from Formula (3), and the hydrogen atom on the benzene ring in these structures is a methyl group, an ethyl group, a propyl group, an isopropyl group, (It may be substituted with at least one group selected from the group consisting of a butyl group, an isobutyl group, a t-butyl group, a fluorine atom, and a trifluoromethyl group.)