JP2005041938A - Organic insulating film-forming composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic insulating film-forming composition which can form organic insulating films having high mechanical strength. <P>SOLUTION: [1] The organic insulating film-forming composition is characterized by containing a compound having at least three -C≡CH groups in the molecule. [2] A method for producing an organic insulating film is characterized by comprising a process for coating a composition described in the above-mentioned [1] on a substrate and then thermally treating the coated composition at an oxygen concentration of <1 %. [3] An organic insulating film obtained by the production method described in the above-mentioned [2]. [4] An organic insulating film described in the above-mentioned [3], wherein the hardness and elastic modulus of the organic insulating film are ≥1 GPa and ≥10 GPa, respectively. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

【０００９】
式（１）中、ｎは３または４を表わし、Ｘ^１は、−Ｃ≡ＣＨ基以外の基で置換されていてもよい炭素数４〜２０の脂環式炭化水素基、または−Ｃ≡ＣＨ基以外の基で置換されていてもよい芳香環を有する基を表わし、Ｙ^１、Ｚ^１は、それぞれ独立に、単結合、−Ｃ≡ＣＨ基以外の基で置換されていてもよい芳香環を有する基、−Ｏ−または−ＣＯ−を表わす。
【００１０】
式（１）中、Ｘ^１において、炭素数４〜２０の脂環式炭化水素基としては、例えば、シクロブタン環、シクロペンタン環、シクロヘキサン環、シクロヘプタン環、アダマンタン環、ノルボルネン環などを有する３価または４価の基が挙げられる。
−Ｃ≡ＣＨ基以外の置換基としては、例えば、アルキル基、アルコキシ基、アルケニル基、炭素数３〜１０のアルキニル基、アリール基、置換基を有してもよいトリアルキルシリル基、ヒドロキシル基などが挙げられる。
ここで、アルキル基としては、例えば、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ブチル基、イソブチル基、ペンチル基、へキシル基などが挙げられる。
アルコキシ基としては、例えば、メトキシ基、エトキシ基、プロポキシ基などが挙げられる。
アルケニル基としては、例えば、ビニル基、アリル基、ブテニル基、ペンテニル基、ヘキセニル基、２−メチルアリル基、ブタジエニル基などが挙げられる。
炭素数３〜１０のアルキニル基としては、例えば、プロパルギル基、ブチニル基、ペンチニル基、ブタジイニル基、ヘプチニル基などが挙げられる。
アリール基としては、例えば、フェニル基、ジフェニル基、ナフチル基、アントラセニル基、フルオレニル基などが挙げられる。
置換基を有してもよいトリアルキルシリル基としては、例えば、トリメチルシリル基、トリエチルシリル基、トリイソプロピルシリル基、ジメチルエチルシリル基などが挙げられる。
【００１１】
芳香環を有する基としては、例えば、ベンゼン環、ジフェニル環、ナフタレン環、アントラセン環、フルオレン環などを有する３価または４価の基などが挙げられる。
−Ｃ≡ＣＨ基以外の置換基としては、例えば、アルキル基、アルコキシ基、アルケニル基、炭素数３〜１０のアルキニル基、アリール基、置換基を有してもよいトリアルキルシリル基、ヒドロキシル基などが挙げられる。
ここで、アルキル基、アルコキシ基、アルケニル基、炭素数３〜１０のアルキニル基、アリール基、置換基を有してもよいトリアルキルシリル基としては、前記と同じものが挙げられる。
【００１２】
式（１）中、Ｙ^１、Ｚ^１における芳香環を有する基としては、例えば、ベンゼン環、ジフェニル環、ナフタレン環、アントラセン環、フルオレン環を有する２価の基などが挙げられる。
−Ｃ≡ＣＨ基以外の置換基としては、例えば、アルキル基、アルコキシ基、アルケニル基、炭素数３〜１０のアルキニル基、アリール基、置換基を有してもよいトリアルキルシリル基、ヒドロキシル基などが挙げられる。
アルキル基、アルコキシ基、アルケニル基、炭素数３〜１０のアルキニル基、アリール基、置換基を有してもよいトリアルキルシリル基としては、前記と同じものが挙げられる。
【００１３】
耐熱性の観点から、前記式（１）におけるＸ^１が、ベンゼン環、ジフェニル環、ナフタレン環、アントラセン環、アダマンタン環を有する３価または４価の基であることが好ましく、ベンゼン環、アダマンタン環を有する３価または４価の基であることがより好ましい。
【００１４】
また、耐熱性の観点から、前記式（１）におけるＹ^１が、ベンゼン環、ジフェニル環、ナフタレン環、アントラセン環、アダマンタン環を有する２価の基で、Ｚ^１が、酸素原子であるか、Ｙ^１とＺ^１がともに単結合であることが好ましく、Ｙ^１が、ベンゼン環を有する２価の基で、Ｚ^１が、酸素原子であるか、Ｙ^１とＺ^１がともに単結合であることがより好ましい。
【００１５】
これらの中で、前記式（１）におけるＸ^１がベンゼン環、アダマンタン環を有する３価または４価の基で、Ｙ^１がベンゼン環を有する２価の基で、Ｚ^１が酸素原子であるか、Ｘ^１がベンゼン環、アダマンタン環を有する３価または４価の基で、Ｙ^１、Ｚ^１がともに単結合であることがさらに好ましい。
【００１６】
式（１）で示される化合物は、以下の化合物の少なくとも１つであることが特に好ましい。

【００１７】
式（２）中、ｍは２または３を表わし、Ｘ^２は、−Ｃ（Ｒ^１）（Ｒ^２）−、＞Ｃ（Ｒ^３）−、−Ｃ≡ＣＨ基以外の基で置換されていてもよい炭素数４〜２０の脂環式炭化水素を有する基、−Ｃ≡ＣＨ基以外の基で置換されていてもよい芳香環を有する基、−Ｏ−または−ＣＯ−を表わし、Ｒ^１〜Ｒ^３は、それぞれ独立に、水素原子を表わすか、ヒドロキシル基、または置換されていてもよい炭素数１〜１０のアルキル基を表わし、Ｙ^２、Ｚ^２は、それぞれ独立に、単結合、−Ｃ≡ＣＨ基以外の基で置換されていてもよい芳香環を有する基、−Ｏ−または−ＣＯ−を表わす。
【００１８】
式（２）中、Ｘ^２において、炭素数４〜２０の脂環式炭化水素基としては、例えば、シクロブタン環、シクロペンタン環、シクロヘキサン環、シクロヘプタン環、アダマンタン環、ノルボルネン環などを有する２価または３価の基などが挙げられる。
また、芳香環を有する基としては、例えば、ベンゼン環、ジフェニル環、ナフタレン環、アントラセン環、フルオレン環などを有する２価または３価の基などが挙げられる。
−Ｃ≡ＣＨ基以外の置換基としては、例えば、アルキル基、アルコキシ基、アルケニル基、炭素数３〜１０のアルキニル基、アリール基、置換基を有してもよいトリアルキルシリル基、ヒドロキシル基などが挙げられる。
ここで、アルキル基、アルコキシ基、アルケニル基、炭素数３〜１０のアルキニル基、アリール基、置換基を有してもよいトリアルキルシリル基としては、前記と同じものが挙げられる。
【００１９】
式（２）中、Ｒ^１〜Ｒ^３における炭素数１〜１０のアルキル基としては、例えば、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ブチル基、イソブチル基、ペンチル基、へキシル基などが挙げられる。
炭素数１〜１０のアルキル基置換基としては、例えば、アルコキシ基、アルケニル基、炭素数３〜１０のアルキニル基、アリール基、置換基を有してもよいトリアルキルシリル基、ヒドロキシル基などが挙げられる。
ここで、アルコキシ基、アルケニル基、炭素数３〜１０のアルキニル基、アリール基、置換基を有してもよいトリアルキルシリル基としては、前記と同じものが挙げられる。
【００２０】
式（２）中、Ｙ^２、Ｚ^２において、芳香環を有する基としては、例えば、ベンゼン環、ジフェニル環、ナフタレン環、アントラセン環、フルオレン環などを有する２価の基などが挙げられる。
−Ｃ≡ＣＨ基以外の置換基としては、例えば、アルキル基、アルコキシ基、アルケニル基、炭素数３〜１０のアルキニル基、アリール基、置換基を有してもよいトリアルキルシリル基、ヒドロキシル基などが挙げられる。
ここで、アルキル基、アルコキシ基、アルケニル基、炭素数３〜１０のアルキニル基、アリール基、置換基を有してもよいトリアルキルシリル基としては、前記と同じものが挙げられる。
【００２１】
耐熱性の観点から、前記式（２）におけるＸ^２が、ベンゼン環、ジフェニル環、ナフタレン環、アントラセン環、フルオレン環、シクロヘキサン環、アダマンタン環を有する２価または３価の基、カルボニル基、アルキリデン基、アルキリジン基であることが好ましく、フルオレン環、シクロヘキサン環、アダマンタン環を有する２価または３価の基、カルボニル基、アルキリデン基、アルキリジン基であることがより好ましい。
【００２２】
また、耐熱性の観点から、前記式（２）におけるＹ^２がベンゼン環基、ジフェニル環、ナフタレン環を、アントラセン環、アダマンタン環を有する２価の基で、Ｚ^２が、酸素原子であるか、Ｙ^２とＺ^２がともに単結合であることが好ましく、Ｙ^２がベンゼン環を有する２価の基で、Ｚ^２が酸素原子であるか、Ｙ^２とＺ^２がともに単結合であることがより好ましい。
【００２３】
これらの中で、前記式（２）におけるＸ^２がフルオレン環、シクロヘキサン環、アダマンタン環を有する２価または３価の基、カルボニル基、アルキリデン基、アルキリジン基で、Ｙ^２がベンゼン環を有する２価の基で、Ｚ^２が酸素原子であるか、Ｘ^２がフルオレン環、シクロヘキサン環、アダマンタン環を有する２価または３価の基、カルボニル基、アルキリデン基、アルキリジン基で、Ｙ^２、Ｚ^２がともに単結合であることがさらに好ましい。
【００２４】
式（２）で示される化合物は、以下の化合物の少なくとも１つであることが特に好ましい。

【００２５】
分子内に−Ｃ≡ＣＨ基を少なくとも３個有する化合物のＧＰＣによるポリスチレン換算重量平均分子量は、５０００以下であることが好ましく、３０００以下であることがより好ましく、１５００以下であることがさらに好ましい。
該分子量が５０００を超えると、分子内の−Ｃ≡ＣＨ基の割合が低下することにより、架橋密度が低下し、硬度、弾性率が十分でない傾向がある。
【００２６】
本発明の有機絶縁膜形成用組成物は、分子内に−Ｃ≡ＣＨ基を少なくとも３個有する化合物を含有するものであるが、さらに有機溶剤を配合して塗布液としてもよい。
該有機溶剤としては、分子内に−Ｃ≡ＣＨ基を少なくとも３個有する化合物を溶解可能なものであれば特に限定されない。
該有機溶剤としては、例えば、メタノール、エタノール、イソプロパノール、１−ブタノール、２−エトキシメタノール、３−メトキシプロパノール等のアルコール系溶剤、アセチルアセトン、メチルエチルケトン、メチルイソブチルケトン、３−ペンタノン、２−ヘプタノン、３−ヘプタノン、シクロヘキサノン等のケトン系溶剤、酢酸プロピル、酢酸ブチル、酢酸イソブチル、酢酸ペンチル、プロピオン酸メチル、プロピオン酸エチル、酪酸メチル、プロピレングリコールモノメチルエーテルアセテート、乳酸エチル等のエステル系溶剤、ジイソプロピルエーテル、ジブチルエーテル、ジオキサン、アニソール、フェネトール、ベラトロール、ジフェニルエーテル等のエーテル系溶剤、ベンゼン、トルエン、メシチレン、エチルベンゼン等の芳香族炭化水素系溶剤、クロロホルム、クロロベンゼン、ジクロロエチレン、トリクロロエチレン等のハロゲン系溶剤、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジエチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチルプロピオンアミド，Ｎ−メチルピロリドン等のアミド系溶剤、ペンタン、ヘキサン、ヘプタン等の脂肪族炭化水素系溶剤などが挙げられ、これらは工業的に入手が容易であるため好適に使用される。
【００２７】
これらの有機溶剤は、分子内に−Ｃ≡ＣＨ基を少なくとも３個有する化合物の溶解性、塗布液自体の塗布性が良好に維持できる範囲で任意に選択することが可能であり、１種または２種以上を組み合わせて用いてもよい。
【００２８】
該有機溶剤を配合した塗布液として用いる場合、その全固形分濃度、すなわち、［分子内に−Ｃ≡ＣＨ基を少なくとも３個有する化合物／［分子内に−Ｃ≡ＣＨ基を少なくとも３個有する化合物＋有機溶剤配合量］］×１００は、５〜５０％であることが好ましい。該濃度は、得られる塗布膜の膜厚や段差埋め込み性改良等の目的に応じて適宜調整することができる。
【００２９】
本発明の有機絶縁膜形成用組成物には、さらに添加剤を配合してもよい。
該添加剤としては、例えば、シランカップリング剤、チタンカップリング剤等のカップリング剤、界面活性剤、整泡剤、有機過酸化物等の触媒などが挙げられる。
カップリング剤は基板との密着性を向上させるために、界面活性剤は塗布性の安定化のために、有機過酸化物等の触媒はモノマーの架橋温度を低下させるためにそれぞれ配合してもよい。
【００３０】
有機絶縁膜の形成に用いられる基板としては、例えば、ガラス、石英、金属、セラミック、シリコン、ＧａＡｓ、ＳｉＯ_２、ＳｉＮ、ＳｉＣなどの基板が挙げられる。
【００３１】
該基板への有機絶縁膜形成用組成物の塗布方法としては、例えば、スピンコーティング、ローラーコーティング、ディップコーティング、スプレー法などが挙げられる。
【００３２】
基板に塗布された分子内に−Ｃ≡ＣＨ基を少なくとも３個有する化合物を含む組成物を架橋せしめる方法としては、例えば、加熱処理法、紫外線照射法等が挙げられる。
加熱処理法としては、例えば、オーブン、ホットプレート、ファーネス炉などを使用する方法、ＲＴＰ（ランプ加熱ヒーター）等によるキセノンランプを使用した光照射加熱などが挙げられる。
【００３３】
加熱処理は、酸素濃度１％未満の雰囲気で行うことが好ましく、酸素濃度１００ｐｐｍ未満の雰囲気で行うことがより好ましい。
酸素濃度１％未満の雰囲気としては、例えば、減圧雰囲気、不活性ガス雰囲気、または真空下などを挙げることができる。
減圧雰囲気は、１〜２０Ｐａ程度であることが好ましい。
不活性ガスとしては、例えば、ヘリウム、窒素、アルゴン等が挙げられる。
加熱処理の温度は、４００℃以下であることが好ましい。４００℃以下で加熱することにより、基板に塗布された分子内に−Ｃ≡ＣＨ基を少なくとも３個有する化合物の分解を抑制することができる傾向がある。
【００３４】
得られた有機絶縁膜の硬度、弾性率は、有機絶縁膜の表面近傍での硬度、弾性率であり、ＨＹＳＩＴＲＯＮ社製Ｈｙｓｉｔｏｒｏｎ ＴｒｉｂｏＳｃｏｐｅ Ｍｉｃｒｏｍｅｃｈａｎｉｃａｌ Ｔｅｓｔ装置を用いてナノインデンテーション法により測定した値である。なお、表面近傍とは、有機絶縁膜の膜厚の１／１０〜１／６の深度で、具体的には１５ｎｍ〜５０ｎｍをいう。また、硬度、弾性率の測定には、ベルコビッチ圧子（ダイアモンド製）を用いた。
該有機絶縁膜の硬度は１ＧＰａ以上であることが好ましく、弾性率が１０ＧＰａ以上であることが好ましい。
【００３５】
本発明の有機絶縁膜形成用組成物から得られる有機絶縁膜は、比較的低温で架橋可能であることから、短時間で容易に製造することが可能である。
該有機絶縁膜は、低誘電率である上、高硬度、高弾性率であり、耐熱性、耐薬品性にも優れていることから、半導体などの電子材料用の絶縁膜として好適に使用される。
【００３６】
【実施例】
以下、本発明を実施例に基いて更に詳細に説明するが、本発明が実施例により限定されるものではないことは言うまでもない。
【００３７】
製造例１
化合物Ａの製造
１０００ｍＬ４つ口フラスコにジブロモアダマンタン３０．０ｇ（１０２ｍｍｏｌ）、ブロモベンゼン１６０．２ｇ（１．０２ｍｏｌ）及びジクロロメタン５７０ｇを仕込み、氷水で５℃まで冷却した。ここに、無水塩化鉄（ＩＩＩ）０．８３ｇ（５．１ｍｍｏｌ）を加え、１２時間かけて室温まで昇温しながら攪拌を続けた。反応液を１Ｎ塩酸３００ｇに添加し、攪拌後、水層を除去した。有機層を１Ｎ塩酸１００ｇで１回洗浄し、さらにイオン交換水１００ｇで４回洗浄した。ジクロロメタンと過剰ブロモベンゼンを減圧蒸留で除去した後、残さにメタノール３００ｇを加え、攪拌した。沈殿したオイル状物を取り出し、テトラヒドロフラン３０ｇを加えて溶解させ、メタノール３００ｇ中に滴下した。沈殿したオイル状物を取り出して減圧乾燥し、オイル状物を３８．５ｇ得た。このオイル状物３７．４ｇを１０００ｍＬ４つ口フラスコに仕込み、テトラキス（トリフェニルホスフィン）パラジウム４．３６ｇ、よう化銅（Ｉ）１．４４ｇ及びトリエチルアミン３７４ｇを加え、オイル状物を溶解させた。ここに、トリメチルシリルアセチレン４１．２ｇを１時間かけて滴下し、８０℃まで昇温した。同温度で８時間反応させ、さらに室温まで冷却後、１６時間攪拌を続けた。不溶物を濾別し、トルエン１５０ｇで洗浄した。濾液と洗液を混合して濃縮し、残さをカラム（固定相；シリカゲル６０、展開液；ヘキサン／トルエン）で精製した。主生成物７．８０ｇをメタノール７８ｇ、テトラヒドロフラン２３４ｇの混合溶媒に溶解させ、炭酸カリウム１．６５ｇを加え、室温で１０時間攪拌した。溶媒を減圧留去し、残さにトルエン８０ｇ、１Ｎ塩酸３０ｇを加え、攪拌後、水層を除去した。さらに１Ｎ塩酸２０ｇを加え、攪拌後、水層を除去した。有機層をイオン交換水３０ｍＬで３回洗浄し、さらに、１％蓚酸水３０ｇで２回、イオン交換水３０ｍＬで４回洗浄し、トルエンを減圧溜去下した。１，３，５−トリス（４−エチニルフェニル）アダマンタン４．２ｇを得た。これを化合物Ａとする。
【００３８】
製造例２
化合物Ｂの製造
２００ｍＬ４つ口フラスコにジブロモアダマンタン５．０ｇ（１７ｍｍｏｌ）、臭化アルミニウム２．３ｇ（９ｍｍｏｌ）及びｍ−ジブロモベンゼン１００ｍＬを仕込み、６０℃で１０時間攪拌した。冷却後、反応液を濃塩酸１０ｇを溶解させた氷水１５０ｇに添加し、攪拌後、水相を除去した。過剰ジブロモベンゼンを減圧蒸留で除去した後、残さに塩化メチレン１００ｍＬを添加・溶解させ、水及び食塩水で洗浄後、硫酸マグネシウムで乾燥させた。乾燥剤をろ別後、エバポレータで塩化メチレンを濃縮し、メタノール１００ｍＬを加えて攪拌した。析出した結晶をろ別し、減圧乾燥させた。この結晶６．０ｇを２００ｍＬ４つ口フラスコに仕込み、ジクロロビス（トリフェニルホスフィン）パラジウム２００ｍｇ、トリフェニルホスフィン４００ｍｇ、よう化銅（Ｉ）１８０ｍｇ及びトリエチルアミン１００ｍＬを加え、７０〜８０℃まで昇温した。トリメチルシリルアセチレン６．７ｇを１時間かけて滴下し、同温度で４時間反応させた。冷却後、溶媒を留去し、残渣にジエチルエーテル２００ｍＬを加え、不溶塩をろ過した。ろ液を１Ｎ塩酸、飽和食塩水および超純水で洗浄し、エーテル相を硫酸マグネシウムで乾燥させた。乾燥剤をろ別し、エーテルを留去し、残渣をカラム（固定相；シリカゲル６０、展開液；ヘキサン／塩化メチレン）で生成した。主生成物５．９ｇをメタノール１５０ｍＬ、テトラヒドロフラン１００ｍＬに溶解させ、炭酸カリウム０．５ｇを加え、室温で４時間攪拌した。溶媒を減圧留去し、残渣に塩化メチレン２００ｍＬ、１Ｎ塩酸１００ｍＬを加え、攪拌後、塩酸相を除去した。塩化メチレン相を超純水１００ｍＬで３回洗浄し、塩化メチレン相から溶媒を留去・減圧乾燥し、ビス（ジエチニルフェニル）アダマンタン３．２ｇを得た。これを化合物Ｂとする。
【００３９】
製造例３
化合物Ｃの製造
５００ｍＬ４つ口フラスコに１，３−ビス（４−ヒドロキシフェニル）アダマンタン６．４ｇ（２０ｍｍｏｌ）、１，３−ジブロモ−５−フルオロベンゼン１０．４ｇ（４１ｍｍｏｌ）及び炭酸カリウム２２．４ｇ（６０ｍｍｏｌ）、トルエン１６８ｇ、ジメチルスルホキシド８４ｇを仕込み、１２０℃まで徐々に昇温し、この温度で４５時間保温を続けた。室温まで冷却後、イオン交換水１５０ｇと酢酸２１ｇを加え、攪拌後、水層を除いた。有機層をさらに１００ｇのイオン交換水にて洗浄し、減圧濃縮した。ここにトルエン２０ｇを加えて６０℃まで昇温させ、メタノール７０ｇを加えて室温まで徐々に冷却した。析出した結晶を濾取し、メタノール１００ｇで洗浄した。白色結晶として１，３−ビス（４−（３，５−ジブロモフェニルオキシ）フェニル）アダマンタンを１５．４ｇ（収率９８％）を得た。
１，３−ビス（４−（３，５−ジブロモフェニルオキシ）フェニル）アダマンタン１４．２ｇ（１８ｍｍｏｌ）を５００ｍＬ４つ口フラスコに仕込み、テトラキス（トリフェニルホスフィン）パラジウム０．６２ｇ、よう化銅（Ｉ）０．２１ｇ及びトリエチルアミン１４２ｇとトルエン１００ｇを加えた。ここに、トリメチルシリルアセチレン１０．６ｇを１時間かけて滴下し、８０℃まで昇温した。同温度で４０時間反応させた。この間、１２時間目と２６時間目にそれぞれ３．７ｇ、３．６ｇのトリメチルシリルアセチレンを加えた。室温まで冷却後、不溶物を濾別し、トルエン１２０ｇで洗浄した。濾液と洗液を混合して濃縮し、残さをカラム（固定相；シリカゲル６０、展開液；ヘキサン／トルエン）で精製した。主生成物として、１２．６ｇ（収率８２％）の１，３−ビス（４−（３，５−ビス（トリメチルシリルエチニル）フェニルオキシ）フェニル）アダマンタンを得た。
１，３−ビス（４−（３，５−ビス（トリメチルシリルエチニル）フェニルオキシ）フェニル）アダマンタン１２．０ｇ（１４ｍｍｏｌ）をメタノール１２０ｇ、テトラヒドロフラン２４０ｇの混合溶媒に溶解させ、炭酸カリウム１．９３ｇを加え、室温で１０時間攪拌した。溶媒を減圧留去し、残さにトルエン５０ｇを加え、酢酸２．４ｇ、イオン交換水２５ｇを加えて中和し、水層を除去した。有機層を１Ｎ塩酸２０ｇで１回、イオン交換水２５ｍＬで４回洗浄した。さらに、１％蓚酸水３０ｇで２回、イオン交換水２０ｍＬで４回洗浄し、トルエンを減圧留去下した。残さにメタノール５０ｇを加えた。結晶を濾取し、メタノール５０ｇで洗浄した。１，３−ビス（４−（３，５−ジエチニルフェニルオキシ）フェニル）アダマンタン６．４ｇ（収率８０％）を得た。これを化合物Ｃとする。
【００４０】
製造例４
化合物Ｄの製造
５００ｍＬ４つ口フラスコに、４，４’−（９Ｈ−フルオレン−９−イリデン）ビスフェノール（８．８ｇ）、１，３−ジブロモ−５−フルオロベンゼン（１２．７ｇ）、炭酸カリウム（１３．８ｇ）、トルエン（１００ｇ）、ＤＭＳＯ（２００ｇ）を仕込み、窒素気流下、１２０℃／５ｈｒ保温攪拌を行なった。トルエン、酢酸、水を加え分液し、油層を減圧留去してテトラブロモ体である中間体Ｄ１を得た。
５００ｍＬ４つ口フラスコに、上記で得られた中間体Ｄ１の一部（１１．６ｇ）、トリエチルアミン（２００ｇ）、ＣｕＩ（Ｉ）（０．５ｇ）を仕込み、Ａｒ気流下、室温にて３０分間攪拌を行った。Ｐｄ（０）（ＴＰＰ）_４（１．８ｇ）、トリメチルシリルアセチレン（７．９ｇ）を仕込んだ後、８０℃に昇温し、５ｈｒ保温攪拌を行った。反応マスをろ過し、ろ液を濃縮した後、トルエンにてカラム処理を行い、濃縮してテトラ（トリメチルシリルエチニル）体である中間体Ｄ２を得た。
上で得られた中間体Ｄ２をそのまま３００ｍＬ４つ口フラスコに仕込み、トルエン５０ｇ、メタノール５０ｇ、炭酸カリウム１１．６ｇを仕込み、室温にて１８時間攪拌を行った。反応マスをそのまま酢酸で中和し、トルエンを加えて水洗を行なった後、トルエンを減圧留去した。得られたテトラエチニル体モノマーを化合物Ｄとする。
【００４１】
製造例５
化合物Ｅの製造
ジブロモアダマンタンをトリブロモアダマンタンに変えた以外は製造例２と同様な処理を行い、トリス（ジエチニルフェニル）アダマンタン４．５ｇを得た。これを化合物Ｅとする。
【００４２】
製造例６
化合物Ｆの製造
５００ｍＬ４つ口フラスコに、１，１’，１“−トリヒドロキシフェニルエタン（６．１ｇ）、１，３−ジブロモ−５−フルオロベンゼン（１５．２ｇ）、炭酸カリウム（１３．８ｇ）、トルエン（１００ｇ）、ＤＭＳＯ（２００ｇ）を仕込み、窒素気流下、１２０℃／５ｈｒ保温攪拌を行なった。トルエン、酢酸、水を加え分液し、油層を減圧留去してヘキサブロモ体である中間体Ｆ１を得た。このヘキサブロモ体を用い、製造例４と同様にしてエチニルカップリングおよび保護基の脱離を行ない、化合物Ｆを得た。
【００４３】
製造例７
化合物Ｇの製造
５００ｍＬ４つ口フラスコに、４，４’−ジフルオロベンゾフェノン（５．５ｇ）、２，４−ジブロモフェノール（１２．６ｇ）、炭酸カリウム（１３．８ｇ）、トルエン（１００ｇ）、ＤＭＳＯ（２００ｇ）を仕込み、窒素気流下、１２０℃／５ｈｒ保温攪拌を行なった。トルエン、酢酸、水を加え分液し、油層を減圧留去して中間体Ｇ１を得た。このテトラブロモ体を用い、製造例４と同様にしてエチニルカップリングおよび保護基の脱離を行ない、化合物Ｇを得た。
【００４４】
製造例８
化合物Ｈの製造
５００ｍＬ４つ口フラスコに無水臭化アルミニウム５．０３ｇ（１９ｍｍｏｌ）を仕込み、５℃まで冷却した。ジブロモアダマンタン１５．０ｇ（５１ｍｍｏｌ）、ヨードベンゼン２６０．２ｇ（１．２８ｍｏｌ）の混合物を仕込んだ。１２時間かけて室温まで昇温しながら攪拌を続けた。更に６０℃まで昇温し、この温度で４時間保温を続けた。冷却後、反応液を濃塩酸２０ｇとイオン交換水１２０ｇの混合液に注いだ。この混合物を分液し、有機層を１０％亜硫酸ナトリウム水溶液１００ｇで３回、イオン交換水１００ｇで３回洗浄した。得られた有機層にメタノール４００ｇを加え、攪拌した。沈殿したオイル状物を取り出し、メタノール２００ｇを加え、攪拌した。沈殿したオイル状物を取り出し、更にメタノール２００ｇを加え、攪拌した。得られたオイル状物をテトラヒドロフラン４０ｇに溶解し、メタノール２００ｇ中に滴下した。析出した結晶を濾取し、テトラヒドロフラン４０ｇに溶解し、メタノール２００ｇ中に滴下した。析出した結晶を濾取して乾燥し、白色結晶１８．５ｇを得た。この結晶１７．８ｇを５００ｍＬ４つ口フラスコに仕込み、テトラキス（トリフェニルホスフィン）パラジウム０．５７ｇ、よう化銅（Ｉ）０．１９ｇ及びトリエチルアミン１７８ｇを加えた。ここに、トリメチルシリルアセチレン１３．０ｇを滴下して加え、８０℃まで昇温した。同温度で４時間反応させ、さらに室温まで冷却後、１６時間攪拌を続けた。不溶物を濾別し、トルエン７５ｇで洗浄した。濾液と洗液を混合して濃縮し、残さをカラム（固定相；シリカゲル６０、展開液；ヘキサン／トルエン）で精製した。主生成物１２．２ｇをメタノール１２２ｇ、テトラヒドロフラン２４４ｇの混合溶媒に溶解させ、炭酸カリウム１．１６ｇを加え、室温で１時間攪拌した。溶媒を減圧留去し、残さにジクロロメタン１５０ｇ、１Ｎ塩酸１００ｇを加え、攪拌後、水層を除去した。さらに有機層をイオン交換水１００ｍＬで洗浄し、さらに、１％蓚酸水７５ｇで２回、イオン交換水７５ｍＬで３回洗浄し、ジクロロメタンを減圧留去下した。得られた結晶を化合物Ｈとする。
【００４５】
製造例９
化合物Ｉの製造
５００ｍＬ４つ口フラスコにジブロモアダマンタン１０．０ｇ（３４ｍｍｏｌ）、４−ブロモジフェニルエーテル８４．７ｇ（０．３４ｍｏｌ）及びジクロロメタン１７０ｇを仕込み、氷水で５℃まで冷却した。ここに、無水塩化鉄（ＩＩＩ）０．２８ｇ（１．７ｍｍｏｌ）を加えた。この温度で６時間攪拌を続け、さらに室温まで昇温し、この温度で１０時間攪拌を続けた。反応液にジクロロメタン８０ｇを加え、イオン交換水２００ｇで２回、さらに１００ｇで２回洗浄した。ジクロロメタンを減圧蒸留で除去した後、残さをカラム（固定相；シリカゲル６０、展開液；ヘキサン／トルエン）で精製した。１，３−ビス（４−（４−ブロモフェニルオキシ）フェニル）アダマンタン９．２ｇをオイル状物として得た。このオイル状物を２００ｍＬ４つ口フラスコに仕込み、テトラキス（トリフェニルホスフィン）パラジウム０．５０ｇ、よう化銅（Ｉ）０．１７ｇ及びトリエチルアミン９２ｇを加え、オイル状物を溶解させた。ここに、トリメチルシリルアセチレン４．３ｇを１時間かけて滴下し、８０℃まで昇温した。同温度で５５時間反応させた。この間、２０時間目と３４時間目にそれぞれ６．５ｇ、５．８ｇのトリメチルシリルアセチレンを加えた。室温まで冷却後、不溶物を濾別し、トルエン７０ｇで洗浄した。濾液と洗液を混合して濃縮し、残さをカラム（固定相；シリカゲル６０、展開液；ヘキサン／トルエン）で精製した。主生成物４．０ｇをメタノール４０ｇ、テトラヒドロフラン１２０ｇの混合溶媒に溶解させ、炭酸カリウム０．８３ｇを加え、室温で２８時間攪拌した。溶媒を減圧留去し、残さにトルエン３０ｇ、２Ｎ塩酸７ｇとイオン交換水１０ｇを加え、攪拌後、水層を除去した。さらに１Ｎ塩酸３ｇとイオン交換水１０ｇを加え、攪拌後、水層を除去した。有機層をイオン交換水１０ｍＬで３回洗浄し、さらに１％蓚酸水１０ｇで２回、イオン交換水１０ｍＬで３回洗浄し、トルエンを減圧留去下した。１，３−ビス（４−（４−エチニルフェニルオキシ）フェニル）アダマンタン２．７ｇを得た。これを化合物Ｉとする。
【００４６】
製造例１０
化合物Ｊの製造
ブロモアダマンタン２１．５ｇ（０．１ｍｏｌ）、ジフェニルエーテル８．５ｇ（０．０５ｍｏｌ）及び四塩化炭素５０ｍＬを２００ｍＬ４つ口フラスコに仕込み、氷浴で冷却しながら、塩化アルミニウム１０．８ｇ（０．０８ｍｏｌ）を１時間かけて少量ずつ仕込んだ。冷却下１時間、室温に戻して１時間、更にオイルバスを設置し、内温４０℃で４時間反応させた。再度、氷浴を設置し、内温を１０℃以下にした後、１Ｎ ＨＣｌ８０ｍＬを滴下した。次いで、ＴＨＦ５０ｍＬを仕込み、生成物を溶解させた後、不溶塩をセライト５１５をプレコートしたフィルターでろ過し、ろ液から水相を除去した。次いで、飽和食塩水で四塩化炭素相を洗浄した後、硫酸マグネシウムで乾燥させた。乾燥剤をろ別し、減圧蒸留で溶媒を留去した。残さにメタノール２５０ｇを加え、攪拌し、析出した結晶をろ過し、減圧乾燥を行い、ビスアダマンチルジフェニルエーテル２１ｇを得た。これを５．０ｇ（１１ｍｍｏｌ）、臭素１２ｍＬ（２３ｍｍｏｌ）とともに１００ｍＬ４つ口フラスコに仕込み、氷浴で冷却しながら、４時間反応させた。塩化メチレン１５０ｍＬを加え、内容物を溶解させた後、１０％亜硫酸ナトリウム水溶液５００ｍＬ中に滴下した。水相を除去し、イオン交換水で洗浄した後、塩化メチレンを除去した。残さにＴＨＦ２５ｇを加えて溶解させた後、メタノール３００ｍＬ中に投入し、結晶を析出させた。結晶をろ過・眼圧乾燥させ、ビスアダマンチルジブロモジフェニルエーテル５．２ｇを得た。これを３ｇ分取し、ビス（トリフェニルホスフィン）ジクロロパラジウム２０ｍｇ、よう化銅８０ｍｇ、トリフェニルホスフィン４０ｍｇ及びトリエチルアミン５０ｍＬと共に１００ｍＬ４つ口フラスコに入れ、７５℃まで昇温した。トリメチルシリルアセチレン１．４８ｇを３０分かけて滴下し、同温度で６時間反応させた。冷却後、反応マスから不溶塩をろ別し、ろ液からトリエチルアミンを留去後、残さに塩化メチレン１００ｍＬを加え、１ＮＨＣｌ５０ｍＬで洗浄し、更にイオン交換水で有機相を洗浄した。有機相から塩化メチレンを留去し、残さをシリカゲルカラムクロマトグラフィー（固定相：シリカゲル６０、展開相 塩化メチレン／ｎ−ヘキサン＝１／２）で精製した。主成分フラクションを集め、展開相を留去し、残さにメタノール５０ｍＬ、ＴＨＦ５０ｍＬ、炭酸ナトリウム０．５ｇを加え、４時間室温で攪拌した。溶媒を留去し、残さに塩化メチレン１００ｍＬを加え、１Ｎ ＨＣｌ５０ｍＬで洗浄し、更にイオン交換水で洗浄した。有機相を約 ２０ｍＬまで濃縮し、メタノール２００ｍＬに投入して、ビスアダマンチルジエチニルジフェニルエーテル１．２ｇを得た。これを化合物Ｊとする。
【００４７】
塗布液の調製
塗布液１
製造例１で得られた化合物Ａをアニソールで固形分１０重量％になるように調整した。さらに調製された溶液を、０．１μｍＰＴＦＥフィルターで公知の方法により濾過し、塗布液を調製した。
塗布液２
製造例１で得られた化合物Ａの代わりに製造例２で得られた化合物Ｂを用いた以外は塗布液１に準拠して塗布液を調整した。
塗布液３
製造例１で得られた化合物Ａの代わりに製造例３で得られた化合物Ｃを用いた以外は塗布液１に準拠して塗布液を調整した。
塗布液４
製造例１で得られた化合物Ａの代わりに製造例４で得られた化合物Ｄを用いた以外は塗布液１に準拠して塗布液を調整した。
塗布液５
製造例１で得られた化合物Ａの代わりに製造例５で得られた化合物Ｅを用いた以外は塗布液１に準拠して塗布液を調整した。
塗布液６
製造例１で得られた化合物Ａの代わりに製造例６で得られた化合物Ｆを用いた以外は塗布液１に準拠して塗布液を調整した。
塗布液７
製造例１で得られた化合物Ａの代わりに製造例７で得られた化合物ＧをＮＭＰで固形分１０重量％になるように調整した。さらに調製された溶液を、０．１μｍＰＴＦＥフィルターで公知の方法により濾過し、塗布液を調製した。
塗布液８
製造例１で得られた化合物Ａの代わりに製造例８で得られた化合物Ｈを用いた以外は塗布液１に準拠して塗布液を調整した。

塗布液９
製造例１で得られた化合物Ａの代わりに製造例９で得られた化合物Ｉを用いた以外は塗布液１に準拠して塗布液を調整した。

塗布液１０
製造例１で得られた化合物Ａの代わりに製造例１０で得られた化合物Ｊを用いた以外は塗布液１に準拠して塗布液を調整した。

【００４８】
実施例１
調製された塗布液１を、４インチシリコンウェハー上に約１ｍｌ滴下した。その後、このウェハーを５００ｒｐｍで３秒間スピンさせてから、２０００ｒｐｍの速度で１５秒間スピンさせた。コーティングしたウェハーを１５０℃で１分間焼き付けた。次いで、その焼き付けたウェハーを炉内で、窒素雰囲気中、４００℃／３０分保持することにより硬化させた。得られた硬化膜の比誘電率は、水銀プローブ法で、動作周波数１ＭＨｚのＣ―Ｖ測定（エス・エス・エム社製、ＳＳＭ４９５型）を用い測定した。また、硬度、弾性率は、ＨＹＳＩＴＲＯＮ社製Ｈｙｓｉｔｏｒｏｎ ＴｒｉｂｏＳｃｏｐｅ Ｍｉｃｒｏｍｅｃｈａｎｉｃａｌ Ｔｅｓｔ装置を用い測定した。結果を表１に示す。
【００４９】
実施例２
塗布液１の代わりに塗布液２を用いた以外は実施例１に準拠して塗布膜を製造し、比誘電率、硬度、弾性率を測定した。結果を表１に示す。
【００５０】
実施例３
塗布液１の代わりに塗布液３を用いた以外は実施例１に準拠して塗布膜を製造し、比誘電率、硬度、弾性率を測定した。結果を表１に示す。
【００５１】
実施例４
塗布液１の代わりに塗布液４を用いた以外は実施例１に準拠して塗布膜を製造し、比誘電率、硬度、弾性率を測定した。結果を表１に示す。
【００５２】
実施例５
塗布液１の代わりに塗布液５を用いた以外は実施例１に準拠して塗布膜を製造し、比誘電率、硬度、弾性率を測定した。結果を表１に示す。
【００５３】
実施例６
塗布液１の代わりに塗布液６を用いた以外は実施例１に準拠して塗布膜を製造し、比誘電率、硬度、弾性率を測定した。結果を表１に示す。
【００５４】
実施例７
塗布液１の代わりに塗布液７を用いた以外は実施例１に準拠して塗布膜を製造し、比誘電率、硬度、弾性率を測定した。結果を表１に示す。
【００５５】
比較例１
塗布液１の代わりに塗布液８を用いた以外は実施例１に準拠して塗布膜を製造し、比誘電率、硬度、弾性率を測定した。結果を表１に示す。
【００５６】
比較例２
塗布液１の代わりに塗布液９を用いた以外は実施例１に準拠して塗布膜を製造し、比誘電率、硬度、弾性率を測定した。結果を表１に示す。
【００５７】
比較例３
塗布液１の代わりに塗布液１０を用いた以外は実施例１に準拠して塗布膜を製造し、比誘電率、硬度、弾性率を測定した。結果を表１に示す。
【００５８】
【表１】

【００５９】
実施例１〜７の硬化膜の硬度、弾性率は、それぞれ１ＧＰａ以上、１０ＧＰａ以上であり、分子内にエチニル基を２個有するモノマーである比較例１〜３に比べて優れた値を示した。
【００６０】
【発明の効果】
本発明によれば、高い機械強度を有する有機絶縁膜を形成し得る有機絶縁膜形成用組成物を提供することが可能となる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a composition for forming an organic insulating film.
[0002]
[Prior art]
In recent years, in the field of electronic materials, the delay time due to an increase in inter-wire resistance and an increase in electric capacity has become a serious problem as semiconductors are highly integrated, increased in speed, and improved in performance. In order to reduce the delay time and increase the speed of the device, it is necessary to use an insulating film having a low dielectric constant.
By the way, in the process of forming a fine wiring in an insulating film with a low dielectric constant, the wiring is formed after patterning on the insulating film, but chemical mechanical polishing (hereinafter referred to as chemical mechanical polishing) (hereinafter referred to as chemical mechanical polishing) is performed for planarization. CMP)) is performed. In this CMP, a high mechanical strength is required for the insulating film.
As a material for an insulating film having a low dielectric constant, for example, a composition comprising a polymer obtained by polymerizing 1,2-diiodobenzene and 4,4′-diethynyldiphenyl ether in the presence of a palladium catalyst is known. However, the mechanical strength of the insulating film obtained from the composition cannot be said to be sufficient.
[0003]
[Patent Document 1]
JP 2002-322246 A
[0004]
[Problems to be solved by the invention]
The objective of this invention is providing the composition for organic insulating film formation which can form the organic insulating film which has high mechanical strength.
[0005]
[Means for Solving the Problems]
As a result of intensive investigations to find a composition for forming an organic insulating film that can solve the above-described problems, the present inventors contain a compound having three or more —C≡CH groups in the molecule. The present inventors have found that the composition can form an organic insulating film having high mechanical strength, and have completed the present invention.
[0006]
That is, the present invention provides a composition for forming an organic insulating film characterized by containing a compound having at least three —C≡CH groups in the molecule.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The composition for forming an organic insulating film of the present invention contains a compound having at least three —C≡CH groups in the molecule. It is preferable that the composition for forming an organic insulating film of the present invention does not contain a heat transpiration compound and / or a heat decomposable compound used when forming an organic insulating film having a porous chamber.
[0008]
The compound having at least three —C≡CH groups in the molecule is preferably at least one compound selected from the group consisting of compounds represented by the following formulas (1) and (2).

[0009]
In the formula (1), n represents 3 or 4, and X¹Has an alicyclic hydrocarbon group having 4 to 20 carbon atoms which may be substituted with a group other than —C≡CH group, or an aromatic ring which may be substituted with a group other than —C≡CH group Represents the group Y¹, Z¹Each independently represents a single bond, a group having an aromatic ring which may be substituted with a group other than —C≡CH group, —O— or —CO—.
[0010]
In formula (1), X¹In C., the alicyclic hydrocarbon group having 4 to 20 carbon atoms includes, for example, a trivalent or tetravalent group having a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, an adamantane ring, a norbornene ring, or the like. It is done.
Examples of the substituent other than —C≡CH group include an alkyl group, an alkoxy group, an alkenyl group, an alkynyl group having 3 to 10 carbon atoms, an aryl group, an optionally substituted trialkylsilyl group, and a hydroxyl group. Etc.
Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, and a hexyl group.
Examples of the alkoxy group include a methoxy group, an ethoxy group, and a propoxy group.
Examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, a 2-methylallyl group, and a butadienyl group.
Examples of the alkynyl group having 3 to 10 carbon atoms include a propargyl group, a butynyl group, a pentynyl group, a butadiynyl group, and a heptynyl group.
Examples of the aryl group include a phenyl group, a diphenyl group, a naphthyl group, an anthracenyl group, and a fluorenyl group.
Examples of the trialkylsilyl group which may have a substituent include a trimethylsilyl group, a triethylsilyl group, a triisopropylsilyl group, and a dimethylethylsilyl group.
[0011]
Examples of the group having an aromatic ring include a trivalent or tetravalent group having a benzene ring, a diphenyl ring, a naphthalene ring, an anthracene ring, a fluorene ring, and the like.
Examples of the substituent other than —C≡CH group include an alkyl group, an alkoxy group, an alkenyl group, an alkynyl group having 3 to 10 carbon atoms, an aryl group, an optionally substituted trialkylsilyl group, and a hydroxyl group. Etc.
Here, as the alkyl group, the alkoxy group, the alkenyl group, the alkynyl group having 3 to 10 carbon atoms, the aryl group, and the trialkylsilyl group which may have a substituent, the same ones as described above may be mentioned.
[0012]
In formula (1), Y¹, Z¹Examples of the group having an aromatic ring include a divalent group having a benzene ring, a diphenyl ring, a naphthalene ring, an anthracene ring, and a fluorene ring.
Examples of the substituent other than —C≡CH group include an alkyl group, an alkoxy group, an alkenyl group, an alkynyl group having 3 to 10 carbon atoms, an aryl group, an optionally substituted trialkylsilyl group, and a hydroxyl group. Etc.
Examples of the alkyl group, alkoxy group, alkenyl group, alkynyl group having 3 to 10 carbon atoms, aryl group, and trialkylsilyl group which may have a substituent include the same groups as described above.
[0013]
From the viewpoint of heat resistance, X in the formula (1)¹Is preferably a trivalent or tetravalent group having a benzene ring, diphenyl ring, naphthalene ring, anthracene ring or adamantane ring, more preferably a trivalent or tetravalent group having a benzene ring or an adamantane ring. preferable.
[0014]
Further, from the viewpoint of heat resistance, Y in the formula (1)¹Is a divalent group having a benzene ring, diphenyl ring, naphthalene ring, anthracene ring, adamantane ring,¹Is an oxygen atom or Y¹And Z¹Are preferably single bonds, Y¹Is a divalent group having a benzene ring and Z¹Is an oxygen atom or Y¹And Z¹Are more preferably a single bond.
[0015]
Among these, X in the formula (1)¹Is a trivalent or tetravalent group having a benzene ring or an adamantane ring,¹Is a divalent group having a benzene ring and Z¹Is an oxygen atom or X¹Is a trivalent or tetravalent group having a benzene ring or an adamantane ring,¹, Z¹More preferably, both are single bonds.
[0016]
The compound represented by the formula (1) is particularly preferably at least one of the following compounds.

[0017]
In the formula (2), m represents 2 or 3, and X²Is -C (R¹) (R²)-,> C (R³)-, A group having an alicyclic hydrocarbon having 4 to 20 carbon atoms which may be substituted with a group other than -C≡CH group, an aromatic ring which may be substituted with a group other than -C≡CH group Represents a group having-, -O- or -CO-, R¹~ R³Each independently represents a hydrogen atom, a hydroxyl group, or an optionally substituted alkyl group having 1 to 10 carbon atoms;², Z²Each independently represents a single bond, a group having an aromatic ring which may be substituted with a group other than —C≡CH group, —O— or —CO—.
[0018]
In formula (2), X²As the alicyclic hydrocarbon group having 4 to 20 carbon atoms, for example, a divalent or trivalent group having a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, an adamantane ring, a norbornene ring, etc. Can be mentioned.
Examples of the group having an aromatic ring include a divalent or trivalent group having a benzene ring, a diphenyl ring, a naphthalene ring, an anthracene ring, a fluorene ring, and the like.
Examples of the substituent other than —C≡CH group include an alkyl group, an alkoxy group, an alkenyl group, an alkynyl group having 3 to 10 carbon atoms, an aryl group, an optionally substituted trialkylsilyl group, and a hydroxyl group. Etc.
Here, as the alkyl group, the alkoxy group, the alkenyl group, the alkynyl group having 3 to 10 carbon atoms, the aryl group, and the trialkylsilyl group which may have a substituent, the same ones as described above may be mentioned.
[0019]
In formula (2), R¹~ R³Examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, and hexyl group.
Examples of the alkyl group substituent having 1 to 10 carbon atoms include an alkoxy group, an alkenyl group, an alkynyl group having 3 to 10 carbon atoms, an aryl group, an optionally substituted trialkylsilyl group, and a hydroxyl group. Can be mentioned.
Here, the same thing as the above is mentioned as an alkoxy group, an alkenyl group, a C3-C10 alkynyl group, an aryl group, and the trialkylsilyl group which may have a substituent.
[0020]
In formula (2), Y², Z²In the above, examples of the group having an aromatic ring include a divalent group having a benzene ring, a diphenyl ring, a naphthalene ring, an anthracene ring, a fluorene ring, and the like.
Examples of the substituent other than —C≡CH group include an alkyl group, an alkoxy group, an alkenyl group, an alkynyl group having 3 to 10 carbon atoms, an aryl group, an optionally substituted trialkylsilyl group, and a hydroxyl group. Etc.
Here, as the alkyl group, the alkoxy group, the alkenyl group, the alkynyl group having 3 to 10 carbon atoms, the aryl group, and the trialkylsilyl group which may have a substituent, the same ones as described above may be mentioned.
[0021]
From the viewpoint of heat resistance, X in the formula (2)²Is preferably a divalent or trivalent group having a benzene ring, diphenyl ring, naphthalene ring, anthracene ring, fluorene ring, cyclohexane ring, adamantane ring, carbonyl group, alkylidene group, alkylidyne group, fluorene ring, cyclohexane It is more preferably a ring, a divalent or trivalent group having an adamantane ring, a carbonyl group, an alkylidene group, or an alkylidine group.
[0022]
Further, from the viewpoint of heat resistance, Y in the formula (2)²Is a divalent group having a benzene ring group, a diphenyl ring or a naphthalene ring, an anthracene ring or an adamantane ring;²Is an oxygen atom or Y²And Z²Are preferably single bonds, Y²Is a divalent group having a benzene ring and Z²Is an oxygen atom or Y²And Z²Are more preferably a single bond.
[0023]
Among these, X in the formula (2)²Is a divalent or trivalent group having a fluorene ring, a cyclohexane ring or an adamantane ring, a carbonyl group, an alkylidene group or an alkylidine group,²Is a divalent group having a benzene ring and Z²Is an oxygen atom or X²Is a divalent or trivalent group having a fluorene ring, a cyclohexane ring or an adamantane ring, a carbonyl group, an alkylidene group or an alkylidine group,², Z²More preferably, both are single bonds.
[0024]
The compound represented by the formula (2) is particularly preferably at least one of the following compounds.

[0025]
The weight average molecular weight in terms of polystyrene by GPC of a compound having at least three —C≡CH groups in the molecule is preferably 5000 or less, more preferably 3000 or less, and even more preferably 1500 or less.
When the molecular weight exceeds 5000, the proportion of —C≡CH groups in the molecule decreases, so that the crosslinking density decreases, and the hardness and elastic modulus tend to be insufficient.
[0026]
The composition for forming an organic insulating film of the present invention contains a compound having at least three —C≡CH groups in the molecule, but may further contain an organic solvent to form a coating solution.
The organic solvent is not particularly limited as long as it can dissolve a compound having at least three —C≡CH groups in the molecule.
Examples of the organic solvent include alcohol solvents such as methanol, ethanol, isopropanol, 1-butanol, 2-ethoxymethanol, 3-methoxypropanol, acetylacetone, methylethylketone, methylisobutylketone, 3-pentanone, 2-heptanone, 3 -Ketone solvents such as heptanone and cyclohexanone, propyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, methyl propionate, ethyl propionate, methyl butyrate, propylene glycol monomethyl ether acetate, ethyl lactate and other ester solvents, diisopropyl ether, Ether solvents such as dibutyl ether, dioxane, anisole, phenetol, veratrol, diphenyl ether, benzene, toluene, mesitylene, ethylbenzene Aromatic hydrocarbon solvents, halogen solvents such as chloroform, chlorobenzene, dichloroethylene, trichloroethylene, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N-methylpropionamide, N- Examples include amide solvents such as methylpyrrolidone, and aliphatic hydrocarbon solvents such as pentane, hexane, and heptane, and these are preferably used because they are easily available industrially.
[0027]
These organic solvents can be arbitrarily selected as long as the solubility of the compound having at least three —C≡CH groups in the molecule and the coating property of the coating solution itself can be maintained satisfactorily. Two or more kinds may be used in combination.
[0028]
When used as a coating liquid in which the organic solvent is blended, the total solid content concentration, that is, [a compound having at least three —C≡CH groups in the molecule / [having at least three —C≡CH groups in the molecule] Compound + amount of organic solvent]] × 100 is preferably 5 to 50%. The concentration can be appropriately adjusted in accordance with the purpose of improving the film thickness of the obtained coating film and the step embedding property.
[0029]
You may mix | blend an additive further with the composition for organic insulating film formation of this invention.
Examples of the additive include coupling agents such as silane coupling agents and titanium coupling agents, catalysts such as surfactants, foam stabilizers, and organic peroxides.
Coupling agents may be added to improve adhesion to the substrate, surfactants may be added to stabilize coatability, and organic peroxides and other catalysts may be added to reduce the crosslinking temperature of the monomers. Good.
[0030]
Examples of the substrate used for forming the organic insulating film include glass, quartz, metal, ceramic, silicon, GaAs, and SiO.₂, SiN, SiC and the like.
[0031]
Examples of the method for applying the composition for forming an organic insulating film to the substrate include spin coating, roller coating, dip coating, and spraying.
[0032]
Examples of the method for crosslinking a composition containing a compound having at least three —C≡CH groups in the molecule applied to the substrate include a heat treatment method and an ultraviolet irradiation method.
Examples of the heat treatment method include a method using an oven, a hot plate, a furnace, and the like, and light irradiation heating using a xenon lamp by an RTP (lamp heater).
[0033]
The heat treatment is preferably performed in an atmosphere having an oxygen concentration of less than 1%, and more preferably performed in an atmosphere having an oxygen concentration of less than 100 ppm.
Examples of the atmosphere having an oxygen concentration of less than 1% include a reduced pressure atmosphere, an inert gas atmosphere, and a vacuum.
The reduced pressure atmosphere is preferably about 1 to 20 Pa.
Examples of the inert gas include helium, nitrogen, and argon.
It is preferable that the temperature of heat processing is 400 degrees C or less. By heating at 400 ° C. or lower, there is a tendency that decomposition of a compound having at least three —C≡CH groups in the molecule applied to the substrate can be suppressed.
[0034]
The hardness and elastic modulus of the obtained organic insulating film are the hardness and elastic modulus in the vicinity of the surface of the organic insulating film, and are values measured by a nanoindentation method using a Hysitron TriScope Micromechanical Test apparatus manufactured by HYSITRON. The vicinity of the surface means a depth of 1/10 to 1/6 of the thickness of the organic insulating film, specifically, 15 nm to 50 nm. In addition, a Belkovic indenter (manufactured by Diamond) was used for measurement of hardness and elastic modulus.
The organic insulating film preferably has a hardness of 1 GPa or more and an elastic modulus of 10 GPa or more.
[0035]
Since the organic insulating film obtained from the composition for forming an organic insulating film of the present invention can be crosslinked at a relatively low temperature, it can be easily produced in a short time.
The organic insulating film has a low dielectric constant, high hardness, high elastic modulus, and excellent heat resistance and chemical resistance. Therefore, it is suitably used as an insulating film for electronic materials such as semiconductors. The
[0036]
【Example】
EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, it cannot be overemphasized that this invention is not limited by an Example.
[0037]
Production Example 1
Production of Compound A
A 1000 mL four-necked flask was charged with 30.0 g (102 mmol) of dibromoadamantane, 160.2 g (1.02 mol) of bromobenzene and 570 g of dichloromethane, and cooled to 5 ° C. with ice water. To this, 0.83 g (5.1 mmol) of anhydrous iron (III) chloride was added, and stirring was continued while raising the temperature to room temperature over 12 hours. The reaction solution was added to 300 g of 1N hydrochloric acid, and the aqueous layer was removed after stirring. The organic layer was washed once with 100 g of 1N hydrochloric acid and further washed four times with 100 g of ion-exchanged water. Dichloromethane and excess bromobenzene were removed by distillation under reduced pressure, and then 300 g of methanol was added to the residue and stirred. The precipitated oily substance was taken out, dissolved by adding 30 g of tetrahydrofuran, and dropped into 300 g of methanol. The precipitated oily substance was taken out and dried under reduced pressure to obtain 38.5 g of an oily substance. 37.4 g of this oily substance was charged into a 1000 mL four-necked flask, and 4.36 g of tetrakis (triphenylphosphine) palladium, 1.44 g of copper (I) iodide and 374 g of triethylamine were added to dissolve the oily substance. The trimethylsilyl acetylene 41.2g was dripped here over 1 hour, and it heated up to 80 degreeC. The mixture was reacted at the same temperature for 8 hours, further cooled to room temperature, and then stirred for 16 hours. Insoluble matter was filtered off and washed with 150 g of toluene. The filtrate and washings were mixed and concentrated, and the residue was purified with a column (stationary phase; silica gel 60, developing solution; hexane / toluene). 7.80 g of the main product was dissolved in a mixed solvent of 78 g of methanol and 234 g of tetrahydrofuran, 1.65 g of potassium carbonate was added, and the mixture was stirred at room temperature for 10 hours. The solvent was distilled off under reduced pressure, and 80 g of toluene and 30 g of 1N hydrochloric acid were added to the residue. After stirring, the aqueous layer was removed. Further, 20 g of 1N hydrochloric acid was added, and after stirring, the aqueous layer was removed. The organic layer was washed 3 times with 30 mL of ion-exchanged water, further washed twice with 30 g of 1% oxalic acid water and 4 times with 30 mL of ion-exchanged water, and toluene was distilled off under reduced pressure. 4.2 g of 1,3,5-tris (4-ethynylphenyl) adamantane was obtained. This is designated Compound A.
[0038]
Production Example 2
Production of compound B
A 200 mL four-necked flask was charged with 5.0 g (17 mmol) of dibromoadamantane, 2.3 g (9 mmol) of aluminum bromide and 100 mL of m-dibromobenzene, and stirred at 60 ° C. for 10 hours. After cooling, the reaction solution was added to 150 g of ice water in which 10 g of concentrated hydrochloric acid was dissolved, and the aqueous phase was removed after stirring. After excess dibromobenzene was removed by distillation under reduced pressure, 100 mL of methylene chloride was added to and dissolved in the residue, washed with water and brine, and then dried over magnesium sulfate. After filtering off the desiccant, methylene chloride was concentrated with an evaporator, and 100 mL of methanol was added and stirred. The precipitated crystals were filtered off and dried under reduced pressure. 6.0 g of this crystal was charged into a 200 mL four-necked flask, 200 mg of dichlorobis (triphenylphosphine) palladium, 400 mg of triphenylphosphine, 180 mg of copper (I) iodide and 100 mL of triethylamine were added, and the temperature was raised to 70 to 80 ° C. Trimethylsilylacetylene 6.7g was dripped over 1 hour, and it was made to react at the same temperature for 4 hours. After cooling, the solvent was distilled off, 200 mL of diethyl ether was added to the residue, and the insoluble salt was filtered off. The filtrate was washed with 1N hydrochloric acid, saturated brine and ultrapure water, and the ether phase was dried over magnesium sulfate. The desiccant was filtered off, the ether was distilled off, and the residue was produced on a column (stationary phase; silica gel 60, developing solution; hexane / methylene chloride). 5.9 g of the main product was dissolved in 150 mL of methanol and 100 mL of tetrahydrofuran, 0.5 g of potassium carbonate was added, and the mixture was stirred at room temperature for 4 hours. The solvent was distilled off under reduced pressure, and 200 mL of methylene chloride and 100 mL of 1N hydrochloric acid were added to the residue. After stirring, the hydrochloric acid phase was removed. The methylene chloride phase was washed 3 times with 100 mL of ultrapure water, and the solvent was distilled off from the methylene chloride phase and dried under reduced pressure to obtain 3.2 g of bis (diethynylphenyl) adamantane. This is designated Compound B.
[0039]
Production Example 3
Production of Compound C
In a 500 mL four-necked flask, 6.4 g (20 mmol) of 1,3-bis (4-hydroxyphenyl) adamantane, 10.4 g (41 mmol) of 1,3-dibromo-5-fluorobenzene and 22.4 g (60 mmol) of potassium carbonate, 168 g of toluene and 84 g of dimethyl sulfoxide were charged, the temperature was gradually raised to 120 ° C., and the temperature was kept at this temperature for 45 hours. After cooling to room temperature, 150 g of ion-exchanged water and 21 g of acetic acid were added, and after stirring, the aqueous layer was removed. The organic layer was further washed with 100 g of ion exchange water and concentrated under reduced pressure. 20 g of toluene was added thereto, the temperature was raised to 60 ° C., 70 g of methanol was added, and the mixture was gradually cooled to room temperature. The precipitated crystals were collected by filtration and washed with 100 g of methanol. As a white crystal, 15.4 g (yield 98%) of 1,3-bis (4- (3,5-dibromophenyloxy) phenyl) adamantane was obtained.
14.3 g (18 mmol) of 1,3-bis (4- (3,5-dibromophenyloxy) phenyl) adamantane was charged into a 500 mL four-necked flask, and 0.62 g of tetrakis (triphenylphosphine) palladium, copper iodide (I ) 0.21 g, 142 g triethylamine and 100 g toluene. Here, 10.6 g of trimethylsilylacetylene was added dropwise over 1 hour, and the temperature was raised to 80 ° C. The reaction was carried out at the same temperature for 40 hours. During this time, 3.7 g and 3.6 g of trimethylsilylacetylene were added at 12 and 26 hours, respectively. After cooling to room temperature, insoluble matters were filtered off and washed with 120 g of toluene. The filtrate and washings were mixed and concentrated, and the residue was purified with a column (stationary phase; silica gel 60, developing solution; hexane / toluene). As the main product, 12.6 g (yield 82%) of 1,3-bis (4- (3,5-bis (trimethylsilylethynyl) phenyloxy) phenyl) adamantane was obtained.
12.0 g (14 mmol) of 1,3-bis (4- (3,5-bis (trimethylsilylethynyl) phenyloxy) phenyl) adamantane is dissolved in a mixed solvent of 120 g of methanol and 240 g of tetrahydrofuran, and 1.93 g of potassium carbonate is added. And stirred at room temperature for 10 hours. The solvent was distilled off under reduced pressure, and 50 g of toluene was added to the residue, followed by neutralization by adding 2.4 g of acetic acid and 25 g of ion-exchanged water, and the aqueous layer was removed. The organic layer was washed once with 20 g of 1N hydrochloric acid and four times with 25 mL of ion-exchanged water. Furthermore, it was washed twice with 30 g of 1% oxalic acid water and four times with 20 mL of ion-exchanged water, and toluene was distilled off under reduced pressure. 50 g of methanol was added to the residue. The crystals were collected by filtration and washed with 50 g of methanol. 6.4 g (yield 80%) of 1,3-bis (4- (3,5-diethynylphenyloxy) phenyl) adamantane was obtained. This is designated Compound C.
[0040]
Production Example 4
Production of compound D
In a 500 mL four-necked flask, 4,4 ′-(9H-fluorene-9-ylidene) bisphenol (8.8 g), 1,3-dibromo-5-fluorobenzene (12.7 g), potassium carbonate (13.8 g) , Toluene (100 g) and DMSO (200 g) were charged, and the mixture was stirred while maintaining a temperature of 120 ° C./5 hr under a nitrogen stream. Toluene, acetic acid and water were added for liquid separation, and the oil layer was distilled off under reduced pressure to obtain a tetrabromo intermediate D1.
A 500 mL four-necked flask was charged with a part (11.6 g) of intermediate D1 obtained above, triethylamine (200 g), and CuI (I) (0.5 g), and stirred at room temperature for 30 minutes under an Ar stream. Went. Pd (0) (TPP)₄(1.8 g) and trimethylsilylacetylene (7.9 g) were charged, and the mixture was heated to 80 ° C. and stirred for 5 hours while maintaining the temperature. After filtering the reaction mass and concentrating the filtrate, column treatment was performed with toluene and concentration was performed to obtain an intermediate D2 which is a tetra (trimethylsilylethynyl) isomer.
Intermediate D2 obtained above was charged as it was into a 300 mL four-necked flask, 50 g of toluene, 50 g of methanol, and 11.6 g of potassium carbonate were charged, and the mixture was stirred at room temperature for 18 hours. The reaction mass was neutralized with acetic acid as it was, and after adding toluene and washing with water, toluene was distilled off under reduced pressure. The obtained tetraethynyl monomer is referred to as Compound D.
[0041]
Production Example 5
Production of Compound E
The same treatment as in Production Example 2 was carried out except that dibromoadamantane was changed to tribromoadamantane to obtain 4.5 g of tris (diethynylphenyl) adamantane. This is designated Compound E.
[0042]
Production Example 6
Production of compound F
In a 500 mL four-necked flask, 1,1 ′, 1 ″ -trihydroxyphenylethane (6.1 g), 1,3-dibromo-5-fluorobenzene (15.2 g), potassium carbonate (13.8 g), toluene ( 100 g) and DMSO (200 g) were added, and the mixture was stirred under a nitrogen stream at 120 ° C. for 5 hr, and separated by adding toluene, acetic acid, and water, and the oil layer was distilled off under reduced pressure to obtain an intermediate F1 that is a hexabromo compound. Using this hexabromo compound, ethynyl coupling and elimination of the protecting group were carried out in the same manner as in Production Example 4 to obtain compound F.
[0043]
Production Example 7
Production of compound G
A 500 mL four-necked flask is charged with 4,4′-difluorobenzophenone (5.5 g), 2,4-dibromophenol (12.6 g), potassium carbonate (13.8 g), toluene (100 g), DMSO (200 g). Then, the mixture was stirred while maintaining a temperature of 120 ° C./5 hr under a nitrogen stream. Toluene, acetic acid and water were added for liquid separation, and the oil layer was distilled off under reduced pressure to obtain Intermediate G1. Using this tetrabromo compound, ethynyl coupling and removal of the protecting group were carried out in the same manner as in Production Example 4 to obtain compound G.
[0044]
Production Example 8
Production of compound H
A 500 mL four-necked flask was charged with 5.03 g (19 mmol) of anhydrous aluminum bromide and cooled to 5 ° C. A mixture of 15.0 g (51 mmol) of dibromoadamantane and 260.2 g (1.28 mol) of iodobenzene was charged. Stirring was continued while raising the temperature to room temperature over 12 hours. The temperature was further raised to 60 ° C., and the temperature was kept at this temperature for 4 hours. After cooling, the reaction solution was poured into a mixed solution of 20 g of concentrated hydrochloric acid and 120 g of ion exchange water. The mixture was separated, and the organic layer was washed 3 times with 100 g of a 10% aqueous sodium sulfite solution and 3 times with 100 g of ion-exchanged water. To the obtained organic layer, 400 g of methanol was added and stirred. The precipitated oily matter was taken out, 200 g of methanol was added and stirred. The precipitated oily substance was taken out, and 200 g of methanol was further added and stirred. The obtained oily substance was dissolved in 40 g of tetrahydrofuran and dropped into 200 g of methanol. The precipitated crystals were collected by filtration, dissolved in 40 g of tetrahydrofuran, and dropped into 200 g of methanol. The precipitated crystals were collected by filtration and dried to obtain 18.5 g of white crystals. 17.8 g of this crystal was charged into a 500 mL four-necked flask, and 0.57 g of tetrakis (triphenylphosphine) palladium, 0.19 g of copper (I) iodide and 178 g of triethylamine were added. To this, 13.0 g of trimethylsilylacetylene was added dropwise, and the temperature was raised to 80 ° C. The reaction was carried out at the same temperature for 4 hours, and after further cooling to room temperature, stirring was continued for 16 hours. Insoluble material was filtered off and washed with 75 g of toluene. The filtrate and washings were mixed and concentrated, and the residue was purified with a column (stationary phase; silica gel 60, developing solution; hexane / toluene). 12.2 g of the main product was dissolved in a mixed solvent of 122 g of methanol and 244 g of tetrahydrofuran, 1.16 g of potassium carbonate was added, and the mixture was stirred at room temperature for 1 hour. The solvent was distilled off under reduced pressure, and 150 g of dichloromethane and 100 g of 1N hydrochloric acid were added to the residue. After stirring, the aqueous layer was removed. Further, the organic layer was washed with 100 mL of ion exchange water, further washed twice with 75 g of 1% oxalic acid water and 3 times with 75 mL of ion exchange water, and dichloromethane was distilled off under reduced pressure. The obtained crystal is referred to as Compound H.
[0045]
Production Example 9
Preparation of Compound I
A 500 mL four-necked flask was charged with 10.0 g (34 mmol) of dibromoadamantane, 84.7 g (0.34 mol) of 4-bromodiphenyl ether and 170 g of dichloromethane, and cooled to 5 ° C. with ice water. To this, 0.28 g (1.7 mmol) of anhydrous iron (III) chloride was added. Stirring was continued at this temperature for 6 hours, the temperature was further raised to room temperature, and stirring was continued at this temperature for 10 hours. 80 g of dichloromethane was added to the reaction solution, and the mixture was washed twice with 200 g of ion-exchanged water and further twice with 100 g. After the dichloromethane was removed by distillation under reduced pressure, the residue was purified with a column (stationary phase; silica gel 60, developing solution; hexane / toluene). 9.2 g of 1,3-bis (4- (4-bromophenyloxy) phenyl) adamantane was obtained as an oil. This oily substance was charged into a 200 mL four-necked flask, and 0.50 g of tetrakis (triphenylphosphine) palladium, 0.17 g of copper (I) iodide and 92 g of triethylamine were added to dissolve the oily substance. Here, 4.3 g of trimethylsilylacetylene was dropped over 1 hour, and the temperature was raised to 80 ° C. The reaction was carried out at the same temperature for 55 hours. During this time, 6.5 g and 5.8 g of trimethylsilylacetylene were added at 20 and 34 hours, respectively. After cooling to room temperature, the insoluble material was filtered off and washed with 70 g of toluene. The filtrate and washings were mixed and concentrated, and the residue was purified with a column (stationary phase; silica gel 60, developing solution; hexane / toluene). 4.0 g of the main product was dissolved in a mixed solvent of 40 g of methanol and 120 g of tetrahydrofuran, 0.83 g of potassium carbonate was added, and the mixture was stirred at room temperature for 28 hours. The solvent was distilled off under reduced pressure, and 30 g of toluene, 7 g of 2N hydrochloric acid and 10 g of ion-exchanged water were added to the residue, and the aqueous layer was removed after stirring. Further, 3 g of 1N hydrochloric acid and 10 g of ion-exchanged water were added, and after stirring, the aqueous layer was removed. The organic layer was washed 3 times with 10 mL of ion-exchanged water, further washed twice with 10 g of 1% oxalic acid water and 3 times with 10 mL of ion-exchanged water, and toluene was distilled off under reduced pressure. 2.7 g of 1,3-bis (4- (4-ethynylphenyloxy) phenyl) adamantane was obtained. This is designated Compound I.
[0046]
Production Example 10
Production of Compound J
20.8 g (0.1 mol) of bromoadamantane, 8.5 g (0.05 mol) of diphenyl ether and 50 mL of carbon tetrachloride were charged into a 200 mL four-necked flask, and cooled with an ice bath, 10.8 g (0.08 mol) of aluminum chloride. Was charged in small portions over an hour. Under cooling, the temperature was returned to room temperature for 1 hour, an oil bath was further installed, and the reaction was carried out at an internal temperature of 40 ° C. for 4 hours. Once again, an ice bath was set to bring the internal temperature to 10 ° C. or lower, and 80 mL of 1N HCl was added dropwise. Next, 50 mL of THF was charged to dissolve the product, and then the insoluble salt was filtered through a filter precoated with Celite 515, and the aqueous phase was removed from the filtrate. Next, the carbon tetrachloride phase was washed with a saturated saline solution and then dried over magnesium sulfate. The desiccant was filtered off and the solvent was distilled off under reduced pressure. To the residue, 250 g of methanol was added and stirred, and the precipitated crystals were filtered and dried under reduced pressure to obtain 21 g of bisadamantyl diphenyl ether. This was charged into a 100 mL four-necked flask together with 5.0 g (11 mmol) and bromine 12 mL (23 mmol), and reacted for 4 hours while cooling in an ice bath. After 150 mL of methylene chloride was added to dissolve the contents, the solution was added dropwise to 500 mL of a 10% aqueous sodium sulfite solution. After removing the aqueous phase and washing with ion exchange water, methylene chloride was removed. After adding 25 g of THF to the residue and dissolving it, it was poured into 300 mL of methanol to precipitate crystals. The crystals were filtered and dried under intraocular pressure to obtain 5.2 g of bisadamantyl dibromodiphenyl ether. 3 g of this was collected and put into a 100 mL four-necked flask together with 20 mg of bis (triphenylphosphine) dichloropalladium, 80 mg of copper iodide, 40 mg of triphenylphosphine and 50 mL of triethylamine, and the temperature was raised to 75 ° C. 1.48 g of trimethylsilylacetylene was added dropwise over 30 minutes and reacted at the same temperature for 6 hours. After cooling, insoluble salts were filtered off from the reaction mass, triethylamine was distilled off from the filtrate, 100 mL of methylene chloride was added to the residue, washed with 50 mL of 1N HCl, and the organic phase was further washed with ion-exchanged water. Methylene chloride was distilled off from the organic phase, and the residue was purified by silica gel column chromatography (stationary phase: silica gel 60, developing phase methylene chloride / n-hexane = 1/2). The main component fractions were collected, the developing phase was distilled off, 50 mL of methanol, 50 mL of THF and 0.5 g of sodium carbonate were added to the residue and stirred at room temperature for 4 hours. The solvent was distilled off, 100 mL of methylene chloride was added to the residue, washed with 50 mL of 1N HCl, and further washed with ion-exchanged water. The organic phase was concentrated to about 20 mL and poured into 200 mL of methanol to obtain 1.2 g of bisadamantyldiethynyl diphenyl ether. This is designated Compound J.
[0047]
Preparation of coating solution
Coating liquid 1
Compound A obtained in Production Example 1 was adjusted with anisole to a solid content of 10% by weight. Further, the prepared solution was filtered by a known method with a 0.1 μm PTFE filter to prepare a coating solution.
Coating liquid 2
A coating solution was prepared according to the coating solution 1 except that the compound B obtained in Production Example 2 was used instead of the compound A obtained in Production Example 1.
Coating liquid 3
A coating solution was prepared according to the coating solution 1 except that the compound C obtained in Production Example 3 was used instead of the compound A obtained in Production Example 1.
Coating liquid 4
A coating solution was prepared according to the coating solution 1 except that the compound D obtained in Production Example 4 was used instead of the compound A obtained in Production Example 1.
Coating liquid 5
A coating solution was prepared according to the coating solution 1 except that the compound E obtained in Production Example 5 was used instead of the compound A obtained in Production Example 1.
Coating liquid 6
A coating solution was prepared according to the coating solution 1 except that the compound F obtained in Production Example 6 was used instead of the compound A obtained in Production Example 1.
Coating liquid 7
Instead of the compound A obtained in Production Example 1, the compound G obtained in Production Example 7 was adjusted with NMP to a solid content of 10% by weight. Further, the prepared solution was filtered by a known method with a 0.1 μm PTFE filter to prepare a coating solution.
Coating liquid 8
A coating solution was prepared according to the coating solution 1 except that the compound H obtained in Production Example 8 was used instead of the compound A obtained in Production Example 1.

Coating liquid 9
A coating solution was prepared according to the coating solution 1 except that the compound I obtained in Production Example 9 was used instead of the compound A obtained in Production Example 1.

Coating solution 10
A coating solution was prepared according to the coating solution 1 except that the compound J obtained in Production Example 10 was used instead of the compound A obtained in Production Example 1.

[0048]
Example 1
About 1 ml of the prepared coating solution 1 was dropped on a 4-inch silicon wafer. The wafer was then spun at 500 rpm for 3 seconds and then spun at 2000 rpm for 15 seconds. The coated wafer was baked at 150 ° C. for 1 minute. The baked wafer was then cured in a furnace by holding it at 400 ° C./30 minutes in a nitrogen atmosphere. The relative dielectric constant of the obtained cured film was measured by a mercury probe method using CV measurement (SSM 495, manufactured by SSM Co.) having an operating frequency of 1 MHz. The hardness and elastic modulus were measured using a Hysitron TriboScope Micromechanical Test apparatus manufactured by HYSITRON. The results are shown in Table 1.
[0049]
Example 2
A coating film was produced according to Example 1 except that the coating solution 2 was used instead of the coating solution 1, and the relative dielectric constant, hardness, and elastic modulus were measured. The results are shown in Table 1.
[0050]
Example 3
A coating film was produced according to Example 1 except that the coating solution 3 was used instead of the coating solution 1, and the relative dielectric constant, hardness, and elastic modulus were measured. The results are shown in Table 1.
[0051]
Example 4
A coating film was produced according to Example 1 except that the coating solution 4 was used instead of the coating solution 1, and the relative dielectric constant, hardness, and elastic modulus were measured. The results are shown in Table 1.
[0052]
Example 5
A coating film was produced according to Example 1 except that the coating solution 5 was used instead of the coating solution 1, and the relative dielectric constant, hardness, and elastic modulus were measured. The results are shown in Table 1.
[0053]
Example 6
A coating film was produced according to Example 1 except that the coating solution 6 was used instead of the coating solution 1, and the relative dielectric constant, hardness, and elastic modulus were measured. The results are shown in Table 1.
[0054]
Example 7
A coating film was produced according to Example 1 except that the coating solution 7 was used instead of the coating solution 1, and the relative dielectric constant, hardness, and elastic modulus were measured. The results are shown in Table 1.
[0055]
Comparative Example 1
A coating film was produced according to Example 1 except that the coating solution 8 was used instead of the coating solution 1, and the relative dielectric constant, hardness, and elastic modulus were measured. The results are shown in Table 1.
[0056]
Comparative Example 2
A coating film was produced according to Example 1 except that the coating solution 9 was used instead of the coating solution 1, and the relative dielectric constant, hardness, and elastic modulus were measured. The results are shown in Table 1.
[0057]
Comparative Example 3
A coating film was produced according to Example 1 except that the coating solution 10 was used instead of the coating solution 1, and the relative dielectric constant, hardness, and elastic modulus were measured. The results are shown in Table 1.
[0058]
[Table 1]

[0059]
The hardness and elastic modulus of the cured films of Examples 1 to 7 were 1 GPa or more and 10 GPa or more, respectively, and showed superior values as compared with Comparative Examples 1 to 3 which are monomers having two ethynyl groups in the molecule. .
[0060]
【The invention's effect】
ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the composition for organic insulating film formation which can form the organic insulating film which has high mechanical strength.

Claims (11)

A composition for forming an organic insulating film, comprising a compound having at least three —C≡CH groups in the molecule. The compound having at least three -C≡CH groups in the molecule is at least one compound selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the formula (2): The composition according to 1.

(In the formula, n represents 3 or 4, m represents 2 or 3, and X ¹ represents an alicyclic hydrocarbon having 4 to 20 carbon atoms which may be substituted with a group other than —C≡CH group. Represents a group having an aromatic ring which may be substituted with a group or a group other than —C≡CH group, and Y ¹ and Z ¹ are each independently a single bond, substituted with a group other than —C≡CH group Represents an optionally substituted aromatic ring group, —O—, or —CO—, and X ² represents —C (R ¹ ) (R ² ) —,> C (R ³ ) —, —C≡CH. An alicyclic hydrocarbon group having 4 to 20 carbon atoms which may be substituted with a group other than the group, a group having an aromatic ring which may be substituted with a group other than —C≡CH group, —O—, or represents ^-CO-, R 1 to R ³ each independently represent a hydrogen atom, a hydroxyl group or an optionally substituted carbon, Represent 1-10 alkyl ^group, Y 2, ^{Z 2} are each independently a single bond, a group having an aromatic ring which may be substituted with a group other than a -C≡CH group, -O-, or - Represents CO-) The composition according to claim 2, wherein X ¹ is a group having a benzene ring or a group having an adamantane ring. The composition according to claim 2 or 3, wherein Y ¹ is a group having a benzene ring, Z ¹ is an oxygen atom, or Y ¹ and Z ¹ are both single bonds. X ² is a carbonyl group, a group having an adamantane ring, a group having a fluorene ring, a group having a cyclohexane ring, an alkylidene group having 1 to 20 carbon atoms, or an alkylidine group having 1 to 20 carbon atoms. The composition in any one of. The composition according to any one of claims 2 to 5, wherein Y ² is a group having a benzene ring, Z ² is an oxygen atom, or Y ² and Z ² are both single bonds. A method for producing an organic insulating film, comprising a step of applying the composition according to any one of claims 1 to 6 to a substrate and performing a heat treatment at an oxygen concentration of less than 1%. The manufacturing method of Claim 7 which heat-processes under pressure reduction, an inert gas atmosphere, or a vacuum. The manufacturing method of Claim 7 or 8 which heat-processes below 400 degreeC. An organic insulating film obtained by the manufacturing method according to claim 7. The organic insulating film according to claim 10, having a hardness of 1 GPa or more and an elastic modulus of 10 GPa or more.