JP4087037B2 - Positive photosensitive resin composition - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は高感度でパターニング特性に優れたポジ型感光性樹脂組成物に関するものである。
【０００２】
【従来の技術】
従来、半導体素子の表面保護膜、層間絶縁膜には、耐熱性が優れ、また卓越した電気特性、機械特性等を有するポリイミド樹脂が用いられているが、近年半導体素子の高集積化、大型化、パッケージの薄型化、小型化、半田リフローによる表面実装への移行により耐熱サイクル性、耐熱ショック性等の著しい向上の要求があり、更に高性能の樹脂が必要とされるようになってきた。
【０００３】
一方、ポリイミド樹脂自身に感光性を付与する技術が最近注目を集めてきており、例えば下記式（４）に示される感光性ポリイミド樹脂が挙げられる。
【化４】
これを用いるとパターン作成工程の一部が簡略化でき、工程短縮および歩留まり向上の効果はあるが、現像の際にＮ−メチル−２−ピロリドン等の溶剤が必要となるため、安全性、取り扱い性に問題がある。
そこで最近、アルカリ水溶液で現像ができるポジ型の感光性樹脂が開発されている。例えば、特開平１−６０６３０号公報においてはヒドロキシポリイミド樹脂から得られたポジ型感光性樹脂組成物が開示されている。
【０００５】
これら感光性樹脂を実際に使用する場合、特に重要となるのは感光性樹脂の感度である。低感度であると露光時間が長くなりスループットが低下するため、より高感度なものが求めらているが、ヒドロキシポリイミド樹脂から得られるポジ型感光性樹脂組成物においては市場の要求を十分に満足させるものはなかった。
【０００６】
【発明が解決しようとする課題】
本発明は高感度でパターニング特性に優れたポジ型感光性樹脂組成物を提供することを目的とする。
【０００７】
本発明は、一般式（１）で示される、３，３´，４，４´―ジフェニルスルホンテトラカルボン酸二無水物とアミノフェノールを反応して得られる、数平均分子量が９，３１２以上のヒドロキシポリイミド（Ａ）１００重量部と、ジアゾナフトキノン化合物（Ｂ）１〜５０重量部とを含むことを特徴とするポジ型感光性樹脂組成物である。
【化５】
【発明の実施の形態】
本発明に用いられる一般式（１）のヒドロキシポリイミドのＸは例えば、
【化６】
【０００９】
また式（１）のＹは例えば、
【化７】
【００１０】
また式（１）のＥは、水素原子、あるいはアルケニル基を少なくとも１つ含む脂肪族または環式化合物のカルボン酸誘導体のいずれであっても良い。後者は例えば、５−ノルボルネン−２，３−ジカルボン酸無水物、無水マレイ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。
【００１１】
本発明に用いる式（２）のビスアミノフェノールのＡは例えば、
【化８】
【００１２】
本発明に用いる式（３）のテトラカルボン酸二無水物のＢは例えば、
【化９】
【００１３】
本発明で用いるジアゾナフトキノン化合物は１，２−ナフトキノンジアジド構造を有する化合物であり、米国特許明細書第２，７７２，９７２号、第２，７９７，２１３号、第３，６６９，６５８号により公知の物質である。
【００１４】
例えば下記のものが挙げられる。
【化１０】
これらの中で特に好ましいものとしては下記のものがある。
【化１２】
また本発明で用いる感光剤（Ｂ）のヒドロキシポリイミド（Ａ）への配合量は、ヒドロキシポリイミド１００重量部に対して１〜５０重量部である。配合量が１重量部未満だと樹脂のパターニング特性が不良となり、逆に５０重量部を越えると感度が大幅に低下するため好ましくない。
【００１７】
本発明におけるポジ型感光性樹脂組成物には、必要によりレベリング剤、シランカップリング剤等の添加剤を添加することができる。
本発明においてはこれらの成分を溶剤に溶解しワニス状にして使用する。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、ピ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ツモノメテルエーテル、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が挙げられ、単独でも混合して用いてもよい。
【００１８】
本発明のポジ型感光性樹脂組成物の使用方法は、まず該組成物を適当な支持体、例えばシリコンウェハー、セラミック基板、アルミ基板等に塗布する。塗布量は、半導体装置の場合、硬化後の最終膜厚が０．１〜２０μｍになるよう塗布する。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ある。
次に６０〜１３０℃でプリベークして塗膜を乾燥した後、所望のパターン形状に化学線を照射する。化学線としては、Ｘ線、電子線、紫外線、可視光線等が使用できるが、２００〜５００ｎｍの波長のものが好ましい。
【００１９】
次に照射部を現像液で溶解除去することによりレリーフパターンを得る。現像液としては、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、珪酸ナトリウム、メタ珪酸ナトリウム、アンモニア水等の無機アルカリ類、エチルアミン。ｎ−プロピルアミン等の第一アミン類、ジエチルアミン、ジ−ｎ−プロピルアミン等の第二アミン類、トリエチルアミン、メチルエチルジアミン等の第三アミン類、ジメチルエタノールアミン、トリエタノールアミン等のアルコールアミン類、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド等の第四級アンモニウム塩等のアルカリ類の水溶液、およびこれにメタノール、エタノールのごときアルコール類等の水溶性有機溶媒や界面活性剤を適当量添加した水溶液を好適に使用することができる。
現像方法としては、スプレー、パドル、浸漬、超音波等の方式が可能である。
【００２０】
次に現像によって形成したレリーフパターンをリンスする。リンス液としては蒸留水を使用する。次に加熱処理を行い、耐熱性に富む最終パターンを得る。
【００２１】
【実施例】
以下、実施例により本発明を具体的に説明する。
＜実施例１＞
＊ヒドロキシポリイミドの合成
温度計、攪拌機、原料仕込口および窒素ガス導入口を備えた３００ｍｌ四つ口セパラブルフラスコ中にヘキサフルオロ−２，２−ビス（３−アミノ−４−ヒドロキシフェニル）プロパン２０．０ｇ（０．０５５モル）と３，３’，４，４’−ジフェニルスルホンテトラカルボン酸二無水物２０．０ｇ（０．０５６モル）とγブチロラクトン１６０．０ｇを加え、２０℃を保持しながら３時間攪拌し、アミド化反応を行った。その後、反応系内にトルエンを３２ｇ加え、１３０〜１４０℃で３時間還流し共沸させることにより、系外に環化反応の副生成物である水を留去した。次にトルエンの減圧留去を３０分間行った後、室温まで冷却した。得られた反応混合液を濾過後、水／メタノール＝３／１の溶液に投入、沈殿物を回収し純水で充分に洗浄した後、真空下で乾燥し目的のヒドロキシポリイミドを得た。
また、得られたヒドロキシポリイミドについて数平均分子量を測定したところ、１４７４２（ｇ／モル）であった。
【００２２】
＊ポジ型感光性樹脂組成物の作製
このヒドロキシポリイミド３０ｇ、下記式の構造を有するジアゾキノン化合物（Ｑ−１）６．０ｇをγ−ブチロラクトン７０ｇに溶解させた後、０．２μｍのテフロンフィルターで濾過し感光性樹脂組成物を得た。
【化１３】
＊特性評価
このポジ型感光性樹脂組成物をシリコンウェハー上にスピンコーターを用いて塗布した後、ホットプレートにて１２０℃で４分乾燥し、膜厚約７．５μｍの塗膜を得た。この塗膜にｇ線ステッパー露光線ＮＳＲ−１５０５Ｇ３Ａ（ニコン（株）製）によりテストパターンを有するマスクを介して２５ｍＪ／ｃｍ2から２５ｍＪ／ｃｍ2ずつ増やして１２５０ｍＪ／ｃｍ2まで露光を行った。
次に２．３８％のテトラアンモニウムヒドロキシド水溶液の現像液に４０秒間浸漬することにより露光部を溶解除去した後、純水で３０秒間リンスした。その結果、露光量４５０ｍＪ／ｃｍ2で照射した部分よりパターンが形成されていることが確認できた。この時の未露光部の膜厚は５μｍであった。
一部の実施例では、パターン形成後のスカム（現像抜け残り）を測定した。
【００２４】
＜実施例２＞
実施例１におけるヘキサフルオロ−２，２−ビス（３−アミノ−４−ヒドロキシフェニル）プロパンの量を２０．２ｇ（０．０５５モル）、３，３’，４，４’−ジフェニルスルホンテトラカルボン酸二無水物の量を１９．８ｇ（０．０５５モル）に変更した他は、実施例１と同様にしてヒドロキシポリイミドを製作し、実施例１と同様の評価を行った。更にスカムの評価を行った。
＜実施例３＞
実施例１におけるヘキサフルオロ−２，２−ビス（３−アミノ−４−ヒドロキシフェニル）プロパンの量を２０．４ｇ（０．０５６モル）、３，３’，４，４’−ジフェニルスルホンテトラカルボン酸二無水物の量を１９．６ｇ（０．０５５モル）に変更した他は、実施例１と同様にしてヒドロキシポリイミドを製作し、実施例１と同様の評価を行った。
＜実施例４＞
実施例１におけるヘキサフルオロ−２，２−ビス（３−アミノ−４−ヒドロキシフェニル）プロパンの量を２０．７ｇ（０．０５７モル）、３，３’，４，４’−ジフェニルスルホンテトラカルボン酸二無水物の量を１９．３ｇ（０．０５４モル）に変更した他は、実施例１と同様にしてヒドロキシポリイミドを製作し、実施例１と同様の評価を行った。
＜実施例５＞
実施例１におけるヘキサフルオロ−２，２−ビス（３−アミノ−４−ヒドロキシフェニル）プロパンの量を２１．１ｇ（０．０５８モル）、３，３’，４，４’−ジフェニルスルホンテトラカルボン酸二無水物の量を１８．９ｇ（０．０５３モル）に変更した他は、実施例１と同様にしてヒドロキシポリイミドを製作し、実施例１と同様の評価を行った。
＜実施例６＞
実施例１におけるヘキサフルオロ−２，２−ビス（３−アミノ−４−ヒドロキシフェニル）プロパンの量を２１．３ｇ（０．０５８モル）、３，３’，４，４’−ジフェニルスルホンテトラカルボン酸二無水物の量を１８．７ｇ（０．０５２モル）に変更した他は、実施例１と同様にしてヒドロキシポリイミドを製作し、実施例１と同様の評価を行った。
＜実施例７＞
実施例１におけるヘキサフルオロ−２，２−ビス（３−アミノ−４−ヒドロキシフェニル）プロパンの量を１９．７ｇ（０．０５４モル）、３，３’，４，４’−ジフェニルスルホンテトラカルボン酸二無水物の量を２０．３ｇ（０．０５７モル）に変更した他は、実施例１と同様にしてヒドロキシポリイミドを製作し、実施例１と同様の評価を行った。
＜実施例８＞
実施例１におけるヘキサフルオロ−２，２−ビス（３−アミノ−４−ヒドロキシフェニル）プロパンの量を１９．５ｇ（０．０５３モル）、３，３’，４，４’−ジフェニルスルホンテトラカルボン酸二無水物の量を１８．５ｇ（０．０５７モル）に変更した他は、実施例１と同様にしてヒドロキシポリイミドを製作し、実施例１と同様の評価を行った。
＜実施例９＞
実施例１におけるヘキサフルオロ−２，２−ビス（３−アミノ−４−ヒドロキシフェニル）プロパンの量を１９．３ｇ（０．０５３モル）、３，３’，４，４’−ジフェニルスルホンテトラカルボン酸二無水物の量を２０．７ｇ（０．０５８モル）に変更した他は、実施例１と同様にしてヒドロキシポリイミドを製作し、実施例１と同様の評価を行った。
＜実施例１０＞
温度計、攪拌機、原料仕込口および窒素ガス導入口を備えた３００ｍｌ四つ口セパラブルフラスコ中にヘキサフルオロ−２，２−ビス（３−アミノ−４−ヒドロキシフェニル）プロパン２０．７ｇ（０．０５６モル）と３，３’，４，４’−ジフェニルスルホンテトラカルボン酸二無水物１０．１ｇ（０．０２８モル）と３，３’，４，４’−ベンゾフェノンテトラカルボン酸二無水物９．１ｇ（０．０２８モル）とγ−ブチロラクトン１６０．０ｇを加え、２０℃を保持しながら３時間攪拌し、アミド化反応を行った他は、実施例１と同様にしてヒドロキシポリイミドを製作し、実施例１と同様の評価を行った。またスカムの評価も行った。
【００２５】
＜比較例１＞
実施例１におけるヘキサフルオロ−２，２−ビス（３−アミノ−４−ヒドロキシフェニル）プロパンの量を２３．１ｇ（０．０６３モル）、３，３’，４，４’−ジフェニルスルホンテトラカルボン酸二無水物の量を１６．９ｇ（０．０４７モル）に変更した他は、実施例１と同様にしてヒドロキシポリイミドを製作し、実施例１と同様の評価を行ったが、得られた樹脂の分子量が５０１４（ｇ／モル）と低く、現像時に全て溶解してしまった。
＜比較例２＞
実施例１におけるヘキサフルオロ−２，２−ビス（３−アミノ−４−ヒドロキシフェニル）プロパンの量を１８．０ｇ（０．０４９モル）、３，３’，４，４’−ジフェニルスルホンテトラカルボン酸二無水物の量を２２．０ｇ（０．０６１モル）に変更した他は、実施例１と同様にしてヒドロキシポリイミドを製作し、実施例１と同様の評価を行ったが、得られた樹脂の分子量が６２３２（ｇ／モル）と低く、現像時に全て溶解してしまった。
＜比較例３＞
温度計、攪拌機、原料仕込口および窒素ガス導入口を備えた３００ｍｌ四つ口セパラブルフラスコ中にヘキサフルオロ−２，２−ビス（３−アミノ−４−ヒドロキシフェニル）プロパン１７．９ｇ（０．０５６モル）とヘキサフルオロ−２，２−ビス（３，４−フタル酸無水物）プロパン２２．１ｇ（０．０５０モル）とγ−ブチロラクトン１６０．０ｇを加え、２０℃を保持しながら３時間攪拌し、アミド化反応を行った他は、実施例１と同様にしてヒドロキシポリイミドを製作し、実施例１と同様の評価を行ったが、１２５０ｍＪ／ｃｍ2までの露光ではパターンが形成されなかった。
＜比較例４＞
温度計、攪拌機、原料仕込口および窒素ガス導入口を備えた３００ｍｌ四つ口セパラブルフラスコ中にヘキサフルオロ−２，２−ビス（３−アミノ−４−ヒドロキシフェニル）プロパン２１．５ｇ（０．０５９モル）と３，３’，４，４’−ジフェニルエーテルテトラカルボン酸二無水物１８．５ｇ（０．０６０モル）とγ−ブチロラクトン１６０．０ｇを加え、２０℃を保持しながら３時間攪拌し、アミド化反応を行った他は、実施例１と同様にしてヒドロキシポリイミドを製作し、実施例１と同様の評価を行ったが、１２５０ｍＪ／ｃｍ2までの露光ではパターンが形成されなかった。
＜比較例５＞
温度計、攪拌機、原料仕込口および窒素ガス導入口を備えた３００ｍｌ四つ口セパラブルフラスコ中にヘキサフルオロ−２，２−ビス（３−アミノ−４−ヒドロキシフェニル）プロパン２１．１ｇ（０．０５８モル）と３，３’，４，４’−ベンゾフェノンテトラカルボン酸二無水物１８．９ｇ（０．０５９モル）とγ−ブチロラクトン１６０．０ｇを加え、２０℃を保持しながら３時間攪拌し、アミド化反応を試みたが、この際に反応溶液がゲル化し以後の評価はできなかった。
＜比較例６＞
温度計、攪拌機、原料仕込口および窒素ガス導入口を備えた３００ｍｌ四つ口セパラブルフラスコ中にヘキサフルオロ−２，２−ビス（３−アミノ−４−ヒドロキシフェニル）プロパン２１．８ｇ（０．０６０モル）と３，３’，４，４’−ベンゾフェノンテトラカルボン酸二無水物１５．３ｇ（０．０４７モル）とピロメリット酸二無水物２．９ｇ（０．０１３モル）とγ−ブチロラクトン１６０．０ｇを加え、２０℃を保持しながら３時間攪拌し、アミド化反応を行った他は、実施例１と同様にしてヒドロキシポリイミドを製作し、実施例１と同様の評価を行ったが、現像抜けのこり（スカム）が多くパターン形状は満足できるものでなかった。
＜比較例７＞
実施例１０におけるヘキサフルオロ−２，２−ビス（３−アミノ−４−ヒドロキシフェニル）プロパンの量を２０．９ｇ（０．０５７モル）、３，３’，４，４’−ジフェニルスルホンテトラカルボン酸二無水物の量を６．１ｇ（０．０１７モル）、３，３’，４，４’−ベンゾフェノンテトラカルボン酸二無水物の量を１２．９ｇ（０．０４０モル）に変更した他は、実施例１０と同様にしてヒドロキシポリイミドを製作し、実施例１０と同様の評価を行ったが、１２５０ｍＪ／ｃｍ2までの露光ではパターンが形成されなかった。
【００２６】
実施例３〜６、比較例２、参考例１〜６の評価結果を表１に示す。
【表１】
参考例２、７〜８、比較例３〜５の評価結果を表２に示す。
【表２】
【発明の効果】
本発明により、高感度かつパターン形状の優れたポジ型感光性樹脂組成物を得ることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a positive photosensitive resin composition having high sensitivity and excellent patterning characteristics.
[0002]
[Prior art]
Conventionally, polyimide resin having excellent heat resistance and excellent electrical and mechanical properties has been used for the surface protection film and interlayer insulation film of semiconductor elements. There has been a demand for significant improvement in heat cycle resistance, heat shock resistance, and the like due to the shift to surface mounting by package thinning, size reduction, and solder reflow, and higher performance resins have been required.
[0003]
On the other hand, techniques for imparting photosensitivity to the polyimide resin itself have recently attracted attention, and examples thereof include a photosensitive polyimide resin represented by the following formula (4).
[Formula 4]
If this is used, part of the pattern creation process can be simplified, and there is an effect of shortening the process and improving the yield. However, since a solvent such as N-methyl-2-pyrrolidone is required for development, safety and handling There is a problem with sex.
Therefore, a positive photosensitive resin that can be developed with an aqueous alkali solution has recently been developed. For example, Japanese Patent Application Laid-Open No. 1-60630 discloses a positive photosensitive resin composition obtained from a hydroxypolyimide resin.
[0005]
When these photosensitive resins are actually used, the sensitivity of the photosensitive resin is particularly important. Low sensitivity requires longer exposure time and lower throughput, so a higher sensitivity is required, but the positive photosensitive resin composition obtained from hydroxypolyimide resin sufficiently satisfies the market requirements. There was nothing to do.
[0006]
[Problems to be solved by the invention]
An object of the present invention is to provide a positive photosensitive resin composition having high sensitivity and excellent patterning characteristics.
[0007]
The present invention has a number average molecular weight of 9,312 or more obtained by reacting 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride represented by the general formula (1) with aminophenol. A positive photosensitive resin composition comprising 100 parts by weight of a hydroxypolyimide (A) and 1 to 50 parts by weight of a diazonaphthoquinone compound (B).
[Chemical formula 5]
DETAILED DESCRIPTION OF THE INVENTION
X of the hydroxypolyimide of the general formula (1) used in the present invention is, for example,
[Chemical 6]
[0009]
Y in formula (1) is, for example,
[Chemical 7]
[0010]
E in the formula (1) may be either a hydrogen atom or a carboxylic acid derivative of an aliphatic or cyclic compound containing at least one alkenyl group. Examples of the latter include, but are not limited to, 5-norbornene-2,3-dicarboxylic anhydride, maleic anhydride and the like.
[0011]
A of the bisaminophenol of the formula (2) used in the present invention is, for example,
[Chemical 8]
[0012]
B of the tetracarboxylic dianhydride of the formula (3) used in the present invention is, for example,
[Chemical 9]
[0013]
The diazonaphthoquinone compound used in the present invention is a compound having a 1,2-naphthoquinonediazide structure and is known from US Pat. Nos. 2,772,972, 2,797,213, and 3,669,658. It is a substance.
[0014]
For example, the following are mentioned.
[Chemical Formula 10]
Among these, the following are particularly preferable.
Embedded image
Moreover, the compounding quantity to the hydroxypolyimide (A) of the photosensitive agent (B) used by this invention is 1-50 weight part with respect to 100 weight part of hydroxypolyimide. If the blending amount is less than 1 part by weight, the patterning characteristics of the resin will be poor, and conversely if it exceeds 50 parts by weight, the sensitivity will be greatly reduced, which is not preferable.
[0017]
If necessary, additives such as a leveling agent and a silane coupling agent can be added to the positive photosensitive resin composition in the present invention.
In the present invention, these components are dissolved in a solvent and used in the form of a varnish. 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, pyropyrene 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- Examples thereof include methoxypropionate and may be used alone or in combination.
[0018]
In the method of using the positive photosensitive resin composition of the present invention, first, the composition is applied to a suitable support such as a silicon wafer, a ceramic substrate, an aluminum substrate and the like. In the case of a semiconductor device, the coating amount is applied so that the final film thickness after curing is 0.1 to 20 μm. Examples of the coating method include spin coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, and the like.
Next, after prebaking at 60 to 130 ° C. to dry the coating film, actinic radiation is applied to the desired pattern shape. As the actinic radiation, X-rays, electron beams, ultraviolet rays, visible rays and the like can be used, but those having a wavelength of 200 to 500 nm are preferable.
[0019]
Next, a relief pattern is obtained by dissolving and removing the irradiated portion with a developer. Developers include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, and ethylamine. Primary amines such as n-propylamine, secondary amines such as diethylamine and di-n-propylamine, tertiary amines such as triethylamine and methylethyldiamine, alcohol amines such as dimethylethanolamine and triethanolamine , Quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and the like, and an appropriate amount of a water-soluble organic solvent such as methanol and ethanol, and a surfactant were added thereto. An aqueous solution can be suitably used.
As a developing method, methods such as spraying, paddle, dipping, and ultrasonic waves are possible.
[0020]
Next, the relief pattern formed by development is rinsed. Distilled water is used as the rinse liquid. Next, heat treatment is performed to obtain a final pattern with high heat resistance.
[0021]
【Example】
Hereinafter, the present invention will be described specifically by way of examples.
<Example 1>
* Hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane 20 in a 300 ml four-necked separable flask equipped with a hydroxypolyimide synthesis thermometer, stirrer, raw material inlet and nitrogen gas inlet 0.02 g (0.055 mol), 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride 20.0 g (0.056 mol) and γ-butyrolactone 160.0 g were added and maintained at 20 ° C. While stirring for 3 hours, an amidation reaction was carried out. Thereafter, 32 g of toluene was added to the reaction system, and refluxed at 130 to 140 ° C. for 3 hours to effect azeotropy, thereby distilling off water, which was a byproduct of the cyclization reaction, outside the system. Next, toluene was distilled off under reduced pressure for 30 minutes, and then cooled to room temperature. The obtained reaction mixture was filtered and then poured into a solution of water / methanol = 3/1. The precipitate was collected, washed thoroughly with pure water, and then dried under vacuum to obtain the desired hydroxypolyimide.
Moreover, when the number average molecular weight was measured about the obtained hydroxy polyimide, it was 14742 (g / mol).
[0022]
* Preparation of positive photosensitive resin composition 30 g of this hydroxypolyimide and 6.0 g of diazoquinone compound (Q-1) having the structure of the following formula were dissolved in 70 g of γ-butyrolactone, and then filtered through a 0.2 μm Teflon filter. A photosensitive resin composition was obtained.
Embedded image
* Characteristic evaluation This positive photosensitive resin composition was applied onto a silicon wafer using a spin coater and then dried on a hot plate at 120 ° C. for 4 minutes to obtain a coating film having a thickness of about 7.5 μm. Was exposed to 1250 mJ / cm 2 increased from 25 mJ / cm 2 through a mask having a test pattern by 25 mJ / cm 2 by g-line stepper exposure line NSR-1505G3A the coated film (manufactured by Nikon Corporation).
Next, the exposed portion was dissolved and removed by immersing in a 2.38% aqueous solution of tetraammonium hydroxide for 40 seconds, and then rinsed with pure water for 30 seconds. As a result, it was confirmed that a pattern was formed from a portion irradiated with an exposure amount of 450 mJ / cm 2 . At this time, the film thickness of the unexposed portion was 5 μm.
In some examples, scum (development residue) after pattern formation was measured.
[0024]
<Example 2>
The amount of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane in Example 1 was 20.2 g (0.055 mol) and 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic. A hydroxypolyimide was produced in the same manner as in Example 1 except that the amount of acid dianhydride was changed to 19.8 g (0.055 mol), and the same evaluation as in Example 1 was performed. Further, scum was evaluated.
<Example 3>
The amount of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane in Example 1 was 20.4 g (0.056 mol) and 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic. A hydroxypolyimide was produced in the same manner as in Example 1 except that the amount of acid dianhydride was changed to 19.6 g (0.055 mol), and the same evaluation as in Example 1 was performed.
<Example 4>
The amount of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane in Example 1 was 20.7 g (0.057 mol) and 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic. A hydroxypolyimide was produced in the same manner as in Example 1 except that the amount of acid dianhydride was changed to 19.3 g (0.054 mol), and the same evaluation as in Example 1 was performed.
<Example 5>
The amount of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane in Example 1 was 21.1 g (0.058 mol) and 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic. A hydroxypolyimide was produced in the same manner as in Example 1 except that the amount of acid dianhydride was changed to 18.9 g (0.053 mol), and the same evaluation as in Example 1 was performed.
<Example 6>
The amount of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane in Example 1 was 21.3 g (0.058 mol) and 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic. A hydroxypolyimide was produced in the same manner as in Example 1 except that the amount of acid dianhydride was changed to 18.7 g (0.052 mol), and the same evaluation as in Example 1 was performed.
<Example 7>
The amount of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane in Example 1 was 19.7 g (0.054 mol), 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic. A hydroxypolyimide was produced in the same manner as in Example 1 except that the amount of acid dianhydride was changed to 20.3 g (0.057 mol), and the same evaluation as in Example 1 was performed.
<Example 8>
The amount of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane in Example 1 was 19.5 g (0.053 mol), 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic. A hydroxypolyimide was produced in the same manner as in Example 1 except that the amount of acid dianhydride was changed to 18.5 g (0.057 mol), and the same evaluation as in Example 1 was performed.
<Example 9>
The amount of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane in Example 1 was 19.3 g (0.053 mol), 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic. A hydroxypolyimide was produced in the same manner as in Example 1 except that the amount of acid dianhydride was changed to 20.7 g (0.058 mol), and the same evaluation as in Example 1 was performed.
<Example 10>
In a 300 ml four-necked separable flask equipped with a thermometer, a stirrer, a raw material charging port, and a nitrogen gas inlet, 20.7 g of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane (0. 056 mol), 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride 10.1 g (0.028 mol) and 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride 9 0.1 g (0.028 mol) and 160.0 g of γ-butyrolactone were added and stirred for 3 hours while maintaining 20 ° C., and the amidation reaction was performed. The same evaluation as in Example 1 was performed. Scum was also evaluated.
[0025]
<Comparative Example 1>
The amount of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane in Example 1 was 23.1 g (0.063 mol), 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic. A hydroxypolyimide was produced in the same manner as in Example 1 except that the amount of acid dianhydride was changed to 16.9 g (0.047 mol), and the same evaluation as in Example 1 was performed. The molecular weight of the resin was as low as 5014 (g / mol), and it was completely dissolved during development.
<Comparative example 2>
The amount of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane in Example 1 was 18.0 g (0.049 mol), 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic. A hydroxypolyimide was produced in the same manner as in Example 1 except that the amount of acid dianhydride was changed to 22.0 g (0.061 mol), and the same evaluation as in Example 1 was performed. The molecular weight of the resin was as low as 6232 (g / mol), and it was completely dissolved during development.
<Comparative Example 3>
In a 300 ml four-necked separable flask equipped with a thermometer, a stirrer, a raw material charging port and a nitrogen gas inlet, 17.9 g of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane (0. 056 mol), 22.2 g (0.050 mol) of hexafluoro-2,2-bis (3,4-phthalic anhydride) propane and 160.0 g of γ-butyrolactone were added, and the mixture was maintained at 20 ° C. for 3 hours. Except for stirring and amidation reaction, hydroxypolyimide was produced in the same manner as in Example 1 and evaluated in the same manner as in Example 1, but no pattern was formed by exposure up to 1250 mJ / cm 2. It was.
<Comparative example 4>
In a 300 ml four-necked separable flask equipped with a thermometer, a stirrer, a raw material charging port and a nitrogen gas inlet, 21.5 g of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane (0. 059 mol), 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride 18.5 g (0.060 mol) and 160.0 g of γ-butyrolactone were added and stirred for 3 hours while maintaining 20 ° C. Aside from the amidation reaction, hydroxypolyimide was produced in the same manner as in Example 1 and evaluated in the same manner as in Example 1. However, no pattern was formed by exposure up to 1250 mJ / cm 2 .
<Comparative Example 5>
In a 300 ml four-necked separable flask equipped with a thermometer, a stirrer, a raw material charging port and a nitrogen gas inlet, 21.1 g of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane (0. 058 mol), 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride 18.9 g (0.059 mol) and γ-butyrolactone 160.0 g were added, and the mixture was stirred for 3 hours while maintaining 20 ° C. An amidation reaction was attempted. At this time, the reaction solution gelled and no further evaluation was possible.
<Comparative Example 6>
In a 300 ml four-necked separable flask equipped with a thermometer, a stirrer, a raw material charging port and a nitrogen gas inlet, 21.8 g of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane (0. 060 mol), 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride 15.3 g (0.047 mol), pyromellitic dianhydride 2.9 g (0.013 mol) and γ-butyrolactone Although 160.0 g was added and the mixture was stirred for 3 hours while maintaining at 20 ° C. to perform the amidation reaction, hydroxypolyimide was produced in the same manner as in Example 1, and the same evaluation as in Example 1 was performed. The pattern shape was unsatisfactory because of a large amount of development omission (scum).
<Comparative Example 7>
The amount of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane in Example 10 was 20.9 g (0.057 mol) and 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic. The amount of acid dianhydride was changed to 6.1 g (0.017 mol) and the amount of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride was changed to 12.9 g (0.040 mol). Produced a hydroxypolyimide in the same manner as in Example 10 and evaluated it in the same manner as in Example 10. However, no pattern was formed by exposure up to 1250 mJ / cm 2 .
[0026]
Table 1 shows the evaluation results of Examples 3 to 6, Comparative Example 2, and Reference Examples 1 to 6.
[Table 1]
The evaluation results of Reference Examples 2 and 7 to 8 and Comparative Examples 3 to 5 are shown in Table 2.
[Table 2]
【The invention's effect】
According to the present invention, a positive photosensitive resin composition having high sensitivity and excellent pattern shape can be obtained.
Claims (1)
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| KR100981830B1 (en) | 2005-09-22 | 2010-09-13 | 히다치 가세이듀퐁 마이쿠로시스데무즈 가부시키가이샤 | Negative photosensitive resin composition, method of pattern forming and electronic part |
| JP4969941B2 (en) * | 2006-08-02 | 2012-07-04 | ソニーケミカル＆インフォメーションデバイス株式会社 | Polyimide composition, flexible wiring board and method for producing flexible wiring board |
| EP2133743B1 (en) | 2007-03-12 | 2018-01-24 | Hitachi Chemical DuPont Microsystems, Ltd. | Photosensitive resin composition, process for producing patterned hardened film with use thereof and electronic part |
| KR101640143B1 (en) * | 2007-04-02 | 2016-07-18 | 닛산 가가쿠 고교 가부시키 가이샤 | Positive Photosensitive Resin Composition, Cured Film Thereof, and Display Element |
| JP5316417B2 (en) | 2007-10-29 | 2013-10-16 | 日立化成デュポンマイクロシステムズ株式会社 | Positive photosensitive resin composition, pattern manufacturing method, and electronic component |
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