JP4573084B2 - Photosensitive resin composition, method for producing relief pattern using the same, and method for producing heat-resistant coating film - Google Patents

Description

式中Ｒ¹、Ｒ²、Ｒ³は独立に水素、炭素数１〜８のアルキル基、炭素数１〜８のアルコキシ基、炭素数１〜８のアルキリデン基、炭素数４〜８のシクロアルキル基、炭素数４〜８のシクロアルケニル基、炭素数１〜６のフェノキシアルキル基、フェニル基、電子供与性基および/または電子吸引性基が置換したフェニル基、ベンジル基、電子供与性基および/または電子吸引性基が置換したベンジル基等が挙げられる。炭素数１〜８のアルキル基としては、直鎖上のアルキル基の他に、置換基を有するアルキル基、例えばイソプロピル基、イソブチル基、ｔ-ブチル基等も含む。これらの置換基の中で、合成の簡便性、アミンイミドの溶解性等の点から、炭素数１〜８のアルキル基、炭素数６〜８のシクロアルキル基、炭素数１〜６のフェノキシアルキル基が好ましい。また、Ｒ⁴は独立に炭素数１〜５のアルキル基、水酸基、炭素数４〜８のシクロアルキル基、炭素数１〜５のアルコキシ基、フェニル基を表す。
上記一般式(１)中のＡｒ¹は一般式（I）〜(XIII)で表される芳香族基であり、
【化２】

式中Ｒ⁵〜Ｒ²⁸は独立に、水素、炭素数１〜８のアルキル基、炭素数１〜８のアルコキシ基、炭素数１〜８のアルキルチオ基、炭素数１〜８のアルキリデン基、炭素数４〜８のシクロアルキル基、炭素数４〜８のシクロアルケニル基、アミノ基、炭素数１〜６のアルキルアミノ基、炭素数１〜３のジアルキルアミノ基、モルフォリノ基、メルカプト基、水酸基、炭素数１〜６のヒドロキシアルキル基、フッ素、塩素、臭素等のハロゲン、炭素数１〜６のエステル基、炭素数１〜６のカルボニル基、アルデヒド基、シアノ基、トリフルオロメチル基、シアノ基、ニトロ基、ベンゾイル基、フェニル基、電子供与性基および/または電子吸引性基が置換したフェニル基、電子供与性基および/または電子吸引性基が置換したベンジル基である。また式中Ｕ〜Ｚは、炭素、窒素、酸素、硫黄原子のいずれかである。
また、前記一般式（２）中のＡｒ²は、次式（XIV）〜（XXII）で示される芳香族基であり、
【化３】

Ｒ²⁹〜Ｒ³⁶は独立に、水素、炭素数１〜８のアルキル基、炭素数１〜８のアルコキシ基、炭素数１〜８のアルキルチオ基、炭素数１〜８のアルキリデン基、炭素数４〜８のシクロアルキル基、炭素数４〜８のシクロアルケニル基、アミノ基、炭素数１〜６のアルキルアミノ基、炭素数１〜３のジアルキルアミノ基、モルフォリノ基、メルカプト基、水酸基、炭素数１〜６のヒドロキシアルキル基、フッ素、塩素、臭素等のハロゲン、炭素数１〜６のエステル基、炭素数１〜６のカルボニル基、アルデヒド基、シアノ基、トリフルオロメチル基、シアノ基、ニトロ基、フェニル基、電子供与性基および/または電子吸引性基が置換したフェニル基、電子供与性基および/または電子吸引性基が置換したベンジル基である。また式中Ｗは、炭素、窒素、炭素数１〜６のアルキル基が置換した窒素、酸素、硫黄であり、Ｘ〜Ｚは独立に、炭素、窒素、酸素、硫黄原子である。
Ａｒ¹と同様に熱的な安定性、吸収波長の点から、Ｒ²⁹〜Ｒ³⁶の置換基としては、電子吸引性基である炭素数１〜６のカルボニル基、シアノ基、ニトロ基が好ましい。
【０００７】
アミンイミド化合物の合成は、公知の方法を用いることができる。例えば、Ｅｎｃｙｃｌｏｐｅｄｉａ ｏｆ Ｐｏｌｙｍｅｒ Ｓｃｉｅｎｃｅ ａｎｄ Ｅｎｇｉｎｅｅｒｉｎｇ、Ｊｏｈｎ Ｗｉｌｅｙ ＆ Ｓｏｎｓ Ｌｔｄ．、(１９８５年)、第１巻、ｐ７４０に記載されているように、対応するカルボン酸エステルとハロゲン化ヒドラジン及びナトリウムアルコキサイドとの反応やカルボン酸エステルとヒドラジン及びエポキシ化合物との反応から得ることができる。
合成の簡便性、安全性を考慮すると、対応するカルボン酸エステルとヒドラジン及びエポキシ化合物からの合成法が特に好ましい。合成温度、合成時間に関しては、使用する出発物質の分解等が無ければ特に制限を受けないが、一般的には０〜１００℃の温度で３０分〜７日間攪拌することによって目的のアミンイミド化合物を得ることができる。
【０００８】
本発明において用いるポリアミド酸としては、特に制限無く公知のものを使用しうるが、例えば、テトラカルボン酸二無水物とジアミン化合物を付加重合させて得られるものが挙げられる。
【０００９】
テトラカルボン酸二無水物としては、例えば、ピロメリット酸二無水物、３，３’，４，４’−ベンゾフェノンテトラカルボン酸二無水物、３，３’，４，４’−ビフェニルテトラカルボン酸二無水物、１，２，５，６-ナフタレンカルボン酸二無水物、１，２，３，６，７−ナフタレンテトラカルボン酸二無水物、２，３，５，６−ピリジンテトラカルボン酸二無水物、１，４，５，８−ナフタレンテトラカルボン酸二無水物、３，４，９，１０−ペリレンテトラカルボン酸二無水物、４，４’−スルホニルジフタル酸二無水物、ｍ-ターフェニル-３，３”，４，４”-テトラカルボン酸二無水物、ｐ-ターフェニル-３，３”，４，４”-テトラカルボン酸二無水物、４，４’-オキシジフタル酸二無水物、１，１，１，３，３，３−ヘキサフルオロ-２，２−ビス（２，３−ジカルボキシフェニル）プロパン二無水物、２，２−ビス（２，３−ジカルボキシフェニル）プロパン二無水物、２，２−ビス（３，４-ジカルボキシフェニル）プロパン二無水物、１，１，１，３，３，３−ヘキサフルオロ-２，２’-ビス[４−(２，３−ジカルボキシフェノキシ)フェニル]プロパン二無水物、１，１，１，３，３，３−ヘキサフルオロ-２，２’-ビス[４−(３，４−ジカルボキシフェノキシ)フェニル]プロパン二無水物が挙げられる。これらのテトラカルボン酸二無水物は単独で又は２種以上を組合わせて使用される。
【００１０】
ジアミン化合物としては、例えば、ｐ-フェニレンジアミン、ｍ-フェニレンジアミン、ｐ−キシリレンジアミン、ｍ−キシリレンジアミン、１，５−ジアミノナフタレン、ベンジジン、３，３’−ジメチルベンジジン、３，３’−ジメトキシベンジジン、４，４’（又は３，４’−、３，３’−、２，４’−）-ジアミノジフェニルメタン、４，４’（又は３，４’−、３，３’−、２，４’−）-ジアミノジフェニルエーテル、４，４’（又は３，４’−、３，３’−、２，４’−）-ジアミノジフェニルスルホン、４，４’（又は３，４’−、３，３’−、２，４’−）-ジアミノジフェニルスルフィド、４，４’-ベンゾフェノンジアミン、３，３’-ベンゾフェノンジアミン、４，４’−ジ（４−アミノフェノキシ）フェニルスルホン、４，４’−ビス（４−アミノフェノキシ）フェニルスルホン、４，４’−ビス（４−アミノフェノキシ）ビフェニル、１，４−ビス（４−アミノフェノキシ）ベンゼン、１，３−ビス(４−アミノフェノキシ)ベンゼン、１，１，１，３，３，３−ヘキサフルオロ-２，２-ビス（４−アミノフェニル）プロパン、２，２−ビス[４−(４−アミノフェノキシ)フェニル]プロパン、３，３−ジメチル−４，４’−ジアミノジフェニルメタン、３，３’，５，５’−テトラメチル-４，４’-ジアミノジフェニルメタン、４，４’-ジ（３−アミノフェノキシ）フェニルスルホン、３，３’−ジアミノジフェニルスルホン、２，２’−ビス(４−アミノフェニル)プロパン、４，４’−（９−フルオレニリデン）ジアニリン等の芳香族ジアミン、２，７−ジアミノフルオレン、２，６−ジアミノピリジン、２，４−ジアミノピリジン、２，４−ジアミノピリミジン、２，４−ジアミノ-ｓ-トリアジン、２，７−ジアミノベンゾフラン、２，７−ジアミノカルバゾール、３，７−ジアミノフェノチアジン、２，５−ジアミノ-１，３，４−チアジアゾール、２，４−ジアミノ-６−フェニル-ｓ-トリアジン等の複素環式ジアミン、トリメチレンジアミン、テトラメチレンジアミン、ヘキサメチレンジアミン、２，２−ジメチルプロピレンジアミン、ジアミノポリシロキサン等の脂肪族ジアミンなどが挙げられる。これらのジアミン化合物は、単独で又は２種以上を組み合わせて使用される。
【００１１】
本発明の(ａ)アミンイミド化合物の添加量としては、(ｂ)ポリアミド酸の固形分１００重量部に対して、０．１〜５０重量部が好ましく、１〜３０重量部がさらに好ましい。アミンイミド化合物が０．１重量部未満では感度不足となって、イミド化を促進することができない。また、５０重量部を超えた場合には、加熱後にフィルム中にアミンイミドの光分解生成物が多量に残存するため、フィルム物性が低下する傾向にある。
【００１２】
本発明で用いる増感剤は、感光性樹脂組成物に悪影響を及ぼさない限り、公知の一重項増感剤、三重項増感剤を用いることができる。例えば、ナフタレン、アントラセン、ピレン等の芳香族化合物誘導体、カルバゾール誘導体、芳香族カルボニル化合物、ベンゾフェノン誘導体、チオキサントン誘導体、クマリン誘導体等が好適に用いられる。特にこの中でも、一重項増感剤としては、ナフタレン誘導体、アントラセン誘導体、カルバゾール誘導体、三重項増感剤としては、チオキサントン誘導体、ベンゾフェノン誘導体が最も好ましい。例えば、１−メチルナフタレン、２−メチルナフタレン、１−フルオロナフタレン、１−クロロナフタレン、２−クロロナフタレン、１−ブロモナフタレン、２−ブロモナフタレン、１−ヨードナフタレン、２−ヨードナフタレン、１−ナフトール、２−ナフトール、１−メトキシナフタレン、２−メトキシナフタレン、１，４−ジシアノナフタレン、アントラセン、１，２−ベンズアントラセン、９，１０−ジクロロアントラセン、９，１０−ジブロモアントラセン、９，１０−ジフェニルアントラセン、９−シアノアントラセン、９，１０−ジシアノアントラセン、２，６，９，１０−テトラシアノアントラセン、カルバゾール、９−メチルカルバゾール、９−フェニルカルバゾール、９−プロペ−２−イニル−９Ｈ−カルバゾール、９−プロピル−９Ｈ−カルバゾール、９−ビニルカルバゾール、９Ｈ−カルバゾール−９−エタノール、９−メチル−３−ニトロ−９Ｈ−カルバゾール、９−メチル−３，６−ジニトロ−９Ｈ−カルバゾール、９−オクタノイルカルバゾール、９−カルバゾールメタノール、９−カルバゾールプロピオン酸、９−カルバゾールプロピオニトリル、９−デシル−３，６−ジニトロ-９Ｈ−カルバゾール、９−エチル−３，６−ジニトロ−９Ｈ−カルバゾール、９−エチル−３−ニトロカルバゾール、９−エチルカルバゾール、９−イソプロピルカルバゾール、９−（エトキシカルボニルメチル）カルバゾール、９−(モルホリノメチル)カルバゾール、９−アセチルカルバゾール、９−アリルカルバゾール、９−ベンジル−９Ｈ−カルバゾール、９−カルバゾール酢酸、９−(２−ニトロフェニル)カルバゾール、９−(４−メトキシフェニル)カルバゾール、９−（１−エトキシ−２−メチル−プロピル）−9Ｈ-カルバゾール、３−ニトロカルバゾール、４−ヒドロキシカルバゾール、３，６−ジニトロ−９Ｈ−カルバゾール、３，６−ジフェニル−９Ｈ−カルバゾール、２−ヒドロキシカルバゾール、３，６−ジアセチル−９−エチルカルバゾール、ベンゾフェノン、４−フェニルベンゾフェノン、４，４’-ビス(ジメトキシ)ベンゾフェノン、４，４’−ビス(ジメチルアミノ)ベンゾフェノン、４，４’−ビス(ジエチルアミノ)ベンゾフェノン、２−ベンゾイル安息香酸メチルエステル、２−メチルベンゾフェノン、３−メチルベンゾフェノン、４−メチルベンゾフェノン、３，３’−ジメチル−４−メトキシベンゾフェノン、２，４，６−トリメチルベンゾフェノン、[４−（４−メチルフェニルチオ）フェニル]−フェニルメタノン、キサントン、チオキサントン、２−クロロチオキサントン、４−クロロチオキサントン、２−イソプロピルチオキサントン、４−イソプロピルチオキサントン、２，４−ジメチルチオキサントン、２，４−ジエチルチオキサントン、１−クロロ−４−プロポキシチオキサントンが挙げられる。これらは、単独で用いるほかに、複数を組み合わせて用いても良い。増感剤の使用量は、増感剤の吸収波長及びモル吸光係数を参考にする必要があるが、一般的にアミンイミド化合物１重量部に対して０．０１〜１０重量部であり、０.１〜５重量部が特に好ましい。増感剤が０.０１重量部未満になると光吸収の効率が低くなり、１０重量部を超えると感光性樹脂組成物全体に光が届かない恐れがある。
【００１３】
本発明の感光性樹脂組成物は、必要に応じてカップリング剤等の密着向上剤、レベリング剤、可塑剤、有機または無機充填材などの添加剤を適宜添加してもよい。
【００１４】
本発明の感光性樹脂組成物は、必要に応じて有機溶剤を使用してもよい。使用できる溶剤としては、アミンイミド化合物及びポリアミド酸に十分な溶解性を示すものであれば、特に制限は受けない。例えば、アセトン、アセトニトリル、メチルエチルケトン、ジエチルケトン、シクロヘキサノン、トルエン、クロロホルム、メタノール、エタノール、１−プロパノール、２−プロパノール、１−ブタノール、ｔ-ブタノール、エチレングリコールモノメチルエーテル、キシレン、テトラヒドロフラン、ジオキサン、Ｎ，Ｎ-ジメチルアセトアミド、Ｎ，Ｎ-ジメチルホルムアミド、Ｎ−メチル−2−ピロリドン、γ−ブチロラクトン、ジメチルスルホキシド、エチレンカーボネート、スルホラン等が挙げられる。これらの有機溶剤は、単独で又は２種以上を組み合わせて用いられる。そのような有機溶剤の使用量は、特に制限は無いが、塗工性の点から、組成物の固形分が５〜９５重量％となるような量が好ましく、１０〜５０重量％となるような量がより好ましい。
【００１５】
本発明の感光性樹脂組成物は、浸漬法、スプレー法、スクリーン印刷法、回転塗布法等によってシリコンウェーハ、金属基板、ガラス基板、セラミック基板等の基材上に塗布され、有機溶剤を含む場合は、それらの有機溶剤の大部分を加熱乾燥することにより、粘着性のない塗膜とすることができる。この塗膜上に、パターン状あるいは全面に活性光線を照射する。照射する活性光線としては、紫外線、遠紫外線、可視光、電子線、Ｘ線などがある。活性光線を照射した後、８０〜３００℃で５秒〜１時間加熱して、イミド化を促進させる。パターン状に活性光線を照射した場合には、未照射部を適当な現像液で溶解除去することにより、所望のレリーフパターンを得る。
【００１６】
現像液としては、特に制限はないが、例えば、炭酸ナトリウムやテトラメチルアンモニウムヒドロオキサイド（ＴＭＨ）を含有した水溶液等のアルカリ水溶液、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチル―２−ピロリドン等の良溶媒と低級アルコール、水、芳香族炭化水素等の貧溶媒との混合液などが用いられる。また、現像後に、イミド化を完全にするために、１００〜３５０℃で５分〜２時間加熱しても良い。このようにして得られたレリーフパターンは、ＳｉＯ_２、ＳｉＮ等の無機物を用いて形成されたパッシベーション膜をドライエッチング等により加工することができる。
【００１７】
【実施例】
以下に、本発明を実施例に基づいて具体的に説明するが、本発明はこれに限定されるものではない。
【００１８】
アミンイミドの合成１(アミンイミド１)
ｐ-ニトロ安息香酸メチルエステル(２.００ｇ、１１ｍｍｏｌ)、Ｎ，Ｎ−ジメチルヒドラジン(０.６６g、１１ｍｍｏｌ)、フェニルグリシジルエーテル（１.６６ｇ、１１ｍｍｏｌ）をｔｅｒｔ−ブタノール（１５.０ｇ）に添加し、５０℃で１０時間攪拌した後、さらに室温（２５℃）で４８時間攪拌したところ、白色沈殿が生成した。これを濾別した後、酢酸エチルで２度洗浄し、真空乾燥機で乾燥させてアミンイミド化合物を得た。収量３.６７ｇ、収率８５％、融点１４６−１４７℃であった。
【００１９】
アミンイミドの合成２（アミンイミド２）
ｐ-シアノ安息香酸メチルエステル(２.００ｇ、１２ｍｍｏｌ)、Ｎ，Ｎ−ジメチルヒドラジン(０.７５ｇ、１２ｍｍｏｌ)、フェニルグリシジルエーテル（１.８６ｇ、１２ｍｍｏｌ）をｔｅｒｔ−ブタノール（１０ｇ）に添加し、５０℃で７２時間攪拌した後、さらに室温で４８時間攪拌した。得られた反応溶液をロータリーエバポレータでｔｅｒｔ−ブタノールを除去した後、酢酸エチル１０ｇを加えて再結晶を行って白色のアミンイミド化合物を得た。収量２.７４ｇ、収率６５％、融点１４８−１４９℃であった。
【００２０】
（実施例１）
４，４’−ジアミノジフェニルエーテルとピロメリット酸二無水物とを等モルで常法により反応させて得られたポリアミド酸のＮ−メチル−２−ピロリドン溶液１０ｇ（固形分２０重量％）に、上記合成によって得られたアミンイミド化合物１を０.０４ｇ配合して、感光性樹脂溶液とした。この感光性樹脂溶液をシリコーンウェハ上に回転塗布し、ホットプレート上１００℃で２００秒加熱し、感光性塗膜とした。乾燥後の膜厚は１０μｍであった。塗膜上にフォトマスクを介し超高圧水銀灯を光源とするミラープロジェクション露光機で３６６ｎｍの照射量が３Ｊ/ｃｍ^２となるように露光を行った後、ホットプレート上１５０℃で６０秒加熱した。このあと、１.６８ＮのＴＭＨ（テトラメチルアンモニウムヒドロオキサイド）水溶液で浸漬現像を行い、次いで純水でリンスしたところ、露光部のパターンが残存したネガ型のレリーフパターンが得られた。
【００２１】
(実施例２)
アミンイミド化合物１の代わりにアミンイミド化合物２を０.０４ｇ使用し、かつ増感剤としてベンゾフェノンを０.０２ｇ使用した以外は、実施例１と同様にパターン形成を試みたところ、露光部のパターンが残存したネガ型のレリーフパターンが得られた。
【００２２】
(比較例１)
アミンイミド化合物１を添加しない他は、実施例１と同様にパターン形成を試みたところ、露光部、未露光部に関係なく、全て現像時に溶解し、レリーフパターンは得られなかった。
【００２３】
【発明の効果】
本発明によれば、光照射を行うことにより低温でポリアミド酸のイミド化を促進し、さらに、貯蔵安定性に優れる硬化性組成物を提供することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a photosensitive resin composition comprising an amine imide compound that generates a base upon irradiation with actinic rays and a polyamic acid, a method for producing a relief pattern, and a method for producing a heat-resistant coating film.
[0002]
[Prior art]
Photo-curing technology has been applied in a wide range of fields from paints to semiconductor materials, taking advantage of features such as low-temperature curing, process shortening, short-time curing, and microfabrication compared to conventional thermosetting technologies. . In particular, in the field of semiconductor materials, photosensitive polyimide having a heat resistance of 250 ° C. or higher is used as a surface protective film for the purpose of circuit protection. For photosensitive polyimide, several methods for imparting photosensitivity are known. Typical examples include those obtained by esterifying a carboxylic acid of a polyamic acid with hydroxyethyl acrylate as proposed in Japanese Patent Publication No. 55-41422, and those proposed in Japanese Patent Laid-Open No. 54-145794. It is known that an amino acrylate is blended with such a polyamic acid and a photosensitive group is introduced by a salt bond. These materials are prepared by dissolving a photosensitive material (photo radical initiator, polyfunctional acrylate monomer) or the like in a polar solvent such as N-methylpyrrolidone (NMP) or N, N-dimethylacetamide (DMAC), and so on. After coating on the base material, exposure and development in a pattern using actinic rays to form a pattern, followed by heating at 300 ° C. or higher, imidization of polyamic acid and added photosensitive material, etc. Is decomposed and volatilized to obtain the desired polyimide. However, the photosensitive material does not completely volatilize even when heated, and remains in the film, so that there is a problem that the physical properties (adhesive strength, elastic modulus, heat resistance, etc.) of the heated film are lowered.
As a method for solving the above problem, a method using a polyamic acid and a photobase generator has been reported. This is an application of promoting the imidization reaction of polyamic acid at a low temperature of 300 ° C. or lower in the presence of a base catalyst. For example, Polym. Bull. As represented by volume 30, page 369, 1993, the o-nitrobenzyl carbamate derivative is exposed to light to generate a base, and then exposed through a mask to generate the base only in the exposed area. After that, heating is performed to imidize only the exposed portion, and development is performed with a solvent or an alkaline aqueous solution in which the polyamic acid in the unexposed portion is dissolved to produce a negative pattern.
[0003]
[Problems to be solved by the invention]
However, in the case of conventional photobase generators, since the base generated by light irradiation is a primary or secondary amine, there is a drawback that the basicity is low and the ability to promote imidization is low. Furthermore, since the base generation efficiency of these photobase generators upon irradiation with actinic rays is very low, long-time exposure is required, and there is a problem that the process cannot be shortened.
[0004]
The present invention relates to a photosensitive resin composition in which amine imide is used in combination with polyamic acid as a photobase generator that efficiently generates a sufficiently strong base even at a low exposure amount, a method for producing a relief pattern, and a method for producing a heat-resistant coating film. It is to provide.
[0005]
[Means for Solving the Problems]
As a result of intensive studies in view of the above, the present invention has found that an amine imide compound efficiently generates a tertiary amine that is a strong base by irradiation with actinic rays, and can promote the imidization reaction of polyamic acid at a low temperature. Although it is described in JP-A-10-139748 that an amine imide compound generates a tertiary amine by heating, it is not described that a tertiary amine is generated by irradiation with actinic rays.
The present invention is a photosensitive resin composition comprising [1] (a) an amine imide compound that generates a base upon irradiation with actinic rays, and (b) a polyamic acid.
The present invention is the photosensitive resin composition according to the above [1], further comprising [2] (c) a singlet or triplet sensitizer.
The present invention also provides [3] (c) wherein the singlet or triplet sensitizer is at least one of a naphthalene derivative, an anthracene derivative, a carbazole derivative, a thioxanthone derivative, and a benzophenone derivative. ] The photosensitive resin composition of description.
Moreover, this invention irradiates the coating film which consists of the photosensitive resin composition in any one of [4] said [1] thru | or [3] with actinic light in the pattern form, and heated at 50-180 degreeC. Then, the relief pattern manufacturing method is characterized in that an unirradiated portion is developed and removed.
Furthermore, the present invention is [5] a method for producing a heat-resistant coating film, characterized in that the coating film comprising the photosensitive resin composition described above is irradiated with actinic rays over the entire surface and heated at 80 to 300 ° C. is there.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
The amine imide compound used in the present invention is not particularly limited as long as it is a compound that generates a base upon irradiation with actinic rays. For example, as a typical amine imide compound, it is represented by the following general formula (1) or (2),
[Chemical 1]

In the formula, R ¹ , R ² and R ³ are independently hydrogen, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkylidene group having 1 to 8 carbon atoms, and a cycloalkyl having 4 to 8 carbon atoms. A phenyl group, a benzyl group, an electron donating group substituted with a group, a cycloalkenyl group having 4 to 8 carbon atoms, a phenoxyalkyl group having 1 to 6 carbon atoms, a phenyl group, an electron donating group and / or an electron withdrawing group, and And / or a benzyl group substituted with an electron-withdrawing group. As a C1-C8 alkyl group, the alkyl group which has a substituent other than a linear alkyl group, for example, an isopropyl group, an isobutyl group, t-butyl group etc. are included. Among these substituents, from the viewpoint of ease of synthesis, solubility of amine imide, etc., an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 6 to 8 carbon atoms, and a phenoxyalkyl group having 1 to 6 carbon atoms. Is preferred. R ⁴ independently represents an alkyl group having 1 to 5 carbon atoms, a hydroxyl group, a cycloalkyl group having 4 to 8 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a phenyl group.
Ar ¹ in the general formula (1) is an aromatic group represented by the general formulas (I) to (XIII),
[Chemical 2]

In the formula, R ^{5 to} R ²⁸ are independently hydrogen, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkylthio group having 1 to 8 carbon atoms, an alkylidene group having 1 to 8 carbon atoms, carbon A cycloalkyl group having 4 to 8 carbon atoms, a cycloalkenyl group having 4 to 8 carbon atoms, an amino group, an alkylamino group having 1 to 6 carbon atoms, a dialkylamino group having 1 to 3 carbon atoms, a morpholino group, a mercapto group, a hydroxyl group, C1-C6 hydroxyalkyl group, halogen such as fluorine, chlorine, bromine, C1-C6 ester group, C1-C6 carbonyl group, aldehyde group, cyano group, trifluoromethyl group, cyano group , A nitro group, a benzoyl group, a phenyl group, a phenyl group substituted with an electron donating group and / or an electron withdrawing group, a benzyl group substituted with an electron donating group and / or an electron withdrawing group. In the formula, U to Z are any of carbon, nitrogen, oxygen, and sulfur atoms.
Ar ² in the general formula (2) is an aromatic group represented by the following formulas (XIV) to (XXII):
[Chemical 3]

R ^{29 to} R ³⁶ are independently hydrogen, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkylthio group having 1 to 8 carbon atoms, an alkylidene group having 1 to 8 carbon atoms, or a carbon number of 4 Cycloalkyl group having 8 to 8 carbon atoms, cycloalkenyl group having 4 to 8 carbon atoms, amino group, alkylamino group having 1 to 6 carbon atoms, dialkylamino group having 1 to 3 carbon atoms, morpholino group, mercapto group, hydroxyl group, carbon number 1-6 hydroxyalkyl group, halogen such as fluorine, chlorine, bromine, ester group having 1-6 carbon atoms, carbonyl group having 1-6 carbon atoms, aldehyde group, cyano group, trifluoromethyl group, cyano group, nitro group A phenyl group substituted with a group, a phenyl group, an electron donating group and / or an electron withdrawing group, a benzyl group substituted with an electron donating group and / or an electron withdrawing group. In the formula, W is nitrogen, oxygen, and sulfur substituted with carbon, nitrogen, and an alkyl group having 1 to 6 carbon atoms, and X to Z are independently carbon, nitrogen, oxygen, and sulfur atoms.
Like Ar ¹ , from the viewpoint of thermal stability and absorption wavelength, the substituent of R ^{29 to} R ³⁶ is preferably an electron-withdrawing group having 1 to 6 carbon atoms, a cyano group, or a nitro group. .
[0007]
A known method can be used for the synthesis of the amine imide compound. See, for example, Encyclopedia of Polymer Science and Engineering, John Wiley & Sons Ltd. (1985), Volume 1, p. 740, obtained from the reaction of the corresponding carboxylic acid ester with a halogenated hydrazine and sodium alkoxide or the reaction of a carboxylic acid ester with hydrazine and an epoxy compound. be able to.
In view of the ease of synthesis and safety, a synthesis method from the corresponding carboxylic acid ester, hydrazine and an epoxy compound is particularly preferred. The synthesis temperature and synthesis time are not particularly limited as long as the starting materials to be used are not decomposed. Generally, the desired amine imide compound is obtained by stirring at a temperature of 0 to 100 ° C. for 30 minutes to 7 days. Obtainable.
[0008]
As the polyamic acid used in the present invention, known ones can be used without any particular limitation, and examples thereof include those obtained by addition polymerization of tetracarboxylic dianhydride and a diamine compound.
[0009]
Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, and 3,3 ′, 4,4′-biphenyltetracarboxylic acid. Dianhydride, 1,2,5,6-naphthalenecarboxylic dianhydride, 1,2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic acid Anhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 4,4'-sulfonyldiphthalic dianhydride, m- Terphenyl-3,3 ", 4,4" -tetracarboxylic dianhydride, p-terphenyl-3,3 ", 4,4" -tetracarboxylic dianhydride, 4,4'-oxydiphthalic acid Anhydride, 1,1,1,3,3,3-hexafluoro-2, -Bis (2,3-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane Dianhydride, 1,1,1,3,3,3-hexafluoro-2,2′-bis [4- (2,3-dicarboxyphenoxy) phenyl] propane dianhydride, 1,1,1, 3,3,3-hexafluoro-2,2'-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride. These tetracarboxylic dianhydrides are used alone or in combination of two or more.
[0010]
Examples of the diamine compound include p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, m-xylylenediamine, 1,5-diaminonaphthalene, benzidine, 3,3′-dimethylbenzidine, 3,3 ′. -Dimethoxybenzidine, 4,4 '(or 3,4'-, 3,3'-, 2,4'-)-diaminodiphenylmethane, 4,4 '(or 3,4'-, 3,3'-, 2,4 '-)-diaminodiphenyl ether, 4,4' (or 3,4'-, 3,3'-, 2,4 '-)-diaminodiphenyl sulfone, 4,4' (or 3,4'-) 3,3′-, 2,4 ′-)-diaminodiphenyl sulfide, 4,4′-benzophenone diamine, 3,3′-benzophenone diamine, 4,4′-di (4-aminophenoxy) phenyl sulfone, 4, , 4'-bis (4-aminophenoxy ) Phenylsulfone, 4,4′-bis (4-aminophenoxy) biphenyl, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,1,1, 3,3,3-hexafluoro-2,2-bis (4-aminophenyl) propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 3,3-dimethyl-4,4 ′ -Diaminodiphenylmethane, 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 4,4'-di (3-aminophenoxy) phenylsulfone, 3,3'-diaminodiphenylsulfone, 2, , 2′-bis (4-aminophenyl) propane, aromatic diamines such as 4,4 ′-(9-fluorenylidene) dianiline, 2,7-diaminofluorene, 2,6-diaminopyridine, 2,4 Diaminopyridine, 2,4-diaminopyrimidine, 2,4-diamino-s-triazine, 2,7-diaminobenzofuran, 2,7-diaminocarbazole, 3,7-diaminophenothiazine, 2,5-diamino-1,3 , 4-thiadiazole, 2,4-diamino-6-phenyl-s-triazine and other heterocyclic diamines, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, 2,2-dimethylpropylenediamine, diaminopolysiloxane, etc. Examples include aliphatic diamines. These diamine compounds are used alone or in combination of two or more.
[0011]
The addition amount of the (a) amine imide compound of the present invention is preferably 0.1 to 50 parts by weight, more preferably 1 to 30 parts by weight with respect to 100 parts by weight of the solid content of (b) polyamic acid. If the amine imide compound is less than 0.1 parts by weight, the sensitivity is insufficient and imidization cannot be promoted. Moreover, when it exceeds 50 weight part, since the photodecomposition product of amine imide remains in a film after heating, it exists in the tendency for a film physical property to fall.
[0012]
As the sensitizer used in the present invention, known singlet sensitizers and triplet sensitizers can be used as long as they do not adversely affect the photosensitive resin composition. For example, aromatic compound derivatives such as naphthalene, anthracene, and pyrene, carbazole derivatives, aromatic carbonyl compounds, benzophenone derivatives, thioxanthone derivatives, and coumarin derivatives are preferably used. Of these, naphthalene derivatives, anthracene derivatives, carbazole derivatives, and triplet sensitizers are most preferred as singlet sensitizers, and thioxanthone derivatives and benzophenone derivatives. For example, 1-methylnaphthalene, 2-methylnaphthalene, 1-fluoronaphthalene, 1-chloronaphthalene, 2-chloronaphthalene, 1-bromonaphthalene, 2-bromonaphthalene, 1-iodonaphthalene, 2-iodonaphthalene, 1-naphthol 2-naphthol, 1-methoxynaphthalene, 2-methoxynaphthalene, 1,4-dicyanonaphthalene, anthracene, 1,2-benzanthracene, 9,10-dichloroanthracene, 9,10-dibromoanthracene, 9,10-diphenyl Anthracene, 9-cyanoanthracene, 9,10-dicyanoanthracene, 2,6,9,10-tetracyanoanthracene, carbazole, 9-methylcarbazole, 9-phenylcarbazole, 9-prop-2-ynyl-9H-carbazole, 9 Propyl-9H-carbazole, 9-vinylcarbazole, 9H-carbazole-9-ethanol, 9-methyl-3-nitro-9H-carbazole, 9-methyl-3,6-dinitro-9H-carbazole, 9-octanoylcarbazole 9-carbazolemethanol, 9-carbazolepropionic acid, 9-carbazolepropionitrile, 9-decyl-3,6-dinitro-9H-carbazole, 9-ethyl-3,6-dinitro-9H-carbazole, 9-ethyl -3-nitrocarbazole, 9-ethylcarbazole, 9-isopropylcarbazole, 9- (ethoxycarbonylmethyl) carbazole, 9- (morpholinomethyl) carbazole, 9-acetylcarbazole, 9-allylcarbazole, 9-benzyl-9H-carbazole , 9- Ruvazole acetic acid, 9- (2-nitrophenyl) carbazole, 9- (4-methoxyphenyl) carbazole, 9- (1-ethoxy-2-methyl-propyl) -9H-carbazole, 3-nitrocarbazole, 4-hydroxycarbazole 3,6-dinitro-9H-carbazole, 3,6-diphenyl-9H-carbazole, 2-hydroxycarbazole, 3,6-diacetyl-9-ethylcarbazole, benzophenone, 4-phenylbenzophenone, 4,4′-bis (Dimethoxy) benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 2-benzoylbenzoic acid methyl ester, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone 3,3′-dimethyl-4- Toxibenzophenone, 2,4,6-trimethylbenzophenone, [4- (4-methylphenylthio) phenyl] -phenylmethanone, xanthone, thioxanthone, 2-chlorothioxanthone, 4-chlorothioxanthone, 2-isopropylthioxanthone, 4- Examples include isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 1-chloro-4-propoxythioxanthone. These may be used alone or in combination. The amount of the sensitizer used is required to refer to the absorption wavelength and the molar extinction coefficient of the sensitizer, but is generally 0.01 to 10 parts by weight with respect to 1 part by weight of the amine imide compound. 1 to 5 parts by weight is particularly preferred. If the sensitizer is less than 0.01 parts by weight, the light absorption efficiency is lowered, and if it exceeds 10 parts by weight, the light may not reach the entire photosensitive resin composition.
[0013]
The photosensitive resin composition of the present invention may optionally contain additives such as an adhesion improver such as a coupling agent, a leveling agent, a plasticizer, an organic or inorganic filler, as necessary.
[0014]
The photosensitive resin composition of the present invention may use an organic solvent as necessary. The solvent that can be used is not particularly limited as long as it exhibits sufficient solubility in the amine imide compound and the polyamic acid. For example, acetone, acetonitrile, methyl ethyl ketone, diethyl ketone, cyclohexanone, toluene, chloroform, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, t-butanol, ethylene glycol monomethyl ether, xylene, tetrahydrofuran, dioxane, N, Examples thereof include N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, γ-butyrolactone, dimethyl sulfoxide, ethylene carbonate, sulfolane and the like. These organic solvents are used alone or in combination of two or more. The amount of such an organic solvent used is not particularly limited, but is preferably such that the solid content of the composition is from 5 to 95% by weight, and from 10 to 50% by weight from the viewpoint of coating properties. More preferred.
[0015]
When the photosensitive resin composition of the present invention is applied on a substrate such as a silicon wafer, a metal substrate, a glass substrate, or a ceramic substrate by an immersion method, a spray method, a screen printing method, a spin coating method, or the like, and contains an organic solvent Can be formed into a non-sticky coating film by heating and drying most of these organic solvents. Actinic rays are irradiated onto the coating film or the entire surface of the coating film. Examples of the actinic rays to be irradiated include ultraviolet rays, far ultraviolet rays, visible light, electron beams, and X-rays. After irradiating actinic rays, it heats at 80-300 degreeC for 5 second-1 hour, and promotes imidation. When actinic rays are irradiated in a pattern, a desired relief pattern is obtained by dissolving and removing unirradiated portions with an appropriate developer.
[0016]
There are no particular restrictions on the developer, but examples include alkaline aqueous solutions such as aqueous solutions containing sodium carbonate and tetramethylammonium hydroxide (TMH), N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl. A mixture of a good solvent such as 2-pyrrolidone and a poor solvent such as lower alcohol, water, and aromatic hydrocarbon is used. Further, after the development, in order to complete imidization, the film may be heated at 100 to 350 ° C. for 5 minutes to 2 hours. The relief pattern thus obtained can be processed by dry etching or the like on a passivation film formed using an inorganic material such as SiO ₂ or SiN.
[0017]
【Example】
Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited thereto.
[0018]
Synthesis of amine imide 1 (amine imide 1)
Add p-nitrobenzoic acid methyl ester (2.00 g, 11 mmol), N, N-dimethylhydrazine (0.66 g, 11 mmol), phenylglycidyl ether (1.66 g, 11 mmol) to tert-butanol (15.0 g). After stirring at 50 ° C. for 10 hours and further stirring at room temperature (25 ° C.) for 48 hours, a white precipitate was formed. This was filtered off, washed twice with ethyl acetate, and dried in a vacuum dryer to obtain an amine imide compound. The yield was 3.67 g, the yield was 85%, and the melting point was 146-147 ° C.
[0019]
Synthesis of amine imide 2 (amine imide 2)
p-Cyanobenzoic acid methyl ester (2.00 g, 12 mmol), N, N-dimethylhydrazine (0.75 g, 12 mmol), phenylglycidyl ether (1.86 g, 12 mmol) are added to tert-butanol (10 g), After stirring at 50 ° C. for 72 hours, the mixture was further stirred at room temperature for 48 hours. After removing tert-butanol from the obtained reaction solution with a rotary evaporator, 10 g of ethyl acetate was added and recrystallization was performed to obtain a white amineimide compound. The yield was 2.74 g, the yield was 65%, and the melting point was 148-149 ° C.
[0020]
Example 1
To 10 g (solid content 20% by weight) of an N-methyl-2-pyrrolidone solution of polyamic acid obtained by reacting 4,4′-diaminodiphenyl ether and pyromellitic dianhydride in equimolar amounts by a conventional method, 0.04 g of amine imide compound 1 obtained by synthesis was blended to prepare a photosensitive resin solution. This photosensitive resin solution was spin-coated on a silicone wafer and heated on a hot plate at 100 ° C. for 200 seconds to form a photosensitive coating film. The film thickness after drying was 10 μm. The coating film was exposed with a mirror projection exposure machine using an ultrahigh pressure mercury lamp as a light source through a photomask so that the irradiation dose at 366 nm was 3 J / cm ^2, and then heated at 150 ° C. for 60 seconds on a hot plate. Thereafter, immersion development was performed with a 1.68N TMH (tetramethylammonium hydroxide) aqueous solution, followed by rinsing with pure water. As a result, a negative relief pattern in which the pattern of the exposed portion remained was obtained.
[0021]
(Example 2)
When pattern formation was attempted in the same manner as in Example 1 except that 0.04 g of amine imide compound 2 was used instead of amine imide compound 1 and 0.02 g of benzophenone was used as a sensitizer, the pattern of the exposed portion remained. A negative relief pattern was obtained.
[0022]
(Comparative Example 1)
When pattern formation was attempted in the same manner as in Example 1 except that the amine imide compound 1 was not added, all of them were dissolved during development regardless of the exposed and unexposed areas, and no relief pattern was obtained.
[0023]
【The invention's effect】
ADVANTAGE OF THE INVENTION According to this invention, imidation of a polyamic acid can be accelerated | stimulated by low temperature by light irradiation, and also the curable composition excellent in storage stability can be provided.

Claims (5)

A photosensitive resin composition comprising (a) an amine imide compound that generates a base upon irradiation with active light, and (b) a polyamic acid. The photosensitive resin composition according to claim 1, further comprising (c) a singlet or triplet sensitizer. 3. The photosensitive resin composition according to claim 2, wherein (c) the singlet or triplet sensitizer is at least one of a naphthalene derivative, an anthracene derivative, a carbazole derivative, a thioxanthone derivative, and a benzophenone derivative. A coating film comprising the photosensitive resin composition according to any one of claims 1 to 3 is irradiated with an actinic ray in a pattern and heated at 50 to 180 ° C, and then an unirradiated portion is developed and removed. A method for producing a relief pattern characterized by the above. 4. Production of a heat-resistant coating film, wherein the coating film comprising the photosensitive resin composition according to any one of claims 1 to 3 is irradiated with actinic rays over the entire surface and heated at 80 to 300 ° C. Method.