JP2004198678A - Positive photosensitive resin precursor composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an alkali-developable positive photosensitive resin precursor composition having small shrinkage during curing and high heat resistance. <P>SOLUTION: The positive photosensitive resin precursor composition contains (a) a polymer consisting mainly of a structural unit expressed by formula (1); (b) a compound having a phenolic hydroxyl group expressed by formula (2); and (c) an esterified quinone diazide compound. In formula (1), R<SP>1</SP>represents a ≥2C organic group having the valance from 2 to 8, R<SP>2</SP>represents a ≥2C organic group having the valance from 2 to 6, and each p and q represents an integer from 0 to 4 satisfying p+q>0. In formula (2), R<SP>4</SP>represents a hydrogen atom or a 1-20C organic group, R<SP>5</SP>represents one of a hydrogen atom, a hydroxyl group and 1-20C organic groups, a represents an integer from 0 to 3, b represents an integer from 2 to 6, and c represents an integer from 0 to 4. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

【００２１】
（式中Ｒ¹は２個以上の炭素原子を有する２価から８価の有機基、Ｒ²は２個以上の炭素原子を有する２価から６価の有機基であり、Ｒ¹およびＲ²の少なくとも１つに芳香族環を有する。Ｒ³は水素、または炭素数１から２０までの有機基を示し、同一であっても異なっても良い。ｎは１０から１０００００までの整数、ｍは０から４までの整数、ｐ、ｑは０から４までの整数を示す。ただしｐ+ｑ＞０である。）
【００２２】
【化８】

【００２３】
（式中Ｒ⁴は水素または炭素数１〜２０の有機基を示す。Ｒ⁵は水素、水酸基および炭素数１〜２０の有機基から選ばれる１種を示す。ａは０から３の整数を示し、ｂは３から６の整数、ｃは０から４の整数を示す。）
【００２４】
【発明の実施の形態】
本発明における一般式（１）で表される構造単位を主成分とするポリマーとは、加熱あるいは適当な触媒により、イミド環、オキサゾール環、その他の環状構造を有するポリマーとなり得るものである。環構造となることで、耐熱性、耐溶剤性が飛躍的に向上する。
【００２５】
上記一般式（１）は、水酸基を有したポリアミド及びポリイミド酸、ポリアミド酸エステルを表しており、この水酸基の存在のために、アルカリ水溶液に対する溶解性が水酸基を有さないポリアミド酸よりも良好になる。特に、水酸基の中でもフェノール性の水酸基がアルカリ水溶液に対する溶解性より好ましい。
【００２６】
また、フッ素原子を一般式（１）中に１０重量％以上有することで、アルカリ水溶液で現像する際に、膜の界面に撥水性が適度に出るために、界面のしみこみなどが抑えられる。しかしながら、フッ素原子含有量が２０重量％を越えると、アルカリ水溶液に対する溶解性が低下すること、熱処理により環状構造にしたポリマーの耐有機溶媒性が低下すること、発煙硝酸に対する溶解性が低下する傾向がある。したがって、フッ素原子は１０重量％以上２０重量％以下含まれることが好ましい。
【００２７】
上記一般式（１）中、Ｒ¹（ＣＯＯＲ³）_m（ＯＨ）_p部分は酸二無水物の構造成分を表している。この酸二無水物は芳香族環を含有し、かつ水酸基を１個〜４個有した２個以上の炭素原子を有する２価〜８価の有機基であることが好ましく、炭素数６〜３０の３価または４価の有機基であることがさらに好ましい。
【００２８】
具体的には、下記一般式（３）に示されるような構造のものが好ましい。
【００２９】
【化９】

【００３０】
（式中Ｒ⁶、Ｒ⁸は炭素数２〜２０の２価〜４価の有機基を示し、Ｒ⁷は炭素数３〜２０の３価〜６価の有機基を示し、Ｒ⁹、Ｒ¹⁰は水素または炭素数１〜２０の有機基を示す。ｏ、ｓは０から２までの整数、ｒは１〜４までの整数を示す）。
【００３１】
Ｒ⁶、Ｒ⁸は得られるポリマーの耐熱性より芳香族環を含んだものが好ましく、その中でも特に好ましい構造としてトリメリット酸、トリメシン酸、ナフタレントリカルボン酸残基のようなものを挙げることができる。また、水酸基はアミド結合と隣り合った位置にあることが好ましい。このような例として、フッ素原子を含んだ、ビス（３−アミノ−４−ヒドロキシフェニル）ヘキサフルオロプロパン、ビス（３−ヒドロキシ−４−アミノフェニル）ヘキサフルオロプロパン、フッ素原子を含まない、ビス（３−アミノ−４−ヒドロキシフェニル）プロパン、ビス（３−ヒドロキシ−４−アミノフェニル）プロパン、３，３’−ジアミノ−４，４’−ジヒドロキシビフェニル、３，３’−ジアミノ−４，４’−ジヒドロキシビフェニル、２，４−ジアミノ−フェノール、２，５−ジアミノフェノール、１，４−ジアミノ−２，５−ジヒドロキシベンゼンのアミノ基が結合したものなどを挙げることができる。
【００３２】
また 一般式（１）のＲ¹（ＣＯＯＲ³）_m（ＯＨ）_p部分が一般式（３）で表される化合物の中で、好ましい化合物を例示すると下記に示したような構造のものが挙げられるが、これらに限定されない。
【００３３】
【化１０】

【００３４】
また、アルカリに対する溶解性、感光性能、耐熱性を損なわない範囲で、Ｒ¹（ＣＯＯＲ³）_m（ＯＨ）_p部分を水酸基を有していないテトラカルボン酸、ジカルボン酸で変性することもできる。この例としては、ピロメリット酸、ベンゾフェノンテトラカルボン酸、ビフェニルテトラカルボン酸、ジフェニルエーテルテトラカルボン酸、ジフェニルスルホンテトラカルボン酸などの芳香族テトラカルボン酸やそのカルボキシル基２個をメチル基やエチル基にしたジエステル化合物、ブタンテトラカルボン酸、シクロペンタンテトラカルボン酸などの脂肪族のテトラカルボン酸やそのカルボキシル基２個をメチル基やエチル基にしたジエステル化合物、テレフタル酸、イソフタル酸、ジフェニルエーテルジカルボン酸、ナフタレンジカルボン酸などの芳香族ジカルボン酸、アジピン酸などの脂肪族ジカルボン酸などを挙げることができる。Ｒ³を含む成分に水酸基のある化合物を使用する場合、Ｒ¹を含む成分に必ずしも水酸基は必要なく、上記したテトラカルボン酸、ジカルボン酸をＲ¹を含む成分として使用できる。ここで、変性は、酸成分の５０モル％以下の変性が好ましいが、さらに好ましくは３０モル％以下である。５０モル％を越えて変性を行うと、アルカリに対する溶解性、感光性が損なわれる恐れがある。
【００３５】
一般式（１）中、Ｒ²を含む部分はジアミンの構造成分を表している。この中で、Ｒ²（ＯＨ）_qの好ましい例としては、得られるポリマーの耐熱性より芳香族を有し、かつ水酸基を有するものが好ましく、具体的な例としてはフッ素原子を有した、ビス（アミノ−ヒドロキシ−フェニル）ヘキサフルオロプロパン、フッ素原子を有さない、ジアミノジヒドロキシピリミジン、ジアミノジヒドロキシピリジン、ヒドロキシ−ジアミノ−ピリミジン、ジアミノフェノール、ジヒドロキシベンチジンなどの化合物や一般式（４）、（５）、（６）に示す構造のものをあげることができる。
【００３６】
【化１１】

【００３７】
（式中Ｒ¹¹、Ｒ¹³は炭素数２〜２０の３価〜４価の有機基を示し、Ｒ¹²は炭素数２〜３０の２価の有機基を示す。ｔ、ｕは１または２を示す。）
【００３８】
【化１２】

【００３９】
（式中Ｒ¹⁴、Ｒ¹⁶は炭素数２〜２０までの２価の有機基を示し、Ｒ¹⁵は、炭素数３〜２０の３価〜６価の有機基を示す。ｖは１〜４までの整数を示す。）
【００４０】
【化１３】

【００４１】
（式中Ｒ¹⁷は炭素数２〜２０の２価の有機基を示し、Ｒ¹⁸は、炭素数３〜２０の３価〜６価の有機基を示す。ｗは１〜４までの整数を示す。）
この中で、Ｒ¹¹〜Ｒ¹²は、得られるポリマーの耐熱性の点から芳香族環を有した有機基が好ましい。
【００４２】
一般式（１）のＲ²（ＯＨ）_qを一般式（４）で表される具体例を下記に示す。
【００４３】
【化１４】

【００４４】
また、一般式（１）のＲ²（ＯＨ）_qを一般式（５）で表される具体例を下記に示す。
【００４５】
【化１５】

【００４６】
また、一般式（１）のＲ²（ＯＨ）_qを一般式（６）で表される具体例を下記に示す。
【００４７】
【化１６】

【００４８】
一般式（４）において、Ｒ¹¹、Ｒ¹³は炭素数２〜２０の３価〜４価の有機基を示しており、得られるポリマーの耐熱性の点から芳香族環を有したものが好ましい。具体的には、ヒドロキシフェニル基、ジヒドロキシフェニル基、ヒドロキシナフチル基、ジヒドロキシナフチル基、ヒドロキシビフェニル基、ジヒドロキシビフェニル基、ビス（ヒドロキシフェニル）ヘキサフルオロプロパン基、ビス（ヒドロキシフェニル）プロパン基、ビス（ヒドロキシフェニル）スルホン基、ヒドロキシジフェニルエーテル基、ジヒドロキシジフェニルエーテル基など例示することができる。また、ヒドロキシシクロヘキシル基、ジヒドロキシシクロヘキシル基などの脂肪族の基も使用することができる。Ｒ¹²は炭素数２〜３０までの２価の有機基を表している。得られるポリマーの耐熱性の点から芳香族を有した２価の基がよく、このような例としてはフェニル基、ビフェニル基、ジフェニルエーテル基、ジフェニルヘキサフルオロプロパン基、ジフェニルプロパン基、ジフェニルスルホン基などをあげることができるが、これ以外にも脂肪族のシクロヘキシル基なども使用することができる。
【００４９】
一般式（５）において、Ｒ¹⁴、Ｒ¹⁶は炭素数２〜２０までの２価の有機基を表している。得られるポリマーの耐熱性の点から芳香族を有した２価の基がよく、このような例としてはフェニル基、ビフェニル基、ジフェニルエーテル基、ジフェニルヘキサフルオロプロパン基、ジフェニルプロパン基、ジフェニルスルホン基などをあげることができるが、これ以外にも脂肪族のシクロヘキシル基なども使用することができる。Ｒ¹⁵は、炭素数３〜２０の３価〜６価の有機基を示しており、得られるポリマーの耐熱性の点から芳香族環を有したものが好ましい。具体的には、ヒロドキシフェニル基、ジヒドロキシフェニル基、ヒドロキシナフチル基、ジヒドロキシナフチル基、ヒドロキシビフェニル基、ジヒドロキシビフェニル基、ビス（ヒドロキシフェニル）ヘキサフルオロプロパン基、ビス（ヒドロキシフェニル）プロパン基、ビス（ヒドロキシフェニル）スルホン基、ヒドロキシジフェニルエーテル基、ジヒドロキシジフェニルエーテル基などを挙げることができる。また、ヒドロキシシクロヘキシル基、ジヒドロキシシクロヘキシル基などの脂肪族の基も使用することができる。
【００５０】
一般式（６）においてＲ¹⁷は炭素数２〜２０より選ばれる２価の有機基を表している。得られるポリマーの耐熱性から芳香族を有した２価の基がよく、このような例としては、フェニル基、ビフェニル基、ジフェニルエーテル基、ジフェニルヘキサフルオロプロパン基、ジフェニルプロパン基、ジフェニルスルホン基などをあげることができるが、これ以外にも脂肪族のシクロヘキシル基なども使用することができる。Ｒ¹⁸は炭素数３〜２０より選ばれる３価〜６価の有機基を示しており、得られるポリマーの耐熱性の点から芳香族環を有したものが好ましい。具体的には、ヒドロキシフェニル基、ジヒドロキシフェニル基、ヒドロキシナフチル基、ジヒドロキシナフチル基、ヒドロキシビフェニル基、ジヒドロキシビフェニル基、ビス（ヒドロキシフェニル）ヘキサフルオロプロパン基、ビス（ヒドロキシフェニル）プロパン基、ビス（ヒドロキシフェニル）スルホン基、ヒドロキシジフェニルエーテル基、ジヒドロキシジフェニルエーテル基などを挙げることができる。また、ヒドロキシシクロヘキシル基、ジヒドロキシシクロヘキシル基などの脂肪族の基も使用することができる。
【００５１】
一般式（１）のＲ²（ＯＨ）_qの内の１〜４０モル％は、他のジアミン成分を用いて変性することもできる。これらの例としては、フェニレンジアミン、ジアミノジフェニルエーテル、アミノフェノキシベンゼン、ジアミノジフェニルメタン、ジアミノジフェニルスルホン、ビス（トリフルオロメチル）ベンチジン、ビス（アミノフェノキシフェニル）プロパン、ビス（アミノフェノキシフェニル）スルホン、あるいはこれらの芳香族環をアルキル基やハロゲン原子で置換した化合物などを挙げることができる。また、脂肪族のシクロヘキシルジアミン、メチレンビスシクロヘキシルアミンなどが挙げられるが、このようなジアミン成分を４０モル％を越えて共重合すると得られるポリマーの耐熱性が低下する。Ｒ¹成分に水酸基のある化合物を使用する場合、Ｒ³成分に水酸基は必ずしも必要なく、上記した水酸基のないジアミンを使用できる。
【００５２】
一般式（１）のＲ³は水素、または炭素数１〜２０の有機基を表している。得られるポジ型感光性樹脂前駆体溶液の安定性からは、Ｒ³は有機基が好ましいが、アルカリ水溶液の溶解性の点からは水素が好ましい。本発明においては、水素原子とアルキル基を混在させることができる。このＲ³の水素と有機基の量を制御することで、アルカリ水溶液に対する溶解速度が変化するので、この調整により適度な溶解速度を有したポジ型感光性樹脂前駆体組成物を得ることができる。好ましい範囲は、Ｒ³の１０％〜９０％が水素原子であることである。Ｒ³の炭素数が２０を越えるとアルカリ水溶液に溶解しなくなるため好ましくない。これらの点から、Ｒ³は、炭素数１〜１６までの炭化水素基を少なくとも１つ以上含有し、その他は水素原子であることが好ましい。
【００５３】
一般式（１）のｍはカルボキシル基の数を示しており、０〜４までの整数を示している。一般式（１）のｎは本発明のポリマーの構造単位の繰り返し数を示しており、１０〜１０００００の範囲である。
【００５４】
一般式（１）で表される構造単位としてポリヒドロキシアミドを使用することも出来る。このようなポリヒドロキシアミドの製造方法としては、例えば、ビスアミノフェノール化合物とジカルボン酸を縮合反応させることで得ることが出来る。具体的には、ジシクロヘキシルカルボジイミド（ＤＣＣ）のような脱水縮合剤と酸を反応させ、ここにビスアミノフェノール化合物を加える方法やピリジンなどの３級アミンを加えたビスアミノフェノール化合物の溶液にジカルボン酸ジクロリドの溶液を滴下する方法などがある。
【００５５】
ポリヒドロキシアミドを使用する場合、ポリヒドロキシアミドの溶液にナフトキノンジアジドスルホン酸エステルのような感光剤を加えることで、紫外線で露光した部分をアルカリ水溶液で除去できるポジ型の感光性耐熱性樹脂前駆体組成物を得ることが出来る。
【００５６】
さらに、基板との接着性を向上させるために、耐熱性を低下させない範囲で 一般式（１）のＲ¹、Ｒ²にシロキサン構造を有する脂肪族の基を共重合してもよい。具体的には、ジアミン成分として、ビス（３−アミノプロピル）テトラメチルジシロキサン、ビス（ｐ−アミノ−フェニル）オクタメチルペンタシロキサンなどを１〜１０モル％共重合したものなどがあげられる。
【００５７】
本発明のポジ型感光性樹脂前駆体組成物に含まれる（ａ）ポリマーは、一般式（１）で表される構造単位のみからなるものであっても良いし、他の構造単位との共重合体あるいはブレンド体であっても良い。その際、一般式（１）で表される構造単位を９０モル％以上含有していることが好ましい。共重合あるいはブレンドに用いられる構造単位の種類および量は最終加熱処理によって得られるポリイミド系ポリマの耐熱性を損なわない範囲で選択することが好ましい。
【００５８】
本発明に使用する（ａ）ポリマーは、公知の方法により合成される。例えば、低温中でテトラカルボン酸２無水物とジアミン化合物を反応させる方法、テトラカルボン酸２無水物とアルコールとによりジエステルを得、その後、アミンと縮合剤の存在下で反応させる方法、テトラカルボン酸２無水物とアルコールとによりジエステルを得、その後、残りのジカルボン酸を酸クロリド化し、アミンと反応させる方法などで合成することができる。
【００５９】
次に、本発明で使用する下記一般式（２）で示される（ｂ）化合物について記載する。
【００６０】
【化１７】

【００６１】
（式中Ｒ⁴は水素または炭素数１〜２０の有機基を示す。Ｒ⁵は水素、水酸基および炭素数１〜２０の有機基から選ばれる１種。ａは０から３の整数を示し、ｂは２から６の整数、ｃは０から４の整数を示す）。
【００６２】
一般式（２）のＲ⁴は、好ましくは、水素原子または炭素数１〜６の有機基、更に好ましくは水素原子、メチル基、エチル基、tert-ブチル基のいずれかである。Ｒ⁵は、好ましくは水素、水酸基、メチル基、tert-ブチル基、ビニル基から選ばれる１種以上である。
【００６３】
本発明における一般式（２）で表されたフェノール性水酸基を有する化合物としては、たとえば、以下の構造の化合物が挙げられる。
【００６４】
【化１８】

【００６５】
このようなフェノール性水酸基を有する化合物の添加量としては、（ａ）のポリマー１００重量部に対して、好ましくは１から５０重量部であり、さらに好ましくは３から４０重量部の範囲である。
【００６６】
次に、（ｃ）エステル化したキノンジアジド化合物について記載する。
【００６７】
本発明に添加されるキノンジアジド化合物としては、フェノール性水酸基を有した化合物にナフトキノンジアジドのスルホン酸がエステルで結合した化合物が好ましく使用される。これらは、単独でも二種類以上混合しても使用することができる。ここで用いられるフェノール性水酸基を有する化合物は、本発明に用いる（ｂ）一般式（２）で表されるフェノール性水酸基を有する化合物と同じでも、異なるものであってもいい。例えば一般式（２）に該当しないような化合物としては、ナフトール、テトラヒドロキシベンゾフェノン、没食子酸メチルエステル、ビスフェノールＡ、メチレンビスフェノール、ＴｒｉｓＰ−ＨＡＰ（商品名、本州化学工業（株）製）、ＢｉｓＰ−ＡＰ（商品名、本州化学工業（株）製）、ＴｒｉｓＰ−ＨＡＰ（商品名、本州化学工業（株）製）、ＴｒｉｓＰ−ＰＡ（商品名、本州化学工業（株）製）、ＢｉｓＲＳ−２Ｐ、ＢｉｓＰＧ−２６Ｘ、ＢｉｓＯＣ−ＯＣＨＰ、ＢｉｓＰ−ＯＣＨＰ、ＢｉｓＰＣ−ＯＣＨＰ、Ｂｉｓ２５Ｘ−ＯＣＨＰ、Ｂｉｓ２６Ｘ−ＯＣＨＰ、ＢｉｓＯＣＨＰ−ＯＣ、Ｂｉｓ２３６Ｔ−ＯＣＨＰ、メチレントリス−ＦＲ−ＣＲ、ＢｉｓＲＳ−２６Ｘ、ＢｉｓＲＳ−ＯＣＨＰ（以上、商品名、本州化学工業（株）製）、ＢＩＲ−ＯＣ、ＢＩＰ−ＰＣ、ＢＩＲ−ＰＣ、ＢＩＲ−ＰＴＢＰ、ＢＩＲ−ＰＣＨＰ、ＢＩＰ−ＢＩＯＣ−Ｆ、４ＰＣ、ＢＩＲ−ＢＩＰＣ−Ｆ（以上、商品名、旭有機材工業（株）製）等のフェノール性水酸基を有する化合物の５−ナフトキノンジアジドスルホニルエステル化合物、４−ナフトキノンジアジドスルホニルエステル化合物が挙げられるが、これらに限定されない。
【００６８】
４−ナフトキノンジアジドスルホニルエステル化合物は水銀灯のｉ線領域に吸収を持っており、ｉ線露光に適しており、５−ナフトキノンジアジドスルホニルエステル化合物は水銀灯のｇ線領域まで吸収が伸びており、ｇ線露光に適している。本発明においては、４−ナフトキノンジアジドスルホニルエステル化合物、５−ナフトキノンジアジドスルホニルエステル化合物のどちらも好ましく使用することが出来るが、露光する波長によって４−ナフトキノンジアジドスルホニル、エステル化合物、５−ナフトキノンジアジドスルホニルエステル化合物を選択することがより好ましい。また、同一分子中に４−ナフトキノンジアジドスルホニル基、５−ナフトキノンジアジドスルホニル基を併用したナフトキノンジアジドスルホニルエステル化合物を使用することもできるし、４−ナフトキノンジアジドスルホニルエステル化合物と５−ナフトキノンジアジドスルホニルエステル化合物を混合して使用することもできる。
【００６９】
本発明に使用する（ｃ）エステル化したキノンジアジド化合物は、フェノール性水酸基を有する化合物と、キノンジアジドスルホン酸化合物とのエステル化反応によって、合成することが可能であって、公知の方法により合成することができる。
【００７０】
このようなエステル化したキノンジアジドを使用することで解像度、感度、残膜率が向上する。
【００７１】
また、エステル化したナフトキノンジアジド化合物の分子量が１５００を越えると、その後の熱処理においてナフトキノンジアジド化合物が十分に熱分解しないために、得られる膜の耐熱性が低下したり、機械特性が低下したり、接着性が低下するなどの問題が生じる可能性がある。このような観点から、好ましいエステル化したキノンジアジド化合物の分子量は３００〜１５００である。さらに好ましくは、３５０〜１２００である。また、このようなエステル化したキノンジアジド化合物の添加量としては、（ａ）のポリマー１００重量部に対して、好ましくは１から５０重量部であり、さらに好ましくは３から４０重量部の範囲である。
【００７２】
（ｃ）エステル化したキノンジアジド化合物を添加することで、現像後の未露光部の膜減りが大幅に低下し、良好なパターンを短い現像時間で得ることが出来る。
【００７３】
本発明のポジ型感光性樹脂前駆体組成物には、必要に応じて、該ポジ型感光性耐熱性前駆体組成物と基板との塗れ性を向上させる目的等で界面活性剤、乳酸エチルやプロピレングリコールモノメチルエーテルアセテートなどのエステル類、エタノールなどのアルコール類、シクロヘキサノン、メチルイソブチルケトンなどのケトン類、テトラヒドロフラン、ジオキサンなどのエ−テル類を混合しても良い。また、２酸化ケイ素、２酸化チタンなどの無機粒子、あるいはポリイミドの粉末などを添加することもできる。
【００７４】
さらに、シリコンウエハーなどの下地基板との接着性を高めるために、シランカップリング剤、チタンキレート剤などをポジ型感光性耐熱性樹脂前駆体組成物のワニスに０．５から１０重量％添加したり、下地基板をこのような薬液で前処理したりすることもできる。
【００７５】
ワニスに添加する場合、メチルメタクリロキシジメトキシシラン、３−アミノプロピルトリメトキシシランなどのシランカップリング剤、チタンキレート剤、アルミキレート剤をワニス中の（ａ）ポリマーに対して０．５から１０重量％添加する方法が好ましく使用される。
【００７６】
基板を処理する場合、上記したカップリング剤をイソプロパノール、エタノール、メタノール、水、テトラヒドロフラン、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテル、乳酸エチル、アジピン酸ジエチルなどの溶媒に０．５から２０重量％溶解させた溶液をスピンコート、浸漬、スプレー塗布、蒸気処理などで表面処理をする方法が好ましく使用される。場合によっては、その後、５０℃から３００℃までの温度をかけることで、基板と上記カップリング剤との反応を進行させる方法が好ましく使用される。
【００７７】
次に、本発明のポジ型感光性耐熱性前駆体組成物を用いて耐熱性樹脂パターンを形成する好ましい方法について説明する。
【００７８】
ポジ型感光性耐熱性前駆体組成物を基板上に塗布する。基板としてはシリコンウエハー、セラミックス類、ガリウムヒ素などが用いられるが、これらに限定されない。塗布方法としてはスピンナを用いた回転塗布、スプレー塗布、ロールコーティングなどの方法があり、特に制限無く使用できる。また、塗布膜厚は、塗布手法、組成物の固形分濃度、粘度などによって異なるが、通常、乾燥後の膜厚が、０．１から１５０μｍになるように塗布される。
【００７９】
次に、ポジ型感光性耐熱性前駆体組成物を塗布した基板を乾燥して、感光性耐熱性前駆体組成物皮膜を得る。乾燥はオーブン、ホットプレート、赤外線などを使用し、５０度から１５０度の範囲で１分から数時間行うのが好ましい。
【００８０】
次に、この感光性耐熱性前駆体組成物皮膜上に所望のパターンを有するマスクを通して化学線を照射し、露光する。露光に用いられる化学線としては紫外線、可視光線、電子線、Ｘ線などがあるが、水銀灯のｉ線（３６５ｎｍ）、ｈ線（４０５ｎｍ）、ｇ線（４３６ｎｍ）を用いるのが好ましい。
【００８１】
耐熱性樹脂のパタ−ンを形成するには、露光後、現像液を用いて露光部を除去することによって達成される。現像液としては、テトラメチルアンモニウムの水溶液、ジエタノールアミン、ジエチルアミノエタノール、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウム、トリエチルアミン、ジエチルアミン、メチルアミン、ジメチルアミン、酢酸ジメチルアミノエチル、ジメチルアミノエタノール、ジメチルアミノエチルメタクリレート、シクロヘキシルアミン、エチレンジアミン、ヘキサメチレンジアミンなどのアルカリ性を示す化合物の水溶液が好ましい。また場合によっては、これらのアルカリ水溶液にＮ−メチル−２−ピロリドン、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、ジメチルスルホキシド、γ−ブチロラクロン、ジメチルアクリルアミドなどの極性溶媒、メタノール、エタノール、イソプロパノールなどのアルコール類、乳酸エチル、プロピレングリコールモノメチルエーテルアセテートなどのエステル類、シクロペンタノン、シクロヘキサノン、イソブチルケトン、メチルイソブチルケトンなどのケトン類などを単独あるいは数種を組み合わせたものを添加してもよい。現像後は水にてリンス処理をする。ここでもエタノール、イソプロピルアルコールなどのアルコール類、乳酸エチル、プロピレングリコールモノメチルエーテルアセテートなどのエステル類などを水に加えてリンス処理をしても良い。
【００８２】
現像後、２００℃から５００℃の温度を加えて耐熱性樹脂皮膜に変換する。この加熱処理は温度を選び、段階的に昇温するか、ある温度範囲を選び連続的に昇温しながら５分から５時間実施することが好ましい。一例としては、１３０℃、２００℃、３５０℃で各３０分づつ熱処理する方法がある。あるいは室温より４００℃まで２時間かけて直線的に昇温するなどの方法が挙げられる。
【００８３】
本発明のポジ型感光性耐熱性前駆体組成物を用いて形成した耐熱性樹脂皮膜の用途は特に限定されないが、好ましくは、半導体のパッシベーション膜、半導体素子の保護膜、高密度実装用多層配線の層間絶縁膜などの用途に用いられる。
【００８４】
【実施例】
以下実施例および技術をあげて本発明を説明するが、本発明はこれらの例によって限定されるものではない。なお、実施例中のポジ型感光性耐熱性樹脂前駆体組成物の作製、評価は以下の方法により行った。
【００８５】
感光性ポリイミド前駆体膜の作製
６インチシリコンウエハー上に、ポジ型感光性耐熱性樹脂前駆体組成物（以下ワニスと呼ぶ）をプリベーク後の膜厚が１４μｍとなるように塗布し、ついでホットプレート（東京エレクトロン（株）製Ｍａｒｋ−７）を用いて、１２０℃で３分プリベークすることにより、感光性ポリイミド前駆体膜を得た。
【００８６】
膜厚の測定方法
大日本スクリーン製造（株）製ラムダエースＳＴＭ−６０２を使用し、屈折率１．６４で測定を行った。
【００８７】
露光
露光機（ＧＣＡ社製ｉ線ステッパーＤＳＷ−８０００）に、パターンの切られたレチクルをセットし、露光時間を変化させ（３６５ｎｍの強度）てｉ線露光を行った。
【００８８】
現像
東京エレクトロン（株）製Ｍａｒｋ−７の現像装置を用い、５０回転で水酸化テトラメチルアンモニウムの２．３８％水溶液を１０秒間噴霧した。この後、０回転で６０秒間静置し、４００回転で水にてリンス処理、３０００回転で１０秒振り切り乾燥した。
【００８９】
残膜率の算出
残膜率は以下の式に従って算出した。
残膜率（％）＝（現像後の膜厚÷プリベーク後の膜厚）×１００
感度の算出
露光、現像後、５０μｍのライン・アンド・スペースパターン（１Ｌ／１Ｓ）を１対１の幅に形成する露光時間（以下、これを最適露光時間という）を求めた。
【００９０】
解像度の算出
露光、現像後、５０μｍのライン・アンド・スペースパターン（１Ｌ／１Ｓ）を１対１の幅に形成する最適露光時間における最小のパターン寸法を解像度とした。
【００９１】
収縮率の算出
作製された感光性ポリイミド前駆体膜を、光洋リンドバーグ（株）製イナートオーブンＩＮＨ−２１ＣＤを用いて、窒素気流下（酸素濃度２０ｐｐｍ以下）、１４０℃で３０分、その後、３５０℃まで１時間で昇温して３５０℃で１時間熱処理をし、キュア膜を作製した。収縮率は以下の式に従って算出した。
収縮率（％）＝（プリベーク後の膜厚−キュア後の膜厚）÷プリベーク後の膜厚×１００。
【００９２】
合成例１ ヒドロキシル基含有酸無水物の合成
乾燥窒素気流下、２，２−ビス（３−アミノ−４−ヒドロキシフェニル）ヘキサフルオロプロパン（ＢＡＨＦ）１８．３ｇ（０．０５モル）とアリルグリシジルエーテル３４．２ｇ（０．３モル）をガンマブチロラクトン１００ｇに溶解させ、−１５℃に冷却した。ここにガンマブチロラクトン５０ｇに溶解させた無水トリメリット酸クロリド２２．１ｇ（０．１１モル）を反応液の温度が０℃を越えないように滴下した。滴下終了後、０℃で４時間反応させた。この溶液をロータリーエバポレーターで濃縮して、トルエン１Ｌに投入して下記酸無水物（１）を得た。
【００９３】
【化１９】

【００９４】
合成例２ ヒドロキシル基含有ジアミン化合物（１）の合成
ＢＡＨＦ１８．３ｇ（０．０５モル）をアセトン１００ｍｌ、プロピレンオキシド１７．４ｇ（０．３モル）に溶解させ、−１５℃に冷却した。ここに４−ニトロベンゾイルクロリド２０．４ｇ（０．１１モル）をアセトン１００ｍｌに溶解させた溶液を滴下した。滴下終了後、−１５℃で４時間反応させ、その後室温に戻した。析出した白色固体をろ別し、５０℃で真空乾燥した。次いで、該白色固体３０ｇを３００ｍｌのステンレスオートクレーブに入れ、メチルセルソルブ２５０ｍｌに分散させ、５％パラジウム−炭素を２ｇ加えた。ここに水素を風船で導入して、還元反応を室温で行った。約２時間後、風船がこれ以上しぼまないことを確認して反応を終了させた。反応終了後、ろ過して触媒であるパラジウム化合物を除き、ロータリーエバポレーターで濃縮し、下記ジアミン化合物（１）を得た。得られた固体をそのまま反応に使用した。
【００９５】
【化２０】

【００９６】
合成例３ ヒドロキシル基含有ジアミン（２）の合成
２−アミノ−４−ニトロフェノール１５．４ｇ（０．１モル）をアセトン５０ｍｌ、プロピレンオキシド３０ｇ（０．３４モル）に溶解させ、−１５℃に冷却した。ここにイソフタル酸クロリド１１．２ｇ（０．０５５モル）をアセトン６０ｍｌに溶解させた溶液を徐々に滴下した。滴下終了後、−１５℃で４時間反応させた。その後、室温に戻して生成している沈殿をろ過で集めた。この沈殿をＧＢＬ２００ｍｌに溶解させて、５％パラジウム−炭素３ｇを加えて、激しく攪拌した。ここに水素ガスを入れた風船を取り付け、室温で水素ガスの風船がこれ以上縮まない状態になるまで攪拌を続け、さらに２時間水素ガスの風船を取り付けた状態で攪拌した。攪拌終了後、ろ過でパラジウム化合物を除き、溶液をロータリーエバポレーターで半量になるまで濃縮した。ここにエタノールを加えて、再結晶を行い、下記ジアミン（２）の結晶を得た。
【００９７】
【化２１】

【００９８】
合成例４ ヒドロキシル基含有ジアミン（３）の合成
２−アミノ−４−ニトロフェノール１５．４ｇ（０．１モル）をアセトン１００ｍｌ、プロピレンオキシド１７．４ｇ（０．３モル）に溶解させ、−１５℃に冷却した。ここに４−ニトロベンゾイルクロリド２０．４ｇ（０．１１モル）をアセトン１００ｍｌに溶解させた溶液を徐々に滴下した。滴下終了後、−１５℃で４時間反応させた。その後、室温に戻して生成している沈殿をろ過で集めた。この後、合成例２と同様にして下記ジアミン（３）の結晶を得た。
【００９９】
【化２２】

【０１００】
合成例５ キノンジアジド化合物（１）の合成
乾燥窒素気流下、ＢｉｓＰＧ−２６Ｘ（商品名、本州化学工業（株）製）、１９．７１ｇ（０．０５モル）と５−ナフトキノンジアジドスルホニル酸クロリド１３．５６ｇ（０．０５モル）と４−ナフトキノンジアジドスルホニル酸クロリド１３．１４ｇ（０．０５モル）を１，４−ジオキサン４５０ｇに溶解させ、室温にした。ここに、１，４−ジオキサン５０ｇと混合させたトリエチルアミン１０．１２ｇを系内が３５℃以上にならないように滴下した。滴下後、３０℃で２時間攪拌した。トリエチルアミン塩を濾過し、ろ液を水に投入させた。その後、析出した沈殿をろ過で集めた。この沈殿を真空乾燥機で乾燥させ、下記キノンジアジド化合物（１）を得た。ここで、式中の比はモル比である。
【０１０１】
【化２３】

【０１０２】
合成例６ キノンジアジド化合物（２）の合成
乾燥窒素気流下、ＢＩＲ−ＰＴＢＰ（商品名、旭有機材工業（株）製）１９．７２ｇ（０．０５モル）と４−ナフトキノンジアジドスルホニル酸クロリド２６．８６ｇ（０．１モル）を１，４−ジオキサン４５０ｇに溶解させ、室温にした。ここに、１，４−ジオキサン５０ｇと混合させたトリエチルアミン１０．１２ｇを系内が３５℃以上とならないように滴下し、滴下後、３０℃で２時間攪拌した。トリエチルアミン塩を濾過し、ろ液を水に投入させた。その後、析出した沈殿をろ過で集めた。この沈殿を真空乾燥機で乾燥させ、下記キノンジアジド化合物（２）を得た。式中の比はモル比である。
【０１０３】
【化２４】

【０１０４】
合成例７ キノンジアジド化合物（３）の合成
乾燥窒素気流下、２−ナフトール７．２１ｇ（０．０５モル）と５−ナフトキノンジアジドスルホニル酸クロリド１３．４３ｇ（０．０５モル）を１，４−ジオキサン４５０ｇに溶解させ、室温にした。ここに、１，４−ジオキサン５０ｇと混合させたトリエチルアミン５．０６ｇを用い、合成例６と同様にして、下記キノンジアジド化合物（３）を得た。
【０１０５】
【化２５】

【０１０６】
合成例８ キノンジアジド化合物（４）の合成
乾燥窒素気流下、ＴｒｉｓＰ ＨＡＰ（商品名、本州化学工業（株）製）、１５．３１ｇ（０．０５モル）と５−ナフトキノンジアジドスルホニル酸クロリド４０．２８ｇ（０．１５モル）を１，４−ジオキサン４５０ｇに溶解させ、室温にした。ここに、１，４−ジオキサン５０ｇと混合させたトリエチルアミン１５．１８ｇを用い、合成例６と同様にして、下記キノンジアジド化合物（４）を得た。
【０１０７】
【化２６】

【０１０８】
合成例９ キノンジアジド化合物（５）の合成
乾燥窒素気流下、４−イソプロピルフェノール６．８１ｇ（０．０５モル）と５−ナフトキノンジアジドスルホニル酸クロリド１３．４３ｇ（０．０５モル）を１，４−ジオキサン４５０ｇに溶解させ、室温にした。ここに、１，４−ジオキサン５０ｇと混合させたトリエチルアミン５．０６ｇを用い、合成例６と同様にして、下記キノンジアジド化合物（５）を得た。
【０１０９】
【化２７】

【０１１０】
合成例１０ キノンジアジド化合物（６）の合成
乾燥窒素気流下、ビスフェノールＡ １１．４１ｇ（０．０５モル）と５−ナフトキノンジアジドスルホニル酸クロリド２６．８６ｇ（０．１モル）を１，４−ジオキサン４５０ｇに溶解させ、室温にした。ここに、１，４−ジオキサン５０ｇと混合させたトリエチルアミン１０．１２ｇを用い、合成例６と同様にして、下記キノンジアジド化合物（６）を得た。
【０１１１】
【化２８】

【０１１２】
合成例１１ キノンジアジド化合物（７）の合成
乾燥窒素気流下、ベンゼン−１，２，３−トリカルボキシ トリス−（（２−ヒドロキシフェニル）アミド）２４．２ｇ（０．０５モル）と５−ナフトキノンジアジドスルホニル酸クロリド４０．２８ｇ（０．１５モル）を１，４−ジオキサン４５０ｇに溶解させ、室温にした。ここに、１，４−ジオキサン５０ｇと混合させたトリエチルアミン１０．１２ｇを用い、合成例６と同様にして、下記キノンジアジド化合物（７）を得た。
【０１１３】
【化２９】

【０１１４】
合成例１２ キノンジアジド化合物（８）の合成
乾燥窒素気流下、Ｎ，Ｎ'ビス-(2-ヒドロキシフェニル)-テレフタルイミド ２４．２ｇ（０．０５モル）１７．４２ｇ（０．０５モル）と５−ナフトキノンジアジドスルホニル酸クロリド２６．８６ｇ（０．１モル）を１，４−ジオキサン４５０ｇに溶解させ、室温にした。ここに、１，４−ジオキサン５０ｇと混合させたトリエチルアミン１０．１２ｇを用い、合成例６と同様にして、下記キノンジアジド化合物（８）を得た。
【０１１５】
【化３０】

【０１１６】
合成例１３ フェノール性水酸基を有する化合物（１）の合成
乾燥窒素気流下、２−アミノフェノール（東京化成（株）製）１６．４ｇ（０．１５モル）をＮＭＰ１００ｇに溶解させ氷浴につけ０℃にした。その後、トリメソリルクロライド（東京化成（株）製）１３．１ｇ（０．０５モル）をＮＭＰ２０ｇに溶解させ滴下ロートで滴下し、２時間攪拌させた。反応終了後、溶液を水３Ｌに投入して白色の沈殿を集めた。この沈殿をろ過で集めて、水で３回洗浄した後、８０℃の真空乾燥機で２０時間乾燥し、下記フェノール性水酸基を有する化合物（１）を得た。
【０１１７】
【化３１】

【０１１８】
合成例１４ フェノール性水酸基を有する化合物（２）の合成
乾燥窒素気流下、２−アミノ−ｍ−クレゾール（東京化成（株）製）１８．４ｇ（０．１５モル）をＮＭＰ１００ｇに溶解させ氷浴につけ０℃にした。その後、トリメソリルクロライド（東京化成（株）製）１３．１ｇ（０．０５モル）をＮＭＰ２０ｇに溶解させ滴下ロートで滴下し、２時間攪拌させた。反応終了後、溶液を水３Ｌに投入して白色の沈殿を集めた。この沈殿をろ過で集めて、水で３回洗浄した後、８０℃の真空乾燥機で２０時間乾燥し、下記フェノール性水酸基を有する化合物（２）を得た。
【０１１９】
【化３２】

【０１２０】
合成例１６ フェノール性水酸基を有する化合物（３）の合成
乾燥窒素気流下、２−アミノ−４−ｔｅｒｔ−ブチルフェノール（アルドリッジ製） ２４．８ｇ（０．１５モル）をＮＭＰ１００ｇに溶解させ氷浴につけ０℃にした。その後、トリメソリルクロライド（東京化成（株）製）１３．１ｇ（０．０５モル）をＮＭＰ２０ｇに溶解させ滴下ロートで滴下し、２時間攪拌させた。反応終了後、溶液を水３Ｌに投入して白色の沈殿を集めた。この沈殿をろ過で集めて、水で３回洗浄した後、８０℃の真空乾燥機で２０時間乾燥し、下記フェノール性水酸基を有する化合物（３）を得た。
【０１２１】
【化３３】

【０１２２】
合成例１７ フェノール性水酸基を有する化合物（４）の合成
乾燥窒素気流下、２−アミノフェノール（東京化成（株）製）１０．９ｇ（０．１０モル）をＮＭＰ１００ｇに溶解させ氷浴につけ０℃にした。その後、テレフタロイル クロライド（アルドリッジ社製）１０．０ｇ（０．０５モル）をＮＭＰ２０ｇに溶解させ滴下ロートで滴下し、２時間攪拌させた。反応終了後、溶液を水３Ｌに投入して白色の沈殿を集めた。この沈殿をろ過で集めて、水で３回洗浄した後、８０℃の真空乾燥機で２０時間乾燥し、下記フェノール性水酸基を有する化合物（４）を得た。
【０１２３】
【化３４】

【０１２４】
合成例１８ フェノール性水酸基を有する化合物（５）の合成
乾燥窒素気流下、４‐アミノリゾシノ−ルハイドロクロライド（アルドリッジ社製）１６．１ｇ（０．１０モル）をＮＭＰ１００ｇに溶解させ氷浴につけ０℃にした。その後、テレフタロイル クロライド（アルドリッジ社製）１０．０ｇ（０．０５モル）をＮＭＰ２０ｇに溶解させ滴下ロートで滴下し、２時間攪拌させた。反応終了後、溶液を水３Ｌに投入して白色の沈殿を集めた。この沈殿をろ過で集めて、水で３回洗浄した後、８０℃の真空乾燥機で２０時間乾燥し、下記フェノール性水酸基を有する化合物（５）を得た。
【０１２５】
【化３５】

【０１２６】
実施例１
乾燥窒素気流下、４，４’−ジアミノフェニルエーテル５．０１ｇ（０．０２５モル）、１，３−ビス（３−アミノプロピル）テトラメチルジシロキサン１．２４ｇ（０．００５モル）をＮ−メチル−２−ピロリドン（ＮＭＰ）５０ｇに溶解させた。ここに合成例１で得られたヒドロキシ基含有酸無水物２１．４ｇ（０．０３モル）をＮＭＰ１４ｇとともに加えて、２０℃で１時間反応させ、次いで５０℃で４時間反応させた。その後、Ｎ、Ｎ−ジメチルホルムアミドジメチルアセタール７．１４ｇ（０．０６モル）をＮＭＰ５ｇで希釈した溶液を１０分かけて滴下した。滴下後、５０℃で３時間攪拌しポリマー溶液（１）を得た。
【０１２７】
得られたポリマー溶液（１）４０ｇに合成例５で得られたキノンジアジド化合物（３）２．０ｇ、合成例１３で得られたェノール性水酸基を有する化合物（１）１．０ｇを加えて感光性ポリイミド前駆体組成物のワニスＡを得た。得られたワニスＡを用いて、シリコンウエハー上に感光性ポリイミド前駆体膜を作製、露光、現像し、ワニスの感度、残膜率、解像度、収縮率について評価を行った。評価結果をまとめて表１に示す。
【０１２８】
実施例２
乾燥窒素気流下、合成例２で得られたヒドロキシル基含有ジアミン（１）１５．１ｇ（０．０２５モル）をＮ−メチル−２−ピロリドン（ＮＭＰ）５０ｇに溶解させた。ここに合成例１で得られたヒドロキシ基含有酸無水物１７．５ｇ（０．０２５モル）をピリジン３０ｇとともに加えて、６０℃で６時間反応させた。反応終了後、溶液を水２Ｌに投入して、ポリマー固体の沈殿をろ過で集めた。ポリマー固体を８０℃の真空乾燥機で２０時間乾燥し、白色の固体（２）を得た。得られた該白色の固体（２）１０ｇを計り、合成例８で得られたキノンジアジド化合物（４）２ｇ、合成例１４で得られたフェノール性水酸基を有する化合物（２）２．０ｇ、ビニルトリメトキシシラン１ｇとをガンマブチロラクトン３０ｇに溶解させて感光性ポリイミド前駆体組成物のワニスＢを得た。得られたワニスＢを用いて、シリコンウエハー上に感光性ポリイミド前駆体膜を作製、露光、現像し、ワニスの感度、残膜率、解像度、収縮率について評価を行った。
【０１２９】
実施例３
乾燥窒素気流下、合成例３で得られたヒドロキシル基含有ジアミン化合物（２）１７．０ｇ（０．０４５モル）、１，３−ビス（３−アミノプロピル）テトラメチルジシロキサン１．２４ｇ（０．００５モル）をＮＭＰ５０ｇに溶解させた。ここに３，３’，４，４’−ジフェニルエーテルテトラカルボン酸無水物１２．４ｇ（０．０４モル）をＮＭＰ２１ｇとともに加えて、２０℃で１時間反応させ、次いで５０℃で２時間反応させた。ここに無水マレイン酸０．９８ｇ（０．０１モル）を加え、５０℃で２時間攪拌後、Ｎ，Ｎ−ジメチルホルムアミドジエチルアセタール１４．７ｇ（０．１モル）をＮＭＰ５ｇで希釈した溶液を１０分かけて滴下した。滴下後、５０℃で３時間攪拌しポリマー溶液（３）を得た。得られたポリマー溶液（３）３０ｇに合成例９で得られたキノンジアジド化合物（５）１．６ｇ、合成例１６で得られたフェノール性水酸基を有する化合物（３）０．８ｇを溶解させて感光性ポリイミド前駆体組成物のワニスＣを得た。得られたワニスＣを用いて、シリコンウエハー上に感光性ポリイミド前駆体膜を作製、露光、現像し、ワニスの感度、残膜率、解像度、収縮率について評価を行った。
【０１３０】
実施例４
乾燥窒素気流下、合成例４で得られたヒドロキシル基含有ジアミン化合物（３）６．０８ｇ（０．０２５モル）と４，４’−ジアミノジフェニルエーテル４．５１ｇ（０．０２２５モル）と１，３−ビス（３−アミノプロピル）テトラメチルジシロキサン０．６２ｇ（０．００２５モル）をＮＭＰ７０ｇに溶解させた。ヒドロキシル基含有酸無水物２４．９９ｇ（０．０３５モル）、３，３’，４，４’−ビフェニルテトラカルボン酸２無水物４．４１ｇ（０．０１５モル）を室温でＮＭＰ２５ｇとともに加え、そのまま室温で１時間、その後、５０℃で２時間攪拌した。ついで、グリシジルメチルエーテル１７．６ｇ（０．２モル）をＮＭＰ１０ｇで希釈した溶液を加え、７０℃で６時間攪拌しポリマー溶液（４）を得た。得られたポリマー溶液（４）４０ｇに、合成例１０で得られたキノンジアジド化合物（６）２．５ｇ、合成例１７で得られた本発明で使用されるフェノール性水酸基を有する化合物（４）２．０ｇを溶解させて感光性ポリイミド前駆体組成物のワニスＤを得た。得られたワニスＤを用いて、シリコンウエハー上に感光性ポリイミド前駆体膜を作製、露光、現像し、ワニスの感度、残膜率、解像度、収縮率について評価を行った。
【０１３１】
実施例５
乾燥窒素気流下、２，２−ビス（３−アミノ−４−ヒドロキシフェニル）ヘキサフルオロプロパン１８．３ｇ（０．０５モル）をＮ−メチル−２−ピロリドン（ＮＭＰ）５０ｇ、グリシジルメチルエーテル２６．４ｇ（０．３モル）に溶解させ、溶液の温度を−１５℃まで冷却した。ここにジフェニルエーテルジカルボン酸ジクロリド７．３８ｇ（０．０２５モル）、イソフタル酸ジクロリド５．０８ｇ（０．０２５モル）をガンマブチロラクトン２５ｇに溶解させた溶液を内部の温度が０℃を越えないように滴下した。滴下終了後、６時間−１５℃で攪拌を続けた。反応終了後、溶液を水３Ｌに投入して白色の沈殿を集めた。この沈殿をろ過で集めて、水で３回洗浄した後、８０℃の真空乾燥機で２０時間乾燥し白色のポリマー固体（５）を得た。得られたポリマー固体（５）５０ｇに合成例５で得られたキノンジアジド化合物（１）２．５ｇ、合成例１６で得られたフェノール性水酸基を有する化合物（３）を溶解させて感光性ポリイミド前駆体組成物のワニスＥを得た。得られたワニスＥを用いて、シリコンウエハー上に感光性ポリイミド前駆体膜を作製、露光、現像し、ワニスの感度、残膜率、解像度、収縮率について評価を行った。
【０１３２】
実施例６
実施例１で得られたポリマー溶液（１）４０ｇに合成例１２で得られたキノンジアジド化合物（８）２．０ｇ、合成例１７で得られたフェノール性水酸基を有する化合物（４）２．０ｇを溶解させて感光性ポリイミド前駆体組成物のワニスＦを得た。得られたワニスＦを用いて、シリコンウエハー上に感光性ポリイミド前駆体膜を作製、露光、現像し、ワニスの感度、残膜率、解像度、収縮率について評価を行った。
【０１３３】
実施例７
実施例４で得られたポリマー溶液（４）４０ｇに合成例６で得られたキノンジアジド化合物（２）２．０ｇ、合成例１８で得られたフェノール性水酸基を有する化合物（５）２．０ｇを溶解させて感光性ポリイミド前駆体組成物のワニスＧを得た。得られたワニスＧを用いて、シリコンウエハー上に感光性ポリイミド前駆体膜を作製、露光、現像し、ワニスの感度、残膜率、解像度、収縮率について評価を行った。
【０１３４】
実施例８
実施例５で得られたポリマー固体（５）１０．０ｇに合成例８で得られたキノンジアジド化合物（４）２．０ｇ、合成例１４で得られたフェノール性水酸基を有する化合物（２）１．０ｇをＮＭＰ３０ｇに溶解させて感光性ポリベンゾオキサゾール前駆体組成物のワニスＨを得た。得られたワニスＨを用いて、シリコンウエハー上に感光性ポリベンゾオキサゾール前駆体膜を作製、露光、現像し、ワニスの感度、残膜率、解像度、収縮率について評価を行った。
【０１３５】
実施例９
乾燥窒素気流下、合成例３で得られたジアミン化合物（２）１５．１ｇ（０．０２５モル）と４，４’−ジアミノジフェニルエーテル４．５ｇ（０．０２２５モル）と１，３−ビス（３−アミノプロピル）テトラメチルジシロキサン０．６２ｇ（０．００２５モル）をＧＢＬ１００ｇに溶解させた。ここに３，３’，４，４’−ベンゾフェノンテトラカルボン酸二無水物１６．１ｇ（０．０５０モル）を室温でＧＢＬ３３ｇとともに加え、そのまま室温で１時間、その後５０℃で４時間反応させポリマー溶液（６）を得た。得られたポリマー溶液（６）５０ｇに、合成例１１で得られたキノンジアジド化合物（７）７．６ｇを溶解させて感光性ポリイミド前駆体組成物のワニスＩを得た。得られたワニスＩを用いて、シリコンウエハー上に感光性ポリイミド前駆体膜を作製、露光、現像し、ワニスの感度、残膜率、解像度について評価を行った。
【０１３６】
実施例１０
乾燥窒素気流下、４，４’−ジアミノジフェニルエーテル１９．０ｇ（０．０９５モル）、１，３−ビス（３−アミノプロピル）テトラメチルジシロキサン１．２４ｇ（０．００５モル）をＧＢＬ３５０ｇに溶解させた。ここに合成例１で得られた酸無水物７１．４ｇ（０．１モル）をＧＢＬ４０ｇとともに加えて、２０℃で１時間反応させ、次いで５０℃で４時間反応させポリマー溶液（７）を得た。得られたポリマー溶液５０ｇ（７）に合成例１２で得られたキノンジアジド化合物（８）２０．０ｇをＧＢＬ１０ｇと共に加えて感光性ポリイミド前駆体組成物のワニスＪを得た。得られたワニスＪを用いて、シリコンウエハー上に感光性ポリイミド前駆体膜を作製、露光、現像し、ワニスの感度、残膜率、解像度について評価を行った。
【０１３７】
比較例１
実施例１で得られたポリマー溶液（１）４０ｇに合成例７で得られたキノンジアジド化合物（３）２．０ｇ、下記化学式で示されるフェノール性水酸基を有する化合物Ｂｉｓ−ＲＳ−２Ｐ（商品名、本州化学工業（株）製）１．０ｇを加えて感光性ポリイミド前駆体組成物のワニスＫを得た。得られたワニスＫを用いて、シリコンウエハー上に感光性ポリイミド前駆体膜を作製、露光、現像し、ワニスの感度、残膜率、解像度、収縮率について評価を行った。
【０１３８】
【化３６】

【０１３９】
比較例２
実施例２で得たポリマー固体（２）１０ｇを計り、合成例８で得られたキノンジアジド化合物（４）２ｇ、下記化学式で示されるフェノール性水酸基を有する化合物ＢｉｓＰＧ−２６Ｘ（商品名、本州化学工業（株）製）２．０ｇ、ビニルトリメトキシシラン１ｇとをガンマブチロラクトン３０ｇに溶解させて感光性ポリイミド前駆体組成物のワニスＬを得た。得られたワニスＬを用いて、シリコンウエハー上に感光性ポリイミド前駆体膜を作製、露光、現像し、ワニスの感度、残膜率、解像度、収縮率について評価を行った。
【０１４０】
【化３７】

【０１４１】
比較例３
実施例３で得られたポリマー溶液（３）３０ｇに合成例９で得られたキノンジアジド化合物（５）１．６ｇ、下記化学式で示されるフェノール性水酸基を有する化合物Ｂｉｓ−ＲＳ−３Ｐ ０．８ｇを溶解させて感光性ポリイミド前駆体組成物のワニスＭを得た。得られたワニスＭを用いて、シリコンウエハー上に感光性ポリイミド前駆体膜を作製、露光、現像し、ワニスの感度、残膜率、解像度、収縮率について評価を行った。
【０１４２】
【化３８】

【０１４３】
比較例４
実施例１で得られたポリマー溶液（１）４０ｇに合成例７で得られたキノンジアジド化合物（３）２．０ｇを溶解させて感光性ポリイミド前駆体組成物のワニスＮを得た。得られたワニスＮを用いて、シリコンウエハー上に感光性ポリイミド前駆体膜を作製、露光、現像し、ワニスの感度、残膜率、解像度、収縮率について評価を行った。
【０１４４】
比較例５
実施例１で得られたポリマー溶液（１）４０ｇに合成例７で得られたキノンジアジド化合物（３）２．０ｇ、下記化学式で示されるＴｒｉｓＰ−ＰＡ（商品名、本州化学工業（株）製）１．０ｇを溶解させて感光性ポリイミド前駆体組成物のワニスＯを得た。得られたワニスＯを用いて、シリコンウエハー上に感光性ポリイミド前駆体膜を作製、露光、現像し、ワニスの感度、残膜率、解像度、収縮率について評価を行った。
【０１４５】
【化３９】

【０１４６】
比較例６
合成例１４で得られたポリマー固体（２）３０ｇに合成例９で得られたキノンジアジド化合物（５）１．６ｇ、下記化学式で示されるＢｉｓＰ−ＡＰ（商品名、本州化学工業（株）製）０．８ｇを溶解させて感光性ポリイミド前駆体組成物のワニスＰを得た。得られたワニスＰを用いて、シリコンウエハー上に感光性ポリイミド前駆体膜を作製、露光、現像し、ワニスの感度、残膜率、解像度、収縮率について評価を行った。
【０１４７】
【化４０】

【０１４８】
実施例、比較例の評価結果については、まとめて表１に示した。本発明のポジ型感光性樹脂前駆体組成物を使用した実施例は、収縮率が小さく解像度に優れていた。一方、一般式（２）で示されるフェノール性水酸基を有する化合物を使用しない比較例は、相対的に収縮率が大きく、解像度に劣っていた。
【０１４９】
【表１】

【０１５０】
【発明の効果】
本発明によれば、アルカリ水溶液で現像でき、解像度、感度、残膜率、キュア後の収縮率の優れたポジ型の感光性樹脂前駆体組成物を得ることができる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a positive photosensitive polyimide precursor composition suitable for a surface protective film, an interlayer insulating film, and the like of a semiconductor element, in which a portion exposed to ultraviolet light is dissolved in an aqueous alkaline solution.
[0002]
[Prior art]
As a positive-type heat-resistant resin precursor composition in which the exposed portion is dissolved by alkali development, those obtained by adding naphthoquinone diazide to a polyamic acid or those obtained by adding naphthoquinone diazide to a soluble polyimide having a hydroxyl group, having a hydroxyl group A product obtained by adding naphthoquinonediazide to a polyamide has been known.
[0003]
However, in the case of adding naphthoquinone diazide to ordinary polyamic acid, the desired pattern cannot be obtained in most cases because the solubility of the carboxyl group of polyamic acid is higher than the dissolution inhibiting effect of naphthoquinone diazide on alkali. There was a problem. Then, in order to control the alkali solubility of the polyamic acid, a polyamic acid derivative in which the carboxyl group of the polyamic acid is protected with an ester group has been developed. However, in the case where naphthoquinone diazide is added to this polyamic acid derivative, the dissolution inhibiting effect of naphthoquinone diazide on alkali becomes very large, and a desired pattern can be obtained, but in most cases, a very large decrease in sensitivity is caused. There was a problem. On the other hand, it has been studied to add various compounds having phenolic hydroxyl groups to the polyamic acid derivative obtained by adding naphthoquinonediazide.
[0004]
Examples of the compound having a phenolic hydroxyl group include a compound obtained by adding a photosensitive diazoquinone compound and a phenolic compound to a polyamide (for example, see Patent Documents 1 to 5), and a compound obtained by adding a quinonediazide compound esterified to a polyimide and a phenolic compound (for example, There is a positive photosensitive resin composition using indophenol as a dissolution accelerator (for example, see Patent Document 7). However, the thermal decomposition temperature of these compounds having a phenolic hydroxyl group is lower than that of polymers, and lacks heat resistance. Shrinkage after curing increases, resulting in deterioration of pattern shape and sensitivity, and the heat resistance of the resin itself. Had led to a decline.
[0005]
As a material having a small shrinkage, there is a material obtained by adding a filler to an alkali-soluble resin (for example, see Patent Documents 8 to 9). In these materials, a filler is added. Had to be done in. Further, there is a product using a compound containing a phenolic hydroxyl group that promotes dissolution and an alkoxymethyl group that crosslinks with the polymer in one molecule (for example, see Patent Documents 10 to 11). However, there has been a problem that the water absorption of the carrier film becomes large.
[0006]
[Patent Document 1]
JP-A-9-302221 (pages 1 to 6)
[0007]
[Patent Document 2]
JP-A-11-65107 (pages 1 to 5, pages 9 to 12)
[0008]
[Patent Document 3]
JP-A-11-102609 (pages 1 to 3, pages 12 to 19)
[0009]
[Patent Document 4]
JP-A-11-109620 (pages 1 to 2, page 5, pages 15 to 18)
[0010]
[Patent Document 5]
JP-A-11-242338 (pages 1 to 3, 11 to 19)
[0011]
[Patent Document 6]
JP-A-13-64507 (pages 1 to 4)
[0012]
[Patent Document 7]
JP-A-2002-88066 (pages 1 to 5)
[0013]
[Patent Document 8]
JP-A-13-142209 (pages 1 to 4)
[0014]
[Patent Document 9]
JP-A-2002-202593 (pages 1 to 10)
[0015]
[Patent Document 10]
JP-A-2001-312051 (pages 1 to 3)
[0016]
[Patent Document 11]
JP 2001-312063 A (pages 1 to 3)
[0017]
[Problems to be solved by the invention]
An object of the present invention is to solve the drawbacks of the prior art, and more specifically, to provide a positive photosensitive resin precursor composition which has a small shrinkage during curing and high heat resistance.
[0018]
[Means for Solving the Problems]
The present invention has been found that by adding a compound having a specific phenolic hydroxyl group having heat resistance to a polyimide precursor and a naphthoquinonediazide compound, shrinkage during curing is reduced and heat resistance is increased. It has been reached. The mechanism by which such an effect is obtained is not clear, but it is considered that the compound having a phenolic hydroxyl group in the resin precursor composition undergoes intramolecular dehydration ring closure during curing.
[0019]
The present invention has the following structure as its gist. That is, (a) a polymer having a structural unit represented by the general formula (1) as a main component, (b) a compound having a phenolic hydroxyl group represented by the general formula (2), and (c) an esterified quinonediazide. A positive photosensitive resin precursor composition comprising a compound.
[0020]
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[0021]
(Where R ¹ Is a divalent to octavalent organic group having two or more carbon atoms, R ^Two Is a divalent to hexavalent organic group having two or more carbon atoms; ¹ And R ^Two At least has an aromatic ring. R ^Three Represents hydrogen or an organic group having 1 to 20 carbon atoms, which may be the same or different. n is an integer from 10 to 100,000, m is an integer from 0 to 4, and p and q are integers from 0 to 4. However, p + q> 0. )
[0022]
Embedded image

[0023]
(Where R ^Four Represents hydrogen or an organic group having 1 to 20 carbon atoms. R ^Five Represents one selected from hydrogen, a hydroxyl group, and an organic group having 1 to 20 carbon atoms. a represents an integer of 0 to 3, b represents an integer of 3 to 6, and c represents an integer of 0 to 4. )
[0024]
BEST MODE FOR CARRYING OUT THE INVENTION
The polymer having a structural unit represented by the general formula (1) as a main component in the present invention is a polymer which can be converted into a polymer having an imide ring, an oxazole ring, or another cyclic structure by heating or an appropriate catalyst. By having a ring structure, heat resistance and solvent resistance are dramatically improved.
[0025]
The general formula (1) represents a polyamide having a hydroxyl group, a polyimide acid, and a polyamic acid ester. Due to the presence of the hydroxyl group, the solubility in an aqueous alkali solution is better than that of a polyamic acid having no hydroxyl group. Become. In particular, among the hydroxyl groups, a phenolic hydroxyl group is more preferable than the solubility in an aqueous alkaline solution.
[0026]
In addition, when the fluorine atom is contained in the general formula (1) in an amount of 10% by weight or more, when developing with an aqueous alkaline solution, the water repellency appears at the interface of the film moderately. However, when the fluorine atom content exceeds 20% by weight, the solubility in an aqueous alkali solution decreases, the organic solvent resistance of the polymer formed into a cyclic structure by heat treatment decreases, and the solubility in fuming nitric acid decreases. There is. Therefore, it is preferable that the fluorine atom is contained in an amount of 10% by weight or more and 20% by weight or less.
[0027]
In the above general formula (1), R ¹ (COOR ^Three ) _m (OH) _p The part represents the structural component of the acid dianhydride. This acid dianhydride is preferably a divalent to octavalent organic group containing an aromatic ring and having 2 to 2 carbon atoms having 1 to 4 hydroxyl groups, and having 6 to 30 carbon atoms. Is more preferably a trivalent or tetravalent organic group.
[0028]
Specifically, those having a structure represented by the following general formula (3) are preferable.
[0029]
Embedded image

[0030]
(Where R ⁶ , R ⁸ Represents a divalent to tetravalent organic group having 2 to 20 carbon atoms; ⁷ Represents a trivalent to hexavalent organic group having 3 to 20 carbon atoms; ⁹ , R ^Ten Represents hydrogen or an organic group having 1 to 20 carbon atoms. o and s represent an integer of 0 to 2, and r represents an integer of 1 to 4).
[0031]
R ⁶ , R ⁸ Is preferably one containing an aromatic ring in view of the heat resistance of the obtained polymer. Among them, particularly preferred structures include those such as trimellitic acid, trimesic acid and naphthalene tricarboxylic acid residues. Further, the hydroxyl group is preferably located at a position adjacent to the amide bond. Such examples include bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-hydroxy-4-aminophenyl) hexafluoropropane containing a fluorine atom, and bis (3-amino-4-aminophenyl) hexafluoropropane containing no fluorine atom. 3-amino-4-hydroxyphenyl) propane, bis (3-hydroxy-4-aminophenyl) propane, 3,3′-diamino-4,4′-dihydroxybiphenyl, 3,3′-diamino-4,4 ′ -Dihydroxybiphenyl, 2,4-diamino-phenol, 2,5-diaminophenol, and 1,4-diamino-2,5-dihydroxybenzene having an amino group bonded thereto.
[0032]
Further, R in the general formula (1) ¹ (COOR ^Three ) _m (OH) _p Of the compounds represented by the general formula (3), preferred compounds include those having the following structures, but are not limited thereto.
[0033]
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[0034]
Further, as long as the solubility in alkali, the photosensitive performance, and the heat resistance are not impaired, R ¹ (COOR ^Three ) _m (OH) _p The portion can be modified with a tetracarboxylic acid or dicarboxylic acid having no hydroxyl group. For example, aromatic tetracarboxylic acids such as pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, diphenylethertetracarboxylic acid, and diphenylsulfonetetracarboxylic acid, and two carboxyl groups thereof were converted to methyl groups or ethyl groups. Diester compounds, aliphatic tetracarboxylic acids such as butanetetracarboxylic acid and cyclopentanetetracarboxylic acid, and diester compounds in which two carboxyl groups are converted to methyl groups or ethyl groups, terephthalic acid, isophthalic acid, diphenylether dicarboxylic acid, naphthalenedicarboxylic acid Examples thereof include aromatic dicarboxylic acids such as acids, and aliphatic dicarboxylic acids such as adipic acid. R ^Three When a compound having a hydroxyl group is used as the component containing ¹ Is not necessarily required for the component containing ¹ Can be used as a component containing Here, the modification is preferably at most 50 mol% of the acid component, more preferably at most 30 mol%. If the denaturation is more than 50 mol%, the solubility in alkali and the photosensitivity may be impaired.
[0035]
In the general formula (1), R ^Two Represents a structural component of the diamine. In this, R ^Two (OH) _q As a preferable example, a compound having an aromatic group and a hydroxyl group is preferable in view of the heat resistance of the obtained polymer, and specific examples thereof include bis (amino-hydroxy-phenyl) hexafluoropropane having a fluorine atom. Compounds having no fluorine atom, such as diaminodihydroxypyrimidine, diaminodihydroxypyridine, hydroxy-diamino-pyrimidine, diaminophenol, dihydroxybenzidine and those having structures represented by general formulas (4), (5) and (6) Can be given.
[0036]
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[0037]
(Where R ¹¹ , R ¹³ Represents a trivalent to tetravalent organic group having 2 to 20 carbon atoms; ¹² Represents a divalent organic group having 2 to 30 carbon atoms. t and u represent 1 or 2. )
[0038]
Embedded image

[0039]
(Where R ¹⁴ , R ¹⁶ Represents a divalent organic group having 2 to 20 carbon atoms; ^Fifteen Represents a trivalent to hexavalent organic group having 3 to 20 carbon atoms. v shows the integer of 1-4. )
[0040]
Embedded image

[0041]
(Where R ¹⁷ Represents a divalent organic group having 2 to 20 carbon atoms; ¹⁸ Represents a trivalent to hexavalent organic group having 3 to 20 carbon atoms. w represents an integer of 1 to 4. )
In this, R ¹¹ ~ R ¹² Is preferably an organic group having an aromatic ring from the viewpoint of heat resistance of the obtained polymer.
[0042]
R of the general formula (1) ^Two (OH) _q Is shown below by a general formula (4).
[0043]
Embedded image

[0044]
In addition, R in the general formula (1) ^Two (OH) _q Is shown below by the general formula (5).
[0045]
Embedded image

[0046]
In addition, R in the general formula (1) ^Two (OH) _q Is shown below by the general formula (6).
[0047]
Embedded image

[0048]
In the general formula (4), R ¹¹ , R ¹³ Represents a trivalent to tetravalent organic group having 2 to 20 carbon atoms, and preferably has an aromatic ring from the viewpoint of heat resistance of the obtained polymer. Specifically, hydroxyphenyl, dihydroxyphenyl, hydroxynaphthyl, dihydroxynaphthyl, hydroxybiphenyl, dihydroxybiphenyl, bis (hydroxyphenyl) hexafluoropropane, bis (hydroxyphenyl) propane, bis (hydroxy (Phenyl) sulfone group, hydroxydiphenylether group, dihydroxydiphenylether group and the like. In addition, aliphatic groups such as a hydroxycyclohexyl group and a dihydroxycyclohexyl group can also be used. R ¹² Represents a divalent organic group having 2 to 30 carbon atoms. From the viewpoint of heat resistance of the obtained polymer, a divalent group having an aromatic group is preferred. Examples of such a group include a phenyl group, a biphenyl group, a diphenyl ether group, a diphenylhexafluoropropane group, a diphenylpropane group, and a diphenylsulfone group. And an aliphatic cyclohexyl group and the like can also be used.
[0049]
In the general formula (5), R ¹⁴ , R ¹⁶ Represents a divalent organic group having 2 to 20 carbon atoms. From the viewpoint of heat resistance of the obtained polymer, a divalent group having an aromatic group is preferred. Examples of such a group include a phenyl group, a biphenyl group, a diphenyl ether group, a diphenylhexafluoropropane group, a diphenylpropane group, and a diphenylsulfone group. And an aliphatic cyclohexyl group and the like can also be used. R ^Fifteen Represents a trivalent to hexavalent organic group having 3 to 20 carbon atoms, and preferably has an aromatic ring from the viewpoint of heat resistance of the obtained polymer. Specifically, a hydroxyphenyl group, a dihydroxyphenyl group, a hydroxynaphthyl group, a dihydroxynaphthyl group, a hydroxybiphenyl group, a dihydroxybiphenyl group, a bis (hydroxyphenyl) hexafluoropropane group, a bis (hydroxyphenyl) propane group, Examples thereof include a (hydroxyphenyl) sulfone group, a hydroxydiphenyl ether group, and a dihydroxydiphenyl ether group. In addition, aliphatic groups such as a hydroxycyclohexyl group and a dihydroxycyclohexyl group can also be used.
[0050]
In the general formula (6), R ¹⁷ Represents a divalent organic group selected from C2 to C20. A divalent group having an aromatic group is preferred from the viewpoint of heat resistance of the obtained polymer. Examples of such a group include a phenyl group, a biphenyl group, a diphenyl ether group, a diphenylhexafluoropropane group, a diphenylpropane group, and a diphenylsulfone group. Examples thereof include aliphatic cyclohexyl groups and the like. R ¹⁸ Represents a trivalent to hexavalent organic group selected from 3 to 20 carbon atoms, and preferably has an aromatic ring from the viewpoint of heat resistance of the obtained polymer. Specifically, hydroxyphenyl, dihydroxyphenyl, hydroxynaphthyl, dihydroxynaphthyl, hydroxybiphenyl, dihydroxybiphenyl, bis (hydroxyphenyl) hexafluoropropane, bis (hydroxyphenyl) propane, bis (hydroxy Phenyl) sulfone group, hydroxydiphenylether group, dihydroxydiphenylether group and the like. In addition, aliphatic groups such as a hydroxycyclohexyl group and a dihydroxycyclohexyl group can also be used.
[0051]
R of the general formula (1) ^Two (OH) _q Of these, 1 to 40 mol% can be modified using another diamine component. Examples of these include phenylenediamine, diaminodiphenyl ether, aminophenoxybenzene, diaminodiphenylmethane, diaminodiphenylsulfone, bis (trifluoromethyl) benzidine, bis (aminophenoxyphenyl) propane, bis (aminophenoxyphenyl) sulfone, and Examples thereof include compounds in which an aromatic ring is substituted with an alkyl group or a halogen atom. In addition, aliphatic cyclohexyldiamine, methylenebiscyclohexylamine and the like can be mentioned, but when such a diamine component is copolymerized in an amount exceeding 40 mol%, the heat resistance of the obtained polymer decreases. R ¹ When a compound having a hydroxyl group is used as the component, R ^Three A hydroxyl group is not necessarily required as a component, and the above-mentioned diamine having no hydroxyl group can be used.
[0052]
R of the general formula (1) ^Three Represents hydrogen or an organic group having 1 to 20 carbon atoms. From the stability of the obtained positive photosensitive resin precursor solution, R ^Three Is preferably an organic group, but is preferably hydrogen from the viewpoint of solubility of the aqueous alkali solution. In the present invention, a hydrogen atom and an alkyl group can be mixed. This R ^Three By controlling the amounts of hydrogen and organic groups, the dissolution rate in an alkaline aqueous solution changes, so that a positive photosensitive resin precursor composition having an appropriate dissolution rate can be obtained by this adjustment. A preferred range is R ^Three Is from 90% to 90% of hydrogen atoms. R ^Three When the number of carbon atoms exceeds 20, it is not preferable because it does not dissolve in an alkaline aqueous solution. From these points, R ^Three Preferably contains at least one hydrocarbon group having 1 to 16 carbon atoms, and the others are preferably hydrogen atoms.
[0053]
M in the general formula (1) indicates the number of carboxyl groups, and indicates an integer from 0 to 4. N in the general formula (1) indicates the number of repeating structural units of the polymer of the present invention, and is in the range of 10 to 100,000.
[0054]
Polyhydroxyamide can also be used as a structural unit represented by the general formula (1). Such a polyhydroxyamide can be produced, for example, by subjecting a bisaminophenol compound and a dicarboxylic acid to a condensation reaction. Specifically, a method of reacting an acid with a dehydrating condensing agent such as dicyclohexylcarbodiimide (DCC) and adding a bisaminophenol compound thereto or a solution of a bisaminophenol compound containing a tertiary amine such as pyridine in a dicarboxylic acid solution is used. There is a method of dropping a solution of dichloride.
[0055]
When using polyhydroxyamide, a positive photosensitive heat-resistant resin precursor that can remove a portion exposed to ultraviolet light with an alkaline aqueous solution by adding a photosensitizing agent such as naphthoquinonediazidesulfonic acid ester to the solution of polyhydroxyamide. A composition can be obtained.
[0056]
Further, in order to improve the adhesiveness to the substrate, the R of the general formula (1) may be used as long as heat resistance is not reduced. ¹ , R ^Two May be copolymerized with an aliphatic group having a siloxane structure. Specific examples of the diamine component include those obtained by copolymerizing bis (3-aminopropyl) tetramethyldisiloxane, bis (p-amino-phenyl) octamethylpentasiloxane, etc. at 1 to 10 mol%.
[0057]
The polymer (a) contained in the positive photosensitive resin precursor composition of the present invention may be composed of only the structural unit represented by the general formula (1), or may be used together with another structural unit. It may be a polymer or a blend. In that case, it is preferable that the structural unit represented by the general formula (1) is contained in an amount of 90 mol% or more. The type and amount of the structural unit used in the copolymerization or blending are preferably selected within a range that does not impair the heat resistance of the polyimide polymer obtained by the final heat treatment.
[0058]
The polymer (a) used in the present invention is synthesized by a known method. For example, a method of reacting a tetracarboxylic dianhydride with a diamine compound at a low temperature, a method of obtaining a diester with a tetracarboxylic dianhydride and an alcohol, and then reacting the diester with an amine in the presence of a condensing agent, The diester can be obtained by using a dianhydride and an alcohol, and then the remaining dicarboxylic acid is converted to an acid chloride and reacted with an amine.
[0059]
Next, the compound (b) represented by the following general formula (2) used in the present invention will be described.
[0060]
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[0061]
(Where R ^Four Represents hydrogen or an organic group having 1 to 20 carbon atoms. R ^Five Is one selected from hydrogen, a hydroxyl group and an organic group having 1 to 20 carbon atoms. a represents an integer of 0 to 3, b represents an integer of 2 to 6, and c represents an integer of 0 to 4).
[0062]
R of the general formula (2) ^Four Is preferably a hydrogen atom or an organic group having 1 to 6 carbon atoms, and more preferably a hydrogen atom, a methyl group, an ethyl group, or a tert-butyl group. R ^Five Is preferably at least one selected from hydrogen, a hydroxyl group, a methyl group, a tert-butyl group, and a vinyl group.
[0063]
Examples of the compound having a phenolic hydroxyl group represented by the general formula (2) in the present invention include a compound having the following structure.
[0064]
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[0065]
The amount of such a compound having a phenolic hydroxyl group to be added is preferably 1 to 50 parts by weight, more preferably 3 to 40 parts by weight, based on 100 parts by weight of the polymer (a).
[0066]
Next, (c) the esterified quinonediazide compound will be described.
[0067]
As the quinonediazide compound to be added to the present invention, a compound in which a sulfonic acid of naphthoquinonediazide is bonded to a compound having a phenolic hydroxyl group by an ester is preferably used. These can be used alone or in combination of two or more. The compound having a phenolic hydroxyl group used here may be the same as or different from the compound having a phenolic hydroxyl group (b) represented by the general formula (2) used in the present invention. For example, compounds not falling under the general formula (2) include naphthol, tetrahydroxybenzophenone, gallic acid methyl ester, bisphenol A, methylene bisphenol, TrisP-HAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BisP- AP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), TrisP-HAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BisRS-2P, BisPG-26X, BisOC-OCHP, BisP-OCHP, BisPC-OCHP, Bis25X-OCHP, Bis26X-OCHP, BisOCHP-OC, Bis236T-OCHP, Methylenetris-FR-CR, BisRS-26X, BisRS-OCHP Name, manufactured by Honshu Chemical Industry Co., Ltd. , BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F (all trade names, manufactured by Asahi Organic Materials Industry Co., Ltd.), etc. 5-naphthoquinonediazidosulfonyl ester compound and 4-naphthoquinonediazidosulfonylester compound of a compound having a phenolic hydroxyl group.
[0068]
The 4-naphthoquinonediazidosulfonyl ester compound has an absorption in the i-line region of a mercury lamp and is suitable for i-line exposure, and the 5-naphthoquinonediazidosulfonyl ester compound has an absorption extending to the g-line region of the mercury lamp, Suitable for exposure. In the present invention, both 4-naphthoquinonediazidosulfonyl ester compound and 5-naphthoquinonediazidosulfonylester compound can be preferably used, but 4-naphthoquinonediazidosulfonyl ester compound, 5-naphthoquinonediazidosulfonylester depending on the wavelength of light to be exposed. It is more preferred to select a compound. Further, a naphthoquinonediazidosulfonyl ester compound in which a 4-naphthoquinonediazidosulfonyl group and a 5-naphthoquinonediazidosulfonyl group are used together in the same molecule can be used, or a 4-naphthoquinonediazidosulfonylester compound and a 5-naphthoquinonediazidosulfonylester compound can be used. Can also be used as a mixture.
[0069]
The esterified quinonediazide compound (c) used in the present invention can be synthesized by an esterification reaction between a compound having a phenolic hydroxyl group and a quinonediazidesulfonic acid compound, and can be synthesized by a known method. Can be.
[0070]
Use of such an esterified quinonediazide improves resolution, sensitivity, and residual film ratio.
[0071]
Further, when the molecular weight of the esterified naphthoquinonediazide compound exceeds 1500, the naphthoquinonediazide compound does not thermally decompose sufficiently in the subsequent heat treatment, so that the heat resistance of the obtained film is reduced or the mechanical properties are reduced, Problems such as a decrease in adhesion may occur. From such a viewpoint, the preferred esterified quinonediazide compound has a molecular weight of 300 to 1500. More preferably, it is 350 to 1200. The amount of the esterified quinonediazide compound is preferably 1 to 50 parts by weight, more preferably 3 to 40 parts by weight, based on 100 parts by weight of the polymer (a). .
[0072]
(C) By adding the esterified quinonediazide compound, the film loss of the unexposed area after development is significantly reduced, and a good pattern can be obtained in a short development time.
[0073]
In the positive photosensitive resin precursor composition of the present invention, if necessary, a surfactant, ethyl lactate or the like for the purpose of improving the coatability between the positive photosensitive heat-resistant precursor composition and the substrate. Esters such as propylene glycol monomethyl ether acetate, alcohols such as ethanol, ketones such as cyclohexanone and methyl isobutyl ketone, and ethers such as tetrahydrofuran and dioxane may be mixed. In addition, inorganic particles such as silicon dioxide and titanium dioxide, or powder of polyimide can also be added.
[0074]
Further, in order to enhance the adhesion to an underlying substrate such as a silicon wafer, a silane coupling agent, a titanium chelating agent, etc. are added to the varnish of the positive photosensitive heat-resistant resin precursor composition in an amount of 0.5 to 10% by weight. Alternatively, the underlying substrate can be pre-treated with such a chemical solution.
[0075]
When added to the varnish, a silane coupling agent such as methylmethacryloxydimethoxysilane, 3-aminopropyltrimethoxysilane, a titanium chelating agent, or an aluminum chelating agent is added in an amount of 0.5 to 10 wt. % Is preferably used.
[0076]
When treating the substrate, the above coupling agent is added to a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diethyl adipate in a proportion of 0.5 to 20% by weight. A method of subjecting the dissolved solution to surface treatment by spin coating, dipping, spray coating, steam treatment, or the like is preferably used. In some cases, a method of applying a temperature of 50 ° C. to 300 ° C. thereafter to allow the reaction between the substrate and the coupling agent to proceed is preferably used.
[0077]
Next, a preferred method for forming a heat-resistant resin pattern using the positive photosensitive heat-resistant precursor composition of the present invention will be described.
[0078]
A positive photosensitive heat-resistant precursor composition is applied on a substrate. As the substrate, a silicon wafer, ceramics, gallium arsenide, or the like is used, but is not limited thereto. Examples of the coating method include spin coating using a spinner, spray coating, and roll coating, and can be used without any particular limitation. The coating thickness varies depending on the coating method, the solid content concentration of the composition, the viscosity, and the like, but is usually applied so that the thickness after drying is 0.1 to 150 μm.
[0079]
Next, the substrate coated with the positive photosensitive heat-resistant precursor composition is dried to obtain a photosensitive heat-resistant precursor composition film. Drying is preferably performed in an oven, a hot plate, an infrared ray, or the like, at a temperature of 50 to 150 degrees for 1 minute to several hours.
[0080]
Next, the photosensitive heat-resistant precursor composition film is exposed to actinic radiation through a mask having a desired pattern. Actinic rays used for exposure include ultraviolet rays, visible rays, electron beams, X-rays, and the like, and it is preferable to use i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a mercury lamp.
[0081]
The pattern of the heat-resistant resin is formed by removing the exposed portion using a developer after the exposure. As a developing solution, an aqueous solution of tetramethylammonium, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethyl An aqueous solution of a compound exhibiting alkalinity such as aminoethyl methacrylate, cyclohexylamine, ethylenediamine, and hexamethylenediamine is preferred. In some cases, a polar solvent such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, dimethylacrylamide, methanol, ethanol, Even if alcohols such as isopropanol, ethyl lactate, esters such as propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone and methyl isobutyl ketone are added alone or in combination of several kinds. Good. After development, it is rinsed with water. Here, rinsing treatment may be performed by adding alcohols such as ethanol and isopropyl alcohol, and esters such as ethyl lactate and propylene glycol monomethyl ether acetate to water.
[0082]
After development, the film is converted into a heat-resistant resin film by applying a temperature of 200 ° C. to 500 ° C. This heat treatment is preferably carried out for 5 minutes to 5 hours while selecting the temperature and increasing the temperature stepwise, or while selecting a certain temperature range and continuously increasing the temperature. As an example, there is a method of performing heat treatment at 130 ° C., 200 ° C., and 350 ° C. for 30 minutes each. Alternatively, a method of linearly raising the temperature from room temperature to 400 ° C. over 2 hours may be used.
[0083]
The use of the heat-resistant resin film formed using the positive-type photosensitive heat-resistant precursor composition of the present invention is not particularly limited, but is preferably a passivation film of a semiconductor, a protective film of a semiconductor element, and a multilayer wiring for high-density mounting. It is used for applications such as interlayer insulating films.
[0084]
【Example】
Hereinafter, the present invention will be described with reference to examples and techniques, but the present invention is not limited to these examples. The preparation and evaluation of the positive photosensitive heat-resistant resin precursor composition in the examples were performed by the following methods.
[0085]
Preparation of photosensitive polyimide precursor film
A 6-inch silicon wafer is coated with a positive photosensitive heat-resistant resin precursor composition (hereinafter, referred to as varnish) so as to have a thickness of 14 μm after pre-baking, and then a hot plate (Mark manufactured by Tokyo Electron Ltd.) By performing prebaking at 120 ° C. for 3 minutes using -7), a photosensitive polyimide precursor film was obtained.
[0086]
How to measure film thickness
The measurement was performed at a refractive index of 1.64 using Lambda Ace STM-602 manufactured by Dainippon Screen Mfg. Co., Ltd.
[0087]
exposure
The pattern-cut reticle was set in an exposure machine (i-line stepper DSW-8000 manufactured by GCA), and i-line exposure was performed while changing the exposure time (intensity of 365 nm).
[0088]
developing
Using a Mark-7 developing device manufactured by Tokyo Electron Limited, a 2.38% aqueous solution of tetramethylammonium hydroxide was sprayed at 50 rpm for 10 seconds. Thereafter, the plate was allowed to stand still at 0 rotation for 60 seconds, rinsed with water at 400 rotations, and shake-dried at 3000 rotations for 10 seconds.
[0089]
Calculation of residual film ratio
The residual film ratio was calculated according to the following equation.
Remaining film ratio (%) = (film thickness after development / film thickness after pre-bake) × 100
Calculation of sensitivity
After exposure and development, an exposure time (hereinafter, referred to as an optimum exposure time) for forming a 50 μm line-and-space pattern (1L / 1S) in a one-to-one width was determined.
[0090]
Calculation of resolution
After exposure and development, the resolution was defined as the minimum pattern size at the optimal exposure time for forming a 50 μm line-and-space pattern (1 L / 1 S) in a one-to-one width.
[0091]
Calculation of shrinkage
The prepared photosensitive polyimide precursor film was subjected to an inert oven INH-21CD manufactured by Koyo Lindberg Co., Ltd. under nitrogen stream (oxygen concentration: 20 ppm or less) at 140 ° C. for 30 minutes, and then to 350 ° C. for 1 hour. The temperature was raised and heat treatment was performed at 350 ° C. for 1 hour to produce a cured film. The shrinkage was calculated according to the following equation.
Shrinkage (%) = (film thickness after pre-bake−film thickness after cure) ÷ film thickness after pre-bake × 100.
[0092]
Synthesis Example 1 Synthesis of hydroxyl group-containing acid anhydride
Under a stream of dry nitrogen, 18.3 g (0.05 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF) and 34.2 g (0.3 mol) of allyl glycidyl ether were gamma-treated. It was dissolved in 100 g of butyrolactone and cooled to -15 ° C. To this, 22.1 g (0.11 mol) of trimellitic anhydride chloride dissolved in 50 g of gamma butyrolactone was added dropwise so that the temperature of the reaction solution did not exceed 0 ° C. After the completion of the dropwise addition, the reaction was carried out at 0 ° C. for 4 hours. This solution was concentrated using a rotary evaporator, and then added to 1 L of toluene to obtain the following acid anhydride (1).
[0093]
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[0094]
Synthesis Example 2 Synthesis of diamine compound (1) containing hydroxyl group
18.3 g (0.05 mol) of BAHF was dissolved in 100 ml of acetone and 17.4 g (0.3 mol) of propylene oxide, and cooled to -15 ° C. A solution of 20.4 g (0.11 mol) of 4-nitrobenzoyl chloride dissolved in 100 ml of acetone was added dropwise thereto. After the completion of the dropwise addition, the reaction was carried out at −15 ° C. for 4 hours, and then returned to room temperature. The precipitated white solid was separated by filtration and dried at 50 ° C. in vacuo. Next, 30 g of the white solid was placed in a 300 ml stainless steel autoclave, dispersed in 250 ml of methyl cellosolve, and 2 g of 5% palladium-carbon was added. Here, hydrogen was introduced by a balloon, and the reduction reaction was performed at room temperature. After about 2 hours, it was confirmed that the balloon did not deflate any more, and the reaction was terminated. After completion of the reaction, the mixture was filtered to remove the palladium compound as a catalyst, and concentrated by a rotary evaporator to obtain the following diamine compound (1). The obtained solid was directly used for the reaction.
[0095]
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[0096]
Synthesis Example 3 Synthesis of hydroxyl-containing diamine (2)
15.4 g (0.1 mol) of 2-amino-4-nitrophenol was dissolved in 50 ml of acetone and 30 g (0.34 mol) of propylene oxide, and cooled to -15 ° C. A solution prepared by dissolving 11.2 g (0.055 mol) of isophthalic acid chloride in 60 ml of acetone was gradually added dropwise thereto. After the completion of the dropwise addition, the reaction was carried out at -15 ° C for 4 hours. Thereafter, the temperature was returned to room temperature, and the generated precipitate was collected by filtration. This precipitate was dissolved in 200 ml of GBL, 3 g of 5% palladium-carbon was added, and the mixture was vigorously stirred. A balloon filled with hydrogen gas was attached thereto, and stirring was continued at room temperature until the hydrogen gas balloon did not shrink any more, and further stirred for 2 hours with the hydrogen gas balloon attached. After completion of the stirring, the palladium compound was removed by filtration, and the solution was concentrated to a half volume with a rotary evaporator. Ethanol was added thereto and recrystallization was performed to obtain the following diamine (2) crystals.
[0097]
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[0098]
Synthesis Example 4 Synthesis of hydroxyl-containing diamine (3)
15.4 g (0.1 mol) of 2-amino-4-nitrophenol was dissolved in 100 ml of acetone and 17.4 g (0.3 mol) of propylene oxide, and cooled to -15 ° C. A solution of 20.4 g (0.11 mol) of 4-nitrobenzoyl chloride dissolved in 100 ml of acetone was gradually added dropwise thereto. After the completion of the dropwise addition, the reaction was carried out at -15 ° C for 4 hours. Thereafter, the temperature was returned to room temperature, and the generated precipitate was collected by filtration. Thereafter, crystals of the following diamine (3) were obtained in the same manner as in Synthesis Example 2.
[0099]
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[0100]
Synthesis Example 5 Synthesis of quinonediazide compound (1)
Under dry nitrogen flow, BisPG-26X (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), 19.71 g (0.05 mol), 13.56 g (0.05 mol) of 5-naphthoquinonediazidosulfonyl chloride and 4- 13.14 g (0.05 mol) of naphthoquinonediazidosulfonylic acid chloride was dissolved in 450 g of 1,4-dioxane and brought to room temperature. To this, 10.12 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the inside of the system did not reach 35 ° C. or higher. After the dropwise addition, the mixture was stirred at 30 ° C. for 2 hours. The triethylamine salt was filtered, and the filtrate was poured into water. Thereafter, the deposited precipitate was collected by filtration. The precipitate was dried with a vacuum drier to obtain the following quinonediazide compound (1). Here, the ratio in the formula is a molar ratio.
[0101]
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[0102]
Synthesis Example 6 Synthesis of quinonediazide compound (2)
Under a dry nitrogen stream, 19.72 g (0.05 mol) of BIR-PTBP (trade name, manufactured by Asahi Organic Materials Co., Ltd.) and 26.86 g (0.1 mol) of 4-naphthoquinonediazidosulfonyl chloride were mixed with 1 It was dissolved in 450 g of 4-dioxane and brought to room temperature. Here, 10.12 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the inside of the system did not become 35 ° C. or higher, and the mixture was stirred at 30 ° C. for 2 hours. The triethylamine salt was filtered, and the filtrate was poured into water. Thereafter, the deposited precipitate was collected by filtration. The precipitate was dried with a vacuum drier to obtain the following quinonediazide compound (2). The ratios in the formula are molar ratios.
[0103]
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[0104]
Synthesis Example 7 Synthesis of quinonediazide compound (3)
Under a dry nitrogen stream, 7.21 g (0.05 mol) of 2-naphthol and 13.43 g (0.05 mol) of 5-naphthoquinonediazidosulfonyl chloride were dissolved in 450 g of 1,4-dioxane, and the mixture was brought to room temperature. Here, the following quinonediazide compound (3) was obtained in the same manner as in Synthesis Example 6 using 5.06 g of triethylamine mixed with 50 g of 1,4-dioxane.
[0105]
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[0106]
Synthesis Example 8 Synthesis of quinonediazide compound (4)
Under dry nitrogen flow, TrisP HAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), 15.31 g (0.05 mol) and 40.28 g (0.15 mol) of 5-naphthoquinonediazidosulfonyl chloride in 1,4 were added. -Dissolved in 450 g of dioxane and brought to room temperature. Here, the following quinonediazide compound (4) was obtained in the same manner as in Synthesis Example 6 using 15.18 g of triethylamine mixed with 50 g of 1,4-dioxane.
[0107]
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[0108]
Synthesis Example 9 Synthesis of quinonediazide compound (5)
Under a dry nitrogen stream, 6.81 g (0.05 mol) of 4-isopropylphenol and 13.43 g (0.05 mol) of 5-naphthoquinonediazidosulfonyl chloride were dissolved in 450 g of 1,4-dioxane, and the mixture was brought to room temperature. Here, the following quinonediazide compound (5) was obtained in the same manner as in Synthesis Example 6 using 5.06 g of triethylamine mixed with 50 g of 1,4-dioxane.
[0109]
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[0110]
Synthesis Example 10 Synthesis of quinonediazide compound (6)
Under a stream of dry nitrogen, 11.41 g (0.05 mol) of bisphenol A and 26.86 g (0.1 mol) of 5-naphthoquinonediazidosulfonyl chloride were dissolved in 450 g of 1,4-dioxane, and the mixture was brought to room temperature. Here, the following quinonediazide compound (6) was obtained in the same manner as in Synthesis Example 6 using 10.12 g of triethylamine mixed with 50 g of 1,4-dioxane.
[0111]
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[0112]
Synthesis Example 11 Synthesis of quinonediazide compound (7)
Under a dry nitrogen stream, 24.2 g (0.05 mol) of benzene-1,2,3-tricarboxytris-((2-hydroxyphenyl) amide) and 40.28 g (0.15 g) of 5-naphthoquinonediazidosulfonyl chloride were used. Mol) was dissolved in 450 g of 1,4-dioxane and brought to room temperature. Here, the following quinonediazide compound (7) was obtained in the same manner as in Synthesis Example 6 using 10.12 g of triethylamine mixed with 50 g of 1,4-dioxane.
[0113]
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[0114]
Synthesis Example 12 Synthesis of quinonediazide compound (8)
Under a dry nitrogen stream, N, N'bis- (2-hydroxyphenyl) -terephthalimide 24.2 g (0.05 mol) 17.42 g (0.05 mol) and 5-naphthoquinonediazidosulfonylic acid chloride 26.86 g ( 0.1 mol) was dissolved in 450 g of 1,4-dioxane and brought to room temperature. Here, the following quinonediazide compound (8) was obtained in the same manner as in Synthesis Example 6 using 10.12 g of triethylamine mixed with 50 g of 1,4-dioxane.
[0115]
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[0116]
Synthesis Example 13 Synthesis of compound (1) having phenolic hydroxyl group
Under a dry nitrogen stream, 16.4 g (0.15 mol) of 2-aminophenol (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 100 g of NMP and placed in an ice bath to reach 0 ° C. Thereafter, 13.1 g (0.05 mol) of trimesolyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 20 g of NMP, dropped with a dropping funnel, and stirred for 2 hours. After completion of the reaction, the solution was poured into 3 L of water to collect a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80 ° C. for 20 hours to obtain the following compound (1) having a phenolic hydroxyl group.
[0117]
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[0118]
Synthesis Example 14 Synthesis of compound (2) having phenolic hydroxyl group
Under a dry nitrogen stream, 18.4 g (0.15 mol) of 2-amino-m-cresol (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 100 g of NMP, and the solution was placed in an ice bath and brought to 0 ° C. Thereafter, 13.1 g (0.05 mol) of trimesolyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 20 g of NMP, dropped with a dropping funnel, and stirred for 2 hours. After completion of the reaction, the solution was poured into 3 L of water to collect a white precipitate. The precipitate was collected by filtration, washed with water three times, and then dried in a vacuum dryer at 80 ° C. for 20 hours to obtain the following compound (2) having a phenolic hydroxyl group.
[0119]
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[0120]
Synthesis Example 16 Synthesis of compound (3) having phenolic hydroxyl group
Under a dry nitrogen stream, 24.8 g (0.15 mol) of 2-amino-4-tert-butylphenol (manufactured by Aldridge) was dissolved in 100 g of NMP and placed in an ice bath to reach 0 ° C. Thereafter, 13.1 g (0.05 mol) of trimesolyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 20 g of NMP, dropped with a dropping funnel, and stirred for 2 hours. After completion of the reaction, the solution was poured into 3 L of water to collect a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80 ° C. for 20 hours to obtain the following compound (3) having a phenolic hydroxyl group.
[0121]
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[0122]
Synthesis Example 17 Synthesis of compound (4) having phenolic hydroxyl group
Under a stream of dry nitrogen, 10.9 g (0.10 mol) of 2-aminophenol (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 100 g of NMP, and the solution was placed in an ice bath and cooled to 0 ° C. Then, 10.0 g (0.05 mol) of terephthaloyl chloride (manufactured by Aldridge) was dissolved in 20 g of NMP, dropped with a dropping funnel, and stirred for 2 hours. After completion of the reaction, the solution was poured into 3 L of water to collect a white precipitate. The precipitate was collected by filtration, washed with water three times, and dried with a vacuum dryer at 80 ° C. for 20 hours to obtain the following compound (4) having a phenolic hydroxyl group.
[0123]
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[0124]
Synthesis Example 18 Synthesis of Compound (5) Having Phenolic Hydroxyl Group
Under a dry nitrogen stream, 16.1 g (0.10 mol) of 4-aminorhizocinol hydrochloride (manufactured by Aldridge) was dissolved in 100 g of NMP and placed in an ice bath to reach 0 ° C. Then, 10.0 g (0.05 mol) of terephthaloyl chloride (manufactured by Aldridge) was dissolved in 20 g of NMP, dropped with a dropping funnel, and stirred for 2 hours. After completion of the reaction, the solution was poured into 3 L of water to collect a white precipitate. The precipitate was collected by filtration, washed three times with water, and dried in a vacuum dryer at 80 ° C. for 20 hours to obtain the following compound (5) having a phenolic hydroxyl group.
[0125]
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[0126]
Example 1
Under a stream of dry nitrogen, 5.01 g (0.025 mol) of 4,4′-diaminophenyl ether and 1.24 g (0.005 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane were added to N- It was dissolved in 50 g of methyl-2-pyrrolidone (NMP). Here, 21.4 g (0.03 mol) of the hydroxy group-containing anhydride obtained in Synthesis Example 1 was added together with 14 g of NMP, reacted at 20 ° C. for 1 hour, and then reacted at 50 ° C. for 4 hours. Thereafter, a solution prepared by diluting 7.14 g (0.06 mol) of N, N-dimethylformamide dimethyl acetal with 5 g of NMP was added dropwise over 10 minutes. After the dropwise addition, the mixture was stirred at 50 ° C. for 3 hours to obtain a polymer solution (1).
[0127]
To 40 g of the obtained polymer solution (1), 2.0 g of the quinonediazide compound (3) obtained in Synthesis Example 5 and 1.0 g of the compound having an enol hydroxyl group (1) obtained in Synthesis Example 13 were added, followed by photosensitivity. Varnish A of a polyimide precursor composition was obtained. Using the obtained varnish A, a photosensitive polyimide precursor film was formed on a silicon wafer, exposed and developed, and the varnish was evaluated for sensitivity, residual film ratio, resolution, and shrinkage. Table 1 summarizes the evaluation results.
[0128]
Example 2
Under a dry nitrogen stream, 15.1 g (0.025 mol) of the hydroxyl group-containing diamine (1) obtained in Synthesis Example 2 was dissolved in 50 g of N-methyl-2-pyrrolidone (NMP). Here, 17.5 g (0.025 mol) of the hydroxy group-containing anhydride obtained in Synthesis Example 1 was added together with 30 g of pyridine, and reacted at 60 ° C. for 6 hours. After completion of the reaction, the solution was poured into 2 L of water, and a precipitate of polymer solid was collected by filtration. The polymer solid was dried in a vacuum dryer at 80 ° C. for 20 hours to obtain a white solid (2). 10 g of the obtained white solid (2) was weighed, 2 g of the quinonediazide compound (4) obtained in Synthesis Example 8, 2.0 g of the compound (2) having a phenolic hydroxyl group obtained in Synthesis Example 14, 1 g of methoxysilane was dissolved in 30 g of gamma-butyrolactone to obtain a varnish B of a photosensitive polyimide precursor composition. Using the obtained varnish B, a photosensitive polyimide precursor film was formed on a silicon wafer, exposed and developed, and the varnish was evaluated for sensitivity, residual film ratio, resolution, and shrinkage.
[0129]
Example 3
Under a stream of dry nitrogen, 17.0 g (0.045 mol) of the hydroxyl group-containing diamine compound (2) obtained in Synthesis Example 3 and 1.24 g of 1,3-bis (3-aminopropyl) tetramethyldisiloxane (0 (0.005 mol) was dissolved in 50 g of NMP. To this, 12.4 g (0.04 mol) of 3,3 ', 4,4'-diphenylethertetracarboxylic anhydride was added together with 21 g of NMP, reacted at 20 ° C for 1 hour, and then reacted at 50 ° C for 2 hours. . 0.98 g (0.01 mol) of maleic anhydride was added thereto, and the mixture was stirred at 50 ° C. for 2 hours, and then a solution prepared by diluting 14.7 g (0.1 mol) of N, N-dimethylformamide diethyl acetal with 5 g of NMP was added. Dropped over minutes. After the dropwise addition, the mixture was stirred at 50 ° C. for 3 hours to obtain a polymer solution (3). 1.6 g of the quinonediazide compound (5) obtained in Synthesis Example 9 and 0.8 g of the compound (3) having a phenolic hydroxyl group obtained in Synthesis Example 16 were dissolved in 30 g of the obtained polymer solution (3) and exposed to light. A varnish C of a functional polyimide precursor composition was obtained. Using the obtained varnish C, a photosensitive polyimide precursor film was formed on a silicon wafer, exposed and developed, and the varnish was evaluated for sensitivity, residual film ratio, resolution, and shrinkage.
[0130]
Example 4
Under a dry nitrogen stream, 6.08 g (0.025 mol) of the hydroxyl group-containing diamine compound (3) obtained in Synthesis Example 4, 4.51 g (0.0225 mol) of 4,4′-diaminodiphenyl ether and 1,3 0.62 g (0.0025 mol) of -bis (3-aminopropyl) tetramethyldisiloxane was dissolved in 70 g of NMP. 24.99 g (0.035 mol) of a hydroxyl group-containing acid anhydride and 4.41 g (0.015 mol) of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride are added together with 25 g of NMP at room temperature, and the mixture is added as it is. The mixture was stirred at room temperature for 1 hour and then at 50 ° C. for 2 hours. Subsequently, a solution obtained by diluting 17.6 g (0.2 mol) of glycidyl methyl ether with 10 g of NMP was added, and the mixture was stirred at 70 ° C. for 6 hours to obtain a polymer solution (4). To 40 g of the obtained polymer solution (4), 2.5 g of the quinonediazide compound (6) obtained in Synthesis Example 10 and the compound (4) 2 having a phenolic hydroxyl group used in the present invention obtained in Synthesis Example 17 and used in the present invention. 0.0g was dissolved to obtain a varnish D of a photosensitive polyimide precursor composition. Using the obtained varnish D, a photosensitive polyimide precursor film was formed on a silicon wafer, exposed and developed, and the varnish was evaluated for sensitivity, residual film ratio, resolution, and shrinkage.
[0131]
Example 5
Under a stream of dry nitrogen, 18.3 g (0.05 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was added to 50 g of N-methyl-2-pyrrolidone (NMP) and glycidyl methyl ether. The solution was dissolved in 4 g (0.3 mol), and the temperature of the solution was cooled to -15 ° C. A solution prepared by dissolving 7.38 g (0.025 mol) of diphenyl ether dicarboxylic acid dichloride and 5.08 g (0.025 mol) of isophthalic dichloride in 25 g of gamma-butyrolactone was dropped so that the internal temperature did not exceed 0 ° C. did. After completion of the dropwise addition, stirring was continued at −15 ° C. for 6 hours. After completion of the reaction, the solution was poured into 3 L of water to collect a white precipitate. The precipitate was collected by filtration, washed with water three times, and dried in a vacuum dryer at 80 ° C. for 20 hours to obtain a white polymer solid (5). 2.5 g of the quinonediazide compound (1) obtained in Synthesis Example 5 and the compound (3) having a phenolic hydroxyl group obtained in Synthesis Example 16 were dissolved in 50 g of the obtained polymer solid (5) to prepare a photosensitive polyimide precursor. A varnish E of the body composition was obtained. Using the obtained varnish E, a photosensitive polyimide precursor film was formed on a silicon wafer, exposed and developed, and the varnish was evaluated for sensitivity, residual film ratio, resolution, and shrinkage.
[0132]
Example 6
To 40 g of the polymer solution (1) obtained in Example 1, 2.0 g of the quinonediazide compound (8) obtained in Synthesis Example 12 and 2.0 g of the compound (4) having a phenolic hydroxyl group obtained in Synthesis Example 17 were added. The varnish F of the photosensitive polyimide precursor composition was obtained by dissolving. Using the obtained varnish F, a photosensitive polyimide precursor film was formed on a silicon wafer, exposed and developed, and the varnish was evaluated for sensitivity, residual film ratio, resolution, and shrinkage.
[0133]
Example 7
To 40 g of the polymer solution (4) obtained in Example 4, 2.0 g of the quinonediazide compound (2) obtained in Synthesis Example 6 and 2.0 g of the compound (5) having a phenolic hydroxyl group obtained in Synthesis Example 18 were added. The varnish G of the photosensitive polyimide precursor composition was obtained by dissolving. Using the obtained varnish G, a photosensitive polyimide precursor film was prepared on a silicon wafer, exposed and developed, and the varnish was evaluated for sensitivity, residual film ratio, resolution, and shrinkage.
[0134]
Example 8
2.0 g of the quinonediazide compound (4) obtained in Synthesis Example 8 and 10.0 g of the phenolic hydroxyl group-containing compound (2) obtained in Synthesis Example 14 were added to 10.0 g of the polymer solid (5) obtained in Example 5. 0 g was dissolved in 30 g of NMP to obtain a varnish H of a photosensitive polybenzoxazole precursor composition. Using the obtained varnish H, a photosensitive polybenzoxazole precursor film was formed on a silicon wafer, exposed and developed, and the varnish was evaluated for sensitivity, residual film ratio, resolution, and shrinkage.
[0135]
Example 9
Under a stream of dry nitrogen, 15.1 g (0.025 mol) of the diamine compound (2) obtained in Synthesis Example 3, 4.5 g (0.0225 mol) of 4,4′-diaminodiphenyl ether and 1,3-bis ( 0.62 g (0.0025 mol) of (3-aminopropyl) tetramethyldisiloxane was dissolved in 100 g of GBL. To this, 16.1 g (0.050 mol) of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride was added at room temperature together with 33 g of GBL, and the mixture was reacted at room temperature for 1 hour and then at 50 ° C for 4 hours. Solution (6) was obtained. In 50 g of the obtained polymer solution (6), 7.6 g of the quinonediazide compound (7) obtained in Synthesis Example 11 was dissolved to obtain Varnish I of a photosensitive polyimide precursor composition. Using the obtained varnish I, a photosensitive polyimide precursor film was formed on a silicon wafer, exposed and developed, and the varnish was evaluated for sensitivity, residual film ratio, and resolution.
[0136]
Example 10
Under dry nitrogen flow, 19.0 g (0.095 mol) of 4,4′-diaminodiphenyl ether and 1.24 g (0.005 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane were dissolved in 350 g of GBL. I let it. Here, 71.4 g (0.1 mol) of the acid anhydride obtained in Synthesis Example 1 was added together with 40 g of GBL, and the mixture was reacted at 20 ° C. for 1 hour, and then reacted at 50 ° C. for 4 hours to obtain a polymer solution (7). Was. To 50 g of the obtained polymer solution (7), 20.0 g of the quinonediazide compound (8) obtained in Synthesis Example 12 was added together with 10 g of GBL to obtain a varnish J of a photosensitive polyimide precursor composition. Using the obtained varnish J, a photosensitive polyimide precursor film was formed on a silicon wafer, exposed and developed, and the varnish was evaluated for sensitivity, residual film ratio, and resolution.
[0137]
Comparative Example 1
To 40 g of the polymer solution (1) obtained in Example 1, 2.0 g of the quinonediazide compound (3) obtained in Synthesis Example 7, a compound Bis-RS-2P having a phenolic hydroxyl group represented by the following chemical formula (trade name, 1.0 g of Honshu Chemical Industry Co., Ltd.) was added to obtain a varnish K of a photosensitive polyimide precursor composition. Using the obtained varnish K, a photosensitive polyimide precursor film was formed on a silicon wafer, exposed and developed, and the varnish sensitivity, residual film ratio, resolution, and shrinkage were evaluated.
[0138]
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[0139]
Comparative Example 2
10 g of the polymer solid (2) obtained in Example 2 was weighed, 2 g of the quinonediazide compound (4) obtained in Synthesis Example 8, a compound BisPG-26X having a phenolic hydroxyl group represented by the following chemical formula (trade name, Honshu Chemical Industry Co., Ltd.) 2.0 g and vinyltrimethoxysilane (1 g) were dissolved in gamma-butyrolactone (30 g) to obtain a varnish L of a photosensitive polyimide precursor composition. Using the obtained varnish L, a photosensitive polyimide precursor film was formed on a silicon wafer, exposed and developed, and the varnish sensitivity, remaining film ratio, resolution, and shrinkage were evaluated.
[0140]
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[0141]
Comparative Example 3
To 30 g of the polymer solution (3) obtained in Example 3, 1.6 g of the quinonediazide compound (5) obtained in Synthesis Example 9 and 0.8 g of a compound Bis-RS-3P having a phenolic hydroxyl group represented by the following chemical formula were added. The varnish M of the photosensitive polyimide precursor composition was obtained by dissolving. Using the obtained varnish M, a photosensitive polyimide precursor film was formed on a silicon wafer, exposed and developed, and the varnish was evaluated for sensitivity, residual film ratio, resolution, and shrinkage.
[0142]
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[0143]
Comparative Example 4
In 40 g of the polymer solution (1) obtained in Example 1, 2.0 g of the quinonediazide compound (3) obtained in Synthesis Example 7 was dissolved to obtain a varnish N of a photosensitive polyimide precursor composition. Using the obtained varnish N, a photosensitive polyimide precursor film was formed on a silicon wafer, exposed and developed, and the varnish was evaluated for sensitivity, residual film ratio, resolution, and shrinkage.
[0144]
Comparative Example 5
In 40 g of the polymer solution (1) obtained in Example 1, 2.0 g of the quinonediazide compound (3) obtained in Synthesis Example 7, TrisP-PA represented by the following chemical formula (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) 1.0 g was dissolved to obtain a varnish O of a photosensitive polyimide precursor composition. Using the obtained varnish O, a photosensitive polyimide precursor film was formed on a silicon wafer, exposed and developed, and the varnish was evaluated for sensitivity, residual film ratio, resolution, and shrinkage.
[0145]
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[0146]
Comparative Example 6
1.6 g of the quinonediazide compound (5) obtained in Synthesis Example 9 in 30 g of the polymer solid (2) obtained in Synthesis Example 14 and BisP-AP represented by the following chemical formula (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) 0.8 g was dissolved to obtain a varnish P of a photosensitive polyimide precursor composition. Using the obtained varnish P, a photosensitive polyimide precursor film was formed on a silicon wafer, exposed and developed, and the varnish was evaluated for sensitivity, residual film ratio, resolution, and shrinkage.
[0147]
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[0148]
Table 1 shows the evaluation results of the examples and comparative examples. In the examples using the positive photosensitive resin precursor composition of the present invention, the shrinkage was small and the resolution was excellent. On the other hand, the comparative example in which the compound having a phenolic hydroxyl group represented by the general formula (2) was not used had a relatively large shrinkage ratio and poor resolution.
[0149]
[Table 1]

[0150]
【The invention's effect】
According to the present invention, it is possible to obtain a positive photosensitive resin precursor composition which can be developed with an aqueous alkali solution and has excellent resolution, sensitivity, residual film ratio, and shrinkage after curing.

Claims (5)

(A) a polymer having a structural unit represented by the general formula (1) as a main component, (b) a compound having a phenolic hydroxyl group represented by the general formula (2), and (c) an esterified quinonediazide compound. A positive photosensitive resin precursor composition characterized by containing:

Wherein R ¹ is a divalent to octavalent organic group having two or more carbon atoms, R ² is a divalent to hexavalent organic group having two or more carbon atoms, and R ¹ and R ² R ³ represents hydrogen or an organic group having 1 to 20 carbon atoms, and may be the same or different, n is an integer of 10 to 100,000, and m is An integer from 0 to 4, p and q each represent an integer from 0 to 4, provided that p + q> 0.

(Wherein R ⁴ represents hydrogen or an organic group having 1 to 20 carbon atoms. R ⁵ is one selected from hydrogen, a hydroxyl group and an organic group having 1 to 20 carbon atoms. A represents an integer of 0 to 3, b represents an integer of 2 to 6, and c represents an integer of 0 to 4.) The positive photosensitive resin precursor according to claim 1, wherein the R ¹ (COOR ³ ) _m (OH) _p portion of the general formula (1) has a structure represented by the general formula (3). Composition.

(Wherein R ^6, R ⁸ represents a divalent to tetravalent organic group having 2 to 20 carbon atoms, R ⁷ is a trivalent to hexavalent organic group having 3 to 20 carbon atoms, R ^9, R ¹⁰ represents hydrogen or an organic group having 1 to 20 carbon atoms.o and s represent an integer of 0 to 2, and r represents an integer of 1 to 4.) R ² (OH) _q moiety of general formula (1) is characterized by having a structure represented by the general formula (4), according to claim 1 positive photosensitive resin precursor composition.

(In the formula, R ¹¹ and R ¹³ represent a trivalent to tetravalent organic group having 2 to 20 carbon atoms, and R ¹² represents a divalent organic group having 2 to 30 carbon atoms. T and u represent 1 or 2 Is shown.) R ² (OH) _q moiety of general formula (1) is characterized by having a structure represented by the general formula (5), according to claim 1 positive photosensitive resin precursor composition.

(In the formula, R ¹⁴ and R ¹⁶ each represent a divalent organic group having 2 to 20 carbon atoms, and R ¹⁵ represents a trivalent to hexavalent organic group having 3 to 20 carbon atoms. Indicates an integer up to.) The positive photosensitive resin precursor composition according to claim 1, wherein the R ² (OH) _q portion of the general formula (1) has a structure represented by the general formula (6).

(In the formula, R ¹⁷ represents a divalent organic group having 2 to 20 carbon atoms, and R ¹⁸ represents a trivalent to hexavalent organic group having 3 to 20 carbon atoms. W represents an integer of 1 to 4. Shown.)