JP2004095773A - Composition for semiconductor device, and method for manufacturing semiconductor device using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic flattening material used for a semiconductor device having excellent removability. <P>SOLUTION: This composition for the semiconductor device becomes insoluble in an organic solvent and/or an alkaline aqueous solution by light and/or heat treatment (pretreatment), and the composition to be dry etched has an etching rate of 1.2 times or more after posttreatment with respect to the composition after light and/or heat treatment (posttreatment) and contains (a) a polymer soluble in an organic low molecular weight compound of a liquid at 23°C at atmospheric pressure, and (b) a low molecular weight compound having a polymerizable group and/or a crosslinkable group. <P>COPYRIGHT: (C)2004,JPO

Description

【００３３】
（式中、Ｒ^１、Ｒ^３は、水素原子、メチル基、ハロゲン、メチロール基を表す。Ｒ^４、Ｒ^５は炭素数１から２０のアルキル基、―（ＣＨＲ^６ＯＣＨＲ^７）_ｌ−、―Ｒ^８ＣＯ−、を示す。Ｒ^６、Ｒ^７、Ｒ^８は炭素数１〜２０のアルキル基、芳香族を含有する有機基から選ばれ、それぞれ同じでも異なっていてもよい。ｐ、ｑは、０または１の整数を示す。Ｒ^２は、酸や熱により解離する解離性基を示す。また、ｎ、ｍは０〜６までの整数であり、ｎ＋ｍ＞０である）。
【００３４】
一般式（Ｉ）で表される化合物は、例えば、上記のカルボキシル基を有する重合性モノマーのうち、（メタ）アクリロイル基を有するものの酸クロリドとアルコール類とを、トリエチルアミン等を触媒としての反応させる方法、上記のカルボキシル基を有する重合性モノマーのうち、（メタ）アクリロイル基を有するものと、ビニルエーテル類とを、ｐ−トルエンスルホン酸ピリジニウム等を触媒として付加反応させる方法、上記のカルボキシル基を有する重合性モノマーのうち、（メタ）アクリロイル基を有するものと、アクリレートとを加熱により付加反応させる方法、上記の水酸基を１つ有するラジカル重合性モノマー（４）と、ビニルエーテル類とを、ｐ−トルエンスルホン酸ピリジニウム等を触媒として付加反応させるの４種の方法等により容易に合成することができる。
【００３５】
上記で示されるように、Ｒ^２で表される解離性基は、アルコール類の構造成分であり、ビニルエーテル類の構造成分であり、アクリレート類の構造成分である。
【００３６】
ここでいうアルコール類としては、例えば、ＤＭ−ＢＩ２５Ｘ−Ｆ、４６ＤＭＯＣ、４６ＤＭＯＩＰＰ、４６ＤＭＯＥＰ、ＴＭ−ＢＩＰ−Ａ（以上商品名、旭有機材工業（株）製）、ＤＭＬ−ＭＢＰＣ、ＤＭＬ−ＭＢＯＣ、ＤＭＬ−ＯＣＨＰ、ＤＭＬ−ＰＣ、ＤＭＬ−ＰＣＨＰ、ＤＭＬ−ＰＴＢＰ、ＤＭＬ−３４Ｘ、ＤＭＬ−ＥＰ、ＤＭＬ−ＰＯＰ、ＤＭＬ−ＯＣ、ジメチロール−Ｂｉｓ−Ｃ、ジメチロール−ＢｉｓＯＣ−Ｐ、ＤＭＬ−ＢｉｓＯＣ−Ｚ、ＤＭＬ−ＢｉｓＯＣＨＰ−Ｚ、ＤＭＬ−ＰＦＰ、ＤＭＬ−ＰＳＢＰ、ＤＭＬ−ＭＢ２５、ＤＭＬ−ＭＴｒｉｓＰＣ、ＤＭＬ−Ｂｉｓ２５Ｘ−３４ＸＬ、ＤＭＬ−Ｂｉｓ２５Ｘ−ＰＣＨＰ、ＴｒｉＭＬ−Ｐ、ＴｒｉＭＬ−３５ＸＬ、ＴｒｉＭＬ−ＴｒｉｓＣＲ−ＨＡＰ、ＴＭＬ−ＢＰ、ＴＭＬ−ＨＱ、ＴＭＬ−ｐｐ−ＢＰＦ、ＴＭＬ−ＢＰＡ、ＴＭＯＭ−ＢＰ、ＨＭＬ−ＴＰＰＨＢＡ、ＨＭＬ−ＴＰＨＡＰ（以上商品名、本州化学工業（株）製）、ｔ−ブタノール、ジアセトンアルコール、トリアセトンジアルコール、２，５−ジメチル−２，５−ヘキサンジオール、２，４−ジメチル−２，４−ペンタンジオール、３−メチル−１，３−ブタンジオール、α，α’−ジヒドロキシ−１，３−ジイソプロピルベンゼン、α，α’−ジヒドロキシ−１，４−ジイソプロピルベンゼン、α，α’，α’’−トリヒドロキシ−１，３，５−トリイソプロピルベンゼン、が挙げられる。
【００３７】
これらの中、好ましくは、トリアセトンジアルコール、２，５−ジメチル−２，５−ヘキサンジオール、α，α’−ジヒドロキシ−１，３−ジイソプロピルベンゼン、α，α’−ジヒドロキシ−１，４−ジイソプロピルベンゼン、α，α’，α’’−トリヒドロキシ−１，３，５−トリイソプロピルベンゼン等である。
【００３８】
ここでいうビニルエーテル類としては、エチルビニルエーテル、ｎ−プロピルビニルエーテル、イソプロピルビニルエーテル、ｎ−ブチルビニルエーテル、イソブチルビニルエーテル、オクタドデシルビニルエーテル、シクロヘキシルビニルエーテル、ブタンジオールモノビニルエーテル、シクロヘキサンジメタノールモノビニルエーテル、ｔ−ブチルビニルエーテル、ｔ−アミルビニルエーテル、エチルヘキシルビニルエーテル、ドデシルビニルエーテル、エチレングリコールモノビニルエーテル、エチレングリコールブチルビニルエーテル、ヘキサンジオールモノビニルエーテル、ジエチレングリコールモノビニルエーテル、トリエチレングリコールモノビニルエーテル、ジエチルアミノエチルビニルエーテル、ブタンジオールジビニルエーテル、シクロヘキサンジメタノールジビニルエーテル、ジエチレングリコールジビニルエーテル、トリエチレングリコールジビニルエーテル、エチレングリコールジビニルエーテル、ヘキサンジオールジビニルエーテル、テトラエチレングリコールジビニルエーテル、トリメチロールプロパントリビニルエーテル等が挙げられる。これらの中、特に好ましくは、シクロヘキサンジメタノールジビニルエーテル、ジエチレングリコールジビニルエーテル、トリエチレングリコールジビニルエーテル、テトラエチレングリコールジビニルエーテル、トリメチロールプロパントリビニルエーテル等である。
【００３９】
ここでいうアクリレート類としては、上記その他のラジカル重合性モノマーで例示した（メタ）アクリレート類、（メタ）アクリレート類のうち、アクリレート類、アクリルアミド類に相当するもの、エチレングリコールジアクリレート、テトラエチレングリコールジアクリレート、ポリエチレングリコールジアクリレート、１，４−ブタンジオールジアクリレート、１，６−ヘキサンジオールジアクリレート、ネオペンチルグリコールジアクリレート、トリメチロールプロパントリオキシエチルアクリレート、トリシクロデカンジメタノールジアクリレート、ジシクロペンタジエンジアクリレート、トリシクロデカニルジアクリレート、トリメチロールプロパントリオキシプロピルアクリレート、トリス−２−ヒドロキシエチルイソシアヌレートトリアクリレート、トリス−２−ヒドロキシエチルイソシアヌレートジアクリレート、「ビスコート３７００」（大阪有機社製）が挙げられる。
【００４０】
また、分解性モノマー（５）であるビニルエーテル類は、上記の酸および／または熱により解離する解離性基を有する一般式（Ｉ）で表される化合物の構造成分であるビニルエーテル類と同一のものを用いることができる。
【００４１】
また、上記分解性モノマー（５）は、本発明の（ａ）成分のラジカル重合性ポリマーや、反応性基含有ポリマーの中、上記のフェノール性水酸基またはカルボキシル基を有するラジカル重合性モノマーの単独重合体ポリマーおよび／または該ラジカル重合性モノマーとそれ以外のラジカル重合性モノマーの共重合体ポリマーに、上記のエポキシ基を含有するラジカル重合性モノマーを添加し、エポキシ基を開環付加させることによって得られたポリマーや、上記のエポキシ基を含有するラジカル重合性モノマーの単独重合体ポリマーおよび／または該ラジカル重合性モノマーとそれ以外のラジカル重合性モノマーの共重合体ポリマーに、上記のフェノール性水酸基またはカルボキシル基を有するラジカル重合性モノマーを添加し、エポキシ基を開環付加させることによって得られたポリマーに、ゲル化しない程度に好ましく導入することができる。
【００４２】
その導入量は、ポリマーを構成する全モノマー１００重量部に対して、８０重量部以下である。分解性モノマー（５）を導入した（ａ）成分は、その後の光および／または熱処理（後処理）により、分解等の化学構造変化を起こす。上記分解性モノマー（５）を導入した（ａ）成分の好ましい重量平均分子量は、６００００以下、特に好ましくは１０００〜４００００である。６００００を越えると、組成物にした場合、粘度が高くなり、塗布作業性に劣るという問題がある。
【００４３】
反応性希釈モノマー（６）としては、例えば、重合性基を１つ有する単官能性化合物として、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、ブトキシエチル（メタ）アクリレート、エチルジエチレングリコール（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ポリエチレングリコール（メタ）アクリレート、ポリプロピレングリコール（メタ）アクリレート、メチルトリメチレングリコール（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート、７−アミノ−３，７−ジメチルオクチル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ラウリル（メタ）アクリレート、ビニルピロリドン、Ｎ−ビニルカプロラクタム、ビニルフェノール、アクリルアミド、酢酸ビニル、上記の分解性モノマー（５）の構造成分として示されたビニルエーテル類のモノビニルエーテルに相当するもの、スチレン、「ＡＲＯＮＩＸ　Ｍ−１１４」（東亜合成化学（株）製）、「ＡＲＯＮＩＸ　Ｍ−１１３」（同）、「ＴＣ−１１０Ｓ」（日本化薬（株）製）、重合性基を多数有する多官能性化合物としては、トリメチロールプロパントリ（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、１，４−ブタンジオールジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、トリメチロールプロパントリオキシエチル（メタ）アクリレート、トリシクロデカンジメタノールジ（メタ）アクリレート、ジシクロペンタジエンジ（メタ）アクリレート、トリシクロデカニルジ（メタ）アクリレート、トリメチロールプロパントリオキシプロピル（メタ）アクリレート、トリス−２−ヒドロキシエチルイソシアヌレートトリ（メタ）アクリレート、トリス−２−ヒドロキシエチルイソシアヌレートジ（メタ）アクリレート、「ビスコート３７００」（大阪有機社製）、上記の分解性モノマー（５）の構造成分として示されたビニルエーテル類のモノビニルエーテル以外のもの等が挙げられる。これらの化合物は、２種以上組合わせて用いることもできる。
【００４４】
熱架橋性モノマー（７）としては、たとえば、これら架橋性基を１つ有するものとしてＭＬ−２６Ｘ、ＭＬ−２４Ｘ、ＭＬ−２３６ＴＭＰ、４−メチロール３Ｍ６Ｃ、ＭＬ−ＭＣ、ＭＬ−ＴＢＣ（商品名、本州化学工業（株）製）、Ｐ−ａ型ベンゾオキサジン（商品名、四国化成工業（株）製）、３−エチル３−ヒドロキシメチルオキセタン、オキセタンカルボン酸、ヘキシルオキセタン、オキセタンメタクリレート、ベンジルオキセタン、アリルオキセタン、オキセタンモノブチルエーテル、グリシドール、ブチルグリシジルエーテル等、２つ有するものとしてＤＭ−ＢＩ２５Ｘ−Ｆ、４６ＤＭＯＣ、４６ＤＭＯＩＰＰ、４６ＤＭＯＥＰ（商品名、旭有機材工業（株）製）、ＤＭＬ−ＭＢＰＣ、ＤＭＬ−ＭＢＯＣ、ＤＭＬ−ＯＣＨＰ、ＤＭＬ−ＰＣ、ＤＭＬ−ＰＣＨＰ、ＤＭＬ−ＰＴＢＰ、ＤＭＬ−３４Ｘ、ＤＭＬ−ＥＰ、ＤＭＬ−ＰＯＰ、ＤＭＬ−ＯＣ、ジメチロール−Ｂｉｓ−Ｃ、ジメチロール−ＢｉｓＯＣ−Ｐ、ＤＭＬ−ＢｉｓＯＣ−Ｚ、ＤＭＬ−ＢｉｓＯＣＨＰ−Ｚ、ＤＭＬ−ＰＦＰ、ＤＭＬ−ＰＳＢＰ、ＤＭＬ−ＭＢ２５、ＤＭＬ−ＭＴｒｉｓＰＣ、ＤＭＬ−Ｂｉｓ２５Ｘ−３４ＸＬ、ＤＭＬ−Ｂｉｓ２５Ｘ−ＰＣＨＰ（商品名、本州化学工業（株）製）、ニカラックＭＸ−２９０（商品名、（株）三和ケミカル製）、Ｂ−ａ型ベンゾオキサジン、Ｂ−ｍ型ベンゾオキサジン（商品名、四国化成工業（株）製）、２，６−ジメトキシメチル−４−ｔ−ブチルフェノール、２，６−ジメトキシメチル−ｐ−クレゾール、２，６−ジアセトキシメチル−ｐ−クレゾール、カーボネートビスオキセタン、キシリレンビスオキセタン、アジペートビスオキセタン、テレフタレートビスオキセタン、シクロヘキサンジカルボン酸ビスオキセタン、ＭＤＩビスオキセタン等、３つ有するものとしてＴｒｉＭＬ−Ｐ、ＴｒｉＭＬ−３５ＸＬ、ＴｒｉＭＬ−ＴｒｉｓＣＲ−ＨＡＰ（商品名、本州化学工業（株）製）等、４つ有するものとしてＴＭ−ＢＩＰ−Ａ（商品名、旭有機材工業（株）製）、ＴＭＬ−ＢＰ、ＴＭＬ−ＨＱ、ＴＭＬ−ｐｐ−ＢＰＦ、ＴＭＬ−ＢＰＡ、ＴＭＯＭ−ＢＰ（商品名、本州化学工業（株）製）、ニカラックＭＸ−２８０、ニカラックＭＸ−２７０（商品名、（株）三和ケミカル製）等、６つ有するものとしてＨＭＬ−ＴＰＰＨＢＡ、ＨＭＬ−ＴＰＨＡＰ（商品名、本州化学工業（株）製）が挙げられる。
【００４５】
これらのうち、本発明では熱架橋性基を少なくとも２つ含有するものが好ましく、特に好ましくは、２つ有するものとして４６ＤＭＯＣ、４６ＤＭＯＥＰ（商品名、旭有機材工業（株）製）、ＤＭＬ−ＭＢＰＣ、ＤＭＬ−ＭＢＯＣ、ＤＭＬ−ＯＣＨＰ、ＤＭＬ−ＰＣ、ＤＭＬ−ＰＣＨＰ、ＤＭＬ−ＰＴＢＰ、ＤＭＬ−３４Ｘ、ＤＭＬ−ＥＰ、ＤＭＬ−ＰＯＰ、ジメチロール−ＢｉｓＯＣ−Ｐ、ＤＭＬ−ＰＦＰ、ＤＭＬ−ＰＳＢＰ、ＤＭＬ−ＭＴｒｉｓＰＣ（商品名、本州化学工業（株）製）、ニカラックＭＸ−２９０（商品名、（株）三和ケミカル製）、Ｂ−ａ型ベンゾオキサジン、Ｂ−ｍ型ベンゾオキサジン（商品名、四国化成工業（株）製）、２，６−ジメトキシメチル−４−ｔ−ブチルフェノール、２，６−ジメトキシメチル−ｐ−クレゾール、２，６−ジアセトキシメチル−ｐ−クレゾール、カーボネートビスオキセタン、キシリレンビスオキセタン、アジペートビスオキセタン、テレフタレートビスオキセタン、シクロヘキサンジカルボン酸ビスオキセタン、ＭＤＩビスオキセタン等、３つ有するものとしてＴｒｉＭＬ−Ｐ、ＴｒｉＭＬ−３５ＸＬ（商品名、本州化学工業（株）製）等、４つ有するものとしてＴＭ−ＢＩＰ−Ａ（商品名、旭有機材工業（株）製）、ＴＭＬ−ＢＰ、ＴＭＬ−ＨＱ、ＴＭＬ−ｐｐ−ＢＰＦ、ＴＭＬ−ＢＰＡ、ＴＭＯＭ−ＢＰ（商品名、本州化学工業（株）製）、ニカラックＭＸ−２８０、ニカラックＭＸ−２７０（商品名、（株）三和ケミカル製）等、６つ有するものとしてＨＭＬ−ＴＰＰＨＢＡ、ＨＭＬ−ＴＰＨＡＰ（商品名、本州化学工業（株）製）等が挙げられる。これらの化合物は、２種以上組合わせて用いることもできる。
【００４６】
（ｂ）成分のうち、分解性モノマー（５）を導入して得られた（ａ）成分は、それ自体が、その後の光および／または熱処理（後処理）により、分解等の化学構造変化を起こすため、（ｂ）成分との併用に関しては、組成物中では、限定されす用いることができる。これらを組み合わせる場合、（ａ）成分１００重量部に対して、（ｂ）成分は、好ましくは４０００重量部以下、特に好ましくは３０００重量部以下である。４０００重量部を越えると、組成物にした場合、粘度が低くなり、基板に塗布した場合にはじきなどの塗布作業性に劣るという問題がある場合がある。
【００４７】
（ｂ）成分のうち、分解性モノマー（５）を導入していない（ａ）成分は、それ自体が、その後の光および／または熱処理（後処理）により、分解等の化学構造変化を起こさないため、組成物中では、（ｂ）成分の分解性モノマー（５）と併用して用いることができる。
【００４８】
これらを組み合わせる場合、（ａ）成分１００重量部に対して、（ｂ）成分は、好ましくは１０〜４０００重量部、特に好ましくは１０〜３０００重量部である。４０００重量部を越えると、組成物にした場合、粘度が低くなり、基板に塗布した場合にはじきなどの塗布作業性に劣るという問題がある場合がある。また、１０重量部を下回ると、後処理後のエッチングレートが、前処理後のエッチングレートに対し、１．２倍を下回ることがあり、好ましくない。
【００４９】
さらに（ｂ）成分が分解性モノマー（５）である場合、それ自体が、その後の光および／または熱処理（後処理）により、分解等の化学構造変化を起こすため、組成物中では、（ａ）成分と併用せず単独で、または、それ以外の（ｂ）成分と併用して用いることもできる。
【００５０】
これらを組み合わせる場合、分解性モノマー（５）１００重量部に対して、それ以外の（ｂ）成分は、好ましくは４０００重量部以下、特に好ましくは３０００重量部以下である。４０００重量部を越えると、組成物にした場合、粘度が低くなり、基板に塗布した場合にはじきなどの塗布作業性に劣るという問題がある場合がある。
【００５１】
本発明に用いられる（ｃ）成分の酸発生剤は、発生する酸によって、（ａ）成分および／または、（ｂ）成分の分解を促進する作用を有するものである。
【００５２】
（ｃ）成分の酸発生剤としては、例えば、ビス（ｐ−トルエンスルホニル）ジアゾメタン、ビス（１，１−ジメチルエチルスルホニル）ジアゾメタン、ビス（シクロヘキシルスルホニル）ジアゾメタン、ｐ−ビス（２，４−ジメチルフェニルスルホニル）ジアゾメタンなどのビススルホニルジアゾメタン類、ｐ−トルエンスルホン酸−２−ニトロベンジル、ｐ−トルエンスルホン酸−２，６−ジニトロベンジル、ｐ−トリフルオロメチルベンゼンスルホン酸−２，４−ジニトロベンジルなどのニトロベンジル誘導体、ピロガロールのメタンスルホン酸エステル、ピロガロールのベンゼンスルホン酸エステル、ピロガロールのｐ−トルエンスルホン酸エステルなどのピロガロールと脂肪族又は芳香族スルホン酸エステル、ジフェニルヨードニウムヘキサフルオロフォスフェート、（４−メトキシフェニル）フェニルヨードニウムトリフルオロメタンスルホネート、ビス（ｐ−ｔｅｒｔ−ブチルフェニル）ヨードニウムトリフルオロメタンスルホネート、トリフェニルスルホニウムヘキサフルオロフォスフェート、（ｐ−ｔｅｒｔ−ブチルフェニル）ジフェニルスルホニウムトリフルオロメタンスルホネートなどのオニウム塩、ヘンゾイントシレート、α−メチルベンゾイントシレートなどのベンゾイントシレート類、２−（４−メトキシフェニル）−４，６−ビス（トリクロロメチル）−１，３，５−トリアジン、２−［２−（２−フリル）エテニル］−４，６−ビス（トリクロロメチル）−１，３，５−トリアジン、２−［２−（５−メチル−２−フリル）エテニル］−４，６−ビス（トリクロロメチル）−１，３，５−トリアジン、２−［２−（３，５−ジメトキシフェニル）エテニル］−４，６−ビス（トリクロロメチル）−１，３，５−トリアジン、２−［２−（３，４−ジメトキシフェニル）エテニル］−４，６−ビス（トリクロロメチル）−１，３，５−トリアジン、２−（３，４−メチレンジオキシフェニル）−４，６−ビス（トリクロロメチル）−１，３，５−トリアジン、トリス（１，３−ジブロモプロピル）−１，３，５−トリアジン、トリス（２，３−ジブロモプロピル）−１，３，５−トリアジン、トリス（２，３−ジブロモプロピル）ソシアヌレートなどのハロゲン含有トリアジン化合物、α−（トルエンスルホニルオキシイミノ）−フェニルアセトニトリル、α−（ｐ−クロロベンゼンスルホニルオキシイミノ）−フェニルアセトニトリル、α−（４−ニトロベンゼンスルホニルオキシイミノ）−フェニルアセトニトリル、α−（４−ニトロ−２−トリフルオロメチルベンゼンスルホニルオキシイミノ）−フェニルアセトニトリル、α−（ベンゼンスルホニルオキシイミノ）−４−クロロフェニルアセトニトリル、α−（ベンゼンスルホニルオキシイミノ）−２，４−ジクロロフェニルアセトニトリル、α−（ベンゼンスルホニルオキシイミノ）−２，６−ジクロロフェニルアセトニトリル、α−（ベンゼンスルホニルオキシイミノ）−４−メトキシフェニルアセトニトリル、α−（２−クロロベンゼンスルホニルオキシイミノ）−４−メトキシフェニルアセトニトリル、α−（ベンゼンスルホニルオキシイミノ）−２−チエニルアセトニトリル、α−（４−ドデシルベンゼンスルホニルオキシイミノ）−フェニルアセトニトリル、α−（４−トルエンスルホニルオキシイミノ）−４−メトキシフェニルアセトニトリル、α−（４−ドデシルベンゼンスルホニルオキシイミノ）−４−メトキシフェニルアセトニトリル、α−（トリスルホニルオキシイミノ）−３−チエニルアセトニトリル、α−（メチルスルホニルオキシシイミノ）−フェニルアセトニトリル、α−（メチルスルホニルオキシイミノ）−４−メトキシフェニルアセトニトリル、α−（トリフルオロメチルスルホニルオキシイミノ）−フェニルアセトニトリル、α−（トリフルオロメチルスルホニルオキシイミノ）−４−メトキシフェニルアセトニトリル、α−（エチルスルホニルオキシイミノ）−４−メトキシフェニルアセトニトリル、α−（プロピルスルホニルオキシイミノ）−４−メチルフェニルアセトトニトリル、α−（メチルスルホニルオキシイミノ）−４−ブロモフェニルアセトニトリル、α−（メチルスルホニルオキシイミノ）−１−シクロペンテニルアセトニトリル、α−（メチルスルホニルオキシイミノ）−１−シクロヘキセニルアセトニトリル、α−（メチルスルホニルオキシイミノ）−１−シクロヘプテニルアセトニトリル、α−（メチルスルホニルオキシイミノ）−１−シクロオクテニルアセトニトリル、α−（トリフルオロメチルスルホニルオキシイミノ）−１−シクロペンテニルアセトニトリル、α−（トリフルオロメチルスルホニルオキシイミノ）−１−シクロヘキセニルアセトニトリル、α−（エチルスルホニルオキシイミノ）−エチルアセトニトリル、α−（プロピルスルホニルオキシイミノ）−プロピルアセトニトリル、α−（シクロヘキシルスルホニルオキシイミノ）−シクロペンチルアセトニトリル、α−（シクロヘキシルスルホニルオキシイミノ）−シクロヘキシルアセトニトリル、α−（シクロヘキシルスルホニルオキシイミノ）−１−シクロペンテニルアセトニトリル、α−（１−ナフチルスルホニルオキシイミノ）−４−メトキシベンジルシアニド、α−（２−ナフチルスルホニルオキシイミノ）−４−メトキシベンジルシアニド、α−（１−ナフチルスルホニルオキシイミノ）ベンジルシアニド、α−（２−ナフチルスルホニルオキシイミノ）ベンジルシアニド、α−（１０−カンファスルホニルオキシイミノ）−４−メトキシベンジルシアニド、α−（１０−カンファスルホニルオキシイミノ）ベンジルシアニド、α−（３−カンファスルホニルオキシイミノ）−４−メトキシベンジルシアニド、α−（３−ブロモ−１０−カンファスルホニルオキシイミノ）−４−メトキシベンジルシアニドなどのオキシムスルホネート系化合物や、Ｎ−メチルスルホニルオキシスクシンイミド、Ｎ−イソプロピルスルホニルオキシスクシンイミド、Ｎ−クロロエチルスルホニルオキシスクシンイミド、Ｎ−（ｐ−メトキシフェニル）スルホニルオキシスクシンイミド、Ｎ−（ｐ−ビニルフェニル）スルホニルオキシスクシンイミド、Ｎ−ナフチルスルホニルオキシスクシンイミド、Ｎ−フェニルスルホニルオキシスクシンイミド、Ｎ−（２，４，６−トリメチルフェニル）スルホニルオキシスクシンイミド、Ｎ−メチルスルホニルオキシマレイミド、Ｎ−イソプロピルスルホニルオキシマレイミド、Ｎ−クロロエチルスルホニルオキシマレイミド、Ｎ−（ｐ−メトキシフェニル）スルホニルオキシマレイミド、Ｎ−（ｐ−ビニルフェニル）スルホニルオキシマレイミド、Ｎ−ナフチルスルホニルオキシマレイミド、Ｎ−フェニルスルホニルオキシマレイミド、Ｎ−（２，４，６−トリメチルフェニル）スルホニルオキシマレイミド、Ｎ−メチルスルホニルオキシフタルイミド、Ｎ−イソプロピルスルホニルオキシフタルイミド、Ｎ−クロロエチルスルホニルオキシフタルイミド、Ｎ−（ｐ−メトキシフェニル）スルホニルオキシフタルイミド、Ｎ−（ｐ−ビニルフェニル）スルホニルオキシフタルイミド、Ｎ−ナフチルスルホニルオキシフタルイミド、Ｎ−フェニルスルホニルオキシフタルイミド、Ｎ−（２，４，６−トリメチルフェニル）スルホニルオキシシフタルイミドなどのイミド系化合物や、ビスオキシムスルホネート系化合物を挙げることができる。
【００５３】
これらの中、好ましくは、ジフェニルヨードニウムヘキサフルオロフォスフェート、（４−メトキシフェニル）フェニルヨードニウムトリフルオロメタンスルホネート、ビス（ｐ−ｔｅｒｔ−ブチルフェニル）ヨードニウムトリフルオロメタンスルホネートである。これらは２種以上用いることもできる。
【００５４】
本発明の（ｃ）成分の添加量は、（ａ）成分および／または（ｂ）成分の合計１００重量部に対して、０．１〜４０重量部が好ましく、特に好ましくは、０．１〜３０重量部である。
【００５５】
本発明に用いられる（ｄ）成分のラジカル発生剤は、発生するラジカルによって、（ａ）成分および／または、（ｂ）成分の前記前処理における有機溶剤および／または、アルカリ水溶液の不溶化を促進する作用を有するものである。
【００５６】
（ｄ）成分のラジカル発生剤としては、例えば、２，２’−アゾビスイソブチロニトリル、２，２’−アゾビス（２，４−ジメチルバレロニトリル）、２，２’−アゾビス（４−メトキシ−２，４−ジメチルバレロニトリル）などのアゾ化合物、ベンゾイルパーオキシド、ラウロイルパーオキシド、ｔ−ブチルパーオキシピバレート、１，１’−ビス（ｔ−ブチルパーオキシ）シクロヘキサンなどの有機過酸化物および過酸化水素、アセトフェノン、アセトフェノンベンジルケタール、アントラキノン、１−（４−イソプロピルフェニル）−２−ヒドロキシ−２−メチルプロパン−１−オン、カルバゾール、キサントン、４−クロロベンゾフェノン、４，４′−ジアミノベンゾフェノン、１，１−ジメトキシデオキシベンゾイン、３，３′−ジメチル−４−メトキシベンゾフェノン、チオキサントン、１−（４−ドデシルフェニル）−２−ヒドロキシ−２−メチルプロパン−１−オン、２−メチル−１−〔４−（メチルチオ）フェニル〕−２−モルフォリノ−プロパン−１−オン、トリフェニルアミン、２，４，６−トリメチルベンゾイルジフェニルホスフィンオキサイド、１−ヒドロキシシクロヘキシルフェニルケトン、２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン、フルオレノン、フルオレン、ベンジルメチルケタール、ベンズアルデヒド、ベンゾインエチルエーテル、ベンゾインプロピルエーテル、ベンゾフェノン、ミヒラーケトン、３−メチルアセトフェノン、３，３′，４，４′−テトラ（ｔ−ブチルパーオキシカルボニル）ベンゾフェノン（ＢＴＴＢ）、２−ジメトキシ−１，２−ジフェニルエタン−１−オン、１−［４−（２−ヒドロキシエトキシ）−フェニル］−２−ヒドロキシ−２−メチル−１−プロパン−１−オン、等が挙げられる。
【００５７】
これらのうち、２，２’−アゾビスイソブチロニトリル、２，２’−アゾビス（２，４−ジメチルバレロニトリル）、２−ベンジル−２−ジメチルアミノ−１−（４−モルフォリノフェニル）−ブタノン−１、２−メチル−１［４−（メチルチオ）フェニル］−２−モリフォリノプロパン−１−オン、１−ヒドロキシ−シクロヘキシル−フェニル−ケトン、２−ジメトキシ−１，２−ジフェニルエタン−１−オン、１−［４−（２−ヒドロキシエトキシ）−フェニル］−２−ヒドロキシ−２−メチル−１−プロパン−１−オン、２−ヒドロキシ−２−メチル−１−フェニル−プロパン−１−オン等が好ましい。これらは２種以上用いることもできる。
【００５８】
本発明のラジカル発生剤は、（ａ）成分および／または（ｂ）成分の合計量１００重量部に対して、０．００１〜３０重量部であり、好ましくは０．００５〜２０重量部添加される。
【００５９】
また本発明では、組成物の塗布性の向上たとえばストリエーション（塗布すじあと）を防止させるために界面活性剤を配合することもできる。界面活性剤としては、たとえば、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオレイルエーテルなどのポリオキシエチレンアルキルエーテル類、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテルなどのポリオキシエチレンアリールエーテル類、ポリオキシエチレンジラウレート、ポリオキシエチレンジステアレートなどのポリオキシエチレンジアルキルエステル類などのノニオン系界面活性剤、エフトップＥＦ３０１、同３０３、同３５２（新秋田化成（株）製）、メガファックＦ１７１、同Ｆ１７２、同Ｆ１７３（大日本インキ化学工業（株）製）、フロラードＦＣ−４３０、同ＦＣ−４３１（住友スリーエム（株）製）、アサヒガードＡＧ７１０、サーフロンＳ−３８２、同ＳＣ−１０１、同ＳＣ−１０２、同ＳＣ−１０３、同ＳＣ−１０４、同ＳＣ−１０５、同ＳＣ−１０６（旭硝子（株）製）などの名称で市販されているフッ素系界面活性剤、オルガノシロキサンポリマーＫＰ３４１（信越化学工業（株）製）、（メタ）アクリル酸系共重合体ポリフローＮｏ．　５７、７５、７７、９５（共栄社油脂化学工業（株）製）などが挙げられる。これらは２種以上用いることもできる。このような界面活性剤は、組成物全量を１００重量部とするとき、２重量部以下好ましくは１重量部以下の量で含有していてもよい。また本発明に係る組成物は、基板との密着性を向上させるために接着助剤を含んでいてもよい。このような接着助剤としては、シランカップリング剤などが挙げられる。さらに本発明に係る組成物は、必要に応じて帯電防止剤、保存安定剤、消泡剤などを含んでいてもよい。本発明に係る組成物は、上記のような各成分を均一に混合することによって容易に調製することができる。
【００６０】
このような組成物は、２３℃大気圧下で液体である有機低分子化合物に溶解させて溶液状態で用いられる。
【００６１】
ここでいう２３℃大気圧下で液体である有機低分子化合物とは、上記の反応希釈モノマー（６）や、（ａ）成分を製造する際に用いられた重合溶媒などの有機溶剤に加えて、その他の有機溶剤も使用できる。
【００６２】
ここでいうその他の有機溶剤としては、例えば、Ｎ−メチルホルムアミド、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ−メチルホルムアニリド、Ｎ−メチルアセトアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチルピロリドン、ジメチルスルホキシド、ベンジルエチルエーテル、ジヘキシルエーテル、アセトニルアセトン、イソホロン、カプロン酸、カプリル酸、１−オクタノール、１−ノナノール、ベンジルアルコール、酢酸ベンジル、安息香酸エチル、シュウ酸ジエチル、マレイン酸ジエチル、γ−ブチロラクトン、炭酸エチレン、炭酸プロピレン、フェニルセロソルブアセテート、ジアセトンアルコール、２−ヘプタノン、シクロヘキサノなどが挙げられる。
【００６３】
これら２３℃大気圧下で液体である有機低分子化合物のうち、溶解性、各成分との反応性および塗膜の形成のしやすさから、プロピレングリコールモノエチルエーテルなどのプロピレングリコールエーテル類、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プロピレングリコールアルキルエーテルアセテート類、２−ヒドロキシプロピオン酸エチルなどのエステル類、２−ヘプタノン、シクロヘキサノンなどのケトン類、ジアセトンアルコール、反応希釈モノマー（６）が好ましく用いられる。本発明では、組成物は、固形分濃度が好ましくは５〜１００重量％となるように上記２３℃大気圧下で液体である有機低分子化合物を溶媒として溶解させた溶液として、被塗布物に塗布される。また、上記のように調製された組成物溶液は、孔径０．２μｍ程度のミリポアフィルタなどを用いて濾過した後、使用に供することもできる。このように調製された本発明の組成物溶液は、長期間の貯蔵安定性にも優れる。
【００６４】
次に、本発明の組成物の使用方法について説明する。本発明の組成物を、まず、基板表面に塗布し、有機溶剤および／または、アルカリ水溶液に不溶の塗膜を形成する。
【００６５】
その方法としては、有機溶剤を溶解溶媒として使用した組成物の場合は、（Ａ）基板表面に塗布後、加熱により溶媒を除去と同時に不溶化させる方法、（Ｂ）基板表面に塗布後、加熱により溶媒を除去し、その後、光を照射または、前記よりも高温でさらに加熱し不溶化させる方法が挙げられる。
【００６６】
反応希釈モノマー（６）を溶解溶媒として使用した組成物の場合は、（Ｃ）基板表面に塗布後、加熱または、光照射により不溶化させる方法、が挙げられる。
【００６７】
基板表面への基板表面への塗布方法は特に限定されず、例えば、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用いられる。また、塗膜の膜厚は、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１００μｍになるように塗布される。
【００６８】
次に、該不溶化した塗膜を、前記よりもさらに高い温度で加熱または光照射後、エッチングガスで、ドライエッチング処理して除去する。
【００６９】
本発明でいう光照射で用いられる光としては、紫外線、可視光線、電子線、Ｘ線などの化学線があげられるが、本発明では水銀灯のｉ線（３６５ｎｍ）、ｈ線（４０５ｎｍ）、ｇ線（４３６ｎｍ）を用いるのが好ましい。
【００７０】
また、ここで用いられるエッチングガスとしては、例えば、酸素、フッ素、ＣＦ_４、ＣＨＦ_３、アルゴン、Ｃ_４Ｆ_８等が挙げられる。これらエッチングガスを１種以上を混合して、ドライエッチング処理し、組成物を基板から除去する。本発明では、前記後処理後のエッチングレートが、前記前処理後のエッチングレートと比較して、好ましくは１．２倍以上であり、特に好ましくは１．４倍以上であり、さらに好ましくは２倍以上である。１．２倍を下回ると、配線溝形成後にドライエッチングで孔内の該組成物を、完全に除去することが難しく、残留組成物により、接続抵抗の増加などの問題が半導体素子に発生し好ましくない。ドライエッチング処理は、たとえば、ドライエッチング装置にて圧力を７５０ｍＴｏｒｒ、エッチングガスとして、ＣＨＦ_３、ＣＦ_４、アルゴン混合ガスを使用し、その流量を、各々１０、９０、９５０ｓｃｃｍ、ＲＦ投入電力を９００Ｗ、基板温度を４０℃、エッチング時間１２０秒の条件や、圧力を６０ｍＴｏｒｒ、エッチングガスとして、アルゴン、ＣＦ_４、酸素混合ガスを使用し、その流量を、各々４８．８４、０．６７、０．４９ｓｃｃｍ、ＲＦ投入電力を５０Ｗ、基板温度を２５℃、エッチング時間６０秒の条件等で行う。また、ここで言う加熱条件は、各成分の種類、配合割合、などによっても異なるが、通常６０℃〜２５０℃で１０秒〜１０分程度である。
【００７１】
組成物除去に関して、ドライエッチング処理以外に、半発明の組成物であれば、ドライエッチング処理に替えて、剥離液により溶解除去しても良い。
【００７２】
ここでいう剥離液としては、有機溶剤および／または、アルカリ水溶液が用いられる。
【００７３】
本発明で用いられる剥離液としてはたとえば、Ｎ−メチル−２−ピロリドン、Ｎ−アセチル−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、ヘキサメチルホスホルトリアミドなどを単独あるいはメタノール、エタノール、イソプロピルアルコール、メチルカルビトール、エチルカルビトール、トルエン、キシレン、乳酸エチル、ピルビン酸エチル、プロピレングリコールモノメチルエーテルアセテート、メチル−３−メトキシプロピオネート、エチル−３−エトキシプロピオネート、２−ヘプタノン、酢酸エチルなどの有機溶剤や、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挙げられ、特に、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、トリエチルアミン等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。
【００７４】
上記剥離液による剥離時間は通常、５秒〜３時間であり、剥離は、液盛り法、ディッピング法などのいずれでも良い。剥離後、流水洗浄を３０〜１８０秒間行い、圧縮空気や圧縮窒素で風乾させる。
【００７５】
また、本発明の組成物を用いて、多層配線構造を有する半導体装置を製造するための多層配線構造形成は、例えば、以下のようにして行われる。
【００７６】
下層配線上に形成された層間絶縁膜上に、孔パターンにパターニングされたフォトレジスト膜を形成し、これをマスクとして、ドライエッチング法により層間絶縁膜をエッチングし、下層配線に到達する深い孔をまず形成する。次に、本発明の組成物を塗布、光および／または熱処理により不溶化し、この孔の埋め込みを行う。穴埋めされた層間絶縁膜上に、反射防止材料を形成し、さらにその上に、溝パターンにパターニングされたフォトレジスト膜を形成、その後、光および／または熱処理し、このフォトレジスト膜をマスクとして、反射防止膜、層間絶縁膜および、孔内の該組成物を同じにエッチングする。孔内の該組成物の除去と同じに溝を形成し、溝と孔に銅を埋め込み配線を形成する。さらに、配線上に、層間絶縁膜を形成し、上記のように、孔、溝形成、銅埋め込み、層間絶縁膜を形成等の工程を繰り返すことによって多層配線構造が形成される。
【００７７】
また、上記のフォトレジスト膜をマスクとして、反射防止膜、層間絶縁膜および、孔内の該組成物を同じにエッチングしても、孔内の組成物が除去できず残存した場合、その直後に、有機溶剤または、アルカリ水溶液で除去する工程を入れることもできる。
【００７８】
【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、実施例中の組成物の評価は以下の方法により行った。
【００７９】
１．前処理後の組成物膜の作製
以下に示す前処理法１、前処理法２、前処理法３のいずれかの方法により、前処理操作後の組成物膜を作製した。
【００８０】
前処理法１
６インチシリコンウエハー上に、組成物（以下ワニスと呼ぶ）をプリベーク後の膜厚が２μｍ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、所定の温度で所定の時間プリベークすることにより、組成物膜を得た。
【００８１】
前処理法２
６インチシリコンウエハー上に、組成物（以下ワニスと呼ぶ）をプリベーク後の膜厚が２μｍ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、１３０℃で２分プリベークしさらに、露光機（キャノン（株）製コンタクトアライナーＰＬＡ５０１Ｆ）で、紫外線強度１０ｍＷ／ｃｍ^２（３６５ｎｍ換算）で、所定の時間、紫外線全波長露光をすることにより、組成物膜を得た。
【００８２】
前処理法３
６インチシリコンウエハー上に、組成物（以下ワニスと呼ぶ）を紫外線照射後の膜厚が２μｍとなるように塗布し、ついで、露光機（キャノン（株）製コンタクトアライナーＰＬＡ５０１Ｆ）で、紫外線強度１０ｍＷ／ｃｍ^２（３６５ｎｍ換算）で、所定の時間、紫外線全波長露光をすることにより、組成物膜を得た。
【００８３】
２．後処理後の組成物膜の作製
以下に示す後処理法１、後処理法２のいずれかの方法により、後処理操作後の組成物膜を作製した。
【００８４】
後処理法１
前記前処理操作により形成された組成物膜を、さらに、ホットプレート（東京エレクトロン（株）製Ｍａｒｋ−７）を用いて、所定の温度で所定の時間ベーク処理した。
【００８５】
後処理法２
前記前処理操作により形成された組成物膜を、さらに、露光機（キャノン（株）製コンタクトアライナーＰＬＡ５０１Ｆ）で、紫外線強度１０ｍＷ／ｃｍ^２（３６５ｎｍ換算）で、所定の時間、紫外線全波長露光処理した。
【００８６】
３．作製された膜の評価
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１．５１０で測定を行った。
【００８７】
前処理後の組成物膜の不溶性の評価
上記１の前処理後の組成物膜について、アルカリ水溶液に対する不溶性を評価する場合は、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１２０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後、組成物の膜厚を測定し、アルカリ水溶液処理する前の膜の膜厚と比較し、膜減りが無いか評価した。
【００８８】
有機溶剤に対する不溶性を評価する場合は、東京エレクトロン（株）製Ｍａｒｋ−７の現像装置を用い、５０回転でプロピレングリコールモノメチルエーテルアセテート／乳酸エチル＝７／３（重量比）の溶剤を６０秒間噴霧した。この後、４００回転でプロピレングリコールモノメチルエーテルアセテートにてリンス処理、３０００回転で１０秒振り切り乾燥した後、組成物の膜厚を測定し、有機溶剤処理する前の膜の膜厚と比較し、膜減りが無いか評価した。
【００８９】
エッチングレートの比較
上記１の前処理後の組成物膜と、上記２の後処理後の膜を（株）サムコインターナショナル研究所社製の異方性ドライエッチング装置（ＲＩＥ−１０Ｎ）にて、圧力を６０ｍＴｏｒｒ、エッチングガスとして、アルゴン、ＣＦ_４、酸素の混合ガスを使用し、その流量を、各々以下のように設定、ＲＦ投入電力を２００Ｗ、基板温度を２５℃、エッチング時間６０秒の条件でドライエッチングを行い、エッチングレート比を比較した。
【００９０】
設定１：アルゴン／ＣＦ_４／酸素＝４７．７３ｓｃｃｍ／１．３１ｓｃｃｍ／０．９５ｓｃｃｍ
設定２：アルゴン／ＣＦ_４／酸素＝０ｓｃｃｍ／４８ｓｃｃｍ／２ｓｃｃｍ
設定３：アルゴン／ＣＦ_４／酸素＝０ｓｃｃｍ／５０ｓｃｃｍ／０ｓｃｃｍ
エッチングレート比
エッチングレート比を以下の方法で算出した。
エッチングレート比＝後処理後の組成物膜のエッチングレート÷前処理後の組成物膜のエッチングレート。
【００９１】
剥離性（溶解性）の評価
上記２の後処理後の組成物膜について、アルカリ剥離の場合は、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１２０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、組成物残差の有無を光学顕微鏡にて観察し、剥離性を判断した。
【００９２】
有機溶剤剥離の場合は、東京エレクトロン（株）製Ｍａｒｋ−７の現像装置を用い、５０回転γ−ブチロラクトン／乳酸エチル＝７／３（重量比）の溶剤を６０秒間噴霧した。この後、４００回転でプロピレングリコールモノメチルエーテルアセテートにてリンス処理、３０００回転で１０秒振り切り乾燥し、組成物残差の有無を光学顕微鏡にて観察し、剥離性を判断した。
【００９３】
合成例１　分解性モノマー（ａ）の合成
乾燥空気気流下、２，５−ジメチル−２，５−ヘキサンジオール（東京化成工業（株）社製）１４．６ｇ（０．１モル）とメタクリル酸クロリド２２．０ｇ（０．２１モル）をジクロロメタン１００ｇに溶解させ、−１５℃に冷却した。ここにトリエチルアミン２１．３ｇ（０．２１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１時間反応させた。その後室温で２時間攪拌した。トリエチルアミン塩を濾過し、有機層を飽和炭酸水素ナトリウム溶液で３回洗浄した。その後、有機層のジクロロメタンを減圧留去し、分解性モノマー（ａ）２５．４ｇを得た。
【００９４】
合成例２　分解性モノマー（ｂ）の合成
乾燥空気気流下、シクロヘキサンジメタノールジビニルエーテル（ＢＡＳＦ社製）１９．６ｇ（０．１モル）とメタクリル酸１８．１ｇ（０．２１モル）、をジクロロメタン１００ｇに溶解させ、ｐ−トルエンスルホン酸のピリジン塩０．０１ｇを触媒として添加し、０℃で１時間反応させた。その後室温で２時間攪拌した。ｐ−トルエンスルホン酸のピリジン塩触媒を濾過し、有機層を飽和炭酸水素ナトリウム溶液で３回洗浄した。その後、有機層のジクロロメタンを減圧留去し、分解性モノマー（ｂ）３３．２ｇを得た。
【００９５】
合成例３　分解性モノマー（ｃ）の合成
乾燥空気気流下、１，４−ブタンジオールジアクリレート（東京化成工業（株）社製）２２．６ｇ（０．１モル）とメタクリル酸１８．１ｇ（０．２１モル）、をジクロロメタン１００ｇに溶解させ、ｐ−トルエンスルホン酸のピリジン塩０．０１ｇを触媒として添加し、０℃で１時間反応させた。その後室温で２時間攪拌した。ｐ−トルエンスルホン酸のピリジン塩触媒を濾過し、有機層を飽和炭酸水素ナトリウム溶液で３回洗浄した。その後、有機層のジクロロメタンを減圧留去し、分解性モノマー（ｃ）３５．９ｇを得た。
【００９６】
実施例１
乾燥窒素気流下、２，２’−アゾビス（２，４−ジメチルバレロニトリル）５ｇ、プロピレングリコールモノメチルエーテールアセテート２００ｇ、メタアクリル酸２５ｇ、メタアクリル酸メチル４０ｇ、ヒドロキシエチルメタアクリレート１０ｇを仕込み溶解させ、７０℃で４時間攪拌反応させた。反応終了後、アルカリ可溶性ラジカル重合性ポリマー溶液を、ヘキサン１０００ｇ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１０時間乾燥した。
【００９７】
このようにして得たポリマーの固体１０ｇを計り、ジエチレングリコールジビニルエーテル、５０ｇを加えて組成物のワニスＡを得た。
【００９８】
得られたワニスＡを用いて前記のようにシリコンウエハ上に、前処理法１に従い、１３０℃３分プリベークすることにより前処理後の組成物膜を作製、さらに後処理法１にしたがい１６０℃２分ベークすることにより後処理後の組成物膜を作製した。得られたこれらの組成物膜につき、不溶性、上記設定１によるエッチングレートの比較、剥離性等所定の評価をおこなった。
【００９９】
実施例２
乾燥窒素気流下、２，２’−アゾビス（２，４−ジメチルバレロニトリル）５ｇ、プロピレングリコールモノメチルエーテールアセテート２００ｇ、上記合成例１で得られた分解性モノマー（ａ）２５ｇ、メタアクリル酸１０ｇ、メタクリル酸ｔ−ブチル１０ｇ、２−ヒドロキシブチルメタクリレート３ｇ、連鎖移動剤として、３−メルカプトプロピオン酸エチル３ｇを仕込み溶解させ、７０℃で４時間攪拌反応させた。反応終了後、ラジカル重合性ポリマー溶液を、ヘキサン１０００ｇ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１０時間乾燥した。
【０１００】
このようにして得たポリマーの固体１０ｇを計り、プロピレングリコールジメタクリレート１０ｇ、酸発生剤として、ジフェニルヨードニウムヘキサフルオロフォスフェート３ｇ、ラジカル発生剤として２−ジメトキシ−１，２−ジフェニルエタン−１−オン２ｇを加えて組成物のワニスＢを得た。
【０１０１】
得られたワニスＢを用いて前記のようにシリコンウエハ上に、前処理法３に従い、３０秒間紫外線照射することにより前処理後の組成物膜を作製、さらに後処理法１にしたがい１６０℃２分ベークすることにより後処理後の組成物膜を作製した。得られたこれらの組成物膜につき、不溶性、上記設定２によるエッチングレートの比較、剥離性等所定の評価をおこなった。
【０１０２】
実施例３
攪拌機のついた反応容器に、イソボルニルメタクリレート２００ｇ、２，４−トリレンジイソシアネート５６６ｇ、ジブチル錫ジラウレート２ｇ、および２，６−ジ−ｔ−ブチル−４−メチルフェノール３ｇを仕込んだ。次いで、反応容器を冷却しながら、ヒドロキシエチルメタクリレート３７７ｇを、内温が２５℃を超えないように攪拌しながら徐々に添加した。添加終了後、内温を２０〜４０℃に保ちながら、さらに１時間攪拌した。ついで、ポリオキシテトラメチレングリコール（分子量６５０）１０５７ｇを添加し、６０℃で５時間、攪拌を続けた。残留イソシアネート基が０．１重量％以下であることを確認した後、内容物を取り出し、両末端にアクリロイル基が結合したウレタンメタクリレートポリマー（重量平均分子量１２３０）のイソボルニルメタアクリレート溶液を得た。
【０１０３】
このようにして得たポリマー溶液１１ｇを計り、１，９−ノナンジオールジメタクリレート１０ｇ、上記合成例２で得られた分解性モノマー（ｃ）２５ｇ、酸発生剤として、（４−メトキシフェニル）フェニルヨードニウムトリフルオロメタンスルホネート、３ｇ、ラジカル発生剤として、２，２’−アゾビスイソブチロニトリル２ｇ、γ−ブチロラクトン５０ｇを加えて組成物のワニスＣを得た。
【０１０４】
得られたワニスＣを用いて前記のようにシリコンウエハ上に、前処理法２に従い、１２０℃４分プレベーク後、３０秒間紫外線照射することにより前処理後の組成物膜を作製、さらに後処理法１にしたがい１７０℃２分ベークすることにより後処理後の組成物膜を作製した。得られたこれらの組成物膜につき、不溶性、上記設定２によるエッチングレートの比較、剥離性等所定の評価をおこなった。
【０１０５】
実施例４
乾燥窒素気流下、２，２’−アゾビス（２，４−ジメチルバレロニトリル）５ｇ、プロピレングリコールモノメチルエーテールアセテート２００ｇ、上記合成例１で得られた分解性モノマー（ａ）２５ｇ、メタアクリル酸エチル４０ｇ、メタクリル酸１５ｇ、連鎖移動剤として、３−メルカプトプロピオン酸２ｇを仕込み溶解させ、７０℃で４時間攪拌反応させた。その後１００℃で２時間攪拌し、残留重合開始剤を分解した後、グリシジルメタクリレート１０ｇを添加し、８０℃で３時間反応させた。反応終了後、反応性基含有ポリマー溶液を、ヘキサン１０００ｇ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３０℃の真空乾燥機で５時間乾燥した。
【０１０６】
このようにして得たポリマーの固体１０ｇを計り、プロピレングリコールジメタクリレート１０ｇ、上記合成例２で得られた分解性モノマー（ｂ）１０ｇ、酸発生剤として、ビス（ｐ−ｔｅｒｔ−ブチルフェニル）ヨードニウムトリフルオロメタンスルホネート３ｇ、ラジカル発生剤として、２−メチル−１［４−（メチルチオ）フェニル］−２−モリフォリノプロパン−１−オン２ｇを加えて組成物のワニスＤを得た。
【０１０７】
得られたワニスＤを用いて前記のようにシリコンウエハ上に、前処理法３に従い、３０秒間紫外線照射することにより前処理後の組成物膜を作製、さらに後処理法２にしたがい３０秒間紫外線を照射することにより後処理後の組成物膜を作製した。得られたこれらの組成物膜につき、不溶性、上記設定３によるエッチングレートの比較、剥離性等所定の評価をおこなった。
【０１０８】
実施例５
実施例４で得られたワニスＤを用いて前記のようにシリコンウエハ上に、前処理法１に従い、１３０℃２分プリベークすることにより前処理後の組成物膜を作製、さらに後処理法１にしたがい１７０℃２分ベークの後処理操作することにより後処理後の組成物膜を作製した。得られたこれらの組成物膜につき、不溶性、上記設定３によるエッチングレートの比較、剥離性等所定の評価をおこなった。
【０１０９】
実施例６
実施例４で合成したポリマーを用いず、プロピレングリコールジメタクリレート１０ｇ、上記合成例２で得られた分解性モノマー（ｂ）１０ｇ、酸発生剤として、ビス（ｐ−ｔｅｒｔ−ブチルフェニル）ヨードニウムトリフルオロメタンスルホネート３ｇ、ラジカル発生剤として、２−メチル−１［４−（メチルチオ）フェニル］−２−モリフォリノプロパン−１−オン２ｇを加えて組成物のワニスＥを得た。得られたワニスＥを用いて実施例４と同様の評価を行った。
【０１１０】
実施例７
多層配線構造を有する半導体装置を製造するための多層配線構造形成は、以下のようにして行った。下層配線上に形成された層間絶縁膜上に、孔パターンにパターニングされたフォトレジスト膜を形成し、これをマスクとして、ドライエッチング法により層間絶縁膜をエッチングし、下層配線に到達する深い孔をまず形成した。次に、実施例１で得られたワニスＡを塗布し、１３０℃３分ベークすることによって、この孔の埋め込みを行った。穴埋めされた層間絶縁膜上に、反射防止材料を形成し、さらにその上に、溝パターンにパターニングされたフォトレジスト膜を形成、その後、１６０℃２分処理した後、このフォトレジスト膜をマスクとして、反射防止膜、層間絶縁膜および、孔内の該組成物を同じにエッチングした。孔内の該組成物の除去と同じに溝を形成し、溝と孔に銅を埋め込み配線を形成した。さらに、配線上に、層間絶縁膜を形成し、上記のように、孔、溝形成、銅埋め込み、層間絶縁膜を形成等の工程を５回繰り返すことによって多層配線構造を形成した。
【０１１１】
比較例１
ｍ／ｐクレゾールノボラック系のＯＦＰＲ−８００（東京応化（株）社製）ｇ線用ポジレジストを用いて前記のようにシリコンウエハ上に前処理法１に従い、１３０℃２分プリベークすることにより前処理後の組成物膜（レジスト膜）を作製、さらに後処理法１にしたがい１７０℃２分ベークの後処理操作することにより後処理後の組成物膜を作製した。得られたこれらの組成物膜につき、不溶性、上記設定３によるエッチングレートの比較、剥離性等所定の評価をおこなった。
【０１１２】
比較例２
ジエチレングリコールジビニルエーテルを１，９−ノナンジオールジメタクリレートに変更した他は、実施例１と同様にしてワニスＡ１を得た。得られたワニスＡ１を用いて実施例１と同様の評価を行った。
【０１１３】
比較例３
ジエチレングリコールジビニルエーテルを１，９−ノナンジオールジメタクリレートに変更し、酸発生剤として、ジフェニルヨードニウムヘキサフルオロフォスフェート３ｇを添加した他は、実施例１と同様にしてワニスＢ１を得た。得られたワニスＢ１を用いて実施例１と同様の評価を行った。
【０１１４】
比較例４
酸発生剤のジフェニルヨードニウムヘキサフルオロフォスフェートを使用しない他は、実施例２と同様にしてワニスＣ１を得た。得られたワニスＣ１を用いて実施例２と同様の評価を行った。
【０１１５】
比較例５
ワニスＡをＯＦＰＲ−８００に変更し、実施例７と同様にして得られた深い孔上に塗布し、１３０℃２分ベークすることによって、この孔の埋め込みを行った。穴埋めされた層間絶縁膜上に、反射防止材料を形成し、さらにその上に、溝パターンにパターニングされたフォトレジスト膜を形成、その後、１７０℃２分処理した後、このフォトレジスト膜をマスクとして、反射防止膜、層間絶縁膜および、孔内のＯＦＰＲ−８００を同じにエッチングした。溝を形成したが、孔内のＯＦＰＲ−８００の除去が行えず、銅を埋め込みによる配線を形成できなかった。
【０１１６】
比較例６
ワニスＡを比較例２で得られたワニスＡ１に変更し、実施例７と同様にして得られた深い孔上に塗布し、１３０℃３分ベークすることによって、この孔の埋め込みを行った。穴埋めされた層間絶縁膜上に、反射防止材料を形成し、さらにその上に、溝パターンにパターニングされたフォトレジスト膜を形成、その後、１６０℃２分処理した後、このフォトレジスト膜をマスクとして、反射防止膜、層間絶縁膜および、孔内のワニスＡ１を同じにエッチングした。溝を形成したが、孔内のワニスＡ１の除去が行えず、銅を埋め込みによる配線を形成できなかった。
【０１１７】
実施例１〜６、比較例１〜４の組成について表１に、評価結果については表２に示した。
【０１１８】
【表１】

【０１１９】
【表２】

【０１２０】
【発明の効果】
本発明によれば、後処理法で得られた膜のエッチングレートが、前処理で得られた組成物膜のエッチングレートより高くなることから、ドライエッチング処理による除去性に優れた組成物を得ることができ、得られた組成物は、特にダマシン法を用いた多層配線構造、およびそのような多層配線構造を形成する際の有機平坦化膜や、反射防止膜等として、好適に用いることができる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a semiconductor device and its manufacture, and more particularly to a multilayer wiring structure formed by using a so-called damascene method, and an organic flattening device used in manufacturing a semiconductor device having such a multilayer wiring structure. The present invention relates to a composition suitable for an oxide film, an antireflection film, and the like.
[0002]
[Prior art]
2. Description of the Related Art As semiconductor devices have been improved in performance and miniaturized, multilayer wiring technology has become a necessary technology in semiconductor device manufacturing. As a method of forming a wiring layer in a semiconductor integrated circuit, a high-melting point metal thin film such as an aluminum (Al) alloy or tungsten (W) is formed on an insulating film, and the same as a wiring pattern on a wiring thin film by a photolithography process. A method is known in which a resist pattern having a shape is formed and a wiring pattern is formed by a dry etching process using the resist pattern as a mask. However, in the method using an Al alloy or the like, there is a problem that the wiring resistance is remarkably increased as the wiring is miniaturized, the wiring delay is increased, and the performance of the semiconductor device is reduced. Particularly in a high-performance logic LSI, a serious problem has arisen as a performance hindrance factor.
[0003]
For this reason, after a metal for wiring having copper (Cu) as a main conductor layer is buried in the groove formed in the insulating film, excess metal outside the groove is removed by CMP (chemical mechanical polishing). A method of forming a wiring pattern in a groove (a so-called damascene method) has been studied.
[0004]
However, multilayer wiring by a damascene method, particularly a dual damascene method (a damascene method in which a wiring groove for forming a wiring and a connection hole in which an interlayer connection wiring is formed, and then a wiring and an interlayer connection wiring are simultaneously formed). It is known that there is the following problem with respect to the formation process of JP-A-2000-349150. A method of forming a groove (wiring groove) and a hole (connection hole) by the dual damascene method is roughly classified into two methods. A hole type and a self-aligned type. In the hole tip method, a deep hole reaching the lower wiring is first formed in an interlayer insulating film (including an inter-line insulating film which is an insulating film for forming wiring) formed on the lower wiring. To form the holes, a photoresist film patterned into a hole pattern is formed on the interlayer insulating film, and using this as a mask, the interlayer insulating film is etched by, for example, a dry etching method. Next, the holes are filled with an anti-reflection material, a resist or the like, and thereafter, a wiring groove is formed in the interlayer insulating film. Similar to the formation of the holes, the wiring grooves are formed by forming a photoresist film patterned into a groove pattern on the interlayer insulating film, and etching the interlayer insulating film using the photoresist film as a mask. The reason why the holes are filled with an anti-reflection material or the like before the formation of the wiring groove is to accurately expose the photoresist film for forming the wiring groove and to improve the processing accuracy. That is, if the hole is not buried, the surface of the photoresist film at that portion does not become flat reflecting the hole shape. If exposure is performed in the presence of such unevenness, the exposure light is scattered at the unevenness existing portions (holes), and a groove pattern is not precisely formed. In particular, since a wiring groove is formed in a hole (connection hole) in which a connection wiring for connecting the upper and lower wiring layers is formed, such a problem of reduction in processing accuracy occurs in many parts. If the holes are filled with an anti-reflection material or the like as described above, the problem of exposing the wiring groove pattern can be almost eliminated. However, the buried material (anti-reflection material or the like) remaining in the hole after the formation of the wiring groove must be removed. However, it is difficult to remove such a filling material, and there is a problem of poor connection between the upper and lower wiring layers or an increase in connection resistance due to the remaining filling material at the bottom of the connection hole. Particularly, in recent miniaturized semiconductor devices, the diameter of the connection hole is reduced and the aspect ratio is also increased, so that the difficulty is further increased.
[0005]
On the other hand, in the self-alignment method, wiring grooves and connection holes can be formed as follows. That is, an interlayer insulating film (the interlayer insulating film in this case does not include an inter-line insulating film for forming a wiring) is formed on the lower wiring, and further a silicon nitride film is formed. The silicon nitride film is subjected to a hole patterning process, and a line insulating film (for example, a silicon oxide film) is formed. That is, an intermediate layer (silicon nitride film layer) processed into a hole pattern is formed between the interlayer insulating film and the line insulating film. Then, a groove pattern is formed in the interline insulating film, and after the groove pattern processing, hole processing is performed using the intermediate layer (the silicon nitride film on which the groove pattern is formed) as a mask. In such a self-alignment method, it is possible to avoid the above-described remaining of the filling material in the hole (connection hole) or a decrease in processing accuracy when performing the groove processing. However, the intermediate layer functions as an etching stopper at the time of groove processing (at the time of etching) and also functions as an etching mask for hole processing. For this reason, the thickness of the intermediate layer needs to be considerably large, and at least about 100 nm. The silicon nitride film is known as a material having a high dielectric constant, and is a major negative factor for lowering the dielectric constant of the interlayer insulating film and the inter-line insulating film. If the dielectric constant between the wirings or between the wiring layers increases, the capacitance between the wirings increases, which hinders the speeding up and performance improvement of the semiconductor device. Further, since the hole is defined in a region where both the wiring and the hole are dry-etched, a misalignment between the mask for forming the hole and the mask for forming the groove may cause a reduction in the finished hole diameter. The reduction in the hole diameter hinders securing of a resistance value required for the inter-line connection wiring, and becomes a hindrance to speeding up and improving the performance of the semiconductor device. In addition, if the groove pattern is enlarged in order to avoid misalignment of the mask, miniaturization of the wiring width and pitch is hindered, and high integration is hindered.
[0006]
[Problems to be solved by the invention]
The present invention solves the above-mentioned problems in which the hole tip method and the self-alignment method are caused, by pre-treatment, insoluble in an organic solvent and / or an alkaline aqueous solution, to avoid miscibility with a resist, etc. It is intended to industrially provide a resin capable of easily removing the composition after the treatment.
[0007]
[Means for Solving the Problems]
That is, the present invention relates to a composition which becomes insoluble in an organic solvent and / or an aqueous alkali solution by light and / or heat treatment (pre-treatment), and is subjected to dry etching treatment after light and / or heat treatment (post-treatment). A composition for a semiconductor device, wherein the post-etching rate is 1.2 times or more the post-treatment etching rate, and the composition contains the following (a) and / or (b): Things.
(A) Polymer soluble in organic low molecular weight compound which is liquid at 23 ° C. and atmospheric pressure
(B) Low molecular weight compounds having a polymerizable group and / or a crosslinkable group
According to another aspect of the present invention, there is provided a semiconductor device comprising a multilayer wiring and an interlayer insulating film that insulates and separates the wiring, a lower wiring layer, an interlayer insulating film covering the lower wiring layer, and an interlayer insulating film on the lower wiring layer. A method of manufacturing a semiconductor device having an upper wiring layer connected to the lower wiring layer through an opening (hole) formed in a film, wherein a wiring groove is formed on an interlayer insulating film on the lower wiring layer. A step of forming a wiring groove pattern layer serving as an etching mask when forming, and a step of forming an opening pattern layer serving as an etching mask when forming a connection opening (hole) on the wiring groove pattern layer A method of manufacturing a semiconductor device, characterized in that an organic planarizing film that is removed by etching during the process is formed using the above resin composition.
[0008]
BEST MODE FOR CARRYING OUT THE INVENTION
By light and / or heat treatment (pre-treatment), it becomes insoluble in an organic solvent and / or an alkaline aqueous solution, and further, after light and / or heat treatment (post-treatment), and dry etching treatment, the etching rate after the post-treatment becomes In order for the etching rate after the treatment to be 1.2 times or more, the composition must undergo a chemical structural change such as decomposition with respect to the resin composition after the pretreatment during the post-treatment. There is. In addition, since these compositions are used by being applied to the surface of a substrate, the compositions themselves need to be liquid at 23 ° C. or more under atmospheric pressure.
[0009]
The component (a) used in the present invention is preferably a polymer having low heat resistance, light resistance, dry etching resistance and the like, which are liable to undergo a chemical structural change during the post-treatment. Preferred polymers include, for example, polyurethane, polyurea, polyester, polycarbonate, polyether, radical polymerizable polymer, and polymer containing reactive group. In the case of a composition, two or more of these polymers can be used. In addition, from the viewpoint of reworkability at the time of semiconductor production, the polymer may be made alkali-soluble by introducing an alkali-soluble group into the molecule. Examples of the alkali-soluble group include a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a thiol group. Among these, a carboxyl group and a phenolic hydroxyl group are preferred from the viewpoint of substrate adhesion.
[0010]
Further, since the composition needs to be liquid at 23 ° C. or higher under atmospheric pressure, the component (a) needs to be a polymer soluble in an organic low-molecular compound which is liquid at 23 ° C. atmospheric pressure. For the component (a) to be soluble in organic low molecular weight compounds that are liquid at 23 ° C. and atmospheric pressure, there is a preferred weight average molecular weight, which is 150,000 or less. When the weight-average molecular weight exceeds 150,000, the composition may not be dissolved in a liquid organic low-molecular compound at 23 ° C. and atmospheric pressure, and a liquid composition may not be obtained. In consideration of the workability of coating, the preferable weight average molecular weight is 60,000 or less, and if it exceeds 60,000, there is a problem that the viscosity increases depending on the type of polymer and the workability of coating is poor. The weight average molecular weight of the polymer is a molecular weight in terms of polystyrene measured using gel permission chromatography (GPC) (HLC-8020 manufactured by Tosoh Corporation).
[0011]
Preferred examples are shown below, but other polymers can also be used as long as the effects of the present invention are not impaired.
[0012]
The polyurethane used in the present invention is obtained, for example, by reacting diol (1), diisocyanate (2), and further, water or monoalcohol (3). The diol (1) used here includes polyether diol, polyester diol, polycaprolactone diol, polycarbonate diol, modified polyorganosiloxane polyol, and the like. Preferred polyether diols are polyoxyethylene diol, polyoxypropylene diol, and the like. Polyoxytetramethylene diol, polyoxybutylene diol, polyoxybutylene-oxyethylene copolymer diol and the like can be mentioned. Examples of the polyester diol include (poly) ethylene glycol, (poly) propylene glycol, (poly) tetramethylene glycol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, 3-methylpentanediol, Examples thereof include those obtained by reacting a dihydric alcohol such as nonanediol with a dibasic acid such as phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, adipic acid, and sebacic acid. The polycaprolactone diol is obtained by reacting ε-caprolactone with a diol such as (poly) ethylene glycol, (poly) tetramethylene glycol, 1,6-hexanediol, neopentyl glycol, and 1,4-butanediol. Things. Further, examples of the polycarbonate diol include commercially available products such as DN-980, DN-981, DN-982, DN-983 (all manufactured by Nippon Polyurethane Co., Ltd.), PC8000 (manufactured by PPG, USA), and PNOC (manufactured by Kuraray). be able to. These may be used in combination of two or more.
[0013]
Examples of the diisocyanate (2) include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,5-naphthalene diisocyanate, and p-phenylene. Diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-biphenylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, methylene bis (4-socrohexyl isocyanate), hydrogenated diphenylmethane Diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, bis (2-isocyanatoethyl) fumarate, 6-isopropyl-1,3-phenyl Examples thereof include diisocyanate, 4-diphenylpropane diisocyanate, and lysine diisocyanate, and preferably include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, isophorone diisocyanate, and hydrogenated diphenylmethane diisocyanate. it can. These may be used in combination of two or more.
[0014]
Further, the monoalcohol (3) is a monoalcohol having no aliphatic or aromatic radical polymerizable group having 1 to 20 carbon atoms. Examples of the monoalcohol include methanol, ethanol, i-propanol, n-butanol, phenol and the like. Among these monoalcohols, it is preferable to use primary and secondary alcohols in consideration of reactivity with urethane. These may be used in combination of two or more.
[0015]
Examples of the method for producing a polyurethane used in the present invention include: producing a polyurethane having an isocyanate group at a terminal by reacting a diisocyanate and a diol, and reacting the diisocyanate with a monoalcohol. To produce a polyurethane having an isocyanate group at the terminal, and reacting the polyurethane with a diol. Polyols other than difunctional with respect to diols, polyisocyanates other than difunctional with respect to diisocyanates or polyamines other than difunctional with respect to diamines can be used together to such an extent that the product does not gel. Is 30 parts by weight or less for each 100 parts by weight of the diol, diamine or diisocyanate. The weight average molecular weight of the preferred polyurethane of the present invention is usually 40,000 or less, particularly preferably 1,000 to 30,000. When the weight average molecular weight exceeds 40000, when the composition is used, there is a problem that the viscosity becomes high and the coating workability is poor. The polyurea of the present invention is, for example, easily obtained by a similar synthesis method by changing a diol used for obtaining a polyurethane to a diamine, or changing a monoalcohol to a primary or secondary monoamine. Can be.
[0016]
The radical polymerizable polymer used in the present invention may be a homopolymer polymer of a radical polymerizable monomer and / or a copolymer polymer of the radical polymerizable monomer and another radical polymerizable monomer by a known polymerization method. Obtained by polymerization.
[0017]
It is preferably obtained by copolymerizing a radically polymerizable monomer in a solvent in the presence of a catalyst (polymerization initiator). As the solvent used at this time, for example, alcohols such as methanol, ethanol, propanol and butanol, cyclic ethers such as tetrahydrofuran and dioxane, cellosolve esters such as methyl cellosolve acetate and ethyl cellosolve acetate, ethylene glycol monomethyl ether, ethylene glycol Glycol ethers such as glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol propyl ether acetate, and fragrances such as benzene, toluene and xylene Group hydrocarbons, meth Ketones such as ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethoxy Ethyl acetate, ethyl hydroxyate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, ethyl acetate, butyl acetate And aprotic polar solvents such as DMF (dimethylformamide) and NMP. These solvents are generally used in an amount of 20 to 1,000 parts by weight based on 100 parts by weight of the polymerizable monomer in total. As the catalyst, those generally known as radical polymerization initiators can be widely used. For example, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4- Azo compounds such as dimethylvaleronitrile) and 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1′- Organic peroxides such as bis (t-butylperoxy) cyclohexane and hydrogen peroxide can be used. When a peroxide is used as the radical polymerization initiator, a redox initiator may be used by using the peroxide together with a reducing agent.
[0018]
Radical polymerizable monomers can be classified into, for example, those having a phenolic hydroxyl group or carboxyl group, those having an epoxy group, and others.
[0019]
Examples of the radical polymerizable monomer having a phenolic hydroxyl group or a carboxyl group include o-hydroxystyrene, m-hydroxystyrene and p-hydroxystyrene, and their alkyl, alkoxy, halogen, haloalkyl, nitro, cyano, amide, and ester. And carboxy-substituted products; polyhydroxyvinylphenols such as vinylhydroquinone, 5-vinylpyrogallol, 6-vinylpyrogallol, 1-vinylphloroglicinol, o-vinylbenzoic acid, m-vinylbenzoic acid, and p -Vinylbenzoic acids and their alkyl, alkoxy, halogen, nitro, cyano, amide, ester substituents, methacrylic acid and acrylic acid, and their haloalkyl, alkoxy, halogen, nitro, cyano Substituents, maleic acid, maleic anhydride, fumaric acid, fumaric anhydride, citraconic acid, mesaconic acid, itaconic acid and divalent unsaturated carboxylic acids such as 1,4-cyclohexenedicarboxylic acid, and methyl, ethyl, Propyl, i-propyl, n-butyl, sec-butyl, ter-butyl, phenyl, o-, m-, p-toluyl half ester and half amide can be mentioned as preferred. Of these, o-hydroxystyrene, m-hydroxystyrene and p-hydroxystyrene, and their alkyl and alkoxy substituents are useful for improving heat deformation resistance, solvent resistance, adhesion to a substrate, storage stability of a solution, and the like. Is preferably used. These may be used in combination of two or more.
[0020]
Examples of the radical polymerizable monomer having an epoxy group include o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl- m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-diglycidyloxymethylstyrene, 2,4-diglycidyloxymethylstyrene, 2,5-diglycidyloxymethylstyrene, 2, 6-diglycidyloxymethylstyrene, 2,3,4-triglycidyloxymethylstyrene, 2,3,5-triglycidyloxymethylstyrene, 2,3,6-triglycidyloxymethylstyrene, 3,4,5- Triglycidyloxy Methylstyrene, 2,4,6-glycidyloxy-methyl styrene, and the like glycidyl (meth) acrylate. Of these, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, glycidyl (meth) acrylate and the like are preferred. These compounds can be used in combination of two or more.
[0021]
Examples of the other radically polymerizable monomers include styrene, and alkyl, alkoxy, halogen, haloalkyl, nitro, cyano, amide, and ester of styrene at α-position, o-position, m-position, or p-position. Substitutes, diolefins such as butadiene, isoprene and chloroprene, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, ter-butyl (meth) acrylate, pentyl (meth) acrylate, neopentyl (meth) acrylate, isoamylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, adamantyl (meth) acrylate, a (Meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, anthracenyl (meth) acrylate, anthraquinonyl (meth) acrylate, piperonyl (meth) acrylate, salicyl (meth) acrylate, benzyl ( (Meth) acrylate, phenesyl (meth) acrylate, cresyl (meth) acrylate, 1,1,1-trifluoroethyl (meth) acrylate, perfluoroethyl (meth) acrylate, perfluoro-n-propyl (meth) acrylate , Perfluoro-i-propyl (meth) acrylate, triphenylmethyl, cumyl (meth) acrylate, 3- (N, N-dimethylamino) propyl (meth) acrylate, 3- (N, N-dimethylamido) (No) ethyl (meth) acrylate, furyl (meth) acrylate, furfuryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, butoxyethyl (meth) acrylate, ethyl diethylene glycol (meth) acrylate, 2-ethylhexyl (meth) acrylate, Phenoxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, polybutylene glycol (meth) acrylate, methyltrimethylene glycol (meth) acrylate, diethylaminoethyl (meth) ) Acrylate, 7-amino-3,7-dimethyloctyl (meth) acrylate, isobornyl (meth) acrylate, lauryl ( TA) Acrylate, “ARONIX M-114” (manufactured by Toa Gosei Chemical Co., Ltd.), “ARONIXM-113” (same as above), “TC-110S” (manufactured by Nippon Kayaku Co., Ltd.), 2-hydroxyethyl (meta) A) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyoctyl (meth) acrylate, pentaerythritol (meth) acrylate, glycerin di (meth) acrylate, dipentaerythritol monohydroxy (meth) acrylate, 1,4-butanediol mono (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, trimethylolpropanedi (meth) acrylate, trimethylolethanedi (meth) acrylate and alkyl glycidyl ether; (Meth) acrylates such as a compound obtained by an addition reaction of a glycidyl group-containing compound such as lylglycidyl ether or glycidyl acrylate with (meth) acrylic acid, (meth) acrylic anilide, (meth) acrylic amide, ) N, N-dimethyl acrylate, N, N-diethyl (meth) acrylate, N, N-dipropyl (meth) acrylate, N, N-diisopropyl (meth) acrylate, anthranilamide (meth) acrylate (Meth) acrylamides, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octadodecyl vinyl ether, cyclohexyl vinyl ether, butanediol monovinyl ether, cyclohexanedi Tanol monovinyl ether, t-butyl vinyl ether, t-amyl vinyl ether, ethylhexyl vinyl ether, dodecyl vinyl ether, ethylene glycol monovinyl ether, ethylene glycol butyl vinyl ether, hexanediol monovinyl ether, diethylene glycol monovinyl ether, triethylene glycol monovinyl ether, diethylaminoethyl vinyl ether, etc. Vinyl ethers, vinyl pyrrolidone, N-vinyl caprolactam, vinyl phenol, acrylamide, vinyl acetate, styrene, acrylonitrile, acrolein, methacrylonitrile, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinyl pyrrolidone, vinyl pyridine , Vinyl acetate, N-phenylmale For example, imide, N- (4-hydroxyphenyl) maleimide, N-methacryloylphthalimide, N-acryloylphthalimide, or the like can be used. These can be used alone or in combination of two or more.
[0022]
Among them, styrene and α-, o-, m- and p-position alkyl, alkoxy, halogen, haloalkyl-substituted styrene, butadiene and isoprene of styrene; methyl (meth) methacrylate, ethyl (meth) methacrylate , N-propyl (meth) methacrylate, N-butyl (meth) methacrylate, furfuryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, butoxyethyl (meth) acrylate, ethyl diethylene glycol (meth) acrylate, 2-ethylhexyl (meth) ) Acrylate, phenoxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, polybutylene glycol (Meth) acrylate, methyltrimethylene glycol (meth) acrylate, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octadodecyl vinyl ether, cyclohexyl vinyl ether, butanediol monovinyl ether, cyclohexane dimethanol monovinyl ether , T-butyl vinyl ether, t-amyl vinyl ether, ethylhexyl vinyl ether, dodecyl vinyl ether, ethylene glycol monovinyl ether, ethylene glycol butyl vinyl ether, hexanediol monovinyl ether, diethylene glycol monovinyl ether, triethylene glycol monovinyl ether, diethylaminoethyl vinyl Nyl ether and the like are particularly preferably used from the viewpoints of heat resistance, light resistance, dry etching resistance, storage stability of a solution, and the like. These compounds can be used in combination of two or more.
[0023]
When alkali-soluble, the preferred copolymerization ratio when a copolymer of a radical polymerizable monomer having a phenolic hydroxyl group and another radical polymerizable monomer is used is a radical polymerizable monomer having a phenolic hydroxyl group and a Radical polymerizable monomer other than the radical polymerizable monomer having a phenolic hydroxyl group or a carboxyl group is preferably 30 parts by weight or less, particularly preferably 5 to 20 parts by weight with respect to a total of 100 parts by weight of the other radical polymerizable monomers. It is. When a copolymer of a radically polymerizable monomer having a carboxyl group and another radically polymerizable monomer is used, the ratio of copolymerization is preferably between the radically polymerizable monomer having a carboxyl group and the other radically polymerizable monomer. Is preferably 90 parts by weight or less, particularly preferably 10 to 80 parts by weight, based on 100 parts by weight of the total. If the ratio of the radical polymerizable monomer exceeds the above-mentioned ratio with respect to the radical polymerizable monomer having a phenolic hydroxyl group or a carboxyl group, alkali development may be difficult. The weight average molecular weight of the preferred radical polymerizable polymer of the present invention is 60,000 or less, particularly preferably 1,000 to 40,000. If it exceeds 40,000, when the composition is used, there is a problem that the viscosity becomes high and the coating workability is poor.
[0024]
The reactive group-containing polymer used in the present invention is, for example, a homopolymer polymer of the above-mentioned radical polymerizable monomer having a phenolic hydroxyl group or a carboxyl group and / or the radical polymerizable monomer and another radical polymerizable monomer. A polymer obtained by adding the above-described epoxy group-containing radical polymerizable monomer to a copolymer polymer of a monomer and subjecting the epoxy group to ring-opening addition, or the above-described epoxy group-containing radical polymerizable monomer. The above-mentioned radical polymerizable monomer having a phenolic hydroxyl group or a carboxyl group is added to a homopolymer polymer and / or a copolymer polymer of the radical polymerizable monomer and another radical polymerizable monomer, and an epoxy group is added. Polymer obtained by ring-opening addition; and Urethane (meth) acrylate polymers, such as urea (meth) acrylate polymers.
[0025]
Among these, a polymer obtained by ring-opening addition of an epoxy group is a radical polymerizable monomer having a phenolic hydroxyl group or a carboxyl group described above or a polymer solution obtained by radical polymerization by a conventionally known polymerization method. It is obtained by adding a radical polymerizable monomer containing an epoxy group, heating at 40 ° C. to 80 ° C. for 2 hours, and subjecting the epoxy group to ring-opening addition. Further, the preferred weight average molecular weight of the polymer is 60,000 or less, particularly preferably 1,000 to 40,000. If it exceeds 40,000, when the composition is used, there is a problem that the viscosity becomes high and the coating workability is poor.
[0026]
The urethane (meth) acrylate polymer can be obtained, for example, by reacting a diol (1) and a diisocyanate (2) used in the above polyurethane with a radical polymerizable monomer (4) having one hydroxyl group.
[0027]
Examples of the radical polymerizable monomer (4) having one hydroxyl group include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyoctyl (meth) acrylate, and pentaerythritol (meth) ) Acrylate, glycerin di (meth) acrylate, dipentaerythritol monohydroxy (meth) acrylate, 1,4-butanediol mono (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, trimethylolpropanedi (meth) acrylate, And trimethylolethanedi (meth) acrylate. Further, compounds obtained by an addition reaction of a glycidyl group-containing compound such as alkyl glycidyl ether, allyl glycidyl ether, glycidyl acrylate and the like with (meth) acrylic acid can also be used. These compounds can be used in combination of two or more.
[0028]
As an example of a method for producing the urethane (meth) acrylate polymer used in the present invention, a polyurethane having an isocyanate group at a terminal is produced by reacting a diisocyanate and a diol, and a radical polymerizable monomer having one hydroxyl group is reacted with the polyurethane. And a method of reacting a diisocyanate with a radical polymerizable monomer having one hydroxyl group to produce a polyurethane having an isocyanate group at a terminal, and reacting the polyurethane with a diol. Polyols other than difunctional with respect to diols, polyisocyanates other than difunctional with respect to diisocyanates or polyamines other than difunctional with respect to diamines can be used together to such an extent that the product does not gel. Is 30 parts by weight or less for each 100 parts by weight of the diol, diamine or diisocyanate. The preferred weight average molecular weight of the urethane (meth) acrylate polymer of the present invention is 40,000, particularly preferably 1,000 to 30,000. If it exceeds 40,000, when the composition is used, there is a problem that the viscosity becomes high and the coating workability is poor.
[0029]
The urea (meth) acrylate polymer used in the present invention may be, for example, changing a diol used to obtain a urethane (meth) acrylate polymer to a diamine, or converting a radical polymerizable monomer having one hydroxyl group into a primary or secondary monomer. It can be easily obtained by changing to a radical polymerizable monomer having one class amine.
[0030]
The component (b) used in the present invention has an effect of promoting the insolubilization of the composition in an organic solvent and / or an alkaline aqueous solution by light and / or heat treatment (pretreatment). Examples of the low molecular weight compound having a polymerizable group and / or a crosslinkable group, which is the component (b) of the present invention, include a polymerizable group and are decomposed by subsequent light and / or heat treatment (post-treatment). A decomposable monomer (5) or a reactive diluent monomer (6) having a polymerizable group and being capable of dissolving and diluting other components of the composition because it is liquid at 23 ° C. under atmospheric pressure. And a heat-crosslinkable monomer (7) capable of causing a cross-linking reaction by heat.
[0031]
Examples of the decomposable monomer (5) here include isopropenyl (meth) acrylate, a compound represented by the general formula (I) having a dissociable group dissociated by acid and / or heat, and vinyl ethers. Other than that, any low molecular compound having a polymerizable group and / or a crosslinkable group may be used as long as it has a dissociation ability by an acid and / or heat.
[0032]
Embedded image

[0033]
(Where R ¹ , R ³ Represents a hydrogen atom, a methyl group, a halogen, or a methylol group. R ⁴ , R ⁵ Is an alkyl group having 1 to 20 carbon atoms, and-(CHR ⁶ OCHR ⁷ ) _l -, -R ⁸ CO-. R ⁶ , R ⁷ , R ⁸ Is selected from an alkyl group having 1 to 20 carbon atoms and an organic group containing an aromatic group, and may be the same or different. p and q each represent an integer of 0 or 1. R ² Represents a dissociable group that dissociates by an acid or heat. Further, n and m are integers from 0 to 6, and n + m> 0.)
[0034]
The compound represented by the general formula (I) is obtained by, for example, reacting an acid chloride of an above-mentioned polymerizable monomer having a carboxyl group and having an (meth) acryloyl group with an alcohol using triethylamine or the like as a catalyst. A method wherein, among the polymerizable monomers having a carboxyl group described above, a monomer having a (meth) acryloyl group and a vinyl ether are subjected to an addition reaction using pyridinium p-toluenesulfonate or the like as a catalyst. A method in which, among the polymerizable monomers, one having a (meth) acryloyl group and an acrylate are subjected to an addition reaction by heating. The above-mentioned radical polymerizable monomer (4) having one hydroxyl group and vinyl ethers are converted into p-toluene. Four types of addition reaction using pyridinium sulfonate, etc. as a catalyst It can be readily synthesized by such.
[0035]
As shown above, R ² Is a structural component of alcohols, a structural component of vinyl ethers, and a structural component of acrylates.
[0036]
Examples of the alcohols here include DM-BI25X-F, 46DMOC, 46DMOPIP, 46DMOP, TM-BIP-A (trade name, manufactured by Asahi Organic Materials Industry Co., Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, DML-PC, DML-PCHP, DML-PTBP, DML-34X, DML-EP, DML-POP, DML-OC, dimethylol-Bis-C, dimethylol-BisOC-P, DML-BisOC-Z, DML-BisOCHP-Z, DML-PFP, DML-PSBP, DML-MB25, DML-MTrisPC, DML-Bis25X-34XL, DML-Bis25X-PCHP, TriML-P, TriML-35XL, TriML-TrisCR-HAP, TML- BP, TM -HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.), t-butanol, diacetone alcohol, triacetone dialcohol , 2,5-dimethyl-2,5-hexanediol, 2,4-dimethyl-2,4-pentanediol, 3-methyl-1,3-butanediol, α, α′-dihydroxy-1,3-diisopropyl Benzene, α, α′-dihydroxy-1,4-diisopropylbenzene, α, α ′, α ″ -trihydroxy-1,3,5-triisopropylbenzene.
[0037]
Of these, preferably, triacetone dialcohol, 2,5-dimethyl-2,5-hexanediol, α, α′-dihydroxy-1,3-diisopropylbenzene, α, α′-dihydroxy-1,4- Diisopropylbenzene, α, α ′, α ″ -trihydroxy-1,3,5-triisopropylbenzene and the like.
[0038]
Examples of the vinyl ethers here include ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octadodecyl vinyl ether, cyclohexyl vinyl ether, butanediol monovinyl ether, cyclohexane dimethanol monovinyl ether, t-butyl vinyl ether, t-amyl vinyl ether, ethylhexyl vinyl ether, dodecyl vinyl ether, ethylene glycol monovinyl ether, ethylene glycol butyl vinyl ether, hexanediol monovinyl ether, diethylene glycol monovinyl ether, triethylene glycol monovinyl ether, diethylaminoethyl vinyl ether, butanediol divinyl Ether, cyclohexanedimethanol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, ethylene glycol divinyl ether, hexanediol divinyl ether, tetraethylene glycol divinyl ether, trimethylolpropane trivinyl ether, and the like. Among them, particularly preferred are cyclohexane dimethanol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, trimethylolpropane trivinyl ether and the like.
[0039]
The acrylates referred to herein include, among the (meth) acrylates and (meth) acrylates exemplified as the above-mentioned other radical polymerizable monomers, those corresponding to acrylates and acrylamides, ethylene glycol diacrylate, tetraethylene glycol Diacrylate, polyethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane trioxyethyl acrylate, tricyclodecane dimethanol diacrylate, dicyclo Pentadiene diacrylate, tricyclodecanyl diacrylate, trimethylolpropane trioxypropyl acrylate, tris-2-hydroxyethyl isocyanur Over Totori acrylate, tris-2-hydroxyethyl isocyanurate diacrylate, "Viscoat 3700" (manufactured by Osaka Organic Corporation).
[0040]
The vinyl ethers that are the decomposable monomer (5) are the same as the vinyl ethers that are structural components of the compound represented by the general formula (I) having a dissociable group that dissociates by the above-mentioned acid and / or heat. Can be used.
[0041]
In addition, the decomposable monomer (5) is a single polymer of the radically polymerizable monomer having a phenolic hydroxyl group or a carboxyl group in the radically polymerizable polymer of the component (a) of the present invention or the polymer having a reactive group. The above-mentioned radical polymerizable monomer containing an epoxy group is added to the coalesced polymer and / or the copolymer polymer of the radical polymerizable monomer and the other radical polymerizable monomer, and the epoxy group is subjected to ring-opening addition. The phenolic hydroxyl group or the homopolymer polymer of the radical polymerizable monomer containing the epoxy group and / or the copolymer polymer of the radical polymerizable monomer and the other radical polymerizable monomer. Add a radical polymerizable monomer having a carboxyl group and add an epoxy group A polymer obtained by ring-opening addition can be introduced preferably so as not to gel.
[0042]
The amount is 80 parts by weight or less based on 100 parts by weight of all monomers constituting the polymer. The component (a) into which the decomposable monomer (5) has been introduced undergoes a chemical structural change such as decomposition by subsequent light and / or heat treatment (post-treatment). The preferred weight average molecular weight of the component (a) into which the decomposable monomer (5) has been introduced is 60,000 or less, particularly preferably 1,000 to 40,000. If it exceeds 60000, there is a problem that when the composition is used, the viscosity becomes high and the coating workability is poor.
[0043]
Examples of the reactive diluent monomer (6) include monofunctional compounds having one polymerizable group, such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate. , Butoxyethyl (meth) acrylate, ethyldiethylene glycol (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, polyethylene glycol (meth) acrylate , Polypropylene glycol (meth) acrylate, methyltrimethylene glycol (meth) acrylate, diethylaminoethyl (meth) acrylate, 7-amino-3,7-dimethyloctane (Meth) acrylate, isobornyl (meth) acrylate, lauryl (meth) acrylate, vinylpyrrolidone, N-vinylcaprolactam, vinylphenol, acrylamide, vinyl acetate, vinyl ether shown as a structural component of the decomposable monomer (5) Styrene, “ARONIX M-114” (manufactured by Toa Gosei Chemical Co., Ltd.), “ARONIX M-113” (mandatory), “TC-110S” (manufactured by Nippon Kayaku Co., Ltd.) ), Polyfunctional compounds having a large number of polymerizable groups include trimethylolpropane tri (meth) acrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, , 4-butanediol Rudi (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropanetrioxyethyl (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, di Cyclopentadiene di (meth) acrylate, tricyclodecanyl di (meth) acrylate, trimethylolpropane trioxypropyl (meth) acrylate, tris-2-hydroxyethyl isocyanurate tri (meth) acrylate, tris-2-hydroxyethyl isocyanate Nurate di (meth) acrylate, "Biscoat 3700" (manufactured by Osaka Organic Co., Ltd.), and the like other than the monovinyl ethers of vinyl ethers shown as structural components of the decomposable monomer (5). . These compounds can be used in combination of two or more.
[0044]
Examples of the thermally crosslinkable monomer (7) include ML-26X, ML-24X, ML-236TMP, 4-methylol 3M6C, ML-MC, and ML-TBC having one of these crosslinkable groups. Honshu Chemical Industry Co., Ltd.), Pa-type benzoxazine (trade name, manufactured by Shikoku Chemical Industry Co., Ltd.), 3-ethyl 3-hydroxymethyloxetane, oxetanecarboxylic acid, hexyloxetane, oxetane methacrylate, benzyloxetane, Allyl oxetane, oxetane monobutyl ether, glycidol, butyl glycidyl ether and the like having two, such as DM-BI25X-F, 46DMOC, 46DMOIPP, 46DMOEP (trade name, manufactured by Asahi Organic Materials Co., Ltd.), DML-MBPC, DML- MBOC, DML-OCHP, DM -PC, DML-PCHP, DML-PTBP, DML-34X, DML-EP, DML-POP, DML-OC, Dimethylol-Bis-C, Dimethylol-BisOC-P, DML-BisOC-Z, DML-BisOCHP-Z , DML-PFP, DML-PSBP, DML-MB25, DML-MTrisPC, DML-Bis25X-34XL, DML-Bis25X-PCHP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), Nikarac MX-290 (trade name, Sanwa Chemical Co., Ltd.), Ba type benzoxazine, Bm type benzoxazine (trade name, manufactured by Shikoku Chemical Industry Co., Ltd.), 2,6-dimethoxymethyl-4-t-butylphenol, 2,6 -Dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, TriML-P, TriML-35XL, TriML-TrisCR-HAP (trade name, trade name) And TM-BIP-A (trade name, manufactured by Asahi Organic Materials Co., Ltd.), TML-BP, TML-HQ, TML-pp-BPF, TML- BPA, TMOM-BP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), Nikarac MX-280, Nikarac MX-270 (trade name, manufactured by Sanwa Chemical Co., Ltd.), etc. HML-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) You.
[0045]
Among these, in the present invention, those containing at least two thermally crosslinkable groups are preferred, and particularly preferably those having two are 46DMOC, 46DMOP (trade names, manufactured by Asahi Organic Materials Industry Co., Ltd.), DML-MBPC , DML-MBOC, DML-OCHP, DML-PC, DML-PCHP, DML-PTBP, DML-34X, DML-EP, DML-POP, Dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (Trade name, manufactured by Honshu Chemical Industry Co., Ltd.), Nikarac MX-290 (trade name, manufactured by Sanwa Chemical Co., Ltd.), Ba-type benzoxazine, Bm-type benzoxazine (trade name, Shikoku Chemical Industry) 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-c Sol, 2,6-diacetoxymethyl-p-cresol, carbonate bisoxetane, xylylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, bisoxetane cyclohexanedicarboxylate, MDI bisoxetane, etc. , TriML-35XL (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (trade name, manufactured by Asahi Organic Materials Co., Ltd.), TML-BP, TML-HQ, etc. TML-pp-BPF, TML-BPA, TMOM-BP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), Nikarac MX-280, Nikarac MX-270 (trade name, manufactured by Sanwa Chemical Co., Ltd.), etc., 6 HML-TPPHBA, HML-TPHAP (trade name, Honshu Chemical) Business Co., Ltd.), and the like. These compounds can be used in combination of two or more.
[0046]
Of the component (b), the component (a) obtained by introducing the decomposable monomer (5) itself undergoes a chemical structural change such as decomposition due to subsequent light and / or heat treatment (post-treatment). Therefore, the combination with the component (b) can be limited in the composition. When these are combined, the component (b) is preferably at most 4000 parts by weight, particularly preferably at most 3000 parts by weight, per 100 parts by weight of the component (a). If the amount exceeds 4,000 parts by weight, there is a problem that when the composition is used, the viscosity becomes low, and when applied to a substrate, the coating workability such as repelling is poor.
[0047]
Of the component (b), the component (a) into which the decomposable monomer (5) has not been introduced does not itself cause a chemical structural change such as decomposition due to subsequent light and / or heat treatment (post-treatment). Therefore, in the composition, it can be used in combination with the decomposable monomer (5) of the component (b).
[0048]
When these are combined, the component (b) is preferably 10 to 4000 parts by weight, particularly preferably 10 to 3000 parts by weight, based on 100 parts by weight of the component (a). If the amount exceeds 4,000 parts by weight, there is a problem that when the composition is used, the viscosity becomes low, and when applied to a substrate, the coating workability such as repelling is poor. If the amount is less than 10 parts by weight, the etching rate after the post-treatment may be less than 1.2 times the etching rate after the pre-treatment, which is not preferable.
[0049]
Further, when the component (b) is a decomposable monomer (5), the composition itself causes a chemical structural change such as decomposition by subsequent light and / or heat treatment (post-treatment). )) Can be used alone without using the component, or can be used in combination with the other component (b).
[0050]
When these are combined, the other component (b) is preferably 4,000 parts by weight or less, particularly preferably 3,000 parts by weight or less, based on 100 parts by weight of the decomposable monomer (5). If the amount exceeds 4,000 parts by weight, there is a problem that when the composition is used, the viscosity becomes low, and when applied to a substrate, the coating workability such as repelling is poor.
[0051]
The acid generator of the component (c) used in the present invention has an action of accelerating the decomposition of the component (a) and / or the component (b) by the generated acid.
[0052]
As the acid generator of the component (c), for example, bis (p-toluenesulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, p-bis (2,4-dimethyl) Bissulfonyldiazomethanes such as phenylsulfonyl) diazomethane, 2-nitrobenzyl p-toluenesulfonate, 2,6-dinitrobenzyl p-toluenesulfonate, and 2,4-dinitrobenzyl p-trifluoromethylbenzenesulfonate Such as nitrobenzyl derivatives, pyrogallol methanesulfonate, pyrogallol benzenesulfonate, and pyrogallol p-toluenesulfonic acid esters such as pyrogallol and aliphatic or aromatic sulfonates, diphenyliodonium Hexafluorophosphate, (4-methoxyphenyl) phenyliodonium trifluoromethanesulfonate, bis (p-tert-butylphenyl) iodonium trifluoromethanesulfonate, triphenylsulfonium hexafluorophosphate, (p-tert-butylphenyl) diphenylsulfonium trifluorofluoride Onium salts such as methanesulfonate; benzoin tosylate such as henzointosylate and α-methylbenzoin tosylate; 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine , 2- [2- (2-furyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (5-methyl-2-furyl) ethenyl] -4 , 6-bis (Trichloromethyl) -1,3,5-triazine, 2- [2- (3,5-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [ 2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (3,4-methylenedioxyphenyl) -4,6-bis ( Trichloromethyl) -1,3,5-triazine, tris (1,3-dibromopropyl) -1,3,5-triazine, tris (2,3-dibromopropyl) -1,3,5-triazine, tris ( Halogen-containing triazine compounds such as 2,3-dibromopropyl) socyanurate, α- (toluenesulfonyloxyimino) -phenylacetonitrile, α- (p-chlorobenzenesulfonyl) Oxyimino) -phenylacetonitrile, α- (4-nitrobenzenesulfonyloxyimino) -phenylacetonitrile, α- (4-nitro-2-trifluoromethylbenzenesulfonyloxyimino) -phenylacetonitrile, α- (benzenesulfonyloxyimino)- 4-chlorophenylacetonitrile, α- (benzenesulfonyloxyimino) -2,4-dichlorophenylacetonitrile, α- (benzenesulfonyloxyimino) -2,6-dichlorophenylacetonitrile, α- (benzenesulfonyloxyimino) -4-methoxyphenyl Acetonitrile, α- (2-chlorobenzenesulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (benzenesulfonyloxyimino) -2-thienylacetonitrile , Α- (4-dodecylbenzenesulfonyloxyimino) -phenylacetonitrile, α- (4-toluenesulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (4-dodecylbenzenesulfonyloxyimino) -4-methoxyphenyl Acetonitrile, α- (trisulfonyloxyimino) -3-thienylacetonitrile, α- (methylsulfonyloxyimino) -phenylacetonitrile, α- (methylsulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (trifluoromethyl Sulfonyloxyimino) -phenylacetonitrile, α- (trifluoromethylsulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (ethylsulfonyloxyimino) -4-methoxyphenylacetone Nitrile, α- (propylsulfonyloxyimino) -4-methylphenylacetonitrile, α- (methylsulfonyloxyimino) -4-bromophenylacetonitrile, α- (methylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α -(Methylsulfonyloxyimino) -1-cyclohexenylacetonitrile, α- (methylsulfonyloxyimino) -1-cycloheptenylacetonitrile, α- (methylsulfonyloxyimino) -1-cyclooctenylacetonitrile, α- (tri Fluoromethylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α- (trifluoromethylsulfonyloxyimino) -1-cyclohexenylacetonitrile, α- (ethylsulfonyloxyimino) -ethyl Setonitrile, α- (propylsulfonyloxyimino) -propylacetonitrile, α- (cyclohexylsulfonyloxyimino) -cyclopentylacetonitrile, α- (cyclohexylsulfonyloxyimino) -cyclohexylacetonitrile, α- (cyclohexylsulfonyloxyimino) -1-cyclo Pentenylacetonitrile, α- (1-naphthylsulfonyloxyimino) -4-methoxybenzylcyanide, α- (2-naphthylsulfonyloxyimino) -4-methoxybenzylcyanide, α- (1-naphthylsulfonyloxyimino) benzyl Cyanide, α- (2-naphthylsulfonyloxyimino) benzyl cyanide, α- (10-camphasulfonyloxyimino) -4-methoxybenzyl cyanide, α- (10-can And sulfonyloxyimino) benzyl cyanide, α- (3-camphasulfonyloxyimino) -4-methoxybenzyl cyanide, α- (3-bromo-10-camphasulfonyloxyimino) -4-methoxybenzyl cyanide and the like. Oxime sulfonate compounds, N-methylsulfonyloxysuccinimide, N-isopropylsulfonyloxysuccinimide, N-chloroethylsulfonyloxysuccinimide, N- (p-methoxyphenyl) sulfonyloxysuccinimide, N- (p-vinylphenyl) sulfonyloxy Succinimide, N-naphthylsulfonyloxysuccinimide, N-phenylsulfonyloxysuccinimide, N- (2,4,6-trimethylphenyl) sulfonyloxysuccinimide, N-methyl Ruphonyloxymaleimide, N-isopropylsulfonyloxymaleimide, N-chloroethylsulfonyloxymaleimide, N- (p-methoxyphenyl) sulfonyloxymaleimide, N- (p-vinylphenyl) sulfonyloxymaleimide, N-naphthylsulfonyloxymaleimide , N-phenylsulfonyloxymaleimide, N- (2,4,6-trimethylphenyl) sulfonyloxymaleimide, N-methylsulfonyloxyphthalimide, N-isopropylsulfonyloxyphthalimide, N-chloroethylsulfonyloxyphthalimide, N- (p -Methoxyphenyl) sulfonyloxyphthalimide, N- (p-vinylphenyl) sulfonyloxyphthalimide, N-naphthylsulfonyloxyphthalimide, N-phthal Sulfonyl sulfonyloxy phthalimide, N- and imide compounds such as (2,4,6-trimethylphenyl) sulfonyloxy shea phthalimide, and bis oxime sulfonate compound.
[0053]
Among them, preferred are diphenyliodonium hexafluorophosphate, (4-methoxyphenyl) phenyliodonium trifluoromethanesulfonate, and bis (p-tert-butylphenyl) iodonium trifluoromethanesulfonate. These may be used in combination of two or more.
[0054]
The addition amount of the component (c) of the present invention is preferably 0.1 to 40 parts by weight, particularly preferably 0.1 to 40 parts by weight, per 100 parts by weight of the total of the component (a) and / or the component (b). 30 parts by weight.
[0055]
The radical generator of the component (d) used in the present invention promotes the insolubilization of the organic solvent and / or the aqueous alkali solution in the pretreatment of the component (a) and / or the component (b) by the generated radical. It has an effect.
[0056]
As the radical generator of the component (d), for example, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4- Azo compounds such as methoxy-2,4-dimethylvaleronitrile), and organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, and 1,1′-bis (t-butylperoxy) cyclohexane. And hydrogen peroxide, acetophenone, acetophenone benzyl ketal, anthraquinone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, carbazole, xanthone, 4-chlorobenzophenone, 4,4'- Diaminobenzophenone, 1,1-dimethoxydeoxybenzoin, 3,3′-dimethyl 4-methoxybenzophenone, thioxanthone, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino- Propan-1-one, triphenylamine, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, fluorenone, fluorene, Benzyl methyl ketal, benzaldehyde, benzoin ethyl ether, benzoin propyl ether, benzophenone, Michler's ketone, 3-methylacetophenone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone (BTTB), - dimethoxy-1- [4- (2-hydroxyethoxy) - phenyl] -2-hydroxy-2-methyl-1-like.
[0057]
Of these, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -Butanone-1,2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-dimethoxy-1,2-diphenylethane -1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-2-methyl-1-phenyl-propane- 1-one and the like are preferred. These may be used in combination of two or more.
[0058]
The radical generator of the present invention is added in an amount of 0.001 to 30 parts by weight, preferably 0.005 to 20 parts by weight, based on 100 parts by weight of the total amount of the component (a) and / or the component (b). You.
[0059]
Further, in the present invention, a surfactant may be blended in order to improve the coatability of the composition, for example, to prevent striation (after coating streaks). Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; and polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether. Nonionic surfactants such as polyoxyethylene dialkyl esters such as oxyethylene aryl ethers, polyoxyethylene dilaurate and polyoxyethylene distearate; F-Top EF301, 303 and 352 (manufactured by Shin-Akita Chemical Co., Ltd.) ), Megafac F171, F172, F173 (manufactured by Dainippon Ink and Chemicals, Inc.), Florado FC-430, FC-431 (manufactured by Sumitomo 3M Limited), Asahi Guard G710, Surflon S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (manufactured by Asahi Glass Co., Ltd.) Fluorine surfactant, organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid copolymer polyflow No. 57, 75, 77, 95 (manufactured by Kyoeisha Yushi Kagaku Kogyo KK) and the like. These may be used in combination of two or more. Such a surfactant may be contained in an amount of 2 parts by weight or less, preferably 1 part by weight or less, when the total amount of the composition is 100 parts by weight. Further, the composition according to the present invention may include an adhesion aid in order to improve the adhesion to the substrate. Examples of such an adhesion aid include a silane coupling agent. Further, the composition according to the present invention may contain an antistatic agent, a storage stabilizer, an antifoaming agent, and the like, if necessary. The composition according to the present invention can be easily prepared by uniformly mixing the above components.
[0060]
Such a composition is used in the form of a solution by dissolving it in a liquid organic low-molecular compound at 23 ° C. and atmospheric pressure.
[0061]
The organic low molecular weight compound which is liquid at 23 ° C. and the atmospheric pressure as referred to herein means an organic solvent such as the above-mentioned reaction diluent monomer (6) or a polymerization solvent used in producing the component (a). And other organic solvents can also be used.
[0062]
Examples of other organic solvents referred to herein include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, Benzyl ethyl ether, dihexyl ether, acetonylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, carbonic acid Examples include ethylene, propylene carbonate, phenyl cellosolve acetate, diacetone alcohol, 2-heptanone, and cyclohexano.
[0063]
Among these organic low-molecular weight compounds which are liquid at 23 ° C. and atmospheric pressure, propylene glycol ethers such as propylene glycol monoethyl ether, propylene glycol, etc., from the viewpoint of solubility, reactivity with each component, and ease of forming a coating film. Propylene glycol alkyl ether acetates such as glycol monomethyl ether acetate, esters such as ethyl 2-hydroxypropionate, ketones such as 2-heptanone and cyclohexanone, diacetone alcohol, and reaction diluent monomer (6) are preferably used. In the present invention, the composition is prepared by dissolving a low-molecular organic compound which is a liquid at 23 ° C. and atmospheric pressure as a solvent so that the solid content concentration is preferably 5 to 100% by weight. Applied. Further, the composition solution prepared as described above can be used after being filtered using a Millipore filter having a pore diameter of about 0.2 μm. The composition solution of the present invention thus prepared is excellent in long-term storage stability.
[0064]
Next, a method for using the composition of the present invention will be described. First, the composition of the present invention is applied to a substrate surface to form a coating film insoluble in an organic solvent and / or an aqueous alkaline solution.
[0065]
As the method, in the case of a composition using an organic solvent as a dissolving solvent, (A) a method in which after coating on the substrate surface, the solvent is removed and the solvent is insolubilized simultaneously with heating; A method of removing the solvent and then irradiating with light or further heating at a higher temperature than the above to insolubilize.
[0066]
In the case of a composition using the reaction diluent monomer (6) as a dissolving solvent, (C) a method of insolubilizing by heating or light irradiation after coating on the substrate surface may be mentioned.
[0067]
The method of coating the substrate surface is not particularly limited, and for example, a method such as spin coating using a spinner, spray coating, or roll coating is used. The thickness of the coating film 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 dried film thickness is 0.1 to 100 μm.
[0068]
Next, the insolubilized coating film is heated or irradiated with light at a higher temperature than the above, and then removed by dry etching with an etching gas.
[0069]
Examples of the light used in the light irradiation according to the present invention include actinic rays such as ultraviolet rays, visible light, electron beams, and X-rays. In the present invention, i-line (365 nm), h-line (405 nm), and g of mercury lamps are used. Preferably, a line (436 nm) is used.
[0070]
The etching gas used here is, for example, oxygen, fluorine, CF ₄ , CHF ₃ , Argon, C ₄ F ₈ And the like. One or more of these etching gases are mixed and dry-etched to remove the composition from the substrate. In the present invention, the etching rate after the post-processing is preferably 1.2 times or more, particularly preferably 1.4 times or more, and more preferably 2 times or more, as compared with the etching rate after the pre-processing. More than double. When the ratio is less than 1.2 times, it is difficult to completely remove the composition in the hole by dry etching after forming the wiring groove, and a problem such as an increase in connection resistance occurs in the semiconductor element due to the residual composition, which is preferable. Absent. The dry etching process is performed, for example, by using a dry etching apparatus at a pressure of 750 mTorr and using CHF as an etching gas. ₃ , CF ₄ Using an argon mixed gas, the flow rates were 10, 90, and 950 sccm, the RF input power was 900 W, the substrate temperature was 40 ° C., the etching time was 120 seconds, the pressure was 60 mTorr, the etching gas was argon, CF, and the like. ₄ An oxygen mixed gas is used at a flow rate of 48.84, 0.67, 0.49 sccm, RF input power of 50 W, a substrate temperature of 25 ° C., and an etching time of 60 seconds. In addition, the heating conditions referred to herein vary depending on the type and blending ratio of each component, but are generally from 60 ° C. to 250 ° C. for about 10 seconds to 10 minutes.
[0071]
Regarding the removal of the composition, in addition to the dry etching treatment, the composition of the semi-invention may be dissolved and removed with a stripping solution instead of the dry etching treatment.
[0072]
An organic solvent and / or an alkaline aqueous solution is used as the stripping solution here.
[0073]
Examples of the stripping solution used in the present invention include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, and hexamethylphosphortriamide. Alone or in methanol, ethanol, isopropyl alcohol, methyl carbitol, ethyl carbitol, toluene, xylene, ethyl lactate, ethyl pyruvate, propylene glycol monomethyl ether acetate, methyl-3-methoxypropionate, ethyl-3-ethoxypro Organic solvents such as pionate, 2-heptanone and ethyl acetate, aqueous solutions of tetramethylammonium, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, charcoal Aqueous solutions of alkaline compounds such as potassium, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine, and the like. An aqueous solution of ammonium or an aqueous solution of an alkaline compound such as diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and triethylamine 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.
[0074]
The stripping time with the stripping solution is usually from 5 seconds to 3 hours, and stripping may be performed by any of a liquid pudging method and a dipping method. After peeling, washing with running water is performed for 30 to 180 seconds, and air-drying is performed with compressed air or compressed nitrogen.
[0075]
Further, the formation of a multilayer wiring structure for manufacturing a semiconductor device having a multilayer wiring structure using the composition of the present invention is performed, for example, as follows.
[0076]
On the interlayer insulating film formed on the lower wiring, a photoresist film patterned into a hole pattern is formed, and using this as a mask, the interlayer insulating film is etched by a dry etching method to form a deep hole reaching the lower wiring. First, it is formed. Next, the composition of the present invention is insolubilized by application, light and / or heat treatment, and the holes are filled. An anti-reflective material is formed on the filled interlayer insulating film, and a photoresist film patterned into a groove pattern is further formed thereon, and thereafter, light and / or heat treatment is performed. Using the photoresist film as a mask, The antireflection film, the interlayer insulating film, and the composition in the hole are etched in the same manner. A groove is formed in the same manner as the removal of the composition in the hole, and copper is embedded in the groove and the hole to form a wiring. Further, a multilayer wiring structure is formed by forming an interlayer insulating film on the wiring and repeating the steps of forming holes and grooves, filling copper, and forming an interlayer insulating film as described above.
[0077]
Also, using the above photoresist film as a mask, the antireflection film, the interlayer insulating film, and the same composition in the hole are etched in the same manner, but if the composition in the hole cannot be removed and remains, immediately after that, , An organic solvent or an aqueous alkaline solution.
[0078]
【Example】
Hereinafter, the present invention will be described with reference to examples and techniques, but the present invention is not limited to these examples. In addition, the evaluation of the composition in an Example was performed by the following method.
[0079]
1. Preparation of composition film after pretreatment
A composition film after the pretreatment operation was prepared by any one of the pretreatment methods 1, 2, and 3 shown below.
[0080]
Pretreatment method 1
On a 6-inch silicon wafer, a composition (hereinafter, referred to as varnish) was applied so that the film thickness after pre-baking was 2 μm, and then, using a hot plate (Mark-7, manufactured by Tokyo Electron Ltd.), The composition film was obtained by pre-baking at a temperature for a predetermined time.
[0081]
Pretreatment method 2
A composition (hereinafter referred to as varnish) is applied on a 6-inch silicon wafer so that the film thickness after prebaking becomes 2 μm, and then 130 ° C. using a hot plate (Mark-7, manufactured by Tokyo Electron Limited). And pre-baking for 2 minutes with an exposure machine (contact aligner PLA501F manufactured by Canon Inc.), and an ultraviolet intensity of 10 mW / cm. ² The composition film was obtained by performing UV exposure at a wavelength of 365 nm (for conversion to 365 nm) for a predetermined time.
[0082]
Pretreatment method 3
A composition (hereinafter, referred to as varnish) is applied on a 6-inch silicon wafer so that the film thickness after irradiation with ultraviolet light becomes 2 μm, and then, with an exposure machine (Contact Aligner PLA501F manufactured by Canon Inc.), the ultraviolet intensity is 10 mW. / Cm ² The composition film was obtained by performing UV exposure at a wavelength of 365 nm (for conversion to 365 nm) for a predetermined time.
[0083]
2. Preparation of composition film after post-treatment
The composition film after the post-processing operation was prepared by any of the following post-processing methods 1 and 2.
[0084]
Post-processing method 1
The composition film formed by the pretreatment was further baked at a predetermined temperature for a predetermined time using a hot plate (Mark-7, manufactured by Tokyo Electron Limited).
[0085]
Post-processing method 2
The composition film formed by the above pretreatment operation was further subjected to an ultraviolet intensity of 10 mW / cm by an exposure machine (contact aligner PLA501F manufactured by Canon Inc.). ² (Converted to 365 nm) for a predetermined period of time to carry out an ultraviolet all-wavelength exposure treatment.
[0086]
3. Evaluation of fabricated film
Measurement method of film thickness
The measurement was performed at a refractive index of 1.510 using Lambda Ace STM-602 manufactured by Dainippon Screen Mfg. Co., Ltd.
[0087]
Evaluation of insolubility of composition film after pretreatment
When evaluating the insolubility of the composition film after the pretreatment in the above 1 in an alkaline aqueous solution, 2.38% of tetramethylammonium hydroxide at 50 rpm using a developing device of Mark-7 manufactured by Tokyo Electron Limited. The aqueous solution was sprayed for 10 seconds. Thereafter, the film is left standing at 0 rotation for 120 seconds, rinsed with water at 400 rotations, shaken off at 3000 rotations for 10 seconds, dried, and then measured for the film thickness of the composition. It was evaluated whether there was no film loss in comparison with.
[0088]
When evaluating the insolubility in an organic solvent, a solvent of propylene glycol monomethyl ether acetate / ethyl lactate = 7/3 (weight ratio) was sprayed for 60 seconds at 50 rotations using a Mark-7 developing device manufactured by Tokyo Electron Limited. did. Thereafter, the film was rinsed with propylene glycol monomethyl ether acetate at 400 rotations, shaken off at 3000 rotations for 10 seconds, and dried. The film thickness of the composition was measured and compared with the film thickness before the organic solvent treatment. We evaluated whether there was no decrease.
[0089]
Comparison of etching rates
The composition film after the above-mentioned 1 pre-treatment and the film after the above-mentioned 2 post-treatment were etched with an anisotropic dry etching apparatus (RIE-10N) manufactured by Samco International Laboratories Co., Ltd. at a pressure of 60 mTorr. As gas, argon, CF ₄ Using a mixed gas of oxygen and oxygen, the flow rates were set as follows, RF input power was 200 W, the substrate temperature was 25 ° C., and the etching time was 60 seconds. Dry etching was performed, and the etching rate ratio was compared. .
[0090]
Setting 1: Argon / CF ₄ /Oxygen=47.73 sccm / 1.31 sccm / 0.95 sccm
Setting 2: Argon / CF ₄ / Oxygen = 0sccm / 48sccm / 2sccm
Setting 3: Argon / CF ₄ / Oxygen = 0 sccm / 50 sccm / 0 sccm
Etching rate ratio
The etching rate ratio was calculated by the following method.
Etching rate ratio = etching rate of composition film after post-treatment / etching rate of composition film after pre-treatment.
[0091]
Evaluation of peelability (solubility)
In the case of alkali stripping of the composition film after the above-mentioned post-treatment 2, a 2.38% aqueous solution of tetramethylammonium hydroxide is used for 10 seconds at 50 rotations using a Mark-7 developing device manufactured by Tokyo Electron Limited. Sprayed. Thereafter, the mixture was allowed to stand still at 0 rotation for 120 seconds, rinsed with water at 400 rotations, shaken off at 3000 rotations for 10 seconds, and dried. The presence or absence of a composition residue was observed with an optical microscope to determine the releasability.
[0092]
In the case of organic solvent peeling, a solvent of 50 rotations of γ-butyrolactone / ethyl lactate = 7/3 (weight ratio) was sprayed for 60 seconds using a Mark-7 developing device manufactured by Tokyo Electron Limited. Thereafter, the film was rinsed with propylene glycol monomethyl ether acetate at 400 rotations, shaken off and dried at 3000 rotations for 10 seconds, and the presence or absence of a composition residue was observed with an optical microscope to determine the releasability.
[0093]
Synthesis Example 1 Synthesis of degradable monomer (a)
In a stream of dry air, 14.6 g (0.1 mol) of 2,5-dimethyl-2,5-hexanediol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 22.0 g (0.21 mol) of methacrylic acid chloride were added. It was dissolved in 100 g of dichloromethane and cooled to -15 ° C. To this, 21.3 g (0.21 mol) of triethylamine 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 1 hour. Thereafter, the mixture was stirred at room temperature for 2 hours. The triethylamine salt was filtered, and the organic layer was washed three times with a saturated sodium hydrogen carbonate solution. Thereafter, dichloromethane in the organic layer was distilled off under reduced pressure to obtain 25.4 g of a decomposable monomer (a).
[0094]
Synthesis Example 2 Synthesis of Degradable Monomer (b)
Under a stream of dry air, 19.6 g (0.1 mol) of cyclohexanedimethanol divinyl ether (manufactured by BASF) and 18.1 g (0.21 mol) of methacrylic acid were dissolved in 100 g of dichloromethane, and p-toluenesulfonic acid was dissolved. 0.01 g of a pyridine salt was added as a catalyst and reacted at 0 ° C. for 1 hour. Thereafter, the mixture was stirred at room temperature for 2 hours. The pyridine salt catalyst of p-toluenesulfonic acid was filtered, and the organic layer was washed three times with a saturated sodium hydrogen carbonate solution. Thereafter, dichloromethane in the organic layer was distilled off under reduced pressure to obtain 33.2 g of a decomposable monomer (b).
[0095]
Synthesis Example 3 Synthesis of degradable monomer (c)
Under dry air flow, 22.6 g (0.1 mol) of 1,4-butanediol diacrylate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 18.1 g (0.21 mol) of methacrylic acid were dissolved in 100 g of dichloromethane. Then, 0.01 g of a pyridine salt of p-toluenesulfonic acid was added as a catalyst and reacted at 0 ° C. for 1 hour. Thereafter, the mixture was stirred at room temperature for 2 hours. The pyridine salt catalyst of p-toluenesulfonic acid was filtered, and the organic layer was washed three times with a saturated sodium hydrogen carbonate solution. Thereafter, dichloromethane in the organic layer was distilled off under reduced pressure to obtain 35.9 g of a decomposable monomer (c).
[0096]
Example 1
Under a stream of dry nitrogen, 5 g of 2,2′-azobis (2,4-dimethylvaleronitrile), 200 g of propylene glycol monomethyl ether acetate, 25 g of methacrylic acid, 40 g of methyl methacrylate, and 10 g of hydroxyethyl methacrylate were charged and dissolved. At 70 ° C. for 4 hours. After completion of the reaction, the alkali-soluble radically polymerizable polymer solution was added to 1000 g of hexane, and a precipitate of polymer solid was collected by filtration. The polymer solid was dried in a vacuum dryer at 80 ° C. for 10 hours.
[0097]
10 g of the polymer solid thus obtained was weighed, and 50 g of diethylene glycol divinyl ether was added thereto to obtain a varnish A of the composition.
[0098]
Using the obtained varnish A, as described above, a pre-baked composition film was formed on a silicon wafer at 130 ° C. for 3 minutes in accordance with the pre-treatment method 1, and then at 160 ° C. according to the post-treatment method 1. By baking for 2 minutes, a composition film after the post-treatment was produced. These composition films thus obtained were subjected to predetermined evaluations such as insolubility, comparison of etching rates according to the above setting 1, and releasability.
[0099]
Example 2
Under a dry nitrogen stream, 5 g of 2,2′-azobis (2,4-dimethylvaleronitrile), 200 g of propylene glycol monomethyl ether acetate, 25 g of the decomposable monomer (a) obtained in Synthesis Example 1 above, and 10 g of methacrylic acid , 10 g of t-butyl methacrylate, 3 g of 2-hydroxybutyl methacrylate, and 3 g of ethyl 3-mercaptopropionate as a chain transfer agent were dissolved therein, and the mixture was stirred and reacted at 70 ° C. for 4 hours. After completion of the reaction, the radical polymerizable polymer solution was charged into 1000 g of hexane, and the precipitate of polymer solid was collected by filtration. The polymer solid was dried in a vacuum dryer at 80 ° C. for 10 hours.
[0100]
10 g of the polymer solid thus obtained was weighed, 10 g of propylene glycol dimethacrylate, 3 g of diphenyliodonium hexafluorophosphate as an acid generator, and 2-dimethoxy-1,2-diphenylethane-1-one as a radical generator. 2 g was added to obtain a varnish B of the composition.
[0101]
Using the varnish B thus obtained, the composition film after the pre-treatment is formed on the silicon wafer by irradiating ultraviolet rays for 30 seconds in accordance with the pre-treatment method 3 according to the pre-treatment method 3 as described above. The composition film after the post-treatment was prepared by baking for minutes. The obtained composition films were subjected to predetermined evaluations such as insolubility, comparison of etching rates according to the above setting 2, and releasability.
[0102]
Example 3
A reaction vessel equipped with a stirrer was charged with 200 g of isobornyl methacrylate, 566 g of 2,4-tolylene diisocyanate, 2 g of dibutyltin dilaurate, and 3 g of 2,6-di-t-butyl-4-methylphenol. Then, while cooling the reaction vessel, 377 g of hydroxyethyl methacrylate was gradually added with stirring so that the internal temperature did not exceed 25 ° C. After completion of the addition, the mixture was further stirred for 1 hour while maintaining the internal temperature at 20 to 40 ° C. Then, 1057 g of polyoxytetramethylene glycol (molecular weight 650) was added, and stirring was continued at 60 ° C. for 5 hours. After confirming that the residual isocyanate group was 0.1% by weight or less, the content was taken out to obtain an isobornyl methacrylate solution of a urethane methacrylate polymer (weight average molecular weight 1230) having acryloyl groups bonded to both ends. .
[0103]
11 g of the polymer solution thus obtained was weighed, 10 g of 1,9-nonanediol dimethacrylate, 25 g of the decomposable monomer (c) obtained in Synthesis Example 2 above, and (4-methoxyphenyl) phenyl as an acid generator Varnish C of the composition was obtained by adding 3 g of iodonium trifluoromethanesulfonate, 2 g of 2,2′-azobisisobutyronitrile and 50 g of γ-butyrolactone as radical generators.
[0104]
Using the obtained varnish C, as described above, a pre-baked composition film was formed on a silicon wafer by pre-baking at 120 ° C. for 4 minutes and then irradiating with ultraviolet rays for 30 seconds according to pre-processing method 2, and further post-processing. By baking at 170 ° C. for 2 minutes according to Method 1, a composition film after post-treatment was prepared. The obtained composition films were subjected to predetermined evaluations such as insolubility, comparison of etching rates according to the above setting 2, and releasability.
[0105]
Example 4
Under a stream of dry nitrogen, 5 g of 2,2′-azobis (2,4-dimethylvaleronitrile), 200 g of propylene glycol monomethyl ether acetate, 25 g of the decomposable monomer (a) obtained in Synthesis Example 1 above, ethyl methacrylate 40 g, 15 g of methacrylic acid, and 2 g of 3-mercaptopropionic acid as a chain transfer agent were charged and dissolved, and the mixture was stirred and reacted at 70 ° C. for 4 hours. After stirring at 100 ° C. for 2 hours to decompose the residual polymerization initiator, 10 g of glycidyl methacrylate was added and reacted at 80 ° C. for 3 hours. After completion of the reaction, the reactive group-containing polymer solution was poured into hexane (1000 g), and a precipitate of polymer solid was collected by filtration. The polymer solid was dried in a vacuum dryer at 30 ° C. for 5 hours.
[0106]
10 g of the polymer solid thus obtained was weighed, 10 g of propylene glycol dimethacrylate, 10 g of the decomposable monomer (b) obtained in Synthesis Example 2 above, and bis (p-tert-butylphenyl) iodonium as an acid generator 3 g of trifluoromethanesulfonate and 2 g of 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one as a radical generator were added to obtain Varnish D of the composition.
[0107]
Using the obtained varnish D, the composition film after the pre-treatment is formed on the silicon wafer by irradiating ultraviolet rays for 30 seconds according to the pre-processing method 3 as described above, and further according to the post-processing method 2, for 30 seconds. Was applied to prepare a composition film after the post-treatment. These composition films thus obtained were subjected to predetermined evaluations such as insolubility, comparison of etching rates according to the above setting 3, and releasability.
[0108]
Example 5
Using the varnish D obtained in Example 4, as described above, a pre-baked composition film was formed on a silicon wafer by prebaking at 130 ° C. for 2 minutes in accordance with the pre-treatment method 1. According to this, a post-treatment composition film was prepared by performing a post-treatment operation of baking at 170 ° C. for 2 minutes. These composition films thus obtained were subjected to predetermined evaluations such as insolubility, comparison of etching rates according to the above setting 3, and releasability.
[0109]
Example 6
Without using the polymer synthesized in Example 4, 10 g of propylene glycol dimethacrylate, 10 g of the decomposable monomer (b) obtained in Synthesis Example 2 above, and bis (p-tert-butylphenyl) iodonium trifluoromethane as an acid generator A varnish E of the composition was obtained by adding 3 g of sulfonate and 2 g of 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one as a radical generator. The same evaluation as in Example 4 was performed using the obtained varnish E.
[0110]
Example 7
Formation of a multilayer wiring structure for manufacturing a semiconductor device having a multilayer wiring structure was performed as follows. On the interlayer insulating film formed on the lower wiring, a photoresist film patterned into a hole pattern is formed, and using this as a mask, the interlayer insulating film is etched by a dry etching method to form a deep hole reaching the lower wiring. First formed. Next, the varnish A obtained in Example 1 was applied and baked at 130 ° C. for 3 minutes to fill the holes. An anti-reflective material is formed on the filled interlayer insulating film, and a photoresist film patterned into a groove pattern is further formed thereon. After that, processing is performed at 160 ° C. for 2 minutes, and the photoresist film is used as a mask. , The antireflection film, the interlayer insulating film, and the composition in the hole were etched in the same manner. A groove was formed in the same manner as the removal of the composition in the hole, and copper was buried in the groove and the hole to form a wiring. Further, an interlayer insulating film was formed on the wiring, and as described above, the steps of forming holes, trenches, burying copper, and forming an interlayer insulating film were repeated five times to form a multilayer wiring structure.
[0111]
Comparative Example 1
m / p cresol novolak-based OFPR-800 (manufactured by Tokyo Ohka Co., Ltd.) is pre-baked at 130 ° C. for 2 minutes on a silicon wafer using a positive resist for g-line according to pretreatment method 1 as described above. A post-treatment composition film (resist film) was prepared, and a post-treatment operation of baking was performed at 170 ° C. for 2 minutes according to post-treatment method 1 to prepare a post-treatment composition film. These composition films thus obtained were subjected to predetermined evaluations such as insolubility, comparison of etching rates according to the above setting 3, and releasability.
[0112]
Comparative Example 2
Varnish A1 was obtained in the same manner as in Example 1, except that diethylene glycol divinyl ether was changed to 1,9-nonanediol dimethacrylate. The same evaluation as in Example 1 was performed using the obtained varnish A1.
[0113]
Comparative Example 3
Varnish B1 was obtained in the same manner as in Example 1, except that diethylene glycol divinyl ether was changed to 1,9-nonanediol dimethacrylate and 3 g of diphenyliodonium hexafluorophosphate was added as an acid generator. The same evaluation as in Example 1 was performed using the obtained varnish B1.
[0114]
Comparative Example 4
A varnish C1 was obtained in the same manner as in Example 2, except that diphenyliodonium hexafluorophosphate as an acid generator was not used. The same evaluation as in Example 2 was performed using the obtained varnish C1.
[0115]
Comparative Example 5
Varnish A was changed to OFPR-800, applied to the deep holes obtained in the same manner as in Example 7, and baked at 130 ° C. for 2 minutes to fill the holes. An anti-reflective material is formed on the filled interlayer insulating film, and a photoresist film patterned into a groove pattern is further formed thereon. After that, the substrate is treated at 170 ° C. for 2 minutes, and the photoresist film is used as a mask. , The antireflection film, the interlayer insulating film, and the OFPR-800 in the hole were etched in the same manner. Although grooves were formed, the OFPR-800 in the holes could not be removed, and wiring could not be formed by embedding copper.
[0116]
Comparative Example 6
Varnish A was changed to varnish A1 obtained in Comparative Example 2, applied to deep holes obtained in the same manner as in Example 7, and baked at 130 ° C. for 3 minutes, thereby embedding these holes. An anti-reflective material is formed on the filled interlayer insulating film, and a photoresist film patterned into a groove pattern is further formed thereon. After that, processing is performed at 160 ° C. for 2 minutes, and the photoresist film is used as a mask. The antireflection film, the interlayer insulating film, and the varnish A1 in the hole were etched in the same manner. Although a groove was formed, the varnish A1 in the hole could not be removed, and wiring could not be formed by embedding copper.
[0117]
Table 1 shows the compositions of Examples 1 to 6 and Comparative Examples 1 to 4, and Table 2 shows the evaluation results.
[0118]
[Table 1]

[0119]
[Table 2]

[0120]
【The invention's effect】
According to the present invention, since the etching rate of the film obtained by the post-processing method is higher than the etching rate of the composition film obtained by the pre-processing, a composition having excellent removability by dry etching is obtained. The obtained composition can be suitably used particularly as a multilayer wiring structure using a damascene method, and an organic flattening film or an antireflection film when forming such a multilayer wiring structure. it can.

Claims (9)

Light and / or heat treatment (pre-treatment) makes the composition insoluble in an organic solvent and / or an alkaline aqueous solution, and further, after light and / or heat treatment (post-treatment), a dry-etching treatment. A composition for a semiconductor device, which is 1.2 times or more the etching rate after the pretreatment, and the composition contains the following (a) and / or (b):
(A) a polymer soluble in an organic low-molecular compound that is liquid at 23 ° C. atmospheric pressure; (b) a low-molecular compound having a polymerizable group and / or a crosslinkable group The composition for a semiconductor device according to claim 1, further comprising (c) an acid generator. The composition according to claim 1, which comprises the component (a) and the component (b) or the component (a), wherein the component (a) has a polymerizable group and / or a crosslinkable group. The composition for a semiconductor device according to claim 1, further comprising: The composition for a semiconductor device according to claim 1, wherein the component (a) contains an acid dissociable group. The composition for a semiconductor device according to claim 1, wherein the component (b) contains an acid dissociable group. 3. The composition for a semiconductor device according to claim 2, wherein the component (c) generates an acid by light and / or heat. The composition for a semiconductor device according to claim 1, wherein the composition for a semiconductor device contains (d) a radical generator that generates a radical by light and / or heat. The composition for a semiconductor device according to claim 1, wherein the light is ultraviolet light. A lower wiring layer; an interlayer insulating film covering the lower wiring layer; and an opening (hole) formed in the interlayer insulating film on the lower wiring layer. A method of manufacturing a semiconductor device having an upper wiring layer connected to the lower wiring layer through a wiring groove, the wiring groove serving as an etching mask when forming a wiring groove on an interlayer insulating film on the lower wiring layer. Etching is removed between the step of forming a pattern layer and the step of forming an opening pattern layer serving as an etching mask when forming a connection opening (hole) on the wiring groove pattern layer. A method for manufacturing a semiconductor device, comprising forming an organic planarization film using the composition according to claim 1.