JP4298391B2 - Blue-violet light-sensitive composition, and image forming material, image forming material, and image forming method using the same - Google Patents

Description

【００２７】
〔式(I) 中、Ｒ¹ 、Ｒ² 、Ｒ⁵ 、及びＲ⁶ は各々独立して、置換基を有していてもよいアルキル基を示し、Ｒ³ 、Ｒ⁴ 、Ｒ⁷ 、及びＲ⁸ は各々独立して、置換基を有していてもよいアルキル基、又は水素原子を示し、Ｒ¹ とＲ² 、Ｒ³ とＲ⁴ 、Ｒ¹ とＲ³ 、Ｒ² とＲ⁴ 、Ｒ⁵ とＲ⁷ 、及びＲ⁶ とＲ⁸ とは各々独立して、含窒素複素環を形成していてもよい。〕
【００２８】
ここで、式(I) 中のＲ¹ 、Ｒ² 、Ｒ⁵ 、及びＲ⁶ のアルキル基の炭素数、並びに、Ｒ³ 、Ｒ⁴ 、Ｒ⁷ 、及びＲ⁸ がアルキル基であるときの炭素数は１〜６であるのが好ましい。又、含窒素複素環を形成する場合、５又は６員環であるのが好ましく、Ｒ¹ とＲ³ 、Ｒ² とＲ⁴ 、Ｒ⁵ とＲ⁷ 、又はＲ⁶ とＲ⁸ が６員環のテトラヒドロキノリン環を形成しているのが好ましく、Ｒ¹ とＲ² とＲ³ とＲ⁴ 、又は／及び、Ｒ⁵ とＲ⁶ とＲ⁷ とＲ⁸ がジュロリジン環を形成しているのが特に好ましい。更に、２位にアルキル基を置換基として有するテトラヒドロキノリン環、或いは該テトラヒドロキノリン環を含むジュロリジン環が殊更好ましい。
【００２９】
前記一般式(I) で表される化合物の具体例としては、例えば、４，４’−ビス（ジメチルアミノ）ベンゾフェノン、４，４’−ビス（ジエチルアミノ）ベンゾフェノン、及び、下記構造の化合物が挙げられる。
【００３０】
【化５】

【００３１】
又、ベンゼン環上のアミノ基に対してｐ−位の炭素原子に複素環基を置換基として有するジアルキルアミノベンゼン系化合物における複素環基としては、窒素原子、酸素原子、又は硫黄原子を含む５又は６員環のものが好ましく、縮合ベンゼン環を有する５員環が特に好ましく、下記一般式(II)で表されるものが好ましい。
【００３２】
【化６】

【００３３】
〔式(II)中、Ｒ¹ 及びＲ² は各々独立して、置換基を有していてもよいアルキル基を示し、Ｒ³ 及びＲ⁴ は各々独立して、置換基を有していてもよいアルキル基、又は水素原子を示し、Ｒ¹ とＲ² 、Ｒ¹ とＲ³ 、及びＲ² とＲ⁴ とは各々独立して、含窒素複素環を形成していてもよく、Ｘは、酸素原子、硫黄原子、ジアルキルメチレン基、イミノ基、又はアルキルイミノ基を示し、複素環に縮合するベンゼン環は置換基を有していてもよい。〕
【００３４】
ここで、式(II)中のＲ¹ 及びＲ² のアルキル基の炭素数、並びに、Ｒ³ 及びＲ⁴ がアルキル基であるときの炭素数は１〜６であるのが好ましく、又、含窒素複素環を形成する場合、５又は６員環であるのが好ましく、Ｒ¹ とＲ³ 、Ｒ² とＲ⁴ 、Ｒ⁵ とＲ⁷ 、又はＲ⁶ とＲ⁸ が６員環のテトラヒドロキノリン環を形成しているのが好ましく、Ｒ¹ とＲ² とＲ³ とＲ⁴ 、又は／及び、Ｒ⁵ とＲ⁶ とＲ⁷ とＲ⁸ がジュロリジン環を形成しているのが特に好ましい。更に、２位にアルキル基を置換基として有するテトラヒドロキノリン環、或いは該テトラヒドロキノリン環を含むジュロリジン環が殊更好ましい。又、Ｘがジアルキルメチレン基であるときのアルキル基の炭素数は１〜６であるのが好ましく、アルキルイミノ基であるときのアルキル基の炭素数は１〜６であるのが好ましい。
【００３５】
前記一般式(II)で表される化合物の具体例としては、例えば、２−（ｐ−ジメチルアミノフェニル）ベンゾオキサゾール、２−（ｐ−ジエチルアミノフェニル）ベンゾオキサゾール、２−（ｐ−ジメチルアミノフェニル）ベンゾ〔４，５〕ベンゾオキサゾール、２−（ｐ−ジメチルアミノフェニル）ベンゾ〔６，７〕ベンゾオキサゾール、２−（ｐ−ジメチルアミノフェニル）ベンゾチアゾール、２−（ｐ−ジエチルアミノフェニル）ベンゾチアゾール、２−（ｐ−ジメチルアミノフェニル）ベンゾイミダゾール、２−（ｐ−ジエチルアミノフェニル）ベンゾイミダゾール、２−（ｐ−ジメチルアミノフェニル）−３，３−ジメチル−３Ｈ−インドール、２−（ｐ−ジエチルアミノフェニル）−３，３−ジメチル−３Ｈ−インドール、及び、下記構造の化合物が挙げられる。
【００３６】
【化７】

【００３７】
又、前記一般式(II)で表される化合物以外の、ベンゼン環上のアミノ基に対してｐ−位の炭素原子に複素環基を置換基として有するジアルキルアミノベンゼン系化合物としては、例えば、２−（ｐ−ジメチルアミノフェニル）ピリジン、２−（ｐ−ジエチルアミノフェニル）ピリジン、２−（ｐ−ジメチルアミノフェニル）キノリン、２−（ｐ−ジエチルアミノフェニル）キノリン、２−（ｐ−ジメチルアミノフェニル）ピリミジン、２−（ｐ−ジエチルアミノフェニル）ピリミジン、２，５−ビス（ｐ−ジエチルアミノフェニル）−１，３，４−オキサジアゾール、２，５−ビス（ｐ−ジエチルアミノフェニル）−１，３，４−チアジアゾール等が挙げられる。
【００３８】
又、ベンゼン環上のアミノ基に対してｐ−位の炭素原子にスルホニルイミノ基を含む置換基を有するジアルキルアミノベンゼン系化合物としては、下記一般式(III) で表されるものが好ましい。
【００３９】
【化８】

【００４０】
〔式(III) 中、Ｒ¹ 及びＲ² は各々独立して、置換基を有していてもよいアルキル基を示し、Ｒ³ 及びＲ⁴ は各々独立して、置換基を有していてもよいアルキル基、又は水素原子を示し、Ｒ¹ とＲ² 、Ｒ¹ とＲ³ 、及びＲ² とＲ⁴ とは各々独立して、含窒素複素環を形成していてもよく、Ｒ⁹ は１価基、又は水素原子を示し、Ｒ¹⁰は１価基を示す。〕
【００４１】
ここで、式(III) 中のＲ¹ 及びＲ² のアルキル基の炭素数、並びに、Ｒ³ 及びＲ⁴ がアルキル基であるときの炭素数は１〜６であるのが好ましく、又、含窒素複素環を形成する場合、５又は６員環であるのが好ましいが、Ｒ³ 及びＲ⁴ は水素原子であるのが好ましい。又、Ｒ⁹ 及びＲ¹⁰の１価基としては、例えば、アルキル基、シクロアルキル基、アルケニル基、シクロアルケニル基、アルコキシ基、アルケニルオキシ基、アシル基、アシルオキシ基、アリール基、アリールオキシ基、アラルキル基、アリールアルケニル基、ヒドロキシ基、ホルミル基、カルボキシル基、カルボン酸エステル基、カルバモイル基、アミノ基、アシルアミノ基、カーバメート基、スルホンアミド基、スルホン酸基、スルホン酸エステル基、スルファモイル基、アルキルチオ基、イミノ基、シアノ基、及び複素環基等が挙げられる。これらの中で、Ｒ⁹ としては水素原子が、又、Ｒ¹⁰としてはアリール基が好ましい。
【００４２】
又、カルボスチリル骨格を形成したジアルキルアミノベンゼン系化合物としては、下記一般式(IV)で表されるものが好ましい。
【００４３】
【化９】

【００４４】
〔式(IV)中、Ｒ¹ 、Ｒ² 、及びＲ¹¹は各々独立して、置換基を有していてもよいアルキル基を示し、Ｒ³ 及びＲ⁴ は各々独立して、置換基を有していてもよいアルキル基、又は水素原子を示し、Ｒ¹ とＲ² 、Ｒ¹ とＲ³ 、及びＲ² とＲ⁴ とは各々独立して、含窒素複素環を形成していてもよく、Ｒ¹²は置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、又は水素原子を示す。〕
【００４５】
ここで、式(IV)中のＲ¹ 、Ｒ² 、及びＲ¹¹のアルキル基の炭素数、並びに、Ｒ³ 、Ｒ⁴ 、及びＲ¹²がアルキル基であるときの炭素数は１〜６であるのが好ましく、又、含窒素複素環を形成する場合、５又は６員環であるのが好ましいが、Ｒ³ 及びＲ⁴ は水素原子であるのが好ましい。又、Ｒ¹²としてはフェニル基であるのが好ましい。
【００４６】
以上の（Ｂ）成分の増感度色素として、本発明においては、前記一般式(I) で表されるジアルキルアミノベンゾフェノン系化合物、前記一般式(III) で表される、ベンゼン環上のアミノ基に対してｐ−位の炭素原子にスルホニルイミノ基を含む置換基を有するジアルキルアミノベンゼン系化合物、又は、前記一般式(IV)で表される、カルボスチリル骨格を形成したジアルキルアミノベンゼン系化合物が特に好ましい。
【００４７】
又、本発明の青紫光感光性組成物を構成する（Ｃ）成分の光重合開始剤は、前記（Ｂ）成分の増感色素等との共存下で光照射されたときに、増感色素の光励起エネルギーを受け取って活性ラジカルを発生し、前記（Ａ）成分のエチレン性不飽和化合物を重合に到らしめるラジカル発生剤であり、本発明においては、ヘキサアリールビイミダゾール系化合物又はチタノセン系化合物のいずれかであることを必須とする。
【００４８】
そのヘキサアリールビイミダゾール系化合物としては、具体的には、例えば、２，２’−ビス（ｏ−メトキシフェニル）−４，４’，５，５’−テトラフェニルビイミダゾール、２，２’−ビス（ｐ−メトキシフェニル）−４，４’，５，５’−テトラフェニルビイミダゾール、２，２’−ビス（フルオロフェニル）−４，４’，５，５’−テトラフェニルビイミダゾール、２，２’−ビス（ｏ−クロロフェニル）−４，４’，５，５’−テトラフェニルビイミダゾール、２，２’−ビス（ｏ−クロロフェニル）−４，４’，５，５’−テトラ（ｐ−メチルフェニル）ビイミダゾール、２，２’−ビス（ｏ−クロロフェニル）−４，４’，５，５’−テトラ（ｐ−メトキシフェニル）ビイミダゾール、２，２’−ビス（ｏ−クロロフェニル）−４，４’，５，５’−テトラ（ｏ，ｐ−ジメトキシフェニル）ビイミダゾール、２，２’−ビス（ｏ，ｐ−ジクロロフェニル）−４，４’，５，５’−テトラ（ｐ−メトキシフェニル）ビイミダゾール、２，２’−ビス（ｏ−クロロフェニル）−４，４’，５，５’−テトラ（ｐ−エトキシカルボニルフェニル）ビイミダゾール、２，２’−ビス（ｏ−クロロフェニル）−４，４’，５，５’−テトラ（ｐ−クロロフェニル）ビイミダゾール、２，２’−ビス（ｏ−クロロフェニル）−４，４’，５，５’−テトラ（ｏ，ｐ−ジクロロフェニル）ビイミダゾール、２，２’−ビス（ｏ，ｐ−ジクロロフェニル）−４，４’，５，５’−テトラ（ｏ，ｐ−ジクロロフェニル）ビイミダゾール、２，２’−ビス（ｏ−クロロフェニル）−４，４’，５，５’−テトラ（ｐ−フルオロフェニル）ビイミダゾール、２，２’−ビス（ｏ−クロロフェニル）−４，４’，５，５’−テトラ（ｏ，ｐ−ジブロモフェニル）ビイミダゾール、２，２’−ビス（ｏ−ブロモフェニル）−４，４’，５，５’−テトラ（ｏ，ｐ−ジクロロフェニル）ビイミダゾール、２，２’−ビス（ｏ−ブロモフェニル）−４，４’，５，５’−テトラ（ｐ−ヨードフェニル）ビイミダゾール、２，２’−ビス（ｏ−ブロモフェニル）−４，４’，５，５’−テトラ（ｐ−クロロ−ｐ−メトキシフェニル）ビイミダゾール、２，２’−ビス（ｏ−ブロモフェニル）−４，４’，５，５’−テトラ（ｏ−クロロ−ｐ−メトキシフェニル）ビイミダゾール、２，２’−ビス（ｏ−クロロフェニル）−４，４’，５，５’−テトラ（ｐ−クロロナフチル）ビイミダゾール等が挙げられる。中で、ヘキサフェニルビイミダゾール化合物が好ましく、そのイミダゾール環上の２，２’−位に結合したベンゼン環のｏ−位がハロゲン原子で置換されたものが更に好ましく、そのイミダゾール環上の４，４’，５，５’−位に結合したベンゼン環が無置換、又は、ハロゲン原子或いはアルコキシカルボニル基で置換されたものが特に好ましい。
【００４９】
又、そのチタノセン系化合物としては、具体的には、例えば、ジシクロペンタジエニルチタニウムジクロライド、ジシクロペンタジエニルチタニウムビスフェニル、ジシクロペンタジエニルチタニウムビス（２，４−ジフルオロフェニル）、ジシクロペンタジエニルチタニウムビス（２，６−ジフルオロフェニル）、ジシクロペンタジエニルチタニウムビス（２，４，６−トリフルオロフェニル）、ジシクロペンタジエニルチタニウムビス（２，３，５，６−テトラフルオロフェニル）、ジシクロペンタジエニルチタニウムビス（２，３，４，５，６−ペンタフルオロフェニル）、ジ（メチルシクロペンタジエニル）チタニウムビス（２，６−ジフルオロフェニル）、ジ（メチルシクロペンタジエニル）チタニウムビス（２，４，６−トリフルオロフェニル）、ジ（メチルシクロペンタジエニル）チタニウムビス（２，３，５，６−テトラフルオロフェニル）、ジ（メチルシクロペンタジエニル）チタニウムビス（２，３，４，５，６−ペンタフルオロフェニル）、ジシクロペンタジエニルチタニウムビス〔２，６−ジフルオロ−３−（１−ピロリル）フェニル〕等が挙げられる。中で、ジシクロペンタジエニル構造とビフェニル構造を有するチタン化合物が好ましく、ビフェニル環のｏ−位がハロゲン原子で置換されたものが特に好ましい。
【００５０】
尚、本発明の感光性組成物における光重合開始剤としては、（Ｃ）成分の前記ヘキサアリールビイミダゾール系化合物又は前記チタノセン系化合物のいずれかを含有することを必須とし、それらが単独で用いられても２種以上が併用されてもよい。又、その他の光重合開始剤を含有していてもよく、その光重合開始剤としては、例えば、ハロメチル化ｓ−トリアジン誘導体、ハロメチル化１，３，４−オキサジアゾール誘導体、有機硼素酸塩、ジアリールヨードニウム塩、カルボニル化合物、及び有機過酸化物等が挙げられる。
【００５１】
又、本発明の青紫光感光性組成物を構成する（Ｄ）成分のアルカリ可溶性樹脂は、基板上への感光性組成物の層としての形成性、及び現像性の向上等を目的とするものであり、本発明においては、そのアルカリ可溶性樹脂として、エチレン性不飽和カルボン酸に由来する構成繰返し単位とエポキシ基含有エチレン性不飽和化合物に由来する構成繰返し単位とを含むカルボキシル基及びエポキシ基含有ビニル系共重合体からなるものであることが必須であり、該共重合体は、エチレン性不飽和カルボン酸に由来する構成繰返し単位とエポキシ基含有エチレン性不飽和化合物に由来する構成繰返し単位の他に、共重合可能な他単量体に由来する構成繰返し単位を含むのが好ましい。
【００５２】
ここで、前記共重合体におけるエチレン性不飽和カルボン酸としては、例えば、（メタ）アクリル酸、クロトン酸等のモノカルボン酸類、マレイン酸、フマル酸、シトラコン酸、メサコン酸、イタコン酸等のジカルボン酸類、琥珀酸モノ〔２−（メタ）アクリロイルオキシエチル〕、フタル酸モノ〔２−（メタ）アクリロイルオキシエチル〕等の多価カルボン酸のモノ〔（メタ）アクリロイルオキシアルキル〕エステル類、ω−カルボキシポリカプロラクトンモノ（メタ）アクリレート等の、両末端にカルボキシル基と水酸基とを有するポリマーのモノ（メタ）アクリレート類等が挙げられ、これらは単独で用いられていてもよく、２種以上を組み合わせて用いられていてもよい。これらの中で、共重合反応性、及び、画像形成材としての感光性組成物層の露光後のアルカリ現像液に対する溶解性等の面から、（メタ）アクリル酸が好ましい。
【００５３】
又、エポキシ基含有エチレン性不飽和化合物としては、例えば、（メタ）アクリル酸グリシジル、（メタ）アクリル酸２−メチルグリシジル、（メタ）アクリル酸３，４−エポキシブチル、（メタ）アクリル酸６，７−エポキシヘプチル等の（メタ）アクリル酸エポキシアルキルエステル類、α−エチルアクリル酸グリシジル、α−ｎ−プロピルアクリルグリシジル、α−ｎ−ブチルアクリルグリシジル、α−エチルアクリル酸６，７−エポキシヘプチル等のα−アルキルアクリル酸エポキシアルキルエステル類、ｏ−ビニルベンジルグリシジルエーテル、ｍ−ビニルベンジルグリシジルエーテル、ｐ−ビニルベンジルグリシジルエーテル等のグリシジルエーテル類、（メタ）アクリル酸３，４−エポキシシクロヘキシルメチル、（メタ）アクリル酸２，３−エポキシシクロペンチルメチル、（メタ）アクリル酸７，８−エポキシ〔トリシクロ［５．２．１．０］デシ−２−イル〕メチル等の（メタ）アクリル酸脂環式エポキシアルキルエステル類等が挙げられ、これらは単独で用いられていてもよく、２種以上を組み合わせて用いられていてもよい。これらの中で、共重合反応性、及び、画像形成材としての感光性組成物層の露光後のアルカリ現像性、及び現像処理後の膜強度等の面から、（メタ）アクリル酸グリシジル、（メタ）アクリル酸３，４−エポキシシクロヘキシルメチル、（メタ）アクリル酸２，３−エポキシシクロペンチルメチル等が好ましい。
【００５４】
又、共重合可能な他単量体としては、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ−プロピル、（メタ）アクリル酸ｉ−プロピル、（メタ）アクリル酸ｎ−ブチル、（メタ）アクリル酸ｉ−ブチル、（メタ）アクリル酸ｓｅｃ−ブチル、（メタ）アクリル酸ｔ−ブチル等の（メタ）アクリル酸アルキルエステル類、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸２−エチルシクロヘキシル、（メタ）アクリル酸イソボロニル、（メタ）アクリル酸トリシクロ〔５．２．１．０^2,6 〕デカン−８−イル、（メタ）アクリル酸（トリシクロ〔５．２．１．０^2,6 〕デカン−８−イルオキシ）エチル等の（メタ）アクリル酸脂環式エステル類、（メタ）アクリル酸フェニル等の（メタ）アクリル酸アリールエステル類、（メタ）アクリル酸ベンジル等の（メタ）アクリル酸アラルキルエステル類、マレイン酸ジエチル、フマル酸ジエチル、イタコン酸ジエチル等のジカルボン酸ジアルキルエステル類、（メタ）アクリル酸２−ヒドロキシエチル、（メタ）アクリル酸２−ヒドロキシプロピル等の（メタ）アクリル酸ヒドロキシアルキルエステル類、スチレン、α−メチルスチレン、α−エチルスチレン等のα−置換アルキルスチレン、ｏ−メチルスチレン、ｍ−メチルスチレン、ｐ−メチルスチレン、２，５−ジメチルスチレン等の核置換アルキルスチレン、ｏ−ヒドロキシスチレン、ｍ−ヒドロキシスチレン、ｐ−ヒドロキシスチレン、ジヒドロキシスチレン等の核置換ヒドロキシスチレン、ｐ−クロロスチレン、ｐ−ブロモスチレン、ジブロモスチレン等の核置換ハロゲン化スチレン等のビニル芳香族化合物類、１，３−ブタジエン、イソプレン、２，３−ジメチル１，３−ブタジエン等の共役ジエン化合物類、（メタ）アクリロニトリル、（メタ）アクリルアミド、Ｎ−メチロール（メタ）アクリルアミド、Ｎ，Ｎ−ジメチル（メタ）アクリルアミド、Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリルアミド等の（メタ）アクリル酸誘導体、及び、酢酸ビニル、塩化ビニル等のビニル化合物類等が挙げられ、これらは単独で用いられていてもよく、２種以上を組み合わせて用いられていてもよい。これらの中で、共重合反応性、及び、画像形成材としての感光性組成物層の露光後のアルカリ現像液に対する溶解性等の面から、（メタ）アクリル酸ｉ−プロピル、（メタ）アクリル酸ｉ−ブチル、（メタ）アクリル酸ｔ−ブチル、（メタ）アクリル酸２−メチルヘキシル等の（メタ）アクリル酸分岐アルキルエステル類、及び、スチレン、α−メチルスチレン等のビニル芳香族化合物類が好ましく、（メタ）アクリル酸ｔ−ブチル、スチレンが特に好ましい。
【００５５】
本発明において、前記共重合体の、前記エチレン性不飽和カルボン酸に由来する構成繰返し単位、前記エポキシ基含有エチレン性不飽和化合物に由来する構成繰返し単位、及び、前記共重合可能な他単量体に由来する構成繰返し単位の各含有割合は、共重合体全量に対して、エチレン性不飽和カルボン酸に由来する構成繰返し単位が５〜３０重量％、エポキシ基含有エチレン性不飽和化合物に由来する構成繰返し単位が５〜４０重量％、共重合可能な他単量体に由来する構成繰返し単位が３０〜９０重量％であるのが好ましく、エチレン性不飽和カルボン酸に由来する構成繰返し単位が１０〜２５重量％、エポキシ基含有エチレン性不飽和化合物に由来する構成繰返し単位が１０〜３５重量％、共重合可能な他単量体に由来する構成繰返し単位が４０〜８０重量％であるのが特に好ましい。
【００５６】
エチレン性不飽和カルボン酸に由来する構成繰返し単位の割合が前記範囲未満では、画像形成材としての感光性組成物層の露光後のアルカリ現像液に対する溶解性が低下する傾向となり、一方、前記範囲超過では、感光性組成物塗布液としての保存安定性が低下する傾向となる。又、エポキシ基含有エチレン性不飽和化合物に由来する構成繰返し単位の割合が前記範囲未満では、現像処理における非画像部分の抜け性が劣り、又、現像処理後の膜強度が低下する傾向となり、一方、前記範囲超過では、感光性組成物塗布液としての保存安定性が低下する傾向となる。又、共重合可能な他単量体に由来する構成繰返し単位の割合が前記範囲未満では、感光性組成物塗布液としての保存安定性が低下したり、現像処理における画像部が膜減りする傾向となり、一方、前記範囲超過では、現像処理における地汚れが発生し易い傾向となる。
【００５７】
又、共重合可能な他単量体の中で、共重合体全量に対して、特に好ましいとする（メタ）アクリル酸ｔ−ブチルに由来する構成繰返し単位の割合が１５〜５０重量％、特には２０〜４５重量％であり、特に好ましいとするスチレンに由来する構成繰返し単位の割合が１５〜４０重量％、特には２０〜３５重量％であるのが好ましい。
【００５８】
尚、これら共重合体は、酸価が３０〜２５０ｍｇ・ＫＯＨ／ｇ、ポリスチレン換算の重量平均分子量が１，０００〜３００，０００であるのが好ましい。
【００５９】
又、本発明の感光性組成物おけるアルカリ可溶性樹脂としては、前記（Ｄ）成分の共重合体の他に、例えば、（メタ）アクリル酸、（メタ）アクリル酸エステル、（メタ）アクリロニトリル、（メタ）アクリルアミド、マレイン酸、スチレン、酢酸ビニル、塩化ビニリデン、マレイミド等の単独又は共重合体、並びに、ポリアミド、ポリエステル、ポリエーテル、ポリウレタン、ポリビニルブチラール、ポリビニルアルコール、ポリビニルピロリドン、アセチルセルロース等を、本発明の効果を損なわない範囲で含有していてもよい。
【００６０】
本発明の青紫光感光性組成物において、前記（Ａ）成分のエチレン性不飽和化合物、前記（Ｂ）成分の増感色素、前記（Ｃ）成分の光重合開始剤、及び前記（Ｄ）成分のアルカリ可溶性樹脂の各含有割合は、感光性組成物の全量に対して、（Ａ）成分が２０〜８０重量％、（Ｂ）成分が０．０１〜３０重量％、（Ｃ）成分が０．１〜３０重量％、（Ｄ）成分が２０〜７０重量％であるのが好ましく、（Ａ）成分が３０〜７０重量％、（Ｂ）成分が０．１〜２０重量％、（Ｃ）成分が０．５〜２０重量％、（Ｄ）成分が３０〜６０重量％であるのが特に好ましい。
【００６１】
又、本発明の青紫光感光性組成物は、光重合開始能力の向上等を目的として、更に、水素供与性化合物を含有していてもよく、その水素供与性化合物としては、例えば、２−メルカプトベンゾチアゾール、２−メルカプトベンゾイミダゾール、２−メルカプトベンゾオキサゾール、３−メルカプト−１，２，４−トリアゾール、２−メルカプト−４（３Ｈ）−キナゾリン、β−メルカプトナフタレン、エチレングリコールジチオプロピオネート、トリメチロールプロパントリスチオプロピオネート、ペンタエリスリトールテトラキスチオプロピオネート等のメルカプト基含有化合物類、ヘキサンジチオール、トリメチロールプロパントリスチオグリコネート、ペンタエリスリトールテトラキスチオプロピオネート等の多官能チオール化合物類、Ｎ，Ｎ−ジアルキルアミノ安息香酸エステル、Ｎ−フェニルグリシン、又はそのエステル、そのアンモニウムやナトリウム塩等の塩、その双極イオン化合物等の誘導体、フェニルアラニン、又はそのエステル、そのアンモニウムやナトリウム塩等の塩、その双極イオン化合物等の誘導体等の芳香族環を有するアミノ酸又はその誘導体類等が挙げられる。中で、本発明においては、メルカプト基含有化合物類、及び、アミノ酸又はその誘導体類が好ましい。
【００６２】
更に、本発明の青紫光感光性組成物は、後述する露光後の膜に耐熱性や耐薬品性等を付与することを目的として、エポキシ基含有化合物を含有していてもよく、そのエポキシ基含有化合物としては、所謂エポキシ樹脂の繰返し単位を構成する、ポリヒドロキシ化合物とエピクロルヒドリンを反応させて得られるポリグリシジルエーテル化合物、ポリカルボン酸化合物とエピクロルヒドリンを反応させて得られるポリグリシジルエステル化合物、及び、ポリアミン化合物とエピクロルヒドリンを反応させて得られるポリグリシジルアミン化合物等の、低分子量物から高分子量物にわたる化合物が挙げられる。
【００６３】
これらのポリグリシジルエーテル化合物として、具体的には、例えば、ポリエチレングリコールのジグリシジルエーテル型エポキシ、ビス（４−ヒドロキシフェニル）のジグリシジルエーテル型エポキシ、ビス（３，５−ジメチル−４−ヒドロキシフェニル）のジグリシジルエーテル型エポキシ、ビスフェノールＦのジグリシジルエーテル型エポキシ、ビスフェノールＡのジグリシジルエーテル型エポキシ、テトラメチルビスフェノールＡのジグリシジルエーテル型エポキシ、エチレンオキシド付加ビスフェノールＡのジグリシジルエーテル型エポキシ、フェノールノボラック型エポキシ、クレゾールノボラック型エポキシ等が挙げられ、これらのポリグリシジルエーテル化合物には、残存するヒドロキシル基に酸無水物や２価の酸化合物を反応させカルボキシル基を導入することもできる。又、ポリグリシジルエステル化合物として、具体的には、例えば、ヘキサヒドロフタル酸のジグリシジルエステル型エポキシ、フタル酸のジグリシジルエステル型エポキシ等が、又、ポリグリシジルアミン化合物として、具体的には、例えば、ビス（４−アミノフェニル）メタンのジグリシジルアミン型エポキシ、イソシアヌル酸のトリグリシジルアミン型エポキシ等が、それぞれ挙げられる。
【００６４】
又、同様の目的のものとして、例えばピロメリット酸二無水物等のテトラカルボン酸又はその誘導体と例えば３，３’−ジメチル−４，４’−ジアミノビフェニル等のジアミンとがアミド結合を形成して得られ、酸官能基又はエチレン性不飽和結合を有するポリイミド前駆体も挙げられる。
【００６５】
本発明の青紫光感光性組成物における前記水素供与性化合物、及び前記エポキシ基含有化合物の各含有割合は、感光性組成物の全量に対して、各々、１０重量％以下であるのが好ましく、５重量％以下であるのが更に好ましい。
【００６６】
更に、本発明の青紫光感光性組成物は、各種添加剤、例えば、ハイドロキノン、ｐ−メトキシフェノール、２，６−ジ−ｔ−ブチル−ｐ−クレゾール等の熱重合防止剤を、感光性組成物の全量に対して２重量％以下、有機又は無機の染顔料からなる着色剤を同じく２０重量％以下、ジオクチルフタレート、ジドデシルフタレート、トリクレジルホスフェート等の可塑剤を同じく４０重量％以下、三級アミンやチオール等の感度特性改善剤を同じく１０重量％以下、色素前駆体を同じく３０重量％以下、の割合で含有していてもよい。
【００６７】
本発明の青紫光感光性組成物は、３９０〜４３０ｎｍの波長域に分光感度の極大ピークを有するのが好ましく、４００〜４２０ｎｍの波長域に分光感度の極大ピークを有するのが更に好ましい。分光感度の極大ピークを前記範囲未満の波長域に有する場合には、感光性組成物として波長３９０〜４３０ｎｍのレーザー光等の露光光源に対する感度が劣り、一方、前記範囲超過の波長域に有する場合には、黄色灯下でのセーフライト性が劣ることとなる。
【００６８】
尚、本発明において、分光感度の極大ピークとは、例えば、「フォトポリマー・テクノロジー」（山岡亜夫著、昭和６３年日刊工業新聞社発行、第２６２頁）等に詳述されているように、基板表面に感光性層を形成した感光性画像形成材試料を、分光感度測定装置を用い、キセノンランプ又はタングステンランプ等の光源から分光した光を、横軸方向に露光波長が直線的に、縦軸方向に露光強度が対数的に変化するように設定して照射して露光した後、現像処理することにより、各露光波長の感度に応じた画像が得られ、その画像高さから画像形成可能な露光エネルギーを算出し、横軸に波長、縦軸にその露光エネルギーの逆数をプロットすることにより得られる分光感度曲線における極大ピークを指す。
【００６９】
又、本発明の青紫光感光性組成物は、波長４１０ｎｍにおける画像形成可能な最小露光量〔Ｓ₄₁₀ 〕が１０ｍＪ／ｃｍ² 以下であるのが好ましく、７ｍＪ／ｃｍ² 以下であるのが更に好ましく、５ｍＪ／ｃｍ² 以下であるのが特に好ましい。この最小露光量〔Ｓ₄₁₀ 〕が前記範囲超過では、レーザー光等の露光光源の露光強度にもよるが、露光時間が長くなって実用性が低下することとなる。尚、この最小露光量〔Ｓ₄₁₀ 〕の下限は小さい程好ましいが、通常１ｍＪ／ｃｍ² 以上である。
【００７０】
又、本発明の青紫光感光性組成物は、前記〔Ｓ₄₁₀ 〕の波長４５０ｎｍにおける画像形成可能な最小露光量〔Ｓ₄₅₀ （ｍＪ／ｃｍ² ）〕に対する比〔Ｓ₄₁₀ ／Ｓ₄₅₀ 〕が０．１以下であるのが好ましく、０．０５以下であるのが更に好ましい。この比〔Ｓ₄₁₀ ／Ｓ₄₅₀ 〕が前記範囲超過では、青紫光感光性と黄色灯下でのセーフライト性を両立させることが困難となる。
【００７１】
又、本発明の青紫光感光性組成物は、波長４５０ｎｍ超過６５０ｎｍ以下の各波長における画像形成可能な最小露光量〔Ｓ_450-650 （ｍＪ／ｃｍ² ）〕の波長４５０ｎｍにおける画像形成可能な最小露光量〔Ｓ₄₅₀ （ｍＪ／ｃｍ² ）〕に対する比〔Ｓ_450-650 ／Ｓ₄₅₀ 〕が１超過であるのが好ましい。この比〔Ｓ_450-650 ／Ｓ₄₅₀ 〕が前記範囲以下では、青紫光感光性と黄色灯下でのセーフライト性を両立させることが困難な傾向となる。
【００７２】
尚、前記波長４１０ｎｍにおける画像形成可能な最小露光量〔Ｓ₄₁₀ 〕、波長４５０ｎｍにおける画像形成可能な最小露光量〔Ｓ₄₅₀ 〕、及び、波長４５０ｎｍ超過６５０ｎｍ以下の各波長における画像形成可能な最小露光量〔Ｓ_450-650 〕は、前述した分光感度測定装置を用いての分光感度の極大ピークの測定において、得られる画像高さから算出される画像形成可能な露光エネルギーとして求められ、その際の、現像液の種類、現像温度、現像時間等の現像条件を変化させて決定される最適現像条件で画像を形成し得る最小露光量を意味し、その最適現像条件としては、通常、ｐＨ１１〜１４のアルカリ現像液に温度２５℃で０．５〜３分浸漬する条件が採られる。
【００７３】
本発明の前記青紫光感光性組成物は、前記各成分を適当な溶剤に溶解或いは分散させた塗布液として、仮支持フィルム上に塗布し乾燥させ、必要に応じて、形成された感光性組成物層表面を被覆フィルムで覆うことにより、所謂ドライフィルムレジスト材等としての、本発明の青紫光感光性画像形成材料とされ、その画像形成材料の感光性組成物層側を、被覆フィルムで覆われている場合にはその被覆フィルムを剥離して、被加工基板上に積層することにより、又は、前記各成分を適当な溶剤に溶解或いは分散させた塗布液として、被加工基板上に直接に塗布し乾燥させることにより、被加工基板上に本発明の青紫光感光性組成物の層が形成された本発明の青紫光感光性画像形成材とされ、その画像形成材の青紫光感光性組成物層を、波長３９０〜４３０ｎｍのレーザー光により走査露光し、現像処理してネガ画像を現出させる画像形成方法としての使用形態に好適に用いられる。
【００７４】
そのドライフィルムレジスト材等としての画像形成材料として用いられる場合における仮支持フィルムとしては、例えば、ポリエチレンテレフタレートフィルム、ポリイミドフィルム、ポリアミドイミドフィルム、ポリプロピレンフィルム、ポリスチレンフィルム等の従来公知のフィルムが用いられる。その際、それらのフィルムが画像形成材料の作製時に必要な耐溶剤性や耐熱性等を有しているものであるときは、それらの仮支持フィルム上に直接に感光性組成物塗布液を塗布し乾燥させて本発明の画像形成材料を作製することができ、又、それらのフィルムが耐溶剤性や耐熱性等の低いものであっても、例えば、ポリテトラフルオロエチレンフィルムや離型フィルム等の離型性を有するフィルム上に先ず感光性組成物層を形成した後、その層上に耐溶剤性や耐熱性等の低い仮支持フィルムを積層し、しかる後、離型性を有するフィルムを剥離することにより、本発明の画像形成材料を作製することもできる。
【００７５】
又、塗布液に用いられる溶剤としては、使用成分に対して十分な溶解度を持ち、良好な塗膜性を与えるものであれば特に制限はないが、例えば、メチルセロソルブ、エチルセロソルブ、メチルセロソルブアセテート、エチルセロソルブアセテート等のセロソルブ系溶剤、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノブチルエーテルアセテート、ジプロピレングリコールジメチルエーテル等のプロピレングリコール系溶剤、酢酸ブチル、酢酸アミル、酪酸エチル、酪酸ブチル、ジエチルオキサレート、ピルビン酸エチル、エチル−２−ヒドロキシブチレート、エチルアセトアセテート、乳酸メチル、乳酸エチル、３−メトキシプロピオン酸メチル等のエステル系溶剤、ヘプタノール、ヘキサノール、ジアセトンアルコール、フルフリルアルコール等のアルコール系溶剤、シクロヘキサノン、メチルアミルケトン等のケトン系溶剤、ジメチルホルムアミド、ジメチルアセトアミド、Ｎ−メチルピロリドン等の高極性溶剤、或いはこれらの混合溶剤、更にはこれらに芳香族炭化水素を添加したもの等が挙げられる。溶剤の使用割合は、感光性組成物の総量に対して、通常、重量比で１〜２０倍程度の範囲である。
【００７６】
又、その塗布方法としては、従来公知の方法、例えば、ナイフコート法、ロールコート法、スプレーコート法、スピンコート法等を用いることができる。その際の塗布量は、後述する画像形成、及びそれに引き続くエッチングやメッキ等の加工性等の面から、乾燥膜厚として、通常５μｍ以上であり、ドライフィルムレジスト材としては１０μｍ以上であるのが好ましく、１５μｍ以上であるのが更に好ましく、又、感度等の面から、２００μｍ以下であるのが好ましく、１００μｍ以下であるのが更に好ましい。尚、その際の乾燥温度としては、例えば、３０〜１５０℃程度、好ましくは４０〜１１０℃程度、乾燥時間としては、例えば、５秒〜６０分間程度、好ましくは１０秒〜３０分間程度が採られる。
【００７７】
又、ドライフィルムレジスト材等としての画像形成材料として用いられる場合には、その画像形成材料が被加工基板に積層されるまでの間、形成された感光性組成物層表面を被覆フィルムで覆うことが好ましく、その被覆フィルムとしては、ポリエチレンフィルム、ポリプロピレンフィルム、ポリテトラフルオロエチレンフィルム等の従来公知のフィルムが用いられる。
【００７８】
又、前記画像形成材料の感光性組成物層側を、被覆フィルムで覆われている場合にはその被覆フィルムを剥離して、加熱、加圧等して積層することにより、又は、前記感光性組成物塗布液を直接に塗布し乾燥させることにより、本発明の画像形成材を作製するにおける被加工基板は、その上に形成される感光性組成物層をレーザー光により走査露光し現像処理することによって現出されたネガ画像をレジストとしてエッチング加工或いはメッキ加工等することにより、その表面に回路や電極等のパターンが形成されるものであり、銅、アルミニウム、金、銀、クロム、亜鉛、錫、鉛、ニッケル等の金属板そのものであってもよいが、通常、例えば、エポキシ樹脂、ポリイミド樹脂、ビスマレイミド樹脂、不飽和ポリエステル樹脂、フェノール樹脂、メラミン樹脂等の熱硬化性樹脂、飽和ポリエステル樹脂、ポリカーボネート樹脂、ポリスルホン樹脂、アクリル樹脂、ポリアミド樹脂、ポリスチレン樹脂、ポリ塩化ビニル樹脂、ポリオレフィン樹脂、弗素樹脂等の熱可塑性樹脂等の樹脂、紙、ガラス、及び、アルミナ、シリカ、硫酸バリウム、炭酸カルシウム等の無機物、又は、ガラス布基材エポキシ樹脂、ガラス不織布基材エポキシ樹脂、紙基材エポキシ樹脂、紙基材フェノール樹脂等の複合材料等からなり、その厚さが０．０２〜１０ｍｍ程度の絶縁性支持体表面に、前記金属或いは酸化インジウム、酸化錫、酸化インジウムドープ酸化錫等の金属酸化物等の金属箔を加熱、圧着ラミネートするか、金属をスパッタリング、蒸着、メッキする等の方法により、その厚さが１〜１００μｍ程度の導電層を形成した金属張積層板が、好ましく用いられる。
【００７９】
尚、前記感光性組成物塗布液を直接に塗布し乾燥させることにより、本発明の画像形成材を作製した場合には、前記被加工基板上に形成された感光性組成物層の酸素による重合禁止作用を防止する等のために、その感光性組成物層上に、例えば、ポリビニルアルコール、ポリビニルピロリドン、ポリエチレンオキサイド、メチルセルロース、カルボキシメチルセルロース、ヒドロキシエチルセルロース等の溶液の塗布、乾燥により形成した保護層が設けられてもよい。
【００８０】
そして、青紫光感光性組成物層を被加工基板上に有する本発明の前記画像形成材は、前記画像形成材料により感光性組成物層が形成されている場合には仮支持フィルムを剥離した後、又は、感光性組成物塗布液を直接に塗布し乾燥させることにより感光性組成物層が形成されている場合であって、前記保護層を有する場合にはその保護層を剥離した後、その感光性組成物層を、青紫光により、好ましくは青紫色レーザー光により走査露光した後、現像処理することにより、前記被加工基板上にネガ画像が形成される。
【００８１】
その露光光源としては、カーボンアーク灯、水銀灯、キセノンランプ、メタルハライドランプ、蛍光ランプ、タングステンランプ、ハロゲンランプ、及び、ＨｅＮｅレーザー、アルゴンイオンレーザー、ＹＡＧレーザー、ＨｅＣｄレーザー、半導体レーザー、ルビーレーザー等のレーザー光源が挙げられるが、特に、波長域３９０〜４３０ｎｍの青紫領域のレーザー光を発生する光源が好ましく、その中心波長が約４０５ｎｍのものであるのが更に好ましい。具体的には、４１０ｎｍを発振する窒化インジウムガリウム半導体レーザー等が挙げられる。
【００８２】
又、レーザー光による走査露光方法は、特に限定されるものではないが、例えば、平面走査露光方式、外面ドラム走査露光方式、内面ドラム走査露光方式等が挙げられ、レーザーの出力光強度を、好ましくは１〜１００ｍＷ、更に好ましくは３〜７０ｍＷ、発振波長を、好ましくは３９０〜４３０ｎｍ、更に好ましくは４００〜４２０ｎｍ、ビームスポット径を、好ましくは２〜３０μｍ、更に好ましくは４〜２０μｍ、走査速度を、好ましくは５０〜５００ｍ／秒、更に好ましくは１００〜４００ｍ／秒、走査密度を、好ましくは２，０００ｄｐｉ以上、更に好ましくは４，０００ｄｐｉ以上として、走査露光する。
【００８３】
又、前記露光後の現像処理は、好ましくはアルカリ成分と界面活性剤とを含有する水性現像液を用いてなされる。そのアルカリ成分としては、例えば、珪酸ナトリウム、珪酸カリウム、珪酸リチウム、珪酸アンモニウム、メタ珪酸ナトリウム、メタ珪酸カリウム、水酸化ナトリウム、水酸化カリウム、水酸化リチウム、炭酸ナトリウム、重炭酸ナトリウム、炭酸カリウム、第二燐酸ナトリウム、第三燐酸ナトリウム、第二燐酸アンモニウム、第三燐酸アンモニウム、硼酸ナトリウム、硼酸カリウム、硼酸アンモニウム等の無機アルカリ塩、モノメチルアミン、ジメチルアミン、トリメチルアミン、モノエチルアミン、ジエチルアミン、トリエチルアミン、モノイソプロピルアミン、ジイソプロピルアミン、モノブチルアミン、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、モノイソプロパノールアミン、ジイソプロパノールアミン等の有機アミン化合物等が挙げられ、その０．１〜５重量％程度の濃度で用いられる。
【００８４】
又、界面活性剤としては、ノニオン性、アニオン性、又は両性界面活性剤が好ましく、特に両性界面活性剤、就中、ベタイン型化合物類が好ましい。界面活性剤は、好ましくは０．０００１〜２０重量％、更に好ましくは０．０００５〜１０重量％、特に好ましくは０．００１〜５重量％の濃度で用いられる。
【００８５】
更に、現像液には、例えば、イソプロピルアルコール、ベンジルアルコール、エチルセロソルブ、ブチルセロソルブ、フェニルセロソルブ、プロピレングリコール、ジアセトンアルコール等の有機溶剤を必要に応じて含有させることができる。又、現像液のｐＨは、９〜１４とするのが好ましく、１１〜１４とするのが更に好ましい。
【００８６】
尚、現像は、通常、前記現像液に画像形成材を浸漬するか、画像形成材に前記現像液をスプレーする等の公知の現像法により、好ましくは１０〜５０℃程度、更に好ましくは２０〜４０℃程度の温度で、５秒〜１０分程度の時間でなされる。又、現像処理後、形成されたネガ画像を、例えば高圧水銀灯等の光源によって照射処理するか、又は／及び、例えば１４０〜１６０℃程度の温度で加熱処理することにより、レジストとしての耐薬品性等の向上を図ることができる。
【００８７】
【実施例】
以下、本発明を実施例により更に具体的に説明するが、本発明はその要旨を越えない限り、以下の実施例に限定されるものではない。
【００８８】
実施例１
被加工基板として、片面に厚み１８μｍの銅箔がラミネートされた厚み１００μｍのポリイミド樹脂の銅張積層基板（サンハヤト社製）を用い、その銅箔上に、青紫光感光性組成物として、（Ａ）成分のエチレン性不飽和化合物としての下記の（Ａ−１）、（Ｂ）成分の増感色素としての下記の（Ｂ−１）、（Ｃ）成分の光重合開始剤としての下記の（Ｃ−１）、及び（Ｄ）成分のアルカリ可溶性樹脂としての下記の（Ｄ−１）の各成分を、ヘキサノン／メチルセロソルブ（重量比５／５）の混合溶剤１，０００重量部に加えて室温で１０分間攪拌して調液した塗布液を、ワイヤーバーを用いて乾燥膜厚が６μｍとなる量で塗布し、８０℃で２分間乾燥させることにより、銅張積層基板上に青紫光感光性組成物層が形成された感光性画像形成材を作製した。
【００８９】
（Ａ−１）ジペンタエリスリトールヘキサアクリレート；５０重量部
（Ｂ−１）下記の化合物；２重量部
【００９０】
【化１０】

【００９１】
（Ｃ−１）２，２’−ビス（ｏ−クロロフェニル）−４，４’，５，５’−テトラフェニルビイミダゾール；５重量部
（Ｄ−１）メタクリル酸（１５重量％）／メタクリル酸グリシジル（３０重量）／メタクリル酸ｔ−ブチル（３０重量％）／スチレン（２５重量％）共重合体（重量平均分子量５０，０００）；５０重量部
【００９２】
得られた感光性画像形成材を、直径７ｃｍのアルミニウム製ドラムに感光性組成物層が外側になるように固定し、波長４０５ｎｍ、０．５ｍＷの半導体レーザー（キコー社製）を用いて、ビームスポット径５０μｍで、ドラム回転数を０．１〜１００ｒｐｍの範囲で変化させることにより露光量を変化させて走査露光した後、０．５重量％の珪酸ナトリウムと０．５重量％の界面活性剤（花王社製「ペレックスＮＢＬ」）とを含有する水溶液を現像液として現像処理することにより走査線画像を形成させ、その線画像が形成されるドラムの最高回転数より露光感度としての最小露光エネルギーを求めたところ、５ｍＪ／ｃｍ² であった。
【００９３】
更に、得られた感光性画像形成材を、前記と同様にして最小露光エネルギーの２倍量で走査露光し現像処理することにより作製したネガ画像をレジストとして、酸化鉄タイプ銅エッチング溶液（サンハヤト社製）に５分間浸漬して非画像部（非露光部）の銅エッチング処理を行い、次いで、３０℃の１重量％水酸化ナトリウム水溶液中に３分間浸漬してレジストを剥離、除去した後、線画像を目視にて観察したところ、非画像部（非露光部）の銅は完全にエッチングされており、且つ、画像部（露光部）の銅のエッチングは全く認められず、良質な線画像が描画されていると共に、レジストとしてのネガ画像は完全に除去されていた。
【００９４】
実施例２
（Ｃ）成分の光重合開始剤を下記の（Ｃ−２）に変えると共に、下記のその他成分（水素供与性化合物）を添加した青紫光感光性組成物を用いた外は、実施例１におけると同様にして、感光性画像形成材を作製した。最小露光エネルギーは４ｍＪ／ｃｍ² であり、又、実施例１におけると同様のエッチング特性を示した。
【００９５】
（Ｃ−２）ジシクロペンタジエニルチタニウムビス〔２，６−ジフルオロ−３−（１−ピロリル）フェニル〕；１重量部
（その他）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）ブタン−１−オン；５重量部
（その他）２，４−ジエチルチオキサントン；０．５重量部
【００９６】
実施例３
（Ｂ）成分の増感色素を下記の（Ｂ−２）に変えた青紫光感光性組成物を用いた外は、実施例１におけると同様にして、感光性画像形成材を作製した。最小露光エネルギーは２０ｍＪ／ｃｍ² であり、又、実施例１におけると同様のエッチング特性を示した。
【００９７】
（Ｂ−２）４，４’−ビス（ジエチルアミノ）ベンゾフェノン；２重量部
【００９８】
実施例４
（Ｂ）成分の増感色素を下記の（Ｂ−３）に変えた青紫光感光性組成物を用いた外は、実施例１におけると同様にして、感光性画像形成材を作製した。最小露光エネルギーは４ｍＪ／ｃｍ² であり、又、実施例１におけると同様のエッチング特性を示した。
【００９９】
（Ｂ−３）下記の化合物；２重量部
【０１００】
【化１１】

【０１０１】
実施例５
（Ｂ）成分の増感色素を下記の（Ｂ−４）に変えた青紫光感光性組成物を用いた外は、実施例１におけると同様にして、感光性画像形成材を作製した。最小露光エネルギーは７ｍＪ／ｃｍ² であり、又、実施例１におけると同様のエッチング特性を示した。
【０１０２】
（Ｂ−４）下記の化合物；２重量部
【０１０３】
【化１２】

【０１０４】
比較例１
光重合開始剤を下記の（Ｃ−３）に変えた青紫光感光性組成物を用いた外は、実施例１におけると同様にして、感光性画像形成材を作製したところ、画像を形成することはできなかった。
【０１０５】
（Ｃ−３）２−（４−メトキシフェニル）−４，６−ビス（トリクロロメチル）−ｓ−トリアジン；５重量部
【０１０６】
比較例２
光重合開始剤を前記の（Ｃ−３）に変えると共に、アルカリ可溶性樹脂を下記の（Ｄ−２）に変えた青紫光感光性組成物を用いた外は、実施例１におけると同様にして、感光性画像形成材を作製したところ、画像を形成することはできなかった。尚、本比較例は、従来技術の欄で挙げた特開２００２−２７８０６４号公報記載の樹脂組成物に相当する。
【０１０７】
（Ｄ−２）メタクリル酸（２０重量％）／メタクリル酸グリシジル（４５重量）／メタクリル酸トリシクロ〔５．２．１．０^2,6 〕デカン−８−イル（２５重量％）／スチレン（１０重量％）共重合体（重量平均分子量５０，０００）；５０重量部
【０１０８】
比較例３
アルカリ可溶性樹脂を下記の（Ｄ−３）に変えた青紫光感光性組成物を用いたこと、及び、現像液として、０．５重量％の炭酸ナトリウムと０．５重量％の界面活性剤（花王社製「ペレックスＮＢＬ」）とを含有する水溶液を用いたこと、の外は、実施例１におけると同様にして感光性画像形成材を作製したところ、最小露光エネルギーは４０ｍＪ／ｃｍ² であった。形成された線画像を目視にて観察したところ、非画像部（非露光部）の銅表面に赤色の薄膜が僅かに残留していた。又、エッチング処理では、非画像部（非露光部）の銅箔の約５％の面積部分がエッチングされていなかった。
【０１０９】
（Ｄ−３）メタクリル酸（４５重量％）／メタクリル酸ｔ−ブチル（３０重量％）／スチレン（２５重量％）共重合体に３，４−エポキシシクロヘキシルメチルアクリレートを反応させて得られた反応生成物（重量平均分子量５０，０００、メタクリル酸成分のカルボキシル基の６６モル％がエポキシ基と反応）；５０重量部
【０１１０】
実施例６
青紫光感光性組成物として、（Ａ）成分のエチレン性不飽和化合物としての下記の（Ａ−２）、（Ａ−３）、（Ｂ）成分の増感色素としての下記の（Ｂ−５）、（Ｃ）成分の光重合開始剤としての下記の（Ｃ−４）、（Ｄ）成分のアルカリ可溶性樹脂としての下記の（Ｄ−４）、及び下記のその他成分（水素供与性化合物）の各成分を、メチルエチルケトン／イソプロパノール（重量比８／２）との混合溶剤１００重量部に加えて、室温で攪拌して調液した塗布液を、仮支持フィルムとしてのポリエチレンテレフタレートフィルム（厚み１９μｍ）上に、アプリケーターを用いて乾燥膜厚が２５μｍとなる量で塗布し、９０℃のオーブンで５分間乾燥させ、形成された感光性組成物層上に、被覆フィルムとしてのポリエチレンフィルム（厚み２５μｍ）を積層し、１日放置することにより、感光性画像形成材料を作製した。
【０１１１】
（Ａ−２）下記の化合物（共栄化学社製「ライトエステル９ＥＧ」）；１５重量部
（Ａ−３）下記の化合物（共栄化学社製「ライトエステルＢＰ−６ＥＭ」）；３０重量部
【０１１２】
【化１３】

【０１１３】
（Ｂ−５）下記の化合物；０．２重量部
【０１１４】
【化１４】

【０１１５】
（Ｃ−４）２，２’−ビス（ｏ−クロロフェニル）−４，４’，５，５’−テトラフェニルビイミダゾール；１５重量部
（Ｄ−４）メタクリル酸（１５重量％）／メタクリル酸グリシジル（３０重量）／メタクリル酸ｔ−ブチル（３０重量％）／スチレン（２５重量％）共重合体（重量平均分子量５０，０００）；５０重量部
（その他）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）ブタン−１−オン；５重量部
（その他）２，４−ジエチルチオキサントン；０．１重量部
【０１１６】
別に、厚み３５μｍの銅箔を貼り合わせたポリイミド樹脂の銅張積層基板（厚み１．５ｍｍ、大きさ２５０ｍｍ×２００ｍｍ）の銅箔表面を、住友スリーエム社製「スコッチブライトＳＦ」を用いてバフロール研磨し、水洗し、空気流で乾燥させて整面し、次いで、これをオーブンで６０℃に予熱した後、その銅張積層板の銅箔上に、前記で得られた感光性画像形成材料を、そのポリエチレンフィルムを剥離しながらその剥離面で、ハンド式ロールラミネーターを用いて、ロール温度１００℃、ロール圧０．３ＭＰａ、ラミネート速度１．５ｍ／分でラミネートすることにより、銅張積層基板上に青紫光感光性組成物層が形成された感光性画像形成材を作製した。
【０１１７】
得られた感光性画像形成材を、直径７ｃｍのアルミニウム製ドラムに感光性組成物層が外側になるように固定し、波長４０５ｎｍ、０．５ｍＷの半導体レーザー（キコー社製）を用いて、ビームスポット径５０μｍで、ドラム回転数を５〜１００ｒｐｍの範囲で変化させることにより露光量を変化させて走査露光した後、０．５重量％の珪酸ナトリウムと０．５重量％の界面活性剤（花王社製「ペレックスＮＢＬ」）とを含有する水溶液を現像液として０．１５ＭＰａとなるように吹き付け、最小現像時間の２倍の時間でスプレー現像することによりネガ画像を現出させ、得られた画像について、露光感度として、１０μｍの線幅が再現するのに要する露光エネルギーを求めたところ、１．０ｍＪ／ｃｍ² であった。
【０１１８】
更に、以下に示す方法で分光感度の極大ピークを測定したところ、約４１０ｎｍであった。
＜分光感度の極大ピーク＞
画像形成材を５０×６０ｍｍの大きさに切り出したサンプルを、回折分光照射装置（ナルミ社製「ＲＭ−２３」）を用い、キセノンランプ（ウシオ電機社製「ＵＩ−５０１Ｃ」）を光源として３５０〜６５０ｎｍの波長域で分光した光を、横軸方向に露光波長が直線的に、縦軸方向に露光強度が対数的に変化するように設定して１０秒間照射して露光し、次いで、３０℃の１重量％炭酸ナトリウムと０．５重量％界面活性剤（花王社製「ペレックスＮＢＬ」）の水溶液を現像液として０．１５ＭＰａとなるように吹き付け、最小現像時間の２倍の時間でスプレー現像することにより、各露光波長の感度に応じた画像が得られ、その画像高さから画像形成可能な露光エネルギーを算出し、横軸に波長、縦軸にその露光エネルギーの逆数をプロットすることにより得られる分光感度曲線における極大ピークを読み取った。
【０１１９】
又、以下に示す方法で波長４１０ｎｍにおける画像形成可能な最小露光量〔Ｓ₄₁₀ （ｍＪ／ｃｍ² ）〕を測定したところ、１．２ｍＪ／ｃｍ² であった。又、波長４１０ｎｍにおける画像形成可能な該最小露光量〔Ｓ₄₁₀ 〕の波長４５０ｎｍにおける画像形成可能な最小露光量〔Ｓ₄₅₀ （ｍＪ／ｃｍ² ）〕に対する比〔Ｓ₄₁₀ ／Ｓ₄₅₀ 〕、及び、波長４５０ｎｍ超過６５０ｎｍ以下の各波長における画像形成可能な最小露光量〔Ｓ_450-650 （ｍＪ／ｃｍ² ）〕の波長４５０ｎｍにおける画像形成可能な最小露光量〔Ｓ₄₅₀ （ｍＪ／ｃｍ² ）〕に対する比〔Ｓ_{45 0-650} ／Ｓ₄₅₀ 〕を測定し、以下の基準で評価したところ、〔Ｓ₄₁₀ ／Ｓ₄₅₀ 〕、及び〔Ｓ_450-650 ／Ｓ₄₅₀ 〕共に「Ａ」であった。
【０１２０】
＜Ｓ₄₁₀ ，Ｓ₄₁₀ ／Ｓ₄₅₀ ，Ｓ_450-650 ／Ｓ₄₅₀ ＞
前記と同様にして３５０〜６５０ｎｍの波長域で波長を変化させて露光し、現像したときの、波長４１０ｎｍにおける画像形成可能な最小露光量〔Ｓ₄₁₀ （ｍＪ／ｃｍ² ）〕と波長４５０ｎｍにおける画像形成可能な最小露光量〔Ｓ₄₅₀ （ｍＪ／ｃｍ² ）〕、及び、波長４５０ｎｍ超過６５０ｎｍ以下の各波長における画像形成可能な最小露光量〔Ｓ_450-650 （ｍＪ／ｃｍ² ）〕をそれぞれ求め、その比〔Ｓ₄₁₀ ／Ｓ₄₅₀ 〕、及び〔Ｓ_450-650 ／Ｓ₄₅₀ 〕を算出し、以下の基準で評価した。
【０１２１】
＜Ｓ₄₁₀ ／Ｓ₄₅₀ の評価基準＞
Ａ：Ｓ₄₁₀ ／Ｓ₄₅₀ が０．０３以下。
Ｂ：Ｓ₄₁₀ ／Ｓ₄₅₀ が０．０３超過０．０５以下。
Ｃ：Ｓ₄₁₀ ／Ｓ₄₅₀ が０．０５超過０．１以下。
Ｄ：Ｓ₄₁₀ ／Ｓ₄₅₀ が０．１超過。
【０１２２】
＜Ｓ_450-650 ／Ｓ₄₅₀ の評価基準＞
Ａ：Ｓ_450-650 ／Ｓ₄₅₀ が１０超過。
Ｂ：Ｓ_450-650 ／Ｓ₄₅₀ が５超過１０以下。
Ｃ：Ｓ_450-650 ／Ｓ₄₅₀ が１超過５以下。
Ｄ：Ｓ_450-650 ／Ｓ₄₅₀ が１以下。
【０１２３】
別に、得られた感光性画像形成材につき、以下に示す方法で、黄色灯下でのセーフライト性を評価したところ、「Ａ」であった。
＜黄色灯下でのセーフライト性＞
画像形成材を黄色灯照明（約４７０ｎｍ以下の波長の光を遮断した条件）下に、１分間、２分間、５分間、１０分間、２０分間、３０分間放置した後、前記と同様にして、走査露光及び現像処理を行い、前記に比して画像に変化が生じるまでの放置時間を求め、以下の基準で評価した。
Ａ：２０分以上
Ｂ：１０分以上２０分未満
Ｃ：１分以上１０分未満
Ｄ：１分未満
【０１２４】
【発明の効果】
本発明は、青紫光に対する感度、及び現像性に優れる感光性組成物であって、特に、ドライフィルムレジスト材として、及び青紫色レーザー光による直接描画に用いるに好適な青紫光感光性組成物、並びにそれを用いた画像形成材料、画像形成材、及び画像形成方法を提供することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an etching resist and plating for forming a printed circuit board, a liquid crystal display element, a plasma display, a large scale integrated circuit, a thin transistor, a semiconductor package, a color filter, a conductive circuit in an organic electroluminescence, an electrode processing substrate, etc. Photosensitive composition used for resists, solder resists, interlayer insulation layers, plasma display resists, color filter resists, color proofs for printing calibration, laser gravure resists, etc., or flexographic printing plates and lithographic printing plate making In particular, the present invention relates to a blue-violet photosensitive composition suitable for direct drawing with a blue-violet laser beam, and an image forming material, an image forming material, and an image forming method using the same.
[0002]
[Prior art]
Conventionally, for forming printed circuit boards, liquid crystal display elements, plasma displays, large-scale integrated circuits, thin transistors, semiconductor packages, color filters, organic electroluminescence, etc., for forming conductive circuits and electrode processing substrates, for example, photosensitive compositions A layer composed of a product is formed on a temporary support film, and a dry film resist material in which the surface of the photosensitive composition layer is covered with a coating film is peeled off from the coating film and laminated on a substrate to be processed. The photosensitive composition layer on the substrate is image-exposed through a mask film on which circuits and electrode patterns are drawn, and then the temporary support film is peeled off, and the difference in solubility in the developer between the exposed and unexposed areas is utilized. Development process is performed to form a resist image corresponding to the circuit pattern. After the processed substrate is etched or plated like Te, by removing the resist image, lithography to form the depicted circuit and the electrode pattern on the mask film on the substrate it has been widely used. However, while this dry film resist material is easy to form a photosensitive composition layer on a substrate to be processed, it is exposed to an image through a temporary support film, and the thickness of the photosensitive composition layer is 10 μm. Due to the above thickness and the like, it has a drawback that it is difficult to obtain high resolution.
[0003]
On the other hand, in recent years, a laser direct drawing method that directly forms an image from digital information such as a computer without using a mask film by using laser light as an exposure light source is not only productive, but also resolution and positional accuracy. As a result, the use of laser light has been actively studied in the lithography method.
[0004]
By the way, various light sources from the ultraviolet region to the infrared region are known as laser light. As laser light that can be used for image exposure, argon ions are used from the viewpoint of output, stability, photosensitive ability, cost, and the like. Lasers, helium neon lasers, YAG lasers, and semiconductor lasers that emit light in the visible to infrared region are the mainstays. For example, an argon ion laser with a wavelength of 488 nm and an FD-YAG laser with a wavelength of 532 nm were used. Lithography has already been put into practical use.
[0005]
However, the conventional photosensitive composition does not always have sufficient sensitivity in the direct drawing method using laser light, and a semiconductor that can stably oscillate in the blue-violet region due to the recent remarkable progress in laser technology. Although lasers can also be used, the output of the blue-violet region is lower than that of other visible regions. Of course, the level of practical use in lithography is not reached.
[0006]
On the other hand, in photopolymerizable photosensitive compositions, hexaarylbiimidazole compounds have long been known as suitable photopolymerization initiators, particularly in the ultraviolet region. Further, for example, hexaarylbiimidazole compounds and ketocoumarin compounds Proposals intended to improve sensitivity by combining with sensitizing dyes such as compounds (for example, see Patent Document 1) and dialkylaminobenzene compounds (for example, see Patent Document 2) have been made. A photosensitive composition comprising a combination of an imidazole compound, a sensitizing dye such as a dialkylaminobenzene compound, and a polymer binder of a specific (meth) acrylic polymer having an ethylenically unsaturated bond in the side chain ( For example, see Patent Document 3).
[0007]
[Patent Document 1]
Japanese Patent Publication No. 5-88244.
[Patent Document 2]
Japanese Patent Publication No. 6-29285.
[Patent Document 3]
JP 2002-296664 A.
[0008]
In addition, for the purpose of improving the sensitivity, developability of the photopolymerizable photosensitive composition, and the durability of the image formed thereby, the α, β-unsaturated monocarboxylic acid adduct of the epoxy resin is polyvalent. Photosensitive composition containing modified epoxy acrylate resin to which carboxylic acid or anhydride thereof is added as a polymer binder, and laminating it on a substrate as a dry film resist material, or coating composition thereof An image forming method in which an image forming material for photoresist, which is coated on a substrate and dried to form a photosensitive composition layer, is exposed and developed with a high-pressure mercury lamp, a visible laser, or an infrared laser (for example, Patent Document 4) , Patent Document 5, and Patent Document 6, etc.), and ethylenically unsaturated carboxylic acid, epoxy group-containing ethylenically unsaturated compound and other ethylenically unsaturated compounds. A method for producing a spacer for a display panel by exposing a composition comprising a copolymer with a polymer as a polymer binder and using a trihalomethyltriazine as a photopolymerization initiator to ultraviolet exposure and developing (see, for example, Patent Document 7). ) Etc. are also known. However, according to the study of the present inventors, the sensitivity and developability as a blue-violet light-sensitive composition still remain room for improvement even though the photosensitive compositions in these proposals.
[0009]
[Patent Document 4]
JP-A-5-204150.
[Patent Document 5]
JP 2000-147767.
[Patent Document 6]
JP 2001-228611 A.
[Patent Document 7]
JP 2002-278064 A.
[0010]
[Problems to be solved by the invention]
The present invention has been made in view of the above-described prior art, and therefore the present invention is a photosensitive composition excellent in sensitivity to blue-violet light and developability, and particularly as a dry film resist material. And a blue-violet light-sensitive composition suitable for direct drawing by a blue-violet laser beam, and an image forming material, an image forming material, and an image forming method using the same.
[0011]
[Means for Solving the Problems]
The present invention relates to a blue-violet photosensitive composition comprising the following components (A), (B), (C), and (D), and the blue-violet photosensitivity on a temporary support film. A blue-violet light-sensitive image forming material in which a layer of the composition is formed, and a blue-violet light-sensitive material in which the blue-violet light-sensitive image forming material is laminated on the substrate to be processed on the blue-violet light-sensitive composition layer side. Image forming material and image forming method for exposing a blue-violet light-sensitive composition layer of the blue-violet light-sensitive image forming material by scanning exposure with a laser beam having a wavelength of 390 to 430 nm and developing the negative image Is the gist.
[0012]
(A) Ethylenically unsaturated compound
(B)With a wavelength of 390 to 430 nmSensitizing dye having a maximum spectral sensitivity peak in the blue-violet region.
(C) A photopolymerization initiator comprising a hexaarylbiimidazole compound or a titanocene compound
(D) Alkali-soluble resin comprising a carboxyl group and an epoxy group-containing vinyl copolymer containing a structural repeating unit derived from an ethylenically unsaturated carboxylic acid and a structural repeating unit derived from an epoxy group-containing ethylenically unsaturated compound
[0013]
DETAILED DESCRIPTION OF THE INVENTION
The ethylenically unsaturated compound of component (A) constituting the blue-violet photosensitive composition of the present invention is a photopolymerization initiator of component (C) described later when the photosensitive composition is irradiated with actinic rays. Is a compound having at least one radically polymerizable ethylenically unsaturated bond in the molecule that undergoes addition polymerization by the action of a photopolymerization initiating system containing, and in some cases, crosslinks and cures.
[0014]
As the ethylenically unsaturated compound in the present invention, a compound having one ethylenically unsaturated bond in the molecule, specifically, for example, (meth) acrylic acid [in the present invention, “(meth) acrylic” Means “acrylic” or / and “methacrylic”. ], Unsaturated carboxylic acids such as crotonic acid, isocrotonic acid, maleic acid, itaconic acid, citraconic acid, and alkyl esters thereof, (meth) acrylonitrile, (meth) acrylamide, styrene, etc. In view of the crosslinkability and the difference in developer solubility between the exposed and non-exposed areas associated therewith, the compound is preferably a compound having two or more ethylenically unsaturated bonds in the molecule. An acrylate compound in which the unsaturated bond is derived from a (meth) acryloyloxy group is particularly preferable.
[0015]
The compounds having two or more ethylenically unsaturated bonds are typically esters of unsaturated carboxylic acids and polyhydroxy compounds, (meth) acryloyloxy group-containing phosphates, hydroxy (meth) acrylates. Examples include urethane (meth) acrylates of a compound and a polyisocyanate compound, and epoxy (meth) acrylates of a (meth) acrylic acid or hydroxy (meth) acrylate compound and a polyepoxy compound.
[0016]
Specific examples of the esters include unsaturated carboxylic acid as described above, ethylene glycol, polyethylene glycol (addition number 2 to 14), propylene glycol, polypropylene glycol (addition number 2 to 14), trimethylene. Glycol, tetramethylene glycol, neopentyl glycol, hexamethylene glycol, nonamethylene glycol, trimethylol ethane, tetramethylol ethane, trimethylol propane, glycerol, pentaerythritol, dipentaerythritol, sorbitol, and their ethylene oxide adducts, propylene Reaction products with aliphatic polyhydroxy compounds such as oxide adducts, diethanolamine, triethanolamine, and more specifically, for example, ethylene glycol di (meth) Acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, tripropylene glycol di (meth) ) Acrylate, tetramethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hexamethylene glycol di (meth) acrylate, nonamethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, tetramethylol Ethane tri (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, Limethylolpropane ethylene oxide addition tri (meth) acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, glycerol propylene oxide addition tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (Meth) acrylate, sorbitol tri (meth) acrylate, sorbitol tetra (meth) acrylate, so Examples thereof include rubitol penta (meth) acrylate, sorbitol hexa (meth) acrylate and the like, and similar crotonate, isocrotonate, maleate, itaconate, citraconate and the like.
[0017]
Furthermore, as the esters, unsaturated carboxylic acids as described above, aromatic polyhydroxy compounds such as hydroquinone, resorcin, pyrogallol, bisphenol F, bisphenol A, or their ethylene oxide adducts or glycidyl group-containing compound adducts In particular, for example, hydroquinone di (meth) acrylate, resorcin di (meth) acrylate, pyrogallol tri (meth) acrylate, bisphenol A di (meth) acrylate, bisphenol A bis [oxyethylene (meth) acrylate] Bisphenol A bis [trioxyethylene (meth) acrylate], bisphenol A bis [pentaoxyethylene (meth) acrylate], bisphenol A bis [hexaoxyethylene (meth) acrylate] Bisphenol A bis [glycidyl ether (meth) acrylate] and the like, and a reaction product of an unsaturated carboxylic acid as described above and a heterocyclic polyhydroxy compound such as tris (2-hydroxyethyl) isocyanurate, specifically, For example, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tri (meth) acrylate, etc., and a reaction product of unsaturated carboxylic acid, polycarboxylic acid and polyhydroxy compound, specifically For example, a condensate of (meth) acrylic acid, phthalic acid and ethylene glycol, a condensate of (meth) acrylic acid, maleic acid and diethylene glycol, a condensate of (meth) acrylic acid, terephthalic acid and pentaerythritol, Condensates of (meth) acrylic acid, adipic acid, butanediol, and glycerin. It is.
[0018]
Specific examples of the (meth) acryloyloxy group-containing phosphates include (meth) acryloyloxyethyl phosphate, bis [(meth) acryloyloxyethyl] phosphate, (meth) acryloyloxyethylene glycol phosphate, and the like. These may be used alone or as a mixture.
[0019]
Specific examples of urethane (meth) acrylates include hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycerol di (meth) acrylate, pentaerythritol tri (meth) acrylate, and tetramethylol. Hydroxy (meth) acrylate compounds such as ethane tri (meth) acrylate and hexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine methyl ester diisocyanate, lysine methyl ester triisocyanate, dimer acid diisocyanate, 1,6,6 Aliphatic polymers such as 11-undecatriisocyanate, 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane Cycloaliphatic polyisocyanates such as isocyanate, cyclohexane diisocyanate, dimethylcyclohexane diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, bicycloheptane triisocyanate, p-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, 4,4′-diphenylmethane diisocyanate, tolidine diisocyanate, 1,5-naphthalene diisocyanate, tris (isocyanate phenylmethane), tris (isocyanate phenyl) thiophosphate, etc. Heterocyclic polyisocyanates such as aromatic polyisocyanates and isocyanurates Aneto, a reaction product of a polyisocyanate compounds and the like.
[0020]
Moreover, as the epoxy (meth) acrylates, specifically, for example, (meth) acrylic acid, or a hydroxy (meth) acrylate compound as described above, (poly) ethylene glycol polyglycidyl ether, (poly) propylene Glycol polyglycidyl ether, (poly) tetramethylene glycol polyglycidyl ether, (poly) pentamethylene glycol polyglycidyl ether, (poly) neopentyl glycol polyglycidyl ether, (poly) hexamethylene glycol polyglycidyl ether, (poly) trimethylol Aliphatic polyepoxy compounds such as propane polyglycidyl ether, (poly) glycerol polyglycidyl ether, (poly) sorbitol polyglycidyl ether, phenol novolac polyepoxy Compounds, brominated phenol novolac polyepoxy compounds, aromatic polyepoxy compounds such as (o-, m-, p-) cresol novolac polyepoxy compounds, bisphenol A polyepoxy compounds, bisphenol F polyepoxy compounds, sorbitan polyglycidyl ethers, Examples thereof include reactants with polyepoxy compounds such as heterocyclic polyepoxy compounds such as triglycidyl isocyanurate and triglycidyl tris (2-hydroxyethyl) isocyanurate.
[0021]
In addition to the above, as other ethylenically unsaturated compounds, for example, (meth) acrylamides such as ethylenebis (meth) acrylamide, allyl esters such as diallyl phthalate, vinyl group-containing compounds such as divinyl phthalate, etc. Is mentioned. These ethylenically unsaturated compounds may be used alone or in combination of two or more.
[0022]
As the ethylenically unsaturated compound of the above component (A), ester (meth) acrylates, (meth) acryloyloxy group-containing phosphates, or urethane (meth) acrylates are preferable in the present invention. ) Acrylates are particularly preferred, and among the ester (meth) acrylates, it has a polyoxyalkylene group such as polyethylene glycol, polypropylene glycol, or a polyethylene oxide adduct of bisphenol A, and two (meth) acryloyloxy groups. The ester (meth) acrylates having the above are particularly preferred.
[0023]
The sensitizing dye of component (B) constituting the blue-violet light-sensitive composition of the present invention has a spectral sensitivity absorption maximum in the blue-violet region having a wavelength of 390 to 430 nm, and efficiently absorbs light in that region. At the same time, the photoexcitation energy is transmitted to the (C) component photopolymerization initiator described later, and the photopolymerization initiator is decomposed to generate active radicals that induce polymerization of the (A) component ethylenically unsaturated compound. In the present invention, the sensitizing dye includes a dialkylaminobenzene compound, a pyromethene compound, a trihydroxypyrimidine derivative, etc. Among them, a dialkylaminobenzene compound is used. preferable.
[0024]
The preferred dialkylaminobenzene compounds include, in particular, dialkylaminobenzophenone compounds, dialkylaminobenzene compounds having a heterocyclic group as a substituent at a carbon atom in the p-position with respect to the amino group on the benzene ring, and benzene rings. Dialkylaminobenzene compounds having a substituent containing a sulfonylimino group at the carbon atom in the p-position with respect to the amino group above, and dialkylaminobenzene compounds having a carbostyryl skeleton are preferred.
[0025]
The dialkylaminobenzophenone compound is preferably a compound represented by the following general formula (I).
[0026]
[Formula 4]

[0027]
[In formula (I), R¹, R², R^FiveAnd R⁶Each independently represents an optionally substituted alkyl group, R^Three, R^Four, R⁷And R⁸Each independently represents an alkyl group which may have a substituent, or a hydrogen atom;¹And R², R^ThreeAnd R^Four, R¹And R^Three, R²And R^Four, R^FiveAnd R⁷And R⁶And R⁸And each independently may form a nitrogen-containing heterocyclic ring. ]
[0028]
Here, R in the formula (I)¹, R², R^FiveAnd R⁶The number of carbon atoms of the alkyl group, and R^Three, R^Four, R⁷And R⁸It is preferable that carbon number is 1-6 when is an alkyl group. Further, when forming a nitrogen-containing heterocycle, it is preferably a 5- or 6-membered ring, and R¹And R^Three, R²And R^Four, R^FiveAnd R⁷Or R⁶And R⁸Preferably form a 6-membered tetrahydroquinoline ring, R¹And R²And R^ThreeAnd R^FourOr / and R^FiveAnd R⁶And R⁷And R⁸Particularly preferably forms a julolidine ring. Furthermore, a tetrahydroquinoline ring having an alkyl group as a substituent at the 2-position or a julolidine ring containing the tetrahydroquinoline ring is particularly preferred.
[0029]
Specific examples of the compound represented by the general formula (I) include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, and compounds having the following structures. It is done.
[0030]
[Chemical formula 5]

[0031]
In addition, the heterocyclic group in the dialkylaminobenzene compound having a heterocyclic group as a substituent at a carbon atom in the p-position with respect to the amino group on the benzene ring includes a nitrogen atom, an oxygen atom, or a sulfur atom. Alternatively, a 6-membered ring is preferable, a 5-membered ring having a condensed benzene ring is particularly preferable, and those represented by the following general formula (II) are preferable.
[0032]
[Chemical 6]

[0033]
[In formula (II), R¹And R²Each independently represents an optionally substituted alkyl group, R^ThreeAnd R^FourEach independently represents an alkyl group which may have a substituent, or a hydrogen atom;¹And R², R¹And R^ThreeAnd R²And R^FourEach independently may form a nitrogen-containing heterocyclic ring, X represents an oxygen atom, a sulfur atom, a dialkylmethylene group, an imino group, or an alkylimino group, and the benzene ring condensed to the heterocyclic ring is It may have a substituent. ]
[0034]
Here, R in the formula (II)¹And R²The number of carbon atoms of the alkyl group, and R^ThreeAnd R^FourWhen is an alkyl group, the number of carbon atoms is preferably 1-6, and when a nitrogen-containing heterocyclic ring is formed, it is preferably a 5- or 6-membered ring, and R¹And R^Three, R²And R^Four, R^FiveAnd R⁷Or R⁶And R⁸Preferably form a 6-membered tetrahydroquinoline ring, R¹And R²And R^ThreeAnd R^FourOr / and R^FiveAnd R⁶And R⁷And R⁸Particularly preferably forms a julolidine ring. Furthermore, a tetrahydroquinoline ring having an alkyl group as a substituent at the 2-position or a julolidine ring containing the tetrahydroquinoline ring is particularly preferred. In addition, when X is a dialkylmethylene group, the alkyl group preferably has 1 to 6 carbon atoms, and when it is an alkylimino group, the alkyl group preferably has 1 to 6 carbon atoms.
[0035]
Specific examples of the compound represented by the general formula (II) include, for example, 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl). ) Benzo [4,5] benzoxazole, 2- (p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2- (p-dimethylaminophenyl) benzothiazole, 2- (p-diethylaminophenyl) benzothiazole 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2- (p-dimethylaminophenyl) -3,3-dimethyl-3H-indole, 2- (p-diethylamino) Phenyl) -3,3-dimethyl-3H-indole and below The compound of the following structure is mentioned.
[0036]
[Chemical 7]

[0037]
In addition to the compounds represented by the general formula (II), examples of the dialkylaminobenzene compounds having a heterocyclic group as a substituent at a carbon atom in the p-position with respect to the amino group on the benzene ring include: 2- (p-dimethylaminophenyl) pyridine, 2- (p-diethylaminophenyl) pyridine, 2- (p-dimethylaminophenyl) quinoline, 2- (p-diethylaminophenyl) quinoline, 2- (p-dimethylaminophenyl) ) Pyrimidine, 2- (p-diethylaminophenyl) pyrimidine, 2,5-bis (p-diethylaminophenyl) -1,3,4-oxadiazole, 2,5-bis (p-diethylaminophenyl) -1,3 , 4-thiadiazole and the like.
[0038]
As the dialkylaminobenzene compound having a substituent containing a sulfonylimino group at the p-position carbon atom with respect to the amino group on the benzene ring, those represented by the following general formula (III) are preferred.
[0039]
[Chemical 8]

[0040]
[In formula (III), R¹And R²Each independently represents an optionally substituted alkyl group, R^ThreeAnd R^FourEach independently represents an alkyl group which may have a substituent, or a hydrogen atom;¹And R², R¹And R^ThreeAnd R²And R^FourEach independently may form a nitrogen-containing heterocycle, R⁹Represents a monovalent group or a hydrogen atom, R^TenRepresents a monovalent group. ]
[0041]
Here, R in the formula (III)¹And R²The number of carbon atoms of the alkyl group, and R^ThreeAnd R^FourWhen is an alkyl group, the number of carbon atoms is preferably 1-6, and when a nitrogen-containing heterocyclic ring is formed, it is preferably a 5- or 6-membered ring.^ThreeAnd R^FourIs preferably a hydrogen atom. Also, R⁹And R^TenAs the monovalent group, for example, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkoxy group, an alkenyloxy group, an acyl group, an acyloxy group, an aryl group, an aryloxy group, an aralkyl group, an arylalkenyl group, Hydroxy group, formyl group, carboxyl group, carboxylic acid ester group, carbamoyl group, amino group, acylamino group, carbamate group, sulfonamide group, sulfonic acid group, sulfonic acid ester group, sulfamoyl group, alkylthio group, imino group, cyano group And heterocyclic groups. Among these, R⁹As a hydrogen atom or R^TenIs preferably an aryl group.
[0042]
Further, as the dialkylaminobenzene compound having a carbostyril skeleton, those represented by the following general formula (IV) are preferable.
[0043]
[Chemical 9]

[0044]
[In formula (IV), R¹, R²And R¹¹Each independently represents an optionally substituted alkyl group, R^ThreeAnd R^FourEach independently represents an alkyl group which may have a substituent, or a hydrogen atom;¹And R², R¹And R^ThreeAnd R²And R^FourEach independently may form a nitrogen-containing heterocycle, R¹²Represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or a hydrogen atom. ]
[0045]
Here, R in the formula (IV)¹, R²And R¹¹The number of carbon atoms of the alkyl group, and R^Three, R^FourAnd R¹²When is an alkyl group, the number of carbon atoms is preferably 1-6, and when a nitrogen-containing heterocyclic ring is formed, it is preferably a 5- or 6-membered ring.^ThreeAnd R^FourIs preferably a hydrogen atom. Also, R¹²Is preferably a phenyl group.
[0046]
As the sensitizing dye of the component (B), in the present invention, a dialkylaminobenzophenone compound represented by the general formula (I), an amino group on the benzene ring represented by the general formula (III) Or a dialkylaminobenzene compound having a substituent containing a sulfonylimino group at the p-position carbon atom, or a dialkylaminobenzene compound having a carbostyryl skeleton represented by the general formula (IV). Particularly preferred.
[0047]
The photopolymerization initiator of the component (C) constituting the blue-violet photosensitive composition of the present invention is a sensitizing dye when irradiated with light in the presence of the sensitizing dye of the component (B). Is a radical generator that generates an active radical by receiving the photoexcitation energy of the above, and leads to polymerization of the ethylenically unsaturated compound of component (A). In the present invention, a hexaarylbiimidazole compound or a titanocene compound It is essential to be one of the following.
[0048]
As the hexaarylbiimidazole compound, specifically, for example, 2,2′-bis (o-methoxyphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′- Bis (p-methoxyphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (fluorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2 , 2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra ( p-methylphenyl) biimidazole, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (p-methoxyphenyl) biimidazole, 2,2′-bis (o-chlorophenyl) ) 4,4 ′, 5,5′-tetra (o, p-dimethoxyphenyl) biimidazole, 2,2′-bis (o, p-dichlorophenyl) -4,4 ′, 5,5′-tetra (p- Methoxyphenyl) biimidazole, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (p-ethoxycarbonylphenyl) biimidazole, 2,2′-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (p-chlorophenyl) biimidazole, 2,2'-bis (o-chlorophenyl) -4,4', 5,5'-tetra (o, p-dichlorophenyl) Biimidazole, 2,2′-bis (o, p-dichlorophenyl) -4,4 ′, 5,5′-tetra (o, p-dichlorophenyl) biimidazole, 2,2′-bis (o-chlorophenyl)- 4, 4 , 5,5′-tetra (p-fluorophenyl) biimidazole, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (o, p-dibromophenyl) biimidazole, 2,2′-bis (o-bromophenyl) -4,4 ′, 5,5′-tetra (o, p-dichlorophenyl) biimidazole, 2,2′-bis (o-bromophenyl) -4,4 ', 5,5'-tetra (p-iodophenyl) biimidazole, 2,2'-bis (o-bromophenyl) -4,4', 5,5'-tetra (p-chloro-p-methoxyphenyl) ) Biimidazole, 2,2′-bis (o-bromophenyl) -4,4 ′, 5,5′-tetra (o-chloro-p-methoxyphenyl) biimidazole, 2,2′-bis (o-) Chlorophenyl) -4,4 ', 5,5'- Examples include tetra (p-chloronaphthyl) biimidazole. Among them, a hexaphenylbiimidazole compound is preferable, and a compound in which the o-position of the benzene ring bonded to the 2,2′-position on the imidazole ring is substituted with a halogen atom is more preferable. Particularly preferred are those in which the benzene ring bonded to the 4 ′, 5,5′-position is unsubstituted or substituted with a halogen atom or an alkoxycarbonyl group.
[0049]
Specific examples of the titanocene compound include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis (2,4-difluorophenyl), and dicyclopentadienyl titanium bisphenyl. Cyclopentadienyl titanium bis (2,6-difluorophenyl), dicyclopentadienyl titanium bis (2,4,6-trifluorophenyl), dicyclopentadienyl titanium bis (2,3,5,6- Tetrafluorophenyl), dicyclopentadienyl titanium bis (2,3,4,5,6-pentafluorophenyl), di (methylcyclopentadienyl) titanium bis (2,6-difluorophenyl), di (methyl Cyclopentadienyl) titanium bis (2,4,6-trif Orophenyl), di (methylcyclopentadienyl) titanium bis (2,3,5,6-tetrafluorophenyl), di (methylcyclopentadienyl) titanium bis (2,3,4,5,6-pentafluoro) Phenyl), dicyclopentadienyl titanium bis [2,6-difluoro-3- (1-pyrrolyl) phenyl] and the like. Of these, titanium compounds having a dicyclopentadienyl structure and a biphenyl structure are preferred, and those in which the o-position of the biphenyl ring is substituted with a halogen atom are particularly preferred.
[0050]
In addition, as a photoinitiator in the photosensitive composition of this invention, it is essential to contain either the said hexaaryl biimidazole type compound or the said titanocene type compound of (C) component, and they are used independently. Or two or more of them may be used in combination. In addition, other photopolymerization initiators may be contained. Examples of the photopolymerization initiator include halomethylated s-triazine derivatives, halomethylated 1,3,4-oxadiazole derivatives, and organoborates. , Diaryliodonium salts, carbonyl compounds, and organic peroxides.
[0051]
The alkali-soluble resin of component (D) constituting the blue-violet photosensitive composition of the present invention is intended to improve the formability and developability of the photosensitive composition layer on the substrate. In the present invention, the alkali-soluble resin contains a carboxyl group and an epoxy group containing a structural repeating unit derived from an ethylenically unsaturated carboxylic acid and a structural repeating unit derived from an epoxy group-containing ethylenically unsaturated compound. It is essential that the copolymer is composed of a vinyl-based copolymer, and the copolymer is composed of a structural repeating unit derived from an ethylenically unsaturated carboxylic acid and a structural repeating unit derived from an epoxy group-containing ethylenically unsaturated compound. In addition, it is preferable to include a constitutional repeating unit derived from another copolymerizable monomer.
[0052]
Here, examples of the ethylenically unsaturated carboxylic acid in the copolymer include monocarboxylic acids such as (meth) acrylic acid and crotonic acid, and dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid. Acids, mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids such as mono [2- (meth) acryloyloxyethyl] oxalate, mono [2- (meth) acryloyloxyethyl] phthalate, ω- Examples include carboxypolycaprolactone mono (meth) acrylates and other polymer mono (meth) acrylates having a carboxyl group and a hydroxyl group at both ends, and these may be used alone or in combination of two or more. May be used. Among these, (meth) acrylic acid is preferable from the viewpoints of copolymerization reactivity and solubility of the photosensitive composition layer as an image forming material in an alkali developer after exposure.
[0053]
Examples of the epoxy group-containing ethylenically unsaturated compound include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, and (meth) acrylic acid 6 , 7-epoxyheptyl and other (meth) acrylic acid epoxy alkyl esters, α-ethyl acrylate glycidyl, α-n-propyl acryl glycidyl, α-n-butyl acryl glycidyl, α-ethyl acrylate 6,7-epoxy Α-alkyl acrylic acid epoxy alkyl esters such as heptyl, glycidyl ethers such as o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3,4-epoxycyclohexyl (meth) acrylic acid Methyl, (meth) acryl (Meth) acrylic acid cycloaliphatic epoxy alkyl such as 2,3-epoxycyclopentylmethyl oxalate, 7,8-epoxy [tricyclo [5.2.1.0] dec-2-yl] methyl (meth) acrylate Esters etc. are mentioned, These may be used independently and may be used in combination of 2 or more type. Among these, glycidyl (meth) acrylate ((meth) acrylate) in terms of copolymerization reactivity, alkali developability after exposure of the photosensitive composition layer as an image forming material, and film strength after development processing, Preference is given to 3,4-epoxycyclohexylmethyl (meth) acrylate and 2,3-epoxycyclopentylmethyl (meth) acrylate.
[0054]
Other copolymerizable monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, (meth) (Meth) acrylic acid alkyl esters such as n-butyl acrylate, i-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, (Meth) acrylic acid 2-ethylcyclohexyl, (meth) acrylic acid isobornyl, (meth) acrylic acid tricyclo [5.2.1.0^2,6 ] Decan-8-yl, (meth) acrylic acid (tricyclo [5.2.1.0^2,6 ] (Meth) acrylic acid alicyclic esters such as decan-8-yloxy) ethyl, (meth) acrylic acid aryl esters such as phenyl (meth) acrylate, and (meth) acrylic such as benzyl (meth) acrylate Dialkyl acid dialkyl esters such as acid aralkyl esters, diethyl maleate, diethyl fumarate and diethyl itaconate, (meth) acrylic acid such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate Nuclear alkyls such as hydroxyalkyl esters, α-substituted alkylstyrenes such as styrene, α-methylstyrene, α-ethylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,5-dimethylstyrene Styrene, o-hydroxystyrene, m-hydroxystyrene , Vinyl aromatic compounds such as nucleus-substituted hydroxystyrene such as p-hydroxystyrene and dihydroxystyrene, nucleus-substituted halogenated styrene such as p-chlorostyrene, p-bromostyrene and dibromostyrene, 1,3-butadiene and isoprene Conjugated diene compounds such as 2,3-dimethyl 1,3-butadiene, (meth) acrylonitrile, (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N- Examples include (meth) acrylic acid derivatives such as dimethylaminoethyl (meth) acrylamide, and vinyl compounds such as vinyl acetate and vinyl chloride. These may be used alone or in combination of two or more. It may be used. Of these, i-propyl (meth) acrylate and (meth) acrylic are from the aspects of copolymerization reactivity and solubility of the photosensitive composition layer as an image forming material in an alkali developer after exposure. (Meth) acrylic acid branched alkyl esters such as i-butyl acid, t-butyl (meth) acrylate, 2-methylhexyl (meth) acrylate, and vinyl aromatic compounds such as styrene and α-methylstyrene Are preferred, and t-butyl (meth) acrylate and styrene are particularly preferred.
[0055]
In the present invention, the copolymer is a constitutional repeating unit derived from the ethylenically unsaturated carboxylic acid, a constitutional repeating unit derived from the epoxy group-containing ethylenically unsaturated compound, and the other copolymerizable monomer. The content ratio of the constitutional repeating unit derived from the body is 5 to 30% by weight of the constitutional repeating unit derived from the ethylenically unsaturated carboxylic acid, based on the total amount of the copolymer, derived from the epoxy group-containing ethylenically unsaturated compound. It is preferable that the constitutional repeating unit is 5 to 40% by weight, the constitutional repeating unit derived from another copolymerizable monomer is 30 to 90% by weight, and the constitutional repeating unit derived from the ethylenically unsaturated carboxylic acid is 10 to 25% by weight, 10 to 35% by weight of structural repeating units derived from an epoxy group-containing ethylenically unsaturated compound, and structural repeating units derived from other copolymerizable monomers It is particularly preferably from 40 to 80 wt%.
[0056]
When the proportion of the structural repeating unit derived from the ethylenically unsaturated carboxylic acid is less than the above range, the solubility of the photosensitive composition layer as an image forming material in the alkali developer after exposure tends to be lowered, whereas the above range If it exceeds the limit, the storage stability as the photosensitive composition coating solution tends to decrease. In addition, if the proportion of the constitutional repeating unit derived from the epoxy group-containing ethylenically unsaturated compound is less than the above range, the non-image portion detachability in the development processing is inferior, and the film strength after the development processing tends to decrease, On the other hand, when the range is exceeded, the storage stability as the photosensitive composition coating solution tends to be lowered. In addition, when the proportion of the constitutional repeating unit derived from another copolymerizable monomer is less than the above range, the storage stability as the photosensitive composition coating solution tends to decrease, or the image area in the development processing tends to decrease in film thickness. On the other hand, if the range is exceeded, background stains tend to occur in the development process.
[0057]
Further, among other copolymerizable monomers, the proportion of the structural repeating unit derived from t-butyl (meth) acrylate is particularly preferably 15 to 50% by weight with respect to the total amount of the copolymer. Is 20 to 45% by weight, and the proportion of the structural repeating unit derived from styrene, which is particularly preferable, is preferably 15 to 40% by weight, particularly preferably 20 to 35% by weight.
[0058]
These copolymers preferably have an acid value of 30 to 250 mg · KOH / g and a polystyrene equivalent weight average molecular weight of 1,000 to 300,000.
[0059]
Examples of the alkali-soluble resin in the photosensitive composition of the present invention include (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylonitrile, (a) other than the copolymer (D). A single or copolymer such as (meth) acrylamide, maleic acid, styrene, vinyl acetate, vinylidene chloride, maleimide, polyamide, polyester, polyether, polyurethane, polyvinyl butyral, polyvinyl alcohol, polyvinyl pyrrolidone, acetyl cellulose, etc. You may contain in the range which does not impair the effect of invention.
[0060]
In the blue-violet light-sensitive composition of the present invention, the ethylenically unsaturated compound (A), the sensitizing dye (B), the photopolymerization initiator (C), and the component (D) The content of each alkali-soluble resin is 20 to 80% by weight for component (A), 0.01 to 30% by weight for component (B), and 0 for component (C) with respect to the total amount of the photosensitive composition. 0.1-30 wt%, (D) component is preferably 20-70 wt%, (A) component is 30-70 wt%, (B) component is 0.1-20 wt%, (C) It is particularly preferable that the component is 0.5 to 20% by weight and the component (D) is 30 to 60% by weight.
[0061]
In addition, the blue-violet photosensitive composition of the present invention may further contain a hydrogen donating compound for the purpose of improving the photopolymerization initiation ability. Examples of the hydrogen donating compound include 2- Mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, 2-mercapto-4 (3H) -quinazoline, β-mercaptonaphthalene, ethylene glycol dithiopropionate Mercapto group-containing compounds such as trimethylolpropane tristhiopropionate and pentaerythritol tetrakisthiopropionate, polyfunctional thiol compounds such as hexanedithiol, trimethylolpropane tristhioglyconate and pentaerythritol tetrakisthiopropionate N, N-dialkylaminobenzoic acid ester, N-phenylglycine, or an ester thereof, a salt such as ammonium or sodium salt thereof, a derivative such as a dipolar compound thereof, phenylalanine or an ester thereof, a salt such as an ammonium or sodium salt thereof And amino acid having an aromatic ring such as a derivative such as a bipolar ion compound or a derivative thereof. Among them, in the present invention, mercapto group-containing compounds and amino acids or derivatives thereof are preferable.
[0062]
Furthermore, the blue-violet light-sensitive composition of the present invention may contain an epoxy group-containing compound for the purpose of imparting heat resistance, chemical resistance, etc. to the film after exposure, which will be described later. As the containing compound, constituting a repeating unit of a so-called epoxy resin, a polyglycidyl ether compound obtained by reacting a polyhydroxy compound and epichlorohydrin, a polyglycidyl ester compound obtained by reacting a polycarboxylic acid compound and epichlorohydrin, and Examples include compounds ranging from low molecular weight substances to high molecular weight substances such as polyglycidylamine compounds obtained by reacting a polyamine compound and epichlorohydrin.
[0063]
Specific examples of these polyglycidyl ether compounds include diglycidyl ether type epoxy of polyethylene glycol, diglycidyl ether type epoxy of bis (4-hydroxyphenyl), and bis (3,5-dimethyl-4-hydroxyphenyl). ) Diglycidyl ether type epoxy, bisphenol F diglycidyl ether type epoxy, bisphenol A diglycidyl ether type epoxy, tetramethylbisphenol A diglycidyl ether type epoxy, ethylene oxide-added bisphenol A diglycidyl ether type epoxy, phenol novolac Type epoxies, cresol novolac type epoxies, etc. These polyglycidyl ether compounds include acid anhydrides and divalent acid compounds on the remaining hydroxyl groups. It is also possible to introduce a carboxyl group to respond. Further, as the polyglycidyl ester compound, specifically, for example, diglycidyl ester type epoxy of hexahydrophthalic acid, diglycidyl ester type epoxy of phthalic acid, and the like, specifically, as the polyglycidyl amine compound, For example, diglycidylamine type epoxy of bis (4-aminophenyl) methane, triglycidylamine type epoxy of isocyanuric acid, and the like can be mentioned.
[0064]
For the same purpose, for example, tetracarboxylic acid such as pyromellitic dianhydride or a derivative thereof and diamine such as 3,3′-dimethyl-4,4′-diaminobiphenyl form an amide bond. And a polyimide precursor having an acid functional group or an ethylenically unsaturated bond.
[0065]
Each content ratio of the hydrogen donating compound and the epoxy group-containing compound in the blue-violet light-sensitive composition of the present invention is preferably 10% by weight or less with respect to the total amount of the photosensitive composition, More preferably, it is 5% by weight or less.
[0066]
Furthermore, the blue-violet light-sensitive composition of the present invention contains various additives, for example, thermal polymerization inhibitors such as hydroquinone, p-methoxyphenol, and 2,6-di-t-butyl-p-cresol. 2% by weight or less based on the total amount of the product, 20% by weight or less of a colorant comprising an organic or inorganic dye / pigment, and 40% by weight or less of a plasticizer such as dioctyl phthalate, didodecyl phthalate or tricresyl phosphate, Sensitivity property improving agents such as tertiary amines and thiols may also be contained in a proportion of 10% by weight or less, and a dye precursor in the same proportion of 30% by weight or less.
[0067]
The blue-violet photosensitive composition of the present invention preferably has a maximum peak of spectral sensitivity in the wavelength range of 390 to 430 nm, and more preferably has a maximum peak of spectral sensitivity in the wavelength range of 400 to 420 nm. When having a maximum peak of spectral sensitivity in a wavelength range less than the above range, the photosensitive composition is inferior in sensitivity to an exposure light source such as a laser beam having a wavelength of 390 to 430 nm, while having in a wavelength range exceeding the above range. Therefore, the safe light property under yellow light is inferior.
[0068]
In the present invention, the maximum peak of spectral sensitivity is, for example, described in detail in “Photopolymer Technology” (Ao Yamaoka, published by Nikkan Kogyo Shimbun, 1988, page 262), etc. Light obtained by spectrally separating a photosensitive image-forming material sample having a photosensitive layer formed on the substrate surface from a light source such as a xenon lamp or a tungsten lamp using a spectral sensitivity measuring device is linearly exposed in the vertical direction with a vertical exposure wavelength. The exposure intensity is set so that it changes logarithmically in the axial direction. After exposure and exposure, an image corresponding to the sensitivity of each exposure wavelength can be obtained by developing, and an image can be formed from that image height. The maximum peak in the spectral sensitivity curve obtained by calculating the exposure energy and plotting the wavelength on the horizontal axis and the reciprocal of the exposure energy on the vertical axis.
[0069]
The blue-violet light-sensitive composition of the present invention has a minimum exposure amount [S₄₁₀] Is 10mJ / cm²Or less, preferably 7 mJ / cm²More preferably, it is 5 mJ / cm.²It is particularly preferred that This minimum exposure [S₄₁₀] Exceeding the above range, depending on the exposure intensity of an exposure light source such as a laser beam, the exposure time becomes longer and the practicality is lowered. This minimum exposure amount [S₄₁₀] Is preferably as small as possible, but usually 1 mJ / cm²That's it.
[0070]
Further, the blue-violet light-sensitive composition of the present invention has the above [S₄₁₀The minimum exposure amount that can form an image at a wavelength of 450 nm [S₄₅₀(MJ / cm²)]] Ratio [S₄₁₀/ S₄₅₀] Is preferably 0.1 or less, and more preferably 0.05 or less. This ratio [S₄₁₀/ S₄₅₀] Exceeding the above range, it becomes difficult to achieve both the blue-violet light sensitivity and the safelight property under a yellow light.
[0071]
In addition, the blue-violet light-sensitive composition of the present invention has a minimum exposure amount that allows image formation at each wavelength of 450 nm to 650 nm [S_450-650(MJ / cm²)] Minimum exposure amount capable of forming an image at a wavelength of 450 nm [S₄₅₀(MJ / cm²)]] Ratio [S_450-650/ S₄₅₀] Is preferably more than 1. This ratio [S_450-650/ S₄₅₀] Below the above range, it tends to be difficult to achieve both the blue-violet light sensitivity and the safelight property under yellow light.
[0072]
The minimum exposure amount [S₄₁₀] Minimum exposure amount capable of forming an image at a wavelength of 450 nm [S₄₅₀, And the minimum exposure amount capable of forming an image at each wavelength of 450 nm to 650 nm [S_450-650] Is obtained as exposure energy capable of image formation calculated from the obtained image height in the measurement of the maximum peak of spectral sensitivity using the above-described spectral sensitivity measuring apparatus, the type of developer at that time, This means the minimum exposure that can form an image under optimum development conditions determined by changing development conditions such as development temperature and development time. As the optimum development conditions, the temperature is usually adjusted to an alkaline developer having a pH of 11 to 14. Conditions for immersion at 25 ° C. for 0.5 to 3 minutes are employed.
[0073]
The blue-violet light-sensitive composition of the present invention is a photosensitive composition that is formed on a temporary support film as a coating solution in which the above components are dissolved or dispersed in an appropriate solvent, and is dried as necessary. By covering the surface of the physical layer with a coating film, the blue-violet light-sensitive image forming material of the present invention as a so-called dry film resist material is formed, and the photosensitive composition layer side of the image forming material is covered with the coating film. If it is, the coating film is peeled off and laminated on the substrate to be processed, or as a coating solution in which the above components are dissolved or dispersed in an appropriate solvent, directly on the substrate to be processed. By applying and drying, the blue-violet light-sensitive image-forming material of the present invention in which the layer of the blue-violet light-sensitive composition of the present invention is formed on the substrate to be processed is obtained, and the blue-violet light-sensitive composition of the image-forming material Material layer, wavelength 3 Scanning exposure by a laser beam of 0～430Nm, it is suitably used in the use form as an image forming method for revealing a negative image by development.
[0074]
As a temporary support film in the case of being used as an image forming material as the dry film resist material, a conventionally known film such as a polyethylene terephthalate film, a polyimide film, a polyamideimide film, a polypropylene film, or a polystyrene film is used. At that time, when those films have the solvent resistance and heat resistance necessary for the production of the image forming material, the photosensitive composition coating solution is directly applied onto the temporary support film. Then, the image forming material of the present invention can be produced by drying, and even if those films have low solvent resistance or heat resistance, for example, polytetrafluoroethylene film, release film, etc. First, a photosensitive composition layer is formed on a film having releasability, and a temporary support film having low solvent resistance and heat resistance is laminated on the layer, and then a film having releasability is formed. By peeling, the image forming material of the present invention can be produced.
[0075]
The solvent used in the coating solution is not particularly limited as long as it has sufficient solubility for the components used and gives good coating properties. For example, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate Cellosolve solvents such as ethyl cellosolve acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol dimethyl ether, etc. Propylene glycol solvents, butyl acetate, amyl acetate, ethyl butyrate, butyl butyrate, diethyl oxalate, ethyl pyruvate Ester solvents such as ethyl-2-hydroxybutyrate, ethyl acetoacetate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, alcohol solvents such as heptanol, hexanol, diacetone alcohol, furfuryl alcohol, cyclohexanone, Examples thereof include ketone solvents such as methyl amyl ketone, highly polar solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, mixed solvents thereof, and those obtained by adding aromatic hydrocarbons thereto. The ratio of the solvent used is usually in the range of about 1 to 20 times by weight with respect to the total amount of the photosensitive composition.
[0076]
As the coating method, a conventionally known method such as a knife coating method, a roll coating method, a spray coating method, a spin coating method or the like can be used. The coating amount at that time is usually 5 μm or more as a dry film thickness, and 10 μm or more as a dry film resist material from the viewpoint of image formation described later and workability such as subsequent etching and plating. The thickness is preferably 15 μm or more, more preferably 200 μm or less, and even more preferably 100 μm or less from the viewpoint of sensitivity and the like. The drying temperature at that time is, for example, about 30 to 150 ° C., preferably about 40 to 110 ° C., and the drying time is, for example, about 5 seconds to 60 minutes, preferably about 10 seconds to 30 minutes. It is done.
[0077]
When used as an image forming material as a dry film resist material, etc., the surface of the formed photosensitive composition layer is covered with a coating film until the image forming material is laminated on a substrate to be processed. As the covering film, a conventionally known film such as a polyethylene film, a polypropylene film, or a polytetrafluoroethylene film is used.
[0078]
In addition, when the photosensitive composition layer side of the image forming material is covered with a coating film, the coating film is peeled off and laminated by heating, pressurizing, or the like. The substrate to be processed in producing the image forming material of the present invention by directly applying and drying the composition coating liquid is scanned and exposed to a photosensitive composition layer formed thereon by laser light and developed. A pattern such as a circuit or an electrode is formed on the surface by etching or plating using the negative image that has been revealed as a resist. Copper, aluminum, gold, silver, chromium, zinc, Although it may be a metal plate itself such as tin, lead, nickel, etc., usually, for example, epoxy resin, polyimide resin, bismaleimide resin, unsaturated polyester resin, phenol Thermosetting resin such as fat, melamine resin, saturated polyester resin, polycarbonate resin, polysulfone resin, acrylic resin, polyamide resin, polystyrene resin, polyvinyl chloride resin, polyolefin resin, resin such as thermoplastic resin, paper , Glass and inorganic materials such as alumina, silica, barium sulfate, calcium carbonate, or composite materials such as glass cloth base epoxy resin, glass nonwoven base epoxy resin, paper base epoxy resin, paper base phenol resin, etc. The metal or metal foil such as indium oxide, tin oxide, indium oxide doped tin oxide or the like is heated and pressure-bonded laminated on the surface of the insulating support having a thickness of about 0.02 to 10 mm. Or the thickness is 1-10 by sputtering, vapor deposition, plating, etc. Metal-clad laminate formed with μm order of the conductive layer is preferably used.
[0079]
In addition, when the image forming material of the present invention is produced by directly applying and drying the photosensitive composition coating liquid, polymerization of the photosensitive composition layer formed on the substrate to be processed by oxygen is performed. In order to prevent the prohibiting action, a protective layer formed by applying a solution such as polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, or the like on the photosensitive composition layer is dried. It may be provided.
[0080]
The image forming material of the present invention having a blue-violet light-sensitive composition layer on a substrate to be processed is after the temporary support film is peeled off when the photosensitive composition layer is formed of the image forming material. Or, when the photosensitive composition layer is formed by directly applying and drying the photosensitive composition coating liquid, and having the protective layer, after peeling the protective layer, The photosensitive composition layer is subjected to scanning exposure with blue-violet light, preferably with blue-violet laser light, and then developed to form a negative image on the substrate to be processed.
[0081]
As the exposure light source, carbon arc lamp, mercury lamp, xenon lamp, metal halide lamp, fluorescent lamp, tungsten lamp, halogen lamp, and laser such as HeNe laser, argon ion laser, YAG laser, HeCd laser, semiconductor laser, ruby laser, etc. Although a light source is mentioned, the light source which generate | occur | produces the laser beam of the blue-violet area | region of wavelength range 390-430 nm is especially preferable, and it is more preferable that the center wavelength is about 405 nm. Specific examples include an indium gallium nitride semiconductor laser that oscillates at 410 nm.
[0082]
Further, the scanning exposure method using laser light is not particularly limited, and examples thereof include a plane scanning exposure method, an outer drum scanning exposure method, an inner drum scanning exposure method, and the like. 1-100 mW, more preferably 3-70 mW, oscillation wavelength, preferably 390-430 nm, more preferably 400-420 nm, beam spot diameter, preferably 2-30 μm, more preferably 4-20 μm, scanning speed. The scanning exposure is preferably performed at 50 to 500 m / sec, more preferably 100 to 400 m / sec, and the scanning density is preferably 2,000 dpi or more, more preferably 4,000 dpi or more.
[0083]
The development processing after the exposure is preferably performed using an aqueous developer containing an alkali component and a surfactant. Examples of the alkali component include sodium silicate, potassium silicate, lithium silicate, ammonium silicate, sodium metasilicate, potassium metasilicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, Inorganic alkali salts such as dibasic sodium phosphate, tribasic sodium phosphate, dibasic ammonium phosphate, tribasic ammonium phosphate, sodium borate, potassium borate, ammonium borate, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, mono Isopropylamine, diisopropylamine, monobutylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine Organic amine compounds and the like, and used at a concentration of about 0.1 to 5 wt%.
[0084]
As the surfactant, nonionic, anionic or amphoteric surfactants are preferable, and amphoteric surfactants, especially betaine type compounds are preferable. The surfactant is preferably used at a concentration of 0.0001 to 20% by weight, more preferably 0.0005 to 10% by weight, and particularly preferably 0.001 to 5% by weight.
[0085]
Furthermore, the developing solution can contain an organic solvent such as isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol, if necessary. Further, the pH of the developer is preferably 9 to 14, and more preferably 11 to 14.
[0086]
The development is usually about 10 to 50 ° C., more preferably 20 to 20 ° C., by a known development method such as immersing the image forming material in the developer or spraying the developer on the image forming material. It is performed at a temperature of about 40 ° C. for a time of about 5 seconds to 10 minutes. Further, after the development processing, the formed negative image is irradiated with a light source such as a high-pressure mercury lamp, or / and heat-treated at a temperature of, for example, about 140 to 160 ° C. Etc. can be improved.
[0087]
【Example】
EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist.
[0088]
Example 1
As a substrate to be processed, a copper-clad laminated substrate (manufactured by Sanhayato Co., Ltd.) of polyimide resin having a thickness of 100 μm in which a copper foil having a thickness of 18 μm is laminated on one side, and a blue-violet photosensitive composition (A The following (A-1) as the ethylenically unsaturated compound of the component), the following (B-1) as the sensitizing dye of the component (B), and the following ( C-1) and the following components (D-1) as the alkali-soluble resin of component (D) were added to 1,000 parts by weight of a mixed solvent of hexanone / methyl cellosolve (weight ratio 5/5). A coating solution prepared by stirring for 10 minutes at room temperature is applied using a wire bar in an amount that results in a dry film thickness of 6 μm, and dried at 80 ° C. for 2 minutes. Photosensitive image-forming material having a photosensitive composition layer formed thereon It was produced.
[0089]
(A-1) Dipentaerythritol hexaacrylate; 50 parts by weight
(B-1) The following compound: 2 parts by weight
[0090]
[Chemical Formula 10]

[0091]
(C-1) 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole; 5 parts by weight
(D-1) methacrylic acid (15% by weight) / glycidyl methacrylate (30% by weight) / t-butyl methacrylate (30% by weight) / styrene (25% by weight) copolymer (weight average molecular weight 50,000); 50 parts by weight
[0092]
The obtained photosensitive image forming material was fixed to an aluminum drum having a diameter of 7 cm so that the photosensitive composition layer was on the outside, and a beam was used using a semiconductor laser (manufactured by Kiko Co., Ltd.) having a wavelength of 405 nm and 0.5 mW. After scanning exposure by changing the exposure amount by changing the drum rotation speed in the range of 0.1 to 100 rpm with a spot diameter of 50 μm, 0.5 wt% sodium silicate and 0.5 wt% surfactant A scanning line image is formed by developing an aqueous solution containing “Pelex NBL” manufactured by Kao Corporation as a developer, and the minimum exposure energy as the exposure sensitivity from the maximum number of revolutions of the drum on which the line image is formed Was determined to be 5 mJ / cm²Met.
[0093]
Furthermore, an iron oxide type copper etching solution (Sunhayato Co., Ltd.) was prepared by using, as a resist, a negative image produced by scanning exposure and developing the obtained photosensitive image forming material at twice the minimum exposure energy in the same manner as described above. After 5 minutes of immersion in a non-image area (non-exposed area), the resist is stripped and removed by immersion in a 1 wt% aqueous sodium hydroxide solution at 30 ° C. for 3 minutes. When the line image was visually observed, the copper in the non-image area (non-exposed area) was completely etched, and the copper in the image area (exposed area) was not observed at all. And the negative image as a resist was completely removed.
[0094]
Example 2
In Example 1, except that the photopolymerization initiator of the component (C) was changed to the following (C-2) and the blue-violet photosensitive composition to which the following other components (hydrogen-donating compound) were added was used. In the same manner as described above, a photosensitive image forming material was produced. Minimum exposure energy is 4 mJ / cm²Moreover, the same etching characteristics as in Example 1 were exhibited.
[0095]
(C-2) Dicyclopentadienyl titanium bis [2,6-difluoro-3- (1-pyrrolyl) phenyl]; 1 part by weight
(Others) 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one; 5 parts by weight
(Others) 2,4-diethylthioxanthone; 0.5 parts by weight
[0096]
Example 3
A photosensitive image forming material was produced in the same manner as in Example 1 except that the blue-violet photosensitive composition in which the sensitizing dye of component (B) was changed to the following (B-2) was used. The minimum exposure energy is 20 mJ / cm²Moreover, the same etching characteristics as in Example 1 were exhibited.
[0097]
(B-2) 4,4'-bis (diethylamino) benzophenone; 2 parts by weight
[0098]
Example 4
A photosensitive image forming material was produced in the same manner as in Example 1 except that the blue-violet photosensitive composition in which the sensitizing dye of component (B) was changed to the following (B-3) was used. Minimum exposure energy is 4 mJ / cm²Moreover, the same etching characteristics as in Example 1 were exhibited.
[0099]
(B-3) The following compound: 2 parts by weight
[0100]
Embedded image

[0101]
Example 5
A photosensitive image forming material was prepared in the same manner as in Example 1 except that the blue-violet photosensitive composition in which the sensitizing dye of component (B) was changed to the following (B-4) was used. Minimum exposure energy is 7mJ / cm²Moreover, the same etching characteristics as in Example 1 were exhibited.
[0102]
(B-4) The following compound: 2 parts by weight
[0103]
Embedded image

[0104]
Comparative Example 1
A photosensitive image forming material was produced in the same manner as in Example 1 except that the blue-violet light-sensitive composition in which the photopolymerization initiator was changed to the following (C-3) was used, and an image was formed. I couldn't.
[0105]
(C-3) 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine; 5 parts by weight
[0106]
Comparative Example 2
The photopolymerization initiator was changed to the above (C-3), and the blue-violet photosensitive composition in which the alkali-soluble resin was changed to the following (D-2) was used in the same manner as in Example 1. When a photosensitive image forming material was produced, an image could not be formed. In addition, this comparative example is corresponded to the resin composition of Unexamined-Japanese-Patent No. 2002-278064 mentioned in the column of a prior art.
[0107]
(D-2) Methacrylic acid (20% by weight) / Glycidyl methacrylate (45% by weight) / Tricyclomethacrylate [5.2.1.0^2,6] Decan-8-yl (25% by weight) / styrene (10% by weight) copolymer (weight average molecular weight 50,000); 50 parts by weight
[0108]
Comparative Example 3
The blue-violet light-sensitive composition in which the alkali-soluble resin was changed to the following (D-3) was used, and 0.5% by weight of sodium carbonate and 0.5% by weight of surfactant (as a developer) A photosensitive image forming material was prepared in the same manner as in Example 1 except that an aqueous solution containing “Perex NBL” manufactured by Kao Corporation was used. The minimum exposure energy was 40 mJ / cm.²Met. When the formed line image was visually observed, a red thin film remained slightly on the copper surface of the non-image part (non-exposed part). Further, in the etching process, an area portion of about 5% of the copper foil in the non-image area (non-exposed area) was not etched.
[0109]
(D-3) Reaction obtained by reacting 3,4-epoxycyclohexylmethyl acrylate with a methacrylic acid (45% by weight) / t-butyl methacrylate (30% by weight) / styrene (25% by weight) copolymer Product (weight average molecular weight 50,000, 66 mol% of carboxyl group of methacrylic acid component reacts with epoxy group); 50 parts by weight
[0110]
Example 6
As a blue-violet photosensitive composition, the following (A-2), (A-3) and (B) as sensitizing dyes as the sensitizing dyes as components (A) and ethylenically unsaturated compounds as components (B-5) ), The following (C-4) as the photopolymerization initiator of the component (C), the following (D-4) as the alkali-soluble resin of the component (D), and the following other components (hydrogen donating compounds): A polyethylene terephthalate film (thickness: 19 μm) as a temporary support film was prepared by adding each of the above components to 100 parts by weight of a mixed solvent of methyl ethyl ketone / isopropanol (weight ratio 8/2) and stirring the solution at room temperature. A polyethylene film (thickness 2) as a coating film is coated on the photosensitive composition layer formed by applying an applicator to the film so that the dry film thickness is 25 μm and drying it in an oven at 90 ° C. for 5 minutes. 5 μm) was laminated and allowed to stand for 1 day to produce a photosensitive image forming material.
[0111]
(A-2) The following compound (“Light Ester 9EG” manufactured by Kyoei Chemical Co., Ltd.); 15 parts by weight
(A-3) The following compound (“Light Ester BP-6EM” manufactured by Kyoei Chemical Co., Ltd.); 30 parts by weight
[0112]
Embedded image

[0113]
(B-5) The following compound: 0.2 part by weight
[0114]
Embedded image

[0115]
(C-4) 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole; 15 parts by weight
(D-4) methacrylic acid (15% by weight) / glycidyl methacrylate (30% by weight) / t-butyl methacrylate (30% by weight) / styrene (25% by weight) copolymer (weight average molecular weight 50,000); 50 parts by weight
(Others) 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one; 5 parts by weight
(Others) 2,4-diethylthioxanthone; 0.1 parts by weight
[0116]
Separately, a copper foil surface of a polyimide resin copper-clad laminate (thickness 1.5 mm, size 250 mm × 200 mm) bonded with a 35 μm-thick copper foil is buffed with “Scotch Bright SF” manufactured by Sumitomo 3M Limited. After washing with water and drying with an air stream, the surface is then preheated to 60 ° C. in an oven, and then the photosensitive image-forming material obtained above is placed on the copper foil of the copper-clad laminate. On the copper-clad laminate by laminating at a roll temperature of 100 ° C., a roll pressure of 0.3 MPa, and a laminating speed of 1.5 m / min using a hand-type roll laminator while peeling off the polyethylene film. A photosensitive image forming material in which a blue-violet light-sensitive composition layer was formed was prepared.
[0117]
The obtained photosensitive image forming material was fixed to an aluminum drum having a diameter of 7 cm so that the photosensitive composition layer was on the outside, and a beam was used using a semiconductor laser (manufactured by Kiko Co., Ltd.) having a wavelength of 405 nm and 0.5 mW. After scanning exposure by changing the exposure amount by changing the drum rotation speed in the range of 5 to 100 rpm with a spot diameter of 50 μm, 0.5 wt% sodium silicate and 0.5 wt% surfactant (Kao An aqueous solution containing “Perex NBL” manufactured by the company is sprayed as a developing solution to a pressure of 0.15 MPa, and spray development is performed in a time twice as long as the minimum developing time to reveal a negative image. As for the exposure sensitivity, the exposure energy required to reproduce the line width of 10 μm was determined to be 1.0 mJ / cm.²Met.
[0118]
Furthermore, when the maximum peak of spectral sensitivity was measured by the method shown below, it was about 410 nm.
<Maximum peak of spectral sensitivity>
A sample obtained by cutting the image forming material into a size of 50 × 60 mm is 350 using a diffraction spectroscopic irradiation device (“RM-23” manufactured by Narumi) and a xenon lamp (“UI-501C” manufactured by USHIO INC.) As a light source. The light dispersed in the wavelength region of ˜650 nm is exposed by irradiating for 10 seconds with the exposure wavelength set linearly in the horizontal axis direction and logarithmically changing the exposure intensity in the vertical axis direction, and then 30 An aqueous solution of 1 wt% sodium carbonate and 0.5 wt% surfactant ("Perex NBL" manufactured by Kao Corporation) is sprayed as a developing solution to a pressure of 0.15 MPa and sprayed for twice the minimum development time. By developing, an image corresponding to the sensitivity of each exposure wavelength is obtained, and the exposure energy capable of forming an image is calculated from the image height, and the wavelength is plotted on the horizontal axis and the inverse of the exposure energy is plotted on the vertical axis. Read a maximum peak in the spectral sensitivity curve obtained by.
[0119]
Further, the minimum exposure amount [S₄₁₀(MJ / cm²)] Was measured to find 1.2 mJ / cm²Met. Also, the minimum exposure amount [S₄₁₀The minimum exposure amount that can form an image at a wavelength of 450 nm [S₄₅₀(MJ / cm²)]] Ratio [S₄₁₀/ S₄₅₀, And the minimum exposure amount capable of forming an image at each wavelength of 450 nm to 650 nm [S_450-650(MJ / cm²)] Minimum exposure amount capable of forming an image at a wavelength of 450 nm [S₄₅₀(MJ / cm²)]] Ratio [S_{45 0-650}/ S₄₅₀] And was evaluated according to the following criteria.₄₁₀/ S₄₅₀] And [S_450-650/ S₄₅₀Both were “A”.
[0120]
<S₄₁₀, S₄₁₀/ S₄₅₀, S_450-650/ S₄₅₀>
In the same manner as described above, the minimum exposure amount capable of forming an image at a wavelength of 410 nm when the exposure is carried out by changing the wavelength in the wavelength range of 350 to 650 nm and developed [S₄₁₀(MJ / cm²)] And the minimum exposure amount that can form an image at a wavelength of 450 nm [S₄₅₀(MJ / cm²)], And the minimum exposure amount capable of forming an image at each wavelength of 450 nm to 650 nm [S_450-650(MJ / cm²)] And the ratio [S₄₁₀/ S₄₅₀] And [S_450-650/ S₄₅₀] Was calculated and evaluated according to the following criteria.
[0121]
<S₄₁₀/ S₄₅₀Evaluation criteria>
A: S₄₁₀/ S₄₅₀Is 0.03 or less.
B: S₄₁₀/ S₄₅₀Is more than 0.03 and less than 0.05.
C: S₄₁₀/ S₄₅₀Is more than 0.05 and 0.1 or less.
D: S₄₁₀/ S₄₅₀Is over 0.1.
[0122]
<S_450-650/ S₄₅₀Evaluation criteria>
A: S_450-650/ S₄₅₀Is over 10.
B: S_450-650/ S₄₅₀Is more than 5 and less than 10.
C: S_450-650/ S₄₅₀Is more than 1 and less than 5.
D: S_450-650/ S₄₅₀Is 1 or less.
[0123]
Separately, with respect to the obtained photosensitive image forming material, the safelight property under a yellow light was evaluated by the method shown below, it was “A”.
<Safelight characteristics under yellow light>
The image forming material was allowed to stand for 1 minute, 2 minutes, 5 minutes, 10 minutes, 20 minutes, 30 minutes under yellow light illumination (conditions in which light having a wavelength of about 470 nm or less was blocked). Scanning exposure and development processing were performed, and the standing time until the image changed compared to the above was obtained, and evaluated according to the following criteria.
A: More than 20 minutes
B: 10 minutes or more and less than 20 minutes
C: 1 minute or more and less than 10 minutes
D: Less than 1 minute
[0124]
【The invention's effect】
The present invention is a photosensitive composition excellent in sensitivity to blue-violet light and developability, and in particular, a blue-violet photosensitive composition suitable for use as a dry film resist material and for direct drawing with a blue-violet laser beam, In addition, an image forming material, an image forming material, and an image forming method using the same can be provided.

Claims (10)

A blue-violet light-sensitive composition comprising the following components (A), (B), (C), and (D):
(A) ethylenically unsaturated compound (B) sensitizing dye having a maximum spectral sensitivity peak in the blue-violet region with a wavelength of 390 to 430 nm (C) a photopolymerization initiator comprising a hexaarylbiimidazole compound or a titanocene compound ( D) Alkali-soluble resin comprising a carboxyl group and an epoxy group-containing vinyl copolymer containing a constitutional repeating unit derived from an ethylenically unsaturated carboxylic acid and a constitutional repeating unit derived from an epoxy group-containing ethylenically unsaturated compound   (D) Component repeating unit derived from (meth) acrylic acid alkyl ester, and repeating unit derived from vinyl aromatic compound, wherein carboxyl group and epoxy group-containing vinyl copolymer as alkali-soluble resin of component (D) The blue-violet light-sensitive composition according to claim 1 comprising a unit. (D) Component repeating unit derived from ethylenically unsaturated carboxylic acid with respect to the total amount of the carboxyl group- and epoxy-group-containing vinyl copolymer as the alkali-soluble resin of the component is 5 to 30% by weight. The structural repeating unit derived from an epoxy group-containing ethylenically unsaturated compound is composed of 5 to 40% by weight, and the structural repeating unit derived from another monomer is composed of 30 to 90% by weight. Blue-violet light-sensitive composition. Ethylenically unsaturated compound of the component (A) has a polyoxyalkylene group, according to any one of claims 1 to 3 containing (meth) acryloyloxy group of the ester having two or more (meth) acrylates Blue-violet light-sensitive composition. The blue-violet light-sensitive composition according to any one of claims 1 to 4 , wherein the sensitizing dye as the component (B) is a dialkylaminobenzene compound. The dialkylaminobenzene compound is a dialkylaminobenzophenone compound represented by the following general formula (I), a dialkylaminobenzene compound having a sulfonylimino group represented by the following general formula (III), and the following general formula (IV The blue-violet light-sensitive composition according to claim 5 , which is any compound selected from the group consisting of dialkylaminobenzene compounds having a carbostyril skeleton represented by

[In the formula (I), R ¹ , R ² , R ⁵ and R ⁶ each independently represents an alkyl group which may have a substituent, and R ³ , R ⁴ , R ⁷ and R ⁸ each independently represents an alkyl group which may have a substituent, or a hydrogen atom, R ¹ and R ² , R ³ and R ⁴ , R ¹ and R ³ , R ² and R ⁴ , R ⁵ and R ⁷ , and R ⁶ and R ⁸ may each independently form a nitrogen-containing heterocycle. ]

[In Formula (III), R ¹ and R ² each independently represents an alkyl group which may have a substituent, and R ⁴ and R ⁴ each independently have a substituent. also alkyl group, or a hydrogen atom, R ¹ and R ^2, R ¹ and R ^3, and each, independently of R ² and R ^4, may form a nitrogen-containing heterocyclic ring, R ⁹ Represents a monovalent group or a hydrogen atom, and R ¹⁰ represents a monovalent group. ]

[In the formula (IV), R ¹ , R ² and R ¹¹ each independently represents an alkyl group which may have a substituent, and R ³ and R ⁴ each independently represents a substituent. An alkyl group which may have or a hydrogen atom, R ¹ and R ² , R ¹ and R ³ , and R ² and R ⁴ may each independently form a nitrogen-containing heterocycle; R ¹² represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or a hydrogen atom. ] A blue-violet light-sensitive image-forming material comprising a layer of the blue-violet light-sensitive composition according to any one of claims 1 to 6 formed on a temporary support film. A blue-violet light-sensitive image forming material comprising the blue-violet light-sensitive image forming material according to claim 7 laminated on a processed substrate on the blue-violet light-sensitive composition layer side. The blue-violet light-sensitive image forming material according to claim 8 , wherein the thickness of the blue-violet light-sensitive composition layer in the blue-violet light-sensitive image forming material laminated on the substrate to be processed is 10 μm or more. The blue-violet light-sensitive photosensitive composition layer of the blue-violet light-sensitive image forming material according to claim 8 or 9 is scanned and exposed with a laser beam having a wavelength of 390 to 430 nm, and developed to produce a negative image. An image forming method.