JP4478843B2 - Package, method for manufacturing package, method for storing package, and method for preventing edge fusion of photosensitive element - Google Patents

Description

（式中、Ｒ¹は水素原子又はメチル基を示し、Ｒ²は炭素数１〜１２のアルキル基を示す）
で表される化合物、これらの化合物のアルキル基に水酸基、エポキシ基、ハロゲン基等が置換した化合物などが挙げられる。
上記一般式（Ｉ）中のＲ²で示される炭素数１〜１２のアルキル基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基及びこれらの構造異性体が挙げられる。
【００３２】
上記一般式（Ｉ）で表される単量体としては、例えば、（メタ）アクリル酸メチルエステル、（メタ）アクリル酸エチルエステル、（メタ）アクリル酸プロピルエステル、（メタ）アクリル酸ブチルエステル、（メタ）アクリル酸ペンチルエステル、（メタ）アクリル酸ヘキシルエステル、（メタ）アクリル酸ヘプチルエステル、（メタ）アクリル酸オクチルエステル、（メタ）アクリル酸２−エチルヘキシルエステル、（メタ）アクリル酸ノニルエステル、（メタ）アクリル酸デシルエステル、（メタ）アクリル酸ウンデシルエステル、（メタ）アクリル酸ドデシルエステル、等が挙げられる。これらは単独で又は２種以上を組み合わせて用いることができる。
【００３３】
前記（Ａ）バインダーポリマーは、アルカリ現像性の見地から、カルボキシル基を含有させることが好ましく、例えば、カルボキシル基を有する重合性単量体とその他の重合性単量体をラジカル重合させることにより製造することができる。
上記カルボキシル基を有する重合性単量体としては、メタクリル酸が好ましい。また、前記（Ａ）バインダーポリマーは、可とう性の見地からスチレン又はスチレン誘導体を重合性単量体として含有させることが好ましい。
【００３４】
上記スチレン又はスチレン誘導体を共重合成分として、密着性及び剥離特性を共に良好にするには、０．１〜３０重量％含むことが好ましく、１〜２８重量％含むことがより好ましく、１．５〜２７重量％含むことが特に好ましい。この含有量が０．１重量％未満では、密着性が劣る傾向があり、３０重量％を超えると、剥離片が大きくなり、剥離時間が長くなる傾向がある。
【００３５】
これらのバインダーポリマーは、単独で又は２種類以上を組み合わせて使用される。２種類以上を組み合わせて使用する場合のバインダーポリマーとしては、例えば、異なる共重合成分からなる２種類以上のバインダーポリマー、異なる重量平均分子量の２種類以上のバインダーポリマー、異なる分散度の２種類以上のバインダーポリマーなどが挙げられる。
【００３６】
前記（Ａ）バインダーポリマーは、重量平均分子量が２０，０００〜２００，０００であることが好ましく、４０，０００〜１２０，０００であることがより好ましい。この重量平均分子量が２０，０００未満では耐現像液性及び膜強度が低下する傾向があり、２００，０００を超えると解像度が低下する傾向がある。但し、重量平均分子量は、ゲルパーミエーションクロマトグラフィー法により測定され、標準ポリスチレンを用いて作成した検量線により換算されたものである。
【００３７】
前記（Ｂ）光重合性化合物としては、例えば、多価アルコールにα，β−不飽和カルボン酸を反応させて得られる化合物、２，２−ビス（４−（（メタ）アクリロキシポリエトキシ）フェニル）プロパン、２，２−ビス（４−（（メタ）アクリロキシポリプロポキシ）フェニル）プロパン、２，２−ビス（４−（（メタ）アクリロキシポリブトキシ）フェニル）プロパン、２，２−ビス（４−（（メタ）アクリロキシポリエトキシポリプロポキシ）フェニル）プロパン等のビスフェノールＡ系（メタ）アクリレート化合物、グリシジル基含有化合物にα、β−不飽和カルボン酸を反応させで得られる化合物、ウレタン結合を有する（メタ）アクリレート化合物等のウレタンモノマー、ノニルフェニルジオキシレン（メタ）アクリレート、γ−クロロ−β−ヒドロキシプロピル−β′−（メタ）アクリロイルオキシエチル−ｏ−フタレート、β−ヒドロキシエチル−β′−（メタ）アクリロイルオキシエチル−ｏ−フタレート、β−ヒドロキシプロピル−β′−（メタ）アクリロイルオキシエチル−ｏ−フタレート、（メタ）アクリル酸アルキルエステル等が挙げられるが、ビスフェノールＡ系（メタ）アクリレート化合物又はウレタン結合を有する（メタ）アクリレート化合物を必須成分とすることが好ましい。これらは単独で又は２種類以上を組み合わせて使用される。
【００３８】
上記多価アルコールにα，β−不飽和カルボン酸を反応させて得られる化合物としては、例えば、エチレン基の数が２〜１４であるポリエチレングリコールジ（メタ）アクリレート、プロピレン基の数が２〜１４であるポリプロピレングリコールジ（メタ）アクリレート、エチレン基の数が２〜１４であり、プロピレン基の数が２〜１４であるポリエチレンポリプロピレングリコールグリコールジ （メタ）アクリレート、トリメチロールプロパンジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、トリメチロールプロパンエトキシトリ（メタ）アクリレート、ＥＯ変性トリメチロールプロパントリ（メタ）アクリレート、ＰＯ変性トリメチロールプロパントリ（メタ）アクリレート、ＥＯ，ＰＯ変性トリメチロールプロパントリ（メタ）アクリレート、テトラメチロールメタントリ（メタ）アクリレート、テトラメチロールメタンテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート等が挙げられる。
上記α，β−不飽和カルボン酸としては、例えば、（メタ）アクリル酸等が拳げられる。
【００３９】
上記２，２−ビス（４−（（メタ）アクリロキシポリエトキシ）フェニル）プロパンとしては、例えば、２，２−ビス（４−（（メタ）アクリロキシジエトキシ）フェニル）プロパン、２，２−ビス（４−（（メタ）アクリロキシトリエトキシ）フェニル）プロパン、２，２−ビス（４−（（メタ）アクリロキシテトラエトキシ）フェニル）プロパン、２，２−ビス（４−（（メタ）アクリロキシペンタエトキシ）フェニル）プロパン、２，２−ビス（４−（（メタ）アクリロキシヘキサエトキシ）フェニル）プロパン、２，２−ビス（４−（（メタ）アクリロキシヘプタエトキシ）フェニル）プロパン、２，２−ビス（４−（（メタ）アクリロキシオクタエトキシ）フェニル）プロパン、２，２−ビス（４−（（メタ）アクリロキシノナエトキシ）フェニル）プロパン、２，２−ビス（４−（（メタ）アクリロキシデカエトキシ）フェニル）プロパン、２，２−ビス（４−（ （メタ）アクリロキシウンデカエトキシ）フェニル）プロパン、２，２−ビス （４−（（メタ）アクリロキシドデカエトキシ）フェニル）プロパン、２，２−ビス（４−（（メタ）アクリロキシトリデカエトキシ）フェニル）プロパン、２，２−ビス（４−（（メタ）アクリロキシテトラデカエトキシ）フェニル）プロパン、２，２−ビス（４−（（メタ）アクリロキシペンタデカエトキシ）フェニル）プロパン、２，２−ビス（４−（（メタ）アクリロキシヘキサデカエトキシ）フェニル）プロパン等が挙げられ、２，２−ビス（４−（メタクリロキシペンタエトキシ）フェニル）プロパンは、ＢＰＥ−５００（新中村化学工業(株)製、製品名）として商業的に入手可能であり、２，２−ビス（４−（メタクリロキシペンタデカエトキシ）フェニル）プロパンは、ＢＰＥ−１３００（新中村化学工業(株)製、製品名）として商業的に入手可能である。これらは単独で又は２種類以上を組み合わせて使用される。
【００４０】
上記２，２−ビス（４−（（メタ）アクリロキシポリプロポキシ）フェニル）プロパンとしては、例えば、２，２−ビス（４−（（メタ）アクリロキシジプロポキシ）フェニル）プロパン、２，２−ビス（４−（（メタ）アクリロキシトリプロポキシ）フェニル）プロパン、２，２−ビス（４−（（メタ）アクリロキシテトラプロポキシ）フェニル）プロパン、２，２−ビス（４−（（メタ）アクリロキシペンタプロポキシ）フェニル）プロパン、２，２−ビス（４−（（メタ）アクリロキシヘキサプロポキシ）フェニル）プロパン、２，２−ビス（４−（ （メタ）アクリロキシヘプタプロポキシ）フェニル）プロパン、２，２−ビス （４−（（メタ）アクリロキシオクタプロポキシ）フェニル）プロパン、２，２−ビス（４−（（メタ）アクリロキシノナプロポキシ）フェニル）プロパン、２，２−ビス（４−（（メタ）アクリロキシデカプロポキシ）フェニル）プロパン、２，２−ビス（４−（（メタ）アクリロキシウンデカプロポキシ）フェニル）プロパン、２，２−ビス（４−（（メタ）アクリロキシドデカプロポキシ）フェニル）プロパン、２，２−ビス（４−（（メタ）アクリロキシトリデカプロポキシ）フェニル）プロパン、２，２−ビス（４−（（メタ）アクリロキシテトラデカプロポキシ）フェニル）プロパン、２，２−ビス（４−（（メタ）アクリロキシペンタデカプロポキシ）フェニル）プロパン、２，２−ビス（４−（（メタ）アクリロキシヘキサデカプロポキシ）フェニル）プロパン等が挙げられる。これらは単独で又は２種類以上を組み合わせて使用される。
【００４１】
上記２，２−ビス（４−（（メタ）アクリロキシポリエトキシポリプロポキシ）フェニル）プロパンとしては、例えば、２，２−ビス（４−（（メタ）アクリロキシジエトキシオクタプロポキシ）フェニル）プロパン、２，２−ビス（４−（（メタ）アクリロキシテトラエトキシテトラプロポキシ）フェニル）プロパン、２，２−ビス（４−（（メタ）アクリロキシヘキサエトキシヘキサプロポキシ）フェニル）プロパン等が挙げられる。これらは単独で又は２種類以上を組み合わせて使用される。
上記グリシジル基含有化合物としては、例えば、トリメチロールプロパントリグリシジルエーテルトリ（メタ）アクリレート、２，２−ビス（４−（メタ）アクリロキシ−２−ヒドロキシ−プロピルオキシ）フェニル等が拳げられる。
【００４２】
上記ウレタンモノマーとしては、例えば、β位にＯＨ基を有する（メタ）アクリルモノマーとイソホロンジイソシアネート、２，６−トルエンジイソシアネート、２，４−トルエンジイソシアネート、１，６−ヘキサメチレンジイソシアネート等のジイソシアネート化合物との付加反応物、トリス（（メタ）アクリロキシテトラエチレングリコールイソシアネート）ヘキサメチレンイソシアヌレート、ＥＯ変性ウレタンジ（メタ）アクリレート、ＥＯ，ＰＯ変性ウレタンジ（メタ）アクリレート等が挙げられる。ＥＯ変性ウレタンジ（メタ）アクリレートとしては、例えば、新中村化学工業(株)製、製品名ＵＡ−１１等が挙げられる。また、ＥＯ，ＰＯ変性ウレタンジ（メタ）アクリレートとしては、例えば、新中村化学工業(株)製、製品名ＵＡ−１３等が挙げられる。
上記（メタ）アクリル酸アルキルエステルとしては、例えば、（メタ）アクリル酸メチルエステル、（メタ）アクリル酸エチルエステル、（メタ）アクリル酸ブチルエステル、（メタ）アクリル酸２−エチルヘキシルエステル等が挙げられる。
なお、ＥＯはエチレンオキサイドを示し、ＥＯ変性された化合物はエチレンオキサイド基のブロック構造を有する。また、ＰＯはプロピレンオキサイドを示し、ＰＯ変性された化合物はプロピレンオキサイド基のブロック構造を有する。
【００４３】
前記（Ｃ）光重合開始剤としては、例えば、ベンゾフェノン、Ｎ，Ｎ′−テトラメチル−４，４′−ジアミノベンゾフェノン（ミヒラーケトン）、Ｎ，Ｎ′−テトラエチル−４，４′−ジアミノベンゾフェノン、４−メトキシ−４′−ジメチルアミノベンゾフェノン、２−ベンジル−２−ジメチルアミノ−１−（４−モルホリノフェニル）−ブタノン−１、２−メチル−１−［４−（メチルチオ）フェニル］−２−モルフォリノ−プロパノン−１等の芳香族ケトン、２−エチルアントラキノン、フェナントレンキノン、２ーｔｅｒｔーブチルアントラキノン、オクタメチルアントラキノン、１，２ーベンズアントラキノン、２，３ーベンズアントラキノン、２ーフェニルアントラキノン、２，３ージフェニルアントラキノン、１ークロロアントラキノン、２ーメチルアントラキノン、１，４−ナフトキノン、９，１０−フェナンタラキノン、２−メチル１，４−ナフトキノン、２，３−ジメチルアントラキノン等のキノン類、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインフェニルエーテル等のベンゾインエーテル化合物、ベンゾイン、メチルベンゾイン、エチルベンゾイン等のベンゾイン化合物、ベンジルジメチルケタール等のベンジル誘導体、２−（ｏ−クロロフェニル）−４，５−ジフェニルイミダゾール二量体、２−（ｏ−クロロフェニル）−４，５−ジ（メトキシフェニル）イミダゾール二量体、２−（ｏ−フルオロフェニル）−４，５−ジフェニルイミダゾール二量体、２−（ｏ−メトキシフェニル）−４，５−ジフェニルイミダゾール二量体、２−（ｐ−メトキシフェニル）−４，５−ジフェニルイミダゾール二量体等の２，４，５−トリアリールイミダゾール二量体、９−フェニルアクリジン、１，７−ビス（９，９′−アクリジニル）ヘプタン等のアクリジン誘導体、Ｎ−フェニルグリシン、Ｎ−フェニルグリシン誘導体、クマリン系化合物などが挙げられる。
【００４４】
また、２つの２，４，５−トリアリールイミダゾールのアリール基の置換基は同一で対象な化合物を与えてもよいし、相違して非対称な化合物を与えてもよい。
また、ジエチルチオキサントンとジメチルアミノ安息香酸の組み合わせのように、チオキサントン系化合物と３級アミン化合物とを組み合わせてもよい。
また、密着性及び感度の見地からは、２，４，５−トリアリールイミダゾール二量体がより好ましい。
これらは、単独で又は２種類以上を組み合わせて使用される。
【００４５】
また、本発明の感光性樹脂組成物には、必要に応じて、分子内に少なくとも１つのカチオン重合可能な環状エーテル基を有する光重合性化合物、カチオン重合開始剤、マラカイトグリーン等の染料、トリブロモフェニルスルホン、ロイコクリスタルバイオレット等の光発色剤、熱発色防止剤、ｐ−トルエンスルホンアミド等の可塑剤、顔料、充填剤、消泡剤、難燃剤、安定剤、密着性付与剤、レベリング剤、剥離促進剤、酸化防止剤、香料、イメージング剤、熱架橋剤などを（Ａ）成分及び（Ｂ）成分の総量１００重量部に対して各々０．０１〜２０重量部程度含有することができる。これらは、単独で又は２種類以上を組み合わせて使用される。
【００４６】
本発明の感光性樹脂組成物は、必要に応じて、メタノール、エタノール、アセトン、メチルエチルケトン、メチルセロソルブ、エチルセロソルブ、トルエン、Ｎ，Ｎ−ジメチルホルムアミド、プロピレングリコールモノメチルエーテル等の溶剤又はこれらの混合溶剤に溶解して固形分３０〜６０重量％程度の溶液として塗布することができる。
【００４７】
本発明の感光性樹脂組成物は、特に制限はないが、金属面、例えば、銅、銅系合金、ニッケル、クロム、鉄、ステンレス等の鉄系合金、好ましくは銅、銅系合金、鉄系合金の表面上に、液状レジストとして塗布して乾燥後、必要に応じて保護フィルムを被覆して用いるか、感光性エレメントの形態で用いられることが好ましい。
【００４８】
また、感光性樹脂組成物層の厚みは、用途により異なるが、乾燥後の厚みで１〜２００μｍであることが好ましく、１〜１００μｍであることがより好ましく、１〜３０μｍであることが特に好ましい。この厚みが１μｍ未満では工業的に塗工困難な傾向があり、２００μｍを超える場合では本発明の効果が小さく、また感度が不十分となり、レジスト底部の光硬化性が悪化する傾向がある。液状レジストに保護フィルムを被覆して用いる場合は、保護フィルムとして、ポリエチレン、ポリプロピレン等の不活性なポリオレフィンフィルム等が用いられるが、感光性樹脂組成物層からの剥離性の見地から、ポリエチレンフィルムが好ましい。
【００４９】
上記感光性エレメントは、例えば、支持体として、ポリエチレンテレフタレート、ポリプロピレン、ポリエチレン、ポリエステル等の耐熱性及び耐溶剤性を有する重合体フィルム上に感光性樹脂組成物を塗布、乾燥することにより得られる。透明性の見地からは、ポリエチレンテレフタレートフィルムを用いることが好ましい。
上記塗布は、ロールコータ、コンマコータ、グラビアコータ、エアーナイフコータ、ダイコータ、バーコータ、スレーコータ等の公知の方法で行うことができる。また、乾燥は、７０〜１５０℃、５〜３０分程度で行うことができる。
また、感光性樹脂組成物層中の残存有機溶剤量は、後の工程での有機溶剤の拡散を防止する点から、２重量％以下とすることが好ましい。
【００５０】
また、これらの重合体フィルムは、後に感光性樹脂組成物層から除去可能でなくてはならないため、除去が不可能となるような表面処理が施されたものであったり、材質であったりしてはならない。これらの重合体フィルムの厚みは、１〜１００μｍとすることが好ましく、１〜３０μｍとすることがより好ましい。この厚みが１μｍ未満の場合、機械的強度が低下し、塗工時に重合体フィルムが破れるなどの問題が発生する傾向があり、３０μｍを超えると解像度が低下し、価格が高くなる傾向がある。
これらの重合体フィルムの一つは感光性樹脂組成物層の支持フィルムとして、他の一つは感光性樹脂組成物の保護フィルムとして感光性樹脂組成物層の両面に積層してもよい。
保護フィルムとしては、感光性樹脂組成物層及び支持体の接着力よりも、感光性樹脂組成物層及び保護フィルムの接着力の方が小さいものが好ましく、また、低フィッシュアイのフィルムが好ましい。
【００５１】
このようにして得られる感光性樹脂組成物層と重合体フィルムとの２層からなる本発明の感光性エレメントは、例えば、そのまま又は感光性樹脂組成物層の他の面に保護フィルムをさらに積層して円筒状の巻芯に巻きとって貯蔵される。
なお、この際支持フィルムが１番外側になるように巻き取られることが好ましい。上記ロール状の感光性エレメントロールの端面には、端面保護の見地から端面セパレータを設置することが好ましく、耐エッジフュージョンの見地から防湿端面セパレータを設置することが好ましい。
また、梱包方法として、透湿性の小さいブラックシートに包んで包装することが好ましい。
上記巻芯としては、例えば、ポリエチレン樹脂、ポリプロピレン樹脂、ポリスチレン樹脂、ポリ塩化ビニル樹脂、ＡＢＳ樹脂（アクリロニトリル−ブタジエン−スチレン共重合体）等のプラスチックなどが挙げられる。
【００５２】
上記感光性エレメントを用いてレジストパターンを製造するに際しては、前記の保護フィルムが存在している場合には、保護フィルムを除去後、感光性樹脂組成物層を加熱しながら回路形成用基板に０．１〜１MPa程度（１〜１０kgf/cm²程度）圧力で圧着することにより積層する方法などが挙げられる。
このようにして積層が完了した感光性樹脂組成物層は、アートワークと呼ばれるネガ又はポジマスクパターンを通して活性光線が画像状に照射される。
次いで、露光後、感光性樹脂組成物層上に支持体が存在している場合には、支持体を除去した後、アルカリ性水溶液、水系現像液、有機溶剤等の現像液によるウエット現像、ドライ現像等で未露光部を除去して現像し、レジストパターンを製造する。
【００５３】
【実施例】
以下、本発明を実施例及び比較例に基づいて詳細に説明する。
【００５４】
実施例１〜３及び比較例１〜２
表１に示す（Ａ）成分、（Ｂ）成分、（Ｃ）成分及びその他の成分を混合し、感光性樹脂組成物の溶液を調製した。
【００５５】
【表１】

【００５６】
次いで、この感光性樹脂組成物の溶液を１６μｍ厚のポリエチレンテレフタレートフイルム上に均一に塗布し、１００℃の熱風対流乾燥機で５分間乾燥し、保護フイルムをラミネートし、感光性エレメントを得た。その後、この感光性エレメントをロール状に巻き取り、さらに５００mm×５００ｍの寸法に切り、巻芯 （ポリエチレン樹脂）にロール状に巻き取り、感光性エレメントロールを得た。
【００５７】
下記表２に示す各種防湿シートを袋状にして、前記感光性エレメントロールを袋状の防湿シートに１本ずつ入れ、乾燥剤を投入し、袋の開口部をヒートシールにより密封した。表２記載の透湿度はＪＩＳ Ｋ ７１２９−１９９２に準拠して測定し、Ａ法により試験温度４０±０．５℃及び相対湿度差９０±２％ＲＨの条件で行った値である。上記防湿シート及び上記乾燥剤の組合せを表３に示す。
【００５８】
【表２】

【００５９】
表２中の防湿シートを下記に詳述する。
▲１▼ファインバリア／ＤＬ／Ｂ−ＰＥ：ファインバリアＡＴ（(株)麗光製商品名）とＢ−ＰＥ（ブラックポリエチレン）フィルムとのドライラミネート品
▲２▼ＯＰＰ／印刷／ＤＬ／ＶＭＣＰＰ：ＯＰＰ（二軸延伸ポリプロピレンフィルム）上に遮光用インクを塗布したフィルムとＶＭＣＰＰ（アルミニウムを蒸着した一軸延伸ポリプロピレンフィルム）とのドライラミネート品
▲３▼及び▲４▼Ｂ−ＰＥ：ブラックポリエチレンフィルム（林産業(株)製商品名ブラックシート）
【００６０】
なお、上記ドライラミネートとは、２つのフィルム間に接着剤を塗布し、温度５０℃で熱圧着し、室温にて４８時間予備エージングした後に４０℃で２４時間本エージングを行う作業である。
【００６１】
【表３】

【００６２】
上記表３の組合せで作製した、サンプルを恒温恒湿槽（タバイエスペック(株)製商品名ＰＲ−４）に投入し、温度３０℃、湿度９０％ＲＨの条件下に放置し、エッジフュージョン試験を１２時間経過毎に行い、結果を表４に示した。なお、試験経過時間１２時間は常温（２３℃、６０％ＲＨ）保管日数１５日に相当し、試験経過時間２４時間は常温保管日数３０日に相当し、試験経過時間３６時間は常温保管日数４５日に相当し、試験経過時間４８時間は常温保管日数６０日に相当し、試験経過時間６０時間は常温保管日数７５日に相当し、試験経過時間７２時間は常温保管日数９０日に相当する。
【００６３】
〔エッジフージョン評価〕
○：エッジフージョンが確認されず、感光性エレメントが良好に使用できる状態
○−：エッジフージョンが若干認められるが、感光性エレメントは良好に使用できる状態
○△：エッジフージョンが発生してはいるが、感光性エレメントは使用できる状態（使用限界）
△：エッジフージョンが発生し、感光性エレメントの使用が不可能である状態
×：エッジフージョンが多量に発生し、感光性エレメントの使用が不可能である状態
【００６４】
【表４】

【００６５】
また、前記エッジフュージョン試験を２４時間行った実施例１〜６及び比較例１〜４の梱包物から感光性エレメントを取り出し、銅張積層板に積層し、３KW超高圧水銀灯ランプを有する露光機（オーク(株)製）ＨＭＷ−２０１Ｂを用い、ネガとしてストーファー２１段ステップタブレットを有するフォトツールと、密着性評価用ネガとして、ライン幅／スペース幅が３０／４００〜２５０／４００ （単位：μｍ）の配線パターンを有するフォトツールを用いて、現像後の残存ステップ段数が８．０となるエネルギー量を求め、その値を感度とした。
次いで、支持フィルムを除去し、３０℃で１．０重量％炭酸ナトリウム水溶液をスプレーすることにより現像した。現像後に密着していた細線のライン幅の最も小さい値を密着性とした。
【００６６】
実施例１〜６の梱包物内の感光性エレメントは比較例１〜４の梱包物内の感光性エレメントよりも感度、密着性、耐色抜け性、イメージング性及び膜厚精度が優れていた。
【００６７】
【発明の効果】
請求項１、２、３、４、５、６、７、８、９、１０、１１、１２又は１３記載の梱包物は、長期保存後の感光性エレメントの感度、密着性、耐色抜け性、イメージング性及び膜厚精度が優れ、感光性エレメントの経時変化を防ぎ、エッジフュージョンの発生を長期間防ぐことができ、保証期間が長く、長期間品質を保持できる。[0001]
BACKGROUND OF THE INVENTION
The present invention is packing To things Related.
[0002]
[Prior art]
The photosensitive element used in the manufacture of printed wiring boards is in the form of a laminated film in which the photosensitive resin composition layer is sandwiched between a support film and a protective film. In use, the photosensitive element is photosensitive while peeling off the protective film. A resin composition layer is laminated on a printed wiring board, selectively irradiated with ultraviolet rays through a predetermined mask, and then developed to form an image on the printed wiring board.
This photosensitive dry film is called in response to a so-called wet method using a conventional photosensitive resin composition solution, but its usage is simple because a film-like photosensitive resin composition layer is used. Recently, it has been used instead of the wet method.
The closer the photosensitive element is to the center of the roll, the more pressure is applied from the outside of the roll to the inside. Fusing phenomenon) is likely to occur. This phenomenon is further facilitated by the influence of humidity.
[0003]
Therefore, (1) a method of applying a separator (protective disk) to the side surface of the photosensitive element roll (Japanese Patent Laid-Open No. 61-95345), (2) a method of placing a dry film in a waterproof container containing a desiccant (special No. 62-44736), (3) a method of applying a laminate covered with a sheet-like desiccant (JP-A-2-54255), and (4) improvement by improving the composition of the photosensitive resin composition. And the like (Japanese Patent Publication No. 2-19941) is known.
[0004]
However, the method (1) is easily affected by the unevenness of the adhesive, and the effect on the center of the roll is low. In the method (2), the humidity inside the container must be maintained at a predetermined level or lower, which is not efficient and is easily affected by the material and structure of the container. In the method (3), dust is easily generated from the desiccant, which deteriorates the quality of the photosensitive element. Furthermore, in the method (4), there are various problems in the prior art, such as limitations on each process such as developability.
[0005]
[Problems to be solved by the invention]
Claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 1 2 Or 13 The described invention is excellent in the sensitivity, adhesion, color loss resistance, imaging property and film thickness accuracy of the photosensitive element after long-term storage, prevents the photosensitive element from changing with time, and prevents the occurrence of edge fusion for a long period of time. It is possible to provide a package that has a long warranty period and can maintain quality for a long time.
[0009]
[Means for Solving the Problems]
In the present invention, a photosensitive element roll obtained by winding a photosensitive element around a cylindrical core and a desiccant have a moisture permeability of 0.02 to 4.5 g / (24 h · m ² ) Laminated black sheet and vapor deposition sheet The present invention relates to a package packaged by a sheet. Moreover, this invention relates to the said package whose desiccant is a zeolite, a silica gel, or a montmorillonite. Moreover, this invention relates to the said package whose weight of a desiccant is 5 g or more. Moreover, this invention relates to the said package in which a desiccant is a sheet form and exists as a protective material in the end surface of the photosensitive element roll. In the present invention, the moisture permeability of the sheet is 0.10 to 4.0 g / (24 h · m ² ).
[0010]
Ma Moreover, this invention relates to the said package which has a protective material on the roll end surface of the photosensitive element roll. Moreover, this invention relates to the said package in which a protective material has a water absorption capability or a moisture absorption capability. Moreover, this invention relates to the said package in which a photosensitive element laminates | stacks sequentially (a) support film and (b) photosensitive resin composition layer. Moreover, this invention relates to the said package which is a photosensitive element which has (c) a protective film further on the surface on the opposite side to (a) support film of (b) photosensitive resin composition layer.
[0011]
The present invention also relates to (b) a photopolymerizable compound in which the photosensitive resin composition layer has (A) a binder polymer, (B) at least one polymerizable ethylenically unsaturated group in the molecule, and (C). The present invention relates to the package containing a photopolymerization initiator.
Moreover, this invention relates to the said package whose (A) binder polymer uses styrene or a styrene derivative as an essential copolymerization component.
The present invention also relates to (B) the above-mentioned package wherein the photopolymerizable compound having at least one polymerizable ethylenically unsaturated group in the molecule contains a bisphenol A-based (meth) acrylate compound as an essential component.
Moreover, this invention relates to the said package whose (C) photoinitiator is a 2,4,5-triaryl imidazole dimer.
[0015]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail. In the present invention, (meth) acrylic acid means acrylic acid and methacrylic acid corresponding thereto, (meth) acrylate means acrylate and corresponding methacrylate, (meth) acryloyl group means acryloyl group and The corresponding methacryloyl group is meant.
[0016]
The package of the present invention comprises a photosensitive element roll obtained by winding a photosensitive element around a cylindrical core and a desiccant with a moisture permeability of 0.02 to 0.02. 4.5 g / (24h ・ m ² ) Laminated black sheet and vapor deposition sheet Wrapped with a sheet.
[0017]
Examples of the desiccant include activated alumina, silica gel, potassium hydroxide, calcium chloride, calcium oxide, calcium bromide, calcium sulfate, asbestos, zinc, zinc chloride, zinc bromide, magnesium oxide, magnesium chlorate, and copper sulfate. , Barium oxide, zeolite, montmorillonite, activated carbon, viscosity, glass wool, diatomaceous earth, molecular sieve, etc. are preferred, zeolite, silica gel or montmorillonite is preferred, and zeolite is more preferred. Moreover, what was reproduced | regenerated can also be used. These may be used alone or in combination of two or more.
Moreover, the said desiccant may exist as a protective material in the end surface of the photosensitive element, and may exist as a winding core which has water absorption ability or moisture absorption ability. When these protective materials or cores are used, the desiccant need not be used.
[0018]
The weight of the desiccant is preferably 1 g or more, more preferably 5 g or more, particularly preferably 5 to 1000 g, and most preferably 5 to 500 g per package. 10 to 300 g is very preferable, and 50 to 200 g is very particularly preferable. If the weight is less than 1 g, the effect of the present invention tends not to be obtained, and if it is too large, the economy tends to be inferior.
[0019]
The moisture permeability of the sheet is 0.02 to 4.5 g / (24 h · m ² ), Preferably 0.05 to 4.3 g / (24 h · m ² ), More preferably 0.10 to 4.0 g / (24 h · m ² ), Particularly preferably 0.15 to 3.5 g / (24 h · m ² ) Is very preferable, 0.20 to 3.0 g / (24 h · m ² ) Is highly preferred, 0.30 to 2.0 g / (24 h · m ² ) Is very highly preferred. This water vapor transmission rate is 0.02g / (24h · m ² ), The availability is inferior, and 4.5 g / (24 h · m ² ) Exceeds the edge fusion of the photosensitive element. In the present invention, the moisture permeability is measured according to JIS K 7129-1992, and is performed by the A method under the conditions of a test temperature of 40 ± 0.5 ° C. and a relative humidity difference of 90 ± 2% RH.
[0020]
The thickness of the sheet is preferably 1 to 100 μm, more preferably 1 to 50, particularly preferably 3 to 30 μm, and extremely preferably 5 to 20 μm. If the thickness is less than 1 μm, the ease of production and availability tends to be inferior, and if it exceeds 100 μm, the economy tends to be inferior.
[0021]
The sheet is not particularly limited as long as it satisfies the above moisture permeability, such as material, thickness, single product, laminated product of multiple sheets. From the viewpoint of storage stability, a black sheet is preferable. The black sheet is not particularly limited as long as it substantially blocks active light.
[0022]
The sheet is preferably a vapor deposition sheet, for example, polyester, polypropylene, polystyrene, polyvinyl chloride, nylon, polycarbonate, polyethylene cellulose triacetate, a copolymer of vinyl chloride and vinylidene chloride, an inorganic powder on a sheet of cellophane, etc. For example, a material obtained by vapor-depositing a material having a water absorbing ability or a moisture absorbing ability such as the above.
Although there is no restriction | limiting in particular as said inorganic powder, For example, what was mentioned above as a desiccant etc. is mentioned. These may be used alone or in combination of two or more.
[0023]
Examples of the sheet include aluminum foil, aluminum vapor deposition film, fine barrier AT (polyester film having aluminum oxide vapor deposited thereon, trade name, manufactured by Reiko Co., Ltd.), Tech Barrier S, Tech Barrier T, Tech Barrier H, Tech barrier V (silica vapor-deposited film, product name manufactured by Mitsubishi Chemical Co., Ltd.), dry barrier product of Fine Barrier AT (trade name, manufactured by Reiko Co., Ltd.) and B-PE (black polyethylene) film, OPP A dry laminate product of a film in which a light-shielding ink is applied on (biaxially stretched polypropylene film) and VMCP (uniaxially stretched polypropylene film on which aluminum is deposited) is available.
The dry laminate is an adhesive applied between two films, thermocompression bonded at a temperature of about 40 to 60 ° C., pre-aged at room temperature for about 24 to 60 hours, and then at about 30 to 50 ° C. for 12 to 12 ° C. This is the work of performing this aging for about 36 hours.
[0024]
The roll end surface of the photosensitive element roll is preferably protected by using a protective material (protective disk). The protective material preferably has water absorption ability or moisture absorption ability, and these protective materials having water absorption ability or moisture absorption ability may be present as the desiccant. A sheet-like film may be sandwiched between the roll end face and the protective material as long as the effects of the present invention are not impaired.
[0025]
The photosensitive element roll and desiccant have a moisture permeability of 0.02 to 0.02. 4.5 g / (24h ・ m ² ) Is not particularly limited, it is preferable to wrap the photosensitive element rolls every 1 to 3 pieces, more preferably every 1 to 2 pieces, and every 1 piece. It is particularly preferable to do this.
[0026]
The sheet is preferably in the form of a bag from the viewpoint of workability, and after opening the photosensitive element and the desiccant into the bag-shaped sheet, the opening of the sheet is welded with heat, a chemical substance (adhesive, etc.), It is preferable to perform bonding or the like.
When using a sheet-like material, place the photosensitive element in the center of the sheet, close the photosensitive element inside the sheet in the same way as folding the sheet, and weld or bond the seam of the sheet in the same way as above. Is preferred. The higher the sealing property of the package, the better. However, the packing can be performed within the technical capability.
Moreover, when putting a desiccant in the inside of a package, it is preferable to put in a core from a viewpoint of workability | operativity.
Examples of the gas inside the package include normal air, dry air, and nitrogen.
[0027]
As the photosensitive element, for example, (a) a support film and (b) a photosensitive resin composition layer are sequentially laminated, and (b) the photosensitive resin composition layer is (A) a binder polymer, ( B) A photopolymerizable compound having at least one polymerizable ethylenically unsaturated group in the molecule and (C) a photopolymerization initiator.
[0028]
Commercially available photosensitive elements can be used, and examples thereof include Hitachi Chemical Co., Ltd., Fotec, Asahi Kasei Kogyo Co., Ltd. Examples include Alfo, Laminar, Odile manufactured by Tokyo Ohka Kogyo Co., Ltd., and Dialon manufactured by Mitsubishi Rayon Co., Ltd.
Among these, the present invention is particularly effective for a photosensitive dry film that can be developed with a weak alkaline aqueous solution.
[0029]
Examples of the (A) binder polymer include acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, and phenol resins. From the viewpoint of alkali developability, an acrylic resin is preferable. These can be used alone or in combination of two or more.
[0030]
The (A) binder polymer can be produced, for example, by radical polymerization of a polymerizable monomer. Examples of the polymerizable monomer include styrene, vinyltoluene, α-methylstyrene, p-methylstyrene, p-ethylstyrene, p-methoxystyrene, p-ethoxystyrene, p-chlorostyrene, and p-bromostyrene. Polymerizable styrene derivatives such as acrylamide, acrylamide such as diacetone acrylamide, esters of vinyl alcohol such as acrylonitrile, vinyl-n-butyl ether, (meth) acrylic acid alkyl ester, (meth) acrylic acid tetrahydrofurfuryl ester, (meta ) Acrylic acid dimethylaminoethyl ester, (meth) acrylic acid diethylaminoethyl ester, (meth) acrylic acid glycidyl ester, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl ( T) acrylate, (meth) acrylic acid, α-bromo (meth) acrylic acid, α-chloro (meth) acrylic acid, β-furyl (meth) acrylic acid, β-styryl (meth) acrylic acid, maleic acid, maleic Examples thereof include acid anhydrides, maleic acid monoesters such as monomethyl maleate, monoethyl maleate and monoisopropyl maleate, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid and propiolic acid.
[0031]
Examples of the (meth) acrylic acid alkyl ester include, for example, the general formula (I)
[Chemical 1]

(Wherein R ¹ Represents a hydrogen atom or a methyl group, R ² Represents an alkyl group having 1 to 12 carbon atoms)
And compounds in which a hydroxyl group, an epoxy group, a halogen group or the like is substituted on the alkyl group of these compounds.
R in the above general formula (I) ² Examples of the alkyl group having 1 to 12 carbon atoms represented by: methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl Groups and their structural isomers.
[0032]
Examples of the monomer represented by the general formula (I) include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, (meth) acrylic acid butyl ester, (Meth) acrylic acid pentyl ester, (meth) acrylic acid hexyl ester, (meth) acrylic acid heptyl ester, (meth) acrylic acid octyl ester, (meth) acrylic acid 2-ethylhexyl ester, (meth) acrylic acid nonyl ester, (Meth) acrylic acid decyl ester, (meth) acrylic acid undecyl ester, (meth) acrylic acid dodecyl ester, and the like. These can be used alone or in combination of two or more.
[0033]
The binder polymer (A) preferably contains a carboxyl group from the viewpoint of alkali developability, and is produced, for example, by radical polymerization of a polymerizable monomer having a carboxyl group and other polymerizable monomers. can do.
As the polymerizable monomer having a carboxyl group, methacrylic acid is preferable. Further, the (A) binder polymer preferably contains styrene or a styrene derivative as a polymerizable monomer from the viewpoint of flexibility.
[0034]
In order to improve both the adhesiveness and the release property using the styrene or styrene derivative as a copolymerization component, it is preferably included in an amount of 0.1 to 30% by weight, more preferably 1 to 28% by weight, It is particularly preferred to contain ~ 27 wt%. If this content is less than 0.1% by weight, the adhesion tends to be inferior, and if it exceeds 30% by weight, the peel piece tends to be large and the peel time tends to be long.
[0035]
These binder polymers are used alone or in combination of two or more. As a binder polymer in the case of using two or more types in combination, for example, two or more types of binder polymers comprising different copolymerization components, two or more types of binder polymers having different weight average molecular weights, and two or more types of binder polymers having different degrees of dispersion are used. Examples thereof include a binder polymer.
[0036]
The (A) binder polymer preferably has a weight average molecular weight of 20,000 to 200,000, and more preferably 40,000 to 120,000. When the weight average molecular weight is less than 20,000, the developer resistance and film strength tend to decrease, and when it exceeds 200,000, the resolution tends to decrease. However, the weight average molecular weight is measured by a gel permeation chromatography method and converted by a calibration curve prepared using standard polystyrene.
[0037]
Examples of the photopolymerizable compound (B) include compounds obtained by reacting polyhydric alcohols with α, β-unsaturated carboxylic acids, 2,2-bis (4-((meth) acryloxypolyethoxy). Phenyl) propane, 2,2-bis (4-((meth) acryloxypolypropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolybutoxy) phenyl) propane, 2,2- Bisphenol A-based (meth) acrylate compounds such as bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane, compounds obtained by reacting α, β-unsaturated carboxylic acids with glycidyl group-containing compounds, Urethane monomers such as (meth) acrylate compounds having a urethane bond, nonylphenyldioxylene (meth) acrylate, γ-chloro B-Hydroxypropyl-β ′-(meth) acryloyloxyethyl-o-phthalate, β-hydroxyethyl-β ′-(meth) acryloyloxyethyl-o-phthalate, β-hydroxypropyl-β ′-(meta ) Acryloyloxyethyl-o-phthalate, (meth) acrylic acid alkyl ester, and the like are mentioned, but it is preferable to use a bisphenol A-based (meth) acrylate compound or a (meth) acrylate compound having a urethane bond as an essential component. These may be used alone or in combination of two or more.
[0038]
Examples of the compound obtained by reacting the polyhydric alcohol with an α, β-unsaturated carboxylic acid include, for example, polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups and 2 to 2 propylene groups. Polypropylene glycol di (meth) acrylate which is 14, polyethylene polyethylene glycol glycol di (meth) acrylate having 2 to 14 ethylene groups and 2 to 14 propylene groups, trimethylolpropane di (meth) acrylate , Trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate, EO modified trimethylolpropane tri (meth) acrylate, PO modified trimethylolpropane tri (meth) acrylate, EO, PO modified trimethylo Tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetra methylol methane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate.
Examples of the α, β-unsaturated carboxylic acid include (meth) acrylic acid.
[0039]
Examples of the 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydiethoxy) phenyl) propane, 2,2 -Bis (4-((meth) acryloxytriethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetraethoxy) phenyl) propane, 2,2-bis (4-((meta ) Acryloxypentaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyheptaethoxy) phenyl) Propane, 2,2-bis (4-((meth) acryloxyoctaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxynonane) Xyl) phenyl) propane, 2,2-bis (4-((meth) acryloxydecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyundecaethoxy) phenyl) propane, 2 , 2-bis (4-((meth) acryloxydodecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytridecaethoxy) phenyl) propane, 2,2-bis (4- ((Meth) acryloxytetradecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentadecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxy) Hexadecaethoxy) phenyl) propane and the like, and 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane is BPE- 500 (manufactured by Shin-Nakamura Chemical Co., Ltd., product name) and 2,2-bis (4- (methacryloxypentadecaethoxy) phenyl) propane is BPE-1300 (Shin-Nakamura Chemical) It is commercially available as a product name manufactured by Kogyo Co., Ltd. These may be used alone or in combination of two or more.
[0040]
Examples of the 2,2-bis (4-((meth) acryloxypolypropoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydipropoxy) phenyl) propane, 2,2 -Bis (4-((meth) acryloxytripropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetrapropoxy) phenyl) propane, 2,2-bis (4-((meta ) Acryloxypentapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyheptapropoxy) phenyl) Propane, 2,2-bis (4-((meth) acryloxyoctapropoxy) phenyl) propane, 2,2-bis (4-((meth)) Acryloxynonapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxydecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyundecapropoxy) phenyl) Propane, 2,2-bis (4-((meth) acryloxydodecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytridecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetradecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentadecapropoxy) phenyl) propane, 2,2-bis (4-((meta And acryloxyhexadecapropoxy) phenyl) propane. These may be used alone or in combination of two or more.
[0041]
Examples of the 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydiethoxyoctapropoxy) phenyl) propane. 2,2-bis (4-((meth) acryloxytetraethoxytetrapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexaethoxyhexapropoxy) phenyl) propane and the like. . These may be used alone or in combination of two or more.
Examples of the glycidyl group-containing compound include trimethylolpropane triglycidyl ether tri (meth) acrylate, 2,2-bis (4- (meth) acryloxy-2-hydroxy-propyloxy) phenyl, and the like.
[0042]
Examples of the urethane monomer include a (meth) acryl monomer having an OH group at the β-position and a diisocyanate compound such as isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, and 1,6-hexamethylene diisocyanate. Addition reaction product, tris ((meth) acryloxytetraethylene glycol isocyanate) hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate, EO, PO-modified urethane di (meth) acrylate, and the like. Examples of the EO-modified urethane di (meth) acrylate include Shin-Nakamura Chemical Co., Ltd., product name UA-11, and the like. Examples of EO and PO-modified urethane di (meth) acrylates include product name UA-13 manufactured by Shin-Nakamura Chemical Co., Ltd.
Examples of the (meth) acrylic acid alkyl ester include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester, (meth) acrylic acid 2-ethylhexyl ester, and the like. .
Note that EO represents ethylene oxide, and the EO-modified compound has a block structure of an ethylene oxide group. PO represents propylene oxide, and the PO-modified compound has a block structure of propylene oxide groups.
[0043]
Examples of the (C) photopolymerization initiator include benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N′-tetraethyl-4,4′-diaminobenzophenone, 4 -Methoxy-4'-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholino -Aromatic ketones such as propanone-1, 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2, 3-diphenylanthraquinone, 1-chloroan Quinones such as laquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenantharaquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, benzoin methyl ether, benzoin ethyl ether, benzoin Benzoin ether compounds such as phenyl ether, benzoin compounds such as benzoin, methylbenzoin and ethylbenzoin, benzyl derivatives such as benzyldimethyl ketal, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o -Chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5- Diphenylimidazole dimer, 2,4,5-triarylimidazole dimer such as-(p-methoxyphenyl) -4,5-diphenylimidazole dimer, 9-phenylacridine, 1,7-bis (9,9'-acridinyl) Examples include acridine derivatives such as heptane, N-phenylglycine, N-phenylglycine derivatives, and coumarin compounds.
[0044]
Further, the substituents of the aryl groups of two 2,4,5-triarylimidazoles may be the same to give the target compound, or differently give an asymmetric compound.
Moreover, you may combine a thioxanthone type compound and a tertiary amine compound like the combination of diethyl thioxanthone and dimethylaminobenzoic acid.
From the viewpoint of adhesion and sensitivity, 2,4,5-triarylimidazole dimer is more preferable.
These are used alone or in combination of two or more.
[0045]
In addition, the photosensitive resin composition of the present invention may contain a photopolymerizable compound having at least one cationically polymerizable cyclic ether group in the molecule, a cationic polymerization initiator, a dye such as malachite green, Photochromic agents such as bromophenylsulfone and leucocrystal violet, thermochromic inhibitors, plasticizers such as p-toluenesulfonamide, pigments, fillers, antifoaming agents, flame retardants, stabilizers, adhesion promoters, leveling agents , A peeling accelerator, an antioxidant, a fragrance, an imaging agent, a thermal crosslinking agent, and the like can be contained in an amount of about 0.01 to 20 parts by weight per 100 parts by weight of the total amount of the component (A) and the component (B). . These are used alone or in combination of two or more.
[0046]
If necessary, the photosensitive resin composition of the present invention is a solvent such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether, or a mixed solvent thereof. And can be applied as a solution having a solid content of about 30 to 60% by weight.
[0047]
The photosensitive resin composition of the present invention is not particularly limited, but a metal surface, for example, an iron-based alloy such as copper, copper-based alloy, nickel, chromium, iron, stainless steel, preferably copper, copper-based alloy, iron-based It is preferable that the surface of the alloy is applied as a liquid resist and dried, and then coated with a protective film if necessary, or used in the form of a photosensitive element.
[0048]
Moreover, although the thickness of the photosensitive resin composition layer changes with uses, it is preferable that it is 1-200 micrometers by the thickness after drying, it is more preferable that it is 1-100 micrometers, and it is especially preferable that it is 1-30 micrometers. . If the thickness is less than 1 μm, it tends to be difficult to apply industrially, and if it exceeds 200 μm, the effect of the present invention is small, the sensitivity is insufficient, and the photocurability at the bottom of the resist tends to deteriorate. In the case of using a liquid resist coated with a protective film, an inert polyolefin film such as polyethylene or polypropylene is used as the protective film, but from the viewpoint of releasability from the photosensitive resin composition layer, a polyethylene film is used. preferable.
[0049]
The photosensitive element can be obtained, for example, by applying and drying a photosensitive resin composition on a polymer film having heat resistance and solvent resistance such as polyethylene terephthalate, polypropylene, polyethylene, and polyester as a support. From the viewpoint of transparency, it is preferable to use a polyethylene terephthalate film.
The application can be performed by a known method such as a roll coater, a comma coater, a gravure coater, an air knife coater, a die coater, a bar coater, or a sley coater. Moreover, drying can be performed at 70-150 degreeC and about 5 to 30 minutes.
Further, the amount of the remaining organic solvent in the photosensitive resin composition layer is preferably 2% by weight or less from the viewpoint of preventing the organic solvent from diffusing in the subsequent step.
[0050]
In addition, these polymer films must be removable from the photosensitive resin composition layer later, and therefore may be subjected to a surface treatment or a material that makes removal impossible. must not. The thickness of these polymer films is preferably 1 to 100 μm, and more preferably 1 to 30 μm. If this thickness is less than 1 μm, the mechanical strength tends to decrease, and problems such as breakage of the polymer film during coating tend to occur, and if it exceeds 30 μm, the resolution tends to decrease and the price tends to increase.
One of these polymer films may be laminated on both sides of the photosensitive resin composition layer as a support film for the photosensitive resin composition layer, and the other as a protective film for the photosensitive resin composition.
As the protective film, those having a smaller adhesive strength between the photosensitive resin composition layer and the protective film than the adhesive strength between the photosensitive resin composition layer and the support are preferable, and a film having a low fish eye is preferable.
[0051]
The photosensitive element of the present invention comprising two layers of the photosensitive resin composition layer and the polymer film thus obtained can be obtained by, for example, further laminating a protective film as it is or on the other surface of the photosensitive resin composition layer. Then, it is wound around a cylindrical core and stored.
In addition, it is preferable to wind up so that a support film may become the outermost side in this case. An end face separator is preferably installed on the end face of the roll-shaped photosensitive element roll from the viewpoint of end face protection, and a moisture-proof end face separator is preferably installed from the viewpoint of edge fusion resistance.
Moreover, as a packing method, it is preferable to wrap and package in a black sheet with low moisture permeability.
Examples of the winding core include plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, and ABS resin (acrylonitrile-butadiene-styrene copolymer).
[0052]
When manufacturing the resist pattern using the photosensitive element, if the protective film is present, the protective film is removed, and then the photosensitive resin composition layer is heated to 0 on the circuit forming substrate. .About 1 to 1 MPa (1 to 10 kgf / cm ² About) a method of laminating by pressure bonding is included.
The photosensitive resin composition layer thus laminated is irradiated with actinic rays in an image form through a negative or positive mask pattern called an artwork.
Next, after exposure, when a support is present on the photosensitive resin composition layer, the support is removed, and then wet development or dry development with a developer such as an alkaline aqueous solution, an aqueous developer, or an organic solvent. The resist pattern is manufactured by removing the unexposed portion and developing the film.
[0053]
【Example】
Hereinafter, the present invention will be described in detail based on examples and comparative examples.
[0054]
Examples 1-3 and Comparative Examples 1-2
(A) component shown in Table 1, (B) component, (C) component, and other components were mixed, and the solution of the photosensitive resin composition was prepared.
[0055]
[Table 1]

[0056]
Next, this photosensitive resin composition solution was uniformly applied onto a 16 μm thick polyethylene terephthalate film, dried for 5 minutes in a hot air convection dryer at 100 ° C., and a protective film was laminated to obtain a photosensitive element. Then, this photosensitive element was wound up into a roll shape, further cut into a size of 500 mm × 500 m, and wound up into a roll shape around a core (polyethylene resin) to obtain a photosensitive element roll.
[0057]
Various moisture-proof sheets shown in Table 2 below were formed into a bag shape, the photosensitive element rolls were put into the bag-shaped moisture-proof sheet one by one, a desiccant was added, and the opening of the bag was sealed by heat sealing. The moisture permeability shown in Table 2 is a value measured according to JIS K 7129-1992 and performed by the A method under the conditions of a test temperature of 40 ± 0.5 ° C. and a relative humidity difference of 90 ± 2% RH. Table 3 shows combinations of the moisture-proof sheet and the desiccant.
[0058]
[Table 2]

[0059]
The moisture-proof sheet in Table 2 is described in detail below.
(1) Fine barrier / DL / B-PE: Dry laminate product of Fine Barrier AT (trade name, manufactured by Reiko Co., Ltd.) and B-PE (black polyethylene) film
(2) OPP / printing / DL / VMCP: A dry laminate product of a film in which a light-shielding ink is applied on OPP (biaxially stretched polypropylene film) and VMCP (uniaxially stretched polypropylene film on which aluminum is deposited).
(3) and (4) B-PE: Black polyethylene film (trade name black sheet manufactured by Hayashi Sangyo Co., Ltd.)
[0060]
The dry laminate is an operation of applying an adhesive between two films, thermocompression bonding at a temperature of 50 ° C., pre-aging at room temperature for 48 hours, and then performing the main aging at 40 ° C. for 24 hours.
[0061]
[Table 3]

[0062]
The sample produced by the combination shown in Table 3 above was put into a constant temperature and humidity chamber (trade name PR-4 manufactured by Tabai Espec Co., Ltd.), left under conditions of a temperature of 30 ° C. and a humidity of 90% RH, and an edge fusion test. Was performed every 12 hours, and the results are shown in Table 4. The test elapsed time of 12 hours corresponds to 15 days of normal temperature (23 ° C., 60% RH) storage, the test elapsed time of 24 hours corresponds to 30 days of normal temperature storage, and the test elapsed time of 36 hours corresponds to 45 days of normal temperature storage. The test elapsed time of 48 hours corresponds to 60 days of normal temperature storage, the test elapsed time of 60 hours corresponds to 75 days of normal temperature storage, and the test elapsed time of 72 hours corresponds to 90 days of normal temperature storage.
[0063]
[Edge Fusion Evaluation]
○: Edge fusion is not confirmed, and the photosensitive element can be used satisfactorily
○-: Some edge fusion is observed, but the photosensitive element can be used well.
○ △: Edge fusion has occurred, but photosensitive element can be used (use limit)
Δ: Edge fusion occurs and the photosensitive element cannot be used
×: A state where a large amount of edge fusion occurs and the photosensitive element cannot be used.
[0064]
[Table 4]

[0065]
In addition, the photosensitive element was taken out from the package of Examples 1 to 6 and Comparative Examples 1 to 4 in which the edge fusion test was performed for 24 hours, and was laminated on a copper-clad laminate, and an exposure machine having a 3 KW super high pressure mercury lamp lamp ( Oak Tool Co., Ltd.) HMW-201B, a photo tool having a stove 21-step tablet as a negative, and a negative for adhesive evaluation, line width / space width is 30/400 to 250/400 (unit: μm) ) Was used to determine the amount of energy at which the number of steps remaining after development was 8.0, and this value was taken as the sensitivity.
The support film was then removed and developed by spraying a 1.0 wt% aqueous sodium carbonate solution at 30 ° C. The smallest value of the line width of the fine lines that adhered after development was defined as adhesion.
[0066]
The photosensitive elements in the packages of Examples 1 to 6 were superior in sensitivity, adhesion, color loss resistance, imaging properties, and film thickness accuracy to the photosensitive elements in the packages of Comparative Examples 1 to 4.
[0067]
【The invention's effect】
Claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 1 2 Or 13 The package described is excellent in sensitivity, adhesion, color loss resistance, imaging property, and film thickness accuracy of the photosensitive element after long-term storage, prevents changes in the photosensitive element over time, and prevents edge fusion from occurring for a long period of time. The warranty period is long and the quality can be maintained for a long time.

Claims (13)

A photosensitive element roll in which a photosensitive element is wound around a cylindrical core and a desiccant are packaged by a sheet obtained by laminating a black sheet having a moisture permeability of 0.02 to 4.5 g / (24 h · m ² ) and a vapor deposition sheet. Packaging.   The package according to claim 1, wherein the desiccant is zeolite, silica gel or montmorillonite.   The package according to claim 1 or 2, wherein the weight of the desiccant is 5 g or more. Drying agent is a sheet packaging material as claimed in any one of claims 1, 2 or 3 is present as a protective material on the end surface of the photosensitive element roll. The package according to any one of claims 1, 2, 3 and 4 , wherein the sheet has a moisture permeability of 0.10 to 4.0 g / (24 h · m ² ). The package of Claim 1, 2, 3, or 5 which has a protective material in the roll end surface of the photosensitive element roll. The package according to claim 6, wherein the protective material has a water absorbing ability or a moisture absorbing ability. The package according to claim 1, 2, 3, 4, 5, 6 or 7 , wherein the photosensitive element is formed by sequentially laminating (a) a support film and (b) a photosensitive resin composition layer. The package according to claim 8, which is a photosensitive element having (c) a protective film on the surface opposite to the (a) support film of the (b) photosensitive resin composition layer. (B) The photosensitive resin composition layer contains (A) a binder polymer, (B) a photopolymerizable compound having at least one polymerizable ethylenically unsaturated group in the molecule, and (C) a photopolymerization initiator. The package according to claim 8 or 9 . The package according to claim 10 , wherein the binder polymer comprises styrene or a styrene derivative as an essential copolymer component. (B) The package according to claim 10 or 11, wherein the photopolymerizable compound having at least one polymerizable ethylenically unsaturated group in the molecule contains a bisphenol A (meth) acrylate compound as an essential component. (C) The package according to claim 10 , 11 or 12 , wherein the photopolymerization initiator is a 2,4,5-triarylimidazole dimer.