JP4186528B2 - Photosensitive lithographic printing plate material - Google Patents

Description

【００６５】
２個以上のウレタン結合及び２個のエチレン性不飽和結合を有する化合物としては、具体的には下記が挙げられる。
【００６６】
【化２】

【００６７】
ウレタン結合を有さず、２個以上のエチレン性不飽和結合を有する化合物としては、具体的には下記が挙げられる。
【００６８】
【化３】

【００６９】
本発明の高分子結合剤は、下記（１）〜（１７）に記載のモノマーの混合物を共重合して得られたビニル系共重合体であることが好ましい。
【００７０】
（１）芳香族水酸基を有するモノマー、例えば、ｏ−（又はｐ−，ｍ−）ヒドロキシスチレン、ｏ−（又はｐ−，ｍ−）ヒドロキシフェニルアクリレート等。
【００７１】
（２）脂肪族水酸基を有するモノマー、例えば、２−ヒドロキシエチルアクリレート、２−ヒドロキシエチルメタクリレート、Ｎ−メチロールアクリルアミド、Ｎ−メチロールメタクリルアミド、４−ヒドロキシブチルメタクリレート、５−ヒドロキシペンチルアクリレート、５−ヒドロキシペンチルメタクリレート、６−ヒドロキシヘキシルアクリレート、６−ヒドロキシヘキシルメタクリレート、Ｎ−（２−ヒドロキシエチル）アクリルアミド、Ｎ−（２−ヒドロキシエチル）メタクリルアミド、ヒドロキシエチルビニルエーテル等。
【００７２】
（３）アミノスルホニル基を有するモノマー、例えば、ｍ−（又はｐ−）アミノスルホニルフェニルメタクリレート、ｍ−（又はｐ−）アミノスルホニルフェニルアクリレート、Ｎ−（ｐ−アミノスルホニルフェニル）メタクリルアミド、Ｎ−（ｐ−アミノスルホニルフェニル）アクリルアミド等。
【００７３】
（４）スルホンアミド基を有するモノマー、例えば、Ｎ−（ｐ−トルエンスルホニル）アクリルアミド、Ｎ−（ｐ−トルエンスルホニル）メタクリルアミド等。
【００７４】
（５）α，β−不飽和カルボン酸類、例えば、アクリル酸、メタクリル酸、マレイン酸、無水マレイン酸、イタコン酸、無水イタコン酸等。
【００７５】
（６）置換又は無置換のアルキルアクリレート、例えば、アクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、アクリル酸ブチル、アクリル酸アミル、アクリル酸ヘキシル、アクリル酸ヘプチル、アクリル酸オクチル、アクリル酸ノニル、アクリル酸デシル、アクリル酸ウンデシル、アクリル酸ドデシル、アクリル酸ベンジル、アクリル酸シクロヘキシル、アクリル酸−２−クロロエチル、Ｎ，Ｎ−ジメチルアミノエチルアクリレート、グリシジルアクリレート等。
【００７６】
（７）置換又は無置換のアルキルメタクリレート、例えば、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸ブチル、メタクリル酸アミル、メタクリル酸ヘキシル、メタクリル酸ヘプチル、メタクリル酸オクチル、メタクリル酸ノニル、メタクリル酸デシル、メタクリル酸ウンデシル、メタクリル酸ドデシル、メタクリル酸ベンジル、メタクリル酸シクロヘキシル、メタクリル酸−２−クロロエチル、Ｎ，Ｎ−ジメチルアミノエチルメタクリレート、グリシジルメタクリレート等。
【００７７】
（８）アクリルアミド又はメタクリルアミド類、例えば、アクリルアミド、メタクリルアミド、Ｎ−エチルアクリルアミド、Ｎ−ヘキシルアクリルアミド、Ｎ−シクロヘキシルアクリルアミド、Ｎ−フェニルアクリルアミド、Ｎ−（４−ニトロフェニル）アクリルアミド、Ｎ−エチル−Ｎ−フェニルアクリルアミド、Ｎ−（４−ヒドロキシフェニル）アクリルアミド、Ｎ−（４−ヒドロキシフェニル）メタクリルアミド等。
【００７８】
（９）弗化アルキル基を含有するモノマー、例えば、トリフルオロエチルアクリレート、トリフルオロエチルメタクリレート、テトラフルオロプロピルメタクリレート、ヘキサフルオロプロピルメタクリレート、オクタフルオロペンチルアクリレート、オクタフルオロペンチルメタクリレート、ヘプタデカフルオロデシルメタクリレート、Ｎ−ブチル−Ｎ−（２−アクリロキシエチル）ヘプタデカフルオロオクチルスルホンアミド等。
【００７９】
（１０）ビニルエーテル類、例えば、エチルビニルエーテル、２−クロロエチルビニルエーテル、プロピルビニルエーテル、ブチルビニルエーテル、オクチルビニルエーテル、フェニルビニルエーテル等。
【００８０】
（１１）ビニルエステル類、例えば、ビニルアセテート、ビニルクロロアセテート、ビニルブチレート、安息香酸ビニル等。
【００８１】
（１２）スチレン類、例えば、スチレン、メチルスチレン、クロロメチルスチレン等。
【００８２】
（１３）ビニルケトン類、例えば、メチルビニルケトン、エチルビニルケトン、プロピルビニルケトン、フェニルビニルケトン等。
【００８３】
（１４）オレフィン類、例えば、エチレン、プロピレン、ｉ−ブチレン、ブタジエン、イソプレン等。
【００８４】
（１５）Ｎ−ビニルピロリドン、Ｎ−ビニルカルバゾール、４−ビニルピリジン等。
【００８５】
（１６）シアノ基を有するモノマー、例えば、アクリロニトリル、メタクリロニトリル、２−ペンテンニトリル、２−メチル−３−ブテンニトリル、２−シアノエチルアクリレート、ｏ−（又はｍ−，ｐ−）シアノスチレン等。
【００８６】
（１７）アミノ基を有するモノマー、例えば、Ｎ，Ｎ−ジエチルアミノエチルメタクリレート、Ｎ，Ｎ−ジメチルアミノエチルアクリレート、Ｎ，Ｎ−ジメチルアミノエチルメタクリレート、ポリブタジエンウレタンアクリレート、Ｎ，Ｎ−ジメチルアミノプロピルアクリルアミド、Ｎ，Ｎ−ジメチルアクリルアミド、アクリロイルモルホリン、Ｎ−ｉ−プロピルアクリルアミド、Ｎ，Ｎ−ジエチルアクリルアミド等。
【００８７】
上記（１）〜（１７）から得られる共重合体は、通常の溶液重合により製造することができる。また、塊状重合または懸濁重合等によっても製造することができる。
【００８８】
重合開始剤としては特に限定されないが、アゾビス系のラジカル発生剤が挙げられ、例えば、２，２′−アゾビスイソブチロニトリル（ＡＩＢＮ）、２，２′−アゾビス（２−メチルブチロニトリル）等が挙げられる。また、これらの重合開始剤の使用量は、共重合体を形成するのに使用されるモノマー全体１００質量部に対し、０．０５〜１０．０質量部（好ましくは０．１〜５質量部）である。
【００８９】
また、溶液重合を行う際に使用される溶媒としては、アルコール系、ケトン系、エステル系、芳香族系の有機溶媒が挙げられ、なかでもエタノール、トルエン、酢酸エチル、ベンゼン、メチルセロソルブ、エチルセロソルブ、アセトン、メチルエチルケトン等の一般にアクリル系ポリマーの良溶媒が挙げられ、なかでも沸点６０〜１２０℃の溶媒が好ましい。溶液重合の場合、上記溶媒を使用し、反応温度として４０〜１２０℃（好ましくは６０〜１１０℃）、反応時間として３〜１０時間（好ましくは５〜８時間）の条件で行うことができる。反応終了後、溶媒を除去して共重合体を得る。また、溶媒を除去せずに引き続き後記の二重結合の導入反応を行うこともできる。
【００９０】
得られる共重合体の分子量は、使用される溶媒および反応温度を調整することによって調節することができる。目的とする分子量の共重合体を得るために使用される溶媒および反応温度等は、使用されるモノマーによって適宜決定することができる。また、特定の溶媒を上記溶媒に混合することによっても得られる共重合体の分子量を調節することができる。このような溶媒としては、例えばメルカプタン系（例えば、ｎ−オクチルメルカプタン、ｎ−ドデシルメルカプタン、ｔ−ドデシルメルカプタン、メルカプトエタノール等）、四塩化炭素系（例えば、四塩化炭素、塩化ブチル、塩化プロピレン等）等が挙げられる。これらの溶媒を上記反応に使用する溶媒に混合する割合は、反応に使用するモノマー、溶媒、反応条件等によって適宜決定することができる。
【００９１】
本発明の一つの形態として、高分子結合剤がカルボキシル基を有するモノマー単位および該カルボキシル基を有するモノマー単位の少なくとも一部にエポキシ基含有不飽和化合物を反応させた単位を構成要素として有する共重合体であることである。
【００９２】
カルボキシル基を有するモノマー単位を有する共重合体は前記（５）α，β−不飽和カルボン酸類、例えばアクリル酸、メタクリル酸、マレイン酸、無水マレイン酸、イタコン酸、無水イタコン酸等、を有するビニル系共重合体が好ましく、カルボキシル基を有するモノマー単位としては、アクリル酸、メタクリル酸が好ましい。
【００９３】
カルボキシル基を有するモノマー単位の少なくとも一部に反応させるエポキシ基含有不飽和化合物としては、例えば、アリルグリシジルエーテル、グリシジル（メタ）アクリレート、α−エチルグリシジル（メタ）アクリレート、グリシジルクロトネート、グリシジルイソクロトネート、クロトニルグリシジルエーテル、イタコン酸モノアルキルモノグリシジルエステル、フマール酸モノアルキルモノグリシジルエステル、マレイン酸モノアルキルモノグリシジルエステル等の脂肪族エポキシ基含有不飽和化合物、又は、３，４−エポキシシクロヘキシルメチル（メタ）アクリレート等の脂環式エポキシ基含有不飽和化合物等が挙げられ、中でもグリシジル（メタ）アクリレートが好ましい。
【００９４】
カルボキシル基を有するモノマー単位の少なくとも一部にエポキシ基含有不飽和化合物を反応させる方法は公知の方法でできる。例えば、反応温度として２０〜１００℃、好ましくは４０〜８０℃、特に好ましくは使用する溶媒の沸点下（還流下）にて、反応時間として２〜１０時間、好ましくは３〜６時間で行うことができる。使用する溶媒としては、上記ビニル系共重合体の重合反応において使用する溶媒が挙げられる。また、重合反応後、溶媒を除去せずにその溶媒をそのまま脂環式エポキシ基含有不飽和化合物の導入反応に使用することができる。また、反応は必要に応じて触媒および重合禁止剤の存在下で行うことができる。ここで、触媒としてはアミン系または塩化アンモニウム系の物質が好ましく、具体的には、アミン系の物質としては、トリエチルアミン、トリブチルアミン、ジメチルアミノエタノール、ジエチルアミノエタノール、メチルアミン、エチルアミン、ｎ−プロピルアミン、イソプロピルアミン、３−メトキシプロピルアミン、ブチルアミン、アリルアミン、ヘキシルアミン、２−エチルヘキシルアミン、ベンジルアミン等が挙げられ、塩化アンモニウム系の物質としては、トリエチルベンジルアンモニウムクロライド等が挙げられる。これらを触媒として使用する場合、使用する脂環式エポキシ基含有不飽和化合物に対して、０．０１〜２０．０質量％の範囲で添加すればよい。また、重合禁止剤としてはハイドロキノン、ハイドロモノメチルエーテル、２，６−ジ−ｔ−ブチルハイドロトルエン等が挙げられ、その使用量は使用する脂環式エポキシ基含有不飽和化合物に対して、０．０１〜５．０質量％である。なお、なお、反応の進行状況は反応系の酸価を測定し、酸価が０になった時点で反応を停止させればよい。
【００９５】
上記高分子結合剤には、必要に応じてポリビニルブチラール樹脂、ポリウレタン樹脂、ポリアミド樹脂、ポリエステル樹脂、エポキシ樹脂、ノボラック樹脂、天然樹脂、他の方法により反応性基を導入した樹脂等、他の任意の高分子結合剤を併用してもよい。
【００９６】
上記した本発明の高分子結合剤は、全高分子結合剤において、５０〜１００質量％であることが好ましく、１００質量％であることがより好ましい。
【００９７】
感光層を塗布し形成する感光性組成物中における高分子結合剤の含有量は、１０〜９０質量％の範囲が好ましく、１５〜７０質量％の範囲が更に好ましく、２０〜５０質量％の範囲で使用することが感度の面から特に好ましい。
【００９８】
本発明の感光性平版印刷版材料に用いることができる光重合開始剤として好ましく使用できるものは、例えば、Ｊ．コーサー（Ｊ．Ｋｏｓａｒ）著「ライト・センシテイブ・システムズ」第５章に記載されるような、カルボニル化合物、有機硫黄化合物、過硫化物、レドックス系化合物、アゾ化合物、ジアゾ化合物、ハロゲン化合物、光還元性色素などが挙げられ、英国特許第１，４５９，５６３号に開示されている化合物も好ましい。
【００９９】
具体的には、以下の例を挙げることができるが、これらに限定されない。即ち、ベンゾインメチルエーテル、ベンゾイン−ｉ−プロピルエーテル、α，α−ジメトキシ−α−フェニルアセトフェノン等のベンゾイン誘導体；ベンゾフェノン、２，４−ジクロロベンゾフェノン、ｏ−ベンゾイル安息香酸メチル、４，４′−ビス（ジメチルアミノ）ベンゾフェノン等のベンゾフェノン誘導体；２−クロロチオキサントン、２−ｉ−プロピルチオキサントン等のチオキサントン誘導体；２−クロロアントラキノン、２−メチルアントラキノン等のアントラキノン誘導体；Ｎ−メチルアクリドン、Ｎ−ブチルアクリドン等のアクリドン誘導体；α，α−ジエトキシアセトフェノン、ベンジル、フルオレノン、キサントン、ウラニル化合物の他、特公昭５９−１２８１号、同６１−９６２１号ならびに特開昭６０−６０１０４号に記載のトリアジン誘導体；特開昭５９−１５０４号、同６１−２４３８０７号に記載の有機過酸化物；特公昭４３−２３６８４号、同４４−６４１３号、同４４−６４１３号、同４７−１６０４号ならびに米国特許第３，５６７，４５３号に記載のジアゾニウム化合物；米国特許第２，８４８，３２８号、同２，８５２，３７９号ならびに同２，９４０，８５３号に記載の有機アジド化合物；特公昭３６−２２０６２号、同３７−１３１０９号、同３８−１８０１５号ならびに同４５−９６１０号に記載のｏ−キノンジアジド類；特公昭５５−３９１６２号、特開昭５９−１４０２３号ならびに「マクロモレキュルス（Ｍａｃｒｏｍｏｌｅｃｕｌｅｓ）」１０巻，１３０７頁（１９７７年）記載の各種オニウム化合物；特開昭５９−１４２２０５号に記載のアゾ化合物；特開平１−５４４４０号、ヨーロッパ特許第１０９，８５１号、同１２６，７１２号ならびに「ジャーナル・オブ・イメージング・サイエンス（Ｊ．Ｉｍａｇ．Ｓｃｉ．）」３０巻，１７４頁（１９８６年）記載の金属アレン錯体；特開平５−２１３８６１号及び同５−２５５３４７号記載の（オキソ）スルホニウム有機硼素錯体；特開昭５９−１５２３９６号、特開昭６１−１５１１９７号に記載のチタノセン類；「コーディネーション・ケミストリー・レビュー（Ｃｏｏｒｄｉｎａｔｉｏｎ Ｃｈｅｍｉｓｔｒｙ Ｒｅｖｉｅｗ）」８４巻，８５〜２７７頁（１９８８年）ならびに特開平２−１８２７０１号に記載のルテニウム等の遷移金属を含有する遷移金属錯体；特開平３−２０９４７７号に記載の２，４，５−トリアリールイミダゾール二量体；四臭化炭素、特開昭５９−１０７３４４号に記載の有機ハロゲン化合物等。
【０１００】
中でも好ましい物は、チタノセン類である。チタノセン類の具体例としては、ジ−シクロペンタジエニル−Ｔｉ−ジ−クロライド、ジ−シクロペンタジエニル−Ｔｉ−ビス−フェニル、ジ−シクロペンタジエニル−Ｔｉ−ビス−２，３，４，５，６−ペンタフルオロフェニ−１−イル、ジ−シクロペンタジエニル−Ｔｉ−ビス−２，３，５，６−テトラフルオロフェニ−１−イル、ジ−シクロペンタジエニル−Ｔｉ−ビス−２，４，６−トリフルオロフェニ−１−イル、ジ−シクロペンタジエニル−Ｔｉ−ビス−２，６−ジフルオロフェニ−１−イル、ジ−シクロペンタジエニル−Ｔｉ−ビス−２，４−ジフルオロフェニ−１−イル、ジ−メチルシクロペンタジエニル−Ｔｉ−ビス−２，３，４，５，６−ペンタフルオロフェニ−１−イル、ジ−メチルシクロペンタジエニル−Ｔｉ−ビス−２，３，５，６−テトラフルオロフェニ−１−イル、ジ−メチルシクロペンタジエニル−Ｔｉ−ビス−２，４−ジフルオロフェニ−１−イル、ビス（シクロペンタジエニル）−ビス（２，６−ジフルオロ−３−（ピリ−１−イル）フェニル）チタニウム（ＩＲＵＧＡＣＵＲＥ７８４：チバスペシャリティーケミカルズ社製）等が挙げられるが、これに限定されるものではない。
【０１０１】
光源にレーザー光を用いる場合、好ましくは感光層に増感色素を添加することがこのましい。
【０１０２】
可視光から近赤外まで波長増感させる化合物としては、例えば、シアニン、フタロシアニン、メロシアニン、ポルフィリン、スピロ化合物、フェロセン、フルオレン、フルギド、イミダゾール、ペリレン、フェナジン、フェノチアジン、ポリエン、アゾ化合物、ジフェニルメタン、トリフェニルメタン、ポリメチンアクリジン、クマリン、ケトクマリン、キナクリドン、インジゴ、スチリル、ピリリウム化合物、ピロメテン化合物、ピラゾロトリアゾール化合物、ベンゾチアゾール化合物、バルビツール酸誘導体、チオバルビツール酸誘導体等が挙げられ、更に欧州特許５６８，９９３号、米国特許４，５０８，８１１号、同５，２２７，２２７号、特開２００１−１２５２５５、特開平１１−２７１９６９号等に記載の化合物も用いられる。
【０１０３】
本発明において、上記の光重合開始剤と増感色素の組合せの好ましい具体例としては、特開２００１−１２５２５５、特開平１１−２７１９６９号に記載のある組合せが挙げられる。
【０１０４】
これら光重合開始剤の配合量は特に限定されないが、好ましくは、本発明に係る付加重合可能なエチレン性不飽和結合含有単量体１００質量部に対して０．１〜２０質量部である。光重合開始剤と増感色素の配合比率は、モル比で１：１００〜１００：１の範囲が好ましい。
【０１０５】
本発明の感光性平版印刷版材料の光重合性感光層の塗布組成物には、上記した成分の他に、感光性平版印刷版材料の製造中あるいは保存中において重合可能なエチレン性不飽和二重結合単量体の不要な重合を阻止するために、重合防止剤を添加することが望ましい。適当な重合防止剤としてはハイドロキノン、ｐ−メトキシフェノール、ジ−ｔ−ブチル−ｐ−クレゾール、ピロガロール、ｔ−ブチルカテコール、ベンゾキノン、４，４′−チオビス（３−メチル−６−ｔ−ブチルフェノール）、２，２′−メチレンビス（４−メチル−６−ｔ−ブチルフェノール）、Ｎ−ニトロソフェニルヒドロキシルアミン第一セリウム塩、２−ｔ−ブチル−６−（３−ｔ−ブチル−２−ヒドロキシ−５−メチルベンジル）−４−メチルフェニルアクリレート、２，２，６，６，−テトラメチルピペリジン誘導体等のヒンダードアミン類等が挙げられる。
【０１０６】
重合防止剤の添加量は、上記組成物の全固形分の質量に対して、約０．０１％〜約５％が好ましい。また必要に応じて、酸素による重合阻害を防止するためにベヘン酸やベヘン酸アミドのような高級脂肪酸誘導体等を添加したり、塗布後の乾燥の過程で感光性層の表面に偏在させてもよい。高級脂肪酸誘導体の添加量は、全組成物の約０．５％〜約１０％が好ましい。
【０１０７】
また、着色剤も使用することができ、着色剤としては、市販のものを含め従来公知のものが好適に使用できる。例えば、改訂新版「顔料便覧」，日本顔料技術協会編（誠文堂新光社）、カラーインデックス便覧等に述べられているものが挙げられる。
【０１０８】
顔料の種類としては、黒色顔料、黄色顔料、赤色顔料、褐色顔料、紫色顔料、青色顔料、緑色顔料、蛍光顔料、金属粉顔料等が挙げられる。具体的には、無機顔料（二酸化チタン、カーボンブラック、グラファイト、酸化亜鉛、プルシアンブルー、硫化カドミウム、酸化鉄、ならびに鉛、亜鉛、バリウム及びカルシウムのクロム酸塩等）及び有機顔料（アゾ系、チオインジゴ系、アントラキノン系、アントアンスロン系、トリフェンジオキサジン系の顔料、バット染料顔料、フタロシアニン顔料及びその誘導体、キナクリドン顔料等）が挙げられる。
【０１０９】
これらの中でも、使用する露光レーザーに対応した分光増感色素の吸収波長域に実質的に吸収を持たない顔料を選択して使用することが好ましく、この場合、使用するレーザー波長での積分球を用いた顔料の反射吸収が０．０５以下であることが好ましい。又、顔料の添加量としては、上記組成物の固形分に対し０．１〜１０質量％が好ましく、より好ましくは０．２〜５質量％である。
【０１１０】
露光光源として、アルゴンレーザー（４８８ｎｍ）又はＳＨＧ−ＹＡＧレーザー（５３２ｎｍ）を使用する場合には、上記の感光波長領域での顔料吸収及び現像後の可視画性の観点から、紫色顔料、青色顔料を用いるのが好ましい。このようなものとしては、例えばコバルトブルー、セルリアンブルー、アルカリブルーレーキ、フォナトーンブルー６Ｇ、ビクトリアブルーレーキ、無金属フタロシアニンブルー、フタロシアニンブルーフアーストスカイブルー、インダンスレンブルー、インジコ、ジオキサンバイオレット、イソビオランスロンバイオレット、インダンスロンブルー、インダンスロンＢＣ等を挙げることができる。これらの中で、より好ましくはフタロシアニンブルー、ジオキサンバイオレットである。
【０１１１】
また、支持体への接着性を向上させるために可塑剤を含有することができる。可塑剤としては、ジメチルフタレート、ジエチルフタレート、ジブチルフタレート、ジヘプチルフタレート、ジ−２−エチルヘキシルフタレート、ジ−ｎ−オクチルフタレート、ジドデシルフタレート、ジイソデシルフタレート、ブチルベンジルフタレート、ジイソノニルフタレート、エチルフタリルエチルグリコール、ジメチルイソフタレート、トリエチレングリコールジカプリレート、ジメチルグリコールフタレート、トリクレジルホスフェート、ジオクチルアジペート、ジブチルセバケート、トリアセチルグリセリンなどを挙げることができる。可塑剤の添加量は、上記組成物の固形分に対し好ましくは約０〜３質量％であり、より好ましくは０．１〜２質量％である。
【０１１２】
また、上記組成物は本発明の性能を損わない範囲で、界面活性剤を塗布性改良剤として含有することができる。その中でも好ましいのはフッ素系界面活性剤である。また、硬化皮膜の物性を改良するために、無機充填剤やジオクチルフタレート、ジメチルフタレート、トリクレジルホスフェート等の可塑剤等の添加剤を加えてもよい。これらの添加量は全固形分の１０％以下が好ましい。
【０１１３】
本発明の感光性平版印刷版材料の光重合性感光層の感光性組成物を調製する際に使用する溶剤としては、例えば、アルコール：多価アルコールの誘導体類では、ｓｅｃ−ブタノール、イソブタノール、ｎ−ヘキサノール、ベンジルアルコール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、１，５−ペンタンジオール、又エーテル類：プロピレングリコールモノブチルエーテル、ジプロピレングリコールモノメチルエーテル、トリプロピレングリコールモノメチルエーテル、又ケトン類、アルデヒド類：ジアセトンアルコール、シクロヘキサノン、メチルシクロヘキサノン、又エステル類：乳酸エチル、乳酸ブチル、シュウ酸ジエチル、安息香酸メチル等が好ましく挙げられる。
【０１１４】
調製された感光性組成物（感光層塗布液）は、従来公知の方法で支持体上に塗布し、乾燥し、感光性平版印刷版材料を作製することができる。塗布液の塗布方法としては、例えばエアドクタコータ法、ブレードコータ法、ワイヤバー法、ナイフコータ法、ディップコータ法、リバースロールコータ法、グラビヤコータ法、キャストコーティング法、カーテンコータ法及び押し出しコータ法等を挙げることができる。
【０１１５】
感光層の乾燥温度は低いと十分な耐刷性を得ることが出来ず、又高過ぎるとマランゴニーを生じてしまうばかりか、非画線部のカブリを生じてしまう。好ましい乾燥温度範囲としては、６０〜１６０℃の範囲が好ましく、より好ましくは８０〜１４０℃、特に好ましくは、９０〜１２０℃の範囲で乾燥することが好ましい。
【０１１６】
本発明の感光性平版印刷版材料の光重合性感光層の上側には、保護層を設けることが好ましい。該保護層（酸素遮断層）は、後述する現像液（一般にはアルカリ水溶液）への溶解性が高いことが好ましい。
【０１１７】
該保護層を構成する素材として好ましい例は、ポリビニルアルコール、ポリサッカライド、ポリビニルピロリドン、ポリエチレングリコール、ゼラチン、膠、カゼイン、ヒドロキシエチルセルロース、カルボキシメチルセルロース、メチルセルロース、ヒドロキシエチル澱粉、アラビアゴム、サクローズオクタアセテート、アルギン酸アンモニウム、アルギン酸ナトリウム、ポリビニルアミン、ポリエチレンオキシド、ポリスチレンスルホン酸、ポリアクリル酸、水溶性ポリアミド等が挙げられる。これらの化合物を単独又は２種以上併用し塗布組成物とし用いることができる。特に好ましい化合物としてはポリビニルアルコールが挙げられる。
【０１１８】
保護層塗布組成物を調製するには、上記の素材を適当な溶剤に溶解して塗布液とすることができ、この塗布液を本発明に係る光重合性感光層上に塗布し、乾燥して保護層を形成することができる。保護層の厚みは０．１〜５．０μｍが好ましく、特に好ましくは０．５〜３．０μｍである。保護層には、更に必要に応じて界面活性剤、マット剤等を含有することができる。
【０１１９】
保護層の塗布方法としても、上記例に挙げた公知の方法を好適に用いることができる。保護層の乾燥温度は、感光層の乾燥温度よりも低い方がより好ましい。好ましくは感光層乾燥温度との差が１０℃以上、より好ましくは２０℃以上である場合が好ましく、その場合の上限はせいぜい５０℃程度が好ましい。
【０１２０】
また、保護層の乾燥温度が、感光層が含有するバインダーのガラス転移温度（Ｔｇ）より低いことが好ましい。保護層の乾燥温度と、感光層が含有するバインダーのガラス転移温度（Ｔｇ）の差は２０℃以上であることが好ましく、より好ましくは４０℃以上であり、その差の上限はせいぜい６０℃程度が好ましい。
【０１２１】
本発明の感光性平版印刷版材料に画像露光する光源としては、例えばレーザー、発光ダイオード、キセノンランプ、キセノンフラッシュランプ、ハロゲンランプ、カーボンアーク燈、メタルハライドランプ、タングステンランプ、高圧水銀ランプ、無電極光源等を挙げることができる。
【０１２２】
一括露光する場合には、光重合性感光層上に、所望の露光画像のネガパターンを遮光性材料で形成したマスク材料を重ね合わせ、露光すればよい。
【０１２３】
発光ダイオードアレイ等のアレイ型光源を使用する場合や、ハロゲンランプ、メタルハライドランプ、タングステンランプ等の光源を、液晶、ＰＬＺＴ等の光学的シャッター材料で露光制御する場合には、画像信号に応じたデジタル露光をすることが可能であり好ましい。この場合は、マスク材料を使用せず、直接書込みを行うことができる。
【０１２４】
レーザー露光の場合には、光をビーム状に絞り画像データに応じた走査露光が可能なので、マスク材料を使用せず、直接書込みを行うのに適している。又、レーザーを光源として用いる場合には、露光面積を微小サイズに絞ることが容易であり、高解像度の画像形成が可能となる。
【０１２５】
レーザー光源としては、アルゴンレーザー、Ｈｅ−Ｎｅガスレーザー、ＹＡＧレーザー、半導体レーザー等を何れも好適に用いることが可能である。レーザーの走査方法としては、円筒外面走査、円筒内面走査、平面走査などがある。円筒外面走査では、記録材料を外面に巻き付けたドラムを回転させながらレーザー露光を行い、ドラムの回転を主走査としレーザー光の移動を副走査とする。円筒内面走査では、ドラムの内面に記録材料を固定し、レーザービームを内側から照射し、光学系の一部又は全部を回転させることにより円周方向に主走査を行い、光学系の一部又は全部をドラムの軸に平行に直線移動させることにより軸方向に副走査を行う。平面走査では、ポリゴンミラーやガルバノミラーとｆθレンズ等を組み合わせてレーザー光の主走査を行い、記録媒体の移動により副走査を行う。円筒外面走査及び円筒内面走査の方が光学系の精度を高め易く、高密度記録には適している。
【０１２６】
本発明では、画像露光後、画像形成反応の促進、感度や耐刷性の向上のため加熱処理が施されることが好ましい。加熱処理の方法は特に限定されないが画像形成面への非接触方式が好ましく、通常の恒温槽、熱風式乾燥機および加熱処理部を装着した市販の自動現像機を使用できる。加熱温度は版面温度で１００〜１３０℃で行うことが好ましい。温度が高すぎると非画像部のかぶりが生じる等の問題があり、また温度が低すぎると感度、耐刷性が不十分等の問題が生じる。加熱時間は５〜６０秒で行うことが好ましい。加熱時間が長すぎると非画像部のかぶりが生じる等の問題があり、また加熱時間が短すぎると感度、耐刷性が不十分等の問題が生じる。露光終了から加熱処理までの時間は３００秒以内であり、出来るだけ短いことが望ましいことは言うまでもない。３００秒を越えると感度、耐刷性が不十分等の問題が生じる。
【０１２７】
本発明の感光性平版印刷版材料の画像露光した光重合性感光層は露光部が硬化する。これを現像液で現像処理することにより、未露光部が除去され画像形成が可能となる。このような現像液としては、従来より知られているアルカリ水溶液が使用できる。珪酸ナトリウム、同カリウム、同アンモニウム；第二燐酸ナトリウム、同カリウム、同アンモニウム；重炭酸ナトリウム、同カリウム、同アンモニウム；炭酸ナトリウム、同カリウム、同アンモニウム；炭酸水素ナトリウム、同カリウム、同アンモニウム；硼酸ナトリウム、同カリウム、同アンモニウム；水酸化ナトリウム、同カリウム、同アンモニウム及び同リチウム等の無機アルカリ剤を使用するアルカリ現像液が挙げられる。
【０１２８】
また、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−ｉ−プロピルアミン、ジ−ｉ−プロピルアミン、トリ−ｉ−プロピルアミン、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−ｉ−プロパノールアミン、ジ−ｉ−プロパノールアミン、エチレンイミン、エチレンジアミン、ピリジン等の有機アルカリ剤も用いることができる。
【０１２９】
これらのアルカリ剤は、単独又は２種以上組み合わせて用いられる。又、該現像液には、必要に応じてアニオン性界面活性剤、両性活性剤やアルコール等の有機溶媒を加えることができる。
【０１３０】
本発明で用いる現像液は、珪酸塩を含有し、ｐＨ１０．０〜１２．５であることが好ましく、より好ましくはｐＨ１０．５〜１２．４の範囲である。係る現像により、本発明の効果が特異的に奏されるものである。即ち、従来不十分であった現像性や感度を十分な性能として引き出すこともさることながら、現像スラッジ性能の改良、耐刷性の改良等の性能も同時に改善できるものである。
【０１３１】
【実施例】
以下、実施例により本発明を更に具体的に説明するが、本発明はこれに限定されるものではない。尚、実施例における「部」は、特に断りない限り「質量部」を表す。
【０１３２】
（高分子結合剤Ａ合成）
窒素気流下の三ツ口フラスコに、メチルメタクリレート（１６２部：１．６２モル）、エチルメタクリレート（１２部：０．１０モル）、メタクリル酸（２６部：０．３０モル）、エタノール４００部及びα，α′−アゾビスイソブチロニトリル（５部）を入れ、窒素気流中８０℃のオイルバスで８時間反応させた。次にエタノールを系外に除去し、残留溶剤を１％以下として、高分子結合剤Ａを得た。重量平均分子量は約５０，０００（ＧＰＣ：ポリスチレン換算）であった。
【０１３３】
（高分子結合剤Ｂの合成）
窒素気流下の三ツ口フラスコに、メチルメタクリレート（１２５部：１．２５モル）、エチルメタクリレート（１２部：０．１０モル）、メタクリル酸（６３部：０．７３モル）、エタノール４００部及びα，α′−アゾビスイソブチロニトリル（５部）を入れ、窒素気流中８０℃のオイルバスで６時間反応させて高分子重合体を得た。その後、該重合体に、トリエチルアンモニウムクロライド４部及びグリシジルメタクリレート（５２部：０．７３モル）を加えて、温度２５℃で３時間反応させて高分子結合剤Ｂを得た。重量平均分子量は約５５，０００（ＧＰＣ：ポリスチレン換算）であった。
【０１３４】
【化４】

【０１３５】
（支持体の作製）
厚さ０．３０ｍｍのアルミニウム板（材質１０５０、調質Ｈ１６）を６５℃に保たれた５％水酸化ナトリウム水溶液に浸漬し、１分間の脱脂処理を行った後、水洗した。この脱脂アルミニウム板を、２５℃に保たれた１０％塩酸水溶液中に１分間浸漬して中和した後、水洗した。次いで、このアルミニウム板を、０．３質量％の塩酸水溶液中で、２５℃、電流密度１００Ａ／ｄｍ²の条件下に交流電流により６０秒間、電解粗面化を行った後、６０℃に保たれた５％水酸化ナトリウム水溶液中で１０秒間のデスマット処理を行った。デスマット処理を行った粗面化アルミニウム板を、１５％硫酸溶液中で、２５℃、電流密度１０Ａ／ｄｍ²、電圧１５Ｖの条件下に１分間陽極酸化処理を行い、更に３％硅酸ナトリウムで９０℃で封孔処理を行って支持体を作製した。この時、表面の中心線平均粗さ（Ｒａ）は０．６５μｍであった。
【０１３６】
（支持体の表面処理）
上記処理を行った後、続けて下記溶液中で浸漬し処理を行った。
【０１３７】
溶液温度 ８０℃
ビニルホスホン酸 ０．２％
ポリビニルホスホン酸 １．５％
上記溶液中にアルミニウム板を３０秒間通し、乾燥した。
【０１３８】
（感光性平版印刷版材料１〜３０の作製）
上記表面処理済み支持体上に、下記組成の光重合性感光層塗工液を乾燥時１．５ｇ／ｍ²になるようワイヤーバーで塗布し、９５℃で１．５分間乾燥した。その後、更に該感光層上に、下記組成のオーバーコート層塗工液を乾燥時２．０ｇ／ｍ²になるようにアプリケーターで塗布し、７５℃で１．５分間乾燥して、感光層上にオーバーコート層を有する感光性平版印刷版材料を作製した。
【０１３９】

【０１４０】
【化５】

【０１４１】
このようにして作製した光重合型感光性平版印刷版材料について、ＦＤ−ＹＡＧレーザー光源を搭載したＣＴＰ露光装置（Ｔｉｇｅｒｃａｔ：ＥＣＲＭ社製）を用いて２５４０ｄｐｉ（ｄｐｉとは１インチ即ち２．５４ｃｍ当たりのドット数を表す）の解像度で画像露光を行った。次いで、現像前に加熱装置部、オーバーコート層を除去する前水洗部、下記現像液組成１を充填した現像部、版面に付着した現像液を取り除く水洗部、画線部保護のためのガム液（ＧＷ−３：三菱化学社製を２倍希釈したもの）を備えたＣＴＰ自動現像機（ＰＨＷ２３−Ｖ：Ｔｅｃｈｎｉｇｒａｐｈ社製）で現像処理を行い、平版印刷版１〜３０を得た。このとき加熱装置部は版面温度１１５℃、版滞在時間１５秒となるように設定した。また露光終了から自現機の加熱装置部への版挿入は６０秒以内に行った。
【０１４２】
現像液組成１（下記添加剤を含有する水溶液）
Ａケイ酸カリ ８．０質量％
ニューコールＢ−１３：日本乳化剤（株）製 ３．０質量％
苛性カリ ｐＨ＝１２．３となる添加量
（平版印刷版の評価）
上記のようにして得られた平版印刷版について、以下の評価をした。評価結果を表１に示す。また、画像形成した感光性平版印刷版材料１〜３０を現像した現像液は、現像液のｐＨが１２．３と低いｐＨでありながら、現像スラッジの発生が抑えられていることが分かった。
【０１４３】
《感度》
画像部の膜減りが観察されず、且つ、１７５線・５０％の網点露光部が、作製した平版印刷版面上で５０％に再現できる露光量の２倍の光量で描画し、これを感度とした。
【０１４４】
《耐刷性》
１７５線の画像を適性露光量で露光、現像して作製した平版印刷版を、印刷機（三菱重工業（株）製ＤＡＩＹＡ１Ｆ−１）で、コート紙、印刷インキ（大日本インキ化学工業社製の、大豆油インキ“ナチュラリス１００”）及び湿し水（東京インク（株）製Ｈ液ＳＧ−５１濃度１．５％）を用いて印刷を行い、ハイライト部の点細り、シャドウ部の絡みの発生する印刷枚数を耐刷性の指標とした。
【０１４５】
《プレートクリーナー耐性》
１７５線の画像を適性露光量で露光、現像して作製した平版印刷版を、プレートクリーナー（エスケー液製造ウルトラプレートクリーナー）に浸漬し、浸漬後、スポンジで擦りながら水洗し、乾燥した後、画像の観察を行った。画像部の欠落が起こり始める浸漬時間をプレートクリーナー耐性の指標とした。
【０１４６】
【表１】

【０１４７】
表１より、本発明の感光性平版印刷版材料は感度、耐刷性、プレートクリーナー耐性において、比較に対し優れた性能を示している。
【０１４８】
（感光性平版印刷版材料３１〜４０の作製）
感光性平版印刷版材料１〜３０の分光増感色素１、２及びＩＲＧＡＣＵＲＥ ７８４を添加するかわりに、下記化合物を添加し、オーバーコートは下記化合物１６を添加して、感光性平版印刷版材料１〜３０と同条件で試料を作製した。
【０１４９】
化合物９ ０．７部
化合物１０ ０．７部
化合物１１ ０．７部
化合物１２ ０．７部
化合物１３ ０．７部
化合物１４ ０．７部
化合物１５ ４．０部
（オーバーコート層（保護層）塗工液）
ポリビニルアルコール（ＧＬ−０５：日本合成化学社製） ８７部
水溶性ポリアミド（Ｐ−７０：東レ社製） １０部
化合物１６ ２部
界面活性剤（サーフィノール４６５：日信化学工業社製） ０．５部
水 ９００部
【０１５０】
【化６】

【０１５１】
発振波長４０５ｎｍのＩｎＧａＮ系半導体レーザーを搭載した自作の装置で露光を行った以外は、感光性平版印刷版材料１〜３０と同様の操作を行い、画像形成、平版印刷版の評価を行った。評価結果を表２に示す。また、画像形成した感光性平版印刷版材料３１〜４０を現像した現像液は、現像液のｐＨが１２．３と低いｐＨでありながら、現像スラッジの発生が抑えられていることが分かった。
【０１５２】
【表２】

【０１５３】
表２より、本発明の感光性平版印刷版材料は感度、耐刷性、プレートクリーナー耐性において、比較に対し優れた性能を示していることが分かる。
【０１５４】
【発明の効果】
本発明によって、感度、耐刷性、プレートクリーナー耐性に優れた感光性平版印刷版材料を提供することができた。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a photosensitive lithographic printing plate material.
[0002]
[Prior art]
Conventionally, there has been known a photosensitive lithographic printing plate material in which a photopolymerizable photosensitive layer and a protective layer are laminated on a support subjected to a hydrophilic surface treatment. In particular, in recent years, in order to quickly obtain a high-resolution lithographic printing plate material, and for the purpose of filmlessness, digital exposure based on image information using a laser is performed and developed to develop a lithographic printing plate. The manufacturing method has been generalized.
[0003]
For example, a light source is modulated by an output signal from an electronic plate making system or an image processing system or an image signal transmitted through a communication line, etc., and a printing plate is formed by directly scanning and exposing a photosensitive material. Systems that do this are known.
[0004]
The photopolymerizable photosensitive layer generally contains an acrylic monomer, an alkali-soluble resin, a photopolymerizable initiator, and, if necessary (especially when performing laser writing), a sensitizing dye to match the wavelength. It is known. It is also known to provide a protective layer for the purpose of preventing polymerization inhibition by oxygen.
[0005]
A long-wavelength visible light source such as an Ar laser (488 nm) or an FD-YAG laser (532 nm) is used as a light source for exposing and making a photopolymerization type photosensitive lithographic printing plate material. Furthermore, in recent years, for example, semiconductor lasers that can continuously oscillate in the 350 to 450 nm region using InGaN-based or ZnSe-based materials have been put into practical use. The scanning exposure system using these short-wave light sources has an advantage that an economical system can be constructed while having a sufficient output because a semiconductor laser can be manufactured at a low cost because of its structure. Furthermore, compared with a system using a conventional FD-YAG or Ar laser, there is a possibility that it can be used for a photosensitive lithographic printing plate material having a short photosensitive area capable of working under a brighter safelight.
[0006]
In a photopolymerization type photosensitive lithographic printing plate material, usually after image exposure, heat treatment as necessary, washing with water for removing the protective layer, development processing for dissolving and removing unexposed portions, washing with water, non-washing A finisher gum treatment for hydrophilizing the image area is performed to obtain a lithographic printing plate. At this time, it is known that after image exposure, a heat treatment is performed to accelerate the polymerization reaction, thereby obtaining high sensitivity and high printing durability.
[0007]
On the other hand, the developer of the photosensitive lithographic printing plate material is usually used at a pH of 12.5 or more as a water-based alkaline developer in order to completely remove the non-image area photosensitive layer, that is, to perform development. Was common. However, in recent years, processing with an alkaline developer having a lower pH has been desired from the viewpoint of workability, safety, environmental suitability, and the like.
[0008]
[Problems to be solved by the invention]
However, the photopolymerization type photosensitive lithographic printing plate material still has insufficient printing durability and insufficient resistance to various plate cleaners for preventing printing stains used during printing. It was.
[0009]
Furthermore, developing with a low pH developer reveals problems such as increase in developability and development sludge amount. On the other hand, development with a low pH developer improves the developability of the photosensitive polymer layer. When trying to increase it, the problem that sensitivity, printing durability, and chemical resistance deteriorated occurred.
[0010]
The present invention has been made in view of such problems, and an object of the present invention is to provide a photosensitive lithographic printing plate material having high image performance and excellent sensitivity, printing durability, and resistance to various plate cleaners. .
[0011]
[Means for Solving the Problems]
The above object of the present invention has been achieved by the following.
[0013]
1 ) A photosensitive lithographic printing plate material having at least one photopolymerizable photosensitive layer containing an ethylenically unsaturated bond-containing monomer capable of addition polymerization, a photopolymerization initiator and a polymer binder on a support. A photosensitive lithographic printing plate material which forms a photocured image by exposing a non-image portion of the photopolymerizable photosensitive layer from a support with a developing solution after imagewise exposure and image-curing the photosensitive layer In the above, the addition-polymerizable ethylenically unsaturated bond-containing monomer is a compound (D) having two or more urethane bonds and four or more ethylenically unsaturated bonds, two or more urethane bonds and two Compound (E) having an ethylenically unsaturated bond in a mass ratio of 5: 1 to 1: 5 and having no urethane bond and having two or more ethylenically unsaturated bonds Ratio [((D) + (E)) :( F) 5: 1 to 1: photosensitive lithographic printing plate material characterized by containing at 1.
[0015]
2 ) A photosensitive lithographic printing plate material having at least one photopolymerizable photosensitive layer containing an ethylenically unsaturated bond-containing monomer capable of addition polymerization, a photopolymerization initiator and a polymer binder on a support. A photosensitive lithographic printing plate material which forms a photocured image by exposing a non-image portion of the photopolymerizable photosensitive layer from a support with a developing solution after imagewise exposure and image-curing the photosensitive layer In the above, the addition-polymerizable ethylenically unsaturated bond-containing monomer is a compound (D) having two or more urethane bonds and four or more ethylenically unsaturated bonds, two or more urethane bonds and two Compound (E) having an ethylenically unsaturated bond in a mass ratio of 5: 1 to 1: 5 and having no urethane bond and having two or more ethylenically unsaturated bonds Ratio [((D) + (E)) :( F) 5: 1 to 1: 1, and the polymer binder includes a monomer unit having a carboxyl group and a unit obtained by reacting an epoxy group-containing unsaturated compound with at least a part of the monomer unit having the carboxyl group A photosensitive lithographic printing plate material, characterized in that it is a copolymer.
[0016]
3 1) The developer according to 1), wherein the developer contains silicate and has a pH of 10.0 to 12.5. Or 2) The photosensitive lithographic printing plate material described in 1.
[0017]
4 1) to 1), wherein heat treatment is performed after image exposure. 3 ). The photosensitive lithographic printing plate material according to any one of the above.
[0018]
5 The heat treatment is performed at a plate temperature of 100 to 130 ° C. for 5 to 60 seconds. 4 ) Photosensitive lithographic printing plate material.
[0019]
6 The heat treatment is performed within 300 seconds after image exposure. 4 ) Photosensitive lithographic printing plate material.
[0020]
7 1) to 1) characterized in that an oxygen blocking layer is provided on the photopolymerizable photosensitive layer. 6 ). The photosensitive lithographic printing plate material according to any one of the above.
[0021]
8 1) to 3), wherein the support is an aluminum support subjected to at least roughening and anodizing treatment. 7 ). The photosensitive lithographic printing plate material according to any one of the above.
[0022]
9 The aluminum support is further subjected to a hydrophilization treatment or a subbing treatment. 8 ) Photosensitive lithographic printing plate material.
[0023]
The present invention is described in more detail below.
The support that can be used for the photosensitive lithographic printing plate material of the present invention is, for example, a metal plate such as aluminum, stainless steel, chromium, or nickel, or a plastic film such as a polyester film, polyethylene film, or polypropylene film, and the aforementioned metal thin film. Can be used, such as polyester film, vinyl chloride film, nylon film, etc., which have been subjected to hydrophilic treatment, but aluminum plates are preferably used. In this case, pure aluminum plates and aluminum alloys are used. It may be a board.
[0024]
Various aluminum alloys can be used as the support, and for example, alloys of metals such as silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, nickel, titanium, sodium, iron, and aluminum are used. .
[0025]
The support that can be used for the photosensitive lithographic printing plate material of the present invention is preferably subjected to a degreasing treatment in order to remove rolling oil on the surface prior to roughening (graining treatment). As the degreasing treatment, a degreasing treatment using a solvent such as trichlene or thinner, an emulsion degreasing treatment using an emulsion such as kesilon or triethanol, or the like is used. In addition, an alkaline aqueous solution such as caustic soda can be used for the degreasing treatment. When an alkaline aqueous solution such as caustic soda is used for the degreasing treatment, dirt and oxide film that cannot be removed only by the degreasing treatment can be removed. When an alkaline aqueous solution such as caustic soda is used for the degreasing treatment, smut is generated on the surface of the support. In this case, the substrate is immersed in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid, or a mixed acid thereof and desmutted. It is preferable to perform the treatment.
[0026]
Examples of the roughening method include a mechanical method and a method of etching by electrolysis.
[0027]
The mechanical roughening method used is not particularly limited, but a brush polishing method and a honing polishing method are preferable. For the roughening by the brush polishing method, for example, a rotating brush using brush bristles having a diameter of 0.2 to 0.8 mm is rotated, and for example, volcanic ash particles having a particle size of 10 to 100 μm are uniformly distributed in water on the support surface. While supplying the dispersed slurry, it can be performed by pressing a brush. The roughening by honing polishing is performed by, for example, uniformly dispersing volcanic ash particles having a particle size of 10 to 100 μm in water, injecting them with pressure from a nozzle, and causing them to collide obliquely with the support surface. it can. Further, for example, abrasive particles having a particle size of 10 to 100 μm are applied to the support surface at intervals of 100 to 200 μm at 2.5 × 10. ^Three -10x10 ^Three Piece / cm ² It is also possible to perform roughening by laminating the coated sheets so as to exist at a density and transferring the rough surface pattern of the sheet by applying pressure.
[0028]
After the surface is roughened by the mechanical surface roughening method, it is preferable to immerse in an aqueous solution of acid or alkali in order to remove the abrasive that has digged into the surface of the support, formed aluminum scraps, and the like. Examples of the acid include sulfuric acid, persulfuric acid, hydrofluoric acid, phosphoric acid, nitric acid, hydrochloric acid, and the like. Examples of the base include sodium chloride and potassium hydroxide. Among these, it is preferable to use an aqueous alkali solution such as sodium hydroxide. The amount of aluminum dissolved on the surface is 0.5 to 5 g / m. ² Is preferred. After the immersion treatment with an alkaline aqueous solution, it is preferable to carry out a neutralization treatment by immersion in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid or a mixed acid thereof.
[0029]
The electrochemical surface roughening method is not particularly limited, but a method of electrochemical surface roughening in an acidic electrolyte is preferable. As the acidic electrolytic solution, an acidic electrolytic solution usually used in an electrochemical surface roughening method can be used, but a hydrochloric acid-based or nitric acid-based electrolytic solution is preferably used. As the electrochemical surface roughening method, for example, methods described in Japanese Patent Publication No. 48-28123, British Patent No. 896,563 and Japanese Patent Laid-Open No. 53-67507 can be used. This roughening method can be generally performed by applying a voltage in the range of 1 to 50 volts, but is preferably selected from the range of 10 to 30 volts. Current density is 10-200A / dm ² The range of 50 to 150 A / dm can be used. ² It is preferable to select from the range. The amount of electricity is 100-5000c / dm ² The range of 100 to 2000 c / dm can be used. ² It is preferable to select from the range. The temperature at which the roughening method is performed can be in the range of 10 to 50 ° C, but is preferably selected from the range of 15 to 45 ° C.
[0030]
When electrochemical surface roughening is performed using a nitric acid-based electrolyte as the electrolyte, it can be generally performed by applying a voltage in the range of 1 to 50 volts, but is selected from the range of 10 to 30 volts. Is preferred. Current density is 10-200A / dm ² The range of 20-100 A / dm can be used. ² It is preferable to select from the range. The amount of electricity is 100-5000c / dm ² The range of 100 to 2000 c / dm can be used. ² It is preferable to select from the range. The temperature at which the electrochemical surface roughening method is performed can be in the range of 10 to 50 ° C, but is preferably selected from the range of 15 to 45 ° C. The concentration of nitric acid in the electrolytic solution is preferably 0.1 to 5% by mass. If necessary, nitrate, chloride, amines, aldehydes, phosphoric acid, chromic acid, boric acid, acetic acid, oxalic acid, and the like can be added to the electrolytic solution.
[0031]
When a hydrochloric acid-based electrolyte is used as the electrolyte, it can be generally applied by applying a voltage in the range of 1 to 50 volts, but is preferably selected from the range of 2 to 30 volts. Current density is 10-200A / dm ² The range of 50 to 150 A / dm can be used. ² It is preferable to select from the range. The amount of electricity is 100-5000c / dm ² The range of 100 to 2000 c / dm can be used. ² Furthermore, 200 to 1000 c / dm ² It is preferable to select from the range. The temperature at which the electrochemical surface roughening method is performed can be in the range of 10 to 50 ° C, but is preferably selected from the range of 15 to 45 ° C. The concentration of hydrochloric acid in the electrolytic solution is preferably 0.1 to 5% by mass. If necessary, nitrate, chloride, amines, aldehydes, phosphoric acid, chromic acid, boric acid, acetic acid, oxalic acid, and the like can be added to the electrolytic solution.
[0032]
After the surface is roughened by the electrochemical surface roughening method, it is preferably immersed in an acid or alkali aqueous solution in order to remove aluminum scraps on the surface. Examples of the acid include sulfuric acid, persulfuric acid, hydrofluoric acid, phosphoric acid, nitric acid, hydrochloric acid, and the like. Examples of the base include sodium hydroxide and potassium hydroxide. Among these, it is preferable to use an alkaline aqueous solution. The amount of aluminum dissolved on the surface is 0.5 to 5 g / m. ² Is preferred. In addition, it is preferable that after the immersion treatment with an alkaline aqueous solution, neutralization treatment is performed by immersion in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid or a mixed acid thereof.
[0033]
The mechanical surface roughening method and the electrochemical surface roughening method may each be used alone for roughing, or the mechanical surface roughening method followed by the electrochemical surface roughening method. You may roughen.
[0034]
Following the roughening treatment, an anodic oxidation treatment can be performed. There is no restriction | limiting in particular in the method of the anodizing process which can be used in this invention, A well-known method can be used. By performing the anodizing treatment, an oxide film is formed on the support. In the anodizing treatment, an aqueous solution containing sulfuric acid and / or phosphoric acid at a concentration of 10 to 50% is used as an electrolytic solution, and a current density of 1 to 10 A / dm. ² The electrolysis method is preferably used, but other methods such as electrolysis at a high current density in sulfuric acid described in US Pat. No. 1,412,768 and those described in US Pat. No. 3,511,661 are described. Examples thereof include a method of electrolysis using phosphoric acid, a method of using a solution containing one or more of chromic acid, oxalic acid, malonic acid and the like. The formed anodic oxidation coating amount is 1-50 mg / dm. ² Is suitable, preferably 10 to 40 mg / dm ² It is. The anodized coating amount is obtained by, for example, immersing an aluminum plate in a chromic phosphate solution (produced by dissolving 85% phosphoric acid solution: 35 ml, chromium oxide (IV): 20 g in 1 L of water), dissolving the oxide coating, It is determined from the measurement of mass change before and after dissolution of the coating on the plate.
[0035]
The anodized support may be sealed as necessary. These sealing treatments can be performed using known methods such as hot water treatment, boiling water treatment, water vapor treatment, sodium silicate treatment, dichromate aqueous solution treatment, nitrite treatment, and ammonium acetate treatment.
[0036]
Furthermore, after performing these treatments, water-soluble resins such as polyvinylphosphonic acid, polymers and copolymers having sulfonic acid groups in the side chain, polyacrylic acid, water-soluble metal salts (for example, zinc borate) Alternatively, an undercoat with a yellow dye, an amine salt or the like is also suitable. Further, a sol-gel treated substrate in which a functional group capable of causing an addition reaction by a radical as disclosed in JP-A-5-304358 is covalently used.
[0037]
As the support, various types can be used as described above. For example, a surface of a polyester film, a vinyl chloride film, a nylon film or the like subjected to a hydrophilic treatment can be used. As the chemical treatment method, sulfuric acid treatment, oxygen plasma etching treatment, corona discharge treatment, provision of a water-soluble resin layer coating layer, etc. are preferably used. In the practice of the present invention, an aluminum plate whose surface has been subjected to roughening treatment, anodizing treatment, sealing treatment and undercoating treatment is particularly preferred.
[0038]
In one embodiment of the present invention, the addition-polymerizable ethylenically unsaturated bond-containing monomer includes two or more compounds (D) having two or more urethane bonds and four or more ethylenically unsaturated bonds. And the compound (E) having two ethylenically unsaturated bonds in a mass ratio of 5: 1 to 1: 5.
[0039]
In another aspect of the present invention, the addition-polymerizable ethylenically unsaturated bond-containing monomer includes a compound (D) having two or more urethane bonds and four or more ethylenically unsaturated bonds. Compound (E) having two or more urethane bonds and two ethylenically unsaturated bonds in a mass ratio of 5: 1 to 1: 5, and having no urethane bond, two or more ethylenically unsaturated groups The compound (F) having a saturated bond is contained in a mass ratio [((D) + (E)) :( F)] 5: 1 to 1: 1.
[0040]
Examples of the compound (D) having two or more urethane bonds and four or more ethylenically unsaturated bonds and the compound (E) having two or more urethane bonds and two ethylenically unsaturated bonds include the following (urethane The monomer is suitably selected from an addition-polymerizable ethylenically unsaturated bond-containing monomer having a group.
[0041]
The compound (F) having no urethane bond and having two or more ethylenically unsaturated bonds can be selected from the following (other monomers containing addition-polymerizable ethylenically unsaturated bonds).
[0042]
In addition, as an embodiment of the present invention, other addition-polymerizable ethylenically unsaturated bond-containing monomers that do not fall under the above (D), (E), and (F) can be used in combination.
[0043]
Examples of the addition-polymerizable ethylenically unsaturated bond-containing monomer having a urethane group include those described in JP-A-57-128716 and JP-A-6-35189.
[0044]
The addition-polymerizable ethylenically unsaturated bond-containing monomer having a urethane group described in JP-A-57-128716 is an acrylate or methacrylate of a polyvalent hydroxy compound having at least two urethane groups in the molecule. A reaction product of glycerol dimethacrylate or glycerol diacrylate with a polyisocyanate obtained by reacting glycerol dimethacrylate or glycerol diacrylate with a polyisocyanate having 2 to 6 OH groups and diisocyanate, or glycerol dimethacrylate or glycerol diacrylate It is a reaction product with diisocyanate. The polyvalent hydroxy compound preferably has 2 or 3 and particularly preferably 2 OH groups.
[0045]
Generally, the diisocyanate is a compound represented by OCN-X-NCO (wherein X is a hydrocarbon group, preferably a saturated aliphatic or alicyclic hydrocarbon group having 2 to 20 carbon atoms). Typically, the reaction product of glycerol dimethacrylate is preferred over the reaction product of glycerol acrylate. The polyvalent isocyanate obtained by the reaction of the polyvalent hydroxy compound and diisocyanate has an average of 2 to 40, preferably 2 to 20, methane groups per molecule. Of the polyvalent hydroxy compounds used for the production of addition-polymerizable ethylenically unsaturated double bond-containing monomers having such urethane groups, representatives saturated with polyether polyvalent hydroxy compounds, etc. HO- [C _p H _2p-v (OH) _v -O-] _m Preference is given to compounds represented by H. p is preferably 2 to 10, particularly 2 to 4. When using unsaturated polyhydric hydroxy compounds, they preferably have 4 to 10 carbon atoms per unit of polyhydric hydroxy compound (also called polyol).
[0046]
Examples of suitable diisocyanates are tolylene diisocyanate, xylylene diisocyanate, naphthylene diisocyanate, hexamethylene diisocyanate, cyclohexylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate and tolylene diisocyanate or diphenylmethane diisocyanate. It is a reaction product of 2 mol and 1 mol of polytetrahydrofuran.
[0047]
Examples of suitable diols are ethylene glycol, propylene glycol, 1,4-butanediol, 2-ethyl-1,6-hexanediol, 1,10-decanediol, 1,4-bis-hydroxymethylcyclohexane, diethylene glycol, Triethylene glycol, polyethylene glycol having a molecular weight of 200 to about 1500 and 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-diphenyl-sulfide, 4,4'-dihydroxy-diphenylmethane, 4,4'-dihydroxy-diphenyl Propane or 4,4'-dihydroxy-diphenylsulfone and 0 to 40 moles of alkylene oxide, polypropylene glycol, polytetrahydrofuran, polybutylene glycol, thiodiethylene glycol or di It is a reaction product of a decoy ethylene glycol.
[0048]
Examples of suitable polyester components are polycaprolactone, polybutyrolactone, polyethylene terephthalate, polypropylene adipate, polybutylene adipate and polyethylene butylene sepassate. Polyester polyols having a molecular weight in the range of about 500 to 3000 are generally very suitable.
[0049]
Apart from this advantageous diol, compounds having 2 to 6 fatty hydroxy groups can also generally be used. Examples of addition polymerizable compounds are glycerol, trimethylolpropane, pentaerythritol, dipentaerythritol and sorbitol. Suitable polyvalent hydroxy compounds include polyester polyols such as lactone polyesters described in US Pat. No. 3,169,945, terminal hydroxy group-containing polyester condensation polymers described in US Pat. No. 3,641,999, US These are hydroxy group-containing polyesters, terminal hydroxy group-containing polyethers and polyester block copolymers, caprolactone polyols and polysiloxane polyols described in Japanese Patent No. 3,931,117.
[0050]
The production of the polymerizable diurethanes or polyurethanes is carried out in a manner known per se, for example as described in U.S. Pat. No. 3,297,745, West German Patent Publication Nos. 2,064,079 and 2,822,190.
[0051]
As the addition-polymerizable ethylenically unsaturated bond-containing monomer having a urethane group described in JP-A-6-35189, a reaction product of monoisocyanate or diisocyanate and a partial ester of a polyhydric alcohol is advantageously used. . Such monomers are described in West German Patent Publication Nos. 2,064,079, 2,361,041, and 2,822,190.
[0052]
Particularly preferred are addition polymerizable compounds containing in the molecule at least one photooxidizable group and at least one urethane group. Suitable photooxidizable groups are in particular thio groups, ureido groups, amino groups and enol groups which may be members of the heterocyclic ring. Examples of these groups are triethanolamino, triphenylamino, thiourea, imidazole, oxazole, thiazole, acetylacetonyl, N-phenylglycine and ascorbic acid groups, preferred are first, second, especially An addition polymerizable compound containing a tertiary amino group.
[0053]
Examples of compounds containing photo-oxidizable groups are described in EP-A-287,818, 353,389 and 364,735. Preferred among the compounds described therein are those containing a ureido group and / or a urethane group in addition to the tertiary amino group.
[0054]
Examples of the addition-polymerizable ethylenically unsaturated double bond-containing monomer having a urethane group contained in the photopolymerizable layer of the present invention include those described in JP-A-57-128716 and JP-A-6-35189. The thing of Unexamined-Japanese-Patent No. 2001-125255 other than the thing of description is mentioned.
[0055]
Addition-polymerizable ethylenically unsaturated bond-containing monomers (hereinafter sometimes referred to as monomers) include known monomers having radically polymerizable ethylenically unsaturated bonds.
[0056]
Specific examples of the compound include 2-ethylhexyl acrylate, 2-hydroxypropyl acrylate, glycerol acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, nonylphenoxyethyl acrylate, tetrahydrofurfuryloxyethyl acrylate, tetrahydrofurfuryloxyhexanol. Monoacrylate, acrylate of ε-caprolactone adduct of 1,3-dioxane alcohol, monofunctional acrylic esters such as 1,3-dioxolane acrylate, or methacrylic acid in which these acrylates are replaced with methacrylate, itaconate, crotonate, or maleate , Itaconic acid, crotonic acid, maleic acid esters such as ethylene glycol diacrylate, triethylene Lucol diacrylate, pentaerythritol diacrylate, hydroquinone diacrylate, resorcin diacrylate, hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, hydroxypivalate, neopentyl glycol diacrylate, neopentyl glycol adipate di Acrylate, diacrylate of ε-caprolactone adduct of neopentyl glycol hydroxypivalate, 2- (2-hydroxy-1,1-dimethylethyl) -5-hydroxymethyl-5-ethyl-1,3-dioxane diacrylate, Tricyclodecane dimethylol acrylate, ε-caprolactone adduct of tricyclodecane dimethylol acrylate, 1,6-hexanedi Difunctional acrylates such as diglycidyl ether diacrylate, or methacrylic acid, itaconic acid, crotonic acid, maleic acid ester, such as trimethylolpropane, in which these acrylates are replaced with methacrylate, itaconate, crotonate, maleate Ε of triacrylate, ditrimethylolpropane tetraacrylate, trimethylolethane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexaacrylate -Caprolactone adduct, pyrogallol triacrylate, propionic acid Polyfunctional acrylic acid ester acids such as pentaerythritol triacrylate, propionic acid / dipentaerythritol tetraacrylate, hydroxypivalylaldehyde-modified dimethylolpropane triacrylate, and their EO-modified products, or their acrylates as methacrylate, itaconate, crotonate And methacrylic acid, itaconic acid, crotonic acid, maleic acid ester, etc., instead of maleate.
[0057]
Prepolymers can also be used as described above. Examples of the prepolymer include compounds as described below, and a prepolymer obtained by introducing acrylic acid or methacrylic acid into an oligomer having an appropriate molecular weight and imparting photopolymerizability can be preferably used. These prepolymers may be used alone or in combination of two or more, and may be used by mixing with the above-mentioned monomers and / or oligomers.
[0058]
Examples of the prepolymer include adipic acid, trimellitic acid, maleic acid, phthalic acid, terephthalic acid, hymic acid, malonic acid, succinic acid, glutaric acid, itaconic acid, pyromellitic acid, fumaric acid, glutaric acid, and pimelic acid. , Polybasic acids such as sebacic acid, dodecanoic acid, tetrahydrophthalic acid, and ethylene glycol, propylene glycol, diethylene glycol, propylene oxide, 1,4-butanediol, triethylene glycol, tetraethylene glycol, polyethylene glycol, glycerin, tri Polyester obtained by introducing (meth) acrylic acid into a polyester obtained by combining polyhydric alcohols such as methylolpropane, pentaerythritol, sorbitol, 1,6-hexanediol, 1,2,6-hexanetriol Acrylates such as bisphenol A, epichlorohydrin, (meth) acrylic acid, and epoxy acrylates in which (meth) acrylic acid is introduced into an epoxy resin such as phenol novolac, epichlorohydrin, (meth) acrylic acid, such as ethylene glycol adipine Acid / tolylene diisocyanate / 2-hydroxyethyl acrylate, polyethylene glycol / tolylene diisocyanate / 2-hydroxyethyl acrylate, hydroxyethylphthalyl methacrylate / xylene diisocyanate, 1,2-polybutadiene glycol / tolylene diisocyanate / 2-hydroxyethyl acrylate , Trimethylolpropane, propylene glycol, tolylene diisocyanate, 2-hydroxyethyl acrylate As described above, urethane acrylates obtained by introducing (meth) acrylic acid into urethane resins, for example, silicone resin acrylates such as polysiloxane acrylate, polysiloxane diisocyanate, 2-hydroxyethyl acrylate, and other oil-modified alkyd resins (meth) Examples thereof include prepolymers such as alkyd-modified acrylates and spirane resin acrylates into which acryloyl groups are introduced.
[0059]
The photopolymerizable photosensitive layer of the photosensitive lithographic printing plate material of the present invention includes a phosphazene monomer, triethylene glycol, isocyanuric acid EO (ethylene oxide) -modified diacrylate, isocyanuric acid EO-modified triacrylate, dimethylol tricyclodecanedi. It contains monomers such as acrylate, trimethylolpropane acrylate benzoate, alkylene glycol type acrylic acid modified, urethane modified acrylate, and addition polymerizable oligomers and prepolymers having structural units formed from the monomer. be able to.
[0060]
Further, examples of the ethylenic monomer used in the photosensitive lithographic printing plate material of the present invention include a phosphate ester compound containing at least one (meth) acryloyl group. The compound is not particularly limited as long as it is a compound in which at least a part of the hydroxyl group of phosphoric acid is esterified and has a (meth) acryloyl group.
[0061]
In addition, JP-A-58-212994, JP-A-66-1649, JP-A-62-46688, JP-A-62-48589, JP-A-62-173295, JP-A-62-187092, JP-A-63-67189, The compound described in No. 1-244891 etc. can be mentioned, and “Chemical product of 11290”, Chemical Industry Daily, p. 286-p. 294, “UV / EB Curing Handbook (raw material)”, Kobunshi Publishing Co., p. The compounds described in 11 to 65 can also be suitably used in the present invention. Of these, compounds having two or more acrylic groups or methacryl groups in the molecule are preferred in the present invention, and those having a molecular weight of 10,000 or less, more preferably 5,000 or less are preferred.
[0062]
The photopolymerizable photosensitive layer of the photosensitive lithographic printing plate material of the present invention contains the above-described monomer in a range of 1.0 to 80.0% by mass in the photosensitive composition of the photosensitive layer. More preferably, it is the range of 3.0-70.0 mass%.
[0063]
Specific examples of the compound having two or more urethane bonds and four or more ethylenically unsaturated bonds include the following.
[0064]
[Chemical 1]

[0065]
Specific examples of the compound having two or more urethane bonds and two ethylenically unsaturated bonds include the following.
[0066]
[Chemical 2]

[0067]
Specific examples of the compound having no urethane bond and having two or more ethylenically unsaturated bonds include the following.
[0068]
[Chemical 3]

[0069]
The polymer binder of the present invention is preferably a vinyl copolymer obtained by copolymerizing a mixture of monomers described in the following (1) to (17).
[0070]
(1) Monomers having an aromatic hydroxyl group, such as o- (or p-, m-) hydroxystyrene, o- (or p-, m-) hydroxyphenyl acrylate, and the like.
[0071]
(2) Monomers having an aliphatic hydroxyl group, such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, N-methylol acrylamide, N-methylol methacrylamide, 4-hydroxybutyl methacrylate, 5-hydroxypentyl acrylate, 5-hydroxy Pentyl methacrylate, 6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate, N- (2-hydroxyethyl) acrylamide, N- (2-hydroxyethyl) methacrylamide, hydroxyethyl vinyl ether and the like.
[0072]
(3) A monomer having an aminosulfonyl group, such as m- (or p-) aminosulfonylphenyl methacrylate, m- (or p-) aminosulfonylphenyl acrylate, N- (p-aminosulfonylphenyl) methacrylamide, N- (P-aminosulfonylphenyl) acrylamide and the like.
[0073]
(4) Monomers having a sulfonamide group, such as N- (p-toluenesulfonyl) acrylamide, N- (p-toluenesulfonyl) methacrylamide and the like.
[0074]
(5) α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride and the like.
[0075]
(6) Substituted or unsubstituted alkyl acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, nonyl acrylate, acrylic Acid decyl, undecyl acrylate, dodecyl acrylate, benzyl acrylate, cyclohexyl acrylate, 2-chloroethyl acrylate, N, N-dimethylaminoethyl acrylate, glycidyl acrylate and the like.
[0076]
(7) substituted or unsubstituted alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, nonyl methacrylate, methacryl Acid decyl, undecyl methacrylate, dodecyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, 2-chloroethyl methacrylate, N, N-dimethylaminoethyl methacrylate, glycidyl methacrylate and the like.
[0077]
(8) Acrylamide or methacrylamides such as acrylamide, methacrylamide, N-ethylacrylamide, N-hexylacrylamide, N-cyclohexylacrylamide, N-phenylacrylamide, N- (4-nitrophenyl) acrylamide, N-ethyl- N-phenylacrylamide, N- (4-hydroxyphenyl) acrylamide, N- (4-hydroxyphenyl) methacrylamide and the like.
[0078]
(9) Monomers containing fluorinated alkyl groups such as trifluoroethyl acrylate, trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, hexafluoropropyl methacrylate, octafluoropentyl acrylate, octafluoropentyl methacrylate, heptadecafluorodecyl methacrylate, N-butyl-N- (2-acryloxyethyl) heptadecafluorooctylsulfonamide and the like.
[0079]
(10) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, phenyl vinyl ether and the like.
[0080]
(11) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate, vinyl benzoate and the like.
[0081]
(12) Styrenes such as styrene, methyl styrene, chloromethyl styrene and the like.
[0082]
(13) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.
[0083]
(14) Olefin such as ethylene, propylene, i-butylene, butadiene, isoprene and the like.
[0084]
(15) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine and the like.
[0085]
(16) Monomers having a cyano group, such as acrylonitrile, methacrylonitrile, 2-pentenenitrile, 2-methyl-3-butenenitrile, 2-cyanoethyl acrylate, o- (or m-, p-) cyanostyrene.
[0086]
(17) A monomer having an amino group, such as N, N-diethylaminoethyl methacrylate, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, polybutadiene urethane acrylate, N, N-dimethylaminopropyl acrylamide, N, N-dimethylacrylamide, acryloylmorpholine, Ni-propylacrylamide, N, N-diethylacrylamide and the like.
[0087]
The copolymer obtained from said (1)-(17) can be manufactured by normal solution polymerization. It can also be produced by bulk polymerization or suspension polymerization.
[0088]
The polymerization initiator is not particularly limited, and examples thereof include azobis-based radical generators such as 2,2′-azobisisobutyronitrile (AIBN) and 2,2′-azobis (2-methylbutyronitrile). ) And the like. Moreover, the usage-amount of these polymerization initiators is 0.05-10.0 mass parts (preferably 0.1-5 mass parts with respect to 100 mass parts of the whole monomers used for forming a copolymer. ).
[0089]
Examples of the solvent used for the solution polymerization include alcohol-based, ketone-based, ester-based, and aromatic organic solvents. Among them, ethanol, toluene, ethyl acetate, benzene, methyl cellosolve, ethyl cellosolve In general, good solvents for acrylic polymers such as acetone, methyl ethyl ketone, and the like are mentioned. Among them, solvents having a boiling point of 60 to 120 ° C. are preferable. In the case of solution polymerization, the above solvent can be used, and the reaction temperature can be 40 to 120 ° C. (preferably 60 to 110 ° C.) and the reaction time can be 3 to 10 hours (preferably 5 to 8 hours). After completion of the reaction, the solvent is removed to obtain a copolymer. Further, the double bond introduction reaction described later can be carried out without removing the solvent.
[0090]
The molecular weight of the resulting copolymer can be adjusted by adjusting the solvent used and the reaction temperature. The solvent, reaction temperature, and the like used to obtain the desired molecular weight copolymer can be appropriately determined depending on the monomer used. Moreover, the molecular weight of the copolymer obtained can also be adjusted by mixing a specific solvent with the said solvent. Examples of such a solvent include mercaptans (for example, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, mercaptoethanol, etc.), carbon tetrachloride (for example, carbon tetrachloride, butyl chloride, propylene chloride, etc.). ) And the like. The ratio of mixing these solvents with the solvent used in the above reaction can be appropriately determined depending on the monomer, solvent, reaction conditions, etc. used in the reaction.
[0091]
In one embodiment of the present invention, the polymer binder includes a monomer unit having a carboxyl group and a co-polymer having, as constituent elements, a unit obtained by reacting an epoxy group-containing unsaturated compound with at least a part of the monomer unit having the carboxyl group. It is a coalescence.
[0092]
A copolymer having a monomer unit having a carboxyl group is a vinyl having the above (5) α, β-unsaturated carboxylic acids, for example, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride and the like. A copolymer is preferred, and the monomer unit having a carboxyl group is preferably acrylic acid or methacrylic acid.
[0093]
Examples of the epoxy group-containing unsaturated compound to be reacted with at least a part of the monomer unit having a carboxyl group include allyl glycidyl ether, glycidyl (meth) acrylate, α-ethylglycidyl (meth) acrylate, glycidyl crotonate, and glycidyl isocroto. Aliphatic epoxy group-containing unsaturated compounds such as nate, crotonyl glycidyl ether, itaconic acid monoalkyl monoglycidyl ester, fumarate monoalkyl monoglycidyl ester, maleic acid monoalkyl monoglycidyl ester, or 3,4-epoxycyclohexylmethyl Examples include alicyclic epoxy group-containing unsaturated compounds such as (meth) acrylate, and glycidyl (meth) acrylate is particularly preferable.
[0094]
A known method can be used to react the epoxy group-containing unsaturated compound with at least a part of the monomer unit having a carboxyl group. For example, the reaction temperature is 20 to 100 ° C., preferably 40 to 80 ° C., particularly preferably at the boiling point (under reflux) of the solvent used, and the reaction time is 2 to 10 hours, preferably 3 to 6 hours. Can do. Examples of the solvent to be used include those used in the polymerization reaction of the vinyl copolymer. In addition, after the polymerization reaction, the solvent can be used as it is for the introduction reaction of the alicyclic epoxy group-containing unsaturated compound without removing the solvent. The reaction can be performed in the presence of a catalyst and a polymerization inhibitor as necessary. Here, the catalyst is preferably an amine-based or ammonium chloride-based material, and specifically, the amine-based material is triethylamine, tributylamine, dimethylaminoethanol, diethylaminoethanol, methylamine, ethylamine, n-propylamine. , Isopropylamine, 3-methoxypropylamine, butylamine, allylamine, hexylamine, 2-ethylhexylamine, benzylamine, and the like, and ammonium chloride-based substances include triethylbenzylammonium chloride and the like. When using these as a catalyst, what is necessary is just to add in 0.01-20.0 mass% with respect to the alicyclic epoxy group containing unsaturated compound to be used. Examples of the polymerization inhibitor include hydroquinone, hydromonomethyl ether, 2,6-di-t-butylhydrotoluene and the like, and the amount used is 0. 0 with respect to the alicyclic epoxy group-containing unsaturated compound used. 01-5.0 mass%. The progress of the reaction may be determined by measuring the acid value of the reaction system and stopping the reaction when the acid value becomes zero.
[0095]
The polymer binder may be any other optional, such as polyvinyl butyral resin, polyurethane resin, polyamide resin, polyester resin, epoxy resin, novolac resin, natural resin, resin having a reactive group introduced by other methods, if necessary. These polymer binders may be used in combination.
[0096]
The above-described polymer binder of the present invention is preferably 50 to 100% by mass and more preferably 100% by mass in the total polymer binder.
[0097]
The content of the polymer binder in the photosensitive composition formed by applying the photosensitive layer is preferably in the range of 10 to 90% by mass, more preferably in the range of 15 to 70% by mass, and in the range of 20 to 50% by mass. It is particularly preferable from the viewpoint of sensitivity.
[0098]
What can be preferably used as a photopolymerization initiator that can be used for the photosensitive lithographic printing plate material of the present invention is described in, for example, Carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo compounds, diazo compounds, halogen compounds, photoreduction as described in Chapter 5 of “Light Sensitive Systems” by J. Kosar And the like, and the compounds disclosed in British Patent 1,459,563 are also preferred.
[0099]
Specifically, the following examples can be given, but the invention is not limited thereto. That is, benzoin derivatives such as benzoin methyl ether, benzoin-i-propyl ether, α, α-dimethoxy-α-phenylacetophenone; benzophenone, 2,4-dichlorobenzophenone, methyl o-benzoylbenzoate, 4,4′-bis (Dimethylamino) benzophenone derivatives such as benzophenone; thioxanthone derivatives such as 2-chlorothioxanthone and 2-i-propylthioxanthone; anthraquinone derivatives such as 2-chloroanthraquinone and 2-methylanthraquinone; N-methylacridone and N-butylacrylic Acridone derivatives such as dong; α, α-diethoxyacetophenone, benzyl, fluorenone, xanthone, uranyl compounds, Japanese Patent Publication Nos. 59-1281, 61-9621, and JP 60-60104 Triazine derivatives described in JP-A-59-1504 and JP-A-61-243807; JP-B-43-23684, JP-A-44-6413, JP-A-44-6413, JP-A-47-1604 And diazonium compounds described in US Pat. No. 3,567,453; organic azide compounds described in US Pat. Nos. 2,848,328, 2,852,379 and 2,940,853; O-quinonediazides described in JP-A-36-22062, JP-A-37-13109, JP-A-38-18015 and JP-A-45-9610; JP-B-55-39162, JP-A-59-14023 and “Macromolecule” Various onium compounds described in Macromolecules, Vol. 10, p. 1307 (1977); Azo compounds described in No. 05; JP-A-1-54440, European Patent Nos. 109,851, 126,712, and “Journal of Imaging Science (J. Imag. Sci.)”, 30, 174 (1986); (oxo) sulfonium organoboron complexes described in JP-A-5-213861 and 5-255347; JP-A-59-152396, JP-A-61-151197 A transition metal complex containing a transition metal such as ruthenium described in “Coordination Chemistry Review” 84, 85-277 (1988) and JP-A-2-182701; 2,4 described in Kaihei 3-209477 , 5-triarylimidazole dimer; carbon tetrabromide, organic halogen compounds described in JP-A-59-107344, and the like.
[0100]
Of these, preferred are titanocenes. Specific examples of titanocenes include di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, and di-cyclopentadienyl-Ti-bis-2,3,4. , 5,6-pentafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti-bis -2,4,6-trifluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2, 4-difluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bi -2,3,5,6-tetrafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,4-difluorophen-1-yl, bis (cyclopentadienyl) -bis ( Examples include, but are not limited to, 2,6-difluoro-3- (pyridin-1-yl) phenyl) titanium (IRUGACURE784: manufactured by Ciba Specialty Chemicals).
[0101]
When laser light is used as the light source, it is preferable to add a sensitizing dye to the photosensitive layer.
[0102]
Examples of the compound for wavelength sensitizing from visible light to near infrared include cyanine, phthalocyanine, merocyanine, porphyrin, spiro compound, ferrocene, fluorene, fulgide, imidazole, perylene, phenazine, phenothiazine, polyene, azo compound, diphenylmethane, Phenylmethane, polymethine acridine, coumarin, ketocoumarin, quinacridone, indigo, styryl, pyrylium compound, pyromethene compound, pyrazolotriazole compound, benzothiazole compound, barbituric acid derivative, thiobarbituric acid derivative and the like, and European Patent 568 , 993, U.S. Pat. Nos. 4,508,811, 5,227,227, JP-A-2001-125255, JP-A-11-271969, and the like.
[0103]
In the present invention, preferred specific examples of the combination of the photopolymerization initiator and the sensitizing dye include combinations described in JP-A Nos. 2001-125255 and 11-271969.
[0104]
Although the compounding quantity of these photoinitiators is not specifically limited, Preferably, it is 0.1-20 mass parts with respect to 100 mass parts of addition-polymerizable ethylenically unsaturated bond containing monomers based on this invention. The mixing ratio of the photopolymerization initiator and the sensitizing dye is preferably in the range of 1: 100 to 100: 1 in terms of molar ratio.
[0105]
In addition to the components described above, the coating composition for the photopolymerizable photosensitive layer of the photosensitive lithographic printing plate material of the present invention includes an ethylenically unsaturated dimer that can be polymerized during production or storage of the photosensitive lithographic printing plate material. In order to prevent unnecessary polymerization of the heavy bond monomer, it is desirable to add a polymerization inhibitor. Suitable polymerization inhibitors include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol) 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxylamine cerium salt, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5) -Methylbenzyl) -4-methylphenyl acrylate, hindered amines such as 2,2,6,6, -tetramethylpiperidine derivatives and the like.
[0106]
The addition amount of the polymerization inhibitor is preferably about 0.01% to about 5% with respect to the mass of the total solid content of the composition. If necessary, higher fatty acid derivatives such as behenic acid and behenic acid amide may be added to prevent polymerization inhibition due to oxygen, or it may be unevenly distributed on the surface of the photosensitive layer during the drying process after coating. Good. The amount of the higher fatty acid derivative added is preferably about 0.5% to about 10% of the total composition.
[0107]
Moreover, a coloring agent can also be used and a conventionally well-known thing can be used conveniently as a coloring agent including a commercially available thing. Examples include those described in the revised new edition “Pigment Handbook”, edited by Japan Pigment Technology Association (Seikodo Shinkosha), Color Index Handbook, and the like.
[0108]
Examples of the pigment include black pigment, yellow pigment, red pigment, brown pigment, purple pigment, blue pigment, green pigment, fluorescent pigment, and metal powder pigment. Specifically, inorganic pigments (titanium dioxide, carbon black, graphite, zinc oxide, Prussian blue, cadmium sulfide, iron oxide, and lead, zinc, barium and calcium chromates) and organic pigments (azo-based, thioindigo) , Anthraquinone, anthanthrone, and triphendioxazine pigments, vat dye pigments, phthalocyanine pigments and derivatives thereof, quinacridone pigments, and the like.
[0109]
Among these, it is preferable to select and use a pigment having substantially no absorption in the absorption wavelength region of the spectral sensitizing dye corresponding to the exposure laser to be used. In this case, an integrating sphere at the laser wavelength to be used is used. It is preferable that the reflection absorption of the used pigment is 0.05 or less. Moreover, as an addition amount of a pigment, 0.1-10 mass% is preferable with respect to solid content of the said composition, More preferably, it is 0.2-5 mass%.
[0110]
When an argon laser (488 nm) or SHG-YAG laser (532 nm) is used as an exposure light source, purple pigments and blue pigments are used from the viewpoints of pigment absorption in the photosensitive wavelength region and visible image properties after development. It is preferable to use it. Such as, for example, cobalt blue, cerulean blue, alkali blue lake, phonatone blue 6G, Victoria blue lake, metal-free phthalocyanine blue, phthalocyanine blue first sky blue, indanthrene blue, indico, dioxane violet, iso Violanthrone Violet, Indanthrone Blue, Indanthrone BC and the like can be mentioned. Among these, phthalocyanine blue and dioxane violet are more preferable.
[0111]
Further, a plasticizer can be contained in order to improve the adhesion to the support. Plasticizers include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, didodecyl phthalate, diisodecyl phthalate, butyl benzyl phthalate, diisononyl phthalate, ethyl phthalyl ethyl Examples include glycol, dimethyl isophthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and triacetyl glycerin. The amount of the plasticizer added is preferably about 0 to 3% by mass, more preferably 0.1 to 2% by mass, based on the solid content of the composition.
[0112]
Moreover, the said composition can contain surfactant as a coating property improving agent in the range which does not impair the performance of this invention. Of these, fluorine-based surfactants are preferred. In order to improve the physical properties of the cured film, additives such as an inorganic filler, a plasticizer such as dioctyl phthalate, dimethyl phthalate, and tricresyl phosphate may be added. These addition amounts are preferably 10% or less of the total solid content.
[0113]
Examples of the solvent used in preparing the photosensitive composition of the photopolymerizable photosensitive layer of the photosensitive lithographic printing plate material of the present invention include, for example, alcohol: polyhydric alcohol derivatives such as sec-butanol, isobutanol, n-hexanol, benzyl alcohol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,5-pentanediol, ethers: propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, ketones, aldehydes Preferred examples include: diacetone alcohol, cyclohexanone, methylcyclohexanone, and esters: ethyl lactate, butyl lactate, diethyl oxalate, methyl benzoate and the like.
[0114]
The prepared photosensitive composition (photosensitive layer coating solution) can be coated on a support by a conventionally known method and dried to prepare a photosensitive lithographic printing plate material. Examples of coating methods for the coating liquid include air doctor coater method, blade coater method, wire bar method, knife coater method, dip coater method, reverse roll coater method, gravure coater method, cast coating method, curtain coater method and extrusion coater method. Can be mentioned.
[0115]
If the drying temperature of the photosensitive layer is low, sufficient printing durability cannot be obtained, and if it is too high, not only marangoni is produced but also fogging of non-image areas is caused. The preferable drying temperature range is preferably 60 to 160 ° C, more preferably 80 to 140 ° C, and particularly preferably 90 to 120 ° C.
[0116]
A protective layer is preferably provided above the photopolymerizable photosensitive layer of the photosensitive lithographic printing plate material of the present invention. The protective layer (oxygen barrier layer) preferably has high solubility in a developer (generally an alkaline aqueous solution) described later.
[0117]
Preferred examples of the material constituting the protective layer include polyvinyl alcohol, polysaccharide, polyvinyl pyrrolidone, polyethylene glycol, gelatin, glue, casein, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, hydroxyethyl starch, gum arabic, sucrose octaacetate, Examples include ammonium alginate, sodium alginate, polyvinylamine, polyethylene oxide, polystyrene sulfonic acid, polyacrylic acid, and water-soluble polyamide. These compounds can be used alone or in combination of two or more as a coating composition. A particularly preferred compound is polyvinyl alcohol.
[0118]
In order to prepare the protective layer coating composition, the above-mentioned material can be dissolved in a suitable solvent to form a coating solution, which is coated on the photopolymerizable photosensitive layer according to the present invention and dried. Thus, a protective layer can be formed. The thickness of the protective layer is preferably from 0.1 to 5.0 μm, particularly preferably from 0.5 to 3.0 μm. The protective layer can further contain a surfactant, a matting agent and the like as required.
[0119]
As the method for applying the protective layer, the known methods listed in the above examples can be preferably used. The drying temperature of the protective layer is more preferably lower than the drying temperature of the photosensitive layer. Preferably, the difference from the photosensitive layer drying temperature is 10 ° C. or more, more preferably 20 ° C. or more, and the upper limit in that case is preferably about 50 ° C. at most.
[0120]
Moreover, it is preferable that the drying temperature of a protective layer is lower than the glass transition temperature (Tg) of the binder which a photosensitive layer contains. The difference between the drying temperature of the protective layer and the glass transition temperature (Tg) of the binder contained in the photosensitive layer is preferably 20 ° C. or more, more preferably 40 ° C. or more, and the upper limit of the difference is at most about 60 ° C. Is preferred.
[0121]
Examples of the light source for image exposure on the photosensitive lithographic printing plate material of the present invention include a laser, a light emitting diode, a xenon lamp, a xenon flash lamp, a halogen lamp, a carbon arc lamp, a metal halide lamp, a tungsten lamp, a high-pressure mercury lamp, and an electrodeless light source. Etc.
[0122]
In the case of batch exposure, a mask material in which a negative pattern of a desired exposure image is formed of a light-shielding material may be superimposed on the photopolymerizable photosensitive layer and exposed.
[0123]
When using an array-type light source such as a light-emitting diode array, or when controlling exposure of a light source such as a halogen lamp, metal halide lamp, or tungsten lamp with an optical shutter material such as liquid crystal or PLZT, digital Exposure is possible and preferable. In this case, direct writing can be performed without using a mask material.
[0124]
Laser exposure is suitable for direct writing without using a mask material because light exposure can be performed in the form of a beam according to image data. When a laser is used as the light source, it is easy to reduce the exposure area to a very small size, and high-resolution image formation is possible.
[0125]
As the laser light source, an argon laser, a He—Ne gas laser, a YAG laser, a semiconductor laser, or the like can be preferably used. Laser scanning methods include cylindrical outer surface scanning, cylindrical inner surface scanning, and planar scanning. In the cylindrical outer surface scanning, laser exposure is performed while rotating a drum around which the recording material is wound, and the rotation of the drum is the main scanning and the movement of the laser light is the sub scanning. In cylindrical inner surface scanning, a recording material is fixed to the inner surface of the drum, a laser beam is irradiated from the inside, and a main scanning is performed in the circumferential direction by rotating a part or all of the optical system. Sub scanning is performed in the axial direction by linearly moving all of them in parallel with the drum axis. In plane scanning, a laser beam main scan is performed by combining a polygon mirror, a galvanometer mirror, and an fθ lens, and a sub-scan is performed by moving a recording medium. Cylindrical outer surface scanning and cylindrical inner surface scanning are easier to increase the accuracy of the optical system and are suitable for high-density recording.
[0126]
In the present invention, it is preferable that after the image exposure, a heat treatment is performed in order to promote an image forming reaction and improve sensitivity and printing durability. The method of the heat treatment is not particularly limited, but a non-contact method to the image forming surface is preferable, and a commercially available automatic processor equipped with a normal thermostatic bath, a hot air dryer and a heat treatment unit can be used. The heating temperature is preferably 100 to 130 ° C. at the plate surface temperature. If the temperature is too high, there are problems such as fogging of non-image areas. If the temperature is too low, problems such as insufficient sensitivity and printing durability occur. The heating time is preferably 5 to 60 seconds. If the heating time is too long, there is a problem such as fogging of the non-image area, and if the heating time is too short, problems such as insufficient sensitivity and printing durability occur. Needless to say, the time from the end of exposure to the heat treatment is within 300 seconds, and it is desirable that the time be as short as possible. If it exceeds 300 seconds, problems such as insufficient sensitivity and printing durability occur.
[0127]
The exposed portion of the photopolymerizable photosensitive layer of the photosensitive lithographic printing plate material of the present invention which has been image-exposed is cured. By developing this with a developing solution, the unexposed area is removed and image formation becomes possible. As such a developer, a conventionally known alkaline aqueous solution can be used. Sodium silicate, potassium, ammonium; dibasic sodium phosphate, potassium, ammonium; sodium bicarbonate, potassium, ammonium; sodium carbonate, potassium, ammonium; sodium bicarbonate, potassium, ammonium; boric acid Examples include sodium, potassium, ammonium; alkaline developers using inorganic alkali agents such as sodium hydroxide, potassium, ammonium, and lithium.
[0128]
Also, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, mono-i-propylamine, di-i-propylamine, tri-i-propylamine, butylamine, monoethanolamine, diethanolamine, triethanolamine, Organic alkali agents such as mono-i-propanolamine, di-i-propanolamine, ethyleneimine, ethylenediamine, and pyridine can also be used.
[0129]
These alkali agents are used alone or in combination of two or more. In addition, an organic solvent such as an anionic surfactant, an amphoteric surfactant or alcohol can be added to the developer as necessary.
[0130]
The developer used in the present invention contains a silicate and preferably has a pH of 10.0 to 12.5, more preferably a pH of 10.5 to 12.4. Such development provides the effects of the present invention specifically. That is, it is possible to simultaneously improve performance such as improvement of development sludge performance and improvement of printing durability as well as drawing out sufficient developability and sensitivity as sufficient performance.
[0131]
【Example】
EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto. In the examples, “parts” represents “parts by mass” unless otherwise specified.
[0132]
(Polymer binder A synthesis)
In a three-necked flask under a nitrogen stream, methyl methacrylate (162 parts: 1.62 mol), ethyl methacrylate (12 parts: 0.10 mol), methacrylic acid (26 parts: 0.30 mol), ethanol 400 parts and α, α'-Azobisisobutyronitrile (5 parts) was added and reacted in an oil bath at 80 ° C. for 8 hours in a nitrogen stream. Next, ethanol was removed from the system, and the residual solvent was adjusted to 1% or less to obtain a polymer binder A. The weight average molecular weight was about 50,000 (GPC: polystyrene conversion).
[0133]
(Synthesis of polymer binder B)
In a three-necked flask under a nitrogen stream, methyl methacrylate (125 parts: 1.25 mol), ethyl methacrylate (12 parts: 0.10 mol), methacrylic acid (63 parts: 0.73 mol), ethanol 400 parts and α, α′-Azobisisobutyronitrile (5 parts) was added and reacted in an oil bath at 80 ° C. in a nitrogen stream for 6 hours to obtain a polymer. Thereafter, 4 parts of triethylammonium chloride and glycidyl methacrylate (52 parts: 0.73 mol) were added to the polymer and reacted at a temperature of 25 ° C. for 3 hours to obtain a polymer binder B. The weight average molecular weight was about 55,000 (GPC: polystyrene conversion).
[0134]
[Formula 4]

[0135]
(Production of support)
An aluminum plate (material 1050, tempered H16) having a thickness of 0.30 mm was immersed in a 5% aqueous sodium hydroxide solution maintained at 65 ° C., degreased for 1 minute, and then washed with water. This degreased aluminum plate was neutralized by dipping in a 10% aqueous hydrochloric acid solution maintained at 25 ° C. for 1 minute, and then washed with water. Next, this aluminum plate was placed in a 0.3% by mass hydrochloric acid aqueous solution at 25 ° C. and a current density of 100 A / dm. ² Electrolytic surface roughening was performed for 60 seconds with an alternating current under the above conditions, followed by desmutting treatment for 10 seconds in a 5% aqueous sodium hydroxide solution maintained at 60 ° C. The surface-roughened aluminum plate subjected to the desmut treatment was subjected to a current density of 10 A / dm at 25 ° C. in a 15% sulfuric acid solution. ² Then, an anodizing treatment was performed for 1 minute under the condition of a voltage of 15 V, and a sealing treatment was further performed at 90 ° C. with 3% sodium oxalate to prepare a support. At this time, the center line average roughness (Ra) of the surface was 0.65 μm.
[0136]
(Surface treatment of support)
After performing the said process, it immersed in the following solution and processed.
[0137]
Solution temperature 80 ℃
Vinylphosphonic acid 0.2%
Polyvinylphosphonic acid 1.5%
An aluminum plate was passed through the solution for 30 seconds and dried.
[0138]
(Preparation of photosensitive lithographic printing plate materials 1-30)
On the surface-treated support, a photopolymerizable photosensitive layer coating solution having the following composition was dried at 1.5 g / m. ² Then, it was applied with a wire bar and dried at 95 ° C. for 1.5 minutes. Thereafter, an overcoat layer coating solution having the following composition was further dried on the photosensitive layer at a drying rate of 2.0 g / m 2. ² The photosensitive lithographic printing plate material having an overcoat layer on the photosensitive layer was prepared by applying with an applicator and drying at 75 ° C. for 1.5 minutes.
[0139]

[0140]
[Chemical formula 5]

[0141]
With respect to the photopolymerization type photosensitive lithographic printing plate material thus produced, 2540 dpi (1 dpi is 2.54 cm per inch) using a CTP exposure apparatus (Tigercat: manufactured by ECRM) equipped with an FD-YAG laser light source. The image exposure was performed at a resolution of (representing the number of dots). Next, a heating unit before development, a pre-water washing part for removing the overcoat layer, a development part filled with the following developer composition 1, a water washing part for removing the developer adhering to the plate surface, and a gum solution for protecting the image line part Development processing was performed with a CTP automatic developing machine (PHW23-V: manufactured by Technigraph) equipped with (GW-3: manufactured by Mitsubishi Chemical Co., Ltd.), and lithographic printing plates 1 to 30 were obtained. At this time, the heating unit was set so that the plate surface temperature was 115 ° C. and the plate staying time was 15 seconds. The plate was inserted into the heating unit of the self-machine after the end of exposure within 60 seconds.
[0142]
Developer composition 1 (aqueous solution containing the following additives)
A Potassium silicate 8.0% by mass
New Coal B-13: Nippon Emulsifier Co., Ltd. 3.0% by mass
Caustic potash added to pH = 12.3
(Evaluation of planographic printing plate)
The lithographic printing plate obtained as described above was evaluated as follows. The evaluation results are shown in Table 1. In addition, it was found that the developing solution in which the imaged photosensitive lithographic printing plate materials 1 to 30 were developed had suppressed the generation of developing sludge while the pH of the developing solution was as low as 12.3.
[0143]
"sensitivity"
No reduction in film thickness is observed in the image area, and the 175 line / 50% halftone dot exposure area draws light with twice the exposure amount that can be reproduced to 50% on the prepared lithographic printing plate surface. It was.
[0144]
<Press life>
A lithographic printing plate produced by exposing and developing a 175-line image with an appropriate exposure amount was printed using a printing machine (DAIYA1F-1 manufactured by Mitsubishi Heavy Industries, Ltd.) and coated paper, printing ink (manufactured by Dainippon Ink & Chemicals, Inc.). , Soybean oil ink “Naturalis 100”) and fountain solution (Tokyo Ink Co., Ltd. H liquid SG-51 concentration 1.5%), the highlight portion is dotted, the shadow portion is entangled Was used as an index of printing durability.
[0145]
<Plate cleaner resistance>
A lithographic printing plate produced by exposing and developing an image of 175 line with an appropriate exposure amount is immersed in a plate cleaner (ESK liquid manufacturing ultra plate cleaner), washed with water while being rubbed with a sponge, dried, and then imaged. Was observed. The immersion time at which the image portion starts to disappear is used as an index of the resistance to the plate cleaner.
[0146]
[Table 1]

[0147]
From Table 1, the photosensitive lithographic printing plate material of the present invention shows superior performance in comparison with respect to sensitivity, printing durability, and plate cleaner resistance.
[0148]
(Preparation of photosensitive lithographic printing plate materials 31-40)
Instead of adding the spectral sensitizing dyes 1 and 2 and IRGACURE 784 of the photosensitive lithographic printing plate materials 1 to 30, the following compound was added, and the overcoat was added the following compound 16 to prepare the photosensitive lithographic printing plate material 1 Samples were prepared under the same conditions as for ˜30.
[0149]
Compound 9 0.7 parts
Compound 10 0.7 parts
Compound 11 0.7 parts
Compound 12 0.7 parts
Compound 13 0.7 parts
Compound 14 0.7 parts
Compound 15 4.0 parts
(Overcoat layer (protective layer) coating solution)
Polyvinyl alcohol (GL-05: Nippon Synthetic Chemical Co., Ltd.) 87 parts
10 parts of water-soluble polyamide (P-70: manufactured by Toray Industries, Inc.)
Compound 16 2 parts
Surfactant (Surfinol 465: Nissin Chemical Industry Co., Ltd.) 0.5 part
900 parts of water
[0150]
[Chemical 6]

[0151]
Image formation and evaluation of the lithographic printing plate were carried out in the same manner as the photosensitive lithographic printing plate materials 1 to 30 except that the exposure was carried out with a self-made apparatus equipped with an InGaN semiconductor laser having an oscillation wavelength of 405 nm. The evaluation results are shown in Table 2. In addition, it was found that the developing solution in which the imaged photosensitive lithographic printing plate materials 31 to 40 were developed had a low pH of 12.3 and the development sludge was suppressed.
[0152]
[Table 2]

[0153]
From Table 2, it can be seen that the photosensitive lithographic printing plate material of the present invention exhibits superior performance in comparison with respect to sensitivity, printing durability, and plate cleaner resistance.
[0154]
【The invention's effect】
According to the present invention, a photosensitive lithographic printing plate material excellent in sensitivity, printing durability, and plate cleaner resistance can be provided.

Claims (9)

  A photosensitive lithographic printing plate material having at least one photopolymerizable photosensitive layer containing an ethylenically unsaturated bond-containing monomer capable of addition polymerization on a support, a photopolymerization initiator, and a polymer binder; In a photosensitive lithographic printing plate material in which a non-image portion of the photopolymerizable photosensitive layer is removed from a support with a developing solution to form a photocured image after imagewise exposure and imagewise photocuring of the photosensitive layer The addition-polymerizable ethylenically unsaturated bond-containing monomer is a compound (D) having two or more urethane bonds and four or more ethylenically unsaturated bonds, two or more urethane bonds and two ethylenes. The compound (E) having an ethylenically unsaturated bond in a mass ratio of 5: 1 to 1: 5, and having no urethane bond and having two or more ethylenically unsaturated bonds (M) [((D) + (E)) :( F)] : 1 to 1: photosensitive lithographic printing plate material characterized by containing at 1. A photosensitive lithographic printing plate material having at least one photopolymerizable photosensitive layer containing an ethylenically unsaturated bond-containing monomer capable of addition polymerization on a support, a photopolymerization initiator, and a polymer binder; In a photosensitive lithographic printing plate material in which a non-image portion of the photopolymerizable photosensitive layer is removed from a support with a developing solution to form a photocured image after imagewise exposure and imagewise photocuring of the photosensitive layer The addition-polymerizable ethylenically unsaturated bond-containing monomer is a compound (D) having two or more urethane bonds and four or more ethylenically unsaturated bonds, two or more urethane bonds and two ethylenes. compounds having sex unsaturated bond (E) in a weight ratio of 5: 1 to 1: contains 5, and compounds having two or more ethylenically unsaturated bond has no urethane bond mass ratio (F) [((D) + (E)) :( F)] : 1 to 1: contains 1, a unit obtained by reacting an epoxy group-containing unsaturated compound to at least a portion of the monomer units wherein the polymer binder has a monomer unit and the carboxyl group having a carboxyl group as a component A photosensitive lithographic printing plate material, characterized by comprising a copolymer. The photosensitive lithographic printing plate material according to claim 1, wherein the developer contains a silicate and has a pH of 10.0 to 12.5 . The photosensitive lithographic printing plate material according to claim 1, wherein heat treatment is performed after the image exposure . The photosensitive lithographic printing plate material according to claim 4, wherein the heat treatment is performed at a plate surface temperature of 100 to 130 ° C. for 5 to 60 seconds . The photosensitive lithographic printing plate material according to claim 4, wherein the heat treatment is performed within 300 seconds after image exposure . The photosensitive planographic printing plate material of any one of claims 1 to 6, wherein Rukoto that having a oxygen barrier layer on the photopolymerizable photosensitive layer. The photosensitive lithographic printing plate material according to claim 1, wherein the support is an aluminum support subjected to at least roughening and anodizing treatment . The photosensitive lithographic printing plate material according to claim 8, wherein the aluminum support is further subjected to a hydrophilic treatment or a subbing treatment .