JP2004077790A - Photosensitive lithographic printing plate material and its processing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive lithographic printing plate material and its processing method in which occurrence of minute point stain (stop stain) that is generated in a nonimage section is prevented when a printer is temporarily stopped after a continuous operation and the printing is restarted and the amount of sluge, that is accumulated in a developer tub and a pretreatment tub after a long process, is reduced and the cleaning work load is reduced. <P>SOLUTION: The lithographic printing plate has a photopolymerization light sensitive layer which includes at least a unit amount body containing a single layer additional polymerizable ethylenic unsaturated bond, a photopolymerization primer and polymerization bonding and a protective layer on an aluminum plate supporting body. The protective layer includes a water-soluble polymerized body and a compound which is represented by a general formula (1). <P>COPYRIGHT: (C)2004,JPO

Description

【００９６】
【化４】

【００９７】
前記一般式（１）で示される化合物は、当業者で一般に知られる方法で合成することができる。
【００９８】
これらの中でも、特に好ましい化合物は１−１、１−３、１−１４である。
前記一般式（１）で表される化合物の保護層への添加量としては、０．００１〜１質量％が好ましく、０．００１〜０．１質量％であることがさらに好ましい。含有させるには、保護層塗布液中に添加し含有させることができる。
【００９９】
（炭素数１〜３のＮ−アルキル置換のＮ−置換イミノジ酢酸又はその塩）
本発明の炭素数１〜３のＮ−アルキル置換のＮ−置換イミノジ酢酸又はその塩（以下、本発明に係るＮ−置換イミノジ酢酸又はその塩）において、Ｎ−アルキルイミノジ酢酸のアルキル基は、炭素数１〜３のアルキル基で、メチル基、エチル基、プロピル基、イソプロピル基である。これらのアルキル基は、ヒドロキシ基で置換されていてもよく、アルキル基中のヒドロキシ基の数は０〜３が好ましい。
【０１００】
本発明に係るＮ−置換イミノジ酢酸又はその塩の具体的化合物を以下に列挙するが、これらに限定されるものではない。
【０１０１】
Ｌ−１：Ｎ−メチルイミノジ酢酸
Ｌ−２：Ｎ−エチルイミノジ酢酸
Ｌ−３：Ｎ−ヒドロキシメチルイミノジ酢酸
Ｌ−４：Ｎ−β−ヒドロキシエチルイミノジ酢酸
Ｌ−５：Ｎ−プロピルイミノジ酢酸
Ｌ−６：Ｎ−α，β−ジヒドロキシエチルイミノジ酢酸
Ｌ−７：Ｎ−α−ヒドロキシエチルイミノジ酢酸
上記例示化合物において、特に好ましくはＬ−１、Ｌ−２、Ｌ−３である。
【０１０２】
本発明に係るＮ−置換イミノジ酢酸又はその塩の保護層への好ましい添加量は、０．００１〜１質量％が好ましく、０．００１〜０．１質量％であることがさらに好ましい。含有させるには、保護層塗布液中に添加し含有させることができる。
【０１０３】
（一般式（２）化合物）
本発明の一般式（２）で示される化合物は、特許請求の範囲に（化２）にて示す化合物を表わすが、具体例を以下に示す。
【０１０４】
【化５】

【０１０５】
また、例えば特開平６−１００８８４号公報に記載の一般式１で示される化合物を挙げることができる。
【０１０６】
これらの中でも、特に好ましくは、β−アラニンジ酢酸又はその塩を挙げることができる。
【０１０７】
本発明の一般式（２）で表される化合物の保護層への好ましい添加量は、０．００１〜１質量％が好ましく、０．００１〜０．１質量％であることがさらに好ましい。含有させるには、保護層塗布液中に添加し含有させることができる。
【０１０８】
上記した様に、本発明においては、保護層に一般式（１）で表される化合物、一般式（２）で表される化合物及び／又は本発明に係るＮ−置換イミノジ酢酸又はその塩を含有することが好ましいが、この中でも特に、一般式（１）で表される化合物が好ましい。
【０１０９】
（画像形成方法）
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。
【０１１０】
一括露光する場合には、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。
【０１１１】
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。
【０１１２】
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。また、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。
【０１１３】
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いず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やすく、高密度記録には適している。
【０１１４】
（現像処理）
本発明の感光性平版印刷版材料の処理方法（以下、本発明の処理方法とも言う）に用いられる現像液及び補充液の主成分は、珪酸、燐酸、炭酸、ホウ酸、フェノール類、糖類、オキシム類及びフッ素化アルコール類から選ばれる少なくとも一種の化合物を含有することが好ましい。また、現像液のｐＨは、８．５より高く１３．０未満の範囲であるアルカリ性水溶液であることが好ましい。さらに好ましくはｐＨ８．５〜１２である。
【０１１５】
これらのうち、フェノール類、糖類、オキシム類及びフッ素化アルコール類の如き弱酸性物質としては、解離指数（ｐＫａ）が１０．０〜１３．２のものが好ましい。このような酸としては、ＰｅｒｇａｍｏｎＰｒｅｓｓ社発行のＩＯＮＩＳＡＴＩＯＮ　ＣＯＮＳＴＡＮＴＳ　ＯＦ　ＯＲＧＡＮＩＣ　ＡＣＩＤＳ　ＩＮＡＱＵＥＯＵＳ　ＳＯＬＵＴＩＯＮなどに記載されているものから選ばれ、具体的には、サリチル酸（ｐＫａ１３．０）、３−ヒドロキシ−２−ナフトエ酸（同１２．８４）、カテコール（同１２．６）、没食子酸（同１２．４）、スルホサリチル酸（同１１．７）、３，４−ジヒドロキシスルホン酸（同１２．２）、３，４−ジヒドロキシ安息香酸（同１１．９４）、１，２，４−トリヒドロキシベンゼン（同１１．８２）、ハイドロキノン（同１１．５６）、ピロガロール（同１１．３４）、ｏ−クレゾール（同１０．３３）、レゾルソノール（同１１．２７）、ｐ−クレゾール（同１０．２７）、ｍ−クレゾール（同１０．０９）などのフェノール性水酸基を有するフェノール類が挙げられる。
【０１１６】
また、糖類としてはアルカリ中でも安定な非還元糖が好ましく用いることができる。非還元糖とは、遊離のアルデヒド基やケトン基を持たず、還元性を示さない糖類であり、還元基同士の結合したトレハロース型少糖類、糖類の還元基と非糖類が結合した配糖体及び糖類に水素添加して還元した糖アルコールに分類され、いずれも本発明に好適に用いられる。トレハロース型少糖類には、サッカロースやトレハロースがあり、配糖体としては、アルキル配糖体、フェノール配糖体、カラシ油配糖体などが挙げられる。また、糖アルコールとしては、例えば、Ｄ，Ｌ−アラビット、リビット、キシリット、Ｄ，Ｌ−ソルビット、Ｄ，Ｌ−マンニット、Ｄ，Ｌ−イジット、Ｄ，Ｌ−タリット、ズリシット及びアロズルシットなどが挙げられる。更に、二糖類の水素添加で得られるマルチトール及びオリゴ糖の水素添加で得られる還元体（還元水あめ）が好適に用いられる。更には、２−ブタノンオキシム（ｐＫａ１２．４５）、アセトキシム（同１２．４２）、１．２−シクロヘプタンジオンオキシム（同１２．３）、２−ヒドロキシベンズアルデヒドオキシム（同１２．１０）、ジメチルグリオキシム（同１１．９）、エタンジアミドジオキシム（同１１．３７）、アセトフェノンオキシム（同１１．３５）などのオキシム類、例えば２，２，３，３−テトラフルオロプロパノール−１（同１２．７４）、トリフルオロエタノール（同１２．３７）、トリクロロエタノール（同１２．２４）などのフッ素化アルコール類が挙げられる。他にも、ピリジン−２−アルデヒド（同１２．６８）、ピリジン−４−アルデヒド（同１２．０５）などのアルデヒド類、アデノシン（同１２．５６）、イノシン（同１２．５）、グアニン（同１２．３）、シトシン（同１２．２）、ヒポキサンチン（同１２．１）、キサンチン（同１１．９）などの核酸関連物質、他に、ジエチルアミノメチルスルホン酸（同１２．３２）、１−アミノ−３，３，３−トリフルオロ安息香酸（同１２．２９）、イソプロピリデンジスルホン酸（同１２．１０）、１，１−エチリデンジホスホン酸（同１１．５４）、１，１−エチリデンジスルホン酸１−ヒドロキシ（同１１．５２）、ベンズイミダゾール（同１２．８６）、チオベンズアミド（同１２．８）、ピコリンチオアミド（同１２．５５）、バルビツル酸（同１２．５）などの弱酸が挙げられる。これらの酸性物質は単独でも、また二種以上を組み合わせて用いてもよい。これらの酸性物質の中で好ましいのは、珪酸、燐酸、炭酸、スルホサリチル酸、サリチル酸及び非還元糖の糖アルコールとサッカロースであり、特に珪酸、Ｄ−ソルビット、サッカロース、還元水あめが適度なｐＨ領域に緩衝作用があることと、低価格であることで好ましい。
【０１１７】
これらの酸性物質の現像液中に占める割合は０．１〜３０質量％が好ましく、更に好ましくは、１〜２０質量％である。上記範囲以下では十分な緩衝作用が得られず、またこの範囲以上の濃度では、高濃縮化し難く、また原価上昇の問題が出てくる。
【０１１８】
これらの酸に組み合わせる塩基としては、例えば、水酸化ナトリウム、同アンモニウム、同カリウム及び同リチウムが好適に用いられる。これらのアルカリ剤は、単独もしくは二種以上を組み合わせて用いられる。その他として、例えば、珪酸カリウム、珪酸ナトリウム、珪酸リチウム、珪酸アンモニウム、メタ珪酸カリウム、メタ珪酸ナトリウム、メタ珪酸リチウム、メタ珪酸アンモニウム、燐酸三カリウム、燐酸三ナトリウム、燐酸三リチウム、燐酸三アンモニウム、燐酸二カリウム、燐酸二ナトリウム、燐酸二リチウム、燐酸二アンモニウム、炭酸カリウム、炭酸ナトリウム、炭酸リチウム、炭酸アンモニウム、炭酸水素カリウム、炭酸水素ナトリウム、炭酸水素リチウム、炭酸水素アンモニウム、ホウ酸カリウム、ホウ酸ナトリウム、ホウ酸リチウム、ホウ酸アンモニウム等が挙げられ、予め形成された塩の形で加えられてもよい。この場合も、水酸化ナトリウム、同アンモニウム、同カリウム及び同リチウムをｐＨ調整に加えることができる。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、モノイソプロピルアミン、ジイソプロピルアミン、トリイソプロピルアミン、ｎ−ブチルアミン、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、モノイソプロパノールアミン、ジイソプロパノールアミン、エチレンイミン、エチレンジアミン、ピリジンなどの有機アルカリ剤も組み合わせて用いられる。最も好ましいものとして珪酸カリウム及び珪酸ナトリウムが挙げられる。珪酸塩の濃度は、ＳｉＯ_２濃度換算で１．０〜３．０質量％が好ましい。また、ＳｉＯ_２とアルカリ金属Ｍのｍｏｌ比（ＳｉＯ_２／Ｍ）が、０．２５〜２の範囲であることがより好ましい。
【０１１９】
なお、本発明で言う現像液とは、現像のスタート時に使用される未使用の液だけでなく、感光性平版印刷版材料の処理によって低下する液の活性度を補正するために補充液が補充され、活性度が保たれた液（いわゆるランニング液）を含む。補充液は従って、現像液より活性度（アルカリ濃度）が高い必要があるので、補充液のｐＨは１３．０を超えていてもよい。
【０１２０】
（界面活性剤）
本発明に用いられる現像液及び補充液には、現像性の促進や現像カスの分散及び印刷版画像部の親インキ性を高める目的で必要に応じて種々界面活性剤や有機溶剤を添加できる。好ましい界面活性剤としては、アニオン系、カチオン系、ノニオン系及び両性界面活性剤が挙げられる。界面活性剤の好ましい例としては、ポリオキシエチレンアルキルエーテル類、ポリオキシエチレンアルキルフェニルエーテル類、ポリオキシエチレンポリスチリルフェニルエーテル類、ポリオキシエチレンポリオキシプロピレンアルキルエーテル類、グリセリン脂肪酸部分エステル類、ソルビタン脂肪酸部分エステル類、ペンタエリスリトール脂肪酸部分エステル類、プロピレングリコールモノ脂肪酸エステル類、しょ糖脂肪酸部分エステル類、ポリオキシエチレンソルビタン脂肪酸部分エステル類、ポリオキシエチレンソルビトール脂肪酸部分エステル類、ポリエチレングリコール脂肪酸エステル類、ポリグリセリン脂肪酸部分エステル類、ポリオキシエチレン化ひまし油類、ポリオキシエチレングリセリン脂肪酸部分エステル類、ポリオキシエチレン−ポリオキシプロピレンブロック共重合体、エチレンジアミンのポリオキシエチレン−ポリオキシプロピレンブロック共重合体付加物、脂肪酸ジエタノールアミド類、Ｎ，Ｎ−ビス−２−ヒドロキシアルキルアミン類、ポリオキシエチレンアルキルアミン、トリエタノールアミン脂肪酸エステル、トリアルキルアミンオキシドなどの非イオン性界面活性剤、脂肪酸塩類、アビエチン酸塩類、ヒドロキシアルカンスルホン酸塩類、アルカンスルホン酸塩類、ジアルキルスルホ琥珀酸エステル塩類、直鎖アルキルベンゼンスルホン酸塩類、分岐鎖アルキルベンゼンスルホン酸塩類、アルキルナフタレンスルホン酸塩類、アルキルジフェニルエーテルスルホン酸塩類、アルキルフェノキシポリオキシエチレンプロピルスルホン酸塩類、ポリオキシエチレンアルキルスルホフェニルエーテル塩類、Ｎ−メチル−Ｎ−オレイルタウリンナトリウム塩、Ｎ−アルキルスルホ琥珀酸モノアミド二ナトリウム塩、石油スルホン酸塩類、硫酸化牛脂油、脂肪酸アルキルエステルの硫酸エステル塩類、アルキル硫酸エステル塩類、ポリオキシエチレンアルキルエーテル硫酸エステル塩類、脂肪酸モノグリセリド硫酸エステル塩類、ポリオキシエチレンアルキルフェニルエーテル硫酸エステル塩類、ポリオキシエチレンスチリルフェニルエーテル硫酸エステル塩類、アルキル燐酸エステル塩類、ポリオキシエチレンアルキルエーテルリン酸エステル塩類、ポリオキシエチレンアルキルフェニルエーテルリン酸エステル塩類、スチレン／無水マレイン酸共重合物の部分鹸化物類、オレフィン／無水マレイン酸共重合物の部分鹸化物類、ナフタレンスルホン酸塩ホルマリン縮合物類などのアニオン界面活性剤、アルキルアミン塩類、テトラブチルアンモニウムブロミド等の第四級アンモニウム塩類、ポリオキシエチレンアルキルアミン塩類、ポリエチレンポリアミン誘導体などのカチオン性界面活性剤、カルボキシベタイン類、アミノカルボン酸類、スルホベタイン類、アミノ硫酸エステル類、イミダゾリン類などの両性界面活性剤が挙げられる。以上に記載の各界面活性剤の中で、ポリオキシエチレンとは、ポリオキシメチレン、ポリオキシプロピレン、ポリオキシブチレンなどのポリオキシアルキレンに読み替えることもでき、それらの界面活性剤もまた包含される。更に好ましい界面活性剤は、分子内にパーフルオロアルキル基を含有するフッ素系の界面活性剤である。このようなフッ素系界面活性剤としては、例えば、パーフルオロアルキルカルボン酸塩、パーフルオロアルキルスルホン酸塩、パーフルオロアルキルリン酸エステルなどのアニオン型、パーフルオロアルキルベタインなどの両性型、パーフルオロアルキルトリメチルアンモニウム塩などのカチオン型及びパーフルオロアルキルアミンオキサイド、パーフルオロアルキルエチレンオキシド付加物、パーフルオロアルキル基及び親水性基含有オリゴマー、パーフルオロアルキル基及び親油性基含有オリゴマー、パーフルオロアルキル基、親水性基及び親油性基含有オリゴマー、パーフルオロアルキル基及び親油性基含有ウレタンなどの非イオン型が挙げられる。上記の界面活性剤は、単独もしくは２種以上を組み合わせて使用することができ、現像液中に０．００１〜１０質量％、より好ましくは０．０１〜５質量％の範囲で添加される。
【０１２１】
（現像安定化剤）
本発明に用いられる現像液及び補充液には、好ましくは、現像安定化剤を用いることができる。好ましい例としては、特開平６−２８２０７９号公報記載の糖アルコールのポリエチレングリコール付加物、テトラブチルアンモニウムヒドロキシドなどのテトラアルキルアンモニウム塩、テトラブチルホスホニウムブロマイドなどのホスホニウム塩及びジフェニルヨードニウムクロライドなどのヨードニウム塩等が挙げられ、更に、特開昭５０−５１３２４号公報記載のアニオン界面活性剤又は両性界面活性剤、また特開昭５５−９５９４６号公報記載の水溶性カチオニックポリマー、特開昭５６−１４２５２８号公報に記載されている水溶性の両性高分子電解質を挙げることができる。更に、特開昭５９−８４２４１号公報のアルキレングリコールが付加された有機ホウ素化合物、特開昭６０−１１１２４６号公報記載のポリオキシエチレン・ポリオキシプロピレンブロック重合型の水溶性界面活性剤、特開昭６０−１２９７５０号公報のポリオキシエチレン・ポリオキシプロピレンを置換したアルキレンジアミン化合物、特開昭６１−２１５５５４号公報記載の重量平均分子量３００以上のポリエチレングリコール、特開昭６３−１７５８５８号公報のカチオン性基を有する含フッ素界面活性剤、特開平２−３９１５７号公報の酸又はアルコールに４モル以上のエチレンオキシドを付加して得られる水溶性エチレンオキシド付加化合物と、水溶性ポリアルキレン化合物などを挙げることができる。
【０１２２】
（有機溶剤）
本発明に用いられる現像液及び現像補充液には、好ましくは更に有機溶剤を用いる。本発明で用いることのできる有機溶剤としては、水に対する溶解度が約１０質量％以下のものが適しており、好ましくは５質量％以下のものから選ばれる。例えば、１−フェニルエタノール、２−フェニルエタノール、３−フェニル−１−プロパノール、４−フェニル−１−ブタノール、４−フェニル−２−ブタノール、２−フェニル−１−ブタノール、２−フェノキシエタノール、２−ベンジルオキシエタノール、ｏ−メトキシベンジルアルコール、ｍ−メトキシベンジルアルコール、ｐ−メトキシベンジルアルコール、ベンジルアルコール、シクロヘキサノール、２−メチルシクロヘキサノール、３−メチルシクロヘキサノール及び４−メチルシクロヘキサノール、Ｎ−フェニルエタノールアミン及びＮ−フェニルジエタノールアミンなどを挙げることができる。有機溶剤の含有量は、使用液の総質量に対して０．１〜５質量％が好ましく、更には０．１〜１質量％が好ましい。
【０１２３】
（還元剤）
本発明に用いられる現像液及び補充液には、必要に応じて還元剤が加えられる。これは印刷版の汚れを防止するものであり、特に感光性ジアゾニウム塩化合物を含むネガ型感光性平版印刷版を現像する際に有効である。好ましい有機還元剤としては、例えば、チオサリチル酸、ハイドロキノン、メトール、メトキシキノン、レゾルシン、２−メチルレゾルシンなどのフェノール化合物、フェニレンジアミン、フェニルヒドラジンなどのアミン化合物が挙げられる。更に好ましい無機の還元剤としては、例えば、亜硫酸、亜硫酸水素酸、亜燐酸、亜燐酸水素酸、亜燐酸二水素酸、チオ硫酸及び亜ジチオン酸などの無機酸のナトリウム塩、カリウム塩、アンモニウム塩などを挙げることができる。これらの還元剤のうち、汚れ防止効果が特に優れているのは亜硫酸塩である。これらの還元剤は、使用時の現像液に対して０．０５〜５質量％の範囲で含有されることが好ましい。
【０１２４】
（有機カルボン酸）
本発明に用いられる現像液及び補充液には、必要に応じて更に有機カルボン酸を加えることもできる。好ましい有機カルボン酸は、炭素原子数６〜２０の脂肪族カルボン酸及び芳香族カルボン酸である。脂肪族カルボン酸の具体的な例としては、カプロン酸、エナンチル酸、カプリル酸、ラウリン酸、ミリスチン酸、パルミチン酸及びステアリン酸などがあり、特に好ましいのは炭素数８〜１２のアルカン酸である。また、炭素鎖中に二重結合を有する不飽和脂肪酸でも、分岐した炭素鎖のものでもよい。芳香族カルボン酸としては、ベンゼン環、ナフタレン環、アントラセン環などにカルボキシル基が置換された化合物で、具体的には、ｏ−クロロ安息香酸、ｐ−クロロ安息香酸、ｏ−ヒドロキシ安息香酸、ｐ−ヒドロキシ安息香酸、ｏ−アミノ安息香酸、ｐ−アミノ安息香酸、２，４−ジヒドロキシ安息香酸、２，５−ジヒドロキシ安息香酸、２，６−ジヒドロキシ安息香酸、２，３−ジヒドロキシ安息香酸、３，５−ジヒドロキシ安息香酸、没食子酸、１−ヒドロキシ−２−ナフトエ酸、３−ヒドロキシ−２−ナフトエ酸、２−ヒドロキシ−１−ナフトエ酸、１−ナフトエ酸、２−ナフトエ酸などがあるがヒドロキシナフトエ酸は特に有効である。上記脂肪族及び芳香族カルボン酸は水溶性を高めるためにナトリウム塩やカリウム塩又はアンモニウム塩として用いるのが好ましい。本発明で用いる現像液の有機カルボン酸の含有量は格別な制限はないが、０．１質量％より低いと効果が十分でなく、また１０質量％以上ではそれ以上の効果の改善が計れないばかりか、別の添加剤を併用する時に溶解を妨げることがある。従って、好ましい添加量は使用時の現像液に対して０．１〜１０質量％であり、よりこのましくは０．５〜４質量％である。
【０１２５】
（その他添加剤）
本発明に用いられる現像液及び補充液には、現像性を高めるために前記の他に以下のような添加剤を加えることができる。例えば、特開昭５８−７５１５２号公報記載のＮａＣｌ、ＫＣｌ、ＫＢｒ等の中性塩、特開昭５９−１２１３３６号公報記載の［Ｃｏ（ＮＨ_３）］_６Ｃｌ_３等の錯体、特開昭５６−１４２２５８号公報記載のビニルベンジルトリメチルアンモニウムクロライドとアクリル酸ナトリウムの共重合体等の両性高分子電解質、特開昭５９−７５２５５号公報記載のＳｉ、Ｔｉ等を含む有機金属界面活性剤、特開昭５９−８４２４１号公報記載の有機ホウ素化合物等が挙げられる。
【０１２６】
本発明に用いられる現像液及び補充液には、更に必要に応じて防腐剤、着色剤、増粘剤、消泡剤及び硬水軟化剤などを含有させることもできる。消泡剤としては、例えば、特開平２−２４４１４３号公報記載の鉱物油、植物油、アルコール、界面活性剤、シリコーン等が挙げられる。硬水軟化剤としては、例えば、ポリ燐酸及びそのナトリウム塩、カリウム塩及びアンモニウム塩、エチレンジアミンテトラ酢酸、ジエチレントリアミンペンタ酢酸、トリエチレンテトラミンヘキサ酢酸、ヒドロキシエチルエチレンジアミントリ酢酸、ニトリロトリ酢酸、１，２−ジアミノシクロヘキサンテトラ酢酸及び１，３−ジアミノ−２−プロパノールテトラ酢酸などのアミノポリカルボン酸及びそれらのナトリウム塩、カリウム塩及びアンモニウム塩、アミノトリ（メチレンホスホン酸）、エチレンジアミンテトラ（メチレンホスホン酸）、ジエチレントリアミンペンタ（メチレンホスホン酸）、トリエチレンテトラミンヘキサ（メチレンホスホン酸）、ヒドロキシエチルエチレンジアミントリ（メチレンホスホン酸）及び１−ヒドロキシエタン−１，１−ジホスホン酸やそれらのナトリウム塩、カリウム塩及びアンモニウム塩を挙げることができる。このような硬水軟化剤はそのキレート化力と使用される硬水の硬度及び硬水の量によって最適値が変化するが、一般的な使用量を示せば、使用時の現像液に０．０１〜５質量％の範囲が好ましい。この範囲より少ない添加量では所期の目的が十分に達成されず、添加量がこの範囲より多い場合は、色抜けなど、画像部への悪影響がでてくる。現像液及び補充液の残余の成分は水である。
【０１２７】
（濃縮液）
また、本発明に用いられる現像液及び補充液は、使用時よりも水の含有量を少なくした濃縮液としておき、使用時に水で希釈するようにしておくことが運搬上有利である。この場合の濃縮度は、各成分が分離や析出を起こさない程度が適当であるが、必要により可溶化剤を加えることが好ましい。可溶化剤としては、特開平６−３２０８１号公報記載のトルエンスルホン酸、キシレンスルホン酸及びそれらのアルカリ金属塩等のいわゆるヒドロトロープ剤が好ましく用いられる。
【０１２８】
本発明に用いる自動現像機は、好ましくは現像浴に自動的に補充液を必要量補充する機構が付与されており、好ましくは一定量を超える現像液は、排出する機構が付与されており、好ましくは現像浴に自動的に水を必要量補充する機構が付与されており、好ましくは感光性平版印刷版材料が通過（以下、通版と言う）を検知する機構が付与されており、好ましくは通版の検知をもとに版の処理面積を推定する機構が付与されており、好ましくは処理面積の推定をもとに補充しようとする補充液及び／又は水の補充量を制御する機構が付与され、好ましくはこれらの補充の補充タイミングを制御する機構が付与されており、好ましくは現像液の温度を制御する機構が付与されており、好ましくは現像液のｐＨ及び／又は電導度を検知する機構が付与されており、好ましくは現像液のｐＨ及び／又は電導度をもとに補充しようとする補充液及び／又は水の補充量を制御する機構が付与されており、好ましくはこれらの補充の補充タイミングを制御する機構が付与されている。
【０１２９】
本発明に用いる自動現像機は、現像工程の前に処理液に版を浸漬させる前処理部を有していることが好ましい。この前処理部は、好ましくは版面に処理液をスプレーする機構が付与されており、好ましくは処理液の温度を２５℃〜６０℃の任意の温度に制御する機構が付与されており、好ましくは版面をローラー状のブラシ（ブラシロール）により擦る機構が付与されている。またこの処理液としては、水などが用いられる。詳しくは後述する。
（後処理）
本発明の感光性平版印刷版材料は、現像処理後、水洗水、界面活性剤等を含有するリンス液、アラビアガムや澱粉誘導体等を主成分とする版面保護剤（フィニッシャー液、保護ガム液、あるいは単にガム液とも言う）で後処理を施される。
【０１３０】
本発明の感光性平版印刷版材料の後処理にはこれらの処理を種々組み合わせて用いることができ、例えば、現像→水洗→界面活性剤を含有するリンス液処理や現像→水洗→フィニッシャー液による処理が好ましい。
【０１３１】
更にリンス液やフィニッシャー液を用いた向流多段処理も好ましい態様である。これらの後処理は、一般に現像部と後処理部とからなる自動現像機を用いて行われる。後処理液は、スプレーノズルから吹き付ける方法、処理液が満たされた処理槽中を浸漬搬送する方法が用いられる。また、現像後一定量の少量の水洗水を版面に供給して水洗し、その廃液を現像液原液の希釈水として再利用する方法も知られている。また、実質的に未使用の処理液で処理するいわゆる使い捨て処理方式も適用できる。このような処理によって得られた平版印刷版は、オフセット印刷機に掛けられ、印刷に用いられる。
【０１３２】
（前処理）
本発明の処理方法おいて、現像液で処理する工程の前に前処理工程（前水洗工程）を設け、保護層を洗浄除去することが好ましい。
【０１３３】
該前処理工程で用いる処理液（水洗水）は、キレート剤、界面活性剤及び防腐剤から選ばれる少なくとも１種を含有する液が好ましく、また、水洗水は、水道水を使用することができる。
【０１３４】
キレート剤としては、金属イオンと配位結合してキレート化合物を形成する化合物を用いることができる。具体的には、エチレンジアミンテトラ酢酸、そのカリウム塩又はナトリウム塩、トリエチレンテトラミンヘキサ酢酸、そのカリウム塩又はナトリウム塩、ジエチレントリアミンペンタ酢酸、そのカリウム塩又はナトリウム塩、ヒドロキシエチルエチレンジアミントリ酢酸、そのカリウム塩又はナトリウム塩、ニトリオトリ酢酸、そのカリウム塩又はナトリウム塩、１−ヒドロキシエタン−１，１−ジホスホン酸、そのカリウム塩又はナトリウム塩、アミノトリ（メチレンホスホン酸）、そのカリウム塩又はナトリウム塩、ホスホノアルカントリカルボン酸等が挙げられる。これらのキレート剤はそのカリウム塩又はナトリウム塩の代わりに有機アミン塩であるものも有効である。
【０１３５】
キレート剤の添加量は、０．０００１〜３．０質量％の範囲が適当である。
界面活性剤としては、アニオン、ノニオン、カチオン及び両性のいずれの界面活性剤も用いることができるが、アニオン又はノニオン界面活性剤が好ましい。好ましい界面活性剤の種類は保護層や感光層の組成によって異なり、一般に保護層素材の溶解促進剤となり、感光層成分の溶解性が小さいものが好ましい。
【０１３６】
アニオン界面活性剤としては、脂肪酸塩類、アビチェン酸塩類、ヒドロキシアルカンスルホン酸塩類、アルカンスルホン酸塩類、ジアルキルスルホコハク酸塩類、アルキルベンゼンスルホン酸塩類、アルキルナフタレンスルホン酸塩類、アルキルフェノキシポリオキシエチレンプロピルスルホン酸塩類、ポリオキシエチレンアルキルスルホフェニルエーテル塩類、Ｎ−メチル−Ｎ−オレイルタウリンナトリウム類、Ｎ−アルキルスルホコハク酸モノアミド二ナトリウム塩類、石油スルホン酸塩類、硫酸化ヒマシ油、硫酸化牛脂油、脂肪酸アルキルエステルの硫酸エステル塩類、アルキル硫酸エステル塩類、ポリオキシエチレンアルキルエーテル硫酸エステル塩類、脂肪酸モノグリセリド硫酸エステル塩類、ポリオキシエチレンスチリルフェニルエーテル硫酸エステル塩類、アルキル燐酸エステル塩類、ポリオキシエチレンアルキルエーテル燐酸エステル塩類、ポリオキシエチレンアルキルフェニルエーテル燐酸エステル塩類、スチレン−無水マレイン酸共重合物の部分ケン化物類、オレフィン−無水マレイン酸共重合物の部分ケン化物類、ナフタレンスルホン酸塩ホルマリン縮合物類等が挙げられる。
【０１３７】
ノニオン界面活性剤としては、ポリオキシエチレンアルキルエーテル類、ポリオキシエチレンアルキルフェニルエーテル類、ポリオキシエチレンポリスチリルフェニルエーテル類、ポリオキシエチレンポリオキエイプロピレンアルキルエーテル類、グリセリン脂肪酸エステル類、ソルビタン脂肪酸部分エステル類、ペンタエリスリトール脂肪酸部分エステル類、プロピレングリコールモノ脂肪酸エステル、しょ糖脂肪酸部分エステル類、ポリオキシエチレンソルビタン脂肪酸部分エステル類、イエチレングリコール脂肪酸エステル類、ポリイグリセリン脂肪酸部分エステル類、ポリオキシエチレン化ひまし油類、ポリオキシエチレングリセリン脂肪酸部分エステル類、脂肪酸ジエタノールアミド類、Ｎ，Ｎ−ビス−ヒドロキシアルキルアミン類、ポリオキシエチレンアルキルアミン、トリエタノールアミン脂肪酸エステル、トリアルキルアミンオキシド等が挙げられる。
【０１３８】
界面活性剤の好ましい添加量は、０．００５〜１０質量％である。また、界面活性剤に消泡剤を併用することもできる。
【０１３９】
防腐剤としては、フェノール又はその誘導体、ホルマリン、イミダゾール誘導体、デヒドロ酢酸ナトリウム、４−イソチアゾリン−３−オン誘導体、ベンゾイソチアゾリン−３−オン、ベンゾトリアゾール誘導体、アミジングアニジン誘導体、四級アンモニウム塩類、ピロジン，キノリン，グアニジン等の誘導体、ダイアジン、トリアゾール誘導体、オキサゾール，オキサジン誘導体等が挙げられる。
【０１４０】
本発明の処理方法において、前記前処理工程に用いる処理液（水洗水）は、温度を調節して洗浄に用いることが好ましく、２０〜６０℃の範囲が好ましい。
【０１４１】
洗浄の方法は、スプレー、ディップ、塗布等公知の処理液供給技術を用いることができ、適宜ブラシローラーや絞りローラー、ディップ処理における液中シャワーなどの処理促進手段を用いることができる。
【０１４２】
本発明の処理において、前処理工程終了後直ちに現像処理を行ってもよく、また、該工程の後に乾燥工程を経てから現像処理を行ってもよい。
【０１４３】
現像工程の後は、上記した後処理を行うことができる。
また、本発明の処理方法には自動現像機を好適に用いることができ、例えば、図１に示す自動現像機を使用することが好ましい。
【０１４４】
この自動現像機は、前水洗槽１、現像液を有する現像槽２、水道水等を有する水洗槽３、また、Ａは前処理部、Ｂは現像部、Ｃは後処理部、Ｔは感光性平版印刷版材料の搬送路、１１〜１５は感光性平版印刷版搬送用のガイドロール、１６は絞りロール、１７は現像ブラシ等からなり、また、１８ａ、１８ｂはシャワーノズル、１９ａ、１９ｂはポンプで、図中、＊１と＊１、＊２と＊２とはそれぞれ配管で接続されている。
【０１４５】
以上の様に、本発明の感光性平版印刷版材料は、アルミニウム板支持体上に、本発明の光重合性感光層及び保護層を有していることが好ましく、また、これに本発明の処理方法を適用することが好ましい。
【０１４６】
【実施例】
以下に、合成例、支持体作製例、実施例を具体的に示すが、本発明の実施態様は、これらに限定されるものでない。なお、実施例における「部」は、特に断りない限り「質量部」を表す。
【０１４７】
《高分子結合剤の合成》
（高分子結合剤１の合成）
窒素気流下の三ツ口フラスコに、メタクリル酸１２部、メタクリル酸メチル７０部、アクリロニトリル８部、メタクリル酸エチル１０部、エタノール５００部及びα，α′−アゾビスイソブチロニトリル３部を入れ、窒素気流中８０℃のオイルバスで６時間反応させた。その後、トリエチルアンモニウムクロライド３部及びグリシジルメタクリレート２部を加えて３時間反応させ、高分子結合剤１を得た。ＧＰＣを用いて測定した重量平均分子量は約５０，０００、ＤＳＣ（示差熱分析法）を用いて測定したガラス転移温度（Ｔｇ）は約８５℃であった。
【０１４８】
《平版印刷版の作製》
（支持体の作製）
厚さ０．２４ｍｍ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％の硝酸水溶液中で、２５℃、電流密度１００Ａ／ｄｍ^２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／ｄｍ^２、電圧１５Ｖの条件下に１分間陽極酸化処理を行い、支持体１〜８を作製した。これらの表面の中心線平均粗さ（Ｒａ）は０．６５μｍであった。
【０１４９】
（下引き層塗設済み支持体の作製）
上記支持体１〜８上に、下記組成の下引き層塗工液を乾燥付量として０．１ｇ／ｍ^２になるようワイヤーバーで塗布し、９０℃で１分間乾燥し、更に１１０℃で３分間の加熱処理を行って、下引き層塗設済みの支持体１〜８を作製した。
【０１５０】
〈下引き層塗工液〉
γ−メタクリロキシプロピルトリメトキシシラン　　　　　　　　　１部
メチルエチルケトン　　　　　　　　　　　　　　　　　　　　　８０部
シクロヘキサノン　　　　　　　　　　　　　　　　　　　　　　１９部
（感光性平版印刷版材料の作製）
上記下引き層塗設済み支持体１〜８に、それぞれ下記組成の光重合性感光層塗工液を乾燥付量として１．４ｇ／ｍ^２になるようワイヤーバーで塗布し、９５℃で１．５分間乾燥し、感光層を形成した。その後、更に感光層上に、それぞれ下記する組成を有する保護層塗工液を下記表１に記載の様に、乾燥付量として２．０ｇ／ｍ^２と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、感光層上に保護層（酸素遮断層）を有する感光性平版印刷版材料１〜８を作製した。
【０１５１】

【０１５２】
【化６】

【０１５３】
（保護層塗工液）
〈保護層塗工液１〉
ポリビニルアルコール（ＧＬ−０３：日本合成化学社製）　　　　８９部
ポリビニルピロリドン（Ｋ−３０：東京化成社製）　　　　　　　１０部
界面活性剤（Ｆ１４２Ｄ：大日本インキ工業社製）　　　　　　０．５部
水　　　　　　　　　　　　　　　　　　　　　　　　　　　　９００部
〈保護層塗工液２〉
上記保護層塗工液１に、更にエチレンジアミンジコハク酸２ナトリウム（１部）を加えた。
【０１５４】
〈保護層塗工液３〉
上記保護層塗工液１に、更にメチルイミノジ酢酸ナトリウム（１部）を加えた。
【０１５５】
〈保護層塗工液４〉
上記保護層塗工液１に、更にβアラニンジ酢酸ナトリウム（１部）を加えた。
【０１５６】
〈保護層塗工液５〉
上記保護層塗工液２に、更にブチルナフタレンスルホン酸ナトリウム（５部）を加えた。
【０１５７】
〈保護層塗工液６〉
上記保護層塗工液３に、更にブチルナフタレンスルホン酸ナトリウム（５部）を加えた。
【０１５８】
〈保護層塗工液７〉
上記保護層塗工液４に、更にブチルナフタレンスルホン酸ナトリウム（５部）を加えた。
【０１５９】
〈保護層塗工液８〉
上記保護層塗工液１に、更にエチレンジアミン４酢酸２ナトリウム（１部）を加えた。
【０１６０】
《画像の形成》
以上のようにして作製した光重合型の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の解像度で画像露光を行った。なお、ｄｐｉとは２．５４ｃｍ当たりのドット数を表す。次いで、現像前に保護層を除去する前処理部（水道水使用）、下記組成の現像液を充填した現像部、後処理部（水洗処理と画線部保護のためのガム液処理（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）を用いて現像処理を行い、平版印刷版１〜８を得た。
【０１６１】

《評価》
前記作製した平版印刷版１〜８（試料１〜８）を用いて、下記の方法に従って、ストップ汚れの評価を行った。
【０１６２】
（ストップ汚れ）
上記作製した平版印刷版の各画像を、印刷機（三菱重工業社製ＤＡＩＹＡ　１Ｆ−１）にかけコート紙、湿し水（東京インキ社製エッチ液ＳＧ−５１　濃度１．５％）、インキ（東洋インキ製造株製ハイプラスＭ紅）を使用して印刷を行い、５０００枚刷った時点で一旦印刷機を停止し、１時間放置した後印刷を開始し、その時の印刷物１００ｃｍ^２当たりに発生した微点状の汚れをルーペで観察し、その発生個数を計数した。なお、微点状汚れについての判断基準は、発生個数として、１０個以下の場合が最も好ましく、１１〜２９個であれば実用上許容範囲であり、３０個以上であると実用上問題となる、として判定した。結果を表１に示す。
【０１６３】
（スラッジ）
図１に示す自動現像機の前水洗槽１に水道水を１Ｌ、現像槽２に上記現像液を９Ｌ、水洗槽３に水道水３Ｌを仕込み、自動現像機をセットして、画像露光した上記感光性平版印刷版材料１〜８の現像処理をそれぞれ行った。なお、現像処理において、感光性平版印刷版を１ｍ^２通すごとに前水洗槽１に水道水を５０ｍｌ、現像槽２に現像液を５０ｍｌ、水洗槽３に水道水を５０ｍｌをそれぞれ補充しながら、１日に２０ｍ^２づつ３０日間で６００ｍ^２の現像処理を行った。なお、処理条件は、前処理工程を１５秒、現像工程を３０秒、後処理工程を２０秒とした。この一連の処理の後、前水洗槽１の水洗水を排水して前水洗槽１のスラッジ・ヘドロの付着具合を観察した。評価基準は以下の基準を使用した。結果を表１に示す。
【０１６４】
◎：全く認められない
○：スラッジ・ヘドロの発生がわずかに認められるが実用上全く問題がない
△：スラッジ・ヘドロの発生がわずかに認められるが実用上許容範囲にある
×：スラッジ・ヘドロの発生が顕著であり、ポンプの詰まりが発生し、また版に汚れが付着し、実用上問題がある。
【０１６５】
【表１】

【０１６６】
表１より明らかなように、本発明によればストップ汚れが防止でき、また、長期間処理をした場合に発生するスラッジ・ヘドロを低減することもでき、清掃作業の負担を減らすことができる。
【０１６７】
【発明の効果】
本発明により、連続処理において、一旦印刷機を停止した後に印刷を再開した時、非画像部に発生する微点状汚れ（ストップ汚れ）を防止し、また、長期間処理をした場合に現像槽や前処理槽にたまるスラッジ・ヘドロを低減し清掃作業の負担を減らした感光性平版印刷版材料及び感光性平版印刷版材料の処理方法を提供することができた。
【図面の簡単な説明】
【図１】本発明の実施例に使用した、自動現像機の一例を示す概略構成図である。
【符号の説明】
１　　　　　　　前水洗槽
２　　　　　　　現像槽
３　　　　　　　水洗槽
１１〜１５　　　ガイドロール
１６　　　　　　絞りロール
１７　　　　　　現像ブラシ
１８ａ、１８ｂ　シャワーノズル
１９ａ　１９ｂ　ポンプ
Ａ　　　　　　　前処理部
Ｂ　　　　　　　現像部
Ｃ　　　　　　　後処理部
Ｔ　　　　　　　感光性平版印刷版材料の搬送路[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a photosensitive lithographic printing plate material and a method for processing a photosensitive lithographic printing plate material.
[0002]
[Prior art]
Conventional lithographic printing is a printing method that utilizes the fact that water and oil are not essentially mixed.The printing plate surface receives water and repels oil-based ink. An image area for receiving the oil-based ink is formed, and printing is performed by supplying water and the oil-based ink in a printing machine and transferring only the oil-based ink received in the image area to paper. Further, the printing press generally employs an offset printing method in which the oil-based ink received in the image portion of the printing plate is once transferred to a rubber blanket and then transferred to paper.
[0003]
As a support of the photosensitive lithographic printing plate material used in the lithographic printing method, a material having excellent hydrophilicity, water retention, and adhesion to the photosensitive layer is required from the viewpoint of printability. For this reason, an aluminum plate that has been subjected to a surface roughening treatment called graining is usually used.
[0004]
As the surface roughening treatment, a mechanical surface roughening method such as ball polishing, brush polishing, blast polishing, buff polishing, honing polishing, or the like, or electrolysis of the support surface by alternating current or direct current in an acidic electrolyte such as hydrochloric acid or nitric acid. Electrochemical surface roughening methods and the like for processing are known.
[0005]
Since the aluminum plate grained by such a method is relatively soft and easily worn as it is, it is then subjected to an anodic oxidation treatment to form an oxide film. The surface of such a treated aluminum plate is hard and has excellent wear resistance.
[0006]
When the exposed photosensitive lithographic printing plate material is developed with an alkaline aqueous solution, the exposed or unexposed portions of the photosensitive layer are removed, and the surface of the support is exposed. Since the surface of the aluminum plate support is hydrophilic, a portion (non-image portion) where the surface of the support is exposed by development receives water and repels oil-based ink. On the other hand, the portion (image portion) where the photosensitive layer has not been removed by development is lipophilic and repels water to receive oil-based ink.
[0007]
In general, the higher the sensitivity of a photosensitive lithographic printing plate material, the shorter the time required for exposure, and the faster the work can be performed. In addition, when printing using such a photosensitive lithographic printing plate material, the printing press is stopped for a while during registration or during a printing break, and then, when printing is resumed, fine dot-like stains appear on the non-image area. (Hereinafter referred to as "stop stain"), and a technique for maintaining the hydrophilicity of the plate surface of the non-image area has been desired in order to prevent the stop stain.
[0008]
Conventionally, aqueous solutions of alkali metal silicates have been widely used for the development of photosensitive lithographic printing plate materials. The reaction between aluminum on the surface of the support and silicic acid in the developing solution increases the hydrophilicity of the support surface. However, with this technique alone, sufficient hydrophilicity was not maintained, and stop stains could not be completely suppressed.
[0009]
In the case of a photopolymerizable photosensitive lithographic printing plate material of the type that forms a latent image by a free radical reaction between a photo-free radical generator and an ethylenically unsaturated compound, an image is exposed to light using an alkaline aqueous solution. When a photosensitive lithographic printing plate material having a polymerizable photosensitive layer is developed, an excellent lithographic printing plate with high sensitivity can be obtained.
[0010]
However, photosensitive lithographic printing plate materials of the type which form a latent image by the free radical reaction generally have excellent sensitivity, but have the drawback that the free radical reaction is inhibited by oxygen. It is necessary to provide a layer having such an oxygen blocking function (oxygen blocking layer) on the photopolymerizable photosensitive layer, and it is known that a layer containing polyvinyl alcohol as a main component is effective as such an oxygen blocking layer. Have been.
[0011]
In addition, the oxygen barrier layer tends to generate sludge and sludge in the developer by being brought into the developer. Therefore, a step of washing with water before development to remove the oxygen barrier layer (pre-washing or washing with water before development) is performed. It is effective to provide. However, when the photosensitive lithographic printing plate material provided with an oxygen barrier layer containing polyvinyl alcohol as a main component on the photopolymerizable photosensitive layer is repeatedly processed using an automatic developing machine, sludge and sludge are generated in the pre-washing liquid. Therefore, the burden on the work such as cleaning and clogging of the pump has been a problem.
[0012]
Japanese Patent Application Laid-Open No. 10-10754 discloses a technique in which various additives are used in pre-development rinsing water, but no solution including prevention of stop stains described above has been made.
[0013]
[Problems to be solved by the invention]
An object of the present invention is to prevent fine spot-like stains (stop stains) occurring in a non-image portion when printing is resumed after a printing machine is temporarily stopped in a continuous process. It is an object of the present invention to provide a photosensitive lithographic printing plate material and a method for processing a photosensitive lithographic printing plate material, in which sludge and sludge accumulated in a developing tank and a pretreatment tank are reduced to reduce a burden of a cleaning operation.
[0014]
[Means for Solving the Problems]
The above object of the present invention has been achieved by the following configurations.
[0015]
1. Photosensitive lithographic plate having, on an aluminum plate support, at least one photopolymerizable photosensitive layer containing an addition-polymerizable ethylenically unsaturated bond-containing monomer, a photopolymerization initiator and a polymer binder, and a protective layer. A photosensitive lithographic printing plate material, wherein the protective layer contains at least a water-soluble polymer and a compound represented by the general formula (1).
[0016]
2. Photosensitive lithographic plate having, on an aluminum plate support, at least one photopolymerizable photosensitive layer containing an addition-polymerizable ethylenically unsaturated bond-containing monomer, a photopolymerization initiator and a polymer binder, and a protective layer. A printing plate material, wherein the protective layer contains at least a water-soluble polymer and an N-alkyl-substituted N-substituted iminodiacetic acid having 1 to 3 carbon atoms or a salt thereof. .
[0017]
3. Photosensitive lithographic plate having, on an aluminum plate support, at least one photopolymerizable photosensitive layer containing an addition-polymerizable ethylenically unsaturated bond-containing monomer, a photopolymerization initiator and a polymer binder, and a protective layer. A photosensitive lithographic printing plate material, wherein the protective layer contains at least a water-soluble polymer and a compound represented by the general formula (2).
[0018]
4. 2. A method for processing a photosensitive lithographic printing plate material according to 1, wherein the photosensitive lithographic printing plate material is subjected to image exposure, a protective layer is washed away in a water washing step, and then developed.
[0019]
5. 3. A method for processing a photosensitive lithographic printing plate material, which comprises subjecting the photosensitive lithographic printing plate material to image exposure, washing and removing a protective layer in a water washing step, and then developing.
[0020]
6. 4. A method for processing a photosensitive lithographic printing plate material according to 3, wherein the photosensitive lithographic printing plate material is subjected to image exposure, the protective layer is washed away in a water washing step, and then developed.
[0021]
Hereinafter, main components of the photosensitive lithographic printing plate material, an image forming method, a processing method, and the like will be described.
[0022]
(Support)
The support for the photosensitive lithographic printing plate material of the present invention is preferably an aluminum metal plate. In this case, either a pure aluminum plate or an aluminum alloy plate may be used.
[0023]
As the aluminum alloy, various types can be used, and for example, an alloy of aluminum with a metal such as silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, nickel, titanium, sodium, or iron is used.
[0024]
It is preferable that the support is subjected to a degreasing treatment in order to remove rolling oil on the surface prior to roughening (graining treatment). Examples of the degreasing treatment include a degreasing treatment using a solvent such as trichlene and thinner, and an emulsion degreasing treatment using an emulsion such as kesilon and triethanol. In the degreasing treatment, an aqueous solution of an alkali such as caustic soda can also be used. 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 above degreasing treatment can be removed. When an alkaline aqueous solution such as caustic soda is used for the degreasing treatment, smut is formed 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. Preferably, a treatment is applied. Examples of the method of surface roughening include a mechanical method and a method of etching by electrolysis.
[0025]
The mechanical surface roughening method used is not particularly limited, but a brush polishing method and a honing polishing method are preferable. The surface roughening by the brush polishing method is performed, for example, by rotating a rotating brush using brush bristles having a diameter of 0.2 to 0.8 mm, and applying, for example, particles of volcanic ash having a particle size of 10 to 100 μm to water on the support surface. It can be performed by pressing a brush while supplying a uniformly dispersed slurry. For surface roughening by honing polishing, for example, particles of volcanic ash having a particle size of 10 to 100 μm are uniformly dispersed in water, pressure is applied from a nozzle to be ejected, and the surface is made to impinge obliquely on the support surface to perform surface roughening. Can be. Further, for example, abrasive particles having a particle size of 10 to 100 μm are formed on the surface of the support at intervals of 100 to 200 μm by 2.5 × 10 ³ -10 × 10 ³ Pieces / cm ² The sheets can be roughened by laminating the coated sheets so that the sheets are present at a density of 1 and transferring the rough surface pattern of the sheet by applying pressure.
[0026]
After the surface is roughened by the above-mentioned mechanical surface roughening method, it is preferable to immerse the substrate in an aqueous solution of an acid or an alkali in order to remove the abrasive, the formed aluminum dust and the like that have penetrated the surface of the support. As the acid, for example, sulfuric acid, persulfuric acid, hydrofluoric acid, phosphoric acid, nitric acid, hydrochloric acid and the like are used, and as the base, for example, sodium hydroxide, potassium hydroxide and the like are used. Among these, it is preferable to use an aqueous alkali solution such as sodium hydroxide. The dissolution amount of aluminum on the surface is 0.5 to 5 g / m ² Is preferred. After performing the immersion treatment with an alkali aqueous solution, it is preferable to immerse in an acid such as phosphoric acid, nitric acid, sulfuric acid, and chromic acid or a mixed acid thereof to perform a neutralization treatment.
[0027]
Although the electrochemical surface roughening method is not particularly limited, a method of performing electrochemical surface roughening in an acidic electrolyte is preferable. As the acidic electrolytic solution, an acidic electrolytic solution usually used for 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, the methods described in JP-B-48-28123, UK Patent 896,563, and JP-A-53-67507 can be used. This surface 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 10-200 A / dm ² Can be used, but 50 to 150 A / dm ² It is preferable to select from the range. Electricity is 100-5000 c / dm ² Can be used, but 100 to 2000 c / dm ² It is preferable to select from the range. The temperature for performing the surface roughening method may be in the range of 10 to 50 ° C, but is preferably selected from the range of 15 to 45 ° C.
[0028]
When performing electrochemical surface roughening using a nitric acid-based electrolyte as an electrolyte, it can be generally performed by applying a voltage in a range of 1 to 50 volts, but is selected from a range of 10 to 30 volts. Is preferred. Current density is 10-200 A / dm ² Can be used, but 20 to 100 A / dm ² It is preferable to select from the range. Electricity is 100-5000 c / dm ² Can be used, but 100 to 2000 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 nitric acid concentration in the electrolytic solution is preferably from 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.
[0029]
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 10-200 A / dm ² Can be used, but 50 to 150 A / dm ² It is preferable to select from the range. Electricity is 100-5000 c / dm ² Can be used, but 100 to 2000 c / dm ² , And 200-1000 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 electrolyte is preferably 0.1 to 5% by mass.
[0030]
After the surface is roughened by the above-mentioned electrochemical surface roughening method, it is preferable to immerse in an aqueous solution of an acid or alkali to remove aluminum dust and the like on the surface. As the acid, for example, sulfuric acid, persulfuric acid, hydrofluoric acid, phosphoric acid, nitric acid, hydrochloric acid and the like are used, and as the base, for example, sodium hydroxide, potassium hydroxide and the like are used. Among these, it is preferable to use an aqueous alkali solution. The dissolution amount of aluminum on the surface is 0.5 to 5 g / m ² Is preferred. Further, it is preferable that after immersion treatment with an aqueous alkali solution, immersion in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid or a mixed acid thereof to perform neutralization treatment.
[0031]
The mechanical surface roughening method and the electrochemical surface roughening method may be used alone to roughen the surface, or the mechanical surface roughening method may be followed by the electrochemical surface roughening method. The surface may be roughened.
[0032]
Subsequent to the roughening treatment, an anodic oxidation treatment can be performed. The method of the anodic oxidation treatment that can be used in the present invention is not particularly limited, and a known method can be used. By performing the anodic oxidation treatment, an oxide film is formed on the support. In the anodic oxidation 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 the current density is 1 to 10 A / dm. ² A method of electrolysis at a high current density in sulfuric acid described in U.S. Pat. No. 1,412,768, and a method of electrolysis at high current density described in U.S. Pat. No. 3,511,661 are also used. And a method using a solution containing one or more of chromic acid, oxalic acid, malonic acid, and the like. The formed anodized coating amount is 1 to 50 mg / dm. ² Is suitable, and preferably 10 to 40 mg / dm. ² It is. The anodic oxidation coating amount is obtained, for example, by immersing an aluminum plate in a chromic acid phosphoric acid solution (prepared by dissolving 35 g of a 85% phosphoric acid solution and 20 g of chromium (IV) oxide in 1 L of water) to dissolve the oxide film, It can be determined by measuring the change in mass before and after dissolving the coating on the plate.
[0033]
The support subjected to the anodizing treatment may be subjected to a sealing treatment as required. These sealing treatments can be performed using a known method such as hot water treatment, boiling water treatment, steam treatment, sodium silicate treatment, dichromate aqueous solution treatment, nitrite treatment, and ammonium acetate treatment.
[0034]
Further, after performing these treatments, a water-soluble resin such as polyvinylphosphonic acid, a polymer and a copolymer having a sulfonic acid group in a side chain, polyacrylic acid, a water-soluble metal salt (eg, zinc borate) or Those coated with a yellow dye, an amine salt or the like are also suitable. Further, a sol-gel treated substrate having a functional group capable of causing an addition reaction by a radical covalently disclosed in JP-A-5-304358 is preferably used.
[0035]
(Ethylene unsaturated bond-containing monomer capable of addition polymerization)
Radical polymerization is possible with the addition-polymerizable ethylenically unsaturated bond-containing monomer (hereinafter sometimes referred to as monomer) used in the photopolymerizable photosensitive layer (hereinafter sometimes referred to as photosensitive layer) of the present invention. Known monomers having an ethylenically unsaturated bond are included.
[0036]
Specific compounds include, for example, 2-ethylhexyl acrylate, 2-hydroxypropyl acrylate, glycerol acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, nonylphenoxyethyl acrylate, tetrahydrofurfuryloxyethyl acrylate, tetrahydrofurfuryloxyhexanol Monoacrylates such as acrylate, acrylate of ε-caprolactone adduct of 1,3-dioxane alcohol, and 1,3-dioxolane acrylate, or methacrylic acid in which these acrylates are replaced with methacrylate, itaconate, crotonate, and maleate , Itaconic acid, crotonic acid, maleic acid ester such as ethylene glycol diacrylate, triethylene Glycol diacrylate, pentaerythritol diacrylate, hydroquinone diacrylate, resorcinol diacrylate, hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, diacrylate of neopentyl glycol hydroxypivalate, and neopentyl glycol adipate Diacrylate, 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-hexane Bifunctional acrylates such as diacrylates of all diglycidyl ethers, or methacrylic acid, itaconic acid, crotonic acid, maleic acid ester in which these acrylates are replaced with methacrylate, itaconate, crotonate, or maleate, such as trimethylolpropanetriene Ε of acrylate, ditrimethylolpropane tetraacrylate, trimethylolethane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexaacrylate Caprolactone adduct, pyrogallol triacrylate, propion・ Dipentaerythritol triacrylate, propionic acid ・ Polyfunctional acrylates such as dipentaerythritol tetraacrylate, hydroxypivalylaldehyde-modified dimethylolpropane triacrylate, or these acrylates were replaced with methacrylate, itaconate, crotonate, and maleate. Examples include methacrylic acid, itaconic acid, crotonic acid, and maleic ester.
[0037]
Further, a prepolymer can be used in the same manner as described above. Examples of the prepolymer include the compounds 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 also be suitably used. One or more of these prepolymers may be used in combination, or may be used as a mixture with the above-mentioned monomer and / or oligomer.
[0038]
As the prepolymer, for example, 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, pimelic acid, Polybasic acids such as sebacic acid, dodecanoic acid and tetrahydrophthalic acid, and ethylene glycol, propylene glycol, diethylene glycol, propylene oxide, 1,4-butanediol, triethylene glycol, tetraethylene glycol, polyethylene glycol, glycerin and trimethylol Polyester obtained by introducing (meth) acrylic acid into a polyester obtained by bonding a polyhydric alcohol such as propane, pentaerythritol, sorbitol, 1,6-hexanediol, and 1,2,6-hexanetriol. Acrylates, for example, epoxy acrylates obtained by introducing (meth) acrylic acid into an epoxy resin such as bisphenol A / epichlorohydrin / (meth) acrylic acid and phenol novolak / epichlorohydrin / (meth) acrylic acid; for example, ethylene glycol / adipin 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 Of trimethylolpropane / propylene glycol / tolylene diisocyanate / 2-hydroxyethyl acrylate As described above, urethane acrylate in which (meth) acrylic acid is introduced into urethane resin, for example, polysiloxane acrylate, silicone resin acrylates such as polysiloxane / diisocyanate / 2-hydroxyethyl acrylate, and (meth) acryloyl in oil-modified alkyd resin Examples include prepolymers such as alkyd-modified acrylates having introduced groups and spirane resin acrylates.
[0039]
The photopolymerizable photosensitive layer of the present invention includes a phosphazene monomer, triethylene glycol, isocyanuric acid EO (ethylene oxide) -modified diacrylate, isocyanuric acid EO-modified triacrylate, dimethylol tricyclodecane diacrylate, and trimethylolpropane acrylic acid. It may contain a monomer such as a benzoate, an alkylene glycol-type acrylic acid-modified or a urethane-modified acrylate, and an addition-polymerizable oligomer or prepolymer having a structural unit formed from the monomer.
[0040]
Further, examples of the monomer used in the present invention include a phosphate compound containing at least one (meth) acryloyl group. The compound is a compound in which at least a part of the hydroxyl group of phosphoric acid is esterified, and is not particularly limited as long as it has a (meth) acryloyl group.
[0041]
In addition, JP-A-58-212994, JP-A-61-6649, JP-A-62-46688, JP-A-62-48589, JP-A-62-173295, JP-A-62-187092, and JP-A-63-187092. Compounds described in JP-A-67189, JP-A-1-244891 and the like can be mentioned, and furthermore, "11290 Chemical Products", Chemical Daily, p. 286-p. 294, “UV / EB curing handbook (raw material edition)”, Polymer Publishing Association, p. The compounds described in 11 to 65 and the like can also be suitably used in the present invention. Of these, compounds having two or more acrylic or methacrylic 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.
[0042]
The photosensitive layer of the present invention preferably contains the above-mentioned monomer in a range of 1.0 to 80.0% by mass, more preferably 3. It is in the range of 0 to 70.0% by mass.
[0043]
(Polymer binder)
The photosensitive lithographic printing plate material of the present invention contains a polymer binder in the photosensitive layer. As the polymer binder according to the present invention, for example, acrylic polymer, polyvinyl butyral resin, polyurethane resin, polyamide resin, polyester resin, epoxy resin, phenol resin, polycarbonate resin, polyvinyl butyral resin, polyvinyl formal resin, shellac, Other natural resins and the like can be used. Further, two or more of these may be used in combination.
[0044]
In each of the above-mentioned polymer binders, it is preferably a vinyl copolymer obtained by copolymerization of an acrylic monomer, and further, (a) a carboxyl group-containing monomer, (b) ) It is preferably a copolymer of an alkyl methacrylate or an alkyl acrylate.
[0045]
Specific examples of the carboxyl group-containing monomer include α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, and itaconic anhydride. In addition, a carboxylic acid such as a half ester of phthalic acid and 2-hydroxymethacrylate is also preferable.
[0046]
Specific examples of alkyl methacrylate and alkyl acrylate include, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, methacryl Nonyl acid, decyl methacrylate, undecyl methacrylate, dodecyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, nonyl acrylate And unsubstituted alkyl esters such as decyl acrylate, undecyl acrylate, and dodecyl acrylate, and cyclic alkyl esters such as cyclohexyl methacrylate and cyclohexyl acrylate. Ter, benzyl methacrylate, 2-chloroethyl methacrylate, N, N-dimethylaminoethyl methacrylate, glycidyl methacrylate, benzyl acrylate, 2-chloroethyl acrylate, N, N-dimethylaminoethyl acrylate, glycidyl acrylate, etc. Substituted alkyl esters and the like can be mentioned.
[0047]
Furthermore, in the polymer binder according to the present invention, the following monomers (1) to (14) and the like can be used as other copolymerized monomers.
[0048]
(1) Monomers having an aromatic hydroxyl group, for example, o- (or p-, m-) hydroxystyrene, o- (or p-, m-) hydroxyphenyl acrylate and the like.
[0049]
(2) Monomers having an aliphatic hydroxyl group, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, N-methylol acrylamide, N-methylol methacrylamide, 4-hydroxybutyl methacrylate, 5-hydroxypentyl acrylate, 5-hydroxypentyl Methacrylate, 6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate, N- (2-hydroxyethyl) acrylamide, N- (2-hydroxyethyl) methacrylamide, hydroxyethyl vinyl ether and the like.
[0050]
(3) Monomers having an aminosulfonyl group, for example, m- (or p-) aminosulfonylphenyl methacrylate, m- (or p-) aminosulfonylphenyl acrylate, N- (p-aminosulfonylphenyl) methacrylamide, N- ( p-aminosulfonylphenyl) acrylamide and the like.
[0051]
(4) Monomers having a sulfonamide group, for example, N- (p-toluenesulfonyl) acrylamide, N- (p-toluenesulfonyl) methacrylamide and the like.
[0052]
(5) acrylamide or methacrylamides, for example, 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.
[0053]
(6) Monomers containing an alkyl fluoride group, for example, trifluoroethyl acrylate, trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, hexafluoropropyl methacrylate, octafluoropentyl acrylate, octafluoropentyl methacrylate, heptadecafluorodecyl methacrylate, N -Butyl-N- (2-acryloxyethyl) heptadecafluorooctylsulfonamide and the like.
[0054]
(7) Vinyl ethers, for example, ethyl vinyl ether, 2-chloroethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, phenyl vinyl ether and the like.
[0055]
(8) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate, and vinyl benzoate.
[0056]
(9) Styrenes, for example, styrene, methylstyrene, chloromethylstyrene and the like.
[0057]
(10) Vinyl ketones, for example, methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, phenyl vinyl ketone and the like.
[0058]
(11) Olefins, for example, ethylene, propylene, i-butylene, butadiene, isoprene and the like.
[0059]
(12) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine and the like.
[0060]
(13) Monomers having a cyano group, for example, acrylonitrile, methacrylonitrile, 2-pentenenitrile, 2-methyl-3-butenenitrile, 2-cyanoethylacrylate, o- (or m-, p-) cyanostyrene and the like.
[0061]
(14) Monomers having an amino group, for example, 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.
[0062]
Further, other monomers copolymerizable with these monomers may be copolymerized.
Further, an unsaturated bond-containing vinyl copolymer obtained by subjecting a carboxyl group present in the molecule of the vinyl copolymer to an addition reaction of a compound having a (meth) acryloyl group and an epoxy group in the molecule may also be used. Preferred as a polymer binder. Specific examples of the compound containing both an unsaturated bond and an epoxy group in the molecule include glycidyl acrylate, glycidyl methacrylate, and an epoxy group-containing unsaturated compound described in JP-A-11-271969.
[0063]
These copolymers preferably have a weight average molecular weight of from 10,000 to 200,000 as measured by gel permeation chromatography (GPC), but are not limited to this range.
[0064]
The polymer binder, if necessary, polyvinyl butyral resin, polyurethane resin, polyamide resin, polyester resin, epoxy resin, novolak resin, natural resin, etc. You may use together with a copolymer.
[0065]
The content of the polymer binder in the composition for coating the photosensitive layer is preferably from 10 to 90% by mass, more preferably from 15 to 70% by mass, and more preferably from 20 to 50% by mass. Is particularly preferred in terms of sensitivity. Furthermore, the above-mentioned vinyl copolymer is preferably 50 to 100% by mass, more preferably 100% by mass, in the polymer binder.
[0066]
The acid value of the polymer contained in the polymer binder is preferably in the range of 10 to 150, more preferably in the range of 30 to 120, and more preferably in the range of 50 to 90. It is particularly preferable from the viewpoint of balancing the overall polarity, whereby aggregation of the pigment in the coating solution for the photosensitive layer can be prevented.
[0067]
(Photopolymerization initiator)
As the photopolymerization initiator that can be used in the present invention, preferably, for example, J.I. 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 compounds disclosed in British Patent No. 1,459,563 are also preferable.
[0068]
Specifically, the following examples can be given, but are 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, and 4,4′-bis Benzophenone derivatives such as (dimethylamino) 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, as well as JP-B-59-1281, JP-B-61-9621 and JP-A-60-601 No. 04; triazine derivatives described in JP-A Nos. 59-1504 and 61-243807; and organic peroxides described in JP-A Nos. 61-243807; No. 6413, No. 47-1604 and U.S. Pat. No. 3,567,453; diazonium compounds; U.S. Pat. Nos. 2,848,328, 2,852,379 and 2,940,853 Organic azide compounds described in JP-B-36-22062, JP-B-37-13109, JP-B-38-18015 and JP-B-45-9610; JP-B-55-39162. Gazette, JP-A-59-14023, and "Macromolecules", vol. 10, p. 1307 (197) ); Azo compounds described in JP-A-59-142205; JP-A-1-54440, EP 109,851, EP 126,712, and "Journal of Imaging" Science (J. Imag. Sci.), Vol. 30, p. 174 (1986); metallocene complexes described in JP-A-5-213861 and JP-A-5-255347; organoboron complexes of (oxo) sulfonium; Titanocenes described in JP-A-59-152396 and JP-A-61-151197; "Coordination Chemistry Review", Vol. 84, pp. 85-277 (1988), and JP-A-2-182701. Transition of ruthenium etc. Transition metal complex containing metal; 2,4,5-triarylimidazole dimer described in JP-A-3-209777; carbon tetrabromide; organic halogen compound described in JP-A-59-107344 etc.
[0069]
Among them, preferred are titanocenes. Specific examples of titanocenes include di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,3,4. , 5,6-Pentafluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis -2,4,6-trifluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,6-difluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2, 4-difluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bi -2,3,5,6-tetrafluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis-2,4-difluorophenyl-1-yl, bis (cyclopentadienyl) -bis ( 2,6-difluoro-3- (pyr-1-yl) phenyl) titanium (IRUGACURE784: manufactured by Ciba Specialty Chemicals), but is not limited thereto.
[0070]
When laser light is used as the light source, it is preferable to add a sensitizing dye to the photosensitive layer.
[0071]
Compounds that sensitize wavelength from visible light to near infrared include, for example, cyanine, phthalocyanine, merocyanine, porphyrin, spiro compound, ferrocene, fluorene, fulgide, imidazole, perylene, phenazine, phenothiazine, polyene, azo compound, diphenylmethane, triphenyl Methane, polymethine acridine, coumarin, ketocoumarin, quinacridone, indigo, styryl, pyrylium compounds, pyromethene compounds, pyrazolotriazole compounds, benzothiazole compounds, barbituric acid derivatives, thiobarbituric acid derivatives, and the like. No. 993, U.S. Pat. Nos. 4,508,811, 5,227,227, JP-A-2001-125255, JP-A-11-271969 and the like can also be used. .
[0072]
In the present invention, preferred specific examples of the combination of the photopolymerization initiator and the sensitizing dye include the combinations described in JP-A-2001-125255 and JP-A-11-271969.
[0073]
The amount of the polymerization initiator is not particularly limited, but is preferably 0.1 to 20 parts by mass based on 100 parts by mass of the addition-polymerizable ethylenically unsaturated bond-containing monomer according to the present invention. The molar ratio of the photopolymerization initiator and the sensitizing dye is preferably in the range of 1: 100 to 100: 1.
[0074]
(Various additives)
To the coating composition of the photosensitive layer of the present invention, in addition to the above components, a polymerization inhibitor is added to prevent unnecessary polymerization of the monomer during the production or storage of the photosensitive lithographic printing plate material. It is desirable to do. 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), cerium N-nitrosophenylhydroxylamine, 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5) -Methylbenzyl) -4-methylphenyl acrylate and the like.
[0075]
The amount of the polymerization inhibitor to be added is preferably 0.01 to 5% by mass based on the total solid content of the composition. Also, if necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to prevent polymerization inhibition by oxygen, or may be unevenly distributed on the surface of the photosensitive layer in a drying process after coating. Good. The added amount of the higher fatty acid derivative is preferably 0.5 to 10% by mass of the whole composition.
[0076]
A coloring agent can also be used, and conventionally known coloring agents including commercially available coloring agents can be suitably used. For example, those described in the revised new edition “Pigment Handbook”, edited by the Japan Pigment Technical Association (Seibundo Shinkosha), Color Index Handbook, and the like can be mentioned.
[0077]
Examples of the type of the pigment include a black pigment, a yellow pigment, a red pigment, a brown pigment, a violet pigment, a blue pigment, a green pigment, a fluorescent pigment, and a metal powder pigment. Specifically, inorganic pigments (titanium dioxide, carbon black, graphite, zinc oxide, Prussian blue, cadmium sulfide, iron oxide, and chromates of lead, zinc, barium, and calcium, etc.) and organic pigments (azo, thioindigo) , Anthraquinone, anthranthrone, and triphenedioxazine pigments, vat dye pigments, phthalocyanine pigments and derivatives thereof, and quinacridone pigments.
[0078]
Among these, it is preferable to select and use a pigment that does not substantially absorb in the absorption wavelength region of the spectral sensitizing dye corresponding to the exposure laser to be used, and in this case, an integrating sphere at the laser wavelength to be used is used. The reflection and absorption of the pigment used is preferably 0.05 or less. The amount of the pigment to be added is preferably from 0.1 to 10% by mass, more preferably from 0.2 to 5% by mass, based on the solid content of the composition.
[0079]
When an argon laser (488 nm) or an SHG-YAG laser (532 nm) is used as an exposure light source, violet pigments and blue pigments are used from the viewpoints of pigment absorption in the above-described photosensitive wavelength region and visibility after development. Preferably, it is used. Such materials include, for example, cobalt blue, cerulean blue, alkali blue lake, Phonatone blue 6G, Victoria blue lake, metal-free phthalocyanine blue, phthalocyanine blue fast sky blue, indanthrene blue, indico, dioxane violet, isohexane Biolanthrone violet, indanthrone blue, indanthrone BC and the like can be mentioned. Among these, phthalocyanine blue and dioxane violet are more preferred.
[0080]
In addition, the above composition may contain a surfactant as a coatability improver as long as the performance of the present invention is not impaired. Among them, preferred are fluorine-based surfactants.
[0081]
Further, in order to improve the physical properties of the cured film, additives such as an inorganic filler and a plasticizer such as dioctyl phthalate, dimethyl phthalate and tricresyl phosphate may be added. The addition amount of these is preferably 10% by mass or less of the total solid content.
[0082]
(Application)
Solvents used for preparing the photosensitive composition of the photosensitive layer of the present invention include, for example, alcohols (for polyhydric alcohol derivatives, sec-butanol, isobutanol, n-hexanol, benzyl alcohol, diethylene glycol, triethylene glycol, Ethylene glycol, tetraethylene glycol, 1,5-pentanediol), ethers (propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether), ketones, aldehydes (diacetone alcohol, cyclohexanone, methylcyclohexanone) ), Esters (ethyl lactate, butyl lactate, diethyl oxalate, methyl benzoate) and the like.
[0083]
The prepared photosensitive composition (photosensitive layer coating solution) is applied on a support by a conventionally known method and dried to prepare a photosensitive lithographic printing plate material. Examples of the application method of the application liquid include an air doctor coater method, a blade coater method, a wire bar method, a knife coater method, a dip coater method, a reverse roll coater method, a gravure coater method, a cast coating method, a curtain coater method, an extrusion coater method, and the like. Can be mentioned.
[0084]
If the drying temperature of the photosensitive layer is too low, sufficient printing durability cannot be obtained. If the drying temperature is too high, not only Marangoni occurs but also fogging of a non-image area occurs. The preferred drying temperature range is 60 to 160 ° C, more preferably 80 to 140 ° C, and particularly preferably 90 to 120 ° C.
[0085]
(Protective layer)
It is preferable to provide a protective layer (also referred to as an oxygen blocking layer or an overcoat layer) above the photosensitive layer of the present invention. For the protective layer, it is preferable to use a water-soluble polymer that can form a film having low oxygen permeability. Specific examples include polyvinyl alcohol and polyvinyl pyrrolidone. Polyvinyl alcohol has an effect of suppressing oxygen permeation, and polyvinyl pyrrolidone has an effect of securing adhesiveness with an adjacent photosensitive layer.
[0086]
In addition to the above two polymers, if necessary, polysaccharide, polyethylene glycol, gelatin, glue, casein, hydroxyethylcellulose, carboxymethylcellulose, methylcellulose, hydroxyethylstarch, acacia, saccharose octaacetate, ammonium alginate, sodium alginate And water-soluble polymers such as polyvinylamine, polyethylene oxide, polystyrene sulfonic acid, polyacrylic acid, and water-soluble polyamide, and these can be used in combination.
[0087]
Further, the protective layer of the present invention may further contain a surfactant, a matting agent, and the like, if necessary, and it is also preferable to contain a preservative described in JP-A-2001-281872.
[0088]
The protective layer is formed by dissolving the above composition in a suitable solvent, applying the composition on the photosensitive layer, and drying the composition. As the coating solvent, water or alcohols such as methanol, ethanol, i-propanol and the like are preferable.
[0089]
The thickness of the protective layer is preferably from 0.1 to 5.0 μm, particularly preferably from 0.5 to 3.0 μm.
[0090]
In the photosensitive lithographic printing plate material according to the present invention, the peeling force between the photosensitive layer and the protective layer is preferably at least 35 mN / mm, more preferably at least 50 mN / mm, even more preferably at least 75 mN / mm. Preferred compositions of the protective layer include those described in JP-A-10-161645.
[0091]
The peeling force in the present invention is obtained by applying an adhesive tape of a predetermined width having a sufficiently large adhesive force on the protective layer and peeling the protective layer at an angle of 90 degrees with respect to the plane of the photosensitive lithographic printing plate material. It can be determined by measuring the force.
[0092]
(Compound of general formula (1))
The compound of the present invention represented by the general formula (1) represents a compound represented by the formula (1) in the claims, and in the formula of the general formula (1), ₁ , A ₂ , A ₃ And A ₄ Is -CH ₂ OH, -PO ₃ (M ₁ ) ₂ Or -COOM, which may be the same or different. M and M ₁ Represents a hydrogen atom, an ammonium group, an alkali metal atom or an organic ammonium group, respectively. X is an alkylene group having 2 to 6 carbon atoms or-(B ₁ O) _n -B ₂ Represents-. n represents an integer of 1 to 8; ₁ And B ₂ May be the same or different and each represents an alkylene group having 1 to 5 carbon atoms.
[0093]
More specifically, in the general formula (1), A ₁ ~ A ₄ May be the same or different, and -CH ₂ OH, -PO ₃ (M ₁ ) ₂ Or -COOM, and M and M ₁ Represents a hydrogen atom, an ammonium group, an alkali metal atom (eg, sodium or potassium) or an organic ammonium group (eg, a methyl ammonium group, a trimethyl ammonium group, etc.). X represents an alkylene group having 2 to 6 carbon atoms which may be substituted or-(B ₁ O) _n -B ₂ Represents-. Also, B ₁ And B ₂ May be the same or different and each represents an optionally substituted alkylene group having 1 to 5 carbon atoms. Examples of the alkylene group represented by X include ethylene, trimethylene, tetramethylene and the like. Also, B ₁ And B ₂ Examples of the alkylene group represented by are methylene, ethylene, trimethylene and the like. X, B ₁ Or B ₂ Examples of the substituent of the alkylene group represented by include a hydroxyl group, an alkyl group having 1 to 3 carbon atoms (eg, a methyl group, an ethyl group, and the like). n represents an integer of 1 to 8, and preferably 1 to 4.
[0094]
Preferred specific examples of the compound represented by the general formula (1) are shown below, but it should not be construed that the invention is limited thereto.
[0095]
Embedded image

[0096]
Embedded image

[0097]
The compound represented by the general formula (1) can be synthesized by a method generally known to those skilled in the art.
[0098]
Among these, particularly preferred compounds are 1-1, 1-3 and 1-14.
The amount of the compound represented by the general formula (1) added to the protective layer is preferably 0.001 to 1% by mass, and more preferably 0.001 to 0.1% by mass. In order to contain it, it can be added and contained in the coating solution for the protective layer.
[0099]
(C1-C3 N-alkyl-substituted N-substituted iminodiacetic acid or a salt thereof)
In the N-alkyl-substituted iminodiacetic acid or a salt thereof having 1 to 3 carbon atoms of the present invention (hereinafter, the N-substituted iminodiacetic acid or a salt thereof according to the present invention), the alkyl group of the N-alkyliminodiacetic acid is And an alkyl group having 1 to 3 carbon atoms, such as a methyl group, an ethyl group, a propyl group, and an isopropyl group. These alkyl groups may be substituted with a hydroxy group, and the number of hydroxy groups in the alkyl group is preferably 0 to 3.
[0100]
Specific compounds of the N-substituted iminodiacetic acid or a salt thereof according to the present invention are listed below, but are not limited thereto.
[0101]
L-1: N-methyliminodiacetic acid
L-2: N-ethyliminodiacetic acid
L-3: N-hydroxymethyliminodiacetic acid
L-4: N-β-hydroxyethyliminodiacetic acid
L-5: N-propyliminodiacetic acid
L-6: N-α, β-dihydroxyethyliminodiacetic acid
L-7: N-α-hydroxyethyliminodiacetic acid
Among the above exemplified compounds, L-1, L-2 and L-3 are particularly preferred.
[0102]
The preferable addition amount of the N-substituted iminodiacetic acid or a salt thereof according to the present invention to the protective layer is preferably 0.001 to 1% by mass, and more preferably 0.001 to 0.1% by mass. In order to contain it, it can be added and contained in the coating solution for the protective layer.
[0103]
(Compound of general formula (2))
The compound of the present invention represented by the general formula (2) represents the compound represented by the formula (2) in the claims, and specific examples are shown below.
[0104]
Embedded image

[0105]
Further, for example, compounds represented by the general formula 1 described in JP-A-6-100884 can be exemplified.
[0106]
Among these, β-alanine diacetic acid or a salt thereof is particularly preferable.
[0107]
The preferable addition amount of the compound represented by the general formula (2) of the present invention to the protective layer is preferably 0.001 to 1% by mass, more preferably 0.001 to 0.1% by mass. In order to contain it, it can be added and contained in the coating solution for the protective layer.
[0108]
As described above, in the present invention, the compound represented by the general formula (1), the compound represented by the general formula (2) and / or the N-substituted iminodiacetic acid or a salt thereof according to the present invention is contained in the protective layer. It is preferable to contain, but among these, the compound represented by the general formula (1) is particularly preferable.
[0109]
(Image forming method)
Examples of the light source for imagewise exposing 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. And the like.
[0110]
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 overlaid on the photosensitive layer and exposed.
[0111]
When using an array type light source such as a light emitting diode array, or when controlling the exposure of a light source such as a halogen lamp, a metal halide lamp, or a tungsten lamp with an optical shutter material such as a liquid crystal or PLZT, a digital signal corresponding to an image signal is used. Exposure is possible and preferred. In this case, writing can be performed directly without using a mask material.
[0112]
In the case of laser exposure, light can be squeezed into a beam to perform scanning exposure in accordance with image data, so that it is suitable for directly writing without using a mask material. When a laser is used as a light source, the exposure area can be easily reduced to a very small size, and high-resolution image formation is possible.
[0113]
As a laser light source, any of an argon laser, a He—Ne gas laser, a YAG laser, and a semiconductor laser can be suitably used. Laser scanning methods include cylinder outer surface scanning, cylinder inner surface scanning, and plane scanning. In the cylindrical outer surface scanning, laser exposure is performed while rotating a drum around which a recording material is wound around the outer surface, and rotation of the drum is defined as main scanning and movement of laser light is defined as sub-scanning. In the cylindrical inner surface scanning, a recording material is fixed on the inner surface of the drum, a laser beam is irradiated from the inside, and a main scan is performed in the circumferential direction by rotating a part or all of the optical system, and a part of the optical system or Sub-scanning is performed in the axial direction by moving the whole linearly in parallel to the axis of the drum. In the planar scanning, the main scanning of the laser beam is performed by combining a polygon mirror or a galvanometer mirror with an fθ lens, and the sub-scanning is performed by moving the recording medium. Scanning the outer surface of the cylinder and scanning the inner surface of the cylinder are easier to improve the accuracy of the optical system, and are suitable for high-density recording.
[0114]
(Development processing)
The main components of the developer and replenisher used in the method for processing the photosensitive lithographic printing plate material of the present invention (hereinafter, also referred to as the processing method of the present invention) include silicic acid, phosphoric acid, carbonic acid, boric acid, phenols, saccharides, It preferably contains at least one compound selected from oximes and fluorinated alcohols. Further, the pH of the developer is preferably an alkaline aqueous solution having a range of higher than 8.5 and lower than 13.0. More preferably, the pH is 8.5 to 12.
[0115]
Among these, weakly acidic substances such as phenols, saccharides, oximes and fluorinated alcohols preferably have a dissociation index (pKa) of 10.0 to 13.2. Such an acid is selected from those described in IONISATION CONSTANTS OF ORGANIC ACIDS INAQUEOUS SOLUTION published by PergamonPress, and specifically, salicylic acid (pKa13.0), 3-hydroxy-2-naphthoic acid ( 12.84), catechol (12.6), gallic acid (12.4), sulfosalicylic acid (11.7), 3,4-dihydroxysulfonic acid (12.2), 3,4- Dihydroxybenzoic acid (11.94), 1,2,4-trihydroxybenzene (11.82), hydroquinone (11.56), pyrogallol (11.34), o-cresol (10.33) ), Resorsonol (11.27), p-cresol (10.27) , Phenols having a phenolic hydroxyl group such as m- cresol (same 10.09) and the like.
[0116]
As the saccharide, a non-reducing sugar that is stable even in an alkali can be preferably used. Non-reducing sugars are saccharides that do not have a free aldehyde or ketone group and do not exhibit reducibility, and are trehalose-type oligosaccharides in which reducing groups are bonded to each other, and glycosides in which the reducing group of a saccharide is bonded to a non-saccharide. And sugar alcohols obtained by hydrogenating and reducing saccharides, all of which are suitably used in the present invention. Trehalose-type oligosaccharides include saccharose and trehalose, and examples of glycosides include alkyl glycosides, phenol glycosides, and mustard oil glycosides. Examples of sugar alcohols include, for example, D, L-arabit, ribit, xylit, D, L-sorbit, D, L-mannit, D, L-idit, D, L-tallit, zuricit, and allozurcit. Can be Further, maltitol obtained by hydrogenation of disaccharide and reductant (reduced starch syrup) obtained by hydrogenation of oligosaccharide are preferably used. Furthermore, 2-butanone oxime (pKa 12.45), acetoxime (12.42), 1.2-cycloheptanedione oxime (12.3), 2-hydroxybenzaldehyde oxime (12.10), dimethylglyme Oximes such as oxime (11.9), ethanediamide dioxime (11.37) and acetophenone oxime (11.35), for example, 2,2,3,3-tetrafluoropropanol-1 (11.2). 74), fluorinated alcohols such as trifluoroethanol (12.37) and trichloroethanol (12.24). In addition, aldehydes such as pyridine-2-aldehyde (12.68), pyridine-4-aldehyde (12.05), adenosine (12.56), inosine (12.5), and guanine (12.68) 12.3), cytosine (12.2), hypoxanthine (12.1), xanthine (11.9) and other nucleic acid-related substances, as well as diethylaminomethylsulfonic acid (12.32) 1-amino-3,3,3-trifluorobenzoic acid (12.29), isopropylidene disulfonic acid (12.10), 1,1-ethylidene diphosphonic acid (11.54), 1,1 -Ethylidene disulfonic acid 1-hydroxy (11.52), benzimidazole (12.86), thiobenzamide (12.8), picoline thioamide (12.55), barbi Include weak acid, such as Le acid (same 12.5). These acidic substances may be used alone or in combination of two or more. Among these acidic substances, preferred are silicic acid, phosphoric acid, carbonic acid, sulfosalicylic acid, salicylic acid and sugar alcohols of non-reducing sugars and saccharose, particularly silicic acid, D-sorbit, saccharose and reduced starch syrup in an appropriate pH range. It is preferable because it has a buffering action and is inexpensive.
[0117]
The ratio of these acidic substances in the developer is preferably 0.1 to 30% by mass, more preferably 1 to 20% by mass. If the concentration is below the above range, a sufficient buffering effect cannot be obtained, and if the concentration is above this range, it will be difficult to achieve high concentration, and there will be problems of cost increase.
[0118]
As the base to be combined with these acids, for example, sodium hydroxide, ammonium hydroxide, potassium hydroxide and lithium hydroxide are preferably used. These alkaline agents are used alone or in combination of two or more. Others include, for example, potassium silicate, sodium silicate, lithium silicate, ammonium silicate, potassium metasilicate, sodium metasilicate, lithium metasilicate, ammonium metasilicate, tripotassium phosphate, trisodium phosphate, trilithium phosphate, triammonium phosphate, phosphoric acid Dipotassium, disodium phosphate, dilithium phosphate, diammonium phosphate, potassium carbonate, sodium carbonate, lithium carbonate, ammonium carbonate, potassium bicarbonate, sodium bicarbonate, lithium bicarbonate, ammonium bicarbonate, potassium borate, sodium borate , Lithium borate, ammonium borate and the like, and may be added in the form of a preformed salt. Also in this case, sodium hydroxide, ammonium hydroxide, potassium and lithium can be added for pH adjustment. Also, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, Organic alkali agents such as ethyleneimine, ethylenediamine, and pyridine are also used in combination. Most preferred are potassium silicate and sodium silicate. The concentration of silicate is SiO ₂ It is preferably 1.0 to 3.0% by mass in terms of concentration. In addition, SiO ₂ And the molar ratio of alkali metal M (SiO ₂ / M) is more preferably in the range of 0.25 to 2.
[0119]
In the present invention, the term "developer" refers to not only an unused liquid used at the start of development, but also a replenisher for replenishing the replenisher in order to correct the activity of the liquid which is reduced by processing the photosensitive lithographic printing plate material. And a liquid whose activity is maintained (a so-called running liquid). The replenisher may therefore have a higher activity (alkali concentration) than the developer, so the pH of the replenisher may be above 13.0.
[0120]
(Surfactant)
To the developer and replenisher used in the present invention, various surfactants and organic solvents can be added as necessary for the purpose of accelerating the developability, dispersing the development residue and improving the ink affinity of the printing plate image area. Preferred surfactants include anionic, cationic, nonionic and amphoteric surfactants. Preferred examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene polystyryl phenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, glycerin fatty acid partial esters, and sorbitan. Fatty acid partial esters, pentaerythritol fatty acid partial esters, propylene glycol monofatty acid esters, sucrose fatty acid partial esters, polyoxyethylene sorbitan fatty acid partial esters, polyoxyethylene sorbitol fatty acid partial esters, polyethylene glycol fatty acid esters, poly Glycerin fatty acid partial esters, polyoxyethylenated castor oil, polyoxyethylene glycerin fatty acid partial esters, polio Diethylene-polyoxypropylene block copolymer, polyoxyethylene-polyoxypropylene block copolymer adduct of ethylenediamine, fatty acid diethanolamides, N, N-bis-2-hydroxyalkylamines, polyoxyethylene alkylamine, Nonionic surfactants such as triethanolamine fatty acid esters and trialkylamine oxides, fatty acid salts, abietic acid salts, hydroxyalkanesulfonates, alkanesulfonates, dialkylsulfosuccinates, linear alkylbenzenesulfonates , Branched-chain alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl diphenyl ether sulfonates, alkyl phenoxy polyoxyethylene propyl sulfonates, Lioxyethylene alkyl sulfophenyl ether salts, N-methyl-N-oleyl taurine sodium salt, N-alkyl sulfosuccinic acid monoamide disodium salt, petroleum sulfonates, sulfated tallow oil, sulfate esters of fatty acid alkyl esters, alkyl Sulfate, polyoxyethylene alkyl ether sulfate, fatty acid monoglyceride sulfate, polyoxyethylene alkyl phenyl ether sulfate, polyoxyethylene styryl phenyl ether sulfate, alkyl phosphate, polyoxyethylene alkyl ether phosphorus Acid ester salts, polyoxyethylene alkyl phenyl ether phosphate ester salts, styrene / maleic anhydride copolymer partially saponified products, olefin / anhydride Partially saponified maleic acid copolymers, anionic surfactants such as naphthalene sulfonate formalin condensates, quaternary ammonium salts such as alkylamine salts, tetrabutylammonium bromide, polyoxyethylene alkylamine salts, polyethylene Examples include cationic surfactants such as polyamine derivatives, and amphoteric surfactants such as carboxybetaines, aminocarboxylic acids, sulfobetaines, aminosulfates, and imidazolines. Among the surfactants described above, polyoxyethylene can be read as polyoxyalkylene such as polyoxymethylene, polyoxypropylene, and polyoxybutylene, and those surfactants are also included. . Further preferred surfactants are fluorine-based surfactants containing a perfluoroalkyl group in the molecule. Such fluorine-based surfactants include, for example, anionic type such as perfluoroalkyl carboxylate, perfluoroalkyl sulfonate, perfluoroalkyl phosphate, amphoteric type such as perfluoroalkyl betaine, perfluoroalkyl Cationic and perfluoroalkylamine oxides such as trimethylammonium salts, perfluoroalkylethylene oxide adducts, oligomers containing perfluoroalkyl groups and hydrophilic groups, oligomers containing perfluoroalkyl groups and lipophilic groups, perfluoroalkyl groups, hydrophilic Non-ionic forms such as oligomers containing groups and lipophilic groups, urethanes containing perfluoroalkyl groups and lipophilic groups. The above surfactants can be used alone or in combination of two or more, and are added to the developer in an amount of 0.001 to 10% by mass, more preferably 0.01 to 5% by mass.
[0121]
(Development stabilizer)
In the developer and the replenisher used in the present invention, a development stabilizer can be preferably used. Preferred examples thereof include polyethylene glycol adducts of sugar alcohols described in JP-A-6-282079, tetraalkylammonium salts such as tetrabutylammonium hydroxide, phosphonium salts such as tetrabutylphosphonium bromide, and iodonium salts such as diphenyliodonium chloride. And anionic or amphoteric surfactants described in JP-A-50-51324; water-soluble cationic polymers described in JP-A-55-95946; and JP-A-56-142528. And water-soluble amphoteric polymer electrolytes described in Japanese Patent Application Laid-Open Publication No. H11-157, 1988. Further, an organic boron compound to which an alkylene glycol is added as disclosed in JP-A-59-84241, a polyoxyethylene / polyoxypropylene block polymerization type water-soluble surfactant described in JP-A-60-111246, Polyoxyethylene / polyoxypropylene-substituted alkylenediamine compounds described in JP-A-60-129750, polyethylene glycol having a weight average molecular weight of 300 or more described in JP-A-61-215554, and cations described in JP-A-63-175858 A fluorine-containing surfactant having a functional group, a water-soluble ethylene oxide addition compound obtained by adding 4 mol or more of ethylene oxide to an acid or alcohol described in JP-A-2-39157, and a water-soluble polyalkylene compound. it can.
[0122]
(Organic solvent)
The developing solution and the developing replenisher used in the present invention preferably further contain an organic solvent. As the organic solvent that can be used in the present invention, those having a solubility in water of about 10% by mass or less are suitable, and are preferably selected from those having a solubility of 5% by mass or less. For example, 1-phenylethanol, 2-phenylethanol, 3-phenyl-1-propanol, 4-phenyl-1-butanol, 4-phenyl-2-butanol, 2-phenyl-1-butanol, 2-phenoxyethanol, 2-phenoxyethanol, Benzyloxyethanol, o-methoxybenzyl alcohol, m-methoxybenzyl alcohol, p-methoxybenzyl alcohol, benzyl alcohol, cyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol and 4-methylcyclohexanol, N-phenylethanol Examples include amines and N-phenyldiethanolamine. The content of the organic solvent is preferably from 0.1 to 5% by mass, more preferably from 0.1 to 1% by mass, based on the total mass of the used solution.
[0123]
(Reducing agent)
A reducing agent is added to the developer and the replenisher used in the present invention as needed. This prevents contamination of the printing plate, and is particularly effective when developing a negative photosensitive lithographic printing plate containing a photosensitive diazonium salt compound. Preferred organic reducing agents include, for example, phenol compounds such as thiosalicylic acid, hydroquinone, metol, methoxyquinone, resorcin, and 2-methylresorcin; and amine compounds such as phenylenediamine and phenylhydrazine. More preferred inorganic reducing agents include, for example, sodium, potassium and ammonium salts of inorganic acids such as sulfurous acid, bisulfite, phosphorous acid, hydrogen phosphite, dihydrogen phosphite, thiosulfate and dithionite. And the like. Among these reducing agents, sulfites are particularly excellent in the stain prevention effect. These reducing agents are preferably contained in a range of 0.05 to 5% by mass based on the developing solution at the time of use.
[0124]
(Organic carboxylic acid)
The developing solution and the replenisher used in the present invention may further contain an organic carboxylic acid, if necessary. Preferred organic carboxylic acids are aliphatic and aromatic carboxylic acids having 6 to 20 carbon atoms. Specific examples of the aliphatic carboxylic acid include caproic acid, enantiic acid, caprylic acid, lauric acid, myristic acid, palmitic acid and stearic acid, and particularly preferred are alkanoic acids having 8 to 12 carbon atoms. . Further, unsaturated fatty acids having a double bond in the carbon chain or branched fatty acids may be used. As the aromatic carboxylic acid, a compound in which a benzene ring, a naphthalene ring, an anthracene ring, or the like is substituted with a carboxyl group, specifically, o-chlorobenzoic acid, p-chlorobenzoic acid, o-hydroxybenzoic acid, -Hydroxybenzoic acid, o-aminobenzoic acid, p-aminobenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 3 , 5-dihydroxybenzoic acid, gallic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 2-hydroxy-1-naphthoic acid, 1-naphthoic acid, 2-naphthoic acid and the like. Hydroxynaphthoic acid is particularly effective. The above aliphatic and aromatic carboxylic acids are preferably used as a sodium salt, a potassium salt or an ammonium salt in order to enhance water solubility. The content of the organic carboxylic acid in the developer used in the present invention is not particularly limited, but if the content is less than 0.1% by mass, the effect is not sufficient, and if the content is 10% by mass or more, the effect cannot be further improved. In addition, dissolution may be hindered when another additive is used in combination. Therefore, the preferred addition amount is 0.1 to 10% by mass, more preferably 0.5 to 4% by mass, based on the developer used.
[0125]
(Other additives)
The following additives can be added to the developer and replenisher used in the present invention, in addition to the above, in order to enhance developability. For example, neutral salts such as NaCl, KCl and KBr described in JP-A-58-75152 and [Co (NH) described in JP-A-59-121336. ₃ )] ₆ Cl ₃ And amphoteric polymer electrolytes such as a copolymer of vinylbenzyltrimethylammonium chloride and sodium acrylate described in JP-A-56-142258, and Si, Ti and the like described in JP-A-59-75255. Organic metal surfactants, and organic boron compounds described in JP-A-59-84241 are exemplified.
[0126]
The developer and replenisher used in the present invention may further contain a preservative, a colorant, a thickener, a defoamer, a water softener, and the like, if necessary. Examples of the antifoaming agent include mineral oil, vegetable oil, alcohol, surfactant, silicone and the like described in JP-A-2-244143. As the water softener, for example, polyphosphoric acid and its sodium salt, potassium salt and ammonium salt, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, hydroxyethylethylenediaminetriacetic acid, nitrilotriacetic acid, 1,2-diaminocyclohexane Aminopolycarboxylic acids such as tetraacetic acid and 1,3-diamino-2-propanoltetraacetic acid and their sodium, potassium and ammonium salts, aminotri (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta ( Methylenephosphonic acid), triethylenetetraminehexa (methylenephosphonic acid), hydroxyethylethylenediaminetri (methylenephosphonic acid) and 1-hydro Shietan 1,1-diphosphonic acid and their sodium salts, potassium salts and ammonium salts. The optimum value of the water softener varies depending on the chelating power, the hardness of the hard water used and the amount of the hard water. The range of mass% is preferred. If the added amount is less than this range, the intended purpose is not sufficiently achieved, and if the added amount is larger than this range, adverse effects on the image area such as color omission appear. The remaining component of the developer and replenisher is water.
[0127]
(Concentrate)
Further, it is advantageous from the viewpoint of transportation that the developing solution and the replenisher used in the present invention are concentrated solutions having a smaller water content than at the time of use, and are diluted with water at the time of use. In this case, the degree of concentration is appropriately such that each component does not cause separation or precipitation, but it is preferable to add a solubilizing agent if necessary. As the solubilizing agent, a so-called hydrotrope such as toluene sulfonic acid, xylene sulfonic acid and alkali metal salts thereof described in JP-A-6-32081 is preferably used.
[0128]
The automatic developing machine used in the present invention is preferably provided with a mechanism for automatically replenishing a required amount of a replenisher to a developing bath, and preferably a mechanism for discharging a developer exceeding a certain amount is provided, Preferably, a mechanism for automatically replenishing a required amount of water to the developing bath is provided, and preferably, a mechanism for detecting passage of the photosensitive lithographic printing plate material (hereinafter, referred to as “passing through”) is provided. Is provided with a mechanism for estimating the processing area of the plate based on the detection of the printing plate, and preferably a mechanism for controlling the replenishing amount of the replenisher and / or water to be replenished based on the estimation of the processing area. And preferably a mechanism for controlling the timing of replenishment of these replenishers is provided, preferably a mechanism for controlling the temperature of the developer is provided, and preferably the pH and / or the conductivity of the developer are controlled. The mechanism to detect A mechanism for controlling the amount of replenisher and / or water to be replenished, preferably based on the pH and / or conductivity of the developer, and preferably a replenisher for these replenishers. A mechanism for controlling timing is provided.
[0129]
The automatic developing machine used in the present invention preferably has a pre-processing section for immersing the plate in a processing solution before the developing step. The pre-treatment unit is preferably provided with a mechanism for spraying a treatment liquid onto the plate surface, and is preferably provided with a mechanism for controlling the temperature of the treatment liquid to an arbitrary temperature of 25 ° C to 60 ° C, preferably A mechanism for rubbing the plate surface with a roller-shaped brush (brush roll) is provided. Water is used as the treatment liquid. Details will be described later.
(Post-processing)
After the development, the photosensitive lithographic printing plate material of the present invention may be washed with water, a rinsing solution containing a surfactant or the like, a plate surface protecting agent containing a gum arabic or a starch derivative as a main component (finisher solution, protective gum solution, Alternatively, it is simply referred to as a gum solution).
[0130]
These treatments can be used in various combinations for the post-treatment of the photosensitive lithographic printing plate material of the present invention. For example, development → washing → rinsing solution treatment containing a surfactant or development → washing → treatment with a finisher solution Is preferred.
[0131]
Further, a countercurrent multistage treatment using a rinsing liquid or a finisher liquid is also a preferred embodiment. These post-processings are generally performed using an automatic developing machine including a developing section and a post-processing section. A method of spraying the post-treatment liquid from a spray nozzle or a method of immersing and conveying the post-treatment liquid in a treatment tank filled with the treatment liquid is used. There is also known a method in which a small amount of washing water is supplied to the plate after washing and washed with water, and the waste liquid is reused as dilution water of the undiluted developer solution. Further, a so-called disposable processing method in which the processing is performed with a substantially unused processing liquid can also be applied. The planographic printing plate obtained by such a process is set on an offset printing press and used for printing.
[0132]
(Preprocessing)
In the processing method of the present invention, it is preferable to provide a pre-processing step (pre-water washing step) before the step of processing with a developer, and to wash and remove the protective layer.
[0133]
The treatment liquid (rinse water) used in the pretreatment step is preferably a liquid containing at least one selected from a chelating agent, a surfactant and a preservative, and tap water can be used as the rinse water. .
[0134]
As the chelating agent, a compound that coordinates with a metal ion to form a chelate compound can be used. Specifically, ethylenediaminetetraacetic acid, its potassium or sodium salt, triethylenetetramine hexaacetic acid, its potassium or sodium salt, diethylenetriaminepentaacetic acid, its potassium or sodium salt, hydroxyethylethylenediaminetriacetic acid, its potassium salt or Sodium salt, nitriotriacetic acid, potassium or sodium salt thereof, 1-hydroxyethane-1,1-diphosphonic acid, potassium or sodium salt thereof, aminotri (methylenephosphonic acid), potassium or sodium salt thereof, phosphonoalkanetricarboxylic acid Acids and the like. As these chelating agents, those which are organic amine salts instead of their potassium or sodium salts are also effective.
[0135]
The addition amount of the chelating agent is suitably in the range of 0.0001 to 3.0% by mass.
As the surfactant, any of anionic, nonionic, cationic and amphoteric surfactants can be used, but anionic or nonionic surfactants are preferred. The type of the preferred surfactant differs depending on the composition of the protective layer and the photosensitive layer. Generally, a surfactant which serves as a dissolution accelerator for the material of the protective layer and has low solubility of the components of the photosensitive layer is preferred.
[0136]
Examples of the anionic surfactant include fatty acid salts, abichenates, hydroxyalkanesulfonates, alkanesulfonates, dialkylsulfosuccinates, alkylbenzenesulfonates, alkylnaphthalenesulfonates, and alkylphenoxypolyoxyethylenepropylsulfonates. , Polyoxyethylene alkyl sulfophenyl ether salts, sodium N-methyl-N-oleyl taurate, disodium N-alkyl sulfosuccinate monoamides, petroleum sulfonates, sulfated castor oil, sulfated tallow oil, fatty acid alkyl esters Sulfate, alkyl sulfate, polyoxyethylene alkyl ether sulfate, fatty acid monoglyceride sulfate, polyoxyethylene styrylphenyl Ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl phenyl ether phosphates, partially saponified styrene-maleic anhydride copolymers, olefin-maleic anhydride copolymers Saponified products, formalin condensates of naphthalenesulfonate and the like.
[0137]
Nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene polystyryl phenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, glycerin fatty acid esters, and sorbitan fatty acid partial esters , Pentaerythritol fatty acid partial esters, propylene glycol monofatty acid esters, sucrose fatty acid partial esters, polyoxyethylene sorbitan fatty acid partial esters, ethylene glycol fatty acid esters, polyiglycerin fatty acid partial esters, polyoxyethylene castor oil , Polyoxyethylene glycerin fatty acid partial esters, fatty acid diethanolamides, N, N-bis-hydroxyalkylamine , Polyoxyethylene alkylamine, triethanolamine fatty acid esters, trialkylamine oxides and the like.
[0138]
The preferable addition amount of the surfactant is 0.005 to 10% by mass. Further, an antifoaming agent can be used in combination with the surfactant.
[0139]
Examples of preservatives include phenol or derivatives thereof, formalin, imidazole derivatives, sodium dehydroacetate, 4-isothiazolin-3-one derivatives, benzoisothiazolin-3-one, benzotriazole derivatives, amidizing anidine derivatives, quaternary ammonium salts, pyrazine, Derivatives such as quinoline and guanidine, diazines, triazole derivatives, oxazoles, oxazine derivatives and the like can be mentioned.
[0140]
In the treatment method of the present invention, the treatment liquid (washing water) used in the pretreatment step is preferably used for washing by controlling the temperature, and is preferably in a range of 20 to 60 ° C.
[0141]
As a cleaning method, a known processing liquid supply technique such as spraying, dipping, or coating can be used, and a brush roller, a squeezing roller, or a processing accelerating means such as a submerged shower in dipping can be used as appropriate.
[0142]
In the treatment of the present invention, a development treatment may be performed immediately after the completion of the pretreatment step, or a development step may be performed after a drying step after the pretreatment step.
[0143]
After the development step, the above-mentioned post-processing can be performed.
In the processing method of the present invention, an automatic developing machine can be suitably used. For example, it is preferable to use the automatic developing machine shown in FIG.
[0144]
This automatic developing machine includes a pre-washing tank 1, a developing tank 2 having a developing solution, a washing tank 3 having tap water, etc., A is a pre-processing section, B is a developing section, C is a post-processing section, and T is a photosensitive section. The transport path of the photosensitive lithographic printing plate material, 11 to 15 are guide rolls for transporting the photosensitive lithographic printing plate, 16 is a squeezing roll, 17 is a developing brush and the like, 18a and 18b are shower nozzles, 19a and 19b are In the pump, * 1 and * 1, and * 2 and * 2 are connected by piping in the figure.
[0145]
As described above, the photosensitive lithographic printing plate material of the present invention preferably has the photopolymerizable photosensitive layer and the protective layer of the present invention on an aluminum plate support. It is preferable to apply a processing method.
[0146]
【Example】
Hereinafter, synthesis examples, support preparation examples, and examples will be specifically described, but embodiments of the present invention are not limited thereto. In the examples, “parts” means “parts by mass” unless otherwise specified.
[0147]
<< Synthesis of polymer binder >>
(Synthesis of polymer binder 1)
In a three-necked flask under a nitrogen stream, put 12 parts of methacrylic acid, 70 parts of methyl methacrylate, 8 parts of acrylonitrile, 10 parts of ethyl methacrylate, 500 parts of ethanol and 3 parts of α, α'-azobisisobutyronitrile. The reaction was carried out in an air bath at 80 ° C. for 6 hours in an air stream. Thereafter, 3 parts of triethylammonium chloride and 2 parts of glycidyl methacrylate were added and reacted for 3 hours to obtain a polymer binder 1. The weight average molecular weight measured using GPC was about 50,000, and the glass transition temperature (Tg) measured using DSC (differential thermal analysis) was about 85 ° C.
[0148]
<< Preparation of lithographic printing plate >>
(Preparation of support)
A 0.24 mm thick aluminum plate (material 1050, tempered H16) was immersed in a 5% aqueous sodium hydroxide solution maintained at 65 ° C., subjected to a 1-minute degreasing treatment, and then washed with water. The degreased aluminum plate was immersed in a 10% hydrochloric acid aqueous solution maintained at 25 ° C. for 1 minute to neutralize, and then washed with water. Next, this aluminum plate was placed in a 0.3% by mass aqueous nitric acid solution at 25 ° C. and a current density of 100 A / dm. ² After the electrolytic surface roughening was performed with an alternating current for 60 seconds under the conditions described above, a desmut treatment was performed for 10 seconds in a 5% aqueous sodium hydroxide solution kept at 60 ° C. The surface-roughened aluminum plate subjected to desmut treatment is placed in a 15% sulfuric acid solution at 25 ° C. and a current density of 10 A / dm. ² Anodizing treatment was performed for 1 minute under the conditions of a voltage of 15 V to produce supports 1 to 8. The center line average roughness (Ra) of these surfaces was 0.65 μm.
[0149]
(Preparation of support with coated undercoat layer)
On the above-mentioned supports 1 to 8, an undercoat layer coating solution having the following composition was applied in a dry amount of 0.1 g / m 2. ² The resultant was applied with a wire bar, dried at 90 ° C. for 1 minute, and further subjected to a heat treatment at 110 ° C. for 3 minutes to prepare Substrates 1 to 8 on which an undercoat layer had been applied.
[0150]
<Undercoat layer coating liquid>
1 part of γ-methacryloxypropyltrimethoxysilane
80 parts of methyl ethyl ketone
Cyclohexanone 19 parts
(Preparation of photosensitive lithographic printing plate material)
Each of the supports 1 to 8 having the undercoat layer coated thereon was coated with a photopolymerizable photosensitive layer coating solution having the following composition in a dry coverage of 1.4 g / m 2. ² And dried at 95 ° C. for 1.5 minutes to form a photosensitive layer. Thereafter, a coating solution for a protective layer having the following composition was further applied on the photosensitive layer in a dry coverage of 2.0 g / m 2 as shown in Table 1 below. ² The resultant was coated with an applicator and dried at 75 ° C. for 1.5 minutes to prepare photosensitive lithographic printing plate materials 1 to 8 having a protective layer (oxygen blocking layer) on the photosensitive layer.
[0151]

[0152]
Embedded image

[0153]
(Protective layer coating solution)
<Protective layer coating liquid 1>
89 parts of polyvinyl alcohol (GL-03: manufactured by Nippon Synthetic Chemical Company)
Polyvinylpyrrolidone (K-30: manufactured by Tokyo Chemical Industry) 10 parts
Surfactant (F142D: manufactured by Dainippon Ink and Chemicals) 0.5 part
900 parts of water
<Protective layer coating liquid 2>
To the protective layer coating liquid 1, disodium ethylenediaminedisuccinate (1 part) was further added.
[0154]
<Protective layer coating liquid 3>
To the protective layer coating solution 1, sodium methyliminodiacetate (1 part) was further added.
[0155]
<Protective layer coating liquid 4>
To the protective layer coating solution 1, sodium β-alanine diacetate (1 part) was further added.
[0156]
<Protective layer coating liquid 5>
Sodium butylnaphthalenesulfonate (5 parts) was further added to the above-mentioned protective layer coating liquid 2.
[0157]
<Protective layer coating liquid 6>
Sodium butylnaphthalenesulfonate (5 parts) was further added to the above-mentioned protective layer coating liquid 3.
[0158]
<Protective layer coating liquid 7>
Sodium butylnaphthalenesulfonate (5 parts) was further added to the above-mentioned protective layer coating liquid 4.
[0159]
<Protective layer coating liquid 8>
To the protective layer coating liquid 1, disodium ethylenediaminetetraacetate (1 part) was further added.
[0160]
《Image formation》
The photopolymerizable photosensitive lithographic printing plate material produced as described above was subjected to image exposure at a resolution of 2540 dpi by using a CTP exposure apparatus (Tigercat: ECRM) equipped with an FD-YAG laser light source. . Note that dpi represents the number of dots per 2.54 cm. Next, a pre-processing unit (using tap water) for removing the protective layer before development, a developing unit filled with a developing solution having the following composition, and a post-processing unit (washing treatment and gum solution treatment (GW- 3: Developed using a CTP automatic developing machine (PHW23-V: manufactured by Technigraph) equipped with Mitsubishi Chemical Corp. (2-fold dilution)) to obtain planographic printing plates 1 to 8.
[0161]

《Evaluation》
Using the lithographic printing plates 1 to 8 (samples 1 to 8) prepared above, stop stain was evaluated according to the following method.
[0162]
(Stop dirt)
Each image of the lithographic printing plate produced above was applied to a printing machine (DAIYA 1F-1 manufactured by Mitsubishi Heavy Industries, Ltd.), coated paper, dampening solution (etching liquid SG-51, 1.5% concentration, manufactured by Tokyo Ink Co., Ltd.), ink (Toyo) Printing was performed using Ink Manufacturing Co., Ltd. (High Plus M Red), and after printing 5000 sheets, the printing press was temporarily stopped, and left for 1 hour to start printing. ² The fine spot-like stains generated per unit were observed with a loupe, and the number of the generated spots was counted. In addition, as a criterion for determination of fine spots, the number of occurrences is most preferably 10 or less, and if it is 11 to 29, it is a practically allowable range, and if it is 30 or more, there is a practical problem. Was determined. Table 1 shows the results.
[0163]
(Sludge)
1 L of tap water, 9 L of the developing solution in the developing tank 2 and 3 L of tap water in the washing tank 3 of the automatic developing machine shown in FIG. 1, the automatic developing machine was set, and the image was exposed. Each of the photosensitive lithographic printing plate materials 1 to 8 was developed. In the development process, the photosensitive lithographic printing plate was ² Each time the water is passed, 50 ml of tap water is supplied to the pre-washing tank 1, 50 ml of the developing solution is supplied to the developing tank 2, and 50 ml of tap water is supplied to the washing tank 3. ² 600m in 30 days ² Was developed. The processing conditions were 15 seconds for the pre-processing step, 30 seconds for the developing step, and 20 seconds for the post-processing step. After this series of treatments, the washing water in the pre-washing tank 1 was drained, and the condition of the sludge and sludge adhesion in the pre-washing tank 1 was observed. The following evaluation criteria were used. Table 1 shows the results.
[0164]
◎: Not recognized at all
：: Sludge and sludge are slightly observed, but there is no practical problem
Δ: Sludge / sludge is slightly observed, but is within a practically acceptable range.
X: Sludge and sludge are remarkably generated, the pump is clogged, and the plate is stained, which is a practical problem.
[0165]
[Table 1]

[0166]
As is apparent from Table 1, according to the present invention, stop dirt can be prevented, sludge and sludge generated during long-term treatment can be reduced, and the burden of cleaning work can be reduced.
[0167]
【The invention's effect】
Advantageous Effects of Invention According to the present invention, in continuous processing, when printing is once stopped and printing is resumed, fine spot-like stains (stop stains) generated in a non-image portion are prevented, and when processing is performed for a long time, a developing tank is prevented. A photosensitive lithographic printing plate material and a method for processing a photosensitive lithographic printing plate material, in which sludge and sludge accumulated in the pretreatment tank are reduced and the burden of cleaning work is reduced.
[Brief description of the drawings]
FIG. 1 is a schematic configuration diagram showing an example of an automatic developing machine used in an embodiment of the present invention.
[Explanation of symbols]
1 front washing tank
2 Developing tank
3 washing tank
11-15 Guide roll
16 Squeezing roll
17 Developing brush
18a, 18b shower nozzle
19a 19b pump
A Pre-processing unit
B Developing section
C Post-processing unit
T photosensitive material for lithographic printing plate

Claims (6)

Photosensitive lithographic plate having at least one layer of a monomer containing an addition-polymerizable ethylenically unsaturated bond, a photopolymerizable photosensitive layer containing a photopolymerization initiator and a polymer binder, and a protective layer on an aluminum plate support A photosensitive lithographic printing plate material, wherein the protective layer contains at least a water-soluble polymer and a compound represented by the following general formula (1).

[In the formula, A ₁ , A ₂ , A ₃ and A ₄ each represent —CH ₂ OH, —PO ₃ (M ₁ ) ₂ or —COOM, and may be the same or different. M and M ₁ each represent a hydrogen atom, an ammonium group, an alkali metal atom or an organic ammonium group. X is an alkylene group having 2 to 6 carbon atoms _- represents a _{- (B 1 O) n -B} 2. n represents an integer of 1 to 8, and B ₁ and B ₂ may be the same or different and each represents an alkylene group having 1 to 5 carbon atoms. ] Photosensitive lithographic plate having at least one layer of a monomer containing an addition-polymerizable ethylenically unsaturated bond, a photopolymerizable photosensitive layer containing a photopolymerization initiator and a polymer binder, and a protective layer on an aluminum plate support A photosensitive lithographic printing plate material, wherein the protective layer contains at least a water-soluble polymer and an N-alkyl-substituted N-substituted iminodiacetic acid having 1 to 3 carbon atoms or a salt thereof. . Photosensitive lithographic plate having, on an aluminum plate support, at least one photopolymerizable photosensitive layer containing an addition-polymerizable ethylenically unsaturated bond-containing monomer, a photopolymerization initiator and a polymer binder, and a protective layer. A photosensitive lithographic printing plate material, wherein the protective layer contains at least a water-soluble polymer and a compound represented by the following general formula (2).

Wherein, X, Y, Z are each _-CH 2 -, - representing the or -CHOH- - _{(CH 2)} 2. N represents 0 or 1 in each case. ] 2. A method for processing a photosensitive lithographic printing plate material according to claim 1, wherein the photosensitive lithographic printing plate material according to claim 1 is image-exposed, the protective layer is washed away in a washing step, and then developed. 3. A method for processing a photosensitive lithographic printing plate material according to claim 2, wherein the photosensitive lithographic printing plate material according to claim 2 is image-exposed, the protective layer is washed away in a water washing step, and then developed. 4. A method for processing a photosensitive lithographic printing plate material according to claim 3, wherein the photosensitive lithographic printing plate material is subjected to image exposure, the protective layer is washed away in a water washing step, and then developed.

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