JP2005025030A - Method for processing photosensitive lithographic printing plate material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for processing a photosensitive lithographic printing plate material by which dirt in the form of minute spots (stop dirt) can be prevented, the dirt appearing in a non-image part when the printing process is restarted after the operation of the printing machine is temporarily stopped for registering, a break or the like, and by which sludge accumulating in a developing tank during long-term development can be decreased and the cleaning work can be decreased. <P>SOLUTION: The method for processing a photosensitive lithographic printing plate material is carried out by developing a photosensitive lithographic printing plate material with an alkaline aqueous developing solution containing a silicate by 0 to 0.1% in terms of SiO<SB>2</SB>mass and containing a specified surfactant, the plate material having a photosensitive layer of a photopolymerizable photosensitive resin composition containing a monomer having an ethylenically unsaturated bond, a photopolymerization initiator and a polymer binder on an aluminum plate supporting body. The surface of the aluminum supporting body before the photosensitive layer is applied has 5 to 20 atomic% silicon atoms. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

【０１０４】
本発明に係る化合物Ｃは、現像液中に０．０１〜５質量％の範囲で使用することが好ましい。さらに、１〜３質量％の範囲で使用することがなお好ましい。
【０１０５】
また、上記した化合物Ｃにおいて、疎水基の分子量が小さすぎると感光性平版印刷版材料の感光層の現像時での溶解能力が低下し、スラッジ、ヘドロの発生が抑制しにくくなり、一方、疎水基の分子量が大きすぎると、これら化合物の現像液への溶解性が悪くなり均一な現像液を作製・維持しにくくなることから、上記した範囲が好ましい。
【０１０６】
（化合物Ａ）
本発明に係る化合物Ａは、疎水基部分の飽和アルキル基（但し、ポリオキシアルキレン基部分のアルキレン基は含まない）の分子量が、疎水基全体の分子量の０〜２５％であるポリオキシエチレン基を含有するアニオン性界面活性剤を指し、該疎水基全体の分子量の０以上５％以下であるものが好ましい。２５％を越えると、現像した感光性平版印刷版材料から溶出した成分を効果的に溶解することができず、現像液中にスラッジ沈殿を生じやすくなる。
【０１０７】
ここで、「飽和アルキル基の分子量が、疎水基全体の分子量の０〜２５％である」とは、上記化合物Ｃにおいて述べたと同様であり、この場合において、本発明に係る化合物Ａは、幾つかの疎水基を分子が有する場合に、各疎水基が平均して「飽和アルキル基の分子量が、疎水基全体の分子量の０〜２５％である」ことが好ましいが、各疎水基が平均して上記の範囲にないものも有用である。
【０１０８】
また、疎水基の元素についての合計した分子量は、ある程度の大きさを有することが好ましく、分子量が１２０以上２０００以下程度のものが好ましい。
【０１０９】
次に、本発明に係る化合物Ａに係る好ましい例を挙げるが、本発明においては、これらに限定されるものではない。
【０１１０】
【化２】

【０１１１】
本発明に係る化合物Ａは、現像液中に０．０１〜５質量％の範囲で使用することが好ましい。さらに、１〜３質量％の範囲で使用することがなお好ましい。
【０１１２】
また、上記した化合物Ａにおいて、疎水基の分子量が小さすぎると感光性平版印刷版材料の感光層の現像時での溶解能力が低下し、スラッジ、ヘドロの発生が抑制しにくくなり、一方、疎水基の分子量が大きすぎると、これら化合物の現像液への溶解性が悪くなり均一な現像液を作製・維持しにくくなることから、上記した範囲が好ましい。
【０１１３】
（本発明に係る化合物Ｂ）
本発明に係る化合物Ｂは、前記一般式（Ｂ）で表される非イオン性界面活性剤であり、一般式（Ｂ）において、Ｒ_１は置換基を有してもよいアルキル基または置換基を有してもよいアリール基を表す。ｍは１〜３の整数を表し、ｎは２〜３０の整数を表す。
【０１１４】
Ｒ_１で表される置換基を有してもよいアルキル基のアルキル基としては、メチル基、エチル基、ｔ−ブチル基等炭素数１〜２０個までのものを好ましく用いることができ、Ｒ_１で表される置換基を有してもよいアリール基としてはフェニル基、ナフチル基等炭素数１〜１０個までのものを好ましく使用することができる。
【０１１５】
以上のアルキル基、アリール基は置換基を有していても良く、置換基としては、例えば、フッ素原子、塩素原子、臭素原子等のハロゲン原子、エトキシカルボニル基等のアルコキシカルボニル基、メトキシ基、エトキシ基等のアルコキシ基、フェニル基等のアリール基、シアノ基等を挙げることができる。
【０１１６】
化合物Ｂは、疎水基部分（Ｒ_１）の分子量はある程度大きいことが好ましく、７０以上であることが好ましい。特に好ましいのはナフチル基、ベンジル基、炭素数８〜１２のアルキル基である。疎水基の割合が小さいと感光層の溶解性が悪くスラッジを生じる。本化合物は添加量が少ないと感光層の溶解性が悪くスラッジを生じる。多すぎると発泡性が大きくなりすぎたり、感光層の膜減りが発生したりする為、好ましくない。
【０１１７】
化合物Ｂのポリオキシプロピレンの部分（Ｃ_３Ｈ_６Ｏ）_ｎは、（ＣＨ_２ＣＨ_２ＣＨ_２Ｏ）_ｎ、（ＣＨ（ＣＨ_３）ＣＨ_２Ｏ）_ｎ、（ＣＨ_２ＣＨ（ＣＨ_３）Ｏ）_ｎの３種類があり、どの構造でもかまわないが、（ＣＨ_２ＣＨ（ＣＨ_３）Ｏ）_ｎの構造が最も好ましい。ｍの値は１〜３であり、２または３であることが最も好ましい。ｎの値は２〜３０であり、５〜３０であることが最も好ましい。ｎ／ｍは、５以上２０以下の範囲が最も好ましい。ｎ，ｍ，ｍ／ｎの各値は大きすぎても小さすぎても活性剤の親水基と疎水基のバランスを崩してしまい、スラッジの低減、現像性の劣化を生じてしまう。
【０１１８】
本発明に係る化合物Ｂの具体例を下記に示すが、これらに限定されるものではない。
【０１１９】
【化３】

【０１２０】
【化４】

【０１２１】
【化５】

【０１２２】
本発明に係る化合物Ｂは、現像液中に０．０１〜５質量％の範囲で使用することが好ましい。さらに、１〜３質量％の範囲で使用することがなお好ましい。
【０１２３】
また、上記した化合物Ｂにおいて、疎水基の分子量が小さすぎると感光性平版印刷版材料の感光層の現像時での溶解能力が低下し、スラッジ、ヘドロの発生が抑制しにくくなり、一方、疎水基の分子量が大きすぎると、これら化合物の現像液への溶解性が悪くなり均一な現像液を作製・維持しにくくなることから、上記したものが好ましい。
【０１２４】
現像液中に含まれる溶解した感光層成分の析出が起こる為、ｐＨ依存性が低いポリオキシアルキレン基を含有する界面活性剤を現像液に添加することが好ましい。また、アリール基等の不飽和系の疎水基を有する界面活性剤は、溶解した感光層成分の可溶化力が高くより好ましい。
【０１２５】
使用する現像液のｐＨは、１１．０〜１２．５未満の範囲であることが好ましい。
【０１２６】
本発明に係る現像液は、アルカリ剤、界面活性剤、現像安定化剤等を含有することが好ましく、その他の添加剤を含有していても構わない。
【０１２７】
（アルカリ剤）
本発明の処理方法に用いられる現像液および補充液の主成分は、燐酸、炭酸、硼酸、フェノール類、糖類、オキシム類およ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。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。これらのうちフェノール類、糖類、オキシム類およ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（同１３．０）、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。
【０１２８】
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られる。かかる非還元糖とは、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およ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、何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、ズリシットおよ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およ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（同１２．４５）、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、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。
【０１２９】
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。この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、また原価アップの問題が出てくる。これらの酸に組み合わせる塩基としては、水酸化ナトリウム、同アンモニウム、同カリウムおよ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。現像液のｐＨが８．５以下の場合、このような現像液で現像可能な感光性平版印刷版材料から得られる印刷版の画像部は物理的に脆弱であり、印刷中の摩耗が早く十分な耐刷力が得られない。また、その画像部は化学的にも弱く、印刷中にインキ洗浄溶剤やプレートクリーナー等で拭いた部分の画像がダメージを受け、その結果、十分な耐薬品性が得られない。ｐＨが１３．０を越える様な高ｐＨの現像液は皮膚や粘膜へ付着した場合の刺激性が強く、取扱いには十分な注意を必要とし好ましくない。
【０１３０】
その他として、例えば、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、硼酸カリウム、硼酸ナトリウム、硼酸リチウム、硼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、同カリウムおよび同リチウムを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。
【０１３１】
尚、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。
【０１３２】
（界面活性剤）
本発明に用いられる現像液および補充液には、現像性の促進や現像カスの分散およ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。界面活性剤としては、公知のアニオン系界面活性剤、カチオン系界面活性剤、ノニオン系界面活性剤、両性界面活性剤、フッソ系界面活性剤、高分子界面活性剤等が挙げられる。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。
【０１３３】
（現像安定化剤）
本発明に用いられる現像液および補充液には、好ましくは種々現像安定化剤が用いられる。それらの好ましい例として、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およ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が好ましい例として挙げられる。更には、特開昭５０−５１３２４号公報記載のアニオン界面活性剤または両性界面活性剤、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がある。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号公報の酸またはアルコールに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が挙げられる。
【０１３４】
（有機溶剤）
現像液および現像補充液には更に必要により有機溶剤が加えられる。かか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および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および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％であるが、実質的に含まれないことが好ましく、全く含まれないことが特に好ましい。ここで実質的に含まれないとは１質量％以下であることを示す。
【０１３５】
（還元剤）
本発明に用いられる現像液およ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材料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、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、亜硫酸、亜硫酸水素酸、亜リン酸、亜リン酸水素酸、亜リン酸二水素酸、チオ硫酸およ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好ましくは、０．０５〜５質量％の範囲で含有される。
【０１３６】
（有機カルボン酸）
本発明に用いられる現像液およ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およ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、パルミチン酸およ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、枝分かれ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。上記脂肪族およ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また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。
【０１３７】
（その他）
本発明に用いられる現像液および補充液には現像性能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号公報記載の有機硼素化合物等が挙げられる。本発明に用いられる現像液および補充液には更に必要に応じて、防腐剤、着色剤、増粘剤、消泡剤およ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、ポリ燐酸およびそのナトリウム塩、カリウム塩およびアンモニウム塩、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、エチレンジアミンジコハク酸、メチルイミノジ酢酸、βアラニンジ酢酸、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および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およびそれらのナトリウム塩、カリウム塩およびアンモニウム塩、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）および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、カリウム塩およ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およ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％、より好ましくは０．０１〜０．５質量％の範囲である。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。現像液および補充液の残余の成分は水である。得られた現像液の電導度は３〜１００ｍＳ、表面張力は２０〜８０ｄｙｎｅ／ｃｍの範囲であることがより好ましい。
【０１３８】
特開平１１−６５１２９号、特開平１１−６５１２６号、特開２０００−２０６７０６号、特開２０００−８１７１１号、特開２００２−９１０１６号、特開２００２−１７４９０７号、特開２００２−１８２４０１号、特開２００２−１９６５０６号、特開２００２−１９６５０７号、特開２００２−２０２６１６号、特開２００２−２２９１８７号、特開２００２−２０２６１５号、特開２００２−２５１０１９号、特開２００２−３６５８１３，特開２００３−２９４２７号、特開２００３−２１９０８号、特開２００３−１５３１８号、特開２００３−３５９６０号、特開２００３−４３６９３号、特開２００３−４３７０１号、特開２００３−４３７０２号、特開２００３−５７８４９号、特開２００３−６６６２２等に記載されている現像液の素材、版面保護剤等の処理剤およびその素材、自動現像機等についても好適に用いることができる。
【０１３９】
（濃縮液）
本発明に用いられる現像液およ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。かかる可溶化剤としては、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およ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。
【０１４０】
濃縮液の水の含有量をさらに減らし、固形状もしくはペースト状にすることもできる。この場合、一旦現像液にしてから蒸発乾固しても良いが、好ましくは複数の素材を混ぜ合わせる際に水を加えず、または少量の水を加える方法で素材を混ぜ合わせることで濃縮状態とする方法が好ましい。また、この現像液濃縮物は、特開昭５１−６１８３７号、特開平２−１０９０４２号、特開平２−１０９０４３号、特開平３−３９７３５号、特開平５−１４２７８６号、特開平６−２６６０６２号、特開平７−１３３４１等に記載された従来よく知られた方法にて顆粒状、錠剤とすることができる。固形状もしくはペースト状の現像液濃縮物に含まれる素材は、通常の感光性平版印刷版材料の現像液に用いられる成分を使用することができるが、水で希釈してももとに戻らないものは含まない方が好ましい。たとえば、珪酸塩は水分が低くなると石化し水に溶けにくくなるので、珪酸塩の代わりに後述の炭酸塩、燐酸塩、有機酸塩等を含むことが好ましい。
【０１４１】
これらの現像液の濃縮液もしくは固形状もしくはペースト状の濃縮物は、素材種や素材配合比等の異なる複数のパートに分けても良い。これらの濃縮した現像液濃縮物は、現像前に水で所定の濃度に希釈した後現像に使用することが好ましい。またこの現像液濃縮液または濃縮物を現像補充液として用いる場合は、所定の濃度に水で希釈した後、使用中の現像液に投入することが最も好ましいが、所定の濃度より濃い濃度や、所定の濃度に希釈せずそのまま使用中の現像液に投入することも可能である。所定の濃度より濃い濃度や、所定の濃度に希釈せずそのままで現像液濃縮物を使用中の現像液に投入する際は、同じタイミングまたは別のタイミングで使用中の現像液に直接別途に水を添加しても良い。
【０１４２】
（自動現像機）
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、通版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、好ましくは通版の検知および／または処理面積の推定をもとに補充しようとする補充液および／または水の補充量および／または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および／また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および／または電導度をもとに補充しようとする補充液および／または水の補充量および／または補充タイミングを制御する機構が付与されている。また、現像工程後に水洗工程がある場合、使用後の水洗水を現像濃縮液、現像補充液の濃縮液の希釈水として用いることができる。
【０１４３】
本発明に用いる自動現像機は、現像工程の前に前処理液に版を浸漬させる前処理部を有してもよい。この前処理部は、好ましくは版面に前処理液をスプレーする機構が付与されており、好ましくは前処理液の温度を２５℃〜５５℃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により擦る機構が付与されている。またこの前処理液としては、水などが用いられる。
【０１４４】
本発明に用いられる自動現像機は、現像液の水の蒸発分を補うため、水を補充する機能を持つことが好ましい。自動現像機に濃縮現像液を希釈する為の水供給機構があればそれを用いてもよい。水の補充量は時間あたりで決められた水を補充する方法がもっとも簡便で好ましいが、現像液のｐＨ、電動度等のセンサーからの測定値から水補充量を補正してもよい。また、外気の気温および／または湿度、現像液の温度、自動現像機内の空気の温度および／または湿度等を用いての水の補充量に補正をしてもよい。
【０１４５】
また、アルカリ性の現像液が空気中の炭酸ガスを吸収することによる現像液のｐＨの低下や、現像液中の水分の蒸発による現像液の濃縮を防ぐため、現像液液面はできるだけ小さいことが好ましい。浮き蓋等による現像液面の遮蔽は高い効果が得られる。また、自現機内の空気と外部の空気の接触を制限することも有効な方法である。自現機の版材の出入り口は可能な限り小さく、また版材の通過時のみ開口する自動の開閉機構があると好ましい。また、自現機内の空気中の炭酸ガスを除去する方法も効果があり、アルカリ性水溶液やアルカリ性の現像液廃液を自現機内の空気と接触させ、炭酸ガスを除去する方法も有効に使用できる。
【０１４６】
（後処理）
かかる組成の現像液で現像処理された版は水洗水、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フィニッシャーや保護ガム液で後処理を施される。本発明のＰＳ版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、現像後→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リンス液やフィニッシャー液の疲労が少なく好ましい。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。このような自動処理においては、各処理液に処理量や稼働時間等に応じてそれぞれの補充液を補充しながら処理することができる。また、実質的に未使用の後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、多数枚の印刷に用いられる。
【０１４７】
（ガム液）
ガム液は現像液のアルカリ成分除去のため酸や緩衝剤を添加することが好ましく、その他に親水性高分子化合物、キレート剤、潤滑剤、防腐剤及び可溶化剤等を添加することができる。ガム液に親水性高分子化合物を含む場合は現像後の版の傷や汚れを防ぐ保護剤としての機能も付加される。
【０１４８】
本発明に用いられるガム液中に界面活性剤を添加することにより塗布層の面状等が良化する。使用できる界面活性剤としてはアニオン界面活性剤及び／又はノニオン界面活性剤が挙げられる。例えば、アニオン型界面活性剤としては、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、ジアルキルスルホコハク酸塩類、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、ポリオキシエチレンアリールエーテルスルホン酸塩、ポリオキシエチレンナフチルエーテルスルホン酸塩、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ニナトリウム塩類、石油スルホン酸塩類、硝酸化ヒマシ油、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、アルキル硝酸エステル塩類、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。これらの中でもジアルキルスルホコハク酸塩類、アルキル硫酸エステル塩類及びアルキルナフタレンスルホン酸塩類が特に好ましく用いられる。
【０１４９】
又、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アリールエーテル類、ポリオキシエチレンナフチルエーテル、ポリオキシエチレンポリスチリルフェニルエーテル、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、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、ショ糖脂肪酸部分エステル、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、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等が挙げられる。その中でも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エキシプロピレンアルキルエーテル、ポリオキシエチレン−ポリオキシプロピレンブロックポリマー類等が好ましく用いられる。又、弗素系、シリコン系のアニオン、ノニオン界面活性剤も同様に使用することができる。これら界面活性剤は２種以上併用することもできる。例えば互いに異なる２種以上を併用することもできる。例えば互いに異なる２種以上のアニオン界面活性剤の併用やアニオン界面活性剤とノニオン界面活性剤の併用が好ましい。上記界面活性剤の使用量は特に限定する必要はないが、好ましくは後処理液の０．０１〜２０質量％である。
【０１５０】
本発明に用いられるガム液には、上記成分の他必要により湿潤剤として多価アルコール、アルコール及び脂肪族炭化水素を用いることができる。
【０１５１】
多価アルコールの内、好ましい具体例としては、エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、テトラエチレングリコール、ポリエチレングリコール、グリセリン、ソルビトール等が挙げられ、アルコールとしては、プロピルアルコール、ブチルアルコール、ペンタノール、ヘキサノール、ヘプタノール、オクタノール等のアルキルアルコール、ペンジルアルコール、フェノキシエタノール及びフェニルアミノエチルアルコール等の芳香環を有するアルコールが挙げられる。これらの湿潤剤の含有量は、組成物中に０．１〜５０質量％、より好ましくは０．５〜３．０質量％が適当である。
【０１５２】
又、皮膜形成性を向上させる目的で種々の親水性高分子を含有することができる。
【０１５３】
この様な親水性高分子としては従来よりガム液に使用し得るとされるものであれば好適に使用できる。例えば、アラビアガム、繊維素誘導体（例えば、カルボキシメチルセルロース、カルボキシエチルセルロース、メチルセルロース等）及びその変性体、ポリビニルアルコール及びその誘導体、ポリビニルピロリドン、ポリアクリルアミド及びその共重合体、ビニルメチルエーテル／無水マレイン酸共重合体、酢酸ビニル／無水マレイン酸共重合体、スチレン／無水マレイン酸共重合体等が挙げられる。
【０１５４】
本発明に用いられるガム液は、一般的には酸性領域ｐＨ３〜６の範囲で使用する方が有利である。ｐＨを３〜６にするためには一般的には後処理液中に鉱酸、有機酸又は無機塩等を添加して調節する。その添加量は０．０１〜２質量％が好ましい。例えば鉱酸としては硝酸、硫酸、リン酸及びメタリン酸等が挙げられる。
【０１５５】
又、有機酸としては、クエン酸、酢酸、蓚酸、マロン酸、ｐ−トルエンスルホン酸、酒石酸、リンゴ酸、乳酸、レブリン酸、フィチン酸及び有機ホスホン酸等が挙げられる。更に無機塩としては、硝酸マグネシウム、第１リン酸ナトリウム、第２リン酸ナトリウム、硫酸ニッケル、ヘキサメタン酸ナトリウム、トリポリリン酸ナトリウム等が挙げられる。鉱酸、有機酸又は無機塩等の少なくとも１種もしくは２種以上を併用してもよい。
【０１５６】
本発明に用いられるガム液には、防腐剤、消泡剤等を添加することができる。
例えば防腐剤としてはフェノール又はその誘導体、ｏ−フェニルフェノール、ｐ−クロロメタクレゾール、ヒドロキシ安息香酸アルキルエステル、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、ベンズ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、ピリジン、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。好ましい添加量は、細菌、カビ、酵母等に対して、安定に効力を発揮する量であって、細菌、カビ、酵母の種類によっても異なるが、使用時の版面保護剤に対して０．０１〜４質量％の範囲が好ましく、又種々のカビ、殺菌に対して効力のある様に２種以上の防腐剤を併用することが好ましい。又、消泡剤としてはシリコン消泡剤が好ましい。その中で乳化分散型及び可溶化等が何れも使用できる。好ましくは使用時のガム液に対して０．０１〜１．０質量％の範囲が最適である。
【０１５７】
更にキレート化合物を添加してもよい。好ましいキレート化合物としては、例えば、エチレンジアミンテトラ酢酸、そのカリウム塩、そのナトリウム塩；ジエチレントリアミンペンタ酢酸、そのカリウム塩、そのナトリウム塩；トリエチレンテトラミンヘキサ酢酸、そのナトリウム塩；エチレンジアミンジコハク酸、そのカリウム塩、そのナトリウム塩；トリエチレンテトラミンヘキサ酢酸、そのカリウム塩、そのナトリウム塩、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、そのナトリウム塩：ニトリロトリ酢酸、そのナトリウム塩；１−ヒドロキシエタン−１，１−ジホスホン酸、そのカリウム塩、そのナトリウム塩；アミノトリ（メチレンホスホン酸）、そのカリウム塩、そのナトリウム塩等の様な有機ホスホン酸類或いはホスホノアルカントリカルボン酸類を挙げることが出来る。上記キレート剤のナトリウム塩、カリウム塩の代わりに有機アミンの塩も有効である。これらキレート剤はガム液組成中に安定に存在し、印刷性を阻害しないものが選ばれる。添加量としては使用時のガム液に対して０．００１〜１．０質量％が適当である。
【０１５８】
上記成分の他、必要により感脂化剤も添加することができる。例えばテレピン油、キシレン、トルエン、ローヘプタン、ソルベントナフサ、ケロシン、ミネラルスピリット、沸点が約１２０℃〜約２５０℃の石油留分等の炭化水素類、例えばジブチルフタレート、ジヘブチルフタレート、ジ−ｎ−オクチルフタレート、ジ（２−エチルヘキシル）フタレート、ジノニルフタレート、ジデシルフタレート、ジラウリルフタレート、ブチルベンジルフタレート等のフタル酸ジエステル剤、例えばジオクチルアジペート、ブチルグリコールアジペート、ジオクチルアゼレート、ジブチルセバケート、ジ（２−エチルヘキシル）セバケート、ジオクチルセバケート等の脂肪族二塩基酸エステル類、例えばエポキシ化大豆油等のエポキシ化トリグリセリド類、例えばトリクレジルフォスフェート、トリオクチルフォスフェート、トリスクロルエチルフォスフェート等のリン酸エステル類、例えば安息香酸ベンジル等の安息香酸エステル類等の凝固点が１５℃以下で、１気圧下での沸点が３００℃以上の可塑剤が含まれる。
【０１５９】
更にカプロン酸、エナント酸、カプリル酸、ヘラルゴン酸、カプリン酸、ウンデシル酸、ラウリン酸、トリデシル酸、ミリスチン酸、ペンタデシル酸、パルミチン酸、ヘプタデシル酸、ステアリン酸、ノナデカン酸、アラキン酸、ベヘン酸、リグノセリン酸、セロチン酸、ヘプタコサン酸、モンタン酸、メリシン酸、ラクセル酸、イソ吉草酸等の飽和脂肪酸とアクリル酸、クロトン酸、イソクロトン酸、ウンデシレン酸、オレイン酸、エライジン酸、セトレイン酸、ニルカ酸、ブテシジン酸、ソルビン酸、リノール酸、リノレン酸、アラキドン酸、プロピオール酸、ステアロール酸、イワシ酸、タリリン酸、リカン酸等の不飽和脂肪酸も挙げられる。より好ましくは５０℃において液体である脂肪酸であり、更に好ましくは炭素数が５〜２５であり、最も好ましくは炭素数が８〜２１である。これらの感脂化剤は１種もしくは２種以上併用することもできる。使用量として好ましい範囲はガムの０．０１〜１０質量％、より好ましい範囲は０．０５〜５質量％である。
【０１６０】
上記の様な感脂化剤は、ガムを乳化分散型としておき、その油相として含有させてもよく、又可溶化剤の助けを借りて可溶化してもよい。
【０１６１】
本発明において、ガム液の固型分濃度は５〜３０ｇ／ｌが好ましい。ガム膜厚量は自現機のスクイズ手段の条件で制御できる。本発明において、ガム塗布量は１〜１０ｇ／ｍ^２が好ましい。ガム塗布量は１０を越えると、短時間で乾燥するためには、版面を非常に高温にする必要があり、コスト上、安全上不利であり、また本発明の効果が十分に得られない。１ｇ／ｍ^２を下回ると、均一塗布が難しくなり、安定した処理性が得られない。
【０１６２】
本発明において、ガム液の塗布終了から乾燥開始までの時間は３秒以下であることが好ましい。更に好ましくは２秒以下であり、この時間が短いほどインキ着肉性が向上する。
【０１６３】
本発明において、乾燥時間は１〜５秒が好ましい。
本発明において、乾燥方式としては、温風ヒーター、遠赤外線ヒーターなど公知の乾燥方式を用いることができる。
【０１６４】
乾燥工程では、ガム液中の溶媒が乾燥される必要がある。そのために十分な、乾燥温度とヒーター容量を確保する必要がある。乾燥に必要な温度は、ガム液の成分によって異なるが、溶媒が水であるガム液の場合は、通常乾燥温度は５５℃以上であることが好ましい。ヒーター容量は乾燥温度よりも重要で有る場合が多く、その容量は温風乾燥方式の場合は２．６ｋＷ以上が好ましい。容量は大きい程よいが、コストとのバランスで２．６〜７ｋＷが好ましい。
【０１６５】
（現像前水洗水）
本発明において、現像前の洗浄工程で用いる洗浄液は通常水であるが、必要に応じて以下の添加剤を加えることができる。
【０１６６】
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。エチレンジアミンテトラ酢酸、そのカリウム塩、そのナトリウム塩、エチレンジアミンジコハク酸、そのカリウム塩、そのナトリウム塩、トリエチレンテトラミンヘキサ酢酸、そのカリウム塩、そのナトリウム塩、ジエチレントリアミンペンタ酢酸、そのカリウム塩、そのナトリウム塩、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、そのナトリウム塩、ニトリオトリ酢酸、そのカリウム塩、そのナトリウム塩、１−ヒドロキシエタン−１，１−ジホスホン酸、そのカリウム塩、そのナトリウム塩、アミノトリ（メチレンホスホン酸）、そのカリウム塩、そのナトリウム塩、ホスホノアルカントリカルボン酸、エチレンジアミンジコハク酸、そのカリウム塩、そのナトリウム塩等が挙げられる。これらのキレート剤はカリウム塩及びナトリウム塩の代わりに有機アミン塩を有するものも有効である。
【０１６７】
キレート剤の添加量は０〜３．０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何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オーバーコート層や感光層の組成によって異なり、一般にオーバーコート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。
【０１６８】
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。
【０１６９】
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、ショ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。
【０１７０】
界面活性剤の好ましい添加量は０〜１０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。
【０１７１】
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。好ましい例としては、１，２ベンゾイソチアゾリンー３−オン、ｏ−フェニルフェノール、ヒドロキシ安息香酸エチルエステル、クロロクレゾール等が挙げられる。
【０１７２】
本発明の洗浄方法において、現像前洗浄に用いる洗浄液は温度を調節して用いることが好ましく、該温度は１０〜６０℃の範囲が好ましい。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、適宜ブラシや絞りロール、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。
【０１７３】
本発明において、現像前洗浄工程終了後直ちに現像処理を行ってもよく、また、現像前洗浄工程の後に乾燥させてから現像処理を行ってもよい。現像工程の後は、水洗、リンス、ガム引き等公知の後処理を行うことができる。一度以上使用した現像前水洗水は、現像後の水洗水やリンス液、ガム液、現像液の一部もしくは全部として再使用することができる。
【０１７４】
【実施例】
以下、実施例を挙げて本発明を具体的に説明するが、本発明の実施の態様はこれに限定されない。尚、実施例における「部」は、特に断りない限り「質量部」を表す。
【０１７５】
実施例１
（バインダーの合成）
（アクリル系共重合体１の合成）
窒素気流下の三ツ口フラスコに、メタクリル酸３０部、メタクリル酸メチル５０部、メタクリル酸エチル２０部、イソプロピルアルコール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、イソプロピルアルコールの沸点で１時間還流を行った後、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２５部を加えて３時間反応させ、アクリル系共重合体１を得た。ＧＰＣを用いて測定した重量平均分子量は約３５，０００、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。
［支持体１〜４の作製］
（支持体１の作製）
厚さ０．３ｍｍ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、更に８２℃の１．１質量％珪酸カリウム水溶液（ＳｉＯ_２：２６質量％、Ｋ_２Ｏ：１３．５質量％）で処理を行って支持体１を作製した。
【０１７６】
（支持体２の作製）
厚さ０．３ｍｍ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、更に８２℃の１．２％ポリビニルホスホン酸カリウム水溶液で処理を行って支持体２を作製した。
【０１７７】
（支持体３の作製）
厚さ０．３ｍｍ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、更に８０℃の０．６質量％珪酸カリウム水溶液（ＳｉＯ_２：２６質量％、Ｋ_２Ｏ：１３．５質量％）で処理を行い、続けて、０．８質量％のポリビニルホスホン酸水溶液で８４℃で親水化処理を行って支持体３を作製した。
【０１７８】
（支持体４の作製（比較例））
厚さ０．３ｍｍ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、更に７５℃の熱水で親水化処理を行って支持体４を作製した。
【０１７９】
【表１】

【０１８０】
［感光性平版印刷版材料１０１〜１０４の作製］
上記支持体１〜４上に、下記組成の光重合性感光層塗工液１を乾燥時１．５ｇ／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、光重合性感光層を有する光重合性感光層塗布試料を各々得た。
【０１８１】

（※１）アクリル系共重合体１の合成
窒素気流下の三ツ口フラスコに、メタクリル酸３０部、メタクリル酸メチル５０部、メタクリル酸エチル２０部、イソプロピルアルコール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、イソプロピルアルコールの沸点で１時間還流を行った後、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２５部を加えて３時間反応させ、アクリル系共重合体１を得た。ＧＰＣを用いて測定した重量平均分子量は約３５，０００、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。
【０１８２】
【化６】

【０１８３】
尚、Ｍ−３：Ｎ−ｎ−ブチルジエタノールアミン（１モル）、１，３−ビス（１−イソシアナート−１−メチルエチル）ベンゼン（２モル）、２−ヒドロキシプロピレン−１−メタクリレート−３−アクリレート（２モル）の反応生成物（一般記載中に記載あり。）
上記光重合性感光層塗布試料の各々の上（光重合性感光層の上）に、下記組成の酸素遮断層塗工液を乾燥時１．８ｇ／ｍ^２になるようになるようアプリケーターで塗布し、７５℃で１．５分間乾燥して、光重合性感光層上に酸素遮断層を有する感光性平版印刷版材料１０１〜１０４を作製した。
【０１８４】

［感光性平版印刷版材料１０５の作製］
光重合性感光層塗工液１を下記の光重合性感光層塗工液２に変更した以外は、感光性平版印刷版材料１０３と同様にして感光性平版印刷版材料１０５を作製した。
【０１８５】

【０１８６】
【化７】

【０１８７】
［感光性平版印刷版材料１０６の作製］
光重合性感光層塗工液１の分光増感色素Ｄ−１、Ｄ−２をＤ−５、Ｄ−７に変更（使用量は同じ）した（光重合性感光層塗工液３とする）以外は、感光性平版印刷版材料１０３と同様にして感光性平版印刷版材料１０６を作製した。
【０１８８】
【化８】

【０１８９】
感光性平版印刷版材料１０１〜１０４、１０５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２４００ｄｐｉ（ｄｐｉとは２．５４ｃｍ当たりのドット数を表す）の解像度で画像露光（露光パターンは、１００％画像部と、１７５ｌｐｉ（ｌｐｉとは２．５４ｃｍ当たりの線数を表す）５０％のスクエアードットを使用した）を行った。
【０１９０】
また、感光性平版印刷版材料１０６について、４０８ｎｍ、３０ｍＷ出力のレーザーを備えた光源を備えたプレートセッター（タイガーキャット：ＥＣＲＭ社製改造品）を用いて同様の画像露光を行った。
【０１９１】
次いで、現像前に酸素遮断層を除去する前水洗部、下記の現像液を充填した現像部、版面に付着した現像液を取り除く水洗部、画線部保護のための上記のガム液を備えたＣＴＰ自動現像機（ＰＨＷ３２−Ｕ：Ｔｅｃｈｎｉｇｒａｐｈ社製）を用い、画像部、非画像部の面積比率が、１：９になるよう現像処理を５００ｍ^２実施した。約５０ｍｌ／ｍ^２となるように下記現像補充液を補充して現像液の補充を実施した。
【０１９２】
［現像液、現像補充液の作製］
下記の現像液、現像補充液を作製した。
【０１９３】

【０１９４】
【化９】

【０１９５】

［現像液、現像補充液の作製］
下記処方のガム液（フィニッシャー液（版面保護剤））を作製した。
【０１９６】

［評価方法］
（アルミニウム板支持体表面のケイ素原子濃度及びリン原子濃度（原子％））得られた支持体（アルミニウム板支持体）の表面のケイ素原子量濃度及びリン原子濃度（原子％）を、リガク社製走査型蛍光Ｘ線分析装置ＺＳＸ−１００ｅにより測定した。
【０１９７】
（ストップ汚れ）
感光性平版印刷版材料を、自動現像機で５００ｍ^２処理後の状態で現像実施して得られた平版印刷版を、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（東洋インキ社製のＶＯＣゼロインキ“ＴＫハイエコーＳＯＹ１”）を使用して印刷を行い、この印刷に使用した平版印刷版を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再開始し、さらに１００枚印刷した後印刷物上に発生した微点状の汚れを１００ｃｍ^２内の個数で評価した。該微点状の汚れが１０個以下であれば良好。３０個以上であれば実用上問題である。
（良好は１０個以下。問題は３０個以上。）
（スラッジヘドロの評価）
自動現像機で５００ｍ^２処理後の現像終了後の槽内のスラッジヘドロの量を確認した。
【０１９８】
○：現像槽内にわずかにスラッジへドロの発生が見られるが、現像される感光性平版印刷版材料また現像された平版印刷版には付着せず実質上問題はない。また現像槽の清掃作業は水で流す程度で対応可能
△：現像槽内にスラッジへドロ発生が見られ現像槽の清掃作業は水で流すだけでは困難でスポンジ、ブラシ等での擦りが必要。現像される感光性平版印刷版材料また現像された平版印刷版にはスラッジへドロは付着せず現像作業自体は実質上問題はない
×：スラッジへドロが、自現機の循環ポンプに詰まるか、現像後の平版印刷版に付着し汚れ発生。
【０１９９】
結果を表２に示す。
【０２００】
【表２】

【０２０１】
表２から、本発明の構成（感光性平版印刷版材料の処理方法）の場合に、印刷時の見当合わせや休憩等でしばらく印刷機を停止した後、印刷再開時に非画像部に発生する微点状の汚れ（ストップ汚れ）の防止ができ、また、長期間現像処理をした場合に現像浴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すことができることがわかる。
【０２０２】
尚、近年印刷業界においても環境保全が叫ばれ、印刷インキにおいては石油系の揮発性有機化合物（ＶＯＣ）を使用しないインキが開発されその普及が進みつつある。本発明の構成は、このような環境対応の印刷インキ（たとえば、大日本インキ化学工業社製の、大豆油インキ“ナチュラリス１００”、東洋インキ社製のＶＯＣゼロインキ“ＴＫハイエコーＳＯＹ１”、東京インキ社製のプロセスインキ“ソイセルボ”等）を使用した場合に、特に本発明の効果（ストップ汚れの防止、および、現像液に生じるスラッジの低減非画像部への汚れ付着の防止の両立）を顕著に発揮する。
【０２０３】
【発明の効果】
本発明により、印刷時の見当合わせや休憩等でしばらく印刷機を停止した後、印刷再開時に非画像部に発生する微点状の汚れ（ストップ汚れ）の防止ができ、また、長期間現像処理をした場合に現像浴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すことができる感光性平版印刷版材料の処理方法を提供できた。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for processing a photosensitive lithographic printing plate material, and more specifically, a process capable of preventing dirt (stop dirt) occurring in a non-image area and reducing sludge sludge during long-time processing. Regarding the method.
[0002]
[Prior art]
Conventionally, an alkali metal silicate developer has been widely used for developing a photosensitive lithographic printing plate material. An orthoquinonediazide compound is used in combination with a novolak resin in a photosensitive layer of a conventional photosensitive lithographic printing plate material, and an alkaline silicate aqueous solution capable of dissolving the novolak resin is used as a developer. Since this developer has a pH capable of dissolving the novolak resin of the photosensitive layer of about 13, a silicate having a good pH buffering property in the vicinity of pH 13 is contained in the developer, and the developer pH Has been given stability. These developers are described in JP-A-8-160633 (Patent Document 1) and the like. However, when the pH of a developer containing silicic acid is lowered due to dissolution of photosensitive layer components by development or mixing of carbon dioxide in the air, silicic acid is solidified to become sludge and adheres to the developed plate, and the plate is stained. There have been problems such as accumulation in the tank and an increase in the burden of cleaning the developer tank.
[0003]
On the other hand, since a photopolymerization type photosensitive layer containing an ethylenically unsaturated bond-containing compound typified by a photopolymer type CTP plate generally does not use a novolac resin, the pH of the developer is a low pH of less than 12.5. Since it is not necessary to use silicate as a pH buffer, it is possible to design a developer containing no silicate. Further, in this case, when the pH of the developer is lowered, it is possible to receive a merit that silicate is not solidified and sludge is not generated. Such a developer is described in JP-A No. 2002-251019 (Patent Document 2). However, since silicate is a good hydrophilizing agent for the surface of the aluminum plate support, when a developer containing no silicic acid is used, the surface of the aluminum plate support, which is a non-image area of the developed plate material, is sufficiently hydrophilic. It is difficult to obtain the characteristics, and there is a drawback that the image is soiled. In general, the higher the sensitivity of a photosensitive lithographic printing plate, the shorter the time required for exposure, and the faster the operation can be performed. When printing such a photosensitive lithographic printing plate material, after stopping the printing machine for a while due to registration or breaks during printing work, fine dot-like stains that occur in the non-image area when printing resumes occur. In some cases (hereinafter referred to as stop stain), a method for maintaining the hydrophilicity of the plate surface of the non-image area has been particularly desired in order to prevent this stain.
[0004]
Further, when making a lithographic printing plate, a plate surface protective agent is applied in the final step. The purpose of applying the protective agent is not only to protect the hydrophilicity of the non-image area, but also to store it for the period until it is printed after printing, or store it until reuse, fingerprints, oils, dust, etc. It is to prevent the stain caused by the adhesion of the material, to protect it from the generation of scratches, and to further suppress the occurrence of the oxidation stain. Conventionally, as a plate surface protecting agent for a lithographic printing plate, generally gum arabic, cellulose gum or an aqueous solution of a water-soluble polymer having a carboxyl group in the molecule is used. In addition, a plate surface protecting agent containing phosphoric acid-modified starch is disclosed in JP-A-62-11693 (Patent Document 3), and a plate surface protecting agent containing carboxyalkylated starch is disclosed in JP-A 62-7595 (Patent Document 4). JP-A-11-288106 (Patent Document 5) discloses a plate surface protective material containing a specific polyoxyethylene group-containing activator, and many plate surface protective agents containing a water-soluble polymer have been proposed. ing. However, this method alone does not sufficiently maintain the hydrophilicity of the non-image area plate surface, and the stop stain cannot be completely suppressed.
[0005]
[Patent Document 1]
JP-A-8-160633 (page 15)
[0006]
[Patent Document 2]
JP 2002-251019 A (page 34)
[0007]
[Patent Document 3]
Japanese Patent Laid-Open No. Sho 62-11693 (2nd page)
[0008]
[Patent Document 4]
JP 62-7595 A (page 2)
[0009]
[Patent Document 5]
JP 11-288106 A (page 3)
[0010]
[Problems to be solved by the invention]
The present invention has been made in view of the above circumstances, and an object of the present invention is to make fine dots generated in a non-image portion when printing is resumed after stopping the printing machine for a while due to registration or break at the time of printing. Provided is a method for processing a photosensitive lithographic printing plate material that can prevent contamination (stop contamination) and reduce sludge sludge accumulated in a developing bath after long-term development processing, thereby reducing the burden of cleaning work. There is.
[0011]
[Means for Solving the Problems]
The above object of the present invention has been achieved by the following constitution.
[0012]
1. A photosensitive lithographic printing plate material having a photosensitive layer of a photopolymerizable photosensitive resin composition containing an ethylenically unsaturated bond-containing monomer, a photopolymerization initiator and a polymer binder on the surface of an aluminum plate support, silicic acid The salt content is SiO₂A method for processing a photosensitive lithographic printing plate material which is 0 to 0.1% in terms of mass and which is developed with an alkaline aqueous developer containing the compound A, wherein the aluminum plate is supported before the photosensitive layer is coated. A method for treating a photosensitive lithographic printing plate material, wherein the silicon atom concentration on the surface of the body is 5 to 20 atom%.
[0013]
2. A photosensitive lithographic printing plate material having a photosensitive layer of a photopolymerizable photosensitive resin composition containing an ethylenically unsaturated bond-containing monomer, a photopolymerization initiator and a polymer binder on the surface of an aluminum plate support, silicic acid The salt content is SiO₂A method for processing a photosensitive lithographic printing plate material, which is 0 to 0.1% in terms of mass and is developed with an alkaline aqueous developer containing the compound B, wherein the aluminum plate is supported before the photosensitive layer is coated. A method for treating a photosensitive lithographic printing plate material, wherein the silicon atom concentration on the surface of the body is 5 to 20 atom%.
[0014]
3. A photosensitive lithographic printing plate material having a photosensitive layer of a photopolymerizable photosensitive resin composition containing an ethylenically unsaturated bond-containing monomer, a photopolymerization initiator and a polymer binder on the surface of an aluminum plate support, silicic acid The salt content is SiO₂A method for processing a photosensitive lithographic printing plate material, which is 0 to 0.1% in terms of mass and is developed with an alkaline aqueous developer containing the compound C, wherein the aluminum plate is supported before the photosensitive layer is coated. A method for treating a photosensitive lithographic printing plate material, wherein the silicon atom concentration on the surface of the body is 5 to 20 atom%.
[0015]
4). A photosensitive lithographic printing plate material having a photosensitive layer of a photopolymerizable photosensitive resin composition containing an ethylenically unsaturated bond-containing monomer, a photopolymerization initiator and a polymer binder on the surface of an aluminum plate support, silicic acid The salt content is SiO₂A method for processing a photosensitive lithographic printing plate material which is 0 to 0.1% in terms of mass and which is developed with an alkaline aqueous developer containing the compound A, wherein the aluminum plate is supported before the photosensitive layer is coated. A method for treating a photosensitive lithographic printing plate material, characterized in that the phosphorus atom concentration on the surface of the body is 3 to 15 atom%.
[0016]
5. A photosensitive lithographic printing plate material having a photosensitive layer of a photopolymerizable photosensitive resin composition containing an ethylenically unsaturated bond-containing monomer, a photopolymerization initiator and a polymer binder on the surface of an aluminum plate support, silicic acid The salt content is SiO₂A method for processing a photosensitive lithographic printing plate material, which is 0 to 0.1% in terms of mass and is developed with an alkaline aqueous developer containing the compound B, wherein the aluminum plate is supported before the photosensitive layer is coated. A method for treating a photosensitive lithographic printing plate material, characterized in that the phosphorus atom concentration on the surface of the body is 3 to 15 atom%.
[0017]
6). A photosensitive lithographic printing plate material having a photosensitive layer of a photopolymerizable photosensitive resin composition containing an ethylenically unsaturated bond-containing monomer, a photopolymerization initiator and a polymer binder on the surface of an aluminum plate support, silicic acid The salt content is SiO₂A method for processing a photosensitive lithographic printing plate material, which is 0 to 0.1% in terms of mass and is developed with an alkaline aqueous developer containing the compound C, wherein the aluminum plate is supported before the photosensitive layer is coated. A method for treating a photosensitive lithographic printing plate material, characterized in that the phosphorus atom concentration on the surface of the body is 3 to 15 atom%.
[0018]
Hereinafter, the present invention will be described in detail.
In the processing method of the photosensitive lithographic printing plate material of the present invention, the silicon atom concentration on the surface of the aluminum plate support before coating the photosensitive layer is 5 to 20 atomic%, or before coating the photosensitive layer. One feature is that the phosphorus atom concentration on the surface of the aluminum plate support is 3 to 15 atomic%.
[0019]
In the present invention, the concentration of silicon atoms or phosphorus atoms on the surface of the aluminum plate support is, in the case of silicon atoms, a silicon atom concentration of 5 to 20 atom%, and preferably 10 to 15 mol%. When the silicon atom concentration is less than 5 atom%, the hydrophilicity of the aluminum plate support surface is low, and there is a possibility that ink adheres to the non-image area during printing. On the other hand, if it exceeds 20 atomic%, the adhesion between the photosensitive layer and the aluminum plate support is lowered, and the printing durability is deteriorated. Such a property appears particularly remarkably in an ink that does not use a petroleum-based volatile organic compound (VOC). In the case of phosphorus atoms, the phosphorus atom concentration is 3 to 15 atom%, preferably 10 to 15 mol%. If the phosphorus atom concentration is less than 3 atomic%, the hydrophilicity of the aluminum plate support surface is low, and there is a possibility that ink adheres to the non-image area during printing. On the other hand, if it exceeds 15 atomic%, the adhesion between the photosensitive layer and the aluminum plate support is lowered, and the printing durability is deteriorated. Such a property appears particularly remarkably in an ink that does not use a petroleum-based volatile organic compound (VOC). Further, it is also preferred that the silicon atom is 5 to 10 mol% and the phosphorus atom is 5 to 10 mol% at the same time. The silicon atom or phosphorus atom is preferably coated during or after the sealing treatment. When the silicon atom is coated within the scope of the present invention, SiO is coated.₂It is preferable to treat with an aqueous solution containing 0.1 to 2% by mass of a metal silicate alkali salt in terms of conversion, and when the phosphorus atom is covered within the scope of the present invention, 0.1 to 2% by mass of polyvinyl. It is preferable to treat with an aqueous solution containing phosphonic acid or a salt thereof. The temperature for the treatment is preferably 15 to 95 ° C, more preferably 50 to 90 ° C, and particularly preferably 80 to 90 ° C.
[0020]
(Measurement method of atomic weight on the grain surface)
The measurement of the silicon atom concentration or the phosphorus atom concentration on the surface of the printing plate support was performed using an X-ray photoelectron spectroscopy (XPS) surface analyzer.
[0021]
The XPS method is an abbreviation for X-ray photoelectron spectroscopy, and is a method for analyzing the type and chemical bonding state of elements near the sample surface from the energy spectrum of photoelectrons emitted from atoms in the sample by X-ray irradiation. . This method has a characteristic that information within 10 nm from the outermost surface of the sample can be obtained relatively strongly because the photoelectron transmissivity is small. For the X-ray source used in the XPS method, it is necessary to use an anode material having a small energy width in order to avoid the resolution being restricted. Moreover, it must be stable to electron impact for a long time and have an energy of about several thousand eV. It is desirable to use MgKα and AlKα as a radiation source that satisfies such conditions. In addition, when interference between photoelectrons and Auger peak occurs, the energy of Auger electrons does not change depending on the radiation source, so the interference can be solved by measuring with two radiation sources. It is preferable to equip a Mg anode and an Al anode. A monochromator may be installed between the radiation source and the sample. By using a monochromator, X-ray monochromatization can be achieved, eliminating interference by satellites, improving S / N ratio by removing X-rays by bremsstrahlung, and enabling separation of main lines of double lines, etc. An effect is obtained. However, when a non-conductive substance is measured with a monochromator, it may cause a charge-up, and at that time, it is necessary to use a flood gun.
[0022]
There are generally two types of electron energy analyzers that measure the energy of electrons emitted or scattered from the sample surface: a cylindrical mirror analyzer and a concentric hemispherical analyzer. The former has a wide solid angle of electron capture and can be measured with high sensitivity. The latter is excellent in terms of resolution, but has a problem that the solid angle is small and the sensitivity is low. However, the sensitivity of the concentric hemispherical analyzer has been improved by installing a channeltron electron multiplier after the spectrometer, and there is no problem in measurement accuracy. A type of analyzer may be used. In the XPS method, minute changes in the surface affect measurement data. For example, there is a problem of impurity adsorption and contamination caused by leaving in the atmosphere for a long time. In addition, the desorption of the adsorbed substance under ultra-high vacuum at the time of measurement, damage caused by X-rays, and the like are also affected. Therefore, when handling the sample, the measurement must be performed while fully considering the above points. When performing quantification using the measured spectrum, it is necessary to pay attention to the energy shift of the photoelectron peak due to the positive charge accumulated on the sample surface. As a shift correction method,
1. Utilizing contaminated hydrocarbon C1s
2. Use Au 4f7 / 2 deposited on the surface
3. Mixing with reference material
4). Use of low energy electronic flat gun
However, a correction using “contaminated hydrocarbon C1s” in which no special treatment is applied to the sample surface is preferable.
[0023]
There are no particular limitations on the XPS surface analyzer, and any known model can be used. In the present invention, ESCALAB-200R manufactured by VG Scientific, Inc. was used. Mg was used for the X-ray anode, and measurement was performed at an output of 600 W (acceleration voltage: 15 kV, emission current: 40 mA). The energy resolution was set to be 1.5 to 1.7 eV when defined by the half width of a clean Ag3d5 / 2 peak. First, the range of binding energy from 0 eV to 1100 eV was measured at a data acquisition interval of 1.0 eV to determine what elements were detected. Next, with respect to all the detected elements, the data capture interval was set to 0.2 eV, and the photoelectron peak giving the maximum intensity was subjected to narrow scan, and the spectrum of each element was measured. The obtained spectrum is on COMMON DATA PROCESSING SYSTEM (Ver. 2.3 or later is preferable) manufactured by VAMAS-SCA-JAPAN in order not to cause a difference in the content calculation result due to a difference in measuring apparatus or computer. Then, the surface was treated with the same software, and the value of the surface composition was obtained as the atomic concentration.
[0024]
Before performing the quantitative process, a calibration of the Scale Scale was performed for each element, and a 5-point smoothing process was performed. In the quantitative process, the peak area intensity (cps * eV) from which the background was removed was used. For the background treatment, the method by Shirley was used. For the Shirley method, see D.C. A. Shirley, Phys. Rev. , B5, 4709 (1972).
[0025]
(Support)
The support that can be used for the photosensitive lithographic printing plate material according to the present invention is preferably an aluminum plate. In this case, a pure aluminum plate, an aluminum alloy plate, or the like may be used.
[0026]
Various aluminum alloys can be used as the support, such as alloys of aluminum and metals such as silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, nickel, titanium, sodium, iron, etc. Aluminum plates manufactured by various rolling methods can be used. In addition, a recycled aluminum plate obtained by rolling recycled aluminum ingots such as scrap materials and recycled materials that are becoming popular in recent years can also be used.
[0027]
The support that can be used for the photosensitive lithographic printing plate material according to the present invention is preferably subjected to a degreasing treatment in order to remove the rolling oil on the surface prior to roughening (graining treatment). As the degreasing treatment, a degreasing treatment using a solvent such as trichlene or thinner, an emulsion degreasing treatment using an emulsion such as kesilon or triethanol, or the like is used. In addition, an alkaline aqueous solution such as caustic soda can be used for the degreasing treatment. When an alkaline aqueous solution such as caustic soda is used for the degreasing treatment, dirt and oxide film that cannot be removed only by the degreasing treatment can be removed. When an alkaline aqueous solution such as caustic soda is used for the degreasing treatment, smut is generated on the surface of the support. In this case, the substrate is immersed in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid, or a mixed acid thereof and desmutted. It is preferable to perform the treatment.
[0028]
Examples of the roughening method include a mechanical method and a method of etching by electrolysis.
[0029]
The mechanical roughening method used is not particularly limited, but a brush polishing method and a honing polishing method are preferable. The roughening by the brush polishing method is, for example, by rotating a rotating brush using a bristle having a diameter of 0.2 to 0.8 mm, and for example, volcanic ash particles having a particle size of 10 to 100 μm on water. While supplying the uniformly dispersed slurry, the brush can be pressed. The roughening by honing polishing is performed by, for example, uniformly dispersing volcanic ash particles having a particle size of 10 to 100 μm in water, injecting pressure from a nozzle, and causing the surface to collide obliquely with the support surface. Can do. Further, for example, abrasive particles having a particle diameter of 10 to 100 μm are applied to the support surface at an interval of 100 to 200 μm at 2.5 × 10.³-10x10³Piece / cm²It is also possible to perform roughening by laminating the coated sheets so as to exist at a density and transferring the rough surface pattern of the sheet by applying pressure.
[0030]
After the surface is roughened by the mechanical surface roughening method, it is preferable to immerse in an aqueous solution of acid or alkali in order to remove the abrasive that has digged into the surface of the support, formed aluminum scraps, and the like. Examples of the acid include sulfuric acid, persulfuric acid, hydrofluoric acid, phosphoric acid, nitric acid, hydrochloric acid, and the like. Examples of the base include sodium hydroxide and potassium hydroxide. Among these, it is preferable to use an aqueous alkali solution such as sodium hydroxide. The amount of aluminum dissolved on the surface is 0.5 to 5 g / m.²Is preferred. After the immersion treatment with an alkaline aqueous solution, it is preferable to carry out a neutralization treatment by immersion in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid or a mixed acid thereof.
[0031]
The electrochemical surface roughening method is not particularly limited, but a method of electrochemical surface roughening in an acidic electrolyte is preferable. As the acidic electrolytic solution, an acidic electrolytic solution usually used in an electrochemical surface roughening method can be used, but a hydrochloric acid-based or nitric acid-based electrolytic solution is preferably used. As the electrochemical surface roughening method, for example, methods described in Japanese Patent Publication No. 48-28123, British Patent No. 896,563 and Japanese Patent Laid-Open No. 53-67507 can be used. This roughening method can be generally performed by applying a voltage in the range of 1 to 50 volts, but is preferably selected from the range of 10 to 30 volts. Current density is 10 to 200 A / dm²The range of 50 to 150 A / dm can be used.²It is preferable to select from the range. The amount of electricity is 100 to 5000 c / dm²However, it is preferable to select from the range of 100 to 2000 c / dm2. The temperature at which the roughening method is performed can be in the range of 10 to 50 ° C, but is preferably selected from the range of 15 to 45 ° C.
[0032]
When electrochemical surface roughening is performed using a nitric acid-based electrolyte as the electrolyte, it can be generally performed by applying a voltage in the range of 1 to 50 volts, but is selected from the range of 10 to 30 volts. Is preferred. Current density is 10 to 200 A / dm²The range of 20-100 A / dm can be used.²It is preferable to select from the range. The amount of electricity is 100 to 5000 c / dm²The range of 100 to 2000 c / dm can be used.²It is preferable to select from the range. The temperature at which the electrochemical roughening method is performed can be in the range of 10 to 50 ° C, but is preferably selected from the range of 15 to 45 ° C. The concentration of nitric acid in the electrolytic solution is preferably 0.1 to 5% by mass. If necessary, nitrates, chlorides, amines, aldehydes, phosphoric acid, chromic acid, boric acid, acetic acid, oxalic acid, and the like can be added to the electrolytic solution.
[0033]
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 to 200 A / dm²The range of 50 to 150 A / dm can be used.²It is preferable to select from the range. The amount of electricity is 100 to 5000 c / dm²Can be used, but preferably 100 to 2000 c / dm²Furthermore, 200 to 1000 c / dm²It is more preferable to select from the range. The temperature at which the electrochemical roughening method is performed can be in the range of 10 to 50 ° C, but is preferably selected from the range of 15 to 45 ° C. The concentration of hydrochloric acid in the electrolytic solution is preferably 0.1 to 5% by mass. If necessary, nitrates, chlorides, amines, aldehydes, phosphoric acid, chromic acid, boric acid, acetic acid, oxalic acid, and the like can be added to the electrolytic solution.
[0034]
After the surface is roughened by the electrochemical surface roughening method, it is preferably immersed in an acid or alkali aqueous solution in order to remove aluminum scraps on the surface. Examples of the acid include sulfuric acid, persulfuric acid, hydrofluoric acid, phosphoric acid, nitric acid, hydrochloric acid, and the like. Examples of the base include sodium hydroxide and potassium hydroxide. Among these, it is preferable to use an alkaline aqueous solution. The amount of aluminum dissolved on the surface is 0.5 to 5 g / m.²Is preferred. In addition, it is preferable that after the immersion treatment with an alkaline aqueous solution, neutralization treatment is performed by immersion in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid or a mixed acid thereof.
[0035]
The mechanical surface roughening method and the electrochemical surface roughening method may each be used alone for roughening, or the mechanical surface roughening treatment method followed by the electrochemical surface roughening method may be used for roughening. You may face it.
[0036]
Following the roughening treatment, an anodic oxidation treatment can be performed. There is no restriction | limiting in particular in the method of the anodizing process which can be used in this invention, A well-known method can be used. By performing the anodizing treatment, an oxide film is formed on the support. In the anodizing treatment, an aqueous solution containing sulfuric acid and / or phosphoric acid at a concentration of 10 to 50% is used as an electrolytic solution, and a current density of 1 to 10 A / dm.²The electrolysis method is preferably used, but in addition, the method of electrolysis at high current density in sulfuric acid described in US Pat. No. 1,412,768, and the method described in US Pat. No. 3,511,661. Examples thereof include a method of electrolysis using phosphoric acid, a method of using a solution containing one or more of chromic acid, oxalic acid, malonic acid and the like. The formed anodic oxidation coating amount is 1-50 mg / dm.²Is suitable, preferably 10 to 40 mg / dm²It is. The amount of anodic oxidation coating is, for example, by immersing an aluminum plate in a chromic phosphate solution (85% phosphoric acid solution: 35 ml, prepared by dissolving 20 g of chromium (IV) oxide in 1 L of water) to dissolve the oxide layer, It is obtained from mass change measurement before and after dissolution of the coating on the plate.
[0037]
The anodized support may be sealed as necessary. These sealing treatments can be performed using known methods such as hot water treatment, boiling water treatment, water vapor treatment, sodium silicate treatment, dichromate aqueous solution treatment, nitrite treatment, and ammonium acetate treatment.
[0038]
In the present invention, the concentration of silicon atoms or phosphorus atoms on the surface of the aluminum plate support is, in the case of silicon atoms, a silicon atom concentration of 5 to 20 atom%, preferably 10 to 15 mol%, In this case, the phosphorus atom concentration is 3 to 15 atom%, preferably 10 to 15 mol%. Further, it is also preferred that the silicon atom is 5 to 10 mol% and the phosphorus atom is 5 to 10 mol% at the same time. The silicon atom or phosphorus atom is preferably coated during or after the sealing treatment. When the silicon atom is coated within the scope of the present invention, SiO is coated.₂It is preferable to treat with an aqueous solution containing 0.1 to 2% by mass of a metal silicate alkali salt in terms of conversion, and when the phosphorus atom is covered within the scope of the present invention, 0.1 to 2% by mass of polyvinyl. It is preferable to treat with an aqueous solution containing phosphonic acid or a salt thereof. The temperature for the treatment is preferably 15 to 95 ° C, more preferably 50 to 90 ° C, and particularly preferably 80 to 90 ° C.
[0039]
(Photopolymerization initiator)
In the present invention, preferred photopolymerization initiators include bromine compounds, titanocene compounds, monoalkyltriaryl borate compounds, and iron arene complex compounds having a structure represented by the following general formula (1).
[0040]
General formula (1) R¹-CBr₂-(C = O) -R²
Where R¹Represents a hydrogen atom, a bromine atom, an alkyl group, an aryl group, an acyl group, an alkylsulfonyl group, an arylsulfonyl group, or a cyano group. R²Represents a monovalent substituent. R¹And R²May combine to form a ring.
[0041]
General formula (2) CBr₃-(C = O) -XR³
Where R³Represents a monovalent substituent. X is -O-, -NR⁴-Represents. R⁴Represents a hydrogen atom or an alkyl group. R³And R⁴May combine to form a ring.
[0042]
Examples of the titanocene compound include compounds described in JP-A-63-41483 and JP-A-2-291. More preferred specific examples include bis (cyclopentadienyl) -Ti-di-chloride. , Bis (cyclopentadienyl) -Ti-bis-phenyl, bis (cyclopentadienyl) -Ti-bis-2,3,4,5,6-pentafluorophenyl, bis (cyclopentadienyl) -Ti -Bis-2,3,5,6-tetrafluorophenyl, bis (cyclopentadienyl) -Ti-bis-2,4,6-trifluorophenyl, bis (cyclopentadienyl) -Ti-bis-2 , 6-difluorophenyl, bis (cyclopentadienyl) -Ti-bis-2,4-difluorophenyl, bis (methylcyclopentadienyl) -Ti-bi -2,3,4,5,6-pentafluorophenyl, bis (methylcyclopentadienyl) -Ti-bis-2,3,5,6-tetrafluorophenyl, bis (methylcyclopentadienyl) -Ti -Bis-2,6-difluorophenyl (IRUGACURE 727L: manufactured by Ciba Specialty Chemicals), bis (cyclopentadienyl) -bis (2,6-difluoro-3- (py-1-yl) phenyl) titanium (IRUGACURE 784) : Ciba Specialty Chemicals), bis (cyclopentadienyl) -bis (2,4,6-trifluoro-3- (pyridin-1-yl) phenyl) titanium bis (cyclopentadienyl) -bis ( 2,4,6-trifluoro-3- (2-5-dimethylpy-1-yl) phenyl) titanium And the like.
[0043]
Examples of monoalkyl triaryl borate compounds include compounds described in JP-A-62-154024 and JP-A-62-143044, and more preferable specific examples include tetra-n-butylammonium n- Butyl-trinaphthalen-1-yl-borate, tetra-n-butylammonium n-butyl-triphenyl-borate, tetra-n-butylammonium n-butyl-tri- (4-tert-butylphenyl) -borate, tetra-n -Butyl ammonium n-hexyl root- (3-chloro-4-methylphenyl) -borate, tetra-n-butylammonium n-hexyl root- (3-fluorophenyl) -borate and the like.
[0044]
Examples of the iron arene complex compound include compounds described in JP-A-59-219307, and more preferable specific examples include η-benzene- (η-cyclopentadienyl) iron hexafluorophosphate, η -Cumene- (η-cyclopentadienyl) iron hexafluorophosphate, η-fluorene- (η-cyclopentadienyl) iron hexafluorophosphate, η-naphthalene- (η-cyclopentadienyl) iron hexafluorophosphate, η-xylene- (η-cyclopentadienyl) iron hexafluorophosphate, η-benzene- (η-cyclopentadienyl) iron tetrafluoroborate, and the like.
[0045]
In addition, any photopolymerization initiator can be used in combination. For example, J. et al. Carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo, diazo compounds, halogen compounds, and photoreductive dyes as described in Chapter 5 of “Light Sensitive Systems” by J. Kosar Etc. More specific compounds are disclosed in British Patent 1,459,563.
[0046]
That is, the following can be used as a photopolymerization initiator that can be used in combination.
[0047]
Benzoin derivatives such as benzoin methyl ether, benzoin-i-propyl ether, α, α-dimethoxy-α-phenylacetophenone; benzophenone, 2,4-dichlorobenzophenone, methyl o-benzoylbenzoate, 4,4′-bis (dimethyl) Benzophenone derivatives such as amino) benzophenone; thioxanthone derivatives such as 2-chlorothioxanthone and 2-i-propylthioxanthone; anthraquinone derivatives such as 2-chloroanthraquinone and 2-methylanthraquinone; N-methylacridone, N-butylacridone and the like In addition to α, α-diethoxyacetophenone, benzyl, fluorenone, xanthone and uranyl compounds, JP-B-59-1281, 61-9621 and JP-A-60-60104 Triazine derivatives; organic peroxides described in JP-A-59-1504 and JP-A-61-243807; JP-B-43-23684, JP-A-44-6413, JP-A-44-6413, JP-A-47-1604, and US patents Diazonium compounds described in US Pat. No. 3,567,453; organic azide compounds described in US Pat. Nos. 2,848,328 and 2,852,379 and 2,940,853; O-quinonediazides described in JP-A Nos. 13109, 38-18015 and 45-9610; JP-B-55-39162, JP-A-59-14023 and “Macromolecules”, Vol. 10, 1307 Various onium compounds described on page 1977; azo compounds described in JP-A-59-142205 Compound: described in JP-A-1-54440, European Patents 109,851, 126,712 and “Journal of Imaging Science (J. Imag. Sci.)”, Volume 30, p. 174 (1986) (Oxo) sulfonium organoboron complexes described in JP-A-5-213861 and JP-A-5-255347; "Coordination Chemistry Review", 84, 85-277 (1988) And transition metal complexes containing a transition metal such as ruthenium described in JP-A-2-182701; 2,4,5-triarylimidazole dimer described in JP-A-3-209477; carbon tetrabromide, JP Organic halogen compounds described in 59-107344;
[0048]
When laser light is used as the light source, a sensitizing dye is preferably added to the photosensitive layer. It is preferable to use a dye having an absorption maximum wavelength in the vicinity of the wavelength of the light source.
[0049]
Examples of compounds for wavelength sensitization from visible light to near infrared include cyanine, phthalocyanine, merocyanine, porphyrin, spiro compound, ferrocene, fluorene, fulgide, imidazole, perylene, phenazine, phenothiazine, polyene, azo compound, diphenylmethane, triphenyl Ketone alcohol borate complexes such as methane, polymethine acridine, coumarin, coumarin derivatives, ketocoumarin, quinacridone, indigo, styryl, pyrylium compounds, pyromethene compounds, pyrazolotriazole compounds, benzothiazole compounds, barbituric acid derivatives, thiobarbituric acid derivatives, etc. Further, European Patent No. 568,993, US Patent Nos. 4,508,811, 5,227,227, JP 2001-125255 A, JP 11 Compounds described in such Patent 271,969 may also be used.
[0050]
Specific examples of the combination of the photopolymerization initiator and the sensitizing dye include combinations described in JP-A Nos. 2001-125255 and 11-271969.
[0051]
Although the compounding quantity of these polymerization initiators is not specifically limited, Preferably, it is 0.1-20 mass parts with respect to 100 mass parts of compounds which can be addition-polymerized or bridge | crosslinked. The mixing ratio of the photopolymerization initiator and the sensitizing dye is preferably in the range of 1: 100 to 100: 1 in terms of molar ratio.
[0052]
(Ethylenically unsaturated bond-containing monomer)
The compound containing an ethylenic double bond capable of addition polymerization, which is an ethylenically unsaturated bond-containing monomer according to the present invention, is generally used for general radical polymerizable monomers and ultraviolet curable resins. Polyfunctional monomers having a plurality of ethylenic double bonds capable of addition polymerization in the molecule and polyfunctional oligomers can be used. The compound is not limited, but preferred examples include 2-ethylhexyl acrylate, 2-hydroxypropyl acrylate, glycerol acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, nonylphenoxyethyl acrylate, tetrahydrofurfuryloxyethyl acrylate, tetrahydro Furfuryloxyhexanolide acrylate, acrylate of ε-caprolactone adduct of 1,3-dioxane alcohol, monofunctional acrylic acid esters such as 1,3-dioxolane acrylate, or these acrylates as methacrylate, itaconate, crotonate, maleate Methacrylic acid, itaconic acid, crotonic acid, maleic acid esters such as ethylene glycol diacrylate , Triethylene glycol diacrylate, pentaerythritol diacrylate, hydroquinone diacrylate, resorcin diacrylate, hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, dipentylate of hydroxypentylate neopentyl glycol, Diacrylate of neopentyl glycol adipate, Diacrylate of ε-caprolactone adduct of neopentyl glycol hydroxypivalate, 2- (2-hydroxy-1,1-dimethylethyl) -5-hydroxymethyl-5-ethyl-1, Ε-caprolactone adduct of 3-dioxane diacrylate, tricyclodecane dimethylol acrylate, tricyclodecane dimethylol acrylate Difunctional acrylic acid esters such as diglycidyl ether diacrylate of 1,6-hexanediol, or methacrylic acid, itaconic acid, crotonic acid, maleic acid ester in which these acrylates are replaced with methacrylate, itaconate, crotonate, maleate, For example, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, trimethylolethane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, dipentaerythritol Ε-caprolactone adduct of hexaacrylate, pyrogallol triacrylate Polyfunctional acrylic acid esters such as propionic acid / dipentaerythritol triacrylate, propionic acid / dipentaerythritol tetraacrylate, hydroxypivalylaldehyde-modified dimethylolpropane triacrylate, or these acrylates with methacrylate, itaconate, crotonate, Examples thereof include methacrylic acid, itaconic acid, crotonic acid, and maleic acid ester instead of maleate.
[0053]
Prepolymers can also be used as described above. Examples of the prepolymer include compounds as described below, and a prepolymer obtained by introducing acrylic acid or methacrylic acid into an oligomer having an appropriate molecular weight and imparting photopolymerizability can be preferably used. These prepolymers may be used alone or in combination of two or more, and may be used by mixing with the above-mentioned monomers and / or oligomers.
[0054]
Examples of prepolymers include adipic acid, trimellitic acid, maleic acid, phthalic acid, terephthalic acid, hymic acid, malonic acid, succinic acid, glutaric acid, itaconic acid, pyromellitic acid, fumaric acid, glutaric acid, pimelic acid, Polybasic acids such as sebacic acid, dodecanoic acid, tetrahydrophthalic acid, and ethylene glycol, propylene glycol, diethylene glycol, propylene oxide, 1,4-butanediol, triethylene glycol, tetraethylene glycol, polyethylene glycol, glycerin, trimethylol Polyester obtained by introducing (meth) acrylic acid into a polyester obtained by combining polyhydric alcohols such as propane, pentaerythritol, sorbitol, 1,6-hexanediol, 1,2,6-hexanetriol Chlorates such as bisphenol A, epichlorohydrin, (meth) acrylic acid, and epoxy acrylates in which (meth) acrylic acid is introduced into an epoxy resin such as phenol novolac, epichlorohydrin, (meth) acrylic acid, such as ethylene glycol, adipine Acid / tolylene diisocyanate / 2-hydroxyethyl acrylate, polyethylene glycol / tolylene diisocyanate / 2-hydroxyethyl acrylate, hydroxyethylphthalyl methacrylate / xylene diisocyanate, 1,2-polybutadiene glycol / tolylene diisocyanate / 2-hydroxyethyl acrylate , Trimethylolpropane, propylene glycol, tolylene diisocyanate, 2-hydroxyethyl acrylate In addition, urethane acrylates in which (meth) acrylic acid is introduced into urethane resin, for example, silicone resin acrylates such as polysiloxane acrylate, polysiloxane diisocyanate, 2-hydroxyethyl acrylate, etc., and (meth) acryloyl in oil-modified alkyd resins Examples thereof include prepolymers such as alkyd-modified acrylates having introduced groups and spirane resin acrylates.
[0055]
The photopolymerizable photosensitive resin composition according to the present invention includes a phosphazene monomer, triethylene glycol, isocyanuric acid EO (ethylene oxide) -modified diacrylate, isocyanuric acid EO-modified triacrylate, dimethylol tricyclodecane diacrylate, tri Contains monomers such as methylolpropane acrylate benzoate, alkylene glycol type acrylic acid modified acrylate, alkylene glycol type urethane modified acrylate, and addition polymerizable oligomers and prepolymers having structural units formed from the monomer. can do.
[0056]
Furthermore, examples of the ethylenically unsaturated bond-containing monomer that can be used in combination with the present invention include phosphate ester compounds containing at least one (meth) acryloyl group. The compound is not particularly limited as long as it is a compound in which at least part of the hydroxyl group of phosphoric acid is esterified and has a (meth) acryloyl group.
[0057]
In addition, JP-A-58-212994, 61-6649, 62-46688, 62-48589, 62-173295, 62-187092, 63- 67189, JP-A-1-244891, and the like. Further, “11290 Chemical Products”, Chemical Industry Daily, p. 286-p. 294, “UV / EB Curing Handbook (raw material)”, Kobunshi Publishing Co., p. The compounds described in 11 to 65 can also be suitably used in the present invention. Of these, compounds having two or more acrylic groups or methacryl groups in the molecule are preferred in the present invention, and those having a molecular weight of 10,000 or less, more preferably 5,000 or less are preferred.
[0058]
In the present invention, it is preferable to use an addition-polymerizable ethylenically unsaturated bond-containing monomer containing a tertiary amino group in the molecule. Although there is no particular limitation on the structure, a tertiary amine compound having a hydroxyl group modified with glycidyl methacrylate, methacrylic acid chloride, acrylic acid chloride or the like is preferably used. Specifically, collectable compounds described in JP-A-1-165613, JP-A-1-203413, and JP-A-1-197213 are preferably used.
[0059]
Furthermore, the present invention uses a reaction product of a polyhydric alcohol containing a tertiary amino group in the molecule, a diisocyanate compound, and a compound containing an ethylenic double bond capable of addition polymerization with a hydroxyl group in the molecule. Is preferred.
[0060]
Examples of the polyhydric alcohol having a tertiary amino group in the molecule include triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-tert. -Butyldiethanolamine, N, N-di (hydroxyethyl) aniline, N, N, N ', N'-tetra-2-hydroxypropylethylenediamine, p-tolyldiethanolamine, N, N, N', N'- Tetra-2-hydroxyethylethylenediamine, N, N-bis (2-hydroxypropyl) aniline, allyldiethanolamine, 3- (dimethylamino) -1,2-propanediol, 3-diethylamino-1,2-propanediol N, N-di (n-propyl) amino-2,3-propanediol, N, N-di (iso-propyl) amino-2,3-propanediol, 3- (N-methyl-N-benzylamino) ) -1,2-propanediol and the like, but not limited thereto.
[0061]
Examples of the diisocyanate compound include butane-1,4-diisocyanate, hexane-1,6-diisocyanate, 2-methylpentane-1,5-diisocyanate, octane-1,8-diisocyanate, 1,3-diisocyanate methyl-cyclohexanone. 2,2,4-trimethylhexane-1,6-diisocyanate, isophorone diisocyanate, 1,2-phenylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene-2,4-diisocyanate, tolylene- Examples include 2,5-diisocyanate, tolylene-2,6-diisocyanate, 1,3-di (isocyanatomethyl) benzene, 1,3-bis (1-isocyanato-1-methylethyl) benzene, and the like. Limited to Not. Examples of the compound containing an ethylenically unsaturated bond capable of addition polymerization with a hydroxyl group in the molecule include compounds such as MH-1 to MH-13, but are not limited thereto. Preferable examples include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxypropylene-1,3-dimethacrylate, 2-hydroxypropylene-1-methacrylate-3-acrylate, and the like.
[0062]
These reactions can be carried out in the same manner as a method for synthesizing urethane acrylate by a reaction of a normal diol compound, diisocyanate compound, and hydroxyl group-containing acrylate compound.
[0063]
Specific examples of reaction products of polyhydric alcohols containing a tertiary amino group in the molecule, diisocyanate compounds, and compounds containing an ethylenically unsaturated bond capable of addition polymerization with a hydroxyl group in the molecule are shown below. Shown in
[0064]
M-1: Reaction product of triethanolamine (1 mol), hexane-1,6-diisocyanate (3 mol), 2-hydroxyethyl methacrylate (3 mol)
M-2: reaction product of triethanolamine (1 mol), isophorone diisocyanate (3 mol), 2-hydroxyethyl acrylate (3 mol)
M-3: Nn-butyldiethanolamine (1 mol), 1,3-bis (1-isocyanato-1-methylethyl) benzene (2 mol), 2-hydroxypropylene-1-methacrylate-3-acrylate (2 mol) of reaction product
M-4: Reaction of Nn-butyldiethanolamine (1 mol), 1,3-di (isocyanatomethyl) benzene (2 mol), 2-hydroxypropylene-1-methacrylate-3-acrylate (2 mol) Product
M-5: Reaction product of N-methyldiethanolamine (1 mol), tolylene-2,4-diisocyanate (2 mol), 2-hydroxypropylene-1,3-dimethacrylate (2 mol)
In addition, acrylates or alkyl acrylates described in JP-A-1-105238 and JP-A-2-127404 can be used.
[0065]
(Polymer binder)
The photosensitive lithographic printing plate material according to the present invention contains a polymer binder in the photopolymerizable photosensitive layer.
[0066]
Examples of the polymer binder according to the present invention include an acrylic polymer, polyvinyl butyral resin, polyurethane resin, polyamide resin, polyester resin, epoxy resin, phenol resin, polycarbonate resin, polyvinyl butyral resin, polyvinyl formal resin, shellac, and the like. Natural resins can be used. Two or more of these may be used in combination.
[0067]
A vinyl copolymer obtained by copolymerization of acrylic monomers is preferred. Furthermore, the copolymer composition of the polymer binder is preferably a copolymer of (a) a carboxyl group-containing monomer, (b) a methacrylic acid alkyl ester, or an acrylic acid alkyl ester.
[0068]
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, itaconic anhydride and the like. In addition, carboxylic acids such as phthalic acid and 2-hydroxymethacrylate half ester are also preferable.
[0069]
Specific examples of alkyl methacrylates and alkyl esters include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, nonyl methacrylate. , Decyl methacrylate, undecyl methacrylate, dodecyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, nonyl acrylate, acrylic In addition to unsubstituted alkyl esters such as decyl acid, undecyl acrylate and dodecyl acrylate, cyclic alkyl esters such as cyclohexyl methacrylate and cyclohexyl acrylate Substituted alkyl esters such as benzyl methacrylate, 2-chloroethyl methacrylate, N, N-dimethylaminoethyl methacrylate, glycidyl methacrylate, benzyl acrylate, 2-chloroethyl acrylate, N, N-dimethylaminoethyl acrylate, and glycidyl acrylate Also mentioned.
[0070]
Furthermore, the polymer binder according to the present invention can use monomers described in the following (1) to (14) as other copolymerization monomers.
[0071]
1) Monomers having an aromatic hydroxyl group, such as o- (or p-, m-) hydroxystyrene, o- (or p-, m-) hydroxyphenyl acrylate and the like.
[0072]
2) Monomers having an aliphatic hydroxyl group, such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, N-methylol acrylamide, N-methylol methacrylamide, 4-hydroxybutyl methacrylate, 5-hydroxypentyl acrylate, 5-hydroxypentyl methacrylate , 6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate, N- (2-hydroxyethyl) acrylamide, N- (2-hydroxyethyl) methacrylamide, hydroxyethyl vinyl ether and the like.
[0073]
3) A monomer having an aminosulfonyl group, such as m- (or p-) aminosulfonylphenyl methacrylate, m- (or p-) aminosulfonylphenyl acrylate, N- (p-aminosulfonylphenyl) methacrylamide, N- (p -Aminosulfonylphenyl) acrylamide and the like.
[0074]
4) Monomers having a sulfonamide group, such as N- (p-toluenesulfonyl) acrylamide, N- (p-toluenesulfonyl) methacrylamide and the like.
[0075]
5) Acrylamide or methacrylamides such as acrylamide, methacrylamide, N-ethylacrylamide, N-hexylacrylamide, N-cyclohexylacrylamide, N-phenylacrylamide, N- (4-nitrophenyl) acrylamide, N-ethyl-N- Phenylacrylamide, N- (4-hydroxyphenyl) acrylamide, N- (4-hydroxyphenyl) methacrylamide and the like.
[0076]
6) Monomers containing fluorinated alkyl groups such as trifluoroethyl acrylate, trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, hexafluoropropyl methacrylate, octafluoropentyl acrylate, octafluoropentyl methacrylate, heptadecafluorodecyl methacrylate, N- Butyl-N- (2-acryloxyethyl) heptadecafluorooctylsulfonamide and the like.
[0077]
7) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, phenyl vinyl ether and the like.
[0078]
8) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate, vinyl benzoate and the like.
[0079]
9) Styrenes such as styrene, methyl styrene, chloromethyl styrene and the like.
[0080]
10) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.
[0081]
11) Olefins such as ethylene, propylene, i-butylene, butadiene, isoprene and the like.
[0082]
12) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine and the like.
[0083]
13) Monomers having a cyano group, such as acrylonitrile, methacrylonitrile, 2-pentenenitrile, 2-methyl-3-butenenitrile, 2-cyanoethyl acrylate, o- (or m-, p-) cyanostyrene.
[0084]
14) A monomer having an amino group, such as N, N-diethylaminoethyl methacrylate, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, polybutadiene urethane acrylate, N, N-dimethylaminopropyl acrylamide, N, N-dimethylacrylamide, acryloylmorpholine, Ni-propylacrylamide, N, N-diethylacrylamide and the like.
[0085]
Further, other monomers that can be copolymerized with these monomers may be copolymerized.
Furthermore, an unsaturated bond-containing vinyl copolymer obtained by addition-reacting a compound having a (meth) acryloyl group and an epoxy group in the molecule to a carboxyl group present in the molecule of the vinyl copolymer. Is also preferred as a polymer binder.
[0086]
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 No. 11-271969.
[0087]
These copolymers preferably have a weight average molecular weight of 1 to 200,000 as measured by gel permeation chromatography (GPC), but are not limited to this range.
[0088]
The content of the high molecular polymer in the photosensitive layer composition is preferably in the range of 10 to 90% by mass, more preferably in the range of 15 to 70% by mass, and the sensitivity to use in the range of 20 to 50% by mass. Particularly preferred from the viewpoint.
[0089]
Furthermore, the acid value of the resin is preferably used in the range of 10 to 150, more preferably in the range of 30 to 120, and the use in the range of 50 to 90 from the viewpoint of balancing the polarity of the entire photosensitive layer. This is particularly preferable, and it is also possible to prevent aggregation of the pigment in the photosensitive layer coating solution.
[0090]
The coating amount on the support of the photopolymerizable photosensitive layer containing these components is 0.1 g / m in terms of the mass after drying.²~ 5g / m²Is preferably 0.5 g / m²~ 3g / m²Is more preferable.
[0091]
(Oxygen barrier layer)
For the oxygen barrier layer, a water-soluble polymer capable of forming a film having low oxygen permeability is used. Specifically, it contains polyvinyl alcohol and polyvinyl pyrrolidone. Polyvinyl alcohol has an effect of suppressing permeation of oxygen, and polyvinyl pyrrolidone has an effect of ensuring adhesion with an adjacent photosensitive layer.
[0092]
In addition to the above two polymers, polysaccharides, polyethylene glycol, gelatin, glue, casein, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, hydroxyethyl starch, gum arabic, sucrose octaacetate, ammonium alginate, sodium alginate as required Water-soluble polymers such as polyvinylamine, polyethylene oxide, polystyrene sulfonic acid, polyacrylic acid, and water-soluble polyamide can also be used in combination.
[0093]
In the photosensitive lithographic printing plate material according to the present invention, the peeling force between the photosensitive layer and the overcoat layer is preferably 35 g / 10 mm or more, more preferably 50 g / 10 mm or more, still more preferably 75 g / 10 mm or more. Preferred overcoat layer compositions include those described in JP-A-10-10742.
[0094]
The peeling force in the present invention is such that an adhesive tape having a predetermined width having a sufficiently large adhesive force is applied on the overcoat layer and peeled off with the overcoat layer at an angle of 90 degrees with respect to the plane of the photosensitive planographic printing plate material The force of time was measured.
[0095]
The overcoat layer can further contain a surfactant, a matting agent and the like as required. The overcoat layer composition is dissolved in a suitable solvent, applied onto the photosensitive layer and dried to form an overcoat layer. The main component of the coating solvent is particularly preferably water or alcohols such as methanol, ethanol, i-propanol.
[0096]
The thickness of the overcoat layer is preferably from 0.1 to 5.0 μm, particularly preferably from 0.5 to 3.0 μm.
[0097]
As combinations with the configuration of the present invention, JP-A-11-65129, JP-A-11-65126, JP-A-2000-206706, JP-A-2000-81711, JP-A-2002-91014, JP-A-2002-91015 JP, 2002-91016, JP, 2002-91017, JP, 2002-174907, JP, 2002-182401, JP, 2002-196506, JP, 2002-196507, JP, 2002-202616, JP 2002-229187, JP 2002-202615, JP 2002-251019, JP 2002-365813, JP 2003-29427, JP 2003-21908, JP 2003-15318, No. 2003-35960, JP-A No. 2003-43693, The plate material, the plate surface protective agent, the developer material, the automatic developing machine, and the like described in Kaikai 2003-43701, JP-A-2003-43702, JP-A-2003-43703 and the like can also be suitably used. .
[0098]
(Developer)
The developer according to the present invention has a silicate content of SiO.₂It is 0 to 0.1% in terms of mass and is an alkaline aqueous solution containing the compound A, compound B or compound C. Silicate content is SiO₂If it exceeds 0.1% in terms of mass, when the developer is fatigued and its pH is lowered, the silicate is solidified and sludge is easily generated.
[0099]
The compound A, compound B or compound according to the present invention will be described.
(Compound C)
In the compound C according to the present invention, the molecular weight of the saturated alkyl group of the hydrophobic group portion (excluding the alkylene group of the polyoxyalkylene group portion) is 0 to 25% of the molecular weight of the entire hydrophobic group (that is, in the hydrophobic group). Is a nonionic surfactant having a saturated alkyl moiety ratio of 0 to 25%), preferably 0 to 5% of the total molecular weight of the hydrophobic group. If it exceeds 25%, the components eluted from the developed photosensitive lithographic printing plate material cannot be dissolved effectively, and sludge precipitation tends to occur in the developer.
[0100]
Here, “the molecular weight of the saturated alkyl group is 0 to 25% of the molecular weight of the entire hydrophobic group” means that the molecule has two or more hydrophobic groups having a saturated alkyl group in the molecule. The results are calculated in% as a result of calculation using the total molecular weight of all the hydrophobic group elements as the denominator and the molecular weight of the saturated alkyl group element of all the hydrophobic groups as the numerator (saturated alkyl portion). In this case, in the present invention, when a molecule has several hydrophobic groups, the average of each hydrophobic group is “the molecular weight of the saturated alkyl group is 0 to 25% of the molecular weight of the entire hydrophobic group”. However, it is also useful that each hydrophobic group is not on average in the above range.
[0101]
The total molecular weight of the hydrophobic group elements preferably has a certain size, and preferably has a molecular weight of about 120 to 2,000.
[0102]
Next, although the preferable example of the compound C which concerns on this invention is given, in this invention, it is not limited to these.
[0103]
[Chemical 1]

[0104]
The compound C according to the present invention is preferably used in the developer in the range of 0.01 to 5% by mass. Furthermore, it is still more preferable to use in the range of 1-3 mass%.
[0105]
Further, in the above-mentioned compound C, when the molecular weight of the hydrophobic group is too small, the dissolving ability of the photosensitive lithographic printing plate material during development of the photosensitive layer is lowered, and it is difficult to suppress the generation of sludge and sludge. If the molecular weight of the group is too large, the solubility of these compounds in the developer is deteriorated and it becomes difficult to produce and maintain a uniform developer, so the above-mentioned range is preferable.
[0106]
(Compound A)
The compound A according to the present invention comprises a polyoxyethylene group in which the molecular weight of the saturated alkyl group of the hydrophobic group portion (excluding the alkylene group of the polyoxyalkylene group portion) is 0 to 25% of the molecular weight of the entire hydrophobic group Is preferably an anionic surfactant containing 0 to 5% or less of the total molecular weight of the hydrophobic group. If it exceeds 25%, the components eluted from the developed photosensitive lithographic printing plate material cannot be dissolved effectively, and sludge precipitation tends to occur in the developer.
[0107]
Here, “the molecular weight of the saturated alkyl group is 0 to 25% of the molecular weight of the entire hydrophobic group” is the same as described in the compound C, and in this case, the compound A according to the present invention has several compounds. In the case where the molecule has such a hydrophobic group, it is preferable that each hydrophobic group averages “the molecular weight of the saturated alkyl group is 0 to 25% of the molecular weight of the entire hydrophobic group”. Those not in the above range are also useful.
[0108]
The total molecular weight of the hydrophobic group elements preferably has a certain size, and preferably has a molecular weight of about 120 to 2,000.
[0109]
Next, although the preferable example which concerns on the compound A which concerns on this invention is given, in this invention, it is not limited to these.
[0110]
[Chemical formula 2]

[0111]
The compound A according to the present invention is preferably used in the developer in the range of 0.01 to 5% by mass. Furthermore, it is still more preferable to use in the range of 1-3 mass%.
[0112]
In the above-mentioned compound A, if the molecular weight of the hydrophobic group is too small, the dissolving ability of the photosensitive lithographic printing plate material during development of the photosensitive layer is lowered, and it is difficult to suppress the generation of sludge and sludge. If the molecular weight of the group is too large, the solubility of these compounds in the developer is deteriorated and it becomes difficult to produce and maintain a uniform developer, so the above-mentioned range is preferable.
[0113]
(Compound B according to the present invention)
The compound B according to the present invention is a nonionic surfactant represented by the general formula (B). In the general formula (B), R₁Represents an alkyl group which may have a substituent or an aryl group which may have a substituent. m represents an integer of 1 to 3, and n represents an integer of 2 to 30.
[0114]
R₁As the alkyl group of the alkyl group which may have a substituent represented by formula (1), those having 1 to 20 carbon atoms such as methyl group, ethyl group and t-butyl group can be preferably used.₁As the aryl group which may have a substituent represented by formula (1), those having 1 to 10 carbon atoms such as phenyl group and naphthyl group can be preferably used.
[0115]
The above alkyl group and aryl group may have a substituent. Examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom, an alkoxycarbonyl group such as an ethoxycarbonyl group, a methoxy group, Examples thereof include an alkoxy group such as an ethoxy group, an aryl group such as a phenyl group, and a cyano group.
[0116]
Compound B has a hydrophobic group moiety (R₁) Is preferably large to some extent, and preferably 70 or more. Particularly preferred are a naphthyl group, a benzyl group, and an alkyl group having 8 to 12 carbon atoms. If the proportion of hydrophobic groups is small, the solubility of the photosensitive layer is poor and sludge is generated. When this compound is added in a small amount, the solubility of the photosensitive layer is poor and sludge is generated. If the amount is too large, the foaming property becomes too large, or the film thickness of the photosensitive layer is reduced.
[0117]
Polyoxypropylene part of compound B (C₃H₆O)_n(CH₂CH₂CH₂O)_n, (CH (CH₃) CH₂O)_n, (CH₂CH (CH₃O)_nThere are three types, and any structure can be used.₂CH (CH₃O)_nThe structure is most preferred. The value of m is 1 to 3, and most preferably 2 or 3. The value of n is 2-30, and most preferably 5-30. n / m is most preferably in the range of 5 or more and 20 or less. If each value of n, m, m / n is too large or too small, the balance between the hydrophilic group and the hydrophobic group of the active agent is lost, and sludge is reduced and developability is deteriorated.
[0118]
Specific examples of Compound B according to the present invention are shown below, but are not limited thereto.
[0119]
[Chemical Formula 3]

[0120]
[Formula 4]

[0121]
[Chemical formula 5]

[0122]
The compound B according to the present invention is preferably used in the developer in an amount of 0.01 to 5% by mass. Furthermore, it is still more preferable to use in the range of 1-3 mass%.
[0123]
In the above-mentioned compound B, if the molecular weight of the hydrophobic group is too small, the dissolving ability of the photosensitive lithographic printing plate material during development of the photosensitive layer is lowered, and it is difficult to suppress the generation of sludge and sludge. When the molecular weight of the group is too large, the solubility of these compounds in the developer is deteriorated and it becomes difficult to produce and maintain a uniform developer.
[0124]
Since precipitation of the dissolved photosensitive layer component contained in the developer occurs, it is preferable to add a surfactant containing a polyoxyalkylene group having low pH dependency to the developer. In addition, a surfactant having an unsaturated hydrophobic group such as an aryl group is more preferable because the solubilizing power of the dissolved photosensitive layer component is high.
[0125]
The pH of the developer to be used is preferably in the range of 11.0 to less than 12.5.
[0126]
The developer according to the present invention preferably contains an alkali agent, a surfactant, a development stabilizer, and the like, and may contain other additives.
[0127]
(Alkaline agent)
The main component of the developer and replenisher used in the processing method of the present invention preferably contains at least one compound selected from phosphoric acid, carbonic acid, boric acid, phenols, saccharides, oximes and fluorinated alcohols. An alkaline aqueous solution having a pH higher than 8.5 and lower than 13.0 is preferable. More preferably, the pH is 8.5-12. Among these, as weakly acidic substances such as phenols, saccharides, oximes and fluorinated alcohols, those having a dissociation index (pKa) of 10.0 to 13.2 are preferable. Such an acid is selected from those described in IONISATION CONSTANTS OF ORGANIC ACIDS INAQUEOUS SOLUTION published by Pergamon Press, and specifically, salicylic acid (13.0) and 3-hydroxy-2-naphthoic acid. (Same as 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.
[0128]
As the saccharide, a non-reducing sugar that is stable even in an alkali is preferably used. Such non-reducing sugars are saccharides that do not have a free aldehyde group or ketone group and do not exhibit reducing properties, and are trehalose-type oligosaccharides in which reducing groups are bonded to each other, and glycosides in which a reducing group of saccharides and non-saccharides are bonded. These are classified into sugar alcohols reduced by hydrogenation of the body and saccharides, both of which are preferably used in the present invention. Trehalose type oligosaccharides include saccharose and trehalose. Examples of glycosides include alkyl glycosides, phenol glycosides, mustard oil glycosides, and the like. Examples of the sugar alcohol include D, L-arabit, rebit, xylit, D, L-sorbit, D, L-mannit, D, L-exit, D, L-talit, durisit and allozulcit. Furthermore, maltitol obtained by hydrogenation of a disaccharide and a reduced form (reduced water candy) obtained by hydrogenation of an oligosaccharide are preferably used. Furthermore, 2-butanone oxime (12.45), acetoxime (12.42), 1,2-cycloheptanedione oxime (12.3), 2-hydroxybenzaldehyde oxime (12.10), dimethyl Oximes such as glyoxime (11.9), ethanediamide dioxime (11.37) and acetophenone oxime (11.35) such as 2,2,3,3-tetrafluoropropanol-1 (12) .74), trifluoroethanol (12.37), trichloroethanol (12.24), and the like. In addition, aldehydes such as pyridine-2-aldehyde (12.68) and pyridine-4-aldehyde (12.05), adenosine (12.56), inosine (12.5), guanine ( 12.3), nucleic acid-related substances such as cytosine (12.2), hypoxanthine (12.1), xanthine (11.9), diethylaminomethylsulfonic acid (12.32), 1-amino-3,3,3-trifluorobenzoic acid (12.29), isopropylidenedisulfonic acid (12.10), 1,1-ethylidene diphosphonic acid (11.54), 1,1 -1-hydroxyethylidene disulfonate (11.52), benzimidazole (12.86), thiobenzamide (12.8), picolinethioamide (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, phosphoric acid, carbonic acid, sulfosalicylic acid, salicylic acid, and sugar alcohols and saccharose of non-reducing sugar are preferable, and D-sorbite, saccharose, and reduced starch candy have a buffering action in an appropriate pH range. That is preferable because of its low price.
[0129]
The proportion of these acidic substances in the developer is preferably from 0.1 to 30% by mass, and more preferably from 1 to 20% by mass. Below this range, a sufficient buffering effect cannot be obtained, and when the concentration is above this range, it is difficult to achieve high concentration, and the problem of increased costs arises. As the base to be combined with these acids, sodium hydroxide, ammonium, potassium and lithium are preferably used. These alkali agents are used alone or in combination of two or more. When the pH of the developer is 8.5 or less, the image portion of the printing plate obtained from the photosensitive lithographic printing plate material that can be developed with such a developer is physically fragile, and wears quickly during printing. Printing durability is not obtained. Further, the image portion is chemically weak, and the image of the portion wiped with an ink washing solvent or a plate cleaner is damaged during printing, and as a result, sufficient chemical resistance cannot be obtained. A developer having a high pH such that the pH exceeds 13.0 is highly irritating when adhering to the skin or mucous membrane, and is not preferable because it requires sufficient care in handling.
[0130]
Other examples include tripotassium phosphate, trisodium phosphate, trilithium phosphate, triammonium phosphate, dipotassium phosphate, disodium phosphate, dilithium phosphate, diammonium phosphate, potassium carbonate, sodium carbonate, lithium carbonate, ammonium carbonate, carbonate Examples include potassium hydrogen carbonate, sodium hydrogen carbonate, lithium hydrogen carbonate, ammonium hydrogen carbonate, potassium borate, sodium borate, lithium borate, ammonium borate and the like, and may be added in the form of a preformed salt. Again, sodium hydroxide, ammonium, potassium and lithium can be added to the pH adjustment. Moreover, 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.
[0131]
The developing solution referred to in the present invention is not only an unused solution used at the start of development, but also a replenisher solution is replenished to correct the activity of the solution that decreases due to the processing of the photosensitive lithographic printing plate material. In addition, a liquid whose activity is maintained (so-called running liquid) is included. The replenisher therefore needs to have a higher activity (alkali concentration) than the developer, so the pH of the replenisher may exceed 13.0.
[0132]
(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 promoting developability, dispersing development residue, and improving ink affinity of the printing plate image area. Examples of the surfactant include known anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, fluorosurfactants, and polymer surfactants. Surfactant can be used individually or in combination of 2 or more types, and is added in 0.001-10 mass% in a developing solution, More preferably, it is added in 0.01-5 mass%.
[0133]
(Development stabilizer)
For the developer and replenisher used in the present invention, various development stabilizers are 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 such as diphenyliodonium chloride. A salt is a preferred example. Further, anionic surfactants or amphoteric surfactants described in JP-A-50-51324, water-soluble cationic polymers described in JP-A-55-95946, and JP-A-56-142528 are described. There are water-soluble amphoteric polyelectrolytes that have been described. Furthermore, an organic boron compound to which an alkylene glycol is added as described in JP-A-59-84241, a polyoxyethylene / polyoxypropylene block polymerization type water-soluble surfactant as described in JP-A-60-111246, An alkylenediamine compound substituted with polyoxyethylene / polyoxypropylene disclosed in JP-A-60-129750, a polyethylene glycol having a weight average molecular weight of 300 or more described in JP-A-61-215554, and a cation described in JP-A-63-175858 And a water-soluble ethylene oxide addition compound obtained by adding 4 mol or more of ethylene oxide to an acid or alcohol disclosed in JP-A-2-39157, a water-soluble polyalkylene compound, and the like.
[0134]
(Organic solvent)
If necessary, an organic solvent is added to the developer and the development replenisher. As such an organic solvent, those having a solubility in water of about 10% by mass or less are suitable, and are preferably selected from those having 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- Benzyloxyethanol, o-methoxybenzyl alcohol, m-methoxybenzyl alcohol, p-methoxybenzyl alcohol, benzyl alcohol, cyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol and 4-methylcyclohexanol, N-phenylethanol Examples thereof include amines and N-phenyldiethanolamine. The content of the organic solvent is 0.1 to 5% by mass with respect to the total mass of the liquid used, but it is preferably substantially not contained, and particularly preferably not contained at all. Here, “substantially not contained” means 1% by mass or less.
[0135]
(Reducing agent)
A reducing agent is added to the developer and replenisher used in the present invention as necessary. This prevents stains on the printing plate, and is particularly effective when developing a negative photosensitive lithographic printing plate material containing a photosensitive diazonium salt compound. Preferable organic reducing agents include phenol compounds such as thiosalicylic acid, hydroquinone, metol, methoxyquinone, resorcin, and 2-methylresorcin, and amine compounds such as phenylenediamine and phenylhydrazine. More preferable inorganic reducing agents include sodium, potassium and ammonium salts of inorganic acids such as sulfurous acid, bisulfite, phosphorous acid, hydrogen phosphite, dihydrogen phosphite, thiosulfuric acid and dithionite. A salt etc. can be mentioned. Among these reducing agents, sulfites are particularly excellent in the antifouling effect. These reducing agents are preferably contained in the range of 0.05 to 5% by mass with respect to the developer at the time of use.
[0136]
(Organic carboxylic acid)
If necessary, an organic carboxylic acid can be further added to the developer and replenisher used in the present invention. Preferred organic carboxylic acids are aliphatic carboxylic acids and aromatic carboxylic acids having 6 to 20 carbon atoms. Specific examples of the aliphatic carboxylic acid include caproic acid, enanthylic 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, it may be an unsaturated fatty acid having a double bond in the carbon chain or a branched carbon chain. The aromatic carboxylic acid is a compound in which a carboxyl group is substituted on a benzene ring, naphthalene ring, anthracene ring or the like, and specifically includes o-chlorobenzoic acid, p-chlorobenzoic acid, o-hydroxybenzoic acid, p- 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, There are 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. Naphthoic acid is particularly effective. The aliphatic and aromatic carboxylic acids are preferably used as sodium salts, potassium salts or ammonium salts 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 it is less than 0.1% by mass, the effect is not sufficient, and if it is 10% by mass or more, the effect cannot be further improved. In addition, dissolution may be hindered when other additives are used in combination. Therefore, the preferable addition amount is 0.1 to 10% by mass, and more preferably 0.5 to 4% by mass with respect to the developing solution at the time of use.
[0137]
(Other)
In addition to the above, the following additives can be added to the developer and replenisher used in the present invention in order to improve the development performance. For example, neutral salts such as NaCl, KCl, KBr described in JP-A-58-75152, and [Co (NH₃]]₆Cl₃, Amphoteric polymer electrolytes such as a copolymer of vinylbenzyltrimethylammonium chloride and sodium acrylate described in JP-A-56-142258, Si, Ti, etc. described in JP-A-59-75255 Examples thereof include organometallic surfactants and organoboron compounds described in JP-A-59-84241. The developer and replenisher used in the present invention may further contain a preservative, a colorant, a thickener, an antifoaming agent, a hard 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. Examples of water softeners include polyphosphoric acid and its sodium, potassium and ammonium salts, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminedisuccinic acid, methyliminodiacetic acid, β-alaninediacetic acid, triethylenetetraminehexaacetic acid, hydroxyethylethylenediaminetrimethyl. Aminopolycarboxylic acids such as acetic acid, nitrilotriacetic acid, 1,2-diaminocyclohexanetetraacetic 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) Hydroxyethyl ethylene diamine tri (methylene phosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid and their sodium salts, potassium salts and ammonium salts. The optimum value of such a hard water softening agent varies depending on its chelating power, the hardness of the hard water used and the amount of hard water. % By mass, more preferably in the range of 0.01 to 0.5% by mass. If the addition amount is less than this range, the intended purpose is not sufficiently achieved. If the addition amount is more than this range, adverse effects on the image area such as color loss will occur. The remaining component of the developer and replenisher is water. More preferably, the obtained developer has a conductivity of 3 to 100 mS and a surface tension of 20 to 80 dyne / cm.
[0138]
JP-A-11-65129, JP-A-11-65126, JP-A-2000-206706, JP-A-2000-81711, JP-A-2002-91016, JP-A-2002-174907, JP-A-2002-182401, Special JP 2002-196506, JP 2002-196507, JP 2002-202616, JP 2002-229187, JP 2002-202615, JP 2002-251019, JP 2002-365813, JP 2003 -29427, JP 2003-21908, JP 2003-15318, JP 2003-35960, JP 2003-43693, JP 2003-43701, JP 2003-43702, JP 2003-2003. No. 57849, JP 2003-66622 A, etc. Developer material are, treating agent such as the plate surface protective agent and the material can be suitably used for the automatic developing machine or the like.
[0139]
(Concentrated liquid)
It is advantageous in terms of transportation that the developer and replenisher used in the present invention are concentrated solutions in which the water content is less than in use, and diluted with water during use. The degree of concentration in this case is appropriate so that each component does not separate or precipitate, but it is preferable to add a solubilizing agent if necessary. As such a solubilizer, a so-called hydrotrope such as toluenesulfonic acid, xylenesulfonic acid and alkali metal salts thereof described in JP-A-6-32081 is preferably used.
[0140]
The content of water in the concentrate can be further reduced to form a solid or paste. In this case, the developer may be once evaporated and then evaporated to dryness, but it is preferable that the concentrated state is obtained by mixing the materials without adding water when adding a plurality of materials or by adding a small amount of water. Is preferred. Further, this developer concentrate is disclosed in JP-A-51-61837, JP-A-2-109042, JP-A-2-109043, JP-A-3-39735, JP-A-5-142786, JP-A-6-266062. No. 1, JP-A-7-13341, etc., and can be made into granules and tablets by a conventionally well-known method. As the material contained in the solid or paste developer concentrate, the components used in the developer of ordinary photosensitive lithographic printing plate materials can be used, but they do not return to their original form even if diluted with water. It is preferable not to include anything. For example, since silicate is converted into stone when it becomes low in moisture, it becomes difficult to dissolve in water, and therefore it is preferable to contain carbonate, phosphate, organic acid salt, etc. described later instead of silicate.
[0141]
These developer concentrates or solid or paste concentrates may be divided into a plurality of parts having different material types, material mixing ratios, and the like. These concentrated developer concentrates are preferably used for development after dilution to a predetermined concentration with water before development. In addition, when this developer concentrate or concentrate is used as a developer replenisher, it is most preferable to dilute with water to a predetermined concentration and then add it to the developer in use. It is also possible to put it in a developing solution as it is without diluting to a predetermined concentration. When adding the developer concentrate to a developing solution in use at a concentration higher than a predetermined concentration or without diluting to a predetermined concentration, water is added directly to the developing solution in use at the same timing or at another timing. May be added.
[0142]
(Automatic processor)
The automatic developing machine used in the present invention is preferably provided with a mechanism for automatically replenishing a replenisher with a necessary amount in a developing bath, and preferably provided with a mechanism for discharging a developer exceeding a certain amount, Preferably, a mechanism for automatically replenishing a required amount of water to the developing bath is provided, preferably a mechanism for detecting plate passing is provided, and preferably the processing area of the plate based on detection of plate passing A mechanism for controlling the replenishment amount and / or replenishment timing of the replenisher and / or water to be replenished, preferably based on detection of the plate and / or estimation of the processing area. Preferably, a mechanism for controlling the temperature of the developer is provided, preferably a mechanism for detecting the pH and / or conductivity of the developer is provided, preferably the pH of the developer and Or mechanism for controlling the replenishment amount and / or replenishment timing of replenishment solution and / or water attempts to replenish based on conductivity is imparted. Moreover, when there exists a washing process after a image development process, the washing water after use can be used as a dilution water of the concentrate of a development concentrate and a development replenisher.
[0143]
The automatic processor used in the present invention may have a pretreatment unit that immerses the plate in the pretreatment liquid before the development step. The pretreatment unit is preferably provided with a mechanism for spraying the pretreatment liquid onto the plate surface, and preferably provided with a mechanism for controlling the temperature of the pretreatment liquid to an arbitrary temperature of 25 ° C to 55 ° C. Preferably, a mechanism for rubbing the plate surface with a roller-like brush is provided. Moreover, water etc. are used as this pretreatment liquid.
[0144]
The automatic processor used in the present invention preferably has a function of replenishing water in order to compensate for the evaporation of water in the developer. If the automatic processor has a water supply mechanism for diluting the concentrated developer, it may be used. A method of replenishing water determined per hour is the simplest and preferable method for replenishing water. However, the water replenishment amount may be corrected based on measured values from sensors such as pH of the developer and electric power. Further, the replenishment amount of water may be corrected using the temperature and / or humidity of the outside air, the temperature of the developer, the temperature and / or humidity of the air in the automatic developing machine, and the like.
[0145]
Also, the developer surface should be as small as possible in order to prevent the pH of the developer from decreasing due to the absorption of carbon dioxide in the air by the alkaline developer and the concentration of the developer due to evaporation of water in the developer. preferable. A high effect can be obtained by shielding the developer surface with a floating lid or the like. It is also an effective method to limit the contact between the air inside the self-machine and the outside air. It is preferable that the entrance / exit of the plate material of the automatic machine is as small as possible and has an automatic opening / closing mechanism that opens only when the plate material passes. Further, a method of removing carbon dioxide in the air in the self-machine is also effective, and a method of removing carbon dioxide by bringing an alkaline aqueous solution or alkaline developer waste liquid into contact with the air in the self-machine can be used effectively.
[0146]
(Post-processing)
The plate developed with the developer having such a composition is subjected to post-processing with washing water, a rinsing solution containing a surfactant, a finisher mainly composed of gum arabic or starch derivatives, or a protective gum solution. For the post-treatment of the PS plate of the present invention, these treatments can be used in various combinations. For example, a post-development → water wash → surfactant-containing rinse solution treatment or development → water wash → finisher solution treatment is a rinse solution. And less finisher fluid fatigue. Furthermore, a countercurrent multistage process using a rinse liquid or a finisher liquid is also a preferred embodiment. These post-processing are generally performed using an automatic developing machine including a developing unit and a post-processing unit. As the post-treatment liquid, a method of spraying from a spray nozzle or a method of immersing and conveying 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 after development is supplied to the plate surface and washed, and the waste solution is reused as dilution water for the developer stock solution. In such automatic processing, processing can be performed while each replenisher is replenished with each replenisher according to the processing amount, operating time, and the like. In addition, a so-called disposable processing method in which treatment is performed with a substantially unused post-treatment liquid can also be applied. The lithographic printing plate obtained by such processing is loaded on an offset printing machine and used for printing a large number of sheets.
[0147]
(Gum solution)
It is preferable to add an acid or a buffering agent to the gum solution in order to remove alkali components from the developer, and in addition, a hydrophilic polymer compound, a chelating agent, a lubricant, a preservative, a solubilizing agent, and the like can be added. When the gum solution contains a hydrophilic polymer compound, it also has a function as a protective agent for preventing scratches and stains on the developed plate.
[0148]
By adding a surfactant to the gum solution used in the present invention, the surface state of the coating layer is improved. Surfactants that can be used include anionic surfactants and / or nonionic surfactants. For example, anionic surfactants include fatty acid salts, abietic acid salts, hydroxyalkane sulfonates, alkane sulfonates, dialkyl sulfosuccinates, linear alkyl benzene sulfonates, branched alkyl benzene sulfonates, alkyl naphthalene sulfones. Acid salts, alkylphenoxy polyoxyethylene propyl sulfonates, polyoxyethylene alkyl sulfophenyl ether salts, polyoxyethylene aryl ether sulfonates, polyoxyethylene naphthyl ether sulfonates, N-methyl-N-oleyl taurine sodium salts N-alkylsulfosuccinic acid monoamido disodium salts, petroleum sulfonates, nitrated castor oil, sulfated beef tallow oil, sulfate esters of fatty acid alkyl esters, Rualkyl nitrates, polyoxyethylene alkyl ether sulfates, fatty acid monoglyceride sulfates, polyoxyethylene alkylphenyl ether sulfates, polyoxyethylene styryl phenyl ether sulfates, alkyl phosphate esters, polyoxyethylene alkyl ethers Phosphate ester salts, polyoxyethylene alkylphenyl ether phosphate ester salts, partially saponified products of styrene-maleic anhydride copolymer, partially saponified products of olefin-maleic anhydride copolymer, naphthalenesulfonate formalin condensates Etc. Among these, dialkyl sulfosuccinates, alkyl sulfate esters, and alkyl naphthalene sulfonates are particularly preferably used.
[0149]
Nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene aryl ethers, polyoxyethylene naphthyl ether, polyoxyethylene polystyryl phenyl ether, polyoxyethylene polyoxy Propylene alkyl ether, glycerin fatty acid partial ester, sorbitan fatty acid partial ester, pentaerythritol fatty acid partial ester, propylene glycol mono fatty acid ester, sucrose fatty acid partial ester, polyoxyethylene sorbitan fatty acid partial ester, polyoxyethylene sorbitol fatty acid moiety Esters, polyethylene glycol fatty acid esters, polyglycerol fatty acid partial esters, polyoxyethylenated ester List oils, polyoxyethylene glycerin fatty acid partial esters, fatty acid diethanolamides, N, N-bis-2-hydroxyalkylamines, polyoxyethylene alkylamines, triethanolamine fatty acid esters, trialkylamine oxides, etc. It is done. Of these, polyoxyethylene alkylphenyl ethers, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene-polyoxypropylene block polymers and the like are preferably used. Fluorine-based and silicon-based anions and nonionic surfactants can also be used. Two or more of these surfactants can be used in combination. For example, two or more different from each other can be used in combination. For example, a combination of two or more different anionic surfactants or a combination of an anionic surfactant and a nonionic surfactant is preferable. Although the usage-amount of the said surfactant does not need to specifically limit, Preferably it is 0.01-20 mass% of a post-processing liquid.
[0150]
In the gum solution used in the present invention, polyhydric alcohols, alcohols and aliphatic hydrocarbons can be used as a wetting agent in addition to the above components as required.
[0151]
Among the polyhydric alcohols, preferred specific examples include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, tetraethylene glycol, polyethylene glycol, glycerin, sorbitol and the like. Examples of the alcohol include propyl alcohol, butyl alcohol, and pen. Examples include alkyl alcohols such as tanol, hexanol, heptanol, and octanol, and alcohols having an aromatic ring such as pendyl alcohol, phenoxyethanol, and phenylaminoethyl alcohol. The content of these wetting agents is suitably 0.1 to 50% by mass, more preferably 0.5 to 3.0% by mass in the composition.
[0152]
Moreover, various hydrophilic polymers can be contained for the purpose of improving the film-forming property.
[0153]
As such a hydrophilic polymer, any hydrophilic polymer that can be conventionally used in a gum solution can be preferably used. For example, gum arabic, fiber derivatives (eg, carboxymethylcellulose, carboxyethylcellulose, methylcellulose etc.) and modified products thereof, polyvinyl alcohol and derivatives thereof, polyvinylpyrrolidone, polyacrylamide and copolymers thereof, vinyl methyl ether / maleic anhydride copolymer Examples thereof include a polymer, a vinyl acetate / maleic anhydride copolymer, and a styrene / maleic anhydride copolymer.
[0154]
In general, the gum solution used in the present invention is more advantageously used in the acidic range of pH 3 to 6. In order to adjust the pH to 3 to 6, it is generally adjusted by adding a mineral acid, an organic acid, an inorganic salt, or the like in the post-treatment liquid. The addition amount is preferably 0.01 to 2% by mass. Examples of mineral acids include nitric acid, sulfuric acid, phosphoric acid, and metaphosphoric acid.
[0155]
Examples of the organic acid include citric acid, acetic acid, succinic acid, malonic acid, p-toluenesulfonic acid, tartaric acid, malic acid, lactic acid, levulinic acid, phytic acid, and organic phosphonic acid. Further, examples of the inorganic salt include magnesium nitrate, primary sodium phosphate, secondary sodium phosphate, nickel sulfate, sodium hexamethanoate, sodium tripolyphosphate, and the like. You may use together at least 1 sort (s) or 2 or more types, such as a mineral acid, an organic acid, or an inorganic salt.
[0156]
A preservative, an antifoaming agent, etc. can be added to the gum solution used in the present invention.
For example, as a preservative, phenol or a derivative thereof, o-phenylphenol, p-chlorometacresol, hydroxybenzoic acid alkyl ester, formalin, imidazole derivative, sodium dehydroacetate, 4-isothiazolin-3-one derivative, benzoisothiazoline-3- ON, benztriazole derivatives, amiding anidine derivatives, quaternary ammonium salts, derivatives of pyridine, quinoline, guanidine, diazine, triazole derivatives, oxazole, oxazine derivatives and the like. A preferable addition amount is an amount that exerts a stable effect on bacteria, molds, yeasts, etc., and varies depending on the type of bacteria, molds, yeasts, but 0.01% with respect to the plate surface protective agent at the time of use. The range of ˜4% by mass is preferable, and it is preferable to use two or more kinds of preservatives in combination so as to be effective against various molds and sterilization. As the antifoaming agent, a silicon antifoaming agent is preferable. Among them, emulsification dispersion type and solubilization can be used. Preferably, the range of 0.01 to 1.0% by mass with respect to the gum solution at the time of use is optimal.
[0157]
Further, a chelate compound may be added. Preferred chelate compounds include, for example, ethylenediaminetetraacetic acid, potassium salt thereof, sodium salt thereof; diethylenetriaminepentaacetic acid, potassium salt thereof, sodium salt thereof; triethylenetetraminehexaacetic acid, sodium salt thereof; ethylenediamine disuccinic acid, potassium salt thereof. Triethylenetetramine hexaacetic acid, potassium salt thereof, sodium salt thereof, hydroxyethylethylenediaminetriacetic acid, potassium salt thereof, sodium salt thereof: nitrilotriacetic acid, sodium salt thereof; 1-hydroxyethane-1,1-diphosphone Acids, potassium salts, sodium salts; organic phosphonic acids or phosphonoalkanetricarboxylic acids such as aminotri (methylenephosphonic acid), potassium salts, sodium salts, etc. It can be mentioned. An organic amine salt is also effective in place of the sodium salt and potassium salt of the chelating agent. These chelating agents are selected so that they are stably present in the gum solution composition and do not impair the printability. The addition amount is suitably 0.001 to 1.0 mass% with respect to the gum solution at the time of use.
[0158]
In addition to the above components, a sensitizer can be added as necessary. For example, hydrocarbons such as turpentine oil, xylene, toluene, low heptane, solvent naphtha, kerosene, mineral spirit, petroleum fraction having a boiling point of about 120 ° C to about 250 ° C, such as dibutyl phthalate, dihebutyl phthalate, di-n-octyl Phthalic acid diester agents such as phthalate, di (2-ethylhexyl) phthalate, dinonyl phthalate, didecyl phthalate, dilauryl phthalate, butyl benzyl phthalate, such as dioctyl adipate, butyl glycol adipate, dioctyl azelate, dibutyl sebacate, di ( 2-ethylhexyl) aliphatic dibasic acid esters such as sebacate and dioctyl sebacate, epoxidized triglycerides such as epoxidized soybean oil, such as tricresyl phosphate, trioctylfolate Feto, phosphoric acid esters such as tris chloroethyl phosphate, for example, freezing point, such as benzoic acid esters of benzyl benzoate and at 15 ℃ below boiling point at one atmosphere include 300 ° C. or more plasticizers.
[0159]
In addition, caproic acid, enanthic acid, caprylic acid, helargonic acid, capric acid, undecyl acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachic acid, behenic acid, lignoserine Saturated fatty acids such as acid, serotic acid, heptacosanoic acid, montanic acid, melicinic acid, lactelic acid, isovaleric acid, and acrylic acid, crotonic acid, isocrotonic acid, undecylenic acid, oleic acid, elaidic acid, celetic acid, nillic acid, buteticidin Examples also include unsaturated fatty acids such as acid, sorbic acid, linoleic acid, linolenic acid, arachidonic acid, propiolic acid, stearolic acid, sardine acid, talylic acid and licanoic acid. More preferably, it is a fatty acid that is liquid at 50 ° C., more preferably 5 to 25 carbon atoms, and most preferably 8 to 21 carbon atoms. These sensitizers can be used alone or in combination of two or more. A preferable range for the amount used is 0.01 to 10% by mass of the gum, and a more preferable range is 0.05 to 5% by mass.
[0160]
The sensitizers as described above may be prepared by emulsifying and dispersing the gum as an oil phase, or may be solubilized with the help of a solubilizer.
[0161]
In the present invention, the solid content concentration of the gum solution is preferably 5 to 30 g / l. The film thickness of the gum can be controlled by the conditions of the squeeze means of the automatic machine. In the present invention, the gum application amount is 1 to 10 g / m.²Is preferred. If the amount of gum application exceeds 10, the plate surface needs to be very hot in order to dry in a short time, which is disadvantageous in terms of cost and safety, and the effects of the present invention cannot be sufficiently obtained. 1g / m²If it is less than 1, uniform coating becomes difficult and stable processability cannot be obtained.
[0162]
In the present invention, the time from the end of the application of the gum solution to the start of drying is preferably 3 seconds or less. More preferably, it is 2 seconds or less, and the shorter the time is, the better the ink deposition property is.
[0163]
In the present invention, the drying time is preferably 1 to 5 seconds.
In the present invention, as a drying method, a known drying method such as a warm air heater or a far infrared heater can be used.
[0164]
In the drying step, the solvent in the gum solution needs to be dried. Therefore, it is necessary to ensure a sufficient drying temperature and heater capacity. The temperature required for drying varies depending on the components of the gum solution, but in the case of a gum solution in which the solvent is water, the drying temperature is preferably 55 ° C. or higher. The heater capacity is often more important than the drying temperature, and the capacity is preferably 2.6 kW or more in the case of the hot air drying method. The larger the capacity, the better, but 2.6-7 kW is preferable in terms of balance with cost.
[0165]
(Washing water before development)
In the present invention, the washing liquid used in the washing step before development is usually water, but the following additives can be added as necessary.
[0166]
As the chelating agent, a compound that forms a chelate compound by coordination with a metal ion is used. Ethylenediaminetetraacetic acid, its potassium salt, its sodium salt, ethylenediaminedisuccinic acid, its potassium salt, its sodium salt, triethylenetetraminehexaacetic acid, its potassium salt, its sodium salt, diethylenetriaminepentaacetic acid, its potassium salt, its sodium salt Hydroxyethylethylenediaminetriacetic acid, potassium salt thereof, sodium salt thereof, nitriotriacetic acid, potassium salt thereof, sodium salt thereof, 1-hydroxyethane-1,1-diphosphonic acid, potassium salt thereof, sodium salt thereof, aminotri (methylenephosphone) Acid), potassium salt thereof, sodium salt thereof, phosphonoalkanetricarboxylic acid, ethylenediamine disuccinic acid, potassium salt thereof, sodium salt thereof and the like. Those chelating agents having an organic amine salt instead of the potassium salt and sodium salt are also effective.
[0167]
The addition amount of the chelating agent is suitably in the range of 0 to 3.0% by mass.
As the surfactant, any of anionic, nonionic, cationic and amphoteric surfactants can be used, and anionic or nonionic surfactants are preferred. The preferred surfactant type varies depending on the composition of the overcoat layer and the photosensitive layer, and generally serves as a dissolution accelerator for the material of the overcoat layer and preferably has a low solubility for the components of the photosensitive layer.
[0168]
Examples of anionic surfactants include fatty acid salts, abichenates, hydroxyalkanesulfonates, alkanesulfonates, dialkylsulfosuccinates, alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkylphenoxypolyoxyethylenepropylsulfonates , Polyoxyethylene alkylsulfophenyl ether salts, sodium N-methyl-N-oleyl taurate, disodium N-alkylsulfosuccinic acid monoamide, petroleum sulfonates, sulfated castor oil, sulfated beef oil, fatty acid alkyl esters Sulfuric acid ester salts, alkyl sulfuric acid ester salts, polyoxyethylene alkyl ether sulfuric acid ester salts, fatty acid monoglyceride sulfuric acid ester salts, polyoxyethylene styrylpheny Ether sulfate ester salt, alkyl phosphate ester salt, polyoxyethylene alkyl ether phosphate ester salt, polyoxyethylene alkyl phenyl ether phosphate ester salt, partially saponified styrene-maleic anhydride copolymer, olefin-maleic anhydride copolymer And partially saponified products, naphthalenesulfonate formalin condensates and the like.
[0169]
Nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene polystyryl phenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, glycerin fatty acid esters, 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, iethylene glycol fatty acid esters, polyglycerin fatty acid partial esters, polyoxyethylenated castor oil , Polyoxyethylene glycerin fatty acid partial esters, fatty acid diethanolamides, N, N-bis-hydroxyalkylamines Polyoxyethylene alkylamine, triethanolamine fatty acid esters, trialkylamine oxides and the like.
[0170]
A preferable addition amount of the surfactant is 0 to 10% by mass. Further, an antifoaming agent can be used in combination with the surfactant.
[0171]
Examples of preservatives include phenol or derivatives thereof, formalin, imidazole derivatives, sodium dehydroacetate, 4-isothiazolin-3-one derivatives, benzoisothiazolin-3-one, benzotriazole derivatives, amiding anidine derivatives, quaternary ammonium salts, pyrozine, Examples include quinoline and guanidine derivatives, diazine, triazole derivatives, oxazole and oxazine derivatives. Preferred examples include 1,2-benzisothiazolin-3-one, o-phenylphenol, hydroxybenzoic acid ethyl ester, chlorocresol and the like.
[0172]
In the cleaning method of the present invention, the cleaning solution used for cleaning before development is preferably used with the temperature adjusted, and the temperature is preferably in the range of 10 to 60 ° C. As a cleaning method, known processing liquid supply techniques such as spraying, dipping, and coating can be used, and processing promoting means such as a brush, a drawing roll, and a submerged shower in the dip processing can be used as appropriate.
[0173]
In the present invention, the development treatment may be performed immediately after completion of the pre-development washing step, or the development treatment may be performed after drying before the pre-development washing step. After the development step, known post-treatments such as washing with water, rinsing and gumming can be performed. The pre-development rinse water used once or more can be reused as a part or all of the rinse water, rinse solution, gum solution and developer after development.
[0174]
【Example】
EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, the aspect of implementation of this invention is not limited to this. In the examples, “parts” represents “parts by mass” unless otherwise specified.
[0175]
Example 1
(Binder synthesis)
(Synthesis of acrylic copolymer 1)
In a three-necked flask under a nitrogen stream, 30 parts of methacrylic acid, 50 parts of methyl methacrylate, 20 parts of ethyl methacrylate, 500 parts of isopropyl alcohol and 3 parts of α, α'-azobisisobutyronitrile are placed in a nitrogen stream. The reaction was carried out in an oil bath at 0 ° C. for 6 hours. Then, after refluxing for 1 hour at the boiling point of isopropyl alcohol, 3 parts of triethylammonium chloride and 25 parts of glycidyl methacrylate were added and reacted for 3 hours to obtain an acrylic copolymer 1. The weight average molecular weight measured using GPC was about 35,000, and the glass transition temperature (Tg) measured using DSC (differential thermal analysis) was about 85 ° C.
[Production of Supports 1 to 4]
(Preparation of support 1)
An aluminum plate (material 1050, tempered H16) having a thickness of 0.3 mm was immersed in a 5% aqueous sodium hydroxide solution maintained at 65 ° C., degreased for 1 minute, and then washed with water. This degreased aluminum plate was neutralized by immersion in a 10% aqueous hydrochloric acid solution maintained at 25 ° C. for 1 minute, and then washed with water. Next, the aluminum plate was placed in a 0.3% by mass nitric acid aqueous solution at 25 ° C. and a current density of 100 A / dm.²Electrolytic surface roughening was performed for 60 seconds with an alternating current under the above conditions, followed by desmutting treatment for 10 seconds in a 5% aqueous sodium hydroxide solution maintained at 60 ° C. The surface-roughened aluminum plate subjected to the desmut treatment was subjected to a current density of 10 A / dm at 25 ° C. in a 15% sulfuric acid solution.²And anodizing for 1 minute under the condition of a voltage of 15 V, and a 1.1 mass% potassium silicate aqueous solution (SiO2 at 82 ° C.₂: 26% by mass, K₂O: 13.5% by mass) to prepare a support 1.
[0176]
(Preparation of support 2)
An aluminum plate (material 1050, tempered H16) having a thickness of 0.3 mm was immersed in a 5% aqueous sodium hydroxide solution maintained at 65 ° C., degreased for 1 minute, and then washed with water. This degreased aluminum plate was neutralized by immersion in a 10% aqueous hydrochloric acid solution maintained at 25 ° C. for 1 minute, and then washed with water. Next, the aluminum plate was placed in a 0.3% by mass nitric acid aqueous solution at 25 ° C. and a current density of 100 A / dm.²Electrolytic surface roughening was performed for 60 seconds with an alternating current under the above conditions, followed by desmutting treatment for 10 seconds in a 5% aqueous sodium hydroxide solution maintained at 60 ° C. The surface-roughened aluminum plate subjected to the desmut treatment was subjected to a current density of 10 A / dm at 25 ° C. in a 15% sulfuric acid solution.²Then, an anodizing treatment was performed for 1 minute under the condition of a voltage of 15 V, and further a treatment with a 1.2% potassium polyvinylphosphonate aqueous solution at 82 ° C. was performed to produce a support 2.
[0177]
(Preparation of support 3)
An aluminum plate (material 1050, tempered H16) having a thickness of 0.3 mm was immersed in a 5% aqueous sodium hydroxide solution maintained at 65 ° C., degreased for 1 minute, and then washed with water. This degreased aluminum plate was neutralized by immersion in a 10% aqueous hydrochloric acid solution maintained at 25 ° C. for 1 minute, and then washed with water. Next, the aluminum plate was placed in a 0.3% by mass nitric acid aqueous solution at 25 ° C. and a current density of 100 A / dm.²Electrolytic surface roughening was performed for 60 seconds with an alternating current under the above conditions, followed by desmutting treatment for 10 seconds in a 5% aqueous sodium hydroxide solution maintained at 60 ° C. The surface-roughened aluminum plate subjected to the desmut treatment was subjected to a current density of 10 A / dm at 25 ° C. in a 15% sulfuric acid solution.²And anodizing for 1 minute under the condition of a voltage of 15 V, and further 0.6 mass% potassium silicate aqueous solution (SiO 2 at 80 ° C.₂: 26% by mass, K₂O: 13.5% by mass), followed by hydrophilization with a 0.8% by mass polyvinylphosphonic acid aqueous solution at 84 ° C. to prepare Support 3.
[0178]
(Preparation of Support 4 (Comparative Example))
An aluminum plate (material 1050, tempered H16) having a thickness of 0.3 mm was immersed in a 5% aqueous sodium hydroxide solution maintained at 65 ° C., degreased for 1 minute, and then washed with water. This degreased aluminum plate was neutralized by immersion in a 10% aqueous hydrochloric acid solution maintained at 25 ° C. for 1 minute, and then washed with water. Next, the aluminum plate was placed in a 0.3% by mass nitric acid aqueous solution at 25 ° C. and a current density of 100 A / dm.²Electrolytic surface roughening was performed for 60 seconds with an alternating current under the above conditions, followed by desmutting treatment for 10 seconds in a 5% aqueous sodium hydroxide solution maintained at 60 ° C. The surface-roughened aluminum plate subjected to the desmut treatment was subjected to a current density of 10 A / dm at 25 ° C. in a 15% sulfuric acid solution.²Then, an anodizing treatment was performed for 1 minute under the condition of a voltage of 15 V, and further a hydrophilization treatment was performed with hot water at 75 ° C. to prepare a support 4.
[0179]
[Table 1]

[0180]
[Preparation of photosensitive lithographic printing plate materials 101 to 104]
On the above supports 1 to 4, a photopolymerizable photosensitive layer coating solution 1 having the following composition was dried at 1.5 g / m.²Then, the sample was coated with a wire bar and dried at 95 ° C. for 1.5 minutes to obtain photopolymerizable photosensitive layer-coated samples each having a photopolymerizable photosensitive layer.
[0181]

(* 1) Synthesis of acrylic copolymer 1
In a three-necked flask under a nitrogen stream, 30 parts of methacrylic acid, 50 parts of methyl methacrylate, 20 parts of ethyl methacrylate, 500 parts of isopropyl alcohol and 3 parts of α, α'-azobisisobutyronitrile are placed in a nitrogen stream. The reaction was carried out in an oil bath at 0 ° C. for 6 hours. Then, after refluxing for 1 hour at the boiling point of isopropyl alcohol, 3 parts of triethylammonium chloride and 25 parts of glycidyl methacrylate were added and reacted for 3 hours to obtain an acrylic copolymer 1. The weight average molecular weight measured using GPC was about 35,000, and the glass transition temperature (Tg) measured using DSC (differential thermal analysis) was about 85 ° C.
[0182]
[Chemical 6]

[0183]
M-3: Nn-butyldiethanolamine (1 mol), 1,3-bis (1-isocyanato-1-methylethyl) benzene (2 mol), 2-hydroxypropylene-1-methacrylate-3- Reaction product of acrylate (2 mol) (described in general description)
On each photopolymerizable photosensitive layer-coated sample (on the photopolymerizable photosensitive layer), an oxygen barrier layer coating solution having the following composition was dried at 1.8 g / m.²The photosensitive lithographic printing plate materials 101 to 104 having an oxygen blocking layer on the photopolymerizable photosensitive layer were prepared by applying with an applicator so as to become, and drying at 75 ° C. for 1.5 minutes.
[0184]

[Preparation of photosensitive lithographic printing plate material 105]
A photosensitive lithographic printing plate material 105 was produced in the same manner as the photosensitive lithographic printing plate material 103 except that the photopolymerizable photosensitive layer coating solution 1 was changed to the photopolymerizable photosensitive layer coating solution 2 described below.
[0185]

[0186]
[Chemical 7]

[0187]
[Preparation of photosensitive lithographic printing plate material 106]
Spectral sensitizing dyes D-1 and D-2 of photopolymerizable photosensitive layer coating solution 1 were changed to D-5 and D-7 (the same amount used) (photopolymerizable photosensitive layer coating solution 3). Except for the above, a photosensitive lithographic printing plate material 106 was produced in the same manner as the photosensitive lithographic printing plate material 103.
[0188]
[Chemical 8]

[0189]
About photosensitive lithographic printing plate materials 101-104, 105, using a CTP exposure apparatus (Tigercat: manufactured by ECRM) equipped with an FD-YAG laser light source, 2400 dpi (dpi represents the number of dots per 2.54 cm) Image exposure was performed at a resolution (exposure pattern used 100% image area and 175 lpi (where lpi represents the number of lines per 2.54 cm) 50% square dots).
[0190]
The photosensitive lithographic printing plate material 106 was subjected to the same image exposure using a plate setter (Tiger Cat: a modified product manufactured by ECRM) equipped with a light source equipped with a laser of 408 nm and 30 mW output.
[0191]
Next, a pre-water washing part for removing the oxygen blocking layer before development, a developing part filled with the following developer, a water washing part for removing the developer attached to the plate surface, and the above-mentioned gum solution for protecting the image line part were provided. Using a CTP automatic developing machine (PHW32-U: manufactured by Technology), development processing is performed to 500 m so that the area ratio of the image area and the non-image area is 1: 9.²Carried out. About 50ml / m²The following developer replenisher was replenished so that the developer was replenished.
[0192]
[Preparation of developer and developer replenisher]
The following developer and developer replenisher were prepared.
[0193]

[0194]
[Chemical 9]

[0195]

[Preparation of developer and developer replenisher]
A gum solution (finisher solution (plate surface protecting agent)) having the following formulation was prepared.
[0196]

[Evaluation methods]
(Silicon atom concentration and phosphorus atom concentration (atomic%) on the surface of the aluminum plate support) The silicon atomic weight concentration and phosphorus atom concentration (atomic%) on the surface of the obtained support (aluminum plate support) were scanned by Rigaku Corporation. Type X-ray fluorescence analyzer ZSX-100e.
[0197]
(Stop dirt)
The photosensitive lithographic printing plate material is 500m with an automatic processor.²The lithographic printing plate obtained by developing in the state after processing is applied to a printing machine (DAIYA 1F-1 manufactured by Mitsubishi Heavy Industries, Ltd.), coated paper, dampening water (etching solution SG-51 manufactured by Tokyo Ink Co., Ltd., concentration 1. 5%), ink (Toyo Ink VOC zero ink “TK Hi-Echo SOY1”) was used for printing, and when the lithographic printing plate used for this printing was printed 5000 sheets, the printing machine was temporarily stopped, After leaving for 1 hour, printing is restarted, and after printing 100 sheets, the fine dot-like stain generated on the printed matter is 100 cm.²It was evaluated by the number within. It is good if the number of fine spot-like stains is 10 or less. If it is 30 or more, there is a problem in practical use.
(Good is 10 or less. Problem is 30 or more.)
(Evaluation of sludge sludge)
500m with automatic processor²The amount of sludge sludge in the tank after the development after processing was confirmed.
[0198]
○: Slight sludge generation is observed in the developing tank, but it does not adhere to the developed photosensitive lithographic printing plate material or developed lithographic printing plate, and there is substantially no problem. Also, the developer tank can be cleaned with water.
Δ: Sludge is generated in the developing tank, and it is difficult to clean the developing tank simply by flushing with water, and rubbing with a sponge or brush is necessary. The photosensitive lithographic printing plate material to be developed and the developed lithographic printing plate do not adhere to sludge sludge, and the development work itself has no problem.
×: Sludge sludge is clogged in the circulating pump of the self-machine, or adheres to the lithographic printing plate after development and stains occur.
[0199]
The results are shown in Table 2.
[0200]
[Table 2]

[0201]
From Table 2, in the case of the configuration of the present invention (photosensitive lithographic printing plate material processing method), after the printing press is stopped for a while due to registration or break at the time of printing, the fineness generated in the non-image portion when printing is resumed. It can be seen that spot-like dirt (stop dirt) can be prevented, and sludge sludge accumulated in the developing bath can be reduced when developing is performed for a long period of time, thereby reducing the burden of cleaning work.
[0202]
In recent years, environmental preservation has been screamed in the printing industry, and ink that does not use petroleum-based volatile organic compounds (VOC) has been developed and is spreading. The configuration of the present invention is such an environment-friendly printing ink (for example, soybean oil ink “Naturalis 100” manufactured by Dainippon Ink and Chemical, VOC zero ink “TK high echo SOY1” manufactured by Toyo Ink, Tokyo Ink When using process inks such as “Soyselbo” manufactured by the company, the effects of the present invention (particularly the prevention of stop stains and the reduction of sludge generated in the developer and the prevention of stain adhesion to non-image areas) are remarkable. Demonstrate.
[0203]
【The invention's effect】
According to the present invention, after stopping the printing press for a while due to registration or break at the time of printing, it is possible to prevent fine spot-like stains (stop stains) that occur in the non-image area when printing is resumed, and long-term development processing It was possible to provide a method for processing a photosensitive lithographic printing plate material capable of reducing sludge sludge accumulated in the developing bath and reducing the burden of cleaning work.

Claims (6)

A photosensitive lithographic printing plate material having a photosensitive layer of a photopolymerizable photosensitive resin composition containing an ethylenically unsaturated bond-containing monomer, a photopolymerization initiator, and a polymer binder on the surface of an aluminum plate support, silicic acid the content of the salt is a processing method of the photosensitive lithographic printing plate material to development processing with a developer of an alkaline aqueous solution containing is 0 to 0.1 percent and the following compound a with SiO ₂ mass conversion, said photosensitive layer A method for processing a photosensitive lithographic printing plate material, wherein the silicon atom concentration on the surface of the aluminum plate support before coating is 5 to 20 atomic%.
Compound A: An anionic surfactant containing a polyoxyethylene group, wherein the molecular weight of the saturated alkyl group in the hydrophobic group portion is 0 to 25% of the molecular weight of the entire hydrophobic group. A photosensitive lithographic printing plate material having a photosensitive layer of a photopolymerizable photosensitive resin composition containing an ethylenically unsaturated bond-containing monomer, a photopolymerization initiator and a polymer binder on the surface of an aluminum plate support, silicic acid A method for processing a photosensitive lithographic printing plate material, in which a salt content is 0 to 0.1% in terms of SiO ₂ mass and development is performed with an alkaline aqueous developer containing the following compound B, the photosensitive layer comprising: A method for processing a photosensitive lithographic printing plate material, wherein the silicon atom concentration on the surface of the aluminum plate support before coating is 5 to 20 atomic%.
Compound B: Nonionic surfactant represented by the following general formula (B) General formula (B)
_{R 1 -O- (C 3 H 6} O) m - (C 2 H 4 O) n -H
(In the formula, R ₁ represents an alkyl group which may have a substituent or an aryl group which may have a substituent. M represents an integer of 1 to 3, and n represents an integer of 2 to 30. .) A photosensitive lithographic printing plate material having a photosensitive layer of a photopolymerizable photosensitive resin composition containing an ethylenically unsaturated bond-containing monomer, a photopolymerization initiator, and a polymer binder on the surface of an aluminum plate support, silicic acid A method for processing a photosensitive lithographic printing plate material, in which a salt content is 0 to 0.1% in terms of SiO ₂ mass and development is performed with an alkaline aqueous developer containing the following compound C, the photosensitive layer comprising: A method for processing a photosensitive lithographic printing plate material, wherein the concentration of silicon atoms on the surface of the aluminum plate support before coating is 5 to 20 atomic%.
Compound C: A nonionic surfactant, wherein the molecular weight of the saturated alkyl group in the hydrophobic group portion is 0 to 25% of the molecular weight of the entire hydrophobic group. A photosensitive lithographic printing plate material having a photosensitive layer of a photopolymerizable photosensitive resin composition containing an ethylenically unsaturated bond-containing monomer, a photopolymerization initiator and a polymer binder on the surface of an aluminum plate support, silicic acid the content of the salt is a processing method of the photosensitive lithographic printing plate material to development processing with a developer of an alkaline aqueous solution containing is 0 to 0.1 percent and the following compound a with SiO ₂ mass conversion, said photosensitive layer A method for processing a photosensitive lithographic printing plate material, wherein the concentration of phosphorus atoms on the surface of the aluminum plate support before coating is 3 to 15 atomic%.
Compound A: An anionic surfactant containing a polyoxyethylene group, wherein the molecular weight of the saturated alkyl group in the hydrophobic group portion is 0 to 25% of the molecular weight of the entire hydrophobic group. A photosensitive lithographic printing plate material having a photosensitive layer of a photopolymerizable photosensitive resin composition containing an ethylenically unsaturated bond-containing monomer, a photopolymerization initiator and a polymer binder on the surface of an aluminum plate support, silicic acid A method for processing a photosensitive lithographic printing plate material, in which a salt content is 0 to 0.1% in terms of SiO ₂ mass and development is performed with an alkaline aqueous developer containing the following compound B, the photosensitive layer comprising: A method for processing a photosensitive lithographic printing plate material, wherein the concentration of phosphorus atoms on the surface of the aluminum plate support before coating is 3 to 15 atomic%.
Compound B: Nonionic surfactant represented by the following general formula (B) General formula (B)
_{R 1 -O- (C 3 H 6} O) m - (C 2 H 4 O) n -H
(In the formula, R ₁ represents an alkyl group which may have a substituent or an aryl group which may have a substituent. M represents an integer of 1 to 3, and n represents an integer of 2 to 30. .) A photosensitive lithographic printing plate material having a photosensitive layer of a photopolymerizable photosensitive resin composition containing an ethylenically unsaturated bond-containing monomer, a photopolymerization initiator, and a polymer binder on the surface of an aluminum plate support, silicic acid A method for processing a photosensitive lithographic printing plate material, in which a salt content is 0 to 0.1% in terms of SiO ₂ mass and development is performed with an alkaline aqueous developer containing the following compound C, the photosensitive layer comprising: A method for processing a photosensitive lithographic printing plate material, wherein the concentration of phosphorus atoms on the surface of the aluminum plate support before coating is 3 to 15 atomic%.
Compound C: A nonionic surfactant, wherein the molecular weight of the saturated alkyl group in the hydrophobic group portion is 0 to 25% of the molecular weight of the entire hydrophobic group.