JP3778768B2 - Finishing liquid for lithographic printing plates - Google Patents

Description

【００２１】
式中ｎは１〜６の整数。Ｒ₁は水素原子または酸基を持たない水素、炭素、窒素、酸素原子より任意に選ばれる複数の原子からなる置換基で、Ｒ₁が酸素原子を含む場合、酸素原子は必ず２個の炭素原子と結合している。Ｒ₁が窒素原子を含む場合、窒素原子は炭素と複素環をするか、もしくは炭素原子あるいは水素原子より選ばれる３個の原子と結合している。
【００２２】
【化２】

【００２３】
式中ｎ、ｍは１〜６の整数。Ｒ₁、Ｒ₂は水素原子または酸基を持たない水素、炭素、窒素、酸素原子より任意に選ばれる複数の原子からなる置換基で、Ｒ₁、Ｒ₂が酸素原子を含む場合、酸素原子は必ず２個の炭素原子と結合している。Ｒ₁、Ｒ₂が窒素原子を含む場合、窒素原子は炭素と複素環を形成するか、もしくは炭素原子あるいは水素原子より選ばれる３個の原子と結合している。Ｒ₁とＲ₂は互いに連結して環を形成しても良い。
【００２４】
【化３】

【００２５】
式中ｎ、ｍ，ｏは１〜６の整数。、Ｒ₁、Ｒ₂、Ｒ₃は水素原子または酸基を持たない水素、炭素、窒素、酸素原子より任意に選ばれる複数の原子からなる置換基で、Ｒ₁、Ｒ₂、Ｒ₃が酸素原子を含む場合、酸素原子は必ず２個の炭素原子と結合している。Ｒ₁、Ｒ₂、Ｒ₃が窒素原子を含む場合、窒素原子は炭素と複素環を形成するか、もしくは炭素原子あるいは水素原子より選ばれる３個の原子と結合している。Ｒ₁とＲ₂、Ｒ₁とＲ₃もしくはＲ₂とＲ₃互いに連結して環を形成しても良い。
【００２６】
以下にＲ₁、Ｒ₂、Ｒ₃の例を挙げるが本発明はこれに限定されるものではない。Ｒ₁、Ｒ₂、Ｒ₃の置換基のうちで互いに連結していないものの例としては、アルキル基、アルケニル基、シクロアルキル基、フェニル基等の炭化水素、アルコキシ基、アルキレンオキシ基、フェノキシ基等の酸素原子を介したもの、アミノ基、置換アミノ基等の窒素原子を介したもの、さらにトリアゾール、イミダゾール、テトラゾール、オキサゾール、トリアジン、ピペラジン、ピペリジン、モルホリン、イミダゾリジン、ベンゾトリアゾール等の複素環で置換基を形成しても良い。またＲ₁、Ｒ₂、Ｒ₃の置換基は、上記の置換基がさらに上記の置換基で１個以上置換されていても良い。則ち、アルコシアルキル基、アミノアルキル基、アミノアルコキシ基、アミノアルコキシアルコキシ基等の置換基を挙げることができる。
Ｒ₁、Ｒ₂、Ｒ₃の置換基のうちで互いに連結しているものは、上記の置換基同士が連結している場合と考えれば良く、上記から容易に類推できるので特に例示はしない。
【００２７】
以下に化１、化２および化３の具体例を挙げるが本発明はこれらに限定されるものではない。環を形成していないものとしては、エチルアミン、ｎ−プロピルアミン、イソプロピルアミン、ｔ−ブチルアミン、メトキシエチルアミン、メトキシプロピルアミン、エトキシプロピルアミン、エチレンジアミン、１，３ジアミノプロパン、１，２プロパンジアミン、１，４ジアミノブタン、１，５ジアミノペンタン、１，６ジアミノヘキサン、ジエチレントリアミン、トリエチレンテトラミン、ジエチルアミン、ジイソプロピルアミン、Ｎ−エチルジイソプロピルアミン、Ｎ−メチル１，３プロパンジアミン、３，３、ミノプロピルアミン、３−（ジメチルアミノ）プロピルアミン、３−（ジエチルアミノ）プロピルアミン、Ｎ−メチル−３，３'−イミノビス（プロピルアミン）、トリス（２−アミノエチル）アミン等を挙げることができる。環状アミンの中で、ピペラジンおよびその誘導体として、ピペラジン、２−メチルピペラジン、Ｎ−メチルピペラジン、２，５ジメチルピペラジン、２，６ジメチルピペラジン、２−アミノメチルピペラジン、Ｎ−（２−アミノエチル）ピペラジン、１，４−ビスアミノプロピルピペラジン、１−アミノ−４−メチルピペラジン、等を挙げることができる。その他の環状アミンンとして、モルホリン、Ｎ−アミノプロピルモルホリン等のモルホリン類、ピペリジン、ピロリジン、イミダゾリジン、およびその誘導体、トリエチレンジアミン、ヘキサメチレンテトラミン等の環状橋掛け化合物を挙げることができる。
【００２８】
これらのアミン類の添加量に特に規定はないが、好ましくは０．０１〜１モル／リットル、さらに好ましくは０．０５〜０．５モル／リットルである。
【００２９】
仕上げ液のＰＨは、３〜８の間が好ましく、さらに好ましくは４〜７である。一方、スターター液は５〜８が好ましい。ＰＨ調整にはリン酸、硫酸、酢酸その他の有機酸を使用することができる。
【００３０】
本発明の仕上げ液にはリン酸またはその塩を含むことが好ましい。リン酸またはリン酸塩の例としてはリン酸、リン酸ナトリウム、リン酸アンモニウム、リン酸カリウム、トリエタノールアミンンリン酸塩、その他アミンン類とのリン酸塩を挙げることができる。これらの添加量は、好ましくは０．０５〜１モル／リットルの範囲である。
【００３１】
本発明の仕上げ液には、前記化合物の他にアラビヤガム、デキストリン、アルギン酸ナトリウム、アルギン酸のプロピレングリコールエステル、ヒドロキシエチル澱粉、カルボキシメチルセルロース、ヒドロキシエチルセルロース、ポリビニルピロリドン、ポリスチレンスルホン酸、ポリビニルアルコール等の保護コロイド、またはそれらの混合物を含有することができる。また、防腐剤を含有させてもよい。仕上げ液には更にタンパク質分解酵素を含有させるのが好ましい。これら酵素の例としては、ペプシン、レニン、トリプシン、キモトリプシン、カテプシン、パパイン、フィシン、トロンビン、レンニン、コラゲナーゼ、ブロメライン、細菌プロテアーゼを挙げることができる。
【００３２】
本発明の仕上げ液は、銀画像部を親油性にする化合物（親油化剤）を含有させることが好ましい。親油化剤としては、フォーカル・プレス、ロンドン ニューヨーク（１９７２年）発行、アンドレ ロット及びエディス ワイデ著、「フォトグラフィック・シルバー・ハライド・ディヒュージョン・プロセシズ」、１０５、１０６ページに記載されている化合物が挙げられる。例えばメルカプト基またはチオン基を有する化合物、４級アンモニウム化合物等があり、本発明においてはメルカプト基またはチオン基を有する化合物が好ましく用いられる。特に好ましくは、メルカプト基またはチオン基を有する含窒素複素環化合物であり、特公昭４８−２９７２３号、特開昭５８−１２７９２８号に記載されている。以下にその具体例を挙げるが、これらに限定されることはない。
【００３３】
２−メルカプト−４−フェニルイミダゾール、２−メルカプト−１−ベンジルイミダゾール、２−メルカプト−ベンズイミダゾール、１−エチル−２−メルカプト−ベンズイミダゾール、２−メルカプト−１−ブチル−ベンズイミダゾール、１，３−ジエチル−ベンゾイミダゾリン−２−チオン、１，３−ジベンジル−イミダゾリジン−２−チオン、２，２´−ジメルカプト−１，１´−デカメチレン−ジイミダゾリン、２−メルカプト−４−フェニルチアゾール、２−メルカプト−ベンゾチアゾール、２−メルカプトナフトチアゾール、３−エチル−ベンゾチアゾリン−２−チオン、３−ドデシル−ベンゾチアゾリン−２−チオン、２−メルカプト−４，５−ジフェニルオキサゾール、２−メルカプトベンゾオキサゾール、３−ペンチル−ベンゾオキサゾリン−２−チオン、１−フェニル−３−メチルピラゾリン−５−チオン、３−メルカプト−４−アリル−５−ペンタデシル−１，２，４−トリアゾール、３−メルカプト−５−ノニル−１，２，４−トリアゾール、３−メルカプト−４−アセタミド−５−ヘプチル−１，２，４−トリアゾール、３−メルカプト−４−アミノ−５−ヘプタデシル−１，２，４−トリアゾール、２−メルカプト−５−フェニル−１，３，４−チアジアゾール、２−メルカプト−５−フェニル−１，３，４−チアジアゾール、２−メルカプト−５−ｎ−ヘプチル−オキサチアゾール、２−メルカプト−５−ｎヘプチル−オキサジアゾール、２−メルカプト−５−フェニル−１，３，４−オキサジアゾール、２−ヘプタデシル−５−フェニル−１，３，４−オキサジアゾール、５−メルカプト−１−フェニル−テトラゾール、２−メルカプト−５−ニトロピリジン、１−メチル−キノリン−２（１Ｈ）−チオン、３−メルカプト−４−メチル−６−フェニル−ピリダジン、２−メルカプト−５，６−ジフェニル−ピラジン、２−メルカプト−４，６−ジフェニル−１，３，５−トリアジン、２−アミノ−４−メルカプト−６−ベンジル−１，３，５−トリアジン、１，５−ジメルカプト−３，７−ジフェニル−Ｓ−トリアゾリノ〔１，２−ａ〕−Ｓ−トリアゾリン等が挙げられる。
【００３４】
仕上げ液への親油化剤の添加量は、０．０１〜１０ｇ／リットル程度が適当である。上記メルカプト基またはチオン基を有する化合物はアルカリ溶液には溶解するが、中性から弱酸性の仕上げ液には溶解しないため、有機溶剤、アミン化合物（例えばアミノアルコール）、ポリエチレングリコール、第４級アンモニウム塩型カチオン界面活性剤等の溶解助剤を用いて添加することができる。
【００３５】
銀塩印刷版の製版に用いられる現像液には、現像主薬、例えばポリヒドロキシベンゼン類、3-ピラゾリジノン類、アルカリ性物質、例えば水酸化カリウム、水酸化ナトリウム、水酸化リチウム、第３燐酸ナトリウム、あるいはアミン化合物、保恒剤、例えば亜硫酸ナトリウム、粘稠剤、例えばカルボキシメチルセルロース、カブリ防止剤、例えば臭化カリウム、現像変成剤、例えばポリオキシアルキレン化合物、ハロゲン化銀溶剤、例えばチオ硫酸塩、チオシアン酸塩、環状イミド、チオサリチル酸、メソイオン性化合物等の添加剤を含ませることができる。上記親油化剤を含有させてもよい。現像液のｐＨは通常１０〜１４、好ましくは１２〜１４である。
【００３６】
銀塩印刷版の製版に用いられる水洗液には、ｐＨを４〜９、好ましくは５〜７．５の範囲に緩衝させる緩衝剤、例えば燐酸塩緩衝剤、クエン酸塩緩衝剤またはそれらの混合物を含有することができる。また、防腐剤を含有させてもよい。水洗液中には更に上記タンパク質分解酵素及び親油化剤を含有させることが好ましい。
【００３７】
上記水洗液はアルミニウム支持体上のハロゲン化銀乳剤層を完全に除去するために用いるもので、通常、２５〜３５℃の水洗液をジェット方式で吹き付ける方法、または水洗液を吹き付けながらスクラブローラで乳剤層を剥離する方法が採用されている。また、水洗工程は、水洗液を循環させて再利用するクローズドタイプが一般に用いられている。
【００３８】
銀塩印刷版は、前記したようにアルミニウム支持体上に物理現像核及びハロゲン化銀乳剤層を有する。ハロゲン化銀乳剤は、一般に用いられる塩化銀、臭化銀、ヨウ化銀、塩臭化銀、塩ヨウ臭化銀、ヨウ臭化銀等から選択されるが、塩化銀主体（塩化銀５０モル％以上のものを意味する）が好ましい。また乳剤のタイプとしてはネガ型、ポジ型のいずれでもよい。これらのハロゲン化銀乳剤は必要に応じて化学増感あるいはスペクトル増感することができる。
【００３９】
ハロゲン化銀乳剤層の親水性コロイドとしてはゼラチンを用いることがハロゲン化銀粒子を作成する際に好ましい。ゼラチンには酸処理ゼラチン、アルカリ処理ゼラチン等各種ゼラチンを用いることができる。また、それらの修飾ゼラチン（例えばフタル化ゼラチン、アミド化ゼラチンなど）も用いることができる。また、更にポリビニルピロリドン、各種でんぷん、アルブミン、ポリビニルアルコール、アラビアガム、ヒドロキシエチルセルロース、等の親水性高分子化合物を含有させることができる。用いられる親水性コロイドとしては、現像後の剥離性を容易にするために実質的に硬膜剤を含まない親水性コロイド層を用いることが望ましい。
【００４０】
本発明の平版印刷版の乳剤層には、必要に応じてアニオン、カチオン、ベタイン、ノニオン系の各種界面活性剤、カルボキシメチルセルロース等の増粘剤、消泡剤等の塗布助剤、エチレンジアミンテトラアセテート等のキレート剤、ハイドロキノン、ポリヒドロキシベンゼン類、３−ピラゾリジノン類等の現像主薬を含有させてもよい。
【００４１】
本発明に用いられるアルミニウム支持体は粗面化され陽極酸化されたアルミニウム板であり、好ましくは米国特許第５，４２７，８８９号公報に記載されているものが用いられる。
【００４２】
本発明で用いられる物理現像核層の物理現像核としては、公知の銀錯塩拡散転写法に用いられるものでよく、例えば金、銀等のコロイド、パラジウム、亜鉛等の水溶性塩と硫化物を混合した金属硫化物などが使用できる。保護コロイドとして各種親水性コロイドを用いることもできる。これらの詳細及び製法については、例えば、特公昭４８−３０５６２号、特開昭４８−５５４０２号、同５３−２１６０２号、フォーカル・プレス、ロンドン ニューヨーク（1972年）発行、アンドレ ロット及びエディス ワイデ著、「フォトグラフィック・シルバー・ハライド・ディヒュージョン・プロセシズ」を参照し得る。
【００４３】
本発明において、物理現像核層とハロゲン化銀乳剤層の間に、特開平３−１１６１５１号公報記載の水膨潤性中間層、同平４−２８２２９５号公報に記載の疎水性重合体ビーズを含有する中間層を設けてもよい。
【００４４】
以下、本発明を実施例にて詳細に説明する。
【００４５】
【実施例】
実施例１
アルミニウム支持体の電解粗面化処理及び陽極酸化は米国特許第５，４２７，８８９号公報に記載の方法に従って、平均直径約５μｍのプラート上に直径０．０３〜０．３０μｍのピットを１００μｍ²当たり約５，６００個有し、かつこれらのピットの平均直径が０．０８μｍである厚さ０．３０ｍｍのアルミニウム板を得た。このアルミ板は粗面化処理後に陽極酸化したものであり、平均粗さ（Ｒａ）は０．５〜０．６μｍであった。陽極酸化膜量は２．１ｇ／ｍ²であった。
【００４６】
このアルミニウム支持体に硫化パラジウム核液を塗布し、その後乾燥した。物理現像核層に含まれる核量は３ｍｇ／ｍ²であった。
【００４７】
ハロゲン化銀乳剤の調製は、保護コロイドとしてアルカリ処理ゼラチンを用い、コントロールダブルジェット法で平均粒径０．２μｍの、ヘキサクロロイリジウム（IV）酸カリウムを銀１モル当たり０．００６ミリモルドープさせた臭化銀１５モル％、ヨウ化銀０．４モル％の塩ヨウ臭化銀乳剤を調製した。その後、この乳剤をフロキュレーションさせ、洗浄した。さらにこの乳剤に硫黄金増感を施した後、安定剤を添加し、赤色領域に分光感度を持つ増感色素を銀１ｇ当たり３ｍｇ用いて分光増感した。
【００４８】
このようにして作成したハロゲン化銀乳剤に界面活性剤を加えて塗布液を作成した。この乳剤層塗布液を前記物理現像核が塗布されたアルミニウム支持体上に銀量が２ｇ／ｍ²、ゼラチン量が２．５ｇ／ｍ²になるように塗布乾燥して平版印刷材料試料を得た。
【００４９】
上記平版印刷材料を６３３ｎｍの赤色ＬＤレーザーを光源とする出力機で画像出力し、次に製版用プロセッサー（デュポン社製ＳＬＴ−８５Ｎ自動現像機）で処理して平版印刷版を作成した。製版用プロセッサーは、現像処理工程（２１℃、１５秒間浸漬）、水洗処理工程（３５℃の水洗液を１０秒間シャワー噴射しながらスクラブローラで乳剤層をウオッシュオフする）、仕上げ処理工程（２１℃、５秒間シャワー）及び乾燥工程から構成されている。水洗処理工程は、貯留タンクに貯留された３０リットルの水洗液をポンプで循環させて、平版印刷版にシャワー噴射した後、濾過フィルターで濾過して貯留タンクに回収し再使用するクローズドタイプになっている。
【００５０】
用いた現像液、水洗液及び仕上げ液の組成は次の通りである。
＜現像液＞
水酸化ナトリウム ２０ｇ
ハイドロキノン ２０ｇ
１−フェニル−３ピラゾリジノン ２ｇ
無水亜硫酸ナトリウム ８０ｇ
Ｎ−メチルエタノールアミン ６ｇ
チオ硫酸ナトリウム（５水塩） ８ｇ
エチレンジアミン四酢酸ナトリウム塩 ５ｇ
脱イオン水で１０００ｍｌとする。
ｐＨ（２５℃）＝１３．４
【００５１】
＜水洗液＞
２−メルカプト−５−ｎヘプチル−オキサジアゾール ０．５ｇ
トリエタノールアミン １３ｇ
重亜硫酸ナトリウム １０ｇ
リン酸二水素カリウム ４０ｇ
タンパク質分解酵素 １ｇ
水を加えて全量を１０００ｃｃに調整する。ｐＨは６．０に調整した。
タンパク質酵素として、ビオプラーゼＡＬ−１５（細菌プロティナーゼ、長瀬産業（株）製）を用いた。
【００５２】

タンパク質分解酵素として、ビオプラーゼＡＬ−１５（細菌プロティナーゼ、長瀬産業（株）製）を用いた。水酸化ナトリウムにてｐＨは６．５に調整した。さらにこの＜仕上げ液Ａ＞に以下の薬品を２０ｇ添加し硫酸もしくは水酸化ナトリウムでＰＨを、６．５に調整した。
【００５３】
＜仕上げ液Ｂ＞
仕上げ液Ａにトリエタノールアミンを２０ｇ加えて硫酸でＰＨを６．５に調整した。
＜仕上げ液Ｃ＞
仕上げ液Ａにモノエタノールアミンを２０ｇ加えて硫酸でＰＨを６．５に調整した。
＜仕上げ液Ｄ＞
仕上げ液Ａに２アミノ酢酸を２０ｇ加えて水酸化ナトリウムでＰＨを６．５に調整した。
＜仕上げ液Ｅ＞
仕上げ液Ａにエチレンジアミンを２０ｇ加えて硫酸でＰＨを６．５に調整した。
＜仕上げ液Ｆ＞
仕上げ液Ａに１，５ジアミノペンタンを２０ｇ加えて硫酸でＰＨを６．５に調整した。
＜仕上げ液Ｇ＞
仕上げ液Ａに３，３'−ジアミノプロピルアミンを２０ｇ加えて硫酸でＰＨを６．５に調整した。
＜仕上げ液Ｈ＞
仕上げ液ＡにＮ−メチル−３，３'−イミノビス（プロピルアミン）を２０ｇ加えて硫酸でＰＨを６．５に調整した。
＜仕上げ液Ｉ＞
仕上げ液Ａにピペラジンを２０ｇ加えて硫酸でＰＨを６．５に調整した。
＜仕上げ液Ｊ＞
仕上げ液Ａに１−アミノ−４−メチルピペラジンを２０ｇ加えて硫酸でＰＨを６．５に調整した。
＜仕上げ液Ｋ＞
仕上げ液ＡにＮ−（２−アミノエチル）ピペラジンを２０ｇ加えて硫酸でＰＨを６．５に調整した。
＜仕上げ液Ｌ＞
仕上げ液Ａにトリエチレンジアミンを２０ｇ加えて硫酸でＰＨを６．５に調整した。
＜仕上げ液Ｍ＞
仕上げ液Ａにヘキサメチレンテトラミンを２０ｇ加えて硫酸でＰＨを６．５に調整した。
＜仕上げ液Ｎ＞
仕上げ液Ａにモルホリンを２０ｇ加えて硫酸でＰＨを６．５に調整した。
＜仕上げ液Ｏ＞
仕上げ液Ａにイミダゾリジンを２０ｇ加えて硫酸でＰＨを６．５に調整した。
【００５４】
上記記載の方法で作成された平版印刷版を、印刷機スプリント２６（小森コーポレーション社製オフセット印刷機の商標）、インキ（東洋インキ（株）社製のＴＯＹＯハイエコー紅ＭＺ）及び給湿液（日研化学研究所（株）社製のアストロマーク３）を使用して印刷した。印刷は、まず水を送らずにインキだけを版に送って２０枚印刷し、版をインキで全面汚す。その後水を送り非画像部の汚れが水を送り始めてから何枚後に回復するかを観察する。２００枚印刷後、版を印刷機に装着したまま３０分停機し再び同様の方法で印刷を行った。再印刷時に汚れ回復までの印刷枚数が少ない印刷版ほど、安定した保水性を持つ良い印刷版である。
【００５５】
評価の結果を表１に示す。
【００５６】
【表１】
────────────────────────────────────
仕上げ液 はじめの汚れ回復枚数 停機後の汚れ回復枚数 備考
────────────────────────────────────
仕上げ液Ａ ２５枚 １００枚 比較
仕上げ液Ｂ ２５枚 １００枚 比較
仕上げ液Ｃ ２５枚 １００枚 比較
仕上げ液Ｄ ２５枚 １５０枚 比較
仕上げ液Ｅ ２５枚 ４０枚 本発明
仕上げ液Ｆ ２５枚 ４０枚 本発明
仕上げ液Ｇ ２５枚 ３０枚 本発明
仕上げ液Ｈ ２５枚 ２５枚 本発明
仕上げ液Ｉ ２５枚 ２５枚 本発明
仕上げ液Ｊ ２５枚 ２５枚 本発明
仕上げ液Ｋ ２５枚 ２５枚 本発明
仕上げ液Ｌ ２５枚 ２５枚 本発明
仕上げ液Ｍ ２５枚 ２５枚 本発明
仕上げ液Ｎ ２５枚 ３０枚 本発明
仕上げ液Ｏ ２５枚 ３０枚 本発明
────────────────────────────────────
【００５７】
表１の結果から明らかなように、仕上げ液に酸基または水酸基を有しないアミン類を少なくとも一種類以上含有させることによって、停機、再印刷を繰り返した時に発生するインキ汚れを改良したアルミニウム板を支持体とする銀錯塩拡散転写法を利用した平版印刷版の仕上げ液を提供することが可能である。
【００６２】
【発明の効果】
本発明によれば、アルミニウム板を支持体とする平版印刷版の製版処理時に、酸基を有しないアミン類を少なくとも一種類以上含有する仕上げ液を用いることによって、停機、再印刷を繰り返した時に発生するインキ汚れを改良できる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an aluminum plate finisher of the lithographic printing plate using a silver complex diffusion transfer process for the support.
[0002]
[Prior art]
In the field of lithographic printing, lithographic printing plates using an aluminum plate as a support are known as various printing plates including PS plates (pre-sensitized plates) using a photosensitive resin. For example, a thermal plate described in JP-A-7-20629 and JP-A-7-271029, a lithographic printing plate using laser ablation described in JP-A-7-314934 and JP-A-8-48018, and JP-A-5 Silver salt printing plates utilizing the silver complex salt diffusion transfer system described in JP-A Nos. 265216, 5-313206, 7-56345, and 9-6005 are known. The present invention is intended for silver salt printing plates.
[0003]
These printing plates are mainly composed of an image portion formed of a resin layer or physically developed silver and a non-image portion formed of an anodized layer of aluminum. The image portion selectively accepts ink, Printing is performed when the image unit selectively receives water. Therefore, it is necessary that the difference between the lipophilicity and the hydrophilicity between the image area and the non-image area is large. In these lithographic printing plates, after development, the resin layer or the silver halide emulsion layer is removed to expose the aluminum surface, which is a non-image area, and then a finishing solution is applied.
[0004]
The silver salt printing plate can form an image having high sensitivity, high color sensitivity, high resolution, and high sharpness, and is a very advantageous method as an image forming method using light. However, a silver image portion made of metallic silver is less oleophilic than an image portion such as a PS plate formed of a photosensitive resin. Therefore, the silver salt printing plate, when compared with the PS plate or the like, imparts high hydrophilicity in the plate-making process, significantly reducing the lipophilicity of the image area. Therefore, the function of the finishing solution is greatly different between them, not to mention the developing solution. That is, the processing liquid for silver salt printing plates is required to improve the hydrophilicity of the non-image area and the oleophilicity of the image area in a balanced manner.
[0005]
For the above reasons, ink stains in the non-image area during printing are greatly affected by the performance of the finishing liquid.
[0006]
In addition, for the purpose of enhancing the hydrophilicity of the non-image area of the plate or enhancing the oleophilicity of the image area, a liquid called a starter liquid may be applied to the plate surface immediately before printing. By using this starter liquid, it is possible to have a function of further improving the balance between the hydrophilicity of the non-image area and the lipophilicity of the image area.
[0007]
The silver salt printing plate targeted by the present invention has a structure in which a physical development nucleus is supported on a roughened and anodized aluminum support, and a silver halide emulsion layer is further provided thereon, A general plate making method includes a development process, a washing process (wash-off: removal of a silver halide emulsion layer), and a finishing process after exposure.
[0008]
Specifically, a metallic silver image portion is formed on the physical development nuclei by the development process, and the silver halide emulsion layer is removed by the subsequent washing treatment, and the metallic silver image portion (hereinafter referred to as a silver image portion) is formed on the aluminum support. Exposed). At the same time, the anodized aluminum surface itself is exposed as a non-image part.
[0009]
After the washing treatment, a finishing solution containing a protective colloid such as gum arabic, dextrin, carboxymethylcellulose, polystyrene sulfonic acid or the like is usually applied to protect the plate surface and improve the hydrophilicity of the non-image area. A so-called gumming process is performed. This finishing solution is also called a fixing solution or a finishing solution, and generally contains a compound that makes the silver image portion oleophilic (for example, a nitrogen-containing heterocyclic compound having a mercapto group or a thione group). However, the conventional finishing liquid has a problem in that ink stains occur while stopping and reprinting are repeated during printing.
[0010]
[Problems to be solved by the invention]
An object of the present invention is to provide a finishing liquid for a lithographic printing plate using a silver complex diffusion transfer method using an aluminum plate with improved ink stains generated when stopping and reprinting are repeated as a support. In particular, it is to provide a finishing liquid that can prevent non-image areas from being stained even after printing.
[0011]
[Means for Solving the Problems]
The above object of the present invention is a finishing solution of the lithographic printing plate using a silver complex diffusion transfer to the aluminum plate as a support, which contains at least one or more having no amine to acid groups in the finisher Thus it is achieved the finishing solution according to claim.
[0012]
The present inventor presumes the stain generation mechanism at the time of reprinting after stopping once as follows. In conventional finishing liquids as described in JP-A-7-287398, JP-A-7-287399, etc., most of the plate surface hydrophilizing protective agent in the finishing liquid once applied to the printing plate is once printed. It will be washed away and will not remain on the plate. Therefore, the exposed surface of the anodized aluminum appears in the non-image area on the printing plate except for the components of the moisturizing liquid. In general, the anodized film of a silver salt printing plate is not subjected to sealing treatment (blocks the fine holes of the anodized film), and therefore the exposed anodized aluminum surface is susceptible to corrosion in the air. In particular, since the printing press is in a high-temperature and high-humidity state, the anodic oxide film is easily broken and corrosion of aluminum occurs, and aluminum ions are generated therefrom. Aluminum ions easily react with organic substances, in particular organic substances having a carboxyl group, to form lipophilic sites, which become the starting point of soiling.
[0013]
One method for preventing such corrosion is to increase the thickness of the anodized film. Although it is effective to add an anodic oxide film of 5 g / m ² or more, increasing the thickness of the anodic oxide film involves a great amount of power consumption during the production of an aluminum base and is economically expensive. Further, if the anodic oxide film is too thick, defects are likely to occur on the surface. In this background, the present invention is suitable for a lithographic printing plate using an aluminum support having a relatively thin anodic oxide film. A high effect is exhibited when the film is 3.5 g / m ² or less, and further 3 g / m ² or less.
[0014]
Therefore, as a result of intensive studies to achieve the object without increasing the anodic oxide film thickness, the present inventors have made the above object by including at least one or more amines having no acid group or hydroxyl group in the finishing liquid. Found that is achieved.
[0015]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
[0017]
The finishing liquid of the present invention contains at least one amine having no acid group. The acid group here means a substituent that is anionized in an aqueous solution. Specific examples include a carboxyl group, a sulfone group, a phosphone group, and a mercapto group. Furthermore, the acid group referred to in the present invention includes a hydroxyl group even if it is not anionized. Therefore, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid and the like often used as alkanolamines and chelating agents such as ethanolamine do not correspond to the amines having no acid group or hydroxyl group according to the present invention.
[0018]
The amines of the present invention are considered to exhibit an effect when the nitrogen atoms forming the amine skeleton are adsorbed on the anodized aluminum surface. However, since the non-image area of the printing plate surface is constantly exposed to the dampening solution, if these amines have a higher solubility in water than the ability to adsorb on the anodized aluminum surface, during printing, The effect will be lost. Therefore, an amine to which a highly hydrophilic substituent other than an amino group is added is less effective due to its high hydrophilicity. For these reasons, it is considered that an amine having an acid group or a hydroxyl group does not function effectively.
[0019]
The general formulas of compounds preferred in the present invention are shown below.
[0020]
[Chemical 1]

[0021]
In the formula, n is an integer of 1 to 6. R ₁ is a hydrogen atom or a substituent composed of a plurality of atoms arbitrarily selected from hydrogen, carbon, nitrogen, and oxygen atoms having no acid group. When R ₁ contains an oxygen atom, the oxygen atom must be two carbon atoms. It is bonded to an atom. When R ₁ contains a nitrogen atom, the nitrogen atom forms a heterocyclic ring with carbon, or is bonded to three atoms selected from a carbon atom or a hydrogen atom.
[0022]
[Chemical 2]

[0023]
In the formula, n and m are integers of 1 to 6. R ₁ and R ₂ are substituents consisting of a plurality of atoms arbitrarily selected from hydrogen, carbon, nitrogen and oxygen atoms having no hydrogen atom or acid group, and when R ₁ and R ₂ contain an oxygen atom, Is bound to two carbon atoms. When R ₁ and R ₂ contain a nitrogen atom, the nitrogen atom forms a heterocyclic ring with carbon, or is bonded to three atoms selected from a carbon atom or a hydrogen atom. R ₁ and R ₂ may be connected to each other to form a ring.
[0024]
[Chemical 3]

[0025]
In the formula, n, m and o are integers of 1 to 6. , R ₁ , R ₂ , and R ₃ are substituents composed of a plurality of atoms arbitrarily selected from hydrogen, carbon, nitrogen, and oxygen atoms that do not have a hydrogen atom or acid group, and R ₁ , R ₂ , and R ₃ are oxygen When it contains atoms, oxygen atoms are always bonded to two carbon atoms. When R ₁ , R ₂ and R ₃ contain a nitrogen atom, the nitrogen atom forms a heterocyclic ring with carbon, or is bonded to three atoms selected from a carbon atom or a hydrogen atom. R ₁ and R ₂ , R ₁ and R ₃ or R ₂ and R ₃ may be linked to each other to form a ring.
[0026]
Examples of R ₁ , R ₂ , and R ₃ are given below, but the present invention is not limited thereto. Examples of the substituents of R ₁ , R ₂ and R ₃ that are not linked to each other include hydrocarbons such as alkyl groups, alkenyl groups, cycloalkyl groups, and phenyl groups, alkoxy groups, alkyleneoxy groups, and phenoxy groups. Through oxygen atoms such as amino groups, substituted amino groups, etc., and heterocyclic rings such as triazole, imidazole, tetrazole, oxazole, triazine, piperazine, piperidine, morpholine, imidazolidine, benzotriazole A substituent may be formed. In the substituents R ₁ , R ₂ and R ₃ , one or more of the above substituents may be further substituted with the above substituent. That is, substituents such as an alkoxyalkyl group, an aminoalkyl group, an aminoalkoxy group, and an aminoalkoxyalkoxy group can be exemplified.
Of the substituents of R ₁ , R ₂ , and R ₃ , those that are linked to each other may be considered to be cases where the above substituents are linked to each other.
[0027]
Specific examples of Chemical Formula 1, Chemical Formula 2 and Chemical Formula 3 are given below, but the present invention is not limited thereto. Those not forming a ring include ethylamine, n-propylamine, isopropylamine, t-butylamine, methoxyethylamine, methoxypropylamine, ethoxypropylamine, ethylenediamine, 1,3 diaminopropane, 1,2propanediamine, 1 , 4 diaminobutane, 1,5 diaminopentane, 1,6 diaminohexane, diethylenetriamine, triethylenetetramine, diethylamine, diisopropylamine, N-ethyldiisopropylamine, N-methyl 1,3-propanediamine, 3,3, minopropylamine , 3- (dimethylamino) propylamine, 3- (diethylamino) propylamine, N-methyl-3,3′-iminobis (propylamine), tris (2-aminoethyl) amine and the like. The Among cyclic amines, piperazine and its derivatives include piperazine, 2-methylpiperazine, N-methylpiperazine, 2,5 dimethylpiperazine, 2,6 dimethylpiperazine, 2-aminomethylpiperazine, N- (2-aminoethyl) Examples include piperazine, 1,4-bisaminopropylpiperazine, 1-amino-4-methylpiperazine, and the like. Examples of other cyclic amines include morpholines such as morpholine and N-aminopropylmorpholine, piperidine, pyrrolidine, imidazolidine, and derivatives thereof, and cyclic bridged compounds such as triethylenediamine and hexamethylenetetramine.
[0028]
The amount of these amines added is not particularly limited, but is preferably 0.01 to 1 mol / liter, more preferably 0.05 to 0.5 mol / liter.
[0029]
The PH of the finishing liquid is preferably between 3 and 8, more preferably 4-7. On the other hand, as for a starter liquid, 5-8 are preferable. For adjusting the pH, phosphoric acid, sulfuric acid, acetic acid and other organic acids can be used.
[0030]
The finishing liquid of the present invention preferably contains phosphoric acid or a salt thereof. Examples of phosphoric acid or phosphate include phosphoric acid, sodium phosphate, ammonium phosphate, potassium phosphate, triethanolamine phosphate, and phosphates with other amines. These addition amounts are preferably in the range of 0.05 to 1 mol / liter.
[0031]
In addition to the above-mentioned compounds, the finishing liquid of the present invention includes arabic gum, dextrin, sodium alginate, propylene glycol ester of alginic acid, hydroxyethyl starch, carboxymethylcellulose, hydroxyethylcellulose, polyvinylpyrrolidone, polystyrene sulfonic acid, polyvinyl alcohol and other protective colloids, Or a mixture thereof. Moreover, you may contain a preservative. The finishing liquid preferably further contains a proteolytic enzyme. Examples of these enzymes include pepsin, renin, trypsin, chymotrypsin, cathepsin, papain, ficin, thrombin, rennin, collagenase, bromelain, and bacterial protease.
[0032]
The finishing liquid of the present invention preferably contains a compound (lipophilic agent) that makes the silver image part oleophilic. As a lipophilic agent, compounds described in “Photographic Silver Halide Diffusion Processes”, pages 105 and 106, published by Focal Press, London New York (1972), written by Andrerot and Edith Weide. Is mentioned. For example, there are a compound having a mercapto group or a thione group, a quaternary ammonium compound, etc., and a compound having a mercapto group or a thione group is preferably used in the present invention. Particularly preferred are nitrogen-containing heterocyclic compounds having a mercapto group or a thione group, which are described in JP-B-48-29723 and JP-A-58-127828. Although the specific example is given to the following, it is not limited to these.
[0033]
2-mercapto-4-phenylimidazole, 2-mercapto-1-benzylimidazole, 2-mercapto-benzimidazole, 1-ethyl-2-mercapto-benzimidazole, 2-mercapto-1-butyl-benzimidazole, 1,3 -Diethyl-benzimidazoline-2-thione, 1,3-dibenzyl-imidazolidine-2-thione, 2,2'-dimercapto-1,1'-decamethylene-diimidazoline, 2-mercapto-4-phenylthiazole, 2 -Mercapto-benzothiazole, 2-mercaptonaphthothiazole, 3-ethyl-benzothiazoline-2-thione, 3-dodecyl-benzothiazoline-2-thione, 2-mercapto-4,5-diphenyloxazole, 2-mercaptobenzoxazole , 3-pentyl-be Nzooxazoline-2-thione, 1-phenyl-3-methylpyrazolin-5-thione, 3-mercapto-4-allyl-5-pentadecyl-1,2,4-triazole, 3-mercapto-5-nonyl-1, 2,4-triazole, 3-mercapto-4-acetamido-5-heptyl-1,2,4-triazole, 3-mercapto-4-amino-5-heptadecyl-1,2,4-triazole, 2-mercapto- 5-phenyl-1,3,4-thiadiazole, 2-mercapto-5-phenyl-1,3,4-thiadiazole, 2-mercapto-5-n-heptyl-oxathiazole, 2-mercapto-5-nheptyl- Oxadiazole, 2-mercapto-5-phenyl-1,3,4-oxadiazole, 2-heptadecyl-5-phenyl-1,3 -Oxadiazole, 5-mercapto-1-phenyl-tetrazole, 2-mercapto-5-nitropyridine, 1-methyl-quinoline-2 (1H) -thione, 3-mercapto-4-methyl-6-phenyl-pyridazine 2-mercapto-5,6-diphenyl-pyrazine, 2-mercapto-4,6-diphenyl-1,3,5-triazine, 2-amino-4-mercapto-6-benzyl-1,3,5-triazine 1,5-dimercapto-3,7-diphenyl-S-triazolino [1,2-a] -S-triazoline and the like.
[0034]
The amount of the lipophilic agent added to the finishing liquid is suitably about 0.01 to 10 g / liter. The above-mentioned compound having a mercapto group or thione group dissolves in an alkaline solution, but does not dissolve in a neutral to weakly acidic finish solution. Therefore, an organic solvent, an amine compound (for example, amino alcohol), polyethylene glycol, quaternary ammonium It can be added using a dissolution aid such as a salt-type cationic surfactant.
[0035]
Developers used for plate making of silver salt printing plates include developing agents such as polyhydroxybenzenes, 3-pyrazolidinones, alkaline substances such as potassium hydroxide, sodium hydroxide, lithium hydroxide, tribasic sodium phosphate, or Amine compounds, preservatives such as sodium sulfite, thickeners such as carboxymethylcellulose, antifoggants such as potassium bromide, development modifiers such as polyoxyalkylene compounds, silver halide solvents such as thiosulfate, thiocyanic acid Additives such as salts, cyclic imides, thiosalicylic acid, mesoionic compounds and the like can be included. You may contain the said lipophilic agent. The pH of the developer is usually 10-14, preferably 12-14.
[0036]
The washing solution used for making a silver salt printing plate contains a buffering agent having a pH of 4 to 9, preferably 5 to 7.5, such as a phosphate buffer, a citrate buffer or a mixture thereof. Can be contained. Moreover, you may contain a preservative. The washing solution preferably further contains the proteolytic enzyme and a lipophilic agent.
[0037]
The above washing solution is used to completely remove the silver halide emulsion layer on the aluminum support. Usually, a method of spraying a washing solution of 25 to 35 ° C. by a jet method or a scrub roller while blowing the washing solution. A method of peeling the emulsion layer is employed. In the washing process, a closed type in which the washing solution is circulated and reused is generally used.
[0038]
As described above, the silver salt printing plate has physical development nuclei and a silver halide emulsion layer on an aluminum support. The silver halide emulsion is selected from generally used silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodobromide, silver iodobromide, etc., but mainly silver chloride (50 mol of silver chloride) % Or more) is preferred. The emulsion type may be either a negative type or a positive type. These silver halide emulsions can be chemically or spectrally sensitized as necessary.
[0039]
As the hydrophilic colloid of the silver halide emulsion layer, gelatin is preferably used when preparing silver halide grains. Various gelatins such as acid-treated gelatin and alkali-treated gelatin can be used as the gelatin. In addition, modified gelatins such as phthalated gelatin and amidated gelatin can also be used. Furthermore, hydrophilic polymer compounds such as polyvinyl pyrrolidone, various starches, albumin, polyvinyl alcohol, gum arabic, and hydroxyethyl cellulose can be contained. As the hydrophilic colloid to be used, it is desirable to use a hydrophilic colloid layer substantially free of a hardener in order to facilitate release after development.
[0040]
In the emulsion layer of the lithographic printing plate of the present invention, anionic, cationic, betaine, nonionic surfactants, thickeners such as carboxymethylcellulose, coating aids such as antifoaming agents, ethylenediaminetetraacetate, as necessary A developing agent such as a chelating agent such as hydroquinone, polyhydroxybenzenes, and 3-pyrazolidinones may be contained.
[0041]
The aluminum support used in the present invention is a roughened and anodized aluminum plate, preferably the one described in US Pat. No. 5,427,889.
[0042]
The physical development nuclei of the physical development nuclei layer used in the present invention may be those used in a known silver complex diffusion transfer method. For example, colloids such as gold and silver, water-soluble salts such as palladium and zinc, and sulfides. Mixed metal sulfides can be used. Various hydrophilic colloids can also be used as the protective colloid. For details and production methods thereof, see, for example, JP-B-48-30562, JP-A-48-55402, 53-21602, Focal Press, London New York (1972), written by Andre Lot and Edith Weide, You may refer to “Photographic Silver Halide Diffusion Processes”.
[0043]
In the present invention, a water-swellable intermediate layer described in JP-A-3-116151 and a hydrophobic polymer bead described in JP-A-4-282295 are included between the physical development nucleus layer and the silver halide emulsion layer. An intermediate layer may be provided.
[0044]
Hereinafter, the present invention will be described in detail with reference to examples.
[0045]
【Example】
Example 1
The electrolytic surface-roughening treatment and anodization of the aluminum support were carried out according to the method described in US Pat. No. 5,427,889, and pits having a diameter of 0.03 to 0.30 μm were formed on a plate having an average diameter of about 5 μm to 100 μm ^2. An aluminum plate having a thickness of 0.30 mm having about 5,600 per hole and an average diameter of these pits of 0.08 μm was obtained. This aluminum plate was anodized after the roughening treatment, and the average roughness (Ra) was 0.5 to 0.6 μm. The amount of the anodic oxide film was 2.1 g / m ² .
[0046]
A palladium sulfide core solution was applied to the aluminum support and then dried. The amount of nuclei contained in the physical development nucleus layer was 3 mg / m ² .
[0047]
The silver halide emulsion was prepared by using alkali-treated gelatin as a protective colloid, and an odor doped with 0.006 mmol of potassium hexachloroiridium (IV) having a mean particle size of 0.2 μm per mol of silver by a control double jet method. A silver chloroiodobromide emulsion containing 15 mol% of silver chloride and 0.4 mol% of silver iodide was prepared. The emulsion was then flocculated and washed. The emulsion was further subjected to sulfur gold sensitization, and then a stabilizer was added, followed by spectral sensitization using 3 mg of sensitizing dye having a spectral sensitivity in the red region per 1 g of silver.
[0048]
A surfactant was added to the silver halide emulsion thus prepared to prepare a coating solution. The emulsion layer coating solution is applied and dried on an aluminum support coated with the above-mentioned physical development nuclei so that the amount of silver is 2 g / m ² and the amount of gelatin is 2.5 g / m ^2. It was.
[0049]
The lithographic printing material was subjected to image output by an output machine using a red laser of 633 nm as a light source, and then processed by a plate making processor (SLT-85N automatic developing machine manufactured by DuPont) to prepare a lithographic printing plate. The plate-making processor comprises a development processing step (21 ° C., 15 seconds immersion), a water washing processing step (washing off the emulsion layer with a scrub roller while spraying a 35 ° C. water washing solution for 10 seconds), and a finishing processing step (21 ° C. For 5 seconds) and a drying process. The washing process is a closed type in which 30 liters of washing liquid stored in a storage tank is circulated by a pump, showered on a planographic printing plate, filtered through a filtration filter, collected in a storage tank, and reused. ing.
[0050]
The composition of the used developer, washing solution and finishing solution is as follows.
<Developer>
Sodium hydroxide 20g
Hydroquinone 20g
1-phenyl-3-pyrazolidinone 2g
80 g of anhydrous sodium sulfite
N-methylethanolamine 6g
Sodium thiosulfate (pentahydrate) 8g
Ethylenediaminetetraacetic acid sodium salt 5g
Bring to 1000 ml with deionized water.
pH (25 ° C.) = 13.4
[0051]
<Washing liquid>
2-mercapto-5-nheptyl-oxadiazole 0.5 g
Triethanolamine 13g
Sodium bisulfite 10g
Potassium dihydrogen phosphate 40g
Proteolytic enzyme 1g
Add water to adjust total volume to 1000cc. The pH was adjusted to 6.0.
As a protein enzyme, biolase AL-15 (bacterial proteinase, manufactured by Nagase Sangyo Co., Ltd.) was used.
[0052]

Bioprolase AL-15 (bacterial proteinase, manufactured by Nagase Sangyo Co., Ltd.) was used as a proteolytic enzyme. The pH was adjusted to 6.5 with sodium hydroxide. Further, 20 g of the following chemical was added to this <Finishing liquid A>, and the pH was adjusted to 6.5 with sulfuric acid or sodium hydroxide.
[0053]
<Finishing liquid B>
20g of triethanolamine was added to the finishing liquid A, and PH was adjusted to 6.5 with sulfuric acid.
<Finishing liquid C>
20 g of monoethanolamine was added to the finishing liquid A, and the pH was adjusted to 6.5 with sulfuric acid.
<Finishing liquid D>
20 g of 2-aminoacetic acid was added to the finishing liquid A, and PH was adjusted to 6.5 with sodium hydroxide.
<Finishing liquid E>
20 g of ethylenediamine was added to the finishing liquid A, and the pH was adjusted to 6.5 with sulfuric acid.
<Finishing liquid F>
20 g of 1,5-diaminopentane was added to the finishing liquid A, and the pH was adjusted to 6.5 with sulfuric acid.
<Finishing liquid G>
20 g of 3,3′-diaminopropylamine was added to the finishing solution A, and the pH was adjusted to 6.5 with sulfuric acid.
<Finishing liquid H>
20 g of N-methyl-3,3′-iminobis (propylamine) was added to the finishing liquid A, and the pH was adjusted to 6.5 with sulfuric acid.
<Finishing liquid I>
20 g of piperazine was added to the finishing liquid A, and the pH was adjusted to 6.5 with sulfuric acid.
<Finishing liquid J>
20 g of 1-amino-4-methylpiperazine was added to the finishing liquid A, and the pH was adjusted to 6.5 with sulfuric acid.
<Finishing liquid K>
20 g of N- (2-aminoethyl) piperazine was added to the finishing liquid A, and the pH was adjusted to 6.5 with sulfuric acid.
<Finishing liquid L>
20 g of triethylenediamine was added to the finishing liquid A, and the pH was adjusted to 6.5 with sulfuric acid.
<Finishing liquid M>
20 g of hexamethylenetetramine was added to the finishing solution A, and the pH was adjusted to 6.5 with sulfuric acid.
<Finish N>
20 g of morpholine was added to the finishing solution A, and the pH was adjusted to 6.5 with sulfuric acid.
<Finishing liquid O>
20 g of imidazolidine was added to the finishing solution A, and the pH was adjusted to 6.5 with sulfuric acid.
[0054]
A lithographic printing plate prepared by the above-described method is prepared by using a printing machine Sprint 26 (trademark of offset printing machine manufactured by Komori Corporation), ink (TOYO Hi-Echo Red MZ manufactured by Toyo Ink Co., Ltd.) and a dampening liquid (Sun Printing was carried out using Astro Mark 3) manufactured by Kenkyuken Co., Ltd. First, 20 sheets are printed by sending only ink to the plate without sending water, and the plate is completely soiled with ink. Thereafter, water is fed, and the number of sheets after the dirt in the non-image area starts to be fed is observed. After printing 200 sheets, the plate was stopped for 30 minutes with the printing machine mounted, and printing was performed in the same manner again. A printing plate having a smaller number of printed sheets until the stain is recovered at the time of reprinting is a better printing plate having stable water retention.
[0055]
The evaluation results are shown in Table 1.
[0056]
[Table 1]
────────────────────────────────────
Finishing liquid Number of original stains recovered after stopping Remarks ─────────────────────────────────────
Finishing liquid A 25 sheets 100 sheets Comparative finishing liquid B 25 sheets 100 sheets Comparative finishing liquid C 25 sheets 100 sheets Comparative finishing liquid D 25 sheets 150 sheets Comparative finishing liquid E 25 sheets 40 sheets Present invention finishing liquid F 25 sheets 40 sheets Present invention Finishing liquid G 25 sheets 30 Inventive finishing liquid H 25 sheets 25 Invented finishing liquid I 25 sheets 25 Invented finishing liquid J 25 sheets 25 Invented finishing liquid K 25 sheets 25 Invented finishing liquid L 25 sheets 25 sheets of the present invention finishing liquid M 25 sheets 25 sheets of the present invention finishing liquid N 25 sheets 30 sheets of the present invention finishing liquid O 25 sheets 30 sheets of the present invention ─────────────────── ─────────────────
[0057]
As is apparent from the results in Table 1, an aluminum plate improved in ink stains generated when stopping and reprinting are repeated by containing at least one amine having no acid group or hydroxyl group in the finishing liquid. It is possible to provide a lithographic printing plate finishing liquid using a silver complex diffusion transfer method as a support.
[0062]
【The invention's effect】
According to the present invention, repeated during a lithographic printing plate platemaking process for the aluminum plate as a support, by a Turkey with the final solution containing acid groups at least one or more having no amines and stop machine, reprinting Ink smear that occurs when the ink is discharged can be improved.

Claims (1)

Roughened physical development nuclei carried on anodized on aluminum support, a further dressing fluid lithographic printing plate utilizing silver complex diffusion transfer in which a silver halide emulsion layer thereon, said A finishing liquid comprising at least one amine having no acid group or hydroxyl group in the finishing liquid.