JP4032167B2 - Support for photosensitive lithographic printing plate material, photosensitive lithographic printing plate material, and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive planographic printing plate material excellent in the adhesiveness of a photopolymerizable layer to the support, capable of ensuring both printing resistance and improvement in stain of a non-printing area and capable of obtaining a high resolution planographic printing plate and to provide a method for producing the same. <P>SOLUTION: A support for a photosensitive planographic printing plate material is a surface-roughened metal support treated with an aqueous solvent containing at least A) polyvinylphosphonic acid and B) an amino-containing compound. <P>COPYRIGHT: (C)2003,JPO

Description

【００６９】
式中、Ｒ₁は１価のエチレン性付加重合性基を有する有機基を表し、アクリロイル基、メタクリルロイル基、ビニル基等を挙げることができ、アクリロイル基またはメタクリロイル基が特に好ましい。Ｙは、炭素数１〜１０の２価の連結基を表し、アルキレン基、アリーレン基、アルケニレン基、アルキニレン基、−ＳＯ₂−、−ＳＯ−、−Ｏ−、−Ｓ−、−Ｎ（Ｒ₁₀）−、−（Ｃ＝Ｏ）−、−ＣＯＯ−、−（Ｐ＝Ｏ）−、−ＣＯＮＨ−等の基を単独または組合わせて構成される２価の連結基を挙げることができる。但し、Ｒ₁₀は水素原子、アルキル基、アリール基またはアラルキル基を表す。上記の中でも、アルキレン基、−Ｏ−、−（Ｃ＝Ｏ）−、−ＣＯＯ−、−ＣＯＮＨ−で表される基を単独または組合わせて構成される２価の連結基が好ましい。
【００７０】
Ｒ₂及びＲ₃は、それぞれ、水素原子、アルキル基、シクロアルキル基、アラルキル基、アリール基、アルケニル基、シクロアルケニル基、アルキニル基またはヘテロ環を表し、好ましくは、水素原子、アルキル基またはヘテロ環を表す。エチレン性付加重合性基は、後述する公知のものを挙げることができる。
【００７１】
本発明に係る、１分子中にアミノ基及びエチレン性付加重合性基を有する化合物の具体的な例としては、Ｎ，Ｎ−ジメチルアミノエチルアクリレート、Ｎ，Ｎ−ジエチルアミノエチルアクリレート、Ｎ，Ｎ−ジメチルアミノプロピルアクリレート、Ｎ，Ｎ−ジエチルアミノプロピルアクリレート、Ｎ，Ｎ−ジメチルアミノブチルアクリレート、Ｎ，Ｎ−ジエチルアミノブチルアクリレート及びＮ，Ｎ−ジメチルアミノエチルメタクリレート、Ｎ，Ｎ−ジエチルアミノエチルメタクリレート、Ｎ，Ｎ−ジメチルアミノプロピルメタクリレート、Ｎ，Ｎ−ジエチルアミノプロピルメタクリレート、Ｎ，Ｎ−ジメチルアミノブチルメタクリレート、Ｎ，Ｎ−ジエチルアミノブチルメタクリレート、Ｎ，Ｎ−ジメチルアミノエチルアクリルアミド、Ｎ，Ｎ−ジエチルアミノプロピルアクリルアミド、Ｎ，Ｎ−ジメチルアミノエチルメタクリルアミド、Ｎ，Ｎ−ジメチルアミノプロピルメタクリルアミド、Ｎ，Ｎ−ジエチルアミノエチルメタクリルアミド、Ｎ，Ｎ−ジエチルアミノプロピルメタクリルアミド、２−ビニルピリジン、４−ビニルピリジン、アリルアミン、２−メチルアリルアミン、ジアリルアミンなどが挙げられるが、特にこれらに限定されない。しかし光反応性の面から不飽和基としてアクリル基、またはメタクリル基を有するアミノ化合物が望ましい。
【００７２】
また、次の化合物も好ましく本発明に使用することができる。
【００７３】
【化２】

【００７４】
（１分子中にアミノ基を２個以上有する化合物）
また、本発明に係るアミノ基を有する化合物としては、１分子中にアミノ基を２個以上有する化合物も好ましく用いることができ、この化合物におけるアミノ基は、１級、２級、３級または４級のアミノ基のいずれでも構わないが、１級或いは２級のアミノ基が好ましい。好ましいアミノ基としては、下記式で表される化合物であるが、これに限定されない。
【００７５】
【化３】

【００７６】
式中、Ｒ₄は、炭素数１〜２２の２価の有機基（好ましくは、アルキレン基、アリーレン基、アルケニレン基、アルキニレン基、−ＳＯ₂−、−ＳＯ−、−Ｏ−、−Ｓ−、−Ｎ（Ｒ₁₀）−、−（Ｃ＝Ｏ）−、−ＣＯＯ−、−（Ｐ＝Ｏ）−、−ＣＯＮＨ−などの基を単独または組合わせて構成される２価の連結基またはシロキサン結合を有する２価の基を挙げることができる。但し、Ｒ₁₀は水素原子、アルキル基、アリール基またはアラルキル基を表す。
【００７７】
これらの中で好ましいものは、アルキレン基、アリーレン基、−Ｏ−、−（Ｃ＝Ｏ）−、−ＣＯＯ−、−ＣＯＮＨ−などの基を単独または組合わせて構成される２価の連結基である。
【００７８】
具体的には、３，３’−ジアミノビフェニル、３，４’−ジアミノビフェニル、４，４’−ジアミノビフェニル、３，３’−ジアミノジフェニルメタン、３，４’−ジアミノジフェニルメタン、４，４’−ジアミノジフェニルメタン、２，２−（３，３’−ジアミノジフェニル）プロパン、２，２−（３，４’−ジアミノジフェニル）プロパン、２，２−（４，４’−ジアミノジフェニル）プロパン、２，２−（３，３’−ジアミノジフェニル）ヘキサフルオロプロパン、２，２−（３，４’−ジアミノジフェニル）ヘキサフルオロプロパン、２，２−（４，４’−ジアミノジフェニル）ヘキサフルオロプロパン、３，３’−オキシジアニリン、３，４’−オキシジアニリン、４，４’−オキシジアニリン、３，３’−ジアミノジフェニルスルフィド、３，４’−ジアミノジフェニルスルフィド、４，４’−ジアミノジフェニルスルフィド、３，３’−ジアミノジフェニルスルホン、３，４’−ジアミノジフェニルスルホン、４，４’−ジアミノジフェニルスルホン、１，３−ビス［１−（３−アミノフェニル）−１−メチルエチル］ベンゼン、１，３−ビス［１−（４−アミノフェニル）−１−メチルエチル］ベンゼン、１，４−ビス［１−（３−アミノフェニル）］ベンゼン、１，３−ビス（３−アミノフェノキシ）ベンゼン、１，３−ビス（４−アミノフェノキシ）ベンゼン、１，４−ビス（３−アミノフェノキシ）ベンゼン、１，４−ビス（４−アミノフェノキシ）ベンゼン、３，３’−ビス（３−アミノフェノキシ）ジフェニルエーテル、３，３’−ビス（４−アミノフェノキシ）ジフェニルエーテル、３，４’−ビス（３−アミノフェノキシ）ジフェニルエーテル、３，４’−ビス（４−アミノフェノキシ）ジフェニルエーテル、４，４’−ビス（３−アミノフェノキシ）ジフェニルエーテル、４，４’−ビス（４−アミノフェノキシ）ジフェニルエーテル、１，４−ビス［１−（４−アミノフェニル）−１−メチルエチル−ビス（３−アミノフェノキシ）］ビフェニル、３，３’−ビス（４−アミノフェノキシ）ビフェニル、３，４’−ビス（３−アミノフェノキシ）ビフェニル、３，４’−ビス（４−アミノフェノキシ）ビフェニル、４，４’−ビス（３−アミノフェノキシ）ビフェニル、４，４’−ビス（４−アミノフェノキシ）ビフェニル、ビス［４−（３−アミノフェノキシ）フェニル］スルホン、ビス［４−（４−アミノフェノキシ）フェニル］スルホン、２，２−ビス［３−（３−アミノフェノキシ）フェニル］プロパン、２，２−ビス［３−（４−アミノフェノキシ）フェニル］プロパン、２，２−ビス［４−（３−アミノフェノキシ）フェニル］プロパン、２，２−ビス［４−（４−アミノフェノキシ）フェニル］プロパン、２，２−ビス［３−（３−アミノフェノキシ）フェニル］ヘキサフルオロプロパン、２，２−ビス［３−（４−アミノフェノキシ）フェニル］ヘキサフルオロプロパン、２，２−ビス［４−（３−アミノフェノキシ）フェニル］ヘキサフルオロプロパン、２，２−ビス［４−（４−アミノフェノキシ）フェニル］ヘキサフルオロプロパン、９，９−ビス（３−アミノフェニル）フルオレン、９，９−ビス（４−アミノフェニル）フルオレン、メチレンジアミン、ヘキサメチレンジアミン、ドデカメチレンジアミン等を挙げることができる。）またはシロキサン結合を有する２価の基を表す。
【００７９】
具体的な例として、４，４’−ジアミノジフェニルエーテル、４，４’−ジアミノジフェニルメタン、４，４’−ジアミノジフェニルスルホン、４，４’−ジアミノジフェニルサルファイド、ｍ−フェニレンジアミン、ｐ−フェニレンジアミン、２，４−ジアミノトルエン、２，５−ジアミノトルエン、２，６−ジアミノトルエン、ベンジジン、３，３’−ジメチルベンジジン、３，３’−ジメトキシベンジジン、ｏ−トリジン、４，４”−ジアミノターフェニル、１，５−ジアミノナフタレン、２，５−ジアミノピリジン、３，３’−ジメチル−４，４’−ジアミノジフェニルメタン、４，４’−ビス（ｐ−アミノフェノキシ）ビフェニル、２，２−ビス［４−（ｐ−アミノフェノキシ）フェニル］プロパン、ヘキサヒドロ−４，７−メタノインダニレンジメチレンジアミンなどが挙げられるが、特にこれらに限定されない。また無機基板との接着性を良好にする為にシロキサンジアミンを用いることが好ましい。好ましく用いられるものは下記式で表されるシロキサンジアミンが挙げられる。
【００８０】
【化４】

【００８１】
式中、Ｒ₅は、炭素数１〜１０の２価の有機基（好ましくは、アルキレン基、アリーレン基、アルケニレン基、アルキニレン基、−ＳＯ₂−、−ＳＯ−、−Ｏ−、−Ｓ−、−Ｎ（Ｒ₁₀）−、−（Ｃ＝Ｏ）−、−ＣＯＯ−、−（Ｐ＝Ｏ）−、−ＣＯＮＨ−などの基を単独または組合わせて構成される２価の連結基を挙げられる。但し、Ｒ₁₀は、水素原子、アルキル基、アリール基またはアラルキル基を表す）を表す。ｍは１〜１０の整数を表す。
【００８２】
これらの中で好ましいものは、アルキレン基またはアリーレン基を単独または組合わせて構成される２価の連結基である。
【００８３】
Ｒ₆、Ｒ₇、Ｒ₈またはＲ₉は、それぞれ独立に、水素原子、アルキル基、シクロアルキル基、アラルキル基、アリール基、アルケニル基、シクロアルケニル基、アルキニル基またはヘテロ環を表す。これらの中で好ましいものは、水素原子またはアルキル基である。
【００８４】
当該シロキサンジアミンは、本発明において使用される場合、本発明に係る１分子中にアミノ基を２個以上有する化合物において、その１〜２０モル％の範囲で用いることが好ましい。これにより、接着性向上効果が発揮され、また、耐熱性能も良好となり好ましい。
【００８５】
シロキサンジアミンの具体例としては、ビス（３−アミノプロピル）テトラメチルジシロキサン、ビス（１０−アミノデカメチレン）テトラメチルジシロキサン、アミノプロピル末端のジメチルシロキサン４量体、８量体、ビス（３−アミノフェノキシメチル）テトラメチルジシロキサンなどが挙げられる。本発明ではこれらの１分子中にアミノ基を２個以上有する化合物を１種または２種以上用いることができる。
【００８６】
また、本発明に係る１分子中にアミノ基を２個以上有する化合物の具体例として好ましいものは、以下のものを挙げることができる。
【００８７】
【化５】

【００８８】
（エチレン性付加重合性基を有する化合物）
本発明に用いるエチレン性付加重合性基を有する化合物は、公知の単量体（以下、単に単量体と称する場合もある）を挙げることができるが、具体的なものとしては、例えば、２−エチルヘキシルアクリレート、２−ヒドロキシプロピルアクリレート、グリセロールアクリレート、テトラヒドロフルフリルアクリレート、フェノキシエチルアクリレート、ノニルフェノキシエチルアクリレート、テトラヒドロフルフリルオキシエチルアクリレート、テトラヒドロフルフリルオキシヘキサノリドアクリレート、１，３−ジオキサンアルコールのε−カプロラクトン付加物のアクリレート、１，３−ジオキソランアクリレート等の単官能アクリル酸エステル類、或いはこれらのアクリレートをメタクリレート、イタコネート、クロトネート、マレエートに代えたメタクリル酸、イタコン酸、クロトン酸、マレイン酸エステル、例えば、エチレングリコールジアクリレート、ポリテトラメチレングリコールジアクリレート、トリエチレングルコールジアクリレート、ペンタエリスリトールジアクリレート、ハイドロキノンジアクリレート、レゾルシンジアクリレート、ヘキサンジオールジアクリレート、ネオペンチルグリコールジアクリレート、トリプロピレングリコールジアクリレート、ヒドロキシピバリン酸ネオペンチルグリコールのジアクリレート、ネオペンチルグリコールアジペートのジアクリレート、ヒドロキシピバリン酸ネオペンチルグリコールのε−カプロラクトン付加物のジアクリレート、２−（２−ヒドロキシ−１，１−ジメチルエチル）−５−ヒドロキシメチル−５−エチル−１，３−ジオキサンジアクリレート、トリシクロデカンジメチロールアクリレート、トリシクロデカンジメチロールアクリレートのε−カプロラクトン付加物、１，６−ヘキサンジオールのジグリシジルエーテルのジアクリレート等の２官能アクリル酸エステル類、或いはこれらのアクリレートをメタクリレート、イタコネート、クロトネート、マレエートに代えたメタクリル酸、イタコン酸、クロトン酸、マレイン酸エステル、例えばトリメチロールプロパントリアクリレート、ジトリメチロールプロパンテトラアクリレート、トリメチロールエタントリアクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート、ジペンタエリスリトールテトラアクリレート、ジペンタエリスリトールペンタアクリレート、ジペンタエリスリトールヘキサアクリレート、ジペンタエリスリトールヘキサアクリレートのε−カプロラクトン付加物、ピロガロールトリアクリレート、プロピオン酸−ジペンタエリスリトールトリアクリレート、プロピオン酸−ジペンタエリスリトールテトラアクリレート、ヒドロキシピバリルアルデヒド変性ジメチロールプロパントリアクリレート等の多官能アクリル酸エステル酸、或いはこれらのアクリレートをメタクリレート、イタコネート、クロトネート、マレエートに代えたメタクリル酸、イタコン酸、クロトン酸、マレイン酸エステル等を挙げることができ、これらのオリゴマーも使用することができる。
【００８９】
また、上記単量体によるプレポリマーも上記同様に使用することができる。プレポリマーとしては、後述する様な化合物等が挙げることができ、また、適当な分子量のオリゴマーにアクリル酸、またはメタクリル酸を導入し、光重合性を付与したプレポリマーも好適に使用できる。これらプレポリマーは、１種または２種以上を併用してもよいし、上述の単量体及び／またはオリゴマーと混合して用いてもよい。
【００９０】
プレポリマーとしては、例えばアジピン酸、トリメリット酸、マレイン酸、フタル酸、テレフタル酸、ハイミック酸、マロン酸、こはく酸、グルタール酸、イタコン酸、ピロメリット酸、フマル酸、グルタール酸、ピメリン酸、セバシン酸、ドデカン酸、テトラヒドロフタル酸等の多塩基酸と、エチレングリコール、プロピレングルコール、ジエチレングリコール、プロピレンオキサイド、１，４−ブタンジオール、トリエチレングリコール、テトラエチレングリコール、ポリエチレングリコール、グリセリン、トリメチロールプロパン、ペンタエリスリトール、ソルビトール、１，６−ヘキサンジオール、１，２，６−ヘキサントリオール等の多価のアルコールの結合で得られるポリエステルに（メタ）アクリル酸を導入したポリエステルアクリレート類、例えば、ビスフェノールＡ−エピクロルヒドリン−（メタ）アクリル酸、フェノールノボラック−エピクロルヒドリン−（メタ）アクリル酸のようにエポキシ樹脂に（メタ）アクリル酸を導入したエポキシアクリレート類、例えば、エチレングリコール−アジピン酸−トリレンジイソシアネート−２−ヒドロキシエチルアクリレート、ポリエチレングリコール−トリレンジイソシアネート−２−ヒドロキシエチルアクリレート、ヒドロキシエチルフタリルメタクリレート−キシレンジイソシアネート、１，２−ポリブタジエングリコール−トリレンジイソシアネート−２−ヒドロキシエチルアクリレート、トリメチロールプロパン−プロピレングリコール−トリレンジイソシアネート−２−ヒドロキシエチルアクリレートのように、ウレタン樹脂に（メタ）アクリル酸を導入したウレタンアクリレート、例えば、ポリシロキサンアクリレート、ポリシロキサン−ジイソシアネート−２−ヒドロキシエチルアクリレート等のシリコーン樹脂アクリレート類、その他、油変性アルキッド樹脂に（メタ）アクリロイル基を導入したアルキッド変性アクリレート類、スピラン樹脂アクリレート類等のプレポリマーが挙げられる。
【００９１】
上記するエチレン性付加重合性基を有する化合物は、また、本発明に係る感光性平版印刷版材料の光重合性層（感光層とも言う）にも適用することができる。
【００９２】
本発明に係る感光層には、また、ホスファゼンモノマー、トリエチレングリコール、イソシアヌール酸エチレンオキサイド（ＥＯ）変性ジアクリレート、イソシアヌール酸ＥＯ変性トリアクリレート、ジメチロールトリシクロデカンジアクリレート、トリメチロールプロパンアクリル酸安息香酸エステル、アルキレングリコールタイプアクリル酸変性、ウレタン変性アクリレート等の単量体及び該単量体から形成される構成単位を有する付加重合性のオリゴマー及びプレポリマーを含有することができる。
【００９３】
本発明に好ましく用いられる単量体として、少なくとも１つのエチレン性二重結合基を有する燐酸エステル化合物が挙げられる。該化合物は、燐酸の水酸基の少なくとも一部がエステル化された化合物であり、分子内にエチレン性二重結合を有していればよく、特に好ましくは（メタ）アクリロイル基を有する化合物である。
【００９４】
この他に特開昭５８−２１２９９４号公報、同６１−６６４９号公報、同６２−４６６８８号公報、同６２−４８５８９号公報、同６２−１７３２９５号公報、同６２−１８７０９２号公報、同６３−６７１８９号公報、特開平１−２４４８９１号公報等に記載の化合物などを挙げることができ、更に「１１２９０の化学商品」化学工業日報社、ｐ．２８６〜ｐ．２９４に記載の化合物、「ＵＶ・ＥＢ硬化ハンドブック（原料編）」高分子刊行会、ｐ．１１〜６５に記載の化合物なども本発明においては好適に用いることができる。これらの中で、分子内に２個以上のアクリル基またはメタクリル基を有する化合物が本発明においては好ましく、更に分子量が１０，０００以下、より好ましくは５，０００以下のものが好ましい。
【００９５】
本発明に係る感光層には、上記した単量体を、感光層を塗布する感光性組成物の１．０〜８０．０質量％の範囲で含有するのが好ましく、より好ましくは３．０〜７０．０質量％の範囲である。
【００９６】
（高分子結合剤）
本発明に係る感光層等は、高分子結合剤（バインダー）を含有することが好ましい。当該高分子結合材は、下記（１）〜（１７）に記載のモノマー（単量体）の少なくとも１種からなるビニル系共重合体を含有することが好ましい。
【００９７】
（１）芳香族水酸基を有するモノマー、例えばｏ−（またはｐ−，ｍ−）ヒドロキシスチレン、ｏ−（またはｐ−，ｍ−）ヒドロキシフェニルアクリレート等。
【００９８】
（２）脂肪族水酸基を有するモノマー、例えば２−ヒドロキシエチルアクリレート、２−ヒドロキシエチルメタクリレート、Ｎ−メチロールアクリルアミド、Ｎ−メチロールメタクリルアミド、４−ヒドロキシブチルメタクリレート、５−ヒドロキシペンチルアクリレート、５−ヒドロキシペンチルメタクリレート、６−ヒドロキシヘキシルアクリレート、６−ヒドロキシヘキシルメタクリレート、Ｎ−（２−ヒドロキシエチル）アクリルアミド、Ｎ−（２−ヒドロキシエチル）メタクリルアミド、ヒドロキシエチルビニルエーテル等。
【００９９】
（３）アミノスルホニル基を有するモノマー、例えばｍ−（またはｐ−）アミノスルホニルフェニルメタクリレート、ｍ−（またはｐ−）アミノスルホニルフェニルアクリレート、Ｎ−（ｐ−アミノスルホニルフェニル）メタクリルアミド、Ｎ−（ｐ−アミノスルホニルフェニル）アクリルアミド等。
【０１００】
（４）スルホンアミド基を有するモノマー、例えばＮ−（ｐ−トルエンスルホニル）アクリルアミド、Ｎ−（ｐ−トルエンスルホニル）メタクリルアミド等。
【０１０１】
（５）α，β−不飽和カルボン酸類、例えばアクリル酸、メタクリル酸、マレイン酸、無水マレイン酸、イタコン酸、無水イタコン酸等。
【０１０２】
（６）置換または無置換のアルキルアクリレート、例えばアクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、アクリル酸ブチル、アクリル酸アミル、アクリル酸ヘキシル、アクリル酸ヘプチル、アクリル酸オクチル、アクリル酸ノニル、アクリル酸デシル、アクリル酸ウンデシル、アクリル酸ドデシル、アクリル酸ベンジル、アクリル酸シクロヘキシル、アクリル酸−２−クロロエチル、Ｎ，Ｎ−ジメチルアミノエチルアクリレート、グリシジルアクリレート等。
【０１０３】
（７）置換または無置換のアルキルメタクリレート、例えばメタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸ブチル、メタクリル酸アミル、メタクリル酸ヘキシル、メタクリル酸ヘプチル、メタクリル酸オクチル、メタクリル酸ノニル、メタクリル酸デシル、メタクリル酸ウンデシル、メタクリル酸ドデシル、メタクリル酸ベンジル、メタクリル酸シクロヘキシル、メタクリル酸−２−クロロエチル、Ｎ，Ｎ−ジメチルアミノエチルメタクリレート、グリシジルメタクリレート等。
【０１０４】
（８）アクリルアミドまたはメタクリルアミド類、例えばアクリルアミド、メタクリルアミド、Ｎ−エチルアクリルアミド、Ｎ−ヘキシルアクリルアミド、Ｎ−シクロヘキシルアクリルアミド、Ｎ−フェニルアクリルアミド、Ｎ−（４−ニトロフェニル）アクリルアミド、Ｎ−エチル−Ｎ−フェニルアクリルアミド、Ｎ−（４−ヒドロキシフェニル）アクリルアミド、Ｎ−（４−ヒドロキシフェニル）メタクリルアミド等。
【０１０５】
（９）弗化アルキル基を含有するモノマー、例えばトリフルオロエチルアクリレート、トリフルオロエチルメタクリレート、テトラフルオロプロピルメタクリレート、ヘキサフルオロプロピルメタクリレート、オクタフルオロペンチルアクリレート、オクタフルオロペンチルメタクリレート、ヘプタデカフルオロデシルメタクリレート、Ｎ−ブチル−Ｎ−（２−アクリロキシエチル）ヘプタデカフルオロオクチルスルホンアミド等。
【０１０６】
（１０）ビニルエーテル類、例えば、エチルビニルエーテル、２−クロロエチルビニルエーテル、プロピルビニルエーテル、ブチルビニルエーテル、オクチルビニルエーテル、フェニルビニルエーテル等。
【０１０７】
（１１）ビニルエステル類、例えばビニルアセテート、ビニルクロロアセテート、ビニルブチレート、安息香酸ビニル等。
【０１０８】
（１２）スチレン類、例えばスチレン、メチルスチレン、クロロメチルスチレン等。
【０１０９】
（１３）ビニルケトン類、例えばメチルビニルケトン、エチルビニルケトン、プロピルビニルケトン、フェニルビニルケトン等。
【０１１０】
（１４）オレフィン類、例えばエチレン、プロピレン、ｉ−ブチレン、ブタジエン、イソプレン等。
【０１１１】
（１５）Ｎ−ビニルピロリドン、Ｎ−ビニルカルバゾール、４−ビニルピリジン等。
【０１１２】
（１６）シアノ基を有するモノマー、例えばアクリロニトリル、メタクリロニトリル、２−ペンテンニトリル、２−メチル−３−ブテンニトリル、２−シアノエチルアクリレート、ｏ−（またはｍ−，ｐ−）シアノスチレン等。
【０１１３】
（１７）アミノ基を有するモノマー、例えばＮ，Ｎ−ジエチルアミノエチルメタクリレート、Ｎ，Ｎ−ジメチルアミノエチルアクリレート、Ｎ，Ｎ−ジメチルアミノエチルメタクリレート、ポリブタジエンウレタンアクリレート、Ｎ，Ｎ−ジメチルアミノプロピルアクリルアミド、Ｎ，Ｎ−ジメチルアクリルアミド、アクリロイルモルホリン、Ｎ−ｉ−プロピルアクリルアミド、Ｎ，Ｎ−ジエチルアクリルアミド等。
【０１１４】
上記高分子結合剤には、必要に応じてポリビニルブチラール樹脂、ポリウレタン樹脂、ポリアミド樹脂、ポリエステル樹脂、エポキシ樹脂、ノボラック樹脂、天然樹脂等、他の任意の高分子結合剤が、上記の本発明に係るビニル系共重合体と併用されてもよい。
【０１１５】
本発明に係る感光層を塗布する組成物中における上記高分子結合剤の含有量は、感光層について１０〜９０質量％の範囲が好ましく、１５〜７０質量％の範囲が更に好ましく、２０〜５０質量％の範囲で使用することが感度の面から特に好ましい。更に、上記のビニル系共重合体は、該高分子結合剤において、５０〜１００質量％であることが好ましく、１００質量％であることがより好ましい。
【０１１６】
本発明に係る高分子結合剤に含まれる重合体の酸価については、１０〜１５０の範囲で使用するのが好ましく、３０〜１２０の範囲がより好ましく、５０〜９０の範囲で使用することが、感光層全体の極性のバランスをとる観点から特に好ましく、これにより感光層塗布液での顔料の凝集を防ぐことなどができる。
【０１１７】
（活性光線によりラジカルを発生させる化合物）
本発明に係る光重合性層（感光層）には活性光線によりラジカルを発生させる化合物（以下、光重合開始剤とも言う）を用いることが好ましく、光重合開始剤として好ましく使用できるものは、例えばＪ．コーサー（Ｊ．Ｋｏｓａｒ）著「ライト・センシテイブ・システムズ」第５章に記載されるような、カルボニル化合物、有機硫黄化合物、過硫化物、レドックス系化合物、アゾ化合物、ジアゾ化合物、ハロゲン化合物、光還元性色素などが挙げられ、英国特許第１，４５９，５６３号に開示されている化合物も好ましい。
【０１１８】
具体的には、以下の例を挙げることができるが、これらに限定されない。すなわち、ベンゾインメチルエーテル、ベンゾイン−ｉ−プロピルエーテル、α，α´−ジメトキシ−α−フェニルアセトフェノン等のベンゾイン誘導体；ベンゾフェノン、２，４−ジクロロベンゾフェノン、ｏ−ベンゾイル安息香酸メチル、４，４′−ビス（ジメチルアミノ）ベンゾフェノン等のベンゾフェノン誘導体；２−クロロチオキサントン、２−ｉ−プロピルチオキサントン等のチオキサントン誘導体；２−クロロアントラキノン、２−メチルアントラキノン等のアントラキノン誘導体；Ｎ−メチルアクリドン、Ｎ−ブチルアクリドン等のアクリドン誘導体；α，α´−ジエトキシアセトフェノン、ベンジル、フルオレノン、キサントン、ウラニル化合物の他、特公昭５９−１２８１号公報、同６１−９６２１号公報並びに特開昭６０−６０１０４号公報に記載のトリアジン誘導体；特開昭５９−１５０４号公報、同６１−２４３８０７号公報に記載の有機過酸化物；特公昭４３−２３６８４号公報、同４４−６４１３号公報、同４４−６４１３号公報、同４７−１６０４号公報並びに米国特許第３，５６７，４５３号に記載のジアゾニウム化合物；米国特許第２，８４８，３２８号、同２，８５２，３７９号並びに同２，９４０，８５３号に記載の有機アジド化合物；特公昭３６−２２０６２号公報、同３７−１３１０９号公報、同３８−１８０１５号公報並びに同４５−９６１０号公報に記載のｏ−キノンジアジド類；特公昭５５−３９１６２号公報、特開昭５９−１４０２３号公報並びに「マクロモレキュルス（Ｍａｃｒｏｍｏｌｅｃｕｌｅｓ）」１０巻，１３０７頁（１９７７年）記載の各種オニウム化合物；特開昭５９−１４２２０５号公報に記載のアゾ化合物；特開平１−５４４４０号公報、ヨーロッパ特許第１０９，８５１号、同１２６，７１２号並びに「ジャーナル・オブ・イメージング・サイエンス（Ｊ．Ｉｍａｇ．Ｓｃｉ．）」３０巻，１７４頁（１９８６年）記載の金属アレン錯体；特開平５−２１３８６１号及び同５−２５５３４７号記載の（オキソ）スルホニウム有機硼素錯体；特開昭５９−１５２３９６号公報、特開昭６１−１５１１９７号公報に記載のチタノセン類；「コーディネーション・ケミストリー・レビュー（Ｃｏｏｒｄｉｎａｔｉｏｎ Ｃｈｅｍｉｓｔｒｙ Ｒｅｖｉｅｗ）」８４巻，８５〜２７７頁（１９８８年）並びに特開平２−１８２７０１号公報に記載のルテニウム等の遷移金属を含有する遷移金属錯体；特開平３−２０９４７７号公報に記載の２，４，５−トリアリールイミダゾール二量体；四臭化炭素、特開昭５９−１０７３４４号公報に記載の有機ハロゲン化合物等を挙げることができる。
【０１１９】
中でも好ましいものは、チタノセン類である。チタノセン類の具体例としては、ジ−シクロペンタジエニル−Ｔｉ−ジ−クロライド、ジ−シクロペンタジエニル−Ｔｉ−ビス―フェニル、ジ−シクロペンタジエニル−Ｔｉ−ビス−２，３，４，５，６−ペンタフルオロフェニ−１−イル、ジ−シクロペンタジエニル−Ｔｉ−ビス−２，３，５，６−テトラフルオロフェニ−１−イル、ジ−シクロペンタジエニル−Ｔｉ−ビス−２，４，６−トリフルオロフェニ−１−イル、ジ−シクロペンタジエニル−Ｔｉ−ビス−２，６−ジフルオロフェニ−１−イル、ジ−シクロペンタジエニル−Ｔｉ−ビス−２，４−ジフルオロフェニ−１−イル、ジ−メチルシクロペンタジエニル−Ｔｉ−ビス−２，３，４，５，６−ペンタフルオロフェニ−１−イル、ジ−メチルシクロペンタジエニル−Ｔｉ−ビス−２，３，５，６−テトラフルオロフェニ−１−イル、ジ−メチルシクロペンタジエニル−Ｔｉ−ビス−２，４−ジフルオロフェニ−１−イル、ビス（シクロペンタジエニル）−ビス（２，６−ジフルオロ−３−（ピリ−１−イル）フェニル）チタニウム（ＩＲＵＧＡＣＵＲＥ７８４：チバスペシャリティーケミカルズ社製）等が挙げられるが、これに限定されるものではない。
【０１２０】
光源にレーザー光を用いる場合、好ましくは感光層に増感色素を添加することが好ましい。
【０１２１】
可視光から近赤外まで波長増感させる化合物としては、例えばシアニン、フタロシアニン、メロシアニン、ポルフィリン、スピロ化合物、フェロセン、フルオレン、フルギド、イミダゾール、ペリレン、フェナジン、フェノチアジン、ポリエン、アゾ化合物、ジフェニルメタン、トリフェニルメタン、ポリメチンアクリジン、クマリン、ケトクマリン、キナクリドン、インジゴ、スチリル、ピリリウム化合物、ピロメテン化合物、ピラゾロトリアゾール化合物、ベンゾチアゾール化合物、バルビツール酸誘導体、チオバルビツール酸誘導体等が挙げられ、更に欧州特許第５６８，９９３号、米国特許第４，５０８，８１１号、同５，２２７，２２７号、特開２００１−１２５２５５公報、特開平１１−２７１９６９号公報等に記載の化合物も用いられる。
【０１２２】
本発明において、上記の光重合開始剤と増感色素の組合せの好ましい具体例としては、特開２００１−１２５２５５公報、特開平１１−２７１９６９号公報に記載のある組合せが挙げられる。
【０１２３】
これら重合開始剤の感光層中での含有量は特に限定されないが、本発明に係るエチレン性付加重合性基を有する化合物１００質量部に対して０．１〜２０質量部が好ましい。また、光重合開始剤と増感色素の配合比率は、モル比で１：１００〜１００：１の範囲が、好ましい。
【０１２４】
（各種添加剤）
本発明に係る光重合性感光層の塗布組成物には、上記した成分の他に、感光性平版印刷版材料の製造中或いは保存中において重合可能なエチレン性不飽和二重結合単量体の不要な重合を阻止する為に、重合防止剤を添加することが望ましい。適当な重合防止剤としてはハイドロキノン、ｐ−メトキシフェノール、ジ−ｔ−ブチル−ｐ−クレゾール、ピロガロール、ｔ−ブチルカテコール、ベンゾキノン、４，４′−チオビス（３−メチル−６−ｔ−ブチルフェノール）、２，２′−メチレンビス（４−メチル−６−ｔ−ブチルフェノール）、Ｎ−ニトロソフェニルヒドロキシルアミン第一セリウム塩、２−ｔ−ブチル−６−（３−ｔ−ブチル−２−ヒドロキシ−５−メチルベンジル）−４−メチルフェニルアクリレート等が挙げられる。
【０１２５】
重合防止剤の添加量は、上記組成物の全固形分の質量に対して、０．０１〜５％が好ましい。また必要に応じて、酸素による重合阻害を防止する為にベヘン酸やベヘン酸アミドのような高級脂肪酸誘導体等を添加したり、塗布後の乾燥の過程で感光層の表面に偏在させてもよい。高級脂肪酸誘導体の添加量は、全組成物の０．５％〜１０％が好ましい。
【０１２６】
また、着色剤も使用することができ、着色剤としては、市販のものを含め従来公知のものが好適に使用できる。例えば、改訂新版「顔料便覧」，日本顔料技術協会編（誠文堂新光社）、カラーインデックス便覧等に述べられているものが挙げられる。
【０１２７】
顔料の種類としては、黒色顔料、黄色顔料、赤色顔料、褐色顔料、紫色顔料、青色顔料、緑色顔料、蛍光顔料、金属粉顔料等が挙げられる。具体的には、無機顔料（二酸化チタン、カーボンブラック、グラファイト、酸化亜鉛、プルシアンブルー、硫化カドミウム、酸化鉄、並びに鉛、亜鉛、バリウム及びカルシウムのクロム酸塩等）及び有機顔料（アゾ系、チオインジゴ系、アントラキノン系、アントアンスロン系、トリフェンジオキサジン系の顔料、バット染料顔料、フタロシアニン顔料及びその誘導体、キナクリドン顔料等）が挙げられる。
【０１２８】
これらの中でも、使用する露光レーザーに対応した分光増感色素の吸収波長域に実質的に吸収を持たない顔料を選択して使用することが好ましく、この場合、使用するレーザー波長での積分球を用いた顔料の反射吸収が０．０５以下であることが好ましい。また、顔料の添加量としては、上記組成物の固形分に対し０．１〜１０質量％が好ましく、より好ましくは０．２〜５質量％である。
【０１２９】
露光光源として、アルゴンレーザー（４８８ｎｍ）またはＳＨＧ−ＹＡＧレーザー（５３２ｎｍ）を使用する場合には、上記の感光波長領域での顔料吸収及び現像後の可視画性の観点から、紫色顔料、青色顔料を用いるのが好ましい。この様なものとしては、例えばコバルトブルー、セルリアンブルー、アルカリブルーレーキ、フォナトーンブルー６Ｇ、ビクトリアブルーレーキ、無金属フタロシアニンブルー、フタロシアニンブルーフアーストスカイブルー、インダンスレンブルー、インジコ、ジオキサンバイオレット、イソビオランスロンバイオレット、インダンスロンブルー、インダンスロンＢＣ等を挙げることができる。これらの中で、より好ましくはフタロシアニンブルー、ジオキサンバイオレットである。
【０１３０】
また、上記組成物は、本発明の性能を損わない範囲で、界面活性剤を塗布性改良剤として含有することができる。その中でも好ましいのはフッ素系界面活性剤である。
【０１３１】
また、硬化皮膜の物性を改良する為に、無機充填剤やジオクチルフタレート、ジメチルフタレート、トリクレジルホスフェート等の可塑剤等の添加剤を加えてもよい。これらの添加量は全固形分の１０％以下が好ましい。
【０１３２】
（塗布）
本発明に係る感光層や中間層などの塗布組成物を調製する際に使用する溶剤としては、例えば、アルコール：多価アルコールの誘導体類では、ｓｅｃ−ブタノール、イソブタノール、ｎ−ヘキサノール、ベンジルアルコール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、１，５−ペンタンジオール、またエーテル類：プロピレングリコールモノブチルエーテル、ジプロピレングリコールモノメチルエーテル、トリプロピレングリコールモノメチルエーテル、またケトン類、アルデヒド類：ジアセトンアルコール、シクロヘキサノン、メチルシクロヘキサノン、またエステル類：乳酸エチル、乳酸ブチル、シュウ酸ジエチル、安息香酸メチル等が好ましく挙げられる。
【０１３３】
調製された塗布組成物（層塗布液）は、従来公知の方法で支持体上に塗布し、乾燥し、感光性平版印刷版材料を作製することができる。塗布液の塗布方法としては、例えばエアドクタコータ法、ブレードコータ法、ワイヤーバー法、ナイフコータ法、ディップコータ法、リバースロールコータ法、グラビヤコータ法、キャストコーティング法、カーテンコータ法及び押し出しコータ法等を挙げることができる。
【０１３４】
感光層の乾燥温度は、低いと十分な耐刷性を得ることができず、また高過ぎるとマランゴニーを生じてしまうばかりか、非画線部のカブリを生じてしまう。好ましい乾燥温度範囲としては、６０〜１６０℃の範囲が好ましく、より好ましくは８０〜１４０℃、特に好ましくは、９０〜１２０℃の範囲で乾燥することが好ましい。
【０１３５】
（オーバーコート層）
本発明に係る感光層の上側には、オーバーコート層（保護層ないし酸素遮断層とも言う）を設けることが好ましい。該層は、後述する現像液（一般にはアルカリ水溶液）への溶解性が高いことが好ましい。
【０１３６】
保護層を構成する素材として好ましい例は、ポリビニルアルコール、ポリサッカライド、ポリビニルピロリドン、ポリエチレングリコール、ゼラチン、膠、カゼイン、ヒドロキシエチルセルロース、カルボキシメチルセルロース、メチルセルロース、ヒドロキシエチル澱粉、アラビアゴム、サクローズオクタアセテート、アルギン酸アンモニウム、アルギン酸ナトリウム、ポリビニルアミン、ポリエチレンオキシド、ポリスチレンスルホン酸、ポリアクリル酸、水溶性ポリアミド等が挙げられる。これらの化合物を単独または２種以上併用し塗布組成物とし用いることができる。特に好ましい化合物としてはポリビニルアルコールが挙げられる。
【０１３７】
保護層塗布組成物を調製するには、上記の素材を適当な溶剤に溶解して塗布液とすることができ、この塗布液を本発明に係る光重合性感光層上に塗布し、乾燥して保護層を形成することができる。保護層の厚みは感光性平版印刷版材料として、０．１〜５．０μｍが好ましく、特に好ましくは０．５〜３．０μｍである。保護層には、更に必要に応じて界面活性剤、マット剤等を含有することができる。
【０１３８】
保護層の塗布方法としても、上記例に挙げた公知の方法を好適に用いることができる。保護層の乾燥温度は、感光層の乾燥温度よりも低い方がより好ましい。好ましくは感光層乾燥温度との差が１０℃以上、より好ましくは２０℃以上である場合が好ましく、その場合の上限はせいぜい５０℃程度が好ましい。
【０１３９】
また、保護層の乾燥温度が、感光層が含有するバインダーのガラス転移温度（Ｔｇ）より低いことが好ましい。保護層の乾燥温度と、感光層が含有するバインダーのガラス転移温度（Ｔｇ）の差は２０℃以上であることが好ましく、より好ましくは４０℃以上であり、その差の上限はせいぜい６０℃程度が好ましい。
【０１４０】
（製造方法）
本発明に係る感光性平版印刷版材料は、次の様な製造方法により製造されることが好ましい。すなわち、上記の如くの粗面化された金属支持体上に、上記したエチレン性付加重合性基を有する化合物及び活性光線によりラジカルを発生させる化合物を含有する光重合性層を上記の如く塗布形成する方法が好ましく、更には、以下のａからｄの工程を順次有する製造方法がより好ましい。
ａ） 金属支持体を酸性媒体中で電気化学的に粗面化する工程
ｂ） 前記金属支持体表面を、▲１▼：Ａ）ＰＶＰＡ及びＢ）アミノ基を有する化合物を含有する水系溶媒、▲２▼：▲１▼に更にＣ）エチレン性付加重合性基を有する化合物を含有する水系溶媒及び▲３▼：ＰＶＰＡとアミノ基を有する化合物が反応した反応生成物を含有する水系溶媒、以上の少なくとも１種にて処理する工程
ｃ） エチレン性付加重合性基を有する化合物及び活性光線によりラジカルを発生させる化合物を含有してなる光重合性層を設ける工程
ｄ） オーバーコート層を設ける工程
また、前記複数の工程の中に、更に、金属支持体を機械的に粗面化する工程を有する場合が好ましく、また、前記ｂ）工程の前に、ＰＶＰＡを含有する水系溶媒にて処理する工程を有することが本発明において好ましい。
【０１４１】
（画像形成方法）
本発明の感光性平版印刷版材料に画像露光する光源としては、例えばレーザー、発光ダイオード、キセノンフラッシュランプ、ハロゲンランプ、カーボンアーク灯、メタルハライドランプ、タングステンランプ、高圧水銀ランプ、無電極光源等を挙げることができる。キセノンランプ、ハロゲンランプ、カーボンアーク灯、メタルハライドランプ、タングステンランプ、高圧水銀ランプ、無電極光源等が好ましく用いることができる。
【０１４２】
一括露光する場合には、感光性平版印刷版材料上に、所望の露光画像のパターンを遮光性材料で形成したマスク材料を重ね合わせ、全面に露光すればよい。
【０１４３】
発光ダイオードアレイ等のアレイ型光源を使用する場合や、ハロゲンランプ、メタルハライドランプ、タングステンランプ等の光源を、液晶、ＰＬＺＴ等の光学的シャッター材料で露光制御する場合には、画像信号に応じたデジタル露光をすることが可能であり好ましい。この場合は、マスク材料を使用せず、直接書込みを行うことができる。
【０１４４】
レーザー露光の場合には、光をビーム状に絞り画像データに応じた走査露光が可能なので、マスク材料を使用せず、直接書込みを行うのに適している。また、レーザーを光源として用いる場合には、露光面積を微小サイズに絞ることが容易であり、高解像度の画像形成が可能となる。
【０１４５】
レーザー光源としては、アルゴンレーザー、Ｈｅ−Ｎｅガスレーザー、ＹＡＧレーザー、半導体レーザー等をいずれも好適に用いることが可能である。レーザーの走査方法としては、円筒外面走査、円筒内面走査、平面走査などがある。円筒外面走査では、記録材料を外面に巻き付けたドラムを回転させながらレーザー露光を行い、ドラムの回転を主走査としレーザー光の移動を副走査とする。円筒内面走査では、ドラムの内面に記録材料を固定し、レーザービームを内側から照射し、光学系の一部または全部を回転させることにより円周方向に主走査を行い、光学系の一部または全部をドラムの軸に平行に直線移動させることにより軸方向に副走査を行う。平面走査では、ポリゴンミラーやガルバノミラーとｆθレンズ等を組合せてレーザー光の主走査を行い、記録媒体の移動により副走査を行う。円筒外面走査及び円筒内面走査の方が光学系の精度を高め易く、高密度記録には適している。
【０１４６】
（現像液）
画像露光した光重合性感光層は露光部が硬化する。これをアルカリ現像液で現像処理することにより、未露光部が除去され画像形成が可能となる。この様な現像液としては、従来より知られているアルカリ水溶液が使用できる。例えばケイ酸ナトリウム、同カリウム、同アンモニウム；第二燐酸ナトリウム、同カリウム、同アンモニウム；重炭酸ナトリウム、同カリウム、同アンモニウム；炭酸ナトリウム、同カリウム、同アンモニウム；炭酸水素ナトリウム、同カリウム、同アンモニウム；ホウ酸ナトリウム、同カリウム、同アンモニウム；水酸化ナトリウム、同カリウム、同アンモニウム及び同リチウム等の無機アルカリ剤を使用するアルカリ現像液が挙げられる。
【０１４７】
また、モノメチルアミン、ジメチルアミン、トリメチルアミン、モノエチルアミン、ジエチルアミン、トリエチルアミン、モノ−ｉ−プロピルアミン、ジ−ｉ−プロピルアミン、トリ−ｉ−プロピルアミン、ブチルアミン、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、モノ−ｉ−プロパノールアミン、ジ−ｉ−プロパノールアミン、エチレンイミン、エチレンジアミン、ピリジン等の有機アルカリ剤も用いることができる。
【０１４８】
これらのアルカリ剤は、単独または２種以上組合せて用いられる。また、該現像液には、必要に応じてアニオン性界面活性剤、両性活性剤やアルコール等の有機溶媒を加えることができる。
【０１４９】
本発明に係る現像では、ケイ酸アルカリを含有するｐＨ１２．５未満の現像液で現像することが好ましく、ｐＨ１０．５〜１２．４の範囲がより好ましい。
【０１５０】
【実施例】
以下、本発明を実施例にて説明するが、本発明はこれらに限定されるものではない。尚、実施例における「部」は、特に断りない限り「質量部」を表す。
【０１５１】
実施例１
（バインダーの合成）
窒素気流下の三ツ口フラスコに、メタクリル酸１２部、メタクリル酸メチル７０部、アクリロニトリル８部、メタクリル酸エチル１０部、エタノール５００部及びα、α′−アゾビスイソブチロニトリル３部を入れ、窒素気流中８０℃のオイルバスで６時間反応させた。その後、トリエチルアンモニウムクロライド３部及びグリシジルメタクリレート２部を加えて３時間反応させ、アクリル系共重合体１を得た。ＧＰＣ（ゲルパーミエーションクロマトグラフィー）を用いて測定した質量平均分子量は約５０，０００、ＤＳＣ（示差熱分析法）を用いて測定したガラス転移温度（Ｔｇ）は約８５℃であった。
【０１５２】
（支持体１の作製）
厚さ０．２４ｍｍのアルミニウム板（材質１０５０，調質Ｈ１６）を６５℃に保たれた５％水酸化ナトリウム水溶液に浸漬し、１分間の脱脂処理を行った後、水洗した。この脱脂アルミニウム板を、２５℃に保たれた１０％塩酸水溶液中に１分間浸漬して中和した後、水洗した。次いで、このアルミニウム板を、０．３質量％の硝酸水溶液中で、２５℃、電流密度１００Ａ／ｄｍ²の条件下に交流電流により６０秒間、電解粗面化を行った後、６０℃に保たれた５％水酸化ナトリウム水溶液中で１０秒間のデスマット処理を行った。デスマット処理を行った粗面化アルミニウム板を、１５％硫酸溶液中で、２５℃、電流密度１０Ａ／ｄｍ²、電圧１５Ｖの条件下に１分間陽極酸化処理を行った。この時、表面の中心線平均粗さ（Ｒａ）は０．６５μｍであった。
【０１５３】
上記処理を行った後、続けて下記水溶液及び条件で浸漬し処理を行った。

上記溶液中にアルミニウム板を３０秒間通し、乾燥した。
【０１５４】
【化６】

【０１５５】
（感光性平版印刷版材料の作製）
上記支持体上に、下記組成の光重合性の感光層塗工液を乾燥時１．４ｇ／ｍ²になるようワイヤーバーで塗布し、９５℃で１．５分間乾燥した。その後、更に該感光層上に、下記組成のオーバーコート層塗工液を乾燥時２．０ｇ／ｍ²になるようにアプリケーターで塗布し、７５℃で１．５分間乾燥して、感光層上にオーバーコート層を有する平版印刷版材料を作製した。
【０１５６】

【０１５７】
【化７】

【０１５８】
（画像形成）
以上の様に作製した感光性平版印刷版材料について、ＦＤ−ＹＡＧレーザー光源を搭載したＣＴＰ露光装置（Ｔｉｇｅｒｃａｔ：ＥＣＲＭ社製）を用いて２５４０ｄｐｉ（ｄｐｉとは、２．５４ｃｍ当たりのドット数を表す）の解像度で画像露光を行った。次いで、現像前にオーバーコート層を除去する前水洗部、下記組成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、画線部保護の為のガム液（ＧＷ−３：三菱化学社製を２倍希釈したもの）を備えたＣＴＰ自動現像機（ＰＨＷ３２−Ｖ：Ｔｅｃｈｎｉｇｒａｐｈ社製）でプレヒート（１００℃１０秒）／現像処理を行い、平版印刷版を得た。
【０１５９】

（平版印刷版の評価）
上記のようにして得られた平版印刷版について、以下の評価を行い結果を表１に示す。尚、実施例２以下についても同様に行い結果を表２に示した。
【０１６０】
《感度》
画像部の膜減りが観察されず、且つ、１７５線・５０％の網点露光部が、作製した平版印刷版面上で５０％に再現できる露光量の２倍の光量で描画し、感度とした。
【０１６１】
《耐刷力》
１７５線の画像を適性露光量で露光、現像して作製した平版印刷版を、印刷機（三菱重工業（株）製ＤＡＩＹＡ１Ｆ−１）で、コート紙、印刷インク（東洋インク（株）製トーヨーキングハイエコーＭ紅）及び湿し水（東京インク（株）製Ｈ液ＳＧ−５１濃度１．５％）を用いて印刷を行い、１０００枚連続印刷後、クリーナーで版面をふき、ハイライト部の点細り、シャドウ部の絡みの発生する印刷枚数を耐刷力の指標とした。耐刷力１回は１０００枚連続印刷後クリーナーでふく作業を指す。多いほど耐刷力がよいことを示す。
【０１６２】
《汚し回復》
１０００枚連続印刷後クリーナーでふき、１５分後に印刷を再開し、非画線部の地汚れがなくなる枚数とした。少ないほど良好であることを示す。
【０１６３】
《９０％アミ再現》
上記レーザー描画パワーでリニアリティ未補正でアミ点を描画して、９０％に再現されるはずのアミ点領域を５００倍の光学顕微鏡で撮影し、２ｍｍ×２ｍｍの範囲の画像部の面積を算出してアミ点％として示す。
【０１６４】
【表１】

【０１６５】
以上の様に、本発明の感光性平版印刷版材料では、感度、耐刷力、汚れ回復、リニアリティの性能について優れ、また、エチレン性付加重合性基を有する化合物を併用する場合及びアミノ基及びエチレン性付加重合性基を有する化合物をする場合において、より好ましい性能を示すことが分かる。
【０１６６】
実施例２
以下のＰＶＰＡとジメチルアミノエチルメタクリレート（共栄社化学社製：ライトエステルＤＭ）の混合液を添加比率を変化して調整し、ＰＶＰＡ変性物を作製した。ＰＶＰＡ繰り返し単位に対するライトエステルの付加率は表２の量であった。
【０１６７】
〈溶液温度〉 ８０℃
ビニルホスフォン酸 ０．２質量部
ＰＶＰＡ １．５質量部
ジメチルアミノエチルメタクリレート 表２に示す濃度
希釈溶剤 １００質量部（表２に示す種類）
上記溶液中にアルミニウム板を３０秒間通し、乾燥した。
【０１６８】
上記の評価に加え、以下の評価を行った。
≪溶解性≫
得られた上記変性物の溶解溶剤（表２に記載の溶剤。尚、ＭＥＫとは、メチルエチルケトンを表す）に対し２５℃環境撹拌下で溶解度％を確認した。
【０１６９】
≪付加率≫
ＰＶＰＡホモポリマーの酸価とＰＶＰＡエステルの酸価の比により算出した。
【０１７０】
【表２】

【０１７１】
上記の結果から、いずれも好ましい性能を示すが、付加率が５０モル％以下において汚し回復、リニアリティの性能が優れることが分かる。
【０１７２】
実施例３
（支持体２の作製）
厚さ０．２４ｍｍのアルミニウム板（材質１０５０，調質Ｈ１６）を６５℃に保たれた５％水酸化ナトリウム水溶液に浸漬し、１分間の脱脂処理を行った後、水洗した。この脱脂アルミニウム板を、研磨媒体として微細グレードアルミナ（平均粒子径〜５ミクロン）及び微細グレード石英（〜５ミクロン）（アルミナ対石英７０：３０重良比）からなる固形分１５％のスラリーを使用しウェブ方向と反対方向に２５０ｒｐｍで回転する単一の直径５４．８ｃｍブラシでブラシかけ処理を行うことで機械的に粗面化した後、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／ｄｍ²の条件下に交流電流により６０秒間、電解粗面化を行った後、６０℃に保たれた５％水酸化ナトリウム水溶液中で１０秒間のデスマット処理を行った。デスマット処理を行った粗面化アルミニウム板を、１５％硫酸溶液中で、２５℃、電流密度１０Ａ／ｄｍ²、電圧１５Ｖの条件下に１分間陽極酸化処理を行った。この時、表面の中心線平均粗さ（Ｒａ）は０．７５μｍであった。こうして得られた支持体２及び上記の支持体１について、ＰＶＰＡ処理を行った。ＰＶＰＡ処理としては、下記の処理（ＰＶＰＡ処理１または２）をした。
【０１７３】
〈溶液温度〉 ８０℃
〈ＰＶＰＡ処理１〉
ビニルホスフォン酸 ０．２質量部
ＰＶＰＡ １．５質量部
イオン交換水 １００質量部
〈ＰＶＰＡ処理２〉
ビニルホスフォン酸 ０．２質量部
ＰＶＰＡ １．５質量部
ジメチルアミノエチルメタクリレート ０．５質量部
イオン交換水 １００質量部
上記溶液中に支持体を２０秒間侵漬し、乾燥した。
【０１７４】
実施例３においては、試料１〜３として、上記の支持体１、２とＰＶＰＡ処理１、２について、下記の様な組合せの処理を行った。尚、感光層及びオーバーコート層については、実施例１と同様にして感光性平版印刷版材料を作製した。
【０１７５】
試料１：支持体１にＰＶＰＡ処理２を施す。
試料２：支持体２にＰＶＰＡ処理２を施す。
【０１７６】
試料３：支持体２にＰＶＰＡ処理１及び２を施す。
実施例１と同様に評価し、結果を表３に示した。
【０１７７】
【表３】

【０１７８】
本発明の製造方法によれば、良好な性能を得ることができるが、特に機械的粗面化及び電気化学的粗面化を行った支持体において高い耐刷力を得ることができる。また、ＰＶＰＡ処理１と２を併用することで、好ましい汚し回復の性能が得られることが分かる。
【０１７９】
【発明の効果】
本発明は、光重合層と支持体との接着性に優れ、耐刷力と非画線部の汚れ改良の両立ができ、更には、高解像度で保存性も良好な平版印刷版を得ることができる感光性平版印刷版材料用支持体及び感光性平版印刷版材料並びにその製造方法を提供することができた。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a support for a photosensitive lithographic printing plate material excellent in printing durability, stain recovery and linearity, a photosensitive lithographic printing plate material, and a method for producing the same.
[0002]
[Prior art]
Conventionally, there has been known a photosensitive lithographic printing plate material in which a photopolymerizable layer and a protective layer are laminated on a support subjected to a hydrophilic surface treatment. In particular, in recent years, in order to obtain a high-resolution lithographic printing plate material quickly, and for the purpose of filmlessness, digital exposure based on image information using a laser is performed and developed to develop a lithographic printing plate. The manufacturing method has been generalized.
[0003]
For example, a light source is modulated by an output signal from an electronic plate-making system or an image processing system or an image signal transmitted through a communication line, etc., and a photosensitive lithographic printing plate material is directly scanned and exposed to a lithographic plate. Systems for forming printing plates are known.
[0004]
The photopolymerizable layer generally contains an acrylic monomer, an alkali-soluble resin, a photopolymerizable initiator, and, if necessary (especially when performing laser writing), a sensitizing dye to match the wavelength. It is known.
[0005]
It is also known to provide a protective layer (oxygen blocking layer) for the purpose of preventing polymerization inhibition due to oxygen.
[0006]
A long-wavelength visible light source such as an Ar laser (488 nm) or an FD-YAG laser (532 nm) is used as a light source for exposing and making a photopolymerization type photosensitive lithographic printing material. Furthermore, in recent years, for example, semiconductor lasers that can continuously oscillate in the 350 to 450 nm region using InGaN-based or ZnSe-based materials have been put into practical use. The scanning exposure system using these short-wave light sources has an advantage that an economical system can be constructed while having a sufficient output because a semiconductor laser can be manufactured at a low cost because of its structure. Furthermore, there is a possibility that a photosensitive lithographic printing plate material having a shorter photosensitive area capable of working under a brighter safe light can be used as compared with a system using a conventional FD-YAG or Ar laser. .
[0007]
In photopolymerization type photosensitive lithographic printing plate materials, usually after image exposure, if necessary, heat treatment, water washing for removing the protective layer, development treatment for dissolving and removing unexposed portions, water washing treatment, non-washing A finisher gum treatment is performed to make the image area hydrophilic, and a lithographic printing plate is obtained.
[0008]
Such a photopolymerization type photosensitive lithographic printing plate material generally has a low printing durability, and in order to increase the printing durability, as described in JP-B-46-35685, polyvinyl phosphonic acid is used. However, even if these technologies are used, the printing durability is still inadequate, and attempts are made to improve the adhesion between the photosensitive layer and the support. However, when the processing amount of such processing is increased, there is a problem that the non-image portion is stained.
[0009]
In addition, there are known techniques for providing an intermediate layer between the support and the photosensitive layer, and coupling or diazonium treatment of the support, both of which increase the cost and improve printing durability and non-image. The level of soiling was not satisfactory.
[0010]
[Problems to be solved by the invention]
Accordingly, an object of the present invention is to solve the above problems. That is, in the present invention, it is excellent in the adhesion between the photopolymerizable layer and the support, and it is possible to achieve both the printing durability and the improvement of stains in the non-image area, and furthermore, a lithographic printing plate having a high resolution. It is an object to provide a support for a photosensitive lithographic printing plate material, a photosensitive lithographic printing plate material, and a method for producing the same.
[0011]
[Means for Solving the Problems]
The above object of the present invention has been achieved by the following.
[0012]
1. A roughened metal support comprising at least A) polyvinyl phosphonic acid and B) 1st or 2nd class A support for a photosensitive lithographic printing plate material, which is treated with an aqueous solvent containing a compound containing an amino group.
[0013]
2. 2. The photosensitive lithographic printing plate material support according to 1 above, wherein the aqueous solvent further contains a compound having C) an ethylenic addition polymerizable group.
[0014]
3. 2. The photosensitive lithographic printing plate material support according to 1 above, wherein the compound having an amino group is D) a compound having an amino group and an ethylenic addition polymerizable group.
[0015]
4). Photosensitive lithographic printing comprising a roughened metal support and treated with an aqueous solvent containing at least a reaction product obtained by reacting polyvinyl phosphonic acid with a compound having an amino group Plate material support.
[0016]
5. The support for a photosensitive lithographic printing plate material as described in 4 above, wherein the addition ratio of the compound having an amino group to the repeating unit of the polyvinyl phosphonic acid is 0.01 to 50 mol%.
[0017]
6). A photosensitive lithographic printing plate material having a photopolymerizable layer containing a compound having an ethylenic addition polymerizable group and a compound capable of generating radicals by actinic light on a roughened metal support, the metal The support is 1) : A) polyvinyl phosphonic acid and B) 1st or 2nd class An aqueous solvent containing a compound having an amino group, 2) : 1) And C) an aqueous solvent containing a compound having an ethylenic addition polymerizable group, and 3) A photosensitive lithographic printing plate material treated with at least one selected from aqueous solvents containing a reaction product obtained by reacting a compound having polyvinyl phosphonic acid and an amino group.
[0018]
7). The reaction product obtained by the reaction between the polyvinyl phosphonic acid and the compound having an amino group is in the range of 0.01 to 50 mol% as the addition ratio of the compound having an amino group to the repeating unit of the polyvinyl phosphonic acid. 7. The photosensitive lithographic printing plate material as described in 6 above.
[0019]
8). A method for producing a photosensitive lithographic printing plate material comprising a photopolymerizable layer containing a compound having an ethylenic addition polymerizable group and a compound capable of generating radicals by actinic rays on a roughened metal support. A process for producing a photosensitive lithographic printing plate material comprising the following steps a to d:
a) Electrochemical roughening of the metal support in an acidic medium
b) the surface of the metal support; 1) : A) polyvinyl phosphonic acid and B) 1st or 2nd class An aqueous solvent containing a compound having an amino group, 2) : 1) And C) an aqueous solvent containing a compound having an ethylenic addition polymerizable group, and 3) : Treatment with an aqueous solvent containing a reaction product obtained by reacting a compound having polyvinyl phosphonic acid and an amino group, at least one of the above
c) A step of providing a photopolymerizable layer comprising a compound having an ethylenic addition polymerizable group and a compound that generates radicals by actinic rays.
d) Step of providing an overcoat layer
9. 9. The method for producing a photosensitive lithographic printing plate material as described in 8 above, wherein the steps a to d further comprise a step of mechanically roughening the metal support.
[0020]
10. 9. The method for producing a photosensitive lithographic printing plate material as described in 8 above, further comprising a step of treating with an aqueous solvent containing polyvinyl phosphonic acid before the step b).
[0024]
That is, in the present invention, when a compound having an amino group is contained in the PVPA bath at the time of PVPA (polyvinyl phosphonic acid) treatment, which is performed as a pretreatment of the support, the above compound is amine-added to the PVPA polymer, It is found that a reactive group is easily introduced into the polymer, and the reactivity between the PVPA itself or the support of the above compound itself and the reactivity between the reactive group newly imparted to PVPA and the photopolymerizable layer. Attention has been made to find a new treatment that does not cause high adhesion between the support and the photopolymerizable layer and storage dirt, and the present invention has been achieved.
[0025]
Furthermore, the present invention does not necessarily require a three-layer coating type production line of intermediate layer / photopolymerizable layer (photosensitive layer) / overcoat layer (oxygen barrier layer) as conventionally performed. Since the pretreatment bath and the photosensitive layer / oxygen barrier layer can be applied, it is very advantageous in terms of cost.
[0026]
The present invention can provide a printing plate with high resolution, high printing durability, and good stains on non-image areas at low cost.
[0027]
(Metal support)
The metal support according to the present invention (hereinafter also referred to as a support) is, for example, a metal plate such as aluminum, stainless steel, chromium, or nickel, or a plastic film such as a polyester film, polyethylene film, or polypropylene film. A laminate or vapor-deposited metal thin film can be used, and a polyester film, a vinyl chloride film, a nylon film or the like subjected to a hydrophilic treatment can be used, but an aluminum support is preferably used, In this case, pure aluminum or aluminum alloy may be used.
[0028]
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, and iron. It is done.
[0029]
The support 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.
[0030]
Examples of the roughening method in the present invention include a mechanical method and an electrochemical method, but it is preferable to perform roughening electrochemically in an acidic medium, and in this case, mechanically You may combine the method of roughening.
[0031]
The method of electrochemically roughening is not particularly limited, but a method of electrochemically roughening in an acidic medium, that is, 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.
[0032]
This roughening method can be generally performed by applying a voltage in the range of 1 to 50 volts, but it is preferable to set the voltage from a range of 10 to 30 volts.
[0033]
Current density is 10 to 200 A / dm ² The range of 50 to 150 A / dm can be used. ² It is preferable to select from the range. The amount of electricity is 100 to 5000 c / dm ² The range of 100 to 2000 c / dm can be used. ² It is preferable to select from the range.
[0034]
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.
[0035]
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 / dm ² The range of 20-100 A / dm can be used. ² It is preferable to select from the range. The amount of electricity is 100 to 5000 c / dm ² The range of 100 to 2000 c / dm can be used. ² It is preferable to select from the range. The temperature at which the electrochemical roughening method is performed can be in the range of 10 to 50 ° C, but is preferably selected from the range of 15 to 45 ° C. The concentration of nitric acid in the electrolytic solution is preferably 0.1 to 5% by mass. If necessary, nitrate, chloride, amines, aldehydes, phosphoric acid, chromic acid, boric acid, acetic acid, oxalic acid, and the like can be added to the electrolytic solution.
[0036]
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 / dm ² The range of 50 to 150 A / dm can be used. ² It is preferable to select from the range. The amount of electricity is 100 to 5000 c / dm ² The range of 100 to 2000 c / dm can be used. ² Furthermore, 200 to 1000 c / dm ² It is preferable to select from the range. The temperature at which the electrochemical roughening method is performed can be in the range of 10 to 50 ° C, but is preferably selected from the range of 15 to 45 ° C. The concentration of hydrochloric acid in the electrolytic solution is preferably 0.1 to 5% by mass. If necessary, nitrate, chloride, amines, aldehydes, phosphoric acid, chromic acid, boric acid, acetic acid, oxalic acid, and the like can be added to the electrolytic solution.
[0037]
After the surface is roughened by the electrochemical surface roughening method, it is preferably immersed in an acid or alkali aqueous solution in order to remove aluminum scraps on the surface. Examples of the acid include sulfuric acid, persulfuric acid, hydrofluoric acid, phosphoric acid, nitric acid, hydrochloric acid, and the like. Examples of the base include sodium hydroxide and potassium hydroxide. Among these, it is preferable to use an alkaline aqueous solution. The amount of aluminum dissolved on the surface is 0.5 to 5 g / m. ² Is preferred. Moreover, it is preferable to perform a neutralization process by immersing in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid or a mixed acid thereof after the immersion treatment with an alkaline aqueous solution.
[0038]
Further, the method of mechanically roughening according to the present invention 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 size of 10 to 100 μm are applied to the support surface at an interval of 100 to 200 μm at 2.5 × 10 5. ^Three -10x10 ^Three Piece / cm ² It is also possible to perform roughening by laminating the coated sheets so as to exist at a density and transferring the rough surface pattern of the sheet by applying pressure.
[0039]
After roughening by the above 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, the 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. ² Is preferred. After the immersion treatment with an alkaline aqueous solution, it is preferable to carry out a neutralization treatment by immersion in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid or a mixed acid thereof.
[0040]
The mechanical surface roughening treatment method and the electrochemical surface roughening method as described above may be used independently to roughen the surface, or may be combined to roughen the surface. Is preferred.
[0041]
Next, the support can be anodized. There is no restriction | limiting in particular in the method of the anodizing process which can be used in this invention, A well-known method can be used. By performing the anodizing treatment, an oxide film is formed on the support. In the anodizing treatment, an aqueous solution containing sulfuric acid and / or phosphoric acid at a concentration of 10 to 50% is used as an electrolytic solution, and a current density of 1 to 10 A / dm. ² The electrolysis method is preferably used, but in addition, a method of electrolysis at a high current density in sulfuric acid described in US Pat. No. 1,412,768 and a 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. ² Is suitable, preferably 10 to 40 mg / dm ² It 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.
[0042]
The anodized support may be sealed as necessary. These sealing treatments can be performed using a known method such as hot water treatment, boiling water treatment, steam treatment, sodium silicate treatment, dichromate aqueous solution treatment, nitrite treatment, ammonium acetate treatment.
[0043]
The support subjected to anodization treatment or sealing treatment as necessary is preferably treated with an aqueous solvent containing PVPA after the treatment, and the aqueous solvent is an aqueous solution. Is preferred.
[0044]
The aqueous solution containing PVPA is preferably an aqueous solution containing 0.01 to 30% of PVPA in concentration, and particularly preferably an aqueous solution of 0.05 to 10%. If the content concentration is smaller than this, the effect of the present invention is small, and if it is large, the liquid viscosity is high and handling may be difficult, and the above range can be used as a preferable range.
[0045]
In addition, it is preferable that the aqueous solution further contains a compound other than PVPA, and examples of the contained compound include conventionally known water-soluble resins, water-dispersible inorganic fine particles, acids, bases and the like.
[0046]
Specifically, as the water-soluble resin, these hydrophilic resins include, for example, polyvinyl alcohol, polysaccharide, polyvinyl pyrrolidone, polyethylene glycol, gelatin, glue, casein, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, hydroxyethyl starch, Sucrose octaacetate, ammonium alginate, sodium alginate, polyvinylamine, polyallylamine, polystyrene sulfonic acid, polyacrylic acid, water-soluble polyamide, maleic anhydride copolymer and the like.
[0047]
Examples of the water-dispersible inorganic fine particles include colloidal silica and necklace-shaped colloidal silica described in JP-A No. 2001-232746.
[0048]
Examples of acids include phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, other strong acids, and salts thereof.
[0049]
Examples of bases include sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonium hydroxide, tetramethylammonium hydroxide, and tetrabutylammonium hydroxide.
[0050]
In the present invention, the compound that can be used together with these PVPAs is preferably from 0 to 40%, more preferably from 0 to 20%, as the concentration in the aqueous solution.
[0051]
The treatment time for the treatment with the aqueous solution containing PVPA according to the present invention is preferably from 0.5 seconds to 3 minutes, more preferably from 1 second to 1 minute, and particularly preferably from 2 seconds to 30 seconds. If the amount is less than this, the effects of the present invention may be reduced. If the amount is more than this, the productivity is inferior, so the above range is preferable.
[0052]
The treatment temperature during treatment with the aqueous solution is preferably such that the aqueous solution temperature and the substrate to be treated are in the range of 40 to 100 ° C., more preferably 50 to 90 ° C., particularly 60 to 80 ° C. preferable. If the temperature is lower than this, the effect of the present invention may be small. If the temperature is higher than this, the above-described range is preferable from the viewpoint of production stability.
[0053]
Moreover, although the PVPA process which concerns on this invention is as showing next, it performs about the support body which performed the above-mentioned PVPA process performed as needed. That is, the PVPA treatment of the present invention comprises (1): A) PVPA and B) an aqueous solvent containing a compound having an amino group, (2): (1) and C) ethylenic addition polymerization. It is preferable to treat with an aqueous solvent containing a compound having a reactive group and (3): an aqueous solvent containing a reaction product obtained by reacting PVPA with an amino group, at least one of the above. Water is preferred.
[0054]
In the present invention, the compound (1) having an amino group is a compound having an amino group and an ethylenic addition polymerizable group.
[0055]
The aqueous solvent referred to in the present invention refers to a solvent containing water as a main component, and the mass% of water in the solvent is preferably 50% or more, more preferably 70% or more. The aqueous solvent is preferably an aqueous solution of the above-described PVPA and each compound (compounds contained in the above (1) to (3)).
[0056]
Moreover, in this invention, the case where it carries out using the PVPA process of the said invention and the above-mentioned PVPA process together is more preferable.
[0057]
The aqueous solution used for the PVPA treatment of the present invention is preferably an aqueous solution containing PVPA as a main component. The ratio in the mass of PVPA and each of the above-mentioned compounds (the total when they are mixed) is preferably 99.99: 0.01 to 30:70, more preferably Is in the range of 99.9: 0.1-50: 50.
[0058]
The PVPA referred to in the present invention refers to a polymer having a vinyl phosphonic acid skeleton, and preferably has a vinyl phosphonic acid repeating unit of 50% or more, more preferably 70% or more of all repeating units.
[0059]
The molecular weight Mw of the PVPA is preferably 1,000 to 1,000,000, more preferably 2000 to 500,000.
[0060]
Moreover, the pH of the aqueous solution of PVPA (concentration 10%) is preferably in the range of 1 to 4, and more preferably in the range of 1.2 to 2.5.
[0061]
In the aqueous solution used for the PVPA treatment of the present invention, other solvents can be used in combination with water. The solvent that can be used is not particularly limited as long as it is a water-based organic solvent, but alcohol-based solvents, glycol-based solvents, and ether-based solvents are preferable, and alcohol-based solvents are particularly preferable.
[0062]
In the present invention, it is also possible to preferably use a pH adjuster using an acid such as acetic acid / hydrochloric acid or a base such as ammonia / sodium hydroxide.
[0063]
(Compound having an amino group)
The compound having an amino group according to the present invention is taken into the polymer chain by reacting with the hydroxyl group of PVPA, and dissolves as the reaction proceeds due to the water solubility of the polymer. A compound having an amino group with respect to the repeating unit of PVPA because the water solubility of PVPA deteriorates, resulting in a decrease in reactivity with the support, and a disadvantage of causing a decrease in the stability of the processing solution. Is preferably in the range of 0.01 to 50 mol%. More preferably, the range of 0.05 to 45 mol%, particularly 0.1 to 40 mol% is preferable. The addition rate can be analyzed by NMR (nuclear magnetic resonance analysis), IR (infrared analysis), or the like.
[0064]
From this point of view, it is preferable that the compound having an amino group has a higher water solubility, and it is particularly preferable that the compound having a solubility of 1% by mass or more in pure water at normal pressure and 25 ° C. within 24 hours.
[0065]
Further, the amino group of the compound having an amino group according to the present invention may be a primary, secondary, tertiary or quaternary amino group, but a primary or secondary amino group is preferred.
[0066]
As the compound having an amino group according to the present invention, a compound having an amino group and an ethylenic addition polymerizable group can be preferably used.
[0067]
(Compound having amino group and ethylenic addition polymerizable group)
The amino group of the compound having an amino group and an ethylenic addition polymerizable group according to the present invention may be either a primary, secondary, tertiary or quaternary amino group, but a primary or secondary amino group. Is preferred. A preferable compound having an amino group and an ethylenic addition polymerizable group in one molecule is a compound represented by the following formula, but is not limited thereto.
[0068]
[Chemical 1]

[0069]
Where R ₁ Represents an organic group having a monovalent ethylenic addition polymerizable group, and examples thereof include an acryloyl group, a methacryloyl group, and a vinyl group, and an acryloyl group or a methacryloyl group is particularly preferable. Y represents a divalent linking group having 1 to 10 carbon atoms, an alkylene group, an arylene group, an alkenylene group, an alkynylene group, -SO. ₂ -, -SO-, -O-, -S-, -N (R _Ten )-,-(C = O)-, -COO-,-(P = O)-, -CONH- and the like. However, R _Ten Represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group. Among the above, a divalent linking group constituted by an alkylene group, —O—, — (C═O) —, —COO—, or —CONH— alone or in combination is preferable.
[0070]
R ₂ And R _Three Each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, an alkenyl group, a cycloalkenyl group, an alkynyl group or a heterocyclic ring, preferably a hydrogen atom, an alkyl group or a heterocyclic ring. Examples of the ethylenic addition polymerizable group include known ones described later.
[0071]
Specific examples of the compound having an amino group and an ethylenic addition polymerizable group in one molecule according to the present invention include N, N-dimethylaminoethyl acrylate, N, N-diethylaminoethyl acrylate, N, N- Dimethylaminopropyl acrylate, N, N-diethylaminopropyl acrylate, N, N-dimethylaminobutyl acrylate, N, N-diethylaminobutyl acrylate and N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, N, N -Dimethylaminopropyl methacrylate, N, N-diethylaminopropyl methacrylate, N, N-dimethylaminobutyl methacrylate, N, N-diethylaminobutyl methacrylate, N, N-dimethylaminoethyl acrylamide, N N-diethylaminopropylacrylamide, N, N-dimethylaminoethylmethacrylamide, N, N-dimethylaminopropylmethacrylamide, N, N-diethylaminoethylmethacrylamide, N, N-diethylaminopropylmethacrylamide, 2-vinylpyridine, 4 -Vinyl pyridine, allylamine, 2-methylallylamine, diallylamine, etc. are mentioned, but not particularly limited thereto. However, an amino compound having an acrylic group or a methacryl group as an unsaturated group is desirable from the viewpoint of photoreactivity.
[0072]
The following compounds are also preferably used in the present invention.
[0073]
[Chemical 2]

[0074]
(Compound having two or more amino groups in one molecule)
In addition, as the compound having an amino group according to the present invention, a compound having two or more amino groups in one molecule can be preferably used, and the amino group in this compound is primary, secondary, tertiary or 4 Any of primary amino groups may be used, but primary or secondary amino groups are preferred. A preferred amino group is a compound represented by the following formula, but is not limited thereto.
[0075]
[Chemical 3]

[0076]
Where R _Four Is a divalent organic group having 1 to 22 carbon atoms (preferably an alkylene group, an arylene group, an alkenylene group, an alkynylene group, -SO ₂ -, -SO-, -O-, -S-, -N (R _Ten )-,-(C = O)-, -COO-,-(P = O)-, -CONH-, and the like. Can be mentioned. However, R _Ten Represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group.
[0077]
Among these, a divalent linking group constituted by an alkylene group, an arylene group, —O—, — (C═O) —, —COO—, —CONH— or the like alone or in combination is preferable. It is.
[0078]
Specifically, 3,3′-diaminobiphenyl, 3,4′-diaminobiphenyl, 4,4′-diaminobiphenyl, 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 4,4′- Diaminodiphenylmethane, 2,2- (3,3′-diaminodiphenyl) propane, 2,2- (3,4′-diaminodiphenyl) propane, 2,2- (4,4′-diaminodiphenyl) propane, 2, 2- (3,3′-diaminodiphenyl) hexafluoropropane, 2,2- (3,4′-diaminodiphenyl) hexafluoropropane, 2,2- (4,4′-diaminodiphenyl) hexafluoropropane, 3 , 3′-oxydianiline, 3,4′-oxydianiline, 4,4′-oxydianiline, 3,3′-diaminodiphenyl sulfide, 3,4′-di Minodiphenyl sulfide, 4,4′-diaminodiphenyl sulfide, 3,3′-diaminodiphenyl sulfone, 3,4′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfone, 1,3-bis [1- (3 -Aminophenyl) -1-methylethyl] benzene, 1,3-bis [1- (4-aminophenyl) -1-methylethyl] benzene, 1,4-bis [1- (3-aminophenyl)] benzene 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) ) Benzene, 3,3′-bis (3-aminophenoxy) diphenyl ether, 3,3′-bis (4-aminophenoxy) diphenyl ether, 3 , 4′-bis (3-aminophenoxy) diphenyl ether, 3,4′-bis (4-aminophenoxy) diphenyl ether, 4,4′-bis (3-aminophenoxy) diphenyl ether, 4,4′-bis (4- Aminophenoxy) diphenyl ether, 1,4-bis [1- (4-aminophenyl) -1-methylethyl-bis (3-aminophenoxy)] biphenyl, 3,3′-bis (4-aminophenoxy) biphenyl, 3, , 4′-bis (3-aminophenoxy) biphenyl, 3,4′-bis (4-aminophenoxy) biphenyl, 4,4′-bis (3-aminophenoxy) biphenyl, 4,4′-bis (4- Aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl Sulfone, 2,2-bis [3- (3-aminophenoxy) phenyl] propane, 2,2-bis [3- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-amino) Phenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3- (3-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [ 3- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (3-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] Hexafluoropropane, 9,9-bis (3-aminophenyl) fluorene, 9,9-bis (4-aminophenyl) fluorene, methylenedi , Hexamethylene diamine, can be exemplified dodecamethylene diamine. ) Or a divalent group having a siloxane bond.
[0079]
Specific examples include 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenyl sulfide, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,6-diaminotoluene, benzidine, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, o-tolidine, 4,4 "-diaminoter Phenyl, 1,5-diaminonaphthalene, 2,5-diaminopyridine, 3,3′-dimethyl-4,4′-diaminodiphenylmethane, 4,4′-bis (p-aminophenoxy) biphenyl, 2,2-bis [4- (p-aminophenoxy) phenyl] propane, hexahydro-4,7-methanoindanile Examples include, but are not limited to, dimethylenediamine, etc. In addition, it is preferable to use siloxane diamine in order to improve adhesion to an inorganic substrate, and siloxane diamine represented by the following formula is preferably used. Can be mentioned.
[0080]
[Formula 4]

[0081]
Where R _Five Is a divalent organic group having 1 to 10 carbon atoms (preferably an alkylene group, an arylene group, an alkenylene group, an alkynylene group, -SO ₂ -, -SO-, -O-, -S-, -N (R _Ten )-,-(C = O)-, -COO-,-(P = O)-, -CONH- and the like. However, R _Ten Represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group. m represents an integer of 1 to 10.
[0082]
Among these, a divalent linking group constituted by an alkylene group or an arylene group alone or in combination is preferable.
[0083]
R ₆ , R ₇ , R ₈ Or R ₉ Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, an alkenyl group, a cycloalkenyl group, an alkynyl group or a heterocyclic ring. Among these, a hydrogen atom or an alkyl group is preferable.
[0084]
When the siloxane diamine is used in the present invention, it is preferably used in the range of 1 to 20 mol% in the compound having two or more amino groups in one molecule according to the present invention. Thereby, the adhesive improvement effect is exhibited, and the heat resistance performance is also good, which is preferable.
[0085]
Specific examples of the siloxane diamine include bis (3-aminopropyl) tetramethyldisiloxane, bis (10-aminodecamethylene) tetramethyldisiloxane, aminopropyl-terminated dimethylsiloxane tetramer, octamer, bis (3 -Aminophenoxymethyl) tetramethyldisiloxane and the like. In the present invention, one or more compounds having two or more amino groups in one molecule can be used.
[0086]
Specific examples of the compound having two or more amino groups in one molecule according to the present invention include the following.
[0087]
[Chemical formula 5]

[0088]
(Compound having an ethylenic addition polymerizable group)
Examples of the compound having an ethylenic addition polymerizable group used in the present invention include known monomers (hereinafter sometimes simply referred to as monomers). Specific examples thereof include 2 -Ethylhexyl acrylate, 2-hydroxypropyl acrylate, glycerol acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, nonylphenoxyethyl acrylate, tetrahydrofurfuryloxyethyl acrylate, tetrahydrofurfuryloxyhexanolide acrylate, 1,3-dioxane alcohol Monofunctional acrylates such as acrylate of ε-caprolactone adduct, 1,3-dioxolane acrylate, or these acrylates may be methacrylate, itaconate, crotonate, maleate Methacrylic acid, itaconic acid, crotonic acid, maleic acid ester, such as ethylene glycol diacrylate, polytetramethylene glycol diacrylate, triethylene glycol diacrylate, pentaerythritol diacrylate, hydroquinone diacrylate, resorcindi Acrylate, hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, diacrylate of neopentyl glycol hydroxypivalate, diacrylate of neopentyl glycol adipate, ε-caprolactone adduct of neopentyl glycol hydroxypivalate Diacrylate, 2- (2-hydroxy-1,1-dimethylethyl) -5-hydroxymethyl-5 Bifunctional acrylic esters such as til-1,3-dioxane diacrylate, tricyclodecane dimethylol acrylate, ε-caprolactone adduct of tricyclodecane dimethylol acrylate, diglycidyl ether diacrylate of 1,6-hexanediol Methacrylic acid, itaconic acid, crotonic acid, maleic acid ester such as trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, trimethylolethane triacrylate, pentane Erythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pen Acrylate, dipentaerythritol hexaacrylate, ε-caprolactone adduct of dipentaerythritol hexaacrylate, pyrogallol triacrylate, propionic acid-dipentaerythritol triacrylate, propionic acid-dipentaerythritol tetraacrylate, hydroxypivalyl aldehyde modified dimethylol Examples include polyfunctional acrylic acid esters such as propane triacrylate, or methacrylic acid, itaconic acid, crotonic acid, maleic acid ester, etc. in which these acrylates are replaced by methacrylate, itaconate, crotonate, maleate, and oligomers thereof. Can be used.
[0089]
Moreover, the prepolymer by the said monomer can also be used similarly to the above. Examples of the prepolymer include compounds as described below, and a prepolymer in which acrylic acid or methacrylic acid is introduced into an oligomer having an appropriate molecular weight to impart photopolymerizability can be suitably 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.
[0090]
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 Acrylates such as bisphenol A-epichlorohydrin- (meth) acrylic acid, phenol novolac-epichlorohydrin- (meth) acrylic acid, and epoxy acrylates in which (meth) acrylic acid is introduced into an epoxy resin, 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 Of trimethylolpropane-propylene glycol-tolylene diisocyanate-2-hydroxyethyl acrylate In addition, urethane acrylates in which (meth) acrylic acid is introduced into urethane resins, for example, silicone resin acrylates such as polysiloxane acrylate and polysiloxane-diisocyanate-2-hydroxyethyl acrylate, and (meth) acryloyl in oil-modified alkyd resins. Examples thereof include prepolymers such as alkyd-modified acrylates having introduced groups and spirane resin acrylates.
[0091]
The compound having an ethylenic addition polymerizable group described above can also be applied to a photopolymerizable layer (also referred to as a photosensitive layer) of the photosensitive lithographic printing plate material according to the present invention.
[0092]
In the photosensitive layer according to the present invention, phosphazene monomer, triethylene glycol, isocyanuric acid ethylene oxide (EO) -modified diacrylate, isocyanuric acid EO-modified triacrylate, dimethylol tricyclodecane diacrylate, trimethylol propane acrylic It can contain monomers such as acid benzoic acid esters, alkylene glycol type acrylic acid-modified, urethane-modified acrylates, and addition-polymerizable oligomers and prepolymers having structural units formed from the monomers.
[0093]
Examples of the monomer preferably used in the present invention include a phosphate ester compound having at least one ethylenic double bond group. The compound is a compound in which at least a part of the hydroxyl group of phosphoric acid is esterified, and may have an ethylenic double bond in the molecule, and particularly preferably a compound having a (meth) acryloyl group.
[0094]
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. Among 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.
[0095]
In the photosensitive layer according to the present invention, the above-mentioned monomer is preferably contained in the range of 1.0 to 80.0% by mass of the photosensitive composition for coating the photosensitive layer, more preferably 3.0. It is in the range of ˜70.0% by mass.
[0096]
(Polymer binder)
The photosensitive layer according to the present invention preferably contains a polymer binder (binder). The polymer binder preferably contains a vinyl copolymer composed of at least one of the monomers described in (1) to (17) below.
[0097]
(1) Monomers having an aromatic hydroxyl group, such as o- (or p-, m-) hydroxystyrene, o- (or p-, m-) hydroxyphenyl acrylate, and the like.
[0098]
(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.
[0099]
(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.
[0100]
(4) Monomers having a sulfonamide group, such as N- (p-toluenesulfonyl) acrylamide, N- (p-toluenesulfonyl) methacrylamide and the like.
[0101]
(5) α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride and the like.
[0102]
(6) substituted or unsubstituted alkyl acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, nonyl acrylate, acrylic acid Decyl, undecyl acrylate, dodecyl acrylate, benzyl acrylate, cyclohexyl acrylate, 2-chloroethyl acrylate, N, N-dimethylaminoethyl acrylate, glycidyl acrylate, and the like.
[0103]
(7) substituted or unsubstituted alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, nonyl methacrylate, methacrylic acid Decyl, undecyl methacrylate, dodecyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, 2-chloroethyl methacrylate, N, N-dimethylaminoethyl methacrylate, glycidyl methacrylate and the like.
[0104]
(8) Acrylamide or methacrylamides such as acrylamide, methacrylamide, N-ethylacrylamide, N-hexylacrylamide, N-cyclohexylacrylamide, N-phenylacrylamide, N- (4-nitrophenyl) acrylamide, N-ethyl-N -Phenylacrylamide, N- (4-hydroxyphenyl) acrylamide, N- (4-hydroxyphenyl) methacrylamide and the like.
[0105]
(9) Monomers containing alkyl fluoride 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.
[0106]
(10) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, phenyl vinyl ether and the like.
[0107]
(11) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate, vinyl benzoate and the like.
[0108]
(12) Styrenes such as styrene, methyl styrene, chloromethyl styrene and the like.
[0109]
(13) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.
[0110]
(14) Olefins such as ethylene, propylene, i-butylene, butadiene, isoprene and the like.
[0111]
(15) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine and the like.
[0112]
(16) Monomers having a cyano group, such as acrylonitrile, methacrylonitrile, 2-pentenenitrile, 2-methyl-3-butenenitrile, 2-cyanoethyl acrylate, o- (or m-, p-) cyanostyrene.
[0113]
(17) A monomer having an amino group, such as N, N-diethylaminoethyl methacrylate, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, polybutadiene urethane acrylate, N, N-dimethylaminopropyl acrylamide, N , N-dimethylacrylamide, acryloylmorpholine, Ni-propylacrylamide, N, N-diethylacrylamide and the like.
[0114]
The polymer binder may include other arbitrary polymer binders such as polyvinyl butyral resin, polyurethane resin, polyamide resin, polyester resin, epoxy resin, novolac resin, natural resin, etc. You may use together with the vinyl type copolymer which concerns.
[0115]
The content of the polymer binder in the composition for coating the photosensitive layer according to the invention is preferably in the range of 10 to 90% by mass, more preferably in the range of 15 to 70% by mass with respect to the photosensitive layer. It is particularly preferable in terms of sensitivity to use in the range of mass%. Furthermore, the vinyl copolymer is preferably 50 to 100% by mass, and more preferably 100% by mass in the polymer binder.
[0116]
The acid value of the polymer contained in the polymer binder according to the present invention is preferably used in the range of 10 to 150, more preferably in the range of 30 to 120, and in the range of 50 to 90. From the viewpoint of balancing the polarity of the entire photosensitive layer, it is particularly preferable, and this makes it possible to prevent aggregation of the pigment in the photosensitive layer coating solution.
[0117]
(Compound that generates radicals by actinic rays)
For the photopolymerizable layer (photosensitive layer) according to the present invention, it is preferable to use a compound that generates radicals by actinic rays (hereinafter also referred to as a photopolymerization initiator). J. et al. Carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo compounds, diazo compounds, halogen compounds, photoreduction as described in Chapter 5 of “Light Sensitive Systems” by J. Kosar And the like, and the compounds disclosed in British Patent 1,459,563 are also preferred.
[0118]
Specifically, the following examples can be given, but the invention is not limited thereto. That is, benzoin derivatives such as benzoin methyl ether, benzoin-i-propyl ether, α, α′-dimethoxy-α-phenylacetophenone; benzophenone, 2,4-dichlorobenzophenone, methyl o-benzoylbenzoate, 4,4′- Benzophenone derivatives such as bis (dimethylamino) benzophenone; thioxanthone derivatives such as 2-chlorothioxanthone and 2-i-propylthioxanthone; anthraquinone derivatives such as 2-chloroanthraquinone and 2-methylanthraquinone; N-methylacridone and N-butyl In addition to acridone derivatives such as acridone; α, α′-diethoxyacetophenone, benzyl, fluorenone, xanthone, uranyl compounds, Japanese Patent Publication Nos. 59-1281, 61-9621, and Japanese Patent Laid-Open No. 60-60 Triazine derivatives described in JP-A-60104; organic peroxides described in JP-A Nos. 59-1504 and 61-243807; JP-B-43-23684, JP-A-44-6413, JP-A-44- Diazonium compounds described in US Pat. Nos. 6413, 47-1604 and 3,567,453; US Pat. Nos. 2,848,328, 2,852,379 and 2,940,853 Organic azide compounds described in Japanese Patent Publication No. 36-22062, 37-13109, 38-18015, and 45-9610; o-quinonediazides described in Japanese Patent Publication No. 55-39162 Gazette, JP-A-59-14023 and “Macromolecules”, Vol. 10, p. 1307 ( 1977); azo compounds described in JP-A-59-142205; JP-A-1-54440, European Patent Nos. 109,851, 126,712 and “Journal of Imaging Science (J. Imag. Sci.), Vol. 30, page 174 (1986); (oxo) sulfonium organoboron complexes described in JP-A-5-213861 and JP-A-5-255347; Titanocenes described in JP-A-59-152396 and JP-A-61-151197; “Coordination Chemistry Review”, 84, 85-277 (1988) and JP-A-2- Ruthenium described in 182701 Transition metal complexes containing the following transition metals: 2,4,5-triarylimidazole dimer described in JP-A-3-209477; carbon tetrabromide, organic described in JP-A-59-107344 A halogen compound etc. can be mentioned.
[0119]
Of these, preferred are titanocenes. Specific examples of titanocenes include di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, and di-cyclopentadienyl-Ti-bis-2,3,4. , 5,6-pentafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti-bis -2,4,6-trifluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2, 4-difluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bi -2,3,5,6-tetrafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,4-difluorophen-1-yl, bis (cyclopentadienyl) -bis ( Examples include, but are not limited to, 2,6-difluoro-3- (pyridin-1-yl) phenyl) titanium (IRUGACURE784: manufactured by Ciba Specialty Chemicals).
[0120]
When laser light is used as the light source, it is preferable to add a sensitizing dye to the photosensitive layer.
[0121]
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 Examples include methane, polymethine acridine, coumarin, ketocoumarin, quinacridone, indigo, styryl, pyrylium compound, pyromethene compound, pyrazolotriazole compound, benzothiazole compound, barbituric acid derivative, thiobarbituric acid derivative and the like, and further, European Patent No. 568. , 993, U.S. Pat. Nos. 4,508,811, 5,227,227, JP-A-2001-125255, JP-A-11-271969, etc. It is needed.
[0122]
In the present invention, preferred specific examples of the combination of the photopolymerization initiator and the sensitizing dye include combinations described in JP-A Nos. 2001-125255 and 11-271969.
[0123]
Although content in the photosensitive layer of these polymerization initiators is not specifically limited, 0.1-20 mass parts is preferable with respect to 100 mass parts of compounds which have an ethylenic addition polymeric group based on this invention. The blending 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.
[0124]
(Various additives)
In addition to the components described above, the coating composition for the photopolymerizable photosensitive layer according to the present invention contains an ethylenically unsaturated double bond monomer that can be polymerized during the production or storage of the photosensitive lithographic printing plate material. In order to prevent unnecessary polymerization, it is desirable to add a polymerization inhibitor. Suitable polymerization inhibitors include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol) 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxylamine cerium salt, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5) -Methylbenzyl) -4-methylphenyl acrylate and the like.
[0125]
The addition amount of the polymerization inhibitor is preferably 0.01 to 5% with respect to the mass of the total solid content of the composition. If necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to prevent polymerization inhibition by oxygen, or it may be unevenly distributed on the surface of the photosensitive layer in the drying process after coating. . The amount of the higher fatty acid derivative added is preferably 0.5% to 10% of the total composition.
[0126]
Moreover, a coloring agent can also be used and a conventionally well-known thing can be used conveniently as a coloring agent including a commercially available thing. Examples include those described in the revised new edition “Pigment Handbook”, edited by Japan Pigment Technology Association (Seikodo Shinkosha), Color Index Handbook, and the like.
[0127]
Examples of the pigment include black pigment, yellow pigment, red pigment, brown pigment, purple pigment, blue pigment, green pigment, fluorescent pigment, and metal powder pigment. Specifically, inorganic pigments (titanium dioxide, carbon black, graphite, zinc oxide, Prussian blue, cadmium sulfide, iron oxide, and lead, zinc, barium and calcium chromates) and organic pigments (azo-based, thioindigo) , Anthraquinone, anthanthrone, and triphendioxazine pigments, vat dye pigments, phthalocyanine pigments and derivatives thereof, quinacridone pigments, and the like.
[0128]
Among these, it is preferable to select and use a pigment having substantially no absorption in the absorption wavelength region of the spectral sensitizing dye corresponding to the exposure laser to be used. In this case, an integrating sphere at the laser wavelength to be used is used. It is preferable that the reflection absorption of the used pigment is 0.05 or less. Moreover, as addition amount of a pigment, 0.1-10 mass% is preferable with respect to solid content of the said composition, More preferably, it is 0.2-5 mass%.
[0129]
When an argon laser (488 nm) or SHG-YAG laser (532 nm) is used as an exposure light source, purple pigments and blue pigments are used from the viewpoints of pigment absorption in the photosensitive wavelength region and visible image properties after development. It is preferable to use it. For example, cobalt blue, cerulean blue, alkaline blue lake, phonatone blue 6G, Victoria blue lake, metal-free phthalocyanine blue, phthalocyanine blue first sky blue, indanthrene blue, indico, dioxane violet, iso Violanthrone Violet, Indanthrone Blue, Indanthrone BC and the like can be mentioned. Among these, phthalocyanine blue and dioxane violet are more preferable.
[0130]
Moreover, the said composition can contain surfactant as a coating property improving agent in the range which does not impair the performance of this invention. Of these, fluorine-based surfactants are preferred.
[0131]
Moreover, in order to improve the physical properties of the cured film, additives such as inorganic fillers and plasticizers such as dioctyl phthalate, dimethyl phthalate and tricresyl phosphate may be added. These addition amounts are preferably 10% or less of the total solid content.
[0132]
(Application)
Examples of the solvent used when preparing a coating composition such as a photosensitive layer and an intermediate layer according to the present invention include, for example, alcohol: polyhydric alcohol derivatives, sec-butanol, isobutanol, n-hexanol, benzyl alcohol. , Diethylene glycol, triethylene glycol, tetraethylene glycol, 1,5-pentanediol, ethers: propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, ketones, aldehydes: diacetone alcohol, Preferred examples include cyclohexanone, methylcyclohexanone, and esters: ethyl lactate, butyl lactate, diethyl oxalate, methyl benzoate and the like.
[0133]
The prepared coating composition (layer coating solution) can be coated on a support by a conventionally known method and dried to prepare a photosensitive lithographic printing plate material. Examples of coating methods for the coating liquid include an air doctor coater method, a blade coater method, a wire bar method, a knife coater method, a dip coater method, a reverse roll coater method, a gravure coater method, a cast coating method, a curtain coater method, and an extrusion coater method. Can be mentioned.
[0134]
If the drying temperature of the photosensitive layer is low, sufficient printing durability cannot be obtained. If the drying temperature is too high, not only marangoni is produced but also fogging of non-image areas occurs. The preferable drying temperature range is preferably 60 to 160 ° C, more preferably 80 to 140 ° C, and particularly preferably 90 to 120 ° C.
[0135]
(Overcoat layer)
An overcoat layer (also referred to as a protective layer or an oxygen blocking layer) is preferably provided on the upper side of the photosensitive layer according to the present invention. The layer preferably has high solubility in a developing solution (generally an alkaline aqueous solution) described later.
[0136]
Preferred examples of the material constituting the protective layer include polyvinyl alcohol, polysaccharide, polyvinyl pyrrolidone, polyethylene glycol, gelatin, glue, casein, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, hydroxyethyl starch, gum arabic, sucrose octaacetate, and alginic acid. Examples include ammonium, sodium alginate, polyvinylamine, polyethylene oxide, polystyrene sulfonic acid, polyacrylic acid, and water-soluble polyamide. These compounds can be used alone or in combination of two or more as a coating composition. A particularly preferred compound is polyvinyl alcohol.
[0137]
In order to prepare the protective layer coating composition, the above-mentioned material can be dissolved in a suitable solvent to form a coating solution, which is coated on the photopolymerizable photosensitive layer according to the present invention and dried. Thus, a protective layer can be formed. The thickness of the protective layer is preferably from 0.1 to 5.0 [mu] m, particularly preferably from 0.5 to 3.0 [mu] m, as the photosensitive lithographic printing plate material. The protective layer can further contain a surfactant, a matting agent and the like as required.
[0138]
As the method for applying the protective layer, the known methods listed in the above examples can be preferably used. The drying temperature of the protective layer is more preferably lower than the drying temperature of the photosensitive layer. Preferably, the difference from the photosensitive layer drying temperature is 10 ° C. or more, more preferably 20 ° C. or more, and the upper limit in that case is preferably about 50 ° C. at most.
[0139]
Moreover, it is preferable that the drying temperature of a protective layer is lower than the glass transition temperature (Tg) of the binder which a photosensitive layer contains. The difference between the drying temperature of the protective layer and the glass transition temperature (Tg) of the binder contained in the photosensitive layer is preferably 20 ° C. or more, more preferably 40 ° C. or more, and the upper limit of the difference is at most about 60 ° C. Is preferred.
[0140]
(Production method)
The photosensitive lithographic printing plate material according to the present invention is preferably produced by the following production method. That is, a photopolymerizable layer containing the above-described compound having an ethylenic addition polymerizable group and a compound capable of generating radicals by actinic rays is coated and formed on the roughened metal support as described above. In addition, a production method having the following steps a to d is more preferred.
a) Electrochemical roughening of the metal support in an acidic medium
b) The surface of the metal support is provided with (1): A) PVPA and B) an aqueous solvent containing a compound having an amino group, (2): (1) and C) a compound having an ethylenic addition polymerizable group. A water-based solvent containing water and (3): an aqueous solvent containing a reaction product obtained by reacting PVPA with an amino group-containing compound, a step of treating with at least one of the above
c) A step of providing a photopolymerizable layer comprising a compound having an ethylenic addition polymerizable group and a compound that generates radicals by actinic rays.
d) Step of providing an overcoat layer
In addition, it is preferable that the plurality of steps further include a step of mechanically roughening the metal support, and before the step b), the step is performed with an aqueous solvent containing PVPA. It is preferable in this invention to have a process.
[0141]
(Image forming method)
Examples of the light source for image exposure on the photosensitive lithographic printing plate material of the present invention include a laser, a light emitting diode, a xenon flash lamp, a halogen lamp, a carbon arc lamp, a metal halide lamp, a tungsten lamp, a high pressure mercury lamp, and an electrodeless light source. be able to. A xenon lamp, a halogen lamp, a carbon arc lamp, a metal halide lamp, a tungsten lamp, a high-pressure mercury lamp, an electrodeless light source and the like can be preferably used.
[0142]
In the case of batch exposure, a mask material in which a pattern of a desired exposure image is formed of a light-shielding material is superimposed on the photosensitive lithographic printing plate material, and the entire surface may be exposed.
[0143]
When using an array-type light source such as a light-emitting diode array, or when controlling exposure of a light source such as a halogen lamp, metal halide lamp, or tungsten lamp with an optical shutter material such as liquid crystal or PLZT, digital Exposure is possible and preferable. In this case, direct writing can be performed without using a mask material.
[0144]
Laser exposure is suitable for direct writing without using a mask material because light exposure can be performed in the form of a beam according to image data. When a laser is used as a light source, it is easy to reduce the exposure area to a very small size, and high-resolution image formation is possible.
[0145]
As the laser light source, an argon laser, a He—Ne gas laser, a YAG laser, a semiconductor laser, or the like can be preferably used. Laser scanning methods include cylindrical outer surface scanning, cylindrical inner surface scanning, and planar scanning. In the cylindrical outer surface scanning, laser exposure is performed while rotating a drum around which the recording material is wound, and the rotation of the drum is the main scanning and the movement of the laser light is the sub scanning. In cylindrical inner surface scanning, a recording material is fixed to the inner surface of the drum, a laser beam is irradiated from the inside, and a main scanning is performed in the circumferential direction by rotating a part or all of the optical system. Sub scanning is performed in the axial direction by linearly moving all of them in parallel with the drum axis. In plane scanning, a laser beam main scan is performed by combining a polygon mirror, a galvanometer mirror, and an fθ lens, and a sub-scan is performed by moving a recording medium. Cylindrical outer surface scanning and cylindrical inner surface scanning are easier to increase the accuracy of the optical system and are suitable for high-density recording.
[0146]
(Developer)
The exposed portion of the photopolymerizable photosensitive layer subjected to image exposure is cured. By developing this with an alkaline developer, the unexposed areas are removed and image formation becomes possible. As such a developer, a conventionally known alkaline aqueous solution can be used. For example, sodium silicate, potassium, ammonium; dibasic sodium phosphate, potassium, ammonium; sodium bicarbonate, potassium, ammonium; sodium carbonate, potassium, ammonium; sodium bicarbonate, potassium, ammonium An alkali developer using an inorganic alkaline agent such as sodium borate, potassium, ammonium; sodium hydroxide, potassium, ammonium and lithium;
[0147]
Also, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, mono-i-propylamine, di-i-propylamine, tri-i-propylamine, butylamine, monoethanolamine, diethanolamine, triethanolamine, Organic alkali agents such as mono-i-propanolamine, di-i-propanolamine, ethyleneimine, ethylenediamine, and pyridine can also be used.
[0148]
These alkali agents are used alone or in combination of two or more. In addition, an organic solvent such as an anionic surfactant, an amphoteric surfactant or alcohol can be added to the developer as necessary.
[0149]
In the development according to the present invention, the development is preferably performed with a developer containing alkali silicate and having a pH of less than 12.5, and more preferably in the range of pH 10.5 to 12.4.
[0150]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these. In the examples, “parts” represents “parts by mass” unless otherwise specified.
[0151]
Example 1
(Binder synthesis)
A three-necked flask under a nitrogen stream is charged with 12 parts of methacrylic acid, 70 parts of methyl methacrylate, 8 parts of acrylonitrile, 10 parts of ethyl methacrylate, 500 parts of ethanol and 3 parts of α, α'-azobisisobutyronitrile. The reaction was carried out in an air stream at 80 ° C. for 6 hours. Thereafter, 3 parts of triethylammonium chloride and 2 parts of glycidyl methacrylate were added and reacted for 3 hours to obtain an acrylic copolymer 1. The mass average molecular weight measured using GPC (gel permeation chromatography) was about 50,000, and the glass transition temperature (Tg) measured using DSC (differential thermal analysis) was about 85 ° C.
[0152]
(Preparation of support 1)
An aluminum plate (material 1050, tempered H16) having a thickness of 0.24 mm was immersed in a 5% aqueous sodium hydroxide solution maintained at 65 ° C., degreased for 1 minute, and then washed with water. This degreased aluminum plate was neutralized by dipping in a 10% aqueous hydrochloric acid solution maintained at 25 ° C. for 1 minute, and then washed with water. Next, 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. ² Electrolytic surface roughening was performed for 60 seconds with an alternating current under the above conditions, followed by desmutting treatment for 10 seconds in a 5% aqueous sodium hydroxide solution maintained at 60 ° C. The surface-roughened aluminum plate subjected to the desmut treatment was subjected to a current density of 10 A / dm at 25 ° C. in a 15% sulfuric acid solution. ² Anodizing was performed for 1 minute under the condition of a voltage of 15V. At this time, the center line average roughness (Ra) of the surface was 0.65 μm.
[0153]
After performing the said process, it immersed in the following aqueous solution and conditions, and processed.

An aluminum plate was passed through the solution for 30 seconds and dried.
[0154]
[Chemical 6]

[0155]
(Preparation of photosensitive lithographic printing plate material)
On the support, a photopolymerizable photosensitive layer coating solution having the following composition was dried at 1.4 g / m. ² Then, it was applied with a wire bar and dried at 95 ° C. for 1.5 minutes. Thereafter, an overcoat layer coating solution having the following composition was further dried on the photosensitive layer at a drying rate of 2.0 g / m 2. ² Then, it was applied with an applicator and dried at 75 ° C. for 1.5 minutes to prepare a lithographic printing plate material having an overcoat layer on the photosensitive layer.
[0156]

[0157]
[Chemical 7]

[0158]
(Image formation)
About the photosensitive lithographic printing plate material produced as described above, 2540 dpi (dpi represents the number of dots per 2.54 cm) using a CTP exposure apparatus (Tigercat: manufactured by ECRM) equipped with an FD-YAG laser light source. ) Image exposure was performed. Next, a pre-washing part for removing the overcoat layer before development, a developing part filled with a developer having the following composition, a washing part for removing the developer adhering to the plate surface, and a gum solution (GW-3) for protecting the image area : Pre-heated (100 ° C. for 10 seconds) / development with a CTP automatic developing machine (PHW32-V: manufactured by Technigraph) equipped with Mitsubishi Chemical Co., Ltd. diluted twice to obtain a lithographic printing plate.
[0159]

(Evaluation of planographic printing plate)
The lithographic printing plate obtained as described above was evaluated as follows and the results are shown in Table 1. In addition, it carried out similarly about Example 2 or less, and the result was shown in Table 2.
[0160]
"sensitivity"
No reduction in film thickness was observed in the image area, and a halftone dot exposure area of 175 lines and 50% was drawn with a light amount twice that of the exposure amount that could be reproduced to 50% on the prepared lithographic printing plate surface. .
[0161]
<Press life>
A lithographic printing plate produced by exposing and developing a 175-line image with an appropriate exposure amount is coated paper, printing ink (Toyo Ink Co., Ltd. Toyo King Co., Ltd.) using a printing machine (DAIYA1F-1 manufactured by Mitsubishi Heavy Industries, Ltd.). High Echo M Red) and dampening water (Tokyo Ink Co., Ltd. H liquid SG-51 concentration 1.5%), printing 1000 sheets continuously, wipe the plate with a cleaner, The number of printed sheets in which the dot thinning and the entanglement of the shadow part occurred was used as an index of printing durability. One printing durability refers to the operation of wiping with a cleaner after printing 1000 sheets continuously. The greater the number, the better the printing durability.
[0162]
《Soil recovery》
After 1000 sheets of continuous printing, the paper was wiped with a cleaner, and printing was resumed 15 minutes later. The smaller the value, the better.
[0163]
《90% net reproduction》
Draw dots with linearity uncorrected with the laser drawing power above, and take a dot area that should be reproduced at 90% with a 500x optical microscope to calculate the area of the image area in the range of 2 mm x 2 mm. The percentage is shown as%.
[0164]
[Table 1]

[0165]
As described above, the photosensitive lithographic printing plate material of the present invention is excellent in performance of sensitivity, printing durability, stain recovery, and linearity, and when used in combination with a compound having an ethylenic addition polymerizable group and an amino group and It can be seen that in the case of a compound having an ethylenic addition polymerizable group, more preferable performance is exhibited.
[0166]
Example 2
The following PVPA and dimethylaminoethyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light Ester DM) were adjusted by changing the addition ratio to prepare a modified PVPA. The addition rate of light ester to the PVPA repeating unit was the amount shown in Table 2.
[0167]
<Solution temperature> 80 ° C
Vinyl phosphonic acid 0.2 parts by mass
PVPA 1.5 parts by mass
Dimethylaminoethyl methacrylate Concentrations shown in Table 2
Diluent solvent 100 parts by mass (type shown in Table 2)
An aluminum plate was passed through the solution for 30 seconds and dried.
[0168]
In addition to the above evaluation, the following evaluation was performed.
≪Solubility≫
The solubility% of the obtained modified solvent for the above-mentioned modified product (solvent described in Table 2. MEK represents methyl ethyl ketone) was confirmed under 25 ° C. environmental stirring.
[0169]
≪Addition rate≫
It calculated by ratio of the acid value of PVPA homopolymer and the acid value of PVPA ester.
[0170]
[Table 2]

[0171]
From the above results, all show preferable performance, but it can be seen that when the addition rate is 50 mol% or less, the stain is recovered and the performance of linearity is excellent.
[0172]
Example 3
(Preparation of support 2)
An aluminum plate (material 1050, tempered H16) having a thickness of 0.24 mm was immersed in a 5% aqueous sodium hydroxide solution maintained at 65 ° C., degreased for 1 minute, and then washed with water. Using this degreased aluminum plate as a polishing medium, a slurry having a solid content of 15% made of fine grade alumina (average particle size ˜5 microns) and fine grade quartz (˜5 microns) (alumina to quartz 70:30 heavy ratio) is used. The surface is mechanically roughened by brushing with a single 54.8 cm diameter brush rotating at 250 rpm in the direction opposite to the web direction, and then immersed in a 10% hydrochloric acid aqueous solution maintained at 25 ° C. for 1 minute. And neutralized, 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. ² Electrolytic surface roughening was performed for 60 seconds with an alternating current under the above conditions, followed by desmutting treatment for 10 seconds in a 5% aqueous sodium hydroxide solution maintained at 60 ° C. The surface-roughened aluminum plate subjected to the desmut treatment was subjected to a current density of 10 A / dm at 25 ° C. in a 15% sulfuric acid solution. ² Anodizing was performed for 1 minute under the condition of a voltage of 15V. At this time, the center line average roughness (Ra) of the surface was 0.75 μm. About the support body 2 obtained in this way and said support body 1, PVPA process was performed. As the PVPA treatment, the following treatment (PVPA treatment 1 or 2) was performed.
[0173]
<Solution temperature> 80 ° C
<PVPA treatment 1>
Vinyl phosphonic acid 0.2 parts by mass
PVPA 1.5 parts by mass
100 parts by mass of ion-exchanged water
<PVPA treatment 2>
Vinyl phosphonic acid 0.2 parts by mass
PVPA 1.5 parts by mass
Dimethylaminoethyl methacrylate 0.5 parts by mass
100 parts by mass of ion-exchanged water
The support was immersed in the solution for 20 seconds and dried.
[0174]
In Example 3, as Samples 1 to 3, the above-described supports 1 and 2 and PVPA treatments 1 and 2 were subjected to the following combinations of treatments. In addition, about the photosensitive layer and the overcoat layer, it carried out similarly to Example 1, and produced the photosensitive lithographic printing plate material.
[0175]
Sample 1: PVPA treatment 2 is applied to the support 1.
Sample 2: PVPA treatment 2 is applied to the support 2.
[0176]
Sample 3: PVPA treatments 1 and 2 are applied to the support 2.
Evaluation was performed in the same manner as in Example 1, and the results are shown in Table 3.
[0177]
[Table 3]

[0178]
According to the production method of the present invention, good performance can be obtained, but high printing durability can be obtained particularly on a support subjected to mechanical surface roughening and electrochemical surface roughening. Further, it can be seen that by using PVPA treatments 1 and 2 in combination, a preferable stain recovery performance can be obtained.
[0179]
【The invention's effect】
The present invention is excellent in adhesiveness between the photopolymerization layer and the support, can achieve both printing durability and improvement in stains in non-image areas, and further obtains a lithographic printing plate having high resolution and good storage stability. It was possible to provide a support for a photosensitive lithographic printing plate material, a photosensitive lithographic printing plate material, and a method for producing the same.

Claims (10)

A roughened metal support, characterized in that it is treated with an aqueous solvent containing at least A) a compound containing polyvinylphosphonic acid and B) a primary or secondary amino group. Photosensitive lithographic printing plate material support.   2. The photosensitive lithographic printing plate material support according to claim 1, wherein the aqueous solvent further contains a compound having C) an ethylenic addition polymerizable group.   2. The photosensitive lithographic printing plate material support according to claim 1, wherein the compound having an amino group is D) a compound having an amino group and an ethylenic addition polymerizable group.   Photosensitive lithographic printing comprising a roughened metal support and treated with an aqueous solvent containing at least a reaction product obtained by reacting polyvinyl phosphonic acid with a compound having an amino group Plate material support.   The support for a photosensitive lithographic printing plate material according to claim 4, wherein the addition ratio of the compound having an amino group to the repeating unit of the polyvinyl phosphonic acid is 0.01 to 50 mol%. A photosensitive lithographic printing plate material having a photopolymerizable layer containing a compound having an ethylenic addition polymerizable group and a compound capable of generating radicals by actinic light on a roughened metal support, the metal The support has 1) : A) polyvinyl phosphonic acid and B) an aqueous solvent containing a compound having a primary or secondary amino group, 2) : 1) and further C) an ethylenic addition polymerizable group. An aqueous solvent containing a compound and 3) : a photosensitive lithographic plate treated with at least one selected from an aqueous solvent containing a reaction product obtained by reacting a compound having polyvinyl phosphonic acid and an amino group Printing plate material.   The reaction product obtained by the reaction between the polyvinyl phosphonic acid and the compound having an amino group is in the range of 0.01 to 50 mol% as the addition ratio of the compound having an amino group to the repeating unit of the polyvinyl phosphonic acid. The photosensitive lithographic printing plate material according to claim 6, which is characterized by: A method for producing a photosensitive lithographic printing plate material comprising a photopolymerizable layer containing a compound having an ethylenic addition polymerizable group and a compound capable of generating radicals by actinic rays on a roughened metal support. A process for producing a photosensitive lithographic printing plate material comprising the following steps a to d:
a) Step of electrochemically roughening a metal support in an acidic medium b) The surface of the metal support has 1) : A) polyvinyl phosphonic acid and B) a primary or secondary amino group An aqueous solvent containing a compound, 2) : 1) a further aqueous solvent containing a compound having an ethylenic addition-polymerizable group, and 3) a reaction product obtained by reacting polyvinyl phosphonic acid with a compound having an amino group Step c) of treating with at least one of the above-mentioned aqueous solvents containing ethylenic compound and step d) of providing a photopolymerizable layer comprising a compound having an ethylenic addition polymerizable group and a compound capable of generating radicals by actinic rays Step of providing an overcoat layer   9. The method for producing a photosensitive lithographic printing plate material according to claim 8, wherein the steps a to d further include a step of mechanically roughening the metal support.   9. The method for producing a photosensitive lithographic printing plate material according to claim 8, further comprising a step of treating with an aqueous solvent containing polyvinyl phosphonic acid before the step b).