JP4108255B2 - Planographic printing plate manufacturing method - Google Patents

Description

【００３４】
式中、Ａは２価の連結基を表す。Ｂは芳香族基あるいは置換芳香族基を表す。Ｄ及びＥはそれぞれ独立して２価の連結基を表す。Ｇは３価の連結基を表す。Ｘ及びＸ'はそれぞれ独立してｐＫａが７以下の酸基あるいはそのアルカリ金属塩あるいはアンモニウム塩を表す。Ｒは水素原子、アルキル基またはハロゲン原子を表す。ａ、ｂ、ｄ、ｅはそれぞれ独立して０または１を表す。ｔは１〜３の整数である。
【００３５】
酸基を有する構成成分の中でより好ましくは、Ａは−ＣＯＯ−または−ＣＯＮＨ−を表し、Ｂはフェニレン基あるいは置換フェニレン基を表し、その置換基は水酸基、ハロゲン原子あるいはアルキル基である。Ｄ及びＥはそれぞれ独立してアルキレン基あるいは分子式がＣ_nＨ_2nＯ、Ｃ_nＨ_2nＳあるいはＣ_nＨ_2n+1Ｎで表される２価の連結基を表す。Ｇは分子式がＣ_nＨ_2n-1、Ｃ_nＨ_2n-1Ｏ、Ｃ_nＨ_2n-1ＳあるいはＣ_nＨ_2nＮで表される３価の連結基を表す。ただし、ここでｎは１〜１２の整数を表す。Ｘ及びＸ'はそれぞれ独立してカルボン酸、スルホン酸、ホスホン酸、硫酸モノエステルあるいは燐酸モノエステルを表す。Ｒは水素原子またはアルキル基を表す。ａ、ｂ、ｄ、ｅはそれぞれ独立して０または１を表すが、ａとｂは同時に０ではない。
【００３６】
酸基を有する構成成分の中で特に好ましくは一般式（１）で示す化合物であり、Ｂはフェニレン基あるいは置換フェニレン基を表し、その置換基は水酸基あるいは炭素数１〜３のアルキル基である。Ｄ及びＥはそれぞれ独立して炭素数１〜２のアルキレン基あるいは酸素原子で連結した炭素数１〜２のアルキレン基を表す。Ｒは水素原子あるいはメチル基を表す。Ｘはカルボン酸基を表す。ａは０であり、ｂは１である。
【００３７】
酸基を有する構成成分の具体例を以下に示す。ただし、本発明はこの具体例に限定されるものではない。アクリル酸、メタクリル酸、クロトン酸、イソクロトン酸、イタコン酸、マレイン酸、無水マレイン酸等が挙げられ、さらに下記のものが挙げられる。
【００３８】
【化２】

【００３９】
【化３】

【００４０】
【化４】

【００４１】
上記のような酸基を有する構成成分は、１種類あるいは２種類以上組み合わせてもよい。
また、上記中間層形成に用いられる高分子化合物の構成成分のオニウム基として好ましいものは、周期律表第Ｖ族あるいは第VI族の原子からなるオニウム基であり、より好ましくは窒素原子、リン原子あるいはイオウ原子からなるオニウム基であり、特に好ましくは窒素原子からなるオニウム基である。また、この高分子化合物は、その主鎖構造がアクリル樹脂やメタクリル樹脂やポリスチレンのようなビニル系ポリマーあるいはウレタン樹脂あるいはポリエステルあるいはポリアミドであるポリマーが好ましい。中でも、主鎖構造がアクリル樹脂やメタクリル樹脂やポリスチレンのようなビニル系ポリマーがさらに好ましい。特に好ましい高分子化合物は、オニウム基を有する構成成分が下記の一般式（３）、一般式（４）あるいは一般式（５）で表される重合可能な化合物であるポリマーである。
【００４２】
【化５】

【００４３】
式中、Ｊは２価の連結基を表す。Ｋは芳香族基あるいは置換芳香族基を表す。Ｍはそれぞれ独立して２価の連結基を表す。Ｙは周期律表第Ｖ族の原子を表し、Ｙ'は周期律表第VI族の原子を表す。Ｚ^-は対アニオンを表す。Ｒ'は水素原子、アルキル基またはハロゲン原子を表す。Ｒ'₁、Ｒ'₂、Ｒ'₃、Ｒ'₅はそれぞれ独立して水素原子あるいは場合によっては置換基が結合してもよいアルキル基、芳香族基、アラルキル基を表し、Ｒ'₄はアルキリジン基あるいは置換アルキリジンを表すが、Ｒ'₁とＲ'₂あるいはＲ'₄とＲ'₅はそれぞれ結合して環を形成してもよい。ｊ、ｋ、ｍはそれぞれ独立して０または１を表す。ｕは１〜３の整数を表す。
【００４４】
オニウム基を有する構成成分の中でより好ましくは、Ｊは−ＣＯＯ−または−ＣＯＮＨ−を表し、Ｋはフェニレン基あるいは置換フェニレン基を表し、その置換基は水酸基、ハロゲン原子あるいはアルキル基である。Ｍはアルキレン基あるいは分子式がＣ_nＨ_2nＯ、Ｃ_nＨ_2nＳあるいはＣ_nＨ_2n+1Ｎで表される２価の連結基を表す。ただし、ここでｎは１〜１２の整数を表す。Ｙは窒素原子またはリン原子を表し、Ｙ'はイオウ原子を表す。Ｚ^-はハロゲンイオン、ＰＦ₆ ^-、ＢＦ₄ ^-あるいはＲ'₆ＳＯ₃ ^-を表す。Ｒ'₆は水素原子またはアルキル基を表す。Ｒ'₁、Ｒ'₂、Ｒ'₃、Ｒ'₅はそれぞれ独立して水素原子あるいは場合によっては置換基が結合してもよい炭素数１〜１０のアルキル基、芳香族基、アラルキル基を表し、Ｒ'₄は炭素数１〜１０のアルキリジン基あるいは置換アルキリジンを表すが、Ｒ'₁とＲ'₂あるいはＲ'₄とＲ'₅はそれぞれ結合して環を形成してもよい。ｊ、ｋ、ｍはそれぞれ独立して０または１を表すが、ｊとｋは同時に０ではない。
【００４５】
オニウム基を有する構成成分の中で特に好ましくは、Ｋはフェニレン基あるいは置換フェニレン基を表し、その置換基は水酸基あるいは炭素数１〜３のアルキル基である。Ｍは炭素数１〜２のアルキレン基あるいは酸素原子で連結した炭素数１〜２のアルキレン基を表す。Ｚ^-は塩素イオンあるいはＲ'₆ＳＯ₃ ^-を表す。Ｒ'₆は水素原子あるいはメチル基を表す。ｊは０であり、ｋは１である。
【００４６】
オニウム基を有する構成成分の具体例を以下に示す。ただし、本発明はこの具体例に限定されるものではない。
【００４７】
【化６】

【００４８】
【化７】

【００４９】
中間層形成に用いる高分子化合物には、上記のようなオニウム基を有する構成成分を１モル％以上、好ましくは５モル％以上含むことが望ましい。オニウム基を有する構成成分が１モル％以上含まれると密着性が一層向上される。また、オニウム基を有する構成成分は１種類あるいは２種類以上組み合わせてもよい。さらに、中間層形成に用いる高分子化合物は、構成成分あるいは組成比あるいは分子量の異なるものを２種類以上混合して用いてもよい。
【００５０】
また、この酸基と共にオニウム基をも有する高分子化合物においては、酸基を有する構成成分を２０モル％以上、好ましくは４０モル％以上含み、オニウム基を有する構成成分を１モル％以上、好ましくは５モル％以上含むことが望ましい。酸基を有する構成成分が２０モル％以上含まれると、アルカリ現像時の溶解除去が一層促進され、また酸基とオニウム基との相乗効果により密着性がなお一層向上される。また、このオニウム基と共に酸基をも有する高分子化合物においても、構成成分あるいは組成比あるいは分子量の異なるものを２種類以上混合して用いてもよいことはいうまでもない。以下に、上記のオニウム基と共に酸基をも有する高分子化合物の代表的な例を示す。なお、ポリマー構造の組成比はモル百分率を表す。
【００５１】
【化８】

【００５２】
【化９】

【００５３】
【化１０】

【００５４】
【化１１】

【００５５】
上記のような中間層形成に用いる、酸基を有するあるいは酸基と共にオニウム基をも有する高分子化合物のいずれも、一般には、ラジカル連鎖重合法を用いて製造することができる（“Textbook of Polymer Science" 3rd ed,(1984)F.W.Billmeyer,A Wiley-Interscience Publication参照）。また、これらの高分子化合物の分子量は広範囲であってもよいが、光散乱法を用いて測定した時、重量平均分子量（Ｍｗ）が５００〜２,０００,０００であることが好ましく、また２,０００〜６００,０００の範囲であることが更に好ましい。また、この高分子化合物中に含まれる未反応モノマー量は広範囲であってもよいが、２０重量％以下であることが好ましく、また１０重量％以下であることがさらにに好ましい。また、酸基と共にオニウム基をも有する高分子化合物の代表的な例の一つとして上記したｐ−ビニル安息香酸とビニルベンジルトリメチルアンモニウムクロリドとの共重合体（表１のＮｏ.１）を例にとって、その合成例を示せば次のとおりである。ｐ−ビニル安息香酸［北興化学工業（株）製］１４６.９ｇ（０.９９ｍｏｌ）、ビニルベンジルトリメチルアンモニウムクロリド４４.２ｇ（０.２１ｍｏｌ）および２−メトキシエタノール４４６ｇを１Ｌの３口フラスコに取り、窒素気流下攪拌しながら、加熱し７５℃に保った。次に２,２−アゾビス（イソ酪酸）ジメチル２.７６ｇ（１２ｍｍｏｌ）を加え、攪拌を続けた。２時間後、２,２−アゾビス（イソ酪酸）ジメチル２.７６ｇ（１２ｍｍｏｌ）を追加した。更に、２時間後、２,２−アゾビス（イソ酪酸）ジメチル２.７６ｇ（１２ｍｍｏｌ）を追加した。２時間攪拌した後、室温まで放冷した。この反応液を攪拌下１２Ｌの酢酸エチル中に注いだ。析出する固体を濾取し、乾燥した。その収量は１８９.５ｇであった。得られた固体は光散乱法で分子量測定を行った結果、重量平均分子量（Ｍｗ）は３.２万であった。他の高分子化合物も同様の方法で合成できる。
【００５６】
酸基とオニウム基を有する中間層は、上記した酸基を有するあるいは酸基と共にオニウム基をも有する高分子化合物（以下単に「高分子化合物」という）を、上述した亜硝酸または亜硝酸塩を含む水溶液で処理し、さらに任意に親水化処理したアルミニウム支持体の上に種々の方法により塗布して設けられる。中間層を設けるために一般的に採用される方法の一つは、メタノール、エタノール、メチルエチルケトンなどの有機溶剤もしくはそれらの混合溶剤あるいはこれら有機溶剤と水との混合溶剤に高分子化合物を溶解させた溶液をアルミニウム支持体上に塗布し、乾燥して設ける方法であり、他の一つは、メタノール、エタノール、メチルエチルケトンなどの有機溶剤もしくはそれらの混合溶剤あるいはこれら有機溶剤と水との混合溶剤に高分子化合物を溶解させた溶液に、アルミニウム支持体を浸漬して高分子化合物を吸着させ、しかる後、水などによって洗浄し、乾燥して設ける方法である。前者の方法では、高分子化合物の０.００５〜１０重量％の濃度の溶液を種々の方法で塗布できる。例えば、バーコーター塗布、回転塗布、スプレー塗布、カーテン塗布などいずれの方法を用いてもよい。また、後者の方法では、溶液の濃度は０.０１〜２０重量％、好ましくは０.０５〜５重量％であり、浸漬温度は２０〜９０℃、好ましくは２５〜５０℃であり、浸漬時間は０.１秒〜２０分、好ましくは２秒〜１分である。
【００５７】
上記の高分子化合物の溶液は、アンモニア、トリエチルアミン、水酸化カリウムなどの塩基性物質や、塩酸、リン酸、硫酸、硝酸などの無機酸、ニトロベンゼンスルホン酸、ナフタレンスルホン酸などの有機スルホン酸、フェニルホスホン酸などの有機ホスホン酸、安息香酸、クマル酸、リンゴ酸などの有機カルボン酸など種々の有機酸性物質、ナフタレンスルホニルクロライド、ベンゼンスルホニルクロライドなどの有機酸クロライド等によりｐＨを調整し、ｐＨ＝０〜１２、より好ましくはｐＨ＝０〜５、の範囲で使用することもできる。また、感光性平版印刷版の調子再現性改良のために黄色染料を添加することもできる。高分子化合物の乾燥後の被覆量は、２〜１００ｍｇ／ｍ²が適当であり、好ましくは５〜５０ｍｇ／ｍ²である。上記被覆量が２ｍｇ／ｍ²よりも少ないと、十分な効果が得られない。また、１００ｍｇ／ｍ²より多くても同様である。
【００５８】
その他にも特開平５-５０７７９に示すゾルゲルコーティング処理、特開平５-２４６１７１に示すホスホン酸類のコーティング処理、特開平６-２３４２８４、特開平６-１９１１７３及び特開平６-２３０５６３に記載のバックコート用素材をコーティングにより処理する方法、特開平６-２６２８７２に示すホスホン酸類の処理、特開平６-２９７８７５に示すコーティング処理、特開平１０-１０９４８０に記載の方法で陽極酸化処理する方法、特願平１０-２５２０７８及び特願平１０-２５３４１１に記載の浸漬処理方法等、何れの方法によっても良い。
【００５９】
（ポジ型感光層）
上記の、任意に陽極酸化処理、粗面化処理等され、任意に中間層が設けられた、一定のフッ素化率を有する支持体上に以下のポジ型感光層を設ける。
【００６０】
ポジ型感光層はポジ型感光性組成物を適宜溶媒等に溶解して上記支持体上に塗布等することにより設けられる。このようなポジ型感光性組成物としては、露光前後で現像液に対する溶解性、または膨潤性が変化するものであればいずれでも使用できる。以下、代表的なポジ型感光性組成物について説明するが、これにより本発明は限定されない。
【００６１】
（ポジ型感光性化合物）
ポジ型感光性組成物中の感光性化合物としては、ｏ−キノンジアジド化合物が挙げられ、その代表例としてｏ−ナフトキノンジアジド化合物が挙げられる。ｏ−ナフトキノンジアジド化合物としては、特公昭４３−２８４０３号公報に記載されている１,２−ジアゾナフトキノンスルホン酸クロリドとピロガロール−アセトン樹脂とのエステルであるものが好ましい。
【００６２】
その他の好適なｏ−キノンジアジド化合物としては、米国特許第３,０４６,１２０号および同第３,１８８,２１０号明細書中に記載されている１,２−ジアゾナフトキノンスルホン酸クロリドとフェノールホルムアルデヒド樹脂とのエステルがある。
【００６３】
その他の有用なｏ−ナフトキノンジアジド化合物としては、数多くの特許に報告され、知られているものが挙げられる。例えば、特開昭４７−５３０３号、同４８−６３８０２号、同４８−６３８０３号、同４８−９６５７５号、同４９−３８７０１号、同４８−１３３５４号、特公昭３７−１８０１５号、同４１−１１２２２号、同４５−９６１０号、同４９−１７４８１号、特開平５−１１４４４号、特開平５−１９４７７号、特開平５−１９４７８号、特開平５−１０７７５５号、米国特許第２,７９７,２１３号、同第３,４５４,４００号、同第３,５４４,３２３号、同第３,５７３,９１７号、同第３,６７４,４９５号、同第３,７８５,８２５号、英国特許第１,２２７,６０２号、同第１,２５１,３４５号、同第１,２６７,００５号、同第１,３２９,８８８号、同第１,３３０,９３２号、ドイツ特許第８５４,８９０号等の各公報または明細書中に記載されているものを挙げることができる。
【００６４】
さらにその他のｏ−キノンジアジド化合物としては、分子量１,０００以下のポリヒドロキシ化合物と１,２−ジアゾナフトキノンスルホン酸クロリドとの反応により得られるｏ−ナフトキノンジアジド化合物も使用することができる。例えば特開昭５１−１３９４０２号、同５８−１５０９４８号、同５８−２０３４３４号、同５９−１６５０５３号、同６０−１２１４４５号、同６０−１３４２３５号、同６０−１６３０４３号、同６１−１１８７４４号、同６２−１０６４５号、同６２−１０６４６号、同６２−１５３９５０号、同６２−１７８５６２号、同６４−７６０４７号、米国特許第３,１０２,８０９号、同第３,１２６,２８１号、同第３,１３０,０４７号、同第３,１４８,９８３号、同第３,１８４,３１０号、同第３,１８８,２１０号、同第４,６３９,４０６号等の各公報または明細書に記載されているものを挙げることができる。
【００６５】
これらのｏ−ナフトキノンジアジド化合物を合成する際には、ポリヒドロキシ化合物のヒドロキシル基に対して１,２−ジアゾナフトキノンスルホン酸クロリドを０.２〜１.２当量反応させることが好ましく、０.３〜１.０当量反応させることがさらに好ましい。１,２−ジアゾナフトキノンスルホン酸クロリドとしては、１,２−ジアゾナフトキノン−５−スルホン酸クロリドが好ましいが、１,２−ジアゾナフトキノン−４−スルホン酸クロリドも用いることができる。また得られるｏ−ナフトキノンジアジド化合物は、１,２−ジアゾナフトキノンスルホン酸エステル基の位置および導入量の種々異なるものの混合物となるが、ヒドロキシル基がすべて１,２−ジアゾナフトキノンスルホン酸エステルに転換された化合物がこの混合物中に占める割合（完全にエステル化された化合物の含有率）は５モル％以上であることが好ましく、さらに好ましくは２０〜９９モル％である。
【００６６】
また、ｏ−ナフトキノンジアジド化合物を用いずにポジ型に作用する感光性化合物として、例えば特公昭５２−２６９６号に記載されているｏ−ニトリルカルビノールエステル基を含有するポリマー化合物やピリジニウム基含有化合物（特開平４−３６５０４９号など）、ジアゾニウム基含有化合物（特開平５−２４９６６４号、特開平６−８３０４７号、特開平６−３２４４９５号、特開平７−７２６２１号など）も使用することができる。さらに光分解により酸を発生する化合物と（特開平４−１２１７４８号、特開平４−３６５０４３号など）、酸により解離するＣ−Ｏ−Ｃ基またはＣ−Ｏ−Ｓｉ基を有する化合物との組み合せ系も使用することができる。例えば光分解により酸を発生する化合物とアセタールまたはＯ、Ｎ−アセタール化合物との組み合せ（特開昭４８−８９００３号など）、オルトエステルまたはアミドアセタール化合物との組み合せ（特開昭５１−１２０７１４号など）、主鎖にアセタールまたはケタール基を有するポリマーとの組み合せ（特開昭５３−１３３４２９号など）、エノールエーテル化合物との組み合せ（特開昭５５−１２９９５号、特開平４−１９７４８号、特開平６−２３０５７４号など）、Ｎ−アシルイミノ炭素化合物との組み合せ（特開昭５５−１２６２３６号など）、主鎖にオルトエステル基を有するポリマーとの組み合せ（特開昭５６−１７３４５号など）、シリルエステル基を有するポリマーとの組み合せ（特開昭６０−１０２４７号など）、およびシリルエーテル化合物との組み合せ（特開昭６０−３７５４９号、特開昭６０−１２１４４６号、特開昭６３−２３６０２８号、特開昭６３−２３６０２９号、特開昭６３−２７６０４６号など）等が挙げられる。感光性組成物中に占めるこれらのポジ型に作用する感光性化合物（上記のような組み合せを含む）の量は１０〜５０質量％が適当であり、より好ましくは１５〜４０質量％である。
【００６７】
（結合剤）
ｏ−キノンジアジド化合物は単独でも感光層を構成し得るが、結合剤（バインダー）としてのアルカリ水に可溶な樹脂と共に使用することが好ましい。このようなアルカリ水に可溶性の樹脂としては、この性質を有するノボラック樹脂があり、たとえばフェノールホルムアルデヒド樹脂、ｍ−クレゾールホルムアルデヒド樹脂、ｐ−クレゾールホルムアルデヒド樹脂、ｍ−／ｐ−混合クレゾールホルムアルデヒド樹脂、フェノール／クレゾール（ｍ−、ｐ−、ｏ−またはｍ−／ｐ−／ｏ−混合のいずれでもよい）混合ホルムアルデヒド樹脂などのクレゾールホルムアルデヒド樹脂などが挙げられる。これらのアルカリ性可溶性高分子化合物は、重量平均分子量が５００〜１００,０００のものが好ましい。その他、レゾール型のフェノール樹脂類も好適に用いられ、フェノール／クレゾール（ｍ−、ｐ−、ｏ−またはｍ−／ｐ−／ｏ−混合のいずれでもよい）混合ホルムアルデヒド樹脂が好ましく、特に特開昭６１−２１７０３４号公報に記載されているフェノール樹脂類が好ましい。
【００６８】
また、フェノール変性キシレン樹脂、ポリヒドロキシスチレン、ポリハロゲン化ヒドロキシスチレン、特開昭５１−３４７１１号公報に開示されているようなフェノール性水酸基を含有するアクリル系樹脂、特開平２−８６６号公報に記載のスルホンアミド基を有するビニル樹脂やウレタン樹脂、特開平７−２８２４４号、特開平７−３６１８４号、特開平７−３６１８５号、特開平７−２４８６２８号、特開平７−２６１３９４号、特開平７−３３３８３９号公報などに記載の構造単位を有するビニル樹脂など種々のアルカリ可溶性の高分子化合物を含有させることができる。特にビニル樹脂においては、以下に示す（１）〜（４）のアルカリ可溶性基含有モノマーから選ばれる少なくとも１種を重合成分として有する皮膜形成性樹脂が好ましい。
【００６９】
（１）Ｎ−（４−ヒドロキシフェニル）アクリルアミドまたはＮ−（４−ヒドロキシフェニル）メタクリルアミド、ｏ−、ｍ−またはｐ−ヒドロキシスチレン、ｏ−またはｍ−ブロモ−ｐ−ヒドロキシスチレン、ｏ−またはｍ−クロル−ｐ−ヒドロキシスチレン、ｏ−、ｍ−またはｐ−ヒドロキシフェニルアクリレートまたはメタクリレート等の芳香族水酸基を有するアクリルアミド類、メタクリルアミド類、アクリル酸エステル類、メタクリル酸エステル類およびビドロキシスチレン類、（２）アクリル酸、メタクリル酸、マレイン酸、無水マレイン酸およびそのハーフエステル、イタコン酸、無水イタコン酸およびそのハーフエステルなどの不飽和カルボン酸、
【００７０】
（３）Ｎ−（ｏ−アミノスルホニルフェニル）アクリルアミド、Ｎ−（ｍ−アミノスルホニルフェニル）アクリルアミド、Ｎ−（ｐ−アミノスルホニルフェニル）アクリルアミド、Ｎ−〔１−（３−アミノスルホニル）ナフチル〕アクリルアミド、Ｎ−（２−アミノスルホニルエチル）アクリルアミドなどのアクリルアミド類、Ｎ−（ｏ−アミノスルホニルフェニル）メタクリルアミド、Ｎ−（ｍ−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）メタクリルアミド、Ｎ−〔１−（３−アミノスルホニル）ナフチル〕メタクリルアミド、Ｎ−（２−アミノスルホニルエチル）メタクリルアミドなどのメタクリルアミド類、また、ｏ−アミノスルホニルフェニルアクリレート、ｍ−アミノスルホニルフェニルアクリレート、ｐ−アミノスルホニルフェニルアクリレート、１−（３−アミノスルホニルフェニルナフチル）アクリレートなどのアクリル酸エステル類などの不飽和スルホンアミド、ｏ−アミノスルホニルフェニルメタクリレート、ｍ−アミノスルホニルフェニルメタクリレート、ｐ−アミノスルホニルフェニルメタクリレート、１−（３−アミノスルホニルフェニルナフチル）メタクリレートなどのメタクリル酸エステル類などの不飽和スルホンアミド、（４）トシルアクリルアミドのように置換基があってもよいフェニルスルホニルアクリルアミド、およびトシルメタクリルアミドのような置換基があってもよいフェニルスルホニルメタクリルアミド。
【００７１】
さらに、これらのアルカリ可溶性基含有モノマーの他に以下に記す（５）〜（１４）のモノマーを共重合した皮膜形成性樹脂が好適に用いられる。（５）脂肪族水酸基を有するアクリル酸エステル類およびメタクリル酸エステル類、例えば、２−ヒドロキシエチルアクリレートまたは２−ヒドロキシエチルメタクリレート、（６）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、アクリル酸シクロヘキシル、アクリル酸オクチル、アクリル酸フェニル、アクリル酸ベンジル、アクリル酸−２−クロロエチル、アクリル酸４−ヒドロキシブチル、グリシジルアクリレート、Ｎ−ジメチルアミノエチルアクリレートなどの（置換）アクリル酸エステル、（７）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、メタクリル酸シクロヘキシル、メタクリル酸オクチル、メタクリル酸フェニル、メタクリル酸ベンジル、メタクリル酸−２−クロロエチル、メタクリル酸４−ヒドロキシブチル、グリシジルメタクリレート、Ｎ−ジメチルアミノエチルメタクリレートなどの（置換）メタクリル酸エステル、
【００７２】
（８）アクリルアミド、メタクリルアミド、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、Ｎ−エチルアクリルアミド、Ｎ−エチルメタクリルアミド、Ｎ−ヘキシルアクリルアミド、Ｎ−ヘキシルメタクリルアミド、Ｎ−シクロヘキシルアクリルアミド、Ｎ−シクロヘキシルメタクリルアミド、Ｎ−ヒドロキシエチルアクリルアミド、Ｎ−ヒドロキシエチルアクリルアミド、Ｎ−フェニルアクリルアミド、Ｎ−フェニルメタクリルアミド、Ｎ−ベンジルアクリルアミド、Ｎ−ベンジルメタクリルアミド、Ｎ−ニトロフェニルアクリルアミド、Ｎ−ニトロフェニルメタクリルアミド、Ｎ−エチル−Ｎ−フェニルアクリルアミドおよびＮ−エチル−Ｎ−フェニルメタクリルアミドなどのアクリルアミドもしくはメタクリルアミド、（９）エチルビニルエーテル、２−クロロエチルビニルエーテル、ヒドロキシ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などのビニルエーテル類、
【００７３】
（１０）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、安息香酸ビニルなどのビニルエステル類、（１１）スチレン、α−メチルスチレン、メチルスチレン、クロロメチルスチレンなどのスチレン類、（１２）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などのビニルケトン類、（１３）エチレン、プロピレン、イソブチレン、ブタジエン、イソプレンなどのオレフィン類、（１４）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、アクリロニトリル、メタクリロニトリルなど。
【００７４】
これらのアルカリ可溶性高分子化合物は、重量平均分子量が５００〜５００,０００のものが好ましい。このようなアルカリ可溶性高分子化合物は１種類あるいは２種類以上を組み合せて使用してもよい。また、かかる高分子化合物の感光性組成物中に占める割合は、８０質量％以下が適当であり、好ましくは３０〜８０質量％、より好ましくは５０〜７０質量％である。この範囲であると現像性および耐刷性の点で好ましい。
【００７５】
さらに、米国特許第４,１２３,２７９号明細書に記載されているように、ｔ−ブチルフェノールホルムアルデヒド樹脂、オクチルフェノールホルムアルデヒド樹脂のような、炭素数３〜８のアルキル基を置換基として有するフェノールとホルムアルデヒドとの縮合物あるいはこれらの縮合物のｏ−ナフトキノンジアジドスルホン酸エステル（例えば特開昭６１−２４３４４６号に記載のもの）を併用することは画像の感脂性を向上させる上で好ましい。
【００７６】
（現像促進剤）
感光性組成物中には、感度アップおよび現像性の向上のために環状酸無水物類、フェノール類および有機酸類を添加することが好ましい。環状酸無水物類としては、米国特許４,１１５,１２８号明細書に記載されている無水フタル酸、テトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、３,６−エンドオキシ−Δ4−テトラヒドロ無水フタル酸、テトラクロル無水フタル酸、無水マレイン酸、クロル無水マレイン酸、α−フェニル無水マレイン酸、無水コハク酸、無水ピロメリット酸などが使用できる。フェノール類としては、ビスフェノールＡ、ｐ−ニトロフェノール、ｐ−エトキシフェノール、２,４,４′−トリヒドロキシベンゾフェノン、２,３,４−トリヒドロキシベンゾフェノン、４−ヒドロキシベンゾフェノン、４,４′,４″−トリヒドロキシ−トリフェニルメタン、４,４′,３″,４″−テトラヒドロキシ−３,５,３′,５′−テトラメチルトリフェニルメタンなどが挙げられる。さらに、有機酸類としては、特開昭６０−８８９４２号、特開平２−９６７５５号公報などに記載されている、スルホン酸類、スルフィン酸類、アルキル硫酸類、ホスホン酸類、リン酸エステル類およびカルボン酸類などがあり、具体的には、ｐ−トルエンスルホン酸、ドデシルベンゼンスルホン酸、ｐ−トルエンスルフィン酸、エチル硫酸、フェニルホスホン酸、フェニルホスフィン酸、リン酸フェニル、リン酸ジフェニル、安息香酸、イソフタル酸、アジピン酸、ｐ−トルイル酸、３,４−ジメトキシ安息香酸、フタル酸、テレフタル酸、１,４−シクロヘキセン−２,２−ジカルボン酸、エルカ酸、ラウリン酸、ｎ−ウンデカン酸、アスコルビン酸などが挙げられる。上記の環状酸無水物類、フェノール類および有機酸類の感光性組成物中に占める割合は、０.０５〜１５質量％が好ましく、より好ましくは０.１〜５質量％である。
【００７７】
（現像安定剤）
また、感光性組成物中には、現像条件に対する処理の安定性（いわゆる現像許容性）を広げるため、特開昭６２−２５１７４０号公報や特開平４−６８３５５号公報に記載されているような非イオン界面活性剤、特開昭５９−１２１０４４号公報、特開平４−１３１４９号公報に記載されているような両性界面活性剤を添加することができる。非イオン界面活性剤の具体例としては、ソルビタントリステアレート、ソルビタンモノパルミテート、ソルビタントリオレート、ステアリン酸モノグリセリド、ポリオキシエチレンソルビタンモノオレート、ポリオキシエチレンノニルフェニルエーテルなどが挙げられる。両性界面活性剤の具体例としては、アルキルジ（アミノエチル）グリシン、アルキルポリアミノエチルグリシン塩酸塩、２−アルキル−Ｎ−カルボキシエチル−Ｎ−ヒドロキシエチルイミダゾリニウムベタインやＮ−テトラデシル−Ｎ,Ｎ−ベタイン型（例えば、商品名アモーゲンＫ、第一工業（株）製）およびアルキルイミダゾリン系（例えば、商品名レボン１５、三洋化成（株）製）などが挙げられる。上記非イオン界面活性剤および両性界面活性剤の感光性組成物中に占める割合は、０.０５〜１５質量％が好ましく、より好ましくは０.１〜５質量％である。
【００７８】
（焼き出し剤、染料、その他）
感光性組成物中には、露光後直ちに可視像を得るための焼出し剤、画像着色剤としての染料やその他のフィラーなどを加えることができる。染料としては、特開平５−３１３３５９号公報に記載の塩基性染料骨格を有するカチオンと、スルホン酸基を唯一の交換基として有し、１〜３個の水酸基を有する炭素数１０以上の有機アニオンとの塩からなる塩基性染料をあげることができる。添加量は、全感光性組成物の０.２〜５質量％である。
【００７９】
また、上記特開平５−３１３３５９号公報に記載の染料と相互作用して色調を変えさせる光分解物を発生させる化合物、例えば特開昭５０−３６２０９号（米国特許３,９６９,１１８号）に記載のｏ−ナフトキノンジアジド−４−スルホン酸ハロゲニド、特開昭５３−３６２２３号（米国特許４,１６０,６７１号）に記載のトリハロメチル−２−ピロンやトリハロメチルトリシジン、特開昭５５−６２４４４号（米国特許２,０３８,８０１号）に記載の種々のｏ−ナフトキノンジアジド化合物、特開昭５５−７７７４２号（米国特許４,２７９,９８２号）に記載の２−トリハロメチル−５−アリール１,３,４−オキサジアゾール化合物などを添加することができる。これらの化合物は単独または混合し使用することができる。これらの化合物のうち４００ｎｍに吸収を有する化合物を先の黄色染料として用いてもよい。
【００８０】
画像の着色剤として前記上記特開平５−３１３３５９号公報に記載の染料以外に他の染料を用いることができる。塩形成性有機染料を含めて好適な染料として油溶性染料および塩基染料を挙げることができる。具体的には、オイルグリーンＢＧ、オイルブルーＢＯＳ、オイルブルー＃６０３、（以上、オリエント化学工業株式会社製）、ビクトリアピュアブルーＢＯＨ、ビクトリアピュアブルーＮＡＰＳ、エチルバイオレット６ＨＮＡＰＳ（以上、保土谷化学工業（株）製）、ローダミンＢ（Ｃ１４５１７０Ｂ）、マラカイトグリーン（Ｃ１４２０００）、メチレンブルー（Ｃ１５２０１５）等を挙げることができる。
【００８１】
また、感光性組成物中には、下記一般式〔Ｉ〕、〔II〕あるいは〔III〕で表わされ、４１７ｎｍの吸光度が４３６ｎｍの吸光度の７０％以上である黄色系染料を添加することができる。
【００８２】
【化１２】

【００８３】
式〔Ｉ〕中、Ｒ¹およびＲ²はそれぞれ独立に水素原子、炭素数１〜１０のアルキル基、アリール基またはアルケニル基を示す。またＲ¹とＲ²は環を形成してもよい。Ｒ³、Ｒ⁴、Ｒ⁵はそれぞれ独立に水素原子、炭素数１〜１０のアルキル基を示す。Ｇ¹、Ｇ²はそれぞれ独立にアルコキシカルボニル基、アリールオキシカルボニル基、アシル基、アリールカルボニル基、アルキルチオ基、アリールチオ基、アルキルスルホニル基、アリールスルホニル基またはフルオロアルキルスルホニル基を示す。またＧ¹とＧ²は環を形成してもよい。さらにＲ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｇ¹、Ｇ²のうち１つ以上に１つ以上のスルホン酸基、カルボキシル基、スルホンアミド基、イミド基、Ｎ−スルホニルアミド基、フェノール性水酸基、スルホンイミド基、またはその金属塩、無機または有機アンモニウム塩を有する。ＹはＯ、Ｓ、ＮＲ（Ｒは水素原子もしくはアルキル基またはアリール基）、Ｓｅ、−Ｃ（ＣＨ₃）₂−、−ＣＨ＝ＣＨ−より選ばれる２価原子団を示し、ｎ1は０または１を示す。
【００８４】
【化１３】

【００８５】
式〔II〕中、Ｒ⁶およびＲ⁷はそれぞれ独立に水素原子、アルキル基、置換アルキル基、アリール基、置換アリール基、ヘテロ環基、置換ヘテロ環基、アリル基または置換アリル基を表わし、また、Ｒ⁶とＲ⁷とは共にそれが結合している炭素原子と共に環を形成しても良い。ｎ2は０、１または２を表わす。Ｇ³およびＧ⁴はそれぞれ独立に、水素原子、シアノ基、アルコキシカルボニル基、置換アルコキシカルボニル基、アリールオキシカルボニル基、置換アリールオキシカルボニル基、アシル基、置換アシル基、アリールカルボニル基、置換アリールカルボニル基、アルキルチオ基、アリールチオ基、アルキルスルホニル基、アリールスルホニル基、フルオロアルキルスルホニル基を表わす。ただし、Ｇ³とＧ⁴が同時に水素原子となることはない。また、Ｇ³とＧ⁴とはそれが結合している炭素原子と共に非金属原子から成る環を形成しても良い。さらにＲ⁶、Ｒ⁷、Ｇ³、Ｇ⁴のうち１つ以上に１つ以上のスルホン酸基、カルボキシル基、スルホンアミド基、イミド基、Ｎ−スルホニルアミド基、フェノール性水酸基、スルホンイミド基、またはその金属塩、無機または有機アンモニウム塩を有する。
【００８６】
【化１４】

【００８７】
式〔III〕中、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹、Ｒ¹²、Ｒ¹³はそれぞれ同じでも異なっていてもよく水素原子、アルキル基、置換アルキル基、アリール基、置換アリール基、アルコキシ基、ヒドロキシル基、アシル基、シアノ基、アルコキシカルボニル基、アリールオキシカルボニル基、ニトロ基、カルボキシル基、クロル基、ブロモ基を表わす。
【００８８】
（ポジ型感光層の形成、その他）
ポジ型感光層は、上記の各感光性組成物の成分を溶解する溶媒に溶かして支持体上に塗布することによって得られる。ここで使用する溶媒としては、γ−ブチロラクトン、エチレンジクロライド、シクロヘキサノン、メチルエチルケトン、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、２−メトキシエチルアセテート、１−メトキシ−２−プロパノール、１−メトキシ−２−プロピルアセテート、トルエン、酢酸エチル、乳酸メチル、乳酸エチル、ジメチルスルホキシド、ジメチルアセトアミド、ジメチルホルムアミド、水、Ｎ−メチルピロリドン、テトラヒドロフルフリルアルコール、アセトン、ジアセトンアルコール、メタノール、エタノール、イソプロパノール、ジエチレングリコールジメチルエーテルなどがあり、これらの溶媒を単独あるいは混合して使用できる。そして、溶液中の感光性組成物成分の濃度（固形分）は、２〜５０質量％が適当である。塗布量としては０.５ｇ／ｍ²〜４.０ｇ／ｍ²が好ましい。０.５ｇ／ｍ²よりも少ないと耐刷性が劣化する。４.０ｇ／ｍ²よりも多いと耐刷性は向上するが、感度が低下してしまう。また、感光性組成物溶液の支持体上への塗布等感光層の形成方法は、従来から知られた種々の方法によることができる。
【００８９】
感光性組成物中には、塗布法を良化するための界面活性剤、例えば、特開昭６２−１７０９５０号公報に記載されているようなフッ素系界面活性剤を添加することができる。好ましい添加量は、全感光性組成物の０.０１〜１質量％であり、さらに好ましくは０.０５〜０.５質量％である。以上のようにして得られた平版印刷版では、原画フィルムに対して忠実な印刷物を得ることができるが、焼ボケおよび印刷物のがさつき感が悪い。焼ボケを改良する方法としてこのようにして設けられた感光層の表面を凹凸にする方法がある。例えば特開昭６１−２５８２５５号公報に記載されているように感光組成物溶液中に数μｍの粒子を添加し、それを塗布する方法があるが、この方法では焼ボケの改良効果も小さくかつがさつき感は全く改良されない。
【００９０】
（露光）
本発明において、感光層を設けた平版印刷版は像露光された後に現像処理される。像露光に用いられる活性光線の光源としてはカーボンアーク灯、水銀灯、メタルハライドランプ、キセノンランプ、タングステンランプ、ケミカルランプなどがある。放射線としては、電子線、Ｘ線、イオンビーム、遠赤外線などがある。また、ｇ線、ｉ線、Ｄｅｅｐ−ＵＶ光、高密度エネルギービーム（レーザービーム）も使用される。レーザービームとしてはヘリウム・ネオンレーザー、アルゴンレーザー、クリプトンレーザー、ヘリウム・カドミウムレーザー、ＫｒＦエキシマーレーザー、半導体レーザー、ＹＡＧレーザーなどが挙げられる。
【００９１】
（現像処理）
次に、本発明の方法における現像処理について説明する。
本発明の方法において使用する現像液は珪酸塩を含まないものを使用する。そのような現像液として好ましいものは、実質的に有機溶剤を含まないアルカリ性の水溶液であり、具体的にはＮａＯＨ、ＫＯＨ、ＬｉＯＨ、第３リン酸ナトリウム、第２リン酸ナトリウム、第３リン酸アンモニウム、第２リン酸アンモニウム、炭酸ナトリウム、重炭酸ナトリウム、炭酸カリウム、アンモニア水などのような水溶液が適当である。さらに好ましくは（ａ）非還元糖から選ばれる少なくとも一種の糖類および（ｂ）少なくとも一種の塩基を含有し、ｐＨが９.０〜１３.５の範囲にある現像液である。以下この現像液について詳しく説明する。なお、本明細書中において、特にことわりのない限り、現像液とは現像開始液（狭義の現像液）と現像補充液とを意味する。
【００９２】
（非還元糖および塩基）
この現像液は、その主成分が、非還元糖から選ばれる少なくとも一つの化合物と、少なくとも一種の塩基からなり、液のｐＨが９.０〜１３.５の範囲であることを特徴とする。かかる非還元糖とは、遊離のアルデヒド基やケトン基を持たず、還元性を示さない糖類であり、還元基同士の結合したトレハロース型少糖類、糖類の還元基と非糖類が結合した配糖体および糖類に水素添加して還元した糖アルコールに分類され、何れも好適に用いられる。トレハロース型少糖類には、サッカロースやトレハロースがあり、配糖体としては、アルキル配糖体、フェノール配糖体、カラシ油配糖体などが挙げられる。また糖アルコールとしてはＤ,Ｌ−アラビット、リビット、キシリット、Ｄ,Ｌ−ソルビット、Ｄ,Ｌ−マンニット、Ｄ,Ｌ−イジット、Ｄ,Ｌ−タリット、ズリシットおよびアロズルシットなどが挙げられる。さらに、二糖類の水素添加で得られるマルチトールおよびオリゴ糖の水素添加で得られる還元体（還元水あめ）が好適に用いられる。これらの中で特に好ましい非還元糖は糖アルコールとサッカロースであり、特にＤ−ソルビット、サッカロース、還元水あめが適度なｐＨ領域に緩衝作用があることと、低価格であることで好ましい。これらの非還元糖は、単独もしくは二種以上を組み合わせて使用でき、それらの現像液中に占める割合は０.１〜３０質量％が好ましく、さらに好ましくは、１〜２０質量％である。この範囲以下では十分な緩衝作用が得られず、またこの範囲以上の濃度では、高濃縮化し難く、また原価アップの問題が出てくる。尚、還元糖を塩基と組み合わせて使用した場合、経時的に褐色に変色し、ｐＨも徐々に下がり、よって現像性が低下するという問題点がある。
【００９３】
非還元糖に組み合わせる塩基としては、珪酸塩以外の従来より知られているアルカリ剤が使用できる。例えば、水酸化ナトリウム、同カリウム、同リチウム、燐酸三ナトリウム、同カリウム、同アンモニウム、燐酸二ナトリウム、同カリウム、同アンモニウム、炭酸ナトリウム、同カリウム、同アンモニウム、炭酸水素ナトリウム、同カリウム、同アンモニウム、硼酸ナトリウム、同カリウム、同アンモニウムなどの無機アルカリ剤が挙げられる。また、モノメチルアミン、ジメチルアミン、トリメチルアミン、モノエチルアミン、ジエチルアミン、トリエチルアミン、モノイソプロピルアミン、ジイソプロピルアミン、トリイソプロピルアミン、ｎ−ブチルアミン、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、モノイソプロピノールアミン、ジイソプロパノールアミン、エチレンイミン、エチレンジアミン、ピリジンなどの有機アルカリ剤も用いられる。これらのアルカリ剤は単独もしくは二種以上を組み合わせて用いられる。これらの中で好ましいのは水酸化ナトリウム、同カリウムである。その理由は、非還元糖に対するこれらの量を調整することにより広いｐＨ領域でｐＨ調整が可能となるためである。また、燐酸三ナトリウム、同カリウム、炭酸ナトリウム、同カリウムなどもそれ自身に緩衝作用があるので好ましい。これらのアルカリ剤は現像液のｐＨを９.０〜１３.５の範囲になるように添加され、その添加量は所望のｐＨ、非還元糖の種類と添加量によって決められるが、より好ましいｐＨ範囲は１０.０〜１３.２である。
【００９４】
現像液にはさらに、糖類以外の弱酸と強塩基からなるアルカリ性緩衝液が併用できる。かかる緩衝液として用いられる弱酸としては、ｐＫａが１０.０〜１３.２のものが好ましい。このような弱酸としては、Pergamon Press社発行のIONISATION CONSTANTS OF ORGANIC ACIDS IN AQUEOUS SOLUTION などに記載されているものから選ばれ、例えば２,２,３,３−テトラフルオロプロパノール−１（ｐＫａ１２.７４）、トリフルオロエタノール（同１２.３７）、トリクロロエタノール（同１２.２４）などのアルコール類、ピリジン−２−アルデヒド（同１２.６８）、ピリジン−４−アルデヒド（同１２.０５）などのアルデヒド類、サリチル酸（同１３.０）、３−ヒドロキシ−２−ナフトエ酸（同１２.８４）、カテコール（同１２.６）、没食子酸（同１２.４）、スルホサリチル酸（同１１.７）、３,４−ジヒドロキシスルホン酸（同１２.２）、３,４−ジヒドロキシ安息香酸（同１１.９４）、１,２,４−トリヒドロキシベンゼン（同１１.８２）、ハイドロキノン（同１１.５６）、ピロガロール（同１１.３４）、ｏ−クレゾール（同１０.３３）、レゾルシノール（同１１.２７）、ｐ−クレゾール（同１０.２７）、ｍ−クレゾール（同１０.０９）などのフェノール性水酸基を有する化合物、
【００９５】
２−ブタノンオキシム（同１２.４５）、アセトキシム（同１２.４２）、１,２−シクロヘプタンジオンジオキシム（同１２.３）、２−ヒドロキシベンズアルデヒドオキシム（同１２.１０）、ジメチルグリオキシム（同１１.９）、エタンジアミドジオキシム（同１１.３７）、アセトフェノンオキシム（同１１.３５）などのオキシム類、アデノシン（同１２.５６）、イノシン（同１２.５）、グアニン（同１２.３）、シトシン（同１２.２）、ヒポキサンチン（同１２.１）、キサンチン（同１１.９）などの核酸関連物質、他に、ジエチルアミノメチルホスホン酸（同１２.３２）、１−アミノ−３,３,３−トリフルオロ安息香酸（同１２.２９）、イソプロピリデンジホスホン酸（同１２.１０）、１,１−エチリデンジホスホン酸（同１１.５４）、１,１−エチリデンジホスホン酸１−ヒドロキシ（同１１.５２）、ベンズイミダゾール（同１２.８６）、チオベンズアミド（同１２.８）、ピコリンチオアミド（同１２.５５）、バルビツル酸（同１２.５）などの弱酸が挙げられる。
【００９６】
これらの弱酸の中で好ましいのは、スルホサリチル酸、サリチル酸である。これらの弱酸に組み合わせる塩基としては、水酸化ナトリウム、同アンモニウム、同カリウムおよび同リチウムが好適に用いられる。これらのアルカリ剤は単独もしくは二種以上を組み合わせて用いられる。上記の各種アルカリ剤は濃度および組み合わせによりｐＨを好ましい範囲内に調整して使用される。
【００９７】
（界面活性剤）
現像液には、現像性の促進や現像カスの分散および印刷版画像部の親インキ性を高める目的で必要に応じて種々界面活性剤や有機溶剤を添加できる。好ましい界面活性剤としては、アニオン系、カチオン系、ノニオン系および両性界面活性剤が挙げられる。界面活性剤の好ましい例としては、ポリオキシエチレンアルキルエーテル類、ポリオキシエチレンアルキルフェニルエーテル類、ポリオキシエチレンポリスチリルフェニルエーテル類、ポリオキシエチレンポリオキシプロピレンアルキルエーテル類、グリセリン脂肪酸部分エステル類、ソルビタン脂肪酸部分エステル類、ペンタエリスリトール脂肪酸部分エステル類、プロピレングリコールモノ脂肪酸エステル類、しょ糖脂肪酸部分エステル類、ポリオキシエチレンソルビタン脂肪酸部分エステル類、ポリオキシエチレンソルビトール脂肪酸部分エステル類、ポリエチレングリコール脂肪酸エステル類、ポリグリセリン脂肪酸部分エステル類、ポリオキシエチレン化ひまし油類、ポリオキシエチレングリセリン脂肪酸部分エステル類、脂肪酸ジエタノールアミド類、Ｎ,Ｎ−ビス−２−ヒドロキシアルキルアミン類、ポリオキシエチレンアルキルアミン、トリエタノールアミン脂肪酸エステル、トリアルキルアミンオキシドなどの非イオン性界面活性剤、
【００９８】
脂肪酸塩類、アビエチン酸塩類、ヒドロキシアルカンスルホン酸塩類、アルカンスルホン酸塩類、ジアルキルスルホ琥珀酸エステル塩類、直鎖アルキルベンゼンスルホン酸塩類、分岐鎖アルキルベンゼンスルホン酸塩類、アルキルナフタレンスルホン酸塩類、アルキルフェノキシポリオキシエチレンプロピルスルホン酸塩類、ポリオキシエチレンアルキルスルホフェニルエーテル塩類、Ｎ−メチル−Ｎ−オレイルタウリンナトリウム塩、Ｎ−アルキルスルホ琥珀酸モノアミド二ナトリウム塩、石油スルホン酸塩類、硫酸化牛脂油、脂肪酸アルキルエステルの硫酸エステル塩類、アルキル硫酸エステル塩類、ポリオキシエチレンアルキルエーテル硫酸エステル塩類、脂肪酸モノグリセリド硫酸エステル塩類、ポリオキシエチレンアルキルフェニルエーテル硫酸エステル塩類、ポリオキシエチレンスチリルフェニルエーテル硫酸エステル塩類、アルキルリン酸エステル塩類、ポリオキシエチレンアルキルエーテルリン酸エステル塩類、ポリオキシエチレンアルキルフェニルエーテルリン酸エステル塩類、スチレン／無水マレイン酸共重合物の部分鹸化物類、オレフィン／無水マレイン酸共重合物の部分鹸化物類、ナフタレンスルホン酸塩ホルマリン縮合物類などのアニオン界面活性剤、アルキルアミン塩類、テトラブチルアンモニウムブロミド等の第四級アンモニウム塩類、ポリオキシエチレンアルキルアミン塩類、ポリエチレンポリアミン誘導体などのカチオン性界面活性剤、カルボキシベタイン類、アミノカルボン酸類、スルホベタイン類、アミノ硫酸エステル類、イミダゾリン類などの両性界面活性剤が挙げられる。以上挙げた界面活性剤の中でポリオキシエチレンとあるものは、ポリオキシメチレン、ポリオキシプロピレン、ポリオキシブチレンなどのポリオキシアルキレンに読み替えることもでき、それらの界面活性剤もまた包含される。
【００９９】
さらに好ましい界面活性剤は、分子内にパーフルオロアルキル基を含有するフッ素系の界面活性剤である。かかるフッ素系界面活性剤としては、パーフルオロアルキルカルボン酸塩、パーフルオロアルキルスルホン酸塩、パーフルオロアルキルリン酸エステルなどのアニオン型、パーフルオロアルキルベタインなどの両性型、パーフルオロアルキルトリメチルアンモニウム塩などのカチオン型およびパーフルオロアルキルアミンオキサイド、パーフルオロアルキルエチレンオキシド付加物、パーフルオロアルキル基および親水性基含有オリゴマー、パーフルオロアルキル基および親油性基含有オリゴマー、パーフルオロアルキル基、親水性基および親油性基含有オリゴマー、パーフルオロアルキル基および親油性基含有ウレタンなどの非イオン型が挙げられる。上記の界面活性剤は、単独もしくは２種以上を組み合わせて使用することができ、現像液中に０.００１〜１０質量％、より好ましくは０.０１〜５質量％の範囲で添加される。
【０１００】
（現像安定化剤）
現像液には、種々の現像安定化剤が用いられる。それらの好ましい例として、特開平６−２８２０７９号公報記載の糖アルコールのポリエチレングリコール付加物、テトラブチルアンモニウムヒドロキシドなどのテトラアルキルアンモニウム塩、テトラブチルホスホニウムブロマイドなどのホスホニウム塩およびジフェニルヨードニウムクロライドなどのヨードニウム塩が好ましい例として挙げられる。さらには、特開昭５０−５１３２４号公報記載のアニオン界面活性剤または両性界面活性剤、また特開昭５５−９５９４６号公報記載の水溶性カチオニックポリマー、特開昭５６−１４２５２８号公報に記載されている水溶性の両性高分子電解質がある。さらに、特開昭５９−８４２４１号公報のアルキレングリコールが付加された有機ホウ素化合物、特開昭６０−１１１２４６号公報記載のポリオキシエチレン・ポリオキシプロピレンブロック重合型の水溶性界面活性剤、特開昭６０−１２９７５０号公報のポリオキシエチレン・ポリオキシプロピレンを置換したアルキレンジアミン化合物、特開昭６１−２１５５５４号公報記載の重量平均分子量３００以上のポリエチレングリコール、特開昭６３−１７５８５８号公報のカチオン性基を有する含フッ素界面活性剤、特開平２−３９１５７号公報の酸またはアルコールに４モル以上のエチレンオキシドを付加して得られる水溶性エチレンオキシド付加化合物と、水溶性ポリアルキレン化合物などが挙げられる。
【０１０１】
（有機溶剤）
現像液は実質的に有機溶剤を含まないものであるが、必要により有機溶剤が加えられる。かかる有機溶剤としては、水に対する溶解度が約１０質量％以下のものが適しており、好ましくは５質量％以下のものから選ばれる。例えば、１−フェニルエタノール、２−フェニルエタノール、３−フェニル−１−プロパノール、４−フェニル−１−ブタノール、４−フェニル−２−ブタノール、２−フェニル−１−ブタノール、２−フェノキシエタノール、２−ベンジルオキシエタノール、ｏ−メトキシベンジルアルコール、ｍ−メトキシベンジルアルコール、ｐ−メトキシベンジルアルコール、ベンジルアルコール、シクロヘキサノール、２−メチルシクロヘキサノール、３−メチルシクロヘキサノールおよび４−メチルシクロヘキサノール、Ｎ−フェニルエタノールアミンおよびＮ−フェニルジエタノールアミンなどを挙げることができる。現像液において実質的に有機溶剤を含まないとは、有機溶剤の含有量が使用液の総重量に対して５質量％以下であることをいう。その使用量は界面活性剤の使用量と密接な関係があり、有機溶剤の量が増すにつれ、界面活性剤の量は増加させることが好ましい。これは界面活性剤の量が少なく、有機溶剤の量を多く用いると有機溶剤が完全に溶解せず、従って、良好な現像性の確保が期待できなくなるからである。
【０１０２】
（還元剤）
現像液にはさらに還元剤を加えることができる。これは印刷版の汚れを防止するものであり、特に感光性ジアゾニウム塩化合物を含むネガ型感光性平版印刷版を現像する際に有効である。好ましい有機還元剤としては、チオサリチル酸、ハイドロキノン、メトール、メトキシキノン、レゾルシン、２−メチルレゾルシンなどのフェノール化合物、フェニレンジアミン、フェニルヒドラジンなどのアミン化合物が挙げられる。さらに好ましい無機の還元剤としては、亜硫酸、亜硫酸水素酸、亜リン酸、亜リン酸水素酸、亜リン酸二水素酸、チオ硫酸および亜ジチオン酸などの無機酸のナトリウム塩、カリウム塩、アンモニウム塩などを挙げることができる。これらの還元剤のうち汚れ防止効果が特に優れているのは亜硫酸塩である。これらの還元剤は使用時の現像液に対して好ましくは、０.０５〜５質量％の範囲で含有される。
【０１０３】
（有機カルボン酸）
現像液にはさらに有機カルボン酸を加えることもできる。好ましい有機カルボン酸は炭素原子数６〜２０の脂肪族カルボン酸および芳香族カルボン酸である。脂肪族カルボン酸の具体的な例としては、カプロン酸、エナンチル酸、カプリル酸、ラウリン酸、ミリスチン酸、パルミチン酸およびステアリン酸などがあり、特に好ましいのは炭素数８〜１２のアルカン酸である。また炭素鎖中に二重結合を有する不飽和脂肪酸でも、枝分かれした炭素鎖のものでもよい。芳香族カルボン酸としては、ベンゼン環、ナフタレン環、アントラセン環などにカルボキシル基が置換された化合物で、具体的には、ｏ−クロロ安息香酸、ｐ−クロロ安息香酸、ｏ−ヒドロキシ安息香酸、ｐ−ヒドロキシ安息香酸、ｏ−アミノ安息香酸、ｐ−アミノ安息香酸、２,４−ジヒドロキシ安息香酸、２,５−ジヒドロキシ安息香酸、２,６−ジヒドロキシ安息香酸、２,３−ジヒドロキシ安息香酸、３,５−ジヒドロキシ安息香酸、没食子酸、１−ヒドロキシ−２−ナフトエ酸、３−ヒドロキシ−２−ナフトエ酸、２−ヒドロキシ−１−ナフトエ酸、１−ナフトエ酸、２−ナフトエ酸などがあるがヒドロキシナフトエ酸は特に有効である。上記脂肪族および芳香族カルボン酸は水溶性を高めるためにナトリウム塩やカリウム塩またはアンモニウム塩として用いるのが好ましい。現像液の有機カルボン酸の含有量は格別な制限はないが、０.１質量％より低いと効果が十分でなく、また１０質量％以上ではそれ以上の効果の改善が計れないばかりか、別の添加剤を併用する時に溶解を妨げることがある。従って、好ましい添加量は使用時の現像液に対して０.１〜１０質量％であり、より好ましくは０.５〜４質量％である。
【０１０４】
（その他）
現像液には、さらに必要に応じて、防腐剤、着色剤、増粘剤、消泡剤および硬水軟化剤などを含有させることもできる。硬水軟化剤としては例えば、ポリ燐酸およびそのナトリウム塩、カリウム塩およびアンモニウム塩、エチレンジアミンテトラ酢酸、ジエチレントリアミンペンタ酢酸、トリエチレンテトラミンヘキサ酢酸、ヒドロキシエチルエチレンジアミントリ酢酸、ニトリロトリ酢酸、１,２−ジアミノシクロヘキサンテトラ酢酸および１,３−ジアミノ−２−プロパノールテトラ酢酸などのアミノポリカルボン酸およびそれらのナトリウム塩、カリウム塩およびアンモニウム塩、アミノトリ（メチレンホスホン酸）、エチレンジアミンテトラ（メチレンホスホン酸）、ジエチレントリアミンペンタ（メチレンホスホン酸）、トリエチレンテトラミンヘキサ（メチレンホスホン酸）、ヒドロキシエチルエチレンジアミントリ（メチレンホスホン酸）および１−ヒドロキシエタン−１,１−ジホスホン酸やそれらのナトリウム塩、カリウム塩およびアンモニウム塩を挙げることができる。
【０１０５】
このような硬水軟化剤はそのキレート化力と使用される硬水の硬度および硬水の量によって最適値が変化するが、一般的な使用量を示せば、使用時の現像液に０.０１〜５質量％、より好ましくは０.０１〜０.５質量％の範囲である。この範囲より少ない添加量では所期の目的が十分に達成されず、添加量がこの範囲より多い場合は、色抜けなど、画像部への悪影響がでてくる。現像液の残余の成分は水である。現像液は、使用時よりも水の含有量を少なくした濃縮液としておき、使用時に水で希釈するようにしておくことが運搬上有利である。この場合の濃縮度は、各成分が分離や析出を起こさない程度が適当である。
【０１０６】
（現像および後処理）
かかる組成の現像液で現像処理された平板印刷版は水洗水、界面活性剤等を含有するリンス液、アラビアガムや澱粉誘導体等を主成分とするフィニッシャーや保護ガム液で後処理を施される。本発明の方法において感光性平板印刷版の後処理にはこれらの処理を種々組み合わせて用いることができる。近年、製版・印刷業界では製版作業の合理化および標準化のため、感光性平板印刷版用の自動現像機が広く用いられている。この自動現像機は、一般に現像部と後処理部からなり、感光性平板印刷版を搬送する装置と、各処理液槽およびスプレー装置からなり、露光済みの感光性平板印刷版を水平に搬送しながら、ポンプで汲み上げた各処理液をスプレーノズルから吹き付けて現像および後処理するものである。また、最近は処理液が満たされた処理液槽中に液中ガイドロールなどによって感光性平板印刷版を浸漬搬送させて現像処理する方法や、現像後一定量の少量の水洗水を版面に供給して水洗し、その廃水を現像液原液の希釈水として再利用する方法も知られている。このような自動処理においては、各処理液に処理量や稼働時間等に応じてそれぞれの補充液を補充しながら処理することができる。また、実質的に未使用の処理液で処理するいわゆる使い捨て処理方式も適用できる。このような処理によって得られた平版印刷版はオフセット印刷機に掛けられ、多数枚の印刷に用いられる。
【０１０７】
【実施例】
以下実施例をもって本発明を説明するが、本発明はこれらの実施例に限定されるものではない。
<支持体の作成方法>
（ａ）下記の表１の成分からなるＡｌ溶湯を調整し、溶湯処理、濾過を行った上で、厚さ５００ｍｍ、幅１２００ｍｍの鋳塊をＤＣ鋳造法で作成し、表面を平均１０ｍｍ面削機で削り取った後、約５時間５５０℃で均熱保持し、温度４００℃に下がったところで、熱間圧延を用いて厚さ２.７ｍｍの圧延板とし、更に連続焼鈍機を使って熱処理を５００℃で行った後、冷間圧延で、厚さ０.２４ｍｍに仕上げた。このアルミ板を幅１０３０ｍｍにした後、連続的に処理を行った。
【０１０８】
【表１】

【０１０９】
（ｂ）アルミニウム板の表面をナイロンブラシと４００メッシュのパミストンの水懸濁液を用い、砂目立てをした後、よく水で洗浄した。苛性ソーダ濃度２６質量％、アルミニウムイオン濃度６.５質量％、温度７０℃でスプレーによるエッチング処理を行い、アルミニウム板を７ｇ／ｍ²溶解した。その後スプレーによる水洗をおこなった。
（ｃ）温度３０℃の硝酸濃度１質量％水溶液（アルミニウムイオン０.５質量％含む）で、スプレーによるデスマット処理を行い、その後スプレーで水洗した。前記デスマットに用いた硝酸水溶液は、硝酸水溶液中で交流を用いて電気化学的な粗面化を行う工程の廃液を用いた。
【０１１０】
（ｄ）６０Ｈｚの交流電圧を用いて連続的に電気化学的な粗面化処理を行った。この時の電解液は、硝酸１質量％水溶液（アルミニウムイオン０.５質量％、アンモニウムイオン０.００７質量％含む）、温度５０℃であった。交流電源波形は図２に示した波形で電流値がゼロからピークに達するまでの時間ＴＰが２ｍｓｅｃ、ｄｕｔｙ比１：１、台形の矩形波交流を用いて、カーボン電極を対極として電気化学的な粗面化処理を行った。補助アノードにはフェライトを用いた。電解槽は２個使用した。
電流密度は電流のピーク値で３０Ａ／ｄｍ²、電気量はアルミニウム板が陽極時の電気量の総和で２３０Ｃ／ｄｍ²であった。補助陽極には電源から流れる電流の５％を分流させた。
その後、スプレーによる水洗を行った。
【０１１１】
（ｅ）アルミニウム板を苛性ソーダ濃度２６質量％、アルミニウムイオン濃度６.５質量％でスプレーによるエッチング処理を７０℃でおこない、アルミニウム板を１ｇ／ｍ²溶解し、前段の交流を用いて電気化学的な粗面化をおこなったときに生成した水酸化アルミニウムを主体とするスマット成分の除去と、生成したピットのエッジ部分を溶解し、エッジ部分を滑らかにした。その後スプレーで水洗した。
（ｆ）温度６０℃の硫酸濃度２５質量％水溶液（アルミニウムイオンを０.５質量％含む）で、スプレーによるデスマット処理をおこない、その後スプレーによる水洗をおこなった。
【０１１２】
（ｇ）陽極酸化装置を使って硫酸濃度１７０g／ｌ（アルミニウムイオンを０.５質量％含む）、温度４０℃、３０Ａ／ｄｍ²、にて陽極酸化量が２.５ｇ／ｍ²になるように陽極酸化処理ををおこなってから、スプレーによる水洗をおこなった。ここまでの基板をＡとした。
次に第２表に示したフッ化物を含む水溶液で処理を行った後、水洗を行い、各基板を作成した。
【０１１３】
得られた基板表面のフッ素化率を下記の装置を用いて下記の条件にて測定した。
装置名：ＰＨＩ−５４００ＭＣ（アルバック・ファイ製）
Ｘ線源：ＭｇＫ_α（４００Ｗ）
Pass energy：７１.５５eV
分析面積：１.１ｍｍφ
光電子の取り出し角度：４５度
【０１１４】
次に上記の如く処理された基板上に、下記に示した高分子化合物を下記処方にて塗布した後、８０℃、１５秒間乾燥した。乾燥後の塗布量は６.５ｍｇ／ｍ₂であった。次に下記感光液Ａを塗布することにより感光層を設けた。乾燥後の感光層塗布量は１.３ｇ/ｍ²であった。さらに真空密着時間を短縮させるため、特公昭６１-２８９８６号記載の方法でマット層を形成させることにより、感光性平版印刷板を作成した。
【０１１５】
〔処方〕
高分子化合物（分子量Ｍｗ＝２.８万）：０.１ｇ
メタノール：１００ｇ
純水：１ｇ
【０１１６】
【化１５】

【０１１７】
〔感光液Ａ〕
１,２−ジアゾナフトキノン−５−スルホニルクロリドとピロガロール−アセトン樹脂とのエステル化物（米国特許第3,635,709号明細書の実施例１に記載されているもの） ０.８ｇ
バインダー
ノボラックＩ(下記構造式参照) １.５ｇ
ノボラックII(下記構造式参照) ０.２ｇ
ノボラック以外の樹脂III(下記構造式参照) ０.４ｇ
ｐ−ノルマルオクチルフェノール−ホルムアルデヒド樹脂 （米国特許第4,123,279号明細書に記載されているもの） ０.０２ｇ
ナフトキノン−１,２−ジアジド−４−スルホン酸クロライド ０.０１ｇ
テトラヒドロ無水フタル酸 ０.０２ｇ
安息香酸 ０.０２ｇ
ピロガロール ０.０５ｇ
４−〔ｐ−Ｎ,Ｎ−ビス（エトキシカルボニルメチル）アミノフェニル〕−２,６−ビス（トリクロロメチル）−Ｓ−トリアジン（以下トリアジンＡと略）０.０７ｇ
ビクトリアピュアブルーＢＯＨ（保土谷化学（株）製の対アニオンを１−ナフタレンスルホン酸に変えた染料） ０.０４５ｇ
Ｆ１７６ＰＦ（フッ素系界面活性剤、大日本インキ化学工業（株）製）０.０１ｇ
メチルエチルケトン １５ｇ
１−メトキシ−２−プロパノール １０ｇ
【０１１８】
【化１６】

【０１１９】
このように作成した感光性平版印刷版を１ｍの距離から３ｋＷのメタルハライドランプにより１分間画像露光し、下記の現像液ＡあるいはＢを用いて富士写真フイルム（株）製ＰＳプロセッサー９００ＶＲを用いて、３０℃１２秒間現像した。
【０１２０】
現像液Ａ（ｐＨ＝１３）：
Ｄ−ソルビトール ５.１重量部
水酸化ナトリウム １.１重量部
トリエタノールアミン・エチレンオキサイド付加物（３０モル） ０.０３重量部
水 ９３.８重量部 現像液Ｂ：
［ＳｉＯ₂］／［Ｎａ₂Ｏ］モル比１.２、ＳｉＯ₂ １.４質量％の珪酸ナトリウム水溶液 １００ 重量部
エチレンジアミン・エチレンオキサイド付加物（３０モル） ０.０３重量部
【０１２１】
上記のように現像処理して得られた平版印刷版について、耐刷性、汚れ性、残色、残膜性能、カス、ヘドロを測定した。その結果を表２に示した。なお、上記性能の評価方法は次のとおりである。
【０１２２】
耐刷性：小森印刷機（株）製印刷機スプリントを用いて、正常に印刷されなくなるまでの印刷枚数をもって評価した。印刷枚数が多いほど耐刷性が良好である。
【０１２３】
汚れ性：ハイデルベルグ社製ＳＯＲ−Ｍ印刷機にて１０００枚印刷後印刷を停止し、３０分間放置する。その後、再度印刷機に取り付けて１００枚印刷した。その時の非画像部のインキの払われた枚数を評価した。枚数が少なければ少ないほど汚れ性能はよい。
【０１２４】
ヘドロ・カス：現像液１リットルに対して、プレート１０ｍ²を処理した後、この時のアルカリ現像液に対する酸化皮膜の溶解の程度を現像液中に残るカスの状態で判定した。
○・・・カス、ヘドロが発生しない
△・・・カス、ヘドロの発生が認められるが、×程は多くない。
×・・・カス、ヘドロが多量に発生する
【０１２５】
残膜：現像後の平版印刷版の非画像部の２８０ｎｍの光での反射光学濃度と感光層塗布前の支持体表面の２８０ｎｍの反射光学濃度の差(ΔＤ)を測定した。ΔＤが少ないほど残膜性能が良い。
【０１２６】
残色：現像後の平版印刷版の非画像部の６００ｎｍの光での反射光学濃度と感光層塗布前の支持体表面の６００ｎｍの光での反射光学濃度の差（ΔＤ）を測定した。ΔＤが少ないほど残色性能が良い。
【０１２７】
下記表から明らかなように支持体のフッ素化率が０.３〜０.９の範囲を有する感光性平版印刷版を珪酸塩を含まない現像液で現像処理した平版印刷版（参考例１〜６及び実施例７）はいずれも汚れ、耐刷、残色、残膜性能に優れ、かつ現像液中のカス、ヘドロも発生しなかった。一方、比較例（１〜４）に示した基板はいずれも汚れ、耐刷性、残色、残膜、カス・ヘドロを両立出来ず、満足のいくものではなかった。
【０１２８】
【表２】

【０１２９】
【発明の効果】
本発明の平版印刷版の製造方法により、残色、残膜性能、汚れ性能及び耐刷性能が共に良好なポジ型感光性平版印刷版が得られ、かつ現像時のカス、ヘドロを抑制できる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a lithographic printing plate having improved developability, corrosion resistance, stain, printing durability, residual color and residual film performance.
[0002]
[Prior art]
A conventional positive photosensitive lithographic printing plate is obtained by providing an ink-receptive photosensitive layer on a hydrophilic support. When the photosensitive layer of such a photosensitive lithographic printing plate is subjected to image exposure and then the exposed photosensitive layer is developed using a developer, the exposed photosensitive layer is removed and the surface of the hydrophilic support is exposed. On the other hand, the photosensitive layer in the non-exposed area remains on the surface of the support to form an ink-receptive image area, whereby a lithographic printing plate is obtained. In such a printing plate, it is necessary to further hydrophilize the non-image area in order to prevent stains caused by ink on the non-image area, but usually a developer containing an alkali metal silicate is used during development. As a result, only the non-image area was made hydrophilic to improve the dirt performance. However, when using a developer containing alkali metal silicate, SiO₂It is easy to deposit solids resulting from the above, or when processing the development waste liquid, if neutralization is performed, SiO₂There was a problem such as the formation of a gel due to the above. In addition, there has been a problem that a lipophilic component such as a dye or a resin dissolved in the developer is re-adsorbed on the alkali metal silicate adhering to the development, and the residual color and the residual film performance are deteriorated.
[0003]
As a developer capable of avoiding these disadvantages, as a development stabilizer, it contains at least one compound selected from saccharides, oximes, phenols, and fluorinated alcohols in an amount of 0.01 mol / liter or more, and an alkali. A developer containing an agent, that is, a silicate-free developer, can be considered, but when a conventional positive photosensitive lithographic printing plate is developed, the anodized film of the aluminum support is dissolved in the developer, In other words, there are other inconveniences, such as debris and sludge, which deteriorates the cleaning performance of the automatic processor and causes clogging of the spray. In addition, if a printing plate developed with such a developer is left at the time of printing, there is a problem that so-called left-off stains are generated, which makes it difficult to remove ink.
[0004]
In order to solve these problems, various treatments for the anodized film of the support have been proposed. Steam treatment, which is said to be capable of preventing dissolution at the time of development, can prevent the residual color of the non-image area and the residual film phenomenon, but it cannot solve the problem of leaving stains. In addition, the silicate treatment on the anodized film can solve the problem of leaving stains in the non-image area, but it has the disadvantage that the printing durability and the residual color performance deteriorate, both of which lead to solving these problems. Not.
[0005]
[Problems to be solved by the invention]
Accordingly, an object of the present invention is to provide a method for producing a lithographic printing plate that has good residual color, residual film performance, printing durability and stain performance, and can suppress residue and sludge in the developer during development. is there.
[0006]
[Means for Solving the Problems]
As a result of earnest research to achieve the above object, the present inventor developed a lithographic printing plate in which a positive photosensitive layer is provided on an aluminum support having a surface satisfying the relationship represented by the following formula without developing a silicate. A positive-type photosensitive lithographic printing plate having good residual color, residual film performance, stain performance and printing durability can be obtained by a lithographic printing plate manufacturing method characterized by developing with a liquid. The present invention was completed by finding that it was possible to suppress dregs and sludge. That is, in the production method of the present invention, the aluminum support has the formula: 0.30 ≦ A / (A + B) ≦ 0.90 (wherein A represents fluorine (1S) obtained by measurement using X-ray photoelectron spectroscopy. ) Represents the peak area (counts · eV / sec), and B satisfies the aluminum (2P) peak area (counts · eV / sec) obtained by X-ray photoelectron spectroscopy. is there.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the method of the present invention will be described in detail. In the method for producing a photosensitive lithographic printing plate of the present invention, the surface of an aluminum support optionally subjected to anodization and roughening treatment is treated so as to have a constant fluorination rate, which will be described later on this aluminum support. This is a method in which a positive photosensitive layer is provided, and after the exposure, it is processed with a developer containing no silicate. The method of the present invention is particularly characterized in that a lithographic printing plate produced using an aluminum support having a certain fluorination rate is developed with a developer containing no silicate.
[0008]
(Aluminum support)
The aluminum support used in the present invention has a surface of 0.30 ≦ A / (A + B) ≦ 0.90 (where A is a fluorine (1S) obtained by measurement using X-ray photoelectron spectroscopy. The peak area (counts · eV / sec) is represented, and B is the peak area of aluminum (2P) obtained by measurement using X-ray photoelectron spectroscopy (hereinafter referred to as ESCA as appropriate) ( (representing counts · eV / sec)).
[0009]
Here, ESCA will be described.
When the surface of the sample is irradiated with X-rays having a constant energy (hν) in an ultrahigh vacuum, electrons (photoelectrons) are emitted from the sample constituent atoms into the vacuum by the photoelectric effect.
At this time, the kinetic energy (E_K) Is represented by formula (I) and E_KIs measured with an energy analyzer, so that the photoelectron binding energy (E_B) Is required.
[0010]
[Expression 1]
E_K= Hν-E_B-Φ (I)
(In the formula, φ represents a work function.)
[0011]
As the irradiated X-ray, Mg-Kα (1253.6 eV) or Al-Kα (1486.6 eV) having a small energy width is used, and the penetration depth of such soft X-ray is about several μm from the sample surface.
However, the photoelectrons generated from the deep part of the sample have a very high probability of losing energy due to inelastic scattering with other atoms before reaching the sample surface, and only the photoelectrons generated on the extreme surface of the sample are other It is analyzed by jumping out while maintaining the relationship of formula (I) without colliding with atoms.
For these reasons, ESCA can measure several nanometers (several tens of inches) on the outermost surface of the sample.
[0012]
In the present invention, the peak area of fluorine (1S) obtained when the surface of an aluminum support is measured by ESCA is A (counts · eV / sec), and the peak area of aluminum (2P) measured in the same manner is B (counts). · EV / sec), both are in the relationship 0.30 ≦ A / (A + B) ≦ 0.90, preferably 0.37 ≦ A / (A + B) ≦ 0.85, and more The range is preferably 0.45 ≦ A / (A + B) ≦ 0.85, most preferably 0.55 ≦ A / (A + B) ≦ 0.90). When A / (A + B) is smaller than 0.30, the content of the inorganic fluorine compound contained in the coating layer is too small, and the intended effect of improving acid resistance and alkali resistance is insufficient. On the other hand, when it exceeds 0.90, there is a problem that the adhesion between the substrate and the photosensitive layer is lowered and the printing durability is deteriorated.
[0013]
Such a support can be obtained by optionally anodizing the support surface and then treating with a fluorine-containing compound or the like. Preferable examples include a method of forming a coating layer containing an inorganic fluorine compound on a support. The coating layer may be formed directly on the aluminum substrate. However, from the viewpoint of durability and effect, the coating layer is preferably formed on the anodized film after anodizing the aluminum support.
[0014]
The coating layer can be formed by bringing the anodized film of the aluminum support into contact with an aqueous solution containing an inorganic fluorine compound. As the inorganic fluorine compound that can be used in the present invention, a metal fluoride is preferable. Specifically, for example, sodium fluoride, calcium fluoride, potassium fluoride, magnesium fluoride, potassium hexafluorozirconium, sodium hexafluorozirconium, sodium hexafluorotitanate, potassium hexafluorotitanate, hexafluorozirconium hydrogen acid , Hexafluorotitanium hydrogen acid, hexafluorozirconium ammonium, hexafluorotitanate ammonium, hexafluorosilicic acid, nickel fluoride, iron fluoride, phosphorous phosphate, ammonium fluoride phosphate, etc. May be used alone, or two or more of them may be used in combination. Preferred inorganic fluorine compounds include sodium fluoride, potassium fluoride, ammonium fluoride and lithium fluoride.
[0015]
The concentration of the inorganic fluorine compound in the aqueous solution is suitably from 0.001 g / liter to 100 g / liter, preferably from 0.01 g / liter to 50 g / liter, more preferably from 0.1 g / liter to 20 g / liter. . The aluminum support of the present invention has, for example, an aqueous solution having a pH of 2 to 6 at 25 ° C., preferably 3 to 5 at a temperature of 20 ° C. to less than 100 ° C., preferably 30 to 70 ° C. It can be obtained by contacting an aluminum substrate for 0.5 seconds to 6 minutes, more preferably 1 second to 30 seconds. The contact method may be immersion in these aqueous solutions, spraying the aqueous solution to the surface on which the anodized film is formed, or contacting the substrate surface in a state where the aqueous solution is vaporized. Any known method can be used as long as the temperature and contact time of the aqueous solution can be controlled.
[0016]
Moreover, when processing with the aqueous solution containing an inorganic fluorine compound for formation of a coating layer, a phosphoric acid process can also be performed in order to improve the hydrophilic property of the support surface.
Examples of the phosphate that can be used for the hydrophilicity-improving treatment of the support according to the present invention include metal phosphates such as alkali metals and alkaline earth metals. Specifically, for example, zinc phosphate, aluminum phosphate, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, monoammonium phosphate, monopotassium phosphate, monosodium phosphate, dihydrogen phosphate Potassium, dipotassium hydrogen phosphate, calcium phosphate, sodium ammonium hydrogen phosphate, diammonium hydrogen phosphate, magnesium hydrogen phosphate, magnesium phosphate, ferrous phosphate, ferric phosphate, sodium dihydrogen phosphate, phosphorus Sodium phosphate, disodium hydrogen phosphate, lead phosphate, diammonium phosphate, calcium dihydrogen phosphate, lithium phosphate, phosphotungstic acid, ammonium phosphotungstate, sodium tungstate phosphate, ammonium phosphomolybdate, phosphomolybdenum Sodium salt . Moreover, sodium phosphite, sodium tripolyphosphate, and sodium pyrophosphate can be mentioned. Preferred examples include sodium dihydrogen phosphate, disodium hydrogen phosphate, potassium dihydrogen phosphate, and dipotassium hydrogen phosphate. These may be used alone or in combination of two or more.
[0017]
When performing such phosphoric acid treatment, a phosphoric acid mixed solution in which these phosphoric acids are mixed with an aqueous solution containing an inorganic fluorine compound may be prepared and used for the treatment. You may process with the process liquid containing phosphoric acid before and after a layer formation process.
The concentration of the phosphate in the aqueous solution is suitably 10 g / liter to 1000 g / liter, preferably 50 g / liter to 200 g / liter. The treatment method can be carried out under the same conditions as previously treated with an aqueous solution containing an inorganic fluorine compound.
[0018]
Moreover, when processing with the aqueous solution containing an inorganic fluorine compound for coating layer formation, a silicate process can also be performed back and forth in order to improve the hydrophilic property of the support surface.
Examples of the silicate that can be used for the hydrophilicity improving treatment of the support according to the present invention include sodium silicate, potassium silicate, and lithium silicate.
[0019]
When performing such a silicate treatment, a mixed solution prepared by mixing these silicates with an aqueous solution containing an inorganic fluorine compound may be prepared and used for the treatment. You may process with the process liquid containing a silicate before and after a process. The concentration of the silicate in the aqueous solution is suitably 0.1 g / liter to 100 g / liter, preferably 1 g / liter to 50 g / liter. The treatment method can be carried out under the same conditions as previously treated with an aqueous solution containing an inorganic fluorine compound.
[0020]
Moreover, when processing with the aqueous solution containing an inorganic fluorine compound for formation of a coating layer, a hydrophilic resin process can also be performed in order to improve the hydrophilic property of the support surface.
Examples of the hydrophilic resin that can be used for the hydrophilicity improving treatment of the support according to the present invention include polyvinylphosphonic acid, polyvinyl alcohol, and CMC.
[0021]
When performing such hydrophilic resin treatment, a mixed liquid prepared by mixing these hydrophilic resins with an aqueous solution containing an inorganic fluorine compound may be prepared and used for the treatment. You may process with the process liquid containing hydrophilic resin before and after a layer formation process.
The concentration of the hydrophilic resin in the aqueous solution is suitably 0.001 g / liter to 100 g / liter, and preferably 0.1 g / liter to 50 g / liter. The treatment method can be carried out under the same conditions as previously treated with an aqueous solution containing an inorganic fluorine compound.
[0022]
Two or more of the above phosphoric acid, silicate, and hydrophilic resin may be used in combination.
[0023]
The aluminum support used in the method of the present invention is a metal mainly composed of dimensionally stable aluminum, and is made of aluminum or an aluminum alloy. In addition to a pure aluminum plate, an alloy plate containing aluminum as a main component and containing a trace amount of foreign elements, or a plastic film or paper laminated or vapor-deposited with aluminum (alloy) is selected. Furthermore, a composite sheet in which an aluminum sheet is bonded to a polyethylene terephthalate film as described in Japanese Patent Publication No. 48-18327 may be used. In the following description, the above-mentioned substrate made of aluminum or an aluminum alloy is generically used as an aluminum support. Examples of the foreign element contained in the aluminum alloy include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, and titanium. The content of the foreign element in the alloy is 10% by mass or less. In the present invention, a pure aluminum plate is suitable, but since completely pure aluminum is difficult to manufacture in the refining technique, it may contain a slightly different element. Thus, the composition of the aluminum plate applied to the present invention is not specified, and a conventionally known material such as JIS A1050, JIS A1100, JIS A3103, JIS A3005, etc. should be used as appropriate. I can do it. Moreover, the thickness of the aluminum support body used for this invention is about 0.1 mm-about 0.6 mm. This thickness can be appropriately changed depending on the size of the printing press, the size of the printing plate, and the purpose.
[0024]
(Graining treatment)
The aluminum support is preferably grained to a more preferable shape in addition to the anodizing treatment. Examples of the graining method include mechanical graining, chemical etching, and electrolytic grain as disclosed in JP-A-56-28893. In addition, the electrochemical graining method that electrochemically grains in hydrochloric acid or nitric acid electrolyte solution, and the wire brush grain method in which the aluminum surface is scratched with a metal wire, and the ball that makes the aluminum surface grainy with a polishing ball and an abrasive. A mechanical graining method such as a grain method or a brush grain method in which the surface is grained with a nylon brush and an abrasive can be used, and the above graining methods can be used alone or in combination.
[0025]
Among them, the method of making a grainy surface usefully used in the present invention is an electrochemical method of chemically graining in a hydrochloric acid or nitric acid electrolyte, and a suitable quantity of electricity is 50C / dm²~ 1000C / dm²Range. More specifically, in an electrolyte containing 0.1 to 50% hydrochloric acid or nitric acid, temperature 20 to 100 ° C., time 1 second to 30 minutes, current density 1 to 200 A / dm.²It is performed using direct current or alternating current under the following conditions. Electrochemical roughening is preferable in terms of improving adhesion between the photosensitive layer and the substrate because it is easy to impart fine irregularities to the surface.
[0026]
By this roughening, craters or honeycomb-like pits having an average diameter of about 0.5 to 20 μm can be generated on the aluminum surface at an area ratio of 30 to 100%. The pits provided here have the effect of making the non-image area of the printing plate less soiled and improving the printing durability. In the electrochemical treatment, an amount of electricity necessary for providing sufficient pits on the surface, that is, the product of the current and the time during which the current is passed is an important condition in the electrochemical roughening. From the viewpoint of energy saving, it is desirable that sufficient pits can be formed with a smaller amount of electricity. As the surface roughness after the roughening treatment, Ra = 0.2 to 0.7 μm is preferable.
[0027]
It is preferable that the aluminum support optionally subjected to the graining treatment is further chemically etched with an acid or an alkali. When an acid is used as an etching agent, it takes time to destroy the fine structure, which is disadvantageous when the present invention is applied industrially, but it can be improved by using an alkali as the etching agent. Examples of the alkali agent suitably used in the present invention include caustic soda, sodium carbonate, sodium aluminate, sodium metasilicate, sodium phosphate, potassium hydroxide, lithium hydroxide, and the like. The concentration of the alkali agent and the treatment temperature are preferable. The ranges are 1 to 50% and 20 to 100 ° C., respectively, and the dissolution amount of Al is 5 to 20 g / m.^ThreeThe conditions are as follows. Pickling is performed to remove dirt (smut) remaining on the surface after etching. As the acid used, nitric acid, sulfuric acid, phosphoric acid, chromic acid, hydrofluoric acid, borohydrofluoric acid and the like are used. In particular, as a method for removing smut after the electrochemical surface roughening treatment, contact with 15 to 65 mass% sulfuric acid at a temperature of 50 to 90 ° C. as described in JP-A-53-12739 is preferable. And the alkali etching method described in Japanese Patent Publication No. 48-28123.
[0028]
(Anodizing treatment)
The aluminum support optionally treated as described above in the method of the present invention is preferably anodized before being fluorinated so as to have a certain fluorination rate. The anodizing treatment can be performed by a method conventionally used in this field. Specifically, sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulfamic acid, benzene sulfonic acid, etc. alone or in combination of two or more of these are used to support aluminum when direct current or alternating current is applied to aluminum in an aqueous solution or non-aqueous solution. An anodized film can be formed on the body surface. In this case, the electrolyte solution may of course contain at least components normally contained in at least an Al alloy plate, an electrode, tap water, groundwater and the like. Further, the second and third components may be added. The second and third components here are, for example, metal ions such as Na, K, Mg, Li, Ca, Ti, Al, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, ammonium ions, and the like. Cation, nitrate ion, carbonate ion, chloride ion, phosphate ion, fluorine ion, sulfite ion, titanate ion, silicate ion, shelf acid ion, etc., and the concentration is O-10000ppm It may be included. The conditions of the anodizing treatment vary depending on the electrolyte used, and thus cannot be determined unconditionally. In general, the concentration of the electrolyte is 1 to 80%, the solution temperature is -5 to 70 ° C., and the current density is 0.7. 5-60A / dm²A voltage of 1 to 100 V and an electrolysis time of 10 to 200 seconds are suitable. Among these anodizing treatments, the method of anodizing at a high current density in a sulfuric acid electrolyte solution described in British Patent 1,412,768 is particularly preferable. In the present invention, the anodized film is 0.5 to 20 g / m.²Preferably, 0.5 g / m²If it is below, the plate is easily scratched, 20 g / m²The above requires a lot of electric power for manufacturing, which is economically disadvantageous. Preferably 1.0 to 10 g / m²It is. More preferably, 1.5-6 g / m²It is.
[0029]
(Middle layer)
In the present invention, a positive photosensitive layer can be directly provided on the aluminum support having the above-mentioned constant fluorination rate. If necessary, an intermediate layer is provided on the support, and each intermediate layer is provided on each intermediate layer. A positive photosensitive layer can also be provided.
[0030]
Examples of the method of providing the intermediate layer include, but are not particularly limited to, immersion treatment with a solution, spray treatment, coating treatment, vapor deposition treatment, sputtering, ion plating, thermal spraying, and plating. As a specific treatment method, for example, a group consisting of at least one amino group, a carboxyl group and a salt group thereof, and a sulfo group and a salt group disclosed in JP-A-60-149491 is selected. And a layer made of a compound having at least one group, selected from compounds having at least one amino group and at least one hydroxyl group, and salts thereof disclosed in JP-A-60-232998 A layer comprising a compound, a layer containing a phosphate disclosed in JP-A-62-19494, and at least one monomer unit having a sulfo group disclosed in JP-A-59-101651. The method of providing the layer etc. which consist of a high molecular compound contained in a molecule | numerator as a unit by coating is mentioned. In addition, phosphonic acids having an amino group such as carboxymethylcellulose, dextrin, gum arabic, 2-aminoethylphosphonic acid, phenylphosphonic acid, naphthylphosphonic acid, alkylphosphonic acid, glycerophosphonic acid, methylene which may have a substituent Organic phosphonic acids such as diphosphonic acid and ethylenediphosphonic acid, optionally substituted organic phosphoric esters such as phenylphosphoric acid, naphthylphosphoric acid, alkylphosphoric acid and glycerophosphoric acid, may have a substituent From organic phosphinic acids such as phenylphosphinic acid, naphthylphosphinic acid, alkylphosphinic acid and glycerophosphinic acid, amino acids such as glycine and β-alanine, and hydrochlorides of amines having hydroxyl groups such as hydrochloride of triethanolamine To be elected There is also a method of providing a compound layer.
[0031]
Further, a silane coupling agent having an unsaturated group may be applied, for example, N-3- (acryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, (3-acryloxypropyl) dimethyl. Methoxysilane, (3-acryloxypropyl) methyldimethoxysilane, (3-acryloxypropyl) trimethoxysilane, 3- (N-allylamino) propyltrimethoxysilane, allyldimethoxysilane, allyltriethoxysilane, allyltrimethoxysilane 3-butenyltriethoxysilane, 2- (chloromethyl) allyltrimethoxysilane, methacrylamidepropyltriethoxysilane, N- (3-methacryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, (methacrylic) Loxydimethyl) dimethylethoxy Silane, methacryloxymethyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxypropyldimethylethoxysilane, methacryloxypropyldimethylmethoxysilane, methacryloxypropylmethyldiethoxysilane, methacryloxypropylmethyldimethoxysilane, methacryloxypropylmethyltri Ethoxysilane, methacryloxypropylmethyltrimethoxysilane, methacryloxypropyltris (methoxyethoxy) silane, methoxydimethylvinylsilane, 1-methoxy-3- (trimethylsiloxy) butadiene, styrylethyltrimethoxysilane, 3- (N-styrylmethyl) -2-aminoethylamino) -propyltrimethoxysilane hydrochloride, vinyldimethylethoxysilane, vinyldiphenyl ester Xysilane, vinylmethyldiethoxysilane, vinylmethyldimethoxysilane, O- (vinyloxyethyl) -N- (triethoxysilylpropyl) urethane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltri-t-butoxysilane, vinyltriisopropoxy Examples include silane, vinyltriphenoxysilane, vinyltris (2-methoxyethoxy) silane, and diallylaminopropylmethoxysilane. Among these, a coupling agent containing an acryloyl group, a methacryloyl group, a vinyl group, or an allyl group is preferable, but a coupling agent containing a methacryloyl group or an acryloyl group in which the reactivity of an unsaturated group is particularly fast is particularly preferable. Further, an intermediate layer of a polymer compound having an acid group and an onium group described in JP-A No. 11-109637 can be more suitably used.
[0032]
(Intermediate layer of polymer compound having acid group and onium group)
As the polymer compound used for forming the intermediate layer, a polymer compound having an acid group or having a component having an onium group together with a component having an acid group is more preferably used. As the acid group of the constituent component of the polymer compound, an acid group having an acid dissociation index (pKa) of 7 or less is preferable, more preferably —COOH, —SO._ThreeH, -OSO_ThreeH, -PO_ThreeH₂, -OPO_ThreeH₂, -CONHSO₂, -SO₂NHSO₂-, Particularly preferably -COOH. A preferred component having an acid group is a polymerizable compound represented by the following general formula (1) or general formula (2).
[0033]
[Chemical 1]

[0034]
In the formula, A represents a divalent linking group. B represents an aromatic group or a substituted aromatic group. D and E each independently represent a divalent linking group. G represents a trivalent linking group. X and X ′ each independently represent an acid group having a pKa of 7 or less, or an alkali metal salt or ammonium salt thereof. R represents a hydrogen atom, an alkyl group or a halogen atom. a, b, d and e each independently represents 0 or 1; t is an integer of 1 to 3.
[0035]
More preferably, A represents -COO- or -CONH-, B represents a phenylene group or a substituted phenylene group, and the substituent is a hydroxyl group, a halogen atom or an alkyl group. D and E are each independently an alkylene group or a molecular formula of C_nH_2nO, C_nH_2nS or C_nH_{2n + 1}A divalent linking group represented by N is represented. G has the molecular formula C_nH_2n-1, C_nH_2n-1O, C_nH_2n-1S or C_nH_2nRepresents a trivalent linking group represented by N; However, n represents the integer of 1-12 here. X and X ′ each independently represents carboxylic acid, sulfonic acid, phosphonic acid, sulfuric acid monoester or phosphoric acid monoester. R represents a hydrogen atom or an alkyl group. a, b, d and e each independently represent 0 or 1, but a and b are not 0 at the same time.
[0036]
Among the constituents having an acid group, a compound represented by the general formula (1) is particularly preferable. B represents a phenylene group or a substituted phenylene group, and the substituent is a hydroxyl group or an alkyl group having 1 to 3 carbon atoms. . D and E each independently represent an alkylene group having 1 to 2 carbon atoms or an alkylene group having 1 to 2 carbon atoms linked by an oxygen atom. R represents a hydrogen atom or a methyl group. X represents a carboxylic acid group. a is 0 and b is 1.
[0037]
Specific examples of the component having an acid group are shown below. However, the present invention is not limited to this specific example. Acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, itaconic acid, maleic acid, maleic anhydride and the like are listed, and the following are further listed.
[0038]
[Chemical 2]

[0039]
[Chemical Formula 3]

[0040]
[Formula 4]

[0041]
You may combine the structural component which has the above acid groups 1 type, or 2 or more types.
Moreover, what is preferable as an onium group as a constituent component of the polymer compound used for forming the intermediate layer is an onium group composed of a group V or group VI atom in the periodic table, more preferably a nitrogen atom or a phosphorus atom. Alternatively, it is an onium group composed of a sulfur atom, and particularly preferably an onium group composed of a nitrogen atom. The polymer compound is preferably a polymer whose main chain structure is vinyl polymer such as acrylic resin, methacrylic resin or polystyrene, urethane resin, polyester or polyamide. Among these, vinyl polymers such as acrylic resin, methacrylic resin, and polystyrene are more preferable for the main chain structure. A particularly preferable polymer compound is a polymer in which a constituent component having an onium group is a polymerizable compound represented by the following general formula (3), general formula (4), or general formula (5).
[0042]
[Chemical formula 5]

[0043]
In the formula, J represents a divalent linking group. K represents an aromatic group or a substituted aromatic group. M independently represents a divalent linking group. Y represents a group V atom in the periodic table, and Y ′ represents a group VI atom in the periodic table. Z^-Represents a counter anion. R ′ represents a hydrogen atom, an alkyl group or a halogen atom. R '₁, R '₂, R '_Three, R '_FiveEach independently represents a hydrogen atom or optionally an alkyl group, an aromatic group or an aralkyl group to which a substituent may be bonded;_FourRepresents an alkylidine group or a substituted alkylidine, R ′₁And R '₂Or R '_FourAnd R '_FiveMay be bonded to each other to form a ring. j, k, and m each independently represents 0 or 1. u represents an integer of 1 to 3.
[0044]
More preferably, among the components having an onium group, J represents —COO— or —CONH—, K represents a phenylene group or a substituted phenylene group, and the substituent is a hydroxyl group, a halogen atom or an alkyl group. M is an alkylene group or the molecular formula is C_nH_2nO, C_nH_2nS or C_nH_{2n + 1}A divalent linking group represented by N is represented. However, n represents the integer of 1-12 here. Y represents a nitrogen atom or a phosphorus atom, and Y ′ represents a sulfur atom. Z^-Is halogen ion, PF₆ ^-, BF_Four ^-Or R '₆SO_Three ^-Represents. R '₆Represents a hydrogen atom or an alkyl group. R '₁, R '₂, R '_Three, R '_FiveEach independently represents a hydrogen atom or an optionally substituted alkyl group, aromatic group or aralkyl group to which a substituent may be bonded, and R ′_FourRepresents an alkylidine group having 1 to 10 carbon atoms or a substituted alkylidine, R ′₁And R '₂Or R '_FourAnd R '_FiveMay be bonded to each other to form a ring. j, k, and m each independently represent 0 or 1, but j and k are not 0 at the same time.
[0045]
Particularly preferably among the components having an onium group, K represents a phenylene group or a substituted phenylene group, and the substituent is a hydroxyl group or an alkyl group having 1 to 3 carbon atoms. M represents an alkylene group having 1 to 2 carbon atoms or an alkylene group having 1 to 2 carbon atoms linked by an oxygen atom. Z^-Is chloride ion or R '₆SO_Three ^-Represents. R '₆Represents a hydrogen atom or a methyl group. j is 0 and k is 1.
[0046]
Specific examples of components having an onium group are shown below. However, the present invention is not limited to this specific example.
[0047]
[Chemical 6]

[0048]
[Chemical 7]

[0049]
The polymer compound used for forming the intermediate layer preferably contains 1 mol% or more, preferably 5 mol% or more of the constituent component having an onium group as described above. When the component having an onium group is contained in an amount of 1 mol% or more, the adhesion is further improved. Moreover, you may combine the structural component which has onium group 1 type, or 2 or more types. Furthermore, the polymer compound used for forming the intermediate layer may be used by mixing two or more compounds having different constituent components, composition ratios or molecular weights.
[0050]
In the polymer compound having an onium group together with the acid group, the component having an acid group is contained in an amount of 20 mol% or more, preferably 40 mol% or more, and the component having an onium group is contained in an amount of 1 mol% or more, preferably It is desirable to contain 5 mol% or more. When the component having an acid group is contained in an amount of 20 mol% or more, dissolution and removal during alkali development is further promoted, and the adhesiveness is further improved by the synergistic effect of the acid group and the onium group. Further, it goes without saying that in the polymer compound having both an onium group and an acid group, two or more types having different constituent components, composition ratios or molecular weights may be used in combination. Below, the typical example of the high molecular compound which has an acid group with said onium group is shown. The composition ratio of the polymer structure represents a mole percentage.
[0051]
[Chemical 8]

[0052]
[Chemical 9]

[0053]
Embedded image

[0054]
Embedded image

[0055]
In general, any of the polymer compounds having an acid group or having an onium group together with an acid group used for forming the intermediate layer as described above can be produced by using a radical chain polymerization method (“Textbook of Polymer Science "3rd ed, (1984) FW Billmeyer, A Wiley-Interscience Publication). Further, the molecular weight of these polymer compounds may be in a wide range, but when measured using a light scattering method, the weight average molecular weight (Mw) is preferably 500 to 2,000,000. More preferably, it is in the range of 1,000,000 to 600,000. The amount of the unreacted monomer contained in the polymer compound may be in a wide range, but is preferably 20% by weight or less, and more preferably 10% by weight or less. In addition, as a typical example of a polymer compound having an onium group together with an acid group, the above-described copolymer of p-vinylbenzoic acid and vinylbenzyltrimethylammonium chloride (No. 1 in Table 1) is taken as an example. Therefore, the synthesis example is as follows. 146.9 g (0.99 mol) of p-vinylbenzoic acid [made by Hokuko Chemical Co., Ltd.], 44.2 g (0.21 mol) of vinylbenzyltrimethylammonium chloride and 446 g of 2-methoxyethanol are placed in a 1 L three-necked flask. The mixture was heated and kept at 75 ° C. with stirring under a nitrogen stream. Next, 2.76 g (12 mmol) of dimethyl 2,2-azobis (isobutyrate) was added and stirring was continued. Two hours later, 2.76 g (12 mmol) of dimethyl 2,2-azobis (isobutyrate) was added. Further, 2.76 g (12 mmol) of dimethyl 2,2-azobis (isobutyrate) was added after 2 hours. After stirring for 2 hours, the mixture was allowed to cool to room temperature. The reaction mixture was poured into 12 L of ethyl acetate with stirring. The precipitated solid was collected by filtration and dried. The yield was 189.5g. The obtained solid was subjected to molecular weight measurement by a light scattering method, and as a result, the weight average molecular weight (Mw) was 32,000. Other polymer compounds can be synthesized by the same method.
[0056]
The intermediate layer having an acid group and an onium group includes the above-described nitrous acid or nitrite containing a polymer compound having an acid group or having an onium group together with the acid group (hereinafter simply referred to as “polymer compound”). It is coated by various methods on an aluminum support that has been treated with an aqueous solution and optionally hydrophilized. One of the methods generally employed for providing the intermediate layer is to dissolve a polymer compound in an organic solvent such as methanol, ethanol, methyl ethyl ketone, or a mixed solvent thereof, or a mixed solvent of these organic solvent and water. The solution is applied to an aluminum support and dried, and the other is an organic solvent such as methanol, ethanol, methyl ethyl ketone or a mixed solvent thereof, or a mixed solvent of these organic solvent and water. In this method, an aluminum support is immersed in a solution in which a molecular compound is dissolved to adsorb the polymer compound, and then washed with water and dried. In the former method, a solution of a polymer compound having a concentration of 0.005 to 10% by weight can be applied by various methods. For example, any method such as bar coater coating, spin coating, spray coating, or curtain coating may be used. In the latter method, the concentration of the solution is 0.01 to 20% by weight, preferably 0.05 to 5% by weight, the immersion temperature is 20 to 90 ° C, preferably 25 to 50 ° C, and the immersion time. Is 0.1 second to 20 minutes, preferably 2 seconds to 1 minute.
[0057]
Solutions of the above polymer compounds include basic substances such as ammonia, triethylamine and potassium hydroxide, inorganic acids such as hydrochloric acid, phosphoric acid, sulfuric acid and nitric acid, organic sulfonic acids such as nitrobenzene sulfonic acid and naphthalene sulfonic acid, phenyl The pH is adjusted with various organic acidic substances such as organic phosphonic acids such as phosphonic acid, organic carboxylic acids such as benzoic acid, coumaric acid and malic acid, and organic acid chlorides such as naphthalenesulfonyl chloride and benzenesulfonyl chloride. -12, more preferably in the range of pH = 0-5. A yellow dye can also be added to improve the tone reproducibility of the photosensitive lithographic printing plate. The coating amount after drying of the polymer compound is 2 to 100 mg / m.²Is suitable, preferably 5 to 50 mg / m²It is. The coating amount is 2 mg / m²If it is less, sufficient effects cannot be obtained. 100 mg / m²Even more is the same.
[0058]
In addition, the sol-gel coating treatment described in JP-A-5-50779, the phosphonic acid coating treatment described in JP-A-5-246171, and the backcoat described in JP-A-6-234284, JP-A-6-191173, and JP-A-6-230563 A method of treating a material by coating, a treatment of phosphonic acids described in JP-A-6-262287, a coating treatment shown in JP-A-6-297875, a method of anodizing treatment by the method described in JP-A-10-109480, and Japanese Patent Application No. 10 -252078 and Japanese Patent Application No. 10-253411 may be performed by any method such as an immersion treatment method.
[0059]
(Positive photosensitive layer)
The following positive photosensitive layer is provided on a support having a certain fluorination rate, which is optionally anodized or roughened, and optionally provided with an intermediate layer.
[0060]
The positive photosensitive layer is provided by dissolving a positive photosensitive composition in a suitable solvent or the like and coating it on the support. As such a positive photosensitive composition, any one can be used as long as the solubility in the developer or the swelling property changes before and after exposure. Hereinafter, although a typical positive photosensitive composition is demonstrated, this invention is not limited by this.
[0061]
(Positive photosensitive compound)
Examples of the photosensitive compound in the positive photosensitive composition include an o-quinonediazide compound, and a typical example thereof is an o-naphthoquinonediazide compound. The o-naphthoquinonediazide compound is preferably an ester of 1,2-diazonaphthoquinonesulfonic acid chloride and pyrogallol-acetone resin described in JP-B-43-28403.
[0062]
Other suitable o-quinonediazide compounds include 1,2-diazonaphthoquinonesulfonic acid chloride and phenol formaldehyde resin described in US Pat. Nos. 3,046,120 and 3,188,210. There is an ester with.
[0063]
Other useful o-naphthoquinonediazide compounds include those reported and known in numerous patents. For example, JP-A-47-5303, 48-63802, 48-63803, 48-96575, 49-38701, 48-13354, 37-18015, 41-41 No. 11222, No. 45-9610, No. 49-17748, JP-A-5-11444, JP-A-5-19477, JP-A-5-19478, JP-A-5-107755, US Pat. No. 2,797, No. 213, No. 3,454,400, No. 3,544,323, No. 3,573,917, No. 3,674,495, No. 3,785,825, British Patent No. 1,227,602, No. 1,251,345, No. 1,267,005, No. 1,329,888, No. 1,330,932, German Patent No. 854,890 Described in each publication or specification It can be given to.
[0064]
Furthermore, as another o-quinonediazide compound, an o-naphthoquinonediazide compound obtained by a reaction of a polyhydroxy compound having a molecular weight of 1,000 or less and 1,2-diazonaphthoquinonesulfonic acid chloride can also be used. For example, JP-A-51-139402, 58-150948, 58-203434, 59-165053, 60-112445, 60-134235, 60-163043, 61-118744. 62-10645, 62-10646, 62-153950, 62-178562, 64-76047, U.S. Pat.Nos. 3,102,809, 3,126,281, No. 3,130,047, No. 3,148,983, No. 3,184,310, No. 3,188,210, No. 4,639,406, etc. Can be mentioned.
[0065]
When synthesizing these o-naphthoquinonediazide compounds, it is preferable to react 0.2 to 1.2 equivalents of 1,2-diazonaphthoquinonesulfonic acid chloride with respect to the hydroxyl group of the polyhydroxy compound. More preferably, the reaction is carried out to ˜1.0 equivalent. As the 1,2-diazonaphthoquinonesulfonic acid chloride, 1,2-diazonaphthoquinone-5-sulfonic acid chloride is preferable, but 1,2-diazonaphthoquinone-4-sulfonic acid chloride can also be used. The obtained o-naphthoquinonediazide compound is a mixture of different positions and introduction amounts of 1,2-diazonaphthoquinonesulfonic acid ester groups, but all hydroxyl groups are converted to 1,2-diazonaphthoquinonesulfonic acid esters. The proportion of the compound in the mixture (the content of the completely esterified compound) is preferably 5 mol% or more, more preferably 20 to 99 mol%.
[0066]
In addition, as a photosensitive compound that acts positively without using an o-naphthoquinonediazide compound, for example, a polymer compound containing an o-nitrile carbinol ester group or a pyridinium group-containing compound described in Japanese Patent Publication No. 52-2696 (Such as JP-A-4-365049) and diazonium group-containing compounds (JP-A-5-249664, JP-A-6-83047, JP-A-6-324495, JP-A-7-72621, etc.) can also be used. . Further, a combination of a compound that generates an acid by photolysis (JP-A-4-121748, JP-A-4-365043, etc.) and a compound having a C—O—C group or a C—O—Si group that is dissociated by an acid Systems can also be used. For example, a combination of a compound that generates an acid upon photolysis and an acetal or O, N-acetal compound (Japanese Patent Laid-Open No. 48-89003), a combination of an ortho ester or an amide acetal compound (Japanese Patent Laid-Open No. 51-120714, etc.) ), A combination with a polymer having an acetal or ketal group in the main chain (Japanese Patent Laid-Open No. 53-133429, etc.), a combination with an enol ether compound (Japanese Patent Laid-Open No. 55-12995, Japanese Patent Laid-Open No. 4-19748, 6-230574, etc.), combinations with N-acyliminocarbon compounds (JP-A 55-126236, etc.), combinations with polymers having an ortho ester group in the main chain (JP-A 56-17345, etc.), silyl Combination with a polymer having an ester group (JP-A-60-10247, etc.), And combinations with silyl ether compounds (JP 60-37549, JP 60-12146, JP 63-236028, JP 63-236029, JP 63-276046, etc.), etc. Is mentioned. 10-50 mass% is suitable for the quantity of the photosensitive compound (including the above combinations) which acts on these positive types in the photosensitive composition, More preferably, it is 15-40 mass%.
[0067]
(Binder)
Although the o-quinonediazide compound alone can constitute the photosensitive layer, it is preferably used together with a resin soluble in alkaline water as a binder (binder). As such a resin soluble in alkaline water, there is a novolak resin having this property. For example, phenol formaldehyde resin, m-cresol formaldehyde resin, p-cresol formaldehyde resin, m- / p-mixed cresol formaldehyde resin, phenol / Cresol (formerly m-, p-, o- or m- / p- / o-mixed) cresol formaldehyde resin such as mixed formaldehyde resin. These alkaline soluble polymer compounds preferably have a weight average molecular weight of 500 to 100,000. In addition, resol type phenol resins are also preferably used, and phenol / cresol (m-, p-, o- or m- / p- / o-mixed) mixed formaldehyde resin is preferred, Phenol resins described in JP-A-61-217034 are preferred.
[0068]
Further, phenol-modified xylene resins, polyhydroxystyrene, polyhalogenated hydroxystyrene, acrylic resins containing phenolic hydroxyl groups as disclosed in JP-A-51-34711, JP-A-2-866 JP-A-7-28244, JP-A-7-36184, JP-A-7-36185, JP-A-7-248628, JP-A-7-261394, JP Various alkali-soluble polymer compounds such as vinyl resins having a structural unit described in JP-A-7-333839 can be contained. In particular, in a vinyl resin, a film-forming resin having at least one selected from the following alkali-soluble group-containing monomers (1) to (4) as a polymerization component is preferable.
[0069]
(1) N- (4-hydroxyphenyl) acrylamide or N- (4-hydroxyphenyl) methacrylamide, o-, m- or p-hydroxystyrene, o- or m-bromo-p-hydroxystyrene, o- or Acrylamides, methacrylamides, acrylates, methacrylates and bidroxystyrenes having an aromatic hydroxyl group such as m-chloro-p-hydroxystyrene, o-, m- or p-hydroxyphenyl acrylate or methacrylate (2) unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride and its half ester, itaconic acid, itaconic anhydride and its half ester,
[0070]
(3) N- (o-aminosulfonylphenyl) acrylamide, N- (m-aminosulfonylphenyl) acrylamide, N- (p-aminosulfonylphenyl) acrylamide, N- [1- (3-aminosulfonyl) naphthyl] acrylamide Acrylamides such as N- (2-aminosulfonylethyl) acrylamide, N- (o-aminosulfonylphenyl) methacrylamide, N- (m-aminosulfonylphenyl) methacrylamide, N- (p-aminosulfonylphenyl) methacryl Methacrylamides such as amide, N- [1- (3-aminosulfonyl) naphthyl] methacrylamide, N- (2-aminosulfonylethyl) methacrylamide, o-aminosulfonylphenyl acrylate, m-aminosulfonylphenol Unsaturated sulfonamides such as acrylic acid esters such as acrylate, p-aminosulfonylphenyl acrylate, 1- (3-aminosulfonylphenylnaphthyl) acrylate, o-aminosulfonylphenyl methacrylate, m-aminosulfonylphenyl methacrylate, p- Unsaturated sulfonamides such as methacrylic acid esters such as aminosulfonylphenyl methacrylate, 1- (3-aminosulfonylphenylnaphthyl) methacrylate, (4) phenylsulfonylacrylamide, which may have a substituent such as tosylacrylamide, and tosyl Phenylsulfonyl methacrylamide optionally having substituents such as methacrylamide.
[0071]
In addition to these alkali-soluble group-containing monomers, film-forming resins obtained by copolymerizing the monomers (5) to (14) described below are preferably used. (5) Acrylic acid esters and methacrylic acid esters having an aliphatic hydroxyl group, such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate, (6) methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate Amyl acrylate, hexyl acrylate, cyclohexyl acrylate, octyl acrylate, phenyl acrylate, benzyl acrylate, 2-chloroethyl acrylate, 4-hydroxybutyl acrylate, glycidyl acrylate, N-dimethylaminoethyl acrylate, etc. (Substitution) Acrylic acid ester, (7) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclomethacrylate Hexyl, octyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-chloroethyl, 4-hydroxybutyl methacrylate, glycidyl methacrylate, N- dimethyl (substituted) methacrylic acid esters such as aminoethyl methacrylate,
[0072]
(8) Acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, N-ethyl acrylamide, N-ethyl methacrylamide, N-hexyl acrylamide, N-hexyl methacrylamide, N-cyclohexyl acrylamide, N-cyclohexyl methacryl Amide, N-hydroxyethylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-phenylmethacrylamide, N-benzylacrylamide, N-benzylmethacrylamide, N-nitrophenylacrylamide, N-nitrophenylmethacrylamide, N Acrylamide or methacrylate such as ethyl-N-phenylacrylamide and N-ethyl-N-phenylmethacrylamide De, (9) ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, phenyl vinyl ether,
[0073]
(10) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate, vinyl benzoate, (11) styrenes such as styrene, α-methylstyrene, methylstyrene, chloromethylstyrene, (12) methyl vinyl ketone , Vinyl ketones such as ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone, (13) olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene, (14) N-vinyl pyrrolidone, N-vinyl carbazole, 4-vinyl Pyridine, acrylonitrile, methacrylonitrile, etc.
[0074]
These alkali-soluble polymer compounds preferably have a weight average molecular weight of 500 to 500,000. Such alkali-soluble polymer compounds may be used alone or in combination of two or more. Moreover, 80 mass% or less is suitable for the ratio for which this high molecular compound accounts in the photosensitive composition, Preferably it is 30-80 mass%, More preferably, it is 50-70 mass%. This range is preferable in terms of developability and printing durability.
[0075]
Furthermore, as described in US Pat. No. 4,123,279, phenol and formaldehyde having an alkyl group having 3 to 8 carbon atoms as a substituent, such as t-butylphenol formaldehyde resin and octylphenol formaldehyde resin. It is preferable to use a condensate with the above or an o-naphthoquinone diazide sulfonic acid ester of these condensates (for example, those described in JP-A No. 61-243446) in order to improve the oil sensitivity of the image.
[0076]
(Development accelerator)
In the photosensitive composition, it is preferable to add cyclic acid anhydrides, phenols and organic acids in order to increase sensitivity and improve developability. Examples of cyclic acid anhydrides include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and 3,6-endooxy-Δ4-tetrahydrophthalic anhydride described in US Pat. No. 4,115,128. Tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, α-phenylmaleic anhydride, succinic anhydride, pyromellitic anhydride and the like can be used. The phenols include bisphenol A, p-nitrophenol, p-ethoxyphenol, 2,4,4'-trihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 4-hydroxybenzophenone, 4,4 ', 4. ″ -Trihydroxy-triphenylmethane, 4,4 ′, 3 ″, 4 ″ -tetrahydroxy-3,5,3 ′, 5′-tetramethyltriphenylmethane and the like. Examples thereof include sulfonic acids, sulfinic acids, alkylsulfuric acids, phosphonic acids, phosphoric esters and carboxylic acids described in JP-A-60-88942 and JP-A-2-96755. P-toluenesulfonic acid, dodecylbenzenesulfonic acid, p-toluenesulfinic acid, ethyl sulfate, phenylphosphine Acid, phenylphosphinic acid, phenyl phosphate, diphenyl phosphate, benzoic acid, isophthalic acid, adipic acid, p-toluic acid, 3,4-dimethoxybenzoic acid, phthalic acid, terephthalic acid, 1,4-cyclohexene-2 2, 2-dicarboxylic acid, erucic acid, lauric acid, n-undecanoic acid, ascorbic acid, etc. The proportion of the cyclic acid anhydrides, phenols and organic acids in the photosensitive composition is 0. 05-15 mass% is preferable, More preferably, it is 0.1-5 mass%.
[0077]
(Development stabilizer)
Further, in the photosensitive composition, as described in Japanese Patent Application Laid-Open Nos. 62-251740 and 4-68355, in order to broaden processing stability (so-called development tolerance) with respect to development conditions. Nonionic surfactants, amphoteric surfactants such as those described in JP-A-59-121044 and JP-A-4-13149 can be added. Specific examples of the nonionic surfactant include sorbitan tristearate, sorbitan monopalmitate, sorbitan trioleate, stearic acid monoglyceride, polyoxyethylene sorbitan monooleate, polyoxyethylene nonylphenyl ether and the like. Specific examples of the amphoteric surfactant include alkyldi (aminoethyl) glycine, alkylpolyaminoethylglycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine and N-tetradecyl-N, N- Examples include betaine type (for example, trade name Amogen K, manufactured by Daiichi Kogyo Co., Ltd.) and alkyl imidazoline series (for example, trade name Levon 15, Sanyo Chemical Co., Ltd.). The proportion of the nonionic surfactant and amphoteric surfactant in the photosensitive composition is preferably 0.05 to 15% by mass, more preferably 0.1 to 5% by mass.
[0078]
(Print-out agent, dye, etc.)
In the photosensitive composition, a printing agent for obtaining a visible image immediately after exposure, a dye as an image coloring agent, other fillers, and the like can be added. As the dye, a cation having a basic dye skeleton described in JP-A-5-313359, an organic anion having 10 to 10 carbon atoms and having 1 to 3 hydroxyl groups as a sole exchange group And basic dyes consisting of salts of The addition amount is 0.2 to 5% by mass of the total photosensitive composition.
[0079]
Further, compounds that generate photodecompositions that interact with the dyes described in JP-A-5-313359 and change the color tone, such as JP-A-50-36209 (US Pat. No. 3,969,118), are disclosed. O-Naphthoquinonediazide-4-sulfonic acid halogenide described in JP-A-53-36223 (US Pat. No. 4,160,671), trihalomethyltricidine, JP-A-55- Various o-naphthoquinonediazide compounds described in 62444 (US Pat. No. 2,038,801), 2-trihalomethyl-5- 5 described in JP-A-55-77742 (US Pat. No. 4,279,982) Aryl 1,3,4-oxadiazole compounds and the like can be added. These compounds can be used alone or in combination. Of these compounds, a compound having absorption at 400 nm may be used as the yellow dye.
[0080]
In addition to the dyes described in JP-A-5-313359, other dyes can be used as image colorants. Examples of suitable dyes including salt-forming organic dyes include oil-soluble dyes and basic dyes. Specifically, Oil Green BG, Oil Blue BOS, Oil Blue # 603 (above, manufactured by Orient Chemical Industry Co., Ltd.), Victoria Pure Blue BOH, Victoria Pure Blue NAPS, Ethyl Violet 6HNAPS (above, Hodogaya Chemical Industry ( Co., Ltd.), rhodamine B (C145170B), malachite green (C142000), methylene blue (C152015) and the like.
[0081]
Further, a yellow dye represented by the following general formula [I], [II] or [III] and having an absorbance at 417 nm of 70% or more of the absorbance at 436 nm may be added to the photosensitive composition. it can.
[0082]
Embedded image

[0083]
In the formula [I], R¹And R²Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group or an alkenyl group. Also R¹And R²May form a ring. R^Three, R^Four, R^FiveEach independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. G¹, G²Each independently represents an alkoxycarbonyl group, aryloxycarbonyl group, acyl group, arylcarbonyl group, alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group or fluoroalkylsulfonyl group. G¹And G²May form a ring. R¹, R², R^Three, R^Four, R^Five, G¹, G²One or more of them have one or more sulfonic acid groups, carboxyl groups, sulfonamido groups, imide groups, N-sulfonylamido groups, phenolic hydroxyl groups, sulfonimide groups, or metal salts thereof, inorganic or organic ammonium salts. . Y is O, S, NR (R is a hydrogen atom, an alkyl group or an aryl group), Se, —C (CH_Three)₂A divalent atomic group selected from-and -CH = CH- is shown, and n1 represents 0 or 1.
[0084]
Embedded image

[0085]
In the formula [II], R⁶And R⁷Each independently represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, a heterocyclic group, a substituted heterocyclic group, an allyl group or a substituted allyl group, and R⁶And R⁷Together with the carbon atom to which it is attached may form a ring. n2 represents 0, 1 or 2. G^ThreeAnd G^FourEach independently represents a hydrogen atom, a cyano group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, an aryloxycarbonyl group, a substituted aryloxycarbonyl group, an acyl group, a substituted acyl group, an arylcarbonyl group, a substituted arylcarbonyl group, an alkylthio group, An arylthio group, an alkylsulfonyl group, an arylsulfonyl group, and a fluoroalkylsulfonyl group are represented. However, G^ThreeAnd G^FourAre not simultaneously hydrogen atoms. G^ThreeAnd G^FourMay form a ring composed of a nonmetallic atom together with the carbon atom to which it is bonded. R⁶, R⁷, G^Three, G^FourOne or more of them have one or more sulfonic acid groups, carboxyl groups, sulfonamido groups, imide groups, N-sulfonylamido groups, phenolic hydroxyl groups, sulfonimide groups, or metal salts thereof, inorganic or organic ammonium salts. .
[0086]
Embedded image

[0087]
In the formula [III], R⁸, R⁹, R^Ten, R¹¹, R¹², R¹³Each may be the same or different, a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an alkoxy group, a hydroxyl group, an acyl group, a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, a nitro group, Represents a carboxyl group, a chloro group and a bromo group.
[0088]
(Positive photosensitive layer formation, etc.)
The positive photosensitive layer can be obtained by dissolving the components of the above photosensitive compositions in a solvent that dissolves them and applying the solution on a support. Solvents used here include γ-butyrolactone, ethylene dichloride, cyclohexanone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2- Propyl acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide, dimethylacetamide, dimethylformamide, water, N-methylpyrrolidone, tetrahydrofurfuryl alcohol, acetone, diacetone alcohol, methanol, ethanol, isopropanol, diethylene glycol dimethyl ether, etc. These solvents can be used alone or in combination. The concentration (solid content) of the photosensitive composition component in the solution is suitably 2 to 50% by mass. The coating amount is 0.5 g / m²~ 4.0 g / m²Is preferred. 0.5g / m²If it is less, the printing durability deteriorates. 4.0g / m²If the amount is more than 1, the printing durability is improved, but the sensitivity is lowered. Moreover, the formation method of photosensitive layers, such as application | coating on the support body of the photosensitive composition solution, can be based on the conventionally well-known various methods.
[0089]
In the photosensitive composition, a surfactant for improving the coating method, for example, a fluorine-based surfactant described in JP-A-62-170950 can be added. A preferable addition amount is 0.01 to 1% by mass of the total photosensitive composition, and more preferably 0.05 to 0.5% by mass. In the lithographic printing plate obtained as described above, a printed material that is faithful to the original image film can be obtained. As a method for improving the burning blur, there is a method of making the surface of the photosensitive layer thus provided uneven. For example, as described in JP-A-61-258255, there is a method in which particles of several μm are added to a photosensitive composition solution and coated therewith. The feeling of roughness is not improved at all.
[0090]
(exposure)
In the present invention, a lithographic printing plate provided with a photosensitive layer is developed after image exposure. Examples of the active light source used for image exposure include a carbon arc lamp, a mercury lamp, a metal halide lamp, a xenon lamp, a tungsten lamp, and a chemical lamp. Examples of radiation include electron beams, X-rays, ion beams, and far infrared rays. Further, g-line, i-line, deep-UV light, and high-density energy beam (laser beam) are also used. Examples of the laser beam include helium / neon laser, argon laser, krypton laser, helium / cadmium laser, KrF excimer laser, semiconductor laser, and YAG laser.
[0091]
(Development processing)
Next, development processing in the method of the present invention will be described.
The developer used in the method of the present invention is one containing no silicate. What is preferable as such a developing solution is an alkaline aqueous solution substantially free of an organic solvent, specifically, NaOH, KOH, LiOH, tribasic sodium phosphate, dibasic sodium phosphate, triphosphoric acid. Aqueous solutions such as ammonium, dibasic ammonium phosphate, sodium carbonate, sodium bicarbonate, potassium carbonate, aqueous ammonia and the like are suitable. More preferred is a developer containing (a) at least one saccharide selected from non-reducing sugars and (b) at least one base and having a pH in the range of 9.0 to 13.5. Hereinafter, the developer will be described in detail. In the present specification, unless otherwise specified, the developing solution means a developing start solution (a developing solution in a narrow sense) and a developing replenisher.
[0092]
(Non-reducing sugar and base)
The developer is characterized in that the main components are at least one compound selected from non-reducing sugars and at least one base, and the pH of the solution is in the range of 9.0 to 13.5. Such non-reducing sugars are saccharides that do not have a free aldehyde group or ketone group and do not exhibit reducing properties, and are trehalose-type oligosaccharides in which reducing groups are bonded to each other, and glycosides in which a reducing group of saccharides and non-saccharides are bonded. It is classified into sugar alcohols reduced by hydrogenating the body and saccharides, and any of them is preferably used. Trehalose type oligosaccharides include saccharose and trehalose. Examples of glycosides include alkyl glycosides, phenol glycosides, mustard oil glycosides, and the like. Examples of the sugar alcohol include D, L-arabit, rebit, xylit, D, L-sorbit, D, L-mannit, D, L-exit, D, L-talit, zulsiit and allozulcit. Furthermore, maltitol obtained by hydrogenation of a disaccharide and a reduced form (reduced water candy) obtained by hydrogenation of an oligosaccharide are preferably used. Among these, sugar alcohol and saccharose are particularly preferred non-reducing sugars, and D-sorbite, saccharose, and reduced syrup are particularly preferred because they have a buffering action in an appropriate pH region and are inexpensive. These non-reducing sugars can be used singly or in combination of two or more, and the proportion of the non-reducing sugar in the developer is preferably 0.1 to 30% by mass, more preferably 1 to 20% by mass. Below this range, a sufficient buffering effect cannot be obtained, and when the concentration is above this range, it is difficult to achieve high concentration, and the problem of increased costs arises. In addition, when reducing sugar is used in combination with a base, there is a problem that the color changes to brown over time, the pH gradually decreases, and thus developability decreases.
[0093]
As the base combined with the non-reducing sugar, conventionally known alkali agents other than silicates can be used. For example, sodium hydroxide, potassium, lithium, trisodium phosphate, potassium, ammonium, disodium phosphate, potassium, ammonium, sodium carbonate, potassium, ammonium, sodium bicarbonate, potassium, ammonium Inorganic alkaline agents such as sodium borate, potassium, and ammonium. Monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropinolamine, diisopropanolamine Organic alkali agents such as ethyleneimine, ethylenediamine, and pyridine are also used. These alkali agents are used alone or in combination of two or more. Of these, sodium hydroxide and potassium are preferred. The reason is that the pH can be adjusted in a wide pH range by adjusting these amounts relative to the non-reducing sugar. Trisodium phosphate, potassium, sodium carbonate, potassium, and the like are also preferable because they have a buffering action. These alkali agents are added so that the pH of the developer is in the range of 9.0 to 13.5, and the addition amount is determined by the desired pH, the type and addition amount of the non-reducing sugar, and more preferable pH. The range is 10.0 to 13.2.
[0094]
Further, an alkaline buffer composed of a weak acid other than saccharides and a strong base can be used in combination with the developer. As the weak acid used as such a buffer, one having a pKa of 10.0 to 13.2 is preferable. Such a weak acid is selected from those described in IONISATION CONSTANTS OF ORGANIC ACIDS IN AQUEOUS SOLUTION published by Pergamon Press, for example, 2,2,3,3-tetrafluoropropanol-1 (pKa 12.74). , Alcohols such as trifluoroethanol (12.37) and trichloroethanol (12.24), aldehydes such as pyridine-2-aldehyde (12.68) and pyridine-4-aldehyde (12.05) , Salicylic acid (13.0), 3-hydroxy-2-naphthoic acid (12.84), catechol (12.6), gallic acid (12.4), sulfosalicylic acid (11.7) 3,4-dihydroxysulfonic acid (12.2), 3,4-dihydroxybenzoic acid (1.94), 1,2,4-trihydroxybenzene (11.82), high Loquinone (11.56), pyrogallol (11.34), o-cresol (10.33), resorcinol (11.27), p-cresol (10.27), m-cresol (10) .09) and other compounds having a phenolic hydroxyl group,
[0095]
2-butanone oxime (12.45), acetoxime (12.42), 1,2-cycloheptanedione dioxime (12.3), 2-hydroxybenzaldehyde oxime (12.10), dimethylglyoxime (11.9), ethanediamide dioxime (11.37), oximes such as acetophenone oxime (11.35), adenosine (12.56), inosine (12.5), guanine (same as above) 12.3), nucleic acid-related substances such as cytosine (12.2), hypoxanthine (12.1), xanthine (11.9), diethylaminomethylphosphonic acid (12.32), 1- Amino-3,3,3-trifluorobenzoic acid (12.29), isopropylidene diphosphonic acid (12.10), 1,1-ethylidene diphosphonic acid (11.54) 1,1-ethylidene diphosphonic acid 1-hydroxy (1.52), benzimidazole (12.86), thiobenzamide (12.8), picoline thioamide (12.55), barbituric acid (12) And weak acids such as .5).
[0096]
Of these weak acids, sulfosalicylic acid and salicylic acid are preferred. As the base to be combined with these weak acids, sodium hydroxide, ammonium, potassium and lithium are preferably used. These alkali agents are used alone or in combination of two or more. The above various alkali agents are used by adjusting the pH within a preferable range depending on the concentration and combination.
[0097]
(Surfactant)
Various surfactants and organic solvents can be added to the developer as needed for the purpose of promoting developability, dispersing development residue, and improving the ink affinity of the printing plate image area. Preferred surfactants include anionic, cationic, nonionic and amphoteric surfactants. Preferred examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene polystyryl phenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, glycerin fatty acid partial esters, sorbitan Fatty acid partial esters, pentaerythritol fatty acid partial esters, propylene glycol mono fatty acid esters, sucrose fatty acid partial esters, polyoxyethylene sorbitan fatty acid partial esters, polyoxyethylene sorbitol fatty acid partial esters, polyethylene glycol fatty acid esters, poly Glycerin fatty acid partial esters, polyoxyethylenated castor oil, polyoxyethylene glycerin fatty acid partial esters, fatty acids Ethanol amides, N, N-bis-2-hydroxyalkylamines, polyoxyethylene alkylamines, triethanolamine fatty acid esters, anionic surfactants such as trialkyl amine oxides,
[0098]
Fatty acid salts, abietic acid salts, hydroxyalkanesulfonic acid salts, alkanesulfonic acid salts, dialkylsulfosuccinic acid ester salts, linear alkylbenzenesulfonic acid salts, branched alkylbenzenesulfonic acid salts, alkylnaphthalenesulfonic acid salts, alkylphenoxypolyoxyethylene Propyl sulfonates, polyoxyethylene alkyl sulfophenyl ether salts, N-methyl-N-oleyl taurine sodium salt, N-alkyl sulfosuccinic acid monoamide disodium salt, petroleum sulfonates, sulfated beef oil, fatty acid alkyl esters Sulfates, alkyl sulfates, polyoxyethylene alkyl ether sulfates, fatty acid monoglyceride sulfates, polyoxyethylene alkylpheny Ether sulfates, polyoxyethylene styryl phenyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkylphenyl ether phosphates, styrene / maleic anhydride copolymers Partial saponified products of olefins, partially saponified products of olefin / maleic anhydride copolymers, anionic surfactants such as naphthalene sulfonate formalin condensates, quaternary ammonium salts such as alkylamine salts and tetrabutylammonium bromide , Cationic surfactants such as polyoxyethylene alkylamine salts, polyethylene polyamine derivatives, carboxybetaines, aminocarboxylic acids, sulfobetaines, aminosulfuric esters, imidazolines What amphoteric surfactants. Among the surfactants listed above, those having polyoxyethylene can be read as polyoxyalkylenes such as polyoxymethylene, polyoxypropylene and polyoxybutylene, and these surfactants are also included.
[0099]
A more preferred surfactant is a fluorosurfactant containing a perfluoroalkyl group in the molecule. Such fluorosurfactants include perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, anionic types such as perfluoroalkyl phosphates, amphoteric types such as perfluoroalkyl betaines, and perfluoroalkyltrimethylammonium salts. Cationic and perfluoroalkylamine oxides, perfluoroalkyl ethylene oxide adducts, perfluoroalkyl group and hydrophilic group-containing oligomers, perfluoroalkyl group and lipophilic group-containing oligomers, perfluoroalkyl groups, hydrophilic groups and lipophilic groups Nonionic types such as group-containing oligomers, perfluoroalkyl groups, and lipophilic group-containing urethanes can be mentioned. The above surfactants can be used alone or in combination of two or more, and are added to the developer in the range of 0.001 to 10% by mass, more preferably 0.01 to 5% by mass.
[0100]
(Development stabilizer)
Various development stabilizers are used in the developer. Preferred examples thereof include polyethylene glycol adducts of sugar alcohols described in JP-A-6-282079, tetraalkylammonium salts such as tetrabutylammonium hydroxide, phosphonium salts such as tetrabutylphosphonium bromide, and iodonium such as diphenyliodonium chloride. A salt is a preferred example. Furthermore, anionic surfactants or amphoteric surfactants described in JP-A-50-51324, water-soluble cationic polymers described in JP-A-55-95946, and JP-A-56-142528 are described. There are water-soluble amphoteric polyelectrolytes that have been described. Further, an organoboron compound to which an alkylene glycol is added as described in JP-A-59-84241, a polyoxyethylene / polyoxypropylene block polymerization type water-soluble surfactant as described in JP-A-60-111246, An alkylenediamine compound substituted with polyoxyethylene / polyoxypropylene disclosed in JP-A-60-129750, a polyethylene glycol having a weight average molecular weight of 300 or more described in JP-A-61-215554, and a cation described in JP-A-63-175858 And a water-soluble ethylene oxide addition compound obtained by adding 4 mol or more of ethylene oxide to an acid or alcohol disclosed in JP-A-2-39157, a water-soluble polyalkylene compound, and the like.
[0101]
(Organic solvent)
The developer is substantially free of an organic solvent, but an organic solvent is added if necessary. As such an organic solvent, those having a solubility in water of about 10% by mass or less are suitable, and are preferably selected from those having 5% by mass or less. For example, 1-phenylethanol, 2-phenylethanol, 3-phenyl-1-propanol, 4-phenyl-1-butanol, 4-phenyl-2-butanol, 2-phenyl-1-butanol, 2-phenoxyethanol, 2- Benzyloxyethanol, o-methoxybenzyl alcohol, m-methoxybenzyl alcohol, p-methoxybenzyl alcohol, benzyl alcohol, cyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol and 4-methylcyclohexanol, N-phenylethanol Examples thereof include amines and N-phenyldiethanolamine. The expression “substantially free of organic solvent” means that the content of the organic solvent is 5% by mass or less based on the total weight of the used solution. The amount used is closely related to the amount of surfactant used, and it is preferable to increase the amount of surfactant as the amount of organic solvent increases. This is because the amount of the surfactant is small, and when the amount of the organic solvent is large, the organic solvent is not completely dissolved, so that it is impossible to expect good developability.
[0102]
(Reducing agent)
A reducing agent can be further added to the developer. This prevents stains on the printing plate, and is particularly effective when developing a negative photosensitive lithographic printing plate containing a photosensitive diazonium salt compound. Preferable organic reducing agents include phenol compounds such as thiosalicylic acid, hydroquinone, metol, methoxyquinone, resorcin, and 2-methylresorcin, and amine compounds such as phenylenediamine and phenylhydrazine. More preferable inorganic reducing agents include sodium, potassium and ammonium salts of inorganic acids such as sulfurous acid, bisulfite, phosphorous acid, hydrogen phosphite, dihydrogen phosphite, thiosulfuric acid and dithionite. A salt etc. can be mentioned. Among these reducing agents, sulfites are particularly excellent in the antifouling effect. These reducing agents are preferably contained in the range of 0.05 to 5% by mass with respect to the developer at the time of use.
[0103]
(Organic carboxylic acid)
An organic carboxylic acid can also be added to the developer. Preferred organic carboxylic acids are aliphatic carboxylic acids and aromatic carboxylic acids having 6 to 20 carbon atoms. Specific examples of the aliphatic carboxylic acid include caproic acid, enanthylic acid, caprylic acid, lauric acid, myristic acid, palmitic acid and stearic acid, and particularly preferred are alkanoic acids having 8 to 12 carbon atoms. . Further, it may be an unsaturated fatty acid having a double bond in the carbon chain or a branched carbon chain. The aromatic carboxylic acid is a compound in which a carboxyl group is substituted on a benzene ring, naphthalene ring, anthracene ring, etc., specifically, o-chlorobenzoic acid, p-chlorobenzoic acid, o-hydroxybenzoic acid, p -Hydroxybenzoic acid, o-aminobenzoic acid, p-aminobenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 3 , 5-dihydroxybenzoic acid, gallic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 2-hydroxy-1-naphthoic acid, 1-naphthoic acid, 2-naphthoic acid, etc. Hydroxynaphthoic acid is particularly effective. The aliphatic and aromatic carboxylic acids are preferably used as sodium salts, potassium salts or ammonium salts in order to enhance water solubility. The content of the organic carboxylic acid in the developer is not particularly limited, but if it is less than 0.1% by mass, the effect is not sufficient, and if it is 10% by mass or more, the effect cannot be further improved. Dissolving may be hindered when using other additives. Therefore, a preferable addition amount is 0.1 to 10% by mass, and more preferably 0.5 to 4% by mass with respect to the developing solution at the time of use.
[0104]
(Other)
The developer may further contain a preservative, a colorant, a thickener, an antifoaming agent, a hard water softening agent, and the like, if necessary. Examples of water softeners include polyphosphoric acid and its sodium, potassium and ammonium salts, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, hydroxyethylethylenediaminetriacetic acid, nitrilotriacetic acid, and 1,2-diaminocyclohexanetetra Aminopolycarboxylic acids such as acetic acid and 1,3-diamino-2-propanoltetraacetic acid and their sodium, potassium and ammonium salts, aminotri (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylene Phosphonic acid), triethylenetetramine hexa (methylenephosphonic acid), hydroxyethylethylenediaminetri (methylenephosphonic acid) and 1 Hydroxyethane-1,1-diphosphonic acid and their sodium salts, potassium salts and ammonium salts.
[0105]
The optimum value of such a water softener varies depending on its chelating power, the hardness of the hard water used and the amount of hard water. % By mass, more preferably in the range of 0.01 to 0.5% by mass. If the addition amount is less than this range, the intended purpose is not sufficiently achieved. If the addition amount is more than this range, adverse effects on the image area such as color loss will occur. The remaining component of the developer is water. It is advantageous in terms of transportation that the developer is a concentrated solution having a water content less than that in use and is diluted with water when in use. In this case, the degree of concentration is appropriate such that each component does not cause separation or precipitation.
[0106]
(Development and post-processing)
The lithographic printing plate developed with a developer having such a composition is subjected to post-treatment with a washing water, a rinse solution containing a surfactant, a finisher mainly composed of gum arabic or starch derivatives, or a protective gum solution. . In the method of the present invention, these treatments can be used in various combinations for the post-treatment of the photosensitive lithographic printing plate. In recent years, automatic developing machines for photosensitive lithographic printing plates have been widely used in the plate making and printing industries in order to rationalize and standardize plate making operations. This automatic developing machine is generally composed of a developing section and a post-processing section, and is composed of an apparatus for conveying a photosensitive lithographic printing plate, each processing liquid tank and a spray device, and horizontally conveys the exposed photosensitive lithographic printing plate. However, each processing liquid pumped up by the pump is sprayed from the spray nozzle to develop and post-process. In addition, recently, a photosensitive lithographic printing plate is immersed in a processing liquid tank filled with processing liquid with a guide roll, etc., and developed, and a small amount of washing water is supplied to the plate surface after development. There is also known a method of washing with water and reusing the waste water as dilution water of the developer stock solution. In such automatic processing, each processing solution can be processed while being replenished with each replenisher according to the processing amount, operating time, and the like. In addition, a so-called disposable processing method in which processing is performed with a substantially unused processing solution can also be applied. The planographic printing plate obtained by such processing is loaded on an offset printing machine and used for printing a large number of sheets.
[0107]
【Example】
  EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples..
<How to make a support>
(A) After preparing an Al molten metal composed of the components shown in Table 1 and performing a molten metal treatment and filtration, an ingot having a thickness of 500 mm and a width of 1200 mm was created by a DC casting method, and the surface was chamfered by an average of 10 mm. After being scraped off with a mill, the temperature is maintained at 550 ° C. for about 5 hours. When the temperature falls to 400 ° C., a hot rolled plate is used to form a 2.7 mm-thick rolled plate, and heat treatment is performed using a continuous annealing machine. After carrying out at 500 degreeC, it finished in thickness 0.24mm by cold rolling. After making this aluminum plate width 1030mm, it processed continuously.
[0108]
[Table 1]

[0109]
(B) The surface of the aluminum plate was grained using a nylon brush and a 400 mesh Pamiston water suspension, and then thoroughly washed with water. Etching is performed by spraying at a caustic soda concentration of 26% by mass, an aluminum ion concentration of 6.5% by mass, and a temperature of 70 ° C.²Dissolved. Thereafter, washing with water was performed by spraying.
(C) A desmut treatment was performed by spraying with a 1% by weight aqueous solution of nitric acid having a temperature of 30 ° C. (including 0.5% by weight of aluminum ions), and then washed with water by spraying. The nitric acid aqueous solution used for the desmut was the waste liquid from the step of electrochemical surface roughening using alternating current in nitric acid aqueous solution.
[0110]
(D) An electrochemical surface roughening treatment was continuously performed using an alternating voltage of 60 Hz. The electrolytic solution at this time was a 1% by mass nitric acid aqueous solution (containing 0.5% by mass aluminum ions and 0.007% by mass ammonium ions) at a temperature of 50 ° C. The AC power source waveform is the waveform shown in FIG. 2. The time until the current value reaches a peak from zero is 2 msec, the duty ratio is 1: 1, trapezoidal rectangular wave AC is used, and the carbon electrode is the counter electrode and is electrochemical. A roughening treatment was performed. Ferrite was used for the auxiliary anode. Two electrolytic cells were used.
The current density is 30 A / dm at the peak current value.²The amount of electricity is 230 C / dm as the total amount of electricity when the aluminum plate is the anode.²Met. 5% of the current flowing from the power source was shunted to the auxiliary anode.
Then, water washing by spraying was performed.
[0111]
(E) The aluminum plate was etched at 70 ° C. at a caustic soda concentration of 26 mass% and an aluminum ion concentration of 6.5 mass%, and the aluminum plate was 1 g / m.²Dissolves and removes the smut component mainly composed of aluminum hydroxide generated when electrochemical roughening is performed using alternating current in the previous stage, dissolves the edge part of the generated pit, and smooths the edge part I made it. Then, it was washed with water with a spray.
(F) A desmut treatment by spraying was performed with a 25% by weight aqueous solution of sulfuric acid having a temperature of 60 ° C. (containing 0.5% by weight of aluminum ions), and then washing with water by spraying.
[0112]
(G) Using an anodic oxidation apparatus, sulfuric acid concentration 170 g / l (containing 0.5 mass% of aluminum ions), temperature 40 ° C., 30 A / dm²The anodic oxidation amount is 2.5 g / m.²After anodizing so as to become, it was washed with water by spraying. The substrate so far is designated as A.
Next, after processing with the aqueous solution containing the fluoride shown in Table 2, each substrate was prepared by washing with water.
[0113]
The fluorination rate of the obtained substrate surface was measured under the following conditions using the following apparatus.
Device name: PHI-5400MC (manufactured by ULVAC-PHI)
X-ray source: MgK_α(400W)
Pass energy: 71.55eV
Analysis area: 1.1mmφ
Photoelectron extraction angle: 45 degrees
[0114]
Next, on the substrate treated as described above, the following polymer compound was applied according to the following formulation and then dried at 80 ° C. for 15 seconds. The coating amount after drying is 6.5 mg / m₂Met. Next, the photosensitive layer was provided by applying the following photosensitive solution A. The photosensitive layer coating amount after drying is 1.3 g / m.²Met. In order to further shorten the vacuum contact time, a photosensitive lithographic printing plate was prepared by forming a mat layer by the method described in JP-B 61-28986.
[0115]
[Prescription]
High molecular compound (molecular weight Mw = 28,000): 0.1 g
Methanol: 100g
Pure water: 1g
[0116]
Embedded image

[0117]
[Photosensitive solution A]
Esterified product of 1,2-diazonaphthoquinone-5-sulfonyl chloride and pyrogallol-acetone resin (described in Example 1 of US Pat. No. 3,635,709) 0.8 g
binder
Novolac I (see the structural formula below) 1.5g
Novolac II (see the structural formula below) 0.2g
Resins III other than novolak (see structural formula below) 0.4 g
p-normal octylphenol-formaldehyde resin (described in US Pat. No. 4,123,279) 0.02 g
Naphthoquinone-1,2-diazide-4-sulfonic acid chloride 0.01 g
Tetrahydrophthalic anhydride 0.02g
Benzoic acid 0.02g
Pyrogallol 0.05g
4- [p-N, N-bis (ethoxycarbonylmethyl) aminophenyl] -2,6-bis (trichloromethyl) -S-triazine (hereinafter abbreviated as triazine A) 0.07 g
Victoria Pure Blue BOH (a dye made by changing the counter anion from Hodogaya Chemical Co., Ltd. to 1-naphthalenesulfonic acid) 0.045 g
F176PF (fluorinated surfactant, manufactured by Dainippon Ink & Chemicals, Inc.) 0.01 g
Methyl ethyl ketone 15g
1-methoxy-2-propanol 10g
[0118]
Embedded image

[0119]
The photosensitive lithographic printing plate thus prepared was image-exposed for 1 minute from a distance of 1 m by a 3 kW metal halide lamp, and using a developer processor A or B below, using a PS processor 900VR manufactured by Fuji Photo Film Co., Ltd. Developed at 30 ° C. for 12 seconds.
[0120]
Developer A (pH = 13):
5.1 parts by weight of D-sorbitol
Sodium hydroxide 1.1 parts by weight
Triethanolamine / ethylene oxide adduct (30 mol) 0.03 parts by weight
93.8 parts by weight of water Developer B:
[SiO₂] / [Na₂O] molar ratio 1.2, SiO₂ 100 parts by weight of 1.4% by weight aqueous sodium silicate solution
Ethylenediamine / ethylene oxide adduct (30 mol) 0.03 parts by weight
[0121]
The lithographic printing plate obtained by the development treatment as described above was measured for printing durability, stain resistance, residual color, residual film performance, residue and sludge. The results are shown in Table 2. The performance evaluation method is as follows.
[0122]
Printing durability: Using a printing machine Sprint manufactured by Komori Printing Co., Ltd., evaluation was made based on the number of printed sheets until normal printing was stopped. The greater the number of printed sheets, the better the printing durability.
[0123]
Dirtiness: Printing is stopped after printing 1,000 sheets with a SOR-M printer manufactured by Heidelberg, and left for 30 minutes. Thereafter, it was attached again to the printing press and printed 100 sheets. At that time, the number of inks on the non-image area was evaluated. The smaller the number, the better the dirt performance.
[0124]
Sludge: 10m plate per liter of developer²After the treatment, the degree of dissolution of the oxide film in the alkaline developer at this time was determined based on the state of residue remaining in the developer.
○ ... No waste or sludge
Δ: Dregs and sludge are observed, but not as many as x.
× ・ ・ ・ Large amount of waste and sludge
[0125]
Residual film: The difference (ΔD) between the reflection optical density at 280 nm of light in the non-image area of the lithographic printing plate after development and the reflection optical density at 280 nm on the support surface before coating of the photosensitive layer was measured. The smaller the ΔD, the better the remaining film performance.
[0126]
Residual color: The difference (ΔD) between the reflection optical density at 600 nm light of the non-image portion of the lithographic printing plate after development and the reflection optical density at 600 nm light on the support surface before coating of the photosensitive layer was measured. The smaller the ΔD, the better the remaining color performance.
[0127]
  As is apparent from the table below, a lithographic printing plate obtained by developing a photosensitive lithographic printing plate having a fluorination rate of the support in the range of 0.3 to 0.9 with a developer containing no silicate (Reference Examples 1-6 and Example 7) Was excellent in dirt, printing durability, residual color, and residual film performance, and no debris or sludge was generated in the developer. On the other hand, all of the substrates shown in Comparative Examples (1 to 4) were not satisfactory because they were not compatible with dirt, printing durability, residual color, residual film, and sludge.
[0128]
[Table 2]

[0129]
【The invention's effect】
According to the method for producing a lithographic printing plate of the present invention, a positive photosensitive lithographic printing plate having good residual color, residual film performance, stain performance and printing durability can be obtained, and dregs and sludge during development can be suppressed.

Claims (2)

A lithographic printing plate having a positive photosensitive layer provided on an aluminum support having a surface that is treated with an aqueous solution containing an inorganic fluorine compound and polyvinylphosphonic acid and satisfying the relationship represented by the following formula: A method for producing a lithographic printing plate, characterized by being developed with
0.30 ≦ A / (A + B) ≦ 0.90 (wherein A represents the peak area (counts · eV / sec) of fluorine (1S) obtained by measurement using X-ray photoelectron spectroscopy, B represents the peak area (counts · eV / sec) of aluminum (2P) obtained by measurement using X-ray photoelectron spectroscopy.   The developer containing no silicate contains (a) at least one saccharide selected from non-reducing sugars and (b) at least one base (excluding silicate), and has a pH of 9.0 to 13.5. The method for producing a lithographic printing plate according to claim 1, wherein the developer is in the range.