JP2004347983A - Developing solution for photosensitive composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a developing solution for a photosensitive composition, the solution to be used for developing a photoresist or the like and suppressing the activity of an alkali component without using an inorganic salt. <P>SOLUTION: The developing solution for a photosensitive composition contains an alkali agent and a water-soluble polymer having 10 or more structures expressed by general formula (I), wherein R<SB>1</SB>represents an ethylene group or a hydroxypropylene group, and/or by general formula (II), wherein R<SB>2</SB>represents an ethylene group or hydroxypropylene group, and having ≥600 molecular weight. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

Ｒ_１はエチレン基、ヒドロキシプロピレン基を表す。
一般式（ＩＩ）
【化４】

Ｒ_２はエチレン基、ヒドロキシプロピレン基を表す。
本発明の感光性組成物用現像液は、一般式（Ｉ）及び又は一般式（ＩＩ）で表される構造を１０個以上持つ分子量６００以上の水溶性高分子とアルカリ剤を含むことを特徴とする。
本発明の感光性組成物用現像液は、水溶性高分子の末端基は水素原子および又は炭素数５以下の直鎖、または分岐アルキル基であることを特徴とする。
本発明の感光性組成物用現像液は、一般式（Ｉ）及び又は一般式（ＩＩ）で表される構造が重量比で７０％以上である水溶性高分子を、０．２〜８重量％含む事を特徴とする
本発明の感光性組成物用現像液は、一般式（Ｉ）及び又は一般式（ＩＩ）で表される単位構造とアルカリ剤のモル比が、アルカリを１として０．３〜３であることを特徴とする。
本発明の感光性組成物用現像液は、芳香族スルホン酸のホルマリン縮合物を含有する事を特徴とする。
本発明の感光性組成物用現像液は、有機ホスホン酸類を含有する事を特徴とする。
本発明の感光性組成物用現像補充液は、一般式（Ｉ）及び又は一般式（ＩＩ）で表される単位構造とアルカリ剤のモル比が感光性組成物用現像液と同等若しくは単位構造に対するアルカリ剤のモル比が処理液よりも高いことを特徴とする。
感光性組成物用現像液及び補充液等の廃液処理に酸性物質を粉体で供給することを特徴とする。
【００１３】
【発明の実施の形態】以下本発明の実施の形態を詳細に説明する。本発明に使用する一般式（Ｉ）及び一般式（ＩＩ）の具体的化合物の例を挙げる。但し、本発明はこれらの化合物に限定されない。
一般式（Ｉ）
【化５】

Ｒ_１はエチレン基、ヒドロキシプロピレン基を表す。
一般式（ＩＩ）
【化６】

Ｒ_２はエチレン基、ヒドロキシプロピレン基を表す。
以上の例として、表１に化合物を示すが、本発明はこれに限定されるものではない。
【表１】

【００１４】
この単位構造を含む水溶性高分子は、６００以上の分子量を持つ事が望ましい。６００以上であれば、感光性組成物を保護し、アルカリ剤から、画像部を保護する事が出来る。より好ましくは１０００以上が好ましく、画像部と非画像部の境がくっきりした処理剤が可能となる。また、水溶性高分子中にこの単位構造が７０重量％以上含まれる事が望ましい。単位構造が７０重量％以上であれば、高アルカリ性の現像液中にあっても感光性樹脂を保護し、画像部の感光性樹脂層の膜減りを抑えることが可能になる。
【００１５】
特に、水溶性高分子の末端基に付くアルキル基が炭素数５以下であれば、親水性高分子が親油性の画像部に強固に吸着し、現像〜水洗工程を過ぎた後まで版面に残り、画像部のインキとの親和性（所謂インキ着肉性）を低下させる事が無く、良好な印刷が可能に出来る。
本発明に使用する親水性高分子のうち一般式（ＩＩ）を持つものは、感光性平版の基材であるアルミニウムが現像液中で強アルカリによって溶解される事を抑え、現像液の活性をより安定的なものに出来る。
【００１６】
一般式（Ｉ）と一般式（ＩＩ）で表される単位構造とアルカリ剤の比率としては、アルカリ剤１モルに対して単位構造０．３〜４モルが望ましく、更に望ましくは０．５〜２モルが望ましい。この場合アルカリ剤とは、他の化合物と塩の形態を取るものを除きフリーの状態の物を１モルと算出するものとする。
単位構造はアルカリ可溶性の樹脂と結びつき画像部の溶解を防ぐ事が出来る。この為、単位構造とアルカリ成分の比率がこの範囲内であれば、感光性樹脂層が薄くなる膜減りと言った現象が生じず、印刷時の耐刷性に影響が生じる事がなく、一方で非画像部の溶解も効率よく行なわれ、コントラストの高い画像が形成される。
【００１７】
一般式（Ｉ）及び一般式（ＩＩ）で表される構造を持つ親水性高分子は、処理液中０．２〜８重量％が望ましい。この程度の添加量であれば、処理液を濃縮液で供給する場合であっても、濃縮性が低下し、保管、流通上問題になる事はなく、又、処理や経時劣化等での液の活性低下を防ぐ為の十分なアルカリ剤を添加しても感光性組成物を十分保護する事が出来る。より好ましくは０．５〜５、更に望ましくは０．８〜３重量％が望ましい。
【００１８】
通常、珪酸塩を使用した場合には、メタ珪酸塩の形などを取るが、半分以上のアルカリ成分は、現像に使われる事無く、珪酸をアルカリ性に保つ為に使用されている、しかし、一般式（Ｉ）及び又は一般式（ＩＩ）の単位構造は、感光性樹脂との相互作用によってアルカリ成分から保護しているのであって、塩の形を形成するわけではないので添加されたアルカリ成分は無駄なく、現像に使用する事が可能になる。この為、従来の珪酸を使用した現像液と同量のアルカリ剤を添加した場合、処理や経時によって現像液の活性が低下する割合を少なくする事が出来、安定して処理を行なう事が出来る。
又、画像部に、一般式（Ｉ），（ＩＩ）で示される化合物が吸着して、アルカリの浸透を阻害する為、画像部と非画像部の溶解性の差異を広げ、コントラストの高い画像を形成させる事が出来る。
【００１９】
Ａ−１、Ａ−２、Ａ−３はポリエチレングリコールとして、市販されているものを使用する事が出来る。
Ａ−４、Ａ−５、は、ポリオキシエチレンのアルキルエーテル類として、市販されている物を使用する事が出来る。
Ａ−６は、ポリオキシエチレン、ポリオキシプロピレンとして、市販されている物を使用する事が出来る。
Ａ−７は、ポリオキシエチレン、ポリオキシプロピレンのアルキルエーテル類として、市販されている物を使用する事が出来る。
Ａ−８は、米国特許第５４６６５６５号明細書に記載の合成法によって容易に合成できる。
Ａ−９はエチレングリコールジグリシジルエーテル１．０ｍｏｌ、ヒドロキシルアミン１．０ｍｏｌを水と混合し、加熱撹拌を行ない容易に合成する事が出来る。
【００２０】
アルカリ剤としては、無機アルカリ剤として水酸化カリウム、水酸化ナトリウム若しくは水酸化リチウム等を用いることができる。又、有機アルカリ剤としては、電子材料用途で一般的に使用されているアンモニウム系アルカリ剤、例えばテトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、コリン等、又、アミン系アルカリ剤としては、例えば、トリエタノールアミン、イノシン、カテコール、ジエタノールアミン、アセチルアセトン、トリス（ヒドロキシメチル）メチルアミン、エチルアミン、ジエチルアミン、トリエチルアミン、シクロヘキシルアミン、ジメチルアミン、メチルアミン、２−アミノエタノール、モノエタノールアミン、フェニルヒドラジン等を用いる事が出来る。
【００２１】
本発明の感光性組成物用現像液には残膜を防ぐ為に、芳香族スルホン酸のホルマリン縮合物を添加することが望ましい
本発明に好ましく用いることができる芳香族スルホン酸ホルマリン縮合物の具体例としては、例えばα−ナフタレンスルホン酸・ホルマリン縮合物、β−ナフタレンスルホン酸・ホルマリン縮合物、β−ナフタレンスルホン酸Ｎａ塩・ホルマリン縮合物、β−ナフタレンスルホン酸Ｋ塩・ホルマリン縮合物、β−ナフタレンスルホン酸Ｃａ塩・ホルマリン縮合物、β−ナフタレンスルホン酸Ｌｉ塩・ホルマリン縮合物、メラミンスルホン酸Ｎａ塩・ホルマリン縮合物、スルホナフタレンＮａ塩・スルホフタール酸Ｎａ塩・ホルマリン縮合物、１−スルホアントラセンＮａ塩・ホルマリン縮合物、ビスフェニルスルホン酸及びそのＮａ塩・ターフェニルジスルホン酸及びそのＮａ塩・ホルムアルデヒド縮合物、アルキル（Ｃ１〜Ｃ１４）ナフタレンスルホン酸Ｎａ塩・ホルマリン縮合物などが挙げられる。
【００２２】
これらの芳香族スルホン酸ホルマリン縮合物は、重合度が４〜６程度の低分子量のもの、重合度が数十程度の高分子量のものなど、その重合度に関らず使用することが可能である。又、これら芳香族スルホン酸ホルマリン縮合物は市販品として容易に入手することが可能であり、例えば、花王株式会社製の「デモール（登録商標）」シリーズやライオン株式会社製の「ポリテイ（登録商標）」シリーズ、などを入手することができる。日産化学工業株式会社製「ＳＭＦ（登録商標）−ＰＧ」「ＳＭＦ（登録商標）−ＰＡ」などを入手することができる。
【００２３】
本発明の感光性組成物用現像液にこれら芳香族スルホン酸ホルマリン縮合物を使用液１リットル当たり０．２ｇ〜２０ｇ、好ましくは０．５ｇ〜１０ｇを含有させることにより、現像時に溶解されるべき感光性組成物が処理液中に拡散していき効率よく処理することが出来る。また、次々に処理を行ない処理剤中に感光性組成物が蓄積した場合、これらの成分が版材に再付着することを防ぎ、長期に渡り、安定した処理が可能になる。
【００２４】
本発明の感光性組成物用現像液には、非画像部の親水性を維持する為に、有機ホスホン酸類を添加することが望ましい。通常、珪酸塩を使用した感光性組成物用処理液は、二酸化ケイ素として、１０〜４０ｇ／リットルのケイ酸アルカリを含む現像液で処理しアルミニウム表面の親水性を安定化している。しかし、本願発明は、実質的に珪酸を含まない事が望ましく、感光性平版の支持体であるアルミニウムの陽極酸化膜が薄い場合等、非画像部の親水性に関して不利にならないように、有機ホスホン酸類を添加して、現像処理を行ないつつ、非画像部のアルミ表面を親水性化する事が出来る。
【００２５】
以下に有機ホスホン酸類を示すが、これらに限定されるものではない。
構造式中、Ｍは各々独立にアルカリ金属又は水素原子を表す。
Ｂ−１
【化７】

Ｂ−２
【化８】

Ｂ−３
【化９】

Ｂ−４
【化１０】

Ｂ−５
【化１１】

Ｂ−６
【化１２】

Ｂ−７
【化１３】

Ｂ−８
【化１４】

Ｂ−９
【化１５】

特に下記一般式（ＩＩＩ）で示される化合物が好適に用いられる。
一般式（ＩＩＩ）
【化１６】

ｎは０から８の整数を表す。
【００２６】
これら有機ホスホン酸化合物は市販品として容易に入手することが可能であり、例えば、三菱モンサント化成株式会社製の「ディクエスト（登録商標）」シリーズなどを入手することができる。
本発明の感光性組成物用現像液にはこれらの化合物の少なくとも１種を含有させ、その総量が使用液１リットル当たり０．１ｇ〜５０ｇとなるように含有させることが好ましい。特に好ましくは１リットル当たり０．２ｇ〜１０ｇの範囲で含有させることによって十分な効果を維持出来る。この範囲の量であれば、非画像部に吸着して版面の親水性を向上させることが出来る。
【００２７】
この他、本発明の感光性組成物用現像液には、水質調整剤としてキレート剤を加えることも望ましい。キレート剤を加えることで濃縮された感光性組成物用処理液を希釈する際に、希釈水に含まれるカルシウムイオンを隠蔽して不要な析出の発生を抑えることができる。好ましいキレート剤としては、例えば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、ニトリロトリ酢酸、Ｌ−グルタミンジ酢酸などが挙げられる。これらはアルカリ金属塩などの塩として添加されてもよい。これらの化合物の総量が使用液１リットル当たり０．１ｇ〜１０ｇとなるように含有させることが好ましい。特に１リットル当たり０．５ｇ〜２ｇの範囲で含有させることによって十分な効果を維持出来る。
【００２８】
この他本発明の感光性組成物用現像液には、実質的に珪酸塩を含まない事が望まれる。実質的にとは、二酸化珪素として、０．５重量％以下の事を云う。この程度の濃度では、処理に必要な十分なアルカリ剤を添加した場合、アルカリの活性を抑える事が出来ないが、自動現像機の汚れや、珪酸アルミの析出は少量に抑える事が出来る。更に０．２重量％以下では、長期の使用を行なった場合でも極僅かな汚れに抑える事が出来るので望ましい。
【００２９】
この他本発明の感光性組成物用現像液及び補充液にはｐＨ緩衝剤として、以下の化合物を用いることも出来る。アルカリ金属のホウ酸塩、炭酸塩、重炭酸塩及びリン酸塩等の無機緩衝剤やサリチル酸、スルホサリチル酸等の有機化合物が挙げられ、更に好ましくはアルカリ金属のリン酸塩、ホウ酸塩、スルホサリチル酸が良い。これにより感光性組成物用処理液の活性を調整する事が出来る。しかし、これら酸解離定数ｐＫａ値が１１．５以上の化合物はアルカリ剤と混合されると緩衝作用によって、感光性樹脂を可溶化する能力を妨げてしまう傾向があり、酸解離定数ｐＫａ値が１１．５以上の化合物は、添加されるアルカリ剤に対して、モル比で２０％以下、更に望ましくは１０％以下が好ましい。特にｐＨによる感度の依存が少ない版材を処理する場合は使用しない事が望ましい。
【００３０】
この他本発明の感光性組成物用現像液及び補充液には、版面への濡れ性を向上させ、溶け難い前記親水性高分子を可溶化して濃縮液を作成する目的で、界面活性剤類を添加しても良い。アニオン型界面活性剤としては、Ｎ−アルキルスルホ琥珀酸モノアミド二ナトリウム塩類、Ｎ−メチル−Ｎ−オレイルタウリンナトリウム塩類、アビエチン酸塩類、アルカンスルホン酸塩類、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、アルキル硫酸エステル塩類、オレフィン−無水マレイン酸共重合物の部分けん化物類、ジアルキルスルホ琥珀酸塩類、スチレン−無水マレイン酸共重合物の部分けん化物類、ナフタレンスルホン酸塩ホルマリン縮合物類、ヒドロキシアルカンスルホン酸塩類、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、ポリオキシエチレンアルキルエーテル燐酸エステル塩類、ポリオキシエチレンアルキルスルフェニルエーテル塩類、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アルキルフェニルエーテル燐酸エステル塩類、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、脂肪酸アルキルエステルの硫酸エステル塩類、脂肪酸モノグリセリド硫酸エステル塩類、脂肪酸塩類、石油スルホン酸塩類、直鎖アルキルベンゼンスルホン酸塩類、分岐鎖アルキルベンゼンスルホン酸塩類、硫酸化ひまし油、硫酸化牛脂油、等が挙げられ、非イオン界面活性剤としては、Ｎ，Ｎ−ビス−２−ヒドロキシアルキルアミン類、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、トリアルキルアミンオキシド類、トリエタノールアミン脂肪酸エステル類、プロピレングリコールモノ脂肪酸エステル類、ペンタエリスリ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、ポリオキシエチレンアルキルアミン類、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グリセリン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、ポリオキシエチレン−ポリオキシプロピレン共重合体類、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化ひまし油類、ポリ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、等が挙げられる。その他、弗素系界面活性剤、シリコン系界面活性剤なども好適に用いられる。これらの界面活性剤を添加する事によって、感光性樹脂層に処理剤が浸透しやすくなり、現像効率を上げることが可能となり、又、非画像部と画像部の境界部を際立たせることが可能になる。
【００３１】
本発明の感光性組成物用現像液は、経時や処理等によって処理液活性が低下した場合には、経時時間、処理量、等の状態によって補充量を推定し添加しても良いし、処理液のｐＨや電導度などの測定値を基に補充液を決定しても良い。補充液としては、スタート液（母液）を使用しても良いが、母液よりも活性の高い液を添加する方が、廃液量の低減に繋がり望ましい。補充液組成としては、母液のアルカリと単位構造のモル比率（アルカリ／単位構造）が高いほうが望ましく、より好ましくは補充による液活性の変動を抑える為に、１〜２倍以内の組成物を添加することが望ましい。更に好ましくは１〜１．７倍以内が望ましい。この範囲であれば、劣化した状態の処理液を元の活性に少量で戻す事ができ、添加による活性の動きも穏やかで、補充量の添加が予定よりも多くなってしまっても、極端な活性の動きを回避することが出来る。
補充液には、現像液と同様に、それ以外の化合物を適宜添加してもよい。
【００３２】
感光性平版を本発明の感光性組成物用現像液で処理した後、排出される廃液は、酸性の物質を添加する事によって、より安全な状態に変化させる事が出来る。通常行なわれているような、酸性物質を溶かした水溶液を添加しても良いが、粉の状態で添加する方が廃液量を抑えられるので望ましい。例えば、ホウ酸、重炭酸、リン酸ニ水素塩などが好適に用いられる。添加量としては、廃液が現像廃液のみの場合、現像廃液と水洗廃液の混合物の場合等によって異なるが、廃液に対して３％から０．１％程度添加することが好ましい。更に、１％から０．３％程度が好ましく、経済的で且つ十分に廃液のｐＨを低下させることが出来る。
【００３３】
本発明の感光性組成物用現像液はこれらの酸性物質を直接添加したとしても、珪酸などによるゲル状の析出物や廃液タンク内に珪酸のこびり付き等が発生しない。これらｐＨを下げた処理剤は、適宜フィルター等の、分離装置を使用して、現像液に溶解していた感光性樹脂を取り除いて、液体部分を現像後の水洗水として再利用しても良い。この様な工程を行なう事で、廃液量を更に減らす事が出来る。
【００３４】
【実施例】
〔実施例１〕次に、本発明を実施例により具体的に説明する。表２に示した組成で、感光性組成物用処理液を作成し性能を確認した。
【表２】

芳香族スルホン酸ホルマリン縮合物１として下記の化合物を使用
【化１７】

芳香族スルホン酸ホルマリン縮合物２として下記の化合物を使用
【化１８】

【００３５】
〔画像部の残存率〕 現像処理前の市販感光材料を反射型濃度計Ｘ−Ｒｉｔｅ（登録商標）３６１Ｔ（Ｘ−Ｒｉｔｅ社製）で色濃度測定し、２１段ステップでウェッジ露光した後、現像処理を以下の条件で行った。現像処理後、画像部の色濃度を測定し、どの程度、感光性樹脂層が減少しているか測定した。
現像時間 １２秒
現像温度 ３０℃
現像後の濃度／現像前の濃度での比較から以下のように評価した。
○：０．９５以上残存している
△：０．８０以上残存している
×：０．６０以下になってしまっている
比較例１，２と本発明１〜７は現像後も画像部が十分残っている。比較例３は若干感光性樹脂層が減少する傾向が見られる。比較例４，５に到っては、感光層がかなり減少し、印刷に耐えうる状態では無くなっている。
【００３６】
〔処理能力▲１▼経時での活性低下〕 自動現像機に表２で示される組成の処理液を入れ、数日間放置する。新液時と放置後の液の活性を２１段ステップでウェッジ露光した感光材料を処理して比較をした。処理条件は３０℃１２秒で行った。
○：０．５段以内、に劣化が収まっている。
△：１．０段程度、溶解段数が変化している。
×：１．５段以上、溶解段数が変化している。
【００３７】
〔処理能力▲２▼処理での活性低下〕 自動現像機に表２で示される組成の処理液を入れ、全面露光を行った市販の感光材料を自動現像機の処理液１リッター当り１５ｍ^２処理を行い劣化させた。２１段ステップでウェッジ露光した感光材料を処理して新液時と劣化時の液活性を比較した。処理条件は３０℃１２秒で行った。
○：０．５段以内、に劣化が収まっている。
△：１．０段程度、溶解段数が変化している。
×：１．５段以上、溶解段数が変化している。
【００３８】
比較例１〜３は、処理や経時によって液の活性が大きく低下している事が確認できる。また、一般式（Ｉ），（ＩＩ）を含まない比較例４、５は新液時から特性に問題があり、比較が不可能であった。本発明１から７は処理、経時による劣化が少なく安定して処理できる事が確認できた。
【００３９】
〔樹脂の再付着性〕 前記試験〔処理能力▲２▼処理での活性低下〕の液で処理した版材を印刷機に掛け印刷状態を確認した。このとき、現像促進の為に使用している、液中シャワーやブラシローラーを外し、樹脂が再付着し易い状態で確認を行った。
○：汚れは全くみられない。
△：非画像部の一部に薄っすらとインキが乗る。
×：非画像部全体に薄っすらとインキが乗る。
【００４０】
比較例１〜５の組成では、攪拌が弱いと、感材によっては再付着が起こり汚れの原因となった。本発明２〜７は芳香族スルホン酸類によって、溶解した感光性組成物成分が分散する為、攪拌が弱くても再付着することはなかった。本発明１は、芳香族スルホン酸類が添加されていない為、若干汚れが付着し易い傾向があるが液活性が高く、水溶性高分子が非画像部を保護する為、比較的良好な状態が得られる。
【００４１】
〔非画像部の溶解性〕 感光材料を通常露光する際の４０％程度で露光を行ない、現像処理を行って非画像部が十分に溶解しているか確認する。現像処理後、版面を水でぬらした後、インキローラーでインキを塗布し、非画像部の状態を確認した、
○：汚れは全くみられない。
△：非画像部の一部に薄っすらとインキが乗る。
×：非画像部全体に薄っすらとインキが乗る。
比較例２は版材によっては感光性樹脂の溶解が迅速には進まず、汚れるケースが生じる。
【００４２】
〔自動現像機の汚れ〕 自動現像機に現像液を充填し、１日８時間稼動させ一週間後、自動現像機から現像液を抜き現像成分の析出の有無を確認した。
○：汚れは全くみられない。
△：ローラーや壁面に現像成分が若干付着しているが、水洗により落ちる。
×：ローラーや壁面に現像成分が固着して、水洗では落ちない。
比較例１，２は珪酸塩を使用しているため、自動現像液に汚れが付着する。比較例３は珪酸塩の量が少ないので汚れも僅かである。本発明の１〜７は全て、現像成分の付着などが見られず綺麗な状態を保っている。
【００４３】
〔非画像部の親水性〕 現像処理の後、水洗のみを行ない、リンスやガム引きは行なわず、印刷機に掛け通常の７０％程度の湿し水供給量で印刷を行ない、印刷物の汚れを確認した。
○：１０００枚後汚れは全くみられない。
△：１０００枚後咥え部分に若干汚れが発生。
×：１０００枚後全体に薄っすらとインキが乗る。
【００４４】
比較例１、２は珪酸を十分に含む現像液での処理である為、版材の親水化性が向上し、汚れが見られない。比較例３は珪酸量が少なく、比較例４，５は入っていない為、汚れが発生する。本発明２〜７は珪酸の替わりに有機ホスホン酸か添加され、版材を親水化するため、汚れが抑えられている。本発明１は珪酸も有機ホスホン酸も添加されていないが、水溶性高分子中に一般式（ＩＩ）で示される構造を含み、版面に水溶性高分子が吸着し、親水性を向上させるため、比較的汚れの発生が改善されている。
【００４５】
〔実施例２〕
次に、以下の条件で感光性組成物を処理し、表３に示した組成で補充を行ない、ランニングテストを行った。
【表３】

【００４６】
〔補充量（ｍｌ）〕 スタート時の感度を１００としたとき、±２０％の範囲で感度を維持するように１ｍ^２辺りの補充を求めた。
表３記載の通り、１ヵ月間ランニングした場合の廃液の量を比較すると、比較例６〜８は感度を維持する為に、多量のアルカリを含む成分を添加しなければならないが、本発明８〜１２は、補充液組成が珪酸の塩といった形を取らない為、効率よく活性を戻す事ができ、少量の補充量で感度が維持できる。
【００４７】
〔処理安定性〕 補充を行なうタイミングを、１ｍ^２毎から１０ｍ^２毎に変更し、補充前と補充後の感度の動きを確認した。
○：補充前後の感度の動きが５％以内。
△：補充前後の感度の動きが８％以内。
×：補充前後の感度の動きが１２％以上。
比較例６〜８は劣化が大きく、補充を行った際の変動も大きい。本発明８〜１２は劣化の幅が小さく、前記水溶性高分子が感光性組成物の溶解を抑えるため安定した処理が行える。
【００４８】
〔水洗水量（ｍｌ）〕 水洗槽の水が濁りを生じると、ローラーに汚れが付着するため、濁りが強くならないように１ｍ^２毎に補充を行った。珪酸塩の濁りは水洗ノズルを詰まらせる為、多目の補充が必要となった。本発明の高分子は水に溶解し易く、少ない補充量でも影響が出なかった。
【００４９】
〔総廃液量（リットル）〕 ６００ｍ^２処理した場合の現像液と水洗水の廃液量
【００５０】
〔自動現像機の感光性樹脂による汚れ〕 ６００ｍ^２処理した時点で自動現像機から処理液を取出し、汚れ具合を確認した。
○：汚れは全くみられない。
△：ローラーや壁面に現像成分が若干付着しているが、水洗により落ちる。
×：ローラーや壁面に現像成分が固着して、水洗では落ちない。
比較例６〜８は、感光性平版の基材であるアルミが溶け出し、現像成分の珪酸との間で析出物を作り、汚れが付着するが、本発明８〜１２は析出物が発生せず汚れの付着も見られない。
【００５１】
〔廃液低ｐＨ化処理による廃液増加率〕 廃液のｐＨを低下させる為に、酸性物質を添加する。酸性物質として、炭酸水素ナトリウムを使用し、廃液１リットル当たり炭酸水素ナトリウム８ｇを直接添加し、廃液ｐＨを１０程度でまで下げた。無攪拌で行なった際にゲル状の析出物が出る廃液に対しては、炭酸水素ナトリウムを８％水溶液又は４％水溶液状態にして添加した。ｐＨを低下させた後、廃液の体積増加率を確認した。
○：廃液を低ｐＨした時、体積増が５％以下
△：廃液を低ｐＨした時、体積増が１０％以下
×：廃液を低ｐＨした時、体積増が２０％以下
【００５２】
比較例６〜８はゲル化防止のため、酸性物質を水溶液状態に希釈して現像廃液に添加する必要があり、ｐＨを下げる時に液量の増加が大きくなってしまう。本発明８から１２は、珪酸を実質的に含まない為、酸性物質を水溶液にする必要が無く、固形のまま添加でき、低ｐＨ化を行なう際、僅かな体積増に抑える事が出来る。
【００５３】
【発明の効果】以上述べたように本発明の請求項１によれば、一般式（Ｉ）及び又は一般式（ＩＩ）で表される構造を１０個以上持つ分子量６００以上の水溶性高分子とアルカリ剤を含むので、珪酸塩などの無機塩を使わず、それに起因する自動現像機の汚れを起こすことなく、しかもアルカリ成分の活性をおさえる安定した効率のよい処理ができる。
【００５４】
又、請求項２によれば、水溶性高分子の末端基は水素原子及び又は炭素数５以下の直鎖、又は分岐アルキル基であるので、高アルカリ性の現像液中にあっても感光性樹脂を保護し、画像部の感光性樹脂の膜減りを抑えることができる。
【００５５】
又、請求項３によれば、一般式（Ｉ）及び又は一般式（ＩＩ）で表される構造が重量比で７０％以上の水溶性高分子を、０．２〜８重量％含むので、親水性高分子が、親油性の画像部に強固に吸着すること、現像、水洗工程を過ぎた後まで版面に残ること、画像部のインキとの親和性を低下させること、これらがなく良好な印刷が可能となる。
【００５６】
又、請求項４によれば、一般式（Ｉ）及び又は一般式（ＩＩ）で表される単位構造とアルカリ剤のモル比が、アルカリ剤を１として０．３〜３であるので、高アルカリ性の現像液中にあっても感光性樹脂を保護し、画像部の感光性樹脂の膜減りを抑えることができる。
【００５７】
又、請求項５によれば、芳香族スルホン酸のホルマリン縮合物を含有するので、溶解すべき感光性組成物の現像液中での溶解拡散が効率よく行われ、蓄積しても版材への再付着を防ぎ、長期安定した処理ができる。
【００５８】
又、請求項６によれば、有機ホスホン酸類を含有するので、非画像部の親水性を維持することができる。
【００５９】
又、請求項７によれば、一般式（Ｉ）及び又は一般式（ＩＩ）で表される単位構造とアルカリ剤のモル比が請求項１〜６いずれか一項の感光性組成物用現像液と同等若しくは高いので、廃液量の低減になり、環境上好ましく、又処理コスト削減にも寄与することができる。
【００６０】
更に、請求項８によれば、請求項１から７の何れか一項の感光性組成物用現像液及び補充液に酸性物質を粉体で供給するので、総廃液量の増加が抑えられ、廃液処理が容易になり、処理コスト削減を達成できる。[0001]
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a developer used for developing a photosensitive composition such as a photoresist used for a lithographic printing plate, an IC circuit, a color filter, a photomask and the like. More specifically, the present invention relates to a developer for a photosensitive composition, which can change the solubility in an alkali by imagewise exposing the photosensitive composition containing an alkali-soluble resin to light or heat.
[0002]
2. Description of the Related Art Conventionally, as a typical lithographic printing plate, a presensitized plate plate (a plate obtained by subjecting an aluminum plate to a roughening treatment and a hydrophilizing treatment and applying a photosensitive layer provided with an o-quinonediazide compound). The so-called PS version is widely used. After the PS plate is brought into close contact with the plate making film, the image is printed by exposing it to ultraviolet light, and the exposed and unexposed parts are treated with an alkaline developer to make use of the difference in solubility in alkali. Was creating an image. In general, silicate has been used as an alkaline developer. Silicates have a high buffering capacity and can stably perform development processing at high pH.
In addition, silicate adheres to the surface of aluminum after dissolving the photosensitive resin, has the effect of improving the hydrophilicity of the plate surface, and is suitable from the viewpoint of the stability of development processing and printability after development processing. And is used in most processing agents in this field.
[0003]
In recent years, computer-to-plate (so-called CTP) technology has been developed to output directly to a printing plate instead of to a film based on digital data as a lithographic plate other than the PS plate, which converts light energy into heat to form an image. Has been used to create a printing plate (see Patent Document 1).
Also in this case, an aqueous solution of silicate is recommended as a developing solution, and a treatment based on a difference in solubility between an image portion and a non-image portion in an alkaline developing solution has been proposed.
However, a developer containing silicate causes precipitation of silicic acid in an automatic developing machine due to long-term use, and depending on the photosensitive resin, penetration into the photosensitive layer is not sufficient, and a residual film is formed on a non-image area. It has been confirmed that the remaining undissolved photosensitive resin remains attached.
[0004]
A photosensitive composition for a PS plate, which is a typical photosensitive resin printing plate made of a combination of naphthoquinonediazide and an alkali-soluble resin, can be dissolved only with an aqueous solution of sodium hydroxide or potassium hydroxide. In this case, it is not possible to dissolve efficiently, but a high-concentration aqueous alkaline solution also dissolves a portion that is desired to be left as an image. For this reason, a developing solution is prepared in the form of a silicate, and its activity is suppressed so that a processing agent containing a high concentration of alkali does not dissolve the image area (see Patent Documents 2 and 3).
[0005]
However, since these developing solutions are highly alkaline with a pH of 12 or more, they absorb carbon dioxide in the air to cause a decrease in pH, and the treatment of the photosensitive composition causes a decrease in pH. For this reason, the activity of the processing solution fluctuates and stable processing becomes difficult. In order to improve the stability of the treatment, the concentration of silicate is increased and the ratio of silicic acid to alkali (SiO ₂ / M ₂ It is effective to increase O), but as the amount of silicic acid increases, ₂ Is easily precipitated and hardens in an automatic developing device, and when it adheres to a roller or the like, the surface of the photosensitive material is damaged, and a state where printing is impossible occurs. These precipitates cannot be easily removed, and require immersion in a highly alkaline cleaning solution for a while, rubbing and the like. Silica to alkali ratio (SiO ₂ / M ₂ If O) is reduced, the precipitation can be reduced, but by itself, the treatment liquid tends to fluctuate, resulting in an unstable state. Even when replenishment is performed to stabilize, the ratio of silicic acid to alkali (SiO ₂ / M ₂ When O) is low, the replenishment amount must be strictly adjusted, and a complicated operation is required. If the developer is constantly replenished and replaced with a fresh developer, the occurrence of precipitation can be suppressed, but the amount of waste liquid increases extremely.
[0006]
Although the development waste liquid is deteriorated, it still has a high pH and corresponds to specially controlled industrial waste, so that there is a problem that it takes time to dispose. When this waste liquid is treated, measures have been taken to lower the pH of the waste liquid by adding an acidic substance (see Patent Literature 4). However, the waste liquid containing silicic acid is gelated at the time of lowering the acidity to acidic, and it is difficult to further process. It becomes form. In order to prevent gelation, when adding acidic substances, it is necessary to dilute the acidic substances and add them in the form of an aqueous solution so that the pH of the waste liquid does not drop sharply. Would.
[0007]
A similar problem occurs in the thermal CTP plate. Further, the thermal CTP plate has a small difference in solubility between the unexposed portion and the exposed portion as compared with the PS plate material. When the activity is high, the density of the image area is reduced and the printing durability is lowered. When the activity is low, the development failure is easily caused and the printing stain is easily generated. When a developer containing a large amount of silicate is used in such a state, the developer does not efficiently penetrate into the photosensitive resin, and a phenomenon such as a residual film remaining in a non-image portion occurs. A developer using a non-reducing sugar as a developer containing no silicic acid has also been proposed (see Patent Document 5). However, saccharides tend to have low stability under strong alkalinity, and it was not possible to add a sufficient amount of an alkali agent.
[0008]
Usually, in the automatic developer processing, washing and rinsing are performed after the development processing. The rinsing processing is performed in an acidic condition so that the rinsing component is easily adsorbed on the plate surface. At this time, if the residual film of the photosensitive composition is still attached to the non-image area, it is firmly re-adhered to the plate surface and cannot be easily removed, and the non-image area has an oil-sensitive portion. In some cases, the remaining print may not be usable.
[0009]
In the case of a developer used for semiconductors, the presence of silicic acid or the like causes contamination of the substrate, resulting in unstable operation and an increase in defective products. However, if the treatment is carried out only with an organic alkali agent such as tetramethylammonium hydroxide, the developing activity becomes too high, and it becomes impossible to reproduce the fine line portion exposed to the pattern. When the concentration of the organic alkali agent is reduced for the purpose of suppressing the development activity, there has been a problem that development does not proceed sufficiently and efficient production cannot be performed.
[0010]
[Patent Document 1] Japanese Patent Application Laid-Open No. 7-285275
[Patent Document 2] JP-A-55-22759
[Patent Document 3] JP-A-5-2273
[Patent Document 4] JP-A-7-31453
[Patent Document 5] JP-A-2003-15319
[0011]
SUMMARY OF THE INVENTION An object of the present invention is to provide a photosensitive lithographic development process in which the generation of precipitates in a developing tank can be suppressed by eliminating silicate contained in a developer. An object of the present invention is to provide a photosensitive lithographic developer capable of obtaining a clear image stably for a long time even in a high alkali. Another object of the present invention is to supply a developing solution that can be processed stably without using an inorganic salt, suppressing development activity, and using a semiconductor-related developing solution.
[0012]
Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that the above object can be easily solved by using the following photosensitive composition developer. The present invention has been reached. That is, the present invention is characterized by containing a water-soluble polymer having a molecular weight of 600 or more and having 10 or more structures represented by the general formula (I) and / or the general formula (II).
General formula (I)
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R ₁ Represents an ethylene group or a hydroxypropylene group.
General formula (II)
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R ₂ Represents an ethylene group or a hydroxypropylene group.
The developer for a photosensitive composition of the present invention is characterized by containing a water-soluble polymer having a molecular weight of 600 or more having 10 or more structures represented by the general formula (I) and / or the general formula (II) and an alkali agent. And
The developer for a photosensitive composition of the present invention is characterized in that the terminal group of the water-soluble polymer is a hydrogen atom and / or a linear or branched alkyl group having 5 or less carbon atoms.
The developer for a photosensitive composition of the present invention contains 0.2 to 8% by weight of a water-soluble polymer having a structure represented by the general formula (I) and / or the general formula (II) having a weight ratio of 70% or more. % Included
In the developer for a photosensitive composition of the present invention, the molar ratio between the unit structure represented by the general formula (I) and / or the general formula (II) and the alkali agent is 0.3 to 3 with respect to alkali. It is characterized by.
The developer for a photosensitive composition of the present invention is characterized by containing a formalin condensate of an aromatic sulfonic acid.
The developer for a photosensitive composition of the present invention is characterized by containing an organic phosphonic acid.
The developer replenisher for a photosensitive composition according to the present invention has a unit structure represented by the general formula (I) and / or the general formula (II) and a molar ratio of an alkali agent equal to or the same as that of the developer for a photosensitive composition. Wherein the molar ratio of the alkali agent to the processing liquid is higher than that of the processing liquid.
The method is characterized in that an acidic substance is supplied as a powder in the treatment of a waste liquid such as a developer for a photosensitive composition and a replenisher.
[0013]
Embodiments of the present invention will be described below in detail. Examples of specific compounds of the general formula (I) and the general formula (II) used in the present invention will be given. However, the present invention is not limited to these compounds.
General formula (I)
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R ₁ Represents an ethylene group or a hydroxypropylene group.
General formula (II)
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R ₂ Represents an ethylene group or a hydroxypropylene group.
The compounds are shown in Table 1 as examples above, but the present invention is not limited to them.
[Table 1]

[0014]
The water-soluble polymer having this unit structure preferably has a molecular weight of 600 or more. When it is 600 or more, the photosensitive composition can be protected and the image area can be protected from the alkali agent. It is more preferably at least 1,000, and a processing agent having a sharp boundary between an image portion and a non-image portion can be obtained. It is desirable that the water-soluble polymer contains the unit structure in an amount of 70% by weight or more. When the unit structure is 70% by weight or more, it is possible to protect the photosensitive resin even in a highly alkaline developing solution, and to suppress a decrease in the thickness of the photosensitive resin layer in the image area.
[0015]
In particular, when the alkyl group attached to the terminal group of the water-soluble polymer has 5 or less carbon atoms, the hydrophilic polymer is firmly adsorbed to the lipophilic image area and remains on the plate until after the development-washing step. Good printing can be achieved without lowering the affinity for the ink in the image area (so-called ink adhesion).
Among the hydrophilic polymers used in the present invention, those having the general formula (II) suppress the aluminum, which is the base material of the photosensitive lithographic plate, from being dissolved by a strong alkali in the developer, and reduce the activity of the developer. It can be more stable.
[0016]
The ratio of the unit structure represented by the general formulas (I) and (II) to the alkali agent is preferably from 0.3 to 4 mol, more preferably from 0.5 to 4 mol, per mol of the alkali agent. Two moles are desirable. In this case, the alkali agent is calculated to be 1 mol in a free state, except for a salt in the form of a salt with another compound.
The unit structure is linked to an alkali-soluble resin and can prevent dissolution of the image area. For this reason, if the ratio of the unit structure to the alkali component is within this range, a phenomenon such as film thinning in which the photosensitive resin layer becomes thin does not occur, and the printing durability during printing is not affected. As a result, the non-image portion is efficiently dissolved, and an image with high contrast is formed.
[0017]
The content of the hydrophilic polymer having the structure represented by the general formula (I) or (II) is desirably 0.2 to 8% by weight in the treatment liquid. With this amount of addition, even when the processing solution is supplied as a concentrated solution, the concentration property is reduced, and there is no problem in storage and distribution. The photosensitive composition can be sufficiently protected even by adding a sufficient alkali agent to prevent the activity of the photosensitive composition from decreasing. More preferably, it is 0.5 to 5, and more preferably 0.8 to 3% by weight.
[0018]
Normally, when silicate is used, it takes the form of metasilicate, etc., but more than half of the alkali component is used to keep the silicic acid alkaline without being used for development. The unit structure of the formula (I) and / or the general formula (II) is protected from the alkali component by the interaction with the photosensitive resin, and does not form a salt form. Can be used for development without waste. Therefore, when the same amount of an alkali agent as a conventional developer using silicic acid is added, the rate of decrease in the activity of the developer due to processing or aging can be reduced, and the processing can be performed stably. .
Further, the compounds represented by the general formulas (I) and (II) are adsorbed on the image area and inhibit the penetration of alkali, so that the difference in solubility between the image area and the non-image area is widened, and an image with high contrast is obtained. Can be formed.
[0019]
As A-1, A-2, and A-3, commercially available polyethylene glycol can be used.
As A-4 and A-5, commercially available products can be used as alkyl ethers of polyoxyethylene.
As A-6, commercially available products can be used as polyoxyethylene and polyoxypropylene.
For A-7, commercially available alkyl ethers of polyoxyethylene and polyoxypropylene can be used.
A-8 can be easily synthesized by the synthesis method described in US Pat. No. 5,466,565.
A-9 can be easily synthesized by mixing 1.0 mol of ethylene glycol diglycidyl ether and 1.0 mol of hydroxylamine with water, heating and stirring.
[0020]
As the alkali agent, potassium hydroxide, sodium hydroxide, lithium hydroxide, or the like can be used as an inorganic alkali agent. Further, as the organic alkali agent, an ammonium-based alkali agent generally used in electronic material applications, such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, and the like, and as the amine-based alkali agent, for example, Use triethanolamine, inosine, catechol, diethanolamine, acetylacetone, tris (hydroxymethyl) methylamine, ethylamine, diethylamine, triethylamine, cyclohexylamine, dimethylamine, methylamine, 2-aminoethanol, monoethanolamine, phenylhydrazine, etc. Can be done.
[0021]
It is desirable to add a formalin condensate of aromatic sulfonic acid in the developer for the photosensitive composition of the present invention in order to prevent a residual film.
Specific examples of the aromatic sulfonic acid formalin condensate that can be preferably used in the present invention include, for example, α-naphthalene sulfonic acid / formalin condensate, β-naphthalene sulfonic acid / formalin condensate, β-naphthalene sulfonic acid Na salt, Formalin condensate, β-naphthalene sulfonic acid K salt / formalin condensate, β-naphthalene sulfonic acid Ca salt / formalin condensate, β-naphthalene sulfonic acid Li salt / formalin condensate, Melamine sulfonic acid Na salt / formalin condensate, Na salt of sulfonaphthalene / Na salt of sulfophthalic acid / formalin condensate, 1-sulfoanthracene Na salt / formalin condensate, bisphenylsulfonic acid and its Na salt / terphenyldisulfonic acid and its Na salt / formaldehyde condensate, alkyl (C1 ~ C14) Naphthalene Such as sulfonic acid Na salt-formalin condensates and the like.
[0022]
These aromatic sulfonic acid formalin condensates can be used regardless of the degree of polymerization, such as those having a low molecular weight of about 4 to 6 and high molecular weights of about several tens of degrees. is there. These aromatic sulfonic acid formalin condensates can be easily obtained as commercial products. For example, the “Demol (registered trademark)” series manufactured by Kao Corporation and the “Polyte (registered trademark)” manufactured by Lion Corporation are available. ) "Series, etc. are available. “SMF (registered trademark) -PG” and “SMF (registered trademark) -PA” manufactured by Nissan Chemical Industries, Ltd. can be obtained.
[0023]
The aromatic sulfonic acid formalin condensate is contained in the developer for photosensitive composition of the present invention in an amount of 0.2 g to 20 g, preferably 0.5 g to 10 g per liter of the working solution, so that the developer can be dissolved at the time of development. The photosensitive composition diffuses into the processing solution and can be processed efficiently. Further, when the photosensitive composition is accumulated in the processing agent by performing the processing one after another, these components are prevented from re-adhering to the plate material, and stable processing can be performed for a long period of time.
[0024]
It is desirable to add an organic phosphonic acid to the developer for the photosensitive composition of the present invention in order to maintain the hydrophilicity of the non-image area. Usually, a processing solution for a photosensitive composition using a silicate is treated with a developer containing 10 to 40 g / l of alkali silicate as silicon dioxide to stabilize the hydrophilicity of the aluminum surface. However, the present invention desirably does not substantially contain silicic acid. By adding an acid, the aluminum surface in the non-image area can be made hydrophilic while performing the development processing.
[0025]
The organic phosphonic acids are shown below, but are not limited thereto.
In the structural formula, M independently represents an alkali metal or a hydrogen atom.
B-1
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B-2
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B-3
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B-4
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B-5
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B-6
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B-7
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B-8
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B-9
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Particularly, a compound represented by the following general formula (III) is preferably used.
General formula (III)
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n represents an integer of 0 to 8.
[0026]
These organic phosphonic acid compounds can be easily obtained as commercial products. For example, “Diequest (registered trademark)” series manufactured by Mitsubishi Monsanto Kasei Co., Ltd. can be obtained.
It is preferable that the developer for a photosensitive composition of the present invention contains at least one of these compounds so that the total amount thereof is 0.1 g to 50 g per liter of the working solution. Particularly preferably, a sufficient effect can be maintained by containing 0.2 g to 10 g per liter. When the amount is within this range, the hydrophilicity of the plate surface can be improved by adsorbing to the non-image portion.
[0027]
In addition, it is desirable to add a chelating agent as a water quality adjusting agent to the developer for a photosensitive composition of the present invention. When diluting the concentrated processing solution for a photosensitive composition by adding a chelating agent, it is possible to hide calcium ions contained in the dilution water and suppress generation of unnecessary precipitation. Preferred chelating agents include, for example, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, nitrilotriacetic acid, L-glutaminediacetic acid and the like. These may be added as salts such as alkali metal salts. It is preferable to contain these compounds so that the total amount of these compounds is 0.1 g to 10 g per liter of the working solution. In particular, a sufficient effect can be maintained by containing 0.5 g to 2 g per liter.
[0028]
In addition, it is desired that the developer for a photosensitive composition of the present invention does not substantially contain a silicate. Substantially means that the content of silicon dioxide is 0.5% by weight or less. At such a concentration, the alkali activity cannot be suppressed when a sufficient alkali agent necessary for the treatment is added, but the contamination of the automatic developing machine and the precipitation of aluminum silicate can be suppressed to a small amount. Further, when the content is 0.2% by weight or less, it is desirable because even a long-term use can suppress very little dirt.
[0029]
In addition, the following compounds can be used as a pH buffer in the developer and replenisher for the photosensitive composition of the present invention. Inorganic buffers such as borates, carbonates, bicarbonates and phosphates of alkali metals, and organic compounds such as salicylic acid and sulfosalicylic acid, and more preferably alkali metal phosphates, borates and sulfo salts. Salicylic acid is good. Thereby, the activity of the processing solution for a photosensitive composition can be adjusted. However, these compounds having an acid dissociation constant pKa of 11.5 or more tend to interfere with the ability to solubilize the photosensitive resin due to a buffering action when mixed with an alkali agent. The compound having a molecular weight of 0.5 or more is preferably 20% or less, more preferably 10% or less, in a molar ratio with respect to the added alkali agent. In particular, it is desirable not to use the plate material when processing a plate material in which the sensitivity is less dependent on pH.
[0030]
In addition to the above, the developer and replenisher for the photosensitive composition of the present invention include a surfactant for the purpose of improving the wettability to the plate surface and solubilizing the hardly soluble hydrophilic polymer to prepare a concentrated solution. May be added. Examples of the anionic surfactant include N-alkylsulfosuccinic acid monoamide disodium salt, N-methyl-N-oleyltaurine sodium salt, abietic acid salt, alkanesulfonic acid salt, alkylnaphthalenesulfonic acid salt, alkylphenoxypolyoxyethylene Propyl sulfonates, alkyl sulfates, partially saponified olefin-maleic anhydride copolymers, dialkyl sulfosuccinates, partially saponified styrene-maleic anhydride copolymers, naphthalene sulfonate formalin condensation Products, hydroxyalkane sulfonates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl sulfenyl ethers, polyoxyethylene Lenalkyl phenyl ether sulfates, polyoxyethylene alkyl phenyl ether phosphates, polyoxyethylene styryl phenyl ether sulfates, fatty acid alkyl sulfates, fatty acid monoglyceride sulfates, fatty acid salts, petroleum sulfonates, Examples thereof include linear alkylbenzene sulfonates, branched alkylbenzene sulfonates, sulfated castor oil, sulfated tallow oil, and the like. Examples of nonionic surfactants include N, N-bis-2-hydroxyalkylamines and glycerin. Fatty acid partial esters, sorbitan fatty acid partial esters, trialkylamine oxides, triethanolamine fatty acid esters, propylene glycol monofatty acid esters, pentaerythritol Fatty acid partial esters, polyethylene glycol fatty acid esters, polyoxyethylene alkylamines, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene glycerin fatty acid partial esters, polyoxyethylene sorbitan fatty acid partial esters , Polyoxyethylene sorbitol fatty acid partial esters, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene-polyoxypropylene copolymers, polyoxyethylene polystyryl phenyl ethers, polyoxyethylene castor oil, poly Examples include glycerin fatty acid partial esters, fatty acid diethanolamides, and the like. In addition, a fluorine-based surfactant, a silicon-based surfactant, and the like are also preferably used. By adding these surfactants, the processing agent can easily penetrate into the photosensitive resin layer, and the development efficiency can be increased. Also, the boundary between the non-image area and the image area can be emphasized. become.
[0031]
The developer for the photosensitive composition of the present invention may be added with an estimated replenishing amount depending on the state of the processing time, the processing amount, and the like, when the processing solution activity decreases with time or processing. The replenisher may be determined based on measured values such as pH and conductivity of the solution. As a replenisher, a start solution (mother liquor) may be used. However, it is desirable to add a liquid having a higher activity than the mother liquor because it leads to a reduction in the amount of waste liquid. As the replenisher composition, it is desirable that the molar ratio of alkali to the unit structure of the mother liquor (alkali / unit structure) is higher. More preferably, a composition within 1 to 2 times is added in order to suppress fluctuations in solution activity due to replenishment. It is desirable to do. More preferably, the ratio is within 1 to 1.7 times. Within this range, the processing solution in a deteriorated state can be returned to the original activity in a small amount, the activity of the activity due to the addition is gentle, and even if the addition of the replenishment amount becomes larger than expected, extreme Active movements can be avoided.
As with the developer, other compounds may be appropriately added to the replenisher.
[0032]
After treating the photosensitive lithographic plate with the developer for a photosensitive composition of the present invention, the discharged waste liquid can be changed to a safer state by adding an acidic substance. An aqueous solution in which an acidic substance is dissolved may be added, as is usually done, but it is preferable to add it in a powder state because the amount of waste liquid can be suppressed. For example, boric acid, bicarbonate, dihydrogen phosphate and the like are preferably used. Although the amount of addition varies depending on the case where the waste liquid is only the development waste liquid, the case of a mixture of the development waste liquid and the washing waste liquid, it is preferable to add about 3% to 0.1% to the waste liquid. Further, the concentration is preferably about 1% to 0.3%, and it is economical and can sufficiently lower the pH of the waste liquid.
[0033]
Even if these acidic substances are directly added to the developer for the photosensitive composition of the present invention, no gel-like precipitate due to silicic acid or the like or sticking of silicic acid in the waste liquid tank occurs. These pH-lowering processing agents may be used as appropriate, such as a filter, to remove the photosensitive resin dissolved in the developer using a separation device, and the liquid portion may be reused as washing water after development. . By performing such a process, the amount of waste liquid can be further reduced.
[0034]
【Example】
[Embodiment 1] Next, the present invention will be specifically described with reference to embodiments. With the composition shown in Table 2, a processing solution for a photosensitive composition was prepared and its performance was confirmed.
[Table 2]

The following compounds are used as aromatic sulfonic acid formalin condensate 1
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The following compounds are used as the aromatic sulfonic acid formalin condensate 2
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[0035]
[Residual Ratio of Image Area] The color density of a commercially available photosensitive material before development processing was measured with a reflection type densitometer X-Rite (registered trademark) 361T (manufactured by X-Rite), and wedge exposure was performed in 21-step steps. The treatment was performed under the following conditions. After the development processing, the color density of the image area was measured to determine how much the photosensitive resin layer had decreased.
Development time 12 seconds
Development temperature 30 ° C
From the comparison of density after development / density before development, evaluation was made as follows.
：: 0.95 or more remains
Δ: 0.80 or more remains
×: less than 0.60
In Comparative Examples 1 and 2 and Inventions 1 to 7, sufficient image portions remain even after development. In Comparative Example 3, there is a tendency that the photosensitive resin layer slightly decreases. In Comparative Examples 4 and 5, the number of photosensitive layers was considerably reduced, and the photosensitive layers were no longer in a state capable of withstanding printing.
[0036]
[Processing ability (1) Decrease in activity over time] A processing solution having the composition shown in Table 2 is placed in an automatic processor and left for several days. The activity of the new solution and that of the solution after standing were compared in a 21-step process by processing the photosensitive material exposed to wedges. The treatment was performed at 30 ° C. for 12 seconds.
：: Deterioration was within 0.5 steps.
Δ: about 1.0 step, the number of dissolution steps changed.
×: 1.5 steps or more, the number of dissolution steps changed.
[0037]
[Processing performance (2) Decrease in activity during processing] A processing solution having the composition shown in Table 2 was placed in an automatic developing machine, and a commercially available photosensitive material which had been subjected to full-surface exposure was subjected to 15 m / liter of processing solution of the automatic developing machine. ² Processed and deteriorated. The wedge-exposed light-sensitive material was processed in a 21-step process, and the liquid activities at the time of fresh solution and at the time of deterioration were compared. The treatment was performed at 30 ° C. for 12 seconds.
：: Deterioration was within 0.5 steps.
Δ: about 1.0 step, the number of dissolution steps changed.
×: 1.5 steps or more, the number of dissolution steps changed.
[0038]
In Comparative Examples 1 to 3, it can be confirmed that the activity of the liquid was significantly reduced by the treatment and the aging. Further, Comparative Examples 4 and 5, which do not contain the general formulas (I) and (II), had problems in properties from the time of the new liquid, and were not comparable. It was confirmed that the present inventions 1 to 7 can be processed stably with little deterioration due to processing and aging.
[0039]
[Reattachability of Resin] A plate material treated with the solution of the above test [processing capacity (2), activity reduction during treatment] was applied to a printing machine to check the printing state. At this time, the underwater shower or the brush roller used for accelerating the development was removed, and the confirmation was performed in a state where the resin easily adhered again.
：: No stain is seen at all.
Δ: Ink is slightly applied to a part of the non-image area.
×: Ink is applied evenly on the entire non-image area.
[0040]
In the compositions of Comparative Examples 1 to 5, when the stirring was weak, some photosensitive materials were re-adhered, causing stains. In the present inventions 2 to 7, since the dissolved photosensitive composition components were dispersed by the aromatic sulfonic acids, they did not adhere again even if the stirring was weak. In the present invention 1, since aromatic sulfonic acids are not added, dirt tends to adhere slightly, but the liquid activity is high, and the water-soluble polymer protects the non-image area, so that a relatively good state is obtained. can get.
[0041]
[Solubility of Non-Image Area] Exposure is performed at about 40% of the normal exposure of the photosensitive material, and development processing is performed to check whether the non-image area is sufficiently dissolved. After development, after wetting the plate surface with water, ink was applied with an ink roller and the state of the non-image area was confirmed.
：: No stain is seen at all.
Δ: Ink is slightly applied to a part of the non-image area.
×: Ink is applied evenly on the entire non-image area.
In Comparative Example 2, the dissolution of the photosensitive resin does not proceed quickly depending on the plate material, and a stain occurs.
[0042]
[Stain of Automatic Developing Machine] The developing solution was filled in the automatic developing machine, operated for 8 hours a day, and after one week, the developing solution was removed from the automatic developing machine to confirm the presence or absence of development component.
：: No stain is seen at all.
Δ: The developing component is slightly adhered to the roller and the wall surface, but falls off by washing with water.
X: The developing component adheres to the roller or the wall surface and does not fall off by washing with water.
In Comparative Examples 1 and 2, since silicate is used, dirt adheres to the automatic developing solution. In Comparative Example 3, the amount of silicate is small, so that the stain is slight. All of Examples 1 to 7 of the present invention maintain a beautiful state without adhesion of a developing component or the like.
[0043]
[Hydrophilicity of non-image area] After the development processing, only washing with water is performed, and rinsing and gumming are not performed. confirmed.
：: No stain is observed after 1000 sheets.
Δ: Stain was slightly generated on the grip after 1000 sheets.
×: The ink is applied slightly even after 1000 sheets.
[0044]
In Comparative Examples 1 and 2, since the treatment was carried out with a developer sufficiently containing silicic acid, the hydrophilicity of the plate material was improved, and no stain was observed. In Comparative Example 3, the amount of silicic acid was small, and Comparative Examples 4 and 5 were not contained, so that stains occurred. In the present inventions 2 to 7, organic phosphonic acid is added instead of silicic acid to make the plate material hydrophilic, so that stains are suppressed. In the present invention 1, neither silicic acid nor organic phosphonic acid is added, but the structure shown by the general formula (II) is contained in the water-soluble polymer, and the water-soluble polymer is adsorbed on the plate surface to improve the hydrophilicity. The occurrence of dirt is relatively improved.
[0045]
[Example 2]
Next, the photosensitive composition was treated under the following conditions, replenished with the composition shown in Table 3, and a running test was performed.
[Table 3]

[0046]
[Replenishment amount (ml)] Assuming that the sensitivity at the start is 100, 1 m is used to maintain the sensitivity within the range of ± 20%. ² I asked for supplements around.
As shown in Table 3, when the amount of waste liquid when running for one month is compared, Comparative Examples 6 to 8 require addition of a large amount of an alkali-containing component in order to maintain sensitivity. In Nos. To 12, the replenisher composition does not take the form of silicic acid salt, so that the activity can be efficiently restored, and the sensitivity can be maintained with a small replenishment amount.
[0047]
[Processing stability] The replenishment timing is 1 m ² 10m from each ² It was changed every time, and the movement of sensitivity before and after replenishment was confirmed.
：: The change in sensitivity before and after replenishment is within 5%.
Δ: The sensitivity change before and after replenishment was within 8%.
X: The sensitivity change before and after replenishment is 12% or more.
Comparative Examples 6 to 8 show large deterioration and large fluctuations when replenishment is performed. In the present inventions 8 to 12, the range of deterioration is small, and the water-soluble polymer suppresses dissolution of the photosensitive composition, so that stable processing can be performed.
[0048]
[Washing water volume (ml)] If the water in the washing tank becomes turbid, dirt will adhere to the rollers. ² Replenishment was performed every time. Silicate turbidity clogged the washing nozzle, requiring additional replenishment. The polymer of the present invention was easily dissolved in water and had no effect even with a small amount of replenishment.
[0049]
[Total waste liquid amount (liter)] 600m ² Waste amount of developer and washing water after processing
[0050]
[Contamination with photosensitive resin of automatic developing machine] 600m ² At the time of processing, the processing liquid was taken out of the automatic developing machine, and the degree of contamination was confirmed.
：: No stain is seen at all.
Δ: The developing component is slightly adhered to the roller and the wall surface, but falls off by washing with water.
X: The developing component adheres to the roller or the wall surface and does not fall off by washing with water.
In Comparative Examples 6 to 8, aluminum serving as the base material of the photosensitive lithographic plate was dissolved, and precipitates were formed between the base and the silicic acid as a developing component, and stains were attached. In the present inventions 8 to 12, precipitates were generated. No stains are observed.
[0051]
[Waste liquid increase rate by waste liquid lowering treatment] To lower the pH of the waste liquid, an acidic substance is added. Sodium bicarbonate was used as an acidic substance, and 8 g of sodium bicarbonate was directly added per liter of waste liquid to lower the pH of the waste liquid to about 10. Sodium bicarbonate was added in the form of an 8% aqueous solution or a 4% aqueous solution to a waste liquid from which a gel-like precipitate appeared when the reaction was performed without stirring. After lowering the pH, the rate of volume increase of the waste liquid was confirmed.
：: Volume increase is 5% or less when waste liquid is low pH
Δ: When the pH of the waste liquid is low, the volume increase is 10% or less.
X: Volume increase is 20% or less when the waste liquid is at low pH.
[0052]
In Comparative Examples 6 to 8, in order to prevent gelation, it is necessary to dilute the acidic substance into an aqueous solution state and add it to the waste development solution, and when the pH is lowered, the amount of the liquid becomes large. In the present inventions 8 to 12, since silicic acid is not substantially contained, it is not necessary to make an acidic substance into an aqueous solution, it can be added in a solid state, and it is possible to suppress a slight increase in volume when lowering the pH.
[0053]
As described above, according to claim 1 of the present invention, a water-soluble polymer having a molecular weight of 600 or more and having at least 10 structures represented by the general formula (I) and / or the general formula (II) And an alkali agent, it is possible to perform a stable and efficient treatment without using inorganic salts such as silicates, causing contamination of an automatic developing machine due to the inorganic salts, and suppressing the activity of alkali components.
[0054]
According to claim 2, since the terminal group of the water-soluble polymer is a hydrogen atom and / or a linear or branched alkyl group having 5 or less carbon atoms, the photosensitive resin can be used even in a highly alkaline developer. And the film loss of the photosensitive resin in the image area can be suppressed.
[0055]
According to the third aspect, the structure represented by the general formula (I) and / or the general formula (II) contains 0.2 to 8% by weight of a water-soluble polymer having a weight ratio of 70% or more. The hydrophilic polymer is strongly adsorbed to the lipophilic image area, developed, remains on the plate until after the washing step, reduces the affinity of the image area with the ink, and has good Printing becomes possible.
[0056]
According to the fourth aspect, the molar ratio between the unit structure represented by the general formula (I) and / or the general formula (II) and the alkali agent is 0.3 to 3 with respect to the alkali agent being 1; The photosensitive resin can be protected even in an alkaline developer, and the film loss of the photosensitive resin in the image area can be suppressed.
[0057]
Further, according to claim 5, since the photosensitive composition contains a formalin condensate of an aromatic sulfonic acid, the photosensitive composition to be dissolved can be efficiently dissolved and diffused in a developing solution. Prevents re-adhesion and long-term stable processing.
[0058]
According to the sixth aspect, since the organic phosphonic acid is contained, the hydrophilicity of the non-image area can be maintained.
[0059]
According to claim 7, the molar ratio between the unit structure represented by the general formula (I) and / or the general formula (II) and the alkali agent is the developing ratio for the photosensitive composition according to any one of claims 1 to 6. Since it is equal to or higher than the liquid, the amount of waste liquid is reduced, which is environmentally preferable and can also contribute to reduction of processing cost.
[0060]
Furthermore, according to claim 8, since the acidic substance is supplied as a powder to the developer and replenisher for the photosensitive composition according to any one of claims 1 to 7, an increase in the total waste liquid amount is suppressed, Waste liquid treatment becomes easy, and reduction in treatment cost can be achieved.

Claims (8)

A developer for a photosensitive composition comprising a water-soluble polymer having a molecular weight of 600 or more and having 10 or more structures represented by the general formula (I) and / or the general formula (II) and an alkali agent.
General formula (I)

R ₁ represents an ethylene group or a hydroxypropylene group.
General formula (II)

R ₂ represents an ethylene group or a hydroxypropylene group. The developer for a photosensitive composition according to claim 1, wherein the terminal group of the water-soluble polymer is a hydrogen atom and / or a linear or branched alkyl group having 5 or less carbon atoms. The structure represented by the general formula (I) and / or the general formula (II) contains 0.2 to 8% by weight of a water-soluble polymer having a weight ratio of 70% or more. 4. The developer for a photosensitive composition according to item 1. The molar ratio between the unit structure represented by the general formula (I) and / or the general formula (II) and the alkali agent is 0.3 to 3 with respect to the alkali agent being 1 to 3. 3. The developer for a photosensitive composition according to any one of 3. 5. The developer for a photosensitive composition according to claim 1, further comprising a formalin condensate of an aromatic sulfonic acid. 5. The developer for a photosensitive composition according to claim 1, further comprising an organic phosphonic acid. The molar ratio between the unit structure represented by the general formula (I) and / or the general formula (II) and the alkali agent is equal to or higher than the developer for the photosensitive composition according to any one of claims 1 to 6. Replenisher for the developer for the photosensitive composition. 8. A method for treating a waste liquid such as a developer for a photosensitive composition, comprising supplying an acidic substance as a powder in the waste liquid treatment of the developer or replenisher for the photosensitive composition according to claim 1. .