JP3586990B2 - Developer for photosensitive resin printing plate and method for producing photosensitive resin printing plate - Google Patents

Description

（式中Ｘ_１ は硫黄（−Ｓ−）、カルボニル基（−ＣＯ−）、エチレン基（−ＣＨ_２ −ＣＨ _２ −）を表す。またＲ_１ 、Ｒ_２ 及びＲ_３ は同一でも異なっていてもよく、水素原子、炭素数が１〜５のアルキル基、炭素数が１〜５のアルコキシル基、Ｆ、Ｃｌ、Ｂｒ、Ｉのハロゲン原子、炭素数が１〜５のヒドロキシアルキル基、炭素数が１〜５のヒドロキシアルコキシル基又は４級アンモニウム塩誘導体を表わす。）
【００２８】
【化２】

（式中Ｘ_２ は下記一般式で示される置換もしくは非置換のベンゾイル基、フェニル基、ナフチル基を表わす。またＲ_４ は水素原子、Ｆ、Ｃｌ、Ｂｒ、Ｉのハロゲン原子、炭素数１〜５のアルコキシル基、ヒドロキシル基、炭素数１〜５のアルキル基、炭素数が１〜５のヒドロキシアルキル基又は炭素数が１〜５のヒドロキシアルコキシル基を表わす。）
【００２９】
【化３】

（式中Ｒ_５ はＦ、Ｃｌ、Ｂｒ、Ｉのハロゲン原子、水素原子、炭素数１〜５のアルキル基、炭素数１〜５のアルコキシル基、炭素数が１〜５のヒドロキシアルキル基、炭素数が１〜５のヒドロキシアルコキシル基又は４級アンモニウム塩誘導体を示す。）
【００３０】
また、式（１）又は（２）の誘導体としては、重合性二重結合を有するものでも本発明の水素引き抜き剤として用いることができる。
この様な化合物として具体的には、ベンゾフェノン、４，４’−ジメトキシベンゾフェノン、４−ヒドロキシベンゾフェノン、アントラキノン、２−メチルアントラキノン、２−エチルアントラキノン、２，４−ジエチルチオキサントン、２−クロロチオキサントンなどが挙げられ、式（１）又は（２）の４級アンモニウム塩誘導体としては、（２−アクリロイルオキシ）（４−ベンゾイルベンジル）ジメチル臭化アンモニウム塩、（４−ベンゾイルベンジル）塩化トリメチルアンモニウム、２−（３−ジメチルアミノ−２−ヒドロキシプロポキシ）−３，４−ジメチル−９Ｈ−チオキサントン−９−オンメソクロライドなどが挙げられる。
この中では、分散性、単位重量当たりの水素引き抜き効果等の点からベンゾフェノンが最も効果的である。
【００３１】
本発明の一つの効果、すなわち非粘着性の感光性樹脂印刷版が得られるという効果が十分に発揮されるためには、水素引き抜き剤を含有した現像液による現像工程において、感光性樹脂印刷版中の樹脂硬化物表面に水素引き抜き剤を付着含浸させることが必要であり、そのためには現像液組成のうち水素引き抜き剤が現像液中に分散していることが必要である。
【００３２】
現像中での水素引き抜き剤の状態は溶解していることが最適であるが、懸濁状態として均一分散していれば効果は発現される。均一分散状態とは、現像中に必要量の水素引き抜き剤が沈降しないで溶解、浮遊している状態を表わし、より詳しくは、後述する適正現像温度において必要量の水素引き抜き剤が２４時間以上沈殿物とならないことを示す。分散状態の水素引き抜き剤の粒径については、粒径が小さい方が硬化部表面への含浸に効果的であり、特に制限するところではないが１０^−５ｃｍ以下のものであることが望ましい。
【００３３】
現像液中で水素引き抜き剤が均一分散していない状態、すなわち現像機槽内で水素引き抜き剤が沈降し、必要量の分散が維持されない状態では、現像機底部に滞留した水素引き抜き剤成分が樹脂硬化部表面層への付着含浸に関与しないため粘着性除去効果が十分でなくなる。またスプレー型現像機では、ノズル部分で結晶化した水素引き抜き剤が詰まることによりスプレー圧の低下が生じ、さらには装置故障の原因と成り得る。
【００３４】
水素引き抜き剤を現像液中で均一分散させるための混合方法としては、次のような方法が挙げられる。
水素引き抜き剤が現像液に溶解あるいは均一分散する場合には、そのまま水素引き抜き剤を現像液に投入し混合する。また現像液の一部を分け取り、水素引き抜き剤を混合したものを現像液に投入しても良い。
【００３５】
しかし、多くの水素引き抜き剤は１０〜２０℃で固体であり、また液体であっても特に水系現像液に対しては溶解あるいは均一分散しないものが多い。このように水素引き抜き剤を溶解あるいは分散する能力に乏しい現像液では、現像液組成の変更あるいは分散助剤の添加によって水素引き抜き剤の溶解性あるいは均一分散性を付与することも可能である。特に２０〜６０℃の現像液使用温度において引火点を持たないことを特徴とする水系現像液では、水素引き抜き剤を乳化し得る界面活性剤の使用が効果的である。
【００３６】
また水素引き抜き剤を単体で現像液に混合しても溶解あるいは均一分散が困難な場合には、あらかじめ現像液中で分散状態になるような方法で混合しなければならない。
例えば（１）あらかじめ水素引き抜き剤を融点まで加熱して液体にしたものを投入し混合する、（２）あらかじめ水素引き抜き剤の固体をミキサー等の機械的粉砕により極微少な粉末にしたものを現像液に投入し混合する方法、（３）あらかじめ水素引き抜き剤と現像液とに溶解性を有する溶媒により水素引き抜き剤溶液を作成し、この溶液を現像液に投入し混合する方法、（４）あらかじめ水素引き抜き剤を溶解あるいは均一分散させる界面活性剤により水素引き抜き剤溶液あるいは均一分散液を作成し、その溶液あるいは均一分散液を現像液に投入し混合する方法等が挙げられる。
【００３７】
液状感光性樹脂の現像液として一般的な水系現像液では、１〜５％の界面活性剤水溶液が用いられており、あらかじめ調合されたウオッシュアウト剤と称する界面活性剤を主剤とする原液を水で希釈し、必要に応じて適量の消泡剤を添加することにより作成される。
水系現像液に使用する界面活性剤に対して水素引き抜き剤の溶解性、分散性が優れる場合には、前述した混合方法（４）を用いてあらかじめ水素引き抜き剤を溶解あるいは均一分散させたウオッシュアウト剤を調合して、現像液を作成することができる。
【００３８】
この方法によれば、現像液作成工程での水素引き抜き剤の単体、溶液あるいは分散液の添加工程がなく、ウオッシュアウト剤の希釈という従来の現像液作成方法により水素引く抜き剤を含有する現像液の作成が可能となり、作業性に優れるばかりか引火点の低い有機溶剤を使用することもないので薬品取り扱い性、作業環境の点でも有利である。
【００３９】
本発明では、樹脂硬化部表面層への水素引き抜き剤の付着含浸を現像工程で行うものであるため、その含浸条件は現像液温度、現像液中の水素引き抜き剤含有量、現像時間により決定される。
現像液の温度は特に制約はなく、通常製版工程において現像性能の点から求められる現像温度で差し支えない。現像液温度を高くすると一般的に現像液に対する水素引き抜き剤の溶解性、均一分散性が向上し、また樹脂硬化部表面の膨潤が大きくなり、水素引き抜き剤の含浸量が増大するために表面粘着性除去効果が増大する。安定した版表面の粘着性除去効果を得るためには、現像液温度が２０〜６０℃に保たれていることが好ましい。
【００４０】
特公昭５６−１６１８２号公報に記載の版浸漬による表面粘着性除去方法では、浸漬時間と水素引き抜き剤濃度の最適化により粘着性除去効果の調整が可能であったが、本発明では現像時間が樹脂硬化部への水素引き抜き剤の含浸時間となるため、現像時間を変えずに効果を出そうとしたとき水素引き抜き剤の含有量で表面粘着性除去効果の調整を行うことになる。したがってこの場合、現像時間については、未露光樹脂を十分に洗い流すことができる時間であればよい。例えば、厚みが５〜７ｍｍの感光性樹脂版の一般的な現像時間は５〜１０分である。
【００４１】
現像液中の水素引き抜き剤の含有量については、感光性樹脂組成物の種類、水素引き抜き剤の種類、現像温度、現像時間、現像方法（スプレー、ブラシ等、これに付随する条件の変化）等により最適含有量は異なるが、十分な表面粘着性除去効果を得るためには、現像液１００重量部に対して水素引き抜き剤０．０１〜１０重量部であり、好ましくは０．０５〜１０重量部である。０．０１重量部以下の含有量では表面粘着性除去効果が十分ではなく、１０重量部を超えた含有量では表面粘着性除去効果の増大がないばかりか、現像液への負荷が大きくなるため現像性への悪影響が生じる。
【００４２】
本発明の効果の一つである非粘着性の感光性樹脂印刷版を得るためには、
（１）水素引き抜き剤を含有する現像液で露光した感光性樹脂を現像すること、
（２）現像後、該硬化版に活性光線を照射して水素引き抜き剤を活性化（励起）して水素引き抜き反応を起こすことが必要である。これら二つの工程を感光性樹脂印刷版の製造工程として一般的な、露光、現像、後露光、乾燥の４つの工程の中で行い、また装置的改良を必要としないことは、本発明の一つであり、効果である。
【００４３】
本発明において、樹脂硬化物表面層への水素引き抜き剤の含浸を現像工程で行うのは、単に現像工程と含浸工程を一体化するといった工程的簡略化のみならず、現像液と樹脂の親和性により水素引き抜き剤の含浸がより効果的に行われることを期待したものである。結果的にメカニズムの詳細は明らかでないが、特開昭５６−１６１８２号公報に記載の方法に対して現像液の化学的性質により表面粘着性の除去効果が増大しているばかりか、表面粘着性除去効果の増大に対しては現像性改善のための現像機の様式が物理的に寄与するところも大きい。
【００４４】
次に本発明の一つである、露光した感光性樹脂を水素引き抜き剤を含有する現像液により現像した後、該硬化版表面に活性光線を照射することを特徴とする感光性樹脂印刷版の製造方法について詳細に説明する。
液状感光性樹脂の露光工程は、液状樹脂を一定厚みに整える成型工程を併せて行われる。この様な液状感光性樹脂の成型・露光工程を行う装置を製版機と呼ぶ。
【００４５】
液状感光性樹脂を用いた凸版印刷用の刷版の成型・露光工程は、（１）紫外線透過性のガラス板上にネガフィルムを置き、薄い保護フィルムでカバーした後、その上に液状感光性樹脂を流し、これが一定の版厚になるようスペーサーを介して支持体となるベースフィルムを貼りあわせ、さらにその上から紫外線透過性のガラス版で押さえつけることによる成型工程、（２）紫外線蛍光灯を光源とする活性光線（３００ｎｍ以上に波長分布を有する）を下部ガラス側からネガフィルムを介して照射し画像形成を行うレリーフ形成露光工程、（３）上部ガラス側から支持体を介して下部と同様の活性光線を短時間照射することにより、版の支持体側全面に均一な薄い硬化樹脂層すなわち床部形成層（バック析出層）を析出させるバック露光工程、を順次行うことで成される。
【００４６】
フレキソ印刷に用いるような刷版の厚みが４ｍｍ以上の場合には、印刷時の印圧に対するレリーフの強度を補うために土台となるシェルフ層を形成する必要がある。この場合、レリーフ露光前に上部ガラス側から専用のネガフィルムを用いたマスキング露光を行う必要がある。
【００４７】
固体（シート）状感光性樹脂は、感光性樹脂層を一定厚みに成型し、保護フィルム層、保護膜層、感光性樹脂層、ベースフィルム（支持体）層からなる複合構成体であるためその露光工程は、（１）紫外線透過性のガラス板上に固体（シート）状感光性樹脂の支持体側が接するように配置し、紫外線蛍光灯を光源とする活性光線を下部ガラス側から照射するバック露光工程、（２）保護フィルムを剥離して露出した保護膜上にネガフィルムを密着させ、上部からネガフィルムを介して下部と同様の活性光線を照射するレリーフ露光工程、を順次行うことで成される。
以上の露光工程は、一般的に行われている方法の一例に過ぎず、本発明の露光工程は、露光後に現像液での現像を必要とする方式であれば、その様式に依らず全てに適応できる。
【００４８】
本発明の現像工程では、前記した水素引き抜き剤を含有する現像液を使用することを特徴としている。しかし現像方法としては、一般的に用いられている現像方法と同様の方法が適用できる。
例えば、現像液中に露光した感光性樹脂版を浸漬する方法、現像液をスプレーノズルから露光した感光性樹脂版面上に吹き付け未硬化樹脂を溶解除去する方法、あるいは浸漬・スプレーにより膨潤した未硬化樹脂をブラシで掻き取る方法などが挙げられ、感光性樹脂の湿式現像に関する公知技術の全てに適応できる。
【００４９】
本発明における現像後硬化版への活性光線照射は、通常製版の後露光工程と供して行うことが望ましいが、通常製版の後露光工程として以下に示す活性光線の適正を満たさない場合、別途適正な活性光線照射工程を付加しなければならない。
【００５０】
水素引き抜き剤を含有した現像液により現像した硬化樹脂版に照射する活性光線は、水素引き抜き剤を効率よく励起させる波長領域に波長を有していることが必要であり、活性光線の波長について特に制限するものではない。上述した有機カルボニル化合物を水素引き抜き剤として用いる場合、特に３００ｎｍ以下の短波長領域に波長分布を有する紫外線を用いることが好ましい。しかし２００ｎｍ以下に波長を有する活性光線を空気中で照射する場合、オゾンの発生、硬化物に対する酸化反応が無視できないため２００〜３００ｎｍの波長領域に分布を有する活性光源が好ましい。たとえば低圧水銀灯、殺菌灯、重水素ランプ等を挙げることができる。
【００５１】
液状感光樹脂製版工程の後露光工程は、機械的強度の促進、表面粘着性除去を主目的とした現像後硬化樹脂版への活性光照射であり、レリーフ露光に用いる３００ｎｍ以上の波長領域に分布を有する活性光源（例えば高圧水銀灯、超高圧水銀灯、紫外線蛍光灯、カーボンアーク灯、キセノンランプ等）と２００〜３００ｎｍの波長領域に分布を有する活性光源を併用して用いられている場合が多いので、本発明の活性光線照射を後露光工程に供して行うことが可能であり、また生産性においても好ましい。
【００５２】
固体（シート）状感光性樹脂製版工程の後露光工程においては、表面粘着性の除去を目的に２００〜３００ｎｍの波長領域に分布を有する活性光線の照射を行うのが一般的であるため、本発明の活性光線照射を後露光工程に供して行うことが可能であり、また生産性においても好ましい。
また該活性光線の照射は、空気中の酸素による重合反応阻害を防止するための水中露光方式で行っても良いし、また空気中、すなわち酸素阻害への対策を行わない方法（空中露光方式）で露光しても良い。
【００５３】
ただし、空中露光方式による該活性光線照射で得られた印刷版は、印刷に供する画像部分表面つまりレリーフ露光により得られた凸部表面では十分に粘着性除去が行われるが、印刷性、版取り扱い性の為に形成されるシェルフ層、バック析出層表面（支持体側から露光し形成する）では十分に粘着性が除去されない場合があり、特に液状感光性樹脂では顕著である。
シェルフ層、バック析出層の表面粘着性が紙粉付着、紙ムケ等へ及ぼす影響は軽微であり、印刷版としては実用可能なものも得られるが、版表面全体に粘着性を除去する方法としては水中後露光方式が望ましい。
【００５４】
十分な表面粘着性除去効果を得るための適正露光量は、硬化樹脂版の樹脂組成、水素引き抜き剤の種類、樹脂組成に対する水素引き抜き剤の含浸量により異なるが、少なくとも５００ｍＪ／ｃｍ^２ （オーク製作所紫外線測定器ＵＶ−Ｍ０２により２５０ｎｍの波長における照射量を測定し、照射時間から算出した値）以上を必要とし、通常１０００〜３０００ｍＪ／ｃｍ^２ の範囲で露光することが好ましい。５０００ｍＪ／ｃｍ^２ 以上の露光量では版表面に微少なクラックが生じるので好ましくない。
乾燥工程は、版表面の水分がなくなるまで行えば良く、特に温度、時間、方式について制限するところではない。
【００５５】
【発明の実施の形態】
印刷版表面の粘着性評価は、直径５０ｍｍ、巾１３ｍｍのアルミニウム輪の円周部表面にポリエチレンフィルムを貼り付けたものをレリーフ表面層に接触させ、アルミニウム輪に５００ｇの荷重をかけて４秒間放置した後、毎分３０ｍｍの速度でアルミニウム輪を引き上げ、アルミニウム輪がレリーフ表面から離れる時の粘着力をプッシュブルゲージで読みとるタイプのタックテスター（東洋精機社製）により行った。タックテスターの値（以後タック値と記載）は小さい方が表面粘着性がない印刷版であるといえる。ただし恒久的粘着性評価では、印刷時に剥がれ落ちてしまうコーティング層がない状態、すなわち感光性樹脂組成中に表面粘着性除去を目的とした化合物が含まれる場合はそれを除去して、感光性樹脂基質の粘着性を測定しなければならない。
【００５６】
タックテスターによる指示値がおよそ５０ｇを超えるものは、印刷版表面に異物が付着して印刷物に不良をきたし、また１００ｇを超えるものは、印刷版を重ね置きしたときに版同志が密着したり、被印刷物が紙である場合には印刷面と紙との粘着により紙ムケの現象が起こる。良好な印刷版としては０ｇであることが望ましいが、３０ｇ以下であれば実用上粘着性に起因する問題は起こり得ないと考えられている。印刷版の中でも特に粘着性が悪いとされている液状感光性樹脂印刷版では、表面粘着性除去の為の何らかの処置を施していない場合、タックテスターによる指示値が１００ｇを超えるものが一般的である。
【００５７】
【実施例】
次に実施例により本発明をさらに詳細に説明するが、本発明はこれに限定されるものではない。
【００５８】
実施例１
特開平１−２４５２４５号公報記載の実施例１により得られる感光性樹脂組成物（以後液状感光性樹脂Ａと記載、ポリエーテル系不飽和ポリウレタンポリマー使用）をＡＬＦ−２１３Ｅ型製版機（旭化成工業（株）製）を用いて露光工程まで終了した７ｍｍ版を作成した。露光量はレリーフ深度２ｍｍ、シェルフ層５ｍｍ、バック析出層１ｍｍ、また６５ ｌｉｎｅ／ｉｎｃｈ３％のハイライト形成が可能となる適正露光条件とした。
【００５９】
液状感光性樹脂Ａを乳化し得るＡＰＲ（登録商標）ウオッシュアウト剤：タイプＷ−８（主剤：アニオン系界面活性剤使用、旭化成工業（株）製）にベンゾフェノンを３．５％の濃度に溶解しウオッシュアウト剤：ＷＺ−８を調合した。 ＡＬ−４００Ｗ型現像機（ドラム回転スプレー式、旭化成工業（株）製）の現像液漕（７０リットル）でＷＺ−８が２％になるよう水で希釈し、消泡剤ＳＨ−４（シリコーン混和物、旭化成工業（株）製）を０．３％添加して現像液とした。結果的にこの現像液中には、０．０７％のベンゾフェノンが含有されていることになる。
【００６０】
準備した現像液を４０℃に温調を行った後、露光工程まで終了した液状感光性樹脂Ａからなる７ｍｍ版を１０分間の現像時間で現像した。
次いで、現像した版を水道水で現像液による泡が落ちる程度に洗浄した後、ＡＬ−２００ＵＰ型後露光機（旭化成工業（株）製）で紫外線蛍光灯、殺菌灯共に２５００ｍＪ／ｃｍ^２ の露光量で水中後露光を行った。
その後ＡＬ−１００Ｐ型乾燥機（旭化成工業（株）製）で版表面の水分が無くなるまで約３０分乾燥を行った後、２０℃恒温室にて一晩放置して印刷版を得た。
【００６１】
得られた液状感光性樹脂Ａ印刷版の印刷に供する画像表面（以下、印画部と略記）をエチルアルコールを染み込ませた布で激しく拭いて、エチルアルコールが揮発した後、版表面粘着性を前記した方法により測定したところ、タック値は０ｇであった。バック析出層についても触感評価により粘着性がないことを確認した。
【００６２】
実施例２
特開平３ー１５７６５７号公報記載の実施例３により得られる感光性樹脂組成物（以後液状感光性樹脂Ｂと記載、ポリエーテル／ポリエステル系不飽和ポリウレタンポリマー使用）を用いて実施例１と同様に露光工程まで終了した７ｍｍ版を作成した。
次いでＷ−８が液状感光性樹脂Ｂをも乳化し得るウオッシュアウト剤であるため、現像液としてＷＺ−８の２％水溶液を用いて、実施例１と同様に現像、水中後露光、乾燥工程を行って印刷版を得た。
得られた液状感光性樹脂Ｂ印刷版の印画部表面エチルアルコール拭き後タック値は２０ｇであった。
【００６３】
実施例３
特公昭５５−０３４９３０号公報に記載の実施例１により得られる感光性樹脂組成物（以後液状感光性樹脂Ｃと記載、１，２−水添ポリブタジエン系不飽和ポリウレタンポリマー使用）をＡＬＦ−２１３Ｅ型製版機を用いて露光工程まで終了した３ｍｍ版を作成した。露光量はレリーフ深度２ｍｍ、バック析出層１ｍｍ、また１００ ｌｉｎｅ／ｉｎｃｈ３％のハイライト形成が可能な最適露光条件とした。
液状感光性樹脂Ｃを乳化し得るＡＰＲウオッシュアウト剤：タイプＷ−６（主剤：ノニオン系界面活性剤、アニオン系界面活性剤併用、旭化成工業（株）製）にベンゾフェノンを５％の濃度に溶解しウオッシュアウト剤：ＷＺ−６を調合した。
【００６４】
ＡＬ−４００Ｗ型現像機の現像液漕（７０リットル）でＷＺ−６が２％になるよう水で希釈し、消泡剤ＳＨ−４を０．３％添加して現像液とした。結果的にこの現像液中には、０．１％のベンゾフェノンが含有されていることになる。
上記組成の現像液：ＷＺ−６の２％水溶液を使い実施例１と同様の方法で成型・露光された液状感光性樹脂Ｃからなる３ｍｍ版を現像、後露光、乾燥して印刷版を得た。
得られた液状感光性樹脂Ｃ印刷版の印画部表面エチルアルコール拭き後タック値は５０ｇであった。
【００６５】
実施例４
特開平５−１３４４１０号公報記載の実施例１により得られる感光性エラストマー組成物をシート状に加圧成型したもの（以後固体（シート）状感光性樹脂Ｄと記載、スチレン／ブタジエン共重合ポリマー使用、２．８４ｍｍ版）をレリーフ深度２ｍｍ、１００ ｌｉｎｅ／ｉｎｃｈ３％のハイライト形成が可能となる露光条件で露光した。
次いでテトラクロルエチレン／ｎ−ブチルアルコール（３／１）の混合液にベンゾフェノンを０．３％溶解した溶液を用いてブラシによる未露光部分の洗い出し（現像）を行い、６０℃で１時間乾燥後、室温一晩放置し、殺菌灯を光源とする後露光装置により露光量１０００ｍＪ／ｃｍ^２ で後露光して印刷版を得た。製版工程はＡＦＰ１５００システム（旭化成工業（株）製）により行った。
得られた固体（シート）状感光性樹脂Ｄ印刷版の印画部表面エチルアルコール拭き後、タック値は３０ｇであった。
【００６６】
実施例５
現像液として、ウオッシュアウト剤Ｗ−８：２％、消泡剤ＳＨ−４：０．３％を含有する水溶液７０リットルに（４−ベンゾイルベンジル）塩化トリメチルアンモニウムを１５０ｇ添加した液を用いること以外は実施例１と同様の方法で印刷版を得た。
得られた液状感光性樹脂Ａ印刷版の印画部表面エチルアルコール拭き後タック値は１０ｇであった。
【００６７】
実施例６
あらかじめベンゾフェノン：５０ｇをエタノール：０．５リットルで溶解し、ベンゾフェノン−エタノール溶液を作成した。
ウオッシュアウト剤Ｗ−８：２％、消泡剤ＳＨ−４：０．３％で調合した水溶液７０リットルに上記ベンゾフェノン／エタノール溶液を添加して現像液とした。結果的にこの現像液中には、０．０７％のベンゾフェノンが含有されていることになる。
該現像液の引火点を測定した結果、９９℃において液が沸騰して引火点は測定不能であった。
上記現像液を用いること以外は実施例１と同様の方法で製版した。
得られた液状感光性樹脂Ａ印刷版の印画部表面エチルアルコール拭き後タック値は０ｇであった。
【００６８】
実施例７
実施例１と同様の方法により現像まで行った版を水道水で界面活性剤による泡が落ちる程度に洗浄した後、ＡＬ−２００ＵＰの水槽に水を入れないで使用して、紫外線蛍光灯、殺菌灯共に２５００ｍＪ／ｃｍ^２ の露光量で後露光を行い、次いで乾燥工程を行うことにより印刷版を得た。
得られた液状感光性樹脂Ａ印刷版の印画部表面エチルアルコール拭き後タック値は１０ｇであった。
バック析出層については、触感による評価の結果、一部でべとつきが残っている部分があることが確認された。
【００６９】
比較例１
ウオッシュアウト剤としてベンゾフェノンの含有されていないＷ−８を使用すること以外はすべて実施例１と同様の方法で製版した。
得られた液状感光性樹脂Ａ印刷版の印画部表面エチルアルコール拭き後タック値は１００ｇであった。
バック析出層については触感評価の結果、全体にべとつきがあることが確認された。
【００７０】
比較例２
ウオッシュアウト剤としてベンゾフェノンの含有されていないＷ−８を使用すること以外はすべて実施例２と同様の方法で製版した。
得られた液状感光性樹脂Ｂ印刷版の印画部表面エチルアルコール拭き後タック値は４００ｇであった。
【００７１】
比較例３
ウオッシュアウト剤としてベンゾフェノンの含有されていないＷ−６を使用すること以外はすべて実施例３と同様の方法で製版した。
得られた印刷版の印画部表面エチルアルコール拭き後タック値は４１０ｇであった。
【００７２】
比較例４
現像液としてベンゾフェノンを添加しないテトラクロルエチレン／ｎ−ブチルアルコール（３／１）の混合液使用すること以外はすべて実施例４と同様の方法で製版した。
得られた固体（シート）状感光性樹脂Ｄ印刷版の印画部表面エチルアルコール拭き後タック値は７０ｇであった。
【００７３】
比較例５
実施例１のＡＬ−２００ＵＰによる水中後露光工程において、殺菌灯を光源とする活性光線の照射を行わず、紫外線蛍光灯だけで後露光を行うこと以外はすべて同様の方法で製版した。
液状感光性樹脂Ａ印刷版の印画部表面エチルアルコール拭き後タック値は４２０ｇであった。
【００７４】
比較例６
比較例１と同様の方法により現像まで行った版を水道水で界面活性剤による泡が落ちる程度に洗浄し、ＡＬ−１００Ｐで版表面の水分が無くなるまで乾燥を行った。その後、ＡＬ−２００ＵＰの水槽に水を入れないで使用して、紫外線蛍光灯、殺菌灯共に２５００ｍＪ／ｃｍ^２ の露光量で後露光し、次いで乾燥工程を行うことにより印刷版を得た。
得られた液状感光性樹脂Ａ印刷版の印画部表面エチルアルコール拭き後タック値は２３０ｇであった。
バック析出層については、触感評価の結果、全体に粘着性を有していることを確認した。
【００７５】
比較例７
比較例１と同様の方法により現像まで行った版を４０℃に加温した０．７ｇ／リットルのベンゾフェノンのエチルアルコール溶液に１０分間浸漬し、版表面のエチルアルコールが揮発するまで室温で放置した後、ＡＬ−２００ＵＰの水槽に水を入れないで使用して紫外線蛍光灯、殺菌灯共に２５００ｍＪ／ｃｍ^２ の露光量で後露光を行うことにより印刷版を得た。
得られた液状感光性樹脂Ａ印刷版の印画部表面エチルアルコール拭き後タック値は４１０ｇであった。
バック析出層について触感評価を行ったところ、未硬化粘着物が手に付着するほどべとつきがあった。
【００７６】
比較例８
ベンゾフェノン／エチルアルコール溶液の濃度を１０ｇ／リットルとする以外は比較例７と同様の方法で製版した。
得られた液状感光性樹脂Ａ印刷版の印画部表面エチルアルコール拭き後タック値は３００ｇであった。
バック析出層については触感評価の結果、全体にべたつきがあることを確認した。
【００７７】
比較例９
比較例１で得られた版を４０℃に加温した１０ｇ／リットルのベンゾフェノンのエチルアルコール溶液に１０分間浸漬し、版表面のエチルアルコールが揮発するまで室温で放置した後、ＡＬ−２００ＵＰの水槽に水を入れないで使用して殺菌灯１０００ｍＪ／ｃｍ^２ で露光を行うことによって印刷版を得た。
得られた液状感光性樹脂Ａ印刷版の印画部表面エチルアルコール拭き後タック値は０ｇであった。
バック析出層についても触感評価を行った結果、べとつきがないことを確認した。
【００７８】
この方法では、表面粘着性除去効果としては十分発揮されているものの、一連の製版工程に加えて版浸漬・乾燥・殺菌光照射といった表面処理工程を付属することから製版時間にかかる影響が大きい。また浸漬液溶媒として有機溶剤（エタノールの引火点は１３℃）を用いるため、取り扱い性、作業環境の点から実用製版設備としては、装置の防爆化、各種排気装置の設置等、大幅な設備的改善が必要となる。
【００７９】
比較例１０
比較例１で得られた版を４０℃に加温した１０ｇ／リットルのベンゾフェノン／水−エチルアルコール溶液（水／エチルアルコール＝１／１）に１０分間浸漬し、版表面の水分が揮発する迄ＡＬ−１００Ｐで乾燥した後、ＡＬ−２００ＵＰの水槽に水を入れないで使用して殺菌灯１０００ｍＪ／ｃｍ^２ で露光を行うことによって印刷版を得た。
得られた液状感光性樹脂Ａ印刷版の印画部表面エチルアルコール拭き後タック値は１０ｇであった。
ベンゾフェノンの水−エチルアルコール溶液の引火点を測定したところ２５℃であった。
【００８０】
ＡＬ−１００Ｐは防爆仕様ではなく引火点２５℃の溶媒の乾燥には適していないため、本格的な製版工程として使用するには装置的改良が必要である。
室温放置による乾燥を試みたが、浸漬後の液きりをよく行っても１時間以上かかってしまい、乾燥が十分でない状態で殺菌灯による露光を行うと液が付着した部分では粘着性除去が十分に行われず１００ｇ前後の測定値を示し、また印刷版表面で外観上問題となるレベルのシミの様な模様が発生した。
【００８１】
【発明の効果】
本発明による感光性樹脂印刷版用現像液は、従来の現像液に比べ取り扱いの点でなんら変わることがない。該現像液を用いた製版方法により得られた感光性樹脂版は、印刷前後ならびに印刷中において版表面の粘着性が現れることはなく、製版を行った後、印刷中、置き版時において版表面に異物が付着することがないため版表面を拭く等の作業を行う必要がなく、その作業性はゴム版を用いる場合とほとんど変わることなく取り扱い得る。
【００８２】
本発明による感光性樹脂印刷版の製造方法では、液状感光性樹脂を用いた印刷版製版工程として挙げられる製版・露光工程、現像（ウオッシュアウト）工程、後露光工程、乾燥工程、また固体（シート）状感光性樹脂を用いた印刷版製版工程として挙げられる露光工程、現像（ウオッシュアウト）工程、乾燥工程、後露光工程の一連の作業工程を増やすことがないため製版コストにかかる影響は全くない。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for producing a photosensitive resin printing plate widely used as a developer for photosensitive resin printing plates containing a hydrogen abstracting agent and a printing plate for letterpress printing using the developing solution (hereinafter referred to as plate making in some cases). Method or plate making).
[0002]
[Prior art]
The photosensitive resin printing plate is generally subjected to a radical polymerization reaction by irradiation with actinic rays, and after an exposure step of curing only the photosensitive layer in the relief portion, unremoved resin other than the relief portion is dissolved and removed with a predetermined washing liquid (developer), or By swelling and dispersing and mechanically removing the resin, it can be obtained by a developing step in which only a cured portion appears on the plate surface as a relief.
[0003]
In general, in the case of a photosensitive resin utilizing a radical polymerization reaction, the reaction of elimination of radical active species occurs in competition with the growth reaction, so that it is difficult to increase the degree of polymerization with high sensitivity, that is, when the reaction rate is increased. The degree of polymerization is determined by the concentration of the initiator. In order to obtain a relief suitable for printing as a photosensitive resin, and to obtain a sensitivity, ie, a reaction speed, necessary for efficiently and simply performing a plate-making operation, a predetermined amount of initiator is required. Since the degree of polymerization is limited and unreacted substances remain even after curing, the obtained printing plate surface is more or less sticky, that is, has tackiness.
[0004]
Plate making of a photosensitive resin printing plate is generally performed in four steps of exposure, development, post-exposure, and drying, and post-exposure cures unreacted substances on the inside and surface of a cured plate obtained after development. This is a step of irradiating the printing plate with an actinic ray in order to increase the mechanical strength or reduce the surface tackiness of the plate. However, even in a printing plate that has been subjected to the post-exposure step, the removal of surface tackiness is not always sufficient.
[0005]
When such a printing plate with a large adhesiveness is used for printing, poor workability at the time of loading and unloading of the printing plate from the printing plate cylinder, adhesion of printing plates to each other during printing, adhesion of dust, and paper dust during printing There are problems such as adhesion of paper and paper waste. In particular, during printing, when paper dust adheres or paper is distorted due to the adhesiveness of the plate, it is necessary to interrupt printing and wipe the plate, which significantly reduces the work efficiency.
[0006]
As a method for solving the above-mentioned problems, at the time of post-exposure, the photosensitive resin layer is immersed in a liquid and irradiated with actinic rays (post-exposure method in water) or post-exposed in an inert gas. A method of accelerating the polymerization of the surface, coating the photosensitive resin plate with various coating materials such as rubber latex and Saran latex to reduce the surface tackiness, or using an oxidizing agent or a reducing agent alone or in combination with a photosensitive resin A method of chemically treating a plate, a method of combining these, or the like is employed. In addition, as one type of coating method, a specific compound having a higher alkyl group is contained in a photosensitive resin composition, and a method for removing surface tackiness utilizing the fact that the compound crystallizes and precipitates on the printing plate surface after plate making (particularly, JP-A-61-120142) has also been proposed.
[0007]
However, these methods have insufficient effects themselves, or even if effective, the handling of the used chemicals may be a problem. Specifically, (1) the coating method has a drawback that the coating layer is peeled off during printing, and the effect persistence is insufficient. (2) Depending on the type of the photosensitive resin composition, the tackiness removal itself may be insufficient even in post-exposure in an atmosphere in which oxygen is blocked, such as in a liquid or an inert gas. (3) In a treatment method using an oxidizing agent and a reducing agent, it is necessary to pay attention to handling of generally used chemicals, and it is necessary to perform rust prevention on a device that comes into contact with the treatment liquid.
[0008]
In particular, (2) forms a three-dimensional structure by blocking radical oxygen and efficiently performing the radical polymerization of the polymerizable double bond in the composition, and increases the mechanical strength and simultaneously reacts unreacted (that is, cross-linked). ) To reduce tackiness by minimizing the presence of a prepolymer. However, in the case where the number of polymerizable double bonds in one molecule of the prepolymer is large, the mechanical strength is increased, but the effect of removing tackiness is insufficient, and the polymerizable double bond is insufficient. When the number of bonds exceeds 2, the actinic ray irradiation time must be very long to achieve a sufficient tackiness removing effect.
[0009]
That is, it is difficult to react all terminal double bonds in the current plate making process, and even if all the double bonds at the prepolymer terminal react, a plate having no tackiness is often not obtained. Therefore, in order to more sufficiently remove the tackiness of the photosensitive resin composition containing such a prepolymer, it is effective to perform a method other than the polymerization of the polymerizable double bond to three-dimensionally crosslink the prepolymer. It is.
[0010]
In Japanese Patent Publication No. 56-16182, three-dimensional cross-linking by a reaction other than a double bond is described. A method of cross-linking by creating a bond between chains is disclosed. That is, after impregnating the surface layer of the cured radical polymerizable resin with a hydrogen abstracting agent capable of abstracting hydrogen atoms in the compound by being irradiated with actinic rays, the impregnated portion of the cured product is 300 nm or less, The method is preferably a method of irradiating an actinic ray having a wavelength of 200 to 300 nm to remove the surface tackiness of the cured product of the radically polymerizable resin.
[0011]
In Japanese Patent Publication No. 56-16182, as a specific description of a method of impregnating a surface layer of a cured product of a radically polymerizable resin with a hydrogen extracting agent, a hydrogen extracting agent is added to ethanol, isopropanol or a mixed solution of water / ethanol (1/4). Examples include dissolving and immersing the cured product in the obtained solution, and spraying the solution onto the cured product surface layer by spraying.
[0012]
[Problems to be solved by the invention]
However, when impregnated with a hydrogen abstracting agent by the above-described method, although the effect of removing surface tackiness is sufficiently recognized, a step of impregnating the plate made in a normal process with the hydrogen abstracting agent is separately required. In addition, the cost of plate making increases due to an increase in plate making steps, a decrease in production volume due to complication, or the introduction of new equipment.
Further, an organic solvent such as alcohol has a low flash point, so that it is difficult to handle in the above-described usage, and new expensive equipment such as an explosion-proof dryer and a forced exhaust device is required.
[0013]
Therefore, the present invention is to improve the workability, productivity or chemical handling in the surface tackiness removing method of Japanese Patent Publication No. 56-16182 utilizing a crosslinking reaction with a hydrogen abstracting agent, and to improve the surface tackiness more effectively. An object of the present invention is to provide a developer for a photosensitive resin printing plate and a method for producing the photosensitive resin printing plate to realize the invention.
[0014]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to solve such problems, and as a result, by adding a hydrogen abstracting agent to a developer, a conventional plate making process (exposure, development, post-exposure) can be performed without newly providing an immersion process. (Drying) to obtain a photosensitive resin printing plate having no tackiness on the plate surface, and completed the present invention.
[0015]
That is, one of the present invention is a developer for a photosensitive resin printing plate, characterized by containing a hydrogen abstracting agent capable of abstracting a hydrogen atom in a compound by being irradiated with an actinic ray. The first is a method for producing a photosensitive resin printing plate, which comprises irradiating an actinic ray to the surface of the obtained cured plate after developing the exposed photosensitive resin with the developer.
[0016]
Hereinafter, the present invention will be described in detail.
The photosensitive resin composition to which the present invention can be applied is not particularly limited, but typical examples of the photosensitive resin composition preferably applicable include the following two types (1) and (2). Can be mentioned.
[0017]
(1) A photosensitive resin composition comprising a prepolymer having at least one polymerizable double bond in a molecule, a photopolymerization initiator, and an ethylenically unsaturated monomer having a polymerizable double bond, the prepolymer Examples thereof include those using at least one kind of unsaturated polyester, unsaturated polyurethane, unsaturated polyamide, unsaturated polyacrylate resin, unsaturated polymethacrylate resin, and various modified products thereof. Examples of such a photosensitive resin composition include those described in JP-A-1-245245, JP-A-3-157657, and JP-A-55-34930.
[0018]
(2) A photosensitive rubber composition comprising at least an unvulcanized rubber, a monomer having an ethylenic double bond, and a photopolymerization initiator, a so-called photosensitive elastomer. For example, a photosensitive resin composition described in JP-A-5-134410 can be exemplified.
[0019]
The developer for a photosensitive resin printing plate comprising a hydrogen abstracting agent according to the present invention will be described in detail.
Components other than the hydrogen-abstracting agent in the developer for a photosensitive resin printing plate according to the present invention, as long as they have an essential role of being able to wash away the uncured portion without eroding the cured reaction portion as a developer. There is no particular limitation. For example, water, an aqueous solution containing a surfactant, an alkaline aqueous solution, an organic solvent, a chlorine-based solvent, or the like that dissolves or emulsifies the uncured portion or swells the resin in the uncured portion can be used.
[0020]
As the hydrogen abstracting agent used in the present invention, an organic carbonyl compound capable of being excited by irradiation with actinic rays and capable of abstracting a hydrogen atom in another compound is preferable. For example, a Norrish type 1 reaction, ie, a reaction in which a carbonyl compound cleaves its α-position under light irradiation, or a type 2 reaction, ie, a ketone having a hydrogen which is abstracted to the γ-position of a carbonyl group is irradiated with light. An organic carbonyl compound which exhibits a similar or higher reaction than the reaction which cleaves into an olefin and a low molecular ketone compound under the following conditions is suitable.
[0021]
Representative organic carbonyl compounds that can be used in the present invention include, for example, benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-chlorobenzophenone, 4-hydroxybenzophenone, 4-benzoyl-4′-methyl- Substituted or unsubstituted benzophenones such as diphenyl sulfide, 3,3′-dimethyl-4-methoxybenzophenone, 4,4′-dichlorobenzophenone and 4-methylbenzophenone;
[0022]
Acetophenone, 4'-methylacetophenone, 2 ', 4'- or 3', 5'-dimethylacetophenone, 4'-methoxyacetophenone, 2-chloro-2-phenylacetophenone, 3 ', 4'-dichloroacetophenone, 4' Substituted or unsubstituted acetophenones such as -hydroxyacetophenone;
[0023]
Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc., benzoin alkyl ether compounds and substituted or unsubstituted aromatic ketones such as deoxybenzoin, benzyl dimethyl ketal, benzyl, 2-naphthyl phenyl ketone, dibenzosuberone Kind;
[0024]
1,4-benzoquinone, 2,6-dimethyl-1,4-benzoquinone, 2,6-dichloro-1,4-benzoquinone, anthraquinone, 2-chloroanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 2, Various o, p-quinones such as 3-dichloro-1,4-naphthoquinone, 2,3-dimethyl-1,4-naphthoquinone, 2-ethyl-1,4-naphthoquinone, phenanthrenequinone, 1,2-naphthoquinone and camphorquinone Compounds;
[0025]
Various organic carbonyl compounds such as substituted or unsubstituted thioxanthones such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-dimethylthioxanthone and 2,4-diethylthioxanthone Can be used as the hydrogen abstracting agent of the present invention.
[0026]
Preferably, the organic carbonyl compound is a compound in which at least one substituted or unsubstituted aromatic is bonded to a carbonyl carbon, and has the structure represented by the following formula (1) or (2). Is effective as the hydrogen abstracting agent of the present invention. At least one compound represented by the formula (1) or (2) may be used. Of course, two or more hydrogen abstracting agents may be used in combination.
[0027]
Embedded image

(Where X₁Is sulfur (-S-), carbonyl group (-CO-), ethylene group (-CH₂−CH ₂ −). Also R₁, R₂And R₃May be the same or different, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxyl group having 1 to 5 carbon atoms, a halogen atom of F, Cl, Br, I, and a carbon atom having 1 to 5 carbon atoms. It represents a hydroxyalkyl group, a hydroxyalkoxyl group having 1 to 5 carbon atoms or a quaternary ammonium salt derivative. )
[0028]
Embedded image

(Where X₂Represents a substituted or unsubstituted benzoyl group, a phenyl group, or a naphthyl group represented by the following general formula. Also R₄Is a hydrogen atom, a halogen atom of F, Cl, Br, I, an alkoxyl group having 1 to 5 carbon atoms, a hydroxyl group, an alkyl group having 1 to 5 carbon atoms, a hydroxyalkyl group having 1 to 5 carbon atoms or a carbon atom having 1 to 5 carbon atoms. Represents 1 to 5 hydroxyalkoxyl groups. )
[0029]
Embedded image

(Where R₅Are halogen atoms of F, Cl, Br and I, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxyl group having 1 to 5 carbon atoms, a hydroxyalkyl group having 1 to 5 carbon atoms, and a carbon atom having 1 to 5 carbon atoms. Represents a hydroxyalkoxyl group or a quaternary ammonium salt derivative. )
[0030]
Further, as the derivative of the formula (1) or (2), those having a polymerizable double bond can be used as the hydrogen abstracting agent of the present invention.
Specific examples of such compounds include benzophenone, 4,4'-dimethoxybenzophenone, 4-hydroxybenzophenone, anthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2,4-diethylthioxanthone, and 2-chlorothioxanthone. Examples of the quaternary ammonium salt derivative of the formula (1) or (2) include (2-acryloyloxy) (4-benzoylbenzyl) dimethylammonium bromide, (4-benzoylbenzyl) trimethylammonium chloride, (3-Dimethylamino-2-hydroxypropoxy) -3,4-dimethyl-9H-thioxanthone-9-one mesochloride and the like.
Among them, benzophenone is the most effective in terms of dispersibility, hydrogen extracting effect per unit weight, and the like.
[0031]
One of the effects of the present invention, that is, the effect of obtaining a non-tacky photosensitive resin printing plate is sufficiently exhibited, in the developing step using a developer containing a hydrogen abstracting agent, the photosensitive resin printing plate. It is necessary to adhere and impregnate the hydrogen extracting agent to the surface of the cured resin in the inside, and for that purpose, it is necessary that the hydrogen extracting agent of the developer composition is dispersed in the developing solution.
[0032]
It is optimal that the state of the hydrogen abstracting agent during development is dissolved, but the effect is exhibited if the agent is uniformly dispersed as a suspended state. The uniformly dispersed state refers to a state in which a required amount of the hydrogen extracting agent is dissolved and floated without sedimentation during the development, and more specifically, a required amount of the hydrogen extracting agent is precipitated for 24 hours or more at an appropriate developing temperature described later. Indicates that it will not be a thing. Regarding the particle size of the hydrogen abstracting agent in a dispersed state, the smaller the particle size, the more effective the impregnation on the surface of the hardened portion.^-5cm or less.
[0033]
In a state where the hydrogen extracting agent is not uniformly dispersed in the developing solution, that is, the hydrogen extracting agent is settled in the developing device tank and the required amount of dispersion is not maintained, the hydrogen extracting agent component retained at the bottom of the developing device is a resin. Since it does not participate in the adhesion and impregnation to the surface layer of the cured portion, the effect of removing the tackiness is insufficient. Further, in a spray type developing machine, a drop in spray pressure occurs due to clogging of a hydrogen extracting agent crystallized in a nozzle portion, which may cause a failure of the apparatus.
[0034]
As a mixing method for uniformly dispersing the hydrogen abstracting agent in the developer, the following method may be used.
When the hydrogen abstracting agent is dissolved or uniformly dispersed in the developer, the hydrogen abstracting agent is directly charged into the developer and mixed. Alternatively, a part of the developing solution may be separated and mixed with a hydrogen extracting agent may be charged into the developing solution.
[0035]
However, many hydrogen abstracting agents are solid at 10 to 20 [deg.] C., and even if they are liquids, many of them do not dissolve or uniformly disperse especially in aqueous developing solutions. In such a developer having a poor ability to dissolve or disperse the hydrogen extracting agent, it is possible to impart solubility or uniform dispersibility of the hydrogen extracting agent by changing the composition of the developing solution or adding a dispersing aid. Particularly, in an aqueous developer characterized by having no flash point at a developer use temperature of 20 to 60 ° C., the use of a surfactant capable of emulsifying a hydrogen abstracting agent is effective.
[0036]
If it is difficult to dissolve or uniformly disperse the hydrogen abstracting agent alone in the developing solution, it must be mixed in advance in such a manner that the hydrogen extracting agent is dispersed in the developing solution.
For example, (1) a liquid prepared by heating a hydrogen extracting agent to a melting point in advance and mixing it is added, and (2) a developer obtained by previously micronizing the solid of the hydrogen extracting agent by mechanical pulverization using a mixer or the like. (3) A method of preparing a hydrogen abstracting agent solution in advance with a solvent having solubility in the hydrogen abstracting agent and the developing solution, and then adding the solution to the developing solution and mixing, (4) Preliminary hydrogen A method of preparing a hydrogen extracting agent solution or a uniform dispersion with a surfactant capable of dissolving or uniformly dispersing the extracting agent, and adding the solution or the uniform dispersion to the developing solution and mixing.
[0037]
In a general aqueous developing solution as a developer for a liquid photosensitive resin, a 1 to 5% aqueous solution of a surfactant is used. And an appropriate amount of an antifoaming agent is added as necessary.
In the case where the solubility and dispersibility of the hydrogen abstracting agent are excellent with respect to the surfactant used in the aqueous developer, a washout in which the hydrogen abstracting agent is previously dissolved or uniformly dispersed using the above-mentioned mixing method (4). The developer can be prepared by mixing the agents.
[0038]
According to this method, there is no step of adding a simple substance, a solution or a dispersion liquid of the hydrogen abstracting agent in the developing solution producing step, and the developing solution containing the hydrogen abstracting agent by the conventional developing method of dilution of the washout agent is used. Is not only excellent in workability but also does not use an organic solvent having a low flash point, which is advantageous in terms of chemical handling and work environment.
[0039]
In the present invention, since the adhesion and impregnation of the hydrogen extraction agent to the resin cured portion surface layer is performed in the development step, the impregnation conditions are determined by the developer temperature, the hydrogen extraction agent content in the developer, and the development time. You.
The temperature of the developing solution is not particularly limited, and may be a developing temperature required in the plate making process from the viewpoint of developing performance. Increasing the temperature of the developer generally improves the solubility and uniform dispersibility of the hydrogen abstracting agent in the developer, increases the swelling of the cured resin surface, and increases the impregnation amount of the hydrogen abstracting agent. The elimination effect increases. In order to obtain a stable effect of removing the tackiness of the plate surface, the temperature of the developer is preferably maintained at 20 to 60 ° C.
[0040]
In the method for removing surface tackiness by plate immersion described in JP-B-56-16182, it was possible to adjust the tackiness removal effect by optimizing the immersion time and the hydrogen abstracting agent concentration. Since the time for impregnating the resin cured portion with the hydrogen extracting agent is the same, the effect of removing the surface tackiness is adjusted by the content of the hydrogen extracting agent when the effect is to be obtained without changing the developing time. Therefore, in this case, the development time may be any time as long as the unexposed resin can be sufficiently washed away. For example, a typical development time of a photosensitive resin plate having a thickness of 5 to 7 mm is 5 to 10 minutes.
[0041]
Regarding the content of the hydrogen abstracting agent in the developer, the type of the photosensitive resin composition, the type of the hydrogen abstracting agent, the developing temperature, the developing time, the developing method (spray, brush, etc., changes in conditions associated therewith), etc. Although the optimum content varies depending on the type, the hydrogen abstracting agent is used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 10 parts by weight, based on 100 parts by weight of the developing solution, in order to obtain a sufficient surface tackiness removing effect. Department. When the content is less than 0.01 part by weight, the effect of removing surface tackiness is not sufficient. When the content exceeds 10 parts by weight, not only does the effect of removing surface tackiness not increase, but also the load on the developer increases. An adverse effect on developability occurs.
[0042]
In order to obtain a non-adhesive photosensitive resin printing plate which is one of the effects of the present invention,
(1) developing the exposed photosensitive resin with a developer containing a hydrogen abstracting agent;
(2) After development, it is necessary to irradiate the hardened plate with an actinic ray to activate (excit) the hydrogen abstracting agent to cause a hydrogen abstracting reaction. It is one aspect of the present invention that these two steps are performed in the four general steps of manufacturing a photosensitive resin printing plate, namely, exposure, development, post-exposure, and drying. One is the effect.
[0043]
In the present invention, impregnating the surface layer of the cured resin with the hydrogen abstracting agent in the developing step is not only simplified in terms of the process of integrating the developing step and the impregnating step, but also the affinity between the developing solution and the resin. It is expected that impregnation with a hydrogen abstracting agent will be performed more effectively. As a result, although the details of the mechanism are not clear, the effect of removing the surface tackiness is increased due to the chemical properties of the developer as well as the method described in JP-A-56-16182. The manner of the developing machine for improving the developability physically contributes greatly to the increase of the removing effect.
[0044]
Next, as one of the present invention, after developing the exposed photosensitive resin with a developer containing a hydrogen abstracting agent, the photosensitive resin printing plate characterized by irradiating the hardened plate surface with actinic rays The manufacturing method will be described in detail.
The step of exposing the liquid photosensitive resin includes a molding step for adjusting the liquid resin to a predetermined thickness. An apparatus for performing such a liquid photosensitive resin molding / exposure step is called a plate making machine.
[0045]
The process of molding and exposing a printing plate for letterpress printing using a liquid photosensitive resin consists of (1) placing a negative film on an ultraviolet-transparent glass plate, covering with a thin protective film, and then applying a liquid photosensitive A molding process in which a resin is flown, a base film serving as a support is attached via a spacer so that the resin has a certain plate thickness, and a pressing process is further performed on the base film with a UV-transmissive glass plate. A relief forming exposure step of forming an image by irradiating an actinic ray (having a wavelength distribution of 300 nm or more) as a light source from the lower glass side through a negative film, and (3) the same as the lower part from the upper glass side via the support A back exposure step of depositing a uniform thin cured resin layer, that is, a floor-forming layer (back-deposited layer) on the entire surface of the plate side by irradiating the plate with actinic light for a short time; It is made by performing sequentially.
[0046]
When the thickness of the printing plate used for flexographic printing is 4 mm or more, it is necessary to form a shelf layer serving as a base in order to supplement the strength of the relief against the printing pressure during printing. In this case, it is necessary to perform masking exposure using a special negative film from the upper glass side before the relief exposure.
[0047]
The solid (sheet) photosensitive resin is a composite structure composed of a protective film layer, a protective film layer, a photosensitive resin layer, and a base film (support) layer, which is formed by molding a photosensitive resin layer to a predetermined thickness. The exposing step is as follows: (1) A back side in which a solid (sheet) photosensitive resin support is placed on a UV-transmissive glass plate so that the support side of the resin is in contact with the UV light from a lower glass side using a fluorescent light source as a light source. An exposure step and (2) a relief exposure step in which a negative film is adhered to the exposed protective film by peeling off the protective film, and the same active light rays as in the lower part are irradiated from above through the negative film through the negative film are sequentially performed. Is done.
The above-described exposure step is merely an example of a generally performed method, and the exposure step of the present invention is not limited to the type that requires development with a developing solution after exposure. Can adapt.
[0048]
In the developing step of the present invention, a developing solution containing the above-described hydrogen abstracting agent is used. However, as a developing method, a method similar to a generally used developing method can be applied.
For example, a method of immersing the exposed photosensitive resin plate in a developer, a method of spraying a developer onto a surface of the exposed photosensitive resin plate from a spray nozzle to dissolve and remove uncured resin, or an uncured resin swollen by immersion / spraying There is a method of scraping the resin with a brush and the like, and the present invention can be applied to all known techniques relating to wet development of a photosensitive resin.
[0049]
Irradiation of actinic rays to the post-development hardened plate in the present invention is preferably performed by performing a post-exposure step of a normal plate-making process. It is necessary to add a proper actinic ray irradiation step.
[0050]
The actinic ray applied to the cured resin plate developed with a developer containing a hydrogen abstracting agent must have a wavelength in a wavelength region that efficiently excites the hydrogen abstracting agent. It is not limiting. When the above-mentioned organic carbonyl compound is used as a hydrogen abstracting agent, it is particularly preferable to use ultraviolet light having a wavelength distribution in a short wavelength region of 300 nm or less. However, when irradiating an actinic ray having a wavelength of 200 nm or less in air, generation of ozone and an oxidation reaction to a cured product cannot be ignored, and therefore, an actinic light source having a distribution in a wavelength region of 200 to 300 nm is preferable. For example, a low-pressure mercury lamp, a germicidal lamp, a deuterium lamp and the like can be mentioned.
[0051]
The post-exposure step of the liquid photosensitive resin plate making step is an actinic light irradiation to the cured post-development resin plate for the main purpose of promoting mechanical strength and removing surface tackiness, and is distributed in a wavelength region of 300 nm or more used for relief exposure. (For example, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, an ultraviolet fluorescent lamp, a carbon arc lamp, a xenon lamp, etc.) and an active light source having a distribution in a wavelength region of 200 to 300 nm. In addition, it is possible to perform the actinic ray irradiation of the present invention by subjecting it to a post-exposure step, and it is also preferable in terms of productivity.
[0052]
In the post-exposure step after the solid (sheet) -shaped photosensitive resin plate making step, it is general to perform irradiation with actinic rays having a distribution in a wavelength region of 200 to 300 nm for the purpose of removing surface tackiness. The actinic ray irradiation of the present invention can be performed by subjecting it to a post-exposure step, and is also preferable in terms of productivity.
Irradiation with the actinic ray may be performed by an underwater exposure method for preventing polymerization reaction inhibition by oxygen in the air, or a method in which no measures are taken against air, ie, oxygen inhibition (air exposure method). May be used for exposure.
[0053]
However, in the printing plate obtained by the actinic ray irradiation by the aerial exposure method, the tackiness is sufficiently removed on the surface of the image portion to be printed, that is, the surface of the convex portion obtained by the relief exposure. In some cases, the tackiness is not sufficiently removed on the surface of the shelf layer and the back-deposited layer (formed by exposing from the support side) formed due to the nature, and particularly in the case of liquid photosensitive resin.
The effect of the surface tackiness of the shelf layer and back deposit layer on paper powder adhesion and paper scumming is negligible, and a practical printing plate can be obtained.However, as a method of removing tackiness on the entire plate surface, Is preferably an underwater post-exposure method.
[0054]
The appropriate amount of exposure for obtaining a sufficient effect of removing surface tackiness varies depending on the resin composition of the cured resin plate, the type of hydrogen extracting agent, and the amount of impregnation of the resin composition with the hydrogen extracting agent, but is at least 500 mJ / cm.²(A value calculated from the irradiation time at a wavelength of 250 nm measured by an ultraviolet meter UV-M02 manufactured by Oak Manufacturing Co., Ltd.) and usually 1000 to 3000 mJ / cm.²Exposure is preferably performed in the range described above. 5000mJ / cm²The above exposure amount is not preferable because minute cracks occur on the plate surface.
The drying step may be performed until the water on the plate surface is exhausted, and there is no particular limitation on the temperature, time and method.
[0055]
BEST MODE FOR CARRYING OUT THE INVENTION
Evaluation of the adhesiveness of the printing plate surface was performed by bringing a polyethylene film adhered to the circumferential surface of an aluminum ring having a diameter of 50 mm and a width of 13 mm into contact with the relief surface layer, applying a load of 500 g to the aluminum ring, and allowing the aluminum ring to stand for 4 seconds. After that, the aluminum ring was pulled up at a speed of 30 mm per minute, and a tack tester (manufactured by Toyo Seiki Co., Ltd.) of a type capable of reading the adhesive force when the aluminum ring was separated from the relief surface with a push bull gauge was used. It can be said that the smaller the value of the tack tester (hereinafter referred to as tack value), the printing plate having no surface tackiness. However, in the evaluation of permanent adhesiveness, if there is no coating layer that peels off during printing, that is, if the compound for the purpose of removing surface tackiness is contained in the photosensitive resin composition, it is removed and the photosensitive resin is removed. The adhesion of the substrate must be measured.
[0056]
When the value indicated by the tack tester exceeds about 50 g, foreign matter adheres to the printing plate surface to cause a defect in the printed matter, and when the value exceeds 100 g, the plates come into close contact when the printing plates are stacked, When the printing material is paper, paper sticking occurs due to adhesion between the printing surface and the paper. A good printing plate is desirably 0 g, but if it is 30 g or less, it is considered that practically no problem due to tackiness can occur. Among the printing plates, in particular, the liquid photosensitive resin printing plate, which is considered to have poor tackiness, when a measure for removing surface tackiness is not applied, a value indicated by a tack tester generally exceeds 100 g. is there.
[0057]
【Example】
Next, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto.
[0058]
Example 1
ALF-213E type plate making machine (Asahi Kasei Kogyo Co., Ltd.) (hereinafter referred to as liquid photosensitive resin A, using a polyether unsaturated polyurethane polymer) obtained in Example 1 described in JP-A-1-245245. 7 mm plate completed up to the exposure step. The exposure amount was set to an appropriate exposure condition that enables formation of a highlight having a relief depth of 2 mm, a shelf layer of 5 mm, a back deposition layer of 1 mm, and 65 lines / inch of 3%.
[0059]
APR (registered trademark) washout agent capable of emulsifying the liquid photosensitive resin A: dissolving benzophenone at a concentration of 3.5% in type W-8 (main agent: using an anionic surfactant, manufactured by Asahi Kasei Kogyo Co., Ltd.) A washout agent: WZ-8 was prepared. In a developer tank (70 liters) of an AL-400W type developing machine (drum rotary spray type, manufactured by Asahi Kasei Kogyo Co., Ltd.), diluted with water so that WZ-8 becomes 2%, an antifoaming agent SH-4 (silicone) 0.3% of an admixture (manufactured by Asahi Kasei Kogyo Co., Ltd.) was used as a developer. As a result, this developer contains 0.07% of benzophenone.
[0060]
After the prepared developer was adjusted to a temperature of 40 ° C., a 7 mm plate made of the liquid photosensitive resin A completed up to the exposure step was developed for a developing time of 10 minutes.
Next, the developed plate was washed with tap water to the extent that bubbles due to the developer were removed, and then the ultraviolet fluorescent lamp and the germicidal lamp were both 2500 mJ / cm using an AL-200UP type post-exposure machine (manufactured by Asahi Kasei Kogyo Co., Ltd.).²Post-exposure in water was performed at an exposure amount of.
Thereafter, the plate was dried for about 30 minutes using an AL-100P dryer (manufactured by Asahi Kasei Kogyo Co., Ltd.) until the surface of the plate became free of moisture, and then left overnight in a constant temperature room at 20 ° C. to obtain a printing plate.
[0061]
The surface of the image (hereinafter, abbreviated as a printing portion) to be used for printing of the obtained liquid photosensitive resin A printing plate was vigorously wiped with a cloth impregnated with ethyl alcohol, and after the ethyl alcohol was volatilized, the plate surface tackiness was reduced. As a result, the tack value was 0 g. The back deposited layer was also confirmed to have no tackiness by tactile evaluation.
[0062]
Example 2
The same as Example 1 using the photosensitive resin composition obtained in Example 3 described in JP-A-3-157657 (hereinafter referred to as liquid photosensitive resin B, using a polyether / polyester unsaturated polyurethane polymer). A 7 mm plate completed up to the exposure step was prepared.
Next, since W-8 is a washout agent capable of emulsifying the liquid photosensitive resin B as well, using a 2% aqueous solution of WZ-8 as a developer, the development, post-exposure in water, and drying steps were performed in the same manner as in Example 1. To obtain a printing plate.
The tack value of the obtained printing plate of the liquid photosensitive resin B after wiping the surface with ethyl alcohol was 20 g.
[0063]
Example 3
ALF-213E type photosensitive resin composition (hereinafter referred to as liquid photosensitive resin C, using 1,2-hydrogenated polybutadiene unsaturated polyurethane polymer) obtained in Example 1 described in JP-B-55-034930. Using a plate making machine, a 3 mm plate completed up to the exposure step was prepared. The exposure amount was set to an optimum exposure condition capable of forming a highlight with a relief depth of 2 mm, a back deposition layer of 1 mm, and 100 lines / inch 3%.
APR washout agent capable of emulsifying the liquid photosensitive resin C: dissolving benzophenone to a concentration of 5% in type W-6 (main agent: nonionic surfactant, combined use of anionic surfactant, manufactured by Asahi Kasei Corporation) Washout agent: WZ-6 was prepared.
[0064]
In a developer tank (70 liters) of an AL-400W type developing machine, WZ-6 was diluted with water so as to have a concentration of 2%, and a defoaming agent SH-4 was added by 0.3% to obtain a developer. As a result, this developer contains 0.1% of benzophenone.
Developing solution of the above composition: a 3 mm plate made of liquid photosensitive resin C molded and exposed in the same manner as in Example 1 using a 2% aqueous solution of WZ-6, developed, post-exposed and dried to obtain a printing plate Was.
The tack value of the printing plate surface of the obtained liquid photosensitive resin C printing plate after wiping with ethyl alcohol was 50 g.
[0065]
Example 4
A pressure-molded sheet of the photosensitive elastomer composition obtained in Example 1 described in JP-A-5-134410 (hereinafter referred to as solid (sheet) -shaped photosensitive resin D, using a styrene / butadiene copolymer) , 2.84 mm plate) was exposed under an exposure condition capable of forming a highlight with a relief depth of 2 mm and 100 line / inch 3%.
Then, the unexposed portion is washed out (developed) with a brush using a solution in which 0.3% of benzophenone is dissolved in a mixed solution of tetrachloroethylene / n-butyl alcohol (3/1), and dried at 60 ° C. for 1 hour. , Allowed to stand at room temperature overnight, and exposure amount of 1000 mJ / cm by a post-exposure device using a germicidal lamp as a light source.²To obtain a printing plate. The plate making process was performed using an AFP1500 system (manufactured by Asahi Kasei Corporation).
After wiping the surface of the printing portion of the obtained solid (sheet) photosensitive resin D printing plate with ethyl alcohol, the tack value was 30 g.
[0066]
Example 5
Except for using a liquid obtained by adding 150 g of (4-benzoylbenzyl) trimethylammonium chloride to 70 liters of an aqueous solution containing a washout agent W-8: 2% and an antifoaming agent SH-4: 0.3% as a developer. A printing plate was obtained in the same manner as in Example 1.
The tack value of the obtained printing plate of the liquid photosensitive resin A after wiping with ethyl alcohol was 10 g.
[0067]
Example 6
Benzophenone: 50 g was previously dissolved in ethanol: 0.5 liter to prepare a benzophenone-ethanol solution.
The above-mentioned benzophenone / ethanol solution was added to 70 L of an aqueous solution prepared with a washout agent W-8: 2% and an antifoaming agent SH-4: 0.3% to prepare a developer. As a result, this developer contains 0.07% of benzophenone.
As a result of measuring the flash point of the developer, the flash point was not measured because the solution was boiling at 99 ° C.
Plate making was performed in the same manner as in Example 1 except that the above developer was used.
The tack value of the printing surface of the liquid photosensitive resin A printing plate obtained after wiping ethyl alcohol was 0 g.
[0068]
Example 7
The plate developed up to the development in the same manner as in Example 1 was washed with tap water to the extent that bubbles due to the surfactant were removed, and then used without putting water in the AL-200UP water tank. 2500mJ / cm for both lamps²The printing plate was obtained by performing post-exposure with the above exposure amount and then performing a drying step.
The tack value of the obtained printing plate of the liquid photosensitive resin A after wiping with ethyl alcohol was 10 g.
As for the back deposited layer, as a result of evaluation by tactile sensation, it was confirmed that some portions had stickiness remaining.
[0069]
Comparative Example 1
Except for using W-8 containing no benzophenone as a washout agent, plate making was performed in the same manner as in Example 1.
The tack value of the obtained printing plate of the liquid photosensitive resin A after wiping the surface with ethyl alcohol was 100 g.
As a result of the tactile evaluation of the back deposited layer, it was confirmed that the whole was sticky.
[0070]
Comparative Example 2
Except for using W-8 containing no benzophenone as a washout agent, plate making was performed in the same manner as in Example 2.
The tack value of the printing surface of the liquid photosensitive resin B printing plate obtained after wiping ethyl alcohol was 400 g.
[0071]
Comparative Example 3
Except for using W-6 containing no benzophenone as a washout agent, plate making was performed in the same manner as in Example 3.
The tack value of the printing plate obtained after wiping the surface of the printing portion with ethyl alcohol was 410 g.
[0072]
Comparative Example 4
Except for using a mixed solution of tetrachloroethylene / n-butyl alcohol (3/1) to which benzophenone was not added as a developer, plate making was performed in the same manner as in Example 4 in all cases.
The tack value of the solid (sheet) -shaped photosensitive resin D printing plate obtained after wiping ethyl alcohol on the printing portion surface was 70 g.
[0073]
Comparative Example 5
In the underwater post-exposure step using AL-200UP in Example 1, plate making was performed in the same manner except that post-exposure was performed using only an ultraviolet fluorescent lamp without irradiating active light using a germicidal lamp as a light source.
The tack value of the printing surface of the liquid photosensitive resin A printing plate after wiping with ethyl alcohol was 420 g.
[0074]
Comparative Example 6
The plate that had been developed by the same method as in Comparative Example 1 was washed with tap water to such an extent that bubbles due to the surfactant were removed, and dried with AL-100P until the surface of the plate became dry. After that, using the water tank of AL-200UP without putting water, both the ultraviolet fluorescent lamp and the germicidal lamp are 2500 mJ / cm.²A post-exposure was performed with the exposure amount of, and then a drying step was performed to obtain a printing plate.
The tack value of the printing surface of the obtained liquid photosensitive resin A printing plate after wiping with ethyl alcohol was 230 g.
As a result of the tactile evaluation, the back deposited layer was confirmed to have adhesiveness as a whole.
[0075]
Comparative Example 7
The plate developed by the same method as in Comparative Example 1 was immersed in a 0.7 g / liter benzophenone ethyl alcohol solution heated to 40 ° C. for 10 minutes, and left at room temperature until the ethyl alcohol on the plate surface volatilized. After that, the UV-fluorescent lamp and the germicidal lamp were used without water in the water tank of AL-200UP to 2500 mJ / cm.²The printing plate was obtained by performing post-exposure with the exposure amount of.
The tack value of the printing surface of the printing portion of the obtained liquid photosensitive resin A after wiping with ethyl alcohol was 410 g.
When the tactile sensation evaluation was performed on the back deposited layer, the uncured adhesive was sticky enough to adhere to the hand.
[0076]
Comparative Example 8
Plate making was performed in the same manner as in Comparative Example 7, except that the concentration of the benzophenone / ethyl alcohol solution was changed to 10 g / liter.
The tack value of the printing surface of the printing plate of the obtained liquid photosensitive resin A after wiping with ethyl alcohol was 300 g.
As a result of the tactile evaluation of the back deposited layer, it was confirmed that the whole was sticky.
[0077]
Comparative Example 9
The plate obtained in Comparative Example 1 was immersed in a 10 g / l benzophenone ethyl alcohol solution heated to 40 ° C. for 10 minutes, and allowed to stand at room temperature until the ethyl alcohol on the plate surface volatilized. Then, an AL-200 UP water tank was used. Germicidal lamp 1000mJ / cm without water²A printing plate was obtained by performing exposure with.
The tack value of the printing surface of the liquid photosensitive resin A printing plate obtained after wiping ethyl alcohol was 0 g.
As a result of evaluation of the tactile sensation of the back deposited layer, it was confirmed that there was no stickiness.
[0078]
Although this method is sufficiently effective in removing surface tackiness, it involves a series of plate-making steps, as well as plate immersion, drying, and sterilization.LightThe addition of a surface treatment step such as spraying has a significant effect on plate making time. In addition, since an organic solvent (flash point of ethanol is 13 ° C) is used as the immersion liquid solvent, explosion-proof equipment, installation of various exhaust devices, etc. are required for practical plate-making equipment in terms of handleability and work environment. Improvement is needed.
[0079]
Comparative Example 10
The plate obtained in Comparative Example 1 was immersed in a 10 g / l benzophenone / water-ethyl alcohol solution (water / ethyl alcohol = 1/1) heated to 40 ° C. for 10 minutes, until the water on the plate surface volatilized. After drying with AL-100P, it is used without putting water in a water tank of AL-200UP and used as a germicidal lamp 1000 mJ / cm.²A printing plate was obtained by performing exposure with.
The tack value of the obtained printing plate of the liquid photosensitive resin A after wiping with ethyl alcohol was 10 g.
The flash point of a water-ethyl alcohol solution of benzophenone was 25 ° C.
[0080]
Since AL-100P is not an explosion-proof specification and is not suitable for drying a solvent having a flash point of 25 ° C., an improvement in equipment is required for use as a full-scale plate making process.
Attempted drying at room temperature, but it took more than one hour to remove the liquid after immersion. If exposure was carried out with a germicidal lamp in a state where drying was not sufficient, the adhesive on the part where the liquid adhered was sufficiently removed. The measurement value was around 100 g, and a pattern such as a stain-like level on the surface of the printing plate, which was a problem in appearance, occurred.
[0081]
【The invention's effect】
The developer for a photosensitive resin printing plate according to the present invention does not change at all in terms of handling as compared with a conventional developer. The photosensitive resin plate obtained by the plate making method using the developer does not show the tackiness of the plate surface before and after printing and before and after printing. There is no need to perform operations such as wiping the plate surface because no foreign matter adheres to the surface, and the workability can be handled almost the same as when using a rubber plate.
[0082]
In the method for producing a photosensitive resin printing plate according to the present invention, a plate making / exposure step, a development (washout) step, a post-exposure step, a drying step, a solid state (sheet) ) There is no impact on the plate making cost because there is no need to add a series of work steps such as an exposure step, a development (washout) step, a drying step, and a post-exposure step which are mentioned as a printing plate making step using the photosensitive resin. .

Claims (2)

A developer for a photosensitive resin printing plate, comprising a hydrogen abstracting agent capable of extracting a hydrogen atom in a compound by being irradiated with an actinic ray. A photosensitive resin printing plate, comprising: developing the exposed photosensitive resin using the photosensitive resin printing plate developer according to claim 1; and irradiating the surface of the obtained cured plate with actinic rays. Manufacturing method.