JP4166957B2 - Photosensitive resin composition for flexographic plates with improved image formability - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明はフレキソ印刷に用いられる版材であるフレキソ印刷用感光性樹脂構成体に関するものである。
【０００２】
【従来の技術】
一般的なフレキソ印刷用樹脂構成体は紫外線に対して透明なポリエステルフィルム等の支持体層、及びその上に設けられた感光性樹脂層からなっている。
この感光性樹脂構成体を用いてフレキソ印刷用の版を作成する場合、まず構成体の支持体層側全面に紫外線を照射することにより感光性樹脂層を部分硬化させて、感光性樹脂層内部に支持体層側界面から、所定の厚みにコントロールされた均一な硬化層を設け、ついで感光性樹脂上部を覆ったネガフィルムを通して感光性樹脂層に紫外線による画像露光を行った後、感光性樹脂層の未露光部分を現像剤で洗い流して目的とする画像、すなわちレリーフ像を形成せしめた印刷版を得る。
【０００３】
ここでネガフィルムには、感光性樹脂層に対する均一密着性が要求される。この均一密着性が不良で、感光性樹脂層とネガフィルムの間に局所的に空気層が形成された場合、画像露光の工程で部分的に紫外線の照射範囲が広がったり、ネガフィルムと感光性樹脂層の界面に介在した空気により反応阻害を受けることにより、露光後の版のレリーフ像はネガフィルムの画像を正確に再現することができなくなる。
【０００４】
一方、フレキソ印刷では１枚のネガフィルムで複数の印刷版を形成するのが一般的であり、このため画像露光後、容易にネガフィルムを剥離、再使用できるよう、ネガフィルムには感光性樹脂層界面に対する良好な剥離性をも有することが求められている。
しかしながら、感光性樹脂層は一般的に粘着性を有しているため, この上にネガフィルムを直接置いた場合、ネガフィルムを感光性樹脂表面に均一に密着させることが困難であるばかりでなく、画像露光後ネガフィルムを感光性樹脂層から剥離する際、感光性樹脂層に貼り付いたネガフィルムが破損して再使用が不可能となりコスト面でも好ましくない。
【０００５】
これらの問題に対処するために、従来感光性樹脂層とネガフィルムの間にスリップ層と呼ばれる薄い可とう性の層が設けられてきた。このスリップ層は感光性樹脂層に対し充分な密着性を有していると同時に、ネガフィルムに対しても充分な剥離性を有している。そこでスリップ層の上に置かれたネガフィルムのさらにその上から、バキュームシートと呼ばれる薄いポリエチレン等のシートを覆い被せ、ネガフィルムとスリップ層の間に介在する空気を、露光機に備えられた真空装置により排気することにより、ネガフィルムをスリップ層に均一に密着させることで均一なレリーフ画像が得られる。さらに画像露光後、系の真空を破壊した後では、スリップ層からネガフィルムを破損させることなく容易に剥離することが可能である。
【０００６】
しかしながら従来のスリップ層を用いた場合、ネガフィルムを透過した後、さらにスリップ層を透過して感光性樹脂層に到達した紫外線は、スリップ層の厚みに相当する分、照射範囲が広がったり、ネガフィルムとスリップ層及びスリップ層と感光性樹脂層との界面での屈折、散乱などにより、本来のレリーフ像よりも広い範囲で感光性樹脂の硬化が起こりやすい。また凸部レリーフ像の断面が、すそのが大きく広がった台形のような形状（このような場合、レリーフのショルダー角が小さいという）になったり、凹部では実質的に必要な彫刻深度が得られなくなったりする。
【０００７】
このような印刷版を用いて印刷をおこなった場合、本来の画像よりも広い範囲にインキが転写され、凸部では太く、凹部では狭い印刷面となるため、最適な印刷品質を得るための印圧許容幅が狭くなるなど、良好な印刷物を得ることが難しくなる。さらに近年高品質の印刷画像の要求から、微細なレリーフ像を得るために紫外線の照射量を増やす傾向にあり、このためレリーフ版のショルダー角は一層小さくなりやすく、その結果、従来のスリップ層を有する感光性樹脂構成体を用いた場合、網点濃度が低い画像を含むレリーフ印刷版において、凸部のショルダー角が大きく且つ凹部の深度が深い、良好な印刷品質を呈するレリーフ像を形成することが益々困難となってきている。
【０００８】
【発明が解決しようとする課題】
本発明は印刷許容幅が広く、網点濃度が低い画像を含むレリーフにおいても良好な印刷品質のフレキソ印刷物を得るために、優れたレリーフ形状を有するフレキソ印刷版を形成することを可能とするスリップ層を設けた感光性樹脂構成体を提供することを課題とするものである。
【０００９】
【課題を解決するための手段】
本発明者らは、前記目的を達成するために鋭意研究を重ねた結果、下記のフレキソ版用感光性樹脂構成体を用いることで、上記の課題を解決できることを見出した。
すなわち、本発明は、少なくとも（Ａ）感光性樹脂層、（Ｂ）層（Ａ）上にあり、少なくとも３２０ｎｍ〜４２０ｎｍの範囲に紫外線吸収領域が存在する化合物を含有し、１種以上の重合体から成るスリップ層を含むフレキソ版用感光性樹脂構成体を提供するものである。
【００１０】
【発明の実施の形態】
以下、本発明を詳細に説明する。
本発明で用いられるフレキソ版用感光性樹脂構成体では、少なくとも、（Ａ）ネガフィルムを通した紫外線照射により選択的に光重合可能で、且つ現像溶剤で現像可能な感光性樹脂層、及び（Ｂ）スリップ層の２つの層が含まれている構造を有している。
【００１１】
本発明におけるスリップ層（Ｂ）は、通常０．５〜２０μｍの厚さであり、且つ感光性樹脂層のレリーフ形成面を均一な厚みで完全に被覆する。このスリップ層（Ｂ）は、少なくとも３２０〜４２０ｎｍの紫外線領域に吸収波長のある化合物を含有していることが必要である。層（Ｂ）に含まれる紫外線吸収化合物の吸収波長領域が少なくともこの範囲を含むとき、露光後のレリーフ形状が、ショルダー角が大きく、凹部の深度が深いものとなる。好ましくは、少なくとも３３０〜４００ｎｍの範囲であり、より好ましくは、３４０〜３８０ｎｍの範囲である。
【００１２】
特に、この紫外線吸収化合物を含有したスリップ層（Ｂ）全体の波長３２０ｎｍ〜３９０ｎｍにおける紫外線透過率が５０〜７０％のときに、本発明の特徴である、微細な画像を含む図柄においてもショルダー角が大きく、凹部の深度も充分確保された良好なレリーフ像を、実用的な画像露光の紫外線照射時間で形成させるという効果が特に顕著である。
このようなスリップ層（Ｂ）全体の紫外線透過率は、例えば検出波長３２０ｎｍ〜３９０ｎｍの光量計（オーク社製 ＭＯ−２）等、通常知られている測定法により容易に知ることができる。
【００１３】
上記の、紫外線吸収化合物としては、例えば、アゾ系油溶染料である、オリエント化学社製 Ｖａｌｉｏｓｏｌ Ｙｅｌｌｏｗ ＭＹＥ、同社製 Ｖａｌｉｆａｓｔ Ｙｅｌｌｏｗ ４１２０、同 ４１２６、保土谷化学社製 ＡｉｚｅｎＳｐｉｌｏｎ Ｙｅｌｌｏｗ ＧＲＨ、三菱化学社製 Ｄｉａｒｅｓｉｎ Ｙｅｌｌｏｗ Ａや、紫外線吸収剤（日本チバガイギー社製 Ｔｉｎｕｖｉｎ １１３０）などが挙げられる。
【００１４】
これら化合物の含有量は、各化合物及びスリップ層（Ｂ）を構成する重合体の紫外線吸光度並びにスリップ層（Ｂ）の厚み等によるが、画像露光工程において、層（Ｂ）の下に位置する層（Ａ）に対して露光硬化に十分な量の紫外線が照射され得る範囲で適宜調整される。一般的には、スリップ層（Ｂ）全重量に対して０．１〜５０％であり、好ましくは、０．１〜３０％である。
スリップ層（Ｂ）を形成する重合体としては、一般的なフレキソ版感光性樹脂構成体用スリップ層として、必要な特性を有するもので、例えばポリアミド、アルキルセルロース、ヒドロキシアルキルセルロース、ニトロセルロース、セルロースエステル、モノビニル置換芳香族炭化水素と共役ジエンの共重合体、およびモノビニル置換芳香族炭化水素と共役ジエンの共重合体の水素添加反応物等より成る群から選ばれる、単独の重合体もしくは２種以上の重合体の組み合わせを挙げることができる。
【００１５】
スリップ層（Ｂ）の成膜方法としては、スリップ層原料となる重合体と所定の紫外線領域吸収化合物を溶媒等に溶解または分散させ、版材の保護層となるフィルム上に塗布、乾燥して得ることができる。この時、スリップ層（Ｂ）の必要な特性を確保する目的で、離型剤、可塑剤、密着力調整剤などを適宜添加することもできる。保護フィルムとしては、通常、寸法安定性、耐熱性、機械的強度から厚さ５０〜２００μｍのポリエステルフィルムが用いられる。
【００１６】
感光性樹脂層（Ａ）を選択的に露光して得られるレリーフ画像は、フレキソ印刷版として一般的に要求される特性を備えているもの、すなわち被印刷体となる紙やフィルムに対して良好な印刷性能を発揮するものであれば特に限定されない。
そのような特性を有する感光性樹脂層（Ａ）を形成するバインダーポリマーの例としては、スチレン−ブタジエン−スチレンブロック共重合体や、スチレン−イソプレン−スチレンブロック共重合体に代表されるモノビニル置換芳香族炭化水素と共役ジエンからなる熱可塑性エラストマーが挙げられる。これらのバインダーポリマーは、最終的に得られるフレキソ印刷版の機械的物性が実用的なレベルとなるためには、感光性樹脂層全体に対して、通常４０〜９０重量％を占める。特に可塑剤エラストマーとして液状ゴム例えば日本石油化学社製 ＬＰＢ、日本曹達社製 ＮＩＳＳＯ ＰＢ、ヒュルス社製 Ｐｏｌｙｏｉｌなどが挙げられ、分子量５００〜５，０００で且つ感光性樹脂層全体に対し５〜４０重量％を含むことが好ましい。
【００１７】
感光性樹脂層（Ａ）はまた、紫外線で重合可能なエチレン性不飽和化合物を含有しており、例えばアクリレート化合物、メタクリレート化合物、マレイミド誘導体、フマール酸エステルなどが挙げられる。
特にその化合物の分子量２００当たりアクリレート基を１個以上含み、且つ１分子中に２個以上のアクリレート基を含む化合物であることがより好ましい。そのような化合物としては、例えばヘキサンジオールジアクリレート、ノナンジオールジアクリレート、長鎖脂肪族ジアクリレート等を挙げることができ、これらジアクリレート化合物群から選ばれる、２種以上のものを混合して用いることもできる。また、必要に応じて他のエチレン性不飽和化合物を用いることもできる。これらのジアクリレート化合物を感光性樹脂中に含有することにより、感光性樹脂層を紫外線で硬化させる工程で、より少ない照射量でレリーフ画像形成が可能となり生産性を向上させることが可能となる。
【００１８】
感光性樹脂層（Ａ）には、さらに光重合開始剤として、感光性樹脂層全体重量に対し３〜２０重量％の芳香族ケトン類やベンゾインエーテル類など公知のラジカル重合開始剤、例えばベンゾフェノン、ミヒラーケトン、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、α−メチルロールベンゾインメチルエーテル、α−メトキシベンゾインメチルエーテル、２，２ジエトキシフェニルアセトフェノン等を挙げることができ、これら化合物の１種若しくは２種以上の組み合わせで使用することができる。
【００１９】
最後にこの感光性樹脂層に要求される特性に応じて、熱重合禁止剤、着色剤などの添加剤を含有することもできる。
感光性樹脂層（Ａ）は種々の方法で調製することができる。例えば、上述した配合成分を、加熱装置を有するニーダーロールミル、又はスクリュー押し出し機で溶融混練し、Ｔ型ダイス、プレス成形機などにより所望の厚さの板状に成形することができる。また溶媒を用い、例えばクロロホルム、テトラクロルエチレン、メチルエチルケトン、トルエンなどの溶媒に溶解して混合し、型枠に流延し溶媒を蒸発させ板状に成形することもできる。
【００２０】
層（Ａ）の下部に位置する支持体層としては、厚みが７５〜３００μの範囲の寸法安定なポリエステルフィルムを用いることができ、場合によっては感光性樹脂層と支持体層を強固に接着させるために、支持体層上に接着層を設けることもできる。
支持体層、接着層、感光性樹脂層、スリップ層、および保護フィルムをこの順に積層させた多層の感光性樹脂構成体にするためには、スリップ層が塗布された保護フィルム、及び接着層が塗布された支持体層間に、感光性樹脂層をラミネート密着することにより得ることができる。
【００２１】
感光性樹脂層を露光硬化させる紫外線光源としては、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、太陽光などがある。
ネガフィルムを介して感光性樹脂層に紫外線を露光することにより所望のレリーフ層を得ることができるが、レリーフ像の高さを調整するためには、支持体層側から全面に紫外線を照射する。このレリーフ形成露光と支持体層側からの露光はどちらを先におこなっても良く、さらに同時におこなっても良いが、画像再現性の観点より支持体側からの露光を先に行うのが好ましい。
【００２２】
感光性樹脂層の露光後、未露光部を洗い出すのに用いられる現像剤としては例えば、テトラクロルエチレン等の塩素系有機溶媒や、石油留分、トルエン、デカリン等の炭化水素類、３−メトキシブチルアセテート、ヘプチルアセテート等のエステル類などの溶剤にプロパノール、ブタノール、ペンタノ−ル等のアルコール類を混合したものを挙げることができる。
以下、実施例に基づき本発明を具体的に説明する。
【００２３】
【実施例１〜４、比較例１】
スリップ層を形成する重合体として、マクロメルト６９００（ヘンケル社製）９０重量部とタフテックＭ１９１３（旭化成社製）１０重量部を、予め加熱ニーダーロールミルにて１５０℃、１００ｒｐｍの条件で５分間混練し、混合ポリマーを調製した。ついでこのポリマーをイソプロピルアルコール／トルエン＝１／１の混合溶媒に溶解し濃度が１５重量％の溶液を調製した。
〔実施例１〕紫外線領域に吸収を持つ染料の、Ｖａｌｉｏｓｏｌ ＹｅｌｌｏｗＭＹＥ（オリエント化学社製）を上記ポリマー溶液７１重量部に対し０．７０重量部、添加してスリップ層溶液を調製した。
〔実施例２〕実施例１の染料を０．８８重量部としスリップ層溶液を調製した。
〔実施例３〕実施例１の染料を０．３５重量部としスリップ層溶液を調製した。
〔実施例４〕実施例１の染料を０．２５重量部としスリップ層溶液を調製した。
〔比較例１〕ポリマー溶液に染料を添加することなく、そのままスリップ層溶液とした。
【００２４】
次にこの溶液を、１００μｍの厚みのカバーシートとなるポリエステルフィルム上に、乾燥後の塗布量が５〜５．５ｇ／ｍ2となるようにブレードコーターを用いて塗布し、８０℃で２分間乾燥しスリップ層が塗布されたカバーシートを得た。これらの紫外線の吸収量を、光源としてＡＦＰ−１５００露光機（旭化成社製 ランプ：フィリップス社製 ６０Ｗ−１０Ｒタイプ）を用い、検出波長３２０〜３９０ｎｍの光量計（オーク社製 ＭＯ−２）にてカバーシートを取り除いたスリップ層の透過率を測定した。結果を表１に示す。
【００２５】
次にクレイトンＤＫＸ−４０５（クレイトンポリマー社製 スチレン−ブタジエン−スチレンブロック共重合体）７０部、Ｂ−２０００（日本石油化学社製 液状ポリブタジエン）２３部、１，９−ノナンジオールジアクリレート７部、２，２−ジメトキシ−２−フェニルアセトフェノン１．５部、２，６−ジ−ｔ−ブチル−ｐ−クレゾール０．３部をともに加熱ニーダーミルで混練し、感光性樹脂組成物を調製した。この感光性樹脂組成物を、１２５μｍのポリエステルフィルムの支持体上に接着層が塗布された支持体層と、実施例１〜４、比較例１で作成したスリップ層を塗布したカバーシート、それぞれ塗布面が感光性樹脂側になるように挟み、３．０ｍｍのスペーサーを用いてプレス機で、１３０℃で油圧２００ｋｇ／ｃｍ2の条件で４分間かけて成形し、スリップ層が異なるフレキソ印刷版用感光性樹脂構成体を得た。
【００２６】
この感光性樹脂構成体を、通常の製版工程にしたがって印刷版を作成した。すなわち、各感光性樹脂構成体を露光機（旭化成社製 ＡＦＰ−１５００露光機）上で、カバーシートを剥離しスリップ層上に、線数１３３ｌｉｎｅ／ｉｎｃｈ、濃度１％の網点、１００μｍ幅の凸線、及び５００μｍ幅の凹線の画像が組み込まれた評価用ネガフィルムを置き、バキュームシートで覆い真空装置によりネガフィルムを密着させた。支持体層側の紫外線ランプ（フィリップス社製 ６０Ｗ−１０Ｒランプ）によりレリーフ体の高さを調製するために２４０ｍＪ／ｃｍ2のバック露光を行い、ついで画像側のレリーフ露光（バック露光と同仕様のランプ）を８０００ｍＪ／ｃｍ2照射した。このときの紫外線ランプの強度を光量計（オーク社製 ＭＯ−２ ＵＶ−３５フィルター）で測定すると、バック露光用の下側紫外線ランプが４．０ｍＷ／ ｃｍ2、レリーフ露光用の上側紫外線ランプが７．９ｍＷ／ｃｍ2であった。
【００２７】
次にテトラクロルエチレン／ｎ−ブタノール＝３／１（容積比）を現像液として、ＡＦＰ−１５００現像機（旭化成社製）にて、版シリンダーに両面テープで各感光性樹脂構成体の支持体側を貼りつけて２５℃の温度で４分間現像を行った。現像後、６０℃の乾燥機（旭化成社製 ＡＦＰ−１５００乾燥機）で２時間乾燥し、レリーフ像を有するフレキソ印刷用の印刷版が得られた。
スリップ層の異なる印刷版の網点部の形成状態と、１００μ幅の凸線の断面より測定したショルダー角、５００μｍ幅の凹線の深さを深度顕微鏡（日商精密光学 ＫＹ−９０）で測定し、表１のような結果が得られた。
良好な印刷品質を有するレリーフ版であるためには、１３３Ｌｉｎｅ／ｉｎｃｈ、網点濃度１％のレリーフ像が形成可能で、１００μｍ幅凸部ショルダー角が５０°以上、且つ５００μｍ幅凹線深度が１００μｍ以上である必要がある。
【００２８】
スリップ層に紫外線領域に吸収波長を持つＶａｌｉｏｓｏｌ Ｙｅｌｌｏｗ ＭＹＥを添加した場合、必要とされる線数１３３ｌｉｎｅ／ｉｎｃｈ、濃度１％の網点の形成が確保され、１００μｍ幅の凸線のショルダー角が大きく、なお且つ５００μｍ幅の凹線の深さが深くなり、印刷に必要な微細なレリーフ像を形成させることと、良好な印刷物を得るための大きなショルダー角を有し凹部の深度が充分確保されたレリーフ像の両立した印刷版を得ることができた。
さらに得られたフレキソ印刷版を用いてポリプロピレンフィルムに印刷したところ、１３３ｌｉｎｅ／ｉｎｃｈ、１％の網点が印刷され、且つ太りの少ない印刷物が得られた。しかも広い印圧の許容幅を有するものであった。
【００２９】
【実施例５】
スリップ層を形成する重合体として、マクロメルト６９００（ヘンケル社製）９０重量部とタフテックＭ１９１３（旭化成社製）１０重量部を、予め加熱ニーダーロールミルにて１５０℃、１００ｒｐｍの条件で５分間混練し、ついでこのポリマー１０重量部、Ｖａｌｉｆａｓｔ Ｙｅｌｌｏｗ ４１２０（オリエント化学社製）０．２重量部をイソプロピルアルコール／トルエン＝１／１の混合溶媒に溶解し濃度が１５重量％のスリップ層溶液を調製した。
【００３０】
実施例１と同様の方法でカバーシート上にスリップ層を形成せしめ、カバーシートを取り除いたスリップ層の３２０〜３９０ｎｍでの透過率を測定したところ、６３％であった。更に実施例１で用いた感光性樹脂層に同様の方法でフレキソ印刷用感光性樹脂構成体を作成し、実施例１記載の製版工程にしたがって印刷版を作成した。線数１３３Ｌｉｎｅ／ｉｎｃｈ、濃度１％の網点が形成し、１００μｍ幅の凸線のショルダー角が５４°、５００μｍ幅の凹線の深さが１８０μｍであった。この印刷版を用いて、コート紙に印刷した結果、実施例１〜４と同様に、１３３Ｌｉｎｅ／ｉｎｃｈの網点が印刷され、且つ太りの少ない印刷物が得られ、しかも印圧許容幅の広いものであった。
【００３１】
【表１】
【発明の効果】
紫外線吸収領域が存在する化合物を含有したスリップ層と感光性樹脂層よりなるフレキソ印刷用樹脂構成体は、ショルダー角が大きく、凹部の深度が充分確保され、しかも微細なレリーフ像が形成することで、得られたフレキソ印刷版は、印圧許容幅が広く、印刷品質が向上する。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a photosensitive resin composition for flexographic printing, which is a plate material used for flexographic printing.
[0002]
[Prior art]
A general resin composition for flexographic printing comprises a support layer such as a polyester film that is transparent to ultraviolet rays, and a photosensitive resin layer provided on the support layer.
When making a flexographic printing plate using this photosensitive resin composition, first, the photosensitive resin layer is partially cured by irradiating ultraviolet rays to the entire surface of the structure on the support layer side. A uniform cured layer controlled to a predetermined thickness is provided from the support layer side interface, and then the photosensitive resin layer is exposed to ultraviolet light through a negative film covering the top of the photosensitive resin, and then the photosensitive resin. The unexposed portion of the layer is washed away with a developer to obtain a printing plate on which a target image, that is, a relief image is formed.
[0003]
Here, the negative film is required to have uniform adhesion to the photosensitive resin layer. If this uniform adhesion is poor and an air layer is locally formed between the photosensitive resin layer and the negative film, the UV irradiation range may be partially expanded in the image exposure process, or the negative film and the photosensitive film may be exposed. Due to the reaction inhibition by the air intervening at the interface of the resin layer, the relief image of the plate after the exposure cannot accurately reproduce the image of the negative film.
[0004]
On the other hand, in flexographic printing, it is common to form a plurality of printing plates with a single negative film. For this reason, the negative film has a photosensitive resin so that the negative film can be easily peeled off and reused after image exposure. It is also required to have good peelability with respect to the layer interface.
However, since the photosensitive resin layer generally has adhesiveness, it is difficult not only to directly adhere the negative film to the photosensitive resin surface when the negative film is directly placed thereon. When the negative film is peeled off from the photosensitive resin layer after image exposure, the negative film attached to the photosensitive resin layer is damaged and cannot be reused, which is not preferable in terms of cost.
[0005]
In order to cope with these problems, conventionally, a thin flexible layer called a slip layer has been provided between the photosensitive resin layer and the negative film. This slip layer has sufficient adhesion to the photosensitive resin layer and at the same time has sufficient peelability to the negative film. Therefore, the negative film placed on the slip layer is further covered with a thin sheet of polyethylene or the like called a vacuum sheet, and the intervening air between the negative film and the slip layer is applied to the vacuum provided in the exposure machine. By evacuating with the apparatus, a uniform relief image can be obtained by uniformly bringing the negative film into close contact with the slip layer. Furthermore, after the image exposure, after breaking the vacuum of the system, it is possible to easily peel off the negative film without damaging the negative film.
[0006]
However, when a conventional slip layer is used, the ultraviolet ray that has passed through the negative film and then passed through the slip layer to reach the photosensitive resin layer has an irradiation range that is equivalent to the thickness of the slip layer. Due to refraction and scattering at the interface between the film and the slip layer and between the slip layer and the photosensitive resin layer, the photosensitive resin is easily cured in a wider range than the original relief image. In addition, the cross-section of the convex relief image has a trapezoidal shape with a widened skirt (in this case, the shoulder angle of the relief is small), and the concave has a substantially necessary engraving depth. It will disappear.
[0007]
When printing is performed using such a printing plate, the ink is transferred over a wider area than the original image, and the printing surface is thicker at the convex part and narrower at the concave part. It becomes difficult to obtain a good printed matter, for example, the allowable pressure width becomes narrow. Furthermore, in recent years, due to the demand for high quality printed images, there has been a tendency to increase the amount of UV irradiation in order to obtain a fine relief image. For this reason, the shoulder angle of the relief plate tends to be further reduced. When using a photosensitive resin composition having a relief printing plate containing an image having a low halftone dot density, a relief image exhibiting good print quality with a large shoulder angle of the convex portion and a deep depth of the concave portion is formed. Is becoming increasingly difficult.
[0008]
[Problems to be solved by the invention]
The present invention provides a flexographic printing plate having an excellent relief shape in order to obtain a flexographic printed matter having a good printing quality even in a relief including an image having a wide printing allowable width and a low dot density. It is an object of the present invention to provide a photosensitive resin structure provided with a layer.
[0009]
[Means for Solving the Problems]
As a result of intensive studies to achieve the above object, the present inventors have found that the above-mentioned problems can be solved by using the following photosensitive resin composition for flexographic plates.
That is, the present invention contains at least a compound on the (A) photosensitive resin layer and (B) layer (A) and having an ultraviolet absorption region in the range of at least 320 nm to 420 nm, and one or more polymers. The photosensitive resin structure for flexographic plates containing the slip layer which consists of these is provided.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
In the photosensitive resin composition for flexographic plates used in the present invention, at least (A) a photosensitive resin layer selectively photopolymerizable by ultraviolet irradiation through a negative film and developable with a developing solvent, and ( B) It has a structure including two layers of slip layers.
[0011]
The slip layer (B) in the present invention is usually 0.5 to 20 μm in thickness, and completely covers the relief forming surface of the photosensitive resin layer with a uniform thickness. This slip layer (B) needs to contain a compound having an absorption wavelength in an ultraviolet region of at least 320 to 420 nm. When the absorption wavelength region of the ultraviolet absorbing compound contained in the layer (B) includes at least this range, the relief shape after exposure has a large shoulder angle and a deep recess. Preferably, it is at least in the range of 330 to 400 nm, and more preferably in the range of 340 to 380 nm.
[0012]
In particular, when the ultraviolet transmittance at a wavelength of 320 nm to 390 nm of the entire slip layer (B) containing this ultraviolet absorbing compound is 50 to 70%, the shoulder angle also in the pattern including a fine image, which is a feature of the present invention. In particular, the effect of forming a good relief image having a large depth and a sufficient depth of the recesses within a practical ultraviolet exposure time for image exposure is particularly remarkable.
The ultraviolet transmittance of the entire slip layer (B) can be easily known by a generally known measurement method such as a light meter (MO-2 manufactured by Oak Co.) having a detection wavelength of 320 nm to 390 nm.
[0013]
Examples of the ultraviolet absorbing compound include, for example, Variosol Yellow MYE manufactured by Orient Chemical Co., Ltd., Variast Yellow 4120, 4126 manufactured by Orient Chemical Co., Ltd., Aizen Spiro Yellow GRH manufactured by Hodogaya Chemical Co., Ltd. Yellow A, an ultraviolet absorber (Tinvin 1130 manufactured by Ciba-Geigy Japan) and the like can be mentioned.
[0014]
The content of these compounds depends on the ultraviolet absorbance of the polymers constituting the respective compounds and the slip layer (B), the thickness of the slip layer (B), etc., but in the image exposure step, the layer located below the layer (B) It adjusts suitably in the range with which sufficient quantity of ultraviolet-rays for exposure hardening can be irradiated with respect to (A). Generally, it is 0.1 to 50%, preferably 0.1 to 30%, based on the total weight of the slip layer (B).
As the polymer for forming the slip layer (B), it has necessary characteristics as a slip layer for a general flexographic photosensitive resin composition. For example, polyamide, alkyl cellulose, hydroxyalkyl cellulose, nitrocellulose, cellulose Single polymer or two kinds selected from the group consisting of ester, monovinyl substituted aromatic hydrocarbon and conjugated diene copolymer, and hydrogenation reaction product of monovinyl substituted aromatic hydrocarbon and conjugated diene copolymer The combination of the above polymers can be mentioned.
[0015]
As a method for forming the slip layer (B), a polymer as a slip layer raw material and a predetermined ultraviolet region absorbing compound are dissolved or dispersed in a solvent or the like, and applied to a film to be a protective layer of a plate material and dried. Obtainable. At this time, for the purpose of ensuring the necessary characteristics of the slip layer (B), a release agent, a plasticizer, an adhesion adjusting agent, and the like can be added as appropriate. As the protective film, a polyester film having a thickness of 50 to 200 μm is usually used in view of dimensional stability, heat resistance, and mechanical strength.
[0016]
The relief image obtained by selectively exposing the photosensitive resin layer (A) has characteristics generally required as a flexographic printing plate, that is, good for paper or film to be printed. If it exhibits a good printing performance, it is not particularly limited.
Examples of the binder polymer for forming the photosensitive resin layer (A) having such properties include styrene-butadiene-styrene block copolymers and monovinyl substituted fragrances represented by styrene-isoprene-styrene block copolymers. And a thermoplastic elastomer composed of a group hydrocarbon and a conjugated diene. These binder polymers usually occupy 40 to 90% by weight with respect to the entire photosensitive resin layer in order for the mechanical properties of the finally obtained flexographic printing plate to be at a practical level. Examples of plasticizer elastomers include liquid rubbers such as LPB manufactured by Nippon Petrochemical Co., Ltd., NISSO PB manufactured by Nippon Soda Co., Ltd., Polyol manufactured by Huls Co., Ltd., etc., having a molecular weight of 500 to 5,000 and 5 to 40 weights with respect to the entire photosensitive resin layer. % Is preferably included.
[0017]
The photosensitive resin layer (A) also contains an ethylenically unsaturated compound that can be polymerized with ultraviolet rays, and examples thereof include acrylate compounds, methacrylate compounds, maleimide derivatives, and fumaric acid esters.
In particular, a compound containing one or more acrylate groups per 200 molecular weight of the compound and two or more acrylate groups in one molecule is more preferable. Examples of such compounds include hexanediol diacrylate, nonanediol diacrylate, long-chain aliphatic diacrylate, and the like, and a mixture of two or more selected from these diacrylate compound groups is used. You can also. Moreover, another ethylenically unsaturated compound can also be used as needed. By containing these diacrylate compounds in the photosensitive resin, it is possible to form a relief image with a smaller dose and improve productivity in the step of curing the photosensitive resin layer with ultraviolet rays.
[0018]
In the photosensitive resin layer (A), as a photopolymerization initiator, 3 to 20% by weight of a known radical polymerization initiator such as aromatic ketones and benzoin ethers based on the total weight of the photosensitive resin layer, for example, benzophenone, Examples include Michler's ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, α-methyl roll benzoin methyl ether, α-methoxybenzoin methyl ether, 2,2 diethoxyphenylacetophenone, etc., one of these compounds Or it can be used in combination of 2 or more types.
[0019]
Finally, additives such as a thermal polymerization inhibitor and a colorant can be contained depending on the properties required for the photosensitive resin layer.
The photosensitive resin layer (A) can be prepared by various methods. For example, the above-described blended components can be melt-kneaded with a kneader roll mill having a heating device or a screw extruder, and formed into a plate having a desired thickness with a T-type die, a press molding machine, or the like. Moreover, it can also melt | dissolve and mix in solvents, such as chloroform, tetrachloroethylene, methyl ethyl ketone, toluene, using a solvent, it can cast in a mold and evaporate a solvent, and can also shape | mold into a plate shape.
[0020]
As the support layer located below the layer (A), a dimensionally stable polyester film having a thickness in the range of 75 to 300 μm can be used. In some cases, the photosensitive resin layer and the support layer are firmly bonded. Therefore, an adhesive layer can be provided on the support layer.
In order to obtain a multilayer photosensitive resin structure in which a support layer, an adhesive layer, a photosensitive resin layer, a slip layer, and a protective film are laminated in this order, a protective film to which a slip layer is applied, and an adhesive layer are provided. It can be obtained by laminating and sticking a photosensitive resin layer between the coated support layers.
[0021]
Examples of the ultraviolet light source for exposing and curing the photosensitive resin layer include a high-pressure mercury lamp, an ultraviolet fluorescent lamp, a carbon arc lamp, a xenon lamp, and sunlight.
A desired relief layer can be obtained by exposing the photosensitive resin layer to ultraviolet rays through a negative film. To adjust the height of the relief image, the entire surface is irradiated with ultraviolet rays from the support layer side. . Either the relief formation exposure or the exposure from the support layer side may be performed first, or may be performed at the same time, but it is preferable to perform the exposure from the support side first from the viewpoint of image reproducibility.
[0022]
Examples of the developer used to wash out the unexposed portion after the exposure of the photosensitive resin layer include, for example, chlorine-based organic solvents such as tetrachloroethylene, hydrocarbons such as petroleum fractions, toluene and decalin, 3-methoxy Examples thereof include a solvent such as butyl acetate, heptyl acetate or the like mixed with an alcohol such as propanol, butanol or pentaanol.
Hereinafter, the present invention will be specifically described based on examples.
[0023]
Examples 1-4, Comparative Example 1
As a polymer for forming a slip layer, 90 parts by weight of Macromelt 6900 (manufactured by Henkel) and 10 parts by weight of Tuftec M1913 (manufactured by Asahi Kasei) are previously kneaded in a heated kneader roll mill for 5 minutes at 150 ° C. and 100 rpm. A mixed polymer was prepared. Subsequently, this polymer was dissolved in a mixed solvent of isopropyl alcohol / toluene = 1/1 to prepare a solution having a concentration of 15% by weight.
[Example 1] Variosol YellowMYE (produced by Orient Chemical Co., Ltd.), a dye having absorption in the ultraviolet region, was added in an amount of 0.70 parts by weight to 71 parts by weight of the polymer solution to prepare a slip layer solution.
Example 2 A slip layer solution was prepared with 0.88 parts by weight of the dye of Example 1.
Example 3 A slip layer solution was prepared with 0.35 parts by weight of the dye of Example 1.
Example 4 A slip layer solution was prepared using 0.25 parts by weight of the dye of Example 1.
[Comparative Example 1] A slip layer solution was used as it was without adding any dye to the polymer solution.
[0024]
Next, this solution was applied onto a polyester film serving as a cover sheet having a thickness of 100 μm using a blade coater so that the coating amount after drying was 5 to 5.5 g / m 2, and the coating was performed at 80 ° C. for 2 minutes. A dried cover sheet with a slip layer applied was obtained. Using an AFP-1500 exposure machine (Asahi Kasei Corporation lamp: Philips 60W-10R type) as a light source, the amount of absorption of these ultraviolet rays was measured with a photometer (MO-2 manufactured by Oak Co.) having a detection wavelength of 320 to 390 nm. The transmittance of the slip layer from which the cover sheet was removed was measured. The results are shown in Table 1.
[0025]
Next, 70 parts of Kraton DKX-405 (styrene-butadiene-styrene block copolymer manufactured by Kraton Polymer Co., Ltd.), 23 parts of B-2000 (liquid polybutadiene manufactured by Nippon Petrochemical Co., Ltd.), 7 parts of 1,9-nonanediol diacrylate, A photosensitive resin composition was prepared by kneading 1.5 parts of 2,2-dimethoxy-2-phenylacetophenone and 0.3 part of 2,6-di-t-butyl-p-cresol together with a heating kneader mill. This photosensitive resin composition was applied to a support layer in which an adhesive layer was applied on a 125 μm polyester film support, and to a cover sheet on which the slip layers prepared in Examples 1 to 4 and Comparative Example 1 were applied. For flexographic printing plates with different slip layers, sandwiched so that the surface is on the photosensitive resin side, molded using a press with a 3.0 mm spacer for 4 minutes at 130 ° C. under a hydraulic pressure of 200 kg / cm 2 A photosensitive resin construct was obtained.
[0026]
A printing plate was prepared from this photosensitive resin construct in accordance with a normal plate making process. That is, each photosensitive resin constituting body was exposed on an exposure machine (AFP-1500 exposure machine manufactured by Asahi Kasei Co., Ltd.), the cover sheet was peeled off, a line number of 133 line / inch, a dot with a concentration of 1%, and a 100 μm width. A negative film for evaluation in which an image of a convex line and a concave line having a width of 500 μm was placed, covered with a vacuum sheet, and the negative film was brought into close contact with a vacuum apparatus. In order to adjust the height of the relief body with an ultraviolet lamp (Philips 60W-10R lamp) on the support layer side, 240 mJ / cm 2 of back exposure was performed, and then the image side relief exposure (with the same specifications as the back exposure). Lamp) was irradiated at 8000 mJ / cm 2 . When the intensity of the ultraviolet lamp at this time is measured with a photometer (MO-2 UV-35 filter manufactured by Oak), the lower ultraviolet lamp for back exposure is 4.0 mW / cm 2 , and the upper ultraviolet lamp for relief exposure is It was 7.9 mW / cm 2 .
[0027]
Next, using tetrachloroethylene / n-butanol = 3/1 (volume ratio) as a developer, an AFP-1500 developer (manufactured by Asahi Kasei Co., Ltd.), a double-sided tape on the plate cylinder on the support side of each photosensitive resin component Then, development was performed at a temperature of 25 ° C. for 4 minutes. After the development, the plate was dried for 2 hours with a dryer at 60 ° C. (AFP-1500 dryer manufactured by Asahi Kasei Co., Ltd.) to obtain a printing plate for flexographic printing having a relief image.
Measure the halftone dot formation of printing plates with different slip layers, shoulder angle measured from the cross section of 100μ wide convex line, and depth of concave line 500μm wide with a depth microscope (Nissho Precision Optics KY-90) As a result, the results shown in Table 1 were obtained.
In order to be a relief plate having good print quality, a relief image of 133 Line / inch, halftone dot density of 1% can be formed, a 100 μm wide convex shoulder angle of 50 ° or more, and a 500 μm wide concave line depth of 100 μm. It is necessary to be above.
[0028]
When Variosol Yellow MYE having an absorption wavelength in the ultraviolet region is added to the slip layer, the required number of lines of 133 lines / inch and the formation of halftone dots with a concentration of 1% are secured, and the shoulder angle of the convex line with a width of 100 μm is large. Moreover, the depth of the concave line having a width of 500 μm is deepened to form a fine relief image necessary for printing, and has a large shoulder angle for obtaining a good printed matter, and the depth of the concave portion is sufficiently secured. A printing plate having both relief images could be obtained.
Furthermore, when the obtained flexographic printing plate was used to print on a polypropylene film, 133 line / inch, 1% halftone dots were printed, and a printed material with less weight was obtained. Moreover, it has a wide tolerance for printing pressure.
[0029]
[Example 5]
As a polymer for forming a slip layer, 90 parts by weight of Macromelt 6900 (manufactured by Henkel) and 10 parts by weight of Tuftec M1913 (manufactured by Asahi Kasei) are previously kneaded in a heated kneader roll mill for 5 minutes at 150 ° C. and 100 rpm. Subsequently, 10 parts by weight of this polymer and 0.2 parts by weight of Valifast Yellow 4120 (manufactured by Orient Chemical Co., Ltd.) were dissolved in a mixed solvent of isopropyl alcohol / toluene = 1/1 to prepare a slip layer solution having a concentration of 15% by weight.
[0030]
A slip layer was formed on the cover sheet in the same manner as in Example 1, and the transmittance at 320 to 390 nm of the slip layer from which the cover sheet was removed was measured and found to be 63%. Further, a photosensitive resin composition for flexographic printing was prepared on the photosensitive resin layer used in Example 1 by the same method, and a printing plate was prepared according to the plate making process described in Example 1. A halftone dot having a line number of 133 Line / inch and a concentration of 1% was formed, the shoulder angle of a convex line having a width of 100 μm was 54 °, and the depth of a concave line having a width of 500 μm was 180 μm. As a result of printing on the coated paper using this printing plate, as in Examples 1 to 4, a 133 Line / inch halftone dot is printed, a printed material with less weight is obtained, and the allowable printing pressure width is wide. Met.
[0031]
[Table 1]
【The invention's effect】
The resin composition for flexographic printing composed of a slip layer containing a compound having an ultraviolet absorbing region and a photosensitive resin layer has a large shoulder angle, a sufficient depth of a concave portion, and a fine relief image is formed. The obtained flexographic printing plate has a wide allowable printing pressure range, and the printing quality is improved.
Claims (5)
モノビニル置換芳香族炭化水素と共役ジエンを重合して得られる熱可塑性エラストマー４０〜９０重量部、分子量が５００〜５，０００の液状ゴム５〜４０重量部、エチレン性不飽和化合物３〜２０重量部、光重合開始剤を０．１〜３重量部から成る組成物より形成された感光性樹脂層（Ａ）、
（Ｂ）層（Ａ）上にあり、少なくとも３２０ｎｍ〜４２０ｎｍの範囲に紫外線吸収領域が存在する化合物を含有する、１種以上の重合体から成るスリップ層、
を含むフレキソ版用感光性樹脂構成体。40 to 90 parts by weight of a thermoplastic elastomer obtained by polymerizing at least a monovinyl-substituted aromatic hydrocarbon and a conjugated diene, 5 to 40 parts by weight of a liquid rubber having a molecular weight of 500 to 5,000, and 3 to 20 parts by weight of an ethylenically unsaturated compound Part, a photosensitive resin layer (A) formed from a composition comprising 0.1 to 3 parts by weight of a photopolymerization initiator,
(B) a slip layer made of one or more polymers containing a compound on the layer (A) and having an ultraviolet absorption region in the range of at least 320 nm to 420 nm,
A photosensitive resin composition for flexographic plates.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2001065340A JP4166957B2 (en) | 2001-03-08 | 2001-03-08 | Photosensitive resin composition for flexographic plates with improved image formability |
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| JP2001065340A JP4166957B2 (en) | 2001-03-08 | 2001-03-08 | Photosensitive resin composition for flexographic plates with improved image formability |
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| JP2002268228A JP2002268228A (en) | 2002-09-18 |
| JP2002268228A5 JP2002268228A5 (en) | 2005-10-27 |
| JP4166957B2 true JP4166957B2 (en) | 2008-10-15 |
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| KR20050074489A (en) * | 2002-10-23 | 2005-07-18 | 가부시키가이샤 구라레 | Curable resin composition and flexographic plate material using the curable resin composition |
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