JP4186278B2 - Direct drawing type waterless planographic printing plate - Google Patents

Description

（ここでｎは２以上の整数である。Ｒは炭素数１〜１０のアルキル、アリール、あるいはシアノアルキル基である。全体のＲの４０％以下がビニル、フェニル、ハロゲン化ビニル、ハロゲン化フェニルであり、Ｒの６０％以上がメチル基であるものが好ましい。また、鎖末端もしくは側鎖のかたちで分子鎖中に少なくとも一つ以上の水酸基を有する。）
本発明のシリコーンゴムとしては、次に示すような縮合型の架橋を行うシリコーンゴム（ＲＴＶ、ＬＴＶ型シリコーンゴム）を用いることが出来る。すなわち、式（II）と式（III ）または式（IV）で表される末端基どうしの縮合によって架橋されるものである。この時、系内に、さらに過剰の架橋剤を存在させてもよい。
【００８２】
【化２】

（ここでＲは式Ｉで説明したＲと同様のものを意味する。）
ここでＲは式Ｉで説明したＲと同様のものを意味する。）
【化３】

（ここでＲは式Ｉで説明したＲと同様のものを意味し、Ｒ¹、Ｒ²は一価の低級アルキル基である。）
【化４】

（ここでＲは式Ｉで説明したＲと同様のものを意味し、Ａｃはアセチル基である。）
このような縮合型の架橋を行う際、錫、亜鉛、鉛、カルシウム、マンガンなどの金属カルボン酸塩、例えばラウリン酸ジブチル錫、錫（II）オクトエ−ト、ナフテン酸塩など、あるいは塩化白金酸のような触媒が添加されてもよい。
【００８３】
これ以外にも、ＳｉＨ基含有ポリジメチルシロキサンや加水分解性官能基含有シラン（もしくはシロキサン）を添加することも有効であり、またゴム強度を向上させる目的で、シリカなどの公知の充填剤を添加させることも任意である。
【００８４】
さらに、本発明においては上記した縮合型シリコーンゴム層の他に、付加型のシリコーンゴム層を用いることも可能であり、取扱い性などの点から好ましい。
【００８５】
付加型シリコーンゴム層は、例えば、分子中に少なくとも２個のビニル基を有するポリオルガノシロキサンと、分子中に少なくとも３個のＳｉＨ基を有するポリオルガノシロキサンおよび白金化合物を適当な溶媒で希釈したものを、感熱層上に塗布し、加熱乾燥して硬化させることによって形成することができる。
【００８６】
分子中に少なくとも２個以上のビニル基を有するオルガノポリシロキサンとしては、分子鎖末端、中間のどちらかにビニル基を有するものが挙げられ、アルケニル基以外の有機基として、置換もしくは非置換のアルキル基、アリール基を有するものが好ましい。また、微量の水酸基を含有していてもよい。
【００８７】
分子中に２個以上のビニル基を有するポリオルガノシロキサンの具体例としては以下のものが挙げられる。
【００８８】
両末端ビニル基のポリジメチルシロキサン、両末端メチル基の（メチルビニルシロキサン）（ジメチルシロキサン）共重合体、両末端ビニル基の（メチルビニルシロキサン）（ジメチルシロキサン）共重合体、両末端ビニル基のポリジメチルシロキサンの２分子以上主鎖間をジメチレン架橋させた化合物、両末端メチル基の（メチル１−ヘキセンシロキサン）（ジメチルシロキサン）共重合体、両末端ビニル基の（メチル１−ヘキセンシロキサン）（ジメチルシロキサン）共重合体等である。
【００８９】
これら分子中に２個以上のビニル基を有するポリオルガノシロキサンは、硬化後のゴム物性の点でその分子量が５，０００以上であることが好ましく、更に好ましくは１０，０００以上である。また、これらは単独で使用することもできるし、複数の種類を任意の比率で混合して使用することもできる。
【００９０】
分子中に少なくとも３個以上のＳｉＨ基を有するポリオルガノシロキサンとしては分子鎖末端、中間のいずれかにＳｉＨ基を有するものが挙げられ、ＳｉＨ基以外の有機基として、置換もしくは非置換のアルキル基、アリール基を有するものが好ましい。
【００９１】
分子中に少なくとも３個以上のＳｉＨ基を有するポリオルガノシロキサンの具体例としては、以下のものが挙げられる。
【００９２】
両末端ＳｉＨ基のポリジメチルシロキサン、両末端メチル基のポリメチルハイドロジェンシロキサン、両末端メチル基の（メチルハイドロジェンシロキサン）（ジメチルシロキサン）共重合体、両末端ＳｉＨ基の（メチルハイドロジェンシロキサン）（ジメチルシロキサン）共重合体、環状ポリメチルハイドロジェンシロキサン等が挙げられる。
【００９３】
上記ビニル基含有ポリオルガノシロキサンとＳｉＨ基含有ポリオルガノシロキサンを混合して使用する際の比率としては、シリコーンゴム組成物中のビニル基数を１とした場合にＳｉＨ基数が１．５〜１５となるような混合比率が好ましく、更に好ましくは１．５〜１２が好ましい。ビニル基数１に対するＳｉＨ基数が１．５未満の場合であると、シリコーンゴム層の硬化性が低下する傾向にあり、１５より大きい場合にはシリコーンゴムが脆くなり耐摩耗性が低下する傾向があり好ましくない。
【００９４】
さらに付加型シリコーンゴム層に好ましく用いられる白金化合物としては、特に限定されないが、白金単体、塩化白金、塩化白金酸、オレフィン配位白金などが挙げられる。これらの中でもオレフィン配位白金が好ましい。
【００９５】
また、付加型シリコーンゴム層の硬化速度を制御する目的で、テトラシクロ（メチルビニル）シロキサンなどのビニル基含有のオルガノポリシロキサン、炭素−炭素三重結合含有のアルコール、アセトン、メチルエチルケトン、メタノール、エタノール、プロピレングリコールモノメチルエーテルなどの反応抑制剤を添加することが好ましい。
【００９６】
これらの組成物の他に、縮合型シリコーンゴム層の組成物である水酸基含有オルガノポリシロキサン、加水分解性官能基含有シラン（もしくはシロキサン）を添加してもよく、またゴム強度を向上させる目的で、シリカなどの公知の充填剤を添加してもよい。
【００９７】
さらに、本発明においてシリコーンゴム層は上記組成物の他に公知のシランカップリング剤を含有することが好ましい。これらのシランカップリング剤は、シリコーンゴム層組成物の固形分に対し、０．１〜５重量％の比率で使用することが好ましく、更に好ましくは０．５〜３重量％である。
【００９８】
これらシリコーンゴム層の膜厚は０．５〜２０ｇ／ｍ２が好ましく、さらに好ましくは０．５〜５ｇ／ｍ２である。膜厚が０．５ｇ／ｍ２よりも小さい場合には印刷版のインキ反撥性が低下する傾向があり、２０ｇ／ｍ２よりも大きい場合には経済的見地から不利であるばかりでなく、インキマイレージが悪くなると言う問題がある。
【００９９】
［基板］本発明の直描型水なし平版印刷版原版に使用する基板としては、寸法的に安定な板状物であれば公知の金属、フィルム等のいずれも使用することができる。この様な寸法的に安定な板状物としては、従来印刷版の基板として使用されたもの等が好ましく挙げられる。かかる基板としては、紙、プラスチック（ポリエチレン、ポリプロピレン、ポリスチレンなど）がラミネ−トされた紙、アルミニウム（アルミニウム合金も含む）、亜鉛、銅などの金属の板、セルロースアセテート、ポリエチレンテレフタレ−ト、ポリエチレン、ポリエステル、ポリアミド、ポリイミド、ポリスチレン、ポリプロピレン、ポリカ−ボネ−ト、ポリビニルアセタ−ルなどのプラスチックのフィルム、上記の如き金属がラミネ−トもしくは蒸着された紙もしくはプラスチックフィルムなどが挙げられる。
【０１００】
これらのうち、アルミニウム板は寸法的に著しく安定であり、しかも安価であるので特に好ましい。また、軽印刷用の基板として用いられているポリエチレンテレフタレ−トフィルムも好ましく使用される。
【０１０１】
［断熱層］本発明の直描型水なし平版印刷版原版は、照射されたレーザーによる熱を基板に逃がすことを防ぐため、断熱層を設けることが効果的である。
【０１０２】
基板と感熱層の接着性を強固にするために従来用いられてきた公知のプライマー層をその代用として用いてもよい。
【０１０３】
本発明で使用する断熱層は、次の条件を満たすことが必要である。すなわち、基板と感熱層とをよく接着し、経時において安定であること、さらに現像液、印刷時に使用する溶剤に対する耐性が高いことである。
【０１０４】
このような条件を満たすものとして、エポキシ樹脂、ポリウレタン樹脂、フェノ−ル樹脂、アクリル樹脂、アルキッド樹脂、ポリエステル樹脂、ポリアミド樹脂、尿素樹脂、ポリビニルブチラール樹脂、カゼイン、ゼラチン等を含むものが挙げられる。これらの中では、ポリウレタン樹脂、ポリエステル樹脂、アクリル樹脂、エポキシ樹脂、尿素樹脂等を単独で、あるいは２種以上を混合して用いることが好ましい。
【０１０５】
また、この断熱層中に顔料、染料等の添加剤を含有させて検版性を向上させることも好ましい。
【０１０６】
断熱層の厚さは被覆層にして０．５〜５０ｇ／ｍ２ が好ましく、より好ましくは１〜１０ｇ／ｍ２である。厚さが０．５ｇ／ｍ２よりも薄いと基板表面の形態欠陥および化学的悪影響の遮断効果に劣り、５０ｇ／ｍ２よりも厚いと経済的見地から不利となるので上記の範囲が好ましい。
【０１０７】
［製造方法］
本発明における直描型水なし平版印刷版原版の製造方法および製版方法について説明する。
【０１０８】
基板上に、リバースロールコーター、エアーナイフコーター、グラビアコーター、ダイコーター、メーヤバーコーターなどの通常のコーターあるいはホエラーのような回転塗布装置を用い、必要に応じて断熱層組成物を塗布し１００〜３００℃で数分間加熱あるいは活性光線照射により硬化させた後、感熱層組成物を塗布し５０〜１８０℃で数十秒から数分間加熱乾燥、必要により硬化させる。
【０１０９】
この後、シリコーンゴム組成物を塗布し５０〜２００℃の温度で数分間熱処理してシリコーンゴム層を得る。その後、必要に応じて保護フィルムをラミネートするか、あるいは保護層を形成する。
【０１１０】
［カバーフィルム］
以上説明されたように構成された直描型水なし平版印刷版のシリコーンゴム層を保護するなどの目的で、シリコーンゴム層の表面にプレーンまたは凹凸処理した保護フィルムをラミネートしたり、現像溶媒に溶解するようなポリマー塗膜を形成することも可能である。
【０１１１】
このようなカバーフィルムの種類としては、ポリエステルフィルム、ポリプロピレンフィルム、ポリビニルアルコールフィルム、エチレン酢酸ビニル共重合体ケン化物フィルム、ポリ塩化ビニリデンフィルム、また各種金属を蒸着したフィルムなどが挙げられる。
【０１１２】
［レーザー照射］
このようにして得られた直描型水なし平版印刷版原版を、保護フィルムを剥離してから、あるいは保護フィルム上からレーザー光で画像状に露光する。
【０１１３】
本発明の製版露光工程で用いられるレーザー光源としては、発信波長領域が３００ｎｍ〜１５００ｎｍの範囲にあるものが用いられる。すなわち、アルゴンイオン、クリプトンイオン、ヘリウム-ネオン、ヘリウム-カドミウム、ルビー、ガラス、ＹＡＧ、チタンサファイア、色素、窒素、金属蒸気、エキシマ、自由電子、半導体などの各種レーザーが使用される。
【０１１４】
これらの中でも本発明の印刷版原版を製版する目的から、近赤外領域付近に発光波長領域が存在する半導体レーザーが好ましく、特に高出力半導体レーザーが好ましく用いられる。
【０１１５】
［現像方法］
現像方法としては、水または有機溶剤の存在もしくは非存在下での摩擦処理により行われる。あるいは、保護フィルムを剥離することによって印刷版上にパターンを形成する、いわゆる剥離現像によっても印刷版を作成することも可能である。
現像処理を行う場合に使用される現像液としては、例えば、水や水に界面活性剤を添加したもの、さらには水に下記の極性溶媒を添加したものや、脂肪族炭化水素類（ヘキサン、ヘプタン、イソパラフィン系炭化水素など）、芳香族炭化水素類（トルエン、キシレンなど）、ハロゲン化炭化水素類（トリクレンなど）などの少なくとも１種類からなる溶媒に、下記の極性溶媒を少なくとも１種類添加したものが用いられる。
【０１１６】
極性溶媒としては、エタノール、プロパノール、イソプロパノール、エチレングリコールなどのアルコール類、エチレングリコールモノエチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、テトラヒドロフランなどのエーテル類、アセトン、メチルエチルケトン、ジアセトンアルコールなどのケトン類、酢酸エチル、乳酸エチル、エチレングリコールモノエチルエーテルアセテートなどのエステル類、カプロン酸、２―エチルヘキサン酸、オレイン酸などのカルボン酸などが挙げられる。
【０１１７】
また、上記の現像液組成には、公知の界面活性剤を添加することも自由に行われる。さらにアルカリ剤、例えば炭酸ナトリウム、モノエタノールアミン、ジエタノールアミン、ジグリコールアミン、モノグリコールアミン、トリエタノールアミン、ケイ酸ナトリウム、ケイ酸カリウム、水酸化カリウム、ホウ酸ナトリウムなどを添加することもできる。
【０１１８】
これらの中では、水あるいは水に界面活性剤を添加したもの、さらにはアルカリを添加した水が好ましく用いられる。
【０１１９】
また、これらの現像液にはクリスタルバイオレット、ビクトリピュアブルー、アストラゾンレッドなどの公知の塩基性染料、酸性染料、油溶性染料を添加して現像と同時に画像部の染色化を行うことができる。
【０１２０】
現像する際には、これらの現像液を、不織布、脱脂綿、布、スポンジ等に含浸させて、版面を拭き取ることによって、現像することができる。
【０１２１】
また、現像は、特開昭６３−１６３３５７号公報に記載されているような自動現像機を用い、上記の現像液で版面を前処理した後に水道水などでシャワーしながら回転ブラシで版面を擦ることによって行うことも好ましい。
【０１２２】
上記の現像液に代えて、温水や水蒸気を版面に噴射することによっても現像が可能である。
【０１２５】
また、本発明は平版印刷版に限られず広く画像形成に応用可能である。例えば、レジストや、カラーフィルターの画素形成、ＰＤＰおよびその他デイスプレイの隔壁形成、さらには凸版印刷版、フレキソ印刷版など。凸版印刷版やフレキソ印刷版への応用例の一つとしては、従来の感光性の凸版印刷版、フレキソ印刷版の上部に本発明の金属キレート化合物層を設けて、レーザーを用いて画像を形成した後、ＵＶ照射により印刷版を作製するというものである。
【０１２６】
以下、本発明を実施例によりさらに詳しく説明する。
【０１２７】
【実施例】
合成例１
（水酸基含有ポリマー微粒子分散液）
１リットルの三口フラスコに攪拌棒、窒素導入管を装着し、この中にスチレン 50g、メタクリル酸グリシジル20g、メタクリル酸2-ヒドロキシエチル 30g、10％ポリビニルアルコール（重合度500）水溶液300g、水 200g、および過硫酸カリウム 0.5gを仕込んだ。窒素ガスを約２分間導入して、フラスコ内雰囲気を窒素で置換した後窒素導入を止め、フラスコを80℃の水浴に浸し、激しく攪拌しながら３時間重合反応を行った。乳白色のポリマー分散液が得られた。
【０１２８】
実施例１
厚さ０．１５ｍｍの脱脂したアルミ板上に下記の組成からなるプライマー液をバーコーターを用いて塗布し、２００℃で２分間乾燥し、膜厚４ｇ／ｍ² の断熱層を塗布した。
【０１２９】
＜断熱層組成（固形分濃度１０重量％）＞
（１）“サンプレン”ＬＱ−Ｔ１３３１（ポリウレタン樹脂、三洋化成工業（株）製） ９０重量部
（２）“タケネート”Ｂ８３０（ブロックドイソシアネート、武田薬品（株）製） ３５重量部
（３）ＳＪ９３７２（エポキシ・フェノール・尿素樹脂、関西ペイント（株）製）８重量部
［溶媒成分］
（４）ジメチルホルムアミド
続いてこの上に下記の感熱層組成物をバーコーターを用いて塗布し、１５０℃で１分間乾燥し、膜厚１．５ｇ／ｍ² の感熱層を設けた。
【０１３０】
＜感熱層組成（固形分濃度１０重量％）＞
（ａ）カーボンブラック分散ロジン変性マレイン酸樹脂 ２５重量部
（内カーボンブラック１０重量部）
（ｂ）鉄（III）アセチルアセトネート（半井化学薬品（株）製） ２０重量部
（ｃ）ＤＭ６２２（エポキシメタクリレート、ナガセ化成工業（株）製）） ３０重量部
（ｄ）“サンプレン”ＬＱ−Ｔ１３３１（ポリウレタン樹脂、三洋化成工業（株） 製） ２５重量部
［溶媒成分］
（１）ジメチルホルムアミド ５０重量部
（２）エチルセロソルブ ２５重量部
（３）メチルイソブチルケトン ２５重量部
続いてこの上に下記の組成を有するシリコーンゴム層組成物をバーコーターを用いて塗布し、１２５℃で１分間乾燥し、膜厚２ｇ／ｍ² のシリコーンゴム層を設けた。
【０１３１】
＜シリコーンゴム層組成（固形分濃度７重量％）＞
（１）ビニル基含有ポリシロキサン １００重量部
（２）ハイドロジェンポリシロキサン ５重量部
（３）重合禁止剤 １重量部
（４）触媒 ２重量部
［溶媒成分］
（１）“アイソパー”Ｅ（エクソン化学（株）製）
上記のようにして得られた積層板に、厚さ８μｍのポリエステルフィルム“ルミラー”（東レ（株）製）をカレンダーローラーを用いてラミネートし、直描型水なし平版印刷版原版を得た。
【０１３２】
この後、この印刷版原版の“ルミラー”を剥離し、ＦＸ４００−ＡＰ（製版機、東レエンジニアリング(株)製）に装着し、半導体レーザー（波長８３０ｎｍ、ビーム直径２０μｍ）を用いて、照射エネルギーを変えながら、露光時間１０μｓで、パルス露光を行った。
【０１３３】
続いて、東レ（株）製自動現像装置ＴＷＬ−６５０により上記露光済みの版の現像を行った。この際、前処理液としては東レ（株）製“ＰＰ−１”を、現像液としては水を、後処理液としては東レ（株）製“ＰＡ−Ｆ”を用いた。
【０１３４】
現像後の版を観察したところ、３００ｍＪ／ｓ（６００ｍＷ）以下ではシリコーンゴム層のみが、それよりエネルギーの高い領域ではシリコーンゴム層と共に感熱層が除去されていた。
【０１３５】
次にハンドローラーで水なし平版用インキ（Ｗａｔｅｒｌｅｓｓ Ｓ、ザ・インクテック（株）製、赤）を、現像済みの版面全面に展開して、画像が再現されるレーザー照射エネルギーを調べた。その結果、１７５ｍＪ／ｓ（３５０ｍＷ）以上の領域において、レーザー照射部のシリコーンゴム層が除去され、画像が再現されていた。
【０１３６】
実施例２
実施例１において、感熱層塗液の組成を以下に示すものに代えた以外は全て同様に印刷版原版を作製した。
【０１３７】
実施例１と同様に評価したところ、２２５ｍＪ／ｓ（４５０ｍＷ）以上４５０ｍＪ／ｓ（９００ｍＷ）以下ではシリコーンゴム層のみが、それよりエネルギーの高い領域ではシリコーンゴム層と共に感熱層が除去されていた。
【０１３８】
＜感熱層組成（固形分濃度１０重量％）＞
（ａ）SPRIT NIGROSINE SJ（Dye Specialities,INC.） １５重量部
（ｂ）鉄（III）アセチルアセトネート（半井化学薬品（株）製） ２０重量部
（ｃ）ＤＭ６２２（エポキシメタクリレート、ナガセ化成工業（株）製）） ３０重量部
（ｄ）“サンプレン”ＬＱ−Ｔ１３３１（ポリウレタン樹脂、三洋化成工業（株） 製） ３５重量部
［溶媒成分］
（１）ジメチルホルムアミド ５０重量部
（２）エチルセロソルブ ２５重量部
（３）メチルイソブチルケトン ２５重量部
比較例１
実施例１において、感熱層塗液の組成を以下に示すものに代えた以外は全て同様に印刷版原版を作製し、同様に評価したところ、レーザー照射のシリコーンゴム層が剥がれず、現像不能状態であり、画像を再現することが出来なかった。
【０１３９】
＜感熱層組成（固形分濃度１０重量％）＞
（ｂ）鉄（III）アセチルアセトネート（半井化学薬品（株）製） ２０重量部
（ｃ）ＤＭ６２２（エポキシメタクリレート、ナガセ化成工業（株）製）） ３０重量部
（ｄ）“サンプレン”ＬＱ−Ｔ１３３１（ポリウレタン樹脂、三洋化成工業（株） 製） ５０重量部
［溶媒成分］
（１）ジメチルホルムアミド ５０重量部
（２）エチルセロソルブ ２５重量部
（３）メチルイソブチルケトン ２５重量部
比較例２
実施例１において、感熱層塗液の組成を以下に示すものに代えた以外は全て同様に版材を作製し、同様に評価したところ、５００ｍＪ／ｓ（１０００ｍＷ）以上でやっとシリコーンゴム層が除去されるという感度の低い版しか得られなかった。
【０１４０】
＜感熱層組成（固形分濃度１０重量％）＞
（ａ）SPRIT NIGROSINE SJ（Dye Specialities,INC.） １５重量部
（ｃ）ＤＭ６２２（エポキシメタクリレート、ナガセ化成工業（株）製）） ３０重量部
（ｄ）“サンプレン”ＬＱ−Ｔ１３３１（ポリウレタン樹脂、三洋化成工業（株） 製） ５５重量部
［溶媒成分］
（１）ジメチルホルムアミド ５０重量部
（２）エチルセロソルブ ２５重量部
（３）メチルイソブチルケトン ２５重量部
実施例３
実施例１において、感熱層塗液の組成を以下に示すものに代えた以外は全て同様に印刷版原版を作製し、同様に評価したところ、２２５ｍＪ／ｓ（４５０ｍＷ）以上４５０ｍＪ／ｓ（９００ｍＷ）以下ではシリコーンゴム層のみが、それよりエネルギーの高い領域ではシリコーンゴム層と共に感熱層が除去されていた。
【０１４１】
＜感熱層組成（固形分濃度１０重量％）＞
（ａ）SPRIT NIGROSINE SJ（Dye Specialities,INC.） １５重量部
（ｂ）“ナーセム”Ti（日本化学産業（株）製） ２０重量部
（ｃ）ＤＭ６２２（エポキシメタクリレート、ナガセ化成工業（株）製）） ３０重量部
（ｄ）“サンプレン”ＬＱ−Ｔ１３３１（ポリウレタン樹脂、三洋化成工業（株） 製） ３５重量部
［溶媒成分］
（１）ジメチルホルムアミド ５０重量部
（２）エチルセロソルブ ２５重量部
（３）メチルイソブチルケトン ２５重量部
実施例４
実施例１において、感熱層塗液の組成を以下に示すものに代えた以外は全て同様に印刷版原版を作製し、同様に評価したところ、１７５ｍＪ／ｓ（３５０ｍＷ）以上４２５ｍＪ／ｓ（８５０ｍＷ）以下ではシリコーンゴム層のみが、それよりエネルギーの高い領域ではシリコーンゴム層と共に感熱層が除去されていた。
【０１４２】
＜感熱層組成（固形分濃度１０重量％）＞
（ａ）“ＫＡＹＡＳＯＲＢ”ＩＲ−８２０Ｂ（赤外光吸収染料、日本化薬（株）製） １０重量部
（ｂ）鉄（III）アセチルアセトネート（半井化学薬品（株）製） ２０重量部
（ｃ）ＤＭ６２２（エポキシメタクリレート、ナガセ化成工業（株）製）） ３０重量部
（ｄ）“サンプレン”ＬＱ−Ｔ１３３１（ポリウレタン樹脂、三洋化成工業（株） 製） ４０重量部
［溶媒成分］
（１）ジメチルホルムアミド ５０重量部
（２）エチルセロソルブ ２５重量部
（３）メチルイソブチルケトン ２５重量部
実施例５
実施例１において、感熱層塗液の組成、およびシリコーンゴム層塗液の組成を以下に示すものに代えた以外は全て同様に印刷版原版を作製し、同様に評価したところ、１７５ｍＪ／ｓ（３５０ｍＷ）以上５００ｍＪ／ｓ（１０００ｍＷ）以下ではシリコーンゴム層のみが、それよりエネルギーの高い領域ではシリコーンゴム層と共に感熱層が除去されていた。
【０１４３】
＜感熱層組成（固形分濃度１０重量％）＞
（ａ）SPRIT NIGROSINE SJ（Dye Specialities,INC.） １５重量部
（ｂ）“アルミキレート”Ｄ（アルミニウム（III）モノアセチルアセトネートビ スエチルアセトアセテート、川研ファインケミカル（株）製） ２０重量部
（ｃ）“スミライトレジン”ＰＲ−５０７３１（ノボラック樹脂、住友デュレス（株）製）） ３０重量部
（ｄ）“サンプレン”ＬＱ−Ｔ１３３１（ポリウレタン樹脂、三洋化成工業（株） 製） ３５重量部
［溶媒成分］
（１）ジメチルホルムアミド ５０重量部
（２）エチルセロソルブ ２５重量部
（３）メチルイソブチルケトン ２５重量部
＜シリコーンゴム層組成（固形分濃度７重量％）＞
（１）ポリジメチルシロキサン（分子量約２５，０００、末端水酸基）
１００重量部
（２）ビニルトリ（メチルエチルケトオキシム）シラン １０重量部
［溶媒成分］
（１）“アイソパー”Ｅ（エクソン化学（株）製）
実施例６
実施例５において、感熱層塗液の組成を以下に示すものに代えた以外は全て同様に印刷版原版を作製し、同様に評価したところ、１２５ｍＪ／ｓ（２５０ｍＷ）以上４００ｍＪ／ｓ（８００ｍＷ）以下ではシリコーンゴム層のみが、それよりエネルギーの高い領域ではシリコーンゴム層と共に感熱層が除去されていた。
【０１４４】
＜感熱層組成（固形分濃度１０重量％）＞
（ａ）“ＫＡＹＡＳＯＲＢ”ＩＲ−８２０Ｂ（赤外光吸収染料、日本化薬（株）製） １０重量部
（ｂ）鉄（III）アセチルアセトネート（半井化学薬品（株）製） ２０重量部
（ｃ）“スミライトレジン”ＰＲ−５０７３１（ノボラック樹脂、住友デュレス（株）製）） ３０重量部
（ｄ）“サンプレン”ＬＱ−Ｔ１３３１（ポリウレタン樹脂、三洋化成工業（株） 製） ４０重量部
［溶媒成分］
（１）ジメチルホルムアミド ５０重量部
（２）エチルセロソルブ ２５重量部
（３）メチルイソブチルケトン ２５重量部
実施例７
実施例５において、感熱層塗液の組成を以下に示すものに代えた以外は全て同様に印刷版原版を作製し、同様に評価したところ、２２５ｍＪ／ｓ（４５０ｍＷ）以上５００ｍＪ／ｓ（１０００ｍＷ）以下ではシリコーンゴム層のみが、それよりエネルギーの高い領域ではシリコーンゴム層と共に感熱層が除去されていた。
【０１４５】
＜感熱層組成（固形分濃度１０重量％）＞
（ａ）SPRIT NIGROSINE SJ（Dye Specialities,INC.） １５重量部
（ｂ）“アルミキレート”Ｄ（アルミニウム（III）モノアセチルアセトネートビ スエチルアセトアセテート、川研ファインケミカル（株）製） １０重量部
（ｃ）“スミラック”ＰＣ−１（レゾール樹脂、住友デュレス（株）製）） ３０重量部
（ｄ）“サンプレン”ＬＱ−Ｔ１３３１（ポリウレタン樹脂、三洋化成工業（株） 製） ４５重量部
［溶媒成分］
（１）ジメチルホルムアミド ５０重量部
（２）エチルセロソルブ ２５重量部
（３）メチルイソブチルケトン ２５重量部
実施例８
実施例５において、感熱層塗液の組成を以下に示すものに代えた以外は全て同様に印刷版原版を作製し、同様に評価したところ、１７５ｍＪ／ｓ（３５０ｍＷ）以上４２５ｍＪ／ｓ（８５０ｍＷ）以下ではシリコーンゴム層のみが、それよりエネルギーの高い領域ではシリコーンゴム層と共に感熱層が除去されていた。
【０１４６】
＜感熱層組成（固形分濃度１０重量％）＞
（ａ）SPRIT NIGROSINE SJ（Dye Specialities,INC.） １５重量部
（ｂ）“アルミキレート”Ｄ（アルミニウム（III）モノアセチルアセトネートビ スエチルアセトアセテート、川研ファインケミカル（株）製） ２０重量部
（ｃ）“スミラック”ＰＣ−１（レゾール樹脂、住友デュレス（株）製）） ３０重量部
（ｄ）“サンプレン”ＬＱ−Ｔ１３３１（ポリウレタン樹脂、三洋化成工業（株） 製） ３５重量部
［溶媒成分］
（１）ジメチルホルムアミド ５０重量部
（２）エチルセロソルブ ２５重量部
（３）メチルイソブチルケトン ２５重量部
比較例３
実施例５において、感熱層塗液の組成を以下に示すものに代えた以外は全て同様に印刷版原版を作製し、同様に評価したところ、４７５ｍＪ／ｓ（９５０ｍＷ）以上でやっとシリコーンゴム層が除去されるという感度の低い版しか得られなかった。
【０１４７】
＜感熱層組成（固形分濃度１０重量％）＞
（ａ）SPRIT NIGROSINE SJ（Dye Specialities,INC.） １５重量部
（ｃ）“スミラック”ＰＣ−１（レゾール樹脂、住友デュレス（株）製）） ３０重量部
（ｄ）“サンプレン”ＬＱ−Ｔ１３３１（ポリウレタン樹脂、三洋化成工業（株） 製） ５５重量部
［溶媒成分］
（１）ジメチルホルムアミド ５０重量部
（２）エチルセロソルブ ２５重量部
（３）メチルイソブチルケトン ２５重量部
実施例９
実施例５において、感熱層塗液の組成を以下に示すものに代えた以外は全て同様に印刷版原版を作製し、同様に評価したところ、１７５ｍＪ／ｓ（３５０ｍＷ）以上４２５ｍＪ／ｓ（８５０ｍＷ）以下ではシリコーンゴム層のみが、それよりエネルギーの高い領域ではシリコーンゴム層と共に感熱層が除去されていた。
【０１４８】
＜感熱層組成（固形分濃度１０重量％）＞
（ａ）SPRIT NIGROSINE SJ（Dye Specialities,INC.） １５重量部
（ｂ）“ナーセム”Ti（日本化学産業（株）製） ２０重量部
（ｃ）“リポキシ”ＶＲ−９０（エポキシアクリレート、昭和高分子（株）製）３０重量部
（ｄ）“サンプレン”ＬＱ−Ｔ１３３１（ポリウレタン樹脂、三洋化成工業（株） 製） ３５重量部
［溶媒成分］
（１）ジメチルホルムアミド ５０重量部
（２）エチルセロソルブ ２５重量部
（３）メチルイソブチルケトン ２５重量部
実施例１０
実施例５において、感熱層塗液の組成、およびシリコーンゴム層塗液の組成を以下に示すものに代えた以外は全て同様に印刷版原版を作製し、同様に評価したところ、１７５ｍＪ／ｓ以上でシリコーンゴム層が除去された版が得られた。
【０１４９】
＜感熱層組成（固形分濃度１０重量％）＞
（ａ）“ＫＡＹＡＳＯＲＢ”ＩＲ−８２０Ｂ（赤外光吸収染料、日本化薬（株）製） １０重量部
（ｂ）“ナーセム”Ti（日本化学産業（株）製） １０重量部
（ｃ）“スミライトレジン”ＰＲ−５０７３１（ノボラック樹脂、住友デュレス（株）製）） ５０重量部
（ｄ）“サンプレン”ＬＱ−Ｔ１３３１（ポリウレタン樹脂、三洋化成工業（株） 製） ３０重量部
［溶媒成分］
（１）ジメチルホルムアミド １０重量部
（２）テトラヒドロフラン ９０重量部
＜シリコーンゴム層組成（固形分濃度７重量％）＞
（１）ビニル基含有ポリシロキサン １００重量部
（２）ハイドロジェンポリシロキサン ５重量部
（３）重合禁止剤 １重量部
（４）触媒 ２重量部
［溶媒成分］
（１）“アイソパー”Ｅ（エクソン化学（株）製）
実施例１１
実施例１０において、感熱層組成物をバーコーターで塗布した後、乾燥を１３０℃で１分間とした以外は全て同様に印刷版原版を作製し、同様に評価したところ、１５０ｍＪ／ｓ以上でシリコーンゴム層が除去された版が得られた。
【０１５０】
実施例１２
厚さ０．２４ｍｍの脱脂したアルミ板上に下記の組成よりなる溶液を塗布し、２００℃、２分間乾燥し、３ｇ／ｍ²の断熱層を設けた。
【０１５１】
＜断熱層組成（固形分濃度１６．７重量％）＞
（１）エポキシ・フェノール樹脂“カンコート”９０Ｔ−２５−３０９４（関西ペイント（株）製） １５重量部
（２）“ホワイト”ＵＬ７Ｅ２６５（住化カラー（株）製、酸化チタン）２重量部
［溶媒成分］
（１）ジメチルホルムアミド ８５重量部
次いで、この断熱層上に次の組成を有する感熱層組成物を塗布し、８０℃で１分間乾燥し、膜厚２ｇ／ｍ²の感熱層を設けた。
【０１５２】
＜感熱層組成（固形分濃度１２．５重量％）＞
（ａ）SPRIT NIGROSINE SJ（Dye Specialities,INC.） ５重量部
（ｂ）“アルミキレート”Ｄ（アルミニウムモノアセチルアセトネートビスエチルアセトアセテート、川研ファインケミカル（株）製） ３０重量部
（ｃ）“スミラック”ＰＣ−１（レゾール樹脂、住友デュレス（株）製））７０重量部
（ｄ）“サンプレン”ＬＱ−９０９Ｌ（ポリウレタン樹脂、三洋化成工業（株）製） ２０重量部
［溶媒成分］
（１）テトラヒドロフラン ８７５重量部
さらに、この感熱層の上に下記の組成を有するシリコーンゴム組成物をバーコーターで塗布した後、１００℃で１分間湿熱硬化させて２．０μｍのシリコーンゴム層を設けた。
【０１５３】
＜シリコーンゴム層組成（固形分濃度８．４重量％）＞
（１）ポリジメチルシロキサン（分子量約３５，０００、末端水酸基）
１００重量部
（２）ビニルトリス（メチルエチルケトオキシム）シラン ９重量部
（３）ジブチル錫ジアセテート ０．５重量部
［溶媒成分］
（１）“アイソパーＥ”（エクソン化学（株）製） １２００重量部
上記のようにして得られた積層板に、厚さ８μｍのポリプロピレンフィルム“トレファン”（東レ（株）製）をカレンダーローラーを用いてラミネートし、直描型水なし平版印刷版原版を得た。
【０１５４】
この後、実施例１と同様にレーザー照射を行い、同様に現像を行った。この際、前処理液としては東レ（株）製“ＰＰ−Ｆ”を、現像液としては水を、後処理液としては東レ（株）製“ＰＡ−Ｆ”を用いた。
【０１５５】
その結果、あるエネルギー領域においてレーザー光が照射された部分のみが残存し、その他の部分はシリコーンゴム層が剥離したポジ型の水なし平版印刷版が得られた。
【０１５６】
さらに、得られた印刷版を印刷機ＨＡＭＡＤＡ ＲＳ４６Ｌ（ハマダ印刷機械（株）製）に取り付け、水なし平版用インキ（ドライオカラーＮＳＩ 藍 大日本インキ化学工業（株）製）を使用して上質紙に印刷を行い、印刷物において画像を再現できたレーザー出力の最小の値（ｍＪ／秒）を調べた結果、２５０ｍＪ／秒であった。
【０１５７】
比較例４
実施例１２において、感熱層中の光熱変換物質である（ａ）SPRIT NIGROSINE SJを抜いた以外は全く同様にして印刷版原版を作製し、同様に評価したところ、シリコーンゴム層が版面全体にわたり剥がれた版しか得られなかった。
【０１５８】
比較例５
実施例１２において、感熱層中の金属キレート化合物である（ｂ）“アルミキレート”Ｄを抜いた以外は全く同様にして印刷版原版を作製し、同様に評価したところ、シリコーンゴム層が版面全体にわたり剥がれた版しか得られなかった。
【０１５９】
実施例１３
厚さ０．２４ｍｍの脱脂したアルミ板上に下記の組成よりなる溶液を塗布し、２００℃、２分間乾燥し、３ｇ／ｍ²の断熱層を設けた。
【０１６０】
＜断熱層組成（固形分濃度１７．１重量％）＞
（１）ポリウレタン樹脂“ミラクトラン”Ｐ２２Ｓ（日本ミラクトラン（株）製） １００重量部
（２）ブロックドイソシアネート“タケネートＢ８３０”（武田薬品工業（株）製） ２０重量部
（３）エポキシ・フェノール・尿素樹脂“ＳＪ９３７２”（関西ペイント（株）製） ８重量部
（４）ジブチル錫ジアセテート ０．５重量部
（５）“ＦＩＮＥＸ”２５（白色顔料、堺化学（株）製） １０重量部
（６）“ＫＥＴ−ＹＥＬＬＯＷ”４０２（黄色顔料、大日本インキ化学工業（株） 製） １０重量部
［溶媒成分］
（１）ジメチルホルムアミド ７２０重量部
この断熱層上に、次の組成を有する感熱層組成物を塗布し、８０℃で１分間乾燥し、膜厚３ｇ／ｍ²の感熱層を設けた。
【０１６１】
＜感熱層組成（固形分濃度１０重量％）＞
（ａ）カーボンブラック分散ロジン変性マレイン酸樹脂 １５重量部
（内カーボンブラック１０重量部）
（ｂ）鉄（III）アセチルアセトネート（半井化学薬品（株）製） １０重量部
（ｃ）“スミライトレジン”ＰＲ−５０７３１（ノボラック樹脂、住友デュレス（株）製）） ２０重量部
（ｄ）“エポキシエステル”３０００Ｍ（水酸基含有アクリレート、共栄社化学（株）製） ２０重量部
（ｅ）“サンプレン”ＬＱ−Ｔ１３３１（ポリウレタン樹脂、三洋化成工業（株） 製） ４０重量部
（ｆ）“ＴＳＬ”８３７０（シリル基含有アクリレート、東芝シリコーン（株）製） ５重量部
［溶媒成分］
（１）Ｎ，Ｎ−ジメチルホルムアミド ２２０重量部
（２）テトラヒドロフラン ７７０重量部
この感熱層の上に下記シリコーンゴム層組成物をバーコーターを用いて塗布し、乾燥膜厚２．０μｍ、乾燥条件は１２０℃×１分間とした以外は全く実施例１２と同様に印刷版原版を作成し、評価を行ったところ、レーザー出力２８０ｍＪ／秒以上でポジ型の水なし平版印刷版が得られた。
【０１６２】
＜シリコーンゴム層組成（固形分濃度９．４重量％）＞
（１）α，ω−ジビニルポリジメチルシロキサン（重合度７７０）１００重量部
（２）ＨＭＳ−５０１（チッソ（株）製 両末端メチル（メチルハイドロジェンシロキサン）（ジメチルシロキサン）共重合体 ＳｉＨ基数／分子量＝０．６９mol/g） ４重量部
（３）オレフィン配位白金 ０．０２重量部
（４）“ＢＹ２４−８０８”（ダウコーニングシリコーン（株）製 反応抑制剤） ０．３重量部
［溶媒成分］
（１）“アイソパー”Ｅ（エッソ化学（株）製） １０００重量部
実施例１４
実施例１３における感熱層を下記に変更し、乾燥膜厚２．５ｇ／ｍ²、乾燥条件は１５０℃×２分間とした以外は全く実施例１３と同様に印刷版原版を作製し、同様の評価を行ったところ、レーザー出力１３０ｍＪ／秒以上でレーザー照射部のシリコーンゴム層が特異的に除去されたネガ型の水なし平版印刷版が得られた。
【０１６３】
さらに、製版後の版を用いて、レーザー出力２００ｍＪ／秒における画線部ベタ部の感熱層の厚さを測定したところ２．３ｇ／ｍ²であり、残存率が９２％であることが判明した。
【０１６４】
＜感熱層組成（固形分濃度２８重量％）＞
（ａ）“ＫＡＹＡＳＯＲＢ”ＩＲ−８２０Ｂ（赤外線吸収染料、日本化薬（株）製） １０重量部
（ｂ）“ナーセム”Ｔｉ（日本化学産業（株）製） １５重量部
（ｃ）ペンタオキシプロピレンジアミン／グリシジルメタクリレート／メチルグリシジルエーテル＝１／３／１ｍｏｌ比付加反応物 １５重量部
（ｄ）ｍ−キシリレンジアミン／グリシジルメタクリレート／メチルグリシジルエーテル＝１／２／２ｍｏｌ比付加反応物 １５重量部
（ｅ）ｍ−キシリレンジアミン／グリシジルメタクリレート／３−グリシドキシプロピルトリメトキシシラン＝１／３／１ｍｏｌ比付加反応物
３重量部
（ｆ）“デナコール”ＥＸ−４１１（ペンタエリスルトールポリグリシジルエーテル、ナガセ化成工業（株）製） ５重量部
（ｇ）“サンプレン”Ｔ−１３３１（ポリウレタン樹脂 三洋化成工業（株）製、 ガラス転移温度Ｔｇ：−３７℃） ３０重量部
（ｈ）マレイン酸 ０．５重量部
（ｉ）“パーヘキサ”３Ｍ（有機過酸化物 日本油脂（株）製） ５重量部
［溶媒成分］
（１）テトラヒドロフラン：２００重量部
（２）ジメチルホルムアミド：５０重量部
また、感熱層の初期弾性率は２０ｋｇｆ／ｍｍ²であった。
【０１６５】
実施例１５
実施例１４における感熱層を下記に変更し、乾燥膜厚２．５ｇ／ｍ²になるように塗布し、８０℃×１分間乾燥した。その後、“アイドルフィン”２０００（岩崎電気（株）製、メタルハライドランプ）を用いて、空気中で感熱層全面に１１ｍＷ／ｃｍ²で１２０秒間紫外線を照射した。
【０１６６】
さらにその後、実施例１４と同じシリコーンゴム層を塗設し、水なし平版印刷版原版を作製した。実施例１４と同様に評価を行ったところ、レーザー出力１３０ｍＪ／秒以上でネガ型の水なし平版印刷版が得られた。
【０１６７】
製版後の版を用いて、レーザー出力２００ｍＪ／秒における画線部ベタ部の感熱層の厚さを測定したところ２．２５ｇ／ｍ²であり、残存率が９０％であることが判明した。
【０１６８】
また、感熱層の初期弾性率は１９ｋｇｆ／ｍｍ²であった。
【０１６９】
＜感熱層組成（固形分濃度２８重量％）＞
（ａ）“ＫＡＹＡＳＯＲＢ”ＩＲ−８２０Ｂ（赤外線吸収染料、日本化薬（株）製） １０重量部
（ｂ）“ナーセム”Ｔｉ（日本化学産業（株）製） １５重量部
（ｃ）ペンタオキシプロピレンジアミン／グリシジルメタクリレート／メチルグリシジルエーテル＝１／３／１ｍｏｌ比付加反応物 １５重量部
（ｄ）ｍ−キシリレンジアミン／グリシジルメタクリレート／メチルグリシジルエーテル＝１／２／２ｍｏｌ比付加反応物 １５重量部
（ｅ）ｍ−キシリレンジアミン／グリシジルメタクリレート／３−グリシドキシプロピルトリメトキシシラン＝１／３／１ｍｏｌ比付加反応物
３重量部
（ｆ）“デナコール”ＥＸ−４１１（ペンタエリスルトールポリグリシジルエーテル、ナガセ化成工業（株）製） ５重量部
（ｇ）“サンプレン”Ｔ−１３３１（ポリウレタン樹脂 三洋化成工業（株）製、 ガラス転移温度Ｔｇ：−３７℃） ３０重量部
（ｈ）マレイン酸 ０．５重量部
（ｉ）“ＩＲＧＡＣＵＲＥ”６５１（Ｃｉｂａ Ｇｅｉｇｙ（株）製 ベンジルジメチルケタール） ２重量部
（ｊ）“ミヒラーケトン”（保土谷化学（株）製 ４，４’−ジメチルアミノ ベンゾフェノン） ５重量部
［溶媒成分］
（１）テトラヒドロフラン ２００重量部
（２）ジメチルホルムアミド ５０重量部
実施例１６
ＥＣ処理を施した厚さ８０μｍのポリエチレンテレフタレートフィルム“ルミラー”（東レ（株）製）の上に、実施例１２と同じ感熱層、同じシリコーンゴム層を設けた。さらに、実施例１２と同じカバーフィルムをラミネートし、直描型水なし平版印刷版原版を得た。
【０１７０】
得られた直描型水なし平版印刷版原版を実施例１２と同様に、レーザー照射を行い、カバーフィルムを剥離した後、水／ジエチレングリコールモノ−２−エチルヘキシルエーテル：９０／１０（重量部／重量部）の混合溶液に１分間浸漬し、さらに精製水を浸した現像パッド（３Ｍ（株）製）を用いて版面を摩擦したところ、レーザー出力２８０ｍＪ／秒以上でレーザー照射部のシリコーンゴム層のみが選択的に残存し、それ以外の部分のシリコーンゴム層が脱離したポジ型の水なし平版印刷版が得られた。
【０１７１】
比較例６
砂目立てしたアルミ板を８０℃に加熱した弗化ジルコニウムの５％水溶液で２分間表面処理し、乾燥して基板とした。この基板上に実施例１の感熱性組成物を乾燥膜厚２．０ｇ／ｍ2になるように塗布し、６０℃で１分間乾燥して直描型印刷版原版原版を作製した。実施例１２と同様にしてレーザー照射を行い、希薄なＰＳ版現像液（富士写真フイルム(株)製ネガタイプ用現像液原液を純水で１０倍に希釈したもの）で現像を行ったところ、レーザー出力１００ｍＪ／秒以上でレーザー照射部のみが選択的に残存したネガ型の水あり平版印刷版が得られた。
【０１７２】
実施例１７
実施例１２における水酸基含有化合物である（ｃ）“スミラック”ＰＣ−１（レゾール樹脂）を（ｃ）“マルカリンカー”ＰＨＭ−Ｃ（ポリ(p-ヒドロキシスチレン)、丸善石油化学(株)製）：７０重量部に変更した以外は全く実施例１２と同様に印刷版原版を作製し、同様に評価した。
【０１７３】
その結果、レーザー出力２８０ｍＪ／秒以上でレーザー照射部のみが選択的に残存したポジ型の平版印刷版が得られた。
【０１７４】
実施例１８
実施例１で得た断熱層の上に、次の組成を有する感熱層組成物を塗布し、１５０℃で１分間乾燥し、膜厚２ｇ／ｍ²の感熱層を設けた。
【０１７５】
＜感熱層組成（固形分濃度１１．６重量％）＞
（ａ）“ＳＯＨＮ ＢＬＡＣＫ”（Waterbase）（三菱化学(株)製、カーボンブラ ックの水分散ペースト） ７重量部
（ｂ）鉄（III）アセチルアセトネート（半井化学薬品（株）製）１０重量部
（ｃ）“ゴーセノール”ＫＬ−０５（ポリビニルアルコール、日本合成化学工業（株）製） ８重量部
（ｄ）合成例１のポリマー １５重量部
（ｅ）“ＴＳＬ”８３５０（γ−グリシドキシプロピルトリメトキシシラン、東芝シリコーン（株）製） ２重量部
［溶媒成分］
（１）精製水 ２８０重量部
（２）エタノール ４０重量部
この感熱層の上に下記の組成を有するシリコーンゴム組成物をバーコーターで塗布した後、１１０℃で１分間湿熱硬化させて２．０μｍのシリコーンゴム層を設け、さらに“トレファン”（東レ（株）製、ポリプロピレンフィルム １２μｍ）をラミネートし、直描型水なし平版印刷版原版を得た。
【０１７６】
＜シリコーンゴム層組成（固形分濃度８．４重量％）＞
（１）ポリジメチルシロキサン（分子量約３５，０００、末端水酸基）１００重量部
（２）エチルトリアセトキシシラン １０重量部
（３）ジブチル錫ジアセテート ０．３重量部
［溶媒成分］
（１）“アイソパーＧ”（エクソン化学（株）製） １２００重量部
レーザー照射後の版は、カバーフィルムを剥離した後、水／ジエチレングリコールモノ−２−エチルヘキシルエーテル：９５／５（重量部／重量部）の混合溶液に１分間浸漬し、さらに精製水を浸した現像パッド（３Ｍ（株）製）を用いて版面を摩擦したところ、レーザー出力１１０ｍＪ／秒以上でレーザー照射部のシリコーンゴム層が除去されたネガ型の水なし平版印刷版が得られた。
【０１７７】
さらに、製版後の版を用いて、レーザー出力２００ｍＪ／秒における画線部ベタ部の感熱層の厚さを測定したところ１．９ｇ／ｍ²であり、残存率９５％であった。
【０１７８】
実施例１９
実施例１８で得られた印刷版原版に、波長１０６４ｎｍ、ビーム径１００μｍ（１／ｅ2）の半導体励起ＹＡＧレーザーを用いて連続線の書き込みを行った。記録エネルギーは０．７５Ｊ／ｃｍ²とした。
【０１７９】
その後、実施例１８と同様に現像処理したところ、レーザー光が照射されたシリコーンゴム層のみが除去されたネガ型の水なし平版印刷版が得られた。
【０１８０】
画線部感熱層の膜厚を測定したところ、１．７５ｇ／ｍ²であり、残存率８７．５％であった。
【０１８１】
実施例２０
砂目立てしたアルミ板を８０℃に加熱した弗化ジルコニウムの５％水溶液で２分間表面処理し、乾燥して基板とした。この基板上に下記の感熱性組成物を乾燥膜厚５．０ｇ／ｍ2になるように塗布し、１５０℃で１分間乾燥した。
【０１８２】
＜感熱層組成（固形分濃度５４重量％）＞
（ａ）“ＫＡＹＡＳＯＲＢ”ＩＲ−８２０Ｂ（赤外線吸収染料、日本化薬（株）製） ５重量部
（ｂ）“アルミキレート”Ａ（アルミニウムトリスアセチルアセトネート、川研ファインケミカル（株）製）２０重量部
（ｃ）“エポキシエステル”８０ＭＦＡ（エポキシアクリレート、共栄社化学（株）製））４０重量部
（ｄ）“ＫＡＹＡＭＥＲ”ＰＭ−２１（含リンモノマー、日本化薬（株）製）５重量部
（ｅ）“サンプレン”ＬＱ−Ｔ１３３１（ポリウレタン樹脂、三洋化成工業（株）製） ４０重量部
（ｆ）トリレンジイソシアネート ５重量部
（ｇ）酢酸 ２重量部
［溶媒成分］
（１）ジメチルホルムアミド ５０重量部
（２）エチルセロソルブ ２５重量部
（３）メチルイソブチルケトン ２５重量部
感熱層上に実施例１８と同じシリコーンゴム層を塗設し、直描型水なし平版印刷版原版を得た。得られた原版は、実施例１８と同様にレーザー照射を行い、同様に現像した。その結果、レーザー出力１１０ｍＪ／秒以上でネガ型の水なし平版印刷版が得られた。
【０１８３】
さらに、製版後の版を用いて、レーザー出力２００ｍＪ／秒における画線部ベタ部の感熱層の厚さを測定したところ４．９ｇ／ｍ²であり、残存率９８％であった。
【０１８４】
実施例２１
厚さ０．２４ｍｍの脱脂したアルミ板上に下記の組成よりなる溶液を塗布し、２００℃、２分間乾燥し、３ｇ／ｍ²の断熱層を設けた。
【０１８５】
＜断熱層組成（固形分濃度１６．７重量％）＞
（１）エポキシ・フェノール樹脂“カンコート”９０Ｔ−２５−３０９４（関西ペイント（株）製） １５重量部
（２）“ＫＡＹＡＳＯＲＢ”ＩＲ−８２０Ｂ（赤外線吸収染料、日本化薬（株）製） ０．１６重量部
［溶媒成分］
（１）ジメチルホルムアミド ８５重量部
この断熱層上に、次の組成を有する感熱層組成物を塗布し、１３０℃で１分間乾燥し、膜厚１ｇ／ｍ²の感熱層を設けた。
【０１８６】
＜感熱層組成（固形分濃度１０重量％）＞
（ａ）“ＫＡＹＡＳＯＲＢ”ＩＲ−８２０Ｂ（赤外光吸収染料、日本化薬（株）製） １０重量部
（ｂ）“ナーセム”Ｔｉ（日本化学産業（株）製） １０重量部
（ｃ）“スミライトレジン”ＰＲ−５０７３１（ノボラック樹脂、住友デュレス（株）製）） ４０重量部
（ｄ）“サンプレン”ＬＱ−Ｔ１３３１（ポリウレタン樹脂、三洋化成工業（株） 製） ３０重量部
（ｅ）N,N,N'-トリ（2-ヒドロキシ-3-メタクリロキシプロピル）-N'-（2-ヒドロキシ-3-トリメトキシシリルプロピルオキシプロピル）ポリオキシプロピレ ンジアミン １０重量部
［溶媒成分］
（１）ジメチルホルムアミド １００重量部
（２）テトラヒドロフラン ７００重量部
（３）イソプロピルアルコール １００重量部
感熱層上に実施例１３と同じシリコーンゴム層を塗設し、直描型水なし平版印刷版原版を得た。得られた原版は、実施例１３と同様にレーザー照射を行い、同様に現像した。その結果、レーザー出力１３０ｍＪ／秒以上でネガ型の水なし平版印刷版が得られた。
【０１８７】
実施例２２
実施例２１の感熱層上に、下記シリコーンゴム層組成物をバーコーターを用いて塗布し、乾燥膜厚２．０μｍ、乾燥条件は１２０℃×１分間とした以外は全く実施例２１と同様に印刷版原版を作成し、評価を行ったところ、レーザー出力１４０ｍＪ／秒以上でネガ型の水なし平版印刷版が得られた。
【０１８８】
＜シリコーンゴム層組成（固形分濃度９．４重量％）＞
（１）α，ω−ジビニルポリジメチルシロキサン（重合度７７０）１００重量部
（２）ＨＭＳ−５０１（チッソ（株）製 両末端メチル（メチルハイドロジェンシロキサン）（ジメチルシロキサン）共重合体 ＳｉＨ基数／分子量＝０．６９mol/g） ４重量部
（３）オレフィン配位白金 ０．０２重量部
（４）“ＢＹ２４−８０８”（ダウコーニングシリコーン（株）製 反応抑制剤） ０．３重量部
（５）ビニルトリ（メチルエチルケトオキシム）シラン ４重量部
［溶媒成分］
（１）“アイソパー”Ｅ（エッソ化学（株）製） １０００重量部
本実施例の結果を表１〜４に示す。
【０１８９】
【表１】

【表２】

【表３】

【表４】

【０１９０】
【発明の効果】
本発明は、直描型水なし平版印刷版原版において、感熱層が（ａ）光熱変換物質と（ｂ）金属キレート化合物を含有することで、レーザー光照射後の煩雑な工程を必要とせずとも画像再現性の良好な直描型水なし平版が得られる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a printing plate precursor that can be printed without using a fountain solution, and more particularly to a direct-drawing waterless lithographic printing plate precursor that can be directly made with a laser beam.
[0002]
[Prior art]
So-called direct plate making, which does not require a plate-making film, is made directly from a manuscript. The so-called direct plate making is simple and does not require skill, is quick enough to obtain a printing plate in a short time, and has quality and cost from various systems. Taking advantage of features such as rationality that can be selected according to the situation, the company has begun to enter not only the light printing industry, but also general offset printing and gravure printing.
[0003]
Particularly recently, various types of lithographic printing materials have been developed due to rapid progress in output systems such as prepress systems, imagesetters, and laser printers.
[0004]
When these lithographic printing plates are classified by the plate making method, a laser beam irradiation method, a thermal head writing method, a voltage application method using a pin electrode, an ink repellent layer or an ink deposit layer is formed by inkjet. The method etc. are mentioned.
[0005]
Among them, the method using laser light is superior to other methods in terms of resolution and plate making speed, and there are many types.
[0006]
In particular, the heat mode type has the advantage that it can be handled in a bright room, and its usefulness has recently been reviewed due to the rapid progress of semiconductor lasers as light sources.
[0007]
For example, JP-A-6-199064, USP5339737, USP5353705, EP0580393, JP-A-6-55723, EP0573091, USP5378580, JP-A-7-164773, JP-A-6- No. 186750, JP-A-7-309001, JP-A-9-104182, JP-A-9-146264, JP-A-9-146265, JP-A-9-236927, JP-A-9-244228 Japanese Laid-Open Patent Publication No. EPO6444047 describes a direct-drawing waterless lithographic printing plate precursor using a laser beam as a light source and a plate making method thereof.
[0008]
The heat-sensitive layer of the thermal destruction type printing plate precursor mainly uses carbon black as a laser light absorbing compound and nitrocellulose as a thermal decomposition compound. The carbon black absorbs the laser beam to be converted into thermal energy, and the heat sensitive layer is destroyed by the heat. Finally, by removing this part by development, the silicone rubber layer on the surface is peeled off at the same time to form an ink-implanted part.
[0009]
However, since this printing plate destroys the heat-sensitive layer and forms an image, the depth of the cell in the image area becomes deep, the ink deposition property at a minute halftone dot is poor, and the ink mileage is poor. there were. Further, there is a problem that the printing plate is inferior in printing durability because a crosslinked structure is formed in order to make the heat-sensitive layer easily destroyed by heat. When the heat-sensitive layer was softened, the sensitivity was extremely lowered, and it was difficult to soften the heat-sensitive layer.
[0010]
Further, this printing plate has a low sensitivity, and there is a problem that a high laser beam intensity is required to destroy the heat-sensitive layer.
[0011]
In JP-A-9-146264, a photothermal conversion layer has a compound that converts laser light into heat, a polymer compound having film-forming ability, a photopolymerization initiator, and a photopolymerizable ethylenically unsaturated compound. In addition, a negative type laser-sensitive dampening water-free lithographic printing plate precursor in which a photothermal conversion layer and a silicone rubber layer are reacted by performing overall exposure with energy rays after forming a silicone rubber layer has been proposed.
[0012]
In this plate material, the entire surface is exposed after the silicone rubber layer is applied, for example, Kobayashi et al. (For example, “Papers of Printing Society, 18, 128 (1979)” and “Journal of Applied Photoengineering, vol. 6,). pp. 65-68 "etc.), the adhesive force between the silicone rubber layer and the photosensitive layer is improved, and as a result, a plate material excellent in image reproducibility and scratch resistance is obtained. . However, as described above, there is a trade-off relationship between flexibility and sensitivity of the photosensitive layer, and there is a problem that sensitivity is particularly low.
[0013]
Japanese Patent Laid-Open No. 9-239842 proposes a peeling development type printing plate containing a substance that generates an acid in a laser-sensitive layer and a polymer compound that decomposes under the action of an acid. There are problems inherent to peeling development, in which two processes, a process and a heating process, are required, and the reproducibility of fine halftone dots is poor.
[0014]
Further, particularly in JP-A-6-55723, EP0573091, and USP5378580, since an Nd-YAG laser is used as a light source, another problem is that the exposure apparatus becomes considerably large. There was also.
[0015]
In addition, US Pat. No. 5,379,698, JP-A-7-314934, and JP-A-9-236927 describe a direct-drawing waterless lithographic printing plate using a metal thin film as a heat-sensitive layer.
[0016]
This printing plate material has a very thin heat-sensitive layer, so that a very sharp image can be obtained and it is advantageous in terms of resolution of the printing plate. There was a problem in that the heat-sensitive layer at the line part peeled off, and the ink adhered, resulting in a defect on the printed matter. In addition, this printing plate also has a problem in that the image-forming portion cells are deepened because the heat-sensitive layer is destroyed and the image area is deepened, resulting in poor ink fillability and ink mileage.
[0017]
In addition to the lithographic printing plate using laser light as described above, as a direct drawing type waterless lithographic printing plate, a heat bonding type directly drawing waterless lithographic printing plate can be considered.
[0018]
In this type of plate material, the silicone rubber layer in the laser light irradiation portion selectively remains and functions as a non-image portion. As the mechanism, the adhesive force between the silicone rubber layer and the laser sensitive layer or the adhesive force between the laser sensitive layer and the underlying substrate is improved in some way by laser light irradiation. The silicone rubber layer, or the silicone rubber layer and the laser-sensitive layer are selectively removed by subsequent processing.
[0019]
As this type of plate material, for example, JP-A-9-68794, JP-A-9-80745, JP-A-9-120157, JP-A-9-197659, and the like have been proposed.
[0020]
The plate material proposed in Japanese Patent Application Laid-Open No. 9-120157 is intended to reproduce an image by advancing the reaction of the photosensitive layer using an acid generated by laser light irradiation as a catalyst. However, in order to advance the reaction after acid generation, a process called heat treatment is required. Furthermore, since the time from acid generation to heat treatment affects the image reproducibility, there is a problem that the image reproducibility becomes unstable.
[0021]
The plate materials proposed in JP-A-9-80745 and JP-A-9-197659 also have a bond capable of reacting in the presence of an acid and a compound capable of generating an acid upon irradiation with actinic rays in the photosensitive layer. Since this is a type in which the reaction is carried out using the generated acid after irradiation with laser light, it has the same problems as described above.
[0022]
[Problems to be solved by the invention]
The present invention provides a direct-drawing waterless lithographic printing plate with good image reproducibility without the need for a complicated process after laser light irradiation in order to improve the drawbacks of the prior art.
[0023]
[Means for Solving the Problems]
That is, the present invention has the following configuration.
[0024]
(1) At least a heat-sensitive layer on the substrate, Silicone rubber layerA heat-sensitive layer comprising: (a) a photothermal conversion substance; and (b)Acetyl acetonate, 2,2,6,6-tetramethyl-3,5-heptanedionate, benzoylacetonate, 1,3-diphenyl-1,3-propanedionate, methyl acetoacetate, ethyl acetoacetate, methacryl Having a ligand selected from oxyethyl acetoacetate, allyl acetoacetate, hexanedionate, heptanedionate, tetramethylheptanedionate and benzoyl acetateMetal chelate compounds, (c)Hydroxyl-containing compoundAnd (d) containing a binder polymerDirect-drawing waterless lithographic printing plate precursor.
(2) At least a heat-sensitive layer on the substrate, Silicone rubber layerA heat-sensitive layer comprising: (a) a photothermal conversion substance; and (b)Acetyl acetonate, 2,2,6,6-tetramethyl-3,5-heptanedionate, benzoylacetonate, 1,3-diphenyl-1,3-propanedionate, methyl acetoacetate, ethyl acetoacetate, methacryl Having a ligand selected from oxyethyl acetoacetate, allyl acetoacetate, hexanedionate, heptanedionate, tetramethylheptanedionate and benzoyl acetateMetal chelate compounds, (c)Hydroxyl-containing compoundAnd (b) a metal chelate compound and (c)Hydroxyl-containing compoundIt has a crosslinked structure formed by the reaction ofDirect-drawing waterless lithographic printing plate precursor.
[0025]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is described in detail below.
[0026]
In the present invention, the direct drawing type means that an image is formed directly on a printing plate from a recording head without using a negative or positive film at the time of exposure.
[0027]
  [Thermosensitive layer] of the present inventionDirect drawing type waterless planographic printing plate precursorIn order to form an image by irradiating laser light, it is necessary to contain “(a) a photothermal conversion substance”.
[0028]
The “(a) photothermal conversion substance” is not particularly limited as long as it absorbs laser light. For example, black pigments such as carbon black, aniline black, and cyanine black, phthalocyanine, naphthalocyanine-based green pigments, Carbon graphite, iron powder, diamine metal complex, dithiol metal complex, phenol thiol metal complex, mercaptophenol metal complex, crystal water-containing inorganic compound, copper sulfate, chromium sulfide, silicate compound, titanium oxide, vanadium oxide It is preferable to add metal oxides such as manganese oxide, iron oxide, cobalt oxide and tungsten oxide, hydroxides and sulfates of these metals, and metal powders such as bismuth, iron, magnesium and aluminum. .
[0029]
Among these, carbon black is preferable from the viewpoints of photothermal conversion, economic efficiency, and handleability.
[0030]
In addition to the above substances, dyes that absorb infrared rays or near infrared rays are also preferably used as photothermal conversion materials.
[0031]
As these dyes, all dyes having a maximum absorption wavelength in the range of 400 nm to 1200 nm can be used. Preferred dyes are cyanine-based, phthalocyanine-based, phthalocyanine metal complex-based, naphthalocyanine-based dyes for electronics and recording. , Naphthalocyanine metal complex, dithiol metal complex, naphthoquinone, anthraquinone, indophenol, indoaniline, pyrylium, thiopyrylium, squarylium, croconium, diphenylmethane, triphenylmethane, triphenylmethanephthal , Triallylmethane, phenothiazine, phenoxazine, fluoran, thiofluorane, xanthene, indolylphthalide, spiropyran, azaphthalide, chromenopyrazole Leucooramine, rhodamine lactam, quinazoline, diazaxanthene, bislactone, fluorenone, monoazo, ketone imine, disazo, polymethine, oxazine, nigrosine, bisazo, bisazostilbene, bis Azooxadiazole, bisazofluorenone, bisazohydroxyperinone, azochrome complex, trisazotriphenylamine, thioindigo, perylene, nitroso, 1: 2 type metal complex, intermolecular CT , Quinoline, quinophthalone, fulgide acid dyes, basic dyes, dyes, oil-soluble dyes, triphenylmethane leuco dyes, cationic dyes, azo disperse dyes, benzothiopyran spiropyrans, 3,9-dibromoant Antron, Indanthron, Feno Rufutarein, sulfo phthalein, ethyl violet, methyl orange, fluorescein, methyl viologen, methylene blue, and the like gym loss betaine.
[0032]
Among these, cyanine dyes, azurenium dyes, squarylium dyes, croconium dyes, azo disperse dyes, bisazostilbenes, which are dyes for electronics and recording and have a maximum absorption wavelength in the range of 700 nm to 900 nm. Dyes, naphthoquinone dyes, anthraquinone dyes, perylene dyes, phthalocyanine dyes, naphthalocyanine metal complex dyes, polymethine dyes, dithiol nickel complex dyes, indoaniline metal complex dyes, intermolecular CT dyes, benzothiopyran dyes Spiropyran, nigrosine dye and the like are preferably used.
[0033]
Further, among these dyes, those having a large molar absorbance coefficient are preferably used. Specifically, ε = 1 × 10^FourOr more, more preferably 1 × 10^FiveThat's it. ε is 1 × 10^FourThis is because if it is smaller, the effect of improving the sensitivity is hardly exhibited.
[0034]
These “(a) photothermal conversion substances” alone have an effect of improving the sensitivity, but the sensitivity can be further improved by using two or more in combination.
[0035]
Further, by using two or more kinds of “(a) photothermal conversion substances” having different absorption wavelengths, it is possible to cope with two or more kinds of lasers having different emission wavelengths.
[0036]
The content of these “(a) photothermal conversion substances” is preferably 0.1 to 70% by weight, more preferably 0.5 to 40% by weight, based on the total heat-sensitive layer composition. When the amount is less than 0.1% by weight, the effect of improving the sensitivity to laser light is not observed, and when the amount is more than 40% by weight, the printing durability of the printing plate tends to be lowered.
[0037]
  Of the present inventionDirect drawing type waterless planographic printing plate precursorThe heat-sensitive layer contains “(b) metal chelate compound”.
[0038]
The “(b) metal chelate compound” as used in the present invention is a complex compound comprising a “central metal” and an “ligand” which is an organic substituent, in which an organic ligand is coordinated to the metal. Or an organometallic compound covalently bonded to an organic functional group.
[0039]
The ligand which is an organic substituent is classified into a monodentate ligand and a polydentate ligand, and preferably has a polydentate ligand, particularly a bidentate ligand.
[0040]
Also, inorganic compounds such as metal oxides are not in that category. These metal chelate compounds are characterized by causing a substitution reaction with a compound containing an active hydrogen group.
[0041]
Examples of the “center metal” include metals from the second period to the sixth period of the periodic table, and among them, metals from the third period to the fifth period are preferable, Al of the third period metal, Ti of the fourth period metal, Mn, Fe, Co, Ni, Cu, Zn, Ge, and the fifth periodic metal In and Sn are particularly preferable.
[0042]
  The “(b) metal chelate compound” is formed between the metal and the organic compound as described above. Examples of such forms include the following specific examples..
[0044]
  Specifically, the chelate moiety is 2,4-pentadionate (acetylacetonate).2, 2,6,6-tetramethyl-3,5-heptanedionate, benzoylacetonateAndMetal pentanedionates (metal acetonates) such as 1,3-diphenyl-1,3-propanedionate, and metal acetoacetates such as methyl acetoacetate, ethyl acetoacetate, methacryloxyethyl acetoacetate and allyl acetoacetateKindCan be mentioned.
[0050]
  MoneySpecific examples of the genus chelate compound include the following compounds.Among them, in the present invention, (b) acetylacetonate, 2,2,6,6-tetramethyl-3,5-heptanedionate, benzoylacetonate, 1,3-diphenyl-1,3-propanedionate, methylacetate A metal chelate compound having a ligand selected from acetate, ethyl acetoacetate, methacryloxyethyl acetoacetate, allyl acetoacetate, hexane dionate, heptane dionate, tetramethyl heptane dionate and benzoyl acetate is used.
[0051]
Specific examples of the aluminum chelate compound include aluminum isopropylate, monosec-butoxyaluminum diisopropylate, aluminum sec-butyrate, ethyl acetate aluminum diisopropylate, propyl acetate aluminum diisopropylate, butyl acetate aluminum diisopropylate, heptyl acetate. Aluminum diisopropylate, hexyl acetate aluminum diisopropylate, octyl acetate aluminum diisopropylate, nonyl acetate aluminum diisopropylate, ethyl acetate aluminum diethylate, ethyl acetate aluminum dibutyrate, ethyl acetate aluminum diheptylate, ethyl acetate aluminum dino Elm , Diethyl acetate aluminum isopropylate, aluminum tris (ethyl acetoacetate), aluminum tris (propyl acetoacetate), aluminum tris (butyl acetoacetate), aluminum tris (hexyl acetoacetate), aluminum tris (nonyl acetoacetate), aluminum tris Acetylacetonate, aluminum bisethylacetoacetate monoacetylacetonate, aluminum diacetylacetonate ethylacetoacetate, aluminum monoacetylacetonate bispropylacetoacetate, aluminum monoacetylacetonate bisbutylacetoacetate, aluminum monoacetylacetonate bishexylacetate Acetate, aluminum monoethylene Acetoacetate bispropyl acetoacetonate, aluminum monoethyl acetoacetate bisbutyl acetoacetonate, aluminum monoethyl acetoacetate bishexyl acetoacetonate, aluminum monoethyl acetoacetate bisnonyl acetoacetonate, aluminum dibutoxide monoacetoacetate, aluminum di Propoxide monoacetoacetate, aluminum dibutoxide monoethyl acetoacetate, aluminum oxide acrylate, aluminum oxide octate, aluminum oxide stearate, trisalizarin aluminum, aluminum-s-butoxide bis (ethylacetoacetate), aluminum di-s-butoxide Ethyl acetoacetate, aluminum-9-octa Decenyl acetoacetate diisopropoxide, aluminum phenoxide, aluminum acrylate, aluminum methacrylate, etc.
[0052]
Specific examples of the titanium chelate compound include isopropyl triisostearoyl titanate, isopropyl tri-n-stearoyl titanate, isopropyl trioctanoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphite) titanate, tetraisopropyl bis (dioctyl) Phosphite) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (di-tridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, Bis (dioctyl pyrophosphate) ethylene titanate, Tris (dioctyl pyrophosphate) ethylene titanate Isopropyl dimethacrylisostearoyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumyl phenyl titanate, isopropyl tri (N-aminoethylaminoethyl) titanate, dicumyl phenyloxyacetate titanate, Diisostearoyl ethylene titanate, isopropyl diisostearoyl cumylphenyl titanate, isopropyl distearoyl methacryl titanate, isopropyl diisostearoyl acryl titanate, isopropyl 4-aminobenzenesulfonyldi (dodecylbenzenesulfonyl) titanate, isopropyltrimethacryl titanate, isopropyldi ( 4-aminobenzoyl) iso Thearoyl titanate, isopropyl tri (dioctyl pyrophosphate) titanate, isopropyl triacryl titanate, isopropyl tri (N, N-dimethylethylamino) titanate, isopropyl trianthranyl titanate, isopropyl octyl, butyl pyrophosphate titanate, isopropyl di (butyl, methyl) Pyrophosphate) titanate, tetraisopropyl di (dilauroyl phosphite) titanate, diisopropyloxyacetate titanate, isostearoyl methacryloxyacetate titanate, isostearoyl acryloxyacetate titanate, di (dioctyl phosphate) oxyacetate titanate, 4-aminobenzenesulfonyldodecyl Benzenesulfonyloxyace Tate titanate, dimethacryloxyacetate titanate, dicumyl phenolate oxyacetate titanate, 4-aminobenzoylisostearoyloxyacetate titanate, diacryloxyacetate titanate, di (octyl, butylpyrophosphate) oxyacetate titanate, isostearoyl methacrylethylene titanate , Di (dioctyl phosphate) ethylene titanate, 4-aminobenzenesulfonyldodecylbenzenesulfonylethylene titanate, dimethacrylethylene titanate, 4-aminobenzoylisostearoyl ethylene titanate, diacrylethylene titanate, dianthranylethylene titanate, di (butyl, methylpyro Phosphate) ethylene titanate, titanium allyl Cetoacetate triisopropoxide, titanium bis (triethanolamine) diisopropoxide, titanium di-n-butoxide (bis-2,4-pentanedionate), titanium diisopropoxide bis (tetramethylheptanedionate), titanium Diisopropoxide bis (ethyl acetoacetate), titanium methacryloxyethyl acetoacetate triisopropoxide, titanium methylphenoxide, titanium oxide bis (pentanedionate), etc.
[0053]
Iron (III) acetylacetonate, dibenzoylmethane iron (II), tropolone iron, tristropolonoiron (III), hinokitiol iron, trishinokithioloiron (III), acetoacetate iron (III), iron (III) benzoyl Acetonate, iron (III) trifluoropentanedionate, salicylaldehyde copper (II), copper (II) acetylacetonate, salicylaldehyde imine copper, kojic acid copper, biscojato copper (II), tropolone copper, bistropolono copper ( II), bis (5-oxynaphthoquinone-1,4) copper, bis (1-oxyanthraquinone) nickel, acetoacetate copper, salicylamine copper, o-oxyazobenzene copper, copper (II) benzoyl acetate, copper (II ) Ethyl acetoacetate, copper (II) methacryloxyethyl acetoacetate, copper ( II) Methoxyethoxy ethoxide, copper (II) 2,4-pentanedionate, copper (II) 2,2,6,6-tetramethyl-3,5-heptanedionate, zinc N, N-dimethylaminoethoxide Side, zinc 2,4-pentanedionate, zinc 2,2,6,6-tetramethyl-3,5-heptanedionate and the like are also preferably used in the present invention.
[0054]
Others: salicylaldehyde cobalt, o-oxyacetophenone nickel, bis (1-oxyxanthone) nickel, nickel pyromeconate, salicylaldehyde nickel, allyltriethylgermane, allyltrimethylgermane, ammoniumtris (oxalate) germanate, bis [bis (trimethylsilyl) ) Amino] germanium (II), carboxyethyl germanium sesquioxide, cyclopentadienyltrimethylgermane, di-n-butyldiacetoxygermane, di-n-butyldichlorogermane, dimethylaminotrimethylgermane, diphenylgermane, hexaallyldigerma Noxan, hexaethyldigermanoxane, hexamethyldigerman, hydroxygermatrane monohydrate, methacryloxymethyltrimethyl Tilgermane, methacryloxytriethylgermane, tetraallylgermane, tetra-n-butylgermane, tetraisopropoxygermane, tri-n-butylgermane, trimethylchlorogermane, triphenylgermane, vinyltriethylgermane, bis (2,4-pentanedio Nate) dichlorotin, di-n-butylbis (2,4-pentanedionate) tin, calcium 2,4-pentanedionate, cerium (III) 2,4-pentanedionate, cobalt (II) 2,4-pentane Dionate, cobalt (III) 2,4-pentanedionate, europium 2,4-pentanedionate, europium (III) thenoyl trifluoroacetonate, indium 2,4-pentanedionate, manganese (II) 2,4 -Pentagonione , Used in the present invention well as manganese (III) 2,4-pentanedionate.
[0055]
  Among these specific examples, the “(b) metal chelate compound” that is particularly preferably used has a bidentate ligand, and in particular acetylacetonate (pentanedionate)., FXanthioneGPtandioneeGThose having tetramethylheptanedionate or benzoylacetonate as a ligand are preferred.
[0056]
  In addition, aluminum, iron (III), titanium acetylacetonate (pentandionate), FXanthioneGPtandioneeGTetramethylheptanedionate, benzoylacetonates and the like are mentioned as preferred compounds.
[0057]
These "(b) metal chelate compounds" can be used alone or in combination of two or more, and the content thereof is 5 to 300 parts by weight with respect to 100 parts by weight of the active hydrogen group-containing compound. 10 to 150 parts by weight is more preferable. If the content is less than 5 parts by weight, it is difficult to form an image. If the content is more than 300 parts by weight, the physical properties of the heat-sensitive layer are likely to deteriorate, and the printing plate tends to have a problem such as printing durability. .
[0058]
In the present invention, when laser light is irradiated, heat is generated by the action of “(a) photothermal conversion substance” in the heat-sensitive layer, and a crosslinked structure of “(b) metal chelate compound” is formed by the heat. The As a result, the adhesive force between the silicone rubber layer and the heat sensitive layer is improved in the laser light irradiated portion. On the other hand, in the non-irradiated portion, such an adhesive force is not improved, and thus the silicone rubber layer or the silicone rubber layer and the heat-sensitive layer are removed by the subsequent development process. In this way, a positive direct-drawing waterless planographic printing plate is obtained.
[0059]
On the other hand, when a crosslinked structure is formed in advance in the heat-sensitive layer, a highly sensitive negative direct-drawing waterless lithographic printing plate can be obtained. That is, the adhesive force between the heat-sensitive layer and the silicone rubber layer in the laser beam irradiation portion is reduced, and the silicone rubber layer in the portion irradiated with the laser beam is removed by subsequent development processing. Although the detailed mechanism is not yet elucidated, it is probable that the cross-linked structure formed at the time of plate preparation was desorbed by the action of heat generated by laser irradiation. As a result, the solvent resistance at the interface between the silicone rubber layer and the heat-sensitive layer changes, and it is considered that the silicone rubber layer in the laser irradiation part is specifically removed by the development treatment.
[0060]
  Of the present inventionDirect drawing type waterless planographic printing plate precursorFrom the viewpoint of forming a crosslinked structure with “(b) metal chelate compound”, it is preferable that the thermosensitive layer further contains “(c) active hydrogen group-containing compound”. Examples of “(c) active hydrogen group-containing compound” include a hydroxyl group-containing compound, an amino group-containing compound, a carboxyl group-containing compound, a thiol group-containing compound, and the like, and a hydroxyl group-containing compound is preferable.
[0061]
Furthermore, as the hydroxyl group-containing compound, either a phenolic hydroxyl group-containing compound or an alcoholic hydroxyl group-containing compound can be used in the present invention.
[0062]
Examples of the phenolic hydroxyl group-containing compound include the following compounds.
[0063]
Hydroquinone, catechol, guaiacol, cresol, xylenol, naphthol, dihydroxyanthraquinone, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, bisphenol A, bisphenol S, phenol formaldehyde novolac resin, resole resin, resorcinbenzaldehyde resin, pyrogallol acetone resin, hydroxystyrene And rosin-modified phenol resins, epoxy-modified phenol resins, lignin-modified phenol resins, aniline-modified phenol resins, melamine-modified phenol resins, and bisphenols.
[0064]
Examples of the alcoholic hydroxyl group-containing compound include the following compounds.
[0065]
Ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,8 -Octanediol, 1,9-nonanediol, 1,10-decanediol, 2-butene-1,4-diol, 5-hexene-1,2-diol, 7-octene-1,2-diol, 3- Mercapto-1,2-propanediol, glycerin, diglycerin, trimethylolpropane, 1,2,4-butanetriol, pentaerythritol, dipentaerythritol, sorbitol, sorbitan, polyvinyl alcohol, cellulose and Derivatives, polymers and copolymers of hydroxyethyl (meth) acrylate and the like.
[0066]
In addition, epoxy acrylate, epoxy methacrylate, polyvinyl butyral resin, polymers having a hydroxyl group introduced by a known method, and the like can also be used in the present invention.
[0067]
As these hydroxyl group-containing compounds, phenolic hydroxyl group-containing compounds are particularly preferably used from the viewpoint of reactivity with metal chelate compounds.
[0068]
These “(c) active hydrogen group-containing compounds” can be used alone or in admixture of two or more, and the content thereof is 5 to 80% by weight based on the total heat-sensitive layer composition. Is more preferable, and 20 to 60% by weight is more preferable. If the content is less than 5% by weight, the sensitivity of the printing plate is lowered. Conversely, if the content is more than 80% by weight, the solvent resistance of the printing plate tends to be lowered.
[0069]
  Of the present inventionDirect drawing type waterless planographic printing plate precursorThe heat-sensitive layer preferably contains “(d) a binder polymer” from the viewpoint of printing durability. In this case, the “(d) binder polymer” is not particularly limited as long as it is soluble in an organic solvent and has film-forming ability, but the glass transition temperature (Tg) of “(d) binder polymer” is 20 The glass transition temperature is preferably 0 ° C. or lower, more preferably 0 ° C. or lower.
[0070]
Specific examples of the binder polymer that is soluble in an organic solvent, has a film-forming ability, and also has a function of maintaining a shape include vinyl polymers, unvulcanized rubber, polyoxides (polyethers), polyesters, and polyurethane. However, the present invention is not limited to these.
[0071]
The content of these “(d) binder polymers” is preferably 5 to 70% by weight, more preferably 10 to 50% by weight, based on the total heat-sensitive layer composition. If the content is less than 5%, the printing durability tends to be lowered, and if it is more than 70% by weight, the sensitivity tends to be lowered.
[0072]
"(D) Binder polymer" may be used alone or in combination with several kinds of polymers.
[0073]
"(E) Other ingredients"
Furthermore, in the present invention, a leveling agent, a surfactant, a dispersant, a plasticizer and the like may be optionally added to the heat sensitive layer as necessary.
[0074]
Addition of various coupling agents such as a silane coupling agent is highly preferred in order to improve the adhesion to the underlying substrate and the heat insulating layer.
[0075]
Moreover, in order to improve adhesiveness with the upper silicone rubber layer, it is also preferable to add a silane coupling agent or an unsaturated group-containing compound.
[0076]
Regarding the physical properties of the heat-sensitive layer thus obtained, the physical properties are preferably within a specific range from the viewpoint of printing characteristics of the obtained printing plate. Examples of such physical properties include tensile properties, and among them, initial elastic modulus during tension. Specifically, the initial elastic modulus at the time of tension of the heat-sensitive layer in the printing plate is 7 kgf / mm.²~ 78kgf / mm²Range, or even 10 kgf / mm²~ 65kgf / mm²It is preferable that it exists in the range.
[0077]
By setting the initial elastic modulus of the heat-sensitive layer in the above range, the characteristics as a printing plate, particularly the printing durability, can be improved. Conversely, the initial elastic modulus is 7 kgf / mm²If it is less than the range, the heat-sensitive layer forming the image line portion is likely to be solid, so that it becomes easy to generate wicking during printing. The initial elastic modulus is 78 kgf / mm²In the above case, the repeated stress applied at the time of printing tends to cause breakage at the adhesive interface between the heat-sensitive layer and the silicone rubber layer, resulting in a decrease in printing durability.
[0078]
The thickness of the heat-sensitive layer is preferably 0.1 to 10 g / m 2 as a coating layer in terms of printing durability of the printing plate and the ability to easily dilute the diluting solvent, and more preferably 1 to 7 g. / M2.
[0079]
[Silicone rubber layer]
As the silicone rubber layer applied to the printing plate of the present invention, a silicone rubber layer used in a conventional waterless lithographic printing plate can be used.
[0080]
Such a silicone rubber layer is obtained by sparsely crosslinking a linear organopolysiloxane (preferably dimethylpolysiloxane). As a typical example, a repeating unit represented by the following formula (I) is used. The thing which has.
[0081]
[Chemical 1]

(Here, n is an integer of 2 or more. R is an alkyl, aryl, or cyanoalkyl group having 1 to 10 carbon atoms. 40% or less of the total R is vinyl, phenyl, vinyl halide, or phenyl halide. And preferably 60% or more of R is a methyl group, and has at least one hydroxyl group in the molecular chain in the form of a chain end or side chain.)
As the silicone rubber of the present invention, a silicone rubber (RTV, LTV type silicone rubber) that performs condensation-type crosslinking as shown below can be used. That is, it is crosslinked by condensation between end groups represented by formula (II) and formula (III) or formula (IV). At this time, an excess of a crosslinking agent may be present in the system.
[0082]
[Chemical 2]

(Here, R means the same as R described in Formula I.)
Here, R means the same as R described in Formula I. )
[Chemical 3]

(Where R is the same as R described in Formula I, and R¹, R²Is a monovalent lower alkyl group. )
[Formula 4]

(Wherein R is the same as R described in Formula I, and Ac is an acetyl group.)
When performing such condensation-type crosslinking, metal carboxylates such as tin, zinc, lead, calcium, manganese, such as dibutyltin laurate, tin (II) octoate, naphthenate, or chloroplatinic acid A catalyst such as may be added.
[0083]
In addition to this, it is also effective to add SiH group-containing polydimethylsiloxane and hydrolyzable functional group-containing silane (or siloxane), and add known fillers such as silica for the purpose of improving rubber strength. It is optional.
[0084]
Furthermore, in the present invention, in addition to the above-mentioned condensation type silicone rubber layer, an addition type silicone rubber layer can also be used, which is preferable from the viewpoint of handleability.
[0085]
The addition type silicone rubber layer is obtained by diluting, for example, a polyorganosiloxane having at least two vinyl groups in a molecule, a polyorganosiloxane having at least three SiH groups in the molecule, and a platinum compound with an appropriate solvent. Can be formed on the heat-sensitive layer by heating, drying and curing.
[0086]
Examples of the organopolysiloxane having at least two or more vinyl groups in the molecule include those having a vinyl group at either the molecular chain end or in the middle. As the organic group other than the alkenyl group, a substituted or unsubstituted alkyl group can be used. And those having an aryl group are preferred. Moreover, you may contain a trace amount hydroxyl group.
[0087]
Specific examples of the polyorganosiloxane having two or more vinyl groups in the molecule include the following.
[0088]
Polydimethylsiloxane of both terminal vinyl groups, (methylvinylsiloxane) (dimethylsiloxane) copolymer of both terminal methyl groups, (methylvinylsiloxane) (dimethylsiloxane) copolymer of both terminal vinyl groups, A compound in which the main chain of two or more molecules of polydimethylsiloxane is dimethylene-crosslinked, (methyl 1-hexene siloxane) (dimethylsiloxane) copolymer of both terminal methyl groups, (methyl 1-hexene siloxane) of both terminal vinyl groups ( Dimethylsiloxane) copolymer and the like.
[0089]
These polyorganosiloxanes having two or more vinyl groups in the molecule preferably have a molecular weight of 5,000 or more, more preferably 10,000 or more, from the viewpoint of rubber physical properties after curing. Moreover, these can also be used independently and can also be used in mixture of several types by arbitrary ratios.
[0090]
Examples of the polyorganosiloxane having at least 3 SiH groups in the molecule include those having a SiH group at either the molecular chain end or in the middle, and a substituted or unsubstituted alkyl group as an organic group other than the SiH group. Those having an aryl group are preferred.
[0091]
Specific examples of the polyorganosiloxane having at least 3 or more SiH groups in the molecule include the following.
[0092]
Polydimethylsiloxane with SiH groups at both ends, polymethylhydrogensiloxane with methyl groups at both ends, (methylhydrogensiloxane) (dimethylsiloxane) copolymer with methyl groups at both ends, and (methylhydrogensiloxane) with SiH groups at both ends (Dimethylsiloxane) copolymer, cyclic polymethylhydrogensiloxane and the like.
[0093]
As a ratio when the vinyl group-containing polyorganosiloxane and the SiH group-containing polyorganosiloxane are mixed and used, when the number of vinyl groups in the silicone rubber composition is 1, the number of SiH groups is 1.5 to 15. Such a mixing ratio is preferable, and 1.5 to 12 is more preferable. When the number of SiH groups relative to 1 vinyl group is less than 1.5, the curability of the silicone rubber layer tends to decrease, and when it exceeds 15, the silicone rubber tends to become brittle and wear resistance tends to decrease. It is not preferable.
[0094]
Furthermore, the platinum compound preferably used for the addition-type silicone rubber layer is not particularly limited, and examples thereof include platinum alone, platinum chloride, chloroplatinic acid, and olefin coordinated platinum. Among these, olefin coordinated platinum is preferable.
[0095]
In addition, for the purpose of controlling the curing rate of the addition type silicone rubber layer, vinyl group-containing organopolysiloxane such as tetracyclo (methylvinyl) siloxane, carbon-carbon triple bond-containing alcohol, acetone, methyl ethyl ketone, methanol, ethanol, propylene It is preferable to add a reaction inhibitor such as glycol monomethyl ether.
[0096]
In addition to these compositions, a hydroxyl group-containing organopolysiloxane or a hydrolyzable functional group-containing silane (or siloxane) which is a composition of a condensation type silicone rubber layer may be added, and for the purpose of improving rubber strength. A known filler such as silica may be added.
[0097]
Furthermore, in the present invention, the silicone rubber layer preferably contains a known silane coupling agent in addition to the above composition. These silane coupling agents are preferably used in a proportion of 0.1 to 5% by weight, more preferably 0.5 to 3% by weight, based on the solid content of the silicone rubber layer composition.
[0098]
The film thickness of these silicone rubber layers is preferably 0.5 to 20 g / m 2, more preferably 0.5 to 5 g / m 2. When the film thickness is smaller than 0.5 g / m 2, the ink repellency of the printing plate tends to be lowered. When the film thickness is larger than 20 g / m 2, not only is it disadvantageous from an economic viewpoint, but ink mileage There is a problem of getting worse.
[0099]
  [Substrate] of the present inventionDirect drawing type waterless planographic printing plate precursorAny known metal, film, etc. can be used as the substrate used for the substrate as long as it is a dimensionally stable plate-like material. As such a dimensionally stable plate-like material, those conventionally used as a substrate for a printing plate are preferably exemplified. Such substrates include paper, paper laminated with plastic (polyethylene, polypropylene, polystyrene, etc.), a metal plate such as aluminum (including aluminum alloy), zinc, copper, cellulose acetate, polyethylene terephthalate, Examples thereof include plastic films such as polyethylene, polyester, polyamide, polyimide, polystyrene, polypropylene, polycarbonate, and polyvinyl acetate, and paper or plastic films on which the above metal is laminated or vapor-deposited.
[0100]
Of these, the aluminum plate is particularly preferred because it is extremely dimensionally stable and inexpensive. A polyethylene terephthalate film used as a substrate for light printing is also preferably used.
[0101]
  [Heat insulation layer] of the present inventionDirect drawing type waterless planographic printing plate precursorIn order to prevent the heat from the irradiated laser from being released to the substrate, it is effective to provide a heat insulating layer.
[0102]
A known primer layer that has been conventionally used to strengthen the adhesion between the substrate and the heat-sensitive layer may be used as a substitute.
[0103]
The heat insulation layer used in the present invention must satisfy the following conditions. That is, the substrate and the heat-sensitive layer are well bonded, stable over time, and have high resistance to the developer and the solvent used during printing.
[0104]
Those satisfying such conditions include those containing epoxy resin, polyurethane resin, phenol resin, acrylic resin, alkyd resin, polyester resin, polyamide resin, urea resin, polyvinyl butyral resin, casein, gelatin and the like. In these, it is preferable to use a polyurethane resin, a polyester resin, an acrylic resin, an epoxy resin, a urea resin etc. independently or in mixture of 2 or more types.
[0105]
Further, it is also preferable to improve the plate inspection property by adding additives such as pigments and dyes in the heat insulating layer.
[0106]
The thickness of the heat insulating layer is preferably 0.5 to 50 g / m 2, more preferably 1 to 10 g / m 2 as a coating layer. If the thickness is less than 0.5 g / m 2, the effect of blocking morphological defects and chemical adverse effects on the substrate surface is poor, and if it is greater than 50 g / m 2, the above range is preferable because it is disadvantageous from an economic standpoint.
[0107]
[Production method]
The production method and plate making method of the direct-drawing waterless lithographic printing plate precursor in the present invention will be described.
[0108]
On the substrate, using a normal coater such as a reverse roll coater, an air knife coater, a gravure coater, a die coater, or a Meyer bar coater, or a spin coater such as a whaler, a heat insulating layer composition is applied as necessary. After being cured at 300 ° C. for several minutes by heating or irradiation with actinic rays, the thermosensitive layer composition is applied, dried at 50 to 180 ° C. for several tens of seconds to several minutes, and cured if necessary.
[0109]
Thereafter, a silicone rubber composition is applied and heat-treated at a temperature of 50 to 200 ° C. for several minutes to obtain a silicone rubber layer. Thereafter, a protective film is laminated or a protective layer is formed as necessary.
[0110]
[Cover film]
For the purpose of protecting the silicone rubber layer of the direct-drawing waterless lithographic printing plate constructed as described above, a plain or uneven protective film is laminated on the surface of the silicone rubber layer, or in a developing solvent. It is also possible to form a polymer coating that dissolves.
[0111]
Examples of such cover films include polyester films, polypropylene films, polyvinyl alcohol films, saponified ethylene vinyl acetate copolymers, polyvinylidene chloride films, and films deposited with various metals.
[0112]
[Laser irradiation]
The direct drawing type waterless lithographic printing plate precursor thus obtained is exposed in an image form with a laser beam after the protective film is peeled off or on the protective film.
[0113]
As the laser light source used in the plate making exposure process of the present invention, one having a transmission wavelength region in the range of 300 nm to 1500 nm is used. That is, various lasers such as argon ions, krypton ions, helium-neon, helium-cadmium, ruby, glass, YAG, titanium sapphire, dye, nitrogen, metal vapor, excimer, free electrons, and semiconductors are used.
[0114]
Among these, for the purpose of making the printing plate precursor of the present invention, a semiconductor laser having an emission wavelength region near the near infrared region is preferable, and a high-power semiconductor laser is particularly preferably used.
[0115]
[Development method]
As a developing method, it is carried out by a friction treatment in the presence or absence of water or an organic solvent. Alternatively, the printing plate can be prepared by so-called peeling development in which a pattern is formed on the printing plate by peeling off the protective film.
Examples of the developer used in the development treatment include, for example, water or water added with a surfactant, water added with the following polar solvent, and aliphatic hydrocarbons (hexane, Heptane, isoparaffinic hydrocarbon, etc.), aromatic hydrocarbons (toluene, xylene, etc.), halogenated hydrocarbons (tricrene, etc.), etc. Things are used.
[0116]
Polar solvents include ethanol, propanol, isopropanol, ethylene glycol and other alcohols, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetrahydrofuran and other ethers, acetone, methyl ethyl ketone, diacetone alcohol and other ketones And esters such as ethyl acetate, ethyl lactate and ethylene glycol monoethyl ether acetate, carboxylic acids such as caproic acid, 2-ethylhexanoic acid and oleic acid.
[0117]
In addition, a known surfactant can be freely added to the developer composition. Further, alkaline agents such as sodium carbonate, monoethanolamine, diethanolamine, diglycolamine, monoglycolamine, triethanolamine, sodium silicate, potassium silicate, potassium hydroxide, sodium borate and the like can be added.
[0118]
Among these, water or water to which a surfactant is added, and water to which an alkali is added are preferably used.
[0119]
In addition, a known basic dye such as Crystal Violet, Victory Pure Blue, or Astrazone Red, an acid dye, or an oil-soluble dye can be added to these developers to dye the image area simultaneously with development.
[0120]
When developing, these developing solutions can be developed by impregnating a nonwoven fabric, absorbent cotton, cloth, sponge or the like and wiping the plate surface.
[0121]
For development, an automatic developing machine as described in JP-A-63-163357 is used, and after pretreatment of the plate surface with the above developer, the plate surface is rubbed with a rotating brush while showering with tap water or the like. It is also preferable to do this.
[0122]
Development can also be performed by spraying warm water or water vapor onto the plate surface in place of the developer.
[0125]
The present invention is not limited to lithographic printing plates and can be widely applied to image formation. For example, resist, color filter pixel formation, PDP and other display partition formation, relief printing plate, flexographic printing plate, and the like. One example of application to relief printing plates and flexographic printing plates is to form a metal chelate compound layer of the present invention on top of a conventional photosensitive relief printing plate or flexographic printing plate and form an image using a laser. After that, a printing plate is prepared by UV irradiation.
[0126]
Hereinafter, the present invention will be described in more detail with reference to examples.
[0127]
【Example】
Synthesis example 1
(Hydroxyl-containing polymer fine particle dispersion)
A 1-liter three-necked flask is equipped with a stirrer and a nitrogen inlet tube. In this, 50 g of styrene, 20 g of glycidyl methacrylate, 30 g of 2-hydroxyethyl methacrylate, 300 g of 10% polyvinyl alcohol (polymerization degree 500) aqueous solution, 200 g of water, And 0.5 g of potassium persulfate was charged. Nitrogen gas was introduced for about 2 minutes, the atmosphere in the flask was replaced with nitrogen, nitrogen introduction was stopped, the flask was immersed in an 80 ° C. water bath, and a polymerization reaction was carried out for 3 hours with vigorous stirring. A milky white polymer dispersion was obtained.
[0128]
Example 1
A primer solution having the following composition was applied onto a degreased aluminum plate having a thickness of 0.15 mm using a bar coater, dried at 200 ° C. for 2 minutes, and a film thickness of 4 g / m.²A heat insulating layer was applied.
[0129]
<Insulation layer composition (solid content concentration 10% by weight)>
(1) "Samprene" LQ-T1331 (polyurethane resin, manufactured by Sanyo Chemical Industries, Ltd.) 90 parts by weight
(2) "Takenate" B830 (Blocked isocyanate, Takeda Pharmaceutical Co., Ltd.) 35 parts by weight
(3) 8 parts by weight of SJ9372 (epoxy / phenol / urea resin, manufactured by Kansai Paint Co., Ltd.)
[Solvent component]
(4) Dimethylformamide
Subsequently, the following heat-sensitive layer composition was applied thereon using a bar coater, dried at 150 ° C. for 1 minute, and a film thickness of 1.5 g / m.²The heat sensitive layer was provided.
[0130]
<Thermosensitive layer composition (solid content concentration 10% by weight)>
(A) Carbon black-dispersed rosin-modified maleic resin 25 parts by weight
(Inner carbon black 10 parts by weight)
(B) Iron (III) acetylacetonate (manufactured by Hanai Chemicals) 20 parts by weight
(C) DM622 (epoxy methacrylate, manufactured by Nagase Kasei Kogyo Co., Ltd.)) 30 parts by weight
(D) "Samprene" LQ-T1331 (polyurethane resin, manufactured by Sanyo Chemical Industries, Ltd.) 25 parts by weight
[Solvent component]
(1) 50 parts by weight of dimethylformamide
(2) Ethyl cellosolve 25 parts by weight
(3) Methyl isobutyl ketone 25 parts by weight
Subsequently, a silicone rubber layer composition having the following composition was applied thereon using a bar coater, dried at 125 ° C. for 1 minute, and a film thickness of 2 g / m.²The silicone rubber layer was provided.
[0131]
<Silicone rubber layer composition (solid content concentration 7% by weight)>
(1) Vinyl group-containing polysiloxane 100 parts by weight
(2) Hydrogen polysiloxane 5 parts by weight
(3) Polymerization inhibitor 1 part by weight
(4) 2 parts by weight of catalyst
[Solvent component]
(1) "Isopar" E (manufactured by Exxon Chemical Co., Ltd.)
A laminated film obtained as described above was laminated with a polyester film “Lumirror” (manufactured by Toray Industries, Inc.) having a thickness of 8 μm using a calender roller to obtain a direct-drawing waterless lithographic printing plate precursor.
[0132]
Thereafter, the “Lumirror” of this printing plate precursor is peeled off, mounted on FX400-AP (plate making machine, manufactured by Toray Engineering Co., Ltd.), and irradiated with a semiconductor laser (wavelength 830 nm, beam diameter 20 μm). While changing, pulse exposure was performed with an exposure time of 10 μs.
[0133]
Subsequently, the exposed plate was developed with an automatic developing device TWL-650 manufactured by Toray Industries, Inc. At this time, “PP-1” manufactured by Toray Industries, Inc. was used as the pretreatment liquid, water was used as the developer, and “PA-F” manufactured by Toray Industries, Inc. was used as the posttreatment liquid.
[0134]
When the developed plate was observed, only the silicone rubber layer was removed at 300 mJ / s (600 mW) or less, and the heat-sensitive layer was removed together with the silicone rubber layer in a region with higher energy.
[0135]
Next, waterless lithographic ink (Waterless S, manufactured by The Inktec Co., Ltd., red) was developed on the entire developed plate surface with a hand roller, and the laser irradiation energy at which the image was reproduced was examined. As a result, in the region of 175 mJ / s (350 mW) or more, the silicone rubber layer of the laser irradiation portion was removed, and the image was reproduced.
[0136]
Example 2
A printing plate precursor was prepared in the same manner as in Example 1 except that the composition of the heat-sensitive layer coating solution was changed to that shown below.
[0137]
When evaluated in the same manner as in Example 1, only the silicone rubber layer was removed at 225 mJ / s (450 mW) or more and 450 mJ / s (900 mW) or less, and the heat-sensitive layer was removed together with the silicone rubber layer at a higher energy region.
[0138]
<Thermosensitive layer composition (solid content concentration 10% by weight)>
(A) SPRIT NIGROSINE SJ (Dye Specialities, INC.) 15 parts by weight
(B) Iron (III) acetylacetonate (manufactured by Hanai Chemicals) 20 parts by weight
(C) DM622 (epoxy methacrylate, manufactured by Nagase Kasei Kogyo Co., Ltd.)) 30 parts by weight
(D) "Samprene" LQ-T1331 (polyurethane resin, manufactured by Sanyo Chemical Industries, Ltd.) 35 parts by weight
[Solvent component]
(1) 50 parts by weight of dimethylformamide
(2) Ethyl cellosolve 25 parts by weight
(3) Methyl isobutyl ketone 25 parts by weight
Comparative Example 1
In Example 1, except that the composition of the heat-sensitive layer coating liquid was changed to the one shown below, a printing plate precursor was prepared in the same manner and evaluated in the same manner, and the laser-irradiated silicone rubber layer was not peeled off and development was impossible. And the image could not be reproduced.
[0139]
<Thermosensitive layer composition (solid content concentration 10% by weight)>
(B) Iron (III) acetylacetonate (manufactured by Hanai Chemicals) 20 parts by weight
(C) DM622 (epoxy methacrylate, manufactured by Nagase Kasei Kogyo Co., Ltd.)) 30 parts by weight
(D) "Samprene" LQ-T1331 (polyurethane resin, manufactured by Sanyo Chemical Industries, Ltd.) 50 parts by weight
[Solvent component]
(1) 50 parts by weight of dimethylformamide
(2) Ethyl cellosolve 25 parts by weight
(3) Methyl isobutyl ketone 25 parts by weight
Comparative Example 2
In Example 1, except that the composition of the heat-sensitive layer coating liquid was changed to that shown below, a plate material was prepared in the same manner and evaluated in the same manner. Finally, the silicone rubber layer was removed at 500 mJ / s (1000 mW) or more. Only a low sensitivity version was obtained.
[0140]
<Thermosensitive layer composition (solid content concentration 10% by weight)>
(A) SPRIT NIGROSINE SJ (Dye Specialities, INC.) 15 parts by weight
(C) DM622 (epoxy methacrylate, manufactured by Nagase Kasei Kogyo Co., Ltd.)) 30 parts by weight
(D) “Samprene” LQ-T1331 (polyurethane resin, manufactured by Sanyo Chemical Industries, Ltd.) 55 parts by weight
[Solvent component]
(1) 50 parts by weight of dimethylformamide
(2) Ethyl cellosolve 25 parts by weight
(3) Methyl isobutyl ketone 25 parts by weight
Example 3
In Example 1, except that the composition of the heat-sensitive layer coating liquid was changed to that shown below, a printing plate precursor was prepared in the same manner and evaluated in the same manner. When evaluated in the same manner, 225 mJ / s (450 mW) to 450 mJ / s (900 mW) In the following, only the silicone rubber layer was removed, and the heat-sensitive layer was removed together with the silicone rubber layer in the higher energy region.
[0141]
<Thermosensitive layer composition (solid content concentration 10% by weight)>
(A) SPRIT NIGROSINE SJ (Dye Specialities, INC.) 15 parts by weight
(B) "Narsem" Ti (manufactured by Nippon Chemical Industry Co., Ltd.) 20 parts by weight
(C) DM622 (epoxy methacrylate, manufactured by Nagase Kasei Kogyo Co., Ltd.)) 30 parts by weight
(D) "Samprene" LQ-T1331 (polyurethane resin, manufactured by Sanyo Chemical Industries, Ltd.) 35 parts by weight
[Solvent component]
(1) 50 parts by weight of dimethylformamide
(2) Ethyl cellosolve 25 parts by weight
(3) Methyl isobutyl ketone 25 parts by weight
Example 4
In Example 1, except that the composition of the heat-sensitive layer coating solution was changed to the one shown below, a printing plate precursor was prepared in the same manner and evaluated in the same manner. In the following, only the silicone rubber layer was removed, and the heat-sensitive layer was removed together with the silicone rubber layer in the higher energy region.
[0142]
<Thermosensitive layer composition (solid content concentration 10% by weight)>
(A) "KAYASORB" IR-820B (infrared light absorbing dye, manufactured by Nippon Kayaku Co., Ltd.) 10 parts by weight
(B) Iron (III) acetylacetonate (manufactured by Hanai Chemicals) 20 parts by weight
(C) DM622 (epoxy methacrylate, manufactured by Nagase Kasei Kogyo Co., Ltd.)) 30 parts by weight
(D) "Samprene" LQ-T1331 (polyurethane resin, manufactured by Sanyo Chemical Industries, Ltd.) 40 parts by weight
[Solvent component]
(1) 50 parts by weight of dimethylformamide
(2) Ethyl cellosolve 25 parts by weight
(3) Methyl isobutyl ketone 25 parts by weight
Example 5
In Example 1, except that the composition of the heat sensitive layer coating liquid and the composition of the silicone rubber layer coating liquid were changed to those shown below, a printing plate precursor was prepared in the same manner and evaluated in the same manner, and 175 mJ / s ( From 350 mW) to 500 mJ / s (1000 mW), only the silicone rubber layer was removed, and the heat sensitive layer was removed together with the silicone rubber layer in the higher energy region.
[0143]
<Thermosensitive layer composition (solid content concentration 10% by weight)>
(A) SPRIT NIGROSINE SJ (Dye Specialities, INC.) 15 parts by weight
(B) "Aluminum chelate" D (Aluminum (III) monoacetylacetonate bisethylacetoacetate, manufactured by Kawaken Fine Chemical Co., Ltd.) 20 parts by weight
(C) "Sumilite resin" PR-50731 (Novolac resin, manufactured by Sumitomo Durres Co., Ltd.)) 30 parts by weight
(D) "Samprene" LQ-T1331 (polyurethane resin, manufactured by Sanyo Chemical Industries, Ltd.) 35 parts by weight
[Solvent component]
(1) 50 parts by weight of dimethylformamide
(2) Ethyl cellosolve 25 parts by weight
(3) Methyl isobutyl ketone 25 parts by weight
<Silicone rubber layer composition (solid content concentration 7% by weight)>
(1) Polydimethylsiloxane (molecular weight about 25,000, terminal hydroxyl group)
100 parts by weight
(2) 10 parts by weight of vinyltri (methylethylketoxime) silane
[Solvent component]
(1) "Isopar" E (manufactured by Exxon Chemical Co., Ltd.)
Example 6
In Example 5, a printing plate precursor was prepared in the same manner except that the composition of the heat-sensitive layer coating liquid was changed to the one shown below, and evaluated in the same manner. 125 mJ / s (250 mW) to 400 mJ / s (800 mW) In the following, only the silicone rubber layer was removed, and the heat-sensitive layer was removed together with the silicone rubber layer in the higher energy region.
[0144]
<Thermosensitive layer composition (solid content concentration 10% by weight)>
(A) "KAYASORB" IR-820B (infrared light absorbing dye, manufactured by Nippon Kayaku Co., Ltd.) 10 parts by weight
(B) Iron (III) acetylacetonate (manufactured by Hanai Chemicals) 20 parts by weight
(C) "Sumilite resin" PR-50731 (Novolac resin, manufactured by Sumitomo Durres Co., Ltd.)) 30 parts by weight
(D) "Samprene" LQ-T1331 (polyurethane resin, manufactured by Sanyo Chemical Industries, Ltd.) 40 parts by weight
[Solvent component]
(1) 50 parts by weight of dimethylformamide
(2) Ethyl cellosolve 25 parts by weight
(3) Methyl isobutyl ketone 25 parts by weight
Example 7
In Example 5, a printing plate precursor was prepared in the same manner except that the composition of the heat-sensitive layer coating liquid was changed to that shown below, and evaluated in the same manner. In the following, only the silicone rubber layer was removed, and the heat-sensitive layer was removed together with the silicone rubber layer in the higher energy region.
[0145]
<Thermosensitive layer composition (solid content concentration 10% by weight)>
(A) SPRIT NIGROSINE SJ (Dye Specialities, INC.) 15 parts by weight
(B) "Aluminum chelate" D (Aluminum (III) monoacetylacetonate bisethylacetoacetate, manufactured by Kawaken Fine Chemical Co., Ltd.) 10 parts by weight
(C) "Sumilac" PC-1 (Resol resin, manufactured by Sumitomo Durres Co., Ltd.)) 30 parts by weight
(D) "Samprene" LQ-T1331 (polyurethane resin, manufactured by Sanyo Chemical Industries, Ltd.) 45 parts by weight
[Solvent component]
(1) 50 parts by weight of dimethylformamide
(2) Ethyl cellosolve 25 parts by weight
(3) Methyl isobutyl ketone 25 parts by weight
Example 8
In Example 5, a printing plate precursor was prepared in the same manner except that the composition of the heat-sensitive layer coating solution was changed to the one shown below, and evaluated in the same manner. In the following, only the silicone rubber layer was removed, and the heat-sensitive layer was removed together with the silicone rubber layer in the higher energy region.
[0146]
<Thermosensitive layer composition (solid content concentration 10% by weight)>
(A) SPRIT NIGROSINE SJ (Dye Specialities, INC.) 15 parts by weight
(B) "Aluminum chelate" D (Aluminum (III) monoacetylacetonate bisethylacetoacetate, manufactured by Kawaken Fine Chemical Co., Ltd.) 20 parts by weight
(C) "Sumilac" PC-1 (Resol resin, manufactured by Sumitomo Durres Co., Ltd.)) 30 parts by weight
(D) "Samprene" LQ-T1331 (polyurethane resin, manufactured by Sanyo Chemical Industries, Ltd.) 35 parts by weight
[Solvent component]
(1) 50 parts by weight of dimethylformamide
(2) Ethyl cellosolve 25 parts by weight
(3) Methyl isobutyl ketone 25 parts by weight
Comparative Example 3
In Example 5, a printing plate precursor was prepared in the same manner except that the composition of the heat-sensitive layer coating liquid was changed to the one shown below, and evaluated in the same manner. When the silicone rubber layer finally reached 475 mJ / s (950 mW) or more, Only a plate with low sensitivity to be removed was obtained.
[0147]
<Thermosensitive layer composition (solid content concentration 10% by weight)>
(A) SPRIT NIGROSINE SJ (Dye Specialities, INC.) 15 parts by weight
(C) "Sumilac" PC-1 (Resol resin, manufactured by Sumitomo Durres Co., Ltd.)) 30 parts by weight
(D) “Samprene” LQ-T1331 (polyurethane resin, manufactured by Sanyo Chemical Industries, Ltd.) 55 parts by weight
[Solvent component]
(1) 50 parts by weight of dimethylformamide
(2) Ethyl cellosolve 25 parts by weight
(3) Methyl isobutyl ketone 25 parts by weight
Example 9
In Example 5, a printing plate precursor was prepared in the same manner except that the composition of the heat-sensitive layer coating solution was changed to the one shown below, and evaluated in the same manner. In the following, only the silicone rubber layer was removed, and the heat-sensitive layer was removed together with the silicone rubber layer in the higher energy region.
[0148]
<Thermosensitive layer composition (solid content concentration 10% by weight)>
(A) SPRIT NIGROSINE SJ (Dye Specialities, INC.) 15 parts by weight
(B) "Narsem" Ti (manufactured by Nippon Chemical Industry Co., Ltd.) 20 parts by weight
(C) "Lipoxy" VR-90 (epoxy acrylate, Showa Polymer Co., Ltd.) 30 parts by weight
(D) "Samprene" LQ-T1331 (polyurethane resin, manufactured by Sanyo Chemical Industries, Ltd.) 35 parts by weight
[Solvent component]
(1) 50 parts by weight of dimethylformamide
(2) Ethyl cellosolve 25 parts by weight
(3) Methyl isobutyl ketone 25 parts by weight
Example 10
In Example 5, except that the composition of the heat-sensitive layer coating liquid and the composition of the silicone rubber layer coating liquid were changed to those shown below, a printing plate precursor was prepared in the same manner and evaluated in the same manner, and 175 mJ / s or more Thus, a plate from which the silicone rubber layer was removed was obtained.
[0149]
<Thermosensitive layer composition (solid content concentration 10% by weight)>
(A) "KAYASORB" IR-820B (infrared light absorbing dye, manufactured by Nippon Kayaku Co., Ltd.) 10 parts by weight
(B) "Narsem" Ti (manufactured by Nippon Chemical Industry Co., Ltd.) 10 parts by weight
(C) "Sumilite resin" PR-50731 (Novolac resin, manufactured by Sumitomo Durres Co., Ltd.)) 50 parts by weight
(D) “Samprene” LQ-T1331 (polyurethane resin, manufactured by Sanyo Chemical Industries, Ltd.) 30 parts by weight
[Solvent component]
(1) 10 parts by weight of dimethylformamide
(2) Tetrahydrofuran 90 parts by weight
<Silicone rubber layer composition (solid content concentration 7% by weight)>
(1) Vinyl group-containing polysiloxane 100 parts by weight
(2) Hydrogen polysiloxane 5 parts by weight
(3) Polymerization inhibitor 1 part by weight
(4) 2 parts by weight of catalyst
[Solvent component]
(1) "Isopar" E (manufactured by Exxon Chemical Co., Ltd.)
Example 11
In Example 10, a printing plate precursor was prepared in the same manner except that the heat-sensitive layer composition was applied with a bar coater and then dried at 130 ° C. for 1 minute. When evaluated in the same manner, silicone at 150 mJ / s or more was obtained. A plate from which the rubber layer was removed was obtained.
[0150]
Example 12
A solution having the following composition was applied on a degreased aluminum plate having a thickness of 0.24 mm, dried at 200 ° C. for 2 minutes, and 3 g / m.²The heat insulation layer was provided.
[0151]
<Insulation layer composition (solid content concentration 16.7 wt%)>
(1) Epoxy / phenol resin “Cancoat” 90T-25-3094 (manufactured by Kansai Paint Co., Ltd.) 15 parts by weight
(2) 2 parts by weight of “White” UL7E265 (manufactured by Sumika Color Co., Ltd., titanium oxide)
[Solvent component]
(1) 85 parts by weight of dimethylformamide
Next, a heat-sensitive layer composition having the following composition was applied onto this heat insulating layer, dried at 80 ° C. for 1 minute, and a film thickness of 2 g / m.²The heat sensitive layer was provided.
[0152]
<Thermal layer composition (solid content concentration 12.5% by weight)>
(A) SPRIT NIGROSINE SJ (Dye Specialities, INC.) 5 parts by weight
(B) "Aluminum chelate" D (aluminum monoacetylacetonate bisethylacetoacetate, manufactured by Kawaken Fine Chemical Co., Ltd.) 30 parts by weight
(C) "Sumilac" PC-1 (Resol resin, manufactured by Sumitomo Dureth Co., Ltd.)) 70 parts by weight
(D) “Samprene” LQ-909L (polyurethane resin, manufactured by Sanyo Chemical Industries, Ltd.) 20 parts by weight
[Solvent component]
(1) 875 parts by weight of tetrahydrofuran
Further, a silicone rubber composition having the following composition was applied on the heat-sensitive layer with a bar coater, and then wet-heat cured at 100 ° C. for 1 minute to provide a 2.0 μm silicone rubber layer.
[0153]
<Silicone rubber layer composition (solid content concentration: 8.4 wt%)>
(1) Polydimethylsiloxane (molecular weight about 35,000, terminal hydroxyl group)
100 parts by weight
(2) 9 parts by weight of vinyltris (methylethylketoxime) silane
(3) Dibutyltin diacetate 0.5 parts by weight
[Solvent component]
(1) "Isopar E" (Exxon Chemical Co., Ltd.) 1200 parts by weight
A laminate film obtained as described above was laminated with a polypropylene film “Trephan” (manufactured by Toray Industries, Inc.) having a thickness of 8 μm using a calendar roller to obtain a direct-drawing waterless lithographic printing plate precursor. .
[0154]
Thereafter, laser irradiation was performed in the same manner as in Example 1, and development was performed in the same manner. At this time, “PP-F” manufactured by Toray Industries, Inc. was used as the pretreatment liquid, water was used as the developer, and “PA-F” manufactured by Toray Industries, Inc. was used as the post-processing liquid.
[0155]
As a result, a positive waterless lithographic printing plate in which only the portion irradiated with the laser beam in a certain energy region remained and the silicone rubber layer was peeled off in the other portions was obtained.
[0156]
Furthermore, the obtained printing plate is attached to a printing machine HAMADA RS46L (made by Hamada Printing Machinery Co., Ltd.), and it is fine using waterless lithographic ink (Dryo Color NSI Ai Dainippon Ink & Chemicals Co., Ltd.). As a result of examining the minimum value (mJ / sec) of the laser output that was able to reproduce the image on the printed matter after printing on paper, it was 250 mJ / sec.
[0157]
Comparative Example 4
In Example 12, a printing plate precursor was prepared in the same manner except that (a) SPRIT NIGROSINE SJ, which is a light-to-heat conversion substance in the heat-sensitive layer, was removed and evaluated in the same manner. As a result, the silicone rubber layer peeled over the entire plate surface. I was only able to get a new version.
[0158]
Comparative Example 5
In Example 12, a printing plate precursor was prepared in the same manner except that (b) “aluminum chelate” D, which is a metal chelate compound in the heat-sensitive layer, was removed and evaluated in the same manner. Only a plate that was peeled over was obtained.
[0159]
Example 13
A solution having the following composition was applied on a degreased aluminum plate having a thickness of 0.24 mm, dried at 200 ° C. for 2 minutes, and 3 g / m.²The heat insulation layer was provided.
[0160]
<Insulation layer composition (solid content concentration 17.1 wt%)>
(1) 100 parts by weight of polyurethane resin “Milactolan” P22S (manufactured by Nippon Milactolan Co., Ltd.)
(2) Blocked isocyanate “Takenate B830” (manufactured by Takeda Pharmaceutical Co., Ltd.) 20 parts by weight
(3) Epoxy / phenol / urea resin “SJ9372” (manufactured by Kansai Paint Co., Ltd.) 8 parts by weight
(4) 0.5 parts by weight of dibutyltin diacetate
(5) "FINEX" 25 (white pigment, manufactured by Sakai Chemical Co., Ltd.) 10 parts by weight
(6) "KET-YELLOW" 402 (yellow pigment, manufactured by Dainippon Ink & Chemicals, Inc.) 10 parts by weight
[Solvent component]
(1) 720 parts by weight of dimethylformamide
On this heat insulation layer, a heat sensitive layer composition having the following composition was applied, dried at 80 ° C. for 1 minute, and a film thickness of 3 g / m.²The heat sensitive layer was provided.
[0161]
<Thermosensitive layer composition (solid content concentration 10% by weight)>
(A) Carbon black dispersed rosin modified maleic resin 15 parts by weight
(Inner carbon black 10 parts by weight)
(B) Iron (III) acetylacetonate (manufactured by Hanai Chemicals) 10 parts by weight
(C) “Sumilite Resin” PR-50731 (Novolac resin, manufactured by Sumitomo Durres Co., Ltd.)) 20 parts by weight
(D) "Epoxy ester" 3000M (hydroxyl group-containing acrylate, manufactured by Kyoeisha Chemical Co., Ltd.) 20 parts by weight
(E) “Samprene” LQ-T1331 (polyurethane resin, manufactured by Sanyo Chemical Industries, Ltd.) 40 parts by weight
(F) “TSL” 8370 (silyl group-containing acrylate, manufactured by Toshiba Silicones Co., Ltd.) 5 parts by weight
[Solvent component]
(1) 220 parts by weight of N, N-dimethylformamide
(2) 770 parts by weight of tetrahydrofuran
On the heat sensitive layer, the following silicone rubber layer composition was applied using a bar coater, and the printing plate precursor was completely the same as in Example 12 except that the dry film thickness was 2.0 μm and the drying conditions were 120 ° C. × 1 minute. Was prepared and evaluated, and a positive waterless lithographic printing plate was obtained with a laser output of 280 mJ / sec or more.
[0162]
<Silicone rubber layer composition (solid content concentration: 9.4 wt%)>
(1) α, ω-divinylpolydimethylsiloxane (degree of polymerization 770) 100 parts by weight
(2) HMS-501 (manufactured by Chisso Corporation, both-end methyl (methylhydrogensiloxane) (dimethylsiloxane) copolymer, SiH group number / molecular weight = 0.69 mol / g) 4 parts by weight
(3) 0.02 parts by weight of olefin coordinated platinum
(4) "BY24-808" (Dow Corning Silicone Co., Ltd. reaction inhibitor) 0.3 parts by weight
[Solvent component]
(1) "Isopar" E (Esso Chemical Co., Ltd.) 1000 parts by weight
Example 14
The heat sensitive layer in Example 13 was changed to the following, and the dry film thickness was 2.5 g / m.²A printing plate precursor was prepared in the same manner as in Example 13 except that the drying conditions were 150 ° C. × 2 minutes, and the same evaluation was made. A negative-type waterless lithographic printing plate specifically removed was obtained.
[0163]
Furthermore, the thickness of the heat-sensitive layer in the solid image area at a laser output of 200 mJ / sec was measured using the plate after plate making, and 2.3 g / m.²It was found that the residual rate was 92%.
[0164]
<Thermosensitive layer composition (solid content concentration 28% by weight)>
(A) "KAYASORB" IR-820B (infrared absorbing dye, manufactured by Nippon Kayaku Co., Ltd.) 10 parts by weight
(B) “Narsem” Ti (manufactured by Nippon Chemical Industry Co., Ltd.) 15 parts by weight
(C) Pentaoxypropylenediamine / glycidyl methacrylate / methyl glycidyl ether = 1/3/1 mol ratio addition reaction product 15 parts by weight
(D) m-xylylenediamine / glycidyl methacrylate / methyl glycidyl ether = 1/2/2 mol ratio addition reaction product 15 parts by weight
(E) m-xylylenediamine / glycidyl methacrylate / 3-glycidoxypropyltrimethoxysilane = 1/3/1 mol ratio addition reaction product
3 parts by weight
(F) “Denacol” EX-411 (pentaerythritol polyglycidyl ether, manufactured by Nagase Chemical Industries, Ltd.) 5 parts by weight
(G) “Samprene” T-1331 (polyurethane resin, Sanyo Chemical Industries, Ltd., glass transition temperature Tg: −37 ° C.) 30 parts by weight
(H) 0.5 parts by weight of maleic acid
(I) "Perhexa" 3M (organic peroxide, manufactured by NOF Corporation) 5 parts by weight
[Solvent component]
(1) Tetrahydrofuran: 200 parts by weight
(2) Dimethylformamide: 50 parts by weight
The initial elastic modulus of the heat sensitive layer is 20 kgf / mm.²Met.
[0165]
Example 15
The heat-sensitive layer in Example 14 was changed to the following, and the dry film thickness was 2.5 g / m.²And then dried at 80 ° C. for 1 minute. Then, using "Idle Fin" 2000 (Iwasaki Electric Co., Ltd., metal halide lamp), 11 mW / cm over the entire surface of the heat sensitive layer in the air.²For 120 seconds.
[0166]
Thereafter, the same silicone rubber layer as in Example 14 was applied to prepare a waterless lithographic printing plate precursor. As a result of evaluation in the same manner as in Example 14, a negative waterless lithographic printing plate was obtained with a laser output of 130 mJ / sec or more.
[0167]
Using the plate after plate making, the thickness of the heat-sensitive layer in the solid image portion at a laser output of 200 mJ / sec was measured to be 2.25 g / m.²It was found that the residual rate was 90%.
[0168]
The initial elastic modulus of the heat sensitive layer is 19 kgf / mm.²Met.
[0169]
<Thermosensitive layer composition (solid content concentration 28% by weight)>
(A) "KAYASORB" IR-820B (infrared absorbing dye, manufactured by Nippon Kayaku Co., Ltd.) 10 parts by weight
(B) “Narsem” Ti (manufactured by Nippon Chemical Industry Co., Ltd.) 15 parts by weight
(C) Pentaoxypropylenediamine / glycidyl methacrylate / methyl glycidyl ether = 1/3/1 mol ratio addition reaction product 15 parts by weight
(D) m-xylylenediamine / glycidyl methacrylate / methyl glycidyl ether = 1/2/2 mol ratio addition reaction product 15 parts by weight
(E) m-xylylenediamine / glycidyl methacrylate / 3-glycidoxypropyltrimethoxysilane = 1/3/1 mol ratio addition reaction product
3 parts by weight
(F) “Denacol” EX-411 (pentaerythritol polyglycidyl ether, manufactured by Nagase Chemical Industries, Ltd.) 5 parts by weight
(G) “Samprene” T-1331 (polyurethane resin, Sanyo Chemical Industries, Ltd., glass transition temperature Tg: −37 ° C.) 30 parts by weight
(H) 0.5 parts by weight of maleic acid
(I) "IRGACURE" 651 (Ciba Geigy benzyl dimethyl ketal) 2 parts by weight
(J) “Michler's ketone” (4,4′-dimethylamino benzophenone manufactured by Hodogaya Chemical Co., Ltd.) 5 parts by weight
[Solvent component]
(1) Tetrahydrofuran 200 parts by weight
(2) 50 parts by weight of dimethylformamide
Example 16
The same heat-sensitive layer and the same silicone rubber layer as in Example 12 were provided on an 80 μm thick polyethylene terephthalate film “Lumirror” (manufactured by Toray Industries, Inc.) subjected to EC treatment. Further, the same cover film as in Example 12 was laminated to obtain a direct drawing type waterless planographic printing plate precursor.
[0170]
  ObtainedDirect drawing type waterless planographic printing plate precursorWas irradiated with a laser in the same manner as in Example 12 and the cover film was peeled off, then immersed in a mixed solution of water / diethylene glycol mono-2-ethylhexyl ether: 90/10 (parts by weight / parts by weight) for 1 minute, When the developing plate (made by 3M Co., Ltd.) immersed in purified water was rubbed, only the silicone rubber layer of the laser irradiated part remained selectively at a laser output of 280 mJ / second or more. A positive waterless lithographic printing plate from which the silicone rubber layer was detached was obtained.
[0171]
  Comparative Example 6
  A grained aluminum plate was surface treated with a 5% aqueous solution of zirconium fluoride heated to 80 ° C. for 2 minutes and dried to obtain a substrate. On this substrate, the thermosensitive composition of Example 1 was applied so as to have a dry film thickness of 2.0 g / m 2 and dried at 60 ° C. for 1 minute to prepare a direct-drawing printing plate precursor. Laser irradiation was carried out in the same manner as in Example 12, and development was carried out with a diluted PS plate developer (a negative type developer stock solution manufactured by Fuji Photo Film Co., Ltd. diluted 10-fold with pure water). A negative water-type lithographic printing plate with an output of 100 mJ / sec or more, in which only the laser irradiation part remained selectively, was obtained.
[0172]
  Example17
  (C) “Sumilac” PC-1 (resole resin), which is a hydroxyl group-containing compound in Example 12, (c) “Marcalinker” PHM-C (poly (p-hydroxystyrene), manufactured by Maruzen Petrochemical Co., Ltd.) : A printing plate precursor was prepared in the same manner as in Example 12 except that the amount was changed to 70 parts by weight, and evaluated in the same manner.
[0173]
As a result, a positive lithographic printing plate in which only the laser irradiated portion remained selectively at a laser output of 280 mJ / second or more was obtained.
[0174]
  Example18
  On the heat insulating layer obtained in Example 1, a heat sensitive layer composition having the following composition was applied, dried at 150 ° C. for 1 minute, and a film thickness of 2 g / m.²The heat sensitive layer was provided.
[0175]
<Thermosensitive layer composition (solid content concentration 11.6 wt%)>
(A) “SONH BLACK” (Waterbase) (Mitsubishi Chemical Corporation, carbon black water dispersion paste) 7 parts by weight
(B) 10 parts by weight of iron (III) acetylacetonate (manufactured by Hanai Chemicals)
(C) "Gohsenol" KL-05 (polyvinyl alcohol, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) 8 parts by weight
(D) Polymer of Synthesis Example 1 15 parts by weight
(E) “TSL” 8350 (γ-glycidoxypropyltrimethoxysilane, manufactured by Toshiba Silicones Co., Ltd.) 2 parts by weight
[Solvent component]
(1) 280 parts by weight of purified water
(2) 40 parts by weight of ethanol
On this heat-sensitive layer, a silicone rubber composition having the following composition was applied with a bar coater, and then wet-heat cured at 110 ° C. for 1 minute to provide a 2.0 μm silicone rubber layer. Co., Ltd., polypropylene film 12 μm) was laminated to obtain a direct-drawing waterless lithographic printing plate precursor.
[0176]
<Silicone rubber layer composition (solid content concentration: 8.4 wt%)>
(1) 100 parts by weight of polydimethylsiloxane (molecular weight about 35,000, terminal hydroxyl group)
(2) 10 parts by weight of ethyltriacetoxysilane
(3) Dibutyltin diacetate 0.3 parts by weight
[Solvent component]
(1) "Isopar G" (Exxon Chemical Co., Ltd.) 1200 parts by weight
The plate after laser irradiation was peeled off the cover film, then immersed in a mixed solution of water / diethylene glycol mono-2-ethylhexyl ether: 95/5 (parts by weight / parts by weight) for 1 minute, and further immersed in purified water. When the plate surface was rubbed using a pad (manufactured by 3M Co., Ltd.), a negative waterless lithographic printing plate from which the silicone rubber layer of the laser irradiated part was removed at a laser output of 110 mJ / second or more was obtained.
[0177]
Further, when the thickness of the heat-sensitive layer in the solid image area at a laser output of 200 mJ / sec was measured using the plate after plate making, 1.9 g / m was measured.²The residual rate was 95%.
[0178]
  Example19
  Example18A continuous line was written on the printing plate precursor obtained in (1) above using a semiconductor-excited YAG laser having a wavelength of 1064 nm and a beam diameter of 100 μm (1 / e 2). Recording energy is 0.75 J / cm²It was.
[0179]
  Then the example18When developed in the same manner as above, a negative waterless lithographic printing plate from which only the silicone rubber layer irradiated with the laser beam was removed was obtained.
[0180]
When the film thickness of the heat sensitive layer of the image area was measured, 1.75 g / m²The residual rate was 87.5%.
[0181]
  Example20
  A grained aluminum plate was surface treated with a 5% aqueous solution of zirconium fluoride heated to 80 ° C. for 2 minutes and dried to obtain a substrate. The following thermosensitive composition was applied onto this substrate so as to have a dry film thickness of 5.0 g / m 2 and dried at 150 ° C. for 1 minute.
[0182]
<Thermosensitive layer composition (solid content concentration 54 wt%)>
(A) "KAYASORB" IR-820B (infrared absorbing dye, manufactured by Nippon Kayaku Co., Ltd.) 5 parts by weight
(B) "Aluminum chelate" A (aluminumTris20 parts by weight of acetylacetonate, manufactured by Kawaken Fine Chemical Co., Ltd.
(C) "Epoxy ester" 80 MFA (epoxy acrylate, manufactured by Kyoeisha Chemical Co., Ltd.)) 40 parts by weight
(D) 5 parts by weight of “KAYAMER” PM-21 (phosphorus-containing monomer, manufactured by Nippon Kayaku Co., Ltd.)
(E) "Samprene" LQ-T1331 (polyurethane resin, manufactured by Sanyo Chemical Industries, Ltd.) 40 parts by weight
(F) Tolylene diisocyanate 5 parts by weight
(G) 2 parts by weight of acetic acid
[Solvent component]
(1) 50 parts by weight of dimethylformamide
(2) Ethyl cellosolve 25 parts by weight
(3) Methyl isobutyl ketone 25 parts by weight
Example on heat sensitive layer18The same silicone rubber layer was applied as above to obtain a direct-drawing waterless lithographic printing plate precursor. The obtained original plate is an example.18Laser irradiation was performed in the same manner as described above, and development was performed in the same manner. As a result, a negative waterless lithographic printing plate was obtained with a laser output of 110 mJ / sec or more.
[0183]
Furthermore, when the thickness of the heat-sensitive layer in the solid image portion at a laser output of 200 mJ / sec was measured using the plate after plate making, it was 4.9 g / m.²The residual rate was 98%.
[0184]
  Example21
  A solution having the following composition was applied on a degreased aluminum plate having a thickness of 0.24 mm, dried at 200 ° C. for 2 minutes, and 3 g / m.²The heat insulation layer was provided.
[0185]
<Insulation layer composition (solid content concentration 16.7 wt%)>
(1) Epoxy / phenol resin “Cancoat” 90T-25-3094 (manufactured by Kansai Paint Co., Ltd.) 15 parts by weight
(2) "KAYASORB" IR-820B (infrared absorbing dye, manufactured by Nippon Kayaku Co., Ltd.) 0.16 parts by weight
[Solvent component]
(1) 85 parts by weight of dimethylformamide
On this heat insulation layer, a heat sensitive layer composition having the following composition was applied, dried at 130 ° C. for 1 minute, and a film thickness of 1 g / m.²The heat sensitive layer was provided.
[0186]
<Thermosensitive layer composition (solid content concentration 10% by weight)>
(A) "KAYASORB" IR-820B (infrared light absorbing dye, manufactured by Nippon Kayaku Co., Ltd.) 10 parts by weight
(B) "Narsem" Ti (manufactured by Nippon Chemical Industry Co., Ltd.) 10 parts by weight
(C) "Sumilite resin" PR-50731 (Novolac resin, manufactured by Sumitomo Durres Co., Ltd.)) 40 parts by weight
(D) “Samprene” LQ-T1331 (polyurethane resin, manufactured by Sanyo Chemical Industries, Ltd.) 30 parts by weight
(E) N, N, N′-tri (2-hydroxy-3-methacryloxypropyl) -N ′-(2-hydroxy-3-trimethoxysilylpropyloxypropyl) polyoxypropylenediamine 10 parts by weight
[Solvent component]
(1) 100 parts by weight of dimethylformamide
(2) 700 parts by weight of tetrahydrofuran
(3) Isopropyl alcohol 100 parts by weight
The same silicone rubber layer as in Example 13 was coated on the heat-sensitive layer to obtain a direct-drawing waterless lithographic printing plate precursor. The obtained original plate was irradiated with laser in the same manner as in Example 13 and developed in the same manner. As a result, a negative waterless lithographic printing plate was obtained with a laser output of 130 mJ / sec or more.
[0187]
  Example22
  Example21The following silicone rubber layer composition was applied onto the heat-sensitive layer using a bar coater, and the dry film thickness was 2.0 μm, and the drying conditions were 120 ° C. × 1 minute.21When a printing plate precursor was prepared and evaluated in the same manner as described above, a negative waterless planographic printing plate was obtained with a laser output of 140 mJ / second or more.
[0188]
<Silicone rubber layer composition (solid content concentration: 9.4 wt%)>
(1) α, ω-divinylpolydimethylsiloxane (degree of polymerization 770) 100 parts by weight
(2) HMS-501 (manufactured by Chisso Corporation, both-end methyl (methylhydrogensiloxane) (dimethylsiloxane) copolymer, SiH group number / molecular weight = 0.69 mol / g) 4 parts by weight
(3) 0.02 parts by weight of olefin coordinated platinum
(4) "BY24-808" (Dow Corning Silicone Co., Ltd. reaction inhibitor) 0.3 parts by weight
(5) 4 parts by weight of vinyltri (methylethylketoxime) silane
[Solvent component]
(1) "Isopar" E (Esso Chemical Co., Ltd.) 1000 parts by weight
The result of a present Example is shown to Tables 1-4.
[0189]
[Table 1]

[Table 2]

[Table 3]

[Table 4]

[0190]
【The invention's effect】
  The present inventionDirect drawing type waterless planographic printing plate precursorIn the above, the heat-sensitive layer contains (a) a photothermal conversion substance and (b) a metal chelate compound, so that a direct-drawing waterless lithographic plate having good image reproducibility can be obtained without requiring a complicated process after laser light irradiation. can get.

Claims (10)

A direct-drawing waterless lithographic printing plate precursor having at least a heat-sensitive layer and a silicone rubber layer on a substrate, the heat-sensitive layer comprising (a) a photothermal conversion substance, (b) acetylacetonate, 2, 2, 6, 6 Tetramethyl-3,5-heptanedionate, benzoylacetonate, 1,3-diphenyl-1,3-propanedionate, methyl acetoacetate, ethyl acetoacetate, methacryloxyethyl acetoacetate, allyl acetoacetate, hexanedio A direct-drawing type characterized by containing a metal chelate compound having a ligand selected from nate, heptanedionate, tetramethylheptanedionate and benzoyl acetate , (c) a hydroxyl group-containing compound and (d) a binder polymer Waterless lithographic printing plate precursor. The direct-drawing waterless lithographic printing plate precursor according to claim 1, wherein the heat-sensitive layer has a crosslinked structure . Claim 2 directly imageable waterless planographic printing plate precursor of, wherein the cross-linked structure is that formed by (b) a metal chelate compound and (c) hydroxyl group-containing compound in the heat-sensitive layer. A direct-drawing waterless lithographic printing plate precursor having at least a heat-sensitive layer and a silicone rubber layer on a substrate, wherein the heat-sensitive layer comprises (a) a photothermal conversion substance, (b) acetylacetonate, 2, 2, 6, 6 Tetramethyl-3,5-heptanedionate, benzoylacetonate, 1,3-diphenyl-1,3-propanedionate, methyl acetoacetate, ethyl acetoacetate, methacryloxyethyl acetoacetate, allyl acetoacetate, hexanedio A metal chelate compound having a ligand selected from nate, heptanedionate, tetramethylheptanedionate and benzoyl acetate , and (c) a hydroxyl group-containing compound , and (b) a metal chelate compound and (c) a hydroxyl group by having a crosslinked structure formed by the reaction of a compound The directly imageable waterless lithographic printing plate precursor to a butterfly. (C) according to claim 1 or 4 directly imageable waterless planographic printing plate precursor, wherein the hydroxyl group-containing compound is a phenolic hydroxyl group-containing compound. The central metal of the metal chelate compound described in (b) is a metal selected from the group consisting of Al, Ti, Mn, Fe, Co, Ni, Cu, Zn, Ge, and In. Directly drawn waterless lithographic printing plate precursor. The metal chelate compound described in (b) is iron (III) acetylacetonate, titanium di-n-butoxide (bis-2,4-pentanedionate), aluminum monoacetylacetonate bisethylacetoacetate, aluminum trisacetylacetonate. The direct-drawing waterless lithographic printing plate precursor according to any one of claims 1 to 6, which is selected . The process according to claim 7 or after exposure of the directly imageable waterless planographic printing plate precursor according, water or surfactant can be developed with a liquid containing a directly imageable waterless planographic printing plate, wherein . The developed direct-drawing waterless planographic printing plate according to claim 8, wherein the layer exposed by peeling of the silicone rubber layer is dyed using a dyeing solution. Plate manufacturing method. The method for producing a direct-drawing waterless lithographic printing plate, wherein the exposed layer according to claim 9 is a heat-sensitive layer.