JP4030241B2 - Silver halide photographic light-sensitive material and planographic printing plate - Google Patents

Description

【０１１６】
本発明に係わる塗布層中には界面活性剤、無機顔料、有機顔料、ＰＨ調節剤、ＰＨ緩衝剤、その他の硬化剤及びアルコール等の有機溶剤等を必要に応じ適宜含ませる事が出来る。界面活性剤は塗布剤の塗布性を良くする為にフッ素系もしくはアニオン系界面活性剤を添加する事が好ましい。無機顔料としては特にシリカ微粒子として粒子径１〜５ミクロン程度のシリカ微粒子を添加した場合にシート自体の滑り性が向上するため給紙特性や排紙特性が向上し、さらに印刷インキの乾燥性が大幅に向上するため特に好ましい。これ以外にも、コロイダルシリカや気相法シリカ、合成シリカなどの各種シリカ微粒子や酸化チタン、アルミナゾル、ジルコニアゾル等の各種無機微粒子或いは、ポリマービーズ等の有機顔料等を添加することも好ましく行われる。
【０１１７】
本発明に係る塗布方法は、一般に良く知られた塗布方法、例えばディップコート法、エアーナイフコート法、カーテンコート法、グラビアコート法等により塗布する事が出来る。かくして塗布された液は続いて乾燥工程において乾燥されるがその条件は室温〜１３０℃で２秒〜３分間であるが、この範囲で温度及び時間を適宜決める事が出来る。本発明の特徴の一つは、上記の塗布層を形成する際に得に加熱処理がいらないことが特徴であり、塗布後の乾燥において溶媒を乾燥させるために加熱を行うものであって、単に送風のみで乾燥が可能であるような場合には（薄層コーテイング等）加熱を必要としない場合もある。
【０１１８】
塗布層の塗布に際しては、塗布に先立ち、印刷用シート基材表面をコロナ処理等の方法で活性化しておくことが望ましい。塗布面質は均一であることが好ましく、そのために下引き層塗液に界面活性剤を添加し、また印刷用シート基材表面に直流電圧を印可して帯電ムラを少なくしておくことが好ましい。
【０１１９】
本発明に係る印刷用シートは、その少なくとも片面上に、上記塗布層を固形分（乾燥塗布量）で好ましくは０．０５〜５ｇ／ｍ²の範囲で設けたことを特徴とするものである。塗布層の更に好ましい範囲は０．５〜２ｇ／ｍ²である。溶剤バリヤー性に関しては該塗布層の厚みを増加する程向上するが、インキに対する接着性に関しては上記の下限程度の厚みでも十分にその機能を発揮できる。
【０１２０】
【実施例】
以下実施例により本発明をさらに詳しく説明するが、効果はもとより本発明はこれら実施例に限定されるものではない。実施例中の部は重量部を示す。
実施例１
厚み１００μmのポリエチレンテレフタレートフィルム支持体上に、下記組成の単一層からなる下引き層を設けた。下引き層の乾燥膜厚は０．２μmになるように塗布乾燥した。
【０１２１】
＜下引き層Ａ−１＞
水分散型ポリウレタンエマルジョン（パーマリンUA-200、三洋化成工業（株）製）
【０１２２】
＜下引き層Ａ−２＞
水分散型ポリウレタンエマルジョン（パーマリンUA-200、三洋化成工業（株）製）と、エポキシ化合物（デナコールEX-521、長瀬産業（株）製）を上記ポリウレタンに対して、固形分で１０重量％含有する。
【０１２３】
＜下引き層Ａ−３＞
水分散型ポリウレタンエマルジョン（パーマリンUA-200、三洋化成工業（株）製）と、ブロックイソシアネート化合物（エラストロンBN-44、第一工業製薬（株）製）を上記ポリウレタンに対して、固形分で１０重量％含有する。
【０１２４】
＜下引き層Ａ−４＞
水分散型ポリウレタンエマルジョン（パーマリンUA-200、三洋化成工業（株）製）と、ヘキサメチロールメラミンを上記ポリウレタンに対して、固形分で１０重量％含有する。
【０１２５】
＜下引き層Ａ−５＞
水分散型ポリウレタンエマルジョン（パーマリンUA-200、三洋化成工業（株）製）と、自己乳化性イソシアネート化合物（デュラネートWB40-80、旭化成工業製薬（株）製）を上記ポリウレタンに対して、固形分で１０重量％含有する。
【０１２６】
＜下引き層Ａ−６＞
水分散型ポリウレタンエマルジョン（パーマリンUA-200、三洋化成工業（株）製）と、自己乳化性イソシアネート化合物（デュラネートWX-1741、旭化成工業製薬（株）製）を上記ポリウレタンに対して、固形分で１０重量％含有する。
【０１２７】
上記の６種類の下引き層の上に、下記組成のハロゲン化銀乳剤層とオーバーコート層を塗布し、乾燥してハロゲン化銀写真感光材料を作製した。
【０１２８】
＜ハロゲン化銀乳剤層＞
コントロールダブルジェットにより、イリジウムを含有する平均粒径０．２５ミクロンの単分散塩臭化銀乳剤（塩化銀７０モル％）を調整した。フローキュレーション法により脱塩、水洗、再溶解し、６−メチル−４−ヒドロキシ−１、３、３ａ、７−テトラザインデンを２ｇ／ｍ²に成るように加え、増感色素としてアンヒドロ−５，５−ジクロロ−９−エチル−３，３’−ジ−（３−スルホプロピル）オキサカルボシアニンヒドロキシドピリジニウムを０．２ｇ／ｍ²に成るように添加した。こうして得られた乳剤にゼラチンを２．５ｇ／ｍ²、ポリエチレングリコール０．１ｇ／ｍ²、界面活性剤を添加し、次いで硬膜剤として２−ヒドロキシ−４，６−ジクロロ−１，３，５−トリアジンナトリウム塩を全ゼラチン量に対して１重量％になるよう添加した。銀量が３．５ｇ／ｍ²になるように塗布した。
【０１２９】
＜オーバーコート層＞
ゼラチン（１ｇ／ｍ²）、界面活性剤、及び２−ヒドロキシ−４，６−ジクロロ−１，３，５−トリアジンナトリウム塩（対ゼラチン３重量％）からなる。
【０１３０】
上記のようにして作製されたそれぞれのハロゲン化銀写真感光材料を４０℃で７日間加温した。かくして得られた各サンプルについて、アルカリ液での接着性を評価した。
【０１３１】
＜アルカリ液での接着試験＞
塗布面にカッターナイフを使用して１ｃｍ角の格子状の傷を入れ、３規定水酸化ナトリウム水溶液中に１０分間浸漬した後、水を含ませた脱脂綿にて表面を強く擦ることで支持体との接着性を評価した。膜面を擦ることでハロゲン化銀乳剤層の剥離が生じた場合を×とし、一部剥離した場合は△とし、剥離が全く認められなかった場合を○とした。それぞれの評価結果を表１に示す。
【０１３２】
【表１】

【０１３３】
上記結果から分かるように、本発明の自己乳化性イソシアネート化合物を用いた下引き層Ａ−５及びＡ−６は、単一層であるにもかかわらず、アルカリ液中で優れた接着性を示す。
【０１３４】
実施例２
実施例１の下引き層の水分散型ポリウレタンエマルジョンを、異なる種類の水分散型ポリウレタンエマルジョン（パーマリンUA-310、三洋化成工業（株）製）に代える以外、実施例１と全く同様にして、下引き層Ｂ−１〜Ｂ−６を作製し、ポリエチレンテレフタレートフィルム支持体上に塗布し乾燥した。次いで、実施例１と同様にしてハロゲン化銀乳剤層とオーバーコート層を塗布して、ハロゲン化銀感光材料を作製した。実施例１と同様にしてアルカリ液での接着性を試験した。その結果、比較の下引き層Ｂ−１〜Ｂ−４を用いたサンプルは、膜剥がれがあったが、本発明の下引き層Ｂ−５及びＢ−６を用いたサンプルは、全く膜剥がれが無かった。
【０１３５】
実施例３
実施例１の下引き層の水分散型ポリウレタンエマルジョンを、塩化ビニリデンラテックス（旭化成工業（株）製のＬ５３６Ｂ、塩化ビニリデン比率９０％以上、水酸基変性ラテックス）に代える以外、実施例１と全く同様にして、下引き層Ｃ−１〜Ｃ−６を作製し、ポリエチレンテレフタレートフィルム支持体上に塗布し乾燥した。次いで、実施例１と同様にしてハロゲン化銀乳剤層とオーバーコート層を塗布して、ハロゲン化銀感光材料を作製した。実施例１と同様にしてアルカリ液での接着性を試験した。その結果、比較の下引き層Ｃ−１〜Ｃ−４を用いたサンプルは、膜剥がれがあったが、本発明の下引き層Ｃ−５及びＣ−６を用いたサンプルは、全く膜剥がれが無かった。
【０１３６】
実施例４
次に、下引き２層構成における本発明の優位性を実証するための実施例を示す。厚み１００μmのポリエチレンテレフタレートフィルムの成膜時に、塩化ビニリデンラテックス（旭化成工業製、Ｌ５３６Ｂ、塩化ビニリデン比率９０％以上、水酸基変性ラテックス）からなる下引き第１層を乾燥厚みが０．１ミクロンになるようにインラインコートした。この下引き第１層の上に、更に下記表２に示す下引き第２層を乾燥膜厚みが０．３μmになるように塗布し、乾燥してポリエチレンテレフタレートフィルム支持体を作成した。尚、下引き第２層中に含有する化合物Ａは樹脂に対して１０重量％である。得られた支持体をさらに１２０℃または１５０℃に調節した乾燥器内で３分間熱処理した支持体も併せて作成した。
【０１３７】
次に、上記各種支持体上に実施例１のハロゲン化銀乳剤層とオーバーコート層を塗布乾燥して、ハロゲン化銀写真感光材料を作製した。これらのサンプルを４０℃で７日間加温した後、アルカリ液接着性と寸法安定性を評価した。
【０１３８】
寸法安定性については、各々のサンプルを幅３０ｃｍ長さ６０ｃｍに裁断し、２０℃２０％の温湿度下で２時間調湿を行った後密着プリンターを使用して間隔５ｃｍで１０本の細線を描いたフィルム原稿に密着させて露光を行い、現像処理を行った試料を作成し、次いで同一の温湿度下で２時間調湿を行った後、原稿との細線のずれを測定することにより評価を行った。数値は原稿の５０ｃｍ幅に対する試料に現像された相当する細線間のずれをミクロン単位で示したものである。値が小さいほど優れていることを意味する。評価結果を表２に示す。
【０１３９】
【表２】

WB-40：自己乳化性イソシアネート化合物（デュラネートWB40-80、旭化成工業製薬（株）製）
WX1741：自己乳化性イソシアネート化合物（デュラネートWX-1741、旭化成工業製薬（株）製）
エポキシ：デナコールEX-521（長瀬産業（株））
ブロックイソシアネート：エラストロンBN-44（第一工業製薬（株））
【０１４０】
上記結果より明らかなように、本発明は熱処理しなくても高い接着性を示す。これに対して、比較は、熱処理なしでは接着性は付与されず、熱処理を行ってもまだ不十分である。また、本発明は比較に比べ寸法安定性に優れている。
【０１４１】
実施例５
実施例４の下引き第１層の塩化ビニリデンラテックスを水分散型ポリウレタンエマルジョン（パーマリンUA-310、三洋化成工業（株）製）に代える以外は、実施例５を繰り返した。その結果、実施例４と同様な結果が得られた。
【０１４２】
実施例６
ポリエチレンテレフタレートフィルム表面に塩化ビニリデンラテックス（旭化成工業製、Ｌ５３６Ｂ、塩化ビニリデン比率９０％以上、水酸基変性ラテックス）を乾燥塗布厚みが０．１ミクロンになるよう塗布された下引き済みポリエステルフィルムを支持体として使用し、この上に下記の処方で示される各塗布層をこの順番で塗布したハロゲン化銀写真感光材料を作成した。
【０１４３】
（１）アンダーコート層
ゼラチン ３部
ＷＢ４０−８０ ０．０４部
水 ９７部
上記の処方に於いて、ＷＢ４０−８０とは、本発明に係わる自己乳化性イソシアネート化合物の例であり、旭化成工業（株）よりデユラネートＷＢ４０−８０ として入手されるものであり、溶剤により８０％濃度に希釈されたものである。上記アンダーコート層塗布液を湿分塗布量１０ｇ／ｍ²（乾燥膜厚約０．３μm）で塗布した。
【０１４４】
（２）ハロゲン化銀乳剤層
乳剤層の処方に於いては、コントロールダブルジェットにより、イリジウムを含有する平均粒径０．２５ミクロンの単分散塩臭化銀乳剤（塩化銀７０モル％）を調整した。フローキュレーション法により脱塩、水洗、再溶解し、６−メチル−４−ヒドロキシ−１、３、３ａ、７−テトラザインデンを２ｇ／ｍ²に成るよ うに加え、増感色素としてアンヒドロ−５，５−ジクロロ−９−エチル−３，３’−ジ−（３−スルホプロピル）オキサカルボシアニンヒドロキシドピリジニウムを０．２ｇ／ｍ²に成るように添加した。こうして得られた乳剤にゼラチンを ２．５ｇ／ｍ²、ポリエチレングリコール０．１ｇ／ｍ²に成るように添加し、次いで本発明に係わる硬膜剤として先のＷＢ４０−８０を全ゼラチン量に対して８重量％になるよう添加した。
【０１４５】
上記のアンダーコート層および乳剤層に含まれる硬膜剤として、ＷＢ４０−８０に代えてホルマリンあるいは２−ヒドロキシ−４，６−ジクロロ−１，３，５−トリアジンのナトリウム塩をそれぞれ同量添加した以外は全く同様にして比較試料１（ホルマリン）および比較試料２（２−ヒドロキシ−４，６−ジクロロ−１，３，５−トリアジンのナトリウム塩）を作成した。
【０１４６】
上記のハロゲン化銀乳剤層を塗布銀量が平米当たり４ｇになるように、アンダーコート塗布面上に塗布し、冷風を与えセットした後、３５℃あるいは７０℃に設定した送風乾燥器内で乾燥させた。得られた写真感光材料試料をキセノン感光計を使用して像露光し、通常の現像処理を行い、最高画像濃度（Ｄｍａｘ）および下地濃度（Ｄｍｉｎ）を透過濃度を測定することで求めた。さらに、乳剤塗布面にカッターナイフを使用して１ｃｍ角の碁盤目状の傷を入れ、３規定水酸化ナトリウム水溶液中に１０分間浸漬した後、水を含ませた脱脂綿にて表面を強く擦ることで支持体との接着性を評価した。膜面を擦ることで感光層の剥離が生じた場合を×とし、一部剥離した場合は△とし、剥離が全く認められなかった場合を○とした。それぞれの評価結果を表３に示した。表３の結果から分るように、７０℃での高温乾燥条件においてもＷＢ４０−８０を添加した試料についてはＤｍｉｎの増加は見られないのに対し、比較試料１および２においては明らかにＤｍｉｎが増加する結果が得られた。さらに、支持体との接着性においては比較試料はアルカリ水溶液中に於いて簡単に感光層皮膜が剥離してしまったが、本実施例で作成した試料は良好な接着性を示した。なお、本実施例において、自己乳化性イソシアネート化合物（ＷＢ４０−８０）の添加の有無による感光材料の感光特性（感度、調子等）への影響は認められず、さらに長期にわたる経時保存においても感光特性への影響は認められなかった。
【０１４７】
【表３】

【０１４８】
参考例１
ポリエチレンテレフタレートフィルム表面に塩化ビニリデンラテックス（旭化成工業製、Ｌ５０２、塩化ビニリデン比率９０％以上、カルボキシル基変性ラテックス）を乾燥塗布厚みが０．１ミクロンになるよう塗布された支持体を用意した。この上に実施例６で乳剤層として使用した本発明１の塗布液（ＷＢ４０−８０）、比較１の塗布液（ホルマリン）あるいは比較２の塗布液（２−ヒドロキシ−４，６−ジクロロ−１，３，５−トリアジンのナトリウム塩）をそれぞれ塗布して、参考試料１、比較試料３及び比較試料４の写真感光材料を作成した。本実施例ではラテックス下引き層の上に乳剤層のみを塗布した。実施例６と全く同様に評価を行い表４に示す結果を得た。実施例１とほぼ同様な結果が得られた。
【０１４９】
【表４】

【０１５０】
実施例８
ポリエチレンテレフタレートフィルム支持体上にポリウレタンエマルジョンとしてパーマリンＵＡ−２００（三洋化成工業（株）製）を使用し、自己乳化性イソシアネート化合物としてＷＸ−１７４１（旭化成工業（株）製）をポリウレタンに対し、固形分比で１０重量％になるよう添加した下引き剤を用い、乾燥膜厚０．２ミクロンになるよう塗布乾燥し下引き加工を行った。これに実施例６で作成した本発明１の乳剤塗液を同様に塗布、乾燥を行い評価を行ったところ実施例６と同様に良好な結果を得た。
【０１５１】
実施例９
ポリエチレンテレフタレートフィルム支持体上にポリウレタンエマルジョンとしてパーマリンＵＡ−１５０（三洋化成工業（株）製）を使用し、乾燥膜厚０．２ミクロンになるよう塗布乾燥し下引き加工を行った。自己乳化性イソシアネート化合物としてＷＸ−１７４１（旭化成工業（株）製）をゼラチンに対し、固形分比で１０重量％になるよう添加したアンダーコート層塗布液と実施例６で作成した本発明１の乳剤塗液をスライドビード塗布方式により同時に重層塗布し、乾燥して感光材料を作成した。実施例６と同様に現像および接着性評価を行ったところ実施例６と同様に良好な結果を得た。
【０１５２】
実施例１０
次に、銀錯塩拡散転写法を利用した平版印刷版について、本発明の優位性を実証するために下記の実施例を行った。
実施例１〜３と同様にして、下引き層Ａ−１〜Ａ−６、Ｂ−１〜Ｂ−６、及びＣ−１〜Ｃ−６が塗布乾燥されたポリエステルフィルム支持体を用意した。
【０１５３】
上記で作製された支持体上に、下記の下塗り層、ハロゲン化銀乳剤層、及び物理現像核を塗布した。
【０１５４】
＜下塗り層（ハレーション防止層）＞
ゼラチン ３５部
2-ヒドロキシ-4,6-ジクロロ-1,3,5-トリアジンナトリウム塩 ７部
水 ２００部
酸化チタン（堺化学社製ＴＲ−１） ５０部
水 １００部
マット剤：富士デヴィドソン社製サイロイド(グレード978) ７．５部
カーボンブラック分散液（固形分３０％） ８部
界面活性剤 ６部
水を加え、全量を６００部とした。
【０１５５】
上記の下塗り層（ハレーション防止層）塗布液を溶液で平米当たり６０ｇになるように塗布乾燥した。さらにこの下塗り層（ハレーション防止層）上にオルソ増感された高コントラスト塩化銀乳剤を硝酸銀に換算して平米当たり１．５ｇ（ゼラチン０．８ｇ／ｍ²）になるよう塗布、乾燥した。 ハロゲン化銀乳剤層に硬膜剤としてホルマリンを使用した。乾燥後、５０℃に調節した乾燥器内で２日間加温した後、特開平８−２１１６１４号明細書中に記載の実施例１に従い、物理現像核液を塗布し、乾燥することで平版印刷版を作成した。
【０１５６】
上記平版印刷版について、下記に示す試験方法で接着性と印刷性を評価した。＜接着試験＞
塗布面にカッターナイフを使用して１ｃｍ角の格子状の傷を入れ、３規定水酸化ナトリウム水溶液中あるいはジメチルホルムアミド（ＤＭＦ）中にそれぞれ１０分間浸漬した後、水を含ませた脱脂綿にて表面を強く擦ることで支持体との接着性を評価した。膜面を擦ることで感光層の剥離が生じた場合を×とし、一部剥離した場合は△とし、剥離が全く認められなかった場合を○とした。
【０１５７】
＜印刷試験＞
平版印刷版を像にしたがって露光した後、下記現像液に３０℃で３０秒間し、現像を行い、引き続いて下記停止液中に３０秒間（２５℃）浸漬し、スクィーズして余分な液を除き、乾燥させた。
【０１５８】
現像液

【０１５９】
停止液
水 ６００ｍｌ
クエン酸 １０ｇ
クエン酸ナトリウム ３５ｇ
コロイダルシリカ（２０％液） ５ｍｌ
エチレングリコール ５ｍｌ
水を加えて全量を１リットルとする。
【０１６０】
上記製版処理によって得られた平版印刷版を、オフセット印刷機リョービ３２００ＣＤに装着し、下記エッチング液で版面を拭いた後、下記の給湿液とインキ（大日本インキ製Ｆグロス墨ＢとＦグロス紺藍）を使用して印刷した。前記Ｆグロス紺藍は当該平版印刷版に対して印刷汚れが出やすいインキの一つである。印刷時の温度は２２℃で湿度は６０％であった。
【０１６１】
エッチング液

【０１６２】
給湿液
ｏ−燐酸 １０ｇ
硝酸ニッケル ５ｇ
亜硝酸ナトリウム ５ｇ
エチレングリコール １００ｍｌ
コロイダルシリカ（２０％液） ２８ｇ
水を加えて全量を２リットルとする。
【０１６３】
印刷性の評価は、印刷汚れの程度および耐刷力から行った。印刷汚れに関しては、全く汚れが無い場合を○とし、部分的に汚れが発生する場合を△とし、前面に汚れが発生する場合を×とした。耐刷力に関しては、２万部以上の印刷物について正常な印刷が行えた場合を○とし、５千部以下の印刷物に於いて画像欠落等が生じた場合を×とし、それらの中間を△とした。試験結果を表５に示す。
【０１６４】
【表５】

【０１６５】
上記結果から明らかなように、本発明の下引き層を用いたサンプルは、１層下引きに係わらず、優れた接着性と印刷性を示す。
【０１６６】
実施例１１
実施例４と同様に２層の下引き層を有するポリエステルフィルム支持体を作製した。これらの支持体上に実施例１０と同様に下塗り層、ハロゲン化銀乳剤層及び物理現像核層を塗布して各種平版印刷版を作製した。かくして作製した平版印刷版について、実施例１０と同様にして耐刷力を評価した。その結果を表６に示す。
【０１６７】
【表６】

【０１６８】
上記結果より、本発明は熱処理しなくても高い耐刷力を示すのに対して、比較は、熱処理なしでは耐刷力は低く、熱処理によって耐刷力は向上するものの、その効果は小さい。
【０１６９】
実施例１２
実施例１１の下引き第１層の塩化ビニリデンラテックスを水分散型ポリウレタンエマルジョン（パーマリンUA-310、三洋化成工業（株）製）に代える以外は、実施例１１を繰り返した。その結果、実施例１１と同様な結果が得られた。
【０１７０】
参考例２
ポリエチレンテレフタレートフィルム支持体表面に塩化ビニリデンラテックス（旭化成工業製、Ｌ５３６Ｂ、塩化ビニリデン比率９０％以上、水酸基変性ラテックス）を乾燥塗布厚みが０．１ミクロンになるよう塗布された下引き済みポリエステルフィルムを支持体として使用し、この上に下記の処方で示される下塗り層を塗布した。
【０１７１】
下塗り層（ハレーション防止層）

水を加え、全量を６００部とした。上記の処方に於いて、ＷＢ４０−８０とは、本発明に係わる自己乳化性イソシアネート化合物の例であり、旭化成工業（株）よりデュラネートＷＢ４０−８０として入手されるものであり、溶剤により８０％濃度に希釈されたものである。
【０１７２】
上記の下塗り層（ハレーション防止層）塗液を溶液で平米当たり６０ｇになるよう該ポリエステルフィルム上に塗布乾燥した。さらにこの下塗り層（ハレーション防止層）上にオルソ増感された高コントラスト塩化銀乳剤を硝酸銀に換算して平米当たり１．５ｇ（ゼラチン０．８ｇ／ｍ²）になるよう塗布、乾燥した。乳剤層には硬膜剤としてホルマリンを使用した。乾燥後、５０℃に調節した乾燥器内で２日間加温した後、特開平８−２１１６１４号明細書中に記載の実施例１に従い、物理現像核液を塗布し、乾燥することで参考試料１の平版印刷版を作成した。
【０１７３】
上記の下塗り層（ハレーション防止層）に含まれる硬膜剤として、ＷＢ４０−８０に代えてホルマリンあるいは２−ヒドロキシ−４，６−ジクロロ−１，３，５−トリアジンのナトリウム塩をそれぞれ同量添加した以外は全く同様にして比較試料１（ホルマリン）および比較試料２（２−ヒドロキシ−４，６−ジクロロ−１，３，５−トリアジンのナトリウム塩）を作成した。
【０１７４】
上記のようにして得られる平版印刷版について、光学ウエッジを通して露光し、実施例１０の現像液及び停止液を用いて現像処理した印刷版を通常の光学濃度計を用いて反射濃度測定を行い、感度（Ｓ）および調子（ガンマγ）を求めた。感度は比較試料１のフレッシュ試料の値を１００とした相対値で示した。また、加温下で保存した場合の劣化を調べるために、フレッシュの版材を５０℃で６日間加熱した。その後、上記と同様に処理を行い、加温処理後の感度（Ｓ’）および調子（γ’）を求めた。結果を表７に示した。
【０１７５】
【表７】

【０１７６】
表７の結果より、下塗り層に自己乳化性イソシアネート（ＷＢ４０）を適用しても、写真性および保存性に何ら悪影響を及ぼさないことが明らかとなった。
【０１７７】
さらに、接着試験と印刷試験を実施例１０と同様に行った。その結果を表８及び表９に示す。表８の結果より支持体との接着性においては比較試料はアルカリ水溶液中に於いて簡単に感光層皮膜が剥離してしまったが、参考試料１は良好な接着性を示した。表９より、参考試料１は比較に比べ耐刷力が優れていることが分かる。
【０１７８】
【表８】

【０１７９】
【表９】

【０１８０】
実施例１４
ポリエチレンテレフタレートフィルム支持体表面に塩化ビニリデンラテックス（旭化成工業製、Ｌ５０２、塩化ビニリデン比率９０％以上、カルボキシル基変性ラテックス）を乾燥塗布厚みが０．１ミクロンになるよう塗布され、さらにこの上層にゼラチン下引き層として、ゼラチン３％水溶液に自己乳化性イソシアネートとしてＷＸ−１７４１（旭化成工業（株）製）を０．３％溶液になるように添加した下引き塗布液を調整し、上記の塩化ビニリデンラテックスで下引きされたポリエチレンテレフタレートフィルム上に乾燥塗膜厚みが０．２ミクロンになるよう塗布、乾燥し、塩化ビニリデンラテックス層およびゼラチン層からなる二層下引きポリエチレンテレフタレートフィルムを作成した。この支持体を使用して、参考例２の参考試料１で示した下塗り層（ハレーション防止層）、乳剤層および物理現像核層を全く同様にして塗布した試料を作成した（本発明２）。さらに参考例２において作成した比較試料１および２と同様に、下塗り層（ハレーション防止層）中の硬膜剤をホルマリンおよび２−ヒドロキシ−４，６−ジクロロ−１，３，５−トリアジンのナトリウム塩をそれぞれ同量添加した本発明試料３および本発明試料４を作成した。参考例２と全く同様に評価を行い表１０に示す結果を得た。この場合、接着性及び印刷性に関しては全ての試料について極めて良好な結果を得た。このことは、自己乳化性イソシアネート化合物を加えた下引き層を予めポリエステル支持体に設けたことによるものである。
【０１８１】
【表１０】

【０１８２】
実施例１５
ポリエチレンテレフタレートフィルム上にポリウレタンエマルジョンとしてパーマリンＵＡ−２００（三洋化成工業（株）製）を使用し、自己乳化性イソシアネート化合物としてＷＸ−１７４１（旭化成工業（株）製）をポリウレタンに対し、固形分比で１０重量％になるよう添加した下引き剤を用い、乾燥膜厚０．２ミクロンになるよう塗布乾燥し下引き加工を行った。これに参考例２の参考試料１で作成した下塗り液（ハレーション防止層）、乳剤塗液および物理現像核塗液を同様に塗布、乾燥を行い評価を行ったところ参考例２の参考試料１と同様に良好な結果を得た。
【０１８３】
実施例１６
ポリエチレンテレフタレートフィルム支持体上にポリウレタンエマルジョンとしてパーマリンＵＡ−１５０（三洋化成工業（株）製）を使用し、乾燥膜厚０．２ミクロンになるよう塗布乾燥し下引き加工を行った。自己乳化性イソシアネート化合物としてＷＸ−１７４１（旭化成工業（株）製）をゼラチンに対し、固形分比で１０重量％になるよう添加した下引き層塗布液（乾燥膜厚が０．３ミクロン）と参考例２の参考試料１で作成した下塗り（ハレーション防止層）塗液および乳剤塗液の３層をスライドビード塗布方式により同時重層塗布し、乾燥後、更に５０℃にて２日間加温を行った後、参考例２と同様に物理現像核塗液を塗布し、平版印刷版を作成した。参考例２と同様に製版処理および接着性評価を行ったところ参考例２の参考試料１と同様に良好な結果を得た。
【０１８４】
参考例３
次に、画像材料用支持体の優位性を以下の参考例にて説明する。
坪量１８０ｇ／ｍ²の紙基体の下引き層が設けられる側のポリオレフィン樹脂層 として酸化チタン、ステアリン酸亜鉛を含むＬＤＰＥ２３ｇ／ｍ²塗設し、反対側の樹脂層としてＬＤＰＥとＨＤＰＥを５０／５０の比２０ｇ／ｍ²塗設した。更に下引き層が設けられる側のポリエチレン表面をコロナ放電処理し、しかるのち、下記の処方による下引き層塗液をエアーナイフコーターで塗布し１２０℃で乾燥して下引き層を設け写真用支持体を作成した。その写真用支持体を２００ｍ／分で走行させその上に通常のモノクロ乳剤及びカラー乳剤を塗布し評価した。結果を表９にまとめた。
【０１８５】
＜参考試料１の下引き層処方＞
ゼラチン ３部
ＷＢ４０−８０ ０．３部
水 ９６部
界面活性剤 １部
【０１８６】
Ｂ４０−８０ ０．３部
水 ９６部
界面活性剤 １部
【０１８７】
上記下引き層の乾燥塗布量は０．０５ｇ／ｍ²である。上記処方に於いて、ＷＢ４０−８０とは、本発明に係わる自己乳化性イソシアネート化合物の例であり、旭化成工業（株）よりデユラネートＷＢ４０−８０として入手されるものであり、溶剤により８０％濃度に希釈されたものである。
【０１８８】
＜参考試料２の下引き層処方＞
上記参考試料１の下引き層処方に於けるゼラチンに代え、ポリウレタンエマルジョンとしてパーマリンＵＡ−１５０（三洋化成工業（株）製）を使用し、乾燥塗布量が０．２ｇ／ｍ²になるよう塗布乾燥し下引き加工を行い、自己乳化性イソシアネート化合物としてＷＸ−１７４１（旭化成工業（株）製）に変えた以外は参考試料１と同様の下引き層を設けた。
【０１８９】
＜参考試料３の下引き層処方＞
参考試料１の下引き層処方に於けるゼラチンに代え、加水分解性シリル基を有する樹脂エマルジョンとしてサンモールＳＷ−１３１（三洋化成工業株式会社製、アクリル−シリコン）を使用した以外は参考試料１と同様の下引き層を設けた。
【０１９０】
＜参考試料４の下引き層処方＞
参考試料１の下引き処方におけるゼラチンに代え、ヒドロキシプロピルセルロース（東京化成工業（株）製、２％粘度３〜６ｃｐｓ）を用いた以外は参考試料１と同様の下引き層を設けた。
【０１９１】
＜比較例１の下引き層処方＞
参考試料１の下引き処方において架橋剤として自己乳化性イソシアネートをホルマリンに変えた以外は参考試料１と同様の下引き層を設けた。
【０１９２】
＜比較例２の下引き層処方＞
参考試料１の下引き処方において架橋剤として自己乳化性イソシアネートをブロックイソシアネート（エラストロンＢＮ−４４、第一工業製薬（株）製）に変えた以外は参考試料１と同様の下引き層を設けた。
【０１９３】
＜比較例３の下引き層処方＞
参考試料２の下引き処方において架橋剤として自己乳化性イソシアネートをエポキシ（デナコールＥＸ−５２１、長瀬産業（株）製）に変えた以外は参考試料２と同様の下引き層を設けた。
【０１９４】
＜比較例４の下引き層処方＞
参考試料３の下引き処方において架橋剤として自己乳化性イソシアネートをヘキサメチロールメラミンに変えた以外は参考試料３と同様の下引き層を設けた。
【０１９５】
上記のようにして作製されたサンプルについて、接着性、写真性及び保存性を評価した。その結果を表１１に示す。
【０１９６】
接着性試験方法として以下の試験を行った。即ち、上記乳剤層を塗布した面にカッターナイフを使用して１ｃｍ角の碁盤目状の傷を入れ、１規定水酸化ナトリウム水溶液中（アルカリ接着試験）に１０分間浸漬した後、水を含ませた脱脂綿にて表面を強く擦ることで支持体との接着性を評価した。膜面を擦ることで表面層の剥離が生じた場合を×とし、一部剥離した場合は△とし、剥離が全く認められなかった場合を○とした。
【０１９７】
写真性評価は通常のモノクロ感材およびカラー感材に対する感度および調子に関する評価を実施したものであり、下引き層の種類により写真特性が影響を受けるか否かを評価したものである。感度および調子の何れにおいても影響が認められなかった場合を○とし、影響が僅かでも認められた場合を×とした。
【０１９８】
保存性評価は、該下引き層を塗布して作成した写真用支持体を５０℃で８５％（相対湿度）に調整した保存庫内で２週間加湿を行った後、常温常湿状態に戻してモノクロ乳剤およびカラー乳剤を塗布して、先と同様な接着性評価を行ったものであり、評価の基準は先と同様にして行った。
【０１９９】
【表１１】

【０２００】
以上の様に、画像形成層と樹脂被覆紙との接着性に優れた画像材料用支持体を得ることが出来、特に乳剤膜付き性及び写真性の優れた写真用支持体を得る事が出来る。
【０２０１】
参考例４
次に、印刷用シートの優位性について以下の参考例を用いて説明する。
合成紙（王子油化合成紙（株）製ＦＰＧ−８０）を基材として、その表面に下記処方からなる塗布剤を塗布乾燥することで印刷用シートを作成した。
【０２０２】
＜参考試料１の塗布剤処方＞
ゼラチン １０部
ＷＢ４０−８０ ３部
シリカ（ミズカシルＰ５２６，平均粒径３ミクロン、水澤化学工業（株）製）
１部
水 ８５部
界面活性剤 １部
【０２０３】
上記塗布剤の乾燥塗布量は２ｇ／ｍ²である。上記の処方に於いて、ＷＢ４０−８０とは、本発明に係わる自己乳化性イソシアネート化合物の例であり、旭化成工業（株）よりデユラネートＷＢ４０−８０として入手されるものであり、溶剤により８０％濃度に希釈されたものである。
【０２０４】
＜参考試料２の塗布剤処方＞
参考試料１の塗布剤処方に於けるゼラチンに代え、ポリウレタンエマルジョンとしてパーマリンＵＡ−１５０（三洋化成工業（株）製）を使用し、自己乳化性イソシアネート化合物としてＷＸ−１７４１（旭化成工業（株）製）に変え、乾燥塗布量が４ｇ／ｍ²になるよう塗布乾燥した以外は全く同様にして印刷用シートを作成した。
【０２０５】
＜参考試料３の塗布剤処方＞
参考試料１の塗布剤処方に於けるゼラチンに代え、加水分解性シリル基を有する樹脂エマルジョンとしてサンモールＳＷ−１３１（三洋化成工業株式会社製；アクリル−シリコン）を使用した以外は参考試料１と同様の塗布層を設けた印刷用シートを作成した。
【０２０６】
＜参考試料４の塗布剤処方＞
参考試料１の塗布剤処方におけるゼラチンに代え、ヒドロキシプロピルセルロース（東京化成工業（株）製、２％粘度３〜６ｃｐｓ）を用いた以外は参考試料１と同様の塗布層を設けた。
【０２０７】
＜参考試料５の塗布剤処方＞
参考試料１の塗布剤処方におけるゼラチンに代え、化１中のＰ−１で示される高分子帯電防止剤を用い、乾燥塗布量を１ｇ／ｍ²に代えた以外は参考試料１と同様の塗布層を設けた。
【０２０８】
＜比較例１＞
比較例１として、塗布剤を塗布しないで、上記の合成紙をそのまま印刷用シートとして使用した。
【０２０９】
＜比較例２の塗布剤処方＞
参考試料１の塗布剤処方において架橋剤として自己乳化性イソシアネートをホルマリンに代えた以外は参考試料１と同様の塗布層を設けた。
【０２１０】
＜比較例３の塗布剤処方＞
参考試料１の塗布剤処方において架橋剤として自己乳化性イソシアネートをブロックイソシアネート（エラストロンＢＮ−４４、第一工業製薬（株）製）に代えた以外は参考試料１と同様の塗布層を設けた。
【０２１１】
＜比較例４の塗布剤処方＞
参考試料２の塗布剤処方において架橋剤として自己乳化性イソシアネートをエポキシ（デナコールＥＸ−５２１、長瀬産業（株）製）に代えた以外は参考試料２と同様の塗布層を設けた。
【０２１２】
＜比較例５の塗布剤処方＞
参考試料３の塗布剤処方において架橋剤として自己乳化性イソシアネートをヘキサメチロールメラミンに代えた以外は参考試料３と同様の塗布層を設けた。
【０２１３】
＜比較例６の塗布剤処方＞
参考試料５の塗布剤処方におけるイソシアネートに代え、比較例４で使用したエポキシ化合物を使用した以外は参考試料５と同様の塗布層を設けた。
【０２１４】
上記にようにして作製した各種印刷用シートについて、以下の評価を行った。その結果を表１２に示す。
【０２１５】
＜水系グラビア印刷評価＞
上記のようにして作成した印刷用シートを用いて、水系グラビアインキとして大日精化工業（株）製ハイドリックＰＥＰを使用し、Ｎｏ．８ドクターバーを用いて塗布層面に塗布乾燥した。塗布した面にカッターナイフを使用して５ｍｍ角の碁盤目状の傷を入れ、粘着テープ（ニチバン（株）製「セロテープ」）を貼り付け、十分に押しつけた後で引き剥がし、インキの剥離の程度を評価した。評価の基準は、粘着テープを引き剥がした面において全くインキの剥離が認められなかった場合を○とし、部分的にインキの剥離が認められた場合を△とし、ほぼ全面に剥離が発生した場合を×とした。
【０２１６】
＜オフセット印刷評価＞
上記の印刷用シートをオフセット印刷機リョービ３２００ＣＤを使用し、印刷インキとしては、大日本インキ製Ｆグロス墨Ｂを用いて印刷を行った。印刷時の温度は２２℃で湿度は６０％であった。オフセット印刷を行った後のシートについてインキに対する接着性を評価するため、上記と同様に、印刷面にカッターナイフを使用して５ｍｍ角の碁盤目状の傷を入れ、粘着テープ（ニチバン（株）製「セロテープ」）を貼り付け、十分に押しつけた後で引き剥がし、インキの剥離の程度を評価した。評価の基準は、粘着テープを引き剥がした面において全くインキの剥離が認められなかった場合を○とし、部分的にインキの剥離が認められた場合を△とし、ほぼ全面に剥離が発生した場合を×とした。
【０２１７】
＜溶剤バリヤー性評価＞
上記のオフセット印刷で得られたシートを印刷直後に印刷面において１０ｃｍ角に裁断し、温度２２℃、相対湿度６０％に調節した室内で２４時間放置し、カールによる４角の高さを測定することで評価を行った。カール高さが３ｍｍ以下である場合を○とし、１０ｍｍ以上の場合を×とし、それらの間である場合を△とした。
【０２１８】
また、参考試料５と比較例６については、評価としてさらに表面抵抗値を測定し、帯電防止性能の尺度とした。帯電防止性能の評価結果は表１３に纏めた。表１３において、フレッシュのサンプルの表面抵抗値の測定は試料を２０℃，６５％の温湿度雰囲気下に１２時間調湿後三菱油化(株)製高抵抗抵抗率計ハイレスタＩＰを使用して測定した。表面抵抗値の測定における水洗後の測定は、試料を４０℃の温水にて５分間水洗し、乾燥後２０℃，６５％の温湿度雰囲気下で１２時間調湿を行った後先の場合と同様に表面抵抗値の測定を行った。尚、こうした耐水性に関する評価は、基体と下引き層との間の耐水接着性を評価するために実施したものである。
【０２１９】
【表１２】

【０２２０】
【表１３】

【０２２１】
＜参考試料６〜１０＞
印刷用基材として２軸延伸され表面をコロナ処理したポリエステルフィルム（ダイアホイル（株）製１００ミクロンＰＥＴフィルムＴ１００）を使用し、上記参考試料１〜５で使用した塗布剤および乾燥塗布量でそれぞれポリエステルフィルム上に塗布乾燥させることで印刷用シートを作成した。参考試料１〜５と全く同様にして評価を行い各対応する印刷用シートについて表１２および表１３に示した結果と同様の結果を得た。但し、ポリエステルフィルム自体の耐溶剤性が高いため、溶剤バリヤー性の評価は全て○であった。
【０２２２】
以上の様に、各種印刷インキでの印刷性に優れた印刷用シートを提供し、また耐水性、インキ接着性に優れ、汎用オフセットインキを使用しても、凹凸やカールなどの問題を生じないオフセット印刷適性に優れた印刷用シートが得られる。
【０２２３】
【発明の効果】
本発明は、ポリエステルフィルム支持体との接着性に優れたハロゲン化銀写真感光材料及び平版印刷版を提供する。ポリエステルフィルム支持体の下引き層として、熱処理を行わずとも接着性の良好な下引き層を与える。
また、画像形成層と樹脂被覆紙との接着性に優れた画像材料用支持体を得ることができ、特に乳剤膜付き性及び写真性の優れた写真用支持体を得る事が出来る。
更に、各種印刷インキでの印刷性に優れた印刷用シートを提供し、また耐水性、インキ接着性に優れ、汎用オフセットインキを使用しても、凹凸やカールなどの問題を生じないオフセット印刷適性に優れた印刷用シートが得られる。[0001]
BACKGROUND OF THE INVENTION
The present invention uses a silver halide photographic light-sensitive material and a lithographic printing plate using silver halide, more specifically, a silver halide photographic light-sensitive material and a lithographic printing plate excellent in adhesiveness to a polyester support, and a resin-coated paper. The present invention relates to a support for image material and a printing sheet.
[0002]
[Prior art]
Silver halide photographic light-sensitive materials using silver halide include plate-making film, color negative film, color positive film, black-and-white negative film, medical X-ray film, scanner film, and lithographic printing plate. The silver photographic light-sensitive material is produced by applying to a polyester film support and drying by aqueous coating using a hydrophilic binder such as gelatin. The surface of the polyester film support is generally hydrophobic. When an aqueous coating solution containing gelatin or the like as a binder is applied to the polyester film surface as it is, the adhesive property between the hydrophilic binder such as gelatin and the polyester film surface is insufficient. When the treatment is performed with an alkali developer, film peeling may occur at the interface, or the binder layer may be easily peeled off from the polyester film support by rubbing the surface.
[0003]
In particular, when used as a lithographic printing plate, since the binder layer on the surface of the printing plate may be peeled off from the support during printing, there may be a problem with printing durability. It is desirable that the adhesiveness of is extremely strong.
[0004]
In order to improve the adhesion of the surface of the polyester film support to the hydrophilic binder, various undercoat layers are widely provided on the surface of the polyester film support. For example, Japanese Patent Application Laid-Open No. 56-140343 gives examples of undercoat layers using styrene-butadiene latex, and Japanese Patent Application Laid-Open Nos. 63-304249 and 64-538 use vinylidene chloride latex. The undercoat layer is described. When a polyester film support provided with an undercoat layer of such a hydrophobic latex is used and a layer containing gelatin or the like as a binder is provided, the adhesion to the support is improved due to the presence of the undercoat layer. There was no case.
[0005]
In the above-described single layer undercoat, it is often difficult to increase the level of adhesiveness to a sufficiently satisfactory level, and it is composed of a further hydrophilic resin on the undercoat layer of the hydrophobic latex. Studies of two-layer subbing in which an undercoat layer is laminated have been widely studied. For example, JP-A-53-67787 discloses a two-layer structure in which a vinylidene chloride latex layer is provided on the first layer and a cellulose ester layer is provided thereon, and JP-A-1-180537, 1 No. -202750 discloses a two-layer undercoating structure in which a water-soluble polymer layer such as gelatin is coated on the first vinylidene chloride layer.
[0006]
However, even in such a two-layer undercoating structure, in order to develop adhesiveness, heat treatment may be required under a high temperature condition of about several hundreds of degrees Celsius after the undercoating is applied. And dimensional stability may be adversely affected. Also, providing two undercoat layers is disadvantageous in terms of manufacturing equipment and productivity.
[0007]
Silver halide photographic light-sensitive materials and lithographic printing plates have been produced using polyester films having an undercoat layer prepared by the conventional technique as described above, but the adhesiveness with the polyester film is still not sufficient. In some cases, problems such as film peeling during printing or printing and poor printing durability may occur.
[0008]
A lithographic printing plate using a silver salt diffusion transfer method (DTR method) using silver halide, particularly a lithographic printing plate having physical development nuclei on a silver halide emulsion layer is disclosed in, for example, US Pat. No. 3,728,114. No. 4,134,769, No. 4,160,670, No. 4,336,321, No. 4,501,811, No. 4,510,228, No. 4 , 621,041 and the like. In these lithographic printing plates, the exposed silver halide crystals are chemically developed by DTR development to form black silver to form hydrophilic non-image areas, while the unexposed silver halide crystals are a developer. The silver salt complexing agent forms a silver salt complex and diffuses to the physical development nuclei on the surface to cause physical development to form an image area mainly composed of ink-accepting physical development silver.
[0009]
Thus, the surface of the lithographic printing plate is covered with a binder mainly composed of gelatin, and a silver image portion made of physically developed silver is formed on the surface of the binder. The offset printing is performed by transferring the ink only to the silver image portion, but as described above, the silver image portion is caused by mechanical wear during printing or penetration of the solvent in the ink. There are problems such as lack of ink and a decrease in ink receptivity.
[0010]
On the other hand, there is known an image material in which an image recording layer is provided on a resin-coated support having a resin coating layer such as polyolefin on both surfaces of a paper substrate. For example, a silver halide photographic material, an ink jet recording material, a heat sensitive recording material, a sublimation heat transfer recording material, a photosensitive heat sensitive recording material, etc. Further, an image forming layer such as a sublimation heat transfer dye image-receiving layer and a light-sensitive thermochromic layer, and an auxiliary function layer such as an undercoat layer, a protective layer, a back layer and an antistatic layer are coated as necessary. In particular, the silver halide photographic composition layer includes a silver halide photographic emulsion layer, a protective layer, an undercoat layer, an intermediate layer or an anti-color mixing layer, an antihalation layer, a filter layer, an ultraviolet absorption layer, a back layer, and an antistatic layer. It is composed of layers and the like and combinations thereof.
[0011]
Conventionally, a resin-coated support having a base paper surface coated with a resin capable of forming a film is well known as a support for image materials. In particular, polyolefin resin-coated paper is used as a silver halide photographic support, and examples include those described in Japanese Patent Publication No. 55-12584 and US Pat. No. 3,501,298. As such a photographic paper support, a polyolefin resin-coated paper is often used instead of the baryta paper which has been used conventionally. The reason for this is that the polyolefin resin-coated paper as a photographic support is hydrophobic, so that the processing solution is less likely to penetrate into the paper layer during development and fixing of photographic paper compared to baryta paper. This is because there is an advantage that the processing time such as drying is shortened.
[0012]
However, such a hydrophobic support cannot be coated with a silver halide photographic emulsion as an aqueous coating solution as it is. As countermeasures for this, flame treatment, corona discharge treatment and subbing treatment are generally known as activation of the hydrophobic support surface, but flame treatment is inconvenient in handling control, and corona treatment takes time after treatment. Even when the emulsion is coated on a photographic support that has been attenuated over time due to the reduction in water wettability of the surface, the adhesion between the emulsion layer and the polyolefin resin-coated surface of the support is reduced, and sufficient emulsion film adhesion cannot be obtained.
[0013]
Therefore, by subtracting latex emulsion, water-soluble synthetic resin, gelatin and a mixture thereof having an affinity for a photographic support subjected to corona discharge before the surface water wettability after corona discharge treatment is lowered, the aging is continued for a long time. After that, it has been studied that the emulsion film adhesion property does not deteriorate even when the emulsion is coated. As the undercoat layer provided on the polyolefin resin-coated support, a gelatin composition is generally used. As the water-soluble polymer other than gelatin, various water-soluble polymers such as polyvinyl alcohol, polyacrylamide, polyvinyl pyrrolidone, carboxymethyl cellulose, and hydroxyethyl cellulose can be used. Various latex emulsions such as acrylic latex and polyester emulsion may be used together as latex emulsion, but blocking may occur when aging is applied for a long time after undercoating, or when aging is applied particularly in high temperature and high humidity conditions. There have been problems such as the occurrence of this phenomenon and the decrease in adhesive strength at the interface when a photographic emulsion layer is provided on the undercoat layer.
[0014]
According to Japanese Patent Application Laid-Open No. 59-31946, as a conventional technique as an improvement means, gelatin calcium ion (Ca⁺⁺) For gelatin-containing photographic coating solutions using gelatin of 2000 ppm or less with respect to dry gelatin, according to JP-A-62-35244, the coating amount is 0.02 g / m.²~ 0.5g / m²However, it is not possible to provide a subbing layer that has good adhesion to the subbing layer, uneven coating of the subbing layer, and an emulsion film. Further, JP-A-5-150398 discloses an example in which gelatin having a jelly strength of 200 g to 260 g and a calcium ion in dry gelatin of 2000 to 4000 ppm is used in the undercoat layer. Was still not enough.
[0015]
As a means for improving the emulsion film adhesion (adhesiveness), various hardeners having a hardening effect on gelatin are usually added to the gelatin subbing layer, and aldehydes such as formalin and glutaraldehyde are used. Addition of various hardeners for known gelatin such as lacquer, chrome alum, methylolmelamine hardener, dichlorotriazine hardener, epoxy hardener, aziridine hardener, active ester hardener However, in any case, there are problems such as insufficient emulsion coating and a short pot life of the coating liquid.
[0016]
For example, Japanese Patent Application Laid-Open No. 63-307879 includes an example of an ink jet recording material having a resin-coated paper as a support, and is not limited to the above-described silver halide photographic material applications. , 774,224 show a thermal transfer recording material using a similar resin-coated paper as a support. A common problem when creating such image materials using a resin-coated support is to improve adhesion between the support and the image forming layer, water resistance, etc., and devise various undercoat layers The actual situation has been studied.
[0017]
On the other hand, in gravure printing, flexographic printing, and offset printing, a paper-like sheet called synthetic paper and a resin sheet imparted with printability are known as printing sheets. Synthetic paper is made from a polyolefin resin with an inorganic filler and a small amount of additives as raw materials, and is formed into a sheet while generating microvoids by biaxially stretched film molding. Is widely used because it is inexpensive and has excellent water resistance and chemical resistance. As the resin sheet, a substrate such as polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polyester, polystyrene, etc. is used, and both of which are given printability are usually used.
[0018]
When printing on the surface of synthetic paper and resin sheets, gravure printing has been performed in the past. However, in the field of gravure printing, due to problems of safety of handling organic solvents, work environment and health problems in recent years. There is an increasing demand to use water-based gravure ink. However, the surface of conventional synthetic paper has poor adhesion to water-based inks, and the peeling of ink from printed matter is remarkable, and it was difficult to use such water-based inks. It is desired to improve the performance.
[0019]
Since offset printing is easy to perform multicolor printing, it is used for printing on paper substrates such as high-quality paper and coated paper, and plastic films such as polyethylene terephthalate sheets. In general, general-purpose offset inks use quick-drying inks that contain drying oil, resin, and mineral oil, which is a high-boiling-point petroleum solvent, as the vehicle in the ink components in order to speed up the drying time. When printing on polyolefin resin sheets such as polyethylene and polypropylene and synthetic paper using mold offset ink, the high-boiling petroleum solvent in general-purpose offset ink causes the resin sheet and synthetic paper as the base material to swell, The resin sheet and the synthetic paper base material itself are difficult to use due to a solvent attack such as partial unevenness or curling of the whole base material.
[0020]
Translucent synthetic paper may be used by inserting it between general printed materials. Even in such a case, the vehicle in the offset ink of the general printed material affects the semitransparent synthetic paper, A general offset ink cannot be used because it causes problems such as curling of the whole, and it cannot be used in combination with a general offset print.
[0021]
For this reason, Japanese Patent Application Laid-Open No. 4-77530 discloses a method of providing a solvent permeation preventing layer on a synthetic paper base material in order to prevent permeation of a high boiling petroleum solvent in offset ink. However, it is necessary to provide a coating agent layer imparted with printability on the solvent permeation preventive layer, which is a problem because the solvent permeation preventive layer itself does not have printability. Furthermore, JP-A-11-107194 includes an example of a synthetic paper provided with a coating layer containing polyvinyl alcohol and polyurethane as resin components, but although the improvement in solvent resistance is recognized, the coating layer There remains room for further improvement in the adhesion and water resistance between the ink and the synthetic paper substrate, and the ink adhesion is still insufficient.
[0022]
For the purpose of improving the adhesion to offset ink, for example, JP-A-7-314622 discloses a laminated sheet (synthetic paper) having a structure in which a uniaxially stretched polyolefin resin film is laminated on the surface of a substrate. The adhesiveness to general-purpose offset ink has not been sufficient yet.
[0023]
One of the more important problems in offset printing is prevention of charging of a printing sheet. Synthetic paper and resin sheets have a property that they are extremely easily charged by friction or the like because plastics having high insulation properties are used as a base material. For this reason, in offset printing, etc., in which a printing sheet is supplied to a printing machine as a sheet, it is suitable for feeding a sheet to the printing machine for each leaf, and is discharged after printing. There is a problem that troubles due to electrostatic adsorption or the like frequently occur in paper discharge suitability.
[0024]
In order to avoid the above troubles, measures have been taken such as applying an antistatic agent such as a surfactant to the surface of the printing sheet, or kneading the antistatic agent into the printing sheet itself. However, the sheet coated with a low molecular weight antistatic agent such as a surfactant has a problem that the antistatic agent migrates into the hygroscopic liquid during offset printing and greatly impairs the desensitizing ability of the moisturizing liquid. Furthermore, even a sheet kneaded with such an antistatic agent may cause problems similarly to a coating type sheet due to bleeding out of the antistatic agent to the surface of the sheet.
[0025]
In order to impart an antistatic function, for example, JP-A-6-18489 discloses a printing sheet provided with a thermosetting coating layer made of a cationic conductive water-soluble resin and an epoxy compound. When the coating layer is formed, the heating temperature needs to be raised to about 100 ° C., and the polyolefin resin sheet has a negative effect on the flatness due to softening of the surface, or the curing reaction by the epoxy compound is slow. For this reason, there has been a problem that a heating treatment such as post-cure may be required after providing the coating layer.
[0026]
[Problems to be solved by the invention]
An object of the present invention is to improve the adhesion between a layer constituting a silver halide photographic light-sensitive material and a polyester film support. In particular, an object of the present invention is to provide a silver halide photographic light-sensitive material in which film peeling does not occur even when processed with an alkali developer. Another object of the present invention is to provide a lithographic printing plate having improved printing durability by improving adhesion between a layer constituting a lithographic printing plate using silver halide and a polyester film support. Furthermore, another object of the present invention is to provide a silver halide photographic light-sensitive material and a lithographic printing plate which can impart high adhesion even with only one undercoat layer and can withstand severe processing conditions such as development processing.
[0027]
Another object of the present invention is to improve the adhesion of the undercoat layer to the support and the image forming layer in an image material using a resin-coated paper provided with an undercoat layer as a support. An object of the present invention is to obtain a support for an image material provided with an undercoat layer that is excellent in coating unevenness of the undercoat layer and having an emulsion film.
[0028]
Another object of the present invention is to provide a printing sheet excellent in printability with various printing inks, and also has excellent water resistance and ink adhesion, and problems such as unevenness and curl even when general-purpose offset ink is used. It is an object of the present invention to provide a printing sheet excellent in offset printing suitability that does not cause the problem.
[0029]
[Means for Solving the Problems]
The above object of the present invention has been achieved by the following invention.
(1) A silver halide photographic light-sensitive material comprising gelatin and a self-emulsifiable isocyanate compound having an ethylene oxide repeating unit and two or more isocyanate groups in at least one layer constituting a silver halide photographic light-sensitive material. material.
(2) A silver halide photographic material comprising a polyester film support provided with an undercoat layer containing a self-emulsifying isocyanate compound having an ethylene oxide repeating unit and two or more isocyanate groups.
(3) In a lithographic printing plate having at least an undercoat layer, a silver halide emulsion layer and a physical development nucleus on a support, at least one layer constituting the lithographic printing plate contains gelatin, an ethylene oxide repeating unit and two or more A lithographic printing plate comprising a self-emulsifiable isocyanate compound having an isocyanate group. (4) An undercoat layer, a silver halide emulsion layer, and a physical development nucleus layer are formed on a polyester film support provided with an undercoat layer containing a self-emulsifying isocyanate compound having an ethylene oxide repeating unit and two or more isocyanate groups. A lithographic printing plate characterized by having at least.
(5) In a support for an image material in which a resin coating layer is provided on both sides of a paper substrate and an undercoat layer is provided on the resin coating surface on which an image recording layer is coated, ethylene is contained in the undercoat layer. A support for an image material comprising a self-emulsifiable isocyanate compound having an oxide repeating unit and two or more isocyanate groups.
(6) In the printing sheet in which the coating layer is provided on at least one side of the substrate, the coating layer includes a self-emulsifiable isocyanate compound having an ethylene oxide repeating unit and two or more isocyanate groups. Sheet for printing.
[0030]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
One object of the present invention is to improve the adhesiveness and printing durability of silver halide photographic light-sensitive materials and lithographic printing plates having a polyester film as a support. The polyester film support here refers to a general polyester film that can be formed as a film of polyethylene terephthalate or polyethylene naphthalate. As for the thickness of the polyester film support body used for this invention, 50-300 micrometers is common.
[0031]
A polyester film support used in a silver halide photographic light-sensitive material is usually improved in adhesiveness with an aqueous coating film such as a gelatin film constituting the silver halide photographic light-sensitive material only after performing a subbing process. In this case, the adhesiveness at the interface with the gelatin layer constituting the silver halide photographic light-sensitive material depends greatly on the type of subbing agent used in the subbing process and the drying conditions or heat treatment conditions after applying the subbing agent. It is what is done. The self-emulsifiable isocyanate compound according to the present invention has both a hydrophobic part and a hydrophilic part in its structure, so that it has an affinity for a hydrophobic polyester film support and an affinity for a hydrophilic gelatin film. It is the feature that it has both of these, and it is the feature that a favorable adhesiveness is expressed in the interface of both. The undercoating resin that can be used in this case is preferably a water-soluble polymer such as gelatin, a hydrophobic latex, or an emulsion. An undercoating layer containing such an undercoating resin and a self-emulsifiable isocyanate compound is applied to the surface of the polyester film. It is a feature of the present invention to use a dried support.
[0032]
Examples of the self-emulsifying isocyanate compound having an ethylene oxide repeating unit and two or more isocyanate groups used in the present invention include Japanese Patent Publication No. 55-7472 (US Pat. No. 3,996,154) and Japanese Patent Application Laid-Open No. Hei 5 (1990). -222150 (US Pat. No. 5,252,696), JP-A-9-71720, JP-A-9-328654, JP-A-10-60073, etc. . Specifically, for example, a polyisocyanate having an isocyanurate structure of a cyclic trimer skeleton formed from an aliphatic or alicyclic diisocyanate in a molecule, or a polyisocyanate having a burette structure, a urethane structure or the like in the molecule. A very preferable example is a polyisocyanate compound having a structure obtained by adding a polyethylene glycol or the like having one terminal etherification to only a part of the polyisocyanate group as a base polyisocyanate. A method for synthesizing an isocyanate compound having such a structure is described in the above specification. Specific examples of such isocyanate compounds are commercially available in which polyisocyanates by cyclic trimerization using hexamethylene diisocyanate or the like as a starting material are used as base polyisocyanates. For example, deyuranate WB40 or WX1741 is available from Asahi Kasei Corporation. And so on.
[0033]
In the isocyanate compound as described above, since the ethylene oxide repeating unit is directly bonded to the hydrophobic base polyisocyanate, an emulsion in which the polyisocyanate portion is separated from the aqueous layer in water is formed, and the polyethylene oxide portion is It has a self-emulsifying function to stabilize the emulsion. Because of this, isocyanate groups that react with water and deactivated continue to exist stably even in water, so even when added to an aqueous coating solution, the pot life is long. In the film formation process, moisture evaporates and the emulsion state is quickly destroyed, and it has the advantage that the crosslinking reaction proceeds rapidly by diffusing into the film.
[0034]
In the self-emulsifiable isocyanate compound, the length of the ethylene oxide repeating unit is preferably about 5 to 50 repeating units. If it is less than this, the self-emulsifying property is poor and it is difficult to show a stable emulsifying property in an aqueous solution, and if it has 50 or more repeating units, it tends to crystallize and become a solid, which is not preferred. Furthermore, the isocyanate content in the self-emulsifiable isocyanate compound is preferably in the range of 8 to 25% by weight.
[0035]
In the present invention, at least one undercoat layer containing the self-emulsifiable isocyanate compound is provided on a polyester film support. The undercoat layer may be composed of only one layer or may be composed of two or more layers. One feature of the present invention is that sufficient adhesiveness required for a silver halide photographic light-sensitive material can be imparted with only one layer.
[0036]
When the undercoat layer is a single layer, it is preferable to use a self-emulsifiable isocyanate compound in combination with a latex or an emulsion. Examples of the latex or emulsion used together with the self-emulsifying isocyanate compound include vinylidene chloride latex, styrene / acrylic latex, styrene / butadiene latex, urethane emulsion, and polyester emulsion. Among these, vinylidene chloride latex and urethane emulsion are preferable. A urethane emulsion is particularly preferable.
[0037]
A particularly preferred example of the vinylidene chloride latex is a latex having a vinylidene chloride content of 80 parts by weight or more, and a copolymer obtained by copolymerizing an acrylic monomer, and more preferably a monomer having a hydroxyl group such as a hydroxyethyl group as an acrylic monomer. A copolymerized latex is very particularly preferred.
[0038]
As the urethane emulsion, a water-dispersed polyurethane emulsion is preferable, and examples thereof include a self-emulsifying polyurethane resin. As the self-emulsifying polyurethane resin, those having a hydrophilic group such as a sulfonic acid group, a carboxy group, a hydroxyl group, and a polyethyleneoxy group in the polyurethane structure are preferable, and commercially available various polyurethane emulsions are preferably used.
[0039]
The content of the self-emulsifiable isocyanate compound in the undercoat layer is 1 mg / m²-10g / m²Is suitable, preferably 1 mg / m²~ 1g / m²Range. The self-emulsifiable isocyanate compound is used in the range of 0.1 to 200% by weight, preferably in the range of 1 to 50% by weight, based on the latex or emulsion described above.
[0040]
In the case of a single undercoat layer, water-soluble polymers such as gelatin, inorganic fine particles and polymers such as silica having a particle size corresponding to the thickness of the undercoat layer (from the thickness of the undercoat layer to several times) for the purpose of preventing blocking, etc. It may contain beads and the like. When the undercoat layer is a single layer, the film thickness (dry film thickness) is preferably formed in the range of 0.01 to 1 micron. If the film thickness is less than this, the effect as the undercoat layer hardly appears, and when it is formed with a thickness exceeding 1 micron, no improvement in the effect as the undercoat layer is observed, rather the curl of the film There may be adverse effects such as worsening the sex.
[0041]
The coating and drying of a single undercoat layer containing a self-emulsifiable isocyanate compound and latex or emulsion can be carried out before or after stretching the film, or off-line in the polyester film production process. In either case, good adhesion can be obtained. From the viewpoint of productivity, it is preferable to apply and dry the undercoat layer before stretching the film. Usually, heat treatment is performed after stretching in the film forming process of the polyester film, but there is no problem even if the heat treatment is performed at a temperature ranging from room temperature to a few hundred degrees or 250 ° C. exceeding 200 ° C. Absent.
[0042]
In the present invention, the undercoat layer may be composed of two layers. In a preferred embodiment in this case, the first layer adjacent to the polyester film support is made of a hydrophobic latex or emulsion as described above, and the second layer is made of a water-soluble polymer such as gelatin. In this case, the self-emulsifiable isocyanate compound is contained in at least one of the layers, but is preferably contained in at least the second layer. The first layer may not contain any self-emulsifiable isocyanate compound, but it may be preferable depending on the type of the hydrophobic latex and emulsion constituting the first layer. The content of the self-emulsifiable isocyanate compound and the ratio to the resin are the same as those of the single undercoat layer described above.
[0043]
The most preferred embodiment of the two-layer structure is a structure in which the first layer is made of a vinylidene chloride latex or a polyurethane emulsion, and the second layer is made of gelatin and a self-emulsifiable isocyanate. The thickness (dry film thickness) of each undercoat layer in the two-layer structure is the same as that in the case of the single layer undercoat described above. Usually, the most preferred undercoat layer thickness is in the range of 0.03 to 0.5 microns each.
[0044]
The first layer can be applied and dried in the same manner as the single layer described above. The application of the second layer is performed after the application and drying of the first layer, but is usually performed after the stretching process of the polyester film. This is because when the second layer containing a water-soluble polymer such as gelatin is applied and dried before film stretching, the gelatin layer is torn by stretching and becomes a discontinuous film, thereby forming an undercoat layer. This is because the above functions may not be exhibited or the transparency of the film may be significantly impaired. The coating and drying of the second layer may be performed in the polyester film manufacturing process (inline), or may be performed by secondary processing (offline) separately from the film manufacturing line.
[0045]
One feature of the two-layer subbing according to the present invention is that, after applying the second layer, sufficient adhesiveness is achieved at a drying temperature of about room temperature to about 80 ° C. without heat treatment at a high temperature (for example, 100 ° C. or higher). It can be expressed. As a result, there is an advantage that a heat treatment apparatus is not required. Yet another advantage of drying the second layer at a relatively low temperature is that it favors dimensional stability.
[0046]
That is, in the heat treatment step usually performed after stretching in the polyester film formation step, the degree of crystallinity is increased, and the amorphous orientation is relaxed, so that the thermal shrinkage rate is lowered and the dimensional stability is improved ( For example, processing technology research group publication, industrial plastic film, 1991, Chapter 4, p.157). However, when an undercoat layer is applied after the heat treatment step and heat treatment is performed, the thermal shrinkage rate may change and the dimensional stability may be impaired. The heat treatment after application of the subbing layer may increase the film strength depending on the composition of the subbing layer and may favor the dimensional stability, but causes instability due to variations in the heat treatment conditions. Therefore, it is preferable not to perform heat treatment for stable dimensional stability. Conventionally, in order to improve the adhesion of the undercoat layer, heat treatment at a high temperature has been required. However, the undercoat layer of the present invention does not require heat treatment, and does not impair dimensional stability. It can be said that it is extremely preferable.
[0047]
For example, JP-A-4-86648, JP-A-4-96055, JP-A-4-184335, and JP-A-4-184431 disclose conventional techniques relating to the above-described two-layer subbing configuration. In the methods described in these, it is important to set the heat treatment conditions at the time of subbing, and the heat treatment conditions at the time of subbing as shown in the present invention are over a wide range (the heat treatment is performed). At least) stable adhesive performance cannot be exhibited, and the adhesiveness is not sufficient.
[0048]
One of the advantages of the above-described subbing process with a single layer is that the influence on the dimensional stability associated with the heat treatment of the second layer in the subbing of two layers can be avoided. In addition, in the case of performing a single layer subbing process made of a hydrophobic latex or emulsion, it is possible to apply the subbing layer before or during the stretching process as compared to the two-layer subbing. Therefore, since the coating width can be shortened as compared with that after stretching, there is an advantage that it is easy to ensure the uniformity of coating. Further, since it is a single layer subbing, there is an advantage that a separate coating and drying device required for the two-layer subbing is unnecessary.
[0049]
As an example of the prior art to be referred to, for example, Japanese Patent Application Laid-Open No. 9-175009 includes an example of an undercoat layer for a polyester film by non-aqueous coating comprising a polyisocyanate and a solvent-soluble resin such as a polyester resin. In this example, it is shown that by performing the subbing process, the adhesiveness is improved when a water-based coating layer is further provided thereon. The silver halide photograph according to the present invention It does not show the undercoat structure for the polyester film support in the use of the photosensitive material, and it may cause peeling at the interface with the support surface, especially when immersed in a strong alkaline solution in the development process. There was no indication. In the present invention, since the undercoat layer is water-based coating, the surface of the undercoat layer has high hydrophilicity, and a hydrophilic polymer is remarkably applied thereon compared to the case of performing solvent-based coating. In this case, the compatibility between the undercoat layer and the hydrophilic polymer layer is improved, and therefore, it is characterized by showing stronger adhesiveness.
[0050]
The silver halide photographic light-sensitive material targeted by the present invention has at least one silver halide emulsion layer on a polyester film support on which the above-mentioned undercoat layer is coated. Examples of the silver halide photographic light-sensitive material include a plate making film, a color negative film, a color positive film, a black and white negative film, a medical X-ray film, a scanner film, and a lithographic printing plate. These silver halide photographic light-sensitive materials have an antihalation layer, an intermediate layer, a protective layer, and a backing layer in addition to the silver halide emulsion layer. In these constituent layers, gelatin is generally used as a binder, and the undercoat layer of the present invention exhibits an excellent effect in terms of adhesion to these gelatin layers. In particular, since the lithographic printing plate is required to have a strong adhesive force and dimensional stability sufficient to withstand printing, the present invention is particularly preferably used.
[0051]
The silver halide photographic light-sensitive material is generally processed with an alkaline developer having a pH of about 9 to 14, but during the development process, film peeling or scratches due to poor adhesion between the support and the gelatin layer are likely to occur. . The undercoat layer of the present invention can impart adhesiveness that can sufficiently withstand the treatment with such an alkaline developer.
[0052]
In addition, a lithographic printing plate using silver halide (for example, a lithographic printing plate using silver complex diffusion transfer described above) is printed with ink and dampening water on the plate surface. Insufficient adhesiveness causes a problem that the silver image portion formed on the gelatin layer and the non-image portion consisting of the gelatin layer itself are partially lost due to mechanical abrasion and ink or dampening water penetration. is there. The undercoat layer of the present invention can provide adhesion that can withstand such severe printing.
[0053]
Further, the silver halide photographic light-sensitive material is required to have dimensional stability, but the polyester film support on which the undercoat layer of the present invention is coated is greatly improved as compared with the conventional one.
[0054]
The above is an explanation of using a self-emulsifiable isocyanate compound in the undercoat layer. Next, at least one layer constituting a silver halide photographic light-sensitive material and a lithographic printing plate according to another embodiment of the present invention. An embodiment in which the above self-emulsifiable isocyanate compound is used together with gelatin will be described. By providing a layer containing gelatin and a self-emulsifiable isocyanate compound on at least one layer constituting the silver halide photographic light-sensitive material, for example, an anchor coat layer without adversely affecting the photographic characteristics and storage stability of the silver halide photographic material. As an overcoat layer, it has characteristics that it can exhibit the function of effectively preventing scratches and rubbing and fogging. In addition to this, the present invention can be applied to any of a layer containing silver halide grains, a backcoat layer, and the like. Among them, as a particularly preferred example, it is applied as the lowermost layer among the layers constituting the photosensitive material, and the layer composed of gelatin or the like on the layer and the hydrophobic surface of the support are particularly well bonded. As mentioned.
[0055]
In the present invention, it has been found that the use of the above self-emulsifiable isocyanate compound together with gelatin gives extremely favorable characteristics when applied to a lithographic printing plate using a silver salt diffusion transfer system. . In other words, by providing a layer containing gelatin and a self-emulsifiable isocyanate compound on at least one layer constituting the lithographic printing plate, it is supported without any adverse effect on the photographic properties and storability of the lithographic printing plate by the silver salt diffusion transfer method. It is characterized by improved adhesion to the body and good printing durability. The self-emulsifiable isocyanate compound can be applied to any of the undercoat layer, silver halide emulsion layer, physical development nucleus layer, backcoat layer and the like constituting the lithographic printing plate. Among them, as a particularly preferred example, it is applied to the undercoat layer which is the lowermost layer of the lithographic printing plate, and the layer composed of gelatin or the like and the hydrophobic surface of the support are bonded very well. Is mentioned as a notable feature. In addition to this, when applied to an emulsion layer, adhesion to both the undercoat layer and the physical development nucleus layer sandwiching the emulsion layer is improved, so that a favorable effect for improving the printing durability is recognized. When self-emulsifiable isocyanate is added to the physical development nucleus layer, the effect of firmly bonding the physical development silver to the surface is recognized, and it is preferably used. When applied to the back coat layer, the adhesion to the support is improved, which is extremely preferable.
[0056]
Various examples of cross-linking agents for gelatin have hitherto been mentioned. Stability in aqueous solution mixed with gelatin, etc. (potential time), cross-linking property during film formation (speed, degree of cross-linking) and post-curing For those that do not satisfy all the desirable properties of (cross-linking progress) and have a short pot life, a special device for performing a mixing method immediately before adding a crosslinking agent to the coating solution immediately before coating may be installed. If the crosslinking rate is slow, or if there is a post-curing film, the product after application must be stored in a warmed warehouse and the heating process must be performed. It was. Furthermore, in the photographic light-sensitive materials containing various additives, there are currently many photographic photosensitive materials that significantly adversely affect photographic characteristics and storage stability.
[0057]
The self-emulsifiable isocyanate compound according to the present invention does not have the above-mentioned various problems, and is characterized by exhibiting extremely advantageous characteristics in the production of silver halide photographic light-sensitive materials and planographic printing plates. In combination with gelatin, it effectively cross-links and does not adversely affect photographic characteristics, and also affects photographic characteristics over a wide range of drying conditions (drying temperature, speed, etc.) during lithographic printing plate manufacture. It is also a feature that does not affect. In the industry, it is well known that the setting of drying conditions is very important, especially when gelatin film dehydrates and crosslinks and shrinks under high speed drying conditions, or there is residual stress in the gelatin film. There is a problem that fog is generated due to the pressure applied to the silver halide crystal. It is also a feature of the present invention that it has been found that the use of self-emulsifiable isocyanate has the effect of suppressing the occurrence of reticulation and fogging even in such problems related to drying conditions. As one of the causes that can exert such an effect, although it is estimated, an appropriate flexible space is formed between the isocyanate groups that are crosslinking points by an alkyl group such as a hexamethylene group. It is conceivable to provide flexibility between the points and prevent excessive stress distortion of the gelatin film.
[0058]
As a prior art, JP-A-9-160172 describes that a silver halide photographic light-sensitive material having a magnetic recording layer contains a polyisocyanate dispersible in water. The polyisocyanate in this specification is not a self-emulsifiable isocyanate having an ethyleneoxy group according to the present invention but a hydrophobic isocyanate compound that cannot be dispersed in water by itself. In this specification, a hydrophobic isocyanate is dispersed in water. A separate emulsifier is used for this purpose. The emulsifier is obtained by reacting polyisocyanate with an alkoxypolyalkylene ether glycol and dialkanolamine. By combining such an emulsifier with a polyisocyanate, a water-dispersible isocyanate compound can be obtained. However, it is easy to inferior in water resistance of the crosslinked coating because the emulsifier is contained in a form that does not bind with the isocyanate involved in crosslinking. Imagine. That is, when the self-emulsifiable isocyanate according to the present invention is used, since the isocyanate compound and the ethyleneoxy part involved in emulsification are chemically bonded, the emulsified component does not elute from the coating, When an emulsifier is used, since the emulsifier polymer component is eluted from the coating, the properties of the coating are changed during the development process, which is not preferable. However, in the self-emulsifiable isocyanate according to the present invention, it is also preferable to add a surfactant separately for the purpose of improving the emulsion dispersion stability, or even when applied to a support in a normal coating solution. Various surfactants are usually used for the purpose of improving the surface wettability. Surfactants used for these normal purposes are mainly low molecular weight compounds, and the amount used is often several percent or less, and the effect on the water resistance of the film is very slight or none. .
[0059]
As another prior art example, JP-A-6-175252 discloses a silver halide photographic light-sensitive material containing a blocked isocyanate blocked with bisulfite. The reactivity of the blocked isocyanate is low, and it is usually necessary to recover the isocyanate group by removing the blocking group by heating or the like. The self-emulsifiable isocyanate according to the present invention is extremely reactive because the active free isocyanate group is left in the reaction as it is, and the undercoat layer is cross-linked without heating. It is.
[0060]
As still another embodiment of the present invention, among the two subbing layers as described above, a second layer and a gelatin-containing layer constituting a silver halide photographic light-sensitive material or a lithographic printing plate are simultaneously laminated. It is an aspect created by coating. That is, a polyester film support provided with an undercoat first layer (preferably composed of a hydrophobic latex or an emulsion) on a polyester film is prepared in advance, at the time of photographic photosensitive material production or lithographic printing plate production, A subbing second layer containing a water-soluble polymer (preferably gelatin) and a self-emulsifying isocyanate compound, and a gelatin-containing layer constituting a photographic light-sensitive material or a lithographic printing plate are simultaneously coated on the above-mentioned support for photosensitivity. To make a material or a lithographic printing plate. As the gelatin layer constituting the silver halide photographic light-sensitive material coated simultaneously with the undercoat second layer, in the case of a photosensitive surface such as a silver halide photosensitive layer and an overcoat layer, a backing layer such as an antihalation layer, The present invention can be applied to both cases where the surface opposite to the photosensitive surface such as an antistatic layer is applied. In any case, it is preferable that each layer contains gelatin. The gelatin layer constituting the lithographic printing plate may be an undercoat layer (for example, a layer having an antihalation function or a cushioning function), a photosensitive surface such as a silver halide photosensitive layer, a physical development nucleus layer, or an antihalation layer. The present invention can be applied to both the case where coating is performed on the surface opposite to the photosensitive surface such as a backing layer such as a layer and an antistatic layer. In any case, it is preferable that each layer contains gelatin.
[0061]
The advantage in the above embodiment is that in the case of carrying out a single layer subbing process comprising a hydrophobic latex and an emulsion, compared with the case of producing the above two-layer subbing polyester support, Since the undercoat agent can be applied before or during the process, the application width can be made narrower than after stretching, which has the advantage of ensuring uniform application. Therefore, it is preferable for the reason that a separate coating and drying device required for the two-layer subbing is unnecessary.
[0062]
The reason why the second subbing layer containing gelatin can be processed simultaneously with the production of the silver halide photographic light-sensitive material or the lithographic printing plate is that the self-emulsifiable isocyanate compound in the gelatin subbing layer forms the subbing layer. This is because it sometimes works effectively without performing any heat treatment and exhibits sufficient adhesion performance required as an undercoat layer. As the isocyanate compound, various blocked isocyanates that can be added to the aqueous coating solution are listed as conventional techniques, and can also be found in JP-A-4-184335. However, when a blocked isocyanate is used, Since the isocyanate group is protected to keep the isocyanate group stable, heating of about 100 ° C. or higher is usually required to remove the protecting group and regenerate the activity of the isocyanate group. As can be seen in the examples described later, the adhesiveness of the film crosslinked by this may be inferior to that of the self-emulsifiable isocyanate compound according to the present invention.
[0063]
The silver halide used in the silver halide photographic light-sensitive material of the present invention or the silver halide emulsion of a lithographic printing plate is not particularly limited, but a surface latent image type silver halide emulsion is preferred. Silver chloride, silver chlorobromide, silver chloroiodobromide, silver iodobromide, silver bromide and the like can be used. When silver chloroiodobromide or silver iodobromide is used, the silver iodide content is preferably in the range of 5 mol% or less. The form, crystal habit, size distribution, etc. of the silver halide grains are not particularly limited, but those having a grain size of 0.7 microns or less are preferred. Silver halide emulsions include gold compounds such as chloroaurate and gold trichloride, sulfur compounds that react with noble metal salts such as rhodium and iridium and silver salts to form silver sulfide, stannous salts, Sensitivity can be increased without reducing the size of particles with a reducing substance such as amines. Further, iron compounds such as salts of noble metals such as rhodium and iridium and red blood salts may be present during physical ripening or nucleation of silver halide grains.
[0064]
In the present invention, the surface latent image type halogenated emulsion means an emulsion composed of silver halide grains having a surface sensitivity higher than the internal sensitivity, and this emulsion is preferably disclosed in US Pat. No. 4,224,401. It has a difference between the surface sensitivity and the internal sensitivity specified in. The silver halide emulsion is desirably monodispersed, and an emulsion having the monodispersibility defined in the above-mentioned US Pat. No. 4,224,401 is particularly preferable. The silver halide emulsion used in the present invention preferably contains a water-soluble rhodium salt (for example, rhodium dichloride, rhodium trichloride, rhodium hexachloride (III) potassium, rhodium (III) ammonium chloride). . The addition amount of the rhodium salt is preferably 1 × 10 −7 mol to 1 × 10 −4 mol per mol of silver halide. The average grain size of the silver halide used in the present invention is preferably 0.7 microns or less, particularly preferably in the range of 0.1 to 0.4 microns. The silver halide grains may have a regular shape such as a cube or octahedron, or a mixed crystal shape, but is preferably a so-called monodisperse emulsion having a relatively narrow grain size distribution. The monodispersed emulsion as used herein refers to an emulsion in which 90%, more preferably 95% of the total number of grains falls within a grain size range of ± 40% of the average grain size. The form of reacting the soluble silver salt and the soluble halogen salt for the preparation of the silver halide emulsion in the present invention is any of a single jet method, a double jet method, a back mixing method formed in the presence of excessive silver ions, etc. Although a means may be used, for the purpose of the present invention, a double jet method in which a soluble silver salt and a soluble halogen salt are simultaneously added in an acidic solution to form particles is particularly preferred. The silver halide emulsion prepared in this manner may or may not be chemically sensitized. When chemically sensitizing, normal sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization, etc. Is used.
[0065]
The silver halide emulsion used in the present invention may be spectrally sensitized with methine dyes or the like. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to cyanine dyes, merocyanine dyes, and complex merocyanine dyes. These sensitizing dyes may be used alone or in combination. A combination of sensitizing dyes is often used for the purpose of supersensitization. In addition to the sensitizing dye, the emulsion itself may contain a dye that does not have spectral sensitization or a substance that does not substantially absorb visible light and exhibits supersensitization.
[0066]
In the silver halide photographic light-sensitive material of the present invention, a hydrazine compound may be contained in the silver halide emulsion layer, and a new aqueous colloid layer adjacent to the surface latent image type silver halide emulsion layer is contained. You may do it. Such a layer is a layer having any function as long as it does not prevent the hydrazine compound from diffusing into the silver halide grains, such as an undercoat layer, an intermediate layer, a filter layer, a protective layer, and an antihalation layer. There may be. The content of the hydrazine compound in the layer depends on the characteristics of the silver halide emulsion used, the chemical structure of the compound, and the development conditions, so that the appropriate content can vary over a wide range. A range of about 1.times.10@-6 to 1.times.10@-2 mole per mole of silver in the latent image type silver halide emulsion is practically useful. In addition to the hydrazine compound, an amine compound or a phosphonium compound, which is a high contrast accelerator, can be contained in the emulsion layer or other layers.
[0067]
When the hydrazine compound is contained in the silver halide emulsion layer, a conventional safelight dye may be added in the emulsion layer or other hydrophilic colloid layer. The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fogging during the production process, storage or photographic processing of the light-sensitive material, or stabilizing the photographic performance. That is, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, mercaptotetrazoles Many compounds conventionally known as antifoggants or stabilizers such as mercaptopyrimidines, mercaptotriazines, thioketo compounds, and azeindenes can be added. Among these, benzotriazoles (for example, 5-methylbenzotriazoles) and nitroindazoles (for example, 5-nitroindazole) are particularly preferable.
[0068]
Binder that can be used for the silver halide emulsion layer, intermediate layer, protective layer, backing layer, or undercoat layer of the lithographic printing plate, silver halide emulsion layer, back coat layer, etc. of the silver halide photographic light-sensitive material of the present invention Alternatively, gelatin is advantageously used as the protective colloid, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives, polyvinyl alcohol A variety of synthetic hydrophilic polymer materials such as mono- or copolymers of polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacramide, polyvinylimidazole, etc. I can do it. As gelatin, lime-processed gelatin, acid-processed gelatin, Bull. Soc. Sci. Photo. Japan, no. 16, p. 30 (1966) may be used, and a hydrolyzate or enzyme degradation product of gelatin can also be used.
[0069]
The photographic light-sensitive material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer. For example, chromium salts (chromium alum etc.), aldehydes (formaldehyde, glyoxal etc.), N-methylol compounds, dioxane derivatives (2,3-dihydroxydioxane etc.), active vinyl compounds, active halogen compounds (2,4-dichloro-6) -Hydroxy-s-triazine etc.) can be used alone or in combination. The compounds described in Research Disclosure No. 17465, Sections XX to BD are added to the photosensitive silver halide emulsion layer or its adjacent layer for the purpose of increasing sensitivity, increasing contrast, or promoting development. I can do it. In particular, it is preferable to add polyethylene glycol or a derivative thereof.
[0070]
The photographic light-sensitive material used in the present invention can contain a water-insoluble or hardly soluble synthetic polymer degradation product in the photographic emulsion layer and other hydrophilic colloid layers for the purpose of improving dimensional stability. For example, alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, vinyl acetate, acrylonitrile, olefin, styrene, etc., alone or in combination, or acrylic acid, methacrylic acid, α , Β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, styrene sulfonic acid and the like can be used as a monomer component.
[0071]
In the lithographic printing plate of the present invention, the physical development nucleus layer present above the silver halide emulsion layer contains physical development nuclei. Physical development nuclei include fine metal particles such as silver, antimony, bismuth, cadmium, cobalt, nickel, lead, palladium, rhodium, gold, platinum, sulfides, polysulfides, selenides of these metals, or their A mixture or a mixed crystal may be used. The physical development nucleus may not contain a hydrophilic binder, but various gelatin derivatives such as gelatin, starch, dialdehyde starch, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, gum arabic, sodium alginate, and other polysaccharides Polymer, polyacrylamide (and its copolymer), polyacrylic acid (and its copolymer), polyvinylpyrrolidone (and its copolymer), other various synthetic water-soluble polymers, etc. can be added. The content is preferably 0.5 g to 3 g or less per square meter. Further, the physical development nucleus layer may contain a developing agent such as hydroquinone, methylhydroquinone and catechol, and formalin and other known hardeners.
[0072]
To the undercoat layer (layer having antihalation function, cushioning function, etc.) according to the present invention, it is also preferable to add various hydrophobic latexes and emulsions as exemplified above in addition to gelatin. Further, pigments such as carbon black and various dyes are preferably added to prevent halation. Further, inorganic fine particles such as titanium oxide and silica are added as a matting agent, and various other photographic additives are also included. The description relating to such an undercoat layer can be found in JP-A-48-5503, JP-A-48-100203, JP-A-49-16507, JP-A-5-80518 and the like.
[0073]
The lithographic printing plate of the present invention may contain an inorganic or organic hardener in the undercoat layer, emulsion layer, physical development nucleus layer and other hydrophilic colloid layers. For example, chromium salts (chromium alum etc.), aldehydes (formaldehyde, glyoxal etc.), N-methylol compounds, dioxane derivatives (2,3-dihydroxydioxane etc.), active vinyl compounds, active halogen compounds (2,4-dichloro-6) -Hydroxy-s-triazine etc.) can be used alone or in combination. The compounds described in Research Disclosure No. 17465, Sections XX to BD are added to the photosensitive silver halide emulsion layer or its adjacent layer for the purpose of increasing sensitivity, increasing contrast, or promoting development. I can do it.
[0074]
The lithographic printing plate according to the present invention may contain a water-insoluble or hardly soluble synthetic polymer degradation product in the undercoat layer, emulsion layer and other hydrophilic colloid layers for the purpose of improving dimensional stability. For example, alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, vinyl acetate, acrylonitrile, olefin, styrene, etc., alone or in combination, or acrylic acid, methacrylic acid, α , Β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, styrene sulfonic acid and the like can be used as a monomer component.
[0075]
Next, the image material support of the present invention will be described. The support is a support in which a resin coating layer is provided on both sides of a paper substrate, and an undercoat layer is provided on the resin coating surface on the side on which the image recording layer is applied. The undercoat layer contains the above-mentioned ethylene oxide repeating unit and a self-emulsifiable isocyanate compound having two or more isocyanate groups.
[0076]
In the present invention, the above-mentioned self-emulsifiable isocyanate compound is used in the undercoat layer of a photographic support provided with a polyolefin resin coating together with various water-soluble polymers or latex emulsions. It has been found that it provides extremely good adhesiveness when it is coated on.
[0077]
The self-emulsifiable isocyanate compound according to the present invention has both a hydrophobic part and a hydrophilic part in its structure, so that it has an affinity for a hydrophobic polyolefin resin coating layer and an affinity for a hydrophilic photographic emulsion film. It is the feature that it has both of these, and it is the feature that a favorable adhesiveness is expressed in the interface of both. The subbing agent that can be used in this case is not particularly limited as long as it is a water-soluble polymer or water-dispersible latex emulsion capable of forming a crosslinked water-resistant film with isocyanate, and among them, gelatin, polyurethane emulsion, and hydrolyzable silyl group. In particular, a resin emulsion having a subbing layer obtained by coating and drying a subbing agent containing such a subbing resin and a self-emulsifying isocyanate on the surface of the polyolefin resin coating layer is used in the present invention. It is the feature.
[0078]
The paper substrate used in the practice of the present invention may be any of ordinary natural pulp paper, synthetic fiber paper, or so-called synthetic paper obtained by imitation of synthetic resin film, but softwood pulp, hardwood pulp, softwood hardwood mixed pulp Natural pulp paper mainly composed of wood pulp is advantageously used. Further, the thickness of the base paper is not particularly limited, but a base paper having good surface smoothness, such as compression by applying pressure with a calender after making the base paper is preferable, and its basis weight is 40 g / m.² ~ 250g / m² However, it is 40 g / m that the effect of the invention is particularly advantageously exhibited.² ~ 120g / m²It is.
[0079]
Various polymer compounds and additives can be contained in the paper base mainly composed of natural pulp which is advantageously used in the practice of the present invention. For example, starch derivatives, polyacrylamide, polyvinyl alcohol derivatives, dry paper strength enhancers such as gelatin, fatty acid salts, rosin derivatives, sizing agents such as dialkyl ketene dimer emulsions, melamine resins, urea resins, polyamide polyamine epichlorohydrin resins, etc. Wet paper strength enhancers, stabilizers, pigments, dyes, fluorescent brighteners, latexes, orientation electrolytes, pH adjusters, and the like can be included in appropriate combinations.
[0080]
The polyolefin resin used in the practice of the present invention is an olefin homopolymer such as low density polyethylene, medium density polyethylene, high density polyethylene, polypropylene, polybutene, polypentene, or two or more olefins such as ethylene-propylene copolymer. Copolymers and mixtures thereof having various densities and melt viscosity indexes (hereinafter simply referred to as MI) can be used alone or as a mixture thereof.
[0081]
In the polyolefin resin coating layer used in the practice of the present invention, white pigments such as titanium oxide, zinc oxide, talc and calcium carbonate, fatty acid amides such as stearamide, arachidic acid amide, stearamide, zinc stearate, stear Fatty acid metal such as calcium phosphate, aluminum stearate, magnesium stearate, zirconium octylate, sodium palmitate, calcium palmitate, sodium laurate, tetrakis [methylene-3 (3,5-di-tert-butyl-4-hydroxy Enyl) propionate] antioxidants such as methane, 2,6-di-tert-butyl-4-methylphenol, blue pigments and dyes such as cobalt blue, ultramarine blue, cerulean blue, phthalocyanine blue, cobalt violet Magenta pigments and dyes such as violet, fast violet and manganese purple, fluorescent brighteners such as bis (tert-butylbenzoxazole) thiophene, bis (methylbenzoxazole) naphthalene, tinuvin 320, tinuvin 326, tinuvin 328 (or more It is preferable to add various additives such as ultraviolet absorbers such as Geigy's trade name) in an appropriate combination.
[0082]
As a method for adding these additives to a resin, preferably a polyolefin resin, a melt mixing method using a heat kneading roll, a Banbury mixer, a kneader, a kneading extruder, etc. is optimal, and all the components are desired from the beginning. A compound containing only the composition ratio may be prepared and used, or a master batch containing each component at a high concentration may be prepared for each component and mixed in a desired ratio.
[0083]
The resin-coated paper used in the practice of the present invention is produced by a so-called extrusion coating method in which a heat-melted resin is cast on a normally running base paper, and preferably both surfaces thereof are coated with the resin. Further, before coating the resin, it is preferable to subject the base paper to an activation treatment, such as corona discharge treatment, flame treatment, etc. The emulsion-coated surface of the resin-coated paper has a glossy surface, matte surface, It has a silky surface and the like, and the back surface is usually a matte surface, and the surface can be subjected to activation treatment such as corona discharge treatment and flame treatment. Although there is no restriction | limiting in the thickness of the resin layer of resin-coated paper, Generally what was extruded and coated to the thickness of about 5 micrometers-30 micrometers is preferable.
[0084]
The photographic support, which is one of the image materials according to the present invention, is provided with various photographic composition layers for color photographic paper, for reverse color photographic paper, for black-and-white photographic paper, and for photosetting photographic paper. It can be used in various applications such as for computer-generated photoprinting paper, for copying photographic paper, for reversal photographic materials, for silver salt diffusion transfer method negatives and positives, and for printing materials.
[0085]
For example, a silver chloride, silver bromide, silver chlorobromide, silver iodobromide, or silver chloroiodobromide emulsion layer can be provided. A silver halide photographic emulsion layer can be provided with a color coupler to provide a multilayer silver halide constituent layer. In addition, a silver salt diffusion transfer image-receiving layer can be provided by containing physical development nuclei. As binders for these photographic constituent layers, hydrophilic polymer substances such as polyvinyl pyrrolidone, polyvinyl alcohol, and polysaccharide sulfate compounds can be used in addition to ordinary gelatin.
[0086]
The above photographic composition layer can contain various additives. For example, as sensitizing dye, cyanine dye, merocyanine dye, etc., as scientific sensitizer, water-soluble gold compound, sulfur compound, etc., as antifoggant or stabilizer, as hydroxytriazolopyrimidine compound, mercapto-heterocyclic compound, etc. Formalin, vinyl sulphone compounds, aziridine compounds, etc. as filming agents, benzene sulphonate, sulphosuccinate, etc. as coating aids, dialkyl hydroquinone compounds, etc. as contamination inhibitors, other fluorescent whitening agents, sharpness improving dyes In addition, an antistatic agent, a pH adjusting agent, a fogging agent, a water-soluble iridium, a water-soluble rhodium compound, and the like can be contained in appropriate combinations when producing and dispersing silver halide.
[0087]
The silver halide photographic material according to the present invention is exposed, developed, and stopped as described in “Photosensitive materials and handling methods” (Kyoritsu Publishing, Goro Miyamoto, Photographic Technology Course 2) according to the photographic material. Processing such as fixing, bleaching and stabilization is performed.
[0088]
Examples of gelatin used in the undercoat layer of the present invention include acid-treated gelatin, alkali-treated gelatin, modified gelatin, and enzyme-treated gelatin, but acid-treated gelatin is preferred. There are no particular restrictions on the jelly strength and calcium ion content of the gelatin used in the present invention, and any commonly available gelatin can be used without particular distinction.
[0089]
Examples of the polyurethane emulsion used in the undercoat layer of the present invention include self-emulsifying polyurethane emulsions described in, for example, U.S. Pat. Nos. 3,905,929, 3,020,598, 4,190,566, 4,594,385 and 5,433,381. However, it is not limited to the examples described in these, and generally a polyurethane emulsion having a hydroxyl group or a carboxyl group is preferably used.
[0090]
Examples of the emulsion having a hydrolyzable silyl group used in the undercoat layer of the present invention include, for example, JP-A-69-1463, JP-A-5-25354, JP-A-10-292023, and US Pat. As described in US Pat. Nos. 5,306,765 and 5,712,340, for example, a vinyl monomer having a hydrolyzable silyl group such as an alkoxysilyl group is polymerized by a method such as emulsion polymerization. It is characterized in that it is dispersed in the form of a stable emulsion in water, and in the dispersed state, since the silyl group is present inside the emulsion and is blocked from water, it is characterized by avoiding hydrolysis. However, when a coating film is formed, the emulsion breaks and the silyl group comes into contact with moisture, whereby hydrolysis proceeds and silanol groups are generated. Silanol groups self-condensate to form a crosslinked structure. In the present invention, silanol groups are bonded to each other by a compound having an isocyanate group.
[0091]
Examples of the hydrolyzable silyl group include an alkoxysilyl group, a thioalkoxysilyl group, a halogenosilyl group, an acyloxysilyl group, an amidosilyl group, an aminoxysilyl group, an alkenyloxysilyl group, an aminosilyl group, and an oximesilyl group. Of these, an alkoxysilyl group is particularly preferred.
[0092]
When a monomer or oligomer having a polymerizable double bond and a hydrolyzable silyl group is used as one of the methods for synthesizing a resin emulsion having a hydrolyzable silyl group, for example, vinylmethyldimethoxysilane is used as vinylsilane. , Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, etc., and (meth) acryloxyalkylsilanes include γ-methacryloxypropyltrimethoxysilane and γ-methacryloxypropylmethyldimethoxysilane. , Γ-acryloxypropyltrimethoxysilane and the like. Furthermore, examples of the oligomer include urethane oligomers, polyether oligomers, polyester oligomers, polyamide oligomers having a vinyl group and an alkoxysilyl group described in JP-A-60-26022.
[0093]
In the undercoat layer of the present invention, a surfactant, an antiseptic, a pH adjusting agent, a PH buffering agent, a gelatin hardener, an alcohol, and the like can be appropriately contained as necessary. It is preferable to add an anionic surfactant to improve the coatability of the emulsion. The coating amount (dry coating amount) of the undercoat layer of the present invention is 0.01 g / m²~ 2g / m²Preferably 0.03 g / m²~ 0.5g / m²It is.
[0094]
The coating method according to the present invention can be applied by generally well-known coating methods such as dip coating, air knife coating, curtain coating, and gravure coating. The liquid thus applied is subsequently dried in a drying step, and the conditions are 40 ° C. to 130 ° C. for 2 seconds to 3 minutes, but the temperature and time can be appropriately determined within this range.
[0095]
When applying the undercoat layer, it is desirable to activate the surface of the resin coating layer by a method such as corona treatment prior to application. The coated surface quality is preferably uniform. For this purpose, it is preferable to add a surfactant to the undercoat layer coating solution and apply a DC voltage to the surface of the resin-coated paper so as to reduce uneven charging.
[0096]
In silver halide photographic light-sensitive materials, especially in light-sensitive materials that use thin resin-coated paper-type supports, gelatin in the silver halide photographic light-sensitive layer expands and contracts due to changes in environmental humidity. However, in order to prevent curling, there is a problem that the hydrophilicity in the emulsion layer is opposite to the emulsion layer coating surface of the photographic support to prevent curling. In general, a backcoat layer is formed by aqueous coating mainly using gelatin as a binder in an amount commensurate with the amount of the conductive colloid. However, even when such a backcoat layer is provided on the resin-coated paper, an emulsion Naturally, it is preferable to form the undercoat layer as described above, similarly to the surface side.
[0097]
The resin-coated paper provided with the undercoat layer as described above is not limited to the use for silver halide photographic light-sensitive materials, but as described at the beginning, ink jet recording materials, heat-sensitive recording materials, sublimation heat transfer recording materials, light-sensitive heat-sensitive recording materials, etc. It can be used very preferably as a support for various image materials. In particular, when an ink receiving layer is provided as an ink jet recording material, it is extremely preferably used since the adhesion of the undercoat layer according to the present invention to a water-based coating layer usually composed of a hydrophilic resin, a pigment or the like is remarkably excellent. I can do it.
[0098]
Next, the printing sheet of the present invention will be described. The printing sheet of the present invention is provided with a coating layer on at least one side of a substrate, and contains the above-mentioned self-emulsifiable isocyanate compound having the ethylene oxide repeating unit and two or more isocyanate groups in the coating layer. It is characterized by that. This makes it possible to print with various printing inks, with excellent water resistance and ink adhesion, and with excellent offset printability that does not cause problems such as unevenness and curl even when using general-purpose offset inks. Is obtained.
[0099]
The self-emulsifiable isocyanate compound used in the printing sheet of the present invention is as described above. In the printing sheet, the above self-emulsifiable isocyanate compound is used together with various water-soluble polymers or latex emulsions in a coating layer provided on at least one side of the printing sheet, so that extremely good adhesion to printing ink is achieved. It has been found to give sex.
[0100]
The base material used for the printing sheet of the present invention mainly includes a paper-like sheet called a synthetic paper and a resin sheet. Synthetic paper is made from a polyolefin resin with an inorganic filler and a small amount of additives as raw materials, and is formed into a sheet while generating microvoids by biaxially stretched film molding. Is widely used because it is inexpensive and has excellent water resistance and chemical resistance. As the resin sheet, a sheet of polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polyester, polystyrene, or the like is used.
[0101]
The self-emulsifiable isocyanate compound according to the present invention has both a hydrophobic part and a hydrophilic part in its structure, so that it has an affinity for the surface of a printing sheet substrate such as a polyolefin resin, which is hydrophobic, and an affinity for a printing ink. It is a feature of the present invention that it has been found that it exhibits not only adhesion to the substrate and water resistance but also good adhesion at the interface between the two.
[0102]
Even when the above self-emulsifiable isocyanate is applied alone to the surface of the printing sheet, the object of the present invention is achieved to some extent, but further optimization is performed depending on the intended printing method and type of printing ink. The coating layer is preferably provided on the surface of the printing sheet using a coating agent according to each case, that is, a coating agent in which various water-soluble resins or latex emulsions are blended together with a self-emulsifying isocyanate.
[0103]
The coating agent that can be used in this case is not particularly limited as long as it is a water-soluble polymer or a water-dispersible latex emulsion capable of forming a crosslinked water-resistant film with isocyanate, and among them, gelatin, polyurethane emulsion, and hydrolyzable silyl group may be used. A resin emulsion having a coating layer in which a coating layer obtained by coating and drying a coating agent containing a coating layer resin and a self-emulsifiable isocyanate on the surface of the printing sheet substrate is a feature of the present invention. .
[0104]
Examples of gelatin used in the coating layer of the present invention include acid-treated gelatin, alkali-treated gelatin, modified gelatin, and enzyme-treated gelatin. Acid-treated gelatin is preferred. There are no particular restrictions on the jelly strength and calcium ion content of the gelatin used in the present invention, and any commonly available gelatin can be used without particular distinction.
[0105]
The printing sheet provided with a coating layer containing gelatin and a self-emulsifying isocyanate as described above has a characteristic that the adhesiveness with a water-based gravure ink is remarkably excellent. Furthermore, since the cross-linked gelatin layer is excellent in solvent resistance and solvent barrier property, it can be used very preferably because it can effectively prevent the ink solvent from penetrating into the substrate even in offset printing.
[0106]
As another preferred example of the polyurethane emulsion used in the coating layer of the present invention, as described in, for example, U.S. Pat. Examples of such self-emulsifying polyurethane emulsions are not limited to the examples described above, and generally polyurethane emulsions having a hydroxyl group or a carboxyl group are preferably used.
[0107]
A printing sheet provided with a coating layer containing the above polyurethane emulsion and self-emulsifiable isocyanate is excellent in solvent resistance and solvent barrier properties, and has good adhesion to general-purpose offset inks. Can be used.
[0108]
Examples of the emulsion having hydrolyzable silyl groups used in the coating layer of the present invention as other preferred examples include, for example, JP-A-69-1463, JP-A-5-25354, and JP-A-10. As described in U.S. Pat. No. 2,920,23, U.S. Pat. Nos. 5,306,765 and 5,712,340, for example, a vinyl monomer having a hydrolyzable silyl group such as an alkoxysilyl group is used. This refers to a polymer that has been polymerized by a method such as emulsion polymerization and is dispersed in the form of a stable emulsion in water. In the dispersed state, the silyl group is blocked from water because it is present inside the emulsion, thus avoiding hydrolysis. It is a feature. However, when a coating film is formed, the emulsion breaks and the silyl group comes into contact with moisture, whereby hydrolysis proceeds and silanol groups are generated. Silanol groups self-condensate to form a cross-linked structure. In the present invention, silanol groups are bonded to each other by a compound having an isocyanate group without heating.
[0109]
Examples of the hydrolyzable silyl group include an alkoxysilyl group, a thioalkoxysilyl group, a halogenosilyl group, an acyloxysilyl group, an amidosilyl group, an aminoxysilyl group, an alkenyloxysilyl group, an aminosilyl group, and an oximesilyl group. Of these, an alkoxysilyl group is particularly preferred.
[0110]
When a monomer or oligomer having a polymerizable double bond and a hydrolyzable silyl group is used as one of the methods for synthesizing a resin emulsion having a hydrolyzable silyl group, for example, vinylmethyldimethoxysilane is used as vinylsilane. , Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, etc., and (meth) acryloxyalkylsilanes include γ-methacryloxypropyltrimethoxysilane and γ-methacryloxypropylmethyldimethoxysilane. , Γ-acryloxypropyltrimethoxysilane and the like. Furthermore, examples of the oligomer include urethane oligomers, polyether oligomers, polyester oligomers, polyamide oligomers having a vinyl group and an alkoxysilyl group described in JP-A-60-26022.
[0111]
A printing sheet provided with a coating layer containing the above-mentioned hydrolyzable silyl group-containing resin emulsion and self-emulsifiable isocyanate can be preferably used for offset printing because of its excellent solvent resistance and solvent barrier properties. It is characterized by good adhesion to ink. Furthermore, since it has good adhesion to water-based gravure inks, it can preferably cope with a wide range of general printing methods including water-based gravure printing.
[0112]
The various coating layers described above are not particularly provided with an antistatic function. In order to impart an antistatic function including improvement of printability, which is another object of the present invention, it is particularly preferable to include a polymer antistatic agent in the coating layer together with the self-emulsifiable isocyanate.
[0113]
Here, the polymer antistatic agent specifically includes a water-soluble polymer containing a cationic group such as a quaternary ammonium base, a water-soluble polymer containing an anionic group such as a sulfonate group, or an oxyethylene group. A nonionic water-soluble polymer containing a substituent such as those having a weight average molecular weight in the range of 1,000 to 1,000,000 can be preferably used.
[0114]
Among the above-mentioned polymer antistatic agents, those that are crosslinked and water-resistant with self-emulsifying isocyanates are particularly preferred, and water-soluble polymers having substituents such as hydroxyl groups and carboxyl groups in addition to the above functional groups. Can be used very preferably. Although the preferable example of a polymeric antistatic agent is shown in Chemical formula 1, the effect of this invention is not limited to these examples. In Chemical Formula 1, the numbers represent parts by weight.
[0115]
[Chemical 1]

[0116]
In the coating layer according to the present invention, a surfactant, an inorganic pigment, an organic pigment, a PH regulator, a PH buffer, other curing agents, an organic solvent such as alcohol, and the like can be appropriately included as necessary. As the surfactant, it is preferable to add a fluorine-based or anionic surfactant in order to improve the coating property of the coating agent. As inorganic pigments, especially when silica fine particles with a particle size of about 1 to 5 microns are added as silica fine particles, the slipperiness of the sheet itself is improved, so the paper feeding characteristics and paper discharge characteristics are improved, and the drying property of the printing ink is further improved. This is particularly preferable because it greatly improves. Besides these, various silica fine particles such as colloidal silica, vapor phase method silica and synthetic silica, various inorganic fine particles such as titanium oxide, alumina sol and zirconia sol, or organic pigments such as polymer beads are preferably added. .
[0117]
The coating method according to the present invention can be applied by generally well-known coating methods such as dip coating, air knife coating, curtain coating, and gravure coating. The liquid thus applied is subsequently dried in a drying step, and the conditions are from room temperature to 130 ° C. for 2 seconds to 3 minutes, but the temperature and time can be appropriately determined within this range. One of the features of the present invention is that no heat treatment is required when forming the coating layer, and heating is performed to dry the solvent in the drying after coating, When drying is possible only by air blowing (such as thin layer coating), heating may not be necessary.
[0118]
When applying the coating layer, it is desirable to activate the surface of the printing sheet base material by a method such as corona treatment prior to coating. It is preferable that the coated surface quality is uniform, and for that purpose, it is preferable to add a surfactant to the undercoat layer coating liquid, and to apply a DC voltage to the surface of the printing sheet substrate to reduce uneven charging. .
[0119]
The printing sheet according to the present invention is preferably 0.05 to 5 g / m in solid content (dry coating amount) on at least one side thereof.²It is provided in the range of. A more preferable range of the coating layer is 0.5 to 2 g / m.²It is. The solvent barrier property is improved as the thickness of the coating layer is increased. However, the adhesive property to ink can sufficiently exhibit its function even with the thickness of the above lower limit.
[0120]
【Example】
The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples as well as the effects. The part in an Example shows a weight part.
Example 1
An undercoat layer composed of a single layer having the following composition was provided on a polyethylene terephthalate film support having a thickness of 100 μm. The undercoat layer was applied and dried so that the dry film thickness was 0.2 μm.
[0121]
<Undercoat layer A-1>
Water-dispersed polyurethane emulsion (Permarin UA-200, manufactured by Sanyo Chemical Industries, Ltd.)
[0122]
<Undercoat layer A-2>
Contains 10% by weight solids of water-dispersed polyurethane emulsion (Permarin UA-200, manufactured by Sanyo Chemical Industries, Ltd.) and epoxy compound (Denacol EX-521, manufactured by Nagase Sangyo Co., Ltd.) To do.
[0123]
<Undercoat layer A-3>
A water-dispersed polyurethane emulsion (Permarin UA-200, manufactured by Sanyo Chemical Industries, Ltd.) and a block isocyanate compound (Elastolon BN-44, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) are 10 solids with respect to the polyurethane. Contains by weight.
[0124]
<Undercoat layer A-4>
A water-dispersed polyurethane emulsion (Permarin UA-200, manufactured by Sanyo Chemical Industries, Ltd.) and hexamethylol melamine are contained in a solid content of 10% by weight with respect to the polyurethane.
[0125]
<Undercoat layer A-5>
A water-dispersed polyurethane emulsion (Permarin UA-200, manufactured by Sanyo Chemical Industries, Ltd.) and a self-emulsifiable isocyanate compound (Duranate WB40-80, manufactured by Asahi Kasei Kogyo Seiyaku Co., Ltd.) in solid content Contains 10% by weight.
[0126]
<Undercoat layer A-6>
A water-dispersed polyurethane emulsion (Permarin UA-200, manufactured by Sanyo Chemical Industries, Ltd.) and a self-emulsifying isocyanate compound (Duranate WX-1741, manufactured by Asahi Kasei Kogyo Co., Ltd.) in solid content Contains 10% by weight.
[0127]
On the above 6 types of undercoat layers, a silver halide emulsion layer and an overcoat layer having the following composition were coated and dried to prepare a silver halide photographic light-sensitive material.
[0128]
<Silver halide emulsion layer>
A monodispersed silver chlorobromide emulsion (silver chloride 70 mol%) containing iridium and having an average particle diameter of 0.25 microns was prepared by a control double jet. Desalted by the flow curation method, washed with water, redissolved, and 6-methyl-4-hydroxy-1, 3, 3a, 7-tetrazaindene was 2 g / m.²In addition, 0.2 g / m of anhydro-5,5-dichloro-9-ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine hydroxydopyridinium was used as a sensitizing dye.²It added so that it might become. The emulsion thus obtained contained 2.5 g / m of gelatin.², Polyethylene glycol 0.1 g / m²Then, a surfactant was added, and then 2-hydroxy-4,6-dichloro-1,3,5-triazine sodium salt was added as a hardener so as to be 1% by weight based on the total gelatin amount. Silver amount 3.5g / m²It applied so that it might become.
[0129]
<Overcoat layer>
Gelatin (1 g / m²), A surfactant, and 2-hydroxy-4,6-dichloro-1,3,5-triazine sodium salt (based on 3% by weight of gelatin).
[0130]
Each silver halide photographic light-sensitive material produced as described above was heated at 40 ° C. for 7 days. About each sample obtained in this way, the adhesiveness in an alkaline solution was evaluated.
[0131]
<Adhesion test with alkaline solution>
Using a cutter knife on the coated surface, make a 1cm square lattice-shaped scratch, soak in a 3N aqueous sodium hydroxide solution for 10 minutes, and then rub the surface strongly with absorbent cotton soaked in water. The adhesion of was evaluated. The case where peeling of the silver halide emulsion layer occurred by rubbing the film surface was evaluated as x, the case where partial peeling occurred was evaluated as △, and the case where no peeling was observed was evaluated as ◯. Each evaluation result is shown in Table 1.
[0132]
[Table 1]

[0133]
As can be seen from the above results, the subbing layers A-5 and A-6 using the self-emulsifiable isocyanate compound of the present invention exhibit excellent adhesiveness in an alkaline solution despite being a single layer.
[0134]
Example 2
Except for replacing the water-dispersed polyurethane emulsion in the undercoat layer of Example 1 with a different type of water-dispersed polyurethane emulsion (Permarin UA-310, manufactured by Sanyo Chemical Industries, Ltd.), exactly the same as Example 1, Undercoat layers B-1 to B-6 were prepared and applied onto a polyethylene terephthalate film support and dried. Subsequently, a silver halide emulsion layer and an overcoat layer were applied in the same manner as in Example 1 to produce a silver halide photosensitive material. In the same manner as in Example 1, adhesion with an alkaline solution was tested. As a result, the samples using the comparative undercoat layers B-1 to B-4 had film peeling, but the samples using the undercoat layers B-5 and B-6 of the present invention were not film peeled at all. There was no.
[0135]
Example 3
Except for substituting the water-dispersed polyurethane emulsion of the undercoat layer of Example 1 with vinylidene chloride latex (L536B manufactured by Asahi Kasei Kogyo Co., Ltd., vinylidene chloride ratio of 90% or more, hydroxyl group-modified latex), exactly the same as Example 1. Undercoat layers C-1 to C-6 were prepared, applied onto a polyethylene terephthalate film support, and dried. Subsequently, a silver halide emulsion layer and an overcoat layer were applied in the same manner as in Example 1 to produce a silver halide photosensitive material. In the same manner as in Example 1, adhesion with an alkaline solution was tested. As a result, the sample using the comparative undercoat layers C-1 to C-4 had film peeling, but the samples using the undercoat layers C-5 and C-6 of the present invention were totally film peeled. There was no.
[0136]
Example 4
Next, an example for demonstrating the superiority of the present invention in the undercoat two-layer structure will be shown. When forming a 100 μm-thick polyethylene terephthalate film, the first subbing layer made of vinylidene chloride latex (Asahi Kasei Kogyo Co., Ltd., L536B, vinylidene chloride ratio 90% or more, hydroxyl group-modified latex) is dried to a thickness of 0.1 microns. Inline coated. On this undercoat first layer, an undercoat second layer shown in Table 2 below was further applied so that the dry film thickness was 0.3 μm and dried to prepare a polyethylene terephthalate film support. In addition, the compound A contained in the undercoat second layer is 10% by weight with respect to the resin. A support obtained by further heat-treating the obtained support for 3 minutes in a drier adjusted to 120 ° C. or 150 ° C. was also prepared.
[0137]
Next, the silver halide emulsion layer and the overcoat layer of Example 1 were applied and dried on the above various supports to produce a silver halide photographic light-sensitive material. These samples were heated at 40 ° C. for 7 days and then evaluated for alkaline liquid adhesion and dimensional stability.
[0138]
Regarding dimensional stability, each sample was cut into a width of 30 cm and a length of 60 cm, and after conditioning for 2 hours at a temperature and humidity of 20 ° C. and 20%, 10 fine lines were formed at an interval of 5 cm using a contact printer. Evaluate by measuring the deviation of the fine line from the original after creating a sample that has been exposed to close contact with the drawn film original, developing a sample, and then adjusting the humidity for 2 hours at the same temperature and humidity Went. The numerical value shows the deviation between corresponding fine lines developed on the sample with respect to the width of 50 cm of the original in micron units. The smaller the value, the better. The evaluation results are shown in Table 2.
[0139]
[Table 2]

WB-40: Self-emulsifiable isocyanate compound (Duranate WB40-80, manufactured by Asahi Kasei Kogyo Co., Ltd.)
WX1741: Self-emulsifying isocyanate compound (Duranate WX-1741, manufactured by Asahi Kasei Kogyo Co., Ltd.)
Epoxy: Denacol EX-521 (Nagase Sangyo Co., Ltd.)
Block isocyanate: Elastron BN-44 (Daiichi Kogyo Seiyaku Co., Ltd.)
[0140]
As is clear from the above results, the present invention exhibits high adhesion even without heat treatment. On the other hand, in comparison, adhesion is not imparted without heat treatment, and it is still insufficient even after heat treatment. Further, the present invention is superior in dimensional stability as compared with the comparison.
[0141]
Example 5
Example 5 was repeated, except that the vinylidene chloride latex of the undercoat first layer of Example 4 was replaced with a water-dispersed polyurethane emulsion (Permarin UA-310, manufactured by Sanyo Chemical Industries, Ltd.). As a result, the same result as in Example 4 was obtained.
[0142]
Example 6
Underlying polyester film coated with polyethylene terephthalate film surface coated with vinylidene chloride latex (Asahi Kasei Kogyo Co., Ltd., L536B, vinylidene chloride ratio 90% or more, hydroxyl group-modified latex) to a dry coating thickness of 0.1 microns as a support A silver halide photographic light-sensitive material was prepared by coating each of the coating layers shown in the following formulation in this order.
[0143]
(1) Undercoat layer
3 parts of gelatin
WB40-80 0.04 parts
97 parts of water
In the above formulation, WB40-80 is an example of a self-emulsifiable isocyanate compound according to the present invention, and is obtained from Asahi Kasei Corporation as deuranate WB40-80. Diluted in Apply the above undercoat layer coating liquid to a moisture application amount of 10 g / m²(Dry film thickness was about 0.3 μm).
[0144]
(2) Silver halide emulsion layer
In the formulation of the emulsion layer, a monodispersed silver chlorobromide emulsion (70 mol% of silver chloride) containing iridium and having an average particle diameter of 0.25 microns was prepared by a control double jet. Desalted by the flow curation method, washed with water, redissolved, and 6-methyl-4-hydroxy-1, 3, 3a, 7-tetrazaindene was 2 g / m.²In addition, 0.2 g / m of anhydro-5,5-dichloro-9-ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine hydroxydopyridinium was used as a sensitizing dye.²It added so that it might become. The emulsion thus obtained contained 2.5 g / m of gelatin.², Polyethylene glycol 0.1 g / m²Then, the above-mentioned WB40-80 was added as a hardener according to the present invention to 8% by weight based on the total gelatin amount.
[0145]
As a hardener contained in the above undercoat layer and emulsion layer, the same amount of formalin or sodium salt of 2-hydroxy-4,6-dichloro-1,3,5-triazine was added instead of WB40-80. Except that, Comparative Sample 1 (Formalin) and Comparative Sample 2 (2-hydroxy-4,6-dichloro-1,3,5-triazine sodium salt) were prepared.
[0146]
Apply the above silver halide emulsion layer on the surface of the undercoat so that the amount of coated silver is 4 g per square meter, set it with cold air, and then dry it in a blow dryer set at 35 ° C or 70 ° C. I let you. The obtained photographic material sample was image-exposed using a xenon sensitometer, subjected to normal development processing, and the maximum image density (Dmax) and the background density (Dmin) were determined by measuring the transmission density. Furthermore, a 1 cm square grid-like scratch was made on the emulsion coating surface using a cutter knife, immersed in a 3N aqueous sodium hydroxide solution for 10 minutes, and then the surface was rubbed strongly with absorbent cotton soaked in water. The adhesion with the support was evaluated. The case where the photosensitive layer was peeled off by rubbing the film surface was rated as x, the case where it was partially peeled was marked as Δ, and the case where no peeling was observed was marked as ○. The respective evaluation results are shown in Table 3. As can be seen from the results in Table 3, Dmin does not increase in the sample to which WB40-80 was added even under high temperature drying conditions at 70 ° C., whereas in Comparative Samples 1 and 2, the Dmin clearly Increasing results were obtained. Furthermore, in terms of adhesion to the support, the comparative sample was easily peeled off in the alkaline aqueous solution, but the sample prepared in this example showed good adhesion. In this example, no influence on the photosensitive properties (sensitivity, tone, etc.) of the photosensitive material due to the presence or absence of the addition of the self-emulsifiable isocyanate compound (WB40-80) was observed. No effect was observed.
[0147]
[Table 3]

[0148]
  Reference example 1
  A support having a polyethylene terephthalate film coated with vinylidene chloride latex (Asahi Kasei Kogyo, L502, vinylidene chloride ratio 90% or more, carboxyl group-modified latex) in a dry coating thickness of 0.1 microns was prepared. On top of this, the coating solution of the present invention 1 (WB40-80), the coating solution of comparison 1 (formalin) or the coating solution of comparison 2 (2-hydroxy-4,6-dichloro-1) used as an emulsion layer in Example 6 was used. , 3,5-triazine sodium salt),Reference sample 1The photographic photosensitive materials of Comparative Sample 3 and Comparative Sample 4 were prepared. In this example, only the emulsion layer was coated on the latex subbing layer. Evaluation was performed in the same manner as in Example 6, and the results shown in Table 4 were obtained. Almost the same result as in Example 1 was obtained.
[0149]
[Table 4]

[0150]
Example 8
Permarine UA-200 (manufactured by Sanyo Kasei Kogyo Co., Ltd.) is used as a polyurethane emulsion on a polyethylene terephthalate film support, and WX-1741 (manufactured by Asahi Kasei Kogyo Co., Ltd.) is solid as a self-emulsifiable isocyanate compound against polyurethane. Using a subbing agent added so as to have a weight ratio of 10% by weight, coating and drying were carried out to obtain a dry film thickness of 0.2 microns. When the emulsion coating solution of the present invention 1 prepared in Example 6 was similarly coated, dried and evaluated, good results were obtained as in Example 6.
[0151]
Example 9
Permarin UA-150 (manufactured by Sanyo Kasei Kogyo Co., Ltd.) was used as a polyurethane emulsion on a polyethylene terephthalate film support, applied and dried to a dry film thickness of 0.2 micron, and subbing was performed. The undercoat layer coating solution in which WX-1741 (manufactured by Asahi Kasei Kogyo Co., Ltd.) as a self-emulsifiable isocyanate compound was added to gelatin so as to have a solid content ratio of 10% by weight and the present invention 1 prepared in Example 6 were used. The emulsion coating solution was simultaneously applied in multiple layers by the slide bead coating method and dried to prepare a photosensitive material. When development and adhesion evaluation were performed in the same manner as in Example 6, good results were obtained as in Example 6.
[0152]
Example 10
Next, in order to demonstrate the superiority of the present invention, a lithographic printing plate using a silver complex diffusion transfer method was subjected to the following examples.
In the same manner as in Examples 1 to 3, polyester film supports on which the undercoat layers A-1 to A-6, B-1 to B-6, and C-1 to C-6 were applied and dried were prepared.
[0153]
The following undercoat layer, silver halide emulsion layer, and physical development nucleus were coated on the support prepared above.
[0154]
<Undercoat layer (antihalation layer)>
Gelatin 35 parts
2-hydroxy-4,6-dichloro-1,3,5-triazine sodium salt 7 parts
200 parts of water
50 parts of titanium oxide (TR-1 manufactured by Sakai Chemical Co., Ltd.)
100 parts of water
Matting agent: 7.5 parts by Fuji Davidson Psyroid (grade 978)
Carbon black dispersion (solid content 30%) 8 parts
Surfactant 6 parts
Water was added to make a total of 600 parts.
[0155]
The undercoat layer (antihalation layer) coating solution was applied and dried with the solution so as to be 60 g per square meter. Further, the high-contrast silver chloride emulsion orthosensitized on the undercoat layer (antihalation layer) is converted to silver nitrate at 1.5 g per square meter (gelatin 0.8 g / m²) And dried. Formalin was used as a hardener in the silver halide emulsion layer. After drying, after heating in a drier adjusted to 50 ° C. for 2 days, lithographic printing is performed by applying a physical development nucleus solution and drying according to Example 1 described in JP-A-8-21614. Created a version.
[0156]
About the said lithographic printing plate, adhesiveness and printability were evaluated by the test method shown below. <Adhesion test>
Using a cutter knife on the coated surface, make a 1cm square lattice of scratches, immerse in 3N sodium hydroxide aqueous solution or dimethylformamide (DMF) for 10 minutes respectively, and then surface with absorbent cotton soaked in water The adhesiveness to the support was evaluated by rubbing strongly. The case where the photosensitive layer was peeled off by rubbing the film surface was rated as x, the case where it was partially peeled was marked as Δ, and the case where no peeling was observed was marked as ○.
[0157]
<Printing test>
After the lithographic printing plate is exposed according to the image, it is developed in the following developer at 30 ° C. for 30 seconds, followed by immersion in the following stop solution for 30 seconds (25 ° C.), and then squeezed to remove excess liquid. , Dried.
[0158]
Developer

[0159]
Stop solution
600 ml of water
Citric acid 10g
Sodium citrate 35g
Colloidal silica (20% solution) 5ml
Ethylene glycol 5ml
Add water to bring the total volume to 1 liter.
[0160]
The lithographic printing plate obtained by the plate making process is mounted on the offset printing machine Ryobi 3200CD, the plate surface is wiped with the following etching solution, and then the following moisturizing liquid and ink (F Nippon ink F gloss ink B and F gloss ink). It was printed using 紺 藍). The F gloss screen is one of inks that are liable to cause printing stains on the planographic printing plate. The temperature during printing was 22 ° C. and the humidity was 60%.
[0161]
Etching solution

[0162]
Moisturizer
10g of o-phosphoric acid
Nickel nitrate 5g
Sodium nitrite 5g
Ethylene glycol 100ml
Colloidal silica (20% solution) 28g
Add water to bring the total volume to 2 liters.
[0163]
The printability was evaluated from the degree of printing stain and printing durability. Regarding printing stains, a case where there was no stain at all was marked with ◯, a case where stains were partially generated was marked with △, and a case where stains occurred on the front surface was marked with ×. Regarding printing durability, ◯ indicates that normal printing can be performed on 20,000 copies or more, and X indicates that image loss or the like occurs in 5,000 copies or less, and △ indicates the middle between them. did. The test results are shown in Table 5.
[0164]
[Table 5]

[0165]
As is clear from the above results, the sample using the undercoat layer of the present invention exhibits excellent adhesion and printability regardless of the single layer undercoat.
[0166]
Example 11
A polyester film support having two undercoat layers as in Example 4 was produced. An undercoat layer, a silver halide emulsion layer, and a physical development nucleus layer were coated on these supports in the same manner as in Example 10 to prepare various lithographic printing plates. The lithographic printing plate thus prepared was evaluated for printing durability in the same manner as in Example 10. The results are shown in Table 6.
[0167]
[Table 6]

[0168]
From the above results, the present invention shows a high printing durability without heat treatment, while the comparison shows that the printing strength is low without heat treatment and the printing strength is improved by heat treatment, but the effect is small.
[0169]
Example 12
Example 11 was repeated except that the vinylidene chloride latex in the first subbing layer of Example 11 was replaced with a water-dispersed polyurethane emulsion (Permarin UA-310, manufactured by Sanyo Chemical Industries, Ltd.). As a result, the same result as in Example 11 was obtained.
[0170]
  Reference example 2
  Supports undercoated polyester film coated with polyethylene terephthalate film on the surface of vinylidene chloride latex (Asahi Kasei Kogyo Co., Ltd., L536B, vinylidene chloride ratio 90% or more, hydroxyl group-modified latex) to a dry coating thickness of 0.1 microns. Used as a body, an undercoat layer represented by the following formulation was applied thereon.
[0171]
Undercoat layer (antihalation layer)

Water was added to make a total of 600 parts. In the above formulation, WB40-80 is an example of a self-emulsifying isocyanate compound according to the present invention, and is obtained as Duranate WB40-80 from Asahi Kasei Kogyo Co., Ltd. Diluted in
[0172]
  The undercoat layer (antihalation layer) coating solution was applied onto the polyester film and dried so that the solution was 60 g per square meter. Further, the high-contrast silver chloride emulsion orthosensitized on the undercoat layer (antihalation layer) is converted to silver nitrate at 1.5 g per square meter (gelatin 0.8 g / m²) And dried. For the emulsion layer, formalin was used as a hardener. After drying, after heating in a drier adjusted to 50 ° C. for 2 days, according to Example 1 described in JP-A-8-21614, a physical development nucleus solution is applied and dried.Reference sample 1A lithographic printing plate was created.
[0173]
As a hardener contained in the undercoat layer (antihalation layer), the same amount of formalin or sodium salt of 2-hydroxy-4,6-dichloro-1,3,5-triazine is added instead of WB40-80. Except that, Comparative Sample 1 (formalin) and Comparative Sample 2 (2-hydroxy-4,6-dichloro-1,3,5-triazine sodium salt) were prepared.
[0174]
The lithographic printing plate obtained as described above is exposed through an optical wedge, the printing plate developed using the developer and stop solution of Example 10 is subjected to reflection density measurement using a normal optical densitometer, Sensitivity (S) and tone (gamma γ) were determined. The sensitivity was shown as a relative value with the value of the fresh sample of Comparative Sample 1 being 100. Further, in order to examine deterioration when stored under heating, the fresh plate material was heated at 50 ° C. for 6 days. Thereafter, the treatment was performed in the same manner as described above, and the sensitivity (S ′) and tone (γ ′) after the heating treatment were obtained. The results are shown in Table 7.
[0175]
[Table 7]

[0176]
  From the results in Table 7,For the undercoat layerIt was revealed that even when the self-emulsifiable isocyanate (WB40) was applied, the photographic properties and the storage stability were not adversely affected.
[0177]
  Further, an adhesion test and a printing test were performed in the same manner as in Example 10. The results are shown in Tables 8 and 9. From the results shown in Table 8, in terms of adhesion to the support, the comparative sample was easily peeled off in the alkaline aqueous solution.Reference sample 1Showed good adhesion. From Table 9,Reference sample 1It can be seen that the printing durability is superior to the comparison.
[0178]
[Table 8]

[0179]
[Table 9]

[0180]
  Example 14
  A polyethylene terephthalate film support was coated with a vinylidene chloride latex (Asahi Kasei Kogyo Co., Ltd., L502, vinylidene chloride ratio 90% or more, carboxyl group-modified latex) in a dry coating thickness of 0.1 micron. As a subbing layer, an undercoating coating solution prepared by adding WX-1741 (manufactured by Asahi Kasei Kogyo Co., Ltd.) as a self-emulsifying isocyanate to a 3% aqueous gelatin solution to a 0.3% solution was prepared, and the above-mentioned vinylidene chloride latex was prepared. The film was coated on the polyethylene terephthalate film sublimated in step 1 so as to have a dry coating thickness of 0.2 microns and dried to prepare a two-layer subbing polyethylene terephthalate film composed of a vinylidene chloride latex layer and a gelatin layer. Using this support,Reference example 2ofReference sample 1A sample was prepared by coating the undercoat layer (antihalation layer), emulsion layer and physical development nucleus layer shown in (2) in exactly the same manner (Invention 2). furtherReference example 2As in Comparative Samples 1 and 2 prepared in 1), the hardener in the undercoat layer (antihalation layer) was the same as the formalin and 2-hydroxy-4,6-dichloro-1,3,5-triazine sodium salt. Sample 3 of the present invention and sample 4 of the present invention were added.Reference example 2Evaluation was performed in the same manner as above, and the results shown in Table 10 were obtained. In this case, very good results were obtained for all samples with respect to adhesion and printability. This is due to the provision of an undercoat layer to which the self-emulsifiable isocyanate compound is added in advance on the polyester support.
[0181]
[Table 10]

[0182]
  Example 15
  Permarine UA-200 (Sanyo Kasei Kogyo Co., Ltd.) is used as a polyurethane emulsion on a polyethylene terephthalate film, and WX-1741 (Asahi Kasei Kogyo Co., Ltd.) is used as a self-emulsifiable isocyanate compound with respect to polyurethane. The subbing agent added so as to be 10% by weight was coated and dried so as to have a dry film thickness of 0.2 microns, and the subbing process was performed. to thisReference example 2ofReference sample 1The undercoating liquid (antihalation layer), emulsion coating liquid and physical development core coating liquid prepared in the same manner were applied, dried and evaluated.Reference example 2ofReference sample 1As well as good results.
[0183]
  Example 16
  Permarin UA-150 (manufactured by Sanyo Kasei Kogyo Co., Ltd.) was used as a polyurethane emulsion on a polyethylene terephthalate film support, applied and dried to a dry film thickness of 0.2 micron, and subbing was performed. Undercoat layer coating solution (dry film thickness is 0.3 micron) in which WX-1741 (manufactured by Asahi Kasei Kogyo Co., Ltd.) as a self-emulsifiable isocyanate compound is added to gelatin so that the solid content ratio is 10% by weight.Reference example 2ofReference sample 1Three layers of the undercoat (antihalation layer) coating solution and emulsion coating solution prepared in 1 were simultaneously applied by the slide bead coating method, dried, and further heated at 50 ° C. for 2 days.Reference example 2A lithographic printing plate was prepared by applying a physical development nucleus coating solution in the same manner as described above.Reference example 2The plate making process and adhesion evaluation were performed in the same way asReference example 2ofReference sample 1As well as good results.
[0184]
  Reference example 3
  Next, a support for image materialThe superiority of the following reference examplesWill be explained.
Basis weight 180g / m²LDPE containing titanium oxide and zinc stearate as the polyolefin resin layer on the side on which the undercoat layer of the paper substrate is provided 23 g / m²Apply LDPE and HDPE as the opposite resin layer, 50/50 ratio 20g / m²Painted. Further, the polyethylene surface on the side on which the undercoat layer is provided is subjected to corona discharge treatment, and then an undercoat layer coating solution according to the following formulation is applied with an air knife coater and dried at 120 ° C. to provide an undercoat layer and support for photography Created the body. The photographic support was run at 200 m / min, and ordinary monochrome and color emulsions were coated thereon for evaluation. The results are summarized in Table 9.
[0185]
<Reference sample 1Undercoat layer prescription>
  3 parts of gelatin
  WB40-80 0.3 parts
  96 parts of water
  Surfactant 1 part
[0186]
B40-80 0.3 part
96 parts of water
Surfactant 1 part
[0187]
The dry coating amount of the undercoat layer is 0.05 g / m.²It is. In the above formulation, WB40-80 is an example of a self-emulsifiable isocyanate compound according to the present invention, and is obtained as Deuranate WB40-80 from Asahi Kasei Corporation. It is diluted.
[0188]
<Reference sample 2Undercoat layer prescription>
  the aboveReference sample 1Instead of gelatin in the undercoat layer formulation, Permarin UA-150 (manufactured by Sanyo Chemical Industries) is used as a polyurethane emulsion, and the dry coating amount is 0.2 g / m.²Except for changing to WX-1741 (Asahi Kasei Kogyo Co., Ltd.) as a self-emulsifiable isocyanate compoundReference sample 1The same undercoat layer was provided.
[0189]
<Reference sample 3Undercoat layer prescription>
  Reference sample 1Except for using Sanmor SW-131 (manufactured by Sanyo Chemical Industries, Ltd., acrylic-silicon) as a resin emulsion having a hydrolyzable silyl group instead of gelatin in the undercoat layer formulation ofReference sample 1The same undercoat layer was provided.
[0190]
<Reference sample 4Undercoat layer prescription>
  Reference sample 1Except that hydroxypropyl cellulose (manufactured by Tokyo Chemical Industry Co., Ltd., 2% viscosity 3 to 6 cps) was used instead of gelatin in the subbing formulation ofReference sample 1The same undercoat layer was provided.
[0191]
<Undercoat layer formulation of Comparative Example 1>
  Reference sample 1Except for changing the self-emulsifiable isocyanate to formalin as a crosslinking agentReference sample 1The same undercoat layer was provided.
[0192]
<Undercoat layer formulation of Comparative Example 2>
  Reference sample 1Except that the self-emulsifiable isocyanate was changed to block isocyanate (Elastolone BN-44, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)Reference sample 1The same undercoat layer was provided.
[0193]
<Undercoat layer formulation of Comparative Example 3>
  Reference sample 2Except changing the self-emulsifiable isocyanate to epoxy (Denacol EX-521, manufactured by Nagase Sangyo Co., Ltd.)Reference sample 2The same undercoat layer was provided.
[0194]
<Undercoat layer formulation of Comparative Example 4>
  Reference sample 3Except that the self-emulsifiable isocyanate was changed to hexamethylolmelamine as a crosslinking agentReference sample 3The same undercoat layer was provided.
[0195]
About the sample produced as mentioned above, adhesiveness, photographic property, and preservability were evaluated. The results are shown in Table 11.
[0196]
The following tests were conducted as adhesion test methods. That is, a 1 cm square grid-shaped scratch was made on the surface coated with the emulsion layer using a cutter knife, immersed in a 1N aqueous sodium hydroxide solution (alkali adhesion test) for 10 minutes, and then water was added. Adhesion with the support was evaluated by rubbing the surface with absorbent cotton. The case where the surface layer was peeled off by rubbing the film surface was evaluated as x, the case where a part of the surface layer was peeled was evaluated as △, and the case where no separation was observed was evaluated as ◯.
[0197]
The evaluation of photographic properties is an evaluation of sensitivity and tone for ordinary monochrome photographic materials and color photographic materials, and evaluates whether photographic characteristics are affected by the type of undercoat layer. The case where no effect was observed in any of the sensitivity and tone was rated as ◯, and the case where even a slight effect was observed was marked as x.
[0198]
The storability was evaluated by humidifying the photographic support prepared by applying the undercoat layer at 50 ° C. in a storage chamber adjusted to 85% (relative humidity) for 2 weeks, and then returning to a normal temperature and normal humidity state. A black and white emulsion and a color emulsion were applied, and the same adhesive evaluation was performed as before, and the evaluation criteria were the same as above.
[0199]
[Table 11]

[0200]
  As above,A support for image material excellent in adhesion between the image forming layer and the resin-coated paper can be obtained, and in particular, a photographic support excellent in emulsion film adhesion and photographic properties can be obtained.
[0201]
  Reference example 4
  next,Advantages of printing sheetsThe following reference exampleWill be described.
Using synthetic paper (FPG-80 manufactured by Oji Oil Chemical Co., Ltd.) as a base material, a coating sheet was prepared by applying and drying a coating agent having the following formulation on the surface thereof.
[0202]
<Reference sample 1Coating formula for>
  10 parts of gelatin
  WB40-80 3 parts
  Silica (Mizukasil P526, average particle size 3 microns, manufactured by Mizusawa Chemical Co., Ltd.)
                            1 copy
  85 parts of water
  Surfactant 1 part
[0203]
The dry coating amount of the above coating agent is 2 g / m.²It is. In the above formula, WB40-80 is an example of a self-emulsifiable isocyanate compound according to the present invention, and is obtained as Deuranate WB40-80 from Asahi Kasei Kogyo Co., Ltd. Diluted in
[0204]
<Reference sample 2Coating formula for>
  Reference sample 1Instead of gelatin in the coating formulation, permarine UA-150 (manufactured by Sanyo Chemical Industries) is used as the polyurethane emulsion, and WX-1741 (manufactured by Asahi Kasei Corporation) is used as the self-emulsifiable isocyanate compound. The dry coating amount is 4 g / m²A printing sheet was prepared in the same manner except that the coating was dried.
[0205]
<Reference sample 3Coating formula for>
  Reference sample 1Except that Sanmor SW-131 (manufactured by Sanyo Chemical Industries, Ltd .; acrylic-silicon) was used as a resin emulsion having a hydrolyzable silyl group instead of gelatin in the coating formulation ofReference sample 1A printing sheet provided with the same coating layer as above was prepared.
[0206]
<Reference sample 4Coating formula for>
  Reference sample 1Except that hydroxypropyl cellulose (manufactured by Tokyo Chemical Industry Co., Ltd., 2% viscosity 3 to 6 cps) was used instead of gelatin in the coating formulation ofReference sample 1The same coating layer was provided.
[0207]
<Reference sample 5Coating formula for>
  Reference sample 1The polymer antistatic agent represented by P-1 in Chemical Formula 1 was used instead of gelatin in the coating agent formulation of 1 and the dry coating amount was 1 g / m.²Except forReference sample 1The same coating layer was provided.
[0208]
<Comparative Example 1>
As Comparative Example 1, the above synthetic paper was used as it was as a printing sheet without applying the coating agent.
[0209]
<Coating agent formulation of Comparative Example 2>
  Reference sample 1Except that the self-emulsifiable isocyanate was replaced with formalin as a crosslinking agent in the coating formulation ofReference sample 1The same coating layer was provided.
[0210]
<Coating agent formulation of Comparative Example 3>
  Reference sample 1Except that the self-emulsifiable isocyanate was replaced with a blocked isocyanate (Elastolon BN-44, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) as a crosslinking agent in the coating formulation ofReference sample 1The same coating layer was provided.
[0211]
<Coating agent formulation of Comparative Example 4>
  Reference sample 2Except that the self-emulsifiable isocyanate was replaced with epoxy (Denacol EX-521, manufactured by Nagase Sangyo Co., Ltd.) as a crosslinking agent in the coating formulation ofReference sample 2The same coating layer was provided.
[0212]
<Coating agent formulation of Comparative Example 5>
  Reference sample 3Except that the self-emulsifiable isocyanate was replaced with hexamethylolmelamine as a crosslinking agent in the coating formulation ofReference sample 3The same coating layer was provided.
[0213]
<Coating agent formulation of Comparative Example 6>
  Reference sample 5Except that the epoxy compound used in Comparative Example 4 was used instead of the isocyanate in the coating formulation ofReference sample 5The same coating layer was provided.
[0214]
The following evaluation was performed about the various printing sheets produced as mentioned above. The results are shown in Table 12.
[0215]
<Water-based gravure printing evaluation>
Using the printing sheet prepared as described above, Daiichi Seika Kogyo Co., Ltd. Hydric PEP was used as the aqueous gravure ink. The coating layer surface was applied and dried using an 8 doctor bar. Use a cutter knife on the coated surface to make a 5mm square grid-like scratch, apply adhesive tape ("Cellotape" manufactured by Nichiban Co., Ltd.), peel it off after fully pressing, and remove the ink. The degree was evaluated. The standard of evaluation is ◯ when no ink peeling was observed on the surface where the adhesive tape was peeled off, and △ when partial ink peeling was observed, when peeling occurred almost on the entire surface Was marked with x.
[0216]
<Offset printing evaluation>
The above printing sheet was printed using Ryobi 3200CD, an offset printing machine, and F gloss black B made by Dainippon Ink was used as printing ink. The temperature during printing was 22 ° C. and the humidity was 60%. In order to evaluate the adhesiveness to the ink of the sheet after offset printing, in the same manner as described above, a 5 mm square grid-shaped scratch was made on the printing surface using a cutter knife, and an adhesive tape (Nichiban Co., Ltd.) The product “cello tape”) was affixed and peeled after sufficiently pressing, and the degree of ink peeling was evaluated. The evaluation criteria are ○ when the ink peeling is not recognized at all on the surface where the adhesive tape is peeled off, △ when the ink peeling is partially recognized, and when the peeling occurs almost entirely Was marked with x.
[0217]
<Solvent barrier evaluation>
The sheet obtained by the above offset printing is cut into a 10 cm square on the printing surface immediately after printing, and left in a room adjusted to a temperature of 22 ° C. and a relative humidity of 60% for 24 hours, and the height of the four corners due to curling is measured. It was evaluated. The case where the curl height was 3 mm or less was rated as ◯, the case where it was 10 mm or more was rated as x, and the case where it was between them was marked as Δ.
[0218]
  Also,Reference sample 5For Comparative Example 6, the surface resistance value was further measured as an evaluation and used as a measure of antistatic performance. The evaluation results of antistatic performance are summarized in Table 13. In Table 13, the surface resistance value of a fresh sample is measured using a high resistance resistivity meter Hiresta IP manufactured by Mitsubishi Oil Chemical Co., Ltd. after conditioning the sample for 12 hours in a temperature and humidity atmosphere of 20 ° C. and 65%. It was measured. The measurement after washing with water in the measurement of the surface resistance value was carried out after washing the sample with warm water at 40 ° C. for 5 minutes, and after drying and conditioning at 20 ° C. and 65% temperature and humidity for 12 hours. Similarly, the surface resistance value was measured. Such water resistance evaluation was performed in order to evaluate the water-resistant adhesion between the substrate and the undercoat layer.
[0219]
[Table 12]

[0220]
[Table 13]

[0221]
<Reference sample6-10>
  A polyester film (100 micron PET film T100 manufactured by Diafoil Co., Ltd.) biaxially stretched and corona-treated on the surface is used as a printing substrate.Reference sampleA printing sheet was prepared by coating and drying on a polyester film with the coating agent and dry coating amount used in 1-5.Reference sampleEvaluation was performed in exactly the same manner as in 1 to 5, and the same results as those shown in Table 12 and Table 13 were obtained for the corresponding printing sheets. However, since the solvent resistance of the polyester film itself was high, the evaluation of the solvent barrier property was all “good”.
[0222]
  As above,Providing printing sheets with excellent printability with various printing inks, excellent water resistance and ink adhesion, and excellent offset printing aptitude that does not cause problems such as unevenness and curl even when general-purpose offset ink is used. A printable sheet is obtained.
[0223]
【The invention's effect】
The present invention provides a silver halide photographic light-sensitive material and a lithographic printing plate excellent in adhesion to a polyester film support. As the undercoat layer of the polyester film support, an undercoat layer having good adhesiveness is provided without performing heat treatment.
Further, it is possible to obtain an image material support excellent in the adhesion between the image forming layer and the resin-coated paper, and in particular, it is possible to obtain a photographic support excellent in emulsion film adhesion and photographic properties.
In addition, it provides printing sheets with excellent printability with various printing inks. Also, it has excellent water resistance and ink adhesion, and even with the use of general-purpose offset inks, it is suitable for offset printing. An excellent printing sheet can be obtained.

Claims (4)

A silver halide photographic light-sensitive material having at least a silver halide emulsion layer on an undercoat layer of a polyester film support, wherein the undercoat layer has an ethylene oxide repeating unit and two or more isocyanate groups. A silver halide photographic light-sensitive material comprising a gelatin-containing layer directly on the undercoat layer. 2. The silver halide photographic light-sensitive material according to claim 1 , wherein the undercoat layer comprises a single layer containing a hydrophobic latex or emulsion and a self-emulsifiable isocyanate compound having an ethylene oxide repeating unit and two or more isocyanate groups. The undercoat layer has a two-layer structure, the first layer on the polyester film support side is made of a hydrophobic latex or emulsion, and the second layer on the gelatin-containing layer side is a water-soluble polymer, an ethylene oxide repeating unit, and two or more The silver halide photographic material according to claim 1 , comprising a self-emulsifiable isocyanate compound having an isocyanate group. 4. The lithographic printing plate according to claim 1, wherein the gelatin-containing layer is an undercoat layer containing gelatin, and is used for a lithographic printing plate having at least a silver halide emulsion layer and a physical development nucleus layer on the undercoat layer. Silver halide photographic light-sensitive material.