JP3654007B2 - Silver halide photographic light-sensitive material and image forming method - Google Patents

Description

【００９４】
乳剤（１０１Ｒ）とは添加するチオ硫酸ナトリウムを２等分し、最初の添加から１０分経過した時点で他方を添加することのみ異なる乳剤（１０２Ｒ）を調製した。
【００９５】
乳剤（１０２Ｒ）とは、２等分したチオ硫酸ナトリウムの添加間隔が６０分であることのみ異なる乳剤（１０３Ｒ）を調製した。
【００９６】
乳剤（１０２Ｒ）とは、２等分したチオ硫酸ナトリウムの添加間隔が１００分であることのみ異なる乳剤（１０４Ｒ）を調製した。
【００９７】
乳剤（１０２Ｒ）とは、２等分したチオ硫酸ナトリウムの添加間隔が２００分であることのみ異なる乳剤（１０５Ｒ）を調製した。
【００９８】
乳剤（１０２Ｒ）とは、チオ硫酸ナトリウムを化学熟成２００分間に渡り、１分当たりの添加量を一定に保ちながら連続添加したことのみ異なる乳剤（１０６Ｒ）を調製した。
【００９９】
乳剤（１０２Ｒ）とはチオ硫酸ナトリウムではなく、塩化金酸を間隔を１０分おいて添加したことのみ異なる乳剤（１０７Ｒ）を調製した。
【０１００】
乳剤（１０３Ｒ）とはチオ硫酸ナトリウムではなく、塩化金酸を間隔を６０分おいて添加したことのみ異なる乳剤（１０８Ｒ）を調製した。
【０１０１】
乳剤（１０４Ｒ）とはチオ硫酸ナトリウムではなく、塩化金酸を間隔を１００分おいて添加したことのみ異なる乳剤（１０９Ｒ）を調製した。
【０１０２】
乳剤（１０５Ｒ）とはチオ硫酸ナトリウムではなく、塩化金酸を間隔を２００分おいて添加したことのみ異なる乳剤（１１０Ｒ）を調製した。
【０１０３】
乳剤（１０６Ｒ）とはチオ硫酸ナトリウムではなく、塩化金酸を化学熟成中２００分にわたり連続的に添加したことのみ異なる乳剤（１１１Ｒ）を調製した。
【０１０４】
（緑感性ハロゲン化銀乳剤の調製）
（Ａ液）と（Ｂ液）の添加時間及び（Ｃ液）と（Ｄ液）の添加時間を変更する以外はＥＭＰ−１と同様にして平均粒径０．４０μｍ、変動係数０．０８、塩化銀含有率９９．５％の単分散立方体乳剤ＥＭＰ−２を得た。次ぎに平均粒径０．５０μｍ、変動係数０．０８、塩化銀含有率９９．５％の単分散立方体乳剤ＥＭＰ−２Ｂを得た。
【０１０５】
上記ＥＭＰ−２に対し、下記化合物を用い５５℃にて最適に化学増感を行った。またＥＭＰ−２Ｂに対しても同様に最適に化学増感した後、増感されたＥＭＰ−２とＥＭＰ−２Ｂを銀量で１：１の割合で混合し、緑感性ハロゲン化銀乳剤（１０１Ｇ）を得た。
【０１０６】
チオ硫酸ナトリウム １×１０^-4／モルＡｇＸ
塩化金酸 １．２×１０^-4／モルＡｇＸ
安定剤 ＳＴＡＢ−１ ２．５×１０^-4モル／モルＡｇＸ
安定剤 ＳＴＡＢ−２ ３．１×１０^-4モル／モルＡｇＸ
安定剤 ＳＴＡＢ−３ ３．１×１０^-4モル／モルＡｇＸ
増感色素 ＧＳ−１ ４×１０^-4モル／モルＡｇＸ
【０１０７】
【化２】

【０１０８】
以下乳剤（１０２Ｒ）〜（１１１Ｒ）と同様にチオ硫酸ナトリウム、塩化金酸を分割添加した乳剤（１０２Ｇ）〜（１１１Ｇ）を調製した。
【０１０９】
（青感性ハロゲン化銀乳剤の調製）
（Ａ液）と（Ｂ液）の添加時間及び（Ｃ液）と（Ｄ液）の添加時間を変更する以外はＥＭＰ−１と同様にして平均粒径０．７１μｍ、変動係数０．０８、塩化銀含有率９９．５％の単分散立方体乳剤ＥＭＰ−３を得た。次ぎに平均粒径０．６４μｍ、変動係数０．０８、塩化銀含有率９９．５％の単分散立方体乳剤ＥＭＰ−３Ｂを得た。
【０１１０】
上記ＥＭＰ−３に対し、下記化合物を用い６０℃にて最適に化学増感を行った。またＥＭＰ−３Ｂに対しても同様に最適に化学増感した後、増感されたＥＭＰ−３とＥＭＰ−３Ｂを銀量で１：１の割合で混合し、青感性ハロゲン化銀乳剤（１０１Ｂ）を得た。
【０１１１】
チオ硫酸ナトリウム １×１０^-4モル／モルＡｇＸ
塩化金酸 １．２×１０^-4モル／モルＡｇＸ
安定剤 ＳＴＡＢ−１ ２×１０^-4モル／モルＡｇＸ
安定剤 ＳＴＡＢ−２ ２．４×１０^-4モル／モルＡｇＸ
安定剤 ＳＴＡＢ−３ ２．１×１０^-4モル／モルＡｇＸ
増感色素 ＢＳ−１ ４×１０^-4モル／モルＡｇＸ
増感色素 ＢＳ−２ １×１０^-4モル／モルＡｇＸ
【０１１２】
【化３】

【０１１３】
以下乳剤（１０２Ｒ）〜（１１１Ｒ）と同様にチオ硫酸ナトリウム、塩化金酸を分割添加した乳剤（１０２Ｂ）〜（１１１Ｂ）を調製した。
【０１１４】
坪量１８０ｇ／ｍ²の紙パルプの両面に高密度ポリエチレンをラミネートし、紙支持体を作製した。但し、乳剤層を塗布する側には、表面処理を施したアナターゼ型酸化チタンを１５重量％の含有量で分散して含む溶融ポリエチレンをラミネートし、反射支持体を作製した。この反射支持体をコロナ放電処理した後、ゼラチン下塗層を設け、さらに以下に示す構成の各層を塗設し、ハロゲン化銀写真感光材料（１０１）を作製する。塗布液は下記のごとく調製した。
【０１１５】
第１層塗布液
イエローカプラー（Ｙ−１）２３．４ｇ、色素画像安定化剤（ＳＴ−１）３．３４ｇ、（ＳＴ−２）３．３４ｇ、（ＳＴ−５）３．３４ｇ、ステイン防止剤（ＨＱ−１）０．３４ｇ、画像安定剤Ａ５．０ｇ、高沸点有機溶媒（ＤＢＰ）３．３３ｇおよび高沸点有機溶媒（ＤＮＰ）１．６７ｇに酢酸エチル６０ｍｌを加え溶解し、この溶液を２０％界面活性剤（ＳＵ−１）７ｍｌを含有する１０％ゼラチン水溶液２２０ｍｌに超音波ホモジナイザーを用いて乳化分散させてイエローカプラー分散液を作製した。この分散液を前記で作製した青感性ハロゲン化銀乳剤１０１Ｂと混合し第１層塗布液を調製した。
【０１１６】
第２層〜第７層塗布液も上記第１層塗布液と同様に表１および表２の塗布量になるように各塗布液を調製した。
【０１１７】
【表１】

【０１１８】
【表２】

【０１１９】
又、硬膜剤として（Ｈ−１）、（Ｈ−２）を添加した。塗布助剤としては、界面活性剤（ＳＵ−２）、（ＳＵ−３）を添加し、表面張力を調整した。また防腐剤ＤＩ−１を添加した。
【０１２０】
ＳＵ−１：トリ−ｉ−プロピルナフタレンスルホン酸ナトリウム
ＳＵ−２：スルホ琥珀酸ジ（２−エチルヘキシル）・ナトリウム塩
ＳＵ−３：スルホ琥珀酸ジ（２，２，３，３，４，４，５，５−オクタフルオロペンチル）・ナトリウム塩
ＤＢＰ ：ジブチルフタレート
ＤＮＰ ：ジノニルフタレート
ＤＯＰ ：ジオクチルフタレート
ＤＩＤＰ：ジ−ｉ−デシルフタレート
ＰＶＰ ：ポリビニルピロリドン
Ｈ−１ ：テトラキス（ビニルスルホニルメチル）メタン
Ｈ−２ ：２，４−ジクロロ−６−ヒドロキシ−ｓ−トリアジン・ナトリウム
画像安定剤Ａ：Ｐ−ｔ−オクチルフェノール
【０１２１】
【化４】

【０１２２】
【化５】

【０１２３】
【化６】

【０１２４】
【化７】

【０１２５】
【化８】

【０１２６】
このようにして感光材料試料（１０１）を作製した。
【０１２７】
更に、感光材料試料（１０１）において第１層、第３層、第５層の各感光性層に使用したハロゲン化銀乳剤を下記表３記載のように変えた他は感光材料試料（１０１）と同様にして、感光材料試料（１０２）〜（１１１）を作製した。
【０１２８】
【表３】

【０１２９】
このようにして作製した感光材料試料（１０１）〜（１１１）について、青光源にヘリウム・カドミウムレーザー（約４２２ｎｍ）、緑の光源としてはヘリウム・ネオンレーザー（約５４４ｎｍ）、赤の光源としてガリウムアルミニウム・砒素半導体レーザー（約７８０ｎｍ）を利用した光学系でビーム径が約８０μｍ、ポリゴンミラーを使用し走査速度１６０ｍ／秒、１画素当たりの露光時間は５×１０^-7秒の条件で下記３種類の露光を行った。
【０１３０】
▲１▼露光量を外部変調器により制御することによりグレー階調露光を１度施した試料及び２度施した試料
▲２▼濃度１．０のグレーパッチが得られるよう均一走査露光した試料
▲３▼濃度２．０となるように「Ａ」の文字をＨｅｌｖｅｔｉｃａ４ポイントから１８ポイントまで大きさを変えて露光した試料
これらを以下の条件で処理した。
【０１３１】

現像処理液の組成を下記に示す。
【０１３２】

水を加えて全量を１リットルとし、タンク液はｐＨ＝１０．１０に、補充液はｐＨ＝１０．６０に調整する。
【０１３３】
漂白定着液タンク液及び補充液
ジエチレントリアミン五酢酸第二鉄アンモニウム２水塩 ６５ｇ
ジエチレントリアミン五酢酸 ３ｇ
チオ硫酸アンモニウム（７０％水溶液） １００ｍｌ
２−アミノ−５−メルカプト−１，３，４−チアジアゾール ２．０ｇ
亜硫酸アンモニウム（４０％） ２７．５ｍｌ
水を加えて全量を１リットルとし、炭酸カリウム又は氷酢酸でｐＨ＝５．０に調整する。
【０１３４】
安定化液タンク液及び補充液
ｏ−フェニルフェノール １．０ｇ
５−クロロ−２−メチル−４−イソチアゾリン−３−オン ０．０２ｇ
２−メチル−４−イソチアゾリン−３−オン ０．０２ｇ
ジエチレングリコール １．０ｇ
蛍光増白剤（チノパールＳＦＰ） ２．０ｇ
１−ヒドロキシエチリデン−１，１−ジホスホン酸 １．８ｇ
塩化ビスマス（４５％水溶液） ０．６５ｇ
硫酸マグネシウム・７水塩 ０．２ｇ
ＰＶＰ １．０ｇ
アンモニア水（水酸化アンモニウム２５％水溶液） ２．５ｇ
ニトリロ三酢酸・三ナトリウム塩 １．５ｇ
水を加えて全量を１リットルとし、硫酸又はアンモニア水でｐＨ＝７．５に調整する。
【０１３５】
（多重露光適性評価）
▲１▼の露光及び上記発色現像を施した試料（１０１）〜（１１１）において、濃度０．５と１．５の間で露光量に対する濃度変化の傾きγをイエロー、マゼンタ、シアンの各々について１回露光での傾きγ１に対する２回露光での傾きγ２の変化率の絶対値を下記のようにして算出し、表４に示した。
【０１３６】
階調変動率（％）＝｛｜γ２―γ１｜／γ１｝×１００
（グレー濃度１．０での濃度ムラ評価）
▲２▼の露光及び上記発色現像を施した試料（１０１）〜（１１１）において、目視での画像ムラを以下の基準で評価した。
【０１３７】
◎：画像ムラはみられない
○：画像ムラがややみられる
△：画像ムラがみられる
×：画像ムラがはっきりとみられる。
【０１３８】
（細線の明瞭さ評価）
▲３▼の露光及び上記発色現像を施した試料（１０１）〜（１１１）について、細線の明瞭さを以下の基準で評価した。
【０１３９】
◎：グレーの細線が明確に区別できる
○：グレーの細線がはっきりと区別できるが輪郭がややぼける
△：グレーの細線の輪郭がぼやけるが区別できる
×：グレーの細線がぼやけ、区別できない。
【０１４０】
表４に結果を示す。
【０１４１】
【表４】

【０１４２】
表４から明らかなように、比較となる試料（１０１）に対して化学増感剤の添加間隔を１０分とした試料（１０２）、（１０７）では多重露光による階調の変動幅が小さくなり、多重露光適性改良効果が得られ、またグレー濃度１．０での濃度安定性も向上していることがわかる。しかし、細線の明瞭さの点では改良効果が不十分である。これに対して添加間隔をひろげた試料（１０３）〜（１０６）、（１０８）〜（１１１）では増感剤種に依らず、添加間隔が１０分では改良できなかった細線明瞭さも改良できることがわかった。
【０１４３】
実施例２
（赤感光性乳剤の調製）
実施例１の試料（１０１）に適用される乳剤（１０１Ｒ）とは、添加する塩化金酸の添加量を同量にして、チオ硫酸ナトリウムの添加量をモル数で塩化金酸の１．３倍量添加し、適切な写真感度が得られるように安定化剤ＳＴＡＢ−１〜ＳＴＡＢ−３の添加量を最適化したことが異なる乳剤（２０１Ｒ）を調製した。
【０１４４】
試料（１０１）に適用される乳剤（１０１Ｒ）とは、添加する塩化金酸の添加量を同量にして、チオ硫酸ナトリウムの添加量をモル数で塩化金酸の１倍量添加し、適切な写真感度が得られるように安定化剤ＳＴＡＢ−１〜ＳＴＡＢ−３の添加量を最適化したことが異なる乳剤（２０２Ｒ）を調製した。
【０１４５】
試料（１０１）に適用される乳剤（１０１Ｒ）とは、添加する塩化金酸の添加量を同量にして、チオ硫酸ナトリウムの添加量をモル数で塩化金酸の０．８倍量添加し、適切な写真感度が得られるように安定化剤ＳＴＡＢ−１〜ＳＴＡＢ−３の添加量を最適化したことが異なる乳剤（２０３Ｒ）を調製した。
【０１４６】
試料（１０１）に適用される乳剤（１０１Ｒ）とは、添加する塩化金酸の添加量を同量にして、チオ硫酸ナトリウムの添加量をモル数で塩化金酸の０．６倍量添加し、適切な写真感度が得られるように安定化剤ＳＴＡＢ−１〜ＳＴＡＢ−３の添加量を最適化したことが異なる乳剤（２０４Ｒ）を調製した。
【０１４７】
試料（１０１）に適用される乳剤（１０１Ｒ）とは、添加する塩化金酸の添加量を同量にして、チオ硫酸ナトリウムの添加量をモル数で塩化金酸の０．４倍量添加し、適切な写真感度が得られるように安定化剤ＳＴＡＢ−１〜ＳＴＡＢ−３の添加量を最適化したことが異なる乳剤（２０５Ｒ）を調製した。
【０１４８】
試料（１０１）に適用される乳剤（１０１Ｒ）とは、添加する塩化金酸の添加量を同量にして、チオ硫酸ナトリウムの添加量をモル数で塩化金酸の０．３倍量添加し、適切な写真感度が得られるように安定化剤ＳＴＡＢ−１〜ＳＴＡＢ−３の添加量を最適化したことが異なる乳剤（２０６Ｒ）を調製した。
【０１４９】
（緑感光性乳剤の調製）
赤感光性乳剤（２０１Ｒ）〜（２０６Ｒ）と同様に実施例１の試料（１０１）に適用される乳剤（１０１Ｇ）に対して塩化金酸とチオ硫酸ナトリウムの添加量比を変化させて緑感光性乳剤（２０１Ｇ）〜（２０６Ｇ）を調製した。
【０１５０】
（青感光性乳剤の調製）
赤感光性乳剤（２０１Ｒ）〜（２０６Ｒ）と同様に実施例１の試料（１０１）に適用される乳剤（１０１Ｂ）に対して塩化金酸とチオ硫酸ナトリウムの添加量比を変化させて緑感光性乳剤（２０１Ｂ）〜（２０６Ｂ）を調製した。
【０１５１】
上記の如く調製した各乳剤を用いて、実施例１と同様の構成でハロゲン化銀写真感光材料（２０１）〜（２０６）を作製した。
【０１５２】
【表５】

【０１５３】
上記試料（２０１）〜（２０６）に対して実施例１と同様に、多重露光適性、グレー濃度１．０での濃度安定性、細線の明瞭さを評価した。
【０１５４】
結果を表６にまとめた。
【０１５５】
【表６】

【０１５６】
表５、表６から明らかなように、（硫黄／金）比が各々１．３／１、１．０／１、０．８／１、０．６／１である試料（２０１）、（２０２）、（２０３）、（２０４）では多重露光階調変動に改良効果が認められるが、他の評価項目（濃度安定性、細線の明瞭さ）にはあまり効果がない。これに対して同比を０．４、０．３と小さくした試料（２０５）、（２０６）では多重露光階調変化、濃度安定性、細線安定性の何れも改良効果が認められており、硫黄増感剤と金増感剤の添加モル比を０．５以下にすることの有用性を認識できる。
【０１５７】
実施例３
（赤感光性乳剤の調製）
実施例１における乳剤（１０１Ｒ）とは染料Ｒ−１を乳剤調製後の塗布液を調製する際にハロゲン化銀１モル当たり１５ｍｇ添加したことのみ異なる乳剤（３０１Ｒ）を調製した。
【０１５８】
乳剤（３０１Ｒ）とはＲ−１を化学熟成開始後１００分で添加したことのみ異なる乳剤（３０２Ｒ）を調製した。
【０１５９】
乳剤（３０１Ｒ）とは、Ｒ−１を化学熟成終了時に添加したことのみ異なる乳剤（３０３Ｒ）を調製した。
【０１６０】
乳剤（３０１Ｒ）とはＲ−１の添加量をハロゲン化銀１モル当たり８ｍｇに変更したことのみ異なる乳剤（３０４Ｒ）を調製した。
【０１６１】
乳剤（３０２Ｒ）とはＲ−１の添加量をハロゲン化銀１モル当たり８ｍｇに変更したことのみ異なる乳剤（３０５Ｒ）を調製した。
【０１６２】
乳剤（３０３Ｒ）とはＲ−１の添加量をハロゲン化銀１モル当たり８ｍｇに変更したことのみ異なる乳剤（３０６Ｒ）を調製した。
【０１６３】
乳剤（３０１Ｒ）とはＲ−１の添加量をハロゲン化銀１モル当たり２ｍｇに変更したことのみ異なる乳剤（３０７Ｒ）を調製した。
【０１６４】
乳剤（３０２Ｒ）とはＲ−１の添加量をハロゲン化銀１モル当たり２ｍｇに変更したことのみ異なる乳剤（３０８Ｒ）を調製した。
【０１６５】
乳剤（３０３Ｒ）とはＲ−１の添加量をハロゲン化銀１モル当たり２ｍｇに変更したことのみ異なる乳剤（３０９Ｒ）を調製した。
【０１６６】
染料Ｒ−１をＲ−２に変更して乳剤（３０１Ｒ）〜（３０９Ｒ）と同様に乳剤（３１０Ｒ）〜（３１８Ｒ）を調製した。
【０１６７】
（緑感光性及び青感光性乳剤の調製）
上記で赤感光性乳剤については染料Ｒ−１，Ｒ−２を各々使用して乳剤（３０１Ｒ）〜（３０９Ｒ）、乳剤（３１０Ｒ）〜（３１８Ｒ）を各々調製したのと同様にして、緑感光性乳剤については染料Ｇ−１，Ｇ−２を、青感光性乳剤については染料Ｂ−１，Ｂ−２を各々使用し、乳剤（３０１Ｇ）〜（３１８Ｇ）、乳剤（３０１Ｂ）〜（３１８Ｂ）を調製した。
【０１６８】
【化９】

【０１６９】
【化１０】

【０１７０】
これら各感光性乳剤を組み合わせて重層試料（３０１）〜（３１８）を実施例１と同様の条件で作製した。
【０１７１】
【表７】

【０１７２】
実施例１と同様に、試料（３０１）〜（３１８）について多重露光適性、グレー濃度１．０での濃度安定性、細線の明瞭さを評価した。
【０１７３】
結果を表８にまとめた。
【０１７４】
【表８】

【０１７５】
表７、表８から明らかなように、染料を塗布液に添加した試料（３０１）、（３１６）のように、若干の改良効果が認められる場合もあるが、効果としては一様でない。これに対して化学熟成中に染料を乳剤中に添加した場合は、添加量が１５ｍｇと多い場合では塗布液添加と同様改良効果の見られる評価項目もあるが、効果の点ではこれらも不十分である。これに対して添加量を８ｍｇ、２ｍｇと減量した水準では、化学熟成中あるいは熟成終了時でも多重露光適性、濃度安定性、細線の明瞭さの各評価項目での効果が確認できる。化学熟成終了時に２ｍｇを添加した試料（３０９）、（３１８）では更なる改良効果が得られていることがわかる。
【０１７６】
実施例４
実施例２で作製した試料（３０１）〜（３１８）で添加する染料Ｂ−１，Ｇ−１，Ｒ−１を減感色素Ｄ−１に、染料Ｂ−２，Ｇ−２，Ｒ−２を減感色素Ｄ−２に、変更したことのみ異なる重層試料（４０１）〜（４１８）を作製した。
【０１７７】
各試料の乳剤構成及び減感色素とその添加量と添加時期を表９にまとめた。
【０１７８】
【化１１】

【０１７９】
【表９】

【０１８０】
これらの試料について、実施例１〜３と同様の評価を実施した。
【０１８１】
結果を表１０にまとめた。
【０１８２】
【表１０】

【０１８３】
表９、表１０から明らかなように、減感色素を塗布液添加した試料においては、実施例３とは異なり添加量に依らず細線安定性に対する効果は確認できない。多重露光適性及び濃度安定性に関しても効果が不十分であることがわかる。
【０１８４】
一方、減感色素を化学熟成中に添加した試料は１５ｍｇと添加量が多い場合では効果が得られる評価項目とそうでない評価項目がある。一方添加量を８ｍｇ、２ｍｇと減量した場合、化学熟成中でも化学熟成終了時でも多重露光適性、濃度安定性、細線安定性の改良効果が得られていることがわかる。また、試料（４０９）、（４１８）に見られるように添加量を２ｍｇと減少させ、かつ化学熟成終了時の添加がより高い発明の効果が得られていることがわかる。
【０１８５】
本発明により、高照度での多重露光による階調変動が小さく、走査露光での画像ムラ及び像滲みが改良されたハロゲン化銀写真感光材料、ハロゲン化銀乳剤及び画像形成方法を提供することができた。
【０１８６】
【発明の効果】
本発明により、高照度での多重露光適性に優れ、走査露光においても文字品質が良好なハロゲン化銀写真感光材料及び画像形成方法を提供することができた。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a silver halide photographic light-sensitive material, and more specifically, a silver halide photographic light-sensitive material that is excellent in multiple exposure suitability at high illuminance and has good character quality even in scanning exposure. Fee And an image forming method.
[0002]
[Prior art]
With the recent development of computer technology, it has become easy to process images read by a scanner on a computer. In addition, studies have been made on the use of silver halide photographic light-sensitive materials for hard copy of images, and image formation by a scanning exposure method has been performed, and technical studies for improving the image quality have been conducted extensively. In general, fine characters and images can be reproduced by reducing the beam diameter of the light source, but on the other hand, the exposure time increases and the occurrence of density unevenness becomes remarkable. Therefore, exposure is generally performed with a beam diameter of about 50 to 100 μm.
[0003]
In order to reduce the occurrence of density unevenness, for example, Japanese Patent Application Laid-Open Nos. 4-249244 and 9-30480 disclose a technique for providing an overlap between rasters. Appropriate beam overlap can reduce image unevenness, but the color shifts despite the fact that the same image data is input for a thin line close to the beam diameter and a large area, and low even for a large area. It has been found that a phenomenon occurs in which the color is shifted between the density part and the high density part.
[0004]
In addition, when image formation is performed by the above-described method, a phenomenon that a fine character cannot be drawn or a striped pattern is crushed in black occurs when a character image is drawn. In order to prevent this image bleeding, it is a general method to contain a dye or colloidal silver in the coating layer or the support. However, although the effect of preventing bleeding is improved by increasing the amount of the dye, a decrease in photographic sensitivity and coloring of the white background after processing occur at the same time.
[0005]
Japanese Patent Application Laid-Open No. 7-20596 discloses a technique including an organic desensitizer in a hydrophilic colloid layer, but is a technique for improving the handling and storage stability of a bright room light-sensitive material. There is no suggestion about the improvement, and there is no specific mention about the correlation between the addition time and the effect.
[0006]
Japanese Patent Application Laid-Open No. 6-11789 discloses a technique of adding chemical sensitizers in a divided manner, and is intended for high sensitivity in a silver iodobromide system. There is no mention of improvements.
[0007]
[Problems to be solved by the invention]
An object of the present invention is to provide a silver halide photographic material that is excellent in multiple exposure at high illuminance and has good character quality even in scanning exposure. Fee And providing an image forming method.
[0008]
[Means for Solving the Problems]
The above object of the present invention has been achieved by the following constitution.
[0009]
1. At least one red-sensitive layer, green-sensitive layer, blue-sensitive layer and non-photosensitive layer each on the reflective support At least one of the red photosensitive layer, the green photosensitive layer, and the blue photosensitive layer has an average silver chloride content of 95% or more, and is a mole of chalcogen sensitizer with respect to the added gold sensitizer. Containing a silver halide emulsion having a ratio of 0.5 or less Silver halide photographic light-sensitive material And 10 ^-6 After exposure for less than a second, color development and image formation are performed, and on the obtained characteristic curve, a straight line passing through a point giving a density of 0.5 and a point giving a density of 1.5 is drawn. And a silver halide photographic light-sensitive material characterized by being within 10%.
[0011]
2 . Each reflective support has at least one red photosensitive layer, green photosensitive layer, blue photosensitive layer and non-photosensitive layer, and at least one of the red photosensitive layer, the green photosensitive layer, and the blue photosensitive layer. Halogen prepared by adding not more than 10 mg of dye or desensitizing dye having a positive sum of polarographic anode potential and polarographic cathodic potential per mole of silver halide in which one layer has an average silver chloride content of 95% or more. A silver halide photographic light-sensitive material containing a silver halide emulsion, and 10 ^-6 After exposure for less than a second, color development and image formation are performed, and on the obtained characteristic curve, a straight line passing through a point giving a density of 0.5 and a point giving a density of 1.5 is drawn. And a silver halide photographic light-sensitive material characterized by being within 10%.
[0012]
3 . 1 to 2 The silver halide photographic light-sensitive material according to any one of 10 ^-6 An image forming method, wherein color development is performed after exposure for less than a second.
[0016]
Details of the present invention will be described below.
[0017]
The characteristic curve in the present invention is 10 ^-6 It is the curve which plotted logE (E is an exposure amount) on the horizontal axis and D (density) on the vertical axis for an image obtained by color development after exposure to high illuminance for seconds or less. Multiple exposure means 10 ^-6 This means that exposure is applied to the same pixel twice or more in the case of high-illuminance exposure for seconds or less. Further, the fluctuation of the average gradient at that time is the gradient when the straight line passing through the point giving the density 0.5 and the point giving the density 1.5 on the characteristic curve obtained by color development after one exposure is drawn. Means fluctuation.
[0018]
Variation in density gradient due to multiple exposure means color variation in printing, and ideally there is no average gradient variation.
[0019]
Examples of the light source for exposing the silver halide photographic light-sensitive material of the present invention include a light emitting diode, a gas laser, a solid laser, a semiconductor laser, a HeNe laser, an Ar laser, and a dye laser in addition to the Xe flashlight. Further, it can be used in either a vertical single mode or a horizontal multi mode, and a light source modulated by high frequency superposition and SHG (second harmonic element) may be used. In particular, in order to design a compact, inexpensive, long-life and high-stability device, it is preferable to use a semiconductor laser, and it is preferable to use a semiconductor laser as at least one of the exposure light sources.
[0020]
When the exposure time in such scanning exposure is defined as the time for exposing the pixel size when the pixel density is 400 dpi, the preferred exposure time is 10 ^-3 Seconds or less, more preferably 10 ^-6 Less than a second.
[0021]
The chemical sensitizer according to the present invention can be used in combination of a sensitizing method using a gold compound and a sensitizing method using a chalcogen sensitizer.
[0022]
As a chalcogen sensitizer applied to the silver halide emulsion according to the present invention, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer and the like can be used, but a sulfur sensitizer is preferred. Examples of the sulfur sensitizer include thiosulfate, allylthiocarbamide thiourea, allyl isothiocyanate, cystine, p-toluenethiosulfonate, rhodanine, and inorganic sulfur.
[0023]
As the gold sensitizer according to the present invention, various gold complexes such as chloroauric acid and gold sulfide can be added. Examples of the ligand compound used include dimethyl rhodanine, thiocyanic acid, mercaptotetrazole, mercaptotriazole and the like.
[0024]
The addition amount of the chemical sensitizer according to the present invention is 1 × 10 5 per mol of silver halide. ^-Four It is preferably less than or equal to a mole, more preferably 1 × 10 ^-Five Less than or equal to
[0025]
According to the study by the present inventors, in order to improve the high-illuminance exposure suitability, uniform and appropriate dispersion of chemical sensitization nuclei formed by chemical ripening is necessary. The ratio of sensitizers was found to be important. The molar ratio of the chalcogen sensitizer to the gold sensitizer according to the present invention needs to be 0.5 or less, but is preferably 0.3 to 0.4.
[0026]
As described above, the homogenization of chemical sensitization nuclei is effective for improving the high-illuminance exposure suitability, but it is also an effective technique to improve the addition method of chemical sensitizers. They found it. Specifically, the chemical sensitizer is not added all at once, but is divided or continuously added. Although the detailed mechanism is unknown, this method makes it possible to say that "when a large amount of chemical sensitizer is supplied into a silver halide emulsion at one time during chemical ripening, the concentration of the sensitizer is not uniform in the emulsion. It is thought that “the variation in the sensitization effect on the resulting silver halide grains” can be avoided. Therefore, as a method for adding the chemical sensitizer according to the present invention, it is necessary to add continuously or intermittently over 10% or more of the entire chemical ripening time, but it is preferable to add over 50% or more. In the case of continuous addition, the addition amount per unit time may be constant, may be different, or may be added as a function. In the case of intermittent addition, the addition interval may be 10% or more of the entire chemical ripening time, and is preferably 50% or more, but the addition amount in the divided addition may be the same or different. Good.
[0027]
The dye which concerns on this invention can use the dye which has absorption in a various wavelength range for the purpose of irradiation prevention and halation prevention. For this purpose, any known compound can be used. In particular, as dyes having absorption in the visible region, the dyes AI-1 to 11 described in JP-A-3-251840, page 308, and JP-A-Hei. The dyes described in JP-A-6-3770 are preferably used. Specific examples of preferred compounds include exemplified compounds (1) to (45) listed in the same publication, page 3, lower left column to page 5, lower left column.
[0028]
The desensitizing dye used in the present invention is preferably a compound in which the sum of the polarographic anode potential and cathode potential is positive, and many such compounds are described in patents or literature, and any desensitizing dye can be used. it can. For example, JP-B 36-17595, 39-20261, 40-26751, 43-13167, 45-8833, 47-8746, 47-10197, 50-37530, U.S. Pat. Nos. 2,271,458, 2,541,472, 3,035,917, 3,062,651, 3,124,458, etc. And the compounds described.
[0029]
Further, the addition amount of the dye and desensitizing dye according to the present invention is required to be 10 mg or less per 1 mol of silver halide, but is preferably 5 mg or less.
[0030]
The addition time of the dye and the desensitizing dye according to the present invention is not particularly limited, but the addition time is preferably at the end of chemical ripening from the viewpoint of achieving both basic performance such as sensitivity and gradation and suitability for exposure to high illumination.
[0031]
On the other hand, when the same dye or the same pigment is added to the coating solution prepared when the emulsion is prepared and coated on the support, it is not preferable because compatibility between multiple exposure suitability and character quality cannot be achieved.
[0032]
The composition of the silver halide emulsion used in the present invention is characterized in that the silver chloride content is 95 mol% or more. If this condition is satisfied, silver chloroiodobromide, silver iodochloride, silver chlorobromide Any silver chloride or silver chlorobromide emulsion having a localized phase having a silver bromide content of 30 mol% or more can be used.
[0033]
The portion containing silver bromide at a high concentration may form a layer as a so-called core / shell emulsion, or it is only partially partially formed by epitaxy bonding to a silver halide emulsion grain. There may only be regions of different composition. The portion where silver bromide is present at a high concentration may be formed in the silver halide grain formation step, or may be formed in the subsequent chemical ripening step or coating solution preparation step. Moreover, when the composition of the inside of a particle and the surface differs, a composition may change continuously and may change discontinuously.
[0034]
Although depending on the composition of the entire silver halide emulsion grain, when the silver bromide content relative to the total silver halide is about 1 mol%, the silver bromide content in the portion containing silver bromide at a high concentration is 40 mol% or more is preferable. In order to make such a silver bromide localized phase, a so-called conversion method in which an aqueous solution of a water-soluble bromide salt such as potassium bromide is added, a simultaneous mixing method or a bromide prepared in advance can be used. You may use the method of adding a silver fine particle and utilizing a recrystallization process. Examples of such silver halide grains include grains described in JP-A-58-95736, JP-A-58-108533, and JP-A-1-183647.
[0035]
The silver bromide content in the portion containing silver bromide at a high concentration can be determined using the method described in JP-A-1-183647, page 22, upper right column. When the silver bromide content thus obtained has a range, the silver bromide content of the portion containing silver bromide at a high concentration referred to in the present invention means the maximum value.
[0036]
In order to obtain a silver halide emulsion according to the present invention, it is advantageous to contain heavy metal ions. Heavy metal ions that can be used for such purposes include Group 8-10 metals such as iron, iridium, platinum, palladium, nickel, rhodium, osmium, ruthenium, and cobalt, and group 12 metals such as cadmium, zinc, and mercury. Group transition metals and ions of lead, rhenium, molybdenum, tungsten, gallium, and chromium can be given. Of these, metal ions of iron, iridium, platinum, ruthenium, gallium and osmium are preferable.
[0037]
These metal ions can be added to the silver halide emulsion in the form of a salt or a complex salt.
[0038]
When the heavy metal ion forms a complex, examples of the ligand include cyanide ion, thiocyanate ion, isothiocyanate ion, chloride ion, bromide ion, iodide ion, carbonyl, ammonia and the like. . Of these, cyanide ion, thiocyanate ion, isothiocyanate ion, chloride ion, bromide ion and the like are preferable.
[0039]
In order to contain a heavy metal ion in the silver halide emulsion according to the present invention, the heavy metal compound is added before formation of silver halide grains, during formation of silver halide grains, and during physical ripening after formation of silver halide grains. What is necessary is just to add in the arbitrary places of each process. In order to obtain a silver halide emulsion satisfying the above-mentioned conditions, the heavy metal compound can be dissolved together with the halide salt and continuously added throughout the grain forming process or a part thereof.
[0040]
When the heavy metal ion is added to the silver halide emulsion, the amount is 1 × 10 5 per mole of silver halide. ^-9 1 x 10 moles or more ^-2 Mole or less is more preferable, especially 1 × 10 ^-8 More than mole 5 × 10 ^-Five The molar amount is preferred.
[0041]
The silver halide grains according to the present invention can have any shape. One preferable example is a cube having a (100) plane as a crystal surface. Also, U.S. Pat. Nos. 4,183,756, 4,225,666, JP-A-55-26589, JP-B-55-42737, The Journal of Photographic Science (J. Photogr. Sci.) 21, 39 (1973) and the like, particles having an octahedron, tetrahedron, dodecahedron, etc. can be produced and used. Furthermore, particles having twin planes may be used.
[0042]
The grain size of the silver halide grains according to the present invention is not particularly limited, but is preferably 0.1 to 1.2 μm, more preferably 0 in view of other photographic performances such as rapid processability and sensitivity. In the range of 2 to 1.0 μm.
[0043]
The particle size distribution of the silver halide grains of the present invention is preferably monodispersed silver halide grains having a coefficient of variation of 0.22 or less, more preferably 0.15 or less, and particularly preferably a coefficient of variation of 0.15 or less. Two or more monodispersed emulsions are added to the same layer. Here, the variation coefficient is a coefficient representing the breadth of the particle size distribution, and is defined by the following equation.
[0044]
Coefficient of variation = S / R
(Here, S represents the standard deviation of the particle size distribution, and R represents the average particle size.)
The particle diameter here means the diameter in the case of spherical silver halide grains, and the diameter when the projected image is converted into a circular image of the same area in the case of grains other than a cube or a sphere. Represent.
[0045]
As a silver halide emulsion preparation apparatus and method, various methods known in the art can be used.
[0046]
The silver halide emulsion according to the present invention may be obtained by any of acidic method, neutral method and ammonia method. The particles may be grown at one time, or may be grown after the seed particles are made. The method for making seed particles and the method for growing them may be the same or different.
[0047]
Further, the form of reacting the soluble silver salt and the soluble halide salt may be any of a forward mixing method, a back mixing method, a simultaneous mixing method, a combination thereof, and the like, but those obtained by the simultaneous mixing method are preferred. Furthermore, the pAg controlled double jet method described in JP-A No. 54-48521 and the like can be used as one type of the simultaneous mixing method.
[0048]
Further, an apparatus for supplying a water-soluble silver salt and a water-soluble halide salt aqueous solution from an adding apparatus disposed in a reaction mother liquor described in JP-A-57-92523 and JP-A-57-92524, German Patent No. 2 , 921,164, etc., an apparatus for continuously adding an aqueous solution of a water-soluble silver salt and a water-soluble halide salt, and a reaction mother liquor outside the reactor described in JP-B-56-501776, etc. An apparatus that forms grains while keeping the distance between silver halide grains constant by taking out and concentrating by ultrafiltration may be used.
[0049]
Further, if necessary, a silver halide solvent such as thioether may be used. Further, a compound having a mercapto group, a nitrogen-containing heterocyclic compound, or a compound such as a sensitizing dye may be added at the time of forming silver halide grains or after the completion of grain formation.
[0050]
The silver halide emulsion according to the present invention is known for the purpose of preventing fogging during the preparation process of a silver halide photographic material, reducing performance fluctuation during storage, and preventing fogging during development. Antifoggants and stabilizers can be used. Examples of preferable compounds that can be used for such purposes include compounds represented by the general formula (II) described in JP-A-2-14636, page 7, lower column, and more preferable specific compounds. As the compounds (IIa-1) to (IIa-8) and (IIb-1) to (IIb-7) described on page 8 of the same publication, and 1- (3-methoxyphenyl) -5-mercapto Examples thereof include compounds such as tetrazole and 1- (4-ethoxyphenyl) -5-mercaptotetrazole. Depending on the purpose, these compounds are added in steps such as a silver halide emulsion grain preparation step, a chemical sensitization step, a chemical sensitization step, and a coating solution preparation step. When chemical sensitization is performed in the presence of these compounds, 1 × 10 6 per mole of silver halide. ^-Five Mol ~ 5x10 ^-Four It is preferably used in a molar amount. When added at the end of chemical sensitization, 1 x 10 per mole of silver halide ^-6 Mol ~ 1 × 10 ^-2 A molar amount is preferred, 1 × 10 ^-Five Mol ~ 5x10 ^-3 Mole is more preferred. In the coating solution preparation step, when added to the silver halide emulsion layer, 1 × 10 5 per mole of silver halide. ^-6 Mol ~ 1 × 10 ^-1 A molar amount is preferred, 1 × 10 ^-Five Mol ~ 1 × 10 ^-2 Mole is more preferred. When added to a layer other than the silver halide emulsion layer, the amount in the coating film is 1 m. ² 1 × 10 per ^-9 Mol ~ 1 × 10 ^-3 A molar amount is preferred.
[0051]
It is preferable to add a fluorescent brightening agent to the light-sensitive material according to the present invention because white background can be improved. Preferred examples of the compound include compounds represented by the general formula II described in JP-A-2-232652.
[0052]
When the silver halide photographic light-sensitive material according to the present invention is used as a color photographic light-sensitive material, the silver halide is spectrally sensitized to a specific region in a wavelength range of 400 to 900 nm in combination with a yellow coupler, a magenta coupler, and a cyan coupler. It has a layer containing an emulsion. The silver halide emulsion contains one or a combination of two or more sensitizing dyes.
[0053]
As the spectral sensitizing dye used in the silver halide emulsion used in the present invention, any known compound can be used. As the blue-sensitive sensitizing dye, it is described in JP-A-3-251840, page 28. BS-1 to 8 can be preferably used alone or in combination. As the green sensitive sensitizing dye, GS-1 to 5 described on page 28 of the same publication are preferably used. As red-sensitive sensitizing dyes, RS-1 to 8 described on page 29 of the same publication are preferably used. In addition, when image exposure is performed from infrared light using a semiconductor laser or the like, it is necessary to use an infrared photosensitive sensitizing dye. As an infrared photosensitive sensitizing dye, JP-A-4-285950 can be used. The pigments of IRS-1 to 11 described in JP-A No. 6-8 are preferably used. Further, these infrared, red, green, and blue sensitive sensitizing dyes are supersensitizers SS-1 to SS-9 described in JP-A-4-285950, pages 8 to 9 and JP-A-5-66515. The compounds S-1 to S-17 described in pages 15 to 17 of the publication are preferably used in combination.
[0054]
The addition amount of the sensitizing dye varies depending on the kind of the sensitizing dye, the halogen composition of the applied silver halide emulsion, the grain size, and the like, but preferably 5 × 10 5 per mole of silver halide. ^-Five ~ 4x10 ^-3 Mole, more preferably 1 × 10 ^-Four ~ 1x10 ^-3 Used in the molar range.
[0055]
These sensitizing dyes may be added at any time from the formation of silver halide grains to the end of chemical sensitization.
[0056]
As a method for adding a sensitizing dye, it may be added as a solution by dissolving it in water-miscible organic solvent such as methanol, ethanol, fluorinated alcohol, acetone, dimethylformamide or water, or as a solid dispersion. However, it is preferable to add it as a solid dispersion because it enhances the effect of the present invention.
[0057]
As a method for dispersing the sensitizing dye, in addition to a method of mechanically crushing and dispersing fine particles having a size of 1 μm or less in an aqueous system using a high-speed stirring type disperser, a pH of 6 to 5 as described in JP-A-58-105141 8. A method of mechanically pulverizing and dispersing fine particles of 1 μm or less in an aqueous system under conditions of 60 to 80 ° C., and presence of a surfactant that suppresses the surface tension described in Japanese Patent Publication No. 60-6496 to 38 dyne / cm or less A method of dispersing below can be used.
[0058]
Examples of the dispersion apparatus that can be used to prepare the dispersion include a high speed stirring type disperser described in FIG. 1 of JP-A-4-125631, a ball mill, a sand mill, an ultrasonic disperser, and the like. be able to.
[0059]
Further, when using these dispersing apparatuses, as described in JP-A-4-125632, a pre-treatment such as dry pulverization is performed in advance, followed by wet dispersion.
[0060]
When a plurality of sensitizing dyes are used in combination, the two sensitizing dyes may be added separately or may be added after mixing in advance.
[0061]
The coupler used in the silver halide photographic light-sensitive material according to the present invention may be any coupler capable of forming a coupling product having a spectral absorption maximum wavelength in a wavelength region longer than 340 nm by a coupling reaction with an oxidized form of a color developing agent. Although a compound can also be used, a typical example is a yellow dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, and a magenta dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 500 to 600 nm. Typical examples of cyan dye-forming couplers having a spectral absorption maximum wavelength in the wavelength range of 600 to 750 nm are typical.
[0062]
Cyan couplers that can be preferably used in the silver halide photographic light-sensitive material according to the present invention are represented by the general formulas (CI) and (C-II) described in JP-A-4-114154, page 5, lower left column. Can be mentioned.
[0063]
The magenta coupler that can be preferably used in the silver halide photographic light-sensitive material according to the present invention is represented by the general formulas (M-I) and (M-II) described in JP-A-4-114154, page 4, upper right column. Can be mentioned. Among the magenta couplers, more preferable is a coupler represented by the general formula (MI) described in the upper right column on page 4 of the same publication, of which the RM of the general formula (MI) is tertiary. Couplers that are alkyl groups are particularly preferred because of their excellent light resistance.
[0064]
As a yellow coupler which can be preferably used in the silver halide photographic light-sensitive material according to the present invention, a coupler represented by the general formula (Y-I) described in the upper right column of page 3 of JP-A-4-114154 is used. Can do. Specific compounds include those described as YC-1 to YC-9 in the lower left column on page 3 of the publication. Among them, a coupler in which RY1 of the general formula [Y-1] in the same publication is an alkoxy group or a coupler represented by the general formula [I] described in JP-A-6-67388 is preferable because it can reproduce yellow with a preferable color tone. Further, compounds represented by the general formula [Y-1] described in JP-A-4-81847, page 1 and JP-A-11-page 17 can also be used.
[0065]
When an oil-in-water emulsion dispersion method is used to add a coupler or other organic compound used in the silver halide photographic light-sensitive material according to the present invention, it is usually a water-insoluble high boiling organic solvent having a boiling point of 150 ° C. or higher. In addition, if necessary, it is dissolved in combination with a low boiling point and / or water-soluble organic solvent, and emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. As a dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser, or the like can be used. A step of removing the low-boiling organic solvent after the dispersion or simultaneously with the dispersion may be added. High-boiling organic solvents that can be used to dissolve and disperse the coupler include phthalates such as dioctyl phthalate, diisodecyl phthalate, and dibutyl phthalate, phosphate esters such as tricresyl phosphate and trioctyl phthalate, Is preferably used. The dielectric constant of the high boiling point organic solvent is preferably 3.5 to 7.0. Two or more high-boiling organic solvents can be used in combination.
[0066]
Further, instead of using a high-boiling organic solvent or in combination with a high-boiling organic solvent, a water-insoluble and organic solvent-soluble polymer compound is dissolved in a low-boiling and / or water-soluble organic solvent as necessary. In addition, a method of emulsifying and dispersing by various dispersing means using a surfactant in a hydrophilic binder such as an aqueous gelatin solution can also be used. Examples of the water-insoluble and organic solvent-soluble polymer used at this time include poly (Nt-butylacrylamide).
[0067]
Compounds containing a hydrophobic group having 8 to 30 carbon atoms and a sulfonic acid group or a salt thereof as one of the surfactants used for dispersing the photographic additive and adjusting the surface tension during coating. Is mentioned. Specific examples include A-1 to A-11 described in JP-A No. 64-26854. A surfactant in which a fluorine atom is substituted for an alkyl group is also preferably used. These dispersions are usually added to a coating solution containing a silver halide emulsion, but the time until the addition to the coating solution after dispersion and the time until the coating after addition to the coating solution should be short, and 10 hours each. Is preferably within 3 hours, and more preferably within 20 minutes.
[0068]
Each of the above couplers is preferably used in combination with an anti-fading agent in order to prevent fading of the formed dye image due to light, heat, humidity and the like. Particularly preferred compounds include phenyl ether compounds represented by general formulas I and II described on page 3 of JP-A-2-66541, phenolic compounds represented by general formula IIIB described in JP-A-3-174150, An amine compound represented by the general formula A described in Japanese Utility Model Laid-Open No. 64-90445 and a metal complex represented by the general formulas XII, XIII, XIV, and XV described in Japanese Patent Application Laid-Open No. 62-182741 are particularly preferable for magenta dyes. . Further, compounds represented by the general formula I 'described in JP-A-1-196049 and compounds represented by the general formula II described in JP-A-5-11417 are particularly preferred for yellow and cyan dyes.
[0069]
For the purpose of shifting the absorption wavelength of the coloring dye, compound (d-11) described in JP-A-4-114154, page 9, lower left column, compound (A'-1), etc., page 10, lower left column, etc. Compounds can be used. In addition, a fluorescent dye releasing compound described in US Pat. No. 4,774,187 can also be used.
[0070]
In the silver halide light-sensitive material according to the present invention, a compound that reacts with an oxidized developing agent is added to the layer between the photosensitive layer to prevent color turbidity or added to the silver halide emulsion layer. It is preferable to improve fog and the like. The compound for this purpose is preferably a hydroquinone derivative, more preferably a dialkyl hydroquinone such as 2,5-di-t-octyl hydroquinone.
[0071]
In the light-sensitive material according to the present invention, it is preferable to add an ultraviolet absorber to prevent static fogging or to improve the light resistance of a dye image. Preferred ultraviolet absorbers include benzotriazoles, and particularly preferred compounds include compounds represented by general formula III-3 described in JP-A-1-250944, and general formula III described in JP-A-64-66646. A compound represented by general formula I described in JP-A No. 63-187240, UV-1L to UV-27L described in JP-A No. 63-187240, JP-A-4-1633, and general formula described in JP-A No. 5-165144. Examples include compounds represented by formulas (I) and (II).
[0072]
In the silver halide photographic light-sensitive material according to the present invention, it is advantageous to use gelatin as a binder. If necessary, other gelatin, gelatin derivatives, gelatin and other polymer graft polymers, proteins other than gelatin are used. Hydrophilic colloids such as sugar derivatives, cellulose derivatives, synthetic hydrophilic polymer materials such as mono- or copolymers can also be used.
[0073]
It is preferable to use a vinylsulfone type hardener or a chlorotriazine type hardener alone or in combination as a hardener for these binders. It is preferable to use the compounds described in JP-A-61-249054 and JP-A-61-245153. In addition, it is preferable to add a preservative and an antifungal agent as described in JP-A-3-157646 in the colloid layer in order to prevent the growth of mold and bacteria which adversely affect photographic performance and image storage stability. In order to improve the physical properties of the surface of the photosensitive material or the processed sample, it is preferable to add a slipping agent or a matting agent described in JP-A-6-118543 and JP-A-2-73250 to the protective layer.
[0074]
As the support used in the silver halide photographic light-sensitive material according to the present invention, any material may be used. Paper coated with polyethylene or polyethylene terephthalate, paper support made of natural pulp or synthetic pulp, vinyl chloride sheet Polypropylene which may contain a white pigment, polyethylene terephthalate support, baryta paper and the like can be used. Especially, the support body which has a water-resistant resin coating layer on both surfaces of a base paper is preferable. As the water resistant resin, polyethylene, polyethylene terephthalate or a copolymer thereof is preferable.
[0075]
As the white pigment used for the support, inorganic and / or organic white pigments can be used, and inorganic white pigments are preferably used. For example, alkaline earth metal sulfate such as barium sulfate, alkaline earth metal carbonate such as calcium carbonate, silica such as fine silicate, synthetic silicate, calcium silicate, alumina, alumina hydrate, oxidation Examples thereof include titanium, zinc oxide, talc, and clay. The white pigment is preferably barium sulfate or titanium oxide.
[0076]
The amount of the white pigment contained in the water-resistant resin layer on the surface of the support is preferably 13% by weight or more, and more preferably 15% by weight or more for improving sharpness.
[0077]
The degree of dispersion of the white pigment in the water-resistant resin layer of the paper support according to the present invention can be measured by the method described in JP-A-2-28640. When measured by this method, the degree of dispersion of the white pigment is preferably 0.20 or less, and more preferably 0.15 or less, as the coefficient of variation described in the above publication.
[0078]
Moreover, it is more preferable that the value of the center plane average roughness (SRa) of the support is 0.15 μm or less, and further 0.12 μm or less, because the effect of good gloss is obtained. Also, in order to improve the whiteness by adjusting the spectral reflection density balance of the white background after treatment in the white pigment-containing water-resistant resin of the reflective support or in the coated hydrophilic colloid layer, a trace amount of ultramarine, oil-soluble dyes, etc. It is preferable to add a blue tinting agent or a red tinting agent.
[0079]
The silver halide photographic light-sensitive material according to the present invention is subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the support surface as necessary, and directly or undercoat layer (adhesion of the support surface, antistatic properties , One or more subbing layers for improving dimensional stability, rub resistance, hardness, antihalation properties, friction properties and / or other properties).
[0080]
When coating a photographic light-sensitive material using a silver halide emulsion, a thickener may be used to improve the coating property. As the coating method, extrusion coating and curtain coating capable of simultaneously coating two or more layers are particularly useful.
[0081]
The present invention is preferably applied to a photosensitive material in which a developing agent is not incorporated in the photosensitive material, and is particularly preferably applied to a photosensitive material that directly forms an image for viewing. Examples thereof include color paper, color reversal paper, photosensitive material for forming a positive image, photosensitive material for display, and photosensitive material for color proof. In particular, it is preferably applied to a photosensitive material having a reflective support.
[0082]
As the aromatic primary amine developing agent used in the present invention, known compounds can be used. Examples of these compounds include the following compounds.
[0083]
CD-1) N, N-diethyl-p-phenylenediamine
CD-2) 2-Amino-5-diethylaminotoluene
CD-3) 2-amino-5- (N-ethyl-N-laurylamino) toluene
CD-4) 4- (N-ethyl-N- (β-hydroxyethyl) amino) aniline
CD-5) 2-Methyl-4- (N-ethyl-N- (β-hydroxyethyl) amino) aniline
CD-6) 4-Amino-3-methyl-N-ethyl-N- (β- (methanesulfonamido) ethyl) aniline
CD-7) N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide
CD-8) N, N-dimethyl-p-phenylenediamine
CD-9) 4-Amino-3-methyl-N-ethyl-N-methoxyethylaniline
CD-10) 4-Amino-3-methyl-N-ethyl-N- (β-ethoxyethyl) aniline
CD-11) 4-Amino-3-methyl-N-ethyl-N- (γ-hydroxypropyl) aniline
In the present invention, the above color developer can be used in any pH range, but it is preferably pH 9.5 to 13.0, more preferably pH 9.8 to 12.0 from the viewpoint of rapid processing. Used.
[0084]
The processing temperature for color development according to the present invention is preferably 35 ° C. or higher and 70 ° C. or lower. The higher the temperature, the shorter the treatment is possible and the better, but it is preferable that the temperature is not so high in terms of the stability of the treatment liquid.
[0085]
The color development time is generally about 3 minutes 30 seconds, but in the present invention, it is preferably within 40 seconds, and more preferably within 25 seconds.
[0086]
In addition to the above color developing agent, known developer component compounds can be added to the color developer. Usually, an alkali agent having a pH buffering action, a development inhibitor such as chloride ions and benzotriazoles, a preservative and a chelating agent are used.
[0087]
The silver halide photographic light-sensitive material of the present invention is subjected to bleaching and fixing after color development. The bleaching process may be performed simultaneously with the fixing process. After the fixing process, a washing process is usually performed. Moreover, you may perform a stabilization process as an alternative to a washing process. As a development processing apparatus used for the development processing of the silver halide photographic light-sensitive material of the present invention, the photosensitive material is applied to the belt even if it is a roller transport type that conveys the light-sensitive material between rollers arranged in a processing tank. It may be an endless belt system that is fixed and transported. However, a processing tank is formed in a slit shape, a processing liquid is supplied to the processing tank, and a photosensitive material is transported and a spray that sprays the processing liquid. A system, a web system by contact with a carrier impregnated with a processing liquid, a system using a viscous processing liquid, or the like can also be used. When processing in large quantities, it is usually performed using an automatic processor, but at this time, the replenishment amount of the replenisher is preferably as small as possible. The most preferable treatment form from the viewpoint of environmental suitability is the replenishment method of tablets. It is adding a processing agent in a form, and the method described in the published technical report 94-16935 is most preferable.
[0088]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention, the embodiment of this invention is not limited to these.
[0089]
Example 1
(Preparation of red-sensitive silver halide emulsion)
The following (A solution) and (B solution) were simultaneously added to 1 liter of 2% gelatin aqueous solution kept at 40 ° C. over 30 minutes while controlling pAg = 7.3 and pH = 3.0. C solution) and (D solution) were simultaneously added over 180 minutes while controlling pAg = 8.0 and pH = 5.5. At this time, the pAg was controlled by the method described in JP-A-59-45437, and the pH was controlled using sulfuric acid or a sodium hydroxide aqueous solution.
[0090]
(Liquid A)
Sodium chloride 3.42g
Potassium bromide 0.03g
200ml with water
(Liquid B)
Silver nitrate 10g
200ml with water
(C liquid)
Sodium chloride 102.7g
K ₂ IrCl ₆ 4x10 ^-8 Mole / Mole Ag
K _Four Fe (CN) ₆ 2 × 10 ^-Five Mole / Mole Ag
Potassium bromide 1.0g
600ml with water
(Liquid D)
300 g of silver nitrate
600ml with water
After the addition, desalting was performed using a 5% aqueous solution of Demol N made by Kao Atlas and a 20% aqueous solution of magnesium sulfate, and then mixed with an aqueous gelatin solution to obtain an average particle size of 0.40 μm and a coefficient of variation in particle size distribution. A monodispersed cubic emulsion EMP-1 having 0.07 and a silver chloride content of 99.5 mol% was obtained. Next, the average particle size was 0.38 μm and the particle size distribution was the same as EMP-1, except that the addition time of (A solution) and (B solution) and the addition time of (C) solution and (D) solution were changed. A monodispersed cubic emulsion EMP-1B having a coefficient of variation of 0.07 and a silver chloride content of 99.5 mol% was obtained.
[0091]
The above EMP-1 was optimally chemically sensitized at 60 ° C. using the following compounds. Similarly, after EMP-1B was optimally chemically sensitized, the sensitized EMP-1 and EMP-1B were mixed at a silver ratio of 1: 1 to obtain a red-sensitive silver halide emulsion (101R). Got.
[0092]
Sodium thiosulfate 1 × 10 ^-Four Mole / Mole AgX
Chloroauric acid 1.2 × 10 ^-Four Mole / Mole AgX
Stabilizer STAB-1 3 × 10 ^-Four Mole / Mole AgX
Stabilizer STAB-2 3 × 10 ^-Four Mole / Mole AgX
Stabilizer STAB-3 3 × 10 ^-Four Mole / Mole AgX
Sensitizing dye RS-1 1 × 10 ^-Four Mole / Mole AgX
Sensitizing dye RS-2 1 × 10 ^-Four Mole / Mole AgX
STAB-1: 1- (3-acetamidophenyl) -5-mercaptotetrazole
STAB-2: 1-phenyl-5-mercaptotetrazole
STAB-3: 1- (4-Ethoxyphenyl) -5-mercaptotetrazole
In the red-sensitive emulsion, SS-1 is 2.0 × 10 6 per mole of silver halide. ^-3 Added.
[0093]
[Chemical 1]

[0094]
Emulsion (102R) which differs from emulsion (101R) only in that sodium thiosulfate to be added was divided into two equal parts, and the other was added when 10 minutes had elapsed from the first addition.
[0095]
Emulsion (103R) which differs from emulsion (102R) only in that the addition interval of bisected sodium thiosulfate was 60 minutes was prepared.
[0096]
Emulsion (104R) which differs from emulsion (102R) only in that the addition interval of bisected sodium thiosulfate was 100 minutes was prepared.
[0097]
An emulsion (105R) was prepared which differs from the emulsion (102R) only in that the addition interval of bisected sodium thiosulfate was 200 minutes.
[0098]
Emulsion (106R) differed from emulsion (102R) only in that sodium thiosulfate was added continuously over 200 minutes of chemical ripening while keeping the addition amount per minute constant.
[0099]
Emulsion (107R) which differs from emulsion (102R) only in that chloroauric acid was added at intervals of 10 minutes instead of sodium thiosulfate was prepared.
[0100]
Emulsion (108R) which differs from emulsion (103R) only in that chloroauric acid was added at intervals of 60 minutes instead of sodium thiosulfate was prepared.
[0101]
Emulsion (109R) which differs from emulsion (104R) only in that chloroauric acid was added at intervals of 100 minutes instead of sodium thiosulfate was prepared.
[0102]
An emulsion (110R) different from the emulsion (105R) only in that chloroauric acid was added at intervals of 200 minutes instead of sodium thiosulfate was prepared.
[0103]
Emulsion (111R) differed from emulsion (106R) only in that chloroauric acid was added continuously over 200 minutes during chemical ripening, not sodium thiosulfate.
[0104]
(Preparation of green sensitive silver halide emulsion)
Except for changing the addition time of (A liquid) and (B liquid) and the addition time of (C liquid) and (D liquid), the average particle size was 0.40 μm, the coefficient of variation was 0.08, as in EMP-1. A monodispersed cubic emulsion EMP-2 having a silver chloride content of 99.5% was obtained. Next, a monodispersed cubic emulsion EMP-2B having an average particle size of 0.50 μm, a coefficient of variation of 0.08, and a silver chloride content of 99.5% was obtained.
[0105]
The EMP-2 was optimally chemically sensitized at 55 ° C. using the following compounds. Similarly, after EMP-2B was optimally chemically sensitized, sensitized EMP-2 and EMP-2B were mixed at a silver ratio of 1: 1 to obtain a green sensitive silver halide emulsion (101G )
[0106]
Sodium thiosulfate 1 × 10 ^-Four / Mol AgX
Chloroauric acid 1.2 × 10 ^-Four / Mol AgX
Stabilizer STAB-1 2.5 × 10 ^-Four Mole / Mole AgX
Stabilizer STAB-2 3.1 × 10 ^-Four Mole / Mole AgX
Stabilizer STAB-3 3.1 × 10 ^-Four Mole / Mole AgX
Sensitizing dye GS-1 4 × 10 ^-Four Mole / Mole AgX
[0107]
[Chemical formula 2]

[0108]
Thereafter, emulsions (102G) to (111G) to which sodium thiosulfate and chloroauric acid were separately added were prepared in the same manner as emulsions (102R) to (111R).
[0109]
(Preparation of blue-sensitive silver halide emulsion)
Except for changing the addition time of (A liquid) and (B liquid) and the addition time of (C liquid) and (D liquid), the average particle size was 0.71 μm, the coefficient of variation was 0.08, as in EMP-1. A monodispersed cubic emulsion EMP-3 having a silver chloride content of 99.5% was obtained. Next, a monodispersed cubic emulsion EMP-3B having an average particle size of 0.64 μm, a coefficient of variation of 0.08, and a silver chloride content of 99.5% was obtained.
[0110]
The EMP-3 was optimally chemically sensitized at 60 ° C. using the following compounds. Similarly, EMP-3B was also chemically sensitized optimally, and then sensitized EMP-3 and EMP-3B were mixed at a silver ratio of 1: 1 to obtain a blue-sensitive silver halide emulsion (101B )
[0111]
Sodium thiosulfate 1 × 10 ^-Four Mole / Mole AgX
Chloroauric acid 1.2 × 10 ^-Four Mole / Mole AgX
Stabilizer STAB-1 2 × 10 ^-Four Mole / Mole AgX
Stabilizer STAB-2 2.4 × 10 ^-Four Mole / Mole AgX
Stabilizer STAB-3 2.1 × 10 ^-Four Mole / Mole AgX
Sensitizing dye BS-1 4 × 10 ^-Four Mole / Mole AgX
Sensitizing dye BS-2 1 × 10 ^-Four Mole / Mole AgX
[0112]
[Chemical 3]

[0113]
Thereafter, emulsions (102B) to (111B) to which sodium thiosulfate and chloroauric acid were separately added were prepared in the same manner as emulsions (102R) to (111R).
[0114]
Basis weight 180g / m ² High density polyethylene was laminated on both sides of the paper pulp to prepare a paper support. However, on the side on which the emulsion layer was applied, a melted polyethylene containing a surface-treated anatase-type titanium oxide dispersed at a content of 15% by weight was laminated to prepare a reflective support. After the reflective support is subjected to corona discharge treatment, a gelatin subbing layer is provided, and each layer having the following constitution is further provided to produce a silver halide photographic light-sensitive material (101). The coating solution was prepared as follows.
[0115]
First layer coating solution
Yellow coupler (Y-1) 23.4 g, dye image stabilizer (ST-1) 3.34 g, (ST-2) 3.34 g, (ST-5) 3.34 g, stain inhibitor (HQ-1 ) 0.34 g, image stabilizer A 5.0 g, high boiling point organic solvent (DBP) 3.33 g and high boiling point organic solvent (DNP) 1.67 g, 60 ml of ethyl acetate was added and dissolved, and this solution was dissolved in 20% surfactant. (SU-1) A yellow coupler dispersion was prepared by emulsifying and dispersing in 220 ml of a 10% gelatin aqueous solution containing 7 ml using an ultrasonic homogenizer. This dispersion was mixed with the blue-sensitive silver halide emulsion 101B prepared above to prepare a first layer coating solution.
[0116]
Each coating solution was prepared so that the coating amounts of the second to seventh layer coating solutions were as shown in Tables 1 and 2 similarly to the first layer coating solution.
[0117]
[Table 1]

[0118]
[Table 2]

[0119]
Moreover, (H-1) and (H-2) were added as a hardening agent. As coating aids, surfactants (SU-2) and (SU-3) were added to adjust the surface tension. Further, preservative DI-1 was added.
[0120]
SU-1: Sodium tri-i-propylnaphthalenesulfonate
SU-2: Sulfosuccinic acid di (2-ethylhexyl) sodium salt
SU-3: Sulfosuccinic acid di (2,2,3,3,4,4,5,5-octafluoropentyl) sodium salt
DBP: Dibutyl phthalate
DNP: dinonyl phthalate
DOP: Dioctyl phthalate
DIDP: Di-i-decyl phthalate
PVP: Polyvinylpyrrolidone
H-1: Tetrakis (vinylsulfonylmethyl) methane
H-2: 2,4-dichloro-6-hydroxy-s-triazine sodium
Image stabilizer A: Pt-octylphenol
[0121]
[Formula 4]

[0122]
[Chemical formula 5]

[0123]
[Chemical 6]

[0124]
[Chemical 7]

[0125]
[Chemical 8]

[0126]
In this way, a photosensitive material sample (101) was produced.
[0127]
Further, in the photosensitive material sample (101), the silver halide emulsion used in each of the first, third and fifth photosensitive layers was changed as shown in Table 3 below. In the same manner as above, photosensitive material samples (102) to (111) were prepared.
[0128]
[Table 3]

[0129]
About the photosensitive material samples (101) to (111) thus prepared, a helium / cadmium laser (about 422 nm) as a blue light source, a helium / neon laser (about 544 nm) as a green light source, and gallium aluminum as a red light source・ Optical system using arsenic semiconductor laser (about 780nm), beam diameter is about 80μm, polygon mirror is used, scanning speed is 160m / sec, exposure time per pixel is 5 × 10 ^-7 The following three types of exposure were performed under the conditions of seconds.
[0130]
(1) A sample subjected to gray-scale exposure once and a sample subjected to twice by controlling the exposure amount with an external modulator
(2) Sample subjected to uniform scanning exposure so as to obtain a gray patch with a density of 1.0
(3) Sample exposed by changing the size of the letter “A” from Helvetica 4 points to 18 points so that the density becomes 2.0
These were processed under the following conditions.
[0131]

The composition of the developing solution is shown below.
[0132]

Water is added to make the total volume 1 liter, and the tank liquid is adjusted to pH = 10.10 and the replenisher is adjusted to pH = 10.60.
[0133]
Bleach fixer tank and replenisher
65 g of diethylenetriaminepentaacetic acid ferric ammonium dihydrate
Diethylenetriaminepentaacetic acid 3g
Ammonium thiosulfate (70% aqueous solution) 100 ml
2-amino-5-mercapto-1,3,4-thiadiazole 2.0 g
Ammonium sulfite (40%) 27.5ml
Add water to bring the total volume to 1 liter, and adjust to pH = 5.0 with potassium carbonate or glacial acetic acid.
[0134]
Stabilizing liquid tank liquid and replenishing liquid
o-Phenylphenol 1.0g
5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g
2-Methyl-4-isothiazolin-3-one 0.02 g
Diethylene glycol 1.0g
Fluorescent brightener (Chinopearl SFP) 2.0g
1-hydroxyethylidene-1,1-diphosphonic acid 1.8 g
Bismuth chloride (45% aqueous solution) 0.65 g
Magnesium sulfate heptahydrate 0.2g
PVP 1.0g
Ammonia water (25% ammonium hydroxide aqueous solution) 2.5 g
Nitrilotriacetic acid trisodium salt 1.5g
Water is added to make a total volume of 1 liter, and the pH is adjusted to 7.5 with sulfuric acid or ammonia water.
[0135]
(Multiple exposure aptitude evaluation)
In the samples (101) to (111) subjected to the exposure (1) and the color development described above, the gradient γ of the change in density with respect to the exposure amount between 0.5 and 1.5 is obtained for each of yellow, magenta, and cyan. The absolute value of the rate of change of the slope γ2 in the second exposure with respect to the slope γ1 in the single exposure was calculated as shown in Table 4 below.
[0136]
Gradation variation rate (%) = {| γ2−γ1 | / γ1} × 100
(Evaluation of density unevenness at gray density of 1.0)
In the samples (101) to (111) subjected to the exposure (2) and the color development, visual image unevenness was evaluated according to the following criteria.
[0137]
A: Image unevenness is not seen
○: Some unevenness in image
Δ: Image unevenness is observed
X: Image unevenness is clearly seen.
[0138]
(Evaluation of clarity of fine lines)
For the samples (101) to (111) subjected to the exposure (3) and the color development described above, the clarity of the fine lines was evaluated according to the following criteria.
[0139]
A: Gray thin line can be clearly distinguished
○: The gray thin line can be clearly distinguished, but the outline is slightly blurred
Δ: The outline of the gray thin line is blurred but can be distinguished
X: Gray thin line is blurred and cannot be distinguished.
[0140]
Table 4 shows the results.
[0141]
[Table 4]

[0142]
As is clear from Table 4, in Samples (102) and (107) in which the addition interval of the chemical sensitizer is 10 minutes with respect to the sample (101) for comparison, the gradation fluctuation range due to multiple exposure is reduced. It can be seen that the effect of improving the multiple exposure suitability is obtained, and the density stability at a gray density of 1.0 is also improved. However, the improvement effect is insufficient in terms of the clarity of the thin line. In contrast, samples (103) to (106) and (108) to (111) with a wide addition interval can improve the clarity of thin lines that could not be improved with an addition interval of 10 minutes, regardless of the type of sensitizer. all right.
[0143]
Example 2
(Preparation of red photosensitive emulsion)
The emulsion (101R) applied to the sample (101) of Example 1 is the same in the amount of chloroauric acid added, and the amount of sodium thiosulfate added is 1.3 mol of chloroauric acid in moles. Double emulsions were added, and emulsions (201R) differing in that the addition amounts of stabilizers STAB-1 to STAB-3 were optimized so as to obtain appropriate photographic sensitivity were prepared.
[0144]
Emulsion (101R) applied to sample (101) is the same as the addition amount of chloroauric acid to be added, and the addition amount of sodium thiosulfate is 1 times the amount of chloroauric acid in moles. Emulsions (202R) differing in that the addition amounts of stabilizers STAB-1 to STAB-3 were optimized so as to obtain excellent photographic sensitivity.
[0145]
Emulsion (101R) applied to sample (101) is the same as the addition amount of chloroauric acid, and the addition amount of sodium thiosulfate is 0.8 times the molar amount of chloroauric acid. A different emulsion (203R) was prepared by optimizing the addition amount of stabilizers STAB-1 to STAB-3 so as to obtain appropriate photographic sensitivity.
[0146]
Emulsion (101R) applied to sample (101) is the same as the addition amount of chloroauric acid, and the addition amount of sodium thiosulfate is 0.6 times the molar amount of chloroauric acid. A different emulsion (204R) was prepared by optimizing the addition amount of stabilizers STAB-1 to STAB-3 so as to obtain appropriate photographic sensitivity.
[0147]
Emulsion (101R) applied to sample (101) is the same amount of chloroauric acid added, and the amount of sodium thiosulfate added is 0.4 times the amount of chloroauric acid in moles. A different emulsion (205R) was prepared by optimizing the addition amount of stabilizers STAB-1 to STAB-3 so as to obtain appropriate photographic sensitivity.
[0148]
Emulsion (101R) applied to sample (101) is the same as the addition amount of chloroauric acid, and the addition amount of sodium thiosulfate is 0.3 times the amount of chloroauric acid in moles. A different emulsion (206R) was prepared by optimizing the addition amount of stabilizers STAB-1 to STAB-3 so as to obtain appropriate photographic sensitivity.
[0149]
(Preparation of green photosensitive emulsion)
Similar to the red photosensitive emulsions (201R) to (206R), the ratio of the addition amount of chloroauric acid and sodium thiosulfate was changed with respect to the emulsion (101G) applied to the sample (101) of Example 1 to change the green sensitivity. Emulsions (201G) to (206G) were prepared.
[0150]
(Preparation of blue-sensitive emulsion)
Similar to the red-sensitive emulsions (201R) to (206R), the ratio of the addition amount of chloroauric acid and sodium thiosulfate to the emulsion (101B) applied to the sample (101) of Example 1 was changed to make the green-sensitive film. Emulsions (201B) to (206B) were prepared.
[0151]
Using the emulsions prepared as described above, silver halide photographic light-sensitive materials (201) to (206) having the same constitution as in Example 1 were produced.
[0152]
[Table 5]

[0153]
As in Example 1, the samples (201) to (206) were evaluated for suitability for multiple exposure, density stability at a gray density of 1.0, and clarity of thin lines.
[0154]
The results are summarized in Table 6.
[0155]
[Table 6]

[0156]
As is clear from Tables 5 and 6, the sample (201) having a (sulfur / gold) ratio of 1.3 / 1, 1.0 / 1, 0.8 / 1, and 0.6 / 1, respectively ( 202), (203), and (204) show an improvement effect on the multiple exposure gradation fluctuation, but are not so effective for other evaluation items (density stability and fine line clarity). On the other hand, the samples (205) and (206) with the same ratio reduced to 0.4 and 0.3 showed improvements in multiple exposure gradation change, density stability, and fine line stability. The usefulness of setting the addition molar ratio of the sensitizer and the gold sensitizer to 0.5 or less can be recognized.
[0157]
Example 3
(Preparation of red photosensitive emulsion)
Emulsion (301R) differed from emulsion (101R) in Example 1 only in that dye R-1 was added in an amount of 15 mg per mole of silver halide when preparing the coating solution after the emulsion was prepared.
[0158]
An emulsion (302R) was prepared which differs from the emulsion (301R) only in that R-1 was added 100 minutes after the start of chemical ripening.
[0159]
An emulsion (303R) different from the emulsion (301R) only in that R-1 was added at the end of chemical ripening was prepared.
[0160]
An emulsion (304R) was prepared which differs from the emulsion (301R) only in that the amount of R-1 added was changed to 8 mg per mole of silver halide.
[0161]
An emulsion (305R) was prepared which differs from the emulsion (302R) only in that the amount of R-1 added was changed to 8 mg per mole of silver halide.
[0162]
An emulsion (306R) was prepared which differs from the emulsion (303R) only in that the amount of R-1 added was changed to 8 mg per mole of silver halide.
[0163]
An emulsion (307R) was prepared which differs from the emulsion (301R) only in that the amount of R-1 added was changed to 2 mg per mole of silver halide.
[0164]
An emulsion (308R) was prepared which differs from the emulsion (302R) only in that the amount of R-1 added was changed to 2 mg per mole of silver halide.
[0165]
An emulsion (309R) was prepared which differs from the emulsion (303R) only in that the amount of R-1 added was changed to 2 mg per mole of silver halide.
[0166]
Emulsions (310R) to (318R) were prepared in the same manner as emulsions (301R) to (309R), except that dye R-1 was changed to R-2.
[0167]
(Preparation of green and blue sensitive emulsions)
For the red-sensitive emulsion, green dyes were prepared in the same manner as emulsions (301R) to (309R) and emulsions (310R) to (318R), respectively, using dyes R-1 and R-2. The dyes G-1 and G-2 are used for the photosensitive emulsion, and the dyes B-1 and B-2 are used for the blue-sensitive emulsion. The emulsions (301G) to (318G) and the emulsions (301B) to (318B) are used. Was prepared.
[0168]
[Chemical 9]

[0169]
[Chemical Formula 10]

[0170]
Multilayer samples (301) to (318) were prepared under the same conditions as in Example 1 by combining these photosensitive emulsions.
[0171]
[Table 7]

[0172]
In the same manner as in Example 1, the samples (301) to (318) were evaluated for suitability for multiple exposure, density stability at a gray density of 1.0, and clarity of thin lines.
[0173]
The results are summarized in Table 8.
[0174]
[Table 8]

[0175]
As is clear from Tables 7 and 8, there are cases where a slight improvement effect is observed as in Samples (301) and (316) in which a dye is added to the coating solution, but the effect is not uniform. On the other hand, when the dye is added to the emulsion during chemical ripening, there are some evaluation items that can be improved as in the case of the addition of the coating solution when the addition amount is as large as 15 mg, but these are insufficient in terms of the effect. It is. On the other hand, at the level where the addition amount is reduced to 8 mg and 2 mg, the effects on the respective evaluation items such as the suitability for multiple exposure, the stability of concentration, and the clarity of fine lines can be confirmed even during chemical ripening or at the end of ripening. It can be seen that the samples (309) and (318) to which 2 mg was added at the end of chemical ripening had further improved effects.
[0176]
Example 4
The dyes B-1, G-1, and R-1 added in the samples (301) to (318) prepared in Example 2 were used as the desensitizing dye D-1, and the dyes B-2, G-2, and R-2. The multilayer samples (401) to (418) were produced which differed only in that they were changed to desensitizing dye D-2.
[0177]
Table 9 summarizes the emulsion composition, desensitizing dye, the amount and timing of addition of each sample.
[0178]
Embedded image

[0179]
[Table 9]

[0180]
About these samples, evaluation similar to Examples 1-3 was implemented.
[0181]
The results are summarized in Table 10.
[0182]
[Table 10]

[0183]
As is clear from Tables 9 and 10, in the sample to which the desensitizing dye was added as a coating solution, unlike Example 3, the effect on the stability of the thin line could not be confirmed regardless of the amount added. It turns out that an effect is inadequate also about multiple exposure aptitude and density stability.
[0184]
On the other hand, the sample to which the desensitizing dye is added during chemical ripening has an evaluation item where the effect is obtained when the addition amount is as large as 15 mg, and an evaluation item which is not. On the other hand, when the addition amount is reduced to 8 mg and 2 mg, it can be seen that the effects of improving the multiple exposure suitability, the density stability, and the fine line stability are obtained both during and after chemical ripening. Further, it can be seen that the effect of the invention is obtained in which the addition amount is reduced to 2 mg as seen in samples (409) and (418), and the addition at the end of chemical ripening is higher.
[0185]
According to the present invention, there are provided a silver halide photographic material, a silver halide emulsion, and an image forming method in which gradation fluctuation due to multiple exposure at high illuminance is small and image unevenness and image blur in scanning exposure are improved. did it.
[0186]
【The invention's effect】
According to the present invention, a silver halide photographic light-sensitive material having excellent multi-exposure suitability at high illuminance and good character quality even in scanning exposure. Fee And an image forming method can be provided.

Claims (3)

Each reflective support has at least one red photosensitive layer, green photosensitive layer, blue photosensitive layer and non-photosensitive layer, and at least one of the red photosensitive layer, the green photosensitive layer, and the blue photosensitive layer. A silver halide photograph in which one layer contains a silver halide emulsion having an average silver chloride content of 95% or more and a molar ratio of chalcogen sensitizer to added gold sensitizer being 0.5 or less. A light-sensitive material, and after exposure for 10 ⁻⁶ seconds or less, color development and image formation are performed, and a straight line passing through a point giving a density of 0.5 and a point giving a density of 1.5 on the obtained characteristic curve And a silver halide photographic light-sensitive material characterized in that the variation of the average gradient is within 10% in multiple exposure. Each reflective support has at least one red photosensitive layer, green photosensitive layer, blue photosensitive layer and non-photosensitive layer, and at least one of the red photosensitive layer, the green photosensitive layer, and the blue photosensitive layer. Halogen prepared by adding not more than 10 mg of dye or desensitizing dye having an average silver chloride content of 95% or more and a positive sum of polarographic anode potential and polarographic cathode potential per mole of silver halide. A silver halide photographic light-sensitive material containing a silver halide emulsion and color-developed and imaged after exposure for 10 ⁻⁶ seconds or less, giving a density of 0.5 on the obtained characteristic curve A silver halide photographic light-sensitive material characterized in that a straight line passing through a point giving a density of 1.5 is drawn and the variation of the average gradient is within 10% in multiple exposure. The silver halide photographic material according to any one of claims 1-2, after exposure of less than 10 ^-6 seconds, the image forming method characterized that you color development.