JP3994738B2 - Silver halide emulsion, silver halide photographic light-sensitive material, silver halide color photographic light-sensitive material, and image forming method using them - Google Patents

Description

【００９９】
（ハロゲン化銀乳剤Ｇ−７〜Ｇ−１３の調製）
上記ハロゲン化銀乳剤Ｇ−１の調製において、Ａ２液、Ａ３液、Ｂ２液及びＢ３液の添加量と臭化物（ＫＢｒ）、シアノ配位子錯体、炭素原子含有錯体の添加量を適宜調整、あるいは組み合わせて、表２に記載の特性値Ａ、特性値Ｂ及び特性値Ｃ（シアノ配位子錯体又は炭素原子含有錯体が存在する領域の深さ）からなるハロゲン化銀乳剤Ｇ−７〜Ｇ−１３を調製した。なお、特性値Ｂ及び特性値Ｃは、ハロゲン化銀粒子表面を０μｍとしたときの距離（μｍ）で表示した。
【０１００】
【表２】

【０１０１】
（緑感性ハロゲン化銀乳剤Ｇ２−１〜Ｇ２−１３の調製）
上記調製したハロゲン化銀乳剤Ｇ−１〜Ｇ−１３に対し、下記の各添加剤をこの順番で１分間隔で添加し、６５℃に保持し、７０分後さらにＳＴＡＢ−１を適切な感度が得られるよう添加し、カブリ−感度の関係が最適となるように化学増感を施し、緑感性ハロゲン化銀乳剤Ｇ２−１〜Ｇ２−１３を調製した。
【０１０２】

（青感性ハロゲン化銀乳剤Ｂ２−１の調製）
前記ハロゲン化銀乳剤Ｇ−１の調製において、Ａ１液、Ｂ１液、Ａ２液、Ｂ２液、Ａ３液及びＢ３液の添加時間を適宜変更した以外は同様にして、平均粒径０．６４μｍ、粒径分布の変動係数０．０７、塩化銀含有率９９．５モル％の単分散立方体乳剤であるハロゲン化銀乳剤Ｂ−１を得た。
【０１０３】
上記ハロゲン化銀乳剤Ｂ−１に対し、下記化合物を用いて６５℃で、この順番で１分間隔で添加し、カブリ−感度の関係が最適となるように化学増感を行い、青感性ハロゲン化銀乳剤Ｂ２−１を調製した。
【０１０４】
１：チオ硫酸ナトリウム ０．８ｍｇ／モルＡｇＸ
２：塩化金酸 １．５×１０^-5モル／モルＡｇＸ
３：安定剤（ＳＴＡＢ−１） ３×１０^-4モル／モルＡｇＸ
４：増感色素（ＢＳ−１） ４×１０^-4モル／モルＡｇＸ
５：増感色素（ＢＳ−２） １×１０^-4モル／モルＡｇＸ
（赤感性ハロゲン化銀乳剤Ｒ２−１の調製）
前記ハロゲン化銀乳剤Ｇ−１の調製において、Ａ１液、Ｂ１液、Ａ２液、Ｂ２液、Ａ３液及びＢ３液の添加時間を適宜変更した以外は同様にして、平均粒径０．４０μｍ、粒径分布の変動係数０．０８、塩化銀含有率９９．５モル％の単分散立方体乳剤であるハロゲン化銀乳剤Ｒ−１を得た。
【０１０５】
上記ハロゲン化銀乳剤Ｒ−１に対し、下記化合物を用いて６５℃で、この順番で１分間隔で添加し、カブリ−感度の関係が最適となるように化学増感を行い、赤感性ハロゲン化銀乳剤Ｒ２−１を調製した。
【０１０６】
１：チオ硫酸ナトリウム １．８ｍｇ／モルＡｇＸ
２：塩化金酸 １．５×１０^-5モル／モルＡｇＸ
３：安定剤（ＳＴＡＢ−１） １．２×１０^-4モル／モルＡｇＸ
４：増感色素（ＲＳ−１） １×１０^-4モル／モルＡｇＸ
５：増感色素（ＲＳ−２） １×１０^-4モル／モルＡｇＸ
ＳＴＡＢ−１：１−（３−アセトアミドフェニル）−５−メルカプトテトラゾール
また、赤感性ハロゲン化銀乳剤Ｒ２−１には、ＳＳ−１をハロゲン化銀１モル当り２．０×１０^-3ｇ添加した。
【０１０７】
【化１】

【０１０８】
《ハロゲン化銀カラー写真感光材料の作製》
（試料１の作製）
坪量１８０ｇ／ｍ²の紙パルプの乳剤層塗布面に、表面処理を施したアナターゼ型酸化チタンを１５質量％の含有量で分散して含む高密度溶融ポリエチレンをラミネートし、裏面には高密度ポリエチレンをラミネートした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、さらに表３、表４に記載の構成からなる各写真構成層を塗設して、ハロゲン化銀カラー写真感光材料である試料１を作製した。
【０１０９】
なお、第２層、第４層、および第７層には硬膜剤として（Ｈ−１）、（Ｈ−２）を添加した。また、各層には、表面張力調整用の塗布助剤として、界面活性剤（ＳＵ−２）、（ＳＵ−３）を添加した。また、各層に防黴剤（Ｆ−１）を全量が０．０４ｇ／ｍ²となるように添加した。尚、表中に記載のハロゲン化銀乳剤は、銀に換算した値で示した。
【０１１０】
【表３】

【０１１１】
【表４】

【０１１２】
試料１の作製に用いた各添加剤の詳細は、以下の通りである。
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
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
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
ＴＯＰ：トリオクチルホスフェート
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
ＨＱ−１：２，５−ジ−ｔ−オクチルハイドロキノン
ＨＱ−２：２，５−ジ−ｓｅｃ−ドデシルハイドロキノン
ＨＱ−３：２，５−ジ−ｓｅｃ−テトラデシルハイドロキノン
ＨＱ−４：２−ｓｅｃ−ドデシル−５−ｓｅｃ−テトラデシルハイドロキノン
ＨＱ−５：２，５−ジ〔（１，１−ジメチル−４−ヘキシルオキシカルボニル）ブチル〕ハイドロキノン
画像安定剤Ａ：Ｐ−ｔ−オクチルフェノール
画像安定剤Ｂ：ポリ（ｔ−ブチルアクリルアミド）
【０１１３】
【化２】

【０１１４】
【化３】

【０１１５】
【化４】

【０１１６】
【化５】

【０１１７】
【化６】

【０１１８】
（試料２〜１３の作製）
〈青感性及び赤感性ハロゲン化銀乳剤Ｂ２−２〜Ｂ２−１３及びＲ２−２〜Ｒ２−１３の調製〉
前記緑感性ハロゲン化銀乳剤Ｇ２−２〜Ｇ２−１３の調製で用いた各ハロゲン化銀乳剤の特性と同様にしたハロゲン化銀乳剤を調製した後、上記青感性ハロゲン化銀乳剤Ｂ２−１及び赤感性ハロゲン化銀乳剤Ｒ２−１と同様の方法で、化学増感及び分光増感を施した青感性ハロゲン化銀乳剤Ｂ２−２〜Ｂ２−１３、赤感性ハロゲン化銀乳剤Ｒ２−２〜Ｒ２−１３を調製した。
【０１１９】
〈ハロゲン化銀カラー写真感光材料の作製〉
上記試料１の作製において、青感性ハロゲン化銀乳剤Ｂ２−１、緑感性ハロゲン化銀乳剤Ｇ２−１、赤感性ハロゲン化銀乳剤Ｒ２−１に代えて、それぞれ青感性ハロゲン化銀乳剤Ｂ２−２〜Ｂ２−１３、緑感性ハロゲン化銀乳剤Ｇ２−２〜Ｇ２−１３、赤感性ハロゲン化銀乳剤Ｒ２−２〜Ｒ２−１３を用いた以外は同様にして、試料２〜１３を作製した。
【０１２０】
《ハロゲン化銀カラー写真感光材料の評価》
上記作製した試料１〜１３について、下記に記載の方法に従って、処理安定性及び潜像安定性の評価を行った。
【０１２１】
（処理安定性の評価）
１０^-6秒露光のキセノンフラッシュ高照度露光用感光計（山下電装（株）製ＳＸ−２０型）を用いてウエッジ露光し、露光した後１０分で下記現像処理工程に従って、発色現像処理１を行った。一方、発色現像処理液１Ｌ当たり漂白定着液を１．２ｍｌ混入した発色現像処理液を用いた以外は同様にして発色現像処理２を行った。
【０１２２】
以上のようにして現像処理を行った各試料のマゼンタ画像反射濃度を、光学濃度計（コニカ製ＰＤＡ−６５型）を用いてマゼンタ濃度を測定し、縦軸−反射濃度（Ｄ）、横軸−露光量（ＬｏｇＥ）からなる特性曲線を作成し、下記式１に従って、発色現像処理１での階調γ（γ１）と発色現像処理２での階調γ（γ２）を測定し、次いで、各々の階調γ値より下式２に従って、変動値ΔγＡを計算した。なお、ΔγＡは、数値が１００に近いほど処理安定性に優れていることを表す。
【０１２３】
式１
階調γ＝１／〔Ｌｏｇ（カブリ＋０．５の濃度を示す露光量）−Ｌｏｇ（カブリ＋１．５の濃度を示す露光量）〕
式２
ΔγＡ＝（γ２／γ１）×１００
（潜像安定性の評価）
１０^-6秒露光のキセノンフラッシュ高照度露光用感光計（山下電装（株）製ＳＸ−２０型）を用いてウエッジ露光し、露光して５分間放置した後、下記の発色現像処理１と同様にして発色現像処理３を行った。一方、上記方法において、露光した後５秒間経過してから同様に発色現像処理４を行った。
【０１２４】
以上のようにして現像処理を行った各試料のマゼンタ画像反射濃度を、光学濃度計（コニカ製ＰＤＡ−６５型）を用いてマゼンタ濃度を測定し、縦軸−反射濃度（Ｄ）、横軸−露光量（ＬｏｇＥ）からなる特性曲線を作成し、下記式３に従って、発色現像処理３での階調γ（γ３）と発色現像処理４での階調γ（γ４）を測定し、次いで、各々の階調γ値より下式４に従って、変動値ΔγＢを計算した。なお、ΔγＢは、数値が１００に近いほど潜像安定性に優れていることを表す。
【０１２５】
式３
階調γ＝１／〔Ｌｏｇ（カブリ＋０．１の濃度を示す露光量）−Ｌｏｇ（カブリ＋０．４の濃度を示す露光量）〕
式４
ΔγＢ＝（γ４／γ３）×１００
（発色現像処理１）
処理工程 処理温度 時間 補充量
発色現像 ３８．０±０．３℃ ４５秒 ８０ｍｌ
漂白定着 ３５．０±０．５℃ ４５秒 １２０ｍｌ
安定化 ３０〜３４℃ ６０秒 １５０ｍｌ
乾燥 ６０〜８０℃ ３０秒
（発色現像処理１の各現像処理液の組成）

それぞれ、水を加えて全量を１リットルとし、タンク液はｐＨを１０．１０に、補充液はｐＨを１０．６０に調整した。
【０１２６】
〈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％水溶液） 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を５．０に調整した。
【０１２７】
〈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（ポリビニルピロリドン） 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を７．５に調整した。
【０１２８】
以上より得られた各評価結果を表５に示す。
【０１２９】
【表５】

【０１３１】
実施例１
《ハロゲン化銀乳剤の調製》
（緑感性ハロゲン化銀乳剤Ｇ２−１４〜Ｇ２−１９の調製）
参考例に記載のハロゲン化銀乳剤Ｇ２−１の調製において、ＳＴＡＢ−１を所定量添加した後、５分後にＫＢｒを０．２８ｇ／モルＡｇＸ量添加する以外は同様にして化学増感処理を施して、ハロゲン化銀乳剤Ｇ２−１４を調製した。次いで、ハロゲン化銀乳剤Ｇ２−１４と同様にして、表６に記載のように、ＫＢｒの第１回目の添加位置及びＫＢｒの第１回目と第２回目の添加間隔を変更した以外は同様にして、ハロゲン化銀乳剤Ｇ２−１５〜Ｇ２−１９を調製した。第１回目及び第２回目のＫＢｒの添加量は、０．２８ｇ／モルＡｇに固定した。
【０１３２】
【表６】

【０１３３】
（青感性及び赤感性ハロゲン化銀乳剤Ｂ２−１４〜Ｂ２−１９、Ｒ２−１４〜Ｒ２−１９の調製）
上記ハロゲン化銀乳剤Ｇ２−１４〜Ｇ２−１９と同様にして、青感性ハロゲン化銀乳剤Ｂ２−１４〜Ｂ２−１９、赤感性ハロゲン化銀乳剤Ｒ２−１４〜Ｒ２−１９を調製した。
【０１３４】
《ハロゲン化銀カラー写真感光材料の作製及び評価》
参考例に記載の試料１の作製において、青感性ハロゲン化銀乳剤Ｂ２−１、緑感性ハロゲン化銀乳剤Ｇ２−１、赤感性ハロゲン化銀乳剤Ｒ２−１に代えて、それぞれ青感性ハロゲン化銀乳剤Ｂ２−１４〜Ｂ２−１９、緑感性ハロゲン化銀乳剤Ｇ２−１４〜Ｇ２−１９、赤感性ハロゲン化銀乳剤Ｒ２−１４〜Ｒ２−１９を用いた以外は同様にして、試料１４〜１９を作製し、参考例に記載の方法に従って、処理安定性及び潜像安定性の評価を行い、得られた結果を表７に示す。
【０１３５】
【表７】

【０１３６】
表７より明らかなように、本発明の試料は、処理安定性及び潜像安定性に対し効果が得られているが、臭化化合物２回の添加の間にカブリ防止剤（ＳＴＡＢ−１）を添加していない試料１５が試料１７より良好であり、さらに臭化化合物の第１回目の添加前にカブリ抑制化合物が添加していない試料１６に対しても良好な結果を示した。また、２回の添加における間隔が短い比較の試料１８では、本発明の効果は得られず、逆にこの間隔が長い試料１９は、良好な結果であった。
【０１３７】
前記実施例１で作製した試料１４〜１９を用いて、光源として、半導体レーザー（発振波長６５０ｎｍ）、Ｈｅ−Ｎｅガスレーザー（発振波長５４４ｎｍ）、Ａｒガスレーザー（発振波長４５８ｎｍ）を用い、光ビームのラスター間重なりが２５％となるように調整した走査露光装置を用いて、画像データに基づき各々のレーザービームに対してＡＯＭにより光量を変調しながら、ポリゴンに反射させて、感光材料上に主走査を行うと同時に、主走査方向に対して垂直方向に感光材料を搬送（副走査）して、１ｃｍ×１ｃｍのパッチ画像で、最大濃度から最小濃度まで段階的にグレーが再現できるように各色の露光量を調整しながら走査露光を行った。露光終了してから１時間後に上記発色現像処理１により処理を行った。このようにして得られたグレーパッチ画像の各ステップに対して濃度計ＰＤＡ−６５（コニカ社製）を用いて反射濃度を測定し、赤色レーザーの露光量に対する赤色光反射濃度のプロット（特性曲線）、緑色レーザーの露光量に対する緑色光反射濃度のプロット、青色レーザーの露光量に対する青色光反射濃度のプロットを作成した。次いで、各色画像に対して、ステップ毎に露光量に対する濃度の微分値を計算してポイントガンマを求め、ポイントガンマが１．０以上となる露光量領域（有効階調領域）を求めた。また、反射濃度０．８から１．８までの平均階調を同時に求めた。
【０１３８】
本発明の各試料は、比較試料に対して、処理安定性、潜像安定性に優れ、かつ各色画像形成層における有効階調領域（ＶＥ）は、いずれも０．６５以上０．８４以下であり、有効階調領域（ＶＥ）が最大となる色画像形成層のＶＥ値と、最小となる色画像形成層のＶＥ値の差（ΔＶＥ）が０以上０．０８以下を安定に再現でき、その結果、細線の再現性が安定に得られることが分かった。
【０１３９】
【発明の効果】
本発明により、ハロゲン化銀カラーペーパーに適した高照度露光時の現像安定性及び高照度露光時の潜像安定性に優れ、かつ細線の再現性が良好なハロゲン化銀乳剤、ハロゲン化銀写真感光材料、ハロゲン化銀カラー写真感光材料及びそれらを用いた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 emulsion, a silver halide photographic light-sensitive material, a silver halide color photographic light-sensitive material, and an image forming method using them, and more specifically, development stability and latent image at high illumination exposure. The present invention relates to a silver halide emulsion, a silver halide photographic light-sensitive material, a silver halide color photographic light-sensitive material having excellent stability and good fine line reproduction stability, and an image forming method using them.
[0002]
[Prior art]
In recent years, silver halide color paper has been handled in various places due to the development of minilab equipment and the like, and accordingly, exposure during printing has also been performed under various conditions and environments. Further, in the market, mixing of the bleaching desilvering processing solution with the color developing processing solution occurs, and the development stability becomes unstable. In recent years, digital processing of images has progressed rapidly, and the need for image formation by scanning exposure of high-intensity light sources such as light-emitting diodes and semiconductor lasers has been rapidly increasing. There is a strong demand for photosensitive materials (hereinafter also simply referred to as photosensitive materials) to have higher illuminance and further suitability for short-time exposure. In particular, it has been proved that the exposure to the processing liquid is more susceptible to exposure at high illuminance, and the latent image stability becomes unstable.
[0003]
That is, there is a strong demand for the appearance of a photosensitive material capable of obtaining a good image in both conventional photographic image formation and image formation by short-time scanning exposure using high-intensity light.
[0004]
On the other hand, Japanese Patent Application Laid-Open No. 64-26837 discloses a high silver chloride emulsion having a region having a high silver bromide content near the top of silver halide grains, and Japanese Patent Application Laid-Open No. 1-105940 discloses a silver bromide locality. It is disclosed that a high silver chloride emulsion excellent in latent image stability and reciprocity failure characteristics can be provided by selectively doping Ir in a region. U.S. Pat. No. 5,627,020 discloses a method for forming a localized region of silver bromide using Ir-doped silver bromide fine particles. It was never enough to improve the stability of latent images. JP-A-11-109534 has a silver bromide-rich phase containing an iridium compound in the vicinity of the surface of silver halide grains, and the iridium compound density is inside the silver bromide-rich phase. It describes silver halide emulsions that have improved reciprocity failure, latent image stability, and high humidity dependence by making the region higher than the outside. These inventions are characterized in that a localized phase containing 10 to 40% of high silver bromide is provided at the top of the silver halide grains, but this is insufficient in terms of the stability and processing stability of the silver halide emulsion. .
[0005]
Japanese Patent Laid-Open No. 2001-188311 has a rich phase of silver bromide and silver iodide in the vicinity of the surface of silver halide grains, and this rich phase is introduced twice before and after the addition of the antifoggant compound. The method for improving the reciprocity law failure and the coating solution stagnation is described, but the storage stability of the silver halide emulsion is insufficient.
[0006]
Examples of disclosure relating to doping of a complex containing a cyano ligand include European Patent Nos. 336,425 and 336,426, JP-A-2-20853, JP-A-2-20854, and JP-A-5-66511. It is widely known in Japanese Patent Nos. 5,132,203, 4,847,191, 3,790,390, and Japanese Patent Publication No. 48-35373. In these patents, it is shown that high sensitivity, reciprocity failure, etc. are improved, but problems still remain in terms of latent image stability and fog resistance in development processing. Furthermore, JP-A Nos. 11-24194, 11-102042, 10-293377, 8-179252, 7-72569, U.S. Pat. Nos. 5,360,712, 5,457,021. No. 5,462, 849, etc., describe the enhancement of sensitivity by an organic ligand compound complex having bipyridine, CO, pyrimidine, imidazole or the like as a ligand. However, the development stability or latent image stability is still insufficient and improvements are desired.
[0007]
[Problems to be solved by the invention]
An object of the present invention is to provide a silver halide emulsion and a halogenated silver halide emulsion, which are suitable for silver halide color paper, have excellent development stability at high illumination exposure and latent image stability at high illumination exposure, and good reproducibility of fine lines. A silver photographic light-sensitive material, a silver halide color photographic light-sensitive material, and an image forming method using them.
[0008]
[Means for Solving the Problems]
As a result of intensive studies in view of the above-mentioned problems, the present inventors have found that the above-described problems of the present invention can be achieved by the configuration described below, and have completed the present invention.
[0009]
  1. In a silver halide emulsion comprising silver chlorobromide grains or silver chloroiodobromide grains having a silver chloride content of 98% or more, the silver chlorobromide grains or silver chloroiodobromide grainsChemical sensitizationSometimes the bromide compound is added at least twice, and chemical sensitization is applied for 60 minutes or more during the addition period.The silver chlorobromide grains or silver chloroiodobromide grains have a region having a silver bromide content of 0.5 to 5% in a region having a depth of 0 to 0.01 μm from the grain surface, and from the grain surface. A doped region of a cyano ligand-containing complex exists at a depth of 0.001 to 0.01 μm, and a region closer to the particle surface than the doped region contains a cyano ligand-containing complex and a carbon atom-containing complex. There is a phase that does notA silver halide emulsion characterized by
[0012]
  2. The silver chlorobromide grain or silver chloroiodobromide grain has a carbon atom-containing complex doped region at a depth of 0.001 to 0.01 μm from the grain surface, and is closer to the grain surface than the doped region. In the region, there is a phase that does not contain a carbon atom-containing complex and a cyano ligand-containing complex.1The silver halide emulsion as described.
[0013]
  3. The silver chlorobromide grains or the silver chloroiodobromide grains are gold sensitized.Or 2A silver halide emulsion described in 1.
[0014]
  4. 50% or more of the total projected area of the silver chlorobromide grain or silver chloroiodobromide grain is a tabular grain having an aspect ratio of 2 or more.3The silver halide emulsion according to any one of the above.
[0015]
  5. It has at least one image forming layer on the support, and the image forming layer is4A silver halide photographic light-sensitive material comprising the silver halide emulsion described in any one of the above.
[0016]
  6. In a silver halide color photographic light-sensitive material having at least one yellow image forming layer, magenta image forming layer, and cyan image forming layer each containing at least photosensitive silver halide on a support, the color image At least one of the forming layers is 1 to4And a silver halide emulsion according to any one of 10^-Ten10 seconds or more^-3The effective gradation region (VE) of the color image obtained by performing color development after exposure with an exposure time of less than 2 seconds is 0.65 or more and 0.84 or less for each color image forming layer, and the effective floor. The halogen having a difference (ΔVE) between 0 and 0.08 or less between the VE value of the color image forming layer having the maximum tone area (VE) and the VE value of the color image forming layer having the minimum tone area (VE) Silver halide color photographic material.
[0017]
  7. Said610 to 10 per pixel.^-Ten10 seconds or more^-3An image forming method comprising performing color development after exposure with an exposure time of seconds or less.
[0020]
  In the invention according to claim 1, in a silver halide emulsion comprising silver chlorobromide grains or silver chloroiodobromide grains having a silver chloride content of 98% or more, the silver chlorobromide grains or silver chloroiodobromide grainsChemical sensitizationSometimes bromide compound is added at least twice and chemical sensitization treatment is more than 60 minutes during the addition periodAnd the silver chlorobromide grains or silver chloroiodobromide grains have a region having a silver bromide content of 0.5 to 5% in a region having a depth of 0 to 0.01 μm from the grain surface, and A cyano ligand-containing complex and a carbon atom-containing complex are present in a region where the doped region of the cyano ligand-containing complex is present at a depth of 0.001 to 0.01 μm from the surface, and closer to the particle surface than the doped region. There is a phase that does not containIt has been found that by satisfying the conditions specified in the present invention, both processing stability and latent image stability can be achieved, and good emulsion stability can be achieved.
  The bromide compound according to the present invention is not particularly limited as long as it is a bromide, but is preferably a water-soluble compound, and examples thereof include KBr, NaBr, AgBrCl, and AgBr. The addition method isIn the chemical sensitization processAlthough it is performed at least twice, it is preferable that the addition interval of the two times is after the addition of the sensitizer and until reaching the appropriate point of the chemical sensitization treatment. The sensitizing treatment is performed for 60 minutes or longer, preferably 120 minutes or longer. It is more preferable to perform the first bromide addition in the presence of an antifoggant. It is more preferable to add an antifoggant after the second bromide addition. Furthermore, it is preferred not to add antifoggant compounds between the two bromide additions.
  Claim1In this invention, the silver chlorobromide grain or the silver chloroiodobromide grain may have a region having a silver bromide content of 0.5 to 5% in a region having a depth of 0 to 0.01 μm from the grain surface. The formation of a silver bromide-containing phase in a silver halide emulsion is characteristic in that the grain size is smaller than that of the host grain, and the grain size is 0.1 μm or less, more preferably 0.07 μm or less. It can also be formed by adding 5 to 5% of silver halide fine grains, but the silver bromide content of the aqueous halide solution added in the double jet addition method known in the art is 0.5 to 5%. It is more preferable to adjust to. The silver bromide content of the finally obtained silver halide emulsion is preferably 0.1 to 0.5 mol% with respect to the total silver amount.
[0021]
By uniformly providing a low silver bromide-containing phase having a silver bromide content of 0.5 to 5% as described above from the grain surface to the subsurface part, both processing stability and latent image stability are achieved. In addition, it has been found that good emulsion stability can be achieved, and a low silver bromide-containing phase having a silver bromide content of 2 to 4% is preferred.
[0022]
  Claims1In this invention, the silver chlorobromide grain or silver chloroiodobromide grain has a doped region of a cyano ligand-containing complex at a depth of 0.001 to 0.01 μm from the grain surface, and The region closer to the particle surface than the doped region is characterized by the presence of a phase that does not contain a cyano ligand-containing complex and a carbon atom-containing complex.
[0023]
The cyano ligand-containing complex according to the present invention is not particularly limited as long as it is a complex in which at least one cyano ligand is coordinated. Preferably, iron, ruthenium or osmium has 4 It is a complex in which two or more are coordinated. Specific examples of the cyano ligand-containing complex that can be used in the present invention are shown below, but the present invention is not limited thereto.
[0024]
  A1: K_FourFe (CN)₆
  A2: K_FourRu (CN)₆
  A3: K_FourOs (CN)₆
  Claim2In the invention according to the invention, the silver chlorobromide grain or the silver chloroiodobromide grain has a doped region of a carbon atom-containing complex at a depth of 0.001 to 0.01 μm from the grain surface, and the doped region The region closer to the particle surface is characterized by the presence of a phase that does not contain a carbon atom-containing complex and a cyano ligand-containing complex.
[0025]
The carbon atom-containing complex according to the present invention is a complex in which at least one ligand containing carbon is coordinated, and specific examples of the compounds are shown below. It is not limited to these.
[0026]
B1: [Ru (byp)₂(S-NH_Three-Phen)]²⁺
B2: Ru (acetylacetonate)_Three
B3: [(NH_Three)_FiveRu-NC-C₆H_Four-CN-Ru (NH_Three)_Five]
(PF₆)_Four
B4: [RuCl₂(Byp)₂]
In addition, the abbreviation described in the said compound is as follows.
[0027]
byp: bipyridine
phen: Phenanthroline
In order to contain each complex compound according to the present invention in the silver halide emulsion of the present invention, each complex compound according to the present invention is added to a silver halide grain pre-formation step, a silver halide grain formation step, or a halogen What is necessary is just to add at the time of becoming the structure which concerns on this invention in each process of the physical ripening process after formation of a silver halide grain. In order to obtain a silver halide emulsion satisfying the grain constitution defined in the present invention, it is preferable to dissolve the complex compound according to the present invention together with a halide salt and add it during the grain formation step.
[0028]
The amount of the complex compound according to the present invention added to the silver halide emulsion is 1 × 10 5 per mole of silver halide.^-9Mole or more, 1 × 10^-2Mole or less is more preferable, especially 1 × 10^-8More than mole 5 × 10^-FiveMolar or less is preferable.
[0029]
In order to obtain the silver halide emulsion of the present invention, heavy metal ions may be further contained inside the grains. Examples of heavy metal ions that can be used include Group 8 to 10 metals such as iron, iridium, platinum, palladium, nickel, rhodium, osmium, ruthenium and cobalt, Group 12 transition metals such as cadmium, zinc and mercury, Examples thereof include lead, rhenium, molybdenum, tungsten, gallium, and chromium ions. Further, a complex having a desensitizing action containing a halogen ion or nitrosyl or thionitrosyl as a ligand may be combined.
[0032]
  Claim6In the invention according to the present invention, a silver halide color photographic light-sensitive material having at least one yellow color image forming layer, magenta color image forming layer and cyan color image forming layer each containing at least a photosensitive silver halide on a support. And at least one of the color image forming layers contains the silver halide emulsion according to any one of claims 1 to 6, and 10 per pixel.^-Ten10 seconds or more^-3The effective gradation region (VE) of the color image obtained by performing color development after exposure with an exposure time of less than 2 seconds is 0.65 or more and 0.84 or less for each color image forming layer, and the effective floor. The difference (ΔVE) between the VE value of the color image forming layer having the maximum tone area (VE) and the VE value of the color image forming layer having the minimum tone region (VE) is 0 to 0.08.
[0033]
The effective gradation region (VE) in the present invention is defined as an exposure amount region where the point gamma value at the time of gray scale output is 1.0 or more. As a result of intensive studies, the present inventors have a great influence on the print image quality at the time of digital exposure. In particular, when the processing time from exposure to development changes, the bleeding of the character image and the scanning exposure streak It has been found that the influence on the ease of delivery is large.
[0034]
The point gamma referred to in the present invention is described in T.W. H. As described in James, “The Theory of the Photographic Process”, 4th edition, page 502,
Point gamma = dD / dLogE (D represents density, E represents exposure)
And represents a differential value at an arbitrary point on a characteristic curve (D-LogE curve) having a vertical axis—density D and a horizontal axis—exposure amount.
[0035]
In the present invention, the exposure time per pixel is 10^-Ten10 seconds or more^-3By satisfying the requirements stipulated in the present invention under the exposure conditions of 2 seconds or less, the intended effect of the present invention can be obtained. In order to clarify the effect of the present invention, the following An evaluation method can be preferably used.
[0036]
That is, using a laser scanning exposure apparatus adjusted so that the overlap between the rasters of the light beam is within the range of 5 to 30%, the 1 cm square patch is exposed on the photosensitive material while changing the exposure amount, Using the following color developer (CDC-1), color development for 45 seconds at 37 ± 0.5 ° C. (after color development, normal bleach-fixing and washing or stabilization treatment are performed) The reflection density of the gray patch portion of the obtained sample is measured, and a characteristic curve composed of the horizontal axis: exposure amount (Log E) and the vertical axis: reflection density (D) is created. The point gamma can be obtained by calculating the differential value. In the present invention, the time from the end of exposure to the start of development is 1 hour.
[0037]
[Color developer (CDC-1)]
800ml of pure water
Triethylenediamine 2g
Diethylene glycol 10g
Potassium bromide 0.02g
Potassium chloride 4.5g
Potassium sulfite 0.25g
N-ethyl-N- (β methanesulfonamidoethyl) -3-methyl-4-
Aminoaniline sulfate 4.0g
5.6 g of N, N-diethylhydroxylamine
Triethanolamine 10.0g
Diethylenetriaminepentaacetic acid sodium salt 2.0 g
30g potassium carbonate
Water is added to bring the total volume to 1 liter, and the pH is adjusted to 10.1 with sulfuric acid or potassium hydroxide.
[0038]
In the present invention, the diameter of the light beam (beam diameter) is defined as the raster width. Here, the light beam diameter is e where the light beam intensity is the maximum intensity (center of the beam).^-2It can be defined as the diameter of a circle formed by taking out the doubled portion, and can be obtained by, for example, a beam monitor combining a slit and a power meter.
[0039]
Next, the constitution of the silver halide emulsion and the constituent factors of the silver halide color photographic light-sensitive material other than those explained above will be explained in detail.
[0040]
The silver halide emulsion of the present invention may be obtained by any of the acidic method, neutral method and ammonia method. Further, the silver halide grains may be grown at once, or may be grown after preparing seed grains. The method of preparing the seed particles and the method of growing the particles may be the same or different.
[0041]
In addition, 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, or a combination thereof, but those obtained by the simultaneous mixing method are preferred. . Furthermore, the pAg controlled double jet method described in JP-A No. 54-48521 can be used as one type of the simultaneous mixing method.
[0042]
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. 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.
[0043]
In the light-sensitive material of the present invention, any silver halide grains can be used. One preferable example is a cube having a (100) plane as a crystal surface. 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), etc., particles having an octahedron, tetrahedron, dodecahedron, etc. can be produced and used. Furthermore, particles having twin planes may be used.
[0044]
  Claim4According to the invention, the silver halide emulsion is characterized in that 50% or more of the total projected area of the silver halide grains is tabular grains having an aspect ratio of 2 or more.
[0045]
In the light-sensitive material of the present invention, silver halide grains having a single shape are preferably used, but it is particularly preferable to add two or more monodispersed silver halide emulsions in the same layer.
[0046]
The particle 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 0.1 μm, considering rapid processability, sensitivity, and other photographic performance. It is in the range of 2 to 1.0 μm. This particle size can be measured using the projected area or diameter approximation of the particle. If the particles are substantially uniform in shape, the particle size distribution can be expressed as a diameter or a projected area.
[0047]
The particle size distribution of the silver halide grains used in the light-sensitive material 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. Two or more monodispersed emulsions of 0.15 or less are added to the same layer. The variation coefficient here is a coefficient representing the breadth of the particle size distribution, and is defined by the following equation.
[0048]
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 having a shape other than a cube or a sphere. .
[0049]
As a silver halide emulsion preparation apparatus and method, various methods known in the art can be used.
[0050]
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. 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.
[0051]
  Claim3The invention according to the present invention is characterized in that the silver halide grains are gold sensitized, but a gold sensitizing method and a sensitizing method using a chalcogen sensitizer can be used in combination. As the chalcogen sensitizer applied to the silver halide emulsion, for example, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer and the like can be used, and among them, a sulfur sensitizer is preferable. Examples of the sulfur sensitizer include thiosulfate, allylthiocarbamide thiourea, allyl isothiocyanate, cystine, p-toluenethiosulfonate, rhodanine, inorganic sulfur and the like. The amount of sulfur sensitizer added is preferably changed depending on the type of silver halide emulsion to be applied and the magnitude of the expected effect, but is generally 5 × 10 5 per mole of silver halide.^-Ten~ 5x10^-FiveIn the molar range, preferably 5 × 10^-8~ 3x10^-FiveA molar range is preferred.
[0052]
As the gold sensitizer, for example, 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. Furthermore, a gold sensitizer containing a sensitizing component such as sulfur or selenium and a gold sensitizer having a group forming silver sulfide or selenium silver are also preferable.
[0053]
The amount of the gold compound used is not uniform depending on the type of silver halide emulsion, the type of compound used, ripening conditions, etc., but usually 1 × 10 6 per mole of silver halide.^-Four~ 1x10^-8Mole is preferred. More preferably 1 × 10^-Five~ 1x10^-8Is a mole. As chemical sensitization of the silver halide emulsion according to the present invention, reduction sensitization may be used.
[0054]
The silver halide emulsion used in the light-sensitive material of the present invention is known for the purpose of preventing fogging that occurs during the preparation process of the light-sensitive material, reducing performance fluctuations during storage, and preventing fogging that occurs 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 the lower column of page 7 of JP-A-2-14636. Specific compounds include compounds (IIa-1) to (IIa-8) and (IIb-1) to (IIb-7) described on page 8 of the same publication, and 1- (3-methoxyphenyl). Examples include compounds such as -5-mercaptotetrazole 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~ 5x10^-FourIt is preferably used in a molar amount. When added at the end of chemical sensitization, 1 x 10 per mole of silver halide^-6~ 1x10^-2A molar amount is preferred, 1 × 10^-Five~ 5x10^-3Mole 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~ 1x10^-1A molar amount is preferred, 1 × 10^-Five~ 1x10^-2Mole is more preferred. In addition, when added to a constituent layer other than the silver halide emulsion layer, the amount in the coating film is 1 m.²1 × 10 per^-9~ 1x10^-3A molar amount is preferred.
[0055]
In the light-sensitive material of the present invention, dyes having absorption in various wavelength ranges can be used for the purpose of preventing irradiation and preventing halation. 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 special dyes can be used. The dyes described in the specification of Kaihei 6-3770 and the dyes described in JP-A-11-119379 are preferably used, and the infrared absorbing dye is described in the lower left column on page 2 of JP-A-1-280750. The compounds represented by the general formulas (I), (II), and (III) described above have preferable spectral characteristics and are preferable without affecting the photographic characteristics of silver halide photographic emulsions and without causing contamination by residual colors. . 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. For the purpose of improving sharpness, the amount of these dyes added is preferably such that the spectral reflection density at 680 nm of the untreated sample of the photosensitive material is 0.7 or more, and more preferably 0.8 or more. preferable.
[0056]
It is preferable to add a fluorescent brightening agent to the light-sensitive material of 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.
[0057]
The silver halide color photographic light-sensitive material of the present invention has a layer containing a silver halide emulsion spectrally sensitized in a specific region of a wavelength region of 400 to 900 nm in combination with a yellow coupler, a magenta coupler, and a cyan coupler. The silver halide emulsion contains one or a combination of two or more sensitizing dyes.
[0058]
As the spectral sensitizing dye used in the silver halide emulsion of the present invention, known compounds can be used. As the blue-sensitive sensitizing dye, BS-1 described in JP-A-3-251840, page 28, can be used. ~ 8 can be preferably used alone or in combination. As the green photosensitive sensitizing dye, GS-1 to GS-5 described on page 28 of the same publication are preferably used. As the red photosensitive sensitizing dye, RS-1 to RS-8 described on page 29 of the same publication are preferably used. In addition, when performing image exposure with infrared light using a semiconductor laser or the like, it is necessary to use an infrared photosensitive sensitizing dye. As the infrared photosensitive sensitizing dye, JP-A-4-285950 is disclosed. The pigments of IRS-1 to IRS-11 described in pages 6 to 8 of the publication are preferably used. Further, these infrared, red, green, and blue photosensitive sensitizing dyes are supersensitizers SS-1 to SS-9 described in JP-A-4-285950, pages 8 to 9 and JP-A-5-66515. It is preferable to use a combination of compounds S-1 to S-17 described in JP-A No. 15-17. These sensitizing dyes may be added at any time from the formation of silver halide grains to the end of chemical sensitization.
[0059]
As a method for adding a sensitizing dye, for example, it may be added as a solution by dissolving in water-miscible organic solvent such as methanol, ethanol, fluorinated alcohol, acetone, dimethylformamide or water, or as a solid dispersion. May be.
[0060]
As the coupler used in the silver halide color photographic light-sensitive material of the present invention, a coupling product having a spectral absorption maximum wavelength in a wavelength region longer than 340 nm can be formed by a coupling reaction with an oxidized color developing agent. Any compound can be used, but particularly representative compounds include yellow dye-forming couplers having a spectral absorption maximum wavelength in the wavelength range of 350 to 500 nm, and magenta dye formation having a spectral absorption maximum wavelength in the wavelength range of 500 to 600 nm. Typical couplers are those known as cyan dye-forming couplers having a spectral absorption maximum wavelength in the wavelength range of 600 to 750 nm.
[0061]
Examples of the cyan coupler that can be preferably used in the silver halide color photographic light-sensitive material of the present invention include general formulas (CI) and (C-II) described in JP-A-4-114154, page 5, lower left column. The coupler represented by these can be mentioned. Specific examples of the compound include those described as CC-1 to CC-9 in the lower right column on page 5 to the lower left column on page 6 of the publication.
[0062]
As the magenta coupler which can be preferably used in the silver halide color photographic light-sensitive material of the present invention, general formulas (M-I) and (M-II) described in JP-A-4-114154, page 4, upper right column. The coupler represented by these can be mentioned. Specific examples of the compound include those described as MC-1 to MC-11 in the lower left column on page 4 to the upper right column on page 5. Among the magenta couplers, a coupler represented by the general formula (M-I) described in the upper right column of page 4 of the same publication is more preferable. Among them, the RM of the general formula (M-I) A coupler in which is a tertiary alkyl group is excellent in light resistance and is particularly preferred. MC-8 to MC-11 described in the upper column of page 5 of the same publication are preferable because they have excellent color reproducibility from blue to purple and red, and are excellent in detail descriptive power.
[0063]
As a yellow coupler which can be preferably used in the silver halide color photographic light-sensitive material of 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 disclosed. Can be mentioned. Specific examples of the compound include those described as YC-1 to YC-9 in the lower left column on page 3 of the same specification. Above all, RY of the general formula [Y-1] in the specification of the publication₁A coupler in which 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 a yellow color having a preferable color tone. Particularly preferred examples of these compounds include YC-8 and YC-9 described in the lower left column of page 4 of JP-A-4-114154 and pages 13 to 14 of JP-A-6-67388. The compound shown by description No (1)-(47) can be mentioned. Further, the most preferable compound is a compound represented by the general formula [Y-1] described in JP-A-4-81847, page 1 and JP-A-11-page 17.
[0064]
In the case of using an oil-in-water emulsion dispersion method as a method for adding a coupler or other organic compound used in the silver halide color photographic light-sensitive material of the present invention, it is usually a water-insoluble high boiling organic solvent having a boiling point of 150 ° C. 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 the 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. Examples of high-boiling organic solvents that can be used to dissolve and disperse couplers include phthalates such as dioctyl phthalate, diisodecyl phthalate, and dibutyl phthalate, and phosphate esters such as tricresyl phosphate and trioctyl phthalate. Alcohols and alcohols are preferably used. The dielectric constant of the high boiling point organic solvent is preferably 3.5 to 7.0. Two or more high boiling point organic solvents can be used in combination.
[0065]
On the other hand, in place of the above method 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. Further, 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 employed. Examples of the water-insoluble and organic solvent-soluble polymer used at this time include poly (Nt-butylacrylamide).
[0066]
Preferred compounds as surfactants used to disperse photographic additives and adjust the surface tension during application include those containing a hydrophobic group having 8 to 30 carbon atoms and a sulfonic acid group or a salt thereof in one molecule. 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 it is preferable that the time until dispersion is added to the coating solution after dispersion and the time from addition to coating after coating is shorter. It is preferably within 10 hours, more preferably within 3 hours, and even more preferably within 20 minutes.
[0067]
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 formula I and general formula II described on page 3 of JP-A-2-665541, and phenols represented by general formula IIIB described in JP-A-3-174150. Compounds, general amines represented by general formula A described in JP-A-64-90445, and metal complexes represented by general formulas XII, XIII, XIV and XV described in JP-A-62-182441 Preferred for magenta dyes. Further, compounds represented by general formula I 'described in JP-A-1-196049 and compounds represented by general formula II described in JP-A-5-11417 are particularly preferred for yellow and cyan dyes.
[0068]
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. can be used. Besides these, fluorescent dye releasing compounds described in US Pat. No. 4,774,187 can also be used.
[0069]
In the silver halide color photographic light-sensitive material of 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 is added to the silver halide-containing 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. Particularly preferred compounds are compounds represented by the general formula II described in JP-A-4-13356, and compounds II-1 to II-14 and pages 17 described on pages 13 to 14 of the same publication. Compound 1 is mentioned.
[0070]
In the silver halide color photographic light-sensitive material of 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 JP-A-64-66646. Compounds represented by general formula III, UV-1L to UV-27L described in JP-A-63-187240, compounds represented by general formula I described in JP-A-4-16333, JP-A-5-165144 And compounds represented by the general formulas (I) and (II) described in Japanese Patent Publication.
[0071]
In the silver halide color photographic light-sensitive material of the present invention, it is advantageous to use gelatin as a binder, but other gelatins such as gelatin derivatives, gelatin and other polymer graft polymers, other than gelatin as necessary. It is also possible to use hydrophilic colloids such as synthetic hydrophilic polymer substances such as proteins, sugar derivatives, cellulose derivatives, and single or copolymers.
[0072]
As the binder hardener, it is preferable to use a vinylsulfone type hardener or a chlorotriazine type hardener alone or in combination. 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 to the colloid layer in order to prevent the growth of mold and bacteria that adversely affect photographic performance and image storage stability. In order to improve the physical properties of the surface of the photosensitive material or processed sample, a slipping agent or matting agent described in JP-A-6-118543 or JP-A-2-73250 is added to the protective layer. Is preferred.
[0073]
As the support used for the photosensitive material of the present invention, any material may be used, including paper coated with polyethylene or polyethylene terephthalate, paper support made of natural pulp or synthetic pulp, vinyl chloride sheet, white pigment Polypropylene, polyethylene terephthalate support, baryta paper or the like that may be used may 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.
[0074]
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 finely divided silicic acid, synthetic silicate, calcium silicate, alumina, alumina hydrate, Examples thereof include titanium oxide, zinc oxide, talc, and clay. Preferred white pigments are barium sulfate and titanium oxide.
[0075]
The amount of the white pigment contained in the water-resistant resin layer on the surface of the support is preferably 13% by mass or more, and more preferably 15% by mass for improving sharpness.
[0076]
In the paper support used in the light-sensitive material of the present invention, the degree of dispersion of the white pigment in the water-resistant resin layer 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.
[0077]
Moreover, when 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, the effect of good gloss is obtained, which is more preferable. In addition, in the water-resistant resin containing the white pigment of the reflective support or in the coated hydrophilic colloid layer, in order to improve the whiteness by adjusting the spectral reflection density balance of the white background after processing, for example, ultramarine, It is preferable to add a slight amount of a bluening agent, a redning agent, or a fluorescent brightening agent such as an oil-soluble dye.
[0078]
The light-sensitive material of the present invention is subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the support surface as necessary, and then each photographic composition layer is directly or undercoat (adhesiveness 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).
[0079]
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.
[0080]
In order to form a photographic image using the photosensitive material of the present invention, the image recorded on the negative may be optically imaged and printed on the photosensitive material to be printed. After conversion to information, the image may be formed on a CRT (cathode ray tube), and the image may be formed on a photosensitive material to be printed and printed, or the intensity of laser light based on digital information. The image may be printed by scanning while changing the above.
[0081]
In the present invention, it is preferably applied to a photosensitive material that does not contain a developing agent, and particularly preferably applied to a photosensitive material that directly forms an image for viewing. For example, color paper, color reversal paper, positive Examples thereof include photosensitive materials for forming images, photosensitive materials for displays, and photosensitive materials for color proofing. 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 color developer can be used in any pH range, but is preferably pH 9.5 to 13.0, more preferably pH 9.8 to 12.0 from the viewpoint of rapid processing. is there.
[0084]
The processing temperature for color development is preferably 35 ° C. or higher and 70 ° C. or lower. The higher the temperature, the shorter the treatment possible and the better. However, it is preferable that the temperature is not so high from the stability of the treatment liquid, and the treatment is preferably performed at 37 ° C. or more and 60 ° C. or less.
[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, a known developer component compound 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 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. The development processing apparatus used for the development processing of the photosensitive material of the present invention is a roller transport type that conveys the photosensitive material between the rollers disposed in the processing tank, and conveys the photosensitive material fixed to the belt. The endless belt method may be used, but the processing tank is formed in a slit shape, the processing liquid is supplied to the processing tank and the photosensitive material is transported, the spraying method of spraying the processing liquid, the processing liquid It is also possible to use a web system by contact with a carrier impregnated with, a system using a viscous treatment liquid, or the like. In the case of processing in large quantities, a running process is usually performed using an automatic processor. At this time, the replenishment amount of the replenisher is preferably as small as possible, and the most preferable processing form in view of environmental suitability is the tablet as a replenishment method. 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]
  Reference example
  << Preparation of silver halide emulsion >>
  (Preparation of silver halide emulsion G-1)
  In 1 liter of 2% gelatin aqueous solution kept at 40 ° C., the following A1 solution and B1 solution were simultaneously added over 20 minutes while controlling pAg = 7.3 and pH = 3.0, and then the following A2 solution and B2 The liquids were simultaneously added over 100 minutes while controlling pAg = 8.0 and pH = 5.5. Subsequently, the following A3 liquid and B3 liquid were simultaneously added over 5 minutes while controlling pAg = 8.0 and pH = 5.5. At this time, the pAg was controlled according to the method described in JP-A-59-45437, and the pH was appropriately controlled using sulfuric acid or a sodium hydroxide aqueous solution.
[0090]
(A1 solution)
Sodium chloride 0.48g
Potassium bromide 0.004g
Water was added to a final volume of 28 ml.
[0091]
(A2 liquid)
Sodium chloride 116.9g
Potassium bromide 0.12g
K₂IrCl₆                                      1.0 × 10^-Fiveg
K_FourFe (CN)₆・ 3H₂O 9.3 × 10^-3g
Water was added to make 597 ml.
[0092]
(A3 liquid)
Sodium chloride 12.5g
K₂IrCl₆                                      5.5 × 10^-7g
K_FourFe (CN)₆・ 3H₂O 4.6 × 10^-Fourg
Water was added to make up to 64 ml.
[0093]
(B1 solution)
Silver nitrate 1.4g
Water was added to a final volume of 28 ml.
[0094]
(B2 liquid)
341 g of silver nitrate
Water was added to make 597 ml.
[0095]
(B3 liquid)
Silver nitrate 35.6g
Water was added to make up to 64 ml.
[0096]
After each of the above solutions was added, desalting was performed using a 5% aqueous solution of Demol N manufactured 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. A silver halide emulsion G-1 which was a monodispersed cube having a coefficient of variation of distribution of 0.08 and a silver chloride content of 99.8 mol% was obtained.
[0097]
(Preparation of silver halide emulsions G-2 to G-6)
In the preparation of the silver halide emulsion G-1, the characteristic value A (surface of silver halide grains described in Table 1) was similarly obtained except that the addition amount of bromide (KBr) was appropriately adjusted and added to the A3 solution. Silver bromide-containing mol% / silver mol present in a region having a depth of 0.006 μm to silver halide emulsion G-2 to characteristic value B (region in which the silver bromide-containing layer according to the present invention is present) G-5 was prepared. Further, in addition to the above changes, the addition amounts of the A2, A3, B2, and B3 solutions were appropriately changed to prepare a silver halide emulsion G-6 having the characteristic values A and B shown in Table 1. . The characteristic value B is expressed as a distance (μm) when the surface of the silver halide grains is 0 μm.
[0098]
[Table 1]

[0099]
(Preparation of silver halide emulsions G-7 to G-13)
In the preparation of the silver halide emulsion G-1, the addition amount of the A2 solution, A3 solution, B2 solution, and B3 solution and the addition amount of bromide (KBr), cyano ligand complex, and carbon atom-containing complex are appropriately adjusted, or In combination, silver halide emulsions G-7 to G- consisting of characteristic value A, characteristic value B and characteristic value C shown in Table 2 (depth of region where cyano ligand complex or carbon atom-containing complex is present). 13 was prepared. The characteristic value B and the characteristic value C are expressed as a distance (μm) when the surface of the silver halide grains is 0 μm.
[0100]
[Table 2]

[0101]
(Preparation of green sensitive silver halide emulsions G2-1 to G2-13)
To the silver halide emulsions G-1 to G-13 prepared above, the following additives were added in this order at intervals of 1 minute, held at 65 ° C., and after 70 minutes, STAB-1 was further treated with an appropriate sensitivity. Was added, and chemical sensitization was performed so that the fog-sensitivity relationship would be optimal, whereby green-sensitive silver halide emulsions G2-1 to G2-13 were prepared.
[0102]

(Preparation of blue-sensitive silver halide emulsion B2-1)
In the preparation of the silver halide emulsion G-1, the average grain size of 0.64 μm, grains was changed in the same manner except that the addition times of the A1, B1, A2, B2, A3 and B3 liquids were appropriately changed. A silver halide emulsion B-1 which was a monodispersed cubic emulsion having a coefficient of variation in diameter distribution of 0.07 and a silver chloride content of 99.5 mol% was obtained.
[0103]
To the above silver halide emulsion B-1, the following compounds were added at 65 ° C. in this order at 1 minute intervals, and chemical sensitization was performed so that the fog-sensitivity relationship would be optimal, and blue-sensitive halogen Silver halide emulsion B2-1 was prepared.
[0104]
1: Sodium thiosulfate 0.8 mg / mol AgX
2: Chloroauric acid 1.5 × 10^-FiveMole / Mole AgX
3: Stabilizer (STAB-1) 3 × 10^-FourMole / Mole AgX
4: Sensitizing dye (BS-1) 4 × 10^-FourMole / Mole AgX
5: Sensitizing dye (BS-2) 1 × 10^-FourMole / Mole AgX
(Preparation of red-sensitive silver halide emulsion R2-1)
In the preparation of the silver halide emulsion G-1, the average grain size of 0.40 μm, grains was changed in the same manner except that the addition times of the A1, B1, A2, B2, A3 and B3 liquids were appropriately changed. A silver halide emulsion R-1 which was a monodispersed cubic emulsion having a coefficient of variation in diameter distribution of 0.08 and a silver chloride content of 99.5 mol% was obtained.
[0105]
To the above silver halide emulsion R-1, the following compounds were added at 65 ° C. in this order at intervals of 1 minute, and chemical sensitization was performed so that the fog-sensitivity relationship would be optimal, and red-sensitive halogen Silver halide emulsion R2-1 was prepared.
[0106]
1: Sodium thiosulfate 1.8 mg / mol AgX
2: Chloroauric acid 1.5 × 10^-FiveMole / Mole AgX
3: Stabilizer (STAB-1) 1.2 × 10^-FourMole / Mole AgX
4: Sensitizing dye (RS-1) 1 × 10^-FourMole / Mole AgX
5: Sensitizing dye (RS-2) 1 × 10^-FourMole / Mole AgX
STAB-1: 1- (3-acetamidophenyl) -5-mercaptotetrazole
Further, in the red-sensitive silver halide emulsion R2-1, SS-1 is 2.0 × 10 6 per mol of silver halide.^-3g was added.
[0107]
[Chemical 1]

[0108]
<< Preparation of silver halide color photographic material >>
(Preparation of sample 1)
Basis weight 180g / m²Reflective support in which a high-density molten polyethylene containing 15% by mass of anatase-type titanium oxide dispersed in the emulsion layer of the paper pulp is laminated and the back side is laminated with high-density polyethylene After subjecting the body to corona discharge treatment, a gelatin subbing layer is provided, and further, each photographic constituent layer having the constitution shown in Tables 3 and 4 is applied to prepare Sample 1 which is a silver halide color photographic light-sensitive material. did.
[0109]
In addition, (H-1) and (H-2) were added as a hardening agent to the second layer, the fourth layer, and the seventh layer. Further, surfactants (SU-2) and (SU-3) were added to each layer as coating aids for adjusting the surface tension. Moreover, the total amount of the antifungal agent (F-1) in each layer is 0.04 g / m.²It added so that it might become. In addition, the silver halide emulsion described in the table is represented by a value converted to silver.
[0110]
[Table 3]

[0111]
[Table 4]

[0112]
Details of each additive used for preparation of Sample 1 are as follows.
SU-1: Sodium tri-i-propylnaphthalenesulfonate
SU-2: Sodium disulfate (2-ethylhexyl) sulfosuccinate
SU-3: sulfosuccinic acid di (2,2,3,3,4,4,5,5-octafluoropentyl) sodium
DBP: Dibutyl phthalate
DNP: dinonyl phthalate
DOP: Dioctyl phthalate
DIDP: Di-i-decyl phthalate
TOP: Trioctyl phosphate
H-1: Tetrakis (vinylsulfonylmethyl) methane
H-2: 2,4-dichloro-6-hydroxy-s-triazine sodium
HQ-1: 2,5-di-t-octyl hydroquinone
HQ-2: 2,5-di-sec-dodecyl hydroquinone
HQ-3: 2,5-di-sec-tetradecyl hydroquinone
HQ-4: 2-sec-dodecyl-5-sec-tetradecylhydroquinone
HQ-5: 2,5-di [(1,1-dimethyl-4-hexyloxycarbonyl) butyl] hydroquinone
Image stabilizer A: Pt-octylphenol
Image stabilizer B: poly (t-butylacrylamide)
[0113]
[Chemical 2]

[0114]
[Chemical 3]

[0115]
[Formula 4]

[0116]
[Chemical formula 5]

[0117]
[Chemical 6]

[0118]
(Preparation of samples 2 to 13)
<Preparation of blue-sensitive and red-sensitive silver halide emulsions B2-2 to B2-13 and R2-2 to R2-13>
After preparing a silver halide emulsion having the same characteristics as the silver halide emulsions used in the preparation of the green-sensitive silver halide emulsions G2-2 to G2-13, the blue-sensitive silver halide emulsion B2-1 and Blue-sensitive silver halide emulsions B2-2 to B2-13 that have been chemically and spectrally sensitized in the same manner as red-sensitive silver halide emulsion R2-1, and red-sensitive silver halide emulsions R2-2 to R2 -13 was prepared.
[0119]
<Preparation of silver halide color photographic material>
In the preparation of Sample 1, blue-sensitive silver halide emulsion B2-1, green-sensitive silver halide emulsion G2-1 and red-sensitive silver halide emulsion R2-1 were used instead of blue-sensitive silver halide emulsion B2-1. Samples 2 to 13 were prepared in the same manner except that ˜B2-13, green sensitive silver halide emulsions G2-2 to G2-13, and red sensitive silver halide emulsions R2-2 to R2-13 were used.
[0120]
<< Evaluation of silver halide color photographic material >>
The prepared samples 1 to 13 were evaluated for processing stability and latent image stability according to the methods described below.
[0121]
(Evaluation of processing stability)
10^-6Using a second exposure xenon flash high illuminance exposure sensitometer (Yamashita Denso Co., Ltd. SX-20 type), wedge exposure was performed, and color development processing 1 was performed according to the following development processing steps 10 minutes after exposure. On the other hand, color development processing 2 was performed in the same manner except that a color development processing solution in which 1.2 ml of bleach-fixing solution was mixed per 1 L of color development processing solution was used.
[0122]
The magenta image reflection density of each sample developed as described above was measured using an optical densitometer (Konica PDA-65 type), and the vertical axis—reflection density (D), horizontal axis -Create a characteristic curve composed of the exposure amount (Log E), measure the gradation γ (γ1) in the color development processing 1 and the gradation γ (γ2) in the color development processing 2 according to the following formula 1, A variation value ΔγA was calculated from each gradation γ value according to the following equation 2. ΔγA indicates that the closer the value is to 100, the better the processing stability.
[0123]
Formula 1
Gradation γ = 1 / [Log (exposure amount indicating fog + 0.5) −Log (exposure amount indicating fog + 1.5)]
Formula 2
ΔγA = (γ2 / γ1) × 100
(Evaluation of latent image stability)
10^-6Using a second-exposure xenon flash high-intensity exposure sensitometer (Yamashita Denso Co., Ltd. Model SX-20), wedge-exposed, left exposed for 5 minutes, and then developed in the same manner as color development process 1 below. Development processing 3 was performed. On the other hand, in the above method, the color development processing 4 was similarly performed after 5 seconds had passed after the exposure.
[0124]
The magenta image reflection density of each sample developed as described above was measured using an optical densitometer (Konica PDA-65 type), and the vertical axis—reflection density (D), horizontal axis -Create a characteristic curve composed of the exposure amount (Log E), measure the gradation γ (γ3) in the color development processing 3 and the gradation γ (γ4) in the color development processing 4 according to the following formula 3, A variation value ΔγB was calculated from each gradation γ value according to the following equation 4. ΔγB indicates that the closer the numerical value is to 100, the better the latent image stability.
[0125]
Formula 3
Gradation γ = 1 / [Log (exposure amount indicating fog + 0.1 density) −Log (exposure amount indicating fog + 0.4 density)]
Formula 4
ΔγB = (γ4 / γ3) × 100
(Color development 1)
Processing process Processing temperature Time Replenishment amount
Color development 38.0 ± 0.3 ℃ 45 seconds 80ml
Bleach fixing 35.0 ± 0.5 ℃ 45 seconds 120ml
Stabilization 30-34 ° C 60 seconds 150ml
Dry 60-80 ° C 30 seconds
(Composition of each developing solution for color development 1)

Water was added to adjust the total volume to 1 liter, the tank liquid was adjusted to pH 10.10, and the replenisher was adjusted to pH 10.60.
[0126]
<Bleach fixer tank solution 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% aqueous solution) 27.5 ml
Water was added to bring the total volume to 1 liter, and the pH was adjusted to 5.0 with potassium carbonate or glacial acetic acid.
[0127]
<Stabilizing liquid tank liquid and replenisher 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 (Polyvinylpyrrolidone) 1.0g
Ammonia water (25% ammonium hydroxide aqueous solution) 2.5 g
Nitrilotriacetic acid trisodium salt 1.5g
Water was added to bring the total volume to 1 liter, and the pH was adjusted to 7.5 with sulfuric acid or aqueous ammonia.
[0128]
Table 5 shows the evaluation results obtained from the above.
[0129]
[Table 5]

[0131]
  Example1
  << Preparation of silver halide emulsion >>
  (Preparation of green sensitive silver halide emulsions G2-14 to G2-19)
  Reference exampleIn the preparation of the silver halide emulsion G2-1 described in 1., a chemical sensitization treatment was carried out in the same manner except that a predetermined amount of STAB-1 was added, and then 0.28 g / mol AgX amount of KBr was added after 5 minutes. A silver halide emulsion G2-14 was prepared. Next, in the same manner as in the silver halide emulsion G2-14, as shown in Table 6, except that the addition position of the first KBr and the addition interval of the first and second KBr were changed. Thus, silver halide emulsions G2-15-1 to G2-19 were prepared. The amount of KBr added in the first and second rounds was fixed at 0.28 g / mol Ag.
[0132]
[Table 6]

[0133]
(Preparation of blue-sensitive and red-sensitive silver halide emulsions B2-14 to B2-19, R2-14 to R2-19)
Blue-sensitive silver halide emulsions B2-14 to B2-19 and red-sensitive silver halide emulsions R2-14 to R2-19 were prepared in the same manner as the silver halide emulsions G2-14 to G2-19.
[0134]
  << Preparation and evaluation of silver halide color photographic materials >>
  Reference exampleIn the preparation of Sample 1 described in 1), instead of the blue-sensitive silver halide emulsion B2-1, the green-sensitive silver halide emulsion G2-1 and the red-sensitive silver halide emulsion R2-1, respectively, the blue-sensitive silver halide emulsion B2 was used. Samples 14 to 19 were prepared in the same manner except that -14 to B2-19, green sensitive silver halide emulsions G2-14 to G2-19, and red sensitive silver halide emulsions R2-14 to R2-19 were used. ,Reference exampleThe processing stability and the latent image stability were evaluated according to the method described in 1), and the obtained results are shown in Table 7.
[0135]
[Table 7]

[0136]
As is apparent from Table 7, the sample of the present invention has an effect on the processing stability and the latent image stability. However, the antifoggant (STAB-1) was added between the two additions of the brominated compound. Sample 15 to which no antifoggant was added was better than Sample 17, and the sample 16 to which no anti-fogging compound was added before the first addition of bromide compound also showed good results. Moreover, the comparative sample 18 having a short interval between the two additions did not provide the effect of the present invention, and conversely, the sample 19 having a long interval gave good results.
[0137]
  Example1Sample prepared14To 19 and using as a light source a semiconductor laser (oscillation wavelength 650 nm), a He-Ne gas laser (oscillation wavelength 544 nm), and an Ar gas laser (oscillation wavelength 458 nm), the overlap between the rasters of the light beam is 25%. Using the scanning exposure apparatus adjusted as described above, the amount of light is modulated by the AOM for each laser beam based on the image data, and reflected on the polygon to perform main scanning on the photosensitive material, and at the same time in the main scanning direction. Scanning exposure while adjusting the exposure amount of each color so that gray can be reproduced stepwise from the maximum density to the minimum density in a 1cm x 1cm patch image by transporting the photosensitive material in the vertical direction (sub-scan) Went. One hour after the exposure was completed, the color development process 1 was performed. The reflection density is measured using a densitometer PDA-65 (manufactured by Konica) for each step of the gray patch image thus obtained, and a plot (characteristic curve) of the red light reflection density against the red laser exposure amount. ), A plot of green light reflection density against green laser exposure, and a plot of blue light reflection density against blue laser exposure. Next, for each color image, the differential value of the density with respect to the exposure amount was calculated for each step to obtain a point gamma, and an exposure amount region (effective gradation region) where the point gamma was 1.0 or more was obtained. In addition, average gradations having a reflection density of 0.8 to 1.8 were obtained simultaneously.
[0138]
Each sample of the present invention is superior in processing stability and latent image stability to the comparative sample, and the effective gradation area (VE) in each color image forming layer is 0.65 or more and 0.84 or less. Yes, the difference (ΔVE) between the VE value of the color image forming layer having the maximum effective gradation area (VE) and the VE value of the color image forming layer having the minimum effective gradation region (VE) can be stably reproduced from 0 to 0.08, As a result, it was found that the reproducibility of the thin line can be obtained stably.
[0139]
【The invention's effect】
According to the present invention, a silver halide emulsion and silver halide photograph that are suitable for silver halide color paper, have excellent development stability at high illumination exposure and latent image stability at high illumination exposure, and good reproducibility of fine lines. It was possible to provide a light-sensitive material, a silver halide color photographic light-sensitive material, and an image forming method using them.

Claims (7)

In a silver halide emulsion comprising silver chlorobromide grains or silver chloroiodobromide grains having a silver chloride content of 98% or more, a bromide compound at the time of chemical sensitization of the silver chlorobromide grains or silver chloroiodobromide grains Is added at least twice, and chemical sensitization treatment is performed for 60 minutes or more during the addition period, and the silver chlorobromide grains or silver chloroiodobromide grains have a depth of 0 to 0.01 μm from the grain surface. A region having a silver bromide content of 0.5 to 5% in the region, and a doped region of a cyano ligand-containing complex is present at a depth of 0.001 to 0.01 μm from the grain surface; and in the region closer doped region on the particle surface, a silver halide emulsion which is characterized that you there is a phase that does not contain cyano ligand-containing complexes and carbon-containing complex. The silver chlorobromide grain or silver chloroiodobromide grain has a doped region of a carbon atom-containing complex at a depth of 0.001 to 0.01 μm from the grain surface, and is closer to the grain surface than the doped area in the region, the silver halide emulsion according to claim 1, characterized in that there is a phase containing no carbon atom-containing complexes and cyano ligand containing complex. 3. The silver halide emulsion according to claim 1, wherein the silver chlorobromide grains or silver chloroiodobromide grains are gold sensitized . The 50% or more of the total projected area of the silver chlorobromide grain or silver chloroiodobromide grain is a tabular grain having an aspect ratio of 2 or more . Silver halide emulsion. A silver halide photographic light-sensitive material comprising at least one image forming layer on a support, the image forming layer containing the silver halide emulsion according to any one of claims 1 to 4. material. In a silver halide color photographic light-sensitive material having at least one yellow image forming layer, magenta image forming layer, and cyan image forming layer each containing at least photosensitive silver halide on a support, the color image At least one of the formation layers contains the silver halide emulsion according to any one of claims 1 to 4, and 10 per pixel. ^-Ten 10 seconds or more ^-3 The effective gradation region (VE) of the color image obtained by performing color development after exposure with an exposure time of less than 2 seconds is 0.65 or more and 0.84 or less for each color image forming layer, and the effective floor. The halogen having a difference (ΔVE) between 0 and 0.08 or less between the VE value of the color image forming layer having the maximum tone area (VE) and the VE value of the color image forming layer having the minimum tone area (VE) Silver halide color photographic material. 10. The silver halide color photographic light-sensitive material according to claim 6, wherein 10 per pixel. ^-Ten 10 seconds or more ^-3 An image forming method comprising performing color development after exposure with an exposure time of seconds or less.