JP2004333842A - Silver halide photographic emulsion - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silver halide photographic emulsion containing silver halide grains having high sensitivity and excellent in granularity. <P>SOLUTION: In the silver halide photographic emulsion containing a dispersion medium and silver halide grains, a coefficient of variation of projected area diameter of the silver halide grains is ≤30%, a coefficient of variation of grain thickness is ≤15%, and ≥50% of the total projected area of the silver halide grains is occupied by tabular silver halide grains having smooth (111) faces as main planes and satisfying a silver iodide content of ≥3 mol%, a projected area diameter of ≥1 μm, and an aspect ratio of ≥8. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

【０１５１】
また、ホルムアルデヒドガスによる写真性能の劣化を防止するために、米国特許４，４１１，９８７号や同第４，４３５，５０３号の各明細書に記載されたホルムアルデヒドと反応して、固定化できる化合物を感光材料に添加することが好ましい。
【０１５２】
本発明には種々のカラーカプラーを使用することができ、その具体例は前出のリサーチ・ディスクロージャーＮｏ．１７６４３、ＶＩＩ−Ｃ〜Ｇ、および同Ｎｏ．３０７１０５、ＶＩＩ−Ｃ〜Ｇに記載された特許に記載されている。
【０１５３】
イエローカプラーとしては、例えば米国特許第３，９３３，５０１号、同第４，０２２，６２０号、同第４，３２６，０２４号、同第４，４０１，７５２号、同第４，２４８，９６１号の各明細書、特公昭５８−１０７３９号公報、英国特許第１，４２５，０２０号、同第１，４７６，７６０号の各明細書、米国特許第３，９７３，９６８号、同第４，３１４，０２３号、同第４，５１１，６４９号の各明細書、欧州特許第２４９，４７３Ａ号明細書、等に記載のものが好ましい。
【０１５４】
マゼンタカプラーとしては５−ピラゾロン系及びピラゾロアゾール系の化合物が好ましく、米国特許第４，３１０，６１９号、同第４，３５１，８９７号の各明細書、欧州特許第７３，６３６号明細書、米国特許第３，０６１，４３２号、同第３，７２５，０６７号の各明細書、リサーチ・ディスクロージャーＮｏ．２４２２０（１９８４年６月）、特開昭６０−３３５５２号公報、リサーチ・ディスクロージャーＮｏ．２４２３０（１９８４年６月）、特開昭６０−４３６５９号、同６１−７２２３８号、同６０−３５７３０号、同５５−１１８０３４号、同６０−１８５９５１号の各公報、米国特許第４，５００，６３０号、同第４，５４０，６５４号、同第４，５５６，６３０号の各明細書、国際公開ＷＯ８８／０４７９５号に記載のものが特に好ましい。
【０１５５】
シアンカプラーとしては、フェノール系及びナフトール系カプラーが挙げられ、米国特許第４，０５２，２１２号、同第４，１４６，３９６号、同第４，２２８，２３３号、同第４，２９６，２００号、同第２，３６９，９２９号、同第２，８０１，１７１号、同第２，７７２，１６２号、同第２，８９５，８２６号、同第３，７７２，００２号、同第３，７５８，３０８号、同第４，３３４，０１１号、同第４，３２７，１７３号の各明細書、西独特許公開第３，３２９，７２９号、欧州特許第１２１，３６５Ａ号、同第２４９，４５３Ａ号の各明細書、米国特許第３，４４６，６２２号、同第４，３３３，９９９号、同第４，７７５，６１６号、同第４，４５１，５５９号、同第４，４２７，７６７号、同第４，６９０，８８９号、同第４，２５４，２１２号、同第４，２９６，１９９号の各明細書、特開昭６１−４２６５８号公報等に記載のものが好ましい。
【０１５６】
ポリマー化された色素形成カプラーの典型例は、米国特許第３，４５１，８２０号、同第４，０８０，２１１号、同第４，３６７，２８２号、同第４，４０９，３２０号、同第４，５７６，９１０号の各明細書、英国特許第２，１０２，１３７号明細書、欧州特許第３４１，１８８Ａ号に記載されている。
【０１５７】
発色色素が適度な拡散性を有するカプラーとしては、米国特許第４，３６６，２３７号明細書、英国特許第２，１２５，５７０号明細書、欧州特許第９６，５７０号明細書、西独特許（公開）第３，２３４，５３３号明細書に記載のものが好ましい。
【０１５８】
発色色素の不要吸収を補正するためのカラード・カプラーは、リサーチ・ディスクロージャーＮｏ．１７６４３のＶＩＩ −Ｇ項、同Ｎｏ．３０７１０５のＶＩＩ −Ｇ項、米国特許第４，１６３，６７０号明細書、特公昭５７−３９４１３号公報、米国特許第４，００４，９２９号、同第４，１３８，２５８号の各明細書、英国特許第１，１４６，３６８号明細書に記載のものが好ましい。また、米国特許第４，７７４，１８１号明細書に記載のカップリング時に放出された蛍光色素により発色色素の不要吸収を補正するカプラーや、米国特許第４，７７７，１２０号明細書に記載の現像主薬と反応して色素を形成しうる色素プレカーサー基を離脱基として有するカプラーを用いることも好ましい。
【０１５９】
カップリングに伴って写真的に有用な残基を放出する化合物もまた本発明で好ましく使用できる。現像抑制剤を放出するＤＩＲカプラーは、前述のＲＤ１７６４３、ＶＩＩ −Ｆ項及び同Ｎｏ．３０７１０５、ＶＩＩ −Ｆ項に記載された特許、特開昭５７−１５１９４４号、同５７−１５４２３４号、同６０−１８４２４８号、同６３−３７３４６号、同６３−３７３５０号の各公報、米国特許第４，２４８，９６２号、同第４，７８２，０１２号の各明細書に記載されたものが好ましい。
【０１６０】
現像時に画像状に造核剤もしくは現像促進剤を放出するカプラーとしては、英国特許第２，０９７，１４０号、同第２，１３１，１８８号の各明細書、特開昭５９−１５７６３８号、同５９−１７０８４０号の各公報に記載のものが好ましい。また、特開昭６０−１０７０２９号、同６０−２５２３４０号、特開平１−４４９４０号、同１−４５６８７号の各公報に記載の現像主薬の酸化体との酸化還元反応により、かぶらせ剤、現像促進剤、ハロゲン化銀溶剤等を放出する化合物も好ましい。
【０１６１】
その他、本発明の感光材料に用いることのできる化合物としては、米国特許第４，１３０，４２７号明細書等に記載の競争カプラー、米国特許第４，２８３，４７２号、同第４，３３８，３９３号、同第４，３１０，６１８号の各明細書等に記載の多当量カプラー、特開昭６０−１８５９５０号、特開昭６２−２４２５２号の各公報等に記載のＤＩＲレドックス化合物放出カプラー、ＤＩＲカプラー放出カプラー、ＤＩＲカプラー放出レドックス化合物もしくはＤＩＲレドックス放出レドックス化合物、欧州特許第１７３，３０２Ａ号、同第３１３，３０８Ａ号の各明細書に記載の離脱後復色する色素を放出するカプラー、ＲＤ．Ｎｏ．１１４４９、同２４２４１、特開昭６１−２０１２４７号の各公報等に記載の漂白促進剤放出カプラー、米国特許第４，５５５，４７７号明細書等に記載のリガンド放出カプラー、特開昭６３−７５７４７号公報に記載のロイコ色素を放出するカプラー、米国特許第４，７７４，１８１号明細書に記載の蛍光色素を放出するカプラーが挙げられる。
【０１６２】
本発明に使用するカプラーは、種々の公知の分散方法により感光材料に導入できる。
【０１６３】
水中油滴分散法に用いられる高沸点溶媒の例は、例えば、米国特許第２，３２２，０２７号明細書に記載されている。
【０１６４】
水中油滴分散法に用いられる常圧での沸点が１７５℃以上の高沸点有機溶剤の具体例としては、フタル酸エステル類（例えば、ジブチルフタレート、ジシクロヘキシルフタレート、ジ−２−エチルヘキシルフタレート、デシルフタレート、ビス（２，４−ジ−ｔｅｒｔ−アミルフェニル）フタレート、ビス（２，４−ジ−ｔｅｒｔ−アミルフェニル）イソフタレート、ビス（１，１−ジエチルプロピル）フタレート）；リン酸またはホスホン酸のエステル類（例えば、トリフェニルホスフェート、トリクレジルホスフェート、２−エチルヘキシルジフェニルホスフェート、トリシクロヘキシルホスフェート、トリ−２−エチルヘキシルホスフェート、トリドデシルホスフェート、トリブトキシエチルホスフェート、トリクロロプロピルホスフェート、ジ−２−エチルヘキシルフェニルホスホネート）；安息香酸エステル類（例えば、２−エチルヘキシルベンゾエート、ドデシルベンゾエート、２−エチルヘキシル−ｐ−ヒドロキシベンゾエート）；アミド類（例えば、Ｎ，Ｎ−ジエチルドデカンアミド、Ｎ，Ｎ−ジエチルラウリルアミド、Ｎ−テトラデシルピロリドン）；アルコール類またはフェノール類（例えば、イソステアリルアルコール、２，４−ジ−ｔｅｒｔ−アミルフェノール）；脂肪族カルボン酸エステル類（例えば、ビス（２−エチルヘキシル）セバケート、ジオクチルアゼレート、グリセロールトリブチレート、イソステアリルラクテート、トリオクチルシトレート）；アニリン誘導体（例えば、Ｎ，Ｎ−ジブチル−２−ブトキシ−５−ｔｅｒｔ−オクチルアニリン）；炭化水素類（例えば、パラフィン、ドデシルベンゼン、ジイソプロピルナフタレン）を例示することができる。また補助溶剤としては、例えば、沸点が約３０℃以上、好ましくは５０℃以上かつ約１６０℃以下の有機溶剤が使用でき、典型例としては、例えば、酢酸エチル、酢酸ブチル、プロピオン酸エチル、メチルエチルケトン、シクロヘキサノン、２−エトキシエチルアセテート、ジメチルホルムアミドが挙げられる。
【０１６５】
ラテックス分散法の工程、効果および含浸用ラテックスの具体例は、例えば、米国特許第４，１９９，３６３号明細書、西独特許出願（ＯＬＳ）第２，５４１，２７４号および、同第２，５４１，２３０号に記載されている。
【０１６６】
本発明のカラー感光材料中には、フェネチルアルコールや特開昭６３−２５７７４７号、同６２−２７２２４８号、および特開平１−８０９４１号の各公報に記載の、例えば、１，２−ベンズイソチアゾリン−３−オン、ｎ−ブチル−ｐ−ヒドロキシベンゾエート、フェノール、４−クロル−３，５−ジメチルフェノール、２−フェノキシエタノール、２−（４−チアゾリル）ベンゾイミダゾールのような各種の防腐剤もしくは防黴剤を添加することが好ましい。
【０１６７】
本発明の乳剤は種々のカラー感光材料に適用することができる。例えば、一般用もしくは映画用のカラーネガフィルム、スライド用もしくはテレビ用のカラー反転フィルム、カラーペーパー、カラーポジフィルムおよびカラー反転ペーパーを代表例として挙げることができる。本発明は、カラーデュープ用フィルムにも特に好ましく使用できる。
【０１６８】
本発明の乳剤を含有する感光材料に使用できる適当な支持体は、例えば、前述のＲＤ．Ｎｏ．１７６４３の２８頁、同Ｎｏ．１８７１６の６４７頁右欄から６４８頁左欄、および同Ｎｏ．３０７１０５の８７９頁に記載されている。
【０１６９】
本発明の乳剤を含有する感光材料は、乳剤層を有する側の全親水性コロイド層の膜厚の総和が２８μｍ以下であることが好ましく、２３μｍ以下がより好ましく、１８μｍ以下が更に好ましく、１６μｍ以下が特に好ましい。また膜膨潤速度Ｔ_１／２が３０秒以下が好ましく、２０秒以下がより好ましい。ここでの膜厚は、２５℃相対湿度５５％調湿下（２日）で測定した膜厚を意味する。また、膜膨潤速度Ｔ_１／２は当該技術分野において公知の手法に従って測定することができ、例えばエー・グリーン（Ａ．Ｇｒｅｅｎ）らによりフォトグラフィック・サイエンス・アンド・エンジニアリング（Ｐｈｏｔｏｇｒ．Ｓｃｉ．Ｅｎｇ．）、１９巻、２号、１２４〜１２９頁に記載の型のスエロメーター（膨潤計）を使用することにより測定できる。なお、Ｔ_１／２は発色現像液で３０℃、３分１５秒処理した時に到達する最大膨潤膜厚の９０％を飽和膜厚とし、飽和膜厚の１／２に到達するまでの時間と定義する。
【０１７０】
膜膨潤速度Ｔ_１／２は、バインダーとしてのゼラチンに硬膜剤を加えること、あるいは塗布後の経時条件を変えることによって調整することができる。
【０１７１】
本発明の乳剤を含有する感光材料は、乳剤層を有する側の反対側に、乾燥膜厚の総和が２μｍ〜２０μｍの親水性コロイド層（バック層と称す）を設けることが好ましい。このバック層には、例えば、前述の光吸収剤、フィルター染料、紫外線吸収剤、スタチック防止剤、硬膜剤、バインダー、可塑剤、潤滑剤、塗布助剤、表面活性剤を含有させることが好ましい。このバック層の膨潤率は１５０〜５００％が好ましい。
【０１７２】
本発明に従ったカラー写真感光材料は、前述のＲＤ．Ｎｏ．１７６４３の２８〜２９頁、同Ｎｏ．１８７１６の６５１頁左欄〜右欄、および同Ｎｏ．３０７１０５の８８０〜８８１頁に記載された通常の方法によって現像処理することができる。
【０１７３】
本発明の乳剤を含有する感光材料の現像処理に用いる発色現像液は、好ましくは芳香族第一級アミン系発色現像主薬を主成分とするアルカリ性水溶液である。この発色現像主薬としては、アミノフェノール系化合物も有用であるが、ｐ−フェニレンジアミン系化合物が好ましく使用され、その代表例としては３−メチル−４−アミノ−Ｎ，Ｎジエチルアニリン、３−メチル−４−アミノ−Ｎ−エチル−Ｎ−β−ヒドロキシエチルアニリン、３−メチル−４−アミノ−Ｎ−エチル−Ｎ−β−メタンスルホンアミドエチルアニリン、３−メチル−４−アミノ−Ｎ−エチル−β−メトキシエチルアニリン、及びこれらの硫酸塩、塩酸塩もしくはｐ−トルエンスルホン酸塩などが挙げられる。これらの中で、特に、３−メチル−４−アミノ−Ｎ−エチル−Ｎ−β−ヒドロキシエチルアニリンの硫酸塩が好ましい。これらの化合物は目的に応じ２種以上併用することもできる。
【０１７４】
発色現像液は、例えば、アルカリ金属の炭酸塩、ホウ酸塩もしくはリン酸塩のようなｐＨ緩衝剤、塩化物塩、臭化物塩、沃化物塩、ベンズイミダゾール類、ベンゾチアゾール類もしくはメルカプト化合物のような現像抑制剤またはかぶり防止剤を含むのが一般的である。また必要に応じて、ヒドロキシルアミン、ジエチルヒドロキシルアミン、亜硫酸塩、Ｎ，Ｎ−ビスカルボキシメチルヒドラジンの如きヒドラジン類、フェニルセミカルバジド類、トリエタノールアミン、カテコールスルホン酸類の如き各種保恒剤；エチレングリコール、ジエチレングリコールのような有機溶剤；ベンジルアルコール、ポリエチレングリコール、四級アンモニウム塩、アミン類のような現像促進剤；色素形成カプラー、競争カプラー、１−フェニル−３−ピラゾリドンのような補助現像主薬；粘性付与剤；アミノポリカルボン酸、アミノポリホスホン酸、アルキルホスホン酸、ホスホノカルボン酸に代表されるような各種キレート剤を用いることができる。キレート剤としては、例えば、エチレンジアミン四酢酸、ニトリル三酢酸、ジエチレントリアミン五酢酸、シクロヘキサンジアミン四酢酸、ヒドロキシエチルイミノジ酢酸、１−ヒドロキシエチリデン−１，１−ジホスホン酸、ニトリロ−Ｎ，Ｎ，Ｎ−トリメチレンホスホン酸、エチレンジアミン−Ｎ，Ｎ，Ｎ，Ｎ−テトラメチレンホスホン酸、エチレンジアミン−ジ（ｏ−ヒドロキシフェニル酢酸）及びそれらの塩を代表例として挙げることができる。
【０１７５】
また、反転処理を実施する場合は、通常黒白現像を行なってから発色現像する。この黒白現像液には、例えば、ハイドロキノンのようなジヒドロキシベンゼン類、例えば、１−フェニル−３−ピラゾリドンのような３−ピラゾリドン類、または例えば、Ｎ−メチル−ｐ−アミノフェノールのようなアミノフェノール類の公知の黒白現像主薬を単独であるいは組み合わせて用いることができる。これらの発色現像液及び黒白現像液のｐＨは、９〜１２であることが一般的である。また、これらの現像液の補充量は、処理するカラー写真感光材料にもよるが、一般に感光材料１平方メートル当たり３リットル以下であり、補充液中の臭化物イオン濃度を低減させておくことにより５００ｍｌ以下にすることもできる。補充量を低減する場合には、処理液の空気との接触面積を小さくすることによって液の蒸発、空気酸化を防止することが好ましい。
【０１７６】
処理槽での写真処理液と空気との接触面積は、以下に定義する開口率で表わすことができる。即ち、
開口率＝［処理液と空気との接触面積（ｃｍ^２）］÷［処理液の容量（ｃｍ^３）］
上記の開口率は０．１以下であることが好ましく、より好ましくは０．００１〜０．０５である。このように開口率を低減させる方法としては、処理槽の写真処理液面に、例えば浮き蓋のような遮蔽物を設ける方法に加えて、特開平１−８２０３３号公報に記載された可動蓋を用いる方法、特開昭６３−２１６０５０号公報に記載されたスリット現像処理方法を挙げることができる。開口率を低減させることは、発色現像及び黒白現像の両工程のみならず、後続の諸工程、例えば、漂白、漂白定着、定着、水洗、安定化の全ての工程において適用することが好ましい。また、現像液中の臭化物イオンの蓄積を抑える手段を用いることにより、補充量を低減することもできる。
【０１７７】
発色現像処理の時間は通常２〜５分の間で設定されるが、高温高ｐＨとし、かつ発色現像主薬を高濃度に使用することにより、更に処理時間の短縮を図ることもできる。
【０１７８】
発色現像後の写真乳剤層は通常漂白処理される。漂白処理は定着処理と同時に行なわれてもよいし（漂白定着処理）、個別に行なわれてもよい。更に処理の迅速化を図るため、漂白処理後に漂白定着処理する処理方法でもよい。さらに、二槽の連続した漂白定着浴で処理すること、漂白定着処理の前に定着処理すること、又は漂白定着処理後に漂白処理することも目的に応じ任意に実施できる。漂白剤としては、例えば、鉄（ＩＩＩ）のような多価金属の化合物、過酸類（特に、過硫酸ソーダは映画用カラーネガフィルムに適する）、キノン類、ニトロ化合物が用いられる。代表的漂白剤としては、鉄（ＩＩＩ）の有機錯塩、例えば、エチレンジアミン四酢酸、ジエチレントリアミン五酢酸、シクロヘキサンジアミン四酢酸、メチルイミノ二酢酸、１，３−ジアミノプロパン四酢酸、グリコールエーテルジアミン四酢酸のようなアミノポリカルボン酸類との錯塩、または、例えば、クエン酸、酒石酸、リンゴ酸との錯塩を用いることができる。これらのうち、エチレンジアミン四酢酸鉄（ＩＩＩ）錯塩、及び１，３−ジアミノプロパン四酢酸鉄（ＩＩＩ）錯塩をはじめとするアミノポリカルボン酸鉄（ＩＩＩ）錯塩は、迅速処理と環境汚染防止の観点から好ましい。さらに、アミノボリカルボン酸鉄（ＩＩＩ）錯塩は、漂白液においても、漂白定着液においても特に有用である。これらのアミノポリカルボン酸鉄（ＩＩＩ）錯塩を用いた漂白液又は漂白定着液のｐＨは通常４．０〜８であるが、処理の迅速化のためにさらに低いｐＨで処理することもできる。
【０１７９】
漂白液、漂白定着液及びそれらの前浴には、必要に応じて漂白促進剤を使用することができる。有用な漂白促進剤の具体例は、次の明細書に記載されている：例えば、米国特許第３，８９３，８５８号明細書、西独特許第１，２９０，８１２号、同第２，０５９，９８８号、特開昭５３−３２７３６号、同５３−５７８３１号、同５３−３７４１８号、同５３−７２６２３号、同５３−９５６３０号、同５３−９５６３１号、同５３−１０４２３２号、同５３−１２４４２４号、同５３−１４１６２３号、同５３−１８４２６号の各公報、リサーチ・ディスクロージャーＮｏ．１７１２９号（１９７８号７月）に記載のメルカプト基またはジスルフィド基を有する化合物；特開昭５１−１４０１２９号に記載のチアゾリジン誘導体；特公昭４５−８５０６号、特開昭５２−２０８３２号、同５３−３２７３５号の各公報、米国特許第３，７０６，５６１号明細書に記載のチオ尿素誘導体、西独特許第１，１２７，７１５号、特開昭５８−１６２３５号公報に記載の沃化物塩；西独特許第９６６，４１０号、同第２，７４８，４３０号に記載のポリオキシエチレン化合物類；特公昭４５−８８３６号公報に記載のポリアミン化合物；その他特開昭４９−４０９４３号、同４９−５９６４４号、同５３−９４９２７号、同５４−３５７２７号、同５５−２６５０６号、同５８−１６３９４０号の各公報に記載の化合物；臭化物イオン等が使用できる。なかでも、メルカプト基またはジスルフィド基を有する化合物が促進効果が大きい観点で好ましく、特に米国特許第３，８９３，８５８号明細書、西独特許第１，２９０，８１２号、特開昭５３−９５６３０号公報に記載の化合物が好ましい。更に、米国特許第４，５５２，８８４号明細書に記載の化合物も好ましい。これらの漂白促進剤は感材中に添加してもよい。撮影用のカラー感光材料を漂白定着するときに、これらの漂白促進剤は特に有効である。
【０１８０】
漂白液や漂白定着液には上記の化合物の他に、漂白ステインを防止する目的で有機酸を含有させることが好ましい。特に好ましい有機酸は、酸解離定数（ｐＫａ）が２〜５である化合物で、具体的には、例えば、酢酸、プロピオン酸、ヒドロキシ酢酸を挙げることができる。
【０１８１】
定着液や漂白定着液に用いられる定着剤としては、例えば、チオ硫酸塩、チオシアン酸塩、チオエーテル系化合物、チオ尿素類、多量の沃化物塩を挙げることができる。このなかではチオ硫酸塩の使用が一般的であり、特にチオ硫酸アンモニウムが最も広範に使用できる。また、チオ硫酸塩と、例えば、チオシアン酸塩、チオエーテル系化合物、チオ尿素の併用も好ましい。定着液や漂白定着液の保恒剤としては、亜硫酸塩、重亜硫酸塩、カルボニル重亜硫酸付加物あるいは欧州特許第２９４，７６９Ａ号明細書に記載のスルフィン酸化合物が好ましい。更に、定着液や漂白定着液には、液の安定化の目的で、各種アミノポリカルボン酸類や有機ホスホン酸類の添加が好ましい。
【０１８２】
本発明において、定着液または漂白定着液には、ｐＨ調整のためにｐＫａが６．０〜９．０の化合物、好ましくはイミダゾール、１−メチルイミダゾール、１−エチルイミダゾール、２−メチルイミダゾールの如きイミダゾール類を０．１〜１０モル／リットル添加することが好ましい。
【０１８３】
脱銀工程の時間の合計は、脱銀不良が生じない範囲で短い方が好ましい。好ましい時間は１分〜３分、更に好ましくは１分〜２分である。また、処理温度は２５℃〜５０℃、好ましくは３５℃〜４５℃である。好ましい温度範囲においては脱銀速度が向上し、かつ処理後のステイン発生が有効に防止される。
【０１８４】
脱銀工程においては、撹拌ができるだけ強化されていることが好ましい。撹拌強化の具体的な方法としては、特開昭６２−１８３４６０号公報に記載の感光材料の乳剤面に処理液の噴流を衝突させる方法や、特開昭６２−１８３４６１号公報に回転手段を用いて撹拌効果を上げる方法が挙げられる。更には、液中に設けられたワイパーブレードと乳剤面を接触させながら感光材料を移動させ、乳剤表面を乱流化することによってより撹拌効果を向上させる方法や、処理液全体の循環流量を増加させる方法が挙げられる。このような撹拌向上手段は、漂白液、漂白定着液、定着液のいずれにおいても有効である。撹拌の向上は、乳剤膜中への漂白剤および、定着剤の供給を速め、結果として脱銀速度を高めるものと考えられる。また、前記の撹拌向上手段は漂白促進剤を使用した場合により有効であり、促進効果を著しく増加させたり、漂白促進剤により定着阻害作用を解消させることができる。
【０１８５】
本発明の乳剤を含有する感光材料の現像に用いられる自動現像機は、特開昭６０−１９１２５７号、同６０−１９１２５８号、同６０−１９１２５９号の各公報に記載の感光材料搬送手段を有していることが好ましい。前記の特開昭６０−１９１２５７号公報に記載のとおり、このような搬送手段は前浴から後浴への処理液の持込みを著しく削減でき、処理液の性能劣化を防止する効果が高い。このような効果は、各工程における処理時間の短縮や処理液補充量の低減に特に有効である。
【０１８６】
本発明の乳剤を含有するハロゲン化銀カラー写真感光材料は、脱銀処理後、水洗及び／又は安定工程を経るのが一般的である。水洗工程での水洗水量は、感光材料の特性（例えば、カプラーのような使用素材による）、用途、更には、例えば、水洗水温、水洗タンクの数（段数）、向流、順流のような補充方式、その他種々の条件に応じて広範囲に設定し得る。このうち、多段向流方式における水洗タンク数と水量の関係は、Ｊｏｕｒｎａｌ ｏｆ ｔｈｅ Ｓｏｃｉｅｔｙ ｏｆ Ｍｏｔｉｏｎ Ｐｉｃｔｕｒｅ ａｎｄ Ｔｅｌｅｖｉｓｉｏｎ Ｅｎｇｉｎｅｅｒｓ 第６４巻、Ｐ．２４８〜２５３（１９５５年５月号）に記載の方法で求めることができる。
【０１８７】
前記文献に記載の多段向流方式によれば、水洗水量を大幅に減少し得るが、タンク内における水の滞留時間の増加によりバクテリアが繁殖し、生成した浮遊物が感光材料に付着するというような問題が生じる。本発明のカラー感光材料の処理おいては、このような問題の解決策として、特開昭６２−２８８８３８号公報に記載のカルシウムイオン、マグネシウムイオンを低減させる方法を極めて有効に用いることができる。また、特開昭５７−８５４２号公報に記載の、例えば、イソチアゾロン化合物やサイアベンダゾール類、塩素化イソシアヌール酸ナトリウムのような塩素系殺菌剤、その他、例えば、ベンゾトリアゾールのような、堀口博著「防菌防黴剤の化学」（１９８６年）三共出版、衛生技術会編「微生物の滅菌、殺菌、防黴技術」（１９８２年）工業技術会、日本防菌防黴学会編「防菌防黴剤事典」（１９８６年）に記載の殺菌剤を用いることもできる。
【０１８８】
本発明の乳剤を含有する感光材料の処理おける水洗水のｐＨは、４〜９、好ましくは５〜８である。水洗水温および水洗時間も、例えば感光材料の特性、用途に応じて種々設定し得るが、一般には、１５〜４５℃で２０秒〜１０分、好ましくは２５〜４０℃で３０秒〜５分の範囲が選択される。更に、本発明の感光材料は、上記水洗に代えて、直接安定液によって処理することもできる。このような安定化処理においては、特開昭５７−８５４３号、同５８−１４８３４号、同６０−２２０３４５号の各公報に記載の公知の方法はすべて用いることができる。
【０１８９】
また、前記水洗処理に続いて、更に安定化処理する場合もある。その例として、撮影用カラー感光材料の最終浴として使用される、色素安定化剤と界面活性剤を含有する安定浴を挙げることができる。色素安定化剤としては、例えば、ホルマリンやグルタルアルデヒドのようなアルデヒド類、Ｎ−メチロール化合物、ヘキサメチレンテトラミンあるいはアルデヒド亜硫酸酸付加物を挙げることができる。この安定浴にも、各種キレート剤や防黴剤を加えることができる。
【０１９０】
上記水洗及び／又は安定液の補充に伴うオーバーフロー液は脱銀工程のような他の工程において再利用することもできる。
【０１９１】
例えば自動現像機を用いた処理において、上記の各処理液が蒸発により濃縮化する場合には、水を加えて濃縮補正することが好ましい。
【０１９２】
本発明の乳剤を含有するハロゲン化銀カラー写真感光材料には、処理の簡略化及び迅速化の目的で発色現像主薬を内蔵させてもよい。内蔵させるためには、発色現像主薬の各種プレカーサーを用いるのが好ましい。例えば、米国特許第３，３４２，５９７号明細書に記載のインドアニリン系化合物、例えば、同第３，３４２，５９９号明細書、リサーチ・ディスクロージャーＮｏ．１４，８５０及び同Ｎｏ．１５，１５９に記載のシッフ塩基型化合物、同Ｎｏ．１３，９２４に記載のアルドール化合物、米国特許第３，７１９，４９２号明細書に記載の金属塩錯体、特開昭５３−１３５６２８号公報に記載のウレタン系化合物を挙げることができる。
【０１９３】
本発明の乳剤を含有するハロゲン化銀カラー感光材料は、必要に応じて、発色現像を促進する目的で、各種の１−フェニル−３−ピラゾリドン類を内蔵してもよい。典型的な化合物は、例えば、特開昭５６−６４３３９号、同５７−１４４５４７号、および同５８−１１５４３８号の各公報に記載されている。
【０１９４】
本発明における各種処理液は、１０℃〜５０℃において使用され得る。通常は３３℃〜３８℃の温度が標準的であるが、より高温にして処理を促進し処理時間を短縮したり、逆により低温にして画質の向上や処理液の安定性の改良を達成することができる。
【０１９５】
【実施例】
［実施例１］
以下、実施例により本発明を具体的に説明するが、本発明の様態はこれに限るものではない。
以下の乳剤調製で分散媒として用いたゼラチン−１〜４は、以下の属性を持つゼラチンである。
【０１９６】
ゼラチン−１：牛骨を原料とする、通常のアルカリ処理オセインゼラチン。
【０１９７】
ゼラチン中の−ＮＨ_２基の化学修飾なし。
【０１９８】
ゼラチン−２：ゼラチン−１の水溶液に、５０℃、ｐＨ９．０の条件下でコハク酸を加えて化学反応させた後、残留するコハク酸を除去して乾燥させたゼラチン。
【０１９９】
ゼラチン中の−ＮＨ_２基が化学修飾された数の割合９５％。
【０２００】
ゼラチン−３：ゼラチン−１に酵素を作用させて低分子量化し、質量平均分子量を１５０００にした後、酵素を失活させて乾燥させたゼラチン。
【０２０１】
ゼラチン中の−ＮＨ_２基の化学修飾なし。
【０２０２】
ゼラチン中のメチオニン基含有率は、４２μｍｏｌ／ｇ。
【０２０３】
ゼラチン−４：ゼラチン−３の水溶液に過酸化水素水を加えて化学反応させた後、残留する過酸化水素をカタラーゼにより失活させたゼラチン。
【０２０４】
ゼラチン中の−ＮＨ_２基の化学修飾なし。
【０２０５】
ゼラチン中のメチオニン基含有率は、３．４μｍｏｌ／ｇ。
【０２０６】
上記のゼラチン−１〜４は、全て脱イオン処理をした後、５％水溶液の３５℃におけるｐＨが６．０となるように調整を行った。
【０２０７】
（種乳剤１）の調製
ＫＢｒを０．９ｇ、前記ゼラチン−３を１ｇ含む水溶液１２００ｃｃを３５℃に保ち撹拌した（１ｓｔ液調製）。
Ａｇ−１水溶液（ＡｇＮＯ_３濃度０．２９Ｍ）３７．５ｃｃと、Ｘ−１水溶液（前記ゼラチン−３濃度１５．５ｇ／Ｌ、ＫＢｒ濃度０．２９５Ｍ）５５ｃｃを同時に一定の流量で添加した（添加１）。
その後ＫＢｒを６ｇ添加し、温度を７５℃に昇温した。昇温の後、Ｇ−１水溶液（前記ゼラチン−２濃度１１７ｇ／Ｌ）３００ｃｃを添加した。この際ｐＨを５．５に調節した。
次いで、Ａｇ−２水溶液（ＡｇＮＯ_３濃度０．５８９Ｍ）７３ｃｃを一定の流量で添加した（添加２）。
【０２０８】
次いで、ベンゼンチオスルホン酸ナトリウムを１ｍｇ添加した。Ａｇ−３水溶液（ＡｇＮＯ_３濃度１．８８Ｍ）５１３ｃｃと、Ｘ−３水溶液（前記ゼラチン−４濃度１８６．７６ｇ／Ｌ、ＫＢｒ濃度０．５６６Ｍ、ＫＩ濃度０．０６２９Ｍ）１４６１ｃｃを特開平１０−４３５７０号公報に記載の撹拌装置を用いて混合し、形成される平均サイズ０．０２５μｍの沃臭化銀微粒子を含むハロゲン化銀写真乳剤を吐出後直ちに連続添加した（添加３）。このとき、Ｘ−２水溶液（ＫＢｒ濃度０．５２５Ｍ）もあわせて添加し、銀電位を飽和カロメル電極に対して０ｍＶに保たれるように調節した。この間ｐＨが５〜６の間に保たれるように調節した。
【０２０９】
その後、通常のフロキュレーション法により脱塩を行い、次いで、攪拌しながら水、ＮａＯＨ、前記のゼラチン−１を添加し、ｐＨ５．８、ｐＡｇが８．８になるように調整した。
【０２１０】
得られた乳剤中には、平均沃化銀含有率９モル％、平均球相当径０．６５μｍ、平均アスペクト比３３の粒子を含んでいた。
【０２１１】
（種乳剤２）の調製
種乳剤１の添加３で用いたＸ−３水溶液のＫＢｒ濃度を０．６１０Ｍ、ＫＩ濃度０．０１８９Ｍに置き換えることで、平均沃化銀含有率２．５モル％、平均球相当径０．６５μｍ、平均アスペクト比３５の粒子からなる乳剤を得た。
【０２１２】
（種乳剤３）の調製
種乳剤１の添加３で用いたＸ−３水溶液のＫＢｒ濃度を０．５９７Ｍ、ＫＩ濃度０．０３１４Ｍに置き換えることで、平均沃化銀含有率２．５モル％、平均球相当径０．６５μｍ、平均アスペクト比３５の粒子からなる乳剤を得た。
【０２１３】
（種乳剤４）の調製
特開２００３−４３６０３号公報の実施例１の種乳剤２に記載されたハロゲン化銀平板粒子の調製方法を参考にした。
ＮａＣｌを０．５４ｇ、および前記ゼラチン−３を０．５ｇ含有する分散媒溶液１２００ｃｃを反応容器に３５℃に保ち、それを撹拌しながらＡｇ−１水溶液（ＡｇＮＯ_３濃度０．２９Ｍ）の硝酸銀とモル比でＫＢｒ／ＮａＣｌが８０／２０となるように調整した濃度０．２９Ｍのハロゲン塩（ＫＢｒ、ＮａＣｌ）水溶液（Ｘ−１）を各々３７．５ｃｃずつ、同時に添加した。
【０２１４】
次いで添加１の後にＫＢｒを６．５ｇ添加した後、７５℃に昇温した。昇温後Ｇ−１水溶液（前記ゼラチン−２濃度１１７ｇ／Ｌ）３００ｃｃを添加した。この際、ｐＨは５．５に調整した。
【０２１５】
次いで、Ａｇ−２水溶液（ＡｇＮＯ_３濃度０．５８９Ｍ）７３ｃｃを一定の流量で添加した（添加２）。
【０２１６】
次いで、ベンゼンチオスルホン酸ナトリウムを１ｍｇ添加した。Ａｇ−３水溶液（ＡｇＮＯ_３濃度１．８８Ｍ）５１３ｃｃと、Ｘ−３水溶液（前記ゼラチン−４濃度１８６．７６ｇ／Ｌ、ＫＢｒ濃度０．５６６Ｍ、ＫＩ濃度０．０６２９Ｍ）１４６１ｃｃを特開平１０−４３５７０号公報に記載の撹拌装置を用いて混合し、形成される平均サイズ０．０２５μｍの沃臭化銀微粒子を含むハロゲン化銀写真乳剤を吐出後直ちに連続添加した（添加３）。このとき、Ｘ−２水溶液（ＫＢｒ濃度０．５２５Ｍ）もあわせて添加し、銀電位を飽和カロメル電極に対して０ｍＶに保たれるように調節した。この間ｐＨが５〜６の間に保たれるように調節した。
【０２１７】
その後、通常のフロキュレーション法により脱塩を行い、次いで、攪拌しながら水、ＮａＯＨ、前記のゼラチン−１を添加し、ｐＨ５．８、ｐＡｇが８．８になるように調整した。
得られた乳剤中は、平均沃化銀含有率９モル％、平均球相当径０．６５μｍ、平均アスペクト比２６の粒子を含んでいた。
【０２１８】
（種乳剤５）の調製
ＫＢｒを０．９ｇ、前記ゼラチン−３を０．１４ｇ含む水溶液１２００ｃｃを３５℃に保ち撹拌した（１ｓｔ液調製）。
Ａｇ−１水溶液（ＡｇＮＯ_３濃度０．１４５Ｍ）３７．５ｃｃとＸ−１溶液（ＫＢｒ濃度０．１４８Ｍ）５５ｃｃとＧ−１溶液（前記ゼラチン−３濃度５０ｇ／Ｌ）８１ｃｃを一定の流量で同時に添加した。（添加１）。
その後ＫＢｒを６ｇ添加し、次いで前記ゼラチン−３を４ｇ添加し、温度を７５℃に昇温した。昇温の後、Ｇ−２水溶液（前記ゼラチン−２濃度１１７ｇ／Ｌ）３００ｃｃを添加した。この際ｐＨを５．５に調節した。
次いで、Ａｇ−２水溶液（ＡｇＮＯ_３濃度０．５８９Ｍ）７３ｃｃを一定の流量で添加した（添加２）。
【０２１９】
次いで、ベンゼンチオスルホン酸ナトリウムを１ｍｇ添加した。次いでＡｇ−３水溶液（ＡｇＮＯ_３濃度０．８８３Ｍ）７３５ｃｃと、Ｘ−３水溶液（前記ゼラチン−４を１７４．３ｇ／Ｌ、ＫＢｒ濃度０．７７１Ｍ、ＫＩ濃度０．０８５７Ｍ）７３５ｃｃを特開平１０−４３５７０号公報に記載の撹拌装置を用いて混合し、形成される平均サイズ０．０２５μｍの沃臭化銀微粒子を含むハロゲン化銀写真乳剤を吐出後直ちに連続添加した（添加３）。このとき、Ｘ−２水溶液（ＫＢｒ濃度０．５２５Ｍ）もあわせて添加し、銀電位を飽和カロメル電極に対して０ｍＶに保たれるように調節した。この間ｐＨが５〜６の間に保たれるように調節した。
【０２２０】
その後、通常のフロキュレーション法により脱塩を行い、次いで、攪拌しながら水、ＮａＯＨ、前記のゼラチン−１を添加し、ｐＨ５．８、ｐＡｇが８．８になるように調整した。
【０２２１】
得られた乳剤中は、平均沃化銀含有率９モル％、平均球相当径０．６５μｍ、平均アスペクト比３３の粒子からなっていた。
【０２２２】
（種乳剤６）の調製
ＫＢｒを０．９ｇ、前記ゼラチン−３を０．５ｇ含む水溶液１２００ｃｃを３５℃に保ち撹拌した（１ｓｔ液調製）。
Ａｇ−１水溶液（ＡｇＮＯ_３濃度０．１４５Ｍ）３７．５ｃｃとＸ−１溶液（前記ゼラチン−３を７．８ｇ／Ｌ、ＫＢｒ濃度０．１４８Ｍ）５５ｃｃを一定の流量で同時に添加した（添加１）。
【０２２３】
その後ＫＢｒを６ｇ添加し、次いで前記ゼラチン−３を４ｇ添加し、温度を７５℃に昇温した。昇温の後、Ｇ−２水溶液（前記ゼラチン−２濃度１１７ｇ／Ｌ）３００ｃｃを添加した。この際ｐＨを５．５に調節した。
次いで、Ａｇ−２水溶液（ＡｇＮＯ_３濃度０．５８９Ｍ）７３ｃｃを一定の流量で添加した（添加２）。
【０２２４】
次いで、ベンゼンチオスルホン酸ナトリウムを１ｍｇ添加した。次いでＡｇ−３水溶液（ＡｇＮＯ_３濃度０．８８３Ｍ）７３５ｃｃと、Ｘ−３水溶液（前記ゼラチン−４を１７４．３ｇ／Ｌ、ＫＢｒ濃度０．７７１Ｍ、ＫＩ濃度０．０８５７Ｍ）７３５ｃｃを特開平１０−４３５７０号公報に記載の撹拌装置を用いて混合し、形成される平均サイズ０．０２５μｍの沃臭化銀微粒子を含むハロゲン化銀写真乳剤を吐出後直ちに連続添加した（添加３）。このとき、Ｘ−２水溶液（ＫＢｒ濃度０．５２５Ｍ）もあわせて添加し、銀電位を飽和カロメル電極に対して＋４０ｍＶに保たれるように調節した。この間ｐＨが５〜６の間に保たれるように調節した。
【０２２５】
その後、通常のフロキュレーション法により脱塩を行い、次いで、攪拌しながら水、ＮａＯＨ、前記のゼラチン−１を添加し、ｐＨ５．８、ｐＡｇが８．８になるように調整した。
【０２２６】
得られた乳剤中は、平均沃化銀含有率９モル％、平均球相当径０．６５μｍ、平均アスペクト比３３の粒子が含まれていた。
【０２２７】
（種乳剤７）の調製
種乳剤２を参考にして種乳剤５を調製した。
ＫＢｒを０．９ｇ、前記ゼラチン−３を０．５ｇ含む水溶液１２００ｃｃを３５℃に保ち撹拌した（１ｓｔ液調製）。
Ａｇ−１水溶液（ＡｇＮＯ_３濃度０．２９Ｍ）の硝酸銀とモル比でＫＢｒ／ＮａＣｌが９５／５となるように調整した（濃度０．２９Ｍ、前記ゼラチン濃度７．８ｇ／Ｌ）のハロゲン塩（ＫＢｒ、ＮａＣｌ）水溶液（Ｘ−１）を各々３７．５ｃｃずつを添加した。
その後ＫＢｒを６．５ｇ添加し、温度を７５℃に昇温した。昇温での熟成過程経た後、Ｇ−１水溶液（前記ゼラチン−２濃度１１７ｇ／Ｌ）３００ｃｃを添加した。
【０２２８】
次いで１Ｎの硫酸を適量添加しｐＨを５．５に調節した。
次いで、Ａｇ−２水溶液（ＡｇＮＯ_３濃度０．５８９Ｍ）７３ｃｃを一定の流量で添加した（添加２）。
【０２２９】
次いで、ベンゼンチオスルホン酸ナトリウムを１ｍｇ添加した。次いでＡｇ−３水溶液（ＡｇＮＯ_３濃度０．８８３Ｍ）７３５ｃｃと、Ｘ−３水溶液（前記ゼラチン−４を１７４．３ｇ／Ｌ、ＫＢｒ濃度０．７７１Ｍ、ＫＩ濃度０．０８５７Ｍ）７３５ｃｃを特開平１０−４３５７０号公報に記載の撹拌装置を用いて混合し、形成される平均サイズ０．０２５μｍの沃臭化銀微粒子を含むハロゲン化銀写真乳剤を吐出後直ちに連続添加した（添加３）。このとき、Ｘ−２水溶液（ＫＢｒ濃度０．５２５Ｍ）もあわせて添加し、銀電位を飽和カロメル電極に対して＋４０ｍＶに保たれるように調節した。この間ｐＨが５〜６の間に保たれるように調節した。
【０２３０】
その後、通常のフロキュレーション法により脱塩を行い、次いで、攪拌しながら水、ＮａＯＨ、前記のゼラチン−１を添加し、ｐＨ５．８、ｐＡｇが８．８になるように調整した。
【０２３１】
得られた乳剤中は、平均沃化銀含有率９モル％、平均球相当径０．６５μｍ、平均アスペクト比３１の粒子からなっていた。
【０２３２】
（種乳剤８）の調製
種乳剤２を参考にして種乳剤６を調製した。
ＫＢｒを０．９ｇ、前記ゼラチン−３を０．５ｇ含む水溶液１２００ｃｃを３５℃に保ち撹拌した（１ｓｔ液調製）。
【０２３３】
Ａｇ−１水溶液（ＡｇＮＯ_３濃度０．２９Ｍ）の硝酸銀とモル比でＫＢｒ／ＮａＣｌが９５／５となるように調整した（濃度０．２９Ｍ、前記ゼラチン濃度７．８ｇ／Ｌ）のハロゲン塩（ＫＢｒ、ＮａＣｌ）水溶液（Ｘ−１）を各々３７．５ｃｃずつを同時に添加した。
【０２３４】
その後ＫＢｒを６．５ｇ添加し、次いで前記ゼラチン−３を４ｇ添加し、温度を７５℃に昇温した。昇温での熟成過程経た後、Ｇ−１水溶液（前記ゼラチン−２濃度１１７ｇ／Ｌ）３００ｃｃを添加した。
【０２３５】
次いで１Ｎの硫酸を適量添加しｐＨを５．５に調節した。
次いで、Ａｇ−２水溶液（ＡｇＮＯ_３濃度０．５８９Ｍ）７３ｃｃを一定の流量で添加した（添加２）。
【０２３６】
次いで、ベンゼンチオスルホン酸ナトリウムを１ｍｇ添加した。次いでＡｇ−３水溶液（ＡｇＮＯ_３濃度０．８８３Ｍ）７３５ｃｃと、Ｘ−３水溶液（前記ゼラチン−４を１７４．３ｇ／Ｌ、ＫＢｒ濃度０．７７１Ｍ、ＫＩ濃度０．０８５７Ｍ）７３５ｃｃを特開平１０−４３５７０号公報に記載の撹拌装置を用いて混合し、形成される平均サイズ０．０２５μｍの沃臭化銀微粒子を含むハロゲン化銀写真乳剤を吐出後直ちに連続添加した（添加３）。このとき、Ｘ−２水溶液（ＫＢｒ濃度０．５２５Ｍ）もあわせて添加し、銀電位を飽和カロメル電極に対して＋４０ｍＶに保たれるように調節した。この間ｐＨが５〜６の間に保たれるように調節した。
【０２３７】
その後、通常のフロキュレーション法により脱塩を行い、次いで、攪拌しながら水、ＮａＯＨ、前記のゼラチン−１を添加し、ｐＨ５．８、ｐＡｇが８．８になるように調整した。
【０２３８】
得られた乳剤中には、平均沃化銀含有率９モル％、平均球相当径０．６５μｍ、平均アスペクト比３１の粒子が含まれていた。
【０２３９】
（Ｅｍ−Ａ１）
＜粒子形成＞
アルカリ処理ゼラチン４６ｇ、ＫＢｒ１．７ｇを含む水溶液１２００ｃｃを７５℃に保ち激しく攪拌した。前述した種乳剤１を３９ｇ加えた後，変成シリコンオイル（日本ユニカ−株式会社製品、Ｌ７６０２）を０．３ｇ添加した。Ｈ_２ＳＯ_４を添加してｐＨを５．５に調整した後、ＡｇＮＯ_３を７．０ｇ含む水溶液７１ｃｃとＫＩを１０モル％含むＫＢｒとＫＩの混合水溶液をダブルジェット法で同時に添加した。この時、銀電位を飽和カロメル電極に対して０ｍＶに保った。ベンゼンチオスルホン酸ナトリウム２ｍｇと二酸化チオ尿素２ｍｇを添加した後、特開平１０−４３５７０号公開に記載の撹拌装置を用いてＡｇＮＯ_３を１７８．５ｇ含む水溶液８００ｃｃと、ＫＢｒを１１２．５ｇ、ＫＩを１７．４ｇおよび前記ゼラチン−４を８０ｇ含んだ水溶液８００ｃｃ（水溶液ａ）を混合し、沃化銀含有率１０モル％の沃化銀微粒子乳剤（平均サイズ：０．０２６μｍ）を調製しながら反応容器内にこの沃化銀乳剤を連続添加した。この時、銀電位を飽和カロメル電極に対して−３０ｍＶに保った。ＡｇＮＯ_３を２４．６ｇ含む水溶液７８．８ｃｃとＫＢｒ水溶液をダブルジェット法で添加した。この時、銀電位を飽和カロメル電極に対してを８．０３に調節した。４０℃に降温し、ＫＢｒを添加して銀電位を飽和カロメル電極に対して−４０ｍＶに調節した後、Ｐ−ヨードアセトアミドベンゼンスルフォン酸ナトリウム（１水和物）を１４．５ｇ含む水溶液を添加してから０．８Ｍの亜硫酸ナトリウム水溶液５７ｃｃを添加し、ｐＨを９．０に制御しながら沃化物イオンを生成した。その後に５５℃まで昇温してからｐＨを５．５にもどした。その後、５５℃に保持したままＡｇＮＯ_３を２４．６ｇ含む水溶液１０５．２ｃｃを添加した。添加中はＫＢｒ水溶液で銀電位を飽和カロメル電極に対して−５０ｍＶに調節した。水洗した後、ゼラチンを添加し４０℃でｐＨ５．８、ｐＡｇ８．７に調整した。
【０２４０】
＜増感＞
化合物１および２を添加した後、６０℃に昇温した。増感色素１および２を添加した後に、チオシアン酸カリウム、塩化金酸、チオ硫酸ナトリウム，Ｎ，Ｎ−ヂメチルセレノウレアを添加し最適に化学増感した。化学増感終了時に化合物３および化合物４を添加した。ここで最適に化学増感するとは、増感色素ならびに各化合物をハロゲン化銀１モルあたり１０^−１から１０^−８モルの添加量範囲から選択したことを意味する。
【０２４１】
【化１】

【０２４２】
【化２】

【０２４３】
【化３】

【０２４４】
【化４】

【０２４５】
【化５】

【０２４６】
【化６】

【０２４７】
（Ｅｍ−Ｂ１）
＜粒子形成＞
アルカリ処理ゼラチン４６ｇ、ＫＢｒ１．７ｇを含む水溶液１２１１ｃｃを７５℃に保ち激しく攪拌した。前述した種乳剤１を３８．４ｇ加えた後、変成シリコンオイル（日本ユニカ−株式会社製品、Ｌ７６０２）を０．３ｇ添加した。Ｈ_２ＳＯ_４を添加してｐＨを５．５に調整した後、ＡｇＮＯ_３を８．９ｇ含む水溶液７１ｃｃとＫＩを１０モル％含むＫＢｒとＫＩの混合水溶液をダブルジェット法で添加した。この時銀電位を飽和カロメル電極に対して０ｍＶに保った。ベンゼンチオスルホン酸ナトリウム２ｍｇと二酸化チオ尿素２ｍｇを添加した後、特開平１０−４３５７０号公開に記載の撹拌装置を用いてＡｇＮＯ_３を１７８．５ｇ含む水溶液８００ｃｃとＫＢｒを１１２．５ｇ、ＫＩを１７．４ｇおよび前記ゼラチン−４を８０ｇ含んだ水溶液８００ｃｃを混合し、沃化銀含有率１０モル％の沃化銀微粒子乳剤（平均サイズ：０．０２６μｍ）を調製しながら反応容器内にこの沃化銀乳剤を連続添加した。この時、銀電位を飽和カロメル電極に対して−３０ｍＶに保った。次いで、ＡｇＮＯ_３を６１．４ｇ含む水溶液１３７．６ｃｃとＫＩを１０モル％含むＫＢｒとＫＩの混合水溶液をダブルジェット法で添加した。この時、銀電位を飽和カロメル電極に対してを最初＋２０ｍＶに、後半は＋１２０ｍＶに保った。５０℃に降温した後，０．３％ＫＩ水溶液５７．８ｃｃを添加した。その後直ちに、ＡｇＮＯ_３を８．８ｇを含む水溶液１９．７ｃｃとＮａＣｌを１．５１ｇ、ＫＢｒを２．４７ｇ含む水溶液２１ｃｃと沃化銀微粒子０．００５ｍｏｌを含む溶液を同時に添加した。この際、添加されるＡｇＮＯ_３１ｍｏｌに対して８．０×１０^−４ｍｏｌのＫ_４［ＲｕＣＮ_６］を存在させた。その後、増感色素を添加した。水洗した後、ゼラチンを添加し４０℃でｐＨ５．８、ｐＡｇ８．７に調整した。
【０２４８】
＜増感＞
化合物１および２を添加した後、６０℃に昇温した。増感色素１および２を添加した後に、チオシアン酸カリウム、塩化金酸、チオ硫酸ナトリウム，Ｎ，Ｎ−ヂメチルセレノウレアを添加し最適に化学増感した。化学増感終了時に化合物３および化合物４を添加した。ここで最適に化学増感するとは、増感色素ならびに各化合物をハロゲン化銀１モルあたり１０^−１から１０^−８モルの添加量範囲から選択したことを意味する。
【０２４９】
（Ｅｍ−Ａ２）
種乳剤１の替わりに種乳剤２を使用し、水溶液ａにおいてＫＢｒを１２１．２ｇ、ＫＩを５．２ｇにした以外はＥｍ−Ａ１と同様にしてＥｍ−Ａ２を得た。
【０２５０】
（Ｅｍ−Ａ３）
種乳剤１の替わりに種乳剤３を使用し、水溶液ａにおいてＫＢｒを１１８．７ｇ、ＫＩを８．７ｇにした以外はＥｍ−Ａ１と同様にしてＥｍ−Ａ３を得た。
【０２５１】
（Ｅｍ−Ａ４）
種乳剤１の替わりに種乳剤４を使用した以外はＥｍ−Ａ１と同様にしてＥｍ−Ａ４を得た。
【０２５２】
（Ｅｍ−Ａ５）
種乳剤１の替わりに種乳剤５を使用した以外はＥｍ−Ａ１と同様にしてＥｍ−Ａ５を得た。
【０２５３】
（Ｅｍ−Ａ６）
種乳剤１の替わりに種乳剤６を使用した以外はＥｍ−Ａ１と同様にしてＥｍ−Ａ６を得た。
【０２５４】
（Ｅｍ−Ａ７）
種乳剤１の替わりに種乳剤７を使用した以外はＥｍ−Ａ１と同様にしてＥｍ−Ａ７を得た。
【０２５５】
（Ｅｍ−Ａ８）
種乳剤１の替わりに種乳剤８を使用した以外はＥｍ−Ａ１と同様にしてＥｍ−Ａ８を得た。
【０２５６】
（Ｅｍ−Ｂ２）
種乳剤１の替わりに種乳剤４を使用した以外はＥｍ−Ｂ１と同様にしてＥｍ−Ｂ２を得た。
【０２５７】
（Ｅｍ−Ｂ３）
種乳剤１の替わりに種乳剤５を使用した以外はＥｍ−Ｂ１と同様にしてＥｍ−Ｂ３を得た。
【０２５８】
（Ｅｍ−Ｂ４）
種乳剤１の替わりに種乳剤６を使用した以外はＥｍ−Ｂ１と同様にしてＥｍ−Ｂ４を得た。
【０２５９】
（Ｅｍ−Ｂ５）
種乳剤１の替わりに種乳剤７を使用した以外はＥｍ−Ｂ１と同様にしてＥｍ−Ｂ５を得た。
【０２６０】
（Ｅｍ−Ｂ６）
種乳剤１の替わりに種乳剤８を使用した以外はＥｍ−Ｂ１と同様にしてＥｍ−Ｂ６を得た。
【０２６１】
（Ｅｍ−Ｃ１）
前記Ｅｍ−Ａ５の増感部分を次のように変更することで、Ｅｍ−Ｃ１を得た。
化合物１および２を添加した後、６０℃に昇温した。増感色素１および２を添加した後に、チオシアン酸カリウム、ビス（１，４，５−トリメチル−１，２，４−トリアゾリウム−３−チオレート金）（１）テトラフルオロボレイト、カルボキシメチルトリメチルチオ尿素、Ｎ，Ｎ−ヂメチルセレノウレアを添加し最適に化学増感した。化学増感終了時に化合物３および化合物４を添加した。ここで、最適に化学増感するとは、増感色素ならびに各化合物をハロゲン化銀１モルあたり１０^−１から１０^−８モルの添加量範囲から選択したことを意味する。
【０２６２】
（Ｅｍ−Ｃ２）
前記Ｅｍ−Ａ５の増感部分を次のように変更することで、Ｅｍ−Ｃ２を得た。
化合物１および２を添加した後、６０℃に昇温した。増感色素１および２を添加した後に，チオシアン酸カリウム、ビス（１，４，５−トリメチル−１，２，４−トリアゾリウム−３−チオレート金（Ｉ））テトラフルオロボレイト，カルボキシメチルトリメチルチオ尿素、Ｎ，Ｎ−ジメチルセレノウレアを添加し最適に化学増感した。化学増感時に化合物５と化合物６の合計が１×１０^−４ｍｏｌ／ｍｏｌＡｇになるように添加した。化学増感終了時に化合物３および化合物４を添加した。ここで，最適に化学増感するとは，増感色素ならびに各化合物をハロゲン化銀１モルあたり１０^−１から１０^−８モルの添加量範囲から選択したことを意味する。
【０２６３】
【化７】

【０２６４】
【化８】

【０２６５】
（Ｅｍ−Ｃ３）
前記Ｅｍ−Ａ５の増感部分を次のように変更することで、Ｅｍ−Ｃ３を得た。
化合物１および２を添加した後、６０℃に昇温した。増感色素２および３を添加した後に，チオシアン酸カリウム、ビス（１，４，５−トリメチル−１，２，４−トリアゾリウム−３−チオレート金（Ｉ））テトラフルオロボレイト、カルボキシメチルトリメチルチオ尿素、Ｎ，Ｎ−ジメチルセレノウレアを添加し最適に化学増感した。化学増感時に化合物５を１×１０^−４ｍｏｌ／ｍｏｌＡｇ添加した。化学増感終了時に化合物３および化合物４を添加した。ここで、最適に化学増感するとは，増感色素ならびに各化合物をハロゲン化銀１モルあたり１０^−１から１０^−８モルの添加量範囲から選択したことを意味する。
【０２６６】
【化９】

【０２６７】
（Ｅｍ−Ｃ４）
前記Ｅｍ−Ａ５の増感部分を次のように変更することで、Ｅｍ−Ｃ４を得た。
【０２６８】
化合物１および２を添加した後、６０℃に昇温した。増感色素１および２を添加した後に，チオシアン酸カリウム、ビス（１，４，５−トリメチル−１，２，４−トリアゾリウム−３−チオレート金（Ｉ））テトラフルオロボレイト、カルボキシメチルトリメチルチオ尿素、Ｎ，Ｎ−ジメチルセレノウレアを添加し最適に化学増感した。化学増感時に化合物５と化合物６の合計が１×１０^−４ｍｏｌ／ｍｏｌＡｇになるように添加した。化学増感終了時に化合物３および化合物４を添加した。その後、増感色素４と増感色素５の合計量がを増感色素１および２の合計量と同じになるように添加した。ここで、最適に化学増感するとは，増感色素ならびに各化合物をハロゲン化銀１モルあたり１０^−１から１０^−８モルの添加量範囲から選択したことを意味する。
【０２６９】
【化１０】

【０２７０】
【化１１】

【０２７１】
（Ｅｍ−Ｃ５）
前記種乳剤５を用いて粒子形成を次のように行い、前記Ｅｍ−Ｃ４と同様の増感を行うことでＥｍ−Ｃ５を調製した。
【０２７２】
＜粒子形成＞
アルカリ処理ゼラチンを４６ｇ、ＫＢｒを１．７ｇ含む水溶液１２１１ｃｃを７５℃に保ち激しく攪拌した。前述した種乳剤３を３８．４ｇ加えた後、変成シリコンオイル（日本ユニカー株式会社製品、Ｌ７６０２）を０．３ｇ添加した。Ｈ_２ＳＯ_４を添加してｐＨを５．５に調整した後、ＡｇＮＯ_３を７．３５ｇを含む水溶液７１ｃｃとＫＩを１０モル％含むＫＢｒとＫＩの混合水溶液をダブルジェット法で添加した。この時、銀電位を飽和カロメル電極に対してを＋０ｍＶに保った。ベンゼンチオスルホン酸ナトリウム２ｍｇと二酸化チオ尿素２ｍｇを添加した後、特開平１０−４３５７０号公報に記載の撹拌装置を用いてＡｇＮＯ_３を１７８．５ｇを含む水溶液８００ｃｃとＫＢｒを１１２．５ｇとＫＩを１７．４ｇおよび前記ゼラチン−４を７６．２ｇ含んだ水溶液８００ｃｃを混合し、沃化銀含有率１０モル％の沃化銀微粒子乳剤（平均サイズ：０．０２６μｍ）を調製しながら反応容器内にこの沃化銀乳剤を連続添加した。この時、銀電位を飽和カロメル電極に対してを−３０ｍＶに保った。ＡｇＮＯ_３を５８．５ｇ含む水溶液１３７．６ｃｃとＫＩを１０モル％含むＫＢｒとＫＩの混合水溶液をダブルジェット法で添加した。この時、銀電位を飽和カロメル電極に対して最初は＋２０ｍＶに、後半は＋１２０ｍＶに保った。
【０２７３】
＜エピタキシャル部の形成＞
引き続き５０℃に降温した後、０．３％ＫＩ水溶液１３８ｃｃを添加した後増感色素１および２を添加した。その後５０℃で保持して撹拌を行った後、ＮａＣｌを８．０５ｇ含む水溶液１４０ｃｃを添加した。その後、ＡｇＮＯ_３を１２．８ｇ含む水溶液７９．９ｃｃを添加および、あらかじめ調製した沃化銀微粒子乳剤（Ａｇ量にして、０．０５ｍｏｌ、平均沃化銀含有率３ｍｏｌ％、平均球相当径：０．０９μｍ）を反応容器に添加した。この際、添加されるＡｇＮＯ_３を１ｍｏｌに対して８．０×１０^−４ｍｏｌのＫ_４［ＲｕＣＮ_６］を存在させた。その後、増感色素１および２を添加した。水洗した後、ゼラチンを添加し４０℃でｐＨ５．８、ｐＡｇ８．７に調整した。
【０２７４】
（Ｅｍ−Ｃ６）
前記Ｅｍ−Ｂ５の増感部分を次のように変更することで、Ｅｍ−Ｃ６を得た。
【０２７５】
化合物１および２を添加した後、６０℃に昇温した。増感色素１および２を添加した後に，チオシアン酸カリウム、ビス（１，４，５−トリメチル−１，２，４−トリアゾリウム−３−チオレート金（Ｉ））テトラフルオロボレイト，カルボキシメチルトリメチルチオ尿素、Ｎ，Ｎ−ジメチルセレノウレアを添加し最適に化学増感した。化学増感時に化合物５と化合物６の合計が１×１０^−４ｍｏｌ／ｍｏｌＡｇになるように添加した。化学増感終了時に化合物３および化合物４を添加した。ここで，最適に化学増感するとは，増感色素ならびに各化合物をハロゲン化銀１モルあたり１０^−１から１０^−８モルの添加量範囲から選択したことを意味する。
【０２７６】
（Ｅｍ−Ｂ）
低分子量ゼラチン０．９６ｇ、ＫＢｒ，０．９ｇを含む水溶液１１９２ｍｌを４０℃に保ち，激しく攪拌した。ＡｇＮＯ_３，１．４９ｇを含む水溶液３７．５ｍｌとＫＢｒを１．５ｇ含む水溶液３７．５ｍｌをダブルジェット法で３０秒間に渡り添加した。ＫＢｒを１．２ｇ添加した後，７５℃に昇温し熟成した。充分熟成した後、アミノ基をトリメリット酸で化学修飾した質量平均分子量１０００００のトリメリット化ゼラチン，３０ｇを添加し，ｐＨを７に調整した。二酸化チオ尿素６ｍｇを添加した。ＡｇＮＯ_３，２９ｇを含む水溶液１１６ｍｌとＫＢｒ水溶液をダブルジェット法で最終流量が初期流量の３倍になるように流量加速して添加した。この時、銀電位を飽和カロメル電極に対して−２０ｍＶに保った。ＡｇＮＯ_３，１１０．２ｇを含む水溶液４４０．６ｍｌとＫＢｒ水溶液をダブルジェット法で最終流量が初期流量の５．１倍になるように流量加速して３０分間に渡り添加した。この時、Ｅｍ−Ａ１の調製で使用した沃化銀微粒子乳剤を沃化銀含有率が１５．８ｍｏｌ％になるように同時に流量加速して添加し、かつ銀電位を飽和カロメル電極に対して０ｍＶに保った。ＡｇＮＯ_３，２４．１ｇを含む水溶液９６．５ｍｌとＫＢｒ水溶液をダブルジェット法で３分間に渡り添加した。この時，銀電位を０ｍＶに保った。エチルチオスルホン酸ナトリウム，２６ｍｇを添加した後、５５℃に降温し，ＫＢｒ水溶液を添加し銀電位を−９０ｍＶに調整した。前述した沃化銀微粒子乳剤をＫＩ質量換算で８．５ｇ添加した。添加終了後、直ちにＡｇＮＯ_３，５７ｇを含む水溶液２２８ｍｌを５分間に渡り添加した。この時、添加終了時の電位が＋２０ｍＶになるようにＫＢｒ水溶液で調整した。Ｅｍ−Ａ１とほぼ同様に水洗し，化学増感した。
【０２７７】
（Ｅｍ−Ｃ）
１ｇ当たり３５μｍｏｌのメチオニンを含有する質量平均分子量１０００００のフタル化率９７％のフタル化ゼラチン１．０２ｇ、ＫＢｒ０．９７ｇを含む水溶液１１９２ｍｌを３５℃に保ち，激しく攪拌した。ＡｇＮＯ_３，４．４７ｇを含む水溶液、４２ｍｌとＫＢｒ，３．１６ｇ含む水溶液、４２ｍｌをダブルジェット法で９秒間に渡り添加した。ＫＢｒを２．６ｇ添加した後、６６℃に昇温し、充分熟成した。熟成終了後、Ｅｍ−Ｂの調製で使用した質量平均分子量１０００００のトリメリット化ゼラチン４１．２ｇとＮａＣｌ，１８．５ｇを添加した。ｐＨを７．２に調整した後、ヂメチルアミンボラン，８ｍｇを添加した。ＡｇＮＯ_３，２６ｇを含む水溶液２０３ｍｌとＫＢｒ水溶液をダブルジェット法で最終流量が初期流量の３．８倍になるように添加した。この時，銀電位を飽和カロメル電極に対して−３０ｍＶに保った。ＡｇＮＯ_３，１１０．２ｇを含む水溶液４４０．６ｍｌとＫＢｒ水溶液をダブルジェット法で最終流量が初期流量の５．１倍になるように流量加速して２４分間に渡り添加した。この時、Ｅｍ−Ａ１の調製で使用した沃化銀微粒子乳剤を沃化銀含有率が２．３ｍｏｌ％になるように同時に流量加速して添加し，かつ銀電位を飽和カロメル電極に対して−２０ｍＶに保った。１Ｎのチオシアン酸カリウム水溶液１０．７ｍｌを添加した後，ＡｇＮＯ_３，２４．１ｇを含む水溶液１５３．５ｍｌとＫＢｒ水溶液をダブルジェット法で２分３０秒間に渡り添加した。この時，銀電位を１０ｍＶに保った。ＫＢｒ水溶液を添加して銀電位を−７０ｍＶに調整した。前述した沃化銀微粒子乳剤をＫＩ質量換算で６．４ｇ添加した。添加終了後，直ちにＡｇＮＯ_３，５７ｇを含む水溶液４０４ｍｌを４５分間に渡り添加した。この時，添加終了時の電位が−３０ｍＶになるようにＫＢｒ水溶液で調整した。Ｅｍ−Ａ１とほぼ同様に水洗し，化学増感した。
【０２７８】
（Ｅｍ−Ｄ）
Ｅｍ−Ｃの調製において核形成時のＡｇＮＯ_３添加量を２．０倍に変更した。そして，最終のＡｇＮＯ_３，５７ｇを含む水溶液４０４ｍｌの添加終了時の電位が＋９０ｍＶになるようにＫＢｒ水溶液で調整するように変更した。それ以外はＥｍ−Ｃとほぼ同様にして調製した。
【０２７９】
（Ｅｍ―Ｅ）
質量平均分子量１５０００の低分子量ゼラチン，０．７１ｇ，ＫＢｒ，０．９２ｇ，Ｅｍ−Ａ１の調製で使用した変成シリコンオイル０．２ｇを含む水溶液１２００ｍｌを３９℃に保ち，ｐＨを１．８に調整し激しく攪拌した。ＡｇＮＯ_３，０．４５ｇを含む水溶液と１．５ｍｏｌ％のＫＩを含むＫＢｒ水溶液をダブルジェット法で１７秒間に渡り添加した。この時，ＫＢｒの過剰濃度を一定に保った。５６℃に昇温し熟成した。充分熟成した後，１ｇ当たり３５μｍｏｌのメチオニンを含有する質量平均分子量１０００００のフタル化率９７％のフタル化ゼラチン２０ｇを添加した。ｐＨを５．９に調整した後，ＫＢｒ，２．９ｇを添加した。ＡｇＮＯ_３，２８．８ｇを含む水溶液２８８ｍｌとＫＢｒ水溶液をダブルジェット法で５３分間に渡り添加した。この時，Ｅｍ−Ａ１の調製で使用した沃化銀微粒子乳剤を沃化銀含有率が４．１ｍｏｌ％になるように同時に添加し，かつ銀電位を飽和カロメル電極に対して−６０ｍＶに保った。ＫＢｒ，２．５ｇを添加した後，ＡｇＮＯ_３，８７．７ｇを含む水溶液とＫＢｒ水溶液をダブルジェット法で最終流量が初期流量の１．２倍になるように流量加速して６３分間に渡り添加した。この時，上述の沃化銀微粒子乳剤を沃化銀含有率が１０．５ｍｏｌ％になるように同時に流量加速して添加し，かつ銀電位を−７０ｍＶに保った。二酸化チオ尿素，１ｍｇを添加した後，ＡｇＮＯ_３，４１．８ｇを含む水溶液１３２ｍｌとＫＢｒ水溶液をダブルジェット法で２５分間に渡り添加した。添加終了時の電位を＋２０ｍＶになるようにＫＢｒ水溶液の添加を調整した。ベンゼンチオスルホン酸ナトリウム，２ｍｇを添加した後，ｐＨを７．３に調整した。ＫＢｒを添加して銀電位を−７０ｍＶに調整した後，上述の沃化銀微粒子乳剤をＫＩ質量換算で５．７３ｇ添加した。添加終了後，直ちにＡｇＮＯ_３，６６．４ｇを含む水溶液６０９ｍｌを１０分間に渡り添加した。添加初期の６分間はＫＢｒ水溶液で銀電位を−７０ｍＶに保った。水洗した後，ゼラチンを添加し４０℃でｐＨ６．５，ｐＡｇ，８．２に調整した。化合物１および２を添加した後，５６℃に昇温した。上述した沃化銀微粒子乳剤を銀１ｍｏｌに対して０．０００４ｍｏｌ添加した後，増感色素６および７を添加した。チオシアン酸カリウム，塩化金酸，チオ硫酸ナトリウム，Ｎ，Ｎ−ヂメチルセレノウレアを添加し最適に化学増感した。化学増感終了時に化合物３および４を添加した。
【０２８０】
【化１２】

【０２８１】
【化１３】

【０２８２】
（Ｅｍ−Ｆ）
Ｅｍ−Ｅの調製において核形成時のＡｇＮＯ_３添加量を３．１倍に変更した以外はＥｍ−Ｅとほぼ同様にして調製した。但しＥｍ−Ｅの増感色素を増感色素８，９および１０に変更した。
【０２８３】
【化１４】

【０２８４】
【化１５】

【０２８５】
【化１６】

【０２８６】
（Ｅｍ−Ｇ）
質量平均分子量１５０００の低分子量ゼラチン０．７０ｇ，ＫＢｒ，０．９ｇ，ＫＩ，０．１７５ｇ，Ｅｍ−Ａ１の調製で使用した変成シリコンオイル０．２ｇを含む水溶液１２００ｍｌを３３℃に保ち，ｐＨを１．８に調製し激しく攪拌した。ＡｇＮＯ_３，１．８ｇを含む水溶液と３．２ｍｏｌ％のＫＩを含むＫＢｒ水溶液をダブルジェット法で９秒間に渡り添加した。この時，ＫＢｒの過剰濃度を一定に保った。６９℃に昇温し熟成した。熟成終了後，１ｇ当たり３５μｍｏｌのメチオニンを含有する質量平均分子量１０００００のアミノ基をトリメリット酸で化学修飾したトリメリット化ゼラチン２７．８ｇを添加した。ｐＨを６．３に調製した後，ＫＢｒ，２．９ｇを添加した。ＡｇＮＯ_３，２７．５８ｇを含む水溶液２７０ｍｌとＫＢｒ水溶液をダブルジェット法で３７分間に渡り添加した。この時、質量平均分子量１５０００の低分子量ゼラチン水溶液とＡｇＮＯ_３水溶液とＫＩ水溶液を特開平１０−４３５７０号公開に記載の磁気カップリング誘導型攪拌機を有する別のチャンバ−内で添加前直前混合して調製した粒子サイズ０．００８μｍの沃化銀微粒子乳剤を沃化銀含有率が４．１ｍｏｌ％になるように同時に添加し，かつ銀電位を飽和カロメル電極に対して−６０ｍＶに保った。ＫＢｒ，２．６ｇを添加した後，ＡｇＮＯ_３，８７．７ｇを含む水溶液とＫＢｒ水溶液をダブルジェット法で最終流量が初期流量の３．１倍になるように流量加速して４９分間に渡り添加した。この時，上述の添加前直前混合して調製した沃化銀微粒子乳剤を沃化銀含有率が７．９ｍｏｌ％になるように同時に流量加速し，かつ銀電位を−７０ｍＶに保った。二酸化チオ尿素，１ｍｇを添加した後，ＡｇＮＯ_３，４１．８ｇを含む水溶液１３２ｍｌとＫＢｒ水溶液をダブルジェット法で２０分間に渡り添加した。添加終了時の電位を＋２０ｍＶになるようにＫＢｒ水溶液の添加を調整した。７８℃に昇温し，ｐＨを９．１に調整した後，ＫＢｒを添加して電位を−６０ｍＶにした。Ｅｍ−Ａ１の調製で使用した沃化銀微粒子乳剤をＫＩ質量換算で５．７３ｇ添加した。添加終了後，直ちにＡｇＮＯ_３，６６．４ｇを含む水溶液３２１ｍｌを４分間に渡り添加した。添加初期の２分間はＫＢｒ水溶液で銀電位を−６０ｍＶに保った。Ｅｍ−Ｆとほぼ同様に水洗し，化学増感した。
【０２８７】
（Ｅｍ−Ｈ）
イオン交換した質量平均分子量１０００００のゼラチン１７．８ｇ，ＫＢｒ，６．２ｇ，ＫＩ，０．４６ｇを含む水溶液を４５℃に保ち激しく攪拌した。ＡｇＮＯ_３，１１．８５ｇを含む水溶液とＫＢｒを３．８ｇ含む水溶液をダブルジェット法で４７秒間に渡り添加した。６３℃に昇温後、イオン交換した質量平均分子量１０００００のゼラチン２４．１ｇを添加し，熟成した。充分熟成した後，ＡｇＮＯ_３，１３３．４ｇを含む水溶液とＫＢｒ水溶液をダブルジェット法で最終流量が初期流量の２．６倍になるように２０分間に渡って添加した。この時，銀電位を飽和カロメル電極に対して＋４０ｍＶに保った。また添加開始１０分後にＫ_２ＩｒＣｌ_６を０．１ｍｇ添加した。ＮａＣｌを７ｇ添加した後，ＡｇＮＯ_３を４５．６ｇ含む水溶液とＫＢｒ水溶液をダブルジェット法で１２分間に渡って添加した。この時，銀電位を＋９０ｍＶに保った。また添加開始から６分間に渡って黄血塩を２９ｍｇ含む水溶液１００ｍｌを添加した。ＫＢｒを１４．４ｇ添加した後，Ｅｍ−Ａ１の調製で使用した沃化銀微粒子乳剤をＫＩ質量換算で６．３ｇ添加した。添加終了後，直ちにＡｇＮＯ_３，４２．７ｇを含む水溶液とＫＢｒ水溶液をダブルジェット法で１１分間に渡り添加した。この時，銀電位を＋９０ｍＶに保った。Ｅｍ−Ｆとほぼ同様に水洗し，化学増感した。
【０２８８】
（Ｅｍ−Ｉ）
Ｅｍ−Ｈの調製において核形成時の温度を３８℃に変更した以外はほぼ同様にして調製した。
【０２８９】
（Ｅｍ−Ｊ）
フタル化率９７％の質量平均分子量１０００００のフタル化ゼラチン，０．３８ｇ，ＫＢｒ，０．９９ｇを含む水溶液１２００ｍｌを６０℃に保ち，ｐＨを２に調整し激しく攪拌した。ＡｇＮＯ_３，１．９６ｇを含む水溶液とＫＢｒ，１．９７ｇ，ＫＩ，０．１７２ｇを含む水溶液をダブルジェット法で３０秒間に渡り添加した。熟成終了後，１ｇ当たり３５μｍｏｌのメチオニンを含有する質量平均分子量１０００００のアミノ基をトリメリット酸で化学修飾したトリメリット化ゼラチン１２．８ｇを添加した。ｐＨを５．９に調整した後，ＫＢｒ，２．９９ｇ，ＮａＣｌ６．２ｇを添加した。ＡｇＮＯ_３，２７．３ｇを含む水溶液６０．７ｍｌとＫＢｒ水溶液をダブルジェット法で３５分間に渡り添加した。この時，銀電位を飽和カロメル電極に対して−５０ｍＶに保った。ＡｇＮＯ_３，６５．６ｇを含む水溶液とＫＢｒ水溶液をダブルジェット法で最終流量が初期流量の２．１倍になるように流量加速して３７分間に渡り添加した。この時，Ｅｍ−Ａ１の調製で使用した沃化銀微粒子乳剤を沃化銀含有率が６．５ｍｏｌ％になるように同時に流量加速して添加し，かつ銀電位を−５０ｍＶに保った。二酸化チオ尿素，１．５ｍｇを添加した後，ＡｇＮＯ_３，４１．８ｇを含む水溶液１３２ｍｌとＫＢｒ水溶液をダブルジェット法で１３分間に渡り添加した。添加終了時の銀電位を＋４０ｍＶになるようにＫＢｒ水溶液の添加を調整した。ベンゼンチオスルホン酸ナトリウム，２ｍｇを添加した後，ＫＢｒを添加して銀電位を−１００ｍＶに調整した。上述の沃化銀微粒子乳剤をＫＩ質量換算で６．２ｇ添加した。添加終了後，直ちにＡｇＮＯ_３，８８．５ｇを含む水溶液３００ｍｌを８分間に渡り添加した。添加終了時の電位が＋６０ｍＶになるようにＫＢｒ水溶液の添加で調整した。水洗した後，ゼラチンを添加し４０℃でｐＨ６．５，ｐＡｇ，８．２に調整した。化合物１および２を添加した後，６１℃に昇温した。増感色素１１，１２，１３および１４を添加した後，Ｋ_２ＩｒＣｌ_６，チオシアン酸カリウム，塩化金酸，チオ硫酸ナトリウム，Ｎ，Ｎ−ヂメチルセレノウレアを添加し最適に化学増感した。化学増感終了時に化合物３および４を添加した。
【０２９０】
【化１７】

【０２９１】
【化１８】

【０２９２】
【化１９】

【０２９３】
【化２０】

【０２９４】
（Ｅｍ−Ｋ）
質量平均分子量１５０００の低分子量ゼラチン４．９ｇ，ＫＢｒ，５．３ｇを含む水溶液１２００ｍｌを６０℃に保ち激しく攪拌した。ＡｇＮＯ_３，８．７５ｇを含む水溶液２７ｍｌとＫＢｒ，６．４５ｇを含む水溶液３６ｍｌを１分間に渡りダブルジェット法で添加した。７７℃に昇温した後，ＡｇＮＯ_３，６．９ｇを含む水溶液２１ｍｌを２．５分間に渡り添加した。ＮＨ_４ＮＯ_３，２６ｇ，１Ｎ，ＮａＯＨ，５６ｍｌを順次，添加した後，熟成した。熟成終了後ｐＨを４．８に調製した。ＡｇＮＯ_３，１４１ｇを含む水溶液４３８ｍｌとＫＢｒを１０２．６ｇ含む水溶液４５８ｍｌをダブルジェット法で最終流量が初期流量の４倍になるように添加した。５５℃に降温した後，ＡｇＮＯ_３，７．１ｇを含む水溶液２４０ｍｌとＫＩを６．４６ｇ含む水溶液をダブルジェット法で５分間に渡り添加した。ＫＢｒを７．１ｇ添加した後，ベンゼンチオスルホン酸ナトリウム，４ｍｇとＫ_２ＩｒＣｌ_６，０．０５ｍｇ添加した。ＡｇＮＯ_３，５７．２ｇを含む水溶液１７７ｍｌとＫＢｒ，４０．２ｇを含む水溶液，２２３ｍｌを８分間に渡ってダブルジェット法で添加した。Ｅｍ−Ｊとほぼ同様に水洗し，化学増感した。
【０２９５】
（Ｅｍ−Ｌ）
Ｅｍ−Ｋの調製において核形成時の温度を４２℃に変更した以外は，ほぼ同様にして調製した。
【０２９６】
（Ｅｍ−Ｍ，Ｎ，Ｏ）
Ｅｍ−ＨまたはＥｍ−Ｉとほぼ同様にして調製した。但し化学増感はＥｍ−Ｊとほぼ同様の方法で行った。
【０２９７】
（Ｅｍ−Ｐ）
Ｅｍ−Ｊに対して、増感色素を５、６および７に変更して化学増感を最適に行ってＥｍ−Ｐを得た。
【０２９８】
このようにして得られたＥｍ−Ａ１〜Ａ８、Ｅｍ−Ｂ１〜Ｂ６、Ｅｍ−Ｃ１〜Ｃ６の形態特性を表１に、Ｅｍ−Ａ１〜Ａ８、Ｅｍ−Ｂ１〜Ｂ６、Ｅｍ−Ｃ１〜Ｃ６およびＥｍ−Ｂ〜Ｐの粒子特性を表２にまとめる。
【０２９９】
【表１−１】

【０３００】
【表１−２】

【０３０１】
【表２】

【０３０２】
１）支持体
本実施例で用いた支持体は、下記の方法により作成した。
ポリエチレン−２，６−ナフタレートポリマー１００質量部と紫外線吸収剤としてＴｉｎｕｖｉｎ Ｐ．３２６（チバ・ガイギーＣｉｂａ−Ｇｅｉｇｙ社製）２質量部とを乾燥した後、３００℃にて溶融後、Ｔ型ダイから押し出し、１４０℃で３．３倍の縦延伸を行い、続いて１３０℃で３．３倍の横延伸を行い、さらに２５０℃で６秒間熱固定して厚さ９０μｍのＰＥＮ（ポリエチレンナフタレート）フィルムを得た。なおこのＰＥＮフィルムにはブルー染料、マゼンタ染料及びイエロー染料（公開技法：公技番号９４−６０２３号記載のＩ−１、Ｉ−４、Ｉ−６、Ｉ−２４、Ｉ−２６、Ｉ−２７、ＩＩ−５）を適当量添加した。さらに、直径２０ｃｍのステンレス巻き芯に巻き付けて、１１０℃、４８時間の熱履歴を与え、巻き癖のつきにくい支持体とした。
【０３０３】
２）下塗層の塗設
上記支持体は、その両面にコロナ放電処理、ＵＶ放電処理、さらにグロー放電処理をした後、それぞれの面にゼラチン０．１ｇ／ｍ^２、ソウジウムα−スルホジ−２−エチルヘキシルサクシネート０．０１ｇ／ｍ^２、サリチル酸０．０４ｇ ／ｍ^２、ｐ−クロロフェノール０．２ｇ／ｍ^２、（ＣＨ_２＝ＣＨＳＯ_２ＣＨ_２ＣＨ_２ＮＨＣＯ）_６ＣＨ_２０．０１２ｇ／ｍ^２、ポリアミド−エピクロルヒドリン重縮合物 ０．０２ｇ／ｍ^２の下塗液を塗布して（１０ｃｃ／ｍ^２、バーコーター使用）、下塗層を延伸時高温面側に設けた。乾燥は１１５℃、６分実施した（乾燥ゾーンのローラーや搬送装置はすべて１１５℃となっている）。
【０３０４】
３）バック層の塗設
下塗後の上記支持体の片方の面にバック層として下記組成の帯電防止層、磁気記録層さらに滑り層を塗設した。
【０３０５】
３−１）帯電防止層の塗設
平均粒径０．００５μｍの酸化スズ−酸化アンチモン複合物の比抵抗は５Ω・ｃｍの微粒子粉末の分散物（２次凝集粒子径約０．０８μｍ）を０．２ｇ／ｍ^２、ゼラチン０．０５ｇ／ｍ^２、（ＣＨ_２＝ＣＨＳＯ_２ＣＨ_２ＣＨ_２ＮＨＣＯ）_２ＣＨ_２ ０．０２ｇ／ｍ^２、ポリ（重合度１０）オキシエチレン−ｐ−ノニルフェノール ０．００５ｇ／ｍ^２及びレゾルシンと塗布した。
【０３０６】
３−２）磁気記録層の塗設
３−ポリ（重合度１５）オキシエチレン−プロピルオキシトリメトキシシラン（１５質量％）で被覆処理されたコバルト−γ−酸化鉄（比表面積４３ｍ^２／ｇ、長軸０．１４μｍ、単軸０．０３μｍ、飽和磁化８９Ａｍ^２／ｋｇ、Ｆｅ^＋２／Ｆｅ^＋３＝６／９４、表面は酸化アルミ酸化珪素で酸化鉄の２質量％で処理されている）０．０６ｇ／ｍ^２をジアセチルセルロース１．２ｇ／ｍ^２（酸化鉄の分散はオープンニーダーとサンドミルで実施した）、硬化剤としてＣ_２Ｈ_５Ｃ（ＣＨ_２ＯＣＯＮＨ−Ｃ_６Ｈ_３（ＣＨ_３）ＮＣＯ）_３０．３ｇ／ｍ^２を、溶媒としてアセトン、メチルエチルケトン、シクロヘキサノンを用いてバーコーターで塗布し、膜厚１．２μｍの磁気記録層を得た。マット剤としてシリカ粒子（０．３μｍ）と３−ポリ（重合度１５）オキシエチレン−プロピルオキシトリメトキシシラン（１５質量％）で処理被覆された研磨剤の酸化アルミ（０．１５μｍ）をそれぞれ１０ｍｇ／ｍ^２となるように添加した。乾燥は１１５℃、６分実施した（乾燥ゾーンの ローラーや搬送装置はすべて１１５℃）。Ｘ−ライト（ブルーフィルター）での磁気記録層のＤＢの色濃度増加分は約０．１、また磁気記録層の飽和磁化モーメントは４．２Ａｍ^２／ｋｇ、保磁力７．３×１０^４Ａ／ｍ、角形比は６５％であった。
【０３０７】
３−３）滑り層の調製
ジアセチルセルロース（２５ｍｇ／ｍ^２）、Ｃ_６Ｈ_１３ＣＨ（ＯＨ）Ｃ_１０Ｈ_２０ＣＯＯＣ_４０Ｈ_８１（化合物ａ，６ｍｇ／ｍ^２）／Ｃ_５０Ｈ_１０１Ｏ（ＣＨ_２ＣＨ_２Ｏ）_１６Ｈ（化合物ｂ，９ｍｇ／ｍ^２）混合物を塗布した。なお、この混合物は、キシレン／プロピレンモノメチルエーテル（１／１）中で１０５℃で溶融し、常温のプロピレンモノメチルエーテル（１０倍量）に注加分散して作製した後、アセトン中で分散物（平均粒径０．０１μｍ）にしてから添加した。マット剤としてシリカ粒子（０．３μｍ）と研磨剤の３−ポリ（重合度１５）オキシエチレンプロピルオキシトリメトキシシラン（１５質量％）で被覆された酸化アルミ（０．１５μｍ）をそれぞれ１５ｍｇ／ｍ^２となるように添加した。乾燥は１１５℃、６分行った（乾燥ゾーンのローラーや搬送装置はすべて１１５℃）。滑り層は、動摩擦係数０．０６（５ｍｍφのステンレス硬球、荷重１００ｇ、スピード６ｃｍ／分）、静摩擦係数０．０７（クリップ法）、また後述する乳剤面と滑り層の動摩擦係数も０．１２と優れた特性であった。
【０３０８】
４）感光層の塗設
次に、前記で得られたバック層の反対側に、下記組成の各層を重層塗布し、カラーネガ感光材料である試料１０１〜１２０を作成した。すなわち、第１４層における沃臭化銀乳剤Ｅｍ−Ａ１をそれぞれ乳剤Ｅｍ−Ａ１〜Ａ８、Ｅｍ−Ｂ１〜Ｂ６、Ｅｍ−Ｃ１〜Ｃ６に置きかえることにより、各々試料１０１〜１２０を作成した。
【０３０９】
（感光層の組成）
各層に使用する素材の主なものは下記のように分類されている；
ＥｘＣ：シアンカプラー ＵＶ ：紫外線吸収剤
ＥｘＭ：マゼンタカプラー ＨＢＳ：高沸点有機溶剤
ＥｘＹ：イエローカプラー Ｈ ：ゼラチン硬化剤
（具体的な化合物は以下の記載で、記号の次に数値が付けられ、後ろに化学式が挙げられている）
各成分に対応する数字は、ｇ／ｍ^２単位で表した塗布量を示し、ハロゲン化銀については銀換算の塗布量を示す。ＡｇＢｒＩ（２）は沃化銀含有率が２モル％である乳剤粒子を表す。
【０３１０】
（試料１０１）
第１層（第１ハレーション防止層）
黒色コロイド銀 銀 ０．１５５
０．０７μｍの表面かぶらせＡｇＢｒＩ（２） 銀 ０．０１
ゼラチン ０．８７
ＥｘＣ−１ ０．００２
ＥｘＣ−３ ０．００２
Ｃｐｄ−２ ０．００１
ＨＢＳ−１ ０．００４
Ｓ−３７ ０．００２。
【０３１１】
第２層（第２ハレーション防止層）
黒色コロイド銀 銀 ０．０６６
ゼラチン ０．４０７
ＥｘＭ−１ ０．０５０
ＥｘＦ−１ ２．０×１０^−３
ＨＢＳ−１ ０．０７４
固体分散染料 ＥｘＦ−２ ０．０１５
固体分散染料 ＥｘＦ−３ ０．０２０。
【０３１２】
第３層（中間層）
０．０７μｍのＡｇＢｒＩ（２） ０．０２０
ＥｘＣ−２ ０．０２２
Ｃｐｄ−１ ０．０５
ＨＳＢ−１ ０．０５
ポリエチルアクリレートラテックス ０．０８５
ゼラチン ０．２９４。
【０３１３】
第４層（低感度赤感乳剤層）
沃臭化銀乳剤Ｅｍ−Ｍ 銀 ０．０６５
沃臭化銀乳剤Ｅｍ−Ｎ 銀 ０．１００
沃臭化銀乳剤Ｅｍ−Ｏ 銀 ０．１５８
ＥｘＣ−１ ０．１０９
ＥｘＣ−３ ０．０４４
ＥｘＣ−４ ０．０７２
ＥｘＣ−５ ０．０１１
ＥｘＣ−６ ０．００３
ＥｘＣ−８ ０．０３
Ｃｐｄ−２ ０．０２５
Ｃｐｄ−４ ０．０２５
ＨＢＳ−１ ０．１７
ゼラチン ０．８０。
【０３１４】
第５層（中感度赤感乳剤層）
沃臭化銀乳剤Ｅｍ−Ｋ 銀 ０．２１
沃臭化銀乳剤Ｅｍ−Ｌ 銀 ０．６２
ＥｘＣ−１ ０．１４
ＥｘＣ−２ ０．０２６
ＥｘＣ−３ ０．０２０
ＥｘＣ−４ ０．１２
ＥｘＣ−５ ０．０１６
ＥｘＣ−６ ０．００７
ＥｘＣ−８ ０．０３
Ｃｐｄ−２ ０．０３６
Ｃｐｄ−４ ０．０２８
ＨＢＳ−１ ０．１６
ゼラチン １．１８。
【０３１５】
第６層（高感度赤感乳剤層）
沃臭化銀乳剤Ｅｍ−Ｊ 銀 １．６７
ＥｘＣ−１ ０．１８
ＥｘＣ−３ ０．０７
ＥｘＣ−６ ０．０４７
Ｃｐｄ−２ ０．０４６
Ｃｐｄ−４ ０．０７７
ＨＢＳ−１ ０．３７
ゼラチン ２．１２。
【０３１６】
第７層（中間層）
Ｃｐｄ−１ ０．０８９
固体分散染料ＥｘＦ−４ ０．０３０
ＨＢＳ−１ ０．０５０
ポリエチルアクリレートラテックス ０．８３
ゼラチン ０．８４。
【０３１７】
第８層（重層効果ドナー層（赤感層へ重層効果を与える層））
沃臭化銀乳剤Ｅｍ−Ｅ 銀 ０．５６０
Ｃｐｄ−４ ０．０３０
ＥｘＭ−２ ０．０９６
ＥｘＭ−３ ０．０２８
ＥｘＹ−１ ０．０３１
ＥｘＧ−１ ０．００６
ＨＢＳ−１ ０．０８５
ＨＢＳ−３ ０．００３
ゼラチン ０．５８。
【０３１８】
第９層（低感度緑感乳剤層）
沃臭化銀乳剤Ｅｍ−Ｇ 銀 ０．３９
沃臭化銀乳剤Ｅｍ−Ｈ 銀 ０．２８
沃臭化銀乳剤Ｅｍ−Ｉ 銀 ０．３５
ＥｘＭ−２ ０．３６
ＥｘＭ−３ ０．０４５
ＥｘＧ−１ ０．００５
ＨＢＳ−１ ０．２８
ＨＢＳ−２ ０．０１
Ｓ−２ ０．２７
ゼラチン １．３９。
【０３１９】
第１０層（中感度緑感乳剤層）
沃臭化銀乳剤Ｅｍ−Ｆ 銀 ０．２０
沃臭化銀乳剤Ｅｍ−Ｇ 銀 ０．２５
ＥｘＣ−６ ０．００９
ＥｘＣ−８ ０．０１
ＥｘＭ−２ ０．０３１
ＥｘＭ−３ ０．０２９
ＥｘＹ−１ ０．００６
ＥｘＭ−４ ０．０２８
ＥｘＧ−１ ０．００５
ＨＢＳ−１ ０．０６４
ＨＢＳ−２ ２．１×１０^−３
ゼラチン ０．４４。
【０３２０】
第１１層（高感度緑感乳剤層）
乳剤Ｅｍ−Ｐ 銀 １．２００
ＥｘＣ−６ ０．００４
ＥｘＣ−８ ０．０１
ＥｘＭ−１ ０．０１６
ＥｘＭ−３ ０．０３６
ＥｘＭ−４ ０．０２０
ＥｘＭ−５ ０．００４
ＥｘＹ−５ ０．００８
ＥｘＭ−２ ０．０１３
Ｃｐｄ−４ ０．００７
ＨＢＳ−１ ０．１８
ポリエチルアクリレートラテックス ０．０９９
ゼラチン １．１１。
【０３２１】
第１２層（イエローフィルター層）
黄色コロイド銀 銀 ０．０４７
Ｃｐｄ−１ ０．１６
固体分散染料ＥｘＦ−５ ０．０１０
固体分散染料ＥｘＦ−６ ０．０１０
ＨＢＳ−１ ０．０８２
ゼラチン １．０５７。
【０３２２】
第１３層（低感度青感乳剤層）
沃臭化銀乳剤Ｅｍ−Ｂ 銀 ０．１８
沃臭化銀乳剤Ｅｍ−Ｃ 銀 ０．２０
沃臭化銀乳剤Ｅｍ−Ｄ 銀 ０．０７
ＥｘＣ−１ ０．０４１
ＥｘＹ−１ ０．０３５
ＥｘＹ−２ ０．７１
ＥｘＹ−３ ０．１０
ＥｘＹ−４ ０．００５
Ｃｐｄ−２ ０．１０
Ｃｐｄ−３ ４．０×１０^−３
ＨＢＳ−１ ０．２４
ゼラチン １．４１。
【０３２３】
第１４層（高感度青感乳剤層）
沃臭化銀乳剤Ｅｍ−Ａ１ 銀 ０．７５
ＥｘＣ−１ ０．０１３
ＥｘＹ−２ ０．３１
ＥｘＹ−３ ０．０５
ＥｘＹ−６ ０．０６２
Ｃｐｄ−２ ０．０７５
Ｃｐｄ−３ １．０×１０^−３
ＨＢＳ−１ ０．１０
ゼラチン ０．９１。
【０３２４】
第１５層（第１保護層）
０．０７μｍのＡｇＢｒＩ（２） 銀 ０．３０
ＵＶ−１ ０．２１
ＵＶ−２ ０．１３
ＵＶ−３ ０．２０
ＵＶ−４ ０．０２５
Ｆ−１１ ０．００９
Ｆ−１８ ０．００５
Ｆ−１９ ０．００５
ＨＢＳ−１ ０．１２
Ｓ−２ ５．０×１０^−２
ゼラチン ２．３。
【０３２５】
第１６層（第２保護層）
Ｈ−１ ０．４０
Ｂ−１（直径１．７μｍ） ５．０×１０^−２
Ｂ−２（直径１．７μｍ） ０．１５
Ｂ−３ ０．０５
Ｓ−１ ０．２０
ゼラチン ０．７５。
【０３２６】
更に、各層に適宜、保存性、処理性、圧力耐性、防黴・防菌性、Ｂ−４ないしＢ−６、Ｆ−１ないしＦ−１８及び、鉄塩、鉛塩、金塩、白金塩、パラジウム塩、イリジウム塩、ルテニウム塩、ロジウム塩が含有されている。また、第８層の塗布液にハロゲン化銀１モル当たり８．５×１０^−３ｇ、第１１層に７．９×１０^−３ｇのカルシウムを硝酸カルシウム水溶液で添加し、試料を作製した。更に帯電防止性をよくするためにＷ−１、Ｗ−６、Ｗ−７、Ｗ−８を少なくとも１種含有しており、塗布性をよくするためＷ−２、Ｗ−５を少なくとも１種含有している。
【０３２７】
有機固体分散染料の調製
下記、ＥｘＦ−３を次の方法で分散した。即ち、水２１．７ミリリットル及び５％水溶液のｐ−オクチルフェノキシエトキシエトキシエタンスルホン酸ソーダ３ミリリットル並びに５％水溶液のｐ−オクチルフェノキシポリオキシエチレンエーテル（重合度１０）０．５ｇとを７００ミリリットルのポットミルに入れ、染料ＥｘＦ−３を５．０ｇと酸化ジルコニウムビーズ（直径１ｍｍ）５００ミリリットルを添加して内容物を２時間分散した。この分散には中央工機製のＢＯ型振動ボールミルを用いた。分散後、内容物を取り出し、１２．５％ゼラチン水溶液８ｇに添加し、ビーズを濾過して除き、染料のゼラチン分散物を得た。染料微粒子の平均粒径は０．４４μｍであった。
【０３２８】
同様にして、固体分散染料ＥｘＦ−４を得た。染料微粒子の平均粒径は０．２４μｍであった。ＥｘＦ−２は欧州特許出願公開（ＥＰ）第５４９，４８９Ａ号明細書の実施例１に記載の微小析出（Ｍｉｃｒｏｐｒｅｃｉｐｉｔａｔｉｏｎ）分散方法により分散した。平均粒径は０．０６μｍであった。
【０３２９】
ＥｘＦ−６の固体分散物を以下の方法で分散した。
水を１８％含むＥｘＦ−６のウェットケーキ２８００ｇに４０００ｇの水及びＷ−２の３％溶液を３７６ｇ加えて攪拌し、ＥｘＦ−６の濃度３２％のスラリーとした。次にアイメックス（株）製ウルトラビスコミル（ＵＶＭ−２）に平均粒径０．５ｍｍのジルコニアビーズを１７００ｍｌ充填し、スラリーを通して周速約１０ｍ／ｓｅｃ、吐出量０．５リットル／ｍｉｎで８時間粉砕した。平均粒径は、０．４５μｍであった。
【０３３０】
上記各層の形成に用いた化合物は、以下に示すとおりである。
【０３３１】
【化２１】

【０３３２】
【化２２】

【０３３３】
【化２３】

【０３３４】
【化２４】

【０３３５】
【化２５】

【０３３６】
【化２６】

【０３３７】
【化２７】

【０３３８】
【化２８】

【０３３９】
【化２９】

【０３４０】
【化３０】

【０３４１】
【化３１】

【０３４２】
【化３２】

【０３４３】
【化３３】

【０３４４】
【化３４】

【０３４５】
【化３５】

【０３４６】
【化３６】

【０３４７】
試料の評価法は以下の通り。富士フイルム（株）製ゼラチンフィルターＳＣ−３９（カットオフ波長が３９０ｎｍである長波長光透過フィルター）と連続ウェッジを通して１／１００秒間露光した。現像は富士写真フイルム社製自動現像機ＦＰ−３６０Ｂを用いて以下により行った。尚、漂白浴のオーバーフロー液を後浴へ流さず、全て廃液タンクへ排出する様に改造を行った。このＦＰ−３６０Ｂは発明協会公開技法９４−４９９２号に記載の蒸発補正手段を搭載している。
処理工程及び処理液組成を以下に示す。
【０３４８】
（処理工程）
工程 処理時間 処理温度 補充量＊ タンク容量
発色現像 ３分 ５秒 ３７．８℃ ２０ミリリットル １１．５リットル
漂 白 ５０秒 ３８．０℃ ５ミリリットル ５ リットル
定着 （１） ５０秒 ３８．０℃ ─ ５ リットル
定着 （２） ５０秒 ３８．０℃ ８ミリリットル ５ リットル
水 洗 ３０秒 ３８．０℃ １７ミリリットル ３ リットル
安定 （２） ２０秒 ３８．０℃ １５ミリリットル ３ リットル
乾 燥 １分３０秒 ６０．０℃
＊補充量は感光材料３５ｍｍ幅１．１ｍ当たり（２４Ｅｘ．１本相当）
安定液及び定着液は（２）から（１）への向流方式であり、水洗水のオーバーフロー液は全て定着浴（２）へ導入した。尚、現像液の漂白工程への持ち込み量、漂白液の定着工程への持ち込み量、及び定着液の水洗工程への持ち込み量は感光材料３５ｍｍ幅１．１ｍ当たりそれぞれ２．５ミリリットル、２．０ミリリットル、２．０ミリリットルであった。また、クロスオーバーの時間はいずれも６秒であり、この時間は前工程の処理時間に包含される。
【０３４９】
上記処理機の開口面積は発色現像液で１００ｃｍ^２、漂白液で１２０ｃｍ^２、その他の処理液は約１００ｃｍ^２であった。
【０３５０】
以下に処理液の組成を示す。

【０３５１】
（漂白液） タンク液（ｇ） 補充液（ｇ）
１，３−ジアミノプロパン四酢酸第二
鉄アンモニウム一水塩 １１３ １７０
臭化アンモニウム ７０ １０５
硝酸アンモニウム １４ ２１
コハク酸 ３４ ５１
マレイン酸 ２８ ４２
水を加えて １．０リットル １．０リットル
ｐＨ〔アンモニア水で調整〕 ４．６ ４．０。
【０３５２】
（定着（１）タンク液）
上記漂白タンク液と下記定着タンク液の５対９５（容量比）混合液
（ｐＨ６．８）。
【０３５３】
（定着（２）） タンク液（ｇ） 補充液（ｇ）
チオ硫酸アンモニウム水溶液 ２４０ミリリットル ７２０ミリリットル
（７５０ｇ／リットル）
イミダゾール ７ ２１
メタンチオスルホン酸アンモニウム ５ １５
メタンスルフィン酸アンモニウム １０ ３０
エチレンジアミン四酢酸 １３ ３９
水を加えて １．０リットル １．０リットル
ｐＨ〔アンモニア水、酢酸で調整〕 ７．４ ７．４５。
【０３５４】
（水洗水）
水道水をＨ型強酸性カチオン交換樹脂（ロームアンドハース社製アンバーライトＩＲ−１２０Ｂ）と、ＯＨ型強塩基性アニオン交換樹脂（同アンバーライトＩＲ−４００）を充填した混床式カラムに通水してカルシウム及びマグネシウムイオン濃度を３ｍｇ／リットル以下に処理し、続いて二塩化イソシアヌール酸ナトリウム２０ｍｇ／リットルと硫酸ナトリウム１５０ｍｇ／リットルを添加した。この液のｐＨは６．５〜７．５の範囲にあった。
【０３５５】
（安定液） タンク液、補充液共通 （単位ｇ）
ｐ−トルエンスルフィン酸ナトリウム ０．０３
ポリオキシエチレン−ｐ−モノノニルフェニルエーテル ０．２
（平均重合度１０）
１，２−ベンゾイソチアゾリン−３−オン・ナトリウム ０．１０
エチレンジアミン四酢酸二ナトリウム塩 ０．０５
１，２，４−トリアゾール １．３
１，４−ビス（１，２，４−トリアゾール−１−
イルメチル）ピペラジン ０．７５
水を加えて １．０リットル
ｐＨ ８．５。
【０３５６】
試料１０１〜１２０に対して前記処理を施した。処理済の試料を青色フィルターで濃度測定することにより写真性能の評価を行った。得られた結果を表３に示す。
【０３５７】
表３より、本発明の乳剤を用いた試料は比較試料に対して、粒状性を改良しつつ、高感度を達成している。
【０３５８】
【表３】

【０３５９】
［実施例２］
（種乳剤９）の調製
ＫＢｒを０．９ｇ、前記ゼラチン−３を１ｇ含む水溶液１２００ｃｃを３５℃に保ち撹拌した（１ｓｔ液調整）。
【０３６０】
Ａｇ−１水溶液（ＡｇＮＯ_３濃度０．２９Ｍ）３７．５ｃｃと、Ｘ−１水溶液（前記ゼラチン−３濃度１５．５ｇ／Ｌ、ＫＢｒ濃度０．２９５Ｍ）５５ｃｃを同時に一定の流量で添加した。（添加１）。
【０３６１】
その後ＫＢｒを６ｇ添加し、温度を７５℃に昇温した。昇温の後、Ｇ−１水溶液（前記ゼラチン−２濃度１１７ｇ／Ｌ）３００ｃｃを添加した。この際ｐＨを５．５に調節した。
次いで、Ａｇ−２水溶液（ＡｇＮＯ_３濃度０．５８９Ｍ）７３ｃｃを一定の流量で添加した（添加２）。
【０３６２】
次いで、ベンゼンチオスルホン酸ナトリウムを１ｍｇ添加した。Ａｇ−３水溶液（ＡｇＮＯ_３濃度１．８８Ｍ）２０９ｃｃと、Ｘ−３水溶液（前記ゼラチン−４濃度１８６．７６ｇ／Ｌ、ＫＢｒ濃度０．５３５Ｍ、ＫＩ濃度０．０９４２Ｍ）５９６ｃｃを特開平１０−４３５７０号公報に記載の撹拌装置を用いて混合し、形成される平均サイズ０．０２５μｍの沃臭化銀超微粒子を含むハロゲン化銀写真乳剤を吐出後直ちに連続添加した（添加３）。このとき、Ｘ−２水溶液（ＫＢｒ濃度０．５２５Ｍ）もあわせて添加し、銀電位を飽和カロメル電極に対して０ｍＶに保たれるように調節した。この間ｐＨが５〜６の間に保たれるように調節した。
【０３６３】
その後、通常のフロキュレーション法により脱塩を行い、次いで、攪拌しながら水、ＮａＯＨ、前記のゼラチン−１を添加し、ｐＨ５．８、ｐＡｇが８．８になるように調整した。
【０３６４】
得られた乳剤は、平均沃化銀含有率１２モル％、平均球相当径０．３８μｍ、平均アスペクト比１２の粒子からなっていた。
【０３６５】
（種乳剤１０）の調製
ＫＢｒを０．９ｇ、前記ゼラチン−３を０．１４ｇ含む水溶液１２００ｃｃを３５℃に保ち撹拌した（１ｓｔ液調整）。
【０３６６】
Ａｇ−１水溶液（ＡｇＮＯ_３濃度０．１４５Ｍ）３７．５ｃｃとＸ−１溶液（ＫＢｒ濃度０．１４８Ｍ）５５ｃｃとＧ−１溶液（前記ゼラチン−３濃度５０ｇ／Ｌ）８１ｃｃを一定の流量で同時に添加した。（添加１）。
【０３６７】
その後ＫＢｒを６ｇ添加し、次いで前記ゼラチン−３を４ｇ添加し、温度を７５℃に昇温した。昇温の後、Ｇ−２水溶液（前記ゼラチン−２濃度１１７ｇ／Ｌ）３００ｃｃを添加した。この際ｐＨを５．５に調節した。
次いで、Ａｇ−２水溶液（ＡｇＮＯ_３濃度０．５８９Ｍ）７３ｃｃを一定の流量で添加した（添加２）。
【０３６８】
次いで、ベンゼンチオスルホン酸ナトリウムを１ｍｇ添加した。次いでＡｇ−３水溶液（ＡｇＮＯ_３濃度０．８８３Ｍ）３００ｃｃと、Ｘ−３水溶液（前記ゼラチン−４を１７４．３ｇ／Ｌ、ＫＢｒ濃度０．７１１Ｍ、ＫＩ濃度０．１４６Ｍ）３００ｃｃを特開平１０−４３５７０号公報に記載の撹拌装置を用いて混合し、形成される平均サイズ０．０２５μｍの沃臭化銀超微粒子を含むハロゲン化銀写真乳剤を吐出後直ちに連続添加した（添加３）。このとき、Ｘ−２水溶液（ＫＢｒ濃度０．５２５Ｍ）もあわせて添加し、銀電位を飽和カロメル電極に対して０ｍＶに保たれるように調節した。この間ｐＨが５〜６の間に保たれるように調節した。
【０３６９】
その後、通常のフロキュレーション法により脱塩を行い、次いで、攪拌しながら水、ＮａＯＨ、前記のゼラチン−１を添加し、ｐＨ５．８、ｐＡｇが８．８になるように調整した。
【０３７０】
得られた乳剤中には、平均沃化銀含有率１２モル％、平均球相当径０．３８μｍ、平均アスペクト比１３の粒子が含まれていた。
【０３７１】
（種乳剤１１）の調製
種乳剤２を参考にして種乳剤１１を調製した。
ＮａＣｌを０．５４ｇ、および前記ゼラチン−３を０．５ｇ含有する分散媒溶液１２００ｃｃを反応容器に３５℃に保ち、それを撹拌しながらＡｇ−１水溶液（ＡｇＮＯ_３濃度０．２９Ｍ）の硝酸銀とモル比でＫＢｒ／ＮａＣｌが８０／２０となるように調整した濃度０．２９Ｍのハロゲン塩（ＫＢｒ、ＮａＣｌ）水溶液（Ｘ−１）を各々３７．５ｃｃずつ、同時に添加した。
【０３７２】
次いで添加１の後にＫＢｒを６．５ｇ添加した後、７５℃に昇温した。昇温後Ｇ−１水溶液（前記ゼラチン−２濃度１１７ｇ／Ｌ）３００ｃｃを添加した。この際、ｐＨは５．５に調整した。
【０３７３】
次いで、Ａｇ−２水溶液（ＡｇＮＯ_３濃度０．５８９Ｍ）７３ｃｃを一定の流量で添加した（添加２）。
【０３７４】
次いで、ベンゼンチオスルホン酸ナトリウムを１ｍｇ添加した。Ａｇ−３水溶液（ＡｇＮＯ_３濃度１．８８Ｍ）１１８６ｃｃと、Ｘ−３水溶液（前記ゼラチン−４濃度１８６．７６ｇ／Ｌ、ＫＢｒ濃度０．５６６Ｍ、ＫＩ濃度０．０６２９Ｍ）３３８０ｃｃを特開平１０−４３５７０号公報に記載の撹拌装置を用いて混合し、形成される平均サイズ０．０２５μｍの沃臭化銀超微粒子を含むハロゲン化銀写真乳剤を吐出後直ちに連続添加した（添加３）。このとき、Ｘ−２水溶液（ＫＢｒ濃度０．５２５Ｍ）もあわせて添加し、銀電位を飽和カロメル電極に対して０ｍＶに保たれるように調節した。この間ｐＨが５〜６の間に保たれるように調節した。
【０３７５】
その後、通常のフロキュレーション法により脱塩を行い、次いで、攪拌しながら水、ＮａＯＨ、前記のゼラチン−１を添加し、ｐＨ５．８、ｐＡｇが８．８になるように調整した。
【０３７６】
得られた乳剤中には、平均沃化銀含有率９．５モル％、平均球相当径０．８５μｍ、平均アスペクト比３３の粒子が含まれていた。
【０３７７】
（種乳剤１２）の調製
種乳剤２を参考にして種乳剤１２を調製した。
ＫＢｒを０．９ｇ、前記ゼラチン−３を０．５ｇ含む水溶液１２００ｃｃを３５℃に保ち撹拌した（１ｓｔ液調整）。
【０３７８】
Ａｇ−１水溶液（ＡｇＮＯ_３濃度０．２９Ｍ）の硝酸銀とモル比でＫＢｒ／ＮａＣｌが９５／５となるように調整した（濃度０．２９Ｍ、前記ゼラチン濃度７．８ｇ／Ｌ）のハロゲン塩（ＫＢｒ、ＮａＣｌ）水溶液（Ｘ−１）を各々３７．５ｃｃずつを同時に添加した。
【０３７９】
その後ＫＢｒを６．５ｇ添加し、次いで前記ゼラチン−３を４ｇ添加し、温度を７５℃に昇温した。昇温での熟成過程経た後、Ｇ−１水溶液（前記ゼラチン−２濃度１１７ｇ／Ｌ）３００ｃｃを添加した。
【０３８０】
次いで１Ｎの硫酸を適量添加しｐＨを５．５に調節した。
次いで、Ａｇ−２水溶液（ＡｇＮＯ_３濃度０．５８９Ｍ）７３ｃｃを一定の流量で添加した（添加２）。
【０３８１】
次いで、ベンゼンチオスルホン酸ナトリウムを１ｍｇ添加した。次いでＡｇ−３水溶液（ＡｇＮＯ_３濃度０．８８３Ｍ）１７００ｃｃと、Ｘ−３水溶液（前記ゼラチン−４を１７４．３ｇ／Ｌ、ＫＢｒ濃度０．７７１Ｍ、ＫＩ濃度０．０８５７Ｍ）１７００ｃｃを特開平１０−４３５７０号公報に記載の撹拌装置を用いて混合し、形成される平均サイズ０．０２５μｍの沃臭化銀超微粒子を含むハロゲン化銀写真乳剤を吐出後直ちに連続添加した（添加３）。このとき、Ｘ−２水溶液（ＫＢｒ濃度０．５２５Ｍ）もあわせて添加し、銀電位を飽和カロメル電極に対して＋４０ｍＶに保たれるように調節した。この間ｐＨが５〜６の間に保たれるように調節した。
【０３８２】
その後、通常のフロキュレーション法により脱塩を行い、次いで、攪拌しながら水、ＮａＯＨ、前記のゼラチン−１を添加し、ｐＨ５．８、ｐＡｇが８．８になるように調整した。
【０３８３】
得られた乳剤中には、平均沃化銀含有率９．５モル％、平均球相当径０．８５μｍ、平均アスペクト比３５の粒子が含まれていた。
【０３８４】
（Ｅｍ−Ｄ１）
アルカリ処理ゼラチン４６ｇ、ＫＢｒ１．７ｇを含む水溶液１２１１ｃｃを７５℃に保ち激しく攪拌した。前述した種乳剤９を１２４ｇ加えた後、変成シリコンオイル（日本ユニカ−株式会社製品、Ｌ７６０２）を０．３ｇ添加した。Ｈ_２ＳＯ_４を添加してｐＨを５．５に調整した後、ＡｇＮＯ_３を６１．４ｇ含む水溶液１３７．６ｃｃとＫＩを１０モル％含むＫＢｒとＫＩの混合水溶液をダブルジェット法で添加した。この時、銀電位を飽和カロメル電極に対してを最初＋２０ｍＶに、後半は＋１２０ｍＶに保った。５０℃に降温した後，０．３％ＫＩ水溶液５７．８ｃｃを添加した。その後直ちに、ＡｇＮＯ_３を８．８ｇ含む水溶液１９．７ｃｃとＮａＣｌを１．５１ｇ、ＫＢｒを２．４７ｇ含む水溶液２１ｃｃと沃化銀微粒子０．００５ｍｏｌを含む溶液を同時に添加した。この際、添加されるＡｇＮＯ_３１ｍｏｌに対して８．０×１０^−４ｍｏｌのＫ_４［ＲｕＣＮ_６］を存在させた。その後、増感色素を添加した。水洗した後、ゼラチンを添加し４０℃でｐＨ５．８、ｐＡｇ８．７に調整した。
【０３８５】
＜増感＞
化合物１および２を添加した後、６０℃に昇温した。増感色素１および２を添加した後に、チオシアン酸カリウム、塩化金酸、チオ硫酸ナトリウム，Ｎ，Ｎ−ヂメチルセレノウレアを添加し最適に化学増感した。化学増感終了時に化合物３および化合物４を添加した。ここで最適に化学増感するとは、増感色素ならびに各化合物をハロゲン化銀１モルあたり１０^−１から１０^−８モルの添加量範囲から選択したことを意味する。
【０３８６】
（Ｅｍ−Ｅ１）
アルカリ処理ゼラチン４６ｇ、ＫＢｒ１．７ｇを含む水溶液１２１１ｃｃを７５℃に保ち激しく攪拌した。前述した種乳剤１１を３５ｇ加えた後、変成シリコンオイル（日本ユニカ−株式会社製品、Ｌ７６０２）を０．３ｇ添加した。Ｈ_２ＳＯ_４を添加してｐＨを５．５に調整した後、ＡｇＮＯ_３を８．９ｇ含む水溶液７１ｃｃとＫＩを１０モル％含むＫＢｒとＫＩの混合水溶液をダブルジェット法で添加した。この時銀電位を飽和カロメル電極に対して０ｍＶに保った。ベンゼンチオスルホン酸ナトリウム２ｍｇと二酸化チオ尿素２ｍｇを添加した後、特開平１０−４３５７０号公開に記載の撹拌装置を用いてＡｇＮＯ_３を１７８．５ｇ含む水溶液８００ｃｃとＫＢｒを１１２．５ｇ、ＫＩを１７．４ｇおよび前記ゼラチン−４を８０ｇ含んだ水溶液８００ｃｃを混合し、沃化銀含有率１０モル％のＡｇＢｒＩ微粒子乳剤（平均サイズ：０．０２６μｍ）を調製しながら反応容器内にこのＡｇＢｒＩ乳剤を連続添加した。この時、銀電位を飽和カロメル電極に対して−３０ｍＶに保った。次いで、ＡｇＮＯ_３を６１．４ｇ含む水溶液１３７．６ｃｃとＫＩを１０モル％含むＫＢｒとＫＩの混合水溶液をダブルジェット法で添加した。この時、銀電位を飽和カロメル電極に対してを最初＋２０ｍＶに、後半は＋１２０ｍＶに保った。５０℃に降温した後，０．３％ＫＩ水溶液５７．８ｃｃを添加した。その後直ちに、ＡｇＮＯ_３を８．８ｇ含む水溶液１９．７ｃｃとＮａＣｌを１．５１ｇ、ＫＢｒを２．４７ｇ含む水溶液２１ｃｃと沃化銀微粒子０．００５ｍｏｌを含む溶液を同時に添加した。この際、添加されるＡｇＮＯ_３１ｍｏｌに対して８．０×１０^−４ｍｏｌのＫ_４［ＲｕＣＮ_６］を存在させた。その後、増感色素を添加した。水洗した後、ゼラチンを添加し４０℃でｐＨ５．８、ｐＡｇ８．７に調整した。
【０３８７】
＜増感＞
化合物１および２を添加した後、６０℃に昇温した。増感色素１および２を添加した後に、チオシアン酸カリウム、塩化金酸、チオ硫酸ナトリウム，Ｎ，Ｎ−ヂメチルセレノウレアを添加し最適に化学増感した。化学増感終了時に化合物３および化合物４を添加した。ここで最適に化学増感するとは、増感色素ならびに各化合物をハロゲン化銀１モルあたり１０^−１から１０^−８モルの添加量範囲から選択したことを意味する。
【０３８８】
（Ｅｍ−Ｄ２）
種乳剤９の替わりに種乳剤１０を使用した以外はＥｍ−Ｄ１と同様にしてＥｍ−Ｄ２を得た。
【０３８９】
（Ｅｍ−Ｄ３）
Ｅｍ−Ｄ２の増感部分を前記Ｅｍ−Ｃ３と同様の増感を行うことでＥｍ−Ｄ３を得た。
【０３９０】
（Ｅｍ−Ｄ４）
Ｅｍ−Ｄ２の増感部分を前記Ｅｍ−Ｃ４と同様の増感を行うことでＥｍ−Ｄ４を得た。
【０３９１】
（Ｅｍ−Ｅ２）
種乳１１の替わりに種乳剤１２を使用した以外はＥｍ−Ｅ１と同様にしてＥｍ−Ｅ２を得た。
【０３９２】
（Ｅｍ−Ｅ３）
Ｅｍ−Ｅ２の増感部分を前記Ｅｍ−Ｃ３と同様の増感を行うことでＥｍ−Ｅ３を得た。
【０３９３】
（Ｅｍ−Ｅ４）
Ｅｍ−Ｅ２の増感部分を前記Ｅｍ−Ｃ４と同様の増感を行うことでＥｍ−Ｅ４を得た。
【０３９４】
このようにして得られたＥｍ−Ｄ１〜Ｄ４、Ｅｍ−Ｅ１〜Ｅ４の形態特性を表４に、粒子特性を表５にまとめる。
【０３９５】
【表４】

【０３９６】
【表５】

【０３９７】
下塗り層を設けてある三酢酸セルロースフィルム支持体に、各乳剤を４０℃で３０分間溶解経時した後、下記（１）、（２）に示すような塗布条件で、前記の乳剤の塗布を行った。
【０３９８】
（１）乳剤層
乳剤・・・各種の乳剤 （銀 １．６３×１０^−２モル／ｍ^２）
カプラ−
ＥｘＭ−１ （２．２６×１０^−３モル／ｍ^２）
ＥｘＹ−５ （８．０×１０^−３ｇ／ｍ^２）
高沸点有機溶媒ＨＢＳ−１ （１．８×１０^−１ｇ／ｍ^２）
ゼラチン （３．２４ｇ／ｍ^２）
界面活性剤 Ｗ−４
（２）保護層
Ｈ−１ （０．０８ｇ／ｍ^２）
ゼラチン （１．８ｇ／ｍ^２）
塗布する乳剤をＥｍ−Ｄ１〜４、Ｅｍ−Ｅ１〜Ｅ４に変えることで、各々試料２０１〜２０８を作成した。
【０３９９】
これらの試料を４０℃、相対湿度７０％の条件下で１４時間硬膜処理を施した。その後、連続ウェッジを通して１ ／１００ 秒間露光を行い、下記の現像処理を行なった試料を緑色フィルターで濃度測定することにより写真感度と長期保存前のカブリ濃度を求めた。感度はかぶり濃度プラス０．２の濃度に到達するのに必要な露光量の逆数の相対値で表示した。感材の保存カブリの評価として、４０℃、相対湿度６０％の条件下で１４日間保存した後、１ ／１００ 秒間露光を行い、下記の現像処理を行なった試料を緑色フィルターで濃度測定し長期保存後のカブリ濃度を求め、保存前後のカブリ濃度差を求めた。
【０４００】
現像は富士写真フイルム社製自動現像機ＦＰ−３６２Ｂを用いて以下により行った。
【０４０１】
処理工程及び処理液組成を以下に示す。
【０４０２】
（処理工程）
工程 処理時間 処理温度 補充量＊ タンク容量
発色現像 ３分５秒 ３８℃ １５Ｍｌ １０．３Ｌ
漂白 ５０秒 ３８℃ ５ｍＬ ３．６Ｌ
定着（１） ５０秒 ３８℃ − ３．６Ｌ
定着（２） ５０秒 ３８℃ ７．５ｍＬ ３．６Ｌ
安定（１） ３０秒 ３８℃ − １．９Ｌ
安定（２） ２０秒 ３８℃ − １．９Ｌ
安定（３） ２０秒 ３８℃ ３０ｍＬ １．９Ｌ
乾燥 １分３０秒 ６０℃
＊補充量は感光材料３５ｍｍ幅１．１ｍ当たり（２４Ｅｘ．１本相当）。
【０４０３】
安定液は（３）→（２）→（１）への向流方式であり、定着液も（２）から（１）へ向流配管で接続されている。また、安定液（２）のタンク液を定着液（２）へ補充量相当１５ｍＬを流入している。更に、発色現像液は下記処方の発色現像液（Ａ）補充液及び発色現像液（Ｂ）補充液をそれぞれ補充量相当１２ｍＬと３ｍＬに分割して合計１５ｍＬとして補充している。なお、現像液の漂白工程への持ち込み量、漂白液の定着工程への持ち込み量及び定着液の水洗工程への持ち込み量は何れも感光材料３５ｍｍ幅１． １ｍ当たり２．０ｍＬであった。また、クロスオーバーの時間は何れも６秒であり、この時間は前工程の処理時間に包含される。
【０４０４】
以下に処理液の組成を示す。
【０４０５】

上記タンク液は下記（発色現像液（Ｂ））混合後の組成を示す。
【０４０６】

上記タンク液は前記（発色現像液（Ａ））混合後の組成を示す。
【０４０７】

【０４０８】

【０４０９】

【０４１０】
試料２０１〜２０８に対して前記処理を施した。処理済の試料を青色フィルターで濃度測定することにより写真性能の評価を行った。得られた結果を表６、表７に示す。
【０４１１】
表６、表７より、本発明の乳剤を用いた試料は比較試料に対して、粒状性を改良しつつ、高感度を達成している。
【０４１２】
【表６】

【０４１３】
【表７】

【０４１４】
【発明の効果】
本発明は、全投影面積の５０％以上を占めるハロゲン化銀粒子の沃化銀含有率が３モル％以上で、かつ投影面積径の単分散性に優れ、かつ粒子厚みの単分散性に優れたハロゲン化銀写真乳剤を用いることで、感度・粒状に優れたハロゲン化銀感光材料を提供できる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a silver halide photographic emulsion which is excellent in sensitivity / granularity ratio and is particularly useful as an emulsion for a blue photosensitive layer.
[0002]
[Prior art]
In silver halide photographic light-sensitive materials, silver halide tabular grains have many advantages and are therefore widely used in the field. In recent years, the technology has been remarkably advanced.
[0003]
As the composition of silver halide grains, silver iodobromide (including silver iodochlorobromide) systems are mainly used in color photographic light-sensitive materials excluding color paper. The silver iodobromide grains contain silver iodide in the silver bromide crystal lattice not exceeding the solid solution limit in the silver bromide (that is, the silver iodide content is 40 mol% or less). In contrast to silver bromide, silver iodobromide has advantages such as improved latent image formation efficiency, improved light absorption (inherent absorption of silver halide), improved adsorption of added adsorbate, and improved graininess.
[0004]
Since the absorption of blue light is increased by increasing the silver iodide content in the silver iodobromide grains, the silver halide grains having a high silver iodide content are particularly suitable as an emulsion for use in a blue light-sensitive layer. Also in the green / red light absorbing emulsion, the quantum sensitivity is increased by increasing the silver iodide content.
[0005]
In the formation of tabular grains having a high silver iodide content, there are problems such as an increase in the distribution of silver iodide content between grains and an increase in the distribution of the equivalent sphere diameter of the grains. The difficulty of forming was high.
[0006]
In the conventional silver iodobromide ion growth by the double jet method, the thickness of tabular silver halide grains tends to increase because of high supersaturation growth, and it is difficult to obtain thin tabular grains. In addition, ion growth has poor monodispersity in thickness, and particles having a uniform thickness cannot be obtained.
[0007]
In the prior art, a monodisperse emulsion is obtained by setting the silver chloride content to 5 mol% or more with respect to the Ag content of the nuclei formed in the nucleation process. Specifically, it is an emulsion composed of silver halide hexagonal tabular grains and has a projected area variation coefficient of 30% or less, and 50% or more of the total projected area of the silver halide hexagonal tabular grains is (111 A silver halide photographic emulsion characterized by having a plane as a main plane and satisfying a silver iodide content of 7 mol% or more, a projected area diameter of 3 μm or more, and an aspect ratio of 8 or more (for example, , See Patent Document 1). Thus, a silver iodobromide emulsion having a small variation coefficient of projected area diameter has been obtained by the advancement of the technology for forming silver iodobromide tabular grains.
[0008]
In the examples of Patent Document 1, an emulsion having a variation coefficient of thickness of 16% is shown as an invention. By improving the monodispersity of the thickness between the particles, the degree of chemical sensitization after the formation of the particles becomes uniform among the particles, and this appears in the photographic performance as an increase in sensitivity and granularity. However, until now, the monodispersity of the thickness between grains in the high-sensitivity emulsion has not been sufficient, and an emulsion having a higher monodispersity in the thickness between grains has been desired.
[0009]
[Patent Document 1]
JP 2003-43603 A
[0010]
[Problems to be solved by the invention]
An object of the present invention is to provide a silver halide photographic emulsion containing silver halide grains having high sensitivity and excellent granularity.
[0011]
[Means for Solving the Problems]
The object of the present invention can be achieved by the following means.
(1) In a silver halide photographic emulsion containing a dispersion medium and silver halide grains, the variation coefficient of the projected area diameter of the silver halide grains is 30% or less, and the variation coefficient of the grain thickness is 15% or less. A silver halide photographic emulsion wherein 50% or more of the total projected area is occupied by silver halide grains satisfying the following (a), (b), (c) and (d):
[0012]
(A) Silver halide tabular grains whose main plane is a smooth (111) plane
(B) Silver iodide content of 3 mol% or more
(C) Projected area diameter of 1 μm or more
(D) An aspect ratio of 8 or more.
[0013]
(2) The silver halide photographic emulsion as described in (1) above, wherein the silver halide grains further satisfy the following (e):
(E) Silver iodide content of 5 mol% or more.
[0014]
(3) The silver halide photographic emulsion as described in (1) or (2) above, wherein the silver halide grains further satisfy the following (f):
[0015]
(F) Sphere equivalent diameter of 0.6 μm to 2.0 μm.
[0016]
(4) The silver halide photographic emulsion according to any one of (1) to (3), wherein the silver halide grains further satisfy the following (g):
(G) It contains at least 10 dislocation lines per particle.
[0017]
(5) The silver halide photographic emulsion according to any one of (1) to (4), wherein the silver halide grains further satisfy the following (h):
(H) It has at least one epitaxial junction per particle at the vertex and / or the outer peripheral portion and / or the main plane portion.
[0018]
(6) Silver iodide fine grains and / or iodobromide formed at least 50% of the total silver amount simultaneously with the addition of the aqueous silver salt solution and the aqueous halogen salt solution and formed outside the vessel in which the growth is performed. The silver halide photographic emulsion as described in any one of (1) to (5) above, which is obtained by adding silver fine particles to a reaction vessel in which grain growth is carried out.
[0019]
(7) The halogenation according to (6), wherein the silver iodide fine particles and / or silver iodobromide fine particles are added continuously to a reaction vessel in which grain growth is performed. Silver photographic emulsion.
[0020]
(8) In the silver halide photographic light-sensitive material having at least one silver halide photographic emulsion layer on the support, at least one of the emulsion layers described in any one of (1) to (7) above A silver halide photographic light-sensitive material comprising the silver halide photographic emulsion described above.
[0021]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in more detail.
The halogen composition of the silver halide grains contained in the silver halide photographic emulsion in the present invention is preferably silver iodobromide or silver iodochlorobromide. As a form of the silver halide grains, 50% or more of the total projected area of the silver halide grains to be contained is tabular grains whose main plane is a smooth (111) plane.
[0022]
In the present invention, tabular grains (hereinafter referred to as tabular grains) refer to silver halide grains having two opposing parallel (111) major planes. The tabular grain of the present invention has one twin plane or two or more parallel twin planes. The twin plane means the (111) plane when ions at all lattice points are mirror images on both sides of the (111) plane.
[0023]
The tabular grains have a triangular shape, a hexagonal shape, or a circular shape when viewed from above, and have outer surfaces parallel to each other. Here, the hexagonal shape means that the ratio of the side having the maximum length to the length of the side having the minimum length is 1 or more and 2 or less. It ’s big. The circular shape means that these are rounded.
[0024]
Silver halide grains not included in the tabular grains include normal crystal grains and grains having two or more twin planes that are non-parallel. The particles having two non-parallel twin planes include triangular pyramids and rods. These are collectively referred to as non-tabular grains.
[0025]
The ratio of the non-tabular grains is preferably 7% or less, more preferably 5% or less, as a ratio of the number of the whole grains. Because non-tabular grains and tabular grains have very different shape characteristics, non-tabular grains are tabular grains when dislocation lines are introduced, epitaxial junctions are introduced, spectral sensitization, or chemical sensitization is applied to increase photographic sensitivity. Not so sensitized. Since the non-tabular grains are grains that do not contribute to the sensitivity, the non-tabular grains cause deterioration of the graininess, so it is preferable that the number is as small as possible.
[0026]
As for the projected area diameter and thickness of the tabular grains, the diameter (projected area diameter) and thickness of a circle having an area equal to the projected area of each grain are obtained by taking a transmission electron micrograph by the replica method. In this case, the thickness is calculated from the length of the shadow of the replica. This observation method also confirms that the main plane is smooth.
[0027]
The emulsion of the present invention is preferably monodisperse. The variation coefficient of the projected area diameter of all silver halide grains constituting the emulsion of the present invention is 30% or less, more preferably 25% or less. The variation coefficient of the thickness of all silver halide tabular grains constituting the emulsion of the present invention is 15% or less, more preferably 12% or less. Further, the variation coefficient of the equivalent sphere diameter of all silver halide grains constituting the emulsion of the present invention is preferably 30% or less, more preferably 25% or less. The equivalent sphere diameter is the diameter of a sphere having a volume equal to the volume of each particle. The volume of each grain can be calculated by the product of the projected area and the thickness of the tabular grain. The coefficient of variation is the value obtained by dividing the standard deviation of the projected area diameter, sphere equivalent diameter, or thickness distribution of each silver halide grain by the average value of the projected area diameter, sphere equivalent diameter, or thickness, respectively, by 100. The value is expressed in%.
[0028]
In the silver halide photographic emulsion of the present invention, 50% or more of the total projected area of the silver halide grains contained is such that the silver iodide content in the silver halide tabular grains is 3 mol with respect to the total silver amount in the grains. % Of silver halide grains. More preferably, the silver iodide content is 5 mol% or more and 20 mol% or less, and more preferably 8 mol% or more and 20 mol% or less with respect to the total silver amount in the grain. The silver chloride content is preferably 10 mol% or less with respect to the total amount of silver in the grain.
[0029]
In the silver halide photographic emulsion of the present invention, 50% or more of the total projected area of the silver halide grains contained is occupied by silver halide grains having a projected area diameter of 1.0 μm or more. The projected area diameter is preferably 1.0 μm or more and 20.0 μm or less, and more preferably 1.0 μm or more and 10.0 μm or less. In the equivalent sphere diameter, it is preferable that 50% or more of the total projected area of the contained silver halide grains is occupied by 0.6 to 2.0 μm of silver halide grains.
[0030]
In the present silver halide photographic emulsion, 50% or more of the total projected area of the silver halide grains contained is occupied by silver halide grains having an aspect ratio of 8 or more, and the aspect ratio is preferably 8 or more and 100 or less, 10 or more and 50 or less are more preferable. The aspect ratio is a value obtained by dividing the projected area diameter of a grain by the thickness of the grain.
[0031]
In the emulsion of the present invention, the relative standard deviation of the silver iodide content distribution between grains is preferably 20% or less. More preferably, it is 10% or less. The relative standard deviation of the silver iodide content between grains can be easily determined by using the EPMA method (Electron-Probe Micro Analyzer method). In this method, a sample in which emulsion grains are well dispersed so as not to contact each other is prepared and irradiated with an electron beam. Elemental analysis of a very small portion can be performed by X-ray analysis by electron beam excitation. Using this method, the halogen composition of individual grains can be determined by determining the characteristic X-ray intensity of silver and iodine emitted from each grain. If the halogen composition is confirmed by the EPMA method for at least 100 grains, the relative standard deviation is likely. The relative standard deviation of the silver iodide content is a value expressed as% by dividing the standard deviation of the distribution of silver iodide content for at least 100 grains by the average silver iodide content and multiplying by 100. .
[0032]
In the silver halide photographic emulsion of the present invention, the area of the (100) plane relative to the average area of the side surface determined from the average projected area diameter and average thickness of all grains is preferably 20% or more with respect to the area of the side surface. . Specifically, 20% to 100% is preferable, and 50% to 90% is more preferable. The side surface refers to a portion sandwiched between two parallel main planes, and the average projected area diameter and average thickness of all particles are measured by transmission electron micrograph photography using the replica method described above. The area of the side surface can be obtained from the product of the circumference and thickness of the projection surface. The crystal plane of the tabular grain is T.W. Tani et al J. Org. Img. Sci,29  165-171 (1985) can be used. Specifically, the ratio of the (100) plane to the (111) plane is obtained by this method, and the ratio of the (100) plane can be obtained from this ratio.
[0033]
The silver halide tabular grains contained in the emulsion of the present invention preferably have a so-called core / shell structure composed of a core portion having different silver iodide contents and a shell portion surrounding the core portion. Good. A core part is a silver halide grain obtained by a nucleation process. The shell part may surround the entire core part, may surround only the side surfaces of the tabular grains of the core part, or may surround only the main flat surface part. The number of shell portions may be one or two or more. When the number of shell parts is two or more, the shell part outside the core part is the first shell, the shell part outside the first shell is the second shell, and the shell part outside is sequentially the third shell, Called the fourth shell.
[0034]
In the silver halide grains of the present invention, dislocation lines may be present in a portion preferably within 20%, more preferably within 10%, of the area from the outer periphery of the grain projection. The dislocation line may exist along the outer peripheral portion in the vicinity of the outer peripheral portion, or may be localized in the vicinity of the corner portion. When viewed from the projection plane, the vicinity of the corner means that when a perpendicular is drawn from the point of x% from the center of the straight line connecting the center of the projected area diameter of each particle to each vertex, This is a three-dimensional part obtained when considering an area surrounded by a perpendicular and the sides that make up each vertex and cutting out perpendicularly to the main plane to include the area. The value of x is preferably 50 or more and less than 100, more preferably 75 or more and less than 100. The average number of dislocation lines present is preferably 10 or more per grain. More preferably, the average number is 20 or more per particle.
[0035]
In the silver halide photographic emulsion of the present invention, silver halide grains having 50% or more of the total projected area may have at least one epitaxial junction. Epitaxial bonding is that the crystal | crystallization which protruded outside is joined to the tabular grain surface. At this time, the crystal protruding outside is named an epitaxial portion. The crystal composition of the epitaxial portion may be the same as that of the silver halide tabular grain that is the growth base of the epitaxial portion, but is preferably not the same. Specific examples include AgBr, AgCl, AgI, AgBrI, AgClI, AgBrCl, AgBrClI, AgSCN. The position of the epitaxial part may be any of the apex part, the outer peripheral part, and the main plane part of the tabular grain, or may extend over a plurality of locations. The apex portion refers to six apexes of hexagonal tabular grains. The outer peripheral portion refers to the six sides of the hexagonal tabular grain and the plane connecting the two main plane portions, that is, the side portion, and the epitaxial portion exists on the six sides and any portion of the side portion. May be. The main plane portion means two main planes referred to as tabular grains, and the epitaxial portion may exist at any position on the main plane. As for the shape of the epitaxial portion, {100} plane, {111} plane, and {110} plane may appear independently on the surface of the epitaxial portion, or a plurality thereof may appear. Further, it may have an irregular shape in which a higher-order surface appears.
[0036]
Below, the preparation method of a silver halide grain is demonstrated.
As a method for preparing a silver halide photographic emulsion, it is common to form silver halide nuclei and then grow silver halide grains to obtain grains of a desired size, and the present invention is also the same. There is no change. Further, the formation of tabular grains includes at least nucleation, ripening, and growth steps. This process is described in detail in US Pat. No. 4,945,037. The growth step is a step of adding silver salt aqueous solution and halogen salt aqueous solution to a reaction vessel by a double jet method to grow silver halide grain nuclei. A method of controlling pAg in the reaction solution in the growth by the double jet method can also be used.
[0037]
For easy understanding, the preparation process of the present invention is divided into a base part forming process ((a) process) and a subsequent outer part forming process ((b) process) for convenience. Although the preparation step of the present invention may basically be only step (a), it is more preferable to carry out step (b) following step (a). The (b) step is (b1) a dislocation introducing step, (b2) a corner dislocation limited introducing step, (b3) an epitaxial bonding step, and any step may be used. For convenience of explanation, the silver halide grains obtained after the completion of the step (a) are named base grains.
[0038]
The step (a) which is a step of forming the base particles will be described. The formation process of the base particle can be manufactured through processes generally well known in the art, that is, a process of nucleation process-ripening process-growth process. Hereinafter, nucleation, ripening, growth, and each process will be described.
[0039]
1. Nucleation process
Tabular grain nucleation is generally carried out by adding a silver salt aqueous solution and an alkali halide aqueous solution to a reaction vessel holding an aqueous solution of a protective colloid, or a silver salt in a protective colloid solution containing an alkali halide. A single jet method in which an aqueous solution is added is used. Moreover, the method of adding aqueous alkali halide solution to the protective colloid solution containing a silver salt as needed can also be used. Moreover, the method of adding silver salt aqueous solution, alkali halide aqueous solution, and a protective colloid solution simultaneously by the triple jet method as needed can be used. At this time, if necessary, a protective colloid component may be contained in the alkali halide aqueous solution. Further, if necessary, a protective colloid solution, a silver salt solution, and an alkali halide aqueous solution are added to a mixer disclosed in JP-A-2-44335, and immediately transferred to a reaction vessel, thereby transferring tabular grains. Nucleation can also be performed. Further, as disclosed in US Pat. No. 5,104,786, nucleation can be performed by passing an aqueous solution containing an alkali halide and a protective colloid solution through a pipe and adding an aqueous silver salt solution thereto.
[0040]
Gelatin is used as the protective colloid, but natural polymers and synthetic polymers other than gelatin can be used as well. The types of gelatin include alkali-treated gelatin, oxidized gelatin obtained by oxidizing methionine groups in gelatin molecules with hydrogen peroxide or the like (methionine content 40 μmol / g or less), amino group-modified gelatin (for example, phthalated gelatin, trimellit Gelatinized gelatin, succinylated gelatin, maleated gelatin, esterified gelatin), and low molecular weight gelatin (mass average molecular weight: 3000 to 40,000). Japanese Patent Publication No. 5-12696 can be referred to for the oxidized gelatin, and Japanese Patent Publications Nos. 8-82883 and 11-143002 can be referred to for the amino group-modified gelatin. Moreover, you may use the lime processing bone gelatin which contains 30% or more of components of molecular weight 280,000 or more in the molecular weight distribution measured by the paggy method described in Unexamined-Japanese-Patent No. 11-237704 as needed. Further, for example, starches described in European Patent No. 758758 and US Pat. No. 5,733,718 may be used. In addition, natural polymers are disclosed in Japanese Patent Publication No. 7-11550, Research Disclosure Magazine Vol. 17643 (December 1978).
[0041]
In nucleation, it is usually preferred that an excess of halogen ions is present before and / or during nucleation. The excess halogen ions in this case are Cl⁻, Br⁻, I⁻These may be used alone or in combination. In the present invention, Br⁻Or Cl⁻Is preferably present. The total halogen ion concentration is preferably 3 × 10^-5mol / liter to 0.1 mol / liter, more preferably 3 × 10^-4mol / liter or more and 0.01 mol / liter or less.
The halogen ion in the halide solution added at the time of nucleation is Br.⁻, Cl⁻, I⁻These may be used alone or in combination. In the present invention, Br⁻, Cl⁻In this case, the silver chloride content in the silver halide nuclei after nucleation is preferably 0 mol% or more and 100 mol% or less, and more preferably 5 mol% or more and 80 mol% or less.
[0042]
The protective colloid may be dissolved in an aqueous alkali halide solution added at the time of nucleation.
[0043]
The temperature during nucleation is preferably from 5 to 60 ° C., but more preferably from 5 to 48 ° C. when fine tabular grains having a sphere equivalent diameter of 0.5 μm or less are produced.
[0044]
The pH of the dispersion medium is preferably 4 or more and 8 or less when amino group-modified gelatin is used, but preferably 2 or more and 8 or less when other gelatin is used.
[0045]
2. Aging process
1. In the nucleation, fine particles other than tabular grains (especially octahedral and single twin grains) are formed. Before entering the growth process described below, it is necessary to eliminate grains other than tabular grains to obtain nuclei having a shape to be tabular grains and having good monodispersity. In order to make this possible, it is well known to perform Ostwald ripening following nucleation.
[0046]
Immediately after nucleation, pBr is adjusted, and then the temperature is increased and ripening is performed until the hexagonal tabular grain ratio reaches the maximum. The protective colloid aqueous solution may be added once or more after the nucleation until the ripening is completed. In this case, the concentration of the protective colloid with respect to the dispersion medium solution is preferably 10% by mass or less. As the additional protective colloid used at this time, the above-mentioned alkali-treated gelatin, amino group-modified gelatin, oxidized gelatin, low molecular weight gelatin, natural polymer, or synthetic polymer may be used. Moreover, you may use the lime processing bone gelatin which contains 30% or more of components of molecular weight 280,000 or more in the molecular weight distribution measured by the paggy method described in Unexamined-Japanese-Patent No. 11-237704 as needed. Further, for example, starches described in European Patent No. 758758 and US Pat. No. 5,733,718 may be used.
[0047]
The aging temperature is preferably 40 to 80 ° C, more preferably 50 to 80 ° C, and pBr is 1.2 to 3.0. The pH is preferably 4 or more and 8 or less when amino group-modified gelatin is present, but is preferably 2 or more and 8 or less for other gelatins.
[0048]
At this time, a silver halide solvent may be added so that grains other than the tabular grains disappear quickly. In this case, the concentration of the silver halide solvent is preferably 0.3 mol / liter or less, and more preferably 0.2 mol / liter or less.
[0049]
It is preferable to ripen in this way so that only substantially 100% tabular grains are obtained.
[0050]
After the ripening, if the silver halide solvent is unnecessary in the next growth process, the silver halide solvent may be removed as follows.
[0051]
(I) NH₃In the case of alkaline silver halide solvents such as₃Ag like⁺It is invalidated by adding an acid with a high solubility product.
(Ii) In the case of a thioether-based silver halide solvent, as described in JP-A-60-136736, H₂O₂It is invalidated by adding an oxidizing agent such as.
[0052]
In the method for producing an emulsion of the present invention, the end of the ripening step is a grain other than tabular grains having a hexagonal or triangular main plane and having at least two twin planes (regular and single twin grains). ) Refers to the time when it disappears. The disappearance of particles other than tabular grains whose main plane is hexagonal or triangular and has at least two twin planes can be confirmed by observing a TEM image of a replica of the grains.
[0053]
In the ripening step, an over-ripening step described in JP-A-11-174606 may be provided as necessary. The over-ripening step is a step of erasing tabular grains having a slow anisotropic growth speed by further aging the tabular grains themselves after ripening (ripening step) until the hexagonal tabular grain ratio reaches the maximum. . When the number of tabular grains obtained in the aging step is 100, it is preferable to reduce the number of tabular grains to 90 or less, more preferably 60 or more and 80 or less by the over-ripening step. .
[0054]
In the method for producing an emulsion of the present invention, conditions such as pBr and temperature in the overripening step can be set to be the same as those in the ripening step. In the overripening step, a silver halide solvent can be added in the same manner as in the ripening step, and the type, concentration, etc. can be set to be the same as those in the ripening step.
[0055]
3. Growth process
The pBr during the crystal growth period following the aging step is preferably maintained at 1.4 to 3.5. When the concentration of the protective colloid in the dispersion medium solution before entering the growth process is low (1% by mass or less), the protective colloid may be additionally added. In addition, protective colloids may be added during the growth process. The timing of additional addition may be any time during the growth process. The protective colloid concentration in the dispersion medium solution is preferably 1 to 10% by mass. As the protective colloid used at this time, the above-mentioned alkali-treated gelatin, amino group-modified gelatin, oxidized gelatin, natural polymer, or synthetic polymer may be used. Moreover, you may use the lime processing bone gelatin which contains 30% or more of components of molecular weight 280,000 or more in the molecular weight distribution measured by the paggy method described in Unexamined-Japanese-Patent No. 11-237704 as needed. Further, for example, starches described in European Patent No. 758758 and US Pat. No. 5,733,718 may be used. The pH during growth is preferably 4 to 8 or less when amino group-modified gelatin is present, and 2 to 8 is preferable otherwise. Ag during crystal growth⁺The halogen ion addition rate is preferably 20 to 100%, preferably 30 to 100% of the crystal critical growth rate. In this case, the addition rate of silver ions and halogen ions is increased as the crystal grows. In this case, as described in Japanese Patent Publication Nos. 48-36890 and 52-16364, the aqueous solution of silver salt and halogen salt aqueous solution is used. The addition rate may be increased and the concentration of the aqueous solution may be increased.
[0056]
When performing the double jet method in which an aqueous silver salt solution and an aqueous halogen salt solution are added simultaneously, in order to prevent the introduction of growth dislocation due to non-uniform silver iodide content, the reaction vessel should be stirred well and the concentration of the added solution should be reduced. It is preferred to dilute.
[0057]
A method of adding silver iodide fine particles prepared outside the reaction vessel simultaneously with the addition of the silver salt aqueous solution and the halogen salt aqueous solution is more preferable, and it is preferable that at least 50% or more of the total silver amount is grown by this method. At this time, the growth temperature is preferably 50 ° C. or higher and 90 ° C. or lower, and more preferably 60 ° C. or higher and 85 ° C. or lower. The silver iodide fine particles to be added may be prepared in advance or may be added while continuously preparing. JP-A-10-43570 can be referred to for the preparation method in this case.
[0058]
The average size of the silver iodide fine particles to be added is preferably 0.01 μm or more and 0.1 μm or less, more preferably 0.02 μm or more and 0.08 μm or less. The silver iodide composition of the tabular grains can be changed depending on the amount of silver iodide emulsion to be added. Here, the size and size distribution of the silver iodide fine grain emulsion are obtained by placing the silver iodide fine grains on a mesh for observation with an electron microscope and directly observing them by a transmission method instead of the carbon replica method. This is because the measurement error becomes large in the observation by the carbon replica method because the particle size is small. The size of the fine particles is defined as the diameter of a circle having the same projected area as the observed particles (projected area diameter). The size distribution of the fine particles is also obtained by using this equal projected area diameter. The silver iodide fine particles most effective in the present invention have a grain size of 0.06 μm or less and 0.02 μm or more, and a grain size distribution variation coefficient of 18% or less.
[0059]
Further, silver iodobromide fine particles may be added in place of the addition of the silver salt aqueous solution and the halogen salt aqueous solution. At this time, tabular grains having a desired silver iodide content can be obtained by making the silver iodide content of the fine grains equal to the silver iodide content of the desired tabular grains. The silver iodobromide fine particles may be prepared in advance, but it is preferable to add them while preparing them continuously. The size of the silver iodobromide fine particles to be added is preferably 0.005 μm or more and 0.05 μm or less, more preferably 0.01 μm or more and 0.03 μm or less. The temperature during growth is preferably 60 ° C. or higher and 90 ° C. or lower, more preferably 70 ° C. or higher and 85 ° C. or lower.
[0060]
Further, the above ion addition method, silver iodide fine particle addition method, and silver iodobromide fine particle addition method may be combined.
[0061]
In the present invention, the tabular grains preferably have dislocation lines, but the base grains preferably do not have dislocation lines in order to reduce pressure desensitization. The dislocation lines of tabular grains are described, for example, in J. Org. F. Hamilton, Phot. Sci. Eng. , 11, 57 (1967), T .; Shiozawa, J. et al. Soc. Photo. Sci. It can be observed by a direct method using a transmission electron microscope at a low temperature described in Japan, 35, 213 (1972). In other words, the silver halide grains taken out carefully so as not to apply a pressure that causes dislocation lines to the grains from the emulsion are placed on a mesh for electron microscope observation to prevent damage (printout, etc.) due to electron beams. Observation is performed by a transmission method in a state where the tube is cooled. At this time, the thicker the particle, the more difficult it is to transmit the electron beam. Therefore, the observation using the high-voltage electron microscope (acceleration voltage of 200 kV or more for a particle having a thickness of 0.25 μm) should be observed more clearly. Can do. From the photograph of the particles obtained by such a method, the position and the number of dislocation lines for each particle when viewed from the direction perpendicular to the main plane can be obtained.
[0062]
Next, step (b) will be described.
First, the (b1) dislocation introduction step will be described. The step (b1) includes a first shell step and a second shell step. Here, for ease of explanation, the substrate particles are considered to be the same as the core portion, and the shell portions provided after that are referred to as the first shell and the second shell. A first shell is provided on the aforementioned base particle. The ratio of the first shell is preferably 1% or more and 10% or less with respect to the total silver amount, and the average silver iodide content thereof is 20 mol% or more and 100 mol% or less. More preferably, the ratio of the first shell is 1% or more and 5% or less with respect to the total silver amount, and the average silver iodide content is 25 mol% or more and 100 mol% or less. For the growth of the first shell on the base grains, an aqueous silver nitrate solution and an aqueous halogen solution containing iodide and bromide are basically added by the double jet method. Alternatively, an aqueous silver nitrate solution and an aqueous halogen solution containing iodide are added by the double jet method. Alternatively, an aqueous halogen solution containing iodide is added by the single jet method.
[0063]
Any of the above methods may be used, or a combination thereof may be used. As is apparent from the average silver iodide content of the first shell, silver iodide can be precipitated in addition to the silver iodobromide mixed crystal when the first shell is formed. In either case, normally, silver iodide disappears and all changes to a silver iodobromide mixed crystal when the next second shell is formed.
[0064]
As a preferred method for forming the first shell, there is a method in which a silver iodobromide or silver iodide fine grain emulsion is added, ripened and dissolved. Further, as a preferred method, there is a method of adding a silver iodide fine grain emulsion and then adding a silver nitrate aqueous solution or a silver nitrate aqueous solution and a halogen aqueous solution. In this case, dissolution of the silver iodide fine grain emulsion is promoted by the addition of an aqueous silver nitrate solution. The silver content of the added silver iodide fine grain emulsion is used as the first shell, and the silver iodide content is 100 mol%. . Then, the added silver nitrate aqueous solution is calculated as the second shell.
[0065]
The addition amount of the silver iodide fine grain emulsion is preferably 1 mol% or more and 10 mol% or less in terms of silver relative to the tabular grain emulsion. Most preferably, it is 2 mol% or more and 7 mol% or less. By selecting this addition amount, dislocation lines are preferably introduced, and the effect of the invention becomes remarkable. The temperature of the system at the time of addition is preferably 40 ° C. or higher and 90 ° C. or lower, and particularly preferably 50 ° C. or higher and 80 ° C. or lower. The silver iodide fine grain emulsion is usually dissolved before being added, but it is necessary to sufficiently increase the stirring efficiency of the system at the time of addition. Preferably, the stirring rotation speed is set higher than usual. The addition of an antifoaming agent is effective to prevent the generation of bubbles during stirring. Specifically, antifoaming agents described in Examples of US Pat. No. 5,275,929 are used.
[0066]
The fine grains contained in the silver iodide fine grain emulsion may be substantially silver iodide, and may contain silver bromide and / or silver chloride as long as they can form mixed crystals. 100% silver iodide is preferred. Silver iodide may preferably have β-form, γ-form and α-form or α-form-like structure as described in US Pat. No. 4,672,026 in its crystal structure. In the present invention, the crystal structure is not particularly limited, but a mixture of β-form and γ-form, more preferably β-form is used. The silver iodide fine grain emulsion described in U.S. Pat. No. 5,004,679 may be formed immediately before addition, or may be any one that has undergone a normal water washing step. Preferably, those subjected to a normal water washing step are used. The silver iodide fine grain emulsion can be easily formed by the method described in US Pat. No. 4,672,026. A double jet addition method of a silver salt aqueous solution and an iodide salt aqueous solution, in which the pI value at the time of grain formation is kept constant, is preferred. Where pI is the I of the system⁻It is the logarithm of the reciprocal of the ion concentration. The type, concentration, presence / absence of silver halide solvent, type, concentration, etc. of the protective colloid agent such as temperature, pI, pH, and gelatin are not particularly limited, but the size of the fine particles is preferably 0.1 μm or less, more preferably 0. 0.07 μm or less is convenient for the present invention. Although it is a fine particle, the particle shape cannot be completely specified, but the variation coefficient of the distribution of the equivalent particle size sphere diameter is preferably 25% or less. In particular, when it is 20% or less, the effect of the present invention is remarkable. Here, the size and size distribution of the silver iodide fine grain emulsion are obtained by placing the silver iodide fine grains on a mesh for observation with an electron microscope and directly observing them by a transmission method instead of the carbon replica method. This is because the measurement error becomes large in the observation by the carbon replica method because the particle size is small. The size of the fine particles is defined as the diameter of a circle having the same projected area as the observed particles (projected area diameter). The size distribution of the fine particles is also obtained by using this equal projected area diameter. The silver iodide fine particles most effective in the present invention have a grain size of 0.06 μm or less and 0.02 μm or more, and a grain size distribution variation coefficient of 18% or less.
[0067]
The silver iodide fine grain emulsion is preferably prepared by the usual water washing described in U.S. Pat. No. 2,614,929 and the like, and adjustment of the concentration of protective colloidal agents such as pH, pI, gelatin and the like after the above grain formation. The silver concentration is adjusted. The pH is preferably 5 or more and 7 or less. The pI value is preferably set to a pI value at which the solubility of silver iodide is minimized or a pI value higher than that value. As the protective colloid agent, ordinary gelatin having an average molecular weight of about 100,000 is preferably used. Low molecular weight gelatin having an average molecular weight of 20,000 or less is also preferably used. In some cases, it is convenient to use a mixture of gelatins having different molecular weights. The amount of gelatin per kg of emulsion is preferably 10 g or more and 100 g or less. More preferably, it is 20 g or more and 80 g or less. The silver amount in terms of silver atom per kg of the emulsion is preferably 10 g or more and 100 g or less. More preferably, it is 20 g or more and 80 g or less. The amount of gelatin and / or silver is preferably selected to be a value suitable for rapidly adding a silver iodide fine grain emulsion.
[0068]
As a more preferable method for forming the first shell, an iodide ion releasing agent described in US Pat. No. 5,496,694 instead of the conventional iodide ion supply method (method of adding free iodide ions) Can be used to form a silver halide phase containing silver iodide while rapidly generating iodide ions.
[0069]
The iodide ion releasing agent releases iodide ions by reaction with an iodide ion release regulator (base and / or nucleophile). Preferred examples of the nucleophilic reagent used in this case include the following chemical species. It is done. For example, hydroxide ion, sulfite ion, hydroxylamine, thiosulfate ion, metabisulfite ion, hydroxamic acids, oximes, dihydroxybenzenes, mercaptans, sulfinate, carboxylate, ammonia, amines, Examples include alcohols, ureas, thioureas, phenols, hydrazines, hydrazides, semicarbazides, phosphines, and sulfides.
[0070]
The release rate and timing of iodide ions can be controlled by controlling the concentration of the base and the nucleophilic reagent, the addition method, and the temperature of the reaction solution. The base is preferably an alkali hydroxide.
[0071]
The preferred concentration range of the iodide ion release agent and the iodide ion release modifier used to rapidly generate iodide ions is 1 × 10.^-7~ 20M, more preferably 1x10^-5-10M, more preferably 1x10^-4~ 5M, particularly preferably 1x10^-3~ 2M.
[0072]
When the concentration exceeds 20M, the amount of the iodide ion releasing agent having a large molecular weight and the amount of the iodide ion releasing agent added is excessively large with respect to the capacity of the particle forming container.
[0073]
1 × 10^-7If it is less than M, the iodide ion releasing reaction rate is slow, and it is difficult to rapidly produce an iodide ion releasing agent, such being undesirable.
[0074]
The temperature range of a preferable reaction liquid is 30-80 degreeC, More preferably, it is 30-75 degreeC, Most preferably, it is 30-60 degreeC.
[0075]
When the temperature is higher than 80 ° C., the iodide ion release reaction rate is generally extremely high, and when the temperature is lower than 30 ° C., the iodide ion release reaction rate is generally extremely low.
[0076]
When a base is used in releasing iodide ions, a change in solution pH may be used. At this time, the pH range preferable for controlling the release rate and timing of iodide ions is 2 to 12, more preferably 3 to 11, particularly preferably 5 to 10, and most preferably adjusted pH is 7. .5 to 10.0. Even under neutral conditions at pH 7, hydroxide ions determined by the ionic product of water act as regulators.
[0077]
A nucleophile and a base may be used in combination, and at this time, the pH may be controlled within the above range to control the release rate and timing of iodide ions.
[0078]
When iodine atoms are released from the iodide ion releasing agent in the form of iodide ions, all iodine atoms may be released or a part of them may remain without being decomposed.
[0079]
A second shell is provided on the above-described base grain and the tabular grain having the first shell. The ratio of the second shell is preferably 10% or more and 40% or less with respect to the total silver amount, and the average silver iodide content thereof is 0 mol% or more and 5 mol% or less. More preferably, the ratio of the second shell is 15% or more and 30% or less with respect to the total silver amount, and the average silver iodide content thereof is 0 mol% or more and 3 mol% or less. The growth of the second shell on the tabular grains having the base grains and the first shell may be in the direction of increasing or decreasing the aspect ratio of the tabular grains. Basically, the second shell is grown by adding an aqueous silver nitrate solution and an aqueous halogen solution containing bromide by the double jet method. Alternatively, after adding an aqueous halogen solution containing bromide, an aqueous silver nitrate solution may be added by a single jet method. The system temperature, pH, type and concentration of protective colloid agent such as gelatin, presence or absence of silver halide solvent, type and concentration can vary widely. As for pBr, in the present invention, it is preferable that pBr at the end of formation of the layer is higher than pBr at the initial stage of formation of the layer. Preferably, the pBr at the initial stage of formation of the layer is 2.9 or less, and the pBr at the end of the formation of the layer is 1.7 or more. More preferably, the pBr at the initial stage of formation of the layer is 2.5 or less, and the pBr at the end of the formation of the layer is 1.9 or more. Most preferably, the pBr at the initial stage of formation of the layer is 2.3 or less and 1 or more. Most preferably, the pBr at the end of the layer is from 2.1 to 4.5.
[0080]
It is preferable that a dislocation line exists in the part of (b1) process. Dislocation lines are preferably present in the vicinity of the edge portion of the tabular grain. The vicinity of the edge part means the outer peripheral part (edge part) of the six sides of the tabular grain and the inner part thereof, that is, the part grown in the step (b1). The average number of dislocation lines present at the edge is preferably 10 or more per grain. More preferably, the average number is 20 or more per particle. When dislocation lines are densely present, or when dislocation lines are observed crossing each other, the number of dislocation lines per grain may not be clearly counted. However, even in these cases, it can be counted to the order of approximately 10, 20, or 30, and it can be clearly distinguished from the case where there are only a few. The average number of dislocation lines per particle is obtained as a number average by counting the number of dislocation lines for 100 grains or more.
[0081]
The tabular grains of the present invention desirably have a uniform dislocation dose distribution between grains. In the emulsion of the present invention, it is preferred that silver halide tabular grains having a major plane containing 10 or more dislocation lines per grain account for 100 to 50% of the projected area of all grains, more preferably 100 to 70. %, Particularly preferably 100 to 90%. If it is less than 50%, it is not preferable in terms of homogeneity between particles.
[0082]
In the present invention, when determining the ratio of dislocation lines and the number of dislocation lines, it is preferable to directly observe the dislocation lines for at least 100 particles, more preferably 200 particles or more, and particularly preferably 300 particles or more. Observe through observation.
[0083]
Next, the (b2) corner part dislocation limited introduction process will be described.
As a first aspect, a method of dissolving only the vicinity of the apex with iodide ions, as a second aspect, a method of simultaneously adding a silver salt solution and an iodide salt solution, as a third aspect, There is a method of substantially dissolving only the vicinity of the apex using a silver halide solvent, and a fourth embodiment is a method via halogen conversion.
[0084]
A method of dissolving with iodide ions, which is the first embodiment, will be described.
By adding iodide ions to the base particles, the vicinity of each apex of the base particles is dissolved and rounded. Subsequently, when a silver nitrate solution and a bromide solution, or a mixed solution of a silver nitrate solution, a bromide solution, and an iodide solution are added simultaneously, the grains further grow and dislocations are introduced near the apex. Regarding this method, reference can be made to the descriptions in JP-A-4-149541 and JP-A-9-189974.
[0085]
The total amount of iodide ions added in this embodiment is based on the value obtained by multiplying the total number of moles of iodide ions by the total number of moles of silver in the base grains multiplied by 100 as I2 (mol%). In order to obtain effective dissolution according to the present invention, it is preferable that (I2-I1) satisfy 0 to 8 with respect to the silver iodide content I1 (mol%) of the grain, and more preferably 0 to 4 It is.
[0086]
In this embodiment, the concentration of iodide ion added is preferably low, specifically, it is preferably 0.2 mol / liter or less, more preferably 0.1 mol / liter. Further, the pAg upon addition of iodide ions is preferably 8.0 or more, more preferably 8.5 or more.
[0087]
Following dissolution of the apex of the base particles by addition of iodide ions to the base particles, a silver nitrate solution is added alone, or a silver nitrate solution and bromide solution, or a mixed solution of silver nitrate solution, bromide solution and iodide solution is simultaneously added. Addition further grows the grains and introduces dislocations near the apex.
[0088]
A method of simultaneous addition of a silver salt solution and an iodide salt solution according to the second embodiment will be described. By rapidly adding a silver salt solution and an iodide salt solution to the base grains, silver iodide or silver halide having a high silver iodide content can be formed as an epitaxial part at the apex of the grains. At this time, the preferable addition time of the silver salt solution and the iodide salt solution is 0.2 to 0.5 minutes, and more preferably 0.5 to 2 minutes. This method is described in detail in JP-A-4-149541 and can be referred to.
[0089]
Following dissolution of the apex of the base particles by addition of iodide ions to the base particles, a silver nitrate solution is added alone, or a silver nitrate solution and bromide solution, or a mixed solution of silver nitrate solution, bromide solution and iodide solution is simultaneously added. Addition further grows the grains and introduces dislocations near the apex.
[0090]
A method using a silver halide solvent which is the third embodiment will be described.
After adding a silver halide solvent to the dispersion medium containing the base grains, and simultaneously adding a silver salt solution and an iodide salt solution, silver iodide or silver iodide is contained at the apex of the base grains dissolved by the silver halide solvent. High-rate silver halide will preferentially grow. At this time, the silver salt solution and the iodide salt solution do not need to be added rapidly. This method is described in detail in JP-A-4-149541, and can be referred to.
[0091]
Following dissolution of the apex of the base particles by addition of iodide ions to the base particles, a silver nitrate solution is added alone, or a silver nitrate solution and bromide solution, or a mixed solution of silver nitrate solution, bromide solution and iodide solution is simultaneously added. Addition further grows the grains and introduces dislocations near the apex.
[0092]
Next, a method through halogen conversion which is the fourth embodiment will be described.
By adding an epitaxial junction growth site support (hereinafter referred to as a site director), for example, a sensitizing dye described in JP-A-58-108526, or a water-soluble iodide, to the base particles, the apex portion of the base particles. In this method, silver chloride is converted into silver iodide or silver halide having a high silver iodide content by adding iodide ions after forming an epitaxial portion of silver chloride. The site director may be a sensitizing dye or a water-soluble thiocyanate ion, but is preferably a water-soluble iodide ion. The iodide ion used is 0.0005 to 1 mol%, preferably 0.001 to 0.5 mol%, based on the base particles. After the addition of iodide ions, the silver chloride epitaxial portion can be formed at the apex portion of the base grain by simultaneously adding the silver salt solution and the chloride salt solution.
[0093]
The halogen conversion by silver chloride iodide ions will be described. A silver halide having a high solubility is converted to a silver halide having a low solubility by adding a halogen ion capable of forming a silver halide having a low solubility. This process is called halogen conversion and is described, for example, in US Pat. No. 4,142,900. In this method, a silver iodide phase is formed at the apex of the base grain by selectively halogen-converting silver chloride having an epitaxial part grown at the apex of the base grain with iodide ions. Details are described in JP-A-4-149541.
[0094]
Following the halogen conversion of silver chloride with an epitaxial portion grown at the apex of the base grain to a silver iodide phase by addition of iodide ions, a silver nitrate solution alone, or a silver nitrate solution and bromide solution, or a silver nitrate solution A mixed solution of bromide solution and iodide solution is added simultaneously to further grow the grains and introduce dislocations near the apex.
[0095]
It is preferable that dislocation lines exist in the step (b2). Dislocation lines are preferably present in the vicinity of the corners of the tabular grains.
[0096]
Next, (b3) the epitaxial bonding step will be described.
Regarding the formation of an epitaxial portion of silver halide on a base grain, as described in US Pat. No. 4,435,501, iodide ion, aminoazaindene, or spectral sensitizing dye adsorbed on the base grain surface, etc. It is shown that the silver salt epitaxial part can be formed at a selected site, for example, the edge or corner of the base grain by the site director. JP-A-8-69069 discloses that a silver salt epitaxial part is formed at a selected portion of an ultrathin tabular grain base grain, and that the epitaxial part is optimally sensitized to achieve high sensitivity. .
[0097]
As the site director, aminoazaindene or spectral sensitizing dyes may be used, iodide ions or thiocyanate ions may be used, and they may be used properly or combined depending on the purpose.
[0098]
By changing the amount of sensitizing dye, iodide ion, and thiocyanate ion, the formation position of the silver salt epitaxial part may be limited to only the main plane part, the outer peripheral part, or the apex part of the base grain. Yes, and combinations of these are possible. The addition amount of aminoazaindene, iodide ion, thiocyanate ion, and spectral sensitizing dye used in the site director is appropriately selected according to the silver amount, surface area, and epitaxial portion formation position of the silver halide base grain to be used. It is preferable. The temperature for forming the silver salt epitaxial part is preferably 40 to 70 ° C, and more preferably 45 to 60 ° C. In this case, the pAg is preferably 9.0 or less, and more preferably 8.0 or less. Thus, by appropriately selecting the type of the site director, the amount added, and the deposition conditions (temperature, pAg, etc.) of the epitaxial junction, the epitaxial portion of the silver salt is formed on the main plane portion, outer peripheral portion, or apex portion of the base particle. It can be formed selectively. The emulsion thus obtained may be selectively sensitized by chemically sensitizing the epitaxial portion as disclosed in JP-A-8-69069. However, following the formation of the silver salt epitaxial portion, the silver salt solution and halogen A salt solution may be added simultaneously for further growth. The halogen salt aqueous solution added at this time is preferably a bromide salt solution or a mixed solution of a bromide salt solution and an iodide salt solution. Moreover, the temperature in this case is preferably 40 to 80 ° C, and more preferably 45 to 70 ° C. In this case, the pAg is preferably 5.5 or more and 9.5 or less, and more preferably 6.0 or more and 9.0 or less.
[0099]
Furthermore, the halogen conversion of the epitaxial part may be performed by adding a halogen solution having a halogen composition different from that of the epitaxial part. Formation of the epitaxial portion and subsequent growth, or halogen conversion, may be carried out subsequently after the formation of the silver halide base grain, or may be carried out after washing / redispersing once after the formation of the base grain, or before chemical sensitization. . The formation of the epitaxial portion and the subsequent growth or halogen conversion may be divided before and after the water washing / redispersion.
[0100]
(B3) Although dislocation lines may not be present in the step, it is more preferable that dislocation lines exist. The dislocation lines are preferably present at the junction between the base particle and the epitaxial portion or at the epitaxial portion, but the dislocation lines may be present at the outer peripheral portion or the apex portion. The average number of dislocation lines present is preferably 10 or more per grain. More preferably, the average number is 20 or more per particle. When dislocation lines are densely present, or when dislocation lines are observed crossing each other, the number of dislocation lines per grain may not be clearly counted. However, even in these cases, it can be counted to the order of approximately 10, 20, or 30, and it can be clearly distinguished from the case where there are only a few. The average number of dislocation lines per particle is obtained as a number average by counting the number of dislocation lines for 100 grains or more.
[0101]
As the protective colloid used in preparing the emulsion of the present invention, it is advantageous to use the gelatin described above, but other hydrophilic colloids can also be used.
[0102]
For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose and cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives Various synthetic hydrophilic polymers such as polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinyl pyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, polyvinylpyrazole, or a single or copolymer Substances can be used.
[0103]
The emulsion of the present invention is preferably washed with water for desalting and dispersed in a newly prepared protective colloid. Gelatin is used as the protective colloid, but natural polymers and synthetic polymers other than gelatin can be used as well. The types of gelatin include alkali-treated gelatin, oxidized gelatin obtained by oxidizing methionine groups in gelatin molecules with hydrogen peroxide or the like (methionine content 40 μmol / g or less), amino group-modified gelatin (for example, phthalated gelatin, trimellit Gelatinized gelatin, succinated gelatin, maleated gelatin, esterified gelatin) may be used. Moreover, you may use the lime processing bone gelatin which contains 30% or more of components of molecular weight 280,000 or more in the molecular weight distribution measured by the paggy method described in Unexamined-Japanese-Patent No. 11-237704 as needed. Further, for example, starches described in European Patent No. 758758 and US Pat. No. 5,733,718 may be used. In addition, natural polymers are disclosed in Japanese Patent Publication No. 7-11550, Research Disclosure Vol. 17643 (December 1978). The temperature for washing with water can be selected according to the purpose, but is preferably selected within the range of 5 ° C to 50 ° C. Although pH at the time of water washing can also be chosen according to the objective, it is preferred to choose between 2-10. More preferably, it is the range of 3-8. Although pAg at the time of water washing can also be selected according to the objective, it is preferable to select between 5-10. The washing method can be selected from a noodle washing method, a dialysis method using a semipermeable membrane, a centrifugal separation method, a coagulation sedimentation method, an ion exchange method, and an ultrafiltration method. In the case of the coagulation sedimentation method, a method using a sulfate, a method using an organic solvent, a method using a water-soluble polymer, a method using a gelatin derivative and the like can be selected.
[0104]
In the formation of the particles of the present invention, for example, JP-A-5-173268, JP-A-5-173269, JP-A-5-173270, JP-A-5-173271, JP-A-6-202258, and JP-A-7-175147. The described polyalkylene oxide block copolymers or the polyalkylene oxide copolymers described, for example, in US Pat. No. 3,089,578 may be present. The time when the compound is present may be any time during the preparation of the particles, but the effect is great when used at an early stage of particle formation.
[0105]
In preparation of the emulsion of the present invention, for example, at the time of grain formation, desalting step, chemical sensitization, or before coating, it is preferable to have a metal ion salt present before coating. When the particles are doped, it is preferably added after the formation of the particles, before the completion of the chemical sensitization after the formation of the particles when used as a particle sensitizer or a chemical sensitizer. A method of doping the entire particle and a method of doping only the core portion or the shell portion of the particle can also be selected. For example, Mg, Ca, Sr, Ba, Al, Sc, Y, La, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ru, Rh, Pd, Re, Os, Ir, Pt, Au, Cd, Hg, Tl, In, Sn, Pb, and Bi can be used. These metals can be added in the form of a salt that can be dissolved during particle formation, such as ammonium salt, acetate salt, nitrate salt, sulfate salt, phosphate salt, hydrate salt, hexacoordinated complex salt, and tetracoordinated complex salt. For example, CdBr₂, CdCl₂, Cd (NO₃)₂, Pb (NO₃)₆, Pb (CH₃COO)₂, K₄[Fe (CN)₆], (NH₄)₄[Fe (CN)₆], K₂IrCl₆, (NH₄)₃RhCl₆, K₄Ru (CN)₆Can be given. The ligand of the coordination compound can be selected from halo, aqua, cyano, cyanate, thiocyanate, nitrosyl, thionitrosyl, oxo and carbonyl. These may use only one type of metal compound, but may be used in combination of two or more.
[0106]
The metal compound is preferably added after being dissolved in water or a suitable organic solvent such as methanol or acetone. In order to stabilize the solution, a method of adding an aqueous hydrogen halide solution (for example, HCl, HBr) or an alkali halide (for example, KCl, NaCl, KBr, NaBr) can be used. Moreover, you may add an acid, an alkali, etc. as needed. The metal compound can be added to the reaction vessel before the particle formation or can be added during the particle formation. In addition, water-soluble silver salt (for example, AgNO₃) Or an aqueous alkali halide solution (for example, NaCl, KBr, KI) and can be added continuously during the formation of silver halide grains. Further, a solution independent of the water-soluble silver salt and alkali halide may be prepared and added continuously at an appropriate time during grain formation. It is also preferable to combine various addition methods.
[0107]
It may be useful to add a chalcogen compound during preparation of an emulsion as described in US Pat. No. 3,772,031. In addition to S, Se, and Te, cyanate, thiocyanate, selenocyanic acid, carbonate, phosphate, and acetate may be present.
[0108]
The silver halide grains of the present invention have a chalcogen sensitization such as sulfur sensitization, selenium sensitization or tellurium sensitization; noble metal sensitization such as gold sensitization or palladium sensitization; at least one of reduction sensitization is a silver halide photograph. It can be applied in any step of the emulsion production process. It is preferable to combine two or more sensitization methods. Various types of emulsions can be prepared depending on the step of chemical sensitization. There are types that embed chemical sensitization nuclei inside the particles, types that embed in a shallow position from the particle surface, or types that make chemical sensitization nuclei on the surface. In the emulsion of the present invention, the location of chemical sensitization nuclei can be selected according to the purpose, but generally preferred is the case where at least one chemical sensitization nucleus is formed in the vicinity of the surface.
[0109]
One chemical sensitization that can be preferably carried out in the present invention is chalcogen sensitization and noble metal sensitization, either alone or in combination, by TH James, The Photographic Process, 4th Edition, Macmillan. 1977, (TH James, The Theory of the Photographic Process, 4th ed, Macmillan, 1977), pages 67-76, and can also be performed using active gelatin. Disclosure, 120, April 1974, 12008; Research Disclosure, Volume 34, June 1975, 13452, U.S. Pat. Nos. 2,642,361, 3,297,446, 3, 772,031, 3,857,711, 3,9 1,714, 4,266,018, and 3,904,415, and British Patent 1,315,755, pAg 5-10, pH 5 At ˜8 and at temperatures of 30-80 ° C., sulfur, selenium, tellurium, gold, platinum, palladium, iridium or combinations of these sensitizers. In the noble metal sensitization, noble metal salts such as gold, platinum, palladium, iridium and the like can be used, and gold sensitization, palladium sensitization and the combined use of both are particularly preferable.
[0110]
In gold sensitization, P.I. Gold salts described in Grafkides, Chimie et Physique Photographic (published by Paul Momtel, 1987, 5th edition), Research Disclosure 307, 307105, and the like can be used.
[0111]
Specifically, in addition to chloroauric acid, potassium chloroaurate, and potassium aurithiocyanate, US Pat. Nos. 2,642,361 (gold sulfide, gold selenide, etc.), 35035049 (thiolate having a water-soluble group) Gold), 5049484 (bis (methylhydantoinato) gold complex, etc.), 5049485 (mesoionic thiolate gold complex such as 1,4,5-trimethyl-1,2,4- Triazolium-3-thiolate gold complex, etc.), macrocyclic heterocyclic gold complexes of 5252455 and 5391727, 5620841, 5700631, 5759760, 5759761, 5912111, Nos. 5912112 and 5939245, JP-A-1-14753 Nos. 8-69074, 8-69075, 9-269554, JP-B 45-29274, German published applications DD-264524A, 264525A, 265474A, 298321A, JP-A-11 The gold compounds described in JP-A Nos. 207959, 11-209825, 11-257428, and 11-302918 can also be used.
[0112]
The palladium compound means a palladium divalent salt or a tetravalent salt. Preferred palladium compounds are R₂PdX₆Or R₂PdX₄It is represented by Here, R represents a hydrogen atom, an alkali metal atom or an ammonium group. X represents a halogen atom and represents a chlorine, bromine or iodine atom.
[0113]
Specifically, K₂PdCl₄, (NH₄)₆PdCl₆, Na₂PdCl₄, (NH₄)₆PdCl₄, Li₂PdCl₄, Na₂PdCl₆Or K₂PdBr₄Is preferred. Gold compounds and palladium compounds are preferably used in combination with thiocyanate or selenocyanate.
[0114]
In sulfur sensitization, unstable sulfur compounds are used. The unstable sulfur compounds described in Grafkides, Chimie et Physique Photographic (published by Paul Momtel, 1987, 5th edition), Research Disclosure 307, 307105, and the like can be used.
[0115]
Specifically, thiosulfate (for example, hypo), thioureas (for example, diphenylthiourea, triethylthiourea, N-ethyl-N ′-(4-methyl-2-thiazolyl) thiourea, dicarboxymethyl- Dimethylthiourea, carboxymethyl-trimethylthiourea), thioamides (eg, thioacetamide), rhodanines (eg, diethylrhodanine, 5-benzylidene-N-ethylrhodanine), phosphine sulfides (eg, trimethylphosphine) Sulfide), thiohydantoins, 4-oxo-oxazolidine-2-thiones, disulfides or polysulfides (eg, dimorpholine disulfide, cystine, hexathiocanthion), mercapto compounds (eg, cysteine), polythionate , Elemental Such known sulfur compounds and active gelatin, such as yellow may also be used. Particularly preferred are thiosulfates, thioureas, phosphine sulfides and rhodanines.
[0116]
In selenium sensitization, unstable selenium compounds are used, and Japanese Patent Publication Nos. 43-13489, 44-15748, JP-A-4-25832, 4-109340, 4-271341, and 5-40324. No. 5-11385, Japanese Patent Application No. Hei 4-202415, No. 4-330495, No. 4-333030, No. 5-4203, No. 5-4204, No. 5-106977, No. 5-236538. Selenium compounds described in JP-A-5-241642 and JP-A-5-286916 can be used.
[0117]
Specifically, colloidal metal selenium, selenoureas (for example, N, N-dimethylselenourea, trifluoromethylcarbonyl-trimethylselenourea, acetyl-trimethylselenourea), selenoamides (for example, selenoamide, N, N -Diethylphenylselenamide), phosphine selenides (eg triphenylphosphine selenide, pentafluorophenyl-triphenylphosphine selenide), selenophosphates (eg tri-p-tolylselenophosphate, Tri-n-butylselenophosphate), selenoketones (for example, selenobenzophenone), isoselenocyanates, selenocarboxylic acids, selenoesters (for example, methoxyphenylselenocarboxy-2,2-dimethoxycyclohexa) Ester), or the like may be used diacylselenides. Furthermore, non-labile selenium compounds described in JP-B Nos. 46-4553 and 52-34492, such as selenious acid, selenocyanic acids (for example, potassium selenocyanate), selenazoles, selenides, etc. Can be used. In particular, phosphine selenides, selenoureas, selenoesters and selenocyanic acids are preferred.
[0118]
In tellurium sensitization, an unstable tellurium compound is used, and JP-A-4-224595, JP-A-4-271341, JP-A-4-3333043, JP-A-5-303157, JP-A-4-185004, and JP-A-4-330495. No. 4-333030, No. 5-4203, No. 5-4204, No. 5-106977, No. 5-286916, etc. can be used.
[0119]
Specifically, phosphine tellurides (for example, butyl-diisopropylphosphine telluride, tributylphosphine telluride, tributoxyphosphine telluride, ethoxydiphenylphosphine telluride), diacyl (di) tellurides ( For example, bis (diphenylcarbamoyl) ditelluride, bis (N-phenyl-N-methylcarbamoyl) ditelluride, bis (N-phenyl-N-methylcarbamoyl) telluride, bis (N-phenyl-N-benzylcarbamoyl) telluride, bis ( Ethoxycarbonyl) telluride), telluroureas (for example, N, N′-dimethylethylenetellurourea, N, N′-diphenylethylenetellurourea) telluramides, telluroesters, etc. may be used.
[0120]
Useful chemical sensitization aids include compounds known to suppress fog and increase sensitivity during the process of chemical sensitization, such as azaindene, azapyridazine, and azapyrimidine. Examples of chemical sensitization aid modifiers are disclosed in U.S. Pat. Nos. 2,131,038, 3,411,914, and 3,554,757, and JP-A-58-126526. And the above-mentioned “Photo Emulsion Chemistry” by Duffin, pages 138 to 143.
[0121]
The amount of the gold sensitizer or chalcogen sensitizer used in the present invention varies depending on the silver halide grains used, chemical sensitization conditions, etc., but it is 10 per mole of silver halide.^-8-10^-2Moles, preferably 10^-7-10^-3It is about a mole.
[0122]
It is preferred to subject the silver halide photographic emulsion of the present invention to reduction sensitization during grain formation, after grain formation and before chemical sensitization, during chemical sensitization, or after chemical sensitization.
[0123]
Here, the reduction sensitization is called a method of adding a reduction sensitizer to a silver halide photographic emulsion, a method of growing or ripening in a low pAg atmosphere called silver ripening having a pAg of 1 to 7, and a method of high pH ripening. Any method of growing or aging in a high pH atmosphere of pH 8-11 can be selected. Two or more methods can be used in combination.
[0124]
The method of adding a reduction sensitizer is a preferable method in that the level of reduction sensitization can be finely adjusted.
[0125]
As reduction sensitizers, for example, stannous salts, ascorbic acid and derivatives thereof, amines and polyamines, hydrazine derivatives, formamidine sulfinic acid, silane compounds, and borane compounds are known. In the reduction sensitization of the present invention, these known reduction sensitizers can be selected and used, and two or more compounds can be used in combination. As a reduction sensitizer, stannous chloride, thiourea dioxide, dimethylamine borane, ascorbic acid and derivatives thereof are preferable compounds. Since the addition amount of the reduction sensitizer depends on the emulsion production conditions, it is necessary to select the addition amount, but it is 10 per mol of silver halide.^-7-10^-3A molar range is suitable.
[0126]
The reduction sensitizer is dissolved in water or an organic solvent such as alcohols, glycols, ketones, esters and amides and added during particle growth. Although it may be added to the reaction vessel in advance, a method of adding it at an appropriate time of particle growth is preferred. Alternatively, a reduction sensitizer may be added in advance to the water solubility of the water-soluble silver salt or water-soluble alkali halide, and silver halide grains may be precipitated using these aqueous solutions. It is also preferable to add the reduction sensitizer solution several times as the particle grows, or to add it continuously for a long time.
[0127]
It is preferable to use an oxidizing agent for silver during the production process of the emulsion of the present invention. The oxidizing agent for silver refers to a compound having an action of acting on metallic silver and converting it into silver ions. Particularly effective are compounds capable of converting extremely fine silver grains by-produced in the process of forming silver halide grains and chemical sensitization into silver ions. The silver ions generated here may form, for example, a silver salt that is hardly soluble in water such as silver halide, silver sulfide, or silver selenide, or a silver salt that is easily soluble in water such as silver nitrate. May be formed. The oxidizing agent for silver may be an inorganic substance or an organic substance. Examples of the inorganic oxidizing agent include ozone, hydrogen peroxide and adducts thereof (for example, NaBO).₂・ H₂O₂・ 3H₂O, 2NaCO₃・ 3H₂O₂, Na₄P₂O₇・ 2H₂O₂2Na₂SO₄・ H₂O₂・ 2H₂O), peroxyacid salts (eg K₂S₂O₈, K₂C₂O₆, K₂P₂O₈), Peroxy complex compounds (for example, K₂[Ti (O₂) C₂O₄] 3H₂O, 4K₂SO₄・ Ti (O₂) OH / SO₄・ 2H₂O, Na₃[VO (O₂) (C₂H₄)₆] 6H₂O), permanganate (eg KMnO)₄), Chromate (eg, K₂Cr₂O₇) Oxygenates, halogen elements such as iodine and bromine, perhalogenates (eg potassium periodate), high valent metal salts (eg potassium hexacyanoferrate) and thiosulfone There is an acid salt.
[0128]
Examples of organic oxidizing agents include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogens (for example, N-bromosuccinimide, chloramine T, An example is chloramine B).
[0129]
Preferred oxidizing agents in the present invention are ozone, hydrogen peroxide and its adducts, halogen elements, inorganic oxidizers of thiosulfonates, and organic oxidizers of quinones. It is a preferred embodiment to use the aforementioned reduction sensitization in combination with an oxidizing agent for silver. The method can be selected from a method of applying reduction sensitization after using an oxidizing agent, a reverse method thereof, or a method of simultaneously coexisting both. These methods can be selected and used in either the particle formation step or the chemical sensitization step.
[0130]
The photographic emulsion of the present invention may contain various compounds for the purpose of preventing fogging during the production process, storage or photographic processing of the light-sensitive material, or stabilizing the photographic performance. That is, thiazoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, amino Triazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines; , Triazaindenes, tetraazaindenes (especially 4-hydroxy substituted (1,3,3a, 7) chitraazaindenes), pentaazaindene Known as antifoggants or stabilizers, such as, it can be added to many compounds. For example, those described in US Pat. Nos. 3,954,474 and 3,982,947, and Japanese Patent Publication No. 52-28660 can be used. One preferred compound is the compound described in JP-A-63-212932. Antifoggants and stabilizers are used at various times before particle formation, during particle formation, after particle formation, water washing process, dispersion after water washing, chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. It can be added depending on the purpose. In addition to the original antifogging and stabilizing effect added during emulsion preparation, control the crystal wall of grains, reduce grain size, reduce grain solubility, control chemical sensitization, It can be used for various purposes such as controlling the arrangement of dyes.
[0131]
The photographic emulsion of the present invention is preferably spectrally sensitized with methine dyes or the like in order to exhibit the effects of the present invention. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of nuclei usually used for cyanine dyes as basic heterocyclic nuclei can be applied to these dyes. That is, for example, pyrroline nucleus, oxazoline nucleus, thiozoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and Nuclei in which aromatic hydrocarbon rings are fused to these nuclei, that is, for example, indolenine nucleus, benzoindolenine nucleus, indole nucleus, benzoxador nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole Nuclei, benzimidazole nuclei and quinoline nuclei are applicable. These nuclei may have a substituent on the carbon atom.
[0132]
The merocyanine dye or the complex merocyanine dye has, as a nucleus having a ketomethylene structure, for example, pyrazolin-5-one nucleus, thiohydantoin nucleus, 2-thiooxazolidine-2,4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine A 5- or 6-membered heterocyclic nucleus of a nucleus or a thiobarbituric acid nucleus can be applied.
[0133]
These sensitizing dyes may be used alone or in combination. The combination of sensitizing dyes is often used for the purpose of supersensitization. Typical examples thereof are U.S. Pat. Nos. 2,688,545, 2,977,229, 3,397,060, 3,522,052, 3,527,641, 3,617,293, 3,628,964, 3,666,480, 3,672,898, 3,679,428, 3,703 No. 3,377, No. 3,769,301, No. 3,814,609, No. 3,837,862, No. 4,026,707, British Patent No. 1,344 , 281 and 1,507,803, Japanese Patent Publication Nos. 43-4936, 53-12375, Japanese Patent Laid-Open Nos. 52-110618, and 52-109925. Yes.
[0134]
Along with the sensitizing dye, the emulsion itself may contain a dye having no spectral sensitizing action or a substance that does not substantially absorb visible light and exhibits supersensitization. The timing when the sensitizing dye is added to the emulsion may be at any stage of emulsion preparation that has been known to be useful so far. Most commonly, it is performed during the period after completion of chemical sensitization and before application, as described in US Pat. Nos. 3,628,969 and 4,225,666. Spectral sensitization can be performed simultaneously with chemical sensitization by adding at the same time as the chemical sensitizer, or can be performed prior to chemical sensitization as described in JP-A No. 58-113928. Spectral sensitization can be started by adding before the completion of silver halide grain precipitation. Furthermore, as taught in U.S. Pat. No. 4,225,666, these said compounds are added separately, i.e. some of these compounds are added prior to chemical sensitization and the remainder It can be added after chemical sensitization, and may be at any time during the formation of silver halide grains, including the method disclosed in US Pat. No. 4,183,756. The amount added is 4 x 10 per mole of silver halide.^-6~ 8x10^-3Can be used in moles.
[0135]
A fragmentable electron donating sensitizer may be used. Electron-donating sensitizers are disclosed in U.S. Pat. Nos. 5,747,235, 5,747,236, 6054260, 5994051, European Patents 7886692A1, 893332A1, JP 2000-181001, 2000. -180999, 2000-181002, 2000-181000, 2000-221626, 2000-221628. The fragmentable electron donating sensitizer may be used at any time during the production process of the photosensitive material. For example, at the time of particle formation, desalting step, chemical sensitization, and before coating. Moreover, it can also add in several steps in these processes. The compound of the present invention is preferably added after being dissolved in water, a water-soluble solvent such as methanol or ethanol, or a mixed solvent thereof. When the compound is dissolved in water, the compound having higher solubility when the pH is increased or decreased may be dissolved at a higher or lower pH and added. The fragmentable electron donating sensitizer is preferably used in the emulsion layer, but may be added to the protective layer or intermediate layer together with the emulsion layer and diffused during coating. The timing of addition of the compound of the present invention is preferably before or after the sensitizing dye, and preferably 1 × 10 5 per mole of silver halide.^-9~ 5x10^-2Mole, more preferably 1 × 10^-8~ 2x10^-3It is contained in the silver halide photographic emulsion layer in a molar ratio.
[0136]
When an electron donating sensitizer capable of fragmentation is used, it is preferable to use a preservability improving agent. As the preservability improver, it is preferable to use compounds described in JP-A Nos. 11-119364 and 2001-42466.
[0137]
The emulsion of the present invention can be used for any photosensitive material, but is preferably used for a multilayer color photographic photosensitive material. It is more preferably used for the blue-sensitive layer of the multilayer color photographic light-sensitive material, and most preferably used for the highest blue-sensitive layer of the multilayer color photographic light-sensitive material. In this case, a high sensitivity / granularity ratio can be obtained due to an increase in blue light absorption based on a high silver iodide content and an increase in blue light absorption based on an increase in the amount of sensitizing dye adsorbed due to the plate shape. . In addition, by improving the monodispersity of the projected area diameter of the grains and decreasing the silver iodide content distribution between grains, the high sensitivity / grain ratio, improved pressure characteristics, improved storage aging characteristics and processing dependency Improvements can be achieved. Further, the scattering of light is reduced by the flat plate shape, and the sharpness of the lower layer is improved.
[0138]
The light-sensitive material produced using the silver halide photographic emulsion of the present invention has at least one silver halide photographic emulsion layer of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer on a support. The number of silver halide photographic emulsion layers and non-photosensitive layers and the layer order are not particularly limited. A typical example is a silver halide photographic light-sensitive material having at least one color-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivity on a support. The photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light. In a multilayer silver halide color photographic light-sensitive material, the unit photosensitive layer is generally used. Are arranged in the order of the red color-sensitive layer, the green color-sensitive layer, and the blue color-sensitive layer from the support side. However, depending on the purpose, the installation order may be reversed, or the installation order may be such that different photosensitive layers are contained in the same color-sensitive layer.
[0139]
A non-photosensitive layer such as an intermediate layer of each layer may be provided between the above-described silver halide photosensitive layers and in the uppermost layer and the lowermost layer.
[0140]
The intermediate layer includes couplers and DIR compounds as described in JP-A Nos. 61-43748, 59-113438, 59-113440, 61-20037, and 61-20038. May be included, and a color mixing inhibitor may be included as normally used.
A plurality of silver halide emulsion layers constituting each unit photosensitive layer are a high-sensitivity emulsion layer and a low-sensitivity emulsion as described in West German Patent 1,121,470 or British Patent 923,045. A two-layer structure of layers can be preferably used. In general, it is preferable that the photosensitivity is gradually decreased toward the support, and a non-photosensitive layer may be provided between the halogen emulsion layers. Further, as described in JP-A-57-112751, 62-200350, 62-206541 and 62-206543, a low-sensitivity emulsion layer is formed on the side away from the support. A high-sensitivity emulsion layer may be provided on the side close to the body.
[0141]
As a specific example, from the side farthest from the support, for example, low sensitivity blue photosensitive layer (BL) / high sensitivity blue photosensitive layer (BH) / high sensitivity green photosensitive layer (GH) / low sensitivity green photosensitive layer (GL ) / High-sensitivity red photosensitive layer (RH) / Low-sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / RH / RL, or BH / BL / GH / GL / RL / It can be installed in the order of RH.
[0142]
Further, as described in JP-B-55-34932, it can be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. Further, as described in JP-A-56-25738 and JP-A-62-63936, the blue photosensitive layer / GL / RL / GH / RH may be installed in this order from the side farthest from the support. it can.
[0143]
In addition, as described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is more sensitive than the middle layer. A silver halide emulsion layer having a low degree is arranged, and an arrangement composed of three layers having different sensitivities in which the sensitivities are gradually lowered toward the support. Even in the case of being composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitive emulsion layer from the side away from the support in the same color-sensitive layer. They may be arranged in the order of / high sensitivity emulsion layer / low sensitivity emulsion layer.
[0144]
In addition, they may be arranged in the order of high sensitivity emulsion layer / low sensitivity emulsion layer / medium sensitivity emulsion layer, or low sensitivity emulsion layer / medium sensitivity emulsion layer / high sensitivity emulsion layer.
[0145]
Further, the arrangement may be changed as described above even when there are four or more layers.
[0146]
Further, as described in JP-A-2000-305228 and JP-A-2000-314940, a reflective layer containing silver halide tabular grains that do not form an image after exposure processing may be disposed.
[0147]
As described above, various layer configurations and arrangements can be selected according to the purpose of each photosensitive material.
[0148]
The above-mentioned various additives are used in the light-sensitive material according to the present invention, but various additives can be used depending on the purpose.
[0149]
These additives are described in more detail in Research Disclosure Item 17643 (December 1978), Item 18716 (November 1979), and Item 308119 (December 1989). These are summarized in the table below.
[0150]

[0151]
Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, a compound that can be immobilized by reacting with formaldehyde described in US Pat. Nos. 4,411,987 and 4,435,503. Is preferably added to the photosensitive material.
[0152]
Various color couplers can be used in the present invention, specific examples of which are described in Research Disclosure No. 1 described above. 17643, VII-CG and G. 307105, described in the patents described in VII-CG.
[0153]
Examples of yellow couplers include U.S. Pat. Nos. 3,933,501, 4,022,620, 4,326,024, 4,401,752, and 4,248,961. No. 58,1039, British Patent No. 1,425,020, No. 1,476,760, U.S. Pat. No. 3,973,968, No. 4 314, 023 and 4,511, 649, European Patent No. 249, 473A, and the like are preferable.
[0154]
The magenta coupler is preferably a 5-pyrazolone compound or a pyrazoloazole compound, such as US Pat. Nos. 4,310,619 and 4,351,897, and European Patent 73,636. U.S. Pat. Nos. 3,061,432 and 3,725,067, Research Disclosure No. 1, U.S. Pat. 24220 (June 1984), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, 61-72238, 60-35730, 55-1118034, 60-185951, US Pat. No. 4,500, Particularly preferred are those described in each specification of No. 630, No. 4,540,654, No. 4,556,630 and International Publication No. WO88 / 04795.
[0155]
Examples of cyan couplers include phenolic and naphtholic couplers, U.S. Pat. Nos. 4,052,212, 4,146,396, 4,228,233, and 4,296,200. No. 2,369,929, No. 2,801,171, No. 2,772,162, No. 2,895,826, No. 3,772,002, No. 3 758,308, 4,334,011, and 4,327,173, West German Patent Publication 3,329,729, European Patent 121,365A, 249 , 453A, U.S. Pat. Nos. 3,446,622, 4,333,999, 4,775,616, 4,451,559, 4,427. No. 767, No. 4,690, 889, No. , No. 254,212, the specification of the same No. 4,296,199, are preferred according to JP 61-42658 Patent Publication.
[0156]
Typical examples of polymerized dye-forming couplers are U.S. Pat. Nos. 3,451,820, 4,080,211, 4,367,282, 4,409,320, No. 4,576,910, British Patent No. 2,102,137 and European Patent No. 341,188A.
[0157]
Examples of couplers in which the coloring dye has an appropriate diffusibility include US Pat. No. 4,366,237, British Patent 2,125,570, European Patent 96,570, West German Patent ( (Publication) Those described in US Pat. No. 3,234,533 are preferred.
[0158]
A colored coupler for correcting unwanted absorption of a coloring dye is Research Disclosure No. No. 17643, VII-G, ibid. No. 307105, VII-G, U.S. Pat. No. 4,163,670, JP-B-57-39413, U.S. Pat. No. 4,004,929, U.S. Pat. No. 4,138,258, Those described in British Patent 1,146,368 are preferred. In addition, a coupler that corrects unnecessary absorption of a coloring dye by a fluorescent dye emitted during coupling described in US Pat. No. 4,774,181, and a coupler described in US Pat. No. 4,777,120. It is also preferable to use a coupler having as a leaving group a dye precursor group capable of reacting with a developing agent to form a dye.
[0159]
Compounds that release photographically useful residues upon coupling can also be preferably used in the present invention. DIR couplers that release a development inhibitor are the above-mentioned RD17643, VII-F terms and Nos. 307105, patents described in paragraph VII-F, JP-A 57-151944, 57-154234, 60-184248, 63-37346, 63-37350, US Pat. Those described in the specifications of 4,248,962 and 4,782,012 are preferred.
[0160]
Examples of couplers that release a nucleating agent or a development accelerator in an image state during development include British Patent Nos. 2,097,140 and 2,131,188, JP-A-59-157638, Those described in JP-A-59-170840 are preferred. Further, a fogging agent is obtained by an oxidation-reduction reaction with an oxidized form of a developing agent described in JP-A-60-107029, JP-A-60-252340, JP-A-1-44940, and JP-A-1-45687. Also preferred are compounds that release development accelerators, silver halide solvents, and the like.
[0161]
Other compounds that can be used in the light-sensitive material of the present invention include competitive couplers described in US Pat. No. 4,130,427 and the like, US Pat. Nos. 4,283,472, 4,338, Multi-equivalent couplers described in each specification of No. 393, No. 4,310,618, DIR redox compound releasing couplers described in JP-A-60-185950, JP-A-62-24252, etc. A DIR coupler releasing coupler, a DIR coupler releasing redox compound or a DIR redox releasing redox compound, a coupler that releases a dye that recovers color after release as described in European Patent Nos. 173,302A and 313,308A, RD. No. 11449, 24241, bleach accelerator releasing couplers described in JP-A-61-201247, ligand releasing couplers described in U.S. Pat. No. 4,555,477, JP-A-63-75747, etc. And a coupler that releases a fluorescent dye described in US Pat. No. 4,774,181.
[0162]
The coupler used in the present invention can be introduced into the photosensitive material by various known dispersion methods.
[0163]
Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in, for example, US Pat. No. 2,322,027.
[0164]
Specific examples of high-boiling organic solvents having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters (for example, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate). Bis (2,4-di-tert-amylphenyl) phthalate, bis (2,4-di-tert-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate); phosphoric acid or phosphonic acid Esters (e.g., triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate Benzoates (eg 2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl-p-hydroxybenzoate); amides (eg N, N-diethyldodecanamide, N, N-diethyllaurylamide, N-tetradecylpyrrolidone); alcohols or phenols (eg, isostearyl alcohol, 2,4-di-tert-amylphenol); aliphatic carboxylic acid esters (eg, bis ( 2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate); aniline derivatives (eg, N, N-dibutyl-2-butoxy-5-tert-octylanily) ); Hydrocarbons (e.g., can be exemplified paraffin, dodecylbenzene, and diisopropylnaphthalene). As the auxiliary solvent, for example, an organic solvent having a boiling point of about 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used. Typical examples include, for example, ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone. , Cyclohexanone, 2-ethoxyethyl acetate, and dimethylformamide.
[0165]
Examples of latex dispersion process steps, effects and impregnating latex are described in, for example, US Pat. No. 4,199,363, West German Patent Application (OLS) No. 2,541,274, and No. 2,541. 230.
[0166]
Examples of the color light-sensitive material of the present invention include phenethyl alcohol and those described in JP-A-63-257747, JP-A-62-272248, and JP-A-1-80941, for example, 1,2-benzisothiazoline- Various preservatives or antifungal agents such as 3-one, n-butyl-p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, 2- (4-thiazolyl) benzimidazole Is preferably added.
[0167]
The emulsion of the present invention can be applied to various color light-sensitive materials. For example, color negative films for general use or movies, color reversal films for slides or television, color paper, color positive film and color reversal paper can be given as representative examples. The present invention can be particularly preferably used for a film for color duplication.
[0168]
Suitable supports that can be used for the light-sensitive material containing the emulsion of the present invention include, for example, the aforementioned RD. No. 17643, page 28, ibid. No. 18716, page 647, right column to page 648, left column, and 307105, page 879.
[0169]
In the light-sensitive material containing the emulsion of the present invention, the total thickness of all hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, still more preferably 18 μm or less, and 16 μm or less. Is particularly preferred. In addition, membrane swelling speed T_1/2Is preferably 30 seconds or shorter, and more preferably 20 seconds or shorter. The film thickness here means a film thickness measured at 25 ° C. and a relative humidity of 55% (2 days). Also, the membrane swelling speed T_1/2Can be measured according to techniques known in the art, such as Photographic Science and Engineering (Vol. Sci. Eng.), Vol. 19, No. 2, 124 by A. Green et al. It can be measured by using a spherometer of the type described on page 129. T_1/2Is defined as the time required to reach 90% of the maximum swelled film thickness when it is processed with a color developer at 30 ° C. for 3 minutes and 15 seconds, and to reach 1/2 of the saturated film thickness.
[0170]
Membrane swelling speed T_1/2Can be adjusted by adding a hardener to gelatin as a binder or changing the aging conditions after coating.
[0171]
The photosensitive material containing the emulsion of the present invention is preferably provided with a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 to 20 μm on the side opposite to the side having the emulsion layer. This back layer preferably contains, for example, the above-described light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, and surfactant. . The swelling ratio of the back layer is preferably 150 to 500%.
[0172]
The color photographic light-sensitive material according to the present invention has the RD. No. 17643, pp. 28-29, ibid. No. 18716, page 651, left column to right column; 307105, pages 880-881, and can be developed by a conventional method.
[0173]
The color developer used for the development processing of the light-sensitive material containing the emulsion of the present invention is preferably an alkaline aqueous solution mainly composed of an aromatic primary amine color developing agent. As this color developing agent, aminophenol compounds are also useful, but p-phenylenediamine compounds are preferably used, and representative examples thereof include 3-methyl-4-amino-N, N diethylaniline, 3-methyl -4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl -Β-methoxyethylaniline, and sulfates, hydrochlorides, or p-toluenesulfonates of these. Of these, sulfate of 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline is particularly preferable. These compounds may be used in combination of two or more depending on the purpose.
[0174]
Color developers include, for example, pH buffering agents such as alkali metal carbonates, borates or phosphates, chloride salts, bromide salts, iodide salts, benzimidazoles, benzothiazoles or mercapto compounds. It is common to include a development inhibitor or an antifogging agent. If necessary, various preservatives such as hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, catecholsulfonic acids; ethylene glycol, Organic solvents such as diethylene glycol; development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines; dye-forming couplers, competitive couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone; viscosity imparting Agents: Various chelating agents represented by aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid and phosphonocarboxylic acid can be used. Examples of chelating agents include ethylenediaminetetraacetic acid, nitrile triacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N- Typical examples include trimethylenephosphonic acid, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof.
[0175]
When reversal processing is performed, color development is usually performed after black and white development. This black-and-white developer includes, for example, dihydroxybenzenes such as hydroquinone, for example 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol. Known black-and-white developing agents can be used alone or in combination. The pH of these color developers and black-and-white developers is generally 9-12. The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per square meter of the light-sensitive material. By reducing the bromide ion concentration in the replenishing solution, 500 ml or less. It can also be. When reducing the replenishment amount, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing liquid with air.
[0176]
The contact area between the photographic processing solution and air in the processing tank can be expressed by the aperture ratio defined below. That is,
Opening ratio = [contact area between treatment liquid and air (cm²)] ÷ [Volume of processing solution (cm³]]
The opening ratio is preferably 0.1 or less, more preferably 0.001 to 0.05. As a method of reducing the aperture ratio in this way, in addition to a method of providing a shielding object such as a floating lid on the photographic processing liquid surface of the processing tank, a movable lid described in JP-A-1-82033 is used. Examples thereof include a slit developing method described in JP-A No. 63-216005. The reduction of the aperture ratio is preferably applied not only in both color development and black-and-white development but also in subsequent steps such as bleaching, bleach-fixing, fixing, washing and stabilization. Further, the replenishment amount can be reduced by using a means for suppressing the accumulation of bromide ions in the developer.
[0177]
The color development time is usually set between 2 and 5 minutes, but the processing time can be further shortened by setting the temperature and pH to a high value and using the color developing agent at a high concentration.
[0178]
The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleaching and fixing process) or may be performed individually. Further, in order to speed up the processing, a processing method of performing bleach-fixing processing after the bleaching processing may be used. Further, depending on the purpose, it is possible to carry out the treatment in two continuous bleach-fixing baths, the fixing treatment before the bleach-fixing treatment, or the bleaching treatment after the bleach-fixing treatment. As the bleaching agent, for example, a compound of a polyvalent metal such as iron (III), peracids (especially sodium persulfate is suitable for a color negative film for movies), quinones and nitro compounds are used. Typical bleaching agents include organic complex salts of iron (III) such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid. Complex salts with aminopolycarboxylic acids or complex salts with, for example, citric acid, tartaric acid and malic acid can be used. Of these, iron (III) complex salts of aminopolycarboxylic acid such as iron (III) complex salt of ethylenediaminetetraacetate and 1,3-diaminopropanetetraacetate are the viewpoints of rapid processing and prevention of environmental pollution. To preferred. Furthermore, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in both a bleaching solution and a bleach-fixing solution. The pH of the bleaching solution or bleach-fixing solution using these iron (III) complex salts of aminopolycarboxylic acid is usually 4.0 to 8. However, the processing can be performed at a lower pH in order to speed up the processing.
[0179]
A bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution, and their pre-bath, if necessary. Specific examples of useful bleach accelerators are described in the following specifications: for example, U.S. Pat. No. 3,893,858, West German Patents 1,290,812, 2,059, No. 988, JP-A Nos. 53-32736, 53-57831, 53-37418, 53-72623, 53-95630, 53-95631, 53-104232, 53- Nos. 124424, 53-141623, 53-18426, Research Disclosure No. Compounds having mercapto groups or disulfide groups described in JP-A No. 17129 (July 1978); thiazolidine derivatives described in JP-A No. 51-140129; JP-B Nos. 45-8506, 52-20832 and 53 No. -32735, thiourea derivatives described in US Pat. No. 3,706,561, West German Patent No. 1,127,715, iodide salt described in JP-A No. 58-16235; Polyoxyethylene compounds described in West German Patent Nos. 966,410 and 2,748,430; polyamine compounds described in Japanese Examined Patent Publication No. 45-8836; other JP-A-49-40943, 49- Compounds described in Japanese Patent Nos. 59644, 53-94927, 54-35727, 55-26506, and 58-163940; Thing ion or the like can be used. Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of a large accelerating effect. In particular, US Pat. No. 3,893,858, West German Patent 1,290,812, and JP-A-53-95630 are preferred. The compounds described in the publication are preferred. Furthermore, the compounds described in US Pat. No. 4,552,884 are also preferable. These bleach accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when a color light-sensitive material for photography is bleach-fixed.
[0180]
In addition to the above compounds, the bleaching solution or the bleach-fixing solution preferably contains an organic acid for the purpose of preventing bleaching stains. Particularly preferred organic acids are compounds having an acid dissociation constant (pKa) of 2 to 5, and specific examples include acetic acid, propionic acid, and hydroxyacetic acid.
[0181]
Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodide salts. Of these, thiosulfate is generally used, and ammonium thiosulfate is most widely used. Further, a combination of thiosulfate and, for example, thiocyanate, thioether compound, or thiourea is also preferable. As a preservative for a fixing solution or a bleach-fixing solution, sulfites, bisulfites, carbonyl bisulfite adducts, or sulfinic acid compounds described in European Patent No. 294,769A are preferable. Further, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution and the bleach-fixing solution for the purpose of stabilizing the solution.
[0182]
In the present invention, the fixing solution or bleach-fixing solution contains a compound having a pKa of 6.0 to 9.0 for pH adjustment, preferably imidazole, 1-methylimidazole, 1-ethylimidazole, 2-methylimidazole, etc. It is preferable to add imidazoles in an amount of 0.1 to 10 mol / liter.
[0183]
The total desilvering time is preferably as short as possible without causing desilvering failure. The preferred time is 1 minute to 3 minutes, more preferably 1 minute to 2 minutes. The processing temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C. In the preferred temperature range, the desilvering rate is improved, and the occurrence of stain after the treatment is effectively prevented.
[0184]
In the desilvering step, it is preferable that the stirring is strengthened as much as possible. Specific methods for strengthening the stirring include a method of causing a jet of a processing solution to collide with the emulsion surface of a photosensitive material described in JP-A-62-183460, and a rotating means in JP-A-62-183461. To increase the stirring effect. Furthermore, the photosensitive material is moved while the wiper blade provided in the solution is in contact with the emulsion surface, and the emulsion surface is turbulent to improve the stirring effect, and the circulation flow rate of the entire processing solution is increased. The method of letting it be mentioned. Such a stirring improving means is effective in any of the bleaching solution, the bleach-fixing solution, and the fixing solution. The improvement in stirring is considered to speed up the supply of the bleaching agent and the fixing agent into the emulsion film and consequently increase the desilvering rate. Further, the above stirring improving means is more effective when a bleaching accelerator is used, and the acceleration effect can be remarkably increased or the fixing inhibiting action can be eliminated by the bleaching accelerator.
[0185]
An automatic developing machine used for developing a photosensitive material containing the emulsion of the present invention has photosensitive material conveying means described in JP-A-60-191257, JP-A-60-191258, and JP-A-60-191259. It is preferable. As described in JP-A-60-191257, such a conveying means can remarkably reduce the carry-in of the processing liquid from the pre-bath to the post-bath and is highly effective in preventing the performance deterioration of the processing liquid. Such an effect is particularly effective in shortening the processing time in each process and reducing the replenishment amount of the processing liquid.
[0186]
The silver halide color photographic light-sensitive material containing the emulsion of the present invention is generally subjected to a washing and / or stabilizing process after desilvering. The amount of water to be washed in the washing step depends on the characteristics of the photosensitive material (for example, depending on the material used such as a coupler), the application, and further, for example, the temperature of the washing water, the number of washing tanks (number of stages), replenishment such as countercurrent and forward flow A wide range can be set according to the system and other various conditions. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent system is described in Journal of the Society of Motion Picture and Television Engineers Vol. 64, p. 248 to 253 (May 1955).
[0187]
According to the multi-stage countercurrent system described in the above-mentioned document, the amount of water to be washed can be greatly reduced. However, bacteria are propagated due to an increase in the residence time of water in the tank, and the generated suspended matter adheres to the photosensitive material. Problems arise. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method for reducing calcium ions and magnesium ions described in JP-A-62-288838 can be used very effectively. In addition, as described in JP-A-57-8542, for example, isothiazolone compounds, siabendazoles, chlorinated bactericides such as chlorinated sodium isocyanurate, and others such as benzotriazole, Hiroshi Horiguchi. "Chemistry of Antibacterial and Antifungal Agents" (1986) Sankyo Publishing, edited by Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982) Industrial Technology Association, Japan The disinfectant described in “Enamel Antibacterial Encyclopedia” (1986) can also be used.
[0188]
The pH of the washing water in the processing of the light-sensitive material containing the emulsion of the present invention is 4 to 9, preferably 5 to 8. The washing water temperature and washing time can also be variously set depending on, for example, the characteristics and application of the photosensitive material. In general, the washing water temperature and washing time are 15 to 45 ° C. for 20 seconds to 10 minutes, preferably 25 to 40 ° C. for 30 seconds to 5 minutes. A range is selected. Furthermore, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the water washing. In such stabilization treatment, all known methods described in JP-A-57-8543, 58-14834 and 60-220345 can be used.
[0189]
Further, a stabilization treatment may be further performed following the water washing treatment. Examples thereof include a stabilizing bath containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photographing. Examples of the dye stabilizer include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts. Various chelating agents and fungicides can also be added to this stabilizing bath.
[0190]
The overflow liquid accompanying the washing and / or replenishment of the stabilizing liquid can be reused in other processes such as a desilvering process.
[0191]
For example, in the processing using an automatic developing machine, when each of the above processing solutions is concentrated by evaporation, it is preferable to correct the concentration by adding water.
[0192]
The silver halide color photographic light-sensitive material containing the emulsion of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing. In order to incorporate them, it is preferable to use various precursors of color developing agents. For example, indoaniline compounds described in US Pat. No. 3,342,597, for example, US Pat. No. 3,342,599, Research Disclosure No. 14,850 and No. No. 15,159, Schiff base type compounds, And aldol compounds described in US Pat. No. 13,924, metal salt complexes described in US Pat. No. 3,719,492, and urethane compounds described in JP-A-53-135628.
[0193]
The silver halide color photographic material containing the emulsion of the present invention may incorporate various 1-phenyl-3-pyrazolidones for the purpose of accelerating color development, if necessary. Typical compounds are described in, for example, JP-A-56-64339, JP-A-57-144547, and JP-A-58-115438.
[0194]
The various processing liquids in the present invention can be used at 10 ° C to 50 ° C. Usually, a temperature of 33 ° C. to 38 ° C. is standard, but the temperature is increased to accelerate the processing and shorten the processing time, or conversely, the temperature is lowered to achieve an improvement in image quality and stability of the processing solution. be able to.
[0195]
【Example】
[Example 1]
Hereinafter, the present invention will be specifically described by way of examples. However, the embodiment of the present invention is not limited thereto.
Gelatin-1 to 4 used as dispersion media in the following emulsion preparation are gelatins having the following attributes.
[0196]
Gelatin-1: Ordinary alkali-treated ossein gelatin made from beef bone.
[0197]
-NH in gelatin₂No chemical modification of the group.
[0198]
Gelatin-2: Gelatin obtained by adding succinic acid to an aqueous solution of gelatin-1 at 50 ° C. and pH 9.0 to cause a chemical reaction, and then removing the remaining succinic acid and drying.
[0199]
-NH in gelatin₂95% of the number of chemically modified groups.
[0200]
Gelatin-3: Gelatin formed by lowering the molecular weight by causing an enzyme to act on gelatin-1 to have a mass average molecular weight of 15000 and then inactivating the enzyme to dry it.
[0201]
-NH in gelatin₂No chemical modification of the group.
[0202]
The methionine group content in gelatin is 42 μmol / g.
[0203]
Gelatin-4: Gelatin prepared by adding hydrogen peroxide to an aqueous solution of gelatin-3 to cause a chemical reaction, and then inactivating the remaining hydrogen peroxide with catalase.
[0204]
-NH in gelatin₂No chemical modification of the group.
[0205]
The methionine group content in gelatin is 3.4 μmol / g.
[0206]
The gelatins 1 to 4 were all deionized and then adjusted so that the pH of a 5% aqueous solution at 35 ° C. was 6.0.
[0207]
Preparation of (seed emulsion 1)
1200 cc of an aqueous solution containing 0.9 g of KBr and 1 g of the gelatin-3 was kept at 35 ° C. and stirred (preparation of the 1st solution).
Ag-1 aqueous solution (AgNO₃37.5 cc) (concentration 0.29M) and 55 cc of the X-1 aqueous solution (the gelatin-3 concentration 15.5 g / L, KBr concentration 0.295M) were simultaneously added at a constant flow rate (addition 1).
Thereafter, 6 g of KBr was added, and the temperature was raised to 75 ° C. After the temperature increase, 300 cc of an aqueous G-1 solution (the gelatin-2 concentration of 117 g / L) was added. At this time, the pH was adjusted to 5.5.
Next, an Ag-2 aqueous solution (AgNO₃73 cc) was added at a constant flow rate (addition 2).
[0208]
Next, 1 mg of sodium benzenethiosulfonate was added. Ag-3 aqueous solution (AgNO₃A stirrer described in JP-A-10-43570 is 513 cc) and 1461 cc of an X-3 aqueous solution (the gelatin-4 concentration 186.76 g / L, KBr concentration 0.566 M, KI concentration 0.0629 M). And a silver halide photographic emulsion containing silver iodobromide fine grains having an average size of 0.025 μm was added continuously immediately after ejection (addition 3). At this time, an X-2 aqueous solution (KBr concentration of 0.525 M) was also added to adjust the silver potential to 0 mV with respect to the saturated calomel electrode. During this time, the pH was adjusted to be maintained between 5 and 6.
[0209]
Thereafter, desalting was performed by a normal flocculation method, and then water, NaOH, and the above gelatin-1 were added with stirring to adjust the pH to 5.8 and the pAg to 8.8.
[0210]
The resulting emulsion contained grains having an average silver iodide content of 9 mol%, an average sphere equivalent diameter of 0.65 μm, and an average aspect ratio of 33.
[0211]
Preparation of (seed emulsion 2)
By replacing the KBr concentration of the X-3 aqueous solution used in Addition 3 of seed emulsion 1 with 0.610M and KI concentration of 0.0189M, the average silver iodide content is 2.5 mol% and the average equivalent sphere diameter is 0.65 μm. An emulsion composed of grains having an average aspect ratio of 35 was obtained.
[0212]
Preparation of (seed emulsion 3)
By replacing the KBr concentration of the X-3 aqueous solution used in Addition 3 of seed emulsion 1 with 0.597M and KI concentration of 0.0314M, the average silver iodide content is 2.5 mol% and the average sphere equivalent diameter is 0.65 μm. An emulsion composed of grains having an average aspect ratio of 35 was obtained.
[0213]
Preparation of (seed emulsion 4)
The method for preparing silver halide tabular grains described in Seed Emulsion 2 of Example 1 of JP-A-2003-43603 was referred to.
1200 cc of a dispersion medium solution containing 0.54 g of NaCl and 0.5 g of the gelatin-3 is kept in a reaction vessel at 35 ° C., and while stirring it, an Ag-1 aqueous solution (AgNO 3₃37.5 cc of each of 0.29M halogen salt (KBr, NaCl) aqueous solution (X-1) adjusted to have a molar ratio of KBr / NaCl of 80/20 and silver nitrate of 0.29M) Added.
[0214]
Then, after addition 1, 6.5 g of KBr was added, and the temperature was raised to 75 ° C. After the temperature rise, 300 cc of an aqueous G-1 solution (concentration of gelatin-2 of 117 g / L) was added. At this time, the pH was adjusted to 5.5.
[0215]
Next, an Ag-2 aqueous solution (AgNO₃73 cc) was added at a constant flow rate (addition 2).
[0216]
Next, 1 mg of sodium benzenethiosulfonate was added. Ag-3 aqueous solution (AgNO₃A stirrer described in JP-A-10-43570 is 513 cc) and 1461 cc of an X-3 aqueous solution (the gelatin-4 concentration 186.76 g / L, KBr concentration 0.566 M, KI concentration 0.0629 M). And a silver halide photographic emulsion containing silver iodobromide fine grains having an average size of 0.025 μm was added continuously immediately after ejection (addition 3). At this time, an X-2 aqueous solution (KBr concentration of 0.525 M) was also added to adjust the silver potential to 0 mV with respect to the saturated calomel electrode. During this time, the pH was adjusted to be maintained between 5 and 6.
[0217]
Thereafter, desalting was performed by a normal flocculation method, and then water, NaOH, and the above gelatin-1 were added with stirring to adjust the pH to 5.8 and the pAg to 8.8.
The obtained emulsion contained grains having an average silver iodide content of 9 mol%, an average sphere equivalent diameter of 0.65 μm, and an average aspect ratio of 26.
[0218]
Preparation of (seed emulsion 5)
1200 cc of an aqueous solution containing 0.9 g of KBr and 0.14 g of gelatin-3 was kept at 35 ° C. and stirred (preparation of 1st solution).
Ag-1 aqueous solution (AgNO₃Concentration 0.145M) 37.5 cc, X-1 solution (KBr concentration 0.148M) 55 cc and G-1 solution (gelatin-3 concentration 50 g / L) 81 cc were added simultaneously at a constant flow rate. (Addition 1).
Thereafter, 6 g of KBr was added, then 4 g of the gelatin-3 was added, and the temperature was raised to 75 ° C. After the temperature increase, 300 cc of an aqueous solution G-2 (concentration of gelatin-2 at 117 g / L) was added. At this time, the pH was adjusted to 5.5.
Next, an Ag-2 aqueous solution (AgNO₃73 cc) was added at a constant flow rate (addition 2).
[0219]
Next, 1 mg of sodium benzenethiosulfonate was added. Next, an Ag-3 aqueous solution (AgNO₃735 cc) and 735 cc of X-3 aqueous solution (the gelatin-4 is 174.3 g / L, KBr concentration 0.771 M, KI concentration 0.0857 M) is a stirrer described in JP-A-10-43570 And a silver halide photographic emulsion containing silver iodobromide fine grains having an average size of 0.025 μm was added continuously immediately after ejection (addition 3). At this time, an X-2 aqueous solution (KBr concentration of 0.525 M) was also added to adjust the silver potential to 0 mV with respect to the saturated calomel electrode. During this time, the pH was adjusted to be maintained between 5 and 6.
[0220]
Thereafter, desalting was performed by a normal flocculation method, and then water, NaOH, and the above gelatin-1 were added with stirring to adjust the pH to 5.8 and the pAg to 8.8.
[0221]
The resulting emulsion was composed of grains having an average silver iodide content of 9 mol%, an average sphere equivalent diameter of 0.65 μm, and an average aspect ratio of 33.
[0222]
Preparation of (seed emulsion 6)
1200 cc of an aqueous solution containing 0.9 g of KBr and 0.5 g of gelatin-3 was kept at 35 ° C. and stirred (preparation of the 1st solution).
Ag-1 aqueous solution (AgNO₃37.5 cc (concentration 0.145M) and 55 cc of X-1 solution (7.8 g / L of gelatin-3, KBr concentration 0.148M) were simultaneously added at a constant flow rate (addition 1).
[0223]
Thereafter, 6 g of KBr was added, then 4 g of the gelatin-3 was added, and the temperature was raised to 75 ° C. After the temperature increase, 300 cc of an aqueous solution G-2 (concentration of gelatin-2 at 117 g / L) was added. At this time, the pH was adjusted to 5.5.
Next, an Ag-2 aqueous solution (AgNO₃73 cc) was added at a constant flow rate (addition 2).
[0224]
Next, 1 mg of sodium benzenethiosulfonate was added. Next, an Ag-3 aqueous solution (AgNO₃735 cc) and 735 cc of X-3 aqueous solution (the gelatin-4 is 174.3 g / L, KBr concentration 0.771 M, KI concentration 0.0857 M) is a stirrer described in JP-A-10-43570 And a silver halide photographic emulsion containing silver iodobromide fine grains having an average size of 0.025 μm was added continuously immediately after ejection (addition 3). At this time, an X-2 aqueous solution (KBr concentration of 0.525 M) was also added to adjust the silver potential to +40 mV with respect to the saturated calomel electrode. During this time, the pH was adjusted to be maintained between 5 and 6.
[0225]
Thereafter, desalting was performed by a normal flocculation method, and then water, NaOH, and the above gelatin-1 were added with stirring to adjust the pH to 5.8 and the pAg to 8.8.
[0226]
The resulting emulsion contained grains having an average silver iodide content of 9 mol%, an average sphere equivalent diameter of 0.65 μm, and an average aspect ratio of 33.
[0227]
Preparation of (seed emulsion 7)
Seed emulsion 2 was prepared with reference to seed emulsion 2.
1200 cc of an aqueous solution containing 0.9 g of KBr and 0.5 g of gelatin-3 was kept at 35 ° C. and stirred (preparation of the 1st solution).
Ag-1 aqueous solution (AgNO₃Halogen salt (KBr, NaCl) aqueous solution (X: 0.29M, gelatin concentration: 7.8 g / L) adjusted to a molar ratio of KBr / NaCl of 95/5. -1) was added in an amount of 37.5 cc each.
Thereafter, 6.5 g of KBr was added, and the temperature was raised to 75 ° C. After the aging process at an elevated temperature, 300 cc of an aqueous G-1 solution (the gelatin-2 concentration of 117 g / L) was added.
[0228]
Next, an appropriate amount of 1N sulfuric acid was added to adjust the pH to 5.5.
Next, an Ag-2 aqueous solution (AgNO₃73 cc) was added at a constant flow rate (addition 2).
[0229]
Next, 1 mg of sodium benzenethiosulfonate was added. Next, an Ag-3 aqueous solution (AgNO₃735 cc) and 735 cc of X-3 aqueous solution (the gelatin-4 is 174.3 g / L, KBr concentration 0.771 M, KI concentration 0.0857 M) is a stirrer described in JP-A-10-43570 And a silver halide photographic emulsion containing silver iodobromide fine grains having an average size of 0.025 μm was added continuously immediately after ejection (addition 3). At this time, an X-2 aqueous solution (KBr concentration of 0.525 M) was also added to adjust the silver potential to +40 mV with respect to the saturated calomel electrode. During this time, the pH was adjusted to be maintained between 5 and 6.
[0230]
Thereafter, desalting was performed by a normal flocculation method, and then water, NaOH, and the above gelatin-1 were added with stirring to adjust the pH to 5.8 and the pAg to 8.8.
[0231]
The resulting emulsion was composed of grains having an average silver iodide content of 9 mol%, an average sphere equivalent diameter of 0.65 μm, and an average aspect ratio of 31.
[0232]
Preparation of (seed emulsion 8)
Seed emulsion 6 was prepared with reference to seed emulsion 2.
1200 cc of an aqueous solution containing 0.9 g of KBr and 0.5 g of gelatin-3 was kept at 35 ° C. and stirred (preparation of the 1st solution).
[0233]
Ag-1 aqueous solution (AgNO₃Halogen salt (KBr, NaCl) aqueous solution (X: 0.29M, gelatin concentration: 7.8 g / L) adjusted to a molar ratio of KBr / NaCl of 95/5. -1) was added simultaneously at 37.5 cc each.
[0234]
Thereafter, 6.5 g of KBr was added, then 4 g of gelatin-3 was added, and the temperature was raised to 75 ° C. After the aging process at an elevated temperature, 300 cc of an aqueous G-1 solution (the gelatin-2 concentration of 117 g / L) was added.
[0235]
Next, an appropriate amount of 1N sulfuric acid was added to adjust the pH to 5.5.
Next, an Ag-2 aqueous solution (AgNO₃73 cc) was added at a constant flow rate (addition 2).
[0236]
Next, 1 mg of sodium benzenethiosulfonate was added. Next, an Ag-3 aqueous solution (AgNO₃735 cc) and 735 cc of X-3 aqueous solution (the gelatin-4 is 174.3 g / L, KBr concentration 0.771 M, KI concentration 0.0857 M) is a stirrer described in JP-A-10-43570 And a silver halide photographic emulsion containing silver iodobromide fine grains having an average size of 0.025 μm was added continuously immediately after ejection (addition 3). At this time, an X-2 aqueous solution (KBr concentration of 0.525 M) was also added to adjust the silver potential to +40 mV with respect to the saturated calomel electrode. During this time, the pH was adjusted to be maintained between 5 and 6.
[0237]
Thereafter, desalting was performed by a normal flocculation method, and then water, NaOH, and the above gelatin-1 were added with stirring to adjust the pH to 5.8 and the pAg to 8.8.
[0238]
The resulting emulsion contained grains having an average silver iodide content of 9 mol%, an average sphere equivalent diameter of 0.65 μm, and an average aspect ratio of 31.
[0239]
(Em-A1)
<Particle formation>
1200 cc of an aqueous solution containing 46 g of alkali-treated gelatin and 1.7 g of KBr was kept at 75 ° C. and stirred vigorously. After adding 39 g of the above-mentioned seed emulsion 1, 0.3 g of modified silicon oil (product of Nippon Unicar Co., Ltd., L7602) was added. H₂SO₄After adjusting pH to 5.5, AgNO₃Was added at the same time by a double jet method, and 71 cc of an aqueous solution containing 7.0 g of KBr and KI containing 10 mol% of a mixed aqueous solution of KBr and KI. At this time, the silver potential was kept at 0 mV with respect to the saturated calomel electrode. After adding 2 mg of sodium benzenethiosulfonate and 2 mg of thiourea dioxide, AgNO3 was used with the stirring device described in JP-A-10-43570.₃Is mixed with 800 cc of an aqueous solution containing 178.5 g, 800 cc of an aqueous solution containing 112.5 g of KBr, 17.4 g of KI and 80 g of the gelatin-4 (aqueous solution a), and an iodide having a silver iodide content of 10 mol% is mixed. The silver iodide emulsion was continuously added to the reaction vessel while preparing a silver fine grain emulsion (average size: 0.026 μm). At this time, the silver potential was kept at −30 mV with respect to the saturated calomel electrode. AgNO₃78.8 cc of an aqueous solution containing 24.6 g and an aqueous KBr solution were added by the double jet method. At this time, the silver potential was adjusted to 8.03 with respect to the saturated calomel electrode. The temperature was lowered to 40 ° C., KBr was added to adjust the silver potential to −40 mV with respect to the saturated calomel electrode, and then an aqueous solution containing 14.5 g of sodium P-iodoacetamidobenzenesulfonate (monohydrate) was added. Thereafter, 57 cc of a 0.8 M sodium sulfite aqueous solution was added, and iodide ions were produced while controlling the pH to 9.0. Thereafter, the temperature was raised to 55 ° C., and then the pH was returned to 5.5. Thereafter, AgNO3 was kept at 55 ° C.₃Was added 105.2 cc of an aqueous solution containing 24.6 g. During the addition, the silver potential was adjusted to −50 mV with respect to the saturated calomel electrode with an aqueous KBr solution. After washing with water, gelatin was added to adjust the pH to 5.8 and pAg 8.7 at 40 ° C.
[0240]
<Sensitization>
After adding compounds 1 and 2, the temperature was raised to 60 ° C. After adding sensitizing dyes 1 and 2, potassium thiocyanate, chloroauric acid, sodium thiosulfate and N, N-dimethylselenourea were added for optimum chemical sensitization. Compound 3 and compound 4 were added at the end of chemical sensitization. Here, optimal chemical sensitization means that the sensitizing dye and each compound are 10 per mol of silver halide.^-1To 10^-8It means that it was selected from the range of molar addition amount.
[0241]
[Chemical 1]

[0242]
[Chemical 2]

[0243]
[Chemical 3]

[0244]
[Formula 4]

[0245]
[Chemical formula 5]

[0246]
[Chemical 6]

[0247]
(Em-B1)
<Particle formation>
1211 cc of an aqueous solution containing 46 g of alkali-treated gelatin and 1.7 g of KBr was kept at 75 ° C. and stirred vigorously. After adding 38.4 g of the above-mentioned seed emulsion 1, 0.3 g of modified silicone oil (Nihon Unicar Co., Ltd. product, L7602) was added. H₂SO₄After adjusting pH to 5.5, AgNO₃Was added by a double jet method with a mixed solution of 71 cc of an aqueous solution containing 8.9 g and KBr and KI containing 10 mol% of KI. At this time, the silver potential was kept at 0 mV with respect to the saturated calomel electrode. After adding 2 mg of sodium benzenethiosulfonate and 2 mg of thiourea dioxide, AgNO3 was used with the stirring device described in JP-A-10-43570.₃A mixture of 800 cc of an aqueous solution containing 178.5 g and 112.5 g of KBr, 800 cc of an aqueous solution containing 17.4 g of KI and 80 g of the gelatin-4, and a silver iodide fine grain emulsion having a silver iodide content of 10 mol% (average The silver iodide emulsion was continuously added to the reaction vessel while preparing a size of 0.026 μm. At this time, the silver potential was kept at −30 mV with respect to the saturated calomel electrode. Then AgNO₃An aqueous solution containing 61.4 g of 137.6 cc and a mixed aqueous solution of KBr and KI containing 10 mol% of KI were added by the double jet method. At this time, the silver potential was initially maintained at +20 mV with respect to the saturated calomel electrode and at +120 mV in the second half. After the temperature was lowered to 50 ° C., 57.8 cc of 0.3% KI aqueous solution was added. Immediately thereafter, AgNO₃19.7 cc of an aqueous solution containing 8.8 g, 21. 1 cc of an aqueous solution containing 1.51 g of NaCl and 2.47 g of KBr and a solution containing 0.005 mol of silver iodide fine particles were added simultaneously. At this time, AgNO to be added₃8.0 × 10 for 1 mol^-4mol K₄[RuCN₆] Was present. Thereafter, a sensitizing dye was added. After washing with water, gelatin was added to adjust the pH to 5.8 and pAg 8.7 at 40 ° C.
[0248]
<Sensitization>
After adding compounds 1 and 2, the temperature was raised to 60 ° C. After adding sensitizing dyes 1 and 2, potassium thiocyanate, chloroauric acid, sodium thiosulfate, and N, N-dimethylselenourea were added for optimum chemical sensitization. Compound 3 and compound 4 were added at the end of chemical sensitization. Here, optimal chemical sensitization means that the sensitizing dye and each compound are 10 per mol of silver halide.^-1To 10^-8It means that it was selected from the range of molar addition amount.
[0249]
(Em-A2)
Em-A2 was obtained in the same manner as Em-A1, except that seed emulsion 2 was used instead of seed emulsion 1 and KBr was changed to 121.2 g and KI was changed to 5.2 g in aqueous solution a.
[0250]
(Em-A3)
Em-A3 was obtained in the same manner as Em-A1, except that seed emulsion 3 was used instead of seed emulsion 1, and KBr was changed to 118.7 g and KI was set to 8.7 g in aqueous solution a.
[0251]
(Em-A4)
Em-A4 was obtained in the same manner as Em-A1, except that seed emulsion 4 was used instead of seed emulsion 1.
[0252]
(Em-A5)
Em-A5 was obtained in the same manner as Em-A1, except that seed emulsion 5 was used instead of seed emulsion 1.
[0253]
(Em-A6)
Em-A6 was obtained in the same manner as Em-A1, except that seed emulsion 6 was used instead of seed emulsion 1.
[0254]
(Em-A7)
Em-A7 was obtained in the same manner as Em-A1, except that seed emulsion 7 was used instead of seed emulsion 1.
[0255]
(Em-A8)
Em-A8 was obtained in the same manner as Em-A1, except that seed emulsion 8 was used instead of seed emulsion 1.
[0256]
(Em-B2)
Em-B2 was obtained in the same manner as Em-B1, except that seed emulsion 4 was used instead of seed emulsion 1.
[0257]
(Em-B3)
Em-B3 was obtained in the same manner as Em-B1, except that seed emulsion 5 was used instead of seed emulsion 1.
[0258]
(Em-B4)
Em-B4 was obtained in the same manner as Em-B1, except that seed emulsion 6 was used instead of seed emulsion 1.
[0259]
(Em-B5)
Em-B5 was obtained in the same manner as Em-B1, except that seed emulsion 7 was used instead of seed emulsion 1.
[0260]
(Em-B6)
Em-B6 was obtained in the same manner as Em-B1, except that seed emulsion 8 was used instead of seed emulsion 1.
[0261]
(Em-C1)
Em-C1 was obtained by changing the sensitized portion of Em-A5 as follows.
After adding compounds 1 and 2, the temperature was raised to 60 ° C. After addition of sensitizing dyes 1 and 2, potassium thiocyanate, bis (1,4,5-trimethyl-1,2,4-triazolium-3-thiolate gold) (1) tetrafluoroborate, carboxymethyltrimethylthio Urea and N, N-dimethylselenourea were added for optimal chemical sensitization. Compound 3 and compound 4 were added at the end of chemical sensitization. Here, optimal chemical sensitization means that the sensitizing dye and each compound are mixed at 10 per mole of silver halide.^-1To 10^-8It means that it was selected from the range of molar addition amount.
[0262]
(Em-C2)
Em-C2 was obtained by changing the sensitized portion of Em-A5 as follows.
After adding compounds 1 and 2, the temperature was raised to 60 ° C. After addition of sensitizing dyes 1 and 2, potassium thiocyanate, bis (1,4,5-trimethyl-1,2,4-triazolium-3-thiolate gold (I)) tetrafluoroborate, carboxymethyltrimethylthio Urea and N, N-dimethylselenourea were added for optimum chemical sensitization. The total of compound 5 and compound 6 is 1 × 10 at the time of chemical sensitization^-4It added so that it might become mol / molAg. Compound 3 and compound 4 were added at the end of chemical sensitization. Here, optimal chemical sensitization means that the sensitizing dye and each compound are added at a rate of 10 per mole of silver halide.^-1To 10^-8It means that it was selected from the range of molar addition amount.
[0263]
[Chemical 7]

[0264]
[Chemical 8]

[0265]
(Em-C3)
Em-C3 was obtained by changing the sensitized portion of Em-A5 as follows.
After adding compounds 1 and 2, the temperature was raised to 60 ° C. After addition of sensitizing dyes 2 and 3, potassium thiocyanate, bis (1,4,5-trimethyl-1,2,4-triazolium-3-thiolate gold (I)) tetrafluoroborate, carboxymethyltrimethylthio Urea and N, N-dimethylselenourea were added for optimum chemical sensitization. 1 × 10 for compound 5 during chemical sensitization^-4mol / mol Ag was added. Compound 3 and compound 4 were added at the end of chemical sensitization. Here, optimal chemical sensitization means that the sensitizing dye and each compound are added at a rate of 10 per mole of silver halide.^-1To 10^-8It means that it was selected from the range of molar addition amount.
[0266]
[Chemical 9]

[0267]
(Em-C4)
Em-C4 was obtained by changing the sensitized portion of Em-A5 as follows.
[0268]
After adding compounds 1 and 2, the temperature was raised to 60 ° C. After addition of sensitizing dyes 1 and 2, potassium thiocyanate, bis (1,4,5-trimethyl-1,2,4-triazolium-3-thiolate gold (I)) tetrafluoroborate, carboxymethyltrimethylthio Urea and N, N-dimethylselenourea were added for optimum chemical sensitization. The total of compound 5 and compound 6 is 1 × 10 at the time of chemical sensitization^-4It added so that it might become mol / molAg. Compound 3 and compound 4 were added at the end of chemical sensitization. Thereafter, the total amount of sensitizing dye 4 and sensitizing dye 5 was added so as to be the same as the total amount of sensitizing dyes 1 and 2. Here, optimal chemical sensitization means that the sensitizing dye and each compound are added at a rate of 10 per mole of silver halide.^-1To 10^-8It means that it was selected from the range of molar addition amount.
[0269]
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[0270]
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[0271]
(Em-C5)
Grain formation was performed using the seed emulsion 5 as follows, and sensitization similar to the Em-C4 was performed to prepare Em-C5.
[0272]
<Particle formation>
1211 cc of an aqueous solution containing 46 g of alkali-treated gelatin and 1.7 g of KBr was kept at 75 ° C. and stirred vigorously. After adding 38.4 g of the above-mentioned seed emulsion 3, 0.3 g of modified silicone oil (Nihon Unicar Co., Ltd. product, L7602) was added. H₂SO₄After adjusting pH to 5.5, AgNO₃71 cc of an aqueous solution containing 7.35 g and a mixed aqueous solution of KBr and KI containing 10 mol% of KI were added by the double jet method. At this time, the silver potential was kept at +0 mV with respect to the saturated calomel electrode. After adding 2 mg of sodium benzenethiosulfonate and 2 mg of thiourea dioxide, AgNO3 was used with the stirring device described in JP-A-10-43570.₃Silver iodide fine grains having a silver iodide content of 10 mol%, mixing 800 cc of an aqueous solution containing 178.5 g, 112.5 g of KBr, 800 cc of an aqueous solution containing 17.4 g of KI and 76.2 g of gelatin-4 The silver iodide emulsion was continuously added to the reaction vessel while preparing an emulsion (average size: 0.026 μm). At this time, the silver potential was kept at −30 mV with respect to the saturated calomel electrode. AgNO₃138.5 cc of an aqueous solution containing 58.5 g and a mixed aqueous solution of KBr and KI containing 10 mol% of KI were added by the double jet method. At this time, the silver potential was initially maintained at +20 mV with respect to the saturated calomel electrode, and maintained at +120 mV in the second half.
[0273]
<Formation of epitaxial part>
Subsequently, the temperature was lowered to 50 ° C., 138 cc of 0.3% KI aqueous solution was added, and sensitizing dyes 1 and 2 were added. After stirring at 50 ° C., 140 cc of an aqueous solution containing 8.05 g of NaCl was added. Then AgNO₃79.9 cc of an aqueous solution containing 12.8 g of silver iodide, and a silver iodide fine grain emulsion (Ag amount, 0.05 mol, average silver iodide content 3 mol%, average sphere equivalent diameter: 0.09 μm) prepared in advance. Added to the reaction vessel. At this time, AgNO to be added₃8.0 × 10 to 1 mol^-4mol K₄[RuCN₆] Was present. Thereafter, sensitizing dyes 1 and 2 were added. After washing with water, gelatin was added to adjust the pH to 5.8 and pAg 8.7 at 40 ° C.
[0274]
(Em-C6)
Em-C6 was obtained by changing the sensitized portion of Em-B5 as follows.
[0275]
After adding compounds 1 and 2, the temperature was raised to 60 ° C. After addition of sensitizing dyes 1 and 2, potassium thiocyanate, bis (1,4,5-trimethyl-1,2,4-triazolium-3-thiolate gold (I)) tetrafluoroborate, carboxymethyltrimethylthio Urea and N, N-dimethylselenourea were added for optimum chemical sensitization. The total of compound 5 and compound 6 is 1 × 10 at the time of chemical sensitization^-4It added so that it might become mol / molAg. Compound 3 and compound 4 were added at the end of chemical sensitization. Here, optimal chemical sensitization means that the sensitizing dye and each compound are added at a rate of 10 per mole of silver halide.^-1To 10^-8It means that it was selected from the range of molar addition amount.
[0276]
(Em-B)
1192 ml of an aqueous solution containing 0.96 g of low molecular weight gelatin and KBr, 0.9 g was kept at 40 ° C. and stirred vigorously. AgNO₃37.5 ml of an aqueous solution containing 1.49 g and 37.5 ml of an aqueous solution containing 1.5 g of KBr were added over 30 seconds by the double jet method. After adding 1.2 g of KBr, the mixture was heated to 75 ° C. and aged. After sufficiently aging, 30 g of trimellitated gelatin having a mass average molecular weight of 100,000, whose amino group was chemically modified with trimellitic acid, was added, and the pH was adjusted to 7. 6 mg of thiourea dioxide was added. AgNO₃, 29 g of an aqueous solution containing 29 g and an aqueous KBr solution were added by a double jet method so that the final flow rate was 3 times the initial flow rate. At this time, the silver potential was kept at −20 mV with respect to the saturated calomel electrode. AgNO₃, 440.6 ml of an aqueous solution containing 110.2 g and an aqueous KBr solution were added over 30 minutes while accelerating the flow rate so that the final flow rate was 5.1 times the initial flow rate by the double jet method. At this time, the silver iodide fine grain emulsion used in the preparation of Em-A1 was added while simultaneously accelerating the flow rate so that the silver iodide content was 15.8 mol%, and the silver potential was 0 mV to the saturated calomel electrode. Kept. AgNO₃, 94.1 ml of an aqueous solution containing 24.1 g and an aqueous KBr solution were added over 3 minutes by the double jet method. At this time, the silver potential was kept at 0 mV. After adding 26 mg of sodium ethylthiosulfonate, the temperature was lowered to 55 ° C., and an aqueous KBr solution was added to adjust the silver potential to −90 mV. 8.5 g of the silver iodide fine grain emulsion described above was added in terms of KI mass. Immediately after the addition, AgNO₃, 228 ml of an aqueous solution containing 57 g was added over 5 minutes. At this time, it adjusted with KBr aqueous solution so that the electric potential at the time of completion | finish of addition might be + 20mV. It was washed with water in the same manner as Em-A1, and chemically sensitized.
[0277]
(Em-C)
1192 ml of an aqueous solution containing 1.02 g of phthalated gelatin containing 35 μmol of methionine per gram and having a mass average molecular weight of 100,000 and a phthalation rate of 97% and 0.97 g of KBr was maintained at 35 ° C. and stirred vigorously. AgNO₃, 4.47 g of an aqueous solution, 42 ml and KBr, 3.16 g of an aqueous solution, 42 ml were added over 9 seconds by the double jet method. After adding 2.6 g of KBr, the temperature was raised to 66 ° C. and fully aged. After completion of aging, 41.2 g of trimellitated gelatin having a mass average molecular weight of 100,000 used in the preparation of Em-B and NaCl, 18.5 g were added. After adjusting the pH to 7.2, 8 mg of dimethylamine borane was added. AgNO₃, 26 g of an aqueous solution containing 26 g and an aqueous KBr solution were added by a double jet method so that the final flow rate was 3.8 times the initial flow rate. At this time, the silver potential was kept at −30 mV with respect to the saturated calomel electrode. AgNO₃, 440.6 ml of an aqueous solution containing 110.2 g and an aqueous KBr solution were added over 24 minutes while accelerating the flow rate so that the final flow rate was 5.1 times the initial flow rate by the double jet method. At this time, the silver iodide fine grain emulsion used in the preparation of Em-A1 was simultaneously added at a flow rate acceleration so that the silver iodide content was 2.3 mol%, and the silver potential was- It was kept at 20 mV. After adding 10.7 ml of 1N aqueous potassium thiocyanate solution, AgNO₃153.5 ml of an aqueous solution containing 24.1 g and an aqueous KBr solution were added over 2 minutes 30 seconds by the double jet method. At this time, the silver potential was kept at 10 mV. An aqueous KBr solution was added to adjust the silver potential to -70 mV. 6.4 g of the above-described silver iodide fine grain emulsion was added in terms of KI mass. Immediately after the addition, AgNO₃, 57 g of an aqueous solution containing 57 g was added over 45 minutes. At this time, it adjusted with KBr aqueous solution so that the electric potential at the time of completion | finish of addition might be -30mV. It was washed with water in the same manner as Em-A1, and chemically sensitized.
[0278]
(Em-D)
AgNO during nucleation in the preparation of Em-C₃The addition amount was changed to 2.0 times. And the final AgNO₃, 57 g of an aqueous solution containing 57 g was changed to adjust with a KBr aqueous solution so that the potential at the end of addition was +90 mV. Otherwise, it was prepared in substantially the same manner as Em-C.
[0279]
(Em-E)
1200 ml of an aqueous solution containing 0.2 g of modified silicone oil used in the preparation of low molecular weight gelatin having a weight average molecular weight of 15000, 0.71 g, KBr, 0.92 g, and Em-A1, is maintained at 39 ° C., and the pH is adjusted to 1.8. And stirred vigorously. AgNO₃An aqueous solution containing 0.45 g and an aqueous KBr solution containing 1.5 mol% KI were added over 17 seconds by the double jet method. At this time, the excessive concentration of KBr was kept constant. The temperature was raised to 56 ° C. and aging was performed. After fully ripening, 20 g of phthalated gelatin having a weight average molecular weight of 100,000 and a phthalation rate of 97% containing 35 μmol of methionine per gram was added. After adjusting the pH to 5.9, KBr, 2.9 g, was added. AgNO₃, 288 ml of an aqueous solution containing 28.8 g and an aqueous KBr solution were added over 53 minutes by the double jet method. At this time, the silver iodide fine grain emulsion used in the preparation of Em-A1 was simultaneously added so that the silver iodide content was 4.1 mol%, and the silver potential was kept at −60 mV with respect to the saturated calomel electrode. . After adding KBr, 2.5g, AgNO₃, 87.7 g of aqueous solution and KBr aqueous solution were added over 63 minutes while accelerating the flow rate so that the final flow rate was 1.2 times the initial flow rate by the double jet method. At this time, the above-described silver iodide fine grain emulsion was added at the same time with the flow rate accelerated so that the silver iodide content was 10.5 mol%, and the silver potential was kept at -70 mV. After adding 1 mg of thiourea dioxide, AgNO₃, 41.8 g of aqueous solution 132 ml and KBr aqueous solution were added over 25 minutes by the double jet method. The addition of the aqueous KBr solution was adjusted so that the potential at the end of the addition was +20 mV. After adding 2 mg of sodium benzenethiosulfonate, the pH was adjusted to 7.3. After KBr was added to adjust the silver potential to -70 mV, 5.73 g of the above-described silver iodide fine grain emulsion was added in terms of KI mass. Immediately after the addition, AgNO₃, 66.4 g of aqueous solution 609 ml was added over 10 minutes. During the initial 6 minutes of addition, the silver potential was kept at -70 mV with an aqueous KBr solution. After washing with water, gelatin was added and adjusted to pH 6.5, pAg, 8.2 at 40 ° C. After adding compounds 1 and 2, the temperature was raised to 56 ° C. After adding 0.0004 mol of the above-described silver iodide fine grain emulsion to 1 mol of silver, sensitizing dyes 6 and 7 were added. Potassium thiocyanate, chloroauric acid, sodium thiosulfate and N, N-dimethylselenourea were added for optimum chemical sensitization. Compounds 3 and 4 were added at the end of chemical sensitization.
[0280]
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[0281]
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[0282]
(Em-F)
AgNO during nucleation in the preparation of Em-E₃It was prepared in substantially the same manner as Em-E except that the addition amount was changed to 3.1 times. However, the sensitizing dye of Em-E was changed to sensitizing dyes 8, 9 and 10.
[0283]
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[0284]
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[0285]
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[0286]
(Em-G)
Maintain a pH of 33O 0 C in an aqueous solution containing 0.20 g of modified silicone oil used in the preparation of 0.70 g of low molecular weight gelatin with a weight average molecular weight of 15000, KBr, 0.9 g, KI, 0.175 g and Em-A1. Prepared to 1.8 and stirred vigorously. AgNO₃An aqueous solution containing 1.8 g and an aqueous KBr solution containing 3.2 mol% KI were added over 9 seconds by the double jet method. At this time, the excessive concentration of KBr was kept constant. The temperature was raised to 69 ° C. and aging was performed. After completion of ripening, 27.8 g of trimellitated gelatin obtained by chemically modifying an amino group having a mass average molecular weight of 100,000 containing 35 μmol of methionine per gram with trimellitic acid was added. After adjusting the pH to 6.3, KBr, 2.9 g, was added. AgNO₃, 270 ml of an aqueous solution containing 27.58 g and an aqueous KBr solution were added over 37 minutes by the double jet method. At this time, a low molecular weight gelatin aqueous solution having a mass average molecular weight of 15000 and AgNO 3₃A silver iodide fine grain emulsion having a grain size of 0.008 μm prepared by mixing an aqueous solution and an aqueous KI solution immediately before addition in another chamber having a magnetic coupling induction stirrer described in JP-A-10-43570 is prepared. It added simultaneously so that a silver halide content rate might be 4.1 mol%, and silver potential was kept at -60mV with respect to a saturated calomel electrode. After adding KBr, 2.6 g, AgNO₃, 87.7 g of aqueous solution and KBr aqueous solution were added over 49 minutes by the double jet method so that the final flow rate was 3.1 times the initial flow rate. At this time, the silver iodide fine grain emulsion prepared by mixing immediately before the above addition was simultaneously accelerated so that the silver iodide content was 7.9 mol%, and the silver potential was kept at -70 mV. After adding 1 mg of thiourea dioxide, AgNO₃, 41.8 g of aqueous solution 132 ml and KBr aqueous solution were added over 20 minutes by the double jet method. The addition of the aqueous KBr solution was adjusted so that the potential at the end of the addition was +20 mV. After raising the temperature to 78 ° C. and adjusting the pH to 9.1, KBr was added to bring the potential to −60 mV. 5.73 g of the silver iodide fine grain emulsion used in the preparation of Em-A1 was added in terms of KI mass. Immediately after the addition, AgNO₃, 36.4 ml of an aqueous solution containing 66.4 g was added over 4 minutes. The silver potential was kept at −60 mV with an aqueous KBr solution for 2 minutes at the beginning of the addition. It was washed with water in the same manner as Em-F and chemically sensitized.
[0287]
(Em-H)
An aqueous solution containing 17.8 g of ion-exchanged gelatin having a weight average molecular weight of 100,000, KBr, 6.2 g, KI, and 0.46 g was kept at 45 ° C. and vigorously stirred. AgNO₃An aqueous solution containing 11.85 g and an aqueous solution containing 3.8 g of KBr were added over 47 seconds by the double jet method. After raising the temperature to 63 ° C., 24.1 g of ion-exchanged gelatin having a mass average molecular weight of 100,000 was added and ripened. After fully ripening, AgNO₃An aqueous solution containing 133.4 g and an aqueous KBr solution were added over 20 minutes by the double jet method so that the final flow rate was 2.6 times the initial flow rate. At this time, the silver potential was kept at +40 mV with respect to the saturated calomel electrode. 10 minutes after the start of addition₂IrCl₆0.1 mg of was added. After adding 7g of NaCl, AgNO₃Of 45.6 g and an aqueous KBr solution were added over 12 minutes by the double jet method. At this time, the silver potential was kept at +90 mV. Further, 100 ml of an aqueous solution containing 29 mg of yellow blood salt was added over 6 minutes from the start of addition. After the addition of 14.4 g of KBr, 6.3 g of the silver iodide fine grain emulsion used in the preparation of Em-A1 was added in terms of KI mass. Immediately after the addition, AgNO₃An aqueous solution containing 42.7 g and an aqueous KBr solution were added over 11 minutes by the double jet method. At this time, the silver potential was kept at +90 mV. It was washed with water in the same manner as Em-F and chemically sensitized.
[0288]
(Em-I)
Em-H was prepared in substantially the same manner except that the temperature during nucleation was changed to 38 ° C.
[0289]
(Em-J)
1200 ml of an aqueous solution containing phthalated gelatin having a phthalation rate of 97% and a weight average molecular weight of 100,000, phthalated gelatin, 0.38 g, KBr, and 0.99 g was maintained at 60 ° C., adjusted to pH 2 and vigorously stirred. AgNO₃An aqueous solution containing 1.96 g and an aqueous solution containing KBr, 1.97 g, KI, and 0.172 g were added over 30 seconds by the double jet method. After completion of ripening, 12.8 g of trimellitated gelatin obtained by chemically modifying an amino group having a mass average molecular weight of 100,000 containing 35 μmol of methionine per gram with trimellitic acid was added. After adjusting the pH to 5.9, KBr, 2.99 g and NaCl 6.2 g were added. AgNO₃20.7 g of aqueous solution and KBr aqueous solution were added over 35 minutes by the double jet method. At this time, the silver potential was kept at −50 mV with respect to the saturated calomel electrode. AgNO₃, 65.6 g of aqueous solution and KBr aqueous solution were added over 37 minutes while accelerating the flow rate so that the final flow rate was 2.1 times the initial flow rate by the double jet method. At this time, the silver iodide fine grain emulsion used in the preparation of Em-A1 was added while simultaneously accelerating the flow rate so that the silver iodide content was 6.5 mol%, and the silver potential was kept at -50 mV. After adding 1.5 mg of thiourea dioxide, AgNO₃, 41.8 g of aqueous solution 132 ml and KBr aqueous solution were added over 13 minutes by the double jet method. The addition of the aqueous KBr solution was adjusted so that the silver potential at the end of the addition was +40 mV. After adding 2 mg of sodium benzenethiosulfonate, KBr was added to adjust the silver potential to -100 mV. The above silver iodide fine grain emulsion was added in an amount of 6.2 g in terms of KI mass. Immediately after the addition, AgNO₃, 88.5 g of aqueous solution 300 ml was added over 8 minutes. Adjustment was made by adding an aqueous KBr solution so that the potential at the end of the addition was +60 mV. After washing with water, gelatin was added and adjusted to pH 6.5, pAg, 8.2 at 40 ° C. After adding compounds 1 and 2, the temperature was raised to 61 ° C. After addition of sensitizing dyes 11, 12, 13 and 14, K₂IrCl₆, Potassium thiocyanate, chloroauric acid, sodium thiosulfate and N, N-dimethylselenourea were added for optimum chemical sensitization. Compounds 3 and 4 were added at the end of chemical sensitization.
[0290]
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[0291]
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[0292]
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[0293]
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[0294]
(Em-K)
1200 ml of an aqueous solution containing 4.9 g of low molecular weight gelatin having a weight average molecular weight of 15000, KBr, and 5.3 g was kept at 60 ° C. and stirred vigorously. AgNO₃27 ml of an aqueous solution containing 8.75 g and 36 ml of an aqueous solution containing KBr, 6.45 g were added by the double jet method over 1 minute. After heating to 77 ° C, AgNO₃, 21 ml of an aqueous solution containing 6.9 g was added over 2.5 minutes. NH₄NO₃, 26 g, 1 N, NaOH, and 56 ml were sequentially added, followed by aging. After completion of aging, the pH was adjusted to 4.8. AgNO₃, 438 ml of an aqueous solution containing 141 g and 458 ml of an aqueous solution containing 102.6 g of KBr were added by a double jet method so that the final flow rate was four times the initial flow rate. After dropping to 55 ° C, AgNO₃, 7.1 g of an aqueous solution containing 7.1 g and an aqueous solution containing 6.46 g of KI were added over 5 minutes by the double jet method. After adding 7.1 g of KBr, sodium benzenethiosulfonate, 4 mg and K₂IrCl₆, 0.05 mg was added. AgNO₃, 177 ml of an aqueous solution containing 57.2 g and 223 ml of an aqueous solution containing 40.2 g of KBr were added by the double jet method over 8 minutes. It was washed with water in the same manner as Em-J and chemically sensitized.
[0295]
(Em-L)
Em-K was prepared in substantially the same manner except that the temperature during nucleation was changed to 42 ° C.
[0296]
(Em-M, N, O)
Prepared in substantially the same manner as Em-H or Em-I. However, chemical sensitization was carried out in substantially the same manner as Em-J.
[0297]
(Em-P)
For Em-J, the sensitizing dye was changed to 5, 6 and 7, and chemical sensitization was optimally performed to obtain Em-P.
[0298]
The morphological characteristics of Em-A1 to A8, Em-B1 to B6, and Em-C1 to C6 thus obtained are shown in Table 1, Em-A1 to A8, Em-B1 to B6, Em-C1 to C6, and The particle characteristics of Em-B to P are summarized in Table 2.
[0299]
[Table 1-1]

[0300]
[Table 1-2]

[0301]
[Table 2]

[0302]
1) Support
The support used in this example was prepared by the following method.
100 parts by mass of polyethylene-2,6-naphthalate polymer and Tinuvin P.I. 326 (manufactured by Ciba-Geigy Ciba-Geigy) was dried, melted at 300 ° C, extruded from a T-die, and stretched 3.3 times at 140 ° C, followed by 130 ° C. The film was stretched by 3.3 times and further heat-fixed at 250 ° C. for 6 seconds to obtain a PEN (polyethylene naphthalate) film having a thickness of 90 μm. The PEN film has a blue dye, a magenta dye, and a yellow dye (public techniques: I-1, I-4, I-6, I-24, I-26, I-27 described in public technical number 94-6023). II-5) was added in an appropriate amount. Furthermore, it was wound around a stainless steel core having a diameter of 20 cm to give a thermal history of 110 ° C. and 48 hours, thereby providing a support that is difficult to curl.
[0303]
2) Application of undercoat layer
The support was subjected to corona discharge treatment, UV discharge treatment, and glow discharge treatment on both sides, and then gelatin 0.1 g / m on each side.²Sodium α-sulfodi-2-ethylhexyl succinate 0.01 g / m², Salicylic acid 0.04 g / m²P-chlorophenol 0.2 g / m², (CH₂= CHSO₂CH₂CH₂NHCO)₆CH₂0.012 g / m²Polyamide-epichlorohydrin polycondensate 0.02 g / m²Apply a primer solution (10cc / m², Using a bar coater), an undercoat layer was provided on the high-temperature surface side during stretching. Drying was carried out at 115 ° C. for 6 minutes (all rollers and transport devices in the drying zone were at 115 ° C.).
[0304]
3) Coating the back layer
An antistatic layer having the following composition, a magnetic recording layer, and a sliding layer were coated as a back layer on one surface of the support after the undercoating.
[0305]
3-1) Application of antistatic layer
The specific resistance of the tin oxide-antimony oxide composite having an average particle size of 0.005 μm is 0.2 g / m of a dispersion of fine particle powder (secondary aggregate particle size of about 0.08 μm) of 5 Ω · cm.², Gelatin 0.05g / m², (CH₂= CHSO₂CH₂CH₂NHCO)₂CH₂  0.02 g / m², Poly (degree of polymerization 10) oxyethylene-p-nonylphenol 0.005 g / m²And coated with resorcin.
[0306]
3-2) Coating of magnetic recording layer
Cobalt-γ-iron oxide coated with 3-poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (15% by mass) (specific surface area 43 m²/ G, long axis 0.14 μm, single axis 0.03 μm, saturation magnetization 89 Am²/ Kg, Fe⁺²/ Fe⁺³= 6/94, the surface is treated with aluminum oxide silicon oxide with 2% by mass of iron oxide) 0.06 g / m²Diacetylcellulose 1.2 g / m²(Iron oxide was dispersed with an open kneader and sand mill)₂H₅C (CH₂OCONH-C₆H₃(CH₃) NCO)₃0.3 g / m²Was coated with a bar coater using acetone, methyl ethyl ketone, and cyclohexanone as a solvent to obtain a magnetic recording layer having a thickness of 1.2 μm. 10 mg each of abrasive aluminum oxide (0.15 μm) coated with silica particles (0.3 μm) and 3-poly (polymerization degree 15) oxyethylene-propyloxytrimethoxysilane (15% by mass) as a matting agent / M²It added so that it might become. Drying was performed at 115 ° C. for 6 minutes (all rollers and conveyors in the drying zone were 115 ° C.). The increase in DB color density of the magnetic recording layer in the X-light (blue filter) is about 0.1, and the saturation magnetization moment of the magnetic recording layer is 4.2 Am.²/ Kg, coercive force 7.3 × 10⁴A / m, the squareness ratio was 65%.
[0307]
3-3) Preparation of sliding layer
Diacetylcellulose (25mg / m²), C₆H₁₃CH (OH) C₁₀H₂₀COOC₄₀H₈₁(Compound a, 6 mg / m²) / C₅₀H₁₀₁O (CH₂CH₂O)₁₆H (Compound b, 9 mg / m²) The mixture was applied. This mixture was prepared by melting at 105 ° C. in xylene / propylene monomethyl ether (1/1), pouring and dispersing in propylene monomethyl ether at room temperature (10-fold amount), and then dispersing the dispersion ( The average particle size was 0.01 μm) and then added. 15 mg / m each of aluminum oxide (0.15 μm) coated with silica particles (0.3 μm) and 3-poly (polymerization degree 15) oxyethylenepropyloxytrimethoxysilane (15% by mass) as a matting agent²It added so that it might become. Drying was performed at 115 ° C. for 6 minutes (all rollers and transport devices in the drying zone were 115 ° C.). The sliding layer has a dynamic friction coefficient of 0.06 (5 mmφ stainless hard ball, load of 100 g, speed of 6 cm / min), static friction coefficient of 0.07 (clipping method), and the dynamic friction coefficient of the emulsion surface and sliding layer described later is also 0.12. Excellent characteristics.
[0308]
4) Coating of photosensitive layer
Next, on the opposite side of the back layer obtained above, each layer having the following composition was applied in layers to prepare Samples 101 to 120 as color negative photosensitive materials. That is, samples 101 to 120 were prepared by replacing the silver iodobromide emulsion Em-A1 in the 14th layer with emulsions Em-A1 to A8, Em-B1 to B6, and Em-C1 to C6, respectively.
[0309]
(Composition of photosensitive layer)
The main materials used in each layer are classified as follows:
ExC: Cyan coupler UV: UV absorber
ExM: Magenta coupler HBS: High boiling point organic solvent
ExY: Yellow coupler H: Gelatin hardener
(Specific compounds are described below, followed by a numerical value followed by a chemical formula.)
The number corresponding to each component is g / m²The coating amount expressed in units is shown. For silver halide, the coating amount in terms of silver is shown. AgBrI (2) represents an emulsion grain having a silver iodide content of 2 mol%.
[0310]
(Sample 101)
First layer (first antihalation layer)
Black colloidal silver Silver 0.155
0.07 μm surface fogging AgBrI (2) Silver 0.01
Gelatin 0.87
ExC-1 0.002
ExC-3 0.002
Cpd-2 0.001
HBS-1 0.004
S-37 0.002.
[0311]
Second layer (second antihalation layer)
Black colloidal silver Silver 0.066
Gelatin 0.407
ExM-1 0.050
ExF-1 2.0 × 10^-3
HBS-1 0.074
Solid disperse dye ExF-2 0.015
Solid disperse dye ExF-3 0.020.
[0312]
Third layer (intermediate layer)
0.07 μm AgBrI (2) 0.020
ExC-2 0.022
Cpd-1 0.05
HSB-1 0.05
Polyethyl acrylate latex 0.085
Gelatin 0.294.
[0313]
4th layer (low sensitivity red sensitive emulsion layer)
Silver iodobromide emulsion Em-M Silver 0.065
Silver iodobromide emulsion Em-N Silver 0.100
Silver iodobromide emulsion Em-O Silver 0.158
ExC-1 0.109
ExC-3 0.044
ExC-4 0.072
ExC-5 0.011
ExC-6 0.003
ExC-8 0.03
Cpd-2 0.025
Cpd-4 0.025
HBS-1 0.17
Gelatin 0.80.
[0314]
5th layer (medium sensitivity red emulsion layer)
Silver iodobromide emulsion Em-K Silver 0.21
Silver iodobromide emulsion Em-L Silver 0.62
ExC-1 0.14
ExC-2 0.026
ExC-3 0.020
ExC-4 0.12
ExC-5 0.016
ExC-6 0.007
ExC-8 0.03
Cpd-2 0.036
Cpd-4 0.028
HBS-1 0.16
Gelatin 1.18.
[0315]
6th layer (high-sensitivity red-sensitive emulsion layer)
Silver iodobromide emulsion Em-J Silver 1.67
ExC-1 0.18
ExC-3 0.07
ExC-6 0.047
Cpd-2 0.046
Cpd-4 0.077
HBS-1 0.37
Gelatin 2.12.
[0316]
7th layer (intermediate layer)
Cpd-1 0.089
Solid disperse dye ExF-4 0.030
HBS-1 0.050
Polyethyl acrylate latex 0.83
Gelatin 0.84.
[0317]
Eighth layer (Multilayer effect donor layer (layer that gives a multilayer effect to the red-sensitive layer))
Silver iodobromide emulsion Em-E Silver 0.560
Cpd-4 0.030
ExM-2 0.096
ExM-3 0.028
ExY-1 0.031
ExG-1 0.006
HBS-1 0.085
HBS-3 0.003
Gelatin 0.58.
[0318]
9th layer (low sensitivity green emulsion layer)
Silver iodobromide emulsion Em-G Silver 0.39
Silver iodobromide emulsion Em-H Silver 0.28
Silver iodobromide emulsion Em-I Silver 0.35
ExM-2 0.36
ExM-3 0.045
ExG-1 0.005
HBS-1 0.28
HBS-2 0.01
S-2 0.27
Gelatin 1.39.
[0319]
10th layer (medium sensitive green sensitive emulsion layer)
Silver iodobromide emulsion Em-F Silver 0.20
Silver iodobromide emulsion Em-G Silver 0.25
ExC-6 0.009
ExC-8 0.01
ExM-2 0.031
ExM-3 0.029
ExY-1 0.006
ExM-4 0.028
ExG-1 0.005
HBS-1 0.064
HBS-2 2.1 × 10^-3
Gelatin 0.44.
[0320]
11th layer (high sensitivity green emulsion layer)
Emulsion Em-P Silver 1.200
ExC-6 0.004
ExC-8 0.01
ExM-1 0.016
ExM-3 0.036
ExM-4 0.020
ExM-5 0.004
ExY-5 0.008
ExM-2 0.013
Cpd-4 0.007
HBS-1 0.18
Polyethyl acrylate latex 0.099
Gelatin 1.11.
[0321]
12th layer (yellow filter layer)
Yellow colloidal silver Silver 0.047
Cpd-1 0.16
Solid disperse dye ExF-5 0.010
Solid disperse dye ExF-6 0.010
HBS-1 0.082
Gelatin 1.057.
[0322]
13th layer (low sensitivity blue-sensitive emulsion layer)
Silver iodobromide emulsion Em-B Silver 0.18
Silver iodobromide emulsion Em-C Silver 0.20
Silver iodobromide emulsion Em-D Silver 0.07
ExC-1 0.041
ExY-1 0.035
ExY-2 0.71
ExY-3 0.10
ExY-4 0.005
Cpd-2 0.10
Cpd-3 4.0 × 10^-3
HBS-1 0.24
Gelatin 1.41.
[0323]
14th layer (high sensitivity blue-sensitive emulsion layer)
Silver iodobromide emulsion Em-A1 Silver 0.75
ExC-1 0.013
ExY-2 0.31
ExY-3 0.05
ExY-6 0.062
Cpd-2 0.075
Cpd-3 1.0 × 10^-3
HBS-1 0.10
Gelatin 0.91.
[0324]
15th layer (first protective layer)
0.07 μm AgBrI (2) Silver 0.30
UV-1 0.21
UV-2 0.13
UV-3 0.20
UV-4 0.025
F-11 0.009
F-18 0.005
F-19 0.005
HBS-1 0.12
S-2 5.0 × 10^-2
Gelatin 2.3.
[0325]
16th layer (second protective layer)
H-1 0.40
B-1 (diameter 1.7 μm) 5.0 × 10^-2
B-2 (diameter 1.7 μm) 0.15
B-3 0.05
S-1 0.20
Gelatin 0.75.
[0326]
Furthermore, storage stability, processability, pressure resistance, antifungal and antibacterial properties, B-4 to B-6, F-1 to F-18, and iron salts, lead salts, gold salts, platinum salts, as appropriate for each layer , Palladium salt, iridium salt, ruthenium salt and rhodium salt are contained. In addition, 8.5 × 10 5 per mol of silver halide in the eighth layer coating solution.^-3g, 7.9 × 10 in the eleventh layer^-3A sample was prepared by adding g calcium in an aqueous calcium nitrate solution. Further, in order to improve the antistatic property, it contains at least one kind of W-1, W-6, W-7 and W-8, and at least one kind of W-2 and W-5 in order to improve the coatability. Contains.
[0327]
Preparation of organic solid disperse dyes
The following ExF-3 was dispersed by the following method. That is, 21.7 ml of water and 3 ml of p-octylphenoxyethoxyethoxyethane sulfonic acid soda in 5% aqueous solution and 0.5 g of 5% aqueous solution of p-octylphenoxypolyoxyethylene ether (degree of polymerization 10) in 700 ml In a pot mill, 5.0 g of dye ExF-3 and 500 ml of zirconium oxide beads (diameter 1 mm) were added, and the contents were dispersed for 2 hours. A BO-type vibrating ball mill manufactured by Chuo Koki was used for this dispersion. After dispersion, the contents were taken out and added to 8 g of a 12.5% aqueous gelatin solution, and the beads were removed by filtration to obtain a gelatin dispersion of the dye. The average particle size of the dye fine particles was 0.44 μm.
[0328]
Similarly, a solid disperse dye ExF-4 was obtained. The average particle diameter of the dye fine particles was 0.24 μm. ExF-2 was dispersed by the microprecipitation dispersion method described in Example 1 of EP 549,489A. The average particle size was 0.06 μm.
[0329]
A solid dispersion of ExF-6 was dispersed by the following method.
To 2800 g of ExF-6 wet cake containing 18% of water, 376 g of 4000 g of water and a 3% solution of W-2 was added and stirred to obtain a slurry of ExF-6 having a concentration of 32%. Next, 1700 ml of zirconia beads having an average particle diameter of 0.5 mm was filled in Ultraviscomil (UVM-2) manufactured by Imex Co., Ltd., and the peripheral speed was about 10 m / sec through the slurry, and the discharge rate was 0.5 l / min for 8 hours. Crushed. The average particle size was 0.45 μm.
[0330]
The compounds used for forming each of the above layers are as shown below.
[0331]
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[0332]
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[0333]
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[0334]
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[0335]
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[0336]
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[0337]
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[0338]
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[0339]
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[0340]
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[0341]
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[0342]
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[0343]
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[0344]
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[0345]
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[0346]
Embedded image

[0347]
The sample evaluation method is as follows. The film was exposed for 1/100 second through a gelatin filter SC-39 (long wavelength light transmission filter having a cut-off wavelength of 390 nm) and a continuous wedge manufactured by FUJIFILM Corporation. Development was performed as follows using an automatic processor FP-360B manufactured by Fuji Photo Film Co., Ltd. In addition, the overflow solution of the bleaching bath was remodeled so as not to flow to the rear bath but to discharge all to the waste liquid tank. This FP-360B is equipped with the evaporation correction means described in JIII Journal of Technical Disclosure No. 94-4992.
The treatment process and the treatment liquid composition are shown below.
[0348]
(Processing process)
Process Processing time Processing temperature Replenishment amount * Tank capacity
Color development 3 minutes 5 seconds 37.8 ° C 20 ml 11.5 liters
Whitening 50 seconds 38.0 ℃ 5ml 5l
Fixing (1) 50 seconds 38.0 ℃-5 liters
Fixing (2) 50 seconds 38.0 ° C 8ml 5l
Washing with water 30 seconds 38.0 ° C 17 ml 3 liters
Stable (2) 20 seconds 38.0 ° C 15 ml 3 liters
Drying 1 minute 30 seconds 60.0 ° C
* Replenishment amount per photosensitive material 35mm width 1.1m (equivalent to 24Ex. 1)
The stabilizing solution and the fixing solution were counter-current from (2) to (1), and all the overflow solution of the washing water was introduced into the fixing bath (2). The amount of developer brought into the bleaching process, the amount of bleaching solution brought into the fixing step, and the amount of fixing solution brought into the water washing step were 2.5 ml and 2.0 ml per 1.1 mm width of the photosensitive material 35 mm, respectively. It was milliliter and 2.0 milliliter. In addition, the crossover time is 6 seconds, and this time is included in the processing time of the previous process.
[0349]
The opening area of the processor is 100 cm with color developer.², 120cm with bleach²Other processing solutions are about 100cm²Met.
[0350]
The composition of the treatment liquid is shown below.

[0351]
(Bleaching solution) Tank solution (g) Replenisher solution (g)
1,3-diaminopropanetetraacetic acid second
Iron ammonium monohydrate 113 170
Ammonium bromide 70 105
Ammonium nitrate 14 21
Succinic acid 34 51
Maleic acid 28 42
Add water 1.0 liter 1.0 liter
pH [adjusted with aqueous ammonia] 4.6 4.0.
[0352]
(Fixing (1) Tank liquid)
5:95 (volume ratio) mixture of the above bleach tank solution and the following fixing tank solution
(PH 6.8).
[0353]
(Fixing (2)) Tank liquid (g) Replenisher (g)
Ammonium thiosulfate aqueous solution 240 ml 720 ml
(750g / liter)
Imidazole 7 21
Ammonium methanethiosulfonate 5 15
Ammonium methanesulfinate 10 30
Ethylenediaminetetraacetic acid 13 39
Add water 1.0 liter 1.0 liter
pH [adjusted with aqueous ammonia and acetic acid] 7.4 7.45.
[0354]
(Washing water)
Tap water is passed through a mixed bed column packed with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH-type strongly basic anion exchange resin (Amberlite IR-400). Then, the calcium and magnesium ion concentrations were adjusted to 3 mg / liter or less, and then sodium isocyanurate dichloride 20 mg / liter and sodium sulfate 150 mg / liter were added. The pH of this solution was in the range of 6.5 to 7.5.
[0355]
(Stabilizer) Tank fluid and replenisher common (Unit: g)
Sodium p-toluenesulfinate 0.03
Polyoxyethylene-p-monononylphenyl ether 0.2
(Average polymerization degree 10)
1,2-Benzisothiazoline-3-one sodium 0.10
Ethylenediaminetetraacetic acid disodium salt 0.05
1,2,4-triazole 1.3
1,4-bis (1,2,4-triazole-1-
Ilmethyl) piperazine 0.75
Add water and add 1.0 liter
pH 8.5.
[0356]
The said process was performed with respect to the samples 101-120. Photographic performance was evaluated by measuring the density of the processed sample with a blue filter. The obtained results are shown in Table 3.
[0357]
From Table 3, the sample using the emulsion of the present invention achieves high sensitivity while improving the graininess compared to the comparative sample.
[0358]
[Table 3]

[0359]
[Example 2]
Preparation of (seed emulsion 9)
1200 cc of an aqueous solution containing 0.9 g of KBr and 1 g of the gelatin-3 was kept at 35 ° C. and stirred (1st solution adjustment).
[0360]
Ag-1 aqueous solution (AgNO₃37.5 cc) (concentration 0.29M) and 55 cc of X-1 aqueous solution (the gelatin-3 concentration 15.5 g / L, KBr concentration 0.295M) were simultaneously added at a constant flow rate. (Addition 1).
[0361]
Thereafter, 6 g of KBr was added, and the temperature was raised to 75 ° C. After the temperature increase, 300 cc of an aqueous G-1 solution (the gelatin-2 concentration of 117 g / L) was added. At this time, the pH was adjusted to 5.5.
Next, an Ag-2 aqueous solution (AgNO₃73 cc) was added at a constant flow rate (addition 2).
[0362]
Next, 1 mg of sodium benzenethiosulfonate was added. Ag-3 aqueous solution (AgNO₃209 cc of X-3 aqueous solution (the gelatin-4 concentration of 186.76 g / L, KBr concentration of 0.535 M, KI concentration of 0.0942 M) and 596 cc of the stirrer described in JP-A-10-43570 And a silver halide photographic emulsion containing silver iodobromide ultrafine particles having an average size of 0.025 μm was added continuously immediately after ejection (addition 3). At this time, an X-2 aqueous solution (KBr concentration of 0.525 M) was also added to adjust the silver potential to 0 mV with respect to the saturated calomel electrode. During this time, the pH was adjusted to be maintained between 5 and 6.
[0363]
Thereafter, desalting was performed by a normal flocculation method, and then water, NaOH, and the above gelatin-1 were added with stirring to adjust the pH to 5.8 and the pAg to 8.8.
[0364]
The obtained emulsion was composed of grains having an average silver iodide content of 12 mol%, an average sphere equivalent diameter of 0.38 μm, and an average aspect ratio of 12.
[0365]
Preparation of (seed emulsion 10)
1200 cc of an aqueous solution containing 0.9 g of KBr and 0.14 g of gelatin-3 was kept at 35 ° C. and stirred (1st solution adjustment).
[0366]
Ag-1 aqueous solution (AgNO₃Concentration 0.145M) 37.5 cc, X-1 solution (KBr concentration 0.148M) 55 cc and G-1 solution (gelatin-3 concentration 50 g / L) 81 cc were added simultaneously at a constant flow rate. (Addition 1).
[0367]
Thereafter, 6 g of KBr was added, then 4 g of the gelatin-3 was added, and the temperature was raised to 75 ° C. After the temperature increase, 300 cc of an aqueous solution G-2 (concentration of gelatin-2 at 117 g / L) was added. At this time, the pH was adjusted to 5.5.
Next, an Ag-2 aqueous solution (AgNO₃73 cc) was added at a constant flow rate (addition 2).
[0368]
Next, 1 mg of sodium benzenethiosulfonate was added. Next, an Ag-3 aqueous solution (AgNO₃300cc of X-3 aqueous solution (174.3 g / L of the gelatin-4, KBr concentration of 0.711M, KI concentration of 0.146M) and 300 cc of the stirrer described in JP-A-10-43570 And a silver halide photographic emulsion containing silver iodobromide ultrafine particles having an average size of 0.025 μm was added continuously immediately after ejection (addition 3). At this time, an X-2 aqueous solution (KBr concentration of 0.525 M) was also added to adjust the silver potential to 0 mV with respect to the saturated calomel electrode. During this time, the pH was adjusted to be maintained between 5 and 6.
[0369]
Thereafter, desalting was performed by a normal flocculation method, and then water, NaOH, and the above gelatin-1 were added with stirring to adjust the pH to 5.8 and the pAg to 8.8.
[0370]
The resulting emulsion contained grains having an average silver iodide content of 12 mol%, an average sphere equivalent diameter of 0.38 μm, and an average aspect ratio of 13.
[0371]
Preparation of (seed emulsion 11)
Seed emulsion 2 was prepared with reference to seed emulsion 2.
1200 cc of a dispersion medium solution containing 0.54 g of NaCl and 0.5 g of the gelatin-3 is kept in a reaction vessel at 35 ° C., and while stirring it, an Ag-1 aqueous solution (AgNO 3₃37.5 cc of each of 0.29M halogen salt (KBr, NaCl) aqueous solution (X-1) adjusted to have a molar ratio of KBr / NaCl of 80/20 and silver nitrate of 0.29M) Added.
[0372]
Then, after addition 1, 6.5 g of KBr was added, and the temperature was raised to 75 ° C. After the temperature rise, 300 cc of an aqueous G-1 solution (concentration of gelatin-2 of 117 g / L) was added. At this time, the pH was adjusted to 5.5.
[0373]
Next, an Ag-2 aqueous solution (AgNO₃73 cc) was added at a constant flow rate (addition 2).
[0374]
Next, 1 mg of sodium benzenethiosulfonate was added. Ag-3 aqueous solution (AgNO₃13.8 cc) and 3380 cc of an X-3 aqueous solution (the gelatin-4 concentration 186.76 g / L, KBr concentration 0.566M, KI concentration 0.0629M) described in JP-A-10-43570 And a silver halide photographic emulsion containing silver iodobromide ultrafine particles having an average size of 0.025 μm was added continuously immediately after ejection (addition 3). At this time, an X-2 aqueous solution (KBr concentration of 0.525 M) was also added to adjust the silver potential to 0 mV with respect to the saturated calomel electrode. During this time, the pH was adjusted to be maintained between 5 and 6.
[0375]
Thereafter, desalting was performed by a normal flocculation method, and then water, NaOH, and the above gelatin-1 were added with stirring to adjust the pH to 5.8 and the pAg to 8.8.
[0376]
The resulting emulsion contained grains having an average silver iodide content of 9.5 mol%, an average sphere equivalent diameter of 0.85 μm, and an average aspect ratio of 33.
[0377]
Preparation of (seed emulsion 12)
Seed emulsion 12 was prepared with reference to seed emulsion 2.
1200 cc of an aqueous solution containing 0.9 g of KBr and 0.5 g of gelatin-3 was maintained at 35 ° C. and stirred (1st solution adjustment).
[0378]
Ag-1 aqueous solution (AgNO₃Halogen salt (KBr, NaCl) aqueous solution (X: 0.29M, gelatin concentration: 7.8 g / L) adjusted to a molar ratio of KBr / NaCl of 95/5. -1) was added simultaneously at 37.5 cc each.
[0379]
Thereafter, 6.5 g of KBr was added, then 4 g of gelatin-3 was added, and the temperature was raised to 75 ° C. After the aging process at an elevated temperature, 300 cc of an aqueous G-1 solution (the gelatin-2 concentration of 117 g / L) was added.
[0380]
Next, an appropriate amount of 1N sulfuric acid was added to adjust the pH to 5.5.
Next, an Ag-2 aqueous solution (AgNO₃73 cc) was added at a constant flow rate (addition 2).
[0381]
Next, 1 mg of sodium benzenethiosulfonate was added. Next, an Ag-3 aqueous solution (AgNO₃1700 cc of X-3 aqueous solution (174.3 g / L of the gelatin-4, KBr concentration of 0.771 M, KI concentration of 0.0857 M) and 1700 cc of the stirrer described in JP-A-10-43570 And a silver halide photographic emulsion containing silver iodobromide ultrafine particles having an average size of 0.025 μm was added continuously immediately after ejection (addition 3). At this time, an X-2 aqueous solution (KBr concentration of 0.525 M) was also added to adjust the silver potential to +40 mV with respect to the saturated calomel electrode. During this time, the pH was adjusted to be maintained between 5 and 6.
[0382]
Thereafter, desalting was performed by a normal flocculation method, and then water, NaOH, and the above gelatin-1 were added with stirring to adjust the pH to 5.8 and the pAg to 8.8.
[0383]
The resulting emulsion contained grains having an average silver iodide content of 9.5 mol%, an average sphere equivalent diameter of 0.85 μm, and an average aspect ratio of 35.
[0384]
(Em-D1)
1211 cc of an aqueous solution containing 46 g of alkali-treated gelatin and 1.7 g of KBr was kept at 75 ° C. and stirred vigorously. After adding 124 g of the above-mentioned seed emulsion 9, 0.3 g of modified silicone oil (Nihon Unicar Co., Ltd. product, L7602) was added. H₂SO₄After adjusting pH to 5.5, AgNO₃An aqueous solution containing 61.4 g of 137.6 cc and a mixed aqueous solution of KBr and KI containing 10 mol% of KI were added by the double jet method. At this time, the silver potential was initially maintained at +20 mV with respect to the saturated calomel electrode and at +120 mV in the second half. After the temperature was lowered to 50 ° C., 57.8 cc of 0.3% KI aqueous solution was added. Immediately thereafter, AgNO₃19.7 cc of an aqueous solution containing 8.8 g, 21 cc of an aqueous solution containing 1.51 g of NaCl and 2.47 g of KBr, and a solution containing 0.005 mol of silver iodide fine particles were added simultaneously. At this time, AgNO to be added₃8.0 × 10 for 1 mol^-4mol K₄[RuCN₆] Was present. Thereafter, a sensitizing dye was added. After washing with water, gelatin was added to adjust the pH to 5.8 and pAg 8.7 at 40 ° C.
[0385]
<Sensitization>
After adding compounds 1 and 2, the temperature was raised to 60 ° C. After adding sensitizing dyes 1 and 2, potassium thiocyanate, chloroauric acid, sodium thiosulfate, and N, N-dimethylselenourea were added for optimum chemical sensitization. Compound 3 and compound 4 were added at the end of chemical sensitization. Here, optimal chemical sensitization means that the sensitizing dye and each compound are 10 per mol of silver halide.^-1To 10^-8It means that it was selected from the range of molar addition amount.
[0386]
(Em-E1)
1211 cc of an aqueous solution containing 46 g of alkali-treated gelatin and 1.7 g of KBr was kept at 75 ° C. and stirred vigorously. After adding 35 g of the above-mentioned seed emulsion 11, 0.3 g of modified silicone oil (Nihon Unicar Co., Ltd. product, L7602) was added. H₂SO₄After adjusting pH to 5.5, AgNO₃Was added by a double jet method with a mixed solution of 71 cc of an aqueous solution containing 8.9 g and KBr and KI containing 10 mol% of KI. At this time, the silver potential was kept at 0 mV with respect to the saturated calomel electrode. After adding 2 mg of sodium benzenethiosulfonate and 2 mg of thiourea dioxide, AgNO3 was used with the stirring device described in JP-A-10-43570.₃A mixture of 800 cc of an aqueous solution containing 178.5 g and 112.5 g of KBr, 800 cc of an aqueous solution containing 17.4 g of KI and 80 g of gelatin-4, and an AgBrI fine grain emulsion having a silver iodide content of 10 mol% (average size: The AgBrI emulsion was continuously added to the reaction vessel while preparing 0.026 μm). At this time, the silver potential was kept at −30 mV with respect to the saturated calomel electrode. Then AgNO₃An aqueous solution containing 61.4 g of 137.6 cc and a mixed aqueous solution of KBr and KI containing 10 mol% of KI were added by the double jet method. At this time, the silver potential was initially maintained at +20 mV with respect to the saturated calomel electrode and at +120 mV in the second half. After the temperature was lowered to 50 ° C., 57.8 cc of 0.3% KI aqueous solution was added. Immediately thereafter, AgNO₃19.7 cc of an aqueous solution containing 8.8 g, 21 cc of an aqueous solution containing 1.51 g of NaCl and 2.47 g of KBr, and a solution containing 0.005 mol of silver iodide fine particles were added simultaneously. At this time, AgNO to be added₃8.0 × 10 for 1 mol^-4mol K₄[RuCN₆] Was present. Thereafter, a sensitizing dye was added. After washing with water, gelatin was added to adjust the pH to 5.8 and pAg 8.7 at 40 ° C.
[0387]
<Sensitization>
After adding compounds 1 and 2, the temperature was raised to 60 ° C. After adding sensitizing dyes 1 and 2, potassium thiocyanate, chloroauric acid, sodium thiosulfate, and N, N-dimethylselenourea were added for optimum chemical sensitization. Compound 3 and compound 4 were added at the end of chemical sensitization. Here, optimal chemical sensitization means that the sensitizing dye and each compound are 10 per mol of silver halide.^-1To 10^-8It means that it was selected from the range of molar addition amount.
[0388]
(Em-D2)
Em-D2 was obtained in the same manner as Em-D1, except that seed emulsion 10 was used instead of seed emulsion 9.
[0389]
(Em-D3)
Em-D3 was obtained by sensitizing the sensitized portion of Em-D2 in the same manner as Em-C3.
[0390]
(Em-D4)
Em-D4 was obtained by sensitizing the sensitized portion of Em-D2 in the same manner as Em-C4.
[0390]
(Em-E2)
Em-E2 was obtained in the same manner as Em-E1, except that seed emulsion 12 was used instead of seed milk 11.
[0392]
(Em-E3)
Em-E3 was obtained by sensitizing the sensitized portion of Em-E2 in the same manner as Em-C3.
[0393]
(Em-E4)
Em-E4 was obtained by sensitizing the sensitized portion of Em-E2 in the same manner as Em-C4.
[0394]
The morphological characteristics of Em-D1 to D4 and Em-E1 to E4 thus obtained are summarized in Table 4, and the particle characteristics are summarized in Table 5.
[0395]
[Table 4]

[0396]
[Table 5]

[0397]
Each emulsion was dissolved for 30 minutes at 40 ° C. on a cellulose triacetate film support provided with an undercoat layer, and the emulsion was then applied under the coating conditions shown in (1) and (2) below. It was.
[0398]
(1) Emulsion layer
Emulsions-various emulsions (silver 1.63 x 10^-2Mol / m²)
Coupler
ExM-1 (2.26 × 10^-3Mol / m²)
ExY-5 (8.0 × 10^-3g / m²)
High boiling point organic solvent HBS-1 (1.8 × 10^-1g / m²)
Gelatin (3.24 g / m²)
Surfactant W-4
(2) Protective layer
H-1 (0.08 g / m²)
Gelatin (1.8g / m²)
Samples 201 to 208 were prepared by changing the emulsion to be applied to Em-D1 to 4 and Em-E1 to E4, respectively.
[0399]
These samples were subjected to hardening for 14 hours under conditions of 40 ° C. and 70% relative humidity. Thereafter, exposure was carried out through a continuous wedge for 1/100 second, and the density of a sample subjected to the following development processing was measured with a green filter to obtain photographic sensitivity and fog density before long-term storage. The sensitivity is expressed as a relative value of the reciprocal of the exposure amount necessary to reach a fog density plus 0.2. For the evaluation of the storage fog of the photosensitive material, the sample was stored for 14 days under conditions of 40 ° C. and relative humidity 60%, exposed to 1/100 second, and subjected to the development processing described below. The fog density after storage was determined, and the fog density difference before and after storage was determined.
[0400]
Development was performed as follows using an automatic processor FP-362B manufactured by Fuji Photo Film Co., Ltd.
[0401]
The treatment process and the treatment liquid composition are shown below.
[0402]
(Processing process)
Process Processing time Processing temperature Replenishment amount * Tank capacity
Color development 3 minutes 5 seconds 38 ° C 15Ml 10.3L
Bleaching 50 seconds 38 ° C 5mL 3.6L
Fixing (1) 50 seconds 38 ° C-3.6L
Fixing (2) 50 seconds 38 ° C 7.5mL 3.6L
Stable (1) 30 seconds 38 ° C-1.9L
Stable (2) 20 seconds 38 ° C-1.9L
Stable (3) 20 seconds 38 ° C 30 mL 1.9 L
Dry 1 min 30 sec 60 ° C
* Replenishment amount per photosensitive material 35mm width 1.1m (equivalent to 24Ex. 1).
[0403]
The stabilizing liquid is a countercurrent system from (3) → (2) → (1), and the fixing liquid is also connected from (2) to (1) by countercurrent piping. Further, 15 mL of the replenishment amount corresponding to the tank liquid of the stabilizing liquid (2) is flowing into the fixing liquid (2). Further, the color developer is replenished as a total of 15 mL by dividing the color developer (A) replenisher and color developer (B) replenisher of the following formulation into 12 mL and 3 mL, respectively, corresponding to the replenishment amount. Note that the amount of the developer brought into the bleaching process, the amount of the bleaching solution brought into the fixing step, and the amount of the fixing solution brought into the water washing step are all 1. It was 2.0 mL per meter. The crossover time is 6 seconds, and this time is included in the processing time of the previous process.
[0404]
The composition of the treatment liquid is shown below.
[0405]

The tank solution has the following composition after mixing (color developer (B)).
[0406]

The tank solution shows the composition after mixing the (color developer (A)).
[0407]

[0408]

[0409]

[0410]
The said process was performed with respect to the samples 201-208. Photographic performance was evaluated by measuring the density of the processed sample with a blue filter. The obtained results are shown in Tables 6 and 7.
[0411]
From Tables 6 and 7, the sample using the emulsion of the present invention achieves high sensitivity while improving the graininess with respect to the comparative sample.
[0412]
[Table 6]

[0413]
[Table 7]

[0414]
【The invention's effect】
In the present invention, the silver iodide content of silver halide grains occupying 50% or more of the total projected area is 3 mol% or more, the projected area diameter is monodispersed, and the grain thickness is monodispersed. By using a silver halide photographic emulsion, it is possible to provide a silver halide light-sensitive material excellent in sensitivity and grain.

Claims (3)

In a silver halide photographic emulsion containing a dispersion medium and silver halide grains, the variation coefficient of the projected area diameter of the silver halide grains is 30% or less, and the variation coefficient of the grain thickness is 15% or less, A silver halide photographic emulsion characterized in that 50% or more of the total projected area is occupied by silver halide grains satisfying the following (a), (b), (c) and (d).
(A) Silver halide tabular grains whose main plane is a smooth (111) plane (b) Silver iodide content 3 mol% or more (c) Projected area diameter 1 μm or more (d) Aspect ratio 8 or more The silver halide photographic emulsion according to claim 1, wherein the silver halide grains further satisfy the following (e):
(E) Silver iodide content of 5 mol% or more The silver halide photographic emulsion according to claim 1 or 2, wherein the silver halide grains further satisfy the following (f).
(F) Sphere equivalent diameter of 0.6 μm to 2.0 μm