JP4053748B2 - Silver halide photographic emulsion and silver halide photographic light-sensitive material using the same - Google Patents

Description

【０１１０】
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。
【０１１１】
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。
【０１１２】
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、特公昭５８−１０７３９号、英国特許第１，４２５，０２０号、同第１，４７６，７６０号、米国特許第３，９７３，９６８号、同第４，３１４，０２３号、同第４，５１１，６４９号、欧州特許第２４９，４７３Ａ号、等に記載のものが好ましい。
【０１１３】
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、欧州特許第７３，６３６号、米国特許第３，０６１，４３２号、同第３，７２５，０６７号、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、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、米国特許第４，５００，６３０号、同第４，５４０，６５４号、同第４，５５６，６３０号、国際公開ＷＯ８８／０４７９５号に記載のものが特に好ましい。
【０１１４】
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、西独特許公開第３，３２９，７２９号、欧州特許第１２１，３６５Ａ号、同第２４９，４５３Ａ号、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、特開昭６１−４２６５８号等に記載のものが好ましい。
【０１１５】
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、英国特許第２，１０２，１３７号、欧州特許第３４１，１８８Ａ号に記載されている。
【０１１６】
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、英国特許第２，１２５，５７０号、欧州特許第９６，５７０号、西独特許（公開）第３，２３４，５３３号に記載のものが好ましい。
【０１１７】
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、特公昭５７−３９４１３号、米国特許第４，００４，９２９号、同第４，１３８，２５８号、英国特許第１，１６，３６８号に記載のものが好ましい。また、米国特許第４，７７４，１８１号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。
【０１１８】
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、米国特許第４，２４８，９６２号、同第４，７８２，０１２号に記載されたものが好ましい。
【０１１９】
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、特開昭５９−１５７６３８号、同５９−１７０８４０号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。
【０１２０】
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号等に記載の多当量カプラー、特開昭６０−１８５９５０号、特開昭６２−２４２５２号等に記載の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号等に記載のリガンド放出カプラー、特開昭６３−７５７４７号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号に記載の蛍光色素を放出するカプラーが挙げられる。
【０１２１】
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。
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号に記載されている。
【０１２２】
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。
【０１２３】
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、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。
【０１２４】
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。
【０１２５】
本発明は種々の感光材料に適用することができるが、種々のカラー感光材料に適用する場合が好ましい。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。
【０１２６】
本発明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。
【０１２７】
本発明の感光材料は、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。
【０１２８】
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。
【０１２９】
本発明の感光材料は、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。
【０１３０】
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。
【０１３１】
本発明の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。
【０１３２】
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。
【０１３３】
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３Ｌとも表記する。）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５０ミリリットル（以下、ミリリットルを「ｍＬ」とも表記する。）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。
【０１３４】
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（cm²）］÷［処理液の容量（cm³）］。
【０１３５】
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号に記載された可動蓋を用いる方法、特開昭６３−２１６０５０号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。
【０１３６】
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。
【０１３７】
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。
【０１３８】
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、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、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、米国特許第３，７０６，５６１号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、西独特許第１，２９０，８１２号、特開昭５３−９５６３０号に記載の化合物が好ましい。更に、米国特許第４，５５２，８８４号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。
【０１３９】
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。
【０１４０】
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。
【０１４１】
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／Ｌ添加することが好ましい。
【０１４２】
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。
【０１４３】
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。
【０１４４】
本発明の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。
【０１４５】
本発明の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。
【０１４６】
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。
【０１４７】
本発明の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号に記載の公知の方法はすべて用いることができる。
【０１４８】
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。
【０１４９】
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。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。
【０１５０】
本発明の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良い。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号記載のインドアニリン系化合物、例えば、同第３，３４２，５９９号、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号に記載の金属塩錯体、特開昭５３−１３５６２８号に記載のウレタン系化合物を挙げることができる。
【０１５１】
本発明の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良い。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号に記載されている。
【０１５２】
本発明における各種処理液は、１０℃〜５０℃において使用される。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。
【０１５３】
また、本発明のハロゲン化銀感光材料は、米国特許第４，５００，６２６号、特開昭６０−１３３４４９号、同５９−２１８４４３号、同６１−２３８０５６号、欧州特許第２１０，６６０Ａ２号などに記載されている熱現像感光材料にも適用できる。
また、本発明のハロゲン化銀カラー写真感光材料は、特公平２−３２６１５号、実公平３−３９７８４号などに記載されているレンズ付きフィルムユニットに適用した場合に、より効果を発現しやすく有効である。
【０１５４】
【実施例】
以下に本発明の実施例を示す。但しこの実施例に限定されるものではない。
（実施例１）
（乳剤の調製）
（種乳剤Ａ）
ＫＢｒを０．９ｇ、通常のアルカリ処理ゼラチン（平均分子量１０万）を３ｇ含む水溶液１２００ｍＬを３５℃に保ち、撹拌した（１ｓｔ液調製）。Ａｇ−１水溶液（１００ｍＬ中にＡｇＮＯ₃を４．９ｇ含有する）３７ｍＬと、Ｘ−１水溶液（１００ｍＬ中にＫＢｒを３．５ｇ含有する）３７ｍＬ、およびＧ−１水溶液（１００ｍＬ中に前記のゼラチンを２．５ｇ含有する）２０ｍＬをトリプルジェット法で、一定の流量で３０秒間にわたり添加した（添加１）。ＫＢｒ５．２ｇを含む水溶液を添加し、温度を７５℃に昇温し、９分間の熟成工程を経た後、Ｇ−２水溶液（１００ｍＬ中に前記のゼラチンを３５ｇ含有する）２００ｍＬを添加した。
【０１５５】
次に、Ａｇ−２水溶液（１００ｍＬ中にＡｇＮＯ₃を１４．９ｇ含有する）１６２ｍＬと、Ｘ−２水溶液（１００ｍＬ中にＫＢｒを８．１ｇ、ＫＩを０．２４ｇ含有する）１５９ｍＬをダブルジェット法で流量を加速しながら２０分間にわたり添加した（添加２）。
【０１５６】
次いで、Ａｇ−３水溶液（１００ｍＬ中にＡｇＮＯ₃を１３．３ｇ含有する）８０３ｍＬと、Ｘ−３水溶液（１００ｍＬ中にＫＢｒを２３．０ｇ、ＫＩを３．６ｇ含有する）をダブルジェット法で流量を加速しながら２５分間にわたり添加した。この時、Ｘ−３水溶液の添加は反応容器内のバルク乳剤溶液の銀電位を０ｍＶ（飽和カロメル電極）に保つように行った（添加３）。
【０１５７】
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、ゼラチンを添加し、５６℃でｐＨ５．８、ｐＡｇ８．８、乳剤１ｋｇ当たりの銀換算の質量１０３．４ｇ、ゼラチン質量１０２ｇになるように調整した。得られた乳剤は、全粒子の９８％以上（粒子個数比）が平行な主平面が（１１１）面である沃臭化銀の平板粒子から成る乳剤であり、平均球相当直径は０．６３μｍであった（以下の種乳剤ＢとＣも同様であった）。
【０１５８】
（種乳剤Ｂ）
上記種乳剤Ａにおいて、以下の変更以外は種乳剤Ａと同様に調製した。
（１ｓｔ液調製）において、ＫＢｒ０．９ｇを０．３ｇに変更し、平均分子量１０万のアルカリ処理ゼラチンを同１万５千のアルカリ処理ゼラチンに変更し、温度３５℃の代わりに３０℃に保った。
（添加１）において、Ｇ−１水溶液に含まれる平均分子量１０万のゼラチンを同１万５千のゼラチンに変更し、Ａｇ−１水溶液とＸ−１水溶液とＧ−１水溶液をトリプルジェット法で一定の流量で３０秒間添加する代わりに１５秒間で添加した。また、７５℃に昇温後の熟成時間を９分から１５分に変更した。
【０１５９】
（種乳剤Ｃ）
上記種乳剤Ｂにおいて、以下の変更以外は種乳剤Ｂと同様に調製した。
（１ｓｔ液調製）において、平均分子量１万５千のアルカリ処理ゼラチンを酸化処理ゼラチン（過酸化水素でメチオニンを酸化させた平均分子量１万５千のゼラチン）に変更した。
【０１６０】
（乳剤１−Ａ）
上記種乳剤Ａを６７ｇと架橋型高分子量ゼラチン（ＰＡＧＩ法により測定された分子量分布は、高分子量成分が１２．４％、低分子量成分が４８．３％）３２ｇ及びＫＢｒを１．４ｇ含む水溶液１２００ｍＬを７５℃、ｐＨ＝５に保ち、撹拌した（１ｓｔ液調製）。
【０１６１】
次に、Ａｇ’−１水溶液（１００ｍＬ中にＡｇＮＯ₃を１６ｇ含有する）９３５ｍＬと、Ｘ’−１水溶液（１００ｍＬ中にＫＢｒを１１．５ｇ、ＫＩを１．８ｇ含有する）をダブルジェット法で流量を加速しながら７０分間にわたり添加した。この時、Ｘ’−１水溶液の添加は反応容器内のバルク乳剤溶液の銀電位を１０ｍＶ（飽和カロメル電極）に保つように行った（添加１）。
【０１６２】
次いで、ベンゼンチオスルホン酸ナトリウム１．８ｍｇを含む水溶液を添加した後、４０℃に降温し、さらに６塩化イリジウムカリウムを０．０８ｍｇを含む水溶液を添加してからＡｇ’−２水溶液（１００ｍＬ中にＡｇＮＯ₃を１６ｇ含有する）２７５ｍＬと、Ｘ’−２水溶液（１００ｍＬ中にＫＢｒを１０．９ｇ、ＫＩを２．７ｇ含有する）をダブルジェット法で２０分間にわたり添加した。この時、Ｘ’−２水溶液の添加は反応容器内のバルク乳剤溶液の銀電位を３０ｍＶ（飽和カロメル電極）に保つように行った（添加２）。
【０１６３】
その後、フェノキシエタノール１０ｍＬを添加し、ＫＩ０．４ｇを含む水溶液を１分間かけて添加した後、下記化１に示す増感色素（ゼラチン分散物）をこの粒子の飽和吸着量の８０％に相当する量だけ添加した。さらに、ヘキサシアノルテニウム（ＩＩ）酸カリウム３ｍｇを含む水溶液を添加した。
【０１６４】
その後、Ａｇ’−３水溶液（１００ｍＬ中にＡｇＮＯ₃を１６ｇ含有する）５５ｍＬとＸ’−３（１００ｍＬ中にＮａＣｌ６ｇとＫＢｒ８．１ｇを含む水溶液）８７ｍＬをダブルジェットで５分間にわたりて添加した（添加３）。
【０１６５】
次に、Ａｇ−４水溶液（１００ｍＬ中にＡｇＮＯ₃を１６ｇ含有する）４１ｍＬとＸ−４水溶液（１００ｍＬ中にＫＢｒ１１．６ｇとＫＩ５．１ｇを含有する）を４分間かけて添加した（添加４）。
最後に下記化２に示す化合物４０ｍｇを添加した。
【０１６６】
【化１】

【０１６７】
【化２】

【０１６８】
続いて、３５℃に降温し、通常の水洗の後、ゼラチン５２ｇを加え４０℃で分散を行い、ｐＨを６．５に、銀電位をＮａＣｌ水溶液を用いて飽和カロメル電極に対して８０ｍＶに調整した。次いで、下記化３に示す化合物４ｍｇを添加し、チオシアン酸カリウム、塩化金酸、チオ硫酸ナトリウムおよびＮ，Ｎ−ジメチルセレノ尿素を順次添加し最適に化学増感を施した後、下記化４に示す水溶性メルカプト化合物を添加することにより化学増感を終了させた。最適な化学増感とは１／１００秒露光時に感度が最高になることである。
【０１６９】
【化３】

【０１７０】
【化４】

【０１７１】
得られた乳剤は、全粒子の９７％以上（粒子個数比）が平行な主平面が（１１１）面である沃塩臭化銀の平板粒子から成る乳剤であり、平均球相当直径は１．７μｍであった。
【０１７２】
（乳剤１−Ｂ）
乳剤１−Ａにおいて以下の変更以外は乳剤１−Ａと同様に調製した。
【０１７３】
乳剤１−Ａの（添加３）において、Ｘ’−３水溶液（１００ｍＬ中にＮａＣｌ６ｇとＫＢｒ８．１ｇを含む水溶液）の代わりに、Ｘ”−３水溶液（１００ｍＬ中にＮａＣｌ８ｇとＫＢｒ４ｇを含む水溶液）を用いた。
【０１７４】
（乳剤１−Ｃ）
乳剤１−Ｂにおいて以下の変更以外は乳剤１−Ｂと同様に調製した。
種乳剤Ａを用いる代わりに上記種乳剤Ｂを用いた。
【０１７５】
（乳剤１−Ｄ）
乳剤１−Ｂにおいて以下の変更以外は乳剤１−Ｂと同様に調製した。
種乳剤Ａを用いる代わりに上記種乳剤Ｃを用いた。
【０１７６】
（乳剤１−Ｅ）
乳剤１−Ａにおいて以下の変更以外は乳剤１−Ａと同様に調製した。
【０１７７】
乳剤１−Ａの（添加１）において、Ａｇ’−１水溶液とＸ’−１水溶液をダブルジェット法で、反応容器内のバルク乳剤溶液の銀電位を１０ｍＶに保つ代わりに−３０ｍＶに保って添加を行った。
【０１７８】
（乳剤１−Ｆ）
乳剤１−Ｅにおいて以下の変更以外は乳剤１−Ｅと同様に調製した。
乳剤１−Ｅの（添加３）において、Ｘ’−３水溶液（１００ｍＬ中にＮａＣｌ６ｇとＫＢｒ８．１ｇを含む水溶液）の代わりに、Ｘ”−３水溶液（１００ｍＬ中にＮａＣｌ８ｇとＫＢｒ４ｇを含む水溶液）を用いた。
【０１７９】
（乳剤１−Ｇ）
乳剤１−Ｆにおいて以下の変更以外は乳剤１−Ｆと同様に調製した。
種乳剤Ａを用いる代わりに上記種乳剤Ｂを用いた。
【０１８０】
（乳剤１−Ｈ）
乳剤１−Ｆにおいて以下の変更以外は乳剤１−Ｆと同様に調製した。
種乳剤Ａを用いる代わりに上記種乳剤Ｃを用いた。
【０１８１】
（乳剤１−Ｉ）
乳剤１−Ａにおいて以下の変更以外は乳剤１−Ａと同様に調製した。
乳剤１−Ａの（添加１）において、Ａｇ’−１水溶液とＸ’−１水溶液をダブルジェット法で添加する代わりに、Ａｇ’−１水溶液（１００ｍＬ中にＡｇＮＯ₃を１６ｇ含有する）９３５ｍＬとＸ’−１水溶液（１００ｍＬ中にＫＢｒを１１．５ｇ、ＫＩを１．８ｇ、過酸化水素でメチオニンを酸化させた平均分子量１万５千のゼラチン２０ｇを含有する）８８８ｍＬを特開平１０−４３５７０号記載の磁気カップリング誘導型攪拌機を有する本体の反応容器とは別のチャンバーで混合して、沃臭化銀の超極微粒子を同時調製し、本体の反応容器に連続的に添加した。この時、沃臭化銀の超極微粒子の添加は反応容器内のバルク乳剤溶液の銀電位を０ｍＶ（飽和カロメル電極）に保つように行った。
【０１８２】
（乳剤１−Ｊ）
乳剤１−Ｉにおいて以下の変更以外は乳剤１−Ｉと同様に調製した。
乳剤１−Ｉの（添加３）において、Ｘ’−３水溶液（１００ｍＬ中にＮａＣｌ６ｇとＫＢｒ８．１ｇを含む水溶液）の代わりに、Ｘ”−３水溶液（１００ｍＬ中にＮａＣｌ８ｇとＫＢｒ４ｇを含む水溶液）を用いた。
【０１８３】
（乳剤１−Ｋ）
乳剤１−Ｊにおいて以下の変更以外は乳剤１−Ｊと同様に調製した。
種乳剤Ａを用いる代わりに上記種乳剤Ｂを用いた。
【０１８４】
（乳剤１−Ｌ）
乳剤１−Ｋにおいて以下の変更以外は乳剤１−Ｋと同様に調製した。
種乳剤Ａを用いる代わりに上記種乳剤Ｃを用いた。
【０１８５】
（乳剤１−Ｍ）
乳剤１−Ｌにおいて以下の変更以外は乳剤１−Ｌと同様に調製した。
【０１８６】
乳剤１−Ｌの（添加３）において、Ｘ”−３水溶液（１００ｍＬ中にＮａＣｌ８ｇとＫＢｒ４ｇを含む水溶液）の代わりに、Ｘ”’−３水溶液（１００ｍＬ中にＮａＣｌ１０ｇを含む水溶液）を用いた。
【０１８７】
上記乳剤１−Ａ〜１−Ｍについて、粒子形状データ、ホスト粒子頂点部にエピタキシャル接合部を１粒子当たり６個有する平板粒子が全粒子に占める割合（個数比）、エピタキシャル接合部に少なくとも１本の転位線を有する平板粒子が全粒子に占める割合（個数比）、２枚の平行な双晶面の間隔が０．０１２あるいは０．００８μm以下の平板粒子が全粒子に占める割合（個数比）を共に下記表１にまとめた（いづれの値も電子顕微鏡を用いて本文記載の方法で観察して求めた）。
【０１８８】
【表１】

【０１８９】
（塗布試料の作成、その評価）
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下記表２に示すような塗布条件で、前記の乳剤１−Ａ−１〜１−Ｍの塗布を行った。
【０１９０】
【表２】

【０１９１】
これらの試料１０１〜１１３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、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秒間露光を行い、後述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及び階調性の評価を行った。
【０１９２】
富士写真フイルム（株）製ネガプロセサーＦＰ−３５０を用い、以下に記載の方法で（液の累積補充量がその母液タンク容量の３倍になるまで）処理した。
【０１９３】

次に、処理液の組成を記す。

【０１９４】

【０１９５】

【０１９６】
（水洗液） タンク液、補充液共通
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／Ｌ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／Ｌと硫酸ナトリウム０．１５ｇ／Ｌを添加した。この液のｐＨは６．５〜７．５の範囲にあった。
【０１９７】

【０１９８】
写真感度及び階調性の結果を下記の表３に示す。感度は得られた特性曲線のかぶり濃度プラス０．１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（試料１０１の感度を１００とした）。また、階調性については特性曲線のかぶり濃度よりも０．２及び０．８高い濃度を示す２点を結ぶ直線の傾きをもって階調の値とし、相対値で表示した（試料１０１の階調の値を１００とした）。
【０１９９】
【表３】

【０２００】
試料１０１〜１０６及び試料１０９から１１０と試料１０７〜１０８及び試料１１１〜１１３との比較から、本発明の乳剤を用いた試料は高感度でかつ階調性の改良された（硬調な）ものであることが分かる。
【０２０１】
（実施例２）
実施例１の乳剤１−Ｄ、１−Ｈ、１−Ｍにおいて、各乳剤の（添加１）の２分前にカテコールジスルホン酸ナトリウム塩１．５ｇを含む水溶液を添加し、１分前に二酸化チオ尿素０．００２ｇを含む水溶液を添加して正孔捕獲ゾーンを付与した乳剤１−Ｄ’、１−Ｈ’、１−Ｍ’を調製して実施例１同様に塗布し、下記の表４に示す試料２０１〜２０６を作成した。写真性能の評価も実施例１同様に行った。結果を下記の表４に示す。
【０２０２】
【表４】

【０２０３】
試料２０１〜２０２と試料２０３〜２０６との比較から、本発明の乳剤を用いた試料は正孔捕獲ゾーンを設けることにより、高感度でかつ階調性の改良された（硬調な）ものであることが分かる。
【０２０４】
（実施例３）
（乳剤の調製）
（Ｅｍ−Ａ）
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。ＡｇＮＯ₃，１．４９ｇ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。ＡｇＮＯ₃，２９ｇ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。ＡｇＮＯ₃，１１０．２ｇ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、同時に粒子サイズ０．０３７μmのＡｇＩ微粒子乳剤をヨウ化銀含有率が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。ＡｇＮＯ₃，２４．１ｇ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ＡｇＩ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ＡｇＮＯ₃，５７ｇ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。水洗した後、ゼラチンを添加し４０℃でｐＨ，５．８、ｐＡｇ，８．７に調整した。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、塩化金酸、チオ硫酸ナトリウム、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。
【０２０５】
【化５】

【０２０６】
【化６】

【０２０７】
【化７】

【０２０８】
【化８】

【０２０９】
【化９】

【０２１０】
【化１０】

【０２１１】
（Ｅｍ−Ｂ）
１ｇ当たり３５μｍｏｌのメチオニンを含有する分子量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。ＡｇＮＯ₃，４．４７ｇ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−Ａの調製で使用した分子量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、ジメチルアミンボラン，８ｍｇを添加した。ＡｇＮＯ₃，２６ｇ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。ＡｇＮＯ₃，１１０．２ｇ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−Ａの調製で使用したＡｇＩ微粒子乳剤をヨウ化銀含有率が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、ＡｇＮＯ₃，２４．１ｇ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ＡｇＩ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ＡｇＮＯ₃，５７ｇ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−Ａとほぼ同様に水洗し、化学増感した。
【０２１２】
（Ｅｍ−Ｃ）
Ｅｍ−Ｂの調製において核形成時のＡｇＮＯ₃添加量を２．０倍に変更した。
そして、最終のＡｇＮＯ₃，５７ｇ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−Ｂとほぼ同様にして調製した。
【０２１３】
（Ｅｍ−Ｄ）
分子量１５０００の低分子量ゼラチン，０．７１ｇ、ＫＢｒ，０．９２ｇ、Ｅｍ−Ａ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。ＡｇＮＯ₃，０．４５ｇ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。ＡｇＮＯ₃，２８．８ｇ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−Ａの調製で使用したＡｇＩ微粒子乳剤をヨウ化銀含有率が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、ＡｇＮＯ₃，８７．７ｇ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ＡｇＩ微粒子乳剤をヨウ化銀含有率が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、ＡｇＮＯ₃，４１．８ｇ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ＡｇＩ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ＡｇＮＯ₃，６６．４ｇ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ＡｇＩ微粒子乳剤を銀１ｍｏｌに対して０．０００４ｍｏｌ添加した後、増感色素３および４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−ジメチルセレノウレアを添加し最適に化学増感した。化学増感終了時に化合物３および４を添加した。
【０２１４】
【化１１】

【０２１５】
【化１２】

【０２１６】
（Ｅｍ−Ｅ）
Ｅｍ−Ｄの調製において核形成時のＡｇＮＯ₃添加量を３．１倍に変更した以外はＥｍ−Ｄとほぼ同様にして調製した。但しＥｍ−Ｄの増感色素を増感色素５、６および７に変更した。
【０２１７】
【化１３】

【０２１８】
【化１４】

【０２１９】
【化１５】

【０２２０】
（Ｅｍ−Ｆ）
分子量１５０００の低分子量ゼラチン０．７０ｇ、ＫＢｒ，０．９ｇ、ＫＩ，０．１７５ｇ、変成シリコンオイル（日本ユニカー株式会社製品 Ｌ７６０２）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。ＡｇＮＯ₃，１．８ｇ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。ＡｇＮＯ₃，２７．５８ｇ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、分子量１５０００の低分子量ゼラチン水溶液とＡｇＮＯ₃水溶液とＫＩ水溶液を特開平１０−４３５７０号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０．００８μのＡｇＩ微粒子乳剤をヨウ化銀含有率が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、ＡｇＮＯ₃，８７．７ｇ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ＡｇＩ微粒子乳剤をヨウ化銀含有率が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、ＡｇＮＯ₃，４１．８ｇ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−Ａの調製で使用したＡｇＩ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ＡｇＮＯ₃，６６．４ｇ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−Ｅとほぼ同様に水洗し、化学増感した。
【０２２１】
（Ｅｍ−Ｇ）
イオン交換した分子量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。ＡｇＮＯ₃、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、ＡｇＮＯ₃，１３３．４ｇ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Ｋ₂ＩｒＣｌ₆を０．１ｍｇ添加した。ＮａＣｌを７ｇ添加した後、ＡｇＮＯ₃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−Ａの調製で使用したＡｇＩ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ＡｇＮＯ₃，４２．７ｇ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−Ｅとほぼ同様に水洗し、化学増感した。
【０２２２】
（Ｅｍ−Ｈ）
Ｅｍ−Ｇ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。
【０２２３】
（Ｅｍ−Ｉ）
フタル化率９７％の分子量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。ＡｇＮＯ₃，１．９６ｇ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。ＡｇＮＯ₃，２７．３ｇ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。ＡｇＮＯ₃，６５．６ｇ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−Ａの調製で使用したＡｇＩ微粒子乳剤をヨウ化銀含有量が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、ＡｇＮＯ₃，４１．８ｇ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ＡｇＩ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ＡｇＮＯ₃，８８．５ｇ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８、９、１０および１１を添加した後、Ｋ₂ＩｒＣｌ₆，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−ジメチルセレノウレアを添加し最適に化学増感した。化学増感終了時に化合物３および４を添加した。
【０２２４】
【化１６】

【０２２５】
【化１７】

【０２２６】
【化１８】

【０２２７】
【化１９】

【０２２８】
（Ｅｍ−Ｊ）
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。ＡｇＮＯ₃，８．７５ｇ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、ＡｇＮＯ₃，６．９ｇを含む水溶液２１ｍＬを２．５分間に渡り添加した。ＮＨ₄ＮＯ₃，２６ｇ、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。ＡｇＮＯ₃，１４１ｇ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、ＡｇＮＯ₃，７．１ｇ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Ｋ₂ＩｒＣｌ₆，０．０５ｍｇ添加した。ＡｇＮＯ₃，５７．２ｇ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−Ｉとほぼ同様に水洗し、化学増感した。
【０２２９】
（Ｅｍ−Ｋ）
Ｅｍ−Ｊ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。
【０２３０】
（Ｅｍ−Ｌ、Ｍ、Ｎ）
Ｅｍ−ＧまたはＥｍ−Ｈとほぼ同様にして調製した。但し化学増感はＥｍ−Ｉとほぼ同様の方法で行った。
【０２３１】
（Ｅｍ-Ｏ）
Ｅｍ−Ｉ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-Ｏを得た。
【０２３２】
このようにして得られたハロゲン化銀乳剤ハロゲン化銀乳剤Ａ〜Ｏの特性を（表５）に示す。
【０２３３】
【表５】

【０２３４】
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。
【０２３５】
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。
【０２３６】
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／ｍ²、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／ｍ²、サリチル酸０．０４ｇ ／ｍ²、ｐ−クロロフェノール０．２ｇ／ｍ²、（ＣＨ₂＝ＣＨＳＯ₂ＣＨ₂ＣＨ₂ＮＨＣＯ）₂ＣＨ₂０．０１２ｇ／ｍ²、ポリアミド−エピクロルヒドリン重縮合物 ０．０２ｇ／ｍ²の下塗液を塗布して（１０ｍＬ／ｍ²、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）。
【０２３７】
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。
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／ｍ²、ゼラチン０．０５ｇ／ｍ²、（ＣＨ₂＝ＣＨＳＯ₂ＣＨ₂ＣＨ₂ＮＨＣＯ）₂ＣＨ₂ ０．０２ｇ／ｍ²、ポリ（重合度１０）オキシエチレン−ｐ−ノニルフェノール ０．００５ｇ／ｍ²及びレゾルシンと塗布した。
【０２３８】
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４３ｍ²／ｇ、長軸０．１４μｍ、単軸０．０３μｍ、飽和磁化８９Ａｍ²／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／ｍ²をジアセチルセルロース１．２ｇ／ｍ²（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Ｃ₂Ｈ₅Ｃ（ＣＨ₂ＯＣ ＯＮＨ−Ｃ₆Ｈ₃（ＣＨ₃）ＮＣＯ）₃０．３ｇ／ｍ²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／ｍ²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Ｄ^B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４．２Ａｍ²／ｋｇ、保磁力７．３×１０⁴Ａ／ｍ、角形比は６５％であった。
【０２３９】
３−３）滑り層の調製
ジアセチルセルロース（２５ｍｇ／ｍ²）、Ｃ₆Ｈ₁₃ＣＨ（ＯＨ）Ｃ₁₀Ｈ₂₀ＣＯＯＣ₄₀Ｈ₈₁（化合物ａ、６ｍｇ／ｍ²）／Ｃ₅₀Ｈ₁₀₁Ｏ（ＣＨ₂ＣＨ₂Ｏ）₁₆Ｈ（化合物ｂ、９ｍｇ／ｍ²）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／ｍ²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。
【０２４０】
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、下記の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３０１〜３０５を作成した。
（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／ｍ²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。
【０２４１】
（試料３０１）
第１層（第１ハレーション防止層）
黒色コロイド銀 銀 ０．１５５
０．０７μ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。
【０２４２】
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。
【０２４３】
第３層（中間層）
０．０７μｍのＡｇＢｒＩ（２） ０．０２０
ＥｘＣ−２ ０．０２２
ポリエチルアクリレートラテックス ０．０８５
ゼラチン ０．２９４。
【０２４４】
第４層（低感度赤感乳剤層）
沃臭化銀乳剤Ｅｍ−Ｌ 銀 ０．０６５
沃臭化銀乳剤Ｅｍ−Ｍ 銀 ０．１００
沃臭化銀乳剤Ｅｍ−Ｎ 銀 ０．１５８
ＥｘＣ−１ ０．１０９
ＥｘＣ−３ ０．０４４
ＥｘＣ−４ ０．０７２
ＥｘＣ−５ ０．０１１
ＥｘＣ−６ ０．００３
Ｃｐｄ−２ ０．０２５
Ｃｐｄ−４ ０．０２５
ＨＢＳ−１ ０．１７
ゼラチン ０．８０。
【０２４５】
第５層（中感度赤感乳剤層）
沃臭化銀乳剤Ｅｍ−Ｊ 銀 ０．２１
沃臭化銀乳剤Ｅｍ−Ｋ 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
Ｃｐｄ−２ ０．０３６
Ｃｐｄ−４ ０．０２８
ＨＢＳ−１ ０．１６
ゼラチン １．１８。
【０２４６】
第６層（高感度赤感乳剤層）
沃臭化銀乳剤Ｅｍ−Ｉ 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。
【０２４７】
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。
【０２４８】
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−Ｄ 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。
【０２４９】
第９層（低感度緑感乳剤層）
沃臭化銀乳剤Ｅｍ−Ｆ 銀 ０．３９
沃臭化銀乳剤Ｅｍ−Ｇ 銀 ０．２８
沃臭化銀乳剤Ｅｍ−Ｈ 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。
【０２５０】
第１０層（中感度緑感乳剤層）
沃臭化銀乳剤Ｅｍ−Ｅ 銀 ０．２０
沃臭化銀乳剤Ｅｍ−Ｆ 銀 ０．２５
ＥｘＣ−６ ０．００９
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。
【０２５１】
第１１層（高感度緑感乳剤層）
沃臭化銀乳剤Ｅｍ−Ｏ 銀 １．２００
ＥｘＣ−６ ０．００４
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。
【０２５２】
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。
【０２５３】
第１３層（低感度青感乳剤層）
沃臭化銀乳剤Ｅｍ−Ａ 銀 ０．１８
沃臭化銀乳剤Ｅｍ−Ｂ 銀 ０．２０
沃臭化銀乳剤Ｅｍ−Ｃ 銀 ０．０７
ＥｘＣ−１ ０．０４１
ＥｘＣ−８ ０．０１２
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。
【０２５４】
第１４層（高感度青感乳剤層）
実施例１の乳剤1-A,1-E,1-H,1-I,1-Mのいずれか 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。
【０２５５】
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。
【０２５６】
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。
【０２５７】
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^-3グラム、第１１層に７．９×１０^-3グラム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。更に帯電防止性を良くするためにＷ−１、Ｗ−６、Ｗ−７、Ｗ−８を少なくとも１種含有しており、塗布性を良くするためＷ−２、Ｗ−５を少なくとも１種含有している。
【０２５８】
有機固体分散染料の分散物の調製
下記、ＥｘＦ−３を次の方法で分散した。即ち、水２１．７ｍＬ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３ｍＬ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７００ｍＬ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）５００ｍＬ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。
同様にして、ＥｘＦ−４の固体分散物を得た。染料微粒子の平均粒径は０．４５μｍ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。
【０２５９】
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０．５Ｌ／ｍｉｎで８時間粉砕した。
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。
【０２６０】
【化２０】

【化２１】

【化２２】

【化２３】

【化２４】

【化２５】

【化２６】

【化２７】

【化２８】

【化２９】

【化３０】

【化３１】

【化３２】

【化３３】

【化３４】

【化３５】

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。
【０２６１】
処理工程及び処理液組成を以下に示す。

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２．５ｍＬ、２．０ｍＬ、２．０ｍＬ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。
上記処理機の開口面積は発色現像液で１００ｃｍ²、漂白液で１２０ｃｍ²、その他の処理液は約１００ｃｍ²であった。
【０２６２】
以下に処理液の組成を示す。
【０２６３】

【０２６４】

【０２６５】
（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）。
【０２６６】

【０２６７】
（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／Ｌ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／Ｌと硫酸ナトリウム１５０ｍｇ／Ｌを添加した。この液のｐＨは６．５〜７．５の範囲にあった。
【０２６８】

【０２６９】
試料３０１〜３０５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。写真感度及び階調性の結果を下記の表６に示す。感度は得られた特性曲線のかぶり濃度プラス０．０５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（試料３０１の感度を１００とした）。また、階調性については特性曲線のかぶり濃度よりも０．１及び０．３高い濃度を示す２点を結ぶ直線の傾きをもって階調の値とし、相対値で表示した（試料３０１の階調の値を１００とした）。
【０２７０】
【表６】

試料３０１と試料３０２〜３０５の比較から、本発明の乳剤を用いた試料は高感度でかつ階調性の改良された（硬調な）ものであることが分かる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a silver halide photographic emulsion having high sensitivity and improved gradation, and a silver halide photographic light-sensitive material using the same.
[0002]
[Prior art]
In recent years, in order to counter the spread of digital cameras, the demand for silver halide emulsions for photography has become increasingly severe, and higher sensitivity has been demanded. In particular, there is a strong demand for a color photographic light-sensitive material with high sensitivity and high image quality that can withstand use even for an inexpensive camera that tends to lack a strobe light amount, such as the widespread use of film with a lens. One of the techniques for increasing the sensitivity and image quality of silver halide emulsions is the use of tabular grains, increasing sensitivity, including the enhancement of color sensitization efficiency by sensitizing dyes, improving the relationship between sensitivity and grain ratio, Advantages such as improved sharpness and improved covering power due to the specific optical properties of grains are known in the industry. Generally, tabular grains with a higher aspect ratio are more advantageous for improving the sensitivity granularity ratio if the volume is the same. It is.
[0003]
As a sensitization method of tabular grains, a sensitization method using an epitaxial junction is known, and the technique is disclosed in JP-A-58-108526 and 59-133540. Further, regarding application to tabular grains having a high aspect ratio, JP-A-8-69069, 8-101472, 8-101474, 8-101475, 8-171162, 8-171163, 8-101473, 8-101476, 9-211762, No. 9-211763, U.S. Pat.Nos. 5,612,176, 5,614,359, 5,629,144, 5,631,126, 5,691,127 No. 5,726,007. In particular, the example of JP-A No. 2000-32196 discloses a method for preparing large sized high aspect ratio tabular grains having an epitaxial junction at the grain apex and a dislocation line at the epitaxial junction. Further, techniques for imparting a hole trapping zone to tabular grains having an epitaxial junction are disclosed in JP-A-10-268456 and JP-A-10-301219.
[0004]
However, in these patent application specifications, a tabular grain having a large size and a high aspect ratio with a small interval between two parallel twin planes, which is a feature of the present invention, and having an epitaxial junction at the grain apex. However, there is no description suggesting that a photographic emulsion with improved sensitivity and gradation can be obtained by grains having dislocation lines at the epitaxial junction and further having a hole trapping zone in the grains.
[0005]
[Problems to be solved by the invention]
In pursuit of high sensitivity, the present inventor has worked on a method for sensitizing tabular grains using epitaxial junction in a silver halide photographic emulsion having a large equivalent circle equivalent diameter and high aspect ratio tabular grains. It has been clarified that the prior art is insufficient in increasing the sensitivity, and that the gradation becomes soft as the size increases.
[0006]
An object of the present invention is to provide an excellent silver halide photographic emulsion having high sensitivity and improved gradation, and a silver halide photographic light-sensitive material using the same.
[0007]
[Means for Solving the Problems]
The present inventor has worked on a method for sensitizing tabular grains using an epitaxial junction in a silver halide emulsion containing a tabular grain having a large equivalent circle diameter and a high aspect ratio. In addition to the introduction of dislocation lines, the distance between the two parallel twin planes of the tabular grains can be reduced unexpectedly with high sensitivity, and at the same time, the problem of gradation softening accompanying the increase in size can be solved. For the first time. Furthermore, it has been found that the addition of a hole-trapping zone in a tabular grain results in a silver halide emulsion exhibiting photographic performance with increasingly high sensitivity and high gradation.
[0008]
  That is, the following silver halide photographic emulsion and a silver halide photographic light-sensitive material containing the same.
  (1) The following (i) to (v) are satisfiedSukoA silver halide photographic emulsion characterized by
(I) Silver iodochlorobromide having the (111) plane as the main surface and two parallel twin planesHexagonal flat plateparticleOccupies 50% or more (number ratio) of all particles.
[0009]
(Ii) Equivalent circle equivalent diameter is 3.0 μm or more and aspect ratio is 8 or moreHexagonal tabular grains account for 50% or more (number ratio) of all grains.
[0010]
(Iii) HostHexagonThere are six silver halide epitaxial junctions per grain selectively at the apex of tabular grains.Epitaxially bonded hexagonal tabular grains account for 50% or more (number ratio) of all grains.
[0011]
(Iv) having at least one dislocation line in the silver halide epitaxial junctionEpitaxially bonded hexagonal tabular grains account for 50% or more (number ratio) of all grains.
[0012]
(V) The distance between the two parallel twin planes is 0.012 μm or less.Hexagonal flat plateparticleAccounts for 50% or more (number ratio) of all particles.
[0013]
(2) The silver halide photographic emulsion as described in (1), wherein the distance between the two parallel twin planes in (v) is 0.008 μm or less.
[0014]
(3) The silver halide photographic emulsion as described in (1), wherein tabular grains satisfying (i) to (v) occupy 70% or more (number ratio) of all grains.
[0015]
(4) The silver halide photographic emulsion as described in (3) above, wherein the distance between the two parallel twin planes in (v) is 0.008 μm or less.
[0016]
(5) The silver halide photographic emulsion as described in any one of (1) to (4), wherein a hole-trapping zone is present in the tabular grain.
[0017]
(6) In the silver halide photographic light-sensitive material having at least one silver halide emulsion layer on the support, at least one of the silver halide emulsion layers is any one of (1) to (5) A silver halide photographic material comprising the silver halide photographic emulsion described above.
[0018]
DETAILED DESCRIPTION OF THE INVENTION
One preferred embodiment of the present invention is a photographic light-sensitive material having at least one layer of the following silver halide photographic emulsion on a support. That is, 50% or more of all grains are composed of silver iodochlorobromide having a (111) plane as the main surface and two parallel twin planes, an equivalent circle equivalent diameter of 3.0 μm or more, and an aspect ratio of 8 The above has six silver halide epitaxial junctions per grain selectively at the apex of the host tabular grain, and at least one dislocation line in the silver halide epitaxial junction. The emulsion is characterized in that it is an epitaxially bonded tabular grain (hereinafter also simply referred to as “tabular grain”) having a space between parallel twin planes of 0.012 μm or less and having a hole trapping zone in the grain. is there.
[0019]
First, the shape of the silver halide emulsion of the present invention will be described.
In the present invention, a tabular grain means a silver halide grain having two opposing parallel (111) main surfaces. The tabular grains used in the present invention have 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. The tabular grains have a triangular shape, a hexagonal shape, or a circular shape in which they are round when the grains are viewed from a direction perpendicular to the main surface, and have outer surfaces parallel to each other.
[0020]
In the emulsion of the present invention, hexagonal tabular grains having an adjacent side ratio (maximum side length / minimum side length) of 1.5 to 1 preferably occupy 100 to 50% of the total number of grains. More preferably 100 to 70%, still more preferably 100 to 80%. In the emulsion of the present invention, more preferably hexagonal tabular grains having an adjacent side ratio (maximum side length / minimum side length) of 1.2 to 1 occupy 100 to 50% of the total number of grains. More preferably, it accounts for 100 to 70%, particularly preferably 100 to 80%. When the shape of the main surface of the tabular grain is a rounded triangle or hexagon, the length of the side of the main surface is the length of the hypothetical triangle or hexagon formed by extending each side. To do. When tabular grains other than the above hexagons are mixed, it is not preferable in terms of homogeneity between grains.
[0021]
In the emulsion of the present invention, tabular grains occupy 50% or more (number ratio) of the total grains by tabular grains having an equivalent circle equivalent diameter of 3.0 μm or more and an aspect ratio of 8 or more. More preferably, 70% or more (number ratio) of the total grains are tabular grains having an equivalent circle equivalent diameter of 3.0 μm or more and an aspect ratio of 8 or more. The larger the equivalent circle equivalent diameter and the larger the aspect ratio, the more the particles occupy.
[0022]
The average equivalent circle equivalent diameter of the tabular grains of the emulsion of the present invention is from 3.0 to 6.0 μm, more preferably from 3.0 to 5.0 μm. Outside these ranges, it is difficult to obtain the effects of the present invention, which is not preferable. The equivalent circle equivalent diameter in the present invention is the diameter of a circle having an area equal to the projected area of the parallel outer surface of the particle. The average equivalent circular equivalent diameter is an arithmetic average of equivalent circular equivalent diameters of all tabular grains in the emulsion.
[0023]
The average aspect ratio of the tabular grains of the emulsion of the present invention is preferably 8 to 100, more preferably 10 to 60, still more preferably 12 to 50. Tabular grains having an average aspect ratio exceeding 100 are difficult to prepare. Further, tabular grains having an average aspect ratio of less than 4 are not preferable because the effects of the present invention are hardly obtained. The average aspect ratio is an arithmetic average of the grain thicknesses of all tabular grains in the emulsion.
[0024]
The ratio of the equivalent circle equivalent diameter to the silver halide grain thickness is called the aspect ratio. That is, it is a value obtained by dividing the equivalent circle diameter of the projected area of each silver halide grain by the grain thickness.
[0025]
The equivalent circle equivalent diameter of the tabular grain is obtained, for example, by taking a transmission electron micrograph by the replica method and obtaining the diameter of a circle having an area equal to the projected area of each grain. The grain thickness cannot be calculated simply from the length of the shadow of the replica due to epitaxial deposition. However, it can be calculated by measuring the length of the shadow of the replica before epitaxial deposition. Alternatively, even after epitaxial deposition, the sample coated with tabular grains can be cut and easily taken by taking an electron micrograph of the cross section.
[0026]
In the emulsion of the present invention, tabular grains having a distance between two parallel twin planes of 0.012 μm or less occupy 50% or more (number ratio) of all grains, and more preferably 70% or more. More preferably, tabular grains having a distance between two parallel twin planes of 0.008 μm or less occupy 50% or more (number ratio) of all grains, and particularly preferably 70% or more. The larger the number of tabular grains having a small interval between two parallel twin planes, the more remarkable the effect of the present invention.
[0027]
The twin plane can be observed using a transmission electron microscope. Specifically, a sample in which tabular grains are arranged substantially parallel to the support is prepared, and this is cut with a diamond knife to prepare a slice having a thickness of about 0.1 μm. By observing the section with a transmission electron microscope, the twin plane of the tabular grain can be detected. When the electron beam passes through the twin plane, a phase shift occurs in the electron wave, so that its existence is recognized.
[0028]
In the present invention, various methods may be selected depending on the case in order to form tabular grains having a small interval between two parallel twin planes. For example, nucleation is preferably performed at 20 to 40 ° C. at a low temperature and high potential of about pAg = 9, or by using low molecular weight gelatin subjected to oxidation treatment.
[0029]
The emulsion of the present invention is preferably composed of monodispersed grains. The variation coefficient of the grain size (equivalent sphere equivalent diameter) distribution of all the grains of the emulsion of the present invention is preferably 35% to 3%, more preferably 25 to 3%, still more preferably 20 to 3%. . The variation coefficient of the equivalent sphere equivalent diameter distribution is obtained by multiplying the value obtained by dividing the variation (standard deviation) of the equivalent sphere equivalent diameter of each tabular grain by the average equivalent sphere equivalent diameter by 100. If the variation coefficient of the equivalent sphere equivalent diameter distribution of all tabular grains exceeds 35%, it is not preferable in terms of homogeneity between grains. Also, it is difficult to prepare an emulsion of less than 3%.
[0030]
The variation coefficient of the equivalent circle equivalent diameter distribution of all the grains of the emulsion of the present invention is preferably 40% to 3%, more preferably 30 to 3%, still more preferably 20 to 3%. The variation coefficient of the equivalent circle equivalent diameter distribution is obtained by multiplying the value obtained by dividing the variation (standard deviation) of the equivalent circle equivalent diameter of each particle by the average equivalent circle equivalent diameter by 100. When the variation coefficient of the equivalent circle equivalent diameter distribution of all particles exceeds 40%, it is not preferable in terms of homogeneity between particles. Also, it is difficult to prepare an emulsion of less than 3%.
[0031]
The variation coefficient of the grain thickness distribution of all tabular grains of the emulsion of the present invention is preferably 25 to 3%, more preferably 20 to 3%, and still more preferably 15 to 3%. The variation coefficient of the grain thickness distribution is obtained by multiplying the value obtained by dividing the grain thickness variation (standard deviation) of each tabular grain by the average grain thickness by 100. If the variation coefficient of the grain thickness distribution of all tabular grains exceeds 25%, it is not preferable in terms of homogeneity between grains. Also, it is difficult to prepare an emulsion of less than 3%.
[0032]
Further, the variation coefficient of the twin plane spacing distribution of all tabular grains of the emulsion of the present invention is preferably 25 to 3%, more preferably 20 to 3%, still more preferably 15 to 3%. The variation coefficient of the twin plane spacing distribution is obtained by multiplying the value obtained by dividing the thickness variation (standard deviation) of the twin plane spacing of each tabular grain by the average twin plane spacing by 100. If the variation coefficient of the twin plane spacing distribution of all tabular grains exceeds 25%, it is not preferable in terms of homogeneity between grains. Also, it is difficult to prepare an emulsion of less than 3%.
[0033]
Next, the composition and structure of the tabular grains used in the present invention will be described.
The silver halide composition of the tabular grains used in the present invention is silver iodochlorobromide. Basically, the host tabular grains are silver iodobromide or silver iodochlorobromide, and the epitaxial junction site is composed of a combination of silver chloride, silver chlorobromide or silver iodochlorobromide. The silver chloride content of the tabular grains (ratio with respect to the total amount of silver combined with the host tabular grains and the epitaxial junction) is preferably 1 mol% or more and 6 mol% or less. More preferably, the silver chloride content is 2 mol% or more and 5 mol% or less. The silver iodide content is preferably 2 mol% or more. More preferably, the silver iodide content is 2 mol% or more and 10 mol% or less.
[0034]
In the host tabular grains of the present invention, the outermost layer containing 18 mol% or more of silver iodide is preferably 20% or less in terms of silver. Here, the silver iodide content of the outermost layer is mol% with respect to the silver of the outermost layer. Although the inner structure of the outermost layer is arbitrary, the silver iodide content is basically less than that of the outermost layer. The outermost layer is preferably 5% or more and 20% or less in terms of silver. More preferably, it is 10% or more and 15% or less. The silver iodide content of the outermost layer is preferably 3 mol% or more and 30 mol% or less. If this condition is deviated, the epitaxial deposition becomes uneven among the grains, so that dislocation lines do not enter and it is difficult to obtain the effects of the present invention.
[0035]
In the present invention, preferably, when the average silver chloride content of all silver halide grains is CL mol%, 70% or more of the total projected area is within the range of silver chloride content of 0.7 CL to 1.3 CL. And particularly preferably in the range of 0.8 CL to 1.2 CL. In the emulsion of the present invention, since the epitaxial deposition is uniform between grains, the silver chloride content distribution between grains is basically monodisperse. More preferably, when the average silver iodide content of all silver halide grains is I mol%, 70% or more of the total projected area is within the range of 0.7I to 1.3I. Particularly preferably in the range of 0.8I to 1.2I. Since the silver iodide content distribution between grains is monodispersed, epitaxial deposition becomes uniform between grains. The EPMA method (Electron Probe Micro Analyzer method) is usually effective for measuring the silver chloride and silver iodide content of each grain. By preparing a sample in which emulsion grains are dispersed so as not to contact each other and analyzing the X-rays emitted by emitting an electron beam, it is possible to perform elemental analysis of a very small region irradiated with the electron beam. . At this time, the measurement is preferably performed by cooling to a low temperature in order to prevent the sample from being damaged by the electron beam.
[0036]
In the emulsion of the present invention, 50% or more (number ratio) of all grains selectively has six silver halide epitaxial junctions per grain at the apex of the host tabular grains. More preferably, 70% or more of all grains are tabular grains having an epitaxial junction at the apexes at the six apexes of the hexagon. Here, the vertex portion is a sector formed by one vertex when the tabular grain is viewed from the direction perpendicular to the main surface and formed by this vertex and two sides constituting this vertex. It means a portion in a sector having a radius of 1/3 of the length of the shorter side. In the present invention, the larger the number of grains having an epitaxial junction at these six apexes, the better. When the shape of the main surface of the tabular grain is a rounded triangle or hexagon, the vertices and sides of the main surface are the vertices and sides of virtual triangles and hexagons formed by extending each side. And Usually, in addition to the epitaxial emulsion of the present invention, an epitaxial junction is formed on the main surface other than the vertex of the tabular grain or on the side other than the vertex. On the other hand, in the present invention, there is no epitaxial junction on the main surface other than the vertex or on the side other than the vertex, and the epitaxial junction is selectively provided only on each of the hexagonal vertexes. Features.
[0037]
The epitaxial junction is silver chloride, silver chlorobromide or silver iodochlorobromide. Preferably, the silver chloride content is 1 mol% or more higher than that of the host tabular grains. More preferably, the silver chloride content is 10 mol% or more higher than the host tabular grains. However, the silver chloride content of the epitaxial junction is preferably 50 mol% or less. The silver bromide content in the epitaxial junction is preferably 30 mol% or more, particularly preferably 50 mol% or more. The silver iodide content in the epitaxial junction is preferably 1 mol% or more and 20 mol% or less. The amount of silver in the epitaxial junction is preferably 1 mol% or more and 10 mol% or less, and more preferably 2 mol% or more and 7 mol% or less of the silver amount of the host tabular grain.
[0038]
The emulsion of the present invention comprises tabular grains having 50% or more (number ratio) of all grains having at least one dislocation line at the epitaxial junction. Preferably, 70% or more of all grains are composed of tabular grains having at least one dislocation line at the epitaxial junction. The emulsion of the present invention is more preferably composed of tabular grains in which 50% or more (number ratio) of all grains have network-like dislocation lines at the epitaxial junction. Most preferably, 70% or more of the total grains are composed of tabular grains having network dislocation lines at the epitaxial junction. Here, the network-like dislocation line is a dislocation line in which a plurality of dislocation lines that cannot be counted as a number are interlaced like a mesh. In a tabular grain having epitaxial junctions at two or more apexes, dislocation lines do not necessarily exist in each epitaxial junction. If the epitaxial junction bonded to at least one apex includes one dislocation line, preferably a network-like dislocation line, it corresponds to the epitaxial emulsion of the present invention. Preferably, 70% or more of the epitaxial junction at the apex includes a network dislocation line. In the present invention, it is preferable that 70% or more (number ratio) of all grains have no dislocation lines other than the epitaxial junction. Dislocation lines provide preferential deposition sites for epitaxial deposition and inhibit the formation of the epitaxial tabular grains of the present invention. Preferably, 70% or more (number ratio) of all particles have zero dislocation lines. In this case, the epitaxial junction is excluded. Most preferably, 90% or more of the total projected area has zero dislocation lines. The dislocation lines of tabular grains are described in, for example, J.A. F. Hamilton, Photo. Sci. Eng. 11, 57, (1967) and T.W. 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, it is possible to observe more clearly using a high-pressure type electron microscope (200 kV or more for a particle having a thickness of 0.25 μm). . From the photograph of the particles obtained by such a method, the position and number of dislocation lines for each particle when viewed from the direction perpendicular to the main surface can be obtained.
[0039]
In the emulsion of the present invention, preferably 70% or more of the total projected area, more preferably 80% or more of the total projected area is not epitaxially joined in a terrace shape on the main surface of the apex of the host tabular grain, It consists of tabular grains that protrude in the lateral direction and epitaxially join. Discrimination between tabular grains that protrude from the top of the main surface in the lateral direction of the host tabular grains and epitaxially join and tabular grains that epitaxially join in a terrace shape on the main surface of the apex of the host tabular grains is performed as follows. . Grains with an area of 60% or more of the portion projected in the side direction not overlapping the apex of the total projected area of the epitaxial junction per grain, extracted arbitrarily from tabular grain replica method electron micrographs Is defined as a tabular grain that protrudes in the lateral direction of the host tabular grain and epitaxially joins. If control is not performed to maintain this shape after epitaxial deposition, dislocation lines disappear due to rearrangement of epitaxial deposition.
[0040]
The epitaxial tabular emulsion of the present invention that satisfies the above conditions can lower the pBr of the emulsion. Here, pBr is the logarithm of the reciprocal of the bromine ion concentration. By making it possible to reduce pBr to 3.5 or less, the storage stability can be remarkably improved. Further, it can be incorporated into a photographic light-sensitive material assembled with silver iodobromide as a basic component, and the processing dependency problem can be solved. More preferably, the emulsion of the present invention has a pBr at 40 ° C. of 3.0 or less, particularly preferably 2.5 or less.
[0041]
The specific method for preparing the above-described epitaxial emulsion of the present invention will be described in detail in two parts: preparation of host tabular grains and preparation of an epitaxial junction.
First, the host tabular grains necessary for preparing the epitaxial emulsion of the present invention will be described in detail. The distribution of silver iodide in the host tabular grains of the present invention is preferably a multiple structure grain having a double structure or more. Here, having a structure with respect to the distribution of silver iodide means that the silver iodide content differs between each structure by 0.5 mol% or more, more preferably by 1 mol% or more. In the present invention, the “outermost layer” of the host tabular grain refers to a layered phase that is on the outermost side of the multiple structure of silver iodide distribution.
[0042]
The structure regarding the silver iodide distribution can be basically obtained by calculation from the prescription value in the grain preparation process. At the interface between the structures, the change in the silver iodide content can change suddenly or slowly. For these confirmations, it is necessary to consider analytical measurement accuracy, but the EPMA method described above is effective. The silver iodide distribution in the grains when the tabular grains are viewed from the direction perpendicular to the main surface can be analyzed by the same method. However, the cross section of the tabular grains can be obtained by solidifying the specimen and using a sample cut into ultrathin sections by a microtome. The intragranular silver iodide distribution can also be analyzed.
[0043]
In the present invention, the host tabular grains preferably have an outermost silver iodide content of 10 mol% or more. The outermost layer is preferably 20% or less with respect to the total silver amount, more preferably 5% or more and 20% or less, and the silver iodide content thereof is 15 mol% or more and 30 mol% or less. Here, the ratio of the outermost layer means the ratio of the amount of silver used for the preparation of the outermost layer to the amount of silver used to obtain the final grains in the host tabular grain preparation step. The silver iodide content means% of the molar ratio of the amount of silver iodide used for the preparation of the outermost layer to the amount of silver used for the preparation of the outermost layer, and the distribution thereof may be uniform or nonuniform. When the distribution of the silver iodide content is not uniform, the silver iodide content is an average value in the outermost layer. More preferably, the ratio of the outermost layer is 10% or more and 15% or less with respect to the total silver amount, and the silver iodide content thereof is 3 mol% or more and 30 mol% or less.
[0044]
The preparation of host tabular grains basically consists of a combination of three steps of nucleation, ripening and growth.
In the nucleation step, gelatin having a low methionine content described in US Pat. Nos. 4,713,320 and 4,942,120 is used, and a high pBr described in US Pat. No. 4,914,014 is used. The nucleation in a short time as described in JP-A-2-222940 is extremely effective in the nucleation step of the particles used in the present invention. In the present invention, the silver nitrate aqueous solution, the halogen aqueous solution and the low molecular weight oxidized gelatin are preferably added within one minute while stirring in the presence of low molecular weight oxidized gelatin at a temperature of 20 ° C. to 40 ° C. At this time, the pBr of the system is preferably 2 or more, and the pH is preferably 7 or less. The concentration of the aqueous silver nitrate solution is preferably 0.6 mol / L or less. Use of the above nucleation method facilitates formation of the epitaxial emulsion of the present invention.
[0045]
In the ripening step, the tabular grain emulsion of the present invention is carried out in the presence of a low concentration base described in US Pat. No. 5,254,453 and at a high pH described in US Pat. No. 5,013,641. It can be used in the aging step. U.S. Pat. Nos. 5,147,771, 5,147,772, 5,147,773, 5,171,659, 5,210,013, and It is possible to add the polyalkylene oxide compound described in No. 252,453 in the aging step or the subsequent growth step. In the present invention, the aging step is preferably performed at a temperature of 50 ° C. or higher and 80 ° C. or lower. It is preferable to reduce pBr to 2 or less immediately after nucleation or during aging. Further, additional gelatin is preferably added immediately after nucleation until the end of ripening. Particularly preferred gelatin has 95% or more of amino groups modified to succination or trimellitation. The use of these gelatins facilitates the preparation of the epitaxial emulsion of the present invention.
[0046]
In the growth step of the present invention, it is preferable to simultaneously add the silver nitrate aqueous solution, the halogen aqueous solution containing bromide and the silver iodide fine grain emulsion described in US Pat. Nos. 4,672,027 and 4,693,964. It is done. The silver iodide fine grain emulsion may be substantially silver iodide, and may contain silver bromide and / or silver chloride as long as it can form a mixed crystal. 100% silver iodide is preferred. Silver iodide may have β-form, γ-form and α-form or α-form-like structure as described in US Pat. No. 4,672,026 in 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 may be formed immediately before the addition described in US Pat. No. 5,004,679 or the like, or may be one that has undergone a normal water washing step. 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 grain size is 0.1 μm or less, more preferably 0.8. A thickness of 07 μm or less is convenient for the present invention. The particle shape cannot be completely specified because it is a fine particle, but the variation coefficient of the particle size distribution 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 particle size is defined as the diameter of a circle having a projected area equal to the observed particle. The particle size distribution is also determined by using this equivalent projected area circle 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.
[0047]
After the formation of the above-mentioned grains, the usual water washing described in US Pat. No. 2,614,929, etc., and the concentration adjustment of protective colloid agents such as pH, pI, gelatin and the concentration adjustment of silver iodide contained are preferably performed. 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. It may be 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 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.
[0048]
The method described in JP-A-2-188874 is most preferably used in the growth step of the present invention. An ultrafine grain emulsion of silver bromide, silver iodobromide or silver iodochlorobromide prepared immediately before the addition is continuously added during the growth of tabular grains, and the ultrafine grain emulsion is dissolved to grow tabular grains. An external mixer for preparing an ultrafine emulsion has a strong stirring ability, and an aqueous silver nitrate solution, an aqueous halogen solution and gelatin are added to the mixer. Gelatin can be added in advance or immediately before mixing with an aqueous silver nitrate solution and / or an aqueous halogen solution, or an aqueous gelatin solution alone. The gelatin preferably has a molecular weight smaller than that of a normal one, particularly preferably 10,000 to 50,000. Gelatin in which the amino group is modified by 90% or more to phthalation, succination or trimellitization and / or oxidation-treated gelatin with a reduced methionine content is particularly preferably used. By using this method, the preparation of the epitaxial emulsion of the present invention is facilitated.
[0049]
In the present invention, it is particularly preferable that 75% or less of all side surfaces of the side surfaces connecting the opposing (111) main surfaces of the host tabular grains are composed of (111) surfaces.
Here, 75% or less of all side surfaces are composed of (111) planes means that there are crystallographic planes other than (111) planes in a ratio higher than 25% of all side surfaces. Usually, the plane can be understood as a (100) plane, but other planes, that is, a (110) plane or a higher index plane can also be included. In the present invention, the effect is remarkable when 70% or less of all side surfaces are constituted by (111) planes.
[0050]
Whether or not 75% or less of all side faces are constituted by (111) faces can be easily determined from an electron micrograph by a carbon replica method with tabular grain shadows. When 75% or more of the normal side faces are composed of (111) faces, in the hexagonal tabular grains, the six side faces directly connected to the (111) main surface are different from each other, and the acute angle to the (111) main surface is different. And connect at an obtuse angle. On the other hand, when 75% or less of all side surfaces are composed of (111) faces, in hexagonal tabular grains, the six side faces directly connected to the (111) main surface are all obtuse angles with respect to the (111) main surface Connect with. By applying shadowing at an angle of 50 ° C. or less, the obtuse angle and the acute angle of the side surface with respect to the main surface can be determined. Preferably, the obtuse angle and the acute angle can be easily determined by shadowing at an angle of 30 ° or less and 10 ° or more.
[0051]
Furthermore, a method using adsorption of a sensitizing dye is effective as a method for obtaining the ratio between the (111) plane and the (100) plane. The ratio of the (111) plane and the (100) plane can be quantitatively determined using the method described in Journal of Chemical Society of Japan, 1984, Vol. 6, pages 942 to 947. Using the ratio and the equivalent circle diameter and thickness of the tabular grains described above, the ratio of the (111) planes on all sides can be calculated. In this case, the tabular grain is assumed to be a cylinder using the equivalent circle diameter and thickness. With this assumption, the ratio of the side surface to the total surface area can be obtained. The value obtained by multiplying the value obtained by dividing the ratio of the (100) plane obtained by the above-described adsorption of the sensitizing dye by the ratio of the above-described side face is 100. If the value is subtracted from 100, the ratio of the (111) plane in all side surfaces can be obtained. In the present invention, it is more preferable that the ratio of the (111) plane in all side surfaces is 65% or less.
[0052]
In the present invention, a method of making 75% or less of all side surfaces of the host tabular grain emulsion (111) plane will be described. Most generally, the ratio of the (111) face of the side face of the host tabular grain emulsion can be determined by the pBr at the time of preparation of the tabular grain emulsion. Preferably, the addition of 30% or more of the silver amount required for forming the outermost layer is set to pBr so that the ratio of the (111) plane of the side surface decreases, that is, the ratio of the (100) plane of the side surface increases. More preferably, the addition of 50% or more of the silver amount required for forming the outermost layer is set to pBr so that the ratio of the (111) plane of the side surface is reduced.
[0053]
As another method, after the total amount of silver is added, the ratio can be increased by setting pBr so that the ratio of the (100) plane of the side surface is increased and aging.
[0054]
The value of pBr that increases the ratio of the (100) side of the side is a wide range of values depending on the system temperature, pH, type and concentration of protective colloid agent such as gelatin, presence / absence of silver halide solvent, type, and concentration. Can change. Usually, it is preferably pBr 2.0 or more and 5 or less. More preferably, it is pBr2.5 or more and 4.5 or less. However, as described above, the value of pBr can be easily changed by the presence of, for example, a silver halide solvent. Examples of the silver halide solvent that can be used in the present invention include U.S. Pat. Nos. 3,271,157, 3,531,286, 3,574,628, and JP-A-54-1019. (A) Organic thioethers described in JP-A-54-158917, etc., (b) thiourea derivatives described in JP-A-53-82408, JP-A-55-77737, JP-A-55-2982, etc. (C) a silver halide solvent having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom as described in JP-A-53-144319, and (d) imidazole as described in JP-A-54-100717 (E) sulfite, (f) ammonia, (g) thiocyanate and the like.
[0055]
Particularly preferred solvents include thiocyanate, ammonia and tetramethylthiourea. The amount of the solvent used varies depending on the type. For example, in the case of thiocyanate, the preferred amount is 1 × 10 5 per mole of silver halide.^-Four1 x 10 moles or more^-2It is below the mole.
[0056]
As a method for changing the plane index of the side surface of the tabular grain emulsion, European Patent No. 515894A1 can be referred to. Further, polyalkylene oxide compounds described in US Pat. No. 5,252,453 and the like can also be used. As an effective method, the surface index modifiers described in U.S. Pat. Nos. 4,680,254, 4,680,255, 4,680,256 and 4,684,607 are used. Can be used. Ordinary photographic spectral sensitizing dyes can also be used as modifiers of the same plane index as described above.
[0057]
In the present invention, the host tabular grains preferably have no dislocation lines. Dislocation lines can be eliminated by using a combination of the nucleation, ripening, and growth steps detailed above.
[0058]
The epitaxial junction necessary for preparing the epitaxial emulsion of the present invention will be described in detail. Epitaxial deposition may be performed immediately after the formation of the host tabular grains, or may be performed after ordinary desalting is performed after the formation of the host tabular grains.
[0059]
Preferably, in the molecular weight distribution measured according to the PAGI method before epitaxial deposition, the high molecular weight component having a molecular weight of about 2 million or more is 5% to 30% and the low molecular weight component having a molecular weight of about 100,000 is 55% or less. It is preferable to contain gelatin in the range. Particularly preferably, in the molecular weight distribution measured according to the PAGI method, the high molecular weight component having a molecular weight of about 2 million or more is in the range of 5% to 15% and the low molecular weight component having a molecular weight of about 100,000 or less is in the range of 50% or less. Contains gelatin. The high molecular weight gelatin is contained in an amount of 10% by mass or more, preferably 30% or more, more preferably 50% or more of the total gelatin amount when performing epitaxial bonding. Although it is effective to add this gelatin before coating, the effect is reduced.
[0060]
Gelatin used in the emulsion of the present invention (hereinafter also referred to as “gelatin of the present invention”) is a collagen tissue that has been rendered water-soluble by degrading its structure with an alkali or acid. In the case of alkali-treated gelatin, sub-α (low molecular weight), α (molecular weight about 100,000), β (molecular weight about 200,000), γ (molecular weight about 300,000), void (high molecular weight), etc. Consists of.
[0061]
The ratio of the gelatin component in the present invention, that is, the molecular weight distribution, was measured by gel permeation chromatography (hereinafter referred to as “GPC method”) according to the internationally determined PAGI method. This method is described in detail in Takashi Ohno, Hiroyuki Kobayashi, Shinya Mizusawa, “Journal of the Photographic Society of Japan”, Vol. 47, No. 4, 1984, pages 237-247.
[0062]
The measurement conditions of the molecular weight distribution of gelatin according to the present invention are shown below.
(Measurement condition)
Column: Shodex Asahipak GS-620 7G (8mm I.D. x 500mm) x 2
Guard column: Shodex Asahipak GS-1G 7B
Eluent: 0.2 mol / liter phosphate buffer (pH 6.8)
Flow rate: 0.8 mL / min
Column temperature: 50 ° C
Detection: UV230nm
Sample concentration: 0.5 wt%
The GPC curve obtained by taking the absorbance on the horizontal axis and the absorbance on the vertical axis first shows the exclusion limit peak, then the β and α component peaks of gelatin, and the retention time becomes longer. As it goes down, it becomes a shape that draws the hem.
[0063]
The proportion of the high molecular weight component having a molecular weight of about 2 million or more in the present invention is determined by calculating the proportion of the exclusion limit peak area. Specifically, a perpendicular line is drawn with respect to the horizontal axis from the minimum point of the GPC curve that appears at the retention time 17th percentile, and the ratio of the area of the high molecular weight side (high molecular weight component) to the total area from the vertical line calculate. The proportion of low molecular weight components having a molecular weight of about 100,000 or less is determined by calculating the proportion of the total area of α components or less. Specifically, a perpendicular line is drawn with respect to the horizontal axis from the minimum point of the GPC curve between the β component peak and the α component peak appearing at the retention time around 23 minutes, and the portion on the low molecular weight side from the perpendicular (low molecular weight component) ) Is calculated as a percentage of the total area.
[0064]
In the gelatin of the present invention, a high molecular weight component having a molecular weight of about 2 million or more is controlled to 5% to 30% and a low molecular weight component having a molecular weight of about 100,000 or less is controlled to 55% or less. If the high molecular weight component exceeds 30%, the filterability is rapidly deteriorated. Further, when the low molecular weight component exceeds 55% and / or when the high molecular weight component is less than 5%, the effect of the present invention is not sufficiently exhibited. In order to exhibit the effect of the present invention, it is particularly preferable that the high molecular weight component having a molecular weight of about 2 million or more is 5% or more and 15% or less and the low molecular weight component having a molecular weight of about 100,000 or less is 50% or less.
[0065]
The gelatin of the present invention may be subjected to the following various modification treatments. For example, phthalated gelatin modified with amino group, succinylated gelatin, trimellit gelatin, pyromellitic gelatin, esterified gelatin modified with carboxyl group, amidated gelatin, formylated gelatin modified with imidazole group, methionine group decreased And oxidized reduced gelatin and increased reduced processed gelatin.
[0066]
On the other hand, other hydrophilic colloids can also be used.
For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose 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. Examples of gelatin include lime-processed gelatin, acid-processed gelatin, and Bull. Soc. Sci. Photo. Japan. No. 16. An enzyme-treated gelatin as described in P30 (1966) may be used, and a hydrolyzate or enzyme-decomposed product of gelatin can also be used.
[0067]
For the preparation of the epitaxial emulsion of the present invention, pH, pAg, gelatin type and concentration, and viscosity are selected. The pH is particularly important, and is preferably 4 or more and 5.5 or less. Particularly preferably, it is 4.5 or more and 5 or less. By setting this pH, epitaxial deposition can be performed uniformly between particles, and the effect of the present invention becomes remarkable.
[0068]
A sensitizing dye is used as a site indicator for epitaxial bonding of the present invention. By selecting the amount and type of the dye used, the epitaxial deposition position can be controlled. The dye is preferably added in an amount of 50% to 90% of the saturated coverage. 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 the cyanine dye. For these dyes, any of nuclei commonly used for cyanine dyes as basic heterocyclic nuclei can be applied. 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.
[0069]
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, 3,703 377, 3,769,301, 3,814,609, 3,837,862, 4,026,707, British Patent 1,344,281, No. 1,507,803, Japanese Patent Publication Nos. 43-4936, 53-12375, Japanese Patent Application Laid-Open Nos. 52-110618, and 52-109925.
Along with the sensitizing dye, a dye that itself does not have spectral sensitizing action or a substance that does not substantially absorb visible light and exhibits supersensitization may be added simultaneously or separately.
[0070]
When the sensitizing dye is adsorbed, it is preferable for the preparation of an epitaxial emulsion that the silver iodide content of the outermost surface layer of the host tabular grain is set higher than that of the outermost layer. Prior to the addition of the sensitizing dye, iodine ions are added. In the present invention, it is most preferable to add the aforementioned AgI fine grain emulsion to increase the silver iodide content on the surface of the host tabular grain. As a result, the distribution of the silver iodide content between the grains becomes uniform, and the adsorption of the sensitizing dye becomes uniform. This makes it possible to prepare the epitaxial emulsion of the present invention. The addition amount of these iodine ions or silver iodide is 1 × 10 5 per mol of silver in the host tabular grains.^-FourTo 1 × 10^-2The molar range is preferably 1 × 10^-3To 5 × 10^-3A molar range is particularly preferred.
[0071]
The epitaxial junction is formed by a solution containing halogen ions and AgNO._ThreeMay be added simultaneously or separately, and may be formed by adding AgCl fine particles, AgBr fine particles, AgI fine particles having a particle diameter smaller than that of the host tabular grains, or a combination of these mixed crystal grains. You may do it. AgNO_ThreeWhen adding the solution, the addition time is preferably 30 seconds or more and 10 minutes or less, and particularly preferably 1 minute or more and 5 minutes or less. In order to form the epitaxial emulsion of the present invention, the concentration of the silver nitrate solution to be added is preferably 1.5 mol / liter or less (hereinafter, the liter is also expressed as “L”), particularly 0.5 mol / L or less. Concentration is preferred. At this time, it is necessary to efficiently stir the system, and it is preferable that the viscosity of the system is low.
[0072]
The amount of silver in the epitaxial junction is preferably 1 mol% or more and 10 mol% or less, and more preferably 2 mol% or more and 7 mol% or less of the silver amount of the host tabular grain. If the amount is too small, an epitaxial emulsion cannot be prepared.
[0073]
The pBr at the time of forming the epitaxial junction is preferably 3.5 or more, particularly preferably 4.0 or more. The temperature is preferably 35 ° C. or higher and 45 ° C. or lower. It is preferable that a 6-cyano metal complex is doped when the epitaxial junction is formed.
[0074]
Among the 6 cyano metal complexes, those containing iron, ruthenium, osmium, cobalt, rhodium, iridium or chromium are preferred. The amount of metal complex added is 10 per mole of silver halide (total silver combined with host and epitaxial junctions).^-910^-2Preferably in the molar range, 10 per mole of silver halide.^-810^-FourMore preferably, it is in the molar range. The metal complex can be added by dissolving in water or an organic solvent. The organic solvent is preferably miscible with water. Examples of the organic solvent include alcohols, ethers, glycols, ketones, esters, and amides.
[0075]
As the metal complex, a 6-cyano metal complex represented by the following formula (I) is particularly preferable. By using an emulsion using a 6-cyano metal complex, a highly sensitive photosensitive material can be obtained, and the effect of suppressing the occurrence of fogging can be obtained even when the photosensitive material is stored for a long period of time.
[0076]
(I) [M (CN)₆]^n-
(Wherein M is iron, ruthenium, osmium, cobalt, rhodium, iridium or chromium, and n is 3 or 4).
[0077]
Specific examples of 6-cyano metal complexes are shown below.
(I-1) [Fe (CN)₆]^Four-
(I-2) [Fe (CN)₆]^3-
(I-3) [Ru (CN)₆]^Four-
(I-4) [Os (CN)₆]^Four-
(I-5) [Co (CN)₆]^3-
(I-6) [Rh (CN)₆]^3-
(I-7) [Ir (CN)₆]^3-
(I-8) [Cr (CN)₆]^Four-.
[0078]
The counter cation of the hexacyano complex is preferably an ion that is easily miscible with water and is compatible with the precipitation operation of the silver halide emulsion. Examples of counter ions include alkali metal ions (eg, sodium ions, potassium ions, rubidium ions, cesium ions, lithium ions), ammonium ions and alkylammonium ions.
[0079]
The emulsion of the present invention is preferably added with the above-described sensitizing dye and / or antifoggant and / or stabilizer described later after epitaxial deposition.
[0080]
In the present invention, it is preferable to lower pBr after this. Epitaxial emulsions other than the present invention cause epitaxial breakdown due to the decrease in pBr, resulting in low photographic performance. On the other hand, in the epitaxial emulsion of the present invention, this pBr can be lowered, and a remarkable effect can be exhibited in storage stability and processability. Preferably, pBr at 40 ° C. is lowered to 3.5 or less. More preferably, the emulsion of the present invention has a pBr at 40 ° C. of 3.0 or less, particularly preferably 2.5 or less. The reduction of pBr is basically carried out by adding bromine ions such as KBr and NaBr. After the epitaxial deposition, it is usually washed with water.
[0081]
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. The pH at the time of washing with water can be selected according to the purpose, but is preferably selected between 2 and 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, and an ion exchange 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.
[0082]
The emulsion of the present invention is preferably subjected to chemical sensitization after epitaxial deposition. 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, 34, June 1975, 13452, U.S. Pat. Nos. 2,642,361, 3,297,446, 3, No. 772,031, No. 3,857,711, No. 3,90 714, 4,266,018, and 3,904,415, and British Patent 1,315,755, pAg 5-10, pH 5-8 and temperature 30-30. At 80 ° C., sulfur, selenium, tellurium, gold, platinum, palladium, iridium or a combination of these sensitizers can be used. 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. In the case of gold sensitization, known compounds such as chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, and gold selenide can be used. The palladium compound means a palladium divalent salt or a tetravalent salt. Preferred palladium compounds are R₂PdX₆Or R₂PdX_FourIt 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.
[0083]
Specifically, K₂PdCl_Four, (NH_Four)₂PdCl₆, Na₂PdCl_Four, (NH_Four)₂PdCl_Four, Li₂PdCl_Four, Na₂PdCl₆Or K₂PdBr_FourIs preferred. Gold compounds and palladium compounds are preferably used in combination with thiocyanate or selenocyanate.
[0084]
As sulfur sensitizers, hypo, thiourea compounds, rhodanine compounds and sulfur described in US Pat. Nos. 3,857,711, 4,266,018 and 4,054,457 Containing compounds can be used. Chemical sensitization can also be performed in the presence of a so-called chemical sensitization aid. 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, 3,554,757, JP-A-58-126526, and the above-mentioned daffine. It is described in the book “photographic emulsion chemistry”, pp. 138-143.
[0085]
The emulsion of the present invention is preferably used in combination with gold sensitization. The preferred amount of gold sensitizer is 1 x 10 per mole of silver halide.^-Four~ 1x10^-7Mole, more preferably 1 × 10^-Five~ 5x10^-7Is a mole. The preferred range of palladium compound is 1 × 10 5 per mole of silver halide.^-3To 5 × 10^-7Is a mole. The preferred range of thiocyanate or selenocyan compound is 5 × 10 5 per mole of silver halide.^-2To 1 × 10^-6Is a mole.
[0086]
The preferred amount of sulfur sensitizer used for the silver halide grains used in the present invention is 1 × 10 5 per mole of silver halide.^-Four~ 1x10^-7Mole, more preferably 1 × 10^-Five~ 5x10^-7Is a mole.
[0087]
Selenium sensitization is a preferred sensitizing method for the emulsion of the present invention. In selenium sensitization, a known unstable selenium compound is used. Specifically, colloidal metal selenium, selenoureas (for example, N, N-dimethylselenourea, N, N-diethylselenourea), selenoketones Selenium compounds such as selenoamides can be used. Selenium sensitization may be preferably used in combination with sulfur sensitization or noble metal sensitization or both.
[0088]
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-6-27573, JP-A-6-175258, 6-180478, 6-208184, 6-208186, 6-317867, 7-140579, 7-301879, 7-301880, etc. Compounds can be used.
[0089]
Specifically, phosphine tellurides (for example, normal butyl-diisopropylphosphine telluride, triisobutylphosphine telluride, trinormal butoxyphosphine telluride, triisopropylphosphine 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), telluramides, telluroesters and the like may be used. Preferred are phosphine tellurides and diacyl (di) tellurides.
[0090]
The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fogging during the production process, storage or photographic processing of the light-sensitive material, or stabilizing the photographic performance. That is, 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) tetraazaindenes), pentaazaindenes 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, 3,982,947, and Japanese Patent Publication No. 52-28660 can be used. One preferred compound is a compound described in JP-A-63-212932. Antifoggants and stabilizers are used before particle formation, during particle formation, after particle formation, water washing step, during dispersion after water washing, during epitaxial formation, before chemical sensitization, during chemical sensitization, after chemical sensitization, before coating. It can be added according to the purpose at various times. 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.
[0091]
Depending on the purpose, it is preferable that a metal ion salt is present before preparing the emulsion of the present invention, for example, during grain formation, epitaxial formation, desalting step, chemical sensitization, and 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 (NO_Three)₂, Pb (NO_Three)₂, Pb (CH_ThreeCOO)₂, K_Three[Fe (CN)₆], (NH_Four)_Four[Fe (CN)₆], K_ThreeIrCl₆, (NH_Four)_ThreeRhCl₆, K_FourRu (CN)₆Can be given. The ligand of the coordination compound can be selected from halo, aco, 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.
[0092]
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 particle formation or can be added during particle formation. In addition, water-soluble silver salt (for example, AgNO_Three) 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.
[0093]
The silver halide photographic emulsion of the present invention preferably contains grains that undergo reduction sensitization during grain formation or after grain formation and have a hole trapping zone at least in the host portion of the grain. The hole trapping zone refers to a region having a function of capturing so-called holes, for example, holes generated in pairs with photoelectrons generated by photoexcitation. As a method for providing such a hole trapping zone, there is a method using a dopant, but in the present invention, it is desirable to provide it by intentional reduction sensitization. The reduction sensitization method includes a method of adding a reduction sensitizer to a silver halide emulsion, a method of growing or ripening in a low pAg atmosphere called silver ripening, and a pH of 8 to 11 called high pH ripening. Either a method of growing or aging in a high pH atmosphere can be selected. Two or more methods can be used in combination.
[0094]
In the present invention, intentional reduction sensitization means an operation of introducing hole-capturing silver nuclei into a part or all of silver halide grains by adding a reduction sensitizer. The hole-capturing silver nucleus means a small silver nucleus having a low development activity, and this silver nucleus can prevent recombination loss during the photosensitive process and increase the sensitivity.
[0095]
The method of adding a reduction sensitizer is a preferable method in that the level of reduction sensitization can be finely adjusted. 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 used in the present invention, these known reduction sensitizers can be selected and used, and two or more kinds of 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.
The reduction sensitizer is dissolved in water or an organic solvent such as alcohols, glycols, ketones, esters and amides and added during particle growth.
[0096]
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, 2NaCO_Three・ 3H₂O₂, Na_FourP₂O₇・ 2H₂O₂2Na₂SO_Four・ H₂O₂・ 2H₂O), peroxyacid salts (eg K₂S₂O₈, K₂C₂O₆, K₂P₂O₈), Peroxy complex compounds (for example, K₂[Ti (O₂) C₂O_Four] 3H₂O, 4K₂SO_Four・ Ti (O₂) OH / SO_Four・ 2H₂O, Na_Three[VO (O₂) (C₂H_Four)₂] 6H₂O), permanganate (eg KMnO)_Four), 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.
[0097]
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).
[0098]
Preferred oxidizing agents used in the present invention are ozone, hydrogen peroxide and its adducts, halogen elements, thiosulfonate inorganic oxidizing agents, and quinone organic oxidizing agents. It is a preferred embodiment to use the aforementioned reduction sensitization in combination with an oxidizing agent for silver. A method of applying reduction sensitization after using an oxidizing agent, a reverse method thereof, or a method of simultaneously coexisting both can be used. These methods can be selected and used in either the particle formation step or the chemical sensitization step.
[0099]
In the light-sensitive material produced using the silver halide emulsion obtained in the present invention, it is sufficient that at least one silver halide emulsion layer is provided on the support. At least one silver halide emulsion layer of each of a light-sensitive layer, a green color-sensitive layer, and a red color-sensitive layer, and among the blue-sensitive layer, the green-sensitive layer, and the red-sensitive layer, At least one is composed of two or more layers having different sensitivities. There are no particular restrictions on the number and order of the silver halide emulsion layers and the non-light-sensitive layers. 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.
[0100]
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.
The intermediate layer includes couplers and DIR compounds as described in JP-A Nos. 61-43748, 59-111438, 59-113440, 61-20037, and 61-20038. And may contain an anti-color mixing agent as commonly used.
[0101]
A plurality of silver halide emulsion layers constituting each unit photosensitive layer are composed of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in West German Patent 1,121,470 or British Patent 923,045. A two-layer structure 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, the low-sensitivity emulsion layer is close to the support on the side away from the support. A high-sensitivity emulsion layer may be provided on the side.
[0102]
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.
[0103]
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 62-63936, the blue photosensitive layer / GL / RL / GH / RH may be installed in this order from the side farthest from the support. .
[0104]
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 photosensitivity is arranged, and an arrangement composed of three layers having different photosensitivities in which the photosensitivity is gradually lowered toward the support. Even in the case of the three layers having different sensitivities, as described in JP-A-59-202464, the 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.
[0105]
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.
[0106]
The layer using the emulsion of the present invention may be a low-sensitivity emulsion layer, a medium-sensitivity emulsion layer, or a high-sensitivity emulsion layer. As the silver halide emulsion having no epitaxial junction, a tabular grain emulsion containing dislocation lines in the fringe part described in JP-A Nos. 11-174606 and 11-295832 is preferably used. This usage can improve the performance of the photosensitive material while reducing the amount of coated silver. The silver amount (mass in silver atoms) of the emulsion used in each emulsion layer is preferably 0.3 to 3 g / m²And more preferably 0.5 to 2 g / m²It is.
Further, the arrangement may be changed as described above even when there are four or more layers.
As described above, various layer configurations and arrangements can be selected according to the purpose of each photosensitive material.
[0107]
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.
[0108]
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.
[0109]

[0110]
Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, a compound capable of reacting with formaldehyde described in U.S. Pat. Nos. 4,411,987 and 4,435,503 is immobilized on a photosensitive material. It is preferable to add.
[0111]
Various color couplers can be used in the present invention, and specific examples thereof are the above-mentioned Research Disclosure No. 17643, VII-CG and No. 307105, described in the patents described in VII-CG.
[0112]
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. 58-10739, British Patent No. 1,425,020, No. 1,476,760, U.S. Pat. No. 3,973,968, No. 4,314,023, No. 4 511,649, European Patent No. 249,473A, and the like.
[0113]
The magenta coupler is preferably a 5-pyrazolone compound or a pyrazoloazole compound. US Pat. Nos. 4,310,619, 4,351,897, EP 73,636, US Pat. No. 061,432, No. 3,725,067, Research Disclosure No. 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. 4,500,630, Nos. 4,540,654, 4,556,630, and International Publication WO88 / 04795 are particularly preferable.
[0114]
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, 4,327,173, West German Patent Publication 3,329,729, European Patents 121,365A, 249,453A, U.S. Pat.Nos. 3,446,622, 4,333,999, 4,775,616, 4,451,559, 4,427,767, 4, No. 690,889, No. 4,254,212 The No. 4,296,199, are preferred according to JP-61-42658 or the like.
[0115]
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.
[0116]
As couplers in which the coloring dye has an appropriate diffusibility, U.S. Pat. No. 4,366,237, British Patent 2,125,570, European Patent 96,570, West German Patent (Publication) 3,234 No. 533 is preferred.
[0117]
Colored couplers for correcting unwanted absorption of chromogenic dyes are Research Disclosure No. No. 17643, VII-G, No. No. 307105, VII-G, U.S. Pat. No. 4,163,670, Japanese Patent Publication No. 57-39413, U.S. Pat. No. 4,004,929, U.S. Pat. No. 4,138,258, British Patent No. 1,16, Those described in No. 368 are preferred. Further, it reacts with a coupler that corrects unnecessary absorption of a coloring dye by a fluorescent dye released during coupling described in US Pat. No. 4,774,181, and a developing agent described in US Pat. No. 4,777,120. It is also preferable to use a coupler having a dye precursor group capable of forming a dye as a leaving group.
[0118]
Compounds that release photographically useful residues upon coupling can also be preferably used in the present invention. DIR couplers that release development inhibitors include those described in RD17643, VII-F, and No. 1 above. 307105, patents described in paragraph VII-F, JP-A-57-151944, 57-154234, 60-184248, 63-37346, 63-37350, US Pat. No. 4,248 No. 962, and No. 4,782,012 are preferred.
[0119]
Examples of couplers that release a nucleating agent or development accelerator in the form of an image during development include British Patent Nos. 2,097,140, 2,131,188, JP-A-59-157638, and 59-170840. Are preferred. Further, a fogging agent and a development accelerator are 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 silver halide solvents and the like.
[0120]
Other compounds that can be used in the light-sensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130,427, U.S. Pat. Nos. 4,283,472 and 4,338,393. No. 4,310,618, etc. Multi-equivalent couplers, JP-A-60-185950, JP-A-62-24252, etc., DIR redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing A redox compound or a DIR redox releasing redox compound, a coupler that releases a dye that recovers color after release described in European Patent Nos. 173,302A and 313,308A; 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, and leucos described in JP-A-63-75747. Examples include couplers that release a dye, and couplers that release a fluorescent dye described in US Pat. No. 4,774,181.
[0121]
The coupler used in the present invention can be introduced into the photosensitive material by various known dispersion methods.
Examples of high boiling solvents used in the oil-in-water dispersion method are described in, for example, US Pat. No. 2,322,027.
[0122]
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.
[0123]
Examples of latex dispersion process steps, effects and impregnating latexes 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. In the issue.
[0124]
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-benzisothiazolin-3-one. Various preservatives or fungicides such as n-butyl-p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, 2- (4-thiazolyl) benzimidazole It is preferable.
[0125]
The present invention can be applied to various photosensitive materials, but is preferably applied to various color photosensitive 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.
[0126]
Suitable supports that can be used in the present invention include, for example, the RD. No. 17643, page 28, ibid. No. 18716, page 647, right column to page 648, left column, and 307105, page 879.
[0127]
In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the side having an emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, still more preferably 18 μm or less, and particularly preferably 16 μm or less. 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.
[0128]
Membrane swelling speed T_1/2Can be adjusted by adding a hardener to gelatin as a binder or changing the aging conditions after coating.
[0129]
In the light-sensitive material of the present invention, a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 to 20 μm is preferably provided 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%.
[0130]
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.
[0131]
The color developer used for the development processing of the light-sensitive material 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.
[0132]
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 the chelating agent 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.
[0133]
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 replenishment amount of these developing solutions is generally expressed as 3 L per square meter of the photosensitive material, although it depends on the color photographic photosensitive material to be processed. ), And by reducing the bromide ion concentration in the replenisher, it can be reduced to 50 milliliters (hereinafter, milliliter is also referred to as “mL”). 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.
[0134]
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 (cm^Three]].
[0135]
The opening ratio is preferably 0.1 or less, more preferably 0.001 to 0.05. As a method for reducing the aperture ratio in this way, a movable lid described in JP-A-1-82033 is used 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. And a slit developing method described in JP-A-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.
[0136]
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.
[0137]
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 salts of ethylenediaminetetraacetic acid and 1,3-diaminopropanetetraacetic acid 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, but the processing can be performed at a lower pH in order to speed up the processing.
[0138]
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, and 2,059,988. JP-A-53-32736, 53-57831, 53-37418, 53-72623, 53-95630, 53-95631, 53-104232, 53-124424. 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. 51-14129; JP-B Nos. 45-8506, 52-20832 and 53 No. -32735, a thiourea derivative described in US Pat. No. 3,706,561, an iodide salt described in West German Patent No. 1,127,715 and JP-A No. 58-16235; West German Patent No. 966,410 No. 2,748,430; polyoxyethylene compounds described in JP-B No. 45-8836; other JP-A Nos. 49-40943, 49-59644, 53-94927 No., 54-35727, 55-26506, 58-163940; bromide ions and 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, and particularly described in US Pat. No. 3,893,858, West German Patent 1,290,812, and JP-A-53-95630. 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.
[0139]
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.
[0140]
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 the preservative for the fixing solution or the bleach-fixing solution, sulfites, bisulfites, carbonyl bisulfite adducts or sulfinic acid compounds described in European Patent No. 294,769A are preferred. 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.
[0141]
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 and the like. It is preferable to add imidazoles in an amount of 0.1 to 10 mol / L.
[0142]
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.
[0143]
In the desilvering step, it is preferable that the stirring is strengthened as much as possible. Specific methods for strengthening stirring include the method of causing a jet of processing solution to collide with the emulsion surface of a light-sensitive material described in JP-A-62-183460, and stirring using a rotating means in JP-A-62-183461. The method of raising the effect is mentioned. 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-mentioned stirring improving means is more effective when a bleaching accelerator is used, and the acceleration effect can be remarkably increased or the fixing inhibitory action can be eliminated by the bleaching accelerator.
[0144]
The automatic developing machine used for developing the photosensitive material of the present invention preferably has the photosensitive material conveying means described in JP-A-60-191257, JP-A-60-191258, and JP-A-60-191259. 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.
[0145]
The silver halide color photographic light-sensitive material of the present invention is generally subjected to water washing and / or stabilization after the desilvering process. 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. 248 to 253 (May 1955).
[0146]
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 of reducing calcium ions and magnesium ions described in JP-A-62-288838 can be used very effectively. Further, as described in JP-A-57-8542, for example, isothiazolone compounds, siabendazoles, chlorinated fungicides such as chlorinated sodium isocyanurate, and others such as benzotriazole, written by Horiguchi Hiroshi “Chemistry of Antibacterial and Antifungal Agents” (1986) Sankyo Publishing, Hygiene Technology Association “Microbial Sterilization, Sterilization, and Antifungal Technology” (1982) Industrial Technology Association of Japan The fungicides described in “Enamel Encyclopedia” (1986) can also be used.
[0147]
The pH of the washing water in the processing of the light-sensitive material 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.
[0148]
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.
[0149]
The overflow liquid accompanying the washing with water and / or the replenishment of the stabilizing liquid can be reused in other processes such as a desilvering process. 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.
[0150]
The silver halide color photographic light-sensitive material 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, an indoaniline compound 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, An aldol compound described in US Pat. No. 13,924, a metal salt complex described in US Pat. No. 3,719,492, and a urethane compound described in JP-A-53-135628 can be used.
[0151]
The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-3-pyrazolidones for the purpose of accelerating color development, if necessary. Typical compounds are described, for example, in JP-A Nos. 56-64339, 57-144547, and 58-115438.
[0152]
The various processing liquids in the present invention are 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.
[0153]
The silver halide light-sensitive material of the present invention is disclosed in U.S. Pat. No. 4,500,626, JP-A-60-133449, 59-218443, 61-238056, European Patent 210,660A2, etc. It can also be applied to the photothermographic material described in 1.
In addition, the silver halide color photographic light-sensitive material of the present invention is effective when it is applied to a film unit with a lens described in Japanese Patent Publication No. 2-332615 and Japanese Utility Model Publication No. 3-39784. It is.
[0154]
【Example】
Examples of the present invention are shown below. However, it is not limited to this embodiment.
Example 1
(Preparation of emulsion)
(Seed emulsion A)
1200 mL of an aqueous solution containing 0.9 g of KBr and 3 g of normal alkali-treated gelatin (average molecular weight 100,000) was kept at 35 ° C. and stirred (preparation of 1st solution). Ag-1 aqueous solution (AgNO in 100 mL_Three4.9 g), 37 mL of an X-1 aqueous solution (containing 3.5 g of KBr in 100 mL), and 20 mL of an aqueous G-1 solution (containing 2.5 g of the gelatin in 100 mL). It was added over 30 seconds at a constant flow rate by the jet method (addition 1). An aqueous solution containing 5.2 g of KBr was added, the temperature was raised to 75 ° C., and after an aging step for 9 minutes, 200 mL of an aqueous solution G-2 (containing 35 g of the gelatin in 100 mL) was added.
[0155]
Next, an Ag-2 aqueous solution (AgNO in 100 mL)_ThreeWas added over 20 minutes while accelerating the flow rate by the double jet method (addition of 149 mL of 14.9 g) and 159 mL of X-2 aqueous solution (containing 8.1 g of KBr and 0.24 g of KI in 100 mL). 2).
[0156]
Then, an Ag-3 aqueous solution (AgNO in 100 mL)_ThreeAnd 3-3 mL of X-3 aqueous solution (containing 23.0 g of KBr and 3.6 g of KI in 100 mL) were added over 25 minutes while accelerating the flow rate by the double jet method. At this time, the addition of the X-3 aqueous solution was performed so as to keep the silver potential of the bulk emulsion solution in the reaction vessel at 0 mV (saturated calomel electrode) (addition 3).
[0157]
Thereafter, desalting was carried out by a usual flocculation method, and then water, NaOH and gelatin were added with stirring, pH 5.8 at 56 ° C., pAg 8.8, and a mass in terms of silver per kg of emulsion 103.4 g. The gelatin mass was adjusted to 102 g. The obtained emulsion is an emulsion composed of tabular grains of silver iodobromide in which 98% or more (grain number ratio) of all grains are parallel and the main plane is the (111) plane, and the average equivalent sphere diameter is 0.63 μm. (The following seed emulsions B and C were also the same).
[0158]
(Seed emulsion B)
The seed emulsion A was prepared in the same manner as the seed emulsion A except for the following changes.
In (1st solution preparation), KBr 0.9 g was changed to 0.3 g, alkali-treated gelatin having an average molecular weight of 100,000 was changed to 15,000 alkali-treated gelatin, and the temperature was kept at 30 ° C. instead of 35 ° C. It was.
In (Addition 1), gelatin having an average molecular weight of 100,000 contained in G-1 aqueous solution is changed to gelatin of 15,000, and Ag-1 aqueous solution, X-1 aqueous solution and G-1 aqueous solution are mixed by triple jet method. Instead of adding for 30 seconds at a constant flow rate, it was added in 15 seconds. Further, the aging time after raising the temperature to 75 ° C. was changed from 9 minutes to 15 minutes.
[0159]
(Seed emulsion C)
The seed emulsion B was prepared in the same manner as the seed emulsion B except for the following changes.
In (1st solution preparation), alkali-treated gelatin having an average molecular weight of 15,000 was changed to oxidized gelatin (gelatin having an average molecular weight of 15,000 obtained by oxidizing methionine with hydrogen peroxide).
[0160]
(Emulsion 1-A)
An aqueous solution containing 67 g of the above seed emulsion A, 32 g of cross-linked high molecular weight gelatin (molecular weight distribution measured by the PAGI method is 12.4% for the high molecular weight component and 48.3% for the low molecular weight component) and 1.4 g of KBr. 1200 mL was kept at 75 ° C. and pH = 5 and stirred (preparation of 1st solution).
[0161]
Next, an Ag′-1 aqueous solution (AgNO in 100 mL)._ThreeAnd 935 mL of X'-1 aqueous solution (containing 11.5 g of KBr and 1.8 g of KI in 100 mL) were added over 70 minutes while accelerating the flow rate by the double jet method. At this time, the X'-1 aqueous solution was added so that the silver potential of the bulk emulsion solution in the reaction vessel was kept at 10 mV (saturated calomel electrode) (addition 1).
[0162]
Next, after adding an aqueous solution containing 1.8 mg of sodium benzenethiosulfonate, the temperature was lowered to 40 ° C., and an aqueous solution containing 0.08 mg of iridium hexachloride was added, and then an aqueous solution of Ag′-2 (into 100 mL) was added. AgNO_ThreeAnd 275 mL of X′-2 aqueous solution (containing 10.9 g of KBr and 2.7 g of KI in 100 mL) were added over 20 minutes by the double jet method. At this time, the X'-2 aqueous solution was added so that the silver potential of the bulk emulsion solution in the reaction vessel was kept at 30 mV (saturated calomel electrode) (addition 2).
[0163]
Thereafter, 10 mL of phenoxyethanol was added and an aqueous solution containing 0.4 g of KI was added over 1 minute, and then the sensitizing dye (gelatin dispersion) shown in the following chemical formula 1 was added in an amount corresponding to 80% of the saturated adsorption amount of the particles. Only added. Further, an aqueous solution containing 3 mg of potassium hexacyanoruthenium (II) was added.
[0164]
Thereafter, an Ag′-3 aqueous solution (AgNO3 in 100 mL)._Three55 mL and X′-3 (an aqueous solution containing NaCl 6 g and KBr 8.1 g in 100 mL) were added by a double jet over 5 minutes (addition 3).
[0165]
Next, an Ag-4 aqueous solution (AgNO in 100 mL)_Three(Containing 16 g) and X-4 aqueous solution (containing 11.6 g of KBr and 5.1 g of KI in 100 mL) were added over 4 minutes (addition 4).
Finally, 40 mg of the compound shown in the following chemical formula 2 was added.
[0166]
[Chemical 1]

[0167]
[Chemical formula 2]

[0168]
Subsequently, the temperature was lowered to 35 ° C., washed with normal water, added with 52 g of gelatin, dispersed at 40 ° C., adjusted to pH 6.5, and silver potential adjusted to 80 mV with respect to a saturated calomel electrode using NaCl aqueous solution. did. Next, 4 mg of the compound shown in the following chemical formula 3 was added, and potassium thiocyanate, chloroauric acid, sodium thiosulfate and N, N-dimethylselenourea were sequentially added to perform chemical sensitization, Chemical sensitization was terminated by adding the indicated water-soluble mercapto compound. Optimal chemical sensitization means that the sensitivity is maximized during 1/100 second exposure.
[0169]
[Chemical Formula 3]

[0170]
[Formula 4]

[0171]
The obtained emulsion is an emulsion composed of tabular grains of silver iodochlorobromide in which 97% or more (grain number ratio) of all grains are parallel and the main plane is the (111) plane, and the average sphere equivalent diameter is 1. It was 7 μm.
[0172]
(Emulsion 1-B)
Emulsion 1-A was prepared in the same manner as Emulsion 1-A, except for the following changes.
[0173]
In (Addition 3) of Emulsion 1-A, instead of an X′-3 aqueous solution (an aqueous solution containing 6 g of NaCl and 8.1 g of KBr in 100 mL), an X ″ -3 aqueous solution (an aqueous solution containing 8 g of NaCl and 4 g of KBr in 100 mL) was used. Using.
[0174]
(Emulsion 1-C)
Emulsion 1-B was prepared in the same manner as Emulsion 1-B, except for the following changes.
Instead of using seed emulsion A, seed emulsion B was used.
[0175]
(Emulsion 1-D)
Emulsion 1-B was prepared in the same manner as Emulsion 1-B, except for the following changes.
Instead of using seed emulsion A, seed emulsion C was used.
[0176]
(Emulsion 1-E)
Emulsion 1-A was prepared in the same manner as Emulsion 1-A, except for the following changes.
[0177]
In (Addition 1) of Emulsion 1-A, Ag'-1 aqueous solution and X'-1 aqueous solution were added by the double jet method while maintaining the silver potential of the bulk emulsion solution in the reaction vessel at -30 mV instead of 10 mV. Went.
[0178]
(Emulsion 1-F)
Emulsion 1-E was prepared in the same manner as Emulsion 1-E, except for the following changes.
In (Addition 3) of Emulsion 1-E, instead of an X′-3 aqueous solution (an aqueous solution containing 6 g of NaCl and 8.1 g of KBr in 100 mL), an X ″ -3 aqueous solution (an aqueous solution containing 8 g of NaCl and 4 g of KBr in 100 mL) was used. Using.
[0179]
(Emulsion 1-G)
Emulsion 1-F was prepared in the same manner as Emulsion 1-F, except for the following changes.
Instead of using seed emulsion A, seed emulsion B was used.
[0180]
(Emulsion 1-H)
Emulsion 1-F was prepared in the same manner as Emulsion 1-F, except for the following changes.
Instead of using seed emulsion A, seed emulsion C was used.
[0181]
(Emulsion 1-I)
Emulsion 1-A was prepared in the same manner as Emulsion 1-A, except for the following changes.
In (Addition 1) of Emulsion 1-A, instead of adding the Ag′-1 aqueous solution and the X′-1 aqueous solution by the double jet method, the Ag′-1 aqueous solution (AgNO_Three935 mL and X'-1 aqueous solution (containing 100 g of 11.5 g of KBr, 1.8 g of KI, and 20 g of gelatin having an average molecular weight of 15,000 obtained by oxidizing methionine with hydrogen peroxide) 888 mL was mixed in a chamber separate from the main reaction vessel having a magnetic coupling induction stirrer described in JP-A-10-43570 to prepare silver iodobromide ultrafine particles at the same time. Added continuously. At this time, silver iodobromide ultrafine particles were added so as to keep the silver potential of the bulk emulsion solution in the reaction vessel at 0 mV (saturated calomel electrode).
[0182]
(Emulsion 1-J)
Emulsion 1-1 was prepared in the same manner as Emulsion 1-1, except for the following changes.
In (Addition 3) of Emulsion 1-1, X′-3 aqueous solution (aqueous solution containing NaCl 8 g and KBr 4 g in 100 mL) was used instead of X′-3 aqueous solution (aqueous solution containing NaCl 6 g and KBr 8.1 g in 100 mL). Using.
[0183]
(Emulsion 1-K)
Emulsion 1-J was prepared in the same manner as Emulsion 1-J, except for the following changes.
Instead of using seed emulsion A, seed emulsion B was used.
[0184]
(Emulsion 1-L)
Emulsion 1-K was prepared in the same manner as Emulsion 1-K, except for the following changes.
Instead of using seed emulsion A, seed emulsion C was used.
[0185]
(Emulsion 1-M)
Emulsion 1-L was prepared in the same manner as Emulsion 1-L, except for the following changes.
[0186]
In (Addition 3) of Emulsion 1-L, an X ″ ′-3 aqueous solution (an aqueous solution containing 10 g of NaCl in 100 mL) was used instead of an X ″ -3 aqueous solution (an aqueous solution containing 8 g of NaCl and 4 g of KBr in 100 mL).
[0187]
Regarding the above emulsions 1-A to 1-M, the grain shape data, the ratio (number ratio) of tabular grains having 6 epitaxial junctions per grain at the host grain apex to the total grains, at least one in the epitaxial junction The ratio of tabular grains having dislocation lines to the total grains (number ratio) The ratio of the number of tabular grains having a distance between two parallel twin planes of 0.012 or 0.008 μm or less to the total grains (number ratio) Are summarized in the following Table 1 (all values were obtained by observing with an electron microscope by the method described in the text).
[0188]
[Table 1]

[0189]
(Preparation of coated sample and its evaluation)
The above emulsions 1-A-1 to 1-M were coated on a cellulose triacetate film support provided with an undercoat layer under the coating conditions shown in Table 2 below.
[0190]
[Table 2]

[0191]
These samples 101 to 113 were subjected to hardening for 14 hours under conditions of 40 ° C. and 70% relative humidity. Then, the sample was subjected to 1/100 second exposure through a gelatin filter SC-39 (long wavelength light transmission filter with a cut-off wavelength of 390 nm) and a continuous wedge manufactured by FUJIFILM Corporation. The photosensitivity and gradation were evaluated by measuring the density with the above.
[0192]
Using a negative processor FP-350 manufactured by Fuji Photo Film Co., Ltd., the treatment was carried out by the method described below (until the cumulative replenishment amount of the liquid became three times the mother liquid tank capacity).
[0193]

Next, the composition of the treatment liquid will be described.

[0194]

[0195]

[0196]
(Washing liquid) Common for tank and replenisher
Tap water was passed through a mixed bed column packed with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas Co.) and OH-type anion exchange resin (Amberlite IR-400), and calcium. And magnesium ion concentration was processed to 3 mg / L or less, and then sodium isocyanurate dichloride 20 mg / L and sodium sulfate 0.15 g / L were added. The pH of this solution was in the range of 6.5 to 7.5.
[0197]

[0198]
The results of photographic sensitivity and gradation are shown in Table 3 below. Sensitivity was displayed as a relative value of the reciprocal of the exposure amount necessary to reach the fog density plus 0.1 density of the obtained characteristic curve (the sensitivity of the sample 101 was 100). As for the gradation, the slope of a straight line connecting two points showing densities 0.2 and 0.8 higher than the fog density of the characteristic curve is used as the gradation value, and displayed as a relative value (the gradation of the sample 101). Of 100).
[0199]
[Table 3]

[0200]
From a comparison between Samples 101 to 106 and Samples 109 to 110 and Samples 107 to 108 and Samples 111 to 113, the sample using the emulsion of the present invention has high sensitivity and improved gradation (high contrast). I understand that there is.
[0201]
(Example 2)
In Emulsions 1-D, 1-H and 1-M of Example 1, an aqueous solution containing 1.5 g of catechol disulfonic acid sodium salt was added 2 minutes before (Addition 1) of each emulsion, and dioxide was added 1 minute before. Emulsions 1-D ′, 1-H ′, and 1-M ′ to which a hole trapping zone was added by adding an aqueous solution containing 0.002 g of thiourea were prepared and applied in the same manner as in Example 1. Table 4 below Samples 201 to 206 shown in FIG. The photographic performance was also evaluated in the same manner as in Example 1. The results are shown in Table 4 below.
[0202]
[Table 4]

[0203]
From a comparison between Samples 201 to 202 and Samples 203 to 206, the sample using the emulsion of the present invention has high sensitivity and improved gradation (high contrast) by providing a hole trapping zone. I understand that.
[0204]
(Example 3)
(Preparation of emulsion)
(Em-A)
1192 mL of an aqueous solution containing 0.96 g of low molecular weight gelatin, KBr, and 0.9 g was kept at 40 ° C. and stirred vigorously. AgNO_Three37.5 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 ripening, 30 g of trimellitated gelatin having a molecular weight of 100000 having a chemically modified amino group with trimellitic acid was added to adjust the pH to 7. 6 mg of thiourea dioxide was added. AgNO_Three, 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. AgNO_Three, 110.2 g containing aqueous solution 440.6 mL and KBr aqueous 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 the same time, an AgI fine grain emulsion having a grain size of 0.037 μm was simultaneously added at an accelerated flow rate so that the silver iodide content was 15.8 mol%, and the silver potential was kept at 0 mV with respect to the saturated calomel electrode. . AgNO_Three, 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 aforementioned AgI fine grain emulsion was added in terms of KI mass. Immediately after the addition, AgNO_Three, 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. After washing with water, gelatin was added and adjusted to pH, 5.8, pAg, 8.7 at 40 ° C. 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 mixed at 10 per mole of silver halide.^-1To 10^-8It means that it was selected from the range of molar addition amount.
[0205]
[Chemical formula 5]

[0206]
[Chemical 6]

[0207]
[Chemical 7]

[0208]
[Chemical 8]

[0209]
[Chemical 9]

[0210]
Embedded image

[0211]
(Em-B)
1192 mL of an aqueous solution containing 1.02 g of phthalated gelatin having a molecular weight of 100,000 and a phthalation rate of 97% containing 35 μmol of methionine per gram and 0.97 g of KBr was maintained at 35 ° C. and stirred vigorously. AgNO_ThreeAn aqueous solution containing 4.47 g, 42 mL and KBr, an aqueous solution containing 3.16 g, and 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 ripening, 41.2 g of trimellitated gelatin having a molecular weight of 100,000 used in the preparation of Em-A and 18.5 g of NaCl were added. After adjusting the pH to 7.2, 8 mg of dimethylamine borane was added. AgNO_Three, 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. AgNO_Three, 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 AgI fine grain emulsion used in the preparation of Em-A was added at a simultaneous flow acceleration so that the silver iodide content was 2.3 mol%, and the silver potential was -20 mV to the saturated calomel electrode. Kept. After adding 10.7 mL of 1N aqueous potassium thiocyanate solution, AgNO_Three153.5 mL of an aqueous solution containing 24.1 g and an aqueous KBr solution were added over 2 minutes and 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 aforementioned AgI fine grain emulsion was added in terms of KI mass. Immediately after the addition, AgNO_Three, 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-A and chemically sensitized.
[0212]
(Em-C)
AgNO during nucleation in the preparation of Em-B_ThreeThe addition amount was changed to 2.0 times.
And the final AgNO_Three, 57 g of 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-B.
[0213]
(Em-D)
1200 mL of an aqueous solution containing 0.21 g of modified silicone oil used in the preparation of low molecular weight gelatin having a molecular weight of 15000, 0.71 g, KBr, 0.92 g and Em-A was kept at 39 ° C., and the pH was adjusted to 1.8 vigorously. Stir. AgNO_ThreeAn 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 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. AgNO_Three, 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 AgI fine grain emulsion used in the preparation of Em-A 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, 2.5 g, AgNO_Three, 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-mentioned AgI 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, AgNO_Three, 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 AgI fine grain emulsion was added in terms of KI mass. Immediately after the addition, AgNO_Three609 mL of an aqueous solution containing 66.4 g 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 AgI fine grain emulsion to 1 mol of silver, sensitizing dyes 3 and 4 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.
[0214]
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[0215]
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[0216]
(Em-E)
AgNO during nucleation in the preparation of Em-D_ThreeIt was prepared in substantially the same manner as Em-D except that the addition amount was changed to 3.1 times. However, the sensitizing dye of Em-D was changed to sensitizing dyes 5, 6 and 7.
[0217]
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[0218]
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[0219]
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[0220]
(Em-F)
1200 mL of an aqueous solution containing 0.70 g of low molecular weight gelatin having a molecular weight of 15000, KBr, 0.9 g, KI, 0.175 g, and 0.2 g of modified silicon oil (product of Nippon Unicar Co., Ltd., L7602) was maintained at 33 ° C., and the pH was adjusted to 1. 8 and stirred vigorously. AgNO_ThreeAn 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 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. AgNO_Three, 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 molecular weight of 15000 and AgNO._ThreeSilver iodide containing AgI fine grain emulsion with a grain size of 0.008μ 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 At the same time, the rate was 4.1 mol%, and the silver potential was kept at -60 mV to the saturated calomel electrode. After adding KBr, 2.6 g, AgNO_Three, 87.7 g of aqueous solution and KBr aqueous solution were added over 49 minutes while accelerating the flow rate so that the final flow rate was 3.1 times the initial flow rate by the double jet method. At this time, the AgI 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, AgNO_Three, 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 AgI fine grain emulsion used in the preparation of Em-A was added in terms of KI mass. Immediately after the addition, AgNO_Three, 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. Washed with water and chemically sensitized in substantially the same manner as Em-E.
[0221]
(Em-G)
An aqueous solution containing 17.8 g of ion-exchanged gelatin having a molecular weight of 100,000, KBr, 6.2 g and KI, 0.46 g was kept at 45 ° C. and stirred vigorously. AgNO_ThreeAn 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 molecular weight of 100,000 was added and aged. After fully aging, AgNO_ThreeAn 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 7 g of NaCl, AgNO_ThreeOf 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 adding 14.4 g of KBr, 6.3 g of the AgI fine grain emulsion used in the preparation of Em-A was added in terms of KI mass. Immediately after the addition, AgNO_ThreeAn 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. Washed with water and chemically sensitized in substantially the same manner as Em-E.
[0222]
(Em-H)
Em-G was prepared in substantially the same manner except that the temperature during nucleation was changed to 38 ° C.
[0223]
(Em-I)
1200 mL of an aqueous solution containing phthalated gelatin having a phthalation rate of 97% and a molecular weight of 100,000, 0.38 g and KBr, 0.99 g was kept at 60 ° C., pH was adjusted to 2, and vigorously stirred. AgNO_ThreeAn aqueous solution containing 1.96 g and an aqueous solution containing KBr, 1.97 g and KI, 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 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. AgNO_Three20.7 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. AgNO_ThreeThe aqueous solution containing 65.6 g and the aqueous KBr solution were added over 37 minutes by 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 AgI fine grain emulsion used in the preparation of Em-A was added at the same time with the flow rate accelerated 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, AgNO_Three, 41.8 g of aqueous solution 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. 6.2 g of the above-mentioned AgI fine grain emulsion was added in terms of KI mass. Immediately after the addition, AgNO_Three300 mL of an aqueous solution containing 88.5 g 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 adding sensitizing dyes 8, 9, 10 and 11, 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.
[0224]
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[0225]
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[0226]
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[0227]
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[0228]
(Em-J)
1200 mL of an aqueous solution containing 4.9 g of low molecular weight gelatin having a molecular weight of 15000 and 5.3 g of KBr was kept at 60 ° C. and stirred vigorously. AgNO_Three27 mL of an aqueous solution containing 8.75 g and 36 mL of an aqueous solution containing KBr, 6.45 g were added by a double jet method over 1 minute. After heating to 77 ° C, AgNO_Three, 21 mL of an aqueous solution containing 6.9 g was added over 2.5 minutes. NH_FourNO_Three, 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. AgNO_Three, 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, AgNO_Three, 7.1 mL 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. AgNO_Three, 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 and chemically sensitized in substantially the same manner as Em-I.
[0229]
(Em-K)
The Em-J was prepared in substantially the same manner except that the temperature during nucleation was changed to 42 ° C.
[0230]
(Em-L, M, N)
Prepared in substantially the same manner as Em-G or Em-H. However, chemical sensitization was carried out in substantially the same manner as Em-I.
[0231]
(Em-O)
For Em-I, the sensitizing dye was changed to 5, 6 and 7, and chemical sensitization was optimally performed to obtain Em-O.
[0232]
The characteristics of the silver halide emulsions A to O thus obtained are shown in Table 5.
[0233]
[Table 5]

[0234]
1) Support
The support used in this example was prepared by the following method.
[0235]
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-shaped 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 technique: 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. Further, 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.
[0236]
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-sulfo di-2-ethylhexyl succinate 0.01 g / m², Salicylic acid 0.04 g / m²P-chlorophenol 0.2 g / m², (CH₂= CHSO₂CH₂CH₂NHCO)₂CH₂0.012 g / m²Polyamide-epichlorohydrin polycondensate 0.02 g / m²Apply a primer solution (10 mL / 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.).
[0237]
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.
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 · cm², 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.
[0238]
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)₂H_FiveC (CH₂OC ONH-C₆H_Three(CH_Three) NCO)_Three0.3 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) treated with silica particles (0.3 μm) and 3-poly (degree of polymerization 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 transporting devices in the drying zone were 115 ° C.). D of magnetic recording layer with X-light (blue filter)^BThe increase in color density is about 0.1, and the saturation magnetization moment of the magnetic recording layer is 4.2 Am²/ Kg, coercive force 7.3 × 10^FourA / m, the squareness ratio was 65%.
[0239]
3-3) Preparation of sliding layer
Diacetylcellulose (25mg / m²), C₆H₁₃CH (OH) C_TenH₂₀COOC₄₀H₈₁(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) and pouring and dispersing in propylene monomethyl ether at room temperature (10 times the amount). The average particle size was 0.01 μm) and then added. 15 mg / m each of aluminum particles (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 balls, 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 the sliding layer described later is 0.12. Excellent characteristics.
[0240]
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 301 to 305 as color negative photosensitive materials.
(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.
[0241]
(Sample 301)
First layer (first antihalation layer)
Black colloidal silver Silver 0.155
0.07μ 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.
[0242]
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.
[0243]
Third layer (intermediate layer)
0.07 μm AgBrI (2) 0.020
ExC-2 0.022
Polyethyl acrylate latex 0.085
Gelatin 0.294.
[0244]
4th layer (low sensitivity red sensitive emulsion layer)
Silver iodobromide emulsion Em-L Silver 0.065
Silver iodobromide emulsion Em-M Silver 0.100
Silver iodobromide emulsion Em-N Silver 0.158
ExC-1 0.109
ExC-3 0.044
ExC-4 0.072
ExC-5 0.011
ExC-6 0.003
Cpd-2 0.025
Cpd-4 0.025
HBS-1 0.17
Gelatin 0.80.
[0245]
5th layer (medium sensitivity red emulsion layer)
Silver iodobromide emulsion Em-J Silver 0.21
Silver iodobromide emulsion Em-K 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
Cpd-2 0.036
Cpd-4 0.028
HBS-1 0.16
Gelatin 1.18.
[0246]
6th layer (high-sensitivity red-sensitive emulsion layer)
Silver iodobromide emulsion Em-I 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.
[0247]
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.
[0248]
Eighth layer (Multilayer effect donor layer (layer that gives a multilayer effect to the red-sensitive layer))
Silver iodobromide emulsion Em-D 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.
[0249]
9th layer (low sensitivity green emulsion layer)
Silver iodobromide emulsion Em-F Silver 0.39
Silver iodobromide emulsion Em-G Silver 0.28
Silver iodobromide emulsion Em-H 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.
[0250]
10th layer (medium sensitive green sensitive emulsion layer)
Silver iodobromide emulsion Em-E Silver 0.20
Silver iodobromide emulsion Em-F Silver 0.25
ExC-6 0.009
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.
[0251]
11th layer (high sensitivity green emulsion layer)
Silver iodobromide emulsion Em-O Silver 1.200
ExC-6 0.004
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.
[0252]
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.
[0253]
13th layer (low sensitivity blue-sensitive emulsion layer)
Silver iodobromide emulsion Em-A Silver 0.18
Silver iodobromide emulsion Em-B Silver 0.20
Silver iodobromide emulsion Em-C Silver 0.07
ExC-1 0.041
ExC-8 0.012
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.
[0254]
14th layer (high sensitivity blue-sensitive emulsion layer)
Emulsion 1-A, 1-E, 1-H, 1-I, 1-M of Example 1 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.
[0255]
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.
[0256]
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.
[0257]
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 salts, iridium salts, ruthenium salts and rhodium salts. In addition, the coating solution for the eighth layer was 8.5 × 10 5 per mole of silver halide.^-3Grams, 7.9 x 10 in the eleventh layer^-3A sample was prepared by adding gram of calcium in an aqueous calcium nitrate solution. Further, at least one of W-1, W-6, W-7, and W-8 is contained for improving antistatic properties, and at least one of W-2 and W-5 is used for improving coating properties. Contains.
[0258]
Preparation of dispersions 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 5% aqueous p-octylphenoxyethoxyethoxyethane sulfonate and 0.5 g of 5% aqueous p-octylphenoxypolyoxyethylene ether (degree of polymerization 10) were placed in a 700 mL pot mill. Then, 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% gelatin aqueous solution, and the beads were removed by filtration to obtain a gelatin dispersion of the dye. The average particle diameter of the dye fine particles was 0.44 μm.
Similarly, a solid dispersion of ExF-4 was obtained. The average particle size of the dye fine particles was 0.45 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.
[0259]
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 pulverized for 8 hours through the slurry at a peripheral speed of about 10 m / sec and a discharge rate of 0.5 L / min. did.
The compounds used for forming each of the above layers are as shown below.
[0260]
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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 an evaporation correction means described in Japanese Society of Invention and Innovation technique 94-4992.
[0261]
The treatment process and the treatment liquid composition are shown below.

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 step, 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 for a photosensitive material 35 mm width 1.1 m, respectively. 2.0 mL. In addition, the crossover time is 6 seconds, and this time is included in the processing time of the previous process.
The opening area of the processor is 100 cm with color developer.², 120cm with bleach²Other processing solutions are about 100cm²Met.
[0262]
The composition of the treatment liquid is shown below.
[0263]

[0264]

[0265]
(Fixing (1) Tank liquid)
5:95 (volume ratio) mixture of the above bleach tank solution and the following fixing tank solution
(PH 6.8).
[0266]

[0267]
(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 / L or less, and then sodium isocyanurate dichloride 20 mg / L and sodium sulfate 150 mg / L were added. The pH of this solution was in the range of 6.5 to 7.5.
[0268]

[0269]
The said process was given with respect to the samples 301-305. Photographic performance was evaluated by measuring the density of the processed sample with a blue filter. The results of photographic sensitivity and gradation are shown in Table 6 below. Sensitivity was displayed as a relative value of the reciprocal of the exposure amount necessary to reach the fog density plus 0.05 density of the obtained characteristic curve (the sensitivity of the sample 301 was 100). In addition, regarding the gradation, the gradient value is expressed by the slope of a straight line connecting two points that are 0.1 and 0.3 higher than the fog density of the characteristic curve, and displayed as a relative value (the gradation of the sample 301). Of 100).
[0270]
[Table 6]

From the comparison between the sample 301 and the samples 302 to 305, it can be seen that the sample using the emulsion of the present invention has high sensitivity and improved gradation (high contrast).

Claims (2)

Silver halide photographic emulsion which is characterized from the following (i) and a score less than the (v).
(I) The silver iodochlorobromide hexagonal tabular grains having the (111) plane as the main surface and two parallel twin planes occupy 50% or more (number ratio) of the total grains.
(Ii) Hexagonal tabular grains having an equivalent circle equivalent diameter of 3.0 μm or more and an aspect ratio of 8 or more occupy 50% or more (number ratio) of all grains .
(Iii) Epitaxially bonded hexagonal tabular grains having six silver halide epitaxial junctions per grain selectively at the apex of the host hexagonal tabular grains account for 50% or more (number ratio) of all grains .
(Iv) Hexagonal tabular grains having an epitaxial junction having at least one dislocation line in the silver halide epitaxial junction account for 50% or more (number ratio) of all grains .
(V) Hexagonal tabular grains in which the distance between the two parallel twin planes is 0.012 μm or less occupy 50% or more (number ratio) of all grains .   2. A silver halide photographic material having at least one silver halide emulsion layer on a support, wherein at least one of the silver halide emulsion layers contains the silver halide photographic emulsion according to claim 1. A silver halide photographic light-sensitive material.