JP4083432B2 - Silver halide photographic emulsion and silver halide photographic light-sensitive material using the same - Google Patents

Description

【０１０９】
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。
【０１１０】
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。
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。
【０１１１】
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。
【０１１２】
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。
【０１１３】
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。
【０１１４】
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。
【０１１５】
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１，１４６，３６８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。
【０１１６】
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。
【０１１７】
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。
【０１１８】
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。
【０１１９】
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。
【０１２０】
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。
【０１２１】
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。
【０１２２】
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。
【０１２３】
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。
【０１２４】
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。
【０１２５】
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。
【０１２６】
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。
【０１２７】
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。
【０１２８】
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。
【０１２９】
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。
【０１３０】
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。
【０１３１】
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以下であり、補充液中の臭化物イオン濃度を低減させておくことにより５００ｍＬ以下にすることもできる。補充量を低減する場合には、処理液の空気との接触面積を小さくすることによって液の蒸発、空気酸化を防止することが好ましい。
【０１３２】
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）］
【０１３３】
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。
【０１３４】
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。
【０１３５】
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。
【０１３６】
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。
【０１３７】
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。
【０１３８】
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。
【０１３９】
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。
【０１４０】
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。
【０１４１】
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。
【０１４２】
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。
【０１４３】
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。
【０１４４】
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。
【０１４５】
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。
【０１４６】
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。
【０１４７】
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。
【０１４８】
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。
【０１４９】
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。
【０１５０】
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。
【０１５１】
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。
【０１５２】
【実施例】
以下に実施例をもって本発明を具体的に説明する。但し、本発明はこれらの実施例に限定されるものではない。
【０１５３】
（実施例−１）
本発明におけるエピタキシャル接合部の塩化銀含量ならびに平板粒子側面の（１１１）面比率の効果ついて説明する。
（乳剤ａの調製）
ＫＢｒ４．１ｇ、平均分子量２００００のゼラチン７．１ｇを含むｐＨを４に調整した水溶液１５００ｍＬを４０℃に保ち撹拌した。ＡｇＮＯ₃（８．４ｇ）水溶液とハロゲン（ＫＢｒ５．９ｇとＫＩ１．１ｇを含有する）水溶液をダブルジェット法で４０秒間に渡り添加した。平均分子量１０００００のコハク化ゼラチン３５．５ｇを加えた後ｐＨを５に調整し、その後５８℃に昇温した。ＡｇＮＯ₃（２．４ｇ）水溶液を２分間に渡り添加した後、６．２５ｍｏｌ／Ｌの硝酸アンモニウム水溶液５９ｍＬと１Ｎの水酸化ナトリウム水溶液５９ｍＬを添加した。１２分間熟成した後、酢酸を添加しｐＨを５に再調整した。第一成長としてＡｇＮＯ₃（１８２．３ｇ）水溶液とＫＢｒ水溶液をダブルジェット法で流量加速して２２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−２０ｍＶに保った。その後、第二成長としてＡｇＮＯ₃（２１．５ｇ）水溶液とＫＩを１７モル％含むＫＢｒ水溶液をダブルジェット法で５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前半の３分間は２０ｍＶに、その後８５ｍＶに保った。以上でエピタキシャル沈着前のホスト平板粒子が完成した。
【０１５４】
３８℃に降温した後ベンズイミダゾリウム１３４ｍｇを加えｐＨを４．５に調整した。ＫＩ（０．５ｇ）水溶液を添加した後、増感色素Ｉ、II、IIIを６：３：１のモル比で飽和被覆量の８０％の比率で添加した。但し増感色素は、特開平１１−５２５０７号に記載の方法で作成した固体微分散物として、使用した。すなわち硝酸ナトリウム０．８質量部および硫酸ナトリウム３．２質量部をイオン交換水４３質量部に溶解し、増感色素１３質量部を添加し、６０℃の条件下でディゾルバー翼を用い２０００ｒｐｍで２０分間分散することにより、増感色素の固体分散物を得た。ヘキサシアノルテニウム（II）酸カリウムを８．０×１０^-5モル（以降ホスト平板粒子の銀量１モルに対して）添加した。ＡｇＮＯ₃（９．２ｇ）水溶液１００ｍＬとＫＢｒ（２．１ｇ）とＮａＣｌ（２．８ｇ）を含むハロゲン水溶液１００ｍＬを一分間に渡りダブルジェット法で添加した。添加終了時の銀電位は飽和カロメル電極に対して＋９０ｍＶであった。
【０１５５】
かぶり防止剤Ｉを１×１０^-4モル添加した後、乳剤を３５℃で常法に従い水洗した後、平均分子量１０００００の脱イオンゼラチンを添加し４０℃で再分散しｐＨを５．５に調整した。５０℃に昇温し、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添加し最適に化学増感を施した。かぶり防止剤Ｉを５×１０^-4モル添加して化学増感を終了した。この乳剤を乳剤ａとした。
【０１５６】
乳剤ａは平均円相当径０．８２μｍ、円相当径の変動係数１８％、平均厚み０．０６５μｍ、厚みの変動係数１７％、平均アスペクト比１２．６の平板粒子であった。また、全投影面積の９０％以上が円相当径０．７μｍ以上で厚み０．０７５μｍ以下の最小の長さを有する辺の長さに対する最大の長さを有する辺の長さの比が１．４以下である六角形平板粒子で占められていた。粒子の切断断面の電子顕微鏡観察から平均双晶面間隔は０．０１０μｍでありその変動係数は１９％であった。低温での透過電子顕微鏡観察の結果、全投影面積の９０％以上がエピタキシャル接合部以外には転位線が観測されなかった。本乳剤はホスト平板粒子の沃化銀含量は１．７５モル％であり、エピタキシャル接合部の銀量はホスト平板粒子に対して４．２９モル％、全銀量に対して４．１１モル％である。
【０１５７】
【化１】

【０１５８】
（乳剤ｂ、ｃ、ｄ、ｅ、ｆの調製）
乳剤ａの調製におけるエピタキシャル沈着時のハロゲン水溶液のＫＢｒとＮａＣｌ量を変更し乳剤ｂ、ｃ、ｄ、ｅ、ｆを調製した。
【０１５９】
（乳剤ｇ、ｈ、ｉ、ｊ、ｋの調製）
乳剤ａの第二成長を以下のように変更して乳剤ｇを調製した。第二成長としてＡｇＮＯ₃（２１．５ｇ）水溶液とＫＢｒ水溶液をダブルジェット法で５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前半の３分間は２０ｍＶに、その後８５ｍＶに保った。この５分間の成長時に同時に添加直前に調製したＡｇＩ微粒子乳剤を沃化銀含量が１７モル％となるように添加した。ＡｇＩ微粒子乳剤は本発明の説明で記載した攪拌機を用い１．９１３質量％のＡｇＮＯ₃水溶液と１．９２質量％のＫＩと１．９質量％の平均分子量２００００のゼラチンを含む水溶液を２５℃で添加して調製した。調製後５秒で添加した。ＡｇＩ微粒子の平均粒子サイズは０．００８８μｍで粒子サイズ分布の変動係数は２４％であった。乳剤ｂ、ｃ、ｄ、ｅに同様の変更を行い乳剤ｈ、ｉ、ｊ、ｋを調製した。乳剤ｇ〜ｋの調製において添加直前に調製した沃化銀微粒子を用いる代わりに予め調製した平均粒子サイズ０．０３μｍ、その変動係数１４％の沃化銀微粒子乳剤を添加することにより乳剤ｇ−２、ｈ−２、ｉ−２、ｊ−２、ｋ−２を調製した。しかしながらいずれの場合も沃化銀微粒子乳剤が溶け残り写真特性の評価ができなかった。
【０１６０】
（乳剤ｌ、ｍ、ｎの調製）
乳剤ｄの第二成長を以下のように変更して乳剤ｌを調製した。５分間のダブルジェット添加時の銀電位を前半の３分間は２０ｍＶに、その後４０ｍＶに保った。この４０ｍＶを０ｍＶ、−２０ｍＶに変更して乳剤ｍ、ｎを調製した。
【０１６１】
（乳剤ｏ、ｐ、ｑの調製）
乳剤ｊの第二成長を以下のように変更して乳剤ｏを調製した。５分間のダブルジェット添加時の銀電位を前半の３分間は２０ｍＶに、その後４０ｍＶに保った。この４０ｍＶを０ｍＶ、−２０ｍＶに変更して乳剤ｐ、ｑを調製した。
【０１６２】
乳剤ａ〜ｑについての特性を表１にまとめて示す。エピタキシャル部の沈着についてはレプリカ法での電子顕微鏡観察から、エピタキシャル部の組成についてはフィ−ルドエミッション型電子銃を搭載した分析電子顕微鏡から、側面の（１１１）面比率については本文中に記した色素吸着を用いた方法で各々求めた。エピタキシャル部の塩化銀含量の粒子内および粒子間の分布の変動係数はいずれの場合も２０％以内であった。表１記載以外の乳剤の特性については基本的に乳剤ａとほぼ同様であった。
【０１６３】
【表１】

【０１６４】
表１の結果から明らかなように、添加直前に調製した沃化銀微粒子乳剤を添加することによりホスト平板粒子を形成した場合に平板粒子側面の（１１１）面比率が増加し、エピタキシャル接合を有する粒子比率が増加することがわかる。
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上記の化学増感を施した乳剤を保護層を設けて塗布し、試料Ｎｏ．１〜１７を作成した。
【０１６５】
【表２】

【０１６６】
これらの試料を４０℃、相対湿度７０％の条件下に１４時間放置した。その後、富士フイルム（株）製ゼラチンフィルターＳＣ−５０と連続ウェッジを通して１／１００秒間露光した。
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。
【０１６７】

【０１６８】
次に、処理液の組成を記す。

【０１６９】
（漂白液） タンク液、補充液共通（単位 ｇ）
エチレンジアミン四酢酸第二鉄アンモニウム二水塩 １２０．０
エチレンジアミン四酢酸二ナトリウム塩 １０．０
臭化アンモニウム １００．０
硝酸アンモニウム １０．０
漂白促進剤 ０．００５モル
（ＣＨ₃）₂Ｎ-ＣＨ₂-ＣＨ₂-Ｓ-Ｓ-ＣＨ₂-ＣＨ₂-Ｎ（ＣＨ₃）₂・２ＨＣｌ
アンモニア水（２７％） １５．０ｍＬ
水を加えて １．０Ｌ
ｐＨ（アンモニア水と硝酸にて調整） ６．３
【０１７０】

【０１７１】
（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。
【０１７２】
（安定液） タンク液、補充液共通（単位 ｇ）
ｐ−トルエンスルフィン酸ナトリウム ０．０３
ポリオキシエチレン−ｐ−モノノニルフェニルエーテル
（平均重合度１０） ０．２
エチレンジアミン四酢酸二ナトリウム塩 ０．０５
１，２，４−トリアゾール １．３
１，４−ビス（１，２，４−トリアゾール−１−
イルメチル）ピペラジン ０．７５
水を加えて １．０Ｌ
ｐＨ ８．５
【０１７３】
処理済みの試料を緑色フィルタ−で濃度測定した。また発色現像の処理時間を３分１５秒から１分１５秒に変更して同様の評価を行い現像進行性を評価した。以上により得られた、かぶりプラス０．２ならびに２．０の濃度での感度値、かぶり値を表３に示す。
【０１７４】
【表３】

【０１７５】
表３の乳剤ａからｆの比較から明らかなようにエピタキシャル接合部の塩化銀含量が本発明の５モル％以上２５モル％以下となることにより感度／かぶり比に優れ、かつ短い処理時間での発色濃度が顕著に増加することがわかる。乳剤ａからｅと乳剤ｇからｋの比較からホスト平板粒子を添加直前に調製した沃化銀微粒子乳剤を添加して形成し側面の（１１１）面比率が高いと同様に感度／かぶり比に優れ、かつ短い処理時間での発色濃度が顕著に増加することがわかる。乳剤ｄとｌからｎの比較ならびに乳剤ｊとｏからｑの比較から本発明のエピタキシャル部の塩化銀含量の効果と平板粒子側面の（１１１）面比率の効果は相乗的であることがわかる。
【０１７６】
（実施例−２）
本発明におけるエピタキシャル部の沃化銀含量、とくに添加直前に調製した沃化銀微粒子乳剤を添加する効果について説明する。
（乳剤ｒ、ｓ、ｔ、ｕ、ｖの調製）
実施例−１の乳剤ｃ、ｄ、ｌ、ｏおよびｑのエピタキシャル接合を以下のように変更して乳剤ｒ、ｓ、ｔ、ｕおよびｖを調製した。３８℃に降温した後ベンズイミダゾリウム１３４ｍｇを加えｐＨを４．５に調整した。ＫＩ（０．５ｇ）水溶液を添加した後、増感色素Ｉ、II、IIIを６：３：１のモル比で飽和被覆量の８０％の比率で添加した。但し増感色素は、特開平１１−５２５０７号に記載の方法で作成した固体微分散物として、使用した。すなわち硝酸ナトリウム０．８質量部および硫酸ナトリウム３．２質量部をイオン交換水４３質量部に溶解し、増感色素１３質量部を添加し、６０℃の条件下でディゾルバー翼を用い２０００ｒｐｍで２０分間分散することにより、増感色素の固体分散物を得た。ヘキサシアノルテニウム（II）酸カリウムを８．０×１０^-5モル（以降ホスト平板粒子の銀量１モルに対して）添加した。ＡｇＮＯ₃（９．２ｇ）水溶液１００ｍＬとＫＢｒ（２．１ｇ）とＮａＣｌ（２．８ｇ）を含むハロゲン水溶液１００ｍＬを一分間に渡りダブルジェット法で添加した。
【０１７７】
このダブルジェット添加時の１分前に添加直前に調製したＡｇＩ微粒子乳剤をエピタキシャル接合部の銀量に対して７モル％量を添加した。ＡｇＩ微粒子乳剤は本発明の説明で記載した攪拌機を用い１．９１３質量％のＡｇＮＯ₃水溶液と１．９２質量％のＫＩと１．９質量％の平均分子量２００００のゼラチンを含む水溶液を２５℃で添加して調製した。調製後５秒で１０秒間に渡り添加した。ＡｇＩ微粒子の平均粒子サイズは０．００８８μｍで粒子サイズ分布の変動係数は２４％であった。添加終了時の銀電位は飽和カロメル電極に対して＋９０ｍＶであった。かぶり防止剤Ｉを１×１０^-4モル添加した後、乳剤を３５℃で常法に従い水洗した後、平均分子量１０００００の脱イオンゼラチンを添加し４０℃で再分散しｐＨを５．５に調整した。５０℃に昇温し、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添加し最適に化学増感を施した。かぶり防止剤Ｉを５×１０^-4モル添加して化学増感を終了した。
【０１７８】
乳剤ｒ〜ｖの調製において添加直前に調製した沃化銀微粒子を用いる代わりに予め調製した平均粒子サイズ０．０３μｍ、その変動係数１４％の沃化銀微粒子乳剤を添加することにより乳剤ｗ、ｘ、ｙ、ｚ、ｚ−２を調製した。しかしながらいずれの場合も沃化銀微粒子乳剤が溶け残り写真特性の評価ができなかった。
【０１７９】
乳剤ｒ〜ｖについての特性を表４にまとめて示す。エピタキシャル部の沈着についてはレプリカ法での電子顕微鏡観察から、エピタキシャル部の組成についてはフィ−ルドエミッション型電子銃を搭載した分析電子顕微鏡から、側面の（１１１）面比率については本文中に記した色素吸着を用いた方法で各々求めた。エピタキシャル部の塩化銀および沃化銀含量の粒子内および粒子間の分布の変動係数はいずれの場合も２０％以内であった。表４記載以外の乳剤の特性については基本的に乳剤ａとほぼ同様であった。
【０１８０】
【表４】

【０１８１】
実施例１と同様に塗布して写真特性を評価した結果を表５に示す。
【０１８２】
【表５】

【０１８３】
表５から明らかなように添加直前に調製した沃化銀微粒子乳剤を添加することによりエピタキシャル部を形成した本発明の乳剤はかぶりが低く高感度である。また処理時間が短い場合の発色濃度が極めて高い。
【０１８４】
（実施例−３）
多層カラ−写真感光材料における本発明の乳剤の効果を示す。
以下の製法によりハロゲン化銀乳剤Ｅｍ−ＡからＥｍ−Ｍを調製した。
（Ｅｍ−Ａの製法）
フタル化率９７％のフタル化した分子量１５０００の低分子量ゼラチン３１．７ｇ、ＫＢｒ３１．７ｇを含む水溶液４２．２Ｌを３５℃に保ち激しく攪拌した。ＡｇＮＯ₃３１６．７ｇを含む水溶液１５８３ｍＬとＫＢｒ２２１．５ｇ、分子量１５０００の低分子量ゼラチン５２．７ｇを含む水溶液１５８３ｍＬをダブルジェット法で１分間に渡り添加した。添加終了後、直ちにＫＢｒ５２．８ｇを加えて、ＡｇＮＯ₃３９８．２ｇを含む水溶液２４８５ｍＬとＫＢｒ２９１．１ｇを含む水溶液２５８１ｍＬをダブルジェット法で２分間に渡り添加した。添加終了後、直ちにＫＢｒ４４．８ｇを添加した。その後、４０℃に昇温し、熟成した。熟成終了後、フタル化率９７％のフタル化した分子量１０００００のゼラチン９２３ｇとＫＢｒ７９．２ｇを添加し、ＡｇＮＯ₃５１０３ｇを含む水溶液１５９４７ｍＬ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１．４倍になるように流量加速して１０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−６０ｍＶに保った。水洗した後、ゼラチンを加えｐＨ５．７、ｐＡｇ８．８、乳剤１ｋｇ当たりの銀換算の質量１３１．８ｇ、ゼラチン質量６４．１ｇに調整し、種乳剤とした。
【０１８５】
フタル化率９７％のフタル化ゼラチン４６ｇ、ＫＢｒ１．７ｇを含む水溶液１２１１ｍＬを７５℃に保ち激しく攪拌した。前述した種乳剤を９．９ｇ加えた後、変成シリコンオイル（日本ユニカー株式会社製品、Ｌ７６０２）を０．３ｇ添加した。Ｈ₂ＳＯ₄を添加してｐＨを５．５に調整した後、ＡｇＮＯ₃７．０ｇを含む水溶液６７．６ｍＬ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６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−２０ｍＶに保った。ベンゼンチオスルホン酸ナトリウム２ｍｇと二酸化チオ尿素２ｍｇを添加した後、ＡｇＮＯ₃１０５．６ｇを含む水溶液３２８ｍＬ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３．７倍になるように流量加速して５６分間に渡り添加した。この時、０．０３７μｍの粒子サイズのＡｇＩ微粒子乳剤をヨウ化銀含有率が２７ｍｏｌ％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−５０ｍＶに保った。
【０１８６】
ＡｇＮＯ₃４５．６ｇを含む水溶液１２１．３ｍＬとＫＢｒ水溶液をダブルジェット法で２２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＋２０ｍＶに保った。８２℃に昇温し、ＫＢｒを添加して銀電位を−８０ｍＶに調整した後、前述したＡｇＩ微粒子乳剤をＫＩ質量換算で６．３３ｇ添加した。添加終了後、直ちに、ＡｇＮＯ₃６６．４ｇを含む水溶液２０６．２ｍＬを１６分間に渡り添加した。添加初期の５分間はＫＢｒ水溶液で銀電位を−８０ｍＶに保った。水洗した後、ゼラチンを添加し４０℃でｐＨ５．８、ｐＡｇ８．７に調整した。化合物１１および１２を添加した後、６０℃に昇温した。増感色素１１および１２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１３および化合物１４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１ｍｏｌあたり１０^-1から１０^-8ｍｏｌの添加量範囲から選択したことを意味する。
【０１８７】
【化２】

【化３】

【化４】

【化５】

【化６】

【化７】

（Ｅｍ−Ｂの製法）
低分子量ゼラチン０．９６ｇ、ＫＢｒ０．９ｇを含む水溶液１１９２ｍＬを４０℃に保ち、激しく攪拌した。ＡｇＮＯ₃１．４９ｇを含む水溶液３７．５ｍＬとＫＢｒを１．０５ｇ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。熟成終了後、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、３５ｇ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。ＡｇＮＯ₃２９ｇ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。
【０１８８】
ＡｇＮＯ₃１１０．２ｇを含む水溶液４４０．６ｍＬとＫＢｒ水溶液をダブルジェット法で最終流量が初期流量の５．１倍になるように流量加速して３０分間に渡り添加した。この時、Ｅｍ−Ａの調製で使用した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。ＡｇＮＯ₃２４．１ｇ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ＡｇＮＯ₃５７ｇを含む水溶液２２８ｍＬを５分間に渡り添加した。この時、添加終了時の電位が＋２０ｍＶになるようにＫＢｒ水溶液で調整した。Ｅｍ−Ａとほぼ同様に水洗し、化学増感した。
【０１８９】
（Ｅｍ−Ｃの製法）
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、ＫＢｒ ０．９ｇを含む水溶液１１９２ｍＬを３５℃に保ち、激しく攪拌した。ＡｇＮＯ₃４．４７ｇを含む水溶液、４２ｍＬとＫＢｒ３．１６ｇ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、６３℃に昇温し、熟成した。熟成終了後、Ｅｍ−Ｂ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。ＡｇＮＯ₃２６ｇ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。ＡｇＮＯ₃１１０．２ｇ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。
【０１９０】
１Ｎのチオシアン酸カリウム水溶液１０．７ｍＬを添加した後、ＡｇＮＯ₃２４．１ｇ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ＡｇＮＯ₃５７ｇ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。
【０１９１】
（Ｅｍ−Ｄの製法）
Ｅｍ−Ｃの調製において核形成時のＡｇＮＯ₃添加量を２．３倍に変更した。そして、最終のＡｇＮＯ₃５７ｇを含む水溶液４０４ｍＬの添加終了時の電位が＋９０ｍＶになるようにＫＢｒ水溶液で調整するように変更した。それ以外はＥｍ−Ｃとほぼ同様にして調製した。
【０１９２】
（Ｅｍ−Ｅの製法）
分子量１５０００の低分子量ゼラチン０．７５ｇ、ＫＢｒ ０．９ｇ、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。ＡｇＮＯ₃０．４５ｇ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１６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。５４℃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、ＫＢｒ２．９ｇを添加した。ＡｇＮＯ₃２８．８ｇ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。
【０１９３】
ＫＢｒ２．５ｇを添加した後、ＡｇＮＯ₃８７．７ｇ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、ＡｇＮＯ₃４１．８ｇ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ＡｇＮＯ₃６６．４ｇ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。
【０１９４】
水洗した後、ゼラチンを添加し４０℃でｐＨ６．５、ｐＡｇ８．２に調整した。化合物１１および１２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１３および１４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１３および１４を添加した。
【０１９５】
【化８】

【化９】

（Ｅｍ−Ｆの製法）
Ｅｍ−Ｅの調製において核形成時のＡｇＮＯ₃添加量を４．１２倍に変更した以外はＥｍ−Ｅとほぼ同様にして調製した。但しＥｍ−Ｅの増感色素を増感色素１２、１５、１６および１７に変更した。
【０１９６】
【化１０】

【化１１】

【化１２】

（Ｅｍ−Ｇの製法）
分子量１５０００の低分子量ゼラチン０．７０ｇ、ＫＢｒ ０．９ｇ、ＫＩ ０．１７５ｇ、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３３℃に保ち、ｐＨを１．８に調製し激しく攪拌した。ＡｇＮＯ₃１．８ｇ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。６２℃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、ＫＢｒ２．９ｇを添加した。ＡｇＮＯ₃２７．５８ｇ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０．００８μｍ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。
【０１９７】
ＫＢｒ２．６ｇを添加した後、ＡｇＮＯ₃８７．７ｇ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、ＡｇＮＯ₃４１．８ｇ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ＡｇＮＯ₃６６．４ｇを含む水溶液３２１ｍＬを４分間に渡り添加した。添加初期の２分間はＫＢｒ水溶液で銀電位を−６０ｍＶに保った。Ｅｍ−Ｆとほぼ同様に水洗し、化学増感した。
【０１９８】
（Ｅｍ−Ｈの製法）
イオン交換した分子量１０００００のゼラチン１７．８ｇ、ＫＢｒ６．２ｇ、ＫＩ ０．４６ｇを含む水溶液を４５℃に保ち激しく攪拌した。ＡｇＮＯ₃１１．８５ｇ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４５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。熟成終了後、ＡｇＮＯ₃１３３．４ｇ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。
【０１９９】
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ＡｇＮＯ₃４２．７ｇを含む水溶液とＫＢｒ水溶液をダブルジェット法で１１分間に渡り添加した。この時、銀電位を＋９０ｍＶに保った。Ｅｍ−Ｆとほぼ同様に水洗し、化学増感した。
【０２００】
（Ｅｍ−Ｉの製法）
Ｅｍ−Ｈの調製において核形成時の温度を３５℃に変更した以外はほぼ同様にして調製した。
【０２０１】
（Ｅｍ−Ｊの製法）
フタル化率９７％の分子量１０００００のフタル化ゼラチン０．３８ｇ、ＫＢｒ ０．９ｇ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。ＡｇＮＯ₃１．９６ｇを含む水溶液とＫＢｒ １．６７ｇ、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、ＫＢｒ２．９９ｇ、ＮａＣｌ ６．２ｇを添加した。ＡｇＮＯ₃２７．３ｇを含む水溶液６０．７ｍＬとＫＢｒ水溶液をダブルジェット法で３１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。ＡｇＮＯ₃６５．６ｇ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。
【０２０２】
二酸化チオ尿素１．５ｍｇを添加した後、ＡｇＮＯ₃４１．８ｇ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ＡｇＮＯ₃８８．５ｇ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、ｐＡｇ８．２に調整した。化合物１１および１２を添加した後、６１℃に昇温した。増感色素１８、１９、２０および２１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１３および１４を添加した。
【０２０３】
【化１３】

【化１４】

【０２０４】
【化１５】

【０２０５】
【化１６】

【０２０６】
（Ｅｍ−Ｋの製法）
分子量１５０００の低分子量ゼラチン４．９ｇ、ＫＢｒ５．３ｇを含む水溶液１２００ｍＬを６０℃に保ち激しく攪拌した。ＡｇＮＯ₃８．７５ｇを含む水溶液２７ｍＬとＫＢｒ６．４５ｇ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。７５℃に昇温した後、ＡｇＮＯ₃６．９ｇを含む水溶液２１ｍＬを２分間に渡り添加した。ＮＨ₄ＮＯ₃２６ｇ、１Ｎ，ＮａＯＨ５６ｍＬを順次、添加した後、熟成した。熟成終了後ｐＨを４．８に調整した。ＡｇＮＯ₃１４１ｇ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。
【０２０７】
５５℃に降温した後、ＡｇＮＯ₃７．１ｇ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。ＡｇＮＯ₃５７．２ｇを含む水溶液１７７ｍＬとＫＢｒ４０．２ｇを含む水溶液２２３ｍＬを８分間に渡ってダブルジェット法で添加した。Ｅｍ−Ｊとほぼ同様に水洗し、化学増感した。
【０２０８】
（Ｅｍ−Ｌの製法）
Ｅｍ−Ｋの調製において核形成時の温度を４０℃に変更した以外は、ほぼ同様にして調製した。
【０２０９】
（Ｅｍ−Ｍの製法）
Ｅｍ−Ｊとほぼ同様にして調製した。但し化学増感はＥｍ−Ｆとほぼ同様の方法で行った。
【０２１０】
Ｅｍ−ＡからＥｍ−Ｍのハロゲン化銀乳剤の特性値を表６にまとめて示した。
【０２１１】
【表６】

【０２１２】
１）支持体
本実施例で用いた支持体は、下記の方法により作成した。
ポリエチレン−２，６−ナフタレートポリマー１００質量部と紫外線吸収剤としてＴｉｎｕｖｉｎ Ｐ．３２６（チバ・ガイギーＣｉｂａ−Ｇｅｉｇｙ社製）２質量部とを乾燥した後、３００℃にて溶融後、Ｔ型ダイから押し出し、１４０℃で３．３倍の縦延伸を行い、続いて１３０℃で３．３倍の横延伸を行い、さらに２５０℃で６秒間熱固定して厚さ９０μｍのＰＥＮ（ポリエチレンナフタレート）フィルムを得た。なお、このＰＥＮフィルムにはブルー染料、マゼンタ染料及びイエロー染料（公開技法：公技番号９４−６０２３号記載のＩ−１、Ｉ−４、Ｉ−６、Ｉ−２４、Ｉ−２６、Ｉ−２７、II−５）を適当量添加した。さらに、直径２０ｃｍのステンレス巻き芯に巻き付けて、１１０℃、４８時間の熱履歴を与え、巻き癖のつきにくい支持体とした。
【０２１３】
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）。
【０２１４】
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。
【０２１５】
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（ＣＨ₂ＯＣＯＮＨ−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。
【０２１６】
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。
【０２１７】
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２０１を作成した。
【０２１８】
（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。
【０２１９】
第１層（第１ハレーション防止層）
黒色コロイド銀 銀 ０．１５５
０．０７μｍの表面かぶらせＡｇＢｒＩ（２） 銀 ０．０１
ゼラチン ０．８７
ＥｘＣ−１ ０．００２
ＥｘＣ−３ ０．００２
Ｃｐｄ−２ ０．００１
ＨＢＳ−１ ０．００４
ＨＢＳ−２ ０．００２
【０２２０】
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
【０２２１】
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
【０２２２】
第４層（低感度赤感乳剤層）
実施例−２の乳剤ｒ 銀 ０．３２３
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
【０２２３】
第５層（中感度赤感乳剤層）
沃臭化銀乳剤Ｋ 銀 ０．２１
沃臭化銀乳剤Ｌ 銀 ０．６２
ＥｘＣ−１ ０．１４
ＥｘＣ−２ ０．０２６
ＥｘＣ−３ ０．０２０
ＥｘＣ−４ ０．１２
ＥｘＣ−５ ０．０１６
ＥｘＣ−６ ０．００７
Ｃｐｄ−２ ０．０３６
Ｃｐｄ−４ ０．０２８
ＨＢＳ−１ ０．１６
ゼラチン １．１８
【０２２４】
第６層（高感度赤感乳剤層）
沃臭化銀乳剤Ｊ 銀 １．４７
ＥｘＣ−１ ０．１８
ＥｘＣ−３ ０．０７
ＥｘＣ−６ ０．０２９
ＥｘＣ−７ ０．０１０
ＥｘＹ−５ ０．００８
Ｃｐｄ−２ ０．０４６
Ｃｐｄ−４ ０．０７７
ＨＢＳ−１ ０．２５
ＨＢＳ−２ ０．１２
ゼラチン ２．１２
【０２２５】
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
【０２２６】
第８層（赤感層へ重層効果を与える層）
沃臭化銀乳剤Ｅ 銀 ０．５６０
Ｃｐｄ−４ ０．０３０
ＥｘＭ−２ ０．０９６
ＥｘＭ−３ ０．０２８
ＥｘＹ−１ ０．０３１
ＥｘＧ−１ ０．００６
ＨＢＳ−１ ０．０８５
ＨＢＳ−３ ０．００３
ゼラチン ０．５８
【０２２７】
第９層（低感度緑感乳剤層）
沃臭化銀乳剤Ｇ 銀 ０．３９
沃臭化銀乳剤Ｈ 銀 ０．２８
沃臭化銀乳剤Ｉ 銀 ０．３５
ＥｘＭ−２ ０．３６
ＥｘＭ−３ ０．０４５
ＥｘＧ−１ ０．００５
ＨＢＳ−１ ０．２８
ＨＢＳ−３ ０．０１
ＨＳＢ−４ ０．２７
ゼラチン １．３９
【０２２８】
第１０層（中感度緑感乳剤層）
沃臭化銀乳剤Ｆ 銀 ０．２０
沃臭化銀乳剤Ｇ 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−３ ２．１×１０^-3
ゼラチン ０．４４
【０２２９】
第１１層（高感度緑感乳剤層）
Ｅｍ−Ｍ 銀 ０．９９
ＥｘＣ−６ ０．００４
ＥｘＭ−１ ０．０１６
ＥｘＭ−３ ０．０３６
ＥｘＭ−４ ０．０２０
ＥｘＭ−５ ０．００４
ＥｘＹ−５ ０．００３
ＥｘＭ−２ ０．０１３
ＥｘＧ−１ ０．００５
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
【０２３０】
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
油溶性染料ＥｘＦ−５ ０．０１０
固体分散染料ＥｘＦ−６ ０．０１０
ＨＢＳ−１ ０．０８２
ゼラチン １．０５７
【０２３１】
第１３層（低感度青感乳剤層）
沃臭化銀乳剤Ｂ 銀 ０．１８
沃臭化銀乳剤Ｃ 銀 ０．２０
沃臭化銀乳剤Ｄ 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
【０２３２】
第１４層（高感度青感乳剤層）
沃臭化銀乳剤Ａ 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
【０２３３】
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−１８ ０．００９
Ｆ−１９ ０．００５
Ｆ−２０ ０．００５
ＨＢＳ−１ ０．１２
ＨＢＳ−４ ５．０×１０^-2
ゼラチン ２．３
【０２３４】
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
【０２３５】
更に、各層に適宜、保存性、処理性、圧力耐性、防黴・防菌性、帯電防止性及び塗布性をよくするために、Ｗ−１ないしＷ−５、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。
【０２３６】
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０．２４μｍであった。
【０２３７】
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。
【０２３８】
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。平均粒径は０．５２μｍであった。
【０２３９】
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。
【化１７】

【０２４０】
【化１８】

【０２４１】
【化１９】

【０２４２】
【化２０】

【０２４３】
【化２１】

【０２４４】
【化２２】

【０２４５】
【化２３】

【０２４６】
【化２４】

【０２４７】
【化２５】

【０２４８】
【化２６】

【０２４９】
【化２７】

【０２５０】
【化２８】

【０２５１】
【化２９】

【０２５２】
【化３０】

【０２５３】
【化３１】

第４層に用いる乳剤を乳剤ｓ、ｔ、ｕ、ｖに変更して試料Ｎｏ２０２、２０３、２０４、２０５を各々作成した。これらの試料を４０℃、相対湿度７０％の条件下で１４時間硬膜処理を施した。その後、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。
【０２５４】
処理工程及び処理液組成を以下に示す。

【０２５５】
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。
【０２５６】
以下に処理液の組成を示す。

【０２５７】

【０２５８】
（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）
【０２５９】

【０２６０】
（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。
【０２６１】

【０２６２】
結果を表７に示す。
【０２６３】
【表７】

【０２６４】
表７から明らかなように、本発明の乳剤を用いることにより感度が高く階調の硬い感材を得ることができることが判る。
【図面の簡単な説明】
【図１】本発明の一実施形態において用いる攪拌装置の概略の構成を示す断面図である。
【符号の説明】
１０ 攪拌装置
１１、１２、１３ 液供給口
１６ 液排出口
１８ 攪拌槽
１９槽本体
２０ シールプレート
２１、２２ 攪拌羽根
２６ 外部磁石
２８、２９ モータ[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a silver halide photographic emulsion and a silver halide photographic light-sensitive material using the same. More particularly, the present invention relates to a silver halide photographic emulsion having a particularly high sensitivity and rapid development, and a silver halide photographic light-sensitive material using the same.
[0002]
[Prior art]
It is generally well known to use tabular silver halide grains (hereinafter referred to as “tabular grains”) in order to obtain a high-sensitivity silver halide photographic light-sensitive material. As a sensitization method of these tabular grains, a sensitization method using an epitaxial junction is disclosed in JP-A-58-108526 and 59-133540. Further, for application to tabular grains having a smaller thickness or a larger equivalent circle diameter, JP-A-8-69069, 8-101472, 8-101474, 8-101475, 8-171162, 8-171163, 8-101473, 8 -101476, 9-211762, 9-211763, U.S. Pat.Nos. 5,612,176, 5,614,359, 5,629,144, 5,631,126, Nos. 5,691,127 and 5,726,007. However, the epitaxial sensitization method using silver chloride as one of the main constituent elements is basically unstable in a photographic photosensitive material assembled with silver iodobromide as a basic constituent element. The reason is that the solubility product of silver chloride is larger than the solubility product of silver bromide and silver iodide and easily undergoes halogen conversion. For this reason, a photosensitive material using an epitaxial emulsion has a drawback that the development progress speed, particularly that of a high density portion is slow. Therefore, it cannot be generalized for use in a general photographic photosensitive material.
[0003]
The inventor of the present invention paid attention to the fact that in the conventional epitaxial emulsion, the epitaxial junction is easily broken by ripening, and the extent is affected by the halogen composition of the epitaxial portion and / or the side structure of the host tabular grain receiving the epitaxial junction. In the conventional epitaxial emulsion using silver chloride, the silver chloride content of the epitaxial junction is higher than 28 mol% as disclosed in the above-mentioned patent. The side structure of the host tabular grains is formed by adding an aqueous silver salt solution and an aqueous bromide salt solution. At this time, silver iodide is introduced by adding in advance a silver iodide Lippmann emulsion prepared in advance as disclosed in the aforementioned patent. However, in this method, since the silver iodide emulsion grains are large in size, the dissolution rate is limited, and the side structure of the host tabular grains cannot be freely controlled. JP-A-2-188874 discloses a method of forming host tabular grains by adding and dissolving only a silver iodobromide fine grain emulsion prepared immediately before addition. However, since dissolution of the silver iodobromide fine grain emulsion is remarkably slowed by increasing the silver iodide content, the side structure of the host tabular grains cannot be freely controlled.
[0004]
[Problems to be solved by the invention]
The object of the present invention is to simultaneously satisfy the high sensitivity of epitaxial tabular grains and the solution to the problem of delay in development, and to provide a silver halide photographic emulsion having low fog and high sensitivity, rapid development progress and hard gradation. It is intended to provide a silver halide photographic light-sensitive material using
[0005]
[Means for Solving the Problems]
The present inventors can solve the instability of the epitaxial emulsion by controlling the silver chloride content of the epitaxial junction, and add the silver iodide fine grain emulsion prepared just before the addition to form the host tabular grains. It was found that the side structure of the particles can be freely controlled. Further, by forming an epitaxial junction using this method and increasing the (111) plane ratio of the side surface, the epitaxial junction is limited to the apex of the tabular grain, and as a result, the development speed is increased, and the present invention is found. Was completed.
[0006]
  That is, the above object has been achieved by the following means (1) to (15).
  (1) containing silver iodochlorobromide tabular grains having a (111) plane as a main surface,The (111) face ratio of the particle side surface is 75% or more,70% or more of the total projected area is from (i) below( iv )A silver halide photographic emulsion characterized by being occupied by grains satisfying
(I) Hexagonal tabular grains in which the ratio of the length of the side having the maximum length to the length of the side having the minimum length is 2 or less
(Ii) At least one vertex of the hexagon has an epitaxial junction having a silver chloride content of 5 mol% or more and 25 mol% or less.
(Iii) Silver chloride content of 0.5 mol% or more and 6 mol% or less
(Iv) Silver iodide content of 0.5 mol% or more and 10 mol% or lessunder
[0007]
  (2) containing silver iodochlorobromide tabular grains having a (111) plane as a main surface,The (111) face ratio of the particle side surface is 75% or more,70% or more of the total projected area is the following (i), (ii ′), (iii)as well as( iv )A silver halide photographic emulsion characterized in that it is occupied by filled grains.
(I) Hexagonal tabular grains in which the ratio of the length of the side having the maximum length to the length of the side having the minimum length is 2 or less
(Ii ') having an epitaxial junction at at least one apex of the hexagon
(Iii) Silver chloride content of 0.5 mol% or more and 6 mol% or less
(Iv) Silver iodide content of 0.5 mol% or more and 10 mol% or lessunder
[0008]
(3) The silver halide photographic emulsion as described in (2), wherein the silver chloride content of the epitaxial junction is 5 mol% or more and 25 mol% or less.
[0009]
(4) The silver halide photographic emulsion as described in (1) or (3), wherein the silver chloride content of the epitaxial junction is from 10 mol% to 20 mol%.
[0010]
(5) The halogenation according to any one of (1), (3) and (4), wherein the silver iodide content of the epitaxial junction is 1 mol% or more and 10 mol% or less. Silver photographic emulsion.
[0011]
  (6) The (111) plane ratio of the side surface is 85% or more.Any one of (1) to (3)The silver halide photographic emulsion described in 1.
[0012]
  (7) 70% or more of the total projected area must meet the following requirements(V)The silver halide photographic emulsion as described in any one of (1) to (6), wherein the silver halide photographic emulsion is occupied by grains satisfying
  (V)  Equivalent circle diameter 0.3 μm or more and thickness 0.2 μm or less
[0013]
(8) The silver halide photographic emulsion as described in any one of (1) to (7), wherein the variation coefficient of the equivalent circle diameter of all the grains is 30% or less.
[0014]
  (9) 70% or more of the total projected area is the above requirement (i) to( iv )(I), (ii '), (iii)as well as( iv ); (I) to(V)Or (i), (ii ′ ′), (iii), (iv)And (v)In addition to( vi )The silver halide photographic emulsion as described in any one of (1) to (8), wherein
  ( vi )  Equivalent circle diameter 0.5 μm or more and 1.2 μm or less, thickness 0.1 μm or less
[0015]
  (10) 70% or more of the total projected area is the above requirement (i) to(iv)(I), (ii '), (iii)as well as( iv ); (I) to(V); (I), (ii '), (iii), (iv)And (v); (I) to( vi )(I), (ii '), (iii), (iv), (v)as well as( vi )In addition to( vii )The silver halide photographic emulsion as described in any one of (1) to (9), wherein:
  ( vii )  There are no dislocation lines other than the epitaxial junction.
[0016]
(11) The silver halide photographic emulsion as described in any one of (1) to (10), wherein a host tabular grain is formed by adding a silver iodide fine grain emulsion prepared immediately before the addition.
[0017]
(12) The silver halide photographic emulsion as described in any one of (5) to (11), wherein an epitaxial portion is formed by adding a silver iodide fine grain emulsion prepared just before the addition.
[0018]
(13) The silver halide photographic emulsion of (11) or (12), wherein the silver iodide fine grain emulsion has a grain size of 0.02 μm or less.
[0019]
(14) The silver halide photographic emulsion as described in (13), wherein the grain size of the silver iodide fine grain emulsion is 0.01 μm or less.
[0020]
(15) A silver halide photographic material having a photosensitive layer containing the silver halide photographic emulsion described in any one of (1) to (14) on a support.
[0021]
BEST MODE FOR CARRYING OUT THE INVENTION
The silver halide photographic emulsion of the present invention will be described below.
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.
[0022]
In the present invention, preferably, 75% or more of the side surfaces connecting the opposing (111) main surfaces of the tabular grains are composed of (111) planes.
Here, 75% or more of all side surfaces are composed of (111) planes means that there are crystallographic planes other than (111) planes at a ratio lower 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 85% or more of all side surfaces are constituted by (111) planes.
[0023]
Whether or not 75% or more of all side faces are constituted by (111) faces can be primarily determined from electron micrographs obtained by the carbon replica method in which the tabular grains are shadowed. When 75% or more of the normal side faces are composed of (111) faces, in the hexagonal tabular grains, the six side faces that are directly connected to the (111) main surface are different from each other in an acute angle with respect to the (111) main surface. And connect at an obtuse angle. On the other hand, when 70% or less of all side surfaces are composed of (111) planes, in hexagonal tabular grains, all six side surfaces directly connected to the (111) main surface are obtuse with respect to the (111) main surface. Connect with. By applying shadowing at an angle of 50 ° 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.
[0024]
As a method for accurately obtaining the ratio between the (111) plane and the (100) plane, a method using adsorption of a sensitizing dye is effective. 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 later, 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 (111) plane ratio of the particle side surface in the present invention can be obtained.
[0025]
The emulsion according to the present invention has a hexagonal main surface in which the ratio of the length of the side having the maximum length to the length of the side having the minimum length of 70% or more of the projected area of all grains is 2 to 1 Are tabular grains. Preferably, a flat plate having a hexagonal main surface in which the ratio of the length of the side having the maximum length to the length of the side having the minimum length of 90% or more of the projected area of all grains is 2 to 1 Particles. More preferably, 90% or more of the total projected area has a hexagonal main surface in which the ratio of the length of the side having the maximum length to the length of the side having the minimum length is 1.5 to 1 Tabular grains.
[0026]
The emulsion of the present invention preferably has a variation coefficient of equivalent circle diameter of all grains of 30% or less. The emulsion of the present invention is preferably monodisperse. The variation coefficient of the equivalent circle diameter of the projected area of all silver halide grains used in the present invention is preferably 30% or less, more preferably 25% or less, and particularly preferably 20% or less. Here, the variation coefficient of the equivalent circle diameter is a value obtained by dividing the standard deviation of the distribution of the equivalent circle diameter of each silver halide grain by the average equivalent circle diameter.
[0027]
The equivalent-circle diameter of the tabular grains is obtained, for example, by taking a transmission electron micrograph by a replica method and obtaining the diameter of a circle having an area equal to the projected area of each grain (equivalent diameter). The 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.
[0028]
The tabular grains used in the present invention preferably have 70% or more of the total projected area with an equivalent circle diameter of 0.3 μm or more and a thickness of 0.2 μm or less. More preferably, 70% or more of the total projected area has an equivalent circle diameter of 0.3 μm to 1.2 μm and a thickness of 0.1 μm or less. Particularly preferably, 90% or more of the total projected area has a circle-equivalent diameter of 0.3 μm to 1.2 μm and a thickness of 0.1 μm or less. Most preferably, 90% or more of the total projected area has a circle-equivalent diameter of 0.5 μm to 1.2 μm and a thickness of 0.1 μm or less. As the equivalent circle diameter is smaller and the thickness is thinner, the control of the (111) plane ratio of the side surface becomes more difficult, so the effect of the present invention becomes remarkably remarkable.
[0029]
The tabular grains used in the present invention are silver iodochlorobromide. Basically, the host tabular grains are silver iodobromide or silver iodochlorobromide, and the epitaxial junction is made of a combination of silver chloride, silver chlorobromide or silver iodochlorobromide. The silver chloride content of the tabular grains of the present invention is 0.5 mol% or more and 6 mol% or less. More preferably, the silver chloride content is 0.7 mol% or more and 5 mol% or less. The silver iodide content of the tabular grains of the present invention is 0.5 mol% or more and 10 mol% or less. More preferably, the silver iodide content is 1 mol% or more and 6 mol% or less.
[0030]
In the present invention, preferably, 70% or more of the total projected area is within a range of 0.7 to 1.3 CL when the average silver chloride content of all grains is CL mol%, Particularly preferably, it is in the range of 0.8 to 1.2 CL. Further, preferably 70% or more of the total projected area is within a range of 0.7 to 1.3 I when the average silver iodide content of all grains is I mol%, Preferably it is in the range of 0.8 to 1.2I. The EPMA method (Electron Probe MicroAnalyzer 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.
[0031]
The emulsion of the present invention is a tabular grain in which 70% or more of the total projected area has an epitaxial junction at at least one of the six apexes of the hexagonal main surface. More preferably, 90% or more of the total projected area is a tabular grain having an epitaxial junction at at least one apex of the six apexes of the hexagonal main surface. Here, the apex portion means a portion in a circle having a radius of 1/3 of the length of the shorter side of the two sides adjacent to the apex when the tabular grain is viewed in the vertical direction from the main surface. In the case of a hexagonal shape in which the vertices of the hexagonal tabular grains are rounded, it can be determined whether or not the above requirement is satisfied for a virtual hexagonal shape formed by extending each side. The grains having at least one epitaxial junction at the apex are the epitaxial emulsion of the present invention. The number of epitaxial junctions is preferably six, one for each of the six apexes. Normally, an epitaxial junction is formed on the main surface of the tabular grain or on the side other than the apex other than the apex of the tabular grain. The judgment of the epitaxial emulsion of the present invention can be made as follows. 100 or more particles are arbitrarily extracted from an electron micrograph of a tabular grain replica, particles having an epitaxial junction at at least one apex, only on the side excluding the apex, only on the main plane excluding the apex, and the apex The particles are classified into three classes: particles having an epitaxial junction only on the side and the main plane excluding, and particles having no epitaxial junction. If the grain having at least one epitaxial junction at the apex is 70% or more of the total projected area, it corresponds to the epitaxial emulsion of the present invention. More preferably, it is 90% or more of the total projected area.
[0032]
The epitaxial junction is silver chloride, silver chlorobromide or silver iodochlorobromide. Preferably, the silver chloride content of the epitaxial junction is 5 mol% or more and 25 mol% or less. More preferably, the silver chloride content of the epitaxial junction is 10 mol% or more and 20 mol% or less. The silver iodide content of the epitaxial junction is preferably 1 mol% or more and 10 mol% or less. By setting the silver chloride content and silver iodide content within these ranges, the epitaxial junction becomes stable, and the effects of the present invention can be remarkably obtained.
[0033]
In the present invention, the silver chloride content and silver iodide content of the epitaxial junction can be measured by the following method. The tabular silver halide grains in the silver halide photographic light-sensitive material are taken out by treating the light-sensitive material with a proteolytic enzyme and centrifuging it. The particles are redispersed and placed on a copper mesh with a support film. The epitaxial junction portion of the grain is subjected to point analysis with a spot diameter reduced to 2 nm or less using an analytical electron microscope to measure the silver chloride content and the silver iodide content. The silver chloride content and silver iodide content should be determined in advance by processing silver halide grains of known content as calibration curves in the same manner and determining the ratio between the characteristic X-ray intensity derived from Ag and the characteristic X-ray intensity derived from halogen. It can ask for. A field emission type electron gun with an electron density higher than that using thermoelectrons is suitable as an analytical electron source for an analytical electron microscope. The halogen composition at the epitaxial junction can be easily reduced by reducing the spot diameter to 1 nm or less. Can be analyzed. When the intergranular variation coefficient of the halogen content in the epitaxial junction is 30% or less, usually 20 particles are measured and averaged to obtain the halogen content. When the intergranular variation coefficient of the halogen content in the epitaxial junction is 20% or less, usually 10 grains are measured and averaged to obtain the halogen content. The interparticle variation coefficient of the halogen content is preferably 20% or less. The total silver amount in the epitaxial junction is preferably 0.5 mol% or more and 10 mol% or less of the silver amount of the host tabular grain, and more preferably 1 mol% or more and 5 mol% or less.
[0034]
In the present invention, it is preferable that 70% or more of the total projected area has 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 of the total projected area has zero dislocation lines. In this case, the epitaxially deposited portion 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. 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 pressure to the grains so that dislocation lines are generated from the emulsion are placed on a mesh for observation with an electron microscope to prevent damage (printout, etc.) due to electron beams. Observation is carried out by the transmission method in a cooled state. 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 by using an electron microscope of a high pressure type (200 kV or more for a particle having a thickness of 0.25 μm). . From the photograph of 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.
[0035]
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.
[0036]
First, the host tabular grains necessary for preparing the epitaxial emulsion of the present invention will be described in detail. As for the distribution of silver iodide in the grain of the host tabular grain of the present invention, a multiple structure grain having a double structure or more is preferred. 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.
[0037]
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.
[0038]
In the present invention, the host tabular grains preferably have a silver iodide content in the outermost shell higher than the silver iodide content in the inner shell. The outermost shell is preferably 1 mol% or more and 40 mol% or less with respect to the total silver amount, and the average silver iodide content thereof is 1 mol% or more and 30 mol% or less. Here, the ratio of the outermost shell means the ratio of the amount of silver used to prepare the outermost shell to the amount of silver used to obtain the final grains. The average silver iodide content means the percentage of the molar ratio of the amount of silver iodide used to prepare the outermost shell to the amount of silver used to prepare the outermost shell, and the distribution may be uniform or non-uniform. . More preferably, the ratio of the outermost shell is 5 mol% or more and 20 mol% or less with respect to the total silver amount, and the average silver iodide content thereof is 5 mol% or more and 20 mol% or less.
[0039]
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 / liter or less. Use of the above nucleation method facilitates formation of the epitaxial emulsion of the present invention.
[0040]
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 60 ° 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.
[0041]
In the growth process 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.
[0042]
The silver iodide fine grain emulsion may be formed immediately before the addition described in US Pat. No. 5,004,679 or the like, and may be any one that has been subjected to a normal water washing step. In order to easily control the (111) plane ratio, the one formed immediately before the addition is preferably used. Here, preparing immediately before the addition means that the time from preparation to addition is within 10 minutes. Preferably it is within 1 minute. 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, and the like of the protective colloid agent such as temperature, pI, pH, and gelatin are not particularly limited, but the grain size is 0.02 μm or less, more preferably 0.8. 01 μm or less is convenient for controlling the (111) face ratio of the side faces of the tabular grains of 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.
[0043]
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. In addition, since the particle size is small and unstable, it is basically necessary to devise methods such as addition of a ripening inhibitor and freezing. 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 0.01 μm or less and 0.005 μm or more and a variation coefficient of grain size distribution of 18% or less.
[0044]
A method using a mixer described in JP-A-10-43570 is most preferably used to add the silver iodide fine grain emulsion prepared immediately before the addition described above.
The mixer is a stirrer equipped with a water-soluble silver salt to be stirred, a predetermined number of supply ports through which the water-soluble halogen salt flows, and a discharge port through which the silver halide fine grain emulsion generated after the stirring process is discharged. It is a stirring device provided with a tank; and stirring means for controlling the stirring state of the liquid in the stirring tank by rotating the stirring blade in the stirring tank. Preferably, the stirring means performs stirring and mixing with two or more stirring blades that are rotationally driven in the stirring tank, and the at least two stirring blades are spaced apart from each other in the stirring tank. They are arranged and driven to rotate in opposite directions. Preferably, each of the stirring blades is magnetically coupled to an external magnet disposed outside the adjacent tank wall, thereby forming a structure having no shaft penetrating the tank wall. Each stirring blade is rotated by rotationally driving a respective external magnet by a motor arranged outside the tank. One of the external magnets coupled to the stirring blade by the magnetic coupling is arranged such that the N extreme surface and the S extreme surface are parallel to the rotation center axis and overlap with the rotation center axis. Use double-sided, double-pole magnets. For the other external magnet, a left-right two-station magnet is used in which the N-pole surface and the S-pole surface are arranged symmetrically with respect to the rotation center axis on a plane perpendicular to the rotation center axis.
[0045]
FIG. 1 shows an embodiment of a mixing container (stirring device) according to the present invention.
The agitation tank 18 includes a tank body 19 having a central axis directed in the vertical direction and a seal plate 20 serving as a tank wall that closes the upper and lower opening ends of the tank body 19. The stirring blades 21 and 22 are spaced apart from the opposite upper and lower ends in the stirring tank 18 and are driven to rotate in opposite directions. The respective stirring blades 21 and 22 constitute a magnetic coupling with an external magnet 26 disposed outside the tank wall in which the respective stirring blades 21 and 22 are close to each other. That is, the stirring blades 21 and 22 are coupled to the external magnets 26 by magnetic force, and are driven to rotate in opposite directions by rotating the external magnets 26 with independent motors 28 and 29.
[0046]
The stirring tank 18 discharges the silver salt aqueous solution, the halogen salt aqueous solution to be stirred, and the liquid supply ports 11, 12, 13 for introducing the colloidal solution as necessary, and the silver halide fine grain emulsion after the stirring process is finished. A discharge port 16 is provided. The silver salt aqueous solution and the halogen salt aqueous solution are preferably added toward the stirring blade, and the angles of the liquid supply ports 11 and 12 are preferably separated as much as possible. That is, 90 ° is preferable to 60 °, and 180 ° is more preferable.
[0047]
A method for preparing a silver iodide fine grain emulsion will be described below. Specifically, (a) stirring rotation speed, (b) residence time, (c) addition method and protective colloid species, (d) additive solution temperature, (e) additive solution concentration, (f) potential will be described in detail. .
[0048]
(A) Stirring rotation speed
When the opposing stirring blades are driven in the mixer, the number of rotations is preferably 1000 rpm to 8000 rpm, more preferably 3000 rpm to 8000 rpm, and most preferably 4000 rpm to 8000 rpm. If it exceeds 8000 rpm, the centrifugal force of the stirring blade becomes too strong, and a back flow to the addition port begins to occur, which is not preferable. Further, the stirring blades rotating in the opposite direction may have the same rotational speed or different rotational speeds.
[0049]
(B) Time spent
The residence time t of the additive liquid introduced into the mixer is expressed by the following.
t = 60V / (a + b + c)
t: Stay time (seconds)
V: Volume of the mixing space of the mixer (milliliter (mL))
a: Silver salt solution addition flow rate (mL / min)
b: Halide salt solution addition flow rate (mL / min)
c: Flow rate of addition of protective colloid solution (mL / min)
[0050]
The residence time t is preferably 0.1 seconds to 5 seconds, more preferably 0.1 seconds to 1 second, and most preferably 0.1 seconds to 0.5 seconds. If the residence time t exceeds 5 seconds, the silver halide fine grains once generated in the mixer grow to have a larger size and the size distribution is widened, which is not preferable. Also, if it is less than 0.1 seconds, the additive solution is unreacted and is discharged out of the mixer, which is not preferable.
[0051]
(C) Addition method and protective colloid seed solution are added to the protective colloid seed mixer, and the following addition method is used.
a. Inject protective colloid solution alone into the mixer. The concentration of the protective colloid is 0.5% or more, preferably 1% or more and 20% or less. The flow rate is at least 20% to 300%, preferably 50% to 200% of the sum of the flow rates of the silver salt solution and the halide solution.
[0052]
b. Include protective colloid in halide salt solution. The concentration of the protective colloid is 0.4% or more, preferably 1% or more and 20% or less.
c. Include protective colloid in the silver salt solution. The concentration of the protective colloid is 0.4% or more, preferably 1% or more and 20% or less. When gelatin is used, silver ions and gelatin form gelatin silver, which is photodecomposed and thermally decomposed to form a silver colloid. Therefore, it is better to add the silver salt aqueous solution and the gelatin solution immediately before use.
[0053]
The methods a to c may be used alone or in combination of two or three of them.
[0054]
In the mixer used in the present invention, gelatin is often used as a protective colloid. Gelatin is usually treated with alkali. In particular, it is preferable to use alkali-treated gelatin that has been subjected to deionization treatment and / or ultrafiltration treatment from which impurity ions or impurities have been removed. In addition to alkali-treated gelatin, acid-treated gelatin, phthalated gelatin, trimellitated gelatin, hatched gelatin, maleated gelatin, and derivative gelatin such as esterified gelatin; low molecular weight gelatin (molecular weight 1000 to 80,000, enzymatically degraded Gelatin, hydrolyzed gelatin with acid and / or alkali, gelatin decomposed with heat); high molecular weight gelatin (molecular weight 110,000 to 300,000); gelatin with methionine content of 40 μmol / g or less; tyrosine content Gelatin of 20 μmol / g or less; oxidized gelatin; gelatin in which methionine is inactivated by alkylation can be used. A mixture of two or more kinds of gelatins may be used.
[0055]
In order to form finer silver halide fine grains using a mixer, the temperature of the solution added to the mixer needs to be kept as low as possible. It is preferable to use low molecular weight gelatin that does not solidify even at temperature. The molecular weight of the low molecular weight gelatin is 50,000 or less, preferably 30,000 or less, more preferably 10,000 or less. Furthermore, a synthetic polymer which is a synthetic colloid having a protective colloid action of silver halide grains is also used in the present invention because it does not solidify even at a low temperature. Furthermore, natural polymers other than gelatin can be used in the present invention as well. No. 7-11550, Research Disclosure Vol. 176, No. 17643 (December 1978).
[0056]
(D) Additive liquid temperature
The temperature of the additive solution is preferably 10 ° C. to 60 ° C., but considering the size reduction and suitability for production, it is more preferably 20 ° C. to 40 ° C., and most preferably 20 ° C. to 30 ° C. In addition, it is preferable to control the temperature of the mixer and the piping portion from the generation of reaction heat in the mixer and prevention of ripening of the formed silver iodide fine particles.
[0057]
(E) Concentration of additive solution
Since the mixer provided outside the reaction vessel is generally not diluted with a bulk solution, when a thick additive solution is used, the size of silver iodide fine particles formed increases and the size distribution deteriorates. There is a tendency. However, since the mixer described above is superior in stirring and mixing as compared with the conventional stirrer, silver iodide ultrafine particles having a small size and a narrow size distribution were formed even when a thick additive solution was used. Specifically, the concentration of the additive solution is preferably 0.4 mol / liter (hereinafter also referred to as “L”) to 1.2 mol / L, and more preferably 0.4 mol / L to 0.8 mol / L. is there. If the concentration of the additive solution is less than 0.4 mol / L, the total silver amount is reduced because it is too thin, which is not practical.
[0058]
(F) Potential
Regarding the potential (excessive amount of halogen) for forming hexagonal silver iodide ultrafine particles, it is preferable to form the pAg region with low solubility from the viewpoint of size reduction. Specifically, the pAg is preferably 8.5 to 11.5, and more preferably 9.5 to 10.5.
[0059]
As a result of repeated examinations of the above (a) to (f), hexagonal silver iodide ultrafine particles having an average sphere equivalent diameter of 0.008 μm to 0.019 μm could be prepared.
The silver iodide ultrafine particles thus prepared are immediately supplied to the reaction vessel. However, immediately means within 10 minutes, preferably within 1 minute. Silver iodide ultrafine particles have a larger grain size with time, so a shorter time is preferable.
[0060]
As described above, in order to add the silver iodide ultrafine particles formed in the mixing vessel outside the reaction vessel to the reaction vessel, they may be added continuously or once stored in the mixing vessel. It may be added after adding. These may be used in combination. However, when it is stored once in the container, the temperature is preferably 40 ° C. or lower, more preferably 20 ° C. or lower. Furthermore, it is preferable that the storage time is as short as possible.
[0061]
In the present invention, a method of making 75% or more of the side surface of the host tabular grain emulsion into the (111) plane will be further described. In the present invention, it is possible to easily control the (111) plane ratio of the side surface by adding the silver iodide fine grain emulsion prepared immediately before the addition at the time of forming the outermost shell of the host tabular grain. At this time, the pBr when the silver iodide fine grain emulsion is added is important. Preferably, the addition of 30% or more of the silver amount required for forming the outermost shell is set to pBr so that the ratio of the (111) plane of the side surface is increased, that is, the ratio of the (100) plane of the side surface is decreased. More preferably, the addition of 50% or more of the amount of silver required for forming the outermost shell is set to pBr so that the ratio of the (111) plane on the side surface increases.
[0062]
The value of pBr that increases the ratio of the (111) plane on the side surface is broad 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 pBr2.0 or less. More preferably, it is pBr2.5 or less. pBr is preferably 1 or more. 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.
[0063]
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.
[0064]
The host tabular grains preferably have no dislocation lines. Dislocation lines can be eliminated by using a combination of the nucleation, ripening, and growth processes described above.
[0065]
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. In the epitaxial emulsion of the present invention, it is preferably performed immediately after the formation of the host tabular grains.
[0066]
For epitaxial formation immediately after host tabular grain formation, pH, pAg, gelatin type and concentration, and viscosity are selected. The gelatin concentration is important and is preferably 50 g or less per liter. Particularly preferably, it is 5 g or more and 40 g or less. When the amount is too small, epitaxial deposition occurs on the main surface of the tabular grain. When the amount is too large, the epitaxial deposition becomes uneven among the grains due to an increase in viscosity.
[0067]
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.
[0068]
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.
[0069]
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]
It is preferable for preparing an epitaxial emulsion that the silver iodide content of the surface composition of the host tabular grains is further increased during the adsorption of the sensitizing dye. Prior to the addition of the sensitizing dye, iodine ions or the aforementioned silver iodide fine grain emulsion is added. The amount of these iodine ions or silver iodide added is 1 × 10 5 with respect to the host tabular grains.^-FourTo 1 × 10^-2The molar range is preferably 1 × 10^-3To 5 × 10^-3The range of is particularly preferable.
[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. In the present invention, it is most preferable to add an aqueous silver nitrate solution and an aqueous solution containing bromide salt and chloride salt by the double jet method, and add a silver iodide fine grain emulsion prepared immediately before or simultaneously with the addition described above. By this method, the silver iodide content of the epitaxial junction can be freely controlled, and the distribution of the silver iodide content of the epitaxial junction between the grains becomes uniform. The preparation method of the silver iodide fine grain emulsion prepared immediately before the addition is basically as described above. 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 / L or less, particularly preferably 0.5 mol / L or less. 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 0.5 mol% or more and 10 mol% or less, and more preferably 1 mol% or more and 5 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 during the formation of the epitaxial portion 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 the 6-cyano metal complex is doped in the epitaxial junction 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 in the finished grain.^-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. The 6-cyano metal complex provides a highly sensitive photosensitive material, and also has the effect of suppressing the occurrence of covering when the photosensitive material is stored for a long period of time.
[0076]
(I) [M (CN)₆]^n-
(In the formula, 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 perform water washing after this. 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.
[0081]
As the protective colloid to be subsequently dispersed, it is advantageous to use gelatin. Most preferred is high molecular weight gelatin obtained by crosslinking ordinary gelatin by a chemical method. By using the gelatin, the epitaxial emulsion of the present invention becomes more stable. On the other hand, other hydrophilic colloids can also be used.
[0082]
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.
[0083]
The emulsion of the present invention is preferably subjected to chemical sensitization after washing and dispersion. 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.
[0084]
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.
[0085]
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.
[0086]
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.
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, 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; for example, thioketo compounds such as oxadrine thione; azaindenes such as , Triazaindenes, tetraazaindenes (especially 4-hydroxy substituted (1,3,3a, 7) chitraazaindenes), pentaazaindene Known as antifoggants or stabilizers, such as, it can be added to many compounds. For example, those described in US Pat. Nos. 3,954,474, 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, during epitaxial formation, in the water washing step, during dispersion after water washing, before chemical sensitization, during chemical sensitization, after chemical sensitization, and 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 kind of metal compound, but may be used in combination of two or more kinds.
[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]
It is preferred to subject the silver halide photographic emulsion of the present invention to reduction sensitization during grain formation, after grain formation and before chemical sensitization, during chemical sensitization, or after chemical sensitization.
Here, reduction sensitization means a method of adding a reduction sensitizer to a silver halide emulsion, a method of growing or ripening in a low pAg atmosphere called pAg 1-7 called silver ripening, and a pH of 8 called high pH ripening. Either a method of growing or aging in an atmosphere having a high pH of ˜11 can be selected. Two or more methods can be used in combination.
[0094]
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.
[0095]
The reduction sensitizer is dissolved in water or an organic solvent such as alcohols, glycols, ketones, esters and amides and added during particle growth. Although it may be added to the reaction vessel in advance, a method of adding it at an appropriate time of particle growth is preferred. Alternatively, a reduction sensitizer may be added in advance to the water solubility of the water-soluble silver salt or water-soluble alkali halide, and silver halide grains may be precipitated using these aqueous solutions. It is also preferable to add the reduction sensitizer solution several times as the particle grows, or to add it continuously for a long time.
[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]
The light-sensitive material produced using the silver halide emulsion obtained in the present invention may have at least one light-sensitive emulsion layer on the support, preferably a blue-sensitive layer, a green-sensitive layer. At least one silver halide emulsion layer of a chromatic layer and a red color sensitive layer is provided. There are no particular restrictions on the number and order of the silver halide emulsion layers and the non-light-sensitive layers. As a typical example, 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.
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.
[0105]
Preferred layers using the emulsion of the present invention are a medium-sensitivity emulsion layer and a low-sensitivity emulsion layer, more preferably a low-sensitivity emulsion layer. 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.
[0106]
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.
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.
[0108]

[0109]
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.
[0110]
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.
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.
[0111]
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.
[0112]
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.
[0113]
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.
[0114]
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.
[0115]
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, JP-B-57-39413, U.S. Pat. No. 4,004,929, U.S. Pat. No. 4,138,258, British Patent 1,146, 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.
[0116]
Compounds that release photographically useful residues upon coupling can also be preferably used in the present invention. DIR couplers that release a development inhibitor include the above-mentioned RD17643, item VII-F, and No. 1 above. No. 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.
[0117]
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.
[0118]
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.
[0119]
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.
[0120]
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.
[0121]
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.
[0122]
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.
[0123]
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.
[0124]
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.
[0125]
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.
[0126]
Membrane swelling speed T_1/2Can be adjusted by adding a hardener to gelatin as a binder or changing the aging conditions after coating.
[0127]
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%.
[0128]
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.
[0129]
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.
[0130]
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.
[0131]
When reversal processing is performed, color development is usually performed after black and white development. This black-and-white developer includes, for example, dihydroxybenzenes such as hydroquinone, for example 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol. Known black-and-white developing agents can be used alone or in combination. The pH of these color developers and black-and-white developers is generally 9-12. The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 L or less per square meter of the light-sensitive material, and can be reduced to 500 mL or less by reducing the bromide ion concentration in the replenishing solution. You can also 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.
[0132]
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]]
[0133]
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.
[0134]
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.
[0135]
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. Among these, iron (III) complex salts of aminopolycarboxylic acid such as iron (III) complex salt of ethylenediaminetetraacetate and 1,3-diaminopropanetetraacetate are the viewpoints of rapid processing and prevention of environmental pollution. To preferred. Furthermore, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in both a bleaching solution and a bleach-fixing solution. The pH of the bleaching solution or bleach-fixing solution using these iron (III) complex salts of aminopolycarboxylic acid is usually 4.0 to 8, but the processing can be performed at a lower pH in order to speed up the processing.
[0136]
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.
[0137]
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.
[0138]
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.
[0139]
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.
[0140]
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.
[0141]
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.
[0142]
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.
[0143]
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).
[0144]
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.
[0145]
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.
[0146]
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.
[0147]
The overflow liquid accompanying the washing and / or 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.
[0148]
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.
[0149]
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.
[0150]
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.
[0151]
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.
[0152]
【Example】
The present invention will be specifically described below with reference to examples. However, the present invention is not limited to these examples.
[0153]
(Example-1)
The effects of the silver chloride content of the epitaxial junction and the (111) plane ratio of the side surfaces of the tabular grains in the present invention will be described.
(Preparation of emulsion a)
1500 mL of an aqueous solution adjusted to pH 4 containing 4.1 g of KBr and 7.1 g of gelatin having an average molecular weight of 20000 was kept at 40 ° C. and stirred. AgNO_Three(8.4 g) An aqueous solution and an aqueous halogen (containing KBr 5.9 g and KI 1.1 g) solution were added over 40 seconds by the double jet method. After adding 35.5 g of succinylated gelatin having an average molecular weight of 100,000, the pH was adjusted to 5, and then the temperature was raised to 58 ° C. AgNO_Three(2.4 g) After adding the aqueous solution over 2 minutes, 59 mL of a 6.25 mol / L aqueous ammonium nitrate solution and 59 mL of a 1N aqueous sodium hydroxide solution were added. After aging for 12 minutes, acetic acid was added to readjust the pH to 5. AgNO as the first growth_Three(182.3 g) The aqueous solution and KBr aqueous solution were added over 22 minutes while accelerating the flow rate by the double jet method. At this time, the silver potential was kept at −20 mV with respect to the saturated calomel electrode. Then, AgNO as the second growth_Three(21.5 g) An aqueous solution and an aqueous KBr solution containing 17 mol% of KI were added over 5 minutes by the double jet method. At this time, the silver potential was kept at 20 mV for the first 3 minutes with respect to the saturated calomel electrode, and then kept at 85 mV. Thus, the host tabular grains before epitaxial deposition were completed.
[0154]
After the temperature was lowered to 38 ° C., 134 mg of benzimidazolium was added to adjust the pH to 4.5. After adding an aqueous KI (0.5 g) solution, sensitizing dyes I, II, and III were added at a molar ratio of 6: 3: 1 at a ratio of 80% of the saturated coating amount. However, the sensitizing dye was used as a solid fine dispersion prepared by the method described in JP-A No. 11-52507. That is, 0.8 parts by mass of sodium nitrate and 3.2 parts by mass of sodium sulfate were dissolved in 43 parts by mass of ion-exchanged water, 13 parts by mass of a sensitizing dye was added, and 20 ° C. at 2000 rpm using a dissolver blade at 60 ° C. By dispersing for a minute, a solid dispersion of a sensitizing dye was obtained. 8.0 × 10 8 potassium hexacyanoruthenium (II)^-FiveMole (hereinafter referred to as 1 mol of silver in the host tabular grains) was added. AgNO_Three(9.2 g) 100 mL of an aqueous solution and 100 mL of an aqueous halogen solution containing KBr (2.1 g) and NaCl (2.8 g) were added by a double jet method over 1 minute. The silver potential at the end of the addition was +90 mV with respect to the saturated calomel electrode.
[0155]
Antifoggant I 1 × 10^-FourAfter the molar addition, the emulsion was washed with water at 35 ° C. according to a conventional method, deionized gelatin having an average molecular weight of 100,000 was added, and redispersed at 40 ° C. to adjust the pH to 5.5. The temperature was raised to 50 ° C., and potassium thiocyanate, chloroauric acid, sodium thiosulfate and N, N-dimethylselenourea were added for optimum chemical sensitization. Antifoggant I 5 × 10^-FourThe chemical sensitization was completed by adding a molar amount. This emulsion was designated as Emulsion a.
[0156]
Emulsion a was a tabular grain having an average equivalent-circle diameter of 0.82 μm, an equivalent-circle diameter variation coefficient of 18%, an average thickness of 0.065 μm, a thickness variation coefficient of 17%, and an average aspect ratio of 12.6. Further, the ratio of the length of the side having the maximum length to the length of the side having the minimum length of 90% or more of the total projected area of the equivalent circle diameter of 0.7 μm or more and the thickness of 0.075 μm or less is 1. It was occupied by hexagonal tabular grains that were 4 or less. According to electron microscopic observation of the cut cross section of the particle, the average twin plane spacing was 0.010 μm and the coefficient of variation was 19%. As a result of observation with a transmission electron microscope at a low temperature, 90% or more of the total projected area showed no dislocation lines other than the epitaxial junction. In this emulsion, the silver iodide content of the host tabular grains is 1.75 mol%, and the silver amount in the epitaxial junction is 4.29 mol% with respect to the host tabular grains and 4.11 mol% with respect to the total silver amount. It is.
[0157]
[Chemical 1]

[0158]
(Preparation of emulsions b, c, d, e, f)
Emulsions b, c, d, e, and f were prepared by changing the amount of KBr and NaCl in the halogen aqueous solution during the epitaxial deposition in the preparation of emulsion a.
[0159]
(Preparation of emulsions g, h, i, j, k)
Emulsion g was prepared by changing the second growth of emulsion a as follows. AgNO as second growth_Three(21.5 g) An aqueous solution and an aqueous KBr solution were added over 5 minutes by the double jet method. At this time, the silver potential was kept at 20 mV for the first 3 minutes with respect to the saturated calomel electrode, and then kept at 85 mV. During the growth for 5 minutes, an AgI fine grain emulsion prepared immediately before the addition was added so that the silver iodide content was 17 mol%. The AgI fine grain emulsion was prepared by using the stirrer described in the description of the present invention to obtain 1.913% by mass of AgNO._ThreeAn aqueous solution containing an aqueous solution, 1.92% by mass of KI and 1.9% by mass of gelatin having an average molecular weight of 20000 was added at 25 ° C. Added 5 seconds after preparation. The average particle size of the AgI fine particles was 0.0088 μm, and the variation coefficient of the particle size distribution was 24%. Emulsions h, i, j, and k were prepared by making the same changes in emulsions b, c, d, and e. In the preparation of emulsions g to k, instead of using silver iodide fine grains prepared immediately before addition, a silver iodide fine grain emulsion having an average grain size of 0.03 μm and a coefficient of variation of 14% was added to prepare emulsion g-2. H-2, i-2, j-2, k-2 were prepared. However, in either case, the silver iodide fine grain emulsion remained undissolved and the photographic characteristics could not be evaluated.
[0160]
(Preparation of emulsions 1, m, n)
Emulsion l was prepared by changing the second growth of emulsion d as follows. The silver potential at the time of double jet addition for 5 minutes was kept at 20 mV for the first 3 minutes and then 40 mV. Emulsions m and n were prepared by changing the 40 mV to 0 mV and -20 mV.
[0161]
(Preparation of emulsions o, p, q)
Emulsion o was prepared by changing the second growth of emulsion j as follows. The silver potential at the time of double jet addition for 5 minutes was kept at 20 mV for the first 3 minutes and then 40 mV. Emulsions p and q were prepared by changing the 40 mV to 0 mV and -20 mV.
[0162]
The characteristics of emulsions a to q are summarized in Table 1. The deposition of the epitaxial portion was observed from an electron microscope by a replica method, the composition of the epitaxial portion was analyzed from an analytical electron microscope equipped with a field emission electron gun, and the (111) plane ratio of the side surface was described in the text. Each was determined by a method using dye adsorption. The variation coefficient of the distribution of the silver chloride content in the epitaxial portion within and between the grains was within 20% in all cases. The characteristics of the emulsion other than those listed in Table 1 were basically the same as those of Emulsion a.
[0163]
[Table 1]

[0164]
As is apparent from the results in Table 1, when the host tabular grains are formed by adding the silver iodide fine grain emulsion prepared immediately before the addition, the (111) plane ratio of the tabular grain side surface is increased and an epitaxial junction is formed. It can be seen that the particle ratio increases.
An emulsion subjected to the above chemical sensitization under the coating conditions shown in Table 2 below was applied to a cellulose triacetate film support provided with an undercoat layer with a protective layer. 1-17 were made.
[0165]
[Table 2]

[0166]
These samples were left under conditions of 40 ° C. and 70% relative humidity for 14 hours. Thereafter, the film was exposed for 1/100 second through a gelatin filter SC-50 manufactured by FUJIFILM Corporation and a continuous wedge.
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).
[0167]

[0168]
Next, the composition of the treatment liquid will be described.

[0169]
(Bleaching solution) Common for tank solution and replenisher solution (Unit: g)
Ethylenediaminetetraacetic acid ferric ammonium dihydrate 120.0
Ethylenediaminetetraacetic acid disodium salt 10.0
Ammonium bromide 100.0
Ammonium nitrate 10.0
Bleach accelerator 0.005 mol
(CH_Three)₂N-CH₂-CH₂-S-S-CH₂-CH₂-N (CH_Three)₂・ 2HCl
Ammonia water (27%) 15.0 mL
Add water and add 1.0L
pH (adjusted with ammonia water and nitric acid) 6.3
[0170]

[0171]
(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) 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.
[0172]
(Stabilizer) Tank fluid and replenisher common (Unit: g)
Sodium p-toluenesulfinate 0.03
Polyoxyethylene-p-monononylphenyl ether
(Average polymerization degree 10) 0.2
Ethylenediaminetetraacetic acid disodium salt 0.05
1,2,4-triazole 1.3
1,4-bis (1,2,4-triazole-1-
Ilmethyl) piperazine 0.75
Add water and add 1.0L
pH 8.5
[0173]
The density of the processed sample was measured with a green filter. The development time was also evaluated by changing the color development processing time from 3 minutes 15 seconds to 1 minute 15 seconds. Table 3 shows the sensitivity values and fog values obtained at the above concentrations of fog plus 0.2 and 2.0.
[0174]
[Table 3]

[0175]
As is clear from the comparison of emulsions a to f in Table 3, the sensitivity / fogging ratio is excellent when the silver chloride content of the epitaxial junction is 5 mol% or more and 25 mol% or less of the present invention, and the processing time is short. It can be seen that the color density increases significantly. From the comparison of emulsions a to e and emulsions g to k, the silver iodide fine grain emulsion prepared just before the addition of the host tabular grains was added and formed, and the high (111) face ratio on the side face has the same excellent sensitivity / fogging ratio. In addition, it can be seen that the color density in a short processing time is remarkably increased. From the comparison of emulsions d and l to n and the comparison of emulsions j and o to q, it can be seen that the effect of the silver chloride content in the epitaxial portion of the present invention and the effect of the (111) face ratio on the side surfaces of the tabular grains are synergistic.
[0176]
(Example-2)
The silver iodide content of the epitaxial portion in the present invention, particularly the effect of adding a silver iodide fine grain emulsion prepared immediately before addition will be described.
(Preparation of emulsions r, s, t, u, v)
Emulsions r, s, t, u and v were prepared by changing the epitaxial junctions of emulsions c, d, l, o and q of Example-1 as follows. After the temperature was lowered to 38 ° C., 134 mg of benzimidazolium was added to adjust the pH to 4.5. After adding an aqueous KI (0.5 g) solution, sensitizing dyes I, II, and III were added at a molar ratio of 6: 3: 1 and 80% of the saturated coverage. However, the sensitizing dye was used as a solid fine dispersion prepared by the method described in JP-A No. 11-52507. That is, 0.8 parts by mass of sodium nitrate and 3.2 parts by mass of sodium sulfate were dissolved in 43 parts by mass of ion-exchanged water, 13 parts by mass of a sensitizing dye were added, and 20 ° C. at 2000 rpm using a dissolver blade at 60 ° C. By dispersing for a minute, a solid dispersion of a sensitizing dye was obtained. 8.0 × 10 8 potassium hexacyanoruthenium (II)^-FiveMole (hereinafter referred to as 1 mol of silver in the host tabular grains) was added. AgNO_Three(9.2 g) 100 mL of an aqueous solution and 100 mL of an aqueous halogen solution containing KBr (2.1 g) and NaCl (2.8 g) were added by a double jet method over 1 minute.
[0177]
One minute before the double jet addition, an AgI fine grain emulsion prepared immediately before the addition was added in an amount of 7 mol% based on the silver amount in the epitaxial junction. The AgI fine grain emulsion was prepared by using the stirrer described in the description of the present invention to obtain 1.913% by mass of AgNO._ThreeAn aqueous solution containing an aqueous solution, 1.92% by mass of KI and 1.9% by mass of gelatin having an average molecular weight of 20000 was added at 25 ° C. It was added over 10 seconds at 5 seconds after preparation. The average particle size of the AgI fine particles was 0.0088 μm, and the variation coefficient of the particle size distribution was 24%. The silver potential at the end of the addition was +90 mV with respect to the saturated calomel electrode. Antifoggant I 1 × 10^-FourAfter the molar addition, the emulsion was washed with water at 35 ° C. according to a conventional method, deionized gelatin having an average molecular weight of 100,000 was added, and redispersed at 40 ° C. to adjust the pH to 5.5. The temperature was raised to 50 ° C., and potassium thiocyanate, chloroauric acid, sodium thiosulfate and N, N-dimethylselenourea were added for optimum chemical sensitization. Antifoggant I 5 × 10^-FourThe chemical sensitization was completed by adding a molar amount.
[0178]
In the preparation of emulsions r to v, instead of using silver iodide fine grains prepared immediately before addition, a silver iodide fine grain emulsion having an average grain size of 0.03 μm and a coefficient of variation of 14% was added to add emulsion w, x , Y, z, z-2 were prepared. However, in either case, the silver iodide fine grain emulsion remained undissolved and the photographic characteristics could not be evaluated.
[0179]
The properties for emulsions r to v are summarized in Table 4. The deposition of the epitaxial portion was observed from an electron microscope by a replica method, the composition of the epitaxial portion was analyzed from an analytical electron microscope equipped with a field emission electron gun, and the (111) plane ratio of the side surface was described in the text. Each was determined by a method using dye adsorption. The variation coefficient of the distribution of the silver chloride and silver iodide contents in the epitaxial portion within and between the grains was within 20% in all cases. The characteristics of the emulsion other than those listed in Table 4 were basically the same as those of Emulsion a.
[0180]
[Table 4]

[0181]
Table 5 shows the results of coating and evaluating the photographic characteristics in the same manner as in Example 1.
[0182]
[Table 5]

[0183]
As is apparent from Table 5, the emulsion of the present invention in which the epitaxial portion is formed by adding the silver iodide fine grain emulsion prepared immediately before the addition has low fog and high sensitivity. In addition, the color density when the processing time is short is extremely high.
[0184]
(Example-3)
The effect of the emulsion of the present invention in a multilayer color photographic light-sensitive material is shown.
Silver halide emulsions Em-A to Em-M were prepared by the following production method.
(Em-A manufacturing method)
42.2 L of an aqueous solution containing 31.7 g of phthalated low molecular weight gelatin having a phthalation rate of 97% and a molecular weight of 15000 and KBr 31.7 g was kept at 35 ° C. and stirred vigorously. AgNO_Three1583 mL of an aqueous solution containing 316.7 g and 1583 mL of an aqueous solution containing 52.7 g of low molecular weight gelatin having a molecular weight of 15000 and 221.5 g of KBr were added over 1 minute by the double jet method. Immediately after the addition, 52.8 g of KBr is added and AgNO_Three2485 mL of an aqueous solution containing 398.2 g and 2581 mL of an aqueous solution containing 291.1 g of KBr were added over 2 minutes by the double jet method. Immediately after the addition, 44.8 g of KBr was added. Then, it heated up to 40 degreeC and matured. After completion of aging, 923 g of phthalated gelatin having a phthalation rate of 97% and a molecular weight of 100,000 were added and 79.2 g of KBr was added._ThreeAn aqueous solution of 15947 mL containing 5103 g and an aqueous KBr solution were added over 10 minutes while accelerating the flow rate so that the final flow rate was 1.4 times the initial flow rate by the double jet method. At this time, the silver potential was kept at −60 mV with respect to the saturated calomel electrode. After washing with water, gelatin was added to adjust the pH to 5.7, pAg 8.8, 131.8 g in terms of silver per kg of emulsion, and 64.1 g of gelatin to make a seed emulsion.
[0185]
1211 mL of an aqueous solution containing 46 g of phthalated gelatin having a phthalation rate of 97% and 1.7 g of KBr was kept at 75 ° C. and vigorously stirred. After adding 9.9 g of the seed emulsion described above, 0.3 g of modified silicone oil (product of Nippon Unicar Co., Ltd., L7602) was added. H₂SO_FourAfter adjusting pH to 5.5, AgNO_ThreeAn aqueous solution containing 7.0 g (67.6 mL) and an aqueous KBr solution were added over 6 minutes while accelerating the flow rate so that the final flow rate was 5.1 times the initial flow rate by the double jet method. At this time, the silver potential was kept at −20 mV with respect to the saturated calomel electrode. After adding 2 mg of sodium benzenethiosulfonate and 2 mg of thiourea dioxide, AgNO_Three328 mL of an aqueous solution containing 105.6 g and an aqueous KBr solution were added over 56 minutes while accelerating the flow rate so that the final flow rate was 3.7 times the initial flow rate by the double jet method. At this time, an AgI fine grain emulsion having a grain size of 0.037 μm was added while simultaneously accelerating the flow rate so that the silver iodide content was 27 mol%, and the silver potential was kept at −50 mV with respect to the saturated calomel electrode.
[0186]
AgNO_Three121.3 mL of an aqueous solution containing 45.6 g and an aqueous KBr solution were added over 22 minutes by the double jet method. At this time, the silver potential was kept at +20 mV with respect to the saturated calomel electrode. The temperature was raised to 82 ° C., KBr was added to adjust the silver potential to −80 mV, and then the aforementioned AgI fine grain emulsion was added in an amount of 6.33 g in terms of KI mass. Immediately after the addition, AgNO_Three206.2 mL of an aqueous solution containing 66.4 g was added over 16 minutes. The silver potential was kept at −80 mV with an aqueous KBr solution for 5 minutes at the beginning of the addition. After washing with water, gelatin was added to adjust the pH to 5.8 and pAg 8.7 at 40 ° C. After adding compounds 11 and 12, the temperature was raised to 60 ° C. After addition of sensitizing dyes 11 and 12, potassium thiocyanate, chloroauric acid, sodium thiosulfate, and N, N-dimethylselenourea were added for optimum chemical sensitization. Compound 13 and Compound 14 were added at the end of chemical sensitization. Here, optimal chemical sensitization means that the sensitizing dye and each compound are added at a rate of 10 per mol of silver halide.^-1To 10^-8It means that it selected from the addition amount range of mol.
[0187]
[Chemical formula 2]

[Chemical Formula 3]

[Formula 4]

[Chemical formula 5]

[Chemical 6]

[Chemical 7]

(Em-B manufacturing method)
1192 mL of an aqueous solution containing 0.96 g of low molecular weight gelatin and 0.9 g of KBr 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 1.05 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 completion of ripening, 35 g of trimellitated gelatin having a molecular weight of 100,000, which was chemically modified with trimellitic acid, was added, and the pH was adjusted to 7. 6 mg of thiourea dioxide was added. AgNO_Three116 mL of an aqueous solution containing 29 g and an aqueous KBr solution were added by a double jet method at a flow rate acceleration so that the final flow rate was three times the initial flow rate. At this time, the silver potential was kept at −20 mV with respect to the saturated calomel electrode.
[0188]
AgNO_Three440.6 mL of an aqueous solution containing 110.2 g and an aqueous KBr solution were added over 30 minutes by 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 the same time with the flow rate accelerated 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. It was. AgNO_Three96.5 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_Three228 mL of an aqueous solution containing 57 g was added over 5 minutes. At this time, it adjusted with KBr aqueous solution so that the electric potential at the time of completion | finish of addition might be + 20mV. It was washed with water in the same manner as Em-A and chemically sensitized.
[0189]
(Em-C manufacturing method)
1192 mL of an aqueous solution containing 1.02 g of phthalated gelatin having a molecular weight of 100,000 and 97% phthalation containing 35 μmol of methionine per gram and 0.9 g of KBr was kept at 35 ° C. and stirred vigorously. AgNO_ThreeAn aqueous solution containing 4.47 g, an aqueous solution containing 42 mL and 3.16 g of KBr, and 42 mL were added over 9 seconds by the double jet method. After adding 2.6 g of KBr, the mixture was heated to 63 ° C. and aged. After completion of ripening, 41.2 g of trimellitated gelatin having a molecular weight of 100,000 used in the preparation of Em-B and 18.5 g of NaCl were added. After adjusting the pH to 7.2, 8 mg of dimethylamine borane was added. AgNO_ThreeAn aqueous solution (203 mL) 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_Three440.6 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 adjusted to −20 mV with respect to the saturated calomel electrode. Kept.
[0190]
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_Three404 mL 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.
[0191]
(Em-D manufacturing method)
AgNO during nucleation in the preparation of Em-C_ThreeThe addition amount was changed to 2.3 times. And the final AgNO_ThreeIt changed so that it might adjust with KBr aqueous solution so that the electric potential at the time of completion | finish of addition of 404 mL of aqueous solution containing 57g might be set to + 90mV. Otherwise, it was prepared in substantially the same manner as Em-C.
[0192]
(Em-E manufacturing method)
1200 mL of an aqueous solution containing 0.75 g of low molecular weight gelatin having a molecular weight of 15000, 0.9 g of KBr, and 0.2 g of modified silicone oil used in the preparation of Em-A was maintained at 39 ° C., adjusted to pH 1.8 and stirred vigorously. . AgNO_ThreeAn aqueous solution containing 0.45 g and an aqueous KBr solution containing 1.5 mol% KI were added over 16 seconds by the double jet method. At this time, the excessive concentration of KBr was kept constant. The temperature was raised to 54 ° C and aging was performed. After completion of the aging, 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, 2.9 g of KBr was added. AgNO_Three288 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.
[0193]
After adding 2.5 g of KBr, AgNO_ThreeAn aqueous solution containing 87.7 g and an aqueous KBr 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_Three132 mL of an aqueous solution containing 41.8 g and an aqueous KBr 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.
[0194]
After washing with water, gelatin was added to adjust the pH to 6.5 and pAg 8.2 at 40 ° C. After adding compounds 11 and 12, 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 13 and 14 were added. Potassium thiocyanate, chloroauric acid, sodium thiosulfate, and N, N-dimethylselenourea were added for optimum chemical sensitization. Compounds 13 and 14 were added at the end of chemical sensitization.
[0195]
[Chemical 8]

[Chemical 9]

(Em-F manufacturing method)
AgNO during nucleation in the preparation of Em-E_ThreeIt was prepared in substantially the same manner as Em-E except that the addition amount was changed to 4.12 times. However, the sensitizing dye of Em-E was changed to sensitizing dyes 12, 15, 16, and 17.
[0196]
[Chemical Formula 10]

Embedded image

Embedded image

(Em-G manufacturing method)
Maintain a pH of 1.8 by maintaining 1200 mL of an aqueous solution containing 0.70 g of low molecular weight gelatin having a molecular weight of 15000, 0.9 g of KBr, 0.175 g of KI and 0.2 g of modified silicone oil used in the preparation of Em-A at 33 ° C. Prepared 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 62 ° 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, 2.9 g of KBr was added. AgNO_Three270 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._ThreeAgI fine grain emulsion with a grain size of 0.008 μm prepared by mixing an aqueous solution and an aqueous KI solution immediately before addition in another chamber having a magnetic coupling induction stirrer described in JP-A-10-43570 contains silver iodide At the same time, the rate was 4.1 mol%, and the silver potential was kept at -60 mV to the saturated calomel electrode.
[0197]
After adding 2.6 g of KBr, AgNO_ThreeAn aqueous solution containing 87.7 g and an aqueous KBr 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_Three132 mL of an aqueous solution containing 41.8 g and an aqueous KBr 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_Three321 mL of an aqueous solution containing 66.4 g was added over 4 minutes. The silver potential was kept at −60 mV with an aqueous KBr solution for 2 minutes at the beginning of the addition. It was washed with water in the same manner as Em-F and chemically sensitized.
[0198]
(Em-H manufacturing method)
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 45 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 aging, AgNO_ThreeAn aqueous solution containing 133.4 g and an aqueous KBr solution were added over 20 minutes so that the final flow rate was 2.6 times the initial flow rate by the double jet method. 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.
[0199]
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. It was washed with water in the same manner as Em-F and chemically sensitized.
[0200]
(Em-I manufacturing method)
Em-H was prepared in substantially the same manner except that the temperature during nucleation was changed to 35 ° C.
[0201]
(Em-J manufacturing method)
1200 mL of an aqueous solution containing 0.38 g of phthalated gelatin having a phthalation rate of 97% and a molecular weight of 100,000 and 0.9 g of KBr was kept at 60 ° C., adjusted to pH 2 and vigorously stirred. AgNO_ThreeAn aqueous solution containing 1.96 g and an aqueous solution containing 1.67 g of KBr and 0.172 g of KI 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, 2.99 g of KBr and 6.2 g of NaCl were added. AgNO_Three60.7 mL of an aqueous solution containing 27.3 g and an aqueous KBr solution were added over 31 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.
[0202]
After adding 1.5 mg of thiourea dioxide, AgNO_Three132 mL of an aqueous solution containing 41.8 g and an aqueous KBr 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 to adjust the pH to 6.5 and pAg 8.2 at 40 ° C. After adding compounds 11 and 12, the temperature was raised to 61 ° C. After addition of sensitizing dyes 18, 19, 20 and 21, K₂IrCl₆Potassium thiocyanate, chloroauric acid, sodium thiosulfate, and N, N-dimethylselenourea were added for optimum chemical sensitization. Compounds 13 and 14 were added at the end of chemical sensitization.
[0203]
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[0204]
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[0205]
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[0206]
(Em-K manufacturing method)
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 6.45 g of KBr were added by a double jet method over 1 minute. After heating to 75 ° C, AgNO_Three21 mL of an aqueous solution containing 6.9 g was added over 2 minutes. NH_FourNO_Three26 g, 1 N, and 56 mL of NaOH were sequentially added, followed by aging. After completion of aging, the pH was adjusted to 4.8. AgNO_Three438 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.
[0207]
After dropping to 55 ° C, AgNO_Three240 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, 4 mg of sodium benzenethiosulfonate and K₂IrCl₆ 0.05 mg was added. AgNO_Three177 mL of an aqueous solution containing 57.2 g and 223 mL of an aqueous solution containing 40.2 g of KBr were added over 8 minutes by the double jet method. Washed with water and chemically sensitized in substantially the same manner as Em-J.
[0208]
(Em-L manufacturing method)
The Em-K was prepared in substantially the same manner except that the temperature during nucleation was changed to 40 ° C.
[0209]
(Em-M manufacturing method)
Prepared in substantially the same manner as Em-J. However, chemical sensitization was carried out in substantially the same manner as Em-F.
[0210]
Table 6 summarizes the characteristic values of the silver halide emulsions from Em-A to Em-M.
[0211]
[Table 6]

[0212]
1) Support
The support used in this example was prepared by the following method.
100 parts by mass of polyethylene-2,6-naphthalate polymer and Tinuvin P.I. 326 (manufactured by Ciba-Geigy Ciba-Geigy) was dried, melted at 300 ° C., extruded from a T-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 techniques: I-1, I-4, I-6, I-24, I-26, I- 27, 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.
[0213]
2) Application of undercoat layer
The support was subjected to corona discharge treatment, UV discharge treatment, and glow discharge treatment on both sides, and then gelatin 0.1 g / m on each side.²Sodium α-sulfodi-2-ethylhexyl succinate 0.01 g / m², Salicylic acid 0.04 g / m²P-chlorophenol 0.2 g / m², (CH₂= CHSO₂CH₂CH₂NHCO)₂CH₂0.012 g / m², Polyamide-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.).
[0214]
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.
[0215]
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 (CH₂OCONH-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%.
[0216]
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.
[0217]
4) Coating of photosensitive layer
Next, a layer 201 having the following composition was applied on the opposite side of the back layer obtained above to prepare a sample 201 as a color negative photosensitive material.
[0218]
(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.
[0219]
First layer (first antihalation layer)
Black colloidal silver Silver 0.155
0.07 μm surface fogging AgBrI (2) Silver 0.01
Gelatin 0.87
ExC-1 0.002
ExC-3 0.002
Cpd-2 0.001
HBS-1 0.004
HBS-2 0.002
[0220]
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
[0221]
Third layer (intermediate layer)
0.07 μm AgBrI (2) 0.020
ExC-2 0.022
Polyethyl acrylate latex 0.085
Gelatin 0.294
[0222]
4th layer (low sensitivity red sensitive emulsion layer)
Emulsion r of Example-2 Silver 0.323
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
[0223]
5th layer (medium sensitivity red emulsion layer)
Silver iodobromide emulsion K Silver 0.21
Silver iodobromide emulsion L Silver 0.62
ExC-1 0.14
ExC-2 0.026
ExC-3 0.020
ExC-4 0.12
ExC-5 0.016
ExC-6 0.007
Cpd-2 0.036
Cpd-4 0.028
HBS-1 0.16
Gelatin 1.18
[0224]
6th layer (high-sensitivity red-sensitive emulsion layer)
Silver iodobromide emulsion J Silver 1.47
ExC-1 0.18
ExC-3 0.07
ExC-6 0.029
ExC-7 0.010
ExY-5 0.008
Cpd-2 0.046
Cpd-4 0.077
HBS-1 0.25
HBS-2 0.12
Gelatin 2.12
[0225]
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
[0226]
Eighth layer (a layer that gives a layered effect to the red sensitive layer)
Silver iodobromide emulsion E Silver 0.560
Cpd-4 0.030
ExM-2 0.096
ExM-3 0.028
ExY-1 0.031
ExG-1 0.006
HBS-1 0.085
HBS-3 0.003
Gelatin 0.58
[0227]
9th layer (low sensitivity green emulsion layer)
Silver iodobromide emulsion G Silver 0.39
Silver iodobromide emulsion H Silver 0.28
Silver iodobromide emulsion I Silver 0.35
ExM-2 0.36
ExM-3 0.045
ExG-1 0.005
HBS-1 0.28
HBS-3 0.01
HSB-4 0.27
Gelatin 1.39
[0228]
10th layer (medium sensitive green sensitive emulsion layer)
Silver iodobromide emulsion F Silver 0.20
Silver iodobromide emulsion G 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-3 2.1 × 10^-3
Gelatin 0.44
[0229]
11th layer (high sensitivity green emulsion layer)
Em-M Silver 0.99
ExC-6 0.004
ExM-1 0.016
ExM-3 0.036
ExM-4 0.020
ExM-5 0.004
ExY-5 0.003
ExM-2 0.013
ExG-1 0.005
Cpd-4 0.007
HBS-1 0.18
Polyethyl acrylate latex 0.099
Gelatin 1.11
[0230]
12th layer (yellow filter layer)
Yellow colloidal silver Silver 0.047
Cpd-1 0.16
Oil-soluble dye ExF-5 0.010
Solid disperse dye ExF-6 0.010
HBS-1 0.082
Gelatin 1.057
[0231]
13th layer (low sensitivity blue-sensitive emulsion layer)
Silver iodobromide emulsion B Silver 0.18
Silver iodobromide emulsion C Silver 0.20
Silver iodobromide emulsion D 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
[0232]
14th layer (high sensitivity blue-sensitive emulsion layer)
Silver iodobromide emulsion A 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
[0233]
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-18 0.009
F-19 0.005
F-20 0.005
HBS-1 0.12
HBS-4 5.0 × 10^-2
Gelatin 2.3
[0234]
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
[0235]
Furthermore, in order to improve storage stability, processability, pressure resistance, antibacterial / antibacterial properties, antistatic properties and coatability as appropriate for each layer, W-1 to W-5, B-4 to B-6, F-1 to F-18 and iron salt, lead salt, gold salt, platinum salt, palladium salt, iridium salt, ruthenium salt and rhodium salt are contained. 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.
[0236]
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 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% aqueous gelatin 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 0.24 μm.
[0237]
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.
[0238]
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 average particle size was 0.52 μm.
[0239]
The compounds used for forming each of the above layers are as shown below.
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[0240]
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[0241]
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[0242]
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[0243]
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[0244]
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[0245]
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[0246]
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[0247]
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[0248]
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[0249]
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[0250]
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[0251]
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[0252]
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[0253]
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Sample Nos. 202, 203, 204, and 205 were prepared by changing the emulsion used in the fourth layer to emulsions s, t, u, and v, respectively. These samples were subjected to hardening for 14 hours under conditions of 40 ° C. and 70% relative humidity. Thereafter, 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.
[0254]
The treatment process and the treatment liquid composition are shown below.

[0255]
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.
[0256]
The composition of the treatment liquid is shown below.

[0257]

[0258]
(Fixing (1) Tank liquid)
5:95 (volume ratio) mixture of the above bleach tank solution and the following fixing tank solution
(PH 6.8)
[0259]

[0260]
(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.
[0261]

[0262]
The results are shown in Table 7.
[0263]
[Table 7]

[0264]
As is apparent from Table 7, it can be seen that a sensitive material having high sensitivity and a high gradation can be obtained by using the emulsion of the present invention.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view showing a schematic configuration of a stirring device used in an embodiment of the present invention.
[Explanation of symbols]
10 Stirrer
11, 12, 13 Liquid supply port
16 Liquid outlet
18 Mixing tank
19 tank body
20 Seal plate
21, 22 Stirrer blade
26 External magnet
28, 29 Motor

Claims (3)

It contains silver iodochlorobromide tabular grains having a (111) plane as the main surface, the (111) plane ratio of the side surfaces of the grains is 75% or more, and 70% or more of the total projected area is from ( i) to ( iv ) A silver halide photographic emulsion characterized by being occupied by grains satisfying
(I) Hexagonal tabular grains in which the ratio of the length of the side having the maximum length to the length of the side having the minimum length is 2 or less (ii) Silver chloride content at at least one vertex of the hexagon (Iii) Silver chloride content of 0.5 mol% or more and 6 mol% or less (iv) Silver iodide content of 0.5 mol% or more and 10 mol% or less under It contains silver iodochlorobromide tabular grains having a (111) plane as the main surface, the (111) plane ratio of the side surfaces of the grains is 75% or more, and 70% or more of the total projected area is the following (i), (ii A silver halide photographic emulsion characterized by being occupied by grains satisfying '), (iii) and ( iv ) .
(I) Hexagonal tabular grains in which the ratio of the length of the side having the maximum length to the length of the side having the minimum length is 2 or less (ii ') Epitaxially bonded to at least one vertex of the hexagon having a part (iii) 6 mol% of silver chloride content is more than 0.5 mol% (iv) the silver iodide content of 10 mol% or less than 0.5 mol%   A silver halide photographic material having a photosensitive layer containing the silver halide photographic emulsion according to claim 1 on a support.

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