JP2005031365A - Silver halide photographic emulsion and silver halide photographic sensitive material using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silver halide photographic emulsion having high sensitivity, high contrast, and good storage stability, and a photographic sensitive material using the emulsion. <P>SOLUTION: In the silver halide emulsion comprising a dispersion medium and silver halide grains, ≥70% of the total projected area of the silver halide grains is occupied by epitaxial tabular grains satisfying the following requirements (i)-(iv): (i) the epitaxial tabular grains are silver iodochlorobromide epitaxial tabular grains having (111) faces as main planes, (ii) the epitaxial tabular grains have an epitaxial portion in at least one vertex of each host tabular grain, (iii) in the epitaxial portion, the ratio (Br/Cl) between an average silver chloride content (Cl mol%) and an average silver bromide content (Br mol%) is in the range of 0.6 to 1.4, (iv) when the volume of the epitaxial portion is represented by Vepi, the volume of the host tabular grain by Vhost, and the relation between these is expressed by Vepi<SP>1/3</SP>=0.34Vhost<SP>1/3</SP>+d, the value d is in the range of 0.3d<SB>0</SB>to 1.7d<SB>0</SB>(where d<SB>0</SB>=0.03). <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

【０１０５】
本発明のハロゲン化銀乳剤を用いて製造される感光材料には種々の色素形成カプラーを使用することができるが、以下のカプラーが特に好ましい。
【０１０６】
イエローカプラー： 欧州特許出願公開第５０２，４２４Ａ号明細書に記載の式（Ｉ），（ＩＩ）で表わされるカプラー； 欧州特許出願公開第５１３，４９６Ａ号明細書に記載の式（１），（２） で表わされるカプラー （特に１８頁のＹ−２８）； 欧州特許出願公開第５６８，０３７Ａ号明細書に記載ののクレーム１の式（Ｉ） で表わされるカプラー； 米国特許第５，０６６，５７６号明細書のカラム１の４５〜５５行目に記載の一般式（Ｉ） で表わされるカプラー； 特開平４−２７４４２５号公報の段落０００８に記載の一般式（Ｉ） で表わされるカプラー； 欧州特許出願公開第４９８，３８１Ａ１号明細書の４０頁のクレーム１に記載のカプラー（特に１８頁のＤ−３５）； 欧州特許出願公開第４４７，９６９Ａ１号明細書の４頁に記載の式（Ｙ） で表わされるカプラー（特にＹ−１（１７頁），Ｙ−５４（４１ 頁））； 米国特許第４，４７６，２１９号明細書のカラム７の３６〜５８行に記載の式（ＩＩ）〜（ＩＶ）で表わされるカプラー（特にＩＩ−１７，１９（カラム１７），ＩＩ−２４（カラム１９））。
【０１０７】
マゼンタカプラー； 特開平３−３９７３７号公報（Ｌ−５７（１１ 頁右下），Ｌ−６８（１２ 頁右下），Ｌ−７７（１３ 頁右下）； 欧州特許４５６，２５７号明細書に記載の Ａ−４ −６３（１３４頁）， Ａ−４ −７３，−７５（１３９頁）； 欧州特許４８６，９６５号明細書に記載のＭ−４，−６（２６ 頁），Ｍ−７（２７頁）； 欧州特許出願公開第５７１，９５９Ａ号明細書に記載のＭ−４５（１９ 頁）；特開平５−２０４１０６号公報に記載の（Ｍ−１）（６ 頁）；特開平４−３６２６３１号公報の段落０２３７に記載のＭ−２２。
【０１０８】
シアンカプラー： 特開平４−２０４８４３号公報に記載のＣＸ−１，３，４，５，１１，１２，１４，１５（１４ 〜１６頁）； 特開平４−４３３４５号公報に記載のＣ−７，１０（３５ 頁），３４，３５（３７頁），（Ｉ−１），（Ｉ−１７）（４２ 〜４３頁）； 特開平６−６７３８５号公報の請求項１に記載の一般式（Ｉａ）または（Ｉｂ）で表わされるカプラー。
【０１０９】
ポリマーカプラー： 特開平２−４４３４５号公報に記載のＰ−１，Ｐ−５（１１頁）。
【０１１０】
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９６，８７３Ｂ号、独国特許第３，２３４，５３３号の各明細書に記載のものが好ましい。
【０１１１】
発色色素の不要吸収を補正するためのカプラーは、欧州特許出願公開第４５６，２５７Ａ１号明細書の５ 頁に記載の式（ＣＩ），（ＣＩＩ），（ＣＩＩＩ），（ＣＩＶ） で表わされるイエローカラードシアンカプラー（特に８４頁のＹＣ−８６）、該欧州特許出願明細書に記載のイエローカラードマゼンタカプラーＥｘＭ−７（２０２ 頁） 、 ＥＸ−１（２４９ 頁） 、 ＥＸ−７（２５１ 頁） 、米国特許第４，８３３，０６９号明細書に記載のマゼンタカラードシアンカプラーＣＣ−９ （カラム８）、ＣＣ−１３（カラム１０） 、米国特許第４，８３７，１３６号明細書に記載の（２）（カラム８）、ＷＯ ９２／１１５７５号明細書のクレーム１に記載の式（Ａ） で表わされる無色のマスキングカプラー（特に３６〜４５頁の例示化合物）が好ましい。
【０１１２】
写真性有用基を放出するカプラーとしては、以下のものが挙げられる。現像抑制剤放出化合物：欧州特許出願公開第３７８，２３６Ａ１号明細書の１１頁に記載の式（Ｉ），（ＩＩ），（ＩＩＩ），（ＩＶ） で表わされる化合物（特にＴ−１０１（３０頁），Ｔ−１０４（３１頁），Ｔ−１１３（３６頁），Ｔ−１３１（４５頁），Ｔ−１４４（５１頁），Ｔ−１５８（５８頁））， 欧州特許出願公開第４３６，９３８Ａ２号明細書の ７頁に記載の式（Ｉ） で表わされる化合物（特にＤ−４９（５１ 頁））、欧州特許出願公開第５６８，０３７Ａ号明細書に記載の式（１） で表わされる化合物（特に（２３）（１１ 頁））、欧州特許出願公開第４４０，１９５Ａ２号明細書の５ 〜６ 頁に記載の式（Ｉ），（ＩＩ），（ＩＩＩ）で表わされる化合物（特に２９頁のＩ−（１） ）；漂白促進剤放出化合物：欧州特許出願公開第３１０，１２５Ａ２号明細書の５ 頁に記載の式（Ｉ），（Ｉ’）で表わされる化合物（特に６１頁の（６０），（６１）） 及び特開平６−５９４１１号公報 の請求項１に記載の式（Ｉ） で表わされる化合物（特に（７）（７ 頁））； リガンド放出化合物：米国特許第４，５５５，４７８号明細書のクレーム１に記載のＬＩＧ−Ｘ で表わされる化合物（特にカラム１２の２１〜４１行目の化合物）；ロイコ色素放出化合物：米国特許第４，７４９，６４１号明細書のカラム３〜８に記載の化合物１〜６；蛍光色素放出化合物：米国特許第４，７７４，１８１号明細書のクレーム１に記載のＣＯＵＰ−ＤＹＥで表わされる化合物（特にカラム７〜１０の化合物１〜１１）；現像促進剤またはカブラセ剤放出化合物：米国特許第４，６５６，１２３号明細書のカラム３に記載の式（１） 、（２） 、（３） で表わされる化合物（特にカラム２５の（Ｉ−２２）） 及び欧州特許出願公開第４５０，６３７Ａ２号明細書の７５頁３６〜３８行目に記載のＥｘＺＫ−２； 離脱して初めて色素となる基を放出する化合物： 米国特許第４，８５７，４４７号明細書のクレーム１に記載の式（Ｉ） で表わされる化合物（特にカラム２５〜３６のＹ−１ 〜Ｙ−１９）。
【０１１３】
カプラー以外の添加剤としては、以下のものが好ましい。
油溶性有機化合物の分散媒： 特開昭６２−２１５２７２号公報に記載のＰ−３，５，１６，１９，２５，３０，４２，４９，５４，５５，６６，８１，８５，８６，９３（１４０〜１４４ 頁）； 油溶性有機化合物の含浸用ラテックス： 米国特許第４，１９９，３６３号明細書に記載のラテックス； 現像主薬酸化体スカベンジャー： 米国特許第４，９７８，６０６号明細書のカラム２の５４〜６２行目に記載の式（Ｉ） で表わされる化合物（特にＩ−，（１），（２），（６），（１２） （カラム４〜５）、米国特許第４，９２３，７８７号明細書のカラム２の５〜１０行目に記載の式（特に化合物１（カラム３）； ステイン防止剤： 欧州特許出願公開第２９８３２１Ａ号明細書の４頁３０〜３３行目に記載の式（Ｉ） 〜（ＩＩＩ），特にＩ−４７，７２，ＩＩＩ−１，２７（２４ 〜４８頁）； 褪色防止剤： 欧州特許出願公開第２９８３２１Ａ号明細書に記載のＡ−６，７，２０，２１，２３，２４，２５，２６，３０，３７，４０，４２，４８，６３，９０，９２，９４，１６４（６９ 〜１１８ 頁）， 米国特許５，１２２，４４４号明細書のカラム２５〜３８に記載のＩＩ−１〜ＩＩＩ−２３， 特にＩＩＩ−１０， 欧州特許出願公開第４７１３４７Ａ号明細書の８ 〜１２頁に記載のＩ−１ 〜ＩＩＩ−４，特にＩＩ−２， 米国特許第５，１３９，９３１号明細書のカラム３２〜４０に記載のＡ−１ 〜４８， 特にＡ−３９，４２； 発色増強剤または混色防止剤の使用量を低減させる素材： 欧州特許出願公開第４１１３２４Ａ号明細書の５ 〜２４頁に記載のＩ−１ 〜ＩＩ−１５，特にＩ−４６； ホルマリンスカベンジャー： 欧州特許出願公開第４７７９３２Ａ号明細書の２４〜２９頁に記載のＳＣＶ−１ 〜２８， 特にＳＣＶ−８； 硬膜剤： 特開平１−２１４８４５号公報の１７頁に記載のＨ−１，４，６，８，１４， 米国特許第４，６１８，５７３号明細書のカラム１３〜２３に記載の式（ＶＩＩ） 〜（ＸＩＩ） で表わされる化合物（Ｈ−１〜５４），特開平２−２１４８５２号公報の８頁右下に記載の式（６） で表わされる化合物（Ｈ−１〜７６），特にＨ−１４， 米国特許第３，３２５，２８７号明細書のクレーム１に記載の化合物； 現像抑制剤プレカーサー： 特開昭６２−１６８１３９号公報に記載のＰ−２４，３７，３９（６〜７ 頁）； 米国特許５，０１９，４９２号明細書のクレーム１に記載の化合物，特にカラム７の２８，２９； 防腐剤、防黴剤： 米国特許第４，９２３，７９０号明細書のカラム３ 〜１５に記載のＩ−１ 〜ＩＩＩ−４３， 特にＩＩ−１，９，１０，１８，ＩＩＩ−２５； 安定剤、かぶり防止剤： 米国特許第４，９２３，７９３号明細書のカラム６ 〜１６に記載のＩ−１ 〜（１４）， 特にＩ−１，６０，（２），（１３）， 米国特許第４，９５２，４８３号明細書のカラム２５〜３２に記載の化合物１〜６５， 特に３６： 化学増感剤： トリフェニルホスフィン セレニド， 特開平５−４０３２４号公報に記載の化合物５０； 染料： 特開平３−１５６４５０号公報の１５〜１８頁に記載のａ−１ 〜ｂ−２０， 特にａ−１，１２，１８，２７，３５，３６，ｂ−５，２７ 〜２９頁に記載のＶ−１ 〜２３， 特にＶ−１， 欧州特許出願公開第４４５６２７Ａ号明細書の３３〜５５頁に記載のＦ−Ｉ−１ 〜Ｆ−ＩＩ−４３，特にＦ−Ｉ−１１，Ｆ−ＩＩ−８，欧州特許出願公開第４５７１５３Ａ号明細書の１７〜２８頁に記載のＩＩＩ−１ 〜３６， 特にＩＩＩ−１，３， 国際出願ＷＯ ８８／０４７９４号パンフレットに記載の８〜２６のＤｙｅ−１ 〜１２４ の微結晶分散体， 欧州特許出願公開第３１９９９９Ａ号明細書の６〜１１頁に記載の化合物１〜２２， 特に化合物１， 欧州特許出願公開第５１９３０６Ａ号明細書に記載の式（１） ないし（３） で表わされる化合物Ｄ−１ 〜８７（３〜２８頁），米国特許第４，２６８，６２２号明細書に記載の式（Ｉ） で表わされる化合物１〜２２ （カラム３〜１０）， 米国特許第４，９２３，７８８号明細書に記載の式（Ｉ） で表わされる化合物（１） 〜（３１） （カラム２〜９）； ＵＶ吸収剤： 特開昭４６−３３３５号公報に記載の式（１） で表わされる化合物（１８ｂ） 〜（１８ｒ），１０１ 〜４２７（６〜９頁），欧州特許出願公開第５２０９３８Ａ号明細書に記載の式（Ｉ） で表わされる化合物（３） 〜（６６）（１０ 〜４４頁） 及び式（ＩＩＩ） で表わされる化合物ＨＢＴ−１ 〜１０（１４ 頁）， 欧州特許出願公開第５２１８２３Ａ号明細書に記載の式（１） で表わされる化合物（１） 〜（３１） （カラム２〜９）。
【０１１４】
本発明は、白黒印画紙、白黒ネガフイルム、レントゲンフイルム、一般用もしくは映画用のカラーネガフイルム、スライド用もしくはテレビ用のカラー反転フイルム、カラーペーパー、カラーポジフイルムおよびカラー反転ペーパーのような種々のカラー感光材料に適用することができる。また、特公平２−３２６１５号、実公平３−３９７８４号の各公報に記載されているレンズ付きフイルムユニット用に好適である。
【０１１５】
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。
【０１１６】
本発明で得られるハロゲン化銀を用いて製造される感光材料は、乳剤層を有する側の全親水性コロイド層の膜厚の総和が２８μｍ以下であることが好ましく、２３μｍ以下がより好ましく、１８μｍ以下が更に好ましく、１６μｍ以下が特に好ましい。また膜膨潤速度Ｔ_１／２は３０秒以下が好ましく、２０秒以下がより好ましい。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％を飽和膜厚としたとき、膜厚がその１／２に到達するまでの時間と定義する。膜厚は、室温２５℃、相対湿度５５％調湿下（２日）で測定した膜厚を意味し、Ｔ_１／２は、エー・グリーン（Ａ．Ｇｒｅｅｎ）らの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卷、２，１２４〜１２９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。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。また、膨潤率は１５０〜４００％が好ましい。膨潤率とは、さきに述べた条件下での最大膨潤膜厚から、式：（最大膨潤膜厚−膜厚）／膜厚 により計算できる。
【０１１７】
本発明で得られるハロゲン化銀を用いて製造される感光材料は、乳剤層を有する側の反対側に、乾燥膜厚の総和が２μｍ〜２０μｍの親水性コロイド層（バック層と称す）を設けることが好ましい。このバック層には、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。
【０１１８】
本発明で得られるハロゲン化銀を用いて製造される感光材料は、前述のＲＤ．Ｎｏ．１７６４３の２８〜２９頁、同Ｎｏ．１８７１６の６５１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。
【０１１９】
次に、本発明に使用されるカラーネガフイルム用の処理液について説明する。
【０１２０】
本発明に使用される発色現像液には、特開平４−１２１７３９号公報の第９頁右上欄１行〜第１１頁左下欄４行に記載の化合物を使用することができる。特に迅速な処理を行う場合の発色現像主薬としては、２−メチル−４−〔Ｎ−エチル−Ｎ−（２−ヒドロキシエチル）アミノ〕アニリン、２−メチル−４−〔Ｎ−エチル−Ｎ−（３−ヒドロキシプロピル）アミノ〕アニリン、２−メチル−４−〔Ｎ−エチル−Ｎ−（４−ヒドロキシブチル）アミノ〕アニリンが好ましい。
【０１２１】
これらの発色現像主薬は発色現像液１リットル（以下、「Ｌ」とも表記する。）あたり０．０１〜０．０８モルの範囲で使用することが好ましく、特には０．０１５〜０．０６モル、更には０．０２〜０．０５モルの範囲で使用することが好ましい。また発色現像液の補充液には、この濃度の１．１〜３倍の発色現像主薬を含有させておくことが好ましく、特に１．３〜２．５倍を含有させておくことが好ましい。
【０１２２】
発色現像液の保恒剤としては、ヒドロキシルアミンが広範に使用できるが、より高い保恒性が必要な場合は、アルキル基やヒドロキシアルキル基、スルホアルキル基、カルボキシアルキル基などの置換基を有するヒドロキシルアミン誘導体が好ましく、具体的にはＮ，Ｎ−ジ（スルホエチル）ヒドロキルアミン、モノメチルヒドロキシルアミン、ジメチルヒドロキシルアミン、モノエチルヒドロキシルアミン、ジエチルヒドロキルアミン、Ｎ，Ｎ−ジ（カルボキシエチル）ヒドロキルアミンが好ましい。上記の中でも、特にＮ，Ｎ−ジ（スルホエチル）ヒドロキルアミンが好ましい。これらはヒドロキシルアミンと併用してもよいが、好ましくはヒドロキシルアミンの代わりに、１種または２種以上使用することが好ましい。
【０１２３】
保恒剤は１Ｌあたり０．０２〜０．２モルの範囲で使用することが好ましく、特に０．０３〜０．１５モル、更には０．０４〜０．１モルの範囲で使用することが好ましい。また補充液においては、発色現像主薬の場合と同様に、母液（処理タンク液）の１．１〜３倍の濃度で保恒剤を含有させておくことが好ましい。
【０１２４】
発色現像液には、発色現像主薬の酸化物のタール化防止剤として亜硫酸塩が使用される。亜硫酸塩は１Ｌあたり０．０１〜０．０５モルの範囲で使用するのが好ましく、特には０．０２〜０．０４モルの範囲が好ましい。補充液においては、これらの１．１〜３倍の濃度で使用することが好ましい。
【０１２５】
また、発色現像液のｐＨは９．８〜１１．０の範囲が好ましいが、特には１０．０〜１０．５が好ましく、また補充液においては、これらの値から０．１〜１．０の範囲で高い値に設定しておくことが好ましい。このようなｐＨを安定して維持するには、炭酸塩、リン酸塩、スルホサリチル酸塩、ホウ酸塩などの公知の緩衝剤が使用される。
【０１２６】
発色現像液の補充量は、感光材料１ｍ^２あたり８０〜１３００ｍＬが好ましいが、環境汚濁負荷の低減の観点から、より少ない方が好ましく、具体的には８０〜６００ｍＬ、更には８０〜４００ｍＬが好ましい。
【０１２７】
発色現像液中の臭化物イオン濃度は、通常、１Ｌあたり０．０１〜０．０６モルであるが、感度を保持しつつカブリを抑制してディスクリミネーションを向上させ、かつ、粒状性を良化させる目的からは、１Ｌあたり０．０１５〜０．０３モルに設定することが好ましい。臭化物イオン濃度をこのような範囲に設定する場合に、補充液には下記の式で算出した臭化物イオンを含有させればよい。ただし、下記の式のＣが負になる時は、補充液には臭化物イオンを含有させないことが好ましい。
【０１２８】
Ｃ＝Ａ−Ｗ／Ｖ
Ｃ：発色現像補充液中の臭化物イオン濃度（モル／Ｌ）
Ａ：目標とする発色現像液中の臭化物イオン濃度（モル／Ｌ）
Ｗ：１ｍ^２の感光材料を発色現像した場合に、感光材料から発色現像液に溶出する臭化物イオンの量（モル）
Ｖ：１ｍ^２の感光材料に対する発色現像補充液の補充量（Ｌ）
【０１２９】
また、補充量を低減した場合や、高い臭化物イオン濃度に設定した場合、感度を高める方法として、１−フェニル−３−ピラゾリドンや１−フェニル−２−メチル−２−ヒドロキシメチル−３−ピラゾリドンに代表されるピラゾリドン類や３，６−ジチア−１，８−オクタンジオールに代表されるチオエーテル化合物などの現像促進剤を使用することも好ましい。
【０１３０】
本発明における漂白能を有する処理液には、特開平４−１２５５５８号公報の第４頁左下欄１６行〜第７頁左下欄６行に記載された化合物や処理条件を適用することができる。
【０１３１】
漂白剤は酸化還元電位が１５０ｍＶ以上のものが好ましいが、その具体例としては特開平５−７２６９４号、同５−１７３３１２号の各公報に記載のものが好ましく、特に１，３−ジアミノプロパン四酢酸、特開平５−１７３３１２号公報の第７頁に記載の具体例１の化合物である第二鉄錯塩が好ましい。
【０１３２】
また、漂白剤の生分解性を向上させるには、特開平４−２５１８４５号公報、同４−２６８５５２号公報、欧州特許第５８８，２８９号明細書、同５９１，９３４号明細書、特開平６−２０８２１３号公報に記載の化合物第二鉄錯塩を漂白剤として使用することが好ましい。これらの漂白剤の濃度は、漂白能を有する液１Ｌあたり０．０５〜０．３モルが好ましく、特に環境への排出量を低減する目的から、０．１モル〜０．１５モルで設計することが好ましい。また、漂白能を有する液が漂白液の場合は、１Ｌあたり０．２モル〜１モルの臭化物を含有させることが好ましく、特に０．３〜０．８モルを含有させることが好ましい。
【０１３３】
漂白能を有する液の補充液には、基本的に以下の式で算出される各成分の濃度を含有させる。これにより、母液中の濃度を一定に維持することができる。
【０１３４】
ＣＲ＝ＣＴ（Ｖ１＋Ｖ２）／Ｖ１＋ＣＰ
ＣＲ ：補充液中の成分の濃度
ＣＴ ：母液（処理タンク液）中の成分の濃度
ＣＰ ：処理中に消費された成分の濃度
Ｖ１ ：１ｍ^２の感光材料に対する漂白能を有する補充液の補充量（ｍＬ）
Ｖ２ ：１ｍ^２の感光材料による前浴からの持ち込み量（ｍＬ）
【０１３５】
その他、漂白液にはｐＨ緩衝剤を含有させることが好ましく、特にコハク酸、マレイン酸、マロン酸、グルタル酸、アジピン酸など、臭気の少ないジカルボン酸を含有させることが好ましい。また、特開昭５３−９５６３０号公報、ＲＤ Ｎｏ．１７１２９、米国特許第３，８９３，８５８号明細書に記載の公知の漂白促進剤を使用することも好ましい。
漂白液には、感光材料１ｍ^２あたり５０〜１０００ｍＬの漂白補充液を補充することが好ましく、特には８０〜５００ｍＬ、さらには１００〜３００ｍＬの補充をすることが好ましい。さらに漂白液にはエアレーションを行うことが好ましい。
【０１３６】
定着能を有する処理液については、特開平４−１２５５５８号公報の第７頁左下欄１０行〜第８頁右下欄１９行に記載の化合物や処理条件を適用することができる。
【０１３７】
特に、定着速度と保恒性を向上させるために、特開平６−３０１１６９号公報に記載の一般式（Ｉ）と（ＩＩ）で表される化合物を、単独あるいは併用して定着能を有する処理液に含有させることが好ましい。またｐ−トルエンスルフィン酸塩をはじめ、特開平１−２２４７６２号公報に記載のスルフィン酸を使用することも、保恒性の向上の上で好ましい。
【０１３８】
漂白能を有する液や定着能を有する液には、脱銀性の向上の観点からカチオンとしてアンモニウムを用いることが好ましいが、環境汚染低減の目的からは、アンモニウムを減少或いはゼロにする方が好ましい。
【０１３９】
漂白、漂白定着、定着工程においては、特開平１−３０９０５９号公報に記載のジェット撹拌を行うことが特に好ましい。
【０１４０】
漂白定着また定着工程における補充液の補充量は、感光材料１ｍ^２あたり１００〜１０００ｍＬであり、好ましくは１５０〜７００ｍＬ、特に好ましくは２００〜６００ｍＬである。
【０１４１】
漂白定着や定着工程には、各種の銀回収装置をインラインやオフラインで設置して銀を回収することが好ましい。インラインで設置することにより、液中の銀濃度を低減して処理できる結果、補充量を減少させることができる。また、オフラインで銀回収して残液を補充液として再利用することも好ましい。
【０１４２】
漂白定着工程や定着工程は複数の処理タンクで構成することができ、各タンクはカスケード配管して多段向流方式にすることが好ましい。現像機の大きさとのバランスから、一般には２タンクカスケード構成が効率的であり、前段のタンクと後段のタンクにおける処理時間の比は、０．５：１〜１：０．５の範囲にすることが好ましく、特には０．８：１〜１：０．８の範囲が好ましい。
【０１４３】
漂白定着液や定着液には、保恒性の向上の観点から金属錯体になっていない遊離のキレート剤を存在させることが好ましいが、これらのキレート剤としては、漂白液に関して記載した生分解性キレート剤を使用することが好ましい。
【０１４４】
水洗および安定化工程に関しては、上記の特開平４−１２５５８号公報の第１２頁右下欄６行〜第１３頁右下欄第１６行に記載の内容を好ましく適用することができる。特に、安定液にはホルムアルデヒドに代わって欧州特許５０４，６０９号、同５１９，１９０号の各明細書に記載のアゾリルメチルアミン類や特開平４−３６２９４３号公報に記載のＮ−メチロールアゾール類を使用することや、マゼンタカプラーを二当量化してホルムアルデヒドなどの画像安定化剤を含まない界面活性剤の液にすることが、作業環境の保全の観点から好ましい。
【０１４５】
また、感光材料に塗布された磁気記録層へのゴミの付着を軽減するには、特開平６−２８９５５９号公報に記載の安定液が好ましく使用できる。
【０１４６】
水洗および安定液の補充量は、感光材料１ｍ^２あたり８０〜１０００ｍＬが好ましく、特には１００〜５００ｍＬ、さらには１５０〜３００ｍＬが、水洗または安定化機能の確保と環境保全のための廃液減少の両面から好ましい範囲である。このような補充量で行う処理においては、バクテリアや黴の繁殖防止のために、チアベンダゾール、１，２−ベンゾイソチアゾリン−３オン、５−クロロ−２−メチルイソチアゾリン−３−オンのような公知の防黴剤やゲンタマイシンのような抗生物質、イオン交換樹脂等によって脱イオン処理した水を用いることが好ましい。脱イオン水と防菌剤や抗生物質は、併用することがより効果的である。
【０１４７】
また、水洗または安定液タンク内の液は、特開平３−４６６５２号、同３−５３２４６号、同３−５５５４２号、同３−１２１４４８号、同３−１２６０３０号の各公報に記載の逆浸透膜処理を行って補充量を減少させることも好ましく、この場合の逆浸透膜は、低圧逆浸透膜であることが好ましい。
【０１４８】
本発明における処理においては、発明協会公開技報、公技番号９４−４９９２に開示された処理液の蒸発補正を実施することが特に好ましい。特に第２頁の（式−１）に基づいて、現像機設置環境の温度及び湿度情報を用いて補正する方法が好ましい。蒸発補正に使用する水は、水洗の補充タンクから採取することが好ましく、その場合は水洗補充水として脱イオン水を用いることが好ましい。
【０１４９】
本発明に用いられる処理剤としては、上記公開技報の第３頁右欄１５行から第４頁左欄３２行に記載のものが好ましい。また、これに用いる現像機としては、第３頁右欄の第２２行から２８行に記載のフイルムプロセサーが好ましい。
【０１５０】
本発明を実施するに好ましい処理剤、自動現像機、蒸発補正方式の具体例については、上記の公開技報の第５頁右欄１１行から第７頁右欄最終行までに記載されている。
【０１５１】
本発明に使用される処理剤の供給形態は、使用液状態の濃度または濃縮された形の液剤、あるいは顆粒、粉末、錠剤、ペースト状、乳液など、いかなる形態でもよい。このような処理剤の例として、特開昭６３−１７４５３号公報には低酸素透過性の容器に収納した液剤、特開平４−１９６５５号公報、同４−２３０７４８号公報には真空包装した粉末あるいは顆粒、同４−２２１９５１号公報には水溶性ポリマーを含有させた顆粒、特開昭５１−６１８３７号公報、特開平６−１０２６２８号公報には錠剤、特表昭５７−５００４８５号公報にはペースト状の処理剤が開示されており、いずれも好ましく使用できるが、使用時の簡便性の面から、予め使用状態の濃度で調製してある液体を使用することが好ましい。
【０１５２】
これらの処理剤を収納する容器には、ポリエチレン、ポリプロピレン、ポリ塩化ビニル、ポリエチレンテレフタレート、ナイロンなどが、単独あるいは複合材料として使用される。これらは要求される酸素透過性のレベルに合わせて選択される。発色現像液などの酸化されやすい液に対しては、低酸素透過性の素材が好ましく、具体的にはポリエチレンテレフタレートやポリエチレンとナイロンの複合材料が好ましい。これらの材料は５００〜１５００μｍの厚さで、容器に使用され、酸素透過性を２０ｍＬ／ｍ^２・２４ｈｒｓ・ａｔｍ以下にすることが好ましい。
【０１５３】
次に本発明に使用されるカラー反転フイルム用の処理液について説明する。
カラー反転フイルム用の処理については、アズテック有限会社発行の公知技術第６号（１９９１年４月１日）第１頁５行〜第１０頁５行、及び第１５頁８行〜第２４頁２行に詳細に記載されており、その内容はいずれも好ましく適用することができる。
【０１５４】
カラー反転フイルムの処理においては、画像安定化剤は調整浴か最終浴に含有される。このような画像安定化剤としては、ホルマリンのほかにホルムアルデヒド重亜硫酸ナトリウム、Ｎ−メチロールアゾール類があげられるが、作業環境の観点からホルムアルデヒド重亜硫酸ナトリウムかＮ−メチロールアゾール類が好ましく、Ｎ−メチロールアゾール類としては、特にＮ−メチロールトリアゾールが好ましい。また、カラーネガフイルムの処理において記載した発色現像液、漂白液、定着液、水洗水などに関する内容は、カラー反転フイルムの処理にも好ましく適用できる。
【０１５５】
上記の内容を含む好ましいカラー反転フイルムの処理剤として、イーストマンコダック社のＥ−６処理剤及び富士写真フイルム（株）のＣＲ−５６処理剤をあげることができる。
【０１５６】
次に、本発明に好ましく用いられる磁気記録層について説明する。
磁気記録層とは、磁性体粒子をバインダー中に分散した水性もしくは有機溶媒系塗布液を支持体上に塗設したものである。
【０１５７】
本発明で用いられる磁性体粒子は、γＦｅ_２Ｏ_３などの強磁性酸化鉄、Ｃｏ被着γＦｅ_２Ｏ_３、Ｃｏ被着マグネタイト、Ｃｏ含有マグネタイト、強磁性二酸化クロム、強磁性金属、強磁性合金、六方晶系のＢａフェライト、Ｓｒフェライト、Ｐｂフェライト、Ｃａフェライトなどを使用できる。Ｃｏ被着γＦｅ_２Ｏ_３などのＣｏ被着強磁性酸化鉄が好ましい。形状としては針状、米粒状、球状、立方体状、板状等いずれでもよい。比表面積ではＳ_ＢＥＴで２０ｍ^２／ｇ以上が好ましく、３０ｍ^２／ｇ以上が特に好ましい。強磁性体の飽和磁化（σｓ）は、好ましくは３．０×１０^４〜３．０×１０^５Ａ／ｍであり、特に好ましくは４．０×１０^４〜２．５×１０^５Ａ／ｍである。強磁性体粒子を、シリカおよび／またはアルミナや有機素材による表面処理を施してもよい。さらに、磁性体粒子は特開平６−１６１０３２に記載された如くその表面にシランカップリング剤またはチタンカップリング剤で処理されてもよい。又特開平４−２５９９１１号公報、同５−８１６５２号公報に記載の表面に無機、有機物を被覆した磁性体粒子も使用できる。
【０１５８】
磁性体粒子に用いられるバインダーは、特開平４−２１９５６９号公報に記載の熱可塑性樹脂、熱硬化性樹脂、放射線硬化性樹脂、反応型樹脂、酸、アルカリまたは生分解性ポリマー、天然物重合体（セルロース誘導体、糖誘導体など）およびそれらの混合物を使用することができる。上記の樹脂のＴｇは−４０℃〜３００℃、質量平均分子量は０．２万〜１００万である。例えばビニル系共重合体、セルロースジアセテート、セルローストリアセテート、セルロースアセテートプロピオネート、セルロースアセテートブチレート、セルローストリプロピオネートなどのセルロース誘導体、アクリル樹脂、ポリビニルアセタール樹脂を挙げることができ、ゼラチンも好ましい。特にセルロースジ（トリ）アセテートが好ましい。バインダーは、エポキシ系、アジリジン系、イソシアネート系の架橋剤を添加して硬化処理することができる。イソシアネート系の架橋剤としては、トリレンジイソシアネート、４，４’−ジフェニルメタンジイソシアネート、ヘキサメチレンジイソシアネート、キシリレンジイソシアネート、などのイソシアネート類、これらのイソシアネート類とポリアルコールとの反応生成物（例えば、トリレンジイソシアナート３ｍｏｌとトリメチロールプロパン１ｍｏｌの反応生成物）、及びこれらのイソシアネート類の縮合により生成したポリイソシアネートなどがあげられ、例えば特開平６−５９３５７号公報に記載されている。
【０１５９】
前述の磁性体を上記バインダー中に分散する方法は、特開平６−３５０９２号公報に記載されているように、ニーダー、ピン型ミル、アニュラー型ミルなどを用いる方法が好ましく、併用も好ましい。特開平５−０８８２８３号公報に記載の分散剤や、その他の公知の分散剤が使用できる。磁気記録層の厚みは０．１μｍ〜１０μｍ、好ましくは０．２μｍ〜５μｍ、より好ましくは０．３μｍ〜３μｍである。磁性体粒子とバインダーの質量比は好ましくは０．５：１００〜６０：１００からなり、より好ましくは１：１００〜３０：１００である。磁性体粒子の塗布量は０．００５〜３ｇ／ｍ^２、好ましくは０．０１〜２ｇ／ｍ^２、さらに好ましくは０．０２〜０．５ｇ／ｍ^２である。磁気記録層の透過イエロー濃度は、０．０１〜０．５０が好ましく、０．０３〜０．２０がより好ましく、０．０４〜０．１５が特に好ましい。磁気記録層は、写真用支持体の裏面に塗布または印刷によって全面またはストライプ状に設けることができる。磁気記録層を塗布する方法としてはエアードクター、ブレード、エアナイフ、スクイズ、含浸、リバースロール、トランスファーロール、グラビヤ、キス、キャスト、スプレイ、ディップ、バー、エクストリュージョン等が利用でき、特開平５−３４１４３６号公報等に記載の塗布液が好ましい。
【０１６０】
磁気記録層に、潤滑性向上、カール調節、帯電防止、接着防止、ヘッド研磨などの機能を合せ持たせてもよいし、別の機能性層を設けて、これらの機能を付与させてもよく、粒子の少なくとも１種がモース硬度５以上の非球形無機粒子の研磨剤が好ましい。非球形無機粒子の組成としては、酸化アルミニウム、酸化クロム、二酸化珪素、二酸化チタン、シリコンカーバイト等の酸化物、炭化珪素、炭化チタン等の炭化物、ダイアモンド等の微粉末が好ましい。これらの研磨剤は、その表面をシランカップリング剤またはチタンカップリング剤で処理されてもよい。これらの粒子は磁気記録層に添加してもよく、また磁気記録層上にオーバーコート（例えば保護層，潤滑剤層など）しても良い。この時使用するバインダーは前述のものが使用でき、好ましくは磁気記録層のバインダーと同じものがよい。磁気記録層を有する感材については、米国特許５，３３６，５８９号、同５，２５０，４０４号、同５，２２９，２５９号、同５，２１５，８７４号、欧州特許４６６，１３０号の各明細書に記載されている。
【０１６１】
次に本発明に用いられるポリエステル支持体について記すが、後述する感材、処理、カートリッジ及び実施例なども含め詳細については、公開技報、公技番号９４−６０２３（発明協会；１９９４．３．１５．）に記載されている。本発明に用いられるポリエステルはジオールと芳香族ジカルボン酸を必須成分として形成され、芳香族ジカルボン酸として２，６−、１，５−、１，４−、及び２，７−ナフタレンジカルボン酸、テレフタル酸、イソフタル酸、フタル酸、ジオールとしてジエチレングリコール、トリエチレングリコール、シクロヘキサンジメタノール、ビスフェノールＡ、ビスフェノールが挙げられる。この重合ポリマーとしては、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリシクロヘキサンジメタノールテレフタレート等のホモポリマーを挙げることができる。特に好ましいのは２，６−ナフタレンジカルボン酸を５０モル％〜１００モル％含むポリエステルである。中でも特に好ましいのはポリエチレン ２，６−ナフタレートである。平均分子量の範囲は約５，０００ないし２００，０００である。本発明のポリエステルのＴｇは５０℃以上であり、さらに９０℃以上が好ましい。
【０１６２】
次にポリエステル支持体は、巻き癖をつきにくくするために熱処理温度は４０℃以上Ｔｇ未満、より好ましくは（Ｔｇ−２０）℃以上Ｔｇ未満で熱処理を行う。熱処理はこの温度範囲内の一定温度で実施してもよく、冷却しながら熱処理してもよい。この熱処理時間は、０．１時間以上１５００時間以下、さらに好ましくは０．５時間以上 ２００時間以下である。支持体の熱処理は、ロール状で実施してもよく、またウェブ状で搬送しながら実施してもよい。表面に凹凸を付与し（例えばＳｎＯ_２やＳｂ_２Ｏ_５等の導電性無機微粒子を塗布する）、面状改良を図ってもよい。又端部にローレットを付与し端部のみ少し高くすることで巻芯部の切り口写りを防止するなどの工夫を行うことが望ましい。これらの熱処理は支持体製膜後、表面処理後、バック層塗布後（帯電防止剤、滑り剤等）、下塗り塗布後のどこの段階で実施してもよい。好ましいのは帯電防止剤塗布後である。
【０１６３】
このポリエステルには紫外線吸収剤を練り込んでも良い。又ライトパイピング防止のため、三菱化成製のＤｉａｒｅｓｉｎ、日本化薬製のＫａｙａｓｅｔ等ポリエステル用として市販されている染料または顔料を練り込むことにより目的を達成することが可能である。
【０１６４】
次に、本発明では支持体と感材構成層を接着させるために、表面処理することが好ましい。薬品処理、機械的処理、コロナ放電処理、火焔処理、紫外線処理、高周波処理、グロー放電処理、活性プラズマ処理、レーザー処理、混酸処理、オゾン酸化処理、などの表面活性化処理が挙げられる。表面処理の中でも好ましいのは、紫外線照射処理、火焔処理、コロナ処理、グロー処理である。
【０１６５】
次に下塗法について述べると、単層でもよく２層以上でもよい。下塗層用バインダーとしては、塩化ビニル、塩化ビニリデン、ブタジエン、メタクリル酸、アクリル酸、イタコン酸、無水マレイン酸などの中から選ばれた単量体を出発原料とする共重合体を始めとして、ポリエチレンイミン、エポキシ樹脂、グラフト化ゼラチン、ニトロセルロース、ゼラチンが挙げられる。支持体を膨潤させる化合物としてレゾルシンとｐ−クロルフェノールがある。下塗層にはゼラチン硬化剤としてはクロム塩（クロム明ばんなど）、アルデヒド類（ホルムアルデヒド、グルタールアルデヒドなど）、イソシアネート類、活性ハロゲン化合物（２，４−ジクロロ−６−ヒドロキシ−Ｓ−トリアジンなど）、エピクロルヒドリン樹脂、活性ビニルスルホン化合物などを挙げることができる。ＳｉＯ_２、ＴｉＯ_２、無機物微粒子またはポリメチルメタクリレート共重合体微粒子（０．０１〜１０μｍ）をマット剤として含有させてもよい。
【０１６６】
また本発明においては、帯電防止剤が好ましく用いられる。それらの帯電防止剤としては、カルボン酸及びカルボン酸塩、スルホン酸塩を含む高分子、カチオン性高分子、イオン性界面活性剤化合物を挙げることができる。
【０１６７】
帯電防止剤として最も好ましいものは、ＺｎＯ、ＴｉＯ_２、ＳｎＯ_２、Ａｌ_２Ｏ_３、Ｉｎ_２Ｏ_３、ＳｉＯ_２、ＭｇＯ、ＢａＯ、ＭｏＯ_３、Ｖ_２Ｏ_５の中から選ばれた少なくとも１種の体積抵抗率が１０^７Ω・ｃｍ以下、より好ましくは１０^５Ω・ｃｍ以下である粒子サイズ０．００１〜１．０μｍ結晶性の金属酸化物あるいはこれらの複合酸化物（Ｓｂ，Ｐ，Ｂ，Ｉｎ，Ｓ，Ｓｉ，Ｃなど）の微粒子、更にはゾル状の金属酸化物あるいはこれらの複合酸化物の微粒子である。感材への含有量としては、５〜５００ｍｇ／ｍ^２が好ましく特に好ましくは１０〜３５０ｍｇ／ｍ^２である。導電性の結晶性酸化物またはその複合酸化物とバインダーの量の比は１／３００〜１００／１が好ましく、より好ましくは１／１００〜１００／５である。
【０１６８】
本発明の感材には滑り性がある事が好ましい。滑り剤含有層は感光層面、バック面ともに用いることが好ましい。好ましい滑り性としては動摩擦係数で０．２５以下０．０１以上である。この時の測定は直径５ｍｍのステンレス球に対し、６０ｃｍ／分で搬送した時の値を表す（２５℃、６０％ＲＨ）。この評価において相手材として感光層面に置き換えてもほぼ同レベルの値となる。
【０１６９】
本発明に使用可能な滑り剤としては、ポリオルガノシロキサン、高級脂肪酸アミド、高級脂肪酸金属塩、高級脂肪酸と高級アルコールのエステル等であり、ポリオルガノシロキサンとしては、ポリジメチルシロキサン、ポリジエチルシロキサン、ポリスチリルメチルシロキサン、ポリメチルフェニルシロキサン等を用いることができる。添加層としては乳剤層の最外層やバック層が好ましい。特にポリジメチルシロキサンや長鎖アルキル基を有するエステルが好ましい。
【０１７０】
本発明の感材にはマット剤が有る事が好ましい。マット剤としては乳剤面、バック面とどちらでもよいが、乳剤側の最外層に添加するのが特に好ましい。マット剤は処理液可溶性でも処理液不溶性でもよく、好ましくは両者を併用することである。例えばポリメチルメタクリレート、ポリ（メチルメタクリレート／メタクリル酸＝９／１または５／５（モル比））、ポリスチレン粒子などが好ましい。粒径としては０．８〜１０μｍが好ましく、その粒径分布も狭いほうが好ましく、平均粒径の０．９〜１．１倍の間に全粒子数の９０％以上が含有されることが好ましい。又マット性を高めるために０．８μｍ以下の微粒子を同時に添加することも好ましく例えばポリメチルメタクリレート（０．２μｍ）、ポリ（メチルメタクリレート／メタクリル酸＝９／１（モル比）、０．３μｍ））、ポリスチレン粒子（０．２５μｍ）、コロイダルシリカ（０．０３μｍ）が挙げられる。
【０１７１】
次に本発明で用いられるフィルムパトローネについて記す。本発明で使用されるパトローネの主材料は金属でも合成プラスチックでもよい。
【０１７２】
好ましいプラスチック材料はポリスチレン、ポリエチレン、ポリプロピレン、ポリフェニルエーテルなどである。更に本発明のパトローネは、各種の帯電防止剤を含有してもよくカーボンブラック、金属酸化物粒子、ノニオン、アニオン、カチオン及びベタイン系界面活性剤またはポリマー等を好ましく用いることが出来る。これらの帯電防止されたパトローネは特開平１−３１２５３７号公報、同１−３１２５３８号公報に記載されている。特に２５℃、２５％ＲＨでの抵抗が１０^１２Ω以下が好ましい。通常プラスチックパトローネは、遮光性を付与するためにカーボンブラックや顔料などを練り込んだプラスチックを使って製作される。パトローネのサイズは現在１３５サイズのままでもよいし、カメラの小型化には、現在の１３５サイズにおける２５ｍｍのカートリッジの径を２２ｍｍ以下とすることも有効である。パトローネのケースの容積は、３０ｃｍ^３以下好ましくは２５ｃｍ^３以下とすることが好ましい。パトローネおよびパトローネケースに使用されるプラスチックの質量は５ｇ〜１５ｇが好ましい。
【０１７３】
更に本発明で用いられる、スプールを回転してフイルムを送り出すパトローネでもよい。またフイルム先端がパトローネ本体内に収納され、スプール軸をフイルム送り出し方向に回転させることによってフイルム先端をパトローネのポート部から外部に送り出す構造でもよい。これらは米国特許４，８３４，３０６号、同５，２２６，６１３号の各明細書に開示されている。本発明に用いられる写真フイルムは現像前のいわゆる生フイルムでもよいし、現像処理された写真フイルムでもよい。又、生フイルムと現像済みの写真フイルムが同じ新パトローネに収納されていてもよいし、異なるパトローネでもよい。
【０１７４】
本発明のカラー写真感光材料は、アドバンスト・フォト・システム（以下、ＡＰシステムという）用ネガフイルムとしても好適であり、富士写真フイルム（株）（以下、富士フイルムという）製ＮＥＸＩＡ Ａ 、ＮＥＸＩＡ Ｆ 、ＮＥＸＩＡ Ｈ （順にＩＳＯ ２００／１００／４００ ）のようにフイルムをＡＰシステムフォーマットに加工し、専用カートリッジに収納したものを挙げることができる。これらのＡＰシステム用カートリッジフイルムは、富士フイルム製エピオンシリーズ（エピオン３００Ｚ等）等のＡＰシステム用カメラに装填して用いられる。また、本発明のカラー写真感光材料は、富士フイルム製フジカラー写ルンですスーパースリムのようなレンズ付きフイルムにも好適である。
【０１７５】
これらにより撮影されたフイルムは、ミニラボシステムでは次のような工程を経てプリントされる。
（１）受付（露光済みカートリッジフイルムをお客様からお預かり）
（２）デタッチ工程（カートリッジから、フイルムを現像工程用の中間カートリッジに移す）
（３）フイルム現像
（４）リアタッチ工程（現像済みのネガフイルムを、もとのカートリッジに戻す）
（５）プリント（Ｃ／Ｈ／Ｐ３タイプのプリントとインデックスプリントをカラーペーパー〔好ましくは富士フイルム製ＳＵＰＥＲ ＦＡ８ 〕に連続自動プリント）
（６）照合・出荷（カートリッジとインデックスプリントをＩＤナンバーで照合し、プリントとともに出荷）
【０１７６】
これらのシステムとしては、富士フイルムミニラボチャンピオンスーパーＦＡ−２９８／ＦＡ−２７８／ＦＡ−２５８／ＦＡ−２３８ 及び富士フイルムデジタルラボシステム フロンティアが好ましい。ミニラボチャンピオンのフイルムプロセサーとしてはＦＰ９２２ＡＬ／ＦＰ５６２Ｂ／ＦＰ５６２Ｂ，ＡＬ／ＦＰ３６２Ｂ／ＦＰ３６２Ｂ，ＡＬ が挙げられ、推奨処理薬品はフジカラージャストイットＣＮ−１６Ｌ及びＣＮ−１６Ｑである。プリンタープロセサーとしては、ＰＰ３００８ＡＲ／ＰＰ３００８Ａ／ＰＰ１８２８ＡＲ／ＰＰ１８２８Ａ／ＰＰ１２５８ＡＲ／ＰＰ１２５８Ａ／ＰＰ７２８ＡＲ ／ＰＰ７２８Ａが挙げられ、推奨処理薬品はフジカラージャストイットＣＰ−４７Ｌ及びＣＰ−４０ＦＡＩＩである。フロンティアシステムでは、スキャナー＆イメージプロセサー ＳＰ−１０００及びレーザープリンター＆ペーパープロセサー ＬＰ−１０００Ｐもしくはレーザープリンター ＬＰ−１０００Ｗが用いられる。デタッチ工程で用いるデタッチャー、リアタッチ工程で用いるリアタッチャーは、それぞれ富士フイルムのＤＴ２００／ＤＴ１００ 及びＡＴ２００／ＡＴ１００ が好ましい。
【０１７７】
ＡＰシステムは、富士フイルムのデジタルイメージワークステーションＡｌａｄｄｉｎ １０００を中心とするフォトジョイシステムにより楽しむこともできる。例えば、Ａｌａｄｄｉｎ １０００に現像済みＡＰシステムカートリッジフイルムを直接装填したり、ネガフイルム、ポジフイルム、プリントの画像情報を、３５ｍｍフイルムスキャナーＦＥ−５５０やフラットヘッドスキャナーＰＥ−５５０を用いて入力し、得られたデジタル画像データを容易に加工・編集することができる。そのデータは、光定着型感熱カラープリント方式によるデジタルカラープリンターＮＣ−５５０ＡＬやレーザー露光熱現像転写方式のピクトログラフィー３０００によって、またはフイルムレコーダーを通して既存のラボ機器によりプリントとして出力することができる。また、Ａｌａｄｄｉｎ １０００は、デジタル情報を直接フロッピー（登録商標）ディスクやＺｉｐディスクに、もしくはＣＤライターを介してＣＤ−Ｒに出力することもできる。
【０１７８】
一方、家庭では、現像済みＡＰシステムカートリッジフイルムを富士フイルム製フォトプレイヤーＡＰ−１に装填するだけでＴＶで写真を楽しむことができるし、富士フイルム製フォトスキャナーＡＳ−１に装填すれば、パソコンに画像情報を高速で連続的に取り込むこともできる。また、フイルム、プリントまたは立体物をパソコンに入力するには、富士フイルム製フォトビジョンＦＶ−１０／ＦＶ−５が利用できる。更に、フロッピー（登録商標）ディスク、Ｚｉｐディスク、ＣＤ−Ｒもしくはハードディスクに記録された画像情報は、富士フイルムのアプリケーションソフトフォトファクトリーを用いてパソコン上で様々に加工して楽しむことができる。パソコンから高画質なプリントを出力するには、光定着型感熱カラープリント方式の富士フイルム製デジタルカラープリンターＮＣ−２／ＮＣ−２Ｄが好適である。
【０１７９】
現像済みのＡＰシステムカートリッジフイルムを収納するには、フジカラーポケットアルバムＡＰ−５ポップＬ、ＡＰ−１ポップＬ、ＡＰ−１ポップＫＧまたはカートリッジファイル１６が好ましい。
【０１８０】
また、本発明で得られるハロゲン化銀乳剤を用いて製造される感光材料は、米国特許第４，５００，６２６号、特開昭６０−１３３４４９号、同５９−２１８４４３号、同６１−２３８０５６号、欧州特許出願公開第２１０，６６０Ａ２号などの明細書並びに公報に記載されている熱現像感光材料にも適用できる。
【０１８１】
また、本発明で得られるハロゲン化銀乳剤を用いて製造される感光材料は、特公平２−３２６１５号、実公平３−３９７８４号などの公報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。
【０１８２】
【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。
【０１８３】
（実施例−１）
本発明の乳剤について説明する。
（乳剤１１の調製）
（ホスト粒子）
ＫＢｒ１．０ｇ、酸化処理ゼラチン１．０ｇを含む水溶液１３００ｍＬを３５℃に保ち撹拌した。ＡｇＮＯ_３（２．０ｇ）水溶液とＫＢｒ（１．５ｇ）と酸化処理ゼラチン（０．９ｇ）を含む水溶液を２０秒間に渡り添加した。ＫＢｒ２．７ｇを含む水溶液を添加した後、５５℃に昇温した。ゼラチン２６ｇを含む水溶液を添加した。その後、第１成長としてＡｇＮＯ_３（１３５ｇ）水溶液とＫＢｒ水溶液を添加した。この時、銀電位を飽和カロメル電極に対して−１５ｍＶに保った。その後、最外層成長としてＡｇＮＯ_３水溶液（３３．５ｇ）とＫＩを含むＫＢｒ水溶液を１８分間に渡って添加した。ＫＩの濃度は沃化銀含有率が４．０モル％になるように調整した。
【０１８４】
温度を３５℃に降温した後、増感色素Ｉ、ＩＩ、ＩＩＩを６０：３９：１のモル比で飽和被覆量の７５％の比率で添加した。但し増感色素は、特開平１１−５２５０７号公報に記載の方法で作成した固体分散物として使用した。
【０１８５】
（エピタキシャル形成部）
この後、ＡｇＮＯ_３（８．５ｇ）水溶液とＮａＣｌ（３．０ｇ）を含む水溶液を添加した。その後、ＡｇＮＯ_３（０．４５ｇ）水溶液とＫＩ（０．４９ｇ）水溶液を添加した。更にその後ＡｇＮＯ_３（７．１ｇ）水溶液とＫＢｒ（４．９ｇ）水溶液を添加した。
【０１８６】
（水洗、後熟部）
続いて、通常の水洗を行った。５４℃で、ハロゲン化銀１モルに対して、チオシアン酸カリウム（１．０×１０^−４モル）、塩化金酸（１．５×１０^−５モル）、チオ硫酸ナトリウム（４．０×１０^−５モル）およびＮ，Ｎ−ジメチルセレノ尿素（２．５×１０^−６モル）を添加し最適に化学増感を施した。かぶり防止剤（化合物Ｉ）（９．５×１０^−４モル）を添加して化学増感を終了した。
【０１８７】
得られた乳剤は平均円相当径０．５３μｍ、円相当径の変動係数１７％、平均厚み０．１０５μｍ、平均アスペクト比５．０の平板粒子を含んでいた。また、全粒子の投影面積の７０％以上が円相当径０．４μｍ以上０．７μｍ以下、厚み０．０７μｍ以上０．１４μｍ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５以下である主表面が（１１１）面の六角形平板粒子であり、少なくとも１つの頂点部にエピタキシャル部を有していた。低温での透過電子顕微鏡観察の結果、全粒子の投影面積の７０％以上の粒子がエピタキシャル部以外の主表面部には転位線を持たず、かつエピタキシャル部に網目状の転位線を有していた。
【０１８８】
【化１】

【０１８９】
（乳剤１２の調製）
乳剤１１よりエピタキシャル形成部を以下の如く変更することにより乳剤１２を調製した。
ＡｇＮＯ_３（８．５ｇ）水溶液とＮａＣｌ（３．０ｇ）を含む水溶液を添加した。その後、ＡｇＮＯ_３（７．５５ｇ）水溶液とＫＩ（０．４９ｇ）並びにＫＢｒ（４．９ｇ）を含む水溶液を添加した。
【０１９０】
（乳剤１３の調製）
乳剤１１よりエピタキシャル形成部を以下の如く変更することにより乳剤１３を調製した。
ＡｇＮＯ_３（１４．３ｇ）水溶液とＮａＣｌ（５．０４ｇ）を含む水溶液を添加した。その後、ＡｇＮＯ_３（０．７６ｇ）水溶液とＫＩ（０．８２ｇ）水溶液を添加した。更にその後ＡｇＮＯ_３（１１．９ｇ）水溶液とＫＢｒ（８．２３ｇ）水溶液を添加した。
【０１９１】
（乳剤１４の調製）
乳剤１１よりエピタキシャル形成部を以下の如く変更することにより乳剤１４を調製した。
ＡｇＮＯ_３（４．２５ｇ）水溶液とＮａＣｌ（１．５ｇ）を含む水溶液を添加した。その後、ＡｇＮＯ_３（０．２３ｇ）水溶液とＫＩ（０．２５ｇ）水溶液を添加した。更にその後ＡｇＮＯ_３（３．６ｇ）水溶液とＫＢｒ（２．５ｇ）水溶液を添加した。
【０１９２】
（乳剤１５の調製）
乳剤１１よりエピタキシャル形成部を以下の如く変更することにより乳剤１５を調製した。
ＡｇＮＯ_３（６．２ｇ）水溶液とＮａＣｌ（２．２ｇ）を含む水溶液を添加した。その後、ＡｇＮＯ_３（０．４５ｇ）水溶液とＫＩ（０．４９ｇ）水溶液を添加した。更にその後ＡｇＮＯ_３（９．４ｇ）水溶液とＫＢｒ（６．５ｇ）水溶液を添加した。
【０１９３】
（乳剤１６の調製）
乳剤１１よりエピタキシャル形成部を以下の如く変更することにより乳剤１６を調製した。
ＡｇＮＯ_３（１２．５ｇ）水溶液とＮａＣｌ（４．４ｇ）を含む水溶液を添加した。その後、ＡｇＮＯ_３（０．４５ｇ）水溶液とＫＩ（０．４９ｇ）水溶液を添加した。更にその後ＡｇＮＯ_３（３．１ｇ）水溶液とＫＢｒ（２．１ｇ）水溶液を添加した。
【０１９４】
（乳剤１７の調製）
乳剤１１よりエピタキシャル形成部を以下の如く変更することにより乳剤１７を調製した。
ＡｇＮＯ_３（１０．５ｇ）水溶液とＮａＣｌ（３．７ｇ）を含む水溶液を添加した。その後、ＡｇＮＯ_３（０．７６ｇ）水溶液とＫＩ（０．８２ｇ）水溶液を添加した。更にその後ＡｇＮＯ_３（１５．７ｇ）水溶液とＫＢｒ（１０．９ｇ）水溶液を添加した。
【０１９５】
（乳剤１８の調製）
特開２００２−１６９２３８号公報の実施例２に記載の乳剤ｉにならって乳剤１８を調製した。得られた乳剤は平均円相当径０．６６μｍ、円相当径の変動係数２０％、平均厚み０．０７μｍ、平均アスペクト比９の平板粒子を含んでいた。また、全粒子の投影面積の７０％以上が、円相当径０．５μｍ以上０．８μｍ以下、厚み０．０５μｍ以上０．０９μｍ以下であり、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５以下である主表面が（１１１）面の六角形平板粒子であり、かつ少なくとも１つの頂点部にエピタキシャル接合を有していた。低温での透過電子顕微鏡観察の結果、全粒子の投影面積の７０％以上の粒子がエピタキシャル部以外の主表面部には転位線を持たず、かつエピタキシャル部に網目状と筋状の転位線を有していた。
【０１９６】
乳剤１１から１８の特性値を表１にまとめて示した。
【０１９７】
【表１】

【０１９８】
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．１０１〜１０８を作成した。
【０１９９】
【表２】

【０２００】
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、富士フィルム（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。
富士写真フィルム（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。
【０２０１】

【０２０２】

【０２０３】

【０２０４】

【０２０５】
（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。
【０２０６】

【０２０７】
処理済みの試料を緑色フィルターで濃度測定した。また露光前に５０℃、相対湿度６０％の条件に１４日保存した試料についても同様の評価を行い保存性について評価した。
【０２０８】
以上により得られた、かぶりプラス０．２の濃度での感度値（かぶり＋０．２の濃度を得るの必要な露光量の逆数の対数値（試料１０１の感度を基準とする相対値））、かぶり値、その他の写真特性を評価した結果を表３に示す。
【０２０９】
【表３】

【０２１０】
表３の結果から明らかなように、本発明の乳剤を用いることにより、高感度でハイライト部の階調が硬調で、かつ保存後の感度変化が小さい感光材料が得られる。さらに、Ｂｒ／Ｃｌが、０．６ないし１．４の範囲内にあり、ｄの値が０．３ｄ_０ないし１．７ｄ_０の範囲内にある平板粒子の全投影面積に占める割合が高い乳剤ほど効果が高いことがわかる。本発明の乳剤条件から逸脱すると、特に感度と保存性の両立が著しく悪化することがわかる。また、乳剤１８は、円相当径が乳剤１１より大きいが、本発明の乳剤条件から逸脱しているために感度が低く、さらに保存後の感度変化も大きい。
【０２１１】
（実施例２）
多層カラー写真感光材料における本発明の乳剤の効果を示す。
本実施例で用いた支持体は、下記の方法により作製した。
【０２１２】
１）第１層及び下塗り層
厚さ９０μｍのポリエチレンナフタレート支持体について、その各々の両面に、処理雰囲気圧力２．６６×１０Ｐａ、雰囲気気体中のＨ_２Ｏ分圧７５％、放電周波数３０ｋＨｚ、出力２５００Ｗ、処理強度０．５ｋＶ・Ａ・分／ｍ^２でグロー放電処理を施した。この支持体上に、第１層として下記組成の塗布液を特公昭５８−４５８９号公報に記載のバー塗布法を用いて、５ｍＬ／ｍ^２の塗布量で塗布した。
【０２１３】

【０２１４】
さらに、第１層を塗設後、直径２０ｃｍのステンレス巻芯に巻付けて、１１０℃（ＰＥＮ支持体のＴｇ：１１９℃）で４８時間加熱処理し熱履歴させてアニール処理をした後、支持体をはさみ第１層側と反対側に乳剤用の下塗り層として下記組成の塗布液をバー塗布法を用いて、１０ｍＬ／ｍ^２の塗布量で塗布した。
【０２１５】

【０２１６】
さらに、後述する第２、第３層を第１層の上に順に塗設し、最後に、後述する組成のカラーネガ感光材料を支持体に対して反対側に重層塗布することによりハロゲン化銀乳剤層付き透明磁気記録媒体を作製した。
【０２１７】
２）第２層（透明磁気記録層）
▲１▼磁性体の分散
Ｃｏ被着γ−Ｆｅ_２Ｏ_３磁性体（平均長軸長：０．２５μｍ、Ｓ_ＢＥＴ：３９ｍ^２／ｇ、Ｈｃ：６．５６×１０^４Ａ／ｍ、σＳ ：７７．１Ａｍ^２／ｋｇ、σｒ ：３７．４Ａｍ^２／ｋｇ）１１００質量部、水２２０質量部及びシランカップリング剤〔３−（ポリ（重合度１０）オキシエチニル）オキシプロピル トリメトキシシラン〕１６５質量部を添加して、オープンニーダーで３時間良く混練した。この粗分散した粘性のある液を７０℃で１昼夜乾燥し水を除去した後、１１０℃で１時間加熱処理し、表面処理をした磁気粒子を作製した。
【０２１８】
さらに以下の処方で、再びオープンニーダーにて４時間混練した。
上記表面処理済み磁気粒子 ８５５ ｇ
ジアセチルセルロース ２５．３ ｇ
メチルエチルケトン １３６．３ ｇ
シクロヘキサノン １３６．３ ｇ
【０２１９】
さらに、以下の処方で、サンドミル（１／４Ｇのサンドミル）にて２０００ｒｐｍ、４時間微細分散した。メディアは１ｍｍφのガラスビーズを用いた。
上記混練液 ４５ ｇ
ジアセチルセルロース ２３．７ ｇ
メチルエチルケトン １２７．７ ｇ
シクロヘキサノン １２７．７ ｇ
【０２２０】
さらに、以下の処方で、磁性体含有中間液を作製した。
▲２▼磁性体含有中間液の作製
上記磁性体微細分散液 ６７４ ｇ
ジアセチルセルロース溶液 ２４２８０ ｇ
（固形分４．３４％、溶媒：メチルエチルケトン／シクロヘキサノン＝１／１）
シクロヘキサノン ４６ ｇ
これらを混合した後、ディスパ−にて撹拌し、「磁性体含有中間液」を作製した。
【０２２１】
以下の処方で本発明のα−アルミナ研磨材分散液を作製した。
（ａ）スミコランダムＡＡ−１．５（平均１次粒子径１．５μｍ， 比表面積１．３ｍ^２／ｇ）粒子分散液の作製
スミコランダムＡＡ−１．５ １５２ｇ
シランカップリング剤ＫＢＭ９０３（信越シリコーン社製） ０．４８ｇ
ジアセチルセルロース溶液 ２２７．５２ｇ
（固形分４．５％、溶媒：メチルエチルケトン／シクロヘキサノン＝１／１）。
【０２２２】
上記処方にて、セラミックコートしたサンドミル（１／４Ｇのサンドミル）を用いて８００ｒｐｍ、４時間微細分散した。メディアは１ｍｍφのジルコニアビーズを用いた。
【０２２３】
（ｂ）コロイダルシリカ粒子分散液（微小粒子）
日産化学（株）製の「ＭＥＫ−ＳＴ」を使用した。
これは、メチルエチルケトンを分散媒とした、平均１次粒子径０．０１５μｍのコロイダルシリカの分散液であり、固形分は３０％である。
【０２２４】
▲３▼第２層塗布液の作製
上記磁性体含有中間液 １９０５３ ｇ
ジアセチルセルロース溶液 ２６４ ｇ
（固形分４．５％、溶媒：メチルエチルケトン／シクロヘキサノン＝１／１）
コロイダルシリカ分散液「ＭＥＫ−ＳＴ」［分散液ｂ］ １２８ ｇ
（固形分３０％）
ＡＡ−１．５分散液［分散液ａ］ １２ ｇ
ミリオネートＭＲ−４００（日本ポリウレタン（株）製） 希釈液２０３ ｇ
（固形分２０％、希釈溶剤：メチルエチルケトン／シクロヘキサノン＝１／１）
メチルエチルケトン １７０ ｇ
シクロヘキサノン １７０ ｇ
【０２２５】
上記を混合・撹拌した塗布液をワイヤーバーにて、塗布量２９．３ｍＬ／ｍ^２になるように塗布した。乾燥は１１０℃で行った。乾燥後の磁性層としての厚みは１．０μｍだった。
【０２２６】
３）第３層（高級脂肪酸エステル滑り剤含有層）
▲１▼滑り剤の分散原液の作製
下記のア液を１００℃加温溶解し、イ液に添加後、高圧ホモジナイザーで分散し、滑り剤の分散原液を作製した。
【０２２７】
ア液
下記化合物 ３９９ 質量部
Ｃ_６Ｈ_１３ＣＨ（ＯＨ）（ＣＨ_２）_１０ＣＯＯＣ_５０Ｈ_１０１
下記化合物 １７１ 質量部
ｎ−Ｃ_５０Ｈ_１０１Ｏ（ＣＨ_２ＣＨ_２Ｏ）_１６Ｈ
シクロヘキサノン ８３０ 質量部
イ液
シクロヘキサノン ８６００ 質量部
【０２２８】
▲２▼球状無機粒子分散液の作製
以下の処方にて、球状無機粒子分散液［ｃ１］を作製した。
【０２２９】
イソプロピルアルコール ９３．５４ 質量部
シランカップリング剤ＫＢＭ９０３（信越シリコーン社製）
化合物１−１：（ＣＨ_３Ｏ）_３Ｓｉ−（ＣＨ_２）_３−ＮＨ_２）５．５３ 質量部
化合物１ ２．９３ 質量部
【化２】

シーホスタＫＥＰ５０ ８８．００ 質量部
（非晶質球状シリカ、平均粒子径０．５μｍ、日本触媒（株）製）
【０２３０】
上記処方にて１０分間撹拌後、更に以下を追添する。
ジアセトンアルコール ２５２．９３ 質量部
上記液を氷冷・攪拌しながら、超音波ホモジナイザー「ＳＯＮＩＦＩＥＲ４５０（ＢＲＡＮＳＯＮ（株）製）」を用いて３時間分散し、球状無機粒子分散液ｃ１を完成させた。
【０２３１】
▲３▼球状有機高分子粒子分散液の作製
以下の処方にて、球状有機高分子粒子分散液［ｃ２］を作製した。
ＸＣ９９−Ａ８８０８（東芝シリコーン（株）製、球状架橋ポリシロキサン粒子、平均粒径０．９μｍ） ６０ 質量部
メチルエチルケトン １２０ 質量部
シクロヘキサノン １２０ 質量部
（固形分２０％、溶媒：メチルエチルケトン／シクロヘキサノン＝１／１）
【０２３２】
氷冷・攪拌しながら、超音波ホモジナイザー「ＳＯＮＩＦＩＥＲ４５０（ＢＲＡＮＳＯＮ（株）製）」を用いて２時間分散し球状有機高分子粒子分散液ｃ２を完成させた。
【０２３３】
▲４▼第３層塗布液の作製
前述、滑り剤分散原液５４２ｇに下記を加え第３層塗布液とした。
ジアセトンアルコール ５９５０ ｇ
シクロヘキサノン １７６ ｇ
酢酸エチル １７００ ｇ
上記シーホスタＫＥＰ５０分散液［ｃ１］ ５３．１ ｇ
上記球状有機高分子粒子分散液［ｃ２］ ３００ ｇ
ＦＣ４３１ ２．６５ ｇ
（３Ｍ（株）製、固形分５０％、溶剤：酢酸エチル）
ＢＹＫ３１０ ５．３ ｇ
（ＢＹＫケミジャパン（株）製、固形分含量２５％）
上記第３層塗布液を第２層の上に１０．３５ｍＬ／ｍ^２の塗布量で塗布し、１１０℃で乾燥後、更に９７℃で３分間後乾燥した。
【０２３４】
４）感光層の塗設
次に、前記で得られたバック層の支持体に対して反対側に、下記の組成の各層を重層塗布し、カラーネガフィルム試料２０１を作成した。
【０２３５】
（感光層の組成）
各成分に対応する数字は、ｇ／ｍ^２単位で表した塗布量を示し、ハロゲン化銀については銀換算の塗布量を示す。
【０２３６】
（試料２０１）
第１層（第１ハレーション防止層）
黒色コロイド銀 銀 ０．０８０
０．０７μｍの沃臭化銀乳剤 銀 ０．０１２
ゼラチン ０．７００
ＥｘＭ−１ ０．０６４
ＥｘＣ−１ ０．００４
ＥｘＣ−３ ０．００４
Ｃｐｄ−２ ０．００２
Ｆ−８ ０．００２
ＨＢＳ−１ ０．０９９
ＨＢＳ−２ ０．０１３
【０２３７】
第２層（第２ハレーション防止層）
黒色コロイド銀 銀 ０．１００
ゼラチン ０．７６７
ＥｘＦ−１ ０．００４
Ｆ−８ ０．００１
固体分散染料 ＥｘＦ−７ ０．１２０
ＥｘＹ−１ ０．０４１
ＨＢＳ−１ ０．０４８
【０２３８】
第３層（中間層）
ＥｘＣ−２ ０．０５４
Ｃｐｄ−１ ０．０９２
ポリエチルアクリレートラテックス ０．２５０
ＨＢＳ−１ ０．０７４
ゼラチン ０．５５８
【０２３９】
第４層（低感度赤感乳剤層）
乳剤１１ 銀 ０．７３
ＥｘＣ−１ ０．４０４
ＥｘＣ−２ ０．０２４
ＥｘＣ−３ ０．０８３
ＥｘＣ−４ ０．２１３
ＥｘＣ−５ ０．０４４
ＥｘＣ−６ ０．０２５
ＥｘＣ−８ ０．０７３
ＥｘＣ−９ ０．０１０
Ｃｐｄ−２ ０．０３５
Ｃｐｄ−４ ０．０３５
Ｃｐｄ−７ ０．０１０
ＵＶ−２ ０．０２２
ＵＶ−３ ０．０４２
ＵＶ−４ ０．００９
ＵＶ−５ ０．０７５
ＨＢＳ−１ ０．２７４
ＨＢＳ−５ ０．０３８
ゼラチン ２．４５７
【０２４０】
第５層（中感度赤感乳剤層）
Ｅｍ−Ｂ 銀 １．０５２
ＥｘＭ−５ ０．０２１
ＥｘＣ−１ ０．３２４
ＥｘＣ−２ ０．０７７
ＥｘＣ−３ ０．０１０
ＥｘＣ−４ ０．１４５
ＥｘＣ−５ ０．０２２
ＥｘＣ−６ ０．０２９
ＥｘＣ−８ ０．０２６
ＥｘＣ−９ ０．０６７
Ｃｐｄ−２ ０．０４６
Ｃｐｄ−４ ０．０２５
Ｃｐｄ−７ ０．０３０
ＨＢＳ−１ ０．２９０
ゼラチン １．０４６
【０２４１】
第６層（高感度赤感乳剤層）
Ｅｍ−Ａ 銀 ０．７３２
ＥｘＭ−５ ０．１５６
ＥｘＣ−１ ０．０７６
ＥｘＣ−３ ０．０２５
ＥｘＣ−６ ０．０３７
ＥｘＣ−８ ０．１３４
ＥｘＣ−９ ０．１０９
ＥｘＣ−１０ ０．１２７
ＥｘＹ−３ ０．０１２
Ｃｐｄ−２ ０．０９０
Ｃｐｄ−４ ０．０９９
Ｃｐｄ−７ ０．０４０
ＨＢＳ−１ ０．２５４
ＨＢＳ−２ ０．１００
ゼラチン １．００６
【０２４２】
第７層（中間層）
Ｃｐｄ−１ ０．０６８
Ｃｐｄ−６ ０．３０９
固体分散染料ＥｘＦ−４ ０．０２０
ＨＢＳ−１ ０．０６８
ポリエチルアクリレートラテックス ０．０６８
ゼラチン ０．５３９
【０２４３】
第８層（赤感層へ重層効果を与える層）
Ｅｍ−Ｅ 銀 ０．３５８
Ｃｐｄ−４ ０．０３０
ＥｘＭ−２ ０．１０１
ＥｘＭ−３ ０．００８
ＥｘＭ−４ ０．０４０
ＥｘＹ−１ ０．０２８
ＥｘＹ−４ ０．０２８
ＥｘＣ−７ ０．０４６
ＨＢＳ−１ ０．３４３
ＨＢＳ−３ ０．００６
ＨＢＳ−５ ０．０３０
ゼラチン ０．８８４
【０２４４】
第９層（低感度緑感乳剤層）
Ｅｍ−Ｈ 銀 ０．２０６
Ｅｍ−Ｉ 銀 ０．２０８
Ｅｍ−Ｊ 銀 ０．２５５
ＥｘＭ−２ ０．３０４
ＥｘＭ−３ ０．０７５
ＥｘＹ−１ ０．０２８
ＥｘＹ−３ ０．０２４
ＥｘＣ−７ ０．０１４
ＨＢＳ−１ ０．５０５
ＨＢＳ−３ ０．０１２
ＨＢＳ−４ ０．０９５
ＨＢＳ−５ ０．０５５
Ｃｐｄ−５ ０．０１０
Ｃｐｄ−７ ０．０２０
ゼラチン １．２８２
【０２４５】
第１０層（中感度緑感乳剤層）
Ｅｍ−Ｇ 銀 ０．４０９
ＥｘＭ−２ ０．０５６
ＥｘＭ−３ ０．０４３
ＥｘＭ−５ ０．００９
ＥｘＹ−３ ０．０１２
ＥｘＣ−６ ０．００８
ＥｘＣ−７ ０．０１０
ＥｘＣ−８ ０．００９
ＥｘＣ−９ ０．００７
ＨＢＳ−１ ０．０４０
ＨＢＳ−３ ０．００１
ＨＢＳ−４ ０．０３０
ＨＢＳ−５ ０．０１５
Ｃｐｄ−５ ０．００２
Ｃｐｄ−７ ０．００８
ゼラチン ０．４０６
【０２４６】
第１１層（高感度緑感乳剤層）
Ｅｍ−Ｆ 銀 ０．４０７
Ｅｍ−Ｈ 銀 ０．１５６
ＥｘＣ−６ ０．００９
ＥｘＣ−８ ０．０１０
ＥｘＣ−９ ０．０１１
ＥｘＭ−１ ０．０１５
ＥｘＭ−２ ０．０５０
ＥｘＭ−３ ０．０１０
ＥｘＭ−４ ０．０３０
ＥｘＭ−５ ０．０３５
ＥｘＭ−６ ０．０１８
ＥｘＹ−３ ０．００７
Ｃｐｄ−３ ０．００５
Ｃｐｄ−４ ０．００７
Ｃｐｄ−５ ０．０１０
Ｃｐｄ−７ ０．０２０
ＨＢＳ−１ ０．２４８
ＨＢＳ−３ ０．００３
ＨＢＳ−４ ０．０９４
ＨＢＳ−５ ０．０３７
ポリエチルアクリレートラテックス ０．０９９
ゼラチン ０．９５０
【０２４７】
第１２層（イエローフィルター層）
Ｃｐｄ−１ ０．０９０
固体分散染料ＥｘＦ−２ ０．０７０
固体分散染料ＥｘＦ−５ ０．０１０
油溶性染料ＥｘＦ−６ ０．０１０
ＨＢＳ−１ ０．０５５
ゼラチン ０．５８９
【０２４８】
第１３層（低感度青感乳剤層）
Ｅｍ−Ｍ 銀 ０．２８７
Ｅｍ−Ｎ 銀 ０．１９４
Ｅｍ−Ｏ 銀 ０．１２７
ＥｘＣ−１ ０．００８
ＥｘＣ−３ ０．０２３
ＥｘＣ−７ ０．０２４
ＥｘＹ−１ ０．０７８
ＥｘＹ−２ ０．３５４
ＥｘＹ−４ ０．０８６
ＥｘＹ−５ ０．３５４
Ｃｐｄ−２ ０．０８２
Ｃｐｄ−３ ０．０１０
ＨＢＳ−１ ０．３３７
ＨＢＳ−５ ０．０７０
ゼラチン １．４７６
【０２４９】
第１４層（高感度青感乳剤層）
Ｅｍ−Ｌ 銀 ０．４０１
Ｅｍ−Ｋ 銀 ０．４０１
ＥｘＭ−５ ０．００８
ＥｘＣ−１ ０．０１３
ＥｘＹ−１ ０．０６１
ＥｘＹ−２ ０．１３９
ＥｘＹ−３ ０．０１０
ＥｘＹ−４ ０．０８０
ＥｘＹ−５ ０．１３０
Ｃｐｄ−２ ０．０８４
Ｃｐｄ−３ ０．００２
Ｃｐｄ−７ ０．０３９
ＨＢＳ−１ ０．１４２
ゼラチン ０．８０５
【０２５０】
第１５層（第１保護層）
０．０７μｍの沃臭化銀乳剤 銀 ０．２０８
ＵＶ−１ ０．１６７
ＵＶ−２ ０．０６６
ＵＶ−３ ０．０９９
ＵＶ−４ ０．０１３
ＵＶ−５ ０．１６０
Ｆ−１１ ０．００８
ＥｘＦ−３ ０．００３
Ｓ−１ ０．０７７
ＨＢＳ−１ ０．１７５
ＨＢＳ−４ ０．０１７
ゼラチン １．００７
【０２５１】
第１６層（第２保護層）
Ｈ−１ ０．４００
Ｂ−１（直径１．７μｍ） ０．０５０
Ｂ−２（直径１．７μｍ） ０．１５０
Ｂ−３ ０．０２９
Ｓ−１ ０．２００
ゼラチン ０．７０８
【０２５２】
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−１１、Ｂ−４ないしＢ−６、Ｆ−１ないしＦ−１９及び、鉛塩、白金塩、イリジウム塩、ロジウム塩が含有されている。
【０２５３】
有機固体分散染料の分散物の調製
第１２層のＥｘＦ−２を次の方法で分散した。
ＥｘＦ−２のウエットケーキ（１７．６質量％の水を含む）２．８００ｋｇ
オクチルフェニルジエトキシメタンスルホン酸ナトリウム
（３１質量％水溶液） ０．３７６ｋｇ
Ｆ−１５（７％水溶液） ０．０１１ｋｇ
水 ４．０２０ｋｇ
計 ７．２１０ｋｇ
（ＮａＯＨでｐＨ＝７．２に調整）
【０２５４】
上記組成のスラリーをディゾルバーで攪拌して粗分散した後、アジテータミルＬＭＫ−４を用い、周速１０ｍ／ｓ、吐出量０．６ｋｇ／ｍｉｎ、０．３ｍｍ径のジルコニアビーズ充填率８０％で分散液の吸光度比が０．２９になるまで分散し、固体微粒子分散物を得た。染料微粒子の平均粒径は０．２９μｍであった。
【０２５５】
同様にして、ＥｘＦ−４およびＥｘＦ−７の固体分散物を得た。染料微粒子の平均粒径はそれぞれ、０．２８μｍ、０．４９μｍであった。ＥｘＦ−５は欧州特許出願公開第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。
【０２５６】
【表４】

【０２５７】
【表５】

【０２５８】
【表６】

【０２５９】
【表７】

【０２６０】
表６に記載の色素を以下に示す。
【０２６１】
【化３】

【０２６２】
【化４】

【０２６３】
【化５】

【０２６４】
【化６】

【０２６５】
【化７】

【０２６６】
【化８】

【０２６７】
【化９】

【０２６８】
【化１０】

【０２６９】
【化１１】

【０２７０】
【化１２】

【０２７１】
【化１３】

【０２７２】
【化１４】

【０２７３】
【化１５】

【０２７４】
【化１６】

【０２７５】
以下、各層に用いた化合物を示す。
【０２７６】
【化１７】

【０２７７】
【化１８】

【０２７８】
【化１９】

【０２７９】
【化２０】

【０２８０】
【化２１】

【０２８１】
【化２２】

【０２８２】
【化２３】

【０２８３】
【化２４】

【０２８４】
【化２５】

【０２８５】
【化２６】

【０２８６】
【化２７】

【０２８７】
【化２８】

【０２８８】
【化２９】

【０２８９】
【化３０】

【０２９０】
上記のハロゲン化銀カラー写真感光材料を試料２０１とする。
【０２９１】
上記試料２０１より、第４層の乳剤１１を乳剤１２〜１８に変更することにより、試料２０２〜２０８を作成した。
【０２９２】
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。
【０２９３】
処理工程及び処理液組成を以下に示す。

【０２９４】
＊補充量は感光材料３５ｍｍ幅１．１ｍ当たり（２４Ｅｘ．１本相当）
安定液及び定着液は（２）から（１）への向流方式であり、水洗水のオーバーフロー液は全て定着浴（２）へ導入した。尚、現像液の漂白工程への持ち込み量、漂白液の定着工程への持ち込み量、及び定着液の水洗工程への持ち込み量は感光材料３５ｍｍ幅１．１ｍ当たりそれぞれ２．５ｍＬ、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１００ｃｍ^２、漂白液で１２０ｃｍ^２、その他の処理液は約１００ｃｍ^２であった。
【０２９５】
以下に処理液の組成を示す。

【０２９６】

【０２９７】
（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）
【０２９８】

【０２９９】
（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。
【０３００】
（安定液） タンク液、補充液共通 （単位ｇ）
ｐ−トルエンスルフィン酸ナトリウム ０．０３
ポリオキシエチレン−ｐ−モノノニルフェニルエーテル ０．２
（平均重合度１０）
１，２−ベンゾイソチアゾリン−３−オン・ナトリウム ０．１０
エチレンジアミン四酢酸二ナトリウム塩 ０．０５
１，２，４−トリアゾール １．３
１，４−ビス（１，２，４−トリアゾール−１−
イルメチル）ピペラジン ０．７５
水を加えて １．０Ｌ
ｐＨ ８．５
【０３０１】
結果を表８に示す。
【０３０２】
【表８】

【０３０３】
表８から明らかなように、本発明の乳剤を低感度層に用いることにより感度が高く硬調で、かつ保存性が良好な感材を得ることができることが判る。
【０３０４】
（実施例３）
本発明の乳剤について、ホスト平板粒子の最高沃化銀含有率が写真性に与える効果について説明する。
【０３０５】
（乳剤３１の調製）
（ホスト粒子）
ＫＢｒ０．８７ｇ、酸化処理ゼラチン０．９５ｇを含む水溶液１１００ｍＬを３５℃に保ち撹拌した。ＡｇＮＯ_３（２．１ｇ）水溶液とＫＢｒ（１．５ｇ）と酸化処理ゼラチン（１ｇ）を含む水溶液を３０秒間に渡り添加した。ＫＢｒ２．６ｇを含む水溶液を添加した後、６５℃に昇温した。琥珀化ゼラチン４１ｇを含む水溶液を添加した。その後、第１成長としてＡｇＮＯ_３（２２５ｇ）水溶液とＫＢｒ水溶液を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。その後、最外層成長としてＡｇＮＯ_３水溶液（３２．１ｇ）とＫＩを含むＫＢｒ水溶液を１８分間に渡って添加した。ＫＩの濃度は沃化銀含有率が６．０モル％になるように調整した。
【０３０６】
増感色素Ｉ、ＩＩ、ＩＩＩを６９：３０：１のモル比で飽和被覆量の８０％の比率で添加し、その後硝酸カルシウム（２．５×１０^−２ｍｏｌ）を添加した。但し増感色素は、特開平１１−５２５０７号公報に記載の方法で作成した固体分散物として使用した。
【０３０７】
（エピタキシャル形成部）
この後、ＡｇＮＯ_３（６．７ｇ）水溶液とＮａＣｌ（２．４ｇ）を含む水溶液を添加した。その後、ＡｇＮＯ_３（０．３５ｇ）水溶液とＫＩ（０．４５ｇ）水溶液を添加した。更にその後ＡｇＮＯ_３（５．６ｇ）水溶液とＫＢｒ（３．８６ｇ）水溶液を添加した。
【０３０８】
（水洗、後熟部）
続いて、通常の水洗を行った。５０℃にて、ハロゲン化銀１モルに対して、チオシアン酸カリウム（１．８×１０^−４モル）、塩化金酸（１．３×１０^−５モル）、チオ硫酸ナトリウム（２．１×１０^−５モル）およびＮ，Ｎ−ジメチルセレノ尿素（８．８×１０^−６モル）を添加し最適に化学増感を施した。かぶり防止剤（化合物Ｉ）（６．９×１０^−４モル）添加して化学増感を終了した。
【０３０９】
本発明の乳剤は平均円相当径０．８７０μｍ、円相当径の変動係数１７％、平均厚み０．０８７μｍ、平均アスペクト比１０．０の平板粒子であった。また、全粒子の投影面積の７０％以上が円相当径０．６μｍ以上１．１μｍ以下、厚み０．０７μｍ以上０．１２μｍ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５以下である主表面が（１１１）面の六角形平板粒子であり、少なくとも１つの頂点部にエピタキシャル接合を有していた。低温での透過電子顕微鏡観察の結果、全粒子の投影面積の７０％以上の粒子がエピタキシャル部以外の主表面部には転位線を持たず、かつエピタキシャル部に網目状の転位線を有していた。
【０３１０】
（乳剤３２、３３の調製）
乳剤３１の最外層の沃化銀含有率を変更することにより乳剤３２、３３を調製した。粒子形状等は銀電位を調整することにより乳剤３１に合わせた。具体的には、それぞれ最外層形成に用いるＫＩの濃度は沃化銀含有率が９モル％、１８モル％になるように調整した。
【０３１１】
（乳剤３４の調製）
特開２００２−１６９２４１号公報の実施例−２に記載の試料Ｎｏ．３にならって乳剤３４を調製した。平均円相当径０．８３０μｍ、円相当径の変動係数１９％、平均厚み０．０８６μｍ、平均アスペクト比９．７の平板粒子であった。また、全粒子の投影面積の７０％以上が円相当径０．６μｍ以上１．１μｍ以下、厚み０．０７μｍ以上０．１２μｍ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５以下である主表面が（１１１）面の六角形平板粒子であり、少なくとも１つの頂点部にエピタキシャル接合を有していた。低温での透過電子顕微鏡観察の結果、全粒子の投影面積の７０％以上の粒子がエピタキシャル部以外の主表面部には転位線を持たず、かつエピタキシャル部に網目状の転位線を有していた。
【０３１２】
乳剤３１〜３４の特性値を表９にまとめて示した。
【０３１３】
【表９】

【０３１４】
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前述実施例１の表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．３０１〜３０４を作成し、実施例１と同じ実験をおこなった。
【０３１５】
【表１０】

【０３１６】
表１０の結果から明らかなように、本発明の乳剤を用いることにより、高感度でハイライト部の階調が硬調で、かつ保存後の感度変化が小さい感光材料が得られる。ホスト平板粒子の最高沃化銀含有率が１０モル％以下である粒子の割合が高いほど効果が大きい。
【０３１７】
（実施例４）
実施例２の試料２０１より、第４層の乳剤１１を乳剤３１〜３４に置き換えることにより、試料４０１〜４０４を作成し、実施例２と同様の実験を行った。結果を表１１に示す。
【０３１８】
【表１１】

【０３１９】
表１１から明らかなように、本発明の乳剤を低感度層に用いることにより感度が高く硬調でかつ保存性が良好な感材を得ることができることが判る。
【０３２０】
（実施例５）
本発明の乳剤について、平板粒子の厚みが与える効果について説明する。
【０３２１】
（乳剤５２、５３の調製）
乳剤１１の第一成長時の銀電位を変更することにより厚みを変更し乳剤５２、５３を調製した。色素による被覆率は７５％にした。
【０３２２】
乳剤５２は平均円相当径０．６１μｍ、円相当径の変動係数１９％、平均厚み０．０８０μｍ、平均アスペクト比７．６の平板粒子であった。また、全粒子の投影面積の７０％以上が円相当径０．４μｍ以上０．８μｍ以下、厚み０．０７μｍ以上０．１１μｍ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５以下である主表面が（１１１）面の六角形平板粒子であり、少なくとも１つの頂点部にエピタキシャル接合を有していた。低温での透過電子顕微鏡観察の結果、全粒子の投影面積の７０％以上の粒子がエピタキシャル部以外の主表面部には転位線を持たず、かつエピタキシャル部に網目状の転位線を有していた。
【０３２３】
乳剤５３は平均円相当径０．７３μｍ、円相当径の変動係数１９％、平均厚み０．０５５μｍ、平均アスペクト比１３．３の平板粒子であった。また、全粒子の投影面積の７０％以上が円相当径０．５μｍ以上０．９μｍ以下、厚み０．０７μｍ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５以下である主表面が（１１１）面の六角形平板粒子であり、少なくとも１つの頂点部にエピタキシャル接合を有していた。低温での透過電子顕微鏡観察の結果、全粒子の投影面積の７０％以上の粒子がエピタキシャル部以外の主表面部には転位線を持たず、かつエピタキシャル部に網目状の転位線を有していた。
【０３２４】
乳剤１１、５２、５３の特性値を表１２にまとめて示した。
【０３２５】
【表１２】

【０３２６】
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前述実施例１の表２に示すような塗布条件で乳剤１１、５２、５３を塗布し、試料Ｎｏ．１０１、５０２、５０３を作成し、実施例１と同じ実験をおこなった。このとき乳剤層用の塗布液は、塗布直前に４０℃で３０分間攪拌されながら保持されていた。次に、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前述実施例１の表２に示すような塗布条件で乳剤１１、５２、５３を塗布し、試料Ｎｏ．１１１、５１２、５１３を作成し、実施例１と同じ実験をおこなった。但し、このとき乳剤層用の塗布液は、塗布直前に４０℃で１０時間攪拌されながら保持されていた以外は試料Ｎｏ．１０１、５０２、５０３と同じ条件で調製、塗布されている。
【０３２７】
【表１３】

【０３２８】
表１３から明らかなように、本発明の乳剤を用いることにより、ハイライト部の階調が硬調で、かつ保存後の感度変化が小さい感光材料が得られるが、乳剤の厚みが０．０７μｍ以上である粒子が全投影面積に占める割合が小さいほど、乳剤塗布液を塗布前に長時間経時させたときの感度低下が大きく、特にその割合が７０％より小さいとき顕著であることがわかる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a silver halide photographic light-sensitive material and a silver halide photographic emulsion used therefor. More particularly, the present invention relates to a silver halide photographic emulsion and a silver halide photographic light-sensitive material which are highly sensitive, high-contrast and excellent in storage stability.
[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 for these tabular grains, a sensitization method using an epitaxial junction is disclosed (for example, see Patent Documents 1 and 2). Among them, as a technique for simultaneously satisfying the sensitivity and storage stability of the epitaxially sensitized tabular grains, a technique focusing on the number of epitaxial junctions existing at the apex of the tabular grains and the number of dislocation lines existing in the epitaxial portion is disclosed (for example, And Patent Document 3). Further, as a technique for simultaneously satisfying the sensitivity and gradation of the epitaxially sensitized tabular grains, the number of epitaxial junctions existing at the vertices of the tabular grains and the host tabular grains having an annular band having a silver iodide content of 4 mol% or more. A focused technique is disclosed (for example, see Patent Document 4).
[0003]
[Patent Document 1]
JP 58-108526 A
[Patent Document 2]
JP 59-133540 A
[Patent Document 3]
JP 2002-169241 A
[Patent Document 4]
JP 2002-169238 A
[0004]
[Problems to be solved by the invention]
In the above-described conventional techniques, the sensitivity and storability are not sufficient, and it has been clarified by the present inventors that it is difficult to satisfy the sensitivity, storability, and gradation simultaneously with these techniques. .
[0005]
The epitaxial sensitization method using silver chloride as a main constituent element is basically unstable in a photographic light-sensitive 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. Therefore, a photosensitive material using an epitaxial emulsion causes a problem that sensitivity is lowered or fog is increased during storage. On the other hand, reducing the silver chloride content can solve the problem at the time of storage, but at the same time causes a problem that the sensitivity is lowered. There was no clear design guideline for an epitaxial emulsion that satisfies both excellent storage stability and high sensitivity at the same time. In addition, the epitaxial sensitization method has a high sensitivity in a shadow portion with a small exposure amount, but has a defect that a gradation in a highlight portion with a large exposure amount becomes soft.
[0006]
The present invention seeks to provide means that can simultaneously satisfy the high sensitivity, high contrast, and storage stability of tabular grains. That is, an object of the present invention is to provide a silver halide photographic emulsion and a photographic light-sensitive material having high sensitivity, high contrast and good storage stability.
[0007]
[Means for Solving the Problems]
The present inventor has found that the above-mentioned problems can be solved by setting the structure and composition of tabular grains serving as a base for performing epitaxial bonding and the preparation conditions at the time of epitaxial bonding to an unprecedented structure, composition and conditions.
[0008]
(1) In a silver halide emulsion containing a dispersion medium and silver halide grains, 70% or more of the total projected area of the silver halide grains is the following (i), (ii), (iii) and (iv) A silver halide photographic emulsion characterized by being occupied by epitaxial tabular grains satisfying the above requirements.
(I) Silver iodochlorobromide epitaxial tabular grains having a (111) plane as the main surface
(Ii) having an epitaxial portion at at least one vertex of the host tabular grain
(Iii) In the epitaxial portion, the ratio (Br / Cl) of the average silver chloride content (Cl mol%) to the average silver bromide content (Br mol%) is in the range of 0.6 to 1.4. is there.
(Iv) The volume of the epitaxial part is Vepi, and the volume of the host tabular grain is Vhost.
Vepi^1/3= 0.34 Vhost^1/3+ D
When d is expressed as 0.3d₀Or 1.7d₀It is in the range. Where d₀= 0.03.
[0009]
(2) In a silver halide emulsion containing a dispersion medium and silver halide grains, 70% or more of the total projected area of the silver halide grains is further occupied by silver halide grains satisfying the requirement (v) below The silver halide photographic emulsion as described in (1) above, wherein
(V) The maximum silver iodide content of the host tabular grains is 10 mol% or less.
[0010]
(3) In a silver halide emulsion containing a dispersion medium and silver halide grains, 70% or more of the total projected area of the silver halide grains is occupied by silver halide grains satisfying the following (vi) requirement The silver halide photographic emulsion as described in (1) or (2) above.
(Vi) The thickness of the tabular grain is 0.07 μm or more.
[0011]
(4) A silver halide photographic light-sensitive material comprising the silver halide photographic emulsion described in any one of (1) to (3) above.
[0012]
DETAILED DESCRIPTION OF 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.
[0013]
The tabular grains have a triangular shape, a hexagonal shape, or a circular shape in which they are round when the grains are viewed from a direction perpendicular to the main surface, and have outer surfaces parallel to each other.
[0014]
In the silver halide photographic emulsion of the present invention, 70% or more of the projected area of all grains is composed of host tabular grains and an epitaxial portion, and an epitaxial satisfying the requirements (i), (ii), (iii) and (iv). One of the characteristics is that it is occupied by tabular grains. More preferably, in the silver halide photographic emulsion of the present invention, 80% or more of the projected area of all grains is occupied by epitaxial tabular grains satisfying the above requirements.
[0015]
The host tabular grains constituting the epitaxial tabular grains of the present invention have a 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 the grains is 2 to 1 is preferably a hexagonal tabular grain. More preferably, it is a hexagonal tabular grain having a 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 the grains is 2 to 1. . More preferably, it is a tabular grain 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 the grains is 1.5 to 1. When the shape of the main surface of the tabular grain is a rounded triangle or hexagon, the length of the side of the main surface is the length of the hypothetical triangle or hexagon formed by extending each side. To do. When tabular grains other than the hexagonal shape described above are mixed, it is difficult to prepare the silver halide photographic emulsion of the present invention, and it is difficult to solve the problems of gradation and storage stability.
[0016]
The emulsion of the present invention is preferably monodisperse. The variation coefficient of the equivalent circle diameter of all silver halide grains used in the present invention is preferably 30% or less, particularly preferably 25% or less, and further 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. When the monodispersity is deteriorated, the epitaxial formation becomes nonuniform between grains, and it becomes difficult to prepare the silver halide photographic emulsion of the present invention.
[0017]
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 circle diameter). The thickness (th) cannot be calculated simply from the length of the shadow of the replica because of the epitaxial portion. However, it can be calculated by measuring the shadow length of the replica of the host tabular grain before epitaxial formation. Alternatively, even after the epitaxial formation, the sample coated with tabular grains can be cut and easily taken by taking an electron micrograph of the cross section.
[0018]
The tabular grains used in the present invention preferably have 70% or more of the projected area of all grains having an equivalent circle diameter of 0.2 to 1.5 μm. More preferably, 70% or more of the projected area of all the grains is 0.3 to 1.0 μm in equivalent circle diameter. In the tabular grains used in the present invention, 70% or more of the projected area of all grains is preferably 0.07 μm or more in thickness. More preferably, 70% or more of the projected area of all the grains is 0.08 μm or more and 0.20 μm or less in thickness.
[0019]
The silver halide composition of the epitaxial tabular grains used in the present invention is silver iodochlorobromide. Basically, the host tabular grains are silver iodobromide or silver iodochlorobromide, and the epitaxial deposition site is silver chloride or silver chlorobromide or silver iodochlorobromide. The silver chloride content of the epitaxial tabular grains is preferably 1 mol% or more and 10 mol% or less, more preferably 2 mol% or more and 6 mol% or less. The silver iodide content is preferably 0.5 mol% or more, more preferably 0.75 mol% or more and 10 mol% or less.
[0020]
In the emulsion of the present invention, the relative standard deviation of the silver iodide content distribution between grains is preferably 20% or less. More preferably, it is 10% or less. The relative standard deviation of the silver iodide content between grains can be easily determined by using the EPMA method (Electron-Probe Micro Analyzer method). In this method, a sample in which emulsion grains are well dispersed so as not to contact each other is prepared and irradiated with an electron beam. Elemental analysis of a very small portion can be performed by X-ray analysis by electron beam excitation. Using this method, the halogen composition of individual grains can be determined by determining the characteristic X-ray intensity of silver and iodine emitted from each grain. If the halogen composition is confirmed by the EPMA method for at least 100 grains, it can be determined whether or not the emulsion is an emulsion according to the present invention. The relative standard deviation of silver iodide content is a value obtained by dividing the standard deviation of the silver iodide content distribution for at least 100 grains by the average silver iodide content and multiplying by 100.
[0021]
The emulsion of the present invention preferably has a relative standard deviation of the silver chloride content distribution between grains of 20% or less. More preferably, it is 10% or less. The measurement method is the same as that described above.
[0022]
The silver halide tabular grains contained in the emulsion of the present invention may preferably have a so-called core / shell structure comprising a core portion having different silver iodide contents and a shell surrounding the core portion. . The shell part may surround the entire core part, may surround only the side surfaces of the tabular grains of the core part, or may surround only the main flat surface part. The number of shells may be one or two or more. When the number of sills is 2 or more, the shell outside the core is called the first shell, the shell outside the first shell is called the second shell, and the shells outside the following are called the third shell and the fourth shell in order. . In this specification, “outermost layer” refers to the outermost shell.
[0023]
The maximum silver iodide content of the host tabular grains of the present invention is characterized by 10 mol% or less. The maximum silver iodide content of the host tabular grains is preferably 8 mol% or less and 3 mol% or more. The position showing the highest silver iodide content is the outermost layer, and this outermost layer is preferably 20% or less with respect to the total silver amount used for grain formation. More preferably, the position showing the highest silver iodide content is the outermost layer, and this outermost layer is 2% or more and 12% or less with respect to the total silver amount used for grain formation. If it deviates from this condition, the epitaxial formation becomes uneven among the grains, and the effect of the present invention is hardly obtained.
[0024]
Examples of the method for measuring the silver iodide content include the following methods. The tabular grain is cut into a ring perpendicular to the main plane and measured by irradiating an electron beam from the cross-sectional direction. That is, the final grain emulsion after grain formation or the grains taken out by centrifugation from the photosensitive material are coated on a triacetyl cellulose support, and the grains are embedded using a resin. An about 40 nm-thick section is cut from this sample with an ultramicrotome and placed on a copper mesh with a support film.
[0025]
A predetermined portion of the grain is subjected to a point analysis with a spot diameter (diameter) reduced to 2 nm or less using an analytical electron microscope to measure the silver iodide content. The silver iodide content can be calculated by treating silver halide grains having a known content as a calibration curve in the same manner and obtaining the ratio of Ag intensity to I intensity in advance. A field emission electron gun with a higher electron density than the one using thermoelectrons is suitable as the analytical electron source for the analytical electron microscope. By narrowing the spot diameter to 1 nm or less, the halogen composition in a minute part can be easily analyzed. it can. In the present invention, silver halide grains are cut into sections every 40 nm by the above method, and each section is scanned at intervals of a spot diameter of 2 nm. The maximum silver iodide content is the maximum value of the silver iodide content when the host part of each slice obtained from one grain is scanned as the scanning range.
[0026]
The silver halide grain of the present invention comprises a host tabular grain and an epitaxial part, and the epitaxial part is present to protrude outward (including the main surface direction and the direction perpendicular to the main surface) from at least one vertex of the host tabular grain. . Here, the vertex portion is a sector formed by one vertex when the tabular grain is viewed from the direction perpendicular to the main surface and formed by this vertex and two sides constituting this vertex. It means the three-dimensional part of the host tabular grain sandwiched between sectors having a radius of 1/3 of the shorter side of the side.
[0027]
Epitaxial tabular grains of the present invention are grains having an epitaxial portion at at least one of the vertex portions, and at most six vertex portions. When the shape of the main surface of the tabular grain is a rounded triangle or hexagon, the vertices and sides of the main surface are the vertices and sides of virtual triangles and hexagons formed by extending each side. And Usually, in addition to the epitaxial tabular grain of the present invention, an epitaxial part is formed on a side other than the main surface or apex part of the tabular grain. Whether or not the requirements for the epitaxial tabular grains of the present invention are satisfied is that 100 or more grains are arbitrarily extracted from an electron micrograph of a tabular grain replica, and grains having an epitaxial portion at one or more apexes are formed. This can be determined by classifying the particles into three classes: particles having an epitaxial portion only on the side other than the side or the main surface other than the apex portion and particles having no epitaxial portion.
[0028]
In the emulsion of the present invention, the ratio (Br / Cl) of the average silver chloride content (mol%) to the average silver bromide content (mol%) in the epitaxial part is at least 70% of the projected area of all grains. It is the characteristic that it exists in the range of thru | or 1.4. More preferably, 80% or more of the projected area of all grains is in the range of Br / Cl of 0.6 to 1.4.
[0029]
The measurement of the halogen composition of the epitaxial portion is examined by the analytical electron microscope. In the present invention, silver halide grains are cut into sections every 40 nm by the above method, and each section is scanned at a spot diameter of 2 nm at intervals of 2 nm, and the three-dimensional silver chloride content distribution and three-dimensional silver bromide in the epitaxial portion are scanned. Obtain the content distribution. The average silver chloride content and the average silver bromide content are obtained by averaging each obtained measurement value in each part. When there are a plurality of slices where an epitaxial portion exists in one particle, the average value of Br / Cl in each epitaxial portion is defined as Br / Cl of the particle.
[0030]
In the emulsion of the present invention, when 70% or more of the projected area of all grains is Vepi as the volume of the epitaxial portion and Vhost as the volume of the host tabular grain
Vepi^1/3= 0.34 Vhost^1/3+ D
And d₀= 0.03, d is 0.3d₀Or 1.7d₀It is the characteristic that it exists in the range. More than 80% of the projected area of all particles has a d value of 0.3d₀Or 1.7d₀It is more preferable that it is in the range. The value of d is 1.7d₀If it seems to exceed, the volume of the epitaxial part is too large relative to the volume of the host tabular grain, and conversion between the host tabular grain and the epitaxial part proceeds and the photographic performance becomes unstable (sensitivity change before and after aging increases). . On the other hand, the value of d is 0.3d₀If it is smaller, the epitaxial portion is too small relative to the host tabular grains, so that a sufficient amount of dislocation lines does not enter and the photographic sensitivity is lowered. The volume Vhost of the host tabular grains is the average equivalent circular diameter Dc of 100 or more epitaxial tabular grains, and the average thickness th of 100 or more tabular grains is π (Dc / 2).²It is the volume of the host tabular grain calculated by fitting to th. When Vepi is the average silver chloride content of the epitaxial tabular grains as Clt and the average silver chloride content of the epitaxial portion is Clepi,
Vepi = {Clt / (Clepi−Clt)} × Vhost
It is defined as Clt is an average value of silver chloride content measured by EPMA method for 100 or more epitaxial tabular grains. Clepi is measured with the analytical electron microscope. The measurement method is the same. When there are a plurality of slices having an epitaxial part per grain, the average silver chloride content of each epitaxial part is taken as the average value.
[0031]
The epitaxial part is silver chloride, silver chlorobromide or silver iodochlorobromide. The silver chloride content in the epitaxial part is preferably 1 mol% or more higher than the host tabular grains. More preferably, the silver chloride content is 10 mol% or more higher than the host tabular grains.
[0032]
In the emulsion of the present invention, it is preferred that 70% or more of the total projected area of silver halide grains is composed of tabular grains having at least one dislocation line in the epitaxial portion. Preferably, 80% or more of the total projected area of the silver halide grains is composed of tabular grains having at least one dislocation line in the epitaxial portion. In the emulsion of the present invention, more preferably, 70% or more of the total projected area of silver halide grains is composed of tabular grains having network-like dislocation lines in the epitaxial part. Most preferably, 80% or more of the total projected area of the silver halide grains is composed of tabular grains having network-like dislocation lines in the epitaxial part. Here, the network-like dislocation line is a dislocation line in which a plurality of dislocation lines that cannot be counted as a number are interlaced like a mesh. In a tabular grain having an epitaxial junction at two or more apex portions, dislocation lines do not necessarily exist in each epitaxial portion. If the epitaxial part bonded to at least one apex part contains one dislocation line, preferably a network-like dislocation line, it corresponds to a tabular grain having at least one dislocation line in the epitaxial part. Preferably, 70% or more of the total projected area of the silver halide grains has an epitaxial portion containing network dislocation lines.
[0033]
In the present invention, it is preferable that 70% or more of the total projected area of the silver halide grains has no dislocation lines other than the epitaxial portion. 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 of silver halide grains has zero dislocation lines. In this case, the epitaxially deposited portion is excluded. Most preferably, 90% or more of the total projected area of the silver halide grains has zero dislocation lines.
[0034]
The dislocation lines of tabular grains are described in, for example, J.A. F. Hamilton, Photo. Sci. Eng. 11, 57, (1967) and T.W. Shiozawa, J. et al. Soc. Photo. Sci. It can be observed by a direct method using a transmission electron microscope at a low temperature described in Japan, 35, 213, (1972). In other words, the silver halide grains taken out carefully so as not to apply a pressure that causes dislocation lines to the grains from the emulsion are placed on a mesh for electron microscope observation to prevent damage (printout, etc.) due to electron beams. Observation is performed by a transmission method in a state where the tube is cooled. At this time, the thicker the particle thickness, the more difficult it is to transmit the electron beam. Therefore, the observation using the high-voltage type electron microscope (acceleration voltage of 200 kV or more for particles having a thickness of 0.25 μm) should be observed more clearly. Can do. From the photograph of the particles obtained by such a method, the position and number of dislocation lines for each particle when viewed from the direction perpendicular to the main surface can be obtained.
[0035]
Hereinafter, the specific method for preparing the above-described epitaxial emulsion of the present invention will be described in detail by dividing it into two, ie, the preparation of the host tabular grains and the preparation of the epitaxial portion.
First, the host tabular grains necessary for preparing the epitaxial emulsion of the present invention will be described in detail. The distribution of silver iodide in the host tabular grains of the present invention is preferably a multiple structure grain having a double structure or more. Here, having a structure with respect to the distribution of silver iodide means that the silver iodide content differs between each structure by 0.5 mol% or more, more preferably by 1 mol% or more.
[0036]
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.
[0037]
The preparation of host tabular grains basically consists of a combination of three steps of nucleation, ripening and growth.
[0038]
In the nucleation step, gelatin having a low methionine content described in US Pat. Nos. 4,713,320 and 4,942,120 is used. US Pat. No. 4,914,014 The nucleation at a high pBr described in (1) and the nucleation in a short time as described in JP-A-2-222940 are 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.
[0039]
In the ripening process, it 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. The tabular grain emulsion of the present invention can be used in the ripening 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 each specification of No. 252,453 in the aging step or the subsequent growth step. In the present invention, the aging step is preferably performed at a temperature of 50 ° C. or higher and 80 ° C. or lower. It is preferable to reduce pBr to 2 or less immediately after nucleation or during aging. Further, additional gelatin is preferably added immediately after nucleation until the end of ripening. Particularly preferred gelatin has 95% or more of amino groups modified to succination or trimellitation.
[0040]
In the growth process of the present invention, 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 are simultaneously added. A method may be used. The fine grains contained in the silver iodide fine grain emulsion may be substantially silver iodide, and may contain silver bromide and / or silver chloride as long as they can form mixed crystals. 100% silver iodide is preferred. Silver iodide can have β-form, γ-form and α-form or α-form-like structure as described in US Pat. No. 4,672,026 in its crystal structure. In the present invention, the crystal structure is not particularly limited, but a mixture of β-form and γ-form, more preferably β-form is used. The silver iodide fine grain emulsion may be formed immediately before the addition described in US Pat. No. 5,004,679, etc., or may be one that has undergone a normal water washing step. The silver iodide fine grain emulsion can be easily formed by the method described in US Pat. No. 4,672,026. A double jet addition method of a silver salt aqueous solution and an iodide salt aqueous solution, in which the pI value at the time of grain formation is kept constant, is preferred. Where pI is the I of the system⁻It is the logarithm of the reciprocal of the ion concentration. The type, concentration, presence / absence of silver halide solvent, type, concentration, etc. of the protective colloid agent such as temperature, pI, pH, gelatin and the like are not particularly limited, but the size of the fine particles is 0.1 μm or less, more preferably 0.8. A thickness of 07 μm or less is convenient for the present invention. The particle shape cannot be completely specified because it is a fine particle, but the variation coefficient of the particle size distribution is preferably 25% or less. In particular, when it is 20% or less, the effect of the present invention is remarkable. Here, the fine grain size and size distribution of the silver iodide fine grain emulsion are obtained by placing the fine grains on a mesh for observation with an electron microscope and directly observing them by a transmission method instead of the carbon replica method. This is because the measurement error becomes large in the observation by the carbon replica method because the particle size is small. The particle size is defined as the diameter of a circle having a projected area equal to the observed particle. The particle size distribution is also obtained by using this equal projected area circle diameter. The most effective fine particles in the present invention have a particle size of 0.06 μm or less and 0.02 μm or more, and a variation coefficient of particle size distribution of 18% or less.
[0041]
After the above-mentioned grain formation, the usual water washing described in US Pat. No. 2,614,929, etc., and the concentration adjustment of protective colloid agents such as pH, pI, gelatin, and the concentration adjustment of silver iodide contained are preferably performed. Is called. The pH is preferably 5 or more and 7 or less. The pI value is preferably set to a pI value at which the solubility of silver iodide is minimized or a pI value higher than that value. As the protective colloid agent, ordinary gelatin having an average molecular weight of about 100,000 is preferably used. Low molecular weight gelatin having an average molecular weight of 20,000 or less is also preferably used. It may be convenient to use a mixture of gelatins having different molecular weights. The amount of gelatin per kg of emulsion is preferably 10 g or more and 100 g or less. More preferably, it is 20 g or more and 80 g or less. The silver amount in terms of silver atom per kg of the emulsion is preferably 10 g or more and 100 g or less. More preferably, it is 20 g or more and 80 g or less. The silver iodide fine grain emulsion is usually dissolved before being added, but it is necessary to sufficiently increase the stirring efficiency of the system at the time of addition. Preferably, the stirring rotation speed is set higher than usual. The addition of an antifoaming agent is effective to prevent the generation of bubbles during stirring. Specifically, antifoaming agents described in Examples of US Pat. No. 5,275,929 are used.
[0042]
A method described in JP-A-2-188874 is preferably used in the growth step of the present invention. A silver bromide, silver iodobromide or silver iodochlorobromide fine grain emulsion prepared immediately before the addition is continuously added during tabular grain growth to dissolve the fine grains to grow tabular grains. An external mixer for preparing a fine grain emulsion has a strong stirring ability, and an aqueous silver nitrate solution, an aqueous halogen solution and gelatin are added to the mixer. Gelatin can be added in advance or immediately before mixing with an aqueous silver nitrate solution and / or an aqueous halogen solution, or an aqueous gelatin solution alone. The gelatin preferably has a molecular weight smaller than that of a normal one, particularly preferably 10,000 to 50,000. Gelatin in which the amino group is modified by 90% or more to phthalation, succination or trimellitization and / or oxidation-treated gelatin with a reduced methionine content is particularly preferably used. By using this method, the preparation of the epitaxial emulsion of the present invention is facilitated.
[0043]
In the present invention, it is preferable that 75% or less of the side surfaces connecting the opposing (111) main surfaces of the host tabular grains are composed of (111) planes.
[0044]
Here, 75% or less of all side surfaces are composed of (111) planes means that there are crystallographic planes other than (111) planes in a ratio higher than 25% of all side surfaces. Usually, the plane can be understood as a (100) plane, but other planes, that is, a (110) plane or a higher index plane can also be included. In the present invention, the effect is remarkable when 70% or less of all side surfaces are constituted by (111) planes.
[0045]
Whether or not 75% or less of all side faces are constituted by (111) faces can be easily 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 75% or less of all side surfaces are composed of (111) faces, in hexagonal tabular grains, the six side faces directly connected to the (111) main surface are all obtuse angles with respect to the (111) main surface. Connect with. By applying shadowing at an angle of 50 ° 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.
[0046]
Furthermore, a method using adsorption of a sensitizing dye is effective as a method for obtaining the ratio between the (111) plane and the (100) plane. The ratio of the (111) plane and the (100) plane can be quantitatively determined using the method described in Journal of Chemical Society of Japan, 1984, Vol. 6, pages 942 to 947. Using the ratio and the equivalent circle diameter and thickness of the tabular grains described above, the ratio of the (111) planes on all sides can be calculated. In this case, the tabular grain is assumed to be a cylinder using the equivalent circle diameter and thickness. With this assumption, the ratio of the side surface to the total surface area can be obtained. A value obtained by multiplying a 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. The ratio of the (100) plane on all the side faces. If the value is subtracted from 100, the ratio of the (111) plane in all side surfaces is obtained. In the present invention, it is more preferable that the ratio of the (111) plane in all side surfaces is 65% or less.
[0047]
In the present invention, a method of making 75% or less of all side surfaces of the host tabular grain emulsion (111) plane will be described. Most generally, the ratio of the (111) face of the side face of the host tabular grain emulsion can be determined by the pBr at the time of preparation of the tabular grain emulsion. Preferably, the addition of 30% or more of the silver amount required for forming the outermost layer is set to pBr so that the ratio of the (111) plane of the side surface decreases, that is, the ratio of the (100) plane of the side surface increases. More preferably, the addition of 50% or more of the silver amount required for forming the outermost layer is set to pBr so that the ratio of the (111) plane of the side surface is reduced.
[0048]
As another method, after the total amount of silver is added, the ratio can be increased by setting pBr so that the ratio of the (100) plane of the side surface is increased and aging.
[0049]
The value of pBr that increases the ratio of the (100) side of the side is a wide range of values depending on the system temperature, pH, type and concentration of protective colloid agent such as gelatin, presence / absence of silver halide solvent, type, and concentration. Can change. Usually, it is preferably pBr 2.0 or more and 5 or less. More preferably, it is pBr2.5 or more and 4.5 or less. However, as described above, the value of pBr can be easily changed by the presence of, for example, a silver halide solvent.
[0050]
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 each specification and publications such as JP-A-54-158917, JP-A-53-82408, JP-A-55-77737, JP-A-55-2982, etc. (B) a thiourea derivative, (c) a silver halide solvent having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom described in JP-A-53-144319, JP-A-54- Examples thereof include (d) imidazoles, (e) sulfite, (f) ammonia, (g) thiocyanate and the like described in Japanese Patent No. 100717.
[0051]
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.^-41 x 10 moles or more^-2It is below the mole.
[0052]
European Patent Application Publication No. 515894A1 and the like can be referred to as a method of changing the face index of the side surface of the tabular grain. Further, polyalkylene oxide compounds described in US Pat. No. 5,252,453 and the like can also be used. As an effective method, the surface index described in each specification such as U.S. Pat. Nos. 4,680,254, 4,680,255, 4,680,256, and 4,684,607. A modifier can be used. Ordinary photographic spectral sensitizing dyes can also be used as modifiers of the same plane index as described above.
[0053]
In the present invention, the host tabular grains preferably have no dislocation lines. Dislocation lines can be eliminated by using a combination of the nucleation, ripening, and growth steps detailed above.
[0054]
The epitaxial formation necessary for the preparation of the emulsion of the present invention will be described in detail. Epitaxial formation 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. Prior to epitaxial formation, high molecular weight gelatin described in JP-A No. 2002-169241 may be used. The outer high molecular weight gelatin is preferably contained in an amount of 10% by mass or more, more preferably 30% or more, still more preferably 50% or more of the total gelatin amount when performing epitaxial bonding. Although it is effective to add this gelatin before coating, the effect is reduced.
[0055]
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 to be used, the epitaxial deposition position can be controlled. The dye is preferably added in an amount of 50% to 95% 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. Any of nuclei usually used for cyanine dyes as basic heterocyclic nuclei can be applied to these dyes. That is, for example, pyrroline nucleus, oxazoline nucleus, thiozoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and Nuclei in which aromatic hydrocarbon rings are fused to these nuclei, that is, for example, indolenine nucleus, benzoindolenine nucleus, indole nucleus, benzoxador nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole Nuclei, benzimidazole nuclei and quinoline nuclei are applicable. These nuclei may have a substituent on the carbon atom.
[0056]
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 Laid-Open Nos. 52-110618, and 52-109925.
[0057]
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.
[0058]
Moreover, you may add the bispyridinium salt of Unexamined-Japanese-Patent No. 2000-250157 simultaneously or separately.
[0059]
During adsorption of the sensitizing dye, the silver iodide content of the outermost surface layer of the host tabular grain may be set higher than the average silver iodide content of the outermost layer. In this case, iodine ions are added prior to the addition of the sensitizing dye. It is preferable to increase the silver iodide content on the surface of the host tabular grains by adding the aforementioned AgI fine grain emulsion. As a result, the distribution of silver iodide content among the grains becomes uniform, and the adsorption of the sensitizing dye becomes uniform. The addition amount of these iodine ions or silver iodide is 1 × 10 5 per mol of silver in the host tabular grains.^-4To 1 × 10^-2The molar range is preferably 1 × 10^-3To 5 × 10^-3A molar range is particularly preferred.
[0060]
The epitaxial part is formed by a solution containing halogen ions and AgNO.₃May be added simultaneously or separately, and may be combined with the addition of silver chloride fine particles, silver bromide fine particles, silver iodide fine particles having a smaller particle diameter than the host tabular grains, or addition of mixed crystal grains thereof. And may be added. As the fine particles, silver chloride fine particles, silver bromide fine particles, silver iodide fine particles, or mixed crystal particles thereof prepared immediately before the addition described in the growth process of the present invention are preferably used. When adding a silver nitrate solution, the addition time is preferably 15 seconds or more and 30 minutes or less, and particularly preferably 30 seconds or more and 20 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 2.5 mol / liter 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.
[0061]
The pBr during the formation of the epitaxial portion is preferably 2.5 or more, and particularly preferably 3.0 or more. The temperature is preferably 35 ° C. or higher and 45 ° C. or lower.
[0062]
The epitaxial tabular grains of the present invention are preferably doped with a 6 cyano metal complex. The site to be doped may be either the host tabular grain, the epitaxial part, or both.
[0063]
Of the 6 cyano metal complexes, those containing iron, ruthenium, osmium, cobalt, rhodium, iridium or chromium are preferred. The amount of the metal complex added is 10 per mole of silver halide (total silver amount including the epitaxial portion and the host portion).^-9Thru 10^-2Preferably in the molar range, 10 per mole of silver halide.^-8Thru 10^-4More 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.
[0064]
As the metal complex, a 6-cyano metal complex represented by the following formula (I) is particularly preferable. By using an emulsion using a 6-cyano metal complex, a highly sensitive photosensitive material can be obtained, and the effect of suppressing the occurrence of fogging can be obtained even when the photosensitive material is stored for a long period of time.
[0065]
(I) [M (CN)₆]^n-
(Wherein M is iron, ruthenium, osmium, cobalt, rhodium, iridium or chromium, and n is 3 or 4).
[0066]
Specific examples of 6-cyano metal complexes are shown below.
(I-1) [Fe (CN)₆]^4-
(I-2) [Fe (CN)₆]^3-
(I-3) [Ru (CN)₆]^4-
(I-4) [Os (CN)₆]^4-
(I-5) [Co (CN)₆]^3-
(I-6) [Rh (CN)₆]^3-
(I-7) [Ir (CN)₆]^3-
(I-8) [Cr (CN)₆]^4-
[0067]
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.
[0068]
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. In the present invention, it is preferable to lower pBr after this. Epitaxial emulsions other than the present invention cause epitaxial breakdown due to the decrease in pBr, resulting in low photographic performance. On the other hand, in the epitaxial emulsion of the present invention, this pBr can be lowered, and a remarkable effect can be exhibited in storage stability and processability. Preferably, pBr at 40 ° C. is lowered to 3.5 or less. More preferably, the emulsion of the present invention has a pBr at 40 ° C. of 3.0 or less, particularly preferably 2.5 or less. The reduction of pBr is basically carried out by adding bromine ions such as KBr and NaBr.
[0069]
After the epitaxial deposition, it is usually washed with water.
The temperature for washing with water can be selected according to the purpose, but is preferably selected within the range of 5 ° C to 50 ° C. Although pH at the time of water washing can also be chosen according to the objective, it is preferred to choose between 2-10. More preferably, it is the range of 3-8. Although pAg at the time of water washing can also be selected according to the objective, it is preferable to select between 5-10. The washing method can be selected from a noodle washing method, a dialysis method using a semipermeable membrane, a centrifugal separation method, a coagulation sedimentation method, 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.
[0070]
The emulsion of the present invention is preferably subjected to chemical sensitization after epitaxial deposition. One chemical sensitization that can be preferably carried out in the present invention is chalcogen sensitization and noble metal sensitization, either alone or in combination, and the Theory of the Photographic Process by TH James. 4th edition, published by McMillan, 1977, (The Theory of the Photographic Process, 4th ed., McMillan, 1977), pages 67 to 76, and can also be carried out using active gelatin. Research Disclosure, 120, April 1974, 12008; Research Disclosure, 34, June 1975, 13452, US Pat. Nos. 2,642,361, 3,297,446, 3 772,031, No. 3,857,711, No. 3 901,714, 4,266,018, and 3,904,415, and British Patent 1,315,755, pAg 4-10, pH 5-5 8 and temperature 30-80 ° C., sulfur, selenium, tellurium, gold, platinum, palladium, iridium or a combination of these sensitizers. In the noble metal sensitization, noble metal salts such as gold, platinum, palladium, iridium and the like can be used, and gold sensitization, palladium sensitization and the combined use of both are particularly preferable. 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 R₂PdX₄It is represented by Here, R represents a hydrogen atom, an alkali metal atom or an ammonium group. X represents a halogen atom and represents a chlorine, bromine or iodine atom.
[0071]
Specifically, K₂PdCl₄, (NH₄)₂PdCl₆, Na₂PdCl₄, (NH₄)₂PdCl₄, Li₂PdCl₄, Na₂PdCl₆Or K₂PdBr₄Is preferred. Gold compounds and palladium compounds are preferably used in combination with thiocyanate or selenocyanate.
[0072]
As sulfur sensitizers, described in hypo, thiourea compounds, rhodanine compounds and U.S. Pat. Nos. 3,857,711, 4,266,018 and 4,054,457. The sulfur-containing compounds that have been used 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 such as azaindene, azapyridazine, and azapyrimidine that are known to suppress fog and increase sensitivity during the process of chemical sensitization. Examples of chemical sensitization aid modifiers are disclosed in U.S. Pat. Nos. 2,131,038, 3,411,914, 3,554,757, and JP-A-58-126526. And the above-mentioned publication and Daphin's "photographic emulsion chemistry", pages 138 to 143.
[0073]
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.^-3~ 1x10^-7Mole, more preferably 1 × 10^-4~ 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.
[0074]
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.^-3~ 1x10^-7Mole, more preferably 1 × 10^-4~ 5x10^-7Is a mole.
[0075]
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.
[0076]
In the 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. Stable tellurium compounds can be used.
[0077]
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.
[0078]
The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fogging during the production process, storage or photographic processing of the light-sensitive material, or stabilizing the photographic performance. That is, thiazoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, amino Triazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines; , Triazaindenes, tetraazaindenes (especially 4-hydroxy substituted (1,3,3a, 7) tetraazaindenes), pentaazaindenes Known as antifoggants or stabilizers, such as, it can be added to many compounds. For example, U.S. Pat. Nos. 3,954,474, 3,982,947, and Japanese Patent Publication No. 52-28660 and those described in the gazette can be used. One of the preferable compounds is a compound described in JP-A-63-212932 and JP-T-29664019.
[0079]
Antifoggants and stabilizers are used before particle formation, during particle formation, after particle formation, water washing step, during dispersion after water washing, during epitaxial formation, before chemical sensitization, during chemical sensitization, after chemical sensitization, before coating. It can be added according to the purpose at various times. In addition to the original antifogging and stabilizing effect added during emulsion preparation, control the crystal wall of grains, reduce grain size, reduce grain solubility, control chemical sensitization, It can be used for various purposes such as controlling the arrangement of dyes.
[0080]
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 or only the shell of the particle can be selected. For example, Mg, Ca, Sr, Ba, Al, Sc, Y, La, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ru, Rh, Pd, Re, Os, Ir, Pt, Au, Cd, Hg, Tl, In, Sn, Pb, and Bi can be used. These metals can be added in the form of a salt that can be dissolved during particle formation, such as ammonium salt, acetate salt, nitrate salt, sulfate salt, phosphate salt, hydrate salt, hexacoordinated complex salt, and tetracoordinated complex salt. For example, CdBr₂, CdCl₂, Cd (NO₃)₂, Pb (NO₃)₂, Pb (CH₃COO)₂, K₃[Fe (CN)₆], (NH₄)₄[Fe (CN)₆], K₂IrCl₆, K₃IrCl₆, (NH₄)₃RhCl₆, K₄Ru (CN)₆Can be given. The ligand of the coordination compound can be selected from halo, aqua, cyano, cyanate, thiocyanate, nitrosyl, thionitrosyl, oxo and carbonyl. These may use only one kind of metal compound, but may be used in combination of two or more kinds.
[0081]
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, AgNO₃) Or an aqueous alkali halide solution (for example, NaCl, KBr, KI) and can be added continuously during the formation of silver halide grains. Further, a solution independent of the water-soluble silver salt and alkali halide may be prepared and added continuously at an appropriate time during grain formation. It is also preferable to combine various addition methods.
[0082]
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.
[0083]
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 silver ripening, and a pH of 8 to 11 called high pH ripening. Any of the methods of growing or aging in the high pH atmosphere can be selected. Two or more methods can be used in combination.
[0084]
The method of adding a reduction sensitizer is a preferable method in that the level of reduction sensitization can be finely adjusted.
[0085]
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.
[0086]
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.
[0087]
It is preferable to use an oxidizing agent for silver during the production process of the emulsion of the present invention. The oxidizing agent for silver refers to a compound having an action of acting on metallic silver and converting it into silver ions. Particularly effective are compounds capable of converting extremely fine silver grains by-produced in the process of forming silver halide grains and chemical sensitization into silver ions. The silver ions generated here may form, for example, a silver salt that is hardly soluble in water such as silver halide, silver sulfide, or silver selenide, or a silver salt that is easily soluble in water such as silver nitrate. May be formed. The oxidizing agent for silver may be an inorganic substance or an organic substance. Examples of the inorganic oxidizing agent include ozone, hydrogen peroxide and adducts thereof (for example, NaBO).₂・ H₂O₂・ 3H₂O, 2NaCO₃・ 3H₂O₂, Na₄P₂O₇・ 2H₂O₂2Na₂SO₄・ H₂O₂・ 2H₂O), peroxyacid salts (eg K₂S₂O₈, K₂C₂O₆, K₂P₂O₈), Peroxy complex compounds (for example, K₂[Ti (O₂) C₂O₄] 3H₂O, 4K₂SO₄・ Ti (O₂) OH / SO₄・ 2H₂O, Na₃[VO (O₂) (C₂H₄)₂] 6H₂O), permanganate (eg KMnO)₄), Chromate (eg, K₂Cr₂O₇) Oxygenates, halogen elements such as iodine and bromine, perhalogenates (eg potassium periodate), high valent metal salts (eg potassium hexacyanoferrate) and thiosulfone There is an acid salt.
[0088]
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).
[0089]
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.
[0090]
The light-sensitive material produced using the silver halide emulsion obtained in the present invention only needs to have at least one light-sensitive layer. Preferably, at least one silver halide emulsion layer of a blue color sensitive layer, a green color sensitive layer, and a red color sensitive layer is provided on the support. It is sufficient that at least one of the layers and the red color-sensitive layer is composed of two or more layers having different sensitivities, and there is no particular limitation on the number of layers and the layer order of the silver halide emulsion layer and the non-photosensitive layer. 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.
[0091]
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.
[0092]
The intermediate layer includes couplers and DIR compounds as described in JP-A Nos. 61-43748, 59-113438, 59-113440, 61-20037, and 61-20038. May be included, and a color mixing inhibitor may be included as normally used.
[0093]
A plurality of silver halide emulsion layers constituting each unit light-sensitive layer is composed of a high-sensitivity emulsion layer, a low-sensitivity emulsion layer, a low-sensitivity emulsion layer, as described in West German Patent 1,121,470 or British Patent 923,045. A two-layer structure of a sensitive emulsion layer can be preferably used. In general, it is preferable that the photosensitivity is gradually decreased toward the support, and a non-photosensitive layer may be provided between the halogen emulsion layers. Further, as described in JP-A-57-112751, 62-200350, 62-206541 and 62-206543, a low-sensitivity emulsion layer is formed on the side away from the support. A high-sensitivity emulsion layer may be provided on the side close to the body.
[0094]
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.
[0095]
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.
[0096]
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. .
[0097]
In addition, as described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is more sensitive than the middle layer. A silver halide emulsion layer having a low degree is arranged, and an arrangement composed of three layers having different sensitivities in which the sensitivities are gradually lowered toward the support. Even in the case of 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.
[0098]
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.
Further, the arrangement may be changed as described above even when there are four or more layers.
[0099]
In order to improve the color reproducibility, U.S. Pat. Nos. 4,663,271, 4,705,744, and 4,707,436, JP-A-62-160448, 63- It is preferable that a multi-layer donor layer (CL) having a spectral sensitivity distribution different from that of the main photosensitive layer such as BL, GL, and RL described in each publication of No. 89850 is disposed adjacent to or close to the main photosensitive layer.
[0100]
A preferred layer using the emulsion of the present invention is a low-sensitivity emulsion layer. As the low-sensitivity emulsion layer, it can be used for any of the red-sensitive low-sensitivity emulsion layer, the green-sensitive low-sensitivity emulsion layer, and the blue-sensitive low-sensitivity emulsion layer. An emulsion layer is preferred. The emulsion of the present invention may be used in the same light sensitive emulsion layer as a silver halide emulsion having no epitaxial junction, but it is preferable not to use it in combination with an emulsion having no epitaxial junction. The emulsion contained in the photosensitive layer other than the photosensitive layer using the emulsion of the present invention may be a silver halide emulsion having no epitaxial junction or a silver halide emulsion having epitaxial.
[0101]
As described above, various layer configurations and arrangements can be selected according to the purpose of each photosensitive material.
[0102]
The light-sensitive material produced using the silver halide emulsion obtained in the present invention preferably uses non-light-sensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a silver halide fine grain which is not exposed during imagewise exposure for obtaining a dye image and is not substantially developed in the developing process, and is preferably not fogged in advance. . The light-insensitive fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may contain silver chloride and / or silver iodide as necessary. Preferably, it contains 0.5 to 10 mol% of silver iodide. The non-photosensitive fine grain silver halide preferably has an average particle size (average value of equivalent circle diameter of projected area) of 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm.
[0103]
The non-photosensitive fine grain silver halide can be prepared by the same method as that for ordinary photosensitive silver halide. The surface of the non-photosensitive fine grain silver halide does not need to be optically sensitized and does not require spectral sensitization. However, prior to adding this to the coating solution, it is preferable to add a known stabilizer such as triazole, azaindene, benzothiazolium, mercapto compound or zinc compound in advance. This fine grain silver halide grain-containing layer can contain colloidal silver.
[0104]
The photographic additives that can be used in the present invention are also described in Research Disclosure (RD), and the relevant locations are shown in the following table.

[0105]
Various dye-forming couplers can be used in the light-sensitive material produced using the silver halide emulsion of the present invention, but the following couplers are particularly preferred.
[0106]
Yellow coupler: coupler represented by the formulas (I) and (II) described in European Patent Application Publication No. 502,424A; Formula (1), (described in European Patent Application Publication No. 513,496A; 2) a coupler (especially Y-28 on page 18); a coupler represented by the formula (I) of claim 1 described in EP 568,037A; US Pat. No. 5,066, A coupler represented by the general formula (I) described in columns 45 to 55 of column 576 of the specification 576; a coupler represented by the general formula (I) described in paragraph 0008 of JP-A-4-274425; Europe A coupler according to claim 1 on page 40 of patent application 498,381A1 (particularly D-35 on page 18); European patent application 447,969A1 Couplers represented by the formula (Y) described on page 4 (especially Y-1 (page 17), Y-54 (page 41)); columns 7 to 36 of US Pat. No. 4,476,219; Couplers represented by formulas (II) to (IV) described in line 58 (particularly II-17, 19 (column 17), II-24 (column 19)).
[0107]
Magenta coupler; JP-A-3-39737 (L-57 (lower right of page 11), L-68 (lower right of page 12), L-77 (lower right of page 13); European Patent No. 456,257 A-4-63 (page 134), A-4-73, -75 (page 139) described; M-4, -6 (page 26), M-7 described in European Patent 486,965 (Page 27); M-45 described in European Patent Application No. 571,959A (page 19); (M-1) described in JP-A-5-204106 (page 6); M-22 described in paragraph 0237 of Japanese Patent No. -362631.
[0108]
Cyan coupler: CX-1,3,4,5,11,12,14,15 (pages 14 to 16) described in JP-A-4-204843; C-7 described in JP-A-4-43345 , 10 (page 35), 34, 35 (page 37), (I-1), (I-17) (pages 42 to 43); general formula (1) of JP-A-6-67385 A coupler represented by Ia) or (Ib).
[0109]
Polymer coupler: P-1, P-5 (page 11) described in JP-A-2-44345.
[0110]
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 96,873B, German Patent 3,234,533. Those described in the respective specifications are preferable.
[0111]
A coupler for correcting unwanted absorption of the coloring dye is yellow represented by the formulas (CI), (CII), (CIII), and (CIV) described on page 5 of European Patent Application Publication No. 456,257A1. Colored cyan coupler (especially YC-86 on page 84), yellow colored magenta coupler ExM-7 (page 202), EX-1 (page 249), EX-7 (page 251) described in the European patent application specification, Magenta colored cyan couplers CC-9 (column 8), CC-13 (column 10) described in US Pat. No. 4,833,069, (2) described in US Pat. No. 4,837,136 ) (Column 8), a colorless masking coupler of the formula (A) according to claim 1 of WO 92/11575 (especially on pages 36 to 45) Exemplary compounds) are preferred.
[0112]
Examples of couplers that release a photographically useful group include the following. Development inhibitor releasing compounds: compounds represented by the formulas (I), (II), (III), (IV) described on page 11 of EP-A-378,236A1 (particularly T-101 (30 Page), T-104 (page 31), T-113 (page 36), T-131 (page 45), T-144 (page 51), T-158 (page 58)), European Patent Application Publication No. 436 , 938A2 specification, the compound represented by the formula (I) described on page 7 (particularly D-49 (page 51)), and the formula (1) described in European Patent Application Publication No. 568,037A. Compounds (especially (23) (page 11)), compounds represented by formulas (I), (II) and (III) described on pages 5 to 6 of European Patent Application Publication No. 440,195A2 (especially 29-page I- (1)); bleach accelerator release compound : Compounds represented by formulas (I) and (I ′) described on page 5 of EP-A-310,125A2 (particularly (60) and (61) on page 61) and JP-A-6-59411 Compound represented by formula (I) according to claim 1 of the publication (especially (7) (page 7)); ligand releasing compound: LIG according to claim 1 of US Pat. No. 4,555,478 A compound represented by -X (especially the compound in columns 21 to 41 of column 12); a leuco dye-releasing compound: compounds 1 to 6 described in columns 3 to 8 of US Pat. No. 4,749,641; fluorescence Dye releasing compound: Compound represented by COUP-DYE described in claim 1 of US Pat. No. 4,774,181 (particularly compounds 1 to 11 in columns 7 to 10); development accelerator or fogging agent releasing compound U.S. Pat. No. 4,656,123, column 3 of the formula (1), (2), (3) (especially (I-22) of column 25) and European Patent Application No. ExZK-2 described on page 75, lines 36 to 38 of specification No. 450,637A2; a compound that releases a group that becomes a dye only after leaving: Description in claim 1 of US Pat. No. 4,857,447 A compound represented by the formula (I): (especially Y-1 to Y-19 in columns 25 to 36).
[0113]
As additives other than couplers, the following are preferable.
Oil-soluble organic compound dispersion medium: P-3, 5, 16, 19, 25, 30, 42, 49, 54, 55, 66, 81, 85, 86, 93 described in JP-A-62-215272 (Pages 140 to 144); Latex for impregnation of oil-soluble organic compound: Latex described in US Pat. No. 4,199,363; Oxidant scavenger developing agent: US Pat. No. 4,978,606 Compounds represented by formula (I) described in columns 2 to 54-62 (particularly I-, (1), (2), (6), (12) (columns 4 to 5), US Pat. , 923,787, column 2, lines 5 to 10 (especially compound 1 (column 3); stain inhibitor: European Patent Application Publication No. 298321A, page 4, lines 30 to 33) Formulas (I) to (II) described in I), in particular I-47,72, III-1,27 (pages 24 to 48); antifading agent: A-6,7,20,21,23 described in EP-A-298321A 24, 25, 26, 30, 37, 40, 42, 48, 63, 90, 92, 94, 164 (pages 69-118), described in columns 25-38 of US Pat. No. 5,122,444. II-1 to III-23, particularly III-10, I-1 to III-4 described on pages 8 to 12 of EP-A-471347A, particularly II-2, US Pat. No. 5,139, A-1 to 48, particularly A-39,42 described in columns 32 to 40 of 931, a material that reduces the amount of color-enhancing agent or anti-color-mixing agent used: of European Patent Application No. 411324A 5-24 pages Described I-1 to II-15, especially I-46; formalin scavenger: SCV-1 to 28, particularly SCV-8, described on pages 24 to 29 of EP-A-477932A; Formulas (VII) to (H) 1, 4, 6, 8, 14 described in JP-A-1-214845, columns 13 to 23 of U.S. Pat. No. 4,618,573, XII) compounds (H-1 to 54), compounds (H-1 to 76) represented by formula (6) described at the lower right of page 8 of JP-A-2-214852, particularly H-14, Compound described in claim 1 of US Pat. No. 3,325,287; Development inhibitor precursor: P-24, 37,39 (pages 6-7) described in JP-A-62-168139; US Patent 5,019 Compound No. 492 of claim 1, especially 28, 29 of column 7; Preservative, antifungal agent: I-1 of columns 3 to 15 of US Pat. No. 4,923,790 III-43, in particular II-1,9,10,18, III-25; Stabilizer, antifoggant: I-1 to (described in columns 6 to 16 of US Pat. No. 4,923,793) 14), especially I-1, 60, (2), (13), compounds 1 to 65 described in columns 25 to 32 of US Pat. No. 4,952,483, especially 36: chemical sensitizer: Triphenylphosphine selenide, compound 50 described in JP-A-5-40324; Dye: a-1 to b-20 described in JP-A-3-156450, pages 15 to 18, particularly a-1,12, 18, 27, 35, 36 b-5, pages 27-29, V-1-23, especially V-1, EP-A 445627A, pages 33-55, F-I-1 to F-II-43. In particular, FI-11, F-II-8, III-1 to 36 described on pages 17 to 28 of EP-A-457153A, particularly III-1,3, international application WO 88/04794. 8 to 26 Dye-1 to 124 microcrystalline dispersion described in the pamphlet of European Patent Application No. 31-22A, particularly compounds 1 to 22 described in European Patent Application Publication No. 319999A, particularly Compound 1, European Patent Application Publication Compounds D-1 to 87 (pages 3 to 28) represented by formulas (1) to (3) described in No. 519306A, and formula (I) described in US Pat. No. 4,268,622 Represented by Compounds 1 to 22 (columns 3 to 10), compounds (1) to (31) (columns 2 to 9) represented by the formula (I) described in US Pat. No. 4,923,788; UV absorber : Compounds (18b) to (18r), 101 to 427 (pages 6 to 9) represented by the formula (1) described in JP-A No. 46-3335, described in European Patent Application No. 520938A Compounds (3) to (66) (pages 10 to 44) represented by formula (I) and compounds HBT-1 to 10 (page 14) represented by formula (III), European Patent Application No. 521823A Compounds (1) to (31) represented by the formula (1) described (Columns 2 to 9).
[0114]
The present invention relates to various color photographic materials such as black and white photographic paper, black and white negative film, X-ray film, color negative film for general use or movie, color reversal film for slide or television, color paper, color positive film and color reversal paper. Can be applied to the material. Moreover, it is suitable for the film unit with a lens described in Japanese Patent Publication Nos. 2-332615 and 3-39784.
[0115]
Suitable supports that can be used in the present invention include, for example, the RD No. described above. 17643, page 28, ibid. No. 18716, page 647, right column to page 648, left column, and 307105, page 879.
[0116]
In the light-sensitive material produced using the silver halide obtained in 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, and more preferably 18 μm. The following is more preferable, and 16 μm or less is particularly preferable. In addition, membrane swelling speed T_1/2Is preferably 30 seconds or shorter, and more preferably 20 seconds or shorter. T_1/2Is defined as the time until the film thickness reaches 1/2 when 90% of the maximum swollen film thickness reached when processed at 30 ° C. for 3 minutes 15 seconds with a color developer is defined as the saturated film thickness. The film thickness means a film thickness measured at room temperature of 25 ° C. and a humidity of 55% relative humidity (2 days)._1/2Is a spherometer of the type described in A. Green et al. Photographic Science and Engineering (Photogr. Sci. Eng.), 19 卷, pages 2,124-129. Can be measured. T_1/2Can be adjusted by adding a hardener to gelatin as a binder or changing the aging conditions after coating. The swelling rate is preferably 150 to 400%. The swelling ratio can be calculated from the maximum swollen film thickness under the conditions described above by the formula: (maximum swollen film thickness-film thickness) / film thickness.
[0117]
The photosensitive material produced using the silver halide obtained in the present invention is provided with a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer. It is preferable. This back layer preferably contains the aforementioned 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%.
[0118]
The light-sensitive material produced using the silver halide obtained in the present invention is the RD. No. 17643, pp. 28-29, ibid. No. 18716, 651, left column to right column; 307105, pages 880-881, and can be developed by a conventional method.
[0119]
Next, the color negative film processing solution used in the present invention will be described.
[0120]
As the color developer used in the present invention, compounds described in JP-A-4-1213939, page 9, upper right column, line 1 to page 11, lower left column, line 4 can be used. In particular, as a color developing agent for rapid processing, 2-methyl-4- [N-ethyl-N- (2-hydroxyethyl) amino] aniline, 2-methyl-4- [N-ethyl-N- (3-Hydroxypropyl) amino] aniline and 2-methyl-4- [N-ethyl-N- (4-hydroxybutyl) amino] aniline are preferred.
[0121]
These color developing agents are preferably used in an amount of 0.01 to 0.08 mol, particularly 0.015 to 0.06 mol per liter of color developer (hereinafter also referred to as “L”). Furthermore, it is preferable to use in the range of 0.02 to 0.05 mol. The color developer replenisher preferably contains 1.1 to 3 times the color developing agent of this concentration, and more preferably 1.3 to 2.5 times.
[0122]
Hydroxylamine can be widely used as a color developer preservative, but if higher preservability is required, it has a substituent such as an alkyl group, a hydroxyalkyl group, a sulfoalkyl group, or a carboxyalkyl group. Hydroxylamine derivatives are preferred, specifically N, N-di (sulfoethyl) hydroxylamine, monomethylhydroxylamine, dimethylhydroxylamine, monoethylhydroxylamine, diethylhydroxylamine, N, N-di (carboxyethyl) hydroxylamine preferable. Among the above, N, N-di (sulfoethyl) hydroxylamine is particularly preferable. These may be used in combination with hydroxylamine, but it is preferable to use one or more in place of hydroxylamine.
[0123]
The preservative is preferably used in the range of 0.02 to 0.2 mol per liter, particularly 0.03 to 0.15 mol, and more preferably in the range of 0.04 to 0.1 mol. preferable. Further, in the replenishing solution, it is preferable to contain a preservative at a concentration of 1.1 to 3 times that of the mother liquor (processing tank solution), as in the case of the color developing agent.
[0124]
In the color developer, sulfite is used as an anti-tarring agent for the oxide of the color developing agent. The sulfite is preferably used in the range of 0.01 to 0.05 mol per liter, particularly preferably in the range of 0.02 to 0.04 mol. In the replenisher, it is preferably used at a concentration of 1.1 to 3 times these.
[0125]
Further, the pH of the color developer is preferably in the range of 9.8 to 11.0, particularly preferably 10.0 to 10.5, and in the replenisher, 0.1 to 1.0 from these values. It is preferable to set a high value within the range. In order to stably maintain such pH, known buffering agents such as carbonate, phosphate, sulfosalicylate, and borate are used.
[0126]
The replenishment amount of color developer is 1m of photosensitive material²80 to 1300 mL per unit is preferable, but from the viewpoint of reducing the environmental pollution load, a smaller amount is preferable, specifically 80 to 600 mL, more preferably 80 to 400 mL.
[0127]
The bromide ion concentration in the color developer is usually 0.01 to 0.06 mol per liter, but it suppresses fogging while maintaining sensitivity, improves discrimination, and improves graininess. In view of the purpose, it is preferable to set the amount to 0.015 to 0.03 mol per liter. When the bromide ion concentration is set in such a range, the replenisher may contain bromide ions calculated by the following formula. However, when C in the following formula becomes negative, it is preferable that the replenisher does not contain bromide ions.
[0128]
C = A-W / V
C: Concentration of bromide ions in the color developer replenisher (mol / L)
A: Bromide ion concentration in target color developer (mol / L)
W: 1m²Amount of bromide ions eluted from the photosensitive material to the color developer when the photosensitive material is color-developed (mol)
V: 1m²Replenishment amount of color development replenisher for light-sensitive materials (L)
[0129]
In addition, when the replenishment amount is reduced or when a high bromide ion concentration is set, as a method for increasing the sensitivity, 1-phenyl-3-pyrazolidone or 1-phenyl-2-methyl-2-hydroxymethyl-3-pyrazolidone is used. It is also preferable to use development accelerators such as thioether compounds typified by pyrazolidones represented by representatives and 3,6-dithia-1,8-octanediol.
[0130]
The compounds and processing conditions described in JP-A-4-125558, page 4, lower left column, line 16 to page 7, lower left column, line 6 can be applied to the processing solution having bleaching ability in the present invention.
[0131]
The bleaching agent preferably has an oxidation-reduction potential of 150 mV or more. Specific examples thereof include those described in JP-A Nos. 5-72694 and 5-173121, particularly 1,3-diaminopropane tetrahydrochloride. Preferred is acetic acid, a ferric complex salt which is the compound of Example 1 described on page 7 of JP-A-5-173712.
[0132]
In order to improve the biodegradability of the bleaching agent, JP-A-4-251845, 4-268552, EP-588,289, 591,934, JP-A-6 It is preferable to use the compound ferric complex described in JP-A-208213 as a bleaching agent. The concentration of these bleaching agents is preferably 0.05 to 0.3 mol per liter of the liquid having bleaching ability, and is designed to be 0.1 to 0.15 mol, particularly for the purpose of reducing discharge to the environment. It is preferable. Moreover, when the liquid which has bleaching ability is a bleaching liquid, it is preferable to contain 0.2-1 mol of bromide per liter, and it is preferable to contain especially 0.3-0.8 mol.
[0133]
The replenisher of the solution having bleaching ability basically contains the concentration of each component calculated by the following formula. Thereby, the concentration in the mother liquor can be kept constant.
[0134]
CR = CT (V1 + V2) / V1 + CP
CR: concentration of the component in the replenisher
CT: Concentration of components in mother liquor (treatment tank liquid)
CP: Concentration of components consumed during processing
V1: 1m²Replenisher volume (mL) of a replenisher with bleaching capacity for light-sensitive materials
V2: 1m²Amount brought in from previous bath by photosensitive material (mL)
[0135]
In addition, it is preferable to include a pH buffer in the bleaching solution, and it is particularly preferable to include a dicarboxylic acid having a low odor such as succinic acid, maleic acid, malonic acid, glutaric acid, and adipic acid. JP-A-53-95630, RD No. It is also preferable to use known bleaching accelerators described in US Pat. No. 17129, US Pat. No. 3,893,858.
1m of photosensitive material is used for bleaching solution.²It is preferable to replenish 50 to 1000 mL of bleaching replenisher, particularly 80 to 500 mL, more preferably 100 to 300 mL. Furthermore, it is preferable to aerate the bleaching solution.
[0136]
For the processing solution having fixing ability, compounds and processing conditions described in JP-A-4-125558, page 7, lower left column, line 10 to page 8, lower right column, line 19 can be applied.
[0137]
In particular, in order to improve the fixing speed and the preservability, a treatment having fixing ability by using the compounds represented by the general formulas (I) and (II) described in JP-A-6-301169 alone or in combination. It is preferable to make it contain in a liquid. In addition, p-toluenesulfinate and the use of sulfinic acid described in JP-A-1-224762 are also preferable in terms of improving the preservability.
[0138]
It is preferable to use ammonium as a cation from the viewpoint of improving the desilvering property in a solution having bleaching ability or a fixing ability, but it is preferable to reduce or eliminate ammonium for the purpose of reducing environmental pollution. .
[0139]
In the bleaching, bleach-fixing, and fixing steps, it is particularly preferable to perform jet stirring described in JP-A-1-309059.
[0140]
The replenishing amount of the replenisher in the bleach-fixing or fixing process is 1 m of photosensitive material.²It is 100-1000 mL per, Preferably it is 150-700 mL, Most preferably, it is 200-600 mL.
[0141]
In the bleach-fixing or fixing step, it is preferable to collect various silver recovery devices in-line or offline to recover silver. By installing in-line, the amount of replenishment can be reduced as a result of processing with reduced silver concentration in the liquid. It is also preferable to recover silver offline and reuse the remaining liquid as a replenisher.
[0142]
The bleach-fixing step and the fixing step can be composed of a plurality of processing tanks, and it is preferable that each tank is cascade-pipe to be a multistage countercurrent system. In general, a two-tank cascade configuration is efficient from the balance with the size of the developing machine, and the ratio of processing times in the preceding tank and the succeeding tank is in the range of 0.5: 1 to 1: 0.5. In particular, the range of 0.8: 1 to 1: 0.8 is preferable.
[0143]
In the bleach-fixing solution and the fixing solution, it is preferable that a free chelating agent that is not a metal complex is present from the viewpoint of improving the preservability, but as these chelating agents, the biodegradability described for the bleaching solution is used. It is preferred to use a chelating agent.
[0144]
Regarding the water washing and stabilization process, the contents described in JP-A-4-12558, page 12, lower right column, line 6 to page 13, lower right column, line 16 can be preferably applied. In particular, azolylmethylamines described in European Patent Nos. 504,609 and 519,190 and N-methylolazoles described in JP-A-4-362943 are used as stabilizers in place of formaldehyde. It is preferable from the viewpoint of maintenance of the working environment to use a surfactant solution that does not contain an image stabilizer such as formaldehyde by using two equivalents of magenta coupler.
[0145]
In order to reduce the adhesion of dust to the magnetic recording layer applied to the photosensitive material, a stabilizer described in JP-A-6-289559 can be preferably used.
[0146]
Washing with water and replenishment amount of stabilizing solution is 1m of photosensitive material²80 to 1000 mL is preferable, and 100 to 500 mL, particularly 150 to 300 mL, is a preferable range from the viewpoints of ensuring washing with water or stabilizing function and reducing waste liquid for environmental conservation. In the treatment carried out at such a replenishment amount, known methods such as thiabendazole, 1,2-benzisothiazolin-3-one, and 5-chloro-2-methylisothiazolin-3-one are used to prevent the growth of bacteria and sputum. It is preferable to use water deionized with an antifungal agent, an antibiotic such as gentamicin, an ion exchange resin or the like. It is more effective to use deionized water together with antibacterial agents and antibiotics.
[0147]
The liquid in the water washing or stabilizing liquid tank is reverse osmosis as described in JP-A-3-46652, JP-A-3-53246, JP-A-3-55542, JP-A-3-121448, and JP-A-3-126030. It is also preferable to reduce the replenishment amount by performing membrane treatment, and the reverse osmosis membrane in this case is preferably a low pressure reverse osmosis membrane.
[0148]
In the processing in the present invention, it is particularly preferable to carry out the evaporation correction of the processing liquid disclosed in JIII Journal of Technical Disclosure No. 94-4992. In particular, a method of correcting using the temperature and humidity information of the developing machine installation environment based on (Formula-1) on the second page is preferable. The water used for evaporation correction is preferably collected from a replenishment tank for washing, in which case deionized water is preferably used as the washing replenishment water.
[0149]
As the treating agent used in the present invention, those described in the third column, right column, line 15 to page 4, left column, line 32 of the above published technical bulletin are preferable. As the developing machine used for this, the film processor described in lines 22 to 28 in the right column on page 3 is preferable.
[0150]
Specific examples of a processing agent, an automatic processor, and an evaporation correction method that are preferable for carrying out the present invention are described from the fifth column, right column, line 11 to the seventh page, right column, last line of the above published technical bulletin. .
[0151]
The treatment agent used in the present invention may be supplied in any form, such as a solution in the concentration or concentrated form of the working solution, or granules, powders, tablets, pastes, and emulsions. As an example of such a treatment agent, JP-A-63-17453 discloses a liquid agent contained in a low oxygen-permeable container, JP-A-4-19655, JP-A-4-230748 discloses vacuum-packed powder. Alternatively, granules, granules containing water-soluble polymers are disclosed in JP-A-4-221951, tablets are disclosed in JP-A-51-61837, JP-A-6-102628, and JP-A-57-5000485 Pasty treatment agents are disclosed, and any of them can be preferably used. However, from the viewpoint of convenience during use, it is preferable to use a liquid prepared in advance at a concentration in use.
[0152]
In the container for storing these treatment agents, polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, nylon and the like are used alone or as a composite material. These are selected according to the required level of oxygen permeability. For an easily oxidized liquid such as a color developer, a low oxygen permeable material is preferable, and specifically, polyethylene terephthalate or a composite material of polyethylene and nylon is preferable. These materials have a thickness of 500-1500 μm and are used for containers and have an oxygen permeability of 20 mL / m.²-It is preferable to be 24 hrs.atm or less.
[0153]
Next, the processing liquid for color reversal film used in the present invention will be described.
Regarding processing for color reversal film, publicly known technology No. 6 (April 1, 1991), page 1 line 5 to page 10, line 5 and page 15, line 8 to page 24, 2 issued by Aztec Co., Ltd. 2 The contents are described in detail in the lines, and any of the contents can be preferably applied.
[0154]
In the processing of the color reversal film, the image stabilizer is contained in the adjustment bath or the final bath. Examples of such image stabilizers include formaldehyde sodium bisulfite and N-methylol azoles in addition to formalin. From the viewpoint of the working environment, sodium formaldehyde bisulfite or N-methylol azoles are preferred, and N-methylol is preferred. As the azole, N-methyloltriazole is particularly preferable. The contents relating to the color developer, bleaching solution, fixing solution, washing water and the like described in the processing of the color negative film can be preferably applied to the processing of the color reversal film.
[0155]
Preferred examples of the color reversal film processing agent containing the above contents include Eastman Kodak E-6 processing agent and Fuji Photo Film Co., Ltd. CR-56 processing agent.
[0156]
Next, the magnetic recording layer preferably used in the present invention will be described.
The magnetic recording layer is obtained by coating a support with an aqueous or organic solvent-based coating liquid in which magnetic particles are dispersed in a binder.
[0157]
The magnetic particles used in the present invention are γFe₂O₃Ferromagnetic iron oxide such as Co-coated γFe₂O₃Co-coated magnetite, Co-containing magnetite, ferromagnetic chromium dioxide, ferromagnetic metal, ferromagnetic alloy, hexagonal Ba ferrite, Sr ferrite, Pb ferrite, Ca ferrite and the like can be used. Co-coated γFe₂O₃Co-coated ferromagnetic iron oxide such as The shape may be any of needle shape, rice grain shape, spherical shape, cubic shape, plate shape and the like. S in specific surface area_BET20m²/ G or more, preferably 30m²/ G or more is particularly preferable. The saturation magnetization (σs) of the ferromagnetic material is preferably 3.0 × 10⁴~ 3.0 × 10⁵A / m, particularly preferably 4.0 × 10⁴~ 2.5 × 10⁵A / m. The ferromagnetic particles may be subjected to a surface treatment with silica and / or alumina or an organic material. Further, the magnetic particles may be treated on the surface with a silane coupling agent or a titanium coupling agent as described in JP-A-6-161032. Also, magnetic particles having a surface coated with inorganic or organic substances as described in JP-A-4-259911 and 5-81652 can be used.
[0158]
The binder used for the magnetic particles is a thermoplastic resin, a thermosetting resin, a radiation curable resin, a reactive resin, an acid, an alkali or a biodegradable polymer, or a natural product polymer described in JP-A-4-219469. (Cellulose derivatives, sugar derivatives, etc.) and mixtures thereof can be used. Tg of said resin is -40 degreeC-300 degreeC, and a mass mean molecular weight is 20,000-1 million. Examples thereof include vinyl copolymers, cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose derivatives such as cellulose acetate butyrate, cellulose tripropionate, acrylic resins, and polyvinyl acetal resins, and gelatin is also preferable. Cellulose di (tri) acetate is particularly preferable. The binder can be cured by adding an epoxy-based, aziridine-based, or isocyanate-based crosslinking agent. Examples of isocyanate-based crosslinking agents include tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and the like, and reaction products of these isocyanates with polyalcohol (for example, tolylene diene). Reaction product of 3 mol of isocyanate and 1 mol of trimethylolpropane), polyisocyanate produced by condensation of these isocyanates, and the like are mentioned, for example, in JP-A-6-59357.
[0159]
The method of dispersing the above-mentioned magnetic material in the binder is preferably a method using a kneader, a pin type mill, an annular type mill, or the like, as described in JP-A-6-35092. Dispersants described in JP-A-5-088283 and other known dispersants can be used. The thickness of the magnetic recording layer is 0.1 μm to 10 μm, preferably 0.2 μm to 5 μm, more preferably 0.3 μm to 3 μm. The mass ratio of the magnetic particles and the binder is preferably 0.5: 100 to 60: 100, more preferably 1: 100 to 30: 100. The coating amount of magnetic particles is 0.005 to 3 g / m², Preferably 0.01-2 g / m²More preferably, 0.02 to 0.5 g / m²It is. The transmission yellow density of the magnetic recording layer is preferably 0.01 to 0.50, more preferably 0.03 to 0.20, and particularly preferably 0.04 to 0.15. The magnetic recording layer can be provided on the entire surface or in a stripe shape on the back surface of the photographic support by coating or printing. As a method for applying the magnetic recording layer, an air doctor, blade, air knife, squeeze, impregnation, reverse roll, transfer roll, gravure, kiss, cast, spray, dip, bar, extrusion, etc. can be used. The coating solution described in Japanese Patent No. 341436 is preferable.
[0160]
The magnetic recording layer may have functions such as lubricity improvement, curl adjustment, antistatic, adhesion prevention, head polishing, etc., or another functional layer may be provided to give these functions. A non-spherical inorganic particle abrasive in which at least one of the particles has a Mohs hardness of 5 or more is preferred. As the composition of the non-spherical inorganic particles, oxides such as aluminum oxide, chromium oxide, silicon dioxide, titanium dioxide, and silicon carbide, carbides such as silicon carbide and titanium carbide, and fine powders such as diamond are preferable. The surface of these abrasives may be treated with a silane coupling agent or a titanium coupling agent. These particles may be added to the magnetic recording layer, or may be overcoated (for example, a protective layer, a lubricant layer, etc.) on the magnetic recording layer. As the binder used at this time, the above-mentioned binders can be used, and the same binder as that for the magnetic recording layer is preferable. The light-sensitive material having a magnetic recording layer is disclosed in US Pat. Nos. 5,336,589, 5,250,404, 5,229,259, 5,215,874, and European Patent 466,130. It is described in each specification.
[0161]
Next, the polyester support used in the present invention will be described. For details including the photosensitive material, processing, cartridge, and examples described later, the published technical report, public technical number 94-6023 (Invention Association; 19944.3. 15.). The polyester used in the present invention is formed with diol and aromatic dicarboxylic acid as essential components, and 2,6-, 1,5-, 1,4- and 2,7-naphthalenedicarboxylic acid, terephthalic as aromatic dicarboxylic acid Examples of the acid, isophthalic acid, phthalic acid, and diol include diethylene glycol, triethylene glycol, cyclohexanedimethanol, bisphenol A, and bisphenol. Examples of this polymer include homopolymers such as polyethylene terephthalate, polyethylene naphthalate, and polycyclohexanedimethanol terephthalate. Particularly preferred is a polyester containing 50 mol% to 100 mol% of 2,6-naphthalenedicarboxylic acid. Of these, polyethylene 2,6-naphthalate is particularly preferred. The average molecular weight range is about 5,000 to 200,000. The Tg of the polyester of the present invention is 50 ° C. or higher, more preferably 90 ° C. or higher.
[0162]
Next, the polyester support is subjected to heat treatment at a heat treatment temperature of 40 ° C. or higher and lower than Tg, more preferably (Tg-20) ° C. or higher and lower than Tg in order to make it difficult to cause curl. The heat treatment may be performed at a constant temperature within this temperature range, or may be performed while cooling. This heat treatment time is 0.1 hours to 1500 hours, more preferably 0.5 hours to 200 hours. The heat treatment of the support may be performed in a roll shape or may be performed while being conveyed in a web shape. Provide unevenness on the surface (for example, SnO₂And Sb₂O₅The surface shape may be improved). It is also desirable to devise measures such as preventing knurling of the core part by imparting knurls to the end part and slightly raising only the end part. These heat treatments may be carried out at any stage after forming the support, after the surface treatment, after applying the back layer (antistatic agent, slip agent, etc.) and after applying the undercoat. Preferred is after application of the antistatic agent.
[0163]
This polyester may be kneaded with an ultraviolet absorber. In order to prevent light piping, the purpose can be achieved by kneading dyes or pigments that are commercially available for polyesters such as Mitsubishi Kasei's Diaresin and Nippon Kayaku's Kayset.
[0164]
Next, in the present invention, it is preferable to perform a surface treatment in order to adhere the support and the light-sensitive material constituting layer. Examples of the surface activation treatment include chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, and ozone oxidation treatment. Among the surface treatments, ultraviolet irradiation treatment, flame treatment, corona treatment, and glow treatment are preferable.
[0165]
Next, regarding the undercoating method, a single layer or two or more layers may be used. As a binder for the undercoat layer, starting from a copolymer starting from a monomer selected from vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid, maleic anhydride, etc. Examples include polyethyleneimine, epoxy resin, grafted gelatin, nitrocellulose, and gelatin. Examples of compounds that swell the support include resorcin and p-chlorophenol. As the gelatin hardener for the undercoat layer, chromium salts (such as chromium alum), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, active halogen compounds (2,4-dichloro-6-hydroxy-S-triazine) Etc.), epichlorohydrin resins, active vinyl sulfone compounds and the like. SiO₂TiO₂In addition, inorganic fine particles or polymethyl methacrylate copolymer fine particles (0.01 to 10 μm) may be contained as a matting agent.
[0166]
In the present invention, an antistatic agent is preferably used. Examples of these antistatic agents include carboxylic acids, carboxylates, polymers containing sulfonates, cationic polymers, and ionic surfactant compounds.
[0167]
The most preferable antistatic agents are ZnO and TiO.₂, SnO₂, Al₂O₃, In₂O₃, SiO₂, MgO, BaO, MoO₃, V₂O₅At least one volume resistivity selected from among 10⁷Ω · cm or less, more preferably 10⁵Particle size of Ω · cm or less 0.001-1.0 μm Crystalline metal oxide or composite oxide of these (Sb, P, B, In, S, Si, C, etc.), and sol These metal oxides or fine particles of these composite oxides. The content of the photosensitive material is 5 to 500 mg / m.²Is particularly preferred, 10 to 350 mg / m²It is. The ratio of the amount of the conductive crystalline oxide or its composite oxide to the binder is preferably 1/300 to 100/1, more preferably 1/100 to 100/5.
[0168]
The light-sensitive material of the present invention preferably has slipperiness. The slip agent-containing layer is preferably used for both the photosensitive layer surface and the back surface. A preferable slip property is 0.25 or less and 0.01 or more in terms of dynamic friction coefficient. The measurement at this time represents a value when the stainless steel sphere having a diameter of 5 mm is conveyed at 60 cm / min (25 ° C., 60% RH). In this evaluation, even if the counterpart material is replaced with the photosensitive layer surface, the value is almost the same.
[0169]
Examples of slip agents that can be used in the present invention include polyorganosiloxanes, higher fatty acid amides, higher fatty acid metal salts, esters of higher fatty acids and higher alcohols, and examples of polyorganosiloxanes include polydimethylsiloxane, polydiethylsiloxane, Styrylmethylsiloxane, polymethylphenylsiloxane, and the like can be used. As the additive layer, the outermost layer of the emulsion layer or the back layer is preferable. In particular, polydimethylsiloxane and esters having a long chain alkyl group are preferred.
[0170]
The light-sensitive material of the present invention preferably contains a matting agent. The matting agent may be either the emulsion surface or the back surface, but is particularly preferably added to the outermost layer on the emulsion side. The matting agent may be soluble in the processing solution or insoluble in the processing solution, and is preferably a combination of both. For example, polymethyl methacrylate, poly (methyl methacrylate / methacrylic acid = 9/1 or 5/5 (molar ratio)), polystyrene particles and the like are preferable. The particle size is preferably 0.8 to 10 μm, the particle size distribution is preferably narrow, and 90% or more of the total number of particles is preferably contained between 0.9 and 1.1 times the average particle size. . It is also preferable to add fine particles of 0.8 μm or less at the same time in order to improve matting properties, for example, polymethyl methacrylate (0.2 μm), poly (methyl methacrylate / methacrylic acid = 9/1 (molar ratio), 0.3 μm) ), Polystyrene particles (0.25 μm), and colloidal silica (0.03 μm).
[0171]
Next, the film cartridge used in the present invention will be described. The main material of the cartridge used in the present invention may be metal or synthetic plastic.
[0172]
Preferred plastic materials are polystyrene, polyethylene, polypropylene, polyphenyl ether and the like. Furthermore, the cartridge of the present invention may contain various antistatic agents, and carbon black, metal oxide particles, nonions, anions, cations and betaine surfactants or polymers can be preferably used. These antistatic cartridges are described in JP-A Nos. 1-312537 and 1-312538. Especially, the resistance at 25 ° C. and 25% RH is 10¹²Ω or less is preferable. Usually, plastic patrone is manufactured using a plastic kneaded with carbon black or pigment to provide light shielding. The size of the cartridge may be the current 135 size, and it is also effective to reduce the diameter of a 25 mm cartridge in the current 135 size to 22 mm or less in order to reduce the size of the camera. The volume of the patrone case is 30 cm.³Less preferably 25cm³The following is preferable. The mass of the plastic used for the cartridge and the cartridge case is preferably 5 to 15 g.
[0173]
Further, a patrone for rotating the spool and feeding the film may be used in the present invention. Alternatively, the film tip may be housed in the cartridge main body, and the film tip may be sent out from the port portion of the cartridge by rotating the spool shaft in the film feed direction. These are disclosed in US Pat. Nos. 4,834,306 and 5,226,613. The photographic film used in the present invention may be a so-called raw film before development or a developed photographic film. Further, the raw film and the developed photographic film may be stored in the same new cartridge, or may be different.
[0174]
The color photographic light-sensitive material of the present invention is also suitable as a negative film for an advanced photo system (hereinafter referred to as AP system), manufactured by Fuji Photo Film Co., Ltd. (hereinafter referred to as Fuji Film), NEXIA A, NEXIA F, The film is processed into an AP system format such as NEXIA H (in order ISO 200/100/400) and stored in a dedicated cartridge. These AP system cartridge films are used by being loaded into an AP system camera such as the Epion series (Epion 300Z, etc.) manufactured by Fuji Film. The color photographic light-sensitive material of the present invention is also suitable for a film with a lens such as a super slim which is a Fuji color copying run made by Fuji Film.
[0175]
The film photographed by these is printed through the following process in the minilab system.
(1) Reception (carrying out the exposed cartridge film from the customer)
(2) Detach process (transfer film from cartridge to intermediate cartridge for development process)
(3) Film development
(4) Rear touch process (return developed negative film back to original cartridge)
(5) Print (C / H / P3 type prints and index prints are continuously automatically printed on color paper [preferably SUPER FA8 manufactured by Fuji Film])
(6) Verification / shipment (Cartridge and index print are verified by ID number and shipped together with the print)
[0176]
As these systems, FUJIFILM Minilab Champion Super FA-298 / FA-278 / FA-258 / FA-238 and FUJIFILM Digital Lab System Frontier are preferred. Minilab Champion film processors include FP922AL / FP562B / FP562B, AL / FP362B / FP362B, AL, and the recommended processing chemicals are Fujicolor Justit CN-16L and CN-16Q. Examples of the printer processor include PP3008AR / PP3008A / PP1828AR / PP1828A / PP1258AR / PP1258A / PP728AR / PP728A, and recommended processing chemicals are Fujicolor Justit CP-47L and CP-40FAII. In the frontier system, a scanner & image processor SP-1000 and a laser printer & paper processor LP-1000P or a laser printer LP-1000W are used. The detacher used in the detaching step and the rear toucher used in the rear touching step are preferably DT200 / DT100 and AT200 / AT100 of Fuji Film, respectively.
[0177]
The AP system can also be enjoyed by a photo joy system centered on Fujifilm's digital image workstation Aladdin 1000. For example, it can be obtained by directly loading developed AP system cartridge film into Aladdin 1000 or inputting image information of negative film, positive film, and print using 35mm film scanner FE-550 or flat head scanner PE-550. Digital image data can be easily processed and edited. The data can be output as a print by a digital color printer NC-550AL using a light fixing type thermal color printing system, a photography 3000 using a laser exposure thermal development transfer system, or by an existing laboratory equipment through a film recorder. Aladdin 1000 can also output digital information directly to a floppy (registered trademark) disk or Zip disk, or to a CD-R via a CD writer.
[0178]
On the other hand, at home, you can enjoy photos on TV just by loading the developed AP system cartridge film into the Fujifilm photo player AP-1, and if you load it into the Fujifilm photo scanner AS-1, Image information can also be captured continuously at high speed. Also, Fujifilm Photo Vision FV-10 / FV-5 can be used to input a film, print, or three-dimensional object into a personal computer. Furthermore, image information recorded on a floppy (registered trademark) disk, Zip disk, CD-R, or hard disk can be variously processed and enjoyed on a personal computer using Fujifilm's application software photo factory. In order to output a high-quality print from a personal computer, a digital color printer NC-2 / NC-2D manufactured by Fuji Film using a light fixing type thermal color printing method is suitable.
[0179]
To store the developed AP system cartridge film, Fuji Color Pocket Album AP-5 Pop L, AP-1 Pop L, AP-1 Pop KG or Cartridge File 16 is preferred.
[0180]
Photosensitive materials produced using the silver halide emulsion obtained in the present invention are disclosed in U.S. Pat. No. 4,500,626, JP-A-60-133449, 59-218443, and 61-238056. The present invention can also be applied to the photothermographic materials described in specifications and publications such as European Patent Application Publication No. 210,660A2.
[0181]
In addition, the light-sensitive material produced using the silver halide emulsion obtained in the present invention is applied to a lens-fitted film unit described in Japanese Patent Publication No. 2-332615 and Japanese Utility Model Publication No. 3-39784. In addition, the effect is more effective and effective.
[0182]
【Example】
The present invention will be specifically described below with reference to examples. However, the present invention is not limited to these examples.
[0183]
(Example-1)
The emulsion of the present invention will be described.
(Preparation of emulsion 11)
(Host particles)
1300 mL of an aqueous solution containing 1.0 g of KBr and 1.0 g of oxidized gelatin was kept at 35 ° C. and stirred. AgNO₃(2.0 g) An aqueous solution containing KBr (1.5 g) and oxidized gelatin (0.9 g) was added over 20 seconds. After adding an aqueous solution containing 2.7 g of KBr, the temperature was raised to 55 ° C. An aqueous solution containing 26 g of gelatin was added. Then, AgNO as the first growth₃(135 g) An aqueous solution and an aqueous KBr solution were added. At this time, the silver potential was kept at -15 mV with respect to the saturated calomel electrode. After that, AgNO as the outermost layer growth₃An aqueous solution (33.5 g) and an aqueous KBr solution containing KI were added over 18 minutes. The concentration of KI was adjusted so that the silver iodide content was 4.0 mol%.
[0184]
After the temperature was lowered to 35 ° C., sensitizing dyes I, II and III were added at a molar ratio of 60: 39: 1 and a ratio of 75% of the saturated coverage. However, the sensitizing dye was used as a solid dispersion prepared by the method described in JP-A-11-52507.
[0185]
(Epitaxial formation part)
After this, AgNO₃An aqueous solution containing (8.5 g) aqueous solution and NaCl (3.0 g) was added. Then AgNO₃(0.45 g) aqueous solution and KI (0.49 g) aqueous solution were added. Then AgNO₃(7.1 g) Aqueous solution and KBr (4.9 g) aqueous solution were added.
[0186]
(Washing, post-ripening part)
Subsequently, ordinary water washing was performed. At 54 ° C., potassium thiocyanate (1.0 × 10 10 per mol of silver halide)^-4Mol), chloroauric acid (1.5 × 10^-5Mol), sodium thiosulfate (4.0 × 10^-5Mol) and N, N-dimethylselenourea (2.5 × 10^-6Mol) was added for optimum chemical sensitization. Antifoggant (Compound I) (9.5 × 10^-4Mol) was added to complete the chemical sensitization.
[0187]
The obtained emulsion contained tabular grains having an average equivalent circle diameter of 0.53 μm, a variation coefficient of equivalent circle diameter of 17%, an average thickness of 0.105 μm, and an average aspect ratio of 5.0. Further, the maximum length with respect to the length of the side having the minimum length, in which 70% or more of the projected area of all the grains has a circle-equivalent diameter of 0.4 μm to 0.7 μm and a thickness of 0.07 μm to 0.14 μm. The main surface having a side length ratio of 5 or less was a (111) -plane hexagonal tabular grain, and had an epitaxial portion at least at one apex. As a result of observation with a transmission electron microscope at a low temperature, 70% or more of the projected area of all the particles has no dislocation lines on the main surface other than the epitaxial part, and has a network-like dislocation line in the epitaxial part. It was.
[0188]
[Chemical 1]

[0189]
(Preparation of emulsion 12)
Emulsion 12 was prepared from emulsion 11 by changing the epitaxial formation portion as follows.
AgNO₃An aqueous solution containing (8.5 g) aqueous solution and NaCl (3.0 g) was added. Then AgNO₃(7.55 g) An aqueous solution containing KI (0.49 g) and KBr (4.9 g) was added.
[0190]
(Preparation of emulsion 13)
Emulsion 13 was prepared from emulsion 11 by changing the epitaxial formation portion as follows.
AgNO₃An aqueous solution containing (14.3 g) aqueous solution and NaCl (5.04 g) was added. Then AgNO₃(0.76 g) aqueous solution and KI (0.82 g) aqueous solution were added. Then AgNO₃(11.9 g) aqueous solution and KBr (8.23 g) aqueous solution were added.
[0191]
(Preparation of emulsion 14)
Emulsion 14 was prepared from emulsion 11 by changing the epitaxial formation portion as follows.
AgNO₃An aqueous solution containing (4.25 g) aqueous solution and NaCl (1.5 g) was added. Then AgNO₃(0.23 g) aqueous solution and KI (0.25 g) aqueous solution were added. Then AgNO₃(3.6 g) Aqueous solution and KBr (2.5 g) aqueous solution were added.
[0192]
(Preparation of emulsion 15)
Emulsion 15 was prepared from emulsion 11 by changing the epitaxial formation portion as follows.
AgNO₃(6.2 g) An aqueous solution containing NaCl (2.2 g) was added. Then AgNO₃(0.45 g) aqueous solution and KI (0.49 g) aqueous solution were added. Then AgNO₃(9.4 g) Aqueous solution and KBr (6.5 g) aqueous solution were added.
[0193]
(Preparation of emulsion 16)
Emulsion 16 was prepared from emulsion 11 by changing the epitaxial formation portion as follows.
AgNO₃An aqueous solution containing (12.5 g) aqueous solution and NaCl (4.4 g) was added. Then AgNO₃(0.45 g) aqueous solution and KI (0.49 g) aqueous solution were added. Then AgNO₃(3.1 g) Aqueous solution and KBr (2.1 g) aqueous solution were added.
[0194]
(Preparation of emulsion 17)
Emulsion 17 was prepared from emulsion 11 by changing the epitaxial formation portion as follows.
AgNO₃(10.5 g) An aqueous solution and an aqueous solution containing NaCl (3.7 g) were added. Then AgNO₃(0.76 g) aqueous solution and KI (0.82 g) aqueous solution were added. Then AgNO₃(15.7 g) Aqueous solution and KBr (10.9 g) aqueous solution were added.
[0195]
(Preparation of emulsion 18)
Emulsion 18 was prepared following Emulsion i described in Example 2 of JP-A No. 2002-169238. The obtained emulsion contained tabular grains having an average equivalent-circle diameter of 0.66 μm, a variation coefficient of equivalent-circle diameter of 20%, an average thickness of 0.07 μm, and an average aspect ratio of 9. In addition, 70% or more of the projected area of all the particles is equivalent to a circle having an equivalent diameter of 0.5 μm or more and 0.8 μm or less, and a thickness of 0.05 μm or more and 0.09 μm or less. The major surface having a length ratio of sides of 5 or less was hexagonal tabular grains having a (111) plane, and had an epitaxial junction at at least one vertex. As a result of observation with a transmission electron microscope at a low temperature, 70% or more of the projected area of all particles have no dislocation lines on the main surface other than the epitaxial part, and network and streak dislocation lines are formed on the epitaxial part. Had.
[0196]
The characteristic values of Emulsions 11 to 18 are summarized in Table 1.
[0197]
[Table 1]

[0198]
An emulsion subjected to the above chemical sensitization under the coating conditions as shown in Table 2 below was applied to a cellulose triacetate film support provided with an undercoat layer with a protective layer. 101-108 were created.
[0199]
[Table 2]

[0200]
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 Fuji Film Co., Ltd. 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).
[0201]

[0202]

[0203]

[0204]

[0205]
(Washing liquid) Common for tank and replenisher
Tap water was passed through a mixed bed column packed with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas Co.) and OH-type anion exchange resin (Amberlite IR-400), and calcium. And magnesium ion concentration was processed to 3 mg / L or less, and then sodium isocyanurate dichloride 20 mg / L and sodium sulfate 0.15 g / L were added. The pH of this solution was in the range of 6.5 to 7.5.
[0206]

[0207]
The density of the treated sample was measured with a green filter. Moreover, the same evaluation was performed on samples stored for 14 days under conditions of 50 ° C. and 60% relative humidity before exposure, and the storage stability was evaluated.
[0208]
Sensitivity value at a density of fog plus 0.2 (logarithm value of reciprocal of exposure necessary to obtain density of fog + 0.2 (relative value based on the sensitivity of the sample 101)) obtained as described above. Table 3 shows the results of evaluating the fog value and other photographic characteristics.
[0209]
[Table 3]

[0210]
As is apparent from the results in Table 3, by using the emulsion of the present invention, a light-sensitive material having high sensitivity, a high gradation in the highlight area, and a small sensitivity change after storage can be obtained. Furthermore, Br / Cl is in the range of 0.6 to 1.4, and the value of d is 0.3d.₀Or 1.7d₀It can be seen that the higher the ratio of tabular grains within the range of the total projected area, the higher the effect. When deviating from the emulsion conditions of the present invention, it can be seen that both sensitivity and storage stability are particularly deteriorated. Emulsion 18 has a larger equivalent circle diameter than emulsion 11, but has a low sensitivity because it deviates from the emulsion conditions of the present invention, and also has a large change in sensitivity after storage.
[0211]
(Example 2)
The effect of the emulsion of the present invention in a multilayer color photographic light-sensitive material is shown.
The support used in this example was produced by the following method.
[0212]
1) First layer and undercoat layer
For a 90 μm thick polyethylene naphthalate support, a treatment atmosphere pressure of 2.66 × 10 Pa, H in the atmosphere₂O partial pressure 75%, discharge frequency 30 kHz, output 2500 W, treatment strength 0.5 kV · A · min / m²Glow discharge treatment was applied. On this support, a coating solution having the following composition as a first layer was applied at a rate of 5 mL / m using the bar coating method described in JP-B-58-4589.²It applied with the application quantity of.
[0213]

[0214]
Further, after coating the first layer, it is wound around a stainless steel core having a diameter of 20 cm, and subjected to a heat treatment at 110 ° C. (Tg of PEN support: 119 ° C.) for 48 hours to carry out an annealing treatment and then support. Using a bar coating method, apply 10 mL / m of a coating solution having the following composition as an undercoat layer for emulsion on the opposite side to the first layer side.²It applied with the application quantity of.
[0215]

[0216]
Further, the second and third layers to be described later are sequentially coated on the first layer, and finally, a color negative photosensitive material having the composition to be described later is coated on the opposite side with respect to the support to form a silver halide emulsion. A layered transparent magnetic recording medium was prepared.
[0217]
2) Second layer (transparent magnetic recording layer)
(1) Dispersion of magnetic material
Co-coated γ-Fe₂O₃Magnetic material (average major axis length: 0.25 μm, S_BET: 39m²/ G, Hc: 6.56 × 10⁴A / m, σS: 77.1 Am²/ Kg, σr: 37.4 Am²/ Kg) 1100 parts by mass, 220 parts by mass of water and 165 parts by mass of a silane coupling agent [3- (poly (polymerization degree 10) oxyethynyl) oxypropyl trimethoxysilane] were added and kneaded well in an open kneader for 3 hours. did. This coarsely dispersed viscous liquid was dried at 70 ° C. for one day and night to remove water, and then heat-treated at 110 ° C. for 1 hour to produce surface-treated magnetic particles.
[0218]
Furthermore, it knead | mixed again with the following prescription for 4 hours with the open kneader.
Surface-treated magnetic particles 855 g
Diacetylcellulose 25.3 g
Methyl ethyl ketone 136.3 g
Cyclohexanone 136.3 g
[0219]
Furthermore, the following formulation was finely dispersed in a sand mill (1 / 4G sand mill) at 2000 rpm for 4 hours. As media, 1 mmφ glass beads were used.
45 g of the above kneaded liquid
Diacetylcellulose 23.7 g
Methyl ethyl ketone 127.7 g
Cyclohexanone 127.7 g
[0220]
Furthermore, the magnetic substance containing intermediate liquid was produced with the following prescription.
(2) Preparation of magnetic substance-containing intermediate solution
Magnetic material fine dispersion 674 g
Diacetylcellulose solution 24280 g
(Solid content: 4.34%, solvent: methyl ethyl ketone / cyclohexanone = 1/1)
Cyclohexanone 46 g
After mixing these, it stirred with the disperser and the "magnetic substance containing intermediate solution" was produced.
[0221]
An α-alumina abrasive dispersion of the present invention was prepared according to the following formulation.
(A) Sumicorundum AA-1.5 (average primary particle size 1.5 μm, specific surface area 1.3 m²/ G) Preparation of particle dispersion
Sumiko Random AA-1.5 152g
Silane coupling agent KBM903 (manufactured by Shin-Etsu Silicone) 0.48g
Diacetylcellulose solution 227.52 g
(Solid content 4.5%, solvent: methyl ethyl ketone / cyclohexanone = 1/1).
[0222]
Using the above formulation, fine dispersion was performed at 800 rpm for 4 hours using a ceramic-coated sand mill (1/4 G sand mill). As media, 1 mmφ zirconia beads were used.
[0223]
(B) Colloidal silica particle dispersion (fine particles)
“MEK-ST” manufactured by Nissan Chemical Co., Ltd. was used.
This is a dispersion of colloidal silica having an average primary particle diameter of 0.015 μm using methyl ethyl ketone as a dispersion medium, and the solid content is 30%.
[0224]
(3) Preparation of second layer coating solution
The above magnetic substance-containing intermediate solution 19053 g
Diacetylcellulose solution 264 g
(Solid content 4.5%, solvent: methyl ethyl ketone / cyclohexanone = 1/1)
Colloidal silica dispersion “MEK-ST” [dispersion b] 128 g
(Solid content 30%)
AA-1.5 dispersion [dispersion a] 12 g
Millionate MR-400 (manufactured by Nippon Polyurethane Co., Ltd.) Diluent 203 g
(Solid content 20%, diluent solvent: methyl ethyl ketone / cyclohexanone = 1/1)
Methyl ethyl ketone 170 g
Cyclohexanone 170 g
[0225]
Using a wire bar, the coating solution obtained by mixing and stirring the above was applied in an amount of 29.3 mL / m.²It applied so that it might become. Drying was performed at 110 ° C. The thickness of the magnetic layer after drying was 1.0 μm.
[0226]
3) Third layer (layer containing higher fatty acid ester slip agent)
(1) Preparation of a dispersion stock solution of slip agent
The following solution A was heated and dissolved at 100 ° C., added to solution A, and then dispersed with a high-pressure homogenizer to prepare a dispersion stock solution of slip agent.
[0227]
A liquid
The following compound 399 mass parts
C₆H₁₃CH (OH) (CH₂)₁₀COOC₅₀H₁₀₁
171 parts by mass of the following compound
n-C₅₀H₁₀₁O (CH₂CH₂O)₁₆H
Cyclohexanone 830 parts by mass
Liquid
Cyclohexanone 8600 parts by mass
[0228]
(2) Preparation of spherical inorganic particle dispersion
A spherical inorganic particle dispersion [c1] was prepared according to the following formulation.
[0229]
Isopropyl alcohol 93.54 parts by mass
Silane coupling agent KBM903 (manufactured by Shin-Etsu Silicone)
Compound 1-1: (CH₃O)₃Si- (CH₂)₃-NH₂5.53 parts by mass
Compound 1 2.93 parts by mass
[Chemical formula 2]

Seahosta KEP50 88.00 parts by mass
(Amorphous spherical silica, average particle size 0.5 μm, manufactured by Nippon Shokubai Co., Ltd.)
[0230]
After stirring for 10 minutes according to the above formulation, the following is added.
Diacetone alcohol 252.93 parts by mass
The above liquid was dispersed for 3 hours using an ultrasonic homogenizer “SONIFIER450 (manufactured by BRANSON Co., Ltd.)” while cooling with ice and stirring to complete a spherical inorganic particle dispersion c1.
[0231]
(3) Preparation of spherical organic polymer particle dispersion
A spherical organic polymer particle dispersion [c2] was prepared according to the following formulation.
XC99-A8808 (manufactured by Toshiba Silicone Co., Ltd., spherical crosslinked polysiloxane particles, average particle size 0.9 μm) 60 parts by mass
Methyl ethyl ketone 120 parts by mass
120 parts by mass of cyclohexanone
(Solid content 20%, solvent: methyl ethyl ketone / cyclohexanone = 1/1)
[0232]
While cooling with ice and stirring, the mixture was dispersed for 2 hours using an ultrasonic homogenizer “SONIFIER450 (manufactured by BRANSON)” to complete a spherical organic polymer particle dispersion c2.
[0233]
(4) Preparation of third layer coating solution
The third layer coating solution was prepared by adding the following to 542 g of the slip agent dispersion stock solution.
Diacetone alcohol 5950 g
Cyclohexanone 176 g
Ethyl acetate 1700 g
Seahosta KEP50 dispersion [c1] 53.1 g
300 g of the above spherical organic polymer particle dispersion [c2]
FC431 2.65 g
(3M Co., Ltd., solid content 50%, solvent: ethyl acetate)
BYK310 5.3 g
(BYK Kemi Japan Co., Ltd., solid content 25%)
10.35 mL / m of the third layer coating solution on the second layer²After coating at 110 ° C., it was further dried at 97 ° C. for 3 minutes.
[0234]
4) Coating of photosensitive layer
Next, on the opposite side to the support of the back layer obtained above, each layer having the following composition was applied in layers to prepare a color negative film sample 201.
[0235]
(Composition of photosensitive layer)
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.
[0236]
(Sample 201)
First layer (first antihalation layer)
Black colloidal silver Silver 0.080
0.07 μm silver iodobromide emulsion Silver 0.012
Gelatin 0.700
ExM-1 0.064
ExC-1 0.004
ExC-3 0.004
Cpd-2 0.002
F-8 0.002
HBS-1 0.099
HBS-2 0.013
[0237]
Second layer (second antihalation layer)
Black colloidal silver Silver 0.100
Gelatin 0.767
ExF-1 0.004
F-8 0.001
Solid disperse dye ExF-7 0.120
ExY-1 0.041
HBS-1 0.048
[0238]
Third layer (intermediate layer)
ExC-2 0.054
Cpd-1 0.092
Polyethyl acrylate latex 0.250
HBS-1 0.074
Gelatin 0.558
[0239]
4th layer (low sensitivity red sensitive emulsion layer)
Emulsion 11 Silver 0.73
ExC-1 0.404
ExC-2 0.024
ExC-3 0.083
ExC-4 0.213
ExC-5 0.044
ExC-6 0.025
ExC-8 0.073
ExC-9 0.010
Cpd-2 0.035
Cpd-4 0.035
Cpd-7 0.010
UV-2 0.022
UV-3 0.042
UV-4 0.009
UV-5 0.075
HBS-1 0.274
HBS-5 0.038
Gelatin 2.457
[0240]
5th layer (medium sensitivity red emulsion layer)
Em-B Silver 1.052
ExM-5 0.021
ExC-1 0.324
ExC-2 0.077
ExC-3 0.010
ExC-4 0.145
ExC-5 0.022
ExC-6 0.029
ExC-8 0.026
ExC-9 0.067
Cpd-2 0.046
Cpd-4 0.025
Cpd-7 0.030
HBS-1 0.290
Gelatin 1.046
[0241]
6th layer (high-sensitivity red-sensitive emulsion layer)
Em-A Silver 0.732
ExM-5 0.156
ExC-1 0.076
ExC-3 0.025
ExC-6 0.037
ExC-8 0.134
ExC-9 0.109
ExC-10 0.127
ExY-3 0.012
Cpd-2 0.090
Cpd-4 0.099
Cpd-7 0.040
HBS-1 0.254
HBS-2 0.100
Gelatin 1.006
[0242]
7th layer (intermediate layer)
Cpd-1 0.068
Cpd-6 0.309
Solid disperse dye ExF-4 0.020
HBS-1 0.068
Polyethyl acrylate latex 0.068
Gelatin 0.539
[0243]
Eighth layer (a layer that gives a layered effect to the red sensitive layer)
Em-E silver 0.358
Cpd-4 0.030
ExM-2 0.101
ExM-3 0.008
ExM-4 0.040
ExY-1 0.028
ExY-4 0.028
ExC-7 0.046
HBS-1 0.343
HBS-3 0.006
HBS-5 0.030
Gelatin 0.884
[0244]
9th layer (low sensitivity green emulsion layer)
Em-H Silver 0.206
Em-I Silver 0.208
Em-J Silver 0.255
ExM-2 0.304
ExM-3 0.075
ExY-1 0.028
ExY-3 0.024
ExC-7 0.014
HBS-1 0.505
HBS-3 0.012
HBS-4 0.095
HBS-5 0.055
Cpd-5 0.010
Cpd-7 0.020
Gelatin 1.282
[0245]
10th layer (medium sensitive green sensitive emulsion layer)
Em-G Silver 0.409
ExM-2 0.056
ExM-3 0.043
ExM-5 0.009
ExY-3 0.012
ExC-6 0.008
ExC-7 0.010
ExC-8 0.009
ExC-9 0.007
HBS-1 0.040
HBS-3 0.001
HBS-4 0.030
HBS-5 0.015
Cpd-5 0.002
Cpd-7 0.008
Gelatin 0.406
[0246]
11th layer (high sensitivity green emulsion layer)
Em-F Silver 0.407
Em-H Silver 0.156
ExC-6 0.009
ExC-8 0.010
ExC-9 0.011
ExM-1 0.015
ExM-2 0.050
ExM-3 0.010
ExM-4 0.030
ExM-5 0.035
ExM-6 0.018
ExY-3 0.007
Cpd-3 0.005
Cpd-4 0.007
Cpd-5 0.010
Cpd-7 0.020
HBS-1 0.248
HBS-3 0.003
HBS-4 0.094
HBS-5 0.037
Polyethyl acrylate latex 0.099
Gelatin 0.950
[0247]
12th layer (yellow filter layer)
Cpd-1 0.090
Solid disperse dye ExF-2 0.070
Solid disperse dye ExF-5 0.010
Oil-soluble dye ExF-6 0.010
HBS-1 0.055
Gelatin 0.589
[0248]
13th layer (low sensitivity blue-sensitive emulsion layer)
Em-M Silver 0.287
Em-N Silver 0.194
Em-O Silver 0.127
ExC-1 0.008
ExC-3 0.023
ExC-7 0.024
ExY-1 0.078
ExY-2 0.354
ExY-4 0.086
ExY-5 0.354
Cpd-2 0.082
Cpd-3 0.010
HBS-1 0.337
HBS-5 0.070
Gelatin 1.476
[0249]
14th layer (high sensitivity blue-sensitive emulsion layer)
Em-L Silver 0.401
Em-K Silver 0.401
ExM-5 0.008
ExC-1 0.013
ExY-1 0.061
ExY-2 0.139
ExY-3 0.010
ExY-4 0.080
ExY-5 0.130
Cpd-2 0.084
Cpd-3 0.002
Cpd-7 0.039
HBS-1 0.142
Gelatin 0.805
[0250]
15th layer (first protective layer)
0.07 μm silver iodobromide emulsion Silver 0.208
UV-1 0.167
UV-2 0.066
UV-3 0.099
UV-4 0.013
UV-5 0.160
F-11 0.008
ExF-3 0.003
S-1 0.077
HBS-1 0.175
HBS-4 0.017
Gelatin 1.007
[0251]
16th layer (second protective layer)
H-1 0.400
B-1 (diameter 1.7 μm) 0.050
B-2 (diameter 1.7 μm) 0.150
B-3 0.029
S-1 0.200
Gelatin 0.708
[0252]
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-11, B-4 to B-6, F-1 thru | or F-19 and lead salt, platinum salt, iridium salt, and rhodium salt are contained.
[0253]
Preparation of dispersions of organic solid disperse dyes
The ExF-2 of the 12th layer was dispersed by the following method.
ExF-2 wet cake (including 17.6% by weight water) 2.800 kg
Sodium octylphenyldiethoxymethanesulfonate
(31 mass% aqueous solution) 0.376 kg
F-15 (7% aqueous solution) 0.011 kg
4.020 kg of water
Total 7.210kg
(Adjusted to pH = 7.2 with NaOH)
[0254]
The slurry having the above composition is roughly dispersed by stirring with a dissolver, and then dispersed using an agitator mill LMK-4 at a peripheral speed of 10 m / s, a discharge rate of 0.6 kg / min, and a 0.3 mm diameter zirconia bead filling rate of 80%. The liquid was dispersed until the absorbance ratio was 0.29 to obtain a solid fine particle dispersion. The average particle size of the dye fine particles was 0.29 μm.
[0255]
Similarly, solid dispersions of ExF-4 and ExF-7 were obtained. The average particle diameters of the fine dye particles were 0.28 μm and 0.49 μm, respectively. ExF-5 was dispersed by the microprecipitation dispersion method described in Example 1 of EP 549,489A. The average particle size was 0.06 μm.
[0256]
[Table 4]

[0257]
[Table 5]

[0258]
[Table 6]

[0259]
[Table 7]

[0260]
The pigments listed in Table 6 are shown below.
[0261]
[Chemical Formula 3]

[0262]
[Formula 4]

[0263]
[Chemical formula 5]

[0264]
[Chemical 6]

[0265]
[Chemical 7]

[0266]
[Chemical 8]

[0267]
[Chemical 9]

[0268]
[Chemical Formula 10]

[0269]
Embedded image

[0270]
Embedded image

[0271]
Embedded image

[0272]
Embedded image

[0273]
Embedded image

[0274]
Embedded image

[0275]
The compounds used for each layer are shown below.
[0276]
Embedded image

[0277]
Embedded image

[0278]
Embedded image

[0279]
Embedded image

[0280]
Embedded image

[0281]
Embedded image

[0282]
Embedded image

[0283]
Embedded image

[0284]
Embedded image

[0285]
Embedded image

[0286]
Embedded image

[0287]
Embedded image

[0288]
Embedded image

[0289]
Embedded image

[0290]
The above silver halide color photographic light-sensitive material is referred to as Sample 201.
[0291]
Samples 202 to 208 were prepared from the sample 201 by changing the emulsion 11 of the fourth layer to emulsions 12 to 18.
[0292]
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.
[0293]
The treatment process and the treatment liquid composition are shown below.

[0294]
* Replenishment amount per photosensitive material 35mm width 1.1m (equivalent to 24Ex. 1)
The stabilizing solution and the fixing solution were a countercurrent system 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, respectively, per photosensitive material 35 mm width 1.1 m, 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.
[0295]
The composition of the treatment liquid is shown below.

[0296]

[0297]
(Fixing (1) Tank liquid)
5:95 (volume ratio) mixture of the above bleach tank solution and the following fixing tank solution
(PH 6.8)
[0298]

[0299]
(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.
[0300]
(Stabilizer) Tank fluid and replenisher common (Unit: g)
Sodium p-toluenesulfinate 0.03
Polyoxyethylene-p-monononylphenyl ether 0.2
(Average polymerization degree 10)
1,2-Benzisothiazoline-3-one sodium 0.10
Ethylenediaminetetraacetic acid disodium salt 0.05
1,2,4-triazole 1.3
1,4-bis (1,2,4-triazole-1-
Ilmethyl) piperazine 0.75
Add water and add 1.0L
pH 8.5
[0301]
The results are shown in Table 8.
[0302]
[Table 8]

[0303]
As is apparent from Table 8, it can be seen that by using the emulsion of the present invention for the low-sensitivity layer, a light-sensitive material having high sensitivity, high contrast and good storage stability can be obtained.
[0304]
(Example 3)
The effect of the highest silver iodide content of the host tabular grains on the photographic properties of the emulsion of the present invention will be described.
[0305]
(Preparation of emulsion 31)
(Host particles)
1100 mL of an aqueous solution containing 0.87 g of KBr and 0.95 g of oxidized gelatin was kept at 35 ° C. and stirred. AgNO₃(2.1 g) An aqueous solution containing KBr (1.5 g) and oxidized gelatin (1 g) was added over 30 seconds. After adding an aqueous solution containing 2.6 g of KBr, the temperature was raised to 65 ° C. An aqueous solution containing 41 g of hatched gelatin was added. Then, AgNO as the first growth₃(225 g) An aqueous solution and an aqueous KBr solution were added at an accelerated flow rate. At this time, the silver potential was kept at −20 mV with respect to the saturated calomel electrode. After that, AgNO as the outermost layer growth₃An aqueous solution (32.1 g) and an aqueous KBr solution containing KI were added over 18 minutes. The concentration of KI was adjusted so that the silver iodide content was 6.0 mol%.
[0306]
Sensitizing dyes I, II, III are added at a molar ratio of 69: 30: 1 and 80% of the saturation coverage, followed by calcium nitrate (2.5 × 10^-2mol) was added. However, the sensitizing dye was used as a solid dispersion prepared by the method described in JP-A-11-52507.
[0307]
(Epitaxial formation part)
After this, AgNO₃(6.7 g) An aqueous solution and an aqueous solution containing NaCl (2.4 g) were added. Then AgNO₃(0.35 g) aqueous solution and KI (0.45 g) aqueous solution were added. Then AgNO₃(5.6 g) Aqueous solution and KBr (3.86 g) aqueous solution were added.
[0308]
(Washing, post-ripening part)
Subsequently, ordinary water washing was performed. At 50 ° C., potassium thiocyanate (1.8 × 10 5 per mol of silver halide)^-4Mol), chloroauric acid (1.3 × 10^-5Mol), sodium thiosulfate (2.1 × 10^-5Mol) and N, N-dimethylselenourea (8.8 × 10 6).^-6Mol) was added for optimum chemical sensitization. Antifoggant (Compound I) (6.9 × 10^-4Mol) was added to complete the chemical sensitization.
[0309]
The emulsion of the present invention was tabular grains having an average equivalent-circle diameter of 0.870 μm, a variation coefficient of equivalent-circle diameter of 17%, an average thickness of 0.087 μm, and an average aspect ratio of 10.0. In addition, the maximum length with respect to the length of the side having the minimum length, in which 70% or more of the projected area of all the grains has an equivalent circle diameter of 0.6 μm to 1.1 μm and a thickness of 0.07 μm to 0.12 μm. The main surface having a side length ratio of 5 or less was a (111) plane hexagonal tabular grain, and had an epitaxial junction at least at one apex. As a result of observation with a transmission electron microscope at a low temperature, 70% or more of the projected area of all the particles has no dislocation lines on the main surface other than the epitaxial part, and has a network-like dislocation line in the epitaxial part. It was.
[0310]
(Preparation of emulsions 32 and 33)
Emulsions 32 and 33 were prepared by changing the silver iodide content in the outermost layer of emulsion 31. The grain shape and the like were adjusted to those of the emulsion 31 by adjusting the silver potential. Specifically, the concentration of KI used for forming the outermost layer was adjusted so that the silver iodide content was 9 mol% and 18 mol%.
[0311]
(Preparation of emulsion 34)
Sample No. described in Example-2 of JP-A-2002-169241. Emulsion 34 was prepared following 3. The tabular grains had an average equivalent circle diameter of 0.830 μm, a variation coefficient of equivalent circle diameter of 19%, an average thickness of 0.086 μm, and an average aspect ratio of 9.7. In addition, the maximum length with respect to the length of the side having the minimum length, in which 70% or more of the projected area of all the particles has an equivalent circle diameter of 0.6 μm to 1.1 μm and a thickness of 0.07 μm to 0.12 μm. The main surface having a side length ratio of 5 or less was a (111) -faced hexagonal tabular grain, and had an epitaxial junction at at least one apex. As a result of observation with a transmission electron microscope at a low temperature, 70% or more of the projected area of all the particles has no dislocation lines on the main surface other than the epitaxial part, and has a network-like dislocation line in the epitaxial part. It was.
[0312]
The characteristic values of the emulsions 31 to 34 are summarized in Table 9.
[0313]
[Table 9]

[0314]
An emulsion subjected to the above chemical sensitization under the coating conditions shown in Table 2 of Example 1 was applied to a cellulose triacetate film support provided with an undercoat layer with a protective layer. 301 to 304 were created and the same experiment as in Example 1 was performed.
[0315]
[Table 10]

[0316]
As is apparent from the results in Table 10, by using the emulsion of the present invention, a photosensitive material having high sensitivity, a high gradation in the highlight area, and a small change in sensitivity after storage can be obtained. The higher the ratio of grains having a maximum silver iodide content of the host tabular grains of 10 mol% or less, the greater the effect.
[0317]
Example 4
Samples 401 to 404 were prepared by replacing the emulsion 11 of the fourth layer with the emulsions 31 to 34 from the sample 201 of Example 2, and the same experiment as in Example 2 was performed. The results are shown in Table 11.
[0318]
[Table 11]

[0319]
As is apparent from Table 11, it can be seen that a sensitive material having high sensitivity, high contrast and good storage stability can be obtained by using the emulsion of the present invention in a low-sensitivity layer.
[0320]
(Example 5)
The effect of tabular grain thickness on the emulsion of the present invention will be described.
[0321]
(Preparation of emulsions 52 and 53)
By changing the silver potential during the first growth of the emulsion 11, the thickness was changed to prepare emulsions 52 and 53. The coverage with the dye was 75%.
[0322]
Emulsion 52 was a tabular grain having an average equivalent-circle diameter of 0.61 μm, a variation coefficient of equivalent-circle diameter of 19%, an average thickness of 0.080 μm, and an average aspect ratio of 7.6. Further, the maximum length with respect to the length of the side having the minimum length, in which 70% or more of the projected area of all the grains has a circle equivalent diameter of 0.4 μm to 0.8 μm and a thickness of 0.07 μm to 0.11 μm. The main surface having a side length ratio of 5 or less was a (111) -faced hexagonal tabular grain, and had an epitaxial junction at at least one apex. As a result of observation with a transmission electron microscope at a low temperature, 70% or more of the projected area of all the particles has no dislocation lines on the main surface other than the epitaxial part, and has a network-like dislocation line in the epitaxial part. It was.
[0323]
Emulsion 53 was a tabular grain having an average equivalent circle diameter of 0.73 μm, a variation coefficient of equivalent circle diameter of 19%, an average thickness of 0.055 μm, and an average aspect ratio of 13.3. Further, 70% or more of the projected area of all the grains has an equivalent diameter of 0.5 μm or more and 0.9 μm or less and a thickness of 0.07 μm or less of the side having the maximum length with respect to the side having the minimum length. The main surface having a length ratio of 5 or less was hexagonal tabular grains having a (111) plane, and had an epitaxial junction at at least one apex. As a result of observation with a transmission electron microscope at a low temperature, 70% or more of the projected area of all the particles has no dislocation lines on the main surface other than the epitaxial part, and has a network-like dislocation line in the epitaxial part. It was.
[0324]
The characteristic values of Emulsions 11, 52 and 53 are summarized in Table 12.
[0325]
[Table 12]

[0326]
Emulsions 11, 52, and 53 were coated on a cellulose triacetate film support provided with an undercoat layer under the coating conditions shown in Table 2 of Example 1 above. 101, 502, and 503 were created and the same experiment as in Example 1 was performed. At this time, the coating solution for the emulsion layer was held while being stirred at 40 ° C. for 30 minutes immediately before coating. Next, emulsions 11, 52 and 53 were coated on the cellulose triacetate film support provided with the undercoat layer under the coating conditions as shown in Table 2 of Example 1 above. 111, 512, and 513 were created and the same experiment as in Example 1 was performed. However, the coating solution for the emulsion layer at this time was the same as that of Sample No. except that the coating solution was held for 10 hours at 40 ° C. while stirring. 101, 502 and 503 are prepared and applied under the same conditions.
[0327]
[Table 13]

[0328]
As is apparent from Table 13, by using the emulsion of the present invention, a light-sensitive material having a high gradation in the highlight area and a small change in sensitivity after storage can be obtained, but the emulsion thickness is 0.07 μm or more. It can be seen that the smaller the ratio of the grains to the total projected area, the greater the decrease in sensitivity when the emulsion coating solution is allowed to elapse for a long time before coating, particularly when the ratio is less than 70%.

Claims (4)

In a silver halide emulsion containing a dispersion medium and silver halide grains, 70% or more of the total projected area of the silver halide grains satisfies the following requirements (i), (ii), (iii) and (iv): A silver halide photographic emulsion characterized by being occupied by filled epitaxial tabular grains.
(I) Silver iodochlorobromide epitaxial tabular grains having a (111) plane as the main surface (ii) having an epitaxial part at at least one apex of the host tabular grains (iii) In the epitaxial part, the average silver chloride content The ratio (Br / Cl) of (Cl mol%) to the average silver bromide content (Br mol%) is in the range of 0.6 to 1.4.
(Iv) Vepi ^1/3 = 0.34 Vhost ^1/3 + d where Vepi is the volume of the epitaxial portion and Vhost is the volume of the host tabular grain.
When expressed as, to the value of d is 0.3 d ₀ not in the range of 1.7 D _0. However, d ₀ = 0.03. In a silver halide emulsion containing a dispersion medium and silver halide grains, 70% or more of the total projected area of the silver halide grains is further occupied by silver halide grains satisfying the requirement (v) below. 2. The silver halide photographic emulsion according to claim 1, wherein:
(V) The maximum silver iodide content of the host tabular grains is 10 mol% or less. In a silver halide emulsion containing a dispersion medium and silver halide grains, 70% or more of the total projected area of the silver halide grains is occupied by silver halide grains satisfying the following requirement (vi): A silver halide photographic emulsion according to claim 1 or 2.
(Vi) The thickness of the tabular grain is 0.07 μm or more. A silver halide photographic light-sensitive material comprising the silver halide photographic emulsion according to any one of claims 1 to 3.