JP4221860B2 - Silver halide emulsion and silver halide photographic light-sensitive material - Google Patents

Description

【００６５】
沃素イオン放出剤と求核試薬を反応させて、沃素イオンを放出させる場合、求核試薬として、水酸化物イオン、亜硫酸イオン、チオ硫酸イオン、スルフィン酸塩、カルボン酸塩、アンモニア、アミン類、アルコール類、尿素類、チオ尿素類、フェノール類、ヒドラジン類、スルフィド類、ヒドロキサム酸類などを用いることができ、水酸化物イオン、亜硫酸イオン、チオ硫酸イオン、スルフィン酸塩、カルボン酸塩、アンモニア、アミン類が好ましく、水酸化物イオン、亜硫酸イオンがより好ましい。
【００６６】
本発明の請求項３３〜４０においては、粒子内の少なくとも２つの高沃度局在相の間に中間相を有する。該高沃度局在相が３つ以上存在する場合には、少なくともいずれか２つの高沃度局在相の間に該中間相を有する。該中間相は均一な組成であってもよく、組成の異なる複数のハロゲン化銀相や沃化銀含有率が連続的に変化するようなハロゲン化銀相から構成されていてもよい。中間相の平均沃化銀含有率は０モル％以上１０モル％以下であり、その比率（銀量比）は粒子銀量の１０％以上７０％以下である。該中間相の平均沃化銀含有率の好ましい値は０モル％以上５モル％以下であり、該中間相の好ましい銀量比は１５％以上５０％以下である。
【００６７】
本発明の請求項３３〜４０においては、前記高沃度局在相のなかで最も外側に位置する高沃度局在相の外側にシェル相を有する。該シェル相は均一な組成であってもよく、組成の異なる複数のハロゲン化銀相や沃化銀含有率が連続的に変化するようなハロゲン化銀相から構成されていてもよい。シェル相の平均沃化銀含有率は０モル％以上１０モル％以下であり、その比率（銀量比）は粒子銀量の１０％以上５０％以下である。該シェル相の平均沃化銀含有率の好ましい値は０モル％以上６モル％以下であり、該シェル相の好ましい銀量比は２０％以上４０％以下である。
【００６８】
本発明の請求項３３〜４０においては、前記高沃度局在相のなかで最も内側に位置する高沃度局在相の内側に内部相を有する。本発明のハロゲン化銀乳剤を、事前に調製したいわゆるハロゲン化銀核粒子やハロゲン化銀種粒子を成長させて形成する場合、該内部相に核粒子や種粒子を含んでいてもよい。また、核粒子や種粒子を該核粒子や種粒子とは異なる組成で成長させて内部相を形成してもよい。即ち、該内部相は均一な組成であってもよく、組成の異なる複数のハロゲン化銀相や沃化銀含有率が連続的に変化するようなハロゲン化銀相から構成されていてもよい。該内部相の平均沃化銀含有率は１０モル％以下であり、その比率（銀量比）は粒子銀量の５％以上６０％以下である。該内部相の平均沃化銀含有率の好ましい値は０モル％以上３モル％以下である。
【００６９】
前記のコアおよび高沃度局在相を除くシェル層は、一般に知られたハロゲン化銀乳剤の調製で形成することができる。本発明のハロゲン化銀乳剤の調製においては、グラフキデ著「写真の物理と化学」、ポールモンテル社刊（Ｐ．Ｇｌａｆｋｉｄｅｓ，Ｃｈｉｍｉｅ ｅｔ Ｐｈｙｓｉｑｕｅ Ｐｈｏｔｏｇｒａｐｈｉｑｕｅ Ｐａｕｌ Ｍｏｎｔｅｌ，１９６７）、ダフィン著「写真乳剤化学」、フォーカルプレス社刊（Ｇ．Ｆ．Ｄｕｆｆｉｎ，Ｐｈｏｔｏｇｒａｐｈｉｃ Ｅｍｕｌｓｉｏｎ Ｃｈｍｉｓｔｒｙ（Ｆｏｃａｌ Ｐｒｅｓｓ，１９６６））、ゼリグマン等著「写真乳剤の製造と塗布」、フォーカルプレス社刊（Ｖ．Ｌ．Ｚｅｌｉｋｍａｎ ｅｔ ａｌ，Ｍａｋｉｎｇ ａｎｄ Ｃｏａｔｉｎｇ Ｐｈｏｔｏｇｒａｐｈｉｃ Ｅｍｕｌｓｉｏｎ，Ｆｏｃａｌ Ｐｒｅｓｓ，１９６４）などに記載された方法を参考にすることもできる。すなわち、酸性法、中性法、アンモニア法等のいずれの方法も用いることができる。また、粒子成長工程において銀塩水溶液とハロゲン化物水溶液を反応させる形式としては片側混合法、同時混合法、それらの組合わせなどのいずれの方法を用いてもよい。粒子を銀イオン過剰の下において形成させる方法（いわゆる逆混合法）を用いることもできる。同時混合法の一つの形式としてハロゲン化銀の生成する液相中のｐＡｇを制御する方法、すなわち、いわゆるコントロールド・タブルジェット法が知られているが、この方法はハロゲン化銀粒子成長工程における粒子間の均質性を高めるために有効であり、例えばコアや高沃度局在層を除くシェル層の形成に好ましく用いることができる。
【００７０】
乳剤調製用の反応容器にあらかじめ沈殿形成したハロゲン化銀粒子を添加する方法、例えば米国特許第４，３３４，０１２号、同第４，３０１，２４１号、同第４，１５０，９９４号に記載の方法等を用いることもできる。特に成長用の銀イオン及びハロゲンイオンの供給源として添加する方法は好ましい態様である。添加方法として一度に全量を添加する、複数回に分散して添加する、あるいは連続的に添加するなどのなかから選んで用いることができる。また本発明に関係するハロゲン化銀粒子の表面を改質させるために種々のハロゲン組成の粒子を添加することも場合により有効である。
【００７１】
粒子成長工程を一定濃度、一定流速で銀塩水溶液とハロゲン化物水溶液を添加する方法以外に、英国特許第１，４６９，４８０号、米国特許第３，６５０，７５７号、同第４，２４２，４４５号に記載されているように濃度を変化させる、あるいは流速を変化させる粒子形成法は好ましい方法である。濃度を増加させる、あるいは流速を増加させることにより、供給する銀塩水溶液とハロゲン化物水溶液を添加時間の一次関数、二次関数、あるいはより複雑な関数で変化させることができる。また必要により供給量を減量することも場合により選択できる。
【００７２】
反応容器の混合機構としては、米国特許第２，９９６，２８７号、同第３，３４２，６０５号、同第３，４１５，６５０号、同第３，７８５，７７７号、西独公開特許第２，５５６，８８５号、同第２，５５５，３６４号に記載されている方法等のなかから選んで用いることができる。
【００７３】
熟成を促進する目的に対してはハロゲン化銀溶剤が有用である。例えば熟成を促進するのに過剰量のハロゲンイオンを反応容器中に存在せしめることが知られている。またハロゲン化銀溶剤等の他の熟成促進剤を用いることもできる。これらの熟成促進剤は、銀塩水溶液やハロゲン化物水溶液を添加する前に反応容器中の分散媒中に全量を配合しておくことができるし、銀塩水溶液やハロゲン化物水溶液、または分散媒を加えると共に反応容器中に導入することもできる。別の態様として、熟成剤を銀塩水溶液やハロゲン化物水溶液の添加とは独立して導入することもできる。ハロゲン化銀溶剤としては、アンモニア、チオシアン酸塩（例えば、ロダンカリ、ロダンアンモニウム）、有機チオエーテル化合物（例えば、米国特許第３，５７４，６２８号、同第３，０２１，２１５号、同第３，０５７，７２４号、同第３，０３８，８０５号、同第４，２７６，３７４号、同第４，２９７，４３９号、同第３，７０４，１３０号、同第４，７８２，０１３号、特開昭５７−１０４９２６号などに記載の化合物）、チオン化合物（例えば、特開昭５３−８２４０８号、同５５−７７７３７号、米国特許第４，７８２，０１３号などに記載されている四置換チオウレアや、特開昭５３−１４４３１９号に記載されている化合物）や、特開昭５７−２０２５３１号に記載されているハロゲン化銀粒子の成長を促進しうるメルトカプト化合物、アミン化合物（例えば、特開昭５４−１００７１７号など）等があげられる。
【００７４】
本発明のハロゲン化銀乳剤は、粒子形成後に脱塩のために水洗し、新しく用意した分散媒を含む水溶液中に分散することが好ましい。水洗の温度は目的に応じて選べるが、５℃〜６０℃の範囲で選ぶことが好ましい。水洗時のｐＨも目的に応じて選べるが２〜１０の間で選ぶことが好ましい。さらに好ましくは３〜８の範囲である。水洗時のｐＡｇも目的に応じて選べるが５〜１０の間で選ぶことが好ましい。水洗の方法としてヌードル水洗法、半透膜を用いた透析法、遠心分離法、凝析沈降法、イオン交換法のなかから選んで用いることができる。凝析沈降法には硫酸塩を用いる方法、有機溶剤を用いる方法、水溶性ポリマーを用いる方法、修飾ゼラチンや変性ゼラチン等のゼラチン誘導体を用いる方法等があるが、本発明の乳剤調製においては特開平５−７２６５８に記載の脱塩方法を用いることが好ましい。
【００７５】
本発明において、個々のハロゲン化銀粒子の沃化銀含有率及び平均沃化銀含有率は、ＥＰＭＡ法（Ｅｌｅｃｔｒｏｎ Ｐｒｏｂｅ Ｍｉｃｒｏ Ａｎａｌｙｚｅｒ法）を用いることにより求めることが可能である。この方法は、乳剤粒子を互いに接触しないように良く分散したサンプルを作製し、電子ビームを照射する電子線励起によるＸ線分析より極微小な部分の元素分析が行える。この方法により、各粒子から放射される銀及び沃度の特性Ｘ線強度を求めることにより、個々の粒子のハロゲン組成が決定できる。少なくとも５０個の粒子についてＥＰＭＡ法により沃化銀含有率を求めれば、これらの平均から平均沃化銀含有率が求められる。また、平均沃化銀含有率の測定は、蛍光Ｘ線分析法、ＩＣＰ（誘導プラズマ）発光分析法、ＩＣＰ質量分析法など、よく知られた他の方法で、乳剤全体の沃化銀含有率を測定することによっても求めることができる。
【００７６】
本発明における平板粒子は、１種類の平板粒子内においては粒子間の沃化銀含有率がより均一になっていることが好ましい。ＥＰＭＡ法により粒子間の沃化銀含有率の分布を測定した時に、相対標準偏差が３０％以下、更には２０％以下であることが好ましい。
【００７７】
本発明の平板粒子の表面のハロゲン組成はＸＰＳ法（Ｘ−ｒａｙ Ｐｈｏｔｏｅｌｅｃｔｒｏｎ Ｓｐｅｃｔｒｏｓｃｏｐｙ法：Ｘ線光電子分光法）によって次のように求められる。すなわち、試料を１．３３×１０^-6Ｐａ以下の超高真空中で−１１０℃以下まで冷却し、プローブ用Ｘ線としてＭｇＫαをＸ線源電圧１５ｋＶ、Ｘ線源電流４０ｍＡで照射し、Ａｇ３ｄ５／２、Ｂｒ３ｄ、Ｉ３ｄ３／２の電子について測定する。測定されたピークの積分強度を感度因子（Ｓｅｎｓｉｔｉｖｉｔｙ Ｆａｃｔｏｒ）で補正し、これらの強度比からハロゲン化銀表面のハライド組成を求める。
【００７８】
本発明のハロゲン化銀粒子のその他の特徴として、ハロゲン化銀粒子の全投影面積の５０％以上が、１粒子当たり１０本以上の転位線をフリンジ部に有する。この場合、転位線の数は１粒子当たり平均２０本以上であることが好ましい。ハロゲン化銀粒子が有する転位線は、例えばＪ．Ｆ．Ｈａｍｉｌｔｏｎ、Ｐｈｏｔｏ．Ｓｃｉ．Ｅｎｇ．１１（１９６７）５７や、Ｔ．Ｓｈｉｏｚａｗａ，Ｊ．Ｓｏｃ．Ｐｈｏｔ．Ｓｃｉ．Ｊａｐａｎ３５（１９７２）２１３に記載の、低温での透過型電子顕微鏡を用いた直接的な方法により観察できる。即ち、乳剤から粒子に転位が発生するほどの圧力をかけないように注意して取り出したハロゲン化銀粒子を、電子顕微鏡用のメッシュに乗せ、電子線による損傷（プリントアウトなど）を防ぐように試料を冷却した状態で透過法により観察を行う。この時、粒子の厚みが厚いほど電子線が透過しにくくなるので、高加速電圧型の電子顕微鏡を用いた法がより鮮明に観察することができる。このような方法によって得られた粒子写真から、個々の粒子における転位線の位置及び数を求めることができる。転位線が密集して存在する場合には、１粒子当たりの転位線の数を明確に数えることはできない場合がある。しかしながら、このような場合においても、おおよそには１０本以上、２０本以上と判別することが可能であり、明らかに数本程度しか存在しない場合とは区別できる。１粒子当たりの転位線の平均数は、１００粒子以上に対して転位線の数を数えて算術平均として求める。
【００７９】
ハロゲン化銀への転位線の導入方法として、高沃化銀含有相に低沃化銀含有相を隣接して形成する方法がある。
【００８０】
本発明のハロゲン化銀乳剤に転位線を沃素イオン放出剤によって導入する場合の好ましい反応条件を以下に示す。
【００８１】
反応温度は７０℃〜３０℃であることが好ましく、６５℃〜３５℃であることがより好ましい。ｐＢｒは１．５０以下であることが好ましく、１．３０以下であることがより好ましく、１．１０以下であることがさらに好ましい。添加する沃素イオン放出剤の量は粒子成長終了後の、総ハロゲン化銀量に対して、０．５〜３ｍｏｌ％であることが好ましい。また、沃素イオン放出反応時に、求核剤として水酸化物イオンを用いる場合、すなわちｐＨの調整によって沃素イオン放出剤を反応させる場合、ｐＨが９．０以上１２．０以下の条件で反応を行うことが好ましく、ｐＨ１０．０以上１１．０以下であることがより好ましい。求核剤として水酸化物イオン以外のものを用いる場合、求核剤の量は、沃素イオン放出剤の量の０．２５倍以上２．０倍以下であることが好ましく、０．５０倍以上１．５倍以下であることがより好ましく、０．８０倍以上１．２倍以下であることが好ましい。求核剤が水酸化物イオン以外である場合の、沃素イオン放出反応時のｐＨは、６．０以上１１．０以下であることが好ましく、７．０以上１０．０以下であることがより好ましい。
【００８２】
本発明のハロゲン化銀乳剤に転位線を沃化銀を含む微粒子乳剤によって、導入する場合の好ましい反応条件を以下に示す。
【００８３】
沃化銀を含む微粒子乳剤を添加する際の温度は７０℃〜３０℃であることが好ましく、６５℃〜３５℃であることがより好ましい。ｐＢｒは１．５０以下であることが好ましく、１．３０以下であることがより好ましく、１．１０以下であることがさらに好ましい。添加する沃化銀を含む微粒子乳剤の量は、沃化銀量にして、粒子成長終了後の総ハロゲン化銀量に対して、０．５〜３ｍｏｌ％であることが好ましい。
【００８４】
ハロゲン化銀粒子の形状として、立方体、八面体、十四面体のような規則的な結晶形を有するいわゆる正常晶と、平板状、じゃがいも状のような変則的な結晶形を有するもの、双晶面のような結晶欠陥をもつもの、あるいはそれらの複合体等が知られているが、本発明のハロゲン化銀乳剤は、ハロゲン化銀粒子の全投影面積の５０％以上が、アスペクト比が３以上の平板状ハロゲン化銀粒子であることが好ましい。さらには、全投影面積の５０％以上が、アスペクト比が５以上の平板状ハロゲン化銀粒子であることがより好ましく、全投影面積の８０％以上が、アスペクト比が５以上の平板状ハロゲン化銀粒子であることが特に好ましい。平板状ハロゲン化銀粒子とは、結晶学的には双晶に分類される結晶形態を有する。双晶とは、一つの粒子内に一つ以上の双晶面を有する結晶であり、ハロゲン化銀粒子における双晶の形態の分類は、クラインとモイザーによる報文「Ｐｈｏｔｏｇｒａｐｈｉｓｈｅ Ｋｏｒｒｅｓｐｏｎｄｅｎｚ」９９巻９９頁、同１００巻５７頁に詳しく述べられている。また、平板状のハロゲン化銀粒子は、クリーブ著「写真の理論と実際」（Ｃｌｅｖｅ，Ｐｈｏｔｏｇｒａｐｈｙ Ｔｈｏｒｙａｎｄ Ｐｒａｃｔｉｃｅ（１９３０）），１３１頁；ガトフ著、フォトグラフィク・サイエンス・アンド・エンジニアリング（Ｇｕｔｏｆｆ，Ｐｈｏｔｏｇｒａｐｈｉｃ Ｓｃｉｅｎｃｅ ａｎｄ Ｅｎｇｉｎｅｅｒｉｎｇ），第１４巻、２４８〜２５７頁（１９７０年）；米国特許第４，４３４，２２６号、同第４，４１４，３１０号、同第４，４３３，０４８号、同第４，４３９，５２０号、及び英国特許第２，１１２，１５７号などに記載の方法を参考にして調製することができる。
【００８５】
本発明に関係する平板状ハロゲン化銀粒子として三角形、六角形、円形などの形状を選ぶこともできるが、米国特許第４，７９７，３５４号に記載されているような六辺の長さがほぼ等しい六角形の平板状ハロゲン化銀粒子が好ましい形態である。また、本発明に関係する平板状ハロゲン化銀粒子は、粒子内に１つまたは互いに平行な２つ以上の双晶面を有するものが好ましい。これらの双晶面は平板状粒子の表面を形成する平面の中で最も広い面積を有する面（主平面とも称する）に対してほぼ平行に存在する。本発明における特に好ましい形態は、平行な２つの双晶面を有する場合である。これらの双晶面は透過型電子顕微鏡を用いて、以下の方法で観察することができる。まず、含有される平板粒子の主平面が、基板に対してほぼ平行に配向するようにハロゲン化銀乳剤を基板上に塗布し、試料を作製する。これをダイヤモンド・カッターを用いて基板に対して垂直に連続的に切削し、厚さ０．１μｍ程度の連続薄切片を得る。この切片を透過型電子顕微鏡で観察することにより双晶面の存在及びその位置を確認することができる。
【００８６】
本発明においてアスペクト比とは、粒径と粒子厚さの比をいう。ここで粒径とは、主平面に対して垂直にその粒子を投影した場合の面積に等しい面積を有する円の直径を意味する。即ち、アスペクト比＝直径／厚さである。平板状ハロゲン化銀粒子の粒径として、米国特許第４，７４８，１０６号に記載されているような平均粒径が０．６μｍ以下の粒子は高画質化にとって好ましく、また平板状粒子の粒子厚さを０．３μｍ以下、より好ましくは０．２μｍ以下に限定するのは鮮鋭性を高める上で好ましい。
【００８７】
ハロゲン化銀粒子の粒径、粒子厚さ、アスペクト比を算出するための個々の粒子の投影面積と厚さは、以下の方法で求めることができる。支持体上に内部標準となる粒径が既知のラテックスボールと、主平面が基板に平行に配向するようにハロゲン化銀粒子とを塗布した試料を作製し、ある角度からカーボン蒸着によりシャドーを施した後、通常のレプリカ法によってレプリカ試料を作製する。同試料の電子顕微鏡写真を撮影し、画像処理装置等を用いて個々の粒子の投影面積と厚さを求める。この場合、粒子の投影面積は内部標準の投影面積から、粒子の厚さは内部標準と粒子の影の長さから算出することができる。
【００８８】
本発明のハロゲン化銀乳剤は、このようにして求められる粒径のばらつきが小さいハロゲン化銀乳剤であることが好ましい。具体的には、粒径の変動係数が２０％以下であることが好ましく、さらには１５％以下であることがより好ましい。粒径の変動係数とは、下式によって定義される値であり、前述のレプリカ法でハロゲン化銀乳剤に含まれるハロゲン化銀粒子の粒径を、任意に３００個以上測定して得られた値を用いて算出する。
【００８９】
粒径の変動係数（％）＝（粒径の標準偏差／粒径の平均値）×１００
米国特許第４，７９７，３５４号、及び特開平２−８３８号には平板化率が高く単分散の六角平板状粒子の製造法が記載されている。また、欧州特許第５１４，７４２号にはポリアルキレンオキサイドブロックコポリマーを用いて粒子サイズ分布の変動係数が１０％未満の平板状粒子を製造する方法についての記載がある。本発明のハロゲン化銀乳剤の調製には、これらの技術を適用することも可能である。
【００９０】
本発明の請求項１，９，１７，２５，３３記載のハロゲン化銀乳剤は、還元増感されていることを特徴とする。本発明において、用いることのできる還元増感法としては、たとえば、Ｐｈｏｔｏｇｒａｐｈｉｃ Ｓｅｎｓｉｔｉｖｉｔｙ（谷忠昭著、Ｏｘｆｏｒｄ ＵｎｉｖｅｒｓｉｔｙＰｒｅｓｓ１９９５）の１８０ページからの記載に各種の還元増感法が示されている。しかし、還元増感の手法は各種知られており、これらに限定されない。すなわち、ハロゲン化銀乳剤に公知の還元剤を添加する方法、銀熟成と呼ばれるｐＡｇ１〜７の低ｐＡｇの雰囲気で成長させるあるいは熟成させる方法、特開平１０−２６８１０号に示されているような高ｐＨ熟成と呼ばれるｐＨ８〜１１の高ｐＨの雰囲気で成長させるあるいは熟成させる方法などが知られており、また２つ以上の方法を併用することもできる。還元増感剤を添加する方法は還元増感のレベルを微妙に調節できる点で好ましい方法である。
【００９１】
還元増感剤として第一錫塩、アミンおよびポリアミン酸、ヒドラジン誘導体、ホルムアミジンスルフィン酸、シラン化合物、ボラン化合物などが公知である。本発明にはこれら公知の化合物から選んで用いることもできる。また２種以上の化合物を併用することもできる。還元増感剤として塩化第一錫、二酸化チオ尿素、ジメチルアミンボランが好ましい化合物である。さらに好ましくは、米国特許第５，３８９，５１０号に記載のアルキニルアミン化合物を選択することができる。還元増感剤の添加量は乳剤製造条件に依存するので添加量を選ぶ必要があるが、ハロゲン化銀１モル当り１０^-7〜１０^-3モルの範囲が適当である。
【００９２】
本発明の還元増感剤としてアスコルビン酸およびその誘導体を用いることもできる。アスコルビン酸およびその誘導体（以下、「アスコルビン酸化合物」という。）の具体例としては以下のものが挙げられる。
【００９３】
（Ａ−１） Ｌ−アスコルビン酸
（Ａ−２） Ｌ−アスコルビン酸ナトリウム
（Ａ−３） Ｌ−アスコルビン酸カリウム
（Ａ−４） ＤＬ−アスコルビン酸
（Ａ−５） Ｄ−アスコルビン酸ナトリウム
（Ａ−６） Ｌ−アスコルビン酸−６−アセテート
（Ａ−７） Ｌ−アスコルビン酸−６−パルミテート
（Ａ−８） Ｌ−アスコルビン酸−６−ベンゾエート
（Ａ−９） Ｌ−アスコルビン酸−５，６−ジアセテート
（Ａ−１０） Ｌ−アスコルビン酸−５，６−Ｏ−イソプロピリデン
本発明に用いられるアスコルビン酸化合物は、従来還元増感剤が好ましく用いられている添加量に比較して多量用いることが望ましい。例えば特公昭５７−３３５７２号には「還元剤の量は通常銀イオンｇにつき０．７５×１０^-2ミリ当量（８×１０^-4モル／ＡｇＸモル）を越えない。硝酸銀ｋｇにつき０．１〜１０ｍｇの量（アスコルビン酸として、１０^-7〜１０^-5モル／ＡｇＸモル）が多くの場合効果的である。」（換算値は発明者らによる）と記述されている。米国特許第２，４８７，８５０号には「還元増感剤として錫化合物の用いることのできる添加量として１×１０^-7〜４４×１０^-6モル」と記載されている。また特開昭５７−１７９８３５号には二酸化チオ尿素の添加量としてハロゲン化銀１モル当り約０．０１ｍｇ〜約２ｍｇ、塩化第一錫として約０．０１ｍｇ〜約３ｍｇを用いるのが適当であると記載されている。本発明に用いられるアスコルビン酸化合物は乳剤の粒子サイズ、ハロゲン組成、乳剤調製の温度、ｐＨ、ｐＡｇなどの要因によって好ましい添加量が依存するが、ハロゲン化銀１モル当り５×１０^-5〜１×１０^-1モルの範囲から選ぶことが望ましい。さらに好ましくは５×１０^-4モル〜１×１０^-2モルの範囲から選ぶことが好ましい。特に好ましいのは１×１０^-3モル〜１×１０^-2モルの範囲から選ぶことである。
【００９４】
還元増感剤は水あるいはアルコール類、グリコール類、ケトン類、エステル類、アミド類などの溶媒に溶かし、粒子形成中、化学増感前あるいは後に添加することができる。乳剤製造工程のどの過程で添加してもよいが、特に好ましいのは粒子成長中に添加する方法である。あらかじめ反応容器に添加するのもよいが、粒子形成の適当な時期に添加する方が好ましい。また水溶性銀塩あるいは水溶性アルカリハライドの水溶液にあらかじめ還元増感剤を添加しておき、これらの水溶液を用いて粒子形成してもよい。また粒子形成に伴って還元増感剤の溶液を何回かに分けて添加しても連続して長時間添加するのも好ましい方法である。
【００９５】
米国特許第３，７７２，０３１号に記載されているようなカルコゲナイド化合物を乳剤調製中に添加する方法も有用な場合がある。Ｓ、Ｓｅ、Ｔｅ以外にもシアン塩、チオシアン塩、セレノシアン酸、炭酸塩、リン酸塩、酢酸塩を存在させてもよい。
【００９６】
本発明の請求項２，１０，１８，２６，３４記載のハロゲン化銀乳剤は、銀核の酸化剤を含有することを特徴としている。銀に対する酸化剤とは、金属銀に作用して銀イオンに変換せしめる作用を有する化合物をいう。特に、ハロゲン化銀粒子の形成過程および化学増感過程において副生するきわめて微小な銀粒子を銀イオンに変換せしめる化合物が有効である。ここで生成する銀イオンは、例えば、ハロゲン化銀、硫化銀、セレン化銀のような水に難溶の銀塩を形成してもよく、又、硝酸銀のような水に易溶の銀塩を形成してもよい。銀に対する酸化剤は、無機物であっても、有機物であってもよい。無機の酸化剤としては、オゾン、過酸化水素及びその付加物（例えば、ＮａＢＯ₂・Ｈ₂Ｏ₂・３Ｈ₂Ｏ、２ＮａＣＯ₃・３Ｈ₂Ｏ₂、Ｎａ₄Ｐ₂Ｏ₇・２Ｈ₂Ｏ₂、２Ｎａ₂ＳＯ₄・Ｈ₂Ｏ₂・Ｈ₂Ｏ）、ペルオキシ酸塩（例えば、Ｋ₂Ｓ₂Ｏ₈、Ｋ₂Ｃ₂Ｏ₆、Ｋ₄Ｐ₂Ｏ₈）、ペルオキシ錯体化合物（例えば、Ｋ₂［Ｔｉ（Ｏ₂）Ｃ₂Ｏ₄］・３Ｈ₂Ｏ、４Ｋ₂ＳＯ₄・Ｔｉ（Ｏ₂）ＯＨ・ＳＯ₄・２Ｈ₂Ｏ、Ｎａ₃［ＶＯ（Ｏ₂）（Ｃ₂Ｏ₄）₂・６Ｈ₂Ｏ］）、過マンガン酸塩（例えばＫＭｎＯ₄）、クロム酸塩（例えばＫ₂Ｃｒ₂Ｏ₇）等の酸素酸塩、沃度や臭素等のハロゲン元素、過ハロゲン酸塩（例えば、過沃素酸カリウム）、高原子価の金属の塩（例えば、ヘキサシアノ第二鉄酸カリウム）及びチオスルホン酸塩等がある。又、有機の酸化剤としては、ｐ−キノン等のキノン類、過酢酸や過安息香酸等の有機過酸化物、活性ハロゲンを放出する化合物（例えば、Ｎ−ブロムサクシンイミド、クロラミンＴ、クロラミンＢ）が挙げられる。
【００９７】
好ましい酸化剤は、オゾン、過酸化水素及びその付加物、ハロゲン元素、チオスルフォン酸塩、キノン類であり、特に好ましくは下記一般式（１）乃至（３）で示されるチオスルフォン酸塩化合物であり、最も好ましいのは一般式（１）で示される化合物である。
【００９８】
（１） Ｒ−ＳＯ₂Ｓ−Ｍ
（２） Ｒ−ＳＯ₂Ｓ−Ｒ₁
（３） Ｒ−ＳＯ₂Ｓ−Ｌ_m−ＳＳＯ₂−Ｒ₂
式中、Ｒ、Ｒ₁、Ｒ₂は脂肪族基、芳香族基或いはヘテロ環基を表し、各々同一でも異なってもよく、又Ｍは陽イオンを表す。Ｌは二価の連結基を表し、ｍは０又は１である。
【００９９】
一般式（１）乃至（３）のチオスルフォン酸系化合物を更に詳しく説明すると、Ｒ、Ｒ₁、Ｒ₂が脂肪族基の場合、飽和又は不飽和の、直鎖、分岐状又は環状の、脂肪族炭化水素基であり、好ましくは炭素数が１〜２２のアルキル基、炭素数が２〜２２のアルケニル基、アルキニル基であり、これらは、置換基を有していてもよい。アルキル基としては、例えばメチル、エチル、プロピル、ブチル、ペンチル、へキシル、オクチル、２−エチルヘキシル、デシル、ドデシル、ヘキサデシル、オクタデシル、シクロヘキシル、イソプロピル及びｔ−ブチルが挙げられる。
【０１００】
アルケニル基としては、例えばアリル、ブテニルが挙げられる。アルキニル基としては、例えばプロパルギル、ブチニルが挙げられる。
【０１０１】
Ｒ、Ｒ₁、Ｒ₂が芳香族基の場合は、単環又は縮合環の芳香族基が含まれ、好ましくは炭素数が６〜２０のもの、例えばフェニル、ナフチルが挙げられる。これらは、置換されていてもよい。
【０１０２】
Ｒ、Ｒ₁、Ｒ₂がヘテロ環基の場合は、窒素、酸素、硫黄、セレン、テルルから選ばれる元素を少なくとも一つ有し、かつ炭素原子を少なくとも１つ有する３乃至１５員環のものであり、好ましくは３〜６員環が好ましく、例えばピロリジン、ピペリジン、ピリジン、テトラヒドロフラン、チオフェン、オキサゾール、チアゾール、イミダゾール、ベンゾチアゾール、ベンズオキサゾール、ベンズイミダゾール、セレナゾール、ベンゾセレナゾール、テルラゾール、トリアゾール、ベンゾトリアゾール、テトラゾール、オキサジアゾール、チアジアゾール環が挙げられる。
【０１０３】
Ｒ、Ｒ₁、Ｒ₂の置換基としては、例えばアルキル基（例えば、メチル、エチル、へキシル）、アルコキシ基（例えば、メトキシ、エトキシ、オクチルオキシ）、アリール基（例えば、フェニル、ナフチル、トリル）、ヒドロキシ基、ハロゲン原子（例えばフッ素、塩素、臭素、沃素）、アリーロキシ基（例えば、フェノキシ）、アルキルチオ基（例えば、メチルチオ、ブチルチオ）、アリールチオ基（例えば、フェニルチオ）、アシル基（例えば、アセチル、プロピオニル、ブチリル、バレリル）、スルホニル基（例えば、メチルスルホニル、フェニルスルホニル）、アシルアミノ基（例えば、アチルアミノ、ベンゾイルアミノ）、スルホニルアミノ基（例えば、メタンスルホニルアミノ、ベンゼンスルホニルアミノ）、アシロキシ基（例えば、アセトキシ、ベンゾキシ）、カルボキシル基、シアノ基、スルホ基、アミノ基、−ＳＯ₂ＳＭ基（Ｍは１価の陽イオンを示す）、−ＳＯ₂Ｒ基（Ｒはアルキル基を示す）が挙げられる。Ｌで表される２価の連結基としては、Ｃ，Ｎ，Ｓ及びＯから選ばれる少なくとも１種を含む原子又は原子団である。
【０１０４】
具体的にはアルキレン基、アルケニレン基、アルキニレン基、アリーレン基、−Ｏ−、−Ｓ−、−ＮＨ−、−ＣＯ−、−ＳＯ₂−等の単独又はこれらの組合せからなるものである。Ｌは好ましくは二価の脂肪族基又は二価の芳香族基である。
【０１０５】
上記二価の脂肪族基としては例えば−（ＣＨ₂）−ｎ（ｎは１〜１２）、−ＣＨ₂−ＣＨ＝ＣＨ−ＣＨ₂−、−ＣＨ₂Ｃ≡ＣＣＨ₂−、−ＣＨ₂−１，４−シクロヘキシレン−ＣＨ₂−、キシリレン基、などが挙げられる。Ｌの二価の芳香族基としては、例えばフェニレン基、ナフチレン基などが挙げられる。これらの置換基は、更にこれまで述べた置換基で置換されていてもよい。
【０１０６】
Ｍは陽イオンを表し、好ましくは、金属イオン又は有機カチオンである。金属イオンとしては、例えばリチウムイオン、ナトリウムイオン、カリウムイオンが挙げられる。有機カチオンとしては、例えばアンモニウムイオン（アンモニウム、テトラメチルアンモニウム、テトラブチルアンモニウム等）、ホスホニウムイオン（テトラフェニルホスホニウム）、グアニジル基が挙げられる。
【０１０７】
一般式（１）乃至（３）で表される化合物がポリマーである場合、その繰り返し単位として例えば以下のものが挙げられる。
【０１０８】
【化２】

【０１０９】
これらのポリマーは、ホモポリマーでもよいし他の共重合モノマーとのコポリマーでもよい。一般式（１）乃至（３）で表される化合物の具体例を以下に挙げるが、これらに限定されるものではない。
【０１１０】
【化３】

【０１１１】
【化４】

【０１１２】
【化５】

【０１１３】
【化６】

【０１１４】
【化７】

【０１１５】
【化８】

【０１１６】
【化９】

【０１１７】
一般式（１）乃至（３）で表される化合物は、特開昭５４−１０１９号、英国特許９７２，２１１、Ｊｏｕｒｎａｌ ｏｆ Ｏｒｇａｎｉｃ Ｃｈｅｍｉｓｔｒｙ（ジャーナル オブ オーガニックケミストリー）５３巻、３９６頁（１９８８）に記載の方法又はそれに準じた方法により合成できる。
【０１１８】
本発明においては、銀１モルに対する一般式（１）乃至（３）で表される化合物の添加量は１０^-7〜１０^-1モルの範囲から選ぶのが望ましい。好ましくは１０^-6〜１０^-2モルの範囲であり、より好ましくは１０^-5〜１０^-3モルの範囲である。一般式（１）乃至（３）で表される化合物はハロゲン化銀乳剤を製造する工程中、例えばハロゲン化銀粒子形成中、化学増感前或いは後のどの段階で添加してもよいが、好ましいのは化学増感前であり、より好ましくは粒子形成中であり、又、一般式（１）乃至（３）で表される化合物は還元増感開始前或いは開始後どちらの段階で添加してもよいが、還元増感開始後に添加することが好ましい。
【０１１９】
一般式（１）乃至（３）で表される化合物を製造工程中に添加せしめるには、写真乳剤に添加剤を加える場合に通常用いられる方法を適用できる。例えば、水溶性の化合物は適当な濃度の水溶液とし、水に不溶又は難溶性の化合物は水と混和しうる適当な有機溶媒、例えばアルコール類、グリコール類、ケトン類、エステル類、アミド類などのうち、写真特性に悪い影響を与えない溶媒に溶解し、溶液として添加できる。
【０１２０】
本発明の請求項３，４，１１，１２，１９，２０，２１，２７，２８，３５，３６記載のハロゲン化銀粒子は、少なくとも１種以上の多価金属化合物を含有する。
【０１２１】
ここで、用語の定義をしておくが、『ドーピング』、あるいは『ドープ』はハロゲン化銀粒子中に銀イオン又はハロゲン化物イオン以外の物質を含有させることを指す。用語『ドーパント』はハロゲン化銀粒子にドープする化合物を指す。用語『メタルドーパント』はハロゲン化銀粒子にドープする多価金属化合物を指す。
【０１２２】
ドーピングをハロゲン化銀粒子に施すにはハロゲン化銀粒子の物理熟成中にドーピングを行ってもよいし、水溶性銀塩および水溶性ハロゲン化アルカリの添加中にドーピングを行ってもよいし、またこれらの添加を一時止めた状想でドーピングを施しその後さらなる沈殿工程を行うという方法でもよいことを意味する。また、ハロゲン化粒子形成終了後にドーピングを施し、ハロゲン化銀粒子の表面にドーパントを導入しても良いし、化学熟成中、前後に導入しても良い。ハロゲン化銀粒子へのドーパントの導入は、高濃度での導入及び／または粒子核形成前、核形成中若しくは核形成直後の導入される場合、ドーパントを粒子成長中に存在させて形成できる。この際、ドーパントの導入は、粒子形成後まで遅延させ、粒子成長の初期に割当の量導入し、好ましくはそのまま継続するか、ハロゲン化銀粒子成長の後段階全体を通じて行う。ハロゲン化銀に有用であることが知られている通常のドーパントはいずれも用いることができる。元素の周期律表内の広範囲の周期及び族から選択される写真学的に有用なドーパントが報告されている。
【０１２３】
本明細書で用いられる周期及び族は、Ａｍｅｒｉｃａｎ Ｃｈｅｍｉｃａｌ Ｓｏｃｉｅｔｙにより採用され、Ｃｈｅｍｉｃａｌ ａｎｄ Ｅｎｇｉｎｅｅｒｉｎｇ Ｎｅｗｓ、１９８５年２月４日、第２６頁に公表されている元素の周期表に基づいている。通常のドーパントには、Ｆｅ、Ｃｏ、Ｎｉ、Ｒｕ、Ｒｈ、Ｐｄ、Ｒｅ、Ｏｓ、Ｉｒ、Ｐｔ、Ｍｇ、Ａｌ、Ｃａ、Ｓｃ、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｃｕ、Ｚｎ、Ｇａ、Ｇｅ、Ａｓ、Ｓｅ、Ｓｒ、Ｙ、Ｍｏ、Ｚｒ、Ｎｂ、Ｃｄ、Ｉｎ、Ｓｎ、Ｓｂ、Ｂａ、Ｌａ、Ｗ、Ａｕ、Ｈｇ、Ｔｌ、Ｐｂ、Ｂｉ、Ｃｅ及びＵ等の元素の周期表の第３〜７周期（最も一般的には第４〜６周期）等の原子、そのイオン及び錯体が含まれる。
【０１２４】
より好ましくはガリウム、インジウム、タリウム、鉛等の原子、そのイオン及び錯体が含まれる。ドーパントは、（ａ）感度の増加、（ｂ）高若しくは低照度相反則不軌の減少、（ｃ）コントラストの変動の増加、低下若しくは減少、（ｄ）圧力感受性の減少、（ｅ）色素減感の減少、（ｆ）安定性（熱不安定性の減少を含む）の増加、（ｇ）最小濃度の減少及び／又は（ｈ）最大濃度の増加に用いることができる。
【０１２５】
Ｒｅｓｅａｒｃｈ Ｄｉｓｃｌｏｓｕｒｅ、第３６７巻、１９９４年１１月、アイテム３６７３６には、浅い電子トラップ（ＳＥＴ）ドーパントを選定する基準のわかりやすい説明がある。特定の好ましい態様では、ドーパントとして下式を満足するヘキサ配位錯体を使用することが意図される。
【０１２６】
〔ＭＬ₆〕ⁿ
式中、Ｍは充満フロンティア軌道多価金属イオン、好ましくはＦｅ²⁺、Ｒｕ²⁺、Ｏｓ²⁺、Ｃｏ³⁺、Ｒｈ³⁺、Ｉｒ³⁺、Ｐｄ⁴⁺若しくはＰｔ⁴⁺であり、Ｌ₆は独立して選択することができる６個の配位錯体リガンドを表すが、但し、リガンドの少なくとも４個はアニオンリガンドであり、リガンドの少なくとも１個（好ましくは少なくとも３個及び最適には少なくとも４個）は何れのハロゲン化物リガンドよりも電気的陰性が高い。ｎは２−、３−若しくは４−である。浅い電子トラップを提供することができるドーパントの具体例を以下に示す。
【０１２７】
ＳＥＴ−１ 〔Ｆｅ（ＣＮ）₆〕^4-
ＳＥＴ−２ 〔Ｒｕ（ＣＮ）₆〕^4-
ＳＥＴ−３ 〔Ｏｓ（ＣＮ）₆〕^4-
ＳＥＴ−４ 〔Ｒｈ（ＣＮ）₆〕^3-
ＳＥＴ−５ 〔Ｉｒ（ＣＮ）₆〕^3-
ＳＥＴ−６ 〔Ｆｅ（ピラジン）（ＣＮ）₅〕^4-
ＳＥＴ−７ 〔ＲｕＣｌ（ＣＮ）₅〕^4-
ＳＥＴ−８ 〔ＯｓＢｒ（ＣＮ）₅〕^4-
ＳＥＴ−９ 〔ＲｈＦ（ＣＮ）₅〕^3-
ＳＥＴ−１０ 〔ＩｒＢｒ（ＣＮ）₅〕^3-
ＳＥＴ−１１ 〔ＦｅＣＯ（ＣＮ）₅〕^3-
ＳＥＴ−１２ 〔ＲｕＦ₂（ＣＮ）₄〕^4-
ＳＥＴ−１３ 〔ＯｓＣｌ₂（ＣＮ）₄〕^4-
ＳＥＴ−１４ 〔ＲｈＩ₂（ＣＮ）₄〕^3-
ＳＥＴ−１５ 〔ＩｒＢｒ₂（ＣＮ）₄〕^3-
ＳＥＴ−１６ 〔Ｒｕ（ＣＮ）₅（ＯＣＮ）〕^4-
ＳＥＴ−１７ 〔Ｒｕ（ＣＮ）₅（Ｎ₃）〕^4-
ＳＥＴ−１８ 〔Ｏｓ（ＣＮ）₅（ＳＣＮ）〕^4-
ＳＥＴ−１９ 〔Ｒｈ（ＣＮ）₅（ＳｅＣＮ）〕^3-
ＳＥＴ−２０ 〔Ｉｒ（ＣＮ）₅（ＨＯＨ）〕^2-
ＳＥＴ−２１ 〔Ｆｅ（ＣＮ）₃Ｃｌ₃〕^3-
ＳＥＴ−２２ 〔Ｒｕ（ＣＯ）₂（ＣＮ）₄〕^3-
ＳＥＴ−２３ 〔Ｏｓ（ＣＮ）Ｃｌ₅〕^4-
ＳＥＴ−２４ 〔Ｃｏ（ＣＮ）₆〕^3-
ＳＥＴ−２５ 〔Ｉｒ（ＣＮ）₄（オキサレート）〕^3-
ＳＥＴ−２６ 〔Ｉｎ（ＮＣＳ）₆〕^3-
ＳＥＴ−２７ 〔Ｇａ（ＮＣＳ）₆〕^3-
ＳＥＴ−２８ 〔Ｃｏ（ＮＯ₂）₆〕^3-
ＳＥＴ−２９ 〔Ｉｒ（ＮＯ₂）₆〕^3-
ＳＥＴ−３０ ＩｎＣｌ₃
ＳＥＴ−３１ Ｇａ（ＮＯ₃）₃
ＳＥＴ−３２ ＴｌＣｌ
ＳＥＴ−３３ Ｐｂ（ＮＯ₃）₂
更に、米国特許第５，０２４，９３１号（Ｅｖａｎｓ等）に記載されているように、オリゴマー配位錯体を用いてスピード増加することも意図される。また、特開平１１−２４１９４号、同１１−１０９５３７号（押山等）に記載されているように、五配位、四配位ドーパントを用いても良いし、特開平１１−１０２０４２号、同１１−１８４０３６号に記載のハロゲン化銀への吸着基を有する配位子を含む金属錯体を使用することも可能である。
【０１２８】
メタルドープの効果を最大限に引き出すｐＡｇ制御について説明する。メタルドーピングの工程とそれ以降のｐＡｇを制御することでメタルドープの効果を最大限に引き出したことにある。ここでメタルドーピングの工程とは具体的にはメタルドープ時にｐＡｇを８．５以下に制御し、それ以降の粒子成長ｐＡｇを９以上に制御することで達成できた。より好ましくはメタルドープ時にｐＡｇを８．３以下に制御し、それ以降のｐＡｇを９．３以上に制御することである。またｐＡｇの操作においては、求める粒子性能によってドープ率を段階的に上昇させるためにｐＡｇを徐々に上げる、或いは段階的に下降させるために徐々に下げる等の工夫が可能である。
【０１２９】
本発明の請求項３，１１，１９，２７，３５記載のハロゲン化銀乳剤は、少なくとも１種の多価金属の６配位シアノ錯体を含有することを特徴としており、特に好ましいメタルドーパントとして、Ｋ₄［Ｆｅ（ＣＮ）₆］、Ｋ₃［Ｆｅ（ＣＮ）₆］、Ｋ₄［Ｒｕ（ＣＮ）₆］が挙げられる。
【０１３０】
メタルドーパントの、ハロゲン化銀粒子中の濃度分布は、粒子を表面から内部へ少しずつ溶解し、各部分のドーパント含有量を測定することにより求められる。具体例として以下に述べる方法があげられる。
【０１３１】
メタルの定量に先立ち、ハロゲン化銀乳剤を以下のように前処理する。まず、乳剤約３０ｍｌに０．２％アクチナーゼ水溶液５０ｍｌを加え、４０℃で３０分間攪拌してゼラチン分解を行なう。この操作を５回繰り返す。遠心分離後、メタノール５０ｍｌで５回、１Ｎ硝酸５０ｍｌで２回，超純水で５回洗浄を繰り返し、遠心分離後ハロゲン化銀のみを分離する。得られたハロゲン化銀の粒子表面部分をアンモニア水溶液あるいはｐＨ調整したアンモニア（アンモニア濃度及びｐＨはハロゲン化銀の種類及び溶解量に応じて変化させる）により溶解する。ハロゲン化銀のうち臭化銀粒子の極表面を溶解する方法としては、ハロゲン化銀２ｇに対し約１０％アンモニア水溶液２０ｍｌを用いて粒子表面より約３％程度の溶解をすることができる。この時、ハロゲン化銀の溶解量はハロゲン化銀の溶解を行なった後のアンモニア水溶液とハロゲン化銀を遠心分離し、得られた上澄み液に存在している銀量を高周波誘導プラズマ質量分析装置（ＩＣＰ−ＭＳ）高周波誘導プラズマ発光分析装置（ＩＣＰ−ＡＥＳ）、あるいは原子吸光にて定量できる。表面溶解後のハロゲン化銀に含まれるメタル量と溶解を行なわないトータルのハロゲン化銀のメタル量の差から、粒子表面約３％に存在するハロゲン化銀１モル当たりのメタル量を求めることができる。メタルの定量方法としては、チオ硫酸アンモニウム水溶液、チオ硫酸ナトリウム水溶液、あるいはシアン化カリウム水溶液に溶解し、マトリックスマッチングしたＩＣＰ−ＭＳ法、ＩＣＰ−ＡＥＳ法、あるいは原子吸光法があげられる。このうち溶剤としてシアン化カリウム、分析装置としてＩＣＰ−ＭＳ（ＦＩＳＯＮ Ｅｌｅｍｅｎｔａｌ Ａｎａｌｙｓｉｓ社製）を用いる場合は、ハロゲン化銀約４０ｍｇを５ｍｌの０．２Ｎシアン化カリウムに溶解後、１０ｐｐｂになるように内標準元素Ｃｓ溶液を添加し、超純水にて１００ｍｌに定容したものを測定試料とする。そしてメタルフリーのハロゲン化銀を用いてマトリックスを合わせた検量線を用いてＩＣＰ−ＭＳにより測定試料中のメタルの定量を行なう。この時、測定試料中の正確な銀量は超純水で１００倍稀釈した測定試料をＩＣＰ−ＡＥＳ、あるいは原子吸光にて定量できる。なお、このような粒子表面の溶解を行なった後、ハロゲン化銀粒子を超純水にて洗浄後、上記と同様な方法で粒子表面の溶解を繰り返すことにより、ハロゲン化銀粒子内部方向のメタル量の定量を行なうことができる。
【０１３２】
本発明の平板粒子のメタルドーパントの好ましい含有量は通常の濃度（ここで、濃度とは、平板状粒子における総銀を基準とした総銀を基準とした濃度である）で有効である。一般的に、浅い電子トラップ形成ドーパントの好ましい濃度は、ハロゲン化銀１モルあたり１×１０^-9モル以上１×１０^-2モル以下の範囲が適当であり、より好ましくは１×１０^-5モル以上１×１０^-3モル以下の範囲が好ましい。
【０１３３】
本発明の請求項４，１２，２０，２８，３６記載のメタルドーパントは、予めハロゲン化銀微粒子乳剤にドープした状態で基盤粒子に添加する事によって、その効果を有効に発現する。この場合、特に好ましいメタルドーパントとして、Ｐｂ（ＮＯ₃）₂、Ｋ₂ＩｒＣｌ₆、Ｋ₃ＩｒＣｌ₆、Ｋ₂ＩｒＢｒ₆、ＩｎＣｌ₃があげられる。このとき、ハロゲン化銀微粒子１モルに対するメタルドーパントの濃度は１×１０^-1モル〜１×１０^-7モルが好ましく、１×１０^-3モル〜１×１０^-5モルが更に好ましい。
【０１３４】
メタルドーパントを予めハロゲン化銀微粒子にドープする方法としては、メタルドーパントをハライド溶液に溶解した状態で微粒子形成を行う事が好ましい。
【０１３５】
ハロゲン化銀微粒子のハロゲン組成は、臭化銀、沃化銀、塩化銀、沃臭化銀、塩臭化銀、塩沃臭化銀のいずれでもよいが、基盤粒子と同じハロゲン組成とする事が好ましい。
【０１３６】
メタルドーパントを含有したハロゲン化銀微粒子の基盤粒子への沈着を行う時期は、基盤粒子形成後から化学増感開始前までの間ならどこでもよいが、脱塩工程終了後から化学増感開始前までの間が特に好ましい。
【０１３７】
基盤乳剤の塩濃度が低い状態で微粒子乳剤を添加する事によって、基盤粒子の活性が最も高い部分に、ハロゲン化銀微粒子はメタルドーパントと共に沈着する。すなわち、本発明の平板粒子のコーナー、エッジを含む外周領域に効率的に沈着させる事ができる。この沈着させるとは、ハロゲン化銀微粒子がそのまま基盤粒子に凝集、吸着するのではなく、ハロゲン化銀微粒子と基盤粒子が共存する反応系内で、ハロゲン化銀微粒子が溶解し、基盤粒子上にハロゲン化銀として再生成させることをいう。すなわち、上記方法で得られた乳剤の一部を取り出し、電子顕微鏡観察を行った際に、ハロゲン化銀微粒子が観察されず、かつ、基盤粒子表面にはエピタキシャル状の突起部分が観察されない事をいう。
【０１３８】
添加するハロゲン化銀微粒子は、基盤粒子１モル当たり１×１０^-7モル〜０．５モルの銀量を添加する事が好ましく、１×１０^-5モル〜１×１０^-1モルの銀量を添加する事が更に好ましい。
【０１３９】
ハロゲン化銀微粒子を沈着させるための物理熟成条件は、３０℃〜７０℃／１０分間〜６０分間の間で任意に選ぶことができる。
【０１４０】
本発明の請求項５，１３，２１，２９，３７に係る発明における粒子間距離制御法について説明する。粒子間距離制御法とは、ハロゲン化銀粒子の形成工程において、粒子の形成を行う反応物溶液を濃縮して、反応物溶液の容積を減少せしめる、あるいは粒子形成のための添加液による容積増加分を濃縮して一定に保つ、あるいは該容積増加を抑制することによって、
平均粒子間距離＝［反応物溶液の容積／反応物溶液中の成長粒子数］１／３
で規定される反応物溶液中のハロゲン化銀粒子間の平均粒子間距離を制御する方法である。
【０１４１】
具体的には、粒子間距離制御法は、ハロゲン化銀粒子形成のための反応容器に、例えば限外濾過装置のような濃縮機構を接続した装置を用いて、粒子の形成工程において水あるいは可溶性物を含む水溶液のみを、反応液から除去することにより達成される。
【０１４２】
該濃縮機構はパイプ等で反応容器に接続され、ポンプ等の反応物溶液の循環機構により反応物溶液を反応容器と濃縮機構間で任意の流量で循環させ、任意に停止させることが可能であり、さらには、該濃縮機構によって反応物溶液から抜きとられる塩を含む水溶液の容量を検出する装置を有し、かつその量を任意に制御することが可能な機構を備える設備である。また、必要に応じてその他の機能を付与することも可能である。
【０１４３】
さらに本発明のハロゲン化銀乳剤を製造する装置としては、温度の設定された水を反応容器に添加し、平均粒子間距離を増大せしめる機構を有する装置である事が好ましい。
【０１４４】
本発明におけるハロゲン化銀粒子の成長過程における粒子間距離の制御は、ハロゲン化銀乳剤の写真性能向上と乳剤収率向上の両立を目的としており、写真性能の劣化を伴う乳剤収率の向上は本発明の意図するところではない。
【０１４５】
本発明に好ましく適用できるハロゲン化銀乳剤の製造装置の一態様として、限外濾過装置によって粒子成長過程における平均粒子間距離を任意に制御し、持続することが可能なハロゲン化銀乳剤の製造装置の一例を図１を参考に説明する。
【０１４６】
反応容器１は最初から、分散媒体３を含有している。この装置は反応容器１に、少なくとも１種の銀塩水溶液、好ましくは硝酸銀水溶液を添加するための銀添加ライン４と、少なくとも１種のハロゲン化塩水溶液、好ましくは臭素や沃素、塩素のアルカリ金属塩水溶液、またはアンモニウム塩水溶液、或いはそれらの混合物を添加するためのハライド添加ライン５を有する。また、ハロゲン化銀乳剤調製過程で、分散媒体及び反応物溶液（分散媒体とハロゲン化銀粒子の混合物）を撹拌するための撹拌機構２を有する。この撹拌機構はあらゆる通常の様式が可能である。銀塩水溶液は銀添加ライン４から、銀添加バルブ２０によって制御された流量で反応容器に添加される。ハロゲン塩水溶液はハライド添加ライン５から、ハライド添加バルブ２１によって制御された流量で反応容器に添加される。この銀添加ライン４およびハライド添加ライン５を通じての溶液の添加は、液面添加でもよいが、より好ましくは撹拌機構２近傍の液中に添加する方がよい。撹拌機構２は、銀塩水溶液およびハロゲン塩水溶液を分散媒体と混合させ、可溶性銀塩が可溶性ハロゲン化物塩と反応してハロゲン化銀を生成することを可能にする。
【０１４７】
第一段階のハロゲン化銀形成中、即ち核生成工程において、基盤となるハロゲン化銀核粒子を含む分散物（反応物溶液）が生成される。続いて必要に応じて熟成工程を経て核形成工程を終了する。その後、銀塩水溶液およびハロゲン塩水溶液の添加を継続すると、第二段階のハロゲン化銀形成、即ち成長工程段階へ移り、その工程で反応生成物として生じた追加のハロゲン化銀が、最初に生成されたハロゲン化銀核粒子の上に沈積して、これら粒子のサイズを増大させる。本発明では、反応容器への銀塩水溶液およびハロゲン塩水溶液の添加による粒子形成過程で、反応容器内の反応物溶液の一部が循環ポンプ１３によって、液取り出しライン８を通して限外濾過ユニット１２に送られ、液戻しライン９を通して反応容器に戻される。その際、液戻しライン９の途中に設けられた圧力調整用バルブ１８により限外濾過ユニット１２にかかる圧力を調節して、反応物溶液中に含まれる水溶性塩の溶液の一部を限外濾過ユニットにより分離し、透過液排出ライン１０を通して系外に排出する。このような方法で、反応容器への銀塩水溶液およびハロゲン塩水溶液の添加による粒子成長過程においても、粒子間距離を任意に制御しながらの粒子形成が可能となる。
【０１４８】
本発明においてこの方法を適用するときには、限外濾過膜によって分離される水溶性塩の溶液の透過液量（限外濾過フラックス）を任意に制御することが好ましい。例えばその場合には、透過液排出ライン１０の途中に設けられた流量調節用バルブ１９を用いて限外濾過フラックスを任意に制御できる。その際、限外濾過ユニット１２の圧力変動を最小限に抑えるために、透過液戻りライン１１の途中に設けられたバルブ２５を開放して透過液戻りライン１１を使用しても良い。あるいは、バルブ２５を閉じて透過液戻りライン１１を使用しなくとも良く、それは操作条件により任意に選択することが可能である。また限外濾過フラックスの検出には透過液排出ライン１０の途中に設けられた流量計１４を使用しても良いし、透過液受け容器２７と秤２８を用いて質量変化により検出しても良い。
【０１４９】
本発明において、粒子成長過程における限外濾過法による濃縮は、粒子形成過程を通じて連続して実施しても良いし、断続的に実施しても良い。但し、粒子成長過程において限外濾過法を適用する場合には、限外濾過工程への反応物溶液の循環を開始した以降は、少なくとも粒子形成終了時まで反応物溶液の循環を継続することが好ましい。従って、濃縮を中断している時も限外濾過ユニットへの反応物溶液の循環は継続していることが好ましい。これは、反応容器内の粒子と限外濾過工程の粒子間における成長偏在を回避するためである。また、限外濾過工程を通る循環流量は十分に高くすることが好ましい。具体的には、ハロゲン化銀反応物溶液の液取り出しラインおよび液戻しラインを含む限外濾過ユニット内における滞留時間は、３０秒以内が好ましく、１５秒以内がより好ましく、さらには１０秒以内が特に好ましい。
【０１５０】
液取り出しライン８、液戻しライン９、限外濾過ユニット１２及び循環ポンプ１３等を含む限外濾過工程の容積は、反応容器容積の容積の３０％以下であることが好ましく、２０％以下であることがより好ましく、１０％以下であることが特に好ましい。
【０１５１】
このように、限外濾過工程を適用することにより、全ハロゲン化銀反応物溶液の容量は粒子形成中任意に低下させることができる。また、添加ライン７から水を添加することによって、ハロゲン化銀反応物溶液の容量を任意に保つことも可能である。
【０１５２】
本発明において、限外濾過を実施する際に用いることができる限外濾過モジュール及び循環ポンプに特別な制限はないが、ハロゲン化銀乳剤に作用して写真性能等に悪影響を及ぼすような材質及び構造は避けることが好ましい。また、限外濾過モジュールに用いられる限外濾過膜の分画分子量も任意に選択することができる。例えば、ハロゲン化銀乳剤に含まれるゼラチン等の分散媒や乳剤調製時に使用した化合物を粒子成長過程で除去したい場合には、除去対象物の分子量以上の分画分子量を有する限外濾過膜を選択することができ、また、除去したくない場合には、除去対象物の分子量以下の分画分子量を有する限外濾過膜を選択することができる。
【０１５３】
本発明において、粒子形成に粒子間距離制御法を用いる、あるいは粒子形成中に粒子間距離制御法を適用するとは、
（１）ハロゲン化銀粒子の形成工程において前記の濃縮機構を用いて、反応物溶液の容積を減少せしめる
（２）ハロゲン化銀粒子の形成工程において前記の濃縮機構を用いて、ハロゲン化銀形成のための添加液量と同量の水あるいは可溶性物を含む水溶液を反応物溶液から除去し、反応物溶液の容積を一定に保持する
（３）ハロゲン化銀粒子の形成工程において前記の濃縮機構を用いて、ハロゲン化銀形成のための添加液の添加と同時に、水あるいは可溶性物を含む水溶液を反応物溶液から除去し、反応物溶液の容積増加を抑制する
以上の（１）〜（３）の操作あるいは、それらの組み合わせを意味する。上記（３）において、反応物溶液の容積は、容積増加の抑制の結果として、増加しても、減少してもよい。
【０１５４】
本発明においては、さらに、上記（１）〜（３）と組み合わせて、下記（４）の操作が好ましく用いられる。
【０１５５】
（４）水あるいは可溶性物を含む水溶液を添加し、反応物溶液の容積を増大せしめる
本発明において、限外濾過装置のような濃縮機構と反応容器間を、乳剤を循環させて水あるいは可溶性物を含む水溶液の除去を行わない状態は、粒子間距離制御法を適用しているとは規定しない。
【０１５６】
本発明において粒子間距離制御法は、必ずしも粒子形成の工程全体に渡って適用する必要は無い。むしろ、粒子形成工程の部分に用いることが好ましい。
【０１５７】
一般にハロゲン化銀乳剤の粒子形成工程は、核形成工程（核生成工程及び核の熟成工程から成る）とそれに続く該核の成長工程に大別される。また、予め造り置いた核乳剤（或いは種乳剤）を別途成長させることも可能である。該成長工程は、第１成長工程、第２成長工程、というようにいくつかの段階を含む場合もある。本発明において粒子間距離制御法は、ハロゲン化銀粒子の成長工程に適用されることが好ましい。
【０１５８】
本発明の乳剤において、転位線を有する粒子の形成に、粒子間距離制御法を適用する場合、粒子間距離制御法は転位線導入の直前および／または転位線導入直後の成長中に適用することが好ましい。具体的には転位線導入の直前および／または転位線導入直後の成長中に反応物溶液の液量を減少せしめるか一定に保持することが好ましい。転位線導入直後の成長中に粒子間距離制御法を適用する場合、転位線導入後から、全銀量の１〜５０％に亘って適用することが好ましく、５〜４０％に亘って適用することが好ましい。
【０１５９】
転位線を導入する場合の、より好ましい粒子間距離制御法の適用形態として、転位線の導入前に反応物溶液の容積を２／３以下に濃縮することがあげられる。さらに好ましくは反応物容積は１／２以下に濃縮され、特に好ましくは反応物容積は１／３以下に濃縮される。粒子間距離は、転位線の導入直前に２．６μｍ以下であることが好ましく、より好ましくは、２．３μｍ以下であり、更に好ましくは２．０μｍ以下であり、特に好ましくは、１．５μｍ以下であり、最も好ましくは１．０μｍ以下である。
【０１６０】
請求項６，１４，２２，３０，３８に係る発明のハロゲン化銀乳剤は、該ハロゲン化銀乳剤に含まれるハロゲン化銀粒子が粒子表面にハロゲン化銀突起物を有することを特徴とする。
【０１６１】
該ハロゲン化銀粒子表面にハロゲン化銀突起物を有するハロゲン化銀乳剤とは、ハロゲン化銀粒子表面にハロゲン化銀突起物を有するハロゲン化銀粒子がハロゲン化銀粒子の全投影面積の３０％以上であるハロゲン化銀乳剤のことをいい、全投影面積の５０％以上がハロゲン化銀粒子表面にハロゲン化銀突起物を有するハロゲン化銀粒子であることが好ましく、全投影面積の７０％以上がハロゲン化銀粒子表面にハロゲン化銀突起物を有するハロゲン化銀粒子であることがさらに好ましい。
【０１６２】
本発明の請求項６，１４，２２，３０，３８に記載の発明において、ハロゲン化銀粒子表面のハロゲン化銀突起物は、エピタキシャルであることが好ましく、該ハロゲン化銀突起物を有するハロゲン化銀粒子は平板状ハロゲン化銀粒子であることが好ましい。
【０１６３】
基板となるハロゲン化銀粒子（以下「ホスト粒子」と呼ぶこともある）の選択された部位にハロゲン化銀突起部をエピタキシャル配置することにより、像様露光での光子吸収ににより放出された伝導帯電子の増感部位への競争が減少され、よって感度が向上することが一般的に言われている。米国特許４，４３５，５０１号では、ホスト平板粒子の表面の選択された部位に銀塩をエピタキシャル付着することによる感度の向上を開示している。該米国特許では感度の増加は銀塩のエピタキシャル付着をホスト平板粒子の表面積の小部分に制限したためとしている。即ち、平板状粒子の主平面の限定された部分へのエピタキシャル配置は、主平面の全部またはほとんどを覆うエピタキシャル配置よりも効率的であり、更に好ましいのは、ホスト粒子のエッジに実質的に制限され、且つ主平面への被覆量が限定されるエピタキシャル配置であり、更に効率的で好ましいのは、ホスト粒子のコーナーまたはその近傍または他の別個の部位に制限されるエピタキシャル配置である。ホスト粒子それ自体の主平面のコーナーの間隔は、光電子競争をほぼ最大感度が実現できる程度に十分減少させる。前記米国特許４，４３５，５０１号では、エピタキシャル付着速度を遅くすることにより、ホスト粒子へのエピタキシャル配置部位の数を減少できると教示している。
【０１６４】
よって、本発明においても、ホスト粒子の表面積にエピタキシャル配置されるハロゲン化銀突起部は、ホスト粒子の表面積の小部分に制限することが好ましく、コーナーまたはその近傍に制限されることが特に好ましい。具体的には５０％未満であることが好ましく３０％未満であることが更に好ましい。また、エピタキシャル配置されるハロゲン化銀突起部の銀量は、ホスト粒子の銀量に対して０．３〜２５％であることが好ましく、０．５〜１５％であることが更に好ましい。
【０１６５】
本発明の最も好ましい態様の１つとしては、エピタキシャル配置されるハロゲン化銀突起部はホスト粒子のコーナーまたはその近傍の制限された位置に形成されることが好ましく、これを達成するための方法としては公知の方法を適用することができる。前記米国特許４，４３５，５０１号では、分光増感色素やアミノアザインデン類を部位指向体（ｓｉｔｅ ｄｉｒｅｃｔｏｒ）として吸着させる方法が開示されており、本発明においても好ましくは適用できる。
【０１６６】
ホスト粒子の構造的崩壊を回避するために、エピタキシャル配置されるハロゲン化銀突起部は、その総溶解度がホスト粒子を形成するハロゲン化銀の総溶解度よりも高いことが好ましい。よって、エピタキシャル配置されるハロゲン化銀突起部は、具体的には塩化銀であることが好ましい。塩化銀は臭化銀のように面心立方格子構造を形成するので、エピタキシャル付着を容易にする。
【０１６７】
ホスト粒子の構造的一体性を保持するために、エピタキシャル付着は、ホスト粒子を形成するハロゲン化物の溶解性を制限する条件下で行われることが好ましい。しかし、エピタキシャル配置されたハロゲン化銀突起部のハロゲン化物が、ホスト粒子からのものであるようにする場合がある。即ち、少量の臭化物及び場合によっては沃化物を含有する塩化銀突起部であるようにする。
【０１６８】
本発明の請求項７，１５，２３，３１，３９に記載のハロゲン化銀乳剤は、該ハロゲン化銀乳剤に含まれるハロゲン化銀粒子が塩化銀を含有することを特徴とする。
【０１６９】
該塩化銀を含有するハロゲン化銀写真乳剤とは、ハロゲン化銀写真乳剤中のハロゲン化銀粒子の平均塩化銀含有率が０．１〜１００モル％であるハロゲン化銀写真乳剤のことをいう。
【０１７０】
本発明の請求項７，１５，２３，３１，３９において、塩化銀を含有するハロゲン化銀写真乳剤中のハロゲン化銀粒子の平均塩化銀含有率は、０．３〜５０モル％であることが好ましく、０．５〜３０モル％がより好ましい。
【０１７１】
本発明の請求項７，１５，２３，３１，３９において、塩化銀以外の構成要素は臭化銀及び／又は沃化銀が好ましく、ハロゲン化銀組成として、塩化銀、沃塩化銀、沃塩臭化銀、塩臭化銀を用いることができる。
【０１７２】
本発明の請求項７，１５，２３，３１，３９において、ハロゲン化銀粒子中の平均塩化銀含有率が１０モル％より低い場合における好ましい形態の１つは、特願平１０−１５２８５２号、特開平１１−１８４０２８号、同１１−２７１９０１号、同１１−２５８７２０号等に記載のハロゲン化銀粒子最表層もしくはハロゲン化銀粒子の特定部分に塩化銀を含有するハロゲン化銀粒子であり、ハロゲン化銀粒子の頂点部に塩化銀を特異的に含有するハロゲン化銀粒子も好ましい。
【０１７３】
本発明の請求項７，１５，２３，３１，３９記載の発明のハロゲン化銀乳剤が塩臭化銀である場合、臭化銀がハロゲン化銀結晶の頂点又はその近傍に局在することが好ましい。このようなハロゲン化銀乳剤は塩化銀又は塩臭化銀粒子結晶上に増感色素又は抑制剤を吸着させた後、臭化銀微粒子を添加して熟成するか、水溶性の臭化物の溶液を添加してハロゲン置換することによって得ることができる。
【０１７４】
また、本発明の請求項７，１５，２３，３１，３９に記載の発明において、ハロゲン化銀粒子中の平均塩化銀含有率が１０モル％より高い場合、特にハロゲン化銀粒子中の平均塩化銀含有率が５０〜１００モル％である場合には、沃化銀及び／または臭化銀をハロゲン化銀粒子中のコア部もしくはシェル部、あるいはハロゲン化銀粒子表面の特定部位に局在させる形態も好ましい。
【０１７５】
本発明のハロゲン化銀乳剤に含まれる分散媒とは、ハロゲン化銀粒子に対する保護コロイド性を有する化合物である。該分散媒は、ハロゲン化銀粒子形成時の核生成工程から粒子成長工程に渡って存在させることが好ましい。本発明で好ましく用いることができる分散媒には、ゼラチンと親水性コロイドがある。ゼラチンとしては、通常分子量１０万程度のアルカリ処理ゼラチンや酸処理ゼラチン、或いは酸化処理したゼラチンや、Ｂｕｌｌ．Ｓｏｃ．Ｓｃｉ．Ｐｈｏｔｏ．Ｊａｐａｎ Ｎｏ．１６，Ｐ３０（１９６６）に記載されたような酵素処理ゼラチンを好ましく用いることができる。特に、ハロゲン化銀粒子の核生成時には平均分子量が１万〜７万のゼラチンを用いることが好ましく、平均分子量が１万〜５万のゼラチンを用いることがさらに好ましい。ゼラチンの平均分子量を小さくするために、ゼラチン分解酵素や過酸化水素等を用いてゼラチンを分解処理することができる。また、同様に核生成時にメチオニン含有量が少ないゼラチンを用いることも好ましい。分散媒単位質量（グラム）当たりのメチオニン含有量としては５０μモル以下が好ましく、２０μモル以下がより好ましい。ゼラチン中のメチオニン含有量は、過酸化水素等を用いてゼラチンを酸化処理することによって低減せしめることができる。
【０１７６】
親水性コロイドとしては、例えば、ゼラチン誘導体、ゼラチンと他の高分子とのグラフトポリマー、アルブミン、カゼインのような蛋白質；ヒドロキシエチルセルロース、カルボキシメチルセルロース、セルロース硫酸エステル類の如きセルロース誘導体、アルギン酸ソーダ、澱粉誘導体のような糖誘導体；ポリビニルアルコール、ポリビニルアルコール部分アセタール、ポリ−Ｎ−ビニルピロリドン、ポリアクリル酸、ポリメタクリル酸、ポリアクリルアミド、ポリビニルイミダゾール、ポリビニルピラゾールのような単一あるいは共重合体の如き多種の合成親水性高分子物質を用いることができる。ゼラチンとしては石灰処理ゼラチンのほか、酸処理ゼラチンやＢｕｌｌ．Ｓｏｃ．Ｓｃｉ．Ｐｈｏｔｏ．Ｊａｐａｎ．Ｎｏ．１６．Ｐ３０（１９６６）に記載されたような酵素処理ゼラチンを用いてもよく、また、ゼラチンの加水分解物や酵素分解物も用いることができる。
【０１７７】
請求項８，１６，２４，３２に係る発明において、ハロゲン化銀乳剤の粒子形成工程においては特開平５−７２６５８号公報、特開平９−１９７５９５号公報、特開平９−２５１１９３号公報などに記載の、ゼラチンのアミノ基を置換した化学修飾ゼラチンを好ましく使用することができる。
【０１７８】
粒子形成工程において化学修飾ゼラチンを用いる場合、粒子形成に用いる全分散倍の１０質量パーセント以上が、該化学修飾ゼラチンであることが好ましく、３０質量パーセント以上である事がより好ましく、５０質量パーセント以上であることがさらに好ましい。アミノ基の置換比率は３０％以上が好ましく、５０％以上がより好ましく、８０％以上がさらに好ましい。
【０１７９】
本発明のハロゲン化銀乳剤には、硫黄増感やセレン増感等のカルコゲン増感、金増感やパラジウム増感当の貴金属増感の少なくとも１つをハロゲン化銀乳剤の製造工程の任意の工程で施こすことができる。また、２種以上の増感法を組み合せることは好ましい。どの工程で化学増感するかによって種々のタイプの乳剤を調製することができる。粒子の内部に化学増感核を埋め込む態様、粒子表面から浅い位置に埋め込む態様、あるいは表面に化学増感核を作る態様がある。本発明が関係するハロゲン化銀乳剤は、目的に応じて化学増感核の場所を選ぶことができる。一般に好ましいのは表面近傍に少なくとも一種の化学増感核を形成する場合である。
【０１８０】
本発明のハロゲン化銀乳剤に対して好ましく実施しうる化学増感方法の一つは、カルコゲン化合物を用いた増感と貴金属を用いた増感の単独又は組合せであり、ジェームス（Ｔ．Ｈ．Ｊａｍｅｓ）著、ザ・フォトグラフィック・プロセス、第４版、マクミラン社刊、１９７７年、（Ｔ．Ｈ．Ｊａｍｅｓ，Ｔｈｅ Ｔｈｅｏｒｙ ｏｆ ｔｈｅ Ｐｈｏｔｏｇｒａｐｈｉｃ Ｐｒｏｃｅｓｓ，４ｔｈ ｅｄ，Ｍａｃｍｉｌｌａｎ，１９７７）６７〜７６頁に記載されるように活性ゼラチンを用いて行うことができるし、またリサーチ・ディスクロージャー１２０巻、１９７４年４月、１２００８；リサーチ・ディスクロージャー、３４巻、１９７５年６月、１３４５２、米国特許第２，６４２，３６１号、同第３，２９７，４４６号、同第３，７７３，０３１号、同第３，８５７，７１１号、同第３，９０１，７１４号、同第４，２２６，０１８号、および同第３，９０４，４１５号、並びに英国特許第１，３１５，７５５号に記載されるようにｐＡｇ５〜１０、ｐＨ５〜８および温度３０〜８０℃において硫黄、セレン、テルル、金、白金、パラジウムまたはこれら増感剤の複数の組合せとすることができる。
【０１８１】
貴金属増感においては、例えば、金、白金、パラジウムの貴金族塩を用いることができ、中でも特に金増感、パラジウム増感あるいは両者の併用が好ましい。金増感の場合には、例えば、塩化金酸、カリウムクロロオーレート、カリウムオーリチオシアネート、硫化金、金セレナイド等の公知の化合物を用いることができる。パラジウム化合物はパラジウム２価塩または４価の塩を意味する。好ましいパラジウム化合物は、Ｒ₂ＰｄＸ₆またはＲ₂ＰｄＸ₄で表される。ここでＲは水素原子、アルカリ金属原子またはアンモニウム基を表す。Ｘはハロゲン原子を表し塩素、臭素または沃素原子を表す。
【０１８２】
具体的には、例えば、Ｋ₂ＰｄＣｌ₄、（ＮＨ₄）₂ＰｄＣｌ₆、Ｎａ₂ＰｄＣｌ₄、（ＮＨ₄）₂ＰｄＣｌ₄、Ｌｉ₂ＰｄＣｌ₄、Ｎａ₂ＰｄＣｌ₆またはＫ₂ＰｄＢｒ₄が好ましい。金化合物およびパラジウム化合物はチオシアン酸塩あるいはセレノシアン酸塩と併用することが好ましい。
【０１８３】
本発明の乳剤に金増感を施す場合の金増感剤の好ましい量は、ハロゲン化銀１モル当り１×１０^-4〜１×１０^-7モルであり、さらに好ましいのは１×１０^-5〜５×１０^-7モルである。パラジウム化合物の好ましい範囲は１×１０^-3から５×１０^-7である。チオシアン化合物あるいはセレノシアン化合物の好ましい範囲は５×１０^-2から１×１０^-6である。
【０１８４】
本発明のハロゲン化銀乳剤に対して好ましく実施しうるカルコゲン増感法の一つに硫黄増感がある。硫黄増感剤としては、ハイポ、チオ尿素系化合物、ロダニン系化合物および米国特許第３，８５７，７１１号、同第４，２２６，０１８号および同第４，０５４，４５７号に記載されている硫黄含有化合物を用いることができる。いわゆる化学増感助剤の存在下に化学増感することもできる。有用な化学増感助剤には、アザインデン、アザピリダジン、アザピリミジンのごとき、化学増感の過程でかぶりを抑制し、且つ感度を増大するものとして知られた化合物が用いられる。化学増感助剤改質剤の例は、米国特許第２，１３１，０３８号、同第３，４１１，９１４号、同第３，５５４，７５７号、特開昭５８−１２６５２６号および前述ダフィン著「写真乳剤化学」、１３８〜１４３頁に記載されている。本発明のハロゲン化銀乳剤に硫黄増感を施す場合の硫黄増感剤量の好ましい量は、ハロゲン化銀１モル当り１×１０^-4〜１×１０^-7モルであり、さらに好ましいのは１×１０^-5〜５×１０^-7モルである。
【０１８５】
本発明のハロゲン化銀乳剤に対して好ましく実施しうるカルコゲン増感法の一つにセレン増感がある。セレン増感において、公知の不安定セレン化合物を用い、具体的には、例えば、コロイド状金属セレニウム、セレノ尿素類（例えば．Ｎ，Ｎ−ジメチルセレノ尿素、Ｎ，Ｎ−ジエチルセレノ尿素等）、セレノケトン類、セレノアミド類のようなセレン化合物を用いることができる。セレン増感は硫黄増感あるいは貴金族増感あるいはその両方と組み合せて用いた方が好ましい。
【０１８６】
本発明のハロゲン化銀乳剤には、感光材料の製造工程、保存中あるいは写真処理中のかぶりを防止し、あるいは写真性能を安定化させる目的で、種々の化合物を含有させることができる。すなわち、チアゾール類、例えば、ベンゾチアゾリウム塩、ニトロイミダゾール類、ニトロベンズイミダゾール類、クロロベンズイミダゾール類、ブロモベンズイミダゾール類、メルカプトチアゾール類、メルカプトベンゾチアゾール類、メルカプトベンズイミダゾール類、メルカプトチアジアゾール類、アミノトリアゾール類、べンゾトリアゾール類、ニトロべンゾトリアゾール類、メルカプトテトラゾール類（特に１−フェニル−５−メルカプトテトラゾール）；メルカプトピリミジン類；メルカプトトリアジン類；例えば、オキサゾリンチオンのようなチオケト化合物；アザインデン類、例えぱ、トリアザインデン類、テトラアザインデン類（特に、４−ヒドロキシ置換（１，３，３ａ，７）テトラアザインデン類）、ペンタアザインデン類のようなかぶり防止剤または安定剤として知られた、多くの化合物を加えることができる。例えば、米国特許第３，９５４，４７４号、同第３，９８２，９４７号、特公昭５２−２８６６０号に記載されたものを用いることができる。好ましい化合物の一つに特開昭６３−２１２９３２号に記載された化合物がある。かぶり防止剤および安定剤は粒子形成前、粒子形成中、粒子形成後、水洗工程、水洗後の分散時、化学増感前、化学増感中、化学増感後、塗布前のいろいろな時期に目的に応じて添加することができる。乳剤調製中に添加して本来のかぶり防止および安定化効果を発現する以外に、粒子の晶壁を制御する、粒子サイズを小さくする、粒子の溶解性を減少させる、化学増感を制御する、色素の配列を制御するなど多目的に用いることができる。
【０１８７】
本発明のハロゲン化銀乳剤には、分光増感色素を含有させることができる。また、本発明のハロゲン化銀粒子に分光増感色素を吸着させることは好ましい態様である。分光増感色素としてはメチン色素類があり、シアニン色素、メロシアニン色素、複合シアニン色素、複合メロシアニン色素、ホロポーラーシアニン色素、へミシアニン色素、スチリル色素およびへミオキソノール色素が包含される。特に有用な色素は、シアニン色素、メロシアニン色素、および複合メロシアニン色索に属する色素である。これらの色素類には、塩基性複素環核としてシアニン色素類に通常利用される核のいずれをも適用できる。すなわち、例えば、ピロリン核、オキサゾリン核、チオゾリン核、ピロール核、オキサゾール核、チアゾール核、セレナゾール核、イミダゾール核、テトラゾール核、ピリジン核；これらの核に脂環式炭化水素環が融合した核；およびこれらの核に芳香族炭化水素環が融含した核、すなわち、例えば、インドレニン核、べンズインドレニン核、インドール核、ベンズオキサゾール核、ナフトオキサゾール核、ベンゾチアゾール核、ナフトチアゾール核、ベンゾセレナゾール核、ベンズイミダゾール核、キノリン核が適用できる。これらの核は炭素原子上に置換されていてもよい。メロシアニン色素または複合メロシアニン色素には、ケトメチレン構造を有する核として、例えば、ピラゾリン−５−オン核、チオヒダントイン核、２−チオキサゾリジン−２，４−ジオン核、チアゾリジン−２，４−ジオン核、ローダニン核およびチオバルビツール酸核のような５〜６員複素環核を適用することができる。
【０１８８】
これらの増感色素は単独に用いてもよいが、それらの組合せを用いてもよく、増感色素の組合せは特に、強色増感の目的でしばしば用いられる。その代表例は米国特許第２，６８８，５４５号、同第２，９７７，２２９号、同第３，３９７，０６０号、同第３，５２２，０５２号、同第３，５２７，６４１号、同第３，６１７，２９３号、同第３，６２８，９６４号、同第３，６６６，４８０号、同第３，６７２，８９８号、同第３，６７９，４２８号、同第３，７０３，３７７号、同第３，７６９，３０１号、同第３，８１４，６０９号、同第３，８３７，８６２号、同第４，０２６，７０７号、英国特許第１，３４４，２８１号、同第１，５０７，８０３号、特公昭４３−４９３６号、同５３−１２３７５号、特開昭５２−１１０６１８号、同５２−１０９９２５号に記載されている。増感色素とともに、それ自身分光増感作用をもたない色素あるいは可視光を実質的に吸収しない物質であって、かつ強色増感を示す物質を、乳剤中に含んでもよい。
【０１８９】
本発明のハロゲン化銀乳剤において通常好ましい分光増感色素の添加時期は、ハロゲン化銀粒子形成後である。もっとも普通には化学増感の完了後塗布前までの時期に行なわれるが、米国特許第３，６２８，９６９号、および同第４，２２５，６６６号に記載されているように化学増感剤と同時期に添加し分光増感を化学増感と同時に行なうことも、特開昭５８−１１３９２８号に記載されているように化学増感に先立って行なうことも出来、またハロゲン化銀粒子沈澱生成の完了前に添加し分光増感を開始することも出来る。さらにまた、米国特許第４，２５５，６６６号に教示されているようにこれらの前記化合物を分けて添加すること、即ちこれらの化合物の一部を化学増感に先立って添加し、残部を化学増感の後で添加することも可能であり、米国特許第４，１８３，７５６号に開示されている方法を始めとしてハロゲン化銀粒子形成中のどの時期であってもよい。添加量は、ハロゲン化銀１モル当り、４×１０^-6〜８×１０^-3モルの範囲で用いることができるが、ハロゲン化銀粒子サイズが０．２〜１．２μｍの場合は、約５×１０^-5〜２×１０^-3モルがより有効である。
【０１９０】
本発明のハロゲン化銀写真乳剤を用いてカラー感光材料を構成する際には、ハロゲン化銀乳剤は、物理熟成、化学熟成及び分光増感を行ったものを使用する。
【０１９１】
このような工程で使用される添加剤は、ＲＤ１７６４３，２３頁III項〜２４頁VI−Ｍ項、ＲＤ１８７１６，６４８〜６４９頁及びＲＤ３０８１１９，９９６頁III−Ａ項〜１０００頁VI−Ｍ項に記載されている。
【０１９２】
本発明に使用できる公知の写真用添加剤も、同じくＲＤ１７６４３，２５頁VIII−Ａ項〜２７頁XIII項、ＲＤ１８７１６，６５０〜６５１頁、ＲＤ３０８１１９，１００３頁VIII−Ａ項〜１０１２頁XXI−Ｅ項に記載のものを用いることができる。
【０１９３】
カラー感光材料には種々のカプラーを使用することができ、その具体例は、ＲＤ１７６４３，２５頁VII−Ｃ〜Ｇ項、ＲＤ３０８１１９，１００１頁VII−Ｃ〜Ｇ項に記載されている。
【０１９４】
本発明に使用する添加剤は、ＲＤ３０８１１９，１００７頁XIV項に記載されている分散法などにより添加することができる。
【０１９５】
本発明においては、前述ＲＤ１７６４３，２８頁XVII項、ＲＤ１８７１６，６４７〜８頁及びＲＤ３０８１１９，１００９頁XVII項に記載される支持体を使用することができる。
【０１９６】
感光材料には、前述ＲＤ３０８１１９，１００２頁VII−Ｋ項に記載されるフィルター層や中間層等の補助層を設けることができる。
【０１９７】
感光材料は、前述ＲＤ３０８１１９，VII−Ｋ項に記載の順層、逆層、ユニット構成等の様々な層構成を採ることができる。
【０１９８】
本発明のハロゲン化銀写真乳剤は、一般用又は映画用のカラーネガフィルム、スライド用又はテレビ用のカラー反転フィルム、カラーペーパー、カラーポジフィルム、カラー反転ペーパーに代表される種々のカラー感光材料に好ましく適用することができる。
【０１９９】
本発明に係る感光材料は、前述のＲＤ１７６４３，２８〜２９頁XIX項、ＲＤ１８７１６，６５１頁及びＲＤ３０８１１９，１０１０〜１０１１頁XIX項に記載される通常の方法によって現像処理することができる。
【０２００】
本発明が関係するハロゲン化銀写真感光材料には、本発明のハロゲン化銀乳剤以外に、双晶面を含まない正常晶でも、日本写真学会編、写真工業の基礎、銀塩写真編（コロナ社）、Ｐ．１６３に解説されているような例、例えば双晶面を一つ含む一重双晶、平行な双晶面を２つ以上含む平行多重双晶、非平行な双晶面を２つ以上含む非平行多重双晶などから目的に応じて選んで用いることができる。また形状の異なる粒子を混合させる例は米国特許第４，８６５，９６４号に開示されているが、必要によりこの方法を選ぶことができる。
【０２０１】
正常晶の場合には（１００）面からなる立方体、（１１１）面からなる八面体、特公昭５５−４２７３７号、特開昭６０−２２２８４２号に開示されている（１１０）面からなる１２面体粒子を用いることができる。さらに、Ｊｏｕｒｎａｌ ｏｆ Ｉｍａｇｉｎｇ Ｓｃｉｅｎｃｅ，３０巻、２４７ページ、１９８６年に報告されているような（２１１）を代表とする（ｈｌｌ）面粒子、（３３１）を代表とする（ｈｈｌ）面粒子、（２１０）面を代表とする（ｈｋ０）面粒子と（３２１）面を代表とする（ｈｋｌ）面粒子も調製法に工夫を要するが、目的に応じて選んで用いることができる。（１００）面と（１１１）面が一つの粒子に共存する１４面体粒子、（１００）面と（１１０）面が共存する粒子など、２つの面あるいは多数の面が共存する粒子も目的に応じて選んで用いることができる。
【０２０２】
本発明に関係するハロゲン化銀粒子には、欧州特許第９６，７２７Ｂ１号、同第６４，４１２Ｂ１号などに開示されているような粒子に丸みをもたらす処理、あるいは西独特許第２，３０６，４４７Ｃ２号、特開昭６０−２２１３２０号に開示されているような表面の改質を行うことも可能である。
【０２０３】
ハロゲン化銀粒子表面は平坦な構造が一般的であるが、意図して凹凸を形成することもできる。特開昭５８−１０６５３２号、同６０−２２１３２０号に記載されている結晶の一部分、例えば頂点あるいは面の中央に穴をあける方法、あるいは米国特許第４，６４３，９６６号に記載されているラッフル粒子がその例である。
【０２０４】
本発明が関係するハロゲン化銀写真感光材料には、本発明のハロゲン化銀乳剤以外に、粒子サイズ分布の広い、いわゆる多分散乳剤でも、サイズ分布の狭い、いわゆる単分散乳剤でも目的に応じて選んで用いることができる。サイズ分布を表す尺度として粒子の投影面積相当直径あるいは体積の球相当直径の変動係数を用いる場合がある。単分散乳剤を用いる場合、変動係数が２０％以下、より好ましくは１５％以下のサイズ分布の乳剤を用いるのがよい。また、感光材料が目標とする階調を満足させるために、実質的に同一の感色性を有する乳剤層において粒子サイズの異なる２種以上の単分散ハロゲン化銀乳剤を同一層に混合または別層に重層塗布することができる。さらに２種類以上の多分散ハロゲン化銀乳剤あるいは単分散乳剤と多分散乳剤との組合わせを混合あるいは重層して使用することもできる。
【０２０５】
本発明のハロゲン化銀乳剤を感光材料として使用する際には、前記の種々の添加剤が用いられるが、それ以外にも目的に応じて種々の添加剤を用いることができる。これらの添加剤は、より詳しくはリサーチディスクロージャーＩｔｅｍ １７６４３（１９７８年１２月）、同Ｉｔｅｍ １８７１６（１９７９年１１月）および同Ｉｔｅｍ ３０８１１９（１９８９年１２月）に記載されている。
【０２０６】
本発明のハロゲン化銀乳剤は、種々の写真感光材料に使用することができる。重要な１つの態様として、本発明のハロゲン化銀乳剤は、少なくとも２層のハロゲン化銀乳剤層を有する多層写真感光材料に使用することが適している。例えばカラーネガフィルム、カラーリバーサルフィルムのような多層写真感光材料である場合、本発明が関係するハロゲン化銀乳剤は高感度層側、低感度層側どちらか一方に用いても良く、両者に用いても良い。
【０２０７】
【実施例】
以下に、本発明を実施例を挙げて具体的に説明するが、本発明はこれらの実施態様に限定されるものではない。
【０２０８】
実施例１
［比較乳剤Ｅｍ１−１の調製］
《コアの形成》
以下の様にしてコアを形成した。
【０２０９】
〔核形成工程〕
反応容器内のＢ−１０１を３０℃に保ち、特開昭６２−１６０１２８号公報記載の混合撹拌装置を用いて撹拌回転数４００回転／分で撹拌しながら、濃硫酸を１／１０に希釈した溶液を２９．０ｍｌ加えてｐＨを２に調整した。反応容器内のｐＢｒは２．２であった。その後、３０℃に保温されたＳ−１０１とＸ−１０１を、ダブルジェット法を用いて一定の流量で１分間で添加し核生成を行った。核生成終了後に４０℃に保温されたＧ−１０１を加えた。
【０２１０】
（Ｂ−１０１）
アルカリ処理不活性ゼラチン（平均分子量１０万） １２．１ｇ
臭化カリウム ３．７ｇ
Ｈ₂Ｏ １２９３．８ｍｌ
（Ｓ−１０１）
硝酸銀 １８．８ｇ
Ｈ₂Ｏ ８４．４ｍｌ
（Ｘ−１０１）
臭化カリウム １３．２ｇ
Ｈ₂Ｏ ８３．９ｍｌ
（Ｇ−１０１）
アルカリ処理不活性ゼラチン（平均分子量１０万） ５２．０ｇ
下記〔化合物Ａ〕の１０質量％メタノール溶液 １．７ｍｌ
Ｈ₂Ｏ １２２０．０ｍｌ
〔化合物Ａ〕ＨＯ（ＣＨ₂ＣＨ₂Ｏ）_m［ＣＨ（ＣＨ₃）ＣＨ₂Ｏ］₂₀（ＣＨ₂ＣＨ₂Ｏ）_nＨ（ｍ＋ｎ＝１０）
反応容器内の溶液を３０分間を要して６０℃に昇温し、さらに３０分間熟成を施した。続いて、２８％アンモニア水溶液を３３．６ｍｌ加え１０％水酸化カリウム水溶液でｐＨを９．３に調整し６分間保持した後、１Ｎの硝酸水溶液を用いてｐＨを５．８に調整した。熟成工程の間、溶液の銀電位（飽和銀−塩化銀電極を比較電極として銀イオン選択電極で測定）を１Ｎの臭化カリウム水溶液を用いて６ｍＶに制御した。
【０２１１】
〔核成長工程〕
核形成工程終了後に、以下のような核成長工程を行ってコア相を形成した。
【０２１２】
ダブルジェット法を用いて３．５Ｎ硝酸銀水溶液Ｓ−１０２と３．５Ｎ臭化カリウム水溶液Ｘ−１０２を流量を加速しながら（終了時と開始時の添加流量の比が約１２倍）３８分間で添加した（この添加で、硝酸銀を１３９．５ｇ消費）。この間溶液の銀電位を１Ｎの臭化カリウム溶液を用いて６ｍＶに制御した。添加終了後にＧ−１０２を加えた。その後再びＳ−１０２とＸ−１０２を流速を加速しながら添加した（この添加で、硝酸銀を４７７．７ｇ消費）。この間も溶液の銀電位を１Ｎの臭化カリウム溶液を用いて６ｍＶに制御した。
【０２１３】
（Ｓ−１０２）
硝酸銀 ６１７．２ｇ
Ｈ₂Ｏ ８９６．２ｍｌ
（Ｘ−１０２）
臭化カリウム ４３２．４ｇ
Ｈ₂Ｏ ８８１．１ｍｌ
（Ｇ−１０２）
アルカリ処理不活性ゼラチン（平均分子量１０万） ８４．０ｇ
前記〔化合物Ａ〕の１０質量％メタノール溶液 ２．３ｍｌ
Ｈ₂Ｏ ６００．０ｍｌ
《第１シェルの形成》
上記コアの形成に続き、３．５Ｎ硝酸銀水溶液Ｓ−１０３と３．５Ｎ臭化カリウム／沃化カリウム水溶液（沃化カリウム１０モル％）Ｘ−１０３を流量を加速しながら添加し第１シェルを形成した。この間溶液の銀電位を１Ｎの臭化カリウム溶液を用いて６ｍＶに制御した。
【０２１４】
（Ｓ−１０３）
硝酸銀 ４３２．０ｇ
Ｈ₂Ｏ ６２７．３ｍｌ
（Ｘ−１０３）
臭化カリウム ２７２．４ｇ
沃化カリウム ４２．２ｇ
Ｈ₂Ｏ ６１４．２ｍｌ
《第２シェルの形成》
上記コア相の形成に続き、３．５Ｎ硝酸銀水溶液Ｓ−１０４と３．５Ｎ臭化カリウム水溶液Ｘ−１０４を流量を加速しながら添加し第２シェルを形成した。この間溶液の銀電位を１Ｎの臭化カリウム溶液を用いて６ｍＶに制御した。
【０２１５】
（Ｓ−１０４）
硝酸銀 ６１２．０ｇ
Ｈ₂Ｏ ８８８．７ｍｌ
（Ｘ−１０４）
臭化カリウム ４２８．７ｇ
Ｈ₂Ｏ ８７３．７ｍｌ
《第３シェルの形成》
上記添加終了後に、反応容器内の溶液温度を３０分を要して４０℃に降温した。その後、Ｚ−１０１液ついでＳＳ−１０１液を添加し、水酸化カリウム水溶液を用いてｐＨを９．３に調整し、４分間熟成しながら沃素イオンを放出させ、高沃度局在層である第３シェルを形成した。その後酢酸水溶液を用いてｐＨを５．０に調整し、次いで３．５Ｎの臭化カリウム水溶液を用いて反応容器内の銀電位を−３９ｍＶに調整した。
【０２１６】
（Ｚ−１０１）
ｐ−ヨードアセトアミドベンゼンスルホン酸ナトリウム ７７．０ｇ
Ｈ₂Ｏ １０００．０ｍｌ
（ＳＳ−１０１）
亜硫酸ナトリウム ２６．８ｇ
Ｈ₂Ｏ ３００．０ｍｌ
《第４シェルの形成》
上記添加に続き、３．５Ｎ硝酸銀水溶液Ｓ−１０５と３．５Ｎ臭化カリウム水溶液Ｘ−１０５を流量を加速しながら添加し第４シェル層を形成した。
【０２１７】
（Ｓ−１０５）
硝酸銀 ７２０．０ｇ
Ｈ₂Ｏ １０４５．５ｍｌ
（Ｘ−１０５）
臭化カリウム ５０４．４ｇ
Ｈ₂Ｏ １０２８．０ｍｌ
核生成時を除き上記の各相形成時の硝酸銀水溶液及びハロゲン塩水溶液の添加は、添加中の新核生成が起こらない範囲で添加速度を高めて行った。シェル相形成終了後に特開平５−７２６５８号に記載の方法に従い脱塩・水洗処理を施し、ゼラチンを加えて良く分散し、４０℃にてｐＨを５．８、ｐＡｇを８．１に調整した。かくして平板状ハロゲン化銀乳剤Ｅｍ１−１が得られた。解析の結果、乳剤Ｅｍ１−１は立方体換算の平均粒径が０．８５μｍ、投影面積の８０％以上がアスペクト比５以上の平板状粒子であることが判った。
【０２１８】
［比較乳剤Ｅｍ１−２〜Ｅｍ１−３の調製］
乳剤Ｅｍ１−１の調製と同様にして乳剤Ｅｍ１−２〜Ｅｍ１−３を調製した。但し、乳剤Ｅｍ１−２〜Ｅｍ１−３はそれぞれの乳剤が表１に示した沃化銀の分布構造となるように、添加する溶液の量やハロゲン塩水溶液の組成を調整した。
【０２１９】
各乳剤の特徴を表１に示す。
［乳剤Ｅｍ１−４〜１−６の調製］
乳剤Ｅｍ１−１〜Ｅｍ１−３の調製において、総添加銀量の６．６％を消費した時点でＲ−１液をラッシュで添加し、総添加銀量の７０％を消費した時点でＴ−１液をラッシュで添加した以外はＥｍ１−１と同様の製造方法により、乳剤Ｅｍ１−４〜１−６を調製した。
【０２２０】
（Ｒ−１）
二酸化チオ尿素 ２１．３ｍｇ
蒸留水 ３７．３ｍｌ
（Ｔ−１）
エタンチオスルフォン酸ナトリウム ７０３．９ｍｇ
蒸留水 ２３４．６ｍｌ
［乳剤Ｅｍ１−７〜Ｅｍ１−９の調製］
乳剤Ｅｍ１−１〜Ｅｍ１−３の調製において、総添加銀量の７０％を消費した時点でＴ−１液をラッシュで添加した以外はＥｍ１−１〜Ｅｍ１−３と同様に、乳剤Ｅｍ１−７〜Ｅｍ１−９を調製した。
【０２２１】
［乳剤Ｅｍ１−１０〜Ｅｍ１−１２の調製］
乳剤Ｅｍ１−１〜Ｅｍ１−３の調製において、総添加銀量の６５％を消費した段階で、ｐＡｇを８．９に調整した後、メタルドーピング剤ＳＥＴ−１（Ｋ₄〔Ｆｅ（ＣＮ）₆〕）を水溶液で２×１０^-6モル／モルＡｇ添加し、メタル添加終了時の総添加銀量が７０％を消費した段階で、ｐＡｇを１０．３に調整した以外はＥｍ１−１〜Ｅｍ１−３と同様の製造方法により、乳剤Ｅｍ１−１０〜Ｅｍ１−１２を調製した。
【０２２２】
［乳剤Ｅｍ１−１３〜Ｅｍ１−１５の調製］
乳剤Ｅｍ１−１０〜Ｅｍ１−１２の調製において、メタルドーピング剤をＳＥＴ−１からＳＥＴ−２（Ｋ₄〔Ｒｕ（ＣＮ）₆〕）に代え、水溶液で１×１０^-5モル／モルＡｇ添加した以外はＥｍ１−１０〜Ｅｍ１−１２と同様に、乳剤Ｅｍ１−１３〜Ｅｍ１−１５を調製した。
【０２２３】
［乳剤Ｅｍ１−１６〜Ｅｍ１−１８の調製］
乳剤Ｅｍ１−１〜Ｅｍ１−３の調製において、粒子成長終了後に、特開平５−７２６５８号に記載の方法に従い脱塩処理を施し、その後、ゼラチン溶液を添加し、乳剤温度を５０℃に調整してＦ−１液を添加した以外は、乳剤Ｅｍ１−１〜Ｅｍ１−３と同様に、乳剤Ｅｍ１−１６〜Ｅｍ１−１８を調製した。
【０２２４】
（Ｆ−１）
Ｋ₂ＩｒＣｌ₆をドープした臭化銀粒子（平均粒径０．０５μｍ）からなる
微粒子乳剤（＊） ３．７６ｇ
＊微粒子乳剤Ｆ−１の調製法は以下の通り：
０．０６モルの臭化カリウムを含む６．０質量％のゼラチン溶液５０００ｍｌに、７．０６モルの硝酸銀を含む水溶液２０００ｍｌと、７．０６モルの臭化カリウム及び４．４×１０^-3モルのＫ₂ＩｒＣｌ₆を含む水溶液２０００ｍｌを、１０分間かけて添加した。微粒子形成中のｐＨは硝酸を用いて２．０に、温度は４０℃に制御した。粒子形成後に、炭酸ナトリウム水溶液を用いてｐＨを６．０に調整した。仕上がり質量は１２．５３ｋｇであった。
【０２２５】
［乳剤Ｅｍ１−１９〜Ｅｍ１−２１の調製］
Ｅｍ１−１〜Ｅｍ１−３の成長工程において限外濾過装置を用い、４０℃に降温すると同時に、反応物溶液を９．１ｌにまで濃縮（濃縮前の容積に対して１／３以下）し、反応容器内の銀電位を−３９ｍＶに調整した後、成長工程終了まで反応物溶液の容積を保持した以外はＥｍ１−１〜Ｅｍ１−３と同様にして乳剤Ｅｍ１−１９〜Ｅｍ１−２１を調製した。
【０２２６】
［乳剤Ｅｍ１−２２〜Ｅｍ１−２４の調製］
乳剤Ｅｍ１−１〜Ｅｍ１−３を４０℃で溶解し、１Ｎ硝酸銀水溶液と１Ｎ沃化カリウム水溶液とを流量比８：１で同時添加し、ｐＢｒ４．０に調整した。引き続き１Ｎ塩化ナトリウム水溶液を乳剤（Ｅｍ１−１〜Ｅｍ１−３）１モル当たり０．０２モル添加し、後出の分光増感色素ＳＤ−６及びＳＤ−７を合計被覆率が７０％になるように２：１の比率で添加し、その後０．５Ｎ硝酸銀水溶液と０．５Ｎ塩化ナトリウム水溶液とを定速で、乳剤（Ｅｍ１−１〜Ｅｍ１−３）１モル当たり０．０５モル同時添加した。この操作により平板状ハロゲン化銀粒子の主としてコーナーとエッジにエピタキシャルが形成された乳剤Ｅｍ１−２２〜Ｅｍ１−２４を調製した。
【０２２７】
［乳剤Ｅｍ１−２５〜Ｅｍ１−２７の調製］
乳剤Ｅｍ１−１〜Ｅｍ１−３を６０℃で溶解し、２Ｎ臭化カリウム水溶液でｐＡｇを８．８に調整して下記のＫ−１液のハロゲン化銀量で０．７モル相当量を１０分で添加し、２０分間熟成し、その後、４０℃においてｐＡｇ８．０６、ｐＨ５．８に調整して乳剤Ｅｍ１−２５〜Ｅｍ１−２７を調製した。
【０２２８】
（Ｋ−１液）
３．０質量％のゼラチンと塩化銀微粒子（平均粒径０．０８μｍ）から成る微粒子乳剤
調製法を以下に示す。
【０２２９】
０．０６モルの塩化ナトリウムを含む６．０質量％のゼラチン溶液５０００ｍｌに７．０６モルの硝酸銀を含む水溶液２０００ｍｌと７．０６モルの塩化ナトリウムを含む水溶液２０００ｍｌとを１０分間かけて等速添加した。微粒子形成中のｐＨは硝酸を用いて３．０に、温度は３０℃に制御した。添加終了後に、炭酸ナトリウム水溶液を用いてｐＨを６．０に調整し、２Ｎ塩化ナトリウム水溶液で４０℃にてｐＡｇ７．５に調製した。
【０２３０】
［乳剤Ｅｍ１−２８〜Ｅｍ１−３０の調製］
乳剤Ｅｍ１−１〜Ｅｍ１−３の調製において、（Ｂ−１０１）、（Ｇ−１０１）および（Ｇ−１０２）に用いるゼラチンの５０質量パーセントをフェニルカルバモイル化ゼラチン（アミノ基の置換率９０％）に置き換えた以外はＥｍ１−１〜Ｅｍ１−３と同様にして乳剤Ｅｍ１−２８〜Ｅｍ１−３０を作製した。
【０２３１】
なお、乳剤Ｅｍ１−１〜Ｅｍ１−３０は、いずれもアスペクト比５以上の平板状粒子が投影面積の８０％以上を占めていた。これらの乳剤はいずれもフリンジ部に１粒子当たり平均２０本以上の転位線が観察された。
【０２３２】
各乳剤の特徴を表１に示す。
【０２３３】
【表１】

【０２３４】
５２℃に保持した乳剤Ｅｍ１−１〜Ｅｍ１−３０の各乳剤に、増感色素ＳＤ−６、ＳＤ−７、ＳＤ−８を加えた。このとき、Ｅｍ−２２〜２４については、乳剤調製時に使用した色素量を差し引いて加えた。２０分間熟成した後、チオ硫酸ナトリウム、トリフェニルフォスフィンセレニド、塩化金酸、チオシアン酸カリウムを添加した。各乳剤ごとに最適な感度−カブリが得られるように増感色素や増感剤の添加量や熟成時間を調整して、１−フェニル−５−メルカプトテトラゾールと４−ヒドロキシ−６−メチル−１，３，３ａ，７−テトラアザインデンを加えて安定化した。
【０２３５】
〔カラー感光材料試料の作製〕
下引き層を施したセルローストリアセテートフィルム支持体上に、下記に示すような組成の各層を順次支持体側から塗布してハロゲン化銀多層カラー写真感光材料の試料１０１を作製した。
【０２３６】
添加量は特に記載しない限り１ｍ²当たりのグラム数を示す。また、ハロゲン化銀とコロイド銀は銀に換算して示し、増感色素（ＳＤで示す）は銀１モル当たりのモル数で示した。
【０２３７】
第１層（ハレーション防止層）
黒色コロイド銀 ０．１６
ＵＶ−１ ０．３０
ＣＭ−１ ０．１２
ＣＣ−１ ０．０３
ＯＩＬ−１ ０．２４
ゼラチン １．３３
第２層（中間層）
沃臭化銀乳剤ｊ ０．１０
ＡＳ−１ ０．１２
ＯＩＬ−１ ０．１５
ゼラチン ０．６７
第３層（低感度赤感色性層）
沃臭化銀乳剤ｃ ０．０５３
沃臭化銀乳剤ｄ ０．１１
沃臭化銀乳剤ｅ ０．１１
ＳＤ−１ ２．２×１０^-5
ＳＤ−２ ５．９×１０^-5
ＳＤ−３ １．２×１０^-4
ＳＤ−４ １．６×１０^-4
ＳＤ−５ １．６×１０^-4
Ｃ−１ ０．１９
ＣＣ−１ ０．００３
ＯＩＬ−２ ０．０９６
ＡＳ−２ ０．００１
ゼラチン ０．４４
第４層（中感度赤感色性層）
沃臭化銀乳剤ｂ ０．２８
沃臭化銀乳剤ｃ ０．３４
沃臭化銀乳剤ｄ ０．５０
ＳＤ−１ １．８×１０^-5
ＳＤ−４ ２．６×１０^-4
ＳＤ−５ ２．８×１０^-4
Ｃ−１ ０．７４
ＣＣ−１ ０．０８１
ＤＩ−１ ０．０２０
ＤＩ−４ ０．００８
ＯＩＬ−２ ０．４２
ＡＳ−２ ０．００３
ゼラチン １．９５
第５層（高感度赤感色性層）
沃臭化銀乳剤ａ １．４５
沃臭化銀乳剤ｅ ０．０７６
ＳＤ−１ ２．３×１０^-5
ＳＤ−２ １．１×１０^-4
ＳＤ−３ １．５×１０^-5
ＳＤ−４ ２．１×１０^-4
Ｃ−２ ０．０８７
Ｃ−３ ０．１２
ＣＣ−１ ０．０３６
ＤＩ−１ ０．０２１
ＤＩ−３ ０．００５
ＢＡＲ−１ ０．０２２
ＯＩＬ−２ ０．１５
ＡＳ−２ ０．００４
ゼラチン １．４０
第６層（中間層）
Ｆ−１ ０．０３
ＡＳ−１ ０．１８
ＯＩＬ−１ ０．２２
ゼラチン １．００
第７層（低感度緑感色性層）
沃臭化銀乳剤ｃ ０．２２
沃臭化銀乳剤ｅ ０．２２
ＳＤ−６ ４．７×１０^-5
ＳＤ−７ ２．６×１０^-4
ＳＤ−８ １．９×１０^-4
ＳＤ−９ １．１×１０_-4
ＳＤ−１０ ２．４×１０^-5
Ｍ−１ ０．３５
ＣＭ−１ ０．０４４
ＤＩ−２ ０．０１０
ＯＩＬ−１ ０．４１
ＡＳ−２ ０．００１
ＡＳ−３ ０．１１
ゼラチン １．２９
第８層（中感度緑感色性層）
沃臭化銀乳剤ｂ ０．９０
沃臭化銀乳剤ｅ ０．０４８
ＳＤ−６ ３．８×１０^-5
ＳＤ−７ ２．６×１０^-4
ＳＤ−８ ３．４×１０^-4
ＳＤ−９ １．６×１０^-4
ＳＤ−１０ ４．４×１０^-5
Ｍ−１ ０．１５
ＣＭ−１ ０．０６２
ＣＭ−２ ０．０３０
ＤＩ−２ ０．０３２
ＯＩＬ−１ ０．２８
ＡＳ−２ ０．００５
ＡＳ−３ ０．０４５
ゼラチン １．００
第９層（高感度緑感色性層）
乳剤Ｅｍ１−１ １．３９
沃臭化銀乳剤ｅ ０．０７３
ＳＤ−６ ４．１×１０^-5
ＳＤ−７ ２．６×１０^-5
ＳＤ−８ ３．７×１０^-4
ＳＤ−１０ ４．９×１０^-5
Ｍ−１ ０．０７１
Ｍ−２ ０．０７３
ＣＭ−２ ０．０１３
ＤＩ−２ ０．００４
ＤＩ−３ ０．００３
ＯＩＬ−１ ０．２７
ＡＳ−２ ０．００８
ＡＳ−３ ０．０４３
ゼラチン １．３５
第１０層（イエローフィルター層）
黄色コロイド銀 ０．０５３
ＡＳ−１ ０．１５
ＯＩＬ−１ ０．１８
Ｘ−１ ０．０６
ゼラチン ０．８３
第１１層（低感度青感色性層）
沃臭化銀乳剤ｇ ０．２２
沃臭化銀乳剤ｈ ０．０９９
沃臭化銀乳剤ｉ ０．１７
ＳＤ−１１ ２．４×１０^-4
ＳＤ−１２ ５．７×１０^-4
ＳＤ−１３ １．３×１０^-4
Ｙ−１ １．０２
ＢＡＲ−１ ０．０２２
ＯＩＬ−１ ０．４２
ＡＳ−２ ０．００３
Ｘ−１ ０．１１
Ｘ−２ ０．１８
ゼラチン １．９５
第１２層（高感度青感色性層）
沃臭化銀乳剤ｆ １．５２
ＳＤ−１１ ８．３×１０^-5
ＳＤ−１２ ２．３×１０^-4
Ｙ−１ ０．２２
ＤＩ−５ ０．１１
ＯＩＬ−１ ０．１３
ＡＳ−２ ０．００３
Ｘ−１ ０．１５
Ｘ−２ ０．２０
ゼラチン １．２０
第１３層（第１保護層）
沃臭化銀乳剤ｊ ０．３０
ＵＶ−１ ０．１１
ＵＶ−２ ０．０５５
流動パラフィン ０．２８
Ｘ−１ ０．０７９
ゼラチン １．００
第１４層（第２保護層）
ＰＭ−１ ０．１３
ＰＭ−２ ０．０１８
ＷＡＸ−１ ０．０２１
ゼラチン ０．５５
上記で用いた沃臭化銀乳剤の特徴を下記に表示する（平均粒径とは同体積の立方体の一辺長）。
【０２３８】
乳剤Ｎｏ． 平均粒径（μｍ） 平均ＡｇＩ量（ｍｏｌ％） 直径／厚み比
沃臭化銀乳剤ａ ０．８５ ４．２ ７．０
沃臭化銀乳剤ｂ ０．７０ ４．２ ６．０
沃臭化銀乳剤ｃ ０．５０ ４．２ ５．０
沃臭化銀乳剤ｄ ０．３８ ８．０ ８面体双晶
沃臭化銀乳剤ｅ ０．２７ ２．０ １４面体正常晶
沃臭化銀乳剤ｆ １．００ ８．０ ４．５
沃臭化銀乳剤ｇ ０．７４ ３．５ ６．２
沃臭化銀乳剤ｈ ０．４４ ４．２ ６．１
沃臭化銀乳剤ｉ ０．３０ １．９ ５．５
沃臭化銀乳剤ｊ ０．０３ ２．０ １．０
上記各乳剤には前述の増感色素を添加し、熟成した後トリフェニルフォスフィンセレナイド、チオ硫酸ナトリウム、塩化金酸、チオシアン酸カリウムを添加し、常法に従い、カブリ、感度関係が最適になるように化学増感を施したものを用いた。
【０２３９】
尚、上記の組成物の他に、塗布助剤ＳＵ−１、ＳＵ−２、ＳＵ−３、分散助剤ＳＵ−４、粘度調整剤Ｖ−１、安定剤ＳＴ−１、ＳＴ−２、重量平均分子量：１０，０００及び重量平均分子量：１００，０００の２種のポリビニルピロリドン（ＡＦ−１、ＡＦ−２）、抑制剤ＡＦ−３、ＡＦ−４、ＡＦ−５、硬膜剤Ｈ−１、Ｈ−２及び防腐剤Ａｓｅ−１を添加した。
【０２４０】
上記試料に用いた化合物の構造を以下に示す。
【０２４１】
【化１０】

【０２４２】
【化１１】

【０２４３】
【化１２】

【０２４４】
【化１３】

【０２４５】
【化１４】

【０２４６】
【化１５】

【０２４７】
【化１６】

【０２４８】
【化１７】

【０２４９】
【化１８】

【０２５０】
【化１９】

【０２５１】
【化２０】

【０２５２】
同様に、増感処理を施した前記乳剤Ｅｍ１−２〜Ｅｍ１−３０を乳剤Ｅｍ１−１の代わりに各々使用して、多層カラー写真感光材料試料１００２〜１０３０を作製した。
【０２５３】
試料１００２〜１０３０に、白色光を用いて１／２００秒、１．６ＣＭＳでステップウェッジ露光した後、下記基準カラー現像処理で処理した。
【０２５４】
《基準カラー現像処理》
処理工程 処理時間 処理温度 補充量＊
発色現像 ３分１５秒 ３８± ０．３℃ ７８０ｍｌ
漂 白 ４５秒 ３８± ２．０℃ １５０ｍｌ
定 着 １分３０秒 ３８± ２．０℃ ８３０ｍｌ
安 定 ６０秒 ３８± ５．０℃ ８３０ｍｌ
乾 燥 １分 ５５± ５．０℃ −
＊補充量は感光材料１ｍ²当たりの値である。
【０２５５】
発色現像液、漂白液、定着液、安定液及びその補充液は、以下のものを使用した。
【０２５６】
発色現像液
水 ８００ｍｌ
炭酸カリウム ３０ｇ
炭酸水素ナトリウム ２．５ｇ
亜硫酸カリウム ３．０ｇ
臭化ナトリウム １．３ｇ
沃化カリウム １．２ｍｇ
ヒドロキシルアミン硫酸塩 ２．５ｇ
塩化ナトリウム ０．６ｇ
４−アミノ−３−メチル−Ｎ−エチル−Ｎ−（β−ヒドロキシルエチル）
アニリン硫酸塩 ４．５ｇ
ジエチレントリアミン五酢酸 ３．０ｇ
水酸化カリウム １．２ｇ
水を加えて１リットルとし、水酸化カリウムまたは２０％硫酸を用いてｐＨ１０．０６に調整する。
【０２５７】
発色現像補充液
水 ８００ｍｌ
炭酸カリウム ３５ｇ
炭酸水素ナトリウム ３ｇ
亜硫酸カリウム ５ｇ
臭化ナトリウム ０．４ｇ
ヒドロキシルアミン硫酸塩 ３．１ｇ
４−アミノ−メチル−Ｎ−エチル−Ｎ−（β−ヒドロキシルエチル）
アニリン硫酸塩 ６．３ｇ
水酸化カリウム ２ｇ
ジエチレントリアミン五酢酸 ３．０ｇ
水を加えて１リットルとし、水酸化カリウムまたは２０％を用いてｐＨ１０．１８に調整する。
【０２５８】
漂白液
水 ７００ｍｌ
１，３−ジアミノプロパン四酢酸鉄（III）アンモニウム １２５ｇ
エチレンジアミン四酢酸 ２ｇ
硝酸ナトリウム ４０ｇ
臭化アンモニウム １５０ｇ
氷酢酸 ４０ｇ
水を加えて１リットルとし、アンモニア水または氷酢酸を用いてｐＨ４．４に調整する。
【０２５９】
漂白補充液
水 ７００ｍｌ
１，３−ジアミノプロパン四酢酸鉄（III）アンモニウム １７５ｇ
エチレンジアミン四酢酸 ２ｇ
硝酸ナトリウム ５０ｇ
臭化アンモニウム ２００ｇ
氷酢酸 ５６ｇ
アンモニア水または氷酢酸を用いてｐＨ４．４に調整後水を加えて１リットルとする。
【０２６０】
定着液
水 ８００ｍｌ
チオシアン酸アンモニウム １２０ｇ
チオ硫酸アンモニウム １５０ｇ
亜硫酸ナトリウム １５ｇ
エチレンジアミン四酢酸 ２ｇ
アンモニア水または氷酢酸を用いてｐＨ６．２に調整後水を加えて１リットルとする。
【０２６１】
定着補充液
水 ８００ｍｌ
チオシアン酸アンモニウム １５０ｇ
チオ硫酸アンモニウム １８０ｇ
亜硫酸ナトリウム ２０ｇ
エチレンジアミン四酢酸 ２ｇ
アンモニア水または氷酢酸を用いてｐＨ６．５に調整後水を加えて１リットルとする。
【０２６２】
安定液及び安定補充液
水 ９００ｍｌ
パラオクチルフェニルポリオキシエチレンエーテル（ｎ＝１０）２．０ｇ
ジメチロール尿素 ０．５ｇ
ヘキサメチレンテトラミン ０．２ｇ
１，２−ベンゾイソチアゾリン−３−オン ０．１ｇ
シロキサン（ＵＣＣ製Ｌ−７７） ０．１ｇ
アンモニア水 ０．５ｍｌ
水を加えて１リットルとした後、アンモニア水または５０％硫酸を用いてｐＨ８．５に調整する。
【０２６３】
得られたカラー多層感光材料試料の感度、ＲＭＳ値、潜像安定性を緑色光を用いて測定した。測定方法及び条件を以下に示す。
【０２６４】
相対感度は、各試料において、未露光部の濃度（＝Ｄｍｉｎ）＋０．１の濃度を与える露光量の逆数を求め、試料１００１の感度を１００とする相対値で示した。相対感度の値が大きいほど感度が高く好ましいことを意味する。
【０２６５】
相対ＲＭＳ値は、ＲＭＳの測定位置は、Ｄｍｉｎ＋０．２の濃度点である。ＲＭＳ値は、各試料の測定位置をイーストマンコダック社製のラッテンフィルター（Ｗ−９９）を装着したマイクロデンシトメーター（スリット幅１０μｍ、スリット長１８０μｍ）で走査し、濃度測定サンプリング数１０００以上の濃度値の標準偏差として求めた。各試料においてＲＭＳ値を求め、試料１００１のＲＭＳ値を１００とする相対値で示した。相対ＲＭＳの値が小さいほど粒状性に優れ好ましいことを意味する。
【０２６６】
潜像安定性の評価は、温度５５℃湿度６５％の環境で５日間保存した試料を経時試料とし、経時試料についても経時前試料と同様の露光・発色現像処理を施して経時前試料に対する経時試料の感度変動を評価した。試料１００１の感度変動を１００として相対値で示し、値が小さい方が変動が少なく好ましい。
【０２６７】
各試料について、得られた結果を表２に示す。
【０２６８】
【表２】

【０２６９】
表から明らかなように、本発明に関わる試料１００５、１００６、１００８、１００９、１０１１、１０１２、１０１４、１０１５、１０１７、１０１８、１０２０、１０２１、１０２３、１０２４、１０２６、１０２７、１０２９、１０３０（本発明の請求項１〜８に記載の発明の構成）は、比較試料１００１、１００２、１００３、１００４、１００７、１０１０、１０１３、１０１６、１０１９、１０２２、１０２５、１０２８に対して高感度で、粒状性、潜像安定性に優れた性能を示した。
【０２７０】
実施例２
［比較乳剤Ｅｍ２−１の調製］
前出の乳剤Ｅｍ１−１と同様にして乳剤Ｅｍ２−１を作製した。
【０２７１】
［比較乳剤Ｅｍ２−２の調製］
第４シェルを以下のように第４シェルおよび第５シェルに変更する以外は乳剤Ｅｍ２−１と同様にして、乳剤Ｅｍ２−２を調製した。
【０２７２】
《第４シェルの形成》
第３シェルの添加に続き、３．５Ｎ硝酸銀水溶液Ｓ−２０１と３．５Ｎ臭化カリウム／沃化カリウム水溶液（沃化カリウム３モル％）Ｘ−２０１を流量を加速しながら添加し第４シェルを形成した。
【０２７３】
（Ｓ−２０１）
硝酸銀 ５７６．０ｇ
Ｈ₂Ｏ ８３６．４ｍｌ
（Ｘ−２０１）
臭化カリウム ３９１．４ｇ
沃化カリウム １６．８９ｇ
Ｈ₂Ｏ ８２１．２ｍｌ
《第５シェルの形成》
上記第４シェルの添加に続き、３．５Ｎ硝酸銀水溶液Ｓ−２０２と３．５Ｎ臭化カリウム水溶液Ｘ−２０２を流量を加速しながら添加し第５シェルを形成した。
【０２７４】
（Ｓ−２０２）
硝酸銀 １４４．０ｇ
Ｈ₂Ｏ ２０９．１ｍｌ
（Ｘ−２０２）
臭化カリウム １００．９ｇ
Ｈ₂Ｏ ２０５．６ｍｌ
［乳剤Ｅｍ２−３の調製］
乳剤Ｅｍ２−２の調製と同様にして乳剤Ｅｍ２−３を調製した。但し、乳剤Ｅｍ２−３は乳剤が表４に示した沃化銀の分布構造となるように、添加する溶液の量やハロゲン塩水溶液の組成を調製した。
【０２７５】
［乳剤Ｅｍ２−４〜２−６の調製］
乳剤Ｅｍ２−１〜Ｅｍ２−３の調製において、総添加銀量の６．６％を消費した時点で実施例１で用いたＲ−１液をラッシュで添加し、総添加銀量の７０％を消費した時点で実施例１で用いたＴ−１液をラッシュで添加した以外はＥｍ２−１と同様の製造方法により、乳剤Ｅｍ２−４〜２−６を調製した。
【０２７６】
［乳剤Ｅｍ２−７〜Ｅｍ２−９の調製］
乳剤Ｅｍ２−１〜Ｅｍ２−３の調製において、総添加銀量の７０％を消費した時点で実施例１で用いたＴ−１液をラッシュで添加した以外はＥｍ２−１〜Ｅｍ２−３と同様に、乳剤Ｅｍ２−７〜Ｅｍ２−９を調製した。
【０２７７】
［乳剤Ｅｍ２−１０〜Ｅｍ２−１２の調製］
乳剤Ｅｍ２−１〜Ｅｍ２−３の調製において、総添加銀量の６５％を消費した段階で、ｐＡｇを８．９に調製した後、メタルドーピング剤ＳＥＴ−１（Ｋ₄〔Ｆｅ（ＣＮ）₆〕）を水溶液で２×１０^-6モル／モルＡｇ添加し、メタル添加終了時の総添加銀量が７０％を消費した段階で、ｐＡｇを１０．３に調製した以外はＥｍ２−１と同様の製造方法により、乳剤Ｅｍ２−１０〜Ｅｍ２−１２を調製した。
【０２７８】
［乳剤Ｅｍ２−１３〜Ｅｍ２−１５の調製］
乳剤Ｅｍ１−１０〜Ｅｍ１−１２の調製において、メタルドーピング剤をＳＥＴ−１からＳＥＴ−２（Ｋ₄〔Ｒｕ（ＣＮ）₆〕）に代え、水溶液で１×１０^-5モル／モルＡｇ添加した以外はＥｍ２−１０〜Ｅｍ２−１２と同様に、乳剤Ｅｍ２−１３〜Ｅｍ２−１５を調製した。
【０２７９】
［乳剤Ｅｍ２−１６〜Ｅｍ２−１８の調製］
乳剤Ｅｍ２−１〜Ｅｍ２−３の調製において、粒子成長終了後に、特開平５−７２６５８号に記載の方法に従い脱塩処理を施し、その後、ゼラチン溶液を添加し、乳剤温度を５０℃に調整して実施例１で用いたＦ−１液を添加した以外は、乳剤Ｅｍ２−１〜Ｅｍ２−３と同様に、乳剤Ｅｍ２−１６〜Ｅｍ２−１８を調製した。
【０２８０】
［乳剤Ｅｍ２−１９〜Ｅｍ２−２１の調製］
Ｅｍ２−１〜Ｅｍ２−３の成長工程において限外濾過装置を用い、４０℃に降温すると同時に、反応物溶液を９．１ｌにまで濃縮（濃縮前の容積に対して１／３以下）し、反応容器内の銀電位を−３９ｍＶに調整した後、成長工程終了まで反応物溶液の容積を保持した以外はＥｍ２−１〜Ｅｍ２−３と同様にして乳剤Ｅｍ２−１９〜Ｅｍ２−２１を調製した。
【０２８１】
［乳剤Ｅｍ２−２２〜Ｅｍ２−２４の調製］
乳剤Ｅｍ２−１〜Ｅｍ２−３を４０℃で溶解し、１Ｎ硝酸銀水溶液と１Ｎ沃化カリウム水溶液とを流量比８：１で同時添加し、ｐＢｒ４．０に調整した。引き続き１Ｎ塩化ナトリウム水溶液を乳剤（Ｅｍ２−１〜Ｅｍ２−３）１モル当たり０．０２モル添加し、前出の分光増感色素ＳＤ−３及びＳＤ−２を合計被覆率が７０％になるように２：１の比率で添加し、その後０．５Ｎ硝酸銀水溶液と０．５Ｎ塩化ナトリウム水溶液とを定速で、乳剤（Ｅｍ２−１〜Ｅｍ２−３）１モル当たり０．０５モル同時添加した。この操作により平板状ハロゲン化銀粒子の主としてコーナーとエッジにエピタキシャルが形成された乳剤Ｅｍ２−２２〜Ｅｍ２−２４を調製した。
【０２８２】
［乳剤Ｅｍ２−２５〜Ｅｍ２−２７の調製］
乳剤Ｅｍ２−１〜Ｅｍ２−３を６０℃で溶解し、２Ｎ臭化カリウム水溶液でｐＡｇを８．８に調整して実施例１で用いたＫ−１液のハロゲン化銀量で０．７モル相当量を１０分で添加し、２０分間熟成し、その後、４０℃においてｐＡｇ８．０６、ｐＨ５．８に調整して乳剤Ｅｍ２−２５〜Ｅｍ２−２７を調製した。
【０２８３】
［乳剤Ｅｍ２−２８〜Ｅｍ２−３０の調製］
乳剤Ｅｍ２−１〜Ｅｍ２−３の調製において、（Ｂ−１０１）、（Ｇ−１０１）および（Ｇ−１０２）に用いるゼラチンの５０質量パーセントをフェニルカルバモイル化ゼラチン（アミノ基の置換率９０％）に置き換えた以外はＥｍ２−１〜Ｅｍ２−３と同様にして乳剤Ｅｍ２−２８〜Ｅｍ２−３０を作製した。
【０２８４】
なお、乳剤Ｅｍ２−１〜Ｅｍ２−３０は、いずれもアスペクト比５以上の平板状粒子が投影面積の８０％以上を占めていた。これらの乳剤はいずれもフリンジ部に１粒子当たり平均２０本以上の転位線が観察された。各乳剤の特徴を表３，４に示す。
【０２８５】
【表３】

【０２８６】
【表４】

【０２８７】
〔カラー感光材料試料の作製〕
実施例１と同様に増感処理を施した前記乳剤Ｅｍ２−１〜Ｅｍ２−３０を実施例１における乳剤Ｅｍ１−１の代わりに各々使用して、多層カラー写真感光材料試料２００１〜２０３０を作製した。
【０２８８】
試料２００１〜２０３０に、白色光を用いて１／２００秒、１．６ＣＭＳでステップウェッジ露光した後、カラー現像処理で処理し、実施例１と同様の評価を行った。各試料について、得られた結果を表５に示す。
【０２８９】
【表５】

【０２９０】
表から明らかなように、本発明に関わる試料２００５、２００６、２００８、２００９、２０１１、２０１２、２０１４、２０１５、２０１７、２０１８、２０２０、２０２１、２０２３、２０２４、２０２６、２０２７、２０２９、２０３０（本発明の請求項９〜１６に記載の発明の構成）は、比較試料２００１、２００２、２００３、２００４、２００７、２０１０、２０１３、２０１６、２０１９、２０２２、２０２５、２０２８に対して高感度で、粒状性、潜像安定性に優れた性能を示した。
【０２９１】
実施例３
［比較乳剤Ｅｍ３−１の調製］
乳剤Ｅｍ１−１と同様にして乳剤Ｅｍ３−１を作製した。
【０２９２】
［比較乳剤Ｅｍ３−２の調製］
第４シェルを以下のように第４シェル、第５シェルおよび第６シェルに変更する以外は乳剤Ｅｍ１−１と同様にして、乳剤Ｅｍ３−２を調製した。乳剤Ｅｍ３−２は、アスペクト比５以上の平板状粒子が投影面積の８０％以上を占めていた。この乳剤はフリンジ部に１粒子当たり平均２０本以上の転位線が観察された。
【０２９３】
《第４シェルの形成》
上記第３シェルの添加に続き、３．５Ｎ硝酸銀水溶液Ｓ−３０１と３．５Ｎ臭化カリウム水溶液Ｘ−３０１を流量を加速しながら添加し第４シェルを形成した。
【０２９４】
（Ｓ−３０１）
硝酸銀 ２４０．０ｇ
Ｈ₂Ｏ ３４８．５ｍｌ
（Ｘ−３０１）
臭化カリウム １６８．１ｇ
Ｈ₂Ｏ ３４２．６ｍｌ
《第５シェルの形成》
第４シェルの添加に続き、３．５Ｎ硝酸銀水溶液Ｓ−３０２と３．５Ｎ臭化カリウム／沃化カリウム水溶液（沃化カリウム３モル％）Ｘ−３０２を流量を加速しながら添加し第５シェルを形成した。
【０２９５】
（Ｓ−３０２）
硝酸銀 ３６０．０ｇ
Ｈ₂Ｏ ５２２．７ｍｌ
（Ｘ−３０２）
臭化カリウム ２４４．６ｇ
沃化カリウム １０．５５ｇ
Ｈ₂Ｏ ５１３．３ｍｌ
《第６シェルの形成》
上記第５シェルの添加に続き、３．５Ｎ硝酸銀水溶液Ｓ−３０３と３．５Ｎ臭化カリウム水溶液Ｘ−３０３を流量を加速しながら添加し第６シェルを形成した。
【０２９６】
（Ｓ−３０３）
硝酸銀 １２０．０ｇ
Ｈ₂Ｏ １７４．２ｍｌ
（Ｘ−３０３）
臭化カリウム ８４．１ｇ
Ｈ₂Ｏ １７１．３ｍｌ
［比較乳剤Ｅｍ３−３の調製］
乳剤Ｅｍ３−２の調製と同様にして乳剤Ｅｍ３−３を調製した。但し、乳剤Ｅｍ３−３は乳剤が表７に示した沃化銀の分布構造となるように、添加する溶液の量やハロゲン塩水溶液の組成を調製した。
【０２９７】
［乳剤Ｅｍ３−４〜３−６の調製］
乳剤Ｅｍ３−１〜Ｅｍ３−３の調製において、総添加銀量の６．６％を消費した時点で実施例１で用いたＲ−１液をラッシュで添加し、総添加銀量の７０％を消費した時点で実施例１で用いたＴ−１液をラッシュで添加した以外はＥｍ３−１と同様の製造方法により、乳剤Ｅｍ３−４〜３−６を調製した。
【０２９８】
［乳剤Ｅｍ３−７〜Ｅｍ３−９の調製］
乳剤Ｅｍ３−１〜Ｅｍ３−３の調製において、総添加銀量の７０％を消費した時点で実施例１で用いたＴ−１液をラッシュで添加した以外はＥｍ３−１〜Ｅｍ３−３と同様に、乳剤Ｅｍ３−７〜Ｅｍ３−９を調製した。
【０２９９】
［乳剤Ｅｍ３−１０〜Ｅｍ３−１２の調製］
乳剤Ｅｍ３−１〜Ｅｍ３−３の調製において、総添加銀量の６５％を消費した段階で、ｐＡｇを８．９に調整した後、メタルドーピング剤ＳＥＴ−１（Ｋ₄〔Ｆｅ（ＣＮ）₆〕）を水溶液で２×１０^-6モル／モルＡｇ添加し、メタル添加終了時の総添加銀量が７０％を消費した段階で、ｐＡｇを１０．３に調整した以外はＥｍ３−１と同様の製造方法により、乳剤Ｅｍ３−１０〜Ｅｍ３−１２を調製した。
【０３００】
［乳剤Ｅｍ３−１３〜Ｅｍ３−１５の調製］
乳剤Ｅｍ３−１０〜Ｅｍ３−１２の調製において、メタルドーピング剤をＳＥＴ−１からＳＥＴ−２（Ｋ₄〔Ｒｕ（ＣＮ）₆〕）に代え、水溶液で１×１０^-5モル／モルＡｇ添加した以外は３−１０〜Ｅｍ３−１２と同様に、乳剤Ｅｍ３−１３〜Ｅｍ３−１５を調製した。
【０３０１】
［乳剤Ｅｍ３−１６〜Ｅｍ３−１８の調製］
乳剤Ｅｍ３−１〜Ｅｍ３−３の調製において、粒子成長終了後に、特開平５−７２６５８号に記載の方法に従い脱塩処理を施し、その後、ゼラチン溶液を添加し、乳剤温度を５０℃に調整して実施例１で用いた（Ｆ−１）液を添加した以外は、乳剤 Ｅｍ３−１〜Ｅｍ３−３と同様に、乳剤Ｅｍ３−１６〜Ｅｍ３−１８を調製した。
【０３０２】
［乳剤Ｅｍ３−１９〜Ｅｍ３−２１の調製］
Ｅｍ３−１〜Ｅｍ３−３の成長工程において限外濾過装置を用い、４０℃に降温すると同時に、反応物溶液を９．１ｌにまで濃縮（濃縮前の容積に対して１／３以下）し、反応容器内の銀電位を−３９ｍＶに調整した後、成長工程終了まで反応物溶液の容積を保持した以外はＥｍ３−１〜Ｅｍ３−３と同様にして乳剤Ｅｍ３−１９〜Ｅｍ３−２１を調製した。
【０３０３】
［乳剤Ｅｍ３−２２〜Ｅｍ３−２４の調製］
乳剤Ｅｍ３−１〜Ｅｍ３−３を４０℃で溶解し、１Ｎ硝酸銀水溶液と１Ｎ沃化カリウム水溶液とを流量比８：１で同時添加し、ｐＢｒ４．０に調整した。引き続き１Ｎ塩化ナトリウム水溶液を乳剤（Ｅｍ３−１〜Ｅｍ３−３）１モル当たり０．０２モル添加し、前出の分光増感色素ＳＤ−３及びＳＤ−２を合計被覆率が７０％になるように２：１の比率で添加し、その後０．５Ｎ硝酸銀水溶液と０．５N塩化ナトリウム水溶液とを定速で、乳剤（Ｅｍ３−１〜Ｅｍ３−３）１モル当たり０．０５モル同時添加した。この操作により平板状ハロゲン化銀粒子の主としてコーナーとエッジにエピタキシャルが形成された乳剤Ｅｍ３−２２〜Ｅｍ３−２４を調製した。
【０３０４】
［乳剤Ｅｍ３−２５〜Ｅｍ３−２７の調製］
乳剤Ｅｍ３−１〜Ｅｍ３−３を６０℃で溶解し、２Ｎ臭化カリウム水溶液でｐＡｇを８．８に調整して実施例１で用いたＫ−１液のハロゲン化銀量で０．７モル相当量を１０分で添加し、２０分間熟成し、その後、４０℃においてｐＡｇ８．０６、ｐＨ５．８に調整して乳剤Ｅｍ３−２５〜Ｅｍ３−２７を調製した。
【０３０５】
［乳剤Ｅｍ３−２８〜Ｅｍ３−３０の調製］
乳剤Ｅｍ３−１〜Ｅｍ３−３の調製において、（Ｂ−１０１）、（Ｇ−１０１）および（Ｇ−１０２）に用いるゼラチンの５０質量パーセントをフェニルカルバモイル化ゼラチン（アミノ基の置換率９０％）に置き換えた以外はＥｍ３−１〜Ｅｍ３−３と同様にして乳剤Ｅｍ３−２８〜Ｅｍ３−３０を作製した。
【０３０６】
なお、乳剤Ｅｍ３−１〜Ｅｍ３−３０は、いずれもアスペクト比５以上の平板状粒子が投影面積の８０％以上を占めていた。これらの乳剤はいずれもフリンジ部に１粒子当たり平均２０本以上の転位線が観察された。各乳剤の特徴を表６，７に示す。
【０３０７】
【表６】

【０３０８】
【表７】

【０３０９】
〔カラー感光材料試料の作製〕
実施例１と同様にして増感処理を施した前記乳剤Ｅｍ３−１〜Ｅｍ３−３０を実施例１における乳剤Ｅｍ１−１の代わりに各々使用して、多層カラー写真感光材料試料３００１〜３０３０を作製した。
【０３１０】
試料３００１〜３０３０に、白色光を用いて１／２００秒、１．６ＣＭＳでステップウェッジ露光した後、カラー現像処理で処理し、実施例１と同様の評価を行った。各試料について、得られた結果を表８に示す。
【０３１１】
【表８】

【０３１２】
表から明らかなように、本発明に関わる試料３００５、３００６、３００８、３００９、３０１１、３０１２、３０１４、３０１５、３０１７、３０１８、３０２０、３０２１、３０２３、３０２４、３０２６、３０２７、３０２９、３０３０（本発明の請求項１７〜２０に記載の発明の構成）は、比較試料３００１、３００２、３００３、３００４、３００７、３０１０、３０１３、３０１６、３０１９、３０２２、３０２５、３０２８に対して高感度で、粒状性、潜像安定性に優れた性能を示した。
【０３１３】
実施例４
［比較乳剤Ｅｍ４−１の調製］
乳剤Ｅｍ１−１と同様にして乳剤Ｅｍ４−１を作製した。
【０３１４】
［比較乳剤Ｅｍ４−２の調製］
核生成工程のＳ−１０１およびＸ−１０１をそれぞれＳ−４０１およびＸ−４０１に変更してコアとし、以下を第１シェル〜第５シェルと名称変更する以外は乳剤乳剤Ｅｍ１−１と同様にして乳剤Ｅｍ４−２を作製した
（Ｓ−４０１）
硝酸銀 １８．８ｇ
Ｈ₂Ｏ ８４．４ｍｌ
（Ｘ−４０１）
臭化カリウム １１．９ｇ
沃化カリウム １．８４ｇ
Ｈ₂Ｏ ８３．６ｍｌ
［比較乳剤Ｅｍ４−３の調製］
第５シェルを以下のように変更する以外は乳剤Ｅｍ４−２と同様にして、乳剤Ｅｍ４−３を調製した。
【０３１５】
《第５シェルの形成》
第４シェルの添加に続き、３．５Ｎ硝酸銀水溶液Ｓ−４０２と３．５Ｎ臭化カリウム／沃化カリウム水溶液（沃化カリウム３モル％）Ｘ−４０２を流量を加速しながら添加し第５シェルを形成した。
【０３１６】
（Ｓ−４０２）
硝酸銀 ５７６．０ｇ
Ｈ₂Ｏ ８３６．４ｍｌ
（Ｘ−４０２）
臭化カリウム ３９１．４ｇ
沃化カリウム １６．８９ｇ
Ｈ₂Ｏ ８２１．２ｍｌ
《第６シェルの形成》
上記第５シェルの添加に続き、３．５Ｎ硝酸銀水溶液Ｓ−４０３と３．５Ｎ臭化カリウム水溶液Ｘ−４０３を流量を加速しながら添加し第６シェルを形成した。
【０３１７】
（Ｓ−４０３）
硝酸銀 １４４．０ｇ
Ｈ₂Ｏ ２０９．１ｍｌ
（Ｘ−４０３）
臭化カリウム １００．９ｇ
Ｈ₂Ｏ ２０５．６ｍｌ
［乳剤Ｅｍ４−４〜４−６の調製］
乳剤Ｅｍ４−１〜Ｅｍ４−３の調製において、総添加銀量の６．６％を消費した時点で実施例１で用いたＲ−１液をラッシュで添加し、総添加銀量の７０％を消費した時点で実施例１で用いたＴ−１液をラッシュで添加した以外はＥｍ４−１と同様の製造方法により、乳剤Ｅｍ４−４〜４−６を調製した。
【０３１８】
［乳剤Ｅｍ４−７〜Ｅｍ４−９の調製］
乳剤Ｅｍ４−１〜Ｅｍ４−３の調製において、総添加銀量の７０％を消費した時点でＴ−１液をラッシュで添加した以外はＥｍ４−１〜Ｅｍ４−３と同様に、乳剤Ｅｍ４−７〜Ｅｍ４−９を調製した。
【０３１９】
［乳剤Ｅｍ４−１０〜Ｅｍ４−１２の調製］
乳剤Ｅｍ４−１〜Ｅｍ４−３の調製において、総添加銀量の６５％を消費した段階で、ｐＡｇを８．９に調整した後、メタルドーピング剤ＳＥＴ−１（Ｋ₄〔Ｆｅ（ＣＮ）₆〕）を水溶液で２×１０^-6モル／モルＡｇ添加し、メタル添加終了時の総添加銀量が７０％を消費した段階で、ｐＡｇを１０．３に調整した以外はＥｍ４−１と同様の製造方法により、乳剤Ｅｍ４−１０〜Ｅｍ４−１２を調製した。
【０３２０】
［乳剤Ｅｍ４−１３〜Ｅｍ４−１５の調製］
乳剤Ｅｍ４−１０〜Ｅｍ４−１２の調製において、メタルドーピング剤をＳＥＴ−１からＳＥＴ−２（Ｋ₄〔Ｒｕ（ＣＮ）₆〕）に代え、水溶液で１×１０^-5モル／モルＡｇ添加した以外はＥｍ４−１０〜Ｅｍ４−１２と同様に、乳剤Ｅｍ４−１３〜Ｅｍ４−１５を調製した。
【０３２１】
［乳剤Ｅｍ４−１６〜Ｅｍ４−１８の調製］
乳剤Ｅｍ４−１〜Ｅｍ４−３の調製において、粒子成長終了後に、特開平５−７２６５８号に記載の方法に従い脱塩処理を施し、その後、ゼラチン溶液を添加し、乳剤温度を５０℃に調整して実施例１で用いたＦ−１液を添加した以外は、乳剤Ｅｍ４−１〜Ｅｍ４−３と同様に、乳剤Ｅｍ４−１６〜Ｅｍ４−１８を調製した。
【０３２２】
［乳剤Ｅｍ４−１９〜Ｅｍ４−２１の調製］
Ｅｍ４−１〜Ｅｍ４−３の成長工程において限外濾過装置を用い、４０℃に降温すると同時に、反応物溶液を９．１ｌにまで濃縮（濃縮前の容積に対して１／３以下）し、反応容器内の銀電位を−３９ｍＶに調整した後、成長工程終了まで反応物溶液の容積を保持した以外はＥｍ４−１〜Ｅｍ４−３と同様にして乳剤Ｅｍ４−１９〜Ｅｍ４−２１を調製した。
【０３２３】
［乳剤Ｅｍ４−２２〜Ｅｍ４−２４の調製］
乳剤Ｅｍ４−１〜Ｅｍ４−３を４０℃で溶解し、１Ｎ硝酸銀水溶液と１Ｎ沃化カリウム水溶液とを流量比８：１で同時添加し、ｐＢｒ４．０に調整した。引き続き１Ｎ塩化ナトリウム水溶液を乳剤（Ｅｍ４−１〜Ｅｍ４−３）１モル当たり０．０２モル添加し、前出の分光増感色素ＳＤ−３及びＳＤ−２を合計被覆率が７０％になるように２：１の比率で添加し、その後０．５Ｎ硝酸銀水溶液と０．５Ｎ塩化ナトリウム水溶液とを定速で、乳剤（Ｅｍ４−１〜Ｅｍ４−３）１モル当たり０．０５モル同時添加した。この操作により平板状ハロゲン化銀粒子の主としてコーナーとエッジにエピタキシャルが形成された乳剤Ｅｍ４−２２〜Ｅｍ４−２４を調製した。
【０３２４】
［乳剤Ｅｍ４−２５〜Ｅｍ４−２７の調製］
乳剤Ｅｍ４−１〜Ｅｍ４−３を６０℃で溶解し、２Ｎ臭化カリウム水溶液でｐＡｇを８．８に調整して実施例１で用いたＫ−１液のハロゲン化銀量で０．７モル相当量を１０分で添加し、２０分間熟成し、その後、４０℃においてｐＡｇ８．０６、ｐＨ５．８に調整して乳剤Ｅｍ４−２５〜Ｅｍ４−２７を調製した。
【０３２５】
［乳剤Ｅｍ４−２８〜Ｅｍ４−３０の調製］
乳剤Ｅｍ４−１〜Ｅｍ４−３の調製において、（Ｂ−１０１）、（Ｇ−１０１）および（Ｇ−１０２）に用いるゼラチンの５０質量パーセントをフェニルカルバモイル化ゼラチン（アミノ基の置換率９０％）に置き換えた以外はＥｍ４−１〜Ｅｍ４−３と同様にして乳剤Ｅｍ４−２８〜Ｅｍ４−３０を作製した。
【０３２６】
なお、乳剤Ｅｍ４−１〜Ｅｍ４−３０は、いずれもアスペクト比５以上の平板状粒子が投影面積の８０％以上を占めていた。これらの乳剤はいずれもフリンジ部に１粒子当たり平均２０本以上の転位線が観察された。各乳剤の特徴を表９，１０に示す。
【０３２７】
【表９】

【０３２８】
【表１０】

【０３２９】
〔カラー感光材料試料の作製〕
実施例１と同様に増感処理を施した前記乳剤Ｅｍ４−１〜Ｅｍ４−３０を実施例１における乳剤Ｅｍ１−１の代わりに各々使用して、多層カラー写真感光材料試料４００１〜４０３０を作製した。
【０３３０】
試料４００１〜４０３０に、白色光を用いて１／２００秒、１．６ＣＭＳでステップウェッジ露光した後、カラー現像処理で処理し、実施例１と同様の評価を行った。各試料について、得られた結果を表１１に示す。
【０３３１】
【表１１】

【０３３２】
表から明らかなように、本発明に関わる試料４００５、４００６、４００８、４００９、４０１１、４０１２、４０１４、４０１５、４０１７、４０１８、４０２０、４０２１、４０２３、４０２４、４０２６、４０２７、４０２９、４０３０（本発明の請求項２５〜３２に記載の発明の構成）は、比較試料４００１、４００２、４００３、４００４、４００７、４０１０、４０１３、４０１６、４０１９、４０２２、４０２５、４０２８に対して高感度で、粒状性、潜像安定性に優れた性能を示した。
【０３３３】
実施例５
［比較乳剤Ｅｍ５−１の調製］
乳剤Ｅｍ１−１と同様にして乳剤Ｅｍ５−１を作製した。
【０３３４】
［比較乳剤Ｅｍ５−２の調製］
《内部相の形成》
乳剤Ｅｍ１−１と同様に核形成工程を行った後、以下の核成長工程を行って内部相を形成した。
【０３３５】
〔核成長工程〕
ダブルジェット法を用いて３．５Ｎ硝酸銀水溶液Ｓ−５０１と３．５Ｎ臭化カリウム水溶液Ｘ−５０１を流量を加速しながら（終了時と開始時の添加流量の比が約１２倍）３８分間で添加した。この間溶液の銀電位を１Ｎの臭化カリウム溶液を用いて６ｍＶに制御した。添加終了後にＧ−５０１を加えた。
【０３３６】
（Ｓ−５０１）
硝酸銀 ８０９．２ｇ
Ｈ₂Ｏ １１７５．０ｍｌ
（Ｘ−５０１）
臭化カリウム ９７．７ｇ
Ｈ₂Ｏ １１５５．３ｍｌ
（Ｇ−５０１）
アルカリ処理不活性ゼラチン（平均分子量１０万） ８４．０ｇ
前記〔化合物Ａ〕の１０質量％メタノール溶液 ２．３ｍｌ
Ｈ₂Ｏ ６００．０ｍｌ
《第１高沃度局在相の形成》
上記添加終了後に、平均粒径０．０３μｍの沃化銀微粒子乳剤を０．２１２モル相当量加えて第１高沃度局在相を形成した。
【０３３７】
《中間相の形成》
上記コア相の形成に続き、３．５Ｎ硝酸銀水溶液Ｓ−５０２と３．５Ｎ臭化カリウム水溶液Ｘ−５０２を流量を加速しながら添加し中間相を形成した。この間溶液の銀電位を１Ｎの臭化カリウム溶液を用いて６ｍＶに制御した。
【０３３８】
（Ｓ−５０２）
硝酸銀 ７６８．０ｇ
Ｈ₂Ｏ １１１５．２ｍｌ
（Ｘ−５０２）
臭化カリウム ５３８．１ｇ
沃化カリウム ６９．０ｇ
Ｈ₂Ｏ １０９６．５ｍｌ
《高沃度局在相の形成》
上記添加終了後に、反応容器内の溶液温度を３０分を要して４０℃に降温した。その後、３．５Ｎの臭化カリウム水溶液を用いて反応容器内の銀電位を−３２ｍＶに調整し、平均粒径０．０３μｍの沃化銀微粒子乳剤溶液を０．２８３モル相当量加えて高沃度局在相を形成した。
【０３３９】
《シェル相の形成》
上記沃化銀微粒子乳剤の添加に続き、３．５Ｎ硝酸銀水溶液Ｓ−５０３と３．５Ｎ臭化カリウム水溶液Ｘ−５０３を流量を加速しながら添加しシェル相を形成した。
【０３４０】
（Ｓ−５０３）
硝酸銀 ７２０．０ｇ
Ｈ₂Ｏ １０４５．５ｍｌ
（Ｘ−５０３）
臭化カリウム ５０４．４ｇ
Ｈ₂Ｏ １０２８．０ｍｌ
核生成時を除き上記の各相形成時の硝酸銀水溶液及びハロゲン塩水溶液の添加は、添加中の新核生成が起こらない範囲で添加速度を高めて行った。シェル相形成終了後に特開平５−７２６５８号に記載の方法に従い脱塩・水洗処理を施し、ゼラチンを加えて良く分散し、４０℃にてｐＨを５．８、ｐＡｇを８．１に調整した。
【０３４１】
［比較乳剤Ｅｍ５−３の調製］
乳剤Ｅｍ５−２の調製と同様にして乳剤Ｅｍ５−３を調製した。但し、乳剤が表１２に示した沃化銀の分布構造となるように、添加する溶液の量やハロゲン塩水溶液の組成を調製した。乳剤Ｅｍ５−３は、いずれもアスペクト比５以上の平板状粒子が投影面積の８０％以上を占めていた。また、これらの乳剤はいずれもフリンジ部に１粒子当たり平均２０本以上の転位線が観察された。
【０３４２】
［乳剤Ｅｍ５−４〜５−６の調製］
乳剤Ｅｍ５−１〜Ｅｍ５−３の調製において、総添加銀量の６．６％を消費した時点で実施例１で用いたＲ−１液をラッシュで添加し、総添加銀量の７０％を消費した時点で実施例１で用いたＴ−１液をラッシュで添加した以外はＥｍ５−１と同様の製造方法により、乳剤Ｅｍ５−４〜５−６を調製した。
【０３４３】
［乳剤Ｅｍ５−７〜Ｅｍ５−９の調製］
乳剤Ｅｍ５−１〜Ｅｍ５−３の調製において、総添加銀量の７０％を消費した時点で実施例１で用いたＴ−１液をラッシュで添加した以外はＥｍ５−１〜Ｅｍ５−３と同様に、乳剤Ｅｍ５−７〜Ｅｍ５−９を調製した。
【０３４４】
［乳剤Ｅｍ５−１０〜Ｅｍ５−１２の調製］
乳剤Ｅｍ５−１〜Ｅｍ５−３の調製において、総添加銀量の６５％を消費した段階で、ｐＡｇを８．９に調製した後、メタルドーピング剤ＳＥＴ−１（Ｋ₄〔Ｆｅ（ＣＮ）₆〕）を水溶液で２×１０^-6モル／モルＡｇ添加し、メタル添加終了時の総添加銀量が７０％を消費した段階で、ｐＡｇを１０．３に調整した以外はＥｍ５−１と同様の製造方法により、乳剤Ｅｍ５−１０〜Ｅｍ５−１２を調製した。
【０３４５】
［乳剤Ｅｍ５−１３〜Ｅｍ５−１５の調製］
乳剤Ｅｍ５−１０〜Ｅｍ５−１２の調製において、メタルドーピング剤をＳＥＴ−１からＳＥＴ−２（Ｋ₄〔Ｒｕ（ＣＮ）₆〕）に代え、水溶液で１×１０^-5モル／モルＡｇ添加した以外はＥｍ５−１０〜Ｅｍ５−１２と同様に、乳剤Ｅｍ５−１３〜Ｅｍ５−１５を調製した。
【０３４６】
［乳剤Ｅｍ５−１６〜Ｅｍ５−１８の調製］
乳剤Ｅｍ５−１〜Ｅｍ５−３の調製において、粒子成長終了後に、特開平５−７２６５８号に記載の方法に従い脱塩処理を施し、その後、ゼラチン溶液を添加し、乳剤温度を５０℃に調整して実施例１で用いたＦ−１液を添加した以外は、乳剤Ｅｍ５−１〜Ｅｍ５−３と同様に、乳剤Ｅｍ５−１６〜Ｅｍ５−１８を調製した。
【０３４７】
［乳剤Ｅｍ５−１９〜Ｅｍ５−２１の調製］
Ｅｍ５−１〜Ｅｍ４−３の成長工程において限外濾過装置を用い、４０℃に降温すると同時に、反応物溶液を９．１ｌにまで濃縮（濃縮前の容積に対して１／３以下）し、反応容器内の銀電位を−３９ｍＶに調整した後、成長工程終了まで反応物溶液の容積を保持した以外はＥｍ５−１〜Ｅｍ５−３と同様にして乳剤Ｅｍ５−１９〜Ｅｍ５−２１を調製した。
【０３４８】
［乳剤Ｅｍ５−２２〜Ｅｍ５−２４の調製］
乳剤Ｅｍ５−１〜Ｅｍ５−３を４０℃で溶解し、１Ｎ硝酸銀水溶液と１Ｎ沃化カリウム水溶液とを流量比８：１で同時添加し、ｐＢｒ４．０に調整した。引き続き１Ｎ塩化ナトリウム水溶液を乳剤（Ｅｍ５−１〜Ｅｍ５−３）１モル当たり０．０２モル添加し、前出の分光増感色素ＳＤ−３及びＳＤ−２を合計被覆率が７０％になるように２：１の比率で添加し、その後０．５Ｎ硝酸銀水溶液と０．５N塩化ナトリウム水溶液とを定速で、乳剤（Ｅｍ５−１〜Ｅｍ５−３）１モル当たり０．０５モル同時添加した。この操作により平板状ハロゲン化銀粒子の主としてコーナーとエッジにエピタキシャルが形成された乳剤Ｅｍ５−２２〜Ｅｍ５−２４を調製した。
【０３４９】
［乳剤Ｅｍ５−２５〜Ｅｍ５−２７の調製］
乳剤Ｅｍ５−１〜Ｅｍ５−３を６０℃で溶解し、２Ｎ臭化カリウム水溶液でｐＡｇを８．８に調整して実施例１で用いたＫ−１液のハロゲン化銀量で０．７モル相当量を１０分で添加し、２０分間熟成し、その後、４０℃においてｐＡｇ８．０６、ｐＨ５．８に調整して乳剤Ｅｍ５−２５〜Ｅｍ５−２７を調製した。
【０３５０】
［乳剤Ｅｍ５−２８〜Ｅｍ５−３０の調製］
乳剤Ｅｍ５−１〜Ｅｍ５−３の調製において、（Ｂ−１０１）、（Ｇ−１０１）および（Ｇ−１０２）に用いるゼラチンの５０質量パーセントをフェニルカルバモイル化ゼラチン（アミノ基の置換率９０％）に置き換えた以外はＥｍ５−１〜Ｅｍ５−３と同様にして乳剤Ｅｍ５−２８〜Ｅｍ５−３０を作製した。
【０３５１】
なお、乳剤Ｅｍ５−１〜Ｅｍ５−３０は、いずれもアスペクト比５以上の平板状粒子が投影面積の８０％以上を占めていた。これらの乳剤はいずれもフリンジ部に１粒子当たり平均２０本以上の転位線が観察された。各乳剤の特徴を表１２に示す。
【０３５２】
【表１２】

【０３５３】
〔カラー感光材料試料の作製〕
実施例１と同様に増感処理を施した前記乳剤Ｅｍ５−１〜Ｅｍ５−３０を実施例１における乳剤Ｅｍ１−１の代わりに各々使用して、多層カラー写真感光材料試料５００１〜５０３０を作製した。
【０３５４】
試料５００１〜５０３０に、白色光を用いて１／２００秒、１．６ＣＭＳでステップウェッジ露光した後、カラー現像処理で処理し、実施例１と同様の評価を行った。各試料について、得られた結果を表１３に示す。
【０３５５】
【表１３】

【０３５６】
表から明らかなように、本発明に関わる試料５００５、５００６、５００８、５００９、５０１１、５０１２、５０１４、５０１５、５０１７、５０１８、５０２０、５０２１、５０２３、５０２４、５０２６、５０２７、５０２９、５０３０（本発明の請求項３３〜４０に記載の発明の構成）は、比較試料５００１、５００２、５００３、５００４、５００７、５０１０、５０１３、５０１６、５０１９、５０２２、５０２５、５０２８に対して高感度で、粒状性、潜像安定性に優れた性能を示した。
【０３５７】
【発明の効果】
本発明により、感度、粒状性、潜像安定性に優れたハロゲン化銀乳剤およびハロゲン化銀写真感光材料を提供することができた。
【図面の簡単な説明】
【図１】本発明に適用できるハロゲン化銀乳剤の製造装置の一例を示す概略図である。
【符号の説明】
１ 反応容器
２ 撹拌機構
３ 分散媒体
４ 銀添加ライン
５ ハライド添加ライン
６ 分散媒体添加ライン
７ 添加ライン
８ 液取り出しライン
９ 液戻しライン
１０ 透過液排出ライン
１１ 透過液戻りライン
１２ 限外濾過ユニット
１３ 循環ポンプ
１４ 流量計
１５、１６、１７ 圧力計
１８ 圧力調整用バルブ
１９ 流量調節用バルブ
２０ 銀添加バルブ
２１ ハライド添加バルブ
２２ 液抜き取りバルブ
２３、２４、２５ バルブ
２６ 限外濾過透過液
２７ 透過液受け容器
２８ 秤
２９、３０ ハロゲン化銀微粒子乳剤添加ライン
３１、３２ 微粒子添加用バルブ[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a silver halide emulsion and a silver halide photographic light-sensitive material. More specifically, the present invention relates to a silver halide emulsion and a silver halide photographic light-sensitive material excellent in sensitivity, graininess, and latent image stability.
[0002]
[Prior art]
The spread of photographing devices such as cameras has been increasing in recent years, and opportunities for taking photographs using silver halide photographic light-sensitive materials have been increasing. The demand for higher sensitivity and higher image quality is also increasing.
[0003]
One of the dominant factors for higher sensitivity and higher image quality of silver halide photographic materials is silver halide grains. Development of silver halide grains aimed at higher sensitivity and higher image quality Has been in the industry for a long time.
[0004]
However, as is generally done, the sensitivity tends to decrease when the grain size of silver halide grains is reduced to improve the image quality, and there is a limit to achieving both high sensitivity and high image quality. there were.
[0005]
A technique for improving the sensitivity / grain size ratio per silver halide grain has been studied in order to achieve higher sensitivity and higher image quality. As one of them, techniques using tabular silver halide grains are described in JP-A Nos. 58-11935, 58-11936, 58-11937, 58-11939, and 59-99433. Has been. When these tabular silver halide grains are compared with so-called normal crystal silver halide grains such as octahedron, tetrahedron, or hexahedron, the surface area becomes larger when the volume of the silver halide grains is the same. Many sensitizing dyes can be adsorbed on the surface of silver particles, and there is an advantage that higher sensitivity can be achieved.
[0006]
In JP-A-6-230491, JP-A-6-235588, JP-A-6-258745, JP-A-6-289516, etc., studies have been made on using tabular silver halide grains having a higher aspect ratio than before.
[0007]
Further, JP-A-63-92942 discloses a technique for providing a core having a high silver iodide content inside a tabular silver halide grain, and JP-A-63-163541 relates to the longest distance between twin planes. Techniques using tabular silver halide grains having a grain thickness ratio of 5 or more are disclosed, and effects on sensitivity and graininess are shown, respectively.
[0008]
JP-A-63-106746 discloses tabular silver halide grains having a substantially layered structure in a direction parallel to two opposing principal planes, and JP-A-1-279237 discloses two tabular silver halide grains. Having a layered structure separated by planes substantially parallel to two opposing main planes, and the average silver iodide content of the outermost layer is at least 1 than the average silver iodide content of the entire silver halide grains A technique for using tabular silver halide grains higher by mol% or more is described.
[0009]
In JP-A-3-121445, silver halide grains composed of an interface layer having parallel twin planes and regions having different iodine content from each other are disclosed in JP-A-63-305343. JP-A-2-34 discloses a tabular silver halide grain having a development start point, and JP-A-2-34 discloses silver halide grains having a (100) plane and a (111) plane.
[0010]
In addition, Japanese Patent Application Laid-Open No. 1-183644 discloses a technique using tabular silver halide grains characterized in that the silver iodide distribution of silver halide containing silver iodide is completely uniform.
[0011]
Also disclosed is a technique for controlling carriers by metal doping, that is, a technique for improving photographic characteristics by mainly containing a polyvalent metal oxide in silver halide grains.
[0012]
Japanese Patent Application Laid-Open Nos. 3-196135 and 3-189441 disclose silver halide emulsions prepared in the presence of an oxidizing agent for silver, and sensitivity and fog when using a silver halide photographic light-sensitive material using the same. The effect on is disclosed.
[0013]
Further, for example, in Japanese Patent Laid-Open No. 63-220238, a technique using a silver halide emulsion containing tabular silver halide grains in which the positions of dislocation lines are defined is disclosed in Japanese Patent Laid-Open No. A technique using a silver halide emulsion containing tabular silver halide grains in which dislocation lines are concentrated is disclosed. In Japanese Patent Publication No. 3-18695, a technique using silver halide grains having a clear core / shell structure is disclosed. However, in Japanese Examined Patent Publication No. 3-31245, a technology relating to a silver halide grain having a core / shell three-layer structure has been taken up and has been studied as a technology for increasing sensitivity.
[0014]
Regarding the core-shell structure, US Pat. No. 4,668,614 improves sensitivity and graininess by using double-structured grains in which the core portion has a high silver iodide content and the shell portion has a low silver iodide content. Techniques for making them disclosed are disclosed. U.S. Pat. No. 4,614,711 is sensitive to triple structure grains having a low silver iodide content in the core part, a high silver iodide content in the intermediate shell and a low silver iodide content in the shell part. And a technique for improving graininess and pressure resistance. In European Patent No. 202,784B, an intermediate shell having an intermediate silver iodide content between the high silver iodide content intermediate shell and the low silver iodide containing shell portion of the triple structure grain is further provided. Further, a technique for improving sensitivity / fogging ratio and graininess by using quadruple structure particles is disclosed. JP-A-7-244345 discloses an inner shell having a silver iodide content of 1 mol% or less, a first coating layer of 2 to 20 mol%, a second coating layer of 3 mol% or less, and a second coating. A technique for improving pressure resistance, sensitivity, latent image storage stability, and incubation resistance by using a grain having a high iodine layer during and after layer formation is disclosed. Further, as a technique similar to this, JP-A-8-314040, JP-A-9-197593, US Pat. No. 5,728,515 and the like are known. However, the recent demand for improvement in photographic performance is insufficient, and further improvements in sensitivity, graininess, and latent image stability have been desired.
[0015]
[Problems to be solved by the invention]
An object of the present invention is to develop a technique capable of improving both sensitivity, graininess, and latent image stability, and to provide a silver halide emulsion and a silver halide photographic light-sensitive material excellent in these characteristics.
[0016]
[Means for Solving the Problems]
The above object of the present invention has been achieved by the following constitution.
[0017]
A silver halide emulsion comprising silver halide grains and a dispersion medium, wherein the silver halide grains have at least a five-layer structure of a core, a first shell, a second shell, a third shell, and a fourth shell from the center. And the core ratio is 5% or more and 50% or less with respect to the total silver amount, the average silver iodide content is 0 mol% or more and 3 mol% or less, and the ratio of the first shell is all 5% to 30% with respect to the silver amount, the average silver iodide content is 3% to 10% by mole, and the ratio of the second shell is 10% to 30% with respect to the total silver amount. The average silver iodide content is 0 mol% or more and 3 mol% or less, and the ratio of the third shell is 0.5% or more and 5% or less with respect to the total silver amount, The average silver iodide content is 40 mol% or more and 100 mol% or less, and the ratio of the fourth shell is based on the total silver amount. A 40% or less is 0% or higher, and the average silver iodide content of not more than 3 mol% to 10 mol%,
(1) A silver halide emulsion characterized by reduction sensitization.
(2) A silver halide emulsion characterized by containing an oxidizing agent for silver nuclei.
(3) A silver halide emulsion comprising a hexacoordinate cyano complex of at least one polyvalent metal.
(4) A silver halide emulsion comprising silver halide fine grains containing at least one polyvalent metal compound.
(5) A silver halide emulsion, wherein the silver halide grains contained in the silver halide emulsion are formed by a grain distance control method.
(6) A silver halide emulsion wherein the silver halide grains contained in the silver halide emulsion have silver halide protrusions on the grain surface.
(7) A silver halide emulsion wherein the silver halide grains contained in the silver halide emulsion contain silver chloride.
(8) Silver halide characterized in that 10 mass percent or more of the dispersion medium used for the formation of silver halide grains contained in the silver halide emulsion is chemically modified gelatin substituted with amino groups emulsion.
[0018]
More preferably, the silver halide grains have at least a five-layer structure of a core, a first shell, a second shell, a third shell, and a fourth shell from the center, and the core ratio is based on the total silver amount. The average silver iodide content is 10% or more and 40% or less, and the ratio of the first shell is 10% or more and 25% or less with respect to the total silver amount. The average silver iodide content is 5 mol% or more and 10 mol% or less, the ratio of the second shell is 15% or more and 25% or less with respect to the total silver amount, and the average silver iodide content is When the ratio of the third shell is 1% or more and 3% or less with respect to the total silver amount, and the average silver iodide content is 60% or more and 100% or less by mole. The ratio of the fourth shell is 15% or more and 30% or less with respect to the total silver amount, and its average iodide Set forth in any one silver halide emulsion of the 1 to 8, wherein the content of 3 mol% to 5 mol% or less.
[0019]
Further, as another embodiment, a silver halide emulsion containing silver halide grains and a dispersion medium, wherein the silver halide grains are arranged from the center to the core, the first shell, the second shell, the third shell, and the fourth shell. The fifth shell has at least a six-layer structure, and the core ratio is 5% or more and 50% or less with respect to the total silver amount, and the average silver iodide content is 0 mol% or more and 3 mol% or less. The ratio of the first shell is 5% to 30% with respect to the total silver amount, the average silver iodide content is 3 mol% to 20 mol%, and the ratio of the second shell is The average silver iodide content is 10 mol% or more and 30 mol% or less with respect to the total silver amount, and the ratio of the third shell is 0.5 mol or less with respect to the total silver amount. % Of silver iodide, and the average silver iodide content is 40 mol% or more and 100 mol% or less, The ratio of 4 shells is 10% or more and 40% or less with respect to the total silver amount, the average silver iodide content is 3 mol% or more and 10 mol% or less, and the ratio of the fifth shell is the total silver amount. 3% or more and 20% or less, and the average silver iodide content is 0 mol% or more and 3 mol% or less,
(9) A silver halide emulsion characterized by reduction sensitization.
(10) A silver halide emulsion characterized by containing an oxidizing agent for silver nuclei.
(11) A silver halide emulsion comprising a hexacoordinate cyano complex of at least one polyvalent metal.
(12) A silver halide emulsion to which silver halide fine grains containing at least one polyvalent metal compound are added.
(13) A silver halide emulsion, wherein the silver halide grains contained in the silver halide emulsion are formed by a grain distance control method.
(14) A silver halide emulsion wherein the silver halide grains contained in the silver halide emulsion have silver halide protrusions on the grain surface.
(15) A silver halide emulsion wherein the silver halide grains contained in the silver halide emulsion contain silver chloride.
(16) Silver halide characterized in that 10 mass percent or more of the dispersion medium used for the formation of silver halide grains contained in the silver halide emulsion is chemically modified gelatin substituted with amino groups emulsion.
[0020]
More preferably, the silver halide grains have at least six layers of a core, a first shell, a second shell, a third shell, a fourth shell, and a fifth shell from the center, and the ratio of the core is all silver. The average silver iodide content is 10% or more and 40% or less with respect to the amount, and the ratio of the first shell is 10% or more and 25% with respect to the total silver amount. The average silver iodide content is 5 mol% or more and 15 mol% or less, the ratio of the second shell is 15% or more and 25% or less with respect to the total silver amount, The silver content is 0 mol% or more and 2 mol% or less, the ratio of the third shell is 1% or more and 3% or less with respect to the total silver amount, and the average silver iodide content is 60 mol% or more and 100 mol%. And the ratio of the fourth shell is 15% or more and 30% or less with respect to the total silver amount, The average silver iodide content is 3 mol% or more and 5 mol% or less, the ratio of the fifth shell is 5% or more and 10% or less with respect to the total silver amount, and the average silver iodide content is 0 17. The silver halide emulsion as described in any one of 9 to 16 above, which is contained in an amount of from mol% to 2 mol%.
[0021]
In another aspect, a silver halide emulsion containing silver halide grains and a dispersion medium, wherein the silver halide grains are arranged from the center to the core, the first shell, the second shell, the third shell, the fourth shell, It has at least a seven-layer structure of a fifth shell and a sixth shell, and the core ratio is 5% or more and 50% or less with respect to the total silver amount, and the average silver iodide content is 0 mol% or more and 3 And the ratio of the first shell is 5% or more and 30% or less with respect to the total silver amount, and the average silver iodide content is 3 mol% or more and 20 mol% or less. The ratio of the total silver content is 10% or more and 30% or less, the average silver iodide content is 0 mol% or more and 3 mol% or less, and the ratio of the third shell is based on the total silver amount. 0.5% or more and 5% or less, and the average silver iodide content is 40 mol% or more and 100 mol% or less The ratio of the fourth shell is 3% or more and 20% or less with respect to the total silver amount, the average silver iodide content thereof is 0 mol% or more and 3 mol% or less, and the ratio of the fifth shell is 10% or more and 40% or less with respect to the silver amount, the average silver iodide content is 3 to 10% by mole, and the ratio of the sixth shell is 3% or more with respect to the total silver amount 20% or less, and the average silver iodide content is 0 mol% or more and 3 mol% or less,
(17) A silver halide emulsion characterized by reduction sensitization.
(18) A silver halide emulsion characterized by containing an oxidizing agent for silver nuclei.
(19) A silver halide emulsion comprising a hexacoordinate cyano complex of at least one polyvalent metal.
(20) A silver halide emulsion wherein silver halide fine grains containing at least one polyvalent metal compound are added.
(21) A silver halide emulsion, wherein the silver halide grains contained in the silver halide emulsion are formed by a grain distance control method.
(22) A silver halide emulsion wherein the silver halide grains contained in the silver halide emulsion have silver halide protrusions on the grain surface.
(23) A silver halide emulsion wherein the silver halide grains contained in the silver halide emulsion contain silver chloride.
(24) Silver halide characterized in that 10 mass percent or more of the dispersion medium used for the formation of silver halide grains contained in the silver halide emulsion is chemically modified gelatin substituted with amino groups emulsion.
[0022]
More preferably, the silver halide grains have at least a seven-layer structure of a core, a first shell, a second shell, a third shell, a fourth shell, a fifth shell, and a sixth shell from the center, The ratio is 10% to 40% with respect to the total silver amount, the average silver iodide content is 0 mol% to 2 mol%, and the ratio of the first shell is 10% with respect to the total silver amount. The average silver iodide content is not less than 5 mol% and not more than 15 mol%, and the ratio of the second shell is not less than 15% and not more than 25% with respect to the total silver amount, The average silver iodide content is 0 mol% or more and 2 mol% or less, the ratio of the third shell is 1% or more and 3% or less with respect to the total silver amount, and the average silver iodide content is 60 Mol% or more and 100 mol% or less, and the ratio of the fourth shell is 5% or more and 10% or less with respect to the total silver amount. The average silver iodide content is 0 mol% or more and 2 mol% or less, and the ratio of the fifth shell is 15% or more and 30% or less with respect to the total silver amount, and the average silver iodide content is And the ratio of the sixth shell is 5% or more and 10% or less with respect to the total silver amount, and the average silver iodide content is 0 mol% or more and 2 mol%. 25. The silver halide emulsion as described in any one of 17 to 24 above, which is not more than%.
[0023]
Further, a silver halide emulsion containing silver halide grains and a dispersion medium, wherein the silver halide grains are arranged from the central portion to the core, the first shell, the second shell, the third shell, the fourth shell, and the fifth shell. , Having at least a seven-layer structure of a sixth shell and having a core ratio of 0.1% to 1% with respect to the total silver amount, and an average silver iodide content of 4 mol% to 20 mol %, The ratio of the first shell is 5% or more and 50% or less with respect to the total silver amount, and the average silver iodide content is 0 mol% or more and 3 mol% or less. The ratio is 5% to 30% with respect to the total silver amount, the average silver iodide content is 3% to 20% by mole, and the ratio of the third shell is 10% with respect to the total silver amount. % To 30%, and the average silver iodide content is 0 mol% to 3 mol%. The ratio of the total silver content is 0.5% or more and 5% or less, the average silver iodide content is 40 mol% or more and 100 mol% or less, and the ratio of the fifth shell is the total silver amount. And the average silver iodide content is 3 mol% or more and 10 mol% or less, and the ratio of the sixth shell is 3% or more and 20% or less with respect to the total silver amount. And the average silver iodide content is 0 mol% or more and 3 mol% or less,
(25) A silver halide emulsion characterized by reduction sensitization.
(26) A silver halide emulsion characterized by containing an oxidizing agent for silver nuclei.
(27) A silver halide emulsion comprising a hexacoordinate cyano complex of at least one polyvalent metal.
(28) A silver halide emulsion to which silver halide fine particles containing at least one polyvalent metal compound are added.
(29) A silver halide emulsion wherein the silver halide grains contained in the silver halide emulsion are formed by a grain distance control method.
(30) A silver halide emulsion wherein the silver halide grains contained in the silver halide emulsion have silver halide protrusions on the surface of the grains.
(31) A silver halide emulsion wherein the silver halide grains contained in the silver halide emulsion contain silver chloride.
(32) The silver halide characterized in that 10 mass percent or more of the dispersion medium used for the formation of silver halide grains contained in the silver halide emulsion is chemically modified gelatin substituted with an amino group. emulsion.
[0024]
More preferably, the silver halide grains have at least a seven-layer structure of a core, a first shell, a second shell, a third shell, a fourth shell, a fifth shell, and a sixth shell from the center, The ratio is 0.2% or more and 0.8% or less with respect to the total silver amount, the average silver iodide content is 10 mol% or more and 15 mol% or less, and the ratio of the first shell is the total silver amount. The average silver iodide content is 10% or more and 40% or less, and the ratio of the second shell is 10% or more and 25% or less with respect to the total silver amount. The average silver iodide content is 5 mol% or more and 15 mol% or less, the ratio of the third shell is 15% or more and 25% or less with respect to the total silver amount, and the average silver iodide content thereof is The content is 0 mol% or more and 2 mol% or less, and the ratio of the fourth shell is 1% or more and 3% based on the total silver amount. The average silver iodide content is 60 mol% or more and 100 mol% or less, and the ratio of the fifth shell is 15% or more and 30% or less with respect to the total silver amount. The silver content is 3 mol% or more and 5 mol% or less, the ratio of the sixth shell is 5% or more and 10% or less with respect to the total silver amount, and the average silver iodide content is 0 mol% or more 33. The silver halide emulsion as described in any one of 25 to 32, which is 2 mol% or less.
[0025]
Furthermore, as another aspect, a silver halide emulsion comprising silver halide grains and a dispersion medium, wherein the silver halide grains are arranged from the center to the internal phase, the first high-iodine localized phase, the intermediate phase, (2) It has at least a five-phase structure of a high iodine locality phase and a shell phase, and the ratio of the internal phase is 5% or more and 60% or less of the grain silver amount, and the average silver iodide content is 0 mol% or more and 10% or less. The ratio of the first and second high-iodine localized phases is 0.5% or more and 5% or less of the amount of grain silver, and the average silver iodide content is higher than 40 mol% and 100%, respectively. The proportion of the intermediate phase is 10% or more and 70% or less of the amount of grain silver, the average silver iodide content is 0 to 10% by mole, and the ratio of shell phase is the amount of grain silver The average silver iodide content is 10 mol% or more and 10 mol% or less.
(33) A silver halide emulsion characterized by reduction sensitization.
(34) A silver halide emulsion characterized by containing an oxidizing agent for silver nuclei.
(35) A silver halide emulsion comprising a hexacoordinate cyano complex of at least one polyvalent metal.
(36) A silver halide emulsion to which silver halide fine grains containing at least one polyvalent metal compound are added.
(37) A silver halide emulsion wherein the silver halide grains contained in the silver halide emulsion are formed by a grain distance control method.
(38) A silver halide emulsion wherein the silver halide grains contained in the silver halide emulsion have silver halide protrusions on the grain surface.
(39) A silver halide emulsion wherein the silver halide grains contained in the silver halide emulsion contain silver chloride.
(40) Silver halide characterized in that 10 mass percent or more of the dispersion medium used for the formation of silver halide grains contained in the silver halide emulsion is chemically modified gelatin substituted with amino groups emulsion.
[0026]
More preferably,
(41) The silver halide as described in any one of 1 to 40 above, wherein 50% or more of the total projected area of the silver halide grains is tabular silver halide grains having an average aspect ratio of 3 or more. emulsion.
(42) Any one of (1) to (41) above, wherein 50% or more of the total projected area of the silver halide grains is a tabular silver halide emulsion having 10 or more dislocation lines per grain in the fringe portion. 2. A silver halide emulsion according to claim 1.
[0027]
Furthermore,
(43) A silver halide photographic light-sensitive material comprising the silver halide emulsion described in any one of 1 to 42 above in at least one silver halide emulsion layer on a support.
[0028]
Hereinafter, the present invention will be described in detail. The silver halide grains having the above-mentioned characteristics contained in the silver halide emulsion of the present invention may be referred to as the silver halide grains of the present invention.
[0029]
The silver halide grains according to claims 1 to 8 of the present invention have at least a quintuple structure of a core, a first shell, a second shell, a third shell, and a fourth shell from the center. The core, the first shell, the second shell, the third shell, and the fourth shell correspond to the time sequence of silver halide preparation. Each preparation process may be performed continuously in this order, and water washing and dispersion processes may be performed between the processes. The amount of silver contained in each of the core, the first shell, the second shell, the third shell, and the fourth shell is selected so as to satisfy the relationship described later and the total silver amount of the grains is just 100%.
[0030]
The ratio of the core of the silver halide grains according to claims 1 to 8 of the present invention is 5% to 50% with respect to the total silver amount, and the average silver iodide content is 0 mol% to 3 mol%. It is as follows. Here, the ratio of the core means the ratio of the amount of silver used to prepare the core to the amount of silver used to obtain the final grains. The average silver iodide content means the percentage of the molar ratio of the amount of silver iodide used for core preparation to the amount of silver used for core preparation, and the distribution may be uniform or non-uniform. Preferably, the ratio of the core is 10% or more and 40% or less with respect to the total silver amount, and the average silver iodide content is 0 mol% or more and 2 mol% or less.
[0031]
A first shell is provided on the core particles described above. The ratio of the first shell is 5% or more and 30% or less with respect to the total silver amount, and the average silver iodide content thereof is 3 mol% or more and 10 mol% or less. Preferably, the ratio of the first shell is 10% or more and 25% or less with respect to the total silver amount, and the average silver iodide content thereof is 5 mol% or more and 10 mol% or less.
[0032]
A second shell is provided on the particles having the core and the first shell described above. The ratio of the second shell is 10% or more and 30% or less with respect to the total silver amount, and the average silver iodide content is 0 mol% or more and 3 mol% or less. Preferably, the ratio of the second shell is 15% or more and 25% or less with respect to the total silver amount, and the average silver iodide content thereof is 0 mol% or more and 2 mol% or less.
[0033]
A third shell which is a high iodine localized phase is provided on the above-described grains having the core, the first shell, and the second shell. The ratio of the third shell is 0.5% or more and 5% or less with respect to the total silver amount, and the average silver iodide content is 40 mol% or more and 100 mol% or less. Preferably, the ratio of the third shell is 1% or more and 3% or less with respect to the total silver amount, and the average silver iodide content is 60 mol% or more and 100 mol% or less.
[0034]
A fourth shell is provided on the particles having the core, the first shell, the second shell, and the third shell described above. The ratio of the fourth shell is 10% or more and 40% or less with respect to the total silver amount, and the average silver iodide content is 3 mol% or more and 10 mol% or less. Preferably, the ratio of the fourth shell is 15% or more and 30% or less with respect to the total silver amount, and the average silver iodide content is 3 mol% or more and 5 mol% or less. Note that the ratio of the average silver iodide content between the adjacent layers is preferably 2 or more.
[0035]
The silver halide grains according to claims 9 to 16 of the present invention have at least a six-fold structure of a core, a first shell, a second shell, a third shell, a fourth shell, and a fifth shell from the center. The core, the first shell, the second shell, the third shell, the fourth shell, and the fifth shell correspond to the time sequence of silver halide preparation. Each preparation process may be performed continuously in this order, and water washing and dispersion processes may be performed between the processes. The amount of silver in each of the core, the first shell, the second shell, the third shell, the fourth shell, and the fifth shell satisfies the relationship described later, and is selected so that the total silver amount of the grains is just 100%. Is done.
[0036]
The ratio of the core of the silver halide grains according to claims 9 to 16 of the present invention is 5% or more and 50% or less with respect to the total silver amount, and the average silver iodide content is 0 mol% or more and 3 mol%. It is as follows. Here, the ratio of the core means the ratio of the amount of silver used to prepare the core to the amount of silver used to obtain the final grains. The average silver iodide content means the percentage of the molar ratio of the amount of silver iodide used for core preparation to the amount of silver used for core preparation, and the distribution may be uniform or non-uniform. Preferably, the ratio of the core is 10% or more and 40% or less with respect to the total silver amount, and the average silver iodide content is 0 mol% or more and 2 mol% or less.
[0037]
A first shell is provided on the core particles described above. The ratio of the first shell is 5% or more and 30% or less with respect to the total silver amount, and the average silver iodide content is 3 mol% or more and 20 mol% or less. Preferably, the ratio of the first shell is 10% or more and 25% or less with respect to the total silver amount, and the average silver iodide content is 5 mol% or more and 15 mol% or less.
[0038]
A second shell is provided on the particles having the core and the first shell described above. The ratio of the second shell is 10% or more and 30% or less with respect to the total silver amount, and the average silver iodide content is 0 mol% or more and 3 mol% or less. Preferably, the ratio of the second shell is 15% or more and 25% or less with respect to the total silver amount, and the average silver iodide content thereof is 0 mol% or more and 2 mol% or less.
[0039]
A third shell which is a high iodine localized phase is provided on the above-described grains having the core, the first shell, and the second shell. The ratio of the third shell is 0.5% or more and 5% or less with respect to the total silver amount, and the average silver iodide content is 40 mol% or more and 100 mol% or less. Preferably, the ratio of the third shell is 1% or more and 3% or less with respect to the total silver amount, and the average silver iodide content is 60 mol% or more and 100 mol% or less.
[0040]
A fourth shell is provided on the particles having the core, the first shell, the second shell, and the third shell described above. The ratio of the fourth shell is 10% or more and 40% or less with respect to the total silver amount, and the average silver iodide content is 3 mol% or more and 10 mol% or less. Preferably, the ratio of the fourth shell is 15% or more and 30% or less with respect to the total silver amount, and the average silver iodide content is 3 mol% or more and 5 mol% or less.
[0041]
A fifth shell is provided on the particles having the core, first shell, second shell, third shell, and fourth shell described above. The ratio of the fifth shell is 3% or more and 20% or less with respect to the total silver amount, and the average silver iodide content is 0 mol% or more and 3 mol% or less. Preferably, the ratio of the fifth shell is 5% or more and 10% or less with respect to the total silver amount, and the average silver iodide content thereof is 0 mol% or more and 2 mol% or less. Note that the ratio of the average silver iodide content between the adjacent layers is preferably 2 or more.
[0042]
The silver halide grains according to claims 17 to 24 of the present invention have at least a sevenfold structure of a core, a first shell, a second shell, a third shell, a fourth shell, a fifth shell, and a sixth shell from the center. Become. The core, first shell, second shell, third shell, fourth shell, fifth shell, and sixth shell correspond to the time sequence of silver halide preparation. Each preparation process may be performed continuously in this order, and water washing and dispersion processes may be performed between the processes. The silver amount of each of the core, the first shell, the second shell, the third shell, the fourth shell, the fifth shell, and the sixth shell satisfies the relationship described later, and the total silver amount of the grains is just 100%. Selected to be.
[0043]
The ratio of the core of the silver halide grains according to claims 17 to 24 of the present invention is 5% or more and 50% or less with respect to the total silver amount, and the average silver iodide content thereof is 0 mol% or more and 3 mol%. It is as follows. Here, the ratio of the core means the ratio of the amount of silver used to prepare the core to the amount of silver used to obtain the final grains. The average silver iodide content means the percentage of the molar ratio of the amount of silver iodide used for core preparation to the amount of silver used for core preparation, and the distribution may be uniform or non-uniform. Preferably, the ratio of the core is 10% or more and 40% or less with respect to the total silver amount, and the average silver iodide content is 0 mol% or more and 2 mol% or less.
[0044]
A first shell is provided on the core particles described above. The ratio of the first shell is 5% or more and 30% or less with respect to the total silver amount, and the average silver iodide content is 3 mol% or more and 20 mol% or less. Preferably, the ratio of the first shell is 10% or more and 25% or less with respect to the total silver amount, and the average silver iodide content is 5 mol% or more and 15 mol% or less.
[0045]
A second shell is provided on the particles having the core and the first shell described above. The ratio of the second shell is 10% or more and 30% or less with respect to the total silver amount, and the average silver iodide content is 0 mol% or more and 3 mol% or less. Preferably, the ratio of the second shell is 15% or more and 25% or less with respect to the total silver amount, and the average silver iodide content thereof is 0 mol% or more and 2 mol% or less.
[0046]
A third shell which is a high iodine localized phase is provided on the above-described grains having the core, the first shell, and the second shell. The ratio of the third shell is 0.5% or more and 5% or less with respect to the total silver amount, and the average silver iodide content is 40 mol% or more and 100 mol% or less. Preferably, the ratio of the third shell is 1% or more and 3% or less with respect to the total silver amount, and the average silver iodide content is 60 mol% or more and 100 mol% or less.
[0047]
A fourth shell is provided on the particles having the core, the first shell, the second shell, and the third shell described above. The ratio of the fourth shell is 3% or more and 20% or less with respect to the total silver amount, and the average silver iodide content is 0 mol% or more and 3 mol% or less. Preferably, the ratio of the fourth shell is 5% or more and 10% or less with respect to the total silver amount, and the average silver iodide content is 0 mol% or more and 2 mol% or less.
[0048]
A fifth shell is provided on the particles having the core, first shell, second shell, third shell, and fourth shell described above. The ratio of the fifth shell is 10% or more and 40% or less with respect to the total silver amount, and the average silver iodide content is 3 mol% or more and 10 mol% or less. Preferably, the ratio of the fifth shell is 15% or more and 30% or less with respect to the total silver amount, and the average silver iodide content thereof is 3 mol% or more and 5 mol% or less.
[0049]
A sixth shell is provided on the particles having the core, first shell, second shell, third shell, fourth shell, and fifth shell described above. The ratio of the sixth shell is 3% or more and 20% or less with respect to the total silver amount, and the average silver iodide content is 0 mol% or more and 3 mol% or less. Preferably, the ratio of the sixth shell is 5% or more and 10% or less with respect to the total silver amount, and the average silver iodide content thereof is 0 mol% or more and 2 mol% or less. Note that the ratio of the average silver iodide content between the adjacent layers is preferably 2 or more.
[0050]
The silver halide grains according to claims 25 to 32 of the present invention have at least a sevenfold structure of a core, a first shell, a second shell, a third shell, a fourth shell, a fifth shell, and a sixth shell from the center. Become. The core, first shell, second shell, third shell, fourth shell, fifth shell, and sixth shell correspond to the time sequence of silver halide preparation. Each preparation process may be performed continuously in this order, and water washing and dispersion processes may be performed between the processes. The silver amount of each of the core, the first shell, the second shell, the third shell, the fourth shell, the fifth shell, and the sixth shell satisfies the relationship described later, and the total silver amount of the grains is just 100%. Selected to be.
[0051]
The ratio of the core of the silver halide grains according to claims 25 to 32 of the present invention is 0.1% or more and 1% or less with respect to the total silver amount, and the average silver iodide content is 4 mol% or more and 20%. It is less than mol%. Here, the ratio of the core means the ratio of the amount of silver used to prepare the core to the amount of silver used to obtain the final grains. The average silver iodide content means the percentage of the molar ratio of the amount of silver iodide used for core preparation to the amount of silver used for core preparation, and the distribution may be uniform or non-uniform. Preferably, the ratio of the core is 0.2% or more and 0.8% or less with respect to the total silver amount, and the average silver iodide content is 10 mol% or more and 15 mol% or less.
[0052]
A first shell is provided on the core particles described above. The ratio of the first shell is 5% or more and 50% or less with respect to the total silver amount, and the average silver iodide content is 0 mol% or more and 3 mol% or less. Preferably, the ratio of the first shell is 10% or more and 40% or less with respect to the total silver amount, and the average silver iodide content thereof is 0 mol% or more and 2 mol% or less.
[0053]
A second shell is provided on the particles having the core and the first shell described above. The ratio of the second shell is 5% or more and 30% or less with respect to the total silver amount, and the average silver iodide content thereof is 3 mol% or more and 20 mol% or less. Preferably, the ratio of the first shell is 10% or more and 25% or less with respect to the total silver amount, and the average silver iodide content is 5 mol% or more and 15 mol% or less.
[0054]
A third shell is provided on the particles having the core and the first and second shells described above. The ratio of the third shell is 10% or more and 30% or less with respect to the total silver amount, and the average silver iodide content is 0 mol% or more and 3 mol% or less. Preferably, the ratio of the third shell is 15% or more and 25% or less with respect to the total silver amount, and the average silver iodide content thereof is 0 mol% or more and 2 mol% or less.
[0055]
A fourth shell which is a high iodine localized layer is provided on the above-described grains having the core, the first shell, the second shell, and the third shell. The ratio of the fourth shell is 0.5% or more and 5% or less with respect to the total silver amount, and the average silver iodide content is 40 mol% or more and 100 mol% or less. Preferably, the ratio of the fourth shell is 1% or more and 3% or less with respect to the total silver amount, and the average silver iodide content is 60 mol% or more and 100 mol% or less.
[0056]
A fifth shell is provided on the particles having the core, first shell, second shell, third shell, and fourth shell described above. The ratio of the fifth shell is 10% or more and 40% or less with respect to the total silver amount, and the average silver iodide content is 3 mol% or more and 10 mol% or less. Preferably, the ratio of the fifth shell is 15% or more and 30% or less with respect to the total silver amount, and the average silver iodide content thereof is 3 mol% or more and 5 mol% or less.
[0057]
A sixth shell is provided on the particles having the core, first shell, second shell, third shell, fourth shell, and fifth shell described above. The ratio of the sixth shell is 3% or more and 20% or less with respect to the total silver amount, and the average silver iodide content is 0 mol% or more and 3 mol% or less. Preferably, the ratio of the sixth shell is 5% or more and 10% or less with respect to the total silver amount, and the average silver iodide content thereof is 0 mol% or more and 2 mol% or less. Note that the ratio of the average silver iodide content between the adjacent layers is preferably 2 or more.
[0058]
In the present invention, the high iodide localized phase is a silver iodide-containing phase having an average silver iodide content of more than 40 mol% and not more than 100 mol%, and the ratio (silver content ratio) is 0. The silver halide phase is 5% or more and 5% or less and has a very high silver iodide content and a small silver content ratio and is localized in the grains. A preferable value of the average silver iodide content of the high iodine localized phase is 95 mol% or more and 100 mol% or less, and a preferable silver amount ratio of the high iodine local phase is 1% or more and 3.5% or less. is there.
[0059]
As a method for forming a high iodine localized phase of the present invention, a silver salt aqueous solution and a halide aqueous solution containing more than 40 mol% of iodide are added by a double jet method, and a silver salt aqueous solution and an iodide aqueous solution are double jet. There is a method of adding by the method. The silver amount ratio of the high iodine localized phase formed by these methods can be obtained from the amount of silver added during the phase formation. Further, the high iodide localized phase can be formed by a method of adding an aqueous iodide solution by a single jet method or a method using an iodide ion releasing agent as described in JP-A-6-11781. In this case, the silver amount ratio of the high-iodine localized phase is determined by an amount of silver equimolar to iodine contained in the added iodide, assuming that halogen conversion by iodide occurs 100%. The composition of the high iodine localized phase formed at this time is set to a silver iodide content of 100%. Further, there is a method in which a silver iodide emulsion containing fine silver iodide fine grains is added to form a high iodine localized phase. In this case, the silver amount ratio of the high iodide local phase is obtained from the silver amount of the silver iodide emulsion. The composition of the high iodine localized phase formed at this time is set to a silver iodide content of 100%. The silver iodide fine grain emulsion can be easily prepared by the method described in US Pat. No. 4,672,026. The average size of the silver iodide fine particles is preferably 0.06 μm or less, more preferably 0.03 μm or less, as a sphere equivalent diameter value. In the present invention, among the above methods, a method of adding a silver salt aqueous solution and an iodide aqueous solution by a double jet, a method of adding a silver iodide fine grain emulsion, or a method using an iodine ion releasing agent is used. Is preferably formed.
[0060]
The iodine ion releasing agent is a compound that releases iodine ions by a reaction with a base or a nucleophile represented by the general formula of “R-I”. Here, R represents a monovalent organic group. R is an alkyl group, alkenyl group, alkynyl group, aryl group, aralkyl group, heterocyclic group, acyl group, carbamoyl group, alkyloxycarbonyl group, aryloxycarbonyl group, alkylsulfonyl group, arylsulfonyl group or sulfamoyl group. It is preferable. R is preferably an organic group having 30 or less carbon atoms, more preferably 20 or less, and even more preferably 10 or less. R preferably has the following substituents, and the substituents may be further substituted with other substituents.
[0061]
Preferred examples of the substituent include halogen, alkyl group, alkenyl group, alkynyl group, aryl group, aralkyl group, heterocyclic group, acyl group, acyloxy group, carbamoyl group, alkyloxycarbonyl group, aryloxycarbonyl group, alkylsulfonyl group, Arylsulfonyl group, sulfamoyl group, alkoxy group, aryloxy group, amino group, acylamino group, ureido group, urethane group, sulfonylamino group, sulfinyl group, phosphoric acid amide group, alkylthio group, arylthio group, cyano group, sulfo group, Examples thereof include a carboxyl group, a hydroxy group, and a nitro group.
[0062]
The iodine ion releasing agent R-I is preferably an iodoalkane, iodoalcohol, iodocarboxylic acid, iodoamide or a derivative thereof, more preferably an iodoamide, iodoalcohol or a derivative thereof, iodoamide substituted with a heterocyclic group. Is more preferred, and the most preferred example is (iodoacetamido) benzene sulfonate.
[0063]
Specific examples of iodine ion releasing agents that can be preferably used are shown below.
[0064]
[Chemical 1]

[0065]
When an iodine ion releasing agent and a nucleophilic reagent are reacted to release iodine ion, hydroxide ion, sulfite ion, thiosulfate ion, sulfinate, carboxylate, ammonia, amines, Alcohols, ureas, thioureas, phenols, hydrazines, sulfides, hydroxamic acids, etc. can be used, hydroxide ions, sulfite ions, thiosulfate ions, sulfinates, carboxylates, ammonia, Amines are preferable, and hydroxide ions and sulfite ions are more preferable.
[0066]
In claims 33 to 40 of the present invention, an intermediate phase is provided between at least two high-iodine localized phases in the grains. When three or more high iodine locality phases are present, the intermediate phase is present between at least any two high iodine local phases. The intermediate phase may have a uniform composition, or may be composed of a plurality of silver halide phases having different compositions or a silver halide phase in which the silver iodide content changes continuously. The average silver iodide content of the intermediate phase is from 0 mol% to 10 mol%, and the ratio (silver content ratio) is from 10% to 70% of the grain silver content. A preferable value of the average silver iodide content of the intermediate phase is from 0 mol% to 5 mol%, and a preferable silver amount ratio of the intermediate phase is from 15% to 50%.
[0067]
In claims 33 to 40 of the present invention, a shell phase is provided outside the high-iodine localized phase located on the outermost side in the high-iodine localized phase. The shell phase may have a uniform composition, or may be composed of a plurality of silver halide phases having different compositions or a silver halide phase in which the silver iodide content changes continuously. The average silver iodide content of the shell phase is from 0 mol% to 10 mol%, and the ratio (silver content ratio) is from 10% to 50% of the grain silver content. A preferable value of the average silver iodide content of the shell phase is 0 to 6 mol%, and a preferable silver amount ratio of the shell phase is 20 to 40%.
[0068]
In claims 33 to 40 of the present invention, the high-iodine localized phase has an internal phase inside the high-iodine localized phase located on the innermost side. When the silver halide emulsion of the present invention is formed by growing previously prepared so-called silver halide nucleus grains or silver halide seed grains, the internal phase may contain nucleus grains or seed grains. Alternatively, the core particles and seed particles may be grown with a composition different from that of the core particles and seed particles to form the internal phase. That is, the internal phase may have a uniform composition, or may be composed of a plurality of silver halide phases having different compositions or a silver halide phase in which the silver iodide content changes continuously. The average silver iodide content of the internal phase is 10 mol% or less, and the ratio (silver content ratio) is 5% or more and 60% or less of the grain silver content. A preferable value of the average silver iodide content of the internal phase is 0 mol% or more and 3 mol% or less.
[0069]
The shell layer excluding the core and the high iodine localized phase can be formed by preparing a generally known silver halide emulsion. In the preparation of the silver halide emulsion of the present invention, Grafkide, “Physics and Chemistry of Photography”, published by Paul Monter (P. Glafkides, Chimie et Physiology Photographic Paul Montel, 1967), “Photographic Emulsion Chemistry”, Duffin, Published by Press (GF Duffin, Photographic Emulsion Chemistry (Focal Press, 1966)), “Production and Coating of Photoemulsions” by Zeligman et al., VL Zelikman et al, Making and Coating Pharming The method described in Emulsion, Focal Press, 1964) can also be referred to. That is, any method such as an acidic method, a neutral method, and an ammonia method can be used. Further, as a form of reacting the silver salt aqueous solution and the halide aqueous solution in the grain growth step, any method such as a one-side mixing method, a simultaneous mixing method, or a combination thereof may be used. A method (so-called back mixing method) in which grains are formed in the presence of excess silver ions can also be used. As one type of the simultaneous mixing method, a method of controlling pAg in a liquid phase in which silver halide is formed, that is, a so-called controlled double jet method is known. This method is used in a silver halide grain growth step. It is effective for enhancing the homogeneity between grains, and can be preferably used for forming a shell layer excluding a core and a high iodine localized layer.
[0070]
A method of adding silver halide grains precipitated in advance to a reaction vessel for emulsion preparation, for example, as described in US Pat. Nos. 4,334,012, 4,301,241 and 4,150,994 These methods can also be used. In particular, a method of adding as a supply source of silver ions and halogen ions for growth is a preferred embodiment. As the addition method, it is possible to select from among adding all at once, adding by dispersing multiple times, or adding continuously. It is also effective in some cases to add grains having various halogen compositions in order to modify the surface of silver halide grains related to the present invention.
[0071]
In addition to the method of adding a silver salt aqueous solution and a halide aqueous solution at a constant concentration and a constant flow rate in the grain growth process, British Patent No. 1,469,480, US Pat. Nos. 3,650,757, 4,242, A particle forming method in which the concentration is changed or the flow rate is changed as described in No. 445 is a preferable method. By increasing the concentration or increasing the flow rate, the supplied silver salt aqueous solution and halide aqueous solution can be changed by a linear function, a quadratic function, or a more complicated function of the addition time. Further, if necessary, the supply amount can be reduced depending on circumstances.
[0072]
As the mixing mechanism of the reaction vessel, U.S. Pat. Nos. 2,996,287, 3,342,605, 3,415,650, 3,785,777, West German Patent No. 2 , 556,885 and 2,555,364, and the like.
[0073]
For the purpose of promoting ripening, a silver halide solvent is useful. For example, it is known that an excessive amount of halogen ions is present in the reaction vessel to promote aging. Other ripening accelerators such as a silver halide solvent can also be used. These ripening accelerators can be mixed in the dispersion medium in the reaction vessel before adding the silver salt aqueous solution or halide aqueous solution, or the silver salt aqueous solution, halide aqueous solution, or dispersion medium can be added. It can also be introduced into the reaction vessel as well as being added. As another embodiment, the ripening agent can be introduced independently of the addition of the aqueous silver salt solution or the aqueous halide solution. Examples of the silver halide solvent include ammonia, thiocyanate (for example, rhodancali, rhodammonium), and organic thioether compounds (for example, U.S. Pat. Nos. 3,574,628, 3,021,215, and 3, No. 057,724, No. 3,038,805, No. 4,276,374, No. 4,297,439, No. 3,704,130, No. 4,782,013, Compounds described in JP-A-57-104926), thione compounds (for example, tetra-substituted compounds described in JP-A-53-82408, JP-A-55-77737, US Pat. No. 4,782,013, etc.) Thiourea, compounds described in JP-A-53-144319), and melts that can promote the growth of silver halide grains described in JP-A-57-202331 Script compounds, amine compounds (e.g., JP-A No. 54-100717) and the like.
[0074]
The silver halide emulsion of the present invention is preferably washed with water for desalting after grain formation and dispersed in an aqueous solution containing a newly prepared dispersion medium. The temperature of washing with water can be selected according to the purpose, but is preferably selected within the range of 5 ° C to 60 ° 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. The coagulation sedimentation method includes a method using a sulfate, a method using an organic solvent, a method using a water-soluble polymer, a method using a gelatin derivative such as modified gelatin and modified gelatin, and the like. It is preferable to use the desalting method described in Kaihei 5-72658.
[0075]
In the present invention, the silver iodide content and the average silver iodide content of individual silver halide grains can be determined by using an EPMA method (Electron Probe Micro Analyzer method). This method makes it possible to prepare a sample in which emulsion grains are well dispersed so as not to contact each other, and to perform an elemental analysis of a very minute portion by X-ray analysis by electron beam excitation in which an electron beam is irradiated. By this method, the halogen composition of individual grains can be determined by obtaining the characteristic X-ray intensity of silver and iodine emitted from each grain. If the silver iodide content is determined by EPMA method for at least 50 grains, the average silver iodide content can be determined from the average of these. The average silver iodide content is measured by other well-known methods such as X-ray fluorescence analysis, ICP (inductive plasma) emission analysis, and ICP mass spectrometry, and the silver iodide content of the whole emulsion. Can also be obtained by measuring.
[0076]
The tabular grains in the present invention preferably have a more uniform silver iodide content between grains in one type of tabular grain. When the distribution of silver iodide content between grains is measured by the EPMA method, the relative standard deviation is preferably 30% or less, more preferably 20% or less.
[0077]
The halogen composition on the surface of the tabular grain of the present invention is determined by the XPS method (X-ray Photoelectron Spectroscopy method: X-ray photoelectron spectroscopy) as follows. That is, the sample was 1.33 × 10^-6Cooling to −110 ° C. or lower in an ultra-high vacuum of Pa or less, and irradiating with MgKα as a probe X-ray with an X-ray source voltage of 15 kV and an X-ray source current of 40 mA. taking measurement. The integrated intensity of the measured peak is corrected with a sensitivity factor, and the halide composition on the surface of the silver halide is determined from these intensity ratios.
[0078]
As another feature of the silver halide grains of the present invention, 50% or more of the total projected area of the silver halide grains has 10 or more dislocation lines per grain in the fringe portion. In this case, the number of dislocation lines is preferably 20 or more on average per particle. The dislocation lines possessed by silver halide grains are described in, for example, J.A. F. Hamilton, Photo. Sci. Eng. 11 (1967) 57, 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 (1972) 213. In other words, silver halide grains taken out carefully so as not to apply pressure to the grains from the emulsion are placed on an electron microscope mesh to prevent damage (printout, etc.) due to electron beams. Observation is performed by the transmission method with the sample cooled. At this time, since the electron beam is less likely to be transmitted as the particle thickness is thicker, a method using a high acceleration voltage electron microscope can be observed more clearly. From the particle photograph obtained by such a method, the position and number of dislocation lines in each particle can be obtained. When dislocation lines are densely present, the number of dislocation lines per grain may not be clearly counted. However, even in such a case, it is possible to discriminate between approximately 10 or more and 20 or more, and it can be distinguished from the case where there are clearly only a few. The average number of dislocation lines per particle is obtained as an arithmetic average by counting the number of dislocation lines for 100 particles or more.
[0079]
As a method for introducing dislocation lines into silver halide, there is a method in which a low silver iodide-containing phase is formed adjacent to a high silver iodide-containing phase.
[0080]
Preferred reaction conditions for introducing dislocation lines into the silver halide emulsion of the present invention with an iodine ion releasing agent are shown below.
[0081]
The reaction temperature is preferably 70 ° C to 30 ° C, and more preferably 65 ° C to 35 ° C. pBr is preferably 1.50 or less, more preferably 1.30 or less, and even more preferably 1.10 or less. The amount of iodine ion releasing agent to be added is preferably 0.5 to 3 mol% with respect to the total amount of silver halide after the completion of grain growth. In the case of using hydroxide ions as a nucleophile during the iodine ion releasing reaction, that is, when the iodine ion releasing agent is reacted by adjusting the pH, the reaction is performed under the condition of pH of 9.0 or more and 12.0 or less. It is preferable that the pH is 10.0 to 11.0. When a substance other than hydroxide ions is used as the nucleophilic agent, the amount of the nucleophilic agent is preferably 0.25 to 2.0 times the amount of the iodine ion releasing agent, and 0.50 or more times. The ratio is more preferably 1.5 times or less, and preferably 0.80 times or more and 1.2 times or less. When the nucleophile is other than hydroxide ions, the pH during the iodine ion releasing reaction is preferably 6.0 or more and 11.0 or less, more preferably 7.0 or more and 10.0 or less. preferable.
[0082]
Preferred reaction conditions for introducing dislocation lines into the silver halide emulsion of the present invention by means of a fine grain emulsion containing silver iodide are shown below.
[0083]
The temperature at which the fine grain emulsion containing silver iodide is added is preferably 70 ° C. to 30 ° C., more preferably 65 ° C. to 35 ° C. pBr is preferably 1.50 or less, more preferably 1.30 or less, and even more preferably 1.10 or less. The amount of the fine grain emulsion containing silver iodide to be added is preferably 0.5 to 3 mol% based on the total silver halide amount after the completion of grain growth in terms of the amount of silver iodide.
[0084]
As the shape of silver halide grains, so-called normal crystals having regular crystal shapes such as cubes, octahedrons and tetradecahedrons, and irregular crystal shapes such as tabular and potato shapes, Known are those having crystal defects such as crystal planes, or composites thereof. The silver halide emulsion of the present invention has an aspect ratio of 50% or more of the total projected area of silver halide grains. Three or more tabular silver halide grains are preferred. Further, it is more preferable that 50% or more of the total projected area is tabular silver halide grains having an aspect ratio of 5 or more, and 80% or more of the total projected area is tabular halogenated having an aspect ratio of 5 or more. Silver particles are particularly preferred. The tabular silver halide grains have a crystal form that is crystallographically classified as twins. A twin is a crystal having one or more twin planes in one grain, and the classification of the form of twins in silver halide grains is described in a report by Klein and Moiser, “Photographie Korrespondenz”, Vol. 99, p. 99. , Vol. 100, p. 57. In addition, tabular silver halide grains are described in “Theory and Practice of Photography” by Clive (Cleve, Photographic Thorough Practice (1930)), p. 131; Gatoff, Photographic Science and Engineering (Gutoff, Photographic Science). and Engineering, 14, 248-257 (1970); U.S. Pat. Nos. 4,434,226, 4,414,310, 4,433,048, 4,439. , 520, and British Patent No. 2,112,157, and the like.
[0085]
The tabular silver halide grains related to the present invention can be selected from shapes such as triangles, hexagons, and circles, but the length of the six sides as described in US Pat. No. 4,797,354 is great. Approximately equal hexagonal tabular silver halide grains are the preferred form. The tabular silver halide grains related to the present invention preferably have one or two or more twin planes parallel to each other in the grains. These twin planes exist substantially parallel to the plane having the largest area (also referred to as a main plane) among the planes forming the surface of the tabular grains. A particularly preferable form in the present invention is a case having two parallel twin planes. These twin planes can be observed by the following method using a transmission electron microscope. First, a silver halide emulsion is coated on a substrate so that the main planes of contained tabular grains are oriented almost parallel to the substrate to prepare a sample. This is continuously cut perpendicularly to the substrate using a diamond cutter to obtain a continuous thin slice having a thickness of about 0.1 μm. By observing this section with a transmission electron microscope, the presence and position of the twin plane can be confirmed.
[0086]
In the present invention, the aspect ratio refers to the ratio between the particle diameter and the particle thickness. Here, the particle size means the diameter of a circle having an area equal to the area when the particles are projected perpendicularly to the main plane. That is, aspect ratio = diameter / thickness. As the grain size of tabular silver halide grains, grains having an average grain size of 0.6 μm or less as described in U.S. Pat. No. 4,748,106 are preferable for improving image quality. Limiting the thickness to 0.3 μm or less, more preferably 0.2 μm or less is preferable in terms of enhancing sharpness.
[0087]
The projected area and thickness of individual grains for calculating the grain size, grain thickness, and aspect ratio of silver halide grains can be determined by the following method. A sample was prepared by applying a latex ball with a known particle size as an internal standard on a support and silver halide grains so that the main plane was oriented parallel to the substrate, and shadowing was performed by carbon deposition from a certain angle. After that, a replica sample is prepared by a normal replica method. An electron micrograph of the sample is taken, and the projected area and thickness of each particle are obtained using an image processing apparatus or the like. In this case, the projected area of the particle can be calculated from the projected area of the internal standard, and the thickness of the particle can be calculated from the length of the internal standard and the shadow of the particle.
[0088]
The silver halide emulsion of the present invention is preferably a silver halide emulsion having a small variation in the required grain size. Specifically, the variation coefficient of the particle size is preferably 20% or less, and more preferably 15% or less. The coefficient of variation of the grain size is a value defined by the following equation, and was obtained by arbitrarily measuring the grain size of silver halide grains contained in the silver halide emulsion by the above-described replica method. Calculate using the value.
[0089]
Coefficient of variation of particle size (%) = (standard deviation of particle size / average value of particle size) × 100
U.S. Pat. No. 4,797,354 and JP-A-2-838 describe methods for producing monodispersed hexagonal tabular grains having a high tabularization rate. In addition, European Patent No. 514,742 describes a method for producing tabular grains having a variation coefficient of grain size distribution of less than 10% using a polyalkylene oxide block copolymer. These techniques can also be applied to the preparation of the silver halide emulsion of the present invention.
[0090]
The silver halide emulsions according to claims 1, 9, 17, 25, and 33 of the present invention are characterized by being reduction sensitized. Examples of reduction sensitization methods that can be used in the present invention include various reduction sensitization methods described in Photographic Sensitivity (Tadaaki Taniaki, Oxford University Press 1995) from page 180. However, various methods of reduction sensitization are known and are not limited thereto. That is, a method of adding a known reducing agent to a silver halide emulsion, a method of growing or ripening in a low pAg atmosphere of pAg 1 to 7 called silver ripening, and a method as disclosed in JP-A-10-26810 A method of growing or aging in a high pH atmosphere called pH ripening called pH ripening is known, and two or more methods can be used in combination. The method of adding a reduction sensitizer is a preferable method in that the level of reduction sensitization can be finely adjusted.
[0091]
Known reduction sensitizers include stannous salts, amines and polyamic acids, hydrazine derivatives, formamidine sulfinic acid, silane compounds, and borane compounds. In the present invention, these known compounds can be selected and used. Two or more compounds can be used in combination. As a reduction sensitizer, stannous chloride, thiourea dioxide, and dimethylamine borane are preferable compounds. More preferably, an alkynylamine compound described in US Pat. No. 5,389,510 can be selected. 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.
[0092]
Ascorbic acid and its derivatives can also be used as the reduction sensitizer of the present invention. Specific examples of ascorbic acid and its derivatives (hereinafter referred to as “ascorbic acid compounds”) include the following.
[0093]
(A-1) L-ascorbic acid
(A-2) Sodium L-ascorbate
(A-3) Potassium L-ascorbate
(A-4) DL-ascorbic acid
(A-5) D-sodium ascorbate
(A-6) L-ascorbic acid-6-acetate
(A-7) L-ascorbic acid-6-palmitate
(A-8) L-ascorbic acid-6-benzoate
(A-9) L-ascorbic acid-5,6-diacetate
(A-10) L-ascorbic acid-5,6-O-isopropylidene
The ascorbic acid compound used in the present invention is desirably used in a large amount as compared with the addition amount for which a reduction sensitizer is conventionally preferably used. For example, in Japanese Patent Publication No. 57-33572, “the amount of reducing agent is usually 0.75 × 10 5 per g of silver ion.^-2Milliequivalent (8 × 10^-FourMol / AgX mol). An amount of 0.1 to 10 mg per kg of silver nitrate (ascorbic acid 10^-7-10^-FiveMole / AgX mole) is often effective. (The conversion value is determined by the inventors). U.S. Pat. No. 2,487,850 states that “1 × 10 as the amount of tin compound that can be used as a reduction sensitizer.^-7~ 44x10^-6Mol ". In JP-A-57-179835, it is appropriate to use about 0.01 mg to about 2 mg per mol of silver halide as the addition amount of thiourea dioxide and about 0.01 mg to about 3 mg as stannous chloride. It is described. The preferred addition amount of the ascorbic acid compound used in the present invention depends on factors such as emulsion grain size, halogen composition, emulsion preparation temperature, pH, and pAg, but 5 × 10 5 per mole of silver halide.^-Five~ 1x10^-1It is desirable to choose from a range of moles. More preferably 5 × 10^-FourMol ~ 1 × 10^-2It is preferable to select from the range of moles. Particularly preferred is 1 × 10^-3Mol ~ 1 × 10^-2Choose from a range of moles.
[0094]
The reduction sensitizer can be dissolved in water or a solvent such as alcohols, glycols, ketones, esters, and amides and added during or before chemical sensitization during particle formation. Although it may be added at any stage of the emulsion production process, a method of adding during grain growth is particularly preferable. Although it may be added to the reaction vessel in advance, it is preferable to add it at an appropriate time of particle formation. Alternatively, a reduction sensitizer may be added in advance to an aqueous solution of a water-soluble silver salt or water-soluble alkali halide, and these aqueous solutions may be used to form particles. It is also preferable to add the reduction sensitizer solution several times as the particles are formed, or to add it continuously for a long time.
[0095]
A method of adding a chalcogenide compound as described in US Pat. No. 3,772,031 during emulsion preparation may be useful. In addition to S, Se, and Te, cyanate, thiocyanate, selenocyanic acid, carbonate, phosphate, and acetate may be present.
[0096]
The silver halide emulsion according to claims 2, 10, 18, 26, and 34 of the present invention is characterized by containing an oxidizing agent for silver nuclei. The oxidizing agent for silver refers to a compound having an action of acting on metallic silver and converting it into silver ions. In particular, a compound that converts very fine silver grains by-produced in the process of forming silver halide grains and chemical sensitization into silver ions is effective. 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. Inorganic oxidants include ozone, hydrogen peroxide and its adducts (eg, NaBO).₂・ H₂O₂・ 3H₂O, 2NaCO_Three・ 3H₂O₂, Na_FourP₂O₇・ 2H₂O₂2Na₂SO_Four・ H₂O₂・ H₂O), peroxyacid salts (eg K₂S₂O₈, K₂C₂O₆, K_FourP₂O₈), Peroxy complex compounds (for example, K₂[Ti (O₂) C₂O_Four] 3H₂O, 4K₂SO_Four・ Ti (O₂) OH / SO_Four・ 2H₂O, Na_Three[VO (O₂) (C₂O_Four)₂・ 6H₂O]), permanganate (eg KMnO)_Four), Chromate (eg K₂Cr₂O₇) Oxyacid salts, halogen elements such as iodine and bromine, perhalogenates (eg, potassium periodate), high valent metal salts (eg, potassium hexacyanoferrate) and thiosulfonates Etc. 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, chloramine B). ).
[0097]
Preferable oxidizing agents are ozone, hydrogen peroxide and its adduct, halogen element, thiosulfonate, and quinones, and particularly preferable are thiosulfonate compounds represented by the following general formulas (1) to (3). And most preferred is the compound represented by the general formula (1).
[0098]
(1) R-SO₂SM
(2) R-SO₂S-R₁
(3) R-SO₂SL_m-SSO₂-R₂
Where R, R₁, R₂Represents an aliphatic group, an aromatic group, or a heterocyclic group, which may be the same or different, and M represents a cation. L represents a divalent linking group, and m is 0 or 1.
[0099]
The thiosulfonic acid compounds of the general formulas (1) to (3) will be described in more detail.₁, R₂Is an aliphatic group, it is a saturated or unsaturated, linear, branched or cyclic aliphatic hydrocarbon group, preferably an alkyl group having 1 to 22 carbon atoms, alkenyl having 2 to 22 carbon atoms Group, an alkynyl group, and these may have a substituent. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, hexadecyl, octadecyl, cyclohexyl, isopropyl and t-butyl.
[0100]
Examples of the alkenyl group include allyl and butenyl. Examples of the alkynyl group include propargyl and butynyl.
[0101]
R, R₁, R₂When is an aromatic group, it includes a monocyclic or condensed ring aromatic group, and preferably has 6 to 20 carbon atoms, such as phenyl and naphthyl. These may be substituted.
[0102]
R, R₁, R₂Is a heterocyclic group, it is a 3- to 15-membered ring having at least one element selected from nitrogen, oxygen, sulfur, selenium and tellurium and having at least one carbon atom, preferably 3 to 6-membered rings are preferred, such as pyrrolidine, piperidine, pyridine, tetrahydrofuran, thiophene, oxazole, thiazole, imidazole, benzothiazole, benzoxazole, benzimidazole, selenazole, benzoselenazole, tellurazole, triazole, benzotriazole, tetrazole, oxadiazole And thiadiazole ring.
[0103]
R, R₁, R₂Examples of the substituents include alkyl groups (eg, methyl, ethyl, hexyl), alkoxy groups (eg, methoxy, ethoxy, octyloxy), aryl groups (eg, phenyl, naphthyl, tolyl), hydroxy groups, halogen atoms (Eg fluorine, chlorine, bromine, iodine), aryloxy group (eg phenoxy), alkylthio group (eg methylthio, butylthio), arylthio group (eg phenylthio), acyl group (eg acetyl, propionyl, butyryl, valeryl) Sulfonyl group (for example, methylsulfonyl, phenylsulfonyl), acylamino group (for example, acylamino, benzoylamino), sulfonylamino group (for example, methanesulfonylamino, benzenesulfonylamino), acyloxy group (for example, acetonitrile) , Benzoxy), a carboxyl group, a cyano group, a sulfo group, an amino group, -SO₂SM group (M represents a monovalent cation), -SO₂R group (R shows an alkyl group) is mentioned. The divalent linking group represented by L is an atom or atomic group containing at least one selected from C, N, S and O.
[0104]
Specifically, an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -O-, -S-, -NH-, -CO-, -SO₂-Or the like, or a combination thereof. L is preferably a divalent aliphatic group or a divalent aromatic group.
[0105]
Examples of the divalent aliphatic group include — (CH₂) -N (n is 1 to 12), -CH₂-CH = CH-CH₂-, -CH₂C≡CCH₂-, -CH₂-1,4-cyclohexylene-CH₂-, A xylylene group, and the like. Examples of the divalent aromatic group for L include a phenylene group and a naphthylene group. These substituents may be further substituted with the substituents described so far.
[0106]
M represents a cation, preferably a metal ion or an organic cation. Examples of the metal ion include lithium ion, sodium ion, and potassium ion. Examples of organic cations include ammonium ions (ammonium, tetramethylammonium, tetrabutylammonium, etc.), phosphonium ions (tetraphenylphosphonium), and guanidyl groups.
[0107]
When the compound represented by the general formulas (1) to (3) is a polymer, examples of the repeating unit include the following.
[0108]
[Chemical formula 2]

[0109]
These polymers may be homopolymers or copolymers with other copolymerization monomers. Specific examples of the compounds represented by the general formulas (1) to (3) are shown below, but are not limited thereto.
[0110]
[Chemical 3]

[0111]
[Formula 4]

[0112]
[Chemical formula 5]

[0113]
[Chemical 6]

[0114]
[Chemical 7]

[0115]
[Chemical 8]

[0116]
[Chemical 9]

[0117]
Compounds represented by the general formulas (1) to (3) are described in JP-A No. 54-1019, British Patent 972,211, Journal of Organic Chemistry (Journal of Organic Chemistry) Volume 53, page 396 (1988). Or a method analogous thereto.
[0118]
In the present invention, the addition amount of the compounds represented by the general formulas (1) to (3) is 10^-7-10^-1It is desirable to select from a range of moles. Preferably 10^-6-10^-2In the molar range, more preferably 10^-Five-10^-3The range of moles. The compounds represented by the general formulas (1) to (3) may be added at any stage during the process of producing a silver halide emulsion, for example, during the formation of silver halide grains, before or after chemical sensitization. Preferred is before chemical sensitization, more preferably during grain formation, and the compounds represented by the general formulas (1) to (3) are added either before or after the start of reduction sensitization. However, it is preferably added after the start of reduction sensitization.
[0119]
In order to add the compounds represented by the general formulas (1) to (3) during the production process, a method usually used when an additive is added to a photographic emulsion can be applied. For example, the water-soluble compound is an aqueous solution having an appropriate concentration, and the water-insoluble or sparingly soluble compound is an appropriate organic solvent miscible with water, such as alcohols, glycols, ketones, esters, amides, etc. Of these, it can be dissolved in a solvent that does not adversely affect photographic properties and added as a solution.
[0120]
The silver halide grains described in claims 3, 4, 11, 12, 19, 20, 21, 27, 28, 35, and 36 of the present invention contain at least one polyvalent metal compound.
[0121]
Here, terms will be defined. “Doping” or “doping” refers to inclusion of a substance other than silver ions or halide ions in silver halide grains. The term “dopant” refers to a compound that is doped into silver halide grains. The term “metal dopant” refers to a polyvalent metal compound that is doped into silver halide grains.
[0122]
Doping may be applied to the silver halide grains during the physical ripening of the silver halide grains, or during the addition of the water-soluble silver salt and the water-soluble alkali halide. This means that doping may be performed in a state where these additions are temporarily stopped, and then a further precipitation step may be performed. Further, doping may be performed after the formation of the halogenated grains, and a dopant may be introduced into the surface of the silver halide grains, or may be introduced before and after chemical ripening. The introduction of the dopant into the silver halide grains can be formed by introducing the dopant at a high concentration and / or in the presence of the dopant during grain growth when introduced before, during or after grain nucleation. At this time, the introduction of the dopant is delayed until after the grain formation, and the allocated amount is introduced at the initial stage of grain growth, and preferably is continued as it is, or is performed throughout the subsequent stage of silver halide grain growth. Any conventional dopant known to be useful for silver halide can be used. Photographically useful dopants selected from a wide range of periods and groups within the periodic table of elements have been reported.
[0123]
The periods and families used herein are based on the Periodic Table of Elements adopted by the American Chemical Society and published in Chemical and Engineering News, February 4, 1985, page 26. Common dopants include Fe, Co, Ni, Ru, Rh, Pd, Re, Os, Ir, Pt, Mg, Al, Ca, Sc, Ti, V, Cr, Mn, Cu, Zn, Ga, Ge, Third of periodic table of elements such as As, Se, Sr, Y, Mo, Zr, Nb, Cd, In, Sn, Sb, Ba, La, W, Au, Hg, Tl, Pb, Bi, Ce and U Atoms, ions and complexes thereof, such as ~ 7 periods (most commonly 4-6 periods).
[0124]
More preferably, atoms such as gallium, indium, thallium and lead, ions and complexes thereof are included. Dopants are (a) increased sensitivity, (b) decreased high or low intensity reciprocity failure, (c) increased, decreased or decreased contrast variation, (d) decreased pressure sensitivity, (e) dye desensitization. (F) increased stability (including decreased thermal instability), (g) decreased minimum concentration and / or (h) increased maximum concentration.
[0125]
Research Disclosure, Vol. 367, November 1994, Item 36736, provides an easy-to-understand description of criteria for selecting shallow electron trap (SET) dopants. In certain preferred embodiments, it is contemplated to use a hexacoordination complex satisfying the following formula as a dopant.
[0126]
[ML₆]ⁿ
Where M is a full frontier orbital polyvalent metal ion, preferably Fe²⁺, Ru²⁺, Os²⁺, Co³⁺, Rh³⁺, Ir³⁺, Pd⁴⁺Or Pt⁴⁺And L₆Represents six coordination complex ligands that can be independently selected, provided that at least four of the ligands are anionic ligands, and at least one of the ligands (preferably at least three and optimally at least four). Are more electronegative than any halide ligand. n is 2-, 3- or 4-. Specific examples of dopants that can provide shallow electron traps are shown below.
[0127]
SET-1 [Fe (CN)₆]^Four-
SET-2 [Ru (CN)₆]^Four-
SET-3 [Os (CN)₆]^Four-
SET-4 [Rh (CN)₆]^3-
SET-5 [Ir (CN)₆]^3-
SET-6 [Fe (pyrazine) (CN)_Five]^Four-
SET-7 [RuCl (CN)_Five]^Four-
SET-8 [OsBr (CN)_Five]^Four-
SET-9 [RhF (CN)_Five]^3-
SET-10 [IrBr (CN)_Five]^3-
SET-11 [FeCO (CN)_Five]^3-
SET-12 [RuF₂(CN)_Four]^Four-
SET-13 [OsCl₂(CN)_Four]^Four-
SET-14 [RhI₂(CN)_Four]^3-
SET-15 [IrBr₂(CN)_Four]^3-
SET-16 [Ru (CN)_Five(OCN)]^Four-
SET-17 [Ru (CN)_Five(N_Three)]^Four-
SET-18 [Os (CN)_Five(SCN)]^Four-
SET-19 [Rh (CN)_Five(SeCN)]^3-
SET-20 [Ir (CN)_Five(HOH)]^2-
SET-21 [Fe (CN)_ThreeCl_Three]^3-
SET-22 [Ru (CO)₂(CN)_Four]^3-
SET-23 [Os (CN) Cl_Five]^Four-
SET-24 [Co (CN)₆]^3-
SET-25 [Ir (CN)_Four(Oxalate)]^3-
SET-26 [In (NCS)₆]^3-
SET-27 [Ga (NCS)₆]^3-
SET-28 [Co (NO₂)₆]^3-
SET-29 [Ir (NO₂)₆]^3-
SET-30 InCl_Three
SET-31 Ga (NO_Three)_Three
SET-32 TlCl
SET-33 Pb (NO_Three)₂
It is further contemplated to increase the speed using oligomeric coordination complexes as described in US Pat. No. 5,024,931 (Evans et al.). Further, as described in JP-A Nos. 11-24194 and 11-109537 (Oshiyama et al.), Five-coordinate and four-coordinate dopants may be used, and JP-A Nos. 11-102042 and 11 It is also possible to use a metal complex containing a ligand having an adsorbing group to silver halide described in No. 184036.
[0128]
The pAg control that maximizes the effect of metal doping will be described. The metal doping process and the subsequent pAg are controlled to maximize the metal doping effect. Specifically, the metal doping step can be achieved by controlling the pAg to 8.5 or less during metal doping and controlling the grain growth pAg thereafter to 9 or more. More preferably, the pAg is controlled to 8.3 or less during metal doping, and the subsequent pAg is controlled to 9.3 or more. Further, in the operation of pAg, it is possible to devise such as gradually increasing pAg in order to increase the doping rate stepwise depending on the required particle performance, or gradually decreasing to decrease stepwise.
[0129]
The silver halide emulsion according to claims 3, 11, 19, 27, and 35 of the present invention is characterized by containing a hexacoordinate cyano complex of at least one polyvalent metal, and as a particularly preferred metal dopant, K_Four[Fe (CN)₆], K_Three[Fe (CN)₆], K_Four[Ru (CN)₆].
[0130]
The concentration distribution of the metal dopant in the silver halide grains can be determined by dissolving the grains little by little from the surface to the inside and measuring the dopant content in each part. Specific examples include the methods described below.
[0131]
Prior to metal quantification, the silver halide emulsion is pretreated as follows. First, 50 ml of 0.2% actinase aqueous solution is added to about 30 ml of the emulsion, and the mixture is stirred at 40 ° C. for 30 minutes for gelatin degradation. This operation is repeated 5 times. After centrifugation, washing is repeated 5 times with 50 ml of methanol, 2 times with 50 ml of 1N nitric acid, and 5 times with ultrapure water. After centrifugation, only the silver halide is separated. The surface portion of the obtained silver halide grains is dissolved by an aqueous ammonia solution or ammonia whose pH is adjusted (the ammonia concentration and pH are changed according to the type and amount of dissolution of silver halide). As a method for dissolving the extreme surface of silver bromide grains in silver halide, about 3% of the grain surface can be dissolved using 20 ml of about 10% aqueous ammonia solution per 2 g of silver halide. At this time, the amount of silver halide dissolved is determined by centrifuging the aqueous ammonia solution and silver halide after dissolution of the silver halide, and determining the amount of silver present in the resulting supernatant by a high frequency induction plasma mass spectrometer. (ICP-MS) It can be quantified by a high frequency induction plasma emission spectrometer (ICP-AES) or by atomic absorption. The amount of metal per mole of silver halide present at about 3% of the grain surface can be determined from the difference between the amount of metal contained in the silver halide after dissolution and the total amount of silver halide not dissolved. it can. Examples of the metal determination method include an ICP-MS method, an ICP-AES method, or an atomic absorption method, which is dissolved in an ammonium thiosulfate aqueous solution, a sodium thiosulfate aqueous solution, or a potassium cyanide aqueous solution, and is matrix-matched. Of these, when potassium cyanide is used as a solvent and ICP-MS (manufactured by FSON Elemental Analysis) is used as an analyzer, an internal standard element Cs solution is prepared so that about 40 mg of silver halide is dissolved in 5 ml of 0.2N potassium cyanide to 10 ppb The sample is made up to a constant volume of 100 ml with ultrapure water and used as a measurement sample. Then, the metal in the measurement sample is quantified by ICP-MS using a calibration curve in which the matrix is combined using metal-free silver halide. At this time, the exact amount of silver in the measurement sample can be quantified by ICP-AES or atomic absorption of the measurement sample diluted 100 times with ultrapure water. After such dissolution of the grain surface, the silver halide grains are washed with ultrapure water, and the dissolution of the grain surface is repeated in the same manner as described above, so that the metal in the inner direction of the silver halide grains is obtained. The amount can be quantified.
[0132]
A preferable content of the metal dopant in the tabular grain of the present invention is effective at a normal concentration (here, the concentration is a concentration based on the total silver based on the total silver in the tabular grain). In general, the preferred concentration of shallow electron trap forming dopant is 1 × 10 6 per mole of silver halide.^-91 x 10 moles or more^-2A range of less than or equal to a mole is suitable, more preferably 1 × 10.^-Five1 x 10 moles or more^-3A molar range is preferred.
[0133]
The effect of the metal dopant according to claims 4, 12, 20, 28, and 36 of the present invention can be effectively exhibited by adding the metal dopant to the base grain in a state doped in advance in a silver halide fine grain emulsion. In this case, as a particularly preferred metal dopant, Pb (NO_Three)₂, K₂IrCl₆, K_ThreeIrCl₆, K₂IrBr₆, InCl_ThreeCan be given. At this time, the concentration of the metal dopant with respect to 1 mol of silver halide fine particles is 1 × 10.^-1Mol ~ 1 × 10^-7Moles are preferred, 1 × 10^-3Mol ~ 1 × 10^-FiveMole is more preferred.
[0134]
As a method of doping silver halide fine particles with a metal dopant in advance, it is preferable to form fine particles in a state where the metal dopant is dissolved in a halide solution.
[0135]
The halogen composition of the silver halide fine grains may be any of silver bromide, silver iodide, silver chloride, silver iodobromide, silver chlorobromide, and silver chloroiodobromide, but the same halogen composition as the base grain. Is preferred.
[0136]
The time for depositing silver halide fine particles containing metal dopant on the base grain may be anywhere from the base grain formation to before the start of chemical sensitization, but from the end of the desalting process to before the start of chemical sensitization. Is particularly preferred.
[0137]
By adding the fine grain emulsion in a state where the salt concentration of the base emulsion is low, the silver halide fine grains are deposited together with the metal dopant on the portion where the base grain has the highest activity. That is, it can be efficiently deposited on the outer peripheral region including the corners and edges of the tabular grains of the present invention. This deposition means that the silver halide fine particles are dissolved in the reaction system in which the silver halide fine particles and the base particles coexist, instead of agglomerating and adsorbing the silver halide fine particles to the base particles as they are. Regeneration as silver halide. That is, when a part of the emulsion obtained by the above method is taken out and observed with an electron microscope, silver halide fine particles are not observed, and epitaxial protrusions are not observed on the surface of the base particle. Say.
[0138]
The silver halide fine particles to be added are 1 × 10 5 per mol of the base grains.^-7It is preferable to add a silver amount of 1 mol to 0.5 mol.^-FiveMol ~ 1 × 10^-1It is more preferable to add a molar amount of silver.
[0139]
Physical ripening conditions for depositing silver halide fine particles can be arbitrarily selected between 30 ° C. and 70 ° C./10 minutes to 60 minutes.
[0140]
The interparticle distance control method in the invention according to claims 5, 13, 21, 29, and 37 of the present invention will be described. The inter-grain distance control method is a method of reducing the volume of the reactant solution by concentrating the reactant solution that forms the grains in the silver halide grain formation process, or increasing the volume by the additive solution for grain formation. By concentrating the minute and keeping it constant, or by suppressing the volume increase,
Average interparticle distance = [volume of reactant solution / number of growing particles in reactant solution] 1/3
Is a method for controlling the average inter-grain distance between silver halide grains in the reactant solution defined in (1).
[0141]
Specifically, the inter-grain distance control method uses a reaction vessel for forming silver halide grains to which a concentrating mechanism such as an ultrafiltration device is connected. This is achieved by removing only the aqueous solution containing the product from the reaction solution.
[0142]
The concentration mechanism is connected to the reaction vessel by a pipe or the like, and the reaction solution solution can be circulated between the reaction vessel and the concentration mechanism at an arbitrary flow rate by the reaction solution circulation mechanism such as a pump, and can be arbitrarily stopped. Furthermore, the apparatus has an apparatus for detecting the volume of an aqueous solution containing a salt extracted from the reactant solution by the concentration mechanism, and a mechanism capable of arbitrarily controlling the amount thereof. In addition, other functions can be added as necessary.
[0143]
Further, the apparatus for producing the silver halide emulsion of the present invention is preferably an apparatus having a mechanism for adding water having a set temperature to the reaction vessel to increase the average inter-grain distance.
[0144]
In the present invention, the control of the distance between grains in the growth process of silver halide grains is aimed at improving both photographic performance and emulsion yield of the silver halide emulsion. This is not the intention of the present invention.
[0145]
As an embodiment of a silver halide emulsion production apparatus that can be preferably applied to the present invention, a silver halide emulsion production apparatus capable of arbitrarily controlling and maintaining the average inter-grain distance in the grain growth process by an ultrafiltration apparatus. An example will be described with reference to FIG.
[0146]
The reaction vessel 1 contains a dispersion medium 3 from the beginning. This apparatus includes a silver addition line 4 for adding at least one aqueous silver salt solution, preferably an aqueous silver nitrate solution, and at least one aqueous halide salt solution, preferably an alkali metal such as bromine, iodine, or chlorine. It has a halide addition line 5 for adding an aqueous salt solution, an aqueous ammonium salt solution, or a mixture thereof. Further, it has a stirring mechanism 2 for stirring the dispersion medium and the reactant solution (mixture of the dispersion medium and silver halide grains) in the silver halide emulsion preparation process. This agitation mechanism can be in any conventional manner. The aqueous silver salt solution is added to the reaction vessel from the silver addition line 4 at a flow rate controlled by the silver addition valve 20. The aqueous halogen salt solution is added from the halide addition line 5 to the reaction vessel at a flow rate controlled by the halide addition valve 21. The addition of the solution through the silver addition line 4 and the halide addition line 5 may be liquid level addition, but is more preferably added to the liquid in the vicinity of the stirring mechanism 2. Agitation mechanism 2 mixes an aqueous silver salt solution and an aqueous halogen salt solution with a dispersion medium, allowing the soluble silver salt to react with the soluble halide salt to produce silver halide.
[0147]
During the silver halide formation in the first stage, that is, in the nucleation step, a dispersion (reactant solution) containing silver halide nuclei as a base is formed. Subsequently, the nucleation step is completed through an aging step as necessary. Thereafter, when the addition of the aqueous silver salt solution and the aqueous halogen salt solution is continued, the process proceeds to the second stage of silver halide formation, that is, the growth process stage, and additional silver halide generated as a reaction product in the process is first formed. It is deposited on the formed silver halide core grains to increase the size of these grains. In the present invention, a part of the reactant solution in the reaction vessel is transferred to the ultrafiltration unit 12 through the liquid removal line 8 by the circulation pump 13 in the particle formation process by adding the silver salt aqueous solution and the halogen salt aqueous solution to the reaction vessel. Sent to the reaction vessel through the liquid return line 9. At that time, the pressure applied to the ultrafiltration unit 12 is adjusted by a pressure adjusting valve 18 provided in the middle of the liquid return line 9 to limit a part of the water-soluble salt solution contained in the reactant solution. It isolate | separates with a filtration unit and discharges out of the system through the permeate discharge line 10. By such a method, it is possible to form particles while arbitrarily controlling the inter-particle distance even in the grain growth process by adding the silver salt aqueous solution and the halogen salt aqueous solution to the reaction vessel.
[0148]
When this method is applied in the present invention, it is preferable to arbitrarily control the permeate amount (ultrafiltration flux) of the water-soluble salt solution separated by the ultrafiltration membrane. For example, in this case, the ultrafiltration flux can be arbitrarily controlled using a flow rate adjusting valve 19 provided in the middle of the permeate discharge line 10. At that time, in order to minimize the pressure fluctuation of the ultrafiltration unit 12, the permeate return line 11 may be used by opening the valve 25 provided in the middle of the permeate return line 11. Alternatively, it is not necessary to close the valve 25 and use the permeate return line 11, which can be arbitrarily selected depending on the operating conditions. The ultrafiltration flux may be detected by using a flow meter 14 provided in the middle of the permeate discharge line 10 or by detecting a change in mass using a permeate receiver 27 and a scale 28. .
[0149]
In the present invention, the concentration by the ultrafiltration method in the particle growth process may be performed continuously throughout the particle formation process, or may be performed intermittently. However, when the ultrafiltration method is applied in the particle growth process, the circulation of the reactant solution may be continued at least until the end of particle formation after the reactant solution circulation to the ultrafiltration step is started. preferable. Accordingly, it is preferable that the circulation of the reactant solution to the ultrafiltration unit is continued even when the concentration is interrupted. This is to avoid uneven growth between the particles in the reaction vessel and the particles in the ultrafiltration step. Moreover, it is preferable that the circulating flow rate through the ultrafiltration step be sufficiently high. Specifically, the residence time in the ultrafiltration unit including the liquid removal line and the liquid return line of the silver halide reactant solution is preferably within 30 seconds, more preferably within 15 seconds, and even more preferably within 10 seconds. Particularly preferred.
[0150]
The volume of the ultrafiltration step including the liquid take-out line 8, the liquid return line 9, the ultrafiltration unit 12, the circulation pump 13, and the like is preferably 30% or less, and 20% or less of the volume of the reaction vessel volume. More preferably, it is particularly preferably 10% or less.
[0151]
Thus, by applying an ultrafiltration step, the volume of the total silver halide reactant solution can be arbitrarily reduced during grain formation. It is also possible to keep the volume of the silver halide reactant solution arbitrarily by adding water from the addition line 7.
[0152]
In the present invention, there are no particular restrictions on the ultrafiltration module and the circulation pump that can be used when carrying out ultrafiltration, but the materials and the like that act on the silver halide emulsion and adversely affect photographic performance, etc. It is preferable to avoid the structure. Moreover, the molecular weight cut off of the ultrafiltration membrane used in the ultrafiltration module can be arbitrarily selected. For example, if you want to remove the dispersion medium such as gelatin contained in the silver halide emulsion or the compound used during the preparation of the emulsion during the grain growth process, select an ultrafiltration membrane with a molecular weight cut off that is higher than the molecular weight of the removal target. In addition, when it is not desired to remove, an ultrafiltration membrane having a fractional molecular weight equal to or lower than the molecular weight of the removal target can be selected.
[0153]
In the present invention, using the interparticle distance control method for particle formation, or applying the interparticle distance control method during particle formation,
(1) In the process of forming silver halide grains, the volume of the reactant solution is reduced by using the concentration mechanism.
(2) In the step of forming silver halide grains, the above-mentioned concentration mechanism is used to remove from the reactant solution an aqueous solution containing the same amount of water or solubles as the amount of the additive solution for silver halide formation, Keep the volume of the solution constant
(3) In the step of forming silver halide grains, using the above-described concentration mechanism, simultaneously with the addition of the additive solution for forming silver halide, water or an aqueous solution containing a soluble substance is removed from the reactant solution, Suppress volume increase of solution
This means the above operations (1) to (3) or a combination thereof. In (3) above, the volume of the reactant solution may be increased or decreased as a result of the suppression of the volume increase.
[0154]
In the present invention, the following operation (4) is preferably used in combination with the above (1) to (3).
[0155]
(4) Add water or an aqueous solution containing soluble substances to increase the volume of the reactant solution
In the present invention, the interparticle distance control method is applied in a state where the emulsion is circulated between the concentration mechanism such as the ultrafiltration device and the reaction vessel without removing water or an aqueous solution containing soluble substances. Is not specified.
[0156]
In the present invention, the interparticle distance control method does not necessarily have to be applied throughout the entire particle formation process. Rather, it is preferably used for the particle forming step.
[0157]
In general, the grain formation process of a silver halide emulsion is roughly divided into a nucleation process (consisting of a nucleation process and a nucleation process) and a subsequent nucleation process. It is also possible to separately grow a nuclear emulsion (or seed emulsion) prepared in advance. The growth process may include several stages such as a first growth process and a second growth process. In the present invention, the inter-grain distance control method is preferably applied to the growth process of silver halide grains.
[0158]
When the intergranular distance control method is applied to the formation of grains having dislocation lines in the emulsion of the present invention, the intergranular distance control method should be applied immediately before the introduction of the dislocation lines and / or during the growth immediately after the introduction of the dislocation lines. Is preferred. Specifically, it is preferable to reduce or keep the liquid amount of the reactant solution immediately before the introduction of the dislocation line and / or during the growth immediately after the introduction of the dislocation line. When the intergranular distance control method is applied during the growth immediately after the introduction of dislocation lines, it is preferably applied over 1 to 50% of the total silver amount after introduction of the dislocation lines, and is applied over 5 to 40%. It is preferable.
[0159]
A more preferable application mode of the interparticle distance control method when introducing dislocation lines is to concentrate the volume of the reactant solution to 2/3 or less before introducing the dislocation lines. More preferably, the reactant volume is concentrated to 1/2 or less, and particularly preferably, the reactant volume is concentrated to 1/3 or less. The interparticle distance is preferably 2.6 μm or less immediately before the introduction of dislocation lines, more preferably 2.3 μm or less, still more preferably 2.0 μm or less, and particularly preferably 1.5 μm or less. And most preferably 1.0 μm or less.
[0160]
The silver halide emulsion of the invention according to claims 6, 14, 22, 30, and 38 is characterized in that the silver halide grains contained in the silver halide emulsion have silver halide protrusions on the grain surface.
[0161]
The silver halide emulsion having silver halide protrusions on the surface of the silver halide grains means that the silver halide grains having silver halide protrusions on the surface of the silver halide grains are 30% of the total projected area of the silver halide grains. The above-mentioned silver halide emulsion is referred to, and 50% or more of the total projected area is preferably silver halide grains having silver halide protrusions on the surface of the silver halide grains, and 70% or more of the total projected area. Are more preferably silver halide grains having silver halide protrusions on the surface of the silver halide grains.
[0162]
In the invention described in claim 6, 14, 22, 30, or 38 of the present invention, the silver halide protrusion on the surface of the silver halide grain is preferably epitaxial, and the halide having the silver halide protrusion. The silver grains are preferably tabular silver halide grains.
[0163]
Conduction emitted by photon absorption during imagewise exposure by epitaxially placing silver halide protrusions at selected sites on the silver halide grains that serve as the substrate (hereinafter sometimes referred to as “host grains”) It is generally said that the competition of band electrons to sensitized sites is reduced, thus improving sensitivity. U.S. Pat. No. 4,435,501 discloses an improvement in sensitivity by epitaxially depositing a silver salt at selected sites on the surface of the host tabular grains. In the US patent, the increase in sensitivity is attributed to limiting the epitaxial deposition of silver salt to a small portion of the surface area of the host tabular grains. That is, the epitaxial placement of a tabular grain on a limited portion of the main plane is more efficient than the epitaxial arrangement covering all or most of the main plane, and more preferably substantially limited to the edge of the host grain. Further, an epitaxial arrangement in which the amount of coating on the main plane is limited, and more efficient and preferable is an epitaxial arrangement limited to the corner of the host particle or in the vicinity thereof, or other separate sites. The spacing between the corners of the main plane of the host particle itself reduces photoelectron competition sufficiently to achieve near maximum sensitivity. U.S. Pat. No. 4,435,501 teaches that the number of epitaxial sites on the host particles can be reduced by slowing the rate of epitaxial deposition.
[0164]
Therefore, also in the present invention, the silver halide protrusions epitaxially arranged on the surface area of the host grain are preferably limited to a small part of the surface area of the host grain, and particularly preferably limited to the corner or the vicinity thereof. Specifically, it is preferably less than 50%, and more preferably less than 30%. Further, the silver amount of the silver halide protrusions epitaxially arranged is preferably 0.3 to 25%, more preferably 0.5 to 15% with respect to the silver amount of the host grain.
[0165]
As one of the most preferred embodiments of the present invention, it is preferable that the epitaxially disposed silver halide protrusions are formed at restricted positions at or near the corners of the host grains. As a method for achieving this, A known method can be applied. US Pat. No. 4,435,501 discloses a method for adsorbing spectral sensitizing dyes and aminoazaindenes as site directors, and can be preferably applied to the present invention.
[0166]
In order to avoid structural collapse of the host grains, it is preferable that the total solubility of the silver halide protrusions arranged epitaxially is higher than the total solubility of the silver halide forming the host grains. Therefore, it is preferable that the silver halide protrusions disposed epitaxially are specifically silver chloride. Since silver chloride forms a face-centered cubic lattice structure like silver bromide, it facilitates epitaxial deposition.
[0167]
In order to maintain the structural integrity of the host particles, the epitaxial deposition is preferably performed under conditions that limit the solubility of the halide that forms the host particles. However, in some cases, the halide of the epitaxially arranged silver halide protrusions is from the host grain. That is, the silver chloride protrusions contain a small amount of bromide and possibly iodide.
[0168]
The silver halide emulsion according to claims 7, 15, 23, 31, and 39 of the present invention is characterized in that the silver halide grains contained in the silver halide emulsion contain silver chloride.
[0169]
The silver halide photographic emulsion containing silver chloride refers to a silver halide photographic emulsion in which the average silver chloride content of silver halide grains in the silver halide photographic emulsion is 0.1 to 100 mol%. .
[0170]
According to Claims 7, 15, 23, 31, and 39 of the present invention, the average silver chloride content of the silver halide grains in the silver halide photographic emulsion containing silver chloride is 0.3 to 50 mol%. Is preferable, and 0.5 to 30 mol% is more preferable.
[0171]
In Claims 7, 15, 23, 31, and 39 of the present invention, the component other than silver chloride is preferably silver bromide and / or silver iodide, and the silver halide composition is silver chloride, silver iodochloride, iodine salt. Silver bromide and silver chlorobromide can be used.
[0172]
In Claims 7, 15, 23, 31, and 39 of the present invention, one of preferred embodiments in the case where the average silver chloride content in the silver halide grains is lower than 10 mol% is described in Japanese Patent Application No. 10-152852, JP-A-11-184028, 11-271901, 11-258720, etc., which are silver halide grains containing silver chloride in the outermost layer of silver halide grains or in a specific portion of the silver halide grains, Silver halide grains that specifically contain silver chloride at the apex of the silver halide grains are also preferred.
[0173]
When the silver halide emulsion of the invention described in claims 7, 15, 23, 31, and 39 of the present invention is silver chlorobromide, the silver bromide may be localized at or near the vertex of the silver halide crystal. preferable. Such silver halide emulsions are prepared by adsorbing a sensitizing dye or inhibitor on a silver chloride or silver chlorobromide grain crystal, and then ripening by adding silver bromide fine particles, or forming a water-soluble bromide solution. It can be obtained by addition and halogen substitution.
[0174]
In the inventions according to claims 7, 15, 23, 31, and 39 of the present invention, when the average silver chloride content in the silver halide grains is higher than 10 mol%, the average chloride in the silver halide grains is particularly high. When the silver content is 50 to 100 mol%, silver iodide and / or silver bromide is localized in the core portion or shell portion in the silver halide grains, or a specific site on the surface of the silver halide grains. The form is also preferred.
[0175]
The dispersion medium contained in the silver halide emulsion of the present invention is a compound having protective colloid properties for silver halide grains. The dispersion medium is preferably present from the nucleation step at the time of silver halide grain formation to the grain growth step. Examples of the dispersion medium that can be preferably used in the present invention include gelatin and hydrophilic colloid. Examples of gelatin include alkali-treated gelatin, acid-treated gelatin having a molecular weight of about 100,000, oxidized gelatin, Bull. Soc. Sci. Photo. Japan No. 16, P30 (1966), enzyme-treated gelatin can be preferably used. In particular, when nucleating silver halide grains, gelatin having an average molecular weight of 10,000 to 70,000 is preferably used, and gelatin having an average molecular weight of 10,000 to 50,000 is more preferably used. In order to reduce the average molecular weight of gelatin, gelatin can be decomposed using gelatin-degrading enzyme, hydrogen peroxide, or the like. Similarly, it is also preferable to use gelatin with a low methionine content during nucleation. The methionine content per unit mass (gram) of the dispersion medium is preferably 50 μmol or less, and more preferably 20 μmol or less. The methionine content in gelatin can be reduced by oxidizing the gelatin with hydrogen peroxide or the like.
[0176]
Examples of hydrophilic colloids include gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose and cellulose sulfates, sodium alginate, starch derivatives Sugar derivatives such as: polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinyl pyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, and various kinds such as copolymers such as polyvinyl pyrazole Synthetic hydrophilic polymer materials can be used. Examples of gelatin include lime-processed gelatin, acid-processed gelatin, and Bull. Soc. Sci. Photo. Japan. No. 16. An enzyme-treated gelatin as described in P30 (1966) may be used, and a hydrolyzate or enzyme-decomposed product of gelatin can also be used.
[0177]
In the invention according to claims 8, 16, 24 and 32, the silver halide emulsion grain forming step is described in JP-A-5-72658, JP-A-9-197595, JP-A-9-251193, and the like. Of these, chemically modified gelatin substituted with an amino group of gelatin can be preferably used.
[0178]
When chemically modified gelatin is used in the particle forming step, 10 mass percent or more of the total dispersion times used for particle formation is preferably the chemically modified gelatin, more preferably 30 mass percent or more, and 50 mass percent or more. More preferably. The substitution ratio of the amino group is preferably 30% or more, more preferably 50% or more, and further preferably 80% or more.
[0179]
In the silver halide emulsion of the present invention, at least one of chalcogen sensitization such as sulfur sensitization and selenium sensitization, gold sensitization, and noble metal sensitization such as palladium sensitization is optionally used in the production process of the silver halide emulsion. Can be applied in the process. Further, it is preferable to combine two or more sensitization methods. Various types of emulsions can be prepared depending on the step of chemical sensitization. There are a mode in which chemical sensitization nuclei are embedded in the interior of the particle, a mode in which the chemical sensitization nuclei are embedded at a shallow position from the particle surface, and a mode in which chemical sensitization nuclei are formed on the surface. In the silver halide emulsion to which the present invention relates, the location of chemical sensitization nuclei can be selected according to the purpose. Generally preferred is the case where at least one chemical sensitization nucleus is formed near the surface.
[0180]
One of the chemical sensitization methods that can be preferably carried out on the silver halide emulsion of the present invention is sensitization using a chalcogen compound and sensitization using a noble metal, either alone or in combination. James), The Photographic Process, 4th edition, published by Macmillan, 1977, (TH James, The Theory of the Photographic Process, 4th ed, McCillan, 1977) pages 67-76. The active gelatin can be used as described above, and Research Disclosure Volume 120, April 1974, 12008; Research Disclosure Volume 34, June 1975, 13452, US Pat. No. 2,642,361 No. 3, 297,446, No. 3,77 No. 3,031, No. 3,857,711, No. 3,901,714, No. 4,226,018, No. 3,904,415, and British Patent No. 1,315,755. Can be sulfur, selenium, tellurium, gold, platinum, palladium or multiple combinations of these sensitizers at pAg 5-10, pH 5-8 and temperature 30-80 ° C.
[0181]
In the noble metal sensitization, for example, a noble metal salt of gold, platinum, or palladium can be used, and gold sensitization, palladium sensitization, or a combination of both is particularly preferable. In the case of gold sensitization, for example, known compounds such as chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, and gold selenide can be used. The palladium compound means a palladium divalent salt or a tetravalent salt. Preferred palladium compounds are R₂PdX₆Or R₂PdX_FourIt is represented by Here, R represents a hydrogen atom, an alkali metal atom or an ammonium group. X represents a halogen atom and represents a chlorine, bromine or iodine atom.
[0182]
Specifically, for example, K₂PdCl_Four, (NH_Four)₂PdCl₆, Na₂PdCl_Four, (NH_Four)₂PdCl_Four, Li₂PdCl_Four, Na₂PdCl₆Or K₂PdBr_FourIs preferred. Gold compounds and palladium compounds are preferably used in combination with thiocyanate or selenocyanate.
[0183]
The preferred amount of gold sensitizer for gold sensitization to the emulsion of the present invention is 1 × 10 5 per mole of silver halide.^-Four~ 1x10^-7Mole, more preferably 1 × 10^-Five~ 5x10^-7Is a mole. The preferred range of the palladium compound is 1 × 10^-3To 5 × 10^-7It is. A preferable range of the thiocyan compound or the selenocyan compound is 5 × 10.^-2To 1 × 10^-6It is.
[0184]
One of the chalcogen sensitization methods that can be preferably carried out for the silver halide emulsion of the present invention is sulfur sensitization. Sulfur sensitizers are described in hypo, thiourea compounds, rhodanine compounds and US Pat. Nos. 3,857,711, 4,226,018 and 4,054,457. Sulfur-containing compounds can be used. Chemical sensitization can also be performed in the presence of a so-called chemical sensitization aid. Useful chemical sensitization aids include compounds known to suppress fogging and increase sensitivity during the process of chemical sensitization, such as azaindene, azapyridazine, and azapyrimidine. Examples of chemical sensitization aid modifiers are disclosed in U.S. Pat. Nos. 2,131,038, 3,411,914, 3,554,757, JP-A-58-126526, and the above-mentioned daffine. It is described in the book “photographic emulsion chemistry”, pp. 138-143. The preferred amount of sulfur sensitizer when sulfur sensitizing the silver halide emulsion of the present invention is 1 × 10 5 per mole of silver halide.^-Four~ 1x10^-7Mole, more preferably 1 × 10^-Five~ 5x10^-7Is a mole.
[0185]
Selenium sensitization is one of the chalcogen sensitization methods that can be preferably carried out for the silver halide emulsion of the present invention. In selenium sensitization, a known unstable selenium compound is used. Specifically, for example, colloidal metal selenium, selenoureas (for example, N, N-dimethylselenourea, N, N-diethylselenourea, etc.), Selenium compounds such as selenoketones and selenoamides can be used. Selenium sensitization is preferably used in combination with sulfur sensitization or noble metal sensitization or both.
[0186]
The silver halide emulsion of the present invention can 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, Aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinethiones; Azaindenes, for example, triazaindenes, tetraazaindenes (especially 4-hydroxy substituted (1,3,3a, 7) tetraazaindenes), pentaazaine Known as antifoggants or stabilizers such as emissions such, it can be added to many compounds. For example, those described in US Pat. Nos. 3,954,474, 3,982,947, and Japanese Patent Publication No. 52-28660 can be used. One preferred compound is a compound described in JP-A-63-212932. Antifoggants and stabilizers are used at various times before particle formation, during particle formation, after particle formation, water washing process, dispersion after water washing, chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. It can be added depending on the purpose. In addition to the original antifogging and stabilizing effect added during emulsion preparation, control the crystal wall of grains, reduce grain size, reduce grain solubility, control chemical sensitization, It can be used for various purposes such as controlling the arrangement of dyes.
[0187]
The silver halide emulsion of the present invention can contain a spectral sensitizing dye. Further, it is a preferred embodiment to adsorb spectral sensitizing dyes to the silver halide grains of the present invention. Spectral sensitizing dyes include methine dyes, and 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 cyanine dyes, merocyanine dyes, and dyes belonging to the complex merocyanine color cord. 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 fused with aromatic hydrocarbon rings in these nuclei, for example, indolenine nucleus, benzindolenin nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselena Zole nucleus, benzimidazole nucleus and quinoline nucleus can be applied. These nuclei may be substituted on carbon atoms. In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, for example, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, 5-6 membered heterocyclic nuclei such as rhodanine nucleus and thiobarbituric acid nucleus can be applied.
[0188]
These sensitizing dyes may be used alone or in combination. The combination of sensitizing dyes is often used for the purpose of supersensitization. Typical examples thereof are U.S. Pat. Nos. 2,688,545, 2,977,229, 3,397,060, 3,522,052, 3,527,641, 3,617,293, 3,628,964, 3,666,480, 3,672,898, 3,679,428, 3,703 377, 3,769,301, 3,814,609, 3,837,862, 4,026,707, British Patent 1,344,281, No. 1,507,803, Japanese Patent Publication Nos. 43-4936, 53-12375, Japanese Patent Application Laid-Open Nos. 52-110618, and 52-109925. Along with the sensitizing dye, a dye that does not itself have a spectral sensitizing action or a substance that does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion.
[0189]
In the silver halide emulsion of the present invention, the generally preferred spectral sensitizing dye is added after the silver halide grains are formed. Most commonly, it is carried out after completion of chemical sensitization and before application, but as described in US Pat. Nos. 3,628,969 and 4,225,666, chemical sensitizers are used. Spectral sensitization can be performed simultaneously with chemical sensitization, or prior to chemical sensitization as described in JP-A-58-113928, and silver halide grains can be precipitated. Spectral sensitization can be started by adding before completion of the production. Furthermore, adding these compounds separately as taught in U.S. Pat. No. 4,255,666, i.e. adding some of these compounds prior to chemical sensitization and the remainder chemically. It can be added after sensitization, and may be any time during the formation of silver halide grains, including the method disclosed in US Pat. No. 4,183,756. The amount added is 4 x 10 per mole of silver halide.^-6~ 8x10^-3It can be used in the molar range, but when the silver halide grain size is 0.2 to 1.2 μm, it is about 5 × 10^-Five~ 2x10^-3Mole is more effective.
[0190]
When a color light-sensitive material is constituted using the silver halide photographic emulsion of the present invention, the silver halide emulsion which has been subjected to physical ripening, chemical ripening and spectral sensitization is used.
[0191]
Additives used in such processes are described in RD17643, page 23, section III to page 24, VI-M, RD18716, page 648-649, and RD308119, page 996, section III-A to page 1000, section VI-M. Has been.
[0192]
Known photographic additives that can be used in the present invention are also RD17643, page 25, section VIII-A to page 27, section XIII, RD18716, page 650-651, RD308119, page 1003, section VIII-A, page 1012 to section XXI-E. Can be used.
[0193]
Various couplers can be used for the color light-sensitive material, and specific examples thereof are described in RD17643, page 25, VII-CG, and RD308119, page 1001, VII-CG.
[0194]
Additives used in the present invention can be added by a dispersion method described in RD308119, page 1007, section XIV.
[0195]
In the present invention, the supports described in RD17643, page 28, XVII, RD18716, pages 647-8, and RD308119, page 1009, XVII can be used.
[0196]
The photosensitive material can be provided with auxiliary layers such as a filter layer and an intermediate layer described in RD308119, page 1002, item VII-K.
[0197]
The photosensitive material can take various layer configurations such as a normal layer, a reverse layer, and a unit configuration described in the above-mentioned RD308119, VII-K.
[0198]
The silver halide photographic emulsion of the present invention is preferably applied to various color light-sensitive materials represented by color negative films for general use or movies, color reversal films for slides or television, color paper, color positive film and color reversal paper. can do.
[0199]
The light-sensitive material according to the present invention can be developed by a conventional method described in RD17643, pages 28 to 29, XIX, RD18716, pages 651 and RD308119, pages 1010 to 1011.
[0200]
In addition to the silver halide emulsion of the present invention, the silver halide photographic light-sensitive material to which the present invention relates includes normal crystals that do not contain twin planes. P.) Examples as described in 163, for example, single twins including one twin plane, parallel multiple twins including two or more parallel twin planes, non-parallel including two or more non-parallel twin planes It can be selected from multiple twins according to the purpose. An example in which particles having different shapes are mixed is disclosed in US Pat. No. 4,865,964, but this method can be selected as necessary.
[0201]
In the case of a normal crystal, a (100) face cube, a (111) face octahedron, and a (110) face dodecahedron disclosed in JP-B-55-42737 and JP-A-60-222842. Particles can be used. Furthermore, Journal of Imaging Science, Vol. 30, p. 247, as reported in 1986 (211) as a representative (hll) face particle, (331) as a representative (hhl) face particle, (210 The (hk0) face particles typified by a) plane and (hkl) face grains typified by a (321) face also require some ingenuity in the preparation method, but can be selected and used according to the purpose. Depending on the purpose, particles with two or many faces coexisting, such as a tetrahedral particle in which (100) face and (111) face coexist in one particle, and a particle in which (100) face and (110) face coexist are used. Can be selected and used.
[0202]
The silver halide grains related to the present invention include a treatment for rounding the grains as disclosed in European Patent Nos. 96,727B1 and 64,412B1, or West German Patent No. 2,306,447C2. And surface modification as disclosed in JP-A-60-221320.
[0203]
The surface of the silver halide grains is generally a flat structure, but irregularities can be formed intentionally. A method of making a hole in a part of a crystal described in JP-A-58-106532 and 60-221320, for example, a vertex or the center of a surface, or a raffle described in US Pat. No. 4,643,966 An example is particles.
[0204]
In addition to the silver halide emulsion of the present invention, the silver halide photographic material to which the present invention relates may be a so-called polydispersed emulsion having a wide grain size distribution or a so-called monodispersed emulsion having a narrow size distribution depending on the purpose. You can choose and use it. In some cases, the coefficient of variation of the projected area equivalent diameter of the particle or the sphere equivalent diameter of the volume is used as a scale representing the size distribution. When a monodispersed emulsion is used, an emulsion having a size distribution with a coefficient of variation of 20% or less, more preferably 15% or less is preferably used. In order to satisfy the target gradation of the light-sensitive material, two or more kinds of monodispersed silver halide emulsions having different grain sizes in an emulsion layer having substantially the same color sensitivity are mixed or separated in the same layer. Multiple layers can be applied to the layers. Further, two or more kinds of polydispersed silver halide emulsions or a combination of a monodispersed emulsion and a polydispersed emulsion can be mixed or overlaid.
[0205]
When the silver halide emulsion of the present invention is used as a light-sensitive material, the above-mentioned various additives are used, but various other additives can be used depending on the purpose. These additives are described in more detail in Research Disclosure Item 17643 (December 1978), Item 18716 (November 1979) and Item 308119 (December 1989).
[0206]
The silver halide emulsion of the present invention can be used for various photographic light-sensitive materials. As an important aspect, the silver halide emulsion of the present invention is suitable for use in a multilayer photographic material having at least two silver halide emulsion layers. For example, in the case of a multilayer photographic material such as a color negative film or a color reversal film, the silver halide emulsion related to the present invention may be used on either the high-sensitivity layer side or the low-sensitivity layer side. Also good.
[0207]
【Example】
EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these embodiments.
[0208]
Example 1
[Preparation of Comparative Emulsion Em1-1]
<Formation of core>
A core was formed as follows.
[0209]
[Nucleation process]
B-101 in the reaction vessel was kept at 30 ° C., and concentrated sulfuric acid was diluted to 1/10 while stirring at a stirring speed of 400 revolutions / minute using a mixing stirrer described in JP-A-62-160128. The pH was adjusted to 2 by adding 29.0 ml of the solution. The pBr in the reaction vessel was 2.2. Thereafter, S-101 and X-101 kept at 30 ° C. were added at a constant flow rate for 1 minute using a double jet method to perform nucleation. After completion of nucleation, G-101 kept at 40 ° C. was added.
[0210]
(B-101)
Alkali-treated inert gelatin (average molecular weight 100,000) 12.1 g
3.7g potassium bromide
H₂O 1293.8ml
(S-101)
Silver nitrate 18.8g
H₂O 84.4ml
(X-101)
Potassium bromide 13.2g
H₂O 83.9ml
(G-101)
Alkali-treated inert gelatin (average molecular weight 100,000) 52.0g
10% by mass methanol solution of the following [Compound A] 1.7 ml
H₂O 1220.0ml
[Compound A] HO (CH₂CH₂O)_m[CH (CH_Three) CH₂O]₂₀(CH₂CH₂O)_nH (m + n = 10)
The solution in the reaction vessel was heated to 60 ° C. over 30 minutes, and further aged for 30 minutes. Subsequently, 33.6 ml of 28% ammonia aqueous solution was added, the pH was adjusted to 9.3 with 10% potassium hydroxide aqueous solution and held for 6 minutes, and then the pH was adjusted to 5.8 using 1N nitric acid aqueous solution. During the ripening step, the silver potential of the solution (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) was controlled to 6 mV using a 1N aqueous potassium bromide solution.
[0211]
[Nuclear growth process]
After completion of the nucleation process, a core growth process as follows was performed to form a core phase.
[0212]
While accelerating the flow rate of 3.5N silver nitrate aqueous solution S-102 and 3.5N potassium bromide aqueous solution X-102 using the double jet method, the ratio of the addition flow rate at the end and start is about 12 times over 38 minutes. Added (139.5 g of silver nitrate was consumed with this addition). During this time, the silver potential of the solution was controlled at 6 mV using a 1N potassium bromide solution. G-102 was added after the addition. Thereafter, S-102 and X-102 were added again while accelerating the flow rate (with this addition, 477.7 g of silver nitrate was consumed). During this time, the silver potential of the solution was controlled to 6 mV using a 1N potassium bromide solution.
[0213]
(S-102)
617.2 g of silver nitrate
H₂O 896.2ml
(X-102)
Potassium bromide 432.4g
H₂O 881.1ml
(G-102)
Alkali-treated inert gelatin (average molecular weight 100,000) 84.0g
10% by mass methanol solution of [Compound A] 2.3 ml
H₂O 600.0ml
<< Formation of the first shell >>
Following the formation of the core, a 3.5N silver nitrate aqueous solution S-103 and a 3.5N potassium bromide / potassium iodide aqueous solution (potassium iodide 10 mol%) X-103 were added while accelerating the flow rate to add a first shell. Formed. During this time, the silver potential of the solution was controlled at 6 mV using a 1N potassium bromide solution.
[0214]
(S-103)
Silver nitrate 432.0g
H₂O 627.3 ml
(X-103)
Potassium bromide 272.4g
Potassium iodide 42.2g
H₂614.2 ml of O
<< Formation of the second shell >>
Following the formation of the core phase, a 3.5N silver nitrate aqueous solution S-104 and a 3.5N potassium bromide aqueous solution X-104 were added while accelerating the flow rate to form a second shell. During this time, the silver potential of the solution was controlled at 6 mV using a 1N potassium bromide solution.
[0215]
(S-104)
Silver nitrate 612.0g
H₂O 888.7 ml
(X-104)
Potassium bromide 428.7g
H₂O 873.7ml
<< Formation of third shell >>
After completion of the addition, the temperature of the solution in the reaction vessel was lowered to 40 ° C. over 30 minutes. Thereafter, the Z-101 solution and then the SS-101 solution are added, the pH is adjusted to 9.3 using an aqueous potassium hydroxide solution, and iodine ions are released while aging for 4 minutes. A third shell was formed. Thereafter, the pH was adjusted to 5.0 using an aqueous acetic acid solution, and then the silver potential in the reaction vessel was adjusted to -39 mV using an aqueous 3.5N potassium bromide solution.
[0216]
(Z-101)
Sodium p-iodoacetamidobenzenesulfonate 77.0 g
H₂O 1000.0ml
(SS-101)
Sodium sulfite 26.8g
H₂O 300.0ml
<< Formation of the fourth shell >>
Following the above addition, 3.5N silver nitrate aqueous solution S-105 and 3.5N potassium bromide aqueous solution X-105 were added while accelerating the flow rate to form a fourth shell layer.
[0217]
(S-105)
Silver nitrate 720.0g
H₂O 1045.5ml
(X-105)
Potassium bromide 504.4g
H₂O 1028.0ml
The addition of the aqueous silver nitrate solution and the aqueous halogen salt solution at the time of forming each phase described above was performed at a higher addition rate within the range where no new nucleation occurred during the addition, except during nucleation. After completion of the shell phase formation, desalting and water washing were performed according to the method described in JP-A-5-72658, gelatin was added and well dispersed, pH was adjusted to 5.8 and pAg was adjusted to 8.1 at 40 ° C. . Thus, tabular silver halide emulsion Em1-1 was obtained. As a result of the analysis, it was found that the emulsion Em1-1 was a tabular grain having an average particle size in terms of cube of 0.85 μm and 80% or more of the projected area having an aspect ratio of 5 or more.
[0218]
[Preparation of Comparative Emulsions Em1-2 to Em1-3]
Emulsions Em1-2 to Em1-3 were prepared in the same manner as the preparation of emulsion Em1-1. However, for the emulsions Em1-2 to Em1-3, the amount of the solution to be added and the composition of the halogen salt aqueous solution were adjusted so that each emulsion had the silver iodide distribution structure shown in Table 1.
[0219]
The characteristics of each emulsion are shown in Table 1.
[Preparation of Emulsions Em1-4 to 1-6]
In the preparation of emulsions Em1-1 to Em1-3, when 6.6% of the total added silver amount was consumed, the R-1 solution was added in rush, and when 70% of the total added silver amount was consumed, T- Emulsions Em1-4 to 1-6 were prepared by the same production method as Em1-1 except that 1 solution was added by rush.
[0220]
(R-1)
Thiourea dioxide 21.3mg
37.3 ml of distilled water
(T-1)
Sodium ethanethiosulfonate 703.9mg
Distilled water 234.6ml
[Preparation of Emulsions Em1-7 to Em1-9]
In the preparation of Emulsions Em1-1 to Em1-3, Emulsions Em1-7 were the same as Em1-1 to Em1-3 except that T-1 solution was added by rush when 70% of the total added silver amount was consumed. ~ Em1-9 was prepared.
[0221]
[Preparation of Emulsions Em1-10 to Em1-12]
In the preparation of emulsions Em1-1 to Em1-3, the pAg was adjusted to 8.9 when 65% of the total amount of added silver was consumed, and then the metal doping agent SET-1 (K_Four[Fe (CN)₆] In aqueous solution 2 × 10^-6The emulsion was prepared in the same manner as in Em1-1 to Em1-3 except that pAg was adjusted to 10.3 when 70% of the total amount of added silver was consumed at the end of the addition of mol / mol Ag. Em1-10 to Em1-12 were prepared.
[0222]
[Preparation of Emulsions Em1-13 to Em1-15]
In the preparation of emulsions Em1-10 to Em1-12, the metal dopant was changed from SET-1 to SET-2 (K_Four[Ru (CN)₆1) with aqueous solution instead of 1 × 10^-FiveEmulsions Em1-13-1 to Em1-15 were prepared in the same manner as Em1-10 to Em1-12, except that mol / mol Ag was added.
[0223]
[Preparation of Emulsions Em1-16 to Em1-18]
In the preparation of emulsions Em1-1 to Em1-3, after completion of grain growth, desalting was performed according to the method described in JP-A-5-72658, and then a gelatin solution was added to adjust the emulsion temperature to 50 ° C. Emulsions Em1-16 to Em1-18 were prepared in the same manner as Emulsions Em1-1 to Em1-3 except that the F-1 solution was added.
[0224]
(F-1)
K₂IrCl₆Made of silver bromide grains doped with (average particle size 0.05 μm)
Fine grain emulsion (*) 3.76 g
* Preparation method of fine grain emulsion F-1 is as follows:
To 5000 ml of a 6.0% by weight gelatin solution containing 0.06 mol of potassium bromide, 2000 ml of an aqueous solution containing 7.06 mol of silver nitrate, 7.06 mol of potassium bromide and 4.4 × 10^-3Mole K₂IrCl₆2000 ml of an aqueous solution containing was added over 10 minutes. During the fine particle formation, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the particle formation, the pH was adjusted to 6.0 using an aqueous sodium carbonate solution. The finished mass was 12.53 kg.
[0225]
[Preparation of Emulsions Em1-19 to Em1-21]
In the growth process of Em1-1 to Em1-3, using an ultrafiltration device, the temperature was lowered to 40 ° C., and at the same time, the reaction solution was concentrated to 9.1 l (1/3 or less of the volume before concentration), After adjusting the silver potential in the reaction vessel to -39 mV, emulsions Em1-19 to Em1-21 were prepared in the same manner as Em1-1 to Em1-3, except that the volume of the reactant solution was maintained until the end of the growth step. .
[0226]
[Preparation of Emulsions Em1-22 to Em1-24]
Emulsions Em1-1 to Em1-3 were dissolved at 40 ° C., and 1N silver nitrate aqueous solution and 1N potassium iodide aqueous solution were simultaneously added at a flow rate ratio of 8: 1 to adjust to pBr4.0. Subsequently, 0.02 mol of 1N aqueous sodium chloride solution is added per mol of the emulsion (Em1-1 to Em1-3), and the spectral sensitizing dyes SD-6 and SD-7 described later are added so that the total coverage becomes 70%. Then, a 0.5N silver nitrate aqueous solution and a 0.5N sodium chloride aqueous solution were simultaneously added at a constant rate of 0.05 mol per mol of the emulsion (Em1-1 to Em1-3). By this operation, emulsions Em1-22 to Em1-24 were prepared in which epitaxials were formed mainly at the corners and edges of the tabular silver halide grains.
[0227]
[Preparation of Emulsions Em1-25 to Em1-27]
Emulsions Em1-1 to Em1-3 were dissolved at 60 ° C., and the pAg was adjusted to 8.8 with 2N aqueous potassium bromide solution. The emulsion was adjusted to pAg 8.06 and pH 5.8 at 40 ° C. to prepare emulsions Em1-25 to Em1-27.
[0228]
(K-1 solution)
Fine grain emulsion composed of 3.0% by weight gelatin and silver chloride fine grains (average grain size 0.08 μm)
The preparation method is shown below.
[0229]
Addition of 2000 ml of an aqueous solution containing 7.06 mol of silver nitrate and 2000 ml of an aqueous solution containing 7.06 mol of sodium chloride to 5000 ml of a 6.0% by mass gelatin solution containing 0.06 mol of sodium chloride over 10 minutes. did. During the fine particle formation, the pH was controlled at 3.0 using nitric acid, and the temperature was controlled at 30 ° C. After completion of the addition, the pH was adjusted to 6.0 using an aqueous sodium carbonate solution and adjusted to a pAg of 7.5 with a 2N aqueous sodium chloride solution at 40 ° C.
[0230]
[Preparation of Emulsions Em1-28 to Em1-30]
In the preparation of emulsions Em1-1 to Em1-3, 50% by weight of the gelatin used for (B-101), (G-101) and (G-102) was converted to phenylcarbamoylated gelatin (amino group substitution rate 90%). Emulsions Em1-28 to Em1-30 were prepared in the same manner as Em1-1 to Em1-3, except that
[0231]
In each of the emulsions Em1-1 to Em1-30, tabular grains having an aspect ratio of 5 or more accounted for 80% or more of the projected area. In any of these emulsions, an average of 20 or more dislocation lines per grain was observed in the fringe portion.
[0232]
The characteristics of each emulsion are shown in Table 1.
[0233]
[Table 1]

[0234]
Sensitizing dyes SD-6, SD-7, and SD-8 were added to each of the emulsions Em1-1 to Em1-30 maintained at 52 ° C. At this time, Em-22 to 24 were added after subtracting the amount of dye used in preparing the emulsion. After aging for 20 minutes, sodium thiosulfate, triphenylphosphine selenide, chloroauric acid, and potassium thiocyanate were added. The amount of sensitizing dye or sensitizer added and the ripening time are adjusted so that optimum sensitivity-fogging is obtained for each emulsion, and 1-phenyl-5-mercaptotetrazole and 4-hydroxy-6-methyl-1 are adjusted. 3,3a, 7-tetraazaindene was added for stabilization.
[0235]
[Preparation of color photosensitive material samples]
A layer 101 of a silver halide multilayer color photographic material was prepared by coating each layer having the following composition on the cellulose triacetate film support provided with the undercoat layer in order from the support side.
[0236]
Addition amount is 1m unless otherwise stated²Indicates the number of grams per unit. Silver halide and colloidal silver are shown in terms of silver, and sensitizing dye (shown as SD) is shown in moles per mole of silver.
[0237]
First layer (Anti-halation layer)
Black colloidal silver 0.16
UV-1 0.30
CM-1 0.12
CC-1 0.03
OIL-1 0.24
Gelatin 1.33
Second layer (intermediate layer)
Silver iodobromide emulsion j 0.10
AS-1 0.12
OIL-1 0.15
Gelatin 0.67
Third layer (low sensitivity red color sensitive layer)
Silver iodobromide emulsion c 0.053
Silver iodobromide emulsion d 0.11
Silver iodobromide emulsion e 0.11
SD-1 2.2 × 10^-Five
SD-2 5.9 × 10^-Five
SD-3 1.2 × 10^-Four
SD-4 1.6 × 10^-Four
SD-5 1.6 × 10^-Four
C-1 0.19
CC-1 0.003
OIL-2 0.096
AS-2 0.001
Gelatin 0.44
4th layer (medium sensitivity red color sensitive layer)
Silver iodobromide emulsion b 0.28
Silver iodobromide emulsion c 0.34
Silver iodobromide emulsion d 0.50
SD-1 1.8 × 10^-Five
SD-4 2.6 × 10^-Four
SD-5 2.8 × 10^-Four
C-1 0.74
CC-1 0.081
DI-1 0.020
DI-4 0.008
OIL-2 0.42
AS-2 0.003
Gelatin 1.95
5th layer (high sensitivity red color sensitive layer)
Silver iodobromide emulsion a 1.45
Silver iodobromide emulsion e 0.076
SD-1 2.3 × 10^-Five
SD-2 1.1 × 10^-Four
SD-3 1.5 × 10^-Five
SD-4 2.1 × 10^-Four
C-2 0.087
C-3 0.12
CC-1 0.036
DI-1 0.021
DI-3 0.005
BAR-1 0.022
OIL-2 0.15
AS-2 0.004
Gelatin 1.40
6th layer (intermediate layer)
F-1 0.03
AS-1 0.18
OIL-1 0.22
Gelatin 1.00
7th layer (low sensitivity green color sensitive layer)
Silver iodobromide emulsion c 0.22
Silver iodobromide emulsion e 0.22
SD-6 4.7 × 10^-Five
SD-7 2.6 × 10^-Four
SD-8 1.9 × 10^-Four
SD-9 1.1 × 10_-Four
SD-10 2.4 × 10^-Five
M-1 0.35
CM-1 0.044
DI-2 0.010
OIL-1 0.41
AS-2 0.001
AS-3 0.11
Gelatin 1.29
8th layer (medium sensitive green color sensitive layer)
Silver iodobromide emulsion b 0.90
Silver iodobromide emulsion e 0.048
SD-6 3.8 × 10^-Five
SD-7 2.6 × 10^-Four
SD-8 3.4 × 10^-Four
SD-9 1.6 × 10^-Four
SD-10 4.4 × 10^-Five
M-1 0.15
CM-1 0.062
CM-2 0.030
DI-2 0.032
OIL-1 0.28
AS-2 0.005
AS-3 0.045
Gelatin 1.00
9th layer (high sensitivity green color sensitive layer)
Emulsion Em1-1 1.39
Silver iodobromide emulsion e 0.073
SD-6 4.1 × 10^-Five
SD-7 2.6 × 10^-Five
SD-8 3.7 × 10^-Four
SD-10 4.9 × 10^-Five
M-1 0.071
M-2 0.073
CM-2 0.013
DI-2 0.004
DI-3 0.003
OIL-1 0.27
AS-2 0.008
AS-3 0.043
Gelatin 1.35
10th layer (yellow filter layer)
Yellow colloidal silver 0.053
AS-1 0.15
OIL-1 0.18
X-1 0.06
Gelatin 0.83
11th layer (low sensitivity blue color sensitive layer)
Silver iodobromide emulsion g 0.22
Silver iodobromide emulsion h 0.099
Silver iodobromide emulsion i 0.17
SD-11 2.4 × 10^-Four
SD-12 5.7 × 10^-Four
SD-13 1.3 × 10^-Four
Y-1 1.02
BAR-1 0.022
OIL-1 0.42
AS-2 0.003
X-1 0.11
X-2 0.18
Gelatin 1.95
12th layer (high sensitivity blue color sensitive layer)
Silver iodobromide emulsion f 1.52
SD-11 8.3 × 10^-Five
SD-12 2.3 × 10^-Four
Y-1 0.22
DI-5 0.11
OIL-1 0.13
AS-2 0.003
X-1 0.15
X-2 0.20
Gelatin 1.20
13th layer (first protective layer)
Silver iodobromide emulsion j 0.30
UV-1 0.11
UV-2 0.055
Liquid paraffin 0.28
X-1 0.079
Gelatin 1.00
14th layer (second protective layer)
PM-1 0.13
PM-2 0.018
WAX-1 0.021
Gelatin 0.55
The characteristics of the silver iodobromide emulsion used above are shown below (the average grain size is the length of one side of a cube having the same volume).
[0238]
Emulsion No. Average particle diameter (μm) Average AgI amount (mol%) Diameter / thickness ratio
Silver iodobromide emulsion a 0.85 4.2 7.0
Silver iodobromide emulsion b 0.70 4.2 6.0
Silver iodobromide emulsion c 0.50 4.2 5.0
Silver iodobromide emulsion d 0.38 8.0 octahedral twin
Silver iodobromide emulsion e 0.27 2.0 tetrahedral normal crystal
Silver iodobromide emulsion f 1.00 8.0 4.5
Silver iodobromide emulsion g 0.74 3.5 6.2
Silver iodobromide emulsion h 0.44 4.2 6.1
Silver iodobromide emulsion i 0.30 1.9 5.5
Silver iodobromide emulsion j 0.03 2.0 1.0
The above sensitizing dyes are added to each of the above emulsions, and after ripening, triphenylphosphine selenide, sodium thiosulfate, chloroauric acid, and potassium thiocyanate are added. The material subjected to chemical sensitization was used.
[0239]
In addition to the above composition, coating aids SU-1, SU-2, SU-3, dispersion aid SU-4, viscosity modifier V-1, stabilizers ST-1, ST-2, weight Two types of polyvinylpyrrolidone (AF-1, AF-2) having an average molecular weight of 10,000 and a weight average molecular weight of 100,000, inhibitors AF-3, AF-4, AF-5, and hardener H-1. , H-2 and preservative Ase-1.
[0240]
The structure of the compound used for the sample is shown below.
[0241]
[Chemical Formula 10]

[0242]
Embedded image

[0243]
Embedded image

[0244]
Embedded image

[0245]
Embedded image

[0246]
Embedded image

[0247]
Embedded image

[0248]
Embedded image

[0249]
Embedded image

[0250]
Embedded image

[0251]
Embedded image

[0252]
Similarly, multilayer color photographic light-sensitive material samples 1002 to 1030 were prepared by using the emulsions Em1-2 to Em1-30 subjected to sensitization instead of the emulsion Em1-1.
[0253]
Samples 1002 to 1030 were subjected to step wedge exposure at 1.6 CMS for 1/200 second using white light, and then processed by the following standard color development processing.
[0254]
<Standard color development processing>
Processing process Processing time Processing temperature Replenishment amount *
Color development 3 minutes 15 seconds 38 ± 0.3 ° C 780 ml
Whitening 45 seconds 38 ± 2.0 ℃ 150ml
Settling time 1 minute 30 seconds 38 ± 2.0 ℃ 830ml
Stable 60 seconds 38 ± 5.0 ℃ 830ml
Drying 1 minute 55 ± 5.0 ° C −
* Replenishment amount is 1m photosensitive material²It is a hit value.
[0255]
The following were used as the color developer, bleaching solution, fixing solution, stabilizing solution and replenisher.
[0256]
Color developer
800ml water
30g potassium carbonate
Sodium bicarbonate 2.5g
Potassium sulfite 3.0g
Sodium bromide 1.3g
Potassium iodide 1.2mg
Hydroxylamine sulfate 2.5g
Sodium chloride 0.6g
4-Amino-3-methyl-N-ethyl-N- (β-hydroxylethyl)
Aniline sulfate 4.5g
Diethylenetriaminepentaacetic acid 3.0g
Potassium hydroxide 1.2g
Add water to 1 liter and adjust to pH 10.06 using potassium hydroxide or 20% sulfuric acid.
[0257]
Color developer replenisher
800ml water
Potassium carbonate 35g
Sodium bicarbonate 3g
Potassium sulfite 5g
Sodium bromide 0.4g
Hydroxylamine sulfate 3.1g
4-Amino-methyl-N-ethyl-N- (β-hydroxylethyl)
Aniline sulfate 6.3g
Potassium hydroxide 2g
Diethylenetriaminepentaacetic acid 3.0g
Add water to 1 liter and adjust to pH 10.18 with potassium hydroxide or 20%.
[0258]
Bleach solution
700ml of water
125 g of iron (III) ammonium 1,3-diaminopropanetetraacetate
Ethylenediaminetetraacetic acid 2g
Sodium nitrate 40g
150g ammonium bromide
Glacial acetic acid 40g
Add water to 1 liter and adjust to pH 4.4 using aqueous ammonia or glacial acetic acid.
[0259]
Bleach replenisher
700ml of water
1,3-diaminopropanetetraacetic acid iron (III) ammonium 175 g
Ethylenediaminetetraacetic acid 2g
Sodium nitrate 50g
200 g of ammonium bromide
Glacial acetic acid 56g
Adjust to pH 4.4 with aqueous ammonia or glacial acetic acid and add water to make 1 liter.
[0260]
Fixer
800ml water
120g ammonium thiocyanate
150g ammonium thiosulfate
Sodium sulfite 15g
Ethylenediaminetetraacetic acid 2g
Adjust to pH 6.2 using aqueous ammonia or glacial acetic acid and add water to make 1 liter.
[0261]
Fixing replenisher
800ml water
150g ammonium thiocyanate
180g ammonium thiosulfate
Sodium sulfite 20g
Ethylenediaminetetraacetic acid 2g
Adjust to pH 6.5 with aqueous ammonia or glacial acetic acid and add water to make 1 liter.
[0262]
Stabilizer and stable replenisher
900ml water
2.0 g of paraoctylphenyl polyoxyethylene ether (n = 10)
Dimethylolurea 0.5g
Hexamethylenetetramine 0.2g
1,2-Benzisothiazolin-3-one 0.1 g
Siloxane (UCC L-77) 0.1g
Ammonia water 0.5ml
After adding water to 1 liter, the pH is adjusted to 8.5 using aqueous ammonia or 50% sulfuric acid.
[0263]
The sensitivity, RMS value, and latent image stability of the obtained color multilayer photosensitive material sample were measured using green light. The measurement method and conditions are shown below.
[0264]
The relative sensitivity was expressed as a relative value where the reciprocal of the exposure amount giving the density of the unexposed area (= Dmin) +0.1 in each sample was obtained, and the sensitivity of the sample 1001 was taken as 100. A larger value of relative sensitivity means higher sensitivity and better sensitivity.
[0265]
For the relative RMS value, the RMS measurement position is a density point of Dmin + 0.2. The RMS value is measured by scanning the measurement position of each sample with a microdensitometer (slit width 10 μm, slit length 180 μm) equipped with Eastman Kodak's Latten filter (W-99), and the number of concentration measurement sampling is 1000 or more. The standard deviation of the concentration value of was determined. The RMS value was obtained for each sample, and indicated as a relative value with the RMS value of the sample 1001 being 100. It means that the smaller the value of the relative RMS, the better the graininess and the better.
[0266]
The latent image stability was evaluated by using a sample stored for 5 days in an environment of temperature 55 ° C. and humidity 65% as a time-lapse sample, and subjecting the time-lapse sample to exposure / color development similar to that of the sample before aging, Sample sensitivity variations were evaluated. The sensitivity variation of the sample 1001 is shown as a relative value with 100, and a smaller value is preferable because there is less variation.
[0267]
The results obtained for each sample are shown in Table 2.
[0268]
[Table 2]

[0269]
As is apparent from the table, samples 1005, 1006, 1008, 1009, 1011, 1012, 1014, 1015, 1017, 1018, 1020, 1021, 1023, 1024, 1026, 1027, 1029, 1030 (invention) according to the present invention. The composition of the invention described in claims 1 to 8 is highly sensitive to the comparative samples 1001, 1002, 1003, 1004, 1007, 1010, 1013, 1016, 1019, 1022, 1025, and 1028, graininess, Excellent performance in latent image stability.
[0270]
Example 2
[Preparation of Comparative Emulsion Em2-1]
Emulsion Em2-1 was prepared in the same manner as the above-mentioned emulsion Em1-1.
[0271]
[Preparation of Comparative Emulsion Em2-2]
Emulsion Em2-2 was prepared in the same manner as Emulsion Em2-1 except that the fourth shell was changed to the fourth and fifth shells as follows.
[0272]
<< Formation of the fourth shell >>
Following the addition of the third shell, a 3.5N silver nitrate aqueous solution S-201 and a 3.5N potassium bromide / potassium iodide aqueous solution (potassium iodide 3 mol%) X-201 were added while accelerating the flow rate, and the fourth shell was added. Formed.
[0273]
(S-201)
Silver nitrate 576.0g
H₂O 836.4ml
(X-201)
Potassium bromide 391.4g
Potassium iodide 16.89g
H₂O 821.2ml
<< Formation of the fifth shell >>
Following the addition of the fourth shell, a 3.5N silver nitrate aqueous solution S-202 and a 3.5N potassium bromide aqueous solution X-202 were added while accelerating the flow rate to form a fifth shell.
[0274]
(S-202)
Silver nitrate 144.0g
H₂O 209.1 ml
(X-202)
Potassium bromide 100.9g
H₂O 205.6ml
[Preparation of Emulsion Em2-3]
Emulsion Em2-3 was prepared in the same manner as Emulsion Em2-2. However, the amount of the solution to be added and the composition of the aqueous halogen salt solution were prepared so that the emulsion Em2-3 had the silver iodide distribution structure shown in Table 4.
[0275]
[Preparation of Emulsions Em2-4 to 2-6]
In the preparation of emulsions Em2-1 to Em2-3, when 6.6% of the total amount of added silver was consumed, the R-1 solution used in Example 1 was added in rush to make 70% of the total amount of added silver. Emulsions Em2-4 to 2-6 were prepared by the same production method as Em2-1 except that the T-1 solution used in Example 1 was added by rush when consumed.
[0276]
[Preparation of Emulsions Em2-7 to Em2-9]
In the preparation of emulsions Em2-1 to Em2-3, the same as Em2-1 to Em2-3 except that the T-1 solution used in Example 1 was added in rush when 70% of the total amount of added silver was consumed Emulsions Em2-7 to Em2-9 were prepared.
[0277]
[Preparation of Emulsions Em2-10 to Em2-12]
In the preparation of emulsions Em2-1 to Em2-3, pAg was adjusted to 8.9 when 65% of the total amount of added silver was consumed, and then metal doping agent SET-1 (K_Four[Fe (CN)₆] In aqueous solution 2 × 10^-6Emulsion Em2-10 was prepared by the same production method as Em2-1 except that pAg was adjusted to 10.3 when 70% of the total amount of silver added at the end of metal addition was consumed. Em2-12 was prepared.
[0278]
[Preparation of Emulsions Em2-13 to Em2-15]
In the preparation of emulsions Em1-10 to Em1-12, the metal dopant was changed from SET-1 to SET-2 (K_Four[Ru (CN)₆1) with aqueous solution instead of 1 × 10^-FiveEmulsions Em2-13 to Em2-15 were prepared in the same manner as Em2-10 to Em2-12, except that mol / mol Ag was added.
[0279]
[Preparation of Emulsions Em2-16 to Em2-18]
In the preparation of emulsions Em2-1 to Em2-3, after the completion of grain growth, desalting was performed according to the method described in JP-A-5-72658, and then a gelatin solution was added to adjust the emulsion temperature to 50 ° C. Emulsions Em2-16 to Em2-18 were prepared in the same manner as Emulsions Em2-1 to Em2-3 except that the F-1 solution used in Example 1 was added.
[0280]
[Preparation of Emulsions Em2-19 to Em2-21]
In the growth process of Em2-1 to Em2-3, using an ultrafiltration device, the temperature was lowered to 40 ° C., and at the same time, the reaction solution was concentrated to 9.1 l (1/3 or less of the volume before concentration), After adjusting the silver potential in the reaction vessel to -39 mV, emulsions Em2-19 to Em2-21 were prepared in the same manner as Em2-1 to Em2-3, except that the volume of the reactant solution was maintained until the end of the growth step. .
[0281]
[Preparation of Emulsions Em2-22 to Em2-24]
Emulsions Em2-1 to Em2-3 were dissolved at 40 ° C., and 1N silver nitrate aqueous solution and 1N potassium iodide aqueous solution were simultaneously added at a flow rate ratio of 8: 1 to adjust to pBr4.0. Subsequently, 0.02 mol of 1N sodium chloride aqueous solution is added per mol of the emulsion (Em2-1 to Em2-3) so that the total coverage of the above-described spectral sensitizing dyes SD-3 and SD-2 is 70%. Then, a 0.5N silver nitrate aqueous solution and a 0.5N sodium chloride aqueous solution were added simultaneously at a constant rate of 0.05 mol per mol of the emulsion (Em2-1 to Em2-3). By this operation, emulsions Em2-22 to Em2-24 in which epitaxials were formed mainly at the corners and edges of the tabular silver halide grains were prepared.
[0282]
[Preparation of Emulsions Em2-25 to Em2-27]
Emulsions Em2-1 to Em2-3 were dissolved at 60 ° C., the pAg was adjusted to 8.8 with 2N aqueous potassium bromide solution, and the silver halide content of the K-1 solution used in Example 1 was 0.7 mol. Equivalent amounts were added in 10 minutes, aged for 20 minutes, and then adjusted to pAg 8.06 and pH 5.8 at 40 ° C. to prepare emulsions Em2-25 to Em2-27.
[0283]
[Preparation of Emulsions Em2-28 to Em2-30]
In the preparation of emulsions Em2-1 to Em2-3, 50% by weight of the gelatin used for (B-101), (G-101) and (G-102) was replaced with phenylcarbamoylated gelatin (amino group substitution rate 90%) Emulsions Em2-28 to Em2-30 were prepared in the same manner as Em2-1 to Em2-3, except for the above.
[0284]
In each of the emulsions Em2-1 to Em2-30, tabular grains having an aspect ratio of 5 or more accounted for 80% or more of the projected area. In any of these emulsions, an average of 20 or more dislocation lines per grain was observed in the fringe portion. The characteristics of each emulsion are shown in Tables 3 and 4.
[0285]
[Table 3]

[0286]
[Table 4]

[0287]
[Preparation of color photosensitive material samples]
Multilayer color photographic material samples 2001 to 2030 were prepared by using the emulsions Em2-1 to Em2-30, which had been sensitized in the same manner as in Example 1, instead of the emulsion Em1-1 in Example 1. .
[0288]
Samples 2001 to 2030 were subjected to step wedge exposure at 1.6 CMS for 1/200 seconds using white light, and then processed by color development, and the same evaluation as in Example 1 was performed. The results obtained for each sample are shown in Table 5.
[0289]
[Table 5]

[0290]
As is apparent from the table, samples 2005, 2006, 2008, 2009, 2011, 2012, 2014, 2015, 2017, 2018, 2020, 2021, 2023, 2024, 2026, 2027, 2029, 2030 (invention) The constitution of the invention described in claims 9 to 16) is highly sensitive to the comparative samples 2001, 2002, 2003, 2004, 2007, 2010, 2013, 2016, 2019, 2022, 2025, 2028, graininess, Excellent performance in latent image stability.
[0291]
Example 3
[Preparation of Comparative Emulsion Em3-1]
Emulsion Em3-1 was prepared in the same manner as Emulsion Em1-1.
[0292]
[Preparation of Comparative Emulsion Em3-2]
Emulsion Em3-2 was prepared in the same manner as Emulsion Em1-1 except that the fourth shell was changed to the fourth, fifth, and sixth shells as follows. In emulsion Em3-2, tabular grains having an aspect ratio of 5 or more occupied 80% or more of the projected area. In this emulsion, an average of 20 or more dislocation lines per grain was observed in the fringe portion.
[0293]
<< Formation of the fourth shell >>
Following the addition of the third shell, a 3.5N silver nitrate aqueous solution S-301 and a 3.5N potassium bromide aqueous solution X-301 were added while accelerating the flow rate to form a fourth shell.
[0294]
(S-301)
Silver nitrate 240.0g
H₂O 348.5 ml
(X-301)
Potassium bromide 168.1g
H₂O 342.6ml
<< Formation of the fifth shell >>
Following the addition of the fourth shell, a 3.5N silver nitrate aqueous solution S-302 and a 3.5N potassium bromide / potassium iodide aqueous solution (3 mol% potassium iodide) X-302 were added while accelerating the flow rate, and the fifth shell was added. Formed.
[0295]
(S-302)
Silver nitrate 360.0g
H₂O 522.7 ml
(X-302)
Potassium bromide 244.6g
Potassium iodide 10.55g
H₂O 513.3 ml
<< Formation of the sixth shell >>
Following the addition of the fifth shell, a 3.5N silver nitrate aqueous solution S-303 and a 3.5N potassium bromide aqueous solution X-303 were added while accelerating the flow rate to form a sixth shell.
[0296]
(S-303)
Silver nitrate 120.0g
H₂O 174.2ml
(X-303)
Potassium bromide 84.1g
H₂O 171.3ml
[Preparation of Comparative Emulsion Em3-3]
Emulsion Em3-3 was prepared in the same manner as Emulsion Em3-2. However, the amount of the solution to be added and the composition of the aqueous halogen salt solution were prepared so that the emulsion Em3-3 had the silver iodide distribution structure shown in Table 7.
[0297]
[Preparation of Emulsions Em3-4 to 3-6]
In the preparation of emulsions Em3-1 to Em3-3, when 6.6% of the total amount of added silver was consumed, the R-1 solution used in Example 1 was added in rush to make 70% of the total amount of added silver. Emulsions Em3-4 to 3-6 were prepared by the same production method as Em3-1 except that the T-1 solution used in Example 1 was added in rush when consumed.
[0298]
[Preparation of Emulsions Em3-7 to Em3-9]
In preparation of emulsions Em3-1 to Em3-3, similar to Em3-1 to Em3-3, except that T-1 solution used in Example 1 was added in rush when 70% of the total added silver amount was consumed. Emulsions Em3-7 to Em3-9 were prepared.
[0299]
[Preparation of Emulsions Em3-10 to Em3-12]
In the preparation of emulsions Em3-1 to Em3-3, after 65% of the total amount of added silver was consumed, the pAg was adjusted to 8.9, and then the metal doping agent SET-1 (K_Four[Fe (CN)₆] In aqueous solution 2 × 10^-6Emulsion Em3-10 was prepared by the same production method as Em3-1 except that pAg was adjusted to 10.3 at the stage where the total amount of silver added at the end of metal addition was 70% at the time of addition of mol / mol Ag. Em3-12 was prepared.
[0300]
[Preparation of Emulsions Em3-13 to Em3-15]
In the preparation of emulsions Em3-10 to Em3-12, the metal doping agent was changed from SET-1 to SET-2 (K_Four[Ru (CN)₆1) with aqueous solution instead of 1 × 10^-FiveEmulsions Em3-13 to Em3-15 were prepared in the same manner as 3-10 to Em3-12, except that mol / mol Ag was added.
[0301]
[Preparation of Emulsions Em3-16 to Em3-18]
In the preparation of emulsions Em3-1 to Em3-3, after completion of grain growth, desalting was performed according to the method described in JP-A-5-72658, and then a gelatin solution was added to adjust the emulsion temperature to 50 ° C. Emulsions Em3-16 to Em3-18 were prepared in the same manner as Emulsions Em3-1 to Em3-3 except that the solution (F-1) used in Example 1 was added.
[0302]
[Preparation of Emulsions Em3-19 to Em3-21]
In the growth process of Em3-1 to Em3-3, using an ultrafiltration device, the temperature was lowered to 40 ° C., and at the same time, the reaction solution was concentrated to 9.1 l (1/3 or less of the volume before concentration), After adjusting the silver potential in the reaction vessel to -39 mV, emulsions Em3-19 to Em3-21 were prepared in the same manner as Em3-1 to Em3-3 except that the volume of the reactant solution was maintained until the end of the growth step. .
[0303]
[Preparation of Emulsions Em3-22 to Em3-24]
Emulsions Em3-1 to Em3-3 were dissolved at 40 ° C., and 1N silver nitrate aqueous solution and 1N potassium iodide aqueous solution were simultaneously added at a flow rate ratio of 8: 1 to adjust to pBr4.0. Subsequently, 0.02 mol of 1N aqueous sodium chloride solution is added per mol of the emulsion (Em3-1 to Em3-3), and the above-mentioned spectral sensitizing dyes SD-3 and SD-2 are added so that the total coverage becomes 70%. Then, a 0.5N silver nitrate aqueous solution and a 0.5N sodium chloride aqueous solution were added simultaneously at a constant rate of 0.05 mol per mol of the emulsion (Em3-1 to Em3-3). By this operation, emulsions Em3-22 to Em3-24 in which epitaxials were formed mainly at the corners and edges of the tabular silver halide grains were prepared.
[0304]
[Preparation of Emulsions Em3-25 to Em3-27]
Emulsions Em3-1 to Em3-3 were dissolved at 60 ° C., the pAg was adjusted to 8.8 with 2N aqueous potassium bromide solution, and the silver halide content of the K-1 solution used in Example 1 was 0.7 mol. A considerable amount was added in 10 minutes, ripened for 20 minutes, and then adjusted to pAg 8.06, pH 5.8 at 40 ° C. to prepare emulsions Em3-25 to Em3-27.
[0305]
[Preparation of Emulsions Em3-28 to Em3-30]
In the preparation of emulsions Em3-1 to Em3-3, 50% by weight of the gelatin used for (B-101), (G-101) and (G-102) was replaced with phenylcarbamoylated gelatin (amino group substitution rate 90%) Emulsions Em3-28 to Em3-30 were prepared in the same manner as Em3-1 to Em3-3, except that
[0306]
In each of the emulsions Em3-1 to Em3-30, tabular grains having an aspect ratio of 5 or more accounted for 80% or more of the projected area. In any of these emulsions, an average of 20 or more dislocation lines per grain was observed in the fringe portion. The characteristics of each emulsion are shown in Tables 6 and 7.
[0307]
[Table 6]

[0308]
[Table 7]

[0309]
[Preparation of color photosensitive material samples]
Multilayer color photographic light-sensitive material samples 3001 to 3030 were prepared by using the emulsions Em3-1 to Em3-30, which had been sensitized in the same manner as in Example 1, instead of the emulsion Em1-1 in Example 1. did.
[0310]
Samples 3001 to 3030 were subjected to step wedge exposure at 1.6 CMS for 1/200 seconds using white light, and then processed by color development, and the same evaluation as in Example 1 was performed. The results obtained for each sample are shown in Table 8.
[0311]
[Table 8]

[0312]
As is apparent from the table, samples 3005, 3006, 3008, 3009, 3011, 3012, 3014, 3015, 3017, 3018, 3020, 3021, 3023, 3024, 3026, 3027, 3029, 3030 (invention) related to the present invention. The constitution of the invention described in claims 17 to 20) is highly sensitive to the comparative samples 3001, 3002, 3003, 3004, 3007, 3010, 3013, 3016, 3019, 3022, 3025, 3028, graininess, Excellent performance in latent image stability.
[0313]
Example 4
[Preparation of Comparative Emulsion Em4-1]
Emulsion Em4-1 was prepared in the same manner as Emulsion Em1-1.
[0314]
[Preparation of Comparative Emulsion Em4-2]
S-101 and X-101 in the nucleation step were changed to S-401 and X-401, respectively, to make the core, and the following were renamed as the first shell to the fifth shell, and the same as Emulsion Em1-1. To produce Emulsion Em4-2.
(S-401)
Silver nitrate 18.8g
H₂O 84.4ml
(X-401)
Potassium bromide 11.9g
Potassium iodide 1.84g
H₂O 83.6ml
[Preparation of Comparative Emulsion Em4-3]
Emulsion Em4-3 was prepared in the same manner as Emulsion Em4-2, except that the fifth shell was changed as follows.
[0315]
<< Formation of the fifth shell >>
Following the addition of the fourth shell, a 3.5N silver nitrate aqueous solution S-402 and a 3.5N potassium bromide / potassium iodide aqueous solution (3 mol% potassium iodide) X-402 were added while accelerating the flow rate to form a fifth shell. Formed.
[0316]
(S-402)
Silver nitrate 576.0g
H₂O 836.4ml
(X-402)
Potassium bromide 391.4g
Potassium iodide 16.89g
H₂O 821.2ml
<< Formation of the sixth shell >>
Following the addition of the fifth shell, a 3.5N silver nitrate aqueous solution S-403 and a 3.5N potassium bromide aqueous solution X-403 were added while accelerating the flow rate to form a sixth shell.
[0317]
(S-403)
Silver nitrate 144.0g
H₂O 209.1 ml
(X-403)
Potassium bromide 100.9g
H₂O 205.6ml
[Preparation of Emulsions Em4-4 to 4-6]
In the preparation of emulsions Em4-1 to Em4-3, when 6.6% of the total added silver amount was consumed, the R-1 solution used in Example 1 was added in rush, and 70% of the total added silver amount was reduced. Emulsions Em4-4 to 4-6 were prepared by the same production method as Em4-1 except that the T-1 solution used in Example 1 was added by rush when consumed.
[0318]
[Preparation of Emulsions Em4-7 to Em4-9]
In the preparation of Emulsions Em4-1 to Em4-3, Emulsions Em4-7 were the same as Em4-1 to Em4-3 except that T-1 solution was added by rush when 70% of the total amount of added silver was consumed. ~ Em4-9 was prepared.
[0319]
[Preparation of Emulsions Em4-10 to Em4-12]
In the preparation of emulsions Em4-1 to Em4-3, the pAg was adjusted to 8.9 when 65% of the total amount of added silver was consumed, and then the metal doping agent SET-1 (K_Four[Fe (CN)₆] In aqueous solution 2 × 10^-6Emulsion Em4-10 was prepared by the same production method as Em4-1 except that pAg was adjusted to 10.3 at the stage where the total amount of added silver at the end of the addition of metal was 70%. Em4-12 was prepared.
[0320]
[Preparation of Emulsions Em4-13 to Em4-15]
In the preparation of emulsions Em4-10 to Em4-12, the metal dopant was changed from SET-1 to SET-2 (K_Four[Ru (CN)₆1) with aqueous solution instead of 1 × 10^-FiveEmulsions Em4-13 to Em4-15 were prepared in the same manner as Em4-10 to Em4-12, except that mol / mol Ag was added.
[0321]
[Preparation of Emulsions Em4-16 to Em4-18]
In the preparation of emulsions Em4-1 to Em4-3, after the completion of grain growth, desalting was performed according to the method described in JP-A-5-72658, and then a gelatin solution was added to adjust the emulsion temperature to 50 ° C. Emulsions Em4-16 to Em4-18 were prepared in the same manner as Emulsions Em4-1 to Em4-3 except that the F-1 solution used in Example 1 was added.
[0322]
[Preparation of Emulsions Em4-19 to Em4-21]
In the growth process of Em4-1 to Em4-3, using an ultrafiltration device, the temperature was lowered to 40 ° C., and at the same time, the reaction solution was concentrated to 9.1 l (less than 1/3 of the volume before concentration), After adjusting the silver potential in the reaction vessel to -39 mV, emulsions Em4-19 to Em4-21 were prepared in the same manner as Em4-1 to Em4-3, except that the volume of the reactant solution was maintained until the end of the growth step. .
[0323]
[Preparation of Emulsions Em4-22 to Em4-24]
Emulsions Em4-1 to Em4-3 were dissolved at 40 ° C., and 1N silver nitrate aqueous solution and 1N potassium iodide aqueous solution were simultaneously added at a flow ratio of 8: 1 to adjust to pBr4.0. Subsequently, 0.02 mol of 1N aqueous sodium chloride solution is added per mol of the emulsion (Em4-1 to Em4-3) so that the total coverage of the spectral sensitizing dyes SD-3 and SD-2 is 70%. Then, a 0.5N silver nitrate aqueous solution and a 0.5N sodium chloride aqueous solution were added simultaneously at a constant rate of 0.05 mol per mol of the emulsion (Em4-1 to Em4-3). By this operation, emulsions Em4-22 to Em4-24 in which epitaxials were formed mainly at the corners and edges of the tabular silver halide grains were prepared.
[0324]
[Preparation of Emulsions Em4-25 to Em4-27]
Emulsions Em4-1 to Em4-3 were dissolved at 60 ° C., the pAg was adjusted to 8.8 with 2N aqueous potassium bromide solution, and the silver halide content of the K-1 solution used in Example 1 was 0.7 mol. A considerable amount was added in 10 minutes, ripened for 20 minutes, and then adjusted to pAg 8.06, pH 5.8 at 40 ° C. to prepare emulsions Em4-25 to Em4-27.
[0325]
[Preparation of Emulsions Em4-28 to Em4-30]
In the preparation of emulsions Em4-1 to Em4-3, 50% by weight of the gelatin used for (B-101), (G-101) and (G-102) was replaced with phenylcarbamoylated gelatin (amino group substitution rate 90%). Emulsions Em4-28 to Em4-30 were prepared in the same manner as Em4-1 to Em4-3, except that they were replaced with.
[0326]
In each of the emulsions Em4-1 to Em4-30, tabular grains having an aspect ratio of 5 or more accounted for 80% or more of the projected area. In any of these emulsions, an average of 20 or more dislocation lines per grain was observed in the fringe portion. The characteristics of each emulsion are shown in Tables 9 and 10.
[0327]
[Table 9]

[0328]
[Table 10]

[0329]
[Preparation of color photosensitive material samples]
Multi-layered color photographic light-sensitive material samples 4001 to 4030 were prepared using the emulsions Em4-1 to Em4-30, which had been sensitized in the same manner as in Example 1, instead of the emulsion Em1-1 in Example 1. .
[0330]
Samples 4001 to 4030 were subjected to step wedge exposure at 1.6 CMS for 1/200 seconds using white light, and then processed by color development, and the same evaluation as in Example 1 was performed. The obtained results are shown in Table 11 for each sample.
[0331]
[Table 11]

[0332]
As is apparent from the table, samples 4005, 4006, 4008, 4009, 4011, 4012, 4014, 4015, 4017, 4018, 4020, 4021, 4023, 4024, 4026, 4027, 4029, 4030 (invention) related to the present invention. The structure of the invention according to claims 25 to 32) is highly sensitive to the comparative samples 4001, 4002, 4003, 4004, 4007, 4010, 4013, 4016, 4019, 4022, 4025, and 4028, graininess, Excellent performance in latent image stability.
[0333]
Example 5
[Preparation of Comparative Emulsion Em5-1]
Emulsion Em5-1 was prepared in the same manner as Emulsion Em1-1.
[0334]
[Preparation of Comparative Emulsion Em5-2]
<Formation of internal phase>
After the nucleation step was performed in the same manner as emulsion Em1-1, the following nucleation step was performed to form an internal phase.
[0335]
[Nuclear growth process]
While accelerating the flow rate of 3.5N aqueous silver nitrate solution S-501 and 3.5N aqueous potassium bromide solution X-501 using the double jet method (ratio of addition flow rate at the end and start is about 12 times) in 38 minutes Added. During this time, the silver potential of the solution was controlled at 6 mV using a 1N potassium bromide solution. G-501 was added after completion of the addition.
[0336]
(S-501)
Silver nitrate 809.2g
H₂O 1175.0ml
(X-501)
Potassium bromide 97.7g
H₂O 1155.3ml
(G-501)
Alkali-treated inert gelatin (average molecular weight 100,000) 84.0g
10% by mass methanol solution of [Compound A] 2.3 ml
H₂O 600.0ml
<< Formation of first high-iodine localized phase >>
After the addition was completed, a silver iodide fine grain emulsion having an average grain size of 0.03 μm was added in an amount corresponding to 0.212 mol to form a first high iodine localized phase.
[0337]
《Formation of intermediate phase》
Following the formation of the core phase, 3.5N aqueous silver nitrate solution S-502 and 3.5N aqueous potassium bromide solution X-502 were added while accelerating the flow rate to form an intermediate phase. During this time, the silver potential of the solution was controlled at 6 mV using a 1N potassium bromide solution.
[0338]
(S-502)
Silver nitrate 768.0g
H₂O 1115.2ml
(X-502)
538.1 g of potassium bromide
Potassium iodide 69.0g
H₂O 1096.5ml
《Formation of high iodine localized phase》
After completion of the addition, the temperature of the solution in the reaction vessel was lowered to 40 ° C. over 30 minutes. Thereafter, the silver potential in the reaction vessel was adjusted to −32 mV using a 3.5N aqueous potassium bromide solution, and a silver iodide fine grain emulsion solution having an average grain size of 0.03 μm was added in an amount corresponding to 0.283 mol to increase the high iodine content. A degree of localized phase was formed.
[0339]
<Formation of shell phase>
Following the addition of the silver iodide fine grain emulsion, a 3.5N silver nitrate aqueous solution S-503 and a 3.5N potassium bromide aqueous solution X-503 were added while accelerating the flow rate to form a shell phase.
[0340]
(S-503)
Silver nitrate 720.0g
H₂O 1045.5ml
(X-503)
Potassium bromide 504.4g
H₂O 1028.0ml
The addition of the aqueous silver nitrate solution and the aqueous halogen salt solution at the time of forming each phase described above was performed at a higher addition rate within the range where no new nucleation occurred during the addition, except during nucleation. After completion of the shell phase formation, desalting and water washing were performed according to the method described in JP-A-5-72658, gelatin was added and well dispersed, pH was adjusted to 5.8 and pAg was adjusted to 8.1 at 40 ° C. .
[0341]
[Preparation of Comparative Emulsion Em5-3]
Emulsion Em5-3 was prepared in the same manner as Emulsion Em5-2. However, the amount of the solution to be added and the composition of the halogen salt aqueous solution were prepared so that the emulsion had the silver iodide distribution structure shown in Table 12. In Emulsion Em5-3, tabular grains having an aspect ratio of 5 or more occupied 80% or more of the projected area. Further, in each of these emulsions, an average of 20 or more dislocation lines per grain was observed in the fringe portion.
[0342]
[Preparation of Emulsions Em5-4 to 5-6]
In the preparation of emulsions Em5-1 to Em5-3, when 6.6% of the total amount of added silver was consumed, the R-1 solution used in Example 1 was added in rush to make 70% of the total amount of added silver. Emulsions Em5-4 to 5-6 were prepared by the same production method as Em5-1 except that the T-1 solution used in Example 1 was added by rush when consumed.
[0343]
[Preparation of Emulsions Em5-7 to Em5-9]
In the preparation of emulsions Em5-1 to Em5-3, the same as Em5-1 to Em5-3, except that T-1 solution used in Example 1 was added in rush when 70% of the total amount of added silver was consumed Emulsions Em5-7 to Em5-9 were prepared.
[0344]
[Preparation of Emulsions Em5-10 to Em5-12]
In the preparation of emulsions Em5-1 to Em5-3, pAg was adjusted to 8.9 when 65% of the total amount of added silver was consumed, and then metal doping agent SET-1 (K_Four[Fe (CN)₆] In aqueous solution 2 × 10^-6Emulsion Em5-10 was prepared by the same production method as Em5-1 except that pAg was adjusted to 10.3 at the stage where the total added silver amount at the end of the metal addition was 70% was consumed. Em5-12 was prepared.
[0345]
[Preparation of Emulsions Em5-13 to Em5-15]
In the preparation of emulsions Em5-10 to Em5-12, the metal dopant was changed from SET-1 to SET-2 (K_Four[Ru (CN)₆1) with aqueous solution instead of 1 × 10^-FiveEmulsions Em5-13 to Em5-15 were prepared in the same manner as Em5-10 to Em5-12, except that mol / mol Ag was added.
[0346]
[Preparation of Emulsions Em5-16 to Em5-18]
In the preparation of emulsions Em5-1 to Em5-3, after the completion of grain growth, desalting was performed according to the method described in JP-A-5-72658, and then a gelatin solution was added to adjust the emulsion temperature to 50 ° C. Emulsions Em5-16 to Em5-18 were prepared in the same manner as Emulsions Em5-1 to Em5-3 except that the F-1 solution used in Example 1 was added.
[0347]
[Preparation of Emulsions Em5-19 to Em5-21]
In the growth process of Em5-1 to Em4-3, using an ultrafiltration device, the temperature was lowered to 40 ° C., and at the same time, the reaction solution was concentrated to 9.1 l (1/3 or less of the volume before concentration), After adjusting the silver potential in the reaction vessel to -39 mV, emulsions Em5-19 to Em5-21 were prepared in the same manner as Em5-1 to Em5-3, except that the volume of the reactant solution was maintained until the end of the growth step. .
[0348]
[Preparation of Emulsions Em5-22 to Em5-24]
Emulsions Em5-1 to Em5-3 were dissolved at 40 ° C., and 1N silver nitrate aqueous solution and 1N potassium iodide aqueous solution were simultaneously added at a flow ratio of 8: 1 to adjust to pBr4.0. Subsequently, 0.02 mol of 1N aqueous sodium chloride solution is added per mol of the emulsion (Em5-1 to Em5-3) so that the total coverage of the above-described spectral sensitizing dyes SD-3 and SD-2 is 70%. Then, a 0.5N silver nitrate aqueous solution and a 0.5N sodium chloride aqueous solution were added simultaneously at a constant rate of 0.05 mol per mol of the emulsion (Em5-1 to Em5-3). By this operation, emulsions Em5-22 to Em5-24 in which epitaxials were formed mainly at the corners and edges of the tabular silver halide grains were prepared.
[0349]
[Preparation of Emulsions Em5-25 to Em5-27]
Emulsions Em5-1 to Em5-3 were dissolved at 60 ° C., the pAg was adjusted to 8.8 with 2N aqueous potassium bromide solution, and the silver halide content of the K-1 solution used in Example 1 was 0.7 mol. A considerable amount was added in 10 minutes, ripened for 20 minutes, and then adjusted to pAg 8.06, pH 5.8 at 40 ° C. to prepare emulsions Em5-25 to Em5-27.
[0350]
[Preparation of Emulsions Em5-28 to Em5-30]
In the preparation of emulsions Em5-1 to Em5-3, 50% by mass of the gelatin used for (B-101), (G-101) and (G-102) was converted to phenylcarbamoylated gelatin (amino group substitution rate 90%). Emulsions Em5-28 to Em5-30 were prepared in the same manner as Em5-1 to Em5-3, except for the above.
[0351]
In each of the emulsions Em5-1 to Em5-30, tabular grains having an aspect ratio of 5 or more occupied 80% or more of the projected area. In any of these emulsions, an average of 20 or more dislocation lines per grain was observed in the fringe portion. Table 12 shows the characteristics of each emulsion.
[0352]
[Table 12]

[0353]
[Preparation of color photosensitive material samples]
Multilayer color photographic light-sensitive material samples 5001 to 5030 were prepared using the emulsions Em5-1 to Em5-30, which had been sensitized in the same manner as in Example 1, instead of the emulsion Em1-1 in Example 1. .
[0354]
Samples 5001 to 5030 were subjected to step wedge exposure at 1.6 CMS for 1/200 seconds using white light, and then processed by color development, and the same evaluation as in Example 1 was performed. The results obtained for each sample are shown in Table 13.
[0355]
[Table 13]

[0356]
As is apparent from the table, samples 5005, 5006, 5008, 5009, 5011, 5012, 5014, 5015, 5017, 5018, 5020, 5021, 5023, 5024, 5026, 5027, 5029, 5030 (invention) related to the present invention. The structure of the invention according to claims 33 to 40) is highly sensitive to the comparative samples 5001, 5002, 5003, 5004, 5007, 5010, 5013, 5016, 5019, 5022, 5025, 5028, graininess, Excellent performance in latent image stability.
[0357]
【The invention's effect】
According to the present invention, a silver halide emulsion and a silver halide photographic light-sensitive material excellent in sensitivity, graininess, and latent image stability could be provided.
[Brief description of the drawings]
FIG. 1 is a schematic view showing an example of a silver halide emulsion production apparatus applicable to the present invention.
[Explanation of symbols]
1 reaction vessel
2 Stirring mechanism
3 Dispersion media
4 Silver addition line
5 Halide addition line
6 Dispersion medium addition line
7 Additive line
8 Liquid removal line
9 Liquid return line
10 Permeate discharge line
11 Permeate return line
12 Ultrafiltration unit
13 Circulation pump
14 Flow meter
15, 16, 17 Pressure gauge
18 Pressure adjusting valve
19 Flow control valve
20 Silver addition valve
21 Halide addition valve
22 Liquid drain valve
23, 24, 25 Valve
26 Ultrafiltration permeate
27 Permeate receiver
28 scales
29, 30 Silver halide fine grain emulsion addition line
31, 32 Valve for adding fine particles

Claims (47)

A silver halide emulsion comprising silver halide grains and a dispersion medium, wherein the silver halide grains have at least a five-layer structure of a core, a first shell, a second shell, a third shell, and a fourth shell from the center. And the core ratio is 5% or more and 50% or less with respect to the total silver amount, the average silver iodide content is 0 mol% or more and 3 mol% or less, and the ratio of the first shell is all 5% to 30% with respect to the silver amount, the average silver iodide content is 3% to 10% by mole, and the ratio of the second shell is 10% to 30% with respect to the total silver amount. The average silver iodide content is 0 mol% or more and 3 mol% or less, and the ratio of the third shell is 0.5% or more and 5% or less with respect to the total silver amount, The average silver iodide content is 40 mol% or more and 100 mol% or less, and the ratio of the fourth shell is based on the total silver amount. A 40% or less is 0% or higher, and the average silver iodide content is 10 mol% or less 3 mol% or more and a silver halide emulsion which is characterized in that it is reduction sensitization. A silver halide emulsion comprising silver halide grains and a dispersion medium, wherein the silver halide grains have at least a five-layer structure of a core, a first shell, a second shell, a third shell, and a fourth shell from the center. And the core ratio is 5% or more and 50% or less with respect to the total silver amount, the average silver iodide content is 0 mol% or more and 3 mol% or less, and the ratio of the first shell is all 5% to 30% with respect to the silver amount, the average silver iodide content is 3% to 10% by mole, and the ratio of the second shell is 10% to 30% with respect to the total silver amount. The average silver iodide content is 0 mol% or more and 3 mol% or less, and the ratio of the third shell is 0.5% or more and 5% or less with respect to the total silver amount, The average silver iodide content is 40 mol% or more and 100 mol% or less, and the ratio of the fourth shell is based on the total silver amount. A 40% or less is 0% or higher, and the average silver iodide content is 10 mol% or less 3 mol% or more silver halide emulsion which is characterized by containing an oxidant Katsugin nucleus. A silver halide emulsion comprising silver halide grains and a dispersion medium, wherein the silver halide grains have at least a five-layer structure of a core, a first shell, a second shell, a third shell, and a fourth shell from the center. And the core ratio is 5% or more and 50% or less with respect to the total silver amount, the average silver iodide content is 0 mol% or more and 3 mol% or less, and the ratio of the first shell is all 5% to 30% with respect to the silver amount, the average silver iodide content is 3% to 10% by mole, and the ratio of the second shell is 10% to 30% with respect to the total silver amount. The average silver iodide content is 0 mol% or more and 3 mol% or less, and the ratio of the third shell is 0.5% or more and 5% or less with respect to the total silver amount, The average silver iodide content is 40 mol% or more and 100 mol% or less, and the ratio of the fourth shell is based on the total silver amount. 0 to 40%, the average silver iodide content is 3 to 10 mol%, and contains at least one 6-coordinate cyano complex of a polyvalent metal Silver halide emulsion. A silver halide emulsion comprising silver halide grains and a dispersion medium, wherein the silver halide grains have at least a five-layer structure of a core, a first shell, a second shell, a third shell, and a fourth shell from the center. And the core ratio is 5% or more and 50% or less with respect to the total silver amount, the average silver iodide content is 0 mol% or more and 3 mol% or less, and the ratio of the first shell is all 5% to 30% with respect to the silver amount, the average silver iodide content is 3% to 10% by mole, and the ratio of the second shell is 10% to 30% with respect to the total silver amount. The average silver iodide content is 0 mol% or more and 3 mol% or less, and the ratio of the third shell is 0.5% or more and 5% or less with respect to the total silver amount, The average silver iodide content is 40 mol% or more and 100 mol% or less, and the ratio of the fourth shell is based on the total silver amount. Silver halide fine grains having an average silver iodide content of 3% to 10% by mole and containing at least one polyvalent metal compound have been added. A silver halide emulsion characterized by A silver halide emulsion comprising silver halide grains and a dispersion medium, wherein the silver halide grains have at least a five-layer structure of a core, a first shell, a second shell, a third shell, and a fourth shell from the center. And the core ratio is 5% or more and 50% or less with respect to the total silver amount, the average silver iodide content is 0 mol% or more and 3 mol% or less, and the ratio of the first shell is all 5% to 30% with respect to the silver amount, the average silver iodide content is 3% to 10% by mole, and the ratio of the second shell is 10% to 30% with respect to the total silver amount. The average silver iodide content is 0 mol% or more and 3 mol% or less, and the ratio of the third shell is 0.5% or more and 5% or less with respect to the total silver amount, The average silver iodide content is 40 mol% or more and 100 mol% or less, and the ratio of the fourth shell is based on the total silver amount. The average silver iodide content is 0% or more and 40% or less, and the silver halide grains contained in the silver halide emulsion use an intergranular distance control method. A silver halide emulsion characterized by being formed into grains. A silver halide emulsion comprising silver halide grains and a dispersion medium, wherein the silver halide grains have at least a five-layer structure of a core, a first shell, a second shell, a third shell, and a fourth shell from the center. And the core ratio is 5% or more and 50% or less with respect to the total silver amount, the average silver iodide content is 0 mol% or more and 3 mol% or less, and the ratio of the first shell is all 5% to 30% with respect to the silver amount, the average silver iodide content is 3% to 10% by mole, and the ratio of the second shell is 10% to 30% with respect to the total silver amount. The average silver iodide content is 0 mol% or more and 3 mol% or less, and the ratio of the third shell is 0.5% or more and 5% or less with respect to the total silver amount, The average silver iodide content is 40 mol% or more and 100 mol% or less, and the ratio of the fourth shell is based on the total silver amount. 0 to 40%, the average silver iodide content is 3 to 10 mol%, and the silver halide grains contained in the silver halide emulsion have silver halide protrusions on the grain surface. A silver halide emulsion characterized by having a product. A silver halide emulsion comprising silver halide grains and a dispersion medium, wherein the silver halide grains have at least a five-layer structure of a core, a first shell, a second shell, a third shell, and a fourth shell from the center. And the core ratio is 5% or more and 50% or less with respect to the total silver amount, the average silver iodide content is 0 mol% or more and 3 mol% or less, and the ratio of the first shell is all 5% to 30% with respect to the silver amount, the average silver iodide content is 3% to 10% by mole, and the ratio of the second shell is 10% to 30% with respect to the total silver amount. The average silver iodide content is 0 mol% or more and 3 mol% or less, and the ratio of the third shell is 0.5% or more and 5% or less with respect to the total silver amount, The average silver iodide content is 40 mol% or more and 100 mol% or less, and the ratio of the fourth shell is based on the total silver amount. 0 to 40%, the average silver iodide content is 3 to 10 mol%, and the silver halide grains contained in the silver halide emulsion contain silver chloride. Characteristic silver halide emulsion. A silver halide emulsion comprising silver halide grains and a dispersion medium, wherein the silver halide grains have at least a five-layer structure of a core, a first shell, a second shell, a third shell, and a fourth shell from the center. And the core ratio is 5% or more and 50% or less with respect to the total silver amount, the average silver iodide content is 0 mol% or more and 3 mol% or less, and the ratio of the first shell is all 5% to 30% with respect to the silver amount, the average silver iodide content is 3% to 10% by mole, and the ratio of the second shell is 10% to 30% with respect to the total silver amount. The average silver iodide content is 0 mol% or more and 3 mol% or less, and the ratio of the third shell is 0.5% or more and 5% or less with respect to the total silver amount, The average silver iodide content is 40 mol% or more and 100 mol% or less, and the ratio of the fourth shell is based on the total silver amount. Dispersion medium used for grain formation of silver halide grains contained in the silver halide emulsion having an average silver iodide content of 0% to 40% and an average silver iodide content of 3% to 10% by mole A silver halide emulsion characterized in that 10% by mass or more of them is chemically modified gelatin substituted with amino groups. A silver halide emulsion comprising silver halide grains and a dispersion medium, wherein the silver halide grains are at least from the central part of the core, the first shell, the second shell, the third shell, the fourth shell, and the fifth shell. The first shell has a six-layer structure, the core ratio is not less than 5% and not more than 50%, and the average silver iodide content is not less than 0% by mole and not more than 3% by mole. Of the total silver amount is 5% to 30%, the average silver iodide content is 3% to 20% by mole, and the ratio of the second shell is to the total silver amount. 10% or more and 30% or less, the average silver iodide content is 0 mol% or more and 3 mol% or less, and the ratio of the third shell is 0.5% or more and 5% or less with respect to the total silver amount. The average silver iodide content is not less than 40 mol% and not more than 100 mol%, and the ratio of the fourth shell is all The average silver iodide content is 3% to 10% by mole, and the ratio of the fifth shell is 3% to 20% with respect to the total silver. A silver halide emulsion having an average silver iodide content of 0 mol% or more and 3 mol% or less and reduction-sensitized. A silver halide emulsion comprising silver halide grains and a dispersion medium, wherein the silver halide grains are at least from the central part of the core, the first shell, the second shell, the third shell, the fourth shell, and the fifth shell. The first shell has a six-layer structure, the core ratio is not less than 5% and not more than 50%, and the average silver iodide content is not less than 0% by mole and not more than 3% by mole. Of the total silver amount is 5% to 30%, the average silver iodide content is 3% to 20% by mole, and the ratio of the second shell is to the total silver amount. 10% or more and 30% or less, the average silver iodide content is 0 mol% or more and 3 mol% or less, and the ratio of the third shell is 0.5% or more and 5% or less with respect to the total silver amount. The average silver iodide content is not less than 40 mol% and not more than 100 mol%, and the ratio of the fourth shell is all The average silver iodide content is 3% to 10% by mole, and the ratio of the fifth shell is 3% to 20% with respect to the total silver. A silver halide emulsion having an average silver iodide content of 0 mol% or more and 3 mol% or less and containing an oxidizing agent for silver nuclei. A silver halide emulsion comprising silver halide grains and a dispersion medium, wherein the silver halide grains are at least from the central part of the core, the first shell, the second shell, the third shell, the fourth shell, and the fifth shell. The first shell has a six-layer structure, the core ratio is not less than 5% and not more than 50%, and the average silver iodide content is not less than 0% by mole and not more than 3% by mole. Of the total silver amount is 5% to 30%, the average silver iodide content is 3% to 20% by mole, and the ratio of the second shell is to the total silver amount. 10% or more and 30% or less, the average silver iodide content is 0 mol% or more and 3 mol% or less, and the ratio of the third shell is 0.5% or more and 5% or less with respect to the total silver amount. The average silver iodide content is not less than 40 mol% and not more than 100 mol%, and the ratio of the fourth shell is all The average silver iodide content is 3% to 10% by mole, and the ratio of the fifth shell is 3% to 20% with respect to the total silver. A silver halide emulsion having an average silver iodide content of 0 mol% or more and 3 mol% or less and containing a hexacoordinate cyano complex of at least one polyvalent metal . A silver halide emulsion comprising silver halide grains and a dispersion medium, wherein the silver halide grains are at least from the central part of the core, the first shell, the second shell, the third shell, the fourth shell, and the fifth shell. The first shell has a six-layer structure, the core ratio is not less than 5% and not more than 50%, and the average silver iodide content is not less than 0% by mole and not more than 3% by mole. Of the total silver amount is 5% to 30%, the average silver iodide content is 3% to 20% by mole, and the ratio of the second shell is to the total silver amount. 10% or more and 30% or less, the average silver iodide content is 0 mol% or more and 3 mol% or less, and the ratio of the third shell is 0.5% or more and 5% or less with respect to the total silver amount. The average silver iodide content is not less than 40 mol% and not more than 100 mol%, and the ratio of the fourth shell is all The average silver iodide content is 3% to 10% by mole, and the ratio of the fifth shell is 3% to 20% with respect to the total silver. A halogen having an average silver iodide content of 0 mol% or more and 3 mol% or less, and silver halide fine particles containing at least one polyvalent metal compound added thereto Silver halide emulsion. A silver halide emulsion comprising silver halide grains and a dispersion medium, wherein the silver halide grains are at least from the central part of the core, the first shell, the second shell, the third shell, the fourth shell, and the fifth shell. The first shell has a six-layer structure, the core ratio is not less than 5% and not more than 50%, and the average silver iodide content is not less than 0% by mole and not more than 3% by mole. Of the total silver amount is 5% to 30%, the average silver iodide content is 3% to 20% by mole, and the ratio of the second shell is to the total silver amount. 10% or more and 30% or less, the average silver iodide content is 0 mol% or more and 3 mol% or less, and the ratio of the third shell is 0.5% or more and 5% or less with respect to the total silver amount. The average silver iodide content is not less than 40 mol% and not more than 100 mol%, and the ratio of the fourth shell is all The average silver iodide content is 3% to 10% by mole, and the ratio of the fifth shell is 3% to 20% with respect to the total silver. And the average silver iodide content is 0 mol% or more and 3 mol% or less, and the silver halide grains contained in the silver halide emulsion are formed using the inter-grain distance control method. A silver halide emulsion characterized by that. A silver halide emulsion comprising silver halide grains and a dispersion medium, wherein the silver halide grains are at least from the central part of the core, the first shell, the second shell, the third shell, the fourth shell, and the fifth shell. The first shell has a six-layer structure, the core ratio is not less than 5% and not more than 50%, and the average silver iodide content is not less than 0% by mole and not more than 3% by mole. Of the total silver amount is 5% to 30%, the average silver iodide content is 3% to 20% by mole, and the ratio of the second shell is to the total silver amount. 10% or more and 30% or less, the average silver iodide content is 0 mol% or more and 3 mol% or less, and the ratio of the third shell is 0.5% or more and 5% or less with respect to the total silver amount. The average silver iodide content is not less than 40 mol% and not more than 100 mol%, and the ratio of the fourth shell is all The average silver iodide content is 3% to 10% by mole, and the ratio of the fifth shell is 3% to 20% with respect to the total silver. The average silver iodide content is 0 mol% or more and 3 mol% or less, and the silver halide grains contained in the silver halide emulsion have silver halide protrusions on the grain surface. Characteristic silver halide emulsion. A silver halide emulsion comprising silver halide grains and a dispersion medium, wherein the silver halide grains are at least from the central part of the core, the first shell, the second shell, the third shell, the fourth shell, and the fifth shell. The first shell has a six-layer structure, the core ratio is not less than 5% and not more than 50%, and the average silver iodide content is not less than 0% by mole and not more than 3% by mole. Of the total silver amount is 5% to 30%, the average silver iodide content is 3% to 20% by mole, and the ratio of the second shell is to the total silver amount. 10% or more and 30% or less, the average silver iodide content is 0 mol% or more and 3 mol% or less, and the ratio of the third shell is 0.5% or more and 5% or less with respect to the total silver amount. The average silver iodide content is not less than 40 mol% and not more than 100 mol%, and the ratio of the fourth shell is all The average silver iodide content is 3% to 10% by mole, and the ratio of the fifth shell is 3% to 20% with respect to the total silver. A silver halide characterized in that the average silver iodide content is 0 mol% or more and 3 mol% or less, and the silver halide grains contained in the silver halide emulsion contain silver chloride. Silver emulsion. A silver halide emulsion comprising silver halide grains and a dispersion medium, wherein the silver halide grains are at least from the central part of the core, the first shell, the second shell, the third shell, the fourth shell, and the fifth shell. The first shell has a six-layer structure, the core ratio is not less than 5% and not more than 50%, and the average silver iodide content is not less than 0% by mole and not more than 3% by mole. Of the total silver amount is 5% to 30%, the average silver iodide content is 3% to 20% by mole, and the ratio of the second shell is to the total silver amount. 10% or more and 30% or less, the average silver iodide content is 0 mol% or more and 3 mol% or less, and the ratio of the third shell is 0.5% or more and 5% or less with respect to the total silver amount. The average silver iodide content is not less than 40 mol% and not more than 100 mol%, and the ratio of the fourth shell is all The average silver iodide content is 3% to 10% by mole, and the ratio of the fifth shell is 3% to 20% with respect to the total silver. 10% by mass of a dispersion medium having an average silver iodide content of 0 mol% or more and 3 mol% or less and used for the formation of silver halide grains contained in the silver halide emulsion. A silver halide emulsion characterized by the above-mentioned chemically modified gelatin substituted with an amino group. A silver halide emulsion comprising silver halide grains and a dispersion medium, wherein the silver halide grains are arranged from the central part to a core, a first shell, a second shell, a third shell, a fourth shell, a fifth shell, It has a 6-shell at least 7-layer structure, the core ratio is 5% or more and 50% or less, and the average silver iodide content is 0 mol% or more and 3 mol% or less. The ratio of the first shell is 5% to 30% with respect to the total silver amount, the average silver iodide content is 3 mol% to 20 mol%, and the ratio of the second shell is total silver. The average silver iodide content is 10% or more and 30% or less with respect to the amount, and the ratio of the third shell is 0.5% or more with respect to the total silver amount. And the average silver iodide content is not less than 40 mol% and not more than 100 mol%. The ratio of the total silver content is 3% or more and 20% or less, the average silver iodide content is 0 mol% or more and 3 mol% or less, and the ratio of the fifth shell is based on the total silver amount. The average silver iodide content is from 10% to 40%, and the ratio of the sixth shell is 3% to 20% of the total silver amount. A silver halide emulsion having an average silver iodide content of 0 mol% or more and 3 mol% or less and reduction-sensitized. A silver halide emulsion comprising silver halide grains and a dispersion medium, wherein the silver halide grains are arranged from the central part to a core, a first shell, a second shell, a third shell, a fourth shell, a fifth shell, It has a 6-shell at least 7-layer structure, the core ratio is 5% or more and 50% or less, and the average silver iodide content is 0 mol% or more and 3 mol% or less. The ratio of the first shell is 5% to 30% with respect to the total silver amount, the average silver iodide content is 3 mol% to 20 mol%, and the ratio of the second shell is total silver. The average silver iodide content is 10% or more and 30% or less with respect to the amount, and the ratio of the third shell is 0.5% or more with respect to the total silver amount. And the average silver iodide content is not less than 40 mol% and not more than 100 mol%. The ratio of the total silver content is 3% or more and 20% or less, the average silver iodide content is 0 mol% or more and 3 mol% or less, and the ratio of the fifth shell is based on the total silver amount. The average silver iodide content is from 10% to 40%, and the ratio of the sixth shell is 3% to 20% of the total silver amount. A silver halide emulsion having an average silver iodide content of not less than 0 mol% and not more than 3 mol% and containing an oxidizing agent for silver nuclei. A silver halide emulsion comprising silver halide grains and a dispersion medium, wherein the silver halide grains are arranged from the central part to a core, a first shell, a second shell, a third shell, a fourth shell, a fifth shell, It has a 6-shell at least 7-layer structure, the core ratio is 5% or more and 50% or less, and the average silver iodide content is 0 mol% or more and 3 mol% or less. The ratio of the first shell is 5% to 30% with respect to the total silver amount, the average silver iodide content is 3 mol% to 20 mol%, and the ratio of the second shell is total silver. The average silver iodide content is 10% or more and 30% or less with respect to the amount, and the ratio of the third shell is 0.5% or more with respect to the total silver amount. And the average silver iodide content is not less than 40 mol% and not more than 100 mol%. The ratio of the total silver content is 3% or more and 20% or less, the average silver iodide content is 0 mol% or more and 3 mol% or less, and the ratio of the fifth shell is based on the total silver amount. The average silver iodide content is from 10% to 40%, and the ratio of the sixth shell is 3% to 20% of the total silver amount. A silver halide emulsion having an average silver iodide content of 0 mol% or more and 3 mol% or less and containing a 6-coordinate cyano complex of at least one polyvalent metal. A silver halide emulsion comprising silver halide grains and a dispersion medium, wherein the silver halide grains are arranged from the central part to a core, a first shell, a second shell, a third shell, a fourth shell, a fifth shell, It has a 6-shell at least 7-layer structure, the core ratio is 5% or more and 50% or less, and the average silver iodide content is 0 mol% or more and 3 mol% or less. The ratio of the first shell is 5% to 30% with respect to the total silver amount, the average silver iodide content is 3 mol% to 20 mol%, and the ratio of the second shell is total silver. The average silver iodide content is 10% or more and 30% or less with respect to the amount, and the ratio of the third shell is 0.5% or more with respect to the total silver amount. And the average silver iodide content is not less than 40 mol% and not more than 100 mol%. The ratio of the total silver content is 3% or more and 20% or less, the average silver iodide content is 0 mol% or more and 3 mol% or less, and the ratio of the fifth shell is based on the total silver amount. The average silver iodide content is from 10% to 40%, and the ratio of the sixth shell is 3% to 20% of the total silver amount. And a silver halide emulsion having an average silver iodide content of not less than 0 mol% and not more than 3 mol%, and further containing silver halide fine grains containing at least one polyvalent metal compound. . A silver halide emulsion comprising silver halide grains and a dispersion medium, wherein the silver halide grains are arranged from the central part to a core, a first shell, a second shell, a third shell, a fourth shell, a fifth shell, It has a 6-shell at least 7-layer structure, the core ratio is 5% or more and 50% or less, and the average silver iodide content is 0 mol% or more and 3 mol% or less. The ratio of the first shell is 5% to 30% with respect to the total silver amount, the average silver iodide content is 3 mol% to 20 mol%, and the ratio of the second shell is total silver. The average silver iodide content is 10% or more and 30% or less with respect to the amount, and the ratio of the third shell is 0.5% or more with respect to the total silver amount. And the average silver iodide content is not less than 40 mol% and not more than 100 mol%. The ratio of the total silver content is 3% or more and 20% or less, the average silver iodide content is 0 mol% or more and 3 mol% or less, and the ratio of the fifth shell is based on the total silver amount. The average silver iodide content is from 10% to 40%, and the ratio of the sixth shell is 3% to 20% of the total silver amount. The average silver iodide content is 0 mol% or more and 3 mol% or less, and the silver halide grains contained in the silver halide emulsion are formed using the inter-grain distance control method. A silver halide emulsion. A silver halide emulsion comprising silver halide grains and a dispersion medium, wherein the silver halide grains are arranged from the central part to a core, a first shell, a second shell, a third shell, a fourth shell, a fifth shell, It has a 6-shell at least 7-layer structure, the core ratio is 5% or more and 50% or less, and the average silver iodide content is 0 mol% or more and 3 mol% or less. The ratio of the first shell is 5% to 30% with respect to the total silver amount, the average silver iodide content is 3 mol% to 20 mol%, and the ratio of the second shell is total silver. The average silver iodide content is 10% or more and 30% or less with respect to the amount, and the ratio of the third shell is 0.5% or more with respect to the total silver amount. And the average silver iodide content is not less than 40 mol% and not more than 100 mol%. The ratio of the total silver content is 3% or more and 20% or less, the average silver iodide content is 0 mol% or more and 3 mol% or less, and the ratio of the fifth shell is based on the total silver amount. The average silver iodide content is from 10% to 40%, and the ratio of the sixth shell is 3% to 20% of the total silver amount. The average silver iodide content is 0 mol% or more and 3 mol% or less, and the silver halide grains contained in the silver halide emulsion have silver halide protrusions on the grain surface. Silver halide emulsion. A silver halide emulsion comprising silver halide grains and a dispersion medium, wherein the silver halide grains are arranged from the central part to a core, a first shell, a second shell, a third shell, a fourth shell, a fifth shell, It has a 6-shell at least 7-layer structure, the core ratio is 5% or more and 50% or less, and the average silver iodide content is 0 mol% or more and 3 mol% or less. The ratio of the first shell is 5% to 30% with respect to the total silver amount, the average silver iodide content is 3 mol% to 20 mol%, and the ratio of the second shell is total silver. The average silver iodide content is 10% or more and 30% or less with respect to the amount, and the ratio of the third shell is 0.5% or more with respect to the total silver amount. And the average silver iodide content is not less than 40 mol% and not more than 100 mol%. The ratio of the total silver content is 3% or more and 20% or less, the average silver iodide content is 0 mol% or more and 3 mol% or less, and the ratio of the fifth shell is based on the total silver amount. The average silver iodide content is from 10% to 40%, and the ratio of the sixth shell is 3% to 20% of the total silver amount. A silver halide emulsion wherein the average silver iodide content is from 0 mol% to 3 mol%, and the silver halide grains contained in the silver halide emulsion contain silver chloride. A silver halide emulsion comprising silver halide grains and a dispersion medium, wherein the silver halide grains are arranged from the central part to a core, a first shell, a second shell, a third shell, a fourth shell, a fifth shell, It has a 6-shell at least 7-layer structure, the core ratio is 5% or more and 50% or less, and the average silver iodide content is 0 mol% or more and 3 mol% or less. The ratio of the first shell is 5% to 30% with respect to the total silver amount, the average silver iodide content is 3 mol% to 20 mol%, and the ratio of the second shell is total silver. The average silver iodide content is 10% or more and 30% or less with respect to the amount, and the ratio of the third shell is 0.5% or more with respect to the total silver amount. And the average silver iodide content is not less than 40 mol% and not more than 100 mol%. The ratio of the total silver content is 3% or more and 20% or less, the average silver iodide content is 0 mol% or more and 3 mol% or less, and the ratio of the fifth shell is based on the total silver amount. The average silver iodide content is from 10% to 40%, and the ratio of the sixth shell is 3% to 20% of the total silver amount. The average silver iodide content is 0 mol% or more and 3 mol% or less, and 10% by mass or more of the dispersion medium used for the formation of silver halide grains contained in the silver halide emulsion, A silver halide emulsion characterized by being chemically modified gelatin substituted with an amino group. A silver halide emulsion comprising silver halide grains and a dispersion medium, wherein the silver halide grains are arranged from the central part to a core, a first shell, a second shell, a third shell, a fourth shell, a fifth shell, It has a 6-shell at least 7-layer structure, and the core ratio is 0.1% or more and 1% or less with respect to the total silver amount, and its average silver iodide content is 4% or more and 20% or less by mole. The ratio of the first shell is 5% or more and 50% or less with respect to the total silver amount, the average silver iodide content is 0 mol% or more and 3 mol% or less, and the ratio of the second shell is 5% to 30% of the total silver amount, the average silver iodide content is 3% to 20% by mole, and the ratio of the third shell is 10% to the total silver amount 30% or less, the average silver iodide content is 0 mol% or more and 3 mol% or less, The rate is 0.5% or more and 5% or less with respect to the total silver amount, the average silver iodide content is 40 mol% or more and 100 mol% or less, and the ratio of the fifth shell is with respect to the total silver amount. The average silver iodide content is 3 mol% or more and 10 mol% or less, and the ratio of the sixth shell is 3% or more and 20% or less with respect to the total silver amount. A silver halide emulsion having an average silver iodide content of from 0 mol% to 3 mol% and subjected to reduction sensitization. A silver halide emulsion comprising silver halide grains and a dispersion medium, wherein the silver halide grains are arranged from the central part to a core, a first shell, a second shell, a third shell, a fourth shell, a fifth shell, It has a 6-shell at least 7-layer structure, and the core ratio is 0.1% or more and 1% or less with respect to the total silver amount, and its average silver iodide content is 4% or more and 20% or less by mole. The ratio of the first shell is 5% or more and 50% or less with respect to the total silver amount, the average silver iodide content is 0 mol% or more and 3 mol% or less, and the ratio of the second shell is 5% to 30% of the total silver amount, the average silver iodide content is 3% to 20% by mole, and the ratio of the third shell is 10% to the total silver amount 30% or less, the average silver iodide content is 0 mol% or more and 3 mol% or less, The rate is 0.5% or more and 5% or less with respect to the total silver amount, the average silver iodide content is 40 mol% or more and 100 mol% or less, and the ratio of the fifth shell is with respect to the total silver amount. The average silver iodide content is 3 mol% or more and 10 mol% or less, and the ratio of the sixth shell is 3% or more and 20% or less with respect to the total silver amount. A silver halide emulsion having an average silver iodide content of 0 mol% or more and 3 mol% or less and containing an oxidizing agent for silver nuclei. A silver halide emulsion comprising silver halide grains and a dispersion medium, wherein the silver halide grains are arranged from the central part to a core, a first shell, a second shell, a third shell, a fourth shell, a fifth shell, It has a 6-shell at least 7-layer structure, and the core ratio is 0.1% or more and 1% or less with respect to the total silver amount, and its average silver iodide content is 4% or more and 20% or less by mole. The ratio of the first shell is 5% or more and 50% or less with respect to the total silver amount, the average silver iodide content is 0 mol% or more and 3 mol% or less, and the ratio of the second shell is 5% to 30% of the total silver amount, the average silver iodide content is 3% to 20% by mole, and the ratio of the third shell is 10% to the total silver amount 30% or less, the average silver iodide content is 0 mol% or more and 3 mol% or less, The rate is 0.5% or more and 5% or less with respect to the total silver amount, the average silver iodide content is 40 mol% or more and 100 mol% or less, and the ratio of the fifth shell is with respect to the total silver amount. The average silver iodide content is 3 mol% or more and 10 mol% or less, and the ratio of the sixth shell is 3% or more and 20% or less with respect to the total silver amount. A silver halide emulsion having an average silver iodide content of 0 mol% or more and 3 mol% or less and containing at least one hexacoordinate cyano complex of a polyvalent metal. A silver halide emulsion comprising silver halide grains and a dispersion medium, wherein the silver halide grains are arranged from the central part to a core, a first shell, a second shell, a third shell, a fourth shell, a fifth shell, It has a 6-shell at least 7-layer structure, and the core ratio is 0.1% or more and 1% or less with respect to the total silver amount, and its average silver iodide content is 4% or more and 20% or less by mole. The ratio of the first shell is 5% or more and 50% or less with respect to the total silver amount, the average silver iodide content is 0 mol% or more and 3 mol% or less, and the ratio of the second shell is 5% to 30% of the total silver amount, the average silver iodide content is 3% to 20% by mole, and the ratio of the third shell is 10% to the total silver amount 30% or less, the average silver iodide content is 0 mol% or more and 3 mol% or less, The rate is 0.5% or more and 5% or less with respect to the total silver amount, the average silver iodide content is 40 mol% or more and 100 mol% or less, and the ratio of the fifth shell is with respect to the total silver amount. The average silver iodide content is 3 mol% or more and 10 mol% or less, and the ratio of the sixth shell is 3% or more and 20% or less with respect to the total silver amount. A silver halide, characterized in that the average silver iodide content is 0 mol% or more and 3 mol% or less, and silver halide fine particles containing at least one polyvalent metal compound are added. emulsion. A silver halide emulsion comprising silver halide grains and a dispersion medium, wherein the silver halide grains are arranged from the central part to a core, a first shell, a second shell, a third shell, a fourth shell, a fifth shell, It has a 6-shell at least 7-layer structure, and the core ratio is 0.1% or more and 1% or less with respect to the total silver amount, and its average silver iodide content is 4% or more and 20% or less by mole. The ratio of the first shell is 5% or more and 50% or less with respect to the total silver amount, the average silver iodide content is 0 mol% or more and 3 mol% or less, and the ratio of the second shell is 5% to 30% of the total silver amount, the average silver iodide content is 3% to 20% by mole, and the ratio of the third shell is 10% to the total silver amount 30% or less, the average silver iodide content is 0 mol% or more and 3 mol% or less, The rate is 0.5% or more and 5% or less with respect to the total silver amount, the average silver iodide content is 40 mol% or more and 100 mol% or less, and the ratio of the fifth shell is with respect to the total silver amount. The average silver iodide content is 3 mol% or more and 10 mol% or less, and the ratio of the sixth shell is 3% or more and 20% or less with respect to the total silver amount. The average silver iodide content is 0 mol% or more and 3 mol% or less, and the silver halide grains contained in the silver halide emulsion are formed using the inter-grain distance control method. Characteristic silver halide emulsion. A silver halide emulsion comprising silver halide grains and a dispersion medium, wherein the silver halide grains are arranged from the central part to a core, a first shell, a second shell, a third shell, a fourth shell, a fifth shell, It has a 6-shell at least 7-layer structure, and the core ratio is 0.1% or more and 1% or less with respect to the total silver amount, and its average silver iodide content is 4% or more and 20% or less by mole. The ratio of the first shell is 5% or more and 50% or less with respect to the total silver amount, the average silver iodide content is 0 mol% or more and 3 mol% or less, and the ratio of the second shell is 5% to 30% of the total silver amount, the average silver iodide content is 3% to 20% by mole, and the ratio of the third shell is 10% to the total silver amount 30% or less, the average silver iodide content is 0 mol% or more and 3 mol% or less, The rate is 0.5% or more and 5% or less with respect to the total silver amount, the average silver iodide content is 40 mol% or more and 100 mol% or less, and the ratio of the fifth shell is with respect to the total silver amount. The average silver iodide content is 3 mol% or more and 10 mol% or less, and the ratio of the sixth shell is 3% or more and 20% or less with respect to the total silver amount. The average silver iodide content is not less than 0 mol% and not more than 3 mol%, and the silver halide grains contained in the silver halide emulsion have silver halide protrusions on the grain surface. Silver halide emulsion. A silver halide emulsion comprising silver halide grains and a dispersion medium, wherein the silver halide grains are arranged from the central part to a core, a first shell, a second shell, a third shell, a fourth shell, a fifth shell, It has a 6-shell at least 7-layer structure, and the core ratio is 0.1% or more and 1% or less with respect to the total silver amount, and its average silver iodide content is 4% or more and 20% or less by mole. The ratio of the first shell is 5% or more and 50% or less with respect to the total silver amount, the average silver iodide content is 0 mol% or more and 3 mol% or less, and the ratio of the second shell is 5% to 30% of the total silver amount, the average silver iodide content is 3% to 20% by mole, and the ratio of the third shell is 10% to the total silver amount 30% or less, the average silver iodide content is 0 mol% or more and 3 mol% or less, The rate is 0.5% or more and 5% or less with respect to the total silver amount, the average silver iodide content is 40 mol% or more and 100 mol% or less, and the ratio of the fifth shell is with respect to the total silver amount. The average silver iodide content is 3 mol% or more and 10 mol% or less, and the ratio of the sixth shell is 3% or more and 20% or less with respect to the total silver amount. A silver halide emulsion wherein the average silver iodide content is 0 mol% or more and 3 mol% or less, and the silver halide grains contained in the silver halide emulsion contain silver chloride. . A silver halide emulsion comprising silver halide grains and a dispersion medium, wherein the silver halide grains are arranged from the central part to a core, a first shell, a second shell, a third shell, a fourth shell, a fifth shell, It has a 6-shell at least 7-layer structure, and the core ratio is 0.1% or more and 1% or less with respect to the total silver amount, and its average silver iodide content is 4% or more and 20% or less by mole. The ratio of the first shell is 5% or more and 50% or less with respect to the total silver amount, the average silver iodide content is 0 mol% or more and 3 mol% or less, and the ratio of the second shell is 5% to 30% of the total silver amount, the average silver iodide content is 3% to 20% by mole, and the ratio of the third shell is 10% to the total silver amount 30% or less, the average silver iodide content is 0 mol% or more and 3 mol% or less, The rate is 0.5% or more and 5% or less with respect to the total silver amount, the average silver iodide content is 40 mol% or more and 100 mol% or less, and the ratio of the fifth shell is with respect to the total silver amount. The average silver iodide content is 3 mol% or more and 10 mol% or less, and the ratio of the sixth shell is 3% or more and 20% or less with respect to the total silver amount. The average silver iodide content is 0 mol% or more and 3 mol% or less, and 10% by mass or more of the dispersion medium used for the formation of silver halide grains contained in the silver halide emulsion. A silver halide emulsion characterized by being chemically modified gelatin substituted with an amino group. A silver halide emulsion comprising silver halide grains and a dispersion medium, wherein the silver halide grains are arranged from the center to an internal phase, a first high-iodine localized phase, an intermediate phase, and a second high-iodine localized phase. , Having at least a five-phase structure of a shell phase, the ratio of the internal phase being 5% or more and 60% or less of the grain silver amount, the average silver iodide content thereof being 0 mol% or more and 10 mol% or less, The ratio of the first and second high-iodine localized phases is 0.5% or more and 5% or less of the grain silver amount, and the average silver iodide content is higher than 40 mol% and 100 mol% or less, respectively. The phase ratio is 10% to 70% of the grain silver amount, the average silver iodide content is 0% to 10% by mole, and the shell phase ratio is 10% to 50% of the grain silver amount. The average silver iodide content is 0 mol% or more and 10 mol% or less, and the reduction sensitization is performed. The silver halide emulsion to be butterflies. A silver halide emulsion comprising silver halide grains and a dispersion medium, wherein the silver halide grains are arranged from the center to an internal phase, a first high-iodine localized phase, an intermediate phase, and a second high-iodine localized phase. , Having at least a five-phase structure of a shell phase, the ratio of the internal phase being 5% or more and 60% or less of the grain silver amount, the average silver iodide content thereof being 0 mol% or more and 10 mol% or less, The ratio of the first and second high-iodine localized phases is 0.5% or more and 5% or less of the grain silver amount, and the average silver iodide content is higher than 40 mol% and 100 mol% or less, respectively. The phase ratio is 10% to 70% of the grain silver amount, the average silver iodide content is 0% to 10% by mole, and the shell phase ratio is 10% to 50% of the grain silver amount. The average silver iodide content is not less than 0 mol% and not more than 10 mol%, and contains an oxidizing agent for silver nuclei. The silver halide emulsion according to claim. A silver halide emulsion comprising silver halide grains and a dispersion medium, wherein the silver halide grains are arranged from the center to an internal phase, a first high-iodine localized phase, an intermediate phase, and a second high-iodine localized phase. , Having at least a five-phase structure of a shell phase, the ratio of the internal phase being 5% or more and 60% or less of the grain silver amount, the average silver iodide content thereof being 0 mol% or more and 10 mol% or less, The ratio of the first and second high-iodine localized phases is 0.5% or more and 5% or less of the grain silver amount, and the average silver iodide content is higher than 40 mol% and 100 mol% or less, respectively. The phase ratio is 10% to 70% of the grain silver amount, the average silver iodide content is 0% to 10% by mole, and the shell phase ratio is 10% to 50% of the grain silver amount. The average silver iodide content is 0 mol% or more and 10 mol% or less, and at least one polyvalent metal The silver halide emulsion which is characterized by containing a hexa-coordinated cyano complex. A silver halide emulsion comprising silver halide grains and a dispersion medium, wherein the silver halide grains are arranged from the center to an internal phase, a first high-iodine localized phase, an intermediate phase, and a second high-iodine localized phase. , Having at least a five-phase structure of a shell phase, the ratio of the internal phase being 5% or more and 60% or less of the grain silver amount, the average silver iodide content thereof being 0 mol% or more and 10 mol% or less, The ratio of the first and second high-iodine localized phases is 0.5% or more and 5% or less of the grain silver amount, and the average silver iodide content is higher than 40 mol% and 100 mol% or less, respectively. The phase ratio is 10% to 70% of the grain silver amount, the average silver iodide content is 0% to 10% by mole, and the shell phase ratio is 10% to 50% of the grain silver amount. The average silver iodide content is 0 mol% or more and 10 mol% or less, and at least one polyvalent metal Silver halide emulsion characterized in that it is added to the silver halide fine particles containing compound. A silver halide emulsion comprising silver halide grains and a dispersion medium, wherein the silver halide grains are arranged from the center to an internal phase, a first high-iodine localized phase, an intermediate phase, and a second high-iodine localized phase. , Having at least a five-phase structure of a shell phase, the ratio of the internal phase being 5% or more and 60% or less of the grain silver amount, the average silver iodide content thereof being 0 mol% or more and 10 mol% or less, The ratio of the first and second high-iodine localized phases is 0.5% or more and 5% or less of the grain silver amount, and the average silver iodide content is higher than 40 mol% and 100 mol% or less, respectively. The phase ratio is 10% to 70% of the grain silver amount, the average silver iodide content is 0% to 10% by mole, and the shell phase ratio is 10% to 50% of the grain silver amount. The average silver iodide content is 0 mol% or more and 10 mol% or less, and is contained in the silver halide emulsion. The silver halide emulsion that the silver halide grains, characterized in that the particles formed using the interparticle distance control method. A silver halide emulsion comprising silver halide grains and a dispersion medium, wherein the silver halide grains are arranged from the center to an internal phase, a first high-iodine localized phase, an intermediate phase, and a second high-iodine localized phase. , Having at least a five-phase structure of a shell phase, the ratio of the internal phase being 5% or more and 60% or less of the grain silver amount, the average silver iodide content thereof being 0 mol% or more and 10 mol% or less, The ratio of the first and second high-iodine localized phases is 0.5% or more and 5% or less of the grain silver amount, and the average silver iodide content is higher than 40 mol% and 100 mol% or less, respectively. The phase ratio is 10% to 70% of the grain silver amount, the average silver iodide content is 0% to 10% by mole, and the shell phase ratio is 10% to 50% of the grain silver amount. The average silver iodide content is 0 mol% or more and 10 mol% or less, and is contained in the silver halide emulsion. That silver halide emulsions the silver halide grains and having a silver halide protrusions on the particle surface. A silver halide emulsion comprising silver halide grains and a dispersion medium, wherein the silver halide grains are arranged from the center to an internal phase, a first high-iodine localized phase, an intermediate phase, and a second high-iodine localized phase. , Having at least a five-phase structure of a shell phase, the ratio of the internal phase being 5% or more and 60% or less of the grain silver amount, the average silver iodide content thereof being 0 mol% or more and 10 mol% or less, The ratio of the first and second high-iodine localized phases is 0.5% or more and 5% or less of the grain silver amount, and the average silver iodide content is higher than 40 mol% and 100 mol% or less, respectively. The phase ratio is 10% to 70% of the grain silver amount, the average silver iodide content is 0% to 10% by mole, and the shell phase ratio is 10% to 50% of the grain silver amount. The average silver iodide content is 0 mol% or more and 10 mol% or less, and is contained in the silver halide emulsion. The silver halide emulsion that the silver halide grains, characterized in that it contains silver chloride. A silver halide emulsion comprising silver halide grains and a dispersion medium, wherein the silver halide grains are arranged from the center to an internal phase, a first high-iodine localized phase, an intermediate phase, and a second high-iodine localized phase. , Having at least a five-phase structure of a shell phase, the ratio of the internal phase being 5% or more and 60% or less of the grain silver amount, the average silver iodide content thereof being 0 mol% or more and 10 mol% or less, The ratio of the first and second high-iodine localized phases is 0.5% or more and 5% or less of the grain silver amount, and the average silver iodide content is higher than 40 mol% and 100 mol% or less, respectively. The phase ratio is 10% to 70% of the grain silver amount, the average silver iodide content is 0% to 10% by mole, and the shell phase ratio is 10% to 50% of the grain silver amount. The average silver iodide content is 0 mol% or more and 10 mol% or less, and is contained in the silver halide emulsion. That more than 10 weight percent of the silver halide dispersion medium used in grain formation of the particles, the silver halide emulsion, characterized in that an amino group substituted chemically modified gelatin. The silver halide grains have at least a five-layer structure of a core, a first shell, a second shell, a third shell, and a fourth shell from the center, and the ratio of the core is 10% or more with respect to the total silver amount. And the average silver iodide content is 0 mol% or more and 2 mol% or less, and the ratio of the first shell is 10% or more and 25% or less with respect to the total silver amount. The silver iodide content is 5 mol% or more and 10 mol% or less, the ratio of the second shell is 15% or more and 25% or less with respect to the total silver amount, and the average silver iodide content is 0 mol% or more 2 mol% or less, the ratio of the third shell is 1% or more and 3% or less with respect to the total silver amount, the average silver iodide content is 60 mol% or more and 100 mol% or less, The shell ratio is 15% or more and 30% or less with respect to the total silver amount, and the average silver iodide content is 3 mol. Set forth in any one silver halide emulsion of claims 1 to 8, characterized in that 5 mol% or less. The silver halide grains have at least a six-layer structure of a core, a first shell, a second shell, a third shell, a fourth shell, and a fifth shell from the center, and the ratio of the core to the total silver amount The average silver iodide content is 10% or more and 40% or less, and the ratio of the first shell is 10% or more and 25% or less with respect to the total silver amount. The average silver iodide content is 5 mol% or more and 15 mol% or less, the ratio of the second shell is 15% or more and 25% or less with respect to the total silver amount, and the average silver iodide content is When the ratio of the third shell is 1% or more and 3% or less with respect to the total silver amount, and the average silver iodide content is 60% or more and 100% or less by mole. And the ratio of the fourth shell is 15% or more and 30% or less with respect to the total silver amount, and the average silver iodide content is The ratio of the fifth shell is 5% or more and 10% or less of the total silver amount, and the average silver iodide content is 0% or more and 2% by mole. The silver halide emulsion according to any one of claims 9 to 16, which is as follows. The silver halide grains have at least a seven-layer structure of a core, a first shell, a second shell, a third shell, a fourth shell, a fifth shell, and a sixth shell from the center, and the ratio of the core is all silver The average silver iodide content is 10% or more and 40% or less with respect to the amount, and the ratio of the first shell is 10% or more and 25% with respect to the total silver amount. The average silver iodide content is 5 mol% or more and 15 mol% or less, the ratio of the second shell is 15% or more and 25% or less with respect to the total silver amount, The silver content is 0 mol% or more and 2 mol% or less, the ratio of the third shell is 1% or more and 3% or less with respect to the total silver amount, and the average silver iodide content is 60 mol% or more and 100 mol%. Mol% or less, and the ratio of the fourth shell is 5% or more and 10% or less of the total silver amount. The silver iodide content is 0 mol% or more and 2 mol% or less, the ratio of the fifth shell is 15% or more and 30% or less, and the average silver iodide content is 3 mol%. The ratio of the sixth shell is 5% to 10% with respect to the total silver amount, and the average silver iodide content is 0% to 2% by mole. 25. A silver halide emulsion as claimed in any one of claims 17 to 24. The silver halide grains have at least a seven-layer structure of a core, a first shell, a second shell, a third shell, a fourth shell, a fifth shell, and a sixth shell from the center, and the ratio of the core is all silver The average silver iodide content is 10% by mole or more and 15% by mole or less, and the ratio of the first shell is 10% by total silver amount. The average silver iodide content is 0 mol% or more and 2 mol% or less, and the ratio of the second shell is 10% or more and 25% or less with respect to the total silver amount, The average silver iodide content is 5 mol% or more and 15 mol% or less, the ratio of the third shell is 15% or more and 25% or less with respect to the total silver amount, and the average silver iodide content is 0 The ratio of the fourth shell is 1% or more and 3% or less with respect to the total silver amount. The average silver iodide content is 60 mol% or more and 100 mol% or less, the ratio of the fifth shell is 15% or more and 30% or less with respect to the total silver amount, and the average silver iodide content is 3 mol % To 5 mol%, the ratio of the sixth shell is 5% to 10% with respect to the total silver amount, and the average silver iodide content is 0 mol% to 2 mol% The silver halide emulsion according to any one of claims 25 to 32, wherein: 45. The silver halide emulsion according to claim 1, wherein 50% or more of the total projected area of the silver halide grains is tabular silver halide grains having an average aspect ratio of 3 or more. The tabular silver halide emulsion according to any one of claims 1 to 45, wherein 50% or more of the total projected area of the silver halide grains is a tabular silver halide emulsion having 10 or more dislocation lines per grain in the fringe portion. A silver halide emulsion as described in the item. 47. A silver halide photographic light-sensitive material comprising the silver halide emulsion according to claim 1 in at least one silver halide emulsion layer on a support.

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