JP3574989B2 - Silver halide photographic emulsion and method for producing the same - Google Patents

Description

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本発明により、高感度な写真乳剤が得られる原因は定かではないが、一つの説明として以下のような推定機構が考えられる。
【００６７】
ハロゲン化銀乳剤粒子中にドープされた本発明のハロゲン化銀への吸着基を配位子の少なくとも一つに有する金属錯体は、６配位シアノ錯体と同様に浅い電子トラップを与える。これは、電子吸引性の大きな置換基を配位子として導入することにより、遷移金属化合物のｄ軌道の配位子場分裂におけるバンドギャップが大きくなり、金属錯体の最低空軌道（ＬＵＭＯ）がハロゲン化銀の伝導体（ＣＢ）近傍に存在するようになるためである。本発明の金属錯体が、ドープされた乳剤粒子においては光電子は一時的にこの浅い電子トラップに捕獲される。
【００６８】
本発明のハロゲン化への吸着基を配位子の少なくとも一つに有する金属錯体のｄ軌道レベルは、６配位シアノ錯体とほぼ同等の位置にあるため、浅い電子トラップの機能についてはほぼ同等の機能を有することができるものと考えられる。
【００６９】
光が粒子によって吸収されると正孔と電子の対が形成され、電子は粒子の結晶構造内を自由に動き回ることができる。シアノ配位子は、配位子場分裂が大きく浅い電子トラップを与えやすく、そのため高感度乳剤を与えやすい。本発明のハロゲン化への吸着基を配位子の少なくとも一つに有する金属錯体がドープされた乳剤粒子においても、配位子の選択により浅い電子トラップの機能を付与することができるため、光電子は一時的にこの浅い電子トラップに捕獲される。本発明のように浅い電子トラップが高濃度に存在する場合には、電子が浅い電子トラップから出てきても、再び近くにある浅い電子トラップに捕獲される確率が高い。このように、光電子は浅いトラップを出たり入ったりしながら、比較的長い寿命をもつことが可能となり、これによって、銀核形成、すなわち潜像形成に寄与する確率を上げることができる。このように、潜像形成のために電子を粒子内にとどめることによって、乳剤の感度を増加させることができる。
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しかしながら、従来の吸着基を持たない金属錯体では特に臭化銀、沃臭化銀系において高ドープ率を実現することは難しく、最終的なハロゲン化銀粒子の表面に金属錯体、もしくは配位子が残存してしまい、化学熟成特に金増感が不活性になってしまい、増感レベルは十分ではないという問題があった。そこでハロゲン化への吸着基を配位子の少なくとも一つに有する金属錯体を用いることにより従来の吸着基を持たない金属錯体よりハロゲン化銀への吸着力が増し、高ドープ率が実現可能になり、従来の吸着基を持たない金属錯体より高感度化が実現できるようになったと推定される。
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ハロゲン化銀への吸着基を配位子の少なくとも一つに有する金属錯体のハロゲン化銀粒子中への添加位置は添加銀量で０〜１００％ならどの位置でも良く、好ましくは３０〜７０％が良い。
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また、ハロゲン化銀への吸着基を配位子の少なくとも一つに有する金属錯体の濃度は、好ましくは１×１０^−８〜５×１０^−４モル／銀モル、より好ましくは１×１０^−６〜５×１０^−５モル／銀モルである。
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ハロゲン化銀への吸着基を配位子の少なくとも一つに有する金属錯体のハロゲン化銀粒子中のドープ量、ドープ率については、ドープされた該錯体の中心金属を原子吸光法、ＩＣＰ法（Ｉｎｄｕｃｔｉｖｅｌｙ Ｃｏｕｐｌｅｄ Ｐｌａｓｍａ Ｓｐｅｃｔｒｏｍｅｔｒｙ； 誘導結合高周波プラズマ分光分析法）及びＩＣＰ−ＭＳ（Ｉｎｄｕｃｔｉｖｅｌｙ Ｃｏｕｐｌｅｄ Ｐｌａｓｍａ Ｍａｓｓ Ｓｐｅｃｔｒｏｍｅｔｒｙ； 誘導結合プラズマ質量分析法）等を用いることにより定量することができる。
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次に、本発明に用いるハロゲン化銀粒子について説明する。
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本発明のハロゲン化銀粒子は、臭化銀、塩化銀、沃化銀、塩臭化銀、塩沃化銀、沃臭化銀、塩沃臭化銀である。それ以外の銀塩、例えばロダン銀、硫化銀、セレン化銀、炭酸銀、リン酸銀、有機酸銀が別粒子として、あるいはハロゲン化銀粒子の一部分として含まれていても良い。現像、脱銀、（漂白、定着及び漂白定着）工程の迅速化が望まれる時には塩化銀含有量が多いハロゲン化銀粒子が望ましい。また適度に現像を抑制させる場合には沃化銀を含有することが好ましい。好ましい沃化銀含量は目的の感光材料によって異なる。例えばＸ−ｒａｙ感材では０．１〜１５モル％、グラフィックアーツ及びマイクロ感材では０．１〜５モル％が好ましい範囲である。カラーネガに代表される撮影感材の場合には好ましくは、１〜３０％の沃化銀を含むハロゲン化銀粒子であり、更に好ましくは５〜２０モル％、特に好ましくは８〜１５モル％である。沃臭化銀粒子に塩化銀を含有させるのは格子ひずみを緩和させる上で好ましい。
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本発明のハロゲン化銀粒子は特公昭４３−１３１６２号、特開昭６１−２１５５４０号、同６０−２２２８４５号、同６０−１４３３３１号、同６１−７５３３７号などに開示されているような粒子の内部と表層が異なるハロゲン組成を有するコア−シェル型あるいは二重構造型の粒子であることが好ましい。また単なる二重構造でなく、特開昭６０−２２２８４４号に開示されているような三重構造、あるいはそれ以上の多層構造にすることや、コア−シェルの二重構造の粒子の表面に異なる組成を有するハロゲン化銀を薄くつけたりすることができる。
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２つ以上のハロゲン化銀が混晶として、あるいは構造をもって存在するハロゲン化銀の場合に粒子間のハロゲン組成分布を制御することが重要である。粒子間のハロゲン組成分布の測定法に関しては特開昭６０−２５４０３２号に記載されている。粒子間のハロゲン分布が均一であることは望ましい特性である。特に変動係数２０％以下の均一性の高い乳剤は好ましい。別の好ましい形態は粒子サイズとハロゲン組成に相関がある乳剤である。例として大サイズ粒子ほどヨード含量が高く、一方、小サイズほどヨード含量が低いような相関がある場合である。目的により逆の相関、他のハロゲン組成での相関を選ぶことができる。この目的のために組成の異なる２つ以上の乳剤を混合させることが好ましい。
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ハロゲン化銀粒子の表面近傍のハロゲン組成を制御することは重要である。表面近傍の沃化銀含量を高くする、あるいは塩化銀含量を高くすることは、色素の吸着性や現像速度を変えるので目的に応じて選ぶことができる。表面近傍のハロゲン組成を変える場合に、粒子全体を包み込む構造でも、粒子の一部分にのみ付着させる構造のどちらも選ぶことができる。例えば（１００）面と（１１１）面からなる１４面体粒子の一方の面のみハロゲン組成を変える、あるいは平板粒子の主平面と側面の一方のハロゲン組成を変える場合である。
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本発明のハロゲン化銀粒子は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。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、Ｊｏｕｒｎａｌｏｆ 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。粒子の撮影面積の円相当直径を粒子厚みで割った値をアスペクト比と呼び、平板状粒子の形状を規定している。アスペクト比が１より大きい平板状粒子は本発明のハロゲン化銀粒子として使用できる。平板状粒子は、クリーブ著「写真の理論と実際」（Ｃｌｅｖｅ，Ｐｈｏｔｏｇｒａｐｈｙ Ｔｈｏｒｙ ａｎｄ 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，ＰｈｏｔｏｇｒａｐｈｉｃｃＳｃｉｅｎｃｅａｎｄ 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号および英国特許第２，１１２，１５７号などに記載の方法により調製することができる。平板状粒子を用いた場合、被覆力が上がること、増感色素による色増感効率が上がることなどの利点があり、先に引用した米国特許第４，４３４，２２６５号に詳しく述べられている。ハロゲン化銀乳剤に含まれるハロゲン化銀粒子を任意に５００個以上選びそれらのアスペクト比から求められる算術平均の値を平均アスペクト比として、１以上１００以下が望ましい。より好ましくは２以上２０以下であり、特に好ましくは３以上ｌ０以下である。平板状粒子の形状として三角形、六角形、円形などを選ぶことができる。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正六角形は好ましい形態である。
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平板状粒子の粒子サイズとして粒子の投影面積の円相当直径を用いることが多いが、米国特許第４，７４８，１０６号に記載されているような平均直径が０．６μｍ以下の粒子は高画質化にとって好ましい。また平板状粒子の形状として粒子厚みを０．５μｍ以下、より好ましくは０．３μｍ以下に限定するのは鮮鋭度を高める上で好ましい。さらに特開昭６３−１６３４５１号に記載されている粒子の厚みと双晶面の面間距離を規定した粒子も好ましいものである。
【００８１】
また、粒子サイズ分布の狭い単分散の平板状粒子を用いるとさらに好ましい結果が得られることがある。米国特許第４，７９７，３５４号および特開平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。これらの平板状粒子を本発明に用いることは好ましい。さらに、粒子厚みの変動係数が３０％以下の厚みの均一性が高い粒子も好ましい。
【００８２】
平板状粒子の場合には透過型の電子顕微鏡により転位線の観察が可能である。転位線を全く含まない粒子、数本の転位を含む粒子あるいは多数の転位を含む粒子を目的に応じて選ぶことは好ましい。また粒子の結晶方位の特定の方向に対して直線的に導入された転位あるいは曲った転位を選ぶこともできるし、粒子全体に渡って導入する、あるいは粒子の特定の部分にのみ導入する、例えば粒子のフリンジ部に限定して転位を導入する、などのなかから選ぶことができる。粒子のフリンジ部とは、平板状粒子の外周のことを指す。転位線の導入は平板状粒子の場合だけでなく正常晶粒子あるいはジャガイモ粒子に代表される不定型粒子の場合にも好ましい。この場合にも粒子の頂点、稜などの特定の部分に限定することは好ましい形態である。
【００８３】
本発明のハロゲン化銀粒子は欧州特許第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ってもよい。
【００８４】
粒子表面が平垣な構造が一般的であるが、意図して凹凸を形成することは場合によって好ましい。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。
【００８５】
本発明のハロゲン化銀粒子及び最終的に得られる粒子の粒子サイズは電子顕微鏡を用いた投影面積の円相当直径、投影面積と粒子厚みから算出する粒子体積の球相当直径あるいはコールターカウンター法による体積の球相当直径などにより評価できる。球相当直径として０．０５μｍ以下の超微粒子から、１０μｍを越える粗大粒子のなかから選んで用いることができる。好ましくは０．１μｍ以上３μｍ以下の粒子を感光性ハロゲン化組粒子として用いることである。
【００８６】
本発明のハロゲン化銀粒子または最終的に得られる粒子は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。サイズ分布を表わ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２５％以下、より好ましくは２０％以下、さらに好ましくは１５％以下のサイズ分布の乳剤を用いるのがよい。
【００８７】
単分散乳剤を粒子数あるいは重量で平均粒子サイズの±３０％以内に全粒子の８０％以上が入るような粒子サイズ分布と規定する場合もある。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。
【００８８】
本発明のハロゲン化銀粒子は、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 ＰｈｙｓｉｑｕｅＰｈｏｔｏｇｒａｐｈｉｑｕｅ，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用いて調製することができる。すなわち、酸性法、中性法、アンモニア法等のいずれもよく、また可溶性銀塩と可溶性ハロゲン塩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粒子の生成する液相中のｐＡｇを一定に保つ方法、すなわち、いわゆるコントロールド・タブルジェット法を用いることもできる。この方法によると、結晶形が規則的で粒子サイズが均一に近いハロゲン化銀粒子が得られる。
【００８９】
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、米国特許第４，３３４，０１２号、同第４，３０１，２４１号、同第４，１５０，９９４号は場合により好ましく、これらは種結晶として用いることができるし、成長用のハロゲン化銀として供給する場合も有効である。後者の場合粒子サイズの小さい乳剤を添加するのが好ましく、添加方法として一度に全量添加、複数回に分散して添加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。
【００９０】
ハロゲン化銀粒子のハロゲン組成の大部分あるいはごく一部分をハロゲン変換法によって変換させる方法は米国特許第３，４７７，８５２号、同第４，１４２，９００号、欧州特許第２７３，４２９号、同第２７３，４３０号、西独公開特許第３，８１９，２４１号などに開示されており、有効な粒子形成法である。より難溶性の銀塩に変換するのに可溶性ハロゲンの溶液あるいはハロゲン化銀粒子を添加することができる。ー度に変換する、複数回に分割して変換する、あるいは連続的に変換するなどの方法から選ぶことができる。
【００９１】
粒子成長を一定濃度、一定流速で可溶性銀塩とハロゲン塩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、供給するハロゲン化銀量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ハロゲン化銀を減量することも場合により好ましい。さらに溶液組成の異なる複数個の可溶性銀塩を添加する、あるいは溶液組成の異なる複数個の可溶性ハロゲン塩を添加する場合に、一方を増加させ、もう一方を減少させるような添加方式も有効な方法である。
【００９２】
可溶性銀塩と可溶性ハロゲン塩の溶液を反応させる時の混合器は米国特許第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のなかから選んで用いることができる。
【００９３】
熟成を促進する目的に対して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器中に存在せしめることが知られている。また他の熟成剤を用いることもできる。これらの熟成剤は銀およびハロゲン化物塩を添加する前に反応器中の分散媒中に全量を配合しておくことができるし、ハロゲン化物塩、銀塩または解膠剤を加えると共に反応器中に導入することもできる。別の変形態様として、熟成剤をハロゲン化銀塩および銀塩添加段階で独立して導入することもできる。
【００９４】
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。
【００９５】
本発明の乳剤の調製時に用いられる保護コロイドとして、及びその他の親水性コロイド層のバインダーとしては、ゼラチンを用いるのが有利であるが、それ以外の親水性コロイドも用いることができる。
【００９６】
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。
【００９７】
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。
【００９８】
本発明の乳剤は脱塩のために水洗し、新しく用意した保護コロイド分散に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℃〜５０℃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。凝析沈降法の場合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、ゼラチン誘導体を用いる方法などから選ぶことができる。
【００９９】
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。
【０１００】
本発明のハロゲン化銀粒子は硫黄増感、セレン増感、金増感、パラジウム増感又は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。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うめ込むタイプ、粒子表面から浅い位置にうめ込むタイプ、あるいは表面に化学増感核を作るタイプがある。本発明の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作った場合である。
【０１０１】
本発明で好ましく実施しうる化学増感の一つはカルコゲナイド増感と貴金属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，Ｍａｃｍｉ１１ａｎ，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３，７７３，０３ｌ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。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、パラジウム増感および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、（Ｒ）_２［ＰｄＸ_６］または（Ｒ）_２［ＰｄＸ_４］で表わされる。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わす。Ｘはハロゲン原子を表わし塩素、臭素または沃素原子を表わす。
【０１０２】
具体的には、例えば、Ｋ_２［ＰｄＣｌ_４］、（ＮＨ_４）_２［ＰｄＣｌ_６］、Ｎａ_２［ＰｄＣｌ_４］、（ＮＨ_４）_２［ＰｄＣｌ_４］、Ｌｉ_２［ＰｄＣｌ_４］、Ｎａ_２［ＰｄＣｌ_６］またはＫ_２［ＰｄＢｒ_４］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。
【０１０３】
硫黄増感剤として、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。
【０１０４】
本発明の乳剤は金増感を併用することが好ましい。金増感剤の好ましい量としてハロゲン化銀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。
【０１０５】
本発明のハロゲン化銀粒子に対して使用する好ましい硫黄増感剤量はハロゲン化銀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×ｌ０^−７モルである。
【０１０６】
本発明の乳剤に対して好ましい増感法としてセレン増感がある。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場合がある。
【０１０７】
本発明に用いられる写真乳剤には、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１一フェニル−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。
【０１０８】
本発明のハロゲン化銀粒子に吸着させる分光増感色素としてはメチン色素があり、従って又最終的に得られる写真乳剤も、メチン色素類その他によって分光増感されることが本発明の効果を発揮するのに好ましい。用いられる色素には、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、ベンズオキサドール核、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。
【０１０９】
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−チオキサソリジン−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。
【０１１０】
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３，７６９，３０ｌ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与、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。
【０１１１】
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。
【０１１２】
本発明の好ましい分光増感色素の添加時期ばハロゲン化銀粒子形成後、微粒子添加前である。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。更にまた米国特許第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。
【０１１３】
添加量は、ハロゲン化銀１モル当り、４×１０^−６〜８×１０^−３モルで用いることができるが、より好ましいハロゲン化銀粒子サイズ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。
【０１１４】
本発明で得られる乳剤を感光材料とする際には、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。
【０１１５】
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。
【０１１６】
本発明のハロゲン化銀乳剤は、更にいずれかの通常の方法により、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、本発明のハロゲン化銀乳剤は上層側、下層側どちらか一方に用いても良く、共に用いても良い。
【０１１７】
【実施例】
以下、実施例によって本発明を詳細に説明するが、本発明の態様はこれに限定されるものではない。以下に示す本発明の要件を満足する乳剤調製、乳剤及び写真要素の実施例を参照することにより、本発明をよりよく理解できる。
【０１１８】
感度はカブリ＋０．２の濃度を与える露光量Ｅ（Ｅは単位；ルクス・秒で表す）の逆数の対数の相対値で表す。
【０１１９】
実施例１
＜種晶乳剤−１の調製＞
以下の様にして種晶乳剤を調整した。
【０１２０】
特公昭５８−５８２８８号に記載の混合撹拌機を用いて、３５℃に調整した下記溶液Ａ１に硝酸銀水溶液（１．１６１モル）と、臭化カリウムと沃化カリウムの混合水溶液（沃化カリウム２モル％）を、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０ｍＶに保ちながら同時混合法により２分を要して添加し、核形成を行った。続いて、６０分の時間を要して液温を６０℃に上昇させ、炭酸ナトリウム水溶液でｐＨを５．０に調整した後、硝酸銀水溶液（５．９０２モル）と、臭化カリウムと沃化カリウムの混合水溶液（沃化カリウム２モル％）を、銀電位を９ｍＶに保ちながら同時混合法により、４２分を要して添加した。添加終了後４０℃に降温しながら、通常のフロキュレーション法を用いて直ちに脱塩、水洗を行った。
【０１２１】
得られた種晶乳剤は、平均球換算直径が０．２４μｍ、平均アスペクト比が４．８、ハロゲン化銀粒子の全投影面積の９０％以上が最大辺長比率（各粒子の最大辺長と最小辺長との比）が１．０〜２．０の六角状の平板状粒子からなる乳剤であった。この乳剤を種晶乳剤−１と称する。
【０１２２】

《沃化銀微粒子乳剤ＳＭＣ−１の調製》
０．０６モルの沃化カリウムを含む６．０重量％のゼラチン水溶液５ｌを激しく撹拌しながら、７．０６モルの硝酸銀水溶液と７．０６モルの沃化カリウム水溶液、各々２ｌを１０分を要して添加した。この間ｐＨは硝酸を用いて２．０に、温度は４０℃に制御した。粒子調製後に、炭酸ナトリウム水溶液を用いてｐＨを５．０に調整した。得られた沃化銀微粒子の平均球換算粒径は０．０５μｍであった。この乳剤をＳＭＣ−１とする。
【０１２３】
（比較乳剤１−１の調製）
０．１７８モル相当の種晶乳剤−１とＨＯ（ＣＨ_２ＣＨ_２Ｏ）_ｍ（ＣＨ（ＣＨ_３）ＣＨ_２Ｏ）_１９．８（ＣＨ_２ＣＨ_２Ｏ）_ｎＨ（ｍ＋ｎ＝９．７７）の１０％エタノール溶液０．５ｍｌを含む、４．５重量％の不活性ゼラチン水溶液７００ｍｌを７５℃に保ち、ｐＡｇを８．４、ｐＨを６．０に調製した後、激しく攪拌しながら同時混合法により以下の手順で粒子形成を行なった。
【０１２４】
１）２．０７７モルの硝酸銀水溶液と０．２１８モルのＳＭＣ−１、及び臭化カリウム水溶液を、ｐＡｇを８．８、ｐＨを６．０に保ちながら添加した。
【０１２５】
２）続いて溶液を６０℃に降温し、ｐＡｇを９．８に調製した。その後、０．７１モルのＳＭＣ−１を添加し、２分間熟成を行なった。（転位線の導入）。
【０１２６】
３）０．９１モルの硝酸銀水溶液と０．０７９モルのＳＭＣ−１、及び臭化カリウム水溶液を、ｐＡｇを９．８、ｐＨを５．０に保ちながら添加した。
【０１２７】
得られた乳剤は、粒径（同体積の立方体１辺長）０．６５μｍ、平均アスペクト比６．５、粒子内部からヨウ化銀含有率２／９．５／Ｘ／８．０モル％（Ｘは転位線導入位置）のハロゲン組成を有する平板状粒子からなる乳剤であった。この乳剤を電子顕微鏡で観察したところ乳剤中の粒子の全投影面積の６０％以上の粒子にフリンジ部と粒子内部双方に５本以上の転位線が観察された。表面沃化銀含有率は、１１．９モル％であった。
【０１２８】
（比較乳剤１−２の調製）
比較乳剤１−１の調製の１）工程において、添加銀量の５０％を添加した段階で、Ｋ_４［Ｆｅ（ＣＮ）_６］を水溶液で１×１０^−５モル／モルＡｇ添加した。この乳剤を比較乳剤１−２とする。
【０１２９】
（比較乳剤１−３の調製）
比較乳剤１−１の調製の１）工程において、添加銀量の５０％を添加した段階で、Ｋ_４［Ｒｕ（ＣＮ）_６］を水溶液で１×１０^−５モル／モルＡｇ添加した。この乳剤を比較乳剤１−３とする。
【０１３０】
（比較乳剤１−４の調製）
比較乳剤１−１の調製の１）工程において、添加銀量の５０％を添加した段階で、Ｋ_３［Ｉｒ（ＣＮ）_６］を水溶液で１×１０^−５モル／モルＡｇ添加した。この乳剤を比較乳剤１−４とする。
【０１３１】
（本発明の乳剤１−５、１−７〜１−１３の調製）
比較乳剤１−２の調製の工程において、Ｋ₄［Ｆｅ（ＣＮ）₆］の代わりに化合物Ｉ−１０、Ｉ−１２、Ｉ−１７、Ｉ−２１、Ｉ−２４、Ｉ−２７、Ｉ−２８、Ｉ−２９を１×１０^-5モル／モルＡｇ添加した。これらの乳剤を乳剤１−５、１−７〜１−１３とする。
【０１３２】
１−２〜１−５、１−７〜１−１３の乳剤の粒径、平均アスペクト比、ハロゲン組成、転位線、表面沃化銀含有率は１−１とほぼ同等であった。
【０１３３】
＜増感＞
次に、上記乳剤１−１〜１−５、１−７〜１−１３それぞれに、次に示す増感を施した。
【０１３４】
ハロゲン化銀０．５モルを含む乳剤を４０℃で溶融し、分光増感色素１および色素２および色素３を合計被覆率が約７０％になるように１：１：１の割合で添加した。その後、トリ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、最適に化学増感を施した後、４−ヒドロキシ−６−メチル−１，３，３ａ，７−テトラアザインデン（ＴＡＩ）、１−フェニル−５−メルカプトテトラゾール（ＰＭＴ）を添加した。
【０１３５】
【化２０】

【０１３６】
＜単層感材試料作製＞
増感が施された乳剤１−１〜１−５、１−７〜１−１３を、灰色銀ハレーション防止層で被覆した酢酸セルロースフィルム支持体にそれぞれ塗布し、この乳剤層を、界面活性剤とビス（ビニルスルホニル）メタン硬膜剤（ゼラチン総重量に対して１．７５重量％）とを含有する４．３ｇ／ｍ²ゼラチン層でオーバーコートした。乳剤塗布量は０．６４６ｇＡｇ／ｍ²であり、この層には、カプラー１、界面活性剤およびゼラチン総量１．０８ｇ／ｍ²も含有させた。このようにして、乳剤１−１〜１−５、１−７〜１−１３に対してそれぞれ単層感材試料１０１〜１０５、１０７〜１１３を得た。
【０１３７】
【化２１】

【０１３８】
＜評価＞
このようにして得られた試料１０１〜１０５、１０７〜１１３を、それぞれ白色光にて０．０１秒ウェッジ露光し、以下の処理工程に従って発色現像した後、光学濃度計（コニカ製ＰＤＡ−６５型）を用いて感度及びカブリを測定した。試料１０１の感度を１００としたときのそれぞれの相対感度、カブリ濃度を表１に示す。また、各試料のドープ率はＩＣＰ法及びＩＣＰ−ＭＳ法により求めた。
【０１３９】
ここでいうドープ率とは乳剤を溶解し、遠心分離した後にゼラチン分解酵素（アクチナーゼ）溶液でゼラチン分解し、遠心分離、純水洗浄を繰り返した後のハロゲン化銀１モルに含有する錯体量を添加量で割って１００を掛けた値である。
【０１４０】
《処理》
処理工程 処理時間 処理温度
発色現像 ２分５０秒 ３８± ０．３℃
漂 白 ４５秒 ３８± ２．０℃
定 着 １分３０秒 ３８± ２．０℃
安 定 ６０秒 ３８± ５．０℃
乾 燥 １分 ５５± ５．０℃
発色現像液、漂白液、定着液、安定液は、以下のものを使用した。
【０１４１】
発色現像液
水 ８００ｃｃ
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、水酸化カリウム又は２０％硫酸を用いてｐＨ１０．０６に調整する。
【０１４２】
漂白液
水 ７００ｃｃ
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、アンモニア水又は氷酢酸を用いてｐＨ４．４に調整する。
【０１４３】
定着液
水 ８００ｃｃ
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
アンモニア水又は氷酢酸を用いてｐＨ６．２に調整後水を加えて１リットルとする。
【０１４４】
安定液
水 ９００ｃｃ
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 ０．５ｃｃ
水を加えて１リットルとした後、アンモニア水又は５０％硫酸を用いてｐＨ８．５に調整する。
【０１４５】
【表１】

【０１４６】
表１を見ても明らかなように、ハロゲン化銀への吸着基を配位子の少なくとも一つに有する金属錯体を添加した乳剤（乳剤１−５、１−７〜１−１３）を用いた試料１０５、１０７〜１１３はドープ率が非常に高く、感度が飛躍的に向上していることがわかり、従来に無い高感度な写真乳剤を得ることができた。
【０１４７】
実施例２
（比較乳剤２−１の調製）
比較乳剤１−１の調製の１）工程において、添加銀量の５０％を添加した段階で、Ｆｅ（ＣＯ）_５を水溶液で１×１０^−５モル／モルＡｇ添加した。この乳剤を比較乳剤２−１とする。
【０１４８】
（本発明の乳剤２−２〜２−４の調製）
比較乳剤１−２の調製の工程において、Ｋ_４［Ｆｅ（ＣＮ）_６］の代わりに化合物ＩＩ−１４、Ｉ−５３、ＩＩ−６６を１×１０^−５モル／モルＡｇ添加した。これらの乳剤を乳剤２−２〜２−４とする。
【０１４９】
増感、単層感材試料作成および評価
上記乳剤２−１〜２−４について実施例１と同様に増感、単層試料作製し、試料２０１〜２０４を得た。このようにして得られた試料２０１〜２０４について、実施例１と同様に感度、カブリを測定した。実施例１で作製した試料１０１の感度を１００としたときのそれぞれの相対感度、カブリ濃度を表２に示す。また、各試料のドープ率はＩＣＰ法及びＩＣＰ−ＭＳ法により求めた。
【０１５０】
【表２】

【０１５１】
表２を見ても明らかなように、ハロゲン化銀への吸着基を配位子の少なくとも一つに有する金属錯体を添加した乳剤（乳剤２−２〜２−４）を用いた試料２０２〜２０４はドープ率が非常に高く、感度が飛躍的に向上していることがわかり、従来に無い高感度な写真乳剤を得ることができた。
【０１５２】
実施例３
（比較乳剤３−１、３−２の調製）
比較乳剤１−１の調製の１）工程において、添加銀量の５０％を消費した段階で、Ｋ_２［Ｐｄ（ＣＮ）_４］、Ｋ_２［Ｐｔ（ＣＮ）_４］を水溶液で１×１０^−５モル／モルＡｇ添加した。この乳剤を乳剤３−１、３−２とする。
【０１５３】
（本発明の乳剤３−３〜３−８の調製）
比較乳剤１−２の調製の工程において、Ｋ［Ｆｅ（ＣＮ）_６］の代わりに化合物ＩＩＩ−１４、ＩＩＩ−１６、ＩＩＩ−５３、ＩＩＩ−５５、ＩＩＩ−６６、ＩＩＩ−６８を１×１０^−５モル／モルＡｇ添加した。これらの乳剤を乳剤３−３〜３−８とする。
【０１５４】
＜増感、単層感材試料作成および評価＞
上記乳剤３−１〜３−８について実施例１と同様に増感、単層試料作製し、試料３０１〜３０８を得た。このようにして得られた試料３０１〜３０８について、実施例１と同様に感度、カブリを測定した。実施例１で作製した試料１０１の感度を１００としたときのそれぞれの相対感度、カブリ濃度を表３に示す。また、各試料のドープ率はＩＣＰ法及びＩＣＰ−ＭＳ法により求めた。
【０１５５】
【表３】

【０１５６】
表３を見ても明らかなように、ハロゲン化銀への吸着基を配位子の少なくとも一つに有する金属錯体を添加した乳剤（乳剤３−３〜３−８）を用いた試料３０３〜３０８はドープ率が非常に高く、感度が飛躍的に向上していることがわかり、従来に無い高感度な写真乳剤を得ることができた。
【０１５７】
実施例４
次に照度不軌改良の実施例を記す。
【０１５８】
（比較乳剤４−１の調製）
比較乳剤１−１の調製の１）工程において、転移線導入後、Ｋ_２ＩｒＣｌ_６を水溶液で１×１０^−７モル／モルＡｇ添加した。この乳剤を乳剤４−１とする。
【０１５９】
（本発明の乳剤４−２〜４−３の調製）
乳剤４−１の調製の工程において、Ｋ_２ＩｒＣｌ_６の代わりに化合物Ｉ−８、Ｉ−２５を１×１０^−７モル／モルＡｇ添加した。これらの乳剤を乳剤４−２〜４−３とする。
【０１６０】
＜増感、単層感材試料作成および評価＞
上記乳剤４−１〜４−３について実施例１と同様に増感、単層試料作製し、試料４０１〜４０３を得た。このようにして得られた試料４０１〜４０３について、実施例１と同様に感度、カブリを測定し、表４記載の露光時間の露光を与えた。実施例１で作製した試料１０１の感度を１００としたときのそれぞれの相対感度、カブリ濃度を表４に示す。また、各試料のドープ率はＩＣＰ法及びＩＣＰ−ＭＳ法により求めた。
【０１６１】
【表４】

【０１６２】
表４を見ても明らかなように、ハロゲン化銀への吸着基を配位子の少なくとも一つに有する金属錯体を添加した乳剤（乳剤４−２〜４−３）を用いた試料４０２〜４０３はドープ率が非常に高く、高照度、低照度不軌共に感度が飛躍的に向上していることがわかり、従来に無い照度不軌改良効果のある写真乳剤を得ることができた。
【０１６３】
実施例５
下引き層を施したトリアセチルセルロース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形成して多層カラー写真感光材料試料５０１を作製した。
【０１６４】
添加量は１ｍ^２当たりのグラム数で表す。但し、ハロゲン化銀とコロイド銀は銀の量に換算し、増感色素（ＳＤで示す）は銀１モル当たりのモル数で示した。
【０１６５】
第１層（ハレーション防止層）
黒色コロイド銀 ０．１６
ＵＶ−１ ０．３
ＣＭ−１ ０．１２３
ＣＣ−１ ０．０４４
ＯＩＬ−１ ０．１６７
ゼラチン １．３３
第２層（中間層）
ＡＳ−１ ０．１６０
ＯＩＬ−１ ０．２０
ゼラチン ０．６９
第３層（低感度赤感色性層）
沃臭化銀ａ ０．２０
沃臭化銀ｂ ０．２９
ＳＤ−６ ２．３７×１０^−５
ＳＤ−７ １．２×１０^−４
ＳＤ−８ ２．４×１０^−４
ＳＤ−９ ２．４×１０^−６
Ｃ−１ ０．３２
ＣＣ−１ ０．０３８
ＯＩＬ−２ ０．２８
ＡＳ−２ ０．００２
ゼラチン ０．７３
第４層（中感度赤感色性層）
沃臭化銀ｃ ０．１０
沃臭化銀ｄ ０．８６
ＳＤ−６ ４．５×１０^−５
ＳＤ−７ ２．３×１０^−４
ＳＤ−８ ４．５×１０^−４
Ｃ−２ ０．５２
ＣＣ−１ ０．０６
ＤＩ−１ ０．０４７
ＯＩＬ−２ ０．４６
ＡＳ−２ ０．００４
ゼラチン １．３０
第５層（高感度赤感色性層）
沃臭化銀ｃ ０．１３
沃臭化銀ｄ １．１８
ＳＤ−６ ３．０×１０^−５
ＳＤ−７ １．５×１０^−４
ＳＤ−８ ３．０×１０^−４
Ｃ−２ ０．０４７
Ｃ−３ ０．０９
ＣＣ−１ ０．０３６
ＤＩ−１ ０．０２４
ＯＩＬ−２ ０．２７
ＡＳ−２ ０．００６
ゼラチン １．２８
第６層（中間層）
ＯＩＬ−１ ０．２９
ＡＳ−１ ０．２３
ゼラチン １．００
第７層（低感度緑感色性層）
沃臭化銀ａ ０．１９
沃臭化銀ｂ ０．０６２
ＳＤ−９ ３．６×１０^−４
ＳＤ−１０ ３．６×１０^−４
カプラー２ ０．１８
ＣＭ−１ ０．０３３
ＯＩＬ−１ ０．２２
ＡＳ−２ ０．００２
ＡＳ−３ ０．０５
ゼラチン ０．６１
第８層（中間層）
ＯＩＬ−１ ０．２６
ＡＳ−１ ０．０５４
ゼラチン ０．８０
第９層（中感度緑感色性層）
沃臭化銀ｅ ０．５４
沃臭化銀ｆ ０．５４
ＳＤ−１１ ３．７×１０^−４
ＳＤ−１２ ７．４×１０^−５
ＳＤ−１３ ５．０×１０^−５
カプラー２ ０．１７
Ｍ−２ ０．３３
ＣＭ−１ ０．０２４
ＣＭ−２ ０．０２９
ＤＩ−２ ０．０２４
ＤＩ−３ ０．００５
ＯＩＬ−１ ０．７３
ＡＳ−３ ０．０３５
ＡＳ−２ ０．００３
ゼラチン １．８０
第１０層（高感度緑感色性層）
沃臭化銀ｆ １．１９
ＳＤ−１１ ４．０×１０^−４
ＳＤ−１２ ８．０×１０^−５
ＳＤ−１３ ５．０×１０^−５
カプラー２ ０．０６５
ＣＭ−２ ０．０２６
ＣＭ−１ ０．０２２
ＤＩ−３ ０．００３
ＤＩ−２ ０．００３
ＯＩＬ−１ ０．１９
ＯＩＬ−２ ０．４３
ＡＳ−３ ０．０１７
ＡＳ−２ ０．０１４
ゼラチン １．２３
第１１層（イエローフィルター層）
黄色コロイド銀 ０．０５
ＯＩＬ−１ ０．１８
ＡＳ−１ ０．１６
ゼラチン １．００
第１２層（低感度青感色性層）
沃臭化銀ｂ ０．２２
沃臭化銀ａ ０．０８
沃臭化銀ｈ ０．０９
ＳＤ−１４ ６．５×１０^−４
ＳＤ−１５ ２．５×１０^−４
カプラー１ ０．７７
ＤＩ−４ ０．０１７
ＯＩＬ−１ ０．３１
ＡＳ−２ ０．００２
ゼラチン １．２９
第１３層（高感度青感色性層）
沃臭化銀ｈ ０．４１
沃臭化銀ｉ ０．６１
ＳＤ−１４ ４．４×１０^−４
ＳＤ−１５ １．５×１０^−４
カプラー１ ０．２３
ＯＩＬ−１ ０．１０
ＡＳ−２ ０．００４
ゼラチン １．２０
第１４層（第１保護層）
沃臭化銀ｊ ０．３０
ＵＶ−１ ０．０５５
ＵＶ−２ ０．１１０
ＯＩＬ−２ ０．３０
ゼラチン １．３２
第１５層（第２保護層）
ＰＭ−１ ０．１５
ＰＭ−２ ０．０４
ＷＡＸ−１ ０．０２
Ｄ−１ ０．００１
ゼラチン ０．５５
上記沃臭化銀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）。
【０１６６】

なお、ハロゲン化銀粒子の形成例として、沃臭化銀ｄ，ｆの製造例を以下に示す。また、沃臭化銀ｊ（以下、乳剤ｊともいう）については特開平１−１８３４１７号、同１−１８３６４４号、同１−１８３６４５号、同２−１６６４４２号に関する記載を参考に作成した。
【０１６７】
《沃臭化銀ｄの調製》
０．１７８モル相当の種晶乳剤−１とＨＯ（ＣＨ_２ＣＨ_２Ｏ）_ｍ（ＣＨ（ＣＨ_３）ＣＨ_２Ｏ）_１９．８（ＣＨ_２ＣＨ_２Ｏ）_ｎＨ（ｍ＋ｎ＝９．７７）の１０％エタノール溶液０．５ｍｌを含む、４．５重量％の不活性ゼラチン水溶液７００ｍｌを７５℃に保ち、ｐＡｇを８．４、ｐＨを５．０に調整した後、激しく撹拌しながら同時混合法により以下の手順で粒子形成を行った。
【０１６８】
１） ３．０９３モルの硝酸銀水溶液と０．２８７モルのＳＭＣ−１、及び臭化カリウム水溶液を、ｐＡｇを８．４、ｐＨを５．０に保ちながら添加した。
【０１６９】
２） 続いて溶液を６０℃に降温し、ｐＡｇを９．８に調製した。その後、０．０７１モルのＳＭＣ−１を添加し、２分間熟成を行った（転位線の導入）。
【０１７０】
３） ０．９５９モルの硝酸銀水溶液と０．０３モルのＳＭＣ−１、及び臭化カリウム水溶液を、ｐＡｇを９．８、ｐＨを５．０に保ちながら添加した。
【０１７１】
尚、粒子形成を通して各溶液は、新核の生成や粒子間のオストワルド熟成が進まないように最適な速度で添加した。上記添加終了後に４０℃で通常のフロキュレーション法を用いて水洗処理を施した後、ゼラチンを加えて再分散し、ｐＡｇを８．１、ｐＨを５．８に調整した。
【０１７２】
得られた乳剤は、粒径（同体積の立方体１辺長）０．７４μｍ、平均アスペクト比５．０、粒子内部からヨウ化銀含有率２／８．５／Ｘ／３モル％（Ｘは転位線導入位置）のハロゲン組成を有する平板状粒子からなる乳剤であった。この乳剤を電子顕微鏡で観察したところ乳剤中の粒子の全投影面積の６０％以上の粒子にフリンジ部と粒子内部双方に５本以上の転位線が観察された。表面沃化銀含有率は、６．７モル％であった。
【０１７３】
《沃臭化銀ｆの調製》
沃臭化銀ｄの調製において、１）の工程でｐＡｇを８．８かつ、添加する硝酸銀量を２．０７７モルＳＭＣ−１の量を０．２１８モルとし、３）の工程で添加する硝酸銀量を０．９１モル、ＳＭＣ−１の量を０．０７９モルとした以外は沃臭化銀ｄと全く同様にして沃臭化銀ｆを調製した。
【０１７４】
得られた乳剤は、粒径（同体積の立方体１辺長）０．６５μｍ、平均アスペクト比６．５、粒子内部からヨウ化銀含有率２／９．５／Ｘ／８．０モル％（Ｘは転位線導入位置）のハロゲン組成を有する平板状粒子からなる乳剤であった。この乳剤を電子顕微鏡で観察したところ乳剤中の粒子の全投影面積の６０％以上の粒子にフリンジ部と粒子内部双方に５本以上の転位線が観察された。表面沃化銀含有率は、１１．９モル％であった。
【０１７５】
上記各乳剤に前述の増感色素を添加、熟成した後、トリ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、かぶり、感度関係が最適になるように化学増感を施した。
【０１７６】
また、沃臭化銀ａ，ｂ，ｃ，ｅ，ｈ，ｉについても、上記沃臭化銀ｄ，ｆに準じて作製し、分光増感、化学増感を施した。
【０１７７】
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、カブリ防止剤ＡＦ−１、重量平均分子量：１０，０００及び重量平均分子量：１，１００，０００の２種のポリビニルピロリドン（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。
【０１７８】
上記試料に用いた化合物の構造を以下に示す。
【０１７９】
【化２２】

【０１８０】
【化２３】

【０１８１】
【化２４】

【０１８２】
【化２５】

【０１８３】
【化２６】

【０１８４】
【化２７】

【０１８５】
【化２８】

【０１８６】
【化２９】

【０１８７】
【化３０】

【０１８８】
上記多層試料で第１０層の沃臭化銀ｆを乳剤１−９に置き換え、実施例１（但し発色現像時間は３分１５秒）と同様の評価を行なった。
【０１８９】
本実施例４のような多層カラー感光材料においても、本発明の効果は実施例１と同様に顕著であることを確認した。
【０１９０】
【発明の効果】
以上の実施例において明らかなように、本発明により高感度でかつ低カブリである乳剤及び／または照度不軌が改良された乳剤を得ることができる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a silver halide photographic emulsion and a method for producing the same, and more particularly to a method containing a metal complex, which can significantly improve the doping efficiency of silver halide grains and thereby improve sensitivity and / or illuminance failure. And a silver halide photographic emulsion.
[0002]
[Prior art]
As a commonly used dopant in a silver halide photographic emulsion and a method for producing the same, an octahedral hexacoordinate metal complex is well known. Here, "dopant" refers to a trace amount of impurities contained in silver halide crystals other than silver or halide ions. In particular, many studies have been made on metal complexes whose central metal is a transition metal (Groups 3 to 12 of the Periodic Table of the Elements) as a dopant for modifying a silver halide emulsion.
[0003]
When the reciprocity law of the photograph is satisfied (that is, when there is no reciprocity failure), the sensitivity of the photographic emulsion becomes constant irrespective of the values of the exposure intensity and the exposure time as long as the products thereof are the same.
[0004]
In the present invention, the high illuminance reciprocity failure means a phenomenon in which the sensitivity of a photographic emulsion becomes lower as the exposure time is shorter when the exposure time is different, although the exposure amount is the same. Similarly, low-illuminance reciprocity failure refers to a phenomenon in which the sensitivity of a photographic emulsion becomes lower as the exposure time is longer when the exposure times are the same but the exposure times are different.
[0005]
Research Disclosure Chapter 308119, Chapters I-D, states that during grain nucleation, metals introduced during grain growth enter the grains as dopants and alter photographic performance depending on their level and location within the grains. It is stated that it can be done.
[0006]
It is known that there is a remarkable difference in the photographic effect of the transition metal compound in the silver halide emulsion between the case where the transition metal compound is added during the formation of the silver halide grains and the case where the transition metal compound is added after the precipitation of the silver halide grains. ing. In the former case, it is generally known that the transition metal compound is incorporated as a dopant into the silver halide grains, and that the amount is very small, but effectively changes the photographic performance. In the latter case, the transition metal compound is adsorbed on the particle surface, but often cannot interact with the particle due to the interaction with the peptizer. In order to obtain the same effect as when the transition metal compound is incorporated inside the silver halide grains by adding the transition metal compound after grain formation, it is necessary to add a higher concentration of the transition metal compound.
[0007]
The technical difference between the metal doping added to the emulsion during the formation of the silver halide grains and the metal sensitizer by adding a transition metal compound to the emulsion after the formation of the silver halide grains is discussed in The transition metal compound introduced into the compound is described in Research Disclosure No. 17643, Chapter IA, and the transition metal compound introduced during chemical sensitization is described in Chapter IIIA of the Research Disclosure.
[0008]
U.S. Pat. No. 4,126,472 discloses that 10 moles per mole of silver halide is used.^-6From 10^-4It discloses that a silver halide emulsion is ripened in the presence of moles of a water-soluble iridium salt, and iridium is used as a grain surface modifier. However, there is no description of a metal complex having at least one ligand having an adsorptive group to silver halide.
[0009]
EP 242190 discloses a halide comprising silver halide grains formed in the presence of one or more complex compounds of trivalent rhodium having 3, 4, 5 or 6 cyanide ligands. Reduction of high intensity failure in silver emulsions is disclosed.
[0010]
U.S. Pat. No. 3,690,888 discloses a process for producing silver halide containing polyvalent metal ions, which comprises the step of producing silver halide grains in the presence of a peptizer consisting mainly of an acrylic polymer. Have been. As the polyvalent metal ion, bismuth, iridium, lead, and / or osmium ion are particularly mentioned, but there is no description about a metal complex having an adsorbing group to silver halide on at least one of the ligands.
[0011]
In these disclosures, it is clearly shown that the ligand is incorporated into the particles together with the transition metal, and the regulation and the effect are not described in the ligand of the transition metal compound.
[0012]
On the other hand, U.S. Patent Nos. 4,835,093, 4,933,272, 4,981,781, 5,037,732, 4,937,180, and 4,945,035 It has been demonstrated that ligands that can form a coordination complex with metal ions can enter the grain crystal structure and can improve photographic performance that cannot be achieved by incorporating transition metal ions alone. ing.
[0013]
European Patents 336,425 and 336,426, JP-A-2-20853 and JP-A-2-20854 disclose six-coordinate rhenium, ruthenium, osmium and iridium metal complexes having at least four cyano ligands. Describes a silver halide emulsion prepared in the presence of a silver halide emulsion, which has excellent sensitivity, gradation, and stability over time, and has improved low light failure.
[0014]
Also, EP-A-336,427 and JP-A-2-20852 disclose that a six-coordinate vanadium, chromium, manganese, iron, ruthenium, osmium, rhenium and iridium metal complex containing a nitrosyl or thionitrosyl ligand is used. A silver halide emulsion having improved low-light reciprocity failure without lowering the light sensitivity is described.
[0015]
Furthermore, in European Patent 336,689 and JP-A-2-20855, sensitivity of a ligand of a hexacoordinate rhenium complex is increased by a metal complex in which halogen, nitrosyl, thionitrosyl, cyan, water and thiocyan are combined. Emulsions that are controlled and have improved low light reciprocity failure are disclosed.
[0016]
JP-A-3-118535 discloses a transition metal complex in which one ligand of a six-coordinate metal complex is carbonyl, and JP-A-3-118536 discloses that two ligands of a six-coordinate metal complex are oxygen. It is disclosed that an emulsion containing a transition metal complex therein is effective for photographic performance.
[0017]
U.S. Pat. No. 5,132,203 discloses a plate containing a hexacoordinate group VIII metal complex having at least four cyanide ligands on the subsurface and a particle surface layer of 20 to 350 DEG which does not contain the complex. It is disclosed that the particulate particles are highly sensitive. Further, EP 508,910 discloses a halogen which is doped with a hexacyanoiron complex on a subsurface and has a surface layer at 20 to 350 ° which does not contain the iron complex and which is sensitized by adding a sensitizing dye. Silver halide emulsions are disclosed. These patents teach that the hexacyano complex is more sensitive when present near the particle surface, but better not to be present near the particle surface. That is, when doping the hexacoordinated cyano metal complex into the grains, the doping position is preferably on the subsurface of the silver halide grains, but when the complex is present on the surface itself, a method for obtaining high sensitivity is completely disclosed. Not.
[0018]
Cyan generated by the interaction between the six-coordinate cyano metal complex and gelatin forms a stable gold cyanide complex with gold ions and is stably present in the emulsion medium. For this reason, it is difficult for gold ions to be adsorbed on the surface of the grains, and the photographic effect due to chemical sensitization is reduced. Therefore, hexacoordinate cyano metal complexes have been doped on the subsurface of silver halide grains. , Sufficient sensitivity could not be obtained. JP-A-6-242537 discloses that in a step of doping a silver halide with a six-coordinate cyano metal complex, a part or all of the dope is adjusted to have a pH value of 7.0 or more so that the complex may have a pH of 7.0 or more. While maximizing its effect while allowing the particles to be present on the particle surface. JP-A-6-289512 discloses a process in which a silver halide is doped with a 6-coordinate cyano metal complex, and thereafter, an amino group or a carboxyl group is nullified (for example, phthalated gelatin, esterified gelatin). Or a method for obtaining high sensitivity by the presence of oxidized gelatin. JP-A-8-29905 discloses that silver halide grains form particles in the presence of a compound which inhibits the reaction between gelatin and cyano complex, for example, salts of zinc, cesium, copper, lead, calcium, barium, or magnesium. To obtain high sensitivity.
[0019]
However, even these methods are not sufficient, and in these disclosed examples, by changing the metal complex to a metal complex having an adsorbing group to silver halide in at least one of the ligands, There is no mention of a method of obtaining high sensitivity by doping a metal compound inside.
[0020]
[Problems to be solved by the invention]
SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide photograph having high sensitivity and low fog and / or improved illuminance failure by doping a metal complex having an adsorbing group on at least one of the ligands into silver halide grains. An object of the present invention is to provide an emulsion and a method for producing the emulsion.
[0021]
[Means for Solving the Problems]
The above object of the present invention has been achieved by the following constitutions.
[0022]
1. At least one of the ligands has an adsorptive group to silver halide at a position of 30 to 70% of the added silver amount for forming silver halide grains, and the central metal is manganese or iron., LeTenium, Paradium,IA method for producing a silver halide photographic emulsion, comprising using a metal complex selected from iridium and platinum. However, a metal complex in which the central metal is Ru and the ligand has an imidazole nucleus is excluded.
[0023]
2.The above-mentioned 1., wherein the metal complex is a metal complex represented by the following general formula (I). The method for producing a silver halide photographic emulsion described in 1 above.
Formula (I) [A _n -MX _(6-n) ] Z
[In the formula, A represents an atom group containing a group adsorbable to silver halide, M represents a central metal, X represents a ligand, n represents an integer of 1 to 6, and when n is 2 or more, Each A may be the same or different, and when (6-n) is 2 or more, each X may be the same or different. Z represents a counter ion necessary for neutralizing the charge of the complex. ]
[0024]
3.The metal complex is represented by the following general formula ( II Wherein the metal complex represented by (1) is used. The method for producing a silver halide photographic emulsion described in 1 above.
The general formula ( II ) [A _n -MX _(5-n) ] Z
[In the formula, A represents an atom group containing a group that can be adsorbed to silver halide, M represents a central metal, X represents a ligand, n represents an integer of 1 to 5, and when n is 2 or more, Each A may be the same or different, and when (5-n) is 2 or more, each X may be the same or different. Z represents a counter ion necessary for neutralizing the charge of the complex. ]
[0025]
4. The metal complex is represented by the following general formula ( III Wherein the metal complex is represented by the formula (1): The method for producing a silver halide photographic emulsion described in 1 above.
The general formula ( III ) [A _n -MX _(4-n) ] Z
[In the formula, A represents an atom group containing a group capable of being adsorbed to silver halide, M represents a central metal, X represents a ligand, n represents an integer of 1 to 4, and when n is 2 or more, Each A may be the same or different, and when (4-n) is 2 or more, each X may be the same or different. Z represents a counter ion necessary for neutralizing the charge of the complex. ]
[0026]
5. 1. ~ 4. 5. A silver halide photographic emulsion produced by the production method according to any one of the above.
[0036]
Hereinafter, the present invention will be described in detail.
[0037]
Specific examples of the metal complex compound having a silver halide adsorption group as one of the ligands used in the present invention include compounds represented by the following general formulas (I) to (III).
[0038]
Formula (I) [A_n-MX_(6-n)] Z
In the formula, A represents an atom group containing a group capable of being adsorbed to silver halide, M represents a central metal, X represents a ligand, n represents an integer of 1 to 6, and when n is 2 or more, A may be the same or different, and when (6-n) is 2 or more, each X may be the same or different. Z represents a counter ion necessary for neutralizing the charge of the complex.
[0039]
Formula (II) [A_n-MX_(5-n)] Z
In the formula, A represents an atom group containing a group capable of being adsorbed to silver halide, M represents a central metal, X represents a ligand, n represents an integer of 1 to 5, and when n is 2 or more, A may be the same or different, and when (5-n) is 2 or more, each X may be the same or different. Z represents a counter ion necessary for neutralizing the charge of the complex.
[0040]
General formula (III) [A_n-MX_(4-n)] Z
In the formula, A represents an atom group containing a group capable of being adsorbed to silver halide, M represents a central metal, X represents a ligand, n represents an integer of 1 to 4, and when n is 2 or more, A may be the same or different, and when (4-n) is 2 or more, each X may be the same or different. Z represents a counter ion necessary for neutralizing the charge of the complex.
[0041]
Next, the general formulas (I) to (III) will be described in detail.
[0042]
In the formula, an atom group having a group capable of adsorbing to silver halide in A is an atom group having a mercapto group (for example, mercaptooxadiazole, mercaptotetrazole, mercaptotriazole, mercaptodiazole, mercaptothiazole, mercaptothiadiazole, mercaptooxazole , A mercaptoimidazole, a mercaptobenzothiazole, a mercaptobenzoxazole, a mercaptobenzimidazole, a mercaptotetrazaindene, a mercaptopyridyl, a mercaptoquinolyl, a 2-mercaptopyridyl, a mercaptophenyl, a mercaptonaphthyl, etc.), an atomic group having a thione group (For example, thiazoline-2-thione, oxazoline-2-thione, imidazoline-2-thione, benzothiazoline-2-thione, benzimidazo Groups that form imino silver (eg, groups such as triazole, tetrazole, benzotriazole, hydroxyazaindene, benzimidazole, indazole, etc.), and an ethynyl group (For example, respective groups such as 2- [N- (2-propynyl) amino] benzothiazole and N- (2-propynyl) carbazole).
[0043]
In the formula, the central metal of M is manganese, iron, LeTenium, Paradium,ISelected from iridium and platinum, more preferably iron, LeTenium, AndAnd iridium.
[0044]
In the formula, the ligand of X may be a neutral ligand such as carbonyl, aqua, amine, triphenylphosphine, or a halide, cyano, nitro, hydride, sulfide, amide, azide, cyanato, thiocyanate. And an anionic ligand such as
[0045]
In the formula, Z represents a necessary counter ion depending on the valence of the complex. The cation may be a hydrogen atom or an alkali metal such as sodium or potassium, or an alkaline earth metal such as calcium, and the anion may be a halogen such as chlorine or bromine. Atoms are preferred.
[0046]
Hereinafter, typical specific examples of the metal complex having an adsorptive group to silver halide used in the present invention as at least one of the ligands will be shown.
[0047]
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[0048]
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[0049]
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[0050]
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[0051]
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[0052]
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[0053]
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[0054]
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[0055]
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[0056]
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[0057]
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[0058]
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[0059]
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[0060]
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[0061]
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[0062]
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[0063]
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[0064]
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[0065]
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[0066]
The reason why a high-sensitivity photographic emulsion can be obtained by the present invention is not clear, but as one explanation, the following estimation mechanism can be considered.
[0067]
The metal complex having at least one of the ligands of the present invention, which is adsorbed on silver halide and doped in silver halide emulsion grains, provides a shallow electron trap similarly to the hexacoordinate cyano complex. This is because by introducing a substituent having a large electron-withdrawing property as a ligand, the band gap in the ligand field splitting of the d-orbital of the transition metal compound becomes large, and the lowest unoccupied orbital (LUMO) of the metal complex becomes halogen. This is because it is present near the silver halide conductor (CB). In emulsion grains doped with the metal complex of the present invention, photoelectrons are temporarily captured by this shallow electron trap.
[0068]
Since the d-orbital level of the metal complex having an adsorptive group for halogenation in at least one of the ligands of the present invention is located at a position substantially equal to that of the six-coordinate cyano complex, the function of the shallow electron trap is substantially equal. It is considered that the function can be provided.
[0069]
When light is absorbed by the particles, pairs of holes and electrons are formed, and the electrons can move freely within the crystal structure of the particles. Cyano ligands tend to provide shallow electron traps with large ligand field splitting, and therefore high sensitivity emulsions. Even in emulsion grains doped with a metal complex having an adsorbing group for halogenation in at least one of the ligands of the present invention, a function of a shallow electron trap can be imparted by the selection of the ligand. Is temporarily captured by this shallow electron trap. When a shallow electron trap exists at a high concentration as in the present invention, even if an electron comes out of the shallow electron trap, there is a high probability that the electron will be captured again by a nearby shallow electron trap. In this way, photoelectrons can have a relatively long lifetime while entering and exiting a shallow trap, thereby increasing the probability of contributing to silver nucleation, ie, latent image formation. Thus, by keeping the electrons within the grains for latent image formation, the sensitivity of the emulsion can be increased.
[0070]
However, it is difficult to achieve a high doping rate especially in a silver bromide or silver iodobromide system with a conventional metal complex having no adsorptive group, and the metal complex or ligand is finally formed on the surface of silver halide grains. Remain, and the chemical ripening, particularly gold sensitization, becomes inactive, and the sensitization level is not sufficient. Thus, by using a metal complex having an adsorbing group for at least one of the ligands for the halogenation, the adsorbing power to silver halide is increased and a high doping ratio can be realized compared to a conventional metal complex having no adsorbing group. It is presumed that higher sensitivity can be realized than the conventional metal complex having no adsorptive group.
[0071]
The metal complex having an adsorbing group to silver halide on at least one of the ligands may be added to the silver halide grains at any position as long as the amount of added silver is 0 to 100%, preferably 30 to 70%. Is good.
[0072]
The concentration of the metal complex having at least one ligand having an adsorptive group to silver halide is preferably 1 × 10 5^-8~ 5 × 10^-4Mole / silver mole, more preferably 1 × 10^-6~ 5 × 10^-5Mole / silver mole.
[0073]
With respect to the doping amount and doping ratio of a metal complex having an adsorbing group to silver halide on at least one of the ligands in silver halide grains, the central metal of the doped complex is determined by an atomic absorption method or an ICP method ( Inductively coupled plasma mass spectrometry (ICP-MS) and inductively coupled plasma mass spectrometry (ICP-MS) can be used.
[0074]
Next, the silver halide grains used in the present invention will be described.
[0075]
The silver halide grains of the present invention are silver bromide, silver chloride, silver iodide, silver chlorobromide, silver chloroiodide, silver bromoiodide, and silver chloroiodobromide. Other silver salts, such as silver rhodan, silver sulfide, silver selenide, silver carbonate, silver phosphate, and organic acid silver, may be contained as separate grains or as part of silver halide grains. When rapid development, desilvering and (bleaching, fixing and bleach-fixing) steps are desired, silver halide grains having a high silver chloride content are desirable. In order to appropriately suppress development, it is preferable to contain silver iodide. The preferred silver iodide content depends on the intended light-sensitive material. For example, the preferred range is 0.1 to 15 mol% for X-ray photographic materials and 0.1 to 5 mol% for graphic arts and micro photographic materials. In the case of a photographic light-sensitive material represented by a color negative, silver halide grains containing 1 to 30% of silver iodide are preferred, more preferably 5 to 20% by mole, particularly preferably 8 to 15% by mole. is there. It is preferred that silver iodobromide grains contain silver chloride in order to reduce lattice strain.
[0076]
The silver halide grains of the present invention can be prepared from grains such as those disclosed in JP-B-43-13162, JP-A-61-215540, JP-A-60-222845, JP-A-60-143331, JP-A-61-75337 and the like. Core-shell or double structure type grains having different halogen compositions in the interior and the surface are preferred. In addition to a mere double structure, a triple structure as disclosed in JP-A-60-222844, or a multilayer structure of more than that, or a different composition on the surface of a core-shell double structure particle Or a thin silver halide having the formula:
[0077]
In the case of silver halides in which two or more silver halides exist as mixed crystals or with a structure, it is important to control the halogen composition distribution between grains. A method for measuring the halogen composition distribution between grains is described in JP-A-60-254032. Uniform halogen distribution between grains is a desirable property. In particular, a highly uniform emulsion having a coefficient of variation of 20% or less is preferable. Another preferred form is an emulsion having a correlation between grain size and halogen composition. As an example, there is a case where the correlation is such that the iodine content increases as the size of the particles increases, while the iodine content decreases as the size of the particles decreases. Depending on the purpose, an inverse correlation or a correlation with another halogen composition can be selected. For this purpose, it is preferable to mix two or more emulsions having different compositions.
[0078]
It is important to control the halogen composition near the surface of the silver halide grains. Increasing the silver iodide content near the surface or increasing the silver chloride content can be selected depending on the purpose because the dye adsorption property and the developing speed are changed. When changing the halogen composition in the vicinity of the surface, either a structure that wraps the entire grain or a structure that adheres only to a part of the grain can be selected. For example, this is a case where the halogen composition is changed only on one side of the tetrahedral grain composed of the (100) plane and the (111) plane, or one of the main plane and the side face of the tabular grain is changed.
[0079]
The silver halide grains of the present invention may be normal crystals containing no twin planes, edited by the Photographic Society of Japan, the basics of the photographic industry, silver salt photography (Corona Co., Ltd.). 163, such as a single twin with one twin plane, a parallel multiple twin with two or more parallel twin planes, a non-parallel with two or more non-parallel twin planes It can be selected from multiple twins or the like depending on the purpose. An example of mixing particles having different shapes is disclosed in U.S. Pat. No. 4,865,964, but this method can be selected as necessary. In the case of a normal crystal, a cube having a (100) plane, an octahedron having a (111) plane, a dodecahedron having a (110) plane disclosed in Japanese Patent Publication No. 55-42737 and Japanese Patent Application Laid-Open No. 60-222842. Particles can be used. Furthermore, (hll) plane particles represented by (211), (hll) plane particles represented by (331), and (210), as reported in Journalof Imaging Science, Vol. 30, p. 247, 1986. The (hk0) -plane particles representing the plane and the (hkl) -plane particles representing the (321) plane also require some contrivance in the preparation method, but they can be selected and used according to the purpose. Particles having two or many coexisting surfaces, such as tetradecahedral particles having (100) and (111) surfaces coexisting in one particle, and particles having (100) and (110) coexisting surfaces, may also be used depending on the purpose. You can use it by choosing. The value obtained by dividing the circle equivalent diameter of the imaging area of the particle by the particle thickness is called an aspect ratio, and defines the shape of the tabular particle. Tabular grains having an aspect ratio of greater than 1 can be used as the silver halide grains of the present invention. Tabular grains are described in Cleeve, "Theory and Practice of Photography" (Cleve, Photographic Thory and Practice (1930)), p. 131; Gatov, Photographic Science and Engineering (Gutoff, Photographic Science, Volume 14, Eng. Eng. 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. When tabular grains are used, there are advantages such as an increase in covering power and an increase in the efficiency of color sensitization by a sensitizing dye, which is described in detail in U.S. Pat. No. 4,434,2265 cited above. . The number of silver halide grains contained in the silver halide emulsion is arbitrarily selected from 500 or more, and the value of the arithmetic average obtained from the aspect ratio thereof is preferably from 1 to 100 as an average aspect ratio. It is more preferably 2 or more and 20 or less, and particularly preferably 3 or more and 10 or less. The shape of the tabular grains can be selected from triangles, hexagons, and circles. A regular hexagon having substantially equal lengths of six sides as described in U.S. Pat. No. 4,797,354 is a preferred form.
[0080]
Although the equivalent circle diameter of the projected area of the grains is often used as the grain size of the tabular grains, grains having an average diameter of 0.6 μm or less as described in US Pat. No. 4,748,106 have high image quality. Is preferred for Further, it is preferable to limit the thickness of the tabular grains to 0.5 μm or less, more preferably 0.3 μm or less, from the viewpoint of enhancing sharpness. Further, particles described in JP-A-63-163451 in which the thickness of the particles and the distance between twin planes are specified are also preferable.
[0081]
When monodisperse tabular grains having a narrow grain size distribution are used, more preferable results may be obtained. U.S. Pat. No. 4,797,354 and JP-A-2-838 describe a method for producing monodisperse hexagonal tabular grains having a high tabularization ratio. Further, EP 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. It is preferable to use these tabular grains in the present invention. Further, a particle having a high uniformity of thickness having a variation coefficient of the particle thickness of 30% or less is also preferable.
[0082]
In the case of tabular grains, dislocation lines can be observed with a transmission electron microscope. It is preferable to select a particle containing no dislocation line, a particle containing several dislocations, or a particle containing many dislocations according to the purpose. It is also possible to select a dislocation or a dislocation that is introduced linearly with respect to a specific direction of the crystal orientation of the grain, or to introduce the dislocation over the entire grain or only a specific portion of the grain, for example. The dislocation can be introduced only in the fringe portion of the particle. The fringe portion of the particle refers to the outer periphery of the tabular particle. Introduction of dislocation lines is preferable not only in the case of tabular grains, but also in the case of normal grains or irregular grains typified by potato grains. Also in this case, it is a preferable embodiment to limit the particle to a specific portion such as a vertex or a ridge.
[0083]
The silver halide grains of the present invention may be treated to impart roundness to the grains as disclosed in European Patent Nos. 96,727B1, 64,412B1, etc., or West German Patent No. 2,306,447C2; The surface may be modified as disclosed in JP-A-60-221320.
[0084]
Generally, the particle surface has a flat structure, but it is sometimes preferable to form irregularities intentionally. JP-A-58-106532 and JP-A-60-221320 disclose a method of forming a hole in a part of a crystal, for example, a vertex or a center of a plane, or a raffle described in U.S. Pat. No. 4,643,966. Particles are an example.
[0085]
The grain size of the silver halide grains of the present invention and the finally obtained grains are the circle equivalent diameter of the projected area using an electron microscope, the sphere equivalent diameter of the grain volume calculated from the projected area and the grain thickness, or the volume by the Coulter counter method. Can be evaluated by the sphere equivalent diameter and the like. Ultrafine particles having a sphere equivalent diameter of 0.05 μm or less and coarse particles exceeding 10 μm can be selected and used. Preferably, particles having a size of 0.1 μm or more and 3 μm or less are used as photosensitive halogenated particles.
[0086]
The silver halide grains of the present invention or the grains finally obtained can be selected from a so-called polydisperse emulsion having a wide grain size distribution and a monodisperse emulsion having a narrow size distribution depending on the purpose. In some cases, a variation coefficient of a diameter equivalent to a projected area of a particle or a diameter equivalent to a sphere of a volume is used as a scale representing a size distribution. When a monodisperse emulsion is used, it is preferable to use an emulsion having a size distribution with a coefficient of variation of 25% or less, more preferably 20% or less, and further preferably 15% or less.
[0087]
The monodisperse emulsion may be defined as having a grain size distribution such that 80% or more of all grains fall within ± 30% of the average grain size by number or weight of grains. 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 are mixed in the same layer or different layers in an emulsion layer having substantially the same color sensitivity. Can be applied in layers. Further, two or more kinds of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion can be used as a mixture or as a mixture.
[0088]
The silver halide grains of the present invention are described in "Physics and Chemistry of Photography" by Grafkid, published by P. Glafkids, Chimie et Physique Photographique, Paul Montel, 1967, "Photographic Emulsion Chemistry" by Duffin, published by Focal Press. (GF Duffin, Photographic Emulsion Chemistry, Focal Press, 1966), "Manufacture and Coating of Photographic Emulsions", by Zeligman et al., Focal Press (VL Zelikman et al., Making and Coating Photographic Photographic Imaging, Co.) , 1964) can be prepared. That is, any of an acidic method, a neutral method, an ammonia method, etc. may be used, and a method of reacting a soluble silver salt and a soluble halide may be any one of a one-sided mixing method, a simultaneous mixing method, and a combination thereof. Good. A method of forming grains in the presence of excess silver ions (a so-called reverse mixing method) can also be used. As one type of the double jet method, a method in which pAg in a liquid phase in which silver halide grains are formed is kept constant, that is, a so-called controlled double jet method can be used. According to this method, silver halide grains having a regular crystal form and a nearly uniform grain size can be obtained.
[0089]
US Pat. Nos. 4,334,012, 4,301,241, and 4,150,994, in which silver halide grains previously formed are added to a reaction vessel for preparing an emulsion, may be optionally added. Preferably, they can be used as seed crystals, and are also effective when supplied as silver halide for growth. In the latter case, it is preferable to add an emulsion having a small grain size, and the addition method can be selected from the method of adding the whole amount at once, adding the emulsion dispersed multiple times, or adding it continuously. It is also effective in some cases to add particles having various halogen compositions to modify the surface.
[0090]
Methods for converting most or only a part of the halogen composition of silver halide grains by a halogen conversion method are described in U.S. Pat. Nos. 3,477,852 and 4,142,900, and EP 273,429 and EP 273,429. No. 273,430 and West German Patent No. 3,819,241 are effective particle forming methods. A solution of a soluble halogen or silver halide grains can be added to convert the silver salt into a hardly soluble silver salt. It can be selected from methods such as conversion at a time, conversion into a plurality of times, or continuous conversion.
[0091]
In addition to the method of adding a soluble silver salt and a halogen salt at a constant concentration and a constant flow rate for grain growth, British Patent Nos. 1,469,480, 3,650,757 and 4,242,445. The particle formation method in which the concentration is changed or the flow rate is changed as described in (1) is a preferred method. By increasing the concentration or increasing the flow rate, the amount of silver halide to be supplied can be changed by a linear function, a quadratic function, or a more complicated function of the addition time. It is also preferable in some cases to reduce the amount of silver halide supplied as necessary. Further, when adding a plurality of soluble silver salts having different solution compositions or adding a plurality of soluble halide salts having different solution compositions, an addition method of increasing one and decreasing the other is also an effective method. It is.
[0092]
Mixers for reacting a solution of a soluble silver salt with a soluble halide salt are disclosed in U.S. Pat. Nos. 2,996,287, 3,342,605, 3,415,650 and 3,785. , 777, West German Published Patent Nos. 2,556,885 and 2,555,364.
[0093]
Silver halide solvents are useful for the purpose of accelerating ripening. For example, it is known to have excess amounts of halogen ions in the reactor to promote ripening. Other ripening agents can also be used. These ripening agents can be incorporated in their entirety in the dispersion medium in the reactor before adding the silver and halide salts, or can be added together with the halide salts, silver salts or peptizers, and added to the reactor. Can also be introduced. As another variant, the ripening agent can be introduced independently during the silver halide and silver salt addition steps.
[0094]
Ammonia, thiocyanates (for example, rhodacali, rhodamon ammonium), and organic thioether compounds (for example, U.S. Pat. Nos. 3,574,628, 3,021,215, 3,057,724, and Nos. 3,038,805, 4,276,374, 4,297,439, 3,704,130, 4,782,013, and JP-A-57-104926. And thione compounds (for example, tetra-substituted thioureas described in JP-A-53-82408 and JP-A-55-77737, U.S. Pat. Compounds described in JP-A-144319), mercapto compounds and amine compounds capable of promoting the growth of silver halide grains described in JP-A-57-202531. If For example, JP-such as No. 54-100717), and the like.
[0095]
Gelatin is advantageously used as a protective colloid used in the preparation of the emulsion of the present invention and as a binder for other hydrophilic colloid layers, but other hydrophilic colloids can also be used.
[0096]
For example, gelatin derivatives, graft polymers of gelatin and other macromolecules, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; Polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylimidazole, or various synthetic hydrophilic polymer materials such as polyvinylpyrazole Can be used.
[0097]
Examples of gelatin include lime-processed gelatin, acid-processed gelatin and Bull. Soc. Sci. Photo. Japan. No. 16. Enzyme-treated gelatin as described in P30 (1966) may be used, and hydrolysates or enzymatic degradation products of gelatin can also be used.
[0098]
The emulsion of the present invention is preferably washed with water for desalting and dispersed in a newly prepared protective colloid. The temperature of water washing can be selected according to the purpose, but is preferably selected in the range of 5 ° C to 50 ° C. The pH at the time of washing can be selected depending on the purpose, but is preferably selected from 2 to 10. More preferably, it is in the range of 3 to 8. The pAg at the time of washing can be selected according to the purpose, but is preferably selected from 5 to 10. The method of washing can be selected from noodle washing, dialysis using a semipermeable membrane, centrifugation, coagulation sedimentation, and ion exchange. In the case of the coagulation sedimentation method, a method using a sulfate, a method using an organic solvent, a method using a water-soluble polymer, a method using a gelatin derivative, and the like can be selected.
[0099]
A method of adding a chalcogenide compound during the preparation of an emulsion as described in U.S. Pat. No. 3,772,031 is sometimes useful. In addition to S, Se, and Te, cyanide, thiocyanate, selenocyanic acid, carbonate, phosphate, and acetate may be present.
[0100]
The silver halide grains of the present invention can be subjected to at least one of sulfur sensitization, selenium sensitization, gold sensitization, palladium sensitization and noble metal sensitization in any step of the production process of a silver halide emulsion. 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 type in which a chemical sensitizing nucleus is embedded in the grain, a type in which the chemical sensitizing nucleus is embedded in a shallow position from the grain surface, and a type in which a chemical sensitizing nucleus is formed on the surface. In the emulsion of the present invention, the location of the chemical sensitization nucleus can be selected according to the purpose. Generally, at least one type of chemical sensitization nucleus is formed near the surface.
[0101]
One of the chemical sensitizations that can be preferably carried out in the present invention is chalcogenide sensitization and noble metal sensitization alone or in combination, and is described by TH (James), The Photographic Process, Fourth Edition, Macmillan. It can be performed using active gelatin as described in pp. 67-76, 1977, (TH James, The Theory of the Photographic Process, 4th ed, Macmillan, 1977). -Disclosure 120, April 1974, 12008; Research Disclosure, 34, June 1975, 13452, U.S. Patent Nos. 2,642,361, 3,297,446, and 3,773 No. 03857, No. 3,857,711, No. 3, PAg 5-10, pH 5-8 and temperature 30 as described in U.S. Pat. Nos. 01,714, 4,226,018, and 3,904,415, and British Patent 1,315,755. At 〜80 ° C., it can be sulfur, selenium, tellurium, gold, platinum, palladium or a combination of a plurality of these sensitizers. In the noble metal sensitization, for example, a noble metal salt of gold, platinum, or palladium can be used, and among them, gold sensitization, palladium sensitization, and a combination of both are preferable. In the case of gold sensitization, for example, known compounds of chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, and gold selenide can be used. The palladium compound means a divalent palladium salt or a tetravalent salt. Preferred palladium compounds are (R)₂[PdX₆] Or (R)₂[PdX₄]. 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.
[0102]
Specifically, for example, K₂[PdCl₄], (NH₄)₂[PdCl₆], Na₂[PdCl₄], (NH₄)₂[PdCl₄], Li₂[PdCl₄], Na₂[PdCl₆] Or K₂[PdBr₄Is preferred. The gold compound and the palladium compound are preferably used in combination with thiocyanate or selenocyanate.
[0103]
As sulfur sensitizers, hypo, thiourea compounds, rhodanine compounds and sulfur described in U.S. Pat. Nos. 3,857,711, 4,226,018 and 4,054,457. Contained compounds can be used. Chemical sensitization can also be performed in the presence of a so-called chemical sensitizer. Useful chemical sensitization aids include compounds known to suppress fog in the process of chemical sensitization and increase sensitivity, such as azaindene, azapyridazine and azapyrimidine. Examples of chemical sensitizer modifiers are described in U.S. Pat. Nos. 2,131,038, 3,411,914, 3,554,757, JP-A-58-126526 and the above-mentioned duffin. The book is described in Photographic Emulsion Chemistry, pp. 138-143.
[0104]
The emulsion of the present invention is preferably used in combination with gold sensitization. The preferred amount of the gold sensitizer is 1 × 10 5 per mol of silver halide.^-4~ 1 × 10^-7Mole, more preferably 1 × 10^-5~ 5 × 10^-7Is a mole. The preferred range of the palladium compound is 1 × 10^-3From 5 × 10^-7It is. The preferred range of the thiocyan compound or selenocyan compound is 5 × 10^-2From 1 × 10^-6It is.
[0105]
The preferred amount of sulfur sensitizer used for the silver halide grains of the present invention is 1 × 10 5 per mol of silver halide.^-4~ 1 × 10^-7Mole, more preferably 1 × 10^-5~ 5 × 10^-7Is a mole.
[0106]
Selenium sensitization is a preferable sensitization method for the emulsion of the present invention. In the selenium sensitization, a known unstable selenium compound is used, and specifically, for example, colloidal metal selenium, selenoureas (for example, N, N-dimethylselenourea, N, N-diethylselenourea, etc.), Selenium compounds such as selenoketones and selenamides can be used. It may be preferable to use selenium sensitization in combination with sulfur sensitization and / or precious metal sensitization.
[0107]
The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the photographic material, or stabilizing photographic performance. That is, thiazoles, for example, benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, Aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 11-phenyl-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines; for example, thioketo compounds such as oxazolinethione; Azaindenes, for example, triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetraazaindenes), pentaazaynes Known as antifoggants or stabilizers such as emissions such, it can be added to many compounds. For example, those described in U.S. Pat. Nos. 3,954,474 and 3,982,947 and JP-B-52-28660 can be used. One of the preferred compounds is a compound described in JP-A-63-212932. Antifoggants and stabilizers can be used at various times before, during, or after particle formation, during the washing step, during dispersion after washing, before chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. It can be added according to the purpose. In addition to exhibiting the original antifogging and stabilizing effects by adding during emulsion preparation, control the crystal wall of the grains, reduce the grain size, reduce the solubility of the grains, control the chemical sensitization, It can be used for various purposes such as controlling the arrangement of dyes.
[0108]
The spectral sensitizing dye to be adsorbed on the silver halide grains of the present invention is a methine dye, and the photographic emulsion finally obtained is also spectrally sensitized by methine dyes and the like to exert the effect of the present invention. It is preferable to do. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine chords. Any of nuclei generally used for cyanine dyes as basic heterocyclic nuclei can be applied to these dyes. That is, for example, a pyrroline nucleus, an oxazoline nucleus, a thiozoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; A nucleus containing an aromatic hydrocarbon ring in these nuclei, that is, for example, an indolenine nucleus, a benzoindolenine nucleus, an indole nucleus, a benzoxadol nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, Selenazole nucleus, benzimidazole nucleus and quinoline nucleus can be applied. These nuclei may be substituted on carbon atoms.
[0109]
In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, for example, a pyrazoline-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, and rhodanine Nuclear and 5- to 6-membered heterocyclic nuclei such as thiobarbituric acid nuclei can be applied.
[0110]
These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for supersensitization. Representative examples are U.S. Pat. Nos. 2,688,545, 2,977,229, 3,397,060, 3,522,052, 3,527,641, No. 3,617,293, No. 3,628,964, No. 3,666,480, No. 3,672,898, No. 3,679,428, No. 3,703 No. 3,377,301, No. 3,814,609, No. 3,837,862, No. 4,026,707, British Patent No. 1,344,281, No. 1,507,803, JP-B-43-4936, JP-B-53-12375, JP-A-52-110618, and JP-A-52-109925.
[0111]
Along with the sensitizing dye, a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion.
[0112]
The preferred timing of adding the spectral sensitizing dye of the present invention is after the formation of silver halide grains and before the addition of fine grains. Most commonly, it is performed after completion of chemical sensitization and before coating, but as described in US Pat. Nos. 3,628,969 and 4,225,666, chemical sensitizers are used. At the same time as the above, spectral sensitization can be carried out at the same time as chemical sensitization, or can be carried out prior to chemical sensitization as described in JP-A-58-113928. It can be added before the completion of the formation to start spectral sensitization. Furthermore, these compounds may be added separately as taught in U.S. Pat. No. 4,255,666, i.e., some of these compounds may be added prior to chemical sensitization and the remainder chemically sensitized. It is also possible to add the silver halide grains after the silver halide grains are formed, and may be added at any time during the formation of silver halide grains, including the method disclosed in U.S. Pat. No. 4,183,756.
[0113]
The addition amount is 4 × 10 4 mol per mol of silver halide.^-6~ 8 × 10^-3The silver halide grains can be used in an amount of about 5 × 10 5 in the case of a more preferred silver halide grain size of 0.2 to 1.2 μm.^-5~ 2 × 10^-3Moles are more effective.
[0114]
When the emulsion obtained in the present invention is used as a light-sensitive material, the above-mentioned various additives are used. In addition, various additives can be used according to the purpose.
[0115]
These additives are described in more detail in Research Disclosure Item 17643 (December 1978), Item 18716 (November 1979) and Item 308119 (December 1989).
[0116]
The silver halide emulsion of the present invention can be used for various photographic materials by any conventional method. As one 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 light-sensitive material such as a color negative film or a color reversal film, the silver halide emulsion of the present invention may be used on either the upper layer side or the lower layer side, or may be used together.
[0117]
【Example】
Hereinafter, the present invention will be described in detail with reference to Examples, but embodiments of the present invention are not limited thereto. The invention can be better understood by reference to the following examples of emulsion preparation, emulsion and photographic elements that satisfy the requirements of the invention.
[0118]
The sensitivity is represented by the relative value of the logarithm of the reciprocal of the exposure amount E (E is expressed in units of lux-second) giving a density of fog + 0.2.
[0119]
Example 1
<Preparation of seed crystal emulsion-1>
A seed crystal emulsion was prepared as follows.
[0120]
Using a mixing stirrer described in JP-B-58-58288, an aqueous solution of silver nitrate (1.161 mol) and a mixed aqueous solution of potassium bromide and potassium iodide (potassium iodide Mol%) was added over 2 minutes by a double jet method while maintaining the silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) at 0 mV to perform nucleation. Subsequently, the temperature of the solution was raised to 60 ° C. over a period of 60 minutes, the pH was adjusted to 5.0 with an aqueous solution of sodium carbonate, and then an aqueous solution of silver nitrate (5.902 mol), potassium bromide and iodide were added. A mixed aqueous solution of potassium (2 mol% of potassium iodide) was added over 42 minutes by a double jet method while keeping the silver potential at 9 mV. After the addition was completed, the temperature was lowered to 40 ° C., and desalting and washing were immediately performed using a normal flocculation method.
[0121]
The resulting seed crystal emulsion had an average sphere-equivalent diameter of 0.24 μm, an average aspect ratio of 4.8, and a maximum side length ratio of 90% or more of the total projected area of the silver halide grains (the maximum side length and the maximum side length of each grain). The emulsion was composed of hexagonal tabular grains having a ratio to the minimum side length of 1.0 to 2.0. This emulsion is referred to as seed crystal emulsion-1.
[0122]

<< Preparation of silver iodide fine grain emulsion SMC-1 >>
While vigorously stirring 5 l of a 6.0% by weight aqueous gelatin solution containing 0.06 mol of potassium iodide, 2 l of a 7.06 mol aqueous solution of silver nitrate and 2 l of a 7.06 mol aqueous solution of potassium iodide each take 10 minutes. And added. During this time, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the preparation of the particles, the pH was adjusted to 5.0 using an aqueous sodium carbonate solution. The average particle size in terms of sphere of the obtained silver iodide fine particles was 0.05 μm. This emulsion is designated as SMC-1.
[0123]
(Preparation of Comparative Emulsion 1-1)
0.178 mol of seed crystal emulsion-1 and HO (CH₂CH₂O)_m(CH (CH₃) CH₂O)_19.8(CH₂CH₂O)_n700 ml of a 4.5% by weight aqueous solution of inert gelatin containing 0.5 ml of a 10% ethanol solution of H (m + n = 9.77) was maintained at 75 ° C., the pAg was adjusted to 8.4, and the pH was adjusted to 6.0. Then, particles were formed by the simultaneous mixing method with vigorous stirring according to the following procedure.
[0124]
1) A 2.077 mol silver nitrate aqueous solution, 0.218 mol SMC-1 and a potassium bromide aqueous solution were added while maintaining the pAg at 8.8 and the pH at 6.0.
[0125]
2) Subsequently, the temperature of the solution was lowered to 60 ° C., and the pAg was adjusted to 9.8. Thereafter, 0.71 mol of SMC-1 was added, and aging was performed for 2 minutes. (Introduction of dislocation lines).
[0126]
3) 0.91 mol of silver nitrate aqueous solution, 0.079 mol of SMC-1 and potassium bromide aqueous solution were added while keeping pAg at 9.8 and pH at 5.0.
[0127]
The resulting emulsion had a grain size (one side length of a cube of the same volume) of 0.65 μm, an average aspect ratio of 6.5, and a silver iodide content of 2 / 9.5 / X / 8.0 mol% from inside the grains ( X was an emulsion composed of tabular grains having a halogen composition at a dislocation line introduction position). When this emulsion was observed with an electron microscope, five or more dislocation lines were observed both in the fringe portion and in the inside of the grains in 60% or more of the total projected area of the grains in the emulsion. The surface silver iodide content was 11.9 mol%.
[0128]
(Preparation of Comparative Emulsion 1-2)
In the step 1) of the preparation of the comparative emulsion 1-1, when 50% of the added silver amount was added, K₄[Fe (CN)₆] With an aqueous solution^-5Mol / mol Ag was added. This emulsion is referred to as Comparative Emulsion 1-2.
[0129]
(Preparation of Comparative Emulsion 1-3)
In the step 1) of the preparation of the comparative emulsion 1-1, when 50% of the added silver amount was added, K₄[Ru (CN)₆] With an aqueous solution^-5Mol / mol Ag was added. This emulsion is referred to as Comparative Emulsion 1-3.
[0130]
(Preparation of Comparative Emulsion 1-4)
In the step 1) of the preparation of the comparative emulsion 1-1, when 50% of the added silver amount was added, K₃[Ir (CN)₆] With an aqueous solution^-5Mol / mol Ag was added. This emulsion is referred to as Comparative Emulsion 1-4.
[0131]
(Emulsion 1-5 of the present invention), 1-7Preparation of ~ 1-13)
In the step of preparing Comparative Emulsion 1-2, K_Four[Fe (CN)₆In place of compound I-10, I-12, I-17, I-21, I-24, I-27, I-28 and I-29 were 1 × 10^-FiveMol / mol Ag was added. These emulsions were prepared as Emulsion 1-5., 1-7１−1-13.
[0132]
1-2-1-5, 1-7 to 1-The grain size, average aspect ratio, halogen composition, dislocation line, and surface silver iodide content of Emulsion No. 13 were almost the same as 1-1.
[0133]
<Sensitization>
Next, the emulsions 1-1 to 1-5, 1-7 to 1-13 were subjected to the following sensitization.
[0134]
An emulsion containing 0.5 mole of silver halide was melted at 40 ° C., and spectral sensitizing dye 1, dye 2 and dye 3 were added at a ratio of 1: 1: 1 so that the total coverage was about 70%. . Thereafter, triphosphine selenide, sodium thiosulfate, chloroauric acid, and potassium thiocyanate were added, and after optimal chemical sensitization according to a conventional method, 4-hydroxy-6-methyl-1,3,3a, 7-Tetraazaindene (TAI), 1-phenyl-5-mercaptotetrazole (PMT) was added.
[0135]
Embedded image

[0136]
<Preparation of single layer photosensitive material sample>
Emulsified 1-1 to 1-5, 1-7 to 1-13 was coated on a cellulose acetate film support coated with a gray silver antihalation layer, and the emulsion layer was coated with a surfactant and bis (vinylsulfonyl) methane hardener (1.75% by weight based on total weight of gelatin). %) And 4.3 g / m^TwoOvercoated with a gelatin layer. Emulsion coating amount is 0.646 gAg / m^TwoThe total amount of coupler 1, surfactant and gelatin was 1.08 g / m 2 in this layer.^TwoWas also contained. Thus, emulsions 1-1 to 1-5, 1-7 to 1-13, the single-layer light-sensitive material samples 101 to105, 107-113 was obtained.
[0137]
Embedded image

[0138]
<Evaluation>
Samples 101 to 101 obtained in this manner105, 107-Each of 113 was exposed to wedges with white light for 0.01 second, and color-developed according to the following processing steps, and then the sensitivity and fog were measured using an optical densitometer (PDA-65 manufactured by Konica). Table 1 shows relative sensitivities and fog densities when the sensitivity of the sample 101 was set to 100. The doping ratio of each sample was determined by an ICP method and an ICP-MS method.
[0139]
The dope ratio as used herein refers to the amount of complex contained in 1 mol of silver halide after dissolving an emulsion, centrifuging, decomposing gelatin with a gelatinase (actinase) solution, repeating centrifugation and washing with pure water. It is a value obtained by dividing by the amount of addition and multiplying by 100.
[0140]
"processing"
Processing step Processing time Processing temperature
Color development 2 min 50 sec 38 ± 0.3 ℃
Bleaching 45 seconds 38 ± 2.0 ° C
1 minute 30 seconds 38 ± 2.0 ℃
Stability 60 seconds 38 ± 5.0 ℃
Drying 1 minute 55 ± 5.0 ℃
The following color developing solutions, bleaching solutions, fixing solutions and stabilizing solutions were used.
[0141]
Color developer
800cc water
30 g of potassium carbonate
2.5 g sodium bicarbonate
Potassium sulfite 3.0g
1.3 g of sodium bromide
Potassium iodide 1.2mg
Hydroxylamine sulfate 2.5g
Sodium chloride 0.6g
4-amino-3-methyl-N-ethyl-N- (β-hydroxylethyl)
4.5 g of aniline sulfate
3.0 g of diethylenetriaminepentaacetic acid
Potassium hydroxide 1.2g
Add water to make up to 1 liter and adjust to pH 10.06 with potassium hydroxide or 20% sulfuric acid.
[0142]
Bleach
700cc water
125 g of iron (III) ammonium 1,3-diaminopropanetetraacetate
2 g of ethylenediaminetetraacetic acid
Sodium nitrate 40g
150 g of ammonium bromide
Glacial acetic acid 40g
Add water to make 1 liter and adjust to pH 4.4 with aqueous ammonia or glacial acetic acid.
[0143]
Fixer
800cc water
Ammonium thiocyanate 120g
Ammonium thiosulfate 150g
Sodium sulfite 15g
2 g of ethylenediaminetetraacetic acid
After adjusting the pH to 6.2 using aqueous ammonia or glacial acetic acid, water is added to make 1 liter.
[0144]
Stabilizing liquid
900cc water
2.0 g of paraoctylphenyl polyoxyethylene ether (n = 10)
0.5 g of dimethylol urea
Hexamethylenetetramine 0.2g
1,2-benzisothiazolin-3-one 0.1 g
Siloxane (UCC L-77) 0.1g
Ammonia water 0.5cc
After adding water to make 1 liter, the pH is adjusted to 8.5 with aqueous ammonia or 50% sulfuric acid.
[0145]
[Table 1]

[0146]
As is clear from Table 1, an emulsion containing a metal complex having at least one ligand having an adsorptive group to silver halide (emulsion 1-5), 1-7Sample 105 using １−1-13), 107It was found that the samples Nos. To 113 had a very high doping ratio, and the sensitivity was dramatically improved. Thus, a photographic emulsion having an unprecedented high sensitivity could be obtained.
[0147]
Example 2
(Preparation of Comparative Emulsion 2-1)
In the step 1) of the preparation of the comparative emulsion 1-1, when 50% of the added silver amount was added, Fe (CO)₅In aqueous solution 1 × 10^-5Mol / mol Ag was added. This emulsion is referred to as Comparative Emulsion 2-1.
[0148]
(Preparation of Emulsions 2-2 to 2-4 of the Present Invention)
In the step of preparing Comparative Emulsion 1-2, K₄[Fe (CN)₆In place of compounds II-14, I-53 and II-66.^-5Mol / mol Ag was added. These emulsions are referred to as emulsions 2-2 to 2-4.
[0149]
Sensitization, preparation and evaluation of single layer photosensitive material sample
The emulsions 2-1 to 2-4 were sensitized and single layer samples were prepared in the same manner as in Example 1 to obtain samples 201 to 204. The sensitivity and fog of the thus obtained samples 201 to 204 were measured in the same manner as in Example 1. Table 2 shows relative sensitivities and fog densities when the sensitivity of the sample 101 manufactured in Example 1 was set to 100. The doping ratio of each sample was determined by an ICP method and an ICP-MS method.
[0150]
[Table 2]

[0151]
As is clear from Table 2, Samples 202 to 202 using emulsions (Emulsions 2-2 to 2-4) to which a metal complex having an adsorbing group to silver halide on at least one of the ligands was added. 204 was found to have a very high doping ratio and drastically improved sensitivity, and a high-sensitivity photographic emulsion never before obtained could be obtained.
[0152]
Example 3
(Preparation of Comparative Emulsions 3-1 and 3-2)
In the step 1) of the preparation of the comparative emulsion 1-1, when 50% of the added silver amount was consumed, K₂[Pd (CN)₄], K₂[Pt (CN)₄] With an aqueous solution^-5Mol / mol Ag was added. This emulsion is referred to as Emulsions 3-1 and 3-2.
[0153]
(Preparation of Emulsions 3-3 to 3-8 of the Present Invention)
In the step of preparing Comparative Emulsion 1-2, K [Fe (CN)₆In place of compounds III-14, III-16, III-53, III-55, III-66, and III-68.^-5Mol / mol Ag was added. These emulsions are referred to as emulsions 3-3 to 3-8.
[0154]
<Sensitization, preparation and evaluation of single-layer photosensitive material sample>
The emulsions 3-1 to 3-8 were sensitized and single layer samples were prepared in the same manner as in Example 1 to obtain samples 301 to 308. The sensitivity and fog of the thus obtained samples 301 to 308 were measured in the same manner as in Example 1. Table 3 shows relative sensitivities and fog densities when the sensitivity of the sample 101 manufactured in Example 1 was set to 100. The doping ratio of each sample was determined by an ICP method and an ICP-MS method.
[0155]
[Table 3]

[0156]
As can be seen from Table 3, Samples 303 to 303 using emulsions (Emulsions 3-3 to 3-8) to which a metal complex having at least one ligand having an adsorbing group to silver halide was added. It was found that the sample 308 had a very high doping ratio, and the sensitivity was dramatically improved, so that a photographic emulsion having a high sensitivity which had never existed before could be obtained.
[0157]
Example 4
Next, an example of improvement of illuminance failure will be described.
[0158]
(Preparation of Comparative Emulsion 4-1)
In the step 1) of the preparation of the comparative emulsion 1-1, after introducing the transition line,₂IrCl₆In aqueous solution 1 × 10^-7Mol / mol Ag was added. This emulsion is referred to as Emulsion 4-1.
[0159]
(Preparation of Emulsions 4-2 to 4-3 of the Present Invention)
In the step of preparing Emulsion 4-1, K₂IrCl₆Was replaced with 1 × 10 of compounds I-8 and I-25.^-7Mol / mol Ag was added. These emulsions are referred to as emulsions 4-2 to 4-3.
[0160]
<Sensitization, preparation and evaluation of single-layer photosensitive material sample>
The emulsions 4-1 to 4-3 were sensitized and single layer samples were prepared in the same manner as in Example 1 to obtain samples 401 to 403. For the samples 401 to 403 thus obtained, the sensitivity and fog were measured in the same manner as in Example 1, and exposure was performed for the exposure time shown in Table 4. Table 4 shows relative sensitivities and fog densities when the sensitivity of the sample 101 manufactured in Example 1 was set to 100. The doping ratio of each sample was determined by an ICP method and an ICP-MS method.
[0161]
[Table 4]

[0162]
As is apparent from Table 4, Samples 402 to 402 using emulsions (Emulsions 4-2 to 4-3) to which a metal complex having an adsorbing group for silver halide as at least one of the ligands was added. No. 403 has a very high doping ratio, and shows that the sensitivity is remarkably improved in both high illuminance and low illuminance failure, and a photographic emulsion having an unprecedented illuminance failure improvement effect was obtained.
[0163]
Example 5
On a triacetyl cellulose film support provided with an undercoat layer, layers having the following compositions were sequentially formed from the support side to prepare a multilayer color photographic light-sensitive material sample 501.
[0164]
Addition amount is 1m²Expressed in grams per unit. However, silver halide and colloidal silver were converted to the amount of silver, and sensitizing dyes (indicated by SD) were shown in moles per mole of silver.
[0165]
First layer (anti-halation layer)
Black colloidal silver 0.16
UV-1 0.3
CM-1 0.123
CC-1 0.044
OIL-1 0.167
Gelatin 1.33
Second layer (middle layer)
AS-1 0.160
OIL-1 0.20
Gelatin 0.69
Third layer (low-sensitivity red-sensitive layer)
Silver iodobromide a 0.20
Silver iodobromide b 0.29
SD-6 2.37 × 10^-5
SD-7 1.2 × 10^-4
SD-8 2.4 × 10^-4
SD-9 2.4 × 10^-6
C-1 0.32
CC-1 0.038
OIL-2 0.28
AS-2 0.002
Gelatin 0.73
4th layer (medium-speed red-sensitive layer)
Silver iodobromide c 0.10
Silver iodobromide d 0.86
SD-6 4.5 × 10^-5
SD-7 2.3 × 10^-4
SD-8 4.5 × 10^-4
C-2 0.52
CC-1 0.06
DI-1 0.047
OIL-2 0.46
AS-2 0.004
Gelatin 1.30
Fifth layer (high-sensitivity red-sensitive layer)
Silver iodobromide c 0.13
Silver iodobromide d 1.18
SD-6 3.0 × 10^-5
SD-7 1.5 × 10^-4
SD-8 3.0 × 10^-4
C-2 0.047
C-3 0.09
CC-1 0.036
DI-1 0.024
OIL-2 0.27
AS-2 0.006
Gelatin 1.28
6th layer (middle layer)
OIL-1 0.29
AS-1 0.23
Gelatin 1.00
7th layer (low sensitivity green color sensitive layer)
Silver iodobromide a 0.19
Silver iodobromide b 0.062
SD-9 3.6 × 10^-4
SD-10 3.6 × 10^-4
Coupler 2 0.18
CM-1 0.033
OIL-1 0.22
AS-2 0.002
AS-3 0.05
Gelatin 0.61
8th layer (middle layer)
OIL-1 0.26
AS-1 0.054
Gelatin 0.80
9th layer (medium speed green color sensitive layer)
Silver iodobromide e 0.54
Silver iodobromide f 0.54
SD-11 3.7 × 10^-4
SD-12 7.4 × 10^-5
SD-13 5.0 × 10^-5
Coupler 2 0.17
M-2 0.33
CM-1 0.024
CM-2 0.029
DI-2 0.024
DI-3 0.005
OIL-1 0.73
AS-3 0.035
AS-2 0.003
Gelatin 1.80
10th layer (highly sensitive green color-sensitive layer)
Silver iodobromide f 1.19
SD-11 4.0 × 10^-4
SD-12 8.0 × 10^-5
SD-13 5.0 × 10^-5
Coupler 2 0.065
CM-2 0.026
CM-1 0.022
DI-3 0.003
DI-2 0.003
OIL-1 0.19
OIL-2 0.43
AS-3 0.017
AS-2 0.014
Gelatin 1.23
11th layer (yellow filter layer)
Yellow colloidal silver 0.05
OIL-1 0.18
AS-1 0.16
Gelatin 1.00
12th layer (low-sensitivity blue-sensitive layer)
Silver iodobromide b 0.22
Silver iodobromide a 0.08
Silver iodobromide h 0.09
SD-14 6.5 × 10^-4
SD-15 2.5 × 10^-4
Coupler 1 0.77
DI-4 0.017
OIL-1 0.31
AS-2 0.002
Gelatin 1.29
13th layer (high-sensitivity blue-sensitive layer)
Silver iodobromide h 0.41
Silver iodobromide i 0.61
SD-14 4.4 × 10^-4
SD-15 1.5 × 10^-4
Coupler 1 0.23
OIL-1 0.10
AS-2 0.004
Gelatin 1.20
Fourteenth layer (first protective layer)
Silver iodobromide j 0.30
UV-1 0.055
UV-2 0.110
OIL-2 0.30
Gelatin 1.32
Fifteenth layer (second protective layer)
PM-1 0.15
PM-2 0.04
WAX-1 0.02
D-1 0.001
Gelatin 0.55
The characteristics of the silver iodobromide are shown below (the average grain size is one side length of a cube of the same volume).
[0166]

As an example of the formation of silver halide grains, a production example of silver iodobromide d and f is shown below. Further, silver iodobromide j (hereinafter also referred to as emulsion j) was prepared with reference to the descriptions of JP-A-1-183417, JP-A-1-183644, JP-A-1-183645, and JP-A-2-166442.
[0167]
<< Preparation of silver iodobromide d >>
0.178 mol of seed crystal emulsion-1 and HO (CH₂CH₂O)_m(CH (CH₃) CH₂O)_19.8(CH₂CH₂O)_n700 ml of a 4.5% by weight aqueous solution of inert gelatin containing 0.5 ml of a 10% ethanol solution of H (m + n = 9.77) was maintained at 75 ° C., the pAg was adjusted to 8.4, and the pH was adjusted to 5.0. Thereafter, particles were formed by the simultaneous mixing method with vigorous stirring according to the following procedure.
[0168]
1) An aqueous solution of 3.093 mol of silver nitrate, 0.287 mol of SMC-1 and an aqueous solution of potassium bromide were added while maintaining the pAg at 8.4 and the pH at 5.0.
[0169]
2) Subsequently, the temperature of the solution was lowered to 60 ° C., and the pAg was adjusted to 9.8. Thereafter, 0.071 mol of SMC-1 was added and aging was performed for 2 minutes (introduction of dislocation lines).
[0170]
3) 0.959 mol of silver nitrate aqueous solution, 0.03 mol of SMC-1 and potassium bromide aqueous solution were added while keeping pAg at 9.8 and pH at 5.0.
[0171]
In addition, each solution was added at an optimum rate so as to prevent formation of new nuclei and Ostwald ripening between particles from proceeding during the particle formation. After completion of the addition, the resultant was subjected to a water washing treatment at 40 ° C. using a normal flocculation method, and gelatin was added for redispersion, and the pAg was adjusted to 8.1 and the pH was adjusted to 5.8.
[0172]
The resulting emulsion had a particle size (one side length of a cube of the same volume) of 0.74 μm, an average aspect ratio of 5.0, and a silver iodide content of 2 / 8.5 / X / 3 mol% (X: This was an emulsion comprising tabular grains having a halogen composition (dislocation line introduction position). When this emulsion was observed with an electron microscope, five or more dislocation lines were observed both in the fringe portion and in the inside of the grains in 60% or more of the total projected area of the grains in the emulsion. The surface silver iodide content was 6.7 mol%.
[0173]
<< Preparation of silver iodobromide f >>
In the preparation of silver iodobromide d, the pAg in step 1) was 8.8, the amount of silver nitrate added was 2.077 mol, the amount of SMC-1 was 0.218 mol, and the silver nitrate added in step 3) Silver iodobromide f was prepared in exactly the same manner as silver iodobromide d except that the amount was 0.91 mol and the amount of SMC-1 was 0.079 mol.
[0174]
The resulting emulsion had a grain size (one side length of a cube of the same volume) of 0.65 μm, an average aspect ratio of 6.5, and a silver iodide content of 2 / 9.5 / X / 8.0 mol% from inside the grains ( X was an emulsion composed of tabular grains having a halogen composition at a dislocation line introduction position). When this emulsion was observed with an electron microscope, five or more dislocation lines were observed both in the fringe portion and in the inside of the grains in 60% or more of the total projected area of the grains in the emulsion. The surface silver iodide content was 11.9 mol%.
[0175]
After adding the above-described sensitizing dye to each of the above emulsions and ripening, triphosphine selenide, sodium thiosulfate, chloroauric acid, and potassium thiocyanate are added, and fogging is performed according to a conventional method so that the sensitivity relationship is optimized. Chemical sensitization was applied.
[0176]
Silver iodobromide a, b, c, e, h, and i were also prepared according to the above silver iodobromide d and f and subjected to spectral sensitization and chemical sensitization.
[0177]
In addition to the above composition, coating aids SU-1, SU-2, SU-3, dispersion aid SU-4, viscosity adjuster V-1, stabilizers ST-1, ST-2, fog Inhibitor AF-1, two kinds of polyvinylpyrrolidone (AF-2) having a weight average molecular weight of 10,000 and a weight average molecular weight of 1,100,000, inhibitors AF-3, AF-4, AF-5, and hard Film agents H-1, H-2 and preservative Ase-1 were added.
[0178]
The structure of the compound used in the above sample is shown below.
[0179]
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[0180]
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[0181]
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[0182]
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[0183]
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[0184]
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[0185]
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[0186]
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[0187]
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[0188]
In the above multilayer sample, the same evaluation as in Example 1 (the color development time was 3 minutes and 15 seconds) was performed, except that the silver iodobromide f in the tenth layer was replaced with the emulsion 1-9.
[0189]
It was confirmed that the effect of the present invention was remarkable in the multilayer color photosensitive material as in Example 4 as in Example 1.
[0190]
【The invention's effect】
As is clear from the above Examples, the present invention can provide an emulsion having high sensitivity and low fog and / or an emulsion having improved illuminance failure.

Claims (5)

30 to 70% of the positions of the added amount of silver halide grain formation, have an adsorption group to silver halide in at least one of the ligands, the central metal is manganese, iron, Le ruthenium, palladium, Lee Rijiumu method of a silver halide photographic emulsion, which comprises using a metal complex selected from platinum. However, it excludes the case where the central metal of the metal complex is Ru and the ligand has an imidazole nucleus. The method for producing a silver halide photographic emulsion according to claim 1, wherein the metal complex is a metal complex represented by the following general formula (I).
Formula (I) [A _n -MX _(6-n) ] Z
[In the formula, A represents an atom group containing a group adsorbable to silver halide, M represents a central metal, X represents a ligand, n represents an integer of 1 to 6, and when n is 2 or more, Each A may be the same or different, and when (6-n) is 2 or more, each X may be the same or different. Z represents a counter ion necessary for neutralizing the charge of the complex. ] The metal complex is represented by the following general formula ( II 2. The method for producing a silver halide photographic emulsion according to claim 1, wherein a metal complex represented by the formula (1) is used.
The general formula ( II ) [A _n -MX _(5-n) ] Z
[In the formula, A represents an atom group containing a group that can be adsorbed to silver halide, M represents a central metal, X represents a ligand, n represents an integer of 1 to 5, and when n is 2 or more, Each A may be the same or different, and when (5-n) is 2 or more, each X may be the same or different. Z represents a counter ion necessary for neutralizing the charge of the complex. ] The metal complex is represented by the following general formula ( III 2. The method for producing a silver halide photographic emulsion according to claim 1, which is a metal complex represented by the formula:
The general formula ( III ) [A _n -MX _(4-n) ] Z
[In the formula, A represents an atom group containing a group adsorbable to silver halide, M represents a central metal, X represents a ligand, n represents an integer of 1 to 4, and when n is 2 or more, Each A may be the same or different, and when (4-n) is 2 or more, each X may be the same or different. Z represents a counter ion necessary for neutralizing the charge of the complex. ] A silver halide photographic emulsion produced by the method for producing a silver halide photographic emulsion according to any one of claims 1 to 4.