JP3999147B2 - Silver halide emulsion, process for producing the same and photographic light-sensitive material - Google Patents

Description

【０００８】
更により細かく、ｐＨ、ｐＡｇを変化させた時の結果から判断すると、該１２面体粒子の好ましい生成領域は、（ｐＡｇ≧２．４でかつ、ＰＩ≧２．４）が好ましく、（ｐＡｇ≧２．７で、かつＰＩ≧２．７）がより好ましい。ｐＨは１〜１２が好ましく、ｐＨ３〜９がより好ましく、ｐＨ４〜８が更に好ましい。ｐＨ３以下では図２ｃに示した粒子が個数で０．１〜１０％の割合で混入し易い。ここでｐＩ＝−log〔Ｉ^-mol／Ｌ〕で、ｐＡｇ＝−log〔Ａｇ⁺mol／Ｌ〕である。
該粒子が丸みを帯びた図１ｅと図６ｃの態様の粒子の好ましい生成領域は、（ｐＡｇ＝１〜２．７）が好ましく、（ｐＡｇ＝１〜２．４）がより好ましい。ｐＨは７〜１２が好ましく、８〜１１がより好ましい。
図２ｂ、ｃに記載の六角柱状粒子の好ましい生成領域は、ｐＨ１〜９が好ましく、ｐＨ１〜７がより好ましく、１〜５が更に好ましい。ｐＡｇは１〜２．７が好ましく、１〜２．４がより好ましい。
該直角平行四辺形状の面が平担である図２のｃやｄ、図６ｄに示した粒子はｐＨ１〜３．９で生じ易く、該面が平担でない図２ｂや図６ｅの粒子はｐＨ４〜８．５で生じ易い。一方の粒子の数比率（％）を６０〜１００、好ましくは８０〜１００、より好ましくは９０〜１００％で作り分けする事ができる。
図３、４および(13)、(14)に記載の１４面体粒子の好ましい生成領域はｐＨ１〜９、好ましくは１〜６で、ｐＩ１〜２．７、好ましくは１．５〜２．５である。その他、前記１２面体粒子を該領域で成長させると、１２面体粒子が該１４面体粒子化し、(13)、(14)記載の乳剤が得られる。
ｐＨ５〜１２、好ましくは９〜１１（表１のＣ₉の条件）で形成すると、平板状粒子が生成する。その粒子構造例を図５、図６ｈに示した。全ＡｇＸ粒子の投影面積の合計の５０〜１００、好ましくは７０〜１００、より好ましくは９０〜１００％がアスペクト比（粒子の円相当投影直径／粒子の厚さ）が１．６〜１００、好ましくは２〜１００で、厚さ（μｍ）が０．０２〜０．５、好ましくは０．０２〜０．３の平板粒子乳剤が得られる。
該１２面体粒子生成のｐＨ、ｐＡｇ条件下で、種晶形成時の温度を５〜５０℃領域で行ない、成長を６０〜９５℃で行った場合、即ち、種晶形成の温度を下げると、１４面体型粒子の生成確率が増す。
一度１４面体粒子を形成すると、該種晶を、該１２面体粒子生成条件下で成長させても、１４面体粒子のまま成長する事から、１４面体粒子は、該粒子特有の結晶欠陥を有していると考えられる。即ち、双晶面、転位線（刃状転位線、ラセン転位線）の枚数、本数、入り方が特定の態様と考えられる。
これらの特性から判断すると、これらの粒子を該結晶欠陥含量の少ない順に書けば、〔該１２面体粒子＞該対称１４面体粒子、該非対称１４面体粒子＞平板粒子〕と考えられる。また、（２）〜（９）記載の１２面体粒子は５０℃以上、好ましくは６０℃以上の高温領域で生成し易い粒子といえる。ここで該結晶欠陥は双晶面、刃状転位線、ラセン転位線を指す。
通常の粒子形成でβ含率がほぼ１００モル％のＡｇＩ粒子を形成する事ができる。これは、そのＸ線回折測定で、２θ＝５０．７９５°や５５．７０３°のγ型特有のピーク強度が、他のβ型の２θ＝５３．１１３°や４２．４４９°のピーク強度の１％以下である事から結論される。また、２５０℃からゆっくり冷却させると（最も安定な構造をとる）、β含率１００％の結晶が得られる事、通常の粒子形成条件でγ含率が７０モル％以上の粒子は得られない事、前記の高温から急冷という特殊手法でγ含率が高くなる事等から、室温近傍でβ型が最も安定と考えられる。しかし、青光吸収端波長は（α＞γ＞β）の順であり、γ型の方がより長波長光まで吸収できる利点がある。この点で、γ含率が高い粒子が好ましい。
γ含率の高い粒子は、表１のＣ₂、Ｃ₄、Ｃ₆、Ｃ₉の領域で得られる。
これらの粒子は、ｐＨ１〜１２、ｐＡｇ＝１〜１０又は、ｐＩ＝１〜１０、温度（℃）０〜１００、好ましくは２〜９０の領域内で最も好ましい組合せを選んで形成する事が好ましい。
該楕円球状粒子は表１のＣ₃の条件で粒子成長させると得られる事から、先ず該１２面体の種晶を形成し、次にAgNO₃とアルカリを添加してＣ₃の条件にもってゆき、該条件下で成長させても得られるし、その方がより好ましい。
粒子形成用分散媒は質量平均分子量が３０００〜１０⁶、好ましくは１０⁴〜３×１０⁵の従来公知のあらゆる水溶性分散媒を０．１〜１５、好ましくは０．３〜１０質量％域で用いる事ができ、分散媒の具体例に関しては文献４、６、特願２００１−２９７０２３号の記載を参考にできる。ゼラチンとしてはアルカリ処理、酸処理ゼラチン、メチオニン含率（μmol/ｇ）が０〜６０のゼラチンと０〜２０の低Ｍｅｔ含率ゼラチン、Ｈ₂Ｏ₂で酸化処理した該低Ｍｅｔ含率ゼラチン；質量平均分子量が３０００〜７０，０００、好ましくは５０００〜４０，０００の該ゼラチン；アミノ基、カルボキシル基、イミダゾール基、アルコール基、アミジノ基、チオエーテル基の１〜６種の基の０．１〜１００、好ましくは１０〜１００％を化学修飾したゼラチンを用いる事ができる。化学修飾として炭素数１〜５０、好ましくは１〜２０の有機化合物が好ましい。
例えばフタル化、ベンゾイル化、アセチル化、トリメリト化、コハク化、メチルエステル化ゼラチンを挙げる事ができる。
例えば表１のＣ₅の条件で、ＡｇＩ粒子を形成した場合、用いる分散媒種がフタル化ゼラチンであり、フタル化率が９５〜１００％の時に、(37)に記載の粒子が形成されるが０．１〜９０％の場合には（９）に記載の粒子が得られる。しかし、アミノ基をアセチル化、ベンゾイル化、トリメリト化したゼラチンや、酸基をエステル化したゼラチンの場合はいずれも、修飾率０．１〜１００％において（９）に記載の粒子が得られる。
その他、後述のゼラチンが好ましい。
なお表１で右端の例えば〔＜２．３、（≧３）〕はｐＡｇ＜２．３、ｐＩ≧３を表わす。
(13)〜(15)、(37)記載の１４面体粒子は粒子表面に凹部（トラフ、溝部ともいう）を有する態様と有しない態様がある。凹部を有する態様例を図４のｄに示した。凹部は(００１)面に平行に入っている。これは(００１)面に平行に双晶面が入った為と考えられる。図７において、一方の原子のみに注目した積層順序で、ＡＢＡＢの積層順序にＡＢＣ積層であるγ型層が積層エラーで積層されたものと考えられる。直線状の凹部は図４ｄに示す如く、(００１)面に平行な外表面の１つおきの面に現れる。これを1枚の凹部と呼ぶ。凹部を２枚有する粒子は、２枚が互いに平行で異なる位置に含有される。
図５、図６ｈに記載態様の平板粒子Ｃ₉はエッジ面に成長促進の結晶欠陥を有する為に、平板粒子となる。該欠陥にはラセン転位線欠陥と、双晶面が形成する凹部がある。該凹部が観察される平板粒子の実在は確認された。該粒子では、それが成長を促進する。該凹部が観察されない粒子は、凹部が小さくて観察され難い粒子であるか、またはラセン転位欠陥含有の粒子であろう。
表１に示したように、該平板粒子のγ型含率が高くなっている。これは多くの双晶面を含有している為であろう。
(97)〜(99)記載の平板粒子や(10)〜(12)記載の粒子の形成途中を調べると、核形成時に種々の種類の粒子が形成され、それに続く過程で、(102)記載の熟成が起っている。これは(10)〜(12)や(97)〜(99)記載の粒子が速く成長して大きくなる為である。該熟成は該同時添加を停止させた状態、または熟成が起る程度の低速度の添加状態（Ａｇ⁺および／またはＸ^-溶液の添加）で行う事もできる。
(10)、(11)記載の粒子はまずＣ₉の条件で平板状種晶Ｃ₉₁を形成し、次に、これを表１のＣ₂の条件で成長させる事により、形成する事もできる。この場合、Ｃ₉₁を高アスペクト比化しておくと、最終的に得られる(10)、(11)記載の平板粒子も、高アスペクト比になる。
(10)、(11)記載の平板粒子Ｃ₂、およびＣ₉₁の各平板粒子のアスペクト比（円相当の投影直径／厚さ）は１．５〜３００が好ましく、２〜３００がより好ましい。厚さ（μｍ）は０．０１〜０．５が好ましく、０．０２〜０．３がより好ましい。
【０００９】
（II−３）粒子表面構造。
前記結果から判断すると、Ａｇ⁺過剰域での生成平衡晶癖は図２の粒子で見られる（１００）類面〔（１００）、（０１０）、（１−１０）面〕である。図７で見られる如く、この面はＡｇ⁺とＸ^-が交互に配置された面であり、AgBr系の（１００）面に該当する。表１のＣ₁、Ｃ₂の条件で生成した図２の形状の粒子の六角形状表面はＡ₂値が０．６〜１．０、好ましくは０．９〜１．０であると考えられる。
一方Ｘ^-過剰域で調製した１４面体粒子の六角形状の（００１）面は、〔Ｘ^-からなる表面の合計面積／（００１）表面の合計面積〕＝Ａ₄値が０．６〜１．０、好ましくは０．７０〜１．０であると考えられる。１４面体粒子の（１０１）類面〔（１０１）、（０１１）、（０１−１）面〕はＡ₃が０．６〜１．０、好ましくは０．７０〜１．０と考えられる。従って１４面体粒子の外表面はＸ^-のみが配置された面が大部分を占め、AgBr系の（１１１）面に該当する。
１２面体粒子の外表面は（１００）面と（００１）面と（１０１）面である。これはAgBr系の（１００）面と（１１１）面からなる１４面体粒子に該当する。該（００１）面はＡｇ⁺のみからなる面とＸ^-のみからなる面が存在し、そのＡ₂値は該粒子の成長条件に依存する。
該粒子の生成条件内で、〔Ａｇ⁺濃度（モル／Ｌ）／Ｘ^-濃度（モル／Ｌ）〕＝Ｂ₄が大きくなればなる程、Ａ₂値が大きくなる。従って（３）〜（９）記載の粒子ではＡ₂が０．７０〜１．０である該粒子と、０．３０１〜０．６９９である該粒子と０．０〜０．３０である該粒子を調製できる。Ｂ₄値は０．０１〜１００が好ましい。
なお、これらの粒子のＡ₂〜Ａ₄値は、粒子形成後に乳剤にＡｇ⁺やＸ^-を添加し、乳剤のｐＡｇやｐＩ値を変化させる事によりＢ₄を変化させて変える事ができる。従って（３）〜(15)記載の粒子では、Ａ₂〜Ａ₄値が０．７０〜１．０である粒子と、０．３０１〜０．６９９である粒子と、０．０〜０．３０である粒子を調製できる。粒子形成時にＢ₄を大きく変化させると、生成粒子の形状が変化するので、大きく変化できない。一方、粒子を形成した後にＡｇ⁺またはＩ^-を添加し、Ｂ₄を変化させる方式の方が、粒子変形を殆んど伴わずにＡ₂〜Ａ₄を大きく変化させる事ができるのでより好ましい。
ここで、粒子上に積層されるＸ^-は、Ｉ^-モル％含率が０〜１００、好ましくは５０〜１００、より好ましくは８０〜１００のハロゲンイオン（Ｃｌ^-、Ｂｒ^-、Ｉ^-）を指す。
これらの粒子は各々目的に応じて好ましく用いる事ができる。例えば化学増感剤に対して反応性の高い面に優先的に化学増感核を形成し、潜像分散を抑制する事。優先的にとは、〔化学増感核の生成量＝カルコゲン原子のモル量／cm²〕が他の面の１．５〜１０⁶、好ましくは３〜１０⁶倍、より好ましくは１０〜１０⁶倍である事を指す。
互いに異なる結晶面上に選択的に形成する事が好ましい。（３）〜（９）記載の粒子では（−１１０）面上に優先的に化学増感核を形成する事がより好ましい。化学増感剤の反応性の大きさは通常（Ａｇ⁺のみが配置された面＞Ａｇ⁺とＸ^-が配置された面＞Ｘ^-が配置された面）の順である。
また、増感色素の吸着特性はＡ₂〜Ａ₄値に依存するのでそれらを好ましい値に調節した後に増感色素を添加し、吸着させればよい。また、増感色素を添加し、粒子に吸着させ、飽和吸着量の１０〜１００、好ましくは４０〜１００％、より好ましくは７０〜１００％だけ吸着させた後に、化学増感剤を添加し、増感色素が吸着していない場所に優先的に化学増感核を形成する事が好ましい。優先的にとは前記規定に従う。
また、異なる結晶面に対する増感色素の吸着特性の差を利用して、該色素の被覆率の低い結晶面上に、化学増感核を優先的に形成する事ができる。即ち、増感色素の吸着量（モル／cm²）比＝Ｂ₅＝〔Ｂ₆結晶面上の吸着量／Ｂ₇結晶面上の吸着量〕が０．０〜０．９、好ましくは０．０〜０．４、より好ましくは０．０〜０．２の状態に色素を吸着させた後に、化学増感剤を添加し、Ｂ₆面上に化学増感核を優先的に形成する。
【００１０】
（II−４）粒子形成中のＡｇ⁺、Ｉ^-濃度の調節方法。
粒子１を形成する場合、粒子形成中の反応溶液のＡｇ⁺とＩ^-の濃度を精密に制御する必要がある。その為に(55)〜(79)に記載の方法を用いる事が好ましい。一般にイオン選択電極を溶液中に入れ、比較電極との電位差を測定すると、特定のイオン濃度と該電位差の大きさが相関する。その相関性を利用して、溶液中のイオン濃度を電気信号として検知する方法が化学の分野で多用されている。ＡｇＸ粒子形成の場合は、Ａｇ⁺および／またはＸ^-に選択的に感応する電極が用いられる。具体例を挙げると、金属銀、ＡｇＸ電極（AgI、AgBr、AgClおよびそれらの２種以上の混晶）、金属銀上に該ＡｇＸ電極を積層させた態様、カルコゲン銀電極（Ag₂S、Ag₂Se、Ag₂Teおよびそれらの２種以上の混晶）があり、金属銀、ＡｇＩ、Ａｇ₂Ｓ電極が好ましい。本発明で銀電位とは比較電極に対するこれらの電極電位を指す。
比較電極としては、１０〜６０℃域で安定な電位を示す電極が用いられる。具体例としてカンコウ電極、（Ａｇ／ハロゲン化銀）電極、〔例えば(Ag/AgCl)、(Ag/AgBr)、(Ag/AgI)電極〕があり、(Ag/AgCl)電極がより好ましい。その詳細に関しては文献９の第１２章の記載を参考にできる。
比較電極と反応溶液を塩橋で接合し、電気的導通をとる事により、両電極電位差を測定できる。比較電極を反応溶液中に入れて該電位差を測定する方法と、比較電極を反応溶液の外に置き、測定する方法があり、後者の方がより好ましい。
比較電極の温度を一定に保つ事が好ましく、２０〜３０、好ましくは２３〜２７℃に保つ事が好ましい。比較電極電位が常に安定した電位を示す。この状態で予め、反応溶液中のＡｇ⁺とＩ^-濃度を種々変化させた時の該電位差を種々の温度に対して求めておく。その関係を利用して、粒子形成中の反応溶液の銀電位を測定し、該値を指定値に保つように、添加するＡｇ⁺またはＸ^-を含む溶液の流量を(55)〜(78)記載の方法で制御する。
反応溶液の銀電位を測定し、（該電位―指定電位）差Ｓ₁を求め、その差に比例した信号（ｋ₁S₁）を添加系に送り、該流量を制御する。これは従来公知のＰＩＤ制御のＰ法に該当する。この場合、制御液の添加速度は平衡添加速度Ｓ₁₀〔例えばＡｇ⁺を指定の添加速度Ｓ₁₁（モル／秒）で添加すると、Ｘ^-の平衡添加速度はＳ₁₁になる〕を基準とし、それに対する増減量が該信号と対応する態様が好ましい。該信号は０．０１〜１００、好ましくは０．０３〜３０、より好ましくは０．０３〜５秒毎に送られる。しかし、該差に比例してＸ^-液の流量を上げると、流量の上げすぎにより、電位が指定電位を通りすぎて大きく下りすぎる事、これを修正する為に流量を下げると、電位が指定電位を通りすぎて大きく上りすぎる事、この事がくり返し起る事（これを電位ハンチングと称する）がある。これを防止する為に次の方法が有効である。
１）この現象は添加するＡｇ⁺、Ｘ^-の平衡添加速度に比例して大きくなる。また、制御すべき反応溶液中のイオン種の濃度Ｓ₁₂（モル／Ｌ）に比例して小さくなる。また、反応溶液量（Ｓ₁₃リットル）に比例して小さくなる。その他、反応溶液の温度、ｐＨにも依存する。これらの基本因子を変化させた時のＣＤＪ制御の信号量の好ましい値（ｋ₁ｋ₂Ｓ₁）を求めておく。粒子形成開始前に、（粒子形成時間vsｋ₂）の関係を制御器にメモリーさせておき、（ｋ₁ｋ₂Ｓ₁）の信号で該流量の増減を行う。従ってｋ₁Ｓ₁の信号でハンチングが生じる粒子形成条件の場合は、｜ｋ₂｜は１０^-6〜０．９８、好ましくは１０^-6〜０．７、より好ましくは１０^-4〜０．３が選ばれる。該ハンチングが大きい程、｜ｋ₂｜はより小さい値が選ばれる。該ハンチングに対して、その他、分散媒、添加剤、ＡｇＸ溶剤の種類や添加量も影響するが、それらの効果を｜ｋ₂｜に含ませる事もできる。
２）該ハンチングの大きさは（該電位差vs.経時時間）の積分値の絶対値Ｓ₂に比例するので、Ｓ₂を求め、（ｋ₃＝１.０＋ｋ₄Ｓ₂）を求める。そしてＣＤＪ信号として（ｋ₁ｋ₂Ｓ₁/ｋ₃）を送信する。
３）該ハンチングの周期Ｓ₃秒を求め〔ｋ₅＝１＋ｋ₆／Ｓ₃〕を求めて、ＣＤＪ信号としてｋ₁ｋ₂Ｓ₁／（ｋ₃ｋ₅）を送信する。周期が短くなる程、ｋ₅は大ききなり、流量の増減幅が抑制される。その他、例えば（Ｓ₃＞Ｓ₄）秒に制御したい場合に、実測値がそれに反して（Ｓ₃＜Ｓ₄）の場合には〔ｋ₅＝１−ｋ₆（Ｓ₄−Ｓ₃）／Ｓ₄〕の信号が形成され、ＣＤＪ信号としてｋ₁ｋ₂Ｓ₁／（ｋ₃ｋ₅）を送信する態様がある。ここで周期は前記くり返しの１周期間を指す。該信号値は、１〜１０００、好ましくは３〜１００秒毎に求められ、制御系にフィードバックされる。
４）その他、従来公知のＰＩＤ制御法のＩとＤの機能を用いる事もできる。即ち、ＩはＳ₁が経時時間に対していつまでも減少しない態様を避ける為に、（Ｓ₁対経時時間）積分値に比例して、添加速度の増減量を増す方法である。ＤはＳ₁値の経時時間に対する変化（ｄＳ₁／ｄｔ）が大きすぎる場合に、該増減量を減らし、ゆっくりすぎる場合には増す方法である。
５）２液の指定流量添加法。
Ａｇ−１液とＸ−１液の添加精度が良ければ、Ａｇ−１液とＸ−１液を指定の流量で同時混合添加し、溶液のＡｇ⁺とＩ^-の濃度を精密に制御する事ができる。
６）３液添加方法、例えばＡｇ−１液とＸ−１液を指定流量で添加し、別のＸ−２液を用いてＣＤＪ制御添加する方法。Ｘ−２液の添加速度（モル／秒）が(56)の態様であれば、Ｘ−２液の添加速度が小さくなり、より制御精度が増す。また、（Ｘ−２）液が(65)記載の希薄溶液であれば更に、該制御精度が増す。
該ＰＩＤ制御、パルスモーターの詳細に関して、また、前記の制御に関して、文献８の記載を参考にできる。
【００１１】
（II−５）エピタキシャル粒子。
高ＡｇＩ含率粒子の欠点は次の通り。１）化学増感を施しても、有効な化学増感核が形成され難い。それはＡｇＩがAgBrよりも難溶性であり、カルコゲン銀との溶解度差が小さい為にハロゲン変換作用を受けにくい事が関係する。２）化学増感核の電子捕獲効率が小さい。３）潜像の現像促進作用が小さい。４）現像速度、定着速度が遅い。これらはAgBrに比べてＡｇＩの特性（例えば水に対する溶解性、イオン結合性比率）がAg₂Sの特性に近い為と考えられる。
粒子１を(21)〜(25)、(52)記載のエピタキシャル型態様で用いた時、これらの欠点が抑制される。低ＡｇＩ含率のエピ部に化学増感核が形成され、該核が電子を捕獲し、潜像を形成し、現像開始点となる為である。現像と定着処理の終了までの時間はその処理温度（℃）を２０〜６０、好ましくは３０〜６０域で高くする事により、短縮化される。
該エピ粒子の形成は、(1)記載の乳剤（以下乳剤１と記す）にＡｇ⁺とＸａ^-液を添加して粒子１の表面上の一部にエピ層AgXbを沈積させればよい。この時粒子１に特別の吸着剤を吸着させた状態で該添加する方法と、該吸着なしの状態で添加する方法がある。該吸着剤としてはシアニン色素、かぶり防止剤、オニウム塩化合物、界面活性剤があり、化合物例とその詳細に関しては後述の文献４、６、１１の記載を参考にできる。該吸着量は飽和吸着量の１０〜１００が好ましく、３０〜１００％がより好ましい。該エピ形成に関しては、文献２の記載を参考にできる。吸着剤を吸着させた方が、エピ形成場所が限定され、好ましい。
粒子１の粒子内に、および／または該エピ相内に(25)〜(30)記載の態様でドープ剤をドープする事ができる。該ドープ剤の存在下にＡｇ⁺とＸ^-を添加し、粒子またはエピ相を成長させると、ドープ剤がドープされる。ドープ剤に関しては後記文献４、６の記載を参考にできる。ドープ剤の存在（モル／Ｌ）は１０^-1〜１０^-8、好ましくは１０^-2〜１０^-7が好ましい。
該ドープ剤が効率良くドープされる為には、まずドープ剤が粒子表面に優先的に強く吸着され、表面から離れない事である。その為にはドープ剤自身が強い吸着特性を有するか、強い吸着基を有するドープ剤（例えば金属錯体では配位子が該特性を有する態様）を用いればよい。強く吸着した状態で、その上にＡｇＸが沈積すればドープされる。ドープ剤がＡｇＩ結晶格子中に効率的に組込まれる為にはＡｇＩと同じ４配位型構造のドープ剤が好ましい。
該エピ形成時または該ドープ時のｐＸ＝−log〔Ｘ^-モル／Ｌ〕は０．５〜１０、好ましくは１〜７、ｐＨは１〜１２、好ましくは２〜１０、温度（℃）は５〜９５、好ましくは１０〜８５、分散媒濃度（ｇ／Ｌ）は１〜１００、好ましくは５〜４０で、最も好ましい組合せを選ぶ事ができる。
【００１２】
（II−６）化学増感、分光増感等。
本発明の乳剤に化学増感剤を添加し、化学増感する事ができる。化学増感剤としてカルコゲン増感剤（イオウ、セレン、テルル増感剤）、貴金属増感剤（金、第８族金属化合物）、還元増感剤の単独、その２種以上のあらゆる比率での併用で用いる事ができる。(50)のAgi⁺濃度低下剤としてかぶり防止剤が有効である。
粒子表面のＡｇ⁺と結合し、〔Ａｇ⁺（表面）⇔Agi⁺〕の化学平衡を左へシフトさせ、Agi⁺濃度を減少させる。これらの化合物、使用法等の詳細に関しては、文献４、６、１１の記載を参考にできる。
粒子１は４３０nmより短波長の青光吸収係数は大きいが、それよりも長波長の青光吸収係数は小さい。従って乳剤１を感材の青感層に用いる場合には、１種以上の青感層用増感色素を添加し、粒子に吸着させ、分光増感する事が好ましい。
緑感層に用いる場合には１種以上の緑感層用増感色素を添加し、赤感層に用いる場合には１種以上の赤感層用増感色素を添加し、分光増感する、それぞれ(53)記載の態様で用い、粒子に色素を飽和吸着量の１０〜１００、好ましくは３０〜１００％だけ吸着させた態様で用いる。
その他、(54)記載の態様で用いる事もできる。３６０〜４４０nm波長域の光を照射して感光させる感光材料に用いる事もできる。光はあらゆる光を用いる事ができ、自然光、ＬＥＤ光、レーザー光、蛍光、放電光、高温物質光等がある。光源に関しては文献７の記載を、該シアニン色素の化合物例と使用方法の詳細に関しては文献４、６、１１の記載を参考にできる。前記色素種は１〜１０種を好ましく用いる事ができ、互いに吸収スペクトル波形の異なる色素や吸着配向の異なる色素を２種以上併用し、好ましい吸収スペクトル波形と吸着配向を形成する事が好ましい。
また、乳剤粒子に吸着させ光を照射した時に、１光子を吸収して２〜４コの電子をＡｇＸ粒子に与える化合物を１０^-8〜１０^-1、好ましくは１０^-6〜１０^-2モル／モルＡｇＸの添加量で添加する事が好ましい。該化合物の詳細に関しては文献１２の記載を参考にできる。
【００１３】
（II−７）粒子１のその他の利用。
粒子１は水に対する溶解度が低い為、可視光に対して透明性が高い超微粒子を形成する事ができる。この為、次の態様で写真感材に利用する事ができる。１）感光層および／または非感光層の分散媒層に粒子１の超微粒子乳剤を添加し、分散させ、分散媒層の可視光に対する屈折率を上げる。感光性ＡｇＸ粒子とその周りの分散媒層との屈折率差を小さくし、ＡｇＸ粒子の光散乱強度を減少させ、現像処理して得られる写真像の鮮鋭度が増す。酸化チタンの如き他の屈折率上昇剤とあらゆる比率〔（粒子１／粒子１以外の他の屈折率上昇剤）のモル量比＝１０^-5〜１０⁵、好ましくは１０^-3〜１０³〕で併用して用いる事もできる。これらの詳細および実施態様に関しては文献５の記載を参考できる。
２）紫外線吸収剤として感光層および／または非感光層の分散媒層に該超微粒子を分散させる。粒子１の固有吸収端は直接許容遷移であり、吸収係数が大きい事から、約４２０nm波長以下の紫外線吸収材料として有効である。この場合、他の紫外線吸収剤とあらゆるモル比率〔（粒子１／粒子１以外の他の紫外線吸収剤）のモル量比が１０^-5〜１０⁵、好ましくは１０^-3〜１０³〕で併用して用いる事もできる。他の紫外線吸収剤に関しては文献４、５の記載を参考にできる。
(16)記載の微粒子を形成する為には粒子１を低溶解度の条件で形成する事が好ましい。その為にはＡｇＸ溶剤（Ａｇ⁺と可溶性錯体を形成する化合物）が実質的に存在しない条件、即ち、その濃度（モル／Ｌ）は０〜１０^-1が好ましく、０〜１０^-3がより好ましく、０〜１０^-6が更に好ましい。また、粒子１の溶解度曲線〔銀の溶解濃度（モル／Ｌ）、対、ｐＡｇの関係を表わす曲線〕で、溶解度が最低溶解度の１．０〜６、好ましくは１．０〜３倍のｐＡｇの条件が好ましい。
該条件ではＡｇ_nＸ_mの錯体濃度も低い為、粒子に結晶欠陥も入り難い為、より小さい微粒子が形成される。
具体的には(113)に記載の条件を用いる事が好ましい。
また、核形成時のＡｇ⁺とＸ^-のダブルジェット添加速度を大きくし、多くの核を形成し、短時間で粒子形成を終了すればよい。即ち、(104)記載の方法を用いればよい。しかし、高速添加すると、無制御な欠陥を有する粒子の生成比率が増す。この場合は、(106)記載の方法を用い、核の保護コロイド性を高くする事が好ましい。更には低温で核形成すればよく、下記条件を用いればよい。
欠陥ができるだけ少ない核や種晶を形成する為には、核形成時の該Ａｇ⁺とＸ^-の添加速度（モル／分）を遅くすればよく、(105)の条件を用いればよい。(106)の方法を併用する事がより好ましい。但し生成核数は少なくなる。必要に応じて(74)、(75)の方法を用いて乳剤を濃縮する事が好ましい。
また、反応溶液の温度の他、ｐＨとｐＡｇ、ｐＩの前記組合せを選ぶ事により、生成粒子サイズが変化するので、最も好ましい組合せを選ぶ事が好ましい。分散媒とＡｇＸ粒子の相互作用が変化し、該サイズが変化する。
(111)、(112)の態様で添加すると、添加溶液が反応溶液と同等の温度で添加される為に、特定の粒子の作り分けが良くなり、より均一な性能の単分散な粒子が形成され、好ましい。図１４にその装置例を示した。
温度（℃）は低い方が溶解度が低く、０〜７０が好ましく、１〜４０がより好ましく、１〜３０が更に好ましい。この場合、分散媒は該低温でゲル化しない分散媒が好ましく、１〜２０℃で、２．０質量％溶液を１５分間静止した時の粘度（Pa・秒）が１０^-4〜０．２、好ましくは１０^-4〜０．１、より好ましくは１０^-4〜０．０５である分散媒が好ましい。前記ゼラチンの場合は、質量平均分子量が３０００〜５０，０００が好ましく、３０００〜３０，０００がより好ましい。また(107)、(108)記載の分散媒も好ましい。
【００１４】
（II−８）その他。
平坦なガラス基板上に該１２面体ＡｇＩ粒子を沈降配向させ、乾燥後にCｕKβ線でＸ線回折を測定すると図８の（ａ）の回折パターンが得られ、（００１）面と（１００）面と（１０１）面の回折ピークが残る。従って、基板に平行に配向した結晶面は（００１）面と（１００）面と（１０１）面である。該六角柱粒子を同様に配向させ、Ｘ線回折を測定すると、図８の（ｂ）の回折パターンが得られ、（１００）と（００１）面の回折パターンが残る。従って、基板に平行に配向した結晶面は（１００）面と（００１）面である。図４に記載の１４面体粒子を同様に配向させ、Ｘ線回折を測定すると、図８の（ｃ）の回折パターンが得られ、（００１）面と（１０１）面の回折パターンが残る。従って、基板に平行に配向した結晶面は（００１）面と（１０１）面である。
粒子が平坦な結晶面を有すれば、その面積に比例して、該結晶面が基板面上に平行密着する確立を有する為、それに比例した強度の結晶面の回折ピークが残る。
【００１５】
【表２】

【００１６】
（９）〜(15)記載の乳剤粒子のゼラチン分散物の乾膜の誘電損失測定を行ない、粒子の暗電導度（σ）特性を調べると、次の事がいえる。２５℃で約０．２μm直径の１２面体粒子Ｃ₅は２つの損失ピークを与え、低周波数側の大きいピーク（fL）は約１０⁶Hzにあり、高周波数側の小さいピーク(fH)は１０⁸あたりにあると推定される。この挙動は同一サイズの八面体AgBr粒子の特性に近い。該粒子にかぶり防止剤１〜３を吸着させるとｆLとｆHは低周波数側にシフトする事と、後記の該粒子サイズ依存性の結果から、ｆLに該当する暗電導度成分は、粒子表面サイトのＡｇ⁺が粒子内に入り込んで生じた格子間銀イオンAgi⁺と考えられる。
表３の（３−１）〜（３−７）記載の１２面体粒子のfLの温度（T°K）変化を測定し、図９にlog（σT）vs.1000/Tをプロットした。その直線の勾配から σT＝Aexp(−△E／ｋT)の△Eを求め、表３に示した。但し、〔fLのピーク周波数＝１０¹¹σ〕と近似した。２５０°Ｋ以上の領域と２５０°Ｋ以下の領域で、該傾きが少し異なったので、両方の△E値を記載した。かぶり防止剤添加によるｆLの低下幅がAgBr系に比べで小さかった。ＡｇＩは軟らかい酸原子と軟らかい塩基原子間の結合であり、硬い酸原子と硬い塩基原子間の結合に比べて軟らかい結合である。結合自由エネルギー△ＧもＡｇＢｒより小さい。この為結晶内でＡｇｉが生成し易く、かつ動き易い。それを反映した現象であろう。これに対しては(26)〜(36)の手法を併用し、更にｆL値を１０^-3〜０．９倍に低下させる事が好ましい。〔△E＝△G_i（Agi⁺の生成エネルギー）＋Ｕ(Agi⁺の移動の活性化エネルギー)〕であり、ＡｇＩではＵ＝０であるから、△E≒△G_iを表わす。
粒子サイズが大きくなるにつれ、ｆL、ｆHはより低周波数にシフトした。例えば約１．１μｍ直径の粒子ではｆLは１０^5.24であった。実施例６の６角柱粒子Ｃ₁（平均直径０．６５μｍ、平均厚さ０．２６μｍ）ではfLは１０^4.5、ｆHは１０^6.05であり、これにかぶり防止剤２を吸着させると、ｆLは減少して消失し、ｆHが１０^5.1の１つのピークになる。この挙動は表１のＣ₉の条件で得られた平板粒子Ｃ₉（平均厚さ０．２５μｍ、平均直径２μｍ）の挙動と似ている。粒子Ｃ₉のfLは１０^4.8で、ｆHは１０^5.8であり、これに該防止剤２を吸着させると、該２つの周波数は殆んど同じで、（ｆL／fH）のピーク強度比が逆転（1/0.95→0.94/1）した。
両粒子では、主平面に平行に双晶面が入っており、それがAgi⁺の移動を防げ、ｆLの周波数を下げていると考えられる。粒子Ｃ₁やＣ₉の主平面が電極面と平行に配向した場合、主平面の表面伝導度は誘電損失に寄与しない。側面や、一部の該非平行に配向した主平面の表面伝導が寄与するだけの為に、fHの周波数が低下していると考えられる。
前記かぶり防止剤の添加量はいずれも約３×１０^-3モル／モルAgX（表３参照）である。
【００１７】
【化１】

【００１８】
該Ｃ₅の乳剤のｐＨ、ｐＡｇを変化させた時のfLの変化をAgBr粒子の場合と比較して表３（ｆL値10^XのX値を記した）に示した。表３はタイプ乳剤とタイプ乳剤にＨＮＯ₃液を加えてｐＨ３にしたもの、ＮａＯＨ液を加えてｐＨ１０．４にしたもの、ＡｇＮＯ₃液を加えてｐＡｇ２．２にしたもの、ＡｇＢｒにはＢｒ^-を、ＡｇＩにはＩ^-液を加えてｐＸ＝２．０としたもの、かぶり防止剤１又は２を（３×１０^-3モル／モルAgX）添加したものの該結果を表わす。立方体AgBr、Ｂ₆と八面体AgBr、Ｂ₇と１２面体AgI、Ｃ₅ではタイプよりもｐH↑でAgi⁺濃度が↓した。これはＧｅｌの−ＮＨ₃ ⁺がＡｇｓ⁺（粒子表面のＡｇ⁺）を不安定にしていたが、ｐＨ↑で−ＮＨ₂に変化し、これがＡｇｓ⁺に配位結合してＡｇｓ⁺を安定化し、Ａｇｓ⁺⇔Ａｇｉ⁺の平衡を左側に移動させた為と解される。Ｂ₆とＢ₇はタイプよりもｐH↓でその逆の現象が生じてAgi⁺濃度が↑した。これはＧｅｌの−ＣＯＯ^-がＡｇｓ⁺を安定化していたが、ｐＨ↓で−ＣＯＯＨに変化し、Ａｇｓ⁺の安定化作用が減少し、該平衡が右に移動した為と解される。しかしＣ₅では該濃度が減少した。これはＡｇＩの疎水性が高く、有機化合物に近い為に、−ＣＯＯ^-の該安定化効果よりも、−ＣＯＯＨとの分子間力による安定化効果の方が大きい為であろう。ｐＨ↑の場合も非イオン性の−ＮＨ₂の分子間力による安定化効果と考えられる。分散媒が粒子表面の原子を安定化させる機構として次の機構がある。１）クーロン相互作用、２）電子対を有するＳ、Ｎ、Ｏ原子とＡｇ⁺との配位結合による安定化作用。Ｈ₂Ｏの配位結合も含まれる。３）−ＣＯＯＨやπ共役結合を有する有機化合物と表面のＡｇＸとの分子間力による相互作用。それぞれの作用の寄与率がＡｇＢｒ系とＡｇＩ系で異なる為と解せる。分子間力に関しては、化学辞典、分子間力、東京化学同人（1994年）の記載を参考にできる。
Ｂ₆とＢ₇ではAg⁺濃度↑でAgi⁺濃度↓した。これは粒子表面にＡｇ⁺が吸着し、粒子全体が＋帯電化することにより、粒子内のＡｇｉ⁺の電気的エネルギーレベルが△ＥｅＶだけ高くなり、Ａｇｉ⁺濃度が減少する為であろう。該表面電荷による粒子内の電位はGaussの法則によるとほぼ等電位であり（従って電位勾配は存在しない）、Ａｇｉ⁺濃度は粒子内のすべての場所で減少する。該減少量は通常、ｅｘｐ（_-ΔＥ／ＫＴ）に比例する。ここでＫはBoltzman定数、Ｔは絶対温度を表わし、単位はＫＴｅＶである。
一方、Ｃ₅ではＡｇ⁺濃度↑でＡｇｉ⁺濃度は逆に増加した。その理由は次の通り。ＡｇＩ粒子とＡｇ⁺とのイオン的相互作用が小さい（ＡｇＩは疎水性）為、該レベル↑が小さい。この為、吸着したＡｇ⁺はＡｇｉ⁺となり、（Ａｇｓ⁺⇔Ａｇｉ⁺）の平衡を右側へ移動させ、該濃度を増すという機構。またはＡｇＩの格子間隔が大きい為に、Ａｇ⁺がその空隙部に直接入り込む機構。または、ＡｇＩは４配位結合で、共有結合性が大きい（結合電子の局在性が大きい）為に、有機高分子の一種と見なす事ができる。従って、溶液中のＡｇ⁺がその高分子の分子間隙間にしみ込んだ態様とも考えられる。但し、Ａｇｉ⁺の動きはＩ^-との相互作用で束縛されている為にその動きは誘電損失特性も示す。Br^-濃度↑でAgi⁺濃度が↑した。これは上記と逆の効果であろう。
Ｃ₅ではＩ^-濃度↑でＡｇｉ⁺濃度が少し減少した。これはＩ^-が粒子表面のＡｇｓ⁺に吸着し、Ａｇｓ⁺濃度を下げる効果。該Ｉ^-が溶液中のＡｇ⁺の濃度を下げ、（溶液中のＡｇ⁺⇔Ａｇｓ⁺＋Ａｇi⁺）の化学平衡を左側にシフトさせた効果が考えられる。
ＡｇＩは該有機高分子に近い特性を有する為に電子の局在性が高く、電気伝導度性が低い。その為、結晶内での光電導度がＡｇＣｌ、ＡｇＢｒと比べて低いという特徴も有する。
従って、AgI系はAgBr系とは異なる感性で、乳剤のｐH、pAg、pIの最適組合せを選ぶ必要がある。但し、表３のタイプ乳剤のｐHは６．４、pAgは中性（pAg＝ｐX）である。
【００１９】
【表３】

【００２０】
β型含率が約１００％のAgI １２面体粒子を、ガラス板上に配向させ、Ｘ線回折を測定する。次に該試料をそのまま２５０〜３００℃でアニールした後、急冷し、γ型化させた後にＸ線回折を測定すると、最大の２１．３°の回折ピークが増大する。この事から、β型の（００１）面がγ型の（１１１）面に変化した事が分る。即ち、β型の〔００１〕ベクトル方向がγ型の〔１１１〕方向に変化した事が分る。
これは１つの結晶内においてβ型とγ型が互いに前記積層欠陥として共存できる事を示している。またその実例はＺｎＳ結晶で見られ、例えばPhilosophical Magazine B,279〜297(2001年）の記載を参考に出来る。図７の〔００１〕方向でＡｇ⁺層の積層位置が（ＡＢＡＢＡＢ／ＣＢＡＢＡ）や（ＡＢＡＢＡＢ／ＣＢＡＣＢＡ）となれば、／の所が双晶面になる。
本発明のＡｇＸ乳剤、およびその応用に関し、その他、特開２０００−２０１８１０号の（００６７）〜（００８７）と、特開２００１−２５５６１１号の（Ｉ−８）項の記載を採用する事ができる。
本発明の乳剤の熱現像感材への適用に関しては後記文献１３の記載を、他の感材への適用に関しては文献１４の記載を参考にできる。
(123)記載の非感光性有機銀塩、熱現像剤、バインダー、支持体に関しては文献１３の記載を参考にできる。
（文献）
１．B.L.J.Byerleyら Journal of Photographic Science, 18巻、53〜59(1970 年)。米国特許第４６７２０２６号、同第４４１４３１０号、同４１８４８７ ８号。
J.E.Maskasky, Physical Review,B43巻 5769〜5772(1991年)。
２．J.E.Maskasky, Phot. Sci.Eng. 25巻, 96〜101(1981年)、米国特許第４０ ９４０８４号、第４１４２９００号、第４４５９３５３号。
３．G.C.Farnell, Journal of Photographic Science, 22巻、228〜237(1974年 )。
４．Research Disclosure 誌、item 17643(1978年12月)、同item 38957(1996 年９月)。
５．欧州特許第９３０５３２Ａ、特開平２０００−３４７３３６号。
６．特願２００１−２９７０２３号、特開２００１−２０１８１０号、特開２００１−２５５６１１号、特開２０００−３４７３３６号、特開平８−６９０６９号、ＵＳ５，３６０，７１２号。
７．久保田広ら編、光学技術ハンドブック、朝倉書店（1975年）。南茂夫ら編、分光技術ハンドブック、朝倉書店(1990年)。
８．化学工業協会編、化学装置便覧、第21章、丸善（1989年）。
９．日本化学会編、化学便覧、基礎編、丸善(1984年)。
10. T.H.James and W.Vanslow Phot.Sci.Eng.,5巻，21〜29(1961年)。
11．T.H.James編、The Theory of the Photographic Process, 第４版、Macmil lan(1977年)。
12．特願２００１−８００号、同８６１６１号、特開２０００−２２１６２号、米国特許第５７４７２３５号、同５７４７２３６号、同６０５４２６０号、同５９９４０５１号。
13．特願２００１−３４９０３１号、同２００１−３４２９８３号、同２００１−３３５６１３号、特開２００１−３３９１１号。
14．特開昭５９−１１９３５０号、同５９−１１９３４４号、米国特許第４６７２０２６号。
【００２１】
【実施例】
以下の「実施例１」、「実施例２」、「実施例３」、「実施例４」、「実施例５」及び「実施例１２」を、それぞれ「参考実施例１」、「参考実施例２」、「参考実施例３」、「参考実施例４」、「参考実施例５」及び「参考実施例１２」と読み替えるものとする。
実施例１．
分散媒溶液１（ゼラチン１を２５ｇ、水１２００ml、KI ０．１ｇを含みpH６．０）を反応容器に入れ、温度を７５℃に保ち、攪拌しながらＡｇ−１液（AgNO₃を１００ml中に３．４ｇ含む）とＸ−１液（KIを１００ml中に３．３６ｇ）を４ml／分で１０分間、同時混合添加し、種晶形成した。２分間熟成した後に、７５℃でＡｇ−２液（AgNO₃を１００ml中に１７ｇ含む）とＸ−２液（KIを１００ml中に１６．７ｇ含む）を用いて、銀電位（金属銀電極、対、２５℃飽和カロメル比較電極、が示す電位。両者はKNO₃含有のカンテン橋で結合されている）を−４０ｍVに保つCDJ添加をした。Ａｇ−２液のスタート流量は２．４ml／分、加速流量０．１６ml／分で９８分間添加した。
この時点で乳剤を１ml採取し、増感色素１を飽和吸着させた後に遠心分離してゼラチンを除去した。水を添加して再分散させ、コロジオン膜を張ったメッシュ板上に１滴をのせ、乾燥させた。カーボン蒸着、Ａｕ−Ｐｄシャドーイング、定着を行ない、レプリカ膜の透過型電顕像（TEM像）を撮影した。粒子の該直径のばらつきの変動係数は０．０６５であり、平均直径は０．２４μｍであった。粒子形は（９）と図２に示した１２面体粒子が、粒子の投影面積の合計の９９％以上を占めた。
Ｘ−２液の添加速度（モル／秒）は、Ａｇ−２液の添加速度（モル／秒）と同一速度である事を基準とし、銀電位が−４０mVより高くなればその電位差に比例して添加速度を増し、低くなればその電位差に比例して下げる方式でCDJ添加した。（II−４）の１）で記載した如く、予備実験で求めたｋ₂を入れたCDJ添加により、CDJ中の電位の振れ幅は、−４０mVを基準として−１４〜＋１４mV内であった。また、全実施例の各添加液は孔数８００の中空管型ゴム多孔膜を通して、直接液中に添加した。これはゴム管に０．５mm直径の針を刺して孔を開けたもので、添加しない時は、孔は閉状態である。
溶液添加は１つの溶液の添加に対し、２つのプランジャーポンプを用いて、(78)記載の交互添加方式の態様で添加した。
【００２２】
実施例２．
実施例１でCDJ添加成長を次の如くにする以外は同じにした。該Ａｇ−２の添加態様は同じだが、Ｘ−２液の添加は初期流量２．２ml／分、加速流量０．１４７ml／分で９８分間、Ａｇ−２と同時混合添加した。この時Ｘ−２１液（１００ml中にKI４．１５ｇ含む）の添加速度を制御して同時混合添加する事により、銀電位を−４０mVに制御した。スタート流量は０．８ml／分で、添加開始の１０秒後から制御した。この制御法による該電位の振れ幅は−４０mVを基準として−１４〜＋１４mV内であった。
得られた乳剤粒子の該TEM像を撮影し、図１０に示した。平均直径は０．２４μｍで、変動係数は０．０５８であった。該１２面体粒子が粒子の投影面積の合計の９９％以上を占めた。
【００２３】
実施例３．
分散媒溶液３（ゼラチン１を３５ｇ、水１５００ml、KIを０．０５ｇ含み、pH６．０）を反応容器に入れ、温度を６２℃に保ち、攪拌しながら、Ａｇ−３１液（１００ml中にAgNO₃を３０ｇ含む）とＸ−３１液（１００ml中にKIを２９．４ｇとゼラチン２を１ｇ含む）を２５ml／分で８分間、直接に液中に、該多孔膜を通して同時混合添加した。
次にスタート流量２５ml／分、加速流量３ml／分で４分間、同時混合添加した。いずれも添加は該交互添加方式を用いた。
得られた乳剤粒子の該ＴＥＭ像を撮影した。平均直径が０．０４μｍで、直径分布の変動係数は０．１０であった。該乳剤の８０mlを採取し、分散媒溶媒３に添加し、７５℃でＡｇ−２液とＸ−２液を用いて、初期流量３．４ml／分、加速流量０．２４ml／分で５０分間、実施例１と同様にして、−４０mVのCDJ添加した。得られた乳剤粒子の該TEM像を撮影した所、投影面積の９８％以上は該１２面体粒子であった。
【００２４】
実施例４．
実施例３で次の事以外は同じにした。Ａｇ−３１液とＸ−３１液の添加速度を１２ml／分で８分間、同時混合添加した。次にスタート流量１２ml／分、加速流量１．２ml／分で１２分間、同時混合添加した。得られた乳剤粒子の平均直径は０．０６μｍで、直径分布の変動係数は０．０９であった。該粒子を実施例３と同様に成長させた所、投影面積の９９％以上は該１２面体粒子であった。
【００２５】
実施例５．
分散媒溶液５（ゼラチン１を２５ｇ、水１２００mlを含み、NaOHでpH１０．０に調節した溶液にAgNO₃を１．２ｇ溶解させた液）を反応容器に入れ、温度を７５℃に保ち、攪拌しながらＡｇ−１液とＸ−４１液（１００ml中にKIを３．３ｇ含む）を４ml／分で１０分間、同時混合添加した。次にＡｇ−２液とＸ−４２液（１００ml中にKIを１６．５６ｇ含む）を用いて、実施例１と同様にして、銀電位を３６０mVに保つCDJ添加をした。Ａｇ−２の添加は初期流量２．４ml／分、加速流量０．１６ml／分で９８分間添加した。
得られた乳剤粒子の該TEM像を撮影し、図１１に示した。粒子構造は、(33)のＡ₅値の平均値が約１．１６の楕円球状であった。平均直径が０．３４μｍで、その直径分布の変動係数は０．０８であった。(33)記載の該粒子が粒子の投影面積の合計の９７％以上を占めた。
該粒子を実施例３と同様に、表１のＣ₅の条件でCDJ-40mVで成長させた所、投影面積の合計の９６％以上が該１２面体粒子であった。
【００２６】
実施例６．
分散媒溶液６（ゼラチン１を２５ｇ、水１２００mlを含み、HNO₃でpH２．０に調節した溶液にAgNO₃１．２ｇ溶解させた液）を反応容器に入れ、温度を７５℃に保ち、攪拌しながらＡｇ−１液とＸ−４１液を４ml／分で１０分間、同時混合添加した。次にＡｇ−２液とＸ−４２液を用いて、実施例１と同様にして、銀電位３９１mVに保つCDJ添加をした。Ａｇ−２の添加は初期流量２．４ml／分、加速流量０．１６ml／分で９８分間添加した。
得られた乳剤粒子のTEM像を撮影した所、粒子形状は図６のｄに示した六角柱状粒子であった。平均直径０．６５μｍ、平均厚さ０．２６μｍ、直径分布の変動係数は０．１４であり、該粒子が全粒子の投影面積の合計の９６％以上を占めた。
【００２７】
実施例７．
分散媒溶液１を反応容器に入れ、温度を４０℃に保ち、終始攪拌しながら、Ａｇ−１液とＸ−１液を４ml／分で８分間、同時混合添加した。次に温度を７５℃に上げ、Ａｇ−２とＸ−２を用い、実施例１と同じ方法で９０分間、−４０mVのCDJ添加した。Ａｇ−２のスタート流量は２．４ml／分、直線加速流量０．２４ml／分で行った。乳剤を１ml採取し、粒子の該レプリカ膜のTEM像をとり、図１２に示した。粒子直径のばらつきの変動係数は０．０６であり、平均直径は０．２１μｍであり、粒子形は図４に示した非対称１４面体粒子であった。該直径分布の変動係数は０．０８７であった。(37)のＡ₆の平均値は約０．２７であり、そのばらつきの分布の変動係数は０．１２であった。
後は実施例１と同様に乳剤の水洗、再分散、化学増感、分光増感、添加剤の添加を行ない、PETベース上に塗布し、試料を得た。
【００２８】
実施例８．
分散媒溶液８（ゼラチン１を３０ｇ、水１３００ml、KI０．０５ｇを含み、pH６．０）を反応容器に入れ、温度を４０℃に保ち、攪拌しながらＡｇ−２液とＸ−２液を８ml／分で８分間、同時混合添加した。次に温度を７５℃に上げ、Ａｇ−２液とＸ−２液を実施例１と同じ方法で１８分間、−４０mVのCDJ添加した。スタート流量は２４ml／分で直線加速流量は２．４ml／分であった。
乳剤を１ml採取し、粒子の該レプリカ膜のTEM像をとり、図１３に示した。非対称型の１４面体粒子であった。平均直径は０．１２μｍで、直径分布の変動係数は０．１１で、Ａ₆の平均値は約０．３２であり、そのばらつきの分布の変動係数は０．１４であった。
【００２９】
実施例９．
分散媒溶液９（ゼラチン２を２５ｇ、KIを０．０５ｇを含み、pH６．０）を反応容器に入れ、温度を１８℃に保ち、攪拌しながらＡｇ−２液とＸ−２液を５ml／分で５分間添加した。次にＡｇ−２液とＸ−２液を用いて、実施例１と同態様の銀電位−４０mVのCDJ添加をした。Ａｇ−２液のスタート流量は５ml／分、加速流量は０．７ml／分で２８分間の添加をした。
この時点で乳剤を１ml採取し実施例１と同様にゼラチンと可溶性塩を除去し、コロジオン膜をはり、カーボン蒸着したメッシュ上に粒子を載せた。乾燥させた後、約−１３０℃に冷却し、TEM像を撮像した。粒子の平均直径は０．０２６μｍ、直径分布の変動係数は０．１１であった。
【００３０】
実施例１０．
分散媒溶液９を反応容器に入れ、温度を１８℃に保ち、攪拌しながら、Ａｇ−１液とＸ−３液（１００ml中にKIを３．３６ｇとゼラチン２を１ｇ含み、ｐH６．０）をスタート流量１ml／分、加速流量１２ml／分で２分間添加した。続いて２５ml／分で５分間同時混合添加した。次にＡｇ−２液とＸ−２液を用いて、実施例１と同態様の銀電位−４０mVのCDJ添加をした。Ａｇ−２液のスタート流量は５ml／分、加速流量は０．７ml／分で２８分間の添加をした。
実施例９と同様に、生成粒子のTEM像を撮影した。粒子の平均直径は０．０２４μｍ、直径分布の変動係数は０．０９であった。
但し、ゼラチン１＝アルカリ処理牛骨ゼラチンをイオン交換樹脂を通して脱塩処理したemptyゼラチン。ゼラチン２＝〔ゼラチン１を含む水溶液にHNO₃を添加し、ｐH０．７とし、温度９０℃で加水分解し、質量平均分子量１５０００とした。限外濾過で脱塩し、添加した酸の９５％を除去した後、NaOHでｐH６．０に中和した。H₂O₂を添加し、混合した後、４０℃で１５時間静置した。Metの１００％がスルフィニル基に変化した。〕
【００３１】
比較例１．
分散媒溶液１１（ゼラチン１を２５ｇ、水１２００ml、KIを２ｇ含みpH６．０）を反応容器に入れ、温度を７５℃に保ち、Ａｇ−１液とＸ−１液を４ml／分で１０分間、同時混合添加した。次にＡｇ−２液とＸ−２液を用い、従来法で銀電位を−４０mVに保つCDJ添加を行った。Ａｇ−２のスタート流量は２．４ml／分、加速流量０．１６ml／分で９８分間添加した。CDJ中の銀電位の振れ幅は、設定値に対し、常時７０mV以上の振れ幅（合計で１４０mV以上）であった。
生成した粒子の該レプリカ膜のTEM像を撮影した所、平均直径０．６μｍ、直径分布の変動係数が０．４、３種類以上の多種の形状の粒子を含む多分散粒子であった。
実施例１〜１０と、比較例１で得られた各乳剤に対して、凝集沈降剤１を添加し、温度を３０℃に下げ、ｐHを４．０近傍に下げ、乳剤をフロック化し、沈降させた。上澄み液を除去し、乳剤を３回水洗した後、ｐHを６．４に上げ、温度を４０℃に上げて再分散した。AgNO₃液とKI液を用いて乳剤のpAgを５．５に調節した。４０℃で増感色素１を飽和吸着量の８５％量で添加し、吸着平衡にした後、温度を６０℃に上げ、化学増感剤１を３．５×１０^-4モル／モルAgX量で添加し、５０分間熟成した。温度を４０℃に下げ、かぶり防止剤３を３×１０^-3モル／モルAgXだけ添加し、同様にｐH６．４、pAg５．５に調節し、３０分間攪拌した。
該乳剤を硬膜剤１含有（０．０１ｇ／ｇゼラチン）の保護層と共にPETベース上に塗布し、乾燥させた。密閉容器に入れ、４０℃で１５時間保持し、硬膜反応を促進した。実施例１〜１０の各乳剤の塗布物を試料１〜１０とし、比較例１の乳剤の塗布物を比較１とした。
【００３２】
実施例１１．
実施例３と４で使用するゼラチンをゼラチン３におきかえる以外は同じにしてＡｇＩ乳剤Ｂ₁₁、Ｂ₁₂を形成した。Ｂ₁₁の生成粒子は平均直径０．０５μｍ、直径分布の変動係数は０．１０であった。Ｂ₁₂では生成粒子は平均直径０．０８μｍ、該変動係数は０．０９であった。該乳剤の８０mlを採取し、分散媒溶液３に添加し、実施例３と同様に成長させた所、両者ともに、投影面積の９９％以上は該１２面体粒子であった。
ゼラチン３＝ゼラチン１に無水フタル酸を作用させ、フタル化率８３％としたもの。
Ｂ₁₁、Ｂ₁₂にHNO₃を添加し、ｐH４とし、乳剤をフロック化させ、沈降させ、上澄み液を除去し、３回水洗した。乳剤の水洗後は、前記同様に再分散等の処置を施し、塗布試料Ｂ₁₁、Ｂ₁₂を得た。
塗布試料を光学ウェッジを通して１０^-2秒間の青光（４５０nm以下の波長光）露光した試料と−blue光（５００nm以上の波長光）露光した試料を作り、文献１０に記載のピロガロール現像液で４０℃で５０分間現像した。停止液に１分間浸した後、定着液（Super Fuji Fix）に３０分間浸し、定着し、次に水洗し、乾燥した。そのセンシトメトリーを行ない、（感度／粒状度）比の結果を表４に示した。比較試料に対し、本発明の試料が（感度／粒状度）で優れている事が確認された。
感度は（カブリ＋０．２）の濃度を与える露光量（ルックス・秒）の逆数で表わし、粒状度は試料を（カブリ＋０．２）の濃度を与える光量で１０^-2秒間一様に露光し、現像処理を行ない、直径４８μｍの円形開口を用い、ミクロデンシトメーターで濃度のバラツキを測定し、ｒｍｓ粒状度σを求めた。その詳細は前記文献１１の第２１章E節に記載されている。
【００３３】
実施例１２．
図１４に示したタイプの反応容器（Ｃ₁＝３）に分散媒水溶液（ゼラチン１を３０ｇ、水１５００ｍｌ、ＫＩ ０．０５ｇを含みｐＨ６．５）を入れ、７０℃に保ち、激しく撹拌しながらＡｇ−１２液（１００ｍｌ中にＡｇＮＯ₃を３ｇとゼラチン４を０．６ｇ含む）を１６０ｍｌ／分で、Ｘ−１２液（１００ｍｌ中にＫＩを２９．３ｇとゼラチン４を１ｇ含みｐＨ６．５）を１５７ｍｌ／分で４分間、定流量添加した。この時、同時にＸ−１２０液（１００ｍｌ中にＫＩを３０ｇとゼラチン０．６ｇ含み、ｐＨ６．５）を添加する事により銀電位を−１０ｍＶに一定に保った。電位の振れ幅は指定値に対し、２０ｍＶ以内であった。添加終了直後から恒湿槽に冷水を入れ、１分間で該温度を３０℃に急冷した。これを乳剤１２ａとした。
乳剤１ｍｌを採取し、該色素１を飽和吸着量の約１３０％だけ添加し、２０℃に冷却した。該粒子を実施例９と同様にしてＴＥＭ像を撮影した。粒子の平均直径は約３０ｎｍであり、サイズ分布の変動係数は０．１２であった。
次に該乳剤の２７ｍｌを採取し、反応容器中〔ゼラチン１を２５ｇ、ＫＩを０．０５ｇ、Ｈ₂Ｏ １２５０ｍｌを有し、ｐＨ６．３、６０℃）に入れ、該微粒子を新核が発生しない速度で成長させた。具体的にはＡｇ−１２１液（１００ｍｌ中にＡｇＮＯ₃を５ｇ含有する）とＸ−１２１液（１００ｍｌ中にＫＩを４．９ｇ含む）を用いて、銀電位を１５０ｍＶに保ちながら、実施例１と同様のＣＤＪ添加を１２分間行った。Ａｇ−１２１液の添加流量はスタート流量３ｍｌ／分、加速流量０．３ｍｌ／分であった。この添加の最初の５分間中に温度を７５℃に昇温した。次にＡｇ−２液とＸ−２液を用いて、銀電位を１５０ｍＶに保ちながら同様のＣＤＪ添加した。Ａｇ−２液の初期流量は２．６ｍｌ／分で加速流量は０．２４ｍｌ／分で、８７分間添加した。１分後に冷却を開始し、２分間で温度を３０℃に下げた。これを乳剤１２ｂとした。
乳剤を１ｍｌ採取し、色素１を該飽和吸着量の約１３０％量だけ添加した。該粒子のレプリカ膜のＴＥＭ像を撮影した。約３０００コの粒子を観察した所、９９％の粒子が該１２面体であり、その平均直径は約０．１５５μｍで、サイズ分布の変動係数は０．０８であった。従って、該微粒子は成長させると１２面体になる微粒子であり、(19)項に該当する粒子である。ゼラチン４はゼラチン１を分解酵素で分解し、平均分子量１５０００としたゼラチンである。
【００３４】
実施例１３．
実施例１２と同じ反応容器に分散媒水溶液（ゼラチン４を３０ｇ、水１５００ｍｌを含み、ｐＨ６．５）を入れ、２０℃に保ち、激しく撹拌しながらＡｇ−１２液を１６０ｍｌ／分で、Ｘ−１２液を１５７ｍｌ／分で４分間、同時混合添加した。この時、同時にＸ−１２０液を添加する事により銀電位を１２０ｍＶに保った。電位の振れ幅は指定値に対し２０ｍＶ以内であった。約１５ｎｍであり、サイズ分布の変動係数は約０．１２であった。これを乳剤１３ａとした。
次に該乳剤の２９ｍｌを採取し、反応容器中〔ゼラチン１を２５ｇ、ＫＩを０．０５ｇ、Ｈ₂Ｏ １２５０ｍｌを有し、ｐＨ６．３、５７℃〕に入れ、該微粒子を新核が発生しない速度で成長させた。具体的にはＡｇ−２液とＸ−２液を用いて、銀電位を１５０ｍＶに保ちながら同様のＣＤＪ添加した。Ａｇ−２液のスタート流量は１．８ｍｌ／分、加速流量０．１３ｍｌ／分で１０５分間添加した。1分後に乳剤を１ｍｌ採取し、色素１を添加し、２０℃に冷却した。該粒子のレプリカ膜のＴＥＭ像を撮影した。約３０００コの粒子を観察した所、９９％の粒子がＡ₆値が０．１８〜０．２５の該１４面体粒子であった。Ａ₆の平均値は０．２１であった。平均直径が０．１４μｍ、変動係数０．０８であった。これを乳剤１３ｂとした。
【００３５】
実施例１４．
実施例１２と同じ反応容器に分散媒水溶液１４（ゼラチン１を２５ｇ、ＫＩを１．２ｇ、Ｈ₂Ｏ １２００ｍｌ含み、ＮａＯＨでｐＨ１０．２に調節）を入れ、６５℃に保ちながら、Ａｇ−１液とＸ−１４液（１００ｍｌ中にＫＩを３．５６ｇ含む）を１２ｍｌ／分で１０分間添加した。温度を７５℃に５分間で上げ、１０分間熟成した後、Ａｇ−２液とＸ−１４液（１００ｍｌ中にＫＩを１６．８４ｇ含む）を用いて、−１９０ｍＶのＣＤＪ添加を３５分間行った。スタート流量は７．２ｍｌ／分、加速流量は０．６４ｍｌ／分であった。添加終了後、５分間熟成した後、温度を３０℃に下げた。
乳剤を１ｍｌ採取し、色素１を該飽和吸着量の約１３０％量だけ添加した。該粒子のレプリカ膜のＴＥＭ像を撮影した。約１０００コの粒子を観察した所、約９３％の粒子が図５ｂに示した形状で、Ｃ₂値が１．０〜３．０、アスペクト比が２〜３０の平板粒子であった。平均投影直径は０．８μｍ、平均Ｃ₂＝１．７、平均アスペクト比＝７．５、直径分布の変動係数は約０．２であった。また、表１と同じ手法で求めたγ型の含率は約４５％であった。該乳剤を乳剤１４とした。
実施例１２〜１３で得られた各乳剤に増感色素１を飽和吸着量の８５％量だけ添加し、吸着平衡させた後、沈降剤１を添加し、前記同様に乳剤を水洗した。温度を４０℃に上げ、フタル化率９６％のフタル化牛骨ゼラチンを添加し、乳剤を再分散させ、ｐＨ６．４、ｐＡｇ５とした。化学増感剤２のメタノール溶液を乳剤１２ａ、１３ａには３×１０^-4、乳剤１２ｂ、１３ｂ、１４には１０^-4（モル／モルAgX）だけ添加し、４７℃で６０分間熟成した。温度を４０℃に下げ、潜像形成効率向上剤１を乳剤１２ａ、１３ａには２×１０^-3、乳剤１２ｂ、１４には５×１０^-4（モル／モルAgX）だけ添加し、３０分間攪拌した。かぶり防止剤３を３×１０^-3モル／モルAgXだけ添加し、ｐＨ６．４、ｐＡｇ５．３に調節した。
各乳剤を硬膜剤１含有の前記保護層と共にＰＥＴベース上に塗布し、乾燥させ、前記同様に処理し、試料を順に１２ａ、１２ｂ、１３ａ、１３ｂ、１４とした。塗布試料を前記と同様に露光し、現像処理し、センシトメトリーを行ない、（感度／粒状度）比の結果を表４に示した。比較試料に対し本発明の試料が（感度／粒状度）で優れている事が確認された。
【００３６】
【化２】

【００３７】
【化３】

【００３８】
【表４】

【００３９】
【発明の効果】
本発明のＡｇＸ乳剤および該乳剤含有の写真感光材料を用いる事により、（感度／粒状度）比の優れたＡｇＸ写真感光材料が得られた。
【図面の簡単な説明】
【図１】粒子構造の概略図を表わす。ａは粒子の上面図を表わし、ｂはそれを右横から見た側面図を表わし、ｃは（１０１）面を上面に配置した時の上面を表わす。ｄはａの粒子を斜め上から見た時の粒子構造を表わす。ｅは楕円球状粒子の上面図を表わす。
【図２】粒子構造の概略図を表わす。ａは上面図を、ｂはａの側面矢印方向から見た側面図を、ｃは粒子を斜め上から見た時の粒子構造を表わす。ｄはCとは異なる構造の粒子を斜め上から見た時の構造例を表わす。
【図３】粒子構造の概略図を表わす。ａは上面図を表わし、ｂはａの矢印方向から見た側面図を表わし、ｃは粒子を斜め上から見た時の粒子構造を表わす。
【図４】粒子構造の概略図を表わす。ａは粒子を斜め上から見た時の粒子構造を表わし、ｂはその側面図を表わし、ｃは別の例の粒子を斜め上から見た時の粒子構造を表わす。ｄは凹部を有する１４面体粒子の例を表わす。
【図５】ａ、ｃは平板粒子の上面図を表わし、ｂはａを斜め上から見た時、ｄはｃを斜め上から見た時の粒子構造を表わす。
【図６】ａは図１のａに、ｂは図１のｃに、ｃは図１のｅに、ｄは図２のｃに、ｅは図２のｂに、ｆは図４のａに、ｆ、ｇは図４のａに、ｈは図５のｂ、ｄに該当する粒子のより詳細な粒子構造例を表わす。
【図７】β型ＡｇＩ結晶の単位格子模型を表わす。
【図８】ＡｇＩ粒子のCuKβ線のＸ線回折パターン図（Ｘ線回折強度と２θの関係図）を表わす。ａは該１２面体粒子の、ｂは該六角柱粒子の、ｃは該１４面体粒子の該パターンを表わす。
【図９】１２面体粒子のfLの温度（T°K）変化を表す図。
【図１０】乳剤粒子の粒子構造を表わす粒子のＴＥＭ像。
【図１１】乳剤粒子の粒子構造を表わす粒子のＴＥＭ像。
【図１２】乳剤粒子の粒子構造を表わす粒子のＴＥＭ像。
【図１３】乳剤粒子の粒子構造を表わす粒子のＴＥＭ像。
【図１４】反応装置の横面断面図を表わす。
【符号の説明】
１．ａ₁、ａ₂、ａ₃は結晶構造を表わす３つの結晶軸を表わす。
２．θは入射Ｘ線ビームと基板面間の角度を表わす。
３．４１は凹部を表わす。
４．６−１は反応溶液を表わす。
５．６−２は中空送液管を表わす。
６．６−３は恒温ジャケットを表わす。
７．６−４は恒温水循環装置を表わす。
８．６−５は混合箱を表わす。[0001]
BACKGROUND OF THE INVENTION
  The present invention relates to a silver halide (hereinafter referred to as “AgX”) emulsion useful in the field of photography and a method for producing the same.And photographic photosensitive material using the sameAbout.
[0002]
[Prior art]
1) The conventional AgI particle formation and AgI characteristics are reviewed in the references 1 and 4 and 5) below. However, monodispersed AgI particles and particles with a specific shape are made separately. I have not been told.
2) Since the blue light intrinsic absorption of AgI is based on a direct allowable transition between energy bands, the absorption coefficient of light having a wavelength of 400 to 430 nm is about 100 times larger than that of AgBr. This has the advantage of efficiently absorbing incident blue light. However, due to inefficiency in the subsequent photosensitivity process and development process, an epitaxial AgX part (abbreviated as “epi part”) having a low AgI content is formed on the AgI grains, and a chemical sensitization nucleus is formed in the epi part. An aspect in which a latent image is formed is proposed. Regarding this, reference can be made to the description in Reference 2 below, and reference to the description in Reference 3 for the blue light absorption coefficient.
3) There are many documents regarding the use of AgI particles in photographic light-sensitive materials, and the documents described in Document 4 can be referred to. However, AgI particles have β-type and γ-type crystal structures near room temperature, and many particle shapes exist.^-Since the silver potential of the reaction solution changes greatly with slight variations in concentration, hunting of the silver potential is greatly increased by adding a CDJ (Controlled-Double-jet) for controlling the silver potential. It is difficult to make a monodisperse size, and there is no report of an embodiment that has realized it. Realization of monodispersion is expected to be used for photosensitive materials.
4) AgI particle formation is changed to Ag⁺Excess (Ag⁺Concentration> I^-Concentration), AgI particles having a high content of face-centered cubic structure (hereinafter referred to as “γ structure”) are obtained.^-It is described in Document 1 that AgI particles having a high content of a hexagonal crystal structure (hereinafter referred to as “β structure”) can be obtained when carried out in excess.
5) Regarding the AgI tabular grain emulsion having an aspect ratio of 8 or more, refer to JP-A-59-119350. Regarding the AgI tabular grain emulsion having an γ-type content of 90 mol% or more and an aspect ratio of 8 or more, JP The description of 59-119344 can be referred to.
6) Yellow AgI emulsion grains having a natural light absorption edge near 480 nm (a body-centered cubic α-type structure content is high) are described in Reference 1 and US Pat. No. 4,672,026.
7) Regarding the use of AgI fine particles as a UV absorber in the UV filter layer of a color photograph, the description in US Pat. No. 2,327,764 can be referred to.
8) In the vicinity of AgX tabular grains (AgCl, AgBr, AgBrI and two or more mixed crystals thereof) spectrally sensitized at a high coverage, high AgI content fine particles are present, and the amount of dye stain generated during development processing is reduced. Regarding suppression, reference can be made to the description in US Pat. No. 4,520,0098.
9) Increasing the refractive index of the dispersion medium layer by mixing one or more of high refractive index fine particles and / or atoms, molecules, ions, and complexes into the dispersion medium layer of the photosensitive material to reduce the light scattering intensity of the AgX particles. This is described in Reference 5.
10) Symmetrical tetrahedral AgI particles having the same area of hexagonal surfaces parallel to each other are described in Japanese Patent Publication No. 63-30616 and US Pat. No. 4,094,684.
[0003]
[Problems to be solved by the invention]
An AgX emulsion that provides higher sensitivity and higher image quality than a conventional AgX emulsion is provided.
[0004]
[Means for Solving the Problems]
  The object of the present invention has been achieved by the following means.
(1) In a silver halide emulsion having at least a dispersion medium, water, and silver halide grains, 88 to 100% of the total projected area of the grains has an AgI content (mol%) of 85 to 100. As for the shape, the outer shape other than the size of the particle isAn octahedron having two parallel hexagonal surfaces and six rectangular surfaces on its side surface, or a shape whose corners and / or ridges are roundedA silver halide emulsion that is a single type and has a circle equivalent projected diameter (μm) of 0.002 to 20.
(2) In a silver halide emulsion having at least a dispersion medium, water, and silver halide grains, 88-100% of the total projected area of the grains has an AgI content (mol%) of 85-100. The external shape other than the size of the particles has two parallel hexagonal surfaces and 12 trapezoidal surfaces in a mirror image relationship with each other. A silver halide emulsion which is a single type of tetrahedron and has a circle equivalent projected diameter (μm) of 0.002 to 20.
(3) The sizes of the two hexagonal faces are different in one particle, (small hexagon area / large hexagon area) = A₆Is 0.1 to 0.92. (2) Silver halide emulsions.
(4) Ag⁺Solution containing X and X⁻The aqueous solution containing the aqueous dispersion medium is added to the aqueous dispersion medium containing the hydrophilic dispersion medium at the same time while keeping the silver potential of the solution constant, thereby having at least the dispersion medium, water, and silver halide grains. Particles of 40 to 100% of the total area have an AgI content (mol%) of 85 to 100, and the shape of the particles is an outer shape other than the size of the particles.An octahedron having two parallel hexagonal surfaces and six rectangular surfaces on its side surface, or a shape whose corners and / or ridges are roundedIn a method for producing a silver halide emulsion of a single type and having a grain equivalent projected diameter (μm) of 0.002 to 20, the silver potential amplitude (mV) at 30 to 100% of the addition time Is a method of producing a silver halide emulsion, wherein the specified value is -50 to +50.
(5) Ag ⁺ Solution containing X and X ⁻ The aqueous solution containing the aqueous dispersion medium is added to the aqueous dispersion medium containing the hydrophilic dispersion medium at the same time while keeping the silver potential of the solution constant, thereby having at least the dispersion medium, water, and silver halide grains. Particles with a total area of 40 to 100% have an AgI content (mol%) of 85 to 100, and the shape of the particles is that the outer shapes other than the size of the particles are two parallel hexagonal surfaces, Twelve trapezoidal surfaces are mirror images of each other on the side surface, and are a single type of tetradecahedron combined with the hexagonal surface, and the equivalent circular projected diameter (μm) of the particles is 0.002 to 20. In the method for producing a silver halide emulsion, the silver potential emulsion has an amplitude (mV) of silver potential of -50 to +50 with respect to a specified value at 30 to 100% of the addition time. Manufacturing method.
(6) The Ag⁺Solution and X⁻At least one of the solutions is directly added to the reaction solution through the hollow tube, (the hollow tube length in the reaction solution / the inner diameter of the reaction vessel) ratio = C₁Is 0.5-50 (4) or (5)A method for producing the silver halide emulsion as described.
(7) The silver potential has an amplitude of −30 to +30 with respect to a specified value (4) or (5)A method for producing the silver halide emulsion as described.
(8) The amplitude of the silver potential is −15 to +15 with respect to the specified value (4) or (5)A method for producing the silver halide emulsion as described.
(9) The total projected area of the particles is 88 to 100% (4) or (5)A method for producing the silver halide emulsion as described.
(10) The total projected area of the particles is 95-100% (4) or (5)A method for producing the silver halide emulsion as described.
(11) In a photographic material in which one or both surfaces of a support are coated with one or more silver halide emulsion layers, at least one silver halide emulsion layer is (1)Or (2)A photographic light-sensitive material comprising the photosensitive silver halide emulsion described above.
  The present invention will be described in further detail.(1) to (123) belowDescribe.
  Of the following (1) to (123), those having a citation relationship with (10) and (13), and (10) and (13) are related to the present invention.
  (1) In a silver halide emulsion having at least a dispersion medium, water, and silver halide grains, the AgI content (mol%) is 88 to 100, preferably 95 to 100% of the total projected area of the grains. 85 to 100, preferably 90 to 100, more preferably 95 to 100. The particle shape is a single type of outer shape other than the particle size, and the circle equivalent projected diameter (μm) of the particle is 0.002. A silver halide emulsion characterized by being from -20, preferably from 0.02 to 10.
(2) The coefficient of variation (standard deviation / average diameter) of the diameter distribution of the particles is 0.01 to 0.5, preferably 0.01 to 0.3, more preferably 0.01 to 0.2, The silver halide emulsion as described in (1), which is preferably from 0.01 to 0.1.
(3) The silver halide emulsion as described in (1) or (2), wherein the shape of at least one surface of the grain is a parallelogram or a rounded edge.
(4) The silver halide emulsion as described in (3), wherein the at least one face is a (001) face or a (002) face of a hexagonal AgI crystal structure (hereinafter referred to as β structure) .
(5) The silver halide emulsion as described in (3), wherein the at least one surface is a (101) surface having a β structure.
(6) The silver halide emulsion as described in (3), wherein the at least one surface is a (1-10) surface having a β structure.
(7) The vertex angle of two sets of the parallelogram or the parallelogram formed by extending the straight portion of the edge is about 60 ° and about 120 ° (3) ) Silver halide emulsions as described.
(8) The vertical angles of two sets of the parallelogram or the parallelogram formed by extending the straight portion of the edge are about 73 ° and about 107 ° (3) ) Silver halide emulsions as described.
(9) Description of (1) to (3), wherein the outer shape of the particle is a dodecahedron type particle having 12 parallelogram faces, or the corners and / or ridges thereof are rounded. Silver halide emulsion.
(10) The shape of the particle is two parallel hexagonal surfaces and sixRectangleThe silver halide emulsion as described in (1), which is an octahedron having the following surface or a shape with rounded corners and / or edges.
(11) The silver halide emulsion as described in (10), wherein the hexagonal surface is a (001) surface or a (002) surface having a β structure.
(12) TheRectangleThe silver halide emulsion according to (10), wherein the surface is a (100) plane having a β structure or a plane equivalent to the (100) plane.
(13) The shape of the particles has two parallel hexagonal surfaces and 12 trapezoidal surfaces in a mirror image relationship with each other, and is a tetrahedron combined with the hexagonal surfaces, Or the silver halide emulsion according to (1), wherein the corners and / or ridges are rounded.
(14) The silver halide emulsion as described in (13), wherein the hexagonal surface is a (001) surface or a (002) surface having a β structure.
(15) The silver halide emulsion as described in (13), wherein the trapezoidal surface is a (101) surface or a surface equivalent to the (101) surface [referred to as (101) surface].
(16) The diameter (μm) of 60 to 100, preferably 80 to 100% of the total projected area of the particles is 0.002 to 0.15, preferably 0.002 to 0.1, and more preferably. The silver halide emulsion as described in (1), wherein is from 0.002 to 0.05.
(17) The silver halide emulsion as described in (1), wherein 40 to 100, preferably 70 to 100, more preferably 90 to 100% of the molar amount of all grains in the emulsion is β structure.
(18) The crystal structure of face-centered cubic AgI in the range of 0.1 to 90, preferably 1 to 80, more preferably 10 to 70% of the molar amount of all grains in the emulsion (hereinafter referred to as γ structure). (1) The silver halide emulsion as described in (1) above.
(19) The particle shape when the particles are further grown under the condition that no new crystal defects (twin planes, dislocation lines) are generated is the particle shape according to any one of (3) to (15). The silver halide emulsion as described in (1) above,
(20) The silver halide emulsion as described in any one of (1) to (18), wherein the grain does not contain a twin plane in the grain.
(21) The particle has an AgI content (mol%) of 0 to 40, preferably 0 to 30, more preferably 0 to 20 on the particle surface (refers to one or more sites of a plane, corner, and ridge). (1) The silver halide emulsion as described in (1) above, which has a silver halide epitaxial portion.
(22) The silver halide emulsion as described in (21), wherein the content of AgCl (mol%) in the epitaxial portion is 0 to 100, preferably 30 to 100, more preferably 60 to 100.
(23) The silver halide emulsion as described in (21), wherein the content of AgBr (mol%) in the epitaxial portion is 0 to 100, preferably 30 to 100, more preferably 60 to 100.
(24) (AgX molar amount of the epitaxial portion / AgX molar amount of the host particle) is 10^-5~ 2, preferably 10^-5~ 0.5, more preferably 10^-3The silver halide emulsion according to (21), wherein the silver halide emulsion is -0.3.
(25) A total amount of 10 or more of a single element or a compound having an atomic number of 1 to 92 in addition to silver and halogen in the grains and / or the epitaxial phase.^-9-10^-1, Preferably 10^-8-10^-2The silver halide emulsion as described in (1) or (21), which contains only (mol / mol AgX).
(26) The dopant is a simple substance of a metal atom [atom on the left side of a line connecting boron B and At in the element long periodic table], or a neutral or ionic substance of the metal atom-containing compound, The silver halide emulsion as described in (25), which is more preferably a transition metal atom or a neutral or ionic compound of a compound.
(27) The compound is a metal complex containing 1 to 3 metal atoms and 2 to 20 ligands, wherein one to all of the ligands are inorganic ligands and / or carbon atoms 1 to The silver halide emulsion as described in (26), which is an organic ligand containing 30.
(28) The silver halide emulsion as described in (27), wherein the metal complex is a tetra or hexa coordination complex.
(29) The silver halide according to (27) or (28), wherein the metal complex has one or two organic ligands and the remaining ligand is an inorganic ligand. emulsion.
(30) The particles contain 10 chalcogen atoms (one or more of S, Se, Te) in the particles.^-2-10^-8, More preferably 10^-3-10^-7(Mol / mol AgX) and / or reduced silver 10^-2-10^-8, Preferably 10^-3-10^-7The silver halide emulsion as described in (1), which contains only (mol / mol AgX).
(31) In the (001) plane of the particles, [Ag⁺The total area of the surfaces / total area of the (001) surface] = A₂The silver halide emulsion as described in any one of (4) to (14), which is from 0.70 to 1.0, from 0.301 to 0.699, or from 0.0 to 0.30.
(32) In the (101) surface of the particle, [X⁻The total area of the surfaces consisting of / (101) the total area of the similar surfaces] = A₃The silver halide emulsion according to any one of (5) to (15), characterized in that is 0.0 to 0.30, 0.301 to 0.699, or 0.70 to 1.0 .
(33) The particle shape is an ellipsoidal body having no flat crystal face, and [the length of the longest axis / the length of the shortest axis] = A₅The silver halide emulsion as described in (1), wherein is 1.02 to 1.6, preferably 1.05 to 1.5.
(35) TheRectangleThe silver halide emulsion as described in (10), wherein the surface is a flat surface having no depressions.
(36) TheRectangleThe silver halide emulsion as described in (10) above, wherein the surface has a depression (non-flat portion) in the surface.
(37) The sizes of the two hexagonal surfaces are different in one particle, and (small hexagonal area / large hexagonal area) = A₆Is 0.01 to 0.92, preferably 0.1 to 0.8, more preferably 0.2 to 0.7, and still more preferably 0.3 to 0.6 (13) -The silver halide emulsion in any one of (15).
(38) The particles are [(Ag⁺Concentration (mol / L) / I⁻Concentration (mol / L)) = A₇Is formed in a reaction solution of 3 to ∞, preferably 10 to ∞, more preferably 100 to ∞, and the β structure content (mol%) of the particles is 77 to 100, preferably 80 to 100, and more. The silver halide emulsion as described in (1), which is preferably from 85 to 100.
(39) A₆(37) The silver halide according to (37), wherein the coefficient of variation of the value variation is 0.01 to 0.3, preferably 0.01 to 0.2, more preferably 0.01 to 0.1. emulsion.
(40) The halogenation according to any one of (1) to (17), wherein the grain contains from 1 to 3 twin planes, preferably parallel to the (001) plane. Silver emulsion.
(41) The emulsion grains are Ag⁺Solution containing X and X⁻(3) to (3), wherein the aqueous solution containing a dispersion medium is added by simultaneous mixing and adding to an aqueous solution containing a dispersion medium, and the temperature of the aqueous dispersion medium solution is 45 to 99, preferably 50 to 90 ° C. The silver halide emulsion according to any one of (9).
(42) An emulsion as described in (1) or (16) is added to Ag⁺Solution containing X and X⁻In a method of forming an aqueous solution containing selenium by simultaneously mixing and adding to a hydrophilic aqueous solution, AgNO to be added₃When 1 to 90, preferably 1 to 70, more preferably 1 to 40% of the total amount of the catalyst is added, one or more adsorbents are added.^-4~ 0.9, preferably 10^-4~ 0.7, more preferably 10^-4A method for producing a silver halide emulsion, which is characterized in that the addition is carried out in such a manner that it is reduced to -0.3.
(43) The adsorbent is one or more of a cyanine dye, an antifoggant, the dopant described in the above (25) to (29), a crystal habit controlling agent, and a water-soluble dispersion medium (42) The silver halide emulsion as described.
(44) New particles are generated by the addition, (number of new particles generated / number of particles before the addition) = 0.05 to 10⁵, Preferably 0.2 to 10⁵(42) The silver halide emulsion as described in (42) above.
(45) Ag in an aqueous solution (reaction solution) containing 0.1 to 20, preferably 0.3 to 5% by weight of a dispersion medium of the emulsion described in (1).⁺Solution containing X and⁻(1) The method for producing a silver halide emulsion according to (1), wherein the silver halide emulsion is formed by simultaneously mixing and adding a solution containing.
(46) 30 to 100, preferably 80 to 100% by mass of the dispersion medium is 1 to 100, preferably 50 to 100%, more preferably 70 to 100% of the total number of amino groups of gelatin. The silver halide emulsion as described in (45), characterized in that the gelatin is preferably chemically modified with 1 to 10 organic compounds.
(47) 30 to 100, preferably 70 to 100% by mass of the dispersion medium is phthalated gelatin having a phthalation rate of 0.1 to 93, preferably 10 to 87%, and the resulting emulsion grains are described in (9). (45) The silver halide emulsion as described in (45) above.
(48) The desalting of the AgX emulsion produced in (46) or (47) is carried out by adjusting the pH of the emulsion to 2 to 5, preferably 3 to 4.5, and flocking the emulsion. The AgX emulsion according to any one of (45) to (47),
(49) pAg of the emulsion when the emulsion is coated on a support, or when chemical ripening is performed by adding a chemical sensitizer to the emulsion, or when a sensitizing dye is added and spectrally sensitized The silver halide emulsion as described in (1), wherein is from 3 to 8, preferably from 3.5 to 6.5.
(50) In the emulsion, interstitial silver ions (Agi) of the grains⁺) By adding a concentration reducing agent and adsorbing it to the particles, the particle Agi⁺The silver halide emulsion according to any one of (1) to (40), wherein the concentration is reduced to 0.8 to 0.001 before addition, preferably 0.5 to 0.01 times .
(51) The emulsion contains 10 chalcogen chemical sensitizers (one or more of sulfur sensitizers, Se sensitizers and Te sensitizers) in a total amount of 10^-2-10^-8, Preferably 10^-3-10^-7(Mol / mol AgX) added and chemically sensitized emulsion, wherein the emulsion grains contain chalcogen atoms (S, Se, Te) in a total amount of 10^-2-10^-8, Preferably 10^-3-10^-7(Mol / mol AgX) only and / or the emulsion contains 10 gold sensitizers.^-2-10^-8, Preferably 10^-3-10^-7(Mol / mol AgX) added and chemically sensitized emulsion, wherein the emulsion grains contain 10 atoms of gold.^-2-10^-8, Preferably 10^-3-10^-7The silver halide emulsion as described in (1), which contains only (mol / mol AgX).
(52) The epitaxial portion is chemically sensitized, and chalcogen atoms (S, Se, Te) are added in a total amount of 10^-2-10^-8, Preferably 10^-3-10^-7(Mol / mol AgX) and / or 10 gold atoms^-2-10^-8, Preferably 10^-3-10^-7The silver halide emulsion as described in (21), which contains only (mol / mol AgX).
(53) The emulsion is a spectrally sensitized emulsion to which one or more cyanine dyes are added, and the added amount of the dye is 10 to 150, preferably 30 to 100, of the saturated adsorption amount. The silver halide emulsion according to (1).
(54) The silver halide emulsion as described in (1), wherein the addition amount of one or more cyanine dyes to the emulsion is from 0 to 9.9, preferably from 0 to 3, of the saturated adsorption amount.
(55) Ag⁺Solution containing X and X⁻In the method for producing an emulsion as described in (1), an aqueous solution containing 1 to 30 is added to an aqueous solution containing a hydrophilic dispersion medium while keeping the silver potential of the solution constant. The silver potential amplitude (mV) is preferably −50 to +50, preferably −30 to +30, more preferably −15 to +15 with respect to the specified value at 60 to 100, more preferably 90 to 100%. A method for producing a silver halide emulsion, wherein
(56) The simultaneous addition method is Ag⁺Aqueous solution (Ag-1) and X⁻Adding an aqueous solution containing X (X-1) at a specified flow rate;⁻And an aqueous solution (X-2) containing an aqueous solution (X-2), which is added while controlling the flow rate so as to keep the silver potential at a specified value. ) / Ag-1 solution addition rate (mol / sec)] = A₈10^-4~ 0.8, preferably 10^-3~ 0.4, more preferably 10^-3The method for producing a silver halide emulsion as described in (55), wherein the silver halide emulsion is .about.0.2.
(57) The simultaneous addition method is Ag⁺Aqueous solution (Ag-1) and X⁻Adding an aqueous solution (X-1) containing, at a specified flow rate, and further Ag⁺An aqueous solution containing Ag (Ag-2) is added while controlling the flow rate so as to keep the silver potential at a specified value, and the addition rate of Ag-2 solution (mol / m Sec) / X-1 solution addition rate (mol / sec)] = A₉10^-4~ 0.8, preferably 10^-3~ 0.4, more preferably 10^-3The method for producing a silver halide emulsion as described in (55), wherein the silver halide emulsion is .about.0.2.
(58) The response speed of the silver potential [hunting cycle (seconds)] is preferably 1 to 300, more preferably 4 to 100, according to any one of (55) to (57) A method for producing a silver halide emulsion.
(59) The simultaneous addition method is Ag⁺An aqueous solution containing Ag (Ag-1) is added at a specified flow rate, and X⁻An aqueous solution (X-1) containing a silver halide emulsion according to (55) or (58), wherein the silver potential is added while controlling the flow rate so as to keep the silver potential at a specified potential. Production method.
(60) The simultaneous addition method is X⁻An aqueous solution (X-1) containing is added at a specified flow rate, and Ag is added.⁺An aqueous solution (Ag-1) containing a silver halide emulsion according to (55) or (58), wherein the silver halide emulsion is added by controlling the flow rate so as to keep the silver potential at a specified potential. Production method.
(61) When the measured silver potential is higher than the specified potential, the X is proportional to the magnitude of the difference between both potentials.⁻When the measured silver potential is lower than the specified potential, the rate of addition of the aqueous solution containing⁻The method for producing a silver halide emulsion as described in any one of (56), (58) and (59), wherein the addition rate of the aqueous solution containing is reduced.
(62) When the measured silver potential is higher than the specified potential, the Ag is proportional to the magnitude of the difference between both potentials.⁺If the measured silver potential is lower than the specified potential, the Ag is proportional to the magnitude of the potential difference.⁺The method for producing a silver halide emulsion as described in any one of (55), (57) and (60), wherein the addition rate of the aqueous solution containing is increased.
(63) [the X⁻Of control of addition rate of aqueous solution containing (mol / sec) / addition rate of (Ag-1) (mol / sec)] = A₁₀10^-4~ 0.3, preferably 10^-4The method for producing a silver halide emulsion as described in (61), wherein the silver halide emulsion is .about.0.1.
(64) [The Ag⁺Of control of addition rate of aqueous solution containing (mol / sec) / addition rate of (X-1) (mol / sec)] = A₁₁10^-4~ 0.3, preferably 10^-4The method for producing a silver halide emulsion according to (62), wherein the silver halide emulsion is .about.0.1.
(65) [Concentration of the (X-2) solution (mol / L) / Concentration of the (Ag-1) solution (mol / L) = A₁₂10^-5~ 0.8, preferably 10^-4~ 0.4, more preferably 10^-4The method for producing a silver halide emulsion as described in (56), wherein the silver halide emulsion is .about.0.2.
(66) [Concentration of the (Ag-2) solution (mol / L) / Concentration of the (X-1) solution (mol / L) = A₁₃10^-5~ 0.8, preferably 10^-4~ 0.4, more preferably 10^-4The method for producing a silver halide emulsion as described in (57), wherein the silver halide emulsion is -0.2.
(67) One or more, preferably two or more of the Ag-1, Ag-2, X-1, and X-2 solutions have an added pore number of 2 to 10¹⁰, Preferably 5-10¹⁰The method for producing a silver halide emulsion as described in any one of (55) to (66), wherein the silver halide emulsion is added directly into the reaction solution (under the liquid surface) from the pores of the core.
(68) Nucleation of the particles is caused by Ag⁺Solution containing X and X⁻Is carried out by the simultaneous mixing addition method of an aqueous solution containing [Ag at the start of the addition⁺Addition rate (mol / sec)] = A₁₄In the following 10 minutes, preferably within 5 minutes.⁺Addition rate (mol / sec)] = A₁₅1.5 to ∞, preferably 2 to 10⁵The method for producing a silver halide emulsion as described in (1) or (45), wherein the method is accelerated twice.
(69) The particle formation is performed under vigorous stirring conditions with a stirring blade, and the rotation speed (rpm) of the stirring blade is 30 to 10⁵, Preferably 300-10⁵, More preferably 1000-10⁵(1), (45), (55), (68) The method for producing a silver halide emulsion according to any one of the above.
(70) Conditions under which the crystal defect does not occur are 60 to 95 ° C., pH 5 to 9, I⁻The concentration (mol / L) is preferably 10^-2-10^-6, More preferably 10^-3-10^-4(19) The method for producing a silver halide emulsion as described in (19) above.
(71) Ag added during the formation of the particles⁺Containing solution and / or X⁻Is added to the vicinity of the stirring blade, the flow rate of the liquid generated by the stirring blade is 1 to 0.1, preferably 1 to 0.3, more preferably 1 to the maximum flow rate. (69) The method for producing a silver halide emulsion as described in (69), wherein the location is 0.7 times.
(72) The condition of the reaction solution during the seed crystal formation and the grain growth of the particle is different by one or more of the following, (addition silver amount during grain growth / addition silver amount during seed crystal formation) = A₁₆2-10¹⁰, Preferably 3-10⁷The method for producing a silver halide emulsion as described in (1) or (55), wherein
a) The temperature (° C.) is different by 5 to 95, preferably 10 to 95, more preferably 15 to 95.
b) The pH is different by 0.3-12, preferably 1-11.
c) pAg or pI differ by 0.2 to 12, preferably 0.5 to 6.
(73) The porous addition hole or the porous addition system having the porous addition hole is composed of a rubber elastic body, and the rubber elastic body has an original length of 1.05 to 20, preferably 1.1 in the operating temperature range. -20, more preferably 1.3 to 10 times the length of the elastically deformable substance, its rubber modulus [Young's modulus (N / m²)] Is 10⁴-10⁹, Preferably 10⁵-10⁸(67) The method for producing a silver halide emulsion as described above.
(74) The method for producing a silver halide emulsion as described in (67) or (73), wherein the addition hole is closed when addition is stopped and the additive solution and the reaction solution are in a non-contact state.
(75) The emulsion is ultrafiltered during and / or after the grain formation,₃ ⁻The content (mol / mol AgX) is reduced to 0 to 90, preferably 0.01 to 40, more preferably 0.01 to 10% before the ultrafiltration (1), (45) (55) The manufacturing method of the silver halide emulsion in any one of.
(76) The method for producing a silver halide emulsion as described in (75), wherein the ultrafiltration is performed by a cross-flow method in which a liquid is fed in a direction parallel to the filter membrane surface.
(77) The Ag⁺And X⁻Is added by a plunger pump having a syringe and a piston, and the driving of the piston is driven by a pulse motor whose (added liquid amount mL / pulse) is determined in advance, and (A₁₇Pulse (sec / sec) (A₁₇The method for producing a silver halide emulsion according to any one of (45) and (55) to (74), wherein the addition is performed at a flow rate of (pulse addition amount / second).
(78) For the addition of one solution, two or more reciprocating plunger pumps are used, and while adding with one pump, a new solution is added to the cylinder with the other pump. (77) The method for producing a silver halide emulsion according to (77), wherein the silver halide emulsion is alternately sucked and added alternately.
(79) The piston is pushed out by an object that advances while rotating, such as a screw nail, and the object rotates and advances according to a preset (the rotation angle / pulse) (77). ) Or (78).
(80) A photographic material comprising one or more layers of the emulsion described in (1) above coated on a support.
(81) The fine particle emulsion described in (16) is used as a filter material for removing UV light in (photosensitive material having one or more AgX emulsion layers on a support), and 350 incident on the photosensitive material A photographic light-sensitive material characterized by absorbing 10 to 100, preferably 30 to 100, more preferably 60 to 100% of light having a wavelength of 370 nm.
(82) a blue-sensitive layer in which the photosensitive material is at least sensitive to blue light to form a yellow dye, a green-sensitive layer to be sensitive to green light to form a magenta dye, and a red feeling to be sensitive to red light to form a cyan dye The photographic light-sensitive material according to (80) or (81), which is a color photographic material having a layer.
(83) The photographic light-sensitive material as described in (81), wherein the layer containing the particles is a non-photosensitive layer and is disposed closer to the subject than the photosensitive layer.
(84) The fine-grain emulsion described in (16) is mixed in at least one photosensitive material having at least one photosensitive layer and a non-photosensitive layer on a support, and the refractive index of the mixed layer with respect to 520 nm light is changed. A photographic light-sensitive material characterized in that it is increased by 0.05 to 1.0, preferably 0.1 to 0.9, more preferably 0.2 to 0.9 with respect to before mixing.
(85) The light scattering density of the light-sensitive material with respect to light having a wavelength of 520 nm is 0.01 to 0.95, preferably 0.01 to 0.6, more preferably 0.01 to 0. The photographic light-sensitive material as described in (84), wherein the photographic light-sensitive material has an aspect reduced to .3.
(86) The fine particles according to (16) are [AgCl, AgBr, AgBrI, or two or more kinds thereof spectrally sensitized by adsorbing a dye having a saturated adsorption amount of 20 to 100, preferably 60 to 100%. In the vicinity of the photosensitive tabular grains having a mixed crystal composition (the aspect ratio is 2 to 500, preferably 4 to 500)], 0.01 to 10 mol, preferably 0.1 to 10 mol% of the molar amount of the tabular grains. Photosensitive materials made to exist in
(87) The fine grain emulsion described in (16) is (water, dispersion medium and AgX grain A₁₈Other AgX Emulsions A₁₉Added to the₁₉The fine particles are dissolved in₁₈Sinking on top, A₁₈60 to 100, preferably 90 to 100% of the total projected area of the particles has an average AgI content (mol%) of 0 to 35, preferably 0 to 20, and a circle equivalent projected diameter of 0.05 to A method for producing a silver halide emulsion, wherein the silver halide emulsion is 20.
(88) A₁₈60 to 100, preferably 90 to 100% of the total projected area of the particles has an aspect ratio (equivalent circular projected diameter / thickness) of 2 to 500 and a thickness (μm) of 0.01 to 0.5, Preferably, it is 0.01-0.3, The manufacturing method of the silver halide emulsion as described in (87) characterized by the above-mentioned.
(89) A silver halide emulsion having at least a dispersion medium, water, and silver halide grains, wherein the silver halide is a mixed crystal of any composition ratio of AgBr, AgCl, AgI and two or more thereof. The average diameter of the emulsion is 0.01 to 20 μm, and the emulsion is Ag while maintaining the silver potential (vs. 25 ° C. saturated calomel electrode) at the specified silver potential in the range of −10 to 300 mV.⁺Solution containing X and⁻A silver halide emulsion characterized by being an emulsion formed by a simultaneous mixing addition method.
(90) (13) to (15), (37), (40) characterized in that the particle has 1 to 3, preferably 1 recess, parallel to the (001) plane on the particle surface. ). The silver halide emulsion according to any one of
(91) Any one of (10) to (17), wherein the particle is a particle obtained by first forming the particle according to (9) and then changing the particle shape during the particle growth. A silver halide emulsion according to any one of the above.
(92) (10) or (11), wherein the grains are grains obtained by first forming the tabular grains shown in FIG. 5 and then changing the grain shape during the grain growth. Silver halide emulsion.
(93) After the particles first form seed crystals of the particles, the seed crystals are converted into the original crystals under the generation conditions of the particles according to (9) or under the conditions of (19) or (70). 1.3 × 10¹⁰, Preferably 2-10⁶The silver halide emulsion as described in (13), which is a grain obtained by growing to a double molar amount.
(94) The seed crystal is first formed in a dispersion medium aqueous solution at 0 to 60 ° C., and the growth is performed at a temperature 3 to 98, preferably 10 to 90 ° C. higher than the seed crystal formation temperature. (13) The silver halide emulsion as described above,
(95) In addition to the fine grain emulsion, the AgI content (mol%) is 0 to 30, preferably 0 to 15, and the diameter (μm) is 0.01 to 0.15, preferably 0.02 to 0.1. AgX₃Fine particles are added, which is A₁₉Dissolved in A₁₈Sinking on top, A₁₈The method for producing a silver halide emulsion as described in (87), wherein the AgI content (mol%) of the AgX layer deposited thereon is from 0.1 to 30, preferably from 0.5 to 20.
(96) In addition to the fine grain emulsion, Ag⁺Solution containing X and X⁻An aqueous solution containing₁₈Sinking on top, A₁₈The method for producing a silver halide emulsion as described in (87), wherein the AgI content (mol%) of the AgX layer deposited thereon is from 0.1 to 30, preferably from 0.5 to 20.
(97) The grains are tabular grains having a {001} plane as a main plane and an aspect ratio (grain projected diameter / grain thickness) of 1.7 to 100, preferably 2 to 100. The silver halide emulsion according to (1).
(98) The silver halide emulsion as described in (97), wherein at least one of the side surfaces of the grain is a {101} plane or a plane equivalent to the {101} plane.
(99) The silver halide emulsion as described in (97), wherein the grain content (mol%) of the grains is from 1 to 70, preferably from 5 to 60, more preferably from 10 to 55.
(100) The particle formation is performed in the order of a nucleation process, an aging process, and a growth process, and the process of nucleation and growth is performed by the simultaneous mixing addition method to the reaction solution (45) A method for producing the silver halide emulsion as described.
(101) The silver halide emulsion as described in (45), wherein the grain formation is performed in the order of a nucleation process and a growth process, and each process is performed by the simultaneous mixing and adding method to the reaction solution. Production method.
(102) In the ripening process, undesired particles are dissolved and deposited on the target particles, whereby the projected area ratio (%) of the target particles is 2 to 10%.⁶, Preferably 5-10⁶(100) The manufacturing method of the silver halide emulsion as described in (100) characterized by making it increase to 2 times.
(103) Ag in the nucleation process and growth process⁺And X⁻The simultaneous mixing addition rate (mol / min) was 10 for each liter of reaction solution.^-5-1.0, preferably 10^-4The method for producing a silver halide emulsion as described in (100) or (101), which is within a range of .about.0.5.
(104) The Ag at the start of the particle formation⁺And X⁻The simultaneous mixing addition rate (mol / min) was 10 for each liter of reaction solution.^-2The method for producing a silver halide emulsion according to (100) or (101), characterized in that it is -0.7, preferably 0.03-0.5.
(105) The Ag at the start of the grain formation⁺And X⁻The simultaneous mixing addition rate (mol / min) was 10 for each liter of reaction solution.^-5~ 9.9 × 10^-3, Preferably 10^-5~ 3x10^-3The method for producing a silver halide emulsion as described in (100) or (101), wherein
(106) The Ag⁺Solution and X⁻(45), (100) to (105), characterized in that at least one or both of the solutions contain a dispersion medium of 0.01 to 10, preferably 0.1 to 5% by mass. A method for producing a silver halide emulsion.
(107) 30 to 100% by mass of the dispersion medium is characterized in that 0 to 1% of the total number of amino groups of gelatin is gelatin that is chemically modified with an organic compound having 1 to 50 carbon atoms (45) Or the manufacturing method of the silver halide emulsion of (106) description.
(108) 30-100% by mass of the dispersion medium has a hydroxyproline (Hyp) content (the number of Hyp groups per 100 amino acid residues) of 0-100, preferably 0.1-60, more preferably 1-30. The method for producing a silver halide emulsion as described in (45) or (106), which is a gelatin.
(109) 30 to 100% by mass of the dispersion medium is an animal living in a cold zone or cold sea having a temperature (° C.) of −50 to 25, preferably −50 to 15, more preferably a fish living in the sea of the cold sea. (45), (106), (108) The method for producing a silver halide emulsion according to any one of (45), (108), which is gelatin extracted from one or more of bone, skin and scale.
(110) The time (min) from the start to the end of the particle formation is 0.2 to 3000, preferably 1 to 1000, more preferably 2 to 100, (45), (100), (101) The method for producing a silver halide emulsion according to any one of (101).
(111) The Ag⁺Solution and X⁻At least one, preferably both of the solutions are added directly into the reaction solution through the hollow tube, (Hollow tube length in reaction solution / inner diameter of reaction vessel) ratio = C₁The method of producing a silver halide emulsion as described in (45), wherein is from 0.5 to 50, preferably from 0.8 to 20, more preferably from 1.5 to 20.
(112) The difference (° C.) between the temperature of the additive solution added from the hollow tube in the reaction solution and the temperature of the reaction solution is 0 to 30, preferably 20 and more preferably 0 to 10 ° C. A method for producing a silver halide emulsion as described in (111).
(113) The silver halide emulsion as described in (45), wherein the reaction solution has a pAg of 2 or more, preferably 2.4 or more, and a pI of 2 or more, preferably 2.4 or more. Manufacturing method.
(114) The method for producing a silver halide emulsion as described in (45), wherein the temperature (° C.) of the reaction solution is 0.1 to 99, preferably 1 to 90, and the pH is 1 to 12. .
(115) The maximum adjacent side ratio of a hexagon formed by extending the hexagon or the straight part of the side [in one hexagon (maximum side length / minimum side length)] = C₂The silver halide according to (10) or (13), characterized in that is 1.0 to 3.0, preferably 1.0 to 2.0, more preferably 1.0 to 1.4 emulsion.
(116) The shape of the main plane is a hexagon or a shape with rounded corners of the hexagon, and the hexagonal or adjacent side ratio of the hexagon formed by extending the straight portion of the side [one Hexagon (maximum side length / minimum side length)] = C₂The silver halide emulsion according to (97), wherein is 1.0 to 3.0, preferably 1.0 to 2.0, more preferably 1.0 to 1.4.
(117) The silver halide emulsion as described in any one of (10), (13) and (116), wherein each apex angle of the hexagon is about 120 °.
(118) The shape of the main plane is a triangle or hexagon, or a shape with rounded corners thereof, and the maximum adjacent side ratio of the hexagon formed by extending the straight part of the hexagon or side [ One hexagon (maximum side length / minimum side length)] = C₂The silver halide emulsion according to (97), characterized in that is 3.1 to ∞, preferably 4 to ∞.
(119) The silver halide emulsion as described in (97), wherein the side surface of the tabular grain has 1 to 5 troughs (ridge-shaped recesses) parallel to the main plane.
(120) The silver halide emulsion as described in (97), wherein the side surface of the tabular grain is parallel to the main plane and has no clear trough.
(122) In a photographic light-sensitive material in which at least one silver halide emulsion layer is coated on one or both sides of a support, at least one silver halide emulsion layer is the photosensitive halogenation described in (1). A photographic light-sensitive material containing a silver emulsion.
(123) The at least one silver halide emulsion layer is a photothermographic material containing the photosensitive silver halide emulsion, a non-photosensitive organic silver salt, a thermal developer and a binder (122). ) The photosensitive material described in the above.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
  Next, the present invention will be described in more detail.The drawings relating to the present invention are FIGS. 2 to 5, d to h in FIG. 6, FIGS. 7 (b) to 8 (c), FIGS. 11, 12, 13, and 14. The drawings and the description of the drawings are for reference only.
(II-1) Description of the grain structure of emulsion grains.
  The particles described in (1) (hereinafter referred to as “particle 1”) may contain AgCl and AgBr in the content described in (1) in addition to AgI. In this case, any ratio (0 to ∞) can be selected as the molar ratio of (AgCl / AgBr).
  Examples of the particle structure described in (3) to (9) include the dodecahedral particles shown in FIG. 1 and FIGS. 6a and 6b, and FIG. 2 as the particle structure example described in (10) to (12). There are hexagonal columnar particles shown in FIGS. 6d and 6e, and examples of the particle structure described in (13) to (15) include tetrahedral particles shown in FIGS. The crystal plane index of the particle surface is considered to be the embodiment shown in FIGS. That is, when particles are oriented and settled on a flat glass substrate surface and measured by X-ray diffraction after drying, (diffraction intensity of a plane parallel to the substrate surface / diffraction intensity of a plane non-parallel to the substrate surface) ratio = B₁Is obtained by using a known crystal structure diagram of AgI and X-ray diffraction data.
  Particles with a clear crystal habit are like dice. Centrifuge the emulsion, remove the supernatant, remove the dispersion medium, add water, re-disperse, and then let the particles settle spontaneously. Since it will land, you can use this. This is because, in the case of powder particles, only a part of the particles satisfy the Bragg condition and contribute to the diffraction intensity, whereas all crystal planes parallel to the substrate surface contribute to the diffraction intensity.
  In addition, by placing particles on a conductive substrate, cooling them to -120 ° C or lower, taking SEM electron micrographs from the top and diagonally, and comparing them with model particles made of cardboard, the shape of the particles can be accurately determined. It is also effective to use it together with comparing with the unit cell structure.
  The particle of e of FIG. 1 represents a particle in which the corners of the dodecahedron-shaped particle are rounded to be elliptical. When these particles are further grown under the conditions of (19) and (70), the dodecahedron particles can be obtained, so that the particles are particles corresponding to the items (3) to (9).
  As shown in FIG. 3, the tetrahedral particles include a particle in which the upper 7-face portion and the lower 7-face portion are mirror-symmetrical, and a particle in which it is asymmetric as shown in FIG. 4. Asymmetrical particles are defined by (37) and (39) and can be preferably used.
  Particle 1 has an α-type crystal structure at a temperature of about 147 ° C. or higher, but exists as (β-type, γ-type, a mixture of both) at about 146 ° C. or lower. Therefore, it exists in this mode of 146 ° C. or lower under a normal room temperature environment. In the case of a mixture, the molar ratio of both can be determined from the powder X-ray diffraction data of the mixture. Regarding the method, Physical Review 161, 848-851 (1967) can be referred to. For β-type and γ-type powder X-ray diffraction data, JCPDS card data (CD-ROM, which can be purchased and searched from Rigaku Denki Co., Ltd. in Japan, for example) can be referenced.
  In addition, the following method is effective. AgI emulsion grains with 100% beta form can be prepared. The powder X-ray diffraction was measured, and the intensity at the diffraction angle 2θ = 2.14 ° was β (20.14) and the intensity at 2θ = 21.39 ° was β (21.39) [β (21. 39) / β (20.14)] = B₂≈ 0.758.
  Next, the sample is heated to about 250 ° C. as it is, then rapidly cooled to room temperature, and X-ray diffraction is measured. Then, the content of γ-type increases, and the diffraction intensity of 20.14 ° peculiar to β-type decreases. For example, it can be seen from the decrease rate that the β-type content is about 37% and the γ-type content is about 63%. At this time, the diffraction intensity of 21.39 ° increases. Its component is the contribution of the content from β-form [this is B₂Calculated from the value] and the contribution of the content from the γ-type. From this, the diffraction intensity [γ (21.39)] of 21.39 ° when the γ-type content is 100% is obtained, and [γ (21.39) / β (21.39)] = B_Three≈4 is obtained. B₂And B_ThreeIf the values are used, approximate values of β and γ type contents in the sample can be obtained. This method is more preferably performed on a sample in which particles are sedimented and oriented on a glass substrate. The particle orientation is fixed, and measurement variation is reduced.
  When the cooling rate is lowered, the β-type content increases, and finally the β-type content becomes 100%. Therefore, the heating temperature is 200 to 400 ° C., and the cooling rate (° C./second) is 0.1 to 10^ThreeBy selecting a preferred combination in the region, particles 1 having a γ-type content (mol%) of 0.1 to 68, preferably 1 to 66, more preferably 10 to 65 can be formed. However, even when the heating temperature was changed in the range of 260 to 400 ° C., the γ-type content did not exceed 70%.
  In addition, powder method X-ray diffraction measurement was performed, and diffraction areas of 2θ = 50.595 ° and 55.703 ° peculiar to γ type and 2θ = 38.356 °, 53.113 ° and 59.389 ° peculiar to β type It is also found by comparing The β and γ contents in Table 1 are shown as a simple area ratio between the ratios of 50.95 ° and 53.113 °. The γ content depended not only on pAg at the time of particle formation but also on pH, temperature, and particle formation time. For example, even if a large amount of γ-type was formed at the beginning of particle formation, the content changed with particle formation time when it dissolved in the subsequent process and deposited as β-type on large β-type particles.
  The hexagons of the hexagonal faces of the particles of FIGS. 2-6 are parallel to each other on the opposite sides, and their apex angles are about 120 °. This reflects the shape of the (001) plane of the hexagonal columnar unit cell of the β-type AgI crystal of FIG. The rhombus (001) plane of FIG. 1a reflects the shape of the (001) plane of the rhomboid columnar unit cell of FIG. The hexagonal shapes of (10) and (13) are also considered to reflect the hexagonal shape of the upper surface of the unit cell.
  Here, for example, the (001) plane is the uppermost I of the unit cell of FIG.^-It does not refer only to the surface consisting of only. I^-Side and Ag⁺Since the surfaces of the layers are alternately stacked and the particles grow,^-When the grain growth is finished at the place where^-(001) plane consisting of Meanwhile, Ag⁺If the grain growth is finished at the place where the layers are stacked, Ag⁺(001) plane consisting of In addition, after particle growth, AgNO_ThreeIs added to the emulsion and I^-Ag on the (001) plane consisting of⁺When layers are stacked, Ag⁺(001) plane consisting of Accordingly, the (001) plane in FIGS. 1 to 5 represents a plane parallel to the (001) plane in FIG. That is, the (001) plane is an expression including the (002) plane. The same applies to the other surfaces, and the expression includes all surfaces parallel to the corresponding surface. In the present invention, the “plane” represents the crystal surface.
  In the above (7) and (8), “about” means that the error is preferably within 5 °, more preferably within 3 °, and even more preferably within 1.5 °. Crystallographically, each apex angle of the surface is constant, but a measurement error may occur, the edge may melt and become unclear, and the measurement error may increase. The same applies to the right angle of the “right-angled parallelogram” in (12). The angles of the trapezoidal faces of the tetrahedral particles described in (13) and FIGS. 3 and 4 are about 73 ° and about 107 °, and the same is true here.
  As shown in (3) to (15), the outer shape in (1) defines the shape of the crystal face, the number of crystal faces, the area ratio between crystal faces in one particle, and the face angle. Refers to the shape. In the case of particles with rounded corners, the shape of the surface formed by extending the straight part of the side is defined. In addition, the radius of curvature of the rounded portion is defined. In the embodiment, the roundness of the rounded particles has a curvature diameter of preferably 0.1 to 30 times, more preferably 0.2 to 10 times the projected diameter of the particles. The variation coefficient of the variation is preferably 0.01 to 0.3, and more preferably 0.01 to 0.2.
  (1) 2 to 5 kinds of the single-type AgX emulsions described can be mixed at any ratio and used.
[0006]
(II-2) Preparation method of the emulsion
(II-2-1) pH, pAg, temperature dependency during particle formation. Ag in an aqueous solution containing a dispersion medium⁺An aqueous solution containing I^-Particles 1 are prepared by simultaneously mixing and adding an aqueous solution containing. At this time, pH (1-12) of the aqueous solution and Ag⁺Concentration (pAg 1-17), I^-When the concentration (pI1 to 17) is changed variously, particles having various shapes are generated. For example, in 1200 ml of a 3% by weight aqueous solution of normal alkali-treated beef bone gelatin at 60 to 90 ° C., Ag-1 solution (AgNO_Three0.2N aqueous solution) and KI-1 aqueous solution (KI 0.2N aqueous solution), while keeping pAg constant, Ag-1 solution is added at 4 ml / min for 10 minutes to form seed crystals. Next, Ag-2 solution (AgNO_Three1N aqueous solution) and X-2 solution (KI 1N aqueous solution), while maintaining the same pAg, Ag-2 solution was added at an initial flow rate of 2.4 ml / min and an acceleration flow rate of 0.16 ml / min for 100 minutes. When seed crystals are grown, the particle formation conditions (C₁~ C₉) And the characteristics of the generated particles are shown in Table 1. The β-type content and the γ-type content are in mol% units. Therefore, the embodiment can be referred to the description in Table 1.
[0007]
[Table 1]

[0008]
Judging from the results when the pH and pAg were changed more finely, the preferred production region of the dodecahedron particles is preferably (pAg ≧ 2.4 and PI ≧ 2.4), and (pAg ≧ 2). And PI ≧ 2.7) are more preferred. The pH is preferably 1 to 12, more preferably 3 to 9, and still more preferably 4 to 8. Below pH 3, the particles shown in FIG. 2c are likely to be mixed at a ratio of 0.1 to 10%. Where pI = −log [I^-mol / L], pAg = −log [Ag⁺mol / L].
(PAg = 1 to 2.7) is preferable, and (pAg = 1 to 2.4) is more preferable as a preferable generation region of the particles of the embodiment of FIGS. 1e and 6c in which the particles are rounded. The pH is preferably 7-12, more preferably 8-11.
The preferable production | generation area | region of the hexagonal columnar particle as described in FIG. 2 b and c is preferably pH 1-9, more preferably pH 1-7, and still more preferably 1-5. The pAg is preferably 1 to 2.7, more preferably 1 to 2.4.
The particles shown in FIGS. 2c and d and FIG. 6d in which the plane of the right parallelogram is flat are likely to occur at pH 1 to 3.9, and the particles in FIG. 2b and FIG. It is likely to occur at -8.5. The number ratio (%) of one of the particles can be divided into 60 to 100, preferably 80 to 100, and more preferably 90 to 100%.
Preferred production regions of the tetrahedral particles described in FIGS. 3, 4 and (13), (14) are pH 1-9, preferably 1-6, and pI 1-2.7, preferably 1.5-2.5. is there. In addition, when the dodecahedron grains are grown in this region, the dodecahedron grains are converted into the dodecahedron grains, and the emulsions described in (13) and (14) are obtained.
pH 5-12, preferably 9-11 (C in Table 1)₉Tabular grains are formed. Examples of the particle structure are shown in FIGS. 5 and 6h. 50 to 100, preferably 70 to 100, more preferably 90 to 100% of the total projected area of all AgX grains has an aspect ratio (grain equivalent projected diameter / grain thickness) of 1.6 to 100, preferably Is a tabular grain emulsion having a thickness (μm) of 0.02 to 0.5, preferably 0.02 to 0.3.
Under the pH and pAg conditions for the formation of the dodecahedron particles, when the temperature at the seed crystal formation is 5 to 50 ° C. and the growth is performed at 60 to 95 ° C., that is, when the seed crystal formation temperature is lowered, The generation probability of tetrahedral particles is increased.
Once the tetrahedral particles are formed, even if the seed crystals are grown under the conditions for generating the dodecahedron particles, they grow as tetrahedral particles. Therefore, the tetrahedral particles have crystal defects peculiar to the particles. It is thought that. That is, the number of twin planes, dislocation lines (edge dislocation lines, helical dislocation lines), the number, and how to enter are considered as specific aspects.
Judging from these characteristics, if these grains are written in ascending order of the crystal defect content, it is considered that [the dodecahedron grains> the symmetric tetrahedral grains, the asymmetric tetrahedral grains> tabular grains]. Further, the dodecahedron particles described in (2) to (9) can be said to be particles that are easily generated in a high temperature region of 50 ° C. or higher, preferably 60 ° C. or higher. Here, the crystal defects indicate twin planes, edge dislocation lines, and helical dislocation lines.
AgI particles having a β content of approximately 100 mol% can be formed by normal particle formation. The X-ray diffraction measurement shows that the peak intensity peculiar to γ type at 2θ = 50.795 ° and 55.703 ° is different from that of other β types at 2θ = 53.113 ° and 42.449 °. It is concluded from the fact that it is 1% or less. Further, when cooled slowly from 250 ° C. (takes the most stable structure), crystals with a β content of 100% can be obtained, and particles with a γ content of 70 mol% or more cannot be obtained under normal particle formation conditions. In addition, the β type is considered to be most stable near room temperature because the γ content is increased by the special method of rapid cooling from the high temperature described above. However, the blue light absorption edge wavelength is in the order of (α> γ> β), and the γ type has an advantage of absorbing even longer wavelength light. In this respect, particles having a high γ content are preferred.
Particles with a high γ content are shown in Table 1₂, C_Four, C₆, C₉Obtained in the region of
These particles are preferably formed by selecting the most preferable combination within the range of pH 1 to 12, pAg = 1 to 10 or pI = 1 to 10, temperature (° C.) 0 to 100, preferably 2 to 90. .
The elliptical spherical particles are represented by C in Table 1._ThreeFirst, the dodecahedron seed crystal is formed, and then AgNO is obtained._ThreeAnd alkali to add C_ThreeIt can be obtained by growing under these conditions, and it is more preferable.
The particle-forming dispersion medium has a mass average molecular weight of 3000 to 10⁶, Preferably 10^Four~ 3x10^FiveAny conventionally known water-soluble dispersion medium can be used in the range of 0.1 to 15, preferably 0.3 to 10% by mass. For specific examples of the dispersion medium, References 4 and 6, Japanese Patent Application No. 2001-297023 can be used. You can refer to the description. Examples of gelatin include alkali-treated, acid-treated gelatin, gelatin having a methionine content (μmol / g) of 0 to 60, gelatin having a low Met content of 0 to 20, H₂O₂The low Met content gelatin oxidized with a gelatin having a mass average molecular weight of 3000 to 70,000, preferably 5000 to 40,000; amino group, carboxyl group, imidazole group, alcohol group, amidino group, thioether group Gelatin obtained by chemically modifying 0.1 to 100, preferably 10 to 100%, of 1 to 6 kinds of groups can be used. As the chemical modification, an organic compound having 1 to 50 carbon atoms, preferably 1 to 20 carbon atoms is preferable.
Examples thereof include phthalated, benzoylated, acetylated, trimellitated, succinated, and methyl esterified gelatin.
For example, C in Table 1_FiveWhen the AgI particles are formed under the above conditions, when the dispersion medium used is phthalated gelatin and the phthalation rate is 95 to 100%, the particles described in (37) are formed. In the case of%, the particles described in (9) are obtained. However, in the case of gelatin in which amino groups are acetylated, benzoylated or trimellitated, or gelatin in which acid groups are esterified, the particles described in (9) can be obtained at a modification rate of 0.1 to 100%.
In addition, gelatin described below is preferable.
In Table 1, for example, [<2.3, (≧ 3)] at the right end represents pAg <2.3 and pI ≧ 3.
The tetradecahedral particles described in (13) to (15) and (37) have an embodiment having a recess (also referred to as a trough or a groove) on the particle surface and an embodiment having no recess. An embodiment having a recess is shown in FIG. The recess is in parallel with the (001) plane. This is thought to be because twin planes entered parallel to the (001) plane. In FIG. 7, it is considered that a γ-type layer, which is an ABC stack, is stacked with a stacking error in the stacking order of ABAB in a stacking order focusing on only one atom. As shown in FIG. 4d, straight concave portions appear on every other surface of the outer surface parallel to the (001) plane. This is called a single recess. The particles having two recesses are contained at different positions in parallel with each other.
Tabular grains C of the embodiment described in FIGS. 5 and 6h₉Has crystal grains for promoting growth on the edge surface, and therefore becomes tabular grains. The defects include a helical dislocation line defect and a recess formed by a twin plane. The existence of tabular grains in which the concave portions were observed was confirmed. For the particles, it promotes growth. The particle in which the recess is not observed may be a particle having a small recess and difficult to be observed, or a particle containing a helical dislocation defect.
As shown in Table 1, the γ-type content of the tabular grains is high. This is probably because it contains many twin planes.
When examining the formation of the tabular grains described in (97) to (99) and the grains described in (10) to (12), various types of grains are formed during nucleation, and in the subsequent process, (102) The aging of has occurred. This is because the particles described in (10) to (12) and (97) to (99) grow faster and become larger. In the ripening, the simultaneous addition is stopped, or the addition state is low enough to cause ripening (Ag⁺And / or X^-(Addition of a solution).
The particles described in (10) and (11) are first C₉Plate-like seed crystal C₉₁This is then converted to C in Table 1₂It can also be formed by growing under the following conditions. In this case, C₉₁When the aspect ratio is increased, the tabular grains described in (10) and (11) finally obtained also have a high aspect ratio.
(10) Tabular grains C described in (11)₂And C₉₁The aspect ratio (projected diameter / thickness equivalent to a circle) of each tabular grain is preferably 1.5 to 300, more preferably 2 to 300. The thickness (μm) is preferably 0.01 to 0.5, and more preferably 0.02 to 0.3.
[0009]
(II-3) Particle surface structure.
Judging from the results, Ag⁺The formation equilibrium crystal habit in the excess region is the (100) surface [(100), (010), (1-10) plane] seen in the particles of FIG. As can be seen in FIG.⁺And X^-Are alternately arranged surfaces, which correspond to the (100) surface of the AgBr system. C in Table 1₁, C₂The hexagonal surface of the particle having the shape shown in FIG.₂The value is considered to be 0.6 to 1.0, preferably 0.9 to 1.0.
Meanwhile X^-The hexagonal (001) plane of the tetrahedral particles prepared in the excess region is [X^-Total area of the surface consisting of / (001) total area of the surface] = A_FourThe value is considered to be 0.6 to 1.0, preferably 0.70 to 1.0. The (101) surface of the tetrahedral particles [(101), (011), (01-1) plane] is A_ThreeIs considered to be 0.6 to 1.0, preferably 0.70 to 1.0. Therefore, the outer surface of the tetrahedral particle is X^-Most of the surface on which only is arranged corresponds to the (111) surface of the AgBr system.
The outer surfaces of the dodecahedron particles are the (100) plane, the (001) plane, and the (101) plane. This corresponds to a tetrahedral particle composed of an AgBr (100) face and a (111) face. The (001) plane is Ag⁺X consisting of only and^-There is a plane consisting of only A₂The value depends on the growth conditions of the grains.
Within the formation conditions of the particles, [Ag⁺Concentration (mol / L) / X^-Concentration (mol / L)] = B_FourThe larger the is, the more A₂The value increases. Therefore, in the particles described in (3) to (9), A₂Can be prepared such that the particle is 0.70 to 1.0, the particle is 0.301 to 0.699, and the particle is 0.0 to 0.30. B_FourThe value is preferably from 0.01 to 100.
In addition, A of these particles₂~ A_FourThe value is the Ag value in the emulsion after grain formation.⁺Or X^-By changing the pAg and pI values of the emulsion._FourYou can change by changing. Therefore, in the particles described in (3) to (15), A₂~ A_FourParticles having a value of 0.70 to 1.0, particles of 0.301 to 0.699, and particles of 0.0 to 0.30 can be prepared. B during particle formation_FourIf the value is greatly changed, the shape of the generated particles changes, so that it cannot be changed greatly. On the other hand, after forming the particles, Ag⁺Or I^-And add B_FourThe method of changing the A is almost without particle deformation.₂~ A_FourCan be changed greatly, which is more preferable.
Here, X stacked on the particle^-I^-Halogen ion (Cl) having a mol% content of 0 to 100, preferably 50 to 100, more preferably 80 to 100^-, Br^-, I^-).
These particles can be preferably used depending on the purpose. For example, chemical sensitization nuclei are formed preferentially on surfaces that are highly reactive with chemical sensitizers, and latent image dispersion is suppressed. Preferentially, [the amount of chemically sensitized nuclei produced = the amount of moles of chalcogen atoms / cm²] Is 1.5 to 10 on the other side⁶, Preferably 3-10⁶Times, more preferably 10 to 10⁶It means that it is double.
It is preferable to selectively form on different crystal planes. In the particles described in (3) to (9), it is more preferable to form chemical sensitization nuclei preferentially on the (−110) plane. The magnitude of reactivity of chemical sensitizers is usually (Ag⁺Surface on which only is placed> Ag⁺And X^-Where X is placed> X^-Is the order of the plane on which the
The adsorption property of the sensitizing dye is A₂~ A_FourSince it depends on the value, a sensitizing dye may be added and adsorbed after adjusting to a preferred value. Further, after adding a sensitizing dye, adsorbing to the particles, adsorbing 10 to 100% of the saturated adsorption amount, preferably 40 to 100%, more preferably 70 to 100%, adding a chemical sensitizer, It is preferable to form a chemical sensitization nucleus preferentially in a place where no sensitizing dye is adsorbed. Preferentially follows the above provisions.
Further, by utilizing the difference in the adsorption property of the sensitizing dye to different crystal planes, chemical sensitization nuclei can be preferentially formed on the crystal plane with a low coverage of the dye. That is, the amount of adsorption of the sensitizing dye (mol / cm²) Ratio = B_Five= [B₆Adsorption amount on crystal face / B₇The amount of adsorption on the crystal plane] is 0.0 to 0.9, preferably 0.0 to 0.4, and more preferably 0.0 to 0.2. And add B₆A chemical sensitization nucleus is preferentially formed on the surface.
[0010]
(II-4) Ag during particle formation⁺, I^-How to adjust the concentration.
When forming the particles 1, Ag of the reaction solution during particle formation⁺And I^-It is necessary to precisely control the concentration of. Therefore, it is preferable to use the method described in (55) to (79). In general, when an ion selective electrode is placed in a solution and the potential difference from the reference electrode is measured, the specific ion concentration correlates with the magnitude of the potential difference. A method of detecting the ion concentration in a solution as an electric signal by utilizing the correlation is frequently used in the chemical field. In the case of AgX particle formation, Ag⁺And / or X^-An electrode is used that is selectively sensitive to. Specific examples include metallic silver, an AgX electrode (AgI, AgBr, AgCl and mixed crystals of two or more thereof), an embodiment in which the AgX electrode is laminated on metallic silver, a chalcogen silver electrode (Ag₂S, Ag₂Se, Ag₂Te and mixed crystals of two or more thereof), metallic silver, AgI, Ag₂S electrodes are preferred. In the present invention, the silver potential refers to these electrode potentials with respect to the reference electrode.
As the reference electrode, an electrode that exhibits a stable potential in the range of 10 to 60 ° C. is used. As specific examples, there are kangkou electrode, (Ag / silver halide) electrode, [for example, (Ag / AgCl), (Ag / AgBr), (Ag / AgI) electrode], and (Ag / AgCl) electrode is more preferable. For details, refer to the description in Chapter 12 of Document 9.
The potential difference between the two electrodes can be measured by joining the reference electrode and the reaction solution with a salt bridge to establish electrical continuity. There are a method of measuring the potential difference by putting a reference electrode in the reaction solution and a method of measuring the potential difference by placing the reference electrode outside the reaction solution, the latter being more preferable.
It is preferable to keep the temperature of the reference electrode constant, preferably 20 to 30, preferably 23 to 27 ° C. The reference electrode potential always shows a stable potential. In this state, Ag in the reaction solution⁺And I^-The potential difference when the concentration is variously changed is obtained for various temperatures. Using this relationship, the silver potential of the reaction solution during grain formation is measured, and Ag added to keep the value at the specified value.⁺Or X^-The flow rate of the solution containing is controlled by the method described in (55) to (78).
The silver potential of the reaction solution is measured, and (the potential−specified potential) difference S₁And a signal proportional to the difference (k₁S₁) To the addition system to control the flow rate. This corresponds to the P method of conventionally known PID control. In this case, the addition rate of the control liquid is equal to the equilibrium addition rate S._Ten[Eg Ag⁺Specified addition rate S₁₁(Mol / sec), X^-The equilibrium addition rate of S is S₁₁It is preferable that the amount of increase / decrease with respect to the signal corresponds to the signal. The signal is sent every 0.01-100, preferably 0.03-30, more preferably 0.03-5 seconds. However, in proportion to the difference, X^-Increasing the flow rate of the liquid causes the potential to pass too much and falls too much due to the increase in the flow rate.If the flow rate is lowered to correct this, the potential passes too much too much because it passes the specified potential. This may occur repeatedly (this is called potential hunting). In order to prevent this, the following method is effective.
1) This phenomenon is caused by adding Ag⁺, X^-Increases in proportion to the equilibrium addition rate. Also, the concentration S of ionic species in the reaction solution to be controlled₁₂It becomes smaller in proportion to (mol / L). Also, the amount of reaction solution (S₁₃In proportion to the liter). In addition, it depends on the temperature and pH of the reaction solution. Preferred value of signal amount of CDJ control when these basic factors are changed (k₁k₂S₁) Before the start of particle formation, (particle formation time vsk₂) Is stored in the controller and (k₁k₂S₁) To increase or decrease the flow rate. Therefore k₁S₁In the case of particle formation conditions where hunting occurs with the signal of | k₂| Is 10^-6~ 0.98, preferably 10^-6~ 0.7, more preferably 10^-Four~ 0.3 is selected. The larger the hunting, the more | k₂A smaller value is selected for |. In addition to this, the type and amount of the dispersion medium, additive, and AgX solvent also affect the hunting.₂It can also be included in |.
2) The magnitude of the hunting is the absolute value S of the integrated value of (the potential difference vs. time elapsed).₂Is proportional to₂(K_Three= 1.0 + k_FourS₂) And as a CDJ signal (k₁k₂S₁/ k_Three).
3) Hunting cycle S_ThreeFind the second [k_Five= 1 + k₆/ S_Three] As the CDJ signal₁k₂S₁/ (K_Threek_Five). The shorter the period, k_FiveBecomes larger and the increase / decrease width of the flow rate is suppressed. Other, for example (S_Three> S_Four) If you want to control in seconds, the measured value is contrary (S_Three<S_Four) [K_Five= 1-k₆(S_Four-S_Three) / S_Four] Is formed, and the CDJ signal is k₁k₂S₁/ (K_Threek_Five) Is transmitted. Here, the period refers to one cycle of the repetition. The signal value is obtained every 1 to 1000, preferably 3 to 100 seconds, and fed back to the control system.
4) In addition, the functions I and D of the conventionally known PID control method can be used. That is, I is S₁In order to avoid an aspect where the time does not decrease indefinitely over time, (S₁This is a method of increasing the increase / decrease amount of the addition rate in proportion to the integral value. D is S₁Change in value over time (dS₁This is a method of decreasing the increase / decrease amount when / dt) is too large and increasing it when it is too slow.
5) Method of adding specified flow rate of two liquids.
If the addition accuracy of Ag-1 solution and X-1 solution is good, Ag-1 solution and X-1 solution are mixed and added at the specified flow rate at the same time.⁺And I^-The concentration of can be precisely controlled.
6) A three-liquid addition method, for example, a method in which Ag-1 liquid and X-1 liquid are added at a specified flow rate, and CDJ control addition is performed using another X-2 liquid. If the addition rate (mol / sec) of X-2 liquid is the aspect of (56), the addition speed of X-2 liquid will become small and control accuracy will increase more. Further, when the (X-2) solution is a dilute solution described in (65), the control accuracy is further increased.
Regarding the details of the PID control and the pulse motor, and the above control, the description in Document 8 can be referred to.
[0011]
(II-5) Epitaxial particles.
The disadvantages of high AgI content particles are as follows. 1) Even if chemical sensitization is performed, it is difficult to form effective chemical sensitization nuclei. This is because AgI is less soluble than AgBr and is less susceptible to halogen conversion due to its small solubility difference from chalcogen silver. 2) The electron capture efficiency of chemically sensitized nuclei is small. 3) The latent image development promoting action is small. 4) Development speed and fixing speed are slow. These have AgI characteristics (for example, solubility in water, ionic bond ratio) compared to AgBr.₂This is considered to be close to the characteristics of S.
When the particles 1 are used in the epitaxial mode described in (21) to (25) and (52), these defects are suppressed. This is because chemical sensitization nuclei are formed in an epi part having a low AgI content, the nuclei capture electrons, form a latent image, and serve as a development starting point. The time until the end of development and fixing processing is shortened by increasing the processing temperature (° C.) in the range of 20 to 60, preferably 30 to 60.
The formation of the epi-grains was achieved by adding Ag to the emulsion described in (1) (hereinafter referred to as emulsion 1)⁺And Xa^-An epilayer AgXb may be deposited on a part of the surface of the particle 1 by adding a liquid. At this time, there are a method of adding the particles 1 with the adsorbent adsorbed on the particles 1 and a method of adding the particles 1 without the adsorption. Examples of the adsorbent include a cyanine dye, an antifoggant, an onium salt compound, and a surfactant. Regarding examples of the compound and details thereof, the descriptions in Documents 4, 6, and 11 described later can be referred to. The adsorption amount is preferably 10 to 100, more preferably 30 to 100% of the saturated adsorption amount. Regarding the epi formation, the description in Document 2 can be referred to. It is preferable to adsorb the adsorbent because the epi-forming site is limited.
The dopant can be doped in the particles 1 and / or in the epiphase in the manner described in (25) to (30). Ag in the presence of the dopant⁺And X^-Is added to grow the grain or epi phase, the dopant is doped. Regarding the doping agent, the descriptions in References 4 and 6 below can be referred to. The presence of the dopant (mol / L) is 10^-1-10^-8, Preferably 10^-2-10^-7Is preferred.
In order for the dopant to be doped efficiently, first, the dopant is strongly adsorbed preferentially on the particle surface and does not leave the surface. For that purpose, the dopant itself has a strong adsorption characteristic or a dopant having a strong adsorption group (for example, a mode in which a ligand has such a characteristic in a metal complex) may be used. If AgX is deposited on the strongly adsorbed state, it is doped. In order for the dopant to be efficiently incorporated into the AgI crystal lattice, the same four-coordinate structure dopant as AgI is preferred.
PX = -log [X at the time of epi formation or doping^-Mol / L] is 0.5 to 10, preferably 1 to 7, pH is 1 to 12, preferably 2 to 10, temperature (° C) is 5 to 95, preferably 10 to 85, and dispersion medium concentration (g / L). L) is 1 to 100, preferably 5 to 40, and the most preferable combination can be selected.
[0012]
(II-6) Chemical sensitization, spectral sensitization, etc.
Chemical sensitization can be carried out by adding a chemical sensitizer to the emulsion of the present invention. As chemical sensitizers, chalcogen sensitizers (sulfur, selenium, tellurium sensitizers), noble metal sensitizers (gold, Group 8 metal compounds), reduction sensitizers alone, in any ratio of two or more of them Can be used in combination. (50) Agi⁺An antifoggant is effective as a concentration reducing agent.
Particle surface Ag⁺Combined with [Ag⁺(Surface) ⇔Agi⁺) Shift the chemical equilibrium to the left, Agi⁺Reduce concentration. Regarding details of these compounds, usage, etc., the descriptions in Documents 4, 6, and 11 can be referred to.
The particle 1 has a large blue light absorption coefficient at a wavelength shorter than 430 nm, but has a smaller blue light absorption coefficient at a longer wavelength. Therefore, when emulsion 1 is used for the blue-sensitive layer of the light-sensitive material, it is preferable to add one or more blue-sensitive layer sensitizing dyes, adsorb them to the grains, and spectrally sensitize them.
When used in a green sensitive layer, one or more sensitizing dyes for green sensitive layer are added, and when used in a red sensitive layer, one or more sensitizing dyes for red sensitive layer are added for spectral sensitization. Are used in the form described in (53), respectively, and the dye is used in a form in which the dye is adsorbed by 10 to 100%, preferably 30 to 100% of the saturated adsorption amount.
In addition, it can be used in the mode described in (54). It can also be used for a photosensitive material that is exposed to light in the wavelength range of 360 to 440 nm. Any light can be used, and there are natural light, LED light, laser light, fluorescence, discharge light, high temperature material light, and the like. Regarding the light source, the description in Reference 7 can be referred to, and the description of References 4, 6, and 11 can be referred to for the details of the compound examples of the cyanine dye and the method of use. 1 to 10 kinds of the dye species can be preferably used, and it is preferable to use two or more kinds of dyes having different absorption spectrum waveforms or dyes having different adsorption orientations to form a preferable absorption spectrum waveform and adsorption orientation.
Further, a compound that absorbs one photon and gives 2 to 4 electrons to AgX grains when adsorbed on emulsion grains and irradiated with light is 10^-8-10^-1, Preferably 10^-6-10^-2It is preferable to add in the addition amount of mol / mol AgX. Regarding the details of the compound, the description in Reference 12 can be referred to.
[0013]
(II-7) Other uses of particle 1
Since the particle 1 has low solubility in water, it can form ultrafine particles that are highly transparent to visible light. For this reason, it can utilize for a photographic material in the following aspect. 1) An ultrafine particle emulsion of particle 1 is added to and dispersed in the dispersion medium layer of the photosensitive layer and / or the non-photosensitive layer, and the refractive index of the dispersion medium layer with respect to visible light is increased. The difference in refractive index between the photosensitive AgX particles and the surrounding dispersion medium layer is reduced, the light scattering intensity of the AgX particles is reduced, and the sharpness of the photographic image obtained by development processing is increased. Molar ratio of other refractive index increasing agents such as titanium oxide and any ratio ((particles 1 / other refractive index increasing agents other than particle 1) = 10^-Five-10^Five, Preferably 10^-3-10^Three] Can also be used together. Regarding these details and embodiments, the description in Reference 5 can be referred to.
2) The ultrafine particles are dispersed in the dispersion layer of the photosensitive layer and / or the non-photosensitive layer as an ultraviolet absorber. Since the intrinsic absorption edge of the particle 1 is a direct allowable transition and has a large absorption coefficient, it is effective as an ultraviolet absorbing material having a wavelength of about 420 nm or less. In this case, the molar ratio of other ultraviolet absorbers and any molar ratio [(ultraviolet absorber other than particle 1 / particle 1) is 10).^-Five-10^Five, Preferably 10^-3-10^Three] Can also be used together. For other ultraviolet absorbers, the descriptions in References 4 and 5 can be referred to.
In order to form the fine particles described in (16), it is preferable to form the particles 1 under conditions of low solubility. For that purpose, AgX solvent (Ag⁺The compound which forms a soluble complex with the compound) is substantially absent, ie, its concentration (mol / L) is 0-10.^-1Is preferred, 0-10^-3Is more preferable, 0-10^-6Is more preferable. Further, in the solubility curve of the particle 1 [curve representing the relationship between the dissolution concentration of silver (mol / L) and the pAg], the solubility is 1.0 to 6, preferably 1.0 to 3 times the pAg of the lowest solubility. These conditions are preferred.
Under these conditions, Ag_nX_mSince the complex concentration is low, it is difficult for crystal defects to enter the particles, so that smaller particles are formed.
Specifically, it is preferable to use the conditions described in (113).
Also, Ag during nucleation⁺And X^-It is only necessary to increase the double jet addition speed to form many nuclei and complete the particle formation in a short time. That is, the method described in (104) may be used. However, when added at high speed, the generation ratio of particles having uncontrolled defects increases. In this case, it is preferable to increase the protective colloid properties of the nucleus using the method described in (106). Furthermore, nucleation may be performed at a low temperature, and the following conditions may be used.
In order to form nuclei and seed crystals with as few defects as possible, the Ag at the time of nucleation⁺And X^-The rate of addition (mol / min) may be slowed down, and the condition (105) may be used. It is more preferable to use the method (106) in combination. However, the number of generated nuclei is reduced. If necessary, it is preferable to concentrate the emulsion using the methods (74) and (75).
In addition to the temperature of the reaction solution, the combination of pH, pAg, and pI is selected to change the size of the produced particles. Therefore, it is preferable to select the most preferable combination. The interaction between the dispersion medium and the AgX particles changes, and the size changes.
When added in the form of (111) and (112), the added solution is added at the same temperature as the reaction solution, so that the specific particles can be made well and monodisperse particles with more uniform performance are formed. And preferred. FIG. 14 shows an example of the apparatus.
The lower the temperature (° C.), the lower the solubility, preferably 0 to 70, more preferably 1 to 40, and still more preferably 1 to 30. In this case, the dispersion medium is preferably a dispersion medium that does not gel at the low temperature, and has a viscosity (Pa · second) of 10% when a 2.0 mass% solution is allowed to stand at 1 to 20 ° C. for 15 minutes.^-Four~ 0.2, preferably 10^-Four~ 0.1, more preferably 10^-FourA dispersion medium of ~ 0.05 is preferred. In the case of the gelatin, the weight average molecular weight is preferably 3000 to 50,000, more preferably 3000 to 30,000. Further, the dispersion medium described in (107) and (108) is also preferable.
[0014]
(II-8) Others.
When the X-ray diffraction is measured by CuKβ ray after the dodecahedron AgI particles are settled and oriented on a flat glass substrate, the diffraction pattern shown in FIG. 8A is obtained, and the (001) plane and (100) plane are obtained. A diffraction peak of (101) plane remains. Accordingly, crystal planes oriented parallel to the substrate are the (001) plane, (100) plane, and (101) plane. When the hexagonal columnar particles are oriented in the same manner and X-ray diffraction is measured, the diffraction pattern shown in FIG. 8B is obtained, and the diffraction patterns on the (100) and (001) planes remain. Accordingly, the crystal planes oriented parallel to the substrate are the (100) plane and the (001) plane. When the tetrahedral particles shown in FIG. 4 are similarly oriented and X-ray diffraction is measured, the diffraction pattern of (c) of FIG. 8 is obtained, and the diffraction patterns of the (001) plane and the (101) plane remain. Accordingly, the crystal planes oriented parallel to the substrate are the (001) plane and the (101) plane.
If the particle has a flat crystal plane, the crystal plane has a probability of being in close contact with the substrate surface in proportion to the area thereof, so that a diffraction peak of the crystal plane with a proportional strength remains.
[0015]
[Table 2]

[0016]
When the dielectric loss of the dry film of the gelatin dispersion of emulsion grains described in (9) to (15) is measured and the dark conductivity (σ) characteristics of the grains are examined, the following can be said. Dodecahedron particle C having a diameter of about 0.2 μm at 25 ° C._FiveGives two loss peaks, a large peak (fL) on the low frequency side is about 10⁶The small peak (fH) on the high frequency side is 10 Hz.⁸Presumed to be around. This behavior is close to that of octahedral AgBr particles of the same size. When the antifoggants 1 to 3 are adsorbed to the particles, fL and fH shift to the low frequency side, and from the result of the particle size dependency described later, the dark conductivity component corresponding to fL is the particle surface site. Ag⁺Interstitial Silver Ion Agi Generated by Entering the Particle⁺it is conceivable that.
The fL temperature (T ° K) change of the dodecahedron particles described in (3-1) to (3-7) in Table 3 was measured, and log (σT) vs. 1000 / T was plotted in FIG. ΔE of σT = Aexp (−ΔE / kT) was determined from the slope of the straight line and is shown in Table 3. However, [peak frequency of fL = 10¹¹σ]. Since the slope was slightly different between the region of 250 ° K or higher and the region of 250 ° K or lower, both ΔE values were described. The decrease in fL due to the addition of the antifoggant was small compared to the AgBr system. AgI is a bond between a soft acid atom and a soft base atom, and is a soft bond compared to a bond between a hard acid atom and a hard base atom. The binding free energy ΔG is also smaller than AgBr. For this reason, Agi is easy to generate and move in the crystal. This is a phenomenon that reflects this. For this, the methods (26) to (36) are used together, and the fL value is set to 10^-3It is preferable to reduce it to 0.9 times. [△ E = △ G_i(Agi⁺Generation energy) + U (Agi⁺Activation energy))], and in AgI, U = 0, so ΔE≈ΔG_iRepresents.
As the particle size increased, fL and fH shifted to lower frequencies. For example, fL is 10 for particles of about 1.1 μm diameter.^5.24Met. Hexagonal columnar particle C of Example 6₁(Average diameter 0.65 μm, average thickness 0.26 μm) fL is 10^4.5, FH is 10^6.05When the antifoggant 2 is adsorbed thereto, fL decreases and disappears, and fH is 10^5.1It becomes one peak. This behavior is shown in Table 1₉Tabular grain C obtained under the conditions of₉Similar to the behavior of (average thickness 0.25 μm, average diameter 2 μm). Particle C₉FL is 10^4.8And fH is 10^5.8When the inhibitor 2 was adsorbed thereto, the two frequencies were almost the same, and the peak intensity ratio of (fL / fH) was reversed (1 / 0.95 → 0.94 / 1).
Both particles have twin planes parallel to the main plane, which is Agi⁺It is considered that the frequency of fL is lowered. Particle C₁Or C₉When the main plane is oriented parallel to the electrode surface, the surface conductivity of the main plane does not contribute to the dielectric loss. It is considered that the frequency of fH is lowered because only the surface conduction of the side surface and part of the non-parallel oriented main plane contributes.
The amount of antifoggant added is about 3 × 10.^-3Mol / mol AgX (see Table 3).
[0017]
[Chemical 1]

[0018]
The C_FiveThe change in fL when the pH and pAg of the emulsion was changed was compared with that in the case of AgBr grains as shown in Table 3 (fL value 10^XThe X value is shown). Table 3 shows type emulsion and HNO for type emulsion_ThreeSolution added to pH 3; NaOH solution added to pH 10.4; AgNO 3_ThreeLiquid to pAg2.2, AgBr is Br^-For AgI,^-The liquid was added to give pX = 2.0, and the antifoggant 1 or 2 was (3 × 10^-3(Mol / mol AgX). Cube AgBr, B₆And octahedron AgBr, B₇And dodecahedron AgI, C_FiveThen, Agi at pH ↑ than type⁺The concentration has dropped. This is Gel's -NH_Three ⁺Is Ags⁺(Ag on the particle surface⁺) Was unstable, but at pH ↑ -NH₂And this is Ags⁺Coordinated to Ags⁺Stabilize the Ags⁺⇔Agi⁺It is understood that the balance of is moved to the left side. B₆And B₇The opposite phenomenon occurs at pH ↓ than type, and Agi⁺The concentration has increased. This is Gel's -COO^-Is Ags⁺Was changed to -COOH at pH ↓, Ags⁺It is understood that the stabilizing action of the slag decreased and the equilibrium shifted to the right. But C_FiveThen the concentration decreased. This is because the high hydrophobicity of AgI is close to that of organic compounds.^-This is because the stabilization effect by intermolecular force with -COOH is larger than the stabilization effect of. Non-ionic -NH also in the case of pH ↑₂This is considered to be a stabilizing effect due to the intermolecular force. There are the following mechanisms for the dispersion medium to stabilize the atoms on the particle surface. 1) Coulomb interaction, 2) S, N, O atoms and Ag with electron pairs⁺Stabilization effect by coordination bond. H₂O coordination bonds are also included. 3) Interaction due to intermolecular force between an organic compound having —COOH or π-conjugated bond and AgX on the surface. It can be understood that the contribution rate of each action is different between the AgBr system and the AgI system. Regarding intermolecular forces, reference can be made to descriptions in the chemical dictionary, intermolecular forces, and Tokyo Kagaku Dojin (1994).
B₆And B₇Then Ag⁺Agi at concentration ↑⁺Concentration ↓. This is because Ag on the particle surface⁺Is adsorbed, and the whole particle is positively charged, whereby Agi in the particle⁺The electrical energy level of A is increased by ΔEeV, and Agi⁺This is because the concentration decreases. The electric potential in the particle due to the surface charge is almost equipotential according to Gauss's law (therefore no potential gradient exists), and Agi⁺The concentration decreases everywhere in the particle. The amount of decrease is usually exp (_-ΔE / KT). Here, K represents a Boltzman constant, T represents an absolute temperature, and the unit is KTeV.
On the other hand, C_FiveThen Ag⁺Agi at concentration ↑⁺Conversely, the concentration increased. The reason is as follows. AgI particles and Ag⁺The level ↑ is small because the ionic interaction with is small (AgI is hydrophobic). For this reason, the adsorbed Ag⁺Is Agi⁺And (Ags⁺⇔Agi⁺) Is moved to the right to increase the concentration. Or because the lattice spacing of AgI is large, Ag⁺Mechanism that goes directly into the gap. Alternatively, AgI can be regarded as a kind of organic polymer because it is a four-coordinate bond and has a large covalent bond (a bond electron has a large localization). Therefore, Ag in the solution⁺It is also considered that the liquid is soaked between the polymer interstices. However, Agi⁺Movement is I^-The movement also shows dielectric loss characteristics because it is constrained by the interaction. Br^-Agi at concentration ↑⁺The concentration has increased. This would be the opposite effect.
C_FiveThen I^-Agi at concentration ↑⁺Concentration decreased slightly. This is I^-Is the particle surface Ags⁺Adsorbed on Ags⁺The effect of reducing the concentration. I^-Is Ag in solution⁺The concentration of (in the solution Ag⁺⇔Ags⁺+ Agi⁺The effect of shifting the chemical equilibrium to the left is considered.
Since AgI has characteristics close to those of the organic polymer, it has high electron localization and low electrical conductivity. Therefore, it also has a feature that the photoconductivity in the crystal is lower than AgCl and AgBr.
Therefore, the AgI system has a sensitivity different from that of the AgBr system, and it is necessary to select an optimum combination of pH, pAg, and pI of the emulsion. However, the pH of the type emulsions in Table 3 is 6.4, and pAg is neutral (pAg = pX).
[0019]
[Table 3]

[0020]
AgI dodecahedron particles having a β-type content of about 100% are oriented on a glass plate and X-ray diffraction is measured. Next, when the sample is annealed at 250 to 300 ° C. as it is, then rapidly cooled and converted into a γ-type, and X-ray diffraction is measured, the maximum diffraction peak at 21.3 ° increases. From this, it can be seen that the β-type (001) plane is changed to the γ-type (111) plane. That is, it can be seen that the β-type [001] vector direction is changed to the γ-type [111] direction.
This indicates that β-type and γ-type can coexist as the stacking fault in one crystal. Moreover, the example is seen by the ZnS crystal | crystallization, for example, the description of Philosophical Magazine B, 279-297 (2001) can be referred. Ag in the [001] direction of FIG.⁺If the stacking position of the layers is (ABABAB / CBABA) or (ABABAB / CBACBA), the / position is a twin plane.
Regarding the AgX emulsion of the present invention and its application, the descriptions in paragraphs (0067) to (0087) of JP-A No. 2000-201810 and (I-8) of JP-A No. 2001-255611 can be employed. .
Regarding the application of the emulsion of the present invention to a heat-developable light-sensitive material, reference can be made to Reference 13 below, and for application to other light-sensitive materials, Reference 14 can be referred to.
Regarding the non-photosensitive organic silver salt, the thermal developer, the binder, and the support described in (123), the description in Reference 13 can be referred to.
(Reference)
1. B.L.J.Byerley et al. Journal of Photographic Science, 18, 53-59 (1970). U.S. Pat. Nos. 4,672,026, 4,414,310 and 4,184,878.
J.E.Maskasky, Physical Review, Volume B43, 5769-5772 (1991).
2. J. E. Maskasky, Phot. Sci. Eng. 25, 96-101 (1981), U.S. Pat. Nos. 4,940,084, 4,142,900 and 4,459,353.
3. G.C. Farnell, Journal of Photographic Science, 22, 228-237 (1974).
4). Research Disclosure, item 17643 (December 1978), item 38957 (September 1996).
5. European Patent No. 930532A, Japanese Patent Laid-Open No. 2000-347336.
6). Japanese Patent Application Nos. 2001-297023, 2001-201810, 2001-255611, 2000-347336, 8-69069, US 5,360,712.
7. Edited by Hiroshi Kubota, Optical Handbook, Asakura Shoten (1975). Edited by Shigeo Minami et al., Spectral Technology Handbook, Asakura Shoten (1990).
8). Edited by Chemical Industry Association, Handbook of Chemical Equipment, Chapter 21, Maruzen (1989).
9. The Chemical Society of Japan, Chemical Handbook, Basics, Maruzen (1984).
10. T.H.James and W.Vanslow Phot.Sci.Eng., 5, 21-29 (1961).
11． T.H.James, The Theory of the Photographic Process, 4th edition, Macmil lan (1977).
12． Japanese Patent Application Nos. 2001-800, 86161, 2000-22162, U.S. Pat. Nos. 5,747,235, 5747236, 6054260, and 5994051.
13. Japanese Patent Application Nos. 2001-349031, 2001-342983, 2001-335613, and JP-A-2001-33911.
14. JP-A-59-119350, 59-119344, US Pat. No. 4,672,026.
[0021]
【Example】
The following “Example 1”, “Example 2”, “Example 3”, “Example 4”, “Example 5” and “Example 12” are referred to as “Reference Example 1” and “Reference Example”, respectively. “Example 2”, “Reference Example 3”, “Reference Example 4”, “Reference Example 5”, and “Reference Example 12” shall be read.
Example 1.
  Dispersion medium solution 1 (25 g of gelatin 1, 1200 ml of water, 0.1 g of KI and pH 6.0) was put in a reaction vessel, kept at a temperature of 75 ° C., and stirred with Ag-1 solution (AgNO_ThreeWas added at the same time at 4 ml / min for 10 minutes to form seed crystals. After aging for 2 minutes, Ag-2 solution (AgNO_ThreeIs contained in 17 ml of 100 ml) and X-2 solution (16.7 g of KI is contained in 100 ml), and a silver potential (a metallic silver electrode, a pair of 25 ° C. saturated calomel reference electrode)._ThreeCDJ was added to keep it at -40 mV). Ag-2 solution was added at a starting flow rate of 2.4 ml / min and an acceleration flow rate of 0.16 ml / min for 98 minutes.
  At this point, 1 ml of the emulsion was collected, and after sensitizing dye 1 was saturated and adsorbed, it was centrifuged to remove gelatin. Water was added for redispersion, and one drop was placed on a mesh plate covered with a collodion film and dried. Carbon deposition, Au-Pd shadowing, and fixing were performed, and a transmission electron microscope image (TEM image) of the replica film was taken. The variation coefficient of variation in the diameter of the particles was 0.065, and the average diameter was 0.24 μm. The particle shape (9) and the dodecahedron particles shown in FIG. 2 accounted for 99% or more of the total projected area of the particles.
  The addition rate (mol / sec) of the X-2 solution is based on the same rate as the addition rate (mol / sec) of the Ag-2 solution. If the silver potential is higher than -40 mV, it is proportional to the potential difference. The CDJ was added in such a manner that the addition rate was increased, and when the addition rate decreased, the rate was decreased in proportion to the potential difference. As described in 1) of (II-4), k obtained in a preliminary experiment₂When CDJ was added, the amplitude of the potential fluctuation in the CDJ was within -14 to +14 mV with reference to -40 mV. In addition, each additive solution in all Examples was directly added to the solution through a hollow tubular rubber porous membrane having 800 pores. This is a rubber tube with a 0.5 mm diameter needle inserted to make a hole, and when not added, the hole is closed.
  In addition to the addition of one solution, the solution was added in the form of the alternating addition method described in (78) using two plunger pumps.
[0022]
Example 2
In Example 1, the same growth was performed except that the CDJ addition growth was performed as follows. The addition mode of the Ag-2 was the same, but the addition of the X-2 solution was performed simultaneously with Ag-2 for 98 minutes at an initial flow rate of 2.2 ml / min and an acceleration flow rate of 0.147 ml / min. At this time, the silver potential was controlled to -40 mV by controlling the addition speed of the X-21 solution (containing 4.15 g of KI in 100 ml) and adding it simultaneously. The starting flow rate was 0.8 ml / min and was controlled 10 seconds after the start of addition. The fluctuation width of the potential by this control method was within -14 to +14 mV with reference to -40 mV.
The TEM image of the obtained emulsion grains was taken and shown in FIG. The average diameter was 0.24 μm and the coefficient of variation was 0.058. The dodecahedron grains accounted for 99% or more of the total projected area of the grains.
[0023]
Example 3
Dispersion medium solution 3 (35 g of gelatin 1, 1500 ml of water, 0.05 g of KI, pH 6.0) was put in a reaction vessel, kept at a temperature of 62 ° C., and stirred, while stirring, Ag-31 solution (AgNO in 100 ml)_Three30 g) and X-31 solution (containing 29.4 g of KI and 1 g of gelatin 2 in 100 ml) were added simultaneously at 25 ml / min for 8 minutes directly into the solution through the porous membrane.
Next, simultaneous mixing addition was performed for 4 minutes at a start flow rate of 25 ml / min and an acceleration flow rate of 3 ml / min. In either case, the alternate addition method was used.
The TEM image of the obtained emulsion grains was taken. The average diameter was 0.04 μm, and the variation coefficient of the diameter distribution was 0.10. 80 ml of the emulsion was sampled and added to the dispersion medium solvent 3. At 75 ° C., using Ag-2 solution and X-2 solution, initial flow rate was 3.4 ml / min and acceleration flow rate was 0.24 ml / min for 50 minutes. In the same manner as in Example 1, -40 mV CDJ was added. When the TEM image of the obtained emulsion grains was taken, 98% or more of the projected area was the dodecahedron grains.
[0024]
Example 4
Example 3 was the same except for the following. Ag-31 solution and X-31 solution were added at the same rate of 12 ml / min for 8 minutes. Next, simultaneous mixing addition was performed for 12 minutes at a start flow rate of 12 ml / min and an acceleration flow rate of 1.2 ml / min. The average diameter of the obtained emulsion grains was 0.06 μm, and the coefficient of variation in diameter distribution was 0.09. When the grains were grown in the same manner as in Example 3, 99% or more of the projected area was the dodecahedron grains.
[0025]
Example 5 FIG.
Dispersion medium solution 5 (containing 25 g of gelatin 1 and 1200 ml of water, and adjusted to pH 10.0 with NaOH)_ThreeWas added to a reaction vessel, the temperature was kept at 75 ° C., and Ag-1 solution and X-41 solution (containing 100 g of KI in 100 ml) were stirred at 4 ml / min. Simultaneous mixing was added for 10 minutes. Then, using Ag-2 solution and X-42 solution (containing 16.56 g of KI in 100 ml), CDJ was added in the same manner as in Example 1 to keep the silver potential at 360 mV. Ag-2 was added at an initial flow rate of 2.4 ml / min and an acceleration flow rate of 0.16 ml / min for 98 minutes.
The TEM image of the obtained emulsion grains was taken and shown in FIG. The particle structure is (33) A_FiveThe average value was an ellipsoidal sphere of about 1.16. The average diameter was 0.34 μm, and the variation coefficient of the diameter distribution was 0.08. The particles described in (33) accounted for 97% or more of the total projected area of the particles.
The particles were treated in the same manner as in Example 3 in Table 1_FiveWhen grown with CDJ-40 mV under the above conditions, 96% or more of the total projected area was the dodecahedron grains.
[0026]
Example 6
Dispersion medium solution 6 (containing 25 g of gelatin 1 and 1200 ml of water, HNO_ThreeTo the solution adjusted to pH 2.0 with AgNO_Three1.2 g dissolved solution) was placed in a reaction vessel, the temperature was kept at 75 ° C., and Ag-1 solution and X-41 solution were simultaneously mixed and added at 4 ml / min for 10 minutes while stirring. Next, using the Ag-2 solution and the X-42 solution, CDJ was added in the same manner as in Example 1 to keep the silver potential at 391 mV. Ag-2 was added at an initial flow rate of 2.4 ml / min and an acceleration flow rate of 0.16 ml / min for 98 minutes.
When a TEM image of the obtained emulsion grains was taken, the grain shape was hexagonal columnar grains shown in FIG. The average diameter was 0.65 μm, the average thickness was 0.26 μm, and the variation coefficient of the diameter distribution was 0.14. The particles accounted for 96% or more of the total projected area of all the particles.
[0027]
Example 7
The dispersion medium solution 1 was put in a reaction vessel, and the temperature was kept at 40 ° C., and Ag-1 solution and X-1 solution were simultaneously mixed and added at 4 ml / min for 8 minutes while stirring all the time. Next, the temperature was raised to 75 ° C., and −40 mV CDJ was added for 90 minutes in the same manner as in Example 1 using Ag-2 and X-2. The start flow rate of Ag-2 was 2.4 ml / min, and the linear acceleration flow rate was 0.24 ml / min. 1 ml of the emulsion was sampled and a TEM image of the replica film of the grains was taken and shown in FIG. The variation coefficient of variation in particle diameter was 0.06, the average diameter was 0.21 μm, and the particle shape was asymmetric tetrahedral particles as shown in FIG. The variation coefficient of the diameter distribution was 0.087. (37) A₆The average value was about 0.27, and the variation coefficient of the variation distribution was 0.12.
Thereafter, the emulsion was washed with water, re-dispersed, chemically sensitized, spectrally sensitized, and additives were added in the same manner as in Example 1 and coated on a PET base to obtain a sample.
[0028]
Example 8 FIG.
Dispersion medium solution 8 (30 g of gelatin 1, 1300 ml of water, 0.05 g of KI, pH 6.0) was put in a reaction vessel, kept at a temperature of 40 ° C., and 8 ml of Ag-2 solution and X-2 solution with stirring. The mixture was added at the same time for 8 minutes. Next, the temperature was raised to 75 ° C., and Ag-2 solution and X-2 solution were added in the same manner as in Example 1 for 18 minutes by adding −40 mV CDJ. The starting flow rate was 24 ml / min and the linear acceleration flow rate was 2.4 ml / min.
1 ml of the emulsion was sampled and a TEM image of the replica film of the grains was taken and shown in FIG. It was an asymmetrical tetrahedral particle. The average diameter is 0.12 μm, the coefficient of variation of the diameter distribution is 0.11, and A₆The average value was about 0.32, and the variation coefficient of the variation distribution was 0.14.
[0029]
Example 9
Dispersion medium solution 9 (25 g of gelatin 2 and 0.05 g of KI, pH 6.0) was put in a reaction vessel, and the temperature was kept at 18 ° C., and Ag-2 solution and X-2 solution were mixed at 5 ml / Added for 5 minutes. Next, using the Ag-2 solution and the X-2 solution, a CDJ having a silver potential of −40 mV was added in the same manner as in Example 1. Ag-2 solution was added at a start flow rate of 5 ml / min and an acceleration flow rate of 0.7 ml / min for 28 minutes.
At this point, 1 ml of the emulsion was sampled and gelatin and soluble salts were removed in the same manner as in Example 1. The collodion film was applied, and the particles were placed on a carbon-deposited mesh. After drying, it was cooled to about −130 ° C. and a TEM image was taken. The average diameter of the particles was 0.026 μm, and the variation coefficient of the diameter distribution was 0.11.
[0030]
Example 10
The dispersion medium solution 9 is put in a reaction vessel, and the temperature is kept at 18 ° C., while stirring, Ag-1 solution and X-3 solution (100 ml contains 3.36 g of KI and 1 g of gelatin 2, pH 6.0) Was added for 2 minutes at a starting flow rate of 1 ml / min and an acceleration flow rate of 12 ml / min. Subsequently, simultaneous mixing was added at 25 ml / min for 5 minutes. Next, using the Ag-2 solution and the X-2 solution, a CDJ having a silver potential of −40 mV was added in the same manner as in Example 1. Ag-2 solution was added at a start flow rate of 5 ml / min and an acceleration flow rate of 0.7 ml / min for 28 minutes.
As in Example 9, a TEM image of the generated particles was taken. The average diameter of the particles was 0.024 μm, and the variation coefficient of the diameter distribution was 0.09.
However, gelatin 1 = empty gelatin obtained by desalting alkali-treated beef bone gelatin through an ion exchange resin. Gelatin 2 = [HNO in aqueous solution containing gelatin 1_ThreeWas added to obtain a pH of 0.7, followed by hydrolysis at a temperature of 90 ° C. to obtain a mass average molecular weight of 15000. After desalting by ultrafiltration to remove 95% of the added acid, it was neutralized to pH 6.0 with NaOH. H₂O₂Was added and mixed, and then allowed to stand at 40 ° C. for 15 hours. 100% of Met changed to sulfinyl group. ]
[0031]
Comparative Example 1
Dispersion medium solution 11 (25 g of gelatin 1, 1200 ml of water, 2 g of KI and pH 6.0) is put in a reaction vessel, the temperature is kept at 75 ° C., and Ag-1 solution and X-1 solution are added at 4 ml / min for 10 minutes. , And added simultaneously. Next, using the Ag-2 solution and the X-2 solution, CDJ was added by a conventional method to keep the silver potential at -40 mV. Ag-2 was added at a start flow rate of 2.4 ml / min and an acceleration flow rate of 0.16 ml / min for 98 minutes. The amplitude of the silver potential in the CDJ was always 70 mV or more (total of 140 mV or more) with respect to the set value.
When a TEM image of the replica film of the generated particles was taken, it was a polydisperse particle containing particles of various shapes having an average diameter of 0.6 μm, a diameter distribution variation coefficient of 0.4, and three or more types.
For each of the emulsions obtained in Examples 1 to 10 and Comparative Example 1, the coagulating sedimentation agent 1 was added, the temperature was lowered to 30 ° C., the pH was lowered to around 4.0, the emulsion was flocked, and the sedimentation was performed. I let you. The supernatant was removed, and the emulsion was washed with water three times. Then, the pH was raised to 6.4 and the temperature was raised to 40 ° C. to redisperse. AgNO_ThreeSolution and KI solution were used to adjust the pAg of the emulsion to 5.5. Sensitizing dye 1 is added at an amount of 85% of the saturated adsorption amount at 40 ° C. to achieve adsorption equilibrium, the temperature is raised to 60 ° C., and chemical sensitizer 1 is added to 3.5 × 10.^-FourMole / mole AgX was added and aged for 50 minutes. The temperature is lowered to 40 ° C., and the antifogging agent 3 is 3 × 10^-3Only mol / mol AgX was added, and similarly adjusted to pH 6.4 and pHAg 5.5, and stirred for 30 minutes.
The emulsion was coated on a PET base with a protective layer containing hardener 1 (0.01 g / g gelatin) and dried. It put into the airtight container and it hold | maintained at 40 degreeC for 15 hours, and accelerated the dural reaction. The emulsion coatings of Examples 1-10 were designated Samples 1-10, and the emulsion coating of Comparative Example 1 was designated Comparative 1.
[0032]
Example 11
AgI Emulsion B was the same except that gelatin 3 used in Examples 3 and 4 was replaced with gelatin 3.₁₁, B₁₂Formed. B₁₁The produced particles had an average diameter of 0.05 μm and a variation coefficient of diameter distribution of 0.10. B₁₂The produced particles had an average diameter of 0.08 μm and a coefficient of variation of 0.09. 80 ml of the emulsion was collected, added to the dispersion medium solution 3 and grown in the same manner as in Example 3. In both cases, 99% or more of the projected area was the dodecahedron grains.
Gelatin 3 = Plate having a phthalation rate of 83% by allowing phthalic anhydride to act on gelatin 1.
B₁₁, B₁₂HNO_ThreeWas added to a pH of 4, and the emulsion was flocculated and allowed to settle, the supernatant was removed and washed three times with water. After the emulsion is washed with water, redispersion and the like are performed in the same manner as described above.₁₁, B₁₂Got.
Apply coated sample through optical wedge to 10^-2Samples exposed to blue light (wavelength light of 450 nm or less) for 2 seconds and samples exposed to -blue light (wavelength light of 500 nm or more) were prepared, and developed with pyrogallol developer described in Reference 10 at 40 ° C. for 50 minutes. After soaking in the stop solution for 1 minute, it was soaked in fixer (Super Fuji Fix) for 30 minutes to fix, then washed with water and dried. The sensitometry was performed, and the result of the (sensitivity / granularity) ratio is shown in Table 4. It was confirmed that the sample of the present invention was superior in (sensitivity / granularity) to the comparative sample.
Sensitivity is represented by the reciprocal of the exposure amount (looks / second) giving a density of (fog + 0.2), and the granularity is 10 as the amount of light giving the density of (fog + 0.2).^-2Exposure was performed uniformly for seconds, development was performed, density variation was measured with a microdensitometer using a circular opening with a diameter of 48 μm, and rms granularity σ was determined. The details are described in Chapter 21 section E of the document 11.
[0033]
Example 12
A reaction vessel of the type shown in FIG.₁= 3) is added dispersion medium aqueous solution (30 g of gelatin 1, 1500 ml of water, 0.05 g of KI, pH 6.5), kept at 70 ° C., Ag-12 liquid (AgNO in 100 ml) with vigorous stirring._Three3 g and 0.6 g of gelatin 4) at 160 ml / min, X-12 solution (29.3 g of KI and 1 g of gelatin 4 in 100 ml, pH 6.5) at 157 ml / min for 4 minutes, constant flow rate Added. At the same time, the silver potential was kept constant at -10 mV by adding X-120 solution (containing 30 g of KI and 0.6 g of gelatin in 100 ml, pH 6.5). The amplitude of the potential fluctuation was within 20 mV of the specified value. Immediately after the addition, cold water was put into a constant humidity bath and the temperature was rapidly cooled to 30 ° C. over 1 minute. This was designated as Emulsion 12a.
1 ml of the emulsion was collected, and the dye 1 was added by about 130% of the saturated adsorption amount and cooled to 20 ° C. A TEM image of the particles was taken in the same manner as in Example 9. The average diameter of the particles was about 30 nm and the coefficient of variation of the size distribution was 0.12.
Next, 27 ml of the emulsion was collected in a reaction container [25 g of gelatin 1, 0.05 g of KI, H₂O 2250 ml, pH 6.3, 60 ° C.), the microparticles were grown at a rate that did not generate new nuclei. Specifically, Ag-121 solution (AgNO in 100 ml)_ThreeCDJ addition was carried out for 12 minutes in the same manner as in Example 1, using X-121 solution (containing 4.9 g of KI in 100 ml) and maintaining the silver potential at 150 mV. The addition flow rate of the Ag-121 liquid was a start flow rate of 3 ml / min and an acceleration flow rate of 0.3 ml / min. The temperature was raised to 75 ° C. during the first 5 minutes of this addition. Next, the same CDJ was added using Ag-2 solution and X-2 solution while keeping the silver potential at 150 mV. The initial flow rate of Ag-2 solution was 2.6 ml / min and the acceleration flow rate was 0.24 ml / min. Cooling was started after 1 minute and the temperature was lowered to 30 ° C. in 2 minutes. This was designated as Emulsion 12b.
1 ml of the emulsion was collected, and Dye 1 was added in an amount of about 130% of the saturated adsorption amount. A TEM image of the replica film of the particles was taken. When about 3000 particles were observed, 99% of the particles were the dodecahedron, the average diameter was about 0.155 μm, and the variation coefficient of the size distribution was 0.08. Accordingly, the fine particles are fine particles that become dodecahedron when grown, and correspond to the item (19). Gelatin 4 is a gelatin having an average molecular weight of 15,000 obtained by degrading gelatin 1 with a degrading enzyme.
[0034]
Example 13
In the same reaction vessel as in Example 12, an aqueous dispersion medium (containing 30 g of gelatin 4, 1500 ml of water, pH 6.5) was kept at 20 ° C., and the Ag-12 solution was added at 160 ml / min with vigorous stirring. 12 liquids were added simultaneously at 157 ml / min for 4 minutes. At this time, the silver potential was kept at 120 mV by adding the X-120 solution at the same time. The potential fluctuation was within 20 mV of the specified value. The variation coefficient of size distribution was about 0.12. This was designated as Emulsion 13a.
Next, 29 ml of the emulsion was collected and placed in a reaction vessel [25 g of gelatin 1, 0.05 g of KI, H₂O 2250 ml, pH 6.3, 57 ° C.) and the microparticles were grown at a rate such that no new nuclei were generated. Specifically, the same CDJ was added using Ag-2 solution and X-2 solution while maintaining the silver potential at 150 mV. Ag-2 solution was added at a start flow rate of 1.8 ml / min and an acceleration flow rate of 0.13 ml / min for 105 minutes. After 1 minute, 1 ml of the emulsion was collected, dye 1 was added, and the mixture was cooled to 20 ° C. A TEM image of the replica film of the particles was taken. When about 3000 particles were observed, 99% of the particles were A.₆The tetrahedral particles had a value of 0.18 to 0.25. A₆The average value of was 0.21. The average diameter was 0.14 μm and the coefficient of variation was 0.08. This was designated as Emulsion 13b.
[0035]
Example 14 FIG.
In the same reaction vessel as in Example 12, the dispersion medium aqueous solution 14 (25 g of gelatin 1, 1.2 g of KI, H₂(Containing 1200 ml of O, adjusted to pH 10.2 with NaOH), and keeping at 65 ° C., Ag-1 solution and X-14 solution (containing 3.56 g of KI in 100 ml) were added at 12 ml / min for 10 minutes. . The temperature was raised to 75 ° C. over 5 minutes and after aging for 10 minutes, -190 mV CDJ addition was performed for 35 minutes using Ag-2 solution and X-14 solution (containing 16.84 g of KI in 100 ml). . The start flow rate was 7.2 ml / min and the acceleration flow rate was 0.64 ml / min. After completion of the addition, after aging for 5 minutes, the temperature was lowered to 30 ° C.
1 ml of the emulsion was collected, and Dye 1 was added in an amount of about 130% of the saturated adsorption amount. A TEM image of the replica film of the particles was taken. When about 1000 particles were observed, about 93% of the particles had the shape shown in FIG.₂It was a tabular grain having a value of 1.0 to 3.0 and an aspect ratio of 2 to 30. Average projected diameter is 0.8μm, average C₂= 1.7, average aspect ratio = 7.5, coefficient of variation of diameter distribution was about 0.2. In addition, the content of γ type determined by the same method as in Table 1 was about 45%. This emulsion was designated as Emulsion 14.
Sensitizing dye 1 was added to each of the emulsions obtained in Examples 12 to 13 in an amount of 85% of the saturated adsorption amount, and after equilibration, precipitating agent 1 was added, and the emulsion was washed with water in the same manner as described above. The temperature was raised to 40 ° C., phthalated bovine bone gelatin having a phthalation rate of 96% was added, and the emulsion was redispersed to pH 6.4 and pAg5. The methanol solution of the chemical sensitizer 2 is 3 × 10 3 for the emulsions 12a and 13a.^-Four10 for emulsions 12b, 13b, 14^-Four(Mole / mole AgX) was added and ripened at 47 ° C. for 60 minutes. The temperature is lowered to 40 ° C., and latent image formation efficiency improver 1 is added to emulsions 12a and 13a at 2 × 10^-35 × 10 for emulsions 12b and 14^-FourOnly (mol / mol AgX) was added and stirred for 30 minutes. Antifoggant 3 3 × 10^-3Only mol / mol AgX was added and adjusted to pH 6.4 and pAg 5.3.
Each emulsion was coated on the PET base together with the protective layer containing the hardener 1, dried and processed in the same manner as above, and the samples were sequentially designated as 12a, 12b, 13a, 13b, and 14. The coated sample was exposed in the same manner as described above, developed, and subjected to sensitometry. The results of (sensitivity / granularity) ratio are shown in Table 4. It was confirmed that the sample of the present invention was superior in (sensitivity / granularity) to the comparative sample.
[0036]
[Chemical 2]

[0037]
[Chemical 3]

[0038]
[Table 4]

[0039]
【The invention's effect】
By using the AgX emulsion of the present invention and the photographic light-sensitive material containing the emulsion, an AgX photographic light-sensitive material having an excellent (sensitivity / granularity) ratio was obtained.
[Brief description of the drawings]
FIG. 1 represents a schematic diagram of a particle structure. a represents a top view of the particle, b represents a side view of the particle as viewed from the right side, and c represents a top surface when the (101) plane is disposed on the top surface. d represents the particle structure when the particles a are viewed obliquely from above. e represents a top view of the elliptical spherical particles.
FIG. 2 represents a schematic diagram of the particle structure. a is a top view, b is a side view as seen from the side arrow direction of a, and c is a particle structure when the particles are seen obliquely from above. d represents a structural example when a particle having a structure different from C is viewed obliquely from above.
FIG. 3 represents a schematic diagram of the particle structure. a represents a top view, b represents a side view viewed from the direction of the arrow a, and c represents a particle structure when the particle is viewed obliquely from above.
FIG. 4 represents a schematic diagram of the particle structure. a represents the particle structure when the particle is viewed obliquely from above, b represents its side view, and c represents the particle structure when another example of the particle is viewed from obliquely above. d represents an example of a tetrahedral particle having a recess.
5A and 5C are top views of tabular grains, b is a grain structure when a is viewed obliquely from above, and d is a grain structure when c is viewed obliquely from above.
6 is a in FIG. 1, b is in c in FIG. 1, c is in e in FIG. 1, d is in c in FIG. 2, e is in b in FIG. 2, and f is in a in FIG. Further, f and g are examples of a more detailed particle structure of particles corresponding to a in FIG. 4 and h is a particle corresponding to b and d in FIG.
FIG. 7 represents a unit cell model of β-type AgI crystal.
FIG. 8 represents an X-ray diffraction pattern (relationship between X-ray diffraction intensity and 2θ) of CuKβ rays of AgI particles. a represents the pattern of the dodecahedron particles, b represents the hexagonal column particles, and c represents the pattern of the tetrahedral particles.
FIG. 9 is a graph showing a change in fL temperature (T ° K) of dodecahedron particles.
FIG. 10 is a TEM image of grains representing the grain structure of emulsion grains.
FIG. 11 is a TEM image of grains representing the grain structure of emulsion grains.
FIG. 12 is a TEM image of grains representing the grain structure of emulsion grains.
FIG. 13 is a TEM image of grains representing the grain structure of emulsion grains.
FIG. 14 represents a cross-sectional side view of the reactor.
[Explanation of symbols]
1. a₁, A₂, A_ThreeRepresents three crystal axes representing the crystal structure.
2. θ represents the angle between the incident X-ray beam and the substrate surface.
3.41 represents a recess.
4.6-1 represents a reaction solution.
5.6-2 represents a hollow liquid feeding tube.
6.6-3 represents a constant temperature jacket.
7.6-4 represents a constant temperature water circulation device.
8.6-5 represents a mixing box.

Claims (11)

In a silver halide emulsion having at least a dispersion medium, water and silver halide grains, 88 to 100% of the total projected area of the grains has an AgI content (mol%) of 85 to 100, and the grain shape is The outer shape other than the particle size is an octahedron having two parallel hexagonal surfaces and six rectangular surfaces on the side surfaces, or a simple shape having rounded corners and / or edges. A silver halide emulsion which is a kind and has a circle equivalent projected diameter (μm) of 0.002 to 20 . In a silver halide emulsion having at least a dispersion medium, water, and silver halide grains, 88 to 100% of the total projected area of the grains has an AgI content (mol%) of 85 to 100, and the shape of the grains is The outer shape other than the size of the particle has two parallel hexagonal surfaces and 12 trapezoidal surfaces on the side surfaces in a mirror image relation, and the hexagonal surfaces are combined into a tetrahedron. A silver halide emulsion which is a single type and has a circle equivalent projected diameter (μm) of 0.002 to 20. The size of the two hexagonal faces is different during one particle, and wherein the (small hexagonal area area / large hexagonal) = A ₆ is 0.1 to 0.92 The silver halide emulsion according to claim 2 . By simultaneously mixing and adding an aqueous solution containing Ag ⁺ and an aqueous solution containing X ⁻ to an aqueous solution containing a hydrophilic dispersion medium while keeping the silver potential of the solution constant, at least the dispersion medium, water, and silver halide grains Particles having a AgI content (mol%) of 85 to 100, and having a shape other than the size of the two particles, is 40 to 100% of the total projected area of the particles. An octahedron having a parallel hexagonal surface and six rectangular surfaces on the side surface, or a single species having rounded corners and / or ridges, and having a circle equivalent projected diameter (μm). In the method for producing a silver halide emulsion of 0.002 to 20, the silver potential amplitude (mV) is −50 to +50 with respect to a specified value at 30 to 100% of the addition time. Method for producing a featured silver halide emulsion . Ag ⁺ Solution containing X and X ⁻ The aqueous solution containing the aqueous dispersion medium is added to the aqueous dispersion solution containing the hydrophilic dispersion medium at the same time while maintaining the silver potential of the solution constant, thereby having at least the dispersion medium, water, and silver halide grains, and projecting the grains. Particles having a total area of 40 to 100% have an AgI content (mol%) of 85 to 100, and the shape of the particles is that the outer shapes other than the size of the particles are two parallel hexagonal surfaces, Twelve trapezoidal surfaces are mirror images of each other on the side surface, and are a single type of tetradecahedron combined with the hexagonal surface, and the equivalent circular projected diameter (μm) of the particles is 0.002 to 20. In the method for producing a silver halide emulsion, the silver potential emulsion has an amplitude (mV) of silver potential of -50 to +50 with respect to a specified value in 30 to 100% of the addition time. Manufacturing method. At least one of the Ag ⁺ solution and the X ⁻ solution is directly added to the reaction solution through the hollow tube, and the ratio of (the hollow tube length in the reaction solution / the inner diameter of the reaction vessel) = C ₁ is 0.5. 6. The method for producing a silver halide emulsion according to claim 4 or 5 , wherein the silver halide emulsion is. 6. The method for producing a silver halide emulsion according to claim 4 , wherein the amplitude of the silver potential is −30 to +30 with respect to a specified value. 6. The method for producing a silver halide emulsion according to claim 4 , wherein the amplitude of the silver potential is −15 to +15 with respect to a specified value. 6. The method for producing a silver halide emulsion according to claim 4 , wherein the total projected area of the grains is 88 to 100%. 6. The method for producing a silver halide emulsion according to claim 4 , wherein the total projected area of the grains is 95 to 100%. In one or photographic material coated with one or more silver halide emulsion layers on both sides of the support, at least one silver halide emulsion layer is sensitive silver halide emulsion according to claim 1 or 2, wherein A photographic light-sensitive material comprising:

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