JP4225664B2 - Method for producing silver halide emulsion - Google Patents

Description

【０００７】
式中、Ｒ¹ 〜Ｒ³ はそれぞれ同じであっても異なってもよく、それぞれ、水素原子、炭素数１〜６０の置換もしくは無置換の、アルキル基、アルケニル基、アラルキル基、アリール基を表わす。該水素原子数は２個以下が好ましく、１個以下がより好ましく、０個が更に好ましい。即ち、炭素数１〜６０の直鎖または分枝アルキル基、シクロアルキル基、炭素数２〜６０のアルケニル基、炭素数６〜６０のアラルキル基、アリール基が好ましい。これらの基は下記置換基で置換されていてもよい。Ｙ^- はアニオン（負荷電の原子または原子群）を表わす。例えば酸基、ＯＨ^- 基、ハロゲンイオンを挙げる事ができ、具体例としてＦ^- 、Ｃｌ^- 、Ｂｒ^- 、Ｉ^- 、ＮＯ₃ ^- 、０．５ＳＯ₄ ^2- 、Ｒ¹ ＣＯＯ^- 、Ｒ¹ −ＳＯ₃ ^- 、ＣｌＯ₃ ^- を挙げる事ができる。Ｒ² はＲ¹ またはＲ³ と閉環を形成する事もできる。なお、該オニウム塩基を１分子中に１基のみ有する化合物の場合や、特に記載がない場合は、（Ｉ−１）〜（Ｉ−８）式の自由結合手はＲ⁴ 基に結合している。Ｒ⁴ 基はＲ¹ 〜Ｒ³ と同じ定義の基を表わす。該置換可能な基として特開平１０−１０４７６９号記載の（ＳＢ１）を挙げる事ができ、例えばハロゲン原子、アルキル基、アルケニル基、アルキニル基、アラルキル基、アリール基、ヘテロ環基、アルコキシ基、アミノ基、カルボキシ基、スルホ基、エステル基である。これらの基はさらに置換されていてもよい。また置換基が二つ以上あるときは同じでも異なっていてもよい。
【０００８】
（Ｉ−１）式でＲ¹ 〜Ｒ⁴ が水素原子以外の原子の場合、該Ｎ⁺ はｐＨ１．０〜１２．０の領域においてｐＨに依存せず、常にＮ⁺ を保つ。しかし、Ｒ¹ 〜Ｒ⁴ の内の１つ以上が水素原子の場合、該水素原子のｐＫａ値（Ｋａは酸解離定数）以上のｐＨにおいては該水素原子がプロトンとして解離し、オニウム塩基ではなくなる確率が増す。この場合は、（該ｐＫａ＋０．３）〜（該ｐＫａ−６）、好ましくは該ｐＫａ〜（該ｐＫａ−５）のｐＨ条件で反応溶液中に該化合物を共存させる事を指す。
【０００９】
前記オニウム塩基を次の態様で２基以上、好ましくは３〜１０³ 基を連結する事もできる。（ａ）２価の連結基Ｌを介して該自由結合手間で、またはＲ¹ 基を介して連結する。Ｌはアルキレン、アリーレン、アルケニレン、−ＳＯ₂ −、−ＳＯ−、−Ｏ−、−Ｓ−、−ＣＯ−、−ＮＲ⁵ −（Ｒ⁵ はアルキル基、アリール基、水素原子を表わす）を単独または組合せて構成されるものを表す。好ましくはアルキレン、アルケニレンである。（ｂ）重合体鎖で結合する。結合されるオニウム塩基は同一種であっても互いに異なっていてもよく、前記（Ｉ−１）〜（Ｉ−８）式の２種以上の基を連結した態様でもよい。その場合の各種オニウム基の総計は２〜１０⁴ 基、好ましくは２〜１０³ 基である。
【００１０】
特にｐＨ１．５〜１２．０領域内にｐＫａ値（Ｋａは酸解離定数）を有する酸解離基を有するモノマーとの共重合体が好ましい。一般式で表わすと、（Ｉ−９）式で表わされる。
【００１１】
【化２】

【００１２】
ここでＲ⁸ は前記Ｒ¹ 〜Ｒ³ と同様の置換基を表わす。Ｒ⁹ は該酸解離基を有する置換基を表わす。ｎ１は１〜１０００、好ましくは２〜３００の整数を表わし、ｎ２、ｎ３は０以上の整数、好ましくは１〜１０⁴ 、より好ましくは２〜１０³ の整数を表わす。
この場合、ｐＨを該ｐＫａ値より上げたり、下げたりする事により、該Ｒ⁹ 基の水溶性の程度を変化させ、該重合体の吸着性を変化させる事ができ好ましい。例えば−ＣＯＯＨ基のような酸基の場合、そのｐＫａ値以上、好ましくは（ｐＫａ＋０．３）以上のｐＨに調節する事により（−ＣＯＯＨ→−ＣＯＯ^- ＋Ｈ⁺ ）となり、該基の親水性が上がりＡｇＸ粒子に吸着していた該重合体の脱着が促進される。即ち、該重合体が不要になった場合に、反応溶液のｐＨ値を調節する事により、該重合体をＡｇＸ粒子から脱着、除去する事ができる利点がある。−ＮＨ₂ 基のような塩基の場合はそのｐＫａ値以下、好ましくは（ｐＫａ−０．３）以下に下げる事により（−ＮＨ₂ ＋Ｈ⁺ →−ＮＨ₃ ⁺ ) となり、水溶性が増す。該解離性基として−ＳＯ₃ Ｍ、−ＳＯ₂ Ｍ、−ＯＳＯ₃ Ｍ、−ＣＯＯＭ、−ＮＨ₂ 、−ＮＨＲ¹ 、−ＮＲ¹ Ｒ³ 、−ＳＯ₄ Ｍ、−ＯＰＯ₃ Ｍ₂ 、（−Ｏ）₂ ＰＯＯＭを挙げる事ができ、好ましくは−ＳＯ₃ Ｍ、−ＳＯ₂ Ｍ、−ＣＯＯＭ、−ＮＨ₂ 、−ＮＨＲ¹ 、−ＯＰＯ₃ Ｍ₂ である。ここでＭはＨ、アルカリ金属、又は−ＮＨ₄ ⁺ を表わす。
【００１３】
またＲ⁸ に親水性基を導入し、（ｎ１／ｎ２）比を種々変化させると、該重合体の吸着特性をほぼ連続的に変化させる事ができ好ましい。該水溶性基としては、−ＯＨ、−ＣＮ、−ＣＯＮＨ₂ 、−ＣＯＯＣＨ₃ 、−（ＣＨ₂ ＣＨ₂ Ｏ）−、−ＣＯＮＨ−を挙げる事ができる。これらの基を合有するモノマーを重合させ、前記（Ｉ−９）式で表わされる化合物を合成すればよい。該（ｎ１／ｎ２）比および（ｎ１／ｎ３）比は１０^-4〜１０⁴ 、好ましくは１０^-3〜１０³ 領域で好ましい比率を選ぶ事ができる。
【００１４】
該水溶性基の例とそのｐＫａ値は次の通りである。−Ｃ₂ Ｈ₄ ＣＯＯＨ（４．６７）、−Ｐｈ−ＣＯＯＨ（４．２０）、−Ｐｈ−（ＣＨ₂)₂ −ＣＯＯＨ（４．６６）、−Ｃ₂ Ｈ₄ ＮＨ₂ 、−Ｐｈ−ＮＨ₂ （４．６５）、ピリジン基（５．４２）、−Ｐｈ−ＯＨ（９．８２）。但し、Ｐｈはフェニレン基を表す。該手法は（ii）〜（viii) の化合物に対しても好ましく用いる事ができる。
（i)の化合物にゼラチンは含まれない。またＮＨ₄ ⁺ 、−ＮＨ₃ ⁺ 基も好ましくは（i)に含まれない。
これらの化合物の具体例を（Ｉ−３１）〜（Ｉ−４６）に示した。
【００１５】
【化３】

【００１６】
【化４】

【００１７】
その他の具体例としてトリアゾール類のオニウム態様であるトリアゾリウム塩を挙げる事ができる。該化合物の詳細に関しては特開平４−３３５６３２号の記載を参考にできる。
これらの内、スルホニウム塩基、ホスホニウム塩基、セレノニウム塩基、アルソニウム塩基、スチボニウム塩基、スタンノニウム塩基、ヨードニウム塩基、複素環４級塩基含有化合物がより好ましい。
【００１８】
【化５】

【００１９】
（２）複素環窒素４級塩基含有化合物。
前記（１）記載のオニウム塩基において複素環窒素４級塩基含有化合物がより好ましい。該塩基を一般式で表わすと（II−１）〜（II−４）式で表わされる。該基を１分子中に１基以上、好ましくは２〜３００基含有する化合物。
【００２０】
【化６】

【００２１】
ここでＡ₁ 〜Ａ₄ は含窒素有機ヘテロ環を完成させる為の非金属原子群を表わし、それぞれが同一でも異なっていてもよい。Ｏ、Ｎ、Ｓ原子を含んでもよく、ベンゼン環が縮環していてもよい。Ａ₁ 〜Ａ₄ で構成されるヘテロ環は置換基を有してもよく、該置換基はそれぞれが同一でも異なっていてもよい。置換基としては前記（ＳＢ１）を挙げる事ができる。好ましい例としてはＡ₁ 〜Ａ₄ が５〜６員環（例えば、ピリジン環、イミダゾール環、チアゾール環、オキサゾール環、ピラジン環、ピリミジン環など）である態様、さらに好ましい例としてピリジン環をあげることができる。該化合物の具体例を（II−１１）〜（II−１６）に示した。
【００２２】
【化７】

【００２３】
（ａ）より好ましい化合物は一般式（II−２１）式と（II−２２）式で表わされる。式中、Ｒ²³、Ｒ²⁴はＲ¹ 、Ｒ² と同様の置換基を表わし、Ａ₅ 〜Ａ₈ はＡ₁ 〜Ａ₃ と同じで、含窒素ヘテロ環を完成させる為の非金属原子群を表わし、それぞれが同じでも異なっていてもよい。ｎ１１は０または１を表わし、分子内塩の場合には０である。ｎ１２は０または１を表わす。Ｌは前記と同じ２価の連結基を表わす。Ｙ^- は前記と同じアニオンを表わす。該化合物の具体例を（II−３１）〜（II−３７）に示した。
【００２４】
【化８】

【００２５】
【化９】

【００２６】
（ｂ）より好ましい化合物例として更に一般式（III −１）式で表わされる化合物を挙げる事ができる。式中、Ｒ³¹は前記Ｒ¹ 、Ｒ² と同様の置換基を表わし、Ｒ³²〜Ｒ³⁶はそれぞれ同じでも、異なっていてもよく、それぞれ水素原子またはこれと置換可能な基を表わす。該置換可能な基として前記ＳＢ１を挙げる事ができる。
Ｒ³²とＲ³³、Ｒ³³とＲ³⁴、Ｒ³⁴とＲ³⁵、Ｒ³⁵とＲ³⁶は縮環していてもよい。但し、Ｒ³²〜Ｒ³⁶の少なくとも１つがアリール基またはアラルキル基である事が好ましく、Ｒ³¹もアリール基またはアラルキル基である事がより好ましい。Ｙ^- は前記Ｙ^-と同じである。
Ｒ³²とＲ³³、Ｒ³³とＲ³⁴、Ｒ³⁴とＲ³⁵、Ｒ³⁵とＲ³⁶は縮環してキノリン環、イソキノリン環、アクリジン環を形成してもよい。以下の（III −２）〜（III −１１）に該化合物の具体的化合物例を示した。
【００２７】
【化１０】

【００２８】
【化１１】

【００２９】
（ｃ）より好ましい化合物例として更に、一般式（Ｉ−９）式で表わされ、かつ、該オニウム塩基が（II−３）式または（II−４）式で表わされる化合物。更には１分子中に該複素環窒素４級塩基と非環状第４級アンモニウム塩基をそれぞれ１基以上含有する化合物を挙げる事ができる。好ましくは各々を１〜１０⁴ 基、好ましくは２〜１０³ 基含有した化合物を挙げる事ができる。その具体的化合物例を（III −２１）に示した。
【００３０】
【化１２】

【００３１】
前記（１）、（２）の化合物の詳細、合成法に関しては米国特許第３０１７２７０号、同５４１８０７８号、同４５２５４４６号、欧州特許第０３９２０９２Ｂ１、特開平２−２９３８３８号、同７−３０６４８９号、同１０−１０４７６９号、同８−２９９０２号、同２−３４号、同８−２２７１１７号、国際公開特許ＷＯ９４／２０５５１号の記載を参考にできる。
【００３２】
（ii）芳香族環に１基以上のヨード基と１基以上の−ＯＨ基が置換した芳香族化合物。ヨード基は１〜８基、好ましくは２〜５基置換している事が好ましく、ヒドロキシ基が１〜３基、置換している事が好ましい。
ここで芳香族化合物とはベンゼン核をもつ炭素環式化合物を指し、ベンゼン環に他のベンゼン環や複素環が縮合した化合物（例えばナフタリン、アントラセン、キノリン、インドール）も含まれる。芳香族環とは該ベンゼン核、該ベンゼン環、該複素環が含まれるが、好ましくは該ベンゼン核、該ベンゼン環を指す。より好ましくは少なくとも１個のヨード置換基を含む８−ヒドロキシキノリン〔一般式は（IV−１）式で表わされる〕、またはイソキノリン類であり、その具体的化合物例を（IV−２）〜（IV−３）に示した。
その他、８−ヒドロキシ−７−ヨード−５−キノリンスルホン酸がある。
Ｒ⁶⁰、Ｒ⁶¹は前記（ＳＢ１）から選ぶ事ができ、極性置換基、ハロ置換基が好ましい。該化合物の詳細に関しては米国特許第５４１１８５２号、（iii)項の文献の記載を参考にできる。
【００３３】
【化１３】

【００３４】
(iii）含窒素複素環式化合物。
４〜７員環中に窒素原子を２つ以上含有する複素環を１分子中に１個以上含有する化合物であり、好ましくは次の化合物を挙げる事ができる。
（ａ）アザインデン類。好ましくはテトラアザインデン類であり、具体例として、キサンチノイド類〔一般式（Ｖ−１）式で表わされ、具体例としてキサンチン、尿酸を挙げる事ができる〕、アミノアザインデン類（具体例としてプリン、アデニン、グアニン、カイネチンがある）がある。
（ｂ）ジアジン類（ピリダジン類、ピリミジン類、ピラジン類）。
この内、置換ピリミジン類が好ましい。該置換基としては前記ＳＢ１を、好ましくはアミノ基を挙げる事ができる。具体的化合物例としてウラシル、シトシン、チミン、（Ｖ−２）〜（Ｖ−５）式の化合物を挙げる事ができる。
これらの化合物の詳細に関しては特公平５−４０２９８号、特開平５−２６５１１１号、同５−２０４０７７号、同５−２３２６１２号、特開昭６４−８３２５号、日本化学会編、新実験化学講座第１４巻、第９章、丸善（１９７８年）の記載を参考にできる。
【００３５】
【化１４】

【００３６】
（iv）シアニン色素類。２個の含窒素複素環をメチン基−ＣＨ＝またはその連鎖で結合した陽イオン構造をもつ色素を指し、酸基を１個以上、より好ましくは１〜２個有する事が好ましい。ここで酸基とは−ＳＯ₃ ^- 、−ＯＳＯ₃ ^- 、−ＣＯＯ^- を指し、好ましくは−ＳＯ₃ ^- 基を指す。イミダシアニン、オキサシアニン、チアシアニン、セレナシアニンおよびその２種の複合シアニンが好ましく、イミダシアニン、オキサシアニンがより好ましい。これらの化合物の詳細に関してはResearch Disclosure 、５０１巻、アイテム３６５４４、１９９４年９月（以後、〔Ｒ．Ｄ．１９９４年〕と記す）、文献９の記載を参考にできる。
【００３７】
（ｖ）〜(viii)。その他に特開昭６２−２９９９６１号に記載された２価イオウ基含有のヘテロ環基を有する化合物、特開昭６３−４１８４５号に記載された２価イオウ基含有の有機化合物、特開平３−２１２６３９号、同４−２８３７４２号に記載されたアミノチオエーテル類、特開昭６２−２１８９５９号に記載のチオ尿素またはその誘導体を挙げる事ができる。これらの化合物の一般式を（VII −１）〜（VII −４）式に示した。
【００３８】
【化１５】

【００３９】
これらの化合物の詳細に関してはそれぞれの化合物に対応する前記文献の記載を参考にできる。
【００４０】
式中のＺ⁷⁰は置換または無置換の飽和または不飽和ヘテロ環をイオウ原子と共に形成するに必要な原子群を表わし、炭素原子、窒素原子、酸素原子、硫黄原子から構成される原子群である。該複素環は３〜８員環であり、該環は他の環と縮合して縮合環を形成してもよい。該複素環は１つ以上の置換基を有してもよい。該置換基としては前記ＳＢ１を挙げる事ができる。
【００４１】
Ｘ⁷⁰はアルキル置換していてもよいアミノ基、四級アルキルアンモニオ基、またはカルボキシ基を表わし、Ｌ⁷⁰、Ｌ⁷¹、Ｌ⁷²は前記Ｌと同じ定義の２価の有機連結基を表わす。Ｙ^- はアニオン基を表わし、前記Ｙ^- と同じ定義である。ｍは四級アルキルアンモニオ基の数と同じである。該アルキル基の炭素数は１〜３が好ましい。
Ｍ⁷⁰は水素原子、アルカリ金属、アルカリ土類金属、置換または無置換のアルキル基、置換または無置換のアリール基、置換または無置換の複素環基を表わす。Ｘ⁷¹はＣＯ又はＳＯ₂ を表わす。Ｒ⁷⁵はヒドロキシ基、置換または無置換の（アルキル基、又はアリール基、又は複素環基、アミノ基、アルコキシ基、アリールオキシ基）を表わす。置換基としては前記ＳＢ１を挙げる事ができる。（VII −４）式の分子の炭素原子総数は３０以下が好ましく、２０以下がより好ましい。
Ｚ₁ 、Ｚ₂ の詳細、具体的化合物例に関してはその他、文献２０（特開平10−１０４７６９号、特開平11−３６４９０２号）の記載を参考にできる。
(i）〜(iii) がより好ましく、(i）が最も好ましい。
オニウム塩がπ共役系を形成した態様（Ｚ₁₁）、特にピリジニウム４級塩基（Ｚ₁₂）の如く環状π共役系を形成した態様（Ｚ₁₃）がより好ましく、該４級窒素原子に炭素数１〜６０個含有する基が共有結合した態様（Ｚ₁₄）が更に好ましく、Ｚ₁₄基含有化合物（Ｚ₁₅）が好ましい。(i）において、（II−３２）、（III −２）、（III −３）式の如く１分子中に置換または無置換のアリール基を１基以上、好ましくは、１〜10基有する化合物がより好ましい。
【００４２】
オニウム塩基はＡｇＸ粒子表面のＸ^- サイトにクーロン相互作用で吸着し、作用を発揮するが、Ｚ₁₃、Ｚ₁₄の態様では分子分極率が大きくなり、該相互作用がより大きくなると考えられる。該基が粒子表面に吸着する事により、〔Ａｇ_n Ｘ_m ^-(m-n)〕の如き負荷電イオンの粒子表面への吸着を促進し、粒子成長を促進する。一方、該アリール基により吸着が強化されているとその疎水性の為に、その脱着確率が低くなり、粒子成長を抑制する。多量に添加すると、後者の作用が支配的となり、粒子成長は大きく抑制される。適量添加では主平面の成長抑制とエッジ面の弱い成長抑制により直径分布の狭い薄い平板粒子が得られる, エッジ面の成長が促進される領域も存在する。
該化合物を八面体ＡｇＸ粒子に吸着させた時、該粒子のイオン電導度を増加させる化合物と減少させる化合物がある。本発明の効果の大きい化合物は減少させる化合物が多い。該粒子の誘電損失の周波数依存性測定において、高周波側の損失ピーク（Ｐ₁)は粒子表面の電導性Ａｇ⁺ に基づき、低周波側の損失ピーク（Ｐ₂)は、粒子内の格子間銀イオン（Ａｇ_i ⁺ ）に基づき、増加させる場合は両者を高周波側に移動させ、減少させる場合は、Ｐ₁ のピーク強度の減少を伴って両者を低周波側に移動させるものが多い。
【００４３】
前記プリン塩基類やピリミジン塩基類のような含窒素複素環化合物の場合、ＡｇＸ粒子に対する吸着性は、該ｐＨ域でｐＨ依存性を示す。該化合物の酸解離定数をＫａとする時、ｐＫａ以上のｐＨで吸着性が高くなる。ここでｐＫａ＝−log(Ｋａ）である。ｐＫａ以下のｐＨではプロトン付加の為、吸着性が低下する。従って、該化合物を好ましくはその（ｐＫａ−０．３）以上、より好ましくはｐＫａ〜（ｐＫａ＋５）のｐＨで分散媒溶液中に共存させる。
Ｚ₁ 、Ｚ₂ は分子内にｐＫａ＝１〜１２、好ましくは２〜１０、より好ましくは３〜９の酸解離性基を１〜１０００基有する事が好ましい。
【００４４】
該化合物群の中でＡｇＸ粒子に対する吸着力の強いものは、該粒子形成時に該双晶面形成を促進し、かつ、薄い平板粒子を生成する。適度の吸着力のものは該双晶面形成を抑制する効果を有する。吸着力が弱すぎるものは無影響といえる。同一化合物でも該効果は濃度、温度にも依存し、濃度が濃くなる程、また温度が低くなる程、該吸着力が強くなる（即ち、吸着滞在時間が長くなる）効果を呈する。また、共存する分散媒の吸着強度が強い時や、その濃度が高い場合、Ｚ₁ 、Ｚ₂ の吸着平衡濃度は減少する為、該効果を得るにはより高濃度のＺ₁ 、Ｚ₂ を必要とする。従って本発明の効果を得る為には該化合物種とその濃度、温度、ｐＨ、ｐＸ、分散媒種、分散媒濃度値を選ぶ必要があり、表１と後述の記載を参考にできる。
（ｉ）の化合物でＸ^- 塩化合物を用いる場合、反応溶液中の（Ｃｌ^- 濃度がＢｒ^- 濃度の２〜∞倍である時はＣｌ^- 塩化合物を用いる事が好ましく、該Ｂｒ^- 濃度がＣｌ^- 濃度の２〜∞倍である時はＢｒ^- 塩化合物を用いる事が好ましい。（ｉ）の化合物は例えばピリジン基含有化合物にハロゲン化アルキル化合物（Ｚ₃ ）をイソプロピルアルコール等の有機溶媒中で反応させると得られ、通常、塩の形で得られる。対イオンの種類は、Ｚ₃ のハロゲンイオンの種類を選ぶ事により選べる。または生成物がＢｒ^- 塩やＩ^- 塩の場合、これをＡｇＣｌ粒子を含む水溶液中に溶解すると、Ｂｒ^- やＩ^- はＣｌ^- とハロゲン置換する。ＡｇＸ粒子を遠心分離除去した水溶液から、Ｃｌ^- 塩を取り出す。または該生成物を水に溶解し、電気透析法で＋極にＸ^- を集めた後、＋極液を別の＋極液と置き換える。これらの方法により、Ｘ^- 種を自由に選択する事ができる。従って前記化合物例のＸ^- 種も自由に選ぶ事ができる。
（Ｉ−４） 実施態様（１）、（２）の説明。
Ａ₃ は通常種晶形成過程（Ａ₂₁）と成長過程（Ａ₂₂）を経て形成され、Ａ₂₁は通常、Ｚ₁ の存在するＡ₄ 中にＡｇ⁺ を含む溶液（Ａｇ⁺ 液）とハロゲンイオン（Ｘ^- ）を含む溶液（Ｘ^- 液）を、攪拌しながら同時混合添加する事によりなされる。
Ａ₂₁の期間はＡｇＸ核形成開始からＡ₂₂開始直前までの期間を指す。Ａｇ⁺ とＸ^- を添加し続けた場合、先ず不安定核が形成され、次にその数が増加する。次にその一部が安定核になり、残りは溶解消滅し、安定核数（種晶数）が一定となる。次のＡ₂₂で該安定核（種晶）が成長し、目的物が得られる。従ってＡ₂₁は該安定核数が一定になるまでの期間を指す。
Ｚ₁ はＡ₂₁のいずれの時点でも添加する事ができるが、該不安定核形成時に前記濃度で存在させる事が好ましい。従って、該核形成開始以前に、Ｚ₁ をＡ₄ 中に該濃度量で添加する事が好ましい。更にＺ₁ をＡ₂₁、Ａ₂₂でＡｇＸ１モルあたり１０^-9〜１．０、好ましくは１０^-8〜０．１モルだけ追加添加する事ができる。追加添加は、一度に全量を添加する事もできるし、連続的に添加する事もできるし、２〜１０³ 回に分けて添加する事もできる。それらの方法の２つ以上を併用する事もできる。添加するＡｇ⁺ 液とＸ^- 液の１つ以上、好ましくは両方に溶液１kgあたり、１０^-8〜１．０モルを添加する事もできる。
添加方法は溶液の他、粉末、溶液中に粉末を懸濁した態様で添加する事もできる。特にＡ₂₁に対して該追加添加方法を用いると、種晶形成中のすべての時期においてＺ₁ の濃度を最適に選ぶ事ができ、より好ましい種晶を形成できる。
これらの態様は（Ｉ−５）の態様に対しても適用できる。
Ｚ₁ が核形成時に存在すると、ＡｇＸ核に対するその適度な吸着力により、双晶面形成が防止される。その他、粒子間合着が防止され、刃状転位、ラセン転位の生成も防止される。Ａ₂₂では、ＡｇＸ粒子に対するその適度な吸着力により新たな新核の発生を防止し、粒子間の成長が均一化し、ＡｇＸ粒子の形状、ＡｇＸ組成が粒子間で均一なＡｇＸ乳剤粒子が得られる。
ＡｇＸ粒子に転位線を導入する工程、ＡｇＸ粒子に該ゲスト部を形成する工程、でＺ₁ が存在すると、転位線導入場所や本数、転位線の長さ、ゲスト部形成場所、ゲスト部のＡｇＸモル量が粒子間で均一化する。それらの量の粒子間バラツキの変動係数は０．０１〜０．５０が好ましく、０．０１〜０．２０がより好ましい。
Ａ₄ 、Ｂ₄ の分散媒溶液の好ましい条件（Ａ₂₅）、より好ましい条件（Ａ₂₆）に関しては表１に記載した。ここでｐＸ＝−ｌｏｇ〔Ｘ^- 〕であり、〔Ｘ^- 〕はＸ^- の濃度（mol/リットル) を表す。最も好ましい該組み合わせ条件領域（Ａ₂₇）を選ぶ事が好ましい。特にＡｇ⁺ とＸ^- の濃度差（モル／リットル）の絶対値｜〔Ａｇ⁺ 〕−〔Ｘ^- 〕｜が０．０〜１０^-1.5が好ましく、０．０〜１０^-2がより好ましく、０．０〜１０^-2.5が最も好ましい。該条件はＡ₃₁に対しても好ましい。
【００４５】
【表１】

【００４６】
（Ｉ−５） 実施態様（３）、（４）の説明。
（Ａ−１） Ｃ₂ の形成と、Ｃ₂ をＢ₃ に添加する方法。
反応容器（Ａ₃₀）中にＢ₄ とＺ₂ を添加し、攪拌しながらＡｇ⁺ 液とＸ^- 液を該溶液中に添加する事によりＣ₂ が得られる。
該形成過程（Ａ₃₁）の好ましい条件（Ａ₂₅、Ａ₂₆）を表１に示した。Ｚ₂ が存在する事により双晶面等の結晶欠陥形成が防止され、更には転位線の導入も防止される。Ｃ₂ を形成し、これをＢ₃ に添加する方法として次の方法がある。
１）Ｃ₂ を後述の脱塩法で脱塩処理した後にＢ₃ に添加する方法。該脱塩により該乳剤中の可溶性塩総量またはＺ₂ 含有量が該処理前の０〜９５％、好ましくは０〜５０％、より好ましくは０〜１０％に減じられる。
２）Ｃ₂ 中の可溶性塩の９５．１〜１００％をＣ₂ 中に存在させたまま、Ｂ₃ に添加する方法。
３）Ｃ₂ の総水分量の１〜１００％、好ましくは２０〜１００％、より好ましくは６０〜１００％を除去した後に添加する方法。該除去法の具体例は次の通り。３−１）大気中で乾燥する方法。３−２）１０^-7〜０．９９気圧、好ましくは１０^-6〜０．３気圧下で水分を蒸発除去する方法。真空凍結乾燥法も含まれる。３−３）遠心分離し、上澄み液を除去する方法。３−４）限外濾過法で水分を除去する方法。３−６）凝集沈降剤を添加し、乳剤を凝集沈降させ、上澄み液を除去する方法。
該脱塩法、該沈降剤に関しては（Ｉ−７）項の記載を参考にできる。
４）Ｃ₁ の形成をバッチ式反応容器中で行ない、形成されたＣ₁ を一度に、または２〜１０⁵ 回に分けてＢ₃ に添加する方法。または連続的に添加する方法。５）Ｃ₁ の形成と、Ｃ₁ の取り出しを同時進行で連続的に行う連続式形成法で形成する方法。これをＢ₃ に連続的に添加する事もできるし、取り出したＣ₁ を容器に入れ、蓄積した後にＢ₃ に添加する事もできる。
６）Ｃ₂ とＢ₃ の溶液条件が異なる場合、Ｃ₂ の条件をＢ₃ の条件またはそれに近い条件に調製した後にＢ₃ に添加する事ができる。例えばｐＨ、ｐＡｇ、温度、分散媒のＡｇＸ粒子への吸着力や分散媒濃度。ｐＨは酸、アルカリの添加によりｐＨ差を０〜３．０に、ｐＸはＡｇ⁺ 液やＸ^- 液の添加により、ｐＸ差を０〜３．０に、温度は反応溶液を冷却または加熱する事により、温度差を０〜４０℃、好ましくは０〜１５℃に調節される。
７）その他、後記文献１０の記載を参考にできる。
該１）〜７）の２つ以上を併用して用いる事が好ましい。
該微粒子の直径は小さい程、溶解し易いが、小さすぎると、Ａｇ⁺ とＸ^- のイオン溶液添加法に近づき、該方法の効果が小さくなる。小さい微粒子を形成する為にはＡｇＸの溶解度の低い条件で形成すればよい。この為には温度（℃）は０〜３０がより好ましく、０〜２０が更に好ましい。また、Ａｇ⁺ 錯体の合計濃度がＡｇ⁺ の濃度の０〜１０² 倍、好ましくは０．０〜１．０倍である事が好ましい。該条件はＡ₂₁に対しても好ましい。
また、粒子形成中に、低分散媒濃度領域を生じさせない事であり、添加するＡｇ⁺ 液とＸ^- 液の少なくとも一方、好ましくは両方に分散媒を質量％で０．０１〜１５、好ましくは０．１０〜５．０だけ溶解状態で存在させる事である。Ａｇ⁺ 液中に添加する場合は、酸（ＨＮＯ₃ 等）を一緒に添加〔分散媒１kgあたり酸を１０^-3〜１０² モル、好ましくは１０^-2〜１０モル添加する〕し、Ａｇ⁺ のＡｇへの変化を防止する事が好ましい。該態様はＡ₂₁に対しても好ましく用いる事ができる。
また、反応溶液のｐＨ、ｐＸ、分散媒濃度、温度をＡ₅ とＣ₁ 形成の目的に対し、表１に記載した領域で最も好ましい組み合わせ条件領域（Ａ₃₂）を選ぶ事が好ましい。
微粒子形成の為にＡｇ⁺ 液とＸ^- 液を短時間内に多量に添加すると、その反応熱で反応溶液の温度が上昇する。これを抑制し、温度（℃）を０〜３０、好ましくは０〜２０、より好ましくは０〜１０に保つ為に次の方法を好ましく用いる事ができる。
１）該Ａｇ⁺ 液とＸ^- 液の少なくとも一方、好ましくは両方の温度（℃）を０〜２５、好ましくは０〜２０に冷却してから添加する。これはａ）該液の貯蔵溶液を予め冷却しておく方法、ｂ）該液が送液管を通して添加される態様であり、かつ、該送液管の全長の０．１〜１００％、好ましくは１〜１００％が冷却剤中を通過した態様。該液は該送液管中を通過する時に冷却される。該送液管外径は細い方が比表面積が大きくなり、冷却効率がよく、０．１〜３００mmが好ましく、０．５〜５０mmがより好ましい。該冷却剤はそれ用に設けたもの、または反応溶液の恒温槽を利用する事ができる。または反応溶液を冷却剤として使用する事もできる。これらの２つ以上を併用する事もできる。
２）Ａｇ⁺ 液とＸ^- 液の添加と同時に、（反応溶液中および／または恒温槽中）に冷却剤〔氷、ガスの固化物（例えばドライアイス）、ガスの液化物（例えば液体窒素、液体酸素、液体空気）〕を添加する。添加量は予め、予備実験で該添加量と添加中または添加後の到達温度の関係を求めておき、目的の温度を達成するに必要な量を一度に、好ましくは２〜１００回に分けて、より好ましくは連続添加で添加する事が好ましい。その合計添加量は反応溶液１リットル当り、０．１〜１０⁴ ｇが好ましく、０．５〜１０³ ｇがより好ましい。
反応溶液中に冷却剤を添加する場合、該ガスの固化物、ガスの液化物を添加する方法は、氷に比べて反応溶液量の増加を伴わない為により好ましい。
Ｃ₁ は形成された後、０．０１秒〜１日、好ましくは０．１秒〜３時間、更に好ましくは０．１秒〜４０分の間にＢ₃ に添加される事が好ましい。
該微粒子中に均一に、または不均一にＡ₁₀態様で異種原子、該化合物をドープする事ができる。
Ｃ₁ と共にＺ₂ の５〜１００％、好ましくは２０〜１００％がＢ₃ に添加されてもよい。この場合、Ｚ₂ はＢ₁ の成長を制御し、より単分散性を良化する。特にＢ₁ が該平板粒子である場合、そのエッジ面の成長を弱く抑制し、速く成長する粒子をなくする。また、小さい種晶粒子が溶解するのを防止し、小さい粒子の生成も抑制する。その結果、サイズ分布の揃った粒子が得られる。しかし、それにはＺ₂ を最適濃度で存在させる必要がある。
Ｃ₁ は特にＡｇＩ含率が高い場合にその効果が大きい。
（Ｉ−１）の３）、４）の態様で前記平板粒子を成長させた時、平板粒子は粒子間で均一に成長し、粒子間特性の均一な平板粒子が得られる。
（Ｉ−６） 分散媒。
（Ａ−１） Ａ₂ 、Ａ₄ 、Ｂ₂ 、Ｂ₄ 用の分散媒に対する一般的記載。
分散媒としては公知の天然または合成、または天然物を化学修飾した水溶性分散媒を用いる事ができ、その質量平均分子量は１０³ 〜１０⁶ が好ましく、５０００〜１０⁶ がより好ましい。該分子量分布の変動係数は０．０１〜０．５０が好ましく、０．０１〜０．２０がより好ましく、０．０１〜０．１０が更に好ましい。単分散な該分散媒例として、分画ゼラチン（例えば限外濾過法で分画したゼラチンで後述の文献１８の記載を参考にできる）がある。また、該係数が０．５１以上の多分散な分散媒、該分子量分布曲線が２つ以上、好ましくは２〜１０個のピークを有する分散媒、低分子量分散媒にその１．２〜１０³ 倍の該分子量の高分子分散媒を混合した分散媒がある。この場合、低分子量分子はその分子サイズに相当する粒子表面〔例えば微粒子や薄い平板粒子のエッジ面、｛１１１｝平板粒子のトラフ部〕に吸着し、その成長を制御し、高分子量分子はマクロな面（例えば主平面）に吸着し、粒子間の凝集を防止する。即ち、より多機能な分散媒といえる。
ゼラチンを用いる場合、そのメチオニン基（Ｍｅｔ）含率（μmol/ｇ）またはチオエーテル基含率（μmol/ｇ）は０．０〜１２０の内、最も好ましいものを用いる事ができる。該含率はチオエーテル基を化学修飾〔該基を酸化し、スルホキシド基やスルホ基に変える事により、またはアルキル化剤（例えばハロゲン化アルキル）により、アルキル化する事により、またはチオニウム化〕する事により減少させる事ができる。一般式で表せば−Ｓ（Ｏ）−、−Ｓ（Ｏ₂)−、−Ｓ（Ｒ⁸⁰）−、−Ｓ⁺ （Ｒ⁸⁰、Ｒ⁸¹）−である。また該酸化体を経由して、−ＳＯ₃ ^2- とする態様もある。該変化した基は該基と見なさない。Ｈ₂ Ｏ₃ を添加して酸化したゼラチンがより好ましい。更には、該酸化後、残存酸化剤の５〜１００％、好ましくは２０〜１００％を除去したゼラチンが好ましい。該基含率を上げる為には、該含率の高い分散媒を選ぶ事や、チオエーテル基含有の炭素数１〜２０の有機化合物を分散媒分子に共有結合させればよい。
アミノ基およびイミダゾール基、カルボキシル基、水酸基の化学修飾率（％）は０．０〜１００が好ましく、１０〜９７がより好ましい。アミノ基の化学修飾は−ＮＨ₂ 基を２級または３級または４級アミノ基に変化させる事や、脱アミノ化する事を指し、一般式で表すと−ＮＨＲ⁸⁰、−Ｎ（Ｒ⁸⁰、Ｒ⁸¹）、−Ｎ（Ｒ⁸⁰、Ｒ⁸¹、Ｒ⁸²）であり、具体例として−ＮＨＣＯ−Ｒ⁸⁰、−ＮＨＳＯ₂ −Ｒ⁸⁰、−Ｎ⁺ （ＣＨ₃) ₃ がある。ここでＲ⁸⁰、Ｒ⁸¹、Ｒ⁸²は水素原子とハロゲン原子を除くＲ⁴ 基と同じ定義である。アミノ基の４級化は該基にハロゲン化有機物（Ｒ⁴ −Ｘ、例えばヨウ化メチル、臭化メチル）を作用させる事により得られる。
アミノ基、イミダゾール基、カルボキシル基、−ＯＨ基の化学修飾に関しては特願平１１−３２２９１３号、及び後記文献１８の記載を参考にできる。
該分散媒がシスチン、システインを含む場合もそのイオウ基を前記メチオニン基と同様に酸化し、スルフイノ基やスルホ基に変える事ができる。核酸類を含む場合はそのアミノ基、イミノ基を前記同様に化学修飾する事ができる。それぞれの修飾率（％）は０〜１００が好ましく、１０〜９７がより好ましい。分散媒として、該分子量と該修飾種と該修飾率のあらゆる組み合わせを用いる事ができる。該修飾種としては、単独種でもよいし、２種以上の併用でもよい。該アミノ基の化学修飾率が１０〜１００％のゼラチンを好ましく用いる事ができる。特にｐＨ６．０〜１２．０で該平板粒子を成長させた時に、平板粒子の厚さ方向への成長が抑制され、好ましい。
該分子量の調節は、分子量を増加させる時は硬膜剤で分子間を架橋する事により、分子量を低下させる時は酵素分解法、低ｐＨ又は高ｐＨ加水分解法、熱分解法等により行う事ができ、その詳細に関しては文献１７、特願平１１−３２２９１３号の記載を参考にできる。
ゼラチン種としてアルカリ処理、酸処理ゼラチン、イオン性不純物を除去したempty ゼラチン、アルギニン基の０．１〜１００％をオルニチン化したゼラチン、分子量分布を制御した分画ゼラチン、核酸塩基含有の質量％が０．０〜１０^-2、好ましくは０．０〜１０^-4のゼラチンがある。ゼラチン源としては特に制限はなく、あらゆる動物の結合組織が用いられるが、通常、（牛、ブタ、魚）の骨、皮が好ましく、アルカリ処理牛骨ゼラチンがより好ましい。分子量分布は変動係数（質量分子量分布の標準偏差／質量平均分子量）で０．０１〜０．６が好ましく、０．０１〜０．２０がより好ましい。
ＡｇＸ粒子に吸着するゼラチン中の残基の吸着力順は〔１）メチオニンの−Ｓ−基＞２）イミダゾール基＞＞３）−ＮＨ₂ 基＞−ＣＯＯＨ基〕であり、特に１）、２）、３）が化学修飾され、１分子あたりの該吸着エネルギーが元の８０〜０．１％、好ましくは５０〜１．０％に低下したゼラチンは平板粒子の成長抑制が小さい為に、薄い平板粒子の生成を可能にするので好ましい。
ゼラチン中の該メチオニン基はＡｇＸ粒子表面上のＡｇ⁺ サイトに吸着し、かぶり防止作用をする。これはかぶり防止剤の作用と同じである。
その他、公知の写真用分散媒、米国特許第５，３８０，６４２号記載のポリビニル化合物、ゼラチンと他の分子とのグラフトポリマーの１種または２種以上のあらゆる比率の混合物を用いる事ができる。これらの分散媒と前記分散媒の詳細に関しては後述の文献と文献１７、１８の記載、および（R.D.1996年）の記載を参考にする事ができる。
Ａ₄ に用いられる分散媒は、無双晶の種晶を形成するに適した分散媒である事が好ましく、ＡｇＸ粒子に対する吸着力が適度に強い分散媒が好ましい。この為に、ヒスチジン基含率（μmol/ｇ) が３〜３００、好ましくは１０〜１００のタンパク質やゼラチンが好ましい。Ｍｅｔ含率（μmol/ｇ) は３〜１２０が好ましく、１０〜８０がより好ましい。イミダゾール基含量の高いゼラチン例として魚、好ましくは３０℃以下の寒海に住む魚の結合組織（骨や皮）から抽出したゼラチンがある。従来公知のゼラチンにこれらの基を有する有機化合物を反応させ、共有結合させる事により合成する事もできる。例えば前記Ｒ⁸⁰、Ｒ⁸¹、Ｒ⁸²にそれらの基を含有させればよい。
分子量は高い程、保護コロイド性が良く、質量平均分子量は１０⁴ 〜１０⁶ が好ましく、１０⁵ 〜１０⁶ がより好ましく、３×１０⁵ 〜１０⁶ が更に好ましい。アミノ基および／または−ＣＯＯＨ基の含有量（μmol/ｇ）は１０〜１０³ が好ましく、１００〜１０³ がより好ましい。
（Ａ−２） Ｂ₄ 用の分散媒。
Ｂ₄ に用いられる分散媒には該保護コロイド性の高い分散媒が好ましい。しかし、Ｃ₁ が形成され、Ｃ₂ をＢ₃ に添加し、Ｃ₁ が溶解する時には分散媒の吸着力は弱い方がＣ₁ が溶解し易い為に好ましい。従って、Ｃ₁ を形成した後に分散媒の吸着力を弱める操作をする事が好ましい。該操作はＣ₁ を形成した後に、Ｃ₂ をＢ₃ に添加するまでの間に行う事ができるし、Ｂ₃ に添加した後に行う事もできる。前者の方が反応系がシンプルであり、より好ましい。
該操作には次の方法がある。
１）酸化剤を添加し分散媒の吸着基を酸化し、その吸着性を低下させる。該酸化剤の標準電極電位（Ｅ₁ ）が高い程、また酸化剤の濃度が高い程、吸着基が酸化される確率が高くなる。吸着基の標準電極電位をＥ₂ とすると、〔Ｅ₁ ＞（Ｅ₂ −０．２）〕である事が好ましく、〔（Ｅ₁ −Ｅ₂ ）＝０．０〜１．２〕である事がより好ましい。該値が高すぎると、酸化剤は水や他の基とも反応し、目的物の酸化効率が低下する為である。該電位は通常、標準水素電極電位を０とする値で示され、該値と化合物例に関しては例えば後述の文献１１と１２の記載を参考にできる。ここで該電位の単位はすべてボルトである。
例えば酸化剤を添加し、チオエーテル基を酸化し、−Ｓ（Ｏ）−、−Ｓ（Ｏ₂)−、−ＳＯ₃ Ｈ基に変える事や、−ＳＨ基を−ＳＯ₃ Ｈ基に変える事、がある。これにより、チオエーテル基含量（μmol/ｇ）を該操作前の０．１〜９５％、好ましくは１．０〜７０％、より好ましくは１．０〜３０％に減少させる。例えばタンパク質（ゼラチンを含む）の場合、Ｍｅｔ含率（μmol/ｇ）が５〜１００の該分散媒を用いてＣ₁ を形成した後、該乳剤に該酸化剤（Ｈ₂ Ｏ₂ 等）を添加し、経時させる事により、該態様を実現する。
２）該吸着基に有機化合物を共有結合させる。例えばチオエーテル基にハロゲン化アルキルを作用させ、スルホニウム化する事や、含窒素複素環含有化合物にハロゲン化アルキルを作用させ窒素原子をアルキル化する事、がある。
３）該吸着基を切断し、除去する事。例えば（-NHCO- + H₂O) →（-NH₂ + -COOH) 。
４）分散媒を低分子量化する。酸またはアルカリ、または酵素により高分子の主鎖を加水分解し、低分子量化する。粒子に対する吸着力は分子量が低下する程、弱くなる。質量平均分子量を元の１０^-3〜０．９倍、好ましくは１０^-3〜０．３倍にする。
５）分散媒を還元する事により該吸着力が弱くなる時は、還元する。
該酸化、還元の試薬、手法の詳細に関しては後述の文献１１、１２の記載を参考にできる。
これらの反応温度（℃）は５〜１００が好ましく、１０〜６０がより好ましい。反応時間（分間）は０．１〜１０⁴ が好ましく、１〜１０³ がより好ましい。反応溶液のｐＨは０．１〜１３が好ましく、１．０〜１２がより好ましい。
該操作により、分散媒のＡｇＸ粒子に対する吸着力は該操作前の吸着力の０．１〜９５％、好ましくは１．０〜７０％、より好ましくは１．０〜３０％に低下する。該吸着力は、同一で同一質量のＡｇＸ粒子に対し、同一質量の分散媒を添加し、吸着平衡にさせた時の吸着熱量で比較する事ができる。例えば〔ゼラチン分散媒のＡｇＸ乳剤を遠心分離し、上澄み液を除去し、次に水を入れ、再分散する事〕を２〜１０回、繰り返して行ない、分散媒を除去した後に、該当分散媒水溶液を添加し、吸着平衡に達するまでの間に発生する総熱量を測定する。
または、該吸着平衡時の分散媒の吸着量で比較する事ができる。例えば該吸着平衡にあるＡｇＸ粒子を静置自然沈降または遠心分離法により沈降させ、上澄み液を除去し、沈澱物を乾燥させる。その一定質量を粉末化し、一定質量のＫＢｒ粉末と混合し、その赤外吸収スペクトル（ＦＴＩＲと称される）を測定する。分散媒の赤外吸収強度（５００〜２０００cm^-1領域）を比較する。
またＡｇ⁺ 液またはＸ^- 液を添加した時の銀電位変化を表す曲線を書いた時、その変曲点に達するまでに添加するＡｇ⁺ またはＸ^- の添加モル量で比較できる。該量が多い程、表面の該当原子に対する該吸着力が大きい。
Ｃ₁ を形成した後、その分散媒の５〜９９％、好ましくは２０〜９９％を除去した後に、Ｂ₃ に添加する事もできる。該除去法例として、後述の脱塩法、遠心分離法、またはその併用法を用い、Ｃ₁ を沈降させ、上澄み液を除去する方法がある。
双晶面等の欠陥形成を防止するには分散媒の吸着強度は強すぎず、弱すぎず、適度である事が好ましい。弱すぎると、粒子間合着が生じ、双晶面等の欠陥が生成する。強すぎると、分散媒が吸着したまま粒子が成長し、それが内部に取り込まれる事により結晶欠陥（例えばラセン転位や刃状転位）が生じる。強い分散媒が高濃度で存在すると、粒子成長は阻害され、新核の発生期間が長くなり、超微粒子が得られる。しかし、該乳剤をＢ₃ に添加した場合、該微粒子は該分散媒に保護され再溶解し難い。また、該分散媒も一緒にＢ₃ に添加され、それがＢ₁ の成長を阻害する。従って弱い吸着力の分散媒で、目的のＡｇＸ微粒子が形成される事が最も好ましい。Ｚ₂ の存在下で形成すると、これが可能となる。これにより実施態様（18）が可能となる。
（Ｉ−７） 脱塩法と、Ｚ₁ 、Ｚ₂ の脱着、除去法。
ＡｇＸ乳剤の脱塩法例として次の方法がある。１）乳剤を２５℃以下に冷却し、ゲル化し、水洗する方法。ヌーデル水洗法とも呼ばれる。２）凝集沈降剤を加えて乳剤を最適ｐＨで沈降させ、水洗する方法。沈降剤としてＮａ₂ ＳＯ₄ の如き無機沈降剤（塩析効果を有する）と、有機沈降剤、アルコールの如き、ゼラチンを不溶性化する有機溶媒がある。有機沈降剤の多くは分散媒分子中のイオン性基の荷電を中和し、その親水性を低下させる事により、水に不溶化し、不溶化凝集させるものである。例えばナフタレンスルホネート、ホルムアルデヒドレジン化合物はゼラチンの−ＮＨ₃ ⁺ 基を荷電中和し、該不溶化させる。３）フタル化ゼラチンの如く、あるｐＨ領域で凝集する分散媒を用い、ｐＨ調節で凝集沈降させる方法。４）遠心分離法、ハイドロサクロン法の利用。５）限外濾過法、遠心濾過法の利用。６）電気透析法の利用。分散媒の等電点ｐＨとのｐＨ差が０〜３、好ましくは０〜１である態様。７）イオン交換樹脂と接触させる方法。これらの詳細については（R.D.1996年）、後述の文献の記載を参考にできる。
本発明で用いる事のできる酸、アルカリ（塩基）に関しては、化学便覧、基礎編、第１０章の記載を参考にでき、ＨＮＯ₃ 、Ｈ₃ ＰＯ₄ 、Ｈ₂ ＳＯ₄ 、ＮａＯＨ、ＫＯＨを好ましく用いる事ができる。
Ａ₃ を化学増感、または化学増感と分光増感し、塗布した感光材料は、特にそのガンマ値が２．０〜２０、好ましくは３．０〜２０の硬調感材において（感度／粒状度）比に優れ、好ましい。
（Ｉ−１）の実施態様でＡｇＸ乳剤を調製した後、塗布直前までの任意の時間に、好ましくは脱塩工程前にＺ₁ 、Ｚ₂ の１．０〜１００％、好ましくは７０〜１００％を脱着させる事ができるし、脱着させ、系外に除去する事ができる。１０〜９８℃、ｐＨ１．０〜１２．５、ｐＸ＝０．５〜５．０の範囲内で最も好ましい組み合わせ条件下で、５秒間〜１０日間、好ましくは１分間〜５時間かけて脱着し、除去する事ができる。該脱着、除去の詳細に関しては特願平１１−３６４９０２号の記載を参考にできる。
その他、該オニウム塩の如きカチオン性有機化合物に対し、アニオン性有機化合物を、Ｚ₁ 、Ｚ₂ の存在量の０．０１〜１０⁵ 倍モル量、好ましくは０．１〜１０⁴ 倍モル量だけ添加して除去する事もできるし、電気透析法で負極側に該化合物を集めて、それを除去する事もできる。該化合物例として分子量が１００〜１０⁶ 、好ましくは１００〜１０⁵ のアニオン性界面活性剤があり、後述の文献１６、（R.D.1996年）の記載を参考にできる。その他、該乳剤の塩濃度を上げ、イオン強度を１．２〜１０⁴ 倍、好ましくは２〜１０⁴ 倍に上げる事により、（ｉ）の化合物を塩析し、除去する方法がある。該化合物は塩析され易く、かつ、軽元素原子からなる為にその比重は水または該乳剤の比重よりも小さい為に、乳剤の表面に浮遊物として塩析され易い。該浮遊物を乳剤から除去すればよい。表面部を吸い取る方法、乳剤を容器の底から静かに出し、表面部を容器中に残す方法等がある。
該添加する可溶性塩に関しては、無機化合物・錯体辞典、講談社（１９９７年）の記載を参考にできる。その他、Ｘ^- 塩が好ましく、ｐＸ＝０．５〜２．５、好ましくは０．７〜２．０で脱着し、塩析する事ができる。Ｘ^- 種としてＣｌ^- 、Ｂｒ^- の単独またはあらゆる比率での併用を用いる事ができる。（オニウム⁺ ）・（Ｘ^- ）←→（オニウム⁺ ）＋（Ｘ^- ）の溶解平衡を左側にシフトさせる為である。
（Ｉ−８）その他。
Ａ₁ 、Ｂ₁₃、好ましくはＡ₁ 、Ｂ₁₅は、コア部のＡｇＩ含率（モル％）が０．１〜４０、好ましくは１〜４０、シェル部のＡｇＩ含率（モル％）が０．０〜２０の２重構造粒子が好ましく、（コア部／シェル部）モル比＝１/10⁴〜10⁴/１が好ましく、１/10³〜10³/1 がより好ましい。粒子サイズ（μm ）は０．１〜２０が好ましい。（コア部のＡｇＩ含率−シェル部のＡｇＩ含率）(mol%)＝０．１〜４０、好ましくは１〜４０、より好ましくは５〜３５である。更にＡｇＸ溶剤濃度（モル／リットル）が０〜１．０、好ましくは０〜０．０１、より好ましくは０〜１０^-5のもとで形成された粒子が好ましい。
Ａｇ⁺ と配位結合し、親水性の大きい化合物はＡｇＸ溶剤として作用し、小さい化合物はかぶり防止剤（Ａ₄₀）や、粒子変形防止剤として作用する。ｐＸ＝２．２以下、好ましくは０．３〜１．７では粒子表面はＸ^- 体であり、Ａ₄₀は殆ど吸着できない。Ａ₄₀はＡｇＸｎ（ｎは２以上の整数）錯体と配位結合し、親水性化し、ＡｇＸ溶剤として作用する。この為、薄平板粒子は厚板化する。従って該領域で温度４０〜１００℃域でのＡ₄₀の使用は避ける事が好ましい。
Ａ₁ 、Ａ₀ の粒子は粒子内が高ｐＨ（ｐＨ８〜１３）および／または還元剤により還元増感され、粒子内に還元銀核、酸化銀核が０．１μm³あたり１〜１０⁸ 個、好ましくは５〜１０⁶ 個存在している事が好ましい。４０〜１００℃で１時間〜１日間、感光材料を保存すると、粒子内の該核は移動し、感材の写真性が変化する。その変化の活性化エネルギー（kjoule/mol) は５０〜７５、好ましくは５７〜６７であり、小さい。これは好ましくない。これを防止する為には粒子形成中に粒子内部に転位線を導入する工程後に還元増感を行ない、転位線上に該核を形成する事や、前記不純物ドープ時に該核を形成し、両者を近接または結合させて存在させ、該核を安定化させる事である。またはＡｇＸ乳剤の塗布後から感材の出荷までの間に４０〜１２０℃、好ましくは５０〜９０℃、湿度１〜７０、好ましくは５〜４０％で１０〜１０⁵ 分間、好ましくは６０〜１０⁴ 分間保存し、該核を化学平衡状態に達せしめる事が好ましい。
または粒子形成後で、化学増感剤添加直前の間に、静置または攪拌しながら該温度、該時間でＡｇＸ乳剤を保持し、該核を化学平衡状態に達せしめる事が好ましい。
該ＡｇＸ粒子、該エピタキシャル粒子、ホスト粒子に対する金属ドープ、金属錯体ドープ、化学増感、分光増感、カラー感材構成の為のカラー素材と層構成、現像処理に関しては、後記文献５の記載を参考にできる。
【００４７】
これらの平板粒子をコアとして内部に転位線を有する前記粒子を形成してもよい。これに関しては後記文献１３の記載を参考にできる。
該粒子をコア粒子とし、コア粒子と異なるＡｇＸ層を積層させ、前記多重構造粒子を形成する事もできる。その詳細に関しては文献１４の記載を参考にできる。
（化学増感）
ＡｇＸ乳剤の化学増感にカルコゲン増感剤〔イオウ増感剤、セレン増感剤、テル増感剤〕、金増感剤の単独、またはその２種以上のあらゆる比率の併用を用いる事ができる。ＡｇＸ粒子１．０モルあたりカルコゲン増感剤の総量と金増感剤の総量はいずれも１０^-9〜１０^-2モルが好ましく、１０^-7〜１０^-4モルがより好ましい。該化合物の詳細に関しては、文献15、 (R.D.1996年) および後述の文献の記載を参考にできる。
高ＡｇＣｌ含率平板粒子乳剤形成の製造に関しては特開平８−２２７１１７号、同９−２８８３２５号、同２−３４号の記載を参考にできる。
該平板粒子乳剤に該高屈折率無機微粒子を添加し、含有させ、該乳剤が支持体上に塗布され感光材料を形成した時に、該分散媒相が該層の感光ピーク波長光に対して実質的に透明であり、該光に対する該分散媒相の屈折率値が該微粒子を含有しない時の該値の１．０３〜２．５倍、好ましくは１．０６〜２．０倍であり、該層中の平板粒子の主平面に対する該光の垂直反射率が、該含有しない時の０．１〜９７％、好ましくは１〜８０％である事が好ましい。
該微粒子は該層中で微粒子間が実質的に合着していなく、（７コ以上、好ましくは３コ以上合着した微粒子のモル量／全微粒子のモル量）が０．０〜０．２が好ましく、０．０〜０．０５がより好ましい。該感光材料が青感層、緑感層、赤感層の１層以上、好ましくは３層、より好ましくは第４感光層をも有するカラー感光材料である事が好ましく、該感光材料が露光され、少なくとも現像過程と定着過程を含む現像処理工程で処理される事が好ましい。該微粒子含有乳剤は後述のすべての感光材料、好ましくはカラー感光材料の感光層として用いる事ができる。拡散転写型カラー感材の場合は、該乳剤中に色材が添加される。該色材、カラー写真用発色剤、添加剤、乳化分散用油に関しては（Ｒ．Ｄ．１９９６年）、特願平１１−２８０２０７号および後述の文献の記載を参考にできる。
該微粒子は結晶、アモルファス、両者の混合物があり、１層以上のコア層と１層以上のシェル層を有する（コア／シェル）構造や多重構造粒子がある。金属酸化物が好ましく、ＴｉＯ₂ 含率（モル％）が１０〜１００、好ましくは５０〜１００がより好ましい。これらの詳細に関しては特願平１１−２８０２０７号、同１１−２１１３６４号の記載を参考にできる。
該粒子の厚さが薄い為、その固有吸収光量が低下する。青光感光乳剤に対してはこれを補う為に３５０〜５３０nm領域内に吸収バンドを有する増感色素を飽和吸着量の２０〜３００％、好ましくは６０〜２００％で吸着させる事が好ましい。
【００４８】
本発明の方法で製造したＡｇＸ乳剤粒子を他の１種以上のＡｇＸ乳剤とブレンドして用いることもできるし、粒径の異なる本発明の乳剤粒子を２種以上ブレンドして用いることもできる。ブレンド比率（ゲストＡｇＸ乳剤モル／ブレンド後のＡｇＸ乳剤モル）は好ましくは０．９９〜０．０１の範囲で適宜、最適比率を選んで用いることができる。本発明の乳剤に粒子形成から塗布工程までの間に添加できる添加剤およびその添加量に特に制限はなく、従来公知のあらゆる写真用添加剤を最適添加量で添加することができる。例えばＡｇＸ溶剤、ＡｇＸ粒子へのドープ剤（例えば第８族貴金属化合物、その他の金属化合物、カルコゲン化合物、ＳＣＮ化物等）、分散媒、かぶり防止剤、増感色素（青、緑、赤、赤外、パンクロ、オルソ用等）、強色増感剤、化学増感剤（イオウ、セレン、テルル、金および第８族貴金属化合物、リン化合物、ロダン化合物、還元増感剤の単独およびその２種以上のあらゆる比率での併用）、かぶらせ剤、乳剤沈降剤、界面活性剤、硬膜剤、染料、色像形成剤、カラー写真用添加剤、可溶性銀塩、潜像安定剤、現像剤（ハイドロキノン系化合物等）、圧力減感防止剤、マット剤、帯電防止剤、寸度安定剤等をあげることができる。
【００４９】
本発明法で調製したＡｇＸ乳剤は、従来公知のあらゆる写真感光材料に用いることができる。例えば、黒白ハロゲン化銀写真感光材料〔例えば、Ｘレイ感材、印刷用感材、印画紙、ネガフィルム、マイクロフィルム、直接ポジ感材、超微粒子乾板感材（ＬＳＩフォトマスク用、シャドーマスク用、液晶マスク用）〕、カラー写真感光材料（例えばネガフィルム、印画紙、反転フィルム、直接ポジカラー感材、銀色素漂白法写真など）に用いることができる。更に拡散転写感光材料（例えば、カラー拡散転写要素、銀塩拡散転写要素）、熱現像感光材料（黒白、カラー）、高密度 digital記録感材、ホログラフィー用感材などをあげることができる。塗布銀量は０．０１〜５０（ｇ／m²）の好ましい値を選ぶことができる。
ＡｇＸ乳剤製造方法（粒子形成、脱塩、化学増感、分光増感、写真用添加剤の添加方法等）および装置、ＡｇＸ粒子構造、支持体、下塗り層、表面保護層、写真感光材料の構成（例えば層構成、銀／発色剤モル比、各層間の銀量比等）と製品形態および保存方法、写真用添加剤の乳化分散、露光、現像方法等に関しても制限はなく、従来もしくは今後公知となるあらゆる技術、態様を用いることができる。これらの詳細に関しては下記文献の記載を参考にすることができる。
【００５０】
文献２０、リサーチ ディスクロージャー（Research Disclosure)誌、（アイテム１７６４３）（１９７８年１２月）、（Ｒ．Ｄ．１９９６年）、ダフィン（Duffin) 著、写真乳剤化学（Photographic Emulsion Chemistry)、Focal Press, New York （１９６６年）、ビル著（E. J. Birr) 、写真用ハロゲン化銀乳剤の安定化（Stabilization of Photographic Silver Halide Emulsion) 、フォーカル プレス（Focal Press)、ロンドン（１９７４年）、ジェームス編（T. H. James)、写真過程の理論（The Theory of Photographic Process) 第４版、マクミラン（Macmillan)、ニューヨーク（１９７７年）
【００５１】
グラフキデ著（P. Glafkides) 、写真の化学と物理（Chimie et Physique Photograph ique) 、第５版、 (Edition del, Usine Nouvelle 、パリ（１９８７年）、同第２版、ポウル モンテル、パリ（１９５７年）、ゼリクマンら（V. L. Zelikman et al.)、写真乳剤の調製と塗布（Making and Coating Photographic Emulsion) 、Focal Press （１９６４年）、ホリスター（K. R. Hollister)ジャーナル オブ イメージング サイエンス（Journal of Imaging Science) 、３１巻、Ｐ．１４８〜１５６（１９８７年）、マスカスキー（J. E. Maskasky) 、同３０巻、Ｐ２４７〜２５４（１９８６年）同３２巻、１６０〜１７７（１９８８年）、同３３巻、１０〜１３（１９８９年）、
【００５２】
フリーザーら編、ハロゲン化銀写真過程の基礎（Die Grundlagen Der Photographischen Prozesse Mit Silverhalogeniden）（Akademische Verlaggesellschaft) 、フランクフルト（１９６８年）。
日化協月報１９８４年、１２月号、Ｐ．１８〜２７、日本写真学会誌、４９巻、７〜１２（１９８６年）、同５２巻、１４４〜１６６（１９８９年）、同５２巻、４１〜４８（１９８９年）、特開昭５８−１１３９２６〜１１３９２８号、同５９−９０８４１号、同５８−１１１９３６号、同６２−９９７５１号、同６０−１４３３３１号、同６０−１４３３３２号、同６１−１４６３０号、同６２−６２５１号、
【００５３】
特開平１−１３１５４１号、同２−８３８号、同８−２２０６６４号、同８−２２７１１７号、同２−１４６０３３号、同３−１５５５３９号、同３−２００９５２号、同３−２４６５３４号、同４−３４５４４号、同２−２８６３８号、同４−１０９２４０号、同２−７３３４６号、同４−１９３３３６号、特願平６−２１５５１３号、ＡｇＸ写真分野のその他の日本特許、米国特許、欧州特許、国際公開（ＷＯ）出願、ジャーナル オブ イメージング サイエンス（Journal of Imaging Science) 、ジャーナル オブ フォトグラフィック サイエンス（Journal of Photographic Science)、フォトグラフィック サイエンス アンド エンジニアリング（Photographic Science and Engineering) 、日本写真学会誌、日本写真学会講演要旨集、International Congress of Photographic Scienceおよび The International East-West Symposium on the Factors Influencing Photographic Sensitivityの講演要旨集。特願平６−１０４０６５号、同５−３２４５０２号。
本発明の乳剤は特開昭６２−２６６５３８号、同６３−２２０２３８号、同６３−３０５３４３号、同５９−１４２５３９号、同６２−２５３１５９号、特開平１−１３１５４１号、同１−２９７６４９号、同２−４２号、同１−１５８４２９号、同３−２２６７３０号、同４−１５１６４９号、特願平４−１７９９６１号、同１１−５７０９７号、欧州特許０５０８３９８Ａ１の実施例の塗布試料の構成乳剤として好ましく用いることができる。
【００５４】
（文献）
１．特開昭５９−１３３５４２号、同６０−９５５３３号、米国特許第３，２０６，３１３号、同３，３１７，３２２号、同３，７６１，２７６号、同４，２６９，９２７号、同３，３６７，７７８号、特開平１−１５８４２９号、同１−２９７６９４号、（R.D.1994年）、および後述の文献。
２．特開昭６３−３０５３４３号、同６４−６２６３１号、同６４−４０９３８号、特開平２−８３８号、同１−２９７６４９号、同２−１４６０３３号、同１−２０１６５１号、同３−１２１４４５号。
３．Journal of Photographic Science,２３巻、２４９頁（１９７５年）。特開昭６４−６２６３１号、（R.D.1996年）。
４．欧州特許第６９９，９４４Ａ号〜６９９，９５１Ａ号、同７０１，１６４Ａ号〜同７０１，１６５Ａ号、特開平５−３４１４２６号、および後述の文献。５．Journal of Imaqing Science, ３２巻、１６０〜１７７頁（１９８８年）、Journal of Colloid and Interface Science, １４０巻、３３５〜３６１頁（１９９０年）、R.D.（1994年）、欧州特許第６９９，９４４Ａ１号〜６９９，９５１Ａ１号、同２１５，６１２Ｂ１号、および後述の文献。
６．写真工学の基礎、銀塩写真編、第３章、コロナ社（１９７９年）。
７．Journal of Imaqing Science, ３０巻、２４７〜２５７（１９８６年）。８．特開平１１−２２３８９５号、同１１−２３１４５０号、同１１−２１８８６２号、同１１−２１８８６３号、同１１−２１８８６５号、同６−１９４７６８号、同７−３１１４３１号、同８−１０６１３７号、同８−３３９０４４号、同９−２１１７６１号、同１１−３０５３６６号、同５−３１３２７３号、同１１−２４９２４８号、同６−３０８６４８号、同６−３０８６４９号。
９．T.H.James 編、The Theory of Photographic Process, 第４版、Macmillan(1977年）。
10. 特開平４−１８４３２６〜同１８４３３０号、同４−３４５４４号、同１−１８３６４４号、同１−１８３４１７号、同２−１６６４４２号、同１１−３０８２８号、同４−１８４３３０号、同４−１８１２４０号、同５−５９６６号、同２−１６７８１８号、米国特許第５，１９６，３００号、（R.D.1996年）。欧州特許第３２３，２１５Ａ号、同４３１，５８４Ａ号、同４０７，５７６Ａ号、同７７９，５３７Ａ号。
11．第４版、電気化学便覧、第３〜第６章、丸善（１９８５年）、改訂４版、化学便覧、基礎編、第１２章、丸善（１９９３年）。
12．特開平１０−１０４７６９号、同８−６９０６９号、新実験化学講座第１５巻、酸化と還元、丸善（１９７６）、井本稔編、講座有機反応機構第１０巻、東京化学同人（１９６５）、小方芳郎編、有機化合物の酸化と還元、南江堂（１９６３年）、特開昭６１−３１３４号、世界科学大事典、「酸化還元」、「酸化工程」、「酸化剤」の項、講談社（１９７７年）、ブリタニカ国際大百科辞典、「酸化と還元」の項、ＴＢＳブリタニカ（１９８８年）。
13. 特開昭６３−２２０２３８号、米国特許第５，４７６，７６０号、特開平８−６２７５４号、同７−２７０９５２号、同６−２３０４９１号、同４−１６６９２６号、同６−２３０４９１号。
14．特開平１−２０１６５１号、同２−２８６３８号、同２−９４３号、同３−１２１４４５号、同５−４５７５７号、特開昭６０−１４３３３１号。
15．特開平８−２２０６６４号、同１１−６５００９号、同９−１９７６０４号、（R.D.1996年）。
16．化学便覧、応用化学編、第１６章、丸善（１９８６年）、堀口博著、新界面活性剤、三共出版（１９７５年）、（R.D.1996年）。
17．米国特許第５，３１８，８８９号、同５，１８７，２５９号、特開平６−２１４３２９号、同５−２６５１１３号、同１−１５８４２６号、井村伸正ら編、生化学ハンドブック、第２０章、２１章、丸善（１９８４年）。
18．米国特許第４，７１３，３２０号、同４，９４２，１２０号、同５，４１２，０７５号、特開平８−８２８８３号、同７−３１１４２８号、同１０−１０６６３号、特願平１０−８７５３５号、日本写真学会誌、第５８巻、２５〜３０（１９９５年）、にかわとゼラチン、第４章、日本にかわ・ゼラチン工業組合（１９８７年）、The Science and Technology of Gelatin,第７章、Academic Press（1977年）、新生化学実験講座１、タンパク質IV、東京化学同人（１９９１年）、水溶性高分子の応用と市場、シーエムシー（１９８４年）、水溶性高分子、化学工業社（１９９０年版）、Research Disclosure 誌、３８９号、item３８９５７（１９９６年９月）（以下、「R.D.1996年」と記す）、谷沢和隆ら著、タンパク質の化学修飾、広川書店（１９９１年）。
19．特開平２−８３８号、同８−８２８８３号、同１０−１０６６３号、同１０−１０４７６９号、同１−２１３６３７号、同１０−１４２７２１号、同１１−６５００９号、同７−９８４８２号、同１０−２９３３７２号、米国特許第５，２１０，０１３号、同５，４３９，７８７号、同５，９６２，２０６号、特願平１１−３６４９０２号、同１１−３２２９１３号。
【００５５】
【実施例】
次に実施例により本発明を更に詳細に説明するが、本発明の実施態様はこれに限定されるものではない。
なお、実施例１及び２はそれぞれ参考例１及び２と読み替えるものとする。
実施例１
ゼラチン溶液１〔水１２００ｇ、ＫＢｒ０．６ｇ、化合物１を１０^-4モル、ゼラチン１を３０ｇ、ＮａＯＨ液でｐＨ６．０に調節〕を反応容器に入れ、６０℃に保ち攪拌しながらＡｇ−１１液〔１００ml中にＡｇＮＯ₃ を１．０ｇとゼラチン１を０．９ｇ、ＨＮＯ₃(１Ｎ)液０．２５mlを含む〕とＸ−１１液〔１００ml中にＫＢｒ０．８ｇ、化合物１を１０^-4モル、ゼラチン１を０．９ｇ、ＮａＯＨ（１Ｎ）液０．２５mlを含む〕を５ml／分で３分間、同時混合添加した。続けてＡｇ−１１液をスタート流量５．０ml／分、加速流量１．５ml／分で１４分間、銀電位制御法でｐＢｒ２．３７に保ちながらＸ−１１液と同時添加した。１分間攪拌した後、ＫＢｒ液を添加し、ｐＢｒ１．５に、ｐＨを６．０に調節した後、ｐＢｒ１．５に保ちながらＡｇ−１２液〔１００ml中にＡｇＮＯ₃を１４ｇ含む〕をスタート流量２．０ml／分、加速流量０．５６ml／分で４４分間、Ｘ−１２液〔１００ml中にＫＢｒを１０．６ｇ含む〕と同時添加した。
次にＡｇ−１３液〔１００ml中にＡｇＮＯ₃ ２８ｇ含む〕をスタート流量１２ml／分、加速流量０．１８ml／分で２０分間、Ｘ−１３液〔１００ml中にＫＢｒを２０．５ｇ含む〕と同時添加した。１分間攪拌した後、次の後処理を行った。Ａｇ−１４液〔１００ml中にＡｇＮＯ₃を１０ｇ含む〕を添加し、ｐＢｒ２．６とした後、増感色素１を飽和吸着量の８５％だけ添加し、温度を７０℃に昇温し、２０分間攪拌した。次にかぶり防止剤（Ｆ１）を（１０^-3モル／モルAgX ）だけ添加し、１５分間攪拌した。これらを吸着させる事により化合物１を脱着させた。次に凝集沈降剤を添加し、温度を３０℃に下げ、ｐＨ４．０とし、乳剤を沈降させ、沈降水洗法で従来法に従って脱塩した。これにより化合物１の９５％以上が除去された。次にゼラチン溶液を添加し、ｐＨ６．４、ｐＢｒ２．６、４０℃で再分散させた。
この時点で乳剤１mlを採取し、粒子のレプリカ膜の透過型電子顕微鏡写真像（以下、「ＴＥＭ像」と記す）を観察し、結果を表２に示した。温度を６０℃に上げ、金増感剤−１〔塩化金酸：ＮａＳＣＮ＝１：２０モル比の水溶液〕をＡｕ量で（８×１０^-6モル／モルAgX ）だけ添加し、２分後にカルコゲナイド増感剤Ｓｘ１をＮａ₂ Ｓ₂ Ｏ₃ 量で（１０^-5モル／モルAgX ）だけ添加し、３０分間熟成した。この乳剤を次の塗布処方で塗布し、硬膜し、裁断試料を得た。ゼラチン２、増粘剤、塗布助剤を加えて、硬膜剤１の入った保護層と共に下塗りした三酢酸セルロース透明ベース上に塗布し、乾燥した。試料を密閉した空カン中に入れ、４０℃で１７時間保存し、硬膜反応を進行させた。次にこれを取り出し、裁断し、試料１−１とした。
（比較例１）
実施例１で化合物１の添加をなくす以外は同じにして塗布裁断した試料１−２を調製した。
【００５６】
【化１６】

【００５７】
実施例２
ゼラチン溶液２〔水１２００ｇ、ＮａＣｌ０．３６ｇ、化合物２を１０^-4モル、ゼラチン１を３０ｇ、ＨＮＯ₃ 液でｐＨ４．５に調節〕を反応容器に入れ、４０℃に保ち、攪拌しながらＡｇ−２１液〔１００ml中にＡｇＮＯ₃ を２．０ｇとゼラチン１を０．９ｇ、化合物２を１０^-4モル、ＨＮＯ₃(１Ｎ）液０．２５mlを含む〕とＸ−２１液〔１００ml中にＮａＣｌ０．７６ｇ、ゼラチン１を０．９ｇ、ＮａＯＨ（１Ｎ）液０．２５mlを含む〕を６．０ml／分で３分間、同時添加した。続けてＡｇ−２１液をスタート流量６．０ml／分、加速流量２．０ml／分で１４分間、銀電位制御法でｐＣｌ ２．３に保ちながらＸ−２１液と同時添加した。ｐＨを６．０に調節した。
次にＡｇ−２２液〔１００ml中にＡｇＮＯ₃ を２０ｇ含む〕をスタート流量３．１ml／分、加速流量０．２ml／分で６０分間、同様にｐＣｌ ２．０に保ちながらＸ−２２液〔１００ml中にＮａＣｌを７．０ｇ含む〕と同時添加した。次にＵ−５をＡｇＩで０．００３モル添加し、６５℃に昇温し、１５分間熟成した。Ａｇ−１４液を添加し、ｐＣｌ ２．３とし、増感色素２を飽和吸着量の８５％だけ添加した。温度を６５℃に上げ、２０分間攪拌した。更にかぶり防止剤（Ｆ２）を（１０^-3モル／モルAgX ）だけ添加し、１５分間攪拌した。次に該沈降剤を添加し、温度を３０℃に下げ、ｐＨ４．０とし、乳剤を沈降させ、脱塩した。これにより化合物２の９５％以上が除去された。次にゼラチン溶液を添加し、ｐＨ６．４、ｐＣｌ ２．６、４０℃で再分散させた。
乳剤１mlを採取し、粒子のレプリカ膜のＴＥＭ像を観察し、結果を表２に示した。温度を５５℃に上げ、かぶり低減剤（Ｆ３）を３×１０^-5モル／モルAgX だけ添加し、１５分間攪拌した。次に該Ｓｘ１をＮａ₂ Ｓ₂ Ｏ₃ 量で（２×１０^-5モル／モルAgX ）だけ添加し、３分後に、塩化金酸を５×１０^-6モル／モルAgX だけ添加し、２０分間熟成した。該乳剤を実施例１と同様に塗布し、硬膜し、裁断し、試料２−１を得た。
（比較例２）
実施例２で化合物１の添加をなくする事、Ｕ−５の代わりにＵ−６を添加する事以外は同じにして、塗布試料２−２を得た。
実施例３
ゼラチン溶液３〔水１２００ml、ゼラチン３を１．７ｇ、ＫＢｒを０．５ｇ含み、ＨＮＯ₃ 液でｐＨ２．３に調節〕を反応容器に入れ、これを温度１．０℃の恒温水槽に入れ、溶液温度を１．０℃に保ちながらＡｇ−３１液〔１００ml中にＡｇＮＯ₃ を６．０ｇ、ゼラチン３を０．１４ｇ、ＨＮＯ₃(１Ｎ）液０．２ml含む〕とＸ−３１液〔１００ml中にＫＢｒ４．２９ｇ、ゼラチン３を０．１４ｇ、ＮａＯＨ（１Ｎ）液０．２ml含む〕を３０ml／分で１分間同時混合添加した。Ａｇ−３１液、Ｘ−３１液は、外径３mmの送液チューブを該恒温水槽中を通し、約１℃に冷却した後、添加した。
ＫＢｒを２．８ｇ添加し、温度を３℃／分で６０℃に上げ、１２分間熟成した。ＮａＯＨ液を添加し、ｐＨ９．１とし、１２分間熟成した。ゼラチン溶液４〔ゼラチン４を２５ｇ、水１７５ｇ含む〕を添加し、ｐＨ７．０に調節した。次にＡｇＢｒ微粒子乳剤（Ｕ−１）をＡｇＢｒ量で０．３２モルとＫＢｒ液を添加し、ｐＢｒ１．６とし、温度を７５℃に上げた。１０分後にＵ−１を０．３２モル添加し、添加した微粒子がほぼ消失した時点である１５分後に温度を６０℃に下げた。Ａｇ−１４液を新核が発生しない添加速度で添加し、ｐＢｒ２．３とした。
増感色素１を飽和吸着量の８５％だけ添加し、２０分間攪拌した。更に（Ｆ１）を（１０^-3モル／モルAgX ）だけ添加し、１５分間攪拌した。沈降剤を添加し、温度を３０℃に下げ、ｐＨ４．０とし、乳剤を沈降させ、脱塩した。これにより化合物１の９５％以上が除去された。ゼラチン溶液２を添加し、４０℃、ｐＨ６．４、ｐＢｒ２．６で再分散させた。乳剤１mlを採取し、粒子のレプリカ膜のＴＥＭ像を観察し、結果を表３に示した。表３のＡ₅₁は、ＡｇＸ粒子の投影面積の合計に対するアスペクト比が２以上の｛１１１｝平板粒子の投影面積割合（％）を示す。
温度を６０℃に上げ、増感剤Ｓｘ１をＮａ₂ Ｓ₂ Ｏ₃ 量で（２×１０^-5モル／モルAgX ）だけ添加し、２分後に金増感剤−１を（８×１０^-6モル／モルAgX ）だけ添加し、３０分間熟成した。該乳剤を実施例１と同様に塗布し、硬膜し、裁断し、試料３−１を得た。
（比較例３）
実施例３でＵ−１の代わりにＵ−２を用いる事以外は実施例３と同様に行い、塗布試料３−２を得た。
実施例４
反応容器にゼラチン溶液〔Ｈ₂ Ｏ１．２kg、ＮａＣｌ ２．７ｇ、化合物３を３×１０^-4モル、ゼラチン１を５ｇ、ｐＨ５．６〕を入れ、３０℃に保ち、攪拌しながらＡｇ−４１液〔１００ml中にＡｇＮＯ₃ を２５．５ｇ含む〕とＸ−４１液〔１００ml中にＮａＣｌ ９．４ｇ、ゼラチン３を１ｇ含み、ｐＨ６．０〕を３０ml／分で１分間同時混合添加し、双晶平板粒子の種晶を形成した。１分後にゼラチン水溶液（ゼラチン１を２５ｇ、化合物４を１０^-4モル含みｐＨ５．６に調節したもの）を２００ｇ添加し、ｐＣｌ １．６とした。
次に６５℃に昇温し、１５分間熟成した。次にＡｇＣｌ微粒子乳剤（Ｕ−３）を０．２モル添加し、２０分間熟成し、次にＵ−３を０．４モル添加し、２０分間熟成した。Ｕ−５をＡｇＩ量で０．００５モル添加し、１５分間熟成した後、Ａｇ−１４液を新核が発生しない添加速度で添加し、ｐＣｌ ２．２とした。
６０℃に下げ、増感色素２を飽和吸着量の８５％だけ添加した。次にかぶり防止剤Ｆ２を（１０^-3モル／モルAgX ）だけ添加し、１５分間攪拌した後、沈降剤を加えた。３０℃に下げ、ｐＨ４．０とし、乳剤を沈降させ、脱塩した。これにより化合物の９５％以上が除去された。ゼラチン溶液を添加し、４０℃、ｐＨ６．４、ｐＣｌ ２．３で再分散させた。生成粒子の該ＴＥＭ像を観察し、結果を表３に示した。｛１１１｝平板粒子乳剤が得られた。
５５℃に昇温し、Ｆ３を（３×１０^-5モル／モルAgX ）だけ添加し、１５分間攪拌した。次にＳｘ１を（２×１０^-5モル／モルAgX ）だけ添加し、次に塩化金酸を（５×１０^-6モル／モルAgX ）だけ添加し、３０分間熟成した。４０℃に下げ、実施例１と同様に塗布し、乾燥、硬膜し、裁断し、試料４−１を得た。
（比較例４）
実施例４でＵ−３の代わりにＵ−４を用いる事、Ｕ−５の代わりにＵ−６を用いる事以外は実施例４と同様に行い、塗布試料４−２を得た。
実施例５
反応容器にゼラチン溶液５〔Ｈ₂ Ｏ１２００ｇ、ゼラチン１を２５ｇ、化合物２を１０^-4モル、ＮａＣｌ ０．８ｇ含み、ｐＨ４．３〕を入れ、３０℃に恒温し、攪拌しながらＡｇ−５１液〔１００ml中にＡｇＮＯ₃ を２０ｇとゼラチン１を１．０ｇ、ＨＮＯ₃ を５×１０^-3モル含む〕とＸ−５１液〔１００ml中にＮａＣｌを７ｇ、ゼラチン１ｇ、ＮａＯＨを５×１０^-3モル含む〕を５０ml／分で３０秒間、同時混合添加し、ＡｇＣｌ微粒子を形成した。２分間攪拌した後、Ｘ−５２液〔１００ml中にＫＢｒ１．５ｇ、ゼラチン１ｇを含む〕を６０ml／分で３０秒間添加した。（３℃／分）で４０℃に昇温し、３分間攪拌した。次にＡｇ−５１液とＸ−５１液を５０ml／分で１分間、同時混合添加した。ＮａＣｌ−５１液〔ＮａＣｌ ０．１ｇ／ml〕を１６ml添加し、ＮａＯＨ液でｐＨ５．２とした。 次に２℃／分で７０℃に昇温し、１２分間熟成した。Ｕ−３をＡｇＣｌで０．２モル添加し、ｐＣｌ １．９とした。２０分間熟成した後、Ｕ−３を０．４モル添加し、ｐＣｌ １．９で３０分間熟成した。次にＡｇ−５１液とＸ−５３液〔１００ml中にＮａＣｌ ７ｇ、ＫＢｒ２．５ｇを含む〕を５ml／分で３分間添加した。増感色素２を飽和吸着量の８５％で添加した。１５分間攪拌した後、Ｆ２を（１０^-3モル／モルAgX ）だけ添加し、１５分間攪拌した。沈降剤を添加し、温度を３０℃に下げ、ｐＨ４．０とし、乳剤を沈降させ、脱塩した。これにより化合物２の９５％以上が除去された。ゼラチン溶液を添加し、４０℃、ｐＨ６．４、ｐＣｌ ２．３で再分散させた。生成粒子の該ＴＥＭ像を観察し、結果を表３に示した。｛１００｝型平板粒子乳剤が得られた。
５５℃に昇温し、Ｓｘ１を（２×１０^-5モル／モルAgX ）だけ添加し、３分後に塩化金酸水溶液を（５×１０^-6モル／モルAgX ）だけ添加し、３０分間熟成した。４０℃に下げ、実施例１と同様に塗布し、乾燥、硬膜し、裁断し、試料５−１を得た。
（比較例５）
実施例５でＵ−３の代わりにＵ−４を用いる事以外は実施例５と同様に行い、塗布試料５−２を得た。
得られた試料を光学ウェッジを通して０．１秒間の白色光露光をし、試料１−１、１−２、３−１、３−２はＭＡＡ−１現像液〔Journal of Photographic Science,２３巻、２４９〜２５６（１９７５年）に記載されている〕で２０℃で１０分間現像した。一方、試料２−１、２−２、４−１、４−２、５−１、５−２はＭＡＡ−２現像液〔ＭＡＡ−１のＫＢｒをＮａＣｌ（０．５８ｇ／リットル）に置換したもの〕で２０℃、４分間現像した。次に停止、定着、水洗、乾燥の各工程を通し、センシトメトリーを行い、（感度／粒状度）比を求め、その相対値（Ａ₅₀）を表２と表３に示した。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秒間の一様に露光し、現像処理を行い、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。その詳細は文献７の第２１章Ｅ節に記載されている。
【００５８】
【表２】

【００５９】
【表３】

【００６０】
【化１７】

【００６１】
（ゼラチン１）：メチオニン含率が約（５μmol/ｇ）で、質量平均分子量が約１０⁵ のゼラチン。
該分子量が約１０⁵ の脱イオン化アルカリ処理牛骨ゼラチン（ＥGel １）の水溶液にＨ₂ Ｏ₂ を添加し、メチオニン基のチオエーテル基をスルホキシド基に酸化した後、残留Ｈ₂ Ｏ₂ をＭｎＯ₂ 粉を入れ、分解除去したもの、ＭｎＯ₂ 粉は濾過で除去されている。
（ゼラチン２）：メチオニン含率が約（４３μmol/ｇ）、質量平均分子量が約５×１０⁵ のゼラチン。ＥGel １を硬膜剤１で分子間架橋し、調製した。
（ゼラチン３）：質量平均分子量が約１５０００、メチオニン基含率（μmol/ｇ）が０であるゼラチン。ＥGel １の水溶液に酵素を添加し、約４０℃、ｐＨ５．５で分解し、低分子量化したゼラチン（ＬGel １）をゼラチン１と同様に、酸化処理したもの。
（ゼラチン４）：質量平均分子量が約３００００でメチオニン基含率が５（μmol/ｇ）のゼラチン。
（ゼラチン５）：ＥGel １のアミノ基の約５０％をトリメリト化したゼラチン。
ＡｇＢｒ微粒子乳剤（Ｕ−１）の調製：ゼラチン溶液３１〔水１２００ml、ゼラチン４を２４ｇ、化合物１を３×１０^-4モル、ＫＢｒを０．３ｇ含み、ＮａＯＨ液でｐＨ６．０に調節〕を反応容器に入れ、これを恒温水槽に入れ、溶液温度を２０℃に保ちながらＡｇ−３５液〔１００ml中にＡｇＮＯ₃ を２０ｇ、ゼラチン４を０．８ｇ、ＨＮＯ₃ を２．５×１０^-4モル含む〕とＸ−３５液〔１００ml中にＫＢｒ１４．０６ｇ、ゼラチン４を０．８ｇ、ＮａＯＨを２．５×１０^-4モル含む〕を共に１５ml／分で１０秒間添加し、続けて７０ml／分で７分間添加した。
この時、Ｃｐ−１水溶液〔化合物１を１００ml中に３×１０^-4モル含む〕を、最初の１０秒間は１．５ml／分で添加し、続けて７ml／分で７分間、同時混合添加した。２分間攪拌した後、これをＵ−１として３０分以内に用いた。生成粒子の平均直径（Ａ₅₂）は約０．０３５μm で、双晶面を２枚以上含む粒子の割合（Ａ₅₃）は０．００％、双晶面を１枚以上含む粒子の割合（Ａ₅₄）も０．０％であった。
（Ｕ−２）の調製：化合物１の添加をすべてなくする事以外はＵ−１の調製と同じにして調製した。Ａ₅₂＝０．０５μm 、Ａ₅₃＝２％、Ａ₅₄＝８％であった。（Ｕ−３）の調製：ゼラチン溶液４１〔水１２００ml、ゼラチン４を２４ｇ、化合物２を３×１０^-4モル、ＮａＣｌを０．３ｇ含み、ＨＮＯ₃ でｐＨ３．５に調節〕を反応容器に入れ、これを２０℃の恒温水槽に入れ、溶液温度を２０℃に保ちながらＡｇ−３５液とＸ−４５液〔１００ml中にＮａＣｌ３．５ｇ、ゼラチン４を０．８ｇ、ＮａＯＨを３×１０^-4モル含む〕を共に３０ml／分で１０秒間添加し、続けて１００ml／分で７分間添加した。
この時、Ｃｐ−２水溶液〔化合物２を１００ml中に２×１０^-4モル含む〕を、最初の１０秒間は３．０ml／分で添加し、続けて１０ml／分で７分間、同時混合添加した。２分後にＨ₂ Ｏ₂ （３．１質量％）を５ml添加し、均一化混合した後、１時間、２０℃で放置し、これにより該ゼラチンのメチオニン基含率（μmol/ｇ）は０となった。攪拌した後、これをＵ−３として用いた。Ａ₅₂＝０．０４μm 、Ａ₅₃＝０．０％、Ａ₅₄＝０．０％であった。
（Ｕ−４）の調製：化合物２の添加をすべてなくする事以外はＵ−３の調製と同じにして調製した。Ａ₅₂＝０．０６μm 、Ａ₅₃＝２．２％、Ａ₅₄＝１０％であった。
ＡｇＩ微粒子（Ｕ−５）の調製：ゼラチン溶液３２〔水１２００ml、ゼラチン４を２４ｇ、化合物１を３×１０^-4モル、ＫＩを０．３ｇ含み、ＮａＯＨ液でｐＨ６．０に調節〕を反応容器に入れ、これを恒温水槽に入れ、溶液温度を２０℃に保ちながら、Ａｇ−３５とＸ−３５液〔１００ml中にＫＩを１９．６ｇ、ゼラチン４を０．８ｇ、ＮａＯＨを３×１０^-4モル含む〕を共に１５ml／分で１０秒間添加し、続けて７０ml／分で７分間添加した。
この時、Ｃｐ−１水溶液を最初の１０秒間は１．５ml／分で添加し、続けて７ml／分で７分間、同時混合添加した。２分後に該Ｈ₂ Ｏ₂ を５ml添加し、均一化混合した後、１時間、２０℃で放置し、これをＵ−５とした。Ａ₅₂＝０．０１４μm 、Ａ₅₃＝０．０％、Ａ₅₄＝０．０％であった。
（Ｕ−６）の調製：化合物１の添加をすべてなくする事以外はＵ−５の調製と同じにして調製した。Ａ₅₂＝０．０２５μm 、Ａ₅₃＝１．８％、Ａ₅₄＝９％であった。
なお、（Ｕ−１）〜（Ｕ−６）はいずれも、添加される反応容器から３m 以内に設置した混合容器内で調製し、添加されるＡｇＸ乳剤と同じｐＨ、ｐＸに調節した後に添加された。Ａｇ⁺ 液とＸ^- 液とＺ₁ 、Ｚ₂ の水溶液はいずれも反応溶液中に存在する混合箱中に添加された。
これらの結果により、本発明の効果が確認された。
【００６２】
【発明の効果】
本発明法を用いる事により（感度／粒状度）比の優れたＡｇＸ写真感光材料が得られた。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing silver halide (hereinafter referred to as "AgX") emulsion grains that are useful in the field of photography.
[0002]
[Prior art]
At least AgX particles (A₆ ), A dispersion medium and water, an AgX emulsion (A₇ ) And mix, A₇ And dissolve A₆ Ag on the surface of⁺And X^-By depositing A₆ The growth method of AgX particles for growing₆ Therefore, many ideas have been proposed for this method. For example, JP-A-1-183644, 4-34544, 4-184326 to 4-184330, U.S. Pat. No. 4,433,048, Research Disclosure, item 38957 (September 1996 issue) You can refer to the description of “RD (1996)”.
In this case, A₇ Disappears immediately after the addition, and A₆ It is preferable that the particles grow quickly and the finally obtained particles have high photographic sensitivity and image quality. The prior art has not fully satisfied this requirement yet.
A normal grain emulsion having substantially no twin plane has a narrow grain size distribution and uniform grain characteristics (average AgX composition of grains, intragranular AgX composition, impurity doping amount, etc.) among grains. If the emulsion is used as it is, an extremely high-contrast image can be obtained and it is still used in many AgX photographic light-sensitive materials. The emulsion is required to further improve sensitivity and image quality.
[0003]
[Problems to be solved by the invention]
An object of the present invention is to provide a method for producing an AgX emulsion having better photographic sensitivity and image quality.
[0004]
[Means for Solving the Problems]
(I-1). The object of the present invention has been achieved by the following embodiments.
  (1) At least silver halide grains (B₁ ) And dispersion medium (B₂ ) And water-containing silver halide emulsion (B_Three) Silver halide fine grains (C) having an average diameter (nm) of 1.0 to 200, preferably 1.0 to 100, more preferably 1.0 to 50.₁ Silver halide emulsion (C)₂) And add C₁ And dissolve B₁ By depositing on top, B₁ In the method of growing silver halide grains for growing C,₁Are particles having a particle number ratio (%) of 60 to 100, preferably 90 to 100, more preferably 99 to 100, and most preferably 99.9 to 100, which are fine particles not having two or more twin planes in the particles, C₁Is the adsorbent described in a2) below (Z₂ 10) per 1.0 liter of reaction solution in a total amount of one or more of^-8-1.0 mol, preferably 10^-7Dispersion medium solution containing ~ 0.1 mol (B_Four ) Is a method for producing a silver halide emulsion.
  a2) Compounds described in the following (i) to (viii): (I) a compound containing one or more onium bases in one molecule, (ii) an aromatic compound in which one or more iodo groups and one or more —OH groups are substituted on the aromatic ring, (iii) a nitrogen-containing compound A heterocyclic compound, a compound containing one or more heterocyclic rings in one molecule containing two or more nitrogen atoms in a 4- to 7-membered ring, (iv) cyanine dyes, (v) containing a divalent sulfur group (Vi) a thiourea compound, (vii) an aminothioether, (viii) a divalent sulfur group-containing organic compound containing 25 or less carbon atoms, gelatin and NH_Four ⁺Except for compounds.
  (2) The C₁ Wherein the particle number ratio (%) is 60 to 100, preferably 90 to 100, more preferably 98 to 100 is a fine particle having no twin plane in the particle1) A method for producing a silver halide emulsion as described above.
  (3) The C₁ [(Total number of particles including two or more twin planes in the particle) / (total number of fine particles)] x_Five , The adsorbent (Z₂The value of the fine particles formed under the same conditions except that the₆ X_Five = (0-0.9) x₆, Preferably (0-0.5) x₆ , More preferably (0-0.2) x₆ The above characterized in that (1) A method for producing a silver halide emulsion as described above.
  (4) The C₁ [(Total number of particles containing one or more twin planes in the particle) / (total number of fine particles)] x₇ , The adsorbent (Z₂The value of the fine particles formed under the same conditions except that the₈ X₇ = (0-0.9) x₈, Preferably (0-0.5) x₈ , More preferably (0-0.2) x₈ The above characterized in that (2) A method for producing a silver halide emulsion as described above.
  (5) B_Three 60 to 100%, preferably 90 to 100%, more preferably 97 to 100% of the total projected area of all the silver halide grains of which the aspect ratio (diameter / thickness) is 1.6 to 500, preferably 2 ˜500, more preferably 4˜500, diameter (μm) 0.05˜20, preferably 0.1˜10, thickness (μm) 0.005˜0.5, preferably 0.005˜0. .3, more preferably 0.01 to 0.1 tabular grains, and the diameter distribution variation coefficient (standard deviation / average value of the distribution) and thickness distribution variation coefficient of the grains are preferably 0.01. -0.6, more preferably 0.01-0.30, still more preferably 0.01-0.10.1) Or (2) A method for producing a silver halide emulsion as described above.
  (6) The tabular grains are {111} tabular grains having a {111} plane as the main plane and 2 to 4, preferably 2 to 3, more preferably 2 twin planes parallel to the main plane. Characteristic said (5) A method for producing a silver halide emulsion as described above.
  (7) The main plane of the tabular grain is a {100} plane, and the outline shape of the main plane is a right-angled parallelogram or a shape whose corners are rounded, and is formed by extending the quadrilateral or the straight part of the side. The ratio of adjacent sides of a quadrilateral [one tabular grain (longest side length / shortest side length)] is preferably 1.0 to 5.0, preferably 1.0 to 2.0. Characterized by (5) A method for producing a silver halide emulsion as described above.
  (8) Compound Z₁ , Z₂ Is a compound containing at least one pyridinium base in one molecule.(1)A method for producing the silver halide emulsion as described.
  (9) The C₁ Formation of the B_Three It is formed in a reaction vessel installed within a distance of 0 to 100 m, preferably 0 to 30 m, more preferably 0 to 5 m from a reaction vessel containing1) Or (2) A method for producing a silver halide emulsion as described above.
  (Ten) The C₁ After the formation of C₂ Z inside₂ 10 to 100%, preferably 30 to 100%, more preferably 80 to 100% of C₂After more removal, the C₂ Is B_Three It is added to the above (1) Or (2) A method for producing a silver halide emulsion as described above.
  (11) The C₁ Is formed in a batch reactor and C₁ Z during the formation of₂ Is 10 per 1.0 mole of AgX^-9-1.0 mol, preferably 10^-8Only 0.1 mol is added, and the amount of AgX in the reaction vessel is Z_FiveWhen doubled, Z₂ Concentration of 10^-3Z_Five -10^Three Z_FiveDouble, preferably 10^-2Z_Five -10² Z_Five It is an aspect in which the concentration is increased by a factor of 2 from the concentration before the increase (1) Or (2) A method for producing a silver halide emulsion as described above.
  (12) The C₁ The AgI content (mol%) is 1.0 to 100, preferably 10 to 100, more preferably 30 to 100.1) Or (2) A method for producing a silver halide emulsion as described above.
  (13) B_Four Is a gelatin having a methionine group content (μmol / g) or a histidine group content (μmol / g) of 0 to 33, preferably 0 to 20, more preferably 0 to 10, preferably 0.1 to 15% by mass. Is an aqueous solution containing 1.0-5,1) Or (2) A method for producing a silver halide emulsion as described above.
  (14) (1) Or (2) Produced silver halide emulsion grains (A₀ ) Is 60 to 100% of the total projected area of all silver halide grains, preferably 90 to 100%, more preferably 97 to 100%, and the aspect ratio (diameter / thickness) is 1.6 to 500, Preferably it is 2-500, More preferably, it is 4-500, A diameter (micrometer) is 0.05-20, Preferably it is 0.1-10, Thickness (micrometer) is 0.005-0.5, Preferably it is 0.00. 005 to 0.3, more preferably 0.01 to 0.1, the main plane is a tabular grain of {111} face or {100} face, and the variation coefficient of the diameter distribution of the grain (standard deviation of the distribution) / Average value), and the variation coefficient of the thickness distribution is preferably 0.01 to 0.6, more preferably 0.01 to 0.30, still more preferably 0.01 to 0.10. Said (1) Or (2) Method for producing the silver halide emulsion described.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
  Next, the present invention will be described in more detail.
  In the present invention, “at least silver halide grains (B ₁ ) And dispersion medium (B ₂ ) And water-containing silver halide emulsion (B _Three ) Average diameter ( nm ) Silver halide fine particles (C ₁ Silver halide fine grain emulsion (C) ₂ ) And add C ₁ And dissolve B ₁ B by depositing on top ₁ In the method of growing silver halide grains for growing C, ₁ Is a particle number ratio (%), and 60 to 100 are fine particles having no more than two twin planes in the particle, and C ₁ Is a 2) The adsorbent described (Z ₂ 10) per 1.0 liter of reaction solution in a total amount of one or more of ^-8 Dispersion medium solution (B _Four ) Is a method for producing a silver halide emulsion.
a 2) next (i) ~ (viii) Compound described in 1. (I) a compound containing one or more onium bases in one molecule; ii ) An aromatic compound in which one or more iodo groups and one or more —OH groups are substituted on the aromatic ring; (iii) A nitrogen-containing heterocyclic compound, a compound containing one or more heterocyclic rings in one molecule containing two or more nitrogen atoms in a 4- to 7-membered ring; iv ) Cyanine dyes, (v) a compound having a divalent sulfur group-containing heterocyclic group, ( vi ) Thiourea compounds, (vii) Aminothioethers, ( viii ) Organic compounds containing divalent sulfur groups containing up to 25 carbon atoms and gelatin and NH _Four ⁺ Except for compounds. ", But other matters are also included for reference.
(I-2) Description of AgX particles.
(A-1) A₁ , B₁ , A₀ Common characteristics.
  The diameter refers to the diameter of a circle having an area equal to the projected area of the particles. There is no particular limitation on the average AgX composition of one particle and the average AgX composition of all particles, and there are mixed crystals of AgCl, AgBr, AgI or any ratio of two or more thereof. The variation coefficient of the interparticle distribution of the composition is preferably 0 to 0.6, more preferably 0 to 0.3, and still more preferably 0 to 0.10.
  The AgX composition structure in the particle includes a uniform composition type and a non-uniform composition type. As an example of the latter, two or more phases in which the AgX composition between adjacent phases in the particle is different in terms of AgCl content, AgBr content, or AgI content by 0.1 to 100, preferably 1 to 80 mol%, preferably There are particles having 2 to 20 phases, and the AgX composition change between adjacent phases is a rapid change type, abrupt or gradual (continuous change type, stepped multistage change type). For example, there are double-structure particles composed of a core layer and a shell layer, and multi-structure particles composed of a layer structure having 2 to 19 shell layers. In addition, particles having a specific layer thickness (μm) defined within a specific value of 0.01 to 1.0, AgI content, AgBr content, AgCl content (mol) of the specific layer %) To a specific value of 0.1 to 99.9, preferably 1 to 90.
  The surface layer [surface ~ (10 nm from the surface) is uniformly applied over the entire surface of the particle or preferentially in a specific place (for example, one to all corners or ridges, the center of the flat surface or the helicopter) The average AgX composition and the AgBr content, the AgBr content, the AgCl content, and the AgCl content are 5 to 100 mol%, preferably 30 to 100 mol% of epitaxially grown portions or mixed crystal portions (usually guest portions) Particles). Here, the term “preferential” refers to [molar amount of the guest part / unit area cm of the surface of the host particle]²] Is 1.2 to ∞ times, preferably 3.0 to ∞ times. Further, there is a particle in which one or more shell layers are laminated using the particle as a core particle.
  10 particles^-2Surface latent image type particles (preferentially formed in a distance region within 1 nm from the surface), shallow inner latent particles, depending on where the latent image is preferentially formed after moderate visible light exposure for 10 seconds (Preferentially formed in a depth region of 1 to about 20 nm from the surface), deep latent particles (preferentially formed in the interior of about 21 nm or more away from the surface). Here, the priority is (number of latent images formed / unit volume cm).^Three) Is 1.3 to ∞ times of other places, preferably 3 to ∞ times.
  Since the latent image formation location corresponds to the formation location of chemical sensitization nuclei (which can be referred to later), the above embodiment corresponds to the formation of chemical sensitization nuclei preferentially at a specific location. Preferential means [Mole amount of chemically sensitized nuclei / unit volume cm^Three ] Is 1.3 to ∞ times of other places, preferably 3 to ∞ times. Regarding the details, reference can be made to the description in Reference 1 below.
  In addition, the formation of the surface latent image [development start location when the surface development is performed for an appropriate exposure of 0.1 to 10 seconds] is preferential to the specific location on the particle surface [ Number of starting points / unit area cm² ) Is 1.3 to ∞ times, preferably 1.6 to ∞ times]. Regarding the details, reference can be made to the description in Document 2. Here, the surface development is to develop only the latent image existing in the surface area with the surface developer. The liquid is a liquid substantially free of AgX solvent. In addition, the liquid includes a normal surface developer, and a suppressed developer in which the developing agent concentration or alkali concentration is diluted to 0.01 to 90%, preferably 0.01 to 30% of the original, and is preferably used. it can. Regarding the developer, the description in Reference 3 below can be referred to.
  An AgX shell layer can be formed on the particles to produce shallow inner latent particles and deep inner latent particles. The above-mentioned moderate refers to an exposure amount that gives a density of (maximum density−minimum density) × 0.5 when exposed through an optical edge and developed, to an exposure amount that is 10 times that amount.
  1-10 dislocation lines inside^Three There are particles that have 60% to 100% of the total number of dislocation lines in the peripheral portion or the same corner region.
  Uniformly or nonuniformly in the grains, reduced silver, silver oxide, chalcogen silver, metal atoms among the elements of atomic numbers 11 to 92, preferably Group 8 metal atoms or ions, metal complexes (inorganic ligands) , An organic ligand, a complex having both ligands, a polynuclear complex having 2 to 20 central metal atoms), a chalcogen element or ion, a chalcogen compound, or a metal oxide at a concentration (mol / mol) Mole AgX) is 10^-Ten -10^-1, Preferably 10^-9-10^-2Can be doped (this mode is A_TenCalled the embodiment). Preferred conditions during pH formation (pH, pAg, addition method, time, temperature, etc. in Table 1)₃₁You can refer to the description. ) And a reducing agent or the compound can be added and doped into the particles.
  CN^-, SCN^-, An imidazole group, a pyridine or bispyridine group, or a complex containing one or more of divalent sulfur-containing organic groups as a ligand. For details on metal complexes and ligands, refer to Reference 4 below, Research Disclosure, item 38957 (September 1996 issue) (hereinafter referred to as (RD 1996)), Inorganic compound and complex dictionary, Kodansha (1997). You can refer to the description.
  In addition, as described in JP-A-11-237710, an organic hole trapping agent can be doped into the particles at the above concentration.
  Examples of the non-uniform doping include a mode in which a specific location on the particle surface and the epitaxial phase are preferentially doped, and a mode in which one or more specific layers of the multi-structured particle are preferentially doped. The guest part can be formed on the surface of 0.1 to 100%, preferably 1 to 50% of the total surface area of the particles. [(Solubility of host particles) − (Solubility of guest part)] has a positive or negative aspect. The total guest part silver mole / host part silver mole is preferably 10^-6-10, more preferably 10^-Four-1.0. For details of the particles having a guest portion, the descriptions in References 4 and 5 (R.D. 1996) described later can be referred to.
  In addition, particles having any structure that satisfy the definition of (I-1) and are conventionally known can be mentioned. Regarding the details of the above-mentioned, reference can be made to the description in the following literature. Structure of particles having two or more twin planes, or one or more twin planes, particles having no twin planes (A₁₁), The description in Reference 6 below can be referred to. Regarding the production conditions of AgI particles and the shape of the particles, the descriptions in Physical Review, 161, 848 (1967), U.S. Pat. No. 4,184,878 and JP-A-59-1119344 can be referred to.
(A-2) A₁ Characteristics.
  A₁ 60 to 100%, preferably 90 to 100%, more preferably 98 to 100% of the total number of AgX particles of A₁₁It is. A₁, A₁₁The surface of {111} face, {100} face, {kko}, {hhl} h> l, {hll} h> l, {hko}, {hkl} alone, or 2 to Seven kinds can be included in any ratio, and the description in Document 7 can be referred to for this aspect. A₁₁Particles having 1 to 50, preferably 1 to 10, screw dislocation lines (A₁₂) And no particles (A₁₃), And particles having 1 to 50 edge dislocation lines (A₁₄) And no particles (A₁₅)
  A₁₁Non-tabular grains having an aspect ratio (diameter / thickness) of 1.0 to 1.59 (A₁₆) And an aspect ratio of 1.6 to 500, preferably 2 to 500, and the main plane is a {100} plane (A)₁₇) A₁₆Examples include cubes, octahedrons, 14-hedrons, rhombic dodecahedrons, rhomboided 24-hedrons, trioctahedrons, tetrahedrons, and hexahedrons. A₁₇About (A-3) description can be referred about.
(A-3) B₁ And A₀ Description.
  B₁ And A₀ Refers to all types of AgX grains that are conventionally known or will be known in the future, and are classified into the following tabular grains and non-tabular grains.
  (1) Tabular grains. Tabular grains having an aspect ratio of 1.6 to 500, preferably 2 to 500, and a thickness (μm) of 0.005 to 0.5, preferably 0.005 to 0.3. Here, the diameter refers to the diameter of a circle having an area equal to the projected area when the main plane of the particle is placed on the substrate surface parallel to the substrate surface and observed from the vertical direction. Thickness refers to the distance between the two major planes of the tabular grain.
  The grains are {111} tabular grains (B₁₁) And {100} tabular grains (B₁₂)are categorized. The former has 2 to 4 twin planes parallel to the main plane, preferably 2 to 3 planes, more preferably 2 and the spacing (nm) between adjacent twin planes is preferably 0.3 to 100, 0.3-50 are more preferable. The variation coefficient of the interval distribution or the outermost parallel twin plane interval distribution is preferably 0.01 to 0.60, more preferably 0.01 to 0.30, and more preferably 0.01 to 0.10. The [thickness / outermost parallel twin plane spacing (interval between two twin planes closest to the main plane)] of the particles is preferably 1.1 to 600, and more preferably 1.5 to 300. Further, as described in JP-A-3-239240, there is a particle in which the distance between the main plane and the twin plane closest to the main plane is defined.
  The shape of the main plane of the particle is a hexagon, a triangle, or a circle with rounded corners, and the ratio of adjacent sides of the hexagon or triangle formed by extending the hexagon, the triangle, or a straight portion of the side. [One tabular grain (long side length / short side length)] is 1.0 to 3.0, preferably 1.0 to 2.0 hexagon, 3.01 to ∞, preferably There are 5 to ∞ triangles. The number of parallel twin planes is preferably 2 for hexagonal tabular grains and 2 to 3 for triangular tabular grains.
  The shape of the main plane of {100} tabular grains is as follows. 1) The shape according to (11) of (I-1), 2) A mode in which 1 to 4, preferably 1 to 3 of 4 corners of the right-angled quadrilateral are missing non-equivalently [one Within particles (maximum missing area / minimum missing area) = Z_Ten≧ 2.0 mode], or a mode in which the corners are rounded, 3) Z_Ten= Mode of 1.0 to 1.99 4) A mode in which the four sides constituting the main plane are curved outwardly. Regarding these details, the description in Reference 8 below can be referred to.
  When the particles are observed with a transmission electron microscope at a low temperature of −100 to −150 ° C., 1 to 20, preferably 1 to 3 dislocation lines are observed, and any incident angle of the electron beam is selected. However, there are particles in which dislocation lines are not observed at all. There is an idea that the dislocation line is a helical dislocation line and a helical dislocation line accompanied by an edge dislocation line. The dislocation lines often disappear from the particles during storage at 0 to 40 ° C. for 1 to 60 days.
  1 to 100%, preferably 5 to 50%, of the total area of the side surfaces of {111} tabular grains is a non- {111} plane [for example, {100} plane, {110} plane, {m₁ , M₂ , M_Three } Surface]. 1 to 100%, preferably 5 to 50% of the total area of the side surfaces of {100} tabular grains is a non- {100} plane [for example, {111} plane, {110} plane, {m_Four, M_Five , M₆ } Surface]. {M₁ , M₂ , M_Three} Surface, {m_Four , M_Five , M₆ } Surface refers to a high index surface that AgX particles can take, and the description in Document 7 can be referred to.
  The emulsion is more preferably an AgX emulsion defined by (19) of (I-1), and further a tabular grain in which the characteristics of the tabular grains are characterized by at least one of the above characteristics.
  (2) Non-tabular grains (B₁₃). Non-tabular grains having an aspect ratio of 1.0 to 1.59, and grains having 1 to 4 twin planes, preferably 1 to 2 grains (B₁₄) And no particles (B₁₅) Furthermore, there are particles that have 1 to 50 helical dislocation lines and particles that do not have any. Furthermore, there are particles that have 1 to 50 edge dislocation lines and particles that do not have any. Regarding the crystal plane on the particle surface and examples of the particle shape, the description in the item (A-2) can be referred to.
(A-4) C₁ Characteristics.
  C₁ The characteristics of A are other than the particle size regulation.₁ The description of the characteristics can be applied. However, C₁ Preferably, the particles having no helical dislocation and / or no edge dislocation account for 60 to 100%, preferably 90 to 100%, more preferably 98 to 100% of the total number of particles. The shape is preferably a cube, octahedron, tetrahedron, or particles with rounded corners (for example, spherical particles). C₁The definition of the diameter of is the same as the above definition.
  C₁ Is preferably a uniform AgX composition type, and the AgX composition difference (mol% difference) between each part in one particle is preferably 0 to 30, preferably 0 to 10.
  A defined by (20) of (I-1)₁ More preferred is a monodisperse AgX emulsion in which 60-100%, preferably 90-100% of the total projected area of all AgX grains of the AgX emulsion is AgX grains as defined by at least one of the above characteristics . Seed crystal [A_Five , B₁ ] (R.D. 1996), reference can be made to the description in the following literature. Especially A_FiveRegarding the description of JP-A-2-146603, B₁₁Regarding the description of documents 5 and 19, B₁₂For the above, the description in Reference 8 can be referred to.
(I-3) Z₁ , Z₂ Description.
  The compounds described in (i) to (viii) will be described.
(I) Onium base-containing compound.
  (1) One or more onium bases represented by the following general formulas (I-1) to (I-8) in one molecule, preferably 1 to 10^Four Group-containing compounds.
[0006]
[Chemical 1]

[0007]
Where R¹ ~ R^Three May be the same or different, and each represents a hydrogen atom, a substituted or unsubstituted alkyl group, alkenyl group, aralkyl group or aryl group having 1 to 60 carbon atoms. The number of hydrogen atoms is preferably 2 or less, more preferably 1 or less, and still more preferably 0. That is, a linear or branched alkyl group having 1 to 60 carbon atoms, a cycloalkyl group, an alkenyl group having 2 to 60 carbon atoms, an aralkyl group having 6 to 60 carbon atoms, and an aryl group are preferable. These groups may be substituted with the following substituents. Y^-Represents an anion (a negatively charged atom or atomic group). For example, acid group, OH^-Groups, halogen ions, and specific examples are F^-, Cl^-, Br^-, I^-, NO_Three ^-, 0.5SO_Four ^2-, R¹ COO^-, R¹ -SO_Three ^-, ClO_Three ^-Can be mentioned. R² Is R¹ Or R^Three And can form a closed ring. In the case of a compound having only one onium base in one molecule or unless otherwise specified, the free bond in the formulas (I-1) to (I-8) is R^Four Bonded to the group. R^Four The group is R¹ ~ R^Three Represents a group having the same definition as. Examples of the substitutable group include (SB1) described in JP-A No. 10-104769, and examples thereof include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a heterocyclic group, an alkoxy group, and an amino group. Group, carboxy group, sulfo group and ester group. These groups may be further substituted. When there are two or more substituents, they may be the same or different.
[0008]
(I-1) R in the formula¹ ~ R^Four N is an atom other than a hydrogen atom, the N⁺Is not dependent on pH in the pH range of 1.0 to 12.0 and is always N⁺Keep. But R¹ ~ R^Four When at least one of the hydrogen atoms is a hydrogen atom, the hydrogen atom dissociates as a proton at a pH equal to or higher than the pKa value (Ka is an acid dissociation constant) of the hydrogen atom, and the probability that it is no longer an onium base increases. In this case, it means that the compound is allowed to coexist in the reaction solution under the pH conditions of (the pKa + 0.3) to (the pKa-6), preferably the pKa to (the pKa-5).
[0009]
2 or more, preferably 3-10, of the onium base in the following manner:^Three Groups can also be linked. (A) the free bond through the divalent linking group L, or R¹ Link through a group. L is alkylene, arylene, alkenylene, -SO₂ -, -SO-, -O-, -S-, -CO-, -NR^Five -(R^Five Represents an alkyl group, an aryl group, or a hydrogen atom) alone or in combination. Alkylene and alkenylene are preferred. (B) Bond with a polymer chain. The onium bases to be bonded may be the same or different from each other, and may be an embodiment in which two or more groups of the formulas (I-1) to (I-8) are linked. In that case, the total of various onium groups is 2-10.^Four Group, preferably 2-10^Three It is a group.
[0010]
In particular, a copolymer with a monomer having an acid dissociation group having a pKa value (Ka is an acid dissociation constant) in the pH 1.5 to 12.0 region is preferable. Expressed by the general formula, it is expressed by the formula (I-9).
[0011]
[Chemical formula 2]

[0012]
Where R⁸ Is R¹ ~ R^Three Represents the same substituent as. R⁹ Represents a substituent having the acid dissociable group. n1 represents an integer of 1 to 1000, preferably 2 to 300, and n2 and n3 are integers of 0 or more, preferably 1 to 10^Four , More preferably 2 to 10^Three Represents an integer.
In this case, by raising or lowering the pH from the pKa value, the RKa⁹ It is preferable because the water solubility of the group can be changed to change the adsorptivity of the polymer. For example, in the case of an acid group such as a -COOH group, (-COOH → -COO) is adjusted by adjusting the pH to the pKa value or more, preferably (pKa + 0.3) or more.^-+ H⁺), The hydrophilicity of the group is increased, and the desorption of the polymer adsorbed on the AgX particles is promoted. That is, when the polymer is no longer necessary, there is an advantage that the polymer can be desorbed and removed from the AgX particles by adjusting the pH value of the reaction solution. -NH₂ In the case of a base such as a group, it is reduced to (−NH) by lowering the pKa value or less, preferably (pKa−0.3) or less.₂ + H⁺→ -NH_Three ⁺) And water solubility increases. -SO as the dissociable group_Three M, -SO₂ M, -OSO_Three M, -COOM, -NH₂ , -NHR¹ , -NR¹ R^Three , -SO_Four M, -OPO_Three M₂ , (-O)₂ POOM can be mentioned, preferably -SO_Three M, -SO₂ M, -COOM, -NH₂ , -NHR¹ , -OPO_Three M₂ It is. Where M is H, alkali metal, or —NH_Four ⁺Represents.
[0013]
Also R⁸ It is preferable to introduce a hydrophilic group into the polymer and to change the (n1 / n2) ratio variously because the adsorption characteristics of the polymer can be changed almost continuously. Examples of the water-soluble group include —OH, —CN, and —CONH.₂ , -COOCH_Three ,-(CH₂ CH₂ O)-and -CONH-. A monomer having these groups may be polymerized to synthesize a compound represented by the formula (I-9). The (n1 / n2) ratio and (n1 / n3) ratio are 10^-Four-10^Four , Preferably 10^-3-10^Three A preferred ratio can be selected in the region.
[0014]
Examples of the water-soluble groups and their pKa values are as follows. -C₂ H_Four COOH (4.67), -Ph-COOH (4.20), -Ph- (CH₂)₂ -COOH (4.66), -C₂ H_Four NH₂ , -Ph-NH₂ (4.65), pyridine group (5.42), -Ph-OH (9.82). However, Ph represents a phenylene group. This method can be preferably used for the compounds (ii) to (viii).
The compound (i) does not contain gelatin. NH_Four ⁺, -NH_Three ⁺Groups are also preferably not included in (i).
Specific examples of these compounds are shown in (I-31) to (I-46).
[0015]
[Chemical 3]

[0016]
[Formula 4]

[0017]
Other specific examples include triazolium salts which are onium forms of triazoles. Regarding the details of the compound, reference can be made to the description in JP-A-4-335632.
Of these, sulfonium base, phosphonium base, selenonium base, arsonium base, stibonium base, stannonium base, iodonium base, and heterocyclic quaternary base-containing compounds are more preferable.
[0018]
[Chemical formula 5]

[0019]
(2) A heterocyclic nitrogen quaternary base-containing compound.
In the onium base described in (1), a heterocyclic nitrogen quaternary base-containing compound is more preferable. The base is represented by the general formulas (II-1) to (II-4). A compound containing 1 or more, preferably 2 to 300, of these groups in one molecule.
[0020]
[Chemical 6]

[0021]
Where A₁ ~ A_Four Represents a group of nonmetallic atoms for completing a nitrogen-containing organic heterocycle, and each may be the same or different. O, N, and S atoms may be included, and the benzene ring may be condensed. A₁ ~ A_Four May have a substituent, and each of the substituents may be the same or different. Examples of the substituent include (SB1). A preferred example is A₁ ~ A_Four Is a 5- to 6-membered ring (for example, a pyridine ring, an imidazole ring, a thiazole ring, an oxazole ring, a pyrazine ring, a pyrimidine ring, etc.), and more preferred examples include a pyridine ring. Specific examples of the compound are shown in (II-11) to (II-16).
[0022]
[Chemical 7]

[0023]
More preferred compounds (a) are represented by formulas (II-21) and (II-22). Where R^{twenty three}, R^{twenty four}Is R¹ , R² Represents a substituent similar to_Five ~ A₈ Is A₁ ~ A_Three And represents a group of non-metallic atoms for completing a nitrogen-containing heterocycle, each of which may be the same or different. n11 represents 0 or 1, and is 0 in the case of an inner salt. n12 represents 0 or 1. L represents the same divalent linking group as described above. Y^-Represents the same anion as described above. Specific examples of the compound are shown in (II-31) to (II-37).
[0024]
[Chemical 8]

[0025]
[Chemical 9]

[0026]
(B) More preferable examples of the compound include compounds represented by the formula (III-1). Where R³¹Is R¹ , R² Represents the same substituent as R³²~ R³⁶May be the same as or different from each other, and each represents a hydrogen atom or a group that can be substituted therefor. Examples of the substitutable group include SB1.
R³²And R³³, R³³And R³⁴, R³⁴And R³⁵, R³⁵And R³⁶May be condensed. However, R³²~ R³⁶Is preferably an aryl group or an aralkyl group, R³¹Is more preferably an aryl group or an aralkyl group. Y^-Is Y^-Is the same.
R³²And R³³, R³³And R³⁴, R³⁴And R³⁵, R³⁵And R³⁶May be condensed to form a quinoline ring, an isoquinoline ring, or an acridine ring. Specific compound examples of the compound are shown in the following (III-2) to (III-11).
[0027]
[Chemical Formula 10]

[0028]
Embedded image

[0029]
(C) As a more preferred compound example, a compound represented by the formula (I-9) formula and the onium base is represented by the formula (II-3) or (II-4). Furthermore, the compound which contains 1 or more each of this heterocyclic nitrogen quaternary base and non-cyclic quaternary ammonium base in 1 molecule can be mentioned. Preferably each 1-10^Four Group, preferably 2-10^Three A group-containing compound can be mentioned. Specific compound examples thereof are shown in (III-21).
[0030]
Embedded image

[0031]
Regarding the details and synthesis methods of the compounds (1) and (2), U.S. Pat. Nos. 3,017,270, 5,418,078, 4,525,446, European Patent No. 03929202B, JP-A-2-2933838, JP-A-7-306489, Reference can be made to the descriptions of Nos. 10-104769, 8-29902, 2-34, 8-227117 and International Publication No. WO94 / 20551.
[0032]
(Ii) An aromatic compound in which one or more iodo groups and one or more —OH groups are substituted on the aromatic ring. The iodo group is preferably substituted with 1 to 8 groups, preferably 2 to 5 groups, and preferably substituted with 1 to 3 hydroxy groups.
Here, the aromatic compound refers to a carbocyclic compound having a benzene nucleus, and includes a compound in which another benzene ring or a heterocyclic ring is condensed to the benzene ring (for example, naphthalene, anthracene, quinoline, indole). The aromatic ring includes the benzene nucleus, the benzene ring, and the heterocyclic ring, and preferably refers to the benzene nucleus and the benzene ring. More preferably, it is 8-hydroxyquinoline containing at least one iodo substituent (general formula is represented by formula (IV-1)) or isoquinolines, and specific examples of compounds (IV-2) to ( Shown in IV-3).
In addition, there is 8-hydroxy-7-iodo-5-quinolinesulfonic acid.
R⁶⁰, R⁶¹Can be selected from the above (SB1), and polar substituents and halo substituents are preferred. With respect to the details of the compound, reference can be made to the description in the literature of US Pat. No. 5,411,852 and item (iii).
[0033]
Embedded image

[0034]
(iii) Nitrogen-containing heterocyclic compounds.
It is a compound containing 1 or more heterocycles containing 2 or more nitrogen atoms in a 4- to 7-membered ring in one molecule, and the following compounds are preferable.
(A) Azaindenes. Tetraazaindenes are preferred, and specific examples include xanthinoids (represented by the formula (V-1), specific examples include xanthine and uric acid), aminoazaindenes (specific examples) Purine, adenine, guanine, and kinetin).
(B) Diazines (pyridazines, pyrimidines, pyrazines).
Of these, substituted pyrimidines are preferred. Examples of the substituent include the SB1, preferably an amino group. Specific examples of the compound include uracil, cytosine, thymine, and compounds of formulas (V-2) to (V-5).
The details of these compounds are described in JP-B-5-40298, JP-A-5-265111, JP-A-5-204077, JP-A-5-232612, JP-A-64-8325, edited by The Chemical Society of Japan, New Experimental Chemistry Course. Reference can be made to the descriptions in Volume 14, Chapter 9, Maruzen (1978).
[0035]
Embedded image

[0036]
(Iv) Cyanine pigments. It refers to a dye having a cation structure in which two nitrogen-containing heterocycles are linked by a methine group -CH = or a chain thereof, and preferably has one or more, more preferably 1-2 acid groups. Here, the acid group is -SO_Three ^-, -OSO_Three ^-, -COO^-Preferably, -SO_Three ^-Refers to the group. Imidacyanine, oxacyanine, thiocyanin, selenocyanine and two complex cyanines thereof are preferred, and imidacyanine and oxacyanin are more preferred. For details of these compounds, reference can be made to Research Disclosure, Vol. 501, Item 36544, September 1994 (hereinafter referred to as [RD 1994]), Reference 9.
[0037]
(V)-(viii). In addition, compounds having a divalent sulfur group-containing heterocyclic group described in JP-A-62-299961, divalent sulfur group-containing organic compounds described in JP-A-63-141845, Examples thereof include aminothioethers described in JP-A Nos. 212439 and 4-283742, and thioureas described in JP-A-62-218959 and derivatives thereof. The general formulas of these compounds are shown in formulas (VII-1) to (VII-4).
[0038]
Embedded image

[0039]
Regarding the details of these compounds, the descriptions in the above-mentioned documents corresponding to the respective compounds can be referred to.
[0040]
Z in the formula⁷⁰Represents an atomic group necessary for forming a substituted or unsubstituted saturated or unsaturated heterocycle together with a sulfur atom, and is an atomic group composed of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom. The heterocyclic ring is a 3- to 8-membered ring, and the ring may be condensed with another ring to form a condensed ring. The heterocycle may have one or more substituents. Examples of the substituent include SB1.
[0041]
X⁷⁰Represents an amino group, a quaternary alkylammonio group, or a carboxy group, which may be alkyl-substituted, and L⁷⁰, L⁷¹, L⁷²Represents a divalent organic linking group having the same definition as L. Y^-Represents an anionic group, Y^-Is the same definition as m is the same as the number of quaternary alkylammonio groups. As for carbon number of this alkyl group, 1-3 are preferable.
M⁷⁰Represents a hydrogen atom, an alkali metal, an alkaline earth metal, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. X⁷¹Is CO or SO₂ Represents. R⁷⁵Represents a hydroxy group, substituted or unsubstituted (alkyl group, aryl group, heterocyclic group, amino group, alkoxy group, aryloxy group). SB1 can be mentioned as a substituent. The total number of carbon atoms in the molecule of formula (VII-4) is preferably 30 or less, and more preferably 20 or less.
Z₁ , Z₂ In addition, with respect to the details and specific compound examples, the description in Reference 20 (Japanese Patent Laid-Open Nos. 10-104769 and 11-364902) can be referred to.
(i) to (iii) are more preferred, and (i) is most preferred.
An embodiment in which an onium salt forms a π-conjugated system (Z₁₁), Especially pyridinium quaternary bases (Z₁₂In which a cyclic π-conjugated system is formed as shown in FIG.₁₃) Is more preferable, in which a group containing 1 to 60 carbon atoms is covalently bonded to the quaternary nitrogen atom (Z₁₄Is more preferred, Z₁₄Group-containing compounds (Z₁₅) Is preferred. In (i), a compound having one or more, preferably 1 to 10, substituted or unsubstituted aryl groups in one molecule as represented by formulas (II-32), (III-2) and (III-3) Is more preferable.
[0042]
Onium base is X on the AgX particle surface.^-Adsorbs to the site by Coulomb interaction and exerts its effect.₁₃, Z₁₄In this embodiment, the molecular polarizability is increased, and the interaction is considered to be further increased. By adsorbing the group to the particle surface, [Ag_nX_m ^-(mn)The adsorption of negatively charged ions such as] on the particle surface is promoted to promote particle growth. On the other hand, if the adsorption is enhanced by the aryl group, the desorption probability is lowered due to the hydrophobicity, and the particle growth is suppressed. When added in a large amount, the latter action becomes dominant and particle growth is greatly suppressed. When added in an appropriate amount, thin tabular grains with a narrow diameter distribution can be obtained by suppressing the growth of the main plane and the weak growth of the edge surface.
When the compound is adsorbed on octahedral AgX particles, there are compounds that increase the ionic conductivity of the particles and compounds that decrease the ionic conductivity. Many of the compounds having a large effect of the present invention are reduced. In the frequency dependence measurement of the dielectric loss of the particles, the loss peak (P₁) Is the conductive Ag on the particle surface.⁺Based on the loss peak (P₂) Are interstitial silver ions (Ag) in the grains._i ⁺) To increase both, move both to the high frequency side, and to decrease,₁In many cases, both of them are moved to the low frequency side with a decrease in the peak intensity.
[0043]
In the case of nitrogen-containing heterocyclic compounds such as the purine bases and pyrimidine bases, the adsorptivity to AgX particles is pH-dependent in the pH range. When the acid dissociation constant of the compound is Ka, the adsorptivity becomes high at a pH of pKa or higher. Here, pKa = −log (Ka). At pH below pKa, the adsorptivity decreases due to proton addition. Therefore, the compound is preferably allowed to coexist in the dispersion medium solution at a pH of (pKa−0.3) or more, more preferably at a pH of pKa to (pKa + 5).
Z₁ , Z₂ Preferably has 1 to 1000 acid dissociable groups of pKa = 1 to 12, preferably 2 to 10, more preferably 3 to 9, in the molecule.
[0044]
Those having a strong adsorptive power to AgX grains in the group of compounds promote the twin plane formation during the grain formation and produce thin tabular grains. Those having an appropriate adsorptive power have the effect of suppressing the twin plane formation. If the adsorption power is too weak, it can be said that there is no effect. Even in the same compound, the effect depends on the concentration and temperature, and as the concentration increases and the temperature decreases, the adsorption force becomes stronger (that is, the adsorption residence time becomes longer). In addition, when the adsorption strength of the coexisting dispersion medium is strong or the concentration is high, Z₁ , Z₂ Since the adsorption equilibrium concentration of Z decreases, to obtain this effect, a higher concentration of Z₁ , Z₂ Need. Therefore, in order to obtain the effect of the present invention, it is necessary to select the compound type and its concentration, temperature, pH, pX, dispersion medium type, and dispersion medium concentration value.
X in the compound of (i)^-When a salt compound is used, (Cl^-Concentration is Br^-Cl when the concentration is 2 to ∞^-It is preferable to use a salt compound, and the Br^-Concentration is Cl^-Br is 2 to ∞ times the concentration^-It is preferable to use a salt compound. The compound (i) is, for example, a halogenated alkyl compound (Z_Three ) In an organic solvent such as isopropyl alcohol, and usually in the form of a salt. The type of counter ion is Z_Three It can be selected by selecting the type of halogen ion. Or the product is Br^-Salt and I^-In the case of a salt, when this is dissolved in an aqueous solution containing AgCl particles, Br^-And I^-Is Cl^-And halogen substitution. From the aqueous solution from which the AgX particles were removed by centrifugation, Cl^-Remove the salt. Alternatively, the product is dissolved in water and X is added to the positive electrode by electrodialysis.^-After collecting the + polar solution with another + polar solution. By these methods, X^-You can choose the seeds freely. Accordingly, X of the above compound example^-You can also choose the seeds freely.
(I-4) Description of Embodiments (1) and (2).
A_Three Is the normal seed crystal formation process (A_{twenty one}) And the growth process (A_{twenty two}), A_{twenty one}Is usually Z₁ A exists_Four Ag inside⁺Containing solution (Ag⁺Liquid) and halogen ions (X^-) Solution (X)^-Liquid) is mixed and added simultaneously with stirring.
A_{twenty one}The period of A is from the start of AgX nucleation._{twenty two}Refers to the period until just before the start. Ag⁺And X^-When continual addition is continued, unstable nuclei are first formed and then the number increases. Next, some of them become stable nuclei, the rest dissolve and disappear, and the number of stable nuclei (number of seed crystals) becomes constant. Next A_{twenty two}Thus, the stable nucleus (seed crystal) grows and the target product is obtained. Therefore A_{twenty one}Indicates the period until the number of stable nuclei becomes constant.
Z₁ Is A_{twenty one}Although it can be added at any time of the above, it is preferably present at the aforementioned concentration when the unstable nuclei are formed. Therefore, before the start of nucleation, Z₁ A_Four It is preferable to add in the concentration amount. Z₁ A_{twenty one}, A_{twenty two}10 per mole of AgX^-9-1.0, preferably 10^-8Additional addition of ~ 0.1 mol can be made. The additional addition can be added all at once, can be added continuously, or 2-10.^Three It can also be added in batches. Two or more of these methods can be used in combination. Ag to be added⁺Liquid and X^-One or more of the liquids, preferably both^-8-1.0 mol can also be added.
In addition to the solution, the addition method may be a powder or a form in which the powder is suspended in the solution. Especially A_{twenty one}When this additional addition method is used, the Z₁ Therefore, a more preferable seed crystal can be formed.
These aspects can also be applied to the aspect (I-5).
Z₁ Is present at the time of nucleation, twinning plane formation is prevented by its moderate adsorptive power to AgX nuclei. In addition, intergranular coalescence is prevented, and generation of edge dislocations and helical dislocations is also prevented. A_{twenty two}Then, the generation of new nuclei is prevented by the moderate adsorption force with respect to the AgX grains, the growth between grains is made uniform, and AgX emulsion grains having a uniform AgX grain shape and AgX composition are obtained.
In the step of introducing dislocation lines into AgX particles, the step of forming the guest part in AgX particles, Z₁ Is present, the dislocation line introduction location and number, the length of the dislocation line, the guest portion formation location, and the AgX molar amount of the guest portion are made uniform among the particles. The variation coefficient of the variation between these particles is preferably 0.01 to 0.50, and more preferably 0.01 to 0.20.
A_Four , B_Four Preferred conditions for the dispersion medium solution (A_{twenty five}), More preferable conditions (A₂₆) Is shown in Table 1. Where pX = −log [X^-] And [X^-] Is X^-Represents the concentration (mol / liter). The most preferable combination condition region (A₂₇) Is preferred. Especially Ag⁺And X^-Absolute value of concentration difference (mol / liter) | [Ag⁺]-[X^-] Is 0.0 to 10^-1.5Is preferred, 0.0-10^-2Is more preferable, and 0.0 to 10^-2.5Is most preferred. The condition is A₃₁Also preferred.
[0045]
[Table 1]

[0046]
(I-5) Description of Embodiments (3) and (4).
(A-1) C₂ Formation and C₂ B_Three How to add to.
Reaction vessel (A₃₀) B in_Four And Z₂ Add Ag and stir with stirring.⁺Liquid and X^-C is added by adding liquid into the solution.₂ Is obtained.
The formation process (A₃₁Preferred conditions (A)_{twenty five}, A₂₆) Is shown in Table 1. Z₂ Therefore, the formation of crystal defects such as twin planes is prevented, and the introduction of dislocation lines is also prevented. C₂ To form B_Three There are the following methods as a method of adding to.
1) C₂ Is desalted by the desalting method described below, and then B_Three How to add to. The total amount of soluble salt in the emulsion or Z₂ The content is reduced to 0-95% before the treatment, preferably 0-50%, more preferably 0-10%.
2) C₂ 95.1 to 100% of the soluble salt in C₂ B is left inside_Three How to add to.
3) C₂ A method of adding after removing 1 to 100%, preferably 20 to 100%, more preferably 60 to 100% of the total water content. Specific examples of the removal method are as follows. 3-1) A method of drying in the air. 3-2) 10^-7~ 0.99 atm, preferably 10^-6A method of evaporating and removing moisture under ~ 0.3 atm. A vacuum freeze-drying method is also included. 3-3) A method of centrifuging and removing the supernatant. 3-4) A method of removing moisture by an ultrafiltration method. 3-6) A method in which a coagulating sedimentation agent is added, the emulsion is coagulated and settled, and the supernatant is removed.
Regarding the desalting method and the precipitating agent, the description in the section (I-7) can be referred to.
4) C₁ Is formed in a batch reactor and the formed C₁ At once or 2-10^Five B divided into times_Three How to add to. Or the method of adding continuously. 5) C₁ Formation and C₁ A method of forming by a continuous forming method in which the removal is continuously performed simultaneously. This is B_Three Can be added continuously to the C₁ B in the container and after accumulation_Three Can also be added.
6) C₂ And B_Three If the solution conditions are different, C₂ The condition of B_Three After preparing to the condition of or close to that of B_Three Can be added. For example, pH, pAg, temperature, adsorption power of the dispersion medium to AgX particles and dispersion medium concentration. pH is adjusted to 0-3.0 by adding acid or alkali, pX is Ag⁺Liquid or X^-By adding the liquid, the pX difference is adjusted to 0 to 3.0, and the temperature is adjusted to 0 to 40 ° C., preferably 0 to 15 ° C., by cooling or heating the reaction solution.
7) In addition, the description in Reference 10 below can be referred to.
It is preferable to use two or more of the above 1) to 7) in combination.
The smaller the diameter of the fine particles, the easier it is to dissolve.⁺And X^-The effect of this method becomes small. In order to form small fine particles, it may be formed under a condition with low solubility of AgX. For this purpose, the temperature (° C.) is more preferably 0-30, and still more preferably 0-20. Ag⁺The total concentration of the complex is Ag⁺0-10 of the concentration of² Times, preferably 0.0 to 1.0 times. The condition is A_{twenty one}Also preferred.
Further, it is not to cause a low dispersion medium concentration region during particle formation.⁺Liquid and X^-In at least one of the liquids, preferably both, the dispersion medium is present in a dissolved state in an amount of 0.01 to 15, preferably 0.10 to 5.0 by mass%. Ag⁺When added to the liquid, acid (HNO_Three Etc.) together (10 acids / kg of dispersion medium)^-3-10² Moles, preferably 10^-210 mol) and Ag⁺It is preferable to prevent the change of Ag to Ag. The embodiment is A_{twenty one}Can also be preferably used.
In addition, the pH, pX, dispersion medium concentration and temperature of the reaction solution are set to A_Five And C₁ For the purpose of formation, the most preferable combination condition region (A₃₂) Is preferred.
Ag for fine particle formation⁺Liquid and X^-When a large amount of liquid is added within a short time, the temperature of the reaction solution rises due to the heat of reaction. In order to suppress this and keep the temperature (° C.) at 0 to 30, preferably 0 to 20, more preferably 0 to 10, the following method can be preferably used.
1) The Ag⁺Liquid and X^-At least one of the liquids, preferably both temperatures (° C.) are cooled to 0 to 25, preferably 0 to 20, and then added. This is a) a method in which the stock solution of the liquid is cooled in advance, b) an aspect in which the liquid is added through a liquid feeding pipe, and 0.1 to 100% of the total length of the liquid feeding pipe, preferably Is a mode in which 1 to 100% has passed through the coolant. The liquid is cooled as it passes through the liquid delivery tube. The thinner the outer diameter of the liquid feeding pipe, the larger the specific surface area, the better the cooling efficiency, and 0.1 to 300 mm is preferable, and 0.5 to 50 mm is more preferable. The coolant may be provided for that purpose or a constant temperature bath for the reaction solution. Alternatively, the reaction solution can be used as a coolant. Two or more of these can be used in combination.
2) Ag⁺Liquid and X^-Simultaneously with the addition of the liquid, a coolant (ice, gas solidified product (eg, dry ice), gas liquefied product (eg, liquid nitrogen, liquid oxygen, liquid air)) is added (in the reaction solution and / or in the thermostatic bath). Added. The amount of addition is determined in advance in a preliminary experiment, the relationship between the amount added and the temperature reached during or after the addition, and the amount necessary to achieve the target temperature is divided into 1 to 100 times, preferably 2 to 100 times. More preferably, it is preferably added by continuous addition. The total addition amount is 0.1 to 10 per liter of the reaction solution.^Four g is preferred, 0.5-10^Three g is more preferable.
When a coolant is added to the reaction solution, the method of adding the gas solidified product or gas liquefied product is more preferable because it does not increase the amount of the reaction solution compared to ice.
C₁ Is formed for 0.01 seconds to 1 day, preferably 0.1 seconds to 3 hours, more preferably 0.1 seconds to 40 minutes._Three It is preferable to add to.
Uniform or non-uniform A in the fine particles_TenIn this embodiment, the heteroatom and the compound can be doped.
C₁ Together with Z₂ 5 to 100%, preferably 20 to 100% of B_Three May be added. In this case, Z₂ Is B₁ To control the growth of and improve the monodispersity. Especially B₁ Is a tabular grain, the growth of the edge face is weakly suppressed, and grains that grow fast are eliminated. In addition, dissolution of small seed crystal particles is prevented, and generation of small particles is also suppressed. As a result, particles having a uniform size distribution are obtained. But it has Z₂ Must be present at an optimal concentration.
C₁ Is particularly effective when the AgI content is high.
When the tabular grains are grown in the manner of (I-1) 3) and 4), the tabular grains grow uniformly between the grains, and tabular grains having uniform grain characteristics can be obtained.
(I-6) Dispersion medium.
(A-1) A₂ , A_Four , B₂ , B_Four General description for a dispersion medium for use.
As the dispersion medium, known natural or synthetic, or water-soluble dispersion medium obtained by chemically modifying a natural product can be used, and its mass average molecular weight is 10^Three -10⁶ Is preferred, 5000-10⁶ Is more preferable. The coefficient of variation of the molecular weight distribution is preferably 0.01 to 0.50, more preferably 0.01 to 0.20, and still more preferably 0.01 to 0.10. Examples of the monodispersed dispersion medium include fractionated gelatin (for example, gelatin fractionated by an ultrafiltration method, which can be referred to the description in Reference 18 described later). In addition, the polydisperse dispersion medium having a coefficient of 0.51 or more, the dispersion medium having two or more, preferably 2 to 10 peaks in the molecular weight distribution curve, and the low molecular weight dispersion medium having 1.2 to 10^Three There is a dispersion medium in which a polymer dispersion medium of double the molecular weight is mixed. In this case, the low molecular weight molecules are adsorbed on the particle surface corresponding to the molecular size (for example, the edge surface of fine particles or thin tabular grains, the trough portion of {111} tabular grains), and the growth is controlled. It adsorbs to a flat surface (for example, main plane) and prevents aggregation between particles. That is, it can be said to be a more multifunctional dispersion medium.
When gelatin is used, the most preferable methionine group (Met) content (μmol / g) or thioether group content (μmol / g) is 0.0 to 120. The content is determined by chemically modifying the thioether group (by oxidizing the group and converting it to a sulfoxide group or sulfo group, or by alkylating with an alkylating agent (eg, alkyl halide), or thionating). Can be reduced. In general formula, -S (O)-, -S (O₂)-, -S (R⁸⁰)-, -S⁺(R⁸⁰, R⁸¹) −. Further, via the oxidant, -SO_Three ^2-There is also an aspect which makes it. The altered group is not considered the group. H₂ O_Three More preferred is gelatin that has been oxidized by adding. Furthermore, gelatin which removed 5 to 100%, preferably 20 to 100% of the remaining oxidizing agent after the oxidation is preferred. In order to increase the group content, a dispersion medium having a high content may be selected, or a thioether group-containing organic compound having 1 to 20 carbon atoms may be covalently bonded to the dispersion medium molecule.
0.0-100 are preferable and, as for the chemical modification rate (%) of an amino group, an imidazole group, a carboxyl group, and a hydroxyl group, 10-97 are more preferable. Chemical modification of the amino group is -NH₂ This refers to changing the group to a secondary, tertiary or quaternary amino group, or deamination. When represented by a general formula, —NHR⁸⁰, -N (R⁸⁰, R⁸¹), -N (R⁸⁰, R⁸¹, R⁸²And, as a specific example, —NHCO—R⁸⁰, -NHSO₂ -R⁸⁰, -N⁺(CH_Three) _Three There is. Where R⁸⁰, R⁸¹, R⁸²Is R excluding hydrogen and halogen atoms^Four It is the same definition as the group. Quaternization of an amino group can be accomplished by adding a halogenated organic compound (R^Four -X, for example, methyl iodide, methyl bromide).
Regarding the chemical modification of the amino group, imidazole group, carboxyl group, and -OH group, reference can be made to the descriptions in Japanese Patent Application No. 11-322913 and Reference 18 below.
When the dispersion medium contains cystine or cysteine, the sulfur group can be oxidized in the same manner as the methionine group, and converted into a sulfino group or a sulfo group. When nucleic acids are included, the amino group and imino group can be chemically modified as described above. Each modification rate (%) is preferably from 0 to 100, and more preferably from 10 to 97. As a dispersion medium, any combination of the molecular weight, the modification species, and the modification rate can be used. The modified species may be a single species or a combination of two or more species. Gelatin having a chemical modification rate of the amino group of 10 to 100% can be preferably used. In particular, when the tabular grains are grown at pH 6.0 to 12.0, the growth in the thickness direction of the tabular grains is suppressed, which is preferable.
The molecular weight is adjusted by crosslinking between molecules with a hardener when increasing the molecular weight, and by enzymatic decomposition, low pH or high pH hydrolysis, thermal decomposition, etc. when decreasing the molecular weight. Regarding the details, reference can be made to Reference 17 and Japanese Patent Application No. 11-322913.
Gelatin species include alkali-treated, acid-treated gelatin, empty gelatin from which ionic impurities have been removed, gelatin with ornitinization of 0.1 to 100% of arginine groups, fractionated gelatin with controlled molecular weight distribution, and mass% containing nucleobase 0.0-10^-2, Preferably 0.0 to 10^-FourThere is no gelatin. The gelatin source is not particularly limited, and any connective tissue of animals can be used. Usually, bone and skin of (cow, pig, fish) are preferable, and alkali-treated beef bone gelatin is more preferable. The molecular weight distribution is preferably a coefficient of variation (standard deviation of mass molecular weight distribution / mass average molecular weight) of 0.01 to 0.6, more preferably 0.01 to 0.20.
The order of the adsorptive power of the residues in gelatin adsorbed on AgX particles is [1) -S-group of methionine> 2) imidazole group >> 3) -NH₂ Group> -COOH group], especially 1), 2) and 3) are chemically modified, and the adsorption energy per molecule is reduced to the original 80 to 0.1%, preferably 50 to 1.0%. The gelatin thus obtained is preferable because it suppresses the growth of tabular grains and enables the formation of thin tabular grains.
The methionine group in gelatin is Ag on the surface of AgX particles.⁺Adsorbs to the site and prevents fogging. This is the same as the action of the antifogging agent.
In addition, a known photographic dispersion medium, a polyvinyl compound described in U.S. Pat. No. 5,380,642, a mixture of one or more graft polymers of gelatin and other molecules can be used in any ratio. Regarding the details of these dispersion media and the above-mentioned dispersion media, it is possible to refer to the following literature, the descriptions in Literatures 17 and 18, and the description in (R.D. 1996).
A_Four The dispersion medium used in is preferably a dispersion medium suitable for forming a twin-free seed crystal, and is preferably a dispersion medium having a moderately strong adsorption force for AgX particles. For this purpose, proteins and gelatin having a histidine group content (μmol / g) of 3 to 300, preferably 10 to 100 are preferred. The Met content (μmol / g) is preferably 3 to 120, more preferably 10 to 80. As an example of gelatin having a high imidazole group content, there is gelatin extracted from connective tissue (bone or skin) of fish, preferably fish living in the cold sea at 30 ° C. or lower. It can also be synthesized by reacting an organic compound having these groups with a conventionally known gelatin and covalently bonding it. For example, R⁸⁰, R⁸¹, R⁸²These groups may be contained in the.
The higher the molecular weight, the better the protective colloid, and the mass average molecular weight is 10^Four -10⁶ 10 is preferred^Five -10⁶ Is more preferable, 3 × 10^Five -10⁶ Is more preferable. The content (μmol / g) of amino group and / or —COOH group is 10 to 10^Three Is preferably 100 to 10^Three Is more preferable.
(A-2) B_Four Dispersion medium for use.
B_Four The dispersion medium used in the above is preferably a dispersion medium having a high protective colloid property. But C₁ Formed, C₂ B_Three Added to C₁ The lower the adsorbing power of the dispersion medium, the more the C₁ Is preferable because it is easily dissolved. Therefore, C₁ It is preferable to perform an operation of weakening the adsorptive power of the dispersion medium after forming the film. The operation is C₁ After forming C₂ B_Three Can be done until it is added to_Three It can also be carried out after addition to. The former is more preferable because the reaction system is simple.
The operation includes the following methods.
1) An oxidizing agent is added to oxidize the adsorbing group of the dispersion medium to reduce its adsorptivity. Standard electrode potential (E₁ ) Is higher and the concentration of the oxidizing agent is higher, the higher the probability that the adsorbing group is oxidized. The standard electrode potential of the adsorbing group is E₂ Then, [E₁ > (E₂ −0.2)] is preferred, and [(E₁ -E₂ ) = 0.0 to 1.2]. If the value is too high, the oxidant reacts with water and other groups, and the oxidation efficiency of the target product decreases. The potential is usually shown as a value where the standard hydrogen electrode potential is 0, and with respect to this value and compound examples, for example, the descriptions in the following references 11 and 12 can be referred to. Here, all the units of the potential are volts.
For example, an oxidizing agent is added to oxidize the thioether group, and —S (O) —, —S (O₂)-, -SO_Three Change to H group, or change -SH group to -SO_Three There are things to change to H group. Thereby, the thioether group content (μmol / g) is reduced to 0.1 to 95%, preferably 1.0 to 70%, more preferably 1.0 to 30% before the operation. For example, in the case of protein (including gelatin), the dispersion medium having a Met content (μmol / g) of 5 to 100 is used.₁ Is formed on the emulsion.₂ O₂ Etc.) is added and aged to achieve this mode.
2) An organic compound is covalently bonded to the adsorbing group. For example, an alkyl halide is allowed to act on a thioether group to form a sulfonium, and an alkyl halide is allowed to act on a nitrogen-containing heterocyclic ring-containing compound to alkylate a nitrogen atom.
3) Cleavage and removal of the adsorbing group. For example (-NHCO- + H₂O) → (-NH₂ + -COOH).
4) Lower the molecular weight of the dispersion medium. Hydrolysis of the main chain of the polymer with acid, alkali, or enzyme reduces the molecular weight. The adsorptive power to particles becomes weaker as the molecular weight decreases. The weight average molecular weight is the original 10^-3~ 0.9 times, preferably 10^-3~ 0.3 times.
5) When the adsorptive power becomes weak by reducing the dispersion medium, it is reduced.
The details of the oxidation and reduction reagents and methods can be referred to the descriptions in References 11 and 12 described later.
5-100 are preferable and, as for these reaction temperature (degreeC), 10-60 are more preferable. Reaction time (min) is 0.1-10^Four Is preferred, 1 to 10^Three Is more preferable. The pH of the reaction solution is preferably from 0.1 to 13, and more preferably from 1.0 to 12.
By this operation, the adsorptive power of the dispersion medium to AgX particles is reduced to 0.1 to 95%, preferably 1.0 to 70%, more preferably 1.0 to 30% of the adsorptive power before the operation. The adsorptive power can be compared by the amount of heat of adsorption when the same mass of dispersion medium is added to the same mass of AgX particles and brought to adsorption equilibrium. For example, after centrifuging [AgX emulsion of gelatin dispersion medium, removing the supernatant, then adding water and redispersing] 2 to 10 times, after removing the dispersion medium, An aqueous solution is added, and the total amount of heat generated until the adsorption equilibrium is reached is measured.
Or it can compare by the adsorption amount of the dispersion medium at the time of this adsorption equilibrium. For example, AgX particles in the adsorption equilibrium are allowed to settle by stationary natural sedimentation or centrifugation, the supernatant is removed, and the precipitate is dried. The fixed mass is pulverized, mixed with a fixed mass of KBr powder, and its infrared absorption spectrum (referred to as FTIR) is measured. Infrared absorption intensity of dispersion medium (500-2000cm^-1Area).
Ag⁺Liquid or X^-When writing a curve representing the change in silver potential when a solution is added, Ag added until the inflection point is reached⁺Or X^-It can be compared with the added molar amount. The greater the amount, the greater the adsorptive power for the corresponding atoms on the surface.
C₁ After forming 5 to 99%, preferably 20 to 99% of the dispersion medium,_Three Can also be added. As an example of the removal method, a desalting method, a centrifugal separation method, or a combination thereof described later is used.₁ There is a method of sedimenting and removing the supernatant.
In order to prevent the formation of defects such as twin planes, it is preferable that the adsorption strength of the dispersion medium is not too strong and not too weak. If too weak, intergranular coalescence occurs and defects such as twin planes are generated. If the strength is too strong, the particles grow while adsorbing the dispersion medium, and crystal defects (for example, helical dislocations and edge dislocations) occur due to the incorporation of the particles. When a strong dispersion medium is present at a high concentration, particle growth is inhibited, the generation period of new nuclei is lengthened, and ultrafine particles are obtained. However, the emulsion_Three When added to, the fine particles are protected by the dispersion medium and hardly dissolve again. In addition, the dispersion medium together with B_Three Is added to B₁ Inhibits growth. Therefore, it is most preferable that target AgX fine particles are formed with a dispersion medium having a weak adsorption force. Z₂ This is possible if formed in the presence of. This enables the embodiment (18).
(I-7) Desalination method and Z₁ , Z₂ Desorption and removal method.
Examples of the desalting method of AgX emulsion include the following method. 1) A method in which an emulsion is cooled to 25 ° C. or lower, gelled and washed with water. It is also called the Nudelle Flushing method. 2) A method of adding a coagulating sedimentation agent to precipitate the emulsion at an optimum pH and washing it with water. Na as a precipitating agent₂SO_FourThere are inorganic precipitating agents (having a salting out effect) such as, organic precipitating agents, and organic solvents that insolubilize gelatin, such as alcohol. Many organic precipitating agents neutralize the charge of ionic groups in the dispersion medium molecules and lower their hydrophilicity, thereby insolubilizing in water and insoluble aggregation. For example, naphthalene sulfonate, formaldehyde resin compound is -NH of gelatin_Three ⁺The group is neutralized by charge and insolubilized. 3) A method in which a dispersion medium that aggregates in a certain pH range, such as phthalated gelatin, is used for aggregation and sedimentation by adjusting pH. 4) Utilization of the centrifugal separation method and hydrocyclone method. 5) Use of ultrafiltration and centrifugal filtration. 6) Use of electrodialysis. A mode in which the pH difference from the isoelectric point pH of the dispersion medium is 0 to 3, preferably 0 to 1. 7) A method of contacting with an ion exchange resin. The details of these (R.D. 1996) can be referred to the description in the following literature.
As for acids and alkalis (bases) that can be used in the present invention, the description in Chapter 10 of the Chemical Handbook, Basics can be referred to._Three , H_Three PO_Four , H₂ SO_Four , NaOH and KOH can be preferably used.
A_Three The photosensitive material coated with chemical sensitization or chemical sensitization and spectral sensitization is particularly sensitive to a high contrast material having a gamma value of 2.0 to 20, preferably 3.0 to 20 (sensitivity / granularity). The ratio is excellent and preferable.
After the preparation of the AgX emulsion in the embodiment of (I-1), Z is carried out at an arbitrary time immediately before coating, preferably before the desalting step.₁ , Z₂ 1.0 to 100%, preferably 70 to 100%, can be desorbed, and desorbed and removed out of the system. Desorption is carried out for 5 seconds to 10 days, preferably 1 minute to 5 hours under the most preferred combination conditions within the range of 10 to 98 ° C., pH 1.0 to 12.5 and pX = 0.5 to 5.0. Can be removed. The details of the desorption and removal can be referred to the description of Japanese Patent Application No. 11-364902.
Other than the cationic organic compound such as the onium salt, an anionic organic compound₁ , Z₂ 0.01-10 of the abundance of^Five Double molar amount, preferably 0.1-10^Four A double molar amount can be added and removed, or the compound can be collected on the negative electrode side by electrodialysis and removed. Examples of the compound have a molecular weight of 100 to 10⁶ , Preferably 100 to 10^Five There are anionic surfactants described below, and the description in Reference 16 (R.D. 1996) described later can be referred to. In addition, the salt concentration of the emulsion is increased and the ionic strength is increased from 1.2 to 10.^Four Double, preferably 2-10^Four There is a method in which the compound (i) is salted out and removed by increasing it twice. The compound is easily salted out, and since it is composed of light element atoms, its specific gravity is smaller than that of water or the emulsion, so that it is easily salted out as a floating substance on the surface of the emulsion. The suspended matter may be removed from the emulsion. There are a method of sucking the surface portion, a method of gently taking out the emulsion from the bottom of the container and leaving the surface portion in the container.
With regard to the soluble salt to be added, the description of the inorganic compound / complex dictionary, Kodansha (1997) can be referred to. Other, X^-A salt is preferable, and it can be desorbed and salted out at pX = 0.5 to 2.5, preferably 0.7 to 2.0. X^-Cl as seed^-, Br^-Can be used alone or in combination at any ratio. (Onium⁺) ・ (X^-) ← → (Onium⁺) + (X^-This is for shifting the dissolution equilibrium to the left.
(I-8) Others.
A₁ , B₁₃, Preferably A₁ , B₁₅Is preferably a double-structured particle having an AgI content (mol%) of the core portion of 0.1 to 40, preferably 1 to 40, and an AgI content (mol%) of the shell portion of 0.0 to 20. Core part / shell part) molar ratio = 1/10^Four~Ten^Four/ 1 is preferred, 1/10^Three~Ten^Three/ 1 is more preferred. The particle size (μm) is preferably from 0.1 to 20. (AgI content of core part-AgI content of shell part) (mol%) = 0.1-40, preferably 1-40, more preferably 5-35. Furthermore, the AgX solvent concentration (mol / liter) is 0 to 1.0, preferably 0 to 0.01, more preferably 0 to 10.^-FiveParticles formed under the conditions are preferred.
Ag⁺A compound having a high hydrophilicity acts as an AgX solvent, and a small compound is an antifoggant (A₄₀) And act as a particle deformation inhibitor. When pX = 2.2 or less, preferably 0.3 to 1.7, the particle surface is X^-Body, A₄₀Can hardly adsorb. A₄₀Coordinates with an AgXn (n is an integer of 2 or more) complex, becomes hydrophilic, and acts as an AgX solvent. For this reason, the thin tabular grains are thickened. Therefore, A in the region of 40-100 ° C. in this region.₄₀Is preferably avoided.
A₁ , A₀ In the particles, the inside of the particles is reduced and sensitized by a high pH (pH 8 to 13) and / or a reducing agent.^Three1-10 per⁸ Pieces, preferably 5-10⁶ It is preferable that there is an individual. When the photosensitive material is stored at 40 to 100 ° C. for 1 hour to 1 day, the nuclei in the particles move, and the photographic properties of the photosensitive material change. The activation energy (kjoule / mol) of the change is 50 to 75, preferably 57 to 67, and is small. This is not preferred. In order to prevent this, reduction sensitization is performed after the step of introducing dislocation lines inside the grains during grain formation, and the nuclei are formed on the dislocation lines, or the nuclei are formed during the impurity doping, It is to exist in close proximity or combined to stabilize the nucleus. Or 10 to 10 at 40 to 120 ° C., preferably 50 to 90 ° C., humidity 1 to 70, preferably 5 to 40%, between the application of the AgX emulsion and the shipment of the photosensitive material.^Five Minutes, preferably 60-10^Four It is preferred to store for a minute to allow the nuclei to reach chemical equilibrium.
Alternatively, it is preferable to hold the AgX emulsion at the temperature and the time while standing or stirring immediately after the grain formation and immediately before adding the chemical sensitizer so that the nucleus reaches a chemical equilibrium state.
Regarding the AgX particles, the epitaxial particles and the host particles, the metal dope, the metal complex dope, the chemical sensitization, the spectral sensitization, the color material and layer constitution for the color sensitizing material constitution, and the development processing, the description in Reference 5 below is given. Can be helpful.
[0047]
You may form the said grain which has a dislocation line inside by using these tabular grains as a core. In this regard, the description in Reference 13 below can be referred to.
The multi-structure particles can be formed by using the particles as core particles and laminating an AgX layer different from the core particles. Regarding the details, reference can be made to the description in Reference 14.
(Chemical sensitization)
For chemical sensitization of AgX emulsions, chalcogen sensitizers (sulfur sensitizers, selenium sensitizers, teller sensitizers), gold sensitizers alone, or a combination of any two or more of them can be used. . The total amount of chalcogen sensitizer and the total amount of gold sensitizer per 1.0 mole of AgX particles was 10^-9-10^-2Moles are preferred, 10^-7-10^-FourMole is more preferred. For details of the compound, reference can be made to Reference 15, (R.D. 1996) and the description of the following reference.
Regarding the production of high AgCl content tabular grain emulsions, the descriptions in JP-A-8-227117, JP-A-9-288325 and JP-A-2-34 can be referred to.
The high refractive index inorganic fine particles are added to and contained in the tabular grain emulsion, and when the emulsion is coated on a support to form a photosensitive material, the dispersion medium phase is substantially free from light of the peak light wavelength of the layer. Transparent, the refractive index value of the dispersion medium phase with respect to the light is 1.03 to 2.5 times, preferably 1.06 to 2.0 times the value when the fine particles are not contained, The vertical reflectance of the light with respect to the main plane of the tabular grain in the layer is 0.1 to 97%, preferably 1 to 80% when not contained.
The fine particles are not substantially fused together in the layer, and the molar amount (7 mol or more, preferably 3 or more mol of fine particles / mol of all fine particles) is 0.0 to 0.00. 2 is preferable, and 0.0 to 0.05 is more preferable. The photosensitive material is preferably a color photosensitive material having at least one of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer, preferably three layers, more preferably a fourth photosensitive layer, and the photosensitive material is exposed. It is preferable that the film is processed in a development process including at least a development process and a fixing process. The fine particle-containing emulsion can be used as a photosensitive layer for all photosensitive materials described below, preferably color photosensitive materials. In the case of a diffusion transfer type color light-sensitive material, a color material is added to the emulsion. Regarding the colorant, the color developing agent for color photography, the additive, and the oil for emulsifying and dispersing (RD 1996), reference can be made to Japanese Patent Application No. 11-280207 and the descriptions in the following literature.
The fine particles include crystal, amorphous, and a mixture of both, and there are (core / shell) structures having one or more core layers and one or more shell layers, and multi-structure particles. Metal oxides are preferred, TiO₂ The content (mol%) is 10 to 100, preferably 50 to 100. Regarding these details, reference can be made to the descriptions in Japanese Patent Application Nos. 11-280207 and 11-212364.
Since the thickness of the particles is thin, the amount of intrinsic absorbed light decreases. In order to compensate for the blue light-sensitive emulsion, it is preferable to adsorb a sensitizing dye having an absorption band in the 350 to 530 nm region at 20 to 300%, preferably 60 to 200% of the saturated adsorption amount.
[0048]
The AgX emulsion grains produced by the method of the present invention can be blended with one or more other AgX emulsions, or two or more emulsion grains of the present invention having different particle diameters can be blended and used. The blend ratio (guest AgX emulsion mole / AgX emulsion mole after blending) is preferably in the range of 0.99 to 0.01, and an optimum ratio can be appropriately selected and used. There are no particular limitations on the additive and the amount of the additive that can be added to the emulsion of the present invention from the grain formation to the coating step, and any conventionally known photographic additive can be added in an optimum amount. For example, AgX solvents, dopants to AgX particles (for example, Group 8 noble metal compounds, other metal compounds, chalcogen compounds, SCN compounds, etc.), dispersion media, antifoggants, sensitizing dyes (blue, green, red, infrared) , Panchromatic, ortho, etc.), supersensitizer, chemical sensitizer (sulfur, selenium, tellurium, gold and group 8 noble metal compounds, phosphorus compounds, rhodan compounds, reduction sensitizers alone or in combination of two or more thereof ), Fogging agent, emulsion precipitating agent, surfactant, hardener, dye, color image forming agent, color photographic additive, soluble silver salt, latent image stabilizer, developer (hydroquinone) Compound, etc.), pressure desensitization inhibitor, matting agent, antistatic agent, dimensional stabilizer and the like.
[0049]
The AgX emulsion prepared by the method of the present invention can be used for any conventionally known photographic light-sensitive material. For example, black and white silver halide photographic light sensitive materials [for example, X-ray sensitive materials, printing sensitive materials, photographic paper, negative films, microfilms, direct positive sensitive materials, ultrafine particle dry plate sensitive materials (for LSI photomasks, shadow masks) , For liquid crystal masks)], and color photographic light-sensitive materials (eg, negative film, photographic paper, reversal film, direct positive color light-sensitive material, silver dye bleaching method photograph, etc.). Further examples include diffusion transfer photosensitive materials (for example, color diffusion transfer elements and silver salt diffusion transfer elements), photothermographic materials (black and white, color), high-density digital recording photosensitive materials, and holographic photosensitive materials. The amount of silver applied is 0.01-50 (g / m²) Can be selected.
AgX emulsion production method (grain formation, desalting, chemical sensitization, spectral sensitization, photographic additive addition method, etc.) and apparatus, AgX grain structure, support, subbing layer, surface protective layer, composition of photographic photosensitive material There are no restrictions regarding the product form and storage method (e.g., layer composition, silver / color former molar ratio, silver amount ratio between layers), emulsification dispersion of photographic additives, exposure, development method, etc., which will be known in the past or in the future. Any technique or embodiment that can be used can be used. Regarding these details, the descriptions in the following documents can be referred to.
[0050]
Reference 20, Research Disclosure, (Item 17643) (December 1978), (RD 1996), by Duffin, Photographic Emulsion Chemistry, Focal Press, New York (1966), Bill (EJ Birr), Stabilization of Photographic Silver Halide Emulsion, Focal Press, London (1974), edited by James (TH James) The Theory of Photographic Process, 4th edition, Macmillan, New York (1977)
[0051]
P. Glafkides, Chemie et Physique Photograph ique, 5th edition, (Edition del, Usine Nouvelle, Paris (1987), 2nd edition, Paul Monter, Paris (1957) ), VL Zelikman et al., Making and Coating Photographic Emulsion, Focal Press (1964), KR Hollister, Journal of Imaging Science, 31 Volume, P.148-156 (1987), JE Maskasky, Volume 30, P247-254 (1986) Volume 32, 160-177 (1988), Volume 33, 10-13 1989),
[0052]
Edited by Freezer et al., Die Grundlagen Der Photographischen Prozesse Mit Silverhalogeniden (Akademische Verlaggesellschaft), Frankfurt (1968).
JCIA Monthly Report 1984, December issue, p. 18-27, Journal of the Japan Society of Photography, 49, 7-12 (1986), 52, 144-166 (1989), 52, 41-48 (1989), Japanese Patent Laid-Open No. 58-11936. 113928, 59-90841, 58-111936, 62-99751, 60-143331, 60-143332, 61-14630, 62-6251,
[0053]
JP-A-1-131541, 2-838, 8-220664, 8-227117, 2-14633, 3-155539, 3-250532, 3-246534, No. 4-34544, No. 2-28638, No. 4-109240, No. 2-73346, No. 4-193336, No. 6-215513, other Japanese patents in the field of AgX photography, US patents, Europe Patent, International Publication (WO) Application, Journal of Imaging Science, Journal of Photographic Science, Photographic Science and Engineering, Journal of the Japan Society of Photography Photographic Society Abstracts, International Congress of Photographic Scien Collection of lectures on ce and The International East-West Symposium on the Factors Influencing Photographic Sensitivity. Japanese Patent Application Nos. 6-104065 and 5-324502.
The emulsions of the present invention are disclosed in JP-A Nos. 62-266538, 63-220238, 63-305343, 59-142539, 62-253159, JP-A-1-131541, 1-297649, 2-42, 1-158429, 3-226730, 4-151649, Japanese Patent Application Nos. 4-179961, 11-57097, and constituent emulsions of coated samples in Examples of European Patent 0508398A1 Can be preferably used.
[0054]
(Reference)
1. JP-A-59-133542, 60-95533, U.S. Pat. Nos. 3,206,313, 3,317,322, 3,761,276, 4,269,927, 3 367, 778, JP-A-1-158429, 1-297694, (RD1994), and documents described later.
2. JP-A-63-305343, JP-A-64-62631, JP-A-64-40938, JP-A-2-838, JP-A-1-297649, JP-A-2-14633, JP-A-1-201651, JP-A-3-121445. .
3. Journal of Photographic Science, 23, 249 (1975). JP-A 64-62631, (R.D. 1996).
4). European Patent Nos. 699,944A to 699,951A, 701,164A to 701,165A, Japanese Patent Application Laid-Open No. 5-341426, and documents described below. 5). Journal of Imaqing Science, 32, 160-177 (1988), Journal of Colloid and Interface Science, 140, 335-361 (1990), RD (1994), European Patent No. 699,944A1 699, 951 A1, 215, 612 B1, and documents described below.
6). Basics of photographic engineering, silver halide photography, Chapter 3, Corona (1979).
7. Journal of Imaqing Science, 30, 247-257 (1986). 8). JP-A Nos. 11-223895, 11-231450, 11-218862, 11-218863, 11-218865, 6-194768, 7-311431, 8-106137, No. 8-339044, No. 9-211761, No. 11-305366, No. 5-313273, No. 11-249248, No. 6-308648, No. 6-308649.
9. T.H.James, The Theory of Photographic Process, 4th edition, Macmillan (1977).
10. JP-A-4-184326 to 184330, 4-34544, 1-183644, 1-183417, 2-166442, 11-30828, 4-184330, 4 No. 181240, No. 5-5966, No. 2-167818, US Pat. No. 5,196,300, (RD1996). European Patent Nos. 323,215A, 431,584A, 407,576A, and 779,537A.
11． 4th Edition, Electrochemical Handbook, Chapters 3-6, Maruzen (1985), 4th revised edition, Chemical Handbook, Basics, Chapter 12, Maruzen (1993).
12． Japanese Patent Application Laid-Open Nos. 10-104769 and 8-69069, New Experimental Chemistry Course Volume 15, Oxidation and Reduction, Maruzen (1976), Satoshi Imoto, Course Organic Reaction Mechanism Volume 10, Tokyo Chemical Doujin (1965), Small Edited by Yoshiro Hokata, Oxidation and reduction of organic compounds, Nanedo (1963), JP-A-61-3134, World Science Encyclopedia, "Oxidation reduction", "Oxidation process", "Oxidizing agent", Kodansha (1977 ), Britannica International Encyclopedia, “Oxidation and Reduction”, TBS Britannica (1988).
13. JP-A-62-220238, US Pat. No. 5,476,760, JP-A-8-62754, JP-A-7-270952, JP-A-6-230491, JP-A-4-166926, JP-A-6-230491 .
14. JP-A-1-2016651, JP-A-2-28638, JP-A-2-943, JP-A-3-121445, JP-A-5-45757, and JP-A-60-143331.
15． JP-A-8-220664, 11-65009, and 9-197604 (R.D. 1996).
16． Chemical Handbook, Applied Chemistry, Chapter 16, Maruzen (1986), Horiguchi Hiroshi, New Surfactant, Sankyo Publishing (1975), (R.D. 1996).
17． U.S. Pat. Nos. 5,318,889, 5,187,259, JP-A-6-214329, 5-265113, 1-158426, edited by Nobumasa Imura, Biochemical Handbook, Chapter 20, Chapter 21, Maruzen (1984).
18． U.S. Pat. Nos. 4,713,320, 4,942,120, 5,412,075, JP-A-8-82883, 7-311428, 10-10663, and Japanese Patent Application No. 10- 87535, Journal of the Photographic Society of Japan, Vol. 58, 25-30 (1995), Niwato Gelatin, Chapter 4, Nippon Niwa-Gelatin Industrial Association (1987), The Science and Technology of Gelatin, Chapter 7, Academic Press (1977), New Chemistry Experiment Course 1, Protein IV, Tokyo Kagaku Dojin (1991), Applications and Markets of Water-Soluble Polymers, CMC (1984), Water-Soluble Polymers, Chemical Industries (1990) Year Edition), Research Disclosure, 389, item 38957 (September 1996) (hereinafter referred to as "RD1996"), Kazutaka Tanizawa et al., Chemical Modification of Protein, Hirokawa Shoten (1991).
19. JP-A-2-838, 8-82883, 10-10663, 10-104769, 1-221337, 10-142721, 11-65009, 7-98482, No. 10-293372, US Pat. Nos. 5,210,013, 5,439,787, 5,962,206, Japanese Patent Application Nos. 11-364902, and 11-322913.
[0055]
【Example】
  EXAMPLES Next, although an Example demonstrates this invention further in detail, the embodiment of this invention is not limited to this.
  In addition, Example 1 and 2 shall be read as the reference examples 1 and 2, respectively.
Example 1
  Gelatin solution 1 [1200 g of water, 0.6 g of KBr, 10 of compound 1^-FourMole, 30 g of gelatin 1, adjusted to pH 6.0 with NaOH solution] were put in a reaction vessel, and kept at 60 ° C. while stirring, Ag-11 solution [AgNO in 100 ml]_Three 1.0g and gelatin 1 0.9g, HNO_Three(1N) solution 0.25 ml] and X-11 solution [100 ml of KBr 0.8 g, compound 1 10^-FourMole, 0.9 g of gelatin 1 and 0.25 ml of NaOH (1N) solution] were added simultaneously at 5 ml / min for 3 minutes. Subsequently, the Ag-11 solution was added simultaneously with the X-11 solution while maintaining the pBr of 2.37 by the silver potential control method at a start flow rate of 5.0 ml / min and an acceleration flow rate of 1.5 ml / min for 14 minutes. After stirring for 1 minute, KBr solution is added, pH is adjusted to 6.0 to pBr1.5, and then Ag-12 solution [AgNO in 100 ml is maintained while maintaining pBr1.5._ThreeWas added at the same time as the X-12 solution (containing 10.6 g of KBr in 100 ml) at a start flow rate of 2.0 ml / min and an acceleration flow rate of 0.56 ml / min for 44 minutes.
  Next, Ag-13 solution [AgNO in 100 ml]_Three 28 g] was added at the same time as solution X-13 (containing 20.5 g of KBr in 100 ml) at a starting flow rate of 12 ml / min and an acceleration flow rate of 0.18 ml / min for 20 minutes. After stirring for 1 minute, the following post-treatment was performed. Ag-14 solution [AgNO in 100 ml_ThreeWas added to obtain a pBr of 2.6, sensitizing dye 1 was added by 85% of the saturated adsorption amount, the temperature was raised to 70 ° C., and the mixture was stirred for 20 minutes. Next, the antifoggant (F1) is added (10^-3Mole / mole AgX) was added and stirred for 15 minutes. Compound 1 was desorbed by adsorbing them. Next, a coagulating sedimentation agent was added, the temperature was lowered to 30 ° C., the pH was adjusted to 4.0, the emulsion was allowed to settle, and desalted according to a conventional method by a sedimentation washing method. This removed over 95% of compound 1. The gelatin solution was then added and redispersed at pH 6.4, pBr 2.6, 40 ° C.
  At this time, 1 ml of the emulsion was collected, and a transmission electron micrograph image (hereinafter referred to as “TEM image”) of the replica film of the grains was observed. The results are shown in Table 2. The temperature was raised to 60 ° C., and gold sensitizer-1 [chloroauric acid: NaSCN = 1: 20 molar ratio aqueous solution] was used in the amount of Au (8 × 10^-6Mol / mol AgX) and after 2 minutes the chalcogenide sensitizer Sx1 was added Na.₂ S₂ O_Three In quantity (10^-FiveMole / mol AgX) was added and aged for 30 minutes. This emulsion was coated according to the following coating formulation and hardened to obtain a cut sample. Gelatin 2, a thickener and a coating aid were added, and the mixture was applied onto a cellulose triacetate transparent base subbed with a protective layer containing a hardener 1 and dried. The sample was placed in a sealed empty can and stored at 40 ° C. for 17 hours to allow the dural reaction to proceed. Next, this was taken out and cut into Sample 1-1.
(Comparative Example 1)
  A sample 1-2 was prepared by coating and cutting in the same manner except that the addition of compound 1 was omitted in Example 1.
[0056]
Embedded image

[0057]
Example 2
Gelatin solution 2 [1200 g of water, 0.36 g of NaCl, 10 of compound 2^-FourMole, 30g of gelatin 1, HNO_Three The solution was adjusted to pH 4.5 with a solution], put in a reaction vessel, kept at 40 ° C., and stirred with stirring Ag-21 solution [AgNO in 100 ml]_Three 2.0 g, gelatin 1 0.9 g, compound 2 10^-FourMol, HNO_Three(Includes 0.25 ml of (1N) solution] and X-21 solution (containing 0.76 g of NaCl, 0.9 g of gelatin 1 and 0.25 ml of NaOH (1N) solution in 100 ml) at 6.0 ml / min for 3 minutes Were simultaneously added. Subsequently, the Ag-21 solution was added simultaneously with the X-21 solution while maintaining pCl 2.3 by a silver potential control method at a start flow rate of 6.0 ml / min and an acceleration flow rate of 2.0 ml / min for 14 minutes. The pH was adjusted to 6.0.
Next, Ag-22 solution [AgNO in 100 ml_Three At the same time as the X-22 solution (containing 7.0 g of NaCl in 100 ml) while maintaining pCl 2.0 for 60 minutes at a starting flow rate of 3.1 ml / min and an accelerating flow rate of 0.2 ml / min. Added. Next, 0.003 mol of U-5 was added as AgI, the temperature was raised to 65 ° C., and aging was performed for 15 minutes. Ag-14 solution was added to make pCl 2.3, and sensitizing dye 2 was added by 85% of the saturated adsorption amount. The temperature was raised to 65 ° C. and stirred for 20 minutes. Further, an antifoggant (F2) is added (10^-3Mole / mole AgX) was added and stirred for 15 minutes. Next, the precipitating agent was added, the temperature was lowered to 30 ° C., the pH was adjusted to 4.0, and the emulsion was precipitated and desalted. This removed over 95% of compound 2. The gelatin solution was then added and redispersed at pH 6.4, pCl 2.6, 40 ° C.
1 ml of the emulsion was collected, and a TEM image of the replica film of the grains was observed. The results are shown in Table 2. Raise the temperature to 55 ° C and add 3 x 10 fog reduction agent (F3).^-FiveOnly mol / mol AgX was added and stirred for 15 minutes. Next, the Sx1 is changed to Na.₂ S₂ O_Three In quantity (2 x 10^-FiveMol / mol AgX) and after 3 minutes 5 × 10 chloroauric acid is added.^-6Only mol / mol AgX was added and aged for 20 minutes. The emulsion was coated in the same manner as in Example 1, cured, and cut to obtain Sample 2-1.
(Comparative Example 2)
A coated sample 2-2 was obtained in the same manner as in Example 2, except that the addition of Compound 1 was omitted and U-6 was added instead of U-5.
Example 3
Gelatin solution 3 [1200 ml water, 1.7 g gelatin 3 and 0.5 g KBr, HNO_Three The solution is adjusted to pH 2.3 with a liquid, placed in a reaction vessel, placed in a constant temperature water bath at a temperature of 1.0 ° C., and kept at a temperature of 1.0 ° C., the Ag-31 solution [AgNO in 100 ml_Three 6.0 g, gelatin 3 0.14 g, HNO_Three(Containing 0.2 ml of (1N) solution) and X-31 solution (4.29 g of KBr, 0.14 g of gelatin 3 and 0.2 ml of NaOH (1N) solution in 100 ml) were added simultaneously at 30 ml / min for 1 minute. . The Ag-31 solution and the X-31 solution were added after passing through a liquid feeding tube having an outer diameter of 3 mm through the constant temperature water bath and cooling to about 1 ° C.
2.8 g of KBr was added, the temperature was raised to 60 ° C. at 3 ° C./min, and the mixture was aged for 12 minutes. NaOH solution was added to pH 9.1 and aged for 12 minutes. Gelatin solution 4 (25 g of gelatin 4 and 175 g of water) was added to adjust the pH to 7.0. Next, 0.32 mol of AgBr fine grain emulsion (U-1) and a KBr solution were added thereto to obtain a pBr of 1.6, and the temperature was raised to 75 ° C. Ten minutes later, 0.32 mol of U-1 was added, and the temperature was lowered to 60 ° C. 15 minutes after the added fine particles almost disappeared. The Ag-14 solution was added at an addition rate at which no new nuclei were generated to obtain pBr2.3.
Sensitizing dye 1 was added by 85% of the saturated adsorption amount and stirred for 20 minutes. Furthermore, (F1) is changed to (10^-3Mole / mole AgX) was added and stirred for 15 minutes. A precipitating agent was added, the temperature was lowered to 30 ° C. to pH 4.0, and the emulsion was allowed to settle and desalted. This removed over 95% of compound 1. Gelatin solution 2 was added and redispersed at 40 ° C., pH 6.4, pBr 2.6. 1 ml of the emulsion was collected, and a TEM image of the replica film of the grains was observed. The results are shown in Table 3. A in Table 3₅₁Indicates the projected area ratio (%) of {111} tabular grains having an aspect ratio of 2 or more with respect to the total projected area of AgX grains.
The temperature is raised to 60 ° C., and the sensitizer Sx1 is Na₂ S₂ O_Three In quantity (2 x 10^-FiveMole / mole AgX) was added, and gold sensitizer-1 was added (8 × 10 10^-6Mole / mol AgX) was added and aged for 30 minutes. The emulsion was applied in the same manner as in Example 1, cured, and cut to obtain Sample 3-1.
(Comparative Example 3)
A coating sample 3-2 was obtained in the same manner as in Example 3 except that U-2 was used instead of U-1 in Example 3.
Example 4
Gelatin solution [H₂ 1.2 kg of O, 2.7 g of NaCl, 3 × 10 of compound 3^-FourMole, 5 g of gelatin 1 and pH 5.6] was added, kept at 30 ° C., Ag-41 solution [AgNO in 100 ml] with stirring._Three 25.5 g) and X-41 solution (9.4 g of NaCl, 9.4 g of NaCl, 1 g of gelatin 3 and pH 6.0) were simultaneously mixed at 30 ml / min for 1 minute, and the seed crystals of twin tabular grains were obtained. Formed. After 1 minute, an aqueous gelatin solution (25 g of gelatin 1 and 10 of compound 4)^-Four200 g of a mixture containing a molar amount adjusted to pH 5.6) was added to obtain pCl 1.6.
Next, the temperature was raised to 65 ° C. and aged for 15 minutes. Next, 0.2 mol of AgCl fine grain emulsion (U-3) was added and ripened for 20 minutes, and then 0.4 mol of U-3 was added and ripened for 20 minutes. After adding 0.005 mol of U-5 in the amount of AgI and aging for 15 minutes, the Ag-14 solution was added at an addition rate at which no new nuclei were generated to give pCl 2.2.
The temperature was lowered to 60 ° C., and sensitizing dye 2 was added by 85% of the saturated adsorption amount. Next, the antifoggant F2 (10^-3Mole / mole AgX) was added and stirred for 15 minutes before adding the precipitating agent. The temperature was lowered to 30 ° C. to pH 4.0, and the emulsion was allowed to settle and desalted. This removed more than 95% of the compound. Gelatin solution was added and redispersed at 40 ° C., pH 6.4, pCl 2.3. The TEM image of the generated particles was observed, and the results are shown in Table 3. A {111} tabular grain emulsion was obtained.
The temperature is raised to 55 ° C. and F3 is (3 × 10^-FiveMole / mole AgX) was added and stirred for 15 minutes. Next, Sx1 is set to (2 × 10^-FiveMol / mol AgX) is added, followed by chloroauric acid (5 × 10^-6Mole / mol AgX) was added and aged for 30 minutes. The temperature was lowered to 40 ° C., coating was performed in the same manner as in Example 1, dried, hardened, and cut to obtain Sample 4-1.
(Comparative Example 4)
A coated sample 4-2 was obtained in the same manner as in Example 4 except that U-4 was used instead of U-3 in Example 4 and U-6 was used instead of U-5.
Example 5
Gelatin solution 5 [H₂ O 1200g, gelatin 1 25g, compound 2 10^-FourMole, 0.8 g of NaCl, pH 4.3] is added, and the temperature is kept at 30 ° C., while stirring, Ag-51 solution [AgNO in 100 ml]_Three 20 g and gelatin 1 1.0 g, HNO_Three 5 × 10^-3M-containing] and X-51 solution [100 g of NaCl 7 g, gelatin 1 g, NaOH 5 × 10^-3The mixture was added at a rate of 50 ml / min for 30 seconds to form AgCl fine particles. After stirring for 2 minutes, solution X-52 (containing 1.5 g of KBr and 1 g of gelatin in 100 ml) was added at 60 ml / min for 30 seconds. The temperature was raised to 40 ° C. at (3 ° C./min) and stirred for 3 minutes. Next, Ag-51 solution and X-51 solution were simultaneously mixed and added at 50 ml / min for 1 minute. 16 ml of NaCl-51 solution [NaCl 0.1 g / ml] was added, and the pH was adjusted to 5.2 with NaOH solution. Next, the temperature was raised to 70 ° C. at 2 ° C./min and aged for 12 minutes. U-3 was added at 0.2 mol in AgCl to give pCl 1.9. After aging for 20 minutes, 0.4 mol of U-3 was added and aged for 30 minutes with pCl 1.9. Next, Ag-51 solution and X-53 solution (containing 7 g of NaCl and 2.5 g of KBr in 100 ml) were added at 5 ml / min for 3 minutes. Sensitizing dye 2 was added at 85% of the saturated adsorption amount. After stirring for 15 minutes, F2 (10^-3Mole / mole AgX) was added and stirred for 15 minutes. A precipitating agent was added, the temperature was lowered to 30 ° C. to pH 4.0, and the emulsion was allowed to settle and desalted. This removed over 95% of compound 2. Gelatin solution was added and redispersed at 40 ° C., pH 6.4, pCl 2.3. The TEM image of the generated particles was observed, and the results are shown in Table 3. A {100} type tabular grain emulsion was obtained.
The temperature is raised to 55 ° C. and Sx1 is set to (2 × 10^-FiveMol / mol AgX) was added, and after 3 minutes, an aqueous chloroauric acid solution was added (5 × 10^-6Mole / mol AgX) was added and aged for 30 minutes. The temperature was lowered to 40 ° C., coating was performed in the same manner as in Example 1, dried, hardened, and cut to obtain a sample 5-1.
(Comparative Example 5)
A coating sample 5-2 was obtained in the same manner as in Example 5 except that U-4 was used instead of U-3 in Example 5.
The obtained sample was exposed to white light for 0.1 seconds through an optical wedge, and Samples 1-1, 1-2, 3-1, 3-2 were MAA-1 developer [Journal of Photographic Science, Vol. 23, 249-256 (1975)] and developed at 20 ° C. for 10 minutes. On the other hand, Samples 2-1, 2-2, 4-1, 4-2, 5-1, and 5-2 were MAA-2 developers [MAA-1 KBr was replaced with NaCl (0.58 g / liter). Development] at 20 ° C. for 4 minutes. Next, sensitometry is performed through the steps of stopping, fixing, washing and drying, and a (sensitivity / granularity) ratio is obtained, and its relative value (A₅₀Are shown in Table 2 and Table 3. Sensitivity is represented by the reciprocal of the exposure amount (looks / second) giving a density of (fog + 0.2), and the granularity is a light quantity giving a density of (fog + 0.2) to 10^-2The film was uniformly exposed for 2 seconds, developed, and the dispersion of density was measured with a microdensitometer using a circular opening having a diameter of 48 μm to determine the rms granularity σ. The details are described in Chapter 21, Section E of Document 7.
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[Table 2]

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[Table 3]

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Embedded image

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(Gelatin 1): Methionine content is about (5 μmol / g) and mass average molecular weight is about 10^Five Gelatin.
The molecular weight is about 10^Five H 2 in an aqueous solution of deionized alkali treated bovine bone gelatin (EGel 1)₂ O₂ After the thioether group of methionine group was oxidized to a sulfoxide group, residual H₂ O₂ MnO₂ Powdered, decomposed and removed, MnO₂ The powder has been removed by filtration.
(Gelatin 2): Methionine content is about (43 μmol / g), mass average molecular weight is about 5 × 10^Five Gelatin. EGel 1 was prepared by intermolecular crosslinking with a hardener 1.
(Gelatin 3): Gelatin having a mass average molecular weight of about 15000 and a methionine group content (μmol / g) of 0. Gelatin (LGel 1), which is obtained by adding an enzyme to an aqueous solution of EGel 1 and decomposing at about 40 ° C. and pH 5.5 to reduce the molecular weight, as in gelatin 1, is oxidized.
(Gelatin 4): Gelatin having a mass average molecular weight of about 30,000 and a methionine group content of 5 (μmol / g).
(Gelatin 5): Gelatin obtained by trimming about 50% of the amino group of EGel 1
Preparation of AgBr fine grain emulsion (U-1): Gelatin solution 31 [1200 ml of water, 24 g of gelatin 4 and 3 × 10 of compound 1^-FourMole, containing 0.3 g of KBr, adjusted to pH 6.0 with NaOH solution] is placed in a reaction vessel, and this is placed in a constant temperature water bath, while maintaining the solution temperature at 20 ° C., Ag-35 solution [AgNO in 100 ml]_Three 20 g, gelatin 4 0.8 g, HNO_Three 2.5 × 10^-FourM-containing] and X-35 solution [KBr 14.06 g, gelatin 4 0.8 g, NaOH 2.5 × 10 in 100 ml]^-FourBoth at 15 ml / min for 10 seconds followed by 70 ml / min for 7 minutes.
At this time, Cp-1 aqueous solution [compound 1 in 3 × 10^-FourWas added at 1.5 ml / min for the first 10 seconds, followed by simultaneous mixing at 7 ml / min for 7 minutes. After stirring for 2 minutes, this was used as U-1 within 30 minutes. Average diameter of produced particles (A₅₂) Is about 0.035 μm, and the ratio of particles containing two or more twin planes (A₅₃) Is 0.00%, the proportion of particles containing one or more twin planes (A₅₄) Was also 0.0%.
Preparation of (U-2): Prepared in the same manner as U-1 except that all additions of compound 1 were eliminated. A₅₂= 0.05 μm, A₅₃= 2%, A₅₄= 8%. Preparation of (U-3): Gelatin solution 41 [1200 ml of water, 24 g of gelatin 4 and 3 × 10 of compound 2^-FourMol, 0.3g NaCl, HNO_Three In a constant temperature water bath at 20 ° C., and while maintaining the solution temperature at 20 ° C., Ag-35 solution and X-45 solution [NaCl 3.5 g in 100 ml, gelatin 4 0.8 g, NaOH 3 × 10^-FourBoth at 30 ml / min for 10 seconds followed by 7 minutes at 100 ml / min.
At this time, an aqueous solution of Cp-2 [compound 2 in 100 ml 2 × 10^-FourWas added at 3.0 ml / min for the first 10 seconds, followed by simultaneous mixing at 10 ml / min for 7 minutes. 2 minutes later₂ O₂ After adding 5 ml of (3.1% by mass) and homogenizing and mixing, the mixture was allowed to stand at 20 ° C. for 1 hour, whereby the methionine group content (μmol / g) of the gelatin became zero. After stirring, this was used as U-3. A₅₂= 0.04 μm, A₅₃= 0.0%, A₅₄= 0.0%.
Preparation of (U-4): Prepared in the same manner as U-3 except that all addition of compound 2 was eliminated. A₅₂= 0.06 μm, A₅₃= 2.2%, A₅₄= 10%.
Preparation of AgI fine particles (U-5): gelatin solution 32 [1200 ml of water, 24 g of gelatin 4 and 3 × 10 of compound 1^-FourMole, containing 0.3 g of KI, adjusted to pH 6.0 with NaOH solution] was placed in a reaction vessel, and this was placed in a constant temperature water bath, while maintaining the solution temperature at 20 ° C., Ag-35 and X-35 solutions [100 ml Inside, 19.6 g of KI, 0.8 g of gelatin 4 and 3 × 10 NaOH^-FourBoth at 15 ml / min for 10 seconds followed by 70 ml / min for 7 minutes.
At this time, the Cp-1 aqueous solution was added at a rate of 1.5 ml / min for the first 10 seconds, followed by simultaneous addition at 7 ml / min for 7 minutes. 2 minutes later₂ O₂ Was added to the mixture, homogenized and mixed, and then allowed to stand at 20 ° C. for 1 hour, which was designated as U-5. A₅₂= 0.014 μm, A₅₃= 0.0%, A₅₄= 0.0%.
Preparation of (U-6): Prepared in the same manner as U-5 except that all addition of compound 1 was eliminated. A₅₂= 0.025 μm, A₅₃= 1.8%, A₅₄= 9%.
All of (U-1) to (U-6) were prepared in a mixing vessel installed within 3 m from the reaction vessel to be added, and added after adjusting to the same pH and pX as the AgX emulsion to be added. It was done. Ag⁺Liquid and X^-Liquid and Z₁ , Z₂ Were added to the mixing box present in the reaction solution.
From these results, the effect of the present invention was confirmed.
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【The invention's effect】
By using the method of the present invention, an AgX photographic light-sensitive material having an excellent (sensitivity / granularity) ratio was obtained.

Claims (4)

Silver halide fine grains (C ₁ ) having an average diameter (nm) of 1.0 to 200 are added to a silver halide emulsion (B ₃ ) having at least silver halide grains (B ₁ ), a dispersion medium (B ₂ ), and water. adding silver halide fine grain emulsion (C ₂₎ containing, dissolved C _1, in the growth process of silver halide grains to grow a B ₁ by depositing on the B _1, C ₁ is the particle number ratio ( 60) to 100 are fine particles having no two or more twin planes in the particles, and C ₁ is a reaction solution 1.0 in a total amount of one or more adsorbents (Z ₂ ) described in a2) below. A method for producing a silver halide emulsion, which is carried out in a dispersion medium solution (B ₄ ) containing 10 ^{−8 to} 1.0 mol per liter.
a2) Compounds described in the following (i) to (viii): (I) a compound containing one or more onium bases in one molecule, (ii) an aromatic compound in which one or more iodo groups and one or more —OH groups are substituted on the aromatic ring, (iii) a nitrogen-containing compound A heterocyclic compound, a compound containing one or more heterocyclic rings in one molecule containing two or more nitrogen atoms in a 4- to 7-membered ring, (iv) cyanine dyes, (v) containing a divalent sulfur group (Vi) a thiourea compound, (vii) an aminothioether, (viii) an organic compound containing a divalent sulfur group and having 25 or less carbon atoms, excluding gelatin and NH ₄ ⁺ . A method of manufacturing a silver halide emulsion of claim 1 wherein said C ₁ is characterized that 60 to 100 in particle number percentage is particulate having no twin planes into the grains. The C ₁ [(Total number of particles including two or more twin planes in the particle) / (total number of fine particles)] x _Five , The adsorbent (Z ₂ The value of the fine particles formed under the same conditions except that the ₆ X _Five = (0-0.9) x ₆ The method for producing a silver halide emulsion according to claim 1, wherein: B _Three 60 to 100% of the total projected area of all silver halide grains having an aspect ratio (diameter / thickness) of 1.6 to 500 and a diameter (μ m ) Is 0.05-20, thickness (μ m ) Is a tabular grain of 0.005 to 0.5, and the variation coefficient of the diameter distribution of the grains (standard deviation / average value of the distribution) and the variation coefficient of the thickness distribution are 0.01 to 0.6. The method for producing a silver halide emulsion according to claim 1 or 2, wherein: