JP3687371B2 - Silver halide photographic emulsion and method for producing the same - Google Patents

Description

【００５９】
本発明のハロゲン化銀乳剤には、公知の方法に従い、物理熟成や他の化学熟成及び分光増感を施すことができる。
【００６０】
このような工程で使用される添加剤としては、ＲＤ１７６４３、同１８７１６及び３０８１１９に記載されているものを用いることができる。下記に記載箇所を示す。
【００６１】
【表２】

【００６２】
本発明に使用できる公知の写真用添加剤も上記リサーチ・ディスクロージャーに記載されている。下記に記載箇所を示す。
【００６３】
【表３】

【００６４】
本発明には種々のカプラーを使用することができ、その具体例は上記リサーチ・ディスクロージャーに記載されている。
【００６５】
下記に関連ある記載箇所を示す。
【００６６】
【表４】

【００６７】
本発明に使用する添加剤は、ＲＤ３０８１１９XIVに記載されている分散法などにより添加することができる。本発明においては、前述ＲＤ１７６４３の２８頁、ＲＤ１８７１６の６４７〜８頁及びＲＤ３０８１１９XIXに記載されている支持体を使用することができる。
【００６８】
本発明の感光材料には、前述ＲＤ３０８１１９VII−Ｋ項に記載されているフィルター層や中間層などの補助層を設けることができ、更に、前述ＲＤ３０８１１９VII−Ｋ項に記載されている順層、逆層、ユニット構成等の様々な層構成をとることができる。
【００６９】
本発明は、一般用もしくは映画用のカラーネガフィルム、スライド用もしくはテレビ用のカラー反転フィルム、カラーペーパー、カラーポジフィルム、カラー反転ペーパーに代表される種々のカラー感光材料に適用することができる。
【００７０】
本発明の感光材料は、前述ＲＤ１７６４３ ２８〜２９頁、ＲＤ１８７１６の６４７頁及びＲＤ３０８１１９XIXに記載された通常の方法によって、現像処理することができる。
【００７１】
本発明のハロゲン化銀粒子は、その成長時の特定時期に写真用有用物質が添加される。本発明でいう写真用有用物質とは、その物質を添加することにより写真性能上効果のある物であり、分光増感色素、カブリ抑制剤、安定剤、増感剤などの写真用に有用な添加剤である。有用物質の添加量は、添加する物質の種類及び添加位置或いは目的効果などによって決められ、添加量は任意である。
【００７２】
以下、本発明に用いられる写真用有用物質の具体例を下記に挙げるが本発明はこれらに限定されるものではない。
【００７３】
【化１】

【００７４】
【化２】

【００７５】
【化３】

【００７６】
【化４】

【００７７】
【化５】

【００７８】
【化６】

【００７９】
【化７】

【００８０】
【化８】

【００８１】
【化９】

【００８２】
【化１０】

【００８３】
【化１１】

【００８４】
【化１２】

【００８５】
【化１３】

【００８６】
本発明においてハロゲン化銀粒子が平板状粒子である場合は、写真用有用物質を取り込ませる位置をコントロール可能となる。例えば（１１１）面を主平面とする平板状粒子の場合、写真用有用物質を成長中の平均粒子間距離が極小値を示す近傍で添加すると粒子の主平面に取り込まれ、平均粒子間距離が極大値を示す近傍で添加すると粒子側面に取り込むことができる。従来の粒子成長方法では有用物質を取り込む位置は実質的に制御することができなかった。
【００８７】
本発明においてハロゲン化粒子は転位を有していてもよい。転位は例えばＪ．Ｆ．Ｈａｍｉｌｔｏｎ，Ｐｈｏｔ．Ｓｃｉ．Ｅｎｇ，５７（１９６７）や、Ｔ．Ｓｈｉｏｚａｗａ，Ｊ．Ｓｏｃ．Ｐｈｏｔ．Ｓｃｉ．Ｊａｐａｎ，３５，２１３（１９７２）に記載の低温での透過型電子顕微鏡を用いた直接的な方法により観察することができる。即ち、乳剤から粒子に転位が発生する程の圧力をかけないよう注意して取りだしたハロゲン化銀粒子を電子顕微鏡観察用のメッシュに載せ、電子線による損傷（プリントアウト等）を防ぐように試料を冷却した状態で透過法により観察を行う。このとき、粒子の厚みが厚いほど電子線が透過しにくくなるので、高圧型（０．２５μｍの厚さの粒子に対して２００ｋＶ以上）の電子顕微鏡を用いた方がより鮮明に観察することができる。
【００８８】
増感色素は単独又は組み合わせて用いてもよく、組み合わせは特に強色増感の目的でしばしば用いられる。また、増感色素とともにそれ自身、分光増感性を持たない色素或いは可視光を実質的に吸収しない物質であって、強色増感作用を示す物質を乳剤層中に含有してもよい。例えば含窒素異節環核基であって置換されたアミノスチルベン化合物（例えば米国特許２，９３３，３９０号、同３，６３５，７２１号記載のもの）、芳香族有機酸ホルムアルデヒド縮合物（例えば米国特許３，７４３，５１０号記載のもの）、カドミウム塩、アザインデン化合物などを含有してもよい。
【００８９】
本発明の粒子の化学熟成の方法は金増感、硫黄増感、還元増感、カルコゲン化合物による増感やそれらの組み合わせが好ましく用いられる。
【００９０】
化学増感法としては、いわゆる硫黄増感、金増感、周期律表VIII族の貴金属（例えばＰｄ，Ｐｔ等）による増感、及びこれらの組み合わせによる増感法を用いることができる。中でも金増感と硫黄増感との組み合わせ、あるいは金増感とセレン化合物による増感との組み合わせが好ましい。セレン化合物の添加量は任意に設定できるが、好ましくは化学増感の際にチオ硫酸ナトリウムと併用することが好ましい。更に好ましくはセレン化合物とチオ硫酸ナトリウムのモル比が２：１以下、更に好ましくは１：１以下のモル比で使用することが好ましい。また、還元増感と併用して行うことも好ましい。
【００９１】
セレン増感の場合、使用するセレン増感剤は従来公知の広範な種類のセレン化合物を使用することが出来る。有用なセレン増感剤としては、コロイドセレン金属、イソセレノシアネート類（例えばソアリルイソセレノシアネート等）、セレノ尿素類（例えば、Ｎ，Ｎ−ジメチルセレノ尿素、Ｎ，Ｎ，Ｎ′−トリエチルセレノ尿素、Ｎ，Ｎ，Ｎ′−トリメチル−Ｎ′−ヘプタフルオロプロピルカルボニルセレノ尿素、Ｎ，Ｎ，Ｎ′−トリメチル−Ｎ′−４−ニトロフェニルカルボニルセレノ尿素等）、セレノケトン類（例えば、セレノアセトン、セレノアセトフェノン等）、セレノアミド類（例えば、セレノアセトアミド、Ｎ，Ｎ−ジメチルセレノベンズアミド等）、セレノカルボン酸類及びセレノエステル類（例えば、２−セレノプロピオン酸、メチル−３−セレノブチレート等）、セレノフォスフォート類（例えば、トリ−ｐ−トリセレノフォスフォート等）、セレナイド類（トリフェニルフォスフィンセレナイド、ジエチルセレナイド、ジエチルジセレナイド等）が挙げられる。特に好ましいセレン増感剤は、セレノ尿素類、セレノアミド類、及びセレノケトン類、セレナイド類である。
【００９２】
セレン増感剤の使用量は、使用するセレン化合物、ハロゲン化銀粒子、化学熟成条件などにより変わるが、一般にハロゲン化銀１モル当たり１０^-8〜１０^-4モル程度を用いる。添加方法は使用するセレン化合物の性質に応じて水またはメタノール、エタノールなどの有機溶媒の単独または混合溶媒に溶解して添加する方法でも良い。また、ゼラチン溶液とあらかじめ混合して添加する方法、あるいは特開平４−１４０７３９号に開示されている方法で有機溶媒可溶性の重合体との混合溶液の乳化分散物の形態で添加する方法でも良い。
【００９３】
セレン増感剤を用いる化学熟成の温度は４０〜９０度の範囲が好ましく、より好ましくは４５〜８０度である。またｐＨは４〜９、ｐＡｇは６〜９．５の範囲が好ましい。
【００９４】
化学増感時または終了時に沃素イオンを供給することは感度や色素吸着の点から好ましい。特に沃化銀の微粒子の形態で添加する方法が好ましい。
【００９５】
化学増感をハロゲン化銀に吸着性を持つ化合物の存在下で行うことも好ましい。化合物として特にアゾール類、ジアゾール類、トリアゾール類、テトラゾール類、インダゾール類、チアゾール類、ピリミジン類、アザインデン類、特にこれらのメルカプト基を有する化合物やベンゼン環を有する化合物が好ましい。
【００９６】
本発明にかかるハロゲン化銀写真感光材料は還元処理を施しても良い。還元増感法としては、還元性化合物を添加する方法、銀熟成と呼ばれるｐＡｇ＝１〜７の銀イオン過剰状態を経過させる方法、高ｐＨ熟成と呼ばれるｐＨ＝８〜１１の高ｐＨ状態を経過させる方法等によってハロゲン化銀乳剤に施しても良い。また、これら２つ以上の方法を併用することもできる。
【００９７】
還元性化合物を添加する方法は、還元増感の程度を微妙に調節出来る点で好ましい。還元性化合物としては、無機又は有機化合物のいずれでもよく、二酸化チオ尿素、第一錫塩、アミン及びポリアミン類、ヒドラジン誘導体、ホルムアミジンスルフィン酸、シラン化合物、ボラン化合物、アスコルビン酸及びその誘導体、亜硫酸塩などが挙げられる。これら還元性化合物の添加量は、その化合物の還元性及びハロゲン化銀の種類、溶解条件などの乳剤製造条件によって異なるが、ハロゲン化銀１モル当たり１×１０^-8〜１×１０^-2モルの範囲が適当である。
【００９８】
これらの還元性化合物は、水あるいはアルコール類などの有機溶媒に溶解させ、ハロゲン化銀粒子成長時から塗布直前までのいずれかの時期に添加される。
【００９９】
本発明のハロゲン化銀乳剤を支持体の片面のみに塗布する場合は、通常アンチハレーション染料含有層を設けることが一般的である。アンチハレーション染料含有層は、乳剤と支持体の間であっても、支持体を挟んで乳剤層の反対側であっても良いが、染料の選択の幅が広がることから乳剤層の反対側にバック層として設けるのが好ましい。染料含有層の露光光源の波長における透過濃度は０．４〜１．５、好ましくは０．４５〜１．２である。染料の添加方法はその性質により水溶液添加、ミセル分散添加、固体分散添加などがある。
【０１００】
【実施例】
以下に、本発明を実施例を挙げて具体的に説明するが、本発明はこれらの実施態様に限定されるものではない。
【０１０１】
以下に示す全ての乳剤は、容積が３２Ｌの反応容器を用いて調製した。また、限外濾過ユニットとしては旭化成ＳＩＰ−１０１３、循環ポンプとしてはＤＡＩＤＯ ＲｏｔａｒｙＰｕｍｐを使用した。限外濾過工程の乳剤循環部分の容積は１．２Ｌであり、１５Ｌ／分の一定流速で乳剤を循環させた。したがって、反応物溶液の滞留時間は４．８秒であり、限外濾過工程の乳剤循環部分の容積は、反応容器の容積の３．８％であった。粒子成長過程における粒子間距離の制御は、上記限外濾過工程における透過フラックスを適宜制御して行った。具体的には、図１の流量調節用バルブ１９の調整によって行った。
【０１０２】
（Ｅｍ−１００の調製）
図１と同様の構成を有する本発明のハロゲン化銀乳剤製造設備を用いて、以下の手順によりハロゲン化銀乳剤を調製した。
【０１０３】
〔核生成工程〕
反応容器内の下記ゼラチン溶液Ｂ−１０１を３０℃に保ち、特開昭６２−１６０１２８号公報記載の混合攪拌装置を用いて攪拌回転数４００回転／分で攪拌しながら、１Ｎの硫酸を用いてｐＨを１．９６に調整した。その後ダブルジェット法を用いてＳ−１０１液とＸ−１０１液を一定の流量で１分間で添加し核形成を行った。
【０１０４】
（Ｂ−１０１）
酸化処理ゼラチン（平均分子量１０万） ３２．４ｇ
臭化カリウム ９．９２ｇ
Ｈ₂Ｏ １２９３８．０ｍｌ
（Ｓ−１０１）
硝酸銀 ５０．４３ｇ
Ｈ₂Ｏ ２２５．９ｍｌ
（Ｘ−１０１）
臭化カリウム ３５．３３ｇ
Ｈ₂Ｏ ２２４．７ｍｌ
〔熟成工程〕
核生成工程終了後に下記Ｇ−１０１液を加えた後、３０分間を要して６０℃に昇温しその状態で２０分間保持した。続いて、アンモニア水溶液を加えてｐＨを９．３に調整し更に７分間保持した後、１Ｎの硝酸水溶液を用いてｐＨを５．８に調整した。この間溶液の銀電位を１Ｎの臭化カリウム溶液を用いて４ｍＶに制御した。
【０１０５】
（Ｇ−１０１）
アルカリ処理不活性ゼラチン（平均分子量１０万） １３９．１ｇ
（化合物Ａ）ポリプロピレンオキシ−ポリエチレンオキシ−ジサクシネート
ナトリウム塩の１０重量％メタノール溶液 ４．６４ｍｌ
Ｈ₂Ｏ ３２６６．０ｍｌ
〔粒子成長工程−１〕
熟成終了後、続いてダブルジェット法を用いてＳ−１０２液とＸ−１０２液を流量を加速しながら（終了時と開始時の添加流量の比が約１２倍）３８分間で添加した。この間溶液の銀電位を１Ｎの臭化カリウム溶液を用いて６ｍＶに制御した。添加終了後に下記Ｇ−１０２液を加え、攪拌回転数を５５０回転／分に調整した後、引き続いてＳ−１０３液とＸ−１０３液を流量を加速しながら（終了時と開始時の添加流量の比が約２倍）４０分間で添加した。この間溶液の銀電位を１Ｎの臭化カリウム溶液を用いて４ｍＶから−２ｍＶに連続的に変化させた。
【０１０６】
（Ｓ−１０２）
硝酸銀 ６３９．８ｇ
Ｈ₂Ｏ ２８６６．２ｍｌ
（Ｘ−１０２）
臭化カリウム ４４８．３ｇ
Ｈ₂Ｏ ２８５０．７ｍｌ
（Ｇ−１０２）
アルカリ処理不活性ゼラチン（平均分子量１０万） ２０３．４ｇ
前記（化合物Ａ）の１０重量％メタノール溶液 ６．２０ｍｌ
Ｈ₂Ｏ １８６７．０ｍｌ
（Ｓ−１０３）
硝酸銀 ９８９．８ｇ
Ｈ₂Ｏ １４３７．２ｍｌ
（Ｘ−１０３）
臭化カリウム ６７９．６ｇ
沃化カリウム １９．３５ｇ
Ｈ₂Ｏ １４１２．０ｍｌ
〔粒子成長工程−２〕
上記添加終了後に、反応容器内の溶液温度を２０分を要して４０℃に降温した。その後、３．５Ｎの臭化カリウム水溶液を用いて反応容器内の銀電位を−５２ｍＶに調整し、続いて平均粒径０．０５μｍのＡｇＩ微粒子乳剤を０．２８３モル相当量加えた後、Ｓ−１０４液とＸ−１０４液を流量を加速しながら（終了時と開始時の添加流量の比が１．２倍）７分間で添加した。
【０１０７】
（Ｓ−１０４）
硝酸銀 ６７２．０ｇ
Ｈ₂Ｏ ９７５．８ｍｌ
（Ｘ−１０４）
臭化カリウム ４７０．８ｇ
Ｈ₂Ｏ ９５９．４ｍｌ
上記乳剤調製における反応容器内の反応物溶液の最大量は２８．９リットルであった。従って、最大０．４９（モル／リットル）×３２リットルに相当するハロゲン化銀乳剤の調製が可能である。
【０１０８】
上記の成長終了後に常法に従い脱塩・水洗処理を施し、ゼラチンを加えて良く分散し、４０℃にてｐＨを５．８、ｐＡｇを８．１に調整した。かくして得られた乳剤をＥｍ−１００（比較乳剤）とする。
【０１０９】
（Ｅｍ−２００の調製）
以下に示す各工程以外は、Ｅｍ−１００と同様にしてＥｍ−２００を調製した。
【０１１０】
〔粒子成長工程−１〕
熟成工程終了後、続いてダブルジェット法を用いてＳ−１０２液とＸ−１０２液を流量を加速しながら（終了時と開始時の添加流量の比が約１２倍）３８分間で添加した。この間溶液の銀電位を１Ｎの臭化カリウム溶液を用いて６ｍＶに制御した。添加終了後にＧ−１０２液を加え、攪拌回転数を５５０回転／分に調整した後、引き続いてＳ−１０３液とＸ−１０３液を流量を加速しながら（終了時と開始時の添加流量の比が約２倍）４０分間で添加した。この間溶液の銀電位を１Ｎの臭化カリウム溶液を用いて４ｍＶから−２ｍＶに連続的に変化させた。また、Ｓ−１０２液及びＸ−１０２液の添加と同時に、反応容器内の反応物溶液を限外濾過ユニットへ循環させて濃縮を実施することにより、平均粒子間距離は粒子成長工程−１の全域に渡って、粒子成長工程−１開始時の平均粒子間距離に保った。
【０１１１】
〔粒子成長工程−２〕
粒子成長工程−１添加終了後に、反応容器内の溶液温度を２０分を要して４０℃に降温した。その後、３．５Ｎの臭化カリウム水溶液を用いて反応容器内の銀電位を−３２ｍＶに調整し、続いて平均粒径０．０５μｍのＡｇＩ微粒子乳剤を０．２８３モル相当量加えた後、Ｓ−１０４液とＸ−１０４液を流量を加速しながら（終了時と開始時の添加流量の比が１．２倍）７分間で添加した。また、粒子成長工程−１から継続して濃縮を実施し、粒子成長工程−２における平均粒子間距離を一次的に減少させ、粒子成長工程−２終了時には粒子成長工程−１開始時の平均粒子間距離の０．７倍となるように制御した。
【０１１２】
Ｅｍ−２００の調製における反応容器内の反応物溶液の最大量は１７．１リットルであった。従って、最大０．８３（モル／リットル）×３２リットルに相当するハロゲン化銀乳剤の調製が可能である。
【０１１３】
（Ｅｍ−３００の調製）
以下の記載以外は、Ｅｍ−２００と同様にしてＥｍ−３００を調製した。
【０１１４】
粒子成長工程−２において、反応容器内の溶液温度を４０℃に降温した後、限外濾過ユニットを用いて、平均粒子間距離を粒子成長工程−１開始時の平均粒子間距離の０．６５倍にし、以降粒子成長終了時までこの平均粒子間距離を保った。
【０１１５】
従って、転位線形成時の平均粒子間距離は１．６μｍであった。Ｅｍ−３００の調製における反応容器内の反応物溶液の最大量は１７．１リットルであった。従って、最大０．８３（モル／リットル）×３２リットルに相当するハロゲン化銀乳剤の調製が可能である。
【０１１６】
（Ｅｍ−４００の調製）
上記のＥｍ３００と同様にして粒子成長工程−２における平均粒子間距離を、粒子成長工程−１開始時の１．１倍にした乳剤を調製し、乳剤Ｅｍ−４００とした。
【０１１７】
上記各乳剤の調製時に、成長過程のハロゲン化銀乳剤のサンプリングを適宜実施して電子顕微鏡で観察したが、何れのハロゲン化銀乳剤においてもハロゲン化銀粒子の成長過程における新たなハロゲン化銀粒子の生成及びその成長は認められなかった。
【０１１８】
以上のように調製した各乳剤の特徴をレプリカ法を用いて調べた。その結果を表５に示す。何れの乳剤においても成長開始時の平均粒子間距離は２．４μｍであった。また、成長終了後の各乳剤中に含まれるハロゲン化銀粒子の立方体換算平均粒径は０．７μｍであった。
【０１１９】
【表５】

【０１２０】
※１：表中の「平均粒子間距離の範囲」とは、（粒子成長工程における平均粒子間距離）／（粒子成長工程開始時の平均粒子間距離）の値の制御幅を表す。
【０１２１】
上記により得られた各々の乳剤のハロゲン化銀１モル当たりの容積が３００ｍｌになるように純水を加えてから５０℃にし、ベンジルアデニン２０ｇ添加し、１０分後に下記分光増感色素Ａ、Ｂを固体微粒子状分散物として各々０．６モル、０．００６モル添加し、更に１０分後、チオシアン酸アンモニウム３×１０^-3モル加え、更に適当量の塩化金酸とチオ硫酸ナトリウムを添加した。化学増感終了６０分前に沃化銀微粒子４ｇ及びトリフェニルホスフィンセレナイド分散物２ｇを添加し、その後、４−ヒドロキシ−６−メチル−１，３，３ａ，７−テトラザインデン（ＴＡＩ）の適量を添加し、化学増感を終了した。
【０１２２】
【化１４】

【０１２３】
上記のトリフェニルホスフィンセレナイド分散液は、次のように調製した。即ち、トリフェニルホスフィンセレナイド１２０ｇを５０℃の酢酸エチル３０ｋｇ中に添加、撹拌し完全に溶解した。一方、写真用ゼラチン３．８ｇを純水３８ｋｇに溶解し、これにドデシルベンゼンスルフォン酸ナトリウム２５ｗｔ％水溶液９３ｇを添加した。次いでこれらの２液を混合して直径１０ｃｍのディゾルバーを有する高速撹拌型分散機により５０℃下において分散翼周速４０ｍ／秒で３０分間分散を行った。その後、速やかに減圧下で酢酸エチルの残留濃度が０．３ｗｔ％以下になるまで酢酸エチルを撹拌しながら除去した。その後、この分散物を純水で希釈して８０ｋｇに仕上げた、このようにして得られた分散液の一部を分取して使用した。
【０１２４】
以上のようにして増感を施した乳剤に後記する添加剤を加え乳剤層塗布液とした。また同時に保護層塗布液も調製した。塗布量は片面当たりの銀量が２．０ｇ／ｍ²で、ゼラチン付き量は１．９ｇ／ｍ²、保護層のゼラチン付き量は０．６ｇ／ｍ²となるように２台のスライドホッパー型コーターを用い支持体上に両面同時塗布を行い、乾燥し試料を得た。なお支持体は厚みが１７５μｍで濃度０．１５に青色着色したＸ線用のポリエチレンテレフタレートフィルムベースの両面に、グリシジルメタクリレート５０ｗｔ％、メチルアクリレート１０ｗｔ％、ブチルメタクリレート４０ｗｔ％の３種モノマーからなる共重合体の濃度が１０ｗｔ％になるように希釈して得た共重合体水性分散液に、下記のフィルター染料及びゼラチンを分散させて下引き液として塗布したものを用いた。
【０１２５】
フィルター染料（固体分散物）
【０１２６】
【化１５】

【０１２７】
乳剤に加えた添加剤は次のとおりである。添加量はハロゲン化銀１モル当たりの量で示す。
【０１２８】
１，１−ジメチロール−１−ブロム−１−ニトロメタン ７０ｍｇ
ポリビニルピロリドン（分子量１０，０００） １．０ｇ
スチレン無水マレイン酸共重合体 ２．５ｇ
ニトロフェニル−トリフェニルホスホニウムクロリド ５０ｍｇ
Ｃ₄Ｈ₉ＯＣＨ₂ＣＨ（ＯＨ）ＣＨ₂Ｎ（ＣＨ₂ＣＯＯＨ）₂ １．０ｇ
１−フェニル−５−メルカプトテトラゾール １５ｍｇ
【０１２９】
【化１６】

【０１３０】
保護層塗布液
次に保護層用塗布液として下記を調製した。添加剤は塗布液１リットル当たりの量で示す。
【０１３１】

【０１３２】
【化１７】

【０１３３】
（現像処理剤の調製）
〈レダクトン類を現像主薬とする固体現像剤の調製〉
造粒物（Ａ₁）
１−フェニル−３−ピラゾリドンを５００ｇ、Ｎ−アセチル−Ｄ，Ｌ−ペニシラミン１０ｇ、グルタルアルデヒド重亜硫酸ナトリウム１０００ｇをそれぞれ市販のバンタムミル中で平均１０μｍになるまで粉砕する。この微粉にＤＴＰＡ・５Ｎａ３００ｇ、ジメゾンＳ（１−フェニル−４−ヒドロキシメチル−４−メチル−３−ピラゾリドン）３００ｇ、エリソルビン酸ナトリウム４０００ｇ、亜硫酸ナトリウム２０００ｇ、１−フェニル−５−メルカプトテトラゾール７．０ｇ、結合剤マンニトール４００ｇを加えミル中で３０分混合して市販の撹拌造粒機中で室温にて約１０分間、３０ｍｌの水を添加することにより造粒した後、造粒物を流動層乾燥機で４０℃にて２時間乾燥して造粒物の水分をほぼ完全に除去する。
【０１３４】
造粒物（Ｂ₁）
炭酸カリウム１００００ｇ、重炭酸ナトリウム１０００ｇをそれぞれ市販のバンタムミル中で平均１０μｍに成る迄粉砕する。各々の微粉に結合剤マンニトール８００ｇ加えミル中で３０分混合して市販の撹拌造粒機中で室温にて約１５分間、３０ｍｌの水を添加することにより造粒した後、造粒物を流動乾燥機で４０℃にて２時間乾燥して造粒物の水分をほぼ完全に除去する。
【０１３５】
〈固体現像剤の作製〉
このようにして得られた造粒物（Ａ₁）と（Ｂ₁）をラウリル硫酸ナトリウム１００ｇと２５℃、４０％ＲＨ以下に調湿された部屋で混合機を用いて１０分間均一に混合した後、得られた混合物を菊水製作所（株）製タフプレストコレクト１５２７ＨＵを改造した打錠機により１錠当たり充填量を１０ｇにして圧縮打錠を行いレダクトン類を主薬とする現像錠剤を作製した。得られたレダクトン類を現像主薬とする固体現像剤は、防湿のためアルミを含有させたピロー袋に３．０リットル量分ずつ封入包装した。
【０１３６】
以下の操作で固体定着剤を作製した。
【０１３７】
造粒物（Ａ₂）
チオ硫酸アンモニウム／チオ硫酸ナトリウム（９０／１０重量比）１５０００ｇ、β−アラニン１５００ｇ、酢酸ナトリウム４０００ｇ、をそれぞれ市販のバンタムミル中で平均１０μｍに成るまで粉砕する。
【０１３８】
この微粉に亜硫酸ナトリウム５００ｇ、Ｎａ₂Ｓ₂Ｏ₅７５０ｇ、結合剤マンニトール１３００ｇを加え水添加量を５０ｍｌにして撹拌造粒を行い、造粒物を流動層乾燥機で４０℃で乾燥して水分をほぼ完全に除去する。
【０１３９】
造粒物（Ｂ₂）
ホウ酸７００ｇ、硫酸アルミ・１８水塩１５００ｇ、琥珀酸１２００ｇを（Ａ₂）と同様に粉砕する。この微粉に硫酸水素ナトリウム２００ｇを加え水添加量３０ｍｌにして撹拌造粒を行い造粒物を流動層乾燥機で４０℃で乾燥して水分を完全に除去する。
【０１４０】
〈固体定着剤の作製〉
このようにして得られた造粒物（Ａ₂）と（Ｂ₂）をラウリル硫酸ナトリウム１５０ｇと２５℃、４０％ＲＨ以下に調湿された部屋で混合機を用いて１０分間均一に混合した後、得られた混合物を菊水製作所（株）製タフプレスコレクト１５２７ＨＵを改造した打錠機により１錠当たり充填量を１０ｇにして圧縮打錠を行い、定着錠剤を作製した。これを、防湿のためにアルミを含有させたピロー袋に３．０リットル量分ずつ封入包装した。
【０１４１】
スタート時の現像タンク内の現像液は、上記固体現像錠剤の１５個を希釈水で希釈して１リットルに調製した。この比率で調整した現像液７．８リットルを自動現像機ＳＲＸ−２０１（コニカ（株）製）に入れ、下記スターターを加えてスタート液として現像槽を満たして処理を開始した。スターター添加量は４０ｃｃ／リットルであった。固体定着剤を２１個を希釈水で希釈して１リットルに調製した。この比率で調整した定着液５．６リットルを同ＳＲＸ−２０１の定着処理タンクに入れてスタート液とした。
【０１４２】
スターター処方
ＫＢｒ ３．５ｇ
ＣＨ₃Ｎ（Ｃ₂Ｈ₆ＮＨＣＯＮＨＣ₂Ｈ₄ＳＣ₂Ｈ₅）₂ ０．０５ｇ
メチル−β−シクロデキストリン ５．０ｇ
メタ重亜硫酸ナトリウム 下記開始液ｐＨになる量
水仕上げ ４０ｃｃ
現像、定着ともに各々の固形剤の投入口にそれぞれの包装袋を手で開封したものをセットし内蔵ケミカルミキサーに錠剤を落とすと同時に温水（２５〜３０℃）を注水し撹拌溶解しながら溶解時間２５分で３．０リットルに調液する。これを現像・定着補充液として用いた。
【０１４３】
現像剤を溶解した時のｐＨは１０．０であった。定着液の溶解ｐＨは４．８０であった。
【０１４４】
〈濃度ムラの評価〉
先に作製した各試料を大角サイズに裁断し、現像処理後の光学濃度が１．０となるように全面均一な露光を施し、前記自動現像機を用いて処理時間４５秒、現像液の補充量２００ｍｌ／ｍ²で処理した。得られた試料について、下記の方法で濃度ムラの評価を行った。
【０１４５】
評価基準
Ａ：濃度ムラが認められない
Ｂ：注視するとフィルム辺縁部に僅かに濃度ムラが認められるが、実用上問題ないレベル
Ｃ：注視するとフィルム全体に僅かに濃度ムラが認められるが、実用上問題ないレベル
Ｄ：フィルム辺縁部にはっきりと濃度ムラが発生し、実用上支障がある
Ｅ：フィルム全面に強く濃度ムラが発生し、実用不可能である。
【０１４６】
〈鮮鋭性の評価〉
得られた試料をスクリーンとしてＳＲＯ−２５０（コニカ（株）製）を用いて、胸部ファントームを通してＸ線露光を行った。濃度ムラ評価試料と同様に自動現像機及び処理剤を用いて処理した試料をシャーカステン上にて鮮鋭性を目視評価した、評価基準としては下記の５段階に分けた。
【０１４７】
Ａ：特に優れる
Ｂ：優れる
Ｃ：普通
Ｄ：やや劣る
Ｅ：劣る
〈感度、カブリの評価〉
得られた試料をスクリーンとしてＳＲＯ−２５０（コニカ（株）製）で挟み、管電圧９０ｋＶｐ、電流２０ｍＡ、時間０．０５秒の条件でＸ線照射を行い距離法にてセンシトメトリーカーブを作製し感度を求めた。なお現像処理は前記の濃度ムラ評価と同じ方法で行った。表中の感度値はＤｍｉｎ＋濃度１．０を得るのに必要なＸ線量の逆数として求め、試料Ｎｏ．１を１００とした場合の相対値で示した。カブリはＤｍｉｎからベース濃度（０．１５）を減じた値である。
【０１４８】
〈ＣＰ（カバーリングパワー）の評価〉
Ｄｍａｘからベース濃度を減じた値を銀付き量（ｇ／ｍ²）で除し、１００を乗じた値であり、下記式２で求めた。
【０１４９】
式２ ＣＰ＝（Ｄｍａｘ−０．１５）／銀付量（ｇ／ｍ²）×１００
〈残色の評価〉
得られた試料の大角サイズを未露光のまま、濃度ムラ評価試料と同じ現像処理を行い、シャーカステン上で残色を下記４段階に目視評価した。
【０１５０】
Ａ：残色が全く認められない
Ｂ：ごく僅かに残色が認められる（実用上問題なし）
Ｃ：残色が認められる（実用上可と不可のボーダーライン）
Ｄ：全面にはっきりと残色が認められる（実用不可）
得られた結果を下記の表６〜８に示す。
【０１５１】
【表６】

【０１５２】
【表７】

【０１５３】
【表８】

【０１５４】
表から明らかなように、本発明の試料は迅速処理に際しても比較試料に対して高感度、高鮮鋭性でカバーリングパワーが優れ、かつ残色や濃度ムラが少ないことが分かる。
【０１５５】
【発明の効果】
本発明によれば、迅速処理にて高感度、高鮮鋭性でカバーリングパワーが優れ、かつ残色や濃度ムラが少ないハロゲン化銀写真乳剤及びその製造方法を提供できた。
【図面の簡単な説明】
【図１】本発明の製造設備に適用できるハロゲン化銀写真乳剤の製造装置の１例を示す概略図である。
【符号の説明】
１ 反応容器
２ 攪拌機構
３ 分散媒体
４，５ 添加ライン
６ 液取り出しライン
７ 液戻しライン
８ 透過液排出ライン
９ 透過液戻りライン
１０ 限外濾過ユニット
１１ 循環ポンプ
１２ 流量計
１３，１４，１５ 圧力計
１６ 圧力調整用バルブ
１７ 流量調整用バルブ
１８ 液抜き取りバルブ
１９，２０，２１ バルブ
２２ 限外濾過透過液
２３ 透過液受け容器
２４ 秤[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a silver halide photographic emulsion, and more particularly to a silver halide photographic emulsion having improved photographic performance and a method for producing the same.
[0002]
[Prior art]
From 1995, ocean disposal of photographic processing liquid waste has been prohibited and incineration processing has been carried out, but land processing of processing liquid waste is not preferable because it leads to a rise in energy and costs. In order to reduce the amount of processing waste liquid, it is desired to reduce the replenishing amount of the processing liquid. However, the reduction of the replenishing amount increases the stagnation time of the liquid in the processing tank, and causes oxidation fatigue of the processing liquid and processing. There is a problem that the density and gamma of the photosensitive material are lowered, and the processing stability is deteriorated.
[0003]
On the other hand, in the case of medical photosensitive materials, it is necessary to promptly provide information from the viewpoint of emergency medical care, and prompt provision of information is required. A silver halide photographic photosensitive material (hereinafter also simply referred to as photosensitive material) is required. ) Rapid processability is strongly demanded.
[0004]
As means for meeting these demands, as conventional techniques, for example, the silver halide grain size is reduced or the covering power is increased by increasing the covering power by using tabular grains having a high aspect ratio and a small grain thickness. It is known to lower the value.
[0005]
However, if the particle size is reduced, the sensitivity is lowered. Therefore, a sensitization technique is required to maintain the conventional sensitivity.
[0006]
JP-A-8-171164 discloses a sensitization technique using epitaxial particles. According to this technique, although it is possible to reduce the particle size, there is a drawback that the pressure resistance, for example, the roller mark resistance of the obtained photosensitive material is deteriorated. Furthermore, the processing with a reduced replenishment amount has a disadvantage that the photographic performance fluctuates greatly, and further improvement has been desired.
[0007]
[Problems to be solved by the invention]
Accordingly, an object of the present invention is to provide a silver halide photographic emulsion capable of obtaining a silver halide photographic light-sensitive material with high sensitivity, high sharpness, excellent covering power, and little residual color and density unevenness by rapid processing, and a method for producing the same. Is in the provision of.
[0008]
[Means for Solving the Problems]
The object of the present invention has been solved by the following constitution.
[0009]
(1) The average intergranular distance in the growth process of silver halide grains defined by the following formula 1 is arbitrarily controlled from the start of grain growth to the end of growth, and 0 of the average intergranular distance at the start of grain growth. When growing to 6 to 1.15 times,Selected from spectral sensitizing dyes, antifoggants, stabilizers and sensitizersA silver halide photographic emulsion comprising silver halide grains to which a useful photographic material is added.
[0010]
      Formula 1 Average distance between particles = (volume of reaction solution / number of grown particles in reaction solution)^1/3
(2) At the time of growth which becomes 0.6 to 1.0 times the average inter-particle distance at the start of grain growth,SaidThe silver halide photographic emulsion as described in (1), which contains silver halide grains to which a useful photographic material is added.
[0012]
(3) Tabular grains having a variation coefficient of volume-converted grain size of silver halide grains contained in the silver halide emulsion of 30% or less, and 50% or more of the total projected area of the silver halide grains having an aspect ratio of 3 to 50 It is characterized by (1)Or (2)A silver halide photographic emulsion as described in the above item.
[0013]
(4) Above (1)-(3The silver halide photographic emulsion is characterized in that the method for controlling the average intergranular distance of the silver halide photographic emulsion according to any one of the above) is controlled by a dispersion medium introducing means, a water introducing means or an aqueous solution discharging means. Production method.
[0014]
(5) The aqueous solution discharge means is performed by an ultrafiltration device (4) A method for producing a silver halide photographic emulsion as described above.
[0015]
The present invention is described in detail below.
[0016]
In general, the silver halide emulsion preparation process is roughly divided into a nucleation process (consisting of a nucleation process and a nucleation process) and a subsequent nucleus growth process. There is also a growth process in which a nuclear emulsion (or seed emulsion) prepared in advance is grown. The growth process may include several stages such as a first growth process and a second growth process.
[0017]
In the present invention, the growth process of silver halide grains means all the growth processes from the formation of nuclei (or seeds) to the end of grain growth, and the start of growth means the start time of the growth process, and the end of growth. Time refers to the end of the growth process.
[0018]
In addition, the average distance between grains in the present invention means the average value of the spatial distance between the centers of gravity of silver halide grains that contribute to the growth in the reaction product (silver halide emulsion) solution during the preparation of the silver halide emulsion. In other words, in the reactant (silver halide emulsion) solution, assuming that all the grown grains have the same space, one side length of a cube having the same volume as the space of one grain. Say. Specifically, it is a value defined by the following formula.
[0019]
Average interparticle distance = [volume of reactant solution / number of growing particles in reactant solution]^1/3
During the growth process of silver halide grains, the amount of the reactant solution in the reaction vessel increases with the growth of the grains, mainly due to the addition of silver salt aqueous solution or halogen salt aqueous solution used for grain growth. To increase. In the silver halide emulsion production facility of the present invention, it is possible to suppress an increase in the average intergranular distance accompanying the grain growth, or to maintain or decrease the average intergranular distance. Here, maintaining the average interparticle distance means that the state having a specific average interparticle distance is maintained for at least 10 seconds.
[0020]
The average distance between grains in the growth process of silver halide grains is directly reflected in the volume of the reaction product (silver halide emulsion) during the growth of silver halide grains. In consideration of improving the yield of the silver halide emulsion, it is preferable that the increase in the average intergranular distance in the growth process is maintained at least 1.15 times or less at the start of the growth. On the other hand, when the average inter-grain distance in the growth process of tabular silver halide grains is reduced, the aspect ratio is lowered. In particular, when the average intergranular distance in the growth process of silver halide grains is smaller than 0.60 times the value at the start of growth, a significant reduction in the aspect ratio occurs, resulting in an improvement in photographic performance as tabular silver halide grains. Features are degraded.
[0021]
Therefore, in the present invention, the value of the average inter-grain distance in the growth process of silver halide grains is preferably controlled in the range of 0.6 to 1.15 times the value at the start of growth. Furthermore, this value in the growth process is preferably 0.65 to 1.05 times, and more preferably 0.7 to 1.0 times.
[0022]
In the present invention, the average inter-grain distance at the start of growth in the silver halide grain growth process is preferably 1.5 μm or more. Furthermore, it is preferable that they are 1.8 micrometers or more and 4.0 micrometers or less, and 2.0 micrometers or more and 3.5 micrometers or less are especially preferable.
[0023]
The average inter-grain distance in the growth process of silver halide grains is 0.6 to 1.15 times the average inter-grain distance at the start of growth from the start of growth to the end of growth. If the number of silver halide grains does not change substantially, the volume of the reactant solution during the growth process is maintained in the range of about 0.22 to about 1.52 times the volume of the reactant solution at the start of growth. It means to be drunk. That is, the reaction is carried out by ultrafiltration so that the volume of the reactant solution does not divide by about 0.22 times the volume of the reactant solution at the start of growth and does not exceed about 1.52 times the volume. Particle growth may be performed while appropriately removing an aqueous solution containing a salt from a physical solution. Here, the aqueous solution containing the salt separated from the reactant solution by the ultrafiltration membrane is referred to as a permeation flux.
[0024]
In the present invention, the control of the distance between grains in the growth process of silver halide grains is aimed at improving both photographic performance and emulsion yield of the silver halide emulsion. This is not the intention of the present invention. In the case where the average inter-grain distance at the start of growth in the growth process of silver halide grains is smaller than the preferred value in the present invention, that is, less than 1.5 μm, the invention emulsion of the example of JP-A-6-67326 As shown in (the average interparticle distance is about 1.1 μm or less), the aspect ratio significantly decreases with concentration. Such a decrease in aspect ratio results in a slight decrease in photographic performance.
[0025]
The method for controlling the average inter-grain distance of the silver halide photographic emulsion of the present invention is preferably controlled by a dispersion medium introducing means, a water introducing means or an aqueous solution discharging means.
[0026]
Furthermore, it is preferable that the aqueous solution discharge means is performed by an ultrafiltration device.
[0027]
Hereinafter, as an embodiment of a production apparatus applicable to the production facility of the silver halide photographic emulsion of the present invention, a halogenation capable of arbitrarily controlling and maintaining an average inter-grain distance in a grain growth process by an ultrafiltration apparatus. An example of a silver emulsion production apparatus will be described with reference to FIG.
[0028]
The reaction vessel 1 contains a dispersion medium 3 from the beginning. This apparatus includes a silver addition line 4 for adding at least one aqueous silver salt solution, preferably an aqueous silver nitrate solution, and at least one aqueous halide salt solution, preferably an alkali metal such as bromine, iodine, or chlorine. It has a halide addition line 5 for adding an aqueous salt solution, an aqueous ammonium salt solution, or a mixture thereof. Further, it has a stirring mechanism 2 for stirring the dispersion medium and the reactant solution (mixture of dispersion medium and silver halide grains) in the silver halide emulsion preparation process. This stirring mechanism can be in any conventional manner. The aqueous silver salt solution is added to the reaction vessel from the silver addition line 4 at a flow rate controlled by the silver addition valve 20. The aqueous halogen salt solution is added from the halide addition line 5 to the reaction vessel at a flow rate controlled by the halide addition valve 21. The addition of the solution through the silver addition line 4 and the halide addition line 5 may be liquid level addition, but is more preferably added to the liquid in the vicinity of the stirring mechanism 2. Agitation mechanism 2 mixes an aqueous silver salt solution and an aqueous halogen salt solution with a dispersion medium, allowing the soluble silver salt to react with the soluble halide salt to produce silver halide.
[0029]
During the silver halide formation in the first stage, that is, in the nucleation step, a dispersion (reactant solution) containing silver halide nuclei as a base is formed. Subsequently, the nucleation step is completed through an aging step as necessary. Thereafter, when the addition of the aqueous silver salt solution and the aqueous halogen salt solution is continued, the process proceeds to the second stage silver halide formation, that is, the growth process stage, and additional silver halide generated as a reaction product in the process is first formed. It is deposited on the formed silver halide core grains to increase the size of these grains. In the present invention, a part of the reactant solution in the reaction vessel is transferred to the ultrafiltration unit 10 through the liquid take-out line 6 by the circulation pump 11 in the particle formation process by adding the silver salt aqueous solution and the halogen salt aqueous solution to the reaction vessel. Sent to the reaction vessel through the liquid return line 7. At that time, the pressure applied to the ultrafiltration unit 10 is adjusted by a pressure adjusting valve 16 provided in the middle of the liquid return line 7 to limit a part of the water-soluble salt solution contained in the reactant solution. They are separated by a filtration unit and discharged out of the system through a permeate discharge line 8. By such a method, it is possible to form particles while arbitrarily controlling the inter-particle distance even in the grain growth process by adding the silver salt aqueous solution and the halogen salt aqueous solution to the reaction vessel.
[0030]
When this method is applied in the present invention, it is preferable to arbitrarily control the amount of permeate (permeation flux; also referred to as ultrafiltration flux) of the water-soluble salt solution separated by the ultrafiltration membrane. For example, in this case, the ultrafiltration flux can be arbitrarily controlled using a flow rate adjusting valve 17 provided in the middle of the permeate discharge line 8. At that time, in order to minimize the pressure fluctuation of the ultrafiltration unit 10, the permeate return line 9 may be used by opening the valve 18 provided in the middle of the permeate return line 9. Alternatively, it is not necessary to close the valve 18 and use the permeate return line 9, which can be arbitrarily selected according to the operating conditions. The ultrafiltration flux may be detected by using a flow meter 12 provided in the middle of the permeate discharge line 8 or by detecting a change in weight using a permeate receiver 23 and a scale 24. .
[0031]
In the present invention, the concentration by the ultrafiltration method in the particle growth process may be performed continuously throughout the particle formation process, or may be performed intermittently. However, when the ultrafiltration method is applied in the particle growth process, the circulation of the reactant solution may be continued at least until the end of particle formation after the reactant solution circulation to the ultrafiltration step is started. preferable. Accordingly, it is preferable that the circulation of the reactant solution to the ultrafiltration unit is continued even when the concentration is interrupted. This is to avoid uneven growth between the particles in the reaction vessel and the particles in the ultrafiltration step. Moreover, it is preferable that the circulating flow rate through the ultrafiltration step be sufficiently high. Specifically, the residence time in the ultrafiltration unit including the liquid removal line and the liquid return line of the silver halide reactant solution is preferably within 30 seconds, more preferably within 15 seconds, and even more preferably within 10 seconds. Particularly preferred.
[0032]
The volume of the ultrafiltration step including the liquid take-out line 6, the liquid return line 7, the ultrafiltration unit 10 and the circulation pump 11 is preferably 30% or less, and 20% or less of the volume of the reaction vessel volume. More preferably, it is particularly preferably 10% or less.
[0033]
Thus, by applying an ultrafiltration step, the volume of the total silver halide reactant solution can be arbitrarily reduced during grain formation. It is also possible to arbitrarily maintain the volume of the silver halide reactant solution by adding water from the addition lines 4 and 5.
[0034]
In the present invention, there are no particular restrictions on the ultrafiltration module and the circulation pump that can be used when carrying out ultrafiltration, but the materials and the like that act on the silver halide emulsion and adversely affect photographic performance, etc. It is preferable to avoid the structure. Moreover, the molecular weight cut off of the ultrafiltration membrane used in the ultrafiltration module can be arbitrarily selected. For example, if you want to remove the dispersion medium such as gelatin contained in the silver halide emulsion or the compound used during the preparation of the emulsion during the grain growth process, select an ultrafiltration membrane that has a molecular weight cut off that is higher than the molecular weight of the object to be removed. In addition, when it is not desired to remove, an ultrafiltration membrane having a fractional molecular weight equal to or lower than the molecular weight of the removal target can be selected.
[0035]
The production equipment and production method of the present invention can be preferably applied to the preparation of tabular silver halide emulsions.
[0036]
Tabular silver halide grains are classified crystallographically as twins. A twin crystal is a crystal having one or more twin planes in one grain, and the classification of the form of twins in silver halide grains is described in a report by Klein and Moiser, “Photographie Korresponden”, Vol. 99, p. 99. , Vol. 100, p. 57. The tabular silver halide grains related to the present invention have one or two or more twin planes parallel to each other in the grains, and these twin planes are planes forming the surface of the tabular grains. Among the surfaces having the largest area (also referred to as a main plane). The most preferable form in the present invention is a case having two parallel twin planes.
[0037]
In the present invention, the aspect ratio refers to a ratio between an area-converted particle diameter and a particle thickness (aspect ratio = diameter / thickness). Here, the area-converted particle diameter means the diameter of a circle having an area equal to the area when the particles are projected perpendicularly to the main plane. The volume-converted particle size means the diameter of a sphere having the same volume as each silver halide grain. The particle thickness is the thickness of the particle in the direction perpendicular to the main plane and generally corresponds to the distance between the two main planes.
[0038]
The projected area and thickness of the particles for calculating the area-converted particle size and the volume-converted particle size are obtained by the following method. A sample was prepared by applying a latex ball with a known particle size as an internal standard on a support and silver halide grains so that the main plane was oriented parallel to the substrate, and shadowed by carbon deposition from a certain angle. Thereafter, a replica sample is prepared by a normal replica method. An electron micrograph of the sample is taken, and the projected area and thickness of each particle are obtained using an image processing apparatus or the like. In this case, the projected area of the particle can be calculated from the projected area of the internal standard, and the thickness of the particle can be calculated from the length of the internal standard and the shadow of the particle. In the present invention, the average value of the aspect ratio, area-converted particle size, particle thickness, and volume-converted particle size is determined by arbitrarily measuring 500 or more silver halide grains contained in the silver halide emulsion using the above replica method. The value obtained as the arithmetic average of them.
[0039]
In the present invention, the variation coefficient of the volume-converted grain size of silver halide grains is a value defined by the following equation using the value obtained from the above measurement. The variation coefficient of the volume-converted grain size of silver halide grains related to the present invention is preferably 0.2 or less, more preferably 0.15 or less, and particularly preferably 0.1 or less.
[0040]
Coefficient of variation of volume equivalent particle size =
(Standard deviation of the volume-converted particle diameter / average value of the volume-converted particle diameter)
Similarly, the coefficient of variation of the area-converted grain size of silver halide grains can be obtained from the above measurement. Here, the variation coefficient of the area-converted particle diameter is a value defined by the following equation. The variation coefficient of the area converted grain size of the silver halide grains related to the present invention is preferably 0.2 or less, more preferably 0.15 or less, and particularly preferably 0.1 or less.
[0041]
Coefficient of variation of area conversion particle size =
(Standard deviation of area-converted particle diameter / average value of area-converted particle diameter)
The silver halide emulsion relating to the present invention is preferably tabular silver halide grains in which 50% or more of the total projected area of the silver halide grains contained in the silver halide emulsion is an aspect ratio of 5 or more. More preferably, 50% or more of the projected area is tabular silver halide grains having an aspect ratio of 8 or more. Further, it is preferred that 80% or more of the total projected area of the silver halide grains contained in the silver halide emulsion is tabular silver halide grains related to the present invention.
[0042]
The tabular silver halide grains related to the present invention have one or two or more parallel twin planes in the grains, but 50% or more of the tabular silver halide grains related to the present invention are grains. It is preferably a tabular grain having two twin planes parallel to each other, more preferably 80% or more. These twin planes can be observed with a transmission electron microscope. The specific method is as follows. First, a silver halide emulsion is coated on a substrate so that the main planes of contained tabular grains are oriented almost parallel to the substrate to prepare a sample. This is continuously cut perpendicularly to the substrate using a diamond cutter to obtain a continuous thin section having a thickness of about 0.1 μm. By observing this section with a transmission electron microscope, the presence and position of the twin plane can be confirmed.
[0043]
The composition of the silver halide grains in the present invention is preferably silver iodobromide, silver bromide, silver chlorobromide, or silver chloroiodobromide. In particular, the silver halide emulsion is preferably silver iodobromide containing silver iodide having an average silver iodide content of 10 mol% or less, and the average silver iodide content is preferably from 0 mol% to 5 mol%. The content is preferably 0 mol% or less, particularly preferably 0 mol% or more and 2 mol% or less. The composition of the silver halide grains can be examined using a composition analysis method such as an EPMA method or an X-ray diffraction method.
[0044]
The average silver iodide content of the surface phase of the silver halide grains according to the present invention is preferably 0.1 mol% or more, more preferably 0.2 mol% or more and 20 mol% or less. More preferably, it is 5 mol% or more and 15 mol% or less.
[0045]
The average silver iodide content of the surface phase of the silver halide grains referred to here is a value obtained using the XPS method or the ISS method. For example, the surface silver iodide content by the XPS method can be obtained as follows. 1 × 10 sample^-FourThe sample is cooled to −155 ° C. or less in an ultrahigh vacuum of torr or less, irradiated with MgKa as an X-ray for probe at an X-ray source current of 40 mA, and measured for Ag3d5 / 2, Br3d, and I3d3 / 2 electrons. The integrated intensity of the measured peak is corrected by a sensitivity factor, and the composition such as the silver iodide content of the silver halide surface phase is determined from these intensity ratios.
[0046]
In the silver halide emulsion relating to the present invention, the silver iodide content between silver halide grains is preferably more uniform. That is, the variation coefficient of the silver iodide content in the silver halide emulsion is preferably 30% or less, and more preferably 20% or less. However, the coefficient of variation here is a value obtained by multiplying the standard deviation of the silver iodide content by the average value of the silver iodide content multiplied by 100, and the silver halide grains contained in the silver halide emulsion Is a value obtained by arbitrarily measuring 500 or more.
[0047]
A photographic silver halide grain is a microcrystal composed of silver chloride, silver bromide, silver iodide, or a solid solution thereof, and two or more phases having different silver halide compositions are formed inside the crystal. Is possible. As a grain having such a structure, a grain composed of an inner core phase and an outer surface phase having different silver halide compositions is known, and is generally called a core / shell type grain. The silver halide grains related to the present invention preferably have a core / shell type grain structure in which the outer surface phase has a higher silver iodide content than the inner core phase.
[0048]
The silver halide emulsions related to the present invention can have dislocation lines. The position where the dislocation line exists is preferably present in the vicinity of the outer peripheral portion, the ridge line, or the apex of the tabular silver halide grain. Speaking of the positional relationship of dislocation introduction in each individual grain, it is preferably introduced after 50% of the total silver amount of the grain, more preferably between 60% and 95%, more preferably 70% or more. Most preferably, it is introduced between 90% or less.
[0049]
As a method for introducing dislocation lines into silver halide grains, for example, a method of adding an aqueous solution containing iodine ions such as potassium iodide and a water-soluble silver salt solution by a double jet, or a method of adding silver iodide fine particles The origin of dislocation lines at a desired position using a known method such as a method of adding only a solution containing iodine ions, a method of using an iodine ion releasing agent as described in JP-A-6-11781 Dislocations can be formed. Among these methods, a method of adding an aqueous solution containing iodine ions and a water-soluble silver salt solution by a double jet, a method of adding silver iodide fine particles, and a method of using an iodine ion releasing agent are preferable.
[0050]
Further, by using the production facility of the present invention, it is possible to dramatically increase the dislocation line introduction efficiency into the silver halide emulsion. For example, it is preferable to control the average inter-grain distance at the time of introducing dislocation lines in the growth process of silver halide grains to be 0.6 to 1.15 times the average inter-grain distance at the start of growth. More preferably, it is controlled to be from 1.0 to 1.0. Specifically, the value of the average interparticle distance at the time of introducing dislocation lines is preferably controlled to 3.2 μm or less, more preferably controlled to 2.8 μm or less, and controlled to 0.90 μm or more and 2.0 μm or less. It is particularly preferable to do this.
[0051]
The dislocation lines possessed by silver halide grains are described in, for example, J.A. F. Hamilton, Photo. Sci. Eng. 11 (1967) 57, and T.W. Shiozawa, J. et al. Soc. Photo. Sci. It can be observed by a direct method using a transmission electron microscope at a low temperature described in Japan 35 (1972) 213. In other words, silver halide grains taken out carefully so as not to apply pressure to the grains from the emulsion are placed on an electron microscope mesh to prevent damage (printout, etc.) due to electron beams. Observation is performed by the transmission method with the sample cooled. At this time, since the electron beam is less likely to be transmitted as the particle thickness is thicker, a method using a high-pressure electron microscope can be observed more clearly. From the particle photograph obtained by such a method, the position and number of dislocation lines in each particle can be obtained.
[0052]
As a preparation form of the silver halide emulsion relating to the present invention, a method known in the art can be appropriately applied. For example, a so-called controlled double jet method or controlled triple jet method for controlling the pAg of the reaction solution during the formation of silver halide grains can be used. Further, a silver halide solvent can be used as necessary, and examples of useful silver halide solvents include ammonia, thioethers, and thioureas. Regarding the thioether, U.S. Pat. Nos. 3,271,151, 3,790,387, 3,574,626 and the like can be referred to. The grain preparation method is not particularly limited, and an ammonia method, a neutral method without using ammonia, an acidic method, or the like can be used. From the viewpoint that fogging at the time of silver halide grain formation can be suppressed, It is preferable to form particles in an environment where the pH (logarithm of the reciprocal of the hydrogen ion concentration) is 5.5 or less, more preferably 4.5 or less.
[0053]
The silver halide emulsion relating to the present invention contains a dispersion medium together with silver halide grains. The dispersion medium is a compound having protective colloid properties for silver halide grains, and is preferably present from the nucleation step to the end of grain growth. Examples of the dispersion medium that can be preferably used in the present invention include gelatin and a protective colloid polymer. As the gelatin, alkali-processed gelatin or acid-processed gelatin having a molecular weight of about 100,000, or low-molecular gelatin or oxidized-processed gelatin having a molecular weight of about 5,000 to 30,000 can be preferably used. In particular, during nucleation, oxidized gelatin, low molecular weight gelatin, or oxidized low molecular weight gelatin can be suitably used.
[0054]
In order to control the silver halide composition between and inside the silver halide grains more precisely, at least part of the silver iodide-containing phase formation of the silver halide grains is supplied only by one or more kinds of silver halide fine grains. Can be formed. For the same reason, at least a part of the silver iodide-containing phase formation of the silver halide grains can be performed in the presence of silver halide grains having a lower solubility than the silver halide grains. As silver halide grains having low solubility, it is desirable to use a silver iodide fine grain emulsion.
[0055]
The volume-converted particle size of silver halide grains related to the present invention is preferably 1.2 μm or less, more preferably 0.1 to 0.8 μm. If it is 0.1 μm or less, it is insufficient to obtain practical sensitivity, and if it is 1.2 μm or more, granular deterioration of the photographic image due to the large particle size is observed.
[0056]
In the silver halide emulsion of the present invention, Research Disclosure No. The technique described in 308119 (hereinafter abbreviated as RD308119) can be used.
[0057]
Shown below is the location.
[0058]
[Table 1]

[0059]
The silver halide emulsion of the present invention can be subjected to physical ripening, other chemical ripening and spectral sensitization according to known methods.
[0060]
As an additive used in such a process, those described in RD17643, 18716 and 308119 can be used. Shown below is the location.
[0061]
[Table 2]

[0062]
Known photographic additives that can be used in the present invention are also described in the above Research Disclosure. Shown below is the location.
[0063]
[Table 3]

[0064]
Various couplers can be used in the present invention, specific examples of which are described in the above Research Disclosure.
[0065]
The following is a relevant description.
[0066]
[Table 4]

[0067]
The additive used in the present invention can be added by the dispersion method described in RD308119XIV. In the present invention, the supports described in RD 17643, page 28, RD18716, pages 647-8, and RD308119XIX can be used.
[0068]
The light-sensitive material of the present invention can be provided with auxiliary layers such as a filter layer and an intermediate layer described in the above-mentioned RD308119VII-K, and further, normal layers and reverse layers described in the above-mentioned RD308119VII-K. Various layer configurations such as a unit configuration can be adopted.
[0069]
The present invention can be applied to various color photosensitive materials represented by color negative films for general use or movies, color reversal films for slides or television, color paper, color positive films, and color reversal papers.
[0070]
The light-sensitive material of the present invention can be developed by the usual methods described in RD 17643, pages 28 to 29, RD 18716, page 647, and RD308119XIX.
[0071]
  The silver halide grains of the present invention are added with a useful photographic material at a specific time during growth. The useful photographic substance as used in the present invention is a substance having an effect on photographic performance by adding the substance.TheSpectral sensitizing dye, fog inhibitor, stabilizer, sensitizationAgentDoCopy ofIt is a useful additive for true use. The addition amount of the useful substance is determined depending on the kind and the addition position of the substance to be added or the purpose effect, and the addition amount is arbitrary.
[0072]
Specific examples of useful photographic materials used in the present invention are listed below, but the present invention is not limited thereto.
[0073]
[Chemical 1]

[0074]
[Chemical 2]

[0075]
[Chemical 3]

[0076]
[Formula 4]

[0077]
[Chemical formula 5]

[0078]
[Chemical 6]

[0079]
[Chemical 7]

[0080]
[Chemical 8]

[0081]
[Chemical 9]

[0082]
[Chemical Formula 10]

[0083]
Embedded image

[0084]
Embedded image

[0085]
Embedded image

[0086]
In the present invention, when the silver halide grains are tabular grains, the position at which the photographic useful substance is taken in can be controlled. For example, in the case of tabular grains having the (111) plane as the main plane, adding a photographic useful substance in the vicinity where the average inter-grain distance during growth shows a minimum value is incorporated into the main plane of the grains, and the average inter-grain distance is If added in the vicinity of the maximum value, it can be taken into the side surface of the particle. In the conventional particle growth method, the position where the useful substance is taken in cannot be substantially controlled.
[0087]
In the present invention, the halogenated particles may have dislocations. For example, J. F. Hamilton, Photo. Sci. Eng, 57 (1967), T.E. Shiozawa, J. et al. Soc. Photo. Sci. It can be observed by a direct method using a transmission electron microscope at a low temperature described in Japan, 35, 213 (1972). In other words, the silver halide grains taken out with care so as not to apply a pressure that causes dislocations from the emulsion to the grains are placed on a mesh for observation with an electron microscope to prevent damage (printout, etc.) due to electron beams. Observation is carried out by the transmission method in a cooled state. At this time, since the electron beam is more difficult to be transmitted as the particle thickness is thicker, it is possible to observe more clearly using a high-pressure type electron microscope (200 kV or more for a particle having a thickness of 0.25 μm). it can.
[0088]
Sensitizing dyes may be used alone or in combination, and the combination is often used particularly for the purpose of supersensitization. In addition to the sensitizing dye, the emulsion layer itself may contain a dye that does not have spectral sensitization or a substance that does not substantially absorb visible light and exhibits a supersensitizing action. For example, an aminostilbene compound substituted with a nitrogen-containing heterocyclic ring nucleus group (for example, those described in US Pat. Nos. 2,933,390 and 3,635,721), an aromatic organic acid formaldehyde condensate (for example, US Patent 3,743,510), cadmium salts, azaindene compounds, and the like.
[0089]
As the method of chemical ripening of the particles of the present invention, gold sensitization, sulfur sensitization, reduction sensitization, sensitization with a chalcogen compound or a combination thereof is preferably used.
[0090]
As the chemical sensitization method, so-called sulfur sensitization, gold sensitization, sensitization with a noble metal of group VIII of the periodic table (for example, Pd, Pt, etc.), and a sensitization method by a combination thereof can be used. Among these, a combination of gold sensitization and sulfur sensitization, or a combination of gold sensitization and sensitization with a selenium compound is preferable. The amount of selenium compound added can be arbitrarily set, but it is preferably combined with sodium thiosulfate during chemical sensitization. More preferably, the molar ratio of the selenium compound and sodium thiosulfate is preferably 2: 1 or less, more preferably 1: 1 or less. It is also preferred to use in combination with reduction sensitization.
[0091]
In the case of selenium sensitization, a wide variety of conventionally known selenium compounds can be used as the selenium sensitizer. Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (eg, soaryl isoselenocyanate), selenoureas (eg, N, N-dimethylselenourea, N, N, N′-triethylseleno). Urea, N, N, N′-trimethyl-N′-heptafluoropropylcarbonylselenourea, N, N, N′-trimethyl-N′-4-nitrophenylcarbonylselenourea, etc.), selenoketones (for example, selenoacetone) , Selenoacetophenone, etc.), selenoamides (eg, selenoacetamide, N, N-dimethylselenobenzamide, etc.), selenocarboxylic acids and selenoesters (eg, 2-selenopropionic acid, methyl-3-selenobutyrate, etc.), Selenophosfort (eg, tri-p-triselenophosphf Over preparative etc.), selenide compound (triphenylphosphine selenide, diethyl selenide, diethyl diselenide, etc.). Particularly preferred selenium sensitizers are selenoureas, selenoamides, selenoketones and selenides.
[0092]
The amount of selenium sensitizer used varies depending on the selenium compound used, silver halide grains, chemical ripening conditions, etc., but generally 10 per mole of silver halide.^-8-10^-FourUse moles. Depending on the properties of the selenium compound used, the addition method may be a method of adding water or an organic solvent such as methanol or ethanol alone or in a mixed solvent. Alternatively, it may be added by mixing in advance with a gelatin solution, or by adding it in the form of an emulsified dispersion of a mixed solution with an organic solvent-soluble polymer by the method disclosed in JP-A-4-140739.
[0093]
The temperature of chemical ripening using a selenium sensitizer is preferably in the range of 40 to 90 degrees, more preferably 45 to 80 degrees. The pH is preferably in the range of 4 to 9, and the pAg is preferably in the range of 6 to 9.5.
[0094]
It is preferable to supply iodine ions at the time of chemical sensitization or completion from the viewpoint of sensitivity and dye adsorption. In particular, a method of adding silver iodide in the form of fine grains is preferable.
[0095]
It is also preferable to perform chemical sensitization in the presence of a compound having an adsorptivity to silver halide. As the compound, azoles, diazoles, triazoles, tetrazoles, indazoles, thiazoles, pyrimidines, azaindenes, particularly compounds having these mercapto groups and compounds having a benzene ring are preferable.
[0096]
The silver halide photographic material according to the present invention may be subjected to a reduction treatment. The reduction sensitization method includes a method of adding a reducing compound, a method of passing a silver ion excess state of pAg = 1-7 called silver ripening, and a high pH state of pH = 8-11 called high pH ripening. The silver halide emulsion may be applied by a method such as Further, these two or more methods can be used in combination.
[0097]
The method of adding a reducing compound is preferable in that the degree of reduction sensitization can be finely adjusted. The reducing compound may be either an inorganic or organic compound, such as thiourea dioxide, stannous salts, amines and polyamines, hydrazine derivatives, formamidine sulfinic acid, silane compounds, borane compounds, ascorbic acid and derivatives thereof, sulfurous acid. Examples include salt. The amount of these reducing compounds to be added varies depending on the reducing properties of the compounds and the emulsion production conditions such as the type of silver halide and dissolution conditions, but 1 × 10 10 per mole of silver halide.^-8~ 1x10^-2A molar range is suitable.
[0098]
These reducing compounds are dissolved in water or an organic solvent such as alcohols and added at any time from the time of silver halide grain growth to just before coating.
[0099]
When coating the silver halide emulsion of the present invention only on one side of the support, it is common to provide an antihalation dye-containing layer. The antihalation dye-containing layer may be between the emulsion and the support, or on the opposite side of the emulsion layer with the support interposed therebetween. It is preferable to provide as a back layer. The transmission density of the dye-containing layer at the wavelength of the exposure light source is 0.4 to 1.5, preferably 0.45 to 1.2. Methods for adding dye include aqueous solution addition, micelle dispersion addition, and solid dispersion addition depending on the properties.
[0100]
【Example】
EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these embodiments.
[0101]
All emulsions shown below were prepared using a reaction vessel with a volume of 32L. In addition, Asahi Kasei SIP-1013 was used as the ultrafiltration unit, and DAIDO Rotary Pump was used as the circulation pump. The volume of the emulsion circulation part in the ultrafiltration step was 1.2 L, and the emulsion was circulated at a constant flow rate of 15 L / min. Therefore, the residence time of the reactant solution was 4.8 seconds, and the volume of the emulsion circulation part in the ultrafiltration step was 3.8% of the volume of the reaction vessel. Control of the interparticle distance in the particle growth process was performed by appropriately controlling the permeation flux in the ultrafiltration step. Specifically, the adjustment was made by adjusting the flow rate adjusting valve 19 in FIG.
[0102]
(Preparation of Em-100)
A silver halide emulsion was prepared by the following procedure using the silver halide emulsion production facility of the present invention having the same structure as that shown in FIG.
[0103]
[Nucleation process]
The following gelatin solution B-101 in the reaction vessel was kept at 30 ° C., and 1N sulfuric acid was used while stirring at a stirring rotation speed of 400 rpm using a mixing stirrer described in JP-A-62-2160128. The pH was adjusted to 1.96. Thereafter, using the double jet method, S-101 solution and X-101 solution were added at a constant flow rate for 1 minute to perform nucleation.
[0104]
(B-101)
Oxidized gelatin (average molecular weight 100,000) 32.4g
Potassium bromide 9.92g
H₂O 1298.0 ml
(S-101)
Silver nitrate 50.43 g
H₂225.9 ml of O
(X-101)
Potassium bromide 35.33g
H₂O 224.7 ml
[Aging process]
After completion of the nucleation step, the following G-101 solution was added, and then the temperature was raised to 60 ° C. over 30 minutes and kept in that state for 20 minutes. Subsequently, an aqueous ammonia solution was added to adjust the pH to 9.3, and the mixture was further maintained for 7 minutes, and then the pH was adjusted to 5.8 using a 1N aqueous nitric acid solution. During this time, the silver potential of the solution was controlled at 4 mV using a 1N potassium bromide solution.
[0105]
(G-101)
Alkali-treated inert gelatin (average molecular weight 100,000) 139.1 g
(Compound A) Polypropyleneoxy-polyethyleneoxy-disuccinate
4.64 ml of a 10 wt% methanol solution of sodium salt
H₂O 3266.0 ml
[Particle Growth Step-1]
After completion of the aging, the S-102 solution and the X-102 solution were added in 38 minutes while accelerating the flow rate (the ratio of the addition flow rate at the end to the start was about 12 times) using the double jet method. During this time, the silver potential of the solution was controlled at 6 mV using a 1N potassium bromide solution. After completion of the addition, the following G-102 solution was added and the stirring rotation speed was adjusted to 550 rpm, and then the S-103 solution and the X-103 solution were accelerated while the addition flow rate was increased at the end and at the start. For about 40 minutes). During this time, the silver potential of the solution was continuously changed from 4 mV to -2 mV using a 1N potassium bromide solution.
[0106]
(S-102)
639.8 g of silver nitrate
H₂O 2866.2 ml
(X-102)
448.3 g of potassium bromide
H₂O 2850.7ml
(G-102)
Alkali-treated inert gelatin (average molecular weight 100,000) 203.4 g
10.20% methanol solution of (Compound A) 6.20 ml
H₂O 1867.0 ml
(S-103)
989.8 g of silver nitrate
H₂O 1437.2 ml
(X-103)
Potassium bromide 679.6g
Potassium iodide 19.35g
H₂O 1412.0ml
[Particle growth step-2]
After completion of the addition, the solution temperature in the reaction vessel was lowered to 40 ° C. over 20 minutes. Thereafter, the silver potential in the reaction vessel was adjusted to −52 mV using a 3.5N potassium bromide aqueous solution, and then 0.283 mol equivalent of an AgI fine grain emulsion having an average particle diameter of 0.05 μm was added. The -104 liquid and the X-104 liquid were added for 7 minutes while accelerating the flow rates (the ratio of the addition flow rate at the end to the start was 1.2 times).
[0107]
(S-104)
672.0 g of silver nitrate
H₂O 975.8ml
(X-104)
Potassium bromide 470.8g
H₂O 959.4ml
The maximum amount of the reactant solution in the reaction vessel in the emulsion preparation was 28.9 liters. Therefore, it is possible to prepare a silver halide emulsion corresponding to a maximum of 0.49 (mol / liter) × 32 liter.
[0108]
After completion of the above growth, desalting and washing were performed according to a conventional method, gelatin was added and well dispersed, and the pH was adjusted to 5.8 and the pAg to 8.1 at 40 ° C. The emulsion thus obtained is named Em-100 (comparative emulsion).
[0109]
(Preparation of Em-200)
Em-200 was prepared in the same manner as Em-100, except for the steps shown below.
[0110]
[Particle Growth Step-1]
After completion of the aging step, the S-102 solution and the X-102 solution were added in 38 minutes while accelerating the flow rates (the ratio of the addition flow rate at the end and the start was about 12 times) using the double jet method. During this time, the silver potential of the solution was controlled at 6 mV using a 1N potassium bromide solution. After completion of the addition, the G-102 solution was added and the stirring rotation speed was adjusted to 550 rpm, and then the S-103 solution and the X-103 solution were accelerated while the flow rates of the addition flow rate at the end and start ( The ratio was approximately twice) and added over 40 minutes. During this time, the silver potential of the solution was continuously changed from 4 mV to -2 mV using a 1N potassium bromide solution. Simultaneously with the addition of the liquid S-102 and the liquid X-102, the reaction solution in the reaction vessel is circulated to the ultrafiltration unit and concentrated, so that the average interparticle distance is the same as that in the particle growth step-1. The average inter-particle distance at the start of the particle growth process-1 was maintained over the entire area.
[0111]
[Particle growth step-2]
After completion of the particle growth step-1 addition, the temperature of the solution in the reaction vessel was lowered to 40 ° C. over 20 minutes. Thereafter, the silver potential in the reaction vessel was adjusted to −32 mV using a 3.5N potassium bromide aqueous solution, and then 0.283 mol equivalent of an AgI fine grain emulsion having an average particle diameter of 0.05 μm was added. The -104 liquid and the X-104 liquid were added for 7 minutes while accelerating the flow rates (the ratio of the addition flow rate at the end to the start was 1.2 times). Concentration is continued from the particle growth step-1 to temporarily reduce the average interparticle distance in the particle growth step-2. At the end of the particle growth step-2, the average particle at the start of the particle growth step-1 The distance was controlled to be 0.7 times the distance.
[0112]
The maximum amount of reactant solution in the reaction vessel in the preparation of Em-200 was 17.1 liters. Accordingly, a silver halide emulsion corresponding to a maximum of 0.83 (mol / liter) × 32 liters can be prepared.
[0113]
(Preparation of Em-300)
Except as described below, Em-300 was prepared in the same manner as Em-200.
[0114]
In the particle growth step-2, after the solution temperature in the reaction vessel is lowered to 40 ° C., the average interparticle distance is set to 0.65 of the average interparticle distance at the start of the particle growth step-1 using an ultrafiltration unit. The average interparticle distance was maintained until the end of grain growth.
[0115]
Therefore, the average interparticle distance at the time of dislocation line formation was 1.6 μm. The maximum amount of the reactant solution in the reaction vessel in the preparation of Em-300 was 17.1 liters. Accordingly, a silver halide emulsion corresponding to a maximum of 0.83 (mol / liter) × 32 liters can be prepared.
[0116]
(Preparation of Em-400)
In the same manner as in Em300, an emulsion was prepared in which the average intergranular distance in the grain growth step-2 was 1.1 times that at the beginning of the grain growth step-1.
[0117]
During the preparation of each of the above emulsions, the silver halide emulsion during the growth process was appropriately sampled and observed with an electron microscope. In any silver halide emulsion, new silver halide grains in the growth process of silver halide grains were observed. Production and growth were not observed.
[0118]
The characteristics of each emulsion prepared as described above were examined using a replica method. The results are shown in Table 5. In any emulsion, the average intergranular distance at the start of the growth was 2.4 μm. Further, the average grain size in terms of cube of silver halide grains contained in each emulsion after completion of the growth was 0.7 μm.
[0119]
[Table 5]

[0120]
* 1: “Range of average interparticle distance” in the table represents the control range of the value of (average interparticle distance in particle growth process) / (average interparticle distance at start of particle growth process).
[0121]
Pure water was added so that each emulsion obtained as described above had a volume of 300 ml per silver halide, and then the temperature was adjusted to 50 ° C., 20 g of benzyladenine was added, and after 10 minutes, the following spectral sensitizing dyes A and B were added. Were added as solid fine particle dispersions in an amount of 0.6 mol and 0.006 mol, respectively, and after 10 minutes, ammonium thiocyanate 3 × 10 3 was added.^-3Mole was added, and appropriate amounts of chloroauric acid and sodium thiosulfate were added. 60 minutes before the end of chemical sensitization, 4 g of silver iodide fine particles and 2 g of triphenylphosphine selenide dispersion were added, and then 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) An appropriate amount of was added to complete the chemical sensitization.
[0122]
Embedded image

[0123]
The above triphenylphosphine selenide dispersion was prepared as follows. That is, 120 g of triphenylphosphine selenide was added to 30 kg of ethyl acetate at 50 ° C. and stirred to dissolve completely. On the other hand, 3.8 g of photographic gelatin was dissolved in 38 kg of pure water, and 93 g of a 25 wt% sodium dodecylbenzenesulfonate aqueous solution was added thereto. Next, these two liquids were mixed and dispersed at a dispersion blade peripheral speed of 40 m / sec for 30 minutes at 50 ° C. with a high-speed stirring disperser having a dissolver having a diameter of 10 cm. Thereafter, the ethyl acetate was rapidly removed under stirring until the residual concentration of ethyl acetate was 0.3 wt% or less under reduced pressure. Thereafter, this dispersion was diluted with pure water to a final volume of 80 kg. A part of the dispersion thus obtained was collected and used.
[0124]
The following additives were added to the emulsion sensitized as described above to prepare an emulsion layer coating solution. At the same time, a protective layer coating solution was also prepared. The coating amount is 2.0 g / m on one side.²And the amount with gelatin is 1.9 g / m²The amount of the protective layer with gelatin is 0.6 g / m²Then, two slide hopper type coaters were used so that both surfaces were simultaneously coated on the support and dried to obtain a sample. The support was 175 μm thick and blue-colored polyethylene terephthalate film base for blue with a concentration of 0.15. The following filter dye and gelatin were dispersed in an aqueous copolymer dispersion obtained by diluting so that the concentration of the coalescence would be 10 wt%, and the resultant was applied as a subbing solution.
[0125]
Filter dye (solid dispersion)
[0126]
Embedded image

[0127]
Additives added to the emulsion are as follows. The amount added is shown as the amount per mole of silver halide.
[0128]
1,1-dimethylol-1-bromo-1-nitromethane 70 mg
Polyvinylpyrrolidone (molecular weight 10,000) 1.0g
Styrene maleic anhydride copolymer 2.5g
Nitrophenyl-triphenylphosphonium chloride 50mg
C_FourH₉OCH₂CH (OH) CH₂N (CH₂COOH)₂        1.0g
1-phenyl-5-mercaptotetrazole 15mg
[0129]
Embedded image

[0130]
Protective layer coating solution
Next, the following was prepared as a coating solution for the protective layer. Additives are shown in amounts per liter of coating solution.
[0131]

[0132]
Embedded image

[0133]
(Preparation of developer)
<Preparation of solid developer using reductone as developing agent>
Granulated product (A₁)
500 g of 1-phenyl-3-pyrazolidone, 10 g of N-acetyl-D, L-penicillamine and 1000 g of glutaraldehyde sodium bisulfite are pulverized in a commercially available bantam mill until the average is 10 μm. To this fine powder, 300 g of DTPA · 5Na, 300 g of dimezone S (1-phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone), 4000 g of sodium erythorbate, 2000 g of sodium sulfite, 7.0 g of 1-phenyl-5-mercaptotetrazole, After adding 400 g of binder mannitol and mixing in a mill for 30 minutes and granulating by adding 30 ml of water for about 10 minutes at room temperature in a commercially available stirred granulator, the granulated product is fluidized bed dryer. And dried at 40 ° C. for 2 hours to almost completely remove moisture from the granulated product.
[0134]
Granulated product (B₁)
10000 g of potassium carbonate and 1000 g of sodium bicarbonate are pulverized in a commercially available bantam mill until the average is 10 μm. 800 g of binder mannitol was added to each fine powder, mixed in a mill for 30 minutes, granulated by adding 30 ml of water in a commercially available stirred granulator at room temperature for about 15 minutes, and the granulated product was fluidized. Drying is performed at 40 ° C. for 2 hours in a dryer to almost completely remove moisture from the granulated product.
[0135]
<Preparation of solid developer>
Granules (A₁) And (B₁) And 100 g of sodium lauryl sulfate in a room conditioned at 25 ° C. and 40% RH or less for 10 minutes using a mixer, and the resulting mixture was mixed with Tough Presto Collect 1527HU manufactured by Kikusui Seisakusho. Using a modified tableting machine, the tableting amount was 10 g per tablet, and compression tableting was carried out to produce a developed tablet mainly containing reductones. The obtained solid developer using the reductone as a developing agent was enclosed and packaged in an amount of 3.0 liters in a pillow bag containing aluminum for moisture prevention.
[0136]
A solid fixing agent was prepared by the following operation.
[0137]
Granulated product (A₂)
15000 g of ammonium thiosulfate / sodium thiosulfate (90/10 weight ratio), 1500 g of β-alanine, and 4000 g of sodium acetate are each pulverized in a commercially available bantam mill to an average of 10 μm.
[0138]
To this fine powder, sodium sulfite 500g, Na₂S₂O_Five750 g and 1300 g of binder mannitol are added, and the amount of water added is 50 ml. Stirring granulation is performed, and the granulated product is dried at 40 ° C. in a fluid bed dryer to almost completely remove moisture.
[0139]
Granulated product (B₂)
700 g boric acid, 1500 g aluminum sulfate 18 hydrate, 1200 g oxalic acid (A₂) 200 g of sodium bisulfate is added to this fine powder, and the amount of water added is 30 ml, followed by stirring granulation. The granulated product is dried at 40 ° C. in a fluidized bed dryer to completely remove moisture.
[0140]
<Preparation of solid fixing agent>
Granules (A₂) And (B₂) With 150 g of sodium lauryl sulfate in a room conditioned at 25 ° C. and 40% RH or less for 10 minutes using a mixer, and the resulting mixture was mixed with Tough Press Collect 1527HU manufactured by Kikusui Seisakusho. A fixed tablet was prepared by compressing the tablet with a modified tableting machine with a filling amount of 10 g per tablet. This was enclosed and packaged in an amount of 3.0 liters in a pillow bag containing aluminum for moisture prevention.
[0141]
The developing solution in the developing tank at the start was prepared to 1 liter by diluting 15 of the solid developing tablets with dilution water. 7.8 liters of the developer adjusted at this ratio was placed in an automatic processor SRX-201 (manufactured by Konica Corporation), and the following starter was added to fill the developer tank as a starter, and processing was started. The amount of starter added was 40 cc / liter. 21 solid fixing agents were diluted with dilution water to prepare 1 liter. 5.6 liters of the fixing solution adjusted at this ratio was placed in the fixing processing tank of the same SRX-201, and used as a starting solution.
[0142]
Starter prescription
KBr 3.5g
CH_ThreeN (C₂H₆NHCONHC₂H_FourSC₂H_Five)₂            0.05g
Methyl-β-cyclodextrin 5.0g
Sodium metabisulfite The amount that makes the following starting solution pH
Water finish 40cc
For both development and fixing, set each packaging bag open by hand at the inlet of each solid agent, drop the tablet into the built-in chemical mixer, and simultaneously add hot water (25-30 ° C) and dissolve while stirring and dissolving. Mix to 3.0 liters in 25 minutes. This was used as a developing / fixing replenisher.
[0143]
The pH when the developer was dissolved was 10.0. The dissolution pH of the fixing solution was 4.80.
[0144]
<Evaluation of density unevenness>
Each sample prepared above is cut into a large-angle size, and the entire surface is uniformly exposed so that the optical density after development processing becomes 1.0, and the processing time is 45 seconds using the automatic developing machine, and the developer is replenished. 200ml / m²Was processed. The obtained sample was evaluated for density unevenness by the following method.
[0145]
Evaluation criteria
A: Density unevenness is not recognized
B: Slight density unevenness is observed at the film edge when gazing, but there is no practical problem
C: Slight density unevenness is observed on the entire film when gazing, but there is no practical problem
D: Density unevenness occurs clearly at the edge of the film, causing practical problems
E: Density unevenness is strongly generated on the entire surface of the film, which is not practical.
[0146]
<Evaluation of sharpness>
The obtained sample was subjected to X-ray exposure through a chest phantom using SRO-250 (manufactured by Konica Corporation) as a screen. Similar to the density unevenness evaluation sample, a sample processed using an automatic processor and a processing agent was visually evaluated for sharpness on a Schaukasten. The evaluation criteria were divided into the following five stages.
[0147]
A: Especially excellent
B: Excellent
C: Normal
D: Slightly inferior
E: Inferior
<Evaluation of sensitivity and fog>
The obtained sample is sandwiched between screens of SRO-250 (manufactured by Konica Corp.), X-ray irradiation is performed under the conditions of tube voltage 90 kVp, current 20 mA, time 0.05 seconds, and a sensitometry curve is prepared by the distance method. The sensitivity was calculated. The development process was performed by the same method as the density unevenness evaluation described above. The sensitivity values in the table are obtained as the reciprocal of the X-ray dose necessary to obtain Dmin + concentration of 1.0. The relative value when 1 is 100 is shown. The fog is a value obtained by subtracting the base concentration (0.15) from Dmin.
[0148]
<Evaluation of CP (covering power)>
The value obtained by subtracting the base concentration from Dmax is the amount with silver (g / m²), Multiplied by 100, and obtained by the following formula 2.
[0149]
Formula 2 CP = (Dmax−0.15) / Amount of silver (g / m²) × 100
<Evaluation of remaining color>
The developed sample was subjected to the same development treatment as that of the sample for evaluating density unevenness while leaving the large-angle size of the obtained sample unexposed, and the residual color was visually evaluated in the following four stages on the Schaukasten.
[0150]
A: No residual color is recognized
B: A very slight residual color is recognized (no problem in practical use)
C: Residual color is recognized (border line that is acceptable and not practical)
D: Residual color is clearly recognized on the entire surface (not practical)
The obtained results are shown in Tables 6 to 8 below.
[0151]
[Table 6]

[0152]
[Table 7]

[0153]
[Table 8]

[0154]
As is apparent from the table, it can be seen that the sample of the present invention has high sensitivity, high sharpness, excellent covering power, and little residual color and density unevenness even with rapid processing.
[0155]
【The invention's effect】
According to the present invention, it is possible to provide a silver halide photographic emulsion having a high sensitivity, a high sharpness, an excellent covering power, a small residual color and density unevenness, and a method for producing the same, by rapid processing.
[Brief description of the drawings]
FIG. 1 is a schematic view showing an example of a silver halide photographic emulsion production apparatus applicable to the production equipment of the present invention.
[Explanation of symbols]
1 reaction vessel
2 Stirring mechanism
3 Dispersion media
4,5 addition line
6 Liquid removal line
7 Liquid return line
8 Permeate discharge line
9 Permeate return line
10 Ultrafiltration unit
11 Circulation pump
12 Flow meter
13, 14, 15 Pressure gauge
16 Pressure adjustment valve
17 Flow adjustment valve
18 Liquid drain valve
19, 20, 21 Valve
22 Ultrafiltration permeate
23 Permeate receiver
24 scales

Claims (5)

The average intergranular distance in the growth process of silver halide grains defined by the following formula 1 is arbitrarily controlled from the start of grain growth to the end of growth, and the average intergranular distance at the start of grain growth is 0.6 to 1. Silver halide grains containing silver halide grains to which a useful photographic material selected from a spectral sensitizing dye, a fog inhibitor, a stabilizer and a sensitizer is added at the time of growth of 1.15 times Photographic emulsion.
Formula 1 Average interparticle distance = (volume of reaction solution / number of growing particles in reaction solution) ^1/3 2. The halogen according to claim 1, comprising silver halide grains to which the photographic useful substance is added at the time of growth which is 0.6 to 1.0 times the average inter-grain distance at the start of grain growth. Silver halide photographic emulsion.   The variation coefficient of the volume conversion grain size of silver halide grains contained in the silver halide emulsion is 30% or less, and 50% or more of the total projected area of the silver halide grains is tabular grains having an aspect ratio of 3 to 50 3. The silver halide photographic emulsion according to claim 1, wherein the silver halide photographic emulsion is present.   The method for controlling the average inter-grain distance of a silver halide photographic emulsion according to any one of claims 1 to 3, which is controlled by a dispersion medium introducing means, a water introducing means or an aqueous solution discharging means. A method for producing a silver photographic emulsion.   5. The method for producing a silver halide photographic emulsion according to claim 4, wherein the aqueous solution discharging means is performed by an ultrafiltration device.

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