JP3779455B2 - Silver halide photographic emulsion, method for producing the same, and silver halide photographic light-sensitive material containing the same - Google Patents

Description

本発明のハロゲン化銀乳剤は、必要により他の乳剤と共に支持体上に一層もしくはそれ以上設けることができる。また、支持体の片側に限らず両面に設けることができる。また、異なる感色性の乳剤として重層することもできる。
【００９０】
本発明のハロゲン化銀乳剤は、黒白ハロゲン化銀写真感光材料（例えば、Ｘレイ感光材料、リス型感光材料、黒白撮影用ネガフィルムなど）やカラー写真感光材料（例えば、カラーネガフィルム、カラー反転フィルム、カラーペーパー等）に用いることができる。さらに、拡散転写用感光材料（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）等にも用いることができる。
【００９１】
本発明の乳剤は、多層からなるカラー感光材料において用いることにより、その写真性能をより発揮することができるので好ましい。本発明の乳剤は、いずれもの感光性層において用いることができるが、特に赤感光性層または緑感光性層で用いることが好ましく、赤感光性層で用いることがさらに好ましい。
【００９２】
本発明のハロゲン化銀写真乳剤、およびそれを用いたハロゲン化銀写真感光材料（以下「本発明の感光材料」ともいう）に用いることのできる種々の技術や無機・有機の素材については一般的にはリサーチ・ディスクロージャーNo. ３０８１１９（１９８９年）に記載されたものを用いることができる。
【００９３】
これに加えて、より具体的には、例えば、本発明のハロゲン化銀写真乳剤が適用できるカラー写真感光材料に用いることができる技術および無機・有機素材については、欧州特許第４３６，９３８Ａ２号の下記の箇所及び下記に引用の特許に記載されている。
【００９４】

また、本発明の感光材料では磁気記録層を設けることも可能である。
【００９５】
本発明に用いられる磁気記録層とは、磁性体粒子をバインダー中に分散した水性もしくは有機溶媒系塗布液を支持体上に塗設したものである。
【００９６】
本発明の感光材料に用いられる磁性体粒子は、γＦｅ_２Ｏ_３などの強磁性酸化鉄、Ｃｏ被着γＦｅ_２Ｏ_３、Ｃｏ被着マグネタイト、Ｃｏ含有マグネタイト、強磁性二酸化クロム、強磁性金属、強磁性合金、六方晶系のＢａフェライト、Ｓｒフェライト、Ｐｂフェライト、Ｃａフェライトなどを使用できる。Ｃｏ被着γＦｅ_２Ｏ_３などのＣｏ被着強磁性酸化鉄が好ましい。形状としては針状、米粒状、球状、立方体状、板状等いずれでもよい。非表面積ではＳ_ＢＥＴで２０ｍ²／ｇ以上が好ましく、３０ｍ²／ｇ以上が特に好ましい。強磁性体の飽和磁化（σｓ）は、好ましくは３．０×１０²〜３．０×１０²Ａ／ｍであり、特に好ましくは４．０×１０²〜２．５×１０²Ａ／ｍである。強磁性体粒子を、シリカおよび／またはアルミナや有機素材による表面処理を施してもよい。さらに、磁性体粒子は特開平６−１６１０３２に記載された如くその表面がシランカップリング剤又はチタンカップリング剤で処理されてもよい。又特開平４−２５９９１１、同５−８１６５２号に記載の表面に無機、有機物を被覆した磁性体粒子も使用できる。
【００９７】
磁性体粒子に用いられるバインダーは、特開平４−２１９５６９に記載の熱可塑性樹脂、熱硬化性樹脂、放射線硬化性樹脂、反応型樹脂、酸、アルカリ又は生分解性ポリマー、天然物重合体（セルロース誘導体、糖誘導体など）およびそれらの混合物を使用することができる。上記の樹脂のＴｇは−４０℃〜３００℃、重量平均分子量は０．２万〜１００万である。例えばビニル系共重合体、セルロースジアセテート、セルローストリアセテート、セルロースアセテートプロピオネート、セルロースアセテートブチレート、セルローストリプロピオネートなどのセルロース誘導体、アクリル樹脂、ポリビニルアセタール樹脂を挙げることができ、ゼラチンも好ましい。特にセルロースジ（トリ）アセテートが好ましい。バインダーは、エポキシ系、アジリジン系、イソシアネート系の架橋剤を添加して硬化処理することができる。イソシアネート系の架橋剤としては、トリレンジイソシアネート、４，４′−ジフェニルメタンジイソシアネート、ヘキサメチレンジイソシアネート、キシリレンジイソシアネート、などのイソシアネート類、これらのイソシアネート類とポリアルコールとの反応生成物（例えば、トリレンジイソシアネート３ｍｏｌとトリメチロールプロパン１ｍｏｌの反応生成物）、及びこれらのイソシアネート類の縮合により生成したポリイソシアネートなどがあげられ、例えば特開平６−５９３５７に記載されている。
【００９８】
前述の磁性体を上記バインダー中に分散する方法は、特開平６−３５０９２に記載されている方法のように、ニーダー、ピン型ミル、アニュラー型ミルなどが好ましく併用も好ましい。特開平５−０８８２８３に記載の分散剤や、その他の公知の分散剤が使用できる。磁気記録層の厚みは０．１μｍ〜１０μｍ、好ましくは０．２μｍ〜５μｍ、より好ましくは０．３μｍ〜３μｍである。磁性体粒子とバインダーの重量比は好ましくは０．５：１００〜６０：１００からなり、より好ましくは１：１００〜３０：１００である。磁性体粒子の塗布量は０．００５〜３ｇ／ｍ²、好ましくは０．０１〜２ｇ／ｍ²、さらに好ましくは０．０２〜０．５ｇ／ｍ²である。磁気記録層の透過イエロー濃度は、０．０１〜０．５０が好ましく、０．０３〜０．２０がより好ましく、０．０４〜０．１５が特に好ましい。磁気記録層は、写真用支持体の裏面に塗布又は印刷によって全面またはストライプ状に設けることができる。磁気記録層を塗布する方法としてはエアードクター、ブレード、エアナイフ、スクイズ、含浸、リバースロール、トランスファーロール、グラビヤ、キス、キャスト、スプレイ、ディップ、バー、エクストリュージョン等が利用でき、特開平５−３４１４３６等に記載の塗布液が好ましい。
【００９９】
磁気記録層に、潤滑性向上、カール調節、帯電防止、接着防止、ヘッド研磨などの機能を合せ持たせてもよいし、別の機能性層を設けて、これらの機能を付与させてもよく、粒子の少なくとも１種以上がモース硬度が５以上の非球形無機粒子の研磨剤が好ましい。非球形無機粒子の組成としては、酸化アルミニウム、酸化クロム、二酸化珪素、二酸化チタン、シリコンカーバイト等の酸化物、炭化珪素、炭化チタン等の炭化物、ダイアモンド等の微粉末が好ましい。これらの研磨剤は、その表面をシランカップリング剤又はチタンカップリング剤で処理されてもよい。これらの粒子は磁気記録層に添加してもよく、また磁気記録層上にオーバーコート（例えば保護層、潤滑剤層など）しても良い。この時使用するバインダーは前述のものが使用でき、好ましくは磁気記録層のバインダーと同じものがよい。磁気記録層を有する感光材料については、米国特許５，３３６，５８９、同５，２５０，４０４、同５，２２９，２５９、同５，２１５，８７４、ＥＰ４６６，１３０に記載されている。
【０１００】
次に磁気記録層を有する本発明の感光材料に好ましく用いられるポリエステル支持体について記すが、上記以外の感光材料、処理、カートリッジ及び実施例なども含め詳細については、公開技報、公技番号９４−６０２３（発明協会；１９９４．３．１５．）に記載されている。本発明に用いられるポリエステルはジオールと芳香族ジカルボン酸を必須成分として形成され、芳香族ジカルボン酸として２，６−、１，５−、１，４−、及び２，７−ナフタレンジカルボン酸、テレフタル酸、イソフタル酸、フタル酸、ジオールとしてジエチレングリコール、トリエチレングリコール、シクロヘキサンジメタノール、ビスフェノールＡ、ビスフェノール等が挙げられる。この重合ポリマーとしては、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリシクロヘキサンジメタノールテレフタレート等のホモポリマーを挙げることができる。特に好ましいのは２，６−ナフタレンジカルボン酸を５０モル％〜１００モル％含むポリエステルである。中でも特に好ましいのはポリエチレン−２，６−ナフタレートである。平均分子量の範囲は約５，０００ないし２００，０００である。本発明のポリエステルのＴｇは５０℃以上であり、さらに９０℃以上が好ましい。
【０１０１】
次にポリエステル支持体は、巻き癖をつきにくくするために熱処理温度は４０℃以上Ｔｇ未満、より好ましくはＴｇ−２０℃以上Ｔｇ未満で熱処理を行う。熱処理はこの温度範囲内の一定温度で実施してもよく、冷却しながら熱処理してもよい。この熱処理時間は、０．１時間以上１５００時間以下、さらに好ましくは０．５時間以上２００時間以下である。支持体の熱処理は、ロール状で実施してもよく、またウェブ状で搬送しながら実施してもよい。表面に凹凸を付与し（例えばＳｎＯ_２やＳｂ_２Ｏ_５等の導電性無機微粒子を塗布する）、面状改良を図ってもよい。又端部にローレットを付与し端部のみ少し高くすることで巻芯部の切り口写りを防止するなどの工夫を行うことが望ましい。これらの熱処理は支持体製膜後、表面処理後、バック層塗布後（帯電防止剤、滑り剤等）、下塗り塗布後のどこの段階で実施してもよい。好ましいのは帯電防止剤塗布後である。
【０１０２】
このポリエステルには紫外線吸収剤を練り込んでも良い。又ライトパイピング防止のため、三菱化成製のＤｉａｒｅｓｉｎ、日本化薬製のＫａｙａｓｅｔ等ポリエステル用として市販されている染料または顔料を練り込むことにより目的を達成することが可能である。
【０１０３】
次に、本発明の感光材料では支持体と感光材料構成層を接着させるために、表面処理することが好ましい。薬品処理、機械的処理、コロナ放電処理、火焔処理、紫外線処理、高周波処理、グロー放電処理、活性プラズマ処理、レーザー処理、混酸処理、オゾン酸化処理、などの表面活性化処理が挙げられる。表面処理の中でも好ましいのは、紫外線照射処理、火焔処理、コロナ処理、グロー処理である。
【０１０４】
本発明の感光材料には滑り性がある事が好ましい。滑り剤含有層は感光層面、バック面ともに用いることが好ましい。好ましい滑り性としては動摩擦係数で０．２５以下０．０１以上である。この時の測定は直径５ｍｍのステンレス球に対し、６０ｃｍ／分で搬送した時の値を表す（２５℃、６０％ＲＨ）。この評価において相手材として感光層面に置き換えてもほぼ同レベルの値となる。
【０１０５】
本発明に使用可能な滑り剤としては、ポリオルガノシロキサン、高級脂肪酸アミド、高級脂肪酸金属塩、高級脂肪酸と高級アルコールのエステル等であり、ポリオルガノシロキサンとしては、ポリジメチルシロキサン、ポリジエチルシロキサン、ポリスチリルメチルシロキサン、ポリメチルフェニルシロキサン等を用いることができる。添加層としては乳剤層の最外層やバック層が好ましい。特にポリジメチルシロキサンや長鎖アルキル基を有するエステルが好ましい。
【０１０６】
本発明の感光材料にはマット剤が有る事が好ましい。マット剤としては乳剤面、バック面とどちらでもよいが、乳剤側の最外層に添加するのが特に好ましい。マット剤は処理液可溶性でも処理液不溶性でもよく、好ましくは両者を併用することである。例えばポリメチルメタクリレート、ポリ（メチルメタクリレート／メタクリル酸＝９／１又は５／５（モル比）、ポリスチレン粒子などが好ましい。粒径としては０．８〜１０μｍが好ましく、その粒径分布も狭いほうが好ましく、平均粒径の０．９〜１．１倍の間に全粒子数の９０％以上が含有されることが好ましい。又マット性を高めるために０．８μｍ以下の微粒子を同時に添加することも好ましく例えばポリメチルメタクリレート（０．２μｍ）、ポリ（メチルメタクリレート／メタクリル酸＝９／１（モル比）、０．３μｍ）、ポリスチレン粒子（０．２５μｍ）、コロイダルシリカ（０．０３μｍ）が挙げられる。次に本発明の感光材料で用いられるフィルムパトローネについて記す。本発明で使用されるパトローネの主材料は金属でも合成プラスチックでもよい。
【０１０７】
好ましいプラスチック材料はポリスチレン、ポリエチレン、ポリプロピレン、ポリフェニルエーテルなどである。更に本発明のパトローネは、各種の帯電防止剤を含有してもよくカーボンブラック、金属酸化物粒子、ノニオン、アニオン、カチオン及びペタイン系界面活性剤又はポリマー等を好ましく用いることが出来る。これらの帯電防止されたパトローネは特開平１−３１２５３７、同１−３１２５３８に記載されている。特に２５℃、２５％ＲＨでの抵抗が１０¹²Ω以下が好ましい。通常プラスチックパトローネは、遮光性を付与するためにカーボンブラックや顔料などを練り込んだプラスチックを使って製作される。パトローネのサイズは現在１３５サイズのままでもよいし、カメラの小型化には、現在の１３５サイズの２５ｍｍのカートリッジの径を２２ｍｍ以下とすることも有効である。パトローネのケースの容積は、３０ｃｍ³以下好ましくは２５ｃｍ³以下とすることが好ましい。パトローネおよびパトローネケースに使用されるプラスチックの重量は５ｇ〜１５ｇが好ましい。
【０１０８】
更に本発明で用いられる、スプールを回転してフイルムを送り出すパトローネでもよい。またフイルム先端がパトローネ本体内に収納され、スプール軸をフイルム送り出し方向に回転させることによってフイルム先端をパトローネのポート部から外部に送り出す構造でもよい。これらは米国特許４，８３４，３０６、同５，２２６，６１３に開示されている。又、現像前のいわゆる生フイルムと現像済みの写真フイルムが同じ新パトローネに収納されていてもよいし、異なるパトローネでもよい。
【０１０９】
本発明のカラー写真感光材料は、アドバンスト・フォト・システム（以下、ＡＰＳという）用カラーネガフイルムとしても好適であり、富士写真フイルム（株）（以下、富士フイルムという）製ＮＥＸＩＡ Ａ、ＮＥＸＩＡ Ｆ、ＮＥＸＩＡ Ｈ（順にＩＳＯ ２００／１００／４００）のようにフイルムをＡＰＳフォーマットに加工し、専用カートリッジに収納したものを挙げることができる。これらのＡＰＳ用カートリッジフイルムは、富士フイルム製エピオン３００Ｚに代表されるエピオンシリーズ等のＡＰＳ用カメラに装填して用いられる。また、本発明のカラー写真感光材料は、富士フイルム製フジカラー写ルンですスーパースリムのようなレンズ付きフイルムにも好適である。
【０１１０】
これらにより撮影されたフイルムは、ミニラボシステムでは次のような行程を経てプリントされる。
（１）受付（露光済みカートリッジフイルムをお客様からお預かり）
（２）デタッチ行程（カートリッジから、フイルムを現像工程用の中間カートリッジに移す）
（３）フイルム現像
（４）リアタッチ工程（現像済みのネガフイルムを、もとのカートリッジに戻す）
（５）プリント（Ｃ、Ｈ、Ｐ ３タイプのプリントとインデックスプリントをカラーペパー［好ましくは富士フイルム製ＳＵＰＥＲ ＦＡ８］に連続プリント）
（６）照合・出荷（カートリッジとインデックスプリントをＩＤナンバーで照合し、プリントとともに出荷）。
【０１１１】
これらのシステムとしては、富士フイルムのミニラボチャンピオンスーパーＦＡ−２９８／ＦＡ−２７８／ＦＡ−２５８／ＦＡ−２３８が好ましい。フイルムプロセサーとしてはＦＰ９２２ＡＬ／ＦＰ５６２Ｂ／ＦＰ５６２ＢＬ／ＦＰ３６２Ｂ／ＦＰ３６２２ＢＬが挙げられ、推奨処理薬品はフジカラージャストイットＣＮ−１６Ｌである。プリンタープロセサーとしては、ＰＰ３００８ＡＲ／ＰＰ３００８Ａ／ＰＰ１８２８ＡＲ／ＰＰ１８２８Ａ／ＰＰ１２５８ＡＲ／ＰＰ１２５８Ａ／ＰＰ７２８ＡＲ／ＰＰ７２８Ａが挙げられ、推奨処理薬品はフジカラージャストイットＣＰ−４７Ｌである。デタッチ行程で用いるデタッチャー、リアタッチ工程で用いるリアタッチャーは、それぞれ富士フイルムのＤＴ２００／ＤＴ１００及びＡＴ２００／ＡＴ１００が好ましい。
【０１１２】
ＡＰＳシステムは、富士フイルムのデジタルイメージワークステーションＡｌａｄｄｉｎ １０００を中心とするフォトジョイシステムにより楽しむこともできる。例えば、Ａｌａｄｄｉｎ １０００に現像済みＡＰＳカートリッジフイルムを直接装填したり、ネガフイルム、ポジフイルム、プリントの画像情報を、３５ｍｍフイルムスキャナーＦＥ−５５０やフラットヘッドスキャナーＰＥ−５５０を用いて入力し、得られたデジタル画像データを容易に加工・編集することができる。そのデータは、光定着型感熱カラープリント方式によるデジタルカラープリンターＮＣ−５５０ＡＬやレーザー露光熱現像転写方式のピクトログラフィー３０００によって、又はフイルムレコーダーを通して既存のラボ機器によりプリントとして出力することができる。また、Ａｌａｄｄｉｎ １０００は、デジタル情報を直接フロッピーディスクやＺｉｐディスクに、もしくはＣＤライターを介してＣＤ−Ｒに出力することもできる。
【０１１３】
一方、家庭では、現像済みＡＰＳカートリッジフイルムを富士フイルム製フォトプレイヤーＡＰ−１に装填するだけでＴＶで写真を楽しむことができるし、富士フイルム製フォトスキャナーＡＳ−１に装填すれば、パソコンに画像情報を高速で連続的に取り込むこともできる。また、フイルム、プリント又は立体物をパソコンに入力するには、富士フイルム製フォトビジョンＦＶ−１０／ＦＶ−５が利用できる。さらに、フロッピーディスク、Ｚｉｐディスク、ＣＤ−Ｒもしくはハードディスクに記録された画像情報は、富士フイルムのアプリケーションソフト フォトファクトリーを用いてパソコン上で様々に加工して楽しむことができる。パソコンから高画質なプリントを出力するには、光定着型感熱カラープリント方式の富士フイルム製デジタルカラープリンターＮＣ−２／ＮＣ−２Ｄが好適である。
【０１１４】
現像済みのＡＰＳカートリッジフイルムを収納するには、フジカラーポケットアルバムＡＰ−５ポップＬ、ＡＰ−１ポップＬ、ＡＰ−１ポップＫＧ又はカートリッジファイル１６が好ましい。
【０１１５】
【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。
【０１１６】
実施例１ トリメリット化ゼラチンによる単分散極薄平板状粒子乳剤の製造法
乳剤１ａ）比較例
反応容器にゼラチン水溶液１０００mＬ（低分子ゼラチン（分子量１５０００脱イオン化アルカリ処理骨ゼラチン）０．５ｇ及び、ＫＢｒ０．３１ｇを含む）を入れ、温度を４０℃に保ちながら、Ａｇ−１液（１００mL中にＡｇＮＯ_３５ｇを含む）とＸ−１液（１００mL中にＫＢｒ３．５ｇを含む）を３０．０mL／分で２０．０mLずつ同時混合添加した。１分間攪拌した後、ＫＢｒ液（１００mL中にＫＢｒ１０ｇを含む）を２２mL添加後、温度を７５℃に昇温した。昇温後５分間の熟成工程を経た後、酸化処理ゼラチン溶液（２５０mL中に酸化処理ゼラチン（メチオニン含率５％以下）３５ｇを含む）を添加した。次に、Ａｇ−２液（１００mL中にＡｇＮＯ_３２０．４ｇを含む）とＸ−２液（１００mL中にＫＢｒ１６．７ｇを含む）をC.D.J.（controlled double jet）で−３０ｍＶに保ったまま、Ａｇ−２液の総添加量が７００mLとなるまで４１分間、４．４mL／分から３１．０mL／分まで添加速度を一定の割合で増加させ添加した。同時に、ＡｇＩ微粒子を用い、成長工程終了後の粒子中の全銀量に対する沃化銀含有量が４．０ｍｏｌ％になるよう乳剤添加を行った。最後に、温度を３５℃に下げ、沈降水洗した。ゼラチン水溶液を加え、４０℃でｐＨ６．０に調節した。
【０１１７】
該粒子のレプリカのＴＥＭ像を観察した。得られた乳剤において、ＡｇＩ ４モル％（粒子内の全銀量を基準として、以下同様）、厚さ０．０６５μｍ、アスペクト比２８．２の粒子の投影面積の和が全投影面積の９７％を占めた。
【０１１８】
乳剤１ｂ）本発明
乳剤１ａに対し、熟成工程後に酸化処理ゼラチン溶液を添加する代わりに、トリメリット化ゼラチン溶液（２５０mL中にトリメリット化ゼラチン３５ｇを含む）を添加し、すぐさまＨＮＯ_３でｐＨを５．８に合わせた以外は全て同じ条件で粒子形成を行った。得られた乳剤において、ＡｇＩ ４モル％、厚さ０．０６４μｍ、アスペクト比２８．９の粒子の投影面積の和が全投影面積の９７％を占めた。
【０１１９】
乳剤１ｃ）本発明
乳剤１ｂに対し、トリメリット化ゼラチン溶液の添加時期を核形成後即添加し、すぐさまＨＮＯ_３でｐＨを５．８に合わせた以外は全て同じ条件で粒子形成を行った。得られた乳剤において、ＡｇＩ ４モル％、厚さ０．０６３μｍ、アスペクト比２９．６の粒子の投影面積の和が全投影面積の９７％を占めた。
【０１２０】
下表に、上記乳剤１ａ〜１ｃにおける熟成工程後、及び最終粒子（成長後）のハロゲン化銀平板粒子における円換算直径の変動係数（ＣＯＶ）並びに厚さを示す。
【０１２１】

この結果から、トリメリット化ゼラチンは酸化処理ゼラチンに対し、同等或いはそれ以上の薄板化効果があり、また成長時、更には熟成時における単分散化効果もあることが分かる。
【０１２２】
実施例２ 過熟成工程による単分散極薄平板状粒子乳剤の製造法
乳剤１Ａ）本発明
反応容器にゼラチン水溶液１０００mL（低分子ゼラチン（分子量１５０００脱イオン化アルカリ処理骨ゼラチン）０．５ｇ及び、ＫＢｒ０．３１ｇを含む）を入れ、温度を４０℃に保ちながら、Ａｇ−１液（１００mL中にＡｇＮＯ_３５ｇを含む）とＸ−１液（１００mL中にＫＢｒ３．５ｇを含む）を３０．０mL／分で２０．０mLずつ同時混合添加した。１分間攪拌した後、ＫＢｒ液（１００mL中にＫＢｒ１０ｇを含む）を２２mL添加後、温度を７５℃に昇温した。昇温後５分間の熟成工程を経た後、過熟成工程を行い、８０％（熟成工程時での平板核数を１００％とした場合）にまで平板自身をオストワルド熟成により減少させた。その後、酸化処理ゼラチン溶液（２５０mL中に酸化処理ゼラチン（メチオニン含率５％以下）３５ｇを含む）を添加し、Ａｇ−２液（１００mL中にＡｇＮＯ_３２０．４ｇを含む）とＸ−２液（１００mL中にＫＢｒ１６．７ｇを含む）をC.D.J.（controlled double jet）で−３０ｍＶに保ったまま、Ａｇ−２液の総添加量が５６０mLとなるまで３５分間、４．４mL／分から２７．０mL／分まで添加速度を一定の割合で増加させ添加した。同時に、ＡｇＩ微粒子を用い、成長工程終了後の粒子中の全銀量に対する沃化銀含有量が４．０ｍｏｌ％になるよう乳剤添加を行った。最後に、温度を３５℃に下げ、沈降水洗した。ゼラチン水溶液を加え、４０℃でｐＨ６．０に調節した。
【０１２３】
該粒子のレプリカのＴＥＭ像を観察した。得られた乳剤において、ＡｇＩ ４モル％、厚さ０．０６５μｍ、アスペクト比２８．９の粒子の投影面積の和が全投影面積の９７％を占めた。
【０１２４】
乳剤１Ｂ）本発明
乳剤１Ａに対し、過熟成工程後に酸化処理ゼラチン溶液を添加する代わりに、トリメリット化ゼラチン溶液（２５０mL中にトリメリット化ゼラチン３５ｇを含む）を添加し、すぐさまＨＮＯ_３でｐＨを５．８に合わせた以外は全て同じ条件で粒子形成を行った。得られた乳剤において、ＡｇＩ ４モル％、厚さ０．０６４μｍ、アスペクト比２９．５の粒子の投影面積の和が全投影面積の９７％を占めた。
【０１２５】
乳剤１Ｃ）本発明
乳剤１Ｂに対し、トリメリット化ゼラチン溶液の添加時期を核形成後即添加し、すぐさまＨＮＯ_３でｐＨを５．８に合わせた以外は全て同じ条件で粒子形成を行った。得られた乳剤において、ＡｇＩ ４モル％、厚さ０．０６３μｍ、アスペクト比３０．２の粒子の投影面積の和が全投影面積の９７％を占めた。
【０１２６】
下表に、上記乳剤１Ａ〜１Ｃにおける過熟成工程後、及び最終粒子（成長後）のハロゲン化銀平板粒子における円換算直径の変動係数（ＣＯＶ）を示す。なお参考のため乳剤１ａ〜１ｃのＣＯＶを（）内に示す。
【０１２７】

【０１２８】
この結果から、過熟成工程後のＣＯＶは熟成工程後のそれに対し、いずれの乳剤も悪化傾向にあるのに対し、成長後の最終粒子はその優劣が逆転した結果となっている。実際、それぞれの円相当径分布から、乳剤１Ａは、乳剤１ａに見られた円相当径の小さな平板が大きく減少し、結果として、分布が良化している事が分かった。また、乳剤１Ｂ、１Ｃは、円相当径の小さな平板の減少は元より、円相当径の大きな平板の頻度も減少しており、結果として分布が良化している事が分かった。
【０１２９】
実施例３ 微粒子添加成長法による単分散極薄平板状粒子乳剤の製造法
次に、本発明の一態様である図１に示した混合器を用い、Ａｇ−３液（１００mL中にＡｇＮＯ_３１０．２ｇを含む溶液）とＸ−３液（１００mL中に低分子量ゼラチン（平均分子量２万）５重量％含むＫＢｒ６．８５ｇ、ＫＩ０．４ｇの溶液）をＡｇ−３液の総添加量が１４００mLとなるまで４１分間、８．８mL／分から６２．０mL／分まで添加速度を一定の割合で増加させ成長工程に添加した以外は、１ａ〜１ｃ、１Ａ〜１Ｃと同様に行った結果を、２ａ〜２ｃ、２Ａ〜２Ｃとし、下表に示す。
【０１３０】

この結果から、本発明である図４に示した混合器を用い、成長工程を微粒子添加方法とすることで、大きく薄板化することが分かる。またその際比較例のＣＯＶは大きく悪化傾向となる一方、本発明の乳剤２ｂ、２ｃ及び２Ａ〜２Ｃは単分散性を維持したまま薄板化している事が分かる。特に本発明乳剤２Ｃは優れた単分散性を維持したまま薄板化していることが分かる。
【０１３１】
一方、分散後の上記乳剤のコーナー部は、若干溶解傾向にあった。これは、極薄平板状粒子乳剤の粒子形態は基本的に不安定であり、何らかの溶解防止手段を施す必要がある事を示している。
極薄平板状粒子乳剤における粒子形態安定性
極薄平板状粒子乳剤における、沃化銀含有量と粒子形態安定性の関係を求めるため以下の実験をおこなった。
【０１３２】
実施例４ 高沃化銀含有単分散沃臭化銀極薄平板状粒子乳剤
該乳剤１ａ〜１ｃ、１Ａ〜１Ｃ及び２ａ〜２ｃ、２Ａ〜２Ｃに対し、成長時の沃化銀含有量（すなわち、最外層の銀量に対する当該最外層に含有される沃化銀量）が６、及び１５モル％になるようＸ−３液を調製した以外は全て同じ条件で粒子形成を行った。下表に、結果として得られた極薄平板状粒子乳剤のハロゲン化銀平板粒子における円換算直径の変動係数（ＣＯＶ）を示す。なお（）内は厚さを示している。
【０１３３】

【０１３４】
この結果から、成長工程を微粒子添加方法とした上記乳剤２ｂ〜２ｃ、２Ａ〜２Ｃはいずれも、乳剤１ａ〜１ｃ、１Ａ〜１Ｃに見られた沃化銀含有量増加による平板厚みの増加が、全く観察されなかった。この結果は、本発明である図４に示した混合器による微粒子添加成長法は、極薄平板状粒子乳剤作成における有用な製造技術であることを示している。
【０１３５】
また、乳剤１ａ及び２ａ（比較例）は沃化銀含有率の増加と共に大きく多分散化した。一方、本発明乳剤のＣＯＶは、いずれも沃化銀含有率の増加と共に若干の分布の悪化がみられるものの、比較例に対しては有為な差となった。特に過熟成過程を具備し、トリメリット化ゼラチンを核形成後即添加した乳剤１Ｃ及び２Ｃ（本発明）は、沃化銀含有率１５モル％といった高沃化銀含有域においても、ＣＯＶ２０％以下といった優れた単分散性を実現できていることが分かる。
【０１３６】
次に粒子厚みの異なる本発明乳剤１Ｃ及び２Ｃに対し、成長時の沃化銀含有率（すなわち、最外層の銀量に対する当該最外層に含有される沃化銀）が０、３、４、６、及び１５モルになるようＸ−３液を調製した以外は全て同じ条件で粒子形成を行った。次に、それぞれ沈降、分散後の化学増感時の温度を考慮に入れた温度（５０℃）で一定に保ち、１５分、３０分、及び６０分での粒子形態をレプリカ法にて観察した。下表にその形態変化の有・無を示す。
【０１３７】

以上の結果から、極薄平板状粒子の溶解性は沃化物含有量の増加と共に抑制される結果となった。一方、その溶解性は、極薄平板状粒子の厚さの減少とともに、増加する事も分かる。以上の結果から、極薄平板状粒子の形態安定化として必要な基盤沃化物含率は、少なくとも４モル％以上、好ましくは６モル％以上、更に好ましくは１５モル％以上であることが分かる。
【０１３８】
実施例５ コア／シエル型単分散沃臭化銀極薄平板状粒子乳剤
次に本発明乳剤２Ｃに対し、最外層の沃化銀含有率が最外層の銀量に対して６モル％及び１５モル％、その他の領域が当該その他の領域の銀量に対して２モル％になるよう変更した以外は全て同じ条件で粒子形成を行った。得られた乳剤は、厚さ０．０４７μｍのコア／シエル極薄平板状粒子が得られた。次に、該乳剤に対し、沈降、分散後の化学増感時の温度を考慮に入れた温度（５０℃）で一定に保ち、１５分、３０分、及び６０分での粒子形態をレプリカ法にて観察した。下表にその形態変化の有・無を示す。
【０１３９】
最外層沃化銀含有量６モル％
コア／シエル比（銀量） １５分 ３０分 ６０分
９５／５ 有り 有り 有り
９０／１０ 無し 有り 有り
８０／２０ 無し 無し 有り
７５／２５ 無し 無し 無し。
【０１４０】
最外層沃化銀含有量１５モル％
コア／シエル比（銀量） １５分 ３０分 ６０分
９５／５ 無し 有り 有り
９０／１０ 無し 無し 有り
８０／２０ 無し 無し 無し
７５／２５ 無し 無し 無し。
【０１４１】
この結果から、最外層の沃化物含率を少なくとも６モル％、好ましくは１５モル％としたコア／シエル構造とすることで、極薄平板状粒子の形態安定化が可能となる事が分かる。また、コア／シエル比としては、１０％以上、好ましくは２０％以上、より好ましくは２５％以上のシエル領域が必要であることが分かる。
単層及び重層感光材料の実施例を次に示す。
【０１４２】
＜粒子形成＞
実施例Ｘ
反応容器にゼラチン水溶液１０００mL（低分子ゼラチン（分子量１５０００脱イオン化アルカリ処理骨ゼラチン）０．５ｇ及び、ＫＢｒ０．３１ｇを含む）を入れ、温度を４０℃に保ちながら、Ａｇ−１液（１００mL中にＡｇＮＯ_３５ｇを含む）とＸ−１液（１００mL中にＫＢｒ３．５ｇを含む）を３０．０mL／分で２０．０mLずつ同時混合添加した。１分間攪拌した後、ＫＢｒ液（１００mL中にＫＢｒ１０ｇを含む）を２２mL添加後、トリメリット化ゼラチン溶液（２５０mL中にトリメリット化ゼラチン３５ｇを含む）を添加し、すぐさまＨＮＯ_３でｐＨを５．８に合わせ温度を７５℃に昇温した。昇温後１０分おきに随時乳剤をサンプリングした。
【０１４３】
該粒子のレプリカのＴＥＭ像を観察し、熟成時間と平板状粒子の円換算直径の変動係数の関係を調べた結果を以下に示す。なお、昇温後〜１０分までは、レギュラー及び一重双晶粒子の混入が確認されたため、核形成−熟成、及び核形成−熟成−過熟成工程を経た核(core)部の円換算直径の変動係数(COVc)は、１０分以降から測定した。
【０１４４】
昇温後 円換算直径の変動係数(COVc)
１０分 １７ ％
２０分 ２５ ％
３０分 ３２ ％
４０分 ４０ ％
５０分 ４４ ％
以上の結果から、熟成工程の終了は、昇温後１０分で、以降は、過熟成工程の段階である。
乳剤Ｘ１）比較例
実施例Ｘにおいて、熟成工程終了後（昇温後１０分）、すぐさま本発明である図４に示した混合器を用い、Ａｇ−２液（１００mL中にＡｇＮＯ_３２０．４ｇを含む溶液）とＸ−２液（１００mL中に低分子ゼラチン（平均分子量２万）５重量％含むＫＢｒ１６．７ｇ、ＫＩ１．０ｇの溶液）を初期流速４．４mL／分から０．６mＬ／分添加速度を一定の割合で増加させ添加し、球相当径が０．７１μｍとなるまで成長を継続した（銀量比７０％）。
【０１４５】
次に、引き続きＡｇ−３液（１００mL中にＡｇＮＯ_３１４．２ｇを含む）とＸ−３液（１００mL中にＫＩ３１．２ｇを含む）をダブルジェット法で４分間にわたって添加した（銀量比４．７５％）。
【０１４６】
最後に、再びＡｇ−２液とＸ−４（１００mL中にＫＢｒ１６．７ｇ含む溶液）をダブルジェット法によりｐＡｇを９．７に保ち１０分間にわたって添加した（銀量比２５．２５％）。
【０１４７】
上記乳剤を３５℃にて公知のフロキュレーション法により水洗し、ゼラチンを加え４０℃とした。
【０１４８】
該粒子のレプリカのＴＥＭ像を観察した。得られた乳剤において、ＡｇＩ ５．５モル％、厚さ０．０５０μｍ、アスペクト比３９．８の粒子の投影面積の和が全投影面積の９７％を占めた。
【０１４９】
乳剤Ｘ２）本発明
乳剤Ｘ１に対し、過熟成工程後（昇温後２０分）、すぐさま成長を開始した以外は、全て同様にして作成した。
【０１５０】
乳剤Ｘ３）本発明
乳剤Ｘ１に対し、過熟成工程後（昇温後３０分）、すぐさま成長を開始した以外は、全て同様にして作成した。
【０１５１】
乳剤Ｘ４）本発明
乳剤Ｘ１に対し、過熟成工程後（昇温後４０分）、すぐさま成長を開始した以外は、全て同様にして作成した。
【０１５２】
乳剤Ｘ５）本発明
乳剤Ｘ１に対し、過熟成工程後（昇温後５０分）、すぐさま成長を開始した以外は、全て同様にして作成した。
【０１５３】
＜分光増感および化学熟成＞
乳剤Ｘ１〜Ｘ５をそれぞれ６２℃に昇温し後掲の増感色素Ｅｘｓ−１を５．５×１０^-4モル／モルＡｇ、ＥｘＳ−２を１．６×１０^-5モル／モルＡｇ、ＥｘＳ−３を５．５×１０^-4モルＡｇ添加し１０分間おいた後、チオ硫酸ナトリウム２．６×１０^-5モル／モルＡｇ、Ｎ，Ｎジメチルセレノウレア１．１×１０^-5モル／モルＡｇ、チオシアン酸カリウム３．０×１０^-3モル／モルＡｇ、塩化金酸８．６×１０^-6モル／モルＡｇ添加し、１／１００秒露光したときの感度が最も高くなるように熟成を行った。このようにして得られた乳剤をＹ１〜Ｙ５とする。
＜塗布試料の作製及びその評価＞
下塗り層を設けてある三酢酸セルロースフィルム支持体上に次の第Ａ表に示すような塗布量で、各乳剤Ｙ１〜Ｙ５及び保護層を塗布し、塗布試料１０１ないし１０５を作成した。
【０１５４】

【０１５５】
【化１】

これらの試料を４０℃、相対湿度７０％の条件下に１４時間放置した後、連続ウエッジを通して１／１００秒間露光し、次の第Ｂ表に示すカラー現像を行った。
【０１５６】
処理済の試料を緑色のフィルターで濃度測定した。得られた結果を後掲の表１に示す。
【０１５７】

次に、処理液の組成を記す。
【０１５８】

【０１５９】

【０１６０】
【化２】

【０１６１】
（水洗液）
水道水をＨ型強酸性カチオン交換樹脂（ロームアンドハース社製アンバーライトＩＲ−１２０Ｂ）と、ＯＨ型アニオン交換樹脂（同アンバーライトＩＲ−４００）を充填した混床式カラムに通水してカルシウムおよびマグネシウムイオン濃度を３ｍｇ／Ｌ以下に処理し、続いて二塩化イソシアヌール酸ナトリウム２０ｍｇ／Ｌと硫酸ナトリウム１．５ｇ／Ｌを添加した。
【０１６２】
この液のｐＨは６．５〜７．５の範囲にある。
【０１６３】

【０１６４】
【表１】

表１において、試料１０１〜１０５の感度および階調は試料１０１の感度および階調を１００としてそれぞれ相対値で表わした。
本発明試料１０２〜１０５は、比較試料１０１に対し、高感化し、且つ階調が大きく硬調であることがわかる。
該写真性能の向上は、過熟成工程の導入による単分散性の向上により達成されており、本発明の効果が顕著であることが分かる。
【０１６５】
＜重層実施例＞
１）支持体
本実施例で用いた支持体は、下記の方法により作成した。
【０１６６】
市販のポリエチレン−２，６−ナフタレートポリマー１００重量部と紫外線吸収剤としてTinuvin Ｐ．３２６（ガイギー社製）を２重量部と常法により乾燥した後、３００℃にて溶融後、Ｔ型ダイから押し出し１４０℃で３．０倍の縦延伸を行い、続いて１３０℃で３．０倍の横延伸を行い、さらに２５０℃で６秒間熱固定して厚さ９０μのＰＥＮフィルムを得た。
【０１６７】
さらに、その一部を直径２０cmのステンレス巻き芯に巻付けて、１１０℃、４８時間の熱履歴を与えた。
【０１６８】
２）下塗層の塗設
上記支持体は、その両面にコロナ放電処理、ＵＶ放電処理、さらにグロー放電処理、および火焔処理をした後、それぞれの面に下記組成の下塗液を塗布して下塗層を延伸時高温面側に設けた。コロナ放電処理はピラー社製ソリッドステートコロナ処理機６ＫＶＡモデルを用い、３０cm幅支持体を２０ｍ／分で処理する。このとき、電流・電圧の読み取り値より被処理物は、０．３７５ＫＶ・Ａ・分／m²の処理がなされた。処理時の放電周波数は、９．６ＫＨｚ、電極と誘導体ロールのギャップクリアランスは、１．６mmであった。又ＵＶ放電処理は、７５℃で加熱しながら放電処理した。さらにグロー放電処理は円柱電極で３０００Ｗの３０秒間照射した。
【０１６９】
ゼラチン ３ｇ
蒸留水 ２５ｍＬ
ソジウムα−スルホジ−２−エチルヘキシルサクシネート ０．０５ｇ
ホルムアルデヒド ０．０２ｇ
サリチル酸 ０．１ｇ
ジアセチルセルロース ０．５ｇ
ｐ−クロロフェノール ０．５ｇ
レゾルシン ０．５ｇ
クレゾール ０．５ｇ
（ＣＨ₂ ＝ＣＨＳＯ₂ ＣＨ₂ ＣＨ₂ ＮＨＣＯ）₂ ＣＨ₂ ０．２ｇ
トリメチロールプロパントリアジン ０．２ｇ
トリメチロールプロパントリストルエンジイソシアネート ０．２ｇ
メタノール １５ｍＬ
アセトン ８５ｍＬ
ホルムアルデヒド ０．０１ｇ
酢酸 ０．０１ｇ
濃塩酸 ０．０１ｇ。
３）バック層の塗設
下塗後の上記支持体の片方の面にバック層として下記組成の帯電防止層、磁気記録層さらに滑り層を付与した。
【０１７０】
３−１）帯電防止層の塗設
３−１−１）導電性微粒子分散液（酸化スズ−酸化アンチモン複合物分散液）の調製
塩化第二スズ水和物２３０重量部と三塩化アンチモン２３重量部をエタノール３０００重量部に溶解し均一溶液を得た。この溶液に１Ｎの水酸化ナトリウム水溶液を前記溶液のｐＨが３になるまで滴下し、コロイド状酸化第二スズと酸化アンチモンの共沈澱を得た。得られた共沈澱を５０℃に２４時間放置し、赤褐色のコロイド状沈澱を得た。
【０１７１】
赤褐色コロイド状沈澱を遠心分離により分離した。過剰なイオンを除くため沈澱に水を加え遠心分離によって水洗した。この操作を３回繰り返し過剰イオンを除去した。
【０１７２】
過剰イオンを除去したコロイド状沈澱２００重量部を水１５００重量部に再分散し、６５０℃に加熱した焼成炉に噴霧し、青味がかった平均粒径０．００５μｍの酸化スズ−酸化アンチモン複合物の微粒子粉末を得た。この微粒子粉末の比抵抗は５Ω・cmであった。
【０１７３】
上記微粒子粉末４０重量部と水６０重量部の混合液をpH７．０に調製し、攪拌機で粗分散の後、横型サンドミル（商品名ダイノミル；ＷＩＬＬＹＡ．ＢＡＣＨＯＦＥＮＡＧ製）で滞留時間が３０分になるまで分散して調製した。この時の二次凝集体の平均粒径は約０．０４μｍであった。
【０１７４】
３−１−２）導電性層の塗設
下記処方を乾燥膜厚が０．２μｍになるように塗設し、１１５℃で６０秒間乾燥した。
【０１７５】
３−１−１）で作製の導電性微粒子分散液 ２０重量部
ゼラチン ２重量部
水 ２７重量部
メタノール ６０重量部
Ｐ−クロロフェノール ０．５重量部
レゾルシン ２重量部
ポリオキシエチレンノニルフェニルエーテル ０．０１重量部
得られた導電性膜の抵抗は、１０8.0 （１００Ｖ）であり、優れた帯電防止性能を有するものであった。
【０１７６】
３−２）磁気記録層の塗設
磁性体Ｃｏ−被着γ−Ｆｅ₂ Ｏ₃ （長軸０．１４μｍ、単軸０．０３μｍの針状、比表面積４１m²／ｇ、飽和磁化８９ｅｍｕ／ｇ、表面は酸化アルミと酸化珪素でそれぞれＦｅ₂ Ｏ₃ の２重量％で表面処理されている。保磁力９３０Ｏｅ、Ｆｅ⁺²／Ｆｅ⁺³比は６／９４）１１００ｇを水２２０ｇ及びポリ（重合度１６）オキシエチレンプロピル、トリメトキシシランのシランカップリング剤を１５０ｇ添加して、オープンニーダー３時間良く混練した。この粗分散した粘性のある液を７０℃で１昼夜乾燥し水を除去した後、１１０℃、１時間加熱して処理をし、表面処理をした磁気粒子を作製した。
【０１７７】
さらに以下の処方で、再びオープンニーダーにて混練した。
【０１７８】
上記表面処理済み磁気粒子 １０００ｇ
ジアセチルセルロース １７ｇ
メチルエチルケトン １００ｇ
シクロヘキサノン １００ｇ
さらに、以下の処方でサンドミル（１／４Ｇ）で２００ｒｐｍ、４時間微細分散した。
【０１７９】
上記混練品 １００ｇ
ジアセチルセルロース ６０ｇ
メチルエチルケトン ３００ｇ
シクロヘキサノン ３００ｇ。
さらにジアセチルセルロースと、硬化剤として C₂H₅C(CH_2OCONH-C₈H₃(CH₃)NCO)₃をバインダーに対して２０ｗｔ％添加した。得られた液の粘度は約８０ｃＰとなるように等量のメチルエチルケトンとシクロヘキサノンで希釈した。又、塗布は上記の導電性層の上にバーコーターで実施し、膜厚は１．２μであった。磁性体の量０．６ｇ／m²となるように塗布した。またマット剤としてシリカ粒子（０．３μｍ）と研磨剤の酸化アルミ（０．５μｍ）をそれぞれ１０mg／m²となるように添加した。乾燥は１１５℃、６分実施した（乾燥ゾーンのローラーや搬送装置はすべて１１５℃となっている）。
【０１８０】
Ｘ−ライトのステータスＭでブルーフィルターを用いた時の、磁気記録層のＤ8 の色濃度の増加分は、約０．１であった。また、磁気記録層の飽和磁化モーメントは４．２ｅｍｕ／m²、保磁力９２３Ｏｅ、角形比は６５％であった。
【０１８１】
３−３）滑り層の調製
下記処方液を化合物の固形分塗布量が下記のようになるように塗布し、１１０℃で５分乾燥させて滑り層を得た。
【０１８２】
ジアセチルセルロース ２５mg／m²
C₆H₁₃CH(OH)C₁₀H₂₀COOC₄₀H₈₁ 化合物ａ ６mg／m²
C₅₀H₁₀₁O(CH₂CH₂O)₁₆H 化合物ｂ ９mg／m²
なお、化合物ａ／化合物ｂ（６：９）は、キシレンとプロピレングリコールモノメチルエーテル（容量比１：１）を同量液中で１０５℃に加熱、溶解し、この液を１０倍量のプロピレングリコールモノメチルエーテル（２５℃）に注加して微細分散液とした。さらに５倍量のアセトン中で希釈し、高圧ホモジナオザー（２００気圧）で再分散を実施し、分散物（平均粒径０．０１μ）にしてから添加して用いた。
【０１８３】
得られた滑り層の性能は、動摩擦係数０．０６（５mmφのステンレス硬球、荷重１００ｇ、スピード６cm／minute) 、静摩擦係数０．０７（クリップ法）であり優れた特性を有する。また後述する乳剤面との滑り特性も動摩擦係数０．１２であった。
【０１８４】
４）感光材料層の塗設
次に、前記で得られたバック層の反対側に下記の組成の各層を重層塗布し、カラーネガ写真フィルムを作成した。
【０１８５】
第５層（高感度赤感乳剤層）に実施例Ｘ記載の乳剤Ｙ１〜Ｙ５を含んでおり、各々試料２０１〜２０５とした。
【０１８６】
（感光層組成）
各層に使用する素材の主なものは下記のように分類されているが、これらの素材の用途は、記載される用途に限られるものではない；
ＥｘＣ：シアンカプラー ＵＶ ：紫外線吸収剤
ＥｘＭ：マゼンタカプラー ＨＢＳ：高沸点有機溶剤
ＥｘＹ：イエローカプラー Ｈ ：ゼラチン硬化剤
ＥｘＳ：増感色素
各成分に対応する数字は、ｇ／m²単位で表した塗布量を示し、ハロゲン化銀については、銀換算の塗布量を示す。ただし増感色素については、同一層のハロゲン化銀１モルに対する塗布量をモル単位で示す。
【０１８７】
（試料２０１）
第１層（ハレーション防止層）
黒色コロイド銀 銀 0.09
ゼラチン 1.60
ＥｘＭ−１ 0.12
ＥｘＦ−１ 2.0×10^-3
固体分散染料ＥｘＦ−２ 0.030
固体分散染料ＥｘＦ−３ 0.040
ＨＢＳ−１ 0.15
ＨＢＳ−２ 0.02。
【０１８８】
第２層（中間層）
沃臭化銀乳剤Ｍ 銀 0.065
ＥｘＣ−２ 0.04
ポリエチルアクリレートラテックス 0.20
ゼラチン 1.04。
【０１８９】
第３層（低感度赤感乳剤層）
沃臭化銀乳剤Ｄ 銀 0.50
ＥｘＣ−１ 0.17
ＥｘＣ−３ 0.030
ＥｘＣ−４ 0.10
ＥｘＣ−５ 0.020
ＥｘＣ−６ 0.010
Ｃｐｄ−２ 0.025
ＨＢＳ−１ 0.10
ゼラチン 0.87。
【０１９０】
第４層（中感度赤感乳剤層）
沃臭化銀乳剤Ｃ 銀 0.70
ＥｘＳ−１ 3.5×10^-4
ＥｘＳ−２ 1.6×10^-5
ＥｘＳ−３ 5.1×10^-4
ＥｘＣ−１ 0.13
ＥｘＣ−２ 0.060
ＥｘＣ−３ 0.0070
ＥｘＣ−４ 0.090
ＥｘＣ−５ 0.015
ＥｘＣ−６ 0.0070
Ｃｐｄ−２ 0.023
ＨＢＳ−１ 0.10
ゼラチン 0.75。
【０１９１】
第５層（高感度赤感乳剤層）
実施例Ｘ記載の乳剤 銀 1.40
ＥｘＳ−１ 2.4×10^-4
ＥｘＳ−２ 1.0×10^-4
ＥｘＳ−３ 3.4×10^-4
ＥｘＣ−１ 0.10
ＥｘＣ−３ 0.045
ＥｘＣ−６ 0.020
ＥｘＣ−７ 0.010
Ｃｐｄ−２ 0.050
ＨＢＳ−１ 0.22
ＨＢＳ−２ 0.050
ゼラチン 1.10。
【０１９２】
第６層（中間層）
Ｃｐｄ−１ 0.090
固体分散染料ＥｘＦ−４ 0.030
ＨＢＳ−１ 0.050
ポリエチルアクリレートラテックス 0.15
ゼラチン 1.10。
【０１９３】
第７層（低感度緑感乳剤層）
沃臭化銀乳剤Ｅ 銀 0.15
沃臭化銀乳剤Ｆ 銀 0.10
沃臭化銀乳剤Ｇ 銀 0.10
ＥｘＳ−４ 3.0×10^-5
ＥｘＳ−５ 2.1×10^-4
ＥｘＳ−６ 8.0×10^-4
ＥｘＭ−２ 0.33
ＥｘＭ−３ 0.086
ＥｘＹ−１ 0.015
ＨＢＳ−１ 0.30
ＨＢＳ−３ 0.010
ゼラチン 0.73。
【０１９４】
第８層（中感度緑感乳剤層）
沃臭化銀乳剤Ｈ 銀 0.80
ＥｘＳ−４ 3.2×10^-5
ＥｘＳ−５ 2.2×10^-4
ＥｘＳ−６ 8.4×10^-4
ＥｘＣ−８ 0.010
ＥｘＭ−２ 0.10
ＥｘＭ−３ 0.025
ＥｘＹ−１ 0.018
ＥｘＹ−４ 0.010
ＥｘＹ−５ 0.040
ＨＢＳ−１ 0.13
ＨＢＳ−３ 4.0×10^-3
ゼラチン 0.80。
【０１９５】
第９層（高感度緑感乳剤層）
沃臭化銀乳剤Ｉ 銀 1.25
ＥｘＳ−４ 3.7×10^-5
ＥｘＳ−５ 8.1×10^-5
ＥｘＳ−６ 3.2×10^-4
ＥｘＣ−１ 0.010
ＥｘＭ−１ 0.020
ＥｘＭ−４ 0.025
ＥｘＭ−５ 0.040
Ｃｐｄ−３ 0.040
ＨＢＳ−１ 0.25
ポリエチルアクリレートラテックス 0.15
ゼラチン 1.33。
【０１９６】
第10層（イエローフィルター層）
黄色コロイド銀 銀 0.015
Ｃｐｄ−１ 0.16
固体分散染料ＥｘＦ−５ 0.060
固体分散染料ＥｘＦ−６ 0.060
油溶性染料ＥｘＦ−７ 0.010
ＨＢＳ−１ 0.60
ゼラチン 0.60。
【０１９７】
第11層（低感度青感乳剤層）
沃臭化銀乳剤Ｊ 銀 0.09
沃臭化銀乳剤Ｋ 銀 0.09
ＥｘＳ−７ 8.6×10^-4
ＥｘＣ−８ 7.0×10^-3
ＥｘＹ−１ 0.050
ＥｘＹ−２ 0.22
ＥｘＹ−３ 0.50
ＥｘＹ−４ 0.020
Ｃｐｄ−２ 0.10
Ｃｐｄ−３ 4.0×10^-3
ＨＢＳ−１ 0.28
ゼラチン 1.20。
【０１９８】
第12層（高感度青感乳剤層）
沃臭化銀乳剤Ｌ 銀 1.00
ＥｘＳ−７ 4.0×10^-4
ＥｘＹ−２ 0.10
ＥｘＹ−３ 0.10
ＥｘＹ−４ 0.010
Ｃｐｄ−２ 0.10
Ｃｐｄ−３ 1.0×10^-3
ＨＢＳ−１ 0.070
ゼラチン 0.70。
【０１９９】
第13層（第１保護層）
ＵＶ−１ 0.19
ＵＶ−２ 0.075
ＵＶ−３ 0.065
ＨＢＳ−１ 5.0×10^-2
ＨＢＳ−４ 5.0×10^-2
ゼラチン 1.8。
【０２００】
第14層（第２保護層）
沃臭化銀乳剤Ｍ 銀 0.10
Ｈ−１ 0.40
Ｂ−１（直径 1.7 μｍ） 5.0×10^-2
Ｂ−２（直径 1.7 μｍ） 0.15
Ｂ−３ 0.05
Ｓ−１ 0.20
ゼラチン 0.70。
【０２０１】
更に、各層に適宜、保存性、処理性、圧力耐性、防黴・防菌性、帯電防止性及び塗布性をよくするためにＷ−１ないしＷ−３、Ｂ−４ないしＢ−６、Ｆ−１ないしＦ−１７及び、鉄塩、鉛塩、金塩、白金塩、パラジウム塩、イリジウム塩
、ロジウム塩が含有されている。
【０２０２】
【表２】

表２において、
（１）乳剤Ｊ〜Ｌは特開平2-191938号の実施例に従い、二酸化チオ尿素とチオスルフォン酸を用いて粒子調製時に還元増感されている。
（２）乳剤Ｃ〜Ｉは特開平3-237450号の実施例に従い、各感光層に記載の分光増感色素とチオシアン酸ナトリウムの存在下に金増感、硫黄増感とセレン増感が施されている。
（３）平板状粒子の調製には特開平1-158426号の実施例に従い、低分子量ゼラチンを使用している。
（４）平板状粒子には特開平3-237450号に記載されているような転位線が高圧電子顕微鏡を用いて観察されている。
（５）乳剤Ｌは特開昭60-143331 号に記載されている内部高ヨードコアーを含有する二重構造粒子である。
【０２０３】
有機固体分散染料の分散物の調製
下記、ＥｘＦ−２を次の方法で分散した。即ち、水21.7ｍＬ及び５％水溶液のｐ−オクチルフェノキシエトキシエトキシエタンスルホン酸ソーダ３ｍＬ並びに５％水溶液のｐ−オクチルフェノキシポリオキシエチレンエ−テル（重合度10） 0.5ｇとを 700ｍＬのポットミルに入れ、染料ＥｘＦ−２を 5.0ｇと酸化ジルコニウムビ−ズ（直径１mm） 500ｍＬを添加して内容物を２時間分散した。この分散には中央工機製のＢＯ型振動ボールミルを用いた。分散後、内容物を取り出し、12.5％ゼラチン水溶液８ｇに添加し、ビーズを濾過して除き、染料のゼラチン分散物を得た。染料微粒子の平均粒径は0.44μｍであった。
【０２０４】
同様にして、ＥｘＦ−３、ＥｘＦ−４及びＥｘＦ−６の固体分散物を得た。染料微粒子の平均粒径はそれぞれ、0.24μｍ、0.45μｍ、0.52μｍであった。ＥｘＦ−５は欧州特許出願公開（EP）第549,489A号明細書の実施例１に記載の微小析出（Microprecipitation）分散方法により分散した。平均粒径は0.06μｍであった。
【０２０５】
【化３】

【０２０６】
【化４】

【０２０７】
【化５】

【０２０８】
【化６】

【０２０９】
【化７】

【０２１０】
【化８】

【０２１１】
【化９】

【０２１２】
【化１０】

【０２１３】
【化１１】

【０２１４】
【化１２】

【０２１５】
【化１３】

【０２１６】
【化１４】

【０２１７】
【化１５】

【０２１８】
【化１６】

【０２１９】
【化１７】

【０２２０】
【化１８】

これらの試料を４０℃、相対湿度７０％の条件に１４時間放置した後、白色光により１／１００秒間の露光を与え、実施例２と同様のカラー現像処理を行った。ただし、発色現像時間を３分１５秒で行った。
【０２２１】
赤色フィルターを通して濃度測定を行い、濃度１．８および２．５を与える露光量の逆数により相対感度を求めた。また、濃度１．８を与える一様な露光を行い、粒状度の測定も行った。
【０２２２】
粒状度は、前述の現像処理を行なった後、マクミラン社刊、“ザ・セオリー・オブ・ザ・フォトグラフィック・プロセス”６１９ページに記述される方法で測定した。
【０２２３】
結果を表３に示す。ただし試料２０１の感度および粒状度をそれぞれ１００とし、それぞれ相対値で表した。
【０２２４】
【表３】

表３より、本発明の乳剤を用いた試料は比較試料に対して、粒状度を改良しつつ、高感度を達成しており、本発明の効果が顕著である。
【０２２５】
【発明の効果】
本発明は、４モル％以上の沃化物を含有した極薄平板状粒子乳剤において、過熟成工程及びアミノ基修飾ゼラチンを用いることで、単分散性に優れた粒子形成が可能となる。また、本発明混合機を用いた微粒子添加成長を、上記発明と併用することで、単分散性を損なうことなく、更なる薄板化が可能となる。
【図面の簡単な説明】
【図１】本発明の１つの実施形態において用いるの攪拌装置の概略構成を示す断面図である。
【図２】本発明の１つの実施形態のハロゲン化銀乳剤の製造工程を示す概略断面図である。
【図３】本発明の１つの実施形態において用いる攪拌装置に使用される磁気カップリングの概略構成を示す斜視図である。
【図４】図３に示した磁気カップリングの作用を示す斜視図である。
【符号の説明】
１ 反応容器
２ 保護コロイド水溶液
３ 撹拌羽根
１０ 攪拌装置
１１，１２，１３ 液供給口
１６ 液排出口
１８ 攪拌槽
１９ 槽本体
２０ シールプレート
２１，２２ 攪拌羽根
２６ 外部磁石
２８，２９ モータ
３１ 回転中心軸線
３３ 両面２極型磁石
３５ 左右２極型磁石
Ｌ 磁力線[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a silver halide photographic emulsion, a method for producing the same, and a silver halide photographic light-sensitive material containing the emulsion. More specifically, the present invention relates to a tabular silver halide emulsion, a process for producing the same, and a silver halide photographic light-sensitive material containing the emulsion.
[0002]
[Prior art]
U.S. Pat. No. 5,250,403 (Antoniades et al.) Records exposure in color photographic elements, particularly the minus blue (red and / or green) portion of the spectrum, in many respects, prior to the present invention. Thus tabular grain emulsions that are representative of the best available emulsions have been disclosed. Antoniodias et al. Disclosed a tabular grain emulsion in which tabular grains having {111} major faces accounted for more than 97% of the total grain projected area. These tabular grains have an average circle equivalent diameter (hereinafter also referred to as “ECD”) of at least 0.7 μm and a thickness of less than 0.07 μm. Tabular grain emulsions having a thickness of less than 0.07 μm are hereinafter referred to as “ultra-thin” tabular grain emulsions. Ultrathin tabular grain emulsions utilize silver efficiently, have an attractive sensitivity-granularity relationship, and have a high level of image sharpness in both emulsion layers and lower emulsion layers. Thus, it is suitable for use in color photographic elements, particularly minus blue recording emulsion layers.
[0003]
As recognized by Buhr et al., Research Disclosure, Vol. 253, Item 25330, May 1985, is recognized as a feature of tabular grains having a thickness in the range of 0.18-0.08 μm. As can be seen, the distinction between ultrathin tabular grain emulsions and other tabular grain emulsions is that tabular grains having a thickness in the range of 0.18 to 0.08 μm are most reflective in the visible spectrum. Is not shown. For multilayer photographic elements, the upper emulsion layer having an average tabular grain thickness in the range of 0.18 to 0.08 [mu] m must be carefully selected because the reflection characteristics vary greatly within the visible spectrum. Selecting ultrathin tabular grain emulsions for the construction of a multilayer photographic element eliminates the need to select different thicknesses in the various emulsion layers above other emulsion layers depending on the spectral reflectance. Thus, ultrathin tabular grain emulsions not only improve photographic performance, but also have the advantage of simplifying the construction of multilayer photographic elements.
[0004]
On the other hand, the presence of iodide in many photographic elements is universally used because it offers the advantage of improved sensitivity (more precisely, the sensitivity-granularity relationship is improved). In particular, an average silver iodide content in the range of 4 to 12 mole percent is typical for multicolor photographic element applications where the release of iodide ions during processing provides a useful interimage effect. Further, as described in European Patent (hereinafter also referred to as “EP”) 0362699A2, the grain morphology of the ultrathin tabular grain emulsion is unstable and may be dissolved during the dispersion process and chemical sensitization process after grain formation. Are known.
[0005]
As is well known in the art, the improvement in monodispersity of tabular grain emulsions greatly affects the improvement of various photographic properties. In particular, an ultrathin tabular grain emulsion has a very large diameter in terms of a circle compared to a conventional tabular grain emulsion, and therefore the influence of the dispersibility on photographic properties is expected to be very large.
[0006]
[Problems to be solved by the invention]
The present invention is a silver halide photographic emulsion containing silver halide grains that are particularly excellent in photographic performance such as sensitivity-granularity, sharpness, gradation, etc., and is excellent in monodispersity, and more particularly in multilayer photographic elements. The first object is to provide a silver halide photographic emulsion useful as an emulsion layer (hereinafter also referred to as “emulsion of the present invention”).
[0007]
The present invention also provides a method for producing the above-described emulsion of the present invention, that is, an ultrathin tabular grain emulsion satisfying the silver iodide content capable of improving the relationship between sensitivity and granularity and excellent in monodispersity. This is the second purpose.
[0008]
A third object of the present invention is to provide a silver halide photographic light-sensitive material containing the emulsion of the present invention.
[0009]
[Means for Solving the Problems]
  (1) Tabular silver halide grains in which 97% or more of the projected area of all grains has a silver iodide content of 4 mol% to 15 mol%, a thickness of less than 0.07 μm, and an aspect ratio of 5 or moreA tabular silver halide grain having a high silver iodide-containing layer having a silver iodide content of 6 mol% or more as an outermost layerAnd a coefficient of variation of the diameter in terms of a circle of the projected area of all tabular grains is less than 30%.
[0012]
  (2)  Amino groups in gelatin (-NH₂Wherein the group is produced in a dispersion medium solution containing gelatin into which at least two carboxyl groups (-COOH groups) are introduced per chemically modified amino group. A method for producing a silver halide photographic emulsion as described in (1).
[0013]
  (3)  An aqueous solution of a water-soluble silver salt and an aqueous solution of a water-soluble halide are supplied from a supply port provided in a closed type stirring tank of the mixer,
  At least one stirring blade not having a rotating shaft penetrating the stirring tank wall is rotationally driven in the stirring tank to control the stirring state of the supplied aqueous solution,
  Discharge the silver halide fine particles generated after the stirring process from the outlet provided in the sealed stirring tank,
  The method for producing a silver halide photographic emulsion as described in (1) above, wherein the silver halide fine grains are supplied to a reaction vessel for causing nucleation and / or grain growth of silver halide grains. .
[0014]
  (4)  In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, at least one of the emulsion layers has the above-mentioned structure.(1)A silver halide photographic light-sensitive material comprising the silver halide photographic emulsion described in 1.
[0015]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is directed to a tabular grain silver halide emulsion containing a dispersion medium and a coprecipitated grain population comprising silver halide tabular grains having an aspect ratio of 5 or greater. 97% or more of the total projected area of the coprecipitated grain population is occupied by silver halide tabular grains, and the coefficient of variation in the circle-converted diameter of the grains of the coprecipitated grain population is less than 30%. .
[0016]
In particularly preferred embodiments of the invention, the silver halide tabular grains may occupy more than 99% of the total projected area of the coprecipitated tabular grains. Furthermore, the coefficient of variation of the circle equivalent diameter of the coprecipitated silver halide grains may be less than 20%.
[0017]
As used herein, the term “tabular grain” refers to a particle having two parallel principal planes in which the principal plane is hexagonal or triangular when viewed from a direction perpendicular to the principal plane. Say. The main plane of such tabular grains is in the {111} crystal plane, and the tabular shape has at least two parallel twin planes (or three or more in some cases) oriented parallel to the main plane. It is generally accepted that this is the case.
In one particularly preferred embodiment of the present specification, more than 90% of the coprecipitated silver halide tabular grains (ratio to the total projected area) have a hexagonal principal plane. Moreover, in the particle | grains which have a hexagonal main plane, it is preferable that the ratio of the side of an adjacent main plane is less than two.
[0018]
As used herein, the “circular equivalent diameter” of a particle is the diameter of a circle having an area equal to the projected area of the particle, and is also referred to as “ECD” for short. The meaning of the term “coefficient of variation” or “COV” for short is recognized in the art. The coefficient of variation in the diameter of a particle in terms of a circle refers to 100 times the standard deviation of the diameter in terms of a circle of a particle divided by the average value of the diameter in terms of a circle of the particle.
[0019]
Any combination of tabular grain ECD and thickness (t) capable of providing an aspect ratio (ECD / t) of at least 5 generally provides photographic advantages. In the present invention, the aspect ratio is preferably 8 or more and 100 or less, and more preferably the aspect ratio is 10 to 80.
[0020]
In the emulsion of the present invention, the ECD may take any value as long as the tabular grains satisfy the requirements specified in the present specification. However, the ECD of the particles in the present invention is preferably less than 10 μm, more preferably less than 6 μm, and even more preferably in the range of 0.5 to less than 6 μm.
[0021]
The tabular grain emulsions of the present invention are directed to ultrathin tabular grain emulsions, ie, emulsions in which the thickness of the silver halide tabular grains is less than 0.07 μm. Particularly preferred ultrathin tabular grain emulsions of the present invention are those in which the thickness of the silver halide tabular grains is within the range of 0.02 to less than 0.06 μm. Ultrathin tabular grain emulsions speed up processing, reduce graininess as a function of silver coverage, increase minus blue (500-700 nm exposure) speed, and reduce blue and minus blue degradation speed. A wide range of photographic advantages such as an increase can be obtained.
[0022]
In the emulsion grains of the present invention, the silver halide contains from 4 mol% to 15 mol% of silver iodobromide based on the total amount of silver in the grains. The silver halide composition is preferably silver iodobromochloride or silver iodobromide, and most preferably silver iodobromide.
[0023]
The tabular silver halide grains contained in the emulsion of the present invention preferably have a so-called core / shell structure composed of a core having different silver iodide contents and a shell surrounding the core. The number of shells may be one or two or more. When the number of shells is two or more, the shell around the outside of the core is referred to as the first shell, the shell around the first shell is referred to as the second shell, and the outer shells are sequentially referred to as the first shell. It is called 3 shells and 4th shells. In the present specification, the term “outermost layer” refers to the outermost (surface) shell. The outermost layer has a silver amount of 10% or more and less than 50%, preferably 20% or more and less than 50%, more preferably 25% or more and less than 50%, based on the amount of silver per grain. The iodide content in the outermost layer is preferably 6 mol% or more based on the amount of silver in the outermost layer. More preferably, the iodide content in the outermost layer is less than 20 mol% based on the amount of silver in the outermost layer, more preferably 8 mol% or more and less than 15 mol%. The outermost layer can contain silver chloride. Silver chloride can be contained so as to be 0.4 to 20 mol% of chloride with respect to the total amount of silver. The halogen composition of the core is preferably pure silver bromide, but can contain 4 mol% or less iodide based on the amount of silver. When the grains contained in the emulsion of the present invention have an epitaxial junction described later, the epitaxial junction is also included in the outermost layer.
[0024]
An important feature of the present invention is the development of a new process for producing monodisperse ultrathin tabular grain emulsions.
[0025]
In general, silver halide emulsions are
Nucleation → Aging → Growth
Can be manufactured by the process. In contrast to the general silver halide emulsion production process, the novel production method of the present invention is the introduction of an overripening process.
[0026]
Hereinafter, each process of nucleation, ripening, over-ripening, and growth will be described.
[0027]
1. Nucleation
As the nucleation process of monodispersed ultrathin tabular grains, a tabular grain nucleation process known per se can be used. That is, the double jet method, which is generally performed by adding a silver salt aqueous solution and an alkali halide aqueous solution to a reaction vessel holding an aqueous solution of gelatin, or the single jet method in which a silver salt aqueous solution is added to a gelatin solution containing an alkali halide. Is used. Moreover, the method of adding aqueous alkali halide solution to the gelatin solution containing a silver salt as needed can also be used. Furthermore, if necessary, a gelatin solution, a silver salt solution, and an aqueous alkali halide solution are added to a mixer disclosed in JP-A-2-44335 and immediately transferred to a reaction vessel to nucleate tabular grains. Can also be done. Further, as disclosed in US Pat. No. 5,104,786, nucleation can be performed by passing an aqueous solution containing an alkali halide and a protective colloid solution through a pipe and adding an aqueous silver salt solution thereto.
[0028]
For nucleation, it is preferable that gelatin is used as a dispersion medium and the dispersion medium is formed under the conditions of pBr of 1 to 4. The concentration of the dispersion medium is preferably 10% by weight or less, and more preferably 1% by weight or less. The temperature during nucleation is preferably from 5 to 60 ° C, but more preferably from 5 to 48 ° C when producing fine tabular grains having an average particle size of 0.5 µm or less.
[0029]
The composition of the alkali halide solution to be added is Br.^-Against I^-The content is not more than the solid solubility limit of AgBrI to be produced, preferably not more than 10 mol%.
[0030]
2. Aging
In the nucleation in 1 above, fine particles other than tabular grains (particularly regular and single twin grains) are formed. Before entering the growth step described below, it is necessary to eliminate grains other than tabular grains to obtain nuclei having a shape to be tabular grains and having good monodispersity. In order to make this possible, it is well known to perform Ostwald ripening following nucleation.
[0031]
Immediately after nucleation, pBr is adjusted, and then the temperature is increased and ripening is performed until the hexagonal tabular grain ratio reaches the maximum. The aging temperature is 40 to 80 ° C., preferably 50 to 80 ° C., and the pBr is 1.2 to 3.0. At this time, a silver halide solvent may be added so that grains other than the tabular grains disappear quickly. In this case, the concentration of the silver halide solvent is preferably 0.3 mol / L (hereinafter referred to as “L”) or less, more preferably 0.2 mol / L or less. As the silver halide solvent, those usually used can be used, but when used as a direct reversal emulsion, NH used on the alkaline side as the silver halide solvent._ThreeMore preferred are silver halide solvents such as thioether compounds used on the neutral and acidic side.
[0032]
Ripening in this way results in approximately ~ 100% tabular grains only.
[0033]
In the method for producing an emulsion of the present invention, the end of the ripening step means grains other than tabular grains having a main plane of hexagon or triangle and having at least two twin planes (regular and single twin crystals). This refers to the point at which the particles have disappeared. The disappearance of grains other than tabular grains having a hexagonal or triangular main plane and having at least two twin planes can be confirmed by observing a TEM image of a replica of the grains.
[0034]
3. Overage
The novel production method of the monodispersed ultrathin tabular grain emulsion of the present invention is different from the general silver halide emulsion production method in which the immediate growth is started after the ripening in 2 above, and the “overripening step” Has been introduced. When an ultrathin tabular grain emulsion is prepared by a general silver halide emulsion production method (nucleation-ripening-growth), a slab whose size has been greatly reduced from the average value of the circle-equivalent diameter (ECD) must be obtained. Many exist, and as a result, dispersibility is greatly deteriorated.
[0035]
This suggests that the anisotropic growth speed of the tabular grains obtained by the ripening process is originally different for each tab.
[0036]
In the specification of the present application, the term “over-ripening step” means a tabular shape having a slow anisotropic growth speed by further aging the tabular grains themselves after ripening (ripening step) until the hexagonal tabular grain ratio reaches the maximum. This is a step of erasing particles. In the ultrathin tabular grain emulsion of the present invention, when the number of tabular grains obtained in the ripening step is 100, the number of tabular grains is preferably reduced to 90 or less by the overripening step. More preferably, it is reduced to 60 or more and 80 or less. It was found that the COV of the tabular grains deteriorated with respect to the COV in the ripening process by the above-mentioned process, but after the growth, a monodispersed ultrathin tabular grain emulsion having no reduced size tabs was obtained. .
[0037]
In the method for producing an emulsion of the present invention, conditions such as pBr and temperature in the overripening step can be set to be the same as those in the ripening step. In the overripening step, a silver halide solvent can be added in the same manner as in the ripening step, and the type, concentration, etc. can be set to be the same as those in the ripening step.
[0038]
4). growth
It is preferable to maintain pBr in the crystal growth period following the over-ripening process at 1.4 to 3.5. When the gelatin concentration in the dispersion medium solution before entering the growth process is low (1% by weight or less), gelatin may be additionally added. At that time, the gelatin concentration in the dispersion medium solution is preferably 1 to 10% by weight.
[0039]
Ag during crystal growth⁺The halogen ion addition rate is preferably 50% or less, preferably 30% or less, more preferably 20% or less of the critical crystal growth rate. In this case, the addition rate of silver ions and halogen ions is increased with crystal growth. In this case, the addition rate of silver salt and halogen salt aqueous solution as described in Japanese Patent Publication Nos. 48-36890 and 52-16364. The concentration of these aqueous solutions may be increased.
[0040]
The means for adding iodide deposited on the nucleus during the growth period is not only a method of directly supplying as halogen ions, but also Ag.⁺, And a method of adding AgI fine particles at the time of supplying halogen ions, a method of supplying them as AgBrI fine particles, and a method of using them together are possible. These fine particles preferably have a sphere equivalent diameter of 0.1 to 0.005 μm, more preferably 0.05 to 0.005 μm.
[0041]
Another means that has contributed to the development of a novel monodispersed ultrathin tabular grain emulsion production method, which is an important feature of the present invention, is that at least 2 carboxyl groups are newly added when the amino group in gelatin is chemically modified. That is, gelatin introduced into the particles is used during grain formation.
[0042]
In order to increase the aspect ratio in the technical field, various attempts have been made to reduce the thickness of tabular grains. Japanese Patent Publication No. 5-12696 discloses a method of preparing tabular grains having a small thickness using gelatin in which methionine groups in gelatin are invalidated with hydrogen peroxide or the like as a dispersion medium. Japanese Patent Application Laid-Open No. 8-82883 discloses a method for preparing thin tabular grains using gelatin in which amino groups and methionine groups are invalidated as a dispersion medium. US Pat. No. 5,380,642 and JP-A-8-292508 disclose a method for preparing thin tabular grains using a synthetic polymer as a dispersion medium.
[0043]
However, all of these techniques, considered to be essential for conventional ultrathin tabular grain emulsions, result in deterioration of monodispersity with increasing silver iodide content.
[0044]
In contrast, by using the amino group-modified gelatin during grain formation, an ultrathin tabular grain emulsion having a small thickness and monodispersed irrespective of the silver iodide content was obtained.
[0045]
Furthermore, the amino group-modified gelatin greatly suppresses the enlarging of some of the plates with high anisotropic growth speed during the overripening step, so at least from the growth step, preferably before the start of the overripening step, More preferably, by adding the amino group-modified gelatin immediately after the nucleation, a monodispersed ultrathin plate in which the tabular grains that are extremely large or small are not present in the grown grains. A grain emulsion was obtained. The amino group-modified gelatin mainly used in the present invention will be described.
[0046]
In the present invention, amino group-modified gelatin conventionally used for forming tabular grains can be used, and for example, those described in JP-A-8-82883 can be used. Amino group-modified gelatin is a primary amino group (-NH₂) Is a secondary amino group (—NH—), a tertiary amino group, or deaminated to obtain tabular grains having a small thickness. In addition, when an acid anhydride such as phthalic anhydride, succinic anhydride, or maleic anhydride is reacted in amino group-modified gelatin, the amino group is modified to form —NH₂Instead of one group, one —COOH group is introduced. Focusing on this introduced -COOH group and increasing the number of introduced -COOH groups, the effect of further reducing the thickness of the tabular grains without polydispersing the grain size distribution was observed.
[0047]
As a specific means for introduction of —COOH group, an amino group (—NH₂) Can be modified. Examples of the reagent are listed below as specific examples, but are not limited thereto.
[0048]
(i) A compound having at least two carboxylic acids (—COOH) that forms at least one acid anhydride in its structure. Examples include trimellitic anhydride, pyromellitic anhydride, merit anhydride, and the like.
(ii) A compound having at least two carboxylic acids and having at least one cyanate in its structure. For example, phenyl isocyanate etc. are mentioned.
(iii) A compound having at least two carboxylic acids and having at least one aldehyde or ketone in its structure.
(iv) A compound having at least two carboxylic acids and having at least one imide ester in its structure.
[0049]
Amino group (-NH₂The substitution rate of the lysine group is -NH of the lysine residue in the gelatin molecule.₂Group (ε-NH₂Group) is 60% or more, preferably 80% or more, more preferably 90% or more.₂Group (α-NH₂Group, ε-NH₂Group, guanidyl group) is 30% or more, preferably 50% or more.
[0050]
Hereinafter, an example of a method for producing a modified gelatin in which an amino group is chemically modified and a carboxyl group is newly introduced will be described. However, the method for producing a modified gelatin used in the present invention is not limited thereto.
[0051]
(Trimeritized gelatin manufacturing method)
Various methods have been developed for the modification of amino groups. For example, U.S. Pat. Nos. 2,525,753, 3,118,766, 2,614,928, 2,614,929, JP-B-40-15585, JP-A-8-82883, and Photographic Society of Japan, Vol. 58, page 25 (1995) You can refer to the description.
[0052]
As a method for producing trimellitated gelatin, the following method described in Journal of the Photographic Society of Japan, Vol. 58, page 25 (1995) can be referred to.
[0053]
After adjusting the pH of a 15% gelatin aqueous solution maintained at 60 ° C. to 9.0, an aqueous trimellitic anhydride solution is added. During the reaction, the pH is kept at 8.75 to 9.25 and the reaction is allowed to proceed for 1 hour. After completion of the reaction, deionization is performed by ultrafiltration. The pH is adjusted to 6.0 and then dried to obtain gelatin powder.
[0054]
The amino group-modified gelatin in the ultrathin tabular grain emulsion production process is preferably present at least before the growth, preferably before the start of the overripening process, and more preferably immediately after the nucleation. Further, the pH in the dispersion medium at that time is preferably 4 or more and 10 or less.
[0055]
In this case, the concentration of gelatin with respect to the dispersion medium solution is preferably 10% by weight or less.
[0056]
Next, a method for producing a novel monodispersed ultrathin tabular grain emulsion using an apparatus contributing to thinning, which is an important feature of the present invention, will be described in detail.
[0057]
That is, an aqueous solution of a water-soluble silver salt and an aqueous solution of a water-soluble halide are supplied from a supply port provided in a closed-type stirring tank of a mixer, and at least one stirring blade not having a rotating shaft penetrating the stirring tank wall is attached to the stirring blade. It is rotated in the stirring tank to control the stirring state of the supplied aqueous solution, and the silver halide fine particles generated after the stirring process are discharged from the outlet provided in the closed-type stirring tank. This is a method for producing a silver halide emulsion by supplying the silver halide fine particles to a reaction vessel for causing nucleation and / or grain growth of silver grains.
[0058]
One embodiment for performing nucleation and / or grain growth by this method is shown in FIG. In FIG. 2, first, the reaction vessel 1 contains a protective colloid aqueous solution 2. The protective colloid aqueous solution is stirred by a stirring blade 3 (a propeller type is shown in this figure) attached to a rotating shaft. A silver salt aqueous solution, a halide salt aqueous solution and, if necessary, a protective colloid aqueous solution are introduced into addition systems (supply ports) 11, 12, and 13, respectively, in a mixer 10 (described later in FIG. 1) installed outside the reaction vessel. (At this time, if necessary, the protective colloid aqueous solution may be added to the silver salt aqueous solution and / or the halide salt aqueous solution.) It introduce | transduces into reaction container 1 by the system (discharge port) 16, and nucleation is performed in reaction container. At this time, the emulsion discharged from the mixer can be stored in a separate container and then added to the reaction container.
[0059]
After nucleation is completed in the reaction vessel, a silver salt aqueous solution, a halide salt aqueous solution and, if necessary, a protective colloid aqueous solution are further introduced into the addition system 11, 12, and 13 into the mixer 10, respectively. (At this time, if necessary, the protective colloid aqueous solution may be added to the silver salt aqueous solution and / or the halide salt aqueous solution.) It is continuously introduced into the reaction vessel 1 by the system 16 and the nuclei already formed in the reaction vessel are grown.
[0060]
FIG. 1 shows an embodiment of a mixer (stirring device) according to this method.
[0061]
If the drive shaft is attached to the stirring blade as in the prior art, and the stirring blade is rotated at such a high speed by a drive device outside the mixer, the sealing between the mixing tank and the drive shaft becomes very difficult. In the present invention, as described below, this problem is solved by not using a drive shaft by rotation by magnetic induction by an agitating blade connected by a magnetic coupling and an external magnet. In FIG. 1, the agitation tank 18 is composed of a tank body 19 having a central axis directed in the vertical direction and a seal plate 20 serving as a tank wall that closes the upper and lower opening ends of the tank body 19. The agitation tank 19 and the seal plate 20 are made of a nonmagnetic material having excellent magnetic permeability. The stirring blades 21 and 22 are spaced apart from the opposite upper and lower ends in the stirring tank 18 and are driven to rotate in opposite directions. Each of the stirring blades 21 and 22 constitutes a magnetic coupling C with an external magnet 26 disposed on the outside of the tank wall (seal plate 20) where the stirring blades 21 and 22 are close to each other. That is, the stirring blades 21 and 22 are coupled to the external magnets 26 by magnetic force, and are rotated in opposite directions by driving the external magnets 26 with independent motors 28 and 29.
[0062]
Further, in FIG. 1, the mixer includes three liquid supply ports 11, 12, and 13 through which a silver salt aqueous solution, a halide salt aqueous solution and, if necessary, a colloid aqueous solution are allowed to flow, and the silver halide fine particles after the stirring process is finished. A stirring tank 18 having a discharge port 16 for discharging the emulsion, and a pair of stirring blades 21 which are stirring means for controlling the stirring state of the liquid in the stirring tank 18 by being rotationally driven in the stirring tank 18. , 22. The mixer 18 is often cylindrical, but a rectangular parallelepiped, a hexagon, and other various shapes are used. Further, the pair of stirring blades are spaced apart from the opposite upper and lower ends in the stirring tank 18 and are driven to rotate in opposite directions. The pair of stirring blades are arranged in the opposite vertical direction in FIG. 1, but may be in the opposite lateral direction or in the oblique direction. In FIG. 1, a pair of two stirring blades are used at opposite positions, but it is also possible to use two or more pairs of even number of four or more stirring blades rotating in opposite directions. It is also possible to use an odd number (including one) of stirring blades that do not make a difference. Further, even more efficient stirring can be performed by using a pair of even number of stirring blades rotating in opposite directions and an odd number (including one) of stirring blades.
[0063]
In the present invention, when driving the stirring blades facing each other in the mixer, it is necessary to rotate the stirring blades at a high speed in order to achieve higher mixing efficiency. The rotational speed is 1000 r. p. m. Above, preferably 3000 r. p. m. Above, more preferably 5000 r. p. m. That's it. A pair of stirring blades rotating in opposite directions may be driven at the same rotational speed or driven at different rotational speeds.
[0064]
FIG. 3 shows the configuration of the magnetic coupling C at the lower end of the stirring tank 18. In the magnetic coupling C of this embodiment, each of the stirring blades 21 and 22 constituting the magnetic coupling C has an N pole surface and an S pole surface with respect to the rotation center axis 31 as illustrated. A double-sided dipole magnet 33 arranged in parallel and overlapping with the rotation center axis 31 in between is used. The external magnet 26 uses left and right bipolar magnets (U-shaped magnets) 35 that are arranged in symmetrical positions with respect to the rotation center axis 31 on a plane in which the N pole surface and the S pole surface are orthogonal to the rotation center axis 31. ing. Contrary to the above, in this magnetic coupling C, the same effect can be obtained by using a double-sided bipolar magnet 33 for the external magnet 26 and a right-and-left bipolar magnet 35 for the stirring blades 21 and 22. You can get an effect.
[0065]
In the magnetic coupling C described above, the magnetic field lines L connecting the external magnet 26 and the stirring blades 21 and 22 are as shown in FIG. 4A. For example, the magnetic coupling is configured by left and right bipolar magnets. As compared with the magnetic flux formed in this case, the diameter of the magnetic flux connecting the magnets can be doubled. At the same time, when the external magnet 26 is rotated, the magnetic flux is deflected as shown in FIG. The magnetic flux viscosity can be prevented, and the coupling strength as a coupling is greatly improved. By using a high-rotation type motor for the motors 28 and 29, the stirring blades 21 and 22 have a high speed. Rotation can be enabled.
[0066]
In the stirring device 10 shown in FIG. 1, the pair of stirring blades 21 and 22 that are opposed to each other in the tank 18 are indicated by a wavy arrow (X) and a solid arrow (Y) in the figure, A different stirring flow is formed in the tank 18. Since the stirring flows formed by the respective stirring blades 21 and 22 have different flow directions, a high-speed turbulent flow that collides with each other and promotes stirring in the tank 18 is realized in the tank 18, and the flow becomes steady. When the rotation speed of the stirring blades 21 and 22 is increased, the formation of a cavity around the rotation axis of the stirring blades 21 and 22 is prevented, and at the same time, the stirring tank is not sufficiently subjected to the stirring action. It is possible to prevent a disadvantage that a steady flow that flows in the tank 18 along the inner peripheral surface of the tank 18 is formed.
[0067]
Moreover, since the stirring blades 21 and 22 in the stirring tank 18 are connected to motors 28 and 29 arranged outside the tank 18 by magnetic coupling, it is necessary to insert a rotating shaft into the tank wall of the tank 18. Since the agitation tank 18 can be made into a closed container structure, leakage of the agitated and mixed liquid to the outside of the tank is prevented, and at the same time, the lubricating oil (sealing liquid) for the rotating shaft is mixed into the tank 18 as an impurity. This can prevent deterioration of the quality of the silver halide emulsion.
[0068]
Further, the magnetic coupling C shown in FIG. 3 is a combination of a so-called front dipole magnet 33 and a left and right dipole magnet 35, and uses a magnetic coupling having a configuration in which the left and right dipole magnets 35 are opposed to each other. Compared with the case, since the coupling strength as a coupling is significantly improved, the stirring blades 21 and 22 can be rotated at a higher speed.
[0069]
The feature of this production method is that it is formed by a mixer having a strong stirring ability, and preferably has a particle size (sphere equivalent diameter) of 0.1 to 0.005 μm, more preferably 0.05 to 0.00. Very fine silver halide grains having a diameter of 005 μm are introduced into the reaction vessel, and are dispersed in the reaction vessel by stirring into the reaction vessel, and the individual particle size is fine, so that they are easily dissolved and again become silver ions. It becomes halide ions and causes uniform nucleation or particle growth in the reaction vessel. Further, the grains generated in the mixer are very fine and the number of grains is very large. From such a large number of grains, silver ions and halide ions (in the case of mixed crystal silver halide, the desired halide). Is released, so that uniform nucleation and growth can occur throughout the protective colloid in the reaction vessel. According to this method, a completely uniform silver halide mixed crystal (Mixed Crystal) can be prepared, and the complete uniformity can be easily confirmed with a cooled transmission electron microscope.
[0070]
In the method for producing an emulsion of the present invention, the ultrafine grains can be used in a nucleation step, a grain growth step, a nucleation step and a grain growth step. Preferably, the ultrafine particles can be used in a particle growth step. The residence time of the additive liquid introduced into the mixer in this method: t (seconds) is represented by the following.
[0071]
t = v / (a + b + c)
v: Volume of the mixing space of the mixer (mL)
a: Amount of silver salt solution added (mL)
b: Added amount of halide salt solution (mL)
c: Addition amount of protective colloid solution (mL)
t is 20 seconds or less, preferably 10 seconds or less, more preferably 5 seconds or less, and even more preferably 2 seconds or less. If the residence time is long, the ultrafine particles once generated in the mixer grow and become a larger size, and the size distribution is widened, which is not preferable.
[0072]
In this method, the protective colloid aqueous solution is added to the mixer, and the following addition method is used.
[0073]
a Inject protective colloid solution alone into the mixer. The concentration of the protective colloid is 0.5% or more, preferably 1% or more, and 20% or less. The flow rate is at least 20% to 300%, preferably 50% to 200% of the sum of the silver salt solution and halide solution.
[0074]
b. Include protective colloid in halide salt solution. The concentration of the protective colloid is 0.4% or more, preferably 1% or more, and 20% or less.
[0075]
c Include protective colloid in the silver salt solution. The concentration of the protective colloid is 0.4% or more, preferably 1% or more and 20% or less. In the case of using gelatin, gelatin silver is made from silver ions and gelatin, and photodecomposition and thermal decomposition are carried out to produce a silver colloid. Therefore, it is better to add an aqueous silver salt solution and a gelatin solution immediately before use.
[0076]
The methods a to c may be used alone or in combination, and three methods may be used simultaneously.
[0077]
In this method, in order to obtain finer particles with a mixer, the temperature of the mixer should be low, and the temperature is preferably 40 ° C. or lower, more preferably 35 ° C. or lower.
[0078]
It is also possible to include a small amount of chloride ion in the ultrathin tabular grain emulsion of the present invention. As disclosed in U.S. Pat. No. 5,372,927 (Delton), it contains 0.4 to 20 mol% of chloride and 10 mol% or less of iodide, based on the total silver content, and halide. Ultrathin tabular grain emulsions, the remainder of which are bromides, are shown by Delton corresponding to curves A and B of US Pat. Nos. 5,061,609 and 5,061,616 (Piggin et al.). Can be prepared by growing grains occupying 5 to 90% of the total silver amount in the pAg-temperature (° C.) boundary (preferably within the boundary of curve B) of curve A. Under these precipitation conditions, the presence of chloride ions actually helps to reduce tabular grain thickness. As described above, the halogen composition of the tabular grains of the emulsion of the present invention is most preferably silver iodobromide. However, as mentioned above, the introduction of chloride ions can be present in the bulk for grain thinning, resulting in chloride ions being incorporated into the base of the tabular grains.
[0079]
In the present invention, the tabular grains preferably contain dislocation lines, silver halide protrusions having an epitaxial junction, or both.
[0080]
The dislocation lines of tabular grains are described in, for example, J. F. Hamilton, Photo. Sci. Eng. 11, 57, (1967) 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, 213, (1972). In other words, silver halide grains taken out carefully so as not to apply a pressure that causes dislocation lines to the grains from the emulsion are placed on a mesh for electron microscope observation to prevent damage (printout, etc.) due to electron beams. Observation is performed by the transmission method with the sample cooled. At this time, the thicker the particle, the more difficult it is to transmit the electron beam. Therefore, it is possible to observe more clearly using a high-pressure type electron microscope (200 kV or more for a 0.25 μm thick particle). it can.
[0081]
From the photograph of the particles obtained by such a method, the position and the number of dislocation lines for each particle when viewed from the direction perpendicular to the main plane can be obtained.
[0082]
The number of dislocation lines is preferably an average of 10 or more per particle. More preferably, the average number is 20 or more per particle. When dislocation lines are densely present, or when dislocation lines are observed crossing each other, the number of dislocation lines per grain may not be clearly counted. However, even in these cases, it can be counted to the order of approximately 10, 20, or 30, and clearly, it can be distinguished from the case where there are only a few. The average number of dislocation lines per particle is obtained as a number average by counting the number of dislocation lines for 100 grains or more.
[0083]
Dislocation lines can be introduced, for example, in the vicinity of the outer periphery of the tabular grain. In this case, the dislocations are substantially perpendicular to the outer periphery, and dislocation lines are generated starting from the position of x% of the distance from the center of the tabular grain to the side (outer periphery) and reaching the outer periphery. The value of x is preferably 10 or more and less than 100, more preferably 30 or more and less than 99, and most preferably 50 or more and less than 98. At this time, the shape formed by connecting the positions where the dislocation lines start is similar to the particle shape, but is not completely similar and may be distorted. This type of dislocation line is not found in the central region of the particle. The direction of dislocation lines is crystallographically approximately (211) but is often serpentine and sometimes intersects.
[0084]
Moreover, even if it has a dislocation line substantially uniformly over the whole region on the outer periphery of a tabular grain, it may have a dislocation line at a local position on the outer periphery. That is, taking hexagonal tabular silver halide grains as an example, dislocation lines may be limited only to the vicinity of six vertices, or dislocation lines may be limited to only one of the vertices. . Conversely, it is possible that the dislocation line is limited to only the sides excluding the vicinity of the six vertices.
[0085]
Further, dislocation lines may be formed over a region including the centers of two parallel main planes of the tabular grains. When dislocation lines are formed over the entire main plane, the direction of the dislocation lines may be approximately (211) in terms of crystallography when viewed from the direction perpendicular to the main plane. It may be formed randomly, and the length of each dislocation line is also random, and it may be observed as a short line on the main plane, or it may be observed as reaching a side (periphery) as a long line. is there. Dislocation lines are often straight or meandering. They often cross each other.
[0086]
As described above, the position of the dislocation line may be limited to the outer periphery, the main plane, or a local position, or may be formed by combining them. That is, it may exist simultaneously on the outer periphery and the main plane.
[0087]
The silver halide protrusion having an epitaxial junction can be formed by the method disclosed in JP-A-58-108526 (Mascasky) and JP-A-8-101472-101476 (Dobendeek etc.).
[0088]
As the silver halide emulsion, those subjected to physical ripening, chemical ripening and spectral sensitization are usually used. The additive used in such a process is Research Disclosure No. 17643, ibid. 18716 and No. 1 307105, and the corresponding part is shown in the following table.
[0089]

If necessary, the silver halide emulsion of the present invention can be provided on a support together with one or more other emulsions. Moreover, it can provide not only on one side of a support body but on both surfaces. It can also be layered as emulsions of different color sensitivity.
[0090]
The silver halide emulsion of the present invention is a black-and-white silver halide photographic light-sensitive material (for example, an X-ray light-sensitive material, a lith-type light-sensitive material, a black-and-white negative film) or a color photographic light-sensitive material (for example, a color negative film, a color reversal film). , Color paper, etc.). Furthermore, it can also be used for photosensitive materials for diffusion transfer (for example, color diffusion transfer elements, silver salt diffusion transfer elements), photothermographic materials (black and white, color), and the like.
[0091]
The emulsion of the present invention is preferably used in a color light-sensitive material composed of multiple layers since its photographic performance can be further exhibited. The emulsion of the present invention can be used in any photosensitive layer, but is particularly preferably used in a red photosensitive layer or a green photosensitive layer, and more preferably in a red photosensitive layer.
[0092]
The silver halide photographic emulsion of the present invention and the various techniques and inorganic / organic materials that can be used for the silver halide photographic light-sensitive material (hereinafter also referred to as “photosensitive material of the present invention”) using the same are generally used. For example, those described in Research Disclosure No. 308119 (1989) can be used.
[0093]
In addition to this, more specifically, for example, technologies and inorganic / organic materials that can be used in color photographic light-sensitive materials to which the silver halide photographic emulsion of the present invention can be applied are described in European Patent No. 436,938A2. It is described in the following places and in the patents cited below.
[0094]

In the light-sensitive material of the present invention, a magnetic recording layer can be provided.
[0095]
The magnetic recording layer used in the present invention is obtained by coating a support with an aqueous or organic solvent-based coating liquid in which magnetic particles are dispersed in a binder.
[0096]
Magnetic particles used in the light-sensitive material of the present invention are γFe₂O₃Ferromagnetic iron oxide such as Co-coated γFe₂O₃Co-coated magnetite, Co-containing magnetite, ferromagnetic chromium dioxide, ferromagnetic metal, ferromagnetic alloy, hexagonal Ba ferrite, Sr ferrite, Pb ferrite, Ca ferrite and the like can be used. Co-coated γFe₂O₃Co-coated ferromagnetic iron oxide such as The shape may be any of needle shape, rice grain shape, spherical shape, cubic shape, plate shape and the like. S for non-surface area_BET20m²/ G or more, preferably 30m²/ G or more is particularly preferable. The saturation magnetization (σs) of the ferromagnetic material is preferably 3.0 × 10²~ 3.0 × 10²A / m, particularly preferably 4.0 × 10²~ 2.5 × 10²A / m. The ferromagnetic particles may be subjected to a surface treatment with silica and / or alumina or an organic material. Further, the surface of the magnetic particles may be treated with a silane coupling agent or a titanium coupling agent as described in JP-A-6-161032. Magnetic particles having a surface coated with an inorganic or organic material as described in JP-A-4-259911 and 5-81652 can also be used.
[0097]
The binder used for the magnetic particles is a thermoplastic resin, thermosetting resin, radiation curable resin, reactive resin, acid, alkali or biodegradable polymer, natural product polymer (cellulose) described in JP-A-4-219469. Derivatives, sugar derivatives and the like) and mixtures thereof. The Tg of the resin is -40 ° C to 300 ° C, and the weight average molecular weight is 20,000 to 1,000,000. Examples thereof include vinyl copolymers, cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose derivatives such as cellulose acetate butyrate, cellulose tripropionate, acrylic resins, and polyvinyl acetal resins, and gelatin is also preferable. Cellulose di (tri) acetate is particularly preferable. The binder can be cured by adding an epoxy-based, aziridine-based, or isocyanate-based crosslinking agent. Examples of isocyanate-based crosslinking agents include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and the like, and reaction products of these isocyanates with polyalcohol (for example, tolylene diene). Reaction product of 3 mol of isocyanate and 1 mol of trimethylolpropane), polyisocyanate produced by condensation of these isocyanates, and the like are mentioned, for example, as described in JP-A-6-59357.
[0098]
As a method of dispersing the above-mentioned magnetic substance in the binder, a kneader, a pin type mill, an annular type mill, etc. are preferable, as in the method described in JP-A-6-35092. Dispersants described in JP-A-5-088283 and other known dispersants can be used. The thickness of the magnetic recording layer is 0.1 μm to 10 μm, preferably 0.2 μm to 5 μm, more preferably 0.3 μm to 3 μm. The weight ratio of the magnetic particles to the binder is preferably 0.5: 100 to 60: 100, more preferably 1: 100 to 30: 100. The coating amount of magnetic particles is 0.005 to 3 g / m², Preferably 0.01-2 g / m²More preferably, 0.02 to 0.5 g / m²It is. The transmission yellow density of the magnetic recording layer is preferably 0.01 to 0.50, more preferably 0.03 to 0.20, and particularly preferably 0.04 to 0.15. The magnetic recording layer can be provided on the entire surface or in a stripe shape on the back surface of the photographic support by coating or printing. As a method for applying the magnetic recording layer, an air doctor, blade, air knife, squeeze, impregnation, reverse roll, transfer roll, gravure, kiss, cast, spray, dip, bar, extrusion, etc. can be used. The coating solution described in 341436 is preferable.
[0099]
The magnetic recording layer may have functions such as lubricity improvement, curl adjustment, antistatic, adhesion prevention, head polishing, etc., or another functional layer may be provided to give these functions. A polishing agent for non-spherical inorganic particles in which at least one of the particles has a Mohs hardness of 5 or more is preferable. As the composition of the non-spherical inorganic particles, oxides such as aluminum oxide, chromium oxide, silicon dioxide, titanium dioxide, and silicon carbide, carbides such as silicon carbide and titanium carbide, and fine powders such as diamond are preferable. The surface of these abrasives may be treated with a silane coupling agent or a titanium coupling agent. These particles may be added to the magnetic recording layer, or may be overcoated (for example, a protective layer, a lubricant layer, etc.) on the magnetic recording layer. As the binder used at this time, the above-mentioned binders can be used, and the same binder as that for the magnetic recording layer is preferable. Photosensitive materials having a magnetic recording layer are described in US Pat. Nos. 5,336,589, 5,250,404, 5,229,259, 5,215,874, and EP466,130.
[0100]
Next, a polyester support preferably used for the light-sensitive material of the present invention having a magnetic recording layer will be described. For details including the light-sensitive material, processing, cartridge, and examples other than those described above, the published technical report, technical number 94 -6023 (Invention Association; 1994. 3.15). The polyester used in the present invention is formed with diol and aromatic dicarboxylic acid as essential components, and 2,6-, 1,5-, 1,4- and 2,7-naphthalenedicarboxylic acid, terephthalic as aromatic dicarboxylic acid Examples of the acid, isophthalic acid, phthalic acid, and diol include diethylene glycol, triethylene glycol, cyclohexane dimethanol, bisphenol A, and bisphenol. Examples of this polymer include homopolymers such as polyethylene terephthalate, polyethylene naphthalate, and polycyclohexanedimethanol terephthalate. Particularly preferred is a polyester containing 50 mol% to 100 mol% of 2,6-naphthalenedicarboxylic acid. Of these, polyethylene-2,6-naphthalate is particularly preferred. The average molecular weight range is about 5,000 to 200,000. The Tg of the polyester of the present invention is 50 ° C. or higher, more preferably 90 ° C. or higher.
[0101]
Next, the polyester support is heat-treated at a heat treatment temperature of 40 ° C. or more and less than Tg, more preferably Tg−20 ° C. or more and less than Tg, in order to make it difficult to cause curl. The heat treatment may be performed at a constant temperature within this temperature range, or may be performed while cooling. This heat treatment time is 0.1 hours to 1500 hours, more preferably 0.5 hours to 200 hours. The heat treatment of the support may be performed in a roll shape or may be performed while being conveyed in a web shape. Provide unevenness on the surface (for example, SnO₂And Sb₂O₅The surface shape may be improved). It is also desirable to devise measures such as preventing knurling of the core part by imparting knurls to the end part and slightly raising only the end part. These heat treatments may be carried out at any stage after forming the support, after the surface treatment, after applying the back layer (antistatic agent, slip agent, etc.) and after applying the undercoat. Preferred is after application of the antistatic agent.
[0102]
This polyester may be kneaded with an ultraviolet absorber. In order to prevent light piping, the purpose can be achieved by kneading dyes or pigments that are commercially available for polyesters such as Mitsubishi Kasei's Diaresin and Nippon Kayaku's Kayset.
[0103]
Next, the photosensitive material of the present invention is preferably subjected to a surface treatment in order to bond the support and the photosensitive material constituting layer. Examples of the surface activation treatment include chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, and ozone oxidation treatment. Among the surface treatments, ultraviolet irradiation treatment, flame treatment, corona treatment, and glow treatment are preferable.
[0104]
The light-sensitive material of the present invention preferably has a slip property. The slip agent-containing layer is preferably used for both the photosensitive layer surface and the back surface. A preferable slip property is 0.25 or less and 0.01 or more in terms of dynamic friction coefficient. The measurement at this time represents a value when the stainless steel sphere having a diameter of 5 mm is conveyed at 60 cm / min (25 ° C., 60% RH). In this evaluation, even if the counterpart material is replaced with the photosensitive layer surface, the value is almost the same.
[0105]
Examples of slip agents that can be used in the present invention include polyorganosiloxanes, higher fatty acid amides, higher fatty acid metal salts, esters of higher fatty acids and higher alcohols, and polyorganosiloxanes include polydimethylsiloxane, polydiethylsiloxane, Styrylmethylsiloxane, polymethylphenylsiloxane, and the like can be used. As the additive layer, the outermost layer of the emulsion layer or the back layer is preferable. In particular, polydimethylsiloxane and esters having a long chain alkyl group are preferred.
[0106]
The light-sensitive material of the present invention preferably has a matting agent. The matting agent may be either the emulsion surface or the back surface, but is particularly preferably added to the outermost layer on the emulsion side. The matting agent may be soluble in the processing solution or insoluble in the processing solution, and is preferably a combination of both. For example, polymethyl methacrylate, poly (methyl methacrylate / methacrylic acid = 9/1 or 5/5 (molar ratio)), polystyrene particles, etc. are preferable, and the particle size is preferably 0.8 to 10 μm and the particle size distribution is narrower. Preferably, 90% or more of the total number of particles is contained in the range of 0.9 to 1.1 times the average particle size, and particles of 0.8 μm or less are added simultaneously in order to improve matting properties. Also preferred are, for example, polymethyl methacrylate (0.2 μm), poly (methyl methacrylate / methacrylic acid = 9/1 (molar ratio), 0.3 μm), polystyrene particles (0.25 μm), colloidal silica (0.03 μm). The film cartridge used in the light-sensitive material of the present invention will be described below.The main material of the cartridge used in the present invention is a metal. It may also be a synthetic plastic.
[0107]
Preferred plastic materials are polystyrene, polyethylene, polypropylene, polyphenyl ether and the like. Furthermore, the cartridge of the present invention may contain various antistatic agents, and carbon black, metal oxide particles, nonions, anions, cations, and peteine surfactants or polymers can be preferably used. These antistatic cartridges are described in JP-A Nos. 1-312537 and 1-312538. Especially, the resistance at 25 ° C. and 25% RH is 10¹²Ω or less is preferable. Usually, plastic patrone is manufactured using a plastic kneaded with carbon black or pigment to provide light shielding. The size of the patrone may be the current 135 size, and it is also effective to reduce the diameter of the 25 mm cartridge of the current 135 size to 22 mm or less in order to reduce the size of the camera. The volume of the patrone case is 30 cm.^ThreeLess preferably 25cm^ThreeThe following is preferable. The weight of the plastic used for the cartridge and the cartridge case is preferably 5 to 15 g.
[0108]
Further, a patrone for rotating the spool and feeding the film may be used in the present invention. Alternatively, the film tip may be housed in the cartridge main body, and the film tip may be sent out from the port portion of the cartridge by rotating the spool shaft in the film feed direction. These are disclosed in U.S. Pat. Nos. 4,834,306 and 5,226,613. Also, a so-called raw film before development and a developed photographic film may be stored in the same new cartridge, or different cartridges.
[0109]
The color photographic light-sensitive material of the present invention is also suitable as a color negative film for an advanced photo system (hereinafter referred to as APS), manufactured by Fuji Photo Film Co., Ltd. (hereinafter referred to as Fuji Film), NEXIA A, NEXIA F, and NEXIA. The film is processed into an APS format such as H (ISO 200/100/400 in order) and stored in a dedicated cartridge. These APS cartridge films are used by being loaded into an APS camera such as the Epion series represented by Fujifilm's Epion 300Z. The color photographic light-sensitive material of the present invention is also suitable for a film with a lens such as a super slim which is a Fuji color copying run made by Fuji Film.
[0110]
The film photographed by these is printed through the following process in the minilab system.
(1) Reception (carrying out the exposed cartridge film from the customer)
(2) Detach process (transfer film from cartridge to intermediate cartridge for development process)
(3) Film development
(4) Rear touch process (return developed negative film back to original cartridge)
(5) Print (C, H, P type prints and index prints are continuously printed on a color paper [preferably SUPER FA8 manufactured by Fujifilm])
(6) Collation / shipment (cartridge and index print are collated by ID number and shipped together with the print).
[0111]
As these systems, Fujifilm's minilab champion Super FA-298 / FA-278 / FA-258 / FA-238 is preferred. Examples of the film processor include FP922AL / FP562B / FP562BL / FP362B / FP3622BL, and the recommended processing chemical is Fujicolor Justit CN-16L. Examples of the printer processor include PP3008AR / PP3008A / PP1828AR / PP1828A / PP1258AR / PP1258A / PP728AR / PP728A, and the recommended processing chemical is FUJICOLOR JUSTIT CP-47L. The detacher used in the detach process and the rear toucher used in the rear touch process are preferably DT200 / DT100 and AT200 / AT100 from Fuji Film, respectively.
[0112]
The APS system can also be enjoyed by a photo joy system centered on Fujifilm's digital image workstation Aladdin 1000. For example, a developed APS cartridge film was directly loaded into Aladdin 1000, or image information of negative film, positive film, or print was input using a 35 mm film scanner FE-550 or a flat head scanner PE-550. Digital image data can be easily processed and edited. The data can be output as a print by a digital color printer NC-550AL using a light-fixing type thermal color printing system, a photography 3000 using a laser exposure thermal development transfer system, or by an existing laboratory apparatus through a film recorder. Aladdin 1000 can also output digital information directly to a floppy disk or Zip disk, or to a CD-R via a CD writer.
[0113]
On the other hand, at home, you can enjoy photos on TV just by loading the developed APS cartridge film into the Fujifilm photo player AP-1, and if you load it into the Fujifilm photo scanner AS-1, you can take pictures on your computer. Information can be captured continuously at high speed. Moreover, in order to input a film, a print, or a three-dimensional object into a personal computer, Photovision FV-10 / FV-5 manufactured by Fuji Film can be used. Furthermore, image information recorded on a floppy disk, Zip disk, CD-R or hard disk can be processed and enjoyed on a personal computer in various ways using Fujifilm's application software Photo Factory. In order to output a high-quality print from a personal computer, a digital color printer NC-2 / NC-2D manufactured by Fuji Film using a light fixing type thermal color printing method is suitable.
[0114]
To store the developed APS cartridge film, Fuji Color Pocket Album AP-5 Pop L, AP-1 Pop L, AP-1 Pop KG or Cartridge File 16 is preferable.
[0115]
【Example】
EXAMPLES Next, although an Example demonstrates this invention further in detail, the embodiment of this invention is not limited to this.
[0116]
Example 1 Production Method of Monodispersed Ultrathin Tabular Grain Emulsion with Trimeritized Gelatin
Emulsion 1a) Comparative example
Place 1000 mL of gelatin aqueous solution (including 0.5 g of low molecular gelatin (molecular weight 15000 deionized alkali-treated bone gelatin) and 0.31 g of KBr) in a reaction vessel and keep the temperature at 40 ° C., while maintaining Ag-1 solution (in 100 mL). AgNO₃5 g) and X-1 solution (containing 3.5 g of KBr in 100 mL) were simultaneously mixed and added at 20.0 mL at 30.0 mL / min. After stirring for 1 minute, 22 mL of KBr solution (containing 10 g of KBr in 100 mL) was added, and the temperature was raised to 75 ° C. After a aging step for 5 minutes after the temperature rise, an oxidized gelatin solution (containing 250 g of oxidized gelatin (methionine content 5% or less) in 250 mL) was added. Next, Ag-2 solution (AgNO in 100 mL)₃20.4 g) and X-2 solution (containing 16.7 g of KBr in 100 mL) were kept at −30 mV by CDJ (controlled double jet) until the total addition amount of Ag-2 solution reached 700 mL. The addition rate was increased at a constant rate from 4.4 mL / min to 31.0 mL / min. At the same time, emulsion was added using AgI fine particles so that the silver iodide content with respect to the total silver amount in the grains after the growth process was 4.0 mol%. Finally, the temperature was lowered to 35 ° C. and washed with settled water. Gelatin aqueous solution was added and adjusted to pH 6.0 at 40 ° C.
[0117]
A TEM image of the replica of the particles was observed. In the obtained emulsion, AgI 4 mol% (the same applies hereinafter based on the total amount of silver in the grains), the sum of the projected areas of grains having a thickness of 0.065 μm and an aspect ratio of 28.2 is 97% of the total projected area. Accounted for.
[0118]
Emulsion 1b) The present invention
To emulsion 1a, instead of adding an oxidized gelatin solution after the ripening step, a trimellitated gelatin solution (containing 35 g of trimellitated gelatin in 250 mL) was added, and immediately HNO₃The particles were formed under the same conditions except that the pH was adjusted to 5.8. In the obtained emulsion, the sum of the projected areas of 4 mol% AgI, 0.064 μm thickness, and 28.9 aspect ratio accounted for 97% of the total projected area.
[0119]
Emulsion 1c) The present invention
To emulsion 1b, add the trimellitic gelatin solution immediately after nucleation and immediately add HNO₃The particles were formed under the same conditions except that the pH was adjusted to 5.8. In the obtained emulsion, the sum of the projected areas of 4 mol% AgI, 0.063 μm thickness and 29.6 aspect ratio accounted for 97% of the total projected area.
[0120]
The following table shows the coefficient of variation (COV) and the thickness of the circle-equivalent diameter in the silver halide tabular grains after the ripening step and in the final grains (after growth) in the emulsions 1a to 1c.
[0121]

From this result, it can be seen that trimellitated gelatin has the same or more thinning effect than oxidized gelatin, and also has a monodispersion effect during growth and further during ripening.
[0122]
Example 2 Production Method of Monodispersed Ultrathin Tabular Grain Emulsion by Overripening Process
Emulsion 1A) The present invention
Place 1000 mL of gelatin aqueous solution (including 0.5 g of low molecular gelatin (molecular weight 15000 deionized alkali-treated bone gelatin) and 0.31 g of KBr) in a reaction vessel, and maintain the temperature at 40 ° C. while maintaining Ag-1 solution (in 100 mL). AgNO₃5 g) and X-1 solution (containing 3.5 g of KBr in 100 mL) were simultaneously mixed and added at 20.0 mL at 30.0 mL / min. After stirring for 1 minute, 22 mL of KBr solution (containing 10 g of KBr in 100 mL) was added, and the temperature was raised to 75 ° C. After the aging process for 5 minutes after the temperature rise, the over-aging process was performed, and the plate itself was reduced to 80% (when the number of plate nuclei in the aging process was 100%) by Ostwald ripening. Thereafter, an oxidized gelatin solution (containing 35 g of oxidized gelatin (containing 5% or less methionine) in 250 mL) was added, and an Ag-2 solution (AgNO in 100 mL) was added.₃20.4 g) and X-2 solution (containing 16.7 g of KBr in 100 mL) while maintaining the CDJ (controlled double jet) at −30 mV until the total addition amount of Ag-2 solution reaches 560 mL. The addition rate was increased at a constant rate from 4.4 mL / min to 27.0 mL / min. At the same time, emulsion was added using AgI fine particles so that the silver iodide content with respect to the total silver amount in the grains after the growth process was 4.0 mol%. Finally, the temperature was lowered to 35 ° C. and washed with settled water. Gelatin aqueous solution was added and adjusted to pH 6.0 at 40 ° C.
[0123]
A TEM image of the replica of the particles was observed. In the obtained emulsion, the sum of the projected areas of 4 mol% AgI, 0.065 μm thickness and 28.9 aspect ratio accounted for 97% of the total projected area.
[0124]
Emulsion 1B) The present invention
To emulsion 1A, instead of adding an oxidized gelatin solution after the overripening step, a trimellitated gelatin solution (containing 35 g of trimellitated gelatin in 250 mL) was added and immediately HNO.₃The particles were formed under the same conditions except that the pH was adjusted to 5.8. In the obtained emulsion, the sum of the projected areas of 4 mol% AgI, 0.064 μm thickness and 29.5 aspect ratio accounted for 97% of the total projected area.
[0125]
Emulsion 1C) The present invention
To emulsion 1B, add the trimellitated gelatin solution immediately after nucleation and immediately add HNO₃The particles were formed under the same conditions except that the pH was adjusted to 5.8. In the obtained emulsion, the sum of the projected areas of 4 mol% AgI, 0.063 μm thickness and 30.2 aspect ratio accounted for 97% of the total projected area.
[0126]
The following table shows the coefficient of variation (COV) of the circle-equivalent diameter in the silver halide tabular grains after the overripening step in the emulsions 1A to 1C and in the final grains (after growth). For reference, the COVs of emulsions 1a to 1c are shown in parentheses.
[0127]

[0128]
From this result, the COV after the over-ripening step tends to deteriorate with respect to that after the ripening step, whereas the superiority and inferiority of the final grains after growth are reversed. Actually, from the respective equivalent circle diameter distributions, it was found that in emulsion 1A, the plate having a small equivalent circle diameter found in emulsion 1a was greatly reduced, and as a result, the distribution was improved. In addition, it has been found that emulsions 1B and 1C have not only the reduction of the flat plate with a small equivalent circle diameter, but also the frequency of the flat plate with a large equivalent circle diameter, and the distribution is improved as a result.
[0129]
Example 3 Production Method of Monodispersed Ultrathin Tabular Grain Emulsion by Fine Particle Addition Growth Method
Next, using the mixer shown in FIG. 1 which is one embodiment of the present invention, an Ag-3 solution (AgNO in 100 mL) was used.₃Solution containing 10.2 g) and X-3 solution (KBr 6.85 g, solution of 0.4 g KI containing 5% by weight of low molecular weight gelatin (average molecular weight 20,000) in 100 mL) and Ag-3 solution added in a total amount of 1400 mL The results obtained in the same manner as 1a to 1c and 1A to 1C except that the addition rate was increased at a constant rate from 8.8 mL / min to 62.0 mL / min for 41 minutes until 2 ˜2c, 2A to 2C and shown in the table below.
[0130]

From this result, it can be seen that the thickness of the plate is greatly reduced by using the mixer shown in FIG. Further, at that time, the COV of the comparative example is greatly deteriorated, while the emulsions 2b, 2c and 2A to 2C of the present invention are thinned while maintaining the monodispersity. In particular, it can be seen that Emulsion 2C of the present invention is thinned while maintaining excellent monodispersity.
[0131]
On the other hand, the corner portion of the emulsion after dispersion was slightly dissolved. This indicates that the grain form of the ultrathin tabular grain emulsion is basically unstable, and it is necessary to apply some dissolution preventing means.
Grain morphology stability in ultrathin tabular grain emulsions.
The following experiment was conducted to determine the relationship between silver iodide content and grain shape stability in an ultrathin tabular grain emulsion.
[0132]
Example 4 Highly silver iodide-containing monodispersed silver iodobromide ultrathin tabular grain emulsion
The emulsions 1a to 1c, 1A to 1C, and 2a to 2c, 2A to 2C have a silver iodide content during growth (that is, the silver iodide content in the outermost layer relative to the silver amount in the outermost layer). Particle formation was performed under the same conditions except that the X-3 solution was prepared to be 6 and 15 mol%. The table below shows the coefficient of variation (COV) of the diameter in terms of a circle in the silver halide tabular grains of the resulting ultrathin tabular grain emulsion. The parentheses indicate the thickness.
[0133]

[0134]
From these results, the above emulsions 2b to 2c and 2A to 2C in which the growth process is a method of adding fine grains are all accompanied by an increase in plate thickness due to an increase in silver iodide content found in emulsions 1a to 1c and 1A to 1C. It was not observed at all. This result indicates that the fine particle addition growth method using the mixer shown in FIG. 4 according to the present invention is a useful production technique in the preparation of an ultrathin tabular grain emulsion.
[0135]
Emulsions 1a and 2a (comparative example) were greatly polydispersed with increasing silver iodide content. On the other hand, the COVs of the emulsions of the present invention were all significant compared to the comparative examples, although some of the distributions deteriorated as the silver iodide content increased. In particular, Emulsions 1C and 2C (invention) having an over-ripening process and immediately added after nucleation of trimellitated gelatin have a COV of 20% or less even in a high silver iodide content region such as a silver iodide content of 15 mol%. It can be seen that such excellent monodispersity can be realized.
[0136]
Next, for the emulsions 1C and 2C of the present invention having different grain thicknesses, the silver iodide content during growth (that is, the silver iodide contained in the outermost layer relative to the amount of silver in the outermost layer) is 0, 3, 4, Particle formation was performed under the same conditions except that the X-3 solution was prepared to 6 and 15 mol. Next, the particle form at 15 minutes, 30 minutes, and 60 minutes was observed by the replica method while keeping constant at a temperature (50 ° C.) taking into account the temperature at the time of chemical sensitization after settling and dispersion. . The following table shows the presence / absence of morphological changes.
[0137]

From the above results, the solubility of the ultrathin tabular grains was suppressed as the iodide content was increased. On the other hand, it can also be seen that the solubility increases with decreasing thickness of the ultrathin tabular grains. From the above results, it can be seen that the base iodide content necessary for stabilizing the morphology of the ultrathin tabular grains is at least 4 mol%, preferably 6 mol% or more, and more preferably 15 mol% or more.
[0138]
Example 5 Core / shell type monodispersed silver iodobromide ultrathin tabular grain emulsion
Next, with respect to the emulsion 2C of the present invention, the silver iodide content in the outermost layer was 6 mol% and 15 mol% with respect to the silver amount in the outermost layer, and the other regions were 2 mol with respect to the silver amount in the other regions. The particles were formed under the same conditions except that the content was changed to be%. The resulting emulsion yielded core / shell ultrathin tabular grains having a thickness of 0.047 μm. Next, the emulsion was kept constant at a temperature (50 ° C.) taking into account the temperature during chemical sensitization after settling and dispersion, and the grain morphology at 15 minutes, 30 minutes and 60 minutes was replicated. Observed. The following table shows the presence or absence of the morphological change.
[0139]
Outermost layer silver iodide content 6 mol%
Core / Ciel ratio (silver amount) 15 minutes 30 minutes 60 minutes
95/5 Yes Yes Yes Yes
90/10 No Yes Yes
80/20 No No Yes
75/25 None None None.
[0140]
Outermost layer silver iodide content 15 mol%
Core / Ciel ratio (silver amount) 15 minutes 30 minutes 60 minutes
95/5 No Yes Yes
90/10 No No Yes
80/20 None None None
75/25 None None None.
[0141]
From this result, it can be seen that by forming a core / shell structure in which the iodide content of the outermost layer is at least 6 mol%, preferably 15 mol%, it is possible to stabilize the morphology of ultrathin tabular grains. Further, it is understood that a shell area of 10% or more, preferably 20% or more, more preferably 25% or more is necessary as the core / shell ratio.
Examples of monolayer and multilayer photosensitive materials are shown below.
[0142]
<Particle formation>
Example X
Place 1000 mL of gelatin aqueous solution (including 0.5 g of low molecular gelatin (molecular weight 15000 deionized alkali-treated bone gelatin) and 0.31 g of KBr) in a reaction vessel, and maintain the temperature at 40 ° C. while maintaining Ag-1 solution (in 100 mL). AgNO₃5 g) and X-1 solution (containing 3.5 g of KBr in 100 mL) were simultaneously mixed and added at 20.0 mL at 30.0 mL / min. After stirring for 1 minute, add 22 mL of KBr solution (containing 10 g of KBr in 100 mL), add trimellitated gelatin solution (containing 35 g of trimellitated gelatin in 250 mL), and immediately add HNO.₃The pH was adjusted to 5.8 and the temperature was raised to 75 ° C. The emulsion was sampled as needed every 10 minutes after the temperature rise.
[0143]
The result of observing a TEM image of the replica of the grain and examining the relationship between the aging time and the coefficient of variation of the circular equivalent diameter of the tabular grain is shown below. In addition, since the mixing of regular and single twin particles was confirmed until 10 minutes after the temperature increase, the diameter of the circle equivalent of the core part that passed through the nucleation-ripening and nucleation-ripening-overripening steps was The coefficient of variation (COVc) was measured after 10 minutes.
[0144]
Coefficient of variation of diameter in terms of circle (COVc) after temperature rise
10 minutes 17%
20 minutes 25%
30 minutes 32%
40 minutes 40%
50 minutes 44%
From the above results, the completion of the aging process is 10 minutes after the temperature rise, and the subsequent stage is the over-aging process.
Emulsion X1) Comparative example
In Example X, immediately after completion of the ripening step (10 minutes after the temperature rise), immediately using the mixer shown in FIG. 4 according to the present invention, Ag-2 solution (AgNO in 100 mL) was used.₃Solution containing 20.4 g) and X-2 solution (16.7 g of KBr containing 5% by weight of low molecular gelatin (average molecular weight 20,000) in 100 mL, solution of 1.0 g of KI) from an initial flow rate of 4.4 mL / min to 0.6 mL The rate of addition was increased at a constant rate, and the growth was continued until the equivalent sphere diameter became 0.71 μm (silver content ratio 70%).
[0145]
Next, the Ag-3 solution (AgNO in 100 mL was continuously added.₃14.2 g) and X-3 solution (containing 31.2 g of KI in 100 mL) were added over 4 minutes by the double jet method (silver amount ratio 4.75%).
[0146]
Finally, Ag-2 solution and X-4 (a solution containing 16.7 g of KBr in 100 mL) were again added over 10 minutes while maintaining pAg at 9.7 by the double jet method (silver content ratio 25.25%).
[0147]
The above emulsion was washed with water by a known flocculation method at 35 ° C., and gelatin was added to reach 40 ° C.
[0148]
A TEM image of the replica of the particles was observed. In the resulting emulsion, the sum of the projected areas of 5.5 mol% AgI, 0.050 μm thickness and 39.8 aspect ratio accounted for 97% of the total projected area.
[0149]
Emulsion X2) The present invention
Emulsion X1 was prepared in the same manner except that growth was started immediately after the overripening step (20 minutes after the temperature increase).
[0150]
Emulsion X3) The present invention
Emulsion X1 was prepared in the same manner except that the growth was started immediately after the overripening step (30 minutes after the temperature increase).
[0151]
Emulsion X4) The present invention
Emulsion X1 was prepared in the same manner except that the growth was started immediately after the overripening step (40 minutes after the temperature increase).
[0152]
Emulsion X5) The present invention
Emulsion X1 was prepared in the same manner except that the growth was started immediately after the overripening step (50 minutes after the temperature increase).
[0153]
<Spectral sensitization and chemical ripening>
Emulsions X1 to X5 were each heated to 62 ° C. and sensitizing dye Exs-1 described below was 5.5 × 10 5^-FourMol / mol Ag, ExS-2 1.6 × 10^-FiveMol / mol Ag, ExS-3 5.5 × 10 5^-FourAfter adding molar Ag for 10 minutes, sodium thiosulfate 2.6 × 10^-FiveMol / mol Ag, N, N dimethylselenourea 1.1 × 10^-FiveMol / mol Ag, potassium thiocyanate 3.0 × 10^-3Mol / mol Ag, chloroauric acid 8.6 × 10^-6Mole / mole Ag was added, and aging was performed so that the sensitivity was highest when exposed to 1/100 second. The emulsions thus obtained are designated Y1 to Y5.
<Preparation of coated sample and its evaluation>
On the cellulose triacetate film support provided with the undercoat layer, the emulsions Y1 to Y5 and the protective layer were applied in the coating amounts as shown in the following Table A to prepare coated samples 101 to 105.
[0154]

[0155]
[Chemical 1]

These samples were allowed to stand for 14 hours under conditions of 40 ° C. and 70% relative humidity, then exposed through a continuous wedge for 1/100 second, and color development shown in the following Table B was performed.
[0156]
The density of the treated sample was measured with a green filter. The results obtained are shown in Table 1 below.
[0157]

Next, the composition of the treatment liquid will be described.
[0158]

[0159]

[0160]
[Chemical formula 2]

[0161]
(Washing solution)
Tap water was passed through a mixed bed column packed with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH-type anion exchange resin (Amberlite IR-400), and calcium. And magnesium ion concentration was processed to 3 mg / L or less, and then sodium isocyanurate dichloride 20 mg / L and sodium sulfate 1.5 g / L were added.
[0162]
The pH of this solution is in the range of 6.5 to 7.5.
[0163]

[0164]
[Table 1]

In Table 1, the sensitivities and gradations of the samples 101 to 105 are expressed as relative values with the sensitivity and gradation of the sample 101 as 100.
It can be seen that the inventive samples 102 to 105 are more sensitive than the comparative sample 101 and have a large gradation and a high contrast.
The improvement of the photographic performance is achieved by the improvement of monodispersity by introducing the over-ripening process, and it can be seen that the effect of the present invention is remarkable.
[0165]
<Multilayer Example>
1) Support
The support used in this example was prepared by the following method.
[0166]
100 parts by weight of a commercially available polyethylene-2,6-naphthalate polymer and Tinuvin P.I. 326 (manufactured by Geigy Co., Ltd.) was dried in a conventional manner with 2 parts by weight, melted at 300 ° C., extruded from a T-shaped die, and stretched 3.0 times at 140 ° C., followed by 3. The film was stretched 0 times and further heat-fixed at 250 ° C. for 6 seconds to obtain a PEN film having a thickness of 90 μm.
[0167]
Further, a part thereof was wound around a stainless steel core having a diameter of 20 cm, and a thermal history of 110 ° C. and 48 hours was given.
[0168]
2) Application of undercoat layer
The above support is subjected to corona discharge treatment, UV discharge treatment, further glow discharge treatment, and flame treatment on both sides, and then an undercoat solution having the following composition is applied to each surface to extend the undercoat layer to the high temperature surface side. Provided. The corona discharge treatment uses a solid state corona treatment machine 6KVA model manufactured by Pillar Co., Ltd., and a 30 cm wide support is treated at 20 m / min. At this time, the object to be processed is 0.375 KV · A · min / m from the current / voltage reading²Was processed. The discharge frequency during the treatment was 9.6 KHz, and the gap clearance between the electrode and the derivative roll was 1.6 mm. The UV discharge treatment was performed while heating at 75 ° C. Further, in the glow discharge treatment, irradiation was performed with a cylindrical electrode at 3000 W for 30 seconds.
[0169]
3g gelatin
25 mL of distilled water
Sodium α-sulfodi-2-ethylhexyl succinate 0.05g
0.02g formaldehyde
0.1g salicylic acid
Diacetylcellulose 0.5g
p-Chlorophenol 0.5g
Resorcin 0.5g
Cresol 0.5g
(CH₂ = CHSO₂ CH₂ CH₂ NHCO)₂ CH₂             0.2g
Trimethylolpropane triazine 0.2g
Trimethylolpropane tristoluene diisocyanate 0.2g
Methanol 15mL
Acetone 85mL
0.01g formaldehyde
Acetic acid 0.01g
Concentrated hydrochloric acid 0.01 g.
3) Coating the back layer
An antistatic layer having the following composition, a magnetic recording layer, and a sliding layer were provided as a back layer on one surface of the support after the undercoating.
[0170]
3-1) Application of antistatic layer
3-1-1) Preparation of conductive fine particle dispersion (tin oxide-antimony oxide composite dispersion)
A homogeneous solution was obtained by dissolving 230 parts by weight of stannic chloride hydrate and 23 parts by weight of antimony trichloride in 3000 parts by weight of ethanol. A 1N sodium hydroxide aqueous solution was added dropwise to the solution until the pH of the solution reached 3, to obtain a coprecipitate of colloidal stannic oxide and antimony oxide. The obtained coprecipitate was allowed to stand at 50 ° C. for 24 hours to obtain a reddish brown colloidal precipitate.
[0171]
The reddish brown colloidal precipitate was separated by centrifugation. In order to remove excess ions, water was added to the precipitate and washed by centrifugation. This operation was repeated three times to remove excess ions.
[0172]
200 parts by weight of colloidal precipitate from which excess ions have been removed are redispersed in 1500 parts by weight of water and sprayed in a baking furnace heated to 650 ° C., and a bluish tin oxide-antimony oxide composite having an average particle size of 0.005 μm A fine particle powder was obtained. The specific resistance of the fine particle powder was 5 Ω · cm.
[0173]
A mixed liquid of 40 parts by weight of the fine particle powder and 60 parts by weight of water is adjusted to pH 7.0, and after coarse dispersion with a stirrer, the residence time becomes 30 minutes with a horizontal sand mill (trade name Dynomill; manufactured by WILLYA. BACHOFENAG). Prepared by dispersing. The average particle size of the secondary aggregate at this time was about 0.04 μm.
[0174]
3-1-2) Coating of conductive layer
The following formulation was applied so that the dry film thickness was 0.2 μm, and dried at 115 ° C. for 60 seconds.
[0175]
Conductive fine particle dispersion prepared in 3-1-1) 20 parts by weight
2 parts by weight of gelatin
27 parts by weight of water
60 parts by weight of methanol
0.5 parts by weight of P-chlorophenol
2 parts by weight of resorcin
Polyoxyethylene nonylphenyl ether 0.01 parts by weight
The resistance of the obtained conductive film was 108.0 (100 V), and had excellent antistatic performance.
[0176]
3-2) Coating of magnetic recording layer
Magnetic Co-deposition γ-Fe₂O_Three(Long axis 0.14 μm, single axis 0.03 μm needle shape, specific surface area 41 m²/ G, saturation magnetization 89 emu / g, surfaces are aluminum oxide and silicon oxide, respectively Fe₂O_Three2% by weight of the surface treatment. Coercive force 930 Oe, Fe⁺²/ Fe⁺³The ratio was 6/94) 1100 g, 220 g of water and 150 g of poly (polymerization degree 16) oxyethylenepropyl, silane coupling agent of trimethoxysilane were added and kneaded well for 3 hours. The coarsely dispersed viscous liquid was dried at 70 ° C. for one day and night to remove water, and then heated and treated at 110 ° C. for 1 hour to produce surface-treated magnetic particles.
[0177]
Furthermore, it knead | mixed with the open kneader again with the following prescription.
[0178]
Surface-treated magnetic particles 1000g
Diacetylcellulose 17g
Methyl ethyl ketone 100g
Cyclohexanone 100g
Furthermore, it was finely dispersed at 200 rpm for 4 hours with a sand mill (1 / 4G) according to the following formulation.
[0179]
100g of the above kneaded product
60g diacetylcellulose
Methyl ethyl ketone 300g
300 g of cyclohexanone.
Diacetylcellulose and C as a curing agent₂H_FiveC (CH_2OCONH-C₈H_Three(CH_Three) NCO)_ThreeWas added at 20 wt% with respect to the binder. The resulting solution was diluted with equal amounts of methyl ethyl ketone and cyclohexanone so that the viscosity was about 80 cP. Moreover, application | coating was implemented with the bar coater on said electroconductive layer, and the film thickness was 1.2 micrometer. Amount of magnetic material 0.6g / m²It applied so that it might become. Further, silica particles (0.3 μm) as a matting agent and aluminum oxide (0.5 μm) as an abrasive are each 10 mg / m.²It added so that it might become. Drying was carried out at 115 ° C. for 6 minutes (all rollers and transport devices in the drying zone were at 115 ° C.).
[0180]
When the blue filter was used with the X-light status M, the increase in the color density of D8 of the magnetic recording layer was about 0.1. The saturation magnetization moment of the magnetic recording layer is 4.2 emu / m.²The coercive force was 923 Oe, and the squareness ratio was 65%.
[0181]
3-3) Preparation of sliding layer
The following formulation solution was applied so that the solid content coating amount of the compound was as follows, and dried at 110 ° C. for 5 minutes to obtain a sliding layer.
[0182]
Diacetylcellulose 25mg / m²
C₆H₁₃CH (OH) C_TenH₂₀COOC₄₀H₈₁  Compound a 6mg / m²
C₅₀H₁₀₁O (CH₂CH₂O)₁₆H Compound b 9mg / m²
Compound a / Compound b (6: 9) was prepared by heating and dissolving xylene and propylene glycol monomethyl ether (volume ratio 1: 1) at 105 ° C. in the same volume of liquid, and adding this liquid to 10 times the amount of propylene glycol. It was poured into monomethyl ether (25 ° C.) to obtain a fine dispersion. Further, the mixture was diluted in 5 times the amount of acetone, re-dispersed with a high-pressure homogenizer (200 atm), added to a dispersion (average particle size 0.01 μm), and then used.
[0183]
The obtained sliding layer has excellent properties such as a dynamic friction coefficient of 0.06 (5 mmφ stainless hard ball, load of 100 g, speed of 6 cm / minute) and a static friction coefficient of 0.07 (clip method). Further, the slipping property with the emulsion surface described later was a dynamic friction coefficient of 0.12.
[0184]
4) Application of photosensitive material layer
Next, on the opposite side of the back layer obtained above, each layer having the following composition was applied in multiple layers to produce a color negative photographic film.
[0185]
The fifth layer (high-sensitivity red-sensitive emulsion layer) contains the emulsions Y1 to Y5 described in Example X, which were designated as Samples 201 to 205, respectively.
[0186]
(Photosensitive layer composition)
The main materials used in each layer are categorized as follows, but the use of these materials is not limited to the use described:
ExC: Cyan coupler UV: UV absorber
ExM: Magenta coupler HBS: High boiling point organic solvent
ExY: Yellow coupler H: Gelatin hardener
ExS: Sensitizing dye
The number corresponding to each component is g / m²The coating amount expressed in units is shown. For silver halide, the coating amount in terms of silver is shown. However, for the sensitizing dye, the coating amount with respect to 1 mol of silver halide in the same layer is shown in mol units.
[0187]
(Sample 201)
First layer (Anti-halation layer)
Black colloidal silver 0.09
Gelatin 1.60
ExM-1 0.12
ExF-1 2.0 × 10^-3
Solid disperse dye ExF-2 0.030
Solid disperse dye ExF-3 0.040
HBS-1 0.15
HBS-2 0.02.
[0188]
Second layer (intermediate layer)
Silver iodobromide emulsion M Silver 0.065
ExC-2 0.04
Polyethyl acrylate latex 0.20
Gelatin 1.04.
[0189]
3rd layer (low sensitivity red sensitive emulsion layer)
Silver iodobromide emulsion D Silver 0.50
ExC-1 0.17
ExC-3 0.030
ExC-4 0.10
ExC-5 0.020
ExC-6 0.010
Cpd-2 0.025
HBS-1 0.10
Gelatin 0.87.
[0190]
Fourth layer (medium sensitivity red emulsion layer)
Silver iodobromide emulsion C Silver 0.70
ExS-1 3.5 × 10^-Four
ExS-2 1.6 × 10^-Five
ExS-3 5.1 × 10^-Four
ExC-1 0.13
ExC-2 0.060
ExC-3 0.0070
ExC-4 0.090
ExC-5 0.015
ExC-6 0.0070
Cpd-2 0.023
HBS-1 0.10
Gelatin 0.75.
[0191]
5th layer (High sensitivity red emulsion layer)
Emulsion described in Example X Silver 1.40
ExS-1 2.4 × 10^-Four
ExS-2 1.0 × 10^-Four
ExS-3 3.4 × 10^-Four
ExC-1 0.10
ExC-3 0.045
ExC-6 0.020
ExC-7 0.010
Cpd-2 0.050
HBS-1 0.22
HBS-2 0.050
Gelatin 1.10.
[0192]
6th layer (intermediate layer)
Cpd-1 0.090
Solid disperse dye ExF-4 0.030
HBS-1 0.050
Polyethyl acrylate latex 0.15
Gelatin 1.10.
[0193]
7th layer (low sensitivity green emulsion layer)
Silver iodobromide emulsion E Silver 0.15
Silver iodobromide emulsion F Silver 0.10
Silver iodobromide emulsion G Silver 0.10
ExS-4 3.0 × 10^-Five
ExS-5 2.1 × 10^-Four
ExS-6 8.0 × 10^-Four
ExM-2 0.33
ExM-3 0.086
ExY-1 0.015
HBS-1 0.30
HBS-3 0.010
Gelatin 0.73.
[0194]
8th layer (medium sensitive green emulsion layer)
Silver iodobromide emulsion H Silver 0.80
ExS-4 3.2 × 10^-Five
ExS-5 2.2 × 10^-Four
ExS-6 8.4 × 10^-Four
ExC-8 0.010
ExM-2 0.10
ExM-3 0.025
ExY-1 0.018
ExY-4 0.010
ExY-5 0.040
HBS-1 0.13
HBS-3 4.0 × 10^-3
Gelatin 0.80.
[0195]
9th layer (high-sensitivity green-sensitive emulsion layer)
Silver iodobromide emulsion I Silver 1.25
ExS-4 3.7 × 10^-Five
ExS-5 8.1 × 10^-Five
ExS-6 3.2 × 10^-Four
ExC-1 0.010
ExM-1 0.020
ExM-4 0.025
ExM-5 0.040
Cpd-3 0.040
HBS-1 0.25
Polyethyl acrylate latex 0.15
Gelatin 1.33.
[0196]
10th layer (yellow filter layer)
Yellow colloidal silver 0.015
Cpd-1 0.16
Solid disperse dye ExF-5 0.060
Solid disperse dye ExF-6 0.060
Oil-soluble dye ExF-7 0.010
HBS-1 0.60
Gelatin 0.60.
[0197]
11th layer (low sensitivity blue-sensitive emulsion layer)
Silver iodobromide emulsion J Silver 0.09
Silver iodobromide emulsion K Silver 0.09
ExS-7 8.6 × 10^-Four
ExC-8 7.0 × 10^-3
ExY-1 0.050
ExY-2 0.22
ExY-3 0.50
ExY-4 0.020
Cpd-2 0.10
Cpd-3 4.0 × 10^-3
HBS-1 0.28
Gelatin 1.20.
[0198]
12th layer (high-sensitivity blue-sensitive emulsion layer)
Silver iodobromide emulsion L Silver 1.00
ExS-7 4.0 × 10^-Four
ExY-2 0.10
ExY-3 0.10
ExY-4 0.010
Cpd-2 0.10
Cpd-3 1.0 × 10^-3
HBS-1 0.070
Gelatin 0.70.
[0199]
13th layer (first protective layer)
UV-1 0.19
UV-2 0.075
UV-3 0.065
HBS-1 5.0 × 10^-2
HBS-4 5.0 × 10^-2
Gelatin 1.8.
[0200]
14th layer (2nd protective layer)
Silver iodobromide emulsion M Silver 0.10
H-1 0.40
B-1 (1.7 μm in diameter) 5.0 × 10^-2
B-2 (Diameter 1.7 μm) 0.15
B-3 0.05
S-1 0.20
Gelatin 0.70.
[0201]
Furthermore, W-1 to W-3, B-4 to B-6, F in order to improve storage stability, processability, pressure resistance, antifungal / antibacterial properties, antistatic properties and coatability as appropriate for each layer. -1 to F-17 and iron salt, lead salt, gold salt, platinum salt, palladium salt, iridium salt
Rhodium salt is contained.
[0202]
[Table 2]

In Table 2,
(1) Emulsions J to L were reduction sensitized at the time of grain preparation using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-91938.
(2) Emulsions C to I were subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate according to the examples of JP-A-3-237450. Has been.
(3) In preparation of tabular grains, low molecular weight gelatin is used according to the examples of JP-A-1-158426.
(4) Dislocation lines as described in JP-A-3-237450 are observed in tabular grains using a high-voltage electron microscope.
(5) Emulsion L is a double-structured grain containing an internal high iodine core as described in JP-A-60-143331.
[0203]
Preparation of dispersions of organic solid disperse dyes
The following ExF-2 was dispersed by the following method. That is, 21.7 mL of water and 3 mL of 5% aqueous p-octylphenoxyethoxyethoxyethane sulfonate and 5 g of 5% aqueous p-octylphenoxypolyoxyethylene ether (degree of polymerization 10) were placed in a 700 mL pot mill. Then, 5.0 g of dye ExF-2 and 500 mL of zirconium oxide beads (diameter 1 mm) were added, and the contents were dispersed for 2 hours. A BO-type vibrating ball mill manufactured by Chuo Koki was used for this dispersion. After the dispersion, the contents were taken out and added to 8 g of a 12.5% gelatin aqueous solution, and the beads were removed by filtration to obtain a gelatin dispersion of the dye. The average particle size of the dye fine particles was 0.44 μm.
[0204]
Similarly, solid dispersions of ExF-3, ExF-4, and ExF-6 were obtained. The average particle diameters of the dye fine particles were 0.24 μm, 0.45 μm, and 0.52 μm, respectively. ExF-5 was dispersed by the microprecipitation dispersion method described in Example 1 of European Patent Application Publication (EP) No. 549,489A. The average particle size was 0.06 μm.
[0205]
[Chemical Formula 3]

[0206]
[Formula 4]

[0207]
[Chemical formula 5]

[0208]
[Chemical 6]

[0209]
[Chemical 7]

[0210]
[Chemical 8]

[0211]
[Chemical 9]

[0212]
[Chemical Formula 10]

[0213]
Embedded image

[0214]
Embedded image

[0215]
Embedded image

[0216]
Embedded image

[0217]
Embedded image

[0218]
Embedded image

[0219]
Embedded image

[0220]
Embedded image

These samples were left under conditions of 40 ° C. and relative humidity 70% for 14 hours, and then exposed to white light for 1/100 second, and the same color development processing as in Example 2 was performed. However, the color development time was 3 minutes and 15 seconds.
[0221]
The density was measured through a red filter, and the relative sensitivity was determined by the reciprocal of the exposure amount giving densities 1.8 and 2.5. Moreover, the uniform exposure which gives the density | concentration 1.8 was performed, and the granularity was also measured.
[0222]
The granularity was measured by the method described in “The Theory of the Photographic Process”, page 619, published by Macmillan Co., Ltd. after the aforementioned development processing.
[0223]
The results are shown in Table 3. However, the sensitivity and granularity of the sample 201 were set to 100, respectively, and expressed as relative values.
[0224]
[Table 3]

From Table 3, the sample using the emulsion of the present invention achieves high sensitivity while improving the granularity as compared with the comparative sample, and the effect of the present invention is remarkable.
[0225]
【The invention's effect】
In the present invention, in an ultrathin tabular grain emulsion containing 4 mol% or more of iodide, grains having excellent monodispersity can be formed by using an overripening step and an amino group-modified gelatin. Further, by using the fine particle addition growth using the mixer of the present invention in combination with the above invention, further thinning can be achieved without impairing monodispersity.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view showing a schematic configuration of a stirring device used in one embodiment of the present invention.
FIG. 2 is a schematic cross-sectional view showing a production process of a silver halide emulsion according to one embodiment of the present invention.
FIG. 3 is a perspective view showing a schematic configuration of a magnetic coupling used in a stirring device used in one embodiment of the present invention.
4 is a perspective view showing an operation of the magnetic coupling shown in FIG. 3. FIG.
[Explanation of symbols]
1 reaction vessel
2 Protective colloid aqueous solution
3 Stirring blade
10 Stirrer
11, 12, 13 Liquid supply port
16 Liquid outlet
18 Mixing tank
19 Tank body
20 Seal plate
21 and 22 stirring blades
26 External magnet
28, 29 Motor
31 Rotation center axis
33 Double-sided bipolar magnet
35 Left and right dipole magnets
L Magnetic field lines

Claims (4)

97% or more of the projected area of all grains are tabular silver halide grains having a silver iodide content of 4 mol% to 15 mol%, a thickness of less than 0.07 μm, and an aspect ratio of 5 or more , The outermost layer is occupied by tabular silver halide grains having a high silver iodide content layer with a silver iodide content of 6 mol% or more , and the variation coefficient of the diameter in terms of circle of the projected area of all tabular grains is A silver halide photographic emulsion that is less than 30%. In a dispersion medium solution containing gelatin into which at least two carboxyl groups (—COOH groups) have been introduced per chemically modified amino group when the amino group (—NH ₂ group) in gelatin is chemically modified 2. The method for producing a silver halide photographic emulsion according to claim 1, wherein the silver halide photographic emulsion is produced. An aqueous solution of a water-soluble silver salt and an aqueous solution of a water-soluble halide are supplied from a supply port provided in a closed type stirring tank of the mixer,
At least one stirring blade not having a rotating shaft penetrating the stirring tank wall is rotationally driven in the stirring tank to control the stirring state of the supplied aqueous solution,
Discharge the silver halide fine particles generated after the stirring process from the outlet provided in the sealed stirring tank,
2. The method for producing a silver halide photographic emulsion according to claim 1, wherein the silver halide fine grains are supplied to a reaction vessel for causing nucleation and / or grain growth of silver halide grains. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein the silver halide photographic emulsion according to claim 1 is contained in at least one of the emulsion layers. Silver halide photographic light-sensitive material.

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