JP3668828B2 - Silver halide photographic material - Google Patents

Description

尚、それぞれの乳剤は、電子顕微鏡観察したところ全粒子に占める平板状粒子の割合は８０％（個数）以上であった。
【００９３】
（支持体の作製）
２，６−ナフタレンジカルボン酸ジメチル１００部、エチレングリコール６０部にエステル交換触媒として酢酸カルシウム水和物０．１部を添加し、常法に従ってエステル交換反応を行った。得られた生成物に、三酸化アンチモン０．０５部、燐酸トリメチルエステル０．０３部を添加した。次いで、徐々に昇温、減圧にし、２９０℃、０．０５ｍｍＨｇの条件で重合を行い、固有粘度０．６０のポリエチレン−２，６−ナフタレートを得た。
【００９４】
これを、１５０℃で８時間真空乾燥した後、３００℃でＴダイから層状に溶融押出し、５０℃の冷却ドラム上に静電印加しながら密着させ、冷却固化させ、未延伸シートを得た。この未延伸シートをロール式縦延伸機を用いて、１３５℃で縦方向に３．３倍延伸した。
【００９５】
得られた１軸延伸フィルムをテンター式横延伸機を用いて、第１延伸ゾーン１４５℃で総横延伸倍率が５０％になるように延伸し、更に、第２延伸ゾーン１５５℃で総横延伸倍率が３．３倍となるように延伸した。次いで、１００℃で２秒間熱処理し、更に、第１熱固定ゾーン２００℃で５秒間熱固定し、第２熱固定ゾーン２４０℃で１５秒間熱固定した。次いで、横方向に５％弛緩処理しながら室温まで３０秒かけて徐冷して、厚さ８５μｍのポリエチレンナフタレートフィルムを得た。
【００９６】
これをステンレス製のコアに巻き付け、１１０℃で４８時間熱処理（アニール処理）して支持体を作製した。
【００９７】
（下引層の塗設）
この支持体の両面に１２Ｗ／ｍ²／ｍｉｎのコロナ放電処理を施し、一方の面に下記下引塗布液Ｂ−１を乾燥膜厚０．４μｍになるように塗布し、その上に１２Ｗ／ｍ²／ｍｉｎのコロナ放電処理を施し、下記下引塗布液Ｂ−２を乾燥膜厚０．０６μｍになるように塗布した。
【００９８】
１２Ｗ／ｍ²／ｍｉｎのコロナ放電処理を施した他方の面には、下記下引塗布液Ｂ−３を乾燥硬膜０．２μｍになるように塗布し、その上に１２Ｗ／ｍ²／ｍｉｎのコロナ放電処理を施し、下記下引塗布液Ｂ−４を乾燥膜厚０．２μｍになるように塗布した。
【００９９】
各層はそれぞれ塗布後９０℃で１０秒間乾燥し、４層塗布後、引き続いて１１０℃で２分間熱処理を行った後、５０℃で３０秒間冷却処理を行った。
【０１００】
〈下引塗布液Ｂ−１〉
ブチルアクリレート／ｔ−ブチルアクリレート／スチレン／２−ヒドロキシエチ
ルアクリレート共重合体（３０／２０／２５／２５重量％）ラテックス液（固形
分３０％） １２５ｇ
化合物（ＵＬ−１） ０．４ｇ
ヘキサメチレン−１，６−ビス（エチレン尿素） ０．０５ｇ
水で１リットルに仕上げる
【０１０１】
〈下引塗布液Ｂ−２〉
スチレン・無水マレイン酸共重合体の水酸化ナトリウム
水溶液（固形分６％） ５０ｇ
化合物（ＵＬ−１） ０．６ｇ
化合物（ＵＬ−２） ０．０９ｇ
シリカ粒子（平均粒径３μｍ） ０．２ｇ
水で１リットルに仕上げる
【０１０２】
〈下引塗布液Ｂ−３〉
ブチルアクリレート／ｔ−ブチルアクリレート／スチレン／２−ヒドロキシエチ
ルアクリレート共重合体（３０／２０／２５／２５重量％）ラテックス液（固形
分３０％） ５０ｇ
化合物（ＵＬ−１） ０．３ｇ
ヘキサメチレン−１，６−ビス（エチレン尿素） １．１ｇ
水で１リットルに仕上げる
ＵＬ−１：ｏ、ｐ−（Ｃ₉Ｈ₁₉）₂Ｃ₆Ｈ₃Ｏ（ＣＨ₂ＣＨ₂Ｏ）₁₂ＳＯ₃Ｎａ
ＵＬ−２：ＣＨ₃ＳＯ₂Ｏ（ＣＨ₂）₃ＯＳＯ₂ＣＨ₃
【０１０３】
〈下引塗布液Ｂ−４〉
酸化錫−酸化アンチモン複合微粒子（平均粒径０．２μｍ）の水分散液（固形分
４０重量％） １０９ｇ
水分散液Ａ ６７ｇ
水で１リットルに仕上げる
水分散液Ａ；ジカルボン酸成分としてテレフタル酸ジメチル６０モル％、イソフタル酸ジメチル３０モル％、５−スルホイソフタル酸ジメチルのナトリウム塩１０モル％、グリコール成分としてエチレングリコール５０モル％、ジエチレングリコール５０モル％を常法により共重合し、この共重合体を９５℃の熱水中で３時間撹拌し、１５重量％の水分散液Ａとした。
【０１０４】
（透明磁気記録層の塗設）
〈磁性塗布液１の調製及び塗設〉
下記組成物（Ａ）をサンドミルを用いて４０時間分散後、平均孔径１０μｍのフィルターで濾過し、磁性塗料を得た。
組成物（Ａ）
Ｃｏ被着γ−Ｆｅ₂Ｏ₃（長軸０．１５μｍ、短軸０．０３μｍ、比表面積４０ｍ
²／ｇ、Ｈｃ＝９００エルステッド） ５部
ジアセチルセルロース（酢化度＝５５％、Ｍｗ＝１８万） １００部
α−アルミナ（平均粒径０．３μｍ） １０部
アセトン ７８０部
シクロヘキサノン ３４０部
【０１０５】
上記磁性塗料にディスパーを用いて空気を巻き込まないように混合した下記組成物（Ｂ）を連続的に添加・混合して磁性塗布液１を作製した。
組成物（Ｂ）
硬膜剤（日本ポリウレタン社製：Ｃ−Ｌ、固形分７５％） ２０部
シクロヘキサノン ４５部
【０１０６】
得られた磁性塗布液１を、前記ポリエチレンナフタレート支持体の下引塗布液Ｂ−３及びＢ−４が塗設された側に乾燥膜厚０．８μｍになるように塗布・乾燥した。
（ハロゲン化銀写真感光材料試料の作成）
前記磁気記録媒体の磁気記録層とは反対側に、前記下引塗布液Ｂ−１及びＢ−２を同一条件で塗設した下引層を設けてある上に、以下に示す組成の写真構成層を順次支持体側から形成して試料１０１〜１０５を得た。それぞれの乳剤は金−硫黄増感を最適に施してから塗布した。
【０１０７】
以下に示す写真構成層の添加量は１ｍ²当たりのグラム数で表す。但し、ハロゲン化銀とコロイド銀は銀の量に換算し、増感色素は銀１モル当たりのモル数で示した。
【０１０８】

【０１０９】

【０１１０】

【０１１１】

【０１１２】

【０１１３】

【０１１４】

【０１１５】

【０１１６】
尚、上記組成物の他に、塗布助剤ＳＵ−１、ＳＵ−２、ＳＵ−３、分散助剤ＳＵ−４、粘度調整剤Ｖ−１、安定剤ＳＴ−１、ＳＴ−２、カブリ防止剤ＡＦ−１（ポリビニルピロリドン、重量平均分子量：１０，０００）、ＡＦ−２（ポリビニルピロリドン、重量平均分子量：１，１００，０００）、抑制剤ＡＦ−３、ＡＦ−４、ＡＦ−５、硬膜剤Ｈ−１、Ｈ−２、Ｈ−３、Ｈ−４及び防腐剤Ａｓｅ−１を添加した。
【０１１７】
上記各試料に用いた化合物の構造を以下に示す。
ＳＵ−１：Ｃ₈Ｆ₁₇ＳＯ₂Ｎ（Ｃ₃Ｈ₇）ＣＨ₂ＣＯＯＫ
ＳＵ−２：Ｃ₈Ｆ₁₇ＳＯ₂ＮＨ（ＣＨ₂）₃Ｎ⁺（ＣＨ₃）₃Ｂｒ^-
ＳＵ−３：スルホ琥珀酸ジ（２−エチルヘキシル）ナトリウム
ＳＵ−４：トリ−ｉ−プロピルナフタレンスルホン酸ナトリウム
ＳＴ−１：４−ヒドロキシ−６−メチル−１，３，３ａ，７−テトラザインデンＳＴ−２：アデニン
ＡＦ−３：１−フェニル−５−メルカプトテトラゾール
ＡＦ−４：１−（４−カルボキシフェニル）−５−メルカプトテトラゾール
ＡＦ−５：１−（３−アセトアミドフェニル）−５−メルカプトテトラゾール
Ｈ−１：〔（ＣＨ₂＝ＣＨＳＯ₂ＣＨ₂）₃ＣＣＨ₂ＳＯ₂ＣＨ₂ＣＨ₂〕₂ＮＣＨ₂ＣＨ₂ＳＯ₃Ｋ
Ｈ−２：２，４−ジクロロ−６−ヒドロキシ−ｓ−トリアジン・ナトリウム
Ｈ−３：ＣＨ₂＝ＣＨＳＯ₂ＣＨ₂ＣＨ（ＯＨ）ＣＨ₂ＳＯ₂ＣＨ＝ＣＨ₂
Ｈ−４：ＣＨ₂＝ＣＨＳＯ₂ＣＨ₂ＣＯＮＨＣＨ₂ＣＨ₂ＮＨＣＯＣＨ₂ＳＯ₂ＣＨ＝ＣＨ₂
ＯＩＬ−１：トリクレジルホスフェート
ＯＩＬ−２：ジ（２−エチルヘキシル）フタレート
ＡＳ−１：２，５−ビス（１，１−ジメチル−４−ヘキシルオキシカルボニルブチル）ハイドロキノン
ＡＳ−２：没食子酸ドデシル
ＡＳ−３：没食子酸ドコシル
ＡＳ−４：２−オクチルオキシ−５−ｔ−オクチル−Ｎ，Ｎ−ジブチルアニリン
ＡＳ−５：２，５−ジ−ｔ−オクチルハイドロキノン
ＡＳ−６：２，５−ジ−ｔ−オクチル−１，４−キノン
【０１１８】
【化１】

【０１１９】
【化２】

【０１２０】
【化３】

【０１２１】
【化４】

【０１２２】
【化５】

【０１２３】
【化６】

【０１２４】
【化７】

【０１２５】
【化８】

【０１２６】
【化９】

【０１２７】
【表２】

表３に、上記各試料に用いた沃臭化銀乳剤Ａ〜Ｉを示す。
【０１２８】
【表３】

【０１２９】
得られた試料について、下記により感度、粒状性（ＲＭＳ）、処理変動における階調安定性（Ｊｉ）の評価を緑色光を用いて行った。得られた結果を表４に示す。
【０１３０】
《感度の評価》
得られた試料に対し、通常のウェッジ露光を与え、下記の処理工程に従って現像処理を行った。
（処理工程）
処理工程 処理時間 処理温度 補充量^*
発色現像 ３分１５秒 ３８±０．３℃ ７８０ｍｌ
漂 白 ４５秒 ３８±２．０℃ １５０ｍｌ
定 着 １分３０秒 ３８±２．０℃ ８３０ｍｌ
安 定 ６０秒 ３８±５．０℃ ８３０ｍｌ
乾 燥 １分 ５５±５．０℃
＊補充量は感光材料１ｍ²当たりの量である。
【０１３１】
発色現像液、漂白液、定着液、安定液及びその補充液には、以下のものを使用した。

水を加えて１リットルとし、水酸化カリウムまたは２０％硫酸を用いて現像液はｐＨ１０．０６に、補充液はｐＨ１０．１８に調整する。
【０１３２】

水を加えて１リットルとし、アンモニア水または氷酢酸を用いて漂白液はｐＨ４．４に、補充液はｐＨ４．０に調整する。
【０１３３】

アンモニア水または氷酢酸を用いて定着液はｐＨ６．２に、補充液はｐＨ６．５に調整後、水を加えて１リットルとする。
【０１３４】

水を加えて１リットルとした後、アンモニア水または５０％硫酸を用いてｐＨ８．５に調整する。
【０１３５】
得られた処理済み試料のグリーン濃度の最小濃度＋０．２の濃度を得るのに必要な露光量の逆数を求め、感度とした。表４には、試料１０５の感度を１００とする相対値で示した。
【０１３６】
《粒状性（ＲＭＳ）の評価》
得られた試料に対し、通常のウェッジ露光を与え、上記の処理工程に従って現像処理を行った。
【０１３７】
得られた処理済み試料のグリーン濃度の最小濃度＋０．２の濃度の位置をイーストマンコダック社製のラッテンフィルター（Ｗ−９９）を装着したマイクロデンシトメーター（スリット幅１０μｍ、スリット長１８０μｍ）で走査し、濃度測定サンプリング数１０００以上の濃度値の変動の標準偏差を求め、粒状性（ＲＭＳ）を評価した。表４には、試料１０５の粒状性（ＲＭＳ）を１００とする相対値で示した。ＲＭＳ値（相対値）が小さい程、粒状性がよいことを意味する。
【０１３８】
《処理変動における階調安定性（Ｊｉ）の評価》
得られた試料に対し、通常のウェッジ露光を与え、上記の処理工程に従って現像処理を行った、また、上記の処理工程において、発色現像処理の時間を２分５０秒に短縮して処理工程を行った。
【０１３９】
得られた処理済み試料から、それぞれ横軸を露光量（ｌｏｇＥ）、縦軸をマゼンタ濃度値とした特性曲線を作成し、それよりＪｉ値を求めた。Ｊｉ値の求め方は次の通りである。
【０１４０】
特性曲線について、最小濃度＋０．５の濃度ｄ₀を与える露光量ｌｏｇＥ₀より更にΔｌｏｇＥ＝−１．２にあるｌｏｇＥ₄までの範囲で、ΔｌｏｇＥ＝−３．０単位毎にとった露光量点ｌｏｇＥ_i（ｉ＝０，１，２，３，４）において得られた濃度がｄ_i（ｉ＝０，１，２，３，４）であった場合、
ｇ_i＝（ｄ_i−ｄ_i-1）／−（ｌｏｇＥ_i−ｌｏｇＥ_i-1）
ｈ＝（ｄ₄−ｄ₀）／−（ｌｏｇＥ₄−ｌｏｇＥ₀）
を算出し、該値からｊ_i＝ｇ_i／ｈをそれぞれ求め、１．００から最も乖離の大きいｊ_iをもって各発色のＪｉとした。
【０１４１】
【表４】

【０１４２】
表４から明らかなように、本発明のハロゲン化銀写真感光材料は、処理変動における階調安定性が優れていることがわかる。また、特に、粒状性も良好であることがわかる。
【０１４３】
実施例２
（ハロゲン化銀乳剤の調製）
特開平１−１３１５４１号公報及び特開平５−１７３２７２号公報に記載と同様の方法で、表５に示す主平面形状、球換算平均粒径、平均ＡｇＩ量を有するハロゲン化銀乳剤を調製した。
【０１４４】
尚、それぞれの乳剤を電子顕微鏡観察したところ、全粒子に占める平板状粒子の割合が８０％（個数）以上の乳剤であった。
【０１４５】
【表５】

【０１４６】
（ハロゲン化銀写真感光材料試料の作成）
第９層（高感度緑感色性層）の沃臭化銀混合乳剤に代え、表６に示す組み合わせでＥＭ−５〜ＥＭ−８を混合した乳剤を用いた以外は実施例１と同様にしてハロゲン化銀写真感光材料試料２０１〜２０５を作成した。
【０１４７】
【表６】

【０１４８】
得られた各試料について、実施例１と全く同様にして、感度、粒状性、処理変動における階調安定性の評価を行った。得られた結果を表７に示す。なお、感度及びＲＭＳ値はそれぞれ試料２０５の値を１００とする相対値で示した。
【０１４９】
【表７】

【０１５０】
表７から明らかなように、本発明のハロゲン化銀写真感光材料は、処理変動における階調安定性が優れていることがわかる。また、特に、粒状性も良好であることがわかる。
【０１５１】
実施例３
（ハロゲン化銀乳剤の調製）
特願平９−２８１９５５号明細書に記載と同様の方法で、表８に示す転位線の長さの平均値、球換算平均粒径、平均ＡｇＩ量を有するハロゲン化銀乳剤を調製した。
【０１５２】
尚、それぞれの乳剤を電子顕微鏡観察したところ、全粒子に占める平板状粒子の割合が８０％（個数）以上の乳剤であった。
【０１５３】
【表８】

【０１５４】
（ハロゲン化銀写真感光材料試料の作成）
第９層（高感度緑感色性層）の沃臭化銀混合乳剤に代え、表９に示す組み合わせでＥＭ−９〜ＥＭ−１２を混合した乳剤を用いた以外は実施例１と同様にしてハロゲン化銀写真感光材料試料３０１〜３０５を作成した。
【０１５５】
【表９】

【０１５６】
得られた各試料について、実施例１と全く同様にして、感度、粒状性、処理変動における階調安定性の評価を行った。得られた結果を表１０に示す。なお、感度及びＲＭＳ値はそれぞれ試料３０５の値を１００とする相対値で示した。
【０１５７】
【表１０】

【０１５８】
表１０から明らかな様に、本発明のハロゲン化銀写真感光材料は処理変動における階調安定性が優れていることがわかる。また、特に粒状性も良好であることがわかる。
【０１５９】
実施例４
（ハロゲン化銀乳剤の調製）
特願平９−２８０４５９号明細書に記載と同様の方法で、表１１に示す球換算平均粒径、平均ＡｇＩ量を有し、また、表１１に示すように主平面上、フリンジ部に転位線を有するハロゲン化銀乳剤を調製した。
【０１６０】
尚、それぞれの乳剤を電子顕微鏡観察したところ、全粒子に占める平板状粒子の割合が８０％（個数）以上の乳剤であった。
【０１６１】
【表１１】

【０１６２】
（ハロゲン化銀写真感光材料試料の作成）
第９層（高感度緑感色性層）の沃臭化銀混合乳剤に代え、表１２に示す組み合わせでＥＭ−１３〜ＥＭ−１６を混合した乳剤を用いた以外は実施例１と同様にしてハロゲン化銀写真感光材料試料４０１〜４０５を作成した。
【０１６３】
【表１２】

【０１６４】
得られた各試料について、実施例１と全く同様にして、感度、粒状性、処理変動における階調安定性の評価を行った。得られた結果を表７に示す。なお、感度及びＲＭＳ値はそれぞれ試料４０５の値を１００とする相対値で示した。
【０１６５】
【表１３】

【０１６６】
表１３から明らかなように、本発明のハロゲン化銀写真感光材料は、処理変動における階調安定性が優れていることがわかる。また、特に、粒状性も良好であることがわかる。
【０１６７】
実施例５
（ハロゲン化銀乳剤の調製）
特願平９−２８０４５９号明細書に記載と同様の方法で、表１４に示す平均アスペクト比、転位線数の平均、球換算平均粒径、平均ＡｇＩ量を有するハロゲン化銀乳剤を調製した。
【０１６８】
尚、それぞれの乳剤を電子顕微鏡観察したところ、全粒子に占める平板状粒子の割合が８０％（個数）以上の乳剤であった。
【０１６９】
【表１４】

【０１７０】
（ハロゲン化銀写真感光材料試料の作成）
第９層（高感度緑感色性層）の沃臭化銀混合乳剤に代え、表１５に示す組み合わせでＥＭ−１７〜ＥＭ−２３を混合した乳剤を用いた以外は実施例１と同様にしてハロゲン化銀写真感光材料試料５０１〜５０８を作成した。
【０１７１】
【表１５】

【０１７２】
得られた各試料について、実施例１と全く同様にして、感度、粒状性、処理変動における階調安定性の評価を行った。得られた結果を表１６に示す。なお、感度及びＲＭＳ値はそれぞれ試料５０８の値を１００とする相対値で示した。
【０１７３】
【表１６】

【０１７４】
表１６から明らかなように、本発明のハロゲン化銀写真感光材料は、処理変動における階調安定性が優れていることがわかる。また、特に、粒状性も良好であることがわかる。
【０１８３】
実施例６
（ハロゲン化銀乳剤の調製）
特願平９−２８１９５５号明細書に記載と同様の方法で、表１７に示す転位線の長さの変動係数、球換算平均粒径、平均ＡｇＩ量を有するハロゲン化銀乳剤を調製した。
【０１８４】
尚、それぞれの乳剤を電子顕微鏡観察したところ、全粒子に占める平板状粒子の割合が８０％（個数）以上の乳剤であった。
【０１８５】
【表１７】

【０１８６】
（ハロゲン化銀写真感光材料試料の作成）
第９層（高感度緑感色性層）の沃臭化銀混合乳剤に代え、表１８に示す組み合わせでＥＭ−２４〜ＥＭ−２７を混合した乳剤を用いた以外は実施例１と同様にしてハロゲン化銀写真感光材料試料６０１〜６０５を作成した。
【０１８７】
【表１８】

得られた各試料について、実施例１と全く同様にして、感度、粒状性、処理変動における階調安定性の評価を行った。得られた結果を表１９に示す。なお、感度及びＲＭＳ値はそれぞれ試料６０５の値を１００とする相対値で示した。
【０１８８】
【表１９】

表１９から明らかなように、本発明のハロゲン化銀写真感光材料は、処理変動における階調安定性が優れていることがわかる。また、特に、粒状性も良好であることがわかる。
【０１８９】
【発明の効果】
本発明により感度を損なうことなく優れた粒状性を達成し、かつ市場で起こる環境変動に対して安定した階調再現を与えるハロゲン化銀カラー写真感光材料を提供する事ができる。[0001]
[Industrial application fields]
The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material having excellent graininess and improved gradation stability in processing fluctuation.
[0002]
[Prior art]
In recent years, in the field of silver halide color photographic light-sensitive materials, higher image quality has been demanded, for example, by reducing the size of a film according to a new standard (advanced photo system).
[0003]
In addition, with the widespread use of compact cameras and lens-equipped films, it is also an important requirement that gradation reproduction be stably obtained against various environmental changes that occur in the market. In response to such demands, many studies have been made centering on improvement of silver halide emulsions.
[0004]
In general, in order to improve the image quality, it is effective to reduce the grain size of silver halide grains, increase the number of grains per unit silver halide amount, and increase the number of coloring points (number of pixels). However, since reducing the particle size causes a decrease in sensitivity, there is a limit to satisfy both high sensitivity and high image quality. Therefore, a technique for improving the sensitivity / size ratio per silver halide grain has been studied. As one of the techniques, a technique using tabular silver halide grains is disclosed in Japanese Patent Application Laid-Open No. 58-11935. No. 58-11936, No. 58-11937, No. 58-11939, No. 59-99433, and the like. A tabular silver halide emulsion (hereinafter also simply referred to as “tabular grain”) is a unit of silver halide grains as compared with an emulsion composed of so-called normal silver halide grains such as hexahedron, octahedron or dodecahedron. Since the surface area per volume is large and more spectral sensitizing dyes can be adsorbed on the particle surface, high sensitivity including improvement in color sensitization efficiency can be expected.
[0005]
In JP-A-63-163451, the ratio (b / a) between the longest distance (a) between two or more parallel twin planes and the thickness (b) of the particles is 5 or more. As a technique using tabular grains, JP-A-1-201649 discloses a technique that simultaneously defines the number of transition lines existing in tabular grains. Japanese Patent Application Laid-Open No. 1-1131541 discloses a technique using tabular grains in which the shape of two parallel main outer surfaces is a circle having a linear portion ratio of 4/5 or less. The effect of improving graininess without lowering the sensitivity has been reported by a technique focusing on twin planes of these tabular grains, introduction of transition lines, control of grain shape, and the like.
[0006]
However, when these silver halide grains are used, there is a problem that gradation stability is impaired due to processing variations.
[0007]
On the other hand, from the viewpoint of gradation stability, JP-A-1-304459, JP-A-4-93941, JP-A-4-40446 and the like disclose at least two kinds of monodispersed silver halides having different average particle diameters. Techniques for incorporating emulsions in the same light sensitive layer or all of the same color sensitive groups are shown.
[0008]
However, the improvement effect of these techniques is insufficient to meet the recent high-level requirements, and further improvement in performance is desired.
[0009]
[Problems to be solved by the invention]
Accordingly, an object of the present invention is to provide a silver halide photographic light-sensitive material that achieves excellent graininess without impairing sensitivity, and provides stable gradation reproduction against environmental fluctuations that occur in the market. is there.
[0010]
[Means for Solving the Problems]
  The above object of the present invention is to
(1) In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, the average value of the distance between twin planes is 30 nm or more in at least one silver halide emulsion layer. A tabular silver halide emulsion (A) having an average distance between twin planes of less than 30 nm and a sphere-converted average grain size equal to or smaller than that of the tabular silver halide emulsion (A) A silver halide photographic material comprising a silver halide emulsion (B). (First invention)
(2) In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, a tabular halogen having a circular main plane in at least one silver halide emulsion layer A silver halide emulsion (D), and a tabular silver halide emulsion (D) having a hexagonal main plane shape and a sphere-equivalent average particle size equal to or smaller than that of the tabular silver halide emulsion (C). A silver halide photographic light-sensitive material characterized by containing. (Second invention)
(3) In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, the average length of dislocation lines is 30 nm or more in at least one silver halide emulsion layer. A tabular silver halide emulsion (E) having an average dislocation line length of less than 30 nm and a sphere-converted average grain size equal to or smaller than that of the tabular silver halide emulsion (E) A silver halide photographic material comprising a silver halide emulsion (F). (Third invention)
(4) In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, a tabular shape having dislocation lines mainly on the main plane in at least one silver halide emulsion layer A silver halide emulsion (G), a tabular silver halide emulsion (H) having a dislocation line only in the fringe portion and having a sphere-equivalent average particle diameter equal to or smaller than that of the tabular silver halide emulsion (G) A silver halide photographic light-sensitive material comprising: (Fourth invention)
(5) In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, one grain having an average aspect ratio of 8 or more in at least one silver halide emulsion layer A tabular silver halide emulsion (I) having 30 or more permeation lines, an average aspect ratio of 5 or more and less than 8 and 30 or more dislocation lines per grain, and a sphere-converted average grain size value of a flat plate A silver halide photographic light-sensitive material containing a tabular silver halide emulsion (J) which is equal to or smaller than the silver halide emulsion (I). (Fifth invention)
(6)In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, a plate having a dislocation line length variation coefficient of less than 25% in at least one silver halide emulsion layer. Tabular silver halide emulsion (M) and tabular silver halide having a dislocation line length variation coefficient of 25% or more and a sphere-equivalent average grain size equal to or smaller than tabular silver halide emulsion (M) A silver halide photographic light-sensitive material comprising an emulsion (N).(Sixth invention)
Is achieved.
[0011]
The present invention will be described in detail below.
[0012]
The tabular silver halide emulsion according to the present invention is a silver halide emulsion containing tabular silver halide grains.
[0013]
Tabular grains are silver halide grains that are crystallographically classified as twins. Twins are silver halide crystals with one or more twin planes in one grain, but the classification of twins is based on the Klein and Moiser publications Photographische Korrespondenz. ) Volume 99, p100, Volume 100, p57.
[0014]
The tabular grains in the present invention have two twin planes parallel to the main plane. The twin plane can be observed with a transmission electron microscope. The specific method is as follows. First, a silver halide photographic emulsion is coated on the support so that the contained tabular grains are oriented substantially parallel to the main plane, thereby preparing a sample. This is cut using a diamond cutter to obtain a thin slice having a thickness of about 0.1 μm. The existence of twin planes can be confirmed by observing this section with a transmission electron microscope.
[0015]
The distance between the two twin planes in the tabular grains according to the present invention is such that the tabular grains showing a cross section cut almost perpendicularly to the main plane can be arbitrarily determined in the observation of the section using the transmission electron microscope. The distance between two twin planes having the shortest distance among the even number of twin planes parallel to the main plane is obtained for each grain and obtained by averaging.
[0016]
In the present invention, the distance between twin planes is a factor that affects the supersaturation state during nucleation, such as gelatin concentration, gelatin species, temperature, iodine ion concentration, pBr, pH, ion supply speed, stirring rotation speed, etc. It can control by selecting appropriately in the combination of various factors. Generally speaking, the distance between twin planes can be narrowed as nucleation is performed in a highly supersaturated state.
[0017]
Details regarding the supersaturation factor can be referred to, for example, descriptions in JP-A-63-92924 and JP-A-1-213737.
[0018]
In the present invention, the thickness of the tabular grains is obtained by obtaining the thickness of each grain in the same manner by observing the section using the above-mentioned transmission electron microscope, and adding and averaging them. The thickness of the tabular grains is preferably 0.05 μm to 1.5 μm, more preferably 0.07 μm to 0.50 μm.
[0019]
In the present invention, the tabular grains are those in which 50% or more of the total projected area has an aspect ratio (particle size / grain thickness) of 5 or more, but preferably 60% or more of the total projected area has an aspect ratio of 5 More preferably, 70% or more of the total projected area has an aspect ratio of 5 or more.
[0020]
The present invention relates to a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, and two kinds of tabular silver halide emulsions in at least one silver halide emulsion layer. contains.
[0021]
In the present invention, the sphere equivalent particle diameter is a particle diameter obtained as a diameter of a sphere having the same volume as the silver halide grains.
[0022]
The tabular grains of the present invention preferably have a sphere-equivalent average particle diameter value of 0.2 μm or more, more preferably 0.3 μm to 3.0 μm.
[0023]
  In the first invention of the present invention, the sphere equivalent average particle size values of the tabular silver halide emulsions (A) and (B) are in the relationship of (A) ≧ (B). The average spherical grain size of the silver halide emulsions (C) and (D) is in the relationship of (C) ≧ (D). In the third invention, the tabular silver halide emulsions (E) and (F) The sphere-converted average particle size is in the relationship of (E) ≧ (F). In the fourth invention of the present invention, the sphere-converted average particle size of the tabular silver halide emulsions (G) and (H) is (G ) ≧ (H), in the fifth invention of the present invention, the spherical equivalent average grain size values of the tabular silver halide emulsions (I) and (J) are in the relationship of (I) ≧ (J),6th inventionIn, the average spherical grain size values of the tabular silver halide emulsions (M) and (N) are in a relationship of (M) ≧ (N).
[0024]
In the present invention, the spherical equivalent particle diameter is obtained by, for example, photographing silver halide grains with an electron microscope at a magnification of 10,000 to 70,000 times and measuring the particle diameter and thickness on the print. be able to. The number of measured particles is indiscriminately 1000 or more.
[0025]
The sphere equivalent average particle diameter r is the frequency ni and ri of particles having a sphere equivalent particle diameter ri.^ThreeProduct ni × ri with^ThreeIs defined as the particle size ri when the maximum value is reached (3 significant digits, rounded off to the least significant digit).
[0026]
The tabular grains of the present invention are preferably monodispersed silver halide emulsions. Here, in the monodispersed silver halide emulsion, the weight of silver halide contained in a grain size range of ± 20% centered on the sphere-converted average grain diameter r is 60% or more of the total silver halide grain weight. Is preferable, more preferably 70% or more, still more preferably 80% or more.
[0027]
In the first invention, the average value of the distance between twin planes of the tabular silver halide emulsion (A) is 30 nm or more, preferably 35 nm or more, and more preferably 38 nm or more. On the other hand, the average value of the distance between twin planes of the tabular silver halide (B) is less than 30 nm, preferably less than 25 nm, and more preferably less than 22 nm.
[0028]
In the second invention, in the tabular silver halide emulsion (C) whose main plane shape is circular, the tabular grains whose main plane shape is circular are all the silver halide grains in the silver halide emulsion. It accounts for 50% or more, preferably 70% or more, more preferably 90% or more of the projected area.
[0029]
Here, a tabular grain having a circular main plane shape means a particle having a circular (111) main plane shape.
[0030]
In general, the shape of the (111) main plane of a tabular grain having two parallel twin planes shows a hexagonal shape, and the circular tabular grain referred to here corresponds to a rounded corner of the hexagonal shape. . The main plane of the circular tabular grains in the present invention is circular, but it may not be completely circular. That is, you may have a linear part in part. When it has a straight part, it is preferable that the side length of the hexagonal flat plate having an adjacent side ratio of 2-1 is 4/5 to 0 (hereinafter referred to as a straight part ratio of 4/5 or less). However, the length of the side when the corner of this hexagonal tabular grain is rounded is the distance between the intersection with the line that extends the straight part of that side and the straight part of the adjacent side. It is represented by Of course, it may be a circular particle having no straight part (that is, a straight part ratio of zero). Preferably, the straight part ratio is 1/2 to 0.
[0031]
As a method for producing a tabular silver halide emulsion having a circular main plane, there is a method in which a second Ostwald ripening is performed after nucleation, first Ostwald ripening and crystal growth.
[0032]
This second aging is preferably performed under the following conditions.
[0033]
That is, temperature; 40 ° C to 80 ° C, preferably 50 ° C to 80 ° C, time; 10 to 100 minutes, preferably 20 to 60 minutes, gelatin concentration; 0.05 to 10% by weight, preferably 1.0 to 5% % By weight, silver halide solvent concentration; 0 to 0.4 mol / L, preferably 10^-Four-0.1 mol / L. pBr is 1.8 to 3.5, preferably 2.0 to 3.0. In particular, when ripening on the low pAg side, tabular grains generally have their edges dissolved, and the dissolved grains are deposited on the main surface of the tabular grains. That is, with the melting of the edge, the aspect ratio decreases while becoming circular. This is because the equilibrium crystal habit is the (100) plane on the low pAg side, and the morphology tends to shift to the equilibrium crystal habit side.
[0034]
The degree of rounding the edges of the hexagonal tabular grains depends on the temperature during the second ripening, the pBr value, the type and concentration of the silver halide solvent used, and specifically, obtained by changing the ripening conditions. Conditions can be set by observing an electron microscopic image of the particles. Normally, increasing the concentration of the silver halide solvent promotes circularization, and Br^-When the concentration is increased, circularization is suppressed.
[0035]
This second ripening step also has an effect of reducing a small amount of non-tabular fine particles present after the formation of hexagonal tabular grains.
[0036]
As another method for producing circular tabular grains, there is a method of growing crystals under low pAg and in the presence of an AgX solvent under low supersaturation after making hexagonal tabular grains. By doing in this way, an edge part becomes round and a (100) surface appears in an edge part.
[0037]
This low pAg condition is pBr 1.8-4.0, preferably 2.0-3.5, and the low supersaturation is 0-40% of the critical growth rate of the emulsion. Moreover, as a density | concentration of the AgX solvent to be used, it is 0-10.^-1Mol / L is preferred.
[0038]
In the second invention, in the tabular silver halide emulsion (D) whose main plane shape is hexagonal, tabular grains whose main plane shape is hexagonal are silver halide grains in the silver halide emulsion. 50% or more, preferably 70% or more, more preferably 90% or more of the total projected area.
[0039]
Here, the hexagonal tabular grains are grains having a (111) plane of hexagonal shape and a maximum adjacent side ratio of 1.0 to 2.0. Here, the maximum adjacent side ratio is a ratio of the length of the side having the maximum length to the length of the side having the minimum length forming the hexagon. The hexagonal tabular grains of the present invention may have rounded corners as long as the maximum adjacent side ratio is 1.0 to 2.0. When the corner is somewhat rounded, the length of the side is expressed by the distance between the intersection of the straight line portion of the side and the line extending the straight line portion of the adjacent side.
[0040]
As for each side which forms the hexagon of the hexagonal tabular grain of the present invention, it is preferable that 1/2 or more thereof is substantially a straight line, particularly 4/5 or more is substantially linear. In the present invention, the adjacent side ratio is more preferably 1.0 to 1.5.
[0041]
The average silver iodide content of the silver halide emulsion of the present invention is preferably 1 mol% or more, more preferably 1 to 10 mol%, and particularly preferably 2 to 8 mol%.
[0042]
The tabular grains of the present invention are preferably emulsions mainly containing silver iodobromide, but may contain silver halides of other compositions such as silver chloride within a range not impairing the effects of the present invention. it can.
[0043]
The silver iodide distribution in the silver halide grains can be detected by various physical measurement methods, for example, at a low temperature as described in the Abstracts of the Annual Meeting of the Photographic Society of Japan, 1981. Luminescence measurement, EPMA method, X-ray diffraction method.
[0044]
In the present invention, the silver iodide content and average silver iodide content of individual silver halide grains can be determined by using the EPMA method (Electron Probe Micro Analyzer method). In this method, a sample in which emulsion grains are well dispersed so as not to touch each other is prepared, an electron beam is irradiated, and X-rays generated by electron beam excitation are analyzed to perform elemental analysis of a very small portion. is there. By this method, the halogen composition of individual grains can be determined by obtaining the characteristic X-ray intensity of silver and iodine emitted from each grain. If the silver iodide content is determined by EPMA method for at least 50 grains, the average silver iodide content can be determined from the average of them.
[0045]
The tabular grains of the present invention preferably have a more uniform silver iodide content between grains. When the distribution of silver iodide content between grains is measured by the EPMA method, the relative standard deviation is preferably 30% or less, more preferably 20% or less.
[0046]
The silver iodide content on the surface of the tabular grains of the present invention is preferably 1 mol% or more, and more preferably 2 to 20 mol%.
[0047]
In the present invention, the surface of tabular grains refers to the outermost layer of grains including the outermost surface of silver halide grains and means the depth of 50 mm from the outermost surface of the grains. The halogen composition on the surface of the tabular grains of the present invention is determined by the XPS method (X-ray Photoelectron Spectroscopy method: X-ray photoelectron spectroscopy) as follows.
[0048]
That is, the sample is 1 × 10^-8Cool to −110 ° C. or less in an ultrahigh vacuum of torr or less, and irradiate MgKα as a probe X-ray with an X-ray source voltage of 15 kV and an X-ray source current of 40 mA. Measure for 2 electrons. The integrated intensity of the measured peak is corrected with a sensitivity factor, and the halide composition on the surface of the silver halide is determined from these intensity ratios.
[0049]
Next, the dislocation lines that the silver halide grains have will be described.
[0050]
Dislocation lines possessed by silver halide grains can be obtained at low temperatures described in, for example, JF Hamilton, Photo. Sci. Eng. 11 (1967) 57 and T. Shiozawa, J. Soc. Photo. Sci. It can be observed by a direct method using a transmission electron microscope. In other words, silver halide grains taken out carefully so as not to apply pressure to the grains from the emulsion are placed on an electron microscope mesh to prevent damage (printout, etc.) due to electron beams. Observation is performed by the transmission method with the sample cooled. At this time, 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 electron microscope. From the particle photograph obtained by such a method, the position, number and length of dislocation lines in each particle can be obtained.
[0051]
In the fourth invention, the tabular silver halide grains (G) having dislocation lines mainly on the main plane are the number of dislocation lines existing in the central region of the main plane is the total number of dislocation lines existing in the grains. On the other hand, it refers to particles that are 80% or more.
[0052]
The central region of the main plane of the tabular grains herein has a radius of 80% of the radius of a circle having the same area as the main plane of the tabular grains, and the tabular shape in the circular portion when the center is shared. A region having the thickness of a particle. On the other hand, the fringe portion of the tabular grains refers to a region having an area corresponding to the annular region outside the central region and existing around the tabular grains and having the thickness of the tabular grains.
[0053]
The number of dislocation lines existing in one particle is measured as follows. A series of particle photographs with different tilt angles with respect to the incident electrons are taken for each particle to confirm the presence of dislocation lines. At this time, the number of dislocation lines that can be counted is counted. When the number of dislocation lines per particle cannot be counted, such as when dislocation lines are densely present or when dislocation lines cross each other, it is counted that there are many dislocation lines.
[0054]
The dislocation lines existing in the central region of the main plane of the tabular grains often form a so-called dislocation network, and the number of the dislocation lines may not be clearly counted. Dislocation lines existing in the peripheral region are observed as lines extending radially from the center of the particle toward the side, but often meander.
[0055]
  Third invention6th inventionIn the tabular grains, the number ratio of 30% or more has a transition line, but the number ratio of 50% or more preferably has a transition line, and the number ratio of 70% or more has a transition line. More preferably, it has.
[0056]
In the third invention, the average transition line length of the tabular silver halide emulsion (E) is 30 nm or more, preferably 35 nm or more. On the other hand, the average value of the transition line length of the tabular silver halide emulsion (F) is less than 30 nm, preferably less than 25 nm.
[0057]
Here, the average value of the length of transition lines means the average value of the length of transition lines existing in one grain. In the tabular silver halide emulsion (E), the number of grains satisfying the above conditions is the number ratio. Although 30% or more is present, it is preferable that particles satisfying the above conditions are present in a number ratio of 50% or more.
[0058]
In the fourth invention, the tabular silver halide emulsion (G) has transition lines mainly on the main plane. Here, having transition lines mainly on the main plane means that the number of transition lines existing on the main plane is 70% or more with respect to the total number of transition lines existing in one particle, but 80% The above is preferably present on the main plane, and more preferably 90% or more is present on the main plane.
[0059]
On the other hand, the tabular silver halide emulsion (H) has transition lines mainly in the fringe portion, and the number thereof is 10 or more. Here, having transition lines mainly only in the fringe part means that the number of transition lines existing in the fringe part is 70% or more with respect to the total number of transition lines existing in one particle, but 80% or more. Is preferably present in the fringe portion, more preferably 90% or more is present in the fringe portion.
[0060]
In the tabular silver halide emulsion (G) and the tabular silver halide emulsion (H), it is necessary that the number of grains satisfying the above-mentioned position of the transition line is 50% or more with respect to the number of grains having the transition line. However, it is preferably 70% or more, more preferably 90% or more.
[0061]
In the fifth invention, the tabular silver halide emulsion (I) has an average aspect ratio of 8 or more and 30 or more transition lines per grain, preferably 40 or more transition lines per grain. More preferably, it has 50 or more transition lines per particle.
[0062]
On the other hand, the tabular silver halide emulsion (J) has an average aspect ratio of 5 or more and less than 8 and has 30 or more transition lines per grain, preferably 40 or more transition lines per grain. More preferably, it has 50 or more transition lines per particle.
[0063]
Here, the number of particles satisfying the condition of the number of transition lines needs to be 50% or more with respect to the number of particles having transition lines, preferably 70% or more, and more preferably 90% or more.
[0064]
  6th inventionThe tabular silver halide emulsion (M) has a variation coefficient of transition line length of less than 25%, preferably 20% or less.
[0065]
On the other hand, the tabular silver halide emulsion (N) has a transition line length variation coefficient of 25% or more, preferably 30% or more.
[0066]
Here, the variation coefficient of the length of the transition line is obtained from the transition line existing in one particle. The number of particles satisfying the above-mentioned coefficient of variation needs to be 70% or more with respect to the number of particles having transition lines, preferably 80% or more, and more preferably 90% or more.
[0067]
As a method for introducing dislocation lines into silver halide grains, for example, an aqueous solution containing iodine ions such as potassium iodide and a water-soluble silver salt solution are added by a double jet, or a fine grain emulsion containing silver iodide is added. Known methods such as a method of adding only a solution containing iodine ions, a method of using an iodine ion releasing agent as described in JP-A-6-11781, and the like can be used. Dislocations that form the origin of dislocation lines can be formed. Among these methods, a method of adding a fine grain emulsion containing silver iodide and a method of using an iodine ion releasing agent are particularly preferable.
[0068]
When an iodine ion releasing agent is used, sodium p-iodoacetamidobenzenesulfonate, 2-iodoethanol, 2-iodoacetamide and the like can be preferably used.
[0069]
In the present invention, the tabular grains may be either grains in which a latent image is mainly formed on the surface or grains mainly formed inside the grains.
[0070]
The tabular grains used in the present invention are produced in the presence of a dispersion medium, that is, in a solution containing the dispersion medium. Here, the aqueous solution containing a dispersion medium refers to a material in which a protective colloid is formed in an aqueous solution by gelatin or other substances that can form a hydrophilic colloid (such as a substance that can serve as a binder), preferably colloidal protection. An aqueous solution containing gelatin.
[0071]
When gelatin is used as the protective colloid, the gelatin may be lime-treated or acid-treated. Details of the gelatin production process are described in Arthur Guice, The Macromolecular Chemistry of Gelatin (Academic Press, 1964).
[0072]
Examples of hydrophilic colloids that can be used as protective colloids other than gelatin include gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, and the like. Sugar derivatives such as cellulose derivatives, sodium alginate, starch derivatives and the like; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. There are a variety of synthetic hydrophilic polymer materials such as coalesces or copolymers.
[0073]
In the case of gelatin, it is preferable to use a gelatin having a jelly strength of 200 or more in the Paguii method.
[0074]
The tabular grains in the present invention are formed from cadmium salts, zinc salts, lead salts, thallium salts, iron salts, rhodium salts, iridium salts, and indium salts (including complex salts) in the process of forming and / or growing the grains. Metal ions can be added using at least one selected from the above, and these metal elements can be contained inside and / or on the particle surface.
[0075]
As a means for forming tabular grains, various methods well known in the art can be used. In other words, the single jet method, controlled double jet method, controlled triple jet method, etc. can be used in any combination, but in order to obtain highly monodisperse grains, the formation of silver halide grains It is important to control the pAg in the liquid phase to be adjusted according to the growth rate of the silver halide grains. As the pAg value, an area of 7.0 to 12 is used, and preferably an area of 7.5 to 11 can be used.
[0076]
In determining the addition rate, the techniques described in JP-A-54-48521 and JP-A-58-49938 can be referred to.
[0077]
The tabular grain preparation process is roughly divided into a nucleation process, an aging process (nucleation aging process), and a subsequent growth process. It is also possible to separately grow a nuclear emulsion (or seed emulsion) prepared in advance. The growth process may include several stages such as a first growth process and a second growth process. The growth process of tabular grains of the present invention means all growth processes from the formation of nuclei (or seeds) to the end of grain growth, and the time of starting growth means the start time of the growing process.
[0078]
During the production of tabular grains, a known silver halide solvent such as ammonia, thioether, thiourea or the like can be present, or a silver halide solvent need not be used.
[0079]
In order to selectively form dislocation lines in the central region of the main plane of the tabular grains, it is important to age so that the pH is increased and the thickness of the tabular grains is increased in the ripening step after nucleation. However, if the pH is too high, the aspect ratio is too low, and control for increasing the aspect ratio in the subsequent growth process becomes difficult. In addition, it may cause unexpected fog deterioration. Therefore, the pH of the aging step is 7.0 to 11.0, the temperature is preferably 40 to 80 ° C., the pH is preferably 8.5 to 10.0, and the temperature is more preferably 50 to 70 ° C.
[0080]
In order to selectively form dislocation lines in the outer peripheral region of the tabular grains, an iodine ion source (for example, silver iodide fine particles, iodine ion releasing agent) for introducing the dislocation lines into the outer peripheral region is used in the growth process. It is important to increase the pAg in the grain growth after being added to the base grain, but if the pAg is too high, so-called Ostwald ripening will proceed simultaneously with grain growth, and the monodispersity of the tabular grains will deteriorate. . Accordingly, the pAg when forming the outer peripheral region of the tabular grains in the growth step is preferably 8 to 12, and more preferably 9.5 to 11. When an iodine ion releasing agent is used as the iodine ion source, dislocation lines can be effectively formed in the outer peripheral region by increasing the amount of addition. The addition amount of the iodine ion releasing agent is preferably 0.5 mol or more, more preferably 2 to 5 mol per mol of silver halide.
[0081]
The tabular grains of the present invention may be those obtained by removing unnecessary soluble salts after completion of the growth of the silver halide grains, or may be contained as is.
[0082]
Further, as described in JP-A-60-138538, desalting can be performed at any point of silver halide growth. Further, the removal of salts can be performed based on the method described in Research Disclosure (hereinafter abbreviated as RD) No. 17643, Item II. Furthermore, in order to remove soluble salts from the emulsion after precipitation or physical ripening, a Nudell water washing method in which gelatin is gelled may be used, and inorganic salts, anionic surfactants, A precipitation method (flocculation) using an anionic polymer (for example, polystyrene sulfonic acid) or a gelatin derivative (for example, acylated gelatin, carbamoylated gelatin, etc.) may be used. Specific examples include the method described in JP-A-5-72658, and these can be preferably used.
[0083]
The tabular grains of the present invention can be chemically sensitized by a conventional method. That is, sulfur sensitization, selenium sensitization, noble metal sensitization using gold or other noble metal compounds can be used alone or in combination.
[0084]
The tabular grains according to the present invention can be optically sensitized to a desired wavelength range using a dye known as a sensitizing dye in the photographic industry. Sensitizing dyes may be used alone or in combination of two or more. A dye that does not have spectral sensitization by itself or a compound that does not substantially absorb visible light, and contains a supersensitizer that enhances the sensitizing action of the sensitizing dye in the emulsion. Also good.
[0085]
An antifoggant, a stabilizer and the like can be added to the tabular grains according to the present invention. It is advantageous to use gelatin as the binder. The emulsion layer and other hydrophilic colloid layers can be hardened and can contain a plasticizer, a water-insoluble or soluble synthetic polymer dispersion (latex).
[0086]
A coupler is used for the emulsion layer of the color photographic light-sensitive material. Furthermore, a development accelerator, a developer, a silver halide solvent, a toning agent, a hardener, a fogging agent, an antifoggant by coupling with a competitive coupler having an effect of color correction and an oxidized form of a developing agent, Compounds that release photographically useful fragments such as chemical sensitizers, spectral sensitizers and desensitizers can be used.
[0087]
The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer and an irradiation prevention layer. These layers and / or the emulsion layer may contain a dye which flows out of the photosensitive material during the development process or is bleached.
[0088]
Matting agents, lubricants, image stabilizers, formalin scavengers, ultraviolet absorbers, fluorescent brighteners, surfactants, development accelerators and development retarders can be added to the photosensitive material.
[0089]
As the support, films such as polyethylene laminated paper, polyethylene terephthalate film, baryta paper, cellulose triacetate can be used.
[0090]
【Example】
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
[0091]
Example 1
(Preparation of silver halide emulsion)
In the same manner as described in JP-A-7-191425, a silver iodobromide emulsion having the average value of the distance between twin planes shown in Table 1, the average particle diameter in terms of sphere, and the average AgI amount was prepared.
[0092]
[Table 1]

Each emulsion was observed with an electron microscope, and the proportion of tabular grains in all grains was 80% (number) or more.
[0093]
(Production of support)
0.1 part of calcium acetate hydrate was added as a transesterification catalyst to 100 parts of dimethyl 2,6-naphthalenedicarboxylate and 60 parts of ethylene glycol, and a transesterification reaction was carried out according to a conventional method. To the obtained product, 0.05 part of antimony trioxide and 0.03 part of trimethyl phosphate were added. Subsequently, the temperature was gradually raised and the pressure was reduced, and polymerization was carried out under the conditions of 290 ° C. and 0.05 mmHg to obtain polyethylene-2,6-naphthalate having an intrinsic viscosity of 0.60.
[0094]
This was vacuum-dried at 150 ° C. for 8 hours, and then melt-extruded in layers from a T die at 300 ° C., closely adhered to a 50 ° C. cooling drum while being electrostatically applied, and cooled and solidified to obtain an unstretched sheet. This unstretched sheet was stretched 3.3 times in the longitudinal direction at 135 ° C. using a roll type longitudinal stretching machine.
[0095]
The obtained uniaxially stretched film was stretched using a tenter-type transverse stretching machine so that the total transverse stretching ratio was 50% in the first stretching zone 145 ° C., and further in the second stretching zone 155 ° C. The film was stretched so that the magnification was 3.3 times. Next, heat treatment was performed at 100 ° C. for 2 seconds, and heat setting was further performed at the first heat setting zone 200 ° C. for 5 seconds, and heat setting was performed at the second heat setting zone 240 ° C. for 15 seconds. Subsequently, the film was gradually cooled to room temperature over 30 seconds while being subjected to a 5% relaxation treatment in the lateral direction to obtain a polyethylene naphthalate film having a thickness of 85 μm.
[0096]
This was wound around a stainless steel core and heat-treated at 110 ° C. for 48 hours (annealing treatment) to produce a support.
[0097]
(Coating the undercoat layer)
12 W / m on both sides of this support²/ Min of corona discharge treatment, and the following undercoat coating solution B-1 is applied on one surface to a dry film thickness of 0.4 μm, and 12 W / m is applied thereon.²/ Min corona discharge treatment was applied, and the following undercoat coating solution B-2 was applied to a dry film thickness of 0.06 μm.
[0098]
12W / m²On the other surface subjected to a corona discharge treatment of / min, the following undercoat coating solution B-3 is applied to a dry hard film of 0.2 μm, and 12 W / m is applied thereon.²/ Min corona discharge treatment was applied, and the following undercoat coating solution B-4 was applied to a dry film thickness of 0.2 μm.
[0099]
Each layer was dried at 90 ° C. for 10 seconds after coating, and after four layers were coated, heat treatment was subsequently performed at 110 ° C. for 2 minutes, followed by cooling at 50 ° C. for 30 seconds.
[0100]
<Undercoating liquid B-1>
Butyl acrylate / t-butyl acrylate / styrene / 2-hydroxyethyl
Polyacrylate copolymer (30/20/25/25% by weight) latex liquid (solid
Min 30%) 125g
Compound (UL-1) 0.4 g
Hexamethylene-1,6-bis (ethyleneurea) 0.05g
Finish to 1 liter with water
[0101]
<Undercoating liquid B-2>
Sodium hydroxide of styrene / maleic anhydride copolymer
Aqueous solution (solid content 6%) 50g
Compound (UL-1) 0.6 g
Compound (UL-2) 0.09 g
Silica particles (average particle size 3μm) 0.2g
Finish to 1 liter with water
[0102]
<Undercoating liquid B-3>
Butyl acrylate / t-butyl acrylate / styrene / 2-hydroxyethyl
Polyacrylate copolymer (30/20/25/25% by weight) latex liquid (solid
30% min) 50g
Compound (UL-1) 0.3 g
Hexamethylene-1,6-bis (ethyleneurea) 1.1g
Finish to 1 liter with water
UL-1: o, p- (C₉H₁₉)₂C₆H_ThreeO (CH₂CH₂O)₁₂SO_ThreeNa
UL-2: CH_ThreeSO₂O (CH₂)_ThreeOSO₂CH_Three
[0103]
<Undercoating liquid B-4>
An aqueous dispersion (solid content) of tin oxide-antimony oxide composite fine particles (average particle size 0.2 μm)
40g) 109g
Water dispersion A 67g
Finish to 1 liter with water
Aqueous dispersion A: 60 mol% dimethyl terephthalate as dicarboxylic acid component, 30 mol% dimethyl isophthalate, 10 mol% sodium salt of dimethyl 5-sulfoisophthalate, 50 mol% ethylene glycol and 50 mol% diethylene glycol as glycol components The copolymer was copolymerized by a conventional method, and the copolymer was stirred in hot water at 95 ° C. for 3 hours to obtain a 15% by weight aqueous dispersion A.
[0104]
(Coating of transparent magnetic recording layer)
<Preparation and coating of magnetic coating solution 1>
The following composition (A) was dispersed using a sand mill for 40 hours, and then filtered through a filter having an average pore diameter of 10 μm to obtain a magnetic paint.
Composition (A)
Co-coated γ-Fe₂O_Three(Major axis 0.15 μm, minor axis 0.03 μm, specific surface area 40 m
²/ G, Hc = 900 oersted) 5 parts
100 parts of diacetylcellulose (degree of acetylation = 55%, Mw = 180,000)
α-alumina (average particle size 0.3 μm) 10 parts
780 parts of acetone
340 parts of cyclohexanone
[0105]
The magnetic coating liquid 1 was prepared by continuously adding and mixing the following composition (B) mixed so as not to entrain air using a disper in the magnetic coating.
Composition (B)
Hardener (manufactured by Nippon Polyurethane Co., Ltd .: CL, solid content 75%) 20 parts
45 parts of cyclohexanone
[0106]
The obtained magnetic coating solution 1 was applied and dried so as to have a dry film thickness of 0.8 μm on the side on which the undercoat coating solutions B-3 and B-4 of the polyethylene naphthalate support were coated.
(Preparation of silver halide photographic material sample)
On the opposite side of the magnetic recording medium from the magnetic recording layer, an undercoat layer in which the undercoat coating liquids B-1 and B-2 are applied under the same conditions is provided, and a photographic composition having the following composition is provided. Layers were sequentially formed from the support side to obtain Samples 101 to 105. Each emulsion was coated after optimal gold-sulfur sensitization.
[0107]
The addition amount of the photographic composition layer shown below is 1 m²Expressed in grams per unit. However, silver halide and colloidal silver were converted to the amount of silver, and sensitizing dyes were shown in moles per mole of silver.
[0108]

[0109]

[0110]

[0111]

[0112]

[0113]

[0114]

[0115]

[0116]
In addition to the above composition, coating aids SU-1, SU-2, SU-3, dispersion aid SU-4, viscosity modifier V-1, stabilizers ST-1, ST-2, fog prevention Agents AF-1 (polyvinylpyrrolidone, weight average molecular weight: 10,000), AF-2 (polyvinylpyrrolidone, weight average molecular weight: 1,100,000), inhibitors AF-3, AF-4, AF-5, hard Film agents H-1, H-2, H-3, H-4 and preservative Ase-1 were added.
[0117]
The structure of the compound used for each sample is shown below.
SU-1: C₈F₁₇SO₂N (C_ThreeH₇) CH₂COOK
SU-2: C₈F₁₇SO₂NH (CH₂)_ThreeN⁺(CH_Three)_ThreeBr^-
SU-3: Sodium di (2-ethylhexyl) sulfosuccinate
SU-4: Sodium tri-i-propylnaphthalenesulfonate
ST-1: 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene ST-2: Adenine
AF-3: 1-phenyl-5-mercaptotetrazole
AF-4: 1- (4-carboxyphenyl) -5-mercaptotetrazole
AF-5: 1- (3-acetamidophenyl) -5-mercaptotetrazole
H-1: [(CH₂= CHSO₂CH₂)_ThreeCCH₂SO₂CH₂CH₂]₂NCH₂CH₂SO_ThreeK
H-2: 2,4-dichloro-6-hydroxy-s-triazine sodium
H-3: CH₂= CHSO₂CH₂CH (OH) CH₂SO₂CH = CH₂
H-4: CH₂= CHSO₂CH₂CONHCH₂CH₂NHCOCH₂SO₂CH = CH₂
OIL-1: tricresyl phosphate
OIL-2: Di (2-ethylhexyl) phthalate
AS-1: 2,5-bis (1,1-dimethyl-4-hexyloxycarbonylbutyl) hydroquinone
AS-2: Dodecyl gallate
AS-3: Docosyl gallate
AS-4: 2-octyloxy-5-t-octyl-N, N-dibutylaniline
AS-5: 2,5-di-t-octyl hydroquinone
AS-6: 2,5-di-t-octyl-1,4-quinone
[0118]
[Chemical 1]

[0119]
[Chemical 2]

[0120]
[Chemical 3]

[0121]
[Formula 4]

[0122]
[Chemical formula 5]

[0123]
[Chemical 6]

[0124]
[Chemical 7]

[0125]
[Chemical 8]

[0126]
[Chemical 9]

[0127]
[Table 2]

Table 3 shows silver iodobromide emulsions A to I used in the above samples.
[0128]
[Table 3]

[0129]
About the obtained sample, the sensitivity, the granularity (RMS), and the gradation stability (Ji) in the process fluctuation | variation were evaluated using green light by the following. Table 4 shows the obtained results.
[0130]
<Evaluation of sensitivity>
The obtained sample was subjected to normal wedge exposure and developed according to the following processing steps.
(Processing process)
Processing process Processing time Processing temperature Replenishment amount^*
Color development 3 minutes 15 seconds 38 ± 0.3 ° C 780ml
Whitening 45 seconds 38 ± 2.0 ℃ 150ml
Fixed 1 minute 30 seconds 38 ± 2.0 ℃ 830ml
Stable 60 seconds 38 ± 5.0 ℃ 830ml
Dry 1 minute 55 ± 5.0 ℃
* Replenishment amount is 1m photosensitive material²It is the amount per hit.
[0131]
The following were used as the color developer, bleaching solution, fixing solution, stabilizing solution and replenisher.

Add water to make 1 liter, and adjust the developer to pH 10.06 and the replenisher to pH 10.18 using potassium hydroxide or 20% sulfuric acid.
[0132]

Add water to make 1 liter, and use aqueous ammonia or glacial acetic acid to adjust the bleaching solution to pH 4.4 and the replenisher to pH 4.0.
[0133]

Use ammonia water or glacial acetic acid to adjust the fixing solution to pH 6.2 and the replenisher to pH 6.5, and then add water to make 1 liter.
[0134]

After adding water to 1 liter, the pH is adjusted to 8.5 using aqueous ammonia or 50% sulfuric acid.
[0135]
The reciprocal of the exposure amount required to obtain the minimum density of green density + 0.2 of the obtained processed sample was obtained and used as sensitivity. Table 4 shows relative values with the sensitivity of the sample 105 as 100.
[0136]
<< Evaluation of granularity (RMS) >>
The obtained sample was subjected to normal wedge exposure and developed according to the above processing steps.
[0137]
A microdensitometer (slit width 10 μm, slit length 180 μm) equipped with a rattan filter (W-99) manufactured by Eastman Kodak Co., Ltd. at the position of the green density +0.2 of the obtained processed sample. And the standard deviation of the fluctuation of the density value with the density measurement sampling number of 1000 or more was obtained, and the graininess (RMS) was evaluated. Table 4 shows relative values with the granularity (RMS) of the sample 105 as 100. A smaller RMS value (relative value) means better graininess.
[0138]
<< Evaluation of gradation stability (Ji) in process fluctuation >>
The obtained sample was subjected to normal wedge exposure and developed according to the above processing steps. In the above processing steps, the color development processing time was shortened to 2 minutes 50 seconds, and the processing steps were performed. went.
[0139]
From the obtained processed samples, characteristic curves with the horizontal axis representing the exposure amount (log E) and the vertical axis representing the magenta density value were prepared, and the Ji value was determined therefrom. The method for obtaining the Ji value is as follows.
[0140]
For the characteristic curve, minimum density + 0.5 density d₀Exposure amount logE giving₀Furthermore, logE at ΔlogE = −1.2_FourExposure point logE taken every ΔlogE = −3.0 units in the range up to_iThe concentration obtained in (i = 0, 1, 2, 3, 4) is d_i(I = 0, 1, 2, 3, 4)
g_i= (D_i-D_i-1) /-(LogE_i-LogE_i-1)
h = (d_Four-D₀) /-(LogE_Four-LogE₀)
And calculate j from the value_i= G_i/ H respectively, j with the largest deviation from 1.00_iWas designated as Ji for each color.
[0141]
[Table 4]

[0142]
As is apparent from Table 4, it can be seen that the silver halide photographic light-sensitive material of the present invention is excellent in gradation stability in processing variations. In particular, it can be seen that the graininess is also good.
[0143]
Example 2
(Preparation of silver halide emulsion)
In the same manner as described in JP-A-1-131541 and JP-A-5-173272, silver halide emulsions having the main plane shape, the sphere-converted average particle diameter, and the average AgI amount shown in Table 5 were prepared.
[0144]
When each emulsion was observed with an electron microscope, the ratio of tabular grains to all grains was 80% (number) or more.
[0145]
[Table 5]

[0146]
(Preparation of silver halide photographic material sample)
Instead of the silver iodobromide mixed emulsion of the ninth layer (high-sensitivity green color-sensitive layer), the same procedure as in Example 1 was used except that an emulsion mixed with EM-5 to EM-8 in the combination shown in Table 6 was used. Thus, silver halide photographic light-sensitive material samples 201 to 205 were prepared.
[0147]
[Table 6]

[0148]
Each sample obtained was evaluated in the same manner as in Example 1 for sensitivity, graininess, and gradation stability in processing variations. The results obtained are shown in Table 7. The sensitivity and the RMS value are shown as relative values with the value of the sample 205 as 100, respectively.
[0149]
[Table 7]

[0150]
As is apparent from Table 7, it can be seen that the silver halide photographic light-sensitive material of the present invention is excellent in gradation stability in processing variations. In particular, it can be seen that the graininess is also good.
[0151]
Example 3
(Preparation of silver halide emulsion)
In the same manner as described in Japanese Patent Application No. 9-281955, silver halide emulsions having an average dislocation line length, a sphere-converted average grain size and an average AgI amount shown in Table 8 were prepared.
[0152]
When each emulsion was observed with an electron microscope, the ratio of tabular grains to all grains was 80% (number) or more.
[0153]
[Table 8]

[0154]
(Preparation of silver halide photographic material sample)
Instead of the silver iodobromide mixed emulsion of the ninth layer (high-sensitivity green color-sensitive layer), the same procedure as in Example 1 was used except that an emulsion mixed with EM-9 to EM-12 in the combination shown in Table 9 was used. Thus, silver halide photographic light-sensitive material samples 301 to 305 were prepared.
[0155]
[Table 9]

[0156]
Each sample obtained was evaluated in the same manner as in Example 1 for sensitivity, graininess, and gradation stability in processing variations. Table 10 shows the obtained results. The sensitivity and the RMS value are shown as relative values with the value of the sample 305 as 100, respectively.
[0157]
[Table 10]

[0158]
As is apparent from Table 10, it can be seen that the silver halide photographic light-sensitive material of the present invention is excellent in gradation stability in processing variations. It can also be seen that the graininess is particularly good.
[0159]
Example 4
(Preparation of silver halide emulsion)
In the same manner as described in the specification of Japanese Patent Application No. 9-280459, it has a sphere-converted average particle diameter and an average AgI amount shown in Table 11, and as shown in Table 11, it is dislocated to the fringe part on the main plane. A silver halide emulsion with lines was prepared.
[0160]
When each emulsion was observed with an electron microscope, the ratio of tabular grains to all grains was 80% (number) or more.
[0161]
[Table 11]

[0162]
(Preparation of silver halide photographic material sample)
Instead of the silver iodobromide mixed emulsion of the ninth layer (high-sensitivity green color-sensitive layer), the same procedure as in Example 1 was used except that an emulsion mixed with EM-13 to EM-16 in the combination shown in Table 12 was used. Thus, silver halide photographic light-sensitive material samples 401 to 405 were prepared.
[0163]
[Table 12]

[0164]
Each sample obtained was evaluated in the same manner as in Example 1 for sensitivity, graininess, and gradation stability in processing variations. The results obtained are shown in Table 7. The sensitivity and the RMS value are shown as relative values with the value of the sample 405 being 100.
[0165]
[Table 13]

[0166]
As is apparent from Table 13, it can be seen that the silver halide photographic light-sensitive material of the present invention is excellent in gradation stability in processing variations. In particular, it can be seen that the graininess is also good.
[0167]
Example 5
(Preparation of silver halide emulsion)
In the same manner as described in Japanese Patent Application No. 9-280459, a silver halide emulsion having the average aspect ratio, the average number of dislocation lines, the sphere-converted average grain size, and the average AgI amount shown in Table 14 was prepared.
[0168]
When each emulsion was observed with an electron microscope, the ratio of tabular grains to all grains was 80% (number) or more.
[0169]
[Table 14]

[0170]
(Preparation of silver halide photographic material sample)
Instead of the silver iodobromide mixed emulsion of the ninth layer (high-sensitivity green color-sensitive layer), the same procedure as in Example 1 was used except that an emulsion mixed with EM-17 to EM-23 in the combination shown in Table 15 was used. Silver halide photographic light-sensitive material samples 501 to 508 were prepared.
[0171]
[Table 15]

[0172]
Each sample obtained was evaluated in the same manner as in Example 1 for sensitivity, graininess, and gradation stability in processing variations. The obtained results are shown in Table 16. The sensitivity and the RMS value are shown as relative values with the value of the sample 508 being 100.
[0173]
[Table 16]

[0174]
As is apparent from Table 16, it can be seen that the silver halide photographic light-sensitive material of the present invention is excellent in gradation stability in processing variations. In particular, it can be seen that the graininess is also good.
[0183]
Example 6
(Preparation of silver halide emulsion)
  In the same manner as described in Japanese Patent Application No. 9-281955,Table 17A silver halide emulsion having a coefficient of variation in dislocation line length, a sphere-equivalent average particle diameter, and an average AgI amount shown in FIG.
[0184]
When each emulsion was observed with an electron microscope, the ratio of tabular grains to all grains was 80% (number) or more.
[0185]
[Table 17]

[0186]
(Preparation of silver halide photographic material sample)
  Instead of the silver iodobromide mixed emulsion of the ninth layer (high sensitivity green color sensitive layer),Table 18In the combination shown inEM-24 to EM-27A silver halide photographic light-sensitive material in the same manner as in Example 1 except that an emulsion mixed withSamples 601-605It was created.
[0187]
[Table 18]

  Each sample obtained was evaluated in the same manner as in Example 1 for sensitivity, graininess, and gradation stability in processing variations. The results obtainedTable 19Shown in In addition, sensitivity and RMS value areSample 605The relative value with the value of 100 as 100 is shown.
[0188]
[Table 19]

  Table 19As is apparent from the above, it can be seen that the silver halide photographic light-sensitive material of the present invention is excellent in gradation stability in processing variations. In particular, it can be seen that the graininess is also good.
[0189]
【The invention's effect】
According to the present invention, it is possible to provide a silver halide color photographic material that achieves excellent graininess without impairing sensitivity and provides stable gradation reproduction against environmental fluctuations that occur in the market.

Claims (6)

In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, a flat plate having an average distance between twin planes of 30 nm or more in at least one silver halide emulsion layer Tabular silver halide emulsion (A) having an average distance between twin planes of less than 30 nm and a sphere-converted average grain size equal to or smaller than that of tabular silver halide emulsion (A) A silver halide photographic light-sensitive material comprising an emulsion (B). In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, a tabular silver halide emulsion having a circular main plane shape in at least one silver halide emulsion layer (C) and a tabular silver halide emulsion (D) having a hexagonal main plane shape and a sphere-equivalent average particle size equal to or smaller than that of the tabular silver halide emulsion (C). A silver halide photographic light-sensitive material characterized by In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, a flat plate having an average length of dislocation lines of 30 nm or more in at least one silver halide emulsion layer Tabular silver halide emulsion (E) having an average dislocation line length of less than 30 nm and a sphere-converted average grain size equal to or smaller than tabular silver halide emulsion (E) A silver halide photographic light-sensitive material comprising an emulsion (F). In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, tabular silver halide having dislocation lines mainly on the main plane in at least one silver halide emulsion layer The emulsion (G) and a tabular silver halide emulsion (H) having dislocation lines only in the fringe portion and having a sphere-equivalent average grain size equal to or smaller than that of the tabular silver halide emulsion (G) A silver halide photographic light-sensitive material characterized by the above. In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, dislocation lines per grain having an average aspect ratio of 8 or more in at least one silver halide emulsion layer. Tabular silver halide emulsion (I) having at least 30 grains, an average aspect ratio of 5 or more and less than 8, having 30 or more dislocation lines per grain, and a sphere equivalent average grain size value of tabular halogenated grains A silver halide photographic light-sensitive material comprising a tabular silver halide emulsion (J) which is equal to or smaller than the silver emulsion (I). In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, a plate having a dislocation line length variation coefficient of less than 25% in at least one silver halide emulsion layer. Tabular silver halide emulsion (M) and tabular silver halide having a dislocation line length variation coefficient of 25% or more and a sphere-equivalent average grain size equal to or smaller than tabular silver halide emulsion (M) A silver halide photographic light-sensitive material comprising an emulsion (N).