JP4039096B2 - Silver halide photographic emulsion - Google Patents
Silver halide photographic emulsion Download PDFInfo
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- JP4039096B2 JP4039096B2 JP2002080559A JP2002080559A JP4039096B2 JP 4039096 B2 JP4039096 B2 JP 4039096B2 JP 2002080559 A JP2002080559 A JP 2002080559A JP 2002080559 A JP2002080559 A JP 2002080559A JP 4039096 B2 JP4039096 B2 JP 4039096B2
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- tabular grains
- grains
- silver halide
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- 239000000839 emulsion Substances 0.000 title claims description 116
- -1 Silver halide Chemical class 0.000 title claims description 95
- 229910052709 silver Inorganic materials 0.000 title claims description 79
- 239000004332 silver Substances 0.000 title claims description 79
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 claims description 29
- 229910021612 Silver iodide Inorganic materials 0.000 claims description 29
- 229940045105 silver iodide Drugs 0.000 claims description 29
- 230000001235 sensitizing effect Effects 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 22
- 229910052740 iodine Inorganic materials 0.000 claims description 21
- 239000011630 iodine Substances 0.000 claims description 21
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 10
- 238000001179 sorption measurement Methods 0.000 claims description 6
- 230000001443 photoexcitation Effects 0.000 claims description 5
- 239000000243 solution Substances 0.000 description 70
- 238000000034 method Methods 0.000 description 58
- 239000000975 dye Substances 0.000 description 36
- 108010010803 Gelatin Proteins 0.000 description 32
- 229920000159 gelatin Polymers 0.000 description 32
- 235000019322 gelatine Nutrition 0.000 description 32
- 235000011852 gelatine desserts Nutrition 0.000 description 32
- 230000035945 sensitivity Effects 0.000 description 32
- 239000008273 gelatin Substances 0.000 description 31
- 239000002245 particle Substances 0.000 description 28
- 239000007864 aqueous solution Substances 0.000 description 27
- 239000010410 layer Substances 0.000 description 23
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 22
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 18
- 238000002360 preparation method Methods 0.000 description 18
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 18
- 230000012010 growth Effects 0.000 description 17
- 239000000463 material Substances 0.000 description 17
- 239000002019 doping agent Substances 0.000 description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 13
- 230000008569 process Effects 0.000 description 12
- 239000003381 stabilizer Substances 0.000 description 12
- 230000005540 biological transmission Effects 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 10
- 206010070834 Sensitisation Diseases 0.000 description 10
- 230000008313 sensitization Effects 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 229910001961 silver nitrate Inorganic materials 0.000 description 9
- 239000013078 crystal Substances 0.000 description 8
- 230000032683 aging Effects 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 7
- 230000005070 ripening Effects 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 229960000583 acetic acid Drugs 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 230000003698 anagen phase Effects 0.000 description 5
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- 150000002894 organic compounds Chemical class 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000000108 ultra-filtration Methods 0.000 description 5
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- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
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- 239000003513 alkali Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
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- ZUIVNYGZFPOXFW-UHFFFAOYSA-N chembl1717603 Chemical compound N1=C(C)C=C(O)N2N=CN=C21 ZUIVNYGZFPOXFW-UHFFFAOYSA-N 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
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- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 125000001360 methionine group Chemical group N[C@@H](CCSC)C(=O)* 0.000 description 2
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- 229910052763 palladium Inorganic materials 0.000 description 2
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- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 2
- 229940116357 potassium thiocyanate Drugs 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 description 2
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- 238000011105 stabilization Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- GGZHVNZHFYCSEV-UHFFFAOYSA-N 1-Phenyl-5-mercaptotetrazole Chemical compound SC1=NN=NN1C1=CC=CC=C1 GGZHVNZHFYCSEV-UHFFFAOYSA-N 0.000 description 1
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- IHWDSEPNZDYMNF-UHFFFAOYSA-N 1H-indol-2-amine Chemical class C1=CC=C2NC(N)=CC2=C1 IHWDSEPNZDYMNF-UHFFFAOYSA-N 0.000 description 1
- OHZAHWOAMVVGEL-UHFFFAOYSA-N 2,2'-bithiophene Chemical compound C1=CSC(C=2SC=CC=2)=C1 OHZAHWOAMVVGEL-UHFFFAOYSA-N 0.000 description 1
- DRGAZIDRYFYHIJ-UHFFFAOYSA-N 2,2':6',2''-terpyridine Chemical compound N1=CC=CC=C1C1=CC=CC(C=2N=CC=CC=2)=N1 DRGAZIDRYFYHIJ-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
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- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- GSQNTYWTOPLQOA-UHFFFAOYSA-M sodium;4-[(2-iodoacetyl)amino]benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(NC(=O)CI)C=C1 GSQNTYWTOPLQOA-UHFFFAOYSA-M 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910052713 technetium Inorganic materials 0.000 description 1
- 150000003536 tetrazoles Chemical class 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229940100050 virazole Drugs 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Description
【０００１】
【発明の属する技術分野】
本発明は、写真感度と粒状性に優れたハロゲン化銀写真乳剤に関する。
【０００２】
【従来の技術】
ハロゲン化銀感光材料（以下、単に感光材料ともいう）は、極めて完成度の高い成熟製品と言われている一方、要求される性能は、高感度、高画質、保存条件による性能変動が少ない等、多岐に亘り、その要求レベルは近年益々高まってきている。特に高感度化、高画質化という点では、昨今のデジタルカメラの技術進歩により、ハロゲン化銀写真感光材料の優位性を保持するために、更なる性能向上が必要である。
【０００３】
一方、より一層の高感度化、高画質化を図るべく、ハロゲン化銀乳剤（以下、単に乳剤ともいう）において、ハロゲン化銀粒子１個当たりの感度／粒子サイズ比を向上させる技術が検討されている。
【０００４】
一般に、ハロゲン化銀乳剤に含まれるハロゲン化銀粒子は、様々な形状を有することが知られている。例えば立方体や八面体、十四面体状の正常晶ハロゲン化銀粒子や、双晶面を一つ又は平行な双晶面を複数有する平板状ハロゲン化銀粒子、非平行な双晶面を有するテトラポット状や棒状のハロゲン化銀粒子等がある。中でも平板状ハロゲン化銀粒子（以下、単に平板粒子ともいう）は、その写真特性として以下の利点を有すると考えられている。
【０００５】
１．粒子体積に対する表面積の比率（以下、比表面積という）が大きく、多量の増感色素を表面に吸着させることができる為、固有感度に対して色増感感度が相対的に高い。
【０００６】
２．平板粒子を含む乳剤を塗布し、乾燥した場合、その粒子が支持体表面に平行に配列する為、塗布層の膜厚を薄くでき、その結果、感光材料の鮮鋭性（シャープネス）の向上を図ることができる。
【０００７】
３．ハロゲン化銀粒子による光散乱が少なく、解像度の高い画像が得られる。
４．青色光に対する感度（固有感度）が低い為、緑感光性層又は赤感光性層に用いた場合、感光材料の構成からイエローフィルター濃度を軽減又は除去することができる。
【０００８】
５．一般的な粒子と同一の感度を達成した際には、粒子形状上の特徴により塗布銀量を少なくでき、その結果、感度／粒状比や自然放射線耐性に優れる。
【０００９】
平板粒子に関係する従来技術としては、例えば米国特許４，４３４，２２６号、同４，４３９，５２０号、同４，４１４，３１０号、同４，４３３，０４８号、同４，４１４，３０６号、同４，４５９，３５３号、特公平４−３６３７４号、同５−１６０１５号、同６−４４１３２号、特開平６−４３６０５号、同６−４３６０６号、同６−２１４３３１号、同６−２２２４８８号、同６−２３０４９３号、同６−２５８７４５号等に、その製造方法ならびに使用技術が開示されている。
【００１０】
上記平板粒子の利点をより効果的に引き出すためには、より高アスペクト比の平板粒子を用いることが有効である。しかし、アスペクト比１２以上の高アスペクト比平板粒子を実際に実用化するためには、下記の幾つかの問題があった。
【００１１】
１．潜像分散により実際には望ましい増感が得られない。理論的には光を吸収する粒子表面積が増加した分、吸収される光量子の数も増加し、写真感度は向上する筈であるが、吸収された光量子は面積の大きい主平面上に形成された多くの感光核に散らばり、現像可能な潜像核を形成する確立は逆に低くなってしまう。よって望ましい写真感度向上が得られない。
【００１２】
２．増感色素の吸着が実際には充分でなく、粒子表面積の向上から見込まれるような光吸収が得られず、写真感度向上が達成されない
３．特開昭６３−２２０２３８号や特開平１−１０２５４７号、同６−２７５６４号、同６−１１７８１号等に記載される転位線技術は、現在では当業界で良く用いられている感度向上技術であり、高アスペクト比乳剤にもこれを組み合わせていくことが事実上必須であるが、アスペクト比１２以上の高アスペクト比平板粒子と転位線を組み合わせようとすると、沃素イオンの導入によって低アスペクト比化してしまうという問題が存在する。これを成長条件の調整で無理に高アスペクト比化しようとしても、粒径分布の劣化が生じるだけであることを発明者らは検討の中で確認している。
【００１３】
高アスペクト比乳剤の問題点を解決するために、米国特許５，４９４，７８９号に開示されているエピタキシャル乳剤など幾つかの構成が提案されてきたが、アスペクト比１２以上の高アスペクト比乳剤を実用化するための上記の三つの問題を全て解決するものでは無かった。即ち、従来の技術では、高アスペクト比平板粒子がもたらすメリットを十分に引き出すことができなかった。
【００１４】
【発明が解決しようとする課題】
本発明の目的は、感度向上と粒状性改良の為された高アスペクト比の平板粒子乳剤を提供することである。
【００１５】
【課題を解決するための手段】
本発明の目的は、以下の構成により達成された。
【００１６】
全粒子の投影面積の８０％以上が平均アスペクト比１２以上の平板状粒子で占められ、かつ該平板状粒子の投影面積の円換算直径の変動係数が３０％未満であり、かつ該平板状粒子の平均表面沃化銀含有率が５〜１５モル％であり、かつ該平板状粒子のコーナー近傍領域の表面沃化銀含有率が３モル％未満であり、
▲１▼かつ該平板状粒子が各辺に１０本以上の転位線を有し、該転位線が非ヨードギャップ型であるハロゲン化銀写真乳剤。
【００１７】
▲２▼かつ該平板状粒子が粒子外周部に浅い電子トラップ中心を有するハロゲン化銀写真乳剤。
【００１８】
▲３▼かつ一つの光量子による光励起で二つ以上の電子をハロゲン化銀に注入可能な機能を有する化合物を含有するハロゲン化銀写真乳剤。
【００１９】
▲４▼かつ該平板状粒子の表面に吸着した増感色素量が単分子層吸着相当量を超える量であるハロゲン化銀写真乳剤。
尚、上記ハロゲン化銀写真乳剤において、▲５▼平板状粒子がコーナー近傍領域にエピタキシャル成長相を有すること、▲６▼全粒子の投影面積の８０％以上が平均アスペクト比２０以上の平板状粒子で占められていることは好ましい態様である。
【００２０】
以下、本発明について詳細に説明する。
本発明のハロゲン化銀乳剤は、平板粒子を含むものである。平板粒子とは、結晶学的には双晶に分類される。
【００２１】
双晶とは、一つの粒子内に一つ以上の双晶面を有するハロゲン化銀結晶であり、双晶の形態の分類はクラインとモイザーによる報文、フォトグラフィッシェ・コレスポンデンツ（Ｐｈｏｔｏｇｒａｐｈｉｓｈｅ Ｋｏｒｒｅｓｐｏｎｄｅｎｚ）９９巻，９９頁、同１００巻，５７頁に詳しく述べられている。
【００２２】
本発明に係る平板粒子は、主平面に平行な双晶面を２枚以上有するものであることが好ましい。
【００２３】
双晶面は透過型電子顕微鏡により観察することができる。具体的な方法は次の通りである。まず、含有される平板粒子が、支持体上にほぼ主平面が平行に配向するように写真乳剤を塗布し、試料を作製する。これをダイヤモンド・カッターを用いて切削し、厚さ０．１μｍ程度の薄切片を得る。この切片を透過型電子顕微鏡で観察することにより、双晶面の存在を確認することができる。本発明の平板粒子における２枚の双晶面間距離は、上記の透過型電子顕微鏡を用いた切片の観察において、主平面に対しほぼ垂直に切断された断面を示す平板粒子を任意に１００個以上選び、主平面に平行な偶数枚の双晶面の内、最も距離の短い２枚の双晶面間距離をそれぞれの粒子について求め、加算平均した場合に、０．０１μｍ以下であることが好ましい。
【００２４】
本発明の乳剤は、又、全粒子の投影面積の８０％以上（１００％も可）が平均アスペクト比１２以上の平板粒子で占められていることを特徴とする。平均アスペクト比は好ましくは１５以上であり、より好ましくは２０以上であるが、上限は１００である。アスペクト比とは、粒径と粒子厚さの比をいう（アスペクト比＝粒径／厚さ）。ここで粒径とは、主平面に対して垂直にその粒子を投影した面積（投影面積）に等しい面積を有する円の直径を意味する。
【００２５】
平板粒子の粒径や厚さ、アスペクト比は、以下の方法（レプリカ法）で求めることができる。即ち、基板である支持体フィルム上に、内部標準となる粒径が既知のラテックスボールと主平面が基板に対して平行に配向するようにハロゲン化銀粒子とを塗布した試料を作製し、一定の角度からカーボン蒸着によるシャドーを施した後、通常のレプリカ法によってレプリカ試料を作製する。この試料の電子顕微鏡写真を撮影し、画像処理装置等を用いて個々の粒子の投影面積と厚さを求める。この時、粒子の投影面積は内部標準の投影面積から、粒子の厚さは内部標準と粒子の影の長さから算出する。本発明における平均アスペクト比は、３００個以上の粒子について求めたアスペクト比の値の個数平均値とする。
【００２６】
本発明の乳剤は、全粒子の投影面積の８０％以上を占める平板粒子の円換算直径の変動係数が３０％未満である。該変動係数は粒子の分布を示す値であり、２５％未満であることが好ましく、２０％未満であることがより好ましい（０％もあり得る）。本発明において円換算直径とは、個々の粒子の投影面積と同じ面積を有する円の直径として定義される。又円換算直径の変動係数は、下式によって定義される値であり、前記レプリカ法で乳剤に含まれるハロゲン化銀粒子の円換算直径を、任意に３００個以上測定して得られた値から求める。
【００２７】
円換算直径の変動係数（％）＝（円換算直径の標準偏差／円換算直径の平均値）×１００
本発明の乳剤は、全粒子の投影面積の８０％以上を占める平板粒子の平均表面沃化銀含有率が５〜１５モル％であり、かつ該平板粒子のコーナー近傍領域の表面沃化銀含有率が３モル％未満（０％でもよい）であることを特徴とする。本発明の乳剤粒子における、このような表面組成の特徴は、主平面上の増感色素の吸着を強化することで光吸収効率を向上し、コーナー近傍領域に化学増感核を集中して潜像分散を防止することで、高感度化、画質向上に寄与しているものと発明者らは考えている。表面の沃化銀含有率を向上することで増感色素の吸着が強化されることは、当業界では良く知られている。
【００２８】
平板粒子の主平面における表面沃化銀含有率の分布を細かく知るためには、高い空間分解能を有する分析手法を用いる必要がある。最も好ましく用いられる分析方法は、ＴＯＦ−ＳＩＭＳ（Ｔｉｍｅ ｏｆ Ｆｌｉｇｈｔ−Ｓｃａｔｔｅｒｉｎｇ Ｉｏｎ Ｍａｓｓ Ｓｐｅｃｔｒｏｓｃｏｐｙ：飛行時間型二次イオン質量分析法）であり、詳しくは特開２０００−１１２０４９号に記載の方法に従う。各々の粒子の主平面部分（ただし、後に規定するコーナー近傍領域を含まない主平面の中心部近傍）の表面沃化銀含有率を少なくとも２００個以上の粒子について測定し、個数平均値を平均表面沃化銀含有率とする。本発明において、平板粒子の平均表面沃化銀含有率は５〜１５モル％であることが必要であり、７〜１３モル％であることが好ましい。
【００２９】
平板粒子のコーナー近傍領域とは、主平面の中心（主平面を２次元図形と捉えた場合の重心）と各コーナー（主平面の角が丸みを帯びている場合には、隣接する辺の接線の交点に最も近い主平面上の点をコーナーとする）を結ぶ線分を引き、該線分上でコーナーから該線分の長さの１／１０の点で該線分に垂直に交わる平面で区切られるコーナーを含む領域と規定される。コーナー近傍領域の沃化銀含有率は、上記ＴＯＦ−ＳＩＭＳを用いて該コーナー近傍領域を測定することにより求めることができる。
【００３０】
平板粒子のコーナー近傍領域の表面沃度を３モル％未満にコントロ−ルする手段として、主平面が表面沃度５〜１５モル％であるホスト粒子を形成後、一旦、粒子コーナーを溶解し、その後、沃素イオン濃度の低い条件でコーナーの成長を行う方法が挙げられる。粒子コーナーの溶解は、アンモニアイオン存在下にｐＨ８．０以上、好ましくは９．０以上で熟成する方法、又はｐＢｒ１．２以下、好ましくは１．０以下の条件下で熟成する方法が好ましく用いられる。熟成時の温度は５０℃以上であることが好ましい。
【００３１】
本発明の請求項１に係る平板粒子は非ヨードギャップ型転位線を有する。以下、転位線について説明する。
【００３２】
ハロゲン化銀粒子の転位線は、例えば、Ｊ．Ｆ．Ｈａｍｉｌｔｏｎ；Ｐｈｏｔ．Ｓｃｉ．Ｅｎｇ．，ｖｏｌ１１，５７（１９６７）や、Ｔ．Ｓｈｉｏｚａｗａ；Ｊ．Ｓｏｃ．Ｐｈｏｔｏ．Ｓｃｉ．Ｊａｐａｎ，ｖｏｌ３５，２１３（１９７２）に記載の、低温での透過型電子顕微鏡を用いた直接的な方法により観察することができる。即ち、乳剤から粒子に新たに転位線が発生する程の圧力をかけないよう注意して取り出したハロゲン化銀粒子を電子顕微鏡観察用のメッシュに載せ、電子線による損傷（プリントアウト等）を防ぐように試料を冷却した状態で透過法により観察を行う。この時、粒子の厚みが厚いほど電子線が透過し難くなるので、高圧型（０．２５μｍの厚さの粒子に対し２００ｋＶ以上）の電子顕微鏡を用いた方が、より鮮明に観察することができる。このような方法によって、個々の粒子における転位線の位置及び数を求めることができる。
【００３３】
ハロゲン化銀粒子への転位線を導入する従来の方法としては、例えば沃化カリウムのような沃素イオンを含む水溶液と、水溶性銀塩溶液をダブルジェットで添加する方法、沃素イオンを含む溶液のみを添加する方法、沃化銀を含む微粒子乳剤を添加する方法、又は沃素イオンを放出する有機化合物を用いる方法などが知られており、特開昭６３−２２０２３８号や特開平１−１０２５４７号、同６−２７５６４号、同６−１１７８１号等に記載されている。以上のように従来知られていた方法は、特開平６−２７５６４号等に記載される様に、粒子成長中に沃素イオンを導入して、結晶格子のギャップ又はミスフィットを形成する方法である。
【００３４】
発明者らの検討の結果、本発明のようなアスペクト比の高いハロゲン化銀粒子を製造しようとする場合、沃素イオンを導入してヨ−ドギャップにより転位を形成しようとすると、アスペクト比が上がらず、高アスペクト比の乳剤は得られない。又、成長の条件を低ｐＢｒ化するという方法で、この問題を解決しようと試みたが、今度は粒子の円換算直径の変動係数が３０％を超えてしまうという問題が発生し、高アスペクト比で分布の揃った平板状乳剤は得られないことが判った。よって発明者らは、ヨードギャップに因らない転位線、即ち非ヨードギャップ型転位線、あるいは転位線に代わる増感手段、例として浅い電子トラップ中心を導入することによって、高アスペクト比で、かつ分布の揃った平板粒子乳剤の増感を達成した。各々の技術については後述する。
【００３５】
本発明においては、前記の沃素イオンを導入して結晶格子のギャップ又はミスフィットを形成する方法以外の方法で意図的にハロゲン化銀粒子に導入した転位線を非ヨードギャップ型の転位線と規定する。平板粒子の転位線がヨードギャップによるものであるものかどうかは、特開平１１−１９０８８５号に記載されるようなＥＰＭＡ法で、転位の形成部分に沃素イオンの局在ピークがあるか否かを測定することで識別できる。転位の形成部分に沃素イオンの局在ピークが認められない場合、非ヨードギャップ型の転位線であると確認できる。
【００３６】
本発明の請求項１に係る乳剤は、全粒子の投影面積の８０％以上を占める平板粒子の内、各辺に１０本以上の転位線を有する粒子が個数比率で６０％以上であることが好ましく、より好ましくは７０％以上、特に好ましくは８０％以上であり、１００％でもよい。尚、転位線数は好ましくは３０本以上であるが、５０本以上になると数えることが難しい。
【００３７】
非ヨードギャップ型の転位線をハロゲン化銀に導入するには、沃素イオン以外のイオン、錯体あるいは化合物をハロゲン化銀格子中に含有させ、結晶格子のミスフィットを形成させることが必要である。好ましい方法として、嵩高い有機化合物のドープが挙げられる。ドープとは、ハロゲン化銀結晶格子中に銀イオンとハライドイオン以外のイオン、原子又は化合物を含有させることであり、ドープするイオン、原子又は化合物をドーパントという。好ましい嵩高い有機化合物のドーパントとしてはピロール、ピラゾール、イミダゾール、トリアゾール、テトラゾール及びそれら誘導体を挙げることができる。これらの有機化合物は、脱プロトン化した陰イオンとしてハロゲン化銀結晶格子中に含有されていてもよい。又、フラン、チオフェン、ピラン、ピリジン、２，２′−ビチオフェン、２，２′−ビピリジン及び２，２′：６′，２″−ターピリジン及びそれらの誘導体も好ましい嵩高い有機化合物のドーパントとして挙げられる。これらドーパントの具体例としては、特開２０００−２４１９２４号の化７〜化９においてＬとして示される化合物が挙げられる。又、これらのドーパントは、銀イオン以外の金属イオンに配位結合した形態でドープされていてもよい。該ドーパントのドープ量は、総ハロゲン化銀量１モル当たり１×１０-6〜５×１０-3モルが好ましい。ドーパントは任意の溶媒に溶解して添加することができる。ドーパントの添加時期は、ハロゲン化銀粒子形成工程の総銀量に対して４０〜９５％の間が好ましく、５０〜９０％の間がより好ましい。
【００３８】
本発明の請求項２に係る乳剤は、全粒子の投影面積の８０％以上を占める平板粒子のうち各辺に１０本以上の転位線を有する粒子が個数比率で３０％未満であることが好ましく、より好ましくは２０％未満であり、特に好ましくは１０％未満である。該乳剤においては転位線によって達成する増感効果を、後述する浅い電子トラップ中心によって達成するため転位線粒子比率が低いことが特徴となる。アスペクト比２０以上の高アスペクト比粒子で転位線を導入する際の問題点は既に述べた通りである。
【００３９】
請求項２に係る平板粒子は、粒子中に浅い電子トラップ中心を粒子外周部中に有する。粒子外周部とは、平板粒子の成長に伴う体積増加において、粒子成長終了時の粒子体積を１００％とした場合に、５０％以降の成長領域として定義される。好ましくは６０％以降の成長領域であり、より好ましくは７０％以降の成長領域である。本発明において、浅い電子トラップ中心とは、ハロゲン化銀のコンダクションバンドより０．２ｅＶ以下、好ましくは０．１ｅＶ以下の深さにおいて電子を捕獲する中心と定義する。
【００４０】
浅い電子トラップ中心の増感効果及びドーパントによるハロゲン化銀粒子への浅い電子トラップ中心の付与の方法については、リサーチ・ディスクロージャ（Ｒｅｓｅａｒｃｈ Ｄｉｓｃｌｏｓｕｒｅ、以下ＲＤ）３６７３６及び米国特許５，７２８，５１７号等に記載されている。浅い電子トラップ中心を付与する具体的なドーパントとして、上記ＲＤでは下記一般式で表される６配位金属錯体を挙げている。
【００４１】
一般式 ［ＭＬ6］n
ここで、Ｍは充満フロンティア軌道多価金属イオン、好ましくはＦｅ+2、Ｏｓ+2、Ｃｏ+3、Ｒｈ+3、Ｉｒ+3、Ｐｄ+4又はＰｔ+4であり、Ｌ6は各々独立して選ばれる六つの配位子を表すが、配位子の少なくとも四つはアニオン性であり、少なくとも一つ（好ましくは三つ、最も好ましくは四つ）は、どのハロゲンイオンよりも電気陰性度が大きい配位子である。ｎは−１、−２、−３又は−４を表す。
【００４２】
又、上記米国特許記載の化合物ＳＥＴ−１〜２７を好ましく用いることができる。該ドーパントのドープ量は、総ハロゲン化銀量１モル当たり１×１０-7〜１×１０-4モルが好ましい。
【００４３】
平板粒子中のドーパントの分布については、特開平１１−１９０８８５号に記載の、粒子を表面から内部へ少しずつ溶解し、各部分のドーパント含有量をＩＣＰ−ＭＳ法によって測定する方法により調べることができる。
【００４４】
本発明の請求項３に係る乳剤は、一つの光量子による光励起で二つ以上の電子をハロゲン化銀に注入可能な機能を有する化合物を含むことを特徴とする。
【００４５】
従来の写真乳剤では、一つの光量子による励起によって増感色素が励起され、ハロゲン化銀の伝導帯に一つの電子を注入し増感色素の酸化体を形成する、これを繰り返すことによって潜像と呼ばれる現像可能な安定な中心が形成されると考えられている。増感色素を含まない乳剤でも、同様に一つの光量子による励起によってハロゲン化銀の伝導帯に一つの電子を生成し、同時に価電子帯に一つの正孔を生成する。前記化合物は、一つの光量子による光励起により一つの電子をハロゲン化銀の伝導帯に注入した後、色素の酸化体あるいはハロゲン化銀価電子帯の正孔と反応し、更にもう一つ１つの電子をハロゲン化銀の伝導体に注入する機能を有する。該化合物は一つの光量子によって得られる電子を２倍にすることの他に、一旦、生成した電子と色素酸化体あるいは正孔が再結合するロス過程を低減することによっても写真乳剤の感度向上に寄与する。
【００４６】
該化合物の機能や反応機構については、Ｎａｔｕｒｅ，４０２巻，８６５頁（１９９９）及びＪ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．，１２２巻，１１９３４頁（２０００）に詳しく記載されている。本発明において、該化合物は色素の酸化体又はハロゲン化銀の正孔と反応した後に開裂反応を生じてもよいし、しなくてもよい。具体的な好ましい化合物としては、米国特許５，７４７，２３６号、同６，０１０，８４１号、同６，０５４，２６０号、同６，１５３，３７１号、特開平１１−２３７７１０号、特願平１１−３５１４７９号、特願２０００−４７１６０号、有機合成化学４９巻，７号，６３６頁（１９９１）に開示された化合物を用いることができる。
【００４７】
該化合物は乳剤の製造工程のどの段階で添加しても構わないが、増感工程以降に添加することが好ましく、増感工程終了後に添加することがより好ましい。該化合物の添加量は、総ハロゲン化銀量１モル当たり１×１０-7〜１×１０-4モルが好ましい。
【００４８】
本発明の請求項４に係る乳剤は、全粒子の投影面積の８０％以上を占める平板粒子表面に吸着した増感色素量が、単分子層吸着相当量を超える量であることを特徴とする。通常、増感色素は粒子表面に単分子層で吸着し、それ以上吸着することは無い。しかし、単分子層相当量を超える量で吸着すれば、粒子単位表面積当たりの光吸収量は向上し、写真感度の向上に繋げることができる。増感色素を単分子層を超える量で吸着させる方法としては、Ｐｈｏｔｏｇｒａｐｈｉｃ Ｓｃｉｅｎｃｅ ａｎｄ Ｅｎｇｉｎｅｅｒｉｎｇ，２０巻，３号，９７頁（１９７６）、特開平１０−１７１０５８号、同１０−２３９７８９号等に記載されるように、カチオン色素とアニオン色素を併用し、静電力を用いて吸着させる方法が知られており、本発明においても、この方法を好ましく用いることができる。
【００４９】
具体的なカチオン色素としては、特開平１０−１７１０５８号を参考にすることができ、該明細書記載のＳ−（１）〜Ｓ−（４０）の色素を好ましく用いることができる。アニオン色素は、当業界で通常用いられている色素を使用することができる。
【００５０】
本発明の請求項５に係る乳剤においては、平板粒子がエピタキシャル成長相を有することを特徴とする。エピタキシャル成長乳剤については、米国特許４，４３５，５０１号、同４，４７１，０５０号、特開平８−６９０６９号、同９−２１１７６２号、同９−２１１７６３号等に記載がある。
【００５１】
本発明においては、エピタキシャル成長相の成長部位を粒子コーナー近傍領域に限定する化合物、即ち、部位ディレクターを用いても用いなくてもよい。部位ディレクターを用いない場合は、エピタキシャル成長に先立って、粒子コーナー近傍領域を低沃度化しておくことで成長部位の限定が達成される。表面近傍の低沃度化という手段に加えて、補助的に増感色素やアミノアザインデン類など、よく知られた部位ディレクターを用いることはできる。
【００５２】
用いることのできるエピタキシャル乳剤は、ハロゲン化銀エピタキシーを総銀の３０モル％未満に限定することが好ましい。更には、０．３〜２０モル％のハロゲン化銀エピタキシーが好ましく、増感効果に対しては約０．５〜１５モル％が最適である。又、エピタキシャル成長相の組成は、塩化銀を５０モル％以上含むことが好ましく、７０モル％以上がより好ましく、９０％以上含むことが更に好ましい。
【００５３】
本発明の乳剤は、先に述べたドーパント以外にも、多価金属化合物をドーパントとして含有させることができる。メタルドーパントとして、Ｍｇ、Ａｌ、Ｃａ、Ｓｃ、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ｇａ、Ｇｅ、Ｓｒ、Ｙ、Ｚｒ、Ｎｂ、Ｍｏ、Ｔｃ、Ｒｕ、Ｒｈ、Ｐｄ、Ｃｄ、Ｓｎ、Ｂａ、Ｃｅ、Ｅｕ、Ｗ、Ｒｅ、Ｏｓ、Ｉｒ、Ｐｔ、Ｈｇ、Ｔｌ、Ｐｄ、Ｂｉ、Ｉｎ等の金属化合物を好ましく用いることができる。
【００５４】
又、ドープする金属化合物は単塩又は金属錯体から選択することが好ましい。金属錯体から選択する場合、６配位、５配位、４配位、２配位錯体が好ましく、八面体６配位、平面４配位錯体がより好ましい。錯体は単核錯体でも多核錯体でもよい。錯体を構成する配位子としては、ＣＮ-、ＣＯ、ＮＯ2 -、１，１０−フェナントロリン、２，２′−ビピリジン、ＳＯ3 -、エチレンジアミン、ＮＨ3、ピリジン、Ｈ2Ｏ、ＮＣＳ-、ＮＣＯ-、ＮＯ3 -、ＳＯ4 2-、ＯＨ-、ＣＯ3 2-、ＳＳＯ3 2-、Ｎ3 -、Ｓ2 -、Ｆ-、Ｃｌ-、Ｂｒ-、Ｉ-などを用いることができる。ＮＣＳ-についてはＮ原子、Ｓ原子のどちらで配位するものでも用いることができる。
【００５５】
本発明の乳剤の製造においては、成長工程の少なくとも一部において限外濾過法による乳剤の濃縮操作を好ましく適用することができる。本発明のように、アスペクト比が高く、分布の揃った平板状乳剤を製造する場合には、希釈環境が好ましいため、生産性を向上するために限外濾過法の適用は好ましい。限外濾過法を用いた乳剤の濃縮操作を行う場合には、特開平１０−３３９９２３号に開示されるハロゲン化銀乳剤の製造設備を好ましく用いることができる。
【００５６】
本発明の乳剤は、分散媒を含むものである。分散媒とは、ハロゲン化銀粒子に対する保護コロイド性を有する化合物である。乳剤の製造工程においては、分散媒を核生成工程から粒子成長終了時に亘って存在させることが好ましい。好ましく用いることができる分散媒として、ゼラチンと親水性コロイドが挙げられる。
【００５７】
ゼラチンとしては、通常、分子量１０万程度のアルカリ処理ゼラチンや酸処理ゼラチン、又は酸化処理したゼラチンや、Ｂｕｌｌ．Ｓｏｃ．Ｓｃｉ．Ｐｈｏｔｏ．Ｊａｐａｎ．Ｎｏ．１６，３０頁（１９６６）に記載されるような酵素処理ゼラチンを好ましく用いることができる。親水性コロイドとしては、例えばゼラチン誘導体、ゼラチンと他の高分子とのグラフトポリマー、アルブミン、カゼインのような蛋白質；ヒドロキシエチルセルロース、カルボキシメチルセルロース、セルロース硫酸エステル類の如きセルロース誘導体；アルギン酸ナトリウム、澱粉誘導体のような糖誘導体；ポリビニルアルコール、ポリビニルアルコール部分アセタール、ポリ−Ｎ−ビニルピロリドン、ポリアクリル酸、ポリメタクリル酸、ポリアクリルアミド、ポリビニルイミダゾール、ポリビニルビラゾールのような単一あるいは共重合体の如き多種の合成親水性高分子物質を用いることができる。
【００５８】
ハロゲン化銀粒子の核生成時には、酸化処理ゼラチンや平均分子量が１万〜５万の低分子量ゼラチン、酸化処理した低分子量ゼラチンを好適に用いることができるが、特に平均分子量が３万以下の低分子量ゼラチン、又は酸化処理した低分子量ゼラチンを用いることが好ましい。この場合、より好ましい平均分子量は１万〜２．５万である。
【００５９】
又、粒子の成長工程においては、酸化処理によってゼラチン１ｇ当たりのメチオニン残基を２０μモル未満に低減した酸化処理ゼラチンが好ましく用いられる。又、粒子の成長工程において化学修飾ゼラチンを用いることも好ましい。用いることができる化学修飾ゼラチンとして、例えば特開平５−７２６５８号、同９−１９７５９５号、同９−２５１１９３号等に記載のアミノ基を置換したゼラチンを挙げることができる。
【００６０】
本発明の乳剤は、ハロゲン化銀粒子の成長終了後に、不要な可溶性塩類を除去したものであっても、あるいは含有させたままのものでもよい。又、特開昭６０−１３８５３８号記載の方法のように、ハロゲン化銀成長の任意の点で脱塩を行なうことも可能である。該塩類を除去する場合には、ＲＤ１７６４３号II項に記載の方法に基づいて行うことができる。更に詳しくは、沈澱形成後、又は物理熟成後の乳剤から可溶性塩を除去するためには、ゼラチンをゲル化させて行うヌーデル水洗法を用いてもよく、又、無機塩類、アニオン性界面活性剤、アニオン性ポリマー（ポリスチレンスルホン酸等）、又はゼラチン誘導体（アシル化ゼラチン、カルバモイル化ゼラチン等）を利用した沈澱法（フロキュレーション）を用いてもよい。
【００６１】
本発明の乳剤は単独で乳剤層に用いる以外に、本発明の効果を損なわない範囲で他の乳剤と混合して用いることができる。同一乳剤層内で、平均粒径の異なる本発明の乳剤を複数混合して用いることは、好ましい使用形態である。
【００６２】
乳剤の製造において、上記以外の条件については、特開昭６１−６６４３号、同６１−１４６３０号、同６１−１１２１４２号、同６２−１５７０２４号、同６２−１８５５６号、同６３−９２９４２号、同６３−１５１６１８号、同６３−１６３４５１号、同６３−２２０２３８号、同６３−３１１２４４号、ＲＤ３８９５７のＩ項及びIII項、ＲＤ４０１４５のXV項等を参考にして、適切な条件を選択することができる。
【００６３】
本発明の乳剤を用いてカラー感光材料を構成する際には、乳剤は、物理熟成、化学熟成及び分光増感を行ったものを使用する。このような工程で使用される添加剤は、ＲＤ３８９５７のIV及びＶ項、同４０１４５のXV項等に記載されている。
【００６４】
本発明に使用できる公知の写真用添加剤も、同じくＲＤ３８９５７のII〜Ｘ項項、同４０１４５のＩ〜XIII項に記載のものを用いることができる。
【００６５】
カラー感光材料を構成する際には、赤、緑及び青感光性ハロゲン化銀乳剤層を設け、各層にカプラーを含有させることができる。これら各層に含まれるカプラーから形成される発色色素は、分光吸収極大が各々少なくとも２０ｎｍ離れていることが好ましい。カプラーとしては、シアンカプラー、マゼンタカプラー、イエローカプラーを用いることが好ましい。各乳剤層とカプラーの組合せとしては、通常、イエローカプラーと青感光性層、マゼンタカプラーと緑感光性層、シアンカプラーと赤感光性層の組合せが用いられるが、これらに限られるものではなく、他の組合せでもよい。
【００６６】
カラー感光材料を構成する際にはＤＩＲ化合物を用いることができる。用いることのできるＤＩＲ化合物の具体例としては、例えば特開平４−１１４１５３号に記載のＤ−１〜Ｄ−３４が挙げられ、これらの化合物を好ましく用いることができる。上記の他にも、米国特許４，２３４，６７８号、同３，２２７，５５４号、同３，６４７，２９１号、同３，９５８，９９３号、同４，４１９，８８６号、同３，９３３，５００号、特開昭５７−５６８３７号、同５１−１３２３９号、米国特許２，０７２，３６３号、同２，０７０，２６６号、ＲＤ４０１４５のXIV項等に記載されるものを挙げることができる。
【００６７】
又、本発明の乳剤を用いてカラー感光材料を構成する際に用いることができるカプラーの具体例は、ＲＤ４０１４５のII項等に記載されている。
【００６８】
本発明の乳剤を用いて感光材料を構成する際に使用する添加剤は、ＲＤ４０１４５のVIII項に記載される分散法などにより添加することができる。
【００６９】
本発明の乳剤を用いた感光材料には、前述のＲＤ３８９５７のXV項等に記載される公知の支持体を使用することができる。
【００７０】
感光材料には、前述のＲＤ３８９５７のXI項に記載されるフィルター層や中間層等の補助層を設けることができる。又、前述のＲＤ３８９５７のXI項に記載の順層、逆層、ユニット構成等の様々な層構成を採ることができる。
【００７１】
本発明に係るハロゲン化銀乳剤は、一般用又は映画用のカラーネガフィルム、スライド用又はテレビ用のカラー反転フィルム、カラーペーパー、カラーポジフィルム、カラー反転ペーパーに代表される種々のカラー感光材料に好ましく適用することができる。
【００７２】
本発明の乳剤を用いた感光材料を現像処理するには、例えばＴ．Ｈ．ジェームズ著：セオリイ・オブ・ザ・ホトグラフィック・プロセス第４版（Ｔｈｅ Ｔｈｅｏｒｙ ｏｆ Ｔｈｅ Ｐｈｏｔｏｇｒａｐｈｉｃ Ｐｒｏｃｅｓｓ Ｆｏｒｔｈ Ｅｄｉｔｉｏｎ）２９１〜３３４頁及びＪ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．，７３巻，３１００頁（１９５１）に記載される、それ自体公知の現像剤を使用することができ、又、前述のＲＤ３８９５７のXVII〜XX項及びＲＤ４０１４５のXXIII項に記載された、通常の方法によって現像処理することができる。
【００７３】
【実施例】
以下に実施例を挙げて本発明を更に具体的に説明するが、本発明はこれらの実施態様に限定されるものではない。尚、特に断りない限り、実施例中の「％」は「質量％」を表す。
【００７４】
実施例１
〈平板状種乳剤１の調製〉
以下の手順で、平板状種乳剤１を調製した。
【００７５】
［核生成工程］
反応容器内で、低分子量ゼラチン（平均分子量１．５万）１６２．８ｇと臭化カリウム２３．６ｇを含む２８．３Ｌの水溶液を１５℃に保ち、特開昭６２−１６０１２８号記載の混合撹拌装置を用いて高速に撹拌しながら、０．５モル／Ｌの硫酸を用いてｐＨを１．９０に調整した。その後、ダブルジェット法を用いて、下記Ｓ−０１液とＸ−０１液を一定の流量で１分間かけて添加し、核形成を行った後、下記Ｇ−０１液を加えた。
【００７６】
Ｓ−０１液：１．２５モル／Ｌの硝酸銀水溶液２０５．７ｍｌ
Ｘ−０１液：１．２５モル／Ｌの臭化カリウム水溶液２０５．７ｍｌ
Ｇ−０１液：アルカリ処理不活性ゼラチン（平均分子量１０万）１２０．５ｇと、下記界面活性剤（ＡＯ−１）の１０％メタノール溶液８．８ｍｌを含む２９２１ｍｌの水溶液。
【００７７】
ＡＯ−１：ＨＯ（ＣＨ2ＣＨ2Ｏ）m［ＣＨ（ＣＨ3）ＣＨ2Ｏ］2Ｏ（ＣＨ2ＣＨ2Ｏ）nＨ（ｍ＋ｎ＝１０）
［熟成工程］
核生成工程終了後に、４５分間を要して６０℃に昇温し、ｐＡｇを９．２に調整した。続いて０．１３６モルのアンモニアを含む水溶液と水酸化カリウム水溶液を加えてｐＨを９．３に調整して６分間保持した後、１モル／Ｌの硝酸を用いてｐＨを６．１に調整した。
【００７８】
［成長工程］
熟成工程終了後、ｐＡｇを９．２に保ちつつ、ダブルジェット法を用いて下記Ｓ−０２液とＸ−０２液とを、流量を加速しながら（開始時と終了時の添加流量の比が約５倍）２０分間で添加した。
【００７９】
Ｓ−０２液：１．２５モル／Ｌの硝酸銀水溶液２６２０ｍｌ
Ｘ−０２液：１．２５モル／Ｌの臭化カリウム２６２０ｍｌ
各溶液を添加終了後、常法に従い脱塩、水洗処理を施し、追加のゼラチンを加えてよく分散した。
【００８０】
以上のようにして得られた乳剤は、平均の円換算直径０．６７μｍ、平均アスペクト比１２．4、粒径の変動係数１５．１％の平板状乳剤であった。これを平板状種乳剤１とする。
【００８１】
〈平板状乳剤Ｅｍ−Ａの調製〉
前記平板状種乳剤１を以下の手順で引き続き成長を行い、平板状乳剤Ｅｍ−Ａを調製した。
【００８２】
０．２１モル相当の平板状種乳剤１と前出の界面活性剤（ＡＯ−１）の１０％メタノール溶液１．０ｍｌを含む１％ゼラチン水溶液１０Ｌを、６０℃、ｐＡｇ９．２に保ちつつ、ダブルジェット法を用いて下記Ｓ−１１液とＸ−１１液を流量を加速しながら（開始時と終了時の添加流量の比が約１０倍）添加してＡ相を形成した。Ａ相形成後の平均アスペクト比は、２４．１であった。
【００８３】
Ｓ−１１液：３．５モル／Ｌの硝酸銀水溶液２０５９ｍｌ
Ｘ−１１液：３．４５モル／Ｌの臭化カリウムと０．０５モル／Ｌの沃化カリウムを含む水溶液２０５９ｍｌ
続けて、下記Ｉ−１１液とＺ−１１液を添加し、水酸化カリウム水溶液でｐＨを９．３に調整し６分間保持した後に、酢酸水溶液でｐＨを５．０、臭化カリウム水溶液でｐＡｇを９．７に調整した。引き続いて、下記Ｓ−１２液とＸ−１２液を添加流量を加速しながら（開始時と終了時の添加流量の比が約２．２倍）添加した。
【００８４】
Ｉ−１１液：ｐ−ヨードアセトアミドベンゼンスルホン酸ナトリウム５７．７ｇを含む水溶液
Ｚ−１１液：亜硫酸ナトリウム２０．０ｇを含む水溶液
Ｓ−１２液：３．５モル／Ｌの硝酸銀水溶液７２６ｍｌ
Ｘ−１２液：３．１５モル／Ｌの臭化カリウムと０．３５モル／Ｌの沃化カリウムを含む水溶液７２６ｍｌ
更に、下記Ｓ−１３液とＸ−１３液を流量を加速しながら（開始時と終了時の添加流量の比が約１．４倍）添加した。
【００８５】
Ｓ−１３液：１．２５モル／Ｌの硝酸銀水溶液５０９ｍｌ
Ｘ−１３液：１．２５モル／Ｌの臭化カリウム水溶液５０９ｍｌ
添加終了後に、特開平５−７２６５８号に記載の方法に従い、脱塩及び水洗処理を施し、ゼラチンを加えて良く分散し、４０℃にてｐＨを５．８、ｐＡｇを８．１に調整した。
【００８６】
続けて、水洗処理後の乳剤を５２℃に保持しながら、増感色素（ＳＤ−１）をハロゲン化銀１モル当たり１．６×１０-3モル加えた。２０分間熟成した後、チオ硫酸ナトリウムを加え、更に塩化金酸とチオシアン酸カリウムを添加した。各乳剤毎に最適な感度が得られるように熟成を行った後、抑制剤（ＡＦ−１）と安定剤（ＳＴ−１）を加えて安定化した。各乳剤に対する増感剤、安定剤の添加量と熟成時間は、最適な感度が得られるように設定した。
【００８７】
ＡＦ−１：１−フェニル−５−メルカプトテトラゾール
ＳＴ−１：４−ヒドロキシ−６−メチル−１，３，３ａ，７−テトラザインデン
【００８８】
【化１】
以上のようにして平板状乳剤Ｅｍ−Ａを得た。Ｅｍ−Ａを解析した結果、平均の円換算直径が２．３７μｍ、平均アスペクト比が１０．５、円換算直径の変動係数２１．０％、粒子表面の平均沃化銀含有率が９．１モル％の平板状粒子から成るものであった。又、平板状乳剤Ｅｍ−Ａには、各辺に、それぞれ１０本以上の転位線を有する平板状粒子が７９％存在していることを確認した（透過型顕微鏡による観察）。
【００９０】
〈平板状ハロゲン化銀乳剤Ｅｍ−Ｂの調製〉
平板状種乳剤１を以下の手順で引き続き成長を行い、平板状乳剤Ｅｍ−Ｂを調製した。
【００９１】
０．２１モル相当の平板状種乳剤１と前出の界面活性剤（ＡＯ−１）の１０％メタノール溶液１．０ｍｌを含む１％ゼラチン水溶液（ただし、ゼラチンとしてメチオニン残基の含有量が９μモル／ｇである酸化処理ゼラチンを用いた）２４Ｌを、６０℃、ｐＡｇ９．２に保ちつつ、ダブルジェット法を用いて下記Ｓ−１１液とＸ−１１液を流量を加速しながら（開始時と終了時の添加流量の比が約１０倍）添加した。
【００９２】
Ｓ−１１液：３．５モル／Ｌの硝酸銀水溶液２０５９ｍｌ
Ｘ−１１液：３．４５モル／Ｌの臭化カリウムと０．０５モル／Ｌの沃化カリウムを含む水溶液２０５９ｍｌ
続けて、ｐＡｇを９．６に調整した後、ｐＡｇを保ちながら下記Ｓ−１２液とＸ−１２液を添加流量を加速しながら（開始時と終了時の添加流量の比が約２．２倍）添加を行なった。
【００９３】
Ｓ−１２液：３．５モル／Ｌの硝酸銀水溶液７２６ｍｌ
Ｘ−１２液：３．１５モル／Ｌの臭化カリウムと０．３５モル／Ｌの沃化カリウムを含む水溶液７２６ｍｌ
更に、下記Ｓ−１３液とＸ−１３液を流量を加速しながら（開始時と終了時の添加流量の比が約１．４倍）添加した。
【００９４】
Ｓ−１３液：１．２５モル／Ｌの硝酸銀水溶液５０９ｍｌ
Ｘ−１３液：１．２５モル／Ｌの臭化カリウム水溶液５０９ｍｌ
ただし、上記Ｓ−１１液、Ｓ−１２液及びＳ−１３液の添加中は、特開平１０−３３９９２３号に記載の装置を用い、反応液の量が一定となるように限外濾過法により反応液の濃縮を行った。
【００９５】
添加終了後に、特開平５−７２６５８号に記載の方法に従い、脱塩及び水洗処理を施し、ゼラチンを加えて良く分散し、４０℃にてｐＨを５．８、ｐＡｇを８．１に調整した。
【００９６】
続けて、水洗処理後の乳剤を５２℃に保持しながら、増感色素（ＳＤ−１）をハロゲン化銀１モル当たり２．０×１０-3モル加えた。２０分間熟成した後、チオ硫酸ナトリウムを加え、更に塩化金酸とチオシアン酸カリウムを添加した。各乳剤毎に最適な感度が得られるように熟成を行った後、抑制剤（ＡＦ−１）と安定剤（ＳＴ−１）を加えて安定化した。各乳剤に対する増感剤、安定剤の添加量と熟成時間は、最適な感度が得られるように設定した。
【００９７】
以上のようにして平板状乳剤Ｅｍ−Ｂを得た。Ｅｍ−Ｂを解析した結果、平均の円換算直径が３．２６μｍ、平均アスペクト比が２７．１、円換算直径の変動係数２４．５％、粒子表面の平均沃化銀含有率が８．５モル％の平板状粒子から成るものであった。又、２００個の平板粒子を透過型顕微鏡にて観察したところ、各辺に、それぞれ１０本以上の転位線を有する平板状粒子は観察されなかった。
【００９８】
〈平板状乳剤Ｅｍ−Ｃの調製〉
下記の工程以外は前記Ｅｍ−Ｂと同様にして乳剤Ｅｍ−Ｃを調製した。
【００９９】
Ｓ−１３液の添加に先立ち、０．４６８モルのアンモニアを含む水溶液と水酸化カリウム水溶液を加えてｐＨを９．２に調整して１０分間保持した後、酢酸水溶液でｐＨを５．０に調整し、使用したアンモニア水溶液、水酸化カリウム溶液、酢酸水溶液の総容量と同量の体積を限外濾過にて濃縮した。
【０１００】
このようにして、平板状乳剤Ｅｍ−Ｃを得た。Ｅｍ−Ｃを解析した結果、平均の円換算直径が３．２４μｍ、平均アスペクト比が２６．８、円換算直径の変動係数２４．７％、粒子表面の平均沃化銀含有率が８．９モル％の平板状粒子であった。又、解析した２００個の粒子全てにおいて、コーナー近傍領域の沃化銀含有率は３モル％未満であった。更に、２００個の平板粒子を透過型顕微鏡にて観察したところ、各辺に、それぞれ１０本以上の転位線を有する平板状粒子は観察されなかった。
【０１０１】
〈平板状ハロゲン化銀乳剤Ｅｍ−Ｄの調製〉
下記の工程以外は前記Ｅｍ−Ｃと同様にして乳剤Ｅｍ−Ｄを調製した。
【０１０２】
Ｓ−１２液の添加に先立ち、２−メチルイミダゾールを１．１×１０-2モル含有する水溶液を添加した。
【０１０３】
このようにして平板状ハロゲン化銀乳剤Ｅｍ−Ｄを得た。Ｅｍ−Ｄを解析した結果、平均の円換算直径が３．２８μｍ、平均アスペクト比が２７．６、円換算直径の変動係数２３．８％、粒子表面の平均沃化銀含有率が８．９モル％の平板状粒子であった。解析した２００個の粒子全てにおいて、コーナー近傍領域の沃化銀含有率は３モル％未満であった。又、２００個の平板粒子を透過型顕微鏡にて観察したところ、各辺に、それぞれ１０本以上の転位線を有する平板状粒子が８２個数％存在することを確認した。
【０１０４】
〈平板状乳剤Ｅｍ−Ｅの調製〉
下記の工程以外はＥｍ−Ｃと同様にして乳剤Ｅｍ−Ｅを調製した。
【０１０５】
Ｓ−１２液の添加に先立ちＫ4［Ｒｕ（ＣＮ）6］を５．３×１０-4モル含有する水溶液を添加した。
【０１０６】
得られた平板状乳剤Ｅｍ−Ｅを解析した結果、平均の円換算直径が３．２８μｍ、平均アスペクト比が２７．６、円換算直径の変動係数２３．８％、粒子表面の平均沃化銀含有率が８．９モル％の平板状粒子であった。解析した２００個の粒子全てにおいてコーナー近傍領域の沃化銀含有率は３モル％未満であった。又、２００個の平板粒子を透過型顕微鏡にて観察したところ、各辺に、それぞれ１０本以上の転位線を有する平板状粒子が１２個数％存在することを確認した。
【０１０７】
〈平板状乳剤Ｅｍ−Ｆの調製〉
Ｅｍ−Ｃの調製において、抑制剤（ＡＦ−１）と安定剤（ＳＴ−１）の添加後に、米国特許６，０５４，２６０号に記載の化合物ＩＮＶ１をハロゲン化銀１モル当たり２．０×１０-6モル添加した以外は、Ｅｍ−Ｃと同様にして乳剤Ｅｍ−Ｆを調製した。ＩＮＶ１は請求項３に記載の一つの光量子による光励起で二つ以上の電子をハロゲン化銀に注入することを可能とする機能を有する化合物である。
【０１０８】
〈平板状ハロゲン化銀乳剤Ｅｍ−Ｇの調製〉
Ｅｍ−Ｃの調製において、増感色素（ＳＤ−１）の添加に先立って増感色素（ＳＤ−２）をハロゲン化銀１モル当たり２．０×１０-3モル加え、５２℃に保持しながら１０分間保持した後、増感色素（ＳＤ−１）を添加した以外はＥｍ−Ｃと同様にして乳剤Ｅｍ−Ｇを調製した。Ｅｍ−Ｇは特開平１０−１７１０５８号の記載を参考にして、カチオン色素（ＳＤ−２）とアニオン色素（ＳＤ−１）を併用し、平板粒子の表面に吸着した増感色素量を単分子層吸着相当量を超える量に増量した平板状乳剤である。
【０１０９】
【化２】
〈平板状乳剤Ｅｍ−Ｈの調製〉
Ｅｍ−Ａの調製において、抑制剤（ＡＦ−１）と安定剤（ＳＴ−１）の添加後に、前出の化合物ＩＮＶ１をハロゲン化銀１モル当たり２．０×１０-6モル添加した以外はＥｍ−Ａと同様にして乳剤Ｅｍ−Ｈを調製した。
【０１１１】
〈平板状乳剤Ｅｍ−Ｉの調製〉
Ｅｍ−Ａの調製において、増感色素（ＳＤ−１）の添加に先立って、増感色素（ＳＤ−２）をハロゲン化銀１モルあたり１．６×１０-3モル加え、５２℃に保持しながら１０分間保持した後、増感色素（ＳＤ−１）を添加した以外はＥｍ−Ａと同様にして乳剤Ｅｍ−Ｉを調製した。Ｅｍ−Ｉは特開平１０−１７１０５８号の記載を参考にして、カチオン色素ＳＤ−２とアニオン色素ＳＤ−１を併用し、平板粒子の表面に吸着した増感色素量を単分子層吸着相当量を超える量に増量した平板状乳剤である。
【０１１２】
〈平板状乳剤Ｅｍ−Ｊの調製〉
Ｅｍ−Ｅの調製において、下記の操作によってエピタキシャル成長相を形成した以外はＥｍ−Ｅと同様にして乳剤Ｅｍ−Ｊを調製した。
【０１１３】
Ｓ−１３液とＸ−１３液の添加終了後、続いて、下記Ｓ−１４液とＸ−１４液を流量を加速しながら（開始時と終了時の添加流量の比が約１．５倍）添加した。
【０１１４】
Ｓ−１４液：１．００モル／Ｌの硝酸銀水溶液５３０ｍｌ
Ｘ−１４液：１．００モル／Ｌの臭化カリウム水溶液５３０ｍｌ
Ｅｍ−Ｊを解析した結果、平均の円換算直径が３．２２μｍ、平均アスペクト比が２６．２、円換算直径の変動係数２４．１％、粒子表面の平均沃化銀含有率が８．３モル％の平板状粒子から成るものであった。解析した２００個の粒子全てにおいて、コーナー近傍領域の表面沃化銀含有率は３モル％未満であった。又電子顕微鏡観察により、平板粒子のコーナー近傍領域に突起状にエピタキシャル成長相が存在することが確認された。更に、２００個の平板粒子を透過型顕微鏡にて観察したところ、各辺に、それぞれ１０本以上の転位線を有する平板状粒子が１２個数％存在することを確認した。
【０１１５】
〈カラー感光材料の作製〉
増感処理を施したＥｍ−Ａ〜Ｅｍ−Ｊの各乳剤に、下記カプラー（Ｍ−１）を酢酸エチル、トリクレジルホスフェートに溶解し、ゼラチンを含む水溶液中に乳化分散した分散物、延展剤、及び硬膜剤等の一般的な写真添加剤を加えて塗布液を調製し、下塗りを施した三酢酸セルロースフィルム支持体上に常法に従い塗布・乾燥してカラー感光材料試料１０１〜１１０を作製した。
【０１１６】
【化３】
これらの試料作製直後に、各試料に対して色温度５４００°Ｋの光源を用い東芝ガラスフィルター（Ｙ−４８）を通してウェッジ露光を行い、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 １分 ３８±５．０℃ ８３０ｍｌ
乾 燥 １分 ５５±５．０℃
＊補充量は感光材料１ｍ2当たりの値である。
【０１１８】
発色現像液、漂白液、定着液、安定液及びその補充液は、以下のものを使用した。
（発色現像液及び発色現像補充液） 現像液 補充液
水 ８００ｍｌ ８００ｍｌ
炭酸カリウム ３０ｇ ３５ｇ
炭酸水素ナトリウム ２．５ｇ ３．０ｇ
亜硫酸カリウム ３．０ｇ ５．０ｇ
臭化ナトリウム １．３ｇ ０．４ｇ
沃化カリウム １．２ｍｇ −
ヒドロキシルアミン硫酸塩 ２．５ｇ ３．１ｇ
塩化ナトリウム ０．６ｇ −
４−アミノ−３−メチル−Ｎ−エチル−Ｎ−（β−ヒドロキシルエチル）
アニリン硫酸塩 ４．５ｇ ６．３ｇ
ジエチレントリアミン五酢酸 ３．０ｇ ３．０ｇ
水酸化カリウム １．２ｇ ２．０ｇ
水を加えて１Ｌとし、水酸化カリウム又は２０％硫酸を用いて発色現像液はｐＨ１０．０６に、補充液はｐＨ１０．１８に調整する。
（定着液及び定着補充液） 定着液 補充液
水 ８００ｍｌ ８００ｍｌ
チオシアン酸アンモニウム １２０ｇ １５０ｇ
チオ硫酸アンモニウム １５０ｇ １８０ｇ
亜硫酸ナトリウム １５ｇ ２０ｇ
エチレンジアミン四酢酸 ２ｇ ２ｇ
アンモニア水又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１Ｌとする。
（安定液及び安定補充液）
水 ９００ｍｌ
ｐ−オクチルフェノールのエチレンオキシド１０モル付加物 ２．０ｇ
ジメチロール尿素 ０．５ｇ
ヘキサメチレンテトラミン ０．２ｇ
１，２−ベンゾイソチアゾリン−３−オン ０．１ｇ
シロキサン（ＵＣＣ製Ｌ−７７） ０．１ｇ
アンモニア水 ０．５ｍｌ
水を加えて１Ｌとした後、アンモニア水又は５０％硫酸を用いてｐＨ８．５に調整する。
【０１１９】
現像済み試料の感度を緑色光を用いて測定した。測定方法及び条件を以下に示す。
【０１２０】
《相対感度》
各試料において、最小濃度（Ｄｍｉｎ）＋０．２の濃度を与える露光量の逆数を感度として求め、Ｅｍ−Ａの試料の感度を１００とする相対値で示した。相対感度の値が大きいほど感度が高く好ましいことを意味する。
【０１２１】
《粒状性》
ＲＭＳ粒状度により評価した。ＲＭＳ粒状度は、緑色光を用い、試料の最小濃度＋０．２の部分を被測定部とし、開口走査面積１８００μｍ2（スリット巾１０μｍ、スリット長１８０μｍ）のマイクロデンシトメーターで走査し、濃度測定サンプリング１０００以上の濃度値の変動の標準偏差の１０００倍値を求め、Ｅｍ−Ａの試料を１００とした相対値で示した。数値が小さいほど粒状性が優れていることを示す。
【０１２２】
【表１】
表１から明らかなように、本発明の構成によれば、写真感度、粒状性の優れた高アスペクト比のハロゲン化銀写真乳剤が提供できる。
【０１２４】
【発明の効果】
本発明によれば、感度向上と粒状性が改良された高アスペクト比の平板状ハロゲン化銀粒子を提供する。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a silver halide photographic emulsion excellent in photographic sensitivity and graininess.
[0002]
[Prior art]
Silver halide light-sensitive materials (hereinafter also referred to simply as light-sensitive materials) are said to be extremely mature products, while the required performance is high sensitivity, high image quality, little performance fluctuation due to storage conditions, etc. The demand level has been increasing in recent years. In particular, in terms of higher sensitivity and higher image quality, further improvements in performance are necessary to maintain the superiority of silver halide photographic light-sensitive materials due to recent technological advances in digital cameras.
[0003]
On the other hand, in order to achieve higher sensitivity and higher image quality, a technique for improving the sensitivity / grain size ratio per silver halide grain in a silver halide emulsion (hereinafter also simply referred to as emulsion) has been studied. ing.
[0004]
In general, it is known that silver halide grains contained in a silver halide emulsion have various shapes. For example, cubic, octahedral, and tetradecahedral normal silver halide grains, tabular silver halide grains having one twin plane or a plurality of parallel twin planes, and non-parallel twin planes Examples include tetrapot-shaped and rod-shaped silver halide grains. Among these, tabular silver halide grains (hereinafter also simply referred to as tabular grains) are considered to have the following advantages as photographic characteristics.
[0005]
1. Since the ratio of the surface area to the particle volume (hereinafter referred to as the specific surface area) is large and a large amount of sensitizing dye can be adsorbed on the surface, the color sensitization sensitivity is relatively high with respect to the intrinsic sensitivity.
[0006]
2. When an emulsion containing tabular grains is applied and dried, the grains are arranged in parallel to the surface of the support, so that the thickness of the coating layer can be reduced, and as a result, the sharpness of the photosensitive material is improved. be able to.
[0007]
3. Light scattering by silver halide grains is small, and an image with high resolution can be obtained.
4). Since the sensitivity (inherent sensitivity) to blue light is low, the yellow filter density can be reduced or eliminated from the structure of the photosensitive material when used in the green photosensitive layer or the red photosensitive layer.
[0008]
5). When the same sensitivity as that of general grains is achieved, the amount of coated silver can be reduced due to the characteristics of the grain shape. As a result, the sensitivity / granularity ratio and natural radiation resistance are excellent.
[0009]
Examples of conventional techniques related to tabular grains include U.S. Pat. Nos. 4,434,226, 4,439,520, 4,414,310, 4,433,048, and 4,414,306. No. 4,459,353, JP-B-4-36374, JP-A-5-16015, JP-A-6-44132, JP-A-6-43605, JP-A-6-43606, JP-A-6-214331, JP-A-6-214331. No. 222488, 6-230493, 6-258745, etc. disclose their production methods and techniques for use.
[0010]
In order to extract the advantages of the tabular grains more effectively, it is effective to use tabular grains having a higher aspect ratio. However, in order to actually put the high aspect ratio tabular grains having an aspect ratio of 12 or more into practical use, there were the following problems.
[0011]
1. The desired sensitization is not actually obtained due to the latent image dispersion. Theoretically, the number of absorbed photons should increase by increasing the surface area of the particles that absorb light, and the photographic sensitivity should improve, but the absorbed photons were formed on the main surface with a large area. On the contrary, the probability of forming developable latent image nuclei is scattered, scattered in many photosensitive nuclei. Therefore, a desirable photographic sensitivity improvement cannot be obtained.
[0012]
2. The absorption of sensitizing dye is not sufficient in practice, the light absorption expected from the improvement in particle surface area cannot be obtained, and the improvement in photographic sensitivity is not achieved.
3. The dislocation line technology described in JP-A-62-220238, JP-A-1-102547, JP-A-6-27564, JP-A-6-11781, etc. is a sensitivity improvement technique that is often used in the present industry. In fact, it is essential to combine this with high aspect ratio emulsions. However, when high aspect ratio tabular grains having an aspect ratio of 12 or more are combined with dislocation lines, the aspect ratio is reduced by introducing iodine ions. There is a problem of end. The inventors have confirmed through examination that even if an attempt is made to forcibly increase the aspect ratio by adjusting the growth conditions, only the deterioration of the particle size distribution occurs.
[0013]
In order to solve the problems of the high aspect ratio emulsion, several configurations such as an epitaxial emulsion disclosed in US Pat. No. 5,494,789 have been proposed. A high aspect ratio emulsion having an aspect ratio of 12 or more has been proposed. It did not solve all the above three problems for practical use. In other words, the conventional technique cannot sufficiently bring out the merits brought about by the high aspect ratio tabular grains.
[0014]
[Problems to be solved by the invention]
It is an object of the present invention to provide a high aspect ratio tabular grain emulsion with improved sensitivity and improved graininess.
[0015]
[Means for Solving the Problems]
The object of the present invention has been achieved by the following constitution.
[0016]
80% or more of the projected area of all grains is occupied by tabular grains having an average aspect ratio of 12 or more, and the variation coefficient of the diameter in terms of circle of the projected area of the tabular grains is less than 30%, and the tabular grains The average surface silver iodide content is 5 to 15 mol%, and the surface silver iodide content in the region near the corner of the tabular grain is less than 3 mol%,
(1) A silver halide photographic emulsion in which the tabular grains have 10 or more dislocation lines on each side, and the dislocation lines are of a non-iodine gap type.
[0017]
(2) A silver halide photographic emulsion in which the tabular grains have shallow electron trap centers at the outer periphery of the grains.
[0018]
(3) A silver halide photographic emulsion containing a compound having a function capable of injecting two or more electrons into silver halide by photoexcitation with one photon.
[0019]
(4) A silver halide photographic emulsion wherein the amount of the sensitizing dye adsorbed on the surface of the tabular grains exceeds the amount equivalent to the adsorption of a monomolecular layer.
In the above silver halide photographic emulsion, (5) tabular grains have an epitaxial growth phase near the corner, and (6) 80% or more of the projected area of all grains is tabular grains having an average aspect ratio of 20 or more. Occupied is a preferred embodiment.
[0020]
Hereinafter, the present invention will be described in detail.
The silver halide emulsion of the present invention contains tabular grains. Tabular grains are classified crystallographically as twins.
[0021]
A twin crystal is a silver halide crystal having one or more twin planes in one grain, and the classification of the twin crystal is classified by Klein and Moiser, Photographie Correspondents (Photographis Korrespondenz). ) 99, 99, 100, 57.
[0022]
The tabular grains according to the present invention preferably have two or more twin planes parallel to the main plane.
[0023]
The twin plane can be observed with a transmission electron microscope. The specific method is as follows. First, a photographic emulsion is coated on the support so that the contained tabular grains are oriented substantially parallel to each other on a support to prepare a sample. This is cut using a diamond cutter to obtain a thin slice having a thickness of about 0.1 μm. By observing this section with a transmission electron microscope, the presence of twin planes can be confirmed. The distance between the two twin planes in the tabular grain of the present invention is such that the number of tabular grains showing a cross section cut substantially perpendicularly to the main plane is 100 in the observation of the section using the transmission electron microscope. When the above selection is made and 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 particle and averaged, it is 0.01 μm or less. preferable.
[0024]
The emulsion of the present invention is also characterized in that 80% or more (100% is acceptable) of the projected area of all grains is occupied by tabular grains having an average aspect ratio of 12 or more. The average aspect ratio is preferably 15 or more, more preferably 20 or more, but the upper limit is 100. The aspect ratio refers to the ratio between the particle diameter and the particle thickness (aspect ratio = particle diameter / thickness). Here, the particle diameter means a diameter of a circle having an area equal to an area (projected area) obtained by projecting the particles perpendicular to the main plane.
[0025]
The particle size, thickness, and aspect ratio of the tabular grains can be determined by the following method (replica method). That is, a sample in which a latex ball having a known particle size as an internal standard and silver halide grains were applied so that the main plane was oriented parallel to the substrate on a support film as a substrate was prepared, and the sample was fixed. After performing the shadowing by carbon deposition from the angle, a replica sample is produced by a normal replica method. An electron micrograph of this sample is taken, and the projected area and thickness of each particle are determined using an image processing apparatus or the like. At this time, the projected area of the particle is calculated from the projected area of the internal standard, and the thickness of the particle is calculated from the length of the internal standard and the shadow of the particle. The average aspect ratio in the present invention is the number average value of the aspect ratio values obtained for 300 or more particles.
[0026]
In the emulsion of the present invention, the coefficient of variation of the circular equivalent diameter of tabular grains occupying 80% or more of the projected area of all grains is less than 30%. The coefficient of variation is a value indicating the distribution of particles, preferably less than 25%, more preferably less than 20% (may be 0%). In the present invention, the diameter in terms of a circle is defined as the diameter of a circle having the same area as the projected area of each particle. The coefficient of variation of the circle-equivalent diameter is a value defined by the following formula, and from the value obtained by arbitrarily measuring 300 or more circle-equivalent diameters of silver halide grains contained in the emulsion by the replica method. Ask.
[0027]
Fluctuation coefficient (%) of the yen-converted diameter = (standard deviation of the circle-converted diameter / average value of the circle-converted diameter) x 100
In the emulsion of the present invention, the average surface silver iodide content of tabular grains occupying 80% or more of the projected area of all grains is 5 to 15 mol%, and the surface silver iodide content in the region near the corners of the tabular grains The rate is less than 3 mol% (may be 0%). The characteristics of the surface composition in the emulsion grains of the present invention are that the absorption of sensitizing dyes on the main plane is enhanced to improve the light absorption efficiency, and the chemical sensitization nuclei are concentrated in the region near the corners and latent. The inventors consider that preventing image dispersion contributes to higher sensitivity and improved image quality. It is well known in the art that the adsorption of sensitizing dyes is enhanced by increasing the surface silver iodide content.
[0028]
In order to know the distribution of the surface silver iodide content in the main plane of the tabular grains in detail, it is necessary to use an analytical method having a high spatial resolution. The analysis method most preferably used is TOF-SIMS (Time of Flight-Scattering Ion Mass Spectroscopy), and the method described in Japanese Patent Application Laid-Open No. 2000-112049 is specifically described. The surface silver iodide content of the main plane part of each grain (however, the center part of the main plane not including the area near the corner defined later) is measured for at least 200 grains, and the number average value is the average surface. The silver iodide content. In the present invention, the average surface silver iodide content of the tabular grains needs to be 5 to 15 mol%, and preferably 7 to 13 mol%.
[0029]
The area near the corner of a tabular grain is the center of the main plane (the center of gravity when the main plane is regarded as a two-dimensional figure) and each corner (when the corner of the main plane is rounded, the tangent of the adjacent side) A line connecting the points on the main plane closest to the intersection of the two points), and a plane perpendicular to the line segment at a point 1/10 of the length of the line segment from the corner on the line segment It is defined as an area including corners separated by. The silver iodide content in the corner vicinity region can be determined by measuring the corner vicinity region using the TOF-SIMS.
[0030]
As a means for controlling the surface iodine in the region near the corner of the tabular grain to less than 3 mol%, after forming the host grain having a main plane having a surface iodine of 5 to 15 mol%, the grain corner is once dissolved. Thereafter, there is a method in which corners are grown under a low iodine ion concentration. For dissolution of the particle corner, a method of aging at pH 8.0 or more, preferably 9.0 or more in the presence of ammonia ions, or a method of aging under conditions of pBr 1.2 or less, preferably 1.0 or less is preferably used. . The aging temperature is preferably 50 ° C. or higher.
[0031]
The tabular grain according to claim 1 of the present invention has non-iodine gap type dislocation lines. Hereinafter, dislocation lines will be described.
[0032]
The dislocation lines of silver halide grains are described in, for example, J. F. Hamilton; Photo. Sci. Eng. , Vol 11, 57 (1967), T. Shiozawa; Soc. Photo. Sci. It can be observed by a direct method using a transmission electron microscope at a low temperature described in Japan, vol 35, 213 (1972). In other words, silver halide grains taken out carefully so as not to apply a pressure that causes new dislocation lines to be generated from the emulsion are placed on a mesh for observation with an electron microscope to prevent damage (printout, etc.) due to electron beams. In this way, the specimen is cooled and observed by the transmission method. At this time, the thicker the particle thickness, 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. By such a method, the position and number of dislocation lines in each particle can be obtained.
[0033]
Conventional methods for introducing dislocation lines into silver halide grains include, for example, an aqueous solution containing iodine ions such as potassium iodide, a method of adding a water-soluble silver salt solution by double jet, and a solution containing iodine ions only. Are known, such as a method of adding a fine grain emulsion containing silver iodide, a method of using an organic compound that releases iodine ions, and the like, and Japanese Patent Laid-Open Nos. 63-220238 and 1-102547, 6-27564, 6-11781, and the like. As described above, the conventionally known method is a method of introducing a gap or misfit of a crystal lattice by introducing iodine ions during grain growth as described in JP-A-6-27564. .
[0034]
As a result of the study by the inventors, when silver halide grains having a high aspect ratio as in the present invention are to be produced, if the dislocation is formed by introducing iodine ions by introducing iodine ions, the aspect ratio does not increase. High aspect ratio emulsions cannot be obtained. In addition, an attempt was made to solve this problem by reducing the growth conditions to pBr, but this time the problem that the coefficient of variation of the diameter of the particles in terms of circle exceeded 30% occurred, resulting in a high aspect ratio. It was found that a tabular emulsion with a uniform distribution could not be obtained. Therefore, the inventors have introduced a dislocation line that does not depend on the iodine gap, that is, a non-iodine gap type dislocation line, or a sensitization means that replaces the dislocation line, for example, a shallow electron trap center, and has a high aspect ratio and Sensitization of tabular grain emulsion with uniform distribution was achieved. Each technique will be described later.
[0035]
In the present invention, a dislocation line intentionally introduced into a silver halide grain by a method other than the method for forming a gap or misfit of a crystal lattice by introducing iodine ions is defined as a non-iodop gap type dislocation line. To do. Whether or not the dislocation lines of the tabular grains are due to an iodine gap is determined by the EPMA method as described in JP-A-11-190885, whether or not there is a local peak of iodine ions in the dislocation formation portion. Can be identified by measuring. When a local peak of iodine ions is not observed in the dislocation formation portion, it can be confirmed that the dislocation line is a non-iodine gap type dislocation line.
[0036]
In the emulsion according to claim 1 of the present invention, among tabular grains occupying 80% or more of the projected area of all grains, grains having 10 or more dislocation lines on each side may be 60% or more in number ratio. More preferably, it is 70% or more, particularly preferably 80% or more, and may be 100%. The number of dislocation lines is preferably 30 or more, but it is difficult to count when the number is 50 or more.
[0037]
In order to introduce non-iodo gap type dislocation lines into silver halide, it is necessary to contain ions, complexes or compounds other than iodine ions in the silver halide lattice to form a crystal lattice misfit. As a preferred method, a bulky organic compound dope can be mentioned. Doping is to contain ions, atoms or compounds other than silver ions and halide ions in the silver halide crystal lattice, and the ions, atoms or compounds to be doped are called dopants. Preferable bulky organic compound dopants include pyrrole, pyrazole, imidazole, triazole, tetrazole and derivatives thereof. These organic compounds may be contained in the silver halide crystal lattice as deprotonated anions. Furan, thiophene, pyran, pyridine, 2,2'-bithiophene, 2,2'-bipyridine and 2,2 ': 6', 2 "-terpyridine and their derivatives are also mentioned as preferred bulky organic compound dopants. Specific examples of these dopants include compounds represented by L in Chemical Formulas 7 to 9 of JP-A No. 2000-241924. These dopants are coordinated to metal ions other than silver ions. The dopant may be doped in the form of 1 × 10 5 per mole of total silver halide.-6~ 5x10-3Mole is preferred. The dopant can be added after being dissolved in an arbitrary solvent. The addition time of the dopant is preferably between 40 and 95%, more preferably between 50 and 90% with respect to the total silver amount in the silver halide grain forming step.
[0038]
In the emulsion according to claim 2 of the present invention, the number of grains having 10 or more dislocation lines on each side among tabular grains occupying 80% or more of the projected area of all grains is preferably less than 30%. , More preferably less than 20%, and particularly preferably less than 10%. The emulsion is characterized by a low dislocation line grain ratio in order to achieve the sensitization effect achieved by dislocation lines by the shallow electron trap center described later. The problems in introducing dislocation lines with high aspect ratio particles having an aspect ratio of 20 or more are as already described.
[0039]
The tabular grain according to claim 2 has a shallow electron trap center in the grain outer periphery. The grain outer peripheral portion is defined as a growth region of 50% or more when the grain volume at the end of grain growth is 100% in the volume increase accompanying the growth of tabular grains. The growth region is preferably 60% or more, and more preferably 70% or more. In the present invention, the shallow electron trap center is defined as a center that captures electrons at a depth of 0.2 eV or less, preferably 0.1 eV or less from the silver halide conduction band.
[0040]
The method of sensitizing shallow electron trap centers and imparting shallow electron trap centers to silver halide grains with a dopant is described in Research Disclosure (RD) 36636 and US Pat. No. 5,728,517. Are listed. As a specific dopant for imparting a shallow electron trap center, the above RD lists a hexacoordinate metal complex represented by the following general formula.
[0041]
General formula [ML6]n
Where M is a full frontier orbital polyvalent metal ion, preferably Fe+2, Os+2, Co+3, Rh+3, Ir+3, Pd+4Or Pt+4And L6Each represents six independently selected ligands, wherein at least four of the ligands are anionic and at least one (preferably three, most preferably four) of which halogen ion Is a ligand with a large electronegativity. n represents -1, -2, -3, or -4.
[0042]
Further, compounds SET-1 to 27 described in the above US patent can be preferably used. The doping amount of the dopant is 1 × 10 5 per mole of total silver halide.-7~ 1x10-FourMole is preferred.
[0043]
The distribution of the dopant in the tabular grains can be examined by the method described in JP-A-11-190885, in which the grains are dissolved little by little from the surface to the inside, and the dopant content of each portion is measured by the ICP-MS method. it can.
[0044]
The emulsion according to claim 3 of the present invention comprises a compound having a function capable of injecting two or more electrons into silver halide by photoexcitation with one photon.
[0045]
In conventional photographic emulsions, the sensitizing dye is excited by excitation by a single photon, and one electron is injected into the conduction band of silver halide to form an oxidant of the sensitizing dye. It is believed that a developable stable center called is formed. Similarly, an emulsion containing no sensitizing dye generates one electron in the conduction band of silver halide and one hole in the valence band simultaneously by excitation by one photon. The compound injects one electron into the silver halide conduction band by photoexcitation with one photon, and then reacts with an oxidant of the dye or a hole in the silver halide valence band. Is injected into the silver halide conductor. In addition to doubling the number of electrons obtained by a single photon, this compound can also improve the sensitivity of photographic emulsions by reducing the loss process of recombination between the generated electrons and oxidized dyes or holes. Contribute.
[0046]
The function and reaction mechanism of the compound are described in Nature, 402, 865 (1999) and J. Am. Am. Chem. Soc. 122, 11934 (2000). In the present invention, the compound may or may not undergo a cleavage reaction after reacting with an oxidized dye or a hole in silver halide. Specific preferred compounds include U.S. Pat. Nos. 5,747,236, 6,010,841, 6,054,260, 6,153,371, JP-A-11-237710, Japanese Patent Application. The compounds disclosed in Japanese Patent Application Laid-Open No. 11-351479, Japanese Patent Application No. 2000-47160, Synthetic Organic Chemistry, Vol. 49, No. 7, 636 (1991) can be used.
[0047]
The compound may be added at any stage of the emulsion production process, but is preferably added after the sensitization process, and more preferably after completion of the sensitization process. The amount of the compound added is 1 × 10 5 per mole of total silver halide.-7~ 1x10-FourMole is preferred.
[0048]
The emulsion according to claim 4 of the present invention is characterized in that the amount of the sensitizing dye adsorbed on the surface of the tabular grains occupying 80% or more of the projected area of all the grains exceeds the amount equivalent to the adsorption of the monomolecular layer. . Usually, the sensitizing dye is adsorbed on the particle surface as a monomolecular layer and does not adsorb any more. However, if it is adsorbed in an amount exceeding the amount equivalent to the monomolecular layer, the amount of light absorption per unit surface area of the particles can be improved, leading to an improvement in photographic sensitivity. The method for adsorbing the sensitizing dye in an amount exceeding the monomolecular layer is described in Photographic Science and Engineering, Vol. 20, No. 3, page 97 (1976), JP-A Nos. 10-171058, 10-239789, and the like. As described above, there is known a method in which a cationic dye and an anionic dye are used in combination and adsorbed using an electrostatic force, and this method can also be preferably used in the present invention.
[0049]
As specific cationic dyes, JP-A-10-171058 can be referred to, and dyes S- (1) to S- (40) described in the specification can be preferably used. As the anionic dye, a dye usually used in the art can be used.
[0050]
The emulsion according to claim 5 of the present invention is characterized in that the tabular grains have an epitaxial growth phase. Epitaxially grown emulsions are described in U.S. Pat. Nos. 4,435,501, 4,471,050, JP-A-8-69069, 9-211762, and 9-211763.
[0051]
In the present invention, a compound that limits the growth site of the epitaxial growth phase to the region near the grain corner, that is, a site director may or may not be used. In the case where the site director is not used, the growth site is limited by lowering the region near the grain corner prior to the epitaxial growth. In addition to means for lowering the iodine in the vicinity of the surface, well-known site directors such as sensitizing dyes and aminoazaindenes can be used supplementarily.
[0052]
Epitaxial emulsions that can be used preferably limit silver halide epitaxy to less than 30 mole percent of total silver. Further, 0.3 to 20 mol% of silver halide epitaxy is preferable, and about 0.5 to 15 mol% is optimal for the sensitizing effect. The composition of the epitaxial growth phase preferably contains 50 mol% or more of silver chloride, more preferably 70 mol% or more, and still more preferably 90% or more.
[0053]
The emulsion of the present invention can contain a polyvalent metal compound as a dopant in addition to the dopant described above. As metal dopants, Mg, Al, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh, Metal compounds such as Pd, Cd, Sn, Ba, Ce, Eu, W, Re, Os, Ir, Pt, Hg, Tl, Pd, Bi, and In can be preferably used.
[0054]
The metal compound to be doped is preferably selected from a single salt or a metal complex. When selecting from a metal complex, a 6-coordinate, a 5-coordinate, a 4-coordinate, and a 2-coordinate complex are preferable, and an octahedral 6-coordinate and a planar 4-coordinate complex are more preferable. The complex may be a mononuclear complex or a polynuclear complex. As a ligand constituting the complex, CN-, CO, NO2 -1,10-phenanthroline, 2,2'-bipyridine, SOThree -, Ethylenediamine, NHThree, Pyridine, H2O, NCS-, NCO-, NOThree -, SOFour 2-, OH-, COThree 2-, SSOThree 2-, NThree -, S2 -, F-, Cl-, Br-, I-Etc. can be used. NCS-As for, those coordinated by either an N atom or an S atom can be used.
[0055]
In the production of the emulsion of the present invention, an emulsion concentration operation by ultrafiltration can be preferably applied in at least a part of the growth process. When producing a tabular emulsion having a high aspect ratio and a uniform distribution as in the present invention, the dilution environment is preferable, and therefore the ultrafiltration method is preferably applied in order to improve productivity. In the case of performing an emulsion concentration operation using an ultrafiltration method, a silver halide emulsion production facility disclosed in JP-A-10-339923 can be preferably used.
[0056]
The emulsion of the present invention contains a dispersion medium. The dispersion medium is a compound having a protective colloid property for silver halide grains. In the emulsion production process, it is preferable that the dispersion medium is present from the nucleation process to the end of grain growth. Examples of the dispersion medium that can be preferably used include gelatin and hydrophilic colloid.
[0057]
As gelatin, usually alkali-treated gelatin, acid-treated gelatin having a molecular weight of about 100,000, oxidized gelatin, Bull. Soc. Sci. Photo. Japan. No. An enzyme-treated gelatin as described in pages 16, 30 (1966) can be preferably used. Examples of hydrophilic colloids include gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose and cellulose sulfates; sodium alginate, starch derivatives Sugar derivatives such as: polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinyl pyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, various kinds such as copolymers such as polyvinyl virazole Synthetic hydrophilic polymer materials can be used.
[0058]
At the time of nucleation of silver halide grains, oxidized gelatin, low molecular weight gelatin having an average molecular weight of 10,000 to 50,000, or oxidized low molecular weight gelatin can be suitably used. Particularly, the low average molecular weight is 30,000 or less. It is preferable to use molecular weight gelatin or oxidized low molecular weight gelatin. In this case, a more preferable average molecular weight is 10,000 to 25,000.
[0059]
In the grain growth step, oxidized gelatin in which the methionine residue per gram of gelatin is reduced to less than 20 μmol by oxidation treatment is preferably used. It is also preferable to use chemically modified gelatin in the grain growth process. Examples of the chemically modified gelatin that can be used include gelatins substituted with amino groups described in JP-A-5-72658, JP-A-9-197595, JP-A-9-251193, and the like.
[0060]
The emulsion of the present invention may be one obtained by removing unnecessary soluble salts after completion of the growth of silver halide grains or as it is contained. Further, desalting can be carried out at any point of silver halide growth, as in the method described in JP-A-60-138538. The removal of the salts can be carried out based on the method described in RD17643, Item II. More specifically, in order to remove soluble salts from the emulsion after precipitation or after physical ripening, a noodle water washing method in which gelatin is gelled may be used, and inorganic salts and anionic surfactants may be used. Alternatively, a precipitation method (flocculation) using an anionic polymer (polystyrene sulfonic acid or the like) or a gelatin derivative (acylated gelatin, carbamoylated gelatin or the like) may be used.
[0061]
The emulsion of the present invention can be used by mixing with other emulsions as long as the effects of the present invention are not impaired, in addition to being used alone in the emulsion layer. It is a preferred mode of use to use a plurality of emulsions of the present invention having different average particle diameters in the same emulsion layer.
[0062]
Regarding the conditions other than the above in the production of the emulsion, JP-A Nos. 61-6643, 61-14630, 61-112142, 62-157024, 62-18556, 63-92942, It is possible to select appropriate conditions with reference to 63-151618, 63-163451, 63-220238, 63-31244, I and III of RD38957, XV of RD40145, etc. it can.
[0063]
When a color light-sensitive material is constituted by using the emulsion of the present invention, an emulsion subjected to physical ripening, chemical ripening and spectral sensitization is used. Additives used in such a process are described in the IV and V terms of RD38957, the XV term of 40145, and the like.
[0064]
As the known photographic additive that can be used in the present invention, those described in the items II to X of RD38957 and the items I to XIII of 40145 can be used.
[0065]
When constituting a color light-sensitive material, red, green and blue light-sensitive silver halide emulsion layers can be provided and couplers can be contained in each layer. The coloring dyes formed from the couplers contained in each of these layers preferably have a spectral absorption maximum at least 20 nm apart. As the coupler, a cyan coupler, a magenta coupler, or a yellow coupler is preferably used. As a combination of each emulsion layer and coupler, a yellow coupler and a blue photosensitive layer, a magenta coupler and a green photosensitive layer, and a combination of a cyan coupler and a red photosensitive layer are usually used, but not limited thereto. Other combinations may be used.
[0066]
A DIR compound can be used when constituting a color light-sensitive material. Specific examples of DIR compounds that can be used include D-1 to D-34 described in JP-A-4-114153, and these compounds can be preferably used. In addition to the above, U.S. Pat. Nos. 4,234,678, 3,227,554, 3,647,291, 3,958,993, 4,419,886, 3, Nos. 933,500, 57-56837, 51-13239, U.S. Pat. Nos. 2,072,363, 2,070,266, RD40145, XIV, and the like. it can.
[0067]
Specific examples of couplers that can be used when constituting a color light-sensitive material using the emulsion of the present invention are described in Section II of RD40145.
[0068]
Additives used in constituting a light-sensitive material using the emulsion of the present invention can be added by the dispersion method described in Section VIII of RD40145.
[0069]
For the light-sensitive material using the emulsion of the present invention, a known support described in the above-mentioned RD38957 item XV can be used.
[0070]
The photosensitive material can be provided with an auxiliary layer such as a filter layer or an intermediate layer described in RD38957, item XI. Various layer configurations such as a normal layer, a reverse layer, and a unit configuration described in the RD38957 item XI can be adopted.
[0071]
The silver halide emulsion according to the present invention is preferably applied to various color light-sensitive materials represented by color negative films for general use or movies, color reversal films for slides or television, color paper, color positive film, and color reversal paper. can do.
[0072]
To develop a light-sensitive material using the emulsion of the present invention, for example, T.W. H. By James: The Theory of The Photographic Process Fourth Edition, pages 291-334 and J. Am. Am. Chem. Soc. 73, page 3100 (1951), a developer known per se can be used, and the usual methods described in the above-mentioned RD38957 XVII to XX and RD40145 XXIII Can be developed.
[0073]
【Example】
EXAMPLES The present invention will be described more specifically with reference to examples below, but the present invention is not limited to these embodiments. Unless otherwise specified, “%” in the examples represents “mass%”.
[0074]
Example 1
<Preparation of tabular seed emulsion 1>
Tabular seed emulsion 1 was prepared by the following procedure.
[0075]
[Nucleation process]
In a reaction vessel, 28.3 L of an aqueous solution containing 162.8 g of low molecular weight gelatin (average molecular weight 15,000) and 23.6 g of potassium bromide is kept at 15 ° C., and mixed and stirred as described in JP-A-62-160128. While stirring at high speed using the apparatus, the pH was adjusted to 1.90 using 0.5 mol / L sulfuric acid. Then, using the double jet method, the following S-01 solution and X-01 solution were added at a constant flow rate over 1 minute to perform nucleation, and then the following G-01 solution was added.
[0076]
S-01 solution: 1.25 mol / L silver nitrate aqueous solution 205.7 ml
Solution X-01: 1.25 mol / L potassium bromide aqueous solution 205.7 ml
G-01 solution: 2921 ml of an aqueous solution containing 120.5 g of alkali-treated inert gelatin (average molecular weight 100,000) and 8.8 ml of a 10% methanol solution of the following surfactant (AO-1).
[0077]
AO-1: HO (CH2CH2O)m[CH (CHThree) CH2O]2O (CH2CH2O)nH (m + n = 10)
[Aging process]
After completion of the nucleation step, the temperature was raised to 60 ° C. over 45 minutes, and the pAg was adjusted to 9.2. Subsequently, an aqueous solution containing 0.136 mol of ammonia and an aqueous potassium hydroxide solution were added to adjust the pH to 9.3 and held for 6 minutes, and then the pH was adjusted to 6.1 using 1 mol / L nitric acid. did.
[0078]
[Growth process]
After completion of the aging step, while maintaining the pAg at 9.2, the following S-02 solution and X-02 solution are accelerated using the double jet method while the flow rate is accelerated (the ratio of the addition flow rate at the start and end is (About 5 times) was added in 20 minutes.
[0079]
S-02 solution: 2620 ml of 1.25 mol / L silver nitrate aqueous solution
Solution X-02: 1.25 mol / L potassium bromide 2620 ml
After the addition of each solution, desalting and washing with water were performed according to conventional methods, and additional gelatin was added and well dispersed.
[0080]
The emulsion thus obtained was a tabular emulsion having an average circle-equivalent diameter of 0.67 μm, an average aspect ratio of 12.4, and a grain size variation coefficient of 15.1%. This is designated as tabular seed emulsion 1.
[0081]
<Preparation of tabular emulsion Em-A>
The tabular seed emulsion 1 was subsequently grown by the following procedure to prepare a tabular emulsion Em-A.
[0082]
While maintaining at 60 ° C. and pAg 9.2, 10 L of 1% gelatin aqueous solution containing 0.21 mol of tabular seed emulsion 1 and 1.0 ml of 10% methanol solution of the above-mentioned surfactant (AO-1), Using the double jet method, the following S-11 solution and X-11 solution were added while accelerating the flow rates (the ratio of the addition flow rate at the start and end was about 10 times) to form the A phase. The average aspect ratio after the formation of the A phase was 24.1.
[0083]
S-11 solution: 2059 ml of 3.5 mol / L silver nitrate aqueous solution
Solution X-11: 2059 ml of an aqueous solution containing 3.45 mol / L potassium bromide and 0.05 mol / L potassium iodide
Subsequently, the following I-11 solution and Z-11 solution were added, the pH was adjusted to 9.3 with an aqueous potassium hydroxide solution and held for 6 minutes, then the pH was 5.0 with an aqueous acetic acid solution, and an aqueous potassium bromide solution. The pAg was adjusted to 9.7. Subsequently, the following S-12 solution and X-12 solution were added while accelerating the addition flow rate (the ratio of the addition flow rate at the start and end was about 2.2 times).
[0084]
Solution I-11: An aqueous solution containing 57.7 g of sodium p-iodoacetamidobenzenesulfonate
Z-11 solution: An aqueous solution containing 20.0 g of sodium sulfite
S-12 solution: 726 ml of 3.5 mol / L silver nitrate aqueous solution
Solution X-12: 726 ml of an aqueous solution containing 3.15 mol / L potassium bromide and 0.35 mol / L potassium iodide
Further, the following S-13 solution and X-13 solution were added while accelerating the flow rates (the ratio of the addition flow rate at the start and end was about 1.4 times).
[0085]
S-13 solution: 509 ml of 1.25 mol / L aqueous silver nitrate solution
Solution X-13: 509 ml of a 1.25 mol / L potassium bromide aqueous solution
After completion of addition, according to the method described in JP-A-5-72658, desalting and washing treatment were performed, gelatin was added and well dispersed, and the pH was adjusted to 5.8 and pAg was adjusted to 8.1 at 40 ° C. .
[0086]
Subsequently, while maintaining the emulsion after washing with water at 52 ° C., the sensitizing dye (SD-1) was added at 1.6 × 10 6 per mole of silver halide.-3Mole was added. After aging for 20 minutes, sodium thiosulfate was added, and chloroauric acid and potassium thiocyanate were further added. After ripening so as to obtain an optimum sensitivity for each emulsion, an inhibitor (AF-1) and a stabilizer (ST-1) were added for stabilization. The amount of sensitizer and stabilizer added to each emulsion and the ripening time were set so as to obtain the optimum sensitivity.
[0087]
AF-1: 1-phenyl-5-mercaptotetrazole
ST-1: 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene
[0088]
[Chemical 1]
Tabular emulsion Em-A was obtained as described above. As a result of analysis of Em-A, the average circle-equivalent diameter was 2.37 μm, the average aspect ratio was 10.5, the coefficient of variation of the circle-equivalent diameter was 21.0%, and the average silver iodide content on the grain surface was 9.1. It consisted of mol% tabular grains. Further, it was confirmed that 79% of tabular grains each having 10 or more dislocation lines were present on each side in the tabular emulsion Em-A (observation with a transmission microscope).
[0090]
<Preparation of tabular silver halide emulsion Em-B>
Tabular seed emulsion 1 was subsequently grown according to the following procedure to prepare tabular emulsion Em-B.
[0091]
1% gelatin aqueous solution containing 0.2 ml of tabular seed emulsion 1 equivalent to 0.21 mol and 1.0 ml of 10% methanol solution of the above-mentioned surfactant (AO-1) (however, the content of methionine residue as gelatin is 9 μm) While maintaining 24 L at 60 ° C. and pAg 9.2 (using oxidized gelatin of mol / g), the following S-11 solution and X-11 solution were accelerated using the double jet method (at the start) And the ratio of the addition flow rate at the end was about 10 times).
[0092]
S-11 solution: 2059 ml of 3.5 mol / L silver nitrate aqueous solution
Solution X-11: 2059 ml of an aqueous solution containing 3.45 mol / L potassium bromide and 0.05 mol / L potassium iodide
Subsequently, after adjusting the pAg to 9.6, while maintaining the pAg, the addition flow rate of the following S-12 solution and X-12 solution is accelerated (the ratio of the addition flow rate at the start and end is about 2.2). Times) was added.
[0093]
S-12 solution: 726 ml of 3.5 mol / L silver nitrate aqueous solution
Solution X-12: 726 ml of an aqueous solution containing 3.15 mol / L potassium bromide and 0.35 mol / L potassium iodide
Further, the following S-13 solution and X-13 solution were added while accelerating the flow rates (the ratio of the addition flow rate at the start and end was about 1.4 times).
[0094]
S-13 solution: 509 ml of 1.25 mol / L aqueous silver nitrate solution
Solution X-13: 509 ml of a 1.25 mol / L potassium bromide aqueous solution
However, during the addition of the S-11 solution, the S-12 solution, and the S-13 solution, an apparatus described in JP-A-10-339923 is used, and an ultrafiltration method is used so that the amount of the reaction solution becomes constant. The reaction solution was concentrated.
[0095]
After completion of addition, according to the method described in JP-A-5-72658, desalting and washing treatment were performed, gelatin was added and well dispersed, and the pH was adjusted to 5.8 and pAg was adjusted to 8.1 at 40 ° C. .
[0096]
Subsequently, while maintaining the emulsion after washing with water at 52 ° C., the sensitizing dye (SD-1) was added at 2.0 × 10 6 per mole of silver halide.-3Mole was added. After aging for 20 minutes, sodium thiosulfate was added, and chloroauric acid and potassium thiocyanate were further added. After ripening so as to obtain an optimum sensitivity for each emulsion, an inhibitor (AF-1) and a stabilizer (ST-1) were added for stabilization. The amount of sensitizer and stabilizer added to each emulsion and the ripening time were set so as to obtain the optimum sensitivity.
[0097]
Tabular emulsion Em-B was obtained as described above. As a result of analyzing Em-B, the average circle-equivalent diameter was 3.26 μm, the average aspect ratio was 27.1, the coefficient of variation of the circle-equivalent diameter was 24.5%, and the average silver iodide content on the grain surface was 8.5. It consisted of mol% tabular grains. When 200 tabular grains were observed with a transmission microscope, tabular grains having 10 or more dislocation lines on each side were not observed.
[0098]
<Preparation of tabular emulsion Em-C>
Except for the following steps, Emulsion Em-C was prepared in the same manner as Em-B.
[0099]
Prior to the addition of solution S-13, an aqueous solution containing 0.468 mol of ammonia and an aqueous potassium hydroxide solution were added to adjust the pH to 9.2 and held for 10 minutes, and then the pH was adjusted to 5.0 with an aqueous acetic acid solution. After adjusting, the volume of the same volume as the total volume of the aqueous ammonia solution, potassium hydroxide solution and acetic acid solution used was concentrated by ultrafiltration.
[0100]
Thus, a tabular emulsion Em-C was obtained. As a result of the analysis of Em-C, the average circle-equivalent diameter was 3.24 μm, the average aspect ratio was 26.8, the coefficient of variation of the circle-equivalent diameter was 24.7%, and the average silver iodide content on the grain surface was 8.9. It was mol% tabular grains. Further, in all the 200 grains analyzed, the silver iodide content in the corner vicinity region was less than 3 mol%. Furthermore, when 200 tabular grains were observed with a transmission microscope, tabular grains having 10 or more dislocation lines on each side were not observed.
[0101]
<Preparation of tabular silver halide emulsion Em-D>
Except for the following steps, Emulsion Em-D was prepared in the same manner as Em-C.
[0102]
Prior to the addition of S-12 solution, 2-methylimidazole was added 1.1 × 10-2A molar aqueous solution was added.
[0103]
Thus, tabular silver halide emulsion Em-D was obtained. As a result of analysis of Em-D, the average circle-equivalent diameter was 3.28 μm, the average aspect ratio was 27.6, the coefficient of variation of the circle-equivalent diameter was 23.8%, and the average silver iodide content on the grain surface was 8.9. It was mol% tabular grains. In all the 200 grains analyzed, the silver iodide content in the corner vicinity region was less than 3 mol%. When 200 tabular grains were observed with a transmission microscope, it was confirmed that 82% by number of tabular grains each having 10 or more dislocation lines were present on each side.
[0104]
<Preparation of tabular emulsion Em-E>
Except for the following steps, Emulsion Em-E was prepared in the same manner as Em-C.
[0105]
Prior to addition of S-12 solutionFour[Ru (CN)6] 5.3 × 10-FourA molar aqueous solution was added.
[0106]
As a result of analysis of the obtained tabular emulsion Em-E, the average circle-equivalent diameter was 3.28 μm, the average aspect ratio was 27.6, the coefficient of variation of the circle-equivalent diameter was 23.8%, and the average silver iodide on the grain surface The content was tabular grains having a content of 8.9 mol%. In all the 200 grains analyzed, the silver iodide content in the corner vicinity region was less than 3 mol%. Further, when 200 tabular grains were observed with a transmission microscope, it was confirmed that 12% by number of tabular grains each having 10 or more dislocation lines were present on each side.
[0107]
<Preparation of tabular emulsion Em-F>
In the preparation of Em-C, after the addition of the inhibitor (AF-1) and the stabilizer (ST-1), the compound INV1 described in US Pat. No. 6,054,260 was converted to 2.0 × per mole of silver halide. 10-6Emulsion Em-F was prepared in the same manner as Em-C, except that the molar amount was added. INV1 is a compound having a function capable of injecting two or more electrons into silver halide by photoexcitation with one photon according to claim 3.
[0108]
<Preparation of tabular silver halide emulsion Em-G>
In the preparation of Em-C, prior to the addition of the sensitizing dye (SD-1), the sensitizing dye (SD-2) was added at 2.0 × 10 6 per mole of silver halide.-3Emulsion Em-G was prepared in the same manner as Em-C, except that a molar amount was added and maintained at 52 ° C. for 10 minutes, and then a sensitizing dye (SD-1) was added. Em-G refers to the description of JP-A-10-171058, and uses a cationic dye (SD-2) and an anionic dye (SD-1) in combination, and determines the amount of sensitizing dye adsorbed on the surface of the tabular grain as a single molecule. It is a tabular emulsion increased to an amount exceeding the layer adsorption equivalent.
[0109]
[Chemical 2]
<Preparation of tabular emulsion Em-H>
In the preparation of Em-A, after addition of the inhibitor (AF-1) and the stabilizer (ST-1), the above compound INV1 was converted to 2.0 × 10 6 per mole of silver halide.-6Emulsion Em-H was prepared in the same manner as Em-A, except that the molar amount was added.
[0111]
<Preparation of tabular emulsion Em-I>
In the preparation of Em-A, prior to the addition of the sensitizing dye (SD-1), the sensitizing dye (SD-2) is added at 1.6 × 10 6 per mole of silver halide.-3An emulsion Em-I was prepared in the same manner as Em-A, except that a molar amount was added and held at 52 ° C. for 10 minutes, and then a sensitizing dye (SD-1) was added. Em-I refers to the description of JP-A-10-171058, and uses the cationic dye SD-2 and the anionic dye SD-1 together, and the amount of the sensitizing dye adsorbed on the surface of the tabular grain is equivalent to the monolayer adsorption amount. Is a tabular emulsion increased to an amount exceeding 1.
[0112]
<Preparation of tabular emulsion Em-J>
In the preparation of Em-E, emulsion Em-J was prepared in the same manner as Em-E, except that an epitaxial growth phase was formed by the following operation.
[0113]
After completion of the addition of the S-13 solution and the X-13 solution, the flow rate of the following S-14 solution and the X-14 solution was accelerated (the ratio of the addition flow rate at the start and end was about 1.5 times). ) Added.
[0114]
Liquid S-14: 530 ml of 1.00 mol / L silver nitrate aqueous solution
Solution X-14: 530 ml of a 1.00 mol / L potassium bromide aqueous solution
As a result of analysis of Em-J, the average circle-equivalent diameter was 3.22 μm, the average aspect ratio was 26.2, the coefficient of variation of the circle-equivalent diameter was 24.1%, and the average silver iodide content on the grain surface was 8.3. It consisted of mol% tabular grains. In all the 200 grains analyzed, the surface silver iodide content in the corner vicinity region was less than 3 mol%. Further, it was confirmed by electron microscope observation that an epitaxially grown phase exists in a protruding shape in a region near the corner of the tabular grain. Furthermore, when 200 tabular grains were observed with a transmission microscope, it was confirmed that 12% by number of tabular grains each having 10 or more dislocation lines were present on each side.
[0115]
<Preparation of color photosensitive material>
The following coupler (M-1) was dissolved in ethyl acetate and tricresyl phosphate in each emulsion of Em-A to Em-J subjected to sensitization treatment, and the dispersion was emulsified and dispersed in an aqueous solution containing gelatin. Color photographic material samples 101 to 110 were prepared by adding a general photographic additive such as an adhesive and a hardening agent to prepare a coating solution, and applying and drying on an undercoated cellulose triacetate film support according to a conventional method. Was made.
[0116]
[Chemical 3]
Immediately after the preparation of these samples, each sample was subjected to wedge exposure through a Toshiba glass filter (Y-48) using a light source having a color temperature of 5400 ° K, 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
Stability 1 min 38 ± 5.0 ℃ 830ml
Dry 1 minute 55 ± 5.0 ℃
* Replenishment amount is 1m photosensitive material2It is a hit value.
[0118]
The following were used as the color developer, bleaching solution, fixing solution, stabilizing solution and replenisher.
(Color developer and color developer replenisher) Developer replenisher
800ml water 800ml
Potassium carbonate 30g 35g
Sodium bicarbonate 2.5g 3.0g
Potassium sulfite 3.0g 5.0g
Sodium bromide 1.3g 0.4g
Potassium iodide 1.2mg −
Hydroxylamine sulfate 2.5 g 3.1 g
Sodium chloride 0.6g −
4-Amino-3-methyl-N-ethyl-N- (β-hydroxylethyl)
Aniline sulfate 4.5 g 6.3 g
Diethylenetriaminepentaacetic acid 3.0 g 3.0 g
Potassium hydroxide 1.2g 2.0g
Add water to make 1 L, and adjust the color developer to pH 10.06 and the replenisher to pH 10.18 using potassium hydroxide or 20% sulfuric acid.
(Fixing solution and fixing replenisher) fixing solution replenisher
800ml water 800ml
Ammonium thiocyanate 120g 150g
Ammonium thiosulfate 150g 180g
Sodium sulfite 15g 20g
Ethylenediaminetetraacetic acid 2g 2g
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 L.
(Stabilizer and stable replenisher)
900ml water
2.0 g of ethylene oxide 10 mol adduct of p-octylphenol
Dimethylolurea 0.5g
Hexamethylenetetramine 0.2g
1,2-Benzisothiazolin-3-one 0.1 g
Siloxane (UCC L-77) 0.1g
Ammonia water 0.5ml
After adding water to 1 L, the pH is adjusted to 8.5 using aqueous ammonia or 50% sulfuric acid.
[0119]
The sensitivity of the developed sample was measured using green light. The measurement method and conditions are shown below.
[0120]
<Relative sensitivity>
In each sample, the reciprocal of the exposure amount giving a density of the minimum density (Dmin) +0.2 was obtained as sensitivity, and expressed as a relative value where the sensitivity of the Em-A sample was 100. A larger value of relative sensitivity means higher sensitivity and better sensitivity.
[0121]
<Granularity>
Evaluation was based on RMS granularity. The RMS granularity uses green light, the portion of the sample with the minimum density of +0.2 is the portion to be measured, and the aperture scanning area is 1800 μm.2Scan with a microdensitometer with a slit width of 10 μm and a slit length of 180 μm, obtain a standard deviation 1000 times the standard deviation of the density value variation over the density measurement sampling 1000, and use the Em-A sample as 100 as a relative value. Indicated. The smaller the value, the better the graininess.
[0122]
[Table 1]
As is apparent from Table 1, according to the constitution of the present invention, a high aspect ratio silver halide photographic emulsion excellent in photographic sensitivity and graininess can be provided.
[0124]
【The invention's effect】
According to the present invention, a high aspect ratio tabular silver halide grain having improved sensitivity and improved graininess is provided.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002080559A JP4039096B2 (en) | 2001-03-30 | 2002-03-22 | Silver halide photographic emulsion |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001-99232 | 2001-03-30 | ||
| JP2001099232 | 2001-03-30 | ||
| JP2002080559A JP4039096B2 (en) | 2001-03-30 | 2002-03-22 | Silver halide photographic emulsion |
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| Publication Number | Publication Date |
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| JP4039096B2 true JP4039096B2 (en) | 2008-01-30 |
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| JP (1) | JP4039096B2 (en) |
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