JPH11258720A - Silver halide photographic emulsion and silver halide photographic sensitive material - Google Patents

Silver halide photographic emulsion and silver halide photographic sensitive material

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Publication number
JPH11258720A
JPH11258720A JP6564298A JP6564298A JPH11258720A JP H11258720 A JPH11258720 A JP H11258720A JP 6564298 A JP6564298 A JP 6564298A JP 6564298 A JP6564298 A JP 6564298A JP H11258720 A JPH11258720 A JP H11258720A
Authority
JP
Japan
Prior art keywords
silver halide
silver
emulsion
solution
halide grains
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
JP6564298A
Other languages
Japanese (ja)
Inventor
Akiya Kondou
暁也 近藤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Konica Minolta Inc
Original Assignee
Konica Minolta Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Konica Minolta Inc filed Critical Konica Minolta Inc
Priority to JP6564298A priority Critical patent/JPH11258720A/en
Publication of JPH11258720A publication Critical patent/JPH11258720A/en
Withdrawn legal-status Critical Current

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Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic emulsion having high sensitivity and excellent graininess and to provide a silver halide photographic sensitive material using this emulsion. SOLUTION: This silver halide photographic emulsion contains a dispersion medium and silver halide particles. In the emulsion, particles satisfying A1 /A2 >1.0, wherein A1 is the silver bromide content in an area near the peak of the outermost layer and A2 is the silver bromide content in the part except for the peak are included by >50% in number. Or, the silver halide photographic emulsion may contain a dispersion medium and silver halide particles described below. The silver halide particle contains silver chloride in the outermost layer satisfying B1 /B2 >1.0, wherein B1 is the average silver iodide content in the outermost layer and B2 is the average silver iodide content in the silver halide particle.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明はハロゲン化銀写真乳
剤に関し、詳しくは、感度、粒状性に優れたハロゲン化
銀写真乳剤及び、該乳剤を用いたハロゲン化銀写真感光
材料（以下、単に感光材料とも称す）に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic emulsion, and more particularly, to a silver halide photographic emulsion having excellent sensitivity and granularity, and a silver halide photographic material using the emulsion (hereinafter simply referred to as "photosensitive material"). Material).

【０００２】[0002]

【従来の技術】カメラ等の撮影機器の普及は近年益々進
み、ハロゲン化銀写真感光材料を用いた写真撮影の機会
も増加してきている。それに伴って感光材料の高感度
化、高画質化に対する要請も益々強くなってきている。2. Description of the Related Art Photographic equipment such as cameras has become increasingly popular in recent years, and opportunities for taking photographs using silver halide photographic materials have been increasing. Along with this, demands for higher sensitivity and higher image quality of photosensitive materials have been increasing.

【０００３】感光材料の高感度化、高画質化に対しての
支配的因子の一つはハロゲン化銀粒子であり、より高感
度化、より高画質化を目指したハロゲン化銀粒子の開発
は従来から当業界で進められてきた。One of the dominant factors for increasing the sensitivity and image quality of photosensitive materials is silver halide grains. The development of silver halide grains aimed at higher sensitivity and higher image quality has been developed. It has traditionally been advanced in the industry.

【０００４】しかし、一般に行われているように、画質
向上のためにハロゲン化銀粒子の粒径を小さくして行く
と感度が低下する傾向にあり、高感度化と高画質化とを
両立させるには限界があった。However, as generally practiced, the sensitivity tends to decrease as the grain size of silver halide grains is reduced in order to improve the image quality, and both high sensitivity and high image quality can be achieved. Had limitations.

【０００５】より一層の高感度化、高画質化を図るべく
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。その一つとして、平板
状ハロゲン化銀粒子を使用する技術が特開昭５８−１１
１９３５号、同５８−１１１９３６号、同５８−１１１
９３７号、同５８−１１３９２７号、同５９−９９４３
３号等に記載されている。これらの平板状ハロゲン化銀
粒子を８面体や１４面体、あるいは６面体などの、いわ
ゆる正常晶ハロゲン化銀粒子と比較すると、ハロゲン化
銀粒子の体積が同じ場合には表面積は大きくなり、従っ
てハロゲン化銀粒子表面に多くの増感色素を吸着させる
ことができ、一層の高感度化を図れる利点がある。Techniques for improving the sensitivity / grain size ratio per silver halide grain have been studied in order to achieve higher sensitivity and higher image quality. As one of them, a technique using tabular silver halide grains is disclosed in JP-A-58-11.
No. 1935, No. 58-111936, No. 58-111
No. 937, No. 58-113927, No. 59-9943
No. 3 and the like. When these tabular silver halide grains are compared with so-called normal-crystal silver halide grains such as octahedral, tetrahedral or hexahedral grains, the surface area increases when the volume of the silver halide grains is the same, and therefore, the surface area increases. Many sensitizing dyes can be adsorbed on the surface of silver halide grains, and there is an advantage that sensitivity can be further enhanced.

【０００６】特開平６−２３０４９１号、同６−２３５
９８８号、同６−２５８７４５号、同６−２８９５１６
号等では、従来より更に高アスペクト比の平板状ハロゲ
ン化銀粒子を用いる検討も為されている。更に、特開昭
６３−９２９４２号には、平板状ハロゲン化銀粒子内部
に沃化銀含有率の高いコアを設ける技術が、特開昭６３
−１６３５４１号には、双晶面間の最も長い距離に対す
る粒子厚みの比が５以上である平板状ハロゲン化銀粒子
を用いる技術が開示されており、それぞれ感度、粒状性
における効果が示されている。JP-A-6-230491, JP-A-6-235
988, 6-258745, 6-289516
Have examined using tabular silver halide grains having a higher aspect ratio than before. Further, JP-A-63-92942 discloses a technique of providing a core having a high silver iodide content inside tabular silver halide grains.
No. 163541 discloses a technique using tabular silver halide grains in which the ratio of the grain thickness to the longest distance between twin planes is 5 or more, and shows effects on sensitivity and graininess, respectively. I have.

【０００７】又、特開昭６３−１０６７４６号には、二
つの相対向する主平面に対して平行な方向に実質的に層
状構造を有する平板状ハロゲン化銀粒子を、特開平１−
２７９２３７号には、二つの相対向する主平面に対して
実質的に平行な面で区切られる層状構造を有し、最外層
の平均沃化銀含有率がハロゲン化銀粒子全体の平均沃化
銀含有率よりも少なくとも１モル％以上高い平板状ハロ
ゲン化銀粒子を、それぞれ用いる技術について記述され
ている。JP-A-63-106746 discloses a tabular silver halide grain having a substantially layered structure in a direction parallel to two opposing main planes.
No. 279237 has a layered structure separated by a plane substantially parallel to two opposite main planes, and the average silver iodide content of the outermost layer is the average silver iodide of the entire silver halide grains. It describes a technique for using tabular silver halide grains at least 1 mol% higher than the content.

【０００８】特開平３−１２１４４５号では、平行な双
晶面を有し、かつ互いに沃度含率の異なる領域を有する
界面層で構成されたハロゲン化銀粒子が、特開昭６３−
３０５３４３号では、頂点近傍に現像開始点を有する平
板状ハロゲン化銀粒子が、特開平２−３４号では（１０
０）面と（１１１）面とを有するハロゲン化銀粒子が、
それぞれ開示されている。Japanese Patent Application Laid-Open No. 3-121445 discloses a silver halide grain composed of an interface layer having parallel twin planes and regions having different iodine contents from each other.
No. 305343, tabular silver halide grains having a development start point near the apex are disclosed in JP-A-2-34 (10).
Silver halide grains having a (0) plane and a (111) plane,
Each is disclosed.

【０００９】その他、特開平１−１８３６４４号には、
沃化銀を含むハロゲン化銀の沃化銀分布が完全に均一で
あることを特徴とする平板状ハロゲン化銀粒子を用いる
技術が開示されている。In addition, Japanese Patent Application Laid-Open No. 1-183644 discloses that
A technique using tabular silver halide grains, characterized in that the silver iodide distribution of silver halide containing silver iodide is completely uniform is disclosed.

【００１０】又、メタルドーピングによりキャリアコン
トロールを図る技術、即ち、ハロゲン化銀粒子中に主と
して多価金属酸化物を含有せしめることにより、写真特
性を改良する技術が開示されている。Further, there is disclosed a technique for controlling carriers by metal doping, that is, a technique for improving photographic characteristics by mainly including a polyvalent metal oxide in silver halide grains.

【００１１】特開平３−１９６１３５号、同３−１８９
６４１号などには、銀に対する酸化剤の存在下で製造さ
れたハロゲン化銀乳剤及びこれを用いた感光材料を用い
た際の感度、カブリに対する効果が開示されている。JP-A-3-196135 and JP-A-3-189
No. 641 and the like disclose a silver halide emulsion produced in the presence of an oxidizing agent for silver and an effect on sensitivity and fog when a photosensitive material using the same is used.

【００１２】更に、例えば特開昭６３−２２０２３８号
においては、転位線の位置を規定した平板状ハロゲン化
銀粒子を含むハロゲン化銀乳剤を用いる技術が、特開平
３−１７５４４０号においては、粒子の頂点近傍に転位
線が集中している平板状ハロゲン化銀粒子を含むハロゲ
ン化銀乳剤を用いる技術が開示され、特公平３−１８６
９５号においては、明確なコア／シェル構造を持つハロ
ゲン化銀粒子を用いる技術が、特公平３−３１２４５号
においては、コア／シェル３層構造のハロゲン化銀粒子
に関する技術が採り上げられ、それぞれ高感度化技術と
して検討されてきた。Further, for example, JP-A-63-220238 discloses a technique using a silver halide emulsion containing tabular silver halide grains in which the position of dislocation lines is defined. Using silver halide emulsions containing tabular silver halide grains in which dislocation lines are concentrated in the vicinity of the vertex is disclosed in Japanese Patent Publication No. 3-186.
No. 95 describes a technique using silver halide grains having a clear core / shell structure, and Japanese Patent Publication No. 3-31245 discusses a technique relating to silver halide grains having a three-layered core / shell structure. It has been studied as a sensitivity enhancement technique.

【００１３】特開平６−１１７８１号、同６−１１７８
２号、同６−２７５６４号、同６−２５０３０９号、同
６−２５０３１０号、同６−２５０３１１号、同６−２
５０３１３号、同６−２４２５２７号等では、ハロゲン
化銀粒子形成において沃化物イオン放出化合物を用いて
高感度化、カブリ・圧力耐性の改良を実現している。JP-A-6-11781 and JP-A-6-1178
No. 2, No. 6-27564, No. 6-250309, No. 6-250310, No. 6-250311, No. 6-2
Nos. 50313, 6-242527, etc., realize high sensitivity and improved fog / pressure resistance by using an iodide ion releasing compound in forming silver halide grains.

【００１４】しかし、これらの従来技術では、高感度化
と高画質化との両立には限界があり、近年の感光材料に
おける要求を満たすには不十分であり、より優れた技術
の開発が望まれていた。However, these conventional techniques have limitations in achieving both high sensitivity and high image quality, and are insufficient to satisfy recent demands on photosensitive materials. Was rare.

【００１５】上記写真性能向上のため、ハロゲン化銀粒
子に対し、よりいっそう効果的な化学増感・色増感を施
すには、ハロゲン化銀粒子表面において、これまで以上
に精緻な感光核サイト及びハロゲン組成の制御を可能と
する技術の開発が必要であり、当業界における従来の検
討は、この要請に対して十分に応えるものではなかっ
た。In order to perform more effective chemical sensitization and color sensitization on silver halide grains in order to improve the photographic performance described above, it is necessary to provide a finer photosensitive nucleus site on the silver halide grain surface than ever. Further, it is necessary to develop a technology that enables control of the halogen composition, and conventional studies in the art have not sufficiently responded to this demand.

【００１６】又、当業界における塩化銀含有ハロゲン化
銀写真乳剤の検討においては、現像性向上効果は確認さ
れつつも、カブリの上昇を伴い、常用感光材料におい
て、感度／画質向上を図るには困難が伴った。In the field of examination of silver halide photographic emulsions containing silver chloride in the art, it has been confirmed that the effect of improving the developability has been confirmed. There was difficulty.

【００１７】[0017]

【発明が解決しようとする課題】従って本発明の目的
は、高感度でありながら、粒状性にも優れるハロゲン化
銀写真乳剤、及び該乳剤を用いたハロゲン化銀写真感光
材料を提供することにある。SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide photographic emulsion having high sensitivity and excellent graininess, and a silver halide photographic material using the emulsion. is there.

【００１８】[0018]

【課題を解決するための手段】本発明者らは鋭意検討の
結果、ハロゲン化銀粒子間の均一性を保ちつつ、ハロゲ
ン化銀粒子最表面近傍のハロゲン化銀相におけるハロゲ
ン化銀相形成時の不要塩類の除去、添加剤添加時におけ
る不均一性の排除、ハロゲン化銀相成長方向の限定等に
より、ハロゲン化銀組成のより精緻な制御及び形成を可
能とし、ハロゲン化銀粒子表面において化学増感、色増
感の各々に対して最適なサイトをそれぞれ作り分けるこ
とを可能とすることにより、従来技術ではなし得なかっ
た感度、カブリレベルの向上を実現させたハロゲン化銀
写真乳剤の開発に成功し、本発明を為すに至った。即
ち、本発明の上記目的は下記構成により達成される。Means for Solving the Problems As a result of intensive studies, the present inventors have found that while maintaining the uniformity between silver halide grains, the silver halide phase in the silver halide phase near the outermost surface of the silver halide grains is formed. Removal of unnecessary salts, elimination of non-uniformity at the time of addition of additives, limitation of the growth direction of silver halide phase, etc., enable more precise control and formation of silver halide composition, Development of silver halide photographic emulsions that can improve the sensitivity and fog level that could not be achieved by conventional technology by making it possible to create optimal sites for sensitization and color sensitization separately. And succeeded in accomplishing the present invention. That is, the above object of the present invention is achieved by the following constitutions.

【００１９】（１）分散媒とハロゲン化銀粒子を含むハ
ロゲン化銀写真乳剤であって、該ハロゲン化銀粒子が最
表層に塩化銀を含有し、かつ該最表層の頂点近傍におけ
る臭化銀含有率をＡ1、最表層の頂点近傍を除いた部分
の臭化銀含有率をＡ2とした時、Ａ1／Ａ2＞１．０であ
るハロゲン化銀粒子が５０％以上（個数）存在するハロ
ゲン化銀写真乳剤。(1) A silver halide photographic emulsion containing a dispersion medium and silver halide grains, wherein the silver halide grains contain silver chloride in the outermost layer and silver bromide near the top of the outermost layer. When the content is A 1 and the content of silver bromide in the portion excluding the vicinity of the top of the outermost layer is A 2 , 50% or more (number) of silver halide grains satisfying A 1 / A 2 > 1.0. Silver halide photographic emulsion present.

【００２０】（２）分散媒とハロゲン化銀粒子を含むハ
ロゲン化銀写真乳剤であって、該ハロゲン化銀粒子が最
表層に塩化銀を含有し、かつ該最表層の沃化銀含有率の
平均値をＢ1、ハロゲン化銀粒子の沃化銀含有率の平均
値をＢ2とした時、Ｂ1／Ｂ2＞１．０であるハロゲン化
銀写真乳剤。(2) A silver halide photographic emulsion containing a dispersion medium and silver halide grains, wherein the silver halide grains contain silver chloride in the outermost layer and the silver iodide content of the outermost layer is B 1 the average value, when the average value of the silver iodide content of the silver halide grains and a B 2, B 1 / B 2 > 1.0 silver halide photographic emulsions.

【００２１】（３）分散媒とハロゲン化銀粒子を含むハ
ロゲン化銀写真乳剤であって、該ハロゲン化銀粒子が
（１１１）面と（１００）面とを有し、最表層に塩化銀
を含有し、かつ該最表層の沃化銀含有率を（１１１）面
でＣ1、（１００）面でＣ2とした時、Ｃ1／Ｃ2＞１．０
であるハロゲン化銀粒子が５０％以上（個数）存在する
ハロゲン化銀写真乳剤。(3) A silver halide photographic emulsion containing a dispersion medium and silver halide grains, wherein the silver halide grains have (111) planes and (100) planes, and silver chloride is formed on the outermost layer. contained, and C 1 silver iodide content of the outermost layer with (111) plane, when the C 2 at (100) plane, C 1 / C 2> 1.0
A silver halide photographic emulsion in which 50% or more (number) of silver halide grains are present.

【００２２】（４）ハロゲン化銀粒子が平板状ハロゲン
化銀粒子である（２）又は（３）に記載のハロゲン化銀
写真乳剤。(4) The silver halide photographic emulsion according to (2) or (3), wherein the silver halide grains are tabular silver halide grains.

【００２３】（５）支持体上のハロゲン化銀乳剤層の少
なくとも１層に、（１）〜（４）のいずれか１項に記載
のハロゲン化銀写真乳剤を含むハロゲン化銀写真感光材
料。(5) A silver halide photographic light-sensitive material comprising the silver halide photographic emulsion according to any one of (1) to (4) in at least one of the silver halide emulsion layers on the support.

【００２４】以下、本発明について具体的に説明する。Hereinafter, the present invention will be described specifically.

【００２５】本発明において、分散媒とは保護コロイド
を構成し得る物質を指すが、該保護コロイドにはゼラチ
ンを用いることが好ましい。In the present invention, the dispersion medium refers to a substance capable of forming a protective colloid, and it is preferable to use gelatin for the protective colloid.

【００２６】分散媒にゼラチンを用いる場合には、該ゼ
ラチンは、石灰処理されたもの、酸処理されたもの、イ
オン交換処理されたもの等を用いることができるが、特
開平７−２６１２９８号記載のアデニン含有量が０．２
ｐｐｍ以下であるゼラチンであることが好ましい。ゼラ
チン製法の詳細は、アーサー・ヴァイス著「ザ・マクロ
モレキュラー・ケミストリー・オブ・ゼラチン」（アカ
デミック・プレス，１９６４年発行）等に記載がある。When gelatin is used as the dispersion medium, lime-treated gelatin, acid-treated gelatin, ion-exchanged gelatin, and the like can be used, as described in JP-A-7-261298. Has an adenine content of 0.2
It is preferred that the gelatin is not more than ppm. Details of the gelatin production method are described in Arthur Weiss's "The Macromolecular Chemistry of Gelatin" (Academic Press, 1964) and the like.

【００２７】又、ゼラチン以外の保護コロイドを形成し
得る物質としては、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
ン等の蛋白質；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等のセル
ロース誘導体；アルギン酸ナトリウム、澱粉誘導体等の
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、ポリビニルピロリドン、ポリアクリ
ル酸、ポリアクリルアミド、ポリメタアクリル酸、ポリ
ビニルイミダゾール、ポリビニルピラゾール等の単一あ
るいは共重合体のような多種の合成又は半合成親水性高
分子物質を挙げることができる。Substances that can form protective colloids other than gelatin include, for example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfate and the like. Cellulose derivatives of the following: sugar derivatives such as sodium alginate and starch derivatives; homo- or copolymers such as polyvinyl alcohol, polyvinyl alcohol partial acetal, polyvinyl pyrrolidone, polyacrylic acid, polyacrylamide, polymethacrylic acid, polyvinyl imidazole, polyvinyl pyrazole, etc. And various kinds of synthetic or semi-synthetic hydrophilic polymer substances.

【００２８】本発明において、ハロゲン化銀粒子の最表
層とは、ハロゲン化銀粒子表面を含み、該ハロゲン化銀
粒子表面から深さ５０Å迄のハロゲン化銀相をいう。In the present invention, the outermost layer of the silver halide grains refers to a silver halide phase including the surface of the silver halide grains and extending to a depth of 50 ° from the surface of the silver halide grains.

【００２９】本発明においては、ハロゲン化銀粒子の最
表層に塩化銀を含有することを特徴とする。The present invention is characterized in that the outermost layer of the silver halide grains contains silver chloride.

【００３０】ハロゲン化銀粒子の最表層に塩化銀を含有
することは、ハロゲン化銀粒子のハロゲン化銀組成をＸ
線回折手法を用いることにより、該最表層の形成前後で
の塩化銀含有比率から確認することができる。When silver chloride is contained in the outermost layer of the silver halide grains, the silver halide composition of the silver halide grains is changed to X.
By using the line diffraction technique, it can be confirmed from the silver chloride content ratio before and after the formation of the outermost layer.

【００３１】Ｘ線回折手法に関しては、基礎分析化学講
座２４「Ｘ線分析」（共立出版）等を参考にすることが
できる。Regarding the X-ray diffraction method, reference can be made to Basic Analytical Chemistry Lecture 24, “X-ray analysis” (Kyoritsu Shuppan).

【００３２】該最表層のハロゲン化銀組成は、塩化銀、
沃塩化銀、沃塩臭化銀、塩臭化銀等の任意のものを用い
ることができる。The silver halide composition of the outermost layer is silver chloride,
Any of silver iodochloride, silver iodochlorobromide, silver chlorobromide and the like can be used.

【００３３】本発明の請求項１に係るハロゲン化銀写真
乳剤（以下、写真乳剤とも略す）は、分散媒とハロゲン
化銀粒子を含む写真乳剤において、該ハロゲン化銀粒子
が最表層に塩化銀を含有し、かつ該ハロゲン化銀粒子の
最表層の頂点近傍における臭化銀含有率をＡ1、最表層
の頂点近傍を除いた部分の臭化銀含有率をＡ2とした
時、Ａ1／Ａ2＞１．０であるハロゲン化銀粒子が５０％
以上（個数）存在することを特徴とする。The silver halide photographic emulsion according to claim 1 of the present invention (hereinafter, also abbreviated as photographic emulsion) is a photographic emulsion containing a dispersion medium and silver halide grains, wherein the silver halide grains are formed of silver chloride on the outermost layer. And the silver bromide content in the vicinity of the vertex of the outermost layer of the silver halide grains is A 1 , and the silver bromide content of the portion excluding the vicinity of the vertex of the outermost layer is A 2 , where A 1 / A 2 > 1.0, 50% of silver halide grains
It is characterized in that the above (number) exists.

【００３４】ハロゲン化銀粒子が非平板状ハロゲン化銀
粒子の場合における頂点とは、ハロゲン化銀粒子の外表
面における角であり、頂点近傍とは、該頂点を中心とし
て、ハロゲン化銀粒子の投影面積円換算粒径の１／１０
に相当する半径で円を描いたときに該円の内側の領域を
いう。In the case where the silver halide grains are non-tabular silver halide grains, the apex is an angle on the outer surface of the silver halide grain, and the vicinity of the apex means that the apex is the center of the apex. 1/10 of the projected area circle equivalent particle size
Means a region inside the circle when a circle is drawn with a radius corresponding to.

【００３５】ハロゲン化銀粒子が平板状ハロゲン化銀粒
子の場合における頂点とは、該平板状ハロゲン化銀粒子
を主平面に対して垂直方向から見た時の投影像の形状が
多角形の場合には、該多角形の角であり、該平板状ハロ
ゲン化銀粒子が丸みを帯びた形状の場合には、直線部分
を延長して接線を引きその交点を頂点とする。The vertex in the case where the silver halide grains are tabular silver halide grains means that the shape of the projected image when the tabular silver halide grains are viewed from a direction perpendicular to the main plane is polygonal. Are the corners of the polygon, and when the tabular silver halide grains have a rounded shape, a straight line portion is extended to draw a tangent line, and the intersection point is defined as the vertex.

【００３６】ハロゲン化銀粒子が平板状ハロゲン化銀粒
子の場合における頂点近傍とは、上記平板状ハロゲン化
銀粒子を主平面に対して垂直方向から見た時の投影像に
おいて、前述により求めた頂点を中心として、平板状ハ
ロゲン化銀粒子の投影面積円換算粒径の１／１０に相当
する半径で円を描いた時に該円の内側の領域をいう。The vicinity of the apex when the silver halide grains are tabular silver halide grains is determined as described above in a projected image when the tabular silver halide grains are viewed from a direction perpendicular to the main plane. When a circle is drawn with a radius corresponding to 1/10 of the projected area circle diameter of the tabular silver halide grains with the vertex as the center, the area inside the circle is referred to.

【００３７】平板状ハロゲン化銀粒子とは、アスペクト
比（ハロゲン化銀粒子の厚みに対する直径の比）が１．
３以上のハロゲン化銀粒子を言う。アスペクト比は、好
ましくは３．０〜１００であり、より好ましくは５．０
〜５０である。The tabular silver halide grains have an aspect ratio (the ratio of the diameter to the thickness of the silver halide grains) of 1.
It refers to three or more silver halide grains. The aspect ratio is preferably from 3.0 to 100, more preferably 5.0.
~ 50.

【００３８】アスペクト比を求めるには、まずハロゲン
化銀粒子直径と厚みとを以下の方法で求める。支持体上
に内部標準となる粒径が既知であるラテックスボール及
び主平面が該支持体に対し平行に配向するように塗布し
た試料を作製し、或る方向からカーボン蒸着法によりシ
ャドーイングを施した後、通常のレプリカ法によりレプ
リカ試料を作製する。同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各々のハロゲン化銀粒子の
投影面積直径と厚みとを求める。この際、ハロゲン化銀
粒子の厚みは、内部標準とハロゲン化銀粒子の影（シャ
ドー）の長さから算出することができる。To determine the aspect ratio, first, the diameter and thickness of a silver halide grain are determined by the following method. A latex ball having a known particle size as an internal standard and a sample coated so that the main plane is oriented parallel to the support are prepared on a support, and shadowing is performed by a carbon deposition method from a certain direction. After that, a replica sample is prepared by a normal replica method. An electron micrograph of the sample is taken, and the projected area diameter and thickness of each silver halide grain are determined using an image processing device or the like. At this time, the thickness of the silver halide grains can be calculated from the internal standard and the length of the shadow of the silver halide grains.

【００３９】ハロゲン化銀粒子の最表層の頂点近傍にお
ける臭化銀含有率Ａ1は、前記ハロゲン化銀粒子の最表
層における上記頂点近傍領域において、等間隔で五つ以
上の箇所で測定を行った臭化銀含有率を平均すること
で、個々のハロゲン化銀粒子について求められ、具体的
には以下の方法による。The silver bromide content A 1 in the vicinity of the apex of the outermost layer of the silver halide grains is measured at five or more places at equal intervals in the area near the apex of the outermost layer of the silver halide grains. The average silver bromide content is determined for each silver halide grain by the following method.

【００４０】写真乳剤中のハロゲン化銀粒子を、蛋白質
分解酵素によりゼラチン分解して取り出した後、メタク
リル樹脂で包埋し、ダイヤモンドカッターで厚さ約５０
０Åの切片を連続的に切り出し、これらの切片の内、ハ
ロゲン化銀粒子表面から深さ５０Å迄のハロゲン化銀相
について、当業界で周知のＥＰＭＡ法（Ｅｌｅｃｔｒｏ
ｎ Ｐｒｏｂｅ Ｍｉｃｒｏ Ａｎａｌｙｚｅｒ）を用
いてスポット径を５０Åに絞った点分析により臭化銀含
有率を測定する。The silver halide grains in the photographic emulsion are decomposed by gelatin with a protease, taken out, embedded in methacrylic resin, and cut with a diamond cutter to a thickness of about 50 mm.
0 ° sections were continuously cut out. Of these sections, the silver halide phase from the surface of the silver halide grains to a depth of 50 ° was subjected to the EPMA method (Electro) well known in the art.
The silver bromide content is measured by point analysis with the spot diameter being narrowed to 50 ° using a Probe Micro Analyzer.

【００４１】最表面の頂点近傍を除いた部分の臭化銀含
有率Ａ2は、前記ハロゲン化銀粒子の最表層において、
頂点近傍を除いて等間隔で２０以上の箇所で測定を行っ
た臭化銀含有率を平均することで求められる。The silver bromide content A 2 of the portion excluding the vicinity of the top of the outermost surface is determined as follows:
It is determined by averaging the silver bromide content measured at 20 or more locations at equal intervals except for the vicinity of the apex.

【００４２】尚、上記方法による測定は、５００個以上
のハロゲン化銀粒子について行うものとする。Incidentally, the measurement by the above method is performed on 500 or more silver halide grains.

【００４３】又、請求項１に係る写真乳剤は、Ａ1／Ａ2
＞１．０であるハロゲン化銀粒子が７０％以上（個数）
存在することが好ましい。更には、Ａ1／Ａ2＞１．３で
あるハロゲン化銀粒子が５０％以上（個数）存在するこ
とが好ましい。Further, the photographic emulsion according to claim 1 has A 1 / A 2
70% or more (number) of silver halide grains with> 1.0
Preferably it is present. Furthermore, silver halide grains is A 1 / A 2> 1.3 is preferably present at least 50% (number).

【００４４】本発明の請求項２に係る写真乳剤は、分散
媒とハロゲン化銀粒子を含む写真乳剤において、該ハロ
ゲン化銀粒子が最表層に塩化銀を含有し、かつ該最表層
の沃化銀含有率の平均値をＢ1、ハロゲン化銀粒子の沃
化銀含有率の平均値をＢ2とした時、Ｂ1／Ｂ2＞１．０
であることを特徴とする。The photographic emulsion according to claim 2 of the present invention is a photographic emulsion containing a dispersion medium and silver halide grains, wherein the silver halide grains contain silver chloride in the outermost layer and iodide in the outermost layer. When the average value of the silver content is B 1 and the average value of the silver iodide content of the silver halide grains is B 2 , B 1 / B 2 > 1.0.
It is characterized by being.

【００４５】本発明において、ハロゲン化銀粒子最表層
の沃化銀含有率は、前記ハロゲン化銀粒子の最表層にお
いて、等間隔で五つ以上の箇所で測定を行った沃化銀含
有率を平均することで、個々のハロゲン化銀粒子につい
て求められ、具体的には前記臭化銀含有率の測定と同様
のＥＰＭＡ法を用いた点分析によればよい。In the present invention, the silver iodide content of the outermost layer of the silver halide grains is determined by measuring the silver iodide content measured at five or more points at equal intervals in the outermost layer of the silver halide grains. By averaging, it is determined for each silver halide grain, and more specifically, a point analysis using the EPMA method similar to the measurement of the silver bromide content may be used.

【００４６】上記方法により個々のハロゲン化銀粒子に
ついて求めたハロゲン化銀粒子最表層の沃化銀含有率を
５００個以上のハロゲン化銀粒子について求め、平均し
たものを最表層の沃化銀含有率の平均値Ｂ1とする。The silver iodide content of the outermost layer of the silver halide grains determined for each silver halide grain by the above method was determined for 500 or more silver halide grains, and the average was used to determine the silver iodide content of the outermost layer. an average value B 1 rate.

【００４７】本発明において、ハロゲン化銀粒子の沃化
銀含有率はＥＰＭＡ法により求める。具体的には、ハロ
ゲン化銀粒子を互いに接触しないようによく分散させた
試料を作製し、液体窒素で−１００℃以下に冷却しなが
ら電子ビームを照射し、個々のハロゲン化銀粒子から放
射される銀及び沃素の特性Ｘ線強度を求めることによ
り、該個々のハロゲン化銀粒子の沃化銀含有率が決定で
きる。In the present invention, the silver iodide content of the silver halide grains is determined by the EPMA method. Specifically, a sample in which silver halide grains are well dispersed so as not to be in contact with each other is prepared, and irradiated with an electron beam while being cooled to −100 ° C. or lower with liquid nitrogen, and emitted from individual silver halide grains. By determining the characteristic X-ray intensity of silver and iodine, the silver iodide content of each silver halide grain can be determined.

【００４８】上記方法により個々のハロゲン化銀粒子に
ついて求めたハロゲン化銀粒子の沃化銀含有率を５００
個以上のハロゲン化銀粒子について求め、平均したもの
を沃化銀含有率の平均値Ｂ2とする。The silver iodide content of each silver halide grain determined by the above method was 500.
Calculated for more than five silver halide grains, to those obtained by averaging the average value B 2 of silver iodide content.

【００４９】本発明の請求項２に係るハロゲン化銀写真
乳剤は、Ｂ1／Ｂ2＞１．３であることが好ましい。The silver halide photographic emulsion according to claim 2 of the present invention preferably satisfies B 1 / B 2 > 1.3.

【００５０】本発明の請求項３に係る写真乳剤は、分散
媒とハロゲン化銀粒子を含む写真乳剤において、該ハロ
ゲン化銀粒子が最表層に塩化銀を含有し、かつ該最表層
の沃化銀含有率を（１１１）面でＣ1、（１００）面で
Ｃ2とした時、Ｃ1／Ｃ2＞１．０であるハロゲン化銀粒
子が５０％以上（個数）存在することを特徴とするが、
より好ましくは７０％以上（個数）である。更には、Ｃ
1／Ｃ2＞１．３であるハロゲン化銀粒子が５０％以上
（個数）存在することが好ましい。A photographic emulsion according to claim 3 of the present invention is a photographic emulsion containing a dispersion medium and silver halide grains, wherein the silver halide grains contain silver chloride in the outermost layer and iodine in the outermost layer. C 1 the silver content in the (111) plane, characterized by the presence (100) when the C 2 in plane, C 1 / C 2> 1.0 at which the silver halide grains is 50% or more (number) But
More preferably, it is 70% or more (number). Furthermore, C
It is preferred that 50% or more (number) of silver halide grains satisfying 1 / C 2 > 1.3 exist.

【００５１】本発明では、前出の切片を連続的に切り出
すＥＰＭＡ法を用いた最表層の沃化銀含有率の測定方法
において、連続的に切り出した切片の形状から、（１１
１）面、（１００）面を区別し、各々の面について最表
層の沃化銀含有率を求め、（１１１）面での値をＣ1、
（１００）面での値をＣ2とする。According to the present invention, in the method for measuring the silver iodide content of the outermost layer using the EPMA method for continuously cutting the above-mentioned section, the shape of the continuously cut section is calculated as (11)
The 1) plane and the (100) plane are distinguished, the silver iodide content of the outermost layer is determined for each plane, and the value on the (111) plane is C 1 ,
The value on the (100) plane is C 2 .

【００５２】尚、上記方法による測定は、５００個以上
のハロゲン化銀粒子について行うものとする。The measurement by the above method is performed on 500 or more silver halide grains.

【００５３】本発明に係る写真乳剤の好ましい製造方法
を以下に述べる。A preferred method for producing the photographic emulsion according to the present invention will be described below.

【００５４】ハロゲン化銀粒子の最表層に塩化銀を含有
させるには、ハロゲン化銀基盤粒子（以下、ホスト粒子
とも称す）形成後に、塩化銀を含有するハロゲン化銀微
粒子を供給することが好ましい。In order to make the outermost layer of silver halide grains contain silver chloride, it is preferable to supply silver halide fine grains containing silver chloride after forming silver halide base grains (hereinafter also referred to as host grains). .

【００５５】該ホスト粒子を含む写真乳剤は、脱塩を施
してあることが好ましく、ホスト粒子上にハロゲン化銀
組成の異なるハロゲン化銀相を複数形成する際には、一
つのハロゲン化銀相形成操作の度に脱塩操作を行い、残
留する不要塩類等を除去することにより、意図しないハ
ロゲン化銀組成のコンバージョンを抑制することがで
き、特に好ましい。The photographic emulsion containing the host grains is preferably desalted. When a plurality of silver halide phases having different silver halide compositions are formed on the host grains, one silver halide phase may be used. It is particularly preferable that undesired conversion of the silver halide composition can be suppressed by performing a desalting operation every time a forming operation is performed to remove residual unnecessary salts and the like.

【００５６】上記脱塩は、例えばリサーチ・ディスクロ
ージャ（Ｒｅｓｅａｒｃｈ Ｄｉｓｃｌｏｓｕｒｅ、以
下ＲＤと略す）１７６４３号II項の方法により行うこと
ができる。更に詳しくは、沈殿生成物又は物理熟成後の
乳剤から不要な可溶性塩類を除去する為には、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など）、あるいはゼラチ
ン誘導体（アシル化ゼラチン、カルバモイル化ゼラチン
等）を利用した沈殿法を用いることができる。The desalting can be carried out, for example, by the method described in Research Disclosure (hereinafter abbreviated as RD) No. 17643 No. II. More specifically, in order to remove unnecessary soluble salts from the precipitated product or the emulsion after physical ripening, a Nudel washing method performed by gelling gelatin may be used,
Further, a precipitation method using an inorganic salt, an anionic surfactant, an anionic polymer (such as polystyrenesulfonic acid), or a gelatin derivative (such as acylated gelatin or carbamoylated gelatin) can be used.

【００５７】その他、化学工学便覧，改訂５版（化学工
学協会編，丸善）９２４〜９５４頁等に記載の限外濾過
を利用した脱塩も、より好ましく用いることができる。In addition, desalting using ultrafiltration described in Chemical Engineering Handbook, Revised 5th Edition (edited by the Society of Chemical Engineers, Maruzen), pages 924 to 954, etc. can be more preferably used.

【００５８】限外濾過脱塩の方法に関しては、ＲＤの１
０２巻１０２０８及び同１３１巻１３１２２、特公昭５
９−４３７２７号、同６２−２７００８号、特開昭６２
−１１３１３７号、同５７−２０９８２３号、同５９−
４３７２７号、同６２−１１３１３７号、同６１−２１
９９４８号、同６２−２３０３５号、同６３−４０１３
７号、同６３−４００３９号、特開平３−１４０９４６
号、同２−１７２８１６号、同２−１７２８１７号、同
４−２２９４２号等に記載の方法を参考にすることがで
きる。Regarding the method of ultrafiltration desalination, one of the RD
02, 10208 and 131, 13122, Shoko 5
Nos. 9-43727 and 62-27008;
-113137, 57-209823, 59-
43727, 62-11137, 61-21
No. 9948, No. 62-23035, No. 63-4013
No. 7, 63-40039, JP-A-3-140946
And the methods described in JP-A Nos. 2-172816, 2-172817 and 4-22942 can be referred to.

【００５９】上記塩化銀を含有するハロゲン化銀微粒子
には、ハロゲン化銀として塩化銀、沃塩化銀、沃塩臭化
銀、塩臭化銀等の任意の組成のものを、目的に応じて用
いることができるが、平均塩化銀含有率は２０〜１００
モル％であることが好ましく、より好ましくは５０〜１
００モル％である。塩化銀を含有するハロゲン化銀微粒
子は、前出の手法により脱塩を施してあることが好まし
く、限外濾過脱塩を施してあることがより好ましい。The silver halide fine grains containing silver chloride may be any silver halide, silver iodochloride, silver iodochlorobromide, silver chlorobromide, etc. as the silver halide depending on the purpose. The average silver chloride content is 20 to 100.
Mol%, more preferably 50 to 1 mol%.
00 mol%. The silver halide fine grains containing silver chloride are preferably desalted by the method described above, and more preferably subjected to ultrafiltration desalting.

【００６０】塩化銀を含有するハロゲン化銀微粒子のホ
スト粒子に対する添加量は、ホスト粒子の銀量の０．１
〜３０モル％であることが好ましく、１〜２０モル％が
更に好ましい。The amount of silver halide fine grains containing silver chloride added to the host grains is 0.1% of the silver content of the host grains.
It is preferably from 30 to 30 mol%, more preferably from 1 to 20 mol%.

【００６１】塩化銀を含有するハロゲン化銀微粒子をホ
スト粒子を含む写真乳剤に対して添加するには、該塩化
銀を含有するハロゲン化銀微粒子を保護コロイドを含む
水溶液中に分散させて添加する方法が好ましく用いられ
る。該ハロゲン化銀微粒子の添加は、漏斗添加あるいは
ポンプ等を用いて関数添加することもでき、２回以上に
分割して添加してもよく、該ハロゲン化銀微粒子の添加
後、必要に応じて熟成を行ってもよい。In order to add silver halide fine grains containing silver chloride to a photographic emulsion containing host grains, the silver halide fine grains containing silver chloride are added by dispersing them in an aqueous solution containing a protective colloid. The method is preferably used. The addition of the silver halide fine particles may be performed by funnel addition or by function addition using a pump or the like, or may be added in two or more portions, and after the silver halide fine particles are added, if necessary. Aging may be performed.

【００６２】塩化銀を含有するハロゲン化銀微粒子の添
加時に、ホスト粒子を含む写真乳剤は温度が４０〜９０
℃であることが好ましく、５０〜８０℃がより好まし
く、ｐＨは３．０〜上８．０であることが好ましく、
４．０〜７．０がより好ましい。When silver halide fine grains containing silver chloride are added, the temperature of the photographic emulsion containing host grains should be 40 to 90.
° C, more preferably 50 to 80 ° C, and the pH is preferably 3.0 to 8.0,
4.0 to 7.0 are more preferred.

【００６３】塩化銀を含有するハロゲン化銀微粒子添加
後のホスト粒子を含むハロゲン化銀写真乳剤のｐＣｌは
０．５〜３．５が好ましく、１．０〜３．０がより好ま
しい。The pCl of the silver halide photographic emulsion containing host grains after the addition of silver halide fine grains containing silver chloride is preferably 0.5 to 3.5, more preferably 1.0 to 3.0.

【００６４】本発明に係る写真乳剤は、特願平９−３４
９４２１号に記載の、分子内にハロゲン化銀への吸着基
とハロゲンイオンを放出可能な置換基を有する化合物を
用いる写真乳剤の製造方法、及び／又はホスト粒子形成
後に限外濾過されたハロゲン化銀微粒子を用いる写真乳
剤の製造方法を用いることにより、ハロゲン化銀組成を
適切に制御し、製造することができるので、特に好まし
い。The photographic emulsion according to the present invention is disclosed in Japanese Patent Application No. 9-34.
No. 9421, a method for producing a photographic emulsion using a compound having a substituent capable of releasing an adsorbable group to silver halide and a halogen ion in the molecule, and / or a halogenated ultrafiltration after formation of host grains It is particularly preferable to use a method for producing a photographic emulsion using silver fine particles, since the silver halide composition can be appropriately controlled and produced.

【００６５】本発明に係る写真乳剤に含まれるハロゲン
化銀粒子は、立方体、八面体、十四面体のような規則的
な結晶構造を持つものでもよいし、球状や板状のような
変則的な結晶形を持つものでもよいが、平板状ハロゲン
化銀粒子が好ましい。これらの粒子において、晶癖（１
００）面と（１１１）面の比率は任意のものが使用でき
る。又、これらの結晶形の複合であってもよく、様々な
結晶形の粒子が混合されていてもよい。二つの対向する
平行な双晶面を有する双晶ハロゲン化銀粒子を用いるこ
ともできるが、その場合にも、平板状ハロゲン化銀粒子
であることが好ましい。The silver halide grains contained in the photographic emulsion according to the present invention may have a regular crystal structure such as cubic, octahedral or tetradecahedral, or may have irregular shapes such as spherical or tabular. Although it may have a typical crystal form, tabular silver halide grains are preferred. In these particles, the crystal habit (1
Any ratio can be used for the ratio between the (00) plane and the (111) plane. Further, a composite of these crystal forms may be used, and particles of various crystal forms may be mixed. Twin silver halide grains having two opposing parallel twin planes can also be used, but in such a case, tabular silver halide grains are preferred.

【００６６】本発明の請求項２及び３に係る写真乳剤に
含まれるハロゲン化銀粒子は、平板状ハロゲン化銀粒子
であることが好ましく、二つの対向する平行な双晶面を
有する双晶ハロゲン化銀粒子がより好ましい。The silver halide grains contained in the photographic emulsions according to claims 2 and 3 of the present invention are preferably tabular silver halide grains, and are twin halogens having two opposed parallel twin planes. Silver halide grains are more preferred.

【００６７】前記の双晶とは、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るが、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
フィッシュ・コレスポンデンツ（Ｐｈｏｔｏｇｒａｐｈ
ｉｓｈｅ Ｋｏｒｒｅｓｐｏｎｄｅｎｔｚ）」９９巻，
９９頁、同１００巻，５７頁に詳しく述べられている。The twins are silver halide crystals having one or more twin planes in one grain. The classification of twins is described in a report by Klein and Moiser, “Photographic Correspondents (Photograph)
ishe Korrespondentz) ", Volume 99,
The details are described on page 99, volume 100, and page 57.

【００６８】ハロゲン化銀粒子の双晶面は、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、平板状ハロゲン化銀粒子の主平面
が、支持体に対してほぼ平行に配向するようにハロゲン
化銀乳剤を支持体上に塗布して試料を作製する。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。The twin plane of the silver halide grains can be observed with a transmission electron microscope. The specific method is as follows. First, a sample is prepared by coating a silver halide emulsion on a support so that the main plane of the tabular silver halide grains is oriented substantially parallel to the support. This is cut using a diamond cutter to a thickness of 0.1 μm
Obtain approximately thin sections. By observing this section with a transmission electron microscope, the presence of twin planes can be confirmed.

【００６９】平板状ハロゲン化銀粒子を用いる場合に
は、ハロゲン化銀粒子の全投影面積の５０％以上が平板
状ハロゲン化銀粒子であることが好ましく、より好まし
くは６０％以上、更に好ましくは８０％以上である。When tabular silver halide grains are used, 50% or more of the total projected area of the silver halide grains is preferably tabular silver halide grains, more preferably 60% or more, and still more preferably. 80% or more.

【００７０】平板状ハロゲン化銀粒子を用いる場合、主
平面に平行な双晶面を２枚有する平板状ハロゲン化銀粒
子の比率がハロゲン化銀粒子個数で６０％以上であるこ
とが好ましく、より好ましくは７０％以上、更に好まし
くは８０％以上である。When tabular silver halide grains are used, the ratio of tabular silver halide grains having two twin planes parallel to the main plane is preferably 60% or more in terms of the number of silver halide grains. It is preferably at least 70%, more preferably at least 80%.

【００７１】本発明において、ハロゲン化銀粒子の平均
粒径は０．２〜１０μｍが好ましく、０．３〜７．０μ
ｍがより好ましく、０．４〜５．０μｍが最も好まし
い。In the present invention, the average grain size of the silver halide grains is preferably from 0.2 to 10 μm, more preferably from 0.3 to 7.0 μm.
m is more preferred, and 0.4 to 5.0 μm is most preferred.

【００７２】本発明において平均粒径とは、粒径ｒｉの
算術平均とする。ただし、有効数字３桁、最小桁数字は
四捨五入し、測定粒子個数は無差別に１０００個以上あ
ることとする。In the present invention, the average particle size is an arithmetic average of the particle size ri. However, three significant figures and the least significant figure are rounded off, and the number of measured particles is indiscriminately 1000 or more.

【００７３】ここでいう粒径ｒｉとは、平板状ハロゲン
化銀粒子の場合には、主平面に対し垂直な方向から見た
時の投影像を同面積の円像に換算した時の直径であり、
平板状ハロゲン化銀粒子以外の形状のハロゲン化銀粒子
においては、該ハロゲン化銀粒子の投影像を同面積の円
像に換算した時の直径である。In the case of tabular silver halide grains, the particle size ri is a diameter obtained by converting a projected image viewed from a direction perpendicular to the main plane into a circular image having the same area. Yes,
In the case of silver halide grains having a shape other than tabular silver halide grains, the diameter is obtained by converting a projected image of the silver halide grains into a circular image having the same area.

【００７４】粒径ｒｉは、ハロゲン化銀粒子を電子顕微
鏡で１万〜７万倍に拡大して撮影し、そのプリント上の
粒子直径又は投影時の面積を実測することにより得られ
る。The particle size ri can be obtained by photographing a silver halide particle with an electron microscope at a magnification of 10,000 to 70,000 and measuring the particle diameter or the area at the time of projection on the print.

【００７５】本発明において、写真乳剤は粒径分布の広
い多分散乳剤、粒径分布の狭い単分散性の乳剤など、任
意のものが用いられるが、単分散性の乳剤であることが
好ましい。In the present invention, any photographic emulsion such as a polydisperse emulsion having a wide particle size distribution and a monodisperse emulsion having a narrow particle size distribution can be used, but a monodisperse emulsion is preferable.

【００７６】単分散性の乳剤とは、下記式によって粒径
分布を定義した時、粒径分布が２０％以下のものであ
り、より好ましくは１６％未満である。The monodisperse emulsion has a particle size distribution of not more than 20%, more preferably less than 16%, when the particle size distribution is defined by the following formula.

【００７７】粒径分布（％）＝（粒径の標準偏差／平均
粒径）×１００ 平均粒径及び標準偏差は前に定義した粒径ｒｉから求め
るものとする。Particle size distribution (%) = (standard deviation of particle size / average particle size) × 100 The average particle size and standard deviation are determined from the particle size ri defined above.

【００７８】本発明の請求項１及び３に係る写真乳剤に
おいて、写真乳剤にはハロゲン化銀として沃塩臭化銀、
臭塩化銀を用いることができ、請求項２に係る写真乳剤
には、ハロゲン化銀として沃塩臭化銀、沃塩化銀を用い
ることができるが、特に沃塩臭化銀であることが好まし
い。In the photographic emulsion according to claims 1 and 3 of the present invention, the photographic emulsion contains silver iodochlorobromide as silver halide;
Silver bromochloride can be used, and in the photographic emulsion according to claim 2, silver iodochlorobromide and silver iodochloride can be used as silver halide, but silver iodochlorobromide is particularly preferable. .

【００７９】本発明において、写真乳剤に含まれるハロ
ゲン化銀粒子の平均沃化銀含有率は０．５〜４０モル％
であることが好ましく、より好ましくは１〜２０モル％
である。又、写真乳剤中に含まれるハロゲン化銀粒子の
臭化銀含有率は、５０〜９９モル％が好ましく、より好
ましくは、７０〜９８モル％である。In the present invention, the silver halide grains contained in the photographic emulsion have an average silver iodide content of 0.5 to 40 mol%.
And more preferably 1 to 20 mol%
It is. The silver bromide content of the silver halide grains contained in the photographic emulsion is preferably from 50 to 99 mol%, more preferably from 70 to 98 mol%.

【００８０】本発明において、写真乳剤中に含まれるハ
ロゲン化銀粒子の塩化銀含有率は１〜３０モル％が好ま
しく、より好ましくは２〜２０モル％である。In the present invention, the silver chloride content of the silver halide grains contained in the photographic emulsion is preferably from 1 to 30 mol%, more preferably from 2 to 20 mol%.

【００８１】本発明に係る写真乳剤に含まれるハロゲン
化銀粒子には、コア／シェル型粒子も好ましく用いるこ
とができる。コア／シェル型粒子とは、コアと該コアを
被覆するシェルとから構成される粒子であり、シェルは
１層又はそれ以上の層によって形成される。コアとシェ
ルの沃化銀含有率は、それぞれ異なることが好ましい。Core / shell type grains can be preferably used as silver halide grains contained in the photographic emulsion according to the present invention. A core / shell type particle is a particle composed of a core and a shell covering the core, and the shell is formed by one or more layers. The silver iodide content of the core and the shell is preferably different from each other.

【００８２】本発明の写真乳剤中のハロゲン化銀粒子
は、その内部に転位線を有することが好ましい。転位線
が存在する位置について特別な限定はないが、ハロゲン
化銀粒子の外周部近傍や稜線近傍、又は頂点近傍に存在
することが好ましい。転位線の導入時期は、ハロゲン化
銀粒子全体の銀量に対して５０％以上であることが好ま
しく、６０〜８５％未満の間で導入されることが更に好
ましい。転位線の本数は、５本以上の転位線を有するハ
ロゲン化銀粒子が３０％以上（個数）存在することが好
ましいが、５０％以上であることがより好ましく、８０
％以上であることが更に好ましい。又、それぞれの場合
において、１粒子中の転位線本数は１０本以上であるこ
とが好ましく、２０本以上であることがより好ましく、
３０本以上であることが更に好ましい。The silver halide grains in the photographic emulsion of the present invention preferably have dislocation lines therein. There is no particular limitation on the position where the dislocation line exists, but it is preferable that it exists near the outer peripheral portion, near the ridge line, or near the vertex of the silver halide grain. The introduction time of dislocation lines is preferably 50% or more, more preferably 60 to less than 85%, based on the total silver content of silver halide grains. The number of dislocation lines is preferably 30% or more (number) of silver halide grains having 5 or more dislocation lines, more preferably 50% or more, and preferably 80% or more.
% Is more preferable. In each case, the number of dislocation lines in one particle is preferably 10 or more, more preferably 20 or more,
More preferably, the number is 30 or more.

【００８３】ハロゲン化銀粒子が有する転位線は、例え
ばＪ．Ｆ．Ｈａｍｉｌｔｏｎ；Ｐｈｏｔｏ．Ｓｃｉ．Ｅ
ｎｇ．１１（１９６７）５７頁や、Ｔ．Ｓｈｉｏｚａｗ
ａ；Ｊ．Ｓｏｃ．Ｐｈｏｔｏ．Ｓｃｉ．Ｊａｐａｎ３５
（１９７２）２１３頁に記載の、低温での透過型電子顕
微鏡を用いた直接的な方法で観察することができる。即
ち、乳剤から粒子に転位線が新たに発生する程の圧力を
掛けないように注意して取り出したハロゲン化銀粒子
を、電子顕微鏡のメッシュに載せ、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する。この時、ハロゲン化銀粒子の
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。The dislocation lines of the silver halide grains are described, for example, in J. Am. F. Hamilton; Photo. Sci. E
ng. 11 (1967), p. 57; Shiozaw
a; Soc. Photo. Sci. Japan35
(1972), p. 213, and can be observed by a direct method using a transmission electron microscope at low temperature. That is, silver halide grains taken out from the emulsion without paying enough pressure to generate new dislocation lines on the grains are placed on a mesh of an electron microscope to prevent damage (printout, etc.) by the electron beam. The specimen is observed by a transmission method in a cooled state. At this time, the thicker the silver halide grains, the more difficult it is for an electron beam to pass therethrough. Therefore, the use of a high-pressure electron microscope enables clearer observation.

【００８４】このような方法によって得られた粒子写真
から、個々のハロゲン化銀粒子における転位線の位置及
び本数を求めることができる。From the grain photograph obtained by such a method, the position and the number of dislocation lines in each silver halide grain can be determined.

【００８５】ハロゲン化銀粒子への転位線の導入方法に
関しては特に限定はなく、例えば沃化カリウムのような
沃素イオン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、沃化銀微粒子を添加する方法、沃素イオ
ン溶液のみを添加する方法、特開平６−１１７８１号等
に記載の沃素イオン放出化合物を用いる方法等の公知の
方法により、ハロゲン化銀粒子中に所望の位置及び量の
転位線を導入することができる。The method for introducing dislocation lines into silver halide grains is not particularly limited. For example, a method in which an aqueous solution of iodide ion such as potassium iodide and a solution of a water-soluble silver salt are added by double jet, the method of introducing silver iodide fine grains. Dislocation at a desired position and amount in silver halide grains can be carried out by a known method such as an addition method, a method of adding only an iodine ion solution, and a method using an iodide ion releasing compound described in JP-A-6-11781. Lines can be introduced.

【００８６】写真乳剤の製造において、ホスト粒子の形
成には、当該分野でよく知られている種々の方法を用い
ることができる。即ちシングル・ジェット法、ダブル・
ジェット法、トリプル・ジェット法又はハロゲン化銀微
粒子供給法等を任意に組み合わせて使用することができ
る。又、ハロゲン化銀が生成される液相中のｐＨ、ｐＡ
ｇをハロゲン化銀の成長速度に合わせてコントロールす
る方法も併せて使用することができる。In the production of a photographic emulsion, various methods well known in the art can be used for forming host grains. That is, single jet method, double jet method
A jet method, a triple jet method, a silver halide fine particle supply method, or the like can be used in any combination. The pH, pA in the liquid phase in which silver halide is produced,
A method of controlling g according to the growth rate of silver halide can also be used.

【００８７】本発明の写真乳剤の製造には種乳剤を用い
ることもできる。種乳剤を用いる場合には、該種乳剤中
のハロゲン化銀粒子は、立方体、八面体、十四面体のよ
うな規則的な結晶構造を持つものでもよいし、球状や板
状のような変則的な結晶形を持つものでもよい。これら
の粒子において晶癖（１００）面と（１１１）面の比率
は任意のものが使用できる。又、これらの結晶形の複合
であってもよく、様々な結晶形の粒子が混合されていて
もよい。For producing the photographic emulsion of the present invention, a seed emulsion may be used. When a seed emulsion is used, the silver halide grains in the seed emulsion may have a regular crystal structure such as cubic, octahedral, or tetradecahedral, or may have a spherical or plate-like shape. It may have an irregular crystal form. In these particles, any ratio can be used for the crystal habit (100) plane and (111) plane. Further, a composite of these crystal forms may be used, and particles of various crystal forms may be mixed.

【００８８】種乳剤を用いる場合、又、種乳剤を用いな
い場合の何れにせよ、ハロゲン化銀核形成及び熟成の条
件としては、当業界で公知の方法を適用することができ
る。Regardless of whether a seed emulsion is used or no seed emulsion is used, the conditions for silver halide nucleation and ripening may be any of those known in the art.

【００８９】写真乳剤の製造には、当業界で公知のハロ
ゲン化銀溶剤を使用することができるが、できれば、ホ
スト平板粒子の形成時には、ハロゲン化銀溶剤の使用
は、核形成後の熟成を除いて避けたほうがよい。ハロゲ
ン化銀溶剤の例としては、（ａ）米国特許３，２７１，
１５７号、同３，５３１，２８９号、同３，５７４，６
２８号、特開昭５４−１０１９号、同５４−１５８９１
７号、及び特公昭５８−３０５７１号等に記載の有機チ
オエーテル類、（ｂ）特開昭５３−８２４０８号、同５
５−２９８２９号及び同５７−７７７３６号等に記載の
チオ尿素誘導体、（ｃ）特開昭５３−１４４３１９号等
に記載の酸素又は硫黄原子と窒素原子で挟まれたチオカ
ルボニル基を有するハロゲン化銀溶剤、（ｄ）特開昭５
４−１００７１７号等に記載のイミダゾール類、（ｅ）
亜硫酸塩、（ｆ）チオシアナート類、（ｇ）アンモニ
ア、（ｈ）特開昭５７−１９６２２８号等に記載のヒド
ロキシアルキルで置換したエチレンジアミン類、（ｉ）
特開昭５７−２０２５３１号等に記載の置換メルカプト
テトラゾール類、（ｊ）水溶性臭化物、（ｋ）特開昭５
８−５４３３３号等に記載のベンゾイミダゾール誘導体
などが挙げられる。For the preparation of a photographic emulsion, a silver halide solvent known in the art can be used. If possible, the use of a silver halide solvent during the formation of host tabular grains is effective for ripening after nucleation. It is better to avoid it. Examples of silver halide solvents include (a) US Pat.
157, 3,531,289, 3,574,6
No. 28, JP-A-54-1019 and JP-A-54-15891.
No. 7, and JP-B-58-30571; (b) JP-A-53-82408;
Thiourea derivatives described in JP-A-5-29829 and JP-A-57-77736, and (c) halogenation having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom described in JP-A-53-144319 and the like. Silver solvent, (d) JP-A-5
Imidazoles described in No. 4-100717, (e)
Sulfites, (f) thiocyanates, (g) ammonia, (h) hydroxyalkyl-substituted ethylenediamines described in JP-A-57-196228 and the like, (i)
Substituted mercaptotetrazoles described in JP-A-57-202531, etc .; (j) water-soluble bromide;
And a benzimidazole derivative described in JP-A-8-54333.

【００９０】本発明の写真乳剤の製造には、酸性法、中
性法、アンモニア法の何れの方法をも用いることができ
るが、酸性法あるいは中性法が好ましい。For the production of the photographic emulsion of the present invention, any of the acidic method, neutral method and ammonia method can be used, but the acidic method or neutral method is preferred.

【００９１】写真乳剤の製造においては、ハライドイオ
ンと銀イオンとを同時に混合しても、何れか一方が存在
する中に他方を混合してもよい。又、ハロゲン化銀結晶
の臨界成長速度を考慮し、ハライドイオンと銀イオンと
を混合釜内のｐＡｇ、ｐＨをコントロールして逐次又は
同時に添加することもできる。ハロゲン化銀形成の任意
の工程で、コンバージョン法を用いてハロゲン化銀粒子
のハロゲン組成を変化させてもよい。In the production of a photographic emulsion, halide ions and silver ions may be mixed simultaneously, or one of them may be mixed with the other. In consideration of the critical growth rate of silver halide crystals, halide ions and silver ions can be added sequentially or simultaneously while controlling the pAg and pH in the mixing vessel. In any step of silver halide formation, the halogen composition of the silver halide grains may be changed by using a conversion method.

【００９２】写真乳剤の製造においては、ハロゲン化銀
粒子を形成する過程及び／又は成長させる過程で、カド
ミウム塩、亜鉛塩、鉛塩、タリウム塩、イリジウム塩
（錯塩を含む）、ロジウム塩（錯塩を含む）、鉄その他
の第VIII族金属の塩（錯塩を含む）等から選ばれる少な
くとも１種を用いて金属イオンを添加し、ハロゲン化銀
粒子内部及び／又は粒子表面にこれらの金属を含有させ
ることができる。In the production of photographic emulsions, cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (including complex salts) and rhodium salts (complex salts) are formed and / or grown during the formation of silver halide grains. ), And metal ions are added using at least one selected from salts of iron and other Group VIII metals (including complex salts), and these metals are contained inside the silver halide grains and / or on the surface of the grains. Can be done.

【００９３】写真乳剤の製造においては、当業界で公知
の手法等を用いて還元増感を行うこともできる。還元増
感は、ハロゲン化銀粒子形成途中あるいは粒子形成後に
行ってもよい。In the production of a photographic emulsion, reduction sensitization can be carried out using a method known in the art. Reduction sensitization may be performed during or after silver halide grain formation.

【００９４】還元増感のより具体的な方法としては、当
業界において銀熟と呼ばれる、ハロゲン化銀粒子に銀イ
オンを供給するなどして低ｐＡｇで熟成・成長させる方
法、アルカリ性化合物等を用いてｐＨを高くして熟成・
成長させる方法、還元剤を添加する方法などから任意の
方法、又はこれらの組合せを用いることができる。As a more specific method of reduction sensitization, a method of ripening and growing at a low pAg by supplying silver ions to silver halide grains, which is called “silver ripening” in the art, an alkaline compound, etc. Aging by raising the pH
Any method such as a method of growing, a method of adding a reducing agent, or a combination thereof can be used.

【００９５】還元剤を用いる場合、例えば二酸化チオ尿
素やアスコルビン酸及びその誘導体、第一錫塩、ボラン
化合物、ヒドラジン誘導体、ホルムアミジンスルフィン
酸、シラン化合物、アミン及びポリアミン類及び亜硫酸
塩等を用いることができるが、好ましくは二酸化チオ尿
素やアスコルビン酸及びその誘導体、第一錫塩が用いら
れる。When a reducing agent is used, for example, thiourea dioxide, ascorbic acid and its derivatives, stannous salts, borane compounds, hydrazine derivatives, formamidinesulfinic acid, silane compounds, amines and polyamines, and sulfites are used. Preferably, thiourea dioxide, ascorbic acid and its derivatives, and stannous salts are used.

【００９６】写真乳剤の製造においては、当業界で公知
の酸化剤を用いることもできる。酸化剤としては、例え
ば過酸化水素（水）及びその付加物：Ｈ2Ｏ2、ＮａＢＯ
2−Ｈ2Ｏ2−３Ｈ2Ｏ、２ＮａＣＯ3−３Ｈ2Ｏ2、Ｎａ4Ｐ
2Ｏ7−２Ｈ2Ｏ2、２Ｎａ2ＳＯ4−Ｈ2Ｏ2−２Ｈ2Ｏ等、
ペルオキシ酸塩：Ｋ2Ｓ2Ｏ3、Ｋ2Ｃ2Ｏ3、Ｋ4Ｐ2Ｏ3、
Ｋ2［Ｔｉ（Ｏ）2Ｃ2Ｏ4］−３Ｈ2Ｏ、過酢酸、オゾ
ン、チオスルホン酸化合物等が挙げられる。In the production of a photographic emulsion, an oxidizing agent known in the art can be used. Examples of the oxidizing agent include hydrogen peroxide (water) and its adducts: H 2 O 2 , NaBO
2 -H 2 O 2 -3H 2 O , 2NaCO 3 -3H 2 O 2, Na 4 P
2 O 7 -2H 2 O 2, 2Na 2 SO 4 -H 2 O 2 -2H 2 O , etc.,
Peroxy acid salts: K 2 S 2 O 3 , K 2 C 2 O 3 , K 4 P 2 O 3 ,
K 2 [Ti (O) 2 C 2 O 4 ] -3H 2 O, peracetic acid, ozone, thiosulfonic acid compound and the like.

【００９７】本発明の写真乳剤の製造においては、上記
還元増感と酸化剤添加とを組み合わせて行うこともでき
る。In the production of the photographic emulsion of the present invention, the reduction sensitization and the addition of an oxidizing agent can be carried out in combination.

【００９８】写真乳剤の製造においては、ハロゲン化銀
粒子形成途中もしくは形成後において物理熟成の進行抑
制あるいは不要塩類の除去等の目的で、前述の方法によ
り脱塩を行うことが好ましい。In the production of a photographic emulsion, desalting is preferably carried out by the above-mentioned method for the purpose of suppressing the progress of physical ripening or removing unnecessary salts during or after the formation of silver halide grains.

【００９９】写真乳剤の製造においては、上記以外の条
件については、特開昭６１−６６４３号、同６１−１４
６３０号、同６１−１１２１４２号、同６２−１５７０
２４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、ＲＤの３６５巻３６５４４、３６７巻３６７３６、
３９１巻３９１２１等を参考にして適切な条件を選択す
ることができる。In the preparation of a photographic emulsion, conditions other than those described above are described in JP-A-61-6643 and JP-A-61-14.
No. 630, No. 61-112142, No. 62-1570
No. 24, No. 62-18556, No. 63-92942
Nos. 63-151618 and 63-163451
Nos. 63-220238 and 63-31244
No., RD 365, 36544, 367, 36736,
Appropriate conditions can be selected with reference to Vol.

【０１００】本発明のハロゲン化銀写真乳剤を用いてカ
ラー感光材料を構成する際には、ハロゲン化銀乳剤は、
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。In constructing a color photographic material using the silver halide photographic emulsion of the present invention, the silver halide emulsion is
Use those that have been subjected to physical ripening, chemical ripening and spectral sensitization.

【０１０１】このような工程で使用される添加剤は、Ｒ
Ｄ１７６４３，２３頁III項〜２４頁VI−Ｍ項、ＲＤ１
８７１６，６４８〜６４９頁及びＲＤ３０８１１９，９
９６頁III−Ａ項〜１０００頁VI−Ｍ項に記載されてい
る。The additive used in such a step is R
D17643, page 23, section III to page 24, section VI-M, RD1
8716, pages 648 to 649 and RD308119, 9
It is described in page 96, section III-A to page 1000, section VI-M.

【０１０２】本発明に使用できる公知の写真用添加剤
も、同じくＲＤ１７６４３，２５頁VIII−Ａ項〜２７頁
XIII項、ＲＤ１８７１６，６５０〜６５１頁、ＲＤ３０
８１１９，１００３頁VIII−Ａ項〜１０１２頁XXI−Ｅ
項に記載のものを用いることができる。Known photographic additives usable in the present invention are also described in RD17643, page 25, VIII-A to page 27.
Section XIII, RD18716, pages 650 to 651, RD30
8119, page 1003, paragraphs VIII-A to 1012, XXI-E
Those described in the section can be used.

【０１０３】カラー感光材料には種々のカプラーを使用
することができ、その具体例は、ＲＤ１７６４３，２５
頁VII−Ｃ〜Ｇ項、ＲＤ３０８１１９，１００１頁VII−
Ｃ〜Ｇ項に記載されている。Various couplers can be used in the color light-sensitive material. Specific examples thereof are RD17643, 25
Page VII-C to G, RD308119, page 1001 VII-
It is described in sections C to G.

【０１０４】本発明に使用する添加剤は、ＲＤ３０８１
１９，１００７頁XIV項に記載されている分散法などに
より添加することができる。The additive used in the present invention is RD3081
19, page 1007, section XIV.

【０１０５】本発明においては、前述ＲＤ１７６４３，
２８頁XVII項、ＲＤ１８７１６，６４７〜８頁及びＲＤ
３０８１１９，１００９頁XVII項に記載される支持体を
使用することができる。In the present invention, the aforementioned RD17643,
Page 28, section XVII, RD 18716, pages 647-8, and RD
The support described in section 308119, page 1009, XVII can be used.

【０１０６】感光材料には、前述ＲＤ３０８１１９，１
００２頁VII−Ｋ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。The photosensitive materials include the aforementioned RD308119,1
An auxiliary layer such as a filter layer or an intermediate layer described in section VII-K on page 002 can be provided.

【０１０７】感光材料は、前述ＲＤ３０８１１９，VII
−Ｋ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。The photosensitive material is RD308119, VII
Various layer configurations such as a normal layer, a reverse layer, and a unit configuration described in the section -K can be adopted.

【０１０８】本発明のハロゲン化銀写真乳剤は、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。The silver halide photographic emulsion of the present invention can be used for various color light-sensitive materials typified by color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films, and color reversal papers. Can be preferably applied.

【０１０９】本発明に係る感光材料は、前述のＲＤ１７
６４３，２８〜２９頁XIX項、ＲＤ１８７１６，６５１
頁及びＲＤ３０８１１９，１０１０〜１０１１頁XIX項
に記載される通常の方法によって現像処理することがで
きる。The light-sensitive material according to the present invention uses the above-mentioned RD17
643, pages 28 to 29, section XIX, RD18716, 651
And RD 308119, pages 1010 to 1011, section XIX.

【０１１０】[0110]

【実施例】以下、実施例を挙げて具体的に説明するが、
本発明はこれらの実施例に限定されない。The present invention will be specifically described below with reference to examples.
The present invention is not limited to these examples.

【０１１１】実施例１ 〈球型種乳剤Ｔ−１の調製〉以下に示す方法によって、
単分散性の球型種乳剤Ｔ−１を調製した。Example 1 <Preparation of spherical seed emulsion T-1>
A monodisperse spherical seed emulsion T-1 was prepared.

【０１１２】 （Ａ−１液） オセインゼラチン ８０ｇ 臭化カリウム ４７．４ｇ 界面活性剤（ＥＯ−１）の１０％メタノール溶液 ２０ｍｌ 水で ８．０リットル （Ｂ−１液） 硝酸銀 １２００ｇ 水で １．６リットル （Ｃ−１液） オセインゼラチン ３２．２ｇ 臭化カリウム ８４０ｇ 水で １．６リットル （Ｄ−１液） アンモニア水（２８％） ４７０ｍｌ ＥＯ−１：ＨＯ（ＣＨ2ＣＨ2Ｏ）m（ＣＨ〔ＣＨ3〕ＣＨ2）19.8（ＣＨ2ＣＨ2Ｏ ）nＨ（ｍ＋ｎ＝９．７７） ４０℃で激しく攪拌したＡ−１液に、Ｂ−１液とＣ−１
液とをダブルジェット法により１１分で添加し、ハロゲ
ン化銀核の生成を行った。この間ｐＢｒは１．６に保っ
た。(A-1 solution) Ossein gelatin 80 g Potassium bromide 47.4 g 10% methanol solution of surfactant (EO-1) 20 ml Water 8.0 liter (B-1 solution) Silver nitrate 1200 g Water 1 1.6 liters (C-1 solution) Ossein gelatin 32.2 g Potassium bromide 840 g 1.6 liters with water (D-1 solution) Ammonia water (28%) 470 ml EO-1: HO (CH 2 CH 2 O) m (CH [CH 3 ] CH 2 ) 19.8 (CH 2 CH 2 O) n H (m + n = 9.77) Solution A-1 which was vigorously stirred at 40 ° C. was mixed with solution B-1 and solution C-1.
The solution was added by a double jet method in 11 minutes to generate silver halide nuclei. During this time, pBr was kept at 1.6.

【０１１３】その後、１２分かけて温度を３０℃に下
げ、更に１８分間熟成を行った。その後、更にＤ−１液
を１分間で添加し、引き続き５分間熟成を行った。その
後、ｐＨを６．０に調製し、直ちに脱塩を行った。Thereafter, the temperature was lowered to 30 ° C. over 12 minutes, and ripening was further performed for 18 minutes. Thereafter, solution D-1 was further added for 1 minute, and subsequently ripening was performed for 5 minutes. Thereafter, the pH was adjusted to 6.0, and desalting was immediately performed.

【０１１４】この種乳剤を電子顕微鏡にて観察したとこ
ろ、互いに平行な２枚の双晶面を持つ平均粒径（投影面
積円換算粒径）０．４３μｍ、粒径分布２０％の単分散
球型乳剤であった。When this seed emulsion was observed with an electron microscope, monodisperse spheres having an average grain size (grain size in terms of projected area circle) of 0.43 μm having two twin planes parallel to each other and a grain size distribution of 20% were obtained. Type emulsion.

【０１１５】〈比較乳剤Ｅｍ−１の調製〉以下に示す溶
液を用い、比較乳剤（Ｅｍ−１）を調製した。<Preparation of Comparative Emulsion Em-1> A comparative emulsion (Em-1) was prepared using the following solution.

【０１１６】 （Ａ−２液） オセインゼラチン ２６８．２ｇ 界面活性剤（ＥＯ−１）の１０％メタノール溶液 １．５ｍｌ 種乳剤（Ｔ−１） ０．３４１モル相当 ２８重量％アンモニア水溶液 ５２８ｍｌ ５６重量％酢酸水溶液 ７９５ｍｌ 水で ５９３０ｍｌ （Ｂ−２液） ３．５Ｎアンモニア性硝酸銀水溶液（硝酸アンモニウムでｐＨを ９．０に調整） ２６７５ｍｌ （Ｃ−２液） ４．０重量％のゼラチンを含む３．５Ｎ臭化カリウム水溶液２６７５ｍｌ （Ｄ−２液） ３．０重量％のゼラチンと沃化銀微粒子（平均粒径０．０５μｍ） から成る微粒子乳剤 ０．８４４モル 調製法を以下に示す。(A-2 solution) Ossein gelatin 268.2 g 10% methanol solution of surfactant (EO-1) 1.5 ml Seed emulsion (T-1) 0.341 mol equivalent 28% by weight aqueous ammonia solution 528 ml 56 2.95% by weight aqueous acetic acid solution 795 ml 5930 ml with water (solution B-2) 3.5 N aqueous ammoniacal silver nitrate solution (pH adjusted to 9.0 with ammonium nitrate) 2675 ml (solution C-2) containing 4.0% by weight gelatin 2675 ml of a 5N aqueous potassium bromide solution (D-2 solution) 0.844 mol of a fine grain emulsion composed of 3.0% by weight of gelatin and silver iodide fine grains (average particle size: 0.05 μm) is described below.

【０１１７】０．０６モルの沃化カリウムを含む６．０
重量％のゼラチン溶液５０００ｍｌに、７．０６モルの
硝酸銀と７．０６モルの沃化カリウムを含む水溶液、各
々２０００ｍｌを１０分間かけて等速添加した。微粒子
形成中のｐＨは硝酸を用いて２．０に、温度は４０℃に
制御した。添加終了後に、炭酸ナトリウム水溶液を用い
てｐＨを６．０に調整した。仕上がり重量は１２．５３
ｋｇであった。6.0 containing 0.06 mol of potassium iodide
An aqueous solution containing 7.06 mol of silver nitrate and 7.06 mol of potassium iodide, 2000 ml each, was added to 5000 ml of a weight% gelatin solution at a constant speed over 10 minutes. During the fine particle formation, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the addition was completed, the pH was adjusted to 6.0 using an aqueous solution of sodium carbonate. 12.53 finished weight
kg.

【０１１８】 （Ｅ−２液） １．７５Ｎ臭化カリウム水溶液 必要量 （Ｆ−２液） ５６重量％酢酸水溶液 必要量 反応容器内で７０℃に保ったＡ−２液に、Ｂ−２液、Ｃ
−２液、Ｄ−２液を同時混合法によって添加した。(E-2 solution) 1.75N Potassium bromide aqueous solution required amount (F-2 solution) 56% by weight acetic acid aqueous solution required amount A-2 solution kept at 70 ° C. in a reaction vessel, B-2 solution , C
Solution 2 and Solution D-2 were added by the simultaneous mixing method.

【０１１９】ここで、Ｂ−２液、Ｃ−２液、Ｄ−２液の
添加速度は、臨界成長速度を考慮し、添加時間に対して
関数様に変化させ、成長している種粒子以外の小粒子の
発生や、成長粒子間のオストワルド熟成による粒径分布
の劣化が起こらないようにした。Ｄ−２液の供給は、ア
ンモニア性硝酸銀とのモル比を表１に示すように粒径
（添加時間）に対して変化させ、多重構造を有するコア
／シェル型ハロゲン化銀粒子を作製した。Here, the addition rates of the liquids B-2, C-2, and D-2 are changed in a function-wise manner with respect to the addition time in consideration of the critical growth rate. The generation of small particles and the deterioration of the particle size distribution due to Ostwald ripening between growing particles were prevented. The supply of Solution D-2 was carried out by changing the molar ratio with respect to the ammoniacal silver nitrate with respect to the particle size (addition time) as shown in Table 1 to produce core / shell type silver halide grains having a multiple structure.

【０１２０】又、Ｅ−２液、Ｆ−２液を用いて、結晶成
長中のｐＨ、ｐＡｇを表１に示すように制御した。尚、
ｐＨ、ｐＡｇの測定は、常法に従い、硫化銀電極、ガラ
ス電極を用いて行った。The pH and pAg during the crystal growth were controlled as shown in Table 1 using the E-2 solution and the F-2 solution. still,
The pH and pAg were measured using a silver sulfide electrode and a glass electrode according to a conventional method.

【０１２１】粒子形成後に、特開平５−７２６５８号に
記載の方法に従い脱塩処理を行い、その後ゼラチンを加
えて分散し、４０℃においてｐＡｇ８．０６、ｐＨ５．
８の乳剤を得た。After the particles are formed, desalting is performed according to the method described in JP-A-5-72658, and then gelatin is added and dispersed, and pAg 8.06 at 40 ° C., pH 5.0.
8 were obtained.

【０１２２】この乳剤中のハロゲン化銀粒子を電子顕微
鏡にて観察したところ、平均粒径１．３８μｍ、粒径分
布１３％であり、ハロゲン化銀粒子表面が殆ど（１１
１）面で構成された八面体双晶ハロゲン化銀粒子であ
り、粒子個数の９７％を占めていた。When the silver halide grains in this emulsion were observed with an electron microscope, the average grain size was 1.38 μm, the grain size distribution was 13%, and the surface of the silver halide grains was almost (11)
1) Octahedral twin silver halide grains composed of planes, occupying 97% of the number of grains.

【０１２３】[0123]

【表１】 [Table 1]

【０１２４】〈比較乳剤Ｅｍ−２の調製〉比較乳剤Ｅｍ
−１の調製において、脱塩処理の代わりに下記の限外濾
過Ａの操作を施した。その後、５０℃にて、ｐＡｇを
８．２に調製し、下記Ｊ−２液のハロゲン化銀量で０．
１５モル相当量を１０分で添加し、２０分間熟成した
後、限外濾過Ａの操作を施し、４０℃においてｐＡｇ
８．０６、ｐＨ５．８に調整すること以外は同様にして
比較乳剤（Ｅｍ−２）を調製した。<Preparation of Comparative Emulsion Em-2> Comparative Emulsion Em
In the preparation of -1, the following operation of ultrafiltration A was performed instead of the desalting treatment. Thereafter, the pAg was adjusted to 8.2 at 50 ° C., and the pAg was adjusted to 0.2 in terms of the amount of silver halide in the following liquid J-2.
After adding 15 mol equivalent in 10 minutes and aging for 20 minutes, the operation of ultrafiltration A was performed, and pAg
A comparative emulsion (Em-2) was prepared in the same manner except that the pH was adjusted to 8.06 and pH 5.8.

【０１２５】（限外濾過Ａ）ハロゲン化銀乳剤を限外濾
過モジュール（旭化成工業社製：分画分子量１３，００
０のポリアクリロニトリル膜を使用したタイプＡリット
ルＰ−１０１０）に通して循環させながら、加水、濃縮
を繰り返し、塩濃度を１／８０にした。(Ultrafiltration A) A silver halide emulsion was treated with an ultrafiltration module (Asahi Kasei Kogyo Co., Ltd .; molecular weight cut off: 13,000).
Water and concentration were repeated while circulating through a type A liter P-1010 using a polyacrylonitrile membrane of No. 0 to reduce the salt concentration to 1/80.

【０１２６】（Ｊ−２液）３．０重量％のゼラチンと臭
化銀微粒子（平均粒径０．０５μｍ）から成る微粒子乳
剤 調製法を以下に示す。(J-2 solution) A method for preparing a fine grain emulsion comprising 3.0% by weight of gelatin and fine grains of silver bromide (average particle size: 0.05 μm) is described below.

【０１２７】０．０６モルの臭化カリウムを含む６．０
重量％のゼラチン溶液５０００ｍｌに、７．０６モルの
硝酸銀を含む水溶液２０００ｍリットルと７．０６モル
の臭化カリウムを含む水溶液２０００ｍｌとを１０分間
かけて等速添加した。微粒子形成中のｐＨは硝酸を用い
て３．０に、温度は３０℃に制御した。添加終了後に、
炭酸ナトリウム水溶液を用いてｐＨを６．０に調整し、
下記の限外濾過Ｂを施し、２Ｎ臭化カリウム水溶液で４
０℃にてｐＡｇ８．０に調整した。6.0 containing 0.06 mol of potassium bromide
2000 ml of an aqueous solution containing 7.06 mol of silver nitrate and 2000 ml of an aqueous solution containing 7.06 mol of potassium bromide were added at a constant rate to 5000 ml of a weight% gelatin solution over 10 minutes. During the formation of fine particles, the pH was controlled at 3.0 using nitric acid, and the temperature was controlled at 30 ° C. After the addition,
Adjust the pH to 6.0 using aqueous sodium carbonate,
The following ultrafiltration B was performed, and 4N with 2N aqueous potassium bromide solution.
The pAg was adjusted to 8.0 at 0 ° C.

【０１２８】（限外濾過Ｂ）ハロゲン化銀乳剤を限外濾
過モジュール（前出：タイプＡリットルＰ−１０１０）
に通して循環させながら、加水、濃縮を繰り返し、塩濃
度を１／５０にした。(Ultrafiltration B) A silver halide emulsion was subjected to an ultrafiltration module (see above: Type A 1 liter P-1010).
Water and concentration were repeated while circulating through the mixture to reduce the salt concentration to 1/50.

【０１２９】〈比較乳剤Ｅｍ−３の調製〉比較乳剤Ｅｍ
−１の調製において、脱塩処理の代わりに前記の限外濾
過Ａの操作を施した。その後、６０℃にて２Ｎ臭化カリ
ウム水溶液でｐＡｇを８．８に調整し、下記Ｋ−２液の
ハロゲン化銀量で１．１モル相当量を１０分で添加し、
２０分間熟成した後、限外濾過Ａの操作を施し、４０℃
においてｐＡｇ８．０６、ｐＨ５．８に調整する以外は
同様にして比較乳剤（Ｅｍ−３）を調製した。<Preparation of Comparative Emulsion Em-3> Comparative Emulsion Em
In the preparation of -1, ultrafiltration A was performed in place of the desalting treatment. Then, the pAg was adjusted to 8.8 with a 2N aqueous potassium bromide solution at 60 ° C., and 1.1 mol equivalent of the silver halide in the following K-2 solution was added in 10 minutes.
After aging for 20 minutes, the operation of ultrafiltration A was performed.
In Comparative Example 2, a comparative emulsion (Em-3) was prepared in the same manner except that pAg was adjusted to 8.06 and pH to 5.8.

【０１３０】（Ｋ−２液）３．０重量％のゼラチンと塩
化銀微粒子（平均粒径０．０８μｍ）から成る微粒子乳
剤 調製法を以下に示す。(K-2 solution) A method for preparing a fine grain emulsion comprising 3.0% by weight of gelatin and fine silver chloride grains (average grain size: 0.08 μm) is described below.

【０１３１】０．０６モルの塩化ナトリウムを含む６．
０重量％のゼラチン溶液５０００ｍｌに、７．０６モル
の硝酸銀を含む水溶液２０００ｍｌと７．０６モルの塩
化ナトリウムを含む水溶液２０００ｍｌとを１０分間か
けて等速添加した。微粒子形成中のｐＨは硝酸を用いて
３．０に、温度は３０℃に制御した。添加終了後、炭酸
ナトリウム水溶液を用いてｐＨを６．０に調整し、上記
の限外濾過Ｂを施し、２Ｎ塩化ナトリウム水溶液で４０
℃にてｐＡｇ７．５に調整した。5. containing 0.06 mol of sodium chloride
To 5000 ml of a 0% by weight gelatin solution, 2,000 ml of an aqueous solution containing 7.06 mol of silver nitrate and 2,000 ml of an aqueous solution containing 7.06 mol of sodium chloride were added at a constant rate over 10 minutes. During the formation of fine particles, the pH was controlled at 3.0 using nitric acid, and the temperature was controlled at 30 ° C. After the addition was completed, the pH was adjusted to 6.0 using an aqueous sodium carbonate solution, subjected to the above ultrafiltration B, and added to a 40% aqueous sodium chloride solution.
It adjusted to pAg7.5 at ° C.

【０１３２】〈本発明乳剤Ｅｍ−４の調製〉比較乳剤Ｅ
ｍ−１の調製において、脱塩処理の代わりに前記の限外
濾過Ａの操作を施した。その後、６０℃にて、２Ｎ臭化
カリウム水溶液でｐＡｇを８．８に調整し、上記Ｋ−２
液のハロゲン化銀量で１．１モル相当量を１０分で添加
し、２０分間熟成した後、５０℃に降温し、ｐＡｇを
８．２に調製して、上記Ｊ−２液のハロゲン化銀量で
０．１５モル相当量を１０分で添加し、２０分間熟成し
た後、限外濾過Ａの操作を施し、４０℃においてｐＡｇ
８．０６、ｐＨ５．８に調整する以外は同様にして本発
明乳剤（Ｅｍ−４）を調製した。<Preparation of Emulsion Em-4 of the Present Invention> Comparative Emulsion E
In the preparation of m-1, the above operation of ultrafiltration A was performed instead of the desalting treatment. Thereafter, the pAg was adjusted to 8.8 with a 2N aqueous potassium bromide solution at 60 ° C.
The solution was added in an amount of 1.1 mol equivalent to the amount of silver halide in 10 minutes, ripened for 20 minutes, cooled to 50 ° C., adjusted pAg to 8.2, and halogenated the J-2 solution. An amount equivalent to 0.15 mol of silver was added in 10 minutes, and after aging for 20 minutes, the operation of ultrafiltration A was performed.
An emulsion of the present invention (Em-4) was prepared in the same manner except that the pH was adjusted to 8.06 and pH 5.8.

【０１３３】〈本発明乳剤Ｅｍ−５の調製〉比較乳剤Ｅ
ｍ−１の調製において、脱塩処理の代わりに前記の限外
濾過Ａの操作を施した。その後、６０℃にて、２Ｎ臭化
カリウム水溶液でｐＡｇを９．０に調整し、前記Ｋ−２
液のハロゲン化銀量で１．８モル相当量を１０分で添加
し、２０分間熟成した後、５０℃に降温し、ｐＡｇを
８．２に調製し、前記Ｊ−２液のハロゲン化銀量で０．
３モル相当量を１０分で添加し、２０分間熟成した後、
限外濾過Ａの操作を施し、４０℃においてｐＡｇ８．０
６、ｐＨ５．８に調整すること以外は同様にして本発明
乳剤（Ｅｍ−５）を調製した。<Preparation of Emulsion Em-5 of the Present Invention> Comparative Emulsion E
In the preparation of m-1, the above operation of ultrafiltration A was performed instead of the desalting treatment. Thereafter, the pAg was adjusted to 9.0 with a 2N aqueous potassium bromide solution at 60 ° C., and the K-2 was adjusted.
A solution equivalent to 1.8 mol of silver halide in the solution was added in 10 minutes, and after aging for 20 minutes, the temperature was lowered to 50 ° C. to adjust the pAg to 8.2, and the silver halide in the solution J-2 was used. 0 in quantity.
After adding 3 mol equivalent in 10 minutes and aging for 20 minutes,
The operation of ultrafiltration A was performed and pAg 8.0 at 40 ° C.
6. An emulsion of the present invention (Em-5) was prepared in the same manner except that the pH was adjusted to 5.8.

【０１３４】上記乳剤Ｅｍ−１〜Ｅｍ−５に含まれるハ
ロゲン化銀粒子のハロゲン化銀組成を前述の方法（Ｘ線
回折）で確認したところ、Ｅｍ−３〜Ｅｍ−５に含まれ
るハロゲン化銀粒子においては、塩化銀を含有している
ことが確認された。The silver halide composition of the silver halide grains contained in the emulsions Em-1 to Em-5 was confirmed by the method described above (X-ray diffraction), and the silver halide grains contained in the emulsions Em-3 to Em-5 were confirmed. It was confirmed that the silver particles contained silver chloride.

【０１３５】乳剤Ｅｍ−１〜Ｅｍ−５を、それぞれ下記
試料処方において、第１０層で沃臭化銀ｇと表示して用
いた。尚、これらの乳剤Ｅｍ−１〜Ｅｍ−５は、下記試
料処方に記載の方法で最適に色増感、化学増感を施して
から用いた。Emulsions Em-1 to Em-5 were each used in the following sample formulation, with the designation being silver iodobromide g in the tenth layer. These emulsions Em-1 to Em-5 were used after being optimally subjected to color sensitization and chemical sensitization by the method described in the following sample formulation.

【０１３６】〈カラー感光材料の作製〉下引層を施した
トリアセチルセルロースフィルム支持体上に、下記に示
す組成の各層を順次支持体側から形成して多層カラー感
光材料試料１０１〜１０５を作製した。各素材の添加量
は１ｍ2当たりのグラム数で示す。ただし、ハロゲン化
銀とコロイド銀は銀の量に換算し、増感色素は同一乳剤
層中の銀１モル当たりのモル数で示した。<Preparation of color photographic material> On a triacetyl cellulose film support provided with an undercoat layer, layers having the following compositions were sequentially formed from the support side to prepare multilayer color photographic material samples 101 to 105. . The amount of each material added is shown in grams per 1 m 2. However, silver halide and colloidal silver were converted to the amount of silver, and the sensitizing dye was indicated by the number of moles per mole of silver in the same emulsion layer.

【０１３７】 第１層（ハレーション防止層） 黒色コロイド銀 ０．１６ 紫外線吸収剤 ＵＶ−１ ０．３ カラードマゼンタカプラー ＣＭ−１ ０．１２３ カラードシアンカプラー ＣＣ−１ ０．０４４ 高沸点溶媒 ＯＩＬ−１ ０．１６７ ゼラチン １．３３ 第２層（中間層） 汚染防止剤 ＡＳ−１ ０．１６ 高沸点溶媒 ＯＩＬ−１ ０．２０ ゼラチン ０．６９ 第３層（低感度赤感色性層） 沃臭化銀ａ ０．１２ 沃臭化銀ｂ ０．２９ 増感色素 ＳＤ−１ ２．３７×１０-5 増感色素 ＳＤ−２ １．２×１０-4 増感色素 ＳＤ−３ ２．４×１０-4 増感色素 ＳＤ−４ ２．４×１０-6 シアンカプラー Ｃ−１ ０．３２ カラードシアンカプラー ＣＣ−１ ０．０３８ 高沸点溶媒 ＯＩＬ−２ ０．２８ 汚染防止剤 ＡＳ−２ ０．００２ ゼラチン ０．７３ 第４層（中感度赤感色性層） 沃臭化銀ｃ ０．１０ 沃臭化銀ｄ ０．８６ 増感色素 ＳＤ−１ ４．５×１０-5 増感色素 ＳＤ−２ ２．３×１０-4 増感色素 ＳＤ−３ ４．５×１０-4 シアンカプラー Ｃ−２ ０．５２ カラードシアンカプラー ＣＣ−１ ０．０６ ＤＩＲ化合物 ＤＩ−１ ０．０４７ 高沸点溶媒 ＯＩＬ−２ ０．４６ 汚染防止剤 ＡＳ−２ ０．００４ ゼラチン １．３０ 第５層（高感度赤感色性層） 沃臭化銀ｃ ０．１３ 沃臭化銀ｄ １．１８ 増感色素 ＳＤ−１ ３．０×１０-5 増感色素 ＳＤ−２ １．５×１０-4 増感色素 ＳＤ−３ ３．０×１０−４ シアンカプラー Ｃ−２ ０．０４７ シアンカプラー Ｃ−３ ０．０９ カラードシアンカプラー ＣＣ−１ ０．０３６ ＤＩＲ化合物 ＤＩ−１ ０．０２４ 高沸点溶媒 ＯＩＬ−２ ０．２７ 汚染防止剤 ＡＳ−２ ０．００６ ゼラチン １．２８ 第６層（中間層） 高沸点溶媒 ＯＩＬ−１ ０．２９ 汚染防止剤 ＡＳ−１ ０．２３ ゼラチン １．００ 第７層（低感度緑感色性層） 沃臭化銀ａ ０．１９ 沃臭化銀ｂ ０．０６２ 増感色素 ＳＤ−４ ３．６×１０−４ 増感色素 ＳＤ−５ ３．６×１０-4 マゼンタカプラー Ｍ−１ ０．１８ カラードマゼンタカプラー ＣＭ−１ ０．０３３ 高沸点溶媒 ＯＩＬ−１ ０．２２ 汚染防止剤 ＡＳ−２ ０．００２ 汚染防止剤 ＡＳ−３ ０．０５ ゼラチン ０．６１ 第８層（中間層） 高沸点溶媒 ＯＩＬ−１ ０．２６ 汚染防止剤 ＡＳ−１ ０．０５４ ゼラチン ０．８０ 第９層（中感度緑感色性層） 沃臭化銀ｅ ０．５４ 沃臭化銀ｆ ０．５４ 増感色素 ＳＤ−６ ３．７×１０-4 増感色素 ＳＤ−７ ７．４×１０-5 増感色素 ＳＤ−８ ５．０×１０-5 マゼンタカプラー Ｍ−１ ０．１７ マゼンタカプラー Ｍ−２ ０．３３ カラードマゼンタカプラー ＣＭ−１ ０．０２４ カラードマゼンタカプラー ＣＭ−２ ０．０２９ ＤＩＲ化合物 ＤＩ−２ ０．０２４ ＤＩＲ化合物 ＤＩ−３ ０．００５ 高沸点溶媒 ＯＩＬ−１ ０．７３ 汚染防止剤 ＡＳ−２ ０．００３ 汚染防止剤 ＡＳ−３ ０．０３５ ゼラチン １．８０ 第１０層（高感度緑感色性層） 沃臭化銀ｇ １．１９ 増感色素 ＳＤ−６ ４．０×１０-4 増感色素 ＳＤ−７ ８．０×１０-5 増感色素 ＳＤ−８ ５．０×１０-5 マゼンタカプラー Ｍ−１ ０．０６５ カラードマゼンタカプラー ＣＭ−１ ０．０２２ カラードマゼンタカプラー ＣＭ−２ ０．０２６ ＤＩＲ化合物 ＤＩ−２ ０．００３ ＤＩＲ化合物 ＤＩ−３ ０．００３ 高沸点溶媒 ＯＩＬ−１ ０．１９ 高沸点溶媒 ＯＩＬ−２ ０．４３ 汚染防止剤 ＡＳ−２ ０．０１４ 汚染防止剤 ＡＳ−３ ０．０１７ ゼラチン １．２３ 第１１層（イエローフィルター層） 黄色コロイド銀 ０．０５ 高沸点溶媒 ＯＩＬ−１ ０．１８ 汚染防止剤 ＡＳ−１ ０．１６ ゼラチン １．００ 第１２層（低感度青感色性層） 沃臭化銀ａ ０．０８ 沃臭化銀ｂ ０．２２ 増感色素 ＳＤ−９ ６．５×１０-4 増感色素 ＳＤ−１０ ２．５×１０-4 イエローカプラー Ｙ−１ ０．７７ ＤＩＲ化合物 ＤＩ−４ ０．０１７ 高沸点溶媒 ＯＩＬ−１ ０．３１ 汚染防止剤 ＡＳ−２ ０．００２ ゼラチン １．２９ 第１３層（高感度青感色性層） 沃臭化銀ｈ ０．４１ 沃臭化銀ｉ ０．６１ 増感色素 ＳＤ−９ ４．４×１０-4 増感色素 ＳＤ−１０ １．５×１０-4 イエローカプラー Ｙ−１ ０．２３ 高沸点溶媒 ＯＩＬ−１ ０．１０ 汚染防止剤 ＡＳ−２ ０．００４ ゼラチン １．２０ 第１４層（第１保護層） 沃臭化銀ｊ ０．３０ 紫外線吸収剤 ＵＶ−１ ０．０５５ 紫外線吸収剤 ＵＶ−２ ０．１１０ 高沸点溶媒 ＯＩＬ−２ ０．３０ ゼラチン １．３２ 第１５層（第２保護層） ポリマー ＰＭ−１ ０．１５ ポリマー ＰＭ−２ ０．０４ 滑り剤 ＷＡＸ−１ ０．０２ 染料 Ｄ−１ ０．００１ ゼラチン ０．５５ 上記沃臭化銀の特徴を以下に表示する（平均粒径とは、
同体積の立方体の一辺長を指す）。First Layer (Antihalation Layer) Black Colloidal Silver 0.16 UV Absorber UV-1 0.3 Colored Magenta Coupler CM-1 0.123 Colored Cyan Coupler CC-1 0.044 High Boiling Solvent OIL-1 0.167 Gelatin 1.33 Second layer (intermediate layer) Stain inhibitor AS-1 0.16 High boiling point solvent OIL-1 0.20 Gelatin 0.69 Third layer (Low sensitivity red-sensitive layer) Silver halide a 0.12 silver iodobromide b 0.29 sensitizing dye SD-1 2.37 × 10 -5 sensitizing dye SD-2 1.2 × 10 -4 sensitizing dye SD-3 2.4 × 10-4 sensitizing dye SD-4 2.4 × 10-6 Cyan coupler C-1 0.32 Colored cyan coupler CC-1 0.038 High boiling point solvent OIL-2 0.28 Stain inhibitor AS-2 0.0. 002 Gelatin 0.73 4th layer Medium-speed red-sensitive layer) Silver iodobromide c 0.10 Silver iodobromide d 0.86 Sensitizing dye SD-1 4.5 × 10 -5 Sensitizing dye SD-2 2.3 × 10 -4 Sensitizing dye SD-3 4.5 × 10 -4 Cyan coupler C-2 0.52 Colored cyan coupler CC-1 0.06 DIR compound DI-1 0.047 High boiling point solvent OIL-2 0.46 Antifouling agent AS-2 0.004 Gelatin 1.30 Fifth layer (high-sensitivity red-sensitive layer) Silver iodobromide c 0.13 Silver iodobromide d 1.18 Sensitizing dye SD-1 3.0 × 10 − 5 Sensitizing dye SD-2 1.5 × 10 -4 Sensitizing dye SD-3 3.0 × 10 -4 Cyan coupler C-2 0.047 Cyan coupler C-3 0.09 Colored cyan coupler CC-10 0.036 DIR compound DI-1 0.024 High boiling point solvent OIL-2 0.27 Stain inhibitor S-2 0.006 Gelatin 1.28 6th layer (intermediate layer) High boiling point solvent OIL-1 0.29 Stain inhibitor AS-1 0.23 Gelatin 1.00 7th layer (Low sensitivity green color sensitive layer) ) Silver iodobromide a 0.19 Silver iodobromide b 0.062 Sensitizing dye SD-4 3.6 × 10 -4 Sensitizing dye SD-5 3.6 × 10 -4 Magenta coupler M-1 18 Colored magenta coupler CM-1 0.033 High boiling solvent OIL-1 0.22 Stain inhibitor AS-2 0.002 Stain inhibitor AS-3 0.05 Gelatin 0.61 Eighth layer (intermediate layer) High boiling point Solvent OIL-1 0.26 Antifouling agent AS-1 0.054 Gelatin 0.80 Ninth layer (medium-speed green-sensitive layer) Silver iodobromide e 0.54 Silver iodobromide f 0.54 Sensitization dyes SD-6 3.7 × 10 sensitized -4 dye SD-7 7.4 × 10 -5 sensitization Containing SD-8 5.0 × 10 -5 Magenta coupler M-1 0.17 Magenta Coupler M-2 0.33 Colored magenta coupler CM-1 0.024 Colored magenta coupler CM-2 0.029 DIR compound DI-2 0.024 DIR compound DI-3 0.005 High boiling point solvent OIL-1 0.73 Stain inhibitor AS-2 0.003 Stain inhibitor AS-3 0.035 Gelatin 1.80 10th layer (high sensitivity green feeling) Color layer) Silver iodobromide g 1.19 Sensitizing dye SD-6 4.0 × 10 -4 Sensitizing dye SD-7 8.0 × 10 -5 Sensitizing dye SD-8 5.0 × 10 − 5 magenta coupler M-1 0.065 colored magenta coupler CM-1 0.022 colored magenta coupler CM-2 0.026 DIR compound DI-2 0.003 DIR compound DI-3 0 003 High boiling solvent OIL-1 0.19 High boiling solvent OIL-2 0.43 Stain inhibitor AS-2 0.014 Stain inhibitor AS-3 0.017 Gelatin 1.23 11th layer (yellow filter layer) Yellow Colloidal silver 0.05 High boiling point solvent OIL-1 0.18 Stain inhibitor AS-1 0.16 Gelatin 1.00 12th layer (low-sensitivity blue-sensitive layer) Silver iodobromide a 0.08 Iodobromide Silver b 0.22 sensitizing dye SD-9 6.5 × 10 -4 sensitizing dye SD-10 2.5 × 10 -4 yellow coupler Y-1 0.77 DIR compound DI-4 0.017 high boiling point solvent OIL-1 0.31 Antifouling agent AS-2 0.002 Gelatin 1.29 13th layer (highly sensitive blue-sensitive layer) Silver iodobromide h 0.41 Silver iodobromide i 0.61 Sensitizing dye SD-9 4.4 × 10 -4 sensitizing dye SD-10 .5 × 10 -4 Yellow coupler Y-1 0.23 High-boiling solvent OIL-1 0.10 antifouling agent AS-2 0.004 Gelatin 1.20 14th layer (first protective layer) Silver iodobromide j 0.30 UV absorber UV-1 0.055 UV absorber UV-2 0.110 High boiling point solvent OIL-2 0.30 Gelatin 1.32 15th layer (second protective layer) Polymer PM-1 0.15 Polymer PM-2 0.04 Slip agent WAX-1 0.02 Dye D-1 0.001 Gelatin 0.55 The characteristics of the above silver iodobromide are shown below (the average particle size is:
It refers to the length of one side of a cube of the same volume).

【０１３８】 乳剤Ｎｏ． 平均粒径(μｍ) 平均ＡｇＩ量(モル％) 直径(円相当)／厚み比 沃臭化銀ａ ０．３０ ２．０ １．０ 沃臭化銀ｂ ０．４０ ８．０ １．４ 沃臭化銀ｃ ０．６０ ７．０ ３．１ 沃臭化銀ｄ ０．７４ ７．０ ５．０ 沃臭化銀ｅ ０．６０ ７．０ ４，１ 沃臭化銀ｆ ０．６５ ８．７ ６．５ 沃臭化銀ｈ ０．６５ ８．０ １．４ 沃臭化銀ｉ １．００ ８．０ ２．０ 沃臭化銀ｊ ０．０５ ２．０ １．０ 尚、本発明の好ましいハロゲン化銀粒子の形成例とし
て、沃臭化銀ｄ，ｆの製造例を以下に示す。又、沃臭化
銀ｊについては、特開平１−１８３４１７号、同１−１
８３６４４号、同１−１８３６４５号、同２−１６６４
４２号に関する記載を参考に調製した。Emulsion No. Average grain size (μm) Average AgI amount (mol%) Diameter (equivalent to circle) / thickness ratio Silver iodobromide a 0.30 2.0 1.0 Silver iodobromide b 0.40 8.0 1.4 Iodine Silver bromide c 0.60 7.0 3.1 Silver iodobromide d 0.74 7.0 5.0 Silver iodobromide e 0.60 7.0 4,1 Silver iodobromide f 0.65 8 0.7 6.5 silver iodobromide h 0.65 8.0 1.4 silver iodobromide i 1.00 8.0 2.0 silver iodobromide j 0.05 2.0 1.0 Production examples of silver iodobromide d and f are shown below as preferred examples of forming silver halide grains of the present invention. Regarding silver iodobromide j, JP-A-1-183417 and 1-1.
No. 83644, No. 1-183645, No. 2-1664
It was prepared with reference to the description relating to No. 42.

【０１３９】まず、種晶乳剤−１を調製した。First, seed crystal emulsion-1 was prepared.

【０１４０】〈種晶乳剤−１の調製〉特公昭５８−５８
２８８号、同５８−５８２８９号に示される混合撹拌機
を用いて、３５℃に調整した下記溶液Ａ１に硝酸銀水溶
液（１．１６１モル）と、臭化カリウムと沃化カリウム
の混合水溶液（沃化カリウム２モル％）を、銀電位（飽
和銀−塩化銀電極を比較電極として銀イオン選択電極で
測定）を０ｍＶに保ちながら同時混合法により２分を要
して添加し、核形成を行った。続いて、６０分の時間を
要して液温を６０℃に上昇させ、炭酸ナトリウム水溶液
でｐＨを５．０に調整した後、硝酸銀水溶液（５．９０
２モル）と、臭化カリウムと沃化カリウムの混合水溶液
（沃化カリウム２モル％）を、銀電位を９ｍＶに保ちな
がら同時混合法により、４２分を要して添加した。添加
終了後４０℃に降温しながら、通常のフロキュレーショ
ン法を用いて直ちに脱塩、水洗を行った。<Preparation of Seed Emulsion-1> JP-B-58-58
No. 288 and No. 58-58289, a silver nitrate aqueous solution (1.161 mol) and a mixed aqueous solution of potassium bromide and potassium iodide (iodide) were added to the following solution A1 adjusted to 35 ° C. Potassium 2 mol%) was added over 2 minutes by the simultaneous mixing method while keeping the silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) at 0 mV to perform nucleation. . Subsequently, the temperature of the solution was raised to 60 ° C. over a period of 60 minutes, and the pH was adjusted to 5.0 with an aqueous sodium carbonate solution.
2 mol) and a mixed aqueous solution of potassium bromide and potassium iodide (potassium iodide 2 mol%) was added over 42 minutes by a double jet method while keeping the silver potential at 9 mV. After the addition was completed, the temperature was lowered to 40 ° C., and desalting and washing were immediately performed using a normal flocculation method.

【０１４１】得られた種晶乳剤は、平均球換算直径が
０．２４μｍ、平均アスペクト比が４．８、ハロゲン化
銀粒子の全投影面積の９０％以上が最大辺長比率（各粒
子の最大辺長と最小辺長との比）が１．０〜２．０の六
角状の平板状粒子から成る乳剤であった。この乳剤を種
晶乳剤−１と称する。The resulting seed crystal emulsion had an average sphere-equivalent diameter of 0.24 μm, an average aspect ratio of 4.8, and a maximum side length ratio of 90% or more of the total projected area of the silver halide grains (maximum ratio of each grain). The emulsion was composed of hexagonal tabular grains having a ratio of a side length to a minimum side length of 1.0 to 2.0. This emulsion is referred to as seed emulsion-1.

【０１４２】 （溶液Ａ１） オセインゼラチン ２４．２ｇ 臭化カリウム １０．８ｇ 界面活性剤（ＥＯ−１）の１０％エタノール溶液 ６．７８ｍｌ １０％硝酸 １１４ｍｌ 水 ９６５７ｍｌ （沃化銀微粒子乳剤ＳＭＣ−１の調製）０．０６モルの
沃化カリウムを含む６．０重量％のゼラチン水溶液５リ
ットルを激しく撹拌しながら、７．０６モルの硝酸銀水
溶液と７．０６モルの沃化カリウム水溶液、各々２リッ
トルを１０分を要して添加した。この間ｐＨは硝酸を用
いて２．０に、温度は４０℃に制御した。粒子調製後
に、炭酸ナトリウム水溶液を用いてｐＨを５．０に調整
した。得られた沃化銀微粒子の平均粒径は０．０５μｍ
であった。この乳剤をＳＭＣ−１とする。(Solution A1) Ossein gelatin 24.2 g Potassium bromide 10.8 g 10% ethanol solution of surfactant (EO-1) 6.78 ml 10% nitric acid 114 ml Water 9657 ml (silver iodide fine grain emulsion SMC-1 Preparation) While stirring vigorously 5 L of a 6.0% by weight aqueous gelatin solution containing 0.06 mol of potassium iodide, 7.0 L of an aqueous solution of silver nitrate and 2 L of a 7.06 mol of aqueous solution of potassium iodide were added. Was added over 10 minutes. During this time, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the preparation of the particles, the pH was adjusted to 5.0 using an aqueous sodium carbonate solution. The average particle size of the obtained silver iodide fine particles is 0.05 μm.
Met. This emulsion is designated as SMC-1.

【０１４３】（沃臭化銀ｄの調製）０．１７８モル相当
の種晶乳剤−１と界面活性剤（ＳＵ−１）の１０％エタ
ノール溶液０．５ｍｌを含む、４．５重量％の不活性ゼ
ラチン水溶液７００ｍｌを７５℃に保ち、ｐＡｇを８．
４、ｐＨを５．０に調整した後、激しく撹拌しながら同
時混合法により以下の手順で粒子形成を行った。(Preparation of silver iodobromide d) A solution containing 0.178 mol of a seed crystal emulsion-1 and 0.5 ml of a 10% ethanol solution of a surfactant (SU-1) was prepared. 700 ml of the active gelatin aqueous solution was kept at 75 ° C., and the pAg was 8.
4. After adjusting the pH to 5.0, particles were formed by the simultaneous mixing method with vigorous stirring according to the following procedure.

【０１４４】１）３．０９３モルの硝酸銀水溶液と０．
２８７モルのＳＭＣ−１及び臭化カリウム水溶液を、ｐ
Ａｇを８．４、ｐＨを５．０に保ちながら添加した。1) 3.093 mol of an aqueous silver nitrate solution and
287 mol of SMC-1 and aqueous potassium bromide solution were added to p
Ag was added while keeping the pH at 8.4 and the pH at 5.0.

【０１４５】２）続いて溶液を６０℃に降温し、ｐＡｇ
を９．８に調整した。その後、０．０７１モルのＳＭＣ
−１を添加し、２分間熟成を行った（転位線の導入）。2) Subsequently, the solution was cooled to 60 ° C.
Was adjusted to 9.8. Then, 0.071 mol of SMC
-1 was added and aging was performed for 2 minutes (introduction of dislocation lines).

【０１４６】３）０．９５９モルの硝酸銀水溶液と０．
０３モルのＳＭＣ−１及び臭化カリウム水溶液を、ｐＡ
ｇを９．８、ｐＨを５．０に保ちながら添加した。3) 0.959 mol of silver nitrate aqueous solution
03 mol of SMC-1 and an aqueous solution of potassium bromide were added to pA
g while maintaining the pH at 9.8 and the pH at 5.0.

【０１４７】尚、粒子形成を通して、各溶液は、新核の
生成や粒子間のオストワルド熟成が進まないように最適
な速度で添加した。Throughout the formation of the particles, each solution was added at an optimum rate so that the formation of new nuclei and the Ostwald ripening between particles did not proceed.

【０１４８】上記添加終了後に、４０℃で通常のフロキ
ュレーション法を用いて水洗処理を施した後、ゼラチン
を加えて再分散し、ｐＡｇを８．１、ｐＨを５．８に調
整した。After completion of the addition, the mixture was washed with water at 40 ° C. using a usual flocculation method, and then gelatin was added to redisperse the mixture. The pAg was adjusted to 8.1 and the pH was adjusted to 5.8.

【０１４９】得られた乳剤は、粒径（同体積の立方体１
辺長）０．７５μｍ、平均アスペクト比５．０、粒子内
部から沃化銀含有率２／８．５／Ｘ／３モル％（Ｘは転
位線導入位置）のハロゲン組成を有する平板状粒子から
成る乳剤であった。この乳剤を電子顕微鏡で観察したと
ころ、乳剤中の粒子の全投影面積の６０％以上の粒子に
フリンジ部と粒子内部双方に５本以上の転位線が観察さ
れた。表面沃化銀含有率は６．７モル％であった。The obtained emulsion had a particle size (cubic 1 of the same volume).
Tabular grains having a halogen composition having a side length of 0.75 μm, an average aspect ratio of 5.0, and a silver iodide content of 2 / 8.5 / X / 3 mol% (X is a dislocation line introduction position) from the inside of the grains. Emulsion. When this emulsion was observed with an electron microscope, five or more dislocation lines were observed in both the fringe portion and the inside of the grains in 60% or more of the total projected area of the grains in the emulsion. The surface silver iodide content was 6.7 mol%.

【０１５０】〈沃臭化銀ｆの調製〉沃臭化銀ｄの調製に
おいて、１）の工程でｐＡｇを８．８、かつ添加する硝
酸銀量を２．０７７モル、ＳＭＣ−１の量を０．２１８
モルとし、３）の工程で添加する硝酸銀量を０．９１モ
ル、ＳＭＣ−１の量を０．０７９モルとした以外は沃臭
化銀ｄと全く同様にして沃臭化銀ｆを調製した。<Preparation of silver iodobromide f> In the preparation of silver iodobromide d, in step 1), the pAg was 8.8, the amount of silver nitrate added was 2.077 mol, and the amount of SMC-1 was 0. .218
Silver iodobromide f was prepared in exactly the same manner as silver iodobromide d except that the amount of silver nitrate added in step 3) was 0.91 mol and the amount of SMC-1 was 0.079 mol. .

【０１５１】得られた乳剤は、粒径（同体積の立方体１
辺長）０．６５μｍ、平均アスペクト比６．５、粒子内
部から沃化銀含有率２／９．５／Ｘ／８モル％（Ｘは転
位線導入位置）のハロゲン組成を有する平板状粒子から
成る乳剤であった。この乳剤を電子顕微鏡で観察したと
ころ、乳剤中の粒子の全投影面積の６０％以上の粒子に
フリンジ部と粒子内部双方に５本以上の転位線が観察さ
れた。表面沃化銀含有率は、１１．９モル％であった。The obtained emulsion had a particle size (cubic 1 of the same volume).
Tabular grains having a halogen composition having a side length of 0.65 μm, an average aspect ratio of 6.5, and a silver iodide content of 2 / 9.5 / X / 8 mol% (where X is a dislocation line introduction position) from the inside of the grains. Emulsion. When this emulsion was observed with an electron microscope, five or more dislocation lines were observed in both the fringe portion and the inside of the grains in 60% or more of the total projected area of the grains in the emulsion. The surface silver iodide content was 11.9 mol%.

【０１５２】上記各乳剤に前述の増感色素を添加、熟成
した後、トリフェニルホスフィンセレナイド、チオ硫酸
ナトリウム、塩化金酸、チオシアン酸カリウムを添加
し、カブリ−感度関係が最適になるように化学増感を施
した。After the above-mentioned sensitizing dyes were added to each of the above emulsions and ripened, triphenylphosphine selenide, sodium thiosulfate, chloroauric acid, and potassium thiocyanate were added to optimize the fog-sensitivity relationship. Chemical sensitization was applied.

【０１５３】沃臭化銀ａ、ｂ、ｃ、ｅ、ｇ、ｈ、ｉにつ
いても、上記沃臭化銀ｄ、ｆに準じ分光増感、化学増感
を施した。Silver bromoiodides a, b, c, e, g, h and i were also subjected to spectral sensitization and chemical sensitization in accordance with the above-mentioned silver bromoiodides d and f.

【０１５４】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Ａ
Ｆ−１（ポリビニルピロリドン，重量平均分子量：１
０，０００），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及び防腐剤
Ａｓｅ−１を添加した。Incidentally, in addition to the above composition, a coating aid SU-
1, SU-2, SU-3, dispersing aid SU-4, viscosity modifier V-1, stabilizers ST-1, ST-2, antifoggant A
F-1 (polyvinylpyrrolidone, weight average molecular weight: 1)
000), AF-2 (polyvinyl pyrrolidone, weight average molecular weight: 1,100,000), inhibitor AF-3,
AF-4, AF-5, hardeners H-1, H-2 and preservative Ase-1 were added.

【０１５５】上記試料に用いた化合物の構造を以下に示
す。The structures of the compounds used in the above samples are shown below.

【０１５６】ＳＵ−１：Ｃ8Ｆ17ＳＯ2Ｎ（Ｃ3Ｈ7）ＣＨ
2ＣＯＯＫ ＳＵ−２：Ｃ8Ｆ17ＳＯ2ＮＨ（ＣＨ2）3Ｎ+（ＣＨ3）3
Ｂｒ− 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−１，３，３
ａ，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）3ＣＣＨ2ＳＯ2
ＣＨ2ＣＨ2〕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 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−３：１，４−ビス（２−テトラデシルオキシカル
ボニルエチル）ピペラジンSU-1: C 8 F 17 SO 2 N (C 3 H 7 ) CH
2 COOK SU-2: C 8 F 17 SO 2 NH (CH 2) 3 N + (CH 3) 3
Br - SU-3: sodium di (2-ethylhexyl) sulfosuccinate SU-4: sodium tri-i-propylnaphthalenesulfonate ST-1: 4-hydroxy-6-methyl-1,3,3
a, 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: [(CH 2 = CHSO 2 CH 2 ) 3 CCH 2 SO 2
CH 2 CH 2] 2 NCH 2 CH 2 SO 3 K H-2: 2,4- dichloro-6-hydroxy -s- triazine sodium 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: 1,4-bis (2-tetradecyloxycarbonylethyl) Piperazine

【０１５７】[0157]

【化１】 Embedded image

【０１５８】[0158]

【化２】 Embedded image

【０１５９】[0159]

【化３】 Embedded image

【０１６０】[0160]

【化４】 Embedded image

【０１６１】[0161]

【化５】 Embedded image

【０１６２】[0162]

【化６】 Embedded image

【０１６３】 （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当たりの値である。(Processing step) Processing step Processing time Processing temperature Replenishment amount * Color development 3 minutes 15 seconds 38 ± 0.3 ° C. 780 ml Bleaching 45 seconds 38 ± 2.0 ° C. 150 ml Fixing 1 minute 30 seconds 38 ± 2. 0 ° C. 830 ml Stability 60 seconds 38 ± 5.0 ° C. 830 ml Drying 1 minute 55 ± 5.0 ° C.-* The replenishing amount is a value per 1 m 2 of the photosensitive material.

【０１６４】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。The following color developing solutions, bleaching solutions, fixing solutions, stabilizing solutions and replenishers were used.

【０１６５】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１リットルとし、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。 Color developing solution and color developing replenishing solution Developer replenishing solution Water 800 ml 800 ml Potassium carbonate 30 g 35 g Sodium bicarbonate 2.5 g 3.0 g Potassium sulfite 3.0 g 5.0 g Sodium bromide 1.3 g 0.4 g iodide Potassium 1.2 mg-Hydroxylamine sulfate 2.5 g 3.1 g Sodium chloride 0.6 g-4-Amino-3-methyl-N-ethyl-N-([beta] -hydroxylethyl) aniline sulfate 4.5 g 6.3 g Diethylenetriaminepentaacetic acid 3.0 g 3.0 g Potassium hydroxide 1.2 g 2.0 g Add water to make 1 liter, and add potassium hydroxide or 20%
The color developing solution is adjusted to pH 10.06 and the replenisher is adjusted to pH 10.18 using sulfuric acid.

【０１６６】漂白液及び漂白補充液 漂白液 補充液 水 ７００ｍｌ ７００ｍｌ １，３−ジアミノプロパン四酢酸鉄（III）アンモニウム １２５ｇ １７５ｇ エチレンジアミン四酢酸 ２ｇ ２ｇ 硝酸ナトリウム ４０ｇ ５０ｇ 臭化アンモニウム １５０ｇ ２００ｇ 氷酢酸 ４０ｇ ５６ｇ 水を加えて１リットルとし、アンモニア水又は氷酢酸を
用いて漂白液はｐＨ４．４に、補充液はｐＨ４．０に調
整する。 Bleaching Solution and Bleaching Replenisher Bleaching Solution Replenisher Water 700 ml 700 ml 1,3-diaminopropanetetraacetate ammonium (III) ammonium 125 g 175 g ethylenediaminetetraacetic acid 2 g 2 g sodium nitrate 40 g 50 g ammonium bromide 150 g 200 g glacial acetic acid 40 g 56 g water To 1 liter, and adjust the pH of the bleaching solution to 4.4 and the pH of the replenishing solution to 4.0 using ammonia water or glacial acetic acid.

【０１６７】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１リット
ルとする。 Fixing solution and fixing replenisher Fixing solution Replenisher Water 800 ml 800 ml Ammonium thiocyanate 120 g 150 g Ammonium thiosulfate 150 g 180 g Sodium sulfite 15 g 20 g Ethylenediaminetetraacetic acid 2 g 2 g Aqueous solution using ammonia water or glacial acetic acid, pH 6.2
Then, the pH of the replenisher is adjusted to 6.5, and then water is added to make 1 liter.

【０１６８】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１リットルとした後、アンモニア水又は５０
％硫酸を用いてｐＨ８．５に調整する。 Stabilizing Solution and Stabilizing Replenisher Water 900 ml p-octylphenol ethylene oxide 10 mol adduct 2.0 g dimethylolurea 0.5 g hexamethylenetetramine 0.2 g 1,2-benzoisothiazolin-3-one 0.1 g siloxane (UCC L-77) 0.1 g ammonia water 0.5 ml water was added to make up to 1 liter.
Adjust to pH 8.5 with% sulfuric acid.

【０１６９】《感度、粒状性の評価》試料１０１〜１０
５に、白色光を用いて１／２００秒、３．２ＣＭＳでス
テップウェッジ露光下後、直ちに上記のカラー現像処理
を施して特性曲線を求めた。<< Evaluation of Sensitivity and Granularity >> Samples 101 to 10
5 was subjected to a step wedge exposure at 1/2200 second and 3.2 CMS using white light, and immediately thereafter, the above-mentioned color development processing was performed to obtain a characteristic curve.

【０１７０】感度は、緑感度（カブリ濃度＋０．１０の
濃度を与える露光量の逆数）を試料１０１の値を１００
とする相対値で示した。The sensitivity was determined by setting the green sensitivity (the reciprocal of the exposure amount that gives a density of fog + 0.10) to the value of the sample 101 as 100.
The relative values are shown below.

【０１７１】粒状性は、ＲＭＳ粒状度（カブリ濃度＋
０．３０のマゼンタ濃度を開口走査面積２５０μｍ２の
マイクロデンシトメーターで走査した時に生じる濃度値
の変動の１０００倍値）を測定し、試料１０１の値を１
００とする相対値で示した。The granularity was determined by the RMS granularity (fog density +
A magenta density of 0.30 was scanned with a microdensitometer having an aperture scanning area of 250 μm 2, and the value of the sample 101 was determined to be 1).
The relative value is set to 00.

【０１７２】表２に試料１０１〜１０５の評価結果を示
す。Table 2 shows the evaluation results of the samples 101 to 105.

【０１７３】[0173]

【表２】 [Table 2]

【０１７４】表２から本発明の乳剤Ｅｍ−４及びＥｍ−
５を用いた試料１０４及び１０５は、比較乳剤Ｅｍ−１
〜Ｅｍ−３を用いた試料１０１〜１０３に比べて、優れ
た感度、粒状性を示した。Table 2 shows that the emulsions Em-4 and Em-
Samples 104 and 105 using Sample No. 5 were Comparative Emulsions Em-1
-Em-3 showed superior sensitivity and granularity as compared with the samples 101 to 103.

【０１７５】実施例２ 〈比較乳剤Ｅｍ−１１の調製〉実施例１における比較乳
剤Ｅｍ−１の調製において、Ｂ−２液、Ｃ−２液、Ｄ−
２液の添加、及び、ｐＨ、ｐＡｇの制御を表３に示すよ
うに制御する事以外は、同様にして、比較乳剤（Ｅｍ−
１１）を調製した。Example 2 <Preparation of Comparative Emulsion Em-11> In the preparation of Comparative Emulsion Em-1 in Example 1, solutions B-2, C-2 and D-
Comparative emulsion (Em-E) was prepared in the same manner except that the addition of the two solutions and the control of pH and pAg were controlled as shown in Table 3.
11) was prepared.

【０１７６】この乳剤中のハロゲン化銀粒子を電子顕微
鏡にて観察したところ、平均粒径１．０３μｍ、粒径分
布１０％であり、ハロゲン化銀粒子表面が殆ど（１０
０）面で構成された六面体双晶ハロゲン化銀粒子であ
り、粒子個数の９６％を占めていた。When the silver halide grains in this emulsion were observed with an electron microscope, the average grain size was 1.03 μm, and the grain size distribution was 10%.
It was a hexahedral twin silver halide grain composed of 0) planes, and accounted for 96% of the number of grains.

【０１７７】[0177]

【表３】 [Table 3]

【０１７８】〈比較乳剤Ｅｍ−１２の調製〉比較乳剤Ｅ
ｍ−１１の調製において、脱塩処理の代わりに前記の限
外濾過Ａの操作を施した。その後、５０℃にてｐＡｇを
８．２に調製し、前記Ｊ−２液のハロゲン化銀量で０．
１５モル相当量を１０分で添加し、２０分間熟成した
後、限外濾過Ａの操作を施し、４０℃においてｐＡｇ
８．０６、ｐＨ５．８に調整する以外は同様にして比較
乳剤（Ｅｍ−１２）を調製した。<Preparation of Comparative Emulsion Em-12> Comparative Emulsion E
In the preparation of m-11, the above operation of ultrafiltration A was performed instead of the desalting treatment. Thereafter, the pAg was adjusted to 8.2 at 50 ° C., and the pAg was adjusted to 0.1 in terms of the silver halide content of the J-2 solution.
After adding 15 mol equivalent in 10 minutes and aging for 20 minutes, the operation of ultrafiltration A was performed, and pAg
A comparative emulsion (Em-12) was prepared in the same manner except that the pH was adjusted to 8.06 and pH 5.8.

【０１７９】〈比較乳剤Ｅｍ−１３の調製〉比較乳剤Ｅ
ｍ−１１の調製において、脱塩処理の代わりに前記の限
外濾過Ａの操作を施した。その後、６０℃にて２Ｎ臭化
カリウム水溶液でｐＡｇを８．８に調整して前記Ｋ−２
液のハロゲン化銀量で１．１モル相当量を１０分で添加
し、２０分間熟成した後、限外濾過Ａの操作を施し、４
０℃においてｐＡｇ８．０６、ｐＨ５．８に調整する以
外は同様にして比較乳剤（Ｅｍ−１３）を調製した。<Preparation of Comparative Emulsion Em-13> Comparative Emulsion E
In the preparation of m-11, the above operation of ultrafiltration A was performed instead of the desalting treatment. Then, the pAg was adjusted to 8.8 with a 2N aqueous potassium bromide solution at 60 ° C.
The solution was added in an amount of 1.1 mol in terms of silver halide in 10 minutes, ripened for 20 minutes, and then subjected to the operation of ultrafiltration A.
A comparative emulsion (Em-13) was prepared in the same manner except that the pAg was adjusted to 8.06 and the pH to 5.8 at 0 ° C.

【０１８０】〈本発明乳剤Ｅｍ−１４の調製〉比較乳剤
Ｅｍ−１１の調製において、脱塩処理の代わりに前記の
限外濾過Ａの操作を施した。その後、６０℃ににて、２
Ｎ臭化カリウム水溶液でｐＡｇを８．８に調整し、前記
Ｋ−２液のハロゲン化銀量で１．１モル相当量を１０分
で添加し、２０分間熟成した後、５０℃に降温し、ｐＡ
ｇを８．２に調製し、前記Ｊ−２液のハロゲン化銀量で
０．１５モル相当量を１０分で添加し、２０分間熟成し
Ｑ後、限外濾過Ａの操作を施し、４０℃においてｐＡｇ
８．０６、ｐＨ５．８に調整する以外は同様にして本発
明乳剤（Ｅｍ−１４）を調製した。<Preparation of Emulsion Em-14 of the Present Invention> In the preparation of comparative emulsion Em-11, the above-mentioned operation of ultrafiltration A was performed instead of the desalting treatment. Then, at 60 ° C., 2
The pAg was adjusted to 8.8 with an aqueous solution of potassium potassium bromide, 1.1 mol equivalent of the silver halide in the K-2 solution was added in 10 minutes, the mixture was aged for 20 minutes, and then cooled to 50 ° C. , PA
g was adjusted to 8.2, an amount equivalent to 0.15 mol of silver halide in the J-2 solution was added in 10 minutes, the mixture was aged for 20 minutes, and after Q, the operation of ultrafiltration A was performed. PAg in ° C
An emulsion of the present invention (Em-14) was prepared in the same manner except that the pH was adjusted to 8.06 and the pH was adjusted to 5.8.

【０１８１】〈本発明乳剤Ｅｍ−１５の調製〉比較乳剤
Ｅｍ−１１の調製において、脱塩処理の代わりに前記の
限外濾過Ａの操作を施した。その後、６０℃に昇温し、
２Ｎ臭化カリウム水溶液でｐＡｇを９．０に調整して前
記Ｋ−２液のハロゲン化銀量で１．８モル相当量を１０
分で添加し、２０分間熟成した後、５０℃に降温し、ｐ
Ａｇを８．２に調製し、前記Ｊ−２液のハロゲン化銀量
で０．３モル相当量を１０分で添加し、２０分間熟成し
た後、限外濾過Ａの操作を施し、４０℃においてｐＡｇ
８．０６、ｐＨ５．８に調整する以外は同様にして本発
明乳剤（Ｅｍ−１５）を調製した。<Preparation of Emulsion Em-15 of the Present Invention> In the preparation of comparative emulsion Em-11, the above-mentioned operation of ultrafiltration A was performed instead of the desalting treatment. Then, the temperature was raised to 60 ° C,
The pAg was adjusted to 9.0 with a 2N aqueous potassium bromide solution, and the amount of silver halide in the K-2 liquid was adjusted to 1.8 mol equivalent to 10 mol.
After aging for 20 minutes, the temperature was lowered to 50 ° C.
Ag was adjusted to 8.2, 0.3 mol equivalent of the silver halide of the J-2 solution was added in 10 minutes, and the mixture was aged for 20 minutes. At pAg
An emulsion of the present invention (Em-15) was prepared in the same manner except that the pH was adjusted to 8.06 and pH 5.8.

【０１８２】上記乳剤Ｅｍ−１１〜Ｅｍ−１５に含まれ
るハロゲン化銀粒子のハロゲン化銀組成をＸ線回折で確
認したところ、Ｅｍ−１３〜Ｅｍ−１５に含まれるハロ
ゲン化銀粒子は塩化銀を含有していることが確認され
た。When the silver halide composition of the silver halide grains contained in the emulsions Em-11 to Em-15 was confirmed by X-ray diffraction, the silver halide grains contained in the emulsions Em-13 to Em-15 were found to be silver chloride. Was confirmed to be contained.

【０１８３】乳剤Ｅｍ−１１〜Ｅｍ−１５を用いて実施
例１と同様に多層カラー感光材料試料１１１〜１１５を
作製し、同様に評価した。結果を表４に示す。Using the emulsions Em-11 to Em-15, multilayer color photographic material samples 111 to 115 were prepared in the same manner as in Example 1, and evaluated in the same manner. Table 4 shows the results.

【０１８４】[0184]

【表４】 [Table 4]

【０１８５】表４から本発明の乳剤Ｅｍ−１４及びＥｍ
−１５を用いた試料１１４及び１１５は、比較乳剤Ｅｍ
−１１〜Ｅｍ−１３を用いた試料１１１〜１１３に比べ
て、優れた感度、粒状性を示した。From Table 4, it can be seen that the emulsions Em-14 and Em of the present invention were obtained.
Samples 114 and 115 using -15 were compared with Comparative Emulsion Em
As compared with Samples 111 to 113 using -11 to Em-13, excellent sensitivity and granularity were exhibited.

【０１８６】実施例３ 〈比較乳剤Ｅｍ−２１の調製〉実施例１における比較乳
剤Ｅｍ−１の調製において、脱塩処理の代わりに前記の
限外濾過Ａの操作を施した。その後、６０℃にて、ｐＡ
ｇを９．０に調製し、前記Ｊ−２液のハロゲン化銀量で
０．８モル相当量を１０分で添加し、２０分間熟成した
後、限外濾過Ａの操作を施し、４０℃においてｐＡｇ
８．０６、ｐＨ５．８に調整する以外は同様にして比較
乳剤（Ｅｍ−２１）を調製した。Example 3 <Preparation of Comparative Emulsion Em-21> In the preparation of Comparative Emulsion Em-1 in Example 1, the above operation of ultrafiltration A was performed instead of the desalting treatment. Then, at 60 ° C., pA
g was adjusted to 9.0, an amount equivalent to 0.8 mol of silver halide in the J-2 solution was added in 10 minutes, the mixture was aged for 20 minutes, and then subjected to the operation of ultrafiltration A at 40 ° C. At pAg
A comparative emulsion (Em-21) was prepared in the same manner except that the pH was adjusted to 8.06 and pH 5.8.

【０１８７】〈比較乳剤Ｅｍ−２２の調製〉実施例１に
おける比較乳剤Ｅｍ−１の調製において、脱塩処理の代
わりに前記の限外濾過Ａの操作を施した。その後、６０
℃にて、ｐＡｇを８．８に調製して、下記Ｊ−３液のハ
ロゲン化銀量で０．３モル相当量を１０分で添加し、２
０分間熟成した後、限外濾過Ａの操作を施し、４０℃に
おいてｐＡｇ８．０６、ｐＨ５．８に調整する以外は同
様にして比較乳剤（Ｅｍ−２２）を調製した。<Preparation of Comparative Emulsion Em-22> In the preparation of Comparative Emulsion Em-1 in Example 1, the above operation of ultrafiltration A was performed instead of the desalting treatment. Then 60
At ℃, the pAg was adjusted to 8.8, and 0.3 mol equivalent of the amount of silver halide in the following J-3 solution was added in 10 minutes.
After aging for 0 minutes, ultrafiltration A was performed, and a comparative emulsion (Em-22) was prepared in the same manner except that the pAg was adjusted to 8.06 and the pH to 5.8 at 40 ° C.

【０１８８】（Ｊ−３液）３．０重量％のゼラチンと沃
臭化銀微粒子（平均粒径０．０５μｍ、沃化銀含有率１
０モル％）から成る微粒子乳剤 調製法を以下に示す。(J-3 solution) 3.0% by weight of gelatin and silver iodobromide fine particles (average particle size: 0.05 μm, silver iodide content: 1)
(0 mol%) is described below.

【０１８９】０．０６モルの臭化カリウムを含む６．０
重量％のゼラチン溶液５０００ｍｌに、７．０６モルの
硝酸銀を含む水溶液２０００ｍｌと６．３５モルの臭化
カリウムと０．７１モルの沃化カリウムを含む水溶液２
０００ｍｌとを１０分間かけて等速添加した。微粒子形
成中のｐＨは、硝酸を用いて３．０に、温度は３０℃に
制御した。添加終了後に、炭酸ナトリウム水溶液を用い
てｐＨを６．０に調整し、前記限外濾過Ｂを施し、２Ｎ
臭化カリウム水溶液で４０℃にてｐＡｇ８．０に調整し
た。6.0 containing 0.06 mol of potassium bromide
2000 ml of an aqueous solution containing 7.06 mol of silver nitrate and an aqueous solution 2 containing 6.35 mol of potassium bromide and 0.71 mol of potassium iodide are added to 5000 ml of a weight% gelatin solution.
000 ml was added at a constant speed over 10 minutes. During the formation of the fine particles, the pH was controlled at 3.0 using nitric acid, and the temperature was controlled at 30 ° C. After the addition was completed, the pH was adjusted to 6.0 using an aqueous sodium carbonate solution, and the ultrafiltration B was performed.
The pAg was adjusted to 8.0 at 40 ° C. with an aqueous potassium bromide solution.

【０１９０】〈比較乳剤Ｅｍ−２３の調製〉実施例１に
おける比較乳剤Ｅｍ−１の調製において、脱塩処理の代
わりに、前記の限外濾過Ａの操作を施した。その後、６
０℃にて、ｐＡｇを８．８に調整し、前記Ｋ−２液のハ
ロゲン化銀量で１．８モル相当量を１０分で添加し、２
０分間熟成した後、限外濾過Ａの操作を施し、４０℃に
おいてｐＡｇ８．０６、ｐＨ５．８に調整する以外は同
様にして比較乳剤（Ｅｍ−２３）を調製した。<Preparation of Comparative Emulsion Em-23> In the preparation of Comparative Emulsion Em-1 in Example 1, the operation of ultrafiltration A was performed instead of the desalting treatment. Then 6
At 0 ° C., the pAg was adjusted to 8.8, and 1.8 mol equivalent of the silver halide in the K-2 solution was added in 10 minutes.
After ripening for 0 minutes, ultrafiltration A was performed, and a comparative emulsion (Em-23) was prepared in the same manner except that the pAg was adjusted to 8.06 and the pH to 5.8 at 40 ° C.

【０１９１】〈本発明乳剤Ｅｍ−２４の調製〉実施例１
における比較乳剤Ｅｍ−１の調製において、脱塩処理の
代わりに、前記の限外濾過Ａの操作を施した。その後、
６０℃にて、ｐＡｇを８．８に調整し、前記Ｋ−２液の
ハロゲン化銀量で１．８モル相当量を１０分で添加し、
２０分間熟成した後、下記Ｋ−３液をハロゲン化銀量で
０．０３モル相当量を加えて３分間熟成し、限外濾過Ａ
の操作を施し、４０℃においてｐＡｇ８．０６、ｐＨ
５．８に調整する以外は同様にして本発明乳剤（Ｅｍ−
２４）を調製した。<Preparation of Emulsion Em-24 of the Invention> Example 1
In the preparation of Comparative Emulsion Em-1, the above-mentioned operation of ultrafiltration A was performed instead of the desalting treatment. afterwards,
At 60 ° C., pAg was adjusted to 8.8, and 1.8 mol equivalent of silver halide in the K-2 solution was added in 10 minutes.
After ripening for 20 minutes, the following K-3 solution was added in an amount equivalent to 0.03 mol of silver halide and ripened for 3 minutes.
At 40 ° C., pAg 8.06, pH
Emulsion of the present invention (Em-
24) was prepared.

【０１９２】（Ｋ−３液）３．０重量％のゼラチンと沃
化銀微粒子（平均粒径０．０５μｍ）から成る微粒子乳
剤 調製法を以下に示す。(K-3 solution) A method for preparing a fine grain emulsion comprising 3.0% by weight of gelatin and fine silver iodide grains (average grain size: 0.05 μm) is described below.

【０１９３】０．０６モルの沃化カリウムを含む６．０
重量％のゼラチン溶液５０００ｍｌに、７．０６モルの
硝酸銀と７．０６モルの沃化カリウムを含む水溶液各々
２０００ｍｌを１０分間かけて等速添加した。微粒子形
成中のｐＨは、硝酸を用いて２．０に、温度は４０℃に
制御した。添加終了後に、炭酸ナトリウム水溶液を用い
てｐＨを６．０に調整し、前記限外濾過Ｂを施した。6.0 containing 0.06 mol of potassium iodide
To 5000 ml of a weight% gelatin solution, 2000 ml of an aqueous solution containing 7.06 mol of silver nitrate and 7.06 mol of potassium iodide was added at a constant speed over 10 minutes. During the formation of the fine particles, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the addition was completed, the pH was adjusted to 6.0 using an aqueous sodium carbonate solution, and the ultrafiltration B was performed.

【０１９４】〈本発明乳剤Ｅｍ−２５の調製〉実施例１
における比較乳剤Ｅｍ−１の調製において、脱塩処理の
代わりに前記の限外濾過Ａの操作を施した。その後、６
０℃にて、ｐＡｇを８．５に調製して、前記Ｋ−２液の
ハロゲン化銀量で１．５モル相当量を１０分で添加し、
２０分間熟成した後、下記Ｌ−３液を加えて、１０％水
酸化カリウム水溶液でｐＨを９．５に上げて３分間保持
した後、１０％硝酸でｐＨを５．０に戻し、限外濾過Ａ
の操作を施し、４０℃においてｐＡｇ８．０６、ｐＨ
５．８に調整する以外は同様にして本発明乳剤（Ｅｍ−
２５）を調製した。<Preparation of Emulsion Em-25 of the Present Invention> Example 1
In the preparation of the comparative emulsion Em-1, the above-mentioned operation of ultrafiltration A was performed instead of the desalting treatment. Then 6
At 0 ° C., the pAg was adjusted to 8.5, and 1.5 mol equivalent of the silver halide in the K-2 solution was added in 10 minutes.
After aging for 20 minutes, the following L-3 solution was added, the pH was raised to 9.5 with a 10% aqueous potassium hydroxide solution, and the mixture was maintained for 3 minutes. Then, the pH was returned to 5.0 with 10% nitric acid. Filtration A
At 40 ° C., pAg 8.06, pH
Emulsion of the present invention (Em-
25) was prepared.

【０１９５】 （Ｌ−３液） ２−ヨードエタノール ０．０５モル 上記乳剤Ｅｍ−２１〜Ｅｍ−２５に含まれるハロゲン化
銀粒子のハロゲン化銀組成をＸ線回折で確認したとこ
ろ、Ｅｍ−２３〜Ｅｍ−２５に含まれるハロゲン化銀粒
子は塩化銀を含有していることが確認された。(L-3 solution) 2-iodoethanol 0.05 mol The silver halide composition of the silver halide grains contained in the above-mentioned emulsions Em-21 to Em-25 was confirmed by X-ray diffraction. To Em-25 were confirmed to contain silver chloride.

【０１９６】乳剤Ｅｍ−２１〜Ｅｍ−２５を用いて実施
例１と同様に多層カラー感光材料試料１２１〜１２５を
作製し、評価した。結果を表５に示す。Using the emulsions Em-21 to Em-25, multilayer color light-sensitive material samples 121 to 125 were prepared and evaluated in the same manner as in Example 1. Table 5 shows the results.

【０１９７】[0197]

【表５】 [Table 5]

【０１９８】表５から本発明の乳剤Ｅｍ−２４及びＥｍ
−２５を用いた試料１２４及び１２５は、比較乳剤Ｅｍ
−２１〜Ｅｍ−２３を用いた試料１２１〜１２３に比べ
て、優れた感度、粒状性を示した。Table 5 shows that the emulsions Em-24 and Em of the present invention were obtained.
Samples 124 and 125 using -25 were prepared as Comparative Emulsion Em
As compared with Samples 121 to 123 using -21 to Em-23, excellent sensitivity and granularity were exhibited.

【０１９９】実施例４ 〈比較乳剤Ｅｍ−３１の調製〉実施例２における比較乳
剤Ｅｍ−１１の調製において、脱塩処理の代わりに前記
の限外濾過Ａの操作を施した。その後、６０℃にて、ｐ
Ａｇを９．０に調整し、前記Ｊ−２液のハロゲン化銀量
で０．８モル相当量を１０分で添加し、２０分間熟成し
た後、限外濾過Ａの操作を施し、４０℃においてｐＡｇ
８．０６、ｐＨ５．８に調整する以外は同様にして比較
乳剤（Ｅｍ−３１）を調製した。Example 4 <Preparation of Comparative Emulsion Em-31> In the preparation of Comparative Emulsion Em-11 in Example 2, the above-mentioned operation of ultrafiltration A was performed instead of the desalting treatment. Then, at 60 ° C., p
Ag was adjusted to 9.0, 0.8 mol equivalent of silver halide in the J-2 solution was added in 10 minutes, and after aging for 20 minutes, the operation of ultrafiltration A was performed, and 40 ° C. At pAg
A comparative emulsion (Em-31) was prepared in the same manner except that the pH was adjusted to 8.06 and pH 5.8.

【０２００】〈比較乳剤Ｅｍ−３２の調製〉実施例２に
おける比較乳剤Ｅｍ−１１の調製において、特開平５−
７２６５８号に記載の方法に従い脱塩処理を行う代わり
に、前記の限外濾過Ａの操作を施した。その後、６０℃
にて、ｐＡｇを８．８に調整し、前記Ｊ−３液のハロゲ
ン化銀量で０．３モル相当量を１０分で添加し、２０分
間熟成した後、限外濾過Ａの操作を施し、４０℃におい
てｐＡｇ８．０６、ｐＨ５．８に調整する以外は同様に
して比較乳剤（Ｅｍ−３２）を調製した。<Preparation of Comparative Emulsion Em-32> In the preparation of Comparative Emulsion Em-11 in Example 2,
Instead of performing the desalting treatment according to the method described in No. 72658, the above operation of ultrafiltration A was performed. Then 60 ° C
The pAg was adjusted to 8.8, 0.3 mol equivalent of the silver halide in the J-3 solution was added in 10 minutes, and the mixture was aged for 20 minutes. A comparative emulsion (Em-32) was prepared in the same manner except that pAg was adjusted to 8.06 and pH 5.8 at 40 ° C.

【０２０１】〈比較乳剤Ｅｍ−３３の調製〉実施例２に
おける比較乳剤Ｅｍ−１１の調製において、脱塩処理の
代わりに前記の限外濾過Ａの操作を施した。その後、６
０℃にて、ｐＡｇを８．８に調整し、前記Ｋ−２液のハ
ロゲン化銀量で１．８モル相当量を１０分で添加し、２
０分間熟成した後、限外濾過Ａの操作を施し、４０℃に
おいてｐＡｇ８．０６、ｐＨ５．８に調整する以外は同
様にして比較乳剤（Ｅｍ−３３）を調製した。<Preparation of Comparative Emulsion Em-33> In the preparation of Comparative Emulsion Em-11 in Example 2, the above operation of ultrafiltration A was performed instead of the desalting treatment. Then 6
At 0 ° C., the pAg was adjusted to 8.8, and 1.8 mol equivalent of the silver halide in the K-2 solution was added in 10 minutes.
After aging for 0 minutes, ultrafiltration A was performed, and a comparative emulsion (Em-33) was prepared in the same manner except that pAg was adjusted to 8.06 and pH 5.8 at 40 ° C.

【０２０２】〈本発明乳剤Ｅｍ−３４の調製〉実施例２
における比較乳剤Ｅｍ−１１の調製において、脱塩処理
の代わりに前記の限外濾過Ａの操作を施した。その後、
６０℃にて、ｐＡｇを８．８に調整し、前記Ｋ−２液の
ハロゲン化銀量で１．８モル相当量を１０分で添加し、
２０分間熟成した後、前記Ｋ−３液をハロゲン化銀量で
０．０３モル相当量を加えて３分間熟成し、限外濾過Ａ
の操作を施し、４０℃においてｐＡｇ８．０６、ｐＨ
５．８に調整する以外は同様にして本発明乳剤（Ｅｍ−
３４）を調製した。<Preparation of Emulsion Em-34 of the Invention> Example 2
In the preparation of the comparative emulsion Em-11, the above operation of ultrafiltration A was performed instead of the desalting treatment. afterwards,
At 60 ° C., pAg was adjusted to 8.8, and 1.8 mol equivalent of silver halide in the K-2 solution was added in 10 minutes.
After ripening for 20 minutes, the K-3 solution was ripened for 3 minutes by adding an amount equivalent to 0.03 mol in terms of silver halide.
At 40 ° C., pAg 8.06, pH
Emulsion of the present invention (Em-
34) was prepared.

【０２０３】〈本発明乳剤Ｅｍ−３５の調製〉実施例２
における比較乳剤Ｅｍ−１１の調製において、脱塩処理
の代わりに前記限外濾過Ａの操作を施した。その後、６
０℃にて、ｐＡｇを８．５に調整し、前記Ｋ−２液のハ
ロゲン化銀量で１．５モル相当量を１０分で添加し、２
０分間熟成した後、前記Ｌ−３液を加えて、１０％水酸
化カリウム水溶液でｐＨを９．５に上げて３分間保持
し、その後、１０％硝酸でｐＨを５．０に戻し、限外濾
過Ａの操作を施し、４０℃においてｐＡｇ８．０６、ｐ
Ｈ５．８に調整する以外は同様にして本発明乳剤（Ｅｍ
−３５）を調製した。<Preparation of Emulsion Em-35 of the Present Invention> Example 2
In the preparation of Comparative Emulsion Em-11, ultrafiltration A was performed instead of desalting. Then 6
At 0 ° C., the pAg was adjusted to 8.5, and an amount equivalent to 1.5 mol of the silver halide in the K-2 solution was added in 10 minutes.
After aging for 0 minutes, the above-mentioned L-3 solution was added, the pH was raised to 9.5 with a 10% aqueous potassium hydroxide solution, and maintained for 3 minutes. Thereafter, the pH was returned to 5.0 with 10% nitric acid, The operation of ultrafiltration A was performed, and pAg 8.06, p
The emulsion of the present invention (Em
-35) was prepared.

【０２０４】上記乳剤Ｅｍ−３１〜Ｅｍ−３５に含まれ
るハロゲン化銀粒子のハロゲン化銀組成をＸ線回折で確
認したところ、Ｅｍ−３３〜Ｅｍ−３５に含まれるハロ
ゲン化銀粒子は、塩化銀を含有していることが確認され
た。When the silver halide composition of the silver halide grains contained in the emulsions Em-31 to Em-35 was confirmed by X-ray diffraction, the silver halide grains contained in the emulsions Em-33 to Em-35 were found to contain chloride. It was confirmed that silver was contained.

【０２０５】乳剤Ｅｍ−３１〜Ｅｍ−３５を用いて実施
例１と同様に多層カラー感光材料試料１３１〜１３５を
作製し、評価した。結果を表６に示す。Using the emulsions Em-31 to Em-35, multilayer color light-sensitive material samples 131 to 135 were prepared and evaluated in the same manner as in Example 1. Table 6 shows the results.

【０２０６】[0206]

【表６】 [Table 6]

【０２０７】表６から本発明の乳剤Ｅｍ−３４及びＥｍ
−３５を用いた試料１３４及び１３５は、比較乳剤Ｅｍ
−３１〜Ｅｍ−３３を用いた試料１３１〜１３３に比べ
て、優れた感度、粒状性を示した。Table 6 shows that the emulsions Em-34 and Em of the present invention were obtained.
Samples 134 and 135 using −35 were compared with comparative emulsion Em.
As compared with samples 131 to 133 using -31 to Em-33, excellent sensitivity and granularity were exhibited.

【０２０８】実施例５ 〈種乳剤Ｔ−３の調製〉以下に示す方法によって、２枚
の平行な双晶面を有する種乳剤Ｔ−３を調製した。Example 5 <Preparation of seed emulsion T-3> Seed emulsion T-3 having two parallel twin planes was prepared by the following method.

【０２０９】 （Ａ−３液） オセインゼラチン ３８．０ｇ 臭化カリウム １１．７ｇ 水で ３４．０リットル （Ｂ−３液） 硝酸銀 ８１０．０ｇ 水で ３８１５ｍｌ （Ｃ−３液） 臭化カリウム ５６７．３ｇ 水で ３８１５ｍｌ （Ｄ−３液） オセインゼラチン １６３．４ｇ 界面活性剤（ＥＯ−１）の１０％メタノール溶液 ５．５ｍｌ 水で ３９６１ｍｌ （Ｅ−３液） 硫酸（１０％） ９１．１ｍｌ （Ｆ−３液） ５６％酢酸水溶液 必要量 （Ｇ−３液） アンモニア水（２８％） １０５．７ｍｌ （Ｈ−３液） 水酸化カリウム１０％水溶液 必要量 特開昭６２−１６０１２８号記載の攪拌装置を用い、３
０℃で激しく攪拌したＡ−３液にＥ−３液を添加し、そ
の後Ｂ−３液とＣ−３液とをダブルジェット法により各
々２７９ｍｌを１分間定速で添加し、ハロゲン化銀核の
生成を行った。(A-3 solution) Ossein gelatin 38.0 g Potassium bromide 11.7 g 34.0 L with water (B-3 solution) Silver nitrate 810.0 g with water 3815 ml (C-3 solution) Potassium bromide 567 0.315 g with water 3815 ml (D-3 solution) 163.4 g of ossein gelatin 10% methanol solution of surfactant (EO-1) 5.5 ml 3961 ml with water (E-3 solution) Sulfuric acid (10%) 91.1 ml (F-3 solution) Required amount of 56% acetic acid aqueous solution (G-3 solution) Ammonia water (28%) 105.7 ml (H-3 solution) 10% aqueous solution of potassium hydroxide Required amount described in JP-A-62-160128 Using a stirrer, 3
Solution E-3 was added to solution A-3 which was vigorously stirred at 0 ° C., and then solution B-3 and solution C-3 were added at a constant rate of 279 ml for 1 minute each by the double jet method to obtain silver halide nuclei. Was generated.

【０２１０】その後、Ｄ−３液を添加し、３１分かけて
温度を６０℃に上げ、更にＧ−３液を添加し、Ｈ−３液
でｐＨを９．３に調整し、６．５分間熟成を行った。そ
の後、Ｆ−３液でｐＨを５．８に調整し、その後、残り
のＢ−３液とＣ−３液とをダブルジェット法により３７
分で加速添加し、直ちに常法にて脱塩を行った。Thereafter, the solution D-3 was added, the temperature was raised to 60 ° C. over 31 minutes, the solution G-3 was further added, the pH was adjusted to 9.3 with the solution H-3, and 6.5. Aging was performed for a minute. Then, the pH was adjusted to 5.8 with F-3 solution, and then the remaining B-3 solution and C-3 solution were mixed by the double jet method to 37.
Min, and desalted immediately by a conventional method.

【０２１１】この種乳剤を電子顕微鏡にて観察したとこ
ろ、互いに平行な２枚の双晶面を持つ平均粒径（投影面
積円換算粒径）０．７２μｍ、粒径分布１６％の単分散
平板種乳剤であった。When this seed emulsion was observed with an electron microscope, a monodispersed flat plate having an average grain size (projected area circle-equivalent grain size) of 0.72 μm having two twin planes parallel to each other and a grain size distribution of 16% was obtained. It was a seed emulsion.

【０２１２】〈比較乳剤Ｅｍ−４１の調製〉以下に示す
溶液を用い、比較乳剤（Ｅｍ−４１）を調製した。<Preparation of Comparative Emulsion Em-41> A comparative emulsion (Em-41) was prepared using the following solution.

【０２１３】 （Ａ−４液） オセインゼラチン ５１９．９ｇ 界面活性剤（ＥＯ−１）の１０％メタノール溶液 １．５ｍｌ 種乳剤Ｔ−３ ５．３モル相当 水で １８．０リットル （Ｂ−４液） ３．５Ｎ硝酸銀水溶液 ２７８７ｍｌ （Ｃ−４液） 臭化カリウム １０２０ｇ 沃化カリウム ２９．１ｇ 水で ２５００ｍｌ （Ｄ−４液） 臭化カリウム ６１８．５ｇ 沃化カリウム ８．７ｇ 水で １５００ｍｌ （Ｅ−４液） 臭化カリウム ２０８．３ｇ 水で １０００ｍｌ （Ｆ−４液） ５６％酢酸水溶液 必要量 （Ｇ−４液） 臭化カリウム ６２４．８ｇ 水で １５００ｍｌ （Ｈ−４液） ３．０重量％のゼラチンと沃化銀微粒子（平均粒径０．０５μｍ） から成る微粒子乳剤 ０．６７２モル相当 調製法を以下に示す。(A-4 solution) Ossein gelatin 519.9 g 10% methanol solution of surfactant (EO-1) 1.5 ml Seed emulsion T-3 5.3 mol equivalent 18.0 liters with water (B- 4 solution) 3.5N silver nitrate aqueous solution 2787 ml (solution C-4) potassium bromide 1020 g potassium iodide 29.1 g with water 2500 ml (solution D-4) potassium bromide 618.5 g potassium iodide 8.7 g with water 1500 ml (solution 4) E-4 solution) Potassium bromide 208.3 g Water 1000 ml (F-4 solution) 56% acetic acid aqueous solution Required amount (G-4 solution) Potassium bromide 624.8 g Water 1500 ml (H-4 solution) 3.0 0.672 mol equivalent of a fine grain emulsion composed of gelatin and silver iodide fine grains (average grain size: 0.05 μm) by weight% is described below.

【０２１４】０．２５４モルの沃化カリウムを含む５．
０％のゼラチン溶液９９４２ｍｌに、１０．５９モルの
硝酸銀と１０．５９モルの沃化カリウムを含む水溶液、
各々３０９２ｍｌを３５分間かけて等速添加し、微粒子
を形成した。微粒子形成中の温度は４０℃に制御した。4. containing 0.254 mol of potassium iodide
An aqueous solution containing 10.59 mol of silver nitrate and 10.59 mol of potassium iodide in 9942 ml of 0% gelatin solution,
3092 ml of each was added at a constant speed over 35 minutes to form fine particles. The temperature during the formation of the fine particles was controlled at 40 ° C.

【０２１５】 （Ｋ−４液） 水酸化カリウム１０％水溶液 必要量 反応容器内にＡ−４液を添加し、７５℃にて激しく攪拌
しながら、Ｂ−４液、Ｃ−４液、Ｄ−４液を表７に示し
た組合せに従って同時混合法によって添加を行い、種結
晶を成長させて比較乳剤Ｅｍ−４１を調製した。(Liquid K-4) 10% aqueous solution of potassium hydroxide Required amount Add Liquid A-4 into a reaction vessel and, while stirring vigorously at 75 ° C., Liquid B-4, Liquid C-4, and Liquid D-4. The four liquids were added by the simultaneous mixing method in accordance with the combinations shown in Table 7, and seed crystals were grown to prepare Comparative Emulsion Em-41.

【０２１６】[0216]

【表７】 [Table 7]

【０２１７】ここで、Ｂ−４液、Ｃ−４液、Ｄ−４液の
添加速度は、臨界成長速度を考慮し、添加時間に対して
関数様に変化させ、成長している種粒子以外の小粒子の
発生や、成長粒子間のオストワルド熟成による粒径分布
の劣化が起こらないようにした。Here, the addition rate of Solution B-4, Solution C-4, and Solution D-4 was changed in a function-wise manner with respect to the addition time in consideration of the critical growth rate. The generation of small particles and the deterioration of the particle size distribution due to Ostwald ripening between growing particles were prevented.

【０２１８】結晶成長は、まず第１添加を反応容器内の
溶液温度を７５℃、ｐＡｇを９．４、ｐＨを４．０にコ
ントロールして行った。この第１添加でＢ−４液の６
５．８％を添加した。その後、３０分間で反応容器内の
溶液温度を４０℃に下げ、Ｇ−４液を用いてｐＡｇを１
０．３に調整し、Ｈ−４液を２分間定速で全量を添加
し、直ちに第２添加を行った。第２添加は反応容器内の
溶液温度を４０℃、ｐＡｇを１０．３、ｐＨを４．０に
コントロールして行い、Ｂ−４液の残りを全て添加し
た。ｐＡｇ及びｐＨのコントロールの為、必要に応じて
Ｅ−４液、Ｆ−４液、Ｋ−４液を添加した。粒子形成後
にｐＨを５．０に調整した。The first growth was carried out by controlling the temperature of the solution in the reaction vessel to 75 ° C., the pAg to 9.4, and the pH to 4.0. In the first addition, 6 of solution B-4 was added.
5.8% was added. Thereafter, the temperature of the solution in the reaction vessel was lowered to 40 ° C. in 30 minutes, and pAg was reduced to 1 using solution G-4.
The solution was adjusted to 0.3, the entire amount of the H-4 solution was added at a constant speed for 2 minutes, and the second addition was immediately performed. The second addition was performed while controlling the temperature of the solution in the reaction vessel to 40 ° C., the pAg to 10.3, and the pH to 4.0, and added the rest of the B-4 solution. For control of pAg and pH, E-4 solution, F-4 solution and K-4 solution were added as needed. After particle formation, the pH was adjusted to 5.0.

【０２１９】粒子形成後に、特開平５−７２６５８号に
記載の方法に従い脱塩処理を行い、ゼラチンを加えて分
散した。その後、６０℃にて、ｐＡｇを１．８に調整
し、上記Ｊ−２液のハロゲン化銀量で０．８モル相当量
を１０分で添加し、２０分間熟成した後、前記の限外濾
過Ａの操作を施し、４０℃においてｐＡｇ８．０６、ｐ
Ｈ５．８に調整する以外は同様にして比較乳剤（Ｅｍ−
４１）を調製した。After the formation of the particles, desalting was carried out according to the method described in JP-A-5-72658, and gelatin was added and dispersed. Then, at 60 ° C., the pAg was adjusted to 1.8, 0.8 mol equivalent of the silver halide in the J-2 solution was added in 10 minutes, and the mixture was ripened for 20 minutes. The operation of filtration A was performed, and pAg 8.06, p
Comparative emulsion (Em-
41) was prepared.

【０２２０】この乳剤中のハロゲン化銀粒子を電子顕微
鏡にて観察したところ、粒子個数で９７％が六角平板状
ハロゲン化銀粒子から成り、平均粒径１．７５μｍ、粒
径分布２０％、平均アスペクト比９．５であった。When the silver halide grains in this emulsion were observed with an electron microscope, 97% of the grains were hexagonal tabular silver halide grains, the average grain size was 1.75 μm, the grain size distribution was 20%, and the average grain size was 20%. The aspect ratio was 9.5.

【０２２１】〈比較乳剤Ｅｍ−４２の調製〉比較乳剤Ｅ
ｍ−４１の調製において、脱塩処理の代わりに前記の限
外濾過Ａの操作を施した。その後、６０℃にて、ｐＡｇ
を８．８に調整し、上記Ｊ−３液のハロゲン化銀量で
０．３モル相当量を１０分で添加し、２０分間熟成し、
その後、限外濾過Ａの操作を施し、４０℃においてｐＡ
ｇ８．０６、ｐＨ５．８に調整する以外は同様にして比
較乳剤（Ｅｍ−４２）を調製した。<Preparation of Comparative Emulsion Em-42> Comparative Emulsion E
In the preparation of m-41, the above operation of ultrafiltration A was performed instead of the desalting treatment. Then, at 60 ° C., pAg
Was adjusted to 8.8, 0.3 mol equivalent of the silver halide in the J-3 solution was added in 10 minutes, and the mixture was ripened for 20 minutes.
Thereafter, the operation of ultrafiltration A was performed, and pA
A comparative emulsion (Em-42) was prepared in the same manner except that the pH was adjusted to 8.06 and the pH to 5.8.

【０２２２】〈比較乳剤Ｅｍ−４３の調製〉比較乳剤Ｅ
ｍ−４１の調製において、脱塩処理の代わりに前記の限
外濾過Ａの操作を施した。その後、６０℃にて、ｐＡｇ
を８．８に調整して、前記Ｋ−２液のハロゲン化銀量で
１．８モル相当量を１０分で添加し、２０分間熟成した
後、限外濾過Ａの操作を施し、４０℃においてｐＡｇ
８．０６、ｐＨ５．８に調整する以外は同様にして比較
乳剤（Ｅｍ−４３）を調製した。<Preparation of Comparative Emulsion Em-43> Comparative Emulsion E
In the preparation of m-41, the above operation of ultrafiltration A was performed instead of the desalting treatment. Then, at 60 ° C., pAg
Was adjusted to 8.8, 1.8 mol equivalent of silver halide in the K-2 solution was added in 10 minutes, the mixture was aged for 20 minutes, and then the operation of ultrafiltration A was performed. At pAg
A comparative emulsion (Em-43) was prepared in the same manner except that the pH was adjusted to 8.06 and pH 5.8.

【０２２３】〈本発明乳剤Ｅｍ−４４の調製〉比較乳剤
Ｅｍ−４１の調製において、脱塩処理の代わりに前記の
限外濾過Ａの操作を施した。その後、６０℃にて、ｐＡ
ｇを８．８に調整し、前記Ｋ−２液のハロゲン化銀量で
１．８モル相当量を１０分で添加し、２０分間熟成した
後、前記Ｋ−３液をハロゲン化銀量で０．０３モル相当
量を加えて３分間熟成し、限外濾過Ａの操作を施し、４
０℃においてｐＡｇ８．０６、ｐＨ５．８に調整する以
外は同様にして本発明乳剤（Ｅｍ−４４）を調製した。<Preparation of Emulsion Em-44 of the Present Invention> In the preparation of Comparative Emulsion Em-41, the above-mentioned operation of ultrafiltration A was performed instead of the desalting treatment. Then, at 60 ° C., pA
g was adjusted to 8.8, 1.8 mol equivalent of silver halide in the K-2 solution was added in 10 minutes, and after ripening for 20 minutes, the K-3 solution was added in silver halide amount. 0.03 mol equivalent was added and the mixture was aged for 3 minutes.
An emulsion of the present invention (Em-44) was prepared in the same manner except that the pAg was adjusted to 8.06 and the pH to 5.8 at 0 ° C.

【０２２４】〈本発明乳剤Ｅｍ−４５の調製〉比較乳剤
Ｅｍ−４１の調製において、脱塩処理の代わりに前記の
限外濾過Ａの操作を施した。その後、６０℃にて、ｐＡ
ｇを８．５に調整し、前記Ｋ−２液のハロゲン化銀量で
１．５モル相当量を１０分で添加し、２０分間熟成した
後、前記Ｌ−３液を加えて、１０％水酸化カリウム水溶
液でｐＨを９．５に上げて３分間保持し、その後、１０
％硝酸でｐＨを５．０に戻し、限外濾過Ａの操作を施
し、４０℃においてｐＡｇ８．０６、ｐＨ５．８に調整
する以外は同様にして本発明乳剤（Ｅｍ−４５）を調製
した。<Preparation of Emulsion Em-45 of the Present Invention> In the preparation of the comparative emulsion Em-41, the above-mentioned operation of ultrafiltration A was performed instead of the desalting treatment. Then, at 60 ° C., pA
g was adjusted to 8.5, 1.5 mol equivalent of silver halide in the K-2 solution was added in 10 minutes, and the mixture was aged for 20 minutes. The pH was raised to 9.5 with aqueous potassium hydroxide and maintained for 3 minutes.
The emulsion of the present invention (Em-45) was prepared in the same manner except that the pH was returned to 5.0 with% nitric acid, the operation of ultrafiltration A was performed, and the pAg was adjusted to 8.06 and the pH was adjusted to 5.8 at 40 ° C.

【０２２５】上記乳剤Ｅｍ−４１〜Ｅｍ−４５に含まれ
るハロゲン化銀粒子のハロゲン化銀組成をＸ線回折で確
認したところ、Ｅｍ−４３〜Ｅｍ−４５に含まれるハロ
ゲン化銀粒子は、塩化銀を含有していることが確認され
た。When the silver halide composition of the silver halide grains contained in the emulsions Em-41 to Em-45 was confirmed by X-ray diffraction, the silver halide grains contained in the emulsions Em-43 to Em-45 were found to be chloride chloride. It was confirmed that silver was contained.

【０２２６】乳剤Ｅｍ−４１〜Ｅｍ−４５を用いて実施
例１と同様に多層カラー感光材料試料１４１〜１４５を
作製し、評価した。結果を表８に示す。Using the emulsions Em-41 to Em-45, multilayer color light-sensitive material samples 141 to 145 were prepared and evaluated in the same manner as in Example 1. Table 8 shows the results.

【０２２７】[0227]

【表８】 [Table 8]

【０２２８】表８から本発明の乳剤Ｅｍ−４４及びＥｍ
−４５を用いた試料１４４及び１４５は、比較乳剤Ｅｍ
−４１〜Ｅｍ−４３を用いた試料１４１〜１４３に比べ
て、優れた感度、粒状性を示した。From Table 8, it can be seen that the emulsions Em-44 and Em of the present invention were obtained.
Samples 144 and 145 using −45 were compared with Comparative Emulsion Em
As compared with Samples 141 to 143 using -41 to Em-43, excellent sensitivity and granularity were exhibited.

【０２２９】実施例６ 〈比較乳剤Ｅｍ−５１の調製〉実施例１における比較乳
剤Ｅｍ−１の調製において、Ｂ−２液、Ｃ−２液、Ｄ−
２液の添加、及び、ｐＨ、ｐＡｇの制御を表９に示すよ
うに制御し、粒子形成後でかつ脱塩前に、前記Ｋ−３液
をハロゲン化銀量で０．０５モル相当量を加えて５分熟
成する以外は同様にして、比較乳剤 （Ｅｍ−５１）を
調製した。Example 6 <Preparation of Comparative Emulsion Em-51> In the preparation of Comparative Emulsion Em-1 in Example 1, solutions B-2, C-2 and D-
The addition of the two solutions and the control of pH and pAg were controlled as shown in Table 9, and after the grain formation and before desalting, the K-3 solution was adjusted to 0.05 mol equivalent of silver halide. In addition, a comparative emulsion (Em-51) was prepared in the same manner except that ripening was performed for 5 minutes.

【０２３０】[0230]

【表９】 [Table 9]

【０２３１】この乳剤中のハロゲン化銀粒子を電子顕微
鏡にて観察したところ、平均粒径１．３５μｍ、粒径分
布１１％であり、ハロゲン化銀粒子表面が（１１１）面
と（１００）面とで構成された十四面体双晶ハロゲン化
銀粒子であり、粒子個数の９０％を占めていた。その主
要表面は（１１１）面であり、全ハロゲン化銀粒子表面
の８０％を占めていた。Observation of the silver halide grains in this emulsion by an electron microscope revealed that the average grain size was 1.35 μm and the grain size distribution was 11%, and the silver halide grains had (111) and (100) faces. And constituted 90% of the number of grains. Its major surface was the (111) plane, which accounted for 80% of the total silver halide grain surface.

【０２３２】〈比較乳剤Ｅｍ−５２の調製〉比較乳剤Ｅ
ｍ−５１の調製において、Ｋ−３液の添加後でかつ脱塩
前に特願平９−３４９４２１号に記載の下記化合物ａを
ハロゲン化銀１モル当たり４．５×１０-4モル添加し、
ｐＨを９．５に上げて５分間保持し、その後ｐＨを５．
８に戻す以外は同様にして比較乳剤（Ｅｍ−５２）を調
製した。<Preparation of Comparative Emulsion Em-52> Comparative Emulsion E
In the preparation of m-51, after the addition of the K-3 solution and before desalting, the following compound a described in Japanese Patent Application No. 9-349421 was added in an amount of 4.5 × 10 -4 mol per mol of silver halide. ,
Raise pH to 9.5 and hold for 5 minutes, then increase pH to 5.
Comparative emulsion (Em-52) was prepared in the same manner except that the composition was returned to 8.

【０２３３】〈比較乳剤Ｅｍ−５３の調製〉比較乳剤Ｅ
ｍ−５１の調製において、粒子形成後に脱塩処理を行う
代わりに、前記の限外濾過Ａの操作を施した。その後、
６０℃にて、ｐＡｇを８．８に調整し、前記Ｋ−２液の
ハロゲン化銀量で１．８モル相当量を１０分で添加し、
２０分間熟成し、前記Ｋ−３液をハロゲン化銀量で０．
０５モル相当量を加えて５分熟成した後、限外濾過Ａの
操作を施し、４０℃においてｐＡｇ８．０６、ｐＨ５．
８に調整することにより、比較乳剤（Ｅｍ−５３）を調
製した。<Preparation of Comparative Emulsion Em-53> Comparative Emulsion E
In the preparation of m-51, the above-mentioned operation of ultrafiltration A was performed instead of performing desalting treatment after particle formation. afterwards,
At 60 ° C., pAg was adjusted to 8.8, and 1.8 mol equivalent of silver halide in the K-2 solution was added in 10 minutes.
After ripening for 20 minutes, the K-3 solution was added in an amount of 0.
After adding an equivalent amount of 05 mol and aging for 5 minutes, the operation of ultrafiltration A was performed, and pAg 8.06, pH 5.0 at 40 ° C.
By adjusting to 8, a comparative emulsion (Em-53) was prepared.

【０２３４】〈本発明乳剤Ｅｍ−５４の調製〉比較乳剤
Ｅｍ−５１の調製において、粒子形成後に脱塩処理を行
う代わりに、前記の限外濾過Ａの操作を施した。その
後、６０℃にて、ｐＡｇを８．８に調整し、前記Ｋ−２
液のハロゲン化銀量で１．８モル相当量を１０分で添加
し、２０分間熟成し、その後、限外濾過Ａの操作を施
し、４０℃においてｐＡｇ８．０６、ｐＨ５．８に調整
した。更に、化合物ａをハロゲン化銀１モル当たり４．
５×１０-4モル添加し、ｐＨを９．５に上げて５分間保
持し、その後ｐＨを５．８に戻し、その後、限外濾過Ａ
の操作を施し、４０℃においてｐＡｇ８．０６、ｐＨ
５．８に調整する以外は同様にして、本発明乳剤（Ｅｍ
−５４）を調製した。<Preparation of Emulsion Em-54 of the Present Invention> In the preparation of Comparative Emulsion Em-51, the above-mentioned operation of ultrafiltration A was performed instead of performing desalting treatment after grain formation. Then, at 60 ° C., the pAg was adjusted to 8.8,
A solution equivalent to 1.8 mol of silver halide in the liquid was added in 10 minutes, ripened for 20 minutes, and then subjected to ultrafiltration A to adjust the pAg to 8.06 and the pH to 5.8 at 40 ° C. Further, compound a was added in an amount of 4.
5 × 10 -4 mol was added and the pH was raised to 9.5 and held for 5 minutes, after which the pH was returned to 5.8 and then ultrafiltration A
At 40 ° C., pAg 8.06, pH
The emulsion of the present invention (Em
-54) was prepared.

【０２３５】〈本発明乳剤Ｅｍ−５５の調製〉比較乳剤
Ｅｍ−５１の調製において、粒子形成後に脱塩処理を行
う代わりに、前記の限外濾過Ａの操作を施した。その
後、６０℃にて、ｐＡｇを８．８に調整して、前記Ｋ−
２液のハロゲン化銀量で１．８モル相当量を１０分で添
加し、２０分間熟成した後、限外濾過Ａの操作を施し、
４０℃においてｐＡｇ８．０６、ｐＨ５．８に調整し
た。更に、特願平９−３４９４２１号に記載の下記化合
物ｂをハロゲン化銀１モル当たり６．０×１０-4モル添
加し、ｐＨを９．５に上げて５分間保持し、その後ｐＨ
を５．８に戻し、その後、限外濾過Ａの操作を施し、４
０℃においてｐＡｇ８．０６、ｐＨ５．８に調整する以
外は同様にして、本発明乳剤（Ｅｍ−５５）を調製し
た。<Preparation of Emulsion Em-55 of the Present Invention> In the preparation of comparative emulsion Em-51, the above-mentioned operation of ultrafiltration A was performed instead of performing desalting treatment after grain formation. Then, at 60 ° C., the pAg was adjusted to 8.8, and the K-
1.8 mol equivalent of silver halide in two liquids was added in 10 minutes, and after aging for 20 minutes, the operation of ultrafiltration A was performed.
At 40 ° C., the pAg was adjusted to 8.06 and pH 5.8. Further, the following compound b described in Japanese Patent Application No. 9-349421 was added at 6.0 × 10 -4 mol per mol of silver halide, the pH was raised to 9.5 and maintained for 5 minutes.
Was returned to 5.8, and then the operation of ultrafiltration A was performed.
An emulsion of the present invention (Em-55) was prepared in the same manner except that the pAg was adjusted to 8.06 and the pH to 5.8 at 0 ° C.

【０２３６】[0236]

【化７】 Embedded image

【０２３７】上記乳剤Ｅｍ−５１〜Ｅｍ−５５に含まれ
るハロゲン化銀粒子のハロゲン化銀組成をＸ線回折で確
認したところ、Ｅｍ−５３〜Ｅｍ−５５に含まれるハロ
ゲン化銀粒子は、塩化銀を含有していることが確認され
た。When the silver halide composition of the silver halide grains contained in the emulsions Em-51 to Em-55 was confirmed by X-ray diffraction, the silver halide grains contained in the emulsions Em-53 to Em-55 showed that It was confirmed that silver was contained.

【０２３８】乳剤Ｅｍ−５１〜Ｅｍ−５５を用いて実施
例１と同様に多層カラー感光材料試料１５１〜１５５を
作製し、評価した。評価結果を表１０に示す。Using the emulsions Em-51 to Em-55, multilayer color light-sensitive material samples 151 to 155 were produced and evaluated in the same manner as in Example 1. Table 10 shows the evaluation results.

【０２３９】[0239]

【表１０】 [Table 10]

【０２４０】表１０から本発明の乳剤Ｅｍ−５４及びＥ
ｍ−５５を用いた試料１５４及び１５５は、比較乳剤Ｅ
ｍ−５１〜Ｅｍ−５３を用いた試料１５１〜１５３に比
べて、優れた感度、粒状性を示した。Table 10 shows that the emulsions Em-54 and E of the present invention
Samples 154 and 155 using m-55 are comparative emulsion E
As compared with Samples 151 to 153 using m-51 to Em-53, excellent sensitivity and granularity were exhibited.

【０２４１】実施例７ 〈比較乳剤Ｅｍ−６１の調製〉実施例５における比較乳
剤Ｅｍ−４１の調製において、Ａ−４液に代えて下記Ａ
−５液を用い、ハロゲン化銀粒子成長中のｐＨを６．０
に維持し、粒子形成後でかつ脱塩前に、前出のＫ−３液
をハロゲン化銀量で０．０４モル相当量を加えて５分熟
成する以外は同様にして比較乳剤（Ｅｍ−６１）を調製
した。Example 7 <Preparation of Comparative Emulsion Em-61> In the preparation of Comparative Emulsion Em-41 in Example 5, the following A was used in place of Solution A-4.
-5 solution and the pH during the growth of silver halide grains was 6.0.
Comparative emulsion (Em-E) was prepared in the same manner except that after the grain formation and before desalting, the above K-3 solution was ripened for 5 minutes by adding an amount equivalent to 0.04 mol of silver halide. 61) was prepared.

【０２４２】 （Ａ−５液） オセインゼラチン ５１９．９ｇ 界面活性剤（ＥＯ−１）の１０％メタノール溶液 ７．２ｍｌ 種乳剤Ｔ−３ ５．３モル相当 水で １８．０リットル この乳剤中のハロゲン化銀粒子を電子顕微鏡にて観察し
たところ、平均粒径１．５５μｍ、粒径分布１６％、平
均アスペクト比８．０の六角平板状単分散ハロゲン化銀
粒子が粒子個数で９０％であり、側面に（１００）面と
（１１１）面とを有していた。(A-5 solution) Ossein gelatin 519.9 g 10% methanol solution of surfactant (EO-1) 7.2 ml Seed emulsion T-3 5.3 mol equivalent 18.0 liters with water in this emulsion Observation of the silver halide grains by an electron microscope showed that hexagonal tabular monodispersed silver halide grains having an average grain size of 1.55 μm, a grain size distribution of 16%, and an average aspect ratio of 8.0 were 90% in terms of the number of grains. There were (100) and (111) planes on the side.

【０２４３】〈比較乳剤Ｅｍ−６２の調製〉比較乳剤Ｅ
ｍ−６１の調製において、Ｋ−３液の添加後でかつ脱塩
前に前出の化合物Ａをハロゲン化銀１モル当たり４．５
×１０-4モル添加し、ｐＨを９．５に上げて５分間保持
し、その後ｐＨを５．８に戻す以外は同様にして比較乳
剤（Ｅｍ−６２）を調製した。<Preparation of Comparative Emulsion Em-62> Comparative Emulsion E
In the preparation of m-61, after the addition of K-3 solution and before desalting, the above-mentioned compound A was added to 4.5 parts per mole of silver halide.
× 10 -4 mol was added, the pH was raised to 9.5 and maintained for 5 minutes, and then a comparative emulsion (Em-62) was prepared in the same manner except that the pH was returned to 5.8.

【０２４４】〈比較乳剤Ｅｍ−６３の調製〉比較乳剤Ｅ
ｍ−６１の調製において、粒子形成後に脱塩処理を行う
代わりに、前記の限外濾過Ａの操作を施した。その後、
６０℃にて、ｐＡｇを８．８に調整し、前記Ｋ−２液の
ハロゲン化銀量で１．８モル相当量を１０分で添加し、
２０分間熟成し、前記Ｋ−３液をハロゲン化銀量で０．
０５モル相当量を加えて５分熟成した後、限外濾過Ａの
操作を施し、４０℃においてｐＡｇ８．０６、ｐＨ５．
８に調整することにより比較乳剤（Ｅｍ−６３）を調製
した。<Preparation of Comparative Emulsion Em-63> Comparative Emulsion E
In the preparation of m-61, the above-mentioned operation of ultrafiltration A was performed instead of performing desalting treatment after particle formation. afterwards,
At 60 ° C., pAg was adjusted to 8.8, and 1.8 mol equivalent of silver halide in the K-2 solution was added in 10 minutes.
After ripening for 20 minutes, the K-3 solution was added in an amount of 0.
After adding an equivalent amount of 05 mol and aging for 5 minutes, the operation of ultrafiltration A was performed, and pAg 8.06, pH 5.0 at 40 ° C.
By adjusting to 8, a comparative emulsion (Em-63) was prepared.

【０２４５】〈本発明乳剤Ｅｍ−６４の調製〉比較乳剤
Ｅｍ−６１の調製において、粒子形成後に脱塩処理を行
う代わりに、前記の限外濾過Ａの操作を施した。その
後、６０℃にて、ｐＡｇを８．８に調整し、前記Ｋ−２
液のハロゲン化銀量で１．８モル相当量を１０分で添加
し、２０分間熟成した後、限外濾過Ａの操作を施し、４
０℃においてｐＡｇ８．０６、ｐＨ５．８に調整した。
更に、化合物Ａをハロゲン化銀１モル当たり４．５×１
０-4モル添加し、ｐＨを９．５に上げて５分間保持し、
その後ｐＨを５．８に戻した後、限外濾過Ａの操作を施
し、４０℃においてｐＡｇ８．０６、ｐＨ５．８に調整
する以外は同様にして、本発明乳剤（Ｅｍ−６４）を調
製した。<Preparation of Emulsion Em-64 of the Present Invention> In the preparation of Comparative Emulsion Em-61, the above-mentioned operation of ultrafiltration A was performed instead of performing desalting treatment after grain formation. Then, at 60 ° C., the pAg was adjusted to 8.8,
The solution was added in an amount of 1.8 mol in terms of silver halide in 10 minutes, and after aging for 20 minutes, the operation of ultrafiltration A was carried out.
The pH was adjusted to 8.06 and pH 5.8 at 0 ° C.
Further, Compound A was added to 4.5 × 1 per mol of silver halide.
0-4 mol was added, the pH was raised to 9.5 and held for 5 minutes,
Thereafter, after the pH was returned to 5.8, the operation of ultrafiltration A was performed, and an emulsion of the present invention (Em-64) was prepared in the same manner except that the pAg was adjusted to 8.06 and the pH was adjusted to 5.8 at 40 ° C. .

【０２４６】〈本発明乳剤Ｅｍ−６５の調製〉比較乳剤
Ｅｍ−６１の調製において、粒子形成後に脱塩処理を行
う代わりに、前記の限外濾過Ａの操作を施した。その
後、６０℃にて、ｐＡｇを８．８に調整し、前記Ｋ−２
液のハロゲン化銀量で１．８モル相当量を１０分で添加
し、２０分間熟成した後、限外濾過Ａの操作を施し、４
０℃においてｐＡｇ８．０６、ｐＨ５．８に調整した。
更に、化合物Ｂをハロゲン化銀１モル当たり６．０×１
０-4モル添加し、ｐＨを９．５に上げて５分間保持し、
その後ｐＨを５．８に戻し、その後、限外濾過Ａの操作
を施し、４０℃においてｐＡｇ８．０６、ｐＨ５．８に
調整する以外は同様にして本発明乳剤（Ｅｍ−６５）を
調製した。<Preparation of Emulsion Em-65 of the Present Invention> In the preparation of comparative emulsion Em-61, the above-mentioned operation of ultrafiltration A was performed instead of performing desalting treatment after grain formation. Then, at 60 ° C., the pAg was adjusted to 8.8,
The solution was added in an amount of 1.8 mol in terms of silver halide in 10 minutes, and after aging for 20 minutes, the operation of ultrafiltration A was carried out.
The pH was adjusted to 8.06 and pH 5.8 at 0 ° C.
Further, Compound B was mixed with 6.0 × 1 per mol of silver halide.
0-4 mol was added, the pH was raised to 9.5 and held for 5 minutes,
Thereafter, the pH was returned to 5.8, and thereafter, the operation of ultrafiltration A was performed, and an emulsion of the present invention (Em-65) was prepared in the same manner except that the pAg was adjusted to 8.06 and the pH was adjusted to 5.8 at 40 ° C.

【０２４７】上記乳剤Ｅｍ−６１〜Ｅｍ−６５に含まれ
るハロゲン化銀粒子のハロゲン化銀組成をＸ線回折で確
認したところ、Ｅｍ−６３〜Ｅｍ−６５に含まれるハロ
ゲン化銀粒子は、塩化銀を含有していることが確認され
た。When the silver halide composition of the silver halide grains contained in the emulsions Em-61 to Em-65 was confirmed by X-ray diffraction, the silver halide grains contained in the emulsions Em-63 to Em-65 showed It was confirmed that silver was contained.

【０２４８】乳剤Ｅｍ−６１〜Ｅｍ−６５を用いて実施
例１と同様に多層カラー感光材料試料１６１〜１６５を
作製し、評価した。結果を表１１に示す。Using the emulsions Em-61 to Em-65, multilayer color photographic material samples 161 to 165 were prepared and evaluated in the same manner as in Example 1. Table 11 shows the results.

【０２４９】[0249]

【表１１】 [Table 11]

【０２５０】表１１から本発明の乳剤Ｅｍ−６４及びＥ
ｍ−６５を用いた試料１６４及び１６５は、比較乳剤Ｅ
ｍ−６１〜Ｅｍ−６３を用いた試料１６１〜１６３に比
べて、優れた感度、粒状性を示した。Table 11 shows that the emulsions Em-64 and E of the present invention
Samples 164 and 165 using m-65 were prepared as Comparative Emulsion E
As compared with Samples 161 to 163 using m-61 to Em-63, excellent sensitivity and granularity were exhibited.

【０２５１】[0251]

【発明の効果】本発明により、感度、粒状性に優れたハ
ロゲン化銀写真乳剤及び、該乳剤を用いたハロゲン化銀
写真感光材料が提供できた。According to the present invention, a silver halide photographic emulsion excellent in sensitivity and granularity and a silver halide photographic material using the emulsion can be provided.

Claims (5)

【特許請求の範囲】[Claims] 【請求項１】 分散媒とハロゲン化銀粒子を含むハロゲ
ン化銀写真乳剤であって、該ハロゲン化銀粒子が最表層
に塩化銀を含有し、かつ該最表層の頂点近傍における臭
化銀含有率をＡ1、最表層の頂点近傍を除いた部分の臭
化銀含有率をＡ2とした時、Ａ1／Ａ2＞１．０であるハ
ロゲン化銀粒子が５０％以上（個数）存在することを特
徴とするハロゲン化銀写真乳剤。1. A silver halide photographic emulsion containing a dispersion medium and silver halide grains, wherein the silver halide grains contain silver chloride in the outermost layer and contain silver bromide in the vicinity of the top of the outermost layer. When the ratio is A 1 and the silver bromide content of the portion excluding the vicinity of the top of the outermost layer is A 2 , 50% or more (number) of silver halide grains satisfying A 1 / A 2 > 1.0 are present. A silver halide photographic emulsion. 【請求項２】 分散媒とハロゲン化銀粒子を含むハロゲ
ン化銀写真乳剤であって、該ハロゲン化銀粒子が最表層
に塩化銀を含有し、かつ該最表層の沃化銀含有率の平均
値をＢ1、ハロゲン化銀粒子の沃化銀含有率の平均値を
Ｂ2とした時、Ｂ1／Ｂ2＞１．０であることを特徴とす
るハロゲン化銀写真乳剤。2. A silver halide photographic emulsion comprising a dispersion medium and silver halide grains, wherein the silver halide grains contain silver chloride in the outermost layer and the average of the silver iodide content of the outermost layer. B 1 value, when the average value of the silver iodide content of the silver halide grains and a B 2, the silver halide photographic emulsion, which is a B 1 / B 2> 1.0. 【請求項３】 分散媒とハロゲン化銀粒子を含むハロゲ
ン化銀写真乳剤であって、該ハロゲン化銀粒子が（１１
１）面と（１００）面とを有し、最表層に塩化銀を含有
し、かつ該最表層の沃化銀含有率を（１１１）面で
Ｃ1、（１００）面でＣ2とした時、Ｃ1／Ｃ2＞１．０で
あるハロゲン化銀粒子が５０％以上（個数）存在するこ
とを特徴とするハロゲン化銀写真乳剤。3. A silver halide photographic emulsion comprising a dispersion medium and silver halide grains, wherein the silver halide grains are (11)
1) and a plane and (100) plane, containing silver chloride in the outermost layer, and C 1 silver iodide content of the outermost layer with (111) plane, and a C 2 at (100) plane A silver halide photographic emulsion characterized in that at least 50% (by number) of silver halide grains satisfying C 1 / C 2 > 1.0 are present. 【請求項４】 ハロゲン化銀粒子が平板状ハロゲン化銀
粒子であることを特徴とする請求項２又は３記載のハロ
ゲン化銀写真乳剤。4. The silver halide photographic emulsion according to claim 2, wherein the silver halide grains are tabular silver halide grains. 【請求項５】 支持体上のハロゲン化銀乳剤層の少なく
とも１層に、請求項１〜４のいずれか１項に記載のハロ
ゲン化銀写真乳剤を含むことを特徴とするハロゲン化銀
写真感光材料。5. A silver halide photographic light-sensitive material comprising a silver halide photographic emulsion according to claim 1 in at least one of the silver halide emulsion layers on a support. material.
JP6564298A 1998-03-16 1998-03-16 Silver halide photographic emulsion and silver halide photographic sensitive material Withdrawn JPH11258720A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP6564298A JPH11258720A (en) 1998-03-16 1998-03-16 Silver halide photographic emulsion and silver halide photographic sensitive material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP6564298A JPH11258720A (en) 1998-03-16 1998-03-16 Silver halide photographic emulsion and silver halide photographic sensitive material

Publications (1)

Publication Number Publication Date
JPH11258720A true JPH11258720A (en) 1999-09-24

Family

ID=13292886

Family Applications (1)

Application Number Title Priority Date Filing Date
JP6564298A Withdrawn JPH11258720A (en) 1998-03-16 1998-03-16 Silver halide photographic emulsion and silver halide photographic sensitive material

Country Status (1)

Country Link
JP (1) JPH11258720A (en)

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