JPH07152102A - Silver halide photographic sensitive material - Google Patents
Silver halide photographic sensitive materialInfo
- Publication number
- JPH07152102A JPH07152102A JP29695993A JP29695993A JPH07152102A JP H07152102 A JPH07152102 A JP H07152102A JP 29695993 A JP29695993 A JP 29695993A JP 29695993 A JP29695993 A JP 29695993A JP H07152102 A JPH07152102 A JP H07152102A
- Authority
- JP
- Japan
- Prior art keywords
- silver halide
- solution
- sensitive material
- emulsion
- silver
- 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.)
- Pending
Links
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は診断能の優れた医療用ハ
ロゲン化銀写真感光材料に関し、詳しくは鮮鋭性および
粒状性を改良し、かつ露光ラチチュードが広いX線用ハ
ロゲン化銀写真感光材料に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a medical silver halide photographic light-sensitive material having excellent diagnostic ability, more specifically, a silver halide photographic light-sensitive material for X-rays having improved sharpness and graininess and a wide exposure latitude. Regarding
【0002】[0002]
【従来の技術】医療用のX線用ハロゲン化銀写真感光材
料においては、生体各部位の撮影にて病巣の早期発見と
誤診を避けるために鮮鋭性が良く、かつ粒状性の優れた
画像が要求される。感光材料の鮮鋭性と粒状性の改良
は、画像の見やすさとその情報量を左右することから診
断能を高めるために極めて重要である。2. Description of the Related Art In medical silver halide photographic light-sensitive materials for X-rays, an image with good sharpness and excellent graininess is obtained in order to avoid early detection and misdiagnosis of lesions by photographing each part of a living body. Required. Improvement of sharpness and graininess of the light-sensitive material is very important for enhancing the diagnostic ability because it affects the visibility of an image and the amount of information.
【0003】一般にX線撮影の最も多い生体部位として
は胃部、胸部及び手足などの骨梁が挙げられるが、これ
らの撮影にて診断能を向上するには低濃度域から高濃度
域にかけて広い露光寛容度(ラチチュード)と、適度な
濃度を有し、画像がつぶれたり飛んだりすることのない
鮮鋭性の優れた画像が必要である。[0003] Generally, the trachea of the stomach, chest, limbs, and the like is mentioned as a living body site where X-rays are most frequently taken, but in order to improve the diagnostic ability in these radiographs, it is wide from a low-concentration region to a high-concentration region. There is a need for an image having excellent exposure latitude (latitude) and moderate density, and having excellent sharpness without the image being crushed or skipped.
【0004】一般的に感光材料の露光ラチチュードを決
めるパラメーターとしてはガンマ(γ)があるが、現在
市販されているX線撮影用感光材料には大別して高γタ
イプ、低γタイプ及び中庸γタイプの3種があって、そ
れぞれ使い分けて用いられている。In general, gamma (γ) is a parameter that determines the exposure latitude of a light-sensitive material, but the commercially available light-sensitive materials for X-ray photography are roughly classified into high γ type, low γ type and moderate γ type. There are three types, each of which is used separately.
【0005】しかしながら、これらのフィルムで高γタ
イプにおいては、優れた鮮鋭性を有する反面、低露光部
画像がつぶれて情報量を少なくする欠点を有し、また低
γタイプでは露光ラチチュードが広いために情報量は優
れるが、鮮鋭性に欠ける欠点を有し、中庸γタイプでは
鮮鋭性、露光ラチチュードともに中程度で特色に欠ける
などそれぞれ一長一短を有しているのが現状である。However, the high γ type of these films has excellent sharpness, but on the other hand, it has a drawback that the image of the low exposed portion is crushed and the amount of information is reduced, and the low γ type has a wide exposure latitude. Although it has excellent information content, it has a drawback that it lacks in sharpness, and the medium γ type has both advantages and disadvantages in that both sharpness and exposure latitude are moderate and lacking in features.
【0006】さらに検診者の体型によってX線の吸収率
が異なってくるため、多人数の集団検診時に各個人毎に
最適な露光量を決定することは非常に困難であった。Further, since the X-ray absorptivity varies depending on the body type of the examiner, it is very difficult to determine the optimum exposure dose for each individual during a mass examination of a large number of people.
【0007】従来よりハロゲン化銀乳剤に対するコント
ラスト、粒状性及び鮮鋭性などの写真性能の向上、改良
には膨大な数の技術が提案されており、例えば特開昭59
-214027号では、特定の現像液を用いて得られるガンマ
(γ)を規定したX線用ハロゲン化銀写真感光材料が提
案されており、さらには特定域のガンマ(γ1〜γ3)
を規定した特開昭61-116346号などが開示されている。A large number of techniques have been proposed in the past for improving and improving photographic performance such as contrast, graininess and sharpness with respect to silver halide emulsions.
No. 214027 proposes a silver halide photographic light-sensitive material for X-rays which defines a gamma (γ) obtained by using a specific developing solution, and further gamma (γ1 to γ3) in a specific range.
Japanese Patent Application Laid-Open No. 61-116346 is disclosed.
【0008】しかしながら、これら技術を含めて従来技
術の多くは、鮮鋭性とラチチュードの両方を同時に改良
し、かつ前述したような生体部位のどの撮影に対しても
診断能を高めることが出来る医療用ハロゲン化銀写真感
光材料を得るまでに至っていないのが現状であった。However, most of the conventional techniques including these techniques are medical ones capable of improving both sharpness and latitude at the same time, and enhancing the diagnostic ability for any imaging of a living body part as described above. The current situation is that a silver halide photographic light-sensitive material has not yet been obtained.
【0009】[0009]
【発明が解決しようとする課題】従って本発明の目的
は、上記従来技術の問題点を解決し、鮮鋭性、粒状性を
改良し、かつ露光ラチチュードが広いX線用ハロゲン化
銀写真感光材料を提供することにある。SUMMARY OF THE INVENTION Therefore, an object of the present invention is to solve the above problems of the prior art, to improve sharpness and graininess, and to provide a silver halide photographic light-sensitive material for X-ray having a wide exposure latitude. To provide.
【0010】[0010]
【課題を解決するための手段】本発明の目的は下記によ
り達成された。The objects of the present invention have been achieved by the following.
【0011】(1)支持体上に少なくとも1層のハロゲン
化銀乳剤層を有するハロゲン化銀写真感光材料におい
て、該乳剤層中のハロゲン化銀粒子が、アスペクト比3
以上で円相当直径が0.5μm以上の平板状粒子、及びアス
ペクト比2以下で球換算粒径が0.2μm以上0.5μm以下の
粒子をそれぞれ1種類以上含有し、かつ全ハロゲン化銀
粒子の平均沃化銀含有率が2.0モル%以下であり、さら
に得られた画像の特性曲線における光学濃度0.3と0.5の
点を結ぶ直線の傾き(γ1)が0.4〜0.7、光学濃度0.5
と1.5の点を結ぶ直線の傾き(γ2)が1.5〜2.0、光学
濃度1.0と2.0を結ぶ直線の傾き(γ3)が2.8〜3.5であ
ることを特徴とするハロゲン化銀写真感光材料。(1) In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, the silver halide grains in the emulsion layer have an aspect ratio of 3
Above, tabular grains having an equivalent circle diameter of 0.5 μm or more and one or more grains each having an aspect ratio of 2 or less and a sphere-converted grain size of 0.2 μm or more and 0.5 μm or less are contained, respectively, and the average iodide of all silver halide grains is contained. The silver halide content is 2.0 mol% or less, and the slope (γ1) of the line connecting the points of optical density 0.3 and 0.5 in the characteristic curve of the obtained image is 0.4 to 0.7, the optical density is 0.5.
A silver halide photographic light-sensitive material characterized in that the slope (γ2) of the line connecting points 1.5 and 1.5 is 1.5 to 2.0, and the slope (γ3) of the line connecting optical densities 1.0 and 2.0 is 2.8 to 3.5.
【0012】(2)支持体上に少なくとも2層以上のハロ
ゲン化銀乳剤層を有するハロゲン化銀写真感光材料にお
いて、支持体から最も離れた乳剤層中のハロゲン化銀粒
子が、アスペクト比3以上で円相当直径が0.5μm以上の
平板状粒子であり、該乳剤層に対して支持体に近い任意
の乳剤層中のハロゲン化銀粒子が、アスペクト比2以下
で球換算粒径が0.2μm以上0.5μm以下の粒子であって、
かつ全ハロゲン化銀粒子の平均沃化銀含有率が2.0モル
%以下であり、さらに該感光材料の特性曲線における光
学濃度0.3と0.5の点を結ぶ直線の傾き(γ1)が0.4〜
0.7で、光学濃度0.5と1.5の点を結ぶ直線の傾き(γ
2)が1.5〜2.0、光学濃度1.0と2.0を結ぶ直線の傾き
(γ3)が2.8〜3.5であることを特徴とするハロゲン化
銀写真感光材料。 (3)アスペクト比3以上で円相当直径が0.5μm以上の平
板状粒子の変動係数が25%以上であり、かつアスペクト
比2以下で球換算粒径が0.2μm以上0.5μm以下の粒子の
変動係数が20%以下であることを特徴とする(1)項及び
(2)項記載のハロゲン化銀写真感光材料。(2) In a silver halide photographic light-sensitive material having at least two silver halide emulsion layers on a support, the silver halide grains in the emulsion layer farthest from the support have an aspect ratio of 3 or more. Is a tabular grain having a circle-equivalent diameter of 0.5 μm or more, and the silver halide grain in any emulsion layer near the support with respect to the emulsion layer has an aspect ratio of 2 or less and a sphere-converted grain size of 0.2 μm or more Particles of 0.5 μm or less,
The average silver iodide content of all silver halide grains is 2.0 mol% or less, and the slope (γ1) of the straight line connecting the optical density points 0.3 and 0.5 in the characteristic curve of the light-sensitive material is 0.4 to
At 0.7, the slope of the line connecting the points of optical density 0.5 and 1.5 (γ
2) The silver halide photographic light-sensitive material is characterized in that the gradient (γ3) of the straight line connecting the optical densities of 1.0 and 2.0 is 2.8 to 3.5. (3) Fluctuation of tabular grains with an aspect ratio of 3 or more and circle equivalent diameter of 0.5 μm or more with a variation coefficient of 25% or more, and with an aspect ratio of 2 or less and a sphere-converted particle size of 0.2 μm or more and 0.5 μm or less The coefficient is less than 20% (1) and
A silver halide photographic light-sensitive material according to the item (2).
【0013】以下、本発明を詳述する。 本発明に用いられる2種のハロゲン化銀粒子のうちの一
方は、アスペクト比(円相当直径/粒子厚みの比)が3
以上、好ましくは5〜8の粒子で、円相当直径は0.5μm
以上、好ましくは0.8μm〜2.0μmの平板状粒子である。The present invention will be described in detail below. One of the two kinds of silver halide grains used in the present invention has an aspect ratio (ratio of equivalent circle diameter / grain thickness) of 3
Above, preferably 5-8 particles, equivalent circle diameter 0.5μm
As described above, tabular grains having a size of 0.8 μm to 2.0 μm are preferable.
【0014】他の一方はアスペクト比2以下、好ましく
は1〜1.5の粒子で、球換算粒径が0.2μm以上0.5μm以
下、好ましくは0.3μm以上0.4μm以下の粒子である。The other one is a particle having an aspect ratio of 2 or less, preferably 1 to 1.5, and a sphere-converted particle diameter of 0.2 μm or more and 0.5 μm or less, preferably 0.3 μm or more and 0.4 μm or less.
【0015】本発明において円相当直径とは、粒子の投
影像を同面積の円像に換算したときの直径を言い、粒子
厚さとは、平板状粒子の互いに対向する2つの主平面間
の距離を言う。粒子の投影面積は、この粒子面積の和か
ら求めることができる。In the present invention, the equivalent circle diameter means a diameter when a projected image of a grain is converted into a circular image having the same area, and the grain thickness means a distance between two principal planes of tabular grains facing each other. Say The projected area of a grain can be calculated from the sum of the grain areas.
【0016】全投影面積及び粒子直径を求めるための投
影面積は、いずれも粒子の重なりが生じない程度に試料
台上に分布されたハロゲン化銀結晶サンプルを、電子顕
微鏡で1万倍〜5万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って
得ることができる(測定個数は無差別に1000個以上ある
こととする。)。The total projected area and the projected area for obtaining the grain diameter are 10,000 times to 50,000 times with an electron microscope for a silver halide crystal sample distributed on the sample stage to the extent that grains do not overlap. It can be obtained by taking a magnified image twice and measuring the particle diameter on the print or the area at the time of projection (the number of measurement is indiscriminately 1000 or more).
【0017】粒子の厚さは電子顕微鏡によって試料を斜
めから観察することにより得ることができる。本発明に
おいて球換算粒径とは、各粒子を同体積の球に換算した
ときの直径である。粒子の体積は上記の方法で得られた
粒子投影面積及び粒子厚さから求めることができる。The thickness of the particles can be obtained by observing the sample obliquely with an electron microscope. In the present invention, the sphere-converted particle diameter is a diameter when each particle is converted into a sphere having the same volume. The grain volume can be determined from the grain projected area and grain thickness obtained by the above method.
【0018】本発明の特に好ましい態様は、アスペクト
比3以上で円相当直径0.5μm以上の平板状粒子の変動係
数が25%以上、好ましくは25%〜35%であり、かつアス
ペクト比2以下で球換算粒径が0.2μm以上0.5μm以下の
粒子の変動係数が20%以下、好ましくは10%〜15%であ
る。In a particularly preferred embodiment of the present invention, the variation coefficient of tabular grains having an aspect ratio of 3 or more and a circle equivalent diameter of 0.5 μm or more is 25% or more, preferably 25% to 35%, and an aspect ratio of 2 or less. The variation coefficient of particles having a sphere-converted particle size of 0.2 μm or more and 0.5 μm or less is 20% or less, preferably 10% to 15%.
【0019】本発明において、変動係数とは、下記式によ
って示される。In the present invention, the coefficient of variation is expressed by the following equation.
【0020】 (粒径標準偏差)/(平均粒径)×100=(変動係数)(%) ここに粒径測定方法は前述の円相当直径測定方法に従う
ものとし、平均粒径は単純平均とする。(Particle size standard deviation) / (average particle size) × 100 = (coefficient of variation) (%) Here, the particle size measurement method is based on the above circle equivalent diameter measurement method, and the average particle size is a simple average. To do.
【0021】(平均粒径)=Σdini/Σni 本発明に用いられる乳剤を得る方法としては、種粒子を
含むゼラチン溶液中に水溶性銀塩溶液と水溶性ハライド
溶液をpAg及びpHの制御下、ダブルジェット法によって
得る方法があり、このような手段を用いることができ
る。(Average particle size) = Σdini / Σni As a method for obtaining the emulsion used in the present invention, a gelatin solution containing seed particles is treated with a water-soluble silver salt solution and a water-soluble halide solution under the control of pAg and pH. There is a method of obtaining by the double jet method, and such means can be used.
【0022】添加速度の決定に当たっては特開昭54-485
21号、同58-49938号を参考することができる。In determining the addition rate, Japanese Patent Laid-Open No. 54-485
21 and 58-49938 can be referred to.
【0023】本発明に用いられるハロゲン化銀乳剤のハ
ロゲン化銀組成は、沃化銀を2.0モル%以下、好ましく
は2.0〜0.05モル%含有する沃臭化銀、沃塩臭化銀のい
ずれのハロゲン化銀を用いてもよい。The silver halide composition of the silver halide emulsion used in the present invention may be silver iodobromide or silver iodochlorobromide containing 2.0 mol% or less of silver iodide, preferably 2.0 to 0.05 mol%. Silver halide may be used.
【0024】また粒子内のハロゲン分布に関しては、均
一構造でも層状構造(コア/シェル構造)をなしていて
もよい。Regarding the halogen distribution in the grains, it may have a uniform structure or a layered structure (core / shell structure).
【0025】本発明に使用できるハロゲン化銀写真乳剤
は、酸性法、中性法及びアンモニア法等のいずれの方法
をとってもよいが、可溶性銀塩と可溶性ハロゲン塩を反
応させる形式としてはダブルジェット法(同時混合法)
を用いることが好ましい。The silver halide photographic emulsion which can be used in the present invention may take any method such as an acidic method, a neutral method and an ammonia method, but a double jet method is used as a method of reacting a soluble silver salt and a soluble halogen salt. (Simultaneous mixing method)
Is preferably used.
【0026】同時混合法の一つの形式としてハロゲン化
銀の生成する液相中のpAgを一定に保つ方法即ち、いわ
ゆるコントロールド・ダブルジェット法を用いることも
できる。この方法によると結晶形が規則的で、粒子サイ
ズが均一に近いハロゲン化銀乳剤が得られる。As one form of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is formed constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.
【0027】また本発明においては微細な沃化銀粒子
(以下、「微粒子」という。)を供給することによる粒
子形成工程を有していてもよい。微粒子の粒子サイズは
ヨードイオンの供給速度を支配するため、その好ましい
粒子サイズはホストのハロゲン化銀粒子のサイズやハロ
ゲン組成によって変わるが、平均球相当直径が0.3μm以
下のものが用いられる。より好ましくは0.1μm以下であ
る。微粒子がホスト粒子上に再結晶化によって積層する
ためには、この微粒子の粒子サイズはホスト粒子の球相
当直径より小さいことが望ましく、さらに好ましくは、
この球相当直径の1/10以下である。微粒子のハロゲン
組成は95モル%以上の沃化銀含量を有しており、好まし
くは純沃化銀である。Further, the present invention may have a grain forming step by supplying fine silver iodide grains (hereinafter referred to as "fine grains"). Since the grain size of fine grains controls the supply rate of iodine ions, the preferable grain size varies depending on the size of the silver halide grains of the host and the halogen composition, but those having an average equivalent spherical diameter of 0.3 μm or less are used. More preferably, it is 0.1 μm or less. In order for the fine particles to be laminated on the host particles by recrystallization, the particle size of the fine particles is preferably smaller than the equivalent spherical diameter of the host particles, and more preferably,
It is 1/10 or less of the equivalent diameter of this sphere. The halogen composition of the fine grains has a silver iodide content of 95 mol% or more, and is preferably pure silver iodide.
【0028】本発明に係るハロゲン化銀乳剤は、バイン
ダーとしてハロゲン化銀を包むための種々の親水性コロ
イドが用いられる。この目的のためにはゼラチンをはじ
めとして例えばポリビニルアルコール、ポリアクリルア
ミドなどの合成ポリマーや、コロイド状アルブミン、ポ
リサッカライド、セルローズ誘導体などの写真用バイン
ダーが用いられてよい。In the silver halide emulsion according to the present invention, various hydrophilic colloids for wrapping silver halide are used as a binder. For this purpose, gelatin as well as synthetic polymers such as polyvinyl alcohol and polyacrylamide, and photographic binders such as colloidal albumin, polysaccharides and cellulose derivatives may be used.
【0029】本発明の実施に際して用いられるハロゲン
化銀乳剤は、ハロゲン化銀粒子の成長の終了後に適当な
方法によって可溶性塩類を除去して化学増感に適するpA
gイオン濃度にすることができる。可溶性塩類を除去す
るための凝集法やヌードル水洗法などは、リサーチ・デ
ィスクロージャー(RD).17643記載の方法を用いてもよ
く、好ましい水洗法としては例えば特公昭35-16086号記
載のスルホン酸基を含む芳香族炭化水素系アルデヒド樹
脂を用いる方法、又は特開昭63-158644号記載の高分子
凝集剤である例示G-3、G-8などを用いる脱塩法を挙
げることができる。The silver halide emulsion used in the practice of the present invention has a pA suitable for chemical sensitization by removing soluble salts by an appropriate method after the growth of silver halide grains is completed.
Can be g-ion concentration. The coagulation method and the noodle washing method for removing soluble salts may be the method described in Research Disclosure (RD) .17643, and a preferable washing method is, for example, a sulfonic acid group described in JP-B-35-16086. And a desalting method using a polymer flocculant such as Exemplified G-3 and G-8 described in JP-A-63-158644.
【0030】本発明は、得られた画像の光学濃度(D)
及び露光量(logE)の座標軸単位長の等しい直角座標
系上の特性曲線において、光学濃度0.3と0.5の点を結ぶ
直線の傾き(γ1)が0.4〜0.7、光学濃度0.5と1.5の点
を結ぶ直線の傾き(γ2)が1.5〜2.0、光学濃度1.0と
2.0を結ぶ直線の傾き(γ3)が2.8〜3.5であることを
特徴とする。The present invention relates to the optical density (D) of the obtained image.
And the characteristic curve on the rectangular coordinate system with the same unit length of the coordinate axis of the exposure dose (logE), the slope (γ1) of the line connecting the points of optical density 0.3 and 0.5 is 0.4 to 0.7, and the point of optical density 0.5 and 1.5 is connected. The slope of the straight line (γ2) is 1.5 to 2.0 and the optical density is 1.0
It is characterized in that the slope (γ3) of the straight line connecting 2.0 is 2.8 to 3.5.
【0031】本発明において前記特性曲線上のベース
(支持体)濃度+0.3の濃度の点と、ベース(支持体)
濃度+0.5の濃度の点を結んだ直線の傾きを(γ1)と
して表し、同様にベース(支持体)濃度+0.5の濃度の
点とベース(支持体)濃度+1.5の濃度の点を結んだ直
線の傾きを(γ2)、ベース(支持体)濃度+1.0の濃
度の点とベース(支持体)濃度+2.0の濃度の点を結ん
だ直線の傾きを(γ3)として表す。In the present invention, the point of the density of the base (support) density + 0.3 on the characteristic curve, and the base (support)
The slope of the line connecting the density points of density +0.5 is expressed as (γ1), and similarly, the point of the density of base (support) +0.5 and the point of the density of base (support) +1.5 The slope of the straight line connecting the two is expressed as (γ2), and the slope of the straight line connecting the base (support) density +1.0 density point and the base (support) density +2.0 density point is expressed as (γ3). .
【0032】これらの直線が露光量(logE)軸と交わ
る角度をθとすればγ=tanθを意味する。If the angle at which these straight lines intersect the exposure (logE) axis is θ, then γ = tan θ.
【0033】本発明の実施態様としては、下記に示す現
像処理条件によって処理したときに得られる前記直角座
標上の特性曲線において、(γ1)が0.4〜0.7、(γ
2)が1.5〜2.0、(γ3)が2.8〜3.5であるハロゲン化
銀写真感光材料を得るようにする。As an embodiment of the present invention, (γ1) is 0.4 to 0.7, (γ) in the characteristic curve on the rectangular coordinate obtained when processed under the following development processing conditions.
A silver halide photographic light-sensitive material having 2) of 1.5 to 2.0 and (γ3) of 2.8 to 3.5 is obtained.
【0034】<処理条件>下記現像液-1及び定着液-1
を用いて、下記の工程に従いローラー搬送型自動現像機
で処理する。<Processing conditions> The following developer-1 and fixer-1
Is processed in a roller-conveying type automatic developing machine according to the following steps.
【0035】 現像液-1 Part-A(12リットル仕上げ) 水酸化カリウム 450g 亜硫酸カリウム(50%溶液) 2280g ジエチレンテトラアミン5酢酸 120g 重炭酸水素ナトリウム 132g 5-メチルベンゾトリアゾール 1.2g 1-フェニル-5-メルカプトテトラゾール 0.2g ハイドロキノン 340g 水を加えて 5000mlに仕上げる Part-B(12リットル仕上げ用) 氷酢酸 170g トリエチレングリコール 185g 1-フェニル-3-ピラゾリドン 22g 5-ニトロインダゾール 0.4g Part-C(12リットル仕上げ用) グルタルアルデヒド重亜硫酸塩 180g スターター 氷酢酸 120g 臭化カリウム 225g 水を加えて 1000mlに仕上げる 現像液の調製は水約5リットルにPart-A、Part-B、Part-
Cを同時添加し、撹拌溶解しながら水を加え12リットル
に仕上げ氷酢酸でpHを10.40に調整する。これを現像補
充液として、この現像補充液に対して前記のスターター
を20ml/l添加しpHを10.26に調整し使用液とする。Developer-1 Part-A (12 liter finish) Potassium hydroxide 450 g Potassium sulfite (50% solution) 2280 g Diethylenetetraamine pentaacetic acid 120 g Sodium hydrogencarbonate 132 g 5-Methylbenzotriazole 1.2 g 1-phenyl-5 -Mercaptotetrazole 0.2g Hydroquinone 340g Add water to finish to 5000ml Part-B (for finishing 12 liters) Glacial acetic acid 170g Triethylene glycol 185g 1-Phenyl-3-pyrazolidone 22g 5-Nitroindazole 0.4g Part-C (12 liters) For finishing) Glutaraldehyde bisulfite 180g Starter Glacial acetic acid 120g Potassium bromide 225g Add water to finish to 1000ml. Prepare the developer with approximately 5 liters of water Part-A, Part-B, Part-
C is added at the same time, water is added while stirring and dissolving to make 12 liter, and pH is adjusted to 10.40 with glacial acetic acid. This is used as a development replenisher, and 20 ml / l of the above starter is added to the development replenisher to adjust the pH to 10.26 to obtain a working solution.
【0036】 定着液-1 Part-A(18リットル仕上げ用) チオ硫酸アンモニウム(70wt/vol%) 6000g 亜硫酸ナトリウム 110g 酢酸ナトリウム・3水塩 450g クエン酸ナトリウム 50g グルコン酸 70g 1-(N,N-ジメチルアミノ)-エチル-5-メルカプトテトラゾール 18g 水を加えて 6000mlに仕上げる Part-B 硫酸アルミニウム 800g 水を加えて 1000mlに仕上げる 定着液の調製は水約5リットルにPart-A、Part-Bを同
時添加し、撹拌溶解しながら水を加え18リットルに仕上
げてから硫酸とNaOHを用いてpHを4.4に調整する。これ
を定着補充液とする。Fixer-1 Part-A (for 18 liter finish) Ammonium thiosulfate (70wt / vol%) 6000g Sodium sulfite 110g Sodium acetate ・ trihydrate 450g Sodium citrate 50g Gluconic acid 70g 1- (N, N-dimethyl) Amino) -ethyl-5-mercaptotetrazole 18g Add water to make 6000ml Part-B Aluminum sulphate 800g Add water to make 1000ml To prepare a fixer, add about 5 liters of Part-A and Part-B at the same time. Then, while stirring and dissolving, water is added to make 18 liter, and then the pH is adjusted to 4.4 using sulfuric acid and NaOH. This is the fixing replenisher.
【0037】処理工程 現像 温度 35℃ 定着 温度 33℃ 水洗 温度 20℃ 乾燥 温度 50℃ 自動現像機SRX-501(コニカ〔株〕製)を用いてDry to Dr
yで45秒処理する。Processing step Development temperature 35 ° C. Fixing temperature 33 ° C. Washing temperature 20 ° C. Drying temperature 50 ° C. Dry to Dr using an automatic processor SRX-501 (manufactured by Konica Corporation)
Process for 45 seconds with y.
【0038】なお、上記条件で処理液組成、処理温度及
び時間は多少の幅があってもよく、又、現像液としてXD-
SR(コニカ〔株〕製)を現像液-1に置き換える以外は全
部上記条件と同様に処理して得られる特性曲線であって
もよい。Under the above conditions, the composition of the processing solution, the processing temperature and the time may vary to some extent.
All the characteristic curves may be obtained by treating under the same conditions as above except that SR (manufactured by Konica Corporation) is replaced with Developer-1.
【0039】露光条件としては、透明支持体の両面に乳
剤層を設けた本発明に係るハロゲン化銀写真感光材料を
濃度傾斜を鏡対称に整合した2枚の光学ウェッジに挟
み、色温度5.400゜Kの光源で両側から同時に、かつ等量
の1/10秒間露光したものである。但し、この条件に限
定されることなく、X線用ハロゲン化銀写真感光材料に
用いられるセンシトメトリー用露光条件であれば使用す
ることができる。As the exposure conditions, the silver halide photographic light-sensitive material according to the present invention having emulsion layers provided on both sides of a transparent support is sandwiched between two optical wedges whose density gradients are mirror-symmetrically aligned, and the color temperature is 5.400 °. It was exposed from both sides of the light source of K at the same time and in the same amount for 1/10 seconds. However, the exposure conditions for sensitometry used for silver halide photographic light-sensitive materials for X-rays can be used without being limited to these conditions.
【0040】本発明に係るハロゲン化銀写真乳剤は、物
理熟成又は化学熟成前後の工程で、各種の写真用添加剤
を用いることができる。In the silver halide photographic emulsion according to the present invention, various photographic additives can be used in the steps before and after physical ripening or chemical ripening.
【0041】このような工程で使用できる化合物として
は例えば、リサーチ・ディスクロージャー(RD)17643、(R
D)18716(1979年11月)及び(RD)308119(1989年12月)に記
載されている各種の化合物が挙げられる。これら3つの
(RD)に記載されている化合物の種類と記載箇所を下記に
掲載した。Examples of the compound that can be used in such a step include Research Disclosure (RD) 17643, (R
D) 18716 (November 1979) and (RD) 308119 (December 1989). These three
The types of compounds described in (RD) and their locations are listed below.
【0042】 添加剤 RD-17643 RD-18716 RD-308119 頁 分類 頁 頁 分類 化学増感剤 23 III 648 右上 996 III 増感色素 23 IV 648〜649 996〜8 IVA 減感色素 23 IV 998 IVB 染料 25〜26 VIII 649〜650 1003 VIII 現像促進剤 29 XXI 648右上 カブリ抑制剤・安定剤 24 IV 649右上 1006〜7 VI 増白剤 24 V 998 V 硬膜剤 26 X 651左 1004〜5 X 界面活性剤 26〜27 XI 650右 1005〜6 XI 可塑剤 27 XII 650右 1006 XII スベリ剤 27 XII マット剤 28 XVI 650右 1008〜9 XVI バインダー 26 XXII 1003〜4 IX 支持体 28 XVII 1009 XVII 本発明のハロゲン化銀写真感光材料に用いられる支持体
としては、上記のRDに記載されているものが挙げられる
が、適当な支持体としてはプラスチックフィルムなど
で、支持体表面は塗布層の接着性をよくするために下引
き層を設けたり、コロナ放電や紫外線照射などが施され
ていてもよい。そして、このように処理された支持体上
の片面あるいは両面に、本発明に係るハロゲン化銀乳剤
を塗布することができる。Additive RD-17643 RD-18716 RD-308119 Page Classification Page Page Classification Chemical sensitizer 23 III 648 Upper right 996 III Sensitizing dye 23 IV 648-649 996-8 IVA Desensitizing dye 23 IV 998 IVB Dye 25 ~ 26 VIII 649 ~ 650 1003 VIII Development accelerator 29 XXI 648 Upper right fog inhibitor / stabilizer 24 IV 649 Upper right 1006-7 VI Whitening agent 24 V 998 V Hardener 26 X 651 Left 1004-5 X Surfactant 26-27 XI 650 Right 1005-6 XI Plasticizer 27 XII 650 Right 1006 XII Sliding Agent 27 XII Matting Agent 28 XVI 650 Right 1008-9 XVI Binder 26 XXII 1003-4 IX Support 28 XVII 1009 XVII Halogenation of the Invention Examples of the support used in the silver photographic light-sensitive material include those described in the above RD, and a suitable support is a plastic film or the like, and the support surface improves the adhesiveness of the coating layer. May be provided with an undercoat layer, or may be subjected to corona discharge or ultraviolet irradiation. The silver halide emulsion of the present invention can be coated on one side or both sides of the support thus treated.
【0043】本発明のハロゲン化銀写真感光材料には、
必要に応じてアンチハレーション層、中間層、フィルタ
ー層などを設けることができる。The silver halide photographic light-sensitive material of the present invention comprises
If necessary, an antihalation layer, an intermediate layer, a filter layer, etc. can be provided.
【0044】医療用X線ラジオグラフィーに本発明を適
用する場合、例えば透過性放射線曝射によって近紫外光
ないし可視光を発生する蛍光体を主成分とする蛍光増感
紙が用いられる。この増感紙を、本発明の乳剤を両面塗
布してなる感光材料両面に密着し露光することが望まし
い。When the present invention is applied to medical X-ray radiography, for example, a fluorescent intensifying screen containing a phosphor as a main component, which emits near-ultraviolet light or visible light upon exposure to penetrating radiation, is used. It is desirable that this intensifying screen is brought into close contact with both sides of a light-sensitive material obtained by coating the emulsion of the present invention on both sides and exposed.
【0045】ここでいう透過性放射線とは、高エネルギ
ーの電磁波であって、X線及びガンマー線を意味する。The penetrating radiation referred to here is an electromagnetic wave of high energy and means X-rays and gamma rays.
【0046】また蛍光増感紙とは、例えばタングステン
酸カルシウムを主とした蛍光成分とする増感紙、或いは
テルビウムで活性化された希土類化合物を主成分とする
蛍光増感紙などをいう。蛍光増感紙としては蛍光成分を
支持体上に均一に塗布したもの、或いは円柱状や円錐状
に塗布したものを用いることができる。特に感度の低い
感光材料を用いる場合、'92 RSNA(北米放射線学会) セ
ッション 868Cで発表されたGerman Karman Karlsruhe N
uclear reserchのマイクロストラクチャー増感紙のよう
に蛍光成分の厚みを増やし、円錐状に塗布することによ
り、増感紙の感度を上げると同時に量子モトルを減らし
て粒状性を良くした蛍光増感紙を使用することが好まし
い。The fluorescent intensifying screen refers to, for example, an intensifying screen mainly containing calcium tungstate as a fluorescent component or a fluorescent intensifying screen mainly containing a rare earth compound activated by terbium. As the fluorescent intensifying screen, a fluorescent component uniformly coated on a support or a cylindrical or conical coating can be used. German Karman Karlsruhe N presented at Session 868C of the '92 RSNA (Radiological Society of America) when using particularly low-sensitivity light-sensitive materials.
By increasing the thickness of the fluorescent component and applying it in a conical shape like the microstructured intensifying screen of uclear reserch, a fluorescent intensifying screen with improved sensitivity and at the same time reduced quantum mottle and improved graininess Preference is given to using.
【0047】本発明の感光材料の処理は例えば、前記の
RD-17643のXX〜XXI、29〜30頁或いは同308119のXX〜XX
I、1011〜1012頁に記載されているような処理液による
処理がなされてよい。The processing of the light-sensitive material of the present invention is carried out by, for example,
RD-17643 XX-XXI, pages 29-30 or 308119 XX-XX
Treatment with a treatment solution as described in I, pages 1011-1010 may be performed.
【0048】白黒写真処理での現像剤としては、ジヒド
ロキシベンゼン類(例えばハイドロキノン)、3-ピラゾ
リドン類(例えば1-フェニル-3-ピラゾリドン)、アミ
ノフェノール類(例えばN-メチル-アミノフェノール)
などを単独もしくは組み合わせて用いることができる。
なお、現像液には公知の例えば保恒剤、アルカリ剤、p
H緩衝剤、カブリ防止剤、硬膜剤、現像促進剤、界面活
性剤、消泡剤、色調剤、硬水軟化剤、溶解助剤、粘性付
与剤などを必要に応じて用いてもよい。Developers for black and white photographic processing include dihydroxybenzenes (eg hydroquinone), 3-pyrazolidones (eg 1-phenyl-3-pyrazolidone), aminophenols (eg N-methyl-aminophenol).
Etc. can be used alone or in combination.
It should be noted that the developer may be a known one such as preservative, alkaline agent, p
An H buffer, an antifoggant, a film hardener, a development accelerator, a surfactant, an antifoaming agent, a toning agent, a water softener, a dissolution aid, a viscosity imparting agent and the like may be used as necessary.
【0049】定着液にはチオ硫酸塩、チオシアン酸塩な
どの定着剤が用いられ、さらに硬膜剤として水溶性のア
ルミニウム塩例えば硫酸アルミニウム或いはカリ明ばん
などを含んでいてもよい。その他保恒剤、pH調整剤、
硬水軟化剤などを含有していてもよい。A fixing agent such as thiosulfate or thiocyanate is used in the fixing solution and may further contain a water-soluble aluminum salt such as aluminum sulfate or potassium alum as a hardening agent. Other preservatives, pH adjusters,
It may contain a water softener and the like.
【0050】本発明の写真感光材料において、写真乳剤
層その他の親水性コロイド層は種々の塗布法により支持
体上または他の層上に塗布できる。塗布にはディップ塗
布法、ローラー塗布法、カーテン塗布法、押しだし塗布
法、スライド・ホッパー法などを用いることができる。
詳しくは(RD)第176巻.P.27-28の「Coating procedure
s」の項に記載されている方法を用ることができる。本
発明の実施に際しては、その他の写真技術において公知
の各種技術を適用することができる。In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other hydrophilic colloid layers can be coated on the support or other layers by various coating methods. For the coating, a dip coating method, a roller coating method, a curtain coating method, an extrusion coating method, a slide hopper method, or the like can be used.
For details, see (RD) Volume 176. P.27-28 `` Coating procedure
The method described in the section "s" can be used. In carrying out the present invention, various techniques known in other photographic techniques can be applied.
【0051】[0051]
【実施例】以下、本発明を実施例にてさらに詳述する。EXAMPLES The present invention will be described in more detail below with reference to examples.
【0052】実施例1 (六角平板状種乳剤EM-Aの調製)以下の方法により六
角平板状種乳剤を作成した。 (n+m=5〜7) <溶液A> オセインゼラチン 60.2g 蒸留水 20.0l HO-(CH2CH2O)n-[CH(CH3)CH2O]17-(CH2CH2O)mH (n+m=5〜7) 10%メタノール水溶液 5.6ml KBr 26.8g 10%H2SO4 144ml <溶液B> 硝酸銀 1487.5g 蒸留水で3500mlにする <溶液C> KBr 1029g KI 29.3g 蒸留水で3500mlにする <溶液D> 1.75N KBr水溶液 下記銀電位制御量 35℃において特公昭58-58288号、同58-58289号に記載さ
れている混合撹拌機を用いて、溶液Aに溶液B及び溶液
Cの各々64.1mlを同時混合法により2分の時間を要して
添加し核形成を行った。Example 1 (Preparation of hexagonal tabular seed emulsion EM-A) A hexagonal tabular seed emulsion was prepared by the following method. (N + m = 5~7) <solution A> ossein gelatin 60.2g Distilled water 20.0l HO- (CH 2 CH 2 O ) n- [CH (CH 3) CH 2 O] 17 - (CH 2 CH 2 O) m H ( n + m = 5 to 7) 10% methanol aqueous solution 5.6 ml KBr 26.8 g 10% H 2 SO 4 144 ml <Solution B> Silver nitrate 1487.5 g Distilled water to 3500 ml <Solution C> KBr 1029 g KI 29.3 g Distilled water to 3500 ml <Solution D> 1.75N KBr aqueous solution At the following silver potential control amount of 35 ° C, use a mixing stirrer described in JP-B-58-58288 and 58-58289 to prepare a solution A. 64.1 ml of each of solution B and solution C was added by the simultaneous mixing method over a period of 2 minutes to perform nucleation.
【0053】溶液B及び溶液Cの添加を停止した後、60
分の時間を要して溶液Aの温度を60℃に上昇させ、再び
溶液Bと溶液Cを同時混合法により各々68.5ml/minの
流量で50分間添加した。この間の銀電位(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)を溶液
Dを用いて+6mVになるように制御した。After stopping the addition of Solution B and Solution C, 60
The temperature of solution A was raised to 60 ° C. over a period of time, and solution B and solution C were again added by the simultaneous mixing method at a flow rate of 68.5 ml / min for 50 minutes. During this period, the silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) was controlled to be +6 mV using the solution D.
【0054】添加終了後3%KOHにてpHを6.0に合わ
せ、直ちに脱塩、水洗を行い種乳剤EM-Aとした。After the addition was completed, the pH was adjusted to 6.0 with 3% KOH, immediately desalted and washed with water to obtain a seed emulsion EM-A.
【0055】このように作成した種乳剤EM-Aは、ハ
ロゲン化銀粒子の全投影面積の90%以上が最大隣接辺比
が1.0〜2.0の六角平板粒子よりなり、六角平板の平均厚
さ0.07μm、平均直径(円直径換算)は0.5μm、変動係数
は25%であることが電子顕微鏡観察により判明した。In the seed emulsion EM-A thus prepared, 90% or more of the total projected area of silver halide grains consisted of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0, and the average thickness of the hexagonal tabular plate was 0.07. It was found by electron microscope observation that the average diameter (circle diameter conversion) was 0.5 μm, and the coefficient of variation was 25%.
【0056】(六角平板状種乳剤EM-Bの調製)溶液A
の温度を60℃に上昇させる時間を30分にする以外は種乳
剤EM-Aと同様に行い種乳剤EM-Bを得た。このよう
に作成した種乳剤EM-Bは、ハロゲン化銀粒子の全投
影面積の90%以上が最大隣接辺比が1.0〜2.0の六角平板
粒子よりなり、六角平板の平均厚さ0.07μm、平均直径
(円直径換算)は0.5μm、変動係数は32%であることが電
子顕微鏡観察により判明した。(Preparation of Hexagonal Tabular Seed Emulsion EM-B) Solution A
A seed emulsion EM-B was obtained in the same manner as the seed emulsion EM-A except that the temperature was raised to 60 ° C. for 30 minutes. In the seed emulsion EM-B thus prepared, 90% or more of the total projected area of silver halide grains consisted of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0, and the average thickness of the hexagonal tabular plate was 0.07 μm, and the average thickness was 0.07 μm. diameter
It was found by electron microscope observation that the (circle diameter conversion) was 0.5 μm and the coefficient of variation was 32%.
【0057】(双晶乳剤EM-1の調製)以下の4種類の
溶液を用いて1.53モル%AgIを含有する本発明の単分散
双晶沃臭化銀乳剤EM-1を作成した。(Preparation of Twin Crystal Emulsion EM-1) A monodispersed twin silver iodobromide emulsion EM-1 of the present invention containing 1.53 mol% AgI was prepared using the following four kinds of solutions.
【0058】 <溶液A> オセインゼラチン 29.4g HO-(CH2CH2O)n-[CH(CH3)CH2O]17-(CH2CH2O)m-H (n+m=5〜7) 10%メタノール水溶液 2.5ml 種乳剤EM-A 0.588モル相当 蒸留水で4800mlとする <溶液B> 硝酸銀 1404.2g 蒸留水で2360mlとする <溶液C> KBr 968g KI 20.6g 蒸留水で2360mlとする <溶液D> 1.75N KBr水溶液 下記銀電位制御量 60℃において、特公昭58-58288号、同58-58289号に記載
の混合撹拌機を用いて溶液Aに溶液B及び溶液Cの全量
を同時混合法により21.26ml/minの流速で111分の時間
を要し添加成長を行った。[0058] <solution A> ossein gelatin 29.4g HO- (CH 2 CH 2 O ) n - [CH (CH 3) CH 2 O] 17 - (CH 2 CH 2 O) mH (n + m = 5~ 7) 10% methanol aqueous solution 2.5ml seed emulsion EM-A 0.588mol equivalent Distilled water to 4800ml <Solution B> Silver nitrate 1404.2g Distilled water to 2360ml <Solution C> KBr 968g KI 20.6g Distilled water to 2360ml <Solution D> 1.75N KBr aqueous solution At the following silver potential control amount of 60 ° C., all the amounts of Solution B and Solution C were simultaneously added to Solution A using the mixing stirrer described in JP-B-58-58288 and 58-58289. Addition growth was performed by the mixing method at a flow rate of 21.26 ml / min for 111 minutes.
【0059】この間の銀電位を溶液Dを用いて+25mVに
なるように制御した。During this period, the silver potential was controlled to be +25 mV by using the solution D.
【0060】添加終了後、下記分光増感色素(A)及び
(B)をハロゲン化銀1モル当たり各々300mg及び15mg添
加した後、過剰な塩類を除去するためデモールN(花王
アトラス社製)水溶液及び硫酸マグネシウム水溶液を用
いて沈澱脱塩を行い、オセインゼラチン92.2gを含むゼ
ラチン水溶液を加え2500mlとして撹拌再分散した。After the addition was completed, the following spectral sensitizing dye (A) and
After adding (B) 300 mg and 15 mg, respectively, per mol of silver halide, precipitation desalting was carried out using an aqueous solution of Demol N (manufactured by Kao Atlas) and an aqueous solution of magnesium sulfate to remove excess salts, and ossein gelatin was added. An aqueous gelatin solution containing 92.2 g was added to 2500 ml, and the mixture was redispersed with stirring.
【0061】分光増感色素(A):5,5'-ジクロロ-9-エチ
ル-3,3'-ジ-(3-スルホプロピル)オキサカルボシアニン
ナトリウム塩の無水物 分光増感色素(B):5,5'-ジ-(ブトキシカルボニル)-1,1'
-ジエチル-3,3'-ジ-(4-スルホブチル)ベンゾイミダゾ
ロカルボシアニンナトリウム塩の無水物 なお、EM-1の粒子約3000個を電子顕微鏡により観
察、測定し、形状を分析したところ、平均粒子直径1.05
μm、平均粒子厚さ0.25μm、球相当粒径0.59μm、変動
係数が18%であった。Spectral sensitizing dye (A): 5,5'-dichloro-9-ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine sodium salt anhydride Spectral sensitizing dye (B) : 5,5'-di- (butoxycarbonyl) -1,1 '
-Diethyl-3,3'-di- (4-sulfobutyl) benzimidazolocarbocyanine sodium salt anhydrous About 3000 particles of EM-1 were observed and measured by an electron microscope, and the shape was analyzed. Average particle diameter 1.05
The average particle thickness was 0.25 μm, the equivalent spherical diameter was 0.59 μm, and the coefficient of variation was 18%.
【0062】(双晶乳剤EM-2の調製)種乳剤EM-Aを
EM-Bにする以外はEM-1と同様の方法により双晶乳
剤EM-2を調製した。EM-2の粒子約3000個を電子顕
微鏡により観察、測定し、形状を分析したところ、平均
粒子直径1.05μm、平均粒子厚さ0.25μm、球相当粒径0.
59μm、変動係数が26%であった。(Preparation of Twin Crystal Emulsion EM-2) Twin crystal emulsion EM-2 was prepared by the same method as EM-1, except that seed emulsion EM-A was changed to EM-B. Approximately 3000 particles of EM-2 were observed and measured by an electron microscope, and the shape was analyzed. The average particle diameter was 1.05 μm, the average particle thickness was 0.25 μm, and the sphere-equivalent particle diameter was 0.
The coefficient of variation was 59 μm and the coefficient of variation was 26%.
【0063】(双晶乳剤EM-3の調製)以下の4種類の
溶液を用いて1.53モル%のAgIを含有する本発明の単分
散双晶沃臭化銀乳剤EM-3を調製した。(Preparation of Twin Crystal Emulsion EM-3) The monodisperse twin silver iodobromide emulsion EM-3 of the present invention containing 1.53 mol% AgI was prepared using the following four kinds of solutions.
【0064】 <溶液A> オセインゼラチン 29.4g HO-(CH2CH2O)n-[CH(CH3)CH2O]17-(CH2CH2O)mH (n+m=5〜7) 10%メタノール水溶液 2.5ml 種乳剤EM-A 1.906モル相当 蒸留水で6250mlとする <溶液B> 硝酸銀 1176g 蒸留水で1976mlとする <溶液C> KBr 811g KI 17.2g 蒸留水で1976mlとする <溶液D> 1.75N KBr水溶液 下記銀電位制御量 60℃において特公昭58-58288号、同58-58289号記載の混
合撹拌機を用いて溶液Aに溶液B及び溶液Cの全量を同
時混合法により21.26ml/minの流速で111分の時間を要
し添加成長を行った。この間の銀電位を溶液Dを用いて
+40mVになるように制御した。[0064] <solution A> ossein gelatin 29.4g HO- (CH 2 CH 2 O ) n - [CH (CH 3) CH 2 O] 17 - (CH 2 CH 2 O) m H (n + m = 5 ~ 7) 10% methanol aqueous solution 2.5 ml seed emulsion EM-A 1.906 mol equivalent Distilled water to 6250 ml <Solution B> Silver nitrate 1176 g Distilled water to 1976 ml <Solution C> KBr 811 g KI 17.2 g Distilled water to 1976 ml <Solution D> 1.75N KBr aqueous solution Simultaneous mixing of all amounts of Solution B and Solution C into Solution A using the mixing stirrer described in JP-B Nos. 58-58288 and 58-58289 at the following silver potential control amount of 60 ° C. Thus, additional growth was performed at a flow rate of 21.26 ml / min for 111 minutes. During this period, the silver potential was controlled to be +40 mV by using the solution D.
【0065】添加終了後、上記の分光増感色素(A)及び
(B)をハロゲン化銀1モル当たり各々450mg及び20mg添
加した後、前記のEM-1と同様の方法により過剰な塩
類を除去してから、オセインゼラチン92.2gを含むゼラ
チン水溶液を加え2500mlとして撹拌再分散した。After the completion of addition, the above-mentioned spectral sensitizing dye (A) and
After adding (B) 450 mg and 20 mg, respectively, per mol of silver halide, remove excess salts by the same method as in EM-1 above, and add an aqueous gelatin solution containing 92.2 g of ossein gelatin to make 2500 ml. Redispersed with stirring.
【0066】EM-3の粒子約3000個を電子顕微鏡によ
り観察、測定し、形状を分析したところ平均粒子直径0.
70μm、平均粒子厚さ0.17μm、球相当粒径0.40μm、変動
係数が20%であった。Approximately 3000 particles of EM-3 were observed and measured by an electron microscope, and the shape was analyzed.
The average particle thickness was 70 μm, the average particle thickness was 0.17 μm, the sphere-equivalent particle size was 0.40 μm, and the coefficient of variation was 20%.
【0067】(双晶乳剤EM-4の調製)EM-AをEM-
Bにする以外はEM-3と同様に行い双晶乳剤EM-4を
調製した。得られたEM-4の粒子約3000個を電子顕微
鏡により観察、測定し、形状を分析したところ平均粒子
直径0.70μm、平均粒子厚さ0.17μm、球相当粒径0.59μ
m、変動係数が30%であった。(Preparation of Twin Emulsion EM-4) EM-A was replaced with EM-
Twin crystal emulsion EM-4 was prepared in the same manner as in EM-3 except that B was used. About 3000 particles of the obtained EM-4 were observed and measured by an electron microscope, and the shape was analyzed. The average particle diameter was 0.70 μm, the average particle thickness was 0.17 μm, and the sphere-equivalent particle diameter was 0.59 μ.
m, the coefficient of variation was 30%.
【0068】(球形双晶種乳剤EM-Cの調製)以下の方
法によって球形双晶種乳剤EM-Cを調製した。(Preparation of Spherical Twin Crystal Emulsion EM-C) A spherical twin seed emulsion EM-C was prepared by the following method.
【0069】 <溶液A> オセインゼラチン 150g KBr 53.1g KI 24g 蒸留水で 7200mlにする <溶液B> 硝酸銀 1500g 蒸留水で 6000mlにする <溶液C> KBr 1327g 1-フェニル-5-メルカプトテトラゾール(メタノールで溶解) 1.2g 蒸留水で 3000mlにする <溶液D> アンモニア水(28%) 705ml 40℃で激しく撹拌した溶液Aに核の生成を行った。この
時のpBrは1.09〜1.15であった。60分を要して温度を20
℃に下げた後、溶液Dを20秒で添加し5分間の熟成を行
った。熟成時のKBr濃度は0.071モル/リットル、アンモ
ニア濃度は0.63モル/リットルであった。<Solution A> Ossein gelatin 150 g KBr 53.1 g KI 24 g Distilled water to 7200 ml <Solution B> Silver nitrate 1500 g Distilled water to 6000 ml <Solution C> KBr 1327 g 1-phenyl-5-mercaptotetrazole (methanol 1.2 g Distilled water to 3000 ml <Solution D> Ammonia water (28%) 705 ml Nuclei were generated in solution A which was vigorously stirred at 40 ° C. The pBr at this time was 1.09 to 1.15. 20 minutes in 60 minutes
After the temperature was lowered to 0 ° C., Solution D was added in 20 seconds and aging was carried out for 5 minutes. The KBr concentration during aging was 0.071 mol / liter, and the ammonia concentration was 0.63 mol / liter.
【0070】その後pHを6.0に合わせ、直ちに脱塩、水
洗を行いEM-Cとした。この種乳剤は電子顕微鏡観察
したところ平均粒径が0.24μm、変動係数18%の単分散
性球形乳剤であった。Thereafter, the pH was adjusted to 6.0, and immediately desalted and washed with water to obtain EM-C. Observation of the seed emulsion with an electron microscope revealed that it was a monodisperse spherical emulsion having an average grain size of 0.24 μm and a coefficient of variation of 18%.
【0071】(球形双晶種乳剤EM-Dの調製)上記の種
乳剤EM-Cにおいて溶液D添加後の熟成を2分間にす
る以外はEM-Cと同様の方法で行い球形双晶種乳剤E
M-Dを調製した。(Preparation of Spherical Twin Crystal Seed Emulsion EM-D) A spherical twin seed emulsion EM-C was prepared in the same manner as EM-C except that the ripening after addition of the solution D was conducted for 2 minutes. E
MD was prepared.
【0072】得られたEM-Dの粒子約3000個を電子顕
微鏡により観察、測定し、形状を分析したところ平均粒
子直径0.24μm、変動係数が26%であった。About 3000 particles of the obtained EM-D were observed and measured by an electron microscope, and the shape was analyzed. As a result, the average particle diameter was 0.24 μm and the coefficient of variation was 26%.
【0073】(双晶乳剤EM-5の調製)種乳剤と以下に
示す3種の溶液を用い、主として平板状双晶からなるハ
ロゲン化銀乳剤EM-5を調製した。(Preparation of Twin Crystal Emulsion EM-5) A silver halide emulsion EM-5 consisting mainly of tabular twin crystals was prepared using a seed emulsion and the following three kinds of solutions.
【0074】 <溶液A> オセインゼラチン 37g HO-(CH2CH2O)n-[CH(CH3)CH2O]17-(CH2CH2O)mH (n+m=5〜7) 10%メタノール水溶液 10ml 種乳剤EM-C 0.475モル相当 蒸留水で 4000mlとする <溶液B> オセインゼラチン 109g KBr 772g KI 16.4g 蒸留水で 4390mlとする <溶液C> 硝酸銀 1119g 蒸留水で 6269mlとする 65℃で激しく撹拌した溶液Aに、溶液Bと溶液Cを112
分でダブルジェット法にて添加した。この間pHは5.8
に、pAgは8.8に終始保った。溶液Bと溶液Cの添加速度
は初期と最終で6.4倍となるように直線的に増加させ
た。<Solution A> Ocein gelatin 37 g HO- (CH 2 CH 2 O) n- [CH (CH 3 ) CH 2 O] 17- (CH 2 CH 2 O) m H ( n + m = 5 ~ 7) 10% methanol aqueous solution 10 ml Emulsion EM-C 0.475 mol equivalent Make up to 4000 ml with distilled water <Solution B> Ocein gelatin 109 g KBr 772 g KI 16.4 g Make up 4390 ml with distilled water <Solution C> Silver nitrate 1119 g 6269 ml with distilled water Solution B and solution C are added to solution A that is vigorously stirred at 65 ° C.
It was added by the double jet method in minutes. During this time, the pH is 5.8
In addition, pAg was kept at 8.8 throughout. The addition rates of solution B and solution C were linearly increased to 6.4 times in the initial and final stages.
【0075】添加終了後、EM-1と同様に増感色素
(A)及び(B)を添加した後、同様の方法により脱塩して
から、オセインゼラチン92.2gを含むゼラチン水溶液を
加え2500mlとして撹拌再分散した。After the addition was completed, a sensitizing dye was prepared in the same manner as in EM-1.
After the addition of (A) and (B), desalting was carried out in the same manner, and then an aqueous gelatin solution containing 92.2 g of ossein gelatin was added and the mixture was redispersed with stirring to 2500 ml.
【0076】EM-5の粒子約3000個を電子顕微鏡によ
り観察、測定し形状を分析したところ、平均粒子直径0.
78μm、平均粒子厚さ0.43μm、球相当粒径0.59μm、変
動係数が16%であった。Approximately 3000 particles of EM-5 were observed and measured by an electron microscope, and the shape was analyzed.
The average particle thickness was 78 μm, the average particle thickness was 0.43 μm, the sphere-equivalent particle size was 0.59 μm, and the coefficient of variation was 16%.
【0077】(双晶乳剤EM-6の調製)EM-CをEM-
Dにする以外はEM-5と同様に行い、双晶乳剤EM-6
を調製した。得られたEM-6の粒子約3000個を電子顕
微鏡により観察、測定し、形状を分析したところ平均粒
子直径0.78μm、平均粒子厚さ0.43μm、球相当粒径0.59
μm、変動係数は22%であった。(Preparation of twinned emulsion EM-6) EM-C was replaced with EM-
Twin emulsion EM-6 is performed in the same manner as EM-5 except that D is used.
Was prepared. About 3000 particles of the obtained EM-6 were observed and measured by an electron microscope, and the shape was analyzed. As a result, the average particle diameter was 0.78 μm, the average particle thickness was 0.43 μm, and the sphere-equivalent particle diameter was 0.59.
μm, the coefficient of variation was 22%.
【0078】(双晶乳剤EM-7の調製)種乳剤と以下に
示す3種の溶液を用い、主として平板状双晶からなるハ
ロゲン化銀乳剤EM-7を調製した。(Preparation of Twin Crystal Emulsion EM-7) Using the seed emulsion and the following three kinds of solutions, a silver halide emulsion EM-7 mainly composed of tabular twin crystals was prepared.
【0079】 <溶液A> オセインゼラチン 37g HO-(CH2CH2O)n-[CH(CH3)CH2O]17-(CH2CH2O)mH (n+m=5〜7) 10%メタノール水溶液 10ml 種乳剤EM-C 1.525モル相当 蒸留水で 6000mlとする <溶液B> オセインゼラチン 109g KBr 649g KI 13.8g 蒸留水で 3694mlとする <溶液C> 硝酸銀 941g 蒸留水で 5272mlとする 65℃で激しく撹拌した溶液Aに、溶液Bと溶液Cを112
分でダブルジェット法にて添加した。この間pHは5.8
に、pAgは8.8に終始保った。溶液Bと溶液Cの添加速度
は初期と最終で6.4倍となるように直線的に増加させ
た。<Solution A> Ocein gelatin 37 g HO- (CH 2 CH 2 O) n- [CH (CH 3 ) CH 2 O] 17- (CH 2 CH 2 O) m H ( n + m = 5 ~ 7) 10% methanol aqueous solution 10 ml seed emulsion EM-C equivalent to 1.525 mol Distilled water to 6000 ml <Solution B> Ocein gelatin 109 g KBr 649 g KI 13.8 g Distilled water to 3694 ml <Solution C> Silver nitrate 941 g Distilled water 5272 ml Solution B and solution C are added to solution A that is vigorously stirred at 65 ° C.
It was added by the double jet method in minutes. During this time, the pH is 5.8
In addition, pAg was kept at 8.8 throughout. The addition rates of solution B and solution C were linearly increased to 6.4 times in the initial and final stages.
【0080】添加終了後、EM-3と同様に分光増感色
素(A)及び(B)を添加した後、同様の方法により脱塩し
てから、オセインゼラチン92.2gを含むゼラチン水溶液
を加え2500mlとして撹拌再分散した。After completion of the addition, the spectral sensitizing dyes (A) and (B) were added in the same manner as in EM-3, desalting was performed in the same manner, and then an aqueous gelatin solution containing 92.2 g of ossein gelatin was added. The mixture was redispersed with stirring as 2500 ml.
【0081】EM-7の粒子約3000個を電子顕微鏡によ
り観察、測定し形状を分析したところ平均粒子直径0.52
7μm、平均粒子厚さ0.29μm、球相当粒径0.40μm、変動
係数が17%であった。Approximately 3000 particles of EM-7 were observed and measured by an electron microscope, and the shape was analyzed. The average particle diameter was 0.52.
The average particle thickness was 7 μm, the average particle thickness was 0.29 μm, the sphere-equivalent particle size was 0.40 μm, and the coefficient of variation was 17%.
【0082】(双晶乳剤EM-8の調製)EM-CをEM-
Dにする以外はEM-7と同様に行い双晶乳剤EM-8を
調製した。得られたEM-8の粒子約3000個を電子顕微
鏡により観察、測定し、形状を分析したところ平均粒子
直径0.527μm、平均粒子厚さ0.29μm、球相当粒径0.40
μm、変動係数が24%であった。(Preparation of Twin Emulsion EM-8) EM-C was replaced with EM-
A twinned crystal emulsion EM-8 was prepared in the same manner as in EM-7 except that D was used. About 3000 particles of the obtained EM-8 were observed and measured by an electron microscope, and the shape was analyzed. As a result, the average particle diameter was 0.527 μm, the average particle thickness was 0.29 μm, and the equivalent spherical diameter was 0.40.
μm, coefficient of variation 24%.
【0083】(単分散立方晶種乳剤EM-Eの調製) <溶液A> オセインゼラチン 30g KBr 1.25g 硝酸(0.1N) 150ml 蒸留水で 7700mlとする <溶液B> KBr 6g KI 0.16g 蒸留水で 740mlとする <溶液C> KBr 680g KI 20g 蒸留水で 2480mlとする <溶液D> 硝酸銀 8.4g 硝酸(0.1N) 32ml 蒸留水で 740mlとする <溶液E> 硝酸銀 91.6g 硝酸(0.1N) 80ml 蒸留水で 2480mlとする 60℃で激しく撹拌した溶液Aに、溶液Bと溶液Dをダブ
ルジェット法により10分間かけて添加した。そして溶液
Cと溶液Eをダブルジェット法により140分間かけて添
加した。このとき初期添加流量は最終添加流量の1/8
で、時間とともに直線的に増加せしめた。これら液を添
加せしめている間はpH=2、pAg=8になるよう一定に
調整した。添加終了後に炭酸ナトリウムでpHを6まで
上げ、KBrを150g加えた後に直ちに脱塩、水洗を行って
平均粒径0.3μmの沃化銀2モル%を含む沃臭化銀の単分
散立方晶種乳剤EM-Eを得た。この乳剤は電子顕微鏡
観察によれば双晶の発生率は個数で1%以下であった。(Preparation of Monodisperse Cubic Seed Emulsion EM-E) <Solution A> Ocein gelatin 30 g KBr 1.25 g Nitric acid (0.1 N) 150 ml Distilled water to 7700 ml <Solution B> KBr 6 g KI 0.16 g Distilled water <Solution C> KBr 680g KI 20g Distilled water to 2480ml <Solution D> Silver nitrate 8.4g Nitric acid (0.1N) 32ml Distilled water to 740ml <Solution E> Silver nitrate 91.6g Nitric acid (0.1N) 80ml Solution B and solution D were added by the double jet method over 10 minutes to solution A that was vigorously stirred at 60 ° C. with distilled water to 2480 ml. Then, the solution C and the solution E were added by the double jet method over 140 minutes. At this time, the initial addition flow rate is 1/8 of the final addition flow rate.
So, it increased linearly with time. While these liquids were being added, the pH was adjusted to 2 and the pH was adjusted to 8 so that the pH was kept constant. After the addition was completed, the pH was raised to 6 with sodium carbonate, 150 g of KBr was added, and immediately thereafter desalting and washing were carried out to obtain a monodisperse cubic crystal of silver iodobromide containing 2 mol% of silver iodide having an average grain size of 0.3 μm. Emulsion EM-E was obtained. According to an electron microscope observation, the occurrence of twins in this emulsion was 1% or less in number.
【0084】(正常晶コア/シェル乳剤EM-9の調
製)以下の5種類の溶液を用いてAgI2.0モル%を含有す
る正常晶乳剤EM-9を製造した。(Preparation of Normal Crystal Core / Shell Emulsion EM-9) A normal crystal emulsion EM-9 containing 2.0 mol% of AgI was prepared using the following 5 kinds of solutions.
【0085】 <溶液A> オセインゼラチン 75.5g HO-(CH2CH2O)n-[CH(CH3)CH2O]17-(CH2CH2O)mH (n+m=5〜7) 10%メタノール水溶液 15ml 種乳剤EM-E 0.928モル相当 蒸留水で 4000mlとする <溶液B> AgNO3 151.3g AgNO3と等量のアンモニア溶液と蒸留水を加えて 848mlとする <溶液C> AgNO3 890.9g AgNO3と等量のアンモニア溶液と蒸留水を加えて 1497mlとする <溶液D> KBr 74.1g KI 44.3g 蒸留水で 848mlにする <溶液E> KBr 623.6g 蒸留水で 1497mlにする 反応釜内に溶液Aを40℃に保ち、さらにアンモニア水と
酢酸を加えpHを9.5に調整した。<Solution A> Ossein gelatin 75.5 g HO- (CH 2 CH 2 O) n- [CH (CH 3 ) CH 2 O] 17- (CH 2 CH 2 O) m H ( n + m = 5 ~ 7) 10% methanol aqueous solution 15 ml seed emulsion EM-E 0.928 mol equivalent Make up to 4000 ml with distilled water <Solution B> AgNO 3 151.3 g AgNO 3 and an equivalent amount of ammonia solution and distilled water to make 848 ml <Solution C > AgNO 3 890.9g Add the same amount of ammonia solution as AgNO 3 and distilled water to make 1497ml <Solution D> KBr 74.1g KI 44.3g Make distilled water 848ml <Solution E> KBr 623.6g Make 1497ml with distilled water Solution A was kept at 40 ° C. in the reaction kettle, and ammonia water and acetic acid were further added to adjust the pH to 9.5.
【0086】アンモニア性銀イオン液にてpAgを7.3に調
整後、pHとpAgを一定に保ちつつ溶液Bと溶液Dをダブ
ルジェット法で添加し、沃化銀30モル%を含む沃臭化銀
層を形成せしめた。After adjusting the pAg to 7.3 with an ammoniacal silver ion solution, the solution B and the solution D were added by the double jet method while keeping the pH and pAg constant, and silver iodobromide containing 30 mol% of silver iodide was added. The layers were allowed to form.
【0087】酢酸とKBrを用いてpHを9.0、pAgを9.0に
調整した後に溶液Cと溶液Eを同時に添加し成長後、粒
径の90%にあたるまで成長させた。このときのpHは9.0
から8.20まで徐々に下げた。After adjusting pH to 9.0 and pAg to 9.0 using acetic acid and KBr, solution C and solution E were added at the same time and grown, and then grown to 90% of the grain size. The pH at this time is 9.0
From 8.20 down gradually.
【0088】KBr液を加えpAgを11にした後に、さらに溶
液Cと溶液Eを加えてpHを徐々に8まで下げながら成
長せしめ、沃化銀2モル%の沃臭化銀乳剤を得た。After KBr solution was added to adjust pAg to 11, solution C and solution E were further added to grow while gradually lowering pH to 8 to obtain a silver iodobromide emulsion containing 2 mol% of silver iodide.
【0089】添加終了後、EM-1と同様に分光増感色
素(A)及び(B)を添加した後、同様の方法により脱塩し
てから、オセインゼラチン92.2gを含むゼラチン水溶液
を加え2500mlとして、撹拌再分散してEM-9とした。After the completion of the addition, the spectral sensitizing dyes (A) and (B) were added in the same manner as in EM-1, followed by desalting in the same manner, and then an aqueous gelatin solution containing 92.2 g of ossein gelatin was added. The amount was 2500 ml and the mixture was stirred and redispersed to obtain EM-9.
【0090】EM-9の粒子約3000個を電子顕微鏡によ
り観察、測定し、形状を分析したところ平均粒子直径0.
59μm、分布の広さが12%の単分散球状粒子であった。Approximately 3000 particles of EM-9 were observed and measured by an electron microscope, and the shape was analyzed.
It was a monodisperse spherical particle having a distribution of 59% and a width of 12%.
【0091】(正常晶コア/シェル乳剤EM-10の調製)
以下の5種類の溶液を用いて2.0モル%AgIを含有する正
常晶乳剤EM-10を調製した。(Preparation of Normal Crystal Core / Shell Emulsion EM-10)
A normal crystal emulsion EM-10 containing 2.0 mol% AgI was prepared using the following 5 kinds of solutions.
【0092】 <溶液A> オセインゼラチン 94.4g HO-(CH2CH2O)n-[CH(CH3)CH2O]17-(CH2CH2O)mH (n+m=5〜7) 10%メタノール水溶液 15ml 種乳剤EM-E 2.09モル相当 蒸留水で 5000mlとする <溶液B> AgNO3 146.6g AgNO3と等量のアンモニア溶液と蒸留水を加えて 822mlとする <溶液C> AgNO3 698.1g AgNO3と等量のアンモニア溶液と蒸留水を加えて 1173mlとする <溶液D> KBr 71.8g KI 42.9g 蒸留水で 822mlにする <溶液E> KBr 488.7g 蒸留水で 1765mlにする 反応釜内に溶液Aを40℃に保ち、さらにアンモニア水と
酢酸を加えpHを9.5に調整した。[0092] <solution A> ossein gelatin 94.4g HO- (CH 2 CH 2 O ) n - [CH (CH 3) CH 2 O] 17 - (CH 2 CH 2 O) m H (n + m = 5 ~ 7) 10% methanol aqueous solution 15 ml seed emulsion EM-E 2.09 mol equivalent Distilled water to make 5000 ml <Solution B> AgNO 3 146.6 g AgNO 3 and an equivalent amount of ammonia solution and distilled water to make 822 ml <Solution C > AgNO 3 698.1g Add ammonia solution equivalent to AgNO 3 and distilled water to make 1173ml <Solution D> KBr 71.8g KI 42.9g Make 822ml with distilled water <Solution E> KBr 488.7g Make 1765ml with distilled water Solution A was kept at 40 ° C. in the reaction kettle, and ammonia water and acetic acid were further added to adjust the pH to 9.5.
【0093】アンモニア性銀イオン液にてpAgを7.3に調
整後、pHとpAgを一定に保ちつつ溶液Bと溶液Dをダブ
ルジェット法で添加し、沃化銀30モル%を含む沃臭化銀
層を形成せしめた。After adjusting the pAg to 7.3 with an ammoniacal silver ion solution, the solution B and the solution D were added by the double jet method while keeping the pH and the pAg constant, and silver iodobromide containing 30 mol% of silver iodide was added. The layers were allowed to form.
【0094】酢酸とKBrを用いてpHを9.0、pAgを9.0に
調整した後に、溶液Cと溶液Eを同時に添加し成長後、
粒径の90%にあたるまで成長させた。このときのpHは
9.0から8.20まで徐々に下げた。After adjusting the pH to 9.0 and the pAg to 9.0 using acetic acid and KBr, solution C and solution E were added at the same time to grow,
It was grown to 90% of the grain size. The pH at this time is
Gradually lowered from 9.0 to 8.20.
【0095】KBr液を加えpAgを11にした後に、さらに溶
液Cと溶液Eを加えてpHを徐々に8まで下げながら成
長せしめ、沃化銀2モル%の沃臭化銀乳剤を得た。After adding the KBr solution to adjust the pAg to 11, the solution C and the solution E were further added to grow while gradually lowering the pH to 8 to obtain a silver iodobromide emulsion containing 2 mol% of silver iodide.
【0096】添加終了後、分光増感色素(A)及び(B)を
ハロゲン化銀1モル当たり各々400mg及び20mg添加した
後、EM-1と同様な方法で脱塩してからオセインゼラ
チン92.2gを含むゼラチン水溶液を加えて2500mlとし、
撹拌再分散しEM-10を得た。After completion of the addition, spectral sensitizing dyes (A) and (B) were added in an amount of 400 mg and 20 mg per mol of silver halide, respectively, and then desalted in the same manner as in EM-1 and then ossein gelatin 92.2 Add gelatin aqueous solution containing g to make 2500 ml,
Redispersion with stirring gave EM-10.
【0097】EM-10の粒子約3000個を電子顕微鏡によ
り観察、測定し、形状を分析したところ平均粒子直径0.
45μm、分布の広さが13%の単分散球状粒子であった。Approximately 3000 particles of EM-10 were observed and measured by an electron microscope, and the shape was analyzed.
The particles were monodisperse spherical particles having a size of 45 μm and a distribution of 13%.
【0098】(正常晶コア/シェル乳剤EM-11の調製)
以下の5種類の溶液を用いて2.0モル%AgIを含有する正
常晶乳剤EM-11を調製した。(Preparation of Normal Crystal Core / Shell Emulsion EM-11)
A normal crystal emulsion EM-11 containing 2.0 mol% AgI was prepared using the following 5 kinds of solutions.
【0099】 <溶液A> オセインゼラチン 94.4g HO-(CH2CH2O)n-[CH(CH3)CH2O]17-(CH2CH2O)mH (n+m=5〜7) 10%メタノール水溶液 15ml 種乳剤EM-E 3.47モル相当 蒸留水で 5000mlとする <溶液B> AgNO3 141.1g AgNO3と等量のアンモニア溶液と蒸留水を加えて 790mlとする <溶液C> AgNO3 469.0g AgNO3と等量のアンモニア溶液と蒸留水を加えて 788mlとする <溶液D> KBr 69.1g KI 41.3g 蒸留水で 790mlにする <溶液E> KBr 328.3g 蒸留水で 788mlにする 反応釜内に溶液Aを40℃に保ち、さらにアンモニア水と
酢酸を加えpHを9.5に調整した。[0099] <solution A> ossein gelatin 94.4g HO- (CH 2 CH 2 O ) n - [CH (CH 3) CH 2 O] 17 - (CH 2 CH 2 O) m H (n + m = 5 〜7) 10% methanol aqueous solution 15 ml seed emulsion EM-E 3.47 mol equivalent Distilled water to make 5000 ml <Solution B> AgNO 3 141.1 g AgNO 3 and an equivalent amount of ammonia solution and distilled water to make 790 ml <Solution C > AgNO 3 469.0g Add ammonia solution equivalent to AgNO 3 and distilled water to make 788ml <Solution D> KBr 69.1g KI 41.3g Make 790ml with distilled water <Solution E> KBr 328.3g Make 788ml with distilled water Solution A was kept at 40 ° C. in the reaction kettle, and ammonia water and acetic acid were further added to adjust the pH to 9.5.
【0100】アンモニア性銀イオン液にてpAgを7.3に調
整後、pHとpAgを一定に保ちつつ溶液Bと溶液Dをダブ
ルジェット法で添加し、沃化銀30モル%を含む沃臭化銀
層を形成せしめた。After adjusting the pAg to 7.3 with an ammoniacal silver ion solution, the solution B and the solution D were added by the double jet method while keeping the pH and the pAg constant, and silver iodobromide containing 30 mol% of silver iodide was added. The layers were allowed to form.
【0101】酢酸とKBrを用いてpHを9.0、pAgを9.0に
調整した後に溶液Cと溶液Eを同時に添加し成長後、粒
径の90%にあたるまで成長させた。このときのpHは9.0
から8.20まで徐々に下げた。After adjusting pH to 9.0 and pAg to 9.0 using acetic acid and KBr, solution C and solution E were added at the same time and grown, and then grown to 90% of the grain size. The pH at this time is 9.0
From 8.20 down gradually.
【0102】KBr液を加え、pAgを11にした後にさらに溶
液Cと溶液Eを加えてpHを徐々に8まで下げながら成
長せしめ沃化銀2モル%の沃臭化銀乳剤を得た。The KBr solution was added to adjust the pAg to 11, and the solutions C and E were further added to grow while gradually lowering the pH to 8 to obtain a silver iodobromide emulsion containing 2 mol% of silver iodide.
【0103】添加終了後、分光増感色素(A)及び(B)を
ハロゲン化銀1モル当たり各々450mg及び20mg添加した
後、EM-1と同様の方法で脱塩してから、オセインゼ
ラチン92.2gを含むゼラチン水溶液を加え2500mlとして
撹拌再分散し、EM-11とした。After the completion of the addition, spectral sensitizing dyes (A) and (B) were added at 450 mg and 20 mg, respectively, per mol of silver halide, desalted in the same manner as in EM-1, and then ossein gelatin was used. An aqueous gelatin solution containing 92.2 g was added to 2500 ml with stirring and redispersion to obtain EM-11.
【0104】EM-10の粒子約3000個を電子顕微鏡によ
り観察、測定し、形状を分析したところ、平均粒子直径
0.38μm、分布の広さが15%の単分散球状粒子であっ
た。Approximately 3000 particles of EM-10 were observed and measured by an electron microscope, and the shape was analyzed.
The particles were monodisperse spherical particles having a width of 0.38 μm and a distribution of 15%.
【0105】(試料の作成)それぞれの乳剤について分光
増感色素(A)及び(B)を各々ハロゲン化銀1モル当たり
140mgと1.4mg添加した後、チオシアン酸アンモニウム塩
を銀1モル当たり7.0×10-4モル、及び適当な量の塩化
金酸とハイポを添加して化学熟成を行い、次いで6μm
のAgI微粒子乳剤を6×10-4モル/Ag1モル添加後、4-
ヒドロキシ-6-メチル-1,3,3a,7-テトラザインデンの3
×10-2モルで安定化した。(Preparation of Sample) Spectral sensitizing dyes (A) and (B) were added to each emulsion per mol of silver halide.
After adding 140 mg and 1.4 mg, ammonium thiocyanate salt was chemically ripened by adding 7.0 × 10 -4 mol per mol of silver, and an appropriate amount of chloroauric acid and hypo, and then 6 μm.
After adding 6 × 10 −4 mol / Ag 1 mol of AgI fine grain emulsion of
Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 3
Stabilized at × 10 -2 mol.
【0106】それぞれの乳剤を表1に示す比率で混合
し、後記の各種添加剤を加えて乳剤塗布液とした。各添
加剤の添加量はハロゲン化銀1モル当たりの量で示す。The respective emulsions were mixed at the ratios shown in Table 1 and various additives described below were added to prepare emulsion coating solutions. The amount of each additive added is indicated by the amount per mol of silver halide.
【0107】 t-ブチル-カテコール 150mg ポリビニルピロリドン(分子量10,000) 1.0g スチレン-無水マレイン酸供重合体 2.5g トリメチロールプロパン 10g ジエチレングリコール 5g ニトロフェニル-トリフェニル-ホスホニウムクロリド 50mg 1,3-ジヒドロキシベンゼン-4-スルホン酸アンモニウム 4g 2-メルカプトベンツイミダゾール-5-スルホン酸ナトリウム 1.5mgT-Butyl-catechol 150 mg Polyvinylpyrrolidone (molecular weight 10,000) 1.0 g Styrene-maleic anhydride copolymer 2.5 g Trimethylolpropane 10 g Diethylene glycol 5 g Nitrophenyl-triphenyl-phosphonium chloride 50 mg 1,3-Dihydroxybenzene-4 -Ammonium sulfonate 4g 2-Mercaptobenzimidazole-5-sodium sulfonate 1.5mg
【0108】[0108]
【化1】 [Chemical 1]
【0109】 n-C4H9OCH2CH(OH)CH2N(CH2COOH)2 1g また保護層液に用いた添加剤は次のとおりである。添加
量はゼラチン1g当たりの量で示す。NC 4 H 9 OCH 2 CH (OH) CH 2 N (CH 2 COOH) 2 1 g The additives used in the protective layer liquid are as follows. The added amount is shown as an amount per 1 g of gelatin.
【0110】 面積平均粒径7μmのポリメチルメタクリレートからなるマット剤 7mg コロイドシリカ(平均粒径0.013μm) 70mg 2,4-ジクロロ-6-ヒドロキシ-1,3,5-トリアジンナトリウム塩 30mg (CH2=CHSO2-CH2-)2O 36mg ソヂウムイソアミルデシルスルホサクシネエート 7mgMatting agent composed of polymethylmethacrylate having an area average particle size of 7 μm 7 mg Colloidal silica (average particle size 0.013 μm) 70 mg 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt 30 mg (CH 2 = CHSO 2 -CH 2- ) 2 O 36mg Sodium isoamyldecyl sulfosuccinate 7mg
【0111】[0111]
【化2】 [Chemical 2]
【0112】以上の塗布液を厚さ180μmの下引き処理済
のブルーに着色したポリエチレンテレフタレートフィル
ムベース上に両面に均一に塗布、乾燥して表1に示すよ
うに試料1〜20を作成した。The above coating solution was uniformly applied to both surfaces of a blue-colored polyethylene terephthalate film base having a thickness of 180 μm and subjected to undercoating treatment, and dried to prepare samples 1 to 20 as shown in Table 1.
【0113】また塗布ゼラチンは両面で3.0g/m2にな
るように全試料について調整を行った。各試料について
塗布銀量は片面分として2.0g/m2になるように調整し
た。Further, all the samples were adjusted so that the coated gelatin was 3.0 g / m 2 on both sides. The amount of silver coated on each sample was adjusted to 2.0 g / m 2 on one side.
【0114】〈センシトメトリー(感度、γ)の評価〉
得られた試料を濃度傾斜を鏡対称に整合した2枚の光学
ウェッジに挟み、色温度5,400゜Kの光源で両側から同時
に、かつ等量の1/10秒間露光後、SRX-501自動現像機
(コニカ〔株〕製)を用い現像液-1及び定着液-1にて現
像温度35℃で45秒処理を行った。<Evaluation of sensitometry (sensitivity, γ)>
The obtained sample is sandwiched between two optical wedges whose density gradients are mirror-symmetrically aligned, exposed at the same time from both sides by a light source with a color temperature of 5,400 ° K, and after an equal amount of 1/10 second exposure, SRX-501 automatic processor
(Manufactured by Konica Corp.) was processed with Developer-1 and Fixer-1 at a developing temperature of 35 ° C. for 45 seconds.
【0115】上記のようにして現像した各試料について
感度を評価した。感度は試料1がカブリ+1.0の濃度を
与えるのに要した爆射エネルギー量の逆数を100とした
相対値で示した。また、このとき、直接撮影用X−レイ
フィルムSR-G(コニカ〔株〕製、製造番号2014A)の感
度は98であった。The sensitivity of each sample developed as described above was evaluated. The sensitivity was shown as a relative value with the reciprocal of the amount of bombardment energy required for Sample 1 to give a density of fog +1.0 as 100. At this time, the sensitivity of the X-ray film SR-G for direct photography (manufactured by Konica Corporation, product number 2014A) was 98.
【0116】〈MTFの評価〉各試料について矩形波チ
ャートを撮影し、コントラスト法によってMTFを測定
した。なお、MTFは空間周波数2.0本/mmの値を示し
た。<Evaluation of MTF> A rectangular wave chart was photographed for each sample, and MTF was measured by the contrast method. In addition, MTF showed the value of spatial frequency of 2.0 lines / mm.
【0117】〈診断性(鮮鋭性、粒状性)の評価〉各試料
をX線用蛍光増感紙SRO-250で挟み、胸部ファントムを
介して肺野部の最高濃度が表2に示すようになるように
曝射時間を変化させてX線撮影を行い、SRX-501自動現
像機を用いてXD-SR現像処理液(コニカ〔株〕製)で35℃
で45秒処理を行った。<Evaluation of Diagnostic Properties (Sharpness, Granularity)> Each sample was sandwiched between X-ray fluorescent intensifying screens SRO-250, and the highest concentration in the lung field through the chest phantom as shown in Table 2. X-ray photography was performed while changing the exposure time so that the temperature was 35 ° C with the XD-SR development processing solution (manufactured by Konica Corporation) using the SRX-501 automatic processor.
For 45 seconds.
【0118】得られた画像の縦隔部及び肺野部について
目視による鮮鋭性と粒状性を下記の5段階で評価した。With respect to the mediastinum and lung field of the obtained image, the visual sharpness and graininess were evaluated by the following 5 grades.
【0119】1.非常に劣る 2.劣る 3.普通 4.良好 5.非常に良好 以上、得られた結果を下記に示す。1. Very inferior 2. Inferior 3. Normal 4. Good 5. Very good results obtained above are shown below.
【0120】[0120]
【表1】 [Table 1]
【0121】[0121]
【表2】 [Table 2]
【0122】実施例2 実施例1の乳剤を、表3の組み合わせで2層重ねて塗布
した試料を作成し、実施例1と同様の評価を行った。Example 2 The emulsion of Example 1 was coated in two layers in the combinations shown in Table 3 to prepare a sample, and the same evaluation as in Example 1 was carried out.
【0123】塗布条件は実施例1に準じ、塗布銀量が片
面2g/m2となるように支持体に近い方から第1層、第
2層の順に塗布した。得られた結果を下記に示す。The coating conditions were the same as in Example 1, and the first layer and the second layer were coated in this order from the side closer to the support so that the coated silver amount was 2 g / m 2 on each side. The results obtained are shown below.
【0124】[0124]
【表3】 [Table 3]
【0125】[0125]
【表4】 [Table 4]
【0126】表から明らかなように本発明の試料は肺野
部、縦隔部における鮮鋭性及び粒状性が優れ画像のシヤ
ープネスが優れていることが分かる。As is apparent from the table, the sample of the present invention is excellent in sharpness and graininess in the lung field and mediastinum, and is excellent in image sharpness.
【0127】[0127]
【発明の効果】本発明により画像の粒状性、鮮鋭性が優
れ、かつ露光のばらつきによる診断性の変化が少ない露
光ラチチュードの広いハロゲン化銀写真感光材料を得る
ことができた。According to the present invention, it is possible to obtain a silver halide photographic light-sensitive material having a wide exposure latitude which is excellent in image graininess and sharpness and has little change in diagnostic ability due to exposure variations.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 岩▲崎▼ 和博 東京都日野市さくら町1番地コニカ株式会 社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Iwa ▲ Saki ▼ Kazuhiro Konica Co., Ltd. 1 Sakura-cho, Hino City, Tokyo
Claims (3)
銀乳剤層を有するハロゲン化銀写真感光材料において、
該乳剤層中のハロゲン化銀粒子が、アスペクト比3以上
で円相当直径が0.5μm以上の平板状粒子、及びアスペク
ト比2以下で球換算粒径が0.2μm以上0.5μm以下の粒子
をそれぞれ1種類以上含有し、かつ全ハロゲン化銀粒子
の平均沃化銀含有率が2.0モル%以下であり、さらに得
られた画像の特性曲線における光学濃度0.3と0.5の点を
結ぶ直線の傾き(γ1)が0.4〜0.7、光学濃度0.5と1.5
の点を結ぶ直線の傾き(γ2)が1.5〜2.0、光学濃度1.
0と2.0を結ぶ直線の傾き(γ3)が2.8〜3.5であること
を特徴とするハロゲン化銀写真感光材料。1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support,
The silver halide grains in the emulsion layer are tabular grains having an aspect ratio of 3 or more and a circle equivalent diameter of 0.5 μm or more, and grains having an aspect ratio of 2 or less and a sphere-converted grain size of 0.2 μm or more and 0.5 μm or less. More than one kind, the average silver iodide content of all silver halide grains is 2.0 mol% or less, and the slope of the straight line connecting the optical density points 0.3 and 0.5 in the characteristic curve of the obtained image (γ1) 0.4 to 0.7, optical density 0.5 and 1.5
The slope (γ2) of the line connecting the points is 1.5 to 2.0, and the optical density is 1.
A silver halide photographic light-sensitive material characterized in that the slope (γ3) of a straight line connecting 0 and 2.0 is 2.8 to 3.5.
ン化銀乳剤層を有するハロゲン化銀写真感光材料におい
て、支持体から最も離れた乳剤層中のハロゲン化銀粒子
が、アスペクト比3以上で円相当直径が0.5μm以上の平
板状粒子であり、該乳剤層に対して支持体に近い任意の
乳剤層中のハロゲン化銀粒子が、アスペクト比2以下で
球換算粒径が0.2μm以上0.5μm以下の粒子であって、か
つ全ハロゲン化銀粒子の平均沃化銀含有率が2.0モル%
以下であり、さらに該感光材料の特性曲線における光学
濃度0.3と0.5の点を結ぶ直線の傾き(γ1)が0.4〜0.7
で、光学濃度0.5と1.5の点を結ぶ直線の傾き(γ2)が
1.5〜2.0、光学濃度1.0と2.0を結ぶ直線の傾き(γ3)
が2.8〜3.5であることを特徴とするハロゲン化銀写真感
光材料。2. A silver halide photographic light-sensitive material having at least two silver halide emulsion layers on a support, wherein the silver halide grains in the emulsion layer farthest from the support have an aspect ratio of 3 or more. It is a tabular grain having a circle-equivalent diameter of 0.5 μm or more, and silver halide grains in any emulsion layer near the support with respect to the emulsion layer have an aspect ratio of 2 or less and a sphere-converted grain size of 0.2 μm or more and 0.5 The average silver iodide content of all silver halide grains is 2.0 mol%
And the slope (γ1) of the line connecting the optical density points 0.3 and 0.5 in the characteristic curve of the light-sensitive material is 0.4 to 0.7.
Then, the slope (γ2) of the straight line connecting the points of optical density 0.5 and 1.5 is
1.5-2.0, slope of the straight line connecting optical density 1.0 and 2.0 (γ3)
Is 2.8 to 3.5, and a silver halide photographic light-sensitive material.
以上の平板状粒子の変動係数が25%以上であり、かつア
スペクト比2以下で球換算粒径が0.2μm以上0.5μm以下
の粒子の変動係数が20%以下であることを特徴とする請
求項1及び請求項2記載のハロゲン化銀写真感光材料。3. A circle equivalent diameter of 0.5 μm with an aspect ratio of 3 or more.
The coefficient of variation of the above tabular grains is 25% or more, and the coefficient of variation of particles having an aspect ratio of 2 or less and a sphere-converted particle size of 0.2 μm or more and 0.5 μm or less is 20% or less. The silver halide photographic light-sensitive material according to claim 1 and claim 2.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP29695993A JPH07152102A (en) | 1993-11-26 | 1993-11-26 | Silver halide photographic sensitive material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP29695993A JPH07152102A (en) | 1993-11-26 | 1993-11-26 | Silver halide photographic sensitive material |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH07152102A true JPH07152102A (en) | 1995-06-16 |
Family
ID=17840412
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP29695993A Pending JPH07152102A (en) | 1993-11-26 | 1993-11-26 | Silver halide photographic sensitive material |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH07152102A (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1130461A3 (en) * | 2000-02-28 | 2002-11-27 | Eastman Kodak Company | High contrast visually adaptive radiographic film and imaging assembly |
EP1130462A3 (en) * | 2000-02-28 | 2002-11-27 | Eastman Kodak Company | Method of providing digital image in radiographic film having visually adaptive contrast |
EP1203982A3 (en) * | 2000-11-06 | 2002-11-27 | Eastman Kodak Company | Visually adaptive radiographic film and imaging assembly |
EP1130463A3 (en) * | 2000-02-28 | 2002-11-27 | Eastman Kodak Company | Rapidly processable and directly viewable radiographic film with visually adative contrast |
-
1993
- 1993-11-26 JP JP29695993A patent/JPH07152102A/en active Pending
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1130461A3 (en) * | 2000-02-28 | 2002-11-27 | Eastman Kodak Company | High contrast visually adaptive radiographic film and imaging assembly |
EP1130462A3 (en) * | 2000-02-28 | 2002-11-27 | Eastman Kodak Company | Method of providing digital image in radiographic film having visually adaptive contrast |
EP1130463A3 (en) * | 2000-02-28 | 2002-11-27 | Eastman Kodak Company | Rapidly processable and directly viewable radiographic film with visually adative contrast |
EP1203982A3 (en) * | 2000-11-06 | 2002-11-27 | Eastman Kodak Company | Visually adaptive radiographic film and imaging assembly |
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