JP806H - Silver halide photographic material for X-ray - Google Patents

Silver halide photographic material for X-ray

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Publication number
JP806H
JP806H JP806H JP 806 H JP806 H JP 806H JP 806 H JP806 H JP 806H
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JP
Japan
Prior art keywords
emulsion
silver halide
gamma
type
ray
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Description

【発明の詳細な説明】 〔技術分野〕 本発明は診断能の高いX線用ハロゲン化銀写真感光材料
に関する。詳しくは、高濃度部の露光ラチチュードが広
くて使い易く、かつ鮮鋭度が高くて診断し易いX線用ハ
ロゲン化銀写真感光材料に関する。 〔従来技術〕 X線用ハロゲン化銀写真感光材料(支持体の両面に感光
性乳剤層を有するものと、片面のみに感光性乳剤層を有
するものとがあるが、以下、両者を含めて単に「X線感
材」と称する。)による生体各部位のX線写真撮影にお
いては、病巣の早期発見および誤診の防止のため診断能
の高いことが求められるが、従来のX線感材は必ずしも
満足できるものではない。 即ち、従来の直接用X線感材は、第1図の写真特性曲線
において、(a)で示す高ガンマ型、(b)で示す低ガンマ
型、(c)で示す中庸型に大別され、該高ガンマ型(a)は、
鮮鋭度は高いが露光ラチチュードが狭いので使い難い
し、該低ガンマ型(b)は、逆に露光ラチチュードは広く
て使い易いが鮮鋭度が低いために診断し難いし、該中庸
タイプ(c)は、鮮鋭度も露光ラチチュードも中程度に過
ぎない。 これら各タイプの直接用X線感材にちうて、本発明と同
じ現像液−1で処理されたときの特性曲線において、光
学濃度0.50と同1.50との間のガンマ(ガンマ1)、およ
び光学濃度2.00と同3.00との間のガンマ(ガンマ2)の
代表例を挙げると表−1に示す通りである。 これら従来タイプの直接用X線感材によるX線写真撮影
の実際例においては次のような重大な欠点ないし不都合
さえ見られる場合があつた。即ち、我国におけるX線写
真撮影の最も多い生体部位は胃であり、描写力を高める
ために造影剤が用いられるが、従来の高ガンマ型直接用
X線感材では、造影剤の部分に露光量を合わせた場合、
造影剤の無い部分は現像後真黒につぶれた像しか得られ
ず、何ら診断に寄与できなかつた。このような現象を避
けるために低ガンマ型直接用X線感材が用いられること
が多いが、このX線感材の場合は、反面、鮮鋭度が低下
するために造影剤を含んだ胃壁部位の診断能が低減す
る。更に別の生体部位のX鮮写真撮影の実際例として、
手や脚などの骨りよう及び軟部組織(肉部ないし軟骨
部)の撮影があるが、この場合においても、従来の高ガ
ンマ型X線感材では骨りようの微細構造の鮮鋭度は高い
が、軟部組織は真黒につぶれてしまい、診断に寄与でき
なかつた。逆に、低ガンマ型X線感材を用いた場合で
は、軟部組織は描写されるが骨りようの鮮鋭度は低かつ
た。 〔発明の目的〕 そこで、本発明の目的は、高鮮鋭度で且つ高濃度部の露
光ラチチュードが広くて、診断能の高いX線感材を提供
することである。 〔発明の構成〕 上記目的を達成する本発明のX線感材は、下記組成の現
像液−1を用いて下記処理条件で処理されたときの特性
曲線において、光学濃度0.50と同1.50との間のガンマが
2.7〜3.3であり、かつ光学濃度2.00と同3.00との間のガ
ンマが1.5〜2.5であることを特徴とする。 現像液−1本発明の好ましい実施態様は、上記現像液−1で処理さ
れたときの特性曲線において、光学濃度0.50と同1.50と
の間のガンマが2.8〜3.1であり、かつ光学濃度2.00と同
3.00との間のガンマが1.7〜2.3であることである。 本発明でいう特性曲線は、次のような光センシトメトリ
ー〔A〕によつて得られる。 (光センシトメトリー〔A〕) 露光は、透明性支持体の両面(又は片面)に感光性乳剤
層を有するX線感材を2枚の光学ウエツジに挾み、色温
度5,400゜Kの光源で両側から同時に且つ等量、1/10秒
間露光する。処理は、下記の工程に従い、ローラー搬送
型等の自動現像機を用いて行う。 このとき用いる現像液は前記現像液−1であり、定着液
は酸性硬膜定着液であれば特に制限はなく、例えばサク
ラXF(小西六写真工業製)などである。 本発明でいうガンマは、特性曲線上のベース(支持体)
濃度+0.50の濃度の点と、ベース濃度+1.50の濃度の点
を結んだ直線の傾きを意味し、またベース濃度+2.00の
濃度の点と、ベース濃度+3.00の濃度の点を結んだ直線
の傾きを意味する。更に詳述すれば、これらの直接が露
光量軸(横軸)と交わる角度をθとすれば、tanθを意
味する。 本発明の特性曲線を得る方法は任意であり、単分散乳
剤、多分散乳剤、コア・シエル型単分散乳剤、コア・シ
エル型多分散乳剤の単用ないし2以上の組合せ利用、粒
径ないし粒度分布のコントロール、ハロゲン化銀晶癖の
適応化、硬膜剤や現像コントロール剤等の写真用添加剤
の利用などいずれの技術によつてもよい。 本発明の特性曲線を得る具体例を挙げると次の通りであ
る。 第1の方法は、大粒子のハロゲン化銀粒子と小粒子のハ
ロゲン化銀粒子を混合含有するハロゲン化銀乳剤を用い
ることである。例えば平均粒径1.35μmの単分散(コア
・シエル型が好ましい)乳剤と平均粒径0.65μmの単分
散(コア・シエル型が好ましい)乳剤とを各々最適に化
学増感後、ハロゲン化銀のモル比で3:1に混合するこ
とによつて達成される。この混合含有の他の例は、例え
ば平均粒径1.25μmの単分散(コア・シエル型が好まし
い)乳剤と平均粒径0.70μmの単分散(コア・シエル型
が好ましい)乳剤とを各々最適に化学増感後、ハロゲン
化銀のモル比で4:1に混合することである。 第2の方法は、単分散乳剤と多分散乳剤の混合によるこ
とである。例えば平均粒径1.35μmの単分散乳剤と平均
粒径0.75μmの多分散乳剤とを各々最適に化学増感後、
ハロゲン化銀のモル比で3:1に混合することによつて
達成される。この混合含有の他の例は、例えば平均粒径
1.15μmの単分散乳剤と平均粒径0.55μmの多分散乳剤
とを各々最適に化学増感後、ハロゲン化銀のモル比で
4:1に混合することである。この方法に用いるハロゲ
ン化銀もコア・シエル型が好ましい。 第3の方法としては、非常に高いガンマを有する感光性
ハロゲン化銀(単分散性、特にコア・シエル型単分散性
が好ましい。)乳剤に対して硬膜剤を多量に使用するな
どの手段によつて硬膜度を高めることが挙げられる。即
ち、硬膜度を高めることによつて、特性曲線の高濃度部
が中濃度部よりも、よりガンマが低下するためである。
硬膜剤の種類や用法等の適用法は当該写真業界において
公知の方法によればよく、例えばアルデヒド化合物、ケ
トン化合物、ムコクロル酸のようなハロゲン置換酸、エ
チレンイミン化合物、ビニルスルフオン化合物等を用い
得る。 第4の方法としては、非常に高いガンマを有する感光性
ハロゲン化銀(単分散性、特にコア・シエル型単分散性
が好ましい)乳剤に対して或る種の現像抑制剤を加える
などの手段によつて、特性曲線の高濃度部を優先的に軟
調化することが挙げられる。このような現像抑制剤の種
類や用法等の適用法は当該写真業界において公知の方法
によればよく、例えばインダゾール化合物やメルカプト
−コハク酸化合物等を好ましく用い得る。 上記本発明の第1および第2の方法等に用いられる単分
散乳剤は、常法により、例えばThe Photographic Journ
al,79,330〜338(1939)にtrivelli,Smithにより報告され
た方法で、平均粒子直径を測定したときに、粒子数又は
重量で少くとも95%の粒子が、平均粒子径の±40%
以内、より好ましくは±30%以内にあるハロゲン化銀
乳剤からなるものがよい。 かかる単分散乳剤の製法は公知であり、例えばJ.Phot.S
ci.,12,242〜251(1963)、特公昭48−36890号、
同52−16364号、特開昭55−142329号の
各広報に記載されており、また特願昭56−65573
号明細書中に記載されている技術を採用することもでき
る。 本発明に用いられるハロゲン化銀はコア・シエル型単分
散性であつてもよく、これらコア・シエル乳剤は特開昭
54−48521号公報等によつて公知である。 本発明に用いられるハロゲン化銀粒子は、例えばT.
H.James著“The Theory of the Photographic Proces
s”第4版,Macmillan社刊(1977年)38〜104頁等の文
献に記載されている中性法、酸性法、アンモニア法、順
混合、逆混合、ダブルズエツト法、コントロールド−ダ
ブルジエツト法、コンヴアージヨン法、コア/シエル法
などの方法を適用して製造することができる。ハロゲン
化銀組成としては、塩化銀、臭化銀、塩臭化銀、沃臭化
銀、塩沃臭化銀などのいずれも用いることができるが、
最も好ましい乳剤は、約10モル%以下の沃化銀を含む沃
臭化銀乳剤である。ハロゲン化銀粒子の粒子サイズは、
特に制限は無いが、0.1〜2μのものが好ましい。また
これらのハロゲン化銀粒子又はハロゲン化銀乳剤中に
は、閃光露光特性の改良の為に、イリジウム塩および/
又はロジウム塩が含有されていてもよい。 ハロゲン化銀の分散剤である親水性保護コロイドとして
はゼラチンが好ましく、その他ゼラチン誘導体、ポリビ
ニルアルコール等各種の天然あるいは合成されたコロイ
ド物質が単独あるいはゼラチンと併用して使用される。 本発明において有利に使用できる増感剤としては、貴金
属増感剤、例えば、金化合物、ルテニウム、ロジウム、
パラジウム、イリジウム、白金等、および硫黄増感剤、
立てば活性ゼラチン、硫黄化合物等又はセレン増感剤、
例えば活性及び不活性セレン化合物等、更に還元増感
剤、例えば1価スズ塩、ポリアミン、シラン化合物、ビ
スアルキルアミノスルフイド、イシノアミノメタンスル
フイン酸、ヒドラジニウム塩、ヒドラジン誘導体等、以
上の4種に大別できる。これらの増感剤を単独に或いは
適宜併用して化学的に増感することができる。更に必要
に応じて、色素類の単独もしくは組合せ使用、またはそ
れらとのスチリル染料との組合せ使用によつて分光増感
や強色増感ができる。 本発明において、ハロゲン化銀乳剤層に、トリアゾール
類、テトラゾール類、イミダゾール類、アザインデン
類、第4級ベンゾチアゾリウム化合物、亜鉛あるいはカ
ドミウム化合物などの安定剤を含有せしめることができ
る。また、第4級アンモニウム塩型またはポリエチレン
グリコール型の増感化合物を含むこともできる。そして
また、グリセリン、1,5−ペンタンジオールのようなジ
ヒドロキシアルカン、エチレンビスグリコール酸エステ
ル、ビス−エトキシジエチレングリコールサクシネー
ト、アクリル酸系の酸アミド、ラテツクう等の適当なゼ
ラチン可塑剤を含むことができる。また、前述した硬膜
剤や、サポニン等の延展剤、あるいはスルホコハう酸塩
等の塗布助剤等種々の写真用添加剤を含有することがで
きる。更に又、必要に応じてカブリ防止剤、紫外線吸収
剤等通常写真に使用される各種添加剤を含ませることも
できる。 本発明に係るX線感材に使用される支持体としては、例
えば、ポリエチレンテレフタレート等のポリエステルフ
イルム、ポリアミドフイルム、ポリカーボネートフイル
ム、スチレンフイルムなどの種々のものが用いられ、こ
れらは青色などに染色されていてもよく、使用目的に応
じて適宜選択すればよい。 〔発明の作用効果〕 本発明によれば、高鮮鋭度と高濃度部の露光ラチチュー
ドの広さを同時に解決したので、診断能の高いX線感材
を提供でき、とくに、造影剤を用いる胃部撮影や、骨り
よう及び軟部組織の撮影の場合における従来タイプの有
する欠点を解消することが可能である。 〔実施例〕 次に実施例を挙げて本発明を例証するが、本発明の実施
態様はこれらに限定されるものではない。 実施例−1 ゼラチン水溶液中に、沃化カリウム2.5モル%を含む臭
化カリウム溶液とアンモニア性硝酸銀溶液とをダブルジ
エツト法で流速を徐々に速めながら添加して、1.05μm
の沃臭化銀正八面体単分散乳剤を得た。更にアンモニア
性硝酸銀溶液と臭化カリウム溶液とをダブルジエツト法
で添加して純臭化銀のシエルをかぶせた。この間pAg
は10.0に保ち、pHは9.0から8.0に徐々に低下させた。
この乳剤を〔A〕とする。この乳剤〔A〕は平均粒径1.
25μmの正八面体単分散乳剤であつた。 また、上記乳剤〔A〕と同様の製法で平均粒径0.65μm
の正八面体単分散乳剤〔B〕を調製した。 更に乳剤〔A〕,〔B〕と同じハライド組成の沃臭化銀
乳剤を順混合法で調製して乳剤〔C〕を得た。この乳剤
〔C〕は平均粒径が1.25μmの双昌型多分散乳剤であつ
た。 また乳剤〔C〕と同様の製法で、平均粒径0.65μmの双
昌型多分散乳剤〔D〕を得た。 脱塩後、これらの乳剤に金増感および硫黄増感をほどこ
した後、4−ヒドロキ−6−メチル−1,3,3a,7−テトラ
ザインデンを加え安定化し、表−2のように乳剤を混合
した。更に延展剤、硬膜剤等の一般的な写真用添加剤を
加えた後、青色に染色され且つ下引きされたポリエチレ
ンテレフタレートフイルムベース上に、各面上に銀量が
30mg/100cm2となるように、両面に塗布、乾燥し、直
接用X線感材の試料(No.1〜10)を作成した。 これらの各試料のセンシトメトリーを本発明の現像液−
1に用いる前記センシトメトリー〔A〕によつて行なつ
た。なお現像機は、ローラー搬送型自動現像機New QX-1
200(小西六写真工業株式会社製)を用いて処理した。 これらの結果を表−2に示す。なお鮮鋭度の評価はOT
F曲線の1.0,1.5,2.0lines/mmの鉛製の矩形波の入つた
OTF測定用チヤートを螢光スクリーンのフロント側の
裏面に密着させ、試料面の、鉛の矩形波で遮蔽されてい
ない部分の濃度が両面で1.0になる様にX線照射し、乳
剤のバツク側の面を剥離し、もう一方の面の矩形波のパ
ターンをサクラ・マイクロデンシトメーターM−5型
(小西六写真工業株式会社製)を用いて、矩形波と直角
方向にスキヤンニング測定した。なお、この時のアパー
チヤーサイズは矩形波の平行方向に230μm、直角方向
に25μmで拡大倍率は100倍である。 また露光ラチチュードの評価は、光学濃度がベース濃度
+カブリ濃度+2.00と同3.00との間の露光量差(対数表
示)で表わした。表−2から明らかなように、本発明の条件を満たす試料
No.2および同No.7は、鮮鋭度が高くかつ高濃度部の露
光ラチチュードも広いことが判る。 実施例−2 実施例−1の乳剤〔A〕を実施例−1と同様に化学増
感、塗布、乾燥して試料No.11〜14を得た。ただ
し、硬膜剤の量を表−3のように変化させた。 センシトメトリー及び画室の評価は実施例−1の如く行
ない、結果を表−3に示した。表−3から明らかなように、本発明の条件を満たす試料
No.12および同No.13は、鮮鋭度が高く、かつ高濃度
部の露光ラチチュードも広いことが判る。 なお硬膜剤をグリオキザールからS−トリアジンに代え
ても、同様の結果が得られた。 実施例−3 実施例−1の乳剤〔A〕と同様に作成した。但し、pA
gを9.0に保つことのみを変えて、乳剤〔E〕を調製し
た。この乳剤〔E〕は平均粒径1.25μmの立方体単分散
乳剤であつた。 この乳剤〔E〕を、実施例−1と同様に化学増感、塗
布、乾燥して試料No.15〜17を得た。但し、乳剤の
添加剤の中に表−4で示すような現像抑制剤を加えた。 これらの試料のセンシトメトリー及び画室の評価は実施
例−1の如く行ない、結果を表−4に示した。表−4から明らかなように、本発明の条件を満たす試料
No.15〜No.17は、鮮鋭度が高くかつ高濃度部の露光
ラチチュードも広いことが判る。 比較例 実施例−1の方法により1.25μmの沃臭化銀八面体単分
散乳剤[A]を得た。また、同様に0.65μmの正八面体
単分散乳剤[B]を得た。更に、1.25μmの双晶型型多
分散乳剤[C]と0.65μmの双晶型多分散乳剤[D]も
同様にして得た。 また、コントロールドダブルジェット法により単分散性
の高い1.15μm沃臭化銀八面体単分散乳剤[E]を得
た。更に、順混合法における混合時間を変えることによ
り[D]より、さらに多分散性な0.55μmの双晶多分散
乳剤[F]を得た。これらの乳剤を用いて、実施例−1
と同様な方法により試料を作製し評価を行なった。乳剤
の混合比率は表中に示す。
TECHNICAL FIELD The present invention relates to a silver halide photographic light-sensitive material for X-rays having high diagnostic ability. More specifically, the present invention relates to a silver halide photographic light-sensitive material for X-rays which has a wide exposure latitude in a high density portion, is easy to use, has a high sharpness and is easy to diagnose. [Prior Art] A silver halide photographic light-sensitive material for X-rays (one having a photosensitive emulsion layer on both sides of a support and one having a light-sensitive emulsion layer on only one side thereof will be referred to below as both). In X-ray photography of each part of a living body by "X-ray sensitive material"), high diagnostic ability is required for early detection of lesions and prevention of misdiagnosis, but conventional X-ray sensitive materials are not always necessary. I'm not satisfied. That is, conventional direct X-ray sensitive materials are roughly classified into a high gamma type shown in (a), a low gamma type shown in (b), and a moderate type shown in (c) in the photographic characteristic curve of FIG. , The high gamma type (a) is
Although the sharpness is high, it is difficult to use because the exposure latitude is narrow, and the low gamma type (b), on the contrary, has a wide exposure latitude and is easy to use, but it is difficult to diagnose due to low sharpness, and the moderate type (c) Has only a moderate sharpness and exposure latitude. In each of these types of direct-use X-ray sensitive materials, in the characteristic curve when treated with the same developer-1 as in the present invention, a gamma (gamma 1) between an optical density of 0.50 and an optical density of 1.50, and Typical examples of gamma (gamma 2) between the optical densities of 2.00 and 3.00 are shown in Table 1. In the actual examples of X-ray photography using these conventional type direct X-ray sensitive materials, the following serious defects or inconveniences were sometimes observed. That is, the most living body part of X-ray photography in Japan is the stomach, and a contrast agent is used to enhance the descriptive power. However, in the conventional high-gamma type direct X-ray sensitive material, the contrast agent portion is exposed. If you match the amount,
After development, the image without a contrast agent gave only a black image, which could not contribute to diagnosis. In order to avoid such a phenomenon, a low gamma type direct X-ray sensitive material is often used. However, in the case of this X-ray sensitive material, on the other hand, since the sharpness decreases, the stomach wall portion containing a contrast agent is reduced. The diagnostic ability of is reduced. As a practical example of X-ray photography of another living body part,
There are images of bones and soft tissues (flesh or cartilage) of hands and legs, and even in this case, the sharpness of the fine structure of bones is high in the conventional high gamma type X-ray sensitive material. However, the soft tissue was crushed in black and could not contribute to the diagnosis. On the contrary, when the low gamma type X-ray sensitive material was used, the soft tissue was depicted, but the sharpness of the bone was low. [Object of the Invention] Therefore, an object of the present invention is to provide an X-ray sensitive material having a high sharpness, a wide exposure latitude in a high density portion, and a high diagnostic ability. [Structure of the Invention] The X-ray sensitive material of the present invention which achieves the above object has a characteristic curve when treated under the following processing conditions using the developer-1 having the following composition. The gamma between
It is characterized in that the gamma between 2.7 and 3.3 and the optical density between 2.00 and 3.00 is 1.5 to 2.5. Developer-1 In a preferred embodiment of the present invention, in the characteristic curve when treated with the developing solution-1, the gamma between the optical densities of 0.50 and 1.50 is 2.8 to 3.1, and the optical density of 2.00 is the same.
The gamma between 3.00 and 1.7 is 2.3. The characteristic curve referred to in the present invention is obtained by the following optical sensitometry [A]. (Photosensitometry [A]) The exposure is carried out by sandwiching an X-ray sensitive material having a photosensitive emulsion layer on both sides (or one side) of a transparent support between two optical wedges and a light source having a color temperature of 5,400 ° K. At the same time, expose both sides at the same amount for 1/10 seconds. The processing is carried out using an automatic processor such as a roller transfer type according to the following steps. The developing solution used at this time is the developing solution-1, and the fixing solution is not particularly limited as long as it is an acidic hardening fixing solution, and is, for example, Sakura XF (manufactured by Konishi Rokusha Kogyo Co., Ltd.). In the present invention, gamma is the base (support) on the characteristic curve.
It means the slope of the straight line connecting the density +0.50 density point and the base density +1.50 density point, and the base density +2.00 density point and the base density +3.00 density point It means the slope of the straight line connecting the. More specifically, if the angle at which these directs intersect the exposure amount axis (horizontal axis) is θ, it means tan θ. The method for obtaining the characteristic curve of the present invention is arbitrary, and a monodisperse emulsion, a polydisperse emulsion, a core-shell type monodisperse emulsion, a single-use or a combination of two or more core-shell type polydisperse emulsions, a grain size or a grain size. Any technique such as control of distribution, adaptation of silver halide crystal habit, use of photographic additives such as hardeners and development control agents may be used. A specific example of obtaining the characteristic curve of the present invention is as follows. The first method is to use a silver halide emulsion containing a mixture of large-grain silver halide grains and small-grain silver halide grains. For example, a monodisperse (preferably core-shell type) emulsion having an average grain size of 1.35 μm and a monodisperse (preferably core-shell type) emulsion having an average grain size of 0.65 μm are each optimally chemically sensitized, and then silver halide is added. It is achieved by mixing in a molar ratio of 3: 1. As another example of this mixed content, for example, a monodisperse (core-shell type) emulsion having an average grain size of 1.25 μm and a monodisperse (core-shell type) emulsion having an average grain size of 0.70 μm are optimally used. After chemical sensitization, the mixture is carried out at a molar ratio of silver halide of 4: 1. The second method is by mixing a monodisperse emulsion and a polydisperse emulsion. For example, after optimally chemically sensitizing a monodisperse emulsion having an average grain size of 1.35 μm and a polydisperse emulsion having an average grain size of 0.75 μm,
This is achieved by mixing the silver halide in a molar ratio of 3: 1. Other examples of this mixed content include, for example, the average particle size.
The optimum is to chemically sensitize a monodisperse emulsion having a grain size of 1.15 μm and a polydisperse emulsion having an average grain size of 0.55 μm, and then mix them at a molar ratio of silver halide of 4: 1. The silver halide used in this method is also preferably the core-shell type. A third method is to use a large amount of a hardener for a photosensitive silver halide (monodispersity, especially core-shell type monodispersity is preferred) emulsion having a very high gamma. Therefore, it is possible to increase the degree of dura. That is, by increasing the degree of hardening, the gamma of the high density part of the characteristic curve becomes lower than that of the middle density part.
The method of applying the type and usage of the hardener may be a method known in the photographic industry, for example, an aldehyde compound, a ketone compound, a halogen-substituted acid such as mucochloric acid, an ethyleneimine compound, a vinylsulfone compound, etc. Can be used. A fourth method is to add a kind of development inhibitor to a photosensitive silver halide (monodispersity, especially core shell type monodispersity is preferable) emulsion having very high gamma. Therefore, it is possible to preferentially soften the high-density portion of the characteristic curve. The kind of such a development inhibitor and the application method such as usage may be a method known in the photographic industry, and for example, an indazole compound or a mercapto-succinic acid compound may be preferably used. The monodisperse emulsion used in the first and second methods of the present invention can be prepared by a conventional method, for example, The Photographic Journ
al, 79 , 330-338 (1939), the method reported by trivelli, Smith measured the average particle diameter and found that at least 95% of the particles by number or weight were ± 40% of the average particle diameter.
Within the range, more preferably within ± 30% of the silver halide emulsion. A method for producing such a monodisperse emulsion is known, and for example, J. Phot.S.
ci., 12 , 242-251 (1963), Japanese Patent Publication No. 48-36890,
No. 52-16364 and Japanese Patent Laid-Open No. 55-142329, and Japanese Patent Application No. 56-65573.
The techniques described in the specification can also be adopted. The silver halide used in the present invention may be a core-shell type monodisperse dispersion, and these core-shell emulsions are known from JP-A-54-48521. The silver halide grains used in the present invention are, for example, those described in T.W.
H. “The Theory of the Photographic Proces” by James
s "4th edition, published by Macmillan (1977), pages 38-104, etc., neutral method, acidic method, ammonia method, forward mixing, back mixing, double-jet method, controlled-double-jet method, It can be produced by applying methods such as the Convurion method, the core / shell method, etc. The silver halide composition includes silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc. Either of can be used,
The most preferred emulsion is a silver iodobromide emulsion containing less than about 10 mol% silver iodide. The grain size of silver halide grains is
There is no particular limitation, but 0.1-2 μm is preferable. Further, in order to improve the flash exposure characteristics, these silver halide grains or silver halide emulsions contain iridium salts and / or
Alternatively, a rhodium salt may be contained. As a hydrophilic protective colloid which is a dispersant for silver halide, gelatin is preferable, and various natural or synthetic colloid substances such as gelatin derivatives and polyvinyl alcohol are used alone or in combination with gelatin. As the sensitizer which can be advantageously used in the present invention, a noble metal sensitizer, for example, a gold compound, ruthenium, rhodium,
Palladium, iridium, platinum, etc., and sulfur sensitizer,
Active gelatin, sulfur compounds, etc. or selenium sensitizer if standing
For example, active and inactive selenium compounds and the like, further reduction sensitizers such as monovalent tin salts, polyamines, silane compounds, bisalkylamino sulfides, isinoaminomethane sulphonic acid, hydrazinium salts, hydrazine derivatives and the like, and the above 4 It can be roughly divided into species. These sensitizers can be chemically sensitized individually or in combination. Further, if necessary, spectral sensitization or supersensitization can be performed by using dyes alone or in combination, or by using them in combination with a styryl dye. In the present invention, the silver halide emulsion layer may contain a stabilizer such as triazoles, tetrazoles, imidazoles, azaindenes, quaternary benzothiazolium compounds, zinc or cadmium compounds. Further, a quaternary ammonium salt type or polyethylene glycol type sensitizing compound may be contained. And it also contains a suitable gelatin plasticizer such as glycerin, dihydroxyalkanes such as 1,5-pentanediol, ethylene bisglycolate ester, bis-ethoxydiethylene glycol succinate, acrylic acid amide, and latex. it can. Further, various photographic additives such as the above-mentioned hardener, spreading agent such as saponin, and coating aid such as sulfosuccinate can be contained. Furthermore, if necessary, various additives commonly used in photography such as antifoggants and ultraviolet absorbers can be included. As the support used for the X-ray sensitive material according to the present invention, for example, various ones such as polyester film such as polyethylene terephthalate, polyamide film, polycarbonate film and styrene film are used, and these are dyed blue or the like. And may be appropriately selected depending on the purpose of use. [Advantageous effects of the invention] According to the present invention, since the high sharpness and the width of the exposure latitude of the high density portion are solved at the same time, it is possible to provide an X-ray sensitive material having a high diagnostic ability, and in particular, a stomach using a contrast agent. It is possible to eliminate the drawbacks of the conventional type in the case of partial imaging and imaging of bone and soft tissue. [Examples] Next, the present invention will be illustrated with reference to Examples, but the embodiments of the present invention are not limited thereto. Example-1 A potassium bromide solution containing 2.5 mol% of potassium iodide and an ammoniacal silver nitrate solution were added to a gelatin aqueous solution by the double jet method while gradually increasing the flow rate to 1.05 μm.
A silver iodobromide octahedron monodisperse emulsion was obtained. Further, an ammoniacal silver nitrate solution and a potassium bromide solution were added by a double jet method to cover with pure silver bromide shell. During this period pAg
Was maintained at 10.0 and the pH was gradually decreased from 9.0 to 8.0.
This emulsion is designated as [A]. This emulsion [A] has an average grain size of 1.
It was a 25 μm regular octahedral monodisperse emulsion. Also, the average grain size is 0.65 μm in the same manner as the above emulsion [A].
A regular octahedral monodisperse emulsion [B] was prepared. Further, a silver iodobromide emulsion having the same halide composition as the emulsions [A] and [B] was prepared by a forward mixing method to obtain an emulsion [C]. This emulsion [C] was a Sosho type polydisperse emulsion having an average grain size of 1.25 μm. Also, a Sochang type polydisperse emulsion [D] having an average particle size of 0.65 μm was obtained by the same production method as the emulsion [C]. After desalting, these emulsions were subjected to gold sensitization and sulfur sensitization, and then 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added to stabilize the emulsion. The emulsions were mixed. Further, after adding general photographic additives such as a spreader and a hardener, the amount of silver on each surface becomes 30 mg / 100 cm 2 on a polyethylene terephthalate film base dyed blue and subbed As described above, both surfaces were coated and dried to prepare samples for direct X-ray sensitive material (No. 1 to 10). Sensitometry of each of these samples was carried out by the developer of the present invention-
The sensitometry [A] used in Example 1 was used. In addition, the developing machine is a roller transport type automatic developing machine New QX-1
It was treated with 200 (manufactured by Konishi Rokusha Kogyo Co., Ltd.). The results are shown in Table-2. The evaluation of sharpness is OT
An OTF measurement chart containing a rectangular wave of 1.0, 1.5, 2.0 lines / mm of the F curve and containing a rectangular wave made of lead was brought into close contact with the back surface of the front side of the fluorescent screen, and was not shielded by the rectangular wave of lead on the sample surface. X-ray irradiation was performed so that the density of the part was 1.0 on both sides, the back side of the emulsion was peeled off, and the rectangular wave pattern on the other side was made using the Sakura Micro Densitometer M-5 (Konishi Roku Photo (Manufactured by Kogyo Co., Ltd.) was used for scanning measurement in the direction perpendicular to the rectangular wave. The aperture size at this time is 230 μm in the parallel direction of the rectangular wave and 25 μm in the perpendicular direction, and the magnification is 100 times. The exposure latitude was evaluated by the difference in exposure amount (logarithmic display) between the optical density of the base density + fog density + 2.00 and 3.00. As is clear from Table 2, samples satisfying the conditions of the present invention
It can be seen that No. 2 and No. 7 have high sharpness and a wide exposure latitude in the high density area. Example-2 The emulsion [A] of Example-1 was chemically sensitized, coated and dried in the same manner as in Example-1 to obtain sample Nos. 11-14. However, the amount of the hardener was changed as shown in Table-3. Sensitometry and evaluation of laboratories were performed as in Example-1, and the results are shown in Table-3. As is clear from Table 3, samples satisfying the conditions of the present invention
It can be seen that No. 12 and No. 13 have high sharpness and a wide exposure latitude in the high density portion. Similar results were obtained even when the hardener was changed from glyoxal to S-triazine. Example-3 It was prepared in the same manner as the emulsion [A] of Example-1. However, pA
Emulsion [E] was prepared except that g was kept at 9.0. This emulsion [E] was a cubic monodisperse emulsion having an average grain size of 1.25 μm. This emulsion [E] was chemically sensitized, coated and dried in the same manner as in Example-1 to obtain sample Nos. 15-17. However, the development inhibitors shown in Table 4 were added to the emulsion additives. The sensitometry of these samples and the evaluation of compartments were performed as in Example-1, and the results are shown in Table-4. As is clear from Table 4, samples satisfying the conditions of the present invention
It can be seen that Nos. 15 to 17 have high sharpness and a wide exposure latitude in the high density portion. Comparative Example By the method of Example 1, a 1.25 μm silver iodobromide octahedral monodisperse emulsion [A] was obtained. Similarly, a regular octahedron monodisperse emulsion [B] of 0.65 μm was obtained. Further, a 1.25 μm twin type polydisperse emulsion [C] and a 0.65 μm twin type polydisperse emulsion [D] were similarly obtained. A 1.15 μm silver iodobromide octahedral monodisperse emulsion [E] having a high monodispersity was obtained by the controlled double jet method. Furthermore, by changing the mixing time in the forward mixing method, a more polydisperse twin crystal polydisperse emulsion [F] of 0.55 μm was obtained from [D]. Using these emulsions, Example-1
A sample was prepared and evaluated in the same manner as in. The mixing ratio of emulsions is shown in the table.

【図面の簡単な説明】 第1図は従来タイプの直接用X線感材の写真特性曲線を
示すグラフである。 図中、(a)は高ガンマ型、(b)は低ガンマ型、(c)は中庸
型を示す。
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a graph showing a photographic characteristic curve of a conventional type direct X-ray sensitive material. In the figure, (a) shows a high gamma type, (b) shows a low gamma type, and (c) shows a moderate type.

Claims (1)

【訂正明細書】 【特許請求の範囲】 【請求項1】下記組成の現像液−1を用いて下記処理条
件で処理されたときの特性曲線において、光学濃度0.50
と同1.50との間のガンマが2.7〜3.3であり、かつ光学濃
度2.00と同3.00との間のガンマが1.5〜2.5であることを
特徴とするX線用ハロゲン化銀写真感光材料。 現像液−1 亜硫酸カリウム 55.0 g ハイドロキノン 25.0 g 1−フエニル−3−ピラゾリドン 1.2 g ホウ酸 10.0 g 水酸化カリウム 21.0 g トリエチレングリコール 17.5 g 5−メチルベンツトリアゾール 0.04g 5−ニトロベンツイミダゾール 0.11g 1−フエニル−5−メルカプトテトラゾール 0.015g 氷酢酸 1.60g 臭化カリウム 4.0 g 水を加えて1に仕上げる。 処理条件 処理温度 処理時間 現像 35℃ 25秒 定着 34℃ 25秒 水洗 33℃ 25秒 乾燥 45℃ 15秒
[Claims] [Claims] [Claims] [Claim 1] An optical density of 0.50 in a characteristic curve when a developer-1 having the following composition is processed under the following processing conditions.
And gamma between 1.50 and 1.50 are 2.7 to 3.3, and gamma between optical density 2.00 and 3.00 is 1.5 to 2.5, a silver halide photographic light-sensitive material for X-rays. Developer-1 Potassium sulfite 55.0 g Hydroquinone 25.0 g 1-Phenyl-3-pyrazolidone 1.2 g Boric acid 10.0 g Potassium hydroxide 21.0 g Triethylene glycol 17.5 g 5-Methylbenztriazole 0.04 g 5-Nitrobenzimidazole 0.11 g 1- Phenyl-5-mercaptotetrazole 0.015g Glacial acetic acid 1.60g Potassium bromide 4.0g Add water to finish to 1. Processing conditions Processing temperature Processing time Development 35 ° C 25 seconds Fixing 34 ° C 25 seconds Washing 33 ° C 25 seconds Drying 45 ° C 15 seconds

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