JPH03612B2

JPH03612B2 -

Info

Publication number: JPH03612B2
Application number: JP9997682A
Authority: JP
Inventors: Koichi Ueda; Hiroaki Shiozawa; Bon Pponda; Akio Suzuki
Original assignee: Konica Minolta Inc
Current assignee: Konica Minolta Inc
Priority date: 1982-06-12
Filing date: 1982-06-12
Publication date: 1991-01-08
Also published as: JPS58217929A

Description

[Detailed description of the invention]

本発明は、Ｘ線写真用のハロゲン化銀写真感光
材料に関する。更に詳しくは、高い感度を有し、
且つカブリの発生が少ないＸ線写真用ハロゲン化
銀写真感光材料に関する。医療用等のラジオグラフイーにおいては、人体
へのＸ線被爆線量を可能な限り軽減し、その上で
情報を正確に記録し、且つこの情報記録の観察を
容易にすることが強く望まれている。また近年の
情報の多量化、多様化に伴い、写真感光材料の迅
速現像処理化が進められている。このような要求に応じる為に、高感度にしてカ
ブリが少なく、かつ安定した写真性能を保持でき
るとともに、高温高湿の長期保存及び高温迅速現
像処理等の苛酷な条件に耐えうる、優れた写真感
光材料の提供が望まれていた。ハロゲン化銀写真感光材料を増感する方法とし
ては、従来から多数の方法が知られているが、そ
れらの方法で、高感度化を図ると、いずれの方法
においてもカブリが発生し易いという欠点を有し
ていた。また近年、要求される高温迅速現像処理におい
ては、現像処理工程が高温度状態で行なわれるた
め、カブリが発生しやすいという不都合を有して
いた。このような問題に対処する為、従来の増感技術
を適宜組合せ、目的とするハロゲン化銀写真感光
材料の製造を試みているが、前述の要求を十分に
満足するものはまだ確立されていない。本発明者はハロゲン化銀写真感光材料におい
て、前記一般式〔〕で示される化合物の少なく
とも１つを添加含有せしめると共に、一般式〔
−ａ〕，〔−ｂ〕又は〔−ｃ〕で示される化合
物の少なくとも１つを併用したところ、高感度を
維持した上で、カブリの抑制効果が著しく向上す
るという全く予想できない結果が得られることを
見出した。本発明の第１の目的は、カブリの発生を伴わな
い、かつ階調性の優れた高感度のＸ線写真用ハロ
ゲン化銀写真感光材料を提供するにある。本発明の第２の目的は、高温高湿下で長期間保
存しても感度低下が少なく、かつカブリの発生を
抑制できるＸ線写真用ハロゲン化銀写真感光材料
を提供するにある。本発明の第３の目的は、高温迅速現像処理した
場合にも、カブリの発生を抑制して高感度を与え
るＸ線写真用ハロゲン化銀写真感光材料を提供す
るにある。上記目的は、下記一般式〔〕で示される化合
物の少なくとも１種と、下記一般式〔−ａ〕、
〔−ｂ〕又は〔−ｃ〕で示される化合物の少
なくとも１種とを組合せて含有することを特徴と
するハロゲン化銀写真感光材料によつて達成され
る。〔式中、Ｒは炭素原子数１〜４の低級アルキル基
（例えば、メチル基、エチル基、プロピル基、ブ
チル基）を表わす。〕〔式中、R₁は水素原子、ヒドロキシル基、それ
ぞれ同種もしくは異種のハロゲン原子、置換基を
有してもよいアルキル基、置換基を有してもよい
アラルキル基、置換基を有してもよいアルコキシ
基、置換基を有してもよいカルボキシメチル基、
−COOM基または−SO₃M基（Ｍは水素原子、ア
ルカリ金属原子もしくはアンモニウム基を表わ
す）を表わし、R₂，R₃，R₄は−COOM基または
−SO₃M基を表わし、n₁，n₂は１、２または３、
n₅は１または２を表わし、n₃，n₄は０または１を
表わす。但し、n3，n₄は共に０であることはな
い。〕そして、上記置換基としては、以下に挙げる各
例示化合物の有する置換基がその代表例として含
まれ、そのうち−COOM基（Ｍは水素原子、ア
ルカリ原子又はアンモニウム基を表わす。以下同
じ。）および−SO₃M基が特に好ましい。次に本発明に用いられる前記一般式〔〕で示
される化合物の具体例を示すが、本発明に用いら
れる化合物はこれによつて限定されるものではな
い。次に、本発明に用いられる一般式〔−ａ〕、
〔−ｂ〕又は〔−ｃ〕で示される化合物の具
体例をあげるが、本発明に用いられる化合物はこ
れらによつて限定されるものではない。 The present invention relates to a silver halide photographic light-sensitive material for X-ray photography. More specifically, it has high sensitivity,
The present invention also relates to a silver halide photographic material for X-ray photography that causes less fog. In medical radiography, it is strongly desired to reduce the X-ray exposure dose to the human body as much as possible, record information accurately, and make it easy to observe this information record. There is. Furthermore, with the recent increase in the amount and diversification of information, rapid processing of photographic light-sensitive materials is progressing. In order to meet these demands, we are developing excellent photographs that are highly sensitive, have little fog, maintain stable photographic performance, and can withstand harsh conditions such as long-term storage at high temperatures and high humidity, and rapid high-temperature processing. There was a desire to provide photosensitive materials. Many methods have been known for sensitizing silver halide photographic materials, but when trying to increase the sensitivity using these methods, each method has the disadvantage that fog is likely to occur. It had Furthermore, in the high-temperature and rapid development processing required in recent years, the development process is carried out at a high temperature, which has the disadvantage of easily causing fogging. In order to deal with these problems, attempts have been made to produce the desired silver halide photographic materials by appropriately combining conventional sensitization techniques, but a material that fully satisfies the above-mentioned requirements has not yet been established. . The present inventor added and contained at least one compound represented by the general formula [] in a silver halide photographic light-sensitive material, and also added and contained at least one compound represented by the general formula [].
When at least one of the compounds represented by -a], [-b], or [-c] is used in combination, a completely unexpected result is obtained in which the fog suppression effect is significantly improved while maintaining high sensitivity. I discovered that. A first object of the present invention is to provide a silver halide photographic material for X-ray photography which is free from fog and has excellent gradation and high sensitivity. A second object of the present invention is to provide a silver halide photographic light-sensitive material for X-ray photography that exhibits little decrease in sensitivity even when stored under high temperature and high humidity for a long period of time, and can suppress the occurrence of fog. A third object of the present invention is to provide a silver halide photographic light-sensitive material for X-ray photography that suppresses fogging and exhibits high sensitivity even when subjected to high-temperature rapid development. The above purpose is to combine at least one compound represented by the following general formula [], and the following general formula [-a],
This can be achieved by a silver halide photographic material containing a combination of at least one compound represented by [-b] or [-c]. [In the formula, R represents a lower alkyl group having 1 to 4 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group). ] [In the formula, R ₁ is a hydrogen atom, a hydroxyl group, a halogen atom of the same or different type, an alkyl group that may have a substituent, an aralkyl group that may have a substituent, or a halogen atom that may have a substituent. Good alkoxy group, carboxymethyl group which may have substituents,
-COOM group or _-SO3M group (M represents a hydrogen atom, alkali metal atom or ammonium group), _R2 , _R3 , _R4 represent -COOM group or _-SO3M group, _n1 ,n ₂ is 1, 2 or 3,
n ₅ represents 1 or 2, and n ₃ and n ₄ represent 0 or 1. However, both n3 and _n4 are never 0. ] Representative examples of the above-mentioned substituents include the substituents of each of the exemplified compounds listed below, among which -COOM group (M represents a hydrogen atom, an alkali atom, or an ammonium group; the same applies hereinafter); The group _-SO3M is particularly preferred. Next, specific examples of the compound represented by the general formula [] used in the present invention will be shown, but the compounds used in the present invention are not limited thereto. Next, the general formula [-a] used in the present invention,
Specific examples of compounds represented by [-b] or [-c] will be given, but the compounds used in the present invention are not limited thereto.

【式】【formula】

【formula】

【式】【formula】

[Developer]

無水亜硫酸ナトリウム 70ｇハイドロキノン 10ｇ無水硼酸１ｇ炭酸ナトリウム−水塩 20ｇ１−フエニル−１，３−ピラゾリドン 0.35ｇ水酸化ナトリウム５ｇ５−メチル−ベンゾトリアゾール 0.05ｇ臭化カリウム５ｇグルタルアルデヒド重亜硫酸塩 15ｇ氷酢酸８ｇ水を加えて１に仕上げる。尚、現像、定着及び水洗工程を一貫して行なう
連続ローラー搬送式自動現像機を用いた。次いで、この各試料をJIS法に基いてセンシト
メトリーを行ない、感度及びカブリを測定した。
その結果を同じく第１表に示す。但し、感度表示は試料No.１の試料感度を100と
する相対感度で示した。 Anhydrous sodium sulfite 70g Hydroquinone 10g Boric anhydride 1g Sodium carbonate hydrate 20g 1-phenyl-1,3-pyrazolidone 0.35g Sodium hydroxide 5g 5-methyl-benzotriazole 0.05g Potassium bromide 5g Glutaraldehyde bisulfite 15g Glacial acetic acid Add 8g water and make up to 1. Incidentally, a continuous roller conveyance type automatic developing machine was used, which performs development, fixing, and water washing steps in an integrated manner. Next, each sample was subjected to sensitometry based on the JIS method to measure sensitivity and fog.
The results are also shown in Table 1. However, the sensitivity is expressed as a relative sensitivity with the sample sensitivity of sample No. 1 as 100.

【表】第１表から明らかなように、一般式〔〕で示
される化合物と一般式〔−ａ〕，〔−ｂ〕又は
〔−ｃ〕で示される化合物を組み合わせて使用
することにより、カブリの発生を抑制しながら感
度の上昇がみられることがわかる。実施例２臭化銀98.4モル％と沃化銀1.6モル％からなる
（１，１，１）面をもつ双晶の高感度沃臭化銀ゼ
ラチン乳剤の硫黄及び金増感の反応終了後に第２
表に示す如く、一般式〔〕および一般式〔−
ａ〕，〔−ｂ〕で示される化合物を添加含有せし
めた。この様にして得られた高感度ハロゲン化銀
乳剤に、常法に従い塗布助剤及び硬膜剤を加えて
ポリエチレンテレフタレートベース上に塗布し、
片面の乾燥膜厚が10μになるように両面塗布し、
この上に３％ゼラチン水溶液からなる保護層を塗
設して、試料No.11〜17を作成した。各試料を実施例１と同じく現像、定着及び水洗
処理し、その写真性能を第２表に示した。なお、
表中に示す感度は、試料No.11の感度値を100とす
る相対値で示す。[Table] As is clear from Table 1, by using the compound represented by the general formula [] in combination with the compound represented by the general formula [-a], [-b] or [-c], fogging can be achieved. It can be seen that sensitivity increases while suppressing the occurrence of . Example 2 After completion of the sulfur and gold sensitization reaction of a high-sensitivity twinned silver iodobromide gelatin emulsion with (1,1,1) planes consisting of 98.4 mol% silver bromide and 1.6 mol% silver iodide, 2
As shown in the table, general formula [] and general formula [−
The compounds represented by a] and [-b] were added and contained. The high-sensitivity silver halide emulsion thus obtained was coated on a polyethylene terephthalate base by adding a coating aid and a hardening agent according to a conventional method.
Coat on both sides so that the dry film thickness on one side is 10μ,
A protective layer consisting of a 3% aqueous gelatin solution was applied thereon to prepare samples Nos. 11 to 17. Each sample was developed, fixed and washed in the same manner as in Example 1, and the photographic performance thereof is shown in Table 2. In addition,
The sensitivity shown in the table is shown as a relative value with the sensitivity value of sample No. 11 as 100.

【表】第２表からも一般式〔〕で示される化合物と
一般式〔−ａ〕，〔−ｂ〕又は〔−ｃ〕で示
される化合物の組み合わせによる高感度化とカプ
リ抑制の効果が明らかである。実施例３実施例１で得られた各試料について保存試験を
行なつた。すなわち、実施例１の各試料を露光前
に下記第３表で示す条件で３日間保存した後、実
施例１と同じく露光、現像処理して写真性能を測
定した。その結果を第３表に示す。なお、各試料
No.は実施例１の試料No.と各々対応し、感度は第１
表の試料No.１を100とする相対感度を示す。[Table] From Table 2, it is clear that the combination of the compound represented by the general formula [] and the compound represented by the general formula [-a], [-b], or [-c] increases sensitivity and suppresses Capri. It is. Example 3 A storage test was conducted on each sample obtained in Example 1. That is, each sample of Example 1 was stored for 3 days under the conditions shown in Table 3 below before exposure, and then exposed and developed in the same manner as in Example 1, and the photographic performance was measured. The results are shown in Table 3. In addition, each sample
The numbers correspond to the sample numbers of Example 1, and the sensitivity is the first
Relative sensitivity is shown with Sample No. 1 in the table as 100.

【表】【table】

【表】第３表から明らかな如く、本発明の試料は長期
間保存しても高い感度を保持した上でカブリの発
生を抑制することがわかる。[Table] As is clear from Table 3, the samples of the present invention maintain high sensitivity even after long-term storage and suppress the occurrence of fog.

Claims

[Claims] 1. A combination of at least one compound represented by the following general formula [] and at least one compound represented by the following general formula [-a], [-b] or [-c] A silver halide photographic material characterized by containing: [In the formula, R represents a lower alkyl group having 1 to 4 carbon atoms. ] [In the formula, R ₁ is a hydrogen atom, a hydroxyl group, a halogen atom of the same or different type, an alkyl group that may have a substituent, an aralkyl group that may have a substituent, or a halogen atom that may have a substituent. Good alkoxy group, carboxymethyl group which may have substituents,
-COOM group or _-SO3M group (M represents a hydrogen atom, alkali metal atom or ammonium group), _R2 , _R3 , _R4 represent -COOM group or _-SO3M group, _n1 , n ₂ is 1, 2 or 3,
n ₅ represents 1 or 2, and n ₃ and n ₄ represent 0 or 1. However, both n ₃ and n ₄ are never 0. ]