JP2004157227A - Silver halide photographic sensitive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material which is satisfactorily uniformly coated and causes less unevenness in development. <P>SOLUTION: In a method for processing the silver halide photographic sensitive material which has at least one photosensitive silver halide photographic emulsion layer on one side or both sides of a support, silver halide emulsion grains in the silver halide emulsion layer are tabular grains having an average thickness of 0.03-0.11 μm and an average aspect ratio of 13-30. The silver halide photographic sensitive material contains at least one fluorine compound selected from the group comprising compounds represented by the formulae Rf<SB>1</SB>-(ORf<SB>2</SB>)<SB>n1</SB>-(L<SB>1</SB>)<SB>m2</SB>-(X<SB>1</SB>)<SB>m1</SB>and [(Rf<SB>3</SB>O)<SB>n2</SB>-(PFC)-CO-Y<SB>2</SB>]<SB>k</SB>-L<SB>2</SB>-(X<SB>2</SB>)<SB>m2</SB>. <P>COPYRIGHT: (C)2004,JPO

Description

【０１３５】
塗布試料の作成
（染料層塗布液の調製）
乳剤下層として塗設する染料層（クロスオーバーカット層）の各成分が、下記の塗布量となるように塗布液を調製した。
【０１３６】
（クロスオーバーカット用染料の調製方法）
染料Ａ（固形１０ｇ）に対してメタノール１５０ｍｌと水５０ｍｌの混合溶媒中で７０℃に制御しながら２時間撹拌し、水のウエットケーキ状染料Ｉ−４６を作製した。その結果、染料結晶中には染料１モルに対してメタノール１モルと水２モルが含まれていた。結晶溶媒の確認方法としては、ウエットケーキを測定用に室温乾燥し、１Ｈ−ＮＭＲにより結晶中のメタノールの存在が確認できた。またカールフィッシャー滴定法により結晶水の存在が確認できた。またこの結晶を１５０℃で加熱すると結晶中のメタノール、および結晶水が放出されることも確認した。このことからウエットケーキ中の染料固形濃度は５０質量％であった。
【０１３７】
（クロスオーバーカット用染料の微結晶水分散物の調製方法）
上述のウエットケーキ状染料を乾燥させないでウエットケーキとして取り扱い、染料固形として３．０ｇを秤取した。分散するための水と分散剤としてデモールＳＮＢ（花王（株）社製）の２５質量％溶液１．２ｇを予め混合した上で、先の染料を添加し、合計が３０ｇとなるように水で調整してから良く混合してスラリーとした。ジルコニア製ビーズを１２０ｇ用意し、スラリーと一緒にベッセルに入れ、１／１６ガロンのサンドグラインダーミル（アイメックス（株）社製）にて１５００ｒｐｍ回転でベッセルを水冷しながら分散した。ジルコニア製ビーズの平均粒径としては、１ｍｍのものを使用し、分散時間は８時間とした。分散終了後、染料の固形分濃度が５質量％となるように水を加えて分散液を取り出した。この染料分散物をＤＰ１とした。
【０１３８】
（染料層塗布液の調製方法）
以下の塗布量となるように水母液に各化合物を添加した。各化合物の添加順に、片面１ｍ^２当たりの素材塗布量を記載した。

このとき、酢酸または水酸化ナトリウムを少量用いてこの塗布液のｐＨを６．０に調整した。塗布量は片側１ｍ^２当たり１２．４ｍｌであった。
【０１３９】
【化２】

【０１４０】
（乳剤層塗布液の調製方法）
以下の塗布量となるように乳剤に各化合物を添加した。片面１ｍ^２当たりの素材塗布量
・塗布銀量 １．２５ｇ
・ゼラチン １．２５ｇ
・デキストラン（平均分子量３．９万） ３４４ｍｇ
・ポリスチレンスルホン酸ナトリウム（平均分子量６０万） ２７ｍｇ
・Ａ−２ １６２ｍｇ
・Ａ−３ １．９ｍｇ
・Ａ−４ ０．３５ｍｇ
・Ａ−５ １．９ｍｇ
・染料−１（オイル乳化物） 染料固形分として ０．３３ｇ
・１，２−ビス（ビニルスルホニルアセトアミド）エタン ５０ｍｇ
このときこの乳剤層の塗布液量は片側１ｍ^２当たり３２．６ｍｌであった。上記における化合物は以下のとおりであった。
【０１４１】
【化３】

【０１４２】
（表面保護層塗布液の調製方法）
以下の塗布量となるように各化合物を添加した。
片面１ｍ^２当たりの素材塗布量
・ゼラチン ０．７６７ｇ
・ポリアクリル酸ナトリウム（平均分子量４０万） ８０ｍｇ
・ポリスチレンスルホン酸ナトリウム（平均分子量６０万）１．１ｍｇ
・マット剤−１（平均粒径３．７μｍ） 固形分として７０ｍｇ
・Ａ−６ １８．１ｍｇ
・Ａ−７ ３４．５ｍｇ
・Ａ−８ ６．８ｍｇ
・Ａ−９ ３．２ｍｇ
・Ａ−１０ １．４ｍｇ
・Ａ−１１ ２．１ｍｇ
・Ａ−１２ １．０ｍｇ
・防腐剤Ｄ ０．９ｍｇ
・ｐ−ベンゾキノン ０．７ｍｇ
このとき水酸化ナトリウムを少量用いてこの表面保護層の塗布液のｐＨを６．８に調整した。塗布量は片側１ｍ^２当たり１０．７ｍｌであった。上記における化合物は以下のとおりであった。
【０１４３】
Ａ−９の代わりに本発明の１−７５、１−７３及び２−９を、Ａ−１０の代わりに１−５１、１−５０及び２−３３を、それぞれ等モルとなるように置きかえること以外は同様にして、表１に示すように各感光材料に添加した。
【化４】

【０１４４】
【化５】

【０１４５】
二軸延伸された厚さ１７５μｍの青色染色（１，４−ビス（２，６−ジエチルアニリノアントラキノンを含有する）ポリエチレンテレフタレート支持体上に、コロナ放電を行い、下記の主成分を含む各塗布液を第１下塗り層、第２下塗り層の順にワイヤーバーコーターにより支持体の両側に塗布した。
【０１４６】
・第１下塗り層（支持体側）
支持体の片側１ｍ^２当たりの塗布液量を４．９ｍｌとした。各添加素材の支持体の片側１ｍ^２当たりの塗布量は以下のとおりである。

乾燥温度 １９０℃
【０１４７】
・第２下塗り層
支持体の片側１ｍ^２当たりの塗布液量を７．９ｍｌとした。各添加素材の支持体の片側１ｍ^２当たりの塗布量は以下のとおりである。

乾燥温度 １８５℃
【０１４８】
（写真材料の塗布方法）
前述のように準備した下塗り塗布された支持体上に支持体側から染料層、乳剤層、表面保護層の構成になるように同時押し出し法により両面に同時塗布し、乾燥した。
【０１４９】
（塗布均一性の評価）
上記のようにして塗布した各感光材料を、白灯下で目視により表面を観察して、次のように５段階で評価した。
５：スポット故障や塗布ムラの発生は全く無い。
４：スポット故障や塗布ムラの発生は僅かにあるが、実用上全く問題無いレベルである。
３：スポット故障や塗布ムラの発生は少しあるが、実用上は許容されるレベルである。
２：スポット故障や塗布ムラの発生があり、実質上許容できないレベルである。
１：スポット故障や塗布ムラが多発しており、実用上全く許容できないレベルである。
結果を表１に示す。
【０１５０】
（処理）
自動現像機：富士写真フィルム（株）社製ＣＥＰＲＯＳ−３０
現像液の調製
【０１５１】

【０１５３】
（処理液の調製）
上記現像液濃度液を上記ＣＥＰＲＯ−３０用処理剤入容器に各パーツ剤毎に充填した。この容器はパーツ剤Ａ、Ｂ、Ｃの各部分容器が容器自身によって一つに連結されているものである。
また、上記定着液濃度も同種の容器に充填した。
まず、現像槽内にスターターとして、酢酸５４ｇと臭化カリウム５５．５ｇを含む水溶液３００ｍｌを添加した。
上記処理剤入容器を逆さにして自現機の側面に装着されている処理液ストックタンクの穿孔刃にさしこんで、キャップの封止膜を破り、容器内の各処理剤をストックタンクに充填した。
【０１５４】
これらの各処理剤を下記の割合で自現機の現像槽、定着槽に、それぞれ自現機に設置されているポンプを作動して満たした。
また、感光材料が４切サイズ換算で８枚処理される毎にも、この割合で、処理剤原液と水とを混合して自現機の処理槽に補充した。
【０１５５】
現像液
パーツ剤Ａ ５５ ｍｌ
パーツ剤Ｂ １０ ｍｌ
パーツ剤Ｃ １０ ｍｌ
水 １２５ ｍｌ
ｐＨ １０．５０
定着液
濃縮液 ８０ ｍｌ
水 １２０ ｍｌ
ｐＨ ４．６２
水洗槽には水道水を満たした。
【０１５６】
また、水あか防止剤として、放線菌を平均粒径１００μｍ、平均孔径３μｍのパーライトに担持させたもの０．４ｇをポリエチレン製のビン（ビン開口部を３００メッシュのナイロン布で覆い、この布より水および菌の流通が可能）に充填したものを３個用意し、そのうちの２個を水洗槽の底部に、１個を水洗水のストックタンク（液量０．２リットル）の底部にそれぞれ沈めた。
【０１５７】
（現像ムラの評価）
塗布された各感光材料の四切サイズ（１０インチ×１２インチ）に、均一な露光を行い、次に記述する処理条件にて黒化濃度が、１．１〜１．３の範囲に入るようにした。処理済感光材料をシャーカステン上で目視観察し、次のように５段階で評価した。
５：全体が均一に黒化していて、現像ムラは全く観察されないレベル。
４：現像ムラの発生は僅かにあるが、実用上全く問題無いレベルである。
３：現像ムラの発生は少しあるが、実用上は許容されるレベルである。
２：現像ムラの発生はがあり、実質上許容できないレベルである。
１：現像ムラの発生はが顕著で、実用上全く許容できないレベルである。
得られた結果を表１に示す。
【０１５８】
【表１】

【０１５９】
表１の結果から明らかなように、Ａ−９やＡ−１０のような比較の含フッ素化合物を用いた場合、ハロゲン化銀粒子の厚みが小さく、アスペクト比が大きくなるにつれて、塗布の均一性及び現像ムラが劣化する。特に、ハロゲン化銀粒子の厚みが０．０８μｍでアスペクト比が２２．５であるハロゲン化銀乳剤Ｂ−１を用いた場合、塗布均一性及び現像ムラが著しく劣化し、実用に耐えないものであった。
一方、本発明における一般式（１）や一般式（２）で表される含フッ素化合物を添加した場合には、ハロゲン化銀粒子の厚みが小さく、アスペクト比が大きい場合でも良好な塗布均一性と現像ムラの無い良好な結果を得ることができた。
このように、一般式（１）や一般式（２）で表される含フッ素化合物を添加によって、ハロゲン化銀の形状に依存せず、良好な塗布性能を示す塗布液となり、かつ、この塗布液を用いて形成された感光材料は、現像ムラが著しく減少した。
【０１６０】
【発明の効果】
本発明によれば塗布の均一性が良好で、現像ムラの少ないハロゲン化銀写真感光材料を提供できる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for processing a silver halide photographic light-sensitive material. In particular, the present invention relates to improvement of coating uniformity and development unevenness of medical X-ray photographic light-sensitive materials.
[0002]
[Prior art]
In recent years, the development processing of silver halide photographic light-sensitive materials in the medical field has progressed in speeding up of automatic processors and lowering of the replenishing liquid amount. Material 1m²It has become common to be less than 350 mL per hit. Such a silver halide photographic light-sensitive material requires a light-sensitive material having a small processing load during development, fixing, washing and drying.
The silver halide photographic light-sensitive material is developed after image exposure to obtain a visualized image, and the image is recognized by its light and shade. Therefore, the silver halide photographic light-sensitive material has a sensitivity suitable for the application and requires high image quality (called image quality). As the image quality, it is required that the maximum density of the image is high and the minimum density is low, the gradation and the graininess are appropriate for the application, and the color tone of the image is preferable. Increasing the maximum density of the image can be achieved simply by increasing the amount of silver halide applied. However, increasing the amount of coated silver is preferable because it increases the load of development processing for image formation, which leads to a decrease in development processing speed and an increase in the amount of waste liquid, resulting in a decrease in productivity and an increase in the burden on the global environment. Absent. In general, the maximum density per unit developed silver amount is referred to as covering power. This increase in covering power is of great interest to emulsion manufacturers as it enables the savings in the amount of silver necessary to maintain a constant optical density, and the improvement of silver halide emulsions to achieve this. A great deal of effort has been made.
[0003]
Patent Document 1 discloses that the developed silver covering power is remarkably increased by using tabular grains having a high aspect ratio and a small grain thickness as a silver halide emulsion.
Further, ultrathin tabular grains having a thickness of 0.07 μm or less are disclosed in Patent Document 2 and the like.
Patent Document 3 discloses a technique related to tabular grains having an epitaxial portion and a high aspect ratio.
[0004]
When the developed silver covering power is increased in this way, a slight non-uniformity in the amount of applied silver results in a large blackening density difference, so that the uniformity of coating becomes important. Similarly, since development unevenness due to development is likely to occur, coating uniformity is important in order to eliminate development unevenness.
[0005]
In other words, a silver halide photographic light-sensitive material using extremely flat tabular grains having a high aspect ratio of silver halide grains can obtain a high silver covering power, but also has good coating uniformity and little development unevenness. Is desired. As a result of research and development on these problems, it has been clarified that the use of the surfactants described in Patent Documents 4 to 6 is effective. However, the improvement effect is not sufficient, and further improvements can be made. It was necessary.
[0006]
[Patent Document 1]
U.S. Pat. No. 4,414,304
[Patent Document 2]
JP-A-6-43605
[Patent Document 3]
JP-A-8-101476
[Patent Document 4]
JP 2001-13629 A (paragraph numbers [0004] to [0031]
[Patent Document 5]
JP 2001-281788 (paragraph numbers [0008] to [0015]
[Patent Document 6]
JP 2002-72394 A (paragraph numbers [0003] to [0012]
[0007]
[Problems to be solved by the invention]
Accordingly, the problem to be solved by the present invention is that the average thickness of the silver halide emulsion grains in the silver halide photographic light-sensitive material is 0.03 μm or more and 0.11 μm or less and the average aspect ratio is 13 or more and 30 or less. Thus, a silver halide photographic light-sensitive material having good coating uniformity and less development unevenness is provided.
[0008]
[Means for Solving the Problems]
The problems to be solved by the present invention have been achieved by the following. That is,
(1) A method of processing a silver halide photographic material having at least one photosensitive silver halide photographic emulsion layer on one side or both sides of a support,
The silver halide emulsion grains in the silver halide emulsion layer are tabular grains having an average thickness of 0.03 to 0.11 μm and an average aspect ratio of 13 to 30;
A silver halide photographic light-sensitive material comprising at least one fluorine-containing compound selected from the group consisting of compounds represented by the following general formulas (1) and (2).
General formula (1)
Rf₁-(ORf₂)_n1-(L₁)_m2-(X₁)_m1
(Where Rf₁Represents an aliphatic group containing at least one fluorine atom, Rf₂Represents an alkylene group containing at least one fluorine atom, n1 and m1 each independently represent an integer of 1 or more, and m2 represents 1 or 0. L₁Represents a linking group and X₁Represents a hydroxyl group, an anionic group or a cationic group. )
General formula (2)
[(Rf₃O)_n2-(PFC) -CO-Y₂]_K-L₂-(X₂)_m2
(Where Rf₃Represents a perfluoroalkyl group having 1 to 4 carbon atoms, RFC represents a perfluorocycloalkyl group, Y₂Represents a linking group containing an oxygen atom or a nitrogen atom, and L₂Represents a bond or a linking group, and X₂Represents an anionic group, a cationic group, a nonionic group or a water-soluble polar group containing an amphoteric group, n2 represents an integer of 1 to 5, K represents an integer of 1 to 3, and m2 represents an integer of 1 to 5 Represents an integer. )
(2) In the above (1), the silver halide emulsion grains are tabular grains having an average thickness of 0.03 μm or more and 0.11 μm or less and an average aspect ratio of 13 or more and 25 or less. The silver halide photographic light-sensitive material described.
(3) The above (1) or (2), wherein the silver halide emulsion grains are silver iodobromide and the silver iodide content is 0.05 mol% or more and 0.45 mol% or less. The silver halide photographic light-sensitive material described in 1.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
The silver halide emulsion used in the present invention will be described. The silver halide emulsion grains of the present invention have any silver halide composition such as silver chloride, silver chlorobromide, silver chloroiodide, silver chloroiodobromide, silver bromide and silver iodobromide. May be. Silver bromide and silver iodobromide are preferable from the viewpoint of obtaining high sensitivity.
The silver iodide content is preferably 1 mol% or less, particularly 0.05 mol% or more and 0.45 mol% or less with respect to the amount of silver contained in the silver halide emulsion grains from the viewpoint of rapid development processing suitability. preferable.
[0010]
In the light-sensitive silver halide emulsion of the present invention, the average aspect ratio of silver halide emulsion grains is preferably 13 or more. The aspect ratio of a silver halide emulsion grain is defined as a value obtained by dividing the equivalent circle diameter of the projected area of one grain by the thickness of the grain. The aspect ratio is preferably 13 or more and 30 or less, and more preferably 13 or more and 25 or less. By setting the aspect ratio within the above range, the developed silver color tone is favorable, and the optical density per unit developed silver amount is most preferable.
The average equivalent circle diameter and the average thickness of the projected area of the silver halide emulsion grains are calculated as the average value of all the silver halide emulsion grains.
The average equivalent circle diameter of the silver halide emulsion grains in the present invention is preferably 0.6 μm or more and 3.0 μm or less, and more preferably 1.0 μm or more and 3.0 μm or less.
The average thickness of the silver halide emulsion grains in the invention is from 0.03 μm to 0.11 μm, preferably from 0.03 μm to 0.08 μm.
[0011]
In the present invention, the silver halide emulsion grains may be double twin grains having two parallel twin planes. Further, it may be a tabular grain having a {111} plane as a main plane or a tabular grain having a {100} plane as a main plane.
[0012]
The silver halide emulsion grains of the present invention are so-called tabular grains having an average thickness of 0.03 μm or more and 0.11 μm or less. In silver halide emulsions, such as cubic, octahedral and tetradecahedral An isotropically grown one or a multifaceted crystal type such as a sphere may be used in combination.
The proportion of tabular silver halide grains having an average thickness of 0.03 μm or more and 0.11 μm or less is preferably such that the sum of the projected areas is 50% or more and 100% or less with respect to the sum of the projected areas of all grains, Preferably they are 70% or more and 100% or less, Most preferably, they are 90% or more and 100% or less.
[0013]
As methods for producing tabular silver halide grains, methods known in the art can be used in appropriate combination.
Further, tabular grains having parallel twin planes and having a {111} plane as a main plane are described in JP-A-58-127927, JP-A-58-11939, and JP-A-58-113928. It can be easily prepared by referring to the prepared methods.
In addition, a seed crystal in which tabular grains are present in a mass of 40% or more in an atmosphere having a relatively low pBr value of pBr 1.3 or less is formed, and silver and a halogen solution are added simultaneously while maintaining the same pBr value. It can also be obtained by growing seed crystals.
In this grain growth process, it is desirable to add silver and halogen solutions so that new crystal nuclei are not generated.
The size of the tabular silver halide grains can be adjusted by controlling the temperature control, the selection of the type and amount of the solvent, the silver salt used during grain growth, and the addition rate of halide.
[0014]
Further, in the present invention, among the tabular silver halide grains, monodispersed hexagonal tabular grains are particularly useful grains.
Details of the structure and production method of monodispersed hexagonal tabular grains are as described in JP-A No. 63-151618.
[0015]
The silver halide emulsion preferable in the present invention may have a uniform crystal structure, but may have a halogen composition different from the inside and the outside, and may have a layered structure. Moreover, it is preferable that the reduction sensitized silver nucleus is included during grain formation.
[0016]
In the present invention, so-called halogen conversion type (conversion type) particles as described in British Patent No. 635841 and US Pat. No. 3,622,318 can be used particularly effectively. The halogen conversion amount is preferably 0.05 mol% to 0.45 mol%, more preferably 0.1 mol% to 0.3 mol%, based on the silver amount.
[0017]
In the silver iodobromide emulsion, grains having a structure having a high iodine layer inside and / or on the surface are particularly preferred.
Further, by converting the surface of the tabular silver halide grains preferable in the present invention into a high iodine type, a silver halide emulsion with higher sensitivity can be obtained.
[0018]
When halogen conversion is performed by the above method, a method in which a silver halide solvent is present is particularly effective. Preferred solvents include thioether compounds, thiocyanates, and tetrasubstituted thioureas. Of these, thioether compounds and thiocyanates are particularly effective. It is preferred to use 0.5 g to 5 g of thiocyanate per mole of silver halide and 0.2 g to 3 g of thioether.
[0019]
As a method for growing silver halide grains of the present invention, any known method can be used. That is, an aqueous silver salt solution and an aqueous halogen salt solution are added to the reaction vessel under efficient stirring. As a specific method, P.I. By Glafkides, Chemie et Physique Photographic (published by Paul Montel, 1967), G.K. F. Duffin, Photographic Emulsion Chemistry (published by The Focal Press, 1966), V.C. L. It can be prepared by a method described in Zelikmanet al, Making and Coating Photographic Emulsion (published by The Focal Press, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method, etc. may be used, and a method of reacting a soluble silver salt and a soluble halogen salt may be any one of a one-side mixing method, a simultaneous mixing method, and a combination thereof. Good.
[0020]
As one form of the simultaneous mixing method, a method of maintaining a constant pAg in a liquid phase in which silver halide is generated, that is, a so-called controlled double jet method can be used. Further, the addition rate of silver nitrate or an aqueous alkali halide solution is changed according to the grain growth rate, as described in British Patent No. 153516, JP-B-48-36890, JP-A-52-16364, etc. It is also preferable that the growth is carried out rapidly within a range not exceeding the critical supersaturation degree using a method or a method of changing the concentration of an aqueous solution as described in US Pat. No. 4,242,445, JP-A-55-158124.
[0021]
Tabular grains are preferably grown by physical ripening (fine grains dissolve and substrate grains grow) in the presence of silver halide fine grains.
[0022]
In the fine grain emulsion addition method, an AgX fine grain emulsion having a diameter of 0.15 μm or less, preferably 0.1 μm or less, more preferably 0.06 to 0.006 μm is added, and tabular grains are grown by Ostwald ripening. The fine grain emulsion can be added continuously or continuously. The fine grain emulsion is mixed with AgNO in a mixer provided near the reaction vessel.₃The solution and the X-salt solution can be supplied and prepared continuously, immediately added to the reaction vessel immediately, or prepared in advance in a batch format in a separate vessel and then added continuously or continuously. You can also. Such a fine grain emulsion can be added in a liquid state or as a dry powder. Also, the dry powder can be mixed with water just before the addition and liquefied for addition. The added fine particles are preferably added in such a manner that they disappear within 20 minutes, more preferably 10 seconds to 10 minutes. When the disappearance time is long, aging occurs between the fine particles, and the particle size increases, which is not preferable. Therefore, it is preferable not to add the whole amount at once. Such fine particles are preferably substantially free of multiple twin particles. Here, the multiple twin grain refers to a grain having two or more twin planes per grain. “Substantially free” refers to a multiple twin grain number ratio of 5% or less, preferably 1% or less, more preferably 0.1% or less. Furthermore, it is preferable that the single twin grain is not substantially contained. Furthermore, it is preferable that substantially no screw dislocation is contained. Here, “substantially free” follows the above definition.
[0023]
In the step of nucleation of tabular silver halide grains, gelatin having a low methionine content described in US Pat. Nos. 4,713,320 and 4,942,120 is used, and US Pat. No. 4,914. , 014 and nucleation at a high pBr as described in JP-A-2-222940 are very effective in the nucleation step of the particles used in the present invention. In particular, gelatin having a methionine content of preferably 0 to 50 μmol / g, more preferably 0 to 40 μmol / g can be preferably used. When such gelatin is used during ripening and growth, thinner tabular grains having a uniform diameter size distribution are formed, which is preferable. In the present invention, the silver nitrate aqueous solution, the halogen aqueous solution and the low molecular weight oxidized gelatin are preferably added within one minute while stirring in the presence of low molecular weight oxidized gelatin at a temperature of 20 ° C. to 40 ° C. At this time, the pBr of the system is preferably 2 or more, and the pH is preferably 7 or less. The concentration of the aqueous silver nitrate solution is preferably 0.6 mol / liter or less. The gelatin preferably has a molecular weight smaller than that of a normal one, particularly preferably 10,000 to 50,000. Gelatin in which the amino group is modified by 90% or more to phthalation, succination or trimellitization and / or oxidation-treated gelatin with a reduced methionine content is particularly preferably used.
[0024]
Further, the aging step can be performed in the presence of a low concentration base described in US Pat. No. 5,254,453, or at a high pH described in US Pat. No. 5,013,641. Also, U.S. Pat. Nos. 5,147,771, 5,147,772, 5,147,773, 5,171,659, 5,210,013, and The polyalkylene oxide compound described in US Pat. No. 5,252,453 can be added in the aging step or the subsequent growth step. In the present invention, the aging step is preferably performed at a temperature of 60 ° C. or higher and 80 ° C. or lower. It is preferable to reduce pBr to 2 or less immediately after nucleation or during aging. Further, additional gelatin is preferably added immediately after nucleation until the end of ripening. Particularly preferred gelatin has 95% or more of amino groups modified to succination or trimellitation.
[0025]
The pH during growth by adding fine particles needs to be 2.0 or more, but is preferably 6 or more and 10 or less. More preferably, the pH is 6 or more and 9 or less.
[0026]
The pCl needs to be 1.0 or more, but is preferably 1.6 or more. More preferably, it is 1.8 to 3.0.
[0027]
The tabular grains of the present invention are preferably silver halide grains having dislocation lines.
[0028]
The dislocation lines of tabular grains are, for example, J. F. Hamilton, Photo. Sci. Eng. ,1157 (1967), and T.W. Shiozawa, J. et al. Soc. Photo. Sci. Japan,35213 (1972), and can be observed by a direct method using a transmission electron microscope at a low temperature. In other words, the silver halide grains taken out carefully so as not to apply a pressure that causes dislocation to the grains from the emulsion are placed on a mesh for electron microscope observation, and the sample is placed to prevent damage (printout, etc.) due to electron beams. Observation is performed by the transmission method in the cooled state. At this time, the thicker the particle, the more difficult it is to transmit the electron beam. Therefore, it is possible to observe more clearly using a high-pressure type electron microscope (200 kV or more for particles having a thickness of 0.25 μm). From the photograph of particles obtained by such a method, the position and number of dislocations for each particle when viewed from the direction perpendicular to the main plane can be obtained.
[0029]
In addition, cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or complex salt thereof, rhodium salt or complex salt thereof, iron salt or complex salt thereof, etc. may coexist in the process of silver halide grain formation or physical ripening.
[0030]
The silver halide grains of the present invention are preferably subjected to chemical sensitization. As chemical sensitization, chalcogen sensitization such as sulfur sensitization, selenium sensitization, and tellurium sensitization, gold sensitization, and reduction sensitization can be used. Preferably, chalcogen sensitization and gold sensitization can be used in combination.
[0031]
In sulfur sensitization, unstable sulfur compounds are used. The unstable sulfur compounds described in Grafkides, Chimie et Physique Photographic (published by Paul Momtel, 1987, 5th edition), Research Disclosure, Vol. 307, No. 307105 can be used. Specifically, thiosulfate (for example, hypo), thioureas (for example, diphenylthiourea, triethylthiourea, N-ethyl-N ′-(4-methyl-2-thiazolyl) thiourea, carboxymethyltriurea. Methylthiourea), thioamides (eg, thioacetamide), rhodanines (eg, diethylrhodanine, 5-benzylidene-N-ethyl-rhodanine), phosphine sulfides (eg, trimethylphosphine sulfide), thiohydantoins, Known sulfur compounds such as 4-oxo-oxazolidine-2-thiones, disulfides or polysulfides (eg, dimorpholine disulfide, cystine, lenthionine), mercapto compounds (eg, cysteine), polythionates, elemental sulfur And active gelatin It can be also used.
[0032]
In selenium sensitization, unstable selenium compounds are used, and Japanese Patent Publication Nos. 43-13489, 44-15748, JP-A-4-25832, JP-A-4-109240, JP-A-4-271341 and 5 The unstable selenium compound described in each specification of -40324 can be used. Specifically, colloidal metal selenium, selenoureas (eg, N, N-dimethylselenourea, trifluoromethylcarbonyl-trimethylselenourea, acetyl-trimethylselenourea), selenoamides (eg, selenoacetamide, N, N-diethylphenylselenamide), phosphine selenides (eg triphenylphosphine selenide, pentafluorophenyltriphenylphosphine selenide), selenophosphates (eg tri-p-tolylselenophosphate, Tri-n-butylselenophosphate), selenoketones (for example, selenobenzophenone), isoselenocyanates, selenocarboxylic acids, selenoesters, diacylselenides and the like may be used. Furthermore, non-labile selenium compounds described in JP-B Nos. 46-4553 and 52-34492, such as selenious acid, potassium selenocyanide, selenazoles, and selenides can also be used.
[0033]
In the tellurium sensitization, unstable tellurium compounds are used, and Canadian Patent No. 80000958, British Patent Nos. 1,295,462 and 1,396,696, JP-A-4-204640, and 4-271341. Nos. 4-3333043 and 5-303157 can be used. Specifically, telluroureas (eg, tetramethyltellurourea, N, N′-dimethylethylenetellurourea, N, N′-diphenylethylenetellurourea), phosphine tellurides (eg, butyl-diisopropylphosphine) Telluride, tributylphosphine telluride, tributoxyphosphine telluride, ethoxy-diphenylphosphine telluride), diacyl (di) tellurides (eg bis (diphenylcarbamoyl) ditelluride, bis (N-phenyl-N-methyl) Carbamoyl) ditelluride, bis (N-phenyl-N-methylcarbamoyl) telluride, bis (N-phenyl-N-benzylcarbamoyl) telluride, bis (ethoxycarbonyl) telluride), isosterulocyanates, telluramides, tellurohydrazides, Te Lose esters (for example, butylhexyl telluroester), telluroketones (for example, telluroacetophenone), colloidal tellurium, (di) tellurides, other tellurium compounds (potassium telluride, telluropentathionate sodium salt), etc. Good.
[0034]
Regarding the gold sensitization, the aforementioned P.P. Gold salts described in Grafkides, Chimie et Physique Photographic (published by Paul Momtel, 1987, 5th edition), Research Disclosure 307, 307105, and the like can be used. Specifically, in addition to chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide and gold selenide, U.S. Pat. Nos. 2,642,361, 5,049,484, and 5,049,485. Gold compounds described in the specification and the like can also be used. Moreover, you may add noble metal salts, such as platinum, palladium, and iridium.
[0035]
The amount of chalcogen sensitizer used in the present invention varies depending on the silver halide grains used, chemical sensitization conditions, etc., but is 10 per mol of silver halide.^-8-10^-2Mole, preferably 10^-7~ 5x10^-3Use about moles.
[0036]
The amount of gold sensitizer and noble metal sensitizer used in the present invention is 10 per mole of silver halide.^-7-10^-2Use about moles. Although there is no restriction | limiting in particular in the conditions of the chemical sensitization in this invention, 6-11 are preferable as pAg, More preferably, it is 7-10, As pH, 4-10 are preferable, As temperature, 40-95 degreeC is preferable. Furthermore, 45-85 degreeC is preferable.
[0037]
Regarding reduction sensitization, the above-mentioned P.I. Known reducing compounds described in Grafkides, Chimie et Physique Photographic (published by Paul Momtel, 1987, 5th edition), Research Disclosure, Vol. 307, No. 307105 can be used. Specifically, aminoiminomethanesulfinic acid (also known as thiourea dioxide), borane compound (for example, dimethylamine borane), hydrazine compound (for example, hydrazine, p-tolylhydrazine), polyamine compound (for example, diethylenetriamine, triethylene) Tetramine), stannous chloride, silane compounds, reductones (eg, ascorbic acid), sulfites, aldehyde compounds, hydrogen gas, and the like may be used. Further, reduction sensitization may be performed in an atmosphere of high pH or excessive silver ions (so-called silver ripening).
[0038]
In the silver halide emulsion of the present invention, the surface of the grain or a part thereof may be subjected to halogen conversion in the chemical sensitization step. As a method for performing halogen conversion, water-soluble bromide salts such as potassium bromide and sodium bromide, water-soluble iodide salts such as potassium iodide and the like can be used alone or in combination, and they can be used as solids or It can be added as an aqueous solution or a gelatin dispersion. Further, addition of silver bromide fine grains of silver bromide, silver iodobromide and silver iodide is also preferably used, and these can be used alone or in combination. When added as fine particles, the average equivalent sphere diameter of the fine particles is preferably 0.1 μm or less, more preferably 0.05 μm or less. The fine particles can be continuously adjusted by supplying a silver nitrate aqueous solution and an alkali halide aqueous solution having an arbitrary composition with a mixer provided in the vicinity of the reaction vessel, and can be immediately added to the reaction vessel. It can also be added after adjusting to a batch type. Further, if necessary, the silver halide fine particles may contain ions or compounds of heavy metals such as iridium, rhodium and platinum.
[0039]
In preparation of the emulsion of the present invention, for example, at the time of grain formation, desalting step, chemical sensitization, or before coating, it is preferable to have a metal ion salt present before coating. When the particles are doped, it is preferably added after the formation of the particles, before the completion of the chemical sensitization after the formation of the particles when used as a particle sensitizer or a chemical sensitizer. A method of doping the entire particle, a method of doping only the core part, only the shell part, only the epitaxial part, or only the base particle of the particle can also be selected. Mg, Ca, Sr, Ba, Al, Sc, Y, LaCr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ru, Rh, Pd, Re, Os, Ir, Pt, Au, Cd, Hg, Tl, In, Sn, Pb, Bi, or the like can be used. These metals can be added in the form of a salt that can be dissolved during particle formation, such as ammonium salt, acetate salt, nitrate salt, sulfate salt, phosphate salt, hydrate salt, hexacoordinated complex salt, and tetracoordinated complex salt. For example, CdBr₂, CdCl₂, Cd (NO₃)₂, Pb (NO₃)₂, Pb (CH₃COO)₂, K₃[Fe (CN)₆], (NH₄)₄[Fe (CN)₆], K₃IrCl₆, (NH₄)₃RhCl₆, K₄Ru (CN)₆Etc. The ligand of the coordination compound can be selected from halo, aco, cyano, cyanate, thiocyanate, nitrosyl, thionitrosyl, oxo and carbonyl. These may use only one type of metal compound, but may be used in combination of two or more.
[0040]
A method of adding a chalcogen compound during preparation of an emulsion as described in US Pat. No. 3,772,031 may be useful. In addition to S, Se, and Te, cyanate, thiocyanate, selenocyanic acid, carbonate, phosphate, and acetate may be present.
[0041]
Chemical sensitization can also be performed in the presence of a so-called chemical sensitization aid. Useful chemical sensitization aids include compounds known to suppress fog and increase sensitivity during the process of chemical sensitization, such as azaindene, azapyridazine, and azapyrimidine. Examples of chemical sensitization aid modifiers include U.S. Pat. Nos. 2,131,038, 3,411,914, 3,554,757, JP-A-58-126526, and the above-mentioned Daphin, "Photographic emulsion chemistry", pages 138-143.
[0042]
It is preferable to use an oxidizing agent for silver during the production process of the emulsion of the present invention. The oxidizing agent for silver means a compound having an action of acting on metallic silver and converting it into silver ions. In particular, a compound that converts very fine silver grains by-produced in the process of forming silver halide grains and chemical sensitization into silver ions is effective. The silver ions generated here may form a silver salt that is hardly soluble in water such as silver halide, silver sulfide, and silver selenide, or may form a silver salt that is easily soluble in water such as silver nitrate. Also good. The oxidizing agent for silver may be an inorganic substance or an organic substance. Inorganic oxidants include ozone, hydrogen peroxide and its adducts (eg, NaBO).₂・ H₂O₂・ 3H₂O, 2NaCO₃・ 3H₂O₂, Na₄P₂O₇・ 2H₂O₂2Na₂SO₄・ H₂O₂・ 2H₂O), peroxyacid salts (eg K)₂S₂O₈, K₂C₂O₆, K₂P₂O₈), Peroxy complex compounds (for example, K2 [Ti (O₂) C₂O₄] 3H₂O, 4K₂SO₄・ Ti (O₂) OH / SO₄・ 2H₂O, Na₈[VO (O₂) (C₂H₄)₂・ 6H₂O], permanganate (eg, KMnO₄), Chromate (eg, K₂Cr₂O₇) Oxyacid salts, halogen elements such as iodine and bromine, perhalogenates (eg potassium periodate), high-valent metal salts (eg potassium hexacyanoferrate) and thiosulfonates is there.
[0043]
Examples of organic oxidizing agents include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogens (for example, N-bromosuccinimide, chloramine T, chloramine B). ) As an example.
It is a preferred embodiment to use the aforementioned reduction sensitization in combination with an oxidizing agent for silver.
[0044]
The silver halide photographic light-sensitive material of the present invention is preferably spectrally sensitized. Examples of spectral sensitizing dyes that can be used for spectral sensitization include cyanine dyes, merocyanine dyes, composite cyanine dyes, composite merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful spectral sensitizing dyes are those belonging to cyanine dyes, merocyanine dyes and complex merocyanine dyes. For these dyes, any of nuclei commonly used for cyanine dyes can be applied as the basic heterocyclic nucleus. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, selenazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, tellurazole nucleus, etc .; Condensed nuclei; and nuclei in which aromatic hydrocarbon rings are condensed to these nuclei, ie, indolenine nuclei, benzindolenine nuclei, indole nuclei, benzoxazole nuclei, naphthoxazole nuclei, benzimidazole nuclei, naphthimidazole nuclei, A benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a naphthoselenazole nucleus, a quinoline nucleus, a benzotelazole nucleus, or the like can be applied. These heterocyclic nuclei may be substituted on carbon atoms.
[0045]
For the merocyanine dye or the composite merocyanine dye, any of nuclei usually used for merocyanine dyes can be applied as the nucleus having a ketomethylene structure. Particularly useful nuclei include pyrazolin-5-one nucleus, thiohydantoin nucleus, 2-thiooxazolidine-2,4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbituric acid nucleus, 2-thio A 5-membered or 6-membered heterocyclic nucleus such as a selenazolidine-2,4-dione nucleus can be applied.
[0046]
There is no restriction | limiting in particular as an addition time of a spectral sensitizing dye, It can add at arbitrary time from a particle formation process to just before application | coating. Specifically, a method of adding at the time of silver halide grain formation, a method of adding at the silver halide emulsion desalting step, a method of adding just before the silver halide emulsion chemical ripening (chemical sensitization) step, silver halide emulsion chemistry There is a method of adding at the time of ripening, after silver halide emulsion chemical ripening, and at the time of preparing a coating solution, but preferably before adding the gold sensitizer and chalcogen sensitizer described above, that is, before chemical sensitization with these compounds. Add to. It is also possible to uniformly attach each halogenated particle by adding the spectral sensitizing dye at a temperature of 25 ° C. or higher and lower than 55 ° C. and then performing chemical ripening by raising the temperature from the addition temperature.
[0047]
In order to contain the spectral sensitizing dye used in the present invention in the silver halide emulsion of the present invention, they may be dispersed directly in the emulsion, or water, methanol, ethanol, propanol, acetone, methyl cellosolve, 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxy-1-propanol, 3-methoxy-1-butanol, 1-methoxy-2-propanol, N, N- A solvent such as dimethylformamide alone or in a mixed solvent may be added to the emulsion. Further, as described in US Pat. No. 3,469,987, etc., a dye is dissolved in a volatile organic solvent, and this solution is dispersed in water or a hydrophilic colloid, and this dispersion is dispersed in an emulsion. As described in JP-B-46-24185, etc., in which a water-insoluble dye is dispersed in a water-soluble solvent without dissolving it, and this dispersion is added to the emulsion. No. 23389, JP-B-44-27555, JP-B-57-22091 and the like, a dye is dissolved in an acid and this solution is added to an emulsion, or an acid or a base is allowed to coexist to form an aqueous solution. As described in U.S. Pat. No. 3,822,135, U.S. Pat. No. 4,006,025, etc., a surfactant is allowed to coexist to form an aqueous solution or colloidal dispersion. Add to the emulsion As described in JP-A-53-102733 and JP-A-58-105141, a method in which a dye is directly dispersed in a hydrophilic colloid, and the dispersion is added to an emulsion. As described in US Pat. No.-74624, a method of dissolving a dye using a compound that shifts red and adding this solution to an emulsion can also be used. In addition, ultrasonic waves can be used for dissolution.
[0048]
Spectral sensitizing dye combinations are often used, particularly for the purpose of supersensitization. Typical examples thereof are U.S. Pat. Nos. 2,688,545, 2,977,229, 3,397,060, 3,522,052, 3,527,641, 3, 617,293, 3,628,964, 3,666,480, 3,672,898, 3,679,428, 3,703,377, 3,769, No. 301, No. 3,614,609, No. 3,837,862, No. 4,026,707, British Patent Nos. 1,344,281, No. 1,507,803 JP-A-43-4936, JP-A-53-12375, JP-A-52-110618, JP-A-52-109925, and the like.
[0049]
Furthermore, these sensitizing dyes do not exhibit spectral sensitizing action themselves, or substances that do not substantially absorb visible light and show a significant increase in spectral sensitization when combined with the sensitizing dye. They may be used in combination with any compound known as a so-called supersensitizer. Representative examples of supersensitizers are bispyridinium salt compounds described in JP-A-59-142541, stilbene derivatives described in JP-B-59-18691, JP-B-49-46932, and the like. Water-soluble bromides such as potassium bromide and potassium iodide, water-soluble iodides, condensates of aromatic compounds and formaldehyde described in US Pat. No. 3,743,510, etc., and cadmium salts And azaindene compounds. The spectral sensitizing dye is added to the emulsion after chemical ripening or before chemical ripening. For the silver halide grains of the present invention, the spectral sensitizing dye is most preferably added during chemical ripening or before chemical ripening (for example, during grain formation or physical ripening).
[0050]
Next, the fluorine-containing compound used for the silver halide photographic light-sensitive material of the present invention will be described.
The fluorine-containing compound in the present invention is a compound represented by the general formula (1) or (2).
[0051]
In the general formula (1), Rf₁Represents an aliphatic group containing at least one fluorine atom, and the aliphatic group preferably has 1 to 18 carbon atoms, more preferably 2 to 12 carbon atoms, and 3 carbon atoms. It is especially preferable that it is ~ 7.
[0052]
In the general formula (1), Rf₂Represents an alkylene group containing at least one fluorine atom, preferably having 1 to 8 carbon atoms, more preferably 2 to 5 carbon atoms, and particularly preferably 2 or 3.
[0053]
In the general formula (1), L₁Represents a linking group. As the linking group, an alkylene group, an arylene group, or a divalent linking group containing a hetero atom is preferable.
[0054]
In the general formula (1), X₁Represents a hydroxyl group, an anionic group, or a cationic group, and the anionic group is preferably a carboxyl group, a sulfonic acid group, or a phosphoric acid group. Ions and the like are preferable. The cationic group is preferably a quaternary alkylammonium group, and the counter anion is preferably a halide ion, p-toluenesulfonic acid ion, or the like.
[0055]
In the general formula (1), n1 and m1 each represent an integer of 1 or more, and n1 is preferably 1 or more and 10 or less, and m1 is preferably 1 or more and 3 or less. m2 represents 1 or 0.
[0056]
In the general formula (2), Rf₃Represents a perfluoroalkyl group having 1 to 4 carbon atoms, and the perfluoroalkyl group is particularly preferably a trifluoromethyl group.
[0057]
In the general formula (2), (PFC) represents a perfluorocycloalkylene group. Examples of the perfluorocycloalkylene group include a perfluorocyclooctylene group, a perfluorocycloheptylene group, and a perfluoro group. Examples thereof include a cyclohexylene group and a perfluorocyclopentylene group, and a perfluorocyclohexylene group is particularly preferable.
[0058]
In the general formula (2), Y₂Represents a linking group containing an oxygen atom or a nitrogen atom, and the linking group is —OCH₂-, -NHCH₂-Is particularly preferred.
[0059]
In the general formula (2), L₂Represents a simple bond or a linking group. Examples of such a linking group include substituted or unsubstituted alkylene (for example, ethylene, n-propylene, or isobutylene), arylene (for example, phenylene), and a combination of alkylene and allylene. (Eg, xylylene), oxydialkylene (eg, CH₂CH₂OCH₂CH₂), Thiodialkylene (e.g., CH₂CH₂SCH₂CH₂In general, a divalent linking group may be mentioned.
[0060]
In the general formula (2), X₂Represents an anionic group, a cationic group, a nonionic group, or a water-solubilized polar group containing an amphoteric group. Examples of the anionic group include CO 2₂H, CO₂M, SO₃H, SO₃M, OSO₃H, OSO₃M, (OCH₂CH₂OSO₃M, OPO (OH)₂, And OPO (OM)₂(In the formula, M represents a metal ion such as sodium, potassium, or calcium, or an ammonium ion). Among them, a carboxyl group, a sulfonic acid group, and a phosphoric acid group are preferable, and sodium is used as a counter cation. Alkali metal ions such as ions and potassium ions, ammonium ions and the like are preferable. The cationic group is preferably a quaternary alkylammonium group, and the counter anion is preferably a halide ion, p-toluenesulfonic acid ion, or the like. As the nonionic group, a hydroxyl group is preferable.
[0061]
In the general formula (2), n2 represents an integer of 1 to 5, K represents an integer of 1 to 3, m2 represents an integer of 1 to 5, n2 is preferably 3, and K is 1 Or 2 is preferable, and m2 is particularly preferably 1.
[0062]
Specific examples of the compound represented by formula (1) or (2) that can be used in the present invention are shown below, but the present invention is not limited thereto.
[0063]
Hereinafter, 1-1 to 1-83 are exemplary compounds represented by the general formula (1).
1-1: C₅F₁₁-(O-CF₂) -O-PO (ONa)₂
1-2: HC₆F₁₂-(O-CF₂) -O-PO (ONa)₂
1-3: C₈F₁₇-(O-CF₂) -O-PO (ONa)₂
1-4: C₁₀F₂₁-(O-CF₂) -O-PO (ONa)₂
1-5: C₁₂F₂₅-(O-CF₂) -O-PO (ONa)₂
1-6: C₃F₇-(OC₂F₄) -O-PO (ONa)₂
1-7: C₄F₉-(OC₂F₄) -O-PO (ONa)₂
1-8: C₅F₁₁-(OC₂F₄) -O-PO (ONa)₂
1-9: C₆F₁₃-(OC₂F₄) -O-PO (ONa)₂
1-10: C₇F₁₅-(OC₂F₄) -O-PO (ONa)₂
1-11: C₉F₁₉-(OC₂F₄) -O-PO (ONa)₂
1-12: C₁₁F₂₃-(OC₂F₄) -O-PO (ONa)₂
1-13: C₃F₇-(O-CF₂)₆-O-PO (ONa)₂
1-14: C₄F₉-(O-CF₂)₆-O-PO (ONa)₂
1-15: C₅F₁₁-(O-CF₂)₅-O-PO (ONa)₂
1-16: HC₆F₁₂-(O-CF₂)₃-O-PO (ONa)₂
1-17: C₃F₇-[O- (CF₂)₃] -COONa
1-18: C₄F₉-[O- (CF₂)₃] -COONa
1-19: C₅F₁₁-[O- (CF₂)₃] -COONa
1-20: HC₇F₁₄-[O- (CF₂)₃] -O-CH (COONa)₂
[0064]
1-21: C₈F₁₇-[O- (CF₂)₃] -O-CH (COONa)₂
1-22: C₃F₇-[O- (CF₂)₅] -COONa
1-23: C₄F₉-[O- (CF₂)₅] -COONa
1-24: C₅F₁₁-[O- (CF₂)₅] -COONa
1-25: C₇F₁₅-[O- (CF₂)₅] -COONa
1-26: C₃F₇-(OC₂F₄)₅-COONa
1-27: C₄F₉-(OC₂F₄)₂-COONa
1-28: C₅F₁₁-(OC₂F₄)₂-COONa
1-29: HC₇F₁₄-(OC₂F₄)₂-COONa
1-30: C₉F₁₉-(OC₂F₄)₂-COONa
1-31: C₂F₅-(OC₂F₄)₃-COONa
1-32: C₂F₅-(OC₂F₄)₅-COONa
1-33: C₃F₇-(OC₂F₄)₄-COONa
1-34: C₄F₉-(OC₂F₄)₃-COONa
1-35: C₅F₁₁-(OC₂F₄)₃-NHCOCH (COONa)₂
1-36: HC₆F₁₂-(OC₂F₄)₃-NHCOCH (COONa)₂
1-37: C₄F₉-(OC₂F₄)₂-OCF₂COONa
1-38: C₅F₁₁-(OC₂F₄)₂-OCF₂COONa
1-39: C₇F₁₅-(OC₂F₄)₂-OCF₂COONa
1-40: C₄F₉-OCF₂-[O- (CF₂)₅] -COOK
[0065]
1-41: C₅F₁₁-OCF₂-[O- (CF₂)₅] -COOK
1-42: HC₆F₁₂-OCF₂-[O- (CF₂)₅] -COOK
1-43: C₄F₉-(OC₂F₄)₅-[O- (CF₂)₃] -COOK
1-44: C₅F₁₁-(OC₂F₄)₂-[O- (CF₂)₃] -COOK
1-45: C₆F₁₃-(OC₂F₄)₂-[O- (CF₂)₃] -COOK
1-46: C₁₂F₂₅-(O-CF₂) -O-SO₃Na
1-47: C₇F₁₅-(OC₂F₄) -OC₃H₆-SO₃Na
1-48: C₄F₉-(O-CF₂)₆-O-SO₃Na
1-49: HC₅F₁₀-(O-CF₂)₅-OC₃H₆-SO₃Na
1-50: HC₆F₁₂-(O-CF₂)₃-O-SO₃Na
1-51: C₅F₁₁-(OC₂F₄)₂-OC₃H₆-SO₃Na
1-52: C₇F₁₅-(OC₂F₄)₂-O-SO₃Na
1-53: C₃F₇-(OC₂F₄)₄-OC₃H₆-SO₃Na
1-54: C₄F₉-(OC₂F₄) 3-O-SO₃Na
1-55: HC₃F₁₀-(OC₂F₄)₃-OC₃H₆-SO₃Na
1-56: C₅F₁₁-OCF₂-[O- (CF₂)₅] -O-SO₃Na
1-57: C₄F₉-(OC₂F₄)₂-[O- (CF₂)₃] -O-SO₃Na
1-58: (HCF₂)₃C- (OC₂F₄)₃-O-SO₃Na
1-59: (CF₃)₂CFCF₂CF₂-(O-CF₂)₅-OC₃H₆-SO₃Na
[0066]
1-60: C₁₁F₂₃-(OC₂F₄) -O-SO₃Na
1-61: C₄F₉-(OC₂F₄)₃-NHCO- (CH₂)₃-N⁺(CH₃)₃, Br-
1-62: C₅F₁₁-(OC₂F₄)₂-NHCO- (CH₂)₃-N⁺(CH₃)₃, Br-
1-63: HC₆F₁₂-(OC₂F₄)₂-NHCO- (CH₂)₃-N⁺(CH₃)₃, Br-
1-64: C₄F₉-(OC₂F₄)₃-O-CH₂-N⁺(CH₃)₂(C₂H₄OH), Br-
1-65: C₅F₁₁-(OC₂F₄)₂-O-CH₂-N⁺(CH₃)₂(C₂H₄OH), Br-
1-66: HC₆F₁₂-(OC₂F₄)₂-O-CH₂-N⁺(CH₃)₂(C₂H₄OH), Br-
1-67: C₅F₁₁-OCF₂-(OC₂F₄) -NHCO- (CH₂)₃-N⁺(CH₃)₃, Br-
1-68: (CF₃)₃C- (OC₂F₄)₃-O-CH₂-N⁺(CH₃)₂(C₂H₄OH), Br-
1-69: C₁₂F₂₅-(O-CF₂) -OH
1-70: C₇F₁₅-(OC₂F₄) -OH
1-71: C₄F₉-(O-CF₂)₆-OC₃H₆-OH
1-72: C₅F₁₁-(O-CF₂)₅-OC₃H₆-OH
1-73: HC₆F₁₂-(O-CF₂)₃-OH
1-74: C₅F₁₁-(OC₂F₄)₂-OC₃H₆-OH
1-75: C₇F₁₅-(OC₂F₄)₂-OC₃H₆-OH
1-76: C₃F₇-(OC₂F₄)₄-OC₃H₆-OH
[0067]
1-77: HC₄F₈-(OC₂F₄)₃-OC (C₂H₄OH)₁₁
1-78: C₅F₁₁-(OC₂F₄)₃-OC₃H₆-OH
1-79: C₅F₁₁-OCF₂-[O- (CF₂)₅] -OH
1-80: C₄F₅-(OC₂F₄)₂-[O- (CF₂)₃] -OH
1-81: (CF₃)₃C- (OC₂F₄)₃-OH
1-82: (HCF₂)₂CFCF₂CF₂-(O-CF₂)₅-OH
1-83: C₁₁F₂₃-(OC₂F₄)₄-OH
[0068]
With respect to the method for synthesizing the fluorine-containing compound represented by the general formula (1), JP-T-10-500950 and JP-A-11-504360 can be referred to.
[0069]
Hereinafter, 2-1 to 2-50 are exemplary compounds represented by the general formula (1).
2-1: (CF₃O)₃(PFC ')-CONHC₃H₆N⁺(CH₃)₂C₂H₄COO⁻
2-2: (CF₃O)₃(PFC ')-CONHC₃H₆N⁺(CH₃)₂C₂H₄SO₃ ⁻
2-3: (CF₃O) (PFC ')-CONHC₃H₆N⁺(CH₃)₂C₂H₄SO₃ ⁻2-4: (CF₃O)₃(PFC ')-CON (C₃H₆SO₃ ⁻) C₃H₆N⁺(CH₃2H
2-5: (CF₃O) (PFC ')-CON (C₃H₆SO₃-) C₃H₆N⁺(CH₃)₂H
2-6: [(CF₃O)₃(PFC ')-COOCH₂]₂CH-CONHC₃H₆N⁺(CH₃)₂C₂H₄SO₃ ⁻
2-7: [(CF₃O)₂(PFC ')-COOCH₂]₂CH-CONHC₃H₆N⁺(CH₃)₂C₂H₄SO₃ ⁻
2-8: [(CF₃O) (PFC ')-COOCH₂]₂CH-CONHC₃H₆N⁺(CH3)₂C₂H₄SO₃ ⁻
2-9: (CF₃O)₃(PFC ')-CONHC₃H₆N⁺(CH₃)₂C₂H₄OH, Cl⁻
2-10: (CF₃O)₂(PFC ')-CONHC₃H₆N⁺(CH₃)₂C₂H₄OH, Cl⁻
[0070]
2-11: (CF₃O) (PFC ')-CONHC₃H₆N⁺(CH₃)₂C₂H₄OH, Cl⁻
2-12: (CF₃O)₃(PFC ')-CONHC₃H₆N⁺(CH₃)₂H, Cl⁻2-13: (CF₃O)₂(PFC ')-CONHC₃H₆N⁺(CH₃)₂H, Cl⁻2-14: (CF₃O) (PFC ')-CONHC₃H₆N⁺(CH₃)₂H, Cl⁻2-15: [(CF₃O)₃(PFC ')-COOCH₂]₂C (CH₃) N + (CH₃)₂H, Cl⁻
2-16: [(CF₃O)₂(PFC ')-COOCH₂]₂C (CH₃) N⁺(CH₃)₂H, Cl⁻
2-17: [(CF₃O) (PFC ')-COOCH₂]₂C (CH₃) N⁺(CH₃)₂H, Cl⁻
2-18: [(CF₃O)₃(PFC ')-COOCH₂]₂CHC₃H₆N⁺(CH₃)₂H, Cl⁻
2-19: [(CF₃O)₂(PFC ')-COOCH₂]₂CHC₃H₆N⁺(CH₃)₂H, Cl⁻
2-20: [(CF₃O) (PFC ')-COOCH₂]₂CHC₃H₆N⁺(CH₃)₂H, Cl⁻
2-21: (CF₃O)₃(PFC ')-COO (C₂H₄O)₁₂H
2-22: (CF₃O)₂(PFC ')-COO (C₂H₄O)₁₂H
2-23: (CF₃O) (PFC ')-COO (C₂H₄O)₁₂H
2-24: (CF₃O)₃(PFC ')-COO (C₂H₄O)₁₅CH₃
2-25: (CF₃O)₂(PFC ')-COO (C₂H₄O)₁₅CH₃
[0071]
2-26: (CF₃O) (PFC ')-COO (C₂H₄O)₁₅CH₃
2-27: [(CF₃O)₃(PFC ')-COOCH₂]₂CHC₃H₆OH
2-28: [(CF₃O)₂(PFC ')-COOCH₂]₂CHC₃H₆OH
2-29: [(CF₃O) (PFC ')-COOCH₂]₂CHC₃H₆OH
2-30: (CF₃O)₃(PFC ')-CONHC₃H₆COONa
2-31: (CF₃O)₂(PFC ')-CONHC₃H₆COONa
2-32: (CF₃O) (PFC ')-CONHC₃HvCOOK
2-33: (CF₃O)₃(PFC ')-CONHC₃H₆SO₃Na
2-34: (CF₃O)₂(PFC ')-CONHC₃H₆SO₃Na
2-35: (CF₃O) (PFC ')-CONHC₃H₆SO₃K
2-36: (CF₃O)₃(PFC ')-CON (C₃H₆SO₃Na) C₃H₇
2-37: (CF₃O)₂(PFC ')-CON (C₃H₆SO₃Na) C₃H₇
2-38: (CF₃O) (PFC ')-CON (C₃H₆SO₃Na) C₃H₇
2-39: [(CF₃O)₃(PFC ')-COOCH₂]₂C (CH₃COONa
2-40: [(CF₃O)₂(PFC ')-COOCH₂]₂C (CH₃COONa
2-41: [(CF₃O) (PFC ')-COOCH₂]₂C (CH₃) COONa2-42: [(CF₃O)₃(PFC ')-COOCH₂]₂C (COONa)₂
2-43: [(CF₃O)₂(PFC ')-COOCH₂]₂C (COONa)₂
2-44: [(CF₃O) (PFC ')-COOCH₂]₂C (COONa)₂
2-45: [(CF₃O)₃(PFC ')-COOCH₂]₂C (CH₃) SO₃Na
2-46: [(CF₃O)₂(PFC ')-COOCH₂]₂C (CH₃) SO₃Na
2-47: [(CF₃O) (PFC ')-COOCH₂]₂C (CH₃) SO₃Na
2-48: [(CF₃O)₃(PFC ')-COOCH₂]₂CHC₃H₆SO₃Na
2-49: [(CF₃O)₂(PFC ')-COOCH₂]₂CHC₃H₆SO₃Na
2-50: [(CF₃O) (PFC ')-COOCH₂]₂CHC₃H₆SO₃Na
[0072]
In the fluorine-containing compound represented by the general formula (2), (PFC ′) represents a perfluorocyclohexylene group, and (CF₃The substitution position of (O) is defined as (CF₃O)₃In the case of 3, 4 and 5 and (CF₃O)₂In the case of 3rd and 4th and (CF₃In the case of O), it is 4th.
[0073]
The compounds represented by the general formulas (1) and (2) used in the present invention are for forming a layer (in particular, a protective layer, an undercoat layer, a back layer, etc.) constituting a silver halide photographic light-sensitive material. It can be used as a surfactant in a coating composition.
[0074]
There is no restriction | limiting in particular about the usage-amount of the compound represented by the said General formula (1) and (2) in this invention, It is contained in the structure of the compound of General formula (1) and (2) to be used, a place to use, and a composition. The amount of use can be arbitrarily determined according to the type and amount of other materials to be used. For example, when used as a coating solution for the uppermost layer of the photosensitive material, the coating amount of the compound in the coating composition is 0.1 to 200 mg / m.²Preferably 0.5 to 50 mg / m²It is more preferable that
[0075]
In the present invention, if at least one selected from the group consisting of the compounds represented by the above general formulas (1) and (2) is used, these two or more types may be mixed and used. Furthermore, you may use together surfactant other than the compound represented by General formula (1) and (2).
[0076]
The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fogging during the production process, storage or photographic processing of the light-sensitive material, or stabilizing the photographic performance. That is, thiazoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, amino Triazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole) and the like; mercaptopyrimidines; mercaptotriazines; For example, triazaindenes, tetraazaindenes (especially 4-hydroxy-6-methyl (1,3,3a, 7) tetraazaindene), pentaa Known as antifoggants or stabilizers, such as indene, it may be added to many compounds. For example, those described in US Pat. Nos. 3,954,474, 3,982,947, and Japanese Patent Publication No. 52-28660 can be used. One of the preferred compounds is the compound described in Japanese Patent Application No. 62-47225. Antifoggants and stabilizers are available in various forms before particle formation, during particle formation, after particle formation, desalting process, during dispersion after desalting, before chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. Depending on the purpose, it can be added at any time.
[0077]
In the present invention, it is also preferable to perform chemical sensitization in the presence of a nucleic acid or a decomposition product thereof before completion of chemical sensitization. As the nucleic acid or its degradation product, those described in JP-A-62-267541 can be used. Nucleic acids used in the present invention include deoxyribonucleic acid (DNA) and ribonucleic acid (RNA), and nucleic acid degradation products include those in the middle of degradation and simple substances such as adenine, guanine, uracil, cytosine and thymine. It is done. In particular, adenine is a preferable nucleic acid degradation product. These can be used alone or in combination. In this case, it goes without saying that the nucleic acid and the nucleic acid degradation product may be used in combination. The amount of the nucleic acid or its degradation product added varies depending on the type of the nucleic acid degradation product, but is 20 mg or more, preferably 100 mg to 1 g, per mole of silver halide. These nucleic acids or nucleic acid degradation products may be used alone or in combination of two or more as described above.
[0078]
In the light-sensitive material of the present invention, a crossover light cut layer can be provided between the light-sensitive emulsion layer and the support, if necessary, for the purpose of sharpening the image. The crossover cut layer is unique to medical X-ray photographic materials having silver halide emulsion layers on both sides, and light from one side affects the silver halide emulsion layer on the other side through the support. This is a means for solving the problem of degrading the image quality. The crossover cut layer can also serve as the non-photosensitive hydrocolloid layer of the present application. A dye corresponding to the photosensitive wavelength region is added to the crossover light cut layer. Any dye can be used as long as it does not leave harmful absorption after development. In particular, it is preferable to add the dye in a solid fine particle dispersed state. The method of adding the dye in a state of solid fine particle dispersion is disclosed in JP-A-2-264936, JP-A-3-210553, JP-A-3-210554, JP-A-3-238447, JP-A-4-14038, JP-A-4-14038. -14039, JP-A-4-125635, JP-A-4-338747, JP-A-6-27589, and the like. Dyes that can be used are, for example, dyes of the general formulas (I) to (VII) described in JP-A-4-21542, compound examples I-1 to I-37, II-1 to II-6, III-1 to III. -36, IV-1 to IV-16, V-1 to V-6, VI-1 to VI-13, VII-1 to VII-5. Dye of general formula (1) described in JP-A-8-73767, Compound Examples 1-6. Dyes of general formulas (VIII) to (XII) described in JP-A-8-87091, compound examples VIII-1 to VIII-5, IX-1 to IX-10, X-1 to X-21, XI-1 to XI-6, XII-1 to XII-7.
[0079]
In addition to these, a method of adsorbing a known dye on a mordant, a method of dissolving a known dye in oil and emulsifying and dispersing it in the form of oil droplets, a method of adsorbing the dye described in JP-A-3-5748 on the surface of an inorganic substance, A method of adsorbing a dye described in Kaihei 2-298939 to a polymer can also be used. As the method for adding the crossover light cut layer to the photosensitive material, those described in each specification can be used.
[0080]
A dye may be added to the photosensitive material of the present invention for the purpose of detecting the position of the photosensitive material. The dye desirably has an absorption spectrum corresponding to the sensitivity maximum wavelength of the detection sensor, and any dye that does not leave harmful absorption after development processing can be used. Preferably, a dye having an absorption maximum at 700 nm to 1400 nm or a fine particle dispersion thereof is used. For example,
(1) Examples of water-soluble dyes that can be decolored during processing include cyanine dyes, pyrylium dyes and aminium dyes of general formulas (I) to (IV) described in JP-A-3-211542, Compound Examples I-1 to I-6 II-1 to II-4, III-1 to III-4, IV-1 to IV-5,
[0081]
(2) Solid fine particle dispersed dyes that can be decolorized during processing include cyanine dyes, pyrylium dyes and aminium dyes of the general formulas (I) to (IV) described in JP-A-3-138640, Compound Examples I-1 to I -28, II-1 to II-10, III-1 to III-6, IV-1 to IV-7,
[0082]
(3) Examples of dyes that do not decolorize during the treatment include tricarbocyanine dyes having general formula (I) to general formula (II) described in Japanese Patent Application No. 6-227983; No. 6-279297, tetracarbocyan dye having a carboxyl group of general formula (I) to general formula (II), compound examples 1 to 19, and general formula (1) to general formula described in Japanese Patent Application No. 7-208569 (3) Cyanine dye having no acid group, Compound Examples 1 to 63, Lake type cyanine dye of the general formula [1] described in JP-A-8-333519, Compound Example No. 1-No. 37,
Etc.
[0083]
In addition to these, pyrylium dyes described in JP-A-62-299959, light scattering particles described in JP-A-63-131135, cyanine dyes described in JP-A-1-266536, oxonol described in JP-A-2-282244 Solid fine particle dispersions of dyes, holopolar cyanine dyes described in JP-A-3-13638, polymer-type cyanine dyes described in JP-A-7-253039, tin-doped indium oxide (ITO) powders described in JP-A-7-113072, Yb described in Kaihei 9-5913³⁺Compounds can also be utilized.
[0084]
There is no particular limitation on the layer to which the dye for the purpose of detecting the position of the photosensitive material is added, and it can be added to the silver halide emulsion layer, the non-photosensitive hydrophilic colloid layer of the present invention, the surface protective layer, etc. As the method, those described in each specification can be used.
[0085]
In the light-sensitive material of the present invention, a compound represented by the general formula (I) of Japanese Patent Application No. 2002-257523 may be used for the purpose of improving the color tone of a silver image. In addition, a dye may be added. The dye has a predetermined maximum absorption wavelength from among pyrazoloazole dyes, anthraquinone dyes, azo dyes, azomethine dyes, oxonol dyes, carbocyanine dyes, styryl dyes, triphenylmethane dyes, indoaniline dyes and indophenol dyes. What you have is selected. Among them, anthraquinone dyes of the general formula (I) described in JP-A-5-34858, azomethine dyes of the general formula (I) described in JP-A-4-247449, and general formula (I) described in JP-A-4-296845, Indoaniline dyes contained in the general formula (I) described in Kaihei 5-43809 and azo dyes described in JP-A-5-341441 are useful.
[0086]
Specific examples of anthraquinone dyes include compounds 1 to 9 described in JP-A-5-341441, and compounds 3-6 to 3-18 and 3-23 to 3-38 described in JP-A-5-165147. . Specifically, compounds 17 to 46 described in JP-A-5-341441 can be used as the azomethine dye. Specifically, compounds 11 to 19 described in JP-A-5-289227, compound 47 described in JP-A-5-341441 and compounds 2-10 to 2-11 described in JP-A-5-165147 are used as indoaniline dyes. can do. Specifically, compounds 10 to 16 described in JP-A-5-341441 can be used as the azo dye.
[0087]
As a method for adding a dye for the purpose of improving the color tone of a silver image to a light-sensitive material, those described in each specification can be used.
[0088]
The silver halide light-sensitive material of the present invention can contain colloidal silica. Colloidal silica has an average particle diameter of 1 to 1000 nm, preferably 5 to 500 nm, more preferably 5 to 100 nm, and its main component is silicon dioxide, and it may contain alumina or sodium alginate as a minor component. Good.
Specific examples of colloidal silica include SNOWTEX 20, SNOWTEX 30, SNOWTEX C, SNOWTEX O and the like under the trade name of Nissan Chemical Co., Ltd. (Tokyo, Japan).
The colloidal silica-containing layer may be any hydrophilic colloid layer such as a surface protective layer, an intermediate layer, a silver halide emulsion layer, an antihalation layer, an undercoat layer, a filter layer, or a backing layer. In the case where it is intended, it is preferably contained in the surface protective layer or the silver halide emulsion layer.
As content of colloidal silica, 1-200 mass% is preferable with respect to the hydrophilic colloid mass of the hydrophilic colloid layer to contain, and 10-100 mass% is the most preferable especially.
The layer containing colloidal silica preferably contains a plastic polymer latex in combination as necessary.
[0089]
The silver halide photographic light-sensitive material of the present invention may contain a polymer latex obtained by polymerizing a monomer that is hardly soluble in water.
[0090]
As such a monomer, for example, acrylic acid esters, methacrylic acid esters, divinylbenzene and the like described in JP-A-7-230135, page 2, 2nd line, 5th line to 17th line can be used.
[0091]
Such a polymer latex may copolymerize the above monomer with another monomer. Examples of the monomer at this time include, for example, JP-A-7-230135, page 2, line 2, line 32 to page 4, line 1 35. The monomers described in the line can be used, and among them, acrylic esters, methacrylic esters, vinyl esters, styrenes, and olefins are preferably used.
Examples of the polymer latex include Lx-1 to Lx-21 of JP-A-7-230135.
[0092]
The silver halide photographic light-sensitive material of the present invention is No. 1 described in Example 1 of JP-A-6-19479. 1-No. Eight matting agents can be preferably used. Further, preferred compound examples 1 to 9 described in paragraph 0023 of JP-A-6-138572 can be preferably used.
[0093]
With regard to the size and the like of these matting agents, they can be preferably used in the sizes and usage amounts described in paragraph 0049 of JP-A No. 6-194779. Two or more kinds of particle size matting agents can be mixed and used. Regarding the particle size distribution of the matting agent, monodispersed particles having a coefficient of variation of 3 to 30% can be used depending on the purpose, or polydispersed particles having 30% or more can be used.
[0094]
In the silver halide photographic light-sensitive material of the present invention, the preferred coating amount of the silver halide emulsion is 1 m per side in terms of silver amount.²The hit is 2.0 g or less. Preferably, it is 0.5 g or more and 1.7 g or less. More preferably, it is 0.8 g or more and 1.5 g or less.
[0095]
The total gelatin coating amount of the non-photosensitive hydrophilic colloid layer in the present invention is 2.5 g or less (total coating amount per side), and 0.5 g / m.²2.5 g / m or more²The following is preferred, particularly preferably 1.0 g / m.²2.1 g / m²It is as follows. In this case, the gelatin coating amount of the protective layer is 0.2 g / m.²1.0 g / m or more²The following is preferred.
[0096]
In the present invention, the swelling ratio of the photosensitive material is the value obtained by subtracting the dry film thickness value from the film thickness value after the photosensitive material is immersed in distilled water at 21 ° C. for 3 minutes. A value obtained by multiplying the value obtained by dividing the state film thickness value by 100 is defined as (%) and can be obtained. The range of a preferable swelling rate is 20% to 220%, more preferably 40% to 150%.
[0097]
In general, a silver halide photographic light-sensitive material is coated with an aqueous coating solution containing a hydrophilic colloid such as gelatin on a support, and then cooled and solidified in low-temperature air at a dry bulb temperature of -10 ° C to 20 ° C. And then dried at an elevated temperature. The mass ratio of gelatin to moisture immediately after coating is usually around 3000%.
This coating solution usually contains various additives such as hydrophilic colloid binder, silver halide grains, surfactant, plasticizer such as polymer latex, gelatin hardener, dye, sensitizing dye, matting agent. Yes.
In the present invention, when the hydrophilic colloid layer coating solution is applied and then dried, wet bulbs are used until the moisture content becomes 100% or less based on the dry amount of binder in the entire coating layer on the side having the silver halide emulsion layer. It is preferable to dry at a temperature of 20 ° C or lower, preferably 19 ° C to 10 ° C.
When two or more hydrophilic colloid layers are simultaneously applied and dried (that is, when there are two or more coating layers to be dried), the amount of water is the sum of the moisture in all layers, the binder drying The amount represents the sum of the dry weight (dry mass) of the binder in all layers.
The wet bulb temperature is the temperature of water droplets in an equilibrium state of humid air, and is lower as the humidity of the air is lower. In the constant rate drying period of the drying process, the wet bulb temperature of the drying air is substantially equal to the surface temperature of the coated sample.
[0098]
Moreover, as for the environmental conditions at the time of winding in roll shape after application | coating and drying, it is preferable that absolute humidity is 1.4 mass% or less, Preferably it is 1.3-0.6 mass%, and is wound up. In the present invention, the product processing of the silver halide photographic light-sensitive material wound in a roll after coating and drying is performed under an environment where the absolute humidity is 1.4% by mass or less, preferably 1.3 to 0.6% by mass. It is preferable to be processed.
Absolute humidity (wt%) represents the state of wet air, and is a percentage of the ratio of the amount of water vapor (kg) in the humid air to the mass (kg) of dry air in the wet air. The silver halide photographic light-sensitive material is placed in a moisture-proof package, and the mouth is sealed with heat seal or the like so that the absolute humidity in the package is 1.4% by mass or less, preferably 1.1 to 0.6. This means that the photosensitive material is balanced at the above absolute humidity.
[0099]
Further, it is particularly preferable that after processing is seasoned in an environment with an absolute humidity of 1.4% by mass or less, and then heat-sealed and sealed in the package in the same environment.
[0100]
There are no particular limitations on the various additives used in the silver halide photographic emulsion and silver halide photographic light-sensitive material of the present invention, and for example, those described in the following corresponding sections of JP-A-2-68539 can be used. .
[0101]
Item Applicable Location
1. Silver halide emulsion and its production method
JP-A-2-68539, page 8, lower right column, line 6 from the lower right column to page 10, upper right column, line 12.
2. Chemical sensitization method
10th page, upper right column, No. 13 to lower left column, 16th line.
3. Antifoggant and stabilizer
10th page, lower left column, line 17 to 11th page, upper left column, line 7 and 3rd page, lower left column, line 2 to 4th page, lower left column.
4). Spectral sensitizing dye
4th page, lower right column, line 4 to 8th page, lower right column.
5). Surfactant and antistatic agent
11th page, upper left column, line 14 to 12th page, upper left column, line 9
6). Matting agent / slip agent
From page 12, upper left column, line 10 to upper right column, line 10.
Plasticizer
From page 14, lower left column, line 10 to lower right column, line 1.
7). Hydrophilic colloid
From page 11, upper right column, line 11 to lower left column, line 16.
8). Hardener
From page 12, lower left column, line 17 to page 13, upper right column, line 6.
9. Support
On page 13, upper right column, lines 7 to 20.
10. Dyes and mordants
From page 13, lower right column, line 1 to page 14, lower left column, line 9.
[0102]
The photographic light-sensitive material of the present invention can be preferably subjected to X-ray photography using, for example, a fluorescent intensifying screen containing the following phosphor as a fluorescent screen.
[0103]
Blue light emitting phosphor
Y₂O₂S: Tb, LaOBr: Tb, BaFCl: Eu
Green light emitting phosphor
Gd₂O₂S: Tb, LaO₂S: Tb
[0104]
As the UV-emitting phosphor, M ′ phase YTaO₄A single compound or a compound to which Gd, Bi, Pb, Ce, Se, Al, Rb, Ca, Cr, Cd, Nb or the like is added, a compound in which Gd, Tm, Gd and Tm, Gd and Ce, or Tb are added to LaOBr, HfZr Oxide alone or a compound to which Ge or Ti alkali metal is added, Y₂O₃A compound alone or with Gd and Eu added, Y₂O₂There are compounds in which Gd is added to S, and compounds in which Gd, Tl, and Ce are used as activators in the matrix of various phosphors. Particularly preferred compounds include M ′ phase YTaO.₄A compound in which Gd and Sr are added alone, a compound in which Gd, Tm, Gd and Tm are added to LaOBr, a compound in which an oxide of HfZr or Ge or Ti alkali metal is added.
[0105]
The particle size of the phosphor is preferably 1 μm or more and 20 μm or less, but can be changed according to required sensitivity and manufacturing problems. The coating amount is 400 g / m²Or more 2000 g / m²Although the following is preferable, it cannot be said unconditionally depending on required sensitivity and image quality. Further, the particle size distribution may be given from the vicinity of the support to the surface with a single intensifying screen. In this case, it is generally known to enlarge the surface particles. The space filling factor of the phosphor is 40% or more, preferably 60% or more.
[0106]
When photographing with the phosphor layers on both sides of the photosensitive material, the amount of phosphor applied on the X-ray incident side and the opposite side can be changed. In general, since the screen is shielded by the intensifying screen on the X-ray incident side, it is known that the application amount of the intensifying screen on the X-ray incident side is reduced particularly when a high sensitivity system is required.
[0107]
Examples of the support used for the screen used in the present invention include paper, a metal plate, and a polymer sheet. Generally, a flexible sheet such as polyethylene terephthalate is used. If necessary, the support may be provided with a reflective layer or a light absorber, or may be provided as a separate layer on the surface.
[0108]
If necessary, the support surface can be slightly uneven, or an adhesive layer for increasing the adhesion to the phosphor layer or a conductive layer can be provided as an undercoat. Examples of the reflective agent include zinc oxide, titanium oxide, and barium sulfate. Titanium oxide and barium sulfate are preferred because the phosphor has a short emission wavelength. The reflective agent may be present not only in the support or between the support and the phosphor layer, but also in the phosphor layer. When it exists in a fluorescent substance layer, it is preferable to make it unevenly distribute around the support body.
[0109]
Examples of the binder used in the screen of the present invention include proteins such as gelatin, polysaccharides such as dextran and corn starch, natural high molecular substances such as gum arabic; polyvinyl butyral, polyvinyl acetate, polyurethane, polyalkyl acrylate, vinylidene chloride, nitro Examples thereof include synthetic polymer materials such as cellulose, fluorine-containing polymers, and polyesters, and mixtures and copolymers thereof. As a preferable binder, the basic performance includes a high transmittance with respect to light emitted from the phosphor. In this respect, gelatin, corn starch, acrylic polymers, fluorine-containing olefin polymers, polymers containing fluorine-containing olefins as copolymer components, styrene / acrylonitrile copolymers, and the like can be mentioned. These binders may have a functional unit that is crosslinked by a crosslinking agent. Further, depending on the required image quality performance, an absorber for light emission from the phosphor may be added to the binder, or a binder having low transmittance may be used. Examples of the absorbent include pigments, dyes, and ultraviolet absorbing compounds. The ratio of phosphor to binder is generally 1: 5 to 50: 1, preferably 1: 1 to 5: 1 in volume ratio. The ratio between the phosphor and the binder may be uniform or non-uniform in the thickness direction.
[0110]
The phosphor layer is usually formed by a coating method using a coating liquid in which a phosphor is dispersed in a binder solution. Examples of the solvent for the coating solution include water or alcohol, organic solvents such as chlorine-containing hydrocarbons, ketones, esters, ether aromatic compounds, and mixtures thereof.
In the coating solution, dispersion stabilizers such as phthalic acid, stearic acid, caproic acid, and surfactant for phosphor particles, and plasticizers such as phosphoric acid ester, phthalic acid ester, glycolic acid ester, polyester, and polyethylene glycol are added. May be.
[0111]
The screen used in the present invention can be provided with a protective layer on the phosphor layer. As the protective layer, a method of coating on the phosphor layer and a method of separately forming a protective layer film and laminating are generally used. In the application method, it may be applied simultaneously with the phosphor layer, or may be applied after the phosphor layer is applied and dried. The protective layer may be the same material as the binder of the phosphor layer or a different material. Examples of the substance used for the protective layer include cellulose derivatives, polyvinyl chloride, melamine, phenolic resins, epoxy resins and the like in addition to the substances mentioned as the binder for the phosphor layer. Preferred materials include gelatin, corn starch, acrylic polymers, olefin polymers containing fluorine, polymers containing fluorine-containing olefins as copolymer components, and styrene / acrylonitrile copolymers. The thickness of the protective layer is generally from 1 μm to 20 μm, preferably from 2 μm to 10 μm, and more preferably from 2 μm to 6 μm. It is preferable to emboss the surface of the protective layer of the present invention. Further, a matting agent may be present in the protective layer, or a substance having a light scattering property for light emission, such as titanium oxide, may be present depending on the desired image.
[0112]
In the protective layer of the screen used in the present invention, surface slipperiness may be imparted. Preferable slip agents include polysiloxane skeleton-containing oligomers and perfluoroalkyl group-containing oligomers.
[0113]
You may provide electroconductivity to the protective layer of this invention. Examples of the conductivity imparting agent include white and transparent inorganic conductive materials and organic antistatic agents. Preferred inorganic conductive materials include ZnO powder, whiskers, and SnO.₂And ITO.
[0114]
As the development processing method of the present invention, reference is made to the methods described in U.S. Pat. can do.
[0115]
It is preferable to use hydroquinone, ascorbic acid, erythorbic acid (a diastereomer of ascorbic acid) and / or a derivative thereof for the developer for processing the light-sensitive material of the present invention.
Ascorbic acid and / or derivatives thereof used in the present invention are described in US Pat.
Specifically, compounds described in US Pat. No. 2,688,549, page 22, first column, line 22 to page 1, second column, line 33, Japanese Patent Publication No. 36-17599, page 1, left column 21 Compounds described from line to line 26, compounds I-1 to I-8 and II-1 to II-4 described on page 4 of JP-A-3-249756, page 4 of JP-A-4-270343 The compounds described in 5th column, 40th line to 50th line can be used.
Of these, ascorbic acid or erythorbic acid (a diastereomer of ascorbic acid) and alkali metal salts such as lithium salts, sodium salts and potassium salts thereof are preferable.
The developing agent is usually preferably used in an amount of 0.01 mol / liter to 0.8 mol / liter, particularly preferably in an amount of 0.1 mol / liter to 0.4 mol / liter.
[0116]
In the present invention, it is desirable to use an auxiliary developing agent exhibiting superadditivity together with the developing agent.
As an auxiliary developing agent exhibiting superadditivity, there is a 1-phenyl-3-pyrazolidone auxiliary developing agent.
1-Phenyl-3-pyrazolidones auxiliary developing agents include 1-phenyl-3-pyrazolidone, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4- Methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-p-aminophenyl-4,4-dimethyl -3-pyrazolidone, 1-p-tolyl-4,4-dimethyl-3-pyrazolidone, 1-p-tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidone and the like. Of these, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone is preferred.
In the present invention, when a 1-phenyl-3-pyrazolidone auxiliary developing agent is used in combination with a developing agent, it is preferably used in an amount of 0.001 mol / liter to 0.1 mol / liter, particularly the latter. Is preferably used in an amount of 0.005 mol / liter to 0.05 mol / liter.
[0117]
Further, as an auxiliary developing agent showing superadditivity, there is a p-aminophenol auxiliary developing agent.
Examples of auxiliary developing agents for p-aminophenols include N-methyl-p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, N- (4-hydroxyphenyl) -glycine, and 2-methyl-p. -Aminophenol, p-benzylaminophenol and the like, among which N-methyl-p-aminophenol is preferable.
In the present invention, when a p-aminophenol auxiliary developing agent is used in combination with a developing agent, it is preferably used in an amount of 0.001 mol / liter to 0.1 mol / liter, particularly p-amino. The phenol auxiliary developing agent is preferably used in an amount of 0.005 mol / liter to 0.05 mol / liter.
[0118]
Antifoggants added to the developer include azole compounds (for example, benzothiazoliums, benzimidazoliums, imidazoles, benzimidazoles, nitroindazoles, triazoles, benzotriazoles, tetrazoles, triazines, etc. ), Mercapto compounds (eg, mercaptothiazoles, mercaptobenzothiazoles, mercaptoimidazoles, mercaptobenzimidazoles, mercaptobenzoxazoles, mercaptothiazoles, mercaptooxadiazoles, mercaptotetrazoles, mercaptopyrimidines, mercaptotriazines Etc.).
In particular, examples of benzotriazoles include 5-methylbenzotriazole, 5-bromobenzotriazole, 5-chlorobenzotriazole, 5-butylbenzotriazole, and benzotriazole. As nitroindazoles, 5-nitroindazole, 6-nitroindazole, 4-nitroindazole, 7-nitroindazole, 3-cyano-5-nitroindazole and the like can be used.
[0119]
In the present invention, as a silver stain preventing agent in the developer, JP-B-56-46585, JP-B-62-4702, JP-B-62-4703, U.S. Pat. No. 4,252,215, U.S. Pat. The compounds described in JP-A No. -203439, JP-A No. 62-56959, JP-A No. 62-178247, JP-A No. 1-200249, JP-A No. 5-503179 and JP-A No. 5-53257 can be used.
[0120]
In the present invention, various known liquids can be used as the fixing liquid. For example, it is a well-known aqueous solution containing thiosulfate, and has a pH of 3.8 or more, preferably 4.2 to 6.2. Examples of the fixing agent include sodium thiosulfate and ammonium thiosulfate. The concentration of the fixing agent can be changed as appropriate, and the fixing solution may contain a water-soluble aluminum salt that acts as a hardener, and examples thereof include aluminum chloride, aluminum sulfate, and potassium alum. In the fixing solution, tartaric acid, citric acid, gluconic acid, or derivatives thereof can be used alone or in combination of two or more. These compounds are preferably added in an amount of 0.005 mol or more per liter of the fixing solution, and it is particularly effective to add 0.01 mol / L to 0.03 mol / L. In the fixing solution, sulfite or bisulfite as a preservative is optionally 10 g or more, preferably 50 g or more, and more preferably 0.2 g or more of acetic acid or boric acid as a pH buffering agent per liter of use solution. Is preferably contained in an amount of 0.5 mol or more. Moreover, a pH adjuster (for example, sulfuric acid), a chelating agent capable of softening water, and compounds described in JP-A-62-278551 can be included.
[0121]
Examples of fixing accelerators include thiourea derivatives described in JP-B Nos. 45-35754, 58-122535 and 58-122536, alcohols having a triple bond in the molecule, and thioethers described in US Pat. No. 4,126,459. Or cyclodextran ethers that free anions, crown ethers, diazacycloundecene, di (hydroxyethyl) butamine, and the like. Mesoionic compounds described in JP-A-7-5654 and 6-273898 can be contained.
[0122]
It is preferable to apply anti-fouling means to the washing bath or stabilizing bath. As the fouling means, an ultraviolet irradiation method described in JP-A-60-263939, a method using a magnetic field described in JP-A-60-263940, and an ion exchange resin described in JP-A-61-131632 are used. The method of using the antibacterial agent described in JP-A-61-115154, JP-A-62-153952, JP-A-62-2220951, and JP-A-62-209532 can be used in combination.
[0123]
Furthermore, L.M. F. West, “Water Quality Criteria”, Photo. Sci. & Eng. , Vol. 9 (1965), M.M. W. Beach, “Microbiological Growth in Motion-picture Processing”, SMTPE Journal Vol. 85 (1976), R.A. D. Deegan, “Photo Processing Wash Water Biocides”, J. Am. Imaging Tech. , Vol. 10, no. 6 (1984) and JP-A-57-8542, 57-58143, 58-105145, 57-132146, 58-18631, 57-97530, 57-157244, Antibacterial agents, antifungal agents, surfactants, and the like described in Kaihei Nos. 6-118583 and 8-248589 can be used in combination.
[0124]
Further, R.C. T.A. Kreinan, J .; Image. Tech. 10 (6), page 242 (1984), isothiazoline-based compounds, Research Disclosure, vol. 205, no. No. 20526 (May 1981), isothiazoline-based compound, Vol. An isothiazoline compound described in 22845 (April 1983), a compound described in JP-A No. 62-209532, and the like can also be used in combination as a fungicide (Microbiocide).
Other compounds as described in "Chemistry of Antibacterial and Antifungal" written by Hiroshi Horiguchi, Mitsui Publishing (Showa 57), "Handbook of Antibacterial and Antifungal Technology", Society of Antibacterial and Antifungal Society, Hakuhodo (Showa 61) May be included.
[0125]
Further, Japanese Patent Application Laid-Open No. 60-235133 discloses a part or all of overflow from the water washing or stabilizing bath caused by replenishing the water washing or stabilizing bath with anti-corrosive means depending on the treatment. Thus, it can be used for diluting a processing solution having a fixing ability, which is the pretreatment step.
[0126]
In the processing system of the present invention, the amount of liquid carried out by the photosensitive material from the developing tank to the fixing tank and from the fixing tank to the washing tank is preferably 0.01 ml or more and 2 ml or less per 4 sheets, and 0.1 ml or more. It is preferably 1.2 ml or less, more preferably 0.1 ml or more and 0.8 ml or less.
When the washing tank is multi-staged, the amount taken out from the washing tank to the washing tank is preferably 0.1 ml or more and 2 ml or less, more preferably 0.1 ml or more and 1.2 ml or less per 4 sheets. More preferably, it is 0.1 ml or more and 0.8 ml or less.
The amount of washing water taken out from the washing tank when entering the drying zone is preferably 0.1 ml or more and 2 ml or less, more preferably 1 ml or less, and even more preferably 0.5 ml or less per 4 pieces of sensitive material. .
[0127]
The light-sensitive material of the present invention is suitable for rapid processing, and the total processing time (Dry to Dry) from when it is carried into the developing tank until the drying step is completed is 90 seconds or less, and further 5 to 60 seconds. preferable.
In this case, development is performed at 25 to 40 ° C. for 5 to 30 seconds, fixing is performed at 25 to 40 ° C. for 5 to 40 seconds, washing is performed at 0 to 40 ° C. for 5 to 30 seconds, and drying is performed at 40 to 120 ° C. for 1 to 30 seconds. Preferably it is done. Each replenishment amount is 1m²It is preferable that the hit developing solution is 30 to 650 ml, the fixing solution is 30 to 650 ml, and the washing water is 30 to 50,000 ml.
[0128]
For details of such processing, reference can be made to the description in the above-mentioned JP-A-9-329875.
[0129]
【Example】
The following examples illustrate the invention.
Example 1
Silver halide emulsion
(Preparation of comparative silver halide emulsion-1)
High aspect ratio grains were prepared by adjusting the pAg at the time of silver halide grain growth.
1178 mL of an aqueous solution containing 0.8 g of KBr and 3.2 g of gelatin having an average molecular weight of 20000 was kept at 35 ° C. and stirred. AgNO₃An aqueous solution (1.6 g), an aqueous KBr (1.16 g) solution, and an aqueous gelatin (1.1 g) solution having an average molecular weight of 20000 were added over 45 seconds by the triple jet method. AgNO₃A solution having a concentration of 0.3 mol / liter was used. Thereafter, the temperature was raised to 75 ° C. over 20 minutes, and 26 g of gelatin having an average molecular weight of 100,000 was added. AgNO₃(209 g) An aqueous solution and an aqueous solution of KBr 99.9 mol% and KI 0.1 mol% were added over 75 minutes while accelerating the flow rate by the control double jet method while maintaining pAg 8.5. Gelatin having an average molecular weight of 100,000 was added and then desalted according to a conventional method. Thereafter, gelatin having an average molecular weight of 100,000 was added and dispersed, and adjusted to pH 5.8 and pAg 8.0 at 40 ° C. to prepare an emulsion. This emulsion contains 1 mol of Ag and 60 g of gelatin per 1 kg of emulsion. The silver halide emulsion grains have an average equivalent circle diameter of 1.2 μm, a variation coefficient of equivalent circle diameter of 21%, an average thickness of 0.12 μm, and an average aspect. The tabular grains had a ratio of 10.
[0130]
(Preparation of silver halide emulsion A-1)
A fine grain emulsion of high aspect ratio grains was prepared using oxidized gelatin during nucleation.
1178 mL of an aqueous solution containing 0.8 g of KBr and 3.2 g of oxidized gelatin having an average molecular weight of 20000 was kept at 35 ° C. and stirred. AgNO₃(1.6 g) Aqueous solution, KBr (1.16 g) aqueous solution, and oxidized gelatin (1.1 g) aqueous solution having an average molecular weight of 20000 were added over 45 seconds by the triple jet method. AgNO₃A solution having a concentration of 0.3 mol / liter was used. Thereafter, the temperature was raised to 75 ° C. over 20 minutes, and 26 g of gelatin having an average molecular weight of 100,000 was added. AgNO₃(209 g) An aqueous solution and an aqueous solution of KBr 99.9 mol% and KI 0.1 mol% were added over 75 minutes while accelerating the flow rate by the control double jet method while maintaining pAg 8.5. Gelatin having an average molecular weight of 100,000 was added and then desalted according to a conventional method. Thereafter, gelatin having an average molecular weight of 100,000 was added and dispersed, and adjusted to pH 5.8 and pAg 8.0 at 40 ° C. to prepare an emulsion. This emulsion contains 1 mol of Ag and 60 g of gelatin per 1 kg of the emulsion. The silver halide emulsion grains have an average equivalent circle diameter of 1.5 μm, a variation coefficient of equivalent circle diameter of 22%, an average thickness of 0.10 μm, and an average aspect. The tabular grains had a ratio of 15.
[0131]
(Preparation of silver halide emulsion B-1)
Fine grain emulsions with higher aspect ratio grains were prepared using oxidized gelatin during nucleation and succinated gelatin during grain growth.
1178 mL of an aqueous solution containing 0.8 g of KBr and 3.2 g of oxidized gelatin having an average molecular weight of 20000 was kept at 35 ° C. and stirred. AgNO₃(1.6 g) Aqueous solution, KBr (1.16 g) aqueous solution, and oxidized gelatin (1.1 g) aqueous solution having an average molecular weight of 20000 were added over 45 seconds by the triple jet method. AgNO₃A solution having a concentration of 0.3 mol / liter was used. Thereafter, the temperature was raised to 75 ° C. over 20 minutes, and 26 g of succinylated gelatin having an average molecular weight of 100,000 was added. AgNO₃(209 g) An aqueous solution and an aqueous solution of KBr 99.9 mol% and KI 0.1 mol% were added over 75 minutes while accelerating the flow rate by the control double jet method while maintaining pAg 8.5. Gelatin having an average molecular weight of 100,000 was added and then desalted according to a conventional method. Thereafter, gelatin having an average molecular weight of 100,000 was added and dispersed, and adjusted to pH 5.8 and pAg 8.0 at 40 ° C. to prepare an emulsion. This emulsion contains 1 mol of Ag and 60 g of gelatin per 1 kg of emulsion. The silver halide emulsion grains have an average equivalent circle diameter of 1.8 μm, a variation coefficient of equivalent circle diameter of 22%, an average thickness of 0.08 μm, and an average aspect. The tabular grains had a ratio of 23.
[0132]
(Chemical sensitization)
Each of the emulsions prepared as described above was chemically sensitized while being kept at 56 ° C. with stirring. First, the following thiosulfonic acid compound-I was added at 10 per mole of silver halide.^-4Next, 0.15 mol% of AgI fine particles having a diameter of 0.03 μm were added with respect to the total silver amount. After 3 minutes, 1 × 10 thiourea dioxide^-6Mole / mole Ag was added and held for 22 minutes for reduction sensitization. Next, 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene was added at 3 × 10 6 per mole of silver halide.^-41 mol per mol of silver halide, with a molar equivalent added and the dispersion of sensitizing dye 1 as the amount of sensitizing dye 1^-3Molar equivalent and the following sensitizing dye aqueous solutions 2, 3 are each 1.0 × 10 6 per mole of silver halide.^-4Mol, 3.0 × 10^-5The molar equivalent was added, and calcium chloride was further added.
A dispersion of sensitizing dye 1 was prepared as follows.
1 g of sensitizing dye 1 is added to 50 ml of distilled water, adjusted to pH 7.0 ± 0.5, mechanically dispersed at 2000 to 2500 rpm using a dissolver at 50 ° C. to 65 ° C., and an average particle size of 1 μm or less. Dispersed in solid fine particles. After dispersion, 50 g of 10% by weight gelatin was added and then cooled.
[0133]
Subsequently, sodium thiosulfate was added at 6 × 10 6 per mole of silver halide.^-6Mole equivalent and selenium compound-1 at 4 × 10 4 per mole of silver halide^-6After the addition of a molar equivalent, chloroauric acid was added at 1 × 10 5 per mole of silver halide.^-5Molar equivalents and potassium thiocyanate at 2 x 10 per mole of silver halide^-3Molar equivalent was added. Further, 67 mg of a nucleic acid (manufactured by Sanyo Kokusaku Pulp Co., Ltd .: trade name RNA-F) was added in an amount equivalent to 67 mg per mole of silver halide. After 40 minutes, water-soluble mercapto compound-1 was added at 1 × 10 5 per mole of silver halide.^-4In addition, the mercapto compound-2 was added in an amount equivalent to 1 mol per mol of silver halide.^-3An equivalent mole was added and cooled to 35 ° C. Thus, chemical sensitization of the emulsion was completed.
[0134]
[Chemical 1]

[0135]
Preparation of coated sample
(Preparation of dye layer coating solution)
A coating solution was prepared so that each component of the dye layer (crossover cut layer) to be coated as an emulsion lower layer had the following coating amount.
[0136]
(Method for preparing dye for crossover cut)
Dye A (solid 10 g) was stirred in a mixed solvent of methanol 150 ml and water 50 ml at 70 ° C. for 2 hours to prepare water wet cake dye I-46. As a result, 1 mol of methanol and 2 mol of water were contained in 1 mol of the dye in the dye crystal. As a method for confirming the crystal solvent, the wet cake was dried at room temperature for measurement, and the presence of methanol in the crystal could be confirmed by 1H-NMR. The presence of crystal water was confirmed by Karl Fischer titration. It was also confirmed that when this crystal was heated at 150 ° C., methanol and water of crystallization were released. From this, the dye solid concentration in the wet cake was 50% by mass.
[0137]
(Method for preparing microcrystalline aqueous dispersion of dye for crossover cut)
The above wet cake-like dye was handled as a wet cake without drying, and 3.0 g of the dye solid was weighed. After mixing 1.2 g of a 25% by weight solution of Demol SNB (manufactured by Kao Corporation) as water and a dispersant for dispersion in advance, the above dye is added, and water is added so that the total becomes 30 g. After adjustment, the mixture was mixed well to obtain a slurry. 120 g of zirconia beads were prepared, put in a vessel together with the slurry, and dispersed in a 1/16 gallon sand grinder mill (manufactured by Imex Co., Ltd.) at 1500 rpm with water cooling. The average particle diameter of the zirconia beads was 1 mm, and the dispersion time was 8 hours. After the completion of dispersion, water was added so that the solid content concentration of the dye was 5% by mass, and the dispersion was taken out. This dye dispersion was designated as DP1.
[0138]
(Method for preparing dye layer coating solution)
Each compound was added to the mother liquor so as to obtain the following coating amount. 1m on each side in the order of addition of each compound²The amount of material applied per hit was described.

At this time, the pH of the coating solution was adjusted to 6.0 using a small amount of acetic acid or sodium hydroxide. Application amount is 1m per side²It was 12.4 ml per unit.
[0139]
[Chemical 2]

[0140]
(Method for preparing emulsion layer coating solution)
Each compound was added to the emulsion so as to have the following coating amount. 1m on one side²Amount of material applied per unit
・ Amount of applied silver 1.25g
-Gelatin 1.25g
Dextran (average molecular weight 39,000) 344mg
-Sodium polystyrene sulfonate (average molecular weight 600,000) 27mg
・ A-2 162mg
・ A-3 1.9mg
・ A-4 0.35mg
・ A-5 1.9mg
・ Dye-1 (oil emulsion) 0.33 g as the solid content of the dye
・ 1,2-Bis (vinylsulfonylacetamido) ethane 50mg
At this time, the coating amount of the emulsion layer is 1 m on one side.²It was 32.6 ml. The compounds in the above were as follows.
[0141]
[Chemical 3]

[0142]
(Method for preparing surface protective layer coating solution)
Each compound was added so that it might become the following coating amounts.
1m on one side²Amount of material applied per unit
・ Gelatin 0.767g
-Sodium polyacrylate (average molecular weight 400,000) 80mg
-Sodium polystyrene sulfonate (average molecular weight 600,000) 1.1mg
Matting agent-1 (average particle size 3.7 μm) 70 mg as solid content
・ A-6 18.1mg
・ A-7 34.5mg
・ A-8 6.8mg
・ A-9 3.2mg
・ A-10 1.4mg
・ A-11 2.1mg
・ A-12 1.0mg
・ Preservative D 0.9mg
・ P-benzoquinone 0.7mg
At this time, the pH of the coating solution for the surface protective layer was adjusted to 6.8 using a small amount of sodium hydroxide. Application amount is 1m per side²It was 10.7 ml per unit. The compounds in the above were as follows.
[0143]
Replacing 1-75, 1-73 and 2-9 of the present invention in place of A-9 and 1-51, 1-50 and 2-33 in place of A-10 so as to be equimolar, respectively. In the same manner as described above, each photosensitive material was added as shown in Table 1.
[Formula 4]

[0144]
[Chemical formula 5]

[0145]
Biaxially stretched 175 μm thick blue dyeing (corresponding to 1,4-bis (2,6-diethylanilinoanthraquinone-containing) polyethylene terephthalate support, corona discharge, each coating containing the following main components: The liquid was applied to both sides of the support with a wire bar coater in the order of the first undercoat layer and the second undercoat layer.
[0146]
・ First undercoat layer (support side)
1m on one side of the support²The amount of coating solution per hit was 4.9 ml. 1m on one side of the support for each additive material²The coating amount per hit is as follows.

Drying temperature 190 ° C
[0147]
・ Second undercoat layer
1m on one side of the support²The amount of the coating solution per unit was 7.9 ml. 1m on one side of the support for each additive material²The coating amount per hit is as follows.

Drying temperature 185 ° C
[0148]
(Coating method for photographic materials)
On the undercoat-coated support prepared as described above, it was simultaneously coated on both sides by the simultaneous extrusion method so as to form a dye layer, an emulsion layer, and a surface protective layer from the support side, and dried.
[0149]
(Evaluation of coating uniformity)
The surface of each photosensitive material coated as described above was visually observed under a white light, and evaluated in five stages as follows.
5: No spot failure or uneven coating occurs.
4: Although spot failure and coating unevenness occur slightly, there is no problem in practical use.
3: Spot failures and coating unevenness occur slightly, but are practically acceptable.
2: Spot failure and coating unevenness occur, and the level is substantially unacceptable.
1: Spot failures and coating unevenness frequently occur, and are practically unacceptable levels.
The results are shown in Table 1.
[0150]
(processing)
Automatic processor: CEPROS-30 manufactured by Fuji Photo Film Co., Ltd.
Preparation of developer
[0151]

[0153]
(Preparation of treatment solution)
The developer concentration solution was filled into the CEPRO-30 treatment agent container for each part agent. In this container, the partial containers A, B, and C are connected together by the container itself.
Further, the same concentration of the fixing solution was filled in the same type of container.
First, 300 ml of an aqueous solution containing 54 g of acetic acid and 55.5 g of potassium bromide was added as a starter in the developing tank.
Invert the container with the treatment agent above and insert it into the perforation blade of the treatment liquid stock tank mounted on the side of the self-machine. Filled.
[0154]
Each of these processing agents was filled in the developing tank and fixing tank of the self-acting machine at the following ratios by operating the pumps installed in the self-acting machine.
Further, every time eight photosensitive materials were processed in terms of four-cut size, the processing agent stock solution and water were mixed at this ratio and replenished to the processing tank of the automatic machine.
[0155]
Developer
Parts agent A 55 ml
Part preparation B 10 ml
Part preparation C 10 ml
125 ml of water
pH 10.50
Fixer
Concentrate 80 ml
120 ml of water
pH 4.62
The washing tank was filled with tap water.
[0156]
In addition, 0.4 g of antibacterial fungi supported on perlite having an average particle diameter of 100 μm and an average pore diameter of 3 μm was covered with a polyethylene bottle (the bottle opening was covered with a 300 mesh nylon cloth, and water was removed from the cloth. 3 of them were prepared, and two of them were submerged in the bottom of the washing tank and one was submerged in the bottom of the stock tank (0.2 liters) of the washing water. .
[0157]
(Evaluation of uneven development)
Uniform exposure is performed on each coated photosensitive material in four-cut size (10 inches × 12 inches) so that the blackening density falls within the range of 1.1 to 1.3 under the processing conditions described below. I made it. The processed photosensitive material was visually observed on a Schaukasten and evaluated in five stages as follows.
5: Level where the whole is uniformly blackened and development unevenness is not observed at all.
4: Although there is slight development unevenness, it is at a level where there is no practical problem.
3: Although development unevenness occurs slightly, it is a practically acceptable level.
2: There is development unevenness, which is a substantially unacceptable level.
1: Occurrence of development unevenness is remarkable and is at a level that is not acceptable in practical use.
The obtained results are shown in Table 1.
[0158]
[Table 1]

[0159]
As is clear from the results in Table 1, when a comparative fluorine-containing compound such as A-9 or A-10 is used, the uniformity of coating increases as the thickness of the silver halide grains decreases and the aspect ratio increases. And development unevenness deteriorates. In particular, when the silver halide emulsion B-1 having a silver halide grain thickness of 0.08 μm and an aspect ratio of 22.5 is used, the coating uniformity and development unevenness are remarkably deteriorated and cannot be practically used. there were.
On the other hand, when the fluorine-containing compound represented by the general formula (1) or the general formula (2) in the present invention is added, the coating uniformity is good even when the thickness of the silver halide grains is small and the aspect ratio is large. And good results without uneven development were obtained.
Thus, by adding the fluorine-containing compound represented by general formula (1) or general formula (2), it becomes a coating liquid showing good coating performance without depending on the shape of silver halide, and this coating. In the photosensitive material formed using the solution, development unevenness was remarkably reduced.
[0160]
【The invention's effect】
According to the present invention, it is possible to provide a silver halide photographic light-sensitive material having good coating uniformity and less development unevenness.

Claims (3)

A method for processing a silver halide photographic light-sensitive material having at least one photosensitive silver halide photographic emulsion layer on one side or both sides of a support,
The silver halide emulsion grains in the silver halide emulsion layer are tabular grains having an average thickness of 0.03 to 0.11 μm and an average aspect ratio of 13 to 30;
A silver halide photographic light-sensitive material containing at least one fluorine-containing compound selected from the group consisting of compounds represented by the following general formulas (1) and (2).
General formula (1)
_{Rf 1 - (ORf 2) n1} - (L 1) m2 - (X 1) m1
Wherein Rf ₁ represents an aliphatic group containing at least one fluorine atom, Rf ₂ represents an alkylene group containing at least one fluorine atom, and n1 and m1 each independently represents an integer of 1 or more. , M2 represents 1 or 0. L ₁ represents a linking group, and X ₁ represents a hydroxyl group, an anionic group or a cationic group.)
General formula (2)
_{[(Rf 3 O) n2 -} (PFC) -CO-Y 2] K -L 2 - (X 2) m2
(Wherein Rf ₃ represents a perfluoroalkyl group having 1 to 4 carbon atoms, RFC represents a perfluorocycloalkyl group, Y ₂ represents a linking group containing an oxygen atom or a nitrogen atom, L ₂ Represents a bond or a linking group, X ₂ represents an anionic group, a cationic group, a nonionic group or a water-soluble polar group containing an amphoteric group, n2 represents an integer of 1 to 5, and K represents 1 to 3 And m2 represents an integer of 1 to 5.) 2. The halogenated silver halide emulsion according to claim 1, wherein the silver halide emulsion grains are tabular grains having an average thickness of 0.03 μm to 0.11 μm and an average aspect ratio of 13 to 25. 3. Silver photographic material. The silver halide emulsion grains are silver iodobromide and have a silver iodide content of 0.05 mol% or more and 0.45 mol% or less. Silver halide photographic light-sensitive material.