JPH10319527A - Silver halide photographic sensitive material and its processing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the silver halide photographic sensitive material and its processing method superior in aptitude to rapid processing and running stability and stability for a long period. SOLUTION: The silver halide photographic sensitive material is provided on a support with a silver halide emulsion layer containing epitaxial silver halide grains joined with flat host silver halide grains and this emulsion contains a palladium compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material (hereinafter sometimes simply referred to as a light-sensitive material or a light-sensitive material) and a processing method thereof. The present invention relates to a silver halide photographic light-sensitive material excellent in long-term storability and a processing method thereof.

[0002]

2. Description of the Related Art Incineration treatment has been carried out in accordance with the ban on the dumping of photographic processing wastewater into the ocean since 1995. Land-based processing of processing wastewater, however, causes an increase in energy and cost, and suppresses processing wastewater. Therefore, a reduction in the amount of replenishment is desired. However, the reduction of the processing waste liquid has the disadvantage that the stagnation time of the liquid in the processing tank is prolonged, oxidative fatigue of the processing liquid is caused, the density and gamma of the photosensitive material to be processed are reduced, and the processing stability is deteriorated. doing.

[0003] In the field of medical X-ray photographic materials, prompt provision of image information is required in order to promptly grasp the condition of a patient and perform prompt treatment from the viewpoint of emergency medical care. There is a strong demand for rapid processing of photosensitive materials.

[0004] As a means for responding to such a demand, the covering power of developed silver is increased by a method such as reducing the average grain size or using tabular grains having a high aspect ratio and a small grain thickness, thereby reducing the amount of coated silver. It is known. However, when the particle size is reduced, the sensitivity is reduced, so that sensitization is necessary to maintain the conventional sensitivity. Until now, various sensitization technologies have been used to reduce the amount of silver in photosensitive materials, and have been working to speed up processing time and reduce processing waste liquid. However, in order to further speed up and reduce processing waste liquid, At present, however, further sensitization technology is required.

[0005] Japanese Patent Application Laid-Open No. 8-1711 discloses an example of a sensitizing technique.
No. 64 discloses a sensitization technique using epitaxial grains, and this technique has made it possible to reduce the particle size. However, according to the study of the present inventor, storage stability for a long time is deteriorated,
It has been found that it has disadvantages such as a decrease in sensitivity and an increase in fog.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic light-sensitive material which is excellent in rapid processing, running stability and long-term storage, and a processing method therefor.

[0007]

The above objects of the present invention are as follows. In a silver halide photographic material having at least one silver halide emulsion layer provided on a support, the silver halide emulsion layer comprises tabular silver halide grains having host grains. A silver halide photographic light-sensitive material containing a silver halide emulsion containing silver halide grains epitaxially bonded to grains, and containing a palladium compound;

[0008] 2. 2. The silver halide photographic light-sensitive material as described in 1 above, wherein the silver halide grains epitaxially bonded are silver halide grains satisfying the following condition A. Condition A: The (1,1,1) plane is a main plane; 0.5 circle equivalent diameter
３3.0 μm and thickness of 0.07-0.7 μm. Including epitaxially deposited silver halide protrusions in a face-centered cubic lattice structure forming an epitaxy junction. The silver halide projections are located at the periphery of the host tabular grains.

3. 3. A method for processing a silver halide photographic light-sensitive material, comprising subjecting the silver halide photographic light-sensitive material according to 1 or 2 to imagewise exposure and then performing photographic processing in a step including a developing and fixing step.

[0010] 4. The replenishment amounts of the developing solution and the fixing solution are each 200 m per 1 m ^{2 of the} processed silver halide photographic light-sensitive material.
3. The method for processing a silver halide photographic light-sensitive material as described in 3 above, wherein the processing is carried out by an automatic development processing system having an amount of 1 or less.

5. 5. The method for processing a silver halide photographic material according to the above item 3 or 4, wherein the developer contains reductones.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The details of the present invention will be described below. [Silver halide grains (including silver halide projections)] As the host tabular silver halide grains in the present invention, conventional silver halide grains can be used without any particular limitation. The description of tabular silver halide grains satisfying this criterion is described in Wi.
Igus et al., US Pat. No. 4,434,226, Kof.
ron et al., US Pat. No. 4,432,226;
U.S. Patent No. 4,433,048 to Yamada et al.
U.S. Pat. No. 4,672,027 to Sugimoto.
o et al., U.S. Patent No. 4,650,012, Yamada.
U.S. Pat. No. 4,679,745 to Maskask.
y U.S. Pat. No. 4,713,320, Nottorf
U.S. Pat. No. 4,722,886 to Sugimoto
U.S. Pat. No. 4,755,456, Goda U.S. Pat. No. 4,755,617, Ellis U.S. Pat.
01522, Ikeda et al., U.S. Pat.
No. 461, U.S. Pat. No. 4,850,350 to Ohashi et al.
No. 95, Makino et al., US Pat.
No. 2, U.S. Pat. No. 491 to Daubendiek et al.
4014, U.S. Pat. No. 496,201 to Aida et al.
No. 5, U.S. Pat. No. 4,985,350 to Ikeda et al., U.S. Pat. No. 5,061,609 to Piggin et al., U.S. Pat. No. 5,061,616 to Piggin et al., U.S. Pat. No. 5,147,771 to Tsur et al.
U.S. Pat. No. 14,177,772 to Tsaur et al., Tsa
ur et al., US Pat. No. 5,147,773, Tsaur
U.S. Pat. No. 5,171,659; Sutton et al., U.S. Pat. No. 5,300,433; Delton, U.S. Pat. No. 5,310,644; Chang et al., U.S. Pat. No. 5,314,793; Black et al., U.S. Pat.
No. 334495, Chaffee et al., US Pat.
358840 and Delton U.S. Pat.
No. 72927, etc.

The silver halide grains used in the present invention are:
After the host tabular silver halide grains are prepared, they are prepared by epitaxy growth. Hereinafter, the silver halide grains at the time of preparing the host tabular silver halide grains will be referred to as “host tabular grains” or simply “tabular grains”.

In the present invention, the halogen composition of the host tabular grains is preferably any of silver bromide, silver iodobromide, silver chlorobromide and silver chloroiodobromide. When silver iodide is contained, the silver iodide content is preferably 0.1 to 10 mol%, and 0.2 to 6 mol%.
Is more preferable, and 0.4 to 2 mol% is particularly preferable. Tabular silver halide grains can contain a small amount of silver chloride. For example, US Pat. No. 5,372,927 discloses silver chlorobromide having a silver chloride content of 0.4 to 20 mol%. It describes tabular grains.

The tabular silver halide grains of the present invention have two opposing parallel main planes, and the main planes are (1,1,1) planes. The circle equivalent diameter is 0.5-3.0
μm, and preferably 0.5 to 2.0 μm. The thickness is 0.07 to 0.7 μm, preferably 0.1 to 0.7 μm
m.

Here, the circle equivalent diameter means an average projected area diameter (hereinafter, referred to as a particle diameter), and is a circle equivalent diameter of the projected area of the tabular silver halide grains (the same projected area as the silver halide grains). And the thickness indicates a distance between two parallel main planes forming tabular silver halide grains.

The tabular silver halide grains used in the present invention are preferably monodisperse emulsions having a narrow grain size distribution, specifically, (standard deviation of grain size / average grain size) × 100 = broad grain size distribution. When the width of the distribution is defined by (%), it is preferably 25% or less, more preferably 20% or less,
Especially preferably, it is 15% or less.

The tabular silver halide grains used in the present invention preferably have a narrow thickness distribution. Specifically, when the distribution width is defined by (standard deviation of thickness / average thickness) × 100 = width (%) of thickness distribution, it is preferably 25% or less, more preferably 20% or less. %, Particularly preferably 15% or less.

The tabular silver halide grains of the present invention are crystallographically classified as twins. Twins are silver halide crystals having one or more twin planes in one grain,
The classification of the twin morphology is described in the report by Klein and Moiser in Photographic Correspondents (Photogr).
aphishe Korrespondenz), Vol. 99, p. 99, and Vol. 100, p. 57.

In the tabular silver halide grains of the present invention, the silver halide projections may be formed on the main plane of the host tabular grains or at the periphery, but are preferably formed at the periphery. . Here, in the present invention, the peripheral portion of the host tabular grain is defined as the outer periphery of the main plane of the tabular grain and a distance from the outer periphery of 10% of the equivalent circle diameter of the host tabular grain.
It indicates a range surrounded by a line portion indicated by a set of points which are%.

The halogen composition of the silver halide projections in the present invention is preferably any of silver bromide, silver iodobromide, silver chlorobromide and silver chloroiodobromide. When silver iodide is contained, the silver iodide content is preferably 0.1 to 13 mol%, and 0.1 to 10 mol%.
Mole% is more preferred.

When the silver halide projections are deposited on the host tabular grains, halide ions are introduced. When a plurality of halide ions are introduced, those having high solubility of the salt with silver may be added. preferable.

Since the solubility of silver iodide is lower than that of silver bromide, and the solubility of silver bromide is lower than that of silver chloride, when halide ions are added in a preferred order,
Chloride ions are most likely to adhere near the joint. In some cases, the projections form a clear layer and can detect regions with high and low chloride ion concentrations, but sometimes cannot be detected when halides are added in a preferred order. This is because both bromide and iodide ions have the ability to replace the chloride of silver chloride deposited earlier to some extent.

In the present invention, the silver halide epitaxy is formed at a position closest to the periphery of the host tabular grains and less than 50% of the (1,1,1) plane of the tabular grains, preferably at (1,1) of the tabular grains. , 1) It is preferred to limit the fraction to a much smaller percentage of the surface, preferably less than 25%, most preferably less than 10% and optimally less than 5%. When the tabular grains include a central region with low iodide concentration and regions located on the sides with high iodide concentration, silver halide epitaxy, typically including the edges and corners of the tabular grains It is preferable to limit to the portion of the tabular grains formed by the region arranged on the side.

In the practice of the present invention, a nominal amount of silver halide epitaxy (about 0.05 mol% based on total silver (including silver in the host and epitaxy)) is effective.
It is preferred to limit silver halide epitaxy to less than 50 mol% of total silver. Generally, 0.3 to 25 mol%
Is preferred, and a concentration of about 0.5 to 15 mol% is generally optimal for sensitization.

The temperature of the emulsion containing the host tabular grains when introducing halide ions is introduced at an arbitrary temperature of 35 to 70 ° C. Further, the pAg is preferably in the range of 6 to 8.5, and the pH is preferably in the range of 4 to 9.

When the silver halide projections are formed on the periphery of the host tabular grains, a compound which acts to limit the site where the silver halide projections are epitaxially attached before introducing the halide ion ( Hereinafter, it will be referred to as a site director.) When the site director is not added, the silver halide projections are precipitated not only on the peripheral portion of the host tabular grain but also on the entire main plane.

The site director preferably used in the present invention may be any one including a compound generally known in the art as a spectral sensitizing dye for silver halide grains,
Specifically, of the cyanine, merocyanine, complex cyanine, complex merocyanine, holopolar, hemicyanine, styryl, hemioxanol dyes, and the like, compounds that form a J-aggregate with silver halide are preferred. In particular, green and red absorbing cyanine dyes are preferred. Further, as a site director of the inorganic compound, iodide, thiocyanide, selenocyanide and the like can also be used.

The temperature of the emulsion containing the host tabular grains when introducing the site director is introduced at an arbitrary temperature of 35 to 70 ° C. Preferably it is 35-60 degreeC.

The emulsion containing host tabular grains at the time of introducing the site director has a pAg of 6 to 8.5 and a pH of 4
The range of ~ 9 is preferred.

The tabular silver halide grains of the present invention may have dislocations. Dislocations are described in F. Hamilt
on, Photo. Sci. Eng. , 57 (196)
7) and T. Shiozawa, J .; Soc. Pho
t. Sci. Japan, 35, 213 (1972) and can be observed by a direct method using a low-temperature transmission electron microscope. That is, the silver halide grains taken out from the emulsion so as not to apply enough pressure to generate dislocations on the grains are placed on a mesh for observation with an electron microscope, and the sample is prepared so as to prevent damage (printout, etc.) by an electron beam. Observation is performed by a transmission method in a state of cooling. At this time, the higher the thickness of the particles, the more difficult it is for the electron beam to pass therethrough. Therefore, a high-pressure type (200 μm for particles having a thickness of 0.25 μm) is used.
(kv or more) can be observed more clearly using an electron microscope.

The tabular silver halide grains used in the present invention may be formed by a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt (including a complex salt), a rhodium during the process of forming and / or growing the grains. Metal ions can be added using at least one selected from salts (including complex salts) and iron salts (including complex salts), and these metal elements can be contained inside and / or on the surface of the particles.

[Spectral Sensitization] In the present invention, in an aqueous system substantially free of an organic solvent and / or a surfactant, 27
The solubility at 2 ° C. is 2 × 10 ⁻⁴ to 4 × 10 ⁻² mol /
Examples of the spectral sensitizing dye represented by 1 include the following compounds.

[0034]

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[0035]

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[0036]

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Various dispersers are effectively used to mechanically pulverize and disperse these spectral sensitizing dyes in an aqueous solvent to form solid fine particles of 1 μm or less. Specifically, a high-speed stirrer, a ball mill, a sand mill, a colloid mill, an ultrasonic disperser, or the like is used. In the present invention, a high-speed stirrer is preferable.

The sensitizing dyes may be used alone or in combination, and the combination is often used particularly for supersensitization. In addition to the sensitizing dye, the emulsion layer may contain a dye having no spectral sensitization or a substance which does not substantially absorb visible light and exhibits supersensitization. For example, a substituted aminostilbene compound which is a nitrogen-containing heterocyclic nucleus group (for example, US Pat. No. 2,933,933)
390 and 3,635,721), formaldehyde condensates of aromatic organic acids (for example, those described in US Pat. No. 3,743,510), cadmium salts, azaindene compounds and the like. .

[Chemical Sensitization] In the method for chemically ripening silver halide grains used in the present invention, gold sensitization, sulfur sensitization, reduction sensitization, sensitization with a chalcogen compound, and combinations thereof are preferably used.

As the chemical sensitization method, so-called sulfur sensitization, gold sensitization, and a sensitization method using a combination thereof can be used. Among them, a combination of gold sensitization and sulfur sensitization or a combination of gold sensitization and sensitization with a selenium compound is preferable. The addition amount of the selenium compound can be arbitrarily set, but it is preferable to use it together with sodium thiosulfate during chemical sensitization. More preferably, the molar ratio of the selenium compound to sodium thiosulfate is 2: 1 or less, more preferably 1: 1 or less. It is also preferable to carry out the reaction in combination with the reduction sensitization.

In the case of selenium sensitization, a wide variety of conventionally known selenium compounds can be used as the selenium sensitizer. Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (eg, allyl isoselenocyanate, etc.), selenoureas (eg, N, N
-Dimethylselenourea, N, N, N'-triethylselenourea, N, N, N'-trimethyl-N'-heptafluoropropylcarbonylselenourea, N, N, N'-trimethyl-N'-4-nitro Phenylcarbonylselenourea, etc.), selenoketones (eg, selenoacetone,
Selenoacetophenone, etc.), selenoamides (for example,
Selenoacetamide, N, N-dimethylselenobenzamide, etc.), selenocarboxylic acids and selenoesters (eg, 2-selenopropionic acid, methyl-3-selenobutyrate, etc.), and selenophosforts (eg,
Tri-p-triselenophosphorate, etc.), and selenides (triphenylphosphine selenide, diethyl selenide, diethyl diselenide, etc.). Particularly preferred selenium sensitizers are selenoureas, selenamides, selenoketones, selenides.

The amount of the selenium sensitizer used depends on the selenium compound used, silver halide grains, chemical ripening conditions and the like, but is generally 1 × 10 ⁻⁸ per mol of silver halide.
〜1 × 10 ⁻⁴ mol is used. Depending on the properties of the selenium compound to be used, the addition may be carried out by dissolving in water or an organic solvent such as methanol or ethanol alone or in a mixed solvent. Further, a method in which the mixture is added in advance with a gelatin solution, or a method in which the mixture is added in the form of an emulsified dispersion of a mixed solution with a polymer soluble in an organic solvent according to the method disclosed in JP-A-4-140739 may be used.

The temperature of chemical ripening using a selenium sensitizer is 4
The range of 0 to 90 ° C is preferable, and more preferably 45 to 8C.
0 ° C. Further, the pH is preferably in the range of 4 to 9, and the pAg is preferably in the range of 6 to 9.5.

It is preferable to supply iodine ions at the time of chemical sensitization or at the end of the chemical sensitization in terms of sensitivity and dye adsorption. Particularly, a method of adding silver iodide in the form of fine grains is preferable.

It is also preferable to carry out the chemical sensitization in the presence of a compound having adsorptivity to silver halide. As the compounds, azoles, diazoles, triazoles, tetrazoles, indazoles, thiazoles, pyrimidines, azaindenes, and particularly compounds having a mercapto group and compounds having a benzene ring are preferable.

The silver halide photographic light-sensitive material processed by the processing method of the present invention may be subjected to reduction sensitization or desensitization processing. Examples of the reduction sensitization method include a method of adding a reducing compound, a method of passing a silver ion excess state of pAg = 1 to 7 called silver ripening, and a method of pH = high ripening.
It may be applied to the silver halide emulsion by, for example, a method of passing a high pH of 8 to 11. Further, these two or more methods can be used in combination.

The method of adding a reducing compound is preferred because the degree of reduction sensitization can be finely adjusted. The reducing compound may be any of inorganic or organic compounds, thiourea dioxide, stannous salts, amines and polyamines, hydrazine derivatives, formamidine sulfinic acid, silane compounds, borane compounds, ascorbic acid and its derivatives,
Sulfites and the like. The amount of the reducing compound to be added varies depending on the reducibility of the compound, the type of silver halide, and emulsion production conditions such as dissolution conditions, but is from 1 × 10 ⁻⁸ to 1 × 10 ⁻² mol per mol of silver halide. Is appropriate. These reducing compounds are dissolved in water or an organic solvent such as alcohols, and added at any time from the time of silver halide grain growth to immediately before coating.

US Pat. Nos. 3,615,613 and 3,6
No. 15,641, No. 3,617,295, No. 3,63
The combination described in US Pat. No. 5,721 or the like is particularly useful.
The sensitizing dye may be added during or during each step of nucleation, growth, desalting, and chemical sensitization, or after chemical sensitization.

[Palladium compound] The light-sensitive material of the present invention contains a palladium compound. The palladium compound is a compound containing divalent or tetravalent palladium, and is preferably a compound represented by M ₂ PdX ₆ or M ₂ PdX ₄ . Here, M represents a hydrogen atom, an alkali metal atom or an ammonium group. X represents a halogen atom, for example, a chlorine, bromine or iodine atom.

The method of incorporating the palladium compound into the light-sensitive material may be an emulsion coating method or a method in which the palladium compound is added to the hydrophilic colloid layer on the side where the emulsion layer is present, but the emulsion layer is preferred. The palladium compound may be added at any stage from emulsion grain formation to coating. The amount of addition is 1 × 10 ⁻⁵ mol to 1 × 10 ⁻² mol, preferably 5 × 10 ⁻⁵ mol, per mol of silver halide.
Mol to 1 × 10 ⁻³ mol.

Hereinafter, specific examples of the palladium compound preferably used in the present invention will be shown, but the present invention is not limited thereto. (Examples of compounds) PdCl ₂ , Pd (NO ₃ ) ₂ , PdSO
₃ , K ₂ PdCl ₄ , (NH ₄ ) ₂ PdCl ₄ , Na ₂
PdCl ₄ , (NH ₄ ) ₂ PdCl ₆ , Li ₂ PdCl
₄ , Na ₂ PdCl ₆ , K ₂ PdBr ₄ These palladium compounds may be added alone, but are preferably added so as to be present at the time of chemical sensitization with a selenium or tellurium compound. The timing of addition may be any timing before the termination of selenium or tellurium sensitization, but is preferably prior to the addition of at least one selenium or tellurium sensitizer. More preferably, before all the chemical sensitizers have been added.

The chemical sensitizer mentioned here is a known chemical sensitizer, for example, a chalcogen sensitizer such as sodium thiosulfate, potassium thiosulfate, triphenylphosphine selenide, chloroauric acid, chloride Noble metal sensitizers such as sodium goldate, and reduction sensitizers such as stannous chloride, sodium borohydride, and ascorbic acid. Preferably, the sensitizing dye in the present invention is added before the chalcogen sensitizer.
In addition, when adding after the noble metal sensitizer, it is preferable to add it at least 10 minutes or more after the completion of the addition of the noble metal sensitizer.

[Other Structure] Gelatin is preferably used as the hydrophilic colloid and the binder used in the present invention, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, albumin, protein hydroxyethylcellulose such as casein, carboxymethylcellulose, cellulose derivatives such as cellulose sulfates, sodium alginate, dextran, sugar derivatives such as starch derivatives, polyvinyl Use of various kinds of synthetic hydrophilic polymer substances such as homopolymers or copolymers of alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Can be. Particularly, it is preferable to use dextran or polyacrylamide having an average molecular weight of 5,000 to 100,000 together with gelatin.

Examples of gelatin include lime-processed gelatin, acid-processed gelatin, and Bull. Soc. Sci. Photo, Japan
an. Mo. 16, 30 (1966), gelatin derivatives (e.g., acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinylsulfonamides, maleimide) Compounds obtained by reacting various compounds such as compounds, polyalkylene oxides, and epoxy compounds).

When a dye capable of decoloring and / or flowing out during development processing is contained in at least any one of the silver halide emulsion layer and the constituent layers other than the emulsion layer, high sensitivity and high sharpness can be obtained. In addition, a photosensitive material having rapid processing suitability can be obtained. The dye used in the photosensitive material may be appropriately selected from dyes that can improve sharpness by absorbing a desired wavelength and removing the influence of the wavelength, depending on the photosensitive material. it can. It is preferable that the dye is decolorized or flows out during the development processing of the light-sensitive material, and the color is not visually recognized when the image is completed.

It is also preferred to add the dye as a solid particulate dispersion. As a method for producing a solid particulate dispersion of a dye, specifically, using a surfactant, for example, using a fine dispersing machine such as a ball mill, a vibration mill, a sand mill, a roller mill, a jet mill, and a disk impeller mill. Can be prepared. Also, after dissolving the dye in a weakly alkaline aqueous solution, a method of precipitating fine solid particles by lowering the pH to weakly acidic or a weakly alkaline solution of the dye and an acidic aqueous solution are simultaneously mixed while adjusting the pH. A dispersion of the dye can be obtained by a method for preparing a finely divided solid. The dye may be used alone,
Also, two or more kinds may be used as a mixture. When two or more kinds are used as a mixture, they may be dispersed independently, and then mixed, or they may be dispersed simultaneously.

The constituent layer to which the dye is added and contained is preferably a silver halide emulsion layer and / or a layer closer to the support, and more preferably a layer added to the coating layer adjacent to the transparent support. It is effective to do. The concentration of the dye is preferably high on the side close to the support.

The amount of the dye to be added can be changed according to the purpose of sharpness. Preferably 0.2 to 20 mg /
m ² , more preferably 0.8 to 15 mg / m ² .

When coloring the silver halide emulsion layer,
A dye may be added to the silver halide emulsion liquid before coating or to the aqueous solution of hydrophilic colloid, and these liquids may be coated on the support directly or through another hydrophilic colloid layer by various methods. .

As described above, it is preferable that the concentration of the dye is higher on the side closer to the support, but a mordanting agent can be used to fix the dye on the side closer to the support. For example, a non-diffusible mordanting agent can be used to bind to at least one of the aforementioned dyes.

The method for bonding the non-diffusible mordant to the dye may be carried out by various methods known in the art, but the method of bonding in a gelatin binder is particularly preferably applied. In addition, a method of binding in an appropriate binder and dispersing in an aqueous gelatin solution by ultrasonic waves or the like can also be applied.

Although the binding ratio is not uniform depending on the compound, usually, the non-diffusible mordant is bound at 0.1 to 10 parts by weight with respect to 1 part by weight of the water-soluble dye. Since the amount added as the water-soluble dye is bonded to the non-diffusible mordant, it can be used in a larger amount than when the dye is used alone.

When incorporated in the light-sensitive material, a constituent layer containing a combination of a dye and a non-diffusible mordant may be newly provided as a constituent layer, and its position can be arbitrarily selected, but it is preferably a transparent support. It is effective to use it as a coating layer adjacent to the body.

As the surfactant for preparing the solid particulate dispersion, any of an anionic surfactant, a nonionic surfactant, a cationic surfactant and an amphoteric surfactant can be used. For example, anions such as alkyl sulfonates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfates, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, and N-acyl-N-alkyl taurines Surfactants and, for example,
Nonionic surfactants such as saponins, alkylene oxide derivatives, and alkyl esters of sugars.

The amount of the anionic activator and / or the nonionic activator to be used is not uniform depending on the kind of the activator or the conditions of the dispersion of the dye, but it is usually 0.1 to 2000 mg per 1 g of the dye. , Preferably 0.5 to 10
The dose may be 00 mg, more preferably 1 to 500 mg. The concentration of the dye in the dispersion is 0.01 to 10% by weight, preferably 0.1 to 5% by weight. The surfactant is preferably added before the start of the dispersion of the dye, and may be further added to the dye dispersion after the completion of the dispersion, if necessary. These anionic activators and / or nonionic activators may be used alone or in combination of two or more, respectively, and both activators may be used in combination.

When the silver halide emulsion is coated on only one side of the support, it is general to provide an antihalation dye-containing layer. The antihalation dye-containing layer may be located between the emulsion and the support or on the opposite side of the emulsion layer with the support interposed therebetween. It is preferably provided as a back layer. The transmission density of the dye-containing layer at the wavelength of the exposure light source is 0.4 to 1.5, preferably 0.45 to 1.2. The method of adding the dye includes aqueous solution addition, micelle dispersion addition, solid dispersion addition, and the like, depending on its properties.

[Processing] The processing method of the present invention employs a developer replenishment amount of 5 to ² per m ^{2 of the} photographic material according to the present invention to be processed.
00 ml and fixer replenishment amount is 5 to 200 ml.

The developing solution used in the processing method of the present invention preferably contains reductones. The reductones are preferably those represented by the following general formula (1).

[0069]

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In the formula, R ¹ and R ² each represent a hydroxyl group, an amino group (including those substituted with an ethyl group, a butyl group, a hydroxyethyl group, an alkyl group having 1 to 10 carbon atoms), an acylamino group ( Acetylamino group, benzoylamino group, etc., alkylsulfonylamino group (methanesulfonylamino group, etc.), arylsulfonylamino group (benzenesulfonylamino group, p-toluenesulfonylamino group, etc.), alkoxycarbonylamino group (methoxycarbonylamino group, etc.) ), Mercapto groups,
Represents an alkylthio group (eg, methylthio group, ethylthio group). Preferred examples of R ¹ and R ² include a hydroxyl group, an amino group, an alkylsulfonylamino group, and an arylsulfonylamino group.

X is a group of atoms necessary to form a 5- to 6-membered ring, and is preferably composed of a carbon atom, an oxygen atom or a nitrogen atom, and two vinyl carbon atoms substituted by R ¹ and R ² And a carbonyl carbon atom to form a 5- to 6-membered ring. Specific examples of the configuration of X include -O-, -C-
^{(R 3) (R 4)} -, - C (R 5) =, - C (= O)
^{-, - N (R 6)} -, - N = combinations thereof.
Here, each of R ³ , R ⁴ , R ⁵ , and R ⁶ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may be substituted (as a substituent, a hydroxyl group, a carboxyl group, a sulfo group, or the like may be mentioned. ), A hydroxyl group and a carboxyl group. Further, the 5- or 6-membered ring may form a saturated or unsaturated condensed ring.

Examples of the 5- or 6-membered ring include dihydrofuranone, dihydropyrone, pyranone, cyclopentenone,
Each ring such as pyrrolinone, pyrazolinone, pyridone, azacyclohexenone, uracil, etc., is preferred,
Examples of the six-membered ring include dihydrofuranone, cyclopentenone, cyclohexenone, pyrazolinone, azacyclohexenone, and uracil. The compound represented by the general formula (1) may form a salt such as lithium, sodium, potassium, and ammonium. Specific examples of the reductone represented by the general formula (1) are shown below, but the present invention is not limited thereto.

Preferred among the specific examples below are ascorbic acid or erythorbic acid (stereoisomer) (1-1).

[0074]

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[0075]

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[0076]

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[0077]

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[0078]

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These compounds are typically ascorbic acid or erythorbic acid or derivatives derived therefrom, and are commercially available or can be easily synthesized by a known synthesis method. The amount of ascorbic acid or erythorbic acid or a derivative thereof according to the present invention is 0.05 to 12 per liter of developer.
0 g, preferably 10 to 60 g, more preferably 40 to
Preferably, it is 50 g.

Examples of the auxiliary developer having superadditivity with the developer represented by the general formula (A) include a 3-pyrazolidone derivative and a p-aminophenol derivative. Less than,
Specific examples of the auxiliary developer will be given below, but it should not be construed that the invention is limited thereto.

1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-4'-hydroxymethyl-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, N-methyl-p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, N- (4-hydroxyphenyl) glycine, 2-methyl-p-amino Phenol, p-benzylaminophenol and the like.

In the method for processing a silver halide photographic light-sensitive material of the present invention, the following dihydroxybenzene-based developer may be used in combination.

[0083]

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In the formula, R ₅ , R ₆ , R ₇ and R ₈ each independently represent a hydrogen atom, an alkyl group, an aryl group, a carboxyl group, a halogen atom, or a sulfo group.

Specific compounds include, for example, hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone,
Examples thereof include 2,5-dimethylhydroquinone and the like, and the one most commonly used is hydroquinone.

In the processing method of the present invention, the processing may be performed using an auxiliary solution for both the developing solution and the fixing solution. The amount of replenishment is not particularly limited, but is 6 to 90 m per one sheet of the photosensitive material.
l of replenisher, preferably 1 to 1 for both developer and fixer.
A replenishment volume of 0 to 40 ml is sufficient.

In the present invention, as a developer for black-and-white photography, in addition to the above-mentioned reductones, for example, dihydroxybenzenes (hydroquinone, etc.), 3-pyrazolidones (1-phenyl-3-pyrazolidone, etc.), aminophenols (N-methyl-aminophenol and the like) can be used alone or in combination.

Further, as a preservative, a developer is disclosed in
In addition to the sulfite described in JP-B-138591, an organic reducing agent can be used, and in addition, a bisulfite adduct of a chelating agent or a hardener described in JP-A-6-138391 can be used. Japanese Patent Application Nos. 4-92947 and 5-9
No. 6118, silver sludge inhibitor, JP-A No. 1-12
It is also preferable to add a cyclodextrin compound described in No. 4853 and an amine compound described in US Pat. No. 4,269,929.

It is necessary to use a buffer for the developer.
Sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borate), potassium borate, o-
Sodium hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, 5-sulfo-
Examples thereof include sodium 2-hydroxybenzoate (sodium 5-sulfosalicylate) and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate).

Examples of the development accelerator include thioether compounds, p-phenylenediamine compounds, quaternary ammonium salts, p-aminophenols, amine compounds, polyalkylene oxides, other 1-phenyl-3-pyrazolidones, and hydrazines. , A mesoionic compound, an ionic compound, imidazoles and the like can be added as necessary.

As antifoggants, alkali metal halides such as potassium iodide and benzotriazole;
6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole,
Organic antifoggants such as 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine can be used.

Further, the developer composition includes methyl cellosolve, methanol, acetone, dimethylformamide, cyclodextrin compound, JP-B-47-33378,
The compounds described in JP-A-44-9509 can be used as an organic solvent for increasing the solubility of the developing agent, and other stain preventing agents, sludge preventing agents and layering effect promoters can also be used.

The fixing solution includes a fixing agent, a chelating agent, and a pH.
Known compounds such as a buffer and a preservative can be used. For example, JP-A-4-242246 or 5-1136
No. 32 can be used.

As the fixing agent, thiosulfate, thiocyanate and the like are used, and may further contain a preservative, a pH adjuster, a water softener and the like.

As an advantageous method for processing the silver halide photographic light-sensitive material of the present invention, processing is performed by an automatic developing machine having a mechanism for supplying a solid processing agent to a processing tank.

As the processing agent supply means, when the solid processing agent is a tablet, Japanese Utility Model Application Laid-Open No. 63-137783,
No. 97522, Japanese Utility Model Laid-Open No. 1-85732, etc., and in the case of granules or powder, Japanese Utility Model Application Laid-Open No. 62-81
964, 63-84151, JP-A 1-2923
No. 75, etc.
Nos. 59 and 63-195345, etc. can be referred to. The place where the solid processing agent is charged is in the processing tank, but it is preferably in communication with the processing section for processing the photosensitive material, where the processing liquid is flowing between the processing section and the processing section. There is preferably a structure in which there is a constant circulation amount of the processing liquid and the dissolved components move to the processing section. Further, the solid processing agent is preferably introduced into a processing liquid whose temperature is controlled.

In the processing method of the present invention, the total processing time (dry to dry) is not particularly limited using an automatic developing machine, but processing is preferably performed in 10 to 90 seconds, and 15 to 90 seconds.
-45 seconds is more preferable, and 15-30 seconds is most preferable.

[0098]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited by these examples. (Preparation of Seed Emulsion) Seed Emulsion-1 was prepared as follows: A1 ossein gelatin 24.2 g water 9657 ml polypropyleneoxy-polyethyleneoxy-disuccinate sodium salt (10% aqueous ethanol solution) 6.78 ml bromide Potassium 10.8 g 10% nitric acid 114 ml B1 2.5 N silver nitrate aqueous solution 2825 ml C1 potassium bromide 841 g with water 2825 ml D1 1.75 N potassium bromide aqueous solution

At 42 ° C, JP-B-58-58288, 5
Solution B using a mixing stirrer described in 8-58289
1 and 464.3 ml of the solution C1 were added thereto by a double jet method over 1.5 minutes to form nuclei. It takes 60 minutes after stopping the addition of the solution B1 and the solution C1 to raise the temperature of the solution A1 to 60 ° C., adjust the pH to 5.0 with 3% KOH, and then again use the solution B1 and the solution C1. Was added at a flow rate of 55.4 ml / min for 42 minutes by the double jet method. This temperature rise from 42 ° C. to 60 ° C. and solution B
1. During the re-simultaneous mixing with C1, the silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) was controlled to +8 mv and +16 mv, respectively, using solution D1.

After the addition was completed, the pH was adjusted to 6 with 3% KOH.
Immediately, desalting and washing were performed. In this seed emulsion, 90% or more of the total projected area of the silver halide grains is composed of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0, and the average thickness of the hexagonal tabular grains is 0.064 μm. It was confirmed with an electron microscope that the diameter (in terms of circular diameter) was 0.595 μm. The variation coefficient of the thickness was 40%, and the variation coefficient of the distance between twin planes was 42%.

(Preparation of Grain-1) Using a seed emulsion-1 and the following four kinds of solutions, a tabular silver halide emulsion [grain-
1] was prepared. A2 Ossein gelatin 34.03 g Polypropylene oxy-polyethylene oxy-disuccinate sodium salt (10% aqueous ethanol solution) 2.25 ml Seed emulsion-1 1.722 mol equivalent Equivalent to 3150 ml with water. B2 1734 g potassium bromide Make up to 3644 ml with water. C2 Silver nitrate 2478g Make up to 4165ml with water. D2 Fine grain emulsion composed of 3% by weight of gelatin and silver iodide grains (average grain size: 0.05 μm) Equivalent to 0.080 mol

*: To 6.64 liters of a 5.0% by weight aqueous gelatin solution containing 0.06 mol of potassium iodide,
Two liters of an aqueous solution containing 7.06 mol of silver nitrate and 7.06 mol of potassium iodide were added over 10 minutes. During the fine particle formation, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the formation of the particles, the pH was adjusted to 6.0 using an aqueous solution of sodium carbonate.

The solution A2 was vigorously stirred in the reaction vessel while maintaining the temperature at 60 ° C., and a part of the solution B2, a part of the solution C2 and half of the solution D2 were added thereto by a double jet method over 5 minutes. Then, half of the remaining amount of the solution B2 and the solution C2 are added over a period of 37 minutes, and a part of the solution B2, a part of the solution C2, and the entire remaining amount of the solution D2 are added over 15 minutes. The total amount of the remaining solutions B2 and C2 was added thereto over 33 minutes. During this time, the pH was 5.8 and the pAg was 8.8.
I kept it at 8. Here, the addition rates of the solution B2 and the solution C2 were changed as a function of time in accordance with the critical growth rate.

After completion of the addition, the emulsion was cooled to 40 ° C.
After performing ultrafiltration desalting by a known method, a 10% gelatin solution was added, and the mixture was stirred at 50 ° C. for 30 minutes and redispersed. After redispersion, the pH was adjusted to 5.80 and the pAg to 8.06 at 40 ° C.

When the obtained silver halide emulsion was observed with an electron microscope, the average grain size was 0.984 μm and the average thickness was 0.1 mm.
Tabular silver halide grains having a size of 22 μm, an average aspect ratio of about 4.5, and a particle size distribution of 18.1% were obtained. Also,
The average of the twin plane distance is 0.020 μm, and grains having a twin plane distance to thickness ratio of 5 or more are 97% (number) of all tabular silver halide grains and 10 or more grains are 49 or more. %, 15
These particles accounted for 17%.

(Preparation of Particle-2)
The mixture was melted at 0 ° C., and pAg was adjusted to 7.5 by simultaneously adding a silver nitrate solution and a potassium iodide solution. At this time, the silver nitrate solution and the potassium iodide solution were added in such a ratio that the silver iodide content of silver halide precipitated in a small amount during this preparation was 12 mol%.

Next, a 2 mol% sodium chloride solution was added to the first amount of [particle-1], and calcium chloride,
Sodium bromide, the same silver iodide fine grain emulsion [grain-1], and a silver nitrate solution were added in this order. The amount of silver nitrate added was 6 mol% based on the total silver amount of the silver halide grains. After all, the composition ratio (mol%) of the halide added in the preparation of the particle-2
Was added so that Cl: Br: I = 42: 42: 16. Observation of the obtained [Grain-2] by electron microscopy revealed that many silver halide projections were epitaxially deposited not only on the peripheral part but also on the entire main plane {(1,1,1) plane}. .

(Preparation of Particle-3) In the preparation of [Particle-2], between the addition of sodium chloride and the addition of calcium chloride, K ₂ PdCl ₄ was added to 5 × 10 ⁻⁵ per mol of silver.
Except for the molar addition, the same as in the preparation of [Particle-2],
[Particle-3] was prepared.

When the obtained [Grain-3] was observed with an electron microscope, silver halide projections epitaxially adhered to the periphery of the main plane {(1,1,1) plane} were observed.

(Chemical sensitization of [Grain-1]) The volume of the obtained [Grain-1] per mole of silver halide was 300 m.
After adding pure water to 50 l, the temperature was raised to 50 ° C, 20 mg of benzyladenine was added, and 10 minutes later, the sensitizing dye (A) was added.
(B) 0.6 mol each as a solid particulate dispersion,
0.006 mol was added, and 10 minutes later, 3 × 10 ⁻³ mol of ammonium thiocyanate was added, and an appropriate amount of chloroauric acid and sodium thiosulfate were further added. 60 seconds before the end of the chemical sensitization, 4 g of silver iodide fine particles and 2 g of triphenylphosphine selenide dispersion were added, and then 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) was added. An appropriate amount was added to complete the chemical sensitization. The obtained emulsion was designated as [Em-1].

The above-mentioned dispersion of triphenylphosphine selenide was prepared as follows. That is, 120 g of triphenylphosphine selenide was added to ethyl acetate 30 at 50 ° C.
It was added to the resulting mixture, stirred and completely dissolved. On the other hand, 3.8 kg of photographic gelatin was dissolved in 38 kg of pure water, and 93 g of a 25 wt% aqueous solution of sodium dodecylbenzenesulfonate was added thereto. Next, these two liquids were mixed and dispersed by a high-speed stirring type disperser having a dissolver having a diameter of 10 cm at a dispersion blade peripheral speed of 40 m / sec at 50 ° C. for 30 minutes. Thereafter, ethyl acetate was removed while stirring under reduced pressure until the residual concentration of ethyl acetate became 0.3 wt% or less. Thereafter, this dispersion was diluted with pure water to finish up to 80 kg. A part of the dispersion thus obtained was fractionated and used in the above experiment.

Sensitizing dye (A): 5,5'-dichloro-9
-Ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine sodium salt anhydride Sensitizing dye (B): 5,5'-di- (butoxycarbonyl) -1,1'-di- Anhydrous sodium ethyl-3,3'-di- (4-sulfobutyl) benzimidazolocarbocyanine

(Chemical Sensitization of [Grain-2]) [Grain-1]
[Grain-2] was subjected to chemical sensitization in the same manner as in [Em-2].

(Chemical sensitization of [particle-3]) [particle-1]
[Grain-3] was subjected to chemical sensitization in the same manner as in the above. The obtained emulsion was designated as [Em-3].

An emulsion additive described below was added to the obtained emulsion to prepare a prepared solution. The pH was adjusted to 6.20 and the silver potential was adjusted to 80 mV (35 ° C.) using sodium carbonate and potassium bromide solutions after preparing the photographic emulsion coating solution.

Using this emulsion coating solution, a sample was prepared as follows. That is, the photographic emulsion layer was adjusted to 1.8 g / m ² per one side in terms of metallic silver, and the amount of gelatin was adjusted to 1.7 g / m ² per one side.

Also, a protective layer solution was prepared using the additives described below. The protective layer was coated simultaneously with the emulsion layer prepared above so that the amount of gelatin per side was 0.7 on both sides of the support at a speed of 80 m / min using two slide hopper coaters together with the emulsion layer prepared above. After drying for 20 seconds, a sample was obtained.

The additives used in the emulsion are as follows. The amount of addition is shown in an amount per mole of silver halide. 1,1-dimethylol-1-bromo-1-nitromethane 10 mg t-butyl-catechol 70 mg polyvinylpyrrolidone (molecular weight 10,000) 1.0 g styrene-maleic anhydride copolymer 2.0 g nitrophenyl-triphenylphosphonium chloride 5 0.0 mg ammonium 1,3-dihydroxybenzene-4-sulfonate 2.0 g 2-mercaptobenzimidazole-5-sodium sulfonate 1.5 mg C ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 1.5 g 1-phenyl-5-mercaptotetrazole 15 mg methacrylic acid-ethyl acrylate copolymer 18 g

[0119]

Embedded image Trimethylolpropane 10g

[0120]

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Next, the additives used in the protective layer liquid are shown. The stated weight is shown in the amount per liter of the coating solution. Lime-treated inert gelatin 58 g Acid-treated gelatin 2 g Sodium-i-amyl-decylsulfosuccinate 1.0 g Polymethyl methacrylate, matting agent having an area average particle size of 3.5 μm 0.4 g Silicon dioxide particles, area average particle size 1 0.2 μm matting agent 0.7 g Ludox AM (manufactured by DuPont) (colloidal silica) 3.0 g Addition of the following surfactants (a), (b) and (c) and a hardener

[0122]

Embedded image Bis-vinylsulfonyl methyl ether 0.4 g

The developing process of the photosensitive material is performed by an automatic developing machine TCX.
-201 (manufactured by Konica) with a Dryto Dry time of 4
It was modified so as to be 0 second, and TC-DF1 (manufactured by Konica) was used as a developer and a fixer as a developer containing reductones. The developing / fixing solution temperature was 35 ° C., and the washing water was 20 ° C. The replenishing amount of the developing solution / fixing solution was set to 160 ml per 1 m ² of the photosensitive material.

<Evaluation of Running Stability> The prepared photosensitive material was cut into large-sized pieces, and the entire surface was uniformly exposed so that the optical density after development processing was 1.0, and the running processing was performed. The running process is 150 sheets per day, the first day (starting liquid state), 750 sheets (5 days)
The sensitometric performance of 1500 sheets (10 days) was determined by the following method. Table 1 shows the results.

(Sensitometry) The obtained film was sandwiched between fluorescent intensifying screens SRO-250 (manufactured by Konica), and irradiated with X-rays under the conditions of a tube voltage of 90 kVp, a current of 100 mA and a time of 0.05 second, and the distance was measured. A sensitometric curve was created by the method to determine the sensitivity. Sensitivity value is "fog +1.0"
Was calculated as the reciprocal of the X-ray dose required to obtain The contrast value was determined as a value obtained by dividing by a logarithmic value difference of an exposure amount necessary to obtain a density difference in a density range of “fog + 0.25 to fog + 2.0”.

<Evaluation of Storage Property>
The difference between the sensitivity when stored for 2 days after application and the sensitivity when stored for 100 days at 50 ° C. and 50% RH was determined. The sensitivity value was determined in the same manner as in the method described in the above sensitometric evaluation. Table 1 shows the results.

In the item of the palladium compound addition position in Table 1, "Step-1" means that the palladium compound was added at the time of chemical sensitization, and "Step-2".
The term "addition" means that it is added during the preparation of the coating solution, that is, it is added to the emulsion coating solution.

[0128]

[Table 1]

[0129]

According to the present invention, there can be provided a silver halide photographic light-sensitive material excellent in rapid processing property, running stability and long-term storage property, and a processing method therefor.

──────────────────────────────────────────────────続 き Continued on front page (51) Int.Cl. ⁶ Identification code FI G03C 5/395 G03C 5/395

Claims (5)

[Claims] 1. A silver halide photographic material comprising at least one silver halide emulsion layer provided on a support, wherein said silver halide emulsion layer has tabular silver halide grains having host grains. A silver halide photographic light-sensitive material containing a silver halide emulsion containing silver halide grains epitaxially bonded to tabular silver halide grains and containing a palladium compound. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the silver halide grains which are epitaxially bonded are silver halide grains satisfying the following condition A. Condition A The (1,1,1) plane is the main plane, and the circle equivalent diameter is 0.5
３3.0 μm and thickness of 0.07-0.7 μm. Including epitaxially deposited silver halide protrusions in a face-centered cubic lattice structure forming an epitaxy junction. The silver halide projections are located at the periphery of the host tabular grains. 3. A method for processing a silver halide photographic light-sensitive material, which comprises subjecting the silver halide photographic light-sensitive material according to claim 1 or 2 to imagewise exposure followed by photographic processing in a step including a development and fixing step. 4. A process according to claim 3, wherein the replenishment amounts of the developing solution and the fixing solution are not more than 200 ml for each 1 m ^{2 of the} silver halide photographic material to be processed. Processing method of silver photographic photosensitive material. 5. A method for processing a silver halide photographic material according to claim 3, wherein said developer contains reductones.