JPH051453B2 - - Google Patents

Description

BACKGROUND OF THE INVENTION TECHNICAL FIELD The present invention relates to a method for developing a silver halide photosensitive material, and particularly to a method for developing a silver halide photosensitive material to obtain a photographic image having high sensitivity, high density, and high gamma. It is related to. Prior art and its problems Silver halide photosensitive materials have a high information recording density;
It is widely used because it has high sensitivity (low light energy required for image recording) and is easy to use. For example, general photographic film is commercially available with a sensitivity of ISO 1000 to 1600, making it possible to take photographs even in very dark places. Furthermore, in the medical field, efforts are being made to reduce the radiation exposure dose as much as possible when diagnosing affected areas by increasing the sensitivity of silver halide photosensitive materials and increasing the luminous efficiency of fluorescent screens. Furthermore, high-sensitivity photographic paper that can be processed with a short exposure time has been developed to be suitable for mass production. Regarding such high-sensitivity silver halide emulsions,
Many researchers have proposed research reports, patents, etc. Generally, methods for obtaining highly sensitive silver halide emulsions include using grains in which the composition of silver halide is silver iodobromide (salt) containing silver iodide, or grains containing gold, palladium, or other group metals. Proposed methods include gold sensitization, sulfur sensitization using hypo, thioether, etc., and reduction sensitization using hydrogen or excess silver (high EAg). In addition, methods for producing silver halide grains include a conversion method in which silver halide is substituted with a more poorly soluble silver halide during grain growth, a method in which silver iodide is epitaxially bonded onto silver chloride grains, and a method in which silver iodide is epitaxially bonded onto silver chloride grains. There are methods such as changing the silver halide composition of the outer layer or growing silver halide on the grains to obtain laminated silver halide grains. However, these silver halide emulsions are generally silver chlorobromide, silver chlorobromoiodide, silver chloroiodide, and silver bromoiodide, mainly consisting of silver bromide and silver iodide.
The development characteristics were not necessarily sufficient. Further, attempts have been made to increase the sensitivity by increasing the size of silver halide grains, but deterioration in development characteristics is unavoidable. Furthermore, since it is difficult to obtain the required density with such silver halide emulsions (low governing power), the amount of silver deposited on photosensitive materials has been increased, which is not convenient from the point of view of resource conservation. . Development characteristics here refer to changes in characteristic values such as sensitivity, gamma, and density of a photosensitive material due to differences in temperature, time, developer activity, etc. during development processing, and the better the development characteristics, the higher the sensitivity and the higher the gamma. , high density can be obtained, or the fluctuation range of the characteristic value is small with respect to changes in conditions such as the developer. Generally, photographic film and X-ray film have
Silver chlorobromide iodide, mainly silver bromide, containing 2 to 6 mol% of silver iodide is used, and the target performance can be obtained by appropriately changing the activity of the developer, processing time, processing temperature, etc. It is being done. The same procedure is used for photographic paper, but
In photo labs that perform a large amount of printing, changes in characteristics due to changes in the composition of a processing solution such as a developer or changes in conditions such as temperature are extremely important in order to obtain a stable finish. Furthermore, in the case of in-house processing by amateurs, it is impossible to have large-scale printing equipment such as a photo lab, and it is desirable that the characteristics be stable even in poorly managed processing. OBJECTS OF THE INVENTION The present invention has been made in view of the above circumstances, and its first object is to develop a silver halide photosensitive material capable of obtaining photographic images with high sensitivity, high gamma, and high density. The purpose is to provide a processing method. A second object of the present invention is to provide a method for developing silver halide photosensitive materials in which photographic properties such as sensitivity, gamma, and photographic image density are less likely to change due to differences in temperature, time, developer activity, etc. during development. It is about providing. A third object of the present invention is to provide a method for developing a silver halide photosensitive material, which allows good photographic properties to be obtained even with a silver halide photosensitive material coated on a support with a small amount of silver halide. . These objects of the present invention are that after imagewise exposure of a silver halide light-sensitive material having at least one halide emulsion layer on a support, 6×10 ^-2 chloride ions are removed in the presence of a developing agent. This is achieved by a method for developing a silver halide photosensitive material, which is characterized by developing with a solution containing a concentration of mol/molar or higher. Specific Structure of the Invention In the present invention, the imagewise exposed silver halide photosensitive material absorbs chloride ions by 6× in the presence of a developing agent.
It is characterized by being developed with a solution containing a concentration of 10 ^-2 mol/or more. The concentration of this chlorine ion in the treatment solution is 6×10 ^-2 mol/
It may be more than 8×10 ⁻² mol/ to 7×10 ⁻¹ mol/. If the chloride ion concentration is less than 6 x 10 ^-2 mol/, ^the effect of the present invention cannot be sufficiently obtained;
If it exceeds this value, other chemicals dissolved in the chlorine ion-containing solution may crystallize and precipitate, which may damage the surface of the silver halide photosensitive material during the development process, which is not preferable. Chlorine ion supply substances that can exist as chlorine ions in the treatment solution include sodium chloride, potassium chloride, ammonium chloride,
Examples include nickel chloride, magnesium chloride, manganese chloride, calcium chloride, and cadmium chloride, among which preferred are sodium chloride, potassium chloride, and ammonium chloride. The chloride ion supplying substance used in the present invention is used in a developer, a processing solution required when developing a photosensitive material containing a developing agent in a silver halide photographic light-sensitive material, or used in a pre-stage of these processing solutions. is added to the processing bath, preferably in the developer. This chloride ion supplying substance may be added to the processing liquid used as it is, or may be preliminarily dissolved in water and added to the processing liquid as an aqueous solution. The timing of addition of the chloride ion supplying substance is not particularly limited as long as it is before or during the development of the silver halide photographic material. In the photographic emulsion layer of the silver halide light-sensitive material of the present invention, any of silver bromide, silver bromoiodide, silver chlorobromoiodide, silver chlorobromide, and silver chloride may be used as the silver halide. Among these, silver chlorobromide, silver chlorobromoiodide, and silver bromoiodide are preferred. These silver halide grains may be coarse or fine, and the grain size distribution may be narrow or wide. In addition, the crystals of these silver halide grains may be normal crystals or twin crystals, and have [100] planes and [111] planes.
Any surface ratio can be used. Further, the crystal structure of these silver halide grains may be uniform from the inside to the outside, or may have a layered structure with different inside and outside. Further, these silver halides may be of a type that forms a latent image mainly on the surface or of a type that forms a latent image inside the grain. These silver halide grains can be prepared by known methods commonly used in the art. In the present invention, it is particularly preferable to use silver halide grains (core/shell type silver halide grains) having a layered structure with a different interior and exterior.
In this case, the surface layer (shell) of silver halide grains
Silver halide having a composition of silver chloride of 50 mol % or less, preferably 35 mol % or less is useful. Further, the content of silver iodide in the surface layer is not limited to the effects of the present invention, but from a practical standpoint, it is preferably about 0 to 8 mol%. Further, the composition of the silver halide in the inner layer is not particularly limited. The silver halide emulsion of the present invention contains chemical sensitizers such as sulfur sensitizers such as sodium thiosulfate, thiourea, allylthiocarbamide, allyl isocyanate, active or inactive selenium sensitizers, and potassium chloride sensitizers. In addition to gold compounds such as aureate and auricul trichloride, palladium compounds such as ammonium chloroparadate and sodium chloroparadate, noble metal sensitizers such as platinum compounds, ruthenium compounds, rhodium compounds, and iridium compounds are used alone or in combination. They may be used together for sensitization. Further, this silver halide emulsion may be reduced-sensitized using a reducing agent. Further, the silver halide emulsion can be optically sensitized to blue sensitivity, green sensitivity, or red sensitivity using an optical sensitizer if necessary. Optical sensitizers that can be used in the present invention include:
Included are cyanines, merocyanines, trinuclear or tetranuclear merocyanines, styryls, holoporacyanines, hemicyanines, oxonols, and hemioxonols. For these optical sensitizers, any of the basic heterocyclic nuclei commonly used for cyanine dyes can be used. That is, pyrrolines, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; nuclei in which an alicyclic hydrocarbon ring is fused to these nuclei; and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus, i.e., an indolenine nucleus, a benzindolenine nucleus, an indole nucleus,
benzoxazole nucleus, naphthoxazole nucleus,
A benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus, etc. are applicable. These nuclei may have substituents on carbon atoms. Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-
Examples include 5- to 6-membered heterocyclic nuclei such as thioxazolidine-2,4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, and thiobarbituric acid nucleus. These nuclei can have substituents such as alkyl, hydroxyalkyl, sulfoalkyl, carboxyalkyl, halogen, phenyl, cyano, and alkoxy. These nuclei may also be fused with a carbocyclic or heterocyclic ring. For specific optical sensitizers, see ``The Theory of the Photographic Process'' by MEES & JAMES.
PHOTOGRAPHIC PROCESS) 3rd edition (1966
Chapter 2 by MACMILLAN and “Spectral Sensitization” by HANS MEIER
(SPECTRAL SENSITIZATION), 1968,
THE FOCAL PRESS
PRESS), U.S. Patent No. 2497748,
No. 2503776, No. 2688545, No. 2912329, No.
No. 3656959, No. 3679428, No. 3672897, No. 3672897, No. 3679428, No. 3672897, No.
No. 3703377, No. 3814609; Special Publication No. 42-14085,
No. 42-27166, No. 43-3406, No. 43-4936,
No. 43-7569, No. 43-10251, No. 43-13498,
No. 43-14497, No. 44-14030, No. 45-26470,
No. 46-11627, No. 46-18107, No. 47-8741,
No. 47-11115, No. 48-42492, No. 49-17725
No.: Japanese Patent Publication No. 53-105217, No. 53-142223, No. 54
-23520, 55-70834, 56-50325, same
Compounds described in No. 57-54936, No. 57-190940, etc. can be used. These optical sensitizers are added to the silver halide emulsion in an amount of 1×10 ^-5 to 3×10 ^-4 mol per mol of silver halide. The optimum amount of the optical sensitizer to be added varies depending on the composition amount of silver halide used, etc., and is determined experimentally. Furthermore, the silver halide emulsion used in the present invention is
Optical sensitization may be carried out using a single optical sensitizer, or there is no problem even if two kinds of optical sensitizers are combined and supercolor sensitized by a known method. The emulsion used in the present invention may contain antifoggants, development inhibitors, stabilizers, etc. in order to keep the surface sensitivity as low as possible and obtain a lower minimum density, and to impart more stable characteristics. For example, compounds having a mercapto group and azaindene compounds are representative examples. In addition, in the present invention, depending on the purpose, coating aids (surfactants), film property modifiers, PH regulators, antistatic agents, thickeners, graininess improvers, mordant brighteners, development speed adjustment It is optional to use additives, matting agents, anti-irradiation dyes, antihalation agents, antioxidants, and the like. The silver halide light-sensitive material used in the present invention may contain a dye-forming coupler. Such dye-forming couplers include yellow dye-forming couplers, magenta dye-forming couplers and cyan dye-forming couplers. Examples of yellow dye-forming couplers include benzoylacetanilide-based and pivaloylacetanilide-based compounds, or 2-equivalent type yellow couplers in which the carbon atom at the coupling position is substituted with a so-called split-off group that can be separated during coupling. Useful. As the magenta dye-forming coupler, 5-pyrazolone type, pyrazolotriazole type, pyrazolinobenzimidazole type, indazolone type or two-equivalent type magenta couplers having a split-off group are useful. As the cyan dye-forming coupler, a phenol type, naphthol type, or two-equivalent type cyan coupler having a split-off group is useful. These dye-forming couplers can be selected arbitrarily;
Moreover, the method of use, the amount used, etc. are not particularly limited. The photographic emulsion of the present invention is combined with a dye-providing substance for diffusion transfer that releases a diffusible dye in response to development of silver halide, and is then subjected to an appropriate development process, and then the desired transfer is carried out on an image-receiving material. It can also be used to obtain images. Examples of such dye-providing substances for diffusion transfer include US Pat. No. 3,227,551;
No. 3227554, No. 3443939, No. 3443940, No. 3443939, No. 3443940, No.
No. 3658824, No. 3698897, No. 3725062, No. 3698897, No. 3725062, No.
No. 3728113, No. 3751406, British Patent No. 840781,
No. 904364, No. 1038331, West German Patent Publication (OLS)
No. 1930215, No. 2214381, No. 2228361, No.
No. 2242762, No. 2317134, No. 2402900, No.
Those described in No. 2406626, No. 2406653, JP-A-49-114424, etc. can be used. Further, in the silver halide light-sensitive material of the present invention, known colored couplers, development inhibitor releasing (DIR) couplers, precursors thereof, and the like can be used as necessary. As a colored coupler, for example, the US patent
No. 3476560, No. 2521908, No. 3034892, Tokko Akira
No. 44-2016, No. 38-22335, No. 43-11304, No. 43-11304, No.
No. 44-32461, JP-A-51-26034 and JP-A No. 52-
Specifications of No. 42121, West German patent application (OLS)
Those described in No. 2418959 can be used. In addition, as a DIR coupler, for example, the U.S. patent
No. 3227554, No. 3617291, No. 3701783, No.
No. 3790384, No. 3632345, West German patent application (OLS)
No. 2414006, No. 2454301, No. 2454301, No. 2454301, No. 2454301, No. 2454301, No. 2454301, No.
No. 2454329, British Patent No. 953454, JP-A-52-69624
No. 49-122335 and Japanese Patent Publication No. 51-16141 can be used. In addition, in order to prevent fading of dye images due to short-wavelength actinic rays, it is useful to use known ultraviolet absorbers, such as thiazolidone, benzotriazole, acrylonitrile, and benzophenone compounds, especially Tinupin PB, Tinupin 120, Tinupin 320 ,same
326, 327, 328 (all manufactured by Ciba Geigy)
These can be used alone or in combination of two or more. In addition to gelatin, the silver halide photosensitive material according to the present invention may contain a suitable gelatin derivative depending on the purpose. Suitable gelatin derivatives include, for example, acylated gelatin, guanidylated gelatin, carmylated gelatin, cyanoethanolated gelatin, and esterified gelatin. Further, in the silver halide photographic light-sensitive material obtained by applying the present invention, other hydrophilic binders can be included in addition to the gelatin according to the present invention in the hydrophilic colloid group. Suitable binders include, in addition to the gelatins mentioned above, colloidal albumin, agar, gum arabic, dextran, alginic acid, cellulose derivatives such as cellulose acetate hydrolyzed to an acetyl content of 10 to 20%, polyacrylamide, and imidized polyacrylamide. , casein, vinyl alcohol polymers containing urethane carboxylic acid groups or cyanoacetyl groups such as vinyl alcohol-vinylaminoacetate copolymers, polyvinyl alcohol, polyvinylpyrrolidone, hydrolyzed polyvinyl acetate, proteins or saturated acylated proteins and monomers having vinyl groups. Obtained by polymerization with Contains polymers, polyvinylpyridine, polyvinylamine, polyaminoethyl methacrylate, polyethyleneamine, etc., and can be added to constituent layers of silver halide photographic materials such as emulsion layers, intermediate layers, protective layers, filter layers, backing layers, etc. depending on the purpose. Furthermore, the hydrophilic binder may contain a suitable plasticizer, lubricant, etc. depending on the purpose. Further, the constituent layers of the silver halide photographic light-sensitive material using the photographic emulsion according to the present invention can be hardened with any suitable hardener. Examples of these hardening agents include chromium salts, zirconium salts, aldehyde-based, halotriazine-based, polyepoxy-based, ethyleneimine-based, vinylsulfone-based, and acryloyl-based hardeners. Further, the silver halide photographic light-sensitive material using the photographic emulsion according to the present invention includes an emulsion layer, a filter layer, an ultraviolet absorbing layer, an intermediate layer, a protective layer, a subbing layer, a backing layer, and an antihalation layer on a support. It is manufactured by coating various photographic constituent layers such as. The silver halide photographic emulsion according to the present invention can be effectively applied to various uses such as black and white general use, X-ray use, color use, false color use, printing use, infrared use, micro use, etc. Rosiers U.S. Patents 3,087,817, 3,185,567 and 2,983,606
U.S. Pat. No. 3,253,915 to Weyerb et al., U.S. Pat. No. 3,227,550 to Whitemore et al., U.S. Pat. No. 3,227,551 to Pearl et al., U.S. Pat.
The present invention can also be applied to color image transfer methods, color diffusion transfer methods, absorption transfer methods, etc., as described in the specifications of No., No. 3415645, and No. 3415646. Any support can be used to coat the photographic emulsion according to the present invention, but typical supports include polyethylene terephthalate film, polycarbonate film, polystyrene film, and polypropylene film, which have been subbed as required. , cellulose acetate film, glass, Paraita paper, polyolefin-in laminated paper such as polyethylene, and the like. Furthermore, depending on the intended use, there is no problem in using a support that has been treated to be white and opaque. Common silver halide developers that can be used in the present invention include polyhydroxybenzenes such as hydroquinone, aminophenols,
Included are 3-pyrazolidones, ascorbic acid and its derivatives, reductones, phenylenediamines, etc., or mixtures thereof. Specifically, hydroquinone, aminophenol, N-methylaminophenol, 1-phenyl-3-pyrazolidone, 1
-Phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, ascorbic acid,
N,N-diethyl-p-phenylenediamine, diethylamino-O-toluidine, 4-amino-3
-Methyl-N-ethyl-N-(β-methanesulfonamidoethyl)aniline, 4-amino-3-
Examples include methyl-N-ethyl-N-(β-hydroxyethyl)aniline. These developers can also be included in the emulsion in advance and allowed to act on the silver halide during immersion in a high pH aqueous solution. The developer solution may further contain specific anti-capri agents and development inhibitors. These developer additives may be optionally incorporated into the layers of the silver halide photographic light-sensitive material. Generally useful anti-capri agents include benzotriazoles such as 5-methylbenzotriazole; benzothiazoles; heterocyclic thiones such as 1-phenyl-5-mercaptotetrazole; aromatic and aliphatic Includes mercapto compounds, etc. The developer may also contain a development accelerator such as a polyalkylene oxide derivative or a quaternary ammonium salt compound. Specific Examples of the Invention The present invention will be described below with reference to Examples, but the present invention is not limited to these Examples. Example 1 A silver chlorobromoiodide emulsion prepared by the ammonia method and containing 20 mol % of silver chloride and 0.5 mol % of silver iodide was prepared as follows. A liquid Gelatin NH ₄ Br KI Pure water 15.0 g 10.0 g 0.83 g 1500ml B liquid NH ₄ Br NaCl Pure water 67.9 g 26.8 g 500ml C liquid AgNO ₃ Aqueous ammonia (conc) Pure water 169.9 g 140. ml 850. ml D liquid {30% acetic acid Amount required to make emulsion PH≒6.0 Solution A was kept at 40°C, and solutions B and C were added simultaneously while stirring, and solution B was injected over 3 minutes and solution C over 4 minutes. After aging for 10 minutes, add solution D to adjust the pH of the emulsion.
Lowered to 5.7. Excess water-soluble salts were removed by a conventional precipitation and water washing method, and a solution containing 30 g of gelatin was added to give a final weight of 1 kg. 4-hydroxy-6-methyl-1,3,3a per mole of silver halide,
After adding 0.2 g of 7-tetrazaindene, 7 mg of hypo, 9 mg of chloroauric acid, and 50 mg of rhodanammon and aging at 60°C for 90 minutes, 50 mg of 1-phenyl-5-meltocaptotetrazole and 170 mg of the following sensitizing dye D-
added. Appropriate amounts of gelatin, coating aids, and hardeners were added to this to form an emulsion layer with a coated silver amount of 4.5 g/m ² and a gelatin amount of 6.0 g/m 2 .
m ² , the protective layer was coated on an undercoated polyester film with a gelatin amount of 1.0 g/m ² and dried. Using this sample, sensitometry was performed as follows. Exposure: KS-7 type sensitometer (manufactured by Konishiroku Photo Industry Co., Ltd.) 2854〓, exposure time 1 second, density difference 0.15 wedge. Development: Development 30± 0.5℃ 30 seconds Fixing 30± 1℃ 30 seconds Washing 20-30℃ 30 seconds Drying 50± 3℃ 30 seconds Developer formulation Phenidone 0.2gr Anhydrous sodium sulfite 14. gr Hydroquinone 5. gr Anhydrous soda 33 gr Potassium bromide 1.1gr Boric anhydride 0.3gr EDTA-2Na 0.8gr NaCl or NaBr (amounts listed in Table 1) Add water to give a finish of 1.0. Fixer formulation Hypo 20 gr Ammonium thiosulfate 150 gr Metakali 12 gr Sodium acetate 18 gr Boric anhydride 4 gr Anhydrous sodium sulfite 15 gr Potash alum 10 gr Add water to make a finish of 1.0.

[Table] *Sensitivity (S) is a relative value based on the sensitivity of sample 1-A. Note that each ion concentration was calculated assuming that NaCl and NaBr are 100% dissociated because they are both strong electrolytes. As is clear from Table 1, the chloride ion concentration
When a silver halide photosensitive material is processed with the developer according to the present invention having a concentration of 0.068 mol/or more, the sensitivity (S), gamma (G) and maximum density (Dmax) increase, and good photographic properties can be obtained. Example 2 Using the emulsion of Example 1, an amount equivalent to 0.2 mole of oil-soluble yellow coupler was further dispersed and added in dibutyl phthalate in a conventional manner during coating to give an emulsion layer with an amount of silver of 2.5 gr/m ² and an amount of gelatin. 3.0gr/m ² and the amount of gelatin in the protective layer is 1.0gr/m ² .
Dry. Using this sample, sensitometry was performed by the following method. Exposure: Same color processing steps as in Example 1 Color development 33°C 2 minutes and 3 minutes Bleach fixing 33°C 1 minute 30 seconds Washing with water 33°C 1 minute 30 seconds Drying 65°C 1 minute Color developer composition Benzyl alcohol 10.0ml Hexamethalin Sodium acid 2.5g Anhydrous sodium sulfite 1.9g Sodium bromide 1.5g Anhydrous sodium carbonate 26.0g N-ethyl-N-β-methanesulfonamidoethyl-4-aminoaniline sulfate 5.0g NaCl (amount shown in Table 2) Water Add 1 and adjust the pH to 10.30 (25℃) using sodium hydroxide Bleach-fix solution composition Ethylenediaminetetra Ammonium iron acetate 61.0g Ethylenediaminetetra Diammonium acetate 5.0g Ammonium thiosulfate 130g Anhydrous sodium sulfite 2.7g Add water Add ammonia water to adjust the pH to 6.50 (25℃).

[Table] From Table 2, it can be seen that high sensitivity and high density can be obtained by adding NaCl, and changes in sensitivity and maximum density when the development time is changed are small. Example 3 Silver chlorobromoiodide emulsions having different silver chloride contents were prepared as follows.

[Table] Keep liquid A at 45℃ and inject liquid C1 in 2 minutes while stirring vigorously. After 5 minutes, add B and C2 solutions simultaneously and inject B solution for 15 minutes and C2 solution for 30 minutes. After 10 minutes, Solution D was injected over 2 minutes, and the mixture was further aged for 30 minutes, and Solution E was added to lower the pH to 5.9. After removing soluble salts by precipitation and washing with water, a solution containing 40 g of gelatin was added to give a final weight of 1 kg. Emulsion-2, 3, 4,
I have prepared 5. 4-hydroxy-6- per mole of silver halide
Methyl-1,3,3a,7-tetrazaindene
0.2 gr, 4 mg of hypo, 5 mg of chloroauric acid, and 20 mg of rhodan ammonium were added, and the time was varied to achieve optimal ripening at 60°C. After that, 40 mg of 2-meltocapto-benzothiazole, the following sensitizing dyes D-2, D-3, D-
Added 4. Furthermore, gelatin, a coating aid, and a hardening agent are added so that the emulsion layer has a silver content of 5.0 g/m ² and gelatin content of 5.0 g/m ² , and the protective layer has a gelatin content including a coating aid and a hardening agent. It was applied onto a subbed polyester film at a concentration of 1.0 g/m ² and colloidal silica at 0.03 g/m ² and dried. In this way, sample 2,
I got 3,4,5. These samples were exposed for 0.2 seconds through a stepped wedge (density difference 0.20) using a KS-7 type sensitometer (converted to 5400〓 with a DG filter).
Development processing was carried out as follows. Processing process Development 20℃ 5 minutes, 8 minutes, 11 minutes Stop 20℃ 1 minute Fixing 20℃ 5 minutes Washing 20℃ 15 minutes Drying 60℃ 5 minutes Developer solution

【table】

【table】 Stop liquid Glacial acetic acid 15ml Finish by adding water 1.0 Fixer Hypo 250g Anhydrous sodium sulfite 15g Glacial acetic acid 15ml Potash alum 15g Boric acid 7.5g Finish by adding water 1.0

【table】

[Table] From the results in Table 3, it can be seen that sensitivity (S) and gamma (G) are higher when each sample is processed with developers B and C of the present invention than when processed with co-developer A. . Furthermore, it can be seen that samples containing silver halide with a high silver bromide ratio have smaller changes in gamma (G) and more stable performance can be obtained. In addition, the amount of gelatin applied using Emulsion 4 was 5.0 g/ ^m2 , and the amount of coated silver was 4.8, 4.6, 4.4, 4.0.
g/m ² and the other conditions were the same as sample-4.
6, 7, 8, and 9 were created. When we investigated the combinations that gave the same performance as sample 4, which was processed for 8 minutes using developer, we found that sample 6 was processed for 8 minutes using developer B, and sample 7 was processed for 7 minutes using developer C. It was also possible to reduce the amount of coated silver halide by about 4-8%. Example 4 Simultaneously mixed, prepared by ammonia method, containing iridium salt 2 x 10 ^-5 mol/mol Ag, approximately 9 mol % silver chloride, 91 mol % silver bromide, 0, 0.3 and 0.8 mol % silver iodide. 200 mg of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene per mole of a silver halide emulsion with an average grain size of 0.50μ consisting of
Hypo 50mg, chlorauric acid 5mg and Rodanammon 50
After adding 40 mg of 1-phenyl-5-mercaptotetrazole and 80 mg of the following sensitizing dye D-5 and 50 mg of the above-mentioned D-1, they were subjected to optimal 2R ripening at 60°C. An anti-irradiation magenta dye, a surfactant, and a hardening agent were added to this and coated on polyethylene laminate paper, and a conventional gelatin protective layer was further provided to prepare samples 4-1, 4-2, and 4-3. Each sample thus obtained was subjected to sensitometry using the method described below to examine changes in gamma. The results are shown in Table 4. Exposure: Using a xenon flash sensitometer (model mark manufactured by EG&G), density difference △D=
Exposure (light emission time 10 ^-6 seconds) is carried out through a 0.15 stepped optical wedge. Development processing Development 35℃ 20 seconds Fixing 35℃ 20 seconds Washing 30℃ 15 seconds Drying 50℃ 20 seconds Developer Sakuradol Type 621 (manufactured by Konishiroku Photo Industry Co., Ltd.)
The solutions to which 0.1 mol/ and 0.4 mol/ of KCl were added respectively are treated solutions F and G, and the comparative treated solution is E.
(However, the KCl content is 0.01 mol/). Fixer Sakura Fixtures Type 821 (Konishi Roku Photo Industry Co., Ltd.)
(manufactured by) Please note that the concentration measurement was performed using a Sakura photoelectric densitometer PDA-
65 was used.

[Table] As is clear from the results in Table 4, it is shown that silver halide having a higher silver iodide ratio can provide higher gamma when combined with the processing solution of the present invention. In addition, high gamma was obtained similarly to the present invention when processing was carried out at 20 DEG C. for 90 seconds using Kodak's D-72 developer instead of processing solution E and adding 0.1 and 0.4 mol/NaCl. Example 5 A color photographic paper was prepared by sequentially layering the following layers on a support made of polyethylene laminate from the support side. Layer 1... After chemically sensitizing a silver chlorobromoiodide emulsion consisting of 0.5 mol % silver iodide and 85 mol % silver bromide using Hypo 2 mg, prepared by the method described in Japanese Patent Publication No. 46-7772. Said sensitizing dye D-1
2.5×10 ^-4 mol, 400 mg of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene was dissolved and dispersed in dibutyl phthalate in a conventional manner to create a yellow coupler of 0.3
In addition, a hardener and a surfactant are added so that the amount of silver coated is 0.4 g/m ² . Layer 2: Coat with gelatin of 1.0 g/m ² . Layer 3: After chemically sensitizing a silver chlorobromide emulsion consisting of 80 mol% silver bromide prepared by the method described in Japanese Patent Publication No. 46-7772 using 1.5 mg of hypo,
Said sensitizing dye D-5 2.3×10 ⁻⁴ mol, 4
-hydroxy-6-methyl-1,3,3a,
Add 400 mg of 7-tetrazaindene, 0.2 mol of magenta coupler dissolved and dispersed in dibutyl phthalate in a conventional manner, and further add a hardening agent,
Add a surfactant and apply the coating so that the amount of silver coated is 0.4 g/m ² . Layer 4...UV absorber dissolved and dispersed in dioctyl phthalate, 0.5g/m ² , gelatin 1.0
Coat so that it is g/m ² . Layer 5...A silver chlorobromide emulsion containing 80 mol% silver bromide prepared by the method described in Japanese Patent Publication No. 46-7772 was chemically sensitized using 1.5 mg of hypo, and then sensitizing dye D shown below was added. -6 0.9×10 ^-4 mol,
4-hydroxy-6-methyl-1,3,
Added 400 mg of 3a,7-tetrazaindene, 0.2 mole of cyan coupler dissolved and dispersed in dibutyl phthalate in a conventional manner, and further added a hardener and a surfactant, resulting in a coated silver amount of 0.3 g/m ²
Paint it so that it looks like this. Layer 6: Coat the same amount of ultraviolet absorber and gelatin as layer 4. Using a sensitometer to measure the blue color on the sample prepared above,
Sensitometry was performed with monochromatic exposure through green and red filters. The processing conditions are as follows. Color development 30℃ 3 minutes Bleach fixing 30℃ 1 minute 30 seconds Washing with water 30℃ 1 minute 30 seconds Drying 80℃ or less Color developer composition N.Ethyl-N-β-methanesulfonamide
4.0g Ethyl-3-methyl-4-aminoaniline sulfate Sodium sulfite (anhydrous) 2.0g Hydroxylamine (sulfate) 2.0g Potassium carbonate 25.g Potassium bromide 1.5g Penzyl alcohol 12.0ml Add water to make 1 Adjust the pH to 10.2 using NaOH. Sodium chloride 0, 1.0, 5.0, 15g/
and color developer CD-H, I, J, K.
And so. Bleach-fix solution composition: Ethylenediaminetetra Sodium iron acetate...60.0g Ammonium thiosulfate...100.0g Sodium bisulfite...10.0g Sodium metabisulfite...3.0g Add water to bring the pH to 1, and adjust the pH to 6 using aqueous ammonia. Adjust to 6. In this way, color developing solution (CD-H, CD-
Table 5 shows the sensitivity and gamma results obtained by processing with I, CD-J, CD-K).

[Table] From the results in Table 5, it can be seen that both the sensitivity and gamma of the image of the silver halide photosensitive material obtained by processing with the color developer according to the present invention are high. Example 6 Silver halide grains were formed in the presence of 5 x 10 ^-6 mol of water-soluble rhodium salt and 3 x 10 ^-6 mol of water-soluble iridium salt, consisting of 5 mol % silver chloride and 95 mol % silver bromide. Silver halide emulsion (average grain size 0.6μm)
was prepared by the ammonia method and sensitized to optimal sensitivity by gold and sulfur sensitization. This silver halide emulsion was added with 1-phenyl-5 as an optical thickener (D-1).
-Mercaptotetrazole, sodium dodecylbenzenesulfonate and formalin were added. Then methylhydroquinone 0.2 molphenidone
Add 0.03 mol of PH regulator and adjust the emulsion to pH with acetic acid.
4.5, multilayer coating was carried out on thin polyethylene laminate paper so that the amount of coated silver was 1.5 g/m ² and the amount of gelatin in the protective layer was 2.0 g/m ² . Table 6 shows the results when the sample thus obtained was developed in the same manner as in Example 1.

[Table] As is clear from the results in Table 6, the silver halide photosensitive material was treated with the developing solution (6-C and 6-D) of the present invention in which the concentration of chloride ions in the developer was 0.06 mol/or more. It can be seen that the sensitivity (S), gamma (G) and maximum density (Dmax) are all high. Further, Table 7 shows the results when similar samples were treated with a developer having the following composition. Developer Solution Developer Solution 6-K Developer Solution 6-L NaOH 30 g 30 g KBr 2.0 g 2.0 g NaCl 0 g 15 g Add water 1 1 Develop with this developer solution (6-K) and (6-L) The results are shown in Table 7.

[Table] From the results in Table 7, the developing processing solution of the present invention (6-
It can be seen that the sensitivity (S) and maximum density (Dmax) of the silver halide photosensitive material treated with L) are increased even when a developing agent is added to the photosensitive material.

Claims (1)

[Claims] 1 After imagewise exposing a silver halide photosensitive material having at least one halide emulsion layer on a support, chloride ions are removed 6× in the presence of a developing agent.
1. A method for developing a silver halide photosensitive material, comprising developing with a solution containing a concentration of 10 ^-2 mol/or more.