JPH0556492B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a method for processing silver halide black-and-white photographic materials, and more particularly to a method for processing silver halide black-and-white photographic materials that can be rapidly processed. [Prior Art] In recent years, processing steps for photographic light-sensitive materials have been becoming more and more rapid, and silver halide black-and-white photographic materials are no exception. The method currently used as the fastest processing method for black and white photographic materials,
There is a stabilization treatment method. The stabilization treatment method is to immerse the unexposed photosensitive silver halide remaining in the photosensitive material in an aqueous solution containing thiocyanate after the development process, even if it is exposed to light afterwards. This is a treatment method that converts silver into a stable silver complex that does not show any change. According to this method, since the water washing process can be omitted, the processing time can be significantly shortened. However, this stabilization treatment method has the following drawbacks. First, since thiocyanate has deliquescent properties, a photographic material subjected to stabilization treatment exhibits so-called stickiness. Second, thiocyanate may generate cyanide ions that are harmful to the human body under certain severe conditions, and its use is undesirable from the standpoint of environmental pollution. Third, photographic materials stabilized using thiocyanate are susceptible to loss of image density or loss during long-term storage. That is, the color of the image, which was initially black and white, changes to yellow or disappears during long-term storage. This development is called fading, and it is particularly likely to occur when the processed photosensitive material is stored under high humidity. Fourthly, as is well known, thiocyanates have the property of corroding metals. Since the stabilization treatment method has the above-mentioned drawbacks, there has been a strong desire for a new rapid treatment method to replace it. As a rapid processing method for black and white photographic materials other than currently known stabilization processing methods, there is a processing method that consists of three steps: development processing, fixing processing and water washing processing. It is often done. In addition, in order to further shorten the development time, a developing agent is added to the photosensitive material in advance, and instead of the usual development process, it is processed with an alkaline activating solution that does not contain any or substantially no developing agent.
A rapid processing method in which fixing processing and water washing processing are successively performed is also known. However, the above-mentioned rapid processing method consisting of the three steps of development processing (or alkali activation processing), fixing processing and water washing processing has a fundamental flaw.
In other words, when the washing process time becomes shorter, the fixer composition incorporated into the photosensitive material during the fixing process is
It cannot be completely removed in the subsequent water-washing process and remains in the photosensitive material even after the water-washing process is finished, so if the processed photosensitive material is stored for a long period of time, the image will fade. In addition, in recent years, it has become necessary to reduce the flow rate of flushing water for environmental protection reasons such as saving water resources and reducing the amount of treated waste liquid. However, when the washing water flow rate is reduced, the fixer composition brought into the washing water is not sufficiently diluted and accumulates in the washing water. It will remain in the material,
This causes a problem in that the durability of the image deteriorates and the image fades due to long-term storage.
In particular, under low-flow washing conditions in which the daily flow rate of washing water is less than the washing tank capacity, it is almost impossible to obtain stable images with little fading. [Object of the Invention] A first object of the present invention is to provide a method for processing a silver halide black-and-white photographic material, which enables rapid processing and provides excellent stability of photographic images after processing. A second object of the present invention is to provide a method for processing silver halide black-and-white photographic materials that can significantly reduce the amount of washing water used in large quantities and the amount of washing water waste. [Structure of the Invention] As a result of extensive research, the present inventor has discovered a method for halogenation that involves processing with a fixing solution containing thiosulfate as a fixing agent and subsequently processing with a water-washing substitute stabilizing solution without substantially washing with water. In a method for processing a silver black-and-white photographic material, the water-washing alternative stabilizer contains a polymer having a pyrrolidone core unit in its molecular structure and a sulfite. It has been discovered that the above object can be achieved by a method of processing materials (referred to as "materials"). A preferred embodiment of the present invention is that the fixer contains at least one selected from water-soluble aluminum salts and borates, more preferably both water-soluble aluminum salts and borates; The objects of the present invention can be achieved to a higher degree depending on the embodiments. The present invention will be explained in detail below. The polymer containing a pyrrolidone nucleus in the molecular structure used in the present invention (including copolymers, hereinafter referred to as the polymer of the present invention) has a main chain or a side chain with a pyrrolidone nucleus. It includes all polymerizable polymers in which an arbitrary number of positions are substituted, and may be a homopolymer or a copolymer obtained by polymerizing two or more types of copolymer components. In the latter case, a monomer as a copolymer component that has a pyrrolidone core unit in its molecular structure is copolymerized with another monomer that does not have a pyrrolidone core unit in its molecular structure and is copolymerized with the monomer as a copolymerization component. It is preferably contained in the copolymer obtained at least 20 mol% or more, particularly preferably 30 mol% or more. In addition, other monomers that do not have a pyrrolidone core unit in their molecular structure to be copolymerized with the monomer as a copolymerization component that has a pyrrolidone core unit in their molecular structure include those that can yield a hydrophilic copolymer. Any can be used. The polymer of the present invention has a weight average molecular weight of 1000 to 70000.
The following are preferred, and typical examples thereof include the following. [Exemplary compounds] [1] Poly-N-vinyl-2-pyrrolidone nucleus (*Note 1) [2] Poly-N-(2-acryloyloxy)
Ethyl-2-pyrrolidone [3] Poly-N-glycidyl-2-pyrrolidone [4] Poly-N-allyl-2-pyrrolidone [5] Copoly-N,N-dimethyl-N-[3(2)
-pyrrolidonyl)-2-hydroxy]propylamine/N'-acrylolimine [6] copoly-N-vinyl-2-pyrrolidone/
N-acryloylmorpholine (molar ratio 42:58) [7] Copoly-N-vinyl-2-pyrrolidone/
N-acryloylpiperidine (molar ratio 35:65) [8] Poly-N-vinyl-2-pyrrolidone/N
-methacryloyl-2-methylimidazole
(molar ratio 55:45)

[9] Copoly-N-(2-acryloyloxy)
-Ethyl-2-pyrrolidone/acrylic acid diethylamide (molar ratio 60:40) [10] Copoly-N-(2-methacryloyloxy)ethyl-2-pyrrolidone/sodium acrylate (molar ratio 75:25) [11] Copoly -N-(3-acryloyloxy)
Propyl-2-pyrrolidone/methyl methacrylate (molar ratio 65:35) [12] Copoly-N,N-dimethyl-N-[3-
(2-pyrrolidonyl)-2-hydroxy]-propylamine-N'-acrylolimine/ethyl acrylate (molar ratio 65:35) [13] Copoly-N-vinyl-2-pyrrolidone/
Vinyl acetate (molar ratio 70:30) [14] Copoly-N-vinyl-2-pyrrolidone/
Methyl acrylate (molar ratio 70:30) [15] Copoly-N-vinyl-2-pyrrolidone/
Styrene (molar ratio 80:20) [16] Copoly-N-vinyl-2-pyrrolidone/
Acrylic acid amide/N-vinyl-2-methylimidazole (molar ratio 50:30:20) [17] Copoly-N-vinyl-2-pyrrolidone/
N-(1,1-dimethyl-3-oxo)-butyl-acrylamide (molar ratio 70:30) [18] Copoly-N-allyl-2-pyrrolidone/
Vinyl acetate (molar ratio 64:36) [19] Copoly-N-vinyl-2-pyrrolidone/
4-vinylpyridine (molar ratio 60:40) [20] Copoly-N-vinyl-2-pyrrolidone/
Ethyl acrylate/acrylic acid monoethanolamine acid (molar ratio 50:45:5) [21] Copoly-N-vinyl-2-pyrrolidone/
piperidinomaleamic acid piperidic acid
(Molar ratio 53:47) [22] Copoly-N-vinylpyrrolidone/4-vinylpyridino-N-methyl iodide
(Molar ratio 42:58) [23] Copoly-N-vinylpyrrolidone/thiourea maleic acid half ammonium salt
(Mole ratio 60:40) *Note (1) Exemplary compound [1] is manufactured by General Aniline & Film Corp.
Aniline and Film Corp.) to PVP K-
15, PVP K-17, PVP K-30, PVP
K-60, PVP K-90 product name, Mata B.
A.S.F. Japan Co., Ltd. (BASF)
Aktiengesellschaft), Corydon 12,
It is commercially available under the trade names of Kollidon 17, Kollidon 25, Kollidon 30, Kollidon 90, Rubiscoll K-17, Rubiscoll K-30, and Rubiscoll K-90. The polymer of the present invention, as mentioned above, is partially commercially available and can be easily obtained.
Published by John Wilery and Sons, Inc. (1961)
2009) Davrille Earl Sorenson, Tay Davrille Campbel (WR Sorenson, TW
Campbell) Preparatives, Methods,
Of, Polymer, Chemistry (Preparative
It can be easily synthesized according to the method described in Methods of Polymer Chemistry. The polymer of the present invention may be used alone, or two
More than one species may be used in combination, and the amount used is in the range of 0.01 g to 100 g, preferably in the range of 0.05 g to 10 g, per one water washing alternative stabilizer. The polymer of the present invention may be added to a stable tank liquid as an alternative to washing, or may be added to a tank replenishment liquid to replenish the stable tank liquid as an alternative to washing, or both may be used in combination. It's okay. In the present invention, after processing with a fixing solution, processing with a washing alternative stabilizing solution without substantially washing with water means processing in a processing tank using a washing alternative stabilizing solution (if the tank consists of a plurality of tanks, the foremost tank thereof) As long as the concentration of the fixer brought into the tank does not fall below 1/200, a single tank or multiple tank counter-current method can be used for a very short period of time between the treatment with the fixer and the treatment with the washing alternative stabilizer. This means that treatments such as rinsing treatment (for 10 seconds or less), auxiliary water washing, and washing promotion bath may be performed. In the present invention, the water-washing alternative stabilizing solution refers to a processing solution for stabilization that is immediately stabilized after processing with a fixer and does not substantially require water-washing. 100 materials
If it is 50 ml or less per cm ² , it is a water washing alternative stabilizing solution of the present invention. In the present invention, the stabilization treatment can be used in one tank or in multiple tanks without any problem, but preferably in one tank or in multiple tanks.
There are 4 tanks. The present invention is most effective when the amount of water-washing substitute stabilizing solution refilled into the stabilizing bath is small, and the replenishing amount ranges from 1 to 50 times the amount brought in from the previous bath per unit area of the photographic material to be processed. Preferably, the effect of the present invention is particularly significant in the range of 2 to 20 times. The water-washing alternative stabilizing solution is used to replenish a small amount of water when processing a photosensitive material, and basically only water can be used, but various compounds can also be added, and compounds that can be preferably used in the present invention include: These include antifungal agents, chelating agents, and metal salts. The antifungal agents preferably used in the water washing alternative stabilizer of the present invention include hydroxybenzoic acid compounds, alkylphenol compounds, thiazole compounds, pyridine compounds, guanidine compounds, carbamate compounds, morpholine compounds, and quaternary phosphonium compounds. These include ammonium-based compounds, urea-based compounds, isoxazole-based compounds, propanolamine-based compounds, sulfamide derivatives, and amino acid-based compounds. The hydroxybenzoic acid compounds include hydroxybenzoic acid and hydroxybenzoic acid ester compounds such as methyl ester, ethyl ester, propyl ester, butyl ester, etc., but preferably n-butyl ester, isobutyl ester, and propyl ester of hydroxybenzoic acid. It is an ester, and more preferably a mixture of the three hydroxybenzoic acid esters. Alkylphenol compounds have an alkyl group
It is a compound having a C1-6 alkyl group as a substituent, and other preferable phenol compounds include orthophenylphenol and orthocyclohexyphenol. The thiazole compound is a compound having a nitrogen atom and a sulfur atom in a five-membered ring, preferably 1,
2-benzisothiazolin 3-one, 2-methyl-4-isothiazolin 3-one, 2-octyl-
4-isothiazolin 3-one, 5-chloro-2-
Methyl-4-isothiazolin-3-one, 2-(4
-thiazoline)benzimidazole. Specifically, pyridine compounds include 2,6-dimethylpyridine, 2,4,6-trimethylpyridine,
Examples include sodium-2-pyridinethiol-1-oxide, and sodium-2-pyridinethiol-1-oxide is preferred. Specifically, guanidine compounds include cyclohexidine, polyhexamethylene biguanidine hydrochloride,
Dodecylguanidine hydrochloride, preferably
Dodecylguanidine and its salts. Carbamate compounds are specifically methyl-1
-(Butylcarbamoyl)-2-benzimidazole carbamate, methylimidazole carbamate, etc. Specific examples of morpholine compounds include 4-(2-nitrobutyl)morpholine and 4-(3-nitrobutyl)morpholine. Quaternary phosphonium compounds include tetraalkylphosphonium salts, tetraalkoxyphosphonium salts, etc., but tetraalkylphosphonium salts are preferred, and more specific preferred compounds include tri-n-butyl-tetradecylphosphonium chloride, tri-phenyl. There is nitrophenylphosphonium chloride. Specific examples of quaternary ammonium compounds include benzalkonium salts, benzethonium salts, tetraalkylammonium salts, and alkylpyridinium salts, and specific examples include dodecyldimethylbenzylammonium chloride, didecyldimethylammonium chloride, laurylpyridinium chloride, etc. . Specifically, the urea-based compounds include N-(3,4-dichlorophenyl)-N'-(4-chlorophenyl)urea, N-(3-trifluoromethyl-4-chlorophenyl)-N'-(4- chlorophenyl) urea, etc. Specific examples of isoxazole compounds include 3-hydroxy-5-methyl-isoxazole. Propanolamine compounds include n-propanols and isopropanols, and specifically,
DL-2-benzylamino-1-propanol,
3-diethylamino-1-propanol, 2-dimethylamino-2-methyl-1-propanol,
Examples include 3-amino-1-propanol, isopropanolamine, diisopropanolamine, NN-dimethyl-isopropanolamine, and the like. Sulfamide derivatives specifically include fluorinated sulfamide, 4-chloro-3,5-dinitrobenzenesulfamide, sulfanilamide, acetosulfamine, sulfapyridine, sulfaguanidine, sulfathiazole, sulfadiazine,
Examples include sulfamerazine, sulfamethazine, sulfisoxazole, homosulfamine, sulfasomidine, sulfaguanidine, sulfamethizole, sulfapyrazine, phthalisosulfathiazole, swashinylsulfathiazole, and the like. Specifically, the amino acid compound is N-lauryl-
There is β-alanine. Among the above-mentioned antifungal agents, compounds preferably used in the present invention are thiazole compounds, pyridine compounds, guanidine compounds, and quaternary ammonium compounds. Furthermore, thiazole compounds are particularly preferred. The amount of the antifungal agent added to the washing substitute stabilizing solution is in the range of 0.002 g to 50 g, preferably in the range of 0.005 g to 10 g, per liter of the washing substitute stabilizing solution. In the present invention, the sulfites (including the replenisher) preferably used in the water washing alternative stabilizing solution include sodium sulfite, potassium sulfite, ammonium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, sodium metabisulfite, and sodium sulfite. Examples include compounds such as potassium bisulfite, ammonium metabisulfite, and hydrosulfite, but any compound that releases sulfite ions may be used. The above sulfite is preferably added in an amount of at least 1 x 10 ^-3 mol/, more preferably 2 x 10 ^-3 mol// to the water washing alternative stabilizing solution.
It is to be added in a range of 1 x 10 ^-1 mol/. In the present invention, the water washing substitute stabilizer preferably contains a chelating agent having a chelate stability constant of 8 or more with respect to iron ions. Here, the chelate stability constant is LGSille′
“Stability Constants of
Metalion Complexes”，The Chemical
Society, London (1964). S.Chaberek・AE
“Organic Sequestering Agents” by Martell,
Wiley (1959). etc. means a commonly known constant. In the present invention, examples of the chelating agent having a chelate stability constant of 8 or more for iron ions include an organic carboxylic acid chelating agent, an organic phosphoric acid chelating agent,
Examples include inorganic phosphoric acid chelating agents and polyhydroxy compounds. Note that the above-mentioned iron ion means ferric ion (Fe ³⁺ ). In the present invention, specific examples of compounds of the chelating agent having a chelate stability constant of 8 or more with ferric ions include the following compounds, but are not limited thereto. Namely, ethylenediamine diorthohydroxyphenylacetic acid, diaminopropanetetraacetic acid, nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, iminodiacetic acid, diethylenetriaminopentaacetic acid, hydroxyethyliminodiacetic acid. Acetic acid, diaminopropanoltetraacetic acid, transcyclohexanediaminetetraacetic acid, ethylenediaminetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediaminetetrakismethylenephosphonic acid,
Nitrilotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 1,1-
Diphosphonoethane-2-carboxylic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxy-1-phosphonopropane-1,2,3-
Examples include tricarboxylic acid, catechol-3,5-disulfonic acid, sodium pyrophosphate, sodium tetrapolyphosphate, and sodium hexametaphosphate. Particularly preferred are A-PO ₃ M ₂ (where M is a hydrogen atom, a sodium atom, or a potassium atom). represents an atom or a cation such as ammonium. A represents an inorganic or organic substance. For example,
2-phosphonobutane-1,2,4-tricarboxylic acid, 1,1-diphosphonoethane-2-carboxylic acid, pyrophosphoric acid, sodium tetrapolyphosphate,
Sodium hexametaphosphate, sodium polyphosphate, nitrilotrimethylenephosphonic acid, ethylenediaminetetraphosphonic acid, diethylenetriaminepentaphosphonic acid, 1-hydroxypropylidene-1,1-diphosphonic acid, 1-aminoethylidene-1,1-diphosphonic acid, 1 -Hydroxyethylidene-1,1-diphosphonic acid and salts thereof. Good results can be obtained when the amount of the chelating agent used in the present invention ranges from 0.01 to 50 g, preferably from 0.05 to 20 g, per one water-washing alternative treatment solution. It is preferable that the water washing substitute stabilizer in the present invention contains a metal salt in combination with the chelating agent. Such metal salts include Ba, Ca, Ce, Co,
In, La, Mn, Ni, Pb, Sn, Zn, Ti, Zr, Mg,
It is a metal salt of Al or Sr, and can be supplied as an inorganic salt such as a halide, hydroxide, sulfate, carbonate, phosphate, or acetate, or as a water-soluble chelating agent. The amount used is in the range of 1 x 10 ^-4 to 1 x 10 ^-1 mol per stabilizer, preferably 4 x 10 ^-4 to 2 x 10 ^{-2 mol.}
mole, more preferably in the range of 8×10 ⁻⁴ to 1×10 ⁻² mole. In addition, commonly known stabilizing bath additives include, for example, fluorescent bleaches, surfactants, organic sulfur compounds, onium salts, formalin, hardeners such as chromium, Japanese Patent Publication No. 39-22095, No. 39- No. 25772, 39-
There are organic sulfur compounds described in JP-A No. 25774 and JP-A-58-114035, but the amount of these compounds added is necessary to maintain the pH of the stabilizing bath according to the present invention, and the amount required during storage of the silver image. Any compound may be used in any combination as long as it does not adversely affect stability and precipitation. The pH of the water washing substitute stabilizer used in the present invention is not particularly limited, but is preferably in the range of PH0.5 to 12.0, more preferably in the range of PH3.0 to 10.0, and particularly preferably in the range of PH6.0 to 9.0. is within the range of The processing temperature during stabilization treatment is 15°C to 60°C.
℃, preferably in the range of 20℃ to 45℃. Further, the treatment time is usually 5 seconds to 3 minutes, and the shorter the time, the more preferable, and the most preferably 10 seconds to 1 minute. In the case of stabilizing treatment in multiple tanks, it is preferable that the treatment takes a shorter time in the earlier tanks, and the treatment time takes longer in the later tanks. In particular, it is desirable to process sequentially with a processing time 20% to 50% longer than in the previous tank. After the stabilization treatment according to the present invention, there is no need for rinsing at all, but rinsing with a small amount of water within an extremely short period of time, surface cleaning with a draining solution containing formalin, surfactants, etc. may be performed as necessary. You can do it as you like. When the method for supplying the washing substitute stabilizing solution in the stabilization treatment step according to the present invention is a multi-tank countercurrent method, it is preferable to supply it to the rear bath and overflow from the front bath. In the thiosulfate-containing fixers of the present invention, thiosulfate is used as a silver complexing agent. Thiosulfates include sodium thiosulfate, potassium thiosulfate, ammonium thiosulfate, etc.
It is used in a range of 10g/-500g/, preferably in a range of 20g/-300g/. In addition to thiosulfate, the fixing solution used in the present invention can have a composition commonly used in fixing solutions, such as silver halide solvents such as sodium thiocyanate, ammonium thiocyanate, thiourea, and amine derivatives; sulfurous acid. sodium,
Sulfites such as ammonium sulfite, sodium bisulfite, potassium metabisulfite; boric acid, borax,
Borates such as sodium metaborate; organic carboxylic acids such as acetic acid, citric acid, tartaric acid, and malic acid; inorganic acids such as sulfuric acid and hydrochloric acid; amines such as ethylenediamine, diethanolamine, and triethanolamine; potassium alum, ammonium alum, etc. Water-soluble aluminum salts such as aluminum chloride, aluminum sulfate, and aluminum chloride; organic compounds such as methanol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polyoxyethylene glycol, and acetone; and, if necessary, potassium iodide and iodide. It may contain iodides such as sodium and other additives. Among the above compounds, water-soluble aluminum salts and borates are particularly effective for the purpose of the present invention. The amount of water-soluble aluminum salt added is preferably 0.5 g to 100 g, more preferably 2 g to 50 g per fixer. The amount of borate added is preferably 0.5 to 50 g, particularly preferably 2 to 30 g, per fixer. Further, in the present invention, it is more preferable to use a water-soluble aluminum salt and a borate together. The pH value of the fixer is preferably in the range of PH3 to 12, particularly preferably in the range of PH3.5 to 8.0. The development process that is generally performed before the fixing solution of the present invention is silver development (the processing solution is a developer), and those having commonly used compositions can be used. Examples of developing agents include hydroquinone, alkylhydroquinone (e.g. methylhydroquinone, dimethylhydroquinone, t-butylhydroquinone), catechol, pyrazole, chlorohydroquinone, dichlorohydroquinone, methoxyhydroquinone, ethoxyhydroquinone, aminophenol developing agent (e.g. N-methyl-p -aminophenol, 2,4-diaminophenol), ascorbic acid developing agent, N-methyl-p-aminophenol sulfate, pyrazolones (e.g. 4-aminopyrazolone), 3
- Pyrazolidone developing agents (e.g. 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-5-
Methyl-3-pyrazolidone, 1-phenyl-4-
Methyl-pyrazolidone, 1,5-diphenyl-3
-pyrazolidone, 1-p-tolyl-3-pyrazolidone, 1-p-hydroxyphenyl-4,4-dimethyl-3-pyrazolidone), etc. are used alone or in combination. In particular, combinations of hydroquinone and 3-pyrazolidones or hydroquinone and aminophenols are suitable from the viewpoint of rapid processing. In addition, the developer may contain preservatives such as sulfites, bisulfites, bisulfite adducts of aldehydes, and hydroxylamines; alkaline agents such as hydroxides, carbonates, and phosphates; and acetic acid, etc. PH regulator; solubilizing agent such as polyethylene glycol; sensitizer such as quaternary ammonium salt; organic solvent such as methanol, diethylene glycol, diethanolamine, dimethylformamide, dimethyl sulfoxide; development accelerator; surfactant;
Antifoaming agent; Color toning agent; Carboxymethyl cellulose,
Viscosifiers such as hydroxyethyl cellulose;
Hardeners such as glutaraldehyde; silver sludge inhibitors; silver halide solvents such as thioethers, thioamides, thiocyanates, thiosulfates; potassium bromide, benzotriazole, 2-mercaptobenzothiazole, 1-phenyl-5 - Various additives such as antifoggants such as mercaptotetrazole; chelating agents such as aminopolycarboxylic acid, aminopolyphosphonic acid, and phosphonocarboxylic acid can be contained. Furthermore, if a developing agent has been added to the photosensitive material in advance, there is no problem in replacing development with alkali activation treatment. The processing solution used in the alkaline activation process can contain any components other than the developing agent used in conventional black and white developers. The pH of the alkaline activation liquid is usually about 10-14, preferably about 11-14. Silver may be recovered by a known method from a processing solution containing a soluble silver complex salt, such as a fixing solution, as well as a washing substitute stabilizing solution used in the processing method of the present invention. For example, electrolysis method (described in French Patent No. 2299667), precipitation method (Japanese Unexamined Patent Publication No. 52-73037, German Patent No. 2331220)
(described in the specification), ion exchange method (Japanese Patent Application Laid-open No. 51-17114
(described in the specification of German Patent No. 2548237) and the metal substitution method (described in the specification of British Patent No. 1353805) can be effectively used. The photosensitive material to which the present invention is applied may be any photosensitive material as long as it leaves a silver image after development processing, but the method of the present invention is suitable for processing X-ray photosensitive materials or printing photosensitive materials. It is advantageous to apply it to Furthermore, the following processing steps (1), (2) and (3) are particularly effective for the present invention. (1) Development-Fixing-Water washing alternative stabilization treatment (2) Alkali-activated treatment-Fixing-Water washing alternative stabilization treatment [Example] The present invention will be specifically explained below with reference to Examples. The mode of implementation of the invention is not limited. Example 1 A high-sensitivity direct X-ray film coated with a silver iodobromide gelatin emulsion (containing 2 mol% silver iodide) on both sides was prepared using a KS-1 type sensitometer (manufactured by Konishi Roku Photo Industry Co., Ltd.) based on the JIS method. ) after white exposure,
The following experiment was conducted. (Experiment-1) Comparison [Developer replenisher] Hydroquinone 10g 1-phenyl-3-pyrazolidone 0.35g Sodium carbonate (monohydrate) 25g Sodium hydroxide 5g 5-methylbenzotriazole 0.15g Glacial acetic acid 15g Boric acid 10g Potassium sulfite 70g Glutar Aldehyde (25% aqueous solution) 20g Diethylenetriaminepentaacetic acid 1.0g Water was added to make 1, and the pH was adjusted to 10.40 with sulfuric acid and potassium hydroxide. [Developer tank fluid] Add the following to developer replenisher 1. Glacial acetic acid 6.0g Brompotash 4.0g [Fixer replenisher and tank fluid] Ammonium thiosulfate 200g Sodium sulfite 20g Acetic acid 30g Boric acid 8g Aluminum sulfate 15g Diethylenetriaminepentaacetic acid pentasodium salt
Add 1.0g water to make 1, then add acetic acid and ammonia to pH
Adjusted to 4.2. [Water washing alternative stable replenisher and tank liquid] Diethylenetriaminepentaacetic acid 1.0g 4-(-nitrobutyl)morpholine 0.1g Water was added to bring the solution to 1, and the pH was adjusted to 6.5 with sulfuric acid and aqueous ammonia. Development processing process Development 35℃ 25 seconds Fixing 35℃ 25 seconds Stabilization as an alternative to washing 30℃ 20 seconds Drying 50℃ Fill the automatic developing machine with the above developer tank liquid, fixing tank liquid, and washing alternative stabilization tank liquid, and the replenishment amount is as follows.
450 ml of developing replenisher, 900 ml of fixing replenisher, and 600 ml of stable replenisher as a substitute for washing per 1 m ² of photosensitive material.
The above photosensitive material was processed and used as a sample. (Experiment-2) Comparison Stabilization as an alternative to water washing in Experiment-1 was performed using running water at 30°C.
The treatment was carried out in the same manner as in Experiment 1, except that the washing time was changed to 20 seconds. Replenishment amount of washing water is 10 per ^m2 of photosensitive material.
And so. (Experiment-3) Comparison Add 1 part of Rubiscoll K-17 of the exemplified compound [1] to the water washing alternative stable replenisher and tank liquid formulation of Experiment-1.
The treatment was carried out in the same manner as in Experiment-1 except that g/g was added. (Experiment-4) Comparison The treatment was carried out in the same manner as in Experiment-3 except that 3 g of sodium sulfite was added to the water washing alternative stable replenisher and tank liquid in Experiment-3. The transmittance density of each stage of the sample obtained in each of the above experiments was measured, and the sample was then subjected to high temperature and high humidity (70°C).
℃, 70% RH) for two weeks, the permeation density of each stage was measured again, and the change in permeation density due to storage of each sample was calculated. The results are shown in Table-1.

[Table] From the results in Table 1, compared to Comparative Experiments 1, 2 and 3, the exemplified compound [1] of the present invention and sulfite were added to the water washing alternative stabilizing solution (Experiment 4).
It can be seen that this is extremely preferable because the decrease in density of the silver image upon storage is small. Furthermore, from a comparison between Experiment 2 and Experiment 4, it was found that the present invention requires less time and amount of water for post-processing with a processing liquid having fixing ability than a conventional development processing method that includes washing with running water. It can be seen that the stability of the resulting photographic image is excellent. Example 2 When the same experiment as in Example-1 was conducted using Exemplified Compounds [4], [11] and [20] in place of Exemplified Compound [1] in Example-1, the results were as follows. Similar effects of the present invention were obtained. [Effects of the Invention] The method of the present invention enables reductions in processing time and amount of water used, and provides photographic images with improved storage stability, compared to conventional processing methods that include water washing. In addition, the method of the present invention improves the stickiness of processed photosensitive materials compared to known stabilization treatment methods, and eliminates problems such as environmental pollution and metal corrosion caused by thiocyanates used in the method. do.

Claims (1)

[Claims] 1. A method for processing a silver halide black-and-white photographic material in which the material is processed with a fixing solution containing thiosulfate as a fixing agent and then processed with a water-washing alternative stabilizer without substantially washing with water, wherein the water-washing alternative stabilizer is , a silver halide containing a polymer having a pyrrolidone core unit in its molecular structure and a sulfite, and characterized in that the amount of replenishment of the water washing alternative stabilizing solution is 1 to 50 times the amount brought in from the previous bath. A method of processing black and white photographic materials.