JPH05216180A - Treating method for silver halide photographic material - Google Patents

Abstract

PURPOSE:To reduce the amount of a developer supplied per unit area to be treated by supplying a required minimum amount of the developer, and, if the amount is not sufficient, supplying the developer in an amount equal to the shortage independently. CONSTITUTION:In a method whereby a black and white silver halide photographic material is treated using an automatic developing machine while a developer is supplied, the developer is supplied in the rate of not more than 400ml per 1m<2> of the silver halide photographic material and a required minimum amount of supply per unit time is predetermined for the automatic developing machine and when the developer is in short of the amount, the shortage is supplied. In this case, the developer used may be the same as a new one used at the start of supply or may be higher in pH and lower in bromine ion concentration than the new one. In the recipe for supplementing the shortage of the required minimum amount of the developer independently of the recipe for replenishing the developer according to the area to be treated of the silver halide photographic material, the developer is preferably higher in hydroquinone concentration than the new one and is substantially equal in bromine ion concentration to the new one.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a black-and-white silver halide light-sensitive material, especially a medical X-ray light-sensitive material, which is carried out by using an automatic processor, and the amount of developer replenisher per unit area of the light-sensitive material. The present invention relates to a processing method by which stable photographic performance can be obtained even when the amount is reduced.

[0002]

2. Description of the Related Art A black and white silver halide light-sensitive material is generally processed in steps of developing, fixing, washing with water and drying after exposure.
Recently, most of them are processed by using an automatic processor (hereinafter abbreviated as an automatic processor). Conventionally, in the case of a so-called sheet-shaped photosensitive material such as an X-ray photographic photosensitive material, it has been general to process the photosensitive material in an amount of 550 ml or more with respect to 1 m ² of the photosensitive material.

However, photographic developer waste has a high chemical oxygen demand (so-called COD) or biological oxygen demand (so-called BOD). Therefore, the developing waste liquid must be chemically or biologically treated to render it harmless before being discharged. Since a great economic burden is imposed on the treatment of these waste liquids, a treatment method with a small amount of the developer replenisher has been desired.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a processing method with a small amount of developing replenisher per unit processing area in the processing of a black-and-white silver halide photographic light-sensitive material, especially an X-ray photographic light-sensitive material using an automatic processor. To provide. Another object of the present invention is to provide a processing method capable of obtaining a photographic property with good stability even when the amount of the developer replenisher is small.

[0005]

The object of the present invention is to provide a method for processing a black-and-white silver halide photographic light-sensitive material while replenishing a replenisher with an automatic developing machine.
It is replenished at a rate of 400 ml or less per m ^2, but the required minimum replenishment amount per unit time is set in advance for the automatic machine and replenishment is made, and when a shortage occurs with respect to this amount, the shortage amount is replenished Is achieved by

The present invention will be described in detail below. The replenisher used may be the same as the new solution used at the start, but pH
May be higher than the new solution and the bromine ion concentration may be lower than the new solution. Furthermore, in addition to the replenisher solution prescription that is replenished according to the processing area of the silver halide light-sensitive material, the shortage of the necessary minimum replenisher solution is replenished. It is preferable that the concentration of hydroquinone is higher than that of the fresh solution at the time of starting the replenisher solution and that the bromine ion concentration is substantially the same.

The photographic light-sensitive material used in the present invention is not particularly limited and is mainly used as a general black-and-white light-sensitive material. Preferably, a system for irradiating a subject such as a human body with X-rays such as X-ray film for direct photographing, X-ray film for indirect photographing, CRT film, etc., and converting the X-rays passing through the subject into visible light for exposure. Used. Examples thereof include medical or industrial X-ray photographic materials, X-ray duplication photographic materials, medical CRT image photographic materials, and the like.

As one of the modes used in the present invention, the aspect ratio of tabular silver halide grains is such that the average value of the diameter of a circle having an area equal to the projected area of each tabular grain and the tabular grain It is given as a ratio of the average value of particles and thickness, and is 4 or more. The preferred silver halide grain form has an aspect ratio of 4 or more and less than 20, more preferably 5 or more and less than 10. Further, the thickness of silver halide grains is preferably 0.3 μm or less, and particularly preferably 0.2 μm or less.

The tabular silver halide grains are preferably present in an amount of 80% by weight, more preferably 90% by weight or more, based on the total silver halide grains. The silver halide that can be used in the silver halide emulsion used in the present invention may be any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, silver chloride and the like. Preferred are silver iodobromide (1 to 0 to 10 mol%), silver bromide, and silver chlorobromide. A
The gI distribution may be internal high concentration or external high concentration.

The tabular silver halide emulsion is a knuck (C
ignac) and Chateau (Chatau) "The evolution of the morphology of physically aged silver bromide crystals (evolution.
Of the Morfolgy of Silver Promide Crystals Dualing Physical Raising) "Science & Industry Photography, Volume 33, No. 2 (1962), pp. 12
1-125, Duffin, "Photographic Emulsion Chemistry (Photogr)
apic emulation chemistr
y) ”Focal Press
s), New York, 1966, p. 66-p. 7
2, A. P. H. Tribelli, W.C.
F. Smith Photographic Journal, 8
0, 285 (1940) and the like, but JP-A-58-127,921, JP-A-58-113,92.
7. It can be easily prepared by referring to the method described in JP-A-58-113,928.

Further, a relatively low pBr of pBr 1.3 or less
It is obtained by forming a seed crystal in which tabular grains are present in an amount of 40% or more by weight in an atmosphere of a certain value, and growing a seed crystal while simultaneously adding a silver and halogen solution while keeping the pBr value at the same level. During this grain growth process, it is desirable to add silver and halogen solutions so that new crystal nuclei are not generated.

The size of tabular silver halide grains can be adjusted by controlling the temperature, selecting the type and amount of solvent, and controlling the addition rate of silver salt and halide used during grain growth. In the process of silver halide grain formation or physical ripening, cadmium salt, zinc salt, lead salt,
A thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt may be present together. If necessary, chemical sensitization can be performed.

As the chemical sensitization method, a gold sensitization method using a so-called gold compound, a sensitization method using a metal such as iridium, platinum, rhodium, or palladium, a sulfur sensitization method using a sulfur-containing compound, and a Se sensitizer using Se are used. A sensitization method, a Te sensitization method using a Te sensitizer, a reduction sensitization method using a complex salt, polyamine, or the like, or a combination of two or more thereof can be used.

The swelling percentage referred to in the present invention is (a) the photographic material is incubated at 38 ° C. and 50% relative humidity for 3 days, and (b) the thickness of the hydrophilic colloid layer is measured,
(C) Immerse the photographic material in distilled water at 21 ° C. for 3 minutes and (d) measure the percentage change in layer thickness compared to the hydrophilic colloid layer thickness measured in step (b). Can be determined by

The swelling percentage of the hydrophilic colloid layer containing at least one silver halide emulsion layer in the present invention is 25.
0 or less, 200% or less as a preferable swelling percentage 3
0% or more, particularly 150% or less and 50% or more are preferable. In the present invention, the swelling percentage is set to 2 from the viewpoints of rapid processing (for example, reduction of drying load) and simplification of processing (for example, omission of treatment dura, reduction of treatment agent and number of parts).
It should be 50% or less.

Such rapid processing and simplification of processing can be better achieved by further reducing the swelling percentage. On the other hand, if the swelling percentage is lowered, the speed of development, fixing, washing with water, etc. is lowered, so it is not preferable to lower it more than necessary. In the present invention, the swelling percentage can be controlled to 250% or less by those skilled in the art by, for example, increasing the amount of the hardener used in the light-sensitive material.

Examples of hardeners that can be used include aldehyde compounds, compounds having an active halogen described in US Pat. No. 3,288,775, and US Pat.
35,718 and the like, compounds having a reactive ethylenically unsaturated group, U.S. Pat. No. 3,091,537
Organic compounds such as an epoxy compound described in the above publication, a halogenocarboxaldehyde such as mucochloric acid, and the like are known. Of these, vinyl sulfone type hardeners are preferable. Further, a polymeric hardener can also be preferably used in the present invention.

As the polymer hardener used in the present invention, a polymer having an active vinyl group or a group which is a precursor thereof is preferable, and among them, a long spacer as described in JP-A-56-142524 is used. A polymer in which an active vinyl group or a group which is a precursor thereof is bonded to a polymer main chain is particularly preferable. The amount of these hardeners added to achieve the swelling percentage of the present invention depends on the type of hardener used and the type of gelatin.

The sensitizing dyes used in the present invention include cyanine dyes, merocyanine dyes, complex cyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes include cyanine dyes, merocyanine dyes, and dyes belonging to complex merocyanine dyes.

Any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, etc .; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these A nucleus in which an aromatic hydrocarbon ring is fused, that is, an indolenine nucleus, a benzindolenine nucleus, an indole nucleus, a benzoxadol nucleus, a naphthoxazole nucleus, a benzthiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzo Imidazole nucleus,
A quinoline nucleus or the like can be applied. These nuclei may be substituted on carbon atoms.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidin-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, and a rhodanine are used. 5 such as nucleus and thiobarbituric acid nucleus
~ 6-membered heterocyclic nuclei can be applied. For example, the compounds described in Research Disclosure 17643, page 23, item IV (December 1978) or the compounds described in the cited documents are used, and more specifically the following compounds can be used. 5,5'-dichloro-
3,3'-Diethylthiacyanine bromide, 5,5'-dichloro-3,3'-di (4-sulfobutyl) -thiacyanine Na salt, 5-methoxy4,5-benzo-3,3'-
Di (3-sulfopropyl) thiacyanine Na salt, 5,
5'-dichloro-3,3'-diethylselenacyanine iodide 5,5'-dichloro-9-ethyl-3,3'-di (3-
Sulfopropyl) thiacarbocyanine pyridinium salt,
Anhydro-5,5'-dichloro-9-ethyl-3-
(4-sulfobutyl) -3'-ethyl hydroxide, 1,1
-Diethyl-2,2'-cyanine bromide, 1,1-dipentyl-2,2'-cyanine perchloric acid, 9-methyl-
3,3'-di (4-sulfobutyl) -thiacarbocyanine pyridinium salt, 5,5'-diphenyl-9-ethyl-3,3'-di (2-sulfoethyl) -oxacarbocyanine Na salt, 5-chloro -5'-phenyl-9-ethyl-3- (3-sulfopropyl) -3 '-(2-sulfoethyl) oxacarbocyanine Na salt, 5,5'-dichloro-9-ethyl-3,3'-di (3-Sulfopropyl) oxacarbocyanine Na salt, 5,5'-dichloro-6,6'-dichloro-1,1'-diethyl-3,3 '
-Di (3-sulfopropyl) imidacarbocyanine Na
When the salt, 5,5'-diphenyl-9-ethyl-3,3'-di (3-sulfopropyl) thiacarbocyanine Na salt, and the sensitizing dye used in the present invention are added to the emulsion, the emulsion is appropriately selected. It is generally before coating on a transparent support, but may be a chemical ripening step or a silver halide grain forming step.

The emulsion layer of the photographic light-sensitive material used in the present invention may contain a polymer such as an alkyl acrylate latex, an emulsion, or a plasticizer such as a polyol such as trimethylolpropane in order to improve pressure characteristics. For the photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material used in the present invention, coating aids, antistatic agents, slipperiness improvement, emulsion dispersion, adhesion prevention and photographic property improvement (for example,
Various surfactants may be included for various purposes such as acceleration of development, hardening, and sensitization.

For example, saponins (steroids), alkylene oxide derivatives (eg polyethylene glycol, polyethylene glycol / polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, Nonionics such as polyalkylene glycol alkyl amines or amides, polyethylene oxide adducts of silicones), glycidol derivatives (eg alkenyl succinic acid polyglycerides, alkyl phenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Surfactants; alkyl carboxylates, alkyl sulfonates, alkylbens Sulfonate, alkylnaphthalene sulphinate, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl Anionic surfactants containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups such as phosphates; amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphorus Amphoteric surfactants such as acid esters, alkyl betaines and amino oxides; alkyl amine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, and aliphatic Or multiple Cationic surfactants such as phosphonium or sulfonium salts containing ring can be used.

As the antistatic agent, especially JP-A-62-1
09044, 62-215272, fluorine-containing surfactants or polymers, JP-A-60-76742.
No. 60, No. 60-80846, No. 60-80848, No. 6
0-80839, 60-76741, 58-2
No. 08743, No. 62-172343, No. 62-17
No. 3459, No. 62-215272, and other nonionic surfactants, or JP-A-57-
The conductive polymers or latices (nonionic, anionic, cationic, amphoteric) described in No. 204540 and No. 62-215272 can be preferably used. As the inorganic antistatic agent, conductive tin oxides, zinc oxides, or composite oxides obtained by doping antimony with metal oxides thereof as described in JP-A-57-118242 can be preferably used.

As the antistatic agent, it is particularly preferable to use a fluorosurfactant. In the present invention, it is preferable that the emulsion layer and / or the other hydrophilic colloid layer contain an organic substance which flows out in the development processing step. When the substance that flows out is gelatin, a gelatin species that is not involved in the crosslinking reaction of gelatin with a hardening agent is preferable, and examples thereof include acetylated gelatin and phthalated gelatin, and those having a small molecular weight are preferable. On the other hand, as polymeric substances other than gelatin, US Pat.
No. 271,158, polyacrylamides, or hydrophilic polymers such as polyvinyl alcohol and polydinylpyrrolidone can be effectively used, and types such as dextran, saccharose, and bullan are also effective. Among them, polyacrylamide and dextran are preferable, and polyacrylamide is a particularly preferable substance. The average molecular weight of these substances is preferably 20,000 or less, more preferably 10,000 or less. It is effective that the amount of outflow in the processing is 10% or more and 50% or less of the total weight of the organic material coated with silver halide grains or less.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the manufacturing process of the light-sensitive material, storage or photographic processing or stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroindazoles,
Nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, azaindenes such as triazaindenes,
Tetraazaindenes (especially 4-hydroxy substitution (1,
3,3a, 7) Tetrazaindenes), pentaazaindenes, etc .; Add many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. be able to.

In the present invention, as a matting agent, US Pat. Nos. 2,992,101, 2,701,245 and 41,428 are used.
94, 4396706 homopolymers of polymethylmethacrylate or copolymers of methylmethacrylate and methacrylic acid, organic compounds such as starch, and fine particles of inorganic compounds such as silica, titanium dioxide, sulfuric acid, and strontium barium. be able to.

The particle size is preferably 1.0 to 10 μm, more preferably 2 to 5 μm. There are no particular restrictions on other various additives used in the light-sensitive material preferably used in the present invention, and for example, JP-A-2-68539.
It is possible to use the materials described in the following relevant portions of the publication.

Item Applicable place 1. Silver halide emulsions and their JP-A-2-68539, page 8, lower right column, lower part, from the 6th line to the same, page 10, upper right column, 12th line. 2. Chemical sensitization method, page 10, upper right column, line 13 to lower left column, line 16 3. Antifoggants / stabilizers, page 10, lower left column, line 17 to page 11, upper left column, line 7 and page 3, lower left column, line 2 to page 4, lower left column. 4. Spectral sensitizing dyes, page 4, lower right column, line 4 to page 8, lower right column. 5. Surfactants / antistatic agents, page 11, upper left column, line 14 to page 12, upper left column, line 9 6. Matting agents, lubricants, plasticizers, page 12, upper left column, line 10 to upper right column, line 10

Page 14, lower left column, line 10 to lower right column, line 1 7. Hydrophilic colloid, page 12, upper right column, line 11 to left lower column, line 16 8. Hardener, page 12, lower left column, line 17 to page 13, upper right column, line 6 9. Support, page 13, upper right column, lines 7 to 20. 10. Dyes and mordants, page 13, lower left column, line 1 to page 14, lower left column, line 9 11. Development processing method JP-A-2-103037, page 16, upper right column, line 7 to page 19, lower left column, line 15 and JP-A-2-115837, page 3, lower right column, line 5 to 6 Top right column, line 10

In the present invention, a developing process for forming a silver image (black and white photographic process) is applied. When using an automatic processor,
This black-and-white processing is usually development, fixing, washing with water (or stabilization)
And drying steps. A combination of a dihydroxybenzene and a 1-phenyl-3-pyrazolidone or an aminophenol-based developing agent is most preferable for the developing agent used in the developing solution used in the present invention because good performance is easily obtained.

Examples of the dihydroxybenzene developing agent used in the present invention include hydroquinone, chlorohydroquinone,
Bromhydroquinone, 2,3-dibromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone,
There are 2,5-dimethylhydroquinone and the like, and hydroquinone is particularly preferable.

The developing agents for 1-phenyl-3-pyrazolidone or its derivatives used in the present invention include 1-phenyl-4,4-dimethyl-3-pyrazolidone and 1-phenyl-4-methyl-4-hydroxymethyl-3. -Pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3
-Such as pyrazolidone. Examples of the p-aminophenol-based developing agent used in the present invention include N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol and N- (4-hydroxyphenyl) glycine. , 2-methyl-p-aminophenol, p-benzylaminophenol, etc.,
Of these, N-methyl-p-aminophenol is preferable.

The developing agent is usually 0.01 mol / liter to
It is preferably used in an amount of 1.2 mol / l.
As a preservative of sulfite used in the present invention, sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite,
Formaldehyde sodium bisulfite and the like. The sulfite content is preferably 0.2 mol / liter or more, more preferably 0.4 mol / liter or more. The upper limit is preferably 1.2 mol / liter.

The pH of the developer used in the present invention is 9 to 13.
The range of up to is preferable. More preferably pH 1
The range is from 0 to 12. The alkaline agents used to set the pH are sodium hydroxide, potassium hydroxide,
Includes pH adjusting agents such as sodium carbonate, potassium carbonate, sodium triphosphate, potassium triphosphate.

Buffers such as JP-A-62-186259 (borate), JP-A-60-93433 (for example, saccharose, acetoxime, 5-sulfosalicylic acid), phosphate and carbonate are used. Good. As additives used in addition to the above components, development inhibitors such as sodium bromide, potassium bromide, potassium iodide: ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dimethylformamide, methyl cellosolve, hexylene. Organic solvent such as glycol, ethanol, methanol: 1-phenyl-5
-A mercapto compound such as mercaptotetrazole and 2-mercaptobenzimidazole-5-sulfonic acid sodium salt, an indazole compound such as 5-nitroindazole, and an antifoggant such as a benztriazole compound of 5-methylbenztriazole If desired, it may further contain a toning agent, a surfactant, an antifoaming agent, a water softening agent, an amino compound described in JP-A-2-208652 and the like.

Further, the compounds described in JP-B-62-62333 and JP-A-3-51844 can be used. In the present invention, a silver stain preventing agent such as the compounds described in JP-A-56-24347 can be used in the developer. The developing solution of the present invention is disclosed in JP-A-56-10624.
Amino compounds such as alkanolamines described in No. 4 can be used.

In addition, L. F. A. Mason, "Photographic Processing, Chemistry," Focal
Those described in Press, pp. 226-229, U.S. Pat. Nos. 2,193,015, 2,592,364, and JP-A-48-64933 may be used. The fixer is an aqueous solution containing thiosulfate and has a pH of
It has 3.8 or more, preferably 4.2 to 5.5. The pH is more preferably 4.65-5.5.

Examples of the fixing agent include sodium thiosulfate and ammonium thiosulfate, which contain thiosulfate ion and ammonium ion as essential components, and ammonium thiosulfate is particularly preferable from the viewpoint of fixing speed. The amount of the fixing agent used can be appropriately changed and is generally about 0.1 to about 6 mol / liter. The fixer may contain water-soluble aluminum salts which act as hardeners, such as aluminum chloride, aluminum sulphate, potassium alum and the like.

Tartaric acid, citric acid or their derivatives may be used alone or in combination of two or more in the fixing solution. It is effective that these compounds contain 0.005 mol or more per liter of the fixer, and particularly 0.01 mol / liter to 0.03 mol / liter is particularly effective. Specifically, tartaric acid, potassium tartrate, sodium tartrate, potassium sodium tartrate, citric acid, sodium citrate, potassium citrate, lithium citrate,
Examples include ammonium citrate.

Preservatives (eg, sulfite, bisulfite), pH buffers (eg, acetic acid, boric acid), pH adjusters (eg, sulfuric acid), chelating agents capable of softening water by water are included in the fixing solution, if desired. And compounds described in Japanese Patent Application No. 60-218562. Most preferably, the fixer concentrate is made up of one agent when the fixer concentrate is replenished to the automatic processor by the method of the present invention as the light-sensitive material is processed along with water to dilute it.

The fixing solution developer can exist stably as one agent at a pH of 4.5 or higher, and more preferably at a pH of 4.
It is 65 or more. This is because if the pH is less than 4.5, the thiosulfate is decomposed and finally sulfided, especially when the fixing solution is left for many years until it is actually used. Therefore, when the pH is in the range of 4.5 or higher, the generation of sulfurous acid gas is small and the working environment is improved. The upper limit of the pH is not so severe, but if the pH is fixed at an excessively high pH, the pH of the membrane becomes high even after washing with water, the swelling of the membrane becomes large, and the drying load becomes large. In a fixing solution for hardening a film using an aluminum salt, the pH for preventing precipitation of the aluminum salt is up to 5.5.

The present invention may be a so-called working solution in which either the developing solution or the fixing solution does not require the above-mentioned dilution water (that is, it is replenished as a stock solution as it is). The supply amount of each concentrated liquid to the treatment tank liquid and the mixing ratio with the diluting water can be variously changed depending on the composition of the concentrating liquid, but the diluting water for the concentrated liquid is generally in a ratio of 1 to 0-8. is there.

In the present invention, the light-sensitive material is developed and fixed, and then washed with water or stabilized. For the washing or stabilizing treatment, any method known in the art can be applied, and water containing various additives known in the art can also be used as washing water or a stabilizing solution. By using anti-mildew water as washing water or stabilizing solution, it is possible not only to save water by replenishing less than 3 liters per 1 m ^{2 of} light-sensitive material, but also to eliminate the need for automatic machine piping. Furthermore, the stock tank can be reduced. That is, the preparation diluting water for the developing solution and the fixing solution and the washing water or the stabilizing solution can be supplied from the common one stock tank, and the automatic developing machine can be made more compact.

When the water treated with antifungal means is used together with the washing water or the stabilizing solution, the generation of scale can be effectively prevented.
0 to 3 liters, preferably 0 to 3 per 1 m ^{2 of the} light-sensitive material
It can save 1 liter of water. Here, when the amount of replenishment is 0, the replenishment amount is 0, that is, the replenishment water is not replenished at all, except that the amount of the wash water in the water wash tank reduced by natural evaporation or the like is appropriately replenished. It refers to the case where a processing method is performed.

As a method of reducing the replenishment amount, a multi-stage countercurrent system (for example, 2 stages, 3 stages, etc.) has been known for a long time. If this multi-stage countercurrent system is applied to the present invention, the photosensitive material after fixing is gradually processed in a clean direction, that is, the processing solution which is not contaminated with the fixing solution is sequentially contacted and processed.
Further efficient water washing is performed. According to this, unstable thiosulfate and the like are appropriately removed, the possibility of discoloration and fading is further reduced, and a more remarkable stabilizing effect is obtained. The amount of flush water is much smaller than before.

When washing with a small amount of washing water in the method of the present invention, it is more preferable to provide the squeeze roller washing tank described in Japanese Patent Application No. 60-172968. Further, a part or all of the overflow liquid from the washing or stabilizing bath produced by supplementing the washing or stabilizing bath with antifungal water depending on the treatment is disclosed in JP-A-60-2351.
As described in No. 33, it can also be used for a processing solution having a fixing ability which is a processing step before that. This is more preferable because the stock water can be saved and the waste liquid can be reduced.

As a mildew-proofing means, there is disclosed in JP-A-60-2639.
Ultraviolet irradiation method described in No. 39, 60-263940
Using the magnetic field described in No. 61-131632
Method to make pure water using the ion exchange resin described in No.
Japanese Patent Application Nos. 60-253807 and 60-295894
No. 61-63030 and No. 61-51396 can be used.

Furthermore, L. B. West “Water
Quality Criteria ”,“ Photo
Sci & Eng. , Vol. 9 No. 6 (19
65), M.A. W. Eachch "Microbilog
ical Growths in Motion-Pic
"Ture Processing", "SMPTE",
Journal Vol. 85, (1976), R.S.
O. Deegan, “Photo Processin”
g Wash Water Biocides ", J. Am.
Imaging Tech. Vol 10, No. 6
(1984) and JP-A-57-8542 and 57-5.
8143, 58-105145, 57-132
No. 146, No. 58-18631, No. 57-97530.
No. 57-157244 and the like, antibacterial agents, antifungal agents, surfactants and the like can also be used in combination.

Further, in the washing bath, R. T. Kreima
n J. Image, Tech10, (6) 242
(1984), isothiazoline compounds, R
ESEARCH DISCROSURE Volume 205,
Isothiazoline compounds described in Item 20526 (May, 1981), Vol. 228, Item.
22845 (April, 1983), isothiazoline compounds described in Japanese Patent Application No. 61-51396, and the like.
It can also be used together as e).

Further, specific examples of the antifungal agent include phenol, 4-chlorophenol, pentachlorophenol,
Cresol, o-phenylphenol, chlorophen,
Dichlorophen, formaldehyde, glutaraldehyde, chloroacetamide, p-hydroxybenzoic acid ester, 2- (4-thiazolyl) -benzimidazole, benzisothiazolin-3-one, dodecyl-benzyl-dimethylammonium chloride, N- (fluoro) Dichloromethylthio) -phthalimide, 2,4
4'-trichloro-2'-hydroxydiphenyl ether and the like.

In addition, as described in "Antibacterial and Antifungal Chemistry" by Hiroshi Horiguchi, Sankyo Publishing (Sho 57), "Antibacterial and Antifungal Technology Handbook", Japan Antibacterial and Antifungal Society, Gihodo (Showa 61) It may contain various chemicals. It is preferable that the water stored in the water stock tank after being subjected to the mildew proofing is used both as the diluting water for the stock solution of the processing solution such as the developing solution fixing solution and as the rinsing water because it requires a small space. However, it is also possible to separately store the preparation diluting water and the washing water (or the stabilizing solution) which have been subjected to the mildew-proofing method and store them in separate tanks, or to take only one of them directly from the tap water.

When stored separately in different tanks, various additives can be added to the washing water (or stabilizing bath) in addition to the antifungal means of the present invention. For example, a chelate compound having a chelate stability log K value with aluminum of 10 or more may be contained. These are effective in preventing whitening in the wash water when the fixing solution contains an aluminum compound as a hardening agent.

Specific examples of the chelating agent include ethylenediaminetetraacetic acid (log K-16.1, the same applies hereinafter), cyclohexanediaminetetraacetic acid (17.6), diaminopropanoltetraacetic acid (13.8), diethylenetriaminepentaacetic acid (18). .4), triethylenetetramine hexaacetic acid (1
9.7) and the like and their sodium salts, potassium salts, and ammonium salts, and the addition amount thereof is preferably 0.01.
It is -10 g / liter, more preferably 0.1-5 g / liter.

Further, JP-A-58-434542 and JP-A-58-434542.
It is also possible to include a silver image stabilizer as described in JP-A-114035 and JP-A-61-83534 in the wash water. Further, various surfactants can be added to the wash water of the present invention for the purpose of preventing unevenness of water droplets. As the surfactant, any of cation type, anion type, nonionic type and amphoteric type may be used. Specific examples of the surfactant include compounds described in "Surfactant Handbook" published by Engineering Book Co., Ltd.

Various compounds are added to the stabilizing bath for the purpose of stabilizing the image. For example, various buffer agents (eg borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, mono) for adjusting the membrane pH (eg pH 3 to 8). Representative examples thereof include carboxylic acids, dicarboxylic acids, polycarboxylic acids and the like) and aldehydes such as formalin. Others, chelating agents, bactericides (thiazole-based, isothiazole-based, halogenated phenols, sulfonylamides, benzotriazole, etc.),
Various additives such as a surfactant, an optical brightener and a hardening agent may be used, and two or more kinds of the same or different target compounds may be used in combination.

Further, it is preferable to add various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate as a film pH adjusting agent for the processor in order to improve the image storability. The developing processing apparatus (automatic developing machine) used in the present invention is disclosed in JP-A-63-163456.
As a substance for adsorbing a sensitizing dye as described in JP-A-3-25436, it is preferable to use a porous organic synthetic resin having no ion exchange group, and it is possible to reduce the amount of replenisher, especially replenisher of fixer. it can.

The porous organic synthetic resin having no ion-exchange group (hereinafter, simply referred to as a porous resin) used in the present invention includes 1) a macrobore having an average pore diameter of 500 nm or less, and 2) a quaternary amine. Organic synthetic resins which do not have functional groups such as groups, carboxy groups, and sulfonic acid groups that dissociate into positive and negative ions. Its specific surface area is 0.
1 m ² / g or more is preferable, 500 to 1000 m ² / g
Is more preferable.

Specifically, this porous resin is: 1) styrene-divinylbenzene copolymer 2) chloromethylstyrene-divinylbenzene copolymer 3) methoxymethylol-divinylbenzene copolymer 4) ethylene-divinylbenzene copolymer Combined Methyl Methacrylate-Divinylbenzene Copolymer 5) Methyl Methacrylate-Divinylbenzene Copolymer 6) Methyl Acrylate-Divinylbenzene Copolymer The method for synthesizing the porous resin is described in Hojo “Chelate Resin / Ion Exchange Resin” Chapter 2 ( Although a method of adding a linear polymer, a method of adding a precipitant, etc. are known as described in (p. 127 et seq.), The method is not limited to these, and any method may be used for synthesis.

A part of the above porous resin is commercially available and can be easily obtained according to the intended use. Next, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

[0061]

【Example】

Example 1 Preparation of tabular silver halide grain emulsion 4.5 g potassium bromide and 2 gelatin in 1 liter of water.
0.6 g, thioether HO (CH ₂ ) ₂ S (CH ₂ )
₂ 5% aqueous solution of S (CH ₂ ) ₂ OH ( _2.5 cc) was added, and the solution was stirred into a container kept at 60 ° C. while stirring silver nitrate aqueous solution 3
7 cc (3.43 g of silver nitrate) and 2.97 g of potassium bromide
And an aqueous solution containing 0.363 g of potassium iodide and 33 cc were added by the double jet method in 37 seconds. Then, an aqueous solution of 0.9 g of potassium bromide was added, and the temperature was raised to 70 ° C. to give 53 cc of an aqueous silver nitrate solution (4.90 g of silver nitrate).
Added over minutes. Here, 15 cc of 25% aqueous ammonia solution was added, and after physically aging for 20 minutes at that temperature, 14 cc of 100% acetic acid solution was added. Subsequently, an aqueous solution of 133.3 g of silver nitrate and an aqueous solution of potassium bromide were added by the control double jet method over 35 minutes while keeping the pAg at 8.5. Next, 10 cc of 2N potassium thiocyanate solution was added. After physically aging for 5 minutes at the same temperature, the temperature was lowered to 35 ° C. Thus, the total silver iodide content was 0.26 mol%, the average projected area diameter was 1.10 μm, the thickness was 0.165 μm, and the diameter variation coefficient was 1.
A monodisperse emulsion containing 8.5% tabular silver halide grains was obtained.

After that, soluble salts were removed by a sedimentation method. The temperature was again raised to 40 ° C., 30 g of gelatin, 2.35 g of phenoxyethanol and 0.8 g of sodium polystyrene sulfonate as a thickener were added, and pH was adjusted to 5.90 and pAg was adjusted to 8.25 with caustic soda and silver nitrate solution. This emulsion was chemically sensitized while being kept at 56 ° C. with stirring.

First, 0.043 mg of thiourea dioxide was added and held for 22 minutes as it was for reduction sensitization. Next, 20 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene and the sensitizing dye shown below

[0064]

[Chemical 1]

400 mg of was added. Further, 0.83 g of calcium chloride was added. Successively thereto, 1.3 mg of sodium thiosulfate and the selenium compound-1 shown below.
2.7 mg, 2.6 mg of chloroauric acid, and 90 mg of potassium thiocyanate were added, and 40 minutes later, the mixture was cooled to 35 ° C. Thus, preparation of tabular halogenated grain emulsion T-1 was completed. Selenium compound-1

[0066]

[Chemical 2]

Preparation of Coating Sample Coating sample 1 was prepared by adding the following chemicals to 1 mol of silver halide of emulsion T-1 to prepare a coating solution. Gelatin (including gelatin in emulsion) 65.6 g Trimethylolpropane 9 g Dextran (average molecular weight 39,000) 18.5 g Sodium polystyrene sulfonate (average molecular weight 600,000) 1.8 g Hardener 1,2-bis (Vinylsulfonylacetamide) ethane Addition amount is adjusted so that the swelling rate is 230%. Compound (A) 34 mg shown below Compound (B) shown below 4.8 g

[0068]

[Chemical 3]

[0069]

[Chemical 4]

The coating solution for the surface protective layer was prepared and prepared so that each component had the following coating amount. Coating liquid for surface protective layer Coating amount Gelatin 0.966 g / m ² Polyacrylic acid acrylate (average molecular weight 400,000) 0.023 g / m ² 4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 0.015 g / m ² following compound (C) 0.013g / m ² following compound (D) 0.045g / m ² following compound (E) 0.0065g / m ² following compounds ( F) 0.003 g / m ² Compound (G) shown below 0.001 g / m ²

[0071]

[Chemical 5]

[0072]

[Chemical 6]

[0073]

[Chemical 7]

[0074]

[Chemical 8]

[0075]

[Chemical 9]

[0076] Polymethyl methacrylate (average particle size 3.7μm) 0.087g / m ² Proxel (adjusted to pH7.4 with NaOH) 0.0005g / m ² subbing layer for dye dispersion D-1 of the following preparation The dye was ball milled by the method described in JP-A-63-197943.

[0077]

[Chemical 10]

434 ml of water and Triton X-2
6.7% of 00 surfactant (TX-200) (trade name)
791 ml of the aqueous solution was placed in a 2 liter ball mill. 20 g of dye were added to this solution. 400 ml of zirconium oxide (ZrO) beads (2 mm diameter) were added and the contents were crushed for 4 days. After this, 160 g of 12.5% gelatin was added. After defoaming, ZrO is filtered.
The beads were removed. Observing the obtained dye dispersion, the particle size of the crushed dye was 0.05 to 1.15μ in diameter.
It has a wide field up to m and has an average particle size of 0.37
was μm.

Further, a centrifugation operation was performed to remove dye particles having a size of 0.9 μm or more. Thus, Dye Dispersion D-1 was obtained. Preparation of Support Corona discharge treatment was performed on a polyethylene terephthalate film having a thickness of 183 μm that was biaxially stretched, and a first undercoat liquid having the following composition was applied to a wire bar coater so that the applied amount was 5.1 cc / m ^2. Applied by 175
It was dried at ° C for 1 minute.

Next, a first undercoat layer was similarly provided on the opposite surface. The polyethylene terephthalate used was one containing 0.04 wt% of the dye having the following structure.

[0081]

[Chemical 11]

First Undercoat Liquid Composition Butadiene-styrene copolymer latex solution ^* (solid content 40% butadiene / styrene weight ratio = 31/69) 79 cc 2,4-dichloro-6-hydroxy-s-triazine sodium salt 4% solution 20.5 cc distilled water 900.5 cc (* Latex solution contains the following emulsion dispersant in an amount of 0.4% by weight based on the latex solids)

[0083]

[Chemical 12]

On the first undercoat layer on both sides, a second undercoat layer having the following composition was applied on each side so that the coating amount was as described below. Coated and dried at ℃. Second undercoat liquid composition Gelatin 160 mg / m ² Dye dispersion D-1 (26 mg / m ² as dye solid content) Matting agent Polymethylmethacrylate having an average particle size of 2.5 μm 2.5 mg / m ² Compound ( H) 8 mg / m ² Compound (I) shown below 0.27 mg / m ²

[0085]

[Chemical 13]

[0086]

[Chemical 14]

Preparation of photographic material On the support prepared as described above, the above emulsion and the coating solution for the surface protective layer were coated on both sides by the simultaneous extrusion method. The coated silver amount per one side was 1.75 g / m ² . The film thus obtained is referred to as film A. (Aspect ratio 6.7 swelling percentage 230%) Similarly, as a comparative example, a film adjusted to have an aspect ratio of 3.0 swelling percentage 230% is designated as film B. Further, as a comparative example, a film adjusted to have an aspect ratio of 6.7 and a swelling percentage of 280% is referred to as film C. Processing Automatic processor, Fuji Photo Film Co., Ltd., CEPRO
Experiments were conducted for a total processing time of 30 seconds by modifying the drive motor and gear of the SM and adjusting the transfer speed. The processing temperature was 35 ° C., and the developer formulation used was the developer replenishers V and W as shown in Table A below. As the fixing solution, CE-F1 manufactured by Fuji Photo Film Co., Ltd. was used.

[0088]

[Table 1]

When processing with an automatic processor, KBr4.0 as a starter per 1 V of developer replenisher V at the start.
g and 6.0 g of acetic acid were added, and the photographic characteristics of the new solution were examined. Furthermore, Fujifilm direct doctor Xray ortho film super H
A running experiment was performed using RS. Further, the minimum replenisher required for the automatic developing machine CEPROS-M used in this experiment was previously set to 1 liter. In Experiment 1, a film of 2.0 m ² was processed every day and 500 ml (1 m
⁽ 250 ml per ² ) was replenished and repeated for 1 month. In Experiment 2, a film of 2.0 m ² was processed every day and 500 ml was replenished, and when the automatic developing machine was restarted the next day, 500 ml of deficit to the replenishment amount, which was defined as 1 liter per day, was added by the developer replenisher V and repeated for 1 month. .. Similarly, in Experiment 3, a film of 2.0 m ² was processed every day and 500 ml was replenished, and when the automatic developing machine was restarted the next day, 500 ml of deficit to the replenishment amount of 1 liter per day was added by the developer replenisher W for one month. Repeated. In Experiment 4, 2.0 m ² of film was processed every day, and 1 liter (500 ml per 1 m ² ) was replenished and repeated for 1 month.
As Experiment 5, 2.10 m ² of film every day.
It was replenished with 5 liters (250 ml per 1 m ² ) and repeated for 1 month. In Experiment 6, 5.0 liters (500 ml per 1 m ² ) of 10.0 m ² film was replenished daily for 1
Repeated for a month. The results obtained are shown in Table B.

[0090]

[Table 2]

[0091]

[Table 3]

[0092]

[Table 4]

Here, the sensitivity means the film A and the developing replenisher V.
Using a new solution added with a starter, the reciprocal of the exposure amount required to obtain a fog plus blackening density of 1.0 at a total processing time of 30 seconds was set to 100 and shown as a relative value. Dmax means a value obtained by subtracting the fog value from the blackening density obtained at an exposure amount 20 times the exposure amount giving a fog plus blackening density of 1.0. The dryness was evaluated organoleptically by the tentacles immediately after the treatment. O indicates that the drying was sufficiently performed and was satisfactory, Δ indicates that it was slightly unsatisfactory, and x indicates that it was not dried.

As is clear from the results of Table B, as in the case of the processing method experiments 2, 3 and 5 of the present invention, 250 ml per 1 m ² of the light-sensitive material was replenished, and this automatic developing machine was replenished per day. In Experiments 2 and 3 in which the required minimum replenishment amount was 1 liter, when the replenishment was performed, the photographic characteristics in which the sensitivity Dmax was the same as that of the fresh solution were obtained even after one month. 250 ml per 1 m ² daily 2 m ²
In the case of Experiment 1 in which the treatment was performed as it was, the decrease in sensitivity Dmax was remarkable after one month. On the other hand, 500m per 1m ²
In the case of Experiment 4 in which 1 liter was replenished per day and 1 liter per day, the photographic performance was stable after one month, but in Experiment 6 in which a large amount of film was processed, the sensitivity was high and the amount of waste liquid was large. Not preferable. After all 1m like the processing method of the present invention
Set a replenishment amount of 250 ml per ² to determine the minimum replenishment amount required per day, and if it is insufficient, the processing method of adding replenishing liquid is stable in photographic performance with a small amount of film processing amount and a small amount of waste liquid It is clear that can be achieved with.

In this example, Fuji Medical X-Ray film Super HR-S, Super HR-A, Super HR-C, Super HR-L, Super HR-H, MI
-NP, MI-NC Fuji image recording film LI-F
It should be noted that the same processing as in this example was obtained by performing development processing with M and LI-HM. Example 2 1. Preparation of silver halide emulsion 40 g of gelatin was dissolved in 1 liter of water, and 6 g of sodium chloride and 0.4 g of potassium bromide were placed in a container heated at 53 ° C.
g, and compound [I]

[0096]

[Chemical 15]

After 60 mg of was added, 600 ml of an aqueous solution containing 100 g of silver nitrate and 600 ml of an aqueous solution containing 56 g of potassium bromide and 7 g of sodium chloride were added by the double jet method to form a core portion of 20 mol% silver chloride. , Then 500 ml of an aqueous solution containing 100 g of silver nitrate
40 g of potassium bromide, 14 g of sodium chloride, and potassium hexachloroiridium (III) (10
^-7 mol / mol silver) 500 ml of an aqueous solution is added by the double jet method to form a shell portion of 40 mol% silver chloride, so-called core / shell type cubic monodisperse salt having an average particle size of 0.35μ. Silver bromide grains were prepared.

This emulsion was added with a desalting machine and 40 g of gelatin, and adjusted to pH 6.0 and pAg 8.5, 2 mg of triethylthiourea, 4 mg of chloroauric acid and 4-hydroxy-6-methyl-1,3,3a, 0.2 g of 7-tetrazaindene was added and chemical sensitization was performed at 60 ° C. 2. Preparation of emulsion coating solution A container in which 850 g of an emulsion was weighed was heated to 40 ° C, and additives were added by the following method to prepare an emulsion coating solution. (Formulation of emulsion coating solution) Emulsion 850 g Spectral sensitizing dye [II] 1.2 × 10 ⁻⁴ mol Supersensitizer [III] 0.8 × 10 ⁻³ mol Preservation improver [IV] 1 × 10 ^-3 mol Polyacrylamide (molecular weight 40,000) 7.5 g Trimethylolpropane 1.6 g Na polystyrene sulfonate 2.4 g Poly (ethyl acrylate / methacrylic acid) latex 16 g N, N'-ethylenebis- (vinylsulfoneacetamide) ) 1.2 g Spectral sensitizing dye [II]

[0099]

[Chemical 16]

Supersensitizer [III]

[0101]

[Chemical 17]

Storability improver [IV]

[0103]

[Chemical 18]

3. Preparation of Surface Protective Layer Coating Solution for Emulsion Layer The container was heated to 40 ° C., and additives were added in the following formulation to prepare a coating solution. (Formulation of coating solution for surface protective layer of emulsion layer) Gelatin 100 g Polyacrylamide (molecular weight 40,000) 10 g Sodium polystyrene sulfonate (molecular weight 600,000) 0.6 g N, N'-ethylenebis- (vinyl sulfone acetamide) 1. 5 g Polymethylmethacrylate fine particles (average particle size 2.0 μm) 2.2 g Sodium t-octylphenoxyethoxyethane sulfonate 1.2 g C ₁₆ H ₃₃ O— (CH ₂ CH ₂ O) ₁₀ —H 2.7 g Polyacrylic acid soda _{4 g C 8 F 17 SO 3} K 70 mg C 8 F 17 SO 2 N (C 3 H 7) (CH 2 CH 2 O) 4 (CH 2) 4 -SO 3 Na 70 mg NaOH (1N) 4 ml Methanol 60 ml Preparation of Back Layer Coating Liquid A container was heated to 40 ° C., and additives were added in the following formulation to prepare a back layer coating liquid. (Back layer coating liquid formulation) Gelatin 80 g Dye [V] 3.1 g Polystyrene sodium sulfonate 0.6 g Poly (ethyl acrylate / methacrylic acid) latex 15 g N, N'-ethylenebis- (vinyl sulfone acetamide) 4. 3g dye [V]

[0105]

[Chemical 19]

5. Preparation of Back Surface Protective Layer Coating Liquid A container was heated to 40 ° C., and additives were added in the following formulation to prepare a coating liquid. (Back surface protective layer coating liquid formulation) Gelatin 80 g Polystyrene sodium sulfonate 0.3 g N, N'-ethylenebis- (vinylsulfonacetamide) 1.7 g Polymethylmethacrylate fine particles 4 g (Average particle size 4.0 μm) t- octyl phenoxy ethoxy ethanesulfonic acid sodium 3.6g NaOH (1N) 6 ml poly (sodium acrylate) _{2 g C 16 H 33 O- (} CH 2 CH 2 O) 10 -H 3.6g C 8 F 17 SO 3 K _{50 mg C 8 F 17 SO 2} N (C 3 H 7) (CH 2 CH 2 O) 4 (CH 2) 4 -SO 3 Na 50 mg methanol 130 ml 6. Preparation of Coating Sample The coating solution for the back layer described above was coated together with the coating solution for the surface protective layer of the back layer on the side of the polyethylene terephthalate support so that the total coating amount of gelatin was 3 g / m ² . Subsequently, the emulsion coating solution and the surface protective layer coating solution described above were applied to the opposite side of the support so that the coating Ag amount was 2.5 g / m ² and the gelatin coating amount of the surface protective layer was 1 g / m ² . It was applied so that 7. Developer composition potassium hydroxide 24 g sodium sulfite 40 g potassium sulfite 50 g diethylenetriaminepentaacetic acid 2.4 g boric acid 10 g hydroquinone 35 g diethylene glycol 11 g 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 6 g 5-Methylbenzotriazole 60 mg Potassium bromide 3 g Acetic acid 1.8 g 2,3,5,6,7,8-Hexahydro-2-thioxo-4 (1H) quinazolinone 0.18 g 2-mercaptobenzimidazole-5 -Sulfonic acid 0.28 g Add water to adjust to 1000 ml pH 10.5 8. Fixer composition Ammonium thiosulfate 140 g Sodium sulfite 15 g Ethylenediaminetetraacetic acid disodium dihydrate 25 mg Sodium hydroxide 6 g Add water to adjust to 1000 ml pH 5.00 Next, the automatic developing machine is FPM-2000 (Fuji 30 seconds processing (dry to dry)
Then, development processing was performed using the above-mentioned coated sample.

The coated sample was kept at 25 ° C. and 60% temperature and humidity and left for 7 days after coating, and subjected to scanning exposure for 10 ⁻⁷ seconds using a semiconductor laser of 780 nm at room temperature.
The development temperature is 35 ° C, the fixing temperature is 32 ° C, and the replenishment amount is B4.
50ml and 25m per size (0.0935m ² ).
1, fixing solution was set to 25 liters, and the number of processed sheets per day was 10, 20, 50, 100, respectively.
Development processing was carried out for 0 days. The operating time per day of the automatic processing machine was set to 8 hours. Regarding the replenishment amount of 25 ml,
The necessary minimum replenishment system of the present invention was adopted, and the replenishment amount was 1250 ml per day. Table C shows the photographic results. The fog value in the photographic properties was measured as a net increase in density with the base density corrected. The gradation G bar is represented by the slope of a straight line connecting the density point of fog +0.25 and the density point of fog +2.00. The sensitivity was obtained as a relative value of the reciprocal of the exposure amount required to obtain a blackened density of fog + 1.0. Dm represents the maximum density.

[0108]

[Table 5]

[0109]

[Table 6]

From the results of Table C, the following can be said. Test No. 1 with a small number of processed sheets per day In Nos. 1 and 2, since the deterioration of the developing solution was large, the photographic property was largely deteriorated, and the performance was not practically usable. Test No. with reduced replenishment amount.
The results of 5 and 6 are similar. In addition, the test No. of the present invention.
In Nos. 6 and 8, the total replenishment amount increases, but the photographic properties are stable, and the performance is satisfactory. In addition, since the photographic properties are stable, the frequency of exchanging liquid in the developing machine developing tank is low,
It can be said to be an advantageous method in the long term. Next, the test No. with many processed sheets per day. Nos. 3 and 4 have stable photographic properties and there is no problem. Similarly, in Test Nos. 9 and 10 of the present invention, the photographic property is not a problem, but the total replenishment amount is halved, the cost is reduced, and the amount of waste liquid is reduced, which is an advantageous method.

[0111]

According to the present invention, a black and white silver halide photographic light-sensitive material can be processed with an automatic processor using a small amount of replenisher to obtain stable photographic performance.

Claims (9)

[Claims] 1. A method of processing a silver halide photographic light-sensitive material, which comprises processing a black-and-white silver halide photographic light-sensitive material with an automatic processor while replenishing a replenisher, wherein the silver halide photographic material is 1 m
Replenish the automatic developing machine with a predetermined minimum amount of replenisher per unit time at a rate of 400 ml or less per ² times, and when a shortage occurs with this amount, supplement the shortage replenisher separately. A method for processing a silver halide photographic light-sensitive material, comprising: 2. A black-and-white silver halide photographic light-sensitive material is an X-ray silver halide light-sensitive material containing silver halide grains having an aspect ratio of 4 or more and having a swelling ratio of 250% or less. The method for processing a silver halide photographic light-sensitive material according to claim 1. 3. A black and white silver halide photographic light-sensitive material is 600.
2. The method for processing a silver halide photographic light-sensitive material according to claim 1, which is a silver halide photographic light-sensitive material for a medical laser imager having a light-sensitive area in the range of ˜850 nm. 4. The method of processing a silver halide photographic light-sensitive material according to claim 1, wherein the unit time is defined as one day and the minimum replenishment amount required for the automatic processor is set. 5. An opening area of a developing tank of an automatic processor is 5
The processing method for a silver halide photographic light-sensitive material according to claim 1, wherein the processing length is 00 cm ² or less. 6. The method of processing a silver halide light-sensitive material according to claim 1, wherein the bromine ion concentration of the replenishing solution is lower than that of the fresh solution at the start and the pH is higher. 7. The method of processing a silver halide light-sensitive material according to claim 1, wherein the fresh solution and the replenishing solution at the start contain an organic antifoggant. 8. The replenisher solution to be replenished due to lack of a predetermined minimum replenishment amount per unit time has a higher hydroquinone concentration than the fresh solution at the start, and the bromine ion concentration is substantially the same. The method for processing a silver halide light-sensitive material according to claim 1. 9. When the automatic developing machine is stopped for a long time exceeding a predetermined unit time, the minimum replenishment amount required increases according to the length of time, and it is calculated and summarized when the automatic developing machine is restarted. The method of processing a silver halide photographic material according to claim 1, wherein the replenishment is performed by replenishing.