JPH0564782B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a method for developing photographic materials, and more particularly to a method for developing photographic materials using an automatic processor that can prevent limescale from forming in the washing water during the washing step. (Prior Art) For example, photographic light-sensitive materials for X-rays and photographic light-sensitive materials for printing are often processed with an automatic processor when they are developed after exposure. That is, the image is developed in a developing tank, a fixing tank, a washing tank, etc. through the steps of development, fixing, washing, and drying. When developing using such an automatic developing machine, it is usually desirable to drain the water from the washing tank at the end of each day's work. (Problems to be solved by the invention) However, for example, in an emergency designated hospital,
In facilities that perform line photography and require the results, it is necessary to keep an automatic processor always ready for processing (standby). In such cases, the flushing water cannot be extracted,
Must be used continuously. If the washing water is not drained for a long time, limescale will form inside the washing tank, causing various problems. That is, when photographic film is processed, limescale adheres to the surface of the film, making it difficult to take photographs.Also, when the film passes through the washing tank, a slip phenomenon occurs in the washing rack, leading to transport failure accidents. In addition, the washing tank and washing rack become dirty, making cleaning difficult.Furthermore, if a solenoid valve is used in the water pipe, limescale may clog the solenoid valve, making it impossible to send washing water. Otherwise, various problems such as non-stop flow of washing water may occur. The same thing applies to the development processing of photosensitive materials for printing using automatic processing machines; if the washing water is left in the washing tank and carried over to the next day, water scale accumulates, staining the rack and adhering to the film surface. Accidents happen. However, the management of draining the washing water every day is troublesome as described above, and problems also remain in terms of workability and water economy, as if the water is drained every day, development cannot be done immediately the next morning. Limescale is mainly composed of filamentous bacteria,
Suspended substances in the water adhere to it, forming a so-called null shape. Therefore, by sterilizing the filamentous bacteria that play a central role, the formation of limescale can be prevented. Several methods have been proposed for sterilization, but they have the following drawbacks. When chlorine or sodium hypochlorite (hereinafter referred to as chlorine, etc.) is used as a disinfectant, the accumulation of chlorine ions may adversely affect the photographic performance of developed film (in the case of sodium hypochlorite, In particular, the drying properties of the film become worse), as well as
The following inconvenience also occurs. That is, since the existing washing tank is made of iron plates, there is a problem in that when chlorine or the like is used, the tank corrodes, making it impossible to use chlorine or the like as a disinfectant for a long period of time. Therefore, it may be possible to modify the tank with a material that is corrosion resistant, but in that case, the cost of modification would be considerable. Therefore, it is desirable to use a non-corrosive disinfectant so that existing equipment can be used as is.
There is also the issue of water pollution regulations. Furthermore, when cresol is used as a disinfectant, there are problems in handling such as the odor of the chemical itself and safety, so it cannot be said to be perfect (Japanese Patent Application Laid-Open No. 59-91440). The present invention was made to solve the problems peculiar to the above-mentioned processing of photographic materials using an automatic processor, and its purpose is to prevent limescale from forming in the washing water during the washing process. The present invention provides a method for developing photographic materials. Other objects of the invention will become apparent from the description below. (Means for Solving the Problems) The above object is to develop a black and white silver halide photographic material using an automatic processor, in which the fixing solution in the fixing step contains a water-soluble aluminum compound, and the automatic developing When the machine is stopped and the washing water in the washing process is not replenished, the washing water in the washing water tank contains at least one of aminopolycarboxylic acids and phosphonic acids.
It has been found that this can be achieved by a method for developing black and white silver halide photographic materials characterized by containing 0.02 g or more per silver halide photographic material. The state in which the automatic developing machine is stopped is not the so-called standby state. In other words, it refers to a state in which heat-up has not occurred after the day's development work has been completed, and development cannot actually be performed. Specific compounds as aminopolycarboxylic acids in the present invention include ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid,
Ethylenediamine-N-(β-oxyethyl)-
N,N',N'-triacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, alkyliminodiacetic acid, dihydroxyethylglycine, ethyl etherdiaminetetraacetic acid, glycol etherdiaminetetraacetic acid, Ethylenediaminetetrapropionic acid, phenylenediaminetetraacetic acid, 1,3-diamino-2-propanoltetraacetic acid, triethylenetetraminehexaacetic acid, hydroxyethyliminoacetic acid, oxybis(ethyleneoxynitrilo)tetraacetic acid, malic acid,
and sodium salts of these polycarboxylic acids,
It is a potassium salt. Specific examples of compounds as the phosphonic acids in the present invention include compounds represented by the following general formulas () to ().

[Table] In the formula, R ₁ to _{R 6} are hydrogen atoms, hydroxyl groups,
Alkyl groups (1 to 3 carbon atoms, e.g. methyl, ethyl, propyl, etc.), amino groups, alkoxy groups (1 to 3 carbon atoms, e.g. methoxy, ethoxy, etc.), alkylamino groups (preferably,
carbon number 1-3), arylamino group (preferably,
carbon number 6-8), and an aryloxy group (preferably carbon number 6-8). R ₇ to _{R 13} are hydrogen atoms, hydroxyl groups, -
COOM, -PO ₃ M ₂ , alkyl group (1 to 3 carbon atoms,
For example, it represents a methyl group, an ethyl group, a propyl group, etc.). _R14 is a hydrogen atom, an alkyl group (1 to 1 carbon atoms)
M represents an alkali metal such as a sodium atom or a potassium atom. Specific compounds represented by the above general formulas () to () include the following.

[Table] ｜ ｜ ｜
OH OH OH

[Table] ｜
_CH2 COOH

【table】 / \
H ₂ O ₃ PCH ₂ | CH ₂ PO ₃ H ₂
CH ₂ PO ₃ H ₂
These compounds are preferably added in the form of sodium and/or potassium salts. Among these compounds, particularly preferred are ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid, ethylenediamine-Nhydroxyethyl-N,N',N'-triacetic acid, propylenediaminetetraacetic acid, triethylenetetraminehexaacetic acid, Examples include aminopolycarboxylic acids such as ethylenediaminetetramethylenephosphonic acid, and sodium salts, potassium salts, and ammonium salts of 1-hydroxyethylidene-1,1-diphosphonic acid. It is sufficient to use one type of the compounds of the present invention for the washing water, but two or more types may be used in combination. The compound of the present invention is preferably contained in an amount of 0.02 g to 20 g, more preferably 0.05 g to 5 g, per 1 g of washing water. Generally, the above aminopolycarboxylic acids and phosphonic acids are known as so-called chelating agents for metals. Therefore, these compounds are used in photographic developers to sequester Ca and Mg ions contained in water.
−Lon: Photographic Processing Chemistry
(Focal Library 1975) is well known and is currently commonly used. These compounds can be used as chelating agents in the fixer, but when aluminum salts are used as hardeners in the fixer, if the amount of these compounds is large, they will form chelates with the aluminum salts and reduce the hardening of the fixer. Since it weakens the film action, the amount added should be within a range that does not sacrifice the hardening performance, that is, usually a maximum of about 0.1 g. Furthermore, even if aluminum salt is not used, the fixing solution is usually used on the acidic side, so that precipitation of Ca and Mg ions contained in water does not occur.
The amount of the compound added as a chelating agent for these metal ions is small. Therefore, it is considered that the amount of the compound of the present invention that can be carried over from the fixing solution to the washing water by a photosensitive material will not exceed 1 mg/kg, no matter how much it is estimated. The amount of the compound used in the present invention far exceeds these ranges and is clearly distinguishable from conventional methods. Also, for example LEWest, Photo Sic.Eng,
Vol. 9, No. 6, 398 (1965) describes that the compound of the present invention is used as a chelating agent in water in the broadest sense of water used for photographic processing. There is no mention of intentional use. Furthermore, these compounds are used in combination with completely different compounds, especially in the field of color processing, to stabilize images during water-saving processing, and in the field of black-and-white processing, they are used in combination with sulfite ions to promote water washing. Although it is sometimes used in washing water (JP-A-57-132146, JP-A-58-18631, JP-A-57-97530, JP-A-57-
It is completely new that these compounds can be used as antibacterial agents in washing water. That's true. Therefore, this compound is a novel compound that cannot be considered under the conventional wisdom of antibacterial agents, and its mechanism of action is not clear at all. Here, in order to maintain the above concentration constant in the washing water used during the treatment, a very large amount of the compound of the present invention is required, and the cost thereof cannot be ignored. However, the compound of the present invention can be added to the above concentration only when the automatic processor has stopped and the washing water has not been replenished, i.e. after the day's development work has been completed (usually at night). It has been found that the above object of the present invention can also be sufficiently achieved by adding it to the water washing tank. This allows further cost reduction. There are various methods for supplying the compound of the present invention to a washing tank, as described below. (1) During normal development processing, wash water that does not contain this compound is flushed out, a certain amount of this compound is added at the end of the day's development work, and the next day the development process is continued by replenishing only water. How to do it. The compound of the present invention may be added in the form of a powder or in the form of a solution. (2) A method of adding a powder or solution of the compound of the present invention using a device that automatically adds a certain amount of the powder or solution of the compound of the present invention into a water washing tank at the end of a day's development work in conjunction with the stop switch of an automatic processor. (3) A method in which the compound of the present invention is placed as a powder or as a solution in a container with fine holes and gradually eluted into washing water. In carrying out the present invention, the washing water to the washing tank is normally replenished at a flow rate of 3 or more ^{per m2} of photosensitive material during the development process, to prevent aluminum salts from the fixer from precipitating in the washing water. This is preferable in order to prevent water from becoming contaminated during treatment due to poor water flow. The washing water of the present invention preferably has a pH of 2 to 7, and more preferably has a pH of 3.5 to 5.5. In order to maintain this PH range, the chelating agent of the present invention can be added in the form of an appropriate sodium salt or potassium salt to maintain a suitable PH range, and an appropriate buffer salt can also be added. You can also do that. Moreover, the number of washing tanks is not limited to one, but can be two or more. When using two or more tanks, it is also possible to use so-called countercurrent washing to increase the efficiency of washing. Further, the antibacterial effect of the present invention is more preferably exhibited when the composition of the fixing solution, which is a pre-bath for the washing step, contains ammonium thiosulfate salt. Depending on the quality of the water used, the washing bath containing the chelating agent of the present invention may include LEWest “Water Quality
Criteria”Photo Sci&Eng.Vol.9No.6 (1965),
MWBeach“Microbiological Growths in
Motion−Picture Processing”SMPTE
Journal Vol85, (1976) R.O.Deegan, “Photo
processing Wash Water Biocides”J.Imaging
Tech.Vol10, No.6 (1984) and JP-A-57-8542
No. 57-58143, No. 58-105145, No. 57-
No. 132146, No. 58-18631, No. 57-97530, No. 132146, No. 58-18631, No. 57-97530, Akira
Antibacterial agents, anti-bacterial agents, surfactants, etc. described in No. 57-157244 and the like can also be used in combination. Furthermore, the water washing bath used in the present invention has RT
Kreiman, J. Image, Tech 10 , (6), 242 (1984)
isothiazoline compounds described in
RESEARCHDISCLOSURE Volume 205, Item 20526
(May issue, 1981), isothiazoline compounds listed in Vol. 228, Item 22845 (April issue, 1983) can also be used together as microbiocides. can. In addition, various surfactants that lower surface tension can be added to this washing bath in order to reduce squeezing unevenness, drying unevenness, etc. Any of nonionic, ionic, and amphoteric surfactants can be used, such as polyoxyalkylene derivatives, amphoteric amino acids (including sulfobetaines), and the like. Such surfactants are covered by U.S. patents.
No. 2600831, US Patent No. 2271622, US Patent
No. 2271623, U.S. Patent No. 2275727, U.S. Patent
No. 2787604, U.S. Patent No. 2816920, U.S. Patent
No. 2739891 and Belgian patent No. 652862. The amount of these additions is preferably 0.005g to 10g/
, more preferably 0.01g to 1g/. Activated carbon can be added to the washing bath or circulation filter to adsorb the processing agent components brought in from the previous bath in the washing water bath, thereby saving water and improving the washing efficiency. Further, the washing bath may contain an organic compound described in JP-A-58-43452 in order to improve the storage stability of the processed silver image. Processing of the image-exposed light-sensitive material in the method of the present invention is generally based on the following steps. (1) Development - Fixation - Washing - Drying (2) Development - Stopping - Fixing - Washing - Drying It is preferable from the viewpoint of speeding up the process that no special process is used between fixing and washing. . However, if necessary, a very short period of rinsing treatment, auxiliary water washing, a known washing promotion bath, etc. may be performed. According to the method of the invention, the developed and fixed photographic material is washed and dried. Washing with water is performed to almost completely remove silver salts dissolved during fixing.
Preferably, the temperature is about 20°C to about 50°C for 10 seconds to 2 minutes. Drying is carried out at a temperature of about 40℃ to about 100℃, and the drying time can be changed depending on the surrounding conditions, but it is usually about 5 seconds to 100℃.
2 minutes is enough. Next, the developer will be explained in detail. The developer contains, for example, the following dihydroxybenzenes as a developing agent. Hydroquinone Chlorohydroquinone Toluhydroquinone Bromohydroquinone Methylhydroquinone 2,5-dimethylhydroquinone 2,3-dichlorohydroquinone 2,5-dibenzoylaminohydroquinone 2,5-Diacetaminohydroquinone Next, the auxiliary developing agent used in the present invention is Examples of 3-pyrazolidone-based developing agents include 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, and 1-phenyl-4. -ethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3
-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone, and the like. Hydroquinones are usually used in an amount of 2g to 50g/, preferably 5g to 35g/, and 3-pyrazolidone developing agents are used in an amount of 0.1g to 3g/, preferably 0.2g/.
g to 2 g/ is used. Especially 1-phenyl-
3-pyrazolidone is preferably used because it has high developing activity. In addition, dialdehyde-based hardeners or their bisulfite adducts are sometimes used in the developer, and specific examples include glutaraldehyde,
α-Methylglutaraldehyde, β-methylglutaraldehyde, maleic dialdehyde, succinic dialdehyde, methoxysuccinic dialdehyde, methylsuccinic dialdehyde, α-methoxy-β-ethoxyglutaraldehyde, α-n-butoxyglutaraldehyde, α, Examples include α-dimethoxysuccinedialdehyde, β-isopropylsuccinedialdehyde, α,α-diethylsuccinedialdehyde, butylmaleindialdehyde, and bisulfite adducts thereof. The dialdehyde compound is used in an amount such that the sensitivity of the photographic layer being processed is not inhibited and the drying time is not significantly increased. Specifically, the amount is 1 to 50 g, preferably 3 to 10 g per developer. Among these, glutaraldehyde or its bisulfite adduct is most commonly used. The developer used in the present invention includes an indazole-based, benzimidazole-based, or benztriazole-based antifoggant, and specifically, 5-
Nitroindazole, 5-p-nitrobenzoylamino-indazole, 1-methyl-5-nitro-indazole, 6-nitroindazole, 3-
Methyl-5-nitro-indazole, 5-nitrobenzimidazole, 2-isopropyl-5-nitrobenzimidazole, 5-nitrobenztriazole, 4-(2-mercapto-1,3,4-
Examples include sodium thiadiazol-2-yl-thio)-butanesulfonate and 5-amino-1,3,4-thiadiazole-2-thiol. The amount of antifoggant contained in the developer of the present invention is usually 0.01 to 10 mmol per developer,
More preferably, it is 0.1 to 2 mmol. Further, specific examples of the sulfite and bisulfite used in the developer of the present invention include sodium sulfite, potassium sulfite, sodium bisulfite, and potassium bisulfite. Further, at this time, metabisulfite (eg, sodium metabisulfite, potassium metabisulfite, etc.) can be used. Furthermore, various organic and inorganic chelating agents can be used in combination in the developer of the present invention. As the inorganic chelating agent, sodium tetrapolyphosphate, sodium hexametaphosphate, etc. can be used. As the organic chelating agent, mainly organic carboxylic acids, aminopolycarboxylic acids, organic phosphonic acids, aminophosphonic acids, and organic phosphonocarboxylic acids can be used. Examples of organic carboxylic acids include acrylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, corkic acid, azuelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, and maleic acid. , itaconic acid, malic acid, citric acid, tartaric acid, etc., but are not limited to these. In addition, examples of aminopolycarboxylic acids include iminodiacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, ethylenediamine monohydroxyethyltriacetic acid, ethylenediaminetetraacetic acid, glycol ether diaminetetraacetic acid, hydroxyethyliminodiacetic acid, diaminopropanoltetraacetic acid, 1,2-diaminopropanetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, 1,3-diamino-2-propanoltetraacetic acid, glycol ether diaminetetraacetic acid, and others JP-A-52-25632
No. 55-67747, No. 57-102624, and the specification of Japanese Patent Publication No. 53-40900. As organic phosphonic acids, US Pat. No. 3,214,454,
3794591, and the hydroxyalkylidene diphosphonic acid described in West German Patent Publication No. 2227639, etc.
Research Disclosure Volume 181, Item 18170 (1979
The compounds described in May 2013) are well known. As aminophosphonic acids, aminotris (methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid, aminotrimethylenephosphonic acid, etc. are well known, but in addition to the above Research
Disclosure No. 18170, JP-A-57-208554, JP-A No. 54
-61125, No. 55-29883, No. 56-97347, etc. can be mentioned. As an organic phosphonocarboxylic acid, JP-A-52-
No. 102726, No. 53-42730, No. 54-121127, No.
No. 55-4024, No. 55-4025, No. 55-126241, No. 55-126241, No. 55-4025, No. 55-126241, No.
No. 55-65955, No. 55-65956, and the aforementioned
Examples include compounds described in Research Disclosure No. 18170 and the like. These chelating agents may be used in the form of alkali metal salts or ammonium salts. The amount of the chelating agent used in combination is preferably 1 x 10 ^-4 mol to 1 mol per developer.
×10 ^-1 mol, more preferably 1 × 10 ^-3 mol to 1 ×
10 ^-2 mol. In addition to the above-mentioned composition, the developer of the present invention may optionally contain a buffer (e.g., carbonate, boric acid, borate, alkanolamine), alkaline agent (e.g., hydroxide, carbonate), solubilizing agent (e.g. , polyethylene glycols, esters thereof), PH regulators (e.g., organic acids such as acetic acid), development accelerators (e.g., various types of agents typified by U.S. Pat. No. 2,648,604, Japanese Patent Publication No. 44-9503, and U.S. Pat. Pyrimidium compounds and other cationic compounds, cationic dyes such as phenosafranin, neutral salts such as thallium nitrate and potassium nitrate, Japanese Patent Publication No. 44-9304
No., U.S. Patent No. 2533990, U.S. Patent No. 2531832, U.S. Patent No.
Nonionic compounds such as polyethylene glycol and its derivatives, polythioethers, etc. described in No. 2950970 and No. 2577127, and organic solvents described in Japanese Patent Publication No. 44-9509 and Belgian Patent No. 682862 are also useful development accelerators. Also, thioether compounds described in US Pat. No. 3,201,242 may be used. Among these, thioether compounds are particularly preferred. ), surfactants, etc. can be contained. The developer further contains a silver colloid dispersant (for example, a mercapto compound), an antifoggant (for example, a halide such as potassium bromide and sodium bromide, and various known antifoggants in addition to the above-mentioned organic antifoggants). (inhibitor) may be included. The developer of the present invention prepared in this manner preferably has a pH of 9 to 13, more preferably PH of 9 to 12. The processing temperature and time are interrelated and determined in relation to the total processing time, but are generally from about 20 DEG C. to about 50 DEG C. and from 10 seconds to 2 minutes. On the other hand, the fixing solution contains thiosulfate and a water-soluble aluminum compound, and if necessary, tartaric acid, citric acid,
It is an aqueous solution containing salts of gluconic acid, boric acid, and these, and preferably has a pH of about 3.8 to about 7.0 (at 20°C).
In the method of the present invention, a stopping step may be provided after development, but the stopping step is generally omitted in roller conveyance type automatic developing machines. Therefore, the developer is brought into the fixer, and the pH of the fixer increases. In order to maintain high reactivity of the fixer containing aluminum compounds, the pH of the fixer should be approximately
It is desirable to adjust the temperature to 3.8 to 5.0 (20℃). The fixing agent includes sodium thiosulfate, ammonium thiosulfate, and the like, which contain thiosulfate ions and ammonium ions as essential components, and ammonium thiosulfate is particularly preferred from the viewpoint of fixing speed. The amount of fixative used can be varied and is generally about
0.1 to about 5 mol/. The water-soluble aluminum salt which mainly acts as a hardening agent in the fixing solution is a compound generally known as a hardening agent for acidic hardening fixing solutions, and includes, for example, aluminum chloride, aluminum sulfate, and potassium alum. The amount used is generally 10 ^-3 to 1 mol/
, preferably 10 ⁻² to 10 ⁻¹ mol/. Further, in order to stabilize the hardening agent, tartaric acid or its derivatives, citric acid or its derivatives can be used alone or in combination of two or more kinds.
It is effective to contain these compounds at 0.005 mol or more per fixer, especially 0.015 mol/~0.05
mol/ is particularly effective. The fixer may optionally contain a preservative (e.g., sulfite, bisulfite), a PH buffer (e.g., boric acid, borate), a PH adjuster (e.g., acetic acid), and a chelating agent (described above). can. The fixing temperature and time are the same as for developing.
Preferably, the temperature is about 20°C to about 50°C for 10 seconds to 2 minutes. A silver halide photographic material applicable to the method of the present invention comprises a support and at least one silver halide emulsion layer coated thereon. Further, the silver halide emulsion layer can be coated not only on one side of the support but also on both sides. Of course, a back layer, an antihalation layer, an intermediate layer, a top layer (for example, a protective layer), etc. can be included if necessary. Silver halide emulsions are silver halides such as silver chloride, silver iodide, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc., combined with hydrophilic colloids (e.g., gelatin,
modified gelatin, colloidal albumin, casein, carboxymethylcellulose, hydroxyethylcellulose, sodium alginate, polyvinyl alcohol, polyvinylpyrrolidone, or a mixture thereof). Silver halide emulsions are usually prepared by combining a water-soluble silver salt (e.g., silver nitrate) and a water-soluble halide salt by methods well known in the art (e.g., single-jet method, double-jet method, controlled-jet method, etc.). are mixed in the presence of water and hydrophilic colloids, and then subjected to physical ripening and chemical ripening such as gold sensitization and/or sulfur sensitization. The emulsions obtained in this way have cubic, octahedral, spherical, and other shapes.
Disclosure Volume 225, Item 22534 (January 1983 issue)
High aspect ratio tabular silver halide grains described in Japanese Patent Publication No. 41
It can also be used in combination with the internal latent image type silver halide grains and the surface latent image type silver halide grains described in JP-A-2068. Silver halide emulsions may contain spectral sensitizers (e.g. cyanine dyes,
merocyanine dyes or mixtures thereof), stabilizers (e.g. 4-hydroxy-6-methyl-1,3,
3a,7-tetrazaindene), sensitizers (e.g.
compounds described in U.S. Pat. No. 3,619,198), antifoggants (e.g., benzotriazole, 5-
nitrobenzimidazole, polyethylene oxide), hardening agents (e.g. formalin, glyoxal, mucochloric acid, 2-hydroxy-4,6
-dichloro-s-triazine), coating aids (e.g. saponin, sodium lauryl sulfate,
Dodecylphenol polyethylene oxide ether, hexadecyltrimethylammonium bromide), etc. can be added. The silver halide emulsion thus produced is coated and dried on a support such as cellulose acetate film or polyethylene terephthalate film by a dip method, an air knife method, or the like. The silver halide photographic material according to the present invention differs in silver halide composition, additives, type of support, etc. depending on its use, but the method of the present invention can be applied to medical or industrial X-ray photographic materials, Duplicate photographic materials for X-ray, photographic materials for medical CRT images, photosensitive materials for printing (e.g. scanner photosensitive materials, net photosensitive materials, line photosensitive materials, return photosensitive materials, etc.) general black and white negative photosensitive materials, black and white photographic paper, etc. Applicable to the washing water of automatic processor processing and tank processing. (Example) Next, the present invention will be specifically described based on an example. Examples 1 to 3 and Comparative Examples 1 to 5 After imagewise exposure of X-ray sensitive material RX manufactured by Fuji Photo Film Co., Ltd., an automatic processor FPM-4000 manufactured by the same company was used.
was filled with the following treatment solution and subjected to running treatment. Γ developer: RD- manufactured by the same company A specified amount of starter was added to fill the tank of an automatic developing machine, and thereafter, a replenisher was added to the tank at 45 ml per quarter cut. Γ Fixer: Composition Ammonium thiosulfate (70%wt/Vol) 200ml Sodium thiosulfate (anhydrous) 30g Sodium sulfite (anhydrous) 20g Boric acid 8g Ethylenediaminetetraacetic acid disodium dihydrate
0.05g Aluminum sulfate 15g Sulfuric acid 2g Glacial acetic acid 22g Adjusted to pH 4.20 with water 1 Replenishment volume: 60ml/4 cuts 1 sheet ΓWash Water Replenished at a rate of 3/min only when processing photosensitive materials. Four-cut size sheets were developed every day at a rate of 100 sheets/day. I didn't drain the water from the washing tank at all, just left it as it was and continued running. On the other hand, after one day's treatment was completed, 4% solutions of various compounds shown in Table 1 were added to the washing tank at a ratio of 80ml to 15.5ml of the washing tank, and the liquid was left overnight without draining, and the next day. Also, the washing process was carried out by running normal washing water. The results are shown in Table 1.

[Table] The compound of the present invention did not cause the growth of algae, making maintenance such as cleaning of an automatic processor easier. Example 4 A silver halide photosensitive material for plate making manufactured by Fuji Film Corporation was processed under the following conditions. Automatic processor FG-660F Developer solution FS-2 38℃, 20 seconds Fixer LF-405 (Fixer with ammonium thiosulfate as main ingredient) Rinse water Well water 4/min After 2 to 5 days, it will be added to the automatic processor's rinse tank. Water scale formed and the roller surface began to become slippery, and after another 1 to 1.5 months, a large amount of water scale was generated, and there were cases in which water scale sometimes adhered to the surface of the treated material and became dirty. Triethylene tetramine, one of the compounds of the present invention, N,N,N',N,N-hexaacetic acid,
After one day's treatment, we installed a washing water tank in which 10g of TTHA was added to the washing tank 20, and when we used it as washing water, no water scale was observed even after more than 3 months had passed, and automatic The washing tank of the developing machine was clean. Examples 5 and 6 and Comparative Examples 6 to 9 Running treatments were carried out using the methods described in Examples 1 to 3, with the fixer composition and water washing conditions changed as shown in Table 2. The fixer composition was the same as that used in Examples 1 to 3, except for the presence or absence of 15 g of aluminum sulfate. When using DTPA as a chelating agent in the washing water, add 60 g of diethylenetriaminepentaacetic acid to 1 part of water, adjust the pH to 4.4 with sodium hydroxide, and add 60 ml of the solution after stopping the automatic processor. The water was left unremoved until processing the next morning.

[Table] (Results of the invention) By using the method of the present invention, it is possible to effectively prevent the formation of limescale in the washing water in automatic processing, which eliminates the need to take the trouble to drain the water every day, and You can avoid problems such as the cost of installing a valve, and you can also use the water left in the tank effectively, and it can be used right away the next day.
You can start developing. Furthermore, the compounds used in the present invention are safe to handle.

Claims (1)

[Claims] 1. When black and white silver halide photographic materials are developed using an automatic processor, the fixing solution in the fixing step contains a water-soluble aluminum compound, and the automatic developer is stopped and the washing water in the washing step is replenished. When the washing water is not used, the washing water in the washing water tank contains at least one of aminopolycarboxylic acids and phosphonic acids per washing water.
A method for developing a black and white silver halide photographic material, characterized in that it contains 0.02g or more.