JPH02247642A - Processing method for silver halide black-and-white photosensitive material increasing efficiency of water saving and enabling antistatic treatment - Google Patents

Abstract

PURPOSE:To enable the recycling of washing water and the antistatic treatment of a photosensitive material and to prevent the increase of the amt. of the residual component of a fixing soln. remaining on the photosensitive material by regenerating and using used washing water and using washing water treated so as to reduce the amt. of specified ions. CONSTITUTION:Washing water is passed through a softening means A such as zeolite so as to reduce the amt. of Ca and Mg ions, the softened washing water is filled into a washing vessel 1 and a water storage vessel 2 and the photosensitive material is washed in the vessel 1. Washing water is automatically replenished from the vessel 2 in accordance with the amt. of the photosensitive material washed and the used washing water overflowing the vessel 1 is stored in the vessel 2. Since the washing water is contaminated by a component (e.g., sodium thiosulfate) having a harmful effect on the photosensitive material in accordance with the progress of washing, the component is removed with an adsorption filter 4 as a regenerating means. When the concn. of the contaminant exceeds a prescribed value, a purifying agent is fed from a vessel 5 to the vessel 2 to reduce the concn. to a value fit for discharge.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for processing silver halide black and white light-sensitive materials.
More specifically, the present invention relates to a method for processing silver halide black-and-white light-sensitive materials that increases water-saving efficiency and enables excellent antistatic treatment.

[Prior Art] Currently, the development of silver halide photosensitive materials is generally carried out using automatic processors, but such automatic processors usually carry out all stages of development, fixing, washing, and drying. After the development and fixing processes have been completed, the photosensitive material is washed with water to remove the processing liquid components from the previous process, especially the fixing liquid components, contained in the material. If this water washing is insufficient, performance problems such as image deterioration over time due to residual fixer components in the material will occur, especially in black and white silver halide photosensitive materials. Therefore, it is necessary to perform sufficient washing with water to sufficiently remove the residual fixer components in the photosensitive material, but sufficient washing as described above is not possible with the amount of washing water stored in the washing tank of an automatic developing machine. Met. For this reason, the current practice is to constantly supply tap water during the flushing process, and to drain the overflowing flushing water directly to the water supply and sewage system.

Under the above circumstances, in recent years, there has been an increasing demand for saving water when washing automatic processors from the viewpoint of saving resources and reducing production costs, and there has also been an increasing demand for technological improvements.

By the way, for example, in the field of printing plate making, dirt, dust, dirt, etc. adhere to the photosensitive material that is readhered in the return process, and due to this, particles within about 30 microns are included in the blackened image obtained after the development process. A defect called a so-called pinhole occurred, and work efficiency was significantly reduced due to countermeasures. The adhesion of dust and the like, which is thought to be the cause of such pinholes, is thought to be largely due to the insulating properties of the photosensitive material itself and accumulated charges due to contact friction and the like. Therefore, as a technique for preventing such charging, various countermeasures have been taken from the photosensitive material side, such as providing an antistatic layer on the photosensitive material, but the effects are not sufficient.
Furthermore, methods of applying antistatic treatment in the development process have been considered.

In particular, the water washing step is the final step of the bath treatment, and according to research by the present inventors, the conductivity is significantly reduced after the water washing step. It was requested.

[Problems to be Solved by the Invention] One method for the above-mentioned antistatic treatment is to remove and lower the concentration of calcium and magnesium ions in the water, which are thought to be the cause of the decrease in conductivity in the water washing step. Conceivable.

However, the conventional method of constantly supplying tap water during washing uses a large amount of water.
It has been difficult in terms of cost and maintenance to constantly perform treatment to reduce calcium ions and magnesium ions on these large amounts of water.

Therefore, a first object of the present invention is to provide a method for processing silver halide black-and-white light-sensitive materials, which makes it possible to reuse washing water and thereby improve water saving efficiency.

A second object of the present invention is to provide a method for processing silver halide black-and-white light-sensitive materials that enables excellent antistatic processing.

A third object of the present invention is to provide a wastewater treatment method that can purify contaminated washing water to the point where it can be drained.

A fourth object of the present invention is to provide a method for processing a silver halide black-and-white light-sensitive material, which prevents an increase in residual fixer components in the silver halide black-and-white light-sensitive material during washing and provides excellent image characteristics.

[Means for Solving the Problems] In view of the above-mentioned problems, the present inventors have conducted extensive research and found that the above-mentioned object of the present invention is to provide an automatic developing device consisting of at least a developing section, a fixing section, and a water washing section. In the method of processing a silver halide black-and-white photosensitive material using a water washing unit, the water washing section includes at least a water washing means for washing the light sensitive material, and water containing used washing water discharged from the water washing means to the water washing means. a water storage means for temporarily storing supplied flush water; and at least one regeneration means for regenerating the used flush water;
a circulation means for circulating the washing water in the washing means and the washing water in the water storage means between the washing means and the water storage means;
This is achieved by providing a method for processing a silver halide black-and-white light-sensitive material, which is characterized in that the washing section uses washing water made of water that has been previously treated to reduce calcium ions and magnesium ions. I found out that it can be done.

Below, the automatic phenomenon device of the present invention will be explained based on the drawings.

FIG. 1 is a schematic diagram schematically showing an example of a water washing section of an automatic developing device of the present invention. According to FIG. 1, the washing section of the developing device of the present invention includes a washing tank 1 for processing a photosensitive material, washing water for replenishing the washing tank 1, and washing water overflowing from the washing tank 1 due to the replenishment. A water storage tank 2 provided in the vicinity of the washing tank 1 for storing water, and a circulation means for replenishing washing water from the water storage tank 2 to the washing tank 1 and sending overflow water from the washing tank 1 to the water storage tank 2. 3, for example, if the contamination concentration of the flush water being circulated by the regeneration means such as a filter 4 provided in the middle of the path from the water storage tank 2 to the flush 1!1 and the circulation means 3 exceeds a predetermined value. A purifying agent supply tank 5 for automatically supplying a purifying agent to the water storage tank 2 to purify it to a level that can be drained, and discharging at least a part of the flush water in the water storage tank 2 after supplying the purifying agent. It consists of a discharge means 6.

That is, at the start of the development process, the washing tank 1 and the water storage tank 2 are filled with unused washing water that has been treated to reduce calcium ions and magnesium ions through the water softening treatment means A using zeolite, and then the water that has been subjected to the development and fixing process is The photosensitive material is washed in the washing tank 1, and washing water is automatically replenished from the water storage tank 2 according to the processing time of the photosensitive material.As a result, the used washing water overflowing from the washing tank 1 is disposed of as before. The water is sent to the water storage tank 2 and temporarily stored without being drained as it is. As the amount of processing increases, by repeating this cycle, the washing water in the washing tank 1 and the water storage tank 2 is removed from the fixing solution components brought in by the photosensitive material or eluted from the photosensitive material, such as dyes, pigments, surfactants, and gelatin. As a result, the washing efficiency is reduced and the finish of the photosensitive material after washing is adversely affected. To prevent this, for example, flush from water tank 2 to 4! ! A filter 4 is installed as a regeneration means between the path from the washing water to the water tank 1 or from the washing tank 1 to the water storage tank 2.
＋), especially thiosulfate ions, limescale, mold, etc., are removed and the washing water is regenerated. Such filters include adsorption filters, which remove adsorbent components from filter a! It is used attached to fibers.

Materials for filters include carbon fiber, aramid fiber, Teflon resin fiber,
Hemp, glass PJA fiber, polyethylene foam, polypropylene foam, etc. are preferably used.

Furthermore, those described in JP-A No. 60-263151 as contact substances can also be used.

It is also preferable to use powder as an adsorbent in the form of a cartridge, fill it in a filling unit, and allow water to pass through it.

The adsorbents mentioned here include those made by pulverizing a mixture of silicon oxide and magnesium using acidic or alkaline adsorbents, and activated carbon fine powders for the purpose of activation such as nickel, calcium, magnesium, tin, and iron. , those mixed with fine particles of metal such as aluminum, and the like. Also, natural stones such as zeolite that have a network of pores,
Synthetic zeolites in general and silica-alumina-based adsorbents are also preferred, and in particular, natural zeolites and synthetic zeolites are activated by supporting the above-mentioned metal fine particles, and the adsorption area is increased to increase their ability as adsorbents. is also preferably used.

Examples of commercially available adsorbents include RyoNami Paper Industries (iM Kyoward series, Kimmyward 400, Kyoward 600, and polypropylene long fiber nonwoven fabric).

The above-mentioned filter can be used in combination with a sheet-like filter made of activated carbon fiber, etc., in order to prevent clogging caused by gelatinized substances such as gelatin and extend its lifetime. As a result, the filter replacement life can be extended. It is possible.

Further, the washing water can be regenerated by separately providing an oxidizing agent supplying means including an oxidizing agent supplying tank as the regeneration means and supplying the oxidizing agent to the water storage WI2 at appropriate times.

Examples of such oxidizing agents include metal or nonmetal oxides, oxide acids or their salts, peroxides, and compounds containing various acid types. Since the main purpose is to decompose the fixer components brought into the water, the above-mentioned acids are preferably sulfuric acid, nitrous acid, nitric acid, hypochlorous acid, etc., and the peroxides are hydrogen peroxide solution. , Fenton's reagent, etc. are preferably used. Ozone is also preferably used.

These oxidizing agents are diluted with water or the like and added to the water storage tank 2 from an oxidizing agent supply tank placed adjacent to the water storage tank 2, but usually, a fixed amount is automatically added from the supply tank as needed. It is added to the water storage tank 2, preferably once every few hours, by opening the supply valve and automatically dropping it. The amount added can be arbitrarily selected depending on the type of photosensitive material, amount of processing, type of processing solution, etc., but since it is thought to be related to the fixer components introduced, it can be added for several hours by setting the timer as described above. In a system that automatically adds the required amount in units, the amount is in the range of 172 mol to several times the equivalent molar amount, especially in the range of 172 mol to the equivalent molar amount, relative to the thiosulfate ion in the fixer brought in. Preferably, it is added. Furthermore, since the fixer component itself actually brought in is proportional to the amount of processed photosensitive material, it is also possible to determine the amount added depending on the amount of processed photosensitive material. Further, the water storage tank 2 can be provided with a known stirring means in order to efficiently perform regeneration.

In the present invention, one type of each of the various regeneration means described above may be selected and used, or two or more types may be used in combination.

As the process further increases and the degree of contamination progresses, it becomes necessary to drain all or at least a portion of the washing water in the water storage tank 2 and replace it with fresh washing water.

However, especially if the level of contamination exceeds the above-mentioned drainage standards, it becomes impossible to drain water to the sewer! Kome,
It is necessary to constantly detect the concentration of contaminants in the flush water and keep the concentration within an acceptable range. For this reason, the concentration of contamination in the flush water is measured by any method, preferably by using a contaminant concentration measuring means for the flush water in the water storage tank 2, and based on the measured value, the concentration of contamination in the purification agent supply tank 5 is automatically measured. A purifying agent is supplied to purify the flushing water in the water tank 2 to an acceptable value. After that, at least a part of the purified washing water is drained by a draining means 6. All of the washing water in the water storage tank 2 may be drained, or only a portion may be drained and replaced with fresh washing water for mixed use.

In the present invention, the contaminant concentration of the washing water refers to the fixer component that is thought to have the greatest effect on the iodine consumption outlet, since it is considered necessary to satisfy the iodine consumption regulations since it is discharged into the sewer. It can be thought of as the concentration of thiosulfate ions such as ammonium thiosulfate and sodium thiosulfate.

As the purifying agent used in the present invention, the same oxidizing agent as that used in the regeneration means described above can be used.

Furthermore, when the oxidizing agent supply tank is provided as a regeneration means, it is preferable that the purifying agent supply tank is used also as the oxidizing agent supply tank.

For example, when the concentration of thiosulfate ions in the washing water in the water storage tank 2 exceeds a value corresponding to the standard value for iodine consumption, these purifying agents can be added according to the concentration, and can be diluted with water etc. The purifying agent is added to the water storage tank 2 from a supply tank 5 located adjacent to the water storage tank 2, but normally it is added automatically in a fixed amount from the supply tank as needed, preferably over several hours. It is added to the water storage tank 2 by opening the supply valve at a rate of about 1 degree and letting it automatically fall. The amount added can be determined through experiments or the like depending on the concentration of thiosulfate ions in the washing water.

In the present invention, OR
Measuring the ORP value with a P (l oxidation reduction potential) electrode,
Based on this, it is possible to automatically add a purifying agent.

Specifically, a sodium thiosulfate solution with a predetermined concentration is adjusted to pH
The amount of purifying agent to be added can be determined by adjusting the pH to 4 or 7, adding sodium hypochlorite, and measuring the iodine consumption, KMnOs overconsumption, and ORP value. That is, for example, with a 0.03N-Na 28203 solution, pH 4
1) H7 (7) When sodium hypochlorite was added to each of the solutions, a rapid rise in the ORP value of the first wave was observed in the pH 7 solution at a certain addition R, and this point was Matched the lowest consumption value. This is 52032-
This shows that the entire amount of was oxidized. Further addition of sodium hypochlorite results in the rise of a second wave of pH 7 solution and p
A rapid rise of the H4 solution is observed.

In this manner, in a neutral or acidic region, purification can be carried out automatically by adding sodium hypochlorite until the voltage reaches +500 to 800 mV using the rise of the ORP value. By such a method, the amount of purifying agent to be added can be determined by measuring the 0RPI in various cases.

The ORP electrode may be placed in a water tank and measured continuously or as needed, or may be inserted into the water tank at any time to perform measurements.

Alternatively, it may be installed in a circulation system outside the water storage tank, inside a washing tank, etc., and the measured value may be used as a substitute for the measured value inside the water storage tank.

By automatically or artificially feeding back this measured value to the purifying agent supply means and activating, for example, an electromagnetic on-off valve, it is possible to supply the required amount of purifying agent to the flushing water in the water tank. The reservoir can also include conventional stirring means to facilitate purification.

Another method for measuring contamination concentration is a method in which the area of the processed light-sensitive material is measured and used as a substitute. That is, since thiosulfate ion, which is a main contaminant, is a component brought in by the processed sensitive material, its amount is considered to approximately correspond to the group, ie, the total area, of the processed sensitive material. Therefore, it is necessary to determine in advance through experiments the contamination concentration when processing a photosensitive material with a predetermined opening and how much R purifying agent is required to purify it to a predetermined value, and then use this result to determine the contamination concentration when processing the photosensitive material. It is sufficient to measure and measure the total area of the photosensitive material and supply a slip purifying agent corresponding to the total area.

Specifically, this method involves detecting the photosensitive material with a sensor installed near the photosensitive material insertion port of the automatic fishing machine, and processing the photosensitive material at a counter connected to the sensor based on the information from this sensor. Count the total area of the sensitive material. If the total area counted exceeds the value corresponding to the predetermined pollution concentration,
The purifying agent is supplied to the water tank a predetermined number of times based on the experimental values. At this time, the device may have a system that inputs the experimental values in advance, calculates the amount of purifying agent corresponding to the total area value, and automatically supplies it, or a total area counter. When the amount exceeds a predetermined value, an alarm will sound, and in response to this, the amount may be supplied artificially based on experiments. The reservoir can also include conventional stirring means to facilitate purification.

By adding the purifying agent as described above, at least a portion of the washing water that has been purified to a predetermined value, at least a value that satisfies the drainage standards, is drained by the draining means 6. The drainage means includes, for example, a solenoid valve that can be opened and closed automatically, but the valve may be configured to open manually after the purifying agent is supplied, or automatically or after the purifying agent supply or purification is confirmed. It may be opened artificially to drain water.

As the washing means of the automatic developing apparatus of the present invention, various conventionally known washing tanks and washing methods can be used. Additionally, water containing various additives known in the art can be used as the rinsing water.

In particular, washing water treated with anti-mildew means is effectively used to prevent limescale from forming in water stagnant in a water tank.

As such anti-mildew means, Japanese Patent Application Laid-Open No. 60-26393
The ultraviolet irradiation method described in No. 9, the method using a magnetic field described in No. 60-263940, the method for purifying water using an ion exchange resin described in No. 61-131632, Japanese Patent Application No. 1983- No. 253807, Go-295894@,
The method using the antibacterial agent described in No. 61-63030 and No. 61-51396 can be used.

, furthermore, 1. E, West Water Qu
alityc rit8r+aNP Photo Sci
&Ena, Vol, 9 N.

6 (1965), N, W, 3each″Micro
biological Growths in fvlo
Non-picture Processing”
SMPTE Journal Vol. 85,
(1976), R.

0, Deeoan, “Photo Proc
essingWashWater B 1ocide
s″J, IaaingTech.

Vol. 10, No. 6 (1984) and JP-A Nos. 57-8542, 57-58143, and 58-1.
No. 05145, No. 57-132146, No. 58-18
No. 631, No. 57-97530, No. 57-15724
Antibacterial agents, anti-inflammatory agents, surfactants, etc. described in No. 4 can also be used in combination.

Furthermore, the washing water includes R, T, ) (written by Reiman, J.

I maae, Tech 10. (6) 242
(1984) isothiazoline compounds, R
ESEARC) Isothiazoline compounds described in DISCLO3IIRE Vol. 205, I tel 1120526 (May 1981 issue), isothiazoline compounds described in I tel 122845 (April 1983 issue), Volume 228 of the same, Gansho 61-51
The compounds described in No. 396, etc. are used as antibacterial agents (M 1c
It can also be used in combination as robiocide.

Furthermore, specific examples of anti-piping agents include phenol, 4-chlorophenol, pentachlorophenol, cresol,
O-phenylphenol, chlorophene, dichlorophene, formaldehyde, geltaraldehyde, chloracetamide, p-hydroxybenzoic acid ester, 2-
(4-Thiazoline)-benzimidazole, benzisothiazolin-3-one, dodecyl-benzyl-dimethylammonium-chloride, N-(fluorodichloromethylthio)-7talimide, 2,4.4'trichloro-
Examples include 2'-hydroxydiphenyl ether.

In addition, methods such as processing with various types of agitation, use of washing accelerators, supply of washing water according to the processing area of the photosensitive material, and use of a squeeze tool to reduce carryover to the washing tank are also used in combination. can do.

The water storage tank 2 of the present invention may be made of vinyl chloride containing an antibacterial agent or the like from the viewpoint of preventing limescale and corrosion, or may be made of nylon-treated material on the inside of the tank.

In the present invention, the circulation means for replenishing the washing water from the water storage tank 2 to the washing tank 1 can be detected by a sensor when the photosensitive material is inserted into an automatic developing machine, and thereby the water is automatically transferred from the water storage tank 2 to the washing tank 1. An electromagnetic valve design may be used in which rinsing water is supplied to the rinsing tank 1 and the supply of rinsing water is stopped when no photosensitive material is detected. At this time, it is preferable to forcibly transfer the flushing water using a high-pressure pump, and the replenishing flushing water m
The number is preferably 10 to 301, more preferably 15 to 252 per 1 f of processed sensitive material area.

Further, the flushing water that overflows from the flushing tank 1 due to the above-mentioned replenishment is directly sent to the water reservoir 2 through piping connected to the water reservoir 2 and is temporarily stored therein.

As described above, as in the present invention, the water saving efficiency is increased by providing a water storage tank and circulating the washing water, and by recycling the washing water, and further by using the washing water that has been subjected to antistatic treatment. The idea of performing processing was discovered for the first time by the present inventors as a result of intensive research, and is completely absent from the prior art.

In the present invention, the washing process is performed using washing water made of water that has been treated to reduce calcium ions and magnesium ions, and this reduction treatment reduces the concentration of calcium ions and magnesium ions in the washing water to 8111CI/1. Hereinafter, it is desirable to reduce it to preferably 41 Mj2 or less in order to provide an excellent antistatic effect.

As the treatment for reducing calcium ions and magnesium ions in the present invention, a method of bringing washing water into contact with zeolite is preferred.

The zeolite used in the present invention is preferably an ion-conversion type zeolite, particularly an insoluble aluminum salt containing Na (AlO2) x (Si 02 ) V
-Z (H20) (D-R formula: j5 is preferred. In the above general formula, both A-type zeolite where X and y are equal and X-type zeolite where X and y are different can be used in the present invention. However, type X zeolite is preferably used because it has an excellent exchange ability for both calcium ions and magnesium ions.

An example of such a zeolite is the molecular sieve LINDEZ 3-300 manufactured by Union Carbide. The zeolite used in the present invention can be of various particle sizes, but particles larger than 30 mesh are preferred when packed in a column and brought into contact with a washing solution.

A specific method for reducing calcium ions and magnesium ions using the above zeolites includes, for example, a method in which these zeolites are packed in a column, and washing water is passed through the column and brought into contact with the column. The time period for which the washing water is brought into contact with the zeolite naturally varies depending on the concentration of ions to be removed, the type of zeolite, etc., and can be selected arbitrarily.

It is preferable that the above-mentioned calcium ion and magnesium ion reduction treatment be performed before supplying the water to the washing section of the developing device, and the reduction treatment may be performed by incorporating a means for reducing each ion such as zeolite into the developing device. Good too.

Further, the washing water used in the washing process only needs to have reduced calcium ions and magnesium ions as described above, and water treated to reduce each ion may be used by mixing with 3 g of water.

The vine silver halide photosensitive material applicable to the automatic developing device of the present invention is a black-and-white photosensitive material, and particularly includes black-and-white negative film, black-and-white reversal film, X-ray film, copying film, printing film, and gravure film.

Furthermore, all of the various conventionally known systems can be used for the developing section, fixing section, and drying section of the automatic developing device used in the present invention.

A combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones is preferably used as a developing agent in the black and white developer applied to the present invention.

Of course, a p-amine phenol developing agent may also be included.

The dihydroxybenzene developing agent used in the present invention includes hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-
Examples include dichlorohydroquinone, 2,3-dibromohydroquinone, 2,5-dimethylhydroquinone, and hydroquinone is particularly preferred.

Developing agents for 1-phenyl-3-pyrazolidone or its derivatives include 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-7enyl-4-methyl-4-humanOxymethyl-3-pyrazolidone, and 1-phenyl-4-methyl-3-pyrazolidone. 4,4-
Examples include dihydroxymethyl-3-pyrazolidone.

As a p-aminophenol developing agent, N-methyl-
〇-aminophenol, p-aminophenol, N-(
β-hydroxyethyl)-p-aminophenol, N-
<4-hydroxyphenyl) glycine, 2-methyl-p
-aminephenol, p-benzylaminophenol, etc., and N-methyl-p-aminophenol is preferred.

The developing agent is preferably used in an amount of usually 0.01 mol/y to 1.2 mol/y.

The pH of the developer used in the present invention is preferably in the range of 9 to 13. More preferably, the pH is in the range of 10 to 12.

Alkaline agents used to set pH include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, trisodium phosphate, and potassium triphosphate.
Contains H regulator.

JP-A-61-28708 (borates), JP-A-60-
No. 93439 (e.g., sucrose, acetoxime, 5-sulfosalicylic acid), phosphates, carbonates, etc.
m agent may also be used.

Additives used in addition to the above ingredients include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite,
Sulfites such as formaldehyde sodium bisulfite;
Development inhibitors such as sodium bromide, potassium bromide, potassium iodide: ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, ethanol,
Solvents such as methanol = 1-phenyl-5-mercaptotetrazole, mercapto compounds such as zimidazole-5-sulfonic acid sodium salt, indazole compounds such as 5-nitroindazole, penztriazole compounds such as 5-methylbenztriazole It may contain antifoggants such as, and further may contain a color toning agent, a surfactant, an antifoaming agent, a water softener, an amino compound described in JP-A-56-106244, etc., if necessary.

In the present invention, silver stain preventive agents such as the compounds described in JP-A-56-24347 can also be used in the developer.

The developer used in the present invention includes Japanese Patent Application Laid-Open No. 56-106244
Amino compounds such as alkanolamines described in No. 1 can be used.

Other than this. F. “Photographic Processing Chemistry” by A. Menn, published by Focal Press (1
966), pp. 226-229, U.S. Patent No. 2, 19
No. 3,015, No. 2,592,364, Japanese Patent Application Publication No. 1973
-64933 etc. may be used.

The fixer used in the present invention is an aqueous solution containing thiosulfate and has a pH of 3.8 or higher, preferably 4.2 to 5.5.

Examples of the fixing agent include sodium thiosulfate and ammonium thiosulfate, 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 fixer used can vary and is generally from about 0.1 to about 6 mol/l. The fixer may also contain water-soluble aluminum salts that act as hardeners, including: Examples include aluminum chloride, ammonium sulfate, and potassium alum.

Tartaric acid, citric acid, or conductors thereof can be used alone or in combination of two or more kinds in the fixer. Those containing 0.005 mol or more of these compounds per 1 fl of fixer are effective, especially 0.005 mol or more. 01 mol/to ~0.0
3 mol/liter is particularly effective.

Specific examples include tartaric acid, potassium tartrate, sodium tartrate, potassium sodium tartrate, citric acid, sodium citrate, potassium citrate, lithium citrate, and ammonium citrate.

The fixer may optionally contain preservatives (e.g. sulfites, bisulfites), pHIl buffers (e.g. acetic acid, nitric acid), Tl
It can contain a HU4 conditioner (for example, sulfuric acid), a chelating agent with water softening ability, and a compound described in Japanese Patent Application No. 13562/1983.

The silver halide black and white photosensitive material used in the present invention will be described below.

The silver halide emulsion used in the black and white light-sensitive material of the present invention includes:
Any silver halide used in ordinary silver halide emulsions, such as silver bromide, silver iodobromide, silver chloride, silver chlorobromide, silver chloroiodobromide, etc., can be used as the silver halide, and is preferably , silver chlorobromide containing 60 mol% or more of silver chloride as a negative silver halide emulsion or 10 mol% as a positive silver halide emulsion
These are silver chlorobromide, silver bromide, and silver iodobromide containing the above-mentioned silver bromide.

The silver halide grains may be obtained by any of the acid method, neutral method, and ammonia method.

Silver halide grains may have a uniform silver halide composition distribution within the grain, or may be core/shell grains in which the silver halide composition differs between the inside and surface layer of the grain, and the latent image is mainly on the surface. It may be a particle that is formed inside the particle, or it may be a particle that is mainly formed inside the particle.

Any shape of the silver halide grains according to the present invention can be used. One preferred example is (100
) plane as the crystal surface.

Also, U.S. Pat. No. 4,183. 756@, 4,225
, 666@, JP-A-55-26589, JP-A-55-
No. 42737, etc., and The. Journal of Photographic Science (J, Photgr, 5
Particles having shapes such as octahedrons, tetradecahedrons, and dodecahedrons can be prepared by the method described in literatures such as Ci), 21.39 (1973), and used.

Furthermore, particles having double-sided surfaces may be used.

Also, any grain size distribution may be used, and an emulsion with a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion with a narrow grain size distribution (referred to as a monodisperse emulsion) may be used alone. Alternatively, several types may be mixed.

As monodisperse silver halide grains in a monodisperse emulsion, the weight of silver halide contained within a grain size range of ±20% around the average grain size r is 60% or more of the weight of all silver halide grains. It is preferable that

Particularly preferred highly monodisperse emulsions of the present invention have a distribution width defined by 20% or less, more preferably 15% or less.

Monodispersed emulsions are disclosed in JP-A-54-48521 and JP-A-58-49.
It can be obtained by referring to No. 938 and No. 60-122935.

Although the photosensitive silver halide emulsion can be used as a so-called primitive emulsion without chemical sensitization, it is usually chemically sensitized.

For chemical sensitization, the G Ifkides or Z
The book by elikman et al. or @ , Friese
rrAde Grundlagen der Fotografisien buOtse Se Mi1~ Zilberhallognieden (
QicQrundlaoen der Photogr
aphischen Prozesse■Eye 3 ilb
erhalogenidenlA kademisch
eVerlagsgesellchart, 196
The method described in 8) can be used.

That is, a sulfur sensitization method using a compound containing sulfur that can react with silver ions or active gelatin, a reduction sensitization method using a reducing substance, a noble metal sensitization method using gold or other noble metal compounds, etc. may be used alone or in combination. Can be used. As sulfur sensitizers, thiosulfates, thioureas, thiazoles, rhodanines, and other compounds can be used, and as reduction sensitizers, stannous salts, amines, hydrazine derivatives, formamidine can be used. Sulfinic acid, silane compounds, etc. can be used, and for noble metal sensitization, in addition to gold complex salts, periodic table materials such as platinum, iridium, and palladium can be used.
Complex salts of group metals can be used.

After completion of the chemical sensitization as described above, for example, 4-hydroxy-6-methyl-1,3,3a, 7-titrazaindene, 5-mercapto-1-phenyltetrazole, 2
- Various stabilizers can also be used, including mercaptobenzothiazole. Furthermore, if necessary, a silver halide solvent such as a thioether, or a crystallization control agent such as a mercapto group-containing compound or a sensitizing dye may be used.

Silver halide grains are produced using cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or their complex salts, rhodium salts or their complex salts, iron salts or their complex salts in the process of forming and/or growing the grains. add metal ions,
It can be included inside the particle and/or on the particle surface.

Unnecessary soluble salts may be removed from the silver halide emulsion after the growth of silver halide grains is completed, or they may be left contained. In the case of removing the salts, it can be carried out based on the method described in Linati Disclosure No. 17643.

In the silver halide black-and-white light-sensitive material according to the present invention, the photographic emulsion may be spectrally sensitized to relatively long wavelength blue light, green light, red light, or infrared light using a sensitizing dye. , cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, viroline nucleus, oxazoline nucleus, thiazoline nucleus, virol nucleus, oxazole nucleus,
Thiazole nucleus, selenazole nucleus, imidazo, -l nucleus, tetrazole nucleus, pyridine nucleus, etc. Nuclei in which an alicyclic hydrocarbon ring is fused to these nuclei, and nuclei in which an aromatic hydrocarbon ring is fused to these nuclei, i.e. , indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or complex merocyanine dyes have ketomethylene structures such as pyrazolin-5-one nucleus, thiohydantoin nucleus, 2-thioxazolidine-2
, 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thioparturic acid group, and the like can be applied.

The sensitizing dye used in the present invention is used at a concentration equivalent to that used in ordinary negative-working silver halide emulsions. In particular, it is advantageous to use the dye at a concentration that does not substantially reduce the inherent sensitivity of the silver halide emulsion. About 1, OX 10-5 to about 5 x 10-mol of sensitizing dye per mole of silver halide is preferred, especially about 4 x 10-5 to 2 x 10-4 mole of sensitizing dye per mole of silver halide. It is preferable to use it at a concentration of .

The silver halide black-and-white light-sensitive material according to the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation and halation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, azo dyes, and the like. Among them, oxonol dyes: hemioxonol dyes and merocyanine dyes are useful.

In the silver halide black-and-white light-sensitive material according to the present invention, when dyes, ultraviolet absorbers, etc. are included in the hydrophilic colloid layer, they may be mordanted with a cationic polymer or the like.

Various compounds can be added to the above photographic emulsion in order to prevent a decrease in sensitivity and the occurrence of fog during the manufacturing process, storage or processing of the silver halide photographic light-sensitive material. Namely, azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (particularly nitro- or halogen-substituted), heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles. mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially 1-phenyl-
5-mercaptotetrazole), mercaptopyridines, the above heterocycles having water-soluble groups such as carboxyl groups and sulfone groups, mercapto compounds, thioketo compounds,
For example, oxazolinthione, azaindenes, such as tetraazaindenes (particularly 4-hydroxy substituted (1,3
Many compounds known as stabilizers can be added, such as 38.7) tetraazaindenes), benzenethiosulfonic acids, benzenesulfinic acids, etc.

Further, the silver halide black-and-white photosensitive material of the present invention has U.S. Pat. No. 3,411,911 and U.S. Pat.
2, Japanese Patent Publication No. 45-53314, etc., may be included.

The silver halide black-and-white light-sensitive material of the present invention may contain the following various additives. For example, styrene-sodium maleate copolymer, thickener or plasticizer such as dextran sulfate, aldehyde type, epoxy type, ethyleneimine type, active halogen type, vinyl sulfone type, isocyanate type,
Various hardeners such as sulfonic acid ester type, carbodiimide type, mucochloric acid type, acyloyl type, etc., especially 2-(2'-hydroxy-5-tertiary butylphenyl)benzotriazole, 2-(2'-hydroxy-3'5') -di-tertiary butylphenyl)benzotriazole, 2-(2-human Oxy3'-tertiary butyl-5'-butylphenyl)-
Examples include ultraviolet absorbers such as 5-chlorobenzotriazole and 2-(2'-hydroxy-3'5'-di-tertiary butylphenyl)-5-chlorobenzotriazole.

Furthermore, anionic, cationic, and nonionic surfactants are used as coating aids, emulsifiers, permeability improvers for processing solutions, antifoaming agents, and surfactants used to control various physical properties of photosensitive materials. Alternatively, amphoteric compounds can be used.

In addition, as an antistatic agent, Japanese Patent Publication No. 46-24159,
JP-A-48-89979, U.S. Patent No. 2,882,15
No. 7, No. 2.972,535, Japanese Unexamined Patent Publication No. 48-2078
No. 5, No. 48-43130, No. 48-90391,
Special Publication No. 46-241'19, No. 46-39312,
There are compounds described in JP-A-48-43809 and JP-A-47-33627.

In the photosensitive material used in the present invention, the constituent layers include matting agents such as silica described in Swiss Patent No. 330.158, glass powder described in French Patent No. 1.296.995,
Inorganic particles such as alkaline earth metals or carbonates such as cadmium and zinc as described in British Patent No. 1,173,181; starch as described in US Patent No. 2,322,037; Belky Patent No. 625,451 or British Patent 981,198
Starch derivatives described in Japanese Patent Publication No. 3643/1983, polyvinyl alcohol described in Japanese Patent Publication No. 3643/1986, Swiss Patent No. 330.15
Organic particles such as polystyrene or polymethyl methacrylate as described in US Pat. No. 8, polyacrylonitrile as described in US Pat. No. 3,079,257, and polycarbonate as described in US Pat.

In the photosensitive material used in the present invention, the constituent layers further include a slippery agent, such as U.S. Pat.
Higher aliphatic higher alcohol esters as described in US Pat. No. 121,060, casein as described in US Pat. .384, U.S. Pat. No. 3,042,522, and U.S. Pat. No. 3,489.567. A dispersion of liquid paraffin can also be used.

As the optical brightener, stilbene-based, triazine-based, pyrazoline-based, coumarin-based, and acetylene-based optical brighteners can be preferably used.

These compounds may be water-soluble, or insoluble ones may be used in the form of a dispersion.

Examples of anionic surfactants include alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-alkyl taurines, sulfosuccinates, etc. acid esters,
Carboxy groups, sulfo groups, phospho groups, such as sulfoalkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphates, etc.
Those containing an acidic group such as a sulfate ester group or a phosphate ester group are preferred.

Preferred examples of the amphoteric surfactant include amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphoric acid esters, alkyl betaines, and amine oxides.

Examples of cationic surfactants include alkylamine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridium and imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocyclic rings. etc. are preferred.

Examples of nonionic surfactants include saponin (steroid type), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene Glycol sorbitan esters, polyalkylene glycol alkyl amines or amides,
Preferred are polyethylene oxide adducts of silicone), glyceed derivatives (eg, alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, and the like.

In the photosensitive material of the present invention, Japanese Patent Application Laid-Open No. 62-21045
A tetrazolium compound, a polyethylene oxide derivative, a phosphorus quaternary salt compound, a hydrazine compound, or the like can be used as a tone-enhancing agent that promotes high contrast as described in Japanese Patent Application Laid-Open No. 8, JP-A-Sho [1i2-139548, etc.].

Gelatin is used as the binder for the photosensitive material used in the present invention, but gelatin derivatives, cellulose derivatives, graft polymers of gelatin and other polymers, other proteins, sugar derivatives, cellulose derivatives, and single or copolymers may also be used. Hydrophilic colloids such as synthetic hydrophilic polymer substances can also be used in combination.

Examples of gelatin include lime-processed gelatin, acid-processed gelatin, and Bulletin Op Society of Japan (Bull, Soc, Sci, Phot).

Oxygen-treated gelatin as described in J. apan) NO 16, p. 30 (1966) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used.

Examples of gelatin derivatives include gelatin and various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acids, alkanesultones, vinyl sulfonamides, maleimide compounds, polyalkyleonoxides, and epoxy compounds. The product obtained by reacting is used.

Proteins such as albumin and casein, cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfate esters, and sugar derivatives such as sodium alginate and starch derivatives may be used in combination with gelatin.

The graft polymer of gelatin and other polymers includes gelatin and derivatives such as acrylic acid, methacrylic acid, their esters and amides, and single (homo) or copolymers of vinyl monomers such as acrylonitrile and styrene. A grafted material can be used. Particularly preferred are graft polymers with polymers which are compatible with gelatin to some extent, such as acrylic acid, acrylamide, methacrylamide, hydroxyalkyl methacrylates and the like.

The photosensitive material of the present invention may further contain various additives depending on the purpose. For more details on these additives, see Research Disclosure Volume 176! tea
17643 (December 1978) and Vol. 187, 1 tea 18716 (November 1979), and the relevant sections are summarized in the table below.

Additive type 1, chemical sensitizer 2, sensitivity increasing agent 3, spectral sensitizer supersensitizer 4, brightener 5, antifogging agent and stabilizer 6, light absorber, filter dye ultraviolet absorber 7 , stain inhibitor 8, dye image stabilizer 9, hardener 10, binder 11, plasticizer/lubricant 12, coating aid/surfactant 13, static inhibitor RD 17643 23 pages 23-24 pages 24 pages 24 ~ 25 pages 25-26 pages 25 right column 25 pages 26 pages 26 pages 21 pages 26-27 pages 21 pages RD 18716 648 pages right column Same as above 648 pages right column ~ 649 right column 649 pages right page 649 right column ~ 650 Pages left column 650 pages left-right column 651 pages left column same as above page 650 right column same as above same as above The support used in the light-sensitive material of the present invention may include α-olefin polymers (for example, polyethylene, polypropylene,
Flexible reflective supports such as paper laminated with ethylene/butene copolymer), synthetic paper, etc., semi-synthetic or synthetic polymers such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, polyamide, etc. These include films consisting of , flexible supports made of these films with reflective layers, metals, and the like.

Among them, polyethylene terephthalate is particularly preferred.

Examples of the undercoat layer that can be used in the photosensitive material of the present invention include an undercoat layer using an organic solvent containing polyhydroxybenzenes, and a water-based latex undercoat layer.

Further, the surface of the cough suppressant layer can usually be treated chemically or physically. Such treatments include surface activation treatments such as chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, activated plasma treatment, laser treatment, mixed acid treatment, and ozone oxidation treatment. .

Furthermore, it is also possible to use an organic desensitizer in which the sum of the anode potential and cathode potential of a polarograph described in JP-A-61-26041 is positive.

The photosensitive material used in the present invention can be exposed using electromagnetic waves in a spectral region to which the emulsion layer constituting the photosensitive material is sensitive. Light sources include natural light (sunlight), tungsten electric lamps, fluorescent lamps, quartz lamps, mercury lamps, microwave UV lamps, xenonark lamps, carbon arc lamps,
xenon flash lamp, cathode ray tube flying spot,
Various laser lights, light emitting diode lights, electron beams, X-rays, γ
Any known light source can be used, such as light emitted from a phosphor excited by radiation, alpha radiation, or the like. Also, JP-A No. 62-210458, etc. (7) UV light source 2370
Preferable results can also be obtained by installing an absorption filter that absorbs wavelengths of nm or less or by using a Uv light source whose main emission wavelength is 370 to 420 r++y+.

The exposure time is not only the 1 millisecond to 1 second exposure time normally used in cameras, but also the exposure shorter than 1 microsecond, for example, the 100 nanosecond to 1 microsecond exposure time using a cathode ray tube or xenon flash tube. It is also possible to provide exposures longer than 1 second. These exposures may be performed continuously or intermittently.

EXAMPLES The present invention will be specifically explained below with reference to Examples.

It should be noted that, as a matter of course, the present invention is not limited to the embodiments described below.

Example-1 (Silver halide emulsion made by M) p) The coating shown below containing 10-5 moles of rhodium per mole of silver was prepared by the Hun 1-Roll double jet method in an acidic atmosphere of 13.0%. Grains with average grain size, silver halide composition, and dispersity were prepared. Particle growth was performed in a system containing 30 mo of benzyladenine per 12 of a 1% gelatin aqueous solution. After mixing silver and halide, 6-methyl-4
-Hydroxy-1,3,3a,7-tetrazaindene was added in an amount of 600 mg per mole of silver halide, followed by washing with water and desalting.

Next, 601 mg of 6-methyl-4-hydroxy-1,3,3a,7-tetrazaindene per mole of silver halide was added, followed by sulfur sensitization.

After sulfur sensitization, 6-methyl-4-hydroxy-1,3,3a,7-tetra1f-1'endene was added as a stabilizer.

Additives were added to each of the above emulsions in the amounts shown below, and latex subbing treated (100 μm thick) polyethylene terephthalate I was prepared on a support as Example 1 of JP-A-59-19941. The following emulsion layer protective film, backing layer, and backing layer protective film were further applied to prepare silver halide photosensitive material samples Nos. 011 to 5.

(Silver halide emulsion layer) Latex polymer: Styrene-butyl acrylate acrylic acid ternary copolymer 1.0 g/f Tetraphenylphosphonium chloride 01M f Saponin 200 u/f Polyethylene glycol 100 m (J/l” dodecyl Sodium benzenesulfonate 100JJ/i2 Hydroquinone 20011!J/i
2 Phenidone 1100I1/f
Styrene-malein 1ift polymer 200m (1/
l' Gallic acid butyl ester 500II 1g/
f Not shown in hydrazine compound or tetrazolium compound-1 5-methylbenzotriazole 30m(+/n'2
-Mercaptobenzimidazole-5-sulfonic acid
30+11(1/f inatoossein gelatin (isoelectric point 4.9) 1.5(1/l' 1-(p-acetylamidophenyl)-5=mercaptotetrazole 30mg/11z silver pot
2.8<1/n' (emulsion layer protective film) W4 was coated as an emulsion layer protective film in the following amount.

Fluorinated dioctyl sulfosuccinate 3001g/
l” Matting agent: Polymethyl methacrylate (average particle size 3.5 μm) 100 Ugly IJ
/l” Lithium nitrate F 3011 / f acid-treated gelatin (isoelectric point 7.0) 1.2
(J/f colloidal silica 501G/
f Styrene-maleic acid copolymer 1100III/
f mordant-styrene copolymer styrene-maleic acid copolymer saponin citrate benzotriazole 0.5 (J/f 100m (1/7 4011g/l' 200mg/f 100IO/l' (backing m> Additives below) It was coated on the support on the opposite side from the emulsion layer so that the amount of coating was achieved.

Hydroquinone 100 Ugly 0/1' Phenidone 30m (J/f Latex polymer: Butyl acrylate backing dye (a) (Backing layer retention 111I) Additives were prepared and coated in the amounts shown below.

Dioctylsulfosuccinate ester 30011<1/n” Matting agent: Polymethyl methacrylate (average particle size 4.0 μra) 10010
/f colloidal silica 301g/l”
Ossein gelatin (isoelectric point 4.9) 1. IL;J
/f Sodium fluorinated dodecylbenzenesulfonate 50 mg/lz Table-1 Ossein gelatin 2, Og/ugly 2 Samples NO31 to 5 obtained as above were exposed to light,
Development processing was carried out using the developer, fixer, and washing solution shown below.

(Exposure method) An electrodeless discharge light source manufactured by Fusion (USA) called "V bulb" which has a maximum specific energy between 400 and 420 nm, or a conventional method called "0 bulb" which has a maximum specific energy between 350 and 380 rv. A light source was attached under the glass plate, and the original and photosensitive material were placed on the glass surface and exposed so that the quality of cut-out characters could be evaluated.

Developer formulation> Hydroquinone 25g 1-phenyl-4,4-dimethyl-3=pyrazolidone
0.4 g sodium bromide
3g5-methylbenzotriazole
0.395-nitroimidazole o
, osg diethylamine propane-1,2-diol 0 Ill Potassium sulfite 5-sodium sulfosalicylate Sodium ethylenediaminetetraacetate Finished to 12 with water.

The pH was adjusted to 11.5 with caustic soda.

Fixer formulation> g (Composition A) Ammonium 5A acid (72.5 weight 1% aqueous solution) 240.
iSodium sulfite +7 C1 Sodium acetate trihydrate 6.5gWIN
``'J Sodium citrate dihydrate 2g acetic acid (90wt 11% aqueous solution) 13.6d (composition) Pure water (ion exchange water) 17d' @ acid (50wt% aqueous solution) 4.7g aluminum sulfate CA1203 (Aqueous solution with converted m content of 8.1% by weight) When using 2G, 5Q fixer, dissolve in water 5oo112 in the order of the above composition A1 composition,
Used for finishing on 1J2.

The pH of this fixer was about 4.3.

For the water washing section, first cut off the water supply valve to the Konica Automatic Processor GR-27 (hereinafter referred to as GR-27), connect it to a vinyl chloride water tank with a volume of approximately 5 (liters), and then 4(l) Fill with water that has been treated to reduce calcium ions and magnesium ions as shown below, and also add rinsing water that has been treated in the same way as 22 to the wash tank of GR-27, so that a total of 62 y of water is circulated. state.

Furthermore, in the middle of the piping route for circulation from the water storage tank to the washing tank, Kiji-Ward 600 adsorbent (manufactured by Donami Paper Co., Ltd.) was attached to polypropylene IaM as a filter element and folded into a cylindrical shape to form a cartridge shape. This was done by interposing a filter formed by Filters like the one above use activated carbon to prolong their lifespan.
1$1 is made into a sheet and attached to the top of the above cartridge for use.

Calcium ion and management ion low treatment A Union Carbide Molecular Sieve L INDE 2B-300 energy column with a pore diameter of 60 mesh is filled with water 401 for the water storage tank of the washing section and water 222 for the washing tank. , 622 in total, to produce water whose calcium and magnesium ion concentrations were reduced to 4 mQl.

Using the above-mentioned apparatus, the above-mentioned exposed samples N091~
No. 5 was processed under the following conditions to evaluate its photographic performance.

Furthermore, the results were compared with the results of the same treatment using tap water that was not subjected to each of the ion reduction treatments described above. The results are not shown in Table-2.

<Development processing conditions> (Process) (Temperature) (Time) Development 35°C 15 seconds fixing 35°C 10 seconds washing Rinse at room temperature 10 seconds Photographic performance evaluation method> (1) Place a net film on the pinhole improvement performance pasting base Then, fix the periphery of the mesh film with transparent scotch tape for plate making, and after exposure and development, the rating is "5" if no pinholes occur, and "1" is the worst level with the most occurrence of pinholes. It was evaluated on a five-point scale.

(2) Cutout character quality is the image quality in which a line width of 50 μm on a line drawing film is reproduced when a portion with a 50% halftone dot area is properly exposed to a photosensitive material for return with a halftone dot area of 50%. A five-point rating was given, with very good cutout character image quality being rated ``5'' and the worst level being ``1''.

Table 2 As is clear from Table 2, when the washing water was treated with calcium ion and magnesium ion reduction treatment, both pinhole improvement and cutout performance were significantly improved.

Furthermore, using the apparatus of the present invention and washing water, we processed 100 consecutive samples of Okine size 508 x 610 mm for the samples shown in Table 1, and then evaluated the photographic performance of the 100th sample, but similar results were obtained. It was done.

Furthermore, when treated using the apparatus of the present invention and washing water,
Even after processing 200 sheets of large gold size, residual hypocorrosion is 0.04
3 (J/f), which was lower than the direct level specified by ANS I (1985), and the regeneration effect of the washing water was sufficiently recognized.

In addition, we processed 200 large-sized sheets and used iodine eraser II 430.
ffiMf1. I) When H6.0 was reached, an experimentally determined amount of 6% hydrogen peroxide solution was added.2
1ffl (!#!, I) H7.2 was able to be discharged in a manner that satisfied the wastewater treatment standards.

[Effects of the Invention] As explained in detail above, by circulating and further regenerating the flushing water according to the present invention, water saving efficiency is greatly improved. Although there are some differences depending on the amount of processed photosensitive material, it is possible to save water by about 1/40 to 1/60.

Further, according to the present invention, a silver halide black-and-white light-sensitive material that has been subjected to excellent antistatic treatment can be obtained.

Further, by using the automatic developing apparatus of the present invention, it is possible to provide a processing method that prevents an increase in the residual fixer component of a silver halide black-and-white light-sensitive material and provides excellent image characteristics.

Furthermore, the automatic developing device of the present invention can improve water saving efficiency and purify used washing water, which should be treated as waste liquid with a high pollution load, to a level where it can be discharged into the sewage system, thereby reducing the user's burden on waste liquid treatment. I can do it.

[Brief explanation of drawings]

FIG. 1 is a schematic view schematically showing an example of a water washing section of an automatic developing device of the present invention.

Claims (3)

[Claims] (1) In a method for processing a silver halide black-and-white photosensitive material using an automatic developing device comprising at least a developing section, a fixing section, and a water washing section, the washing section includes at least a water washing means for washing the photosensitive material with water, and the water washing section. a water storage means for temporarily storing water including used washing water discharged from the means as washing water to be supplied to the washing means; at least one regeneration means for regenerating the used washing water; and the washing means. a circulating means for circulating the washing water in the washing section and the washing water in the water storage means between the washing means and the water storage means, and in the washing section,
1. A method for processing silver halide black-and-white light-sensitive materials, characterized in that the processing is carried out using washing water made of water that has been previously treated to reduce calcium ions and magnesium ions. (2) In a method of processing a silver halide black-and-white photosensitive material using an automatic developing device comprising at least a developing section, a fixing section, and a water washing section, the washing section includes at least a water washing means for washing the photosensitive material with water, and the water washing section. a water storage means for temporarily storing water including used washing water discharged from the means as washing water to be supplied to the washing means; at least one regeneration means for regenerating the used washing water; and the washing means. circulation means for circulating the washing water in the water storage means and the washing water in the water storage means between the washing means and the water storage means; a purifying agent supply means for supplying a purifying agent to the means; and a drainage means for draining at least a part of the washing water in the water storage means after supplying the purifying agent; 1. A method for processing silver halide black and white light-sensitive materials, characterized in that the processing is carried out using washing water made of water that has been treated to reduce ions. (3) The treatment method according to claim (1) or (2), wherein the treatment for reducing calcium ions and magnesium ions is a treatment of bringing them into contact with zeolite.