JPH0321945A - Method for processing silver halide black-and-white photographic sensitive material - Google Patents

Abstract

PURPOSE:To enable water to be saved by circulating rinsing water and supplying an oxidant in accordance with the area of the photosensitive material to be processed to regenerate the water. CONSTITUTION:The photosensitive material with a developer and a fixing agent is rinsed with water in a rinsing bath, the area of the photosensitive material to be processed is detected by a sensor 7, the rinsing water is automatically supplied from a storage tank 2 in accordance with the area to be processed, the used water overflowing from the bath 1 is sent to the tank 2 and temporarily stored there, thus permitting both rinsing waters in the bath 1 and the tank 2 to be contaminated and rinse effect to be deteriorated, and the finish of the photosensitive material after rinsing to be adversely affected. It is prevented by installing a filter 4 in the recirculation course to remove suspensions and an oxidant feeder to supply the oxidant to the tank 2 at a proper time, and to regenerate the rinsing water as a regenerating means, thus permitting the rinsing water to be regenerated and the rinsing efficiency to be enhanced.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for processing silver halide photographic materials, and more specifically, to a method for processing silver halide photographic materials, and more specifically, to a method for processing silver halide photographic materials. This invention relates to a method for processing silver black-and-white photographic materials.

[Background of the invention]

Currently, it is common to develop silver halide photosensitive materials using automatic processors, which usually consist of the following steps: development, fixing, washing, and drying. After the development and fixing processes have been completed, the photosensitive material is washed with water to remove a portion of the processing solution from the previous step, especially a portion of the fixing solution, contained in the material. If this water washing is insufficient, particularly in black-and-white silver halide photosensitive materials, performance problems such as image deterioration over time due to some residual fixing solution in the material may occur. Therefore, it is necessary to perform sufficient washing with water in order to sufficiently remove the residual fixer solution from the photosensitive material, but the amount of washing water contained in the washing basin in an automatic processor does not allow sufficient washing as described above. It was possible. For this reason, the current practice is to constantly supply water during the flushing process, and to drain the overflowing flush water directly into the sewer system.

Under the above-mentioned circumstances, there has recently 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. In other words, problems such as land subsidence in urban areas, increases in water and sewage charges due to capital investment due to lagging behind in sewage treatment facilities compared to Western countries, and water outages due to unique summer weather conditions in specific regions. The demand for conserving washing water in order to cope with this problem is becoming more and more intense in conjunction with the recent increase in processing volume at plate making plants and the problem of the total amount of wastewater i system.

In response to the above-mentioned water-saving requirements, water-free and piping-free systems or countercurrent water washing methods, which perform chemical treatment instead of the conventional water washing treatment, have been proposed for current black-and-white silver halide photosensitive materials, especially for printing plate making. In recent years, automatic processing equipment has become more complex and larger, such as increasing the number of processing tanks, resulting in longer processing lines and slower processing times for photosensitive materials. From the perspective of speeding up, this was completely backwards and could not be applied. For this reason, one possible method is to provide a water storage tank near the washing tank that stores washing water separately from the washing tank that performs the washing process, and circulate the washing water between the water storage tank and the washing tank. However, according to this method, the developing solution, fixing solution and dye from the previous process are carried into the washing water by the photosensitive material being processed.
The concentration of components eluted from photosensitive materials such as dyes, surfactants, and gelatin increases as the amount of processing increases, and especially in recent large-scale processing, the amount of iodine consumed as a legally established water quality standard has increased. As a result, the value exceeds this value in a short period of time, and drainage problems remain. That is, a method that satisfies the problems of water saving efficiency and wastewater treatment at the same time has not yet been found.

On the other hand, the consumption of silver halide photographic materials has been steadily increasing in recent days. For this reason, the number of silver halide photographic materials to be processed has increased, and there is a need to speed up the development process, that is, to increase the amount of processing in the same amount of time. One way to shorten the time for development processing (generally longer than the development, fixing, washing, and drying steps) is to increase the conveyance speed. However, when developing with a roller conveyance automatic developing machine, if the roller conveyance speed is increased in an attempt to shorten the development processing time, the time that the film is in water during the water washing process will be shortened, so the film will not be washed with water. In particular, residual color caused by dyes, spectral sensitizing dyes, etc. caused by insufficient washing with water causes deterioration in image quality.

[Object of the Invention] Accordingly, the first object of the present invention is to provide a method for processing silver halide black-and-white photographic materials that enables recycling of washing water and, as a result, increases water-saving efficiency. be. A second object of the present invention is to provide a method for processing silver halide black-and-white photographic materials with improved residual color in ultra-quick processing with a total processing time of 20 to 60 seconds. A third object of the present invention is to provide a wastewater treatment method that can purify contaminated wash water to the point where it can be drained.

Other purposes will become clear in the following specification.

[Structure of the invention]

In view of the above-mentioned problems, the inventors of the present invention have conducted intensive research and have found that the object of the present invention can be achieved by the following method, and have accomplished the present invention. (1) In a method for processing a silver halide black and white photographic material using an automatic developing device comprising at least a developing section, a fixing section and a water washing section,
a means for the washing section to wash at least the photosensitive material; a water storage means for temporarily storing water containing used washing water discharged from the washing means as washing water supplied to the washing stage S; Regenerating the used washing water f: A regeneration means for adding an oxidizing agent to the water, and 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. and! If: Processing method for silver halide black-and-white photographic material in which washing is performed with washing water in a washing means, or (2) silver halide black-and-white is processed using an automatic developing device consisting of at least a developing section, a fixing section, and a washing section. In a method for processing a photographic light-sensitive material, the water washing section includes at least a washing means for washing the photosensitive material, and a washing water supplied to the washing means, the water containing the used washing water discharged from the washing means. A means of storing water temporarily as a
Regeneration means for adding an oxidizing agent to regenerate spent nuclear washing water; circulation means for circulating between the washing water in the washing means and the water storage means; and washing water circulated by the circulation means. If the contamination concentration in the water storage means 4 exceeds a predetermined value, the water storage means 4 has a purification agent supply means that supplies the purification agent, and a drainage means that drains at least a part of the washing water in the water storage means after supplying the purification agent. and (3) a method for processing a silver halide black-and-white photographic material, in which the halogen silver is washed with one trowel of washing water in the washing means, and (3) halogen is removed using an automatic developing device comprising at least a developing section, a fixing section, and a washing section. In the method of developing a silver halide black and white photographic light-sensitive material, the total processing time is 20 to 60 seconds. This is accomplished by a method.

The present invention will be explained in detail below. The inventors of the present invention, as a result of studies on the washing method with excellent water-saving efficiency, considered the use of an oxidizing agent as a regeneration means for reusing used washing water.

When an oxidizing agent is used, silver halide photographs are washed using the washing water regenerated by the oxidizing agent! It was found that the residual color of the photosensitive material C was reduced even in ultra-quick processing in which the total processing time of development, fixing, and water washing was 20 to 60 seconds.

FIG. 1 is a schematic diagram showing an example of a water washing section of an automatic developing apparatus of the present invention. According to FIG. 1, the washing section of the developing device of the present invention includes a washing PIl for processing the photosensitive material, washing water for replenishing the washing tank IT2, and washing water overflowing from the washing tank I from the replenishment number 2. Water storage tank 2 and water storage tank 2 are provided near the washing tank l for storing water.
A circulation means 3 that replenishes the washing water from the washing tank l and sends the over-7 low water from the washing tank l to the water storage tank 2, and a regeneration means provided in the middle of the path from the water storage fII2 to the washing ml, for example. The filter 4 as one of the means, and the washing water circulated by the circulation means 3.2 The oxidizing agent supply P!
15 and after the oxidizing agent is supplied, the photosensitive material is processed again in the water washing section, or there are two discharge means 6 for discharging at least a part of the pγ washing water in the water storage tank 2.

That is, at the start of the development process, water washing f! ! 1 and the water storage tank 2 with unused washing water, the developed and unfinished photosensitive material was washed with water using the water washing IlIl, and this Kql% material #
4 processing ill: Water storage P accordingly! From 2 onwards, the used rinsing water is automatically replenished, and as a result of 2, the used rinsing water that overflows from the rinsing tank 1 is stored instead of being discharged as is in the past! 21 water is sent and temporarily stored t1s The throughput increases 1; This cycle is repeated 2.
The flushing water in Wl and water tank 2! Optical materials brought in are contaminated by fixer components or components eluted from photosensitive materials such as dyes, pigment surfactants, and gelatin, which reduces washing efficiency and adversely affects the finish of photosensitive materials after washing. It becomes like this. In order to prevent this, for example, a filter 4 is provided between the path from the water storage tank 2 to the washing tank 1, or between the path from the washing tank 1 to the water storage tank 2. In particular, gelatin is used to remove limescale, dirt, etc. and regenerate washing water. For such filters, filter fiber materials such as carbon fiber, aramid fiber, and Teflon wood are recommended due to their heat resistance and chemical resistance. ! ! Sam, hemp, glass fiber, polyethylene foam, polypropylene foam, etc. are preferably used. Also, those described in JP-A-60-263151 as contact substances can also be used. 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.

The washing water can also be regenerated by 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 tank 2 at appropriate times.

Examples of such oxidizing agents include metal or non-metal oxides, oxide acids or their salts, peroxides, compounds containing organic acids, etc. The above acids include sulfuric acid, nitrous acid, and
Nitric acid, hypochlorous acid, etc. are preferred, and as the peroxide, 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. Target 1
The water is added to the water storage tank 2, preferably by opening the supply valve once every few hours and allowing the water to fall automatically. The amount added can be arbitrarily selected depending on the type of photosensitive material, processing amount, type of processing solution, etc., but it is considered to be related to the amount of fixer brought in, so as mentioned above,
11 method 42 automatically adds the required amount in units of several hours by setting a timer, for the thiovL acid ion in the fixer that is brought in! /2 mole to several times equivalent mole range, Special 1:. It is preferably added in an amount ranging from 1/2 mole to equimolar amount. Furthermore, since the amount of the fixer that is 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 fI2 can be provided with a known stirring means in order to efficiently perform regeneration f. In the present invention, one type of regeneration means using the above-mentioned oxidizing agent may be selected and used, or two or more types of regeneration means such as the above-mentioned filter treatment may be used in combination.

As the amount of treatment increases further and the degree of contamination progresses, the storage water P
! ! It becomes necessary to drain all or at least part of the second flushing water and replace it with fresh flushing water.

However, especially if the degree of contamination exceeds the above-mentioned drainage standards, it becomes impossible to drain the water to the sewer system, so it is necessary to constantly detect the concentration of contamination in the flush water and keep the concentration within an allowable 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 the cleaning agent supply tank 5 is automatically measured based on the measured value. A purifying agent is supplied to purify the flush water in water tank 2 to an acceptable level. After this, at least a part of the purified washing water is drained by a drainage means 6. All of the washing water in the water storage tank 2 may be drained, but only part of it may be drained and replaced with fresh washing water for mixed use. In the present invention, the contamination concentration of washing water refers to the concentration of contamination in the fixer or water that is considered to have the most influence on the iodine consumption, 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 thioit acid ions such as thio'fIiw1 ammonium 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.

These purifying agents can be added according to the concentration, for example, when the concentration of sulfate ions in the flush water in the water storage tank 2 exceeds the value corresponding to the standard value of iodine consumption, and they can be diluted with water etc. The purifying agent is then added to the water storage tank 2 from a purifying agent supply tank 5 located adjacent to the water storage tank 2. Usually, it is automatically added from the supply tank in a fixed amount as needed, preferably for several hours. The water is added to the water storage tank 2 in such a way that the supply valve is opened at a rate of approximately 1 degree per day, and the water is automatically dropped. The amount added can be determined through experiments, etc. depending on the thiosulfate ion concentration in the washing water. In the present invention, OR
P C redox potential)! Measuring the ORP value by the poles,
Based on this information, it is possible to automatically add purifying agents. Specifically, a sodium thioate 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, KMnO, consumption, and ORP value. That is,
For example, 0.03 N-Na, S, O. When sodium hypochlorite is added to solutions with pH 4 and pH 7, a rapid rise in the ORP value of the first wave is observed in the pH 7 solution at a certain addition amount, and this point indicates the amount of iodine consumed. coincided with the lowest value of This indicates that the entire amount of S,01- was oxidized. When sodium hypochlorite is further added, a second wave rises for the pH 7 solution and a rapid rise for the pH 4 solution. In this way, in a neutral or acidic region, use the rise of the ORP value to increase the
Purification can be carried out automatically by adding sodium hypochlorite until the voltage reaches ~800 mV. By such a method, the amount of purifying agent to be added can be determined by measuring the ORP value in various cases.

The ORPK pole may be placed in a water tank and measured continuously or as needed, or may be inserted into the water tank at any time for measurement.

Alternatively, it may be installed in a circulation system outside the water storage tank, inside a wash basin, 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 cleaning agent supply means and activating, for example, an electromagnetic on-off valve, it is possible to supply the required amount of cleaning agent to the flush water in the water storage tank. The reservoir can also include conventional stirring means to facilitate purification.

Another method for measuring contamination concentration is to measure the area of the processed photosensitive material and use it as a substitute. That is, since the main contaminant, thio[# ion, is a component brought in by the processed sensitive material, its amount is considered to approximately correspond to the amount of processed sensitive material, that is, the total area. Therefore, it is necessary to determine in advance the contamination concentration when a predetermined amount of pollutant is treated and the amount of purifying agent required to purify it to a predetermined value through experiments, and then use this result to determine the contaminant concentration and the amount of purifying agent required to purify it to a predetermined value. It is sufficient to measure and calculate the total area of the photosensitive material and supply an amount of purifying agent corresponding to the total area.

Specifically, in this method, a sensor installed near the photosensitive material insertion slot of an automatic processor detects the photosensitive material, and based on the information from this sensor, a counter connected to the sensor determines the processing sensitivity. Count the total area of the material. If the total area counted exceeds the value corresponding to the predetermined pollution concentration,
A predetermined amount of purifying agent is supplied to the water tank based on the experimental values. In this case, the apparatus may have a system in which the experimental values are input in advance, and the amount of purifying agent corresponding to the total area value is calculated and automatically supplied, or a total area counter may be provided. If the value exceeds a predetermined value, an alarm will sound, and depending on this, it 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 purified to a predetermined value, at least a value satisfying the drainage standard, 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 automatically after the purifying agent is supplied, or it may be configured to open automatically or manually after the purifying agent is supplied or purification is confirmed. Target: You may open it 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 the formation of limescale in water stagnant in a water storage 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, No. 60-295894,
Methods using antibacterial agents described in Japanese Patent No. 61-63030 and Japanese Patent No. 61-51396 can be used.

Another child is L. E. West"Water Quali
ty Criteria” Photo Sci & E
ng. Vol. 9 No. 6 (1965), N. W.
Beach″Microbiological Grow
thsinMotion-PictureProces
sing'' SMPTE Journal Vol1
85. (1976). R. O. Deegan, “Pho
to Processing Wash Wat
er Biocides” J. Imaging T
ech. Vol. 10, No. 6 (1984) and JP-A Nos. 57-8542, 57-58143, and 5
No. 8-105145, No. 57-132146, No. 58
-18631, 57-97530, 57-15
Antibacterial agents, anti-inflammatory agents, surfactants, etc. described in No. 7244 and the like can also be used in combination.

Furthermore, R. T. Kreiman, J. Ima
ge, Tech10. (6) 242 (1984
) isothiazoline compounds described in IIISE
ARC}l DISCLOSURE Volume 205, lte
Inthiazoline compounds described in m20526 (May 1981 issue), Volume 228, Iteκ2284
5 (April issue, 1983), the compounds described in Japanese Patent Application No. 61-51396, etc. can also be used in combination as an antifouling agent (Microbiocide).

Furthermore, specific examples of anti-piping agents include phenol, 4-chlorophenol, pentachlorophenol, cresol,
0-phenylphenol, chloro7ene, dichlorophene, formaldehyde, glutaraldehyde, chloracetamide, p-hydroxy7benzoic acid ester, 2-
(4-Thiazoline)-benzimidal/-, penzisothiazolin-3-one, doden-benzyl-dimethylammonium-chloride, N-(fluorodichloromethylthio)-7talimide 2.4.4'- }lichlor2' -Hydroxy 77 phenyl ether and the like.

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. I can do two things.

In addition, ultra-quick processing as referred to in this specification means that the leading edge of the film is inserted into an automatic developing machine, and then the film passes through a developing tank, a transfer section, a fixing tank, a transfer section, a washing tank, a transfer section, and a drying section. In other words, the total length of the processing line (1) is the line conveyance speed (
■/sec) divided by t; quotient (sec)) is 20 seconds to 6
This refers to a process that takes 0 seconds. The reason why the time for the transition part should be included here is that it is well known in the industry that even in the transition part, the liquid from the previous process is swollen in the gelatin film, so it is virtually impossible to This is because it can be considered that the processing process is progressing. The details of the present invention will be described below.

The silver halide emulsion used in the light-sensitive material of the present invention includes conventional silver halide emulsions such as silver bromide, silver iodobromide, silver chloride, silver chlorobromide, and silver chloroiodobromide. Any mercury halide used can be used, preferably silver chlorobromide containing 60 mol% or more of silver chloride as a negative-working silver halide emulsion or 10 mol% or more of silver bromide as a positive-working silver halide emulsion. These include silver chlorobromide, silver bromide, and silver iodobromide. The silver halide grains may be obtained by any of the acid method, neutral method and ammonia method.

Silver halide grains have uniform halide l! within the grains. They may have a single composition distribution, or they may be fine grains in which the silver halide composition differs between the inside and the surface layer of the grain, and even if they are grains in which the latent image is mainly formed on the surface, Alternatively, the particles may be formed mainly inside the particles.

Any shape of the halogenated ffl particles according to the present invention can be used. One preferred example is {100
} plane as the crystal surface. In addition, U.S. Pat. hotgr.Sci) - 2
1. Particles having shapes such as octahedrons, tetradecahedrons, and dodecahedrons can be prepared by the method described in literatures such as 39 (1973) and used. Furthermore, particles having twin planes may be used.

The silver halide grains according to the present invention may have a single shape, or may be a mixture of grains of various shapes.
:It can be anything. Also, emulsions with a wide grain size distribution (referred to as polydisperse emulsions) may be used.
Alternatively, an emulsion with a narrow particle size distribution (referred to as a monodisperse emulsion) may be used alone or in combination of several types.

Also, polydisperse emulsions and monodisperse emulsions may be mixed and used. The silver halide emulsion may be a mixture of two or more silver halide emulsions formed separately.

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 chemically sensitized and used as a so-called immature R (primitive) emulsion, it is usually chemically sensitized.

For chemical sensitization, the Glafkides or Z
Eliksan et al.'s book, or}I. Frieser
Di
e Grundlagen der Photog
raphischen Prozesse wit
Silberhalogeniden, Akad
emische Verlagsgesellscha
ft% 1968) can be used.

The silver halide grains used in the emulsion of the present invention may be prepared from cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts, rhodium salts or rust salts during the grain formation process and/or elongation process. Metal ions can be added using iron salts or complex salts to be included inside the particles and/or on the particle surface. In the emulsion of the present invention, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or they may be left in the emulsion. When removing the salts, the method described in Research Disclosure No. 17643 can be used. Invention t: The silver halide photographic light-sensitive material may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye, or for various purposes such as preventing irradiation and halide. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, azo dyes, and the like. Among them, oxonol dyes: hemioxonol dye 0 and merocyanine dyes are useful. In the silver halide photographic 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. These dyes can be preferably used in photosensitive materials for bright room printing, and it is particularly preferable to use them so that the sensitivity to 400 nm light is at least 30 times the sensitivity to 360 nm light.

Gelatin is used as the binder for the photosensitive material used in the present invention, but synthetic materials such as 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 hydrophilic polymer substances can also be used in combination. Gelatin includes lime-treated gelatin, acid-treated gelatin, Bull.Soc.Sci.'Photo.Ja
pan) No. 16. Oxygen-treated gelatin described on page 30 (1966) may be used, and +:O water decomposition products and enzymatic decomposition products of gelatin can also be used. Examples of gelatin derivatives include gelatin with acid halides,
Those obtained by reacting various compounds such as acid anhydrides, incyanates, bromoacetic acids, alkanesultones, vinylsulfonamides, maleimide compounds, polyalkyleonoxides, and epoxy compounds are used. Specific examples are U.S. Pat. No. 2,614.928, U.S. Pat.
No. 132.945, No. 3,186.846, No. 3,3
No. 12.553, British Patent No. 861.414, 1,0
No. 33.189, 1. No. 05.784, Special Publication No. 1977
-26845 etc. Proteins such as albumin and casein, cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and am ester of cellulose, and sugar derivatives such as sodium alginate and starch derivatives may be used in combination with gelatin.

Examples of graft polymers of gelatin and other polymers include gelatin and derivatives such as acrylic acid, methacrylic acid, their esters and amides, and single (homo) or copolymer of vinyl heptanomers such as acrylonitrile and styrene. A grafted version can be used. Particularly preferred are graft polymers with polymers that are compatible with gelatin to some extent, such as acrylic acid, acrylamide, methacrylamide, hydroxyalkyl methacrylate, and the like. These examples include US special pestles 2,7
No. 63.625, No. 2,831.767, No. 2,95
6,884 etc. The photosensitive material of the present invention may further contain various additives depending on the purpose. These additives are described in more detail in Research Disclosure Vol. 176 1 tea
17643 (December 1978) and volume 187 of the same
tea 18716 (November 1979), and the additive RD-17643 R
D-18716 page Classification page Classification chemical sensitizer 23 m 548-upper right sensitizer
Dye 2B IT 648 Right-
649 Left development accelerator 29 XX1 648 - Upper right anti-blur agent 24 VI 649 - Lower right
Fixing agent //
//Ultraviolet absorber 25~26■ 649 right~65
0 left 7 Ilter dye 〃// Hardening agent 26 X 6
51 Right coating aid 26-27 II
650 Right Surfactant 26-271I 650 Right Plasticizer 2 7 II
tt slip agent
〃Matte agent 28
XVI 650 right binder 26
II 651 Right The support used in the photosensitive material of the present invention includes a flexible reflective support such as paper or laminated paper laminated with a σ-refin polymer (e.g., polyethylene, polypropylene, ethylene/butene copolymer), etc. Films made of semi-polymerized or composite polymers such as polyester, cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, and polyamide, and flexible films with reflective layers on these 7 films. Includes supports, metals, etc. Among them, polyethylene terephthalate is particularly preferred.

Furthermore, the surface of these supports can 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. It will be done.

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

The light-sensitive material of the present invention can be exposed to electromagnetic waves in a spectral region to which the emulsion layer constituting the light-sensitive 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 lamps, cathode ray tube flying spots, various laser lights, and light emitting diode lights. Any known light source can be used, such as light emitted from a phosphor excited by electron beams, X-rays, γ-rays, a-rays, etc. Also, JP-A-62
-210458 and other UV light sources may be equipped with an absorption filter that absorbs wavelengths of 370 nm or less, or the emission wavelength may be reduced to 3
Preferable results can also be obtained by using a UV light source whose main wavelength is from 70 to 420 nm.

The concussion light time is not only the π light time of 1 millisecond to 1 second, which is normally used in cameras, but also haze light shorter than 1 microsecond, such as exposure of 100 nanoseconds to 1 microsecond using a cathode ray tube or xenon flash tube. It is also possible to provide exposures longer than 1 second. These tofu light may be performed continuously or intermittently. The present invention can be applied to various photosensitive materials such as for printing, for X-ray, for general negatives, for general positives, and for direct positives. In the present invention, for the development of the photosensitive material, various types of development for black and white using the known method 1 can be used, but this method is particularly effective when processing for a photosensitive material for printing that provides high contrast. ．． In the present invention, fixing solutions that can be used during processing include thiosulfates, sulfites, various acids, salts, fixing accelerators, wetting agents, surfactants, chelating agents, hardeners, etc. can be contained.
Examples include thiovLrI1 salts; sulfites include the potassium, sodium, and ammonium salts of these acids;
Examples of acids include vLrIi, hydrochloric acid, nitric acid, boric acid, formic acid, acetic acid, probionic acid, oxalic acid, tartaric acid, citric acid, malic acid, phthalic acid, etc., and salts include potassium, sodium, ammonium, etc. of these acids. Examples include salt. As the fixing accelerator, Japanese Patent Publication No. 45-35754, Japanese Patent Publication No. 58-122535, Japanese Patent Publication No. 58-122536 are used.
The thiourea derivative described in the issue has 31 in the molecule! Examples include alcohols having a bond, thioethers described in U.S. Pat. It will be done. Examples of moisture conditioners include alkanolamines and alkylene glycols. Examples of the chelating agent include aminoacetic acids such as nitrilotriacetic acid and EDT▲. As a hardening agent, chromium alum, potassium alum, or other compounds such as ^a compounds can be contained. In the present invention, the fixer preferably contains a penta-a compound in order to improve the hardening properties of the dazzling material, and the content thereof is adjusted to
It is more preferable that the amount is 0-1 to 3 g/Q in terms of Q. The preferred concentration of LrI1 contained in the fixer is 0.
03 to 0.4 mol/a, more preferably 0.04
~0.3 mol/Q. The preferred fixer pH is 3.9 to 6.5, and the most preferred pH is 4.2 to 5.3.

〔Example〕

Sixty-two examples of the present invention will be described in detail below, but it goes without saying that the present invention is not limited to these. ! ! ! Example 1 A silver chlorobromide emulsion (containing 65 mol% silver chloride and 3 mol% silver bromide) was prepared by an acidic method. These silver halide grains are monodisperse grains having a cubic crystal structure and an average grain size of 0.25 .mu.m, with more than 90% of the total grains having a size ranging from 0.7 times to 1.3 times the average grain size. For this silver chlorobromide emulsion, 6
6. Temperature of 0°C. Op} {and gold sulfur noble sensitization at 170 mV EA&, as stabilizer 4-hydroxy-6-methyl-1.3.3a. 7-Tetrazaindene was added. The emulsion was separated and the dyes (A), CB), (
C) was added at 250 sg per mole of silver halide to perform spectral sensitization. Furthermore, per mol of silver halide, 300 * g of sodium p-dodecylbenzenesulfonate 2 g of styrene-maleic acid copolymer polymer 2 g of styrene-butyl acrylate acrylic acid copolymer latex (average particle size of about 0.2
5 μm) was added to make the Ag content 3-5 g/m" and the gelatin content 2.0 g/m", and this photographic emulsion layer was prepared as described in Example (1) of JP-A-59-19941. Coated onto a polyethylene terephthalate film base with an undercoat of 1:. At that time, gelatin Jll. O
g/1 As a spreading agent, 30 mg of l-decyl-2-(3-inbentyl)succini-to-2-sulfonic acid sodium
/@'', and a protective layer containing 251 g/wr'' of formalin as a hardening agent was simultaneously applied in 1 liter layer.

Compounds (A), CB), [c] obtained in Sample 1
Samples (A), CB), and (C) were each subjected to illumination using an optical wedge and a tungsten light source.

The following developer and fixer were used. [Developer composition] (Composition A) Pure water
150 all ethylenediaminetetraacetic acid disodium salt 28 diethylene glycol 50 g Potassium sulfite (55% W/V aqueous solution) 100 m.

Potassium carbonate: 50 g Hydroquinone: 15 g Q Diethylene glycol 50 g Ethylenediaminetetraacetic acid disodium salt 25 mg Acetic acid (90% aqueous solution) 0.3 vaQ
5-nitroindazole 110 m
gl-7enyl-3-virazolidone 700
When using mg developer, add the above (set A) to 500 mQ of water.
(Composition B) was dissolved in this order, and the mixture was made up to 112 with water and used.

[Fixer prescription]

(Group A) Ammonium thiosulfate (72.5% w7v aqueous solution) 240
mQ sodium sulfite 17
g Sodium acetate trihydrate 6.5 g Boric acid 6 g Sodium citrate dihydrate 2 g Vinegar a (90%
W/V water soluble H) 13.6mQ(Ji
[1ffi B) Pure water 17 mQR
a (50% 11/II aqueous solution)
4.7g aluminum sulfate 26
．． 5g (aqueous solution with AQ.Oj equivalent content of 8.1% w/w) This is given IQ finish. The pH of this fixer was approximately 4.3.

For the water washing section, cut off the flood valve from the water supply to the automatic developing machine and connect it to a vinyl chloride water tank with a capacity of about 5H, and fill the water tank with 40Q of water and connect it to the automatic developing machine/washing tank. Mo22
A total of 620 pieces of water were circulated by adding wash water of Q.

Furthermore, a polypropylene fiber ``600'' manufactured by Paper Co., Ltd. was attached to the piping route for circulation from the water storage tank to the washing tank, and a filter cartridge was interposed to remove gelatin, dirt, etc. It was used for removal.

Furthermore, as an oxidizing agent, 6% diluted hydrogen peroxide solution was added at 10 liters per 11 areas of the processed photosensitive material. 5~IO. The oxidizing agent was added to the water tank from the oxidizing agent supply tank at a rate of 6 cc. This value was calculated from the amount of fixer components brought in, and the equipment was automated so that the information from the photosensitive material area detection sensor in the automatic processing machine insertion section was used to open and close the solenoid valve in the oxidizing agent supply tank. .

The above-mentioned sample was continuously processed using the above-mentioned apparatus, a photographic characteristic curve was drawn, and the fog density was measured.I2. In addition, for samples processed without applying two lights, we stacked 1,000 films, visually evaluated the remaining color of the film, and evaluated it on a five-point scale.
5" was colorless, and "1" had a strong orange residual color. For general plate making, residual color below "3" is considered to be a major drawback.

The conditions for development, fixing, and washing are as follows.

(Process) (Temperature) (Time) Development 35°C 15 seconds fixing 35°C 15 seconds washing 18°C 10 seconds drying 40°C 10 seconds drying Heat transfer coefficient 180Kcaff/h・m”C automatic developing machine installation environment humidity (temperature) -23℃ (relative humidity) -40%
Each process time includes the so-called wading conveyance time to the next process.Dry to Dry time is 50 seconds.Line speed is 20 seconds.
00 mm/win;, as a comparison with the present invention, processing is carried out in the same manner as in a general automatic processor processing, through development, fixing, and water washing steps, and in the washing step, water is supplied to the washing tank at a rate of 5 Q/sin. Ultra-rapid processing was performed under the same developing conditions as described above. The results obtained are shown in Table II below. Sensitizing dye (B) (C) Table 1 As is clear from Table 1, when the washing water used in the washing process is circulated and reused, an oxidizing agent is supplied as a means of regeneration according to the area of the processed sensitive material. It can be seen that by processing using the apparatus of the present invention and washing water, the reduction in residual color and the occurrence of fog caused by ultra-rapid processing were significantly improved. Mat: Using the apparatus of the present invention and washing water, cut samples (A) to (C) into four pieces in a series of 10 M.
After processing 0 images, the same photographic performance evaluation was performed for the 100th image, and similar results were obtained. In addition, the silver halide photosensitive material sample (A) was prepared using the present invention.
iJ=Thus, the circulating water rinsing water l: The treated area was 201 lj -) f: The sample at the time point was evaluated, and the residual hypo value was 0.04 g/m'', indicating that the photographic performance was good. ANSI (A
merican, national, standard
, institute) was sufficiently guaranteed from the viewpoint of the +1985 noon degree standard value. Also, in order to evaluate the quality of the water circulating in this device, when the total treatment area reaches 201 as described above, the iodine consumption value is 200 mg/O, which satisfies the wastewater standards at this point.

Therefore, there was no need to add hydrogen peroxide to purify the water.

〔Effect of the invention〕

As explained in detail above, by circulating the washing water and further regenerating the water by supplying an oxidizing agent according to the area of the processed sensitive material, the water saving effect is greatly improved. For a user I who is using water at a rate of 12/sin, it is possible to save up to 1/30 to 60 of the amount of water used (=processed photosensitive material l i), although there is a slight difference.

Further, by processing using the apparatus of the present invention, a silver halide black and white photographic light-sensitive material (I) having excellent ultra-rapid processing characteristics can be obtained.

Furthermore, the automatic developing apparatus of the present invention can provide a processing method that prevents an increase in the residual fixer component of a silver halide black-and-white photographic light-sensitive material and provides excellent image characteristics.

Furthermore, the automatic developing device of the present invention improves conservation inefficiency and purifies 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. The burden can be reduced.

[Brief explanation of drawings]

FIG. 1 is a schematic diagram schematically showing an example of the water washing section of the automatic developing device of the present invention. l...Washing rod 2...Water tank 3...Circulation means 4...Filter 5...Purification agent supply tank 6...
・Ejection means

Claims (3)

[Claims] (1) In a method for processing a silver halide black and white photographic light-sensitive 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 means for washing the photosensitive material with water; 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; and a regeneration means for adding an oxidizing agent to regenerate the used washing water. , comprising 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, and performing the washing treatment with the washing water in the washing means. A method for processing a silver halide black and white photographic material, characterized by: (2) In a method for processing a silver halide black and white photographic light-sensitive 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; a water storage means for temporarily storing water including used washing water discharged from the washing means as washing water to be supplied to the washing means; and a regeneration means for adding an oxidizing agent to regenerate the used washing water. and a circulation means for circulating the washing water in the washing means and the water storage means, and a purifying agent is added to the water storage means when the contamination concentration of the washing water being circulated by the circulation means exceeds a predetermined value. It is characterized by having a purifying agent supplying means for supplying the purifying agent, and a drainage means for draining at least a part of the flushing water in the water storage means after supplying the purifying agent, and performing the flushing process with the flushing water in the flushing means. A method for processing a silver halide black and white photographic material. (3) A method for developing a silver halide black and white photographic material using an automatic developing device comprising at least a developing section, a fixing section and a water washing section, characterized in that the total processing time is 20 to 60 seconds. A method for processing a silver halide black-and-white photographic material according to claims (1) and (2).