JPH0519424A - Device for regenerating and purifying washing water for automatic developing machine and method for processing silver halide photosensitive material using the device - Google Patents

Abstract

PURPOSE:To a device for regenerating and purifying the washing water for the automatic developing machine which is compact, inexpensive and handy and can be easily fixed to the developing machine and to process a silver halide photosensitive material using the device. CONSTITUTION:This automatic developing machine for a silver halide photosensitive material consists of a developing part, a fixing part and a washing part 1 and is provided with a means for regenerating washing water, a means 2 for supplying a cleaner contg. an oxidizing agent and preservatives to the washing part when the contaminant concn. in the washing water exceeds a specified value, a means 3 for discharging at least a part of the water in the washing part supplied with the cleaner provided with a means for measuring the contaminant concn. in the washing water the washing part for a fixed contact time and purifying the washing part. A silver halide photosensitive material is processed using the device.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an apparatus for regenerating and purifying washing water for automatic processors and a method for processing a silver halide light-sensitive material using the apparatus. More specifically, it has high water-saving efficiency and excellent finishing performance. The present invention relates to a compact and inexpensive reclaiming and purifying apparatus for washing water for an automatic processor and a method for processing a silver halide light-sensitive material using the apparatus.

[0002]

2. Description of the Related Art At present, the development processing of a silver halide light-sensitive material is generally carried out by using an automatic developing machine. However, such an automatic developing machine is usually used for developing, fixing, washing and drying. The photosensitive material which has been subjected to development and fixing processes is washed with water to remove the processing liquid component of the previous process contained in the material, especially the fixing liquid component, in the washing process. Insufficient washing with water causes performance problems such as deterioration of the image over time due to the residual fixer component in the material, especially in black and white silver halide photosensitive materials. Therefore, it is necessary to perform sufficient water washing in order to sufficiently remove the residual fixer component in the light-sensitive material, but the above-mentioned sufficient water washing cannot be performed with the amount of water washing water stored in the water washing tank in the automatic processor. Met. For this reason, the current situation is that tap water is always supplied during the flushing process and the overflowing flush water is drained to the sewer as it is.

Under the circumstances as described above, in recent years, from the viewpoint of resource saving and production cost reduction, the demand for water saving at the time of washing of the automatic developing machine has been increased, and the demand for technical improvement accompanying this has been increased. That is, problems such as land subsidence in urban areas, rising water and sewerage charges due to capital investment due to delays in sewage treatment facilities compared to Western countries, and water cutoff due to specific weather conditions in summer in specific areas. The demand for saving the amount of washing water in order to meet the above requirements has become stronger and stronger in recent years in combination with the increase in the amount of processing at the plate making machine and the problem of the regulation of the total amount of waste water.

[0004] In response to the above water saving requirements, an anhydrous washing is carried out in which a chemical treatment is carried out instead of the conventionally proposed washing treatment.
The non-piping system or the countercurrent washing method causes the complexity and size of the equipment such as the increase of the processing tank in the present automatic processing equipment for black and white silver halide photographic materials, especially for printing plate making. Since the line becomes long and the processing time of the light-sensitive material becomes long, it is in the opposite direction from the viewpoint of speeding up the processing accompanying the recent large-scale processing, and it is not applicable.

[0005]

Therefore, as one method, a water storage tank for storing water for washing is provided in the vicinity of the water washing tank separately from the water washing tank for performing the water washing treatment between the water washing tank and the water washing tank. A method of circulating wash water is conceivable. According to this method, a photosensitive material such as a phenomenon liquid, a fixing solution component and a dye, a pigment, a surfactant, gelatin, etc., which is brought into the wash water by the light-sensitive material to be processed, is used. As a result, the concentration of the components eluted from the water increases with the increase in the treatment amount, and especially in recent large-scale treatment, the amount of iodine consumed as a legally stipulated water quality standard is exceeded in a short time. Problems with drainage remain.

With respect to the above problems, the present inventors have previously proposed an oxidizing agent supply means as a regenerating means for regenerating used washing water in Japanese Patent Application Nos. 1-65440 and 1-65442. Proposes to provide.

However, in the method of circulating the washing water as described above, the generation of water stains and mold increases due to the long stagnation time in the washing water system, and these are accumulated in the circulation pipe. Techniques for adding chemicals such as bactericides and antifungal agents in order to solve such problems have been conventionally known, but the effect is not sufficient, and the above-mentioned problems of water-saving efficiency and wastewater treatment are accompanied by plaque. A method capable of simultaneously solving the conventional problems such as occurrence of such problems has not been realized yet.

Therefore, a first object of the present invention is to enable the reuse of washing water, and as a result, an apparatus for regenerating and purifying washing water for an automatic processor, which has improved water-saving efficiency, and a silver halide sensitizer using the apparatus. It is to provide a method of processing materials.

A second object of the present invention is to provide an apparatus for regenerating and purifying washing water for an automatic processor capable of removing water stains, molds and the like generated by conventional circulation of washing water.

A third object of the present invention is to provide a method for processing a silver halide light-sensitive material excellent in water saving effect.
It is to provide a more compact and more cost-effective product, and in particular, the present invention also provides the convenience that a conventional automatic developing machine can be easily attached.

A fourth object of the present invention is to provide an apparatus and a treatment method for regenerating and cleaning contaminated washing water and washing water for an automatic processor, which can purify it to the extent that it can be drained.

Further, a fifth object of the present invention is to eliminate the troubles such as adhesion of dirt to the circulation pipe, which is often caused by the conventional stored water saving method, by structurally eliminating the circulation pipe. The purpose of the present invention is to provide a reproduction and purification device.

[0013]

In order to achieve the above object, the apparatus for regenerating and purifying washing water for an automatic processor of the present invention is for a silver halide photosensitive material comprising at least a developing section, a fixing section and a washing section. In the case of processing with an automatic processor, a regenerating means for reprocessing the washing water while treating it, and a purification containing an oxidizer and a preservative in the washing part when the contaminated concentration of the washing water exceeds a predetermined value. A purifying agent supplying means for supplying the agent, a draining means provided with a means for measuring the contaminated concentration of the rinsing water so that at least a part of the rinsing water in the rinsing section can be drained after the cleaning agent is supplied; And a washing section washing means for performing washing with a constant contact time by administering the cleaning agent of a constant concentration to the washing section.

In the regeneration / purification device of the present invention, the regeneration means also serves as the purification agent supply means.

Further, the regeneration purification apparatus of the present invention is characterized in that hydrogen peroxide solution is used as the oxidizing agent.

Further, the processing method of the silver halide photosensitive material of the present invention is characterized in that it is carried out by using the regenerating and purifying apparatus of the present invention.

A water-saving treatment has been realized in which the fixing agent is decomposed in the wash water with a purifying agent and the silver halide sensitizing material is treated while regenerating water. First, after water-saving treatment, wash with an enzyme or the like (Japanese Patent Application No. 2-416392), and use a polyalkylene oxide compound in combination with a fungicide (Japanese Patent Application No. 3-
No. 63901) has been devised to prevent contamination of the automatic developing machine washing tank.

The inventors of the present invention have made earnest studies in order to pursue a technique for preventing dirt from adhering to the washing tank of an automatic processor in further water-saving treatment, and as a result, have solved the problems to be solved by using enzymes, anti-bacterial agents and the like. It was found that the same thing as the cleaning agent for regenerating the wash water can be solved by using it as a cleaning agent in a predetermined concentration range, and further, a higher stain prevention effect than before can be obtained, and the present invention is made. Arrived In addition, by using the same purifying agent as a cleaning agent for regenerating the washing water and for preventing dirt from adhering at the same time, the ease of treatment can be improved.
We were able to improve usability.

The present invention will be described in detail below.

FIG. 1 is a schematic view schematically showing an example of a regenerating and purifying apparatus for washing water for an automatic processor according to the present invention. According to FIG. 1, the apparatus for regenerating and purifying washing water for automatic developing machines according to the present invention,
For supplying an oxidant to the water washing tank 1 of the automatic developing machine for processing the photosensitive material automatically as a reproducing or purifying means based on the photosensitive material processing area information, or for supplying an oxidizing agent as a cleaning means after the automatic developing machine is stopped. The oxidant supply means 2 and an oxidant for decomposing the hypo that is brought into the water washing tank 1 are added, but when a contaminated concentration considered from the accumulation of elution components from the sensitive material is reached, Since it has to be replaced, the drainage means 3 having means for measuring the contaminated concentration of the wash water so that at least a part of the wash water can be drained, and the polyalkylene oxide chain in the wash water in the wash tank 1 And an addition means 4 for allowing the compound having

FIG. 2 is a schematic view schematically showing another example of the regeneration / purification device of the present invention. This is because the purifying agent is sent from the supply tank 2a to the dilution mixing tank 2b at any time by receiving the developer replenishment signal from the automatic developing machine, and is diluted with water to be supplied to the washing tank 1 when a certain concentration of contamination, that is, a certain processing area is reached. It is designed to be used. At this time, the mixed and diluted water is fed from the nozzle injection type supply port from the bottom of the washing section of the automatic processor for the purpose of improving the stirring efficiency.

According to the present invention, the conventional water storage circulation type water-saving system is made more compact, the cost is improved, and the circulation pipe is removed to prevent contamination in the circulation pipe.
As a result, it is possible to provide a regenerating and purifying apparatus for washing water for an automatic processor, which is excellent not only in saving water but also in maintainability.

Examples of the oxidizer used as the regenerating means in the present invention include metal or non-metal oxides, oxyacids or salts thereof, peroxides, compounds containing an organic acid system, and the like. As the oxygen acid, sulfuric acid, nitrous acid, nitric acid, hypochlorous acid, etc. are preferable because the main purpose is to decompose the fixer component brought into the used washing water. Hydrogen oxide water, fentonic acid drug and the like are particularly preferable. Ozone is also preferably used.

These oxidizers are diluted with water or the like and supplied to the washing tank 1. Normally, a fixed amount is automatically added from the supply tank as needed, preferably within 1 time.
It is added to the water washing tank 1 in the form of opening the supply valve at a rate of degree and automatically dropping it. The addition amount depends on the type of photosensitive material, the processing amount,
Although it can be arbitrarily selected depending on the type of treatment liquid,
Since it is considered to correlate with the fixer component that is brought in, in the system where the required amount is automatically added every few hours by the timer setting as described above, the thiosulfate ion in the fixer that is brought in is On the other hand, it is preferably added in the range of 1/2 to several times the molar equivalent, and particularly in the range of 1/2 to 3 times the molar equivalent. Also, since the fixer component itself that is actually brought in is proportional to the amount of processing photosensitive material,
It is also possible to determine the amount to be added depending on the amount of the processing photosensitive material. The washing tank 1 can have known stirring means in order to efficiently regenerate it.

As a stirring means, it is preferable to use a circulation pump in the water washing tank or to put a stirring unit having a small propeller-shaped one into the washing tank of the automatic developing machine to utilize its function.

When the treatment amount further increases and the degree of contamination progresses, it becomes necessary to drain all or at least a part of the washing water in the washing tank 1 and replace it with new washing water. However, especially when the degree of pollution exceeds the above-mentioned drainage standard, drainage to the sewer becomes impossible, so it is necessary to constantly detect the pollutant concentration of the wash water and keep the concentration within the allowable range. For this reason, the pollutant concentration of the wash water is measured by any method, preferably the wash water in the wash tank is measured using a pollutant concentration measuring means, and the measured value is automatically supplied from a separately provided purifying agent supply tank. The purifying agent is supplied to purify the washing water in the washing tank 1 to an allowable value. After this, at least a part of the purified wash water is drained by the drainage means 3. Wash tank 1
The washing water inside may be completely drained, but it is also possible to drain only a part of the washing water and replace it with fresh washing water for mixed use.

In the present invention, the contaminated concentration of washing water is considered to be necessary to satisfy the iodine consumption regulation because the sewer is discharged. It can be considered as the concentration of thiosulfate ions such as ammonium thiosulfate and sodium thiosulfate which are liquid components.

The purifying agent used in the present invention contains the same oxidizing agent and preservative as those used as the above-mentioned regenerating means, and, if necessary, by the addition means 4 different from the purifying agent supply means, the washing tank. A compound having a polyalkylene oxide chain can be added and made to exist therein.
Further, in FIGS. 1 and 2, the adding means 4 is the purifying agent supplying means 2
Although it is provided separately from the above, it is also possible to use it by also using it as a purifying agent containing an oxidizing agent, a preservative, and a compound having a polyalkylene oxide chain. It is preferable in terms of obtaining the effect and making the device compact. In this case as well, the compound having a polyalkylene oxide chain can be added as a purifying agent to the water washing tank so that it is present.

The preservative used in the present invention is used as a stabilizer for oxidizing agents such as hydrogen peroxide, and examples thereof include phosphoric acid, barbituric acid, urea, acetanilide, oxyquinoline,
Tetrasodium pyrophosphate, phenacetin, salicylic acid,
Dipicolinic acid, quinolinic acid, pyridinecarboxylic acid, ED
TA, ethylenediamine tetra (methylene phosphonic acid)
Etc. Although the amount of the preservative used varies depending on the substance, for example, it is 10 ^-7 to 1 times, more preferably 10 ^{-5 to} 0.5 times the weight of hydrogen peroxide, and in the case of an acid, the pH is not more than 5.7 or less. Should be added.

Further, the polyalkylene glycol used in the present invention is
The compound having a side chain is not particularly limited.
However, ethylene glycol is used as a hydrophobic group.
A compound having a general formula HO (C₂H_FourO)_a
-(C₃H₆O)_b-(C₂H_FourO) _cH (a, b, c are positive
A compound represented by (integer) is particularly preferably used.

In the present invention, the average molecular weight is 2000-8500 and the polypropylene glycol (PPG) molecular weight is 1400-240.
0, the weight ratio of ethylene oxide in the total molecule is preferably about 40 to 85%, and in the general formula, a + c is 15%.
It is preferable that 0 and b are about 30.

The compound having a polyalkylene oxide chain used in the present invention is a commercially available product such as a nonionic surfactant of "Pluronic series" manufactured by Asahi Denka Co., Ltd.

In the present invention, the followings are specifically preferable.

The amount of the compound having a polyalkylene oxide chain added is 1 ppm to 1000 ppm, more preferably 10 ppm to 100 ppm, with respect to the washing water, and when it is contained as a cleaning agent, 0.01% to 10% with respect to the cleaning agent. %, More preferably 0.1% to 5%.

It should be noted that the purifying agent supply means as shown in FIGS. 1 and 2 is preferably used in combination with the oxidant supply tank when the oxidant supply tank is provided as the regenerating means from the viewpoint of compactness.

When the concentration of thiosulfate ions in the washing water in the washing tank 1 exceeds the value corresponding to the reference value of iodine consumption, these purifying agents can be added depending on the concentration, such as water. Is diluted with and is added to the washing tank 1 from the purifying agent supply tank arranged adjacent to the washing tank 1.
Usually, a fixed amount is automatically added from the supply tank as needed, and preferably, it is added to the rinsing tank 1 by opening the supply valve and automatically dropping it at a rate of about once per fixed time. The addition amount can be determined by experiments or the like according to the thiosulfate ion concentration in the wash water.

In the present invention, as a means for automatically purifying by supplying a certain amount of a purifying agent according to the thiosulfate ion concentration, the ORP value is measured by an ORP (oxidation-reduction potential) electrode, and purifying is performed based on the measured ORP value. A method of automatically adding the agent is possible. Specifically, a sodium thiosulfate solution having a predetermined concentration is adjusted to pH 4 or pH 7, sodium hypochlorite is added, and iodine consumption, (MnO ₄ consumption and ORP value are measured to determine the amount of purification agent added. That is, for example, with a 0.03 N-Na ₂ S ₂ O ₃ solution, the pH
When sodium hypochlorite was added to each of 1 and pH 7, a sharp rise of the ORP value of the first liquid was observed in the solution of pH 7 at a certain addition amount, and this point was the minimum value of iodine consumption. Matched This indicates that the total amount of S ₂ O ₃ ²⁻ was oxidized. When sodium hypochlorite is further added, the rise of the second solution of the pH 7 solution and the sharp rise of the pH 4 solution are observed. Thus, by utilizing the rise of the neutral or acidic region ORP value, +500 to 800 m
Purification can be performed automatically by adding sodium hypochlorite until V is reached. With such a method, the amount of the cleaning agent added can be determined by measuring the ORP value in various cases.

The above-mentioned ORP electrode may be installed in a water washing tank and measured continuously or as needed, or may be inserted into the water washing tank at any time for measurement. This measured value is fed back to the purifying agent supply means automatically or artificially, and by operating, for example, an electromagnetic opening / closing valve,
A required amount of the cleaning agent can be supplied to the washing water in the washing tank. In the water washing tank, it is possible to have an ordinary well-known stirring means for promoting the purification as described above.

Further, as another method for measuring the contamination concentration, there is a method in which the area of the processed photosensitive material is measured and used as a substitute. That is, since thiosulfate ion, which is a main contaminant, is a component carried by the processed photosensitive material, its amount is considered to correspond approximately to the amount of the photosensitive material to be processed, that is, the total area. Therefore, by conducting an experiment, it is possible to determine in advance the contamination concentration when a predetermined amount of the photosensitive material is treated and the amount of the cleaning agent required to purify it to a predetermined value. It suffices to measure and calculate the total area of the light-sensitive material and supply the amount of the cleaning agent corresponding to this.

As such a method, specifically, a sensitive material is detected by a sensor provided in the vicinity of the sensitive material insertion port of an automatic processor, and a counter connected to the sensor is detected based on the information of this sensor. And count the total area of the processed photosensitive material.
When the counted total area exceeds the value corresponding to the predetermined contamination concentration, a predetermined amount of the purifying agent is supplied to the washing tank based on the experimental value. At this time, the system may have a system in which the experimental value is input in advance and the amount of the cleaning agent corresponding to the total area value is calculated and automatically supplied, or the total area counter is When the value exceeds a predetermined value, an alarm sounds, and in response to this, it may be artificially supplied based on experiments.

As a supply method at this time, it is preferable to supply the necessary purifying agent as it is to the water in the water washing tank as it is in order to enhance the stirring effect thereof, rather than dropping it from the upper part of the water washing tank. In particular, it is preferable to enter the position of 4 to 5 cm or less as an effect of being dissolved in the liquid rather than the water surface of the washing tank.

By adding the purifying agent as described above,
At least a part of the wash water purified to a predetermined value, at least a value that sets the drainage standard, is drained by the drainage means 3. The drainage means has, for example, a solenoid valve and can be opened and closed automatically, but the valve may be opened automatically after the supply of the cleaning agent, or automatically or manually after the cleaning agent supply or cleaning is confirmed. You may open it and drain it.

At this time, in particular, when a prescribed amount of a fixed amount of the purifying agent is added, it is faster to dilute with a small amount of a high-concentration substance and to feed a fixed amount of the substance at once, rather than dropping a small amount of the high-concentration substance. It is good to be stirred. Especially in the diluted state, a part of the rinse water that has been polluted and purified automatically as the amount of water increases is directly discharged to the sewer as overflow drainage. At this time, the purifying agent may be added to the washing tank from one place, but in order to enhance the stirring effect and prevent the adhesion of pollutants due to the circulation effect of the internal water, it is injected by several nozzles. Preferably. In particular, it is particularly preferable that the nozzle holes are fed at two or more locations by pump pressure in order to enhance the injection effect. A type such as a mold in which an injector is placed at the bottom of the washing tank and injected upward from the hole is particularly effective.

It should be noted that the adhesion of dirt, which is apt to occur in a conventional water-saving type automatic processor for washing with accumulated water as in the present invention, is particularly eliminated by eliminating the circulation pipe and incorporating this diffusion effect.

As a result, the water quality in the automatic processor is always kept constant, and the washing tank does not become empty due to the replacement of water during processing, which is particularly preferable from the viewpoint of work efficiency.

In the present invention, the effect of the present invention can be exhibited by using the above-mentioned purifying agent as the following as means for washing the water washing portion of the automatic processor. That is, after the automatic processor is stopped, all the rinsing water in use is drained, and then the water is supplied again to the rinsing tank. A purifying agent having a constant concentration is administered into the washing tank by the purifying agent supply means, and after maintaining a constant contact time, it is drained again.

In the present invention, the constant concentration of the purifying agent means
It is in the range of 600 ppm to 2000 ppm in wash water, especially 800 ppm to 2
It is preferably in the range of 000 ppm. If it is less than 600 ppm, its effect is not exerted, and if it exceeds 2000 ppm, the concentration is too high, which is not desirable for work.

On the other hand, the constant contact time means at least 1
It is at least 2 hours, particularly preferably at least 2 hours. If the contact time is too short, the cleaning effect will not be fully exerted.

As the washing means of the automatic processor to which the present invention is applied, various conventionally known washing tanks and washing methods can be used. In particular, the present invention can be carried out immediately by simply attaching and installing it to a conventional automatic developing machine. In this case, it is particularly preferable to install the cleaning agent in the automatic processor considering the space for installing the cleaning agent supply means and the cleaning agent itself. Specifically, it is preferable that the mechanism shown in FIGS. 1 and 2 be directly absorbed in the automatic processor.

As described above, as in the present invention, the purifying agent supplying means is provided to recycle the washing water to increase the water saving efficiency, and further to purify the contaminated washing water generated by the increase in the treatment amount. The idea of performing wastewater treatment was first discovered by the present inventors as a result of earnest research, and has never been found in the prior art.

The silver halide light-sensitive material applied to the present invention is preferably a black-and-white light-sensitive material, particularly preferably a black-and-white negative film, a black-and-white reversal film, an X-ray film, a copying film, a printing film, a gravure film, a black-and-white paper. , Computer typesetting paper and the like.

Further, for the developing section, fixing section and drying section of the automatic developing machine to which the present invention is applied, any of various conventionally known systems can be used.

A combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones as a developing agent is preferably used in the black-and-white developing solution used. Of course, in addition to this, p
-Aminophenol-based developing agents may be included.

The dihydroxybenzene developing agent used is hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone,
There are 2,5-dichlorohydroquinone, 2,3-dipromhydroquinone, 2,5-dimethylhydroquinone and the like, but hydroquinone is particularly preferable.

The developing agents for 1-phenyl-3-pyrazolidone or its derivatives include 1-phenyl-4,4-dimethyl-3-pyrazolidone and 1-phenyl-4-methyl-.
4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone and the like.

As the P-aminophenol type developing agent, N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, N- (4-hydroxyphenyl) glycine, Two
-Methyl-p-aminophenol, p-benzylaminophenol and the like are available, but N-methyl-p-aminophenol is preferred.

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

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

Alkaline agents used to set the pH include sodium hydroxide, potassium hydroxide, sodium carbonate,
Includes pH adjusters such as potassium carbonate, sodium triphosphate, potassium triphosphate.

JP-A-61-28708 (borate),
Buffering agents such as JP-A-60-93439 (for example, saccharose, acetoxime, 6-sulfosalicylic acid), phosphates and carbonates may be used.

As additives used in addition to the above components, sodium sulfite, potassium sulfite, lithium sulfite,
Sulfites such as ammonium sulfite, sodium bisulfite, potassium metabisulfite and formaldehyde sodium bisulfite; development inhibitors such as sodium bromide, potassium bromide and potassium iodide: ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, Methyl cellosolve, hexylene glycol,
Organic solvents such as ethanol and methanol: 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole-5-mercapto compounds such as sodium salt of sulfonic acid, indazole compounds such as 5-nitroindazole, 5-methylbenztriazole Antifoggants such as benztriazole compounds may also be included, and if necessary, toning agents, surfactants, desensitizers, water softeners, amino compounds described in JP-A-56-106244, and the like. But it's okay.

A silver stain preventing agent, for example, JP-A-56 is used in the developer.
The compounds described in No. 24347 can also be used.

The developer used is, for example, JP-A-56-10.
Amino compounds such as alkanolamines described in 6244 can be used.

Besides this, L. F. A. Meson's "Photographic Processing Chemistry", Focal
You may use what is described in the press publication (1966) pages 226-229, US Patent 2,193,015, 2,592,364, Unexamined-Japanese-Patent No. 48-64933 etc.

The fixing solution used is an aqueous solution containing thiosulfate, and has a pH of 3.8 or higher, preferably 4.2 to 5.5.
Have.

Examples of the fixing agent include sodium thiosulfate and ammonium thiosulfate, which have thiosulfate ion and ammonium ion as essential components, and ammonium thiosulfate is particularly preferable from the viewpoint of fixing speed. The amount of the fixing agent used can be appropriately changed and is generally about 0.1-6.
Mol / liter.

The fixing solution may contain a water-soluble aluminum salt which acts as a hardening agent, and examples thereof include aluminum chloride, ammonium sulfate, potassium alum and the like.

In the fixing solution, tartaric acid, citric acid or their conductors can be used alone or in combination of two or more kinds. It is effective that these compounds contain 0.005 mol or more per liter of the fixing solution, particularly 0.01 mol / liter to 0.03 mol / liter.

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

Preservatives (eg sulfite, bisulfite), pH buffers (eg acetic acid, nitric acid), pH adjusters (eg sulfuric acid), chelating agents having the ability to soften water in water may be used in the fixing solution, if desired. The compounds described in Japanese Patent Application No. 60-213562 may be included.

[0071]

EXAMPLES The present invention will be described more concretely with reference to the following examples.

An automatic processor (automatic processor GR-27 manufactured by Konica Corporation) installed as shown in FIG.
Process the film. Film size All size 508 x 610
The type and amount of the cleaning agent and 0.7 liter of water shown in Table 1 for each processing area corresponding to mm ² are sent into the washing tank as needed based on information from the developer replenishing operation signal of the automatic processor.
At this time, the washing water in the washing tank overflows by the supplemental amount. In this manner, 135 full-size films were processed consecutively each day. At this time, I ₂ consumption and pH were measured as water quality standards. The I ₂ consumption amount and pH were calculated by iodometric titration by collecting from the washing water tank during the treatment. In addition, the stain in the washing tank rack was also evaluated. The above film is a bright room return film CRH (manufactured by Konica Corporation) for plate making printer P-
607 (Light source: Ultra-high pressure mercury lamp URT-CHM-100
0) Exposure and blackening rate of about 20 by Dainippon Screen Co., Ltd.
% Was used.

In this embodiment, hydrogen peroxide solution is used as a cleaning agent (regenerating agent), and the same prescription as the cleaning agent after cleaning the automatic developing machine is used. A cleansing agent was used.

The concentration of the hydrogen peroxide solution used as the regenerant is shown in Table 1, and the concentration of the cleaning agent as the cleaning agent is the same as the hydrogen peroxide solution in this embodiment. is there. The concentration and contact time are shown in the table.

The results are shown in Table 2.

[0076]

[Table 1]

[0077]

[Table 2]

From the above results, according to the present invention, the water quality can be kept constant even if it is continuously used for a long period of time, and it can be operated for a long time without cleaning the washing tank, resulting in a very excellent maintenance-free property. it is obvious.

[0079]

As described in detail above, according to the present invention, it is possible to reuse the washing water for the automatic processor, and as a result, the water saving efficiency is improved. In addition, the contaminated wash water can be purified to the extent that it can be drained, and the problems that occur in the conventional circulation piping can be structurally eliminated. Furthermore, the apparatus of the present invention is compact and inexpensive, and can be easily installed and installed in a conventional automatic developing machine, which is convenient. According to the present invention, it is possible to realize a maintenance-free automatic water-saving processor that is extremely excellent in the effect of preventing dirt from adhering to the wash tank and does not require cleaning of the wash tank.

[Brief description of drawings]

FIG. 1 is a schematic diagram schematically showing the configuration of an embodiment of the present invention.

FIG. 2 is a schematic diagram schematically showing the configuration of another embodiment of the present invention.

[Explanation of symbols]

1 Washing tank (means) 2 Purifying agent supply means 3 drainage means 4 means of addition

Claims (4)

[Claims] 1. A regenerating means for regenerating and treating the washing water when the processing is carried out by an automatic developing machine for silver halide photosensitive materials comprising at least a developing section, a fixing section and a washing section, and the washing water. When the contamination concentration of exceeds a predetermined value, a purifying agent supplying means for supplying a purifying agent containing an oxidizing agent and a preservative to the washing section, and at least a part of the washing water in the washing section can be drained after the purifying agent is supplied. Drainage means having means for measuring the contaminated concentration of washing water, and washing means washing means for performing washing with a constant contact time by administering a constant concentration of the cleaning agent to the washing means after stopping the automatic developing machine An apparatus for regenerating and purifying washing water for automatic developing machines, which comprises: 2. The apparatus for regenerating and purifying wash water for an automatic processor according to claim 1, wherein the regenerating unit also serves as the purifying agent supplying unit. 3. The apparatus for regenerating and purifying wash water for an automatic processor according to claim 1, wherein hydrogen peroxide water is used as the oxidizing agent. 4. A method of processing a silver halide light-sensitive material, which is carried out by using the apparatus for regenerating and purifying washing water for an automatic processor according to claim 1, 2, or 3.