JPH0580463A - 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 process a silver halide photosensitive material by using a device for regenerating and purifying the washing water for an automatic developing machine capable of preventing the generation of water scales caused by mold and bacteria without deteriorating the picture due to the deposition of silver-compd. sludge on the material. CONSTITUTION:A silver halide photosensitive material is processed by an automatic developing machine consisting of at least a developing part, fixing part and water washing part. In this case, the developing machine is provided with a means 2 for regenerating washing water, a means for supplying a purifying agent contg. an oxidizing agent and a preservative to the water washing part when the degree of contamination of the washing water exceeds a specified value, a means 3 furnished with a measure for measuring the degree of contamination of the washing water so that at least a part of the washing water in the water washing part is discharged after the purifying agent is supplied, and a means for automatically supplying a specified amt. of water from a water source 4 after some unprocess time has passed.

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 developing machines and a method for processing a silver halide light-sensitive material using the apparatus. More specifically, it has high water-saving efficiency and is excellent in that no sludge is generated. The present invention relates to a compact and inexpensive apparatus for regenerating and purifying washing water for automatic developing machines, which gives excellent finishing performance, and a method for processing a silver halide light-sensitive material using the apparatus.

[0002]

2. Description of the Related Art At present, 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, particularly the fixing liquid component, in the washing process. Insufficient washing with water causes performance problems such as deterioration of an image with time due to residual fixer components 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 it is impossible to perform sufficient water washing as described above with the amount of washing water stored in the water washing tank in the automatic processor. Met. For this reason, the present situation is that tap water is constantly 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 viewpoints of resource saving and production cost reduction, demands for water saving at the time of rinsing of an automatic developing machine have increased, and technical improvement demands accompanying this have also 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 outages 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 and the problem of the regulation of the total amount of waste water.

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

In recent years, there has been proposed a device for decomposing a fixing component with an oxidizing agent, particularly hydrogen peroxide, as shown in Japanese Patent Application No. 3-63901, and using an oxidizing agent such as hydrogen peroxide. In the case of saving water, silver sulfide precipitates are likely to occur due to the reaction of thiosulfate ion or silver ion as a fixing component and an oxidizing agent, and this may be deposited as sludge on the film to deteriorate the image quality. Further, as a means for preventing sludge of silver compounds, it has been proposed to include a mercapto compound in hydrogen peroxide-treated washing water as in JP-A-63-044654, but a large amount is required to obtain a sufficient effect. Mercapto compound was required, and it was not practical because the running cost was very high.

[0006]

SUMMARY OF THE INVENTION The first object of the present invention is to prevent the deterioration of the image due to the adhesion of silver compound sludge to the light-sensitive material, to have excellent water-saving efficiency, and to prevent the generation of scale caused by mold and bacteria. It is an object of the present invention to provide an apparatus for regenerating and purifying wash water for an automatic processor and a method for processing a silver halide light-sensitive material using the apparatus.

[0007]

Means for Solving the Problems As a result of intensive studies conducted by the present inventors in view of the above problems, the above objects are at least
In the case of processing with an automatic developing machine for a silver halide light-sensitive material comprising a developing section, a fixing section and a washing section, a regenerating unit for reprocessing the washing water and a contaminated concentration of the washing water have a predetermined value. When it exceeds, a cleaning agent supply means containing an oxidizing agent and a preservative in the washing section, and a means for measuring the contaminated concentration of the washing water so that at least a part of the washing water in the washing section can be discharged after the cleaning agent is supplied. Drainage means provided,
And a means for automatically supplying a predetermined amount of water when a certain amount of unprocessed time has elapsed, and a reclaiming and purifying apparatus for washing water for an automatic processor, and a silver halide light-sensitive material using the apparatus. It was found that it was achieved by the processing method of.

In other words, when the untreated time has passed to some extent, that is, before the silver sulfide (AgS) grains have grown, the dilution water is automatically added to suppress the generation of silver sulfide grains. It was successful.

The present invention will be described in more 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,
An oxidant supply means 2 for automatically supplying an oxidant based on the photosensitive material processing area information as a regenerating or purifying means to a water washing tank 1 of an automatic processor for processing a photosensitive material, and a water washing tank 1.
An oxidizer is added to decompose the hypo that is brought in, but if the contaminated concentration is considered from the accumulation of elution components from the light-sensitive material, it is necessary to change the water, so it is less A drainage means 3 equipped with a means for measuring the contaminated concentration of the wash water so that a part of the wash water can be drained, and a compound having a polyalkylene oxide chain or a fungicide in the wash water in the wash tank 1 are present. It is composed of an addition means (not shown).

Here, the purifying agent is sent from the supply tank 2a to the dilution mixing tank 2b at any time by receiving a replenishment signal from the automatic developing machine, is diluted with water, and is supplied to the washing tank 1 when a certain contamination concentration, that is, a certain processing area is reached. It is like this. At this time, the diluted mixed water is fed from the bottom of the washing section of the automatic processor through a nozzle injection type supply port for the purpose of improving the stirring efficiency. The washing process proceeds according to the above principle for the treatment time, but when the untreated time has passed to some extent, that is, when the washing water in the washing tank has not been exchanged and the sludge generation reaction has progressed to some extent, only tap water is washed from the water source 4. It is automatically supplied to the tank to dilute and reduce the concentration of the reaction product in the water washing tank. At this time, the amount of dilution water is preferably 50% to 400%, more preferably 80% to 250% of the capacity of the washing tank. If the amount of dilution water is too small, the sludge prevention effect will be reduced, and if it is too large, the water saving efficiency will be reduced. It is preferable that the dilution water is introduced at regular intervals, for example, every 2 to 4 hours in the unprocessed time, but only when the photosensitive material is not processed once after the dilution water is added. Even if the untreated time exceeds the predetermined time, it is not necessary to add more dilution water. Also,
If the photosensitive material has never been processed after the automatic processor is started up, no dilution water may be added regardless of the unprocessed time. This is because in these cases, the fixing components (thiosulfate ion, silver ion) brought in from the fixing tank are brought into the water washing tank by carryover by the light-sensitive material.

In the present invention, the degree when the untreated time has passed to some extent correlates with the time when silver sulfide precipitation occurs, and is preferably 30 minutes to 10 hours, more preferably 1 hour to 8 hours.

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 water washing tank 1. Normally, however, a fixed amount is automatically added from the supply tank as needed, preferably within a fixed time.
It is added to the water washing tank 1 in the order of degree. The addition amount can be arbitrarily selected depending on the type of the light-sensitive material, the processing amount, the type of the processing liquid, etc. In a system in which the necessary amount is automatically added in a unit, it is in the range of ½ mol to several times the equivalent mol, particularly ½ mol, relative to the thiosulfate ion in the fixing solution to be held.
It is preferably added in the range of 3 to 3 molar equivalents. In addition, since the fixer component itself that is actually brought in is proportional to the amount of the processing photosensitive material, the addition amount can be determined by the amount of the processing photosensitive material. The washing tank 1 can have a known stirring means in order to efficiently regenerate it.

As the stirring means, it is preferable to use a circulation pump in the water washing tank or to put a stirring unit equipped with a small propeller into the washing machine to utilize its function.

When the amount of treatment 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 drainage standard, drainage to the sewer becomes impossible, so it is necessary to constantly detect the contamination 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 the 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 washing 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 has the same oxidizing agent as that used as the above-mentioned regenerating means, but may further contain a preservative, a compound having a polyalkylene oxide chain, and a fungicide. preferable.

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, it is, for example, 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 does not fall below 5.7. Should be added.

The compounds having a polyalkylene oxide chain used in the present invention include the compounds shown below.

[0021]

[Chemical 1]

[0022]

[Chemical 2] The addition amount of the compound having a polyalkylene oxide chain is 1 ppm to 1000 ppm, and more preferably 10 ppm with respect to washing water.
ppm to 100 ppm, and when contained as a cleaning agent, 0.01% to 10%, more preferably 0.1%, based on the cleaning agent.
~ 5%.

The anti-bacterial agent used in the present invention may be any as long as it does not adversely affect the photographic performance, but specifically, it is a thiazolylbenzimidazole compound, an isothiazolone compound, a chlorophenol compound, bromophenol. Compounds, thiocyanate or isothiocyanate compounds, acid azide compounds, diazine or triazine compounds, thiourea compounds, alkylguanidine compounds, quaternary ammonium salts, organic tin or organic zinc compounds,
Cyclohexylphenol-based compound, imidazole and benzimidazole-based compound, sulfamide-based compound,
There are various antibacterial agents and antifungal agents such as active halogen compounds such as chlorinated sodium isocyanurate, chelating agents, sulfite compounds and antibiotics represented by penicillin. In addition, LE West, “Water Quality Cr
iteria "Phot. Sci. and Eng., Vol 9 No. 6 (19
65) disinfectant; JP-A-57-8542, JP-A-58-105145,
Various anti-fungal agents described in 59-126533, 55-111942, and 57-157244; "Chemistry of antibacterial and antifungal" Hiroshi Horiguchi, Sankyo Publishing (sho 57), "Antibacterial and antifungal technology""Handbook" Chemicals such as those described in Japan Society for Antibacterial and Antifungal and Gihodo (Sho 61) can be used.

Specific examples are shown below, but the invention is not limited thereto. 1. 5-chloro-2methyl-4-isothiazoline-3
-On 2. 2- (4-thiazolyl) -benzimidazole 3. Methyl isocyanate 4. 3,5-dichloro-4'-fluoro-thiocarbanilide 5. 4-chloro-3,5-dimethylphenol 6. 2,4,6-trichlorophenol 7. Sodium dehydroacetate 8. Sulfanilamide 9. 3,4,5-Tribromosalicylanilide 10. Potassium sorbate 11. Benzalkonium chloride 12. 1-Bromo-3-chloro-5,5-dimethylhydantoin 13. Monochloroacetamide 14. Monobromoacetamide 15. Monoiodoacetamide 16. Benzimidazole 17. Cyclohexylphenol 18. 2-octyl-isothiazolin-3-one 19. Ethylenediaminetetraacetic acid 20. Nitrilo-N, N, N-trimethinephosphonic acid 21. 1-hydroxyethane-1,1-diphosphonic acid 22. Ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid 23. Chlorinated sodium isocyanurate 24. 2-Methyl-4-isothiazolin-3-one 25. 10,10'-oxybisphenoxyarsine 26. 1,2-benzisothiazolin-3-one

These exemplified compounds are described in US Pat.
2,767,172, 2,767,173, 2,767,174, 2,87
No. 0,015, British Patent No. 848,130, French Patent No. 1,555,416, and the like, their synthesis methods and application examples to other fields are described. There are also commercially available products such as Predentor ON, Permachem PD, Topside 800, Topside EG5, Topside 300, Topside 600 (above Permakem Asia Co., Ltd.), Fineside J-700 (Tokyo Fine Chemical Co., Ltd.). ) Prozel
It can be obtained under the trade name of GXL (manufactured by ICI).

When the above antibacterial agent is supplied in washing water, it is preferably 0.01 to 50 g / liter, more preferably 0.0 to 50 g / liter.
5-20g / l is good. When it is contained as a purifying agent, it is 0.1 to 50 g / liter, more preferably 1 to 20 g / liter based on the purifying agent.

When the oxidant supply tank is provided as the regenerating means, the purifying agent supply means as shown in FIG. 1 is preferably used also as the oxidant supply tank 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 standard value of iodine consumption, these purifying agents can be added depending on the concentration, such as water. Is diluted with and 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 at a rate of about once in a fixed time so that the supply valve is opened and automatically dropped. 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 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 purification 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 lowest 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 carried out automatically by adding sodium hypochlorite until V is reached. By 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 placed in a water washing tank and measured continuously or appropriately as needed, or may be inserted into the water washing tank at any time for measurement. This measured value is fed back to the cleaning agent supply means automatically or artificially, and by operating, for example, an electromagnetic opening / closing valve,
The required amount of the purifying agent can be supplied to the washing water in the washing tank. In the water washing tank, an ordinary well-known stirring means may be provided 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 the main contaminant, thiosulfate ion, 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 light-sensitive 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 the automatic processor, and a counter connected to the sensor is detected based on the information of the sensor. And count the total area of the processed photosensitive material.
When the counted total area exceeds a value corresponding to a predetermined pollution concentration, a predetermined amount of the cleaning agent is supplied to the water 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 An alarm sounds when the value exceeds a predetermined value, and accordingly, the alarm may be artificially supplied based on an experiment.

As a supply method at this time, it is preferable to supply the water to the water in the washing tank as it is, in order to enhance the stirring effect thereof, rather than dropping the required cleaning agent from the upper portion of the 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, an electromagnetic 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 specified amount of a fixed amount of the purifying agent is added as described above, it is quicker to dilute with a small amount of a high-concentration substance and to feed a fixed amount of the substance all at once. It is good to be stirred. Especially in the diluted state, as the amount of water increases, part of the wash water that has been automatically polluted and purified 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 adherence 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 pumping 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 tends to occur in the conventional water-washing type water-saving type automatic developing machine 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, which is particularly preferable in terms of work efficiency. 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 of FIG. 1 is 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 applicable 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.

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

A combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones is preferably used as a developing agent in the black-and-white developing solution used. Of course, 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.

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

As P-aminophenol type developing agents, N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, N- (4-hydroxyphenyl) glydin, 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
The range is.

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, desensitizing agents, water softeners, amino compounds described in JP-A-56-106244, and the like. But it's okay.

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

The developing solution used is described in JP-A-56-10.
Amino compounds such as the 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 to 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, and particularly 0.01 mol / liter to 0.03 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.

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

[0059]

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

Example 1 A film is processed by an automatic processor installed as shown in FIG. The size and size of the cleaning agent and 0.7 liter of water as shown in Table 1 for each processing area corresponding to the total size of the film, 508 x 610 mm ² , are sent into the washing tank as needed based on the information from the developer replenishment signal of the automatic processor. .. At this time, the wash water in the wash water overflows by the supplemental amount. At this time, when the unprocessed time between the treatments was left for 4 hours, the washing tank capacity water was automatically used as the washing tank dilution water by using the timer and the solenoid valve operation.

Comparative Example 1 The same treatment as in Example 1 was carried out except that no diluting water was added even after the untreated time of 4 hours or more.

Comparative Example 2 Treatment was carried out by an ordinary automatic developing machine without any scale prevention and water saving device.

In each of the methods of Example 1 and Comparative Examples 1 and 2, 120 large-size films were intermittently processed for 4 months, 120 sheets per day. As an evaluation, the dirt on the washing tank rack, the amount of water used, and the water quality (amount of iodine consumed, pH) were evaluated. In addition, the film is a light-turning film CRHE-A (manufactured by Konica Co., Ltd.) that is exposed by a plate-making printer P-607 (manufactured by Dainippon Screen Co., Ltd.) and has a blackening rate of about 20%. , The automatic processor is GR-2
7 (manufactured by Konica Corporation) was developed at 28 ° C. for 30 seconds. The results are shown in Table 2.

From the results shown in Table 2, it is clear that according to the present embodiment, there is no image deterioration due to the adhesion of sludge, the generation of scale is prevented, and the water saving efficiency is excellent.

[0065]

[Table 1]

[0066]

[Table 2]

[0067]

EFFECTS OF THE INVENTION The apparatus for regenerating and purifying washing water for automatic processors of the present invention and the treatment method using the apparatus are compact and inexpensive apparatus having high water-saving efficiency, no sludge generation, and excellent finishing performance. And a processing method can be provided.

[Brief description of drawings]

FIG. 1 is a schematic view schematically showing an example of a cleaning and purifying apparatus for washing water for an automatic processor of the present invention.

[Explanation of symbols]

 1 Water washing tank of automatic processor 2 Oxidant supply means 3 Drainage means 4 Water source

Front Page Continuation (72) Inventor Akashi Akashi No. 1 Sakura-cho, Hino City, Tokyo Konica Stock Company

Claims (6)

[Claims] 1. A regenerating unit for reprocessing 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 containing an oxidizing agent and a preservative in the washing section, and washing water so that at least a part of the washing water in the washing section can be drained after the purifying agent is supplied. Rinsing water for automatic processor characterized in that it comprises a draining means having a means for measuring the concentration of contaminants, and a means for automatically supplying a predetermined amount of water when the untreated time has passed to some extent. Regeneration purification device. 2. The apparatus for regenerating and purifying washing water for automatic developing machines according to claim 1, wherein the regenerating unit also serves as the purifying agent supplying unit. 3. The purifying agent contains a compound having at least one polyalkylene oxide chain.
Alternatively, the apparatus for regenerating and purifying washing water for an automatic processor according to 2 above. 4. The apparatus for regenerating and purifying washing water for automatic processors according to claim 1, wherein the purifying agent contains at least one anti-bacterial agent. 5. The apparatus for regenerating and purifying wash water for automatic processors according to claim 1, 2, 3 or 4, wherein hydrogen peroxide is used as the oxidizing agent. 6. A silver halide light-sensitive material, characterized in that the silver halide light-sensitive material is processed using the reclaiming and purifying apparatus for washing water for an automatic processor according to claim 1, 2, 3, 4 or 5. Processing method.