JP2782222B2 - Automatic developing apparatus having built-in water saving mechanism, processing method of silver halide black-and-white photosensitive material using the apparatus, and wastewater processing method - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to an automatic developing apparatus for a silver halide black-and-white photosensitive material, and more particularly, to an automatic developing apparatus having a built-in water saving mechanism and a halogenating apparatus using the automatic developing apparatus. The present invention relates to a method for processing silver black and white photosensitive materials and a method for treating wastewater.

[Prior Art] At present, development processing of a silver halide light-sensitive material is generally performed using an automatic developing machine, and such an automatic developing machine generally includes developing, fixing, washing and drying. The photosensitive material that has been subjected to the developing and fixing processes is subjected to a washing step, in which a processing solution component in the preceding step, particularly a fixing solution component, contained in the material is washed away. If the washing is insufficient, especially in a black-and-white silver halide photosensitive material, performance problems such as deterioration of an image with time due to a residual fixing solution component in the material occur. Therefore, it is necessary to perform sufficient rinsing to sufficiently remove the residual fixing solution components in the photosensitive material. However, as described above, sufficient rinsing cannot be performed with the amount of rinsing water contained in the rinsing tank in the automatic developing machine. Met. For this reason,
At present, tap water is always supplied at the time of rinsing treatment, and overflowing rinsing water is directly discharged to water and sewage.

Under these circumstances, in recent years, from the viewpoint of resource saving and reduction of production cost, there has been an increasing demand for water saving at the time of washing an automatic developing machine, and accordingly, a demand for technical improvement has also increased. In other words, problems such as land subsidence in urban areas, rising water and sewage rates due to capital investment for delays in sewage treatment facilities, and washing water for addressing water outages caused by specific weather conditions in summer in specific areas. The demand for savings has been increasing in recent years, coupled with the increase in throughput at platemaking and the problem of total wastewater regulations.

In response to such water saving requirements, conventionally, for example, an anhydrous washing / no-pipe system in which a water washing process is performed by a countercurrent washing method or a chemical treatment is performed instead of the water washing process has been proposed. It has already been put to practical use in the treatment process.

[Problems to be Solved by the Invention] However, for current black-and-white silver halide photosensitive materials,
Particularly, an automatic developing apparatus for printing plate making is usually relatively large in spite of the fact that each of the developing, fixing, and rinsing steps is constituted by one tank, and thus is relatively large. Applying a piping system to the automatic developing device
Further increase in the size of the apparatus such as an increase in the processing tank is caused. As a result,
The processing line length is longer and the processing time of the photosensitive material is longer. In view of the speeding up of processing in recent mass processing, it is in a completely opposite direction, and practical use has been difficult.
Further, if the processing speed is to be increased in such an apparatus as described above, it is necessary to further increase the processing line speed. In such a case, the physical load on the photosensitive material increases, and Problems such as scratches and peeling of the film surface, or charging of the photosensitive material due to friction.

Therefore, as one method, a method is conceivable in which a water tank for storing washing water is provided in the vicinity of the washing tank separately from the washing tank for performing the washing processing, and the washing water is circulated between the water tank and the washing tank. However, according to this method, the concentrations of the developing solution, the fixing solution component, and the components eluted from the photosensitive material in the previous step brought into the washing water by the photosensitive material to be processed are increased in accordance with the increase in the processing amount, and especially in recent years, In large-scale treatment, the value of iodine consumption as a legally defined water quality standard is exceeded in a short period of time, and a drainage problem remains. That is, a method that simultaneously satisfies the problems of water saving efficiency and wastewater treatment has not been found yet.

Accordingly, a first object of the present invention is to provide an automatic developing apparatus capable of recycling washing water, thereby improving water saving efficiency, and a method for processing a silver halide black-and-white photosensitive material using the apparatus. is there.

A second object of the present invention is to provide an automatic developing apparatus which incorporates a water saving efficiency mechanism which is small in physical load on the photosensitive material, is compact, and has improved maintenance and cost.

A third object of the present invention is to provide an automatic developing apparatus capable of purifying contaminated washing water to the extent that it can be drained.

A fourth object of the present invention is to provide an automatic developing apparatus and a processing method which can prevent an increase in a residual fixing solution component of a silver halide black-and-white photosensitive material at the time of washing and provide excellent image characteristics.

A fifth object of the present invention is to provide a method for treating wastewater of contaminated rinsing water which is generated with the improvement of water saving efficiency.

[Means for Solving the Problems] The present inventors have conducted intensive studies in view of the above problems, and as a result, have found that the object of the present invention is achieved by the following constitutions.

(1) In an automatic developing apparatus for a silver halide black-and-white photosensitive material comprising at least a developing section, a fixing section and a rinsing section, the rinsing section includes at least rinsing means for rinsing the photosensitive material, and use discharged from the rinsing means. Water, including washed water,
Water storage means for temporarily storing as washing water supplied to the washing means; at least one regenerating means for regenerating the used washing water; washing the washing water in the washing means and the washing water in the storage means with the washing means A circulating means for circulating between the means and the water storing means; a purifying agent supplying means for supplying a purifying agent to the water storing means when a contamination concentration of the washing water circulated by the circulating means exceeds a predetermined value; Draining means for draining at least a part of the washing water in the water storing means after supplying the purifying agent, and the washing unit is incorporated therein, and the automatic developing apparatus for a silver halide black-and-white photosensitive material is provided. .

(2) The automatic developing apparatus according to (1), wherein the regenerating means is a filter provided between the washing means and the water storing means.

(3) The automatic developing apparatus according to (1), wherein the regeneration means comprises an oxidant supply means for supplying the oxidant to the water storage means.

(4) The automatic developing device according to (1), wherein the regeneration means comprises a filter provided between the washing means and the water storage means and an oxidant supply means for supplying the oxidant to the water storage means.

(5) The automatic developing device according to (1), wherein the purifying agent is an oxidizing agent.

(6) The automatic developing apparatus according to (1), wherein the purifier supply means also serves as the oxidant supply means.

(7) The black-and-white silver halide light-sensitive material is described in (1) to (1).
(6) A method for processing a silver halide black-and-white light-sensitive material, wherein the processing is performed using the automatic developing device according to any one of (6) and (5).

(8) When processing a silver halide black-and-white photosensitive material using the automatic developing apparatus according to any one of claims (1) to (6), the concentration of contaminated washing water circulated to a predetermined value. In this case, the purifier is supplied from the purifier supply means to the water storage means to purify the washing water in the water storage means, and then at least a part of the wash water in the water storage means is drained by the drainage means. Wastewater treatment method.

Hereinafter, an automatic developing apparatus of the present invention will be described with reference to the drawings.

FIG. 1 is a schematic view schematically showing an example of a washing section of the automatic developing apparatus of the present invention. According to FIG. 1, the washing section of the developing apparatus of the present invention comprises a washing tank 1 for processing a photosensitive material, washing water for replenishing the washing tank 1 and washing water overflowing from the washing tank 1 due to the above replenishment. A water storage tank 2 provided in the automatic developing device and provided near the water cleaning tank 1 for storing water, and replenishing the cleaning water from the water storage tank 2 to the water cleaning tank 1 to store overflow water from the water cleaning tank 1. A circulating means 3 for feeding the liquid to the tank 2, a regenerating means such as a filter 4 provided in the middle of the path from the water tank 2 to the washing tank 1, and more preferably a washing water circulated by the circulating means 3 Automatically when the pollution concentration of the water exceeds a predetermined value
And a discharge means 6 for discharging at least a part of the washing water in the water storage tank 2 after the supply of the cleaning agent. I have. The washing section is provided in the automatic developing apparatus.

That is, at the start of the developing process, the washing tank 1 and the water tank 2 are filled with unused washing water, and then the developed and fixed photosensitive material is washed in the washing tank 1 and stored in accordance with the amount of the photosensitive processing. The washing water is automatically replenished from the tank 2 and, as a result, the used washing water overflowing from the washing tank 1 is sent to the water tank 2 without being drained as it is conventionally, and is temporarily stored. As the throughput increases, this circulation is repeated, whereby the washing water in the washing tank 1 and the water tank 2 is brought in by the photosensitive material, and is eluted from the fixing solution component or the photosensitive material such as dyes, dyes, surfactants, and gelatin. Contamination is caused by the components, and as a result, the washing efficiency is reduced and the finished photosensitive material after washing is adversely affected. To prevent this, for example, a filter 4 is provided as a regenerating means between the path from the water tank 2 to the water tank 1 or the path from the water tank 1 to the water tank 2 to adversely affect the photosensitive material from the water. Influencing components, in particular, thiosulfate ions, scale, mold and the like are removed, and the washing water is regenerated. As such a filter, there is an adsorption filter, and a filter in which an adsorbent component is attached to a filter fiber is used.

As a material of the filter fiber, carbon fiber, aramid fiber, Teflon resin fiber, hemp,
Glass fiber, polyethylene foam, polypropylene foam and the like are preferably used. Also, Japanese Patent Application Laid-Open No. 60-2631
The substance described as a contact substance in the specification of Japanese Patent Publication No. 51 can also be used.

Further, it is also preferable to use a method in which powder is filled in a filling unit in the form of a cartridge as an adsorbent and water is passed through the filling unit.

As the adsorbent referred to herein, an acid, a mixture of silicon oxide and magnesium as an alkali type adsorbent in the form of a fine powder, activated carbon fine powder for the purpose of activation, for example, nickel, calcium, magnesium, tin, iron, aluminum What mixed the metal fine particles, such as these, is mentioned. Further, natural stones such as zeolites having mesh-like pores, and synthetic zeolites in general and silica-alumina type adsorbents are preferable.Particularly, natural zeolite and synthetic zeolites are activated by supporting the above metal fine particles. Also, those having an increased adsorption area and improved ability as an adsorbent are preferably used.

Specific examples of the adsorbent include commercially available products such as Awa Paper Co., Ltd. Kyoward series, Kyoward 400, Kyoward 600, or polypropylene long fiber nonwoven fabric.

For example, the filter can be used in combination with a sheet filter made of, for example, activated carbon fiber to prevent clogging or the like due to a gelled substance such as gelatin. It is possible.

In addition, a separate oxidizing agent supply unit including an oxidizing agent supply tank is provided as a regenerating unit, and the oxidizing agent is supplied to the water storage tank 2 as needed, whereby the washing water can be regenerated.

Examples of such an oxidizing agent include metal or non-metal oxides, oxide acid-based acids or salts thereof, peroxides, compounds containing an organic acid-based compound, and the like. The acid-based acid is sulfuric acid, nitrous acid,
Nitric acid, hypochlorous acid and the like are preferable, and as the peroxide, hydrogen peroxide solution, Fenton's reagent and the like are preferably used. Also, ozone is 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 arranged adjacent to the water storage tank 2, but usually, a fixed amount is automatically added from the supply tank as needed. It is added to the water storage tank 2 in such a manner that the supply valve is opened and automatically dropped at a rate of about once every several hours. The amount of addition can be arbitrarily selected depending on the type of photosensitive material, the amount of processing, the type of processing solution, and the like. In a system in which the required amount is automatically added in units, the molar range is 1/2 mol to several times equivalent mol, especially 1/2 mol to equivalent mol, based on the thiosulfate ion in the fixing solution to be introduced. Is preferably added in the range. In addition, the amount of the fixing solution actually introduced is proportional to the amount of processed light, so that the amount of addition can be determined by the amount of processed light-sensitive material. Further, the water storage tank 2 may have a known stirring means in order to efficiently perform regeneration.

In the present invention, one of each of the above-described various reproducing means may be selected and used, or two or more of them may be used in combination.

If 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 water storage tank 2 and replace it with fresh washing water. However, in particular, when the degree of contamination exceeds the above-mentioned drainage standard, drainage to the sewer becomes impossible. Therefore, it is necessary to always detect the concentration of the washing water contamination and keep the concentration within an allowable range.
Therefore, the contamination concentration of the washing water is measured by any method, preferably, the washing water in the water tank 2 is measured by using the contamination concentration measuring means, and the cleaning agent supply tank 5 automatically outputs the contamination concentration based on the measured value. A purifying agent is supplied to purify the washing water in the water tank 2 to an allowable value. Thereafter, at least a part of the purified washing water can be drained by the drainage means 6. The washing water in the water storage tank 2 may be entirely drained, or only one part may be drained and replaced with fresh washing water to be mixed and used.

In the present invention, the contaminant concentration of the washing water is a fixing liquid component which is considered to have the greatest influence on the iodine consumption since it is considered that it is necessary to satisfy the iodine consumption regulation because the sewerage is discharged. It can be considered as the concentration of thiosulfate ions such as certain ammonium thiosulfate and sodium thiosulfate.

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

Further, when the oxidizing agent supply tank is provided as a regenerating means, the purifying agent supply tank 5 is preferably used in combination with the oxidizing agent supply tank.

For example, when the thiosulfate ion concentration of the washing water in the water tank 2 exceeds the value corresponding to the reference value of the iodine consumption, these purifying agents can be added according to the concentration, and diluted with water or the like. Then, it is added to the water storage tank 2 from the purifying agent supply tank 5 arranged adjacent to the water storage tank 2, but usually it is automatically added from the supply tank by a constant amount as needed, preferably in several hours. It is added to the water storage tank 2 in such a form that the supply valve is opened and dropped automatically at a rate of about one degree. The amount of addition can be determined by experiments or the like according to the thiosulfate ion concentration in the washing water.

As means for supplying a purifying agent in a fixed amount according to the thiosulfate ion concentration and automatically purifying the purifier according to the present invention, OR means
A method is possible in which the ORP value is measured with a P (redox potential) electrode and the purifying agent is automatically added based on the measured ORP value.

Specifically, a sodium thiosulfate solution having a predetermined concentration is adjusted to pH
After adjusting to 4 or pH 7, sodium hypochlorite is added, and the iodine consumption, KMnO ₄ consumption and ORP value are measured to determine the amount of the purifying agent added. That is, for example, 0.03N
-When sodium hypochlorite is added to each of the pH 4 and pH 7 Na ₂ S ₂ O ₃ solutions, the ORP value of the first wave rises sharply in the pH 7 solution at a certain amount. And
This coincided with the lowest value of iodine consumption. This is S ₂ O ₃
² indicates that the entire amount was oxidized. Further addition of sodium hypochlorite leads to the onset of the second wave of pH 7 solution and pH 4
A sharp rise of the solution is observed. Thus, in the neutral or acidic region, the rise of the ORP value is used to increase the value to +500.
Purification can be performed automatically by adding sodium hypochlorite until it reaches ~ 800 mV. By such a method, the amount of the purifying agent to be added can be determined by measuring the ORP value in various cases.

The ORP electrode may be installed in a water storage tank, and may be measured continuously or as needed, or may be measured by inserting the ORP electrode into the water storage tank as needed. Alternatively, the measurement value may be used in a circulation system outside the water storage tank, in a washing tank, or the like, and the measured value may be substituted for the measurement value in the water storage tank.

The measured value is automatically or artificially fed back to the purifying agent supply means, and, for example, by operating an electromagnetic on-off valve or the like, a necessary amount of the purifying agent can be supplied to the flush water in the water storage tank. In the water storage tank, a usual well-known stirring means may be provided to promote purification.

As another method of measuring the concentration of contamination, there is a method of measuring the area of the processed photographic material and substituting it. That is, since thiosulfate ion, which is a main contaminant, is a component carried by the processed light-sensitive material, its amount is considered to substantially correspond to the amount of the processed light-sensitive material, that is, the total area. Therefore,
The concentration of contamination when a predetermined amount of the photosensitive material is processed by an experiment and the amount of the purifying agent required to purify the concentration to a predetermined value are determined in advance, and the processed photosensitive material is used by using the result. May be measured and calculated, and a corresponding amount of the purifying agent may be supplied.

As such a method, specifically, a light-sensitive material is detected by a sensor provided near a light-sensitive material insertion port of an automatic developing machine,
The total area of the processed light-sensitive material is counted by a counter connected to the sensor based on the information of the sensor. When the counted total area exceeds a value corresponding to a predetermined contamination concentration, a predetermined amount of a purifying agent is supplied to the water tank based on the experimental value. At this time, the experimental values are input in advance,
A system for calculating and automatically supplying the amount of the purifying agent corresponding to the total area value may be provided in the apparatus,
When the total area counter exceeds a predetermined value, an alarm sounds, and the alarm may be supplied artificially based on an experiment.
In the water storage tank, a usual well-known stirring means may be provided to promote purification.

By adding the purifying agent as described above, a predetermined value,
At least a part of the washing water purified to at least a value satisfying the drainage standard is drained by the drainage means 6.
The drainage means has, for example, an electromagnetic valve and can be opened and closed automatically. However, the valve may be opened automatically after the supply of the cleaning agent, or automatically or artificially after the supply or purification of the cleaning agent is confirmed. It may open and drain.

As the washing means of the automatic developing apparatus of the present invention, various conventionally known washing tanks and washing methods can be used. Further, water containing various additives known in the art can be used as washing water. In particular, the washing water provided with a fungicide is effectively used for preventing the generation of scale in the water stagnated in the water storage tank.

Examples of such antifungal means include an ultraviolet irradiation method described in JP-A-60-263939, a method using a magnetic field described in JP-A-60-263940, and an ion-exchange resin described in JP-A-61-131632. No. 60-253807, 60
-295894, 61-63030, and 61-51396 using the antibacterial agent can be used.

Furthermore, LEWest “Water Quality Criteria” Photo S
ci & Eng. Vol.9 No.6 (1965), NWBeach “Microbiol
ogical Growths in Motion-Picture Processing "SMPTE
Journal Vol.85, (1976) .RODeegan, “Photo Proces
sing Wash Water Biocides "J.Imaging Tech.Vol.10, No.
6 (1984) and JP-A-57-8542, JP-A-57-58143, and JP-A-57-58143.
-105145, 57-132146, 58-18631, 57-9
No. 7530, antibacterial agents described in Nos. 57-157244 and the like,
Anti-binders, surfactants and the like can be used in combination.

In addition, RTKreiman's J.Image, Tech 10,
(6) Isothiazoline compounds described in 242 (1984), RESEARCH DISCLOSURE Vol. 205, Item 20526 (1981)
The compound described in Japanese Patent Application No. 61-51396, the isothiazoline compound described in Vol. 228, Item 22845 (April 1983, April 1983); Can be used in combination as a bacteriostatic agent (Microbiocide).

Further, specific examples of the anti-binder include phenol, 4-chlorophenol, pentachlorophenol, cresol, o-phenylphenol, chlorophen, dichlorophen, formaldehyde, glutaraldehyde, chloracetamide, p-hydroxybenzoate,
2- (4-thiazoline) -benzimidazole, benzisothiazolin-3-one, dodecyl-benzyl-dimethylammonium chloride, N- (fluorodichloromethylthio) -phthalimide, 2,4,4'-trichloro-2'-hydro Oxydiphenyl ether and the like can be mentioned.

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

The water tank 2 in the present invention can be made of vinyl chloride containing an antibacterial agent or the like, or a tank whose inside is nylon-processed, as the material of the tank, from the viewpoint of preventing water scale and corrosion.

As the circulating means in the present invention, for replenishing the washing water from the water tank 2 to the washing tank 1, for example, when a photosensitive material is inserted into an automatic developing machine, it is detected by a sensor, whereby the water is automatically removed from the water tank 2. An electromagnetic valve design in which the washing water is supplied to the washing tank 1 and the supply of the washing water is stopped when the photosensitive material is not detected may be used. At this time, it is preferable that the washing water is forcibly transferred by a high-pressure pump, and the replenishing washing water amount is preferably from 10 to 30, more preferably from 15 to 25, per 1 m ^{2 of the} processed light-sensitive material area.

Further, the washing water overflowing from the washing tank 1 due to the above replenishment is sent to the water tank 2 as it is through a pipe connected to the water tank 2 and is temporarily stored therein.

The water storage tank, the regenerating means, the circulating means, and the purifying means as described above can be arbitrarily incorporated by effectively utilizing the space at the stage of designing and manufacturing the automatic developing machine.

As described above, a water tank is provided as in the present invention, and rinsing water is circulated and used. By reusing the rinsing water, the water saving efficiency is increased, and further, the contaminated rinsing water generated due to an increase in the treatment amount is purified. The idea of performing wastewater treatment by performing the treatment and performing all of these treatments in a system built in the automatic developing apparatus was found by the present inventors for the first time as a result of earnest research, and is completely seen in the prior art. Not something.

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

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

In the black-and-white developer used in the present invention, a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones is preferably used as a developing agent. Of course, besides this, p-
It may contain an aminophenol-based developing agent.

As the dihydroxybenzene developing agent used in the present invention, hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone,
Although there are 2,5-dimethylhydroquinone and the like, hydroquinone is particularly preferred.

Examples of the developing agents of 1-phenyl-3-pyrazolidone or a derivative thereof include 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, and 1-phenyl- 4,4-dihydroxymethyl-3-pyrazolidone and the like.

Examples of p-aminophenol-based developing agents include N-methyl-p-aminophenol, p-aminophenol, and N-methylphenol.
(Β-hydroxyethyl) -p-aminophenol, N
-(4-hydroxyphenyl) glycine, 2-methyl-
Although there are p-aminophenol, p-benzylaminophenol and the like, N-methyl-p-aminophenol is preferable.

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

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

Alkaline agents used for setting the pH include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate tribasic, and potassium phosphate tribasic.
Contains pH adjusters.

Buffers such as JP-A-61-28708 (borate) and JP-A-60-93439 (for example, saccharose, acetoxime, 5-sulfosalicylic acid), phosphates and carbonates may be used.

Additives used in addition to the above components include sulfites such as sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, sodium formaldehyde sodium bisulfite; sodium bromide, potassium bromide, iodide Development inhibitors such as potassium: organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, ethanol and methanol: 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole-5 -Turnips such as mercapto compounds such as sodium sulfonate, indazole compounds such as 5-nitroindazole, and benztriazole compounds such as 5-methylbenztriazole May include agents, toning if necessary, surfactants, defoamers, water softeners, may contain such amino compounds described in JP-56-106244.

In the present invention, a silver stain inhibitor, for example, a compound described in JP-A-56-24347 can be used in the developer.

Amino compounds such as alkanolamines described in JP-A-56-106244 can be used in the developer used in the present invention.

LFA Meson, "Photographic Processing Chemistry", Focal Press (1966
226-229, U.S. Pat.Nos. 2,193,015 and 2,592,3
No. 64, JP-A-48-64933 and the like may be used.

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

Examples of the fixing agent include sodium thiosulfate and ammonium thiosulfate. Thiosulfuric acid ions and ammonium ions are essential components, and ammonium thiosulfate is particularly preferable from the viewpoint of fixing speed. The amount of the fixing agent to be used can be appropriately changed, and is generally about 0.1 to about 6 mol /. The fixing solution may contain a water-soluble aluminum salt acting as a hardening agent. , Ammonium sulfate, potassium alum and the like.

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

Specifically, there are tartaric acid, potassium tartrate, sodium tartrate, potassium sodium tartrate, citric acid, sodium citrate, potassium citrate, lithium citrate, ammonium citrate and the like.

The fixing solution may optionally contain a preservative (eg, sulfite or bisulfite), a pH buffer (eg, acetic acid or nitric acid), a pH adjuster (eg, sulfuric acid), a chelating agent having a water softening property, The compounds described in JP-A-60-213562 can be included.

[Example] An example of the present invention will be described below.

Experimental Example 1 Konica Fixer 851 (manufactured by Konica Corporation) (1) 300 cc, (2) 500 cc or (3) 700 cc as a fixing solution in water 62, assuming that a fixing solution component is brought into the washing water of the photosensitive material.
And 6% of hydrogen peroxide solution as a purifying agent
A substitution test was performed to determine the amount of purifying agent required to reduce the iodine consumption of the thiosulfuric acid component in the mixed fixing solution to the regulation standard value of 220 mg / or less by adding the solution. The results are shown in FIG. 2 for the above cases (1), (2) and (3). However, the amount of iodine consumed was adjusted to be almost neutral based on the sewage test method, and then a fixed amount of an iodine-potassium iodide solution was added to the sample, and the remaining iodine was left after standing at room temperature for 2 to 3 minutes. It was measured by titration with a 1 / 100N sodium thiosulfate solution.

From FIG. 2, it is sufficient to add hydrogen peroxide in a molar ratio of about 0.9 to 1.25 with respect to ammonium thiosulfate in order to reduce the iodine consumption of each of the three fixer concentrations to 220 mg / or more. You can see that. Similarly, the amount of hydrogen peroxide to be added can be determined for various thiosulfate ion concentrations.

<Example 1> The experiment was performed under the following experimental conditions.

Developing solution: Konica developer type 651K Fixing solution: Konica fixer type 851 Processing material: Konica clear light contact film CRH,
CRHE (Konica Corp.) Konica Clearlight contact film is a plate making printer P-607 (Light Source: Dainippon Screen Co., Ltd.)
Exposure with ultra-high pressure mercury lamp URT-CHM-1000), blackening rate about 50%
A paper size of 508 x 610 mm was used.

First, the supply valve from the water supply to the automatic processor having the same configuration as the Konica Automatic Processor GR-27 was cut off, and a water tank made of polyvinyl chloride having a volume of about 50 was installed in the space near the washing tank in the automatic processor. The water tank was filled with 40 water, and the GR-27 washing tank was also charged with 22 washing water, so that a total of 62 water was circulated. In this state, the aforementioned CRH and CRHE were continuously processed. As a result of continuous processing, 60
Bubbles began to be generated in the circulating water from the point of time of sheet processing. Further, rubber mixing and foam began to be noticeable from the time when the processing amount exceeded 100 sheets. In addition, the total processing 40 sheets, 65 sheets, 85 sheets, 105 sheets, 135 sheets
The levels of residual hypo in CRH and CRHE at the time of processing each of 150, 170, 200, 235, 270, and 300 sheets were checked, and the results are shown in Table 1.

 The residual hypo was measured by the following measuring method.

<Method of measuring residual hypo> One drop of the following detection solution is dropped on the minimum density portion (fog portion) of the processed film and left as it is for 3 minutes. The dripping liquid is absorbed by a blotter (filter paper) and left to dry.
The transmission density (D) of the portion contaminated with the detection solution is measured with a densitometer through a blue filter, and the fog density (Do) of the portion where the detection solution is not dropped is similarly measured to obtain D-Do. The net contamination concentration of residual hypo. This net contamination concentration is confirmed with a calibration curve, and the hypo concentration is read.

Detection solution Pure water 750 cc 28% acetic acid (3: 8) 125 cc silver nitrate 7.5 g Pure water finish 1000 cc Store this in a brown storage bottle and use the one prepared within 3 months.

Next, in the same experiment, KYOWARD 600 adsorbent (manufactured by Awa Paper Co., Ltd.) was attached to polypropylene fiber as a filter element along the piping path for circulation from the water tank to the washing tank, and folded into a cylindrical shape. This was performed with a filter formed by processing into a cartridge shape. In order to extend the lifetime of the filter as described above, activated carbon fibers are formed into a sheet and used in combination with the upper part of the cartridge. Table 1 shows the results of similarly measuring the residual hypo value of the light-sensitive material in the middle of continuous processing.
Shown in

When such is not through the filter, the residual hypo values affected by contamination of the water according to the process sensitive material amount Until continuous processing 150 sheets position is position ² 0.05 g / m becomes more residual The hypo value rises. On the other hand, when a filter is interposed, even if 270 sheets of large and full size are continuously processed, when stored as a recording film compliant with ANSI (1985) as a photographic storage property, the residual hypo Is below the level of 0.05 to 0.100 g / m ² , and it is determined that the image quality can be sufficiently guaranteed. In addition, in the circulation system without the filter, that is, in the circulation system without the regenerating means of the present invention, the generated foam and the floating of the rubber are not seen at all by interposing the filter, and the water quality is visually free of bubbles and odor. Condition.

The processed photosensitive material had excellent finish characteristics without surface scratches or peeling.

Complete processing 40
Table 2 shows the results of calculating the pH value and iodine consumption by sampling the rinsing water in the water storage tank at each of the processing times of 65, 85, 105, 135, 150, 200, and 270 sheets. Shown in

In addition, the same treatment was performed, and the 6% hydrogen peroxide solution obtained from the measured values at the above-mentioned respective treatment times based on the method of Experimental Example 1 was added to the water storage tank from the purifier supply tank having a total capacity of 11, and then the water was stored again. Table 2 shows the results of sampling the washing water in the tank and measuring the pH value and iodine consumption in the same manner.

As is clear from Table 2, by adding 6% hydrogen peroxide solution corresponding to the measured value of iodine consumption at each treatment point to the washing water, it is possible to purify the contaminated washing water to a water quality that can be discharged into sewage. Becomes

[Effects of the Invention] As described in detail above, by circulating and regenerating the washing water according to the present invention, the water saving efficiency is greatly improved. For example, a user who uses the washing water while dripping at a rate of 51 / min. However, although there is a slight difference depending on the amount of the light-sensitive material, water can be saved up to about 40 to 1/60.

In addition, by incorporating the circulating system in the automatic developing apparatus, the physical processing load on the photosensitive material during processing is small, the automatic developing apparatus is compact, and has improved maintenance and cost, and has excellent water saving efficiency. Can be provided.

Further, by the automatic developing apparatus of the present invention, it is possible to provide a processing method capable of preventing an increase in a residual fixing solution component of a silver halide black-and-white photosensitive material and providing excellent image characteristics.

Further, the automatic developing device of the present invention can improve the water-saving efficiency and purify the used washing water, which is to be a waste liquid having a high pollution load, to a level at which sewage can be drained, thereby reducing the burden on the user for waste liquid treatment. Can be.

[Brief description of the drawings]

FIG. 1 is a schematic diagram schematically showing an example of a water washing section of the automatic developing apparatus of the present invention, and FIG. 2 is a diagram showing an iodine consumption amount and an amount of hydrogen peroxide added to ammonium thiosulfate in a substitute experiment of Experimental Example 1. 6 is a graph showing the relationship of. DESCRIPTION OF SYMBOLS 1 ... Rinse tank, 2 ... Water tank 3 ... Circulation means, 4 ... Filter 5 ... Purifier supply tank, 6 ... Discharge means

────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toshisuke Kobayashi 1 Konica Co., Ltd., Sakura-cho, Hino-shi, Tokyo (56) References JP-A-63-199357 (JP, A) JP-A-63-132239 (JP, A) JP-A-63-291679 (JP, A) JP-A-59-166241 (JP, U) (58) Fields investigated (Int. Cl. ⁶ , DB name) G03D 3/00-17 / 00

Claims (8)

(57) [Claims] 1. An automatic developing apparatus for a silver halide black-and-white photosensitive material comprising at least a developing section, a fixing section and a rinsing section, wherein the rinsing section comprises: at least a rinsing means for rinsing the photosensitive material; Storage means for temporarily storing water containing used washing water as washing water supplied to the washing means, at least one regenerating means for regenerating the used washing water, and washing water in the washing means A circulating means for circulating the washing water in the water storing means between the washing means and the water storing means; and when the contaminated concentration of the washing water circulated by the circulating means exceeds a predetermined value, a purifying agent is provided in the water storing means. A purifying agent supplying means for supplying the purifying agent, and a draining means for draining at least a part of the washing water in the water storage means after supplying the purifying agent, and wherein the washing section is incorporated. C Automatic developing system for black and white photosensitive materials. 2. The automatic developing apparatus according to claim 1, wherein the regenerating means is a filter provided between the washing means and the water storing means. 3. An automatic developing apparatus according to claim 1, wherein said regeneration means comprises oxidant supply means for supplying the oxidant to the water storage means. 4. The automatic developing apparatus according to claim 1, wherein the regeneration means comprises a filter provided between the washing means and the water storage means and an oxidant supply means for supplying the oxidant to the water storage means. 5. The automatic developing apparatus according to claim 1, wherein the purifying agent is an oxidizing agent. 6. An automatic developing apparatus according to claim 1, wherein said purifier supply means also serves as an oxidant supply means. 7. A silver halide black-and-white light-sensitive material.
A method for processing a silver halide black-and-white light-sensitive material, wherein the processing is performed by using the automatic developing apparatus according to any one of (1) to (6). 8. When processing a silver halide black-and-white photosensitive material using the automatic developing apparatus according to any one of claims (1) to (6), the contaminant concentration of the circulating washing water is controlled to a predetermined level. When the value is exceeded, the purifying agent is supplied from the purifying agent supply unit to the water storing unit to purify the washing water in the water storing unit, and then, at least a part of the washing water in the water storing unit is drained by the draining unit. Wastewater treatment method.