JP2756855B2 - Automatic processor with excellent water saving efficiency - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to an automatic developing apparatus for a silver halide photosensitive material for printing, and more particularly to a means for recycling washing water,
The present invention relates to an automatic developing device for a silver halide photosensitive material for printing which has excellent water saving efficiency.

[Prior Art] At present, development processing of a silver halide light-sensitive material is generally performed using an automatic developing machine. However, such an automatic developing machine generally includes development, fixing, washing, and drying steps. The photosensitive material which has been subjected to the developing and fixing processes is subjected to a washing step to remove the processing solution components of the previous step, particularly the fixing solution components, contained in the material by washing. 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 the sewer.

Under the circumstances as described above, in recent years, from the viewpoint of resource saving and reduction of production cost, the demand for water saving at the time of washing of the automatic developing machine has been increasing, and the demand for technical improvement accompanying this has been increasing. In other words, problems such as land subsidence in urban areas, rising water and sewage charges due to capital investment for lagging sewage treatment facilities compared to those in Europe and the United States, and water cuts due to specific weather conditions in summer in specific areas Demands for saving flushing water in order to cope with such problems are increasing in recent years, due to the recent increase in the amount of processing at plate-making shops and the problem of total wastewater control.

In response to the above water-saving requirements, an anhydrous washing / no-pipe system or a countercurrent washing method in which a chemical treatment is performed instead of the conventionally proposed washing treatment is used for the current black-and-white silver halide photosensitive material, especially for printing plate making. In the automatic developing equipment, the processing equipment becomes complicated and large, such as an increase in the number of processing tanks. As a result, the processing line becomes longer, and the processing time of photosensitive material becomes longer. From the viewpoint of the above, it was in a completely opposite direction and could not be applied.

Further, in order to speed up the processing in the above-described apparatus, it is necessary to further increase the processing line speed. In such a case, however, the physical burden on the photosensitive material increases, and for example, the charging of the photosensitive material And so on.

[Problems to be Solved by the Invention] As one method for this purpose, 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 treatment, and the water is washed between the water tank and the washing tank. A method of circulating water is conceivable. According to this method, a developer, a fixing solution component and a photosensitive material such as a dye, a dye, a surfactant, and gelatin in the preceding process, which are put into washing water depending on the photosensitive material to be processed. The concentration of eluted components from the water increases as the amount of treatment increases, and especially in recent large-scale treatment, the iodine consumption value as a legally defined water quality standard can be exceeded in a short time, resulting in wastewater The above problems remain.

The present inventors have previously reported the above-mentioned problems in Japanese Patent Application No.
No. 65440 and Japanese Patent Application No. 1-65442 propose to provide an oxidizing agent supply means as a regenerating means for regenerating used washing water.

However, S _2, which is the main component of pollutants in water,
O ₃ when added oxidizing agent with ^{2-decomposing} object S ₂ O ₃ ^2- are readily decomposed water is purified, such as silver complex ions become reaction decomposition product by continuing the long circulation Products such as colloidal silver are generated. For this reason, while reuse is repeated by regenerating the washing water, when a certain concentration is reached, it becomes necessary to renew the washing water in the water storage means.

Accordingly, it is a first object of the present invention to provide an automatic developing apparatus which enables recycling of washing water, thereby improving water saving efficiency, and a method of processing a silver halide photosensitive material for printing using the apparatus. It is in.

A second object of the present invention is to provide an automatic developing apparatus capable of efficiently removing silver ions in order to prevent the generation of insolubilized substances such as colloidal silver which are likely to be generated when an oxidizing agent is used as a means for regenerating washing water. An object of the present invention is to provide a method for processing a silver halide photosensitive material for printing using the apparatus.

Further, 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, and a method for treating contaminated washing water which is produced with an improvement in 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, the object of the present invention is to provide an automatic developing apparatus comprising at least a developing unit, a fixing unit, and a rinsing unit. A washing unit for washing the photosensitive material with water, a water storage unit for temporarily storing water containing used washing water discharged from the washing unit as washing water supplied to the washing unit, and a washing unit for washing the used washing water. A regenerating means having an oxidizing agent supplying means and an ion exchange resin for regenerating, a circulating means for circulating the rinsing water in the rinsing means and the rinsing water in the water storing means between the rinsing means and the water storing means,
Contaminant concentration measuring means for measuring the contaminant concentration of the washing water circulated by the circulating means, and supplying a purifying agent to the water storage means according to the contaminant concentration measured by the contaminant concentration measuring means to regenerate water. Purifying agent supply means for the purpose of
And a drain means for draining at least a part of the circulating washing water when the concentration of the circulating washing water exceeds a predetermined value. I found it.

 Hereinafter, the present invention will be described in more detail.

FIG. 1 is a schematic explanatory view schematically showing one example of the automatic developing apparatus of the present invention. According to FIG. 1, the washing section of the developing device of the present invention comprises a washing tank 1 for processing photosensitive material, and a washing tank 1
Rinsing water for replenishing the water and the replenishment described above, the rinsing tank 1
Rinse tank 1 for storing flush water overflowing from
Water tank 2 provided in the vicinity of
A circulating means 3 for replenishing the washing water and feeding overflow water from the washing tank 1 to the water tank 2;
And a regenerating means such as an oxidizing agent supply means 5 and an ion exchange resin tank 6 provided in the middle of the circulation path, and a circulation unit 3. The purifying means is used as a purifying means for the flushing water which is automatically supplied, for example, a purifying agent is supplied to purify the water to a drainable value, and at least a part of the washing water in the water storage tank 2 is discharged after supplying the purifying agent. And discharge means 7. The regenerating means and the purifying means can be used in common. In FIG. 1, as one of the preferred embodiments, the oxidizing agent supplying means for the regenerating and the purifying means for the drainage referred to in the present invention are the same. It is shown.

That is, after the washing tank 1 and the water tank 2 are filled with unused washing water at the start of the development processing, the developed and fixed photosensitive material is washed with the washing tank 1, and the water is stored in accordance with the processing amount of the photosensitive material. 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, the 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 eluted from the photosensitive material such as a fixing solution component or 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, the filter unit 4, the oxidizing agent supply means 5, and the ion as the regenerating means are provided between the above-mentioned circulation paths such as 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. An exchange resin tank 6 is provided to remove and decompose components, particularly thiosulfate ions or water scale, dust, and silver ions, from the washing water to degrade the photosensitive material, thereby performing a regeneration treatment of the washing water. As such a filter, carbon fiber, aramid fiber, Teflon resin fiber, hemp, glass fiber, polyethylene foam, polypropylene foam and the like are preferably used as the material of the filter fiber from the viewpoint of heat resistance and chemical resistance. Further, those described as a contact substance in JP-A-60-263151 can also be used.

Examples of the oxidizing agent used in the oxidizing agent supply means include metal or nonmetal oxides, oxide acid-based acids or salts thereof, peroxides, and compounds containing an organic acid-based compound. Sulfuric acid, sulfurous acid, nitric acid, hypochlorous acid, etc. are preferable as the above-mentioned acid-based acids because the main purpose is to decompose the fixing solution components brought into the used washing water, and the peroxide is peroxide. Hydrogen water, Fenton's reagent and the like are preferably used. Also, ozone is preferably used.

The amount to be added can be arbitrarily selected depending on the type of photosensitive material, the amount of processing, the type of processing solution, and the like. Is in the range of equimolar amount to several times equivalent molar amount, particularly in the range of 1/2 mole to 5 times molar amount, particularly in equimolar amount to
It is preferably added in a range of 4.5 molar equivalents. In addition, since the amount of the fixing solution component actually introduced is proportional to the amount of the processed light-sensitive material, the amount to be added can be determined based on the amount of the processed light-sensitive material. In addition, the water storage tank 2 may have a known stirring means in order to efficiently perform regeneration.

In the present invention, the addition of an oxidizing agent as a regenerating means is intended to decompose fixing components introduced during washing, especially S ₂ O ₃ ^2- . However, the decomposition reaction mechanism of S ₂ O ₃ ^2- is complicated, and silver thiosulfate ions and the like are decomposed by the influence of the oxidizing agent, and the silver is insolubilized to form colloidal silver, etc., which causes water to be colored, A sediment is generated by the stagnation of time. In order to prevent this, in the present invention, an ion exchange resin for adsorbing and removing silver ions is processed into a cartridge and provided in the middle of the circulation path to efficiently remove silver ions.

As the ion exchange resin used in the present invention, various cation exchange resins can be used alone or in combination with an anion exchange resin. As the cation exchange resin, a strongly acidic Na-type cation exchange resin and also an H-type cation exchange resin are preferable, and a combination of a strongly acidic H-type cation exchange resin and a strongly basic OH-type anion exchange resin is also a preferred embodiment.

The ion exchange resin is preferably a strongly acidic cation exchange resin having a styrene-divinylbenzene copolymer as a base and having a sulfone group as an ion exchange group. Examples of such an ion exchange resin include, for example, Diaion SK-1B or Diaion PK-216 (trade name, manufactured by Mitsubishi Chemical Corporation).
And the like. The substrate of these ion exchange resins preferably has a charge amount of divinylbenzene of 4 to 16% based on the charge amount of all monomers at the time of production. As the anion exchange resin that can be used in combination with the H-type cation exchange resin, a strongly basic anion exchange resin having a styrene-divinylbenzene copolymer as a base and having a tertiary amine or quaternary ammonium group as an exchange group is preferable. .
Examples of such anion exchange resins include, for example, Diaion SA-10A or Diaion PA-418, also manufactured by Mitsubishi Kasei Corporation.

Any known method can be used to remove calcium and magnesium in water with these ion exchange resins, but it is preferable to pass water through a column filled with the ion exchange resin. The speed when passing water is 1 to 100 times the resin volume per hour,
Preferably it is 5 to 50 times.

In the present invention, the water saving efficiency and the purification degree of water are improved by using an ion removing means using an ion exchange resin in combination with the regeneration mechanism using the oxidizing agent.

In the present invention, when the processing amount further increases and the degree of contamination progresses, even if S ₂ O ₃ ^2- is decomposed, the water tank ² may be decomposed, for example, due to coloring or other contamination due to elution of pigment, gelatin or the like.
It is necessary to drain all or at least a part of the washing water and replace it with fresh washing water.

The degree varies depending on the composition of the photosensitive material used, such as additives, and it is necessary to determine the degree of visual observation or transmittance.
Almost 100-200 pieces in almost all sizes.

However, especially when the degree of pollution exceeds the drainage standard, drainage to the sewer becomes impossible,
It is necessary to constantly detect the contaminant concentration of the washing water 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 added to the washing water in the circulation path to purify the washing water in the water storage tank 2 to an allowable value. Thereafter, at least a part of the purified washing water is drained by the drainage means 7. 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.

Possible to simplify the apparatus, and a cleaning agent supply means and the oxidizer supply means since it is aimed at even to decompose around the S ^₂ O ₃ ^2- and the like can also be purified to play thinking from that purpose It is particularly preferred that they are the same.

When the thiosulfate ion concentration of the washing water in the water tank 2 exceeds a value corresponding to the reference value of the iodine consumption, for example, these purifying agents can be added according to the concentration, and diluted with water or the like. Then, it is added from the purifying agent supply tank 5.

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 accordance with the thiosulfate ion concentration and automatically purifying it according to the present invention, a method of measuring an ORP value with an ORP (oxidation-reduction potential) electrode and automatically adding the purifying agent based on the measured ORP value is used. Is possible.

Specifically, a sodium thiosulfate solution having a predetermined concentration is adjusted to pH
Adjust the pH to 4 or 7, add sodium hypochlorite, measure iodine consumption, KMnO ₄ consumption and ORP value to determine the amount of purifying agent added. That is, for example, 0.03N-N
When sodium hypochlorite was added to each of pH 4 and pH 7 in the a ₂ S ₂ O ₃ solution, the ORP value of the first wave sharply increased in the pH 7 solution at a certain amount, This coincided with the lowest value of iodine consumption. This indicates that the entire amount of S ₂ O ₃ ^2- has been oxidized. When sodium hypochlorite is further added, the rise of the second wave of the pH 7 solution and the sharp rise of the pH 4 solution are observed. Thus, in the neutral or acidic region, the rise of the ORP value is used to increase the value from +500 to 80.
Purification can be performed automatically by adding sodium hypochlorite until it reaches 0 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 the purifying agent can be supplied by operating, for example, an electromagnetic on-off valve or the like. 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 photosensitive material and substituting it. That is, since thiosulfate ion, which is a main contaminant, is a component carried by the processed photosensitive material, the amount thereof is considered to substantially correspond to the amount of the processed photosensitive material, that is, the total area. Therefore, the concentration of contamination when a predetermined amount of photosensitive material is processed and how much purifying agent is required to purify the concentration to a predetermined value are determined in advance by experiments, and the processing is performed using this result. Measure and calculate the total area of the photosensitive material,
What is necessary is just to supply the purifying agent of the quantity corresponding to this.

Specifically, as shown in FIG. 1, a photosensitive material is detected by a film sensor 9 provided in the vicinity of a photosensitive material insertion port of an automatic developing machine. The total area of the processed photosensitive material is counted by the connected counter 10. When the counted total area exceeds a value corresponding to a predetermined contamination concentration, a predetermined amount of a purifying agent is supplied based on the experimental value. On this occasion,
The apparatus may have a system in which the experimental values are input in advance, and the amount of the purifying agent corresponding to the total area value is calculated and automatically supplied. Particularly preferably, the replenishment system of the fixing solution and the developing solution of the automatic developing machine is widely used in which the replenishment system is replenished in an area unit according to the processing area. It is to replenish in area units.

In the case of many photosensitive materials, the amount of the oxidizing agent required for the above-mentioned regeneration and the amount of the purifying agent required to satisfy the emission standard are almost the same. Often satisfies the criteria.

In the water storage tank, a usual well-known stirring means may be provided to promote purification. In the present invention, because the addition of an oxidizing agent in the washing water in the middle of the circulation path of the circulation route between the washing tank and the water storage tank, the play degrading the S ^₂ O ₃ ^2- as described above When the water tank is installed outside the washing tank of the automatic developing machine as in the present invention, the reaction of decomposition of S ₂ O ₃ ^2- due to the addition of the oxidizing agent causes a concentration difference in view of its form. And the process is performed uniformly.
That is, the oxidizing agent component is quickly diffused more uniformly without using a special stirring means than in the method in which the oxidizing agent is automatically dropped when the oxidizing agent is added.

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. Method for purifying pure water using the method described in JP-A-60-253807,
Nos. 60-295894, 61-63030 and 61-51396 using the antibacterial agent and the like 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.

Furthermore, RTKreiman's J.Image, Tech10,
(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'-hydroxydiphenyl ether and the like.

In addition, various methods such as processing with 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 a bactericidal agent or the like, or a tank whose inside is processed with Teflon, etc., from the viewpoint of water scale prevention 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 the photosensitive material is inserted into the automatic developing machine, the area is detected by a sensor, and the water is automatically stored. An electromagnetic valve design may be used in which the washing water is supplied from the tank 2 to the washing tank 1 and the supply of the washing water is stopped when the photosensitive material is not detected. On this occasion,
The washing water is preferably forcibly transferred by a high-pressure pump, and the amount of replenishing washing water is preferably from 10 to 30, more preferably from 15 to 25, per 1 m ^{2 of the} processed photosensitive 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.

As described above, by providing a water storage tank as in the present invention, the washing water is circulated and used, and further, the washing water is recycled by using an oxidizing agent and an ion exchange resin to increase the water saving effect and further treat the water. The concept of performing wastewater treatment by purifying contaminated washing water generated by an increase in the amount was found for the first time by the present inventors as a result of earnest research, and is not found at all in the prior art.

The silver halide photographic light-sensitive material applicable to the automatic processor of the present invention is a black-and-white light-sensitive material, particularly a black-and-white negative film,
Black and white reversal film, X-ray film, copy film,
Printing films, gravure films and the like can be mentioned, but they are preferably applied to photosensitive materials for printing.

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

The developing agent used in the black and white developer used in the present invention is different from dihydroxybenzenes in that good performance is easily obtained.
Most preferred are combinations of -phenyl-3-pyrazolidones. Needless to say, a p-aminophenol-based developing agent may also be contained.

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 agent of 1-phenyl-3-pyrazolidone or a derivative thereof used in the present invention include 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone and the like.

Examples of the p-aminophenol-based developing agent used in the present invention include N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, and N- (4-hydroxyphenyl) glycine , 2-methyl-p-aminophenol and p-benzylaminophenol, among which N-methyl-p
-Aminophenol is preferred.

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 to set the pH include pH adjusters such as sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate tribasic, and potassium phosphate tribasic.

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 sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and formaldehyde sodium bisulfite.
The sulfite is preferably at least 0.2 mol / mol, particularly preferably at least 0.4 mol / mol. The upper limit is preferably up to 2.5 mol /.

Additives other than the above components include development inhibitors such as sodium bromide, potassium bromide, and potassium iodide: ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, ethanol, and methanol. Organic solvents such as: 1-phenyl-5-mercaptotetrazole, mercapto compounds such as 2-mercaptobenzimidazole-5-sulfonic acid sodium salt, indazole compounds such as 5-nitroindazole, and benzes such as 5-methylbenztriazole It may contain an antifoggant such as a triazole compound, and further, if necessary, a color tone agent, a surfactant, an antifoaming agent, a hard water softener,
It may contain an amino compound described in 106244 or the like.

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 of 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 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 hardener, and examples thereof include aluminum chloride, 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.

[Examples] Hereinafter, the effects of the present invention will be illustrated by examples.

REFERENCE EXAMPLE 1 Assuming that the fixer component is brought into the rinsing water of the photosensitive material, Konica Fixer 851 (manufactured by Konica Corporation) 300 cc 500 cc 700 cc is mixed into the water 62 as a fixer, and each of them is hydrogen peroxide as a purifying agent. A substitution test was performed to determine the amount of purifying agent required to reduce the iodine consumption to 220 mg / or less, which is the regulatory standard value, for the thiosulfuric acid component in the mixed fixing solution by adding a 6% solution. The results are shown in FIG. 2 for the above cases.
However, after adjusting the sample to almost neutral based on the sewerage test method, a certain amount of iodine was added to this sample in 1 /
It was titrated with a 100 N sodium thiosulfate solution.

From FIG. 2, in order to reduce the iodine consumption of each of the three fixing solution concentrations to 220 mg / or less, it is necessary to add hydrogen peroxide to ammonium thiosulfate in a molar ratio of about 0.9 to 1.25. It turns out to be good. Similarly, the amount of hydrogen peroxide to be added can be determined for various thiosulfate ion concentrations.

Reference Example 2 The experiment was performed under the following experimental conditions.

Automatic developing machine: Processing equipment for printing film and paper Konica Automatic Processor GR-27 Developer: Konica Developer Type 651K Fixing solution: Konica Fixer Type 851 Processing photosensitive material: Konica Ortho Film RHH (manufactured by Konica Corporation) Konica Ortho Film Is a plate-making printer P-607
(Light source: Ultra high pressure mercury lamp URT-CHM-1000) Exposed by Dainippon Screen Co., Ltd.
An 8 × 610 mm one was used.

First, the supply valve from tap water to the Konica Automatic Processor GR-27 was cut off, connected to a water tank made of vinyl chloride of about 50 volumes, and the water tank was filled with 40 waters, for a total of 62 tanks.
Water was circulated. In this state, the RHH film was continuously processed. As a result of the continuous treatment, water was sampled for each number of treated sheets, and the iodine consumption was given as a measure of the water quality. The result is shown in FIG.

[Example 1] An ion-exchange resin cartridge filter represented by the formula (A) was interposed in the middle of a circulation path between a water storage tank and a washing tank installed as shown in Fig. 1 under the same conditions as in Reference Example 2. . In addition, for each processing area corresponding to the entire film size of 508 × 610 mm ² , a specified amount of 6% hydrogen peroxide solution obtained by conversion from FIGS. 2 and 3 is used to replenish the developing solution of the automatic developing machine GR-27. The device was sent into the water storage tank at any time by receiving a replenishment operation signal. In this way, the large-sized film was continuously processed for 135 months each for 6 months. The iodine consumption value and pH value of each water quality at that time were measured. The result is shown in FIG.

Further, the conditions in the water tank with and without the ion exchange resin were compared at various times. Further, the amount of the precipitate in the water storage tank after one month processing and the finishing performance of the photosensitive material after the processing were examined. The results are shown in Tables 1 and 2.

[Effects of the Invention] As described in detail above, the automatic development processing of the present invention efficiently removes silver ions, and thus is easily generated when an oxidizing agent is used as a means for regenerating washing water. Can be prevented from being generated.

Further, the automatic developing apparatus of the present invention enables the reuse of washing water, thereby improving water saving efficiency, and further purifying contaminated washing water to a point where it can be drained. .

Further, by means of the present invention, the means for removing silver ions by the ion exchange resin and the repeated use of water while regenerating water with an oxidizing agent are used. Cost merit is also obtained, which is very effective from the viewpoint of energy saving and resource saving. On the other hand, the occurrence of dirt or the like, which is usually associated with water saving processing, is significantly reduced, and an effect effective for maintainability is brought about.

[Brief description of the drawings]

FIG. 1 is an explanatory flowchart showing one example of the configuration of the automatic developing apparatus of the present invention. FIG. 2 is a graph showing the relationship between the amount of hydrogen peroxide added and the amount of iodine consumed. FIG. 3 is a graph showing the number of continuous treatments and iodine consumption. FIG. 4 is a graph showing the relationship between the number of sheets continuously processed and the consumption of pH and iodine. 1: Rinse tank 2: Water tank 3: Circulation means 4: Filter unit 5: Oxidizing agent (purifying agent) supply means 6: Ion exchange resin tank 7: Drainage means 8: Developer / fixer replenisher tank 9: Film sensor 10: Sensitive material processing area counter 11: Pump 12: Liquid level sensor 13: Rinse water supply section

Claims (1)

(57) [Claims] 1. An automatic developing apparatus comprising at least a developing section, a fixing section and a rinsing section, wherein said rinsing section includes a washing means for washing the photosensitive material with water, and water containing used washing water discharged from said washing means. Water storage means for temporarily storing as the washing water supplied to the washing means, an oxidizing agent supply means for regenerating the used washing water and a regenerating means having an ion exchange resin; washing water and water storage means in the washing means Circulating means for circulating the washing water in the washing water means between the rinsing means and the water storing means, a contaminant concentration measuring means for measuring a contaminant concentration of the rinsing water circulated by the circulating means, and a contaminant concentration measured by the contaminant concentration measuring means. A purifying agent supplying means for supplying a purifying agent to the water storage means in accordance with the contaminated concentration to regenerate the water, and when the concentration of the circulating washing water exceeds a predetermined value, the washing water At least one The automatic developing apparatus, comprising a drainage means for draining.