JPH057468B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a method for recovering silver from a water-washing alternative photographic stabilizer, and more particularly to a method for recovering silver from a stabilizer in a stabilization treatment method that does not include a water-washing step following a desilvering step. [Prior Art] In conventional processing methods including a washing step, silver recovery methods from fixing solutions, bleach-fixing solutions, washing water, etc. include, for example, electrolytic silver recovery method, reduction precipitation method, metal displacement method, ion exchange resin method, Electrolytic dialysis methods, silver sulfide precipitation methods, bacterial precipitation methods, radiolysis methods, etc. are known, and soluble silver salts in various treatment solutions are recovered. On the other hand, recently, for the purpose of environmental conservation, water resources, low cost, pollution, etc., a technology has been developed that directly performs stabilization treatment without washing with water after fixing or bleach-fixing. No. 57-132146, No. 58-
It is disclosed in publications such as No. 14834 and No. 58-18631. Furthermore, as described in JP-A No. 58-134636, the amount of stabilizing solution that does not require water washing is approximately 25 ml to 2.5 ml per 1 m ² of photographic material, preferably 50 ml to 1,000 ml per square meter of photographic material. More preferably 50ml
It is to be refilled with ~200ml. In such a stabilization treatment, a processing solution having fixing ability is introduced into the stabilizing solution, so there has been a need to develop a means for recovering silver from the stabilizing solution. As a result of extensive research into means for recovering silver from a stabilizing solution, the present inventor found that the composition of the stabilizing solution has specificity. In other words, the concentration of soluble silver ions in the stabilizing solution is extremely low because only the amount carried over from the previous solution is present, and if water washing is performed before stabilization treatment, the silver ions will be washed away by the water washing. It was found that the liquid composition has specificity, such that even components that would otherwise be removed are accumulated in the stable liquid. Furthermore, it was found that there are the following differences compared to the fixer. That is, when looking at the ratio of hypo to ammonia water in the fixer and the ratio of hypo to ammonia water in the stabilizer, the ammonia concentration in the stabilizer is relatively high, and the chelate concentration in the stabilizer is high. Furthermore, it was found that there are differences in the fact that they contain specific ingredients such as anti-bacterial agents. The present inventor has conducted further intensive research on methods for recovering silver from a stable solution having a unique composition as described above, and has discovered that the most effective means for recovering silver is an electrolytic method using a specific cathode. It has come to completion. [Object of the Invention] Accordingly, the first object of the present invention is to provide a method for recovering silver from a photographic stabilizer as an alternative to water washing using an electrolytic silver recovery method with high current efficiency. Our objective is to provide a silver recovery method for photographic stabilizers as an alternative to washing with water, which can recover highly pure metallic silver.
The third object is to provide a method for recovering silver from a photographic stabilizer as an alternative to water washing using an electrolytic silver recovery device having a cathode material that is stable for a long time with respect to the stabilizer. Furthermore, a fourth object of the present invention is to provide a method for recovering silver from a water washing alternative stabilizing solution in which the stabilizing solution can be reused. [Summary of the Invention] The method for recovering silver from a photographic stabilizer according to the present invention involves electrolyzing the photographic stabilizer in an anhydrous washing process in which a silver halide photographic light-sensitive material is treated with a photographic stabilizer without substantially washing it with water after a fixing process. In the method for recovering silver from a photographic stabilizer, the cathode material of the electrolytic electrode is stainless steel or titanium steel, and the photographic stabilizer contains at least one of the following chelating agents: shall be. (Chelating agent) Ethylenediaminediorthohydroxyphenylacetic acid, nitrilotriacetic acid, hydroxyethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, diaminopropanoltetraacetic acid, transcyclohexanediaminetetraacetic acid, ethylenediaminetetrakismethylenephosphonic acid, nitrilotrimethylene Phosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid,
1,1-diphosphonoethane-2-carboxylic acid, 2
-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxy-1-phosphonopropane-
1,2,3-tricarboxylic acid, catechol-3,
5-dicarboxylic acid, sodium pyrophosphate, sodium tetrapolyphosphate, sodium hexametaphosphate [Structure of the invention] The electrolytic means in the present invention recovers silver by electrolyzing using an electrolytic silver recovery device. An electrolytic silver recovery device basically has an electrolytic cell and a cathode and an anode made of a specific material in the electrolytic cell, and by passing a direct current through both electrodes, metal silver is deposited on the cathode and the silver is recovered. The purpose is to collect The electrolytic cell used in the present invention is preferably made of an insulating material that can withstand long-term use or repeated use, and synthetic resins such as polyvinyl chloride, polyvinyl methacrylate, polyethylene, polypropylene, and phenol formaldehyde resin are particularly preferably used. . Stainless steel or titanium steel is used as the cathode material of the electrolytic electrode. Stainless steel here is defined as having iron as its main component, with at least 11 to 30% chromium, 0 to 37% nickel, 0 to 4% molybdenum, 0 to 1% titanium, and 0 to 3% copper.
It is an alloy containing Specifically, the stainless steels specified by the Japanese Industrial Standards (JIS) include SUS200 series to 400 series and 600 series (JIS G4303 to G4309 and JIS G4313 to G4315, 1972), SUS/STKS
(JIS G3459−1968, JIS G3463−1968, JIS
G3441-1966), SCS (JIS G5121-1969), D and Y 300-400 series (JIS Z3221-1968, JIS
Z3321−1969), SUH (JIS G4311−1972, JIS
G4312-1972) and SCH (JIS G5122-1969) are used. Among these stainless steels, for example, SUS200 series, 300 series, and 600 series containing at least 11% to 30% chromium and 3% to 20% nickel are preferably used, and more preferably at least chromium.
16~20%, Nickel 10~16%, Molybdenum 1.2~
For example, SUS316, 316L, 316JI, containing 4.0%
316JIL, 317 are used. Titanium steel is a metal whose main component is titanium (including alloys and mixtures with other metals).
The titanium content is preferably at least 50%,
More preferably 90% or more, particularly preferably
More than 99%. The anode material may be any electrical conductor or semiconductor that does not dissolve in electrolysis or in a stabilizing solution and can withstand long-term use or repeated use, especially carbon (including graphite) and/or carbon. Fibers are preferably used. The shapes of the cathode and anode are disk, cylinder, plate, grain,
Although any type of fiber may be used, it is particularly preferable that the cathode is a cylinder, and the anode is a combination of a cylinder and a fiber.
Stirring of the liquid in the tank is important, and stirring by liquid feeding and/or rotation of the cathode is preferred. The cathode and the anode may be separated by a diaphragm, and examples of membrane materials include semipermeable membranes, asbestos membranes, terracotta plates, thin glass, sintered glass, glass fibers, microporous synthetic polymer membranes (e.g.
polyvinyl chloride membrane, polystyrene membrane, polysulfone membrane, polyester membrane, polypropylene membrane, etc.)
and ion exchange membranes. Electrolysis conditions are not particularly limited, but the cathode potential is -
Preferably, the anode potential is in the range of 0.40 to -0.65V, the anode potential is in the range of 0 to 0.20V (vs. saturation Carmel potential), that is, the potential between the electrodes is in the range of 0.40 to 0.80V (including potential due to solution resistance). Next, a recovery method of the present invention incorporating the above-described electrolyzer will be explained. The silver recovery of the present invention is aimed at a water-washing alternative stabilizing solution, but silver is contained in such a stabilizing solution because the silver component desilvered in the previous step of the stabilization process is not recovered or Because they are not collected enough, they are brought in adhering to photographic materials. Even in this case, if there is a means to discharge and recover the silver component from the system by washing with water before the stabilization treatment, the silver component brought into the stabilizing solution is not a subject of consideration, but the present invention does not take into consideration such a method. Since it is unique in that it eliminates washing with water, the silver content introduced is very low in concentration, but cannot be ignored. Also, what is brought into the stabilizing solution is not only the silver component, but also other fixing components, so naturally the ammonia concentration in the fixing solution (vs. hypo) and the ammonia concentration in the stabilizing solution (vs. hypo) are extremely high. , and the ammonia concentration in the stabilizer becomes relatively high. It is clear that there are other differences in the composition of chelating agents, anti-bacterial agents, etc., which will be described later. Although this change in composition is probably caused by changes in the ammonia concentration or low concentration, it was found that the method of recovering silver from the fixer solution could not be directly applied as a means of recovering silver. As a result of various studies, the present invention was discovered. In the present invention, fixing a silver halide photographic light-sensitive material is a treatment for the purpose of desilvering,
Specifically, it is a treatment using a bleach-fixing bath or a fixing bath, and the bleaching agent used in this treatment is not particularly limited, but it is particularly effective when using an organic acid ferric complex salt. Also, the fixing agent is not limited, but it is particularly effective when using thiosulfate, and is more effective when using a fixing bath or a bleach-fixing bath containing an organic acid ferric complex salt and thiosulfate. It is valid. In the present invention, water washing treatment is not performed before the post-fixing stabilization treatment, but the inclusion of treatments such as rinsing is not excluded. Furthermore, a draining bath containing a surfactant and formalin can be provided after the stabilization treatment. The method of bringing the stabilizing solution of the present invention into contact with a photosensitive material is to immerse the photosensitive material in the solution in the same way as a general processing solution. It may be applied to both sides and the conveyor belt, or it may be sprayed onto the conveyor belt. Examples of the chelating agent contained in the stabilizer of the present invention include ethylenediaminediorthohydroxyphenylacetic acid, nitrilotriacetic acid, hydroxyethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, diaminopropanoltetraacetic acid, and transcyclohexanediaminetetraacetic acid. Acetic acid, ethylenediaminetetrakismethylenephosphonic acid, nitrilotrimethylenephosphonic acid, 1-
Hydroxyethylidene-1,1-diphosphonic acid, 1,1-niphosphonoethane-2-carboxylic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxy-1-phosphonopropane-1,2, 3-tricarboxylic acid, catechol-
3,5-dicarboxylic acid, sodium pyrophosphate,
Examples include sodium tetrapolyphosphate and sodium hexametaphosphate, and 1-hydroxyethylidene-1,1-diphosphonic acid and salts thereof are particularly preferred for the effects of the present invention. The amount added is preferably in the range of 0.01 g to 100 g, more preferably in the range of 0.1 g to 50 g per stabilizer. Further, desirable compounds to be added to the stabilizer of the present invention include PH adjusters such as acetic acid, sulfuric acid, hydrochloric acid, nitric acid, sulfanilic acid, potassium hydroxide, sodium hydroxide, ammonium hydroxide, sodium benzoate, hydroxyl, etc. Butyl benzoate, antibiotics,
Anti-bacterial agents such as dehydroacetic acid, potassium sorbate, thiabendazole, ortho-phenylphenol, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-octyl-4-isothiazolin-3-one, Preservatives such as 1-2-benzisothiazolin-3-one, water-soluble metal salts, dispersants such as ethylene glycol, polyethylene glycol, and polyvinylpyrrolidone, hardening agents such as hydrosulfite, sulfite, and formalin, and fluorescent light. Examples include brighteners. The most effective of these compounds are hydrosulfites, sulfites, etc., and they work effectively when added before electrolysis. The pH value of the stabilizer of the present invention is preferably adjusted to PH0.1-10, preferably PH2-9, more preferably
A preferred range is PH6 to 8.5. The recovery of electrolytic silver from the stabilizing solution of the present invention can be carried out from the stabilizing solution waste liquid and/or the stabilizing tank liquid, preferably from the stabilizing liquid waste liquid. In addition, when the stabilizer of the present invention is not reused, electrolytic silver recovery by mixing the fixer and bleach-fixer is more efficient than recovering electrolytic silver from the fixer and bleach-fixer separately. Rising and favorable. The silver to be recovered in the present invention mainly includes silver ions (including silver complexes), silver compounds, metallic silver, and the like. Although the silver concentration is not particularly limited, the effect of the present invention is significant in a low concentration range. Further, the recovery method of the present invention can be carried out in a batch type or a continuous type, and the batch type is a method in which the electrolyte solution is replaced by electrolyzing a certain amount of stable solution for a certain period of time.
The continuous type is a method that constantly supplies stabilizing liquid to the electrolytic cell and simultaneously discharges overflow. In the present invention, a batch type is preferred. In the present invention, it is preferable that the stabilization treatment tank is a multi-stage tank, and that the replenisher is replenished from the last stage tank and uses a backflow system in which it sequentially overflows to the previous stage tank. The number of stabilization treatment tanks is preferably 6 or less, particularly 4.
Preferably below the tank. Of course, it may be a single tank. Further, when the electrolytic silver recovery device is directly connected to the stabilization treatment tank, it is desirable to connect it directly to the first tank near the treatment bath having fixing ability. In this case, it is particularly effective to add the compound that releases sulfite ions, which is preferably used in the present invention, to the first bath and/or second bath near the processing bath having fixing ability. When regenerating the stabilizer of the present invention after recovering electrolytic silver,
Treatment may be performed using activated carbon, ion exchange resin, electrolytic dialysis, reverse osmosis, etc., and it is preferable to add a stabilizing liquid component as a regenerating agent. [Examples] Examples of the present invention will be described below, but the present invention is not limited thereto. Example 1 Color paper manufactured by Roku Konishi Photo Industry Co., Ltd. was printed and then continuously replenished using an automatic developing machine. The treatment steps and composition of the treatment liquid at this time are as follows. Standard processing steps [1] Color development 38°C 3 minutes 30 seconds [2] Bleach-fixing 33°C 1 minute 30 seconds [3] Stabilization 25°C to 30°C 3 minutes [4] Drying 75°C to 80°C approximately 2 minutes Processing liquid composition <color development tank liquid> Benzyl alcohol 15ml Ethylene glycol 15ml Potassium sulfite 2.0g Potassium bromide 1.3g Sodium chloride 0.2g Potassium carbonate 30.0g 3-Methyl-4-amino-N-ethyl-N-
(β-Methanesulfonamidoethyl)-aniline sulfate 5.5g Fluorescent brightener (4.4'-diaminostilbenzsulfonic acid derivative) 1.0g Hydroxylamine sulfate 3.0g 1-hydroxyethylidene 1,1-diphosphonic acid 0.4g Hydroxyethyliminoacetic acid 2.5g Magnesium chloride hexahydrate 0.7g 1,2-hydroxybenzene-3,5-disulfonic acid dinitrium salt 0.2g Add water to make 1g, and add KOH and H ₂ SO ₄ to PH10.20
And so. <Color developer replenisher> Benzyl alcohol 20.0g Ethylene glycol 5.0g Potassium sulfite 3.0g Potassium carbonate 30.0g Hydroxylamine sulfate 4.0g 3-Methyl-4-amino-N-ethyl-N-
(β-methanesulfonamidoethyl)-aniline sulfate 7.5g Fluorescent brightener (4.4'-diaminostilbenzsulfonic acid derivative) 1.5g 1-hydroxyethylidene 1,1-diphosphonic acid 0.5g hydroxyethyliminoacetic acid 3.0 g Magnesium chloride hexahydrate 0.8 g 1,2-hydroxybenzene-3,5-disulfonic acid dinitrium salt 0.2 g Water was added to make 1 g, and the pH was adjusted to 10.70 with KOH. <Bleach-fix tank solution> Ferric ammonium ethylenediaminetetraacetic acid dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100ml Ammonium sulfite (40% solution) 27.5ml Adjust to PH7.1 with potassium carbonate or glacial acetic acid At the same time, water was added to bring the total volume to 1. <Bleach-fixing replenisher A> Ethylenediaminetetraacetic acid ferric ammonium dihydrate 260g Potassium carbonate 42g Water was added to bring the total amount to 1. The pH of this solution is 6.7±0.1. <Bleach-fix replenisher B> Ammonium thiosulfate (70% solution) 500ml Ammonium sulfite (40% solution) 250ml Ethylenediaminetetraacetic acid 17g Glacial acetic acid 85ml Water was added to bring the total volume to 1. The pH of this solution is 5.3±0.1. <Stabilizer> 5-chloro-2-methyl-4-inchazolin-3-one 0.02g 2-methyl-4-inchazolin-3-one
0.02g Ethylene glycol 1.0g 2-octyl-4-inthiazolin-3-one
0.01g 1-hydroxyethylidene-1,1-niphosphonic acid (60% aqueous solution) 1.5g BiCl ₃ (45% aqueous solution) 0.65g MgSO ₄・7H ₂ O 0.2g Aqueous ammonia (25% aqueous solution) 2.5g Nitrilotriacetic acid 1.2g Sodium hydroxide 1.0g Water was added to bring the total amount to 1, and the pH was adjusted to 7.0 with H ₂ SO ₄ . Fill an automatic processor with the color developer tank solution, bleach-fix tank solution, and stabilizer solution mentioned above, and replenish the color developer replenisher, bleach-fixer replenisher A, B, and stabilizer every 3 minutes while processing the color paper. A running test was performed while replenishing the solution through a metering cup. The replenishment amount is 324 ml per 1 m ² of color paper to the color development tank, bleach-fix replenisher A, and bleach-fix replenisher A to the bleach-fix tank.
25 ml of each B was added, and 250 ml of stabilizing solution was added to the stabilization treatment bath. The stabilization processing baths of the automatic processor are the first to third stabilization tanks in the direction of the flow of the photosensitive material, and the final tank is replenished, and the overflow from the final tank is allowed to flow into the preceding tank. Furthermore, a multi-tank countercurrent system was adopted in which this overflow liquid also flows into the preceding tank. Continuous processing was carried out until the total replenishment amount of stabilizing solution was three times the capacity of the stabilizing tank. Experiment-1 Further continuous processing was performed to collect the stabilizer overflow, and using a cylindrical electrolytic silver recovery device as shown in Figure 1, the material of the cathode cylinder 1 (cathode) was changed to aluminum, zinc, brass, copper, Nickel chrome molybdenum steel (nickel 3%, chromium 3%,
Molybdenum 0.6%), carbon steel, stainless steel (JIS)
After changing the voltage between the two electrodes and setting the cathode current density to 0.3A/dm ² for SUS430, SUS304, SUS316, and titanium steel (99.0%),
Electrolysis was performed for 80 minutes. Note that electrolysis is performed by passing current from a DC power supply and rotating the central cathode by a drive motor. The amount of electrodeposited silver and the amount of current were measured for each material of the cathode, and the current efficiency, which indicates the actual amount of electrodeposition relative to the theoretical amount of electrodeposition, was determined and is listed in Table 1. In the figure, 2 is an anode, 3 is a tank cylinder, 4 is a drive inner cylinder, 5 is a large pulley, 6 is a belt, 7 is a drive motor, 8 is a small pulley, 9
1 is a DC power supply section, 10 is a control section, 11 is a float unit, 12 is a brush carbon, 1
3 indicates a slip ring, 14 indicates a liquid supply pump, 15 indicates a drain pump, and 16 indicates a rubber elbow. Experiment-2 Each electrode used in Experiment-1 was immersed in a stabilizing solution overflow for one month and observed for corrosion.
1.

【table】

[Table] Note-1 ○…No corrosion.
△...Corrosion is observed.
×...Significant corrosion.
As is clear from Table 1, when aluminum, zinc, brass, copper, nickel chromium molybdenum steel, or carbon steel is used as the material for the cathode, the current efficiency is low, and it is unstable and corrodes with respect to the stabilizing liquid. It is too easy to put it into practical use. On the other hand, the one made of stainless steel and titanium steel used in the present invention has a high current efficiency, is stable against stabilizing liquid, and is difficult to corrode, and has been found to be very effective. Steel is preferred because it is resistant to corrosion, and titanium steel is most preferred because it has high current efficiency and corrosion resistance and is found to be extremely effective. In addition, when we analyzed the purity of electrodeposited silver, we found that silver sulfide is generated in products other than stainless steel and titanium steel, and the purity is around 95%, whereas in stainless steel and titanium steel, the silver content is over 99%, which is extremely high. I liked it. Example 2 When the overflow bleach-fix solution discharged from the continuous processing of Example 1 was electrolyzed using the electrolytic silver recovery device shown in Figure 1 using SUS316 as the cathode material, the current efficiency was 14%. It was hot. Similarly, when a mixture of bleach-fix overflow and stabilizer overflow was electrolyzed, the current efficiency was 29%. For this reason, the electrolytic silver recovery device used in the present invention has little effect in recovering silver from bleach-fix solutions.
It can be seen that the use of a mixture of the stabilizing solution and the bleach-fixing solution is preferable because the current efficiency is high, similar to the recovery of silver from the stabilizing solution in Example 1. Example 3 Continuous processing was performed using the following stabilizer formulation in place of the stabilizer formulation in Example 1, and the bleach-fix overflow and stabilizer overflow were collected in one tank and used as a sample. <Stabilizer> 5-chloro-2methyl-4-isothiazoline-3
-one 0.02g 2-methyl-4-isothiazolin-3-one
0.02g Ethylene glycol 1.0g (NH ₄ ) ₂ SO ₄ 3.0g Adjusted to 1 with water. To the above sample solution, 20 g of each chelating agent No. 1 to No. 5 shown in Table 2 was added, and the cathode current density was reduced to 0.5 using an electrolytic silver recovery device using SUS316 as the cathode shown in Fig. 1. Set it to A/DM ² ,
Electrolysis was continued until silver sulfide was generated on the surface of the cathode.
The current efficiency and purity of electrodeposited silver were measured for No. 1 to No. 5 and are listed in Table 2.

[Table] As is clear from Table 2, No. 1 without the addition of a chelating agent and No. 2 with the addition of a chelating agent other than the present invention.
Compared to Nos. 3 to 5 containing the chelating agent of the present invention
is found to be superior. It is also found that No. 5, 1-hydroxyethylidene-1,1-diphosphonic acid, is particularly preferred. Comparative Example 1 As a comparison with the method of the present invention, an attempt was made to recover silver by bringing iron wool into contact with a stabilizing solution (ring element precipitation method) as a silver recovery method other than electrolysis, but the silver recovery efficiency was low. We also tried a method of recovering silver as silver sulfide by adding sodium polysulfide to the stabilizing solution (silver sulfide precipitation method), but the precipitation was poor and the silver recovery efficiency was low, making it undesirable. Example 4 In an experiment similar to Example 1, the electrolytic silver recovery device shown in Figure 1 was directly connected to the first stabilization treatment tank, and
Stabilizing liquid was introduced into the electrolytic cell from the first tank using a liquid supply pump, and the overflow was directed back to the first tank. The cathode was made of titanium steel (99%). Stabilizing liquid replenishment amount is stable 1/3 of the 1st tank capacity
The amount of color paper processed in one day is small, and the replenishment amount is 1/1 of the amount of the first tank.
After reaching 10, the electrolytic silver recovery device was operated for one month, and both silver recovery and photographic performance were good. Next, when the amount of replenishment per day was set to 1/30 of that of the first tank, precipitation occurred in all the tanks, resulting in deposits adhering to the color paper after treatment. In the same manner, 0.2 g of hydrosulfite was added per day to the first and second tanks, and the same procedure was performed, with no precipitation occurring and the results were very good. From the above experimental results, it can be seen that hydrosulfite is extremely effective in suppressing the problem of precipitation in the present invention when the amount of treatment per day is small. In addition, it was found that the number of stabilizing tanks of 4 or less is preferable because precipitation due to the above-mentioned small-volume treatment is likely to occur when the number of tanks is 5 or more, particularly in the 5th tank to the 7th tank. Example 5 Regarding the experiment using titanium steel as the cathode material in Experiment 1 of Example 1 Regarding the stabilizing solution after electrolytic silver recovery Anion exchange resin "Diaion WA-20"
(manufactured by Mitsubishi Kasei Corporation), the stabilizer composition of Example 1 was added and reused as a replenisher. As a result, the photographic performance of the color paper was extremely good without any problems.

[Brief explanation of the drawing]

FIG. 1 is a sectional view of an electrolytic silver recovery apparatus preferably used in the present invention. In the figure, 1 indicates a cathode cylinder (cathode), and 2 indicates an anode carbon (anode).

Claims (1)

[Scope of Claims] 1. Silver in a photographic stabilizer in which silver is recovered by electrolyzing the photographic stabilizer in a waterless washing process in which a silver halide photographic light-sensitive material is treated with a photographic stabilizer without substantially washing with water after the fixing process. A method for recovering silver from a photographic stabilizer, wherein the cathode material of the electrolytic electrode is stainless steel or titanium steel, and the photographic stabilizer contains at least one of the following chelating agents. (Chelating agent) Ethylenediaminediorthohydroxyphenylacetic acid, nitrilotriacetic acid, hydroxyethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, diaminopropanoltetraacetic acid, transcyclohexanediaminetetraacetic acid, ethylenediaminetetrakismethylenephosphonic acid, nitrilotrimethylene Phosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid,
1,1-diphosphonoethane-2-carboxylic acid, 2
-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxy-1-phosphonopropane-
1,2,3-tricarboxylic acid, catechol-3,
5-dicarboxylic acid, sodium pyrophosphate, sodium tetrapolyphosphate, sodium hexametaphosphate.