JPS6158029B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for removing bromide ions from a photographic developer using ion exchange membrane electrodialysis. In the photographic development process, a developing agent reduces exposed silver halide to form a silver image, and at this time, halide ions, which are by-products of the silver image formation, are eluted from the photographic material into the developer solution. Among halide ions, iodide ions are exchanged with bromide ions of silver bromide, so bromide ions are mainly accumulated in the developer, which affects photographic properties. Therefore, in order to regenerate and reuse the exhausted developer, it is necessary to remove the bromide ions therein. The exhausted developer solution is allowed to overflow, and this overflow solution is temporarily stored, and when it reaches a certain level, it is introduced into an ion exchange membrane electrodialysis tank to remove bromide ions, and the deficient processing agent component is added again. The so-called batch method used as a replenisher is well known (for example, Japanese Patent Laid-Open No. 51-84636).
No. 51-97432, No. 52-119934). However, with this batch method, although it is possible to remove bromide ions or control the concentration of overflow developer waste, it is possible to directly control the developer in the developer tank of the photo processing machine that actually processes photographic materials. This caused various inconveniences. On the other hand, the method described in Japanese Patent Application Laid-open No. 54-37731 connects the developer tank of the photographic processing machine that is actually performing the processing with the ion exchange membrane electrodialysis tank. By detecting and quantifying halide ions (particularly bromide ions) and controlling the amount of current applied to the electrodialysis tank based on the results, dialysis is carried out so that the bromide ion concentration in the developer is kept constant. This is an improved method in which a deficient processing agent component is additionally added to the overflowing developer and used again as a replenisher (this method is referred to as a continuous regeneration method). This continuous regeneration method is advantageous because the bromide ion concentration in the actual developing tank can be directly controlled, and bromide ions can be automatically removed without any trouble in obtaining the bromide ions. In this method, bromide ions are electrodialyzed while adjusting the amount of current applied so that the concentration of bromide ions in the developer tank of the processing machine is kept constant. When the concentration of bromide ions in the concentration chamber fluid fluctuates, the concentration of bromide ions in the developer solution cannot be kept constant unless the amount of current is varied accordingly. cannot be maintained. In other words, when the concentration in the concentration chamber solution is higher than the concentration in the developer solution, dialysis occurs from the concentration chamber solution to the developer solution, and unless a current is passed to overcome the force that causes this dialysis, bromide ions will be transferred from the developer solution to the concentration chamber solution. Therefore, the current density must be increased as the bromide ion concentration of the concentration chamber liquid increases. By the way, the developer contains various ions other than bromide ions, such as carbonate ions and sulfate ions, and the ring ratio of these ions differs for each ion, so when the current density changes, the number of ions dialyzed changes. The ratio of Therefore, when the concentration of the concentrated solution changes, the ratio of the amounts of each ion dialyzed from the developer solution changes, making it difficult to obtain a regenerated developer solution with a constant composition. Therefore, in the invention of JP-A-54-37731, it was essential to keep the bromide ion concentration of the concentration chamber solution constant in order to obtain a regenerated developer with a constant composition. The present inventors have made the following invention which is both novel and difficult to come up with. In other words, the demineralization chamber of an ion exchange membrane electrodialysis tank consists of multiple anion exchange membranes and multiple cation exchange membranes between the cathode and the anode (the cathode side is the cation exchange membrane, the anode side is the anion exchange membrane). A chamber separated by a membrane) is connected to the developer tank of the processing machine, and the developer is circulated between the demineralization chamber and the developer tank, and this electrodialysis tank is used to maintain a constant bromide ion concentration in the developer. In a method of regenerating developer waste through a controlled amount of current, the electrolyte solution (hereinafter referred to as concentrated The concentration of electrolyte substances in the concentrated chamber solution is increased by supplying and diluting the amount of water corresponding to the amount of development processing (referred to as chamber solution).
He invented a method for removing bromide ions from a photographic developer, which is characterized by carrying out electrodialysis while maintaining a constant concentration within the range of 2 g to 20 g/KBr. In addition, the current density for ion exchange membrane electrodialysis varies depending on the characteristics of the ion exchange membrane and the characteristics of the development treatment waste solution, but 0.02 A/dm ² to 10/dm ² is appropriate, and more preferably 0.11A/ ^dm2 ~3A/ ^dm2
It is. The regeneration method of the present invention includes bromide ions, chloride ions, sulfate ions, thiocyanine ions, sulfite ions, carbonate ions, phosphate ions, borate ions,
This effect is exhibited for all ordinary developing solutions containing at least two or more types of ions such as nitrate ions, phosphonate ions, and bicarbonate ions. The electrodialysis method to which the present invention is effectively applied is Japanese Patent Publication No. 52-34939, Japanese Patent Publication No. 51-84636, 51-85722, 51
−97432, 52−119934, 53−149331, 53−46732,
54−9626, 54−19741, 53−7234, 52−146236,
52-143018 and 54-58028, measure the concentration of bromide ions in the developer to be regenerated and adjust the amount of current so that the concentration of bromide ions in the developer remains constant. Any electrodialysis method for developer waste liquid that is equipped with a device to do this will suffice. In the present invention, in order to supply water in an amount corresponding to the amount of development processing to the concentration chamber solution, it is sufficient to use, for example, a pump synchronized with a replenishment pump that replenishes the replenisher to the developer tank of the processing machine, or Any known method may be used as long as it supplies a fixed amount of water depending on the amount of water to be treated. The developer solution to be regenerated using the present invention can contain known developing agents. As developing agents, dihydroxybenzenes (e.g. hydroquinone), 3-pyrazolidones), e.g. 1-
phenyl-3-pyrazolidone), aminophenols (e.g. N-methyl-p-aminophenol), 1-phenyl-3-pyrazolines, ascorbic acid, and 1.
Heterocyclic compounds such as a fused 2,3,4-tetrahydroquinoline ring and indolene ring, etc.
They can be used alone or in combination. The developer generally contains other well-known preservatives, alkaline agents,
Contains a PH buffering agent, antifogging agent, etc., and may further contain a solubilizing agent, a color toning agent, a development accelerator, a surfactant, an antifoaming agent, a water softener, a hardening agent, a viscosity imparting agent, etc. as necessary. . Color developers that can be regenerated using the present invention generally consist of alkaline aqueous solutions containing color developing agents. The color developing agent is a known primary aromatic amine developer, such as phenylene diamines (e.g., 4-amino-N.N-diethylaniline, 3-amino-N.N-diethylaniline,
-Methyl-4-amino-N・N-diethylaniline, 4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N
-ethyl-N-β-hydroxyethylaniline,
3-Methyl-4-amino-N-ethyl-N-β-
methanesulfamide ethylaniline, 4-amino-3-methyl-N-ethyl-N-β-methoxyethylaniline, etc.) can be used. Other Photography by LFAMason
Processing Chemistry (Focal Press, 1966)
), pages 226-229, U.S. Patent No. 2193015,
Those described in No. 2592364, JP-A-48-64933, etc. may be used. Color developers also contain pH buffering agents such as alkali metal sulfites, carbonates, borates and phosphates, development inhibitors or antifoggants such as bromines, iodides and organic antifoggants. be able to. If necessary, water softeners, preservatives such as hydroxylamine, organic solvents such as benzyl alcohol and diethylene glycol, development accelerators such as polyethylene glycol, quaternary ammonium salts, and amines, dye-forming couplers, competitive couplers, Fogging agents such as sodium borohydride, auxiliary developers such as 1-phenyl-3-pyrazolidone, viscosity-imparting agents, US Pat. No. 4,083,723
It may also contain a polycarboxylic acid chelating agent described in No. 1, an antioxidant described in OLS No. 2622950, and the like. Furthermore, the composition of this developing solution includes LFA.
“Photographic Processing” by Mason
Chemistry” Focal Press (1974), and TH James
Author “The Theory of the Photographic
Process” Macmillan Publishers (1977),
All conventional photographic processing chemicals listed in Research Disclosure No. 17643 (December 1978) are included. EXAMPLE Fujicolor paper was printed and exposed using an automatic developing machine consisting of a developer tank containing 600% developer having the composition shown in Table 1, a bleach-fixer tank containing 200% bleach-fixer having the composition shown in Table 2, and a washing bath. It was developed according to the steps shown in Table 3. Table 1 Benzyl alcohol 15 ml Diethylene glycol 8 ml Disodium ethylenediaminetetraacetic acid 5 g Sodium sulfite 2 g Anhydrous potassium carbonate 30 g Hydroxylamine sulfate 3 g Potassium bromide 0.6 g 4-Amino-N-ethyl-N-(β -methanesulfonamidoethyl)-m-toluidine 3/2
Sulfate/monohydrate 5 g Add water 1 (adjust to pH 10.20) Table 2 Ethylenediaminetetraacetic acid/disodium 2g Ethylenediaminetetraacetic acid ferric salt 40g Sodium sulfite 5g Ammonium thiosulfate 70g Add water 1 Table 3 Development process Color development 3 minutes 30 seconds 33℃ Bleach-fixing 1 minute 30 minutes 33℃ Water washing 1 minute 30 seconds 25-30℃ This developer tank contains a strong basic anion exchange membrane and a strong base anion exchange membrane as shown in Figure 1. Desalination chamber of ion exchange membrane electrodialysis tank made of strongly acidic cation exchange membrane (5 dm ² ×
20 chambers) were connected to circulate the developer. (Ten/
min). On the other hand, in the concentration chamber, solution 10, which was prepared by diluting the above developer to 1/4 and adding 4.85 g of potassium bromide per diluted solution, was circulated. (10/min). Further, platinum-plated titanium was used as an anode in the anode chamber, and stainless steel was used as a cathode in the cathode chamber, and an electrode solution 20 having the following composition was commonly circulated at both ends. (2
/min) Table 4 Electrode solution Sodium carbonate 29.3g Sodium hydrogen carbonate 6.4g Sodium nitrilotriacetate 1g 1 (PH10.20) Here, Fujicolor paper was 8.25cm wide and was developed at 15m/min. In order to compensate for the decrease in the capacity of the developer, 400 ml of a replenisher having the composition shown in Table 5 was added per minute. The overflowing liquid was temporarily stored, and water and replenisher were added to 8 parts of this liquid in an adjusted manner to make 10 parts to prepare a replenisher having the composition shown in Table 5. Table 5 Replenisher composition (in 1) Benzyl alcohol 19 ml Diethylene glycol 10 ml Disodium ethylenediaminetetraacetate 10 g Sodium sulfite 2.4 g Anhydrous potassium carbonate 32 g Hydroxylamine sulfate 3.5 g Potassium bromide 0.48 g 4-Amino-N- Ethyl-N-(β-methanesulfonamidoethyl)-m-toluidine 3/2
Sulfate monohydrate 7.3 g In order to demonstrate the effects of the present invention, as a comparative example, an automatic developing machine was operated continuously without operating the pump 8 in FIG. 1, that is, without adding dilution water to the concentration chamber solution. After continuous operation of this automatic developing machine for 2 hours, 5 hours, and 8 hours, the concentration of bromide ions in the concentration chamber solution, the molar ratio of the amount of bromide ions and the amount of carbonate ions dialyzed from the developer solution, and the developer solution in the developer tank were determined. PH was measured. Next, in order to demonstrate the effects of the present invention, pump 8 was activated and 40 ml of water was added per minute to the concentration chamber liquid to dilute this liquid, while the automatic developing machine was operated under the same conditions as the comparative example. Similarly, the bromide ion concentration of the concentration chamber solution after 2 hours, 5 hours, and 8 hours, the molar ratio of the amount of bromide ions and the amount of carbonate ions dialyzed from the developer (CO ₃ ^-- /Br ^- ), and the developer tank. The pH of the developer inside was measured. These results are summarized in Table 6.

[Table] As is clear from Table 6, in the present invention, the composition of the developer in the developer tank is kept constant even if the same developer replenisher is used for a long period of continuous operation. However, if the present invention is not used, the dialysis ratio of carbonate ions and bromide ions will vary, and if a replenisher with the same composition is used, the pH of the developer in the developer tank will increase, resulting in continuous operation for 5 hours. Later on, the PH changes beyond 0.05, causing serious consequences in terms of photographic performance. Therefore, in this case, it is necessary to adjust the composition of the replenisher depending on the operating time, which is extremely disadvantageous.

[Brief explanation of the drawing]

FIG. 1 is a flowchart showing a specific example of the present invention. The numbers in the figure indicate the following. 1...Developer tank, 2...Tank for storing overflow developer, 3...Tank for adding replenisher and water, 4...Tank for storing an aqueous solution of replenisher, 5...Developer replenisher storage tank , 6...
Electrodialysis tank (- represents a cation exchange membrane,...
... represents an anion exchange membrane. ), 7... concentration chamber liquid tank, 8... pump that operates according to the amount of color paper to be processed, 9... dilution water tank.

Claims (1)

[Claims] 1 Desalination chamber of an ion exchange membrane electrodialysis tank consisting of multiple anion exchange membranes and multiple cation exchange membranes between the cathode and the anode (cation exchange membrane on the cathode side, anion exchange membrane on the anode side) The developer tank of the processing machine is connected to a chamber partitioned by In a method of regenerating a developing waste solution through a controlled amount of current, an electrolyte solution ( The concentration chamber solution (hereinafter referred to as the concentration chamber solution) is diluted by supplying an amount of water corresponding to the amount of development processing, and the concentration of the electrolyte in the concentration chamber solution is adjusted to KBr.
A method for regenerating a photographic developer, characterized by carrying out electrodialysis while maintaining a constant concentration within the range of 2 g to 20 g/converted.