JPS6257018B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for selectively separating a developing agent from a photographic processing solution. Usually, the developer used to process silver halide photographic materials contains phenylene diamine, hydroquinone, pyrazolidone, aminophenol or a derivative thereof as a developing agent, carbonate, borate, or phosphate as an alkaline agent, and antioxidant. It contains developer components such as sulfites and hydroxylamine salts as agents, bromine salts, iodine salts, and 5-nitrobenzimidazole as development inhibitors, and a water-soluble solvent such as benzyl alcohol as a development accelerator. However, it is desired to remove or separate and recover the developing agent from the developing solution for economic reasons, environmental pollution reasons, and photographic property reasons. This applies not only to exhausted developing solution that overflows from the processing tank, but also to all photographic processing solutions containing developing agents.
For example, there is a similar need for a bleach solution, a bleach-fix solution, a fixer solution, a stop solution, etc. that follow the developer solution, and a developer solution that is no longer needed during the course of dissolving the developer solution.
In recent years, developing agents have become extremely expensive due to the soaring prices of raw materials.Furthermore, developing agents have higher biochemical oxygen demand (hereinafter referred to as BOD) and chemical oxygen demand (hereinafter referred to as COD), so they are more expensive than photographic processing solutions. The separation, recovery and removal of these substances is becoming increasingly desirable. Various methods have been proposed and put to practical use in order to separate and recover or remove the developing agent in the processing solution. For example, a removal method using activated carbon proposed in U.S. Pat. No. 3,884,983, a removal method using an organic solvent such as kerosene proposed in U.S. Pat. No. 2,358,053, and JP-A-52-82235.
A removal method using a styrene-divinylbenzene copolymer proposed in the specification of JP-A No. 1983-
Examples include the removal method using a methacrylate copolymer proposed in No. 50737. However, these conventional removal methods also have various practical drawbacks. That is, first, the removal method using activated carbon has excellent removal ability, but the adsorption is strong and the adsorbate cannot be easily separated, and activated carbon is difficult to regenerate. Secondly, removal methods using organic solvents such as kerosene are too dangerous in terms of disaster prevention and occupational safety and health, and cannot be put to practical use. Thirdly, styrene-divinylbenzene copolymer and methacrylate copolymer have excellent removal ability, and separation of adsorbed substances is much easier than activated carbon, but their separation ability is not very high.
It is economically unfavorable when collecting and regenerating the adsorbed matter. Therefore, a first object of the present invention is to provide a new method for selectively separating a developing agent from a photographic processing solution. A second object of the present invention is to provide a novel method for selectively separating a developing agent from a photographic processing solution, which has a high separation ability and an improved recovery and regeneration ability. A third object of the present invention is to provide a novel method that can remove a developing agent with a high pollution load from a photographic processing solution with a simple operation. In order to achieve the above object, the present inventor has conducted various exploratory studies and discovered that improvements can be made by bringing a photographic processing solution into contact with a phenol formaldehyde resin having a phenolic hydroxyl group and a hydroxyl methyl group as functional groups. He was able to complete his invention. Although the phenol formaldehyde resin according to the present invention may have any physical structure, it is preferably porous with a large surface condition, and the phenol formaldehyde resin has a specific surface area of about 1 to 3000 ^{m 2} /g. Furthermore, the specific surface area is approximately 100 to 1000 m ² /g in terms of efficiency in adsorbing and separating the developing agent and recovering the adsorbed developing agent.
Particularly preferably used are phenol formaldehyde resins. Specific examples include Duolite S-761 resin manufactured by Sumitomo Chemical Co., Ltd., but are not limited thereto. Examples of the developing agent according to the present invention include p-phenylenediamine derivatives, polyhydroxybenzene derivatives, 3-pyrazolidone derivatives, aminophenol derivatives, hydroxylamine derivatives, ascorbic acid derivatives, and 1-allyl-3-aminopyrazoline derivatives. , Specific developing agents include, for example, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-β-methanesulfonamidoethylaniline, 4-amino-N・N-
Diethylaniline, N-ethyl-N-β-(β-
methoxyethoxy)ethyl-3-methyl-4-aminoaniline and their salts, such as sulfate, hydrochloride, p-toluenesulfonic acid, as well as hydroquinone, chlorohydroquinone, hydroquinone monosulfonic acid, methylhydroquinone, pyrogallol, catechol. , 2,5-dimethylhydroquinone, 1-phenyl-3-pyrazolidone,
1-phenyl-4-methyl-3-pyrazolidone,
1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone, p-aminophenol,
N-methyl-p-aminophenol, o-aminophenol, 2,4-diaminophenol, ascorbic acid, 1-(p-hydroxyphenyl)-3
-aminopyrazoline, hydroxylamine, N.
Examples include N-diethylhydroxylamine. These developing agents are 0.1g per processing solution 1.
It is used at a concentration of from about 30 g, more preferably from 0.3 to about 15 g. Further, the above-mentioned developing agents can be used alone or in a mixture of two or more kinds in the processing solution. The processing solution according to the present invention can contain, in addition to the above-mentioned developing agent, an alkaline agent commonly used in developing solutions, such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, borax, etc. It may contain additives such as benzyl alcohol, alkali metal halides such as potassium bromide and potassium chloride, development regulators such as citradinic acid, and preservatives such as hydroxylamine and sulfites. Further, the developing agent is present not only in the developer, but also in the bath or washing water that follows the developer. Therefore, the method of the present invention can be applied not only to a developer but also to any processing solution containing a developing agent. Various embodiments are conceivable for carrying out the method of the present invention, for example, the phenol formaldehyde resin of the present invention is present in a photographic processing bath, or the overflow processing solution is continuously or batchwise carried out. It may also be brought into contact with a phenol formaldehyde resin. Any method may be used to bring the treatment liquid of the present invention into contact with the phenol formaldehyde resin of the present invention, but in particular, a cylindrical container is filled with the phenol formaldehyde resin of the present invention to form a resin layer, and the treatment liquid is passed through the container. A so-called column method is preferably used because it has good contact efficiency. The method of the present invention can be applied to color negative film, color paper, color positive film, color reversal film for slides, color reversal film for movies,
It can be applied to any processing solution containing a developing agent for a series of silver halide photographic materials such as TV color reversal film, reversal color paper, black-and-white film, black-and-white paper, X-ray film, and lithographic film. EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the embodiments of the present invention are not limited thereto. Example 1 A developer having the following components was prepared. Potassium carbonate 30g Sodium bicarbonate 2.5g Potassium sulfite 5g Sodium bromide 1.2g Potassium iodide 1.5mg Hydroxylamine sulfate 2.5g Sodium chloride 0.3g Sodium diethylenetriaminepentaacetate 2.5g 4-Amino-3-methyl-N-ethyl-N −(β
-hydroxyethyl)-aniline sulfate 4.6g Potassium hydroxide 1.0g Add water to make 1, potassium hydroxide or 20%
Adjust the pH to 10.06 using sulfuric acid. Cylindrical column 4 with a diameter of 6 inches and a height of 80 inches.
A book was filled with 15 of each of the following substances (A) to (D), and 1,000 ml of the developer was applied from the top of the column at a flow rate of 5.
/min. Γ Filler (A) Duolite S- manufactured by Sumitomo Chemical Co., Ltd.
761 (porous) (inventive example) Γ Filler (B) Activated carbon manufactured by Takeda Pharmaceutical Co., Ltd. (comparative example) Γ 〃 (C) Amberlite XAD-2 manufactured by Rohm and Haas, styrene-divinylbenzene Polymer (comparative example) Γ filling (D) Kynol fiber manufactured by Nippon Kynol Co., Ltd., phenol-formaldehyde copolymer (comparative example) Each component of the developer after passing through was analyzed. Next, water is added to each column after the developer has passed through it.
250 and then 5% sulfuric acid 1000 to separate the adsorbed developing agent. Each component of this developer in sulfuric acid was analyzed. Components of the developer before passing through the column, components of the developer after passing through the column, and sulfuric acid solution when sulfuric acid is passed through the packing after passing through the column when packing (A) of the present invention example is used. The analytical values of the liquid components are shown in Table 1. Furthermore, regarding the developing agent (4-amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline sulfate) in the developer component, when using fillers (A) to (D), The concentration of the developer before passing through the column, the concentration of the developer after passing through the column, and the concentration in the sulfuric acid solution when sulfuric acid was passed through the packing after passing through the developer were determined by analysis and shown in Table 2.

[Table] Components of the developer other than those shown in Table 1 did not change before and after passing through the column.

[Table] Table 1 shows that the phenol formaldehyde resin (A) of the present invention removes the developing agent in the developer component very selectively. Further, as shown in Table 2, although activated carbon removes the developing agent very efficiently, its elution is extremely poor, and the styrene-divinylbenzene copolymer has a somewhat poor efficiency in removing the developing agent and its elution is not very good. Furthermore, non-porous phenol formaldehyde copolymers such as kynol fibers do not remove much developing agent. However, it can be seen that the phenol formaldehyde resin of the present invention removes the developing agent extremely selectively and with high efficiency, and also performs elution with high efficiency. Example 2 A similar experiment was carried out by replacing the developer in Example 1 with the one shown below, and the same results as in Example 1 were obtained. Sodium tripolyphosphate 2g N-methylaminophenol sulfate (developing agent) 3g Sodium sulfite 40g Hydroquinone (developing agent) 6g Sodium carbonate 50g Sodium thiocyanate 1.7g Potassium iodide 6mg Sodium bromide 2g Add water to make 1, then water potassium oxide or 20%
Adjust the pH to 10.2 using sulfuric acid.

Claims (1)

[Claims] 1. A developing agent is added to a photographic processing solution by contacting a photographic processing solution with a phenol formaldehyde resin having a phenolic hydroxyl group and a hydroxymethyl group as functional groups and having a specific surface area of 1 to 3000 m ² /g. How to separate.