JPH11117028A - Separation of silver - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silver concn. of a ppm unit by using a specific resin compsn. having a mercapto group for separating away silver from a silver-contg. soln. contg. silver complex ions having a ligand inclusive of sulfur atoms. SOLUTION: The resin compsn. to be used consists of a polymer or copolymer of a monomer having a thirane ring and is any of four kinds of the resins described below. The resin A is obtd. by bringing the (co)polymer of the monomer of formula I and an alkali hydroxide into reaction and the resin B is the reactant of the monomer copolymer of formula I and an amine of the formula A1 NH2 (A1 is H, alkyl, aminoalkyl). The resin C is a resin having a structural unit of formula II. In the formulae I, II, R1 , R2 are each H, a lower alkyl, a halogen or a monohalomethyl. The resin D is a resin having a structural unit of formula III. In the formula III, R3 denotes H, a lower alkyl, a halogen or a monohalomethyl group and A2 denotes H, an alkyl, or an aminoalkyl group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for separating silver using a novel resin composition. Specifically, a silver-containing solution such as a waste liquid containing a silver complex ion having a ligand containing a sulfur atom discharged from a photographic photosensitive material manufacturing plant, a processing plant (for example, a photo lab) or a silver plating plant is processed. hand,
The present invention relates to a method for separating a silver component.

[0002]

2. Description of the Related Art In recent years, environmental protection and silver resource saving have been emphasized, and there has been a strong demand for a method for reducing pollution and a method for efficiently separating or recovering silver. The following two methods are widely used as methods for separating or recovering silver from a liquid containing a soluble silver salt. (1) A method of displacing dissolved silver by contacting a base metal, which is a metal having a greater ionization tendency than silver. (2) An electrolytic method in which silver is deposited on a cathode by electrolysis.

However, these methods have various disadvantages. For example, the former method requires a base metal (e.g., iron or aluminum) equivalent to silver ions, and the base metal ions are eluted and accumulated in the processing solution, or a bleach-fixing solution containing an organic acid iron chelate complex; Alternatively, in the case of a fixing solution or the like, there are disadvantages such as formation of iron hydroxide, causing clogging of a cartridge or the like, and lowering the efficiency of separating and recovering silver.

In the latter method, in the case of a bleach-fixing solution or a fixing solution containing an organic acid iron chelate complex, a part of the silver electrolytically deposited on the cathode is a bleach-fixing solution containing the organic acid iron chelate complex. It is redissolved in the fixer and has the disadvantage that the amount of precipitated silver per unit charge (hereinafter referred to as current efficiency) is reduced.

Various proposals have been made to solve these drawbacks. For example, the above-mentioned method, that is, the method of recovering electrolytic silver, is described in
No. 6315, No. 52-115723, No. 53-328
No. 69, No. 53-60391, West German Patent No. 2,33
No. 3,018, No. 2,429,288, Belgian Patent No. 780,623, U.S. Pat. No. 3,400,056
No. 3,840,455 and No. 3,964,99
No. 0, 4,069, 127, and the like. The method described in these, the method of adding a reducing agent while changing the potential and electrolysis, the method of using a diaphragm, the electrodialysis method, the method of automatically controlling the current,
Most of the techniques are related to a liquid feeding and stirring method or an improvement of a device such as an electrode or an electrode plate. However, all have the drawbacks that the current efficiency is not yet sufficient, and the device is large and complicated. An even more serious disadvantage is that the electrolytic silver recovery method is suitable for recovering silver from silver salts of 0.1 g or more. It was impossible to do.

Other methods for recovering silver include those using a basic ion-exchange resin, for example, JP-A-49-708.
No. 23, 51-17114, DT2630
No. 661, DL130180 and the like,
Again, although silver can be separated and recovered to some extent, it is difficult to achieve a silver ion concentration of a few ppm level by the ion exchange resin method, and there are problems such as an increase in the size of the apparatus and cost, and the recent growth. The fact is that it is not very applicable in the remarkable minilab market.

[0007]

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to firstly provide an efficient method for separating silver from a silver-containing solution such as a photographic processing solution or a waste solution.
It is an object of the present invention to provide a method for reducing pollution by making it possible to obtain a silver concentration of m units.

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, the present invention has been accomplished.

That is, the objects of the present invention are: Using a resin composition comprising a resin having a mercapto group, a method for separating silver, comprising separating silver from a silver-containing solution containing a silver complex ion having a ligand containing a sulfur atom,

[0010] 2. The method for separating silver according to the above 1, wherein the silver-containing solution is a photographic processing solution or a photographic processing waste liquid,

3. The method for separating silver according to 1 or 2, wherein the resin is synthesized from a polymer or copolymer of a monomer having a thiirane ring.

4. 4. The method for separating silver according to any one of the above 1 to 3, wherein the resin is the following resin A to D.

[0013]

Embedded image [In the formula, R ₁ represents hydrogen, a lower alkyl group, a halogen or a monohalomethyl group. ] A resin having a mercapto group obtained by reacting a polymer and a copolymer of the monomer represented by the formula (1) or a copolymer with another vinyl monomer copolymerizable with the monomer with an alkali hydrosulfide.

Resin B The copolymer of the above formula (I) is represented by the formula A ₁ NH ₂ wherein A ₁ represents a hydrogen atom, an alkyl group or an aminoalkyl group. A resin having a mercapto group obtained by reacting with an amine represented by the formula:

Resin C A resin having a structural unit represented by the following general formula (II).

[0016]

Embedded image [Wherein, R ₂ represents hydrogen, a lower alkyl group, a halogen or a monohalomethyl group. Resin D A resin having a structural unit represented by the following general formula (III).

[0017]

Embedded image [Wherein, R ₃ represents hydrogen, a lower alkyl group, a halogen or a monohalomethyl group, and A ₂ represents a hydrogen atom, an alkyl group, or an aminoalkyl group. According to the resin composition of the present invention achieved by each of the above, by contacting with a silver complex ion solution having a ligand containing a sulfur atom,
Silver component or silver compound can be separated and recovered.

In the case of a photographic processing solution which is a typical example of a silver-containing solution, maintaining a low silver ion concentration in a photographic processing tank while continuously separating and recovering silver ions is necessary for desilvering reaction and the like. This is preferable in order to promote the reaction efficiently or to suppress the generation of silver sludge. Then, the photographic processing solution having a reduced silver ion concentration due to the separation of silver ions is returned to the same photographic processing tank again (in-line processing), or the same photographic processing tank or It can be supplied as a replenisher to other photographic processing tanks, thereby preventing pollution and reusing resources. For example, after washing or washing alternative stabilizer is separated into silver according to the present invention, it is returned to the same washing or washing alternative stabilizer, or another washing solution such as developer, bleaching solution, fixing solution (or bleach-fixing solution) is used. It may be used as a diluent for replenishment of various types of photographic processing solutions. In particular, in the desilvering step in photographic processing, if silver is separated in-line, the desilvering speed can be improved and the replenisher can be reduced.

[0019]

DESCRIPTION OF THE PREFERRED EMBODIMENTS First, the resin composition according to the present invention will be described. Typical examples of the resin composition according to the present invention include the following.

[0020]

Embedded image

[0021]

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The resin composition according to the present invention, which is specifically represented, can be obtained, for example, by polymerizing or copolymerizing a monomer having a thiirane ring. Hereinafter, this point will be described in detail.

The ETMA forming the resin of the present invention may be copolymerized with a hydrophobic monomer and / or a hydrophilic monomer. As the hydrophobic monomer, for example, acrylates,
Methacrylic esters, vinyl esters, olefins, styrenes, crotonic esters, itaconic diesters, maleic diesters, fumaric diesters, allyl compounds, vinyl ethers, vinyl ketones, vinyl heterocyclic compounds, Glycidyl esters,
Examples thereof include hydrophobic monomers obtained by combining one or more selected from unsaturated nitriles and various unsaturated acids. Acrylic esters and / or methacrylic esters and styrenes are preferred as the hydrophobic monomer forming the hydrophobic polymer compound used in the present invention.

The resin used in the present invention may be copolymerized with a hydrophilic monomer in addition to the hydrophobic monomer. Such hydrophilic monomers include acrylic acid, carboxyl group-containing monomers such as methacrylic acid, hydroxyl group-containing monomers such as hydroxyethyl acrylate, alkylene oxide-containing monomers, acrylamides, methacrylamides, Sulfonic acid group monomers, amino group-containing monomers and the like can be preferably used, but include hydroxyl group-containing monomers, carboxyl group-containing monomers, amide group-containing monomers, and sulfone group-containing monomers Is particularly preferred. Since such a hydrophilic monomer is dissolved in water when added in a large amount, it is preferably about 0.1 to 30 wt%, particularly preferably 1.0 to 20 wt%.

The resin used in the present invention has at least 2
It contains a number of copolymerizable ethylenically unsaturated monomers.
Examples of such a monomer include divinylbenzene, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate,
Vinyl groups such as N, N-methylenebisacrylamide
Having three vinyl groups such as trivinylcyclohexane, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, and pentaerythritol trimethacrylate, and four vinyl groups such as pentaerythritol tetraacrylate and pentaerythritol tetramethacrylate Can be mentioned, but it is not particularly limited to these.

Examples of the polymerization method of the resin used in the present invention include an emulsion polymerization method, a solution polymerization method, a bulk polymerization method, a suspension polymerization method, and a radiation polymerization method.

In solution polymerization, a mixture of monomers at a suitable concentration in a solvent (usually a mixture of 40% by weight or less, preferably 10 to 25% by weight with respect to the solvent) is added to about 10% by weight in the presence of an initiator. It is obtained by conducting the polymerization at a temperature of from 200 to 200 ° C, preferably from 30 to 120 ° C, for about 0.5 to 48 hours, preferably for 2 to 20 hours. Any initiator may be used as long as it is soluble in the polymerization solvent. For example, an organic solvent-based initiator such as benzoyl peroxide, azobisisobutyronitrile (AIBN), or tertiary butyl peroxide, and ammonium persulfate (AP)
S), water-soluble initiators such as potassium persulfate and 2,2'-azobis- (2-amidinopropane) -hydrochloride, and redox polymerization combining these with reducing agents such as Fe ²⁺ salts and sodium hydrogen sulfite. Initiators and the like can be mentioned. The solvent may be any solvent that dissolves a mixture of monomers, and examples thereof include water, methanol, ethanol, dimethyl sulfoxide, dimethylformamide, dioxane, and a mixed solvent of two or more of these. After the completion of the polymerization, the unreacted mixture can be separated and removed by pouring the reaction mixture into a medium that does not dissolve the formed copolymer, allowing the product to settle, and then drying.

In the suspension polymerization method, water is used as a dispersion medium, and 10 to 50% by weight of a monomer based on water and 0.05 to 5% by weight of a polymerization initiator, 0.1 to 20% by weight based on the monomer.
About 30 to 100 ° C., preferably 60 to 100 ° C.
It is obtained by polymerizing under stirring at 90 ° C. for 3 to 8 hours. The concentration of the monomer, the amount of the initiator, the reaction temperature, the time and the like can be widely and easily changed.

Examples of the initiator include water-soluble peroxides (eg, potassium persulfate, ammonium persulfate, etc.) and water-soluble azo compounds (eg, 2,2′-azobis- (2-amidinopropane) -hydrochloride, etc.) Or a redox-based polymerization initiator obtained by combining these with a reducing agent such as an Fe ²⁺ salt or sodium bisulfite. As the dispersant, any of a surfactant and / or a water-soluble polymer can be preferably used. As the surfactant, any of an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant can be used, and preferably, an anionic surfactant and / or a nonionic surfactant are used. Activator. Examples of the water-soluble polymer include, for example, a synthetic polymer and a natural water-soluble polymer, and any of them can be preferably used in the present invention. Among them, as the synthetic water-soluble polymer, for example, those having a nonionic group in the molecular structure,
Examples thereof include those having an anionic group and those having a cationic group. Examples of the nonionic group include an ether group, an alkylene oxide group, a hydroxy group, an amide group, and an amino group. Examples of the anionic group include a carboxylic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a sulfonic acid group or a salt thereof, and the like. Examples of the cationic group include a quaternary ammonium base,
And a tertiary amino group. As natural water-soluble polymers, for example, those having a nonionic group in the molecular structure,
Examples thereof include those having an anionic group and those having a cationic group. Examples of the natural water-soluble polymer include those described in detail in a comprehensive technical data collection of water-soluble polymer water-dispersible resins (Management Development Center), and preferably lignin, starch, pullulan, cellulose, dextran, dextrin , Glycogen, alginic acid, gelatin, collagen, guar gum, acacia, laminaran, lichenin, nigran and the like and derivatives thereof. As the derivative of the natural water-soluble polymer, sulfonated, carboxylated, phosphorylated, sulfoalkylated, carboxyalkylated, alkylphosphorylated, and salts thereof are preferably used. Particularly preferably, glucose, gelatin, dextran, cellulose, pullulan,
Glucomannan, dextrin, gellan gum, locust bean gum, xanthan gum and derivatives thereof.

The resin composition according to the present invention preferably has a porous shape such as a chain. The synthesis and purification of a typical example of the resin composition according to the present invention will be described below.

A- (1) Synthesis and Purification of 2,3-Epithiopropyl Methacrylate (ETMA) Monomer A 1dm ³ Erlenmeyer flask was charged with ammonium thiocyanate (N
325 g of H ₄ SCN) was weighed, and methanol 70 was added thereto.
Add 0 cm ^{3 and} dissolve. Next, 500 cm ^{3 of} glycidyl methacrylate is placed in a ² dm ³ Erlenmeyer flask, and 0.05 g of hydroquinone is added as a polymerization inhibitor. The Erlenmeyer flask is cooled in an ice-water bath, and stirred (NH ₄
SCN-methanol) solution from a 1 dm ³ separatory funnel.
Add dropwise over 3 hours. After dropping, add 4 under ice-cooling.
Stirring was continued for ５5 hours, silica gel was added to the obtained crude ETMA, and the mixture was left to dehydrate overnight in a refrigerator. Thereafter, distillation under reduced pressure (75 to 80 ° C./3 mmHg) was performed. In addition, ETMA having a purity of 99% or more was obtained by repeating rectification of ETMA (60 to 65 ° C./3 mmHg) twice.

A- (2) Purification of divinylbenzene (DVB) monomer An appropriate amount of DVB was put into a separating funnel, and 1N cooled sufficiently.
An equivalent amount of NaOH was added, and the polymerization inhibitor in DVB was extracted and removed. Extraction was performed until the lower NaOH layer turned from red to colorless (3-4 times). Thereafter, cooled ion-exchanged water was added in the same amount as divinylbenzene to remove alkali components. This extraction was performed by adding phenolphthalein to the lower aqueous layer until the red color was no longer exhibited (4 to 5 times). After the extraction, silica gel was added, and the mixture was left to dehydrate in a refrigerator overnight.

A- (3) α, α'-azobisisobutyronitrile (AIBN) After recrystallization from ethanol, white needle crystals were filtered by suction, dried and stored in a brown bottle.

A- (4) Synthesis of Alcoholic Potassium Hydrosulfide (KSH) 200 g of potassium hydroxide was dissolved in 800 cm ³ of ethanol, and alcoholic potassium hydrosulfide was synthesized through hydrogen sulfide until the pH became lower than 10.

B- (1) Synthesis of resin (RE) based on 2,3-epithiopropyl methacrylate-divinylbenzene spherical copolymer B- (2) 2,3-epithiopropyl methacrylate-
Synthesis of divinylbenzene spherical copolymer

(1) Preparation of monomer 2,3-epithiopropyl methacrylate (ETMA)
41.52 ml and divinylbenzene (DVB) 8.48
Then, 25 ml of 2,2,4-trimethylpentane (TMP) was added thereto, and 0.5 g of AIBN was further added and dissolved.

(2) Procedure 0.2 g of gelatin was completely dissolved by heating in ion-exchanged water to make the total amount 500 cm ^3. This solution was put into a polymerization apparatus together with 7.5 g of anhydrous sodium sulfate and 10 g of calcium carbonate. The liquid was slowly stirred for about 20 minutes to prepare a dispersion bath. Thereafter, the previously prepared monomer liquid was put into the polymerization apparatus.

First, the monomer particles were dispersed in a gelatin solution by gently stirring, and the rotation speed (about 280 rpm) was adjusted while observing the size of the particles while illuminating with a light.
When the desired size was reached, stirring was continued for about 30 minutes to stabilize the resin balls, and then the liquid temperature was raised to 70 ° C. over 1 hour. This state was continued for about 1 hour, and the liquid temperature was raised to 90 ° C. or more over 2 hours, and the resin was aged for 2 hours. After cooling, the resin balls were separated and immersed in 1N HCl for 1 hour, and then boiled in ion-exchanged water to dissolve the gelatin adhering to the resin balls. The resin balls were separated while hot, and immersed in methanol overnight to extract and remove TMP. 32-6 after drying
The 2-mesh resin was sieved and then rolled on a metal plate having an appropriate inclination to select only spherical particles to obtain the target resin (Chem. 9).

B- (3) Synthesis of Resin Having a Thiel Group and Triethylenetetramine Chain (RE-TTA) 2 g of absolutely dried RE was placed in a pressure-resistant test tube, 25 cm ³ of 1,4-dioxane was added, and the mixture was allowed to stand overnight. The spheres were swollen. Add 5 cm of triethylenetetramine (TTA)
³ and sealed, and reacted at 90 ° C. for 8 hours with occasional shaking in an oil bath. After completion of the reaction, the reaction solution was left to cool, and the filtered resin was washed with methanol and ion-exchanged water.
The unreacted amine was washed and removed by repeating this operation 3 to 4 times. Next, it was immersed in 1N NaOH and washed several times, and then washed in ion-exchanged water until phenolphthalein no longer showed a red color. Finally, after Soxhlet extraction with methanol, air-drying and absolute drying are performed, and the resin having the desired triethylenetetramine chain (RE-TTA)
Was obtained (Chemical formula 9). The synthesized resin was confirmed by elemental analysis.

B- (4) Resin having a thiol group (RE
Synthesis of —KSH) To 1 g of RE was added 6 cm ³ of an alcoholic potassium hydrosulfide (KSH) solution, and the mixture was reacted at 50 ° C. for 1 hour to introduce a thiol group. After the reaction, the resultant was immersed in 1N hydrochloric acid overnight, and washed in ion-exchanged water until phenolphthalein no longer showed a red color (Chem. 9).

[0041]

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Next, a method for separating silver using the resin composition according to the present invention will be described. The photographic processing solution or waste solution of the present invention may be any photographic processing solution or waste solution containing a silver component or a silver compound (containing complex salt), such as a black and white developing solution, a color developing solution, a bleaching solution, a fixing solution, Examples include a bleach-fixing solution, a stabilizing solution or a stabilizing solution instead of washing, a rinsing solution, a pre-washing solution, and the like, or a mixed solution of the above-mentioned processing solutions or waste solutions. In the method for separating silver according to the present invention, a silver component or a silver compound is adsorbed and separated on a resin composition by bringing a silver-containing solution into contact with the resin composition according to the present invention.

According to one preferred embodiment of the present invention, silver is directly recovered from a bleach-fix solution containing an organic acid complex such as an aminopolycarboxylic acid ferric complex as an oxidizing agent, and bleaching is performed. Fixer replenishment amount is, for example, 0.1
By setting it to 5 ml / 100 cm ² , stable photographic performance can be obtained even when a photographic photosensitive material having a high silver content is subjected to running processing.

The case where the method of separating silver according to the present invention is applied in-line to bleach-fixing as a typical example will be described first. The bleach-fix solution used in the present invention may contain iodide and / or thiocyanate. Examples of iodide used include sodium iodide, lithium iodide, potassium iodide, ammonium iodide,
Iodine acetic acid or the like can be used. The amount added is preferably such that the iodide is at least 1 mol per liter of the bleach-fix solution, more preferably 1 mol per liter.
It is used in an added amount of 8 mol. When the amount of iodide per liter is less than 1 mol, the function as a fixing agent is insufficient. Although it may be added in excess of 8 mol, a large effect cannot be obtained even if the addition amount is increased more. The addition amount is more preferably 1.6 mol to 6 mol per liter, particularly preferably 2 mol to 5 mol. This preferred amount also applies to thiocyanates.

The thiocyanate as a preferable fixing agent contained in the bleach-fixing solution of the present invention may be any thiocyanate compound used for causing thiocyanate ions to be contained in the processing solution. Examples of the compound include sodium thiocyanate, potassium thiocyanate, and ammonium thiocyanate. In addition, any soluble thiocyanic acid compound can be used regardless of inorganic salts, organic salts and the like. Particularly preferred are ammonium salts and potassium salts which have a high diffusion rate of the light-sensitive material to be processed into the gelatin layer. These thiocyanate compounds can be used alone or in appropriate combination of two or more. When two thiocyanates are used in combination, the total concentration of the thiocyanate must satisfy the above concentration. Cost. Also in the case of combined use with iodide, it is necessary that the total concentration also satisfies the above-mentioned concentration.

In the present invention, a fixing agent other than the above-mentioned iodide and / or thiocyanate may be used. For example, thiosulfates such as sodium thiosulfate, ammonium thiosulfate and potassium thiosulfate, thiourea, thioether and the like can be used.

The bleach-fix solution is described in JP-B-61-135.
No. 79, No. 60-10303, JP-A-52-1344
No. 33 and No. 52-145029 can be referred to. The temperature of the bleach-fix solution is 10 to 100 ° C
Is preferably 40 to 90 ° C., and more preferably 50 to 90 ° C.
80 ° C. is most preferred. The pH value of the bleach-fixing solution is arbitrary, and is, for example, pH 6.5 or less.
It is in the range of 4.5 to 6.5. The replenishment amount of the bleach-fix replenisher to the bleach-fix solution of the present invention may be a low replenishment amount, for example, may be 30 ml or less per 100 cm ^{2 of the} light-sensitive material to be processed, preferably 0.1 to 30 ml, more preferably 0.5 to 10 ml. Milliliters are preferred. The composition of the bleach-fix replenisher may be the same as or different from the composition of the bleach-fix start solution (starter).

In the desilvering step of the present invention, a single-bath bleach-fixing process is preferably performed, but a process such as bleaching, bleaching → bleach-fixing, bleach-fixing → fixing, bleach-fixing → bleach-fixing is performed. Is also good.

The bleaching agent used in the bleach-fixing solution may be any of known ones, but a ferric organic acid complex salt is particularly preferred. III) It is preferable to include a complex salt. This is a complex of a trivalent iron (ferric) ion and an aminopolycarboxylic acid or a salt thereof. When processing with a bleach-fixing solution subsequent to color development, the bleach-fixing solution may contain a ferric complex salt of a compound represented by the following general formula [A].

[0050]

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In the formula, A _{1 to} A ₄ may be the same or different and each represents —CH ₂ OH, —COOM or —PO ₃ M ₁
Representing the M _2. M, M ₁ and M ₂ each represent a hydrogen atom, sodium, potassium or ammonium. X represents a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms.

Next, the compound represented by formula (A) will be supplementarily described. A _{1 to} A ₄ may be the same or different, and each represents —CH ₂ OH, —COOM, or —PO ₃ M
Represents ₁ M _2, represents _M, M 1, _{M 2} are each a hydrogen atom, sodium, potassium or ammonium. X represents a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms (eg, propylene, butylene, trimethylene, tetramethylene, pentamethylene, etc.), and examples of the substituent include a hydroxyl group. Preferred specific examples of the compound represented by the general formula [A] are shown below.

[0053]

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As the compounds (A-1) to (A-8), besides the above, any of these sodium salts, potassium salts or ammonium salts can be used arbitrarily. Is preferably used.

The second compound of the compound represented by the general formula [A]
The iron complex is 0.002 mol / l of bleach-fixing solution.
A range of 1.0 mol is preferably used, more preferably 0.01 mol to 0.8 mol, particularly preferably 0.03 mol to 0.6 mol.

In the bleach-fixing solution of the present invention, preferred bleaching agents which are used in combination with or in place of the compound represented by the above general formula [A] include the following. [A'-1] Ethylenediaminetetraacetic acid or a salt thereof (a salt of ammonium, sodium, potassium, triethanolamine or the like) [A'-2] trans-1,2-cyclohexanediaminetetraacetic acid or a salt thereof (〃) [A '-3] Dihydroxyethylglycinic acid or a salt thereof (〃) [A'-4] Ethylenediaminetetrakismethylenephosphonic acid or a salt thereof (〃) [A'-5] Nitrilotrismethylenephosphonic acid or a salt thereof (〃) [ A'-6] Diethylenetriaminepentakismethylenephosphonic acid or a salt thereof (〃) [A'-7] Diethylenetriaminepentaacetic acid or a salt thereof (〃) [A'-8] Ethylenediaminediorthohydroxyphenylacetic acid or a salt thereof (〃) [A′-9] hydroxyethylethylenediaminetriacetic acid or a salt thereof (〃) [ A'-10] Ethylenediaminedipropionic acid or a salt thereof (〃) [A'-11] Ethylenediaminediacetic acid or a salt thereof (〃) [A'-12] Glycoletherdiaminetetraacetic acid or a salt thereof (〃) [A ' -13] Hydroxyethyliminodiacetic acid or its salt (〃) [A'-14] Nitrilotriacetic acid or its salt (〃) [A'-15] Nitrilotripropionic acid or its salt (〃) [A'-16] Triethylenetetramine hexaacetic acid or a salt thereof (〃) [A′-17] Ethylenediaminetetrapropionic acid or a salt thereof (〃) The above-mentioned compounds can be mentioned, but of course, the compounds are not limited to these exemplified compounds. In these compounds, A'-1, A'-2, A'-
7, A'-12 is preferred.

The aminopolycarboxylate iron (III) complex salt may be used in the form of a complex salt or an iron (III) salt such as ferric sulfate, ferric chloride, ferric acetate, ferric sulfate. An iron (III) ion complex salt may be formed in a solution using an aminopolycarboxylic acid or a salt thereof with ammonium, ferric phosphate or the like. When used in the form of a complex salt, one kind of complex salt may be used, or two or more kinds of complex salts may be used. On the other hand, when a complex salt is formed in a solution using a ferric salt and an aminopolycarboxylic acid, one or more ferric salts may be used. Further, one or more aminopolycarboxylic acids may be used. In each case, the aminopolycarboxylic acid is replaced with iron (III).
It may be used in excess of forming an ionic complex. The aminopolycarboxylic acid and the iron complex salt may be used as an ammonium salt, a sodium salt, a potassium salt, or a triethanolamine salt, or two or more of these may be used in combination. The bleach-fixing solution or the bleaching solution containing the iron (III) ion complex includes cobalt, copper, nickel, other than iron,
A metal ion complex salt such as zinc may be contained.

The amount of the bleach-fixing solution or the bleaching agent per liter of the bleaching solution used in the present invention is preferably from 0.1 to 3 mol, more preferably from 0.2 to 1.0 mol. The bleach-fixing solution or bleaching solution used in the present invention may be a compound having a mercapto group or a disulfide bond.
No. 61-47961, No. 61-252552,
Bleaching accelerators such as those described in JP-A-61-22295 can be incorporated. The bleach-fixing solution or the bleaching solution used in the present invention may contain various additives. For example, a compound having a pyrrolidone nucleus in the molecular structure can be preferably used. The addition amount is preferably 1 to 100 g / liter, more preferably 5 g / l.
５０50 g / l, and other details
-298499.

In carrying out the silver separation method of the present invention, silver is separated from the above bleach-fixing solution or bleaching solution using the resin composition according to the present invention. The silver separation method may be any method as long as silver can be separated from the bleach-fixing tank solution or the bleaching tank solution.These silver separation is performed by in-line silver separation from the bleach-fixing tank solution or the bleaching tank solution. is there. It is also preferable that the silver separation method of the present invention is applied to an in-line method for other photographic processing solutions.

Next, photographic processing solutions other than the above-mentioned bleach-fixing solution or bleaching solution, which constitute the photographic processing solution or waste solution of the present invention, will be described, but are not limited to the following.
For the color developer, hydroxylamine conventionally used as a preservative may be used, or alternatively,
JP-A-63-146043 and JP-A-63-146042
Nos. 63-146041, 63-146040
And hydroxylamine derivatives described in JP-A Nos. 63-135938 and 63-118748 and JP-A-64-62.
No. 639, hydroxamic acids, hydrazines, hydrazides, phenols, α-hydroxyketones, α
-Aminoketones, sugars, monoamines, diamines,
Quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, condensed amines, and the like may be used as the organic preservative. In particular, a hydroxylamine derivative or a hydrazine derivative is preferably used from the viewpoint of reducing benzyl alcohol as much as possible and improving silver recovery efficiency.

Further, the color developing solution includes dietatolamine,
A compound such as triethanolamine may be contained. The color developing agent used in the color developing solution is preferably a p-phenylenediamine compound having a water-soluble group.
The water-soluble group has at least one on the amino group or the benzene nucleus of the p-phenylenediamine compound,
Specific water-soluble _{group, - (CH 2) n -CH} 2 OH, - (CH 2) m -NHSO 2 - (CH 2) n -CH 3, - (CH 2) m -O- (CH _{2) n -CH 3, - (} CH 2 CH 2 O) n C m H 2m + 1 (m and n each represents an integer of 0 or more), -. COOH group, -SO
_{A 3} H group is preferred. The above color developing agents are usually used in the form of salts such as hydrochloride, sulfate, p-toluenesulfonate and the like.

The color developing solution may contain the following developing solution components in addition to the above components. As an alkaline agent,
For example, sodium hydroxide, potassium hydroxide, silicate,
Sodium metaborate, potassium metaborate, phosphoric acid 3
Sodium, tripotassium phosphate, borax and the like can be used alone or in combination as long as no precipitation occurs and the pH stabilizing effect is maintained. Further, from the necessity of preparation, or for the purpose of increasing ionic strength,
Various salts such as disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium bicarbonate, potassium bicarbonate, and borate can be used.

Further, if necessary, inorganic and organic antifoggants can be added. Furthermore, if necessary, a development accelerator can be used. U.S. Pat. Nos. 2,648,604 and 3,673 as development accelerators
No. 1,247, JP-B-44-9503, various kinds of pyridinium compounds, other cationic compounds, cationic dyes such as phenosafranine, neutral salts such as thallium nitrate, U.S. Pat. , 990
No. 2,531,832, No. 2,950,970
No. 2,577,127 and JP-B-44-9504
Non-ionic compounds such as polyethylene glycol and derivatives thereof and polythioethers described in U.S. Pat. No. 2,304,925, and phenethyl alcohol and others, acetylene glycol, methyl ethyl ketone, cyclohexanone, thioethers and pyridine , Ammonia, hydrazine, amines and the like.

To the color developing solution, benzyl alcohol may be added, or a poorly soluble organic solvent represented by phenethyl alcohol may or may not be added. The color developing solution may contain a triazinylstilbene-based fluorescent whitening agent. Further, in the color developing solution, if necessary, ethylene glycol, methyl cellosolve, methanol, acetone, dimethylformamide,
β-cyclodextrin, and other Japanese Patent Publication No. 47-3337
No. 8, 44-9509.

Further, an auxiliary developer can be used together with the developing agent. These auxiliary developers include, for example, N-methyl-p-aminophenol hexalfate (methol), phenidone, N, N'-diethyl-p-
Aminophenol hydrochloride, N, N, N ', N'-tetramethyl-p-phenylenediamine hydrochloride and the like are known. Furthermore, various additives such as a stain inhibitor, an anti-sludge agent, and a layering effect promoter can be used. In addition, a color developing solution is disclosed in Japanese Patent Application No. 61-1986.
The chelating agents represented by the general formulas [I] to [XV] described in the above description may be added.

Each component of the color developing solution is prepared by adding
It can be adjusted by sequentially adding and stirring. In this case, the component having low solubility in water can be added by mixing with the above-mentioned organic solvent such as triethanolamine. More generally, a concentrated aqueous solution containing a plurality of components each of which can stably coexist, or a solution prepared in advance in a small container in a solid state is added to water, adjusted by stirring, and obtained as a color developing solution. it can. The color developing solution can be used in an arbitrary pH range. When the silver separation method of the present invention is applied in-line, the replenishment amounts of the black-and-white developer and the color developer are not limited, and are, for example, preferably 200 ml / m ² or less, more preferably 5 to 180 ml / m ² . is there.

The treatment method includes a single bath treatment and other various methods, for example, a spray method in which a treatment liquid is sprayed,
Alternatively, a wet method by contact with a carrier impregnated with a processing solution, a developing method using a viscous processing solution, or various processing methods such as slit development can also be used. In general,
After the color development processing, bleaching, fixing or single-bath bleach-fixing processing is performed. The photographic processing solutions used in these are described above.

After processing with the bleaching solution, fixing solution or bleach-fixing solution, washing and / or stabilizing treatment are performed. The stabilizing solution may contain, for example, a sulfite. The sulfite may be any organic or inorganic substance, as long as it releases sulfite ions, but is preferably an inorganic salt. Preferred specific compounds include sodium sulfite, potassium sulfite, ammonium sulfite, ammonium bisulfite,
Examples include potassium bisulfite, sodium bisulfite, sodium metabisulfite, potassium metabisulfite, ammonium metabisulfite and hydrosulfite.

A desirable compound to be added to the stabilizer is an ammonium compound. These are supplied by ammonium salts of various inorganic compounds,
Specifically, ammonium hydroxide, ammonium bromide, ammonium carbonate, ammonium chloride, ammonium hypophosphite, ammonium phosphate, ammonium phosphite,
Ammonium fluoride, ammonium acid fluoride, ammonium fluoroborate, ammonium arsenate, ammonium bicarbonate, ammonium bifluoride, ammonium bisulfate, ammonium sulfate, ammonium iodide, ammonium nitrate, ammonium pentaborate, ammonium acetate, ammonium adipate, Ammonium laurate tricarboxylate, ammonium benzoate, ammonium carbamate, ammonium citrate, ammonium diethyldithiocarbamate, ammonium formate, ammonium hydrogen malate, ammonium hydrogen oxalate, ammonium phthalate, ammonium hydrogen tartrate, ammonium thiosulfate, ammonium sulfite, ethylenediamine Ammonium tetraacetate, ferric ammonium ethylenediaminetetraacetate, Moniumu, ammonium malic acid,
Ammonium maleate, ammonium oxalate, ammonium phthalate, ammonium picrate, ammonium pyrrolidine dithiocarbamate, ammonium salicylate, ammonium succinate, ammonium sulfanilate, ammonium tartrate, ammonium thioglycolate, 2,4,6-trinitrophenol ammonium And so on. These may be used alone or in combination of two or more.

The stabilizer may contain a chelating agent having a chelate stability constant for iron ions of 8 or more. Here, the chelate stability constant is defined as L.C. G. FIG. Sillen
A. E. FIG. Martell, "Stability C
instants of Me-tal-ion Co
plexes ", The Chemical Soc
iety, London (1964). S. Chabe
rek · A. E. FIG. Martell, "Organic
Sequestering Agents ”, Wil
ey (1959) means a constant generally known.

The chelate stability constant for iron ions is 8
Examples of the chelating agent include an organic carboxylic acid chelating agent, an organic phosphoric acid chelating agent, an inorganic phosphoric acid chelating agent,
And polyhydroxy compounds. In addition, the said iron ion means ferric ion (Fe3 ⁺ ).

The chelate stability constant with ferric ion is 8
Specific examples of the chelating agent described above include the following compounds, but are not limited thereto. That is, ethylenediamine diorthohydroxyphenylacetic acid, diaminopropanetetraacetic acid, nitrilotriacetic acid, hydroxyethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, Diaminopropanoltetraacetic acid, transcyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, ethylenediaminetetrakismethylenephosphonic acid, nitrilotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1-
Diphosphonic acid, 1,1-diphosphonoethane-2-carboxylic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxy-1-phosphonopropane-1,2,2
Examples thereof include 3-tricarboxylic acid, catechol-3,5-diphosphonic acid, sodium pyrophosphate, sodium tetrapolyphosphate, and sodium hexametaphosphate, and particularly preferably, diethylenetriaminepentaacetic acid, nitrilotriacetic acid,
Examples thereof include nitrilotrimethylenephosphonic acid and 1-hydroxyethylidene-1,1-diphosphonic acid, among which 1-hydroxyethylidene-1,1-diphosphonic acid is most preferably used.

Other compounds that can be added to generally known stabilizers include polyvinylpyrrolidone (PVP).
K-15, K-30, K-90), organic acid salts (citric acid, acetic acid, succinic acid, oxalic acid, benzoic acid, etc.), pH adjusters (phosphate, borate, hydrochloric acid, sulfuric acid, etc.) Antifungal agents (isothiazolines, phenol derivatives, catechol derivatives, imidazole derivatives, triazole derivatives, thiabendazole derivatives, organic halogen compounds, triazine derivatives, and other fungicide agents known as slime control agents in the paper-pulp industry, etc. ) Or optical brightener, surfactant, preservative, Bi, Mg, Zn, Ni, A
There are metal salts such as 1, Sn, Ti, Zr, etc. These compounds are necessary for maintaining the pH of the stabilizing bath and do not adversely affect the stability during storage of color photographic images and the occurrence of precipitation. To the extent, any compound may be used in any combination.

Various additives, for example, aldehyde compounds and derivatives thereof are used in the stabilizing solution. The case where formalin in the stabilizing solution is substantially zero may be used. Hexamethylenetetramine and its derivatives, methylolurea compounds, and triazine compounds may be used instead of formalin.

After the stabilization treatment, no water washing treatment is required, but rinsing, surface washing and the like by small amount of water washing within an extremely short time can be arbitrarily performed as necessary. It is preferable that a soluble iron salt is present in the stabilizing solution. Examples of the soluble iron salt include ferric chloride, ferrous chloride, ferric phosphate, ferric bromide, ferric nitrate, and ferrous nitrate. Isoinorganic iron salt and ferric ethylenediaminetetraacetic acid salt, 1-hydroxyethylidene-
Ferric 1,1-diphosphonate, ferrous 1-hydroxyethylidene-1,1-diphosphonate, ferrous ethylenediaminetetraacetate, ferric diethylenetriaminepentaacetate, ferrous diethylenetriaminepentaacetate, ferric citrate Organic acids such as ferrous iron, ferrous citrate, ferric ethylenediaminetetramethylenephosphonate, ferrous ethylenediaminetetramethylenephosphonate, ferric nitrilotrimethylenephosphonate, ferric nitrilotriacetic acid, and ferrous nitrilotriacetic acid Iron salts. These organic acid iron salts can be used in the form of a free acid type, such as sodium salt, potassium salt, ammonium salt, lithium salt, alkylammonium salt (triethanolammonium salt, trimethylammonium salt,
Tetramethylammonium salt).

It is also possible to use a stabilizer which has been treated with an ion-exchange resin to reduce calcium ions and magnesium ions to 5 ppm or less, or by using a method in which the above-mentioned antibacterial agent and halogen ion releasing compound are added. Is also good. The pH of the stabilizer is not critical.

The above-mentioned color developing solution, bleach-fixing solution, stabilizing solution, or a processing solution such as a bleaching solution, a fixing solution, a rinsing solution, and other black-and-white developing solutions may contain a water-soluble surfactant. The compounds listed in the above publication may be used.

The photographic processing solution or waste liquid to which the present invention is applied is a processing solution that has processed or processed an exposed photographic material, or a processed waste liquid. All silver halide photographic light-sensitive materials, whether for black-and-white, X-ray or the like, are included. That is, the photosensitive material may be a photosensitive material processed by a so-called internal development method containing a coupler in the photosensitive material, or may be a photosensitive material processed by a so-called external development method,
For example, any photosensitive material such as a color paper, a color negative film, a color positive film, a color reversal film for a slide, a color reversal film for a movie, a color reversal film for a TV, a reversal color paper, a black-and-white photographic light-sensitive material, an X-ray light-sensitive material, etc. was processed. The present invention can be applied to a photographic processing solution or a waste solution. Furthermore, any silver-containing solution discharged from a plating process or any other silver-related factory or any other silver-containing solution can be applied without any particular limitation.

[0079]

According to the present invention, silver can be efficiently separated from a silver complex ion solution having a ligand containing a sulfur atom.

[0080]

The present invention will be further described below with reference to examples. Example 1 Silver ion adsorption from silver thiosulfate solution 0.125 g of each of dried resins P-5 and P-3 was added to 50 cm ^{3 of} silver thiosulfate solution having the following concentrations, followed by stirring at 30 ° C. for 24 hours. . Thereafter, the resin and the aqueous solution were separated, and the concentration of the remaining silver ions in the aqueous solution was measured and determined using a high frequency inductively coupled plasma emission spectrometer (ICPS-5000, manufactured by Shimadzu Corporation). The amount of silver ions adsorbed per gram of the resin was determined by the following equation.

[0081]

(Equation 1) B: Silver ion concentration of blank (ppm) S: Silver ion concentration of sample (ppm) W: Weight of resin (g)

[0082]

[Table 1] From this result, it can be seen that silver can be separated very efficiently.

Example 2 Silver ion adsorption from a silver thiosulfate solution containing ammonium EDTA iron ammonium 0, 3.5, 7.0, and 14.0 wt% of a 0.006 mol / l silver thiosulfate solution
A solution was prepared by adding 0.125 g of the dried resin P-5 and P-3 in 50 cm ^{3 of} the solution and added at 30 ° C.
The mixture was left to stir for 4 hours. Thereafter, the resin and the aqueous solution were separated, and the amount of adsorbed silver ions was measured and calculated in the same manner as in Example 1.

[0084]

[Table 2] This result indicates that silver can be adsorbed efficiently even in the presence of ammonium EDTA iron.

Claims (4)

[Claims] 1. A method for separating silver, comprising separating silver from a silver-containing solution containing a silver complex ion having a ligand containing a sulfur atom using a resin composition comprising a resin having a mercapto group. . 2. The method according to claim 1, wherein said silver-containing solution is a photographic processing solution or a photographic processing waste liquid. 3. The method for separating silver according to claim 1, wherein the resin is synthesized from a polymer or copolymer of a monomer having a thiirane ring. 4. The method for separating silver according to claim 1, wherein the resin is one of the following resins A to D. Resin A embedded image [In the formula, R ₁ represents hydrogen, a lower alkyl group, a halogen or a monohalomethyl group. ] A resin having a mercapto group obtained by reacting a polymer and a copolymer of the monomer represented by the formula (1) or a copolymer with another vinyl monomer copolymerizable with the monomer with an alkali hydrosulfide. Resin B The copolymer of the general formula (I) is represented by the general formula A ₁ NH ₂ wherein A ₁ represents a hydrogen atom, an alkyl group or an aminoalkyl group. A resin having a mercapto group obtained by reacting with an amine represented by the formula: Resin C A resin having a structural unit represented by the following general formula (II). Embedded image [Wherein, R ₂ represents hydrogen, a lower alkyl group, a halogen or a monohalomethyl group. Resin D A resin having a structural unit represented by the following general formula (III). Embedded image [Wherein, R ₃ represents hydrogen, a lower alkyl group, a halogen or a monohalomethyl group, and A ₂ represents a hydrogen atom, an alkyl group, or an aminoalkyl group. ]