JPH06123942A - Silver capturing method from photographic processing solution containing silver - Google Patents

Abstract

PURPOSE:To reduce silver content in the waste solution and to easily capture silver from the waste solution of fixing solution, rinsing solution and washing, solution by carrying a thion and/or thiolate compound and bridging it into contact with a silver-containing photographic processing solution. CONSTITUTION:In a method for capturing silver from the silver-containing photographic processing solution, the thion and/or thiolate compound is carried on a carrier and is brought into contact with the silver-containing photographic processing solution. In this case, an overflow solution 56 from a fixing vessel N3 is introduced into a column filled with the carrier for carrying the compound having a functional group selectively adsorbing silver, silver is captured by passing the solution through the column and a purified water C1' passed through the column low in silver content is discharged to a sewerage. Also a waste solution 57 from a washing vessel W21 is introduced into a reverse osmosis membrane (RO), is separated into a purified water C1 and a silver-containing solution R1, the purified water C1 is replenished to the washing vessel 22 as a washing water, the silver-containingsolution R1 is introduced into the column and silver is captured by passing through the column.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for collecting silver from a silver-containing photographic processing waste liquid generated in the photographic processing of a silver halide photographic light-sensitive material (hereinafter referred to as "light-sensitive material"). In particular,
INDUSTRIAL APPLICABILITY The present invention collects silver from silver-containing photographic waste liquid after fixing processing of color light-sensitive materials and black-and-white light-sensitive materials, and can be reused or discarded as a waste liquid having a very low silver content below the silver emission standard. The present invention relates to a method of processing silver-containing photographic waste liquid.

[0002]

2. Description of the Related Art Generally, a black-and-white light-sensitive material is processed in a process such as black-and-white development, fixing and washing after exposure, and a color light-sensitive material is processed in a process such as color development, desilvering, washing and stabilization after exposure. It is processed. In the processing of black and white photosensitive materials, a black and white developing solution is used for black and white development, and a fixing solution is used for fixing. In the processing of color photosensitive materials, a color developing solution and a desilvering processing are used for color development. Is a bleaching solution, a fixing solution, or a bleach-fixing solution, tap water or ion-exchanged water is used for washing, and a stabilizing solution is used for stabilizing treatment. In any case, after fixing, rinsing with a small amount of water and then washing with water are performed, and stabilization is often omitted.

The temperature of each processing solution is usually adjusted to 20 to 50 ° C., and the light-sensitive material is immersed in these processing solutions for processing. Among these, the fixing process is a process of fixing the silver image by dissolving and removing the remaining silver halide with a suitable silver halide solvent in the process of the black and white photosensitive material,
In the processing of color light-sensitive materials, the reduced silver developed by the bleaching process is oxidatively bleached and rehalogenated with coexisting halogen. Next, the undeveloped silver halide and the rehalogenated silver in the developing section form a complex of silver thiosulfate to be solubilized by the fixing process, and are eluted from the emulsion film into the processing solution. Next, the developer, the bleaching agent, and the fixing agent contained in the emulsion film are washed out by rinsing and washing treatment (including stabilization treatment), and as a result, the image stability can be maintained.

Therefore, the waste liquid of the fixing solution, the rinsing solution and the washing water (including the stabilizing solution) is washed out with silver components such as silver complex salts carried on the light-sensitive material and is present in a considerable concentration. Therefore, due to the pollution of rivers and the like, it was not possible to directly discharge the wastewater into the sewer, and it was necessary to collect these waste liquids. The fee for collecting this waste liquid is high, and it is 10 to 100 yen per liter. Especially in a large laboratory, the amount of washing water required is 5,000 to 50,000 liters per day, and the cost required for recovery is enormous.

As a known method for removing silver from a waste liquid, a silver removal method by adsorption includes metal ion separation using a polymer complex [Chemical Engineering 47, 218 (1983)], and an advanced separation technology using an ion exchange membrane [excellent reading company] , P. 47 (198
9)], a method using a functional separation adsorbent in DIRASS REPORT [Diamond Research, page 17 (198)
9)], and those described in JP-A-3-132656. In the reverse osmosis method (RO), JP-A-50-3 is used.
0360, 50-502463, 50-21564,
Ibid 49-103461, ibid 58-105150, ibid 62
-254151, 63-212935, JP-A-2-2
9740, 3-46652, 3-55542, 3
-126030, the chemical precipitation method includes those described in Kodak Leaflet J-10, page 13, and the electrolysis method, J. P.
S. 20, 13, J. P. S. 23, 216, J. P.
S. 29, 16, J. A. P. E. 5, 141, J.
A. P. E. No. 8,171, which is known in electrodialysis (ED) for concentration of salt, etc.
Examples thereof include those described in JP-A-3-273237. In addition, in-line electrolysis (Ag <0.1 g / of metal replacement method, evaporation method, introduction of economy rinse, Fix (fixing), BF (bleach-fixing). L) etc.

By the way, in recent years, from the viewpoint of environmental protection, regulations on the emission standard of silver that can be discharged into the sewer have become stricter year by year. For example, "Information Ecol
ogy and Safety "Regulations Affecting the Discharg
e of Photographic Processing Solutions, Kodak Publ
ication No. J-102 (1990, September), T
The value of “0.001 to 20 ppm” is set in able1 as the standard for silver emission in the typical urban sewerage law.
The standard value of silver in photo laboratories is "0.5-
The value of "5 ppm" is posted.

[0007] In addition, the US law "Safe"
Drinking Water Act], "Hazardous Materials Transp
Ortation Act], “Toxic Substances Control Act”, etc., also show the regulated value of silver. In addition, regarding sewerage, the CWA (Clean Wa
ter Act) With the enforcement of the revised law, it is becoming severe in many areas.

[0008]

[Problems to be Solved by the Invention]
The need to collect waste liquids such as fixer liquid, rinse liquid, and washing water (including stabilizing liquid) has increased, and the recovery cost has been increasing. From another point of view, it is desirable to collect silver from these waste liquids because silver is an expensive metal and also from the viewpoint of resources.

As an effective method for reducing the content of silver from the waste liquid, for example, dithiocarbamic acid-based Q-10
It has been proposed to use chelating resins such as R (manufactured by Sumitomo Chemical Co., Ltd., trade name) and polyamine UR-3900 (Unitika Co., Ltd., trade name), but as shown in Examples below. In addition, these methods are effective for, for example, silver nitrate solutions, but have little effect on silver-containing photographic processed solutions such as fixing solutions, washing water, and rinsing solutions. There is a demand for a means capable of effectively collecting silver from the used solution to contribute to the recovery of silver, and discharging the waste solution into the sewage as a waste solution having a silver content not more than the above-mentioned regulated value.

Therefore, an object of the present invention is to effectively capture silver from a waste liquid of a fixing solution, a rinsing liquid, and a washing water by a simple means, to significantly reduce the content of silver, and to drain the waste liquid to a sewer or the like. Another object of the present invention is to provide a method for collecting silver from a silver-containing photographic waste liquid which can be reused as washing water or fixing solution water and can recover silver.

[0011]

Means for Solving the Problems The present invention described above has the following (1).
It is achieved by the invention of (8). (1) A method of collecting silver from a silver-containing photographic processed liquid, characterized in that a thione and / or thiolate compound is supported on a carrier, and the silver-containing photographic processed liquid is brought into contact with the carrier. A method of collecting silver from silver photographic processed liquid. (2) The method for collecting silver from a silver-containing photographic processed solution according to claim 1, wherein the thione and / or thiolate compound is represented by the following general formula (I), (II) or (III). .

[0012]

[Chemical 2]

(Wherein R is an alkyl group, an alkenyl group,
Represents an aralkyl group or an aryl group. Q represents an atomic group necessary for forming a 5- or 6-membered heterocycle. M represents a cation group. X and Y are an alkyl group, an alkenyl group, an aralkyl group, an aryl group, a heterocyclic group, -N (R ₁ ) R
_{2, -N (R 3) N} (R 4) R 5, -OR 6 or -SR
Represents ₇ . R ₁ , R ₂ , R ₃ , R ₄ and R ₅ represent a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, an aryl group or a heterocyclic group, R ₆ and R ₇ represent a hydrogen atom,
It represents a cation group, an alkyl group, an alkenyl group, an aralkyl group, an aryl group or a heterocyclic group. (3) The carrier according to (1) above, wherein the carrier carrying the thione and / or thiolate compound is liquid-permeable and is filled with a reaction part having a liquid-permeable carrier-holding mechanism. Method for collecting silver in silver photographic processed liquid. (4) The silver collection method for a silver-containing photographic processed solution according to (1), wherein the solution after silver collection is reused as a photographic processing solution. (5) In a developing device for a silver halide photographic light-sensitive material having a rinse tank provided between a fixing tank and a water washing tank, a means for separating waste water of the water washing tank into clean water and silver-containing solution through a reverse osmosis membrane,
A mechanism for returning the clean water to the washing tank again, and the silver-containing solution described in (3) above.
And a mechanism for permeating silver into the reaction section having the liquid-permeable carrier holding mechanism described in 1 to collect silver. (6) In a silver halide photographic light-sensitive material processing apparatus having at least a fixing capacity tank, the waste liquid of the fixing capacity tank is passed through the reaction section having the liquid permeable carrier holding mechanism described in (3) above to obtain silver. Development apparatus for silver halide photographic light-sensitive material having a mechanism for collecting light. (7) In the development processing apparatus for a silver halide photographic light-sensitive material, wherein a rinse tank is provided between the fixing ability tank and the water washing tank, the waste liquid in the rinse tank is provided with the liquid-permeable carrier holding mechanism described in (3) above. An apparatus for developing and processing a silver halide photographic light-sensitive material having a mechanism for collecting silver by transmitting it to a reaction section of the apparatus. (8) In a developing device for a silver halide photographic light-sensitive material comprising at least a fixing ability tank and a washing tank or a fixing ability tank and a multi-stage rinsing tank, the waste liquid of the washing tank or the rinsing tank is passed through a reverse osmosis membrane to contain clean water. A development processing apparatus for a silver halide photographic light-sensitive material having a waste liquid processing mechanism for dividing clean water into permeation of clean water into a reaction section having a liquid-permeable carrier holding mechanism described in (3) above. (9) A method for collecting silver in a silver-containing photographic processed liquid, wherein the reaction part having the liquid-permeable carrier-holding mechanism according to (3) is a column or a filter bag. (10) The method for collecting silver of a silver-containing photographic processed liquid according to (1), wherein the liquid after silver collection is discarded in sewage. (11) The silver-containing photographic processed liquid from the rinse after fixing is passed through the column to collect silver with the porous carrier,
The method for collecting a silver-containing photographic processed liquid according to (1) above, wherein the waste liquid that has passed through the column is returned to the fixing capacity tank to reduce the replenishment amount to the fixing capacity tank by 1.

[0014]

[Operation] That is, according to the present invention, a compound having a functional group that selectively adsorbs silver is supported on a carrier, and silver is collected by contacting it with a silver-containing photographic processed liquid. is there.
The photographic-processed waste liquid treated in this way can be used again as a replenisher for the processing, and further, the silver can be recovered until the silver concentration is such that it can be discarded directly into the sewage. In the recovery method, as described above, silver can be effectively collected only by the solution containing silver, but the silver-containing processed solution used for photographic processing (all compounds from the light-sensitive material can be eluted into the processing solution). Although the composition is a complex liquid), it is probably because of a complicated existence state mainly composed of silver thiosulfate, and sufficient silver cannot be collected.

Therefore, there has been no processing method that satisfies the silver emission standard such that the amount of silver is, for example, 0.1 ppm or less. On the other hand, according to the configuration of the present invention,
The chelate resin can sufficiently collect silver in a complicated form mainly composed of silver thiosulfate, which is hard to be recovered, and thus can meet the emission standard of silver. Further, the solution after silver collection can be used as a processing solution and replenished with washing water or a fixing solution.

The present invention is capable of recovering silver in a silver-containing solution, but the present invention is particularly effective for recovering silver from a silver-containing photographic processed solution. The photographic processing liquid containing the fixing agent after processing the light-sensitive material has a remarkable effect as compared with the conventional one. The fixing agent that can be used at this time is, for example, preferably a thiosulfate, a thioether, a mercapto compound, a mesoionic compound, or a thiourea compound, and more preferably a thiosulfate-containing fixing agent. Solution, rinse solution after fixing, washing solution after fixing, or silver-containing processed solution from each processing tank. Specific examples of the mesoionic compound are described in JP-A-4-243252.

In the present invention, the silver-containing photographic processed liquid means
This is a liquid obtained by processing a light-sensitive material and is not a newly prepared liquid unused liquid, but is, for example, an overflow liquid from a processing tank.

In the present invention, the thione and / or thiolate compound is a compound having a functional group capable of selectively adsorbing to silver, the compound is carried on a liquid-permeable carrier, and the carrier has a carrier holding mechanism. It is housed in a reaction part, such as a column or a film bag. Silver is collected by passing a photographic processed liquid containing silver through a column or the like in which this carrier is accommodated. Here, selective adsorption with silver means that the thione and / or thiolate compound adsorbs at least silver.

By passing through the reverse osmosis membrane before passing the silver-containing treated liquid through a column or the like, silver can be efficiently collected. In addition, when dealing with areas with strict silver regulations, use a column and multiple reverse osmosis membranes, repeatedly permeate the liquid, or change the order of arrangement, etc. The silver concentration in it can be adjusted appropriately. The solution having a low silver concentration after collecting silver can be directly thrown into sewage or used again as washing water. Further, the solution having a high silver concentration after collecting silver also contains thiosulfate ions together with silver, and can be reused in a fixing capacity tank or a rinse solution after the fixing capacity tank. Here, the fixing ability tank means a processing tank capable of fixing, and examples thereof include a fixing tank and a bleach-fixing tank.

In the present invention, both the water washing and the rinsing liquid have the same function by washing the treatment liquid, but the replenishment amount and the treatment time are different. The washing (W) and the replenishment amount (R) of the rinse are W> R, preferably W is 1.5 times or more, more preferably 2 times or more of R, and specifically, washing water (W) is 400 ml / m ² to 2 liters / m ² , more preferably 500 ml / m ² to 1 liter / m ² , and rinse (R) is 200 ml / m ² or less, more preferably 100 ml / m ² or less. .

[0021] Also, each treatment of washing (W) and rinsing (R)
The time is W> R, preferably 1.5 times or more, more
It is preferably twice or more. Also, in the photo processor
The washing tank is preferably 2-3, and the rinse tank is 1-2.
Is preferred.

Further, the present invention will be described in detail. As the thione and thiolate compounds used in the present invention, various compounds such as thiourea compounds, thiourethane compounds, thioamide compounds, thiocarbonyl compounds, alkylmercapto compounds, arylmercapto compounds, heterocyclic mercapto compounds and dithiocarbamic acid compounds can be used. ,
Preferably, the above general formula (I), (II) or (II
I) can be mentioned.

In the formula, R represents an alkyl group, an alkenyl group, an aralkyl group or an aryl group. Q represents an atomic group necessary for forming a 5- or 6-membered heterocycle. M represents a cationic group. X and Y are alkyl group, alkenyl group, aralkyl group, aryl group, heterocyclic group, -N (R
_{1) R 2, -N (R} 3) N (R 4) R 5, represent -OR ₆ or -SR _7. R ₁ , R ₂ , R ₃ , R ₄ and R ₅
Represents a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, an aryl group or a heterocyclic group, and R ₄ and R ₇ represent a hydrogen atom, a cation group, an alkyl group, an alkenyl group, an aralkyl group, an aryl group or a heterocyclic group. Represent.

The general formula (I), (II) or (II
I) will be described in detail. Examples of the alkyl group, alkenyl group, aralkyl group and aryl group represented by R are as follows. That is, a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms (eg, methyl group, ethyl group, propyl group, hexyl group, isopropyl group, decyl group, dodecyl group, aminoethyl group, octadecyl group), substituted or unsubstituted Substituted alkenyl group having 2 to 40 carbon atoms (for example, vinyl group, propenyl group, 1-
Methyl vinyl group), substituted or unsubstituted carbon number 7 to 4
0 aralkyl group (eg, benzyl group, phenethyl group, 3-carboxyphenylmethyl group, 4-butylphenylethyl group), substituted or unsubstituted carbon number 6 to 40
Aryl groups (eg, phenyl group, naphthyl group, 4-
A methylphenyl group).

Q is preferably at least one of carbon atom, nitrogen atom, oxygen atom, sulfur atom and selenium atom,
It represents a group of atoms necessary for forming a 5- or 6-membered heterocyclic ring composed of atoms. The heterocycle may be fused with a carbon aromatic ring or a heteroaromatic ring. Examples of the heterocycle include tetrazole, triazole, imidazole, thiadiazole, oxadiazole, selenadiazole, oxazole, thiazole, benzoxazole, benzthiazole, benzimidazole, pyrimidine, triazain. Examples thereof include dens, tetraazaindenes, pentaazaindenes and the like.

M is a cation group (for example, an alkali metal atom such as hydrogen atom, sodium atom, potassium atom,
And an alkaline earth metal atom such as a magnesium atom and a calcium atom, an ammonium group, and an ammonium group such as a triethylammonium group). X, Y, R ₁ ,
The alkyl group, alkenyl group, aralkyl group and aryl group represented by R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ have the same meanings as R above.

X, Y, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ ,
The heterocyclic group represented by R ₆ and R ₇ is, for example, a substituted or unsubstituted heterocyclic group having 1 to 40 carbon atoms (for example, pyridyl group, furyl group, thienyl group, imidazolyl group, pyrrolyl group, pyrazolyl group, pyrimidinyl group). , A quinolyl group, a piperidyl group, and a pyrrolidyl group are preferable.

In the general formula (I), the cation groups represented by R ₆ and R ₇ represent alkali metal and ammonium. X and Y may form a ring but do not enolize.
Examples of the ring formed by X and Y include imidazoline-
2-thione ring, imidazolidine-2-thione ring, thiazoline-2-thione ring, thiazolidine-2-thione ring, oxazoline-2-thione ring, oxazolidine-2-thione ring, pyrrolidine-2-thione ring, or each The benzo-condensed ring of the above is mentioned.

Here, R, Q, X, Y, R ₁ , R ₂ ,
R ₃ , R ₄ , R ₅ , R ₆ and R ₇ may be substituted. The following are mentioned as a substituent. Representative substituents include, for example, alkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, aryl groups, alkoxy groups, aryloxy groups, acylamino groups, ureido groups,
Urethane group, sulfonylamino group, sulfamoyl group,
Carbamoyl group, sulfonyl group, sulfinyl group, alkyloxycarbonyl group, aryloxycarbonyl group, acyl group, acyloxy group, alkylthio group, arylthio group, halogen atom, cyano group, nitro group, mercapto group, amino group, hydroxy group, carvone group. Acid, sulfonic acid, etc. are mentioned. These groups may be further substituted. When there are two or more substituents, they may be the same or different.

General formulas (I), (II) and (III)
Among them, preferably R represents an alkyl group having 6 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. Q represents tetrazole, triazole, imidazole, thiadiazole, oxadiazole, tetraazaindene, triazine.

X and Y are alkyl having 1 to 20 carbons.
Group, heterocyclic group having 1 to 20 carbon atoms, -0 to 20 carbon atoms
N (R₁) R₂, C-C20 -N (R₃) N (R
_Four) R _Five, SR having 0 to 20 carbon atoms₇Represents R₁,
R₂, R₃, R_Four, R_FiveAnd R₇Is a hydrogen atom, alkyl
Represents a group or an aryl group. R₇Is a cationic group
May be.

Of the formulas (I), (II) and (III), the formula (II) is more preferable. The compounds of the general formulas (I), (II) and (III) of the present invention are easily available as commercial products and can be easily synthesized by various methods. Specific examples of the thione and thiolate compounds of the present invention are shown below, but the present invention is not limited thereto.

[0033]

[Chemical 3]

[0034]

[Chemical 4]

[0035]

[Chemical 5]

[0036]

[Chemical 6]

[0037]

[Chemical 7]

[0038]

[Chemical 8]

In the present invention, the carrier is any substance which is a porous substance or a fibrous material, which can support the scavenger and which allows the liquid to be treated to pass through the carrier (liquid permeability). Can also be used. Therefore, it may be either an inorganic substance or an organic substance (natural or synthetic). Examples of the porous carrier include a) sponge-like one, b) porous resin, and c) porous ceramic.

A) The sponge may be made of any material, but urethane, polyester, polyamide, polyethylene, melamine, vinyl chloride, polypropylene are preferred, and among them, urethane, polyethylene, cellulose, cellulose ester, modified polysaccharide, polyvinyl alcohol, modified polyvinyl alcohol. , Plastic foam and the like are preferable.

As the plastic foam, polyurethane foam, polystyrene foam, ABS foam, vinyl chloride resin foam, polyethylene foam,
Examples include polypropylene foam, phenol resin foam, urea resin foam, etc. [Synthetic polymer (Shunsuke Murahashi et al .; published by Asakura Shoten, reprinted at 50.3.30, Showa) No. 3
55 to 359].

The density of the sponge is 10 kg / m ^{3 to} 300
Preferably ^{Kg / m 3, 15Kg / m} 3 ~100Kg /
m ³ is more preferable. These sponges are commercially available as industrial foams and are available, for example, from Inoac Corporation. b) The porous resin is called a giant network resin,
Made from polystyrene, polyester, polyamide, etc. The pore size is distributed from 0.001 μm to 0.5 μm.

Amber light XAD is a typical example.
(Rohm and Haas Company) available from Organo Corporation. c) Various porous ceramics announced by Kyocera Corporation can be used as the porous ceramics. The compound may be alumina, zircon, cordierite, silicon carbide or the like, and may have a porous filter-like shape, a honeycomb structure or a pleated structure.

Other porous materials include Engineering Materials Handbook (author Saichi Hatano 1982. Nikkan Kogyo Shinkaisha) No. 322.
Those described on the page and synthetic zeolites such as Munters Zeol manufactured by Tosoh Zeol Co., Ltd. can also be used. The fibrous material has various forms such as a thread form, a cloth form, a cotton form, a mat form and the like depending on the processing situation, but any liquid permeable material may be used. Made from natural fibers, synthetic fibers such as polypropylene and polyester, cellulose fibers,
Vinyl chloride polymer fibers, vinylon fibers, saran fibers, polyester fibers and the like are preferable.

A typical material is Mitsubishi Diamond Marssorb, which is available from Mitsubishi Rayon Engineering Co., Ltd. What is preferably used as the carrier of the present invention is a) or b) in which the liquid can pass through the carrier. Further, a) is more preferable as the method of supporting the carrier because hydrophobic bond is preferable.

The supporting method of the present invention is such that the replenisher does not flow out even if the compound having a functional group that causes selective adsorption with silver (the scavenger) and the carrier are treated with the liquid to be treated. Need to be supported by. Therefore, 1)
Adsorption by hydrophobic interaction, 2) Adsorption by ionic interaction, 3) Adsorption by polar interaction (for example, hydrogen bond), and in some cases, 4) Reactive groups are added to the scavenger and carrier, respectively. It may be carried by. However, 1) is most preferable in order to keep the cost low and to prevent the scavenger from eluting into the water phase when used in the water phase. Therefore, the scavenger used in 1) is preferably soluble in organic solvents, and among the organic solvents, aprotic solvents such as ethyl acetate, acetone, ether, carbon tetrachloride, etc., rather than protic solvents such as alcohols. A compound having extremely high solubility is more preferable.

The following method is convenient for supporting the scavenger on the carrier. That is, a solution of the scavenger in an organic solvent 0.01
The carrier is immersed and stirred in mmol / liter to 1 mmol / liter, preferably 0.1 mmol / liter to 100 mmol / liter. After 5 minutes or more, the carrier is taken out from the solution and dried. Usually, by this operation, 0.01 mmol or more of the scavenger is adsorbed per 1 g of the carrier, and the carrier becomes usable.

The liquid permeability does not mean that the water to be treated flows through the resin surface like a conventionally known chelate resin, and that the scavenger is sufficiently carried inside. In, it is important to have a function of distributing and transmitting not only the surface of this carrier but also the inside of the carrier. For this purpose, a carrier having the above-mentioned a), b), and c) in shape and properties is required, and a) is particularly effective.

From another point of view, the pore size is 0.1 μm or more, preferably 1 if defined roughly by the pore size in the carrier.
It is preferably μ or more, more preferably 5 μ or more.
Also, since there are honeycomb-shaped objects, the upper limit is 2 m.
It is considered to be m or less. As liquid permeability conditions, the fixing waste liquid, the rinse waste liquid, and the part-washing waste liquid have a surface tension of 6 or less.
Since it is 0 dyne / cm or less, this liquid needs to be able to pass through these pore sizes, and there are physicochemical restrictions, but pore sizes of approximately 1 μm to 2 mm can be used.

The liquid permeation conditions are preferably under normal pressure, but may be under increased pressure or reduced pressure if necessary, and it is considered that the required pore size will be mixed at this time.

The reverse osmosis membrane treatment which can be used in the present invention is described in JP-A-49-103461 and JP-A-50-103461.
-21564, 50-5022463, 50-3036.
0, 58-105150, 63-212935, 62-254151, JP-A-2-29740, 3-5.
5542, 3-46652, and 3-126030, and those described in the New Polymer Handbook, page 249, §4.9 reverse osmosis membrane and the like.

In the present invention, the reverse osmosis membrane used in the reverse osmosis device is, for example, a cellulose acetate membrane, an ethyl cellulose / polyacrylic acid membrane, a polyacrylonitrile membrane, or a polyvinylene carbonate membrane. As the structure of the reverse osmosis membrane, any of spiral type, tubular type, hollow fiber type, pleated type, and rod type can be used.

The film area (effective area) is 0.5 to 10
0 m ^2, preferably a 0.8~60m ^2. The washing water and the stabilizing solution used in the present invention are basically tap water or ion-exchanged water. Various compounds may be added to the washing water or the stabilizing solution. For example, a hardener represented by magnesium salt or aluminum salt, or a surfactant for preventing drying load and unevenness, a fluorescent whitening agent for improving whiteness, a sulfite salt as a preservative, etc. is there. Alternatively, L. E. West, “Water Quality Criteria
"Liter Criteria""Photographic Science and Engineering (Photo S)
ci. and Eng. ), Volume 9, No. 6 (196
You may add the compound as described in 5) etc.

In the present invention, the stabilizing liquid is a liquid having an image stabilizing function which cannot be obtained by washing with water. Therefore, in addition to the components added to the washing water, there are components that perform image stabilization. It has been added and is sometimes called a "stabilizing solution". Examples of these components include a liquid added with formalin, bismuth salt, aqueous ammonia, ammonium salt and the like. Furthermore, Japanese Patent Laid-Open No. 2-2
Various washing waters described in Japanese Patent No. 42249 can also be used.

P of the washing water or the stabilizing solution in the present invention
H is usually around 7, but it may become pH 3 to 9 by bringing it from the prebath. The temperature for washing or stabilizing is 5 ° C to 40 ° C, preferably 10 ° C to 35 ° C. If necessary, a heater, a temperature controller, a circulation pump, a filter, a float, a squeegee and the like may be provided in the washing tank or the stabilizing tank.

In the present invention, the rinse liquid used for pre-rinsing treatment is the same as the rinsing water. In the present invention, a fixing solution and a bleach-fixing solution are used for the processing having a fixing ability, which is carried out prior to the washing treatment or the stabilizing treatment. The fixing agent in the fixing solution or the bleach-fixing solution includes thiosulfate. Particularly, ammonium thiosulfate salt is preferable, and its addition amount is 0.1 to 5.0 mol / liter, preferably 0.5 to 2.0 mol / liter. As a preservative, sulfite is generally added, but ascorbic acid, a carbonyl bisulfite adduct, or a carbonyl compound may be added. Further, a buffering agent, a fluorescent whitening agent, a chelating agent, an antifungal agent and the like may be added as required.

The bleach-fixing solution contains an iron complex as a bleaching solution. Among the iron complexes, aminopolycarboxylic acid iron complexes are preferable, and the addition amount thereof is 0.01 to 1.0 mol /
It is 1 liter, preferably 0.05 to 0.50 mol / liter. Various compounds can be used as a bleaching accelerator in the bleach-fixing solution. For example, US Pat.
No. 893858, German Patent No. 1290812, JP-A No. 53-95630, Research Disclosure No. 17129 (July 1978), compounds having a mercapto group or a disulfide group, JP-A No. 50. -140129, the thiazoline derivative, U.S. Pat. No. 3,706,561, the thiourea derivative, JP-A-58-16235, the iodide, and German Patent 2,748,430, the polyethylene oxide. And polyamine compounds described in JP-B-45-8836 can be used.

Further, in a bath having a fixing ability such as bleach-fixing or fixing, if the replenishing amount of the bath is decreased, the silver concentration in the bath increases, and accordingly, a washing bath and / or a stabilizing bath. As the amount of silver brought into the system increases, the need for washing water and recovery of the stabilizing solution becomes great.
Therefore, it is preferable to apply the method of the present invention when the replenishing amount of the bath having fixing ability is small. In addition, JP-A-3
It is also preferable to combine with the method of treating while energizing, which is described in JP-A-273237.

The light-sensitive material used in the present invention is a usual black-and-white silver halide photographic light-sensitive material (for example, a black-and-white light-sensitive material for photographing, a black-and-white light-sensitive material for X-ray, a black-and-white light sensitive material for printing, etc.), a normal multi-layer color. Photosensitive materials (for example, color negative films, color reversal films, color positive films, color negative films for movies, etc.), infrared light sensitive materials for laser scanners and the like can be mentioned.

In the present invention, various treatment liquids are used in addition to the washing water and the stabilizing liquid described above, depending on the treatment step of the light-sensitive material. For details of these treatment liquids and treatment methods, reference can be made to the description in JP-A-3-46652 and the like. The details of the light-sensitive material are also disclosed in JP-A-3-
Reference can be made to the description of No. 46652 and the like.

[0061]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of the present invention will be described below with reference to the accompanying drawings. However, the present invention is not limited to this embodiment. FIG. 1 is a schematic diagram of a photographic processing apparatus according to an embodiment of the present invention. The photographic processor includes a developing tank N1 and a bleaching tank N.
2, a rinse tank NR1, a water washing tank W1, a fixing tank N3, a rinse tank NR2, water washing tanks W21 to W22, and a stabilizing tank N4. The photosensitive material S is conveyed in this order and is transferred to a drying section (not shown). Be dried. Further, the replenishing liquids 11 to 18 are replenished to these processing tanks, and the overflow liquid 19 from the water washing tank W22 has a multistage countercurrent flow to the water washing tank W21. Further, the overflows 51 to 58 are discharged from each processing tank except a part thereof.

The overflow liquid 56 from the fixing tank is introduced into a column filled with a carrier carrying a compound having a functional group capable of selectively adsorbing silver, and is passed through the column to collect silver. Then, the clean water C1 ′ having a low silver concentration that has passed through the column is discharged as it is to the sewage. The silver concentration of this clean water C1 'is 0.01 to 0.04 ppm
A value of (10 to 40 ppb) is shown and there is no problem even if it is discharged as it is.

The waste liquid b7 from the water washing tank W21 is guided to the reverse osmosis membrane (RO), and by the RO, clean water C1 and silver-containing liquid R1.
The clean water C1 is replenished to the washing tank 22 as washing water, and the silver-containing solution R1 is introduced into the column and permeated through the column to collect silver. As a result, the amount of waste liquid from the washing tank and the amount of waste liquid from the rinse tank can be reduced, and by supplementing the washing tank with clean water, the replenishment amount of the washing water can also be reduced. Furthermore, by allowing the silver-containing solution from the reverse osmosis membrane and the overflow solution from the rinse to permeate through the column of the present invention, the silver can be sufficiently collected, and there is no problem even if it is drained to the sewage.

FIG. 2 is a schematic diagram of a photographic processing apparatus according to an embodiment of the present invention, which is suitable for use in a minilab or the like. Development tank N
1, bleaching tank N2, fixing tank N3, washing tanks NS1 to NS2,
The stabilizing tank N4 is provided, and the photosensitive material is conveyed and processed in this order. Each processing tank is replenished with replenishers 21 to 25,
The overflow liquids 61 to 65 are discharged from each processing tank.

The overflow liquid 65 from the fixing tank N3 is passed through a column for collecting silver, and clean water C after collecting silver is obtained.
2'is added to the fixing tank N3. The clean water C2 'contains thiosulfate ions, and reuse as a fixing solution again can reduce the amount of replenishment to the fixing tank.

FIG. 3 is a schematic diagram of a photographic processing apparatus according to an embodiment of the present invention. The photographic processor includes a developing tank N1 and a bleaching tank N.
2, a rinse tank NR1, a water washing tank W1, a fixing tank N3, a rinse tank NR2, water washing tanks W21 to W22, and a stabilizing tank N4. The photosensitive material S is conveyed in this order and is transferred to a drying section (not shown). Be dried. Further, the replenishing liquids 41 to 48 are replenished to these treatment tanks, and the overflow liquid 49 from the water washing tank W22 has a multistage countercurrent flow to the water washing tank W21. Further, the overflows 81 to 87 are discharged from each processing tank except a part thereof.

The overflow solution from the fixing tank is introduced into RO and divided into silver-containing solution R3 and clean water C3.
3 is replenished in the rinse tank NR2, clean water C3 is introduced into the column of the present invention capable of collecting silver, and clean water C3 permeates the column to collect silver. Clean water C after collecting silver
3'has a remarkably low silver concentration and can be discharged as it is to sewage.

[0068]

【Example】

<Example 1> (Comparative experiment) A commercially available chelate resin was packed in a column having a radius of 20 mm to a height of 20 cm, and the following two silver-containing solutions (30 m) were used.
1) was distributed. The filtrate was analyzed for silver. (Silver-containing solution) (A) Silver nitrate solution of Ag 45 ppm (B) Water washing waste solution after fixing in photographic processing of Ag 45 ppm Sumitomo Chemical Q-10R Unitika uR-3900 (dithiocarbamic acid type) (polyamine type) (A): Ag 0.7 ppm Ag 0.2 ppm (b): Ag 11 ppm Ag 7.3 ppm As can be seen from these results, it is found that silver washing effluent, which is expected to mainly contain silver thiosulfate, cannot remove silver using a commercially available chelate resin. . (Invention) Polyurethane (manufactured by INOAC, trade name: flexible urethane foam SC, density: about 30 kg / m)
³ , cell number about 35 cells / 25mm, tensile strength 1.0kg /
A carrier was prepared by adsorbing Compound 14 in an open-cell sponge having a cm ² pore size of about 100 μm) in the following manner. That is, compound 14: 150 mg (0.6 mmo
l) was dissolved in 100 ml of ethyl acetate, 2.5 g of sponge was immersed in the solution and stirred, and the mixture was allowed to stand for about 10 minutes, then the sponge was taken out and air-dried. By this operation, about 40 mg (0.17 mmol) of Compound 14 was adsorbed on the sponge.

This sponge was pressed into a column having a radius of 20 mm to a height of 6 cm. To this, 30 ml of washing water after the fixing solution containing 45 ppm of (b) Ag, which was difficult to remove silver with a chelate resin, was passed through for about 5 minutes. When the Ag in the passage liquid was analyzed by atomic absorption, the concentration was 0.03 ppm. That is, a remarkable silver removing effect was recognized.

Example 2 The same experiment as in Example 1 was conducted using 150 mg of each of the following compounds in place of the compound of Example 1. However, when supporting each compound on the sponge, an organic solvent in which each compound was easily dissolved (shown in parentheses next to the compound number) was used. The results of measuring the Ag concentration of the passing liquid are shown below.

Organic solvent Ag concentration of passing liquid Compound 1 (methanol) 0.05 ppm 〃 3 (acetone) 0.05 〃 〃 4 (methanol) 0.06 〃 〃 6 (methanol) 0.06 〃 7 (acetone) ) 0.06 〃 〃 9 (methanol) 0.04 〃 〃 11 (acetone) 0.04 〃 〃 12 (acetone) 0.04 〃 〃 16 (methanol) 0.05 〃 〃 21 (acetone) 0.04 〃 〃 26 (acetone) 0.04 〃 〃 29 (methanol) 0.04 〃 〃 32 (acetone) 0.04 〃 〃 33 (acetone) 0.04 〃 〃 34 (methanol) 0.06 〃 38 (acetone) 0.06 〃 Good results were obtained as in Example 1.

<Example 3> [Sensitive material] SG400 is used as a main component and an existing sensitive material is used [Processing] The following processing method [Processing machine] FNcp-600II modified machine (Fig. 1) Processing method Processing time Processing Temperature Replenishment amount 135 Color development per 1m 3 minutes 30 seconds 38 ℃ 33ml Bleaching 6 minutes 05 seconds 38 ℃ 25ml ＊ Rinse (NR1) 1 minute 10 seconds 24 ℃ 15ml Washing (W 1) 2 minutes 20 seconds 24 ℃ 600ml constant Arrival 4 minutes 20 seconds 38 ℃ 31ml ＊ Rinse (NR2) 1 minute 05 seconds 24 ℃ 8ml Washing water (1) (W 21) 1 minute 05 seconds 24 ℃ ── ** ＊ Washing water (2) (W 22) 2 minutes 10 Second 24 ℃ 600ml ** Stability 1 minute 05 seconds 38 ℃ 31ml Dry 4 minutes 20 seconds 55 ℃ ＊ Use tap water for rinsing water and rinsing water ** Countercurrent water washing from (2) to (1) The composition of the treatment liquid will be described. (Color developer) Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.1 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 3.2 Sodium sulfite 4.0 4.4 Potassium carbonate 30.0 37.0 Potassium bromide 1.4 0.7 Potassium iodide 1.5 mg -Hydroxylamine sulfate 2.4 2.8 4- (N-ethyl-N-β-hydroxyethylamino) -2-methylaniline sulfate 4.5 5.5 Add water 1.0 liter 1.0 liter pH 10.05 10.10 (bleaching solution) Mother liquor, replenisher Common (unit: g) Ethylenediaminetetraacetic acid ferric sodium trihydrate 100.0 Ethylenediaminetetraacetic acid disodium salt 10.0 Ammonium bromide 140.0 Ammonium nitrate 30.0 Ammonia water (27%) 6.5 ml Water added 1.0 liter pH 6.0 (fixing solution) Mother liquor Common to replenisher (Unit: g) Ethylenediaminetetraacetic acid disodium salt 0.5 Sodium sulfite 7.0 Sodium bisulfite 5.0 Ammonium thiosulfate aqueous solution (70%) 170.0 ml Add water 1.0 liter pH 6.7 (Stabilizer) (Unit: g) Formalin (37%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (Average polymerization 10) 0.3 Ethylenediaminetetraacetic acid disodium salt 0.05 Add water 1.0 liter pH 5.0-8.0

(Treatment 3A) (Comparative Example) (1) In FIG. 1, a reverse osmosis membrane (RO) and CN-1 without a column were used.
We ran under 6 prefabricated conditions (200 lines / day for 1 month). In particular, there were no abnormalities in photographic characteristics within the management. But,
A total of 1.34 liters of waste liquid was discharged per 135 size m. The amount of silver in the total effluent was 130 ppm and could not be poured into the sewage in areas where silver was regulated. In addition, since COD addition is large, separate collection is necessary.

(2) When the N1 and N2, the NR1 and the N3 are recovered, the residual waste liquid is 1.23 liters, and the amount of silver in this is 1300 ppm. (3) When the N1 and N2, NR1 and N3, and NR2 were recovered, the residual waste liquid was 1.23 liters and the silver content was 2 ppm. Even if the policy of (3) is adopted, areas where silver regulations are strict (Ag
<0.1 ppm), sewage cannot be discharged. (Process 3B) (Invention) As shown in FIG. 1, reverse osmosis membrane (RO) [NTR-7 manufactured by Nitto Denko]
197 (polyamide-based composite membrane) is used, 30 kg / cm ²
Used under pressure. The permeated water amount is about 20 liters / minute] and the column [compound 14 of Example 1 supported on urethane, 20 liters column × 4 rows] is used for FNcp-600II.
I set it on a modified machine and ran in the same way, but the photographic performance was within the control. However, the water replenishment amount of W22 is 2
It was set to 00 ml. In this way, compared with Treatment 3A (2), the amount of waste liquid per 135 size m is 1.23 liters →
0.83 liters (33% decrease) and the amount of waste liquid decreases,
Moreover, the concentration of silver contained in this was 0.04 ppm.

Therefore, in the sewage regulation area where the COD regulation is loose and the silver regulation is strict, the sewage can be discharged as it is. (Treatment 3C) (Invention) In Treatment 3B, in a sewage regulation area where both COD and Ag are strict regulations, the liquid after column treatment contains almost no silver, but on the other hand, since the fixer component is contained, it remains as it is. It could not be flushed into the sewer. However, when a shortage of fixing agent and preservative was added to the solution after this treatment and it was used as a fixing replenisher, there was no problem (no desilvering failure occurred).
I was able to process it. By doing so, the amount of newly added fixing agent is reduced, so that the cost of chemicals can be reduced.

<Example 4> [Sensitive material] Example 5 of JP-A-2-250052
Same as. [Treatment liquid, process] Shown below. (Processing machine) FUJIFILM FP-230B modified product (Fig. 2: Minilab) Processing process Processing time Processing temperature Replenishment amount Tank capacity Color development 3 minutes 15 seconds 37.8 ℃ 15ml 10 liters Bleach 30 seconds 38.0 ℃ 5ml 5 liters fixed 1 minute 38.0 ℃ 15ml 10 liters Washed with water (1) 20 seconds 38.0 ℃ ― 5 liters Washed with water (2) 20 seconds 38.0 ℃ 20ml 5 liters Stabilized 20 seconds 38.0 ℃ 20ml 5 liters Dry 1 minute 55 ℃ Replenishment amount Is a countercurrent method of washing from (2) to (1) per 35 mm width 1 m.

The composition of the processing liquid is shown below. (Color developer) Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.1 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 3.2 Sodium sulfite 4.0 4.9 Potassium carbonate 30.0 30.0 Potassium bromide 1.4 ― Potassium iodide 1.5 mg -Hydroxylamine sulfate 2.4 3.6 4- (N-ethyl-N-β-hydroxyethylamino) -2-methylaniline sulfate 4.5 7.2 Water was added to 1.0 liter 1.0 liter pH 10.05 10.10 (bleaching solution) Mother liquor (g) Replenisher (g) 1,3-Diaminopropanetetraacetic acid Ferric ammonium-hydrate 144.0 206.0 1,3-Diaminopropanetetraacetic acid 2.8 4.0 Ammonium bromide 84.0 120.0 Ammonium nitrate 30.0 45.0 Ammonia water (27%) 10.0 1.8 Acetic acid ( 95%) 51.1 73.0 Add water 1.0 liter 1.0 liter pH 4.3 3.4 (fixer) common for mother liquor and replenisher (g) ethylenediaminetetraacetic acid dinatto Lithium salt 1.7 Sodium sulfite 14.0 Sodium bisulfite 10.0 Ammonium thiosulfate aqueous solution (70% weight / volume) 320.0 ml Water is added to 1.0 liter pH 7.2 (Washing liquid) Common for mother liquor and replenisher Tap water is H-type strongly acidic cation exchange resin ( Amberlite IR120B manufactured by Rohm and Haas Co., Ltd. and an OH type anion exchange resin (Amberlite IR-400) are passed through a hemp bed type column to treat the ion concentration of calcium and magnesium to 3 mg / liter or less, Then, 20 mg / liter of sodium isocyanurate dichloride and 1.5 g / liter of sodium sulfate were added. The pH of this liquid was in the range of 6.5 to 7.5. (Stabilizer) Both mother liquor and replenisher (g) Surfactant 0.5

[0078]

[Chemical 9]

[0079] Surfactant _{0.4 [C 10 H 21 -O- (} CH 2 H 2) - 10 H] Triethanolamine 2.0 1, 2-benz-isothiazolin-3-one 0.01 methanol 0.3 Formalin (37%) 1.5 Water In addition 1 liter pH 6.5

(Process 4A) (Comparative Example) (1) Processed without the column shown in FIG. 2 (2 at 200 lines / day)
However, the photographic performance was within the control range and there were no sensory defects. (2) When the replenishment of N3 was reduced to 6 ml, defective fixing occurred and the photographic property exceeded the control range. (Treatment 4B) (Invention) Under the conditions of (2), when a treatment was performed with a column as shown in FIG. 2, no fixing failure occurred, and the photographic property was within the control range.

<Example 5> [0085] Instead of the column of Example 3, a Muse bag filter (filtration grade 50 µ; diameter 178 mm; length 435 mm; filtration area 0.26 m ² ; manufactured by Nissho Co., Ltd .;
Polyester) was packed with about 1 liter of the compound of Example 1 supported on urethane foam,
Using this, these were fixedly installed in a circular shape, prepared in a turret shape that can be sequentially replaced, and used in place of the column in FIG.

After the filter 1 was treated with 50 liters of NR2 overflow, the turret was rotated and treated with filter 2. The column was sequentially rotated, and a new filter was replaced during the waiting time for processing. As a result, it was possible to discharge Ag into the sewage with Ag≈0.04 ppm as in the case of the 3B treatment in Example 3.

<Embodiment 6> A light-sensitive material, a treatment, a processing machine and the same as those in Embodiment 3 were used. However, the processor arrangement is different. (Process 6A) (Comparative Example) Process 3A (1) is exactly the same. (Treatment 6B) (Invention) Same as Treatment 3B, but in the order of installation As shown in FIG. 3, clean water (C) separated through RO is introduced into a column, and a silver-containing solution (R).
Was introduced into the rinse tank (NR2). By doing this, process 6
Compared to A, Treatment 6B has a replenishment amount of NR2 of 8 ml → 0 ml.
Could be reduced to Moreover, when the silver in the filtrate at the end of the column was examined, it could be discharged to the sewage at a level of 1 to 5 ppb at any place where the silver regulation was severe.

<Embodiment 7> A light-sensitive material, a treatment, a treatment machine and the same as those in Embodiment 3 were used. However, the processor arrangement is different. (Process 7A) (Comparative Example) The same as process 3A (1). (Treatment 7B) (Invention) Same as Treatment 3B, except that the silver-containing solution was not introduced into the rinse tank (NR2) as shown in FIG. Compared to Treatment 7A, the concentration of the NR2 recovered filtrate was reduced by about 70% because it was concentrated in the silver-containing solution (R) after RO. Moreover, R
Since the clean water (C) after O passed through the column, it was possible to discharge the sewage even in areas where the silver regulations were strict (Ag = 0.02).
ppm).

<Example 8> As a carrier carrying a scavenger, 1) open-cell polyethylene foam manufactured by INOAC CORPORATION, trade name RP30 # 1, density 25-40 Kg / m ² ,
Pore size approx. 300 μm), 2) synthetic fiber mat (manufactured by Mitsubishi Rayon Engineering Co., Ltd., trade name Diamals Sorb), 3) synthetic zeolite (manufactured by Tosoh Zeol Co., Ltd., trade name Muensters Zeol) 5 each
Compound 14 was loaded in the same manner as in Example 1 using each g. After filling a column with a radius of 20 mm to a height of 6 cm or less, (45) Ag45pp used in Example 1 was used.
After the fixing solution containing m, 30 ml of washing water was passed through for about 5 minutes. When Ag in the wash water that passed through was analyzed by atomic absorption, the concentrations were 1) 0.02 ppm and 2) 0.
It was 02 ppm, 3) 0.05 ppm.

[0086]

INDUSTRIAL APPLICABILITY The present invention effectively captures silver from a fixing solution, a rinsing solution, and a silver-containing photographic processed solution of washing water by a simple means, significantly reduces the silver content, and waste liquid is discharged to sewer or the like. It is possible to provide a method for collecting silver from a silver-containing photographic waste liquid, which can be drained to water or reused as washing water or water for a fixing solution and can recover silver.

[Brief description of drawings]

FIG. 1 is a schematic diagram of a photographic processing apparatus according to an embodiment of the present invention.

FIG. 2 is a schematic view of a photographic processing apparatus according to an embodiment of the present invention, which is suitable for use in a minilab or the like.

FIG. 3 is a schematic diagram of a photographic processing apparatus according to an embodiment of the present invention.

[Explanation of symbols]

 S Photosensitive material N1 Development tank N2 Bleaching tank N3 Fixing tank NR1, NR2 Rinsing tank W1, W21, W22 Washing tank N4 Stabilizing tank RO reverse osmosis membrane R1, R3 Silver-containing solution C1, C1 ', C2', C3, C3 ' Clean water

Claims (8)

[Claims] 1. A method for collecting silver from a silver-containing photographic processed liquid, comprising carrying a thione and / or thiolate compound on a carrier, and bringing the thione and / or thiolate compound into contact with the silver-containing photographic processed liquid. A method of collecting silver from a silver-containing photographic processed liquid. 2. The silver capture from the silver-containing photographic processed solution according to claim 1, wherein the thione and / or thiolate compound is represented by the following general formula (I), (II) or (III). Collection method. [Chemical 1] (In the formula, R represents an alkyl group, an alkenyl group, an aralkyl group, or an aryl group. Q represents an atomic group necessary for forming a 5- or 6-membered heterocycle. M represents a cationic group.
X and Y are an alkyl group, an alkenyl group, an aralkyl group,
Aryl group, a heterocyclic _{group, -N (R 1) R 2} , -N (R
_{3) N (R 4) R} 5, represents a -OR ₆ or -SR _7. R
₁ , R ₂ , R ₃ , R ₄ and R ₅ represent a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, an aryl group or a heterocyclic group, and R ₆ and R ₇ represent a hydrogen atom, a cation group,
It represents an alkyl group, an alkenyl group, an aralkyl group, an aryl group or a heterocyclic group. ) 3. The carrier according to claim 1, wherein the carrier carrying the thione and / or thiolate compound is liquid-permeable and is filled in a reaction part having a liquid-permeable carrier holding mechanism. Method for collecting silver in silver photographic processed liquid. 4. The method for collecting silver of a silver-containing photographic processed solution according to claim 1, wherein the solution after silver collection is reused as a photographic processing solution. 5. A developing device for a silver halide photographic light-sensitive material comprising a rinsing tank provided between a fixing tank and a water washing tank, a means for separating waste water from the water washing tank into clean water and silver-containing solution through a reverse osmosis membrane, A silver halide photographic light-sensitive material having a mechanism for returning clean water to the washing tank again, and a mechanism for permeating the silver-containing solution to the reaction section having the liquid-permeable carrier holding mechanism according to claim 3 to collect silver. Material processing equipment. 6. In a silver halide photographic light-sensitive material processing apparatus having at least a fixing capacity tank, the waste liquid of the fixing capacity tank is permeated to a reaction part having a liquid-permeable carrier holding mechanism according to claim 3. , A developing device for a silver halide photographic light-sensitive material having a mechanism for collecting silver. 7. A development processing apparatus for a silver halide photographic light-sensitive material, comprising a rinse tank provided between a fixing capacity tank and a water washing tank,
4. A development processing apparatus for a silver halide photographic light-sensitive material, which has a mechanism for collecting the silver by allowing the waste liquid in the rinse tank to permeate the reaction section having the liquid-permeable carrier holding mechanism according to claim 3. 8. A development processing apparatus for a silver halide photographic light-sensitive material comprising at least a fixing ability tank and a water washing tank or a fixing ability tank and a multi-stage rinsing tank, wherein waste water of the water washing tank or the rinsing tank is passed through a reverse osmosis membrane to obtain clean water. 4. A silver halide photographic light-sensitive material development processing apparatus having a waste liquid processing mechanism for separating clean water into a reaction section having a liquid permeable carrier holding mechanism according to claim 3, and dividing the water into a silver-containing solution.