US3746543A - Process for the regeneration of fixing photographic solution - Google Patents
Process for the regeneration of fixing photographic solution Download PDFInfo
- Publication number
- US3746543A US3746543A US00129836A US3746543DA US3746543A US 3746543 A US3746543 A US 3746543A US 00129836 A US00129836 A US 00129836A US 3746543D A US3746543D A US 3746543DA US 3746543 A US3746543 A US 3746543A
- Authority
- US
- United States
- Prior art keywords
- fixing solution
- silver
- fixing
- polyethylene glycol
- photographic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title abstract description 37
- 230000008929 regeneration Effects 0.000 title abstract description 8
- 238000011069 regeneration method Methods 0.000 title abstract description 8
- 229920001223 polyethylene glycol Polymers 0.000 abstract description 42
- 229910052709 silver Inorganic materials 0.000 abstract description 30
- 239000004332 silver Substances 0.000 abstract description 30
- 239000002202 Polyethylene glycol Substances 0.000 abstract description 27
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 21
- -1 silver halide Chemical class 0.000 description 21
- 239000012528 membrane Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 10
- 238000011084 recovery Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 7
- 238000005868 electrolysis reaction Methods 0.000 description 7
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 6
- 230000006866 deterioration Effects 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 4
- 150000002334 glycols Chemical class 0.000 description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920000298 Cellophane Polymers 0.000 description 2
- 235000014276 Diplazium esculentum Nutrition 0.000 description 2
- 244000108321 Diplazium esculentum Species 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 150000001449 anionic compounds Chemical class 0.000 description 2
- 150000001767 cationic compounds Chemical class 0.000 description 2
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920001213 Polysorbate 20 Polymers 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- 230000035508 accumulation Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 1
- 239000000244 polyoxyethylene sorbitan monooleate Substances 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
- G03C5/395—Regeneration of photographic processing agents other than developers; Replenishers therefor
Definitions
- This invention relates to a process for regenerating a photographic fixing solution used in the processing of photographic silver halide light-sensitive materials and to a process for using the fixing solution thus generated repeatedly.
- the remaining silver salt is dissolved away in a fixing bath with sodium thiosulfate.
- the step is shown by the following reaction.
- n is believed to be 2 0r 3 and X represents a halogen atom.
- the silver salt and the halide gradually accumulate and the content of free thiosulfate decreases in the fixing solution.
- the exhausted fixing solution contains silver complex salts, it is economically quite profitable to recover silver from the fixing solution using either a chemical method or an electrolytic method.
- a chemical recovery method has generally been employed but when the recovery of silver in the fixing solution is conducted using an electrolytic method, the thiosulfate bonded to the silver ions is liberated forming free ions. Therefore, the employment of the electrolytic recovery method has the advantages that the fixing solution recovers its fixing activity and can be used repeatedly. However, with repeated use of the fixing solution, the properties of the fixing solution are reduced gradually although the concentration of the free thiosulfate is sufliciently high.
- the fixing rate is lowered and insufficient fixation results. Consequently, even employing the electrolytic recovery method, there is a limit in repeating the use of the fixing solution.
- the electrolytic recovery of silver from a fixing solution requires a large cost for the equipment used in the electrolysis and the electric power used, it is important to attempt an economical use of the fixing solution 'by increasing the number of recycled uses of the fixing solution. For the purpose, it is economically quite profitable to prevent the fixing solution from being deteriorated during the repeated electrolysis and reuse.
- An object of the present invention is to provide an economical electrolytic recovery process by preventing the deterioration of a fixing solution during the repeated uses thereof and increasing the number of repeated uses.
- Polyethylene glycols which can be effectively used in this invention are polyethylene glycol and the nonionic, aninonic and cationic derivatives thereof, having a molecular weight for the polyoxyethylene chain of greater than 400, preferably greater than 1,000, and having good solubility in or good swelling characteristics by water.
- the following various kinds of compounds can be used in this invention.
- the molecular weight in polyoxyethylene chain of polyethylene glycol or its derivatives is less than 400, the etfect of the invention is not obtained. As the molecular weight increases, the better the effect obtained. Therefore, the upper limit of the molecular weight is not limited. For example, polyethylene glycols having a molecular weight of 500,000 have been prepared.
- (Ll) Nonionic compounds 1) Polyethylene glycol having a molecular weight of greater than 400 Suitable examples are Carbowax 1540, Carbowax 4000, and Carbowax 1200, made by the Union Carbide and Carbon Chemical Corp., U.S.A.
- Carbowax 1540 has an average molecular weight of from 1300 to 1600, a specific gravity of 1.15 and a solidifying temperature of from 43 to 46 C.
- Polyethylene glycol methyl phenyl ether having a molecular weight of greater than 500 For example, one having a polymerization degree of 50 or 25 in the polyoxyethylene chain is made by Nippon Emulsion K. K., Japan.
- Polyoxyethylene alkyl ether Suitable examples are polyoxyethylene sorbitan monooleate (HLB 15.0), polyoxyethylene sorbitan mono- 3 stearate (HLB 14.9) which are made by the Atlas 00., and polyoxyethylene sorbitan monolaurate having polymerization degree of 30 or 50 made by Nippon Emulsion K. K.
- Polyoxyethylene polyoxypropylene block polymer Suitable examples are Pluorinics L-61, L-62, -L-64, L-68 and L-75, which are made by Wyandotte, U.S.A.
- Polyoxyethylene alkyl ester Suitable examples are polyoxyethylene monostearate (HLB 17.9) made by the Atlas 00., polyoxyethylene dilaurate having a polymerization degree of about 23 made by Nippon Yuski, K.K., Japan, and polyoxyethylene monolaurate having a polymerization degree of 50 made by Nippon Emulsion K.K.
- the drawing illustrates a fixing solution circulating system of a large-scale developing machine equipped with an electrolytic recovery means.
- overflowing liquid from a fixing solution tank (F) of the developing machine is collected in a storage tank (S) and then sent, by means of a pump (P), to an electrolytic cell (C), in which the fixing solution is electrolyzed by an electric current applied to the electrodes from an electric source (E) while stirred by means of an agitator (A) to deposit the silver thus electrolyzed.
- the desilvered fixing solution is sent back to the fixing solution tank (A) of the developing machine through a stock tank (M) and is used repeatedly.
- an appropriate proportion of the solution can, if necessary, be discharged through a drain (D) and at the same time a fresh fixing solution can be supplied from a tank (R).
- the system illustrated in the drawing is only one example and the application of this invention is not limited to this system. Practically, the process of this invention can also be applied to simpler systems having neither a storage tank nor a stock tank, a system without a tank (R) for supplying a fresh fixing solution, and a system having two or more stock tanks.
- the simpler systems are basically the same as shown in the drawing.
- a system composed of a fixing tank equipped with the electrodes for conducting the electrolysis may be employed.
- a portable electrolytic unit may be used for a small-scale developing machine.
- a bag of a semipermeable membrane containing one or more of the polyethylene glycols is suspended in the storage tank of the above-described system.
- the fixing solution in the storage tank enters into the bag of the semipermeable membrane, wherein the fixing solution recovers its fixing activity due to the contact with polyethylene glycols in the bag, and then returns to the developing machine through a circulating system for reuse.
- the bag of the semipermeable membrane can be effectively used not only in the storage tank but also in the electrolytic cell, the stock tank or the fixing solution tank or in any other part of the system.
- a filtering means is provided to a portion of the circulating system for the fixing solution, e.g., to an inlet or an outlet of the electrolytic cell.
- a semipermeable membrane is used as a filter for the filtering means and polyethylene glycol or a derivative thereof is placed in the filtering means between the filters of the semipermeable membrane.
- a pump may be attached to the filtering means to force the circulating solution through the filtering means.
- the semipermeable membrane contributes to the maintenance of the polyethylene glycol or derivative thereof inside the membrane and permits the fixing solution to flow freely through the membrane to the inside thereof to contact the fixing solution with the polyethylene glycols within the membrane.
- Suitable such semipermeable membranes are a cellophane sheet or a vesica of an ox or a pig can be used.
- the fixing solution Due to the contact of the fixing solution with the polyethylene glycols as described above, the deterioration of the fixing solution can be prevented and thus the fixing solution recovers its activity sufficiently after removing the silver therefrom and the fixing solution can be used repeatedly whereby the amount of the fresh replenisher can be markedly reduced.
- the amount of polyethylene glycol or derivative thereof to be used depends upon the circulation speed of the fixing solution and the manner of contacting the fixing solution and polyethylene glycol or derivative thereof. Generally speaking, the larger the amount used, the greater the efiect thereof.
- the fixing solution was repeatedly used for about 100 days by recycling it through the electrolytic silver recovery unit equipped with a container bag containing 1 kg. of the polyethylene glycol while the amount of replenishment was reduced to the minimum needed to keep the tank level.
- contacting the fixing solution with polyethylene glycol continuously is effective and when the polyethylene glycol is contacted with the fixing solution intermittently utilizing the standing period of development, the amount of polyethylene glycols necessary for etfecting the process of this invention is increased.
- polyethylene glycols lose their reactivating power due to their use for a long period of time, they are replaced with fresh polyethylene glycols.
- the process for regenerating the fixing solution of this invention may be applied widely in developing laboratories.
- the process of this invention may be employed either in developing laboratories operating on a large scale in which several developing machines are operated simultaneously and a large amount of a fixing solution is used and is circulated through all of the develop ing machines or in developing laboratories operating on a smaller scale in which small developing machines and portable-type electrolytic means are used and the regeneration of the exhausted fixing solution by electrolysis is conducted overnight or over the weekend.
- the process of this invention is applicable to the fixing solutions used with various light-sensitive materials such as color photographic light-sensitive materials, black and white photographic materials, cinematic films, amateur cinematic films, and X-ray photographic films.
- the process of this invention most effectively is applied to fixing solutions used in the fixing of a photographic material having a high-sensitive silver iodobromide emulsion layer.
- EXAMPLE 1 Using a developing machine for 16 mm. cinematic color photographic reversal films, 56 EK-type Cine Strip Machine (made by PAKO Corporation), about 10,000 feet per week of the film was developed and the silver in the fixing solution used in the process was recovered using a portable small-scale electrolytic means, Ropak -type silver recovering machine (made by PAKO Corporation) during the stands and the fixing solution thus regenerated was used repeatedly. During the process, the total amount of the fixing solution was maintained at a constant level by replenishing just the loss by carry-over (no overflow):
- the fixing speed for the films in the fixing tank shown by the time required for making the film transparent was 25 seconds at the beginning of the operation, but reached 50 seconds after 10 days, and became 70 seconds after days. Finally, the adverse influences of the deterioration of the fixing solution on the qualities of the photographic images obtained due to the development were observed.
- the speed of fixing was greatly reduced. That is, the clearing time was 30 seconds after 10 days from the starting of the operation, 40 seconds after 20 days, and the generation and the reuse of the fixing solution could be continued for a long period of time yet securing sufiiciently good quality for the developed products. In addition, the efficiency in the recovery of silver was not reduced.
- EXAMPLE 2 When the same procedure as in Example 1 was followed using a block polymer of polyethylene glycol and polypropylene glycol, Pluoronic L-62 (made by Wyandotte (30.), instead of the polyethylene glycol used in .Example 1, the regeneration and the reuse of the fixing solution could be conducted for a long period of time as in Example 1.
- Pluoronic L-62 made by Wyandotte (30.
- EXAMPLE 3 The apparatus used in Example 1 was equipped with a storage tank to conduct the electrolytic recovery of silver when the developing processor was operated. In this apparatus, the system was so set that when the concentration of silver became higher than 0.9 g./liter in the fixing solution, the electrolysis started. A semi-permeable membrane bag containing 2 kg. of polyethylene glycol methylphenyl ether having a molecular weight of about 2,200 was immersed in the storage tank.
- polyethylene glycol or derivative having a polyoxyethylene chain having a molecular weight greater than 400.
- said polyethylene glycol derivative is selected from the group consisting of a polyethylene glycol methyl phenyl ether, a polyoxyethylene alkyl ether, a polyoxyethylene nonyl phenyl ether, a polyoxyethylene sorbitan ester, a polyoxyethylenepolyoxypropylene block polymer, a polyoxyethylene alkyl ester, a polyoxyethylene bispyridinium sulfonate, and a pol'yethoxyethyl bissulfuric acid.
- a process for the regeneration of a photographic fixing solution containing dissolved silver comprising contacting a fixing solution used in a photographic developing process with a polyethylene glycol or a derivative thereof; electrolyzing the thus contacted fixing solution and recovering the silver formed; and reusing the thus electrolyzed fixing solution in a photographic developing process.
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Electrolytic Production Of Metals (AREA)
- Photographic Developing Apparatuses (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP45028169A JPS4835492B1 (enrdf_load_stackoverflow) | 1970-04-02 | 1970-04-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3746543A true US3746543A (en) | 1973-07-17 |
Family
ID=12241225
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US00129836A Expired - Lifetime US3746543A (en) | 1970-04-02 | 1971-03-31 | Process for the regeneration of fixing photographic solution |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US3746543A (enrdf_load_stackoverflow) |
| JP (1) | JPS4835492B1 (enrdf_load_stackoverflow) |
| DE (1) | DE2116256A1 (enrdf_load_stackoverflow) |
| GB (1) | GB1297598A (enrdf_load_stackoverflow) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4059446A (en) * | 1975-04-30 | 1977-11-22 | Agfa-Gevaert, N.V. | Processing of photographic silver halide material |
| US4147546A (en) * | 1976-04-19 | 1979-04-03 | Fuji Photo Film Co., Ltd. | Prevention of fog formation in color photographic process |
| US5888707A (en) * | 1996-11-25 | 1999-03-30 | Agfa-Gevaert | Method of processing photographic material |
| CN108531943A (zh) * | 2018-04-16 | 2018-09-14 | 沈阳建筑大学 | 一种纳米银粉体的电化学制备方法 |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4895383A (enrdf_load_stackoverflow) * | 1972-03-17 | 1973-12-07 | ||
| JPS5521333B2 (enrdf_load_stackoverflow) * | 1972-05-04 | 1980-06-09 | ||
| CH584912A5 (enrdf_load_stackoverflow) * | 1973-10-18 | 1977-02-15 | Ciba Geigy Ag | |
| EP0266311B1 (de) * | 1986-10-31 | 1992-06-17 | Ciba-Geigy Ag | Fluoranfarbbildnergemisch und seine Verwendung in Aufzeichnungsmaterialien |
| US5149689A (en) * | 1986-10-31 | 1992-09-22 | Ciba-Geigy Corporation | Fluoran color former mixture and use thereof in recording materials |
| JP6444784B2 (ja) * | 2015-03-19 | 2018-12-26 | Ｊｘ金属株式会社 | 銀、チオ硫酸及び不純物を含む溶液の処理方法、チオ硫酸塩の回収方法及び銀の浸出方法 |
-
1970
- 1970-04-02 JP JP45028169A patent/JPS4835492B1/ja active Pending
-
1971
- 1971-03-31 US US00129836A patent/US3746543A/en not_active Expired - Lifetime
- 1971-04-02 DE DE19712116256 patent/DE2116256A1/de active Pending
- 1971-04-19 GB GB1297598D patent/GB1297598A/en not_active Expired
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4059446A (en) * | 1975-04-30 | 1977-11-22 | Agfa-Gevaert, N.V. | Processing of photographic silver halide material |
| US4147546A (en) * | 1976-04-19 | 1979-04-03 | Fuji Photo Film Co., Ltd. | Prevention of fog formation in color photographic process |
| US5888707A (en) * | 1996-11-25 | 1999-03-30 | Agfa-Gevaert | Method of processing photographic material |
| CN108531943A (zh) * | 2018-04-16 | 2018-09-14 | 沈阳建筑大学 | 一种纳米银粉体的电化学制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| GB1297598A (enrdf_load_stackoverflow) | 1972-11-22 |
| DE2116256A1 (de) | 1971-10-14 |
| JPS4835492B1 (enrdf_load_stackoverflow) | 1973-10-29 |
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