JPS6271952A - Processing of color photography - Google Patents

Abstract

PURPOSE:To reduce the trouble about the pollution of a photographic material due to the generation of a sludge and a tray by recovering an electrolytic silver from a prefixing solution using an electrodialysis method. CONSTITUTION:The color photographic material is processed continuously with a color developer, the prefixing solution and a bleach-fixing solution followed by recovering the electrolytic silver from the prefixing solution using the electrodialysis method. Thus, the blinding of the electrodialysis film is minimized and the silver is recovered with a high recovering rate whereby the silver is almost recovered. Further the supplement of the bleach-fixing solution may be remarkebly reduced, thereby making substantially the recovery of the silver unnecessary in the bleach-fixing solution. As the variation of the composition in the prefixing solution is reduced, the supplememt of the prefixing solution may reduce, and the storage of the prefixing solution is improved and the corrosion of a stainless steel is remarkably reduced.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is capable of electrolytically desilvering silver from a used photographic processing solution, or recovering silver and improving the photographic performance of the photographic processing solution. This paper relates to a color photo processing method that can be reused without problems.

[Conventional technology and its problems]

After imagewise exposure, silver halide photographic materials are processed to obtain images by development and fixing steps. Regarding color photographic materials, there are provided the steps of color development, blanking, fixing, and stabilization treatment, or a bleach-fixing step in which bleaching and fixing are performed in one step.

A water washing process is provided between each process as necessary.

In the fixing or bleach-fixing process, silver halide in the photographic material is dissolved by silver halide solubilizers such as periosulfate and thiocyanate, so silver complex ions are added to the processing solution as processing progresses. It is carefully loaded. In other processes, silver halide solubilizers such as sulfite ions and thiosulfate ions are added as in the fixing and bleach-fixing processes, such as in the development process, or these silver complex ions are present in the photographic material. As the process progresses, silver complex ions accumulate as the process progresses, although the amount is smaller than that in the fixing process. Moreover, the accumulation of silver complex ions is
This significantly reduces the performance of the processing solution, and also poses a serious problem in terms of pollution control when disposing of the processing solution. Therefore, recovery of silver complex ions in the processing solution is desired from the viewpoints of restoring the performance of the processing solution, reducing pollution during disposal, and collecting and reusing useful resources.

Furthermore, from the perspective of pollution prevention and effective use of resources, 8! There is a trend towards low replenishment in the supply of replenisher to the tank, that is, to minimize the supply of replenisher per unit area of photographic light-sensitive material, and this is the cause of excessive accumulation of silver ion concentration. It becomes.

Therefore, it is important to maintain the silver ion concentration in the processing tank at a low concentration while continuously collecting silver ions, in order to proceed with the reaction efficiently, or to prevent them from being carried out on the sensitive material to the next processing stage. This is strongly desired in order to prevent the loss of silver that occurs. Similarly, it is strongly desired to regenerate the liquid after recovering silver ions and use it again as a replenisher from the viewpoint of pollution prevention and resource reuse.

Conventional techniques for desilvering from photographic processing solutions include metal substitution using steel wool or aluminum that utilizes ionization tendency, silver sulfide precipitation under alkaline conditions, reductive precipitation using hydrosulfide, and ion exchange. Ion exchange methods using resins or chelate resins, electrolytic reduction methods using electrolysis, etc. are known.

In the metal replacement method, iron and aluminum are eluted and hydroxide precipitates are formed, making it difficult to reuse the treatment solution, and silver sulfide precipitation and reduction precipitation methods also require time-consuming filtration to recover silver precipitates. Similarly, it is extremely difficult to reuse the processing liquid because it is difficult to recover it or the characteristics of the processing liquid change.

Methods such as ion exchange resin are preferred because they allow the treatment solution to be regenerated and reused, but the silver complex adsorption capacity of the resin is extremely small and is not economically viable.

The electrolysis method itself is a method that has been known for a very long time.
For example, M. L. Schreiber's review journal
Op the Nissembtee (J, of t
he SMPTE) Volume 74, Page 505, 1
Many examples of these prior art can be found in 965.

In particular, improvements to electrode plates for the purpose of improving current efficiency include U.S. Pat.
No. 4, No. 2,158,410, No. 3,840,455
No. 400,056, No. 4,054,503, Second Patent No. 1,093,561, Second Patent Application No. 2,507
, No. 123, No. 2,729,567, No. 674,98
No. 8, No. 1,178,373, Inter-French Patent No. 813,48
3, Italian Patent No. 439.945, Italian Patent No. 421,922, and US Patent No. 2,607゜7 as a device for electrolysis equipment.
No. 21, No. 1,962,306, No. 3,072,55
No. 7, No. 1,900°893, No. 303,942,
No. 195.953, No. 1,866.701, U.S. 4[f2
, No. 110.930, Second Patent No. 712.003, No. 1
, 133° 565, and 1,187,806.

Furthermore, as an efficient method for recovering silver from bleach-fix solutions,
No. 8-18191, U.S. Patent No. 4,036,715, and Second Patent No. 2,528.140, and Second Patent No. 2,80 for a method for separating cathodes and anodes using a diaphragm during electrolysis.
No. 7゜043, No. 2,532.018, Japanese Unexamined Patent Publication No. 1983-
No. 26315, No. 52-102724, No. 53-35
No. 534, Japanese Patent Publication No. 43-30167, etc., and U.S. Patent No. 3 as an automatic control method using current control.
, No. 875,032, No. 3,925.184, 1i
No. 4,006,071, vfrjll 1984-328
69 t, No. 52-115723, Buddhist temple patent 2,27
No. 5,570 describes this in detail. In combination with a treatment liquid regeneration method, an idea described in JP-A-52-72227 can be found.

The specific problem with silver recovery by electrolysis is that the photographic processing solution does not contain only silver complex ions, but also contains many other photographic processing chemicals, all of which are susceptible to oxidation or reduction. The reason is that it is a compound. That is, the electrode does not have selectivity only for silver complex ions.

It is generally known that the reaction on an electrode is determined by the magnitude of the electrode potential corresponding to the set current density or the set 'iri electrode potential and the redox potential of the reactive species. For example, if a used bleach-fix solution containing aminopolycarboxylic acid iron (III) complex salt as a bleaching agent and sodium thiosulfate as a fixing agent is subjected to 'Ki decomposition treatment, aminopolycarboxylic acid iron (Iff) will be produced at the cathode. Since the reduction potential of is more important than the silver deposition potential, the silver deposition reaction occurs competitively with the reduction of iron amyl/polycarboxylate, and if a higher cathode voltage is set, the silver deposition reaction occurs competitively with the reduction reaction of sodium thiosulfate. As a result, a silver sulfide precipitate is formed. Further, the contribution of each reaction to the obtained current (density) is roughly proportional to the number of electrons required for the reaction and the concentration of the reactive species.

Furthermore, the current Sung phenomenon occurs in which the silver precipitated in the 'Ki solution dissolves again. For this reason, under the conditions in which silver is deposited, the ratio of the current density of silver to the total current density (current efficiency) is actually quite low, and the total current (density) is also not very large, so it is difficult to actually recover silver. The speed is surprisingly low. The increase in amyl/polycarboxylic acid iron(II) complex ions generated in this way makes the redox potential of the processing solution less base, which not only reduces the silver bleaching (oxidation) rate but also reduces the image quality of color photographs. In other words, the reduction of the coloring dye that forms the coloring agent, leucoization, causing the dye to become viscous (and causing a serious problem of sagging).Furthermore, at the anode, the color developing agent and sulfite are oxidized, and the oxide heavy It is said that coalescence causes problems such as tar and sulfate formation.

In order to prevent such problems as much as possible, conventional methods have been devised and actually used, such as a rotating cathode plate system using high-speed rotation, or using carbon fibers to lower the current density.

However, in spite of these methods and many of the above-mentioned devices, in any case, in order to sufficiently reduce the concentration of silver ions in the processing solution and eliminate the stress during processing, low current density is used. Also, extremely long electrolysis time is required,
Alternatively, problems such as the formation of sludge may occur due to the excessive accumulation of sulfate ions caused by the formation of silver sulfide or the oxidation of sulfites.
Although recovery of silver from discarded processing solutions has been practiced, recycling it has been considered difficult because the above-mentioned problems occur and cause serious problems to photographic materials.

In addition, with conventional rotating plate electrodes made of stainless steel or titanium, if silver is recovered by electrolysis and then reused many times, it will gradually deteriorate even if the processing machine parts are made of high-quality stainless steel with fairly high corrosion resistance. The drawback was that it corroded, and its reuse was discouraged.

In recent years, processing machines have become smaller due to the decentralization of processing color photographic materials, but these processing methods have become simpler and faster, such as single-bath bleach-fixing (combined with this, the washing process can be reduced). There is a growing trend towards reducing the amount of waste liquid by removing and replenishing the concentration of the processing liquid, and the current situation is that there is a growing concern that the accumulation of silver complex ions will affect processing performance even more than before.

Therefore, it is possible to take advantage of the advantages of the electrolytic method as described above, but when regenerating the fixing device or bleach-fixing solution, it is possible to use an electrolytic method that does not bring about such benefits as fluctuations in photographic processing performance or corrosion of the solution processing surface. A silver recovery method is highly desired. Mata-dokoro! ! There is a strong desire for a compact and high-capacity electrolytic silver recovery method and device when connected to a rocky shore.

[Purpose of the invention]

The first object of the present invention is to use a desilvering technique that does not generate sludge or tar and cause malfunctions such as contamination of photographic materials even if the processing solution is stored after desilvering. The object of the present invention is to provide a color photographic processing method.

A second object is to provide a color photographic processing method that does not cause corrosion to the stainless steel members of an automatic processor even when using a processing solution in which silver has been recovered.

The third object is to provide color photographic processing performance using desilvering technology that minimizes fluctuations due to silver recovery in processing solution components.

The purpose of ttS4 is to provide a color photographic processing method using a silver recovery technique in which banding of iron divalent complexes does not occur even when electrolytic silver recovery is performed.

The fifth purpose is outside the photo! To provide a color photographic processing power method using a silver recovery technique in which the processed liquid is subjected to photographic processing again while recovering ffi from TAn continuously or intermittently, and can also be reused as a replenisher. There is a particular thing.

A sixth object is to provide a color photographic processing method that uses a technology that is built into a small automatic developing tank and allows continuous in-line silver recovery.

[Synopsis and effects of the invention]

As a result of intensive studies by the present inventors, the object of the present invention is to process a color photographic material in succession with a color developing solution, a pre-fixing solution, and a bleach-fixing solution, and to electrolyze the material using an electrodialysis method from the pre-fixing solution. This was achieved through silver recovery.

By recovering silver using the method of the present invention, it is possible to minimize electrodialysis and membrane clogging, and recover silver at a high recovery rate. A significant reduction in replenishment became possible, making it virtually unnecessary to recover silver in the bleach-fix solution. On the other hand, since fluctuations in the composition of the pre-fixer were suppressed, it was possible to reduce the amount of replenishment of the pre-fixer, and at the same time, the storage stability of the solution was improved. Furthermore, the corrosivity of stainless steel has also been greatly reduced. Further, by containing a color developing agent in the pre-fixing solution, the effects of the present invention can be more fully exhibited, and the effect is particularly significant in improving the storage stability of the solution and preventing the occurrence of Xj5 corrosion on stainless steel.

It is clear that recovery of silver from a pre-fixing solution is more advantageous than recovery of silver from a bleach-fixing solution in that it does not contain iron and therefore clogging of the electrodialysis membrane is less likely to occur, resulting in a higher silver recovery rate. However, it is completely inconceivable to improve the desilvering speed in the desilvering process and also facilitate silver recovery. In addition, by performing in-line silver recovery in the Moe setting r1e, it was possible to significantly reduce replenishment, and it was a completely unexpected effect that silver recovery from the subsequent bleach-fix solution was substantially unnecessary. Furthermore, it was completely surprising that the contamination of a color developing agent, which should be removed in conventional silver recovery, actually gave favorable results.

The present invention will be explained in more detail below.

Any electrolytic silver recovery apparatus and electrode electrolysis method can be used in the present invention. For example, a silver recovery tank using a rotating cylindrical electrode, which is commonly used in the past,
The spiral cathode disclosed in U.S. Pat. Further, it is also possible to apply a method such as that described in JP-A-56-696261, in which the anode is separated by a diaphragm and a solution having a composition different from that of the fixing solution is used as the anolyte. Furthermore, narrow patent 2,
1 shown in No. 741.080! A method of contacting with an ion exchange resin after electrolytic silver collection can also be used.

The electrodialysis treatment according to the present invention involves partitioning the cathode and anode of an electrodialysis tank with a diaphragm, filling the partitioned chamber with a stabilizing solution, and passing a direct current to the electrodes.

Preferably, the diaphragm is an ion exchange membrane, and more preferably, the cathode and the anode are alternately partitioned by an anion exchange membrane and a cation exchange membrane, so that a cathode chamber, a plurality of concentration chambers (lI3 electrode (a chamber partitioned by an anion exchange membrane on the side and a cation exchange membrane on the anode side), multiple desalination chambers (a chamber partitioned by a cation exchange membrane on the cathode side and an anion exchange membrane on the anode side)
and an anode chamber.The stabilizing solution is preferably placed in the demineralization chamber, and it is also preferable that it is placed in the cathode chamber.The electrolyte solution placed in the concentration chamber and the anode chamber is separately limited. For example, sodium sulfite, sodium sulfate, sodium chloride, potassium sulfate,
A 0.1-2N solution such as sodium 1,000 sulfate can be preferably used. At this time, it is very preferable to use a processing liquid having fixing ability as the electrolyte solution to be introduced into the concentration chamber and the anode chamber, since no electrolyte solution is required. Further, silver can also be recovered from the electrolyte solution, and as a silver recovery method, an electrolytic method or an ion exchange resin method can be used.

The above ion exchange membrane can also be obtained from commercial products. For example, CIPLE made by Asahi Kasei Corporation, Selemion made by Asahi Glass Co., Ltd., NEOS made by Lil Yamasoda Co., Ltd.
EPT^, Unilex manufactured by Mitsubishi Yuka Co., Ltd., Du Pont
It is known by product names such as 1Nafion manufactured by Ionics, 1ONICS^former ON manufactured by Ionics, and 10NIC3CATION.

Examples of materials for the electrodialysis cell and each pipe include polyvinyl chloride, polypropylene, polyethylene, and rubber-lined iron. Examples of cathode materials include iron, nickel, lead, zinc, titanium alloy stainless steel, etc., and anode materials include platinum, platinum-coated titanium, graphite, lead peroxide, magnetite, and 4102 coated electrode (DS). ＾electrode), etc.

In the processing method of the present invention, the pre-bath of the bleach-fix solution is essentially a fix solution, in which most of the silver salts are dissolved.

The color developing agents used in the present invention include known ones that are widely used in various color photographic processes. These developing agents include ami/7er/-el derivatives and 1/p-phenylenenoamine derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, since they are more stable than in the free state. Additionally, these compounds generally have a color development alQ of about 0.1
g to about 30 g, more preferably about 1 for IQ.
It is used for one period at an agricultural yield of about 15 g to about 15 g.

Examples of the ami-77 ether-based developing agents include 0-7 phenol, p-amino 7-ethyl, and 5-7 ethyl-2.
-hydroxytoluene, 2-ami7-3-hydroxytoluene, 2-hydroxy-3-ami/-1,4-tumethylbenzene, and the like.

Particularly useful aromatic primary amine color developing agents include N, N-
Dialkyl-1]-phenylenenoamine M is a compound, and the alkyl group and phenyl group may be substituted or unsubstituted.

Among them, particularly useful compounds are N,N-diethyl-1)-phenylenediamine hydrochloride, N-methyl-1]
-Phenylenediamine hydrochloride, N,N-tumethyl- []
-phenylenediamine hydrochloride, 2-amino/-51N-dithi/re-N-)'decylamino)-)/renin, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-amino/ Aniline sulfate, N-ethyl-N-β-
Hydroxyethylaminoaniline, t-7mi/-3-methyl-N, N-diethylaniline, 4-ami/-N-(
Examples include 2-7toxyethyl)-N-ethyl-3-methylaniline-p-)reninsulfonate.

The color developing agent according to the present invention may be added as a herbal medicine itself to the pre-fixing solution, or may be added by pre-containing it in the light-sensitive material. It is preferable to bring it into the liquid.

In addition to the above-mentioned aromatic primary amine color developing agent, the color developing solution contains various components normally added to color developing solutions, such as alkaline agents such as hydroxide, sodium carbonate, and potassium carbonate. , alkali metal sulfite, alkali metal bisulfite, alkali metal thiocyanate, alkali metal halide, benzyl alcohol, diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1
, 1-diphosphonic acid, a water softener, a thickening agent, etc. may optionally be contained. The pl+ of this color developer is
Usually 7 or more, most commonly about 10 to about 13.

Furthermore, the influence of fluctuations in 1) and 11 due to color developer brought in is virtually non-existent because the pre-bath mainly consists of the fixing agent composition, and contamination of 5% or more, especially 10% or more, is rather harmful. preferable.

Furthermore, the pI+ in the film after color development is high and inhibits the bleach-fixing reaction, but because of pre-fixing, there is an advantage that the MS ``J'' for the silver reaction in the film is also small.

In the present invention, the pretreatment liquid having fixing ability (hereinafter referred to as prefixing) is a fixing agent, that is, a compound that reacts with silver halide to form a water-soluble complex salt, such as potassium thiosulfate, sodium thiosulfate, thiosulfate, etc. It is a solution containing a periosulfate such as ammonium sulfate, a thiocyanate such as potassium thiocyanate, sodium thiocyanate, ammonium thiocyanate, thiourea, thioether, etc. The pre-fixer contains ammonium sulfite and
Preservatives such as sulfites such as potassium sulfite, ammonium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite, boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, pHfi cuts of various salts such as potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, etc. can be included.

Furthermore, alkali halide or ammonium halide,
For example, it is desirable to contain a large amount of a rehalogenating agent such as potassium bromide, sodium bromide, sodium chloride, or ammonium bromide. Furthermore, substances known to be added to normal fixing solutions, such as alkylamines and polyethylene oxides, can be appropriately added.

It is desirable that the prefix solution contains substantially no bleach (silver), but can contain bleach to a certain extent;
The limit is 0.2 mole or less, more preferably 0.05 mole or less, and most preferably 0.001 mole or less.

In the present invention, the pH of the pre-fixing solution and the bleach-fixing solution may be different or the same, and the pre-fixing tank solution and its replenisher have a lower pH than the bleach-fixing solution to neutralize color development.
pff of the bleach-fix solution in the bleach-fix tank.
is preferably higher than the pre-fixing solution in the pre-fixing tank. In either case, pff can be arbitrarily selected as required, and the optimum value may be selected to achieve the above-mentioned purpose. However, the preferred bleach-fix solution has a pH of +1 tl
-9, particularly preferably 4-8, and the pH of the pre-fixer is 3-]O, particularly preferably 4-9.

Preferably, the pre-fixer is treated while recovering silver, and usually electrolysis, ion exchange, or electrodialysis is used.

In these silver recovery methods, it is preferable that silver be processed while being continuously recovered by an in-line system, and as a result, silver recovery in a bleach-fix solution in a subsequent tank is not necessary.

It is desirable that air oxidation of the bleach-fix solution in the subsequent tank be carried out efficiently, and forced aeration can be performed.

In the present invention, it is preferable to supplement the pre-fixing solution mainly with a fixing agent and the bleach-fixing solution mainly with a fixing agent and a bleaching agent. It is possible to supply and replenish the pre-fixing solution in the pre-fixing tank with a bleaching agent within a range not exceeding the above range.

The amount of bleach used in the bleach-fix solution of the present invention is 60 g or more, preferably 80 g or more, particularly preferably 90 g or more per 11 processing solutions.

Preferred bleaching agents used in the present invention are organic acid r52 iron complex salts, especially ferric complex salts of amyl/bolicallebonic acid or aminopolymethylene phosphoric acid, especially ferric complex salts of aminopolycarboxylic acids. .

As a bleaching agent used in the bleach-fix solution of the present invention, preferred organic acids that form a ferric complex salt include the following.

These P11 acids (eg, organic acetic acids, organic phosphonic acids, etc.) may be alkali metal salts, aluminum salts, or water-soluble amine salts. Specific representative examples of these include the following.

(1) Ethylenedi7minetetraacetic acid (2) Ethylenediaminetetramethylenephosphonic acid (3) Diethylenetriaminepentaacetic acid (4) Noethylenetriaminepentamethylenephosphonic acid (5) Ethylenediamine-N-(β-hydroxyethyl)-N,N',N'-triacetic acid (6) Ethylenediamine-N-(β-hydroxyethyl)-N,N',N'-)rimethylenephosphonic acid (7) Propylenediaminetetraacetic acid (8) Propylenediaminetetramethylenephosphonic acid ( 9) Nitori a threee 1112 (10)
Nitrilotrimethylenephosphonic acid (11) Cyclohexanediaminetetraacetic acid (12) Cyclohexanoaminetitramethylenephosphonic acid (13) Iminoniacetic acid (14) Imi-7 dimethylenephosphonic acid (15)
Dihydroxyethylglycine citric acid (16) Dihydroxyethylglycine methylenephosphonic acid (17) Nohydroxyethylglycine tartaric acid (18)
) Ethyl ether diamine tetraacetic acid (19) Ethyl ether diamine tetramethylene phosphonic acid (20) Glycol ether noamine tetraacetic acid (21
) Glycol ethernoamine titramethylene phosphonic acid (22) Ethylenediamine tetrapropionic acid (2
3) Ethylenediaminetetraacetic acid (24) Ethylenediaminetetramethylenephosphonic acid (25) Ethylenediaminetetraacetic acid nonodium salt (
26) Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt (27) Ethylenediaminetetraacetic acid tetrasodium salt (28) Noethylenetriaminepentaacetic acid pentasodium salt (29) Ethylenediamine-N-(β-hydroxyethyl)-N,N ',N'-Triacetic acid sodium salt (30) Propylenezamine tetraacetic acid sodium salt (
31) 2) Lilotriacetic acid sodium salt (32) Cyclohexannoaminetetraacetic acid sodium salt (33) Noami 7propyl-tetraacetic acid (34)
Cyami/Prop-7-lutetetramethylenephosphonic acid (35) Ethylenediaminenoorthohydroxyphenylacetic acid 36) Ethylenediaminediorthydroxyphenylmethylenephosphonic acid (37) Ethylenenoaminetitramethylenephosphonic acid (38) Triethylenetetraminehexaacetic acid (39) )
) Liethylenetetraminehexamethylenephosphonic acid Preferred organic acids include those having a molecular weight of 300 or more. Bleaching agents include these (depleted with carbonic acid and ferric complex salts, and these complex salts may be ammonium salts, sodium salts, or potassium salts. These bleaching agents may be used alone or in combination of two or more. This is the preferred method.

In addition to these bleaching agents, the bleach-fix solution may contain a fixing agent and any of the following additives.

As fixing agents, compounds which react with silver halides to form water-soluble complex salts, such as thiosulfates such as potassium thiosulfate, sodium thiosulfate, and ammonium thiosulfate;
Examples include thiocyanates such as potassium thiocyanate, sodium thiocyanate, and ammonium thiocyanate, thiourea, and thioether.

In addition to these fixing agents, the bleach-fix solution also contains sulfites such as ammonium sulfite, potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, aqueous ammonium metabisulfite, potassium metabisulfite, and sodium metabisulfite. Boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate,
pH buffering agents consisting of various salts such as ammonium hydroxide can be included.

Furthermore, alkali halide or ammonium halide,
For example, potassium bromide, sodium bromide, sodium chloride, ammonium bromide, etc. It is desirable that the polyelectrode contain a 10-genifying agent. Also, borates, oxalates, acetates,
1) 1141FJj agents such as carbonates and phosphates, alkylamines, polyethylene oxides, etc. which are known to be added to ordinary bleach-fix solutions can be appropriately added.

When supplementing the bleach-fix solution with a bleach-fix solution, it can be divided into two or more component solutions and refilled.

When dividing into two constituent liquids, it is preferable that one (A) be used as a fixing agent and the other (3) be used as a bleaching agent. Bleach content in bleach-fix replenishment 'o, B is 0.2 mol or more per 1e.
L is preferably 0.4 mol or more and 1.5 mol or less.

In addition, in general, 7-m-7 polycarboxylic acid ferric complex salts have a low solubility, so it is not easy to prepare a concentrated solution like the one shown in 4-1 using lj alone. A concentrated solution can be obtained relatively easily by adding aqueous ammonia, potassium carbonate, sodium carbonate, potassium borate, sodium borate, potassium metaborate, sodium metaborate, etc. to increase pl+.

Potassium periosulfate, sodium periosulfate, ammonium thiosulfate, etc. are useful as the fixing agent used in bleach-fix replenisher A, and the content thereof is 11591.
The amount is preferably 0 mol or more, and most preferably 1.5 mol or more and 5.0 mol or less.

In addition, sulfites include ammonium sulfite, potassium sulfite,
Ammonium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite, etc. are useful, and the amount used is 0.3 mol or more per bleach-fix replenisher AIN. and preferably 0.4 mol or more 3.5
It is in the molar range.

The above concentration range is a preferable range from the viewpoint of variation in the liquid composition of the bleach-fixing bath and bleach-fixing ability.

The pH of the bleach-fixing replenisher used in the present invention is preferably set so as to maintain the pH of the bleach-fixing bath at 4.0 to 9.0.

It is preferable not to add bleach to the bleach-fix replenisher A in terms of the storage stability of the processing solution.

Bleach-fix replenisher B preferably contains boric acid, ammonium chloride, ammonium nitrate, etc., in addition to a ferric complex salt of an organic acid such as 7-minoboricarboxylic acid as described above and a suitable alkali agent. In addition, chelation of 7/polycarboxylic acids other than the above-mentioned ttS2 iron salt can be carried out, for example, by including diammonium salt of ethylenediaminetetraacetate.

Bleach-fixing replenisher B also contains fixing agents such as thiosulfates, sulfites, chelating agents such as sulfuric acid and aminopolycarboxylic acids in the glacial acetic acid pond, boric acid, phosphoric acid, sulfuric acid, etc. l) H buffer, thiocyanate, amine, silver halide solvent such as mercaptotriazole, 1-phenyl-3
- Known stain inhibitors such as pyrazolidone, formamidinosulfinic acid, and paraphenylene diamine, polyalkyl heptamine compounds (described in British Patent No. 1,192,481), polyamine compounds (described in Japanese Patent Publication No. 1988-8836)
, ethylene oxide M (described in Narrow Mouth Patent No. 966.410), nitrogen-containing heterocyclic compound (Monkey Patent No. 1,290,8
Known additives (described in No. 12) may be included.

In the present invention, air or oxygen may be blown into the bleach-fix bath and the bleach-fix replenisher storage tank as desired in order to increase the activity of the bleach-fix solution.
or a suitable oxidizing agent such as hydrogen peroxide, bromate,
Persulfates and the like may be added as appropriate.

When carrying out the method of the present invention, silver may be recovered from the pre-fixing solution and/or the bleach-fixing solution by known methods. For example, electrolysis method (described in French Patent No. 2,299,667), precipitation method (
Described in Japanese Patent Application Laid-Open No. 52-73037, Second Patent No. 2331
220), ion exchange method (JP-A-51-1711)
4 (described in Japanese Patent No. 2,548,237), metal substitution method (described in British Patent No. 1,353,805), etc. can be effectively used.

In the treatment method of the present invention, treatment with pruning M solution, 1f!
Preferably, the bath and the bleach-fix treatment bath are connected in a forward flow manner. The most preferable processing method is to perform pre-fixing immediately after color development, but it is also possible to perform pre-fixing treatment directly after color development, such as washing, rinsing, or stopping. The impregnated prebath may be used as a processing liquid prior to prefixing.

After bleach-fixing, stabilization treatment may be performed without washing with water, or washing with water and subsequent stabilization treatment may be performed. In addition to the above steps, known auxiliary steps such as hardening, neutralization, black-and-white development, reversal, and washing with a small amount of water may be added as necessary.

A typical example of a preferred treatment method includes the following steps.

(1) Color development → Pre-fixing → Bleach fixing → 1st stable → 2nd stable → 3rd stable (2) Color development → Moe fixation → Bleach fixing → Washing with a small amount of water → Washing (3) Color development → Prefixing → Bleach fixing →Washing→Stable (4)
Color development → pre-fixing → bleach-fixing → stable (5) color development →
Pre-fixing → bleach-fixing → first stable → second stable (6) color development → washing → pre-fixing → bleach-fixing → washing (or stable) (7) color development → stop → pre-fixing → bleach-fixing → stable However,
In each process, the pre-fixing and bleach-fixing steps include downstream connections.

In addition, in the above specific examples, where the stabilization process is divided into two or more, each of them may be based on the same type of precept or may be based on different types of liquids, and the stabilizing liquid may be divided into two or more stabilizing processes, and the stabilizing liquid may be divided into two or more, and each stabilizing process may be based on the same type of precept or may be based on different types of liquids. These include those that have a fif value and those that have a function to prevent uneven water droplets.

The bleach-fix solution used in the present invention includes various types of a/lt.
It is preferable to add a genus salt. It is also preferable to add these inorganic metal salts after forming them into metal complex salts through various chelate cuttings.

〔Example〕

Hereinafter, the present invention will be explained in detail with reference to Examples, but the embodiments of the present invention are not limited thereto.

The compositions of the pre-fixing solution and bleach-fixing solution used in the Examples are as follows.

[Pre-fixer]

2-Amino-5-mercap)-1,3,4-thianoazole ammonium thiosulfate 100% ammonium sulfite solution 10g Add water to make 1e, add acetic acid or aqueous ammonia to 11H
Adjusted to 6,9.

[) Liquid white determination Adjust the pH to 6.9 using water.

Add 52.2 g of silver bromide to 10Q of previously determined XJ solution (equivalent to a concentration of 38/Q), and use the electrodialysis-electronegative silver recovery device shown in Figure 1 to bring the amount of silver to 0.5 g/Q. Electrolytic silver recovery was carried out until then.

FIG. 1 shows a state in which the electrodialysis cell 21 and the electrolytic cell 38 are connected.

? To explain the electrodialysis tank X, the main body 21 has a cation exchange membrane 24 and an anion exchange membrane 2 between the cathode z2 and the anode 23.
5, which are alternately partitioned into a cathode chamber 2G, an anode chamber 27, a concentration chamber 28 (a chamber partitioned by an anion exchange membrane on the cathode side and a cation exchange membrane on the anode side), and a desalination chamber 29 (a chamber partitioned by a cation exchange membrane on the cathode side). The membrane is formed by a chamber in which the anode side is separated by an anion exchange membrane. ) An electrolyte solution is supplied to the agricultural reduction chamber 28 through a supply pipeline 42 and is caused to flow out through an outflow pipeline 43. Photographic fixer waste liquid is supplied to the desalting chamber Z9 through a supply pipeline 32 and is allowed to flow out through an outflow pipeline 33. An electrolyte solution such as sodium sulfate is supplied to the cathode chamber 26 and the anode chamber 27 through a supply pipeline 36 and flows out through an outflow pipeline 37. II;
! A direct current is applied between 'i22 and the anode 23.

38 electrolytic cells will be explained. A cathode 39 and an anode 40 are installed. Then, the electrolyte solution flowing out from the concentration chamber 2B of the electrolytic dialysis tank 21 is supplied through the supply pipeline 43 and is caused to flow out through the outflow pipeline 42. Cathode 39 and positive (
A direct current is passed between the two.

In the connection between the electrodialysis tank and the electrolytic tank, 30 is a fixer waste circulation tank, and the fixer waste is circulated between the circulation tank 30 and the desalination chamber 29 by a circulation pump 31 and circulation pipelines 32 and 33. It is circulated. 34 is a negative room fluid circulation tank, which includes a circulation pump 35 and a circulation pipeline 36.
．． 37, an electrolyte solution such as sodium sulfate is circulated between the circulation tank 34, the cathode chamber 26, and the positive electrode chamber 27. An electrolyte solution is circulated between the fixed angle tank 38 and the agricultural cotton chamber 28. Direct current is passed between the cathode 22 and anode 23 of the electrodialyzer 21 and between the cathode 39 and anode 40 of the electrolytic cell 38.

The materials for the cathodes (22 and 39) of the electrodialysis cell 21 and the electrolytic cell 38 include iron, nickel, stainless steel, etc., and the materials for the anodes (23 and 40) include iron, platinum, platinum, etc. Examples include M gold titanium. The anion exchange membrane is preferably a strongly basic anion exchange membrane, and the cation exchange membrane is preferably a strongly acidic cation exchange membrane.

Insulating materials such as polyvinyl chloride, rubber, or rubber-lined iron are used as the material for the main body 21 of the electrodialyzer and the main body 38 of the electrolytic cell, and for the piping.

As the electrolyte solution, a solution containing a silver complex forming agent such as sodium thiosulfate or ammonium thiosulfate, which has the property of dissolving silver salts, is desirable. Such solutions contain sulfite) IJ
A decomposition inhibitor such as sodium bisulfite may be added, or a small amount of a reducing agent such as sodium bisulfite may be added to the aminopolycarboxylic acid 11n2a complex salt that may migrate in trace amounts from the fixer waste solution in the desalting chamber. You may. Further, as the electrolyte solution, a conventional photographic fixing solution containing a silver complex forming agent may be used as it is.

Example 1 A color developing agent was added to the pre-fixing solution, and silver was recovered after electrodialysis. A color-developed commercially available color negative film was processed, and the silver concentration 3ε/Q in the pre-fixing solution was repeated 50 times to 0.5 g/Q after silver recovery. (corresponding to clogging) was measured. In addition, the pre-fixing solution after silver recovery was allowed to stand at room temperature, and the time required for precipitation to occur was investigated. The results are shown in Table 1.

Kyo 1) Electrodialysis 0 times, electrolytic silver recovery only 5 times Thu 2) N
-ethyl-N-β-hydroxyethyl-3-methyl-4
-7 Minoaniline sulfate 13) N-Ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-7 Minoaniline sulfate The results in Table 1 indicate that the color developing agent mixed into the pre-fixing solution is It has been shown that clogging of the ion exchange membrane is reduced and the storage stability of the pre-fixer is improved.

Example 2 After adding a color developing agent to the pre-fixing solution and recovering silver, a stainless steel plate (material: 5
OS304) was immersed so that the plate surface was above the liquid level, left at room temperature for 20 days, and its corrosion status was observed. Second result
Shown in the table.

The corrosion status was evaluated using the following 5-level criteria.

+++...Rust has formed on the 81″# surface to the point where it appears in a continuous red and black color, and rust has also formed in other spots.

+10...8! Red-black rust appears on the interface, and other spots appear as well.

10... Thread-like red and black rust appears on the liquid surface.

±...Slight rust has occurred.

−・・・・・・No change at all.

The results in Table 2 show that incorporation of color developing agent into the prefix solution significantly reduces stainless steel corrosion.

Example 3 Silver was recovered in-line from the pre-fix solution so that the silver concentration was always below 0.5 g/l, and the amount of replenishment of the bleach-fix solution was varied to determine the effect on the amount of silver in the bleach-fix solution. I looked into it. The results are shown in Table 3.

The pre-fixer was also replenished and over 70- was brought into the bleach-fixer. The compositions of the pre-fixing replenisher and bleach-fixing replenisher are as follows.

[Pre-fixing replenisher]

2-7mi/-5-mercapto-1,3,4-thiadiazole 2g Ammonium thiosulfate 120g Ammonium sulfite 15g Add water to make 11, add acetic acid or aqueous ammonia to ptt6
．． Adjust to 9.

[) Blank fixing replenisher]

Ethylenenoaminetetraacetic acid iron ([1) ammonium 00g Ethylenenoaminetetraacetic acid tetrasodium salt 402 Add water to make 1p, use acetic acid or aqueous ammonia to make pt1
Adjusted to 6.9.

The replenishment amount is 35 m for both pre-fixing replenisher and bleach-fixing replenisher.
+a The capacity is per 11 liters of color negative film, and the amount of silver in the bleach-fixing solution is that of commercially available 3511II11 color negative film.
This is the silver ion concentration after processing 10,000 films (24 shots) with a constant replenishment amount.

From the results in Table 3, it is clear that by recovering silver from the pre-fixing bath, the silver ion concentration in the bleach tube solution does not increase much even with a low replenishment amount.

Example Using the bleach-fix solution used in Example 3, the desilvering ability of the color negative film after pruning and fixing was investigated. As a result, no desilvering failure occurred in the case where silver was recovered from the previous fixer, but in the case where silver was not recovered, desilvering failure occurred in all cases except when the replenishment amount was 8.75+nQ. Spot-like foreign matter was observed.

〔Effect of the invention〕

By implementing the present invention, the following effects can be obtained.

(1) Silver recovery rate can be increased, and electrodialyzers and electrolyzers can be downsized.

(2) Containing a color developing agent improves the pre-fixer's shelf life and prevents corrosion of stainless steel equipment.

3) # In-line silver recovery of the fixer can significantly reduce the amount of bleach-fix replenishment, and virtually eliminates the need for silver recovery from the bleach-fix.

[Brief explanation of drawings]

FIG. 1 shows an example of an electrodialysis-electrolytic silver recovery apparatus used for silver recovery according to the present invention. 1 Electrodialysis tank 2 Cathode 3 Anode 4 Cation exchange membrane 5 Anion exchange membrane 6 Cathode chamber 7 Anode chamber 8 Concentration chamber 9 Demineralization chamber lO fixer waste liquid circulation tank 11 Circulation pump 12 Supply pipeline (fixer Ml liquid) 13
Outflow pipeline (〃) 14 Cathode chamber liquid circulation tank 15 Circulation pump 16 Supply pipeline (electrolyte bath 8 tank 17
Outflow pipeline (〃) 18 Electrolytic cell 19 Cathode 20 Anode 21 Circulation pump

Claims (3)

[Claims] (1) Silver halide color photographic light-sensitive material with a color developing solution,
1. A color photographic processing method characterized by successive processing with a pre-fixing solution and a bleach-fixing solution, and recovering electrolytic silver from the pre-fixing solution using an electrodialysis method. (2) The color photographic processing method according to claim 1, wherein the pre-fixer contains a color developing agent. (3) A color photographic processing method according to claim 1 or 2, characterized in that the pre-fixer is regenerated in-line by a silver recovery device attached to an automatic processor.