JPH06262181A - Device for developing silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To reduce the amt. of a waste developing soln. and to obtain a system capable of stable development in a photographic developing device having a stage for reducing a photographic developing agent by dipping an anode in the waste developing soln. CONSTITUTION:This developing device has a stage for reducing a photographic developing agent with an electrode. In this case, an anode is dipped in the waste developing soln. Namely, a developing tank 1 (reduction tank) to be filled with a developing soln. and an oxidation tank 2 to be filled with an overflowing waste developing soln. are set adjacent to each other in the electrolytic reduction device, and both tanks are connected with a salt bridge. A cathode 3 and an anode 4 are dipped respectively in the reduction tank 1 and oxidation tank 2. Consequently, a system capable of stable development is obtained even when the waste soln. amt. is reduced.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic development processing apparatus utilizing an electrode reaction.

[0002]

2. Description of the Related Art When a silver halide light-sensitive material after exposure is processed by an automatic processor, the processing agent used is deteriorated by the processing. The major ones of these deteriorations are deterioration due to a development reaction with a photosensitive material and deterioration due to air oxidation. In order to carry out stable processing of a silver halide photographic light-sensitive material, a method of replenishing a replenishing solution and causing an excess solution to overflow has hitherto been adopted. As a method of replenishing,
55-126242, 55-126243, 57-195245, 57-19
5246, 57-195247, 60-104946, 62-238559
JP-A-1-140156 and JP-A-1-140156 disclose means for recovering fatigue by replenishing a developing replenisher continuously or intermittently according to the development processing amount. On the other hand, the photographic processing waste liquid generated by the overflow is conventionally disposed of in the ocean, biologically treated, or incinerated after being properly treated. However, reduction of waste liquid is desired from the viewpoint of global environment protection and treatment cost. As one of the means for solving the problem of reducing the waste liquid, there is a method of reducing the replenishment by electrolytically reducing and regenerating the developing agent that has been oxidized and fatigued.
No. 40 is disclosed. However, in the conventional electrolytic reduction method, since the redox reaction is carried out in the same system, the developing agent reductively regenerated is oxidized again at the anode, resulting in poor efficiency. Also, there is a means of immersing the electrode in the electrolytic solution as a method of dividing the system, but the operation must be complicated because the electrolytic solution must be supplied separately.
It has problems such as occupying space in the electrolytic cell and costly.

Therefore, it has been desired to develop a developing processing apparatus which solves these problems.

[0004]

SUMMARY OF THE INVENTION It is a first object of the present invention to provide a stable development processing system even if the amount of waste liquid is reduced. The second purpose is to use a reduction system with electrodes without the use of an electrolyte solution. Other purposes will be apparent from the following specification.

[0005]

It has been found that the above object can be achieved by the following constitution.

A development processing apparatus for a silver halide photographic light-sensitive material, characterized in that, in a photographic development processing apparatus having a step of reducing a photographic development processing agent with an electrode, an anode is immersed in a development processing waste liquid.

The details will be described below.

Step of reducing photographic developing agent with electrode The step of reducing photographic developing agent with an electrode in the present invention means a developing agent oxidized by a developing reaction of a silver halide photographic light-sensitive material or air oxidation of the developing agent. This refers to the step of reducing the oxidant of the preservative for suppression by energizing the electrode.

Electrolytic Reduction Device The fatigued developing solution may be reduced and regenerated in the developing tank or a part of the waste solution may be taken out and electrolytically regenerated to be a replenishing solution.

The cathode may be immersed in the developing tank and a tank directly connected to the developing tank (extending the life of the developing solution in the developing tank) or in the overflowed developing waste solution (reproducing waste solution). At the cathode, electrolytic reduction occurs and the developing agent (eg, hydroquinone) and preservative are reduced and regenerated and circulated in the developing tank.
The material of the cathode may be any electric conductor or semiconductor that can withstand long-term use. Iron, nickel,
Examples include lead, zinc and stainless steel.

The anode is immersed in a waste developer solution (however, the bath in which the cathode is not immersed). At the anode, unreacted developing agent (eg hydroquinone) is oxidized. The material of the anode may be an insoluble material and an electric conductor. Examples thereof include platinum, platinum-plated titanium, graphite and the like.

The applied potential suitable for electrode reduction is 0.05-100v,
Preferably, it is 0.1-10v, the current density is 0.02-3A / dm ² ,
It is preferably 0.05 to 1.2 A / dm ² .

After the reduction treatment, the regenerant may be fed into the developing tank in a batch treatment.

To regenerate the photographic developer by the electrolytic reduction method of the present invention, immediately before the untreated developer is supplied to the electrolytic reduction tank, JP-A-53-46732, JP-A-52-146236, and JP-A-54-9626. Issue 54
The anion such as bromine ion may be removed by contact treatment with an adsorbent such as polymers and various ion exchange resins described in JP-A-19741 and JP-A-53-132343.

The concentrated solution may be diluted with water in order to carry out electrolytic reduction while maintaining current efficiency.

Processing Agent As the developing agent, dihydroxybenzenes, or a combination of dihydroxybenzenes and pyrazolidones, or dihydroxybenzenes and p-aminophenols is used.

Next, dihydroxybenzenes (for example, hydroquinone, chlorohydroquinone, bromhaodroquinone, isopropylhydroquinone, methylhydroquinone 2,3 dichlorohydroquinone, 2,5 dichlorohydroquinone, 2,3 dibromohydroquinone, 2,5 dimethylhydroquinone. ) And the like, but hydroquinone is particularly preferable.

Examples of pyrazolidones include 1-phenyl-3-pyrazolidone and 1-phenyl-4,4-dimethyl-3-
Examples include pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone.

Examples of aminophenols include N-
Methyl-p-aminophenol, p-aminophenol, N- (β
-Hydroxyethyl) -p-aminophenol, N- (4-hydroxyphenyl) glycine, 2-methyl-p-aminophenol, p-benzylamonophenol, etc.
P-aminophenol is preferred.

The developing agent is usually preferably used in an amount of 0.01 mol to 1.2 mol / liter. The pH of the developer used in the present invention is preferably in the range of 9 to 13, more preferably 10 to 12.

The alkaline agent used for setting the pH includes
Potassium hydroxide, sodium hydroxide, sodium carbonate,
Contains pH adjusters such as potassium carbonate, sodium triphosphate, potassium triphosphate. Buffers such as JP-A-61-28708 (borate), JP-A-60-93439 (for example, saccharose, acetoxime, 5-sulfosalicylic acid), phosphate and carbonate may be used.

Additives used in addition to the above components include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and formaldehyde sodium bisulfite.

As additives used in addition to the above components, development inhibitors such as sodium bromide, potassium bromide and potassium iodide ethylene glycol, diethylene glycol, triethylene glycol, dimethylformaldehyde, methylcellosolve, hexylene glycol, Organic solvents such as ethanol and methanol: 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole
-An antifoggant such as a mercapto compound such as 5-sulfonic acid salt or a benztriazole compound such as 5-nitrobenzimidazole may be included, and if necessary, a toning agent, a surfactant, an antifoaming agent, a water softening agent. Agent, JP-A-56-10624
It may include the amino compound described in No. 4 and the like. In the present invention, a developer containing a silver stain preventing agent, for example, JP-A-56-243
The compounds described in No. 47 can be used.

The developer may contain an amino compound such as an alkanolamine described in JP-A-56-106244.

In addition, LFA Messon, "Photographic Processing Chemistry," published by Focal Press (1966), pages 22-229, US Pat. No. 2,193,015, ibid.
Those described in 2,592,364 and JP-A-48-64933 may be used.

The fixer is an aqueous solution containing thiosulfate,
It has a pH of 3.8 or higher, preferably 4.2 to 5.5.

The fixing agents include sodium thiosulfate and ammonium thiosulfate, and ammonium thiosulfate is particularly preferable from the viewpoint of fixing speed. The amount of the fixing agent used can be appropriately changed and is generally about 0.1 to about 6 mol / liter.

The fixing solution may contain a water-soluble aluminum salt which acts as a hardening agent, and examples thereof include aluminum chloride, aluminum sulfate and potassium alum. Tartaric acid, citric acid or their derivatives may be used alone or in combination in the fixing solution.
It is effective that these compounds contain 0.005 mol or more per liter of the fixing solution, and particularly 0.01 to 0.03 mol / l.

Specific examples include tartaric acid, potassium tartrate, sodium tartrate, potassium sodium tartrate, citric acid, sodium citrate, potassium citrate, lithium citrate, ammonium citrate and the like.

If desired, the fixer may contain a preservative (for example,
Sulfite, bisulfite), pH buffer (e.g., acetic acid, boric acid), pH adjuster (e.g., sulfuric acid), a chelating agent having the ability to soften water and a compound described in Japanese Patent Application No. 60-213562. it can.

The processing method of the present invention is applied to various photosensitive materials such as X-ray, black and white general photosensitive material, CRT photographing, infrared light sensitive material for laser light source, indirect, duplication, printing and plate-making photosensitive material. Applicable to

Photosensitive Material The emulsion used in the photographic light-sensitive material of the present invention can be produced by a known method. For example, Research Disclosure (RD) No. 17643 (December 1978), pages 22-23, 1. Emulsion Preparation and types, and the same (R
D) No. 18716 (November, 1979) -It can be prepared by the method described on page 648.

Also, “The theory of the ph” by TH James
otographic process ”4th edition, published by Macmillan (1977
Pp. 38-104, GF Daufin, "Photographic Emulsion Chemistry", Focal p.
Published by ress (1966), P. Glafkides "Physics and Chemistry of Photography""Chimie et physique photographique" Paul Mon
Published by tel (1967), VL Zelikman et al. "Making and Coating photographic Emul"
It is prepared by the method described in “sion” Focal press, Inc. (1964).

That is, a solution method such as a neutral method, an acidic method or an ammonia method is mixed under conditions such as a forward mixing method, a reverse mixing method, a double jet method, a controlled double jet method or the like, a conversion method, a core / shell method. It can be produced using the particle preparation conditions such as and the like and a combination method thereof. One of the embodiments of the present invention is a monodisperse emulsion in which silver iodide is localized inside the grains.

In the present invention, tabular grains are preferably used. The average grain size of tabular silver halide grains is 0.2
˜2.5 μm is preferable, and 0.5 to 2.0 μm is particularly preferable.

The tabular silver halide emulsion has an average value of grain diameter / thickness (called aspect ratio) (called average aspect ratio) of 3 or more, preferably 6 to 60, more preferably 7 -50, particularly preferably 8-20.

The average thickness is preferably 0.4 μm or less, more preferably 0.3 μm or less, and particularly preferably 0.05 to 0.25 μm. The diameter of the silver halide grain is defined as the equivalent spherical diameter of the grain from the observation of an electron micrograph of the silver halide grain. The thickness of the silver halide grain is defined as the minimum distance between the two parallel planes forming the tabular silver halide grain.

The thickness of the tabular silver halide grains can be determined from an electron micrograph of a silver halide grain shaded or an electron micrograph of a sample slice obtained by coating a silver halide emulsion on a support and drying. .

To obtain the average aspect ratio, the minimum
Measure 100 samples.

In the silver halide emulsion of the present invention, the proportion of tabular silver halide grains in all silver halide grains is 50% or more, preferably 60% or more, particularly preferably 70% or more.

As the tabular silver halide emulsion, those having monodispersity are preferably used, and those having 50% by weight or more of silver halide grains contained in a grain size range of ± 20% around the average grain size are particularly preferable. It is preferably used.

The tabular silver halide emulsion has an optional halogen composition such as silver chloride, silver bromide, silver chloroiodide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc., but has a high sensitivity. Therefore, silver iodochlorobromide is preferable, the average silver iodide content is 0 to 4.0 mol%, particularly preferably 0.2 to 3.0 mol%, and the average silver chloride content is 0 to 5 mol%.

In the tabular silver halide emulsion, the halogen composition may be uniform within the grain or silver iodide may be localized, but the one localized in the central portion is preferred. Used.

The method for producing a tabular silver halide emulsion is described in JP-A Nos. 58-113926, 58-113927, 58-113934 and 6-113.
It is also possible to refer to 2-1855, European Patents 219,849, 219,850 and the like. Further, JP-A-61-6643 can be referred to as a method for producing a monodisperse tabular silver halide emulsion.

As a method for producing a tabular silver iodobromide emulsion having a high aspect ratio, a silver nitrate aqueous solution or a silver nitrate aqueous solution and a halide aqueous solution are simultaneously added to a gelatin aqueous solution whose pBr is kept at 2 or less to form seed crystals. It can be obtained by generating and then growing by the double jet method.

The size of tabular silver halide grains can be controlled by the temperature at the time of grain formation and the rate of addition of an aqueous silver salt and halide solution.

The average silver iodide content of the tabular silver halide emulsion can be controlled by changing the composition of the aqueous halide solution to be added, that is, the ratio of bromide to iodide.

When producing tabular silver halide grains, a silver halide solvent such as ammonia, thioether or thiourea can be used if necessary.

The emulsion may be subjected to a water washing method such as a noodle water washing method or a flocculation sedimentation method in order to remove soluble salts. A preferred washing method is, for example, Japanese Patent Publication Sho
As a particularly preferable desalting method, a method using an aromatic hydrocarbon aldehyde resin containing a sulfo group described in 35-16086, or a method using aggregating polymer agent exemplified G3, G8 described in JP-A-2-7037 is mentioned. To be

The emulsion according to the present invention can use various photographic additives in the steps before and after physical ripening or chemical ripening. Known additives include, for example, RD No. 1764
3 (December 1978), No.18716 (November 1979) and No.18716.
The compound described in 308119 (December 1989) is mentioned. The types of compounds and the places where they are described in these three Research Disclosures are listed below.

Additive RD-17643 RD-18716 RD-308119 Page Classification Page Classification Page Classification Chemical sensitizer 23 III 648 Upper right 996 III Sensitizing dye 23 IV 648-649 996-8 IV Desensitizing dye 23 IV 998 B Dye 25-26 VIII 649-650 1003 VIII Development accelerator 29 XXI 648 Upper right fog inhibitor / stabilizer 24 IV 649 Upper right 1006-7 VI Whitening agent 24 V 998 V Surfactant 26-7 XI 650 Right 1005-6 XI Antistatic agent 27 XII 650 Right 1006 to 7 XIII Plasticizer 27 XII 650 Right 1006 XII Sliding agent 27 XII Matting agent 28 650 Right 1008 to 9 XVI Binder 26 XXII 1003 to 4 IX Support 28 XVII 1009 XVII Photosensitive according to the present invention Examples of the support that can be used as the material include the above-mentioned RD-17643, page 28 and RD-308119, 100.
Examples include those described on page 9. A suitable support is a plastic film or the like, and an undercoat layer may be provided on the surface of these supports in order to improve adhesion of the coating layer, corona discharge, ultraviolet irradiation or the like may be applied.

[0052]

EXAMPLES Examples of the present invention will be described below.
The present invention is not limited to these.

Example 1 A method of extending the life of the developing solution by electrolytically reducing the developing solution in the developing tank to regenerate the developing agent will be described.

Electrolytic Reduction Device 1 The electrolytic reduction device of the present invention will be described with reference to FIG. 1
Is filled with a developing solution in a developing tank (reduction tank). In No. 2, the developing waste liquid overflowed in the oxidation tank is filled.
The cathode 3 and the anode 4 are immersed in the reduction tank 1 and the oxidation tank 2, respectively. The reduction tank 1 and the oxidation tank 2 are connected by a salt bridge.

Regeneration Treatment by Electrolytic Reduction Device The running developer was electrolytically reduced and regenerated as follows. Stainless steel sheet containing molybdenum (Nippon Metal Industry Co., Ltd.)
NTK316 15X100cm thickness 1mm made by NTK316, cathode, carbon sheet (Kureha Chemical Industry Co., Ltd., Kure sheet 15X100 thickness 1m
m) as an anode, using an electrolytic reduction tank
Electrolytic reduction was performed by continuously energizing at 0.8 V and a current density of 1.5 mA / m ² .

Preparation of developer (developer formulation) Potassium sulfite 70 g 1,4-dihydroxybenzene 28 g 1-phenyl-3-pyrazolidone 1.2 g Hydroxyethylethylenediamine triacetate trisodium 8 g Boric acid 10 g 5-Methylbenzotriazole 0.04 g 1- Phenyl-5-mercaptotetrazole 0.01g Sodium metabisulfite 5g Acetic acid (90%) 13g Triethylene glycol 15g 5-Nitroindazole 0.2g Glutaraldehyde 4g Potassium bromide 4g 5-Nitrobenzimidazole 1g Dissolve in 1 liter of water, The solution was adjusted to pH 10.5 with sodium hydroxide.

(Preparation of Fixing Solution) Sodium thiosulfate pentahydrate 4.5 g Ethylenediaminetetraacetic acid disodium 0.5 g Ammonium thiosulfate 150 g Anhydrous sodium sulfite 8 g Potassium acidate 16 g Aluminum sulfate 10-18 hydrate 10 g Sulfuric acid (50 wt%) 5 g Quench Acid 1 g Boric acid 7 g Glacial acetic acid 5 g An aqueous solution of 1 liter was made into a solution of pH 4.2 with glacial acetic acid.

Preparation of seed emulsion 1 Monodisperse cubic grains of silver iodobromide containing 2 mol% of silver iodide having an average grain size of 0.3 μm by the double jet method while controlling at 60 ° C., pAg = 8 and pH = 2.0. Was prepared.

The resulting reaction solution was desalted at 40 ° C. using an aqueous solution of Demol N manufactured by Kao Atlas Co. and an aqueous solution of magnesium sulfate, and then an aqueous gelatin solution was added thereto to re-disperse it to obtain a seed emulsion.

Growth from Seed Emulsion 1 Grains were grown as follows using the seed emulsion described above. First, disperse the seed emulsion in a gelatin aqueous solution kept at 40 ° C,
Furthermore, the pH was adjusted to 9.7 with aqueous ammonia and acetic acid.

To this solution, an aqueous ammoniacal silver nitrate ion solution and an aqueous solution of potassium bromide and potassium iodide were added by the double jet method. During the addition, pAg = 7.3 and pH were controlled to 9.7 to form a layer having a silver iodide content of 35 mol%. Next, an ammoniacal silver nitrate aqueous solution and a potassium bromide aqueous solution were added by the double jet method. The pAg was maintained at 9.0 up to 95% of the target particle size, and the pH was continuously changed from 9.0 to 8.0. afterwards,
The pAg was adjusted to 11.0 and grown to the target particle size while maintaining pH 8.0. Subsequently, the pH was lowered to 6.0 with acetic acid, and 5,5'-dichloro-9-ethyl-3,3-di- (3-sulfopropyl) oxacarbocyanine sodium salt anhydride (desensitizing dye GD-1) was added. 400
mg / mol AgX was added, desalting was performed using an aqueous solution of Demol N manufactured by Kao Atlas and an aqueous solution of magnesium sulfate, and then a gelatin solution was added to redisperse.

By this method, a tetradecahedron having an average silver iodide content of 2.0 mol and a rounded apex has an average grain size of 0.40 μm and 0.65.
μm, 1.00 μm, coefficient of variation (σ / r) of 0.17 and 0, respectively.
16, 0.16 monodisperse silver iodobromide emulsions (A), (B), (C)
Was prepared.

Preparation of Seed Emulsion 2 0.1% hydrogen peroxide treated gelatin vigorously stirred at 40 ° C.
A double-jet method was used to add an equimolar potassium bromide aqueous solution containing a silver nitrate aqueous solution and hydrogen peroxide-treated gelatin to a 05N potassium bromide aqueous solution, and the temperature was 25 ° C for 1.5 minutes to 30 minutes.
After the liquid temperature was lowered to 80 ml, 80 ml of ammonia water (28%) was added per mol of silver nitrate, and stirring was continued for 5 minutes.

Thereafter, the pH was adjusted to 6.0 with acetic acid, desalting was performed using an aqueous solution of Demol N manufactured by Kao Atlas and an aqueous solution of magnesium sulfate, and then an aqueous gelatin solution was added and redispersed.

The resulting seed emulsion was spherical grains having an average grain size of 0.23 μm and a coefficient of variation of 0.28.

Growth from Seed Emulsion 2 Grains were grown as follows using the above seed emulsion. An aqueous solution of potassium bromide and potassium iodide and an aqueous solution of silver nitrate were added by a double jet method to an aqueous solution containing ossein gelatin and propyloxy polyethyleneoxy disuccinate disodium salt vigorously stirred at 75 ° C. During this time pH =
It was kept at 5.8 and pAg = 9.0. After the addition was completed, the pH was adjusted to 6.0 and GD-1 was added at 400 mg / mol AgX. Further, the mixture was desalted at 40 ° C. using a Demol N aqueous solution manufactured by Kao Atlas Co., and then an aqueous gelatin solution was added and redispersed.

By this method, a tabular silver iodobromide emulsion (D) having an average silver iodide content of 1.5 mol% and a projected area diameter of 0.96 μm, a coefficient of variation of 0.25 and an aspect ratio (projected area diameter / grain thickness) of 4.0. Was prepared.

Sample Preparation Each of the obtained emulsions (A), (B), (C) and (D) at 550 ° C. with GD-1 and 5,5′-di- (butoxycarbonyl)-
1,1-diethyl-3,3-di- (4-sulfobutyl) benzimidazolocarbocyanine sodium salt anhydride (weight ratio of 200: 1) (A) was 975 mg per mol of silver halide,
(B) 600 mg, (C) 390 mg, and (D) 500 mg were added.

After 10 minutes, chloroauric acid, sodium thiosulfate,
Ammonium thiocyanate was added for chemical ripening.
15 minutes before the end of ripening, 200 mg of potassium iodide was added per mol of silver halide, and then 4-hydroxy-6-methyl-1,
3,3a, 7-Tetrazaindene was added in an amount of 3 × 10 ^-2 mol per mol of silver halide and dispersed in an aqueous solution containing 70 g of gelatin.

Of the four ripened emulsions, (A),
(B) and (C) were mixed at a weight ratio of 15:65:20 to prepare Emulsion-I, and (D) was used alone as Emulsion-II.

Additives as shown in JP-A-2-301744, page 95, line 16 to page 96, line 20 were added to each of Emulsion-I and Emulsion-II.

Further, 1.2 g of the dye emulsion dispersion shown below was added to prepare an emulsion coating solution.

Preparation Method of Dye Emulsion Dispersion 10 kg of the following dye was dissolved at 55 ° C. in a solvent consisting of 28 liters of tricresylphosphite and 85 liters of ethyl acetate.
This is called an oil-based solvent. On the other hand, a 9.3% gelatin aqueous solution containing 1.35 kg of the following anionic surfactant (AS) is used as an aqueous solvent.

Next, the oil-based solvent and the water-based solvent were placed in a dispersion pot and dispersed while keeping the liquid temperature at 40 ° C.

[0075]

[Chemical 1]

The additives used for the protective layer are as follows. The added amount is shown as an amount per 1 liter of the coating liquid.

Coating solution for protective layer Lime-treated inert gelatin 68 g Acid-treated gelatin 2 g Sodium-i-amyl-n-decylsulfosuccinate 0.3 g Polymethylmethacrylate (matting agent having an area average particle size of 5.0 μm) 1.1 g Silicon dioxide particles (A matting agent having an area average particle diameter of 3.0 μm) 0.5 g Ludox AM (DuPont colloidal silica) 30 g Glyoxal 40% aqueous solution (hardening agent) 1.5 ml CH ₂ = CHSO ₂ CH ₂ ) ₂ O 500 mg

[0078]

[Chemical 2]

The emulsion layer has a silver conversion value of 1.7 g / side per side.
Glycidyl methacrylate-methyl acrylate-with 2 slide hopper type coaters at a speed of 90 m / min so that the amount of m ² , gelatin is 2.5 g / m ² , and the amount of gelatin in the protective layer is 0.99 g / m ^2. Emulsion layer on 175 μm polyethylene terephthalate base coated with an aqueous copolymer dispersion obtained by diluting a butyl methacrylate copolymer (50:10:40 wt%) to a concentration of 10 wt% A protective layer was coated on both sides simultaneously and dried for 2 minutes and 15 seconds to obtain a sample.

<Sensitometry test> The obtained sample was sandwiched between fluorescent intensifying screens KO-250 (manufactured by Konica [Co.]), irradiated with X-rays at a tube voltage of 90 KVP and 20 mA for 0.05 seconds, and developed. ,
The electrolytic reduction tank of the present invention was directly connected to the developer tank of the automatic original imager SRX-501 (manufactured by Konica Corporation) and circulated, and the overflowed developing waste solution was used as an electrolytic solution, with an applied voltage of 8.0 V and a current density of 1.5. While continuously regenerating the developer by electrolyzing at mA / cm ² , the developing temperature is 35 ° C, the fixing temperature is 33 ° C, and the washing water is 3.5 ° L / min at 18 ° C.
The entire treatment process was performed at a drying temperature of 45 ° C. in the 45-second mode shown below.

For replenishment of the developer, a liquid having the same components as the used developer was used as in the conventional method, and the replenishment amount was as shown in Table 1. The number of processed sheets is 50 per day, and the 1st and 300th sheets (6
The sensitivity, gamma, and fog values of the 1000th sheet (after 20 days) and the 1000th sheet (after 20 days) were determined by creating a sensitometric curve by the distance method. Sensitivity value is X required to obtain fog + 1.0 density
It was calculated as the reciprocal of the dose. Gamma is the density of the characteristic curve 1.0
From 2.0 to 2.0.

That is, tan θ is defined as gamma γ, where θ is the inclination of a straight line connecting the points of density 1.0 and 2.0.

The sensitivity is the sensitivity of the first sheet of sample No. 1
The relative sensitivity when 00 was used.

The results are shown in Table 1.

[Treatment Process] Process Treatment temperature (° C.) Treatment time (sec) Insertion-1.2 Development + crossover 35 14.6 Fixing + crossover 33 8.2 Washing + crossover 18 7.2 Squeeze 40 5.7 Drying 45 8.1 Total −45.0

[0086]

[Table 1]

Example 2 The same evaluation as in Example 1 was performed using the following electrolytic reduction apparatus 2 in the case where the waste developer was regenerated by electrolytic reduction and replenished to the developing tank as a replenisher again.

Electrolytic Reduction Device 2 The electrolytic reduction device of the present invention will be described with reference to FIG. 1
Nos. 1 and 12 are filled with the developing waste liquid overflowing in the reducing tank and the oxidizing tank, respectively, and both are partitioned by the anion exchange membrane 5. Cathode 3 and anode 4 are reduction tanks, respectively
11, immersed in the oxidation tank 12. The developing and regenerating solution electrolytically reduced in the reducing tank 11 is circulated by a motor and sent to the developing tank together with the developing solution in use. The anion exchange membrane is Neos
epta AM-3 (manufactured by Tokuyama Soda) was used.

The results are shown in Table 2.

[0090]

[Table 2]

[0091]

According to the present invention, when a silver halide light-sensitive material is run, even if the amount of waste liquid is reduced, there is no fluctuation in photographic performance in the early and latter stages, and stable images can be obtained, and the waste liquid It was also possible to reduce BOD and COD.

[Brief description of drawings]

FIG. 1 is an example (side view) of an electrolytic reduction device.

FIG. 2 is an example (side view) of an electrolytic reduction device.

[Explanation of symbols]

 1 Development tank 2 Oxidation tank 3 Cathode 4 Anode 5 Anion exchange membrane 11 Reduction tank 12 Oxidation tank

Claims (1)

[Claims] 1. A development processing apparatus for a silver halide photographic light-sensitive material, comprising a step of reducing a photographic development processing agent with an electrode, wherein the anode is immersed in a development processing waste liquid.