JPH06242558A - Method and device for developing photosensitive material - Google Patents

Abstract

PURPOSE:To provide a method and device for processing photosensitive material easy in the maintenance of the processing device, simple in the structure of the device, capable of the sufficient energizing regeneration of an inorganic developing agent and excellent in an obtained image quality. CONSTITUTION:A cathode 12 is provided in a developing vessel D filled with a developer containing the inorganic developing agent, an anode 14 is provided in an electrolytic chamber E provided through the developing vessel D and an anion exchange membrane 10, an energizing mechanism 16 for energizing and generating corresponding to a processing quantity is provided and the developer contains ascorbic acid and/or phenidone or the like. By incorporating ascorbic acid or the like in the developer the air oxidation of the inorganic developing agent is prevented, energizing control is mode easy, the processing vessel is simplified, the maintenance of the processing device is made easy and the obtained image quality is made excellent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photographic light-sensitive material processing apparatus and method for processing a silver halide light-sensitive material (hereinafter referred to as a light-sensitive material). A processing device and a processing method.

[0002]

In the wet processing of a silver halide black-and-white light-sensitive material, it is processed in steps such as black-and-white development, fixing and washing after exposure. A black and white developing solution is used for black and white development, a fixing solution is used for fixing, tap water or ion-exchanged water is used for washing, and a stabilizing solution is used for stabilizing treatment.

The inventor of the present invention provided a simple energization processing tank in the processing apparatus to energize the inorganic developing solution and maintain the activity of the developing solution to bring the inorganic developing process to a practicable level (for example, a special method). Kaihei 4-250449, Japanese Patent Application No. 4-11994
No. 4 and No. 4-125409 can be mentioned. ). Further, almost no waste liquid is generated from these processing devices.

[0004]

When processing the photosensitive material and energizing at all times, a constant performance can be always obtained without performance deterioration, but if the developing solution is left untreated and not energized, it is left unattended. It was confirmed that the oxidation-reduction potential increased with time, and the developer was deteriorated by air oxidation. Therefore, if the electricity is supplied depending on the processing amount, the inorganic developing agent is not sufficiently regenerated and the image quality is deteriorated. Further, simply energizing in accordance with the amount of treatment and air oxidation causes fog in the obtained image, so that a desirable result cannot be obtained.

The inventor of the present invention has proposed a processing apparatus which separately processes energization and energization over time in consideration of the oxidation of the developing agent due to the processing of the light-sensitive material and the oxidation of the developing agent due to oxygen in the air (Japanese Patent Application No. 2000-242242). No. 4-283643). This device is equipped with a developing tank equipped with a cathode and two electrolytic chambers equipped with an anode separated by an anion exchange membrane or a composite porous membrane. With respect to the air oxidation during the lapse of time, electricity is applied with the composite porous membrane sandwiched therebetween. As a result, no fog was observed when the air-oxidized component was energized using the anion exchange membrane.

That is, the inorganic developer can be regenerated by removing the bromine ion from the developing tank by energizing the composite porous film with the bromine ion acting as an antifoggant secured. Such a regenerable inorganic development process that does not generate waste liquid becomes more practical. However, since it is necessary to consider the energization of the process and the energization with the passage of time as described above, an increase in the number of processing tanks and a complicated energization control device are required, the processing device becomes large and complicated, and maintenance of the device becomes difficult. .

Therefore, an object of the present invention is to provide a photosensitive device in which the maintenance of the processing device is easy, the structure of the device is simple, and it is possible to sufficiently regenerate the inorganic developing agent by energization and to obtain a good image quality. It is an object of the present invention to provide a material processing apparatus and processing method.

[0008]

SUMMARY OF THE INVENTION The present invention has the following objects.
It is achieved by the following (1) to (4). (1) A cathode is brought into contact with a developing solution containing a developing agent which reacts with silver halide to become an oxidant and returns to a reduced form by giving an electron, and which contains ascorbic acid and a derivative thereof, and the developing solution and an anion exchange membrane. A developing treatment method of treating a silver halide light-sensitive material by bringing an anode into contact with an electrolyte solution which is in contact with the electrode and applying a voltage to both electrodes to carry out an electrification treatment. (2) Ascorbic acid and its derivative were added to the developer in an amount of 0.
The method for processing a light-sensitive material according to (1) above, which comprises from 0.5 to 0.5 mol / liter. (3) 0.1 to 0.1% phenidone and its derivative in the developing solution
The method for processing a light-sensitive material according to (1) or (2) above, which contains 100 mmol / liter. (4) Ascorbic acid and its derivative were added to the developer in an amount of 0.
The method for processing a light-sensitive material according to any one of the above (1) to (3), which contains 1 to 0.4 mol / liter and 0.3 to 30 mmol / liter of phenidone and its derivative. (5) A cathode is provided in a developing tank filled with a developing solution containing a developing agent which reacts with silver halide to become an oxidant and returns to a reduced form by giving an electron, and which contains ascorbic acid and its derivative. A development processing apparatus having an energization mechanism in which an anode is provided in an electrolyte solution provided via an anion exchange membrane, and energization reproduction is performed according to the processing amount of a photosensitive material.

[0009]

That is, the present invention is a processing apparatus which is filled with a metal complex (inorganic) developer containing ascorbic acid and its derivative (ascorbic acid, etc.) and has a developing tank which can be energized. As a result, air oxidation of the inorganic developing agent is suppressed, and it is not necessary to energize the air oxidization component when the developer is aged for a time without treatment and without electricity. The liquid can be sufficiently regenerated, and the device can be simplified and the device can be easily maintained.

Conventionally, since ascorbic acid is hydrolyzed by alkali, it is difficult to use it for photographic processing using an organic developing solution having a high pH of 10.2, and the developing solution has a high pH even in the inorganic developing processing. It was not used because the inorganic developing agent is easily oxidized. On the other hand, in the present invention, the pH of the inorganic developer can be lowered because the inorganic developer can be electrically regenerated and can be electrically regenerated. Therefore, the developer does not contain ascorbic acid. Even if ascorbic acid or the like is not hydrolyzed, the reducing property of ascorbic acid or the like can be effectively acted. Therefore,
It is considered that ascorbic acid or the like suppresses the air oxidation of the inorganic developing agent as a preservative.

If ascorbic acid or the like is contained in the developing solution, not only the oxidation of the inorganic developing agent is prevented but also the sensitivity is increased. Ascorbic acid is very easily oxidized as known as vitamin C, and it was difficult to make the reducing property of ascorbic acid practicable. However, the present inventor combined it with a current-carrying mechanism to improve its reducing property. Enabled

Examples of the ascorbic acid used in the present invention include compounds represented by the following general formula (I).

[0013]

[Chemical 1]

The amount of ascorbic acid contained in the developer of the present invention is 0.05 to 0.5 mol / liter,
It is preferably 0.1 to 0.4 mol / liter. Further, ascorbic acid has a property of being easily oxidized, but since it is combined with a current-carrying mechanism, it is not necessary to replenish it frequently, and replenishment may be about 10% or more of the amount taken out of the photosensitive material.

As one of preferred embodiments of the present invention, phenidone and the like (including derivatives thereof) are contained in the inorganic developer together with ascorbic acid and the like. When the inorganic developer contains phenidone or the like, the sensitivity is further increased. As the ascorbic acid of the present invention, preferred specific examples of the compound represented by the general formula (I) include imino-1-erythroascorbic acid, imino-1-ascorbic acid, imino-d-glucoascorbic acid and d-
Glucoascorbic acid, 1-erythroascorbic acid,
Examples include 1-fucoa ascorbic acid and imino-1-fucoa ascorbic acid.

In the present invention, the total opening of the developer of the developing apparatus is 0.005～1.0Cm ^-1, preferably 0.01~0.3cm ^-1. The total opening degree (K) in the present invention is obtained by dividing the total area (Scm ² ) where the processing liquid in the processing tank comes into contact with air by the total liquid amount (Vcm ³ ) in the processing tank K = S / V ( cm ^-1 ).

The present invention will be described in more detail below. The metal constituting the organometallic complex salt (metal compound) of the transition metal used as the metal complex-type developing agent in the present invention is T
transition metals such as i, V, Cr, Mn, Fe, Co, Ni and Cu, preferably Ti, V, Cr and Fe,
They have the property of being able to assume several different oxidation states.

Therefore, when it is used as a developing agent, theoretically, it is sufficient to use one having an oxidation state smaller than the maximum oxidation state to utilize its reducing power.
In Ti Ti ^3+, the V V ^2+, the Cr Cr ^2+, the Fe Fe ²⁺ is used. Among them, Ti ³⁺ , Fe ^{2+ and the} like are more preferably used.

Such a metal compound is a complex salt, the complex salt having Ti ³⁺ or Fe ²⁺ as a central metal, and the ligand is preferably a multidentate ligand.
Specific examples of such a ligand include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid (EDTA) and diethylenetriaminepentaacetic acid (DTPA) or salts thereof,
Ethylenediamine-N, N, N ', N'-tetramethylene phosphoric acid, 1,3-diaminopropanol-N, N,
Aminopolyphosphoric acids such as N ', N'-tetramethylenephosphoric acid or salts thereof, carboxylic acids such as nitrilotriacetic acid, oxalic acid, citric acid or salts thereof, nitrilo-N, N,
Examples thereof include phosphoric acids such as N-trimethylene phosphoric acid and propylamino-N, N-dimethylene phosphoric acid, and salts thereof.

Among these, EDTA and DTPA
A complex salt having, for example, as a ligand is preferably used. Further, such a complex salt can be formed in a developing solution by adding a metal salt and a ligand compound, and such a method is also preferable in the present invention. For details of such metal compounds, reference can be made to the descriptions in Japanese Examined Patent Publication No. 54-41899 and the documents cited therein.

The content of such a metal compound in the developer is 1 to 100 g / liter, preferably 5 to 50.
It may be g / liter.

Further, such a developing solution may contain various additives such as a pH buffering agent and an antifoggant, and such additives are described in JP-B-54-41.
No. 899, etc. The pH of the developer is 0.5 to 11, more preferably 1 to 11, and preferably 2.5 to 11.
Used in the range of 9.

It is preferable that the developer used for the energization process contains a chelating agent capable of forming a complex salt with a metal. Specific examples of the water-soluble chelating agent are shown below. The following compounds are acids and salts (Li ⁺ , Na ⁺ , K ⁺ , N
H ₄ ⁺ ). (1) Carboxylic acid type (abbreviation) CyDTA: cyclohexanediaminetetraacetic acid trans type DHEG: dihydroxyethylglycine DTPA: diethylenetriaminepentaacetic acid DPTA-OH: diaminopropanoltetraacetic acid EDAPDA: ethylenediaminediacetic acid dipropionic acid EDDA: ethienediaminediacetic acid EDDHA: ethylenediamine diorthohydroxyphenylacetic acid EDDP: ethylenediamine dipropionic acid EDTA-OH: hydroxyethyl ethylenediamine triacetic acid GEDTA: glycol ether diamine tetraacetic acid HIDA: hydroxyethyliminodiacetic acid IDA: iminodiacetic acid methyl-EDTA: diaminopropanetetraacetic acid NTA: nitrilotriacetic acid NTP: nitrilotriapropionate m-PHDTA: metaphenylenedia Emissions tetraacetate TTHA: triethylenetetraminehexaacetic acid m-XDTA: metaxylylene over diamine tetraacetic acid EDTA: ethylenediaminetetraacetic acid Ani hepcidin blue; Chromazurol S; full oxine;
Methyl thymol blue; methyl xylenol blue; circus syncresol red; stilbene fluor blue S; N, N-bis (2-hydroxyethyl) glycine (2) phosphonic acid type, phosphoric acid type ethylenediaminetetrakismethylenephosphonic acid nitrilotrimethylenephosphonic acid 1 -Hydroxyethylidene-1,1-diphosphonic acid 1,1-diphosphonoethane-2-carboxylic acid 2-phosphonobutane-1,2,4-tricarboxylic acid 1-hydroxyethylidene-1,1-diphosphonic acid 1-hydroxy-1-phospho Nopropane-1,2,3-
Tricarboxylic acid Catechol-3,5-diphosphonic acid Sodium pyrophosphate Sodium tetrapolyphosphate Sodium hexametaphosphate α-Alkylphosphonosuccinic acid 1-Hydroxyorgano-1,1-dicarboxylic acid 1-Aminoalkane-1,1-diphosphonic acid 2 -Phosphonobutane-1,2-dicarboxylic acid (3) Hydroxyl group Alizarin complexone; Arsenazo-III; Berylone-II; Bispyrazolone; n-benzoyl-N-
Phenylhydroxylamine; Bromopyrogallol Red; Eriochrome Black T; 1- (1-hydroxy-2-naphthylazo) -6-nitro-2-naphthol-
4-sulfonic acid calcein; calcein blue; calcirome;
Chalcone; Calmagite; Carboxyarsenazo;
Chlorophosphonazo-III; chloranilic acid; chromotropic acid; dimethylsulfonazo-III; dihydroxyazobenzene; dinitrohydroxyazo-III; dinitrosulfonazo-III; 2-furyldioxime; glycine resole red; glyoxal-bis (2
-Hydroxyanyl); naphthylazoxin; naphthylazoxin S; 2-hydroxy-1- (2-hydroxy-4-sulfo-1-naphthylazo) -3-naphthoic acid 2- (2-pyridylazo) chromotropic acid; 1 −
(2-pyridylazo) 2-naphthol; 4- (2-pyridylazo) resorcinol; phenazo; pyrocatechol violet; Tyrone; acetylacetone;
Fluoryltrifluoroacetone; Hexafluoroacetylacetone; Pivaloyltrifluoroacetone;
Trifluoroacetylacetone; N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid; triethanolamine (4) Nitrogen-based and sulfur-based arsmates; bathocuproine; bathocuproine sulfonate; bathophenanthroline; Bathophenanthroline sulfonic acid; bismuthiol-II; 3,3'-diaminobenzidine;diantipyrylmethane;monopyrazolone;murexide;o-phenanthroline; thiooxine These chelating agents prevent the precipitation of components due to mass transfer. Therefore, it is preferable for preventing precipitation due to the water quality of the liquid (for example, containing calcium). Furthermore, it is better to include a metal ion that easily causes redox.
It is also effective in preventing unnecessary reactions at the electrodes. In this case, it is preferable to include a chelating agent having a theoretical metal ion chelating ability of 1.1 mol or more with respect to the metal ion. The theoretical metal ion chelating ability is preferably 1.5 mol or more, more preferably 2.0 mol or more. That is, it is preferable that the chelating agent is present in an excessive amount with respect to the metal ion. This is to prevent the precipitation of metal, the precipitation of calcium in the liquid, and the precipitation caused by the substance moving through the anion exchange membrane.

In this case, it is not preferable for the electrolyte solution to move to the developing solution side, so that the chelating agent used preferably has a large molecular weight. Moreover, chelating agents that are stable with metal ions are preferred. The molecular weight of the chelating agent is 40
It is preferably 0 or more and 1,000,000 or less. It has a molecular weight of 10
If it is larger than 0,000, it will not dissolve in water, and if it is smaller than 400, it will pass through the anion exchange membrane.

The stability constant (generation constant; log K) showing the stability of the chelating agent with metal ions is from 2.0 to
40.0 is preferable. Metals that can be used as a chelating agent include iron, aluminum, titanium, nickel, and cobalt, which are easily available and relatively stable.
Further, when the electrolyte solution is used as the anode side, it is better to add an alkaline buffer solution because a slight amount of acid is generated by energization. On the contrary, when it is used as the cathode side, it is better to add an acidic buffer solution because it produces an alkali.

In the present invention, a developing solution containing a metal compound capable of reducing exposed silver halide as a developing agent is used for the development processing of the black-and-white light-sensitive material. Then, at this time, the developer is brought into contact with the electrolyte solution through the anion exchange membrane, and the cathode is immersed in the developer and the anode is immersed in the electrolyte solution, and the photosensitive material is processed while energizing both electrodes. .

The energization treatment according to the present invention means that a part of the treatment tank is substantially partitioned by an anion exchange membrane, a cathode and an anode are provided through the anion exchange membrane to energize, and no electricity is required through the anion exchange membrane. In this treatment method, a substance or a necessary substance is moved to a desired side, and a liquid component is oxidized or reduced by a reaction on an electrode surface. The number of ions that move through the anion exchange membrane of an electrode reaction or an ionic compound is proportional to the amount of current flowing through the electrode surface according to Faraday's law. A voltage is applied to cause this current, but the voltage must be appropriate,
Usually, it is 0.1-10V, preferably 0.3-5V. If the voltage is lower than this value, the current does not flow, and if the voltage is higher than this value, an unnecessary electrode reaction occurs and the reaction efficiency (current efficiency) with respect to the target is lowered.

Therefore, if a constant current power supply is used, the energization process can be properly controlled only by the time control, but in the case of a power failure or when the power is temporarily cut off, the current is not supplied as set, so this method is used. Is not suitable, and since such a constant current power source is expensive, it is preferable to use a power source that is as inexpensive as possible (battery or secondary battery).

When a battery or a secondary battery is used as a power source, a current decrease due to a voltage decrease occurs and it is difficult to manage the current. In this case, it is necessary to energize so that the current value × time becomes constant with respect to the predetermined processing amount of the photosensitive material. To measure current value x time, use an integrating ammeter (ammeter)
May be used to measure the integrated amount of the current value. As the ammeter, when a constant current power supply is used, various commercially available ammeters can be used, and it is sufficient to integrate only the time when the ammeter flows. When it is not a constant current power source, a commercially available coulomb meter or an integrating ammeter can be used.

For example, the developer can be properly regenerated by energizing the developer so that an electric quantity of a predetermined coulomb is applied to the developer for processing one film for photographing. In an automatic developing apparatus that has many processing tanks to be energized, the cost of the power supply can be reduced if the energization is not performed simultaneously and the time is staggered. Further, when the anion exchange membrane is continuously used, the membrane resistance may increase due to clogging or the like. In this case, if an attempt is made to flow a constant current value, the applied voltage may rise, which may be undesirable. In order to prevent such a case, it is necessary to keep the film resistance below a certain level. On the contrary, in this case, when a constant voltage is applied, the current value gradually decreases. Also at this time, energization processing becomes possible by controlling so that current × time for a predetermined processing amount of the photosensitive material becomes constant.

As described above, the energization process may be controlled by the amount of current according to Faraday's law, but in some cases, the change in the bulk potential of the developer is detected, and this data and the amount of current are combined to obtain the amount of energization. May be determined. The control means at this time may make a fuzzy decision. To measure the redox bulk potential of the developer, the redox potential measuring instrument described in JP-A-60-195544 and 60-195545 can be used. Moreover, this potential may be detected and controlled by the control method described in the publication.

For example, in the case of a developing solution, energization is controlled so that the oxidation-reduction potential is within a predetermined range, and when the oxidation-reduction potential exceeds a set upper limit value, the energization is interrupted to interrupt the oxidation of the developing solution. . The redox potential of the developing solution decreases as the photosensitive material is processed during interruption of energization, but when the redox potential falls below the lower limit value, energization is started to oxidize the developing solution and raise the potential.

In the present invention, the energization is preferably performed during the processing, and by doing so, the development activity can be maintained during the processing. Then, when the processing is completed and, for example, a signal indicating the completion of the processing of the photosensitive material is received, the energization may be terminated.

The cathode used in the present invention may be any electric conductor or semiconductor that can withstand long-term use, but stainless steel is particularly preferable. The anode may be made of an insoluble material and an electric conductor, and specific examples thereof include carbon (graphite), lead dioxide, platinum, gold, titanium and copper, and stainless steel may be used depending on the case. The shape of the both electrodes is preferably a plate shape that is easy to install in the tank, a mesh plate shape or a plate shape with protrusions. The size may be appropriately selected depending on the tank capacity.

As the anion exchange membrane used in the present invention, any one can be used as long as it selectively permeates anions, and a commercially available one can be used as it is. In this case, the anion exchange membrane to be used can be selected according to the valence of the anion which is preferably transferred through the anion exchange membrane. For example, for the purpose of permeating halide ions such as Br ⁻ accumulated in the developing solution, an anion exchange membrane selectively permeating only monovalent anions may be used.

In the present invention, a cation-exchange membrane is used as the diaphragm for partitioning the current-carrying chamber for conducting electricity.
Examples include anion exchange membranes and other permeable membranes. Of these, an anion exchange membrane is preferably used, but any anion exchange membrane may be used as long as it selectively permeates anions, and a commercially available one can be used as it is. . Such anion exchange membranes include Selemion AWV / AMR (manufactured by Asahi Glass), Aciplex A201, A172 (manufactured by Asahi Kasei), Neosepta AM-1 to 3 (manufactured by Tokuyama Soda), Ionac MA-3148 (Ionac Ch).
manufactured by E.Malicals), Nepton AR103PZL
(Made by Ionics) or the like may be used, but Br is preferably used when an energization chamber is provided in the color developing tank for energization.
^- in order to the transmission of a halide ion such as, Selemion AS that selectively transmit monovalent anion
V / ASR (Made by Asahi Glass), Neosepta AFN-
It is preferable to use a commercially available product such as No. 7, Neosepta ACS (manufactured by Tokuyama Soda).

As the permeable membrane, a Yumicron diaphragm (made by Yuasa Battery) used in a storage battery; Torio Higaki, "Fine Electronics and Highly Functional Materials" (CMC, 198).
3rd year), pages 125-132; solid polymer walls; porous polymer plates (for example, xanthone porous film or fiber cloth), porous polyester fiber cloths (for example, Toray Welkey); urethane, polyethylene, polypropylene, etc. A permeable membrane such as a foam wall is used. These can be used instead of the composite porous membrane.

In the present invention, the above-mentioned anion exchange membrane is a generic term for membranes that selectively permeate anions. In this sense, the pore diameter is 0.2 to 20.
It also includes a film of a porous ceramic having a thickness of μm.

As the electrode used for energization, the cathode, which is one of the electrodes, may be any electric conductor or semiconductor capable of withstanding long-term use, such as stainless steel, aluminum, silver, nickel, copper, Examples of the metal material include zinc, brass and titanium, and stainless steel is particularly preferable. The anode may be made of an insoluble material and an electric conductor, and specific examples thereof include carbon (graphite), lead dioxide, platinum, gold, and titanium steel. In some cases, stainless steel may be used. Good. The shape of both electrodes is preferably a plate shape that is easy to install in the tank, a meshed plate shape, or a plate shape with protrusions. The size may be appropriately selected depending on the tank capacity. Furthermore, by forming the plate-shaped electrode extremely thin to have flexibility, the plate-shaped electrode can be easily wound, and the operation of immersing it in the liquid or taking it out in the air becomes easy. Further, with such a configuration, it is possible to adjust the immersion depth of the electrode in the liquid to adjust the substantial electrode area.

The electrolyte solution used in the present invention is not limited, but as the electrolyte, NaCl, KCl, LiCl, N
HaBr such as aBr, KBr, KI, Na ₂ S
Sulfates such as O ₄ , K ₂ SO ₄ , KNO ₃ , NaN
O _3, NH ₄ NO _3, etc. _{nitrate, Na 2 CO 3, K 2} C
It is preferable to use a carbonate such as O ₃ or the like. The concentration of the electrolyte in the electrolyte solution at this time is 0.01 to 30.
%, Preferably 0.01 to 20%. In addition, a diluting solution of the fixing solution can be used. Further, a developing solution, a fixing solution, and a waste water of washing water may be diverted.

Even when ion-exchanged water is used as the rinse liquid itself, the rinse liquid after use should be
Salt, which is a fixer component brought into the photosensitive material, is mixed. Therefore, there is no problem in using the waste liquid even with the rinse liquid,
As a result, the amount of waste liquid can be reduced.

As the above-mentioned rinse solution, a usual one may be used, and preferably, one to which antibacterial agents, antifungal agents, dye eluting agents, decolorizing agents and the like are added. Regarding electrolysis conditions, electrode materials, types of exchange membranes, etc., JP-A-3-273237
Those described in Japanese Patent Publication No. The light-sensitive material in the present invention is various black-and-white light-sensitive materials. For example, black and white negative film, black and white photographic paper, black and white reversal film, black and white reversal photographic paper, black and white positive film, photographic light-sensitive material for plate making, X-ray photographic light-sensitive material, light-sensitive material for micro, color reversal film,
Examples include color reversal printing paper.

The color reversal film and the color reversal photographic paper are color light-sensitive materials, and the black-and-white developer of the present invention can be used as the first developer of the color light-sensitive material.

The pH of such a black-and-white developing solution is 2 to 8.5.
The range of is preferable. More preferably pH 4 to
The range is 7.5. In the present invention, the fixing solution used in the fixing process after the development process of the black-and-white light-sensitive material is an aqueous solution containing a fixing agent and has a pH of 3.8 or more, preferably 4.2 to 7.
Has 0. Examples of the fixing agent 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 3 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. For the fixing solution, tartaric acid, citric acid, gluconic acid or their derivatives can be used alone or in combination of two or more. It is effective that these compounds contain 0.005 mol or more per liter of the fixer, particularly 0.01 to
0.03 mol / l is particularly effective.

Preservatives (eg, sulfite, bisulfite), pH buffering agents (eg, acetic acid, boric acid), pH adjusters (eg, sulfuric acid), chelating agents having a water softening ability may be included in the fixing solution, if desired. Or the compounds described in JP-A-62-78551. In the processing of the black-and-white light-sensitive material, the rinsing processing is performed after the fixing processing. This rinse liquid has a function of removing the residual treatment chemical in the previous step, and is used almost synonymously with washing liquid and washing water.

In this rinse treatment, the photosensitive material 1 m
The replenishment amount can be 3 liters or less per ² parts, and in this case, it is preferable that the rinse liquid is provided with a mildew-proofing means. As the antifungal means, the ultraviolet irradiation method described in JP-A-60-263939, the method using a magnetic field described in JP-A-60-263940, and the ion exchange resin described in JP-A-61-131632 are used. A method of making pure water, a method of blowing ozone, JP-A Nos. 62-115154 and 62-153.
No. 952, No. 62-220951, No. 62-2095.
No. 32 and JP-A-1-91533 can be used.

Furthermore, LF West. “Water Quality
Criteria ”Photo. Sci, & Eng. Vol. 9 No.6 (1965), M.
W. Beach, “Microbiologica1 Growths in Motion-pict
ureProcessing ”SMPTE Journa 1 Vol. 85, (1976), R.
O. Deegan, “Photo Processing Wash Water Biocide
s "J. Imaging Tech 10, No.6 (1984) and JP-A-57.
-8542, 57-58143, 58-105.
No. 145, No. 57-132146, No. 58-1863.
No. 1, No. 57-97530, No. 57-157244 and the like can be used in combination with antibacterial agents, antifungal agents, surfactants and the like.

Furthermore, RT Kreiman, J. Image. Te
ch 10, (6) p. 242 (1984), isothiazoline compounds, Research Disclosure Volume 205, No. 20526 (19
1981, May issue), isothiazoline compounds,
Isothiazoline compounds described in Vol. 228, No. 22845 (April, 1983), JP-A-62-209532.
The compounds described in Japanese Patent Publication No.
It can also be used together as e).

In addition, as described in "Chemistry of Antibacterial and Antifungal", Hiroshi Horiguchi, Sankyo Publishing (Showa 57), "Handbook of Antibacterial and Antifungal Technology", Japan Society of Antibacterial and Antifungal, Hakuhodo (Showa 61) Various compounds may be included. A stabilizing solution may also be used for the processing of the black-and-white light-sensitive material. For details of the processing of the black-and-white light-sensitive material, see JP-A-1-937.
37, JP-A 1-250947, JP-A 2-103
No. 035, JP-A No. 2-103037, and JP-A No. 2-71.
The description in JP-A No. 260, JP-A No. 61-267559 and the like can be referred to.

Details of the black-and-white or color light-sensitive material of the present invention are disclosed in JP-A-1-259359 and the above-mentioned patent documents.

[0052]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of the present invention will be described below with reference to the accompanying drawings. However, the present invention is not limited to this embodiment. FIG. 1 is a schematic plan view of an automatic developing device.
In the automatic developing device, a developing tank 2, a fixing tank 4, and a washing tank 6 are arranged in this order. The developing tank 2 has a developing solution, and the fixing tank 4 has a fixing solution.
The washing tank 6 is filled with washing water. The exposed light-sensitive material (black and white) is sequentially dipped in each processing solution for processing, and the light-sensitive material S that has been washed with water is dried in a drying unit (not shown).

Although the developing tank 2 is filled with the developing solution,
An energizing tank 8 is provided adjacent to the developing tank 2, and the developing tank 2 and the energizing tank 8 are partitioned by an anion exchange membrane 10. An electrolyte solution is filled in the energization tank 8, and the electrolyte solution and the developing solution are in contact with each other via an anion exchange membrane 10. Further, the cathode 12 is installed in contact with the developing solution, and the anode 14 is installed in contact with the electrolyte solution.
14 is energized by a power supply 16.

The timing of energizing the developing solution may be before development processing, during development processing, or after development processing. It is particularly preferable to carry out an energization process before the development process to restore the performance of the developer, and when the development process is actually started, the performance of the developer can be kept in a good state. Deterioration of the developing solution is mainly due to the progress of the developing process and the chelating metal ion which is the developing agent has a high ionic valence.
By immersing the cathode 12 in the developing solution and energizing it, electrons are given from the cathode 14 to the chelate metal ion having a high ionic valence, and the metal ion is reduced and regenerated. Therefore, the energization treatment during the development treatment is preferable in that the development efficiency is improved. Further, the chelate metal ion is also oxidized by oxygen in the air, and as a result, the developing performance is lowered. Therefore, by conducting electricity before the development process,
It is preferable to regenerate a large amount of chelate metal ions having a low ionic valence in the developer to recover the developing performance. As for this, if the opening degree is small, it is not necessary to regenerate by energizing in advance.

As described above, when the opening degree is small, it is not necessary to regenerate the electric current through the passage of time, so that the pH of the developing solution can be set low, so that even if ascorbic acid is contained in the developing solution, it can exist stably. Then, the reducing property of ascorbic acid can prevent air oxidation of the inorganic developing agent. In addition, since the developing tank is energized, electrons are generated from the cathode when energized, and the electrons decompose oxygen that enters the developer from the air and are known as unstable compounds. It is considered that the existing ascorbic acid is present more stably in the developer.

The present invention contains ascorbic acid in the developing solution to eliminate the need for energizing the air-oxidized component of the inorganic developing agent,
The processing device can be simplified and the energization control device can be facilitated. Furthermore, the addition of ascorbic acid to the developer increases the sensitivity of the image. Further, the sensitivity is further increased by including phenidone and the like in the developer together with ascorbic acid.

FIG. 2 is a sectional view of a developing tank of a photosensitive material processing apparatus used in a comparative example and its modification. The processing tank 20 is provided with an electrolytic chamber E1 separated from a developing tank D1 filled with a developer with an anion exchange membrane, a developing chamber D1 is provided with a cathode 27, and an electrolytic chamber E1 is provided with an anode 26. A means Q for energizing is provided between the two electrodes. The processing tank 21 is provided with an electrolytic chamber E2 with a developing tank D2 filled with a developing solution and a permeable membrane 22 separated from each other. A cathode 29 is installed in the developing tank D2 and an anode 28 is installed in the electrolytic chamber E2. A means P for energizing is provided between the two electrodes. In the developing tanks D1 and D2, the developer is circulated by pipes 24 and 25.

The processing tank 20 and the processing tank 21 are used for the processing performed in the embodiment. For example, the energization processing depending on the processing amount of the photosensitive material may be performed by combining the energization means Q using only the processing tank 20 or the energization means P using the processing tank 21 with the energization means Q. In addition, the energization processing depending on the unprocessed elapsed time may be performed by the energizing means Q or may be performed by the energizing means P. There is a difference in the results obtained by each energization method.

The anion exchange membrane used in this embodiment is Satoku Tokuyama; AM-3, and the permeable membrane is Yumicron; 0.2 μm.

FIG. 3 shows a modification of the developing tank of the photosensitive material processing apparatus used in the comparative example. The processing tank 30 is provided with electrolytic chambers E3 and E4 with a developing tank D3 filled with a developing solution and an anion exchange membrane 23 or a permeable membrane 22 separated from each other.
3, a cathode 38 is installed, an electrolysis chamber E3 is equipped with an anode 37, and an electrolysis chamber E4 is equipped with an anode 39.
Means Q for energizing between the both electrodes of the anode 37 and cathode 38 for the processed amount of the photosensitive material, and means for energizing between the both electrodes of the anode 39 and cathode 38 for the unprocessed elapsed time. P is performed. A developing solution is circulated through the pipes 34 and 35 for the electrolytes E3 and E4.

[0061]

【Example】

Example 1 (Photosensitive material): Sample 6 described in Example 1 of Japanese Patent Application No. 4-125407 was used (Processing and formulation): Process Development Fixing Washing time 30 seconds 20 seconds 20 seconds Temperature 38 ° C 38 ° C 38 ° C Prescription The following prescription GR-made by Fuji Photo Film Co., Ltd.
F1 Fixing Agent (Formulation Y: Present Invention) Developer Treatment Formulation 1 liter Formulation Diethylenetriaminepentaacetic acid 78.6 g Ammonia water (25%) 50.0 ml Primary sulfate group (7-hydrate) 44.6 mg Sodium sulfite 5.0 g Phenidone 0.5 g Isoascorbic acid 40 g NaBr 1.5 g Sodium carbonate 30.0 g 2-Mercapto-benzothiazole 50.0 mg pH 8.5 (Formulation X: Comparative example) Water 800 ml Ammonia water (28%) 100 ml * EDTA 60 g citric acid (anhydrous) 38.4 g KBr 1 g ferrous sulfate (7H ₂ O) 55.6 g [FeSO ₄ · 7H ₂ O] pH adjusted to 6.5 to 7.0 1 liter [ EDTA: ferrous sulfate = 2: 1 (molar ratio)] * EDTA (4H) POTITE 4H (EDTA-Free ac d) (manufactured by Wako Pure Chemical Industries, Ltd.)

(Process 1A: Conventional) The processing apparatus shown in FIG. 1 was used, except that the developing tank was changed to that shown in FIG. 2 and only the energizing means Q in FIG. I went. In this case, turn off the air and leave it in the air 2
K if current is applied for a day (energization condition: 1.2V; 2.5mA)
Initial performance was obtained by adding 191 liters of Br (38 ° C. development 30 seconds fixing 20 seconds water washing 20 seconds), but initial performance was not obtained when left in the air.

(Treatment 1B: Comparison) In Treatment 1A, while the treatment liquid is left untreated in the air, the energizing means P shown in FIG. 2 is used so that the initial potential does not change in the developing tank.
Energize once every 0 minutes (energization condition: 2.4 V; 100 m
After A), the same initial performance was obtained on the second day. When the photosensitive material was treated, the electricity was supplied to the electricity supply tank of Q (2 V; 1.5 A), and the performance deterioration was small even in the second week.

(Process 1C: Comparison) FIG. 2 used in Process 1B
In place of the energizable developing tank shown in FIG. 3, the energizing developing tank of FIG. 3 is used and the developing means P and the developing means Q of FIG. 3 are left untreated in the air in the same manner as the treatment 1B. The electricity was separately applied while the material was being processed and when the photosensitive material was processed. As a result, the same result as that of the process 1B was obtained. The apparatus of Process 1C is simpler than that of Process 1B.

(Processing 1D: Inventive) When a developing solution of formulation Y was used by using the processing apparatus shown in FIG. 1 in the processing 1A, it was possible to process the photosensitive material even if it was left untreated in the air. No deterioration of photographic performance was observed with only the energizing means Q.
This state could be maintained for 2 weeks. As shown in Comparative Examples 1B and 1C, stable performance was obtained without using a complicated device and without controlling the energization of the energizing means P and the energizing means Q as shown in FIG. It is presumed that the formulation X and the formulation Y contributed to the stable performance by using only the energizing means Q because the formulation Y contained the ascorbic acid derivative.

Upon detailed examination, it was found that the inclusion of phenidone also contributed a little. The Dmax concentration values (after 2 weeks) are shown below.

[0067]

[Table 1]

Example 2 The same procedure as in Example 1 was carried out except that the components of Formulation Y were changed as shown in Table 2 below, and the period during which the performance of the developing solution could be maintained was examined. The results are shown in Table 2 below. However, Dmax of 4.5 or less is not practical.

[0069]

[Table 2]

In Example 2B of Table 2 above, a formulation excluding phenidone from Formula Y was used, in Comparative Example 2A a formulation excluding ascorbic acid from Formula Y was used, and in Comparative Example 2B, phenidone and ascorbic acid were eliminated. The recipe was used.
As a result, when the developer contains ascorbic acid and phenidone of Example 2A, the difference in performance between the developers on the first day and the 14th day was 0.02, and the performance of the developer was not maintained. It turns out to be sufficient. In addition, Example 2B containing only ascorbic acid in the developing solution had a shorter period of time in which the performance of the developing solution could be maintained than Example 2A containing ascorbic acid and phenidone, but 14 days did not maintain practical performance. To be kept. On the other hand, in Comparative Example 2A in which ascorbic acid was removed from Formulation Y, the performance of the developer declined to 4.20 after 14 days. Furthermore, in Comparative Example 2B which does not contain both ascorbic acid and phenidone, the performance of the developer is deteriorated from the first day.

From the above, when ascorbic acid alone or ascorbic acid and phenidone are contained in the developing solution, it is possible to store for a considerably long time.

<Example 3> The same results were obtained by using the scanner film LS-4000 manufactured by Fuji Photo Film Co., Ltd. as the photosensitive material in the processing 1D of Example 1. That is, an image with good sensitivity was obtained regardless of the presence or absence of Se sensitization.

<Example 4> In Example 4, the relationship between the developing solution and the opening degree of the developing solution portion when the developing solution of the formulation Y of the present invention was processed by the processing apparatus shown in FIG. 1 was examined. It is data when the opening degree K is shown in FIG. (Treatment liquid) Formulation Y of Example 1 (Electrification treatment) The apparatus shown in FIG. 1 used in Example 1 is used. (Running condition): (Photosensitive material) The photosensitive material of Example 1 is cut into quarters.
Processing per sheet / day (Processing): The same as in Example 1 except that the replenishing amount was changed as follows: Replenishing amount of developing solution Formulation Y 0.5 ml / fixing solution GR-F1 5 ml / 4 cuts Washed with tap water 50 ml / 4 cuts However, mother liquor and replenisher are the same (current condition: developer only) Anode: Kureha Chemical's Kureka sheet 5 mm thick 10
0mm × 250mm Cathode: Stainless SUS316 1mm thickness 10
0 mm × 200 mm Anion exchange membrane: Tokuyama Soda AM-3 current density 0.3 A / dm ² ; energization amount 0.6 A × 10 seconds /
Photograph performance: cut in four: Evaluation by Dmax Let K be the opening degree of the developing tank portion of the processing apparatus shown in FIG.
The opening degree is K = Scm ² (surface area of the developing solution in contact with air) / Vcm ³ (developing solution volume).

[0074]

[Table 3]

When the aperture ratio K = 0.01 to 1.0 cm ⁻¹ , the photographic properties can be used almost stably. However, considering the ease of making the processing tank and the absolute value of Dmax, K =
0.03 to 0.30 cm ^-1 can be used.

<Example 5> (Photosensitive material): The same as the photosensitive material of Example 1 (Processing): The same as Example 1 except that the replenishment amount of the processing of Example 1 was changed as follows. Processing solution Replenishing amount Developer Y Prescription Y 0.5 ml / four cut Fixer GR-F1 5 ml / four cut Washing tap water 50 ml / four cut However, mother solution and replenisher same K = 0.1 cm ^-1 can be energized Long-term running was carried out as in Example 4 in a processor having a developing tank.
I was able to run by moving between Dmax = 4.95 and 5.33 for a month.

When K = 0.1 cm ^-1, it was easy to make a machine.

<Example 6> When a long-term running was carried out as in Example 4 in a processor having a developing tank of K = 0.1 cm ^-1 which can be energized, Dmax = 4.95 ~ for 3 months.
I was able to run by transitioning between 5.33. K = 0.1
It was easy to make a machine when it was cm ^-1 . (Treatment process and formulation) Process Development Fixing Washing time 20 seconds 20 seconds 20 seconds Temperature 38 ° C 38 ° C 38 ° C Formulation The following formulation GR-made by Fuji Photo Film Co., Ltd.
F1 fixing agent (formulation Z1: the present invention) developer processing formulation 1 liter formulation diethylenetriaminepentaacetic acid 78.6 g aqueous ammonia (25%) 50.0 ml primary sulfate group (7-hydrate) 44.6 mg sodium sulfite 5.0 g phenidone 0.5 g Isoascorbic acid 40 g NaBr 1.5 g Sodium carbonate 30.0 g 2-Mercapto-benzothiazole 50.0 mg pH 8.5 (Formulation Z2: Comparative example) Formulation Z1 except 40 g of isoascorbic acid was prescribed. Same as Z1 (Prescription Z3: Comparative Example) Phenidone 0.5 g from prescription Z1
Same as formulation Z1 except that (prescription Z4: Comparative Example) same as formulation Z1 except that 40 g of isoascorbic acid and 0.5 g of phenidone were removed from formulation Z1.

The results are shown below. * Since the concentration has not come out, it is not required.

S _1.0 is the logarithmic value of the exposure amount required to obtain D = 1.0, the higher the value, the higher the sensitivity, and the difference of 0.3 is 2
It will be a double difference. Prescription Z3 came to be out of S _1.0 compared to prescription Z4. Moreover, Dmax came out as much as 6.79 times. Prescription Z2 has S _1.0 compared to prescription Z4
Something that doesn't come out came out. Moreover, Dmax came out as much as 5.18 times.

That is, the prescription Z3 has a large effect of increasing Dmax, and the prescription Z2 has a large effect of increasing S _1.0 . Therefore, Z1 which is a mixture of Z2 and Z3 has high sensitivity and Dma
x also becomes significant and becomes larger than the effect of the sum at Dmax as shown below. Z1-Z4 >> (Z2-Z4) + (Z3-Z4) After leaving the formulations of Z4 to Z1 for 1 week, they were treated with a current of 0.6 A for 10 seconds in the current-carrying tank of Example 1 to obtain Dmax.
[Dmax (new state) -Dmax (after 1 week)] resulted in the following concentration.

[0082] That is, it was found that in the liquid containing isoascorbic acid, the decrease in Dmax was remarkably suppressed when combined with energization.

[0083]

According to the present invention, by incorporating ascorbic acid or the like in the developing solution, it is possible to prevent air oxidation of the inorganic developing agent, facilitate the energization control, simplify the processing tank, and further improve the structure of the processing apparatus. Is simple, and maintenance is easy, and the obtained image quality is good.

[Brief description of drawings]

FIG. 1 is a schematic plan view showing a tank configuration of a photosensitive material processing apparatus applied to the present invention.

FIG. 2 is a cross-sectional view showing a configuration of a modified example of an energizable development processing tank of a photosensitive material processing apparatus used in a comparative example.

FIG. 3 is a cross-sectional view showing the configuration of a modified example of the energizable development processing tank of the photosensitive material processing apparatus used in the comparative example.

[Explanation of symbols]

 D developing tank E electrolysis chamber F fixing tank W1 to W2 water washing tank St stabilizing tank 12 cathode 14 anode 10 anion exchange membrane

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[Procedure amendment]

[Submission date] April 26, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0044

[Correction method] Change

[Correction content]

The pH of such a black-and-white developing solution is preferably in the range of 3-9 . More preferably, it is in the range of pH 5-9 . In the present invention, the fixing solution used in the fixing process after the development process of the black-and-white light-sensitive material is an aqueous solution containing a fixing agent and has a pH of 3.8 or more, preferably 4.2 to 7.0. Examples of the fixing agent 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 3 mol / liter.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0051

[Correction method] Change

[Correction content]

Details of the black-and-white or color light-sensitive material of the present invention are disclosed in JP-A-1-259359 and the above-mentioned patent documents. Those
Of the Japanese Patent Application No. 4-125407.
Exceptionally good when using a sensitized light-sensitive material
Performance (quickness, high gamma, high Dmax)
In particular, a selenium-sensitized light-sensitive material is particularly preferable.

Claims (5)

[Claims] 1. A cathode is brought into contact with a developing solution containing a developing agent which reacts with silver halide to become an oxidant and returns to a reduced form by giving an electron, and which contains ascorbic acid and a derivative thereof. A development processing method of processing a silver halide photosensitive material by bringing an anode into contact with an electrolyte solution in contact through an exchange membrane, applying a voltage to both electrodes and conducting an electrification process. 2. The method for processing a light-sensitive material according to claim 1, wherein the developing solution contains ascorbic acid and its derivative in an amount of 0.05 to 0.5 mol / liter. 3. The method for processing a light-sensitive material according to claim 1, wherein the developer contains phenidone and its derivative in an amount of 0.1 to 100 mmol / liter. 4. The developing solution containing ascorbic acid and its derivative in an amount of 0.1 to 0.4 mol / liter and phenidone and its derivative in an amount of 0.3 to 30 mmol / liter. The method for processing a light-sensitive material described in. 5. A cathode is provided in a developing tank filled with a developing solution containing a developing agent which reacts with silver halide to become an oxidant, which returns to a reduced form by donating an electron, and which contains ascorbic acid and its derivative. A development processing apparatus having an energization mechanism in which an anode is provided in an electrolyte solution provided via a tank and an anion exchange membrane, and an energization mechanism is used for energization reproduction according to the processing amount of a photosensitive material.