JPH07239534A - Processing method of silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain high developing property and stable performance without producing waste liquid by incorporating a specified silver halide emulsion into a photosensitive material and incorporating a polymer containing specified repeating unit and/or dextran into the emulsion layer or other hydrophilic colloid layers. CONSTITUTION:A silver halide photographic sensitive material is processed with a black and white developer containing chelate complex salt of transition metal. In this method, the photosensitive material contains a silver halide emulsion comprising planer silver halide particles having >3 aspect ratio. The emulsion layer or other hydrophilic colloid layers contain a polymer containing a repeating unit expressed by formula and/or dextran. In formula, R1 is a hydrogen atom or alkyl group, R2 and R3 may be same or different and are hydrogen atoms, alkyl groups, aryl groups, or aralkyl groups, R2 and R3 may be bonded to form a nitrogen-contg. heteroring, L is a bivalent connecting group, n is 0 to 1, m is 1 to 2, X represents mol% from 70 to 100.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a developing treatment of a silver halide photographic light-sensitive material, and more particularly to a method of treating a silver halide photographic light-sensitive material which has a high developability and is stable with no waste liquid.

[0002]

2. Description of the Related Art A black-and-white light-sensitive material is processed in processes 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 exchange water is used for washing, and a stabilizing solution is used for stabilizing treatment. The temperature of each processing solution is usually adjusted to 20 to 50 ° C., and the light-sensitive material is dipped in these processing solutions for processing.

Among these processing steps, the development processing step is a step in which a developing agent which is a reducing agent acts on silver halide grains exposed by exposure in a photographic emulsion to reduce Ag ⁺ to Ag. . In a black-and-white photograph, a silver image is formed in this way.

At this time, an organic compound such as 3-pyrazolidones or hydroquinone is used as a developing agent, and an alkaline aqueous solution of this is generally used as a developing solution. However, as a developing agent, it is known that not only such an organic compound but also a metal compound having a reducing property with respect to exposed silver halide grains can be used. In this case, the metal compound is a salt or complex of a transition metal such as Panadium-based, Titanium-based, Iron-based or Chromium-based (specifically represented by atomic symbols: Ti, Zr, Hf; V, Nb, Ta, Cr ，
Mo, W; Mn, Tc, Re; Fe, Ru, Os; Co, Rh, Ir, Ni, P
b, Pt, etc.) [Nikkan, 20 (2), 62 (1957);
Ibid, 19 , 40 (1956); Nikkan, 29 31 (1966); Photography Industry,
March issue, 67 (1967); Nikkan, No. 9, 1321 (1980); PS
E, 19 , 283 (1975); Japanese Examined Patent Publication No. 54-41899; Chiba University, Faculty of Engineering, 14 , 1 (1962); ibid, 21 (40), 169 (1970);
Ibid., 18 , 39 (1967); Id., 21 (39), 11 (1970);
0-51731; U.S. Pat. No. 3,942,985;
978 specification; British patent 1,462,972; JP-A-57-78534; PSE, 12 (6), 288 (1968); PSE, 14 (6), 391 (1
970) etc.].

When compared with organic developing agents, these metallic compounds react with preservatives in the developing solution and become irreproducible compounds, but the metallic compounds are not regenerated after development. Can be regenerated by reducing it,
Further, the organic developing agent is used in an alkaline liquid, but the metal compound can be used as an acidic or neutral aqueous solution, which allows less swelling of the gelatin film of the photographic light-sensitive material, and the gelatin of the light-sensitive material. Even if the film strength is lowered, sufficient processing can be carried out, so that the film easily enters the developing agent gelatin film and the development is accelerated. In addition, the carry-out of the treatment liquid to the next bath is reduced, so that the deterioration of the next bath liquid can be prevented. Furthermore,
The metal compound has an advantage that it can be used as a developing agent with a high concentration, but the oxidation-reduction potential of the developer changes with the passage of time or the progress of the development reaction, and the activity level cannot be stably maintained. The obtained image is inferior to the organic developing agent, and there is a defect that the development is slow.

As a method of dealing with such a problem,
A method of performing a developing treatment while electrolytically reducing a compound composed of a metal ion having an increased oxidation number generated along with the developing reaction,
Examples include a method using a large amount of replenisher. The former method of electrolytic reduction requires a certain amount of replenisher to be added because the electrolytic device is large and it is not possible to prevent the accumulation of halide ions, which causes development inhibition.
There is a cost disadvantage. Further, the latter method of increasing the replenishment amount is not only disadvantageous in terms of cost, but should be avoided in terms of environmental protection. There is also a method of activating the developer by adding a metal of the same kind to the metal complex or the metal ion in the treatment liquid (Japanese Patent Publication No. 54-41899), but it is difficult to control the addition amount of the metal. The operation becomes complicated.

Therefore, in a developing solution containing a metal compound as a developing agent, the processing performance can be easily maintained, and further, the sensitivity of an image obtained by processing with the developing solution is high and the fog is small, It is desired to speed up.

[0008]

In order to solve the above problems, the first object of the present invention is to easily maintain the processing performance using a metal compound as a developing agent and obtain an image of good photographic performance. Sensitivity and developability (especially covering power
Another object of the present invention is to provide a processing method of a silver halide photographic light-sensitive material which enhances (CP)).

A second problem is to obtain a non-waste liquid and stable performance by using a metal compound which can be regenerated many times as a developing agent and always maintaining a constant and stable metal compound in a reduced state. Another object of the present invention is to provide a method of processing a silver halide photographic light sensitive material.

A third object of the present invention is to provide a method of processing a silver halide photographic light-sensitive material by using a combination of a light-sensitive material, a processing liquid, and a current-carrying processor, which is stable and is a waste-free liquid.

[0011]

The above object of the present invention is to process a silver halide photographic light-sensitive material with a black-and-white developing solution containing a chelate complex salt of a transition metal, wherein the light-sensitive material is a flat plate having an aspect ratio of 3 or more. And / or dextran or polyhydroxyl containing a silver halide emulsion composed of granular silver halide grains and containing the repeating unit represented by the general formula [1] in the emulsion layer or other hydrophilic colloid layer. It is achieved by a method for processing a silver halide photographic light-sensitive material, which is characterized by containing a substituted benzene compound.

In the method of processing with the black-and-white developing solution, it is a preferred embodiment that the complex salt is brought into a reduced state by applying an electric current before or during the development, and the halogen salt generated by the development processing is removed.

The present invention will be specifically described below.

First, the tabular silver halide grains of the present invention have an average aspect ratio of 3 or more. The aspect ratio is a value expressed by particle diameter / particle thickness, and the larger this value, the flatter the plate. For details, see Research Disclosure 225 Item 22534 p2.
0-58) January issue, 1983 and JP-A-58-127921, 58-11
No. 3926.

The tabular silver halide grains can be produced by appropriately combining the methods known in the art. Tabular silver halide emulsion is Cugnac
And Chateau "Advancement of morphology of silver bromide crystals during physical ripening (Evolution Hoa the Morphorgie of Silver Bromide Crystals Dualing Physical Raping)" Sanence et Industry Rie Photography, Volume 33, No.
(1962) pp.121-125, Duffin, "Photographic Emulsion Chemistry (Photographi
c emulsion Chemistry) "Focal Press
ess), New York, 1966, p.66-72, APH Trivelli, WF Smith Photography
Journal (Photographic Journal), 80, 285 pages (1940
(Year) and Japanese Patent Application Laid-Open No. 58-127921,
58-113927, JP-A-58-113928, U.S. Patent 4,439,520
It can be easily prepared by referring to the method described in No. The projected area diameter of the tabular emulsion of the present invention is 0.3 to 2.0 μm,
It is preferably 0.5 to 1.2 μm. The distance between the flat surfaces (particle thickness) is 0.05 μm to 0.3 μm, particularly 0.1 to 0.
It is preferably 25 μm, and the aspect ratio is preferably 3 or more and less than 20 and particularly preferably 4 or more and less than 8. In the tabular silver halide emulsion of the present invention, silver halide grains having an aspect ratio of 2 or more account for 50% or more (projected area) of all grains,
In particular, it is preferable that 70% or more is present, and the average aspect ratio of the tabular grains is 3 or more, particularly 4 to 8. Among the tabular silver halide grains, monodisperse hexagonal tabular grains are particularly useful grains. The details of the structure and manufacturing method of the monodisperse hexagonal tabular grain according to the present invention are described in JP-A-63-151618.

As the halogen composition of the silver halide emulsion of the present invention, any of silver bromide, silver iodobromide, silver iodochlorobromide and silver chlorobromide may be used, but in order to realize high sensitivity. Further, the silver chloride content is preferably 10 mol% or less. The silver iodide content is preferably less than 1.5 mol%, particularly 0.01 mol% or more and 0.5.
It is preferably less than mol%. The silver halide grains may be composed of a uniform layer, but it is preferable that the inside and surface layers have different halogen compositions, particularly 80% or more of silver bromide, 90% or more of silver bromide, and 95% of silver bromide. It is particularly preferable that at least the outermost surface of the silver halide grains having a mol% or more is a silver iodide-containing layer.

Next, the compound represented by the general formula [1] will be described.

In the general formula [1], R ₁ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, preferably a hydrogen atom or a methyl group.

R ₂ and R ₃ each represent a hydrogen atom, a substituted or unsubstituted alkyl group having 10 or less carbon atoms, an aryl group or an aralkyl group, and may be the same or different.
Examples of the substituent include a hydroxyl group, a lower alkoxy group, a halogen atom, an amide group, a cyano group, a sulfonic acid group and a carboxylic acid group. R ₂ and R ₃ are preferably a hydrogen atom, a methyl group, an ethyl group or a phenyl group, of which a hydrogen atom is most preferred. L represents a divalent linking group,
As an example thereof, carbon number, 1-10 alkylene group, arylene group or ether bond with them, ester bond,
The divalent group obtained by combining an amide bond etc. is mentioned.

N represents 0 or 1, preferably 0, and m
Represents 1 or 2, and 1 is preferable. Further, x represents a molar percentage and represents 70 to 100.

Specific examples of preferred ethylenically unsaturated monomers constituting the repeating unit represented by the general formula [1] are shown below.

[0022]

[Chemical 2]

The repeating unit represented by the general formula [1] may contain two or more kinds of monomer units in order to exhibit a composite function as a polymer.

The high molecular weight polymer according to the present invention contains a monomer represented by the general formula [1] as a polymer constituent unit.
Mol% or more, preferably 80 mol% or more, more preferably 90
It is a compound represented by the following general formula [2] containing at least mol%.

[0025]

[Chemical 3]

In the formula, x represents a mole percentage, and x is 70 to
100 is preferred.

In the formula, A represents a monomer unit obtained by copolymerizing a copolymerizable ethylenically unsaturated monomer. R _{1 to} R ₃ have the same meaning as in the general formula [1].

The following are preferred examples of the compound of the polymer in the invention. (The number of the degree of polymerization represents a mole percentage.)

[0029]

[Chemical 4]

[0030]

[Chemical 5]

[0031]

[Chemical 6]

As a method for producing the above-mentioned polymer, generally, a radical polymerization method in an aqueous solution is industrially used, and the commercial name of acrylamide polymer is Mitsubishi Kasei Co., Ltd.
It is commercially available from and is easily available.

The weight average molecular weight (Mw) of the polymer having a repeating unit represented by the general formula [1] or [2] added to the photographic emulsion layer or its adjacent layer in the present invention is preferably 5,000 to 200,000, It is preferably 7,000 to 100,000, more preferably 15,000 to 70,000. The addition amount of such a polymer can be selected arbitrarily, but the optimum addition amount for increasing the covering power varies depending on the type of photographic emulsion. However, generally 500 mg / m ² or more, preferably 1
It is not less than g / m ^{2 and not} more than 5 g / m ² .

The dextran added to the photographic emulsion layer in the present invention is a dextran-producing bacterium such as leuconostoc, mesenteroites or a native dextran obtained by acting dextran sucrase isolated from a culture solution of these bacteria on a sucrose solution. Is a compound whose molecular weight has been reduced by the partial decomposition method using acid, alkali and enzyme. The weight average molecular weight of dextran used in the present invention is
It is 10,000 to 300,000, preferably 15,000 to 10,000, more preferably 20,000 to 70,000.

The polymer having a repeating unit represented by the general formula [1] and / or dextran used in the present invention is 5 to 50% by weight, based on the total binder in the photographic emulsion.
It is preferable to add 30 to 40% by weight. The photographic emulsion layer containing the polymer and dextran used in the present invention may be any layer, but preferably it is contained in all the photographic emulsion layers. Even better results are obtained when the non-light-sensitive gelatin layer adjacent to the photographic emulsion layer also contains the polymer of the present invention and dextran. The polymer and dextran of the present invention may be added to the non-photosensitive gelatin layer provided in the outermost layer of the light-sensitive material, and the addition amount to these non-photosensitive gelatin layers is 30% based on the binder amount of the addition layer used. It is preferably not more than weight%. The polymer and dextran may be added to the emulsion at any time, but it is suitable to add them after chemical thermal treatment and before coating.

Next, the polyhydroxybenzene compound used in the present invention will be described. In the present invention, polyhydroxybenzenes are added to the emulsion layer and / or other hydrophilic colloid layer. Regarding the technology for adding polyhydroxybenzenes, JP-A-54-40629 and JP-A-56-1936
No. 62-21143, etc. Especially JP-A-62-21
No. 143 shows that the presence of a polyhydroxy-substituted benzene compound in a concentration of less than 5 × 10 ⁻² mol per mol of silver can reduce the pressure sensitivity. Further, in JP-A-64-72141, an amount of a polyhydroxy-substituted benzene compound in a system in which tabular silver halide grains having an aspect ratio of 3 or more is color-sensitized is less than 10 × 10 ^-1 mol per mol of silver. It has been shown that the pressure sensitivity can be reduced by containing However, there is no mention of increasing the development progress. The representative examples of polyhydroxy-substituted benzene compounds that can be preferably used in the present invention are shown below.

[0037]

[Chemical 7]

In the formula, a preferable substituent of X is-
H, -OH, -Cl, -Br, -COOH, -CH 2 CH 2 COOH, -CH (CH
_{2) 2, -CH 3 -C (} CH 2) 3, -OCH 3, -CHO, -SO 3 Na, -COON
a, -SO ₃ K, -COOK and the like. In particular, hydroquinone derivatives are preferably used in the present invention. -SO ₃ Na Among these _{compounds, -COONa, -SO 3 K, -COOK} ,
-Cl and -Br are particularly preferable. The polyhydroxy-substituted benzene compound may be added at either the silver halide emulsion layer or another hydrophilic colloid layer. The addition amount is preferably less than 10 ^-1 mol per mol of silver in the light-sensitive material.

In the present invention, the black-and-white developing solution containing the organic acid complex salt of a transition metal contains pyrazolones, or the theoretical metal ion chelating ability of the chelate forming the complex salt with respect to the metal ion of the transition metal. It may contain a complex salt of 1.1 mol or more. The present invention has a good S / N ratio by containing pyrazolones in a developer containing a complex salt of a transition metal and an organic acid, and further by using an organic acid of 1.1 mol or more with respect to the transition metal. It is possible to obtain a developing solution which hardly causes precipitation of insoluble substances or reduction in the activity level of the developing solution, and a good image can be obtained by processing with this developing solution.

Conventionally, it has been known to add pyrazolones such as phenidone to a developer for the purpose of accelerating the development in organic development, but there is a problem that fog occurs in the obtained image. On the other hand, it has been found that adding pyrazolones such as phenidone as described above to the inorganic developer suppresses development fog and increases the density of shadows. That is, the noise was small and the density was easy to appear, and the so-called S / N ratio was significantly improved.

Furthermore, when an organic acid which forms a complex salt with a metal in a stable manner is added to the inorganic developer in an amount of equimolar or more, preferably 2 mol or more, the properties of the processing solution are remarkably stable and the S of a compound such as a pyrazolone compound is added. It is considered that the effect of improving the / N ratio is great. In terms of cost, the organic acid content is 5 mol or less, preferably 3 mol or less, with respect to the metal.

In the present invention, a compound capable of forming a chelate is preferable as the organic acid which stably forms a complex salt with a metal. As the pyrazolones, phenidone, phenidone Z, dimezone, dimezone S (all are trade names of Ilford) are used. The metal constituting the organometallic complex salt (metal compound) of the transition metal used as a developing agent in the present invention is a transition metal such as Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and preferably Ti, V. , Cr, Fe, which have the property of being able to assume several different oxidation states.

Therefore, when it is used as a developing agent, it is theoretically possible to use a reducing agent having an oxidation state smaller than the maximum oxidation state and utilize its reducing power.
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, and the complex salt has Ti ³⁺ or Fe ²⁺ as a central metal.
The ligand is preferably a polydentate ligand. Specific examples of such a ligand include ethylenediaminetetraacetic acid (EDTA), aminopolycarboxylic acids such as diethylenetriaminepentaacetic acid (DTPA) or salts thereof, and ethylenediamine.
-N, N, N ', N'-tetramethylenephosphoric acid, 1,3-diaminopropanol-N, N, N,'N'-tetramethylenephosphoric acid and other aminopolyphosphoric acids or salts thereof, nitrilotriacetic acid, oxalic acid Examples thereof include carboxylic acids such as acids and citric acids or salts thereof, phosphoric acids such as nitrilo-N, N, N-trimethylenephosphoric acid, propylamino-N, N-dimethylenephosphoric acid and salts thereof, and the like.

Among these, complex salts having EDTA, DTPA or the like as a ligand are 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 more information on such metal compounds,
Reference can be made to the descriptions in Japanese Examined Patent Publication No. 54-41899 and documents cited therein.

The content of such a metal compound in the developing solution is 1 to 100 g / liter, preferably 5 to 50 g / liter.
It should be liters.

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-54-41899. Has been done. The pH of the developer is 0.5 to 11, more preferably 1 to 11, and preferably 2.5 to 9.

The developer used for the main energization treatment is as follows.
It is preferable to include 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 (Ll ⁺ , Na ⁺ , K ⁺ , NH ₄ ⁺ ).

(1) Carboxylic acid type (abbreviation) CyDTA: cyclohexanediaminetetraacetic acid trans type DHEG: dihydroxyethylglycine DTPA: diethylenetriaminepentaacetic acid DPTA-OH: diaminopropanol tetraacetic acid EDAPDA: ethylenediaminediacetic acid dipropionic acid EDDA: ethylenediamine diamine Acetic acid EDDHA: Ethylenediaminedioltohydroxyphenylacetic acid EDDP: Ethylenediaminedipropionic acid EDTA-OH: Hydroxyethylethylenediaminetriacetic acid GEDTA: Glycol ether diaminetetraacetic acid HIDA: Hydroxyethyliminodiacetic acid IDA: Iminodiacetic acid methyl-EDTA: Diaminopropanetetraacetic acid Acetate NTA: Nitrilotriacetic acid NTP: Nitrilotriapropionate m-PHDTA: Meta Enirenjiamin 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-phosphonic acid 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-amino Alkane-1,1-diphosphonic acid 2-phosphonobutane-1,2-dicarboxylic acid (3) Hydroxyl group System Alizarin Complexone; Arsenazo-III; Perilone
-II; bispyrazolone; n-benzoyl-N-phenylhydroxylamine; bromopyrogallol red; Eriochrome black T; 1- (1-hydroxy-2-naphthylazo) -6-nitro-2-naphthol-4-sulfonic acid calcein Casein Blue; Calcyclome; Chalcone; Karma Guide; Carboxyarsenazo; Chlorophosphonazo-III; Chloranilic acid; Chromotropic acid; Dimethylsulfonazo-III; Dihydroxyazobenzene; Dinitrohydroxyazo-III; Dinitrosulfonazo-III; 2-
Furyldioxime; Glycine Cresol Red; Glyoxal-bis (2-hydroxyanil); 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; byrocatechol violet; Tyrone; acetylacetone; fluoryltrifluoroacetone; hexafluoroacetylacetone Pivaloyltrifluoroacetone; Trifluoroacetylacetone; N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid; Triethanolamine (4) Nitrogen-based and sulfur-based acetemates; Bathocuproine; Bathocuproine sulfone Acid; Bathophenan Throline; Bathophenan Lorin sulfonic acid; bismuthiol-II; 3,3'-diaminobenzidine;diantipyrylmethane;monopyrazolone;murexide;o-phenanthroline; thiooxine These chelating agents are used to prevent the precipitation of components due to mass transfer. , 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
It is 1.5 mol or more, and 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 metal precipitation
This is for the purpose of preventing 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 that the electrolyte solution moves 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 400
As described above, it is preferably within 1,000,000. This is because if the molecular weight is more than 1 million, it will not dissolve in water, and if it is less 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 preferably 2.0 to 40.0. Metals that can be used as chelating agents include
Iron, aluminum, titanium, nickel, and cobalt are easily available and relatively stable. Further, when the electrolyte solution is used as the anode side, a slight acid is generated by energization, so it is better to add an alkaline buffer solution. 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, and 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 processing can be properly controlled only by time control, but when a power failure or temporary power cut is made, 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 employ a power source (battery or secondary battery) that is as inexpensive as possible.

When a battery or a secondary battery is used as a power source, a current drop due to a voltage drop 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 a predetermined coulomb amount of electricity is applied to the developer for the processing of 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 the set upper limit value, the energization is interrupted to interrupt the oxidation of the developer. . 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, energization is preferably performed during processing, and by doing so, it becomes possible to maintain the development activity during 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.

In the present invention, a cation-exchange membrane is used as the diaphragm for partitioning the current-carrying chamber for conducting current.
Examples include anion exchange membranes and other permeable membranes. Of these, anion exchange membranes are preferably used.

As the anion exchange membrane used in the present invention, any one may 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 transmitting halide ions such as Br ⁻ accumulated in the developing solution, an anion exchange membrane that selectively transmits only monovalent anions may be used. As such anion exchange membrane, Selemion
AWV / AMR (Made by Asahi Glass), Aciplex A201, A172 (Made by Asahi Kasei), Neosepta AM-1 to 3 (Made by Tokuyama Soda), Ionac MA-3
148 (Ionac Chemicals), Nepton AR103PZL (Ionics
Etc. can also be used, but especially when a color developing tank is provided with an energizing chamber for energization, in order to allow halide ions such as Br ⁻ to permeate, monovalent anions are selectively permeated. Selemion ASV / ASR (Made by Asahi Glass), Neosept
It is preferable to use commercially available products such as aAFN-7 and Neosepta ACS (manufactured by Tokuyama Soda).

As the permeable membrane, the Yumicron diaphragm used in storage batteries (made by Yuasa Battery); Torio Higaki, "Fine Electronics and Highly Functional Materials" (CMC, 1983)
125-132; solid polymer wall; porous polymer plate (eg, xanthone porous film or fiber cloth), porous polyester fiber cloth (eg, Toray Welkey);
A permeable membrane such as a wall of a foam material such as urethane, polyethylene or polypropylene is used.

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

The cathode, which is one of the electrodes used for energization, may be any electric conductor or semiconductor capable of withstanding long-term use, and examples thereof include stainless steel, aluminum, silver, nickel, copper, Examples of the metal material include zinc, brass and titanium, and stainless steel is particularly preferable. Further, the anode may be made of an insoluble material and an electric conductor, and specifically, carbon (graphite), lead dioxide,
Examples include platinum, gold, and titanium steel, and stainless steel may be used in some cases. The shape of 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. 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 the electrolyte may be NaCl, KCl, LiCl, NaBr, KBr, Kl.
Such as halide, Na ₂ SO ₄ , K ₂ SO _4, etc. sulfate, KNO ₃ , N
It is preferable to use nitrates such as aNO ₃ and NH ₄ NO ₃ , carbonates such as Na ₂ CO ₃ and K ₂ CO ₃ . At this time, the concentration of the electrolyte in the electrolyte solution is 0.01 to 30%, preferably 0.01 to 20%.
%And it is sufficient. In addition, a diluting solution of the fixing solution can be used.

In the above, the electrolyte solution is newly prepared and used, but the rinse liquid may be used as the electrolyte solution. Electrolysis conditions, electrode material,
Examples of the type of exchange membrane include those described in the specification of JP-A-3-273237. Even when ion-exchanged water is used as the rinse liquid itself, the rinse liquid after use contains a salt which is a fixing liquid component carried into the photosensitive material S. Therefore, there is no problem in using it as an electrolyte solution, and it is possible to reduce the amount of waste liquid.

As the above-mentioned rinse solution, a usual one may be used, and preferably, one to which antibacterial agents, antibacterial agents, dye eluting agents, decolorizing agents and the like are added. Further, titanium ions or vanadium ions may be added to the black and white developer of the present invention, and titanium ions and vanadium ions are TiCl ₃ , VCl ₃
It was found that the sensitivity was improved by this.

Furthermore, a silver halide solvent may be added to the black and white developer of the present invention, and examples of the silver halide solvent include thiosulfate ion, thioether compound, mesoionic compound, thiourea compound, imidazole compound and mercaptoimidazole. Examples thereof include compounds, mercaptotriazole compounds and mercaptoterazole compounds.
These compounds suppress fog and increase the concentration on the shadow side with respect to Ti ³⁺ and V ³⁺ metal compounds, and improve the S / N ratio.

Furthermore, when the black and white developer of the present invention is a chelating agent iron complex salt, a nitrogen-containing compound may be added, which is preferable because the shadow concentration is increased. As the nitrogen-containing compound, amines, ammonium salts, quaternary ammonium salts, chain-like and cyclic quaternary ammonium salts may be added. For example, ammonium bromide, triethanolamine, tetramethylamine, alkanolamine and the like can be used.

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,
Examples thereof include black and white reversal film, black and white reversal photographic paper, black and white positive film, photographic photosensitive material for plate making, X-ray photographic photosensitive material, microphotosensitive material, color reversal film and color reversal photographic paper. The color reversal film and the color reversal photographic paper described above 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 developer is preferably in the range of 2 to 8.5. More preferably, it is in the range of pH 4 to 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 7.0. 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. In the developing solution system of the present invention, since the developing solution is neutral to acidic, swelling of the emulsion film of the light-sensitive material is small, and thus it is not necessary to use fixing of an acidic hardener, so that aluminum is eliminated from the waste solution of the fixing solution. Is also preferable, and fixing is also speeded up.

The fixing solution may contain a water-soluble aluminum salt which acts as a hardening agent, and examples thereof include aluminum chloride, aluminum sulfate, potassium alum and the like. In the present invention, since the developing treatment can be performed with an acidic to neutral developing solution, the content of the hardener can be reduced and the pollution can be reduced. 0 for hardener
-30 g / l, preferably 0-10 g / l may be added.

The fixing solution is an aqueous solution containing a hardening agent (for example, a water-soluble aluminum compound), acetic acid and a dibasic acid (for example, tartaric acid, citric acid or salts thereof), if necessary, in addition to the fixing agent, and preferably , PH8 or more, more preferably
Having 4.0-5.5. 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 5 mol / liter.

As the above-mentioned dibasic acid, tartaric acid or its derivative, citric acid or its derivative can be used alone or in combination of two or more kinds. It is effective that these compounds contain 0.005 mol or more per liter of the fixing solution, and particularly 0.01 mol / liter to 0.03 mol / liter. Specifically, tartaric acid, potassium tartrate, sodium tartrate, potassium sodium tartrate, ammonium tartrate, potassium ammonium tartrate, and the like can be given.

Examples of citric acid or its derivative effective in the present invention include citric acid, sodium citrate, potassium citrate and the like. If desired, the fixer may further include a preservative (eg, sulfite, bisulfite), a pH buffer (eg, acetic acid, nitric acid), a pH adjusting agent (eg, ammonia, sulfuric acid), and an image preservation improving agent (eg, , Potassium iodide), and a chelating agent.

The light-sensitive material of the present invention has a pretreatment time of 15 seconds to 60 seconds.
It shows excellent performance in rapid development processing by an automatic processor, which is the second. In the rapid development processing of the present invention, the temperature and time of development and fixing are each 25 seconds or less at about 25 ° C to 50 ° C,
Preferably, the temperature is 30 ° C to 40 ° C for 4 seconds to 15 seconds.

For the fixing solution, tartaric acid, citric acid, gluconic acid or their derivatives can be used alone or in combination of two or more kinds. 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 adjusting agents (eg sulfuric acid), chelating agents having the ability to soften water by water are 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 rinse processing is performed after the fixing processing. This rinse liquid has a function of removing the residual treatment chemical in the previous step,
It is used almost synonymously with washing liquid and washing water.

In this rinsing process, 1 m ^{2 of} light-sensitive material was used.
In this case, the replenishing amount can be 3 liters or less, and in this case, it is preferable that the rinse liquid is provided with antifungal means. As the antifungal means, the ultraviolet irradiation method described in JP-A-60-263939, the method using the magnetic field described in JP-A-60-263940,
Japanese Patent Laid-Open No. 61-131632, a method of making pure water using an ion exchange resin, a method of blowing ozone, and Japanese Patent Laid-Open No. 62-115154.
No. 62, No. 62-153952, No. 62-220951, No. 62-209532,
The method using the antibacterial agent described in JP-A-1-91533 can be used.

Furthermore, LFWest. “Eater Quality Cr
iterla "Photo. Sci. & Eng. Vol.9No.6 (1965), MW
Beach, “Microbiologica 1 Growths in Motion-pictur
e Processing "SMPTE Journa 1 Vol.85, (1976), ROD
eegan, “Photo ProcessingWash Wate ； Biocides” J. Im
aging Tech 10, No. 6 (1984) and JP-A-57-8542.
57-58143, 58-105145, 57-132146, 58-186
Nos. 31, 57-97530, 57-157244, and the like may be used in combination with antibacterial agents, antifungal agents, surfactants and the like.

Furthermore, RT Kreiman, J. Image. Tech 1
0, (6) Isothiazoline compounds described in p. 242 (1984), Research Disclosure Vol. 205, No. 20526 (1981).
, May issue), isothiazoline compounds described in Vol. 228, No. 22845 (April, 1983), JP-A-62-209532. Compounds and the like can also be used together as a bacteriostatic agent (Microbiocide).

In addition, as described in "Chemistry of Antibacterial and Antifungal" by 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-1-93737, JP-A-1-250947, and JP-A-2-03035. No. 2, JP-A-2-03037,
Reference can be made to the descriptions in JP-A-2-71260 and JP-A-61-267559.

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.

Embodiments of the present invention will be described below with reference to the accompanying drawings. FIG. 1 is a schematic plan view of an automatic developing device. The automatic developing device includes a developing tank 2, a fixing tank 4, a washing tank 6,
The developing tank 2 is filled with a developing solution, the fixing tank 4 is filled with a fixing solution, and the washing tank 6 is filled with washing water. The exposed light-sensitive material is sequentially dipped in each processing solution for processing, and the light-sensitive material 5 that has been washed with water is dried in a drying unit (not shown).
The developing tank 2 is filled with a developing solution, but an energizing tank 8 is provided adjacent to the developing tank 2, and the developing tank 2 and the energizing tank 8 are provided.
The space between and is separated 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. A cathode 12 is installed in contact with the developing solution, and an anode 14 is installed in contact with the electrolyte solution.
Is installed, and both electrodes 12, 14 are energized by a power supply 16. Further, the developing tank 2 is provided with an electrometer 18 so that the redox potential of the developing solution can be measured. The electrometer 18 is connected to the control device 20, and the power supply 16 can be controlled according to the oxidation-reduction potential of the developing solution measured by the electrometer 18 to control the potential and the energization amount.

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 a developing agent has a high ionic valence, but by dipping the cathode 12 in the developing solution and energizing it, high ions are generated from the cathode 12. An electron is given to the chelating metal ion having a valence as an electron, and the metal ion is reduced and regenerated.
Therefore, the energization treatment during the development treatment is preferable because 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, it is preferable to restore the developing performance by regenerating a large amount of chelate metal ions having a low ionic valence in the developing solution by conducting an electric current treatment before the developing treatment.

FIG. 2 is a sectional view of a modification of the processing apparatus.
In the processing device, a developing tank D, a fixing tank F, and a washing tank W are sequentially arranged. N ₂ gas is introduced into the developing tank D and the fixing tank F, and air is introduced into the washing tank W to raise them in the liquid. It is designed to stir the liquid. The photosensitive material is transported and processed in the same manner as the apparatus shown in FIG.

[0087]

【Example】

Example 1 Preparation of 1 type emulsion 1 Monodisperse cubic crystal of silver iodobromide containing 2 mol% of silver iodide having an average grain size of 0.3 μm by a double jet method while controlling 60 ° C., pAg = 8 and pH = 2.0. Particles were prepared.

The emulsion thus obtained was stored at 40 ° C. at Kao Atlas Co., Ltd.
Demol N (an aldehyde condensate of naphthalene sulfonic acid sodium salt) manufactured by the same company was desalted using an aqueous solution of magnesium sulfate, and then re-dispersed in an aqueous gelatin solution to obtain a seed emulsion.

Grain Growth from Seed Emulsion 1 Grains were grown as follows using the above seed emulsion. 40
The above seed emulsion was dispersed in a gelatin aqueous solution kept at 0 ° C., and the pH was adjusted to 9.7 with aqueous ammonia and acetic acid. An aqueous ammoniacal silver nitrate solution and an aqueous solution of potassium bromide and potassium iodide were added to this solution by the double jet method. During the addition, the pAg was 7.3 and the pH was 9.7, and the silver iodide content was 35 mol%.
Layers were formed. Then, an aqueous ammoniacal silver nitrate solution and an aqueous potassium bromide solution were added by the double jet method, pAg was kept at 9.0 up to 95% of the target particle size, and pH was continuously changed from 8.0 to 9.0. After that, adjust to pAg = 11.0 and pH =
The grain size was grown to the target grain size while maintaining 8.0. Subsequently, the pH was lowered to 6.0 with acetic acid, and then 5,5'- was added as a spectral sensitizing dye.
Anhydrous dichloro-9-ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine sodium salt (spectral sensitizing dye
GD-1) was added at 400 mg / mol AgX, desalted in the same manner as above, and then dispersed in a gelatin aqueous solution.

By this method, the average silver iodide content is 2.0.
In mol%, the average particle size of the tetrahedron with rounded vertices is
Coefficient of variation of 0.1 for 0.40 μm, 0.65 μm, and 1.00 μm
7, 0.16, 0.16 monodisperse silver iodobromide emulsions (A), (B) and
(C) was prepared. The aspect ratio was 1.0 in all cases.

Preparation of Seed Emulsion 2 0.1% containing 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.
After the liquid temperature was lowered to 5 ° C., 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 carried out in the same manner as described above, 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.

Grain Growth from Seed Emulsion 2 Grains were grown as follows using the above seed emulsion. 75 ° C
To an aqueous solution containing ossein gelatin and polyethyleneoxy / polypropyleneoxy-di-succinate-di-sodium salt, which had been vigorously stirred at room temperature, an aqueous solution of potassium bromide and potassium iodide and an aqueous solution of silver nitrate were added by a double jet method.

During this period, pH = 5.8 and pHAg = were kept at 9.0. After the completion of the addition, the pH was adjusted to 6.0, 400 mg / mol AgX of GD-1 as a spectral sensitizing dye was added, desalted in the same manner as above, and redispersed in an aqueous gelatin solution.

By this method, pAg and potassium iodide were changed to obtain a projected area diameter of 0.96 at an average silver iodide content of 1.5 mol%.
μm, coefficient of variation 0.25, aspect ratio 2.0, 3.5, 4.5 and
8.0 tabular silver iodobromide emulsions D-1, D-2, D-3 and D-4 were prepared.

Preparation of Samples The resulting emulsions (A), (B), (C) and D-1 to D-4 were each subjected to the above-mentioned spectral sensitizing dyes GD-1 and 5,5 'at 55 ° C. -The-
(Butoxycarbonyl) -1,1'-di-ethyl-3,3'-di- (4-
(Sulfobutyl) benzimidazolocarbocyanine sodium salt anhydride (GD-2) in a weight ratio of 200: 1 (A) is 975 mg, (B) is 600 mg, and (C) is 390 m per mol of silver halide.
g and D-1 to D-4 were added at 500 mg each.

After 10 minutes, appropriate amounts of chloroauric acid, sodium thiosulfate and ammonium thiocyanate were 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 per mol of silver halide. ^-2 mol was added and then dispersed in an aqueous solution containing 70 g of gelatin.

Of these four types of ripened emulsions,
Emulsions (R-1) were prepared by mixing (A), (B) and (C) in a weight ratio of 15:65:20, and D-1, D-2, D-3 and D-4 were independent. It was used as it was.

To each of these emulsions, as shown in Tables 1 and 2, the exemplified compound of the general formula [1] according to the present invention and the exemplified compounds of dextran and polyhydroxybenzene were added, and then the method described in JP-A-2- No. 301744, page 9, line 16 to 96
Add the additives as shown on page 20, line, and add 1.2 g of the following dye emulsion dispersion per mol of silver halide.
In addition, an emulsion coating solution was prepared.

Preparation Method of Dye Emulsion Dispersion 10 kg of the following dye was dissolved in a solvent consisting of 28 l of tricresylphosphite and 85 l of ethyl acetate at 55 ° C. This is called an oil solvent. On the other hand, the following anionic activator (AS) was added to 1.
Prepare a 9.3% gelatin aqueous solution containing 35 kg, and then put the oil-based solvent and this gelatin aqueous solution in a dispersion kettle and adjust the liquid temperature.
Dispersed while keeping at 40 ° C. To the resulting dispersion, appropriate amounts of phenol and 1,1'-dimethylol-1-bromo-1-nitromethane were added, and the mixture was made up to 240 kg with water.

[0101]

[Chemical 8]

Further, to the liquid for the protective layer, the exemplified compounds of the general formula [I] according to the present invention and the exemplified compounds of dextran and polyhydroxybenzene are added as shown in Tables 1 and 2, and the following per 1 liter is added as a coating liquid additive. Was added.

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 3.5 μm) 1.1 g Silicon dioxide (area average particle size 1.2 μm matting agent) 0.5 g Ludox AM (DuPont colloidal silica) 30 mg Glyoxal 40% aqueous solution 1.5 ml (CH ₂ = CHSO ₂ CH ₂ ) ₂ O 500 mg

[0104]

[Chemical 9]

The coating amount of the exemplary compound of the general formula [1] and the exemplary compounds of dextran and polyhydroxybenzene according to the present invention is the amount in which the polyethylene oxide in the compound is replaced by the weight% shown in Tables 1 and 2. I am adding. Therefore, for the sample containing the compound of the general formula [1] and / or dextran, the amount of gelatin described below is reduced by the weight thereof.

The emulsion layer has a silver conversion value of 2.2 g / side.
m ^2, 2.5 g / m ² by weight with a gelatin protective layer is glycidyl methacrylate at a speed per minute 90m by two slide hopper type coater so as to be 0.99 g / m ² as a weight with gelatin, methyl acrylate, butyl acrylate Emulsion on a 175 μm polyethylene terephthalate base coated with an aqueous copolymer dispersion obtained by diluting the copolymer (50:10:40 wt%) to a concentration of 10 wt%. A layer and a protective layer were simultaneously coated on both sides and dried for 2 minutes and 15 seconds to obtain a sample.

For the developing process, the automatic developing machine SRX-501 (manufactured by Konica Corp.) was remodeled so that the energizing process could be performed, and the developing temperature was 35 ° C., the fixing temperature was 33 ° C., and the washing water was at 18 ° C. 7.5 per minute
Litter was supplied, and the entire treatment process was performed at a drying temperature of 50 ° C. in the 45-second and 30-second modes shown below.

[Treatment Process] Process Treatment temperature (° C) Treatment time (sec) Replenishment amount (ml) Tank capacity (l) Insertion-1.2 0.8 Development + crossover 35 14.6 9.8 0 16.5 Fixing + crossover 33 8.2 5,4 32 9.8 Washing + crossing 18 7.2 4.8 7.5l / min 10.0 Squeeze 40 5.7 3.8 Dry 45 8.1 5.4 Total − 45.0 30.0 Replenishment amount is cut into 4 pieces per sheet.

[0109] Starter potassium bromide _{325g CH 3 N (C 3 H} 6 NHCONHC 2 H 4 SC 2 H 5) 2 1g glacial acetic acid _{150g HS-C 2 H 4 SC} 2 H 4 SC 2 H 4 -SH 1g pure 1 Processing solution for finishing to 1 liter (for 1 liter finish) Water 800 ml Ammonia water 100 ml EDTA ☆ 60 g Citric acid 38.4 g Potassium bromide 3.0 g Ferrous sulfate ・ 7H ₂ O 55.6 g 5-Methylbenztriazole 0.2 g 1-phenyl- 5-mercaptotetrazole 0.02 g N-acetyl-D, L-penicillamine 0.2 g pH Adjust to 6.5-7.0 and add water to make 1 liter.

EDTA: ferrous sulfate = 2: 1 (molar ratio) EDTA (4H) POSITE 4H (EDTA-Free acid) fixer (for 1 liter finish) PART A ammonium thiosulfate (70Wt / Vol%) 210g anhydrous Sodium sulfite 9.2 g Boric acid 1.6 g Gluconic acid 1.84 g Glacial acetic acid 7.5 g Sodium acetate trihydrate 21 g Sodium citrate 2.7 g PART B Aluminum sulfate 3.42 g Sulfuric acid (50%) Glacial acetic acid 5.6 g For developer A and B Add water and stir to dissolve to 12 liters. The pH was adjusted to 10.38, and this was used as a developing replenisher. Starter for 1 liter of this replenisher
Add 20 ml / liter and adjust the pH to 10.18 to make the initial working solution.

The fixing solution is prepared in the same manner to obtain 1 liter. The pH is adjusted to 4.35, which is used as the fixing replenisher and the initial use solution.

After being treated with the above-mentioned developer formulation of the present invention, it was left for 3 months in the air and then was energized for reuse. No precipitation occurred, and even if the energization was repeated several times, the same performance was obtained. . With the formulation of the present invention, nitrogen was turned off and left in the air for 2 days,
After applying electricity (2 V, 1.2 A, 10 minutes), the same photographic performance as that of the initial solution was obtained even if potassium bromide 3 g / l was added for treatment, and no precipitation occurred.

(Sensitometry) The obtained sample was sandwiched between fluorescent intensifying screens KO-250 (manufactured by Konica Corporation), and a tube voltage of 90 KVp, 2
The sensitivity and the gamma were obtained by irradiating 0 mA and 0.05 seconds of X-ray and creating a sensitometric curve by the distance method. The sensitivity value was obtained as the reciprocal of the X-ray dose required to obtain the density of fog +1.0. The results are expressed as relative sensitivity when the sensitivity of Sample No. 1 is 100. Also, gamma is the density of the characteristic curve of 1.0
The gamma value of 2.0, that is, tan θ when the inclination of the straight line connecting the points 1.0 and 2.0 is θ, is defined as gamma (γ).

As a comparison of the developing treatments of the present invention, Tables 1 and 2 also show the photographic performance results obtained by using the conventional hydroquinone developer XD-SR (manufactured by Konica Corporation) for the same developing time.

(Running Stability) A 4-cut film was uniformly exposed to give a density average of 1.0 to the sample of the present invention with the developing unit of the developing apparatus of the present invention being energized as shown in FIG. After processing the sheets, a running developer on the first day and after one month was prepared. At this time, electricity was applied at a voltage of 2 V and 1.5 A (current density 0.4 / dm ² ) for 40 seconds per 1 sheet of 4 cuts. Moreover, the auxiliary solution did not cause overflow from the developing solution because the mother solution of Formulation 1 was replenished in a reduced amount. That is, the waste liquid became 0 by energizing.

Using this developer, the sensitivity and gamma of the sample exposed in the same manner as in the above-mentioned sensitometry were determined by the same method. Tables 1 and 2 also show comparisons when running without energization.

[0117]

[Table 1]

[0118]

[Table 2]

From the results shown in Tables 1 and 2, the sensitivity (S), gamma (γ) and maximum density (Dmax) were remarkably increased by the processing of the light-sensitive material containing the tabular grains according to the present invention and the polymer dextran. To be Further, it can be seen that the inclusion of the polyhydroxybenzene compound increases the developing activity and maintains the sensitometric performance even in the rapid processing. Further, it is found that running stability is improved when the waste liquid is 0 by removing the bromine ions while applying a current-carrying process to reduce the bromine ions, and the stability is remarkably improved in combination with the light-sensitive material of the present invention. .

[0120]

According to the present invention, the processing performance using a metal compound as a developing agent can be easily maintained, and the sensitivity and the developability (particularly CP) can be increased in order to obtain an image of good photographic performance, and it can be reproduced many times. A silver halide by a combination of a light-sensitive material, a processing solution, and a current-carrying processor, in which a stable metal compound in a stable reduced state is always maintained by using a stable metal compound as a developing agent It was possible to provide a method for processing a photographic light-sensitive material.

[Brief description of drawings]

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

FIG. 2 is a sectional view of a modified example of the processing apparatus applied to the present invention.

[Explanation of symbols]

 2 Developing tank 4 Fixing tank 6 Washing tank 8 Energizing tank 10 Anion 12 Cathode 14 Anode 16 Power supply 18 Potentiometer 20 Controller S Photosensitive material D Developing tank F Fixing tank W Washing tank

Claims (3)

[Claims] 1. A method of processing a silver halide photographic light-sensitive material with a black-and-white developing solution containing a chelate complex salt of a transition metal, wherein the light-sensitive material comprises tabular silver halide grains having an aspect ratio of 3 or more. And a polymer containing a repeating unit represented by the following general formula [1] and / or dextran in the emulsion layer or other hydrophilic colloid layer. Material processing method. [Chemical 1] [In the formula, R ₁ represents a hydrogen atom or an alkyl group, and R ₂ , R _2
3 may be the same or different and represent a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, and R ₂ and R ₃ may be bonded to each other to form a nitrogen-containing heterocycle. L is 2
Represents a valent linking group, n represents 0-1 and m represents 1-2. x
Represents a molar percentage and represents 70 to 100. ] 2. A method of treating a silver halide photographic light-sensitive material with a black-and-white developing solution containing a chelate complex salt of a transition metal, wherein the silver halide emulsion layer or other hydrophilic colloid layer is polyhydroxy-substituted. A method of processing a silver halide photographic light-sensitive material, which comprises a benzene compound. 3. The method of processing with the black-and-white developing solution, wherein the complex salt is brought into a reduced state by applying an electric current before or during development, and a halogen salt generated by the development processing is removed. The method for processing a silver halide photographic light-sensitive material as described in 1 or 2.