JPH03146948A - Processing method for silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain photographic performance which is excellent in stability by controlling the equil. concn. of the bromine ions in a developing soln. to a prescribed specified concn. CONSTITUTION:The desalting chamber of an electrodialysis cell 11 using an ion exchange membrane and the developing soln. tank 1 of a development processing machine are coupled and the developing soln. is circulated therebetween. The current of the quantity controlled to attain the specified bromide ion concn. in the developing soln. is passed to this electrodialysis cell to regenerate the waste developing soln. The developing soln. is supplied from a line 12 to the desalting chamber in the cell 11 and is discharged from the line 13 after the electrodialysis. The soln. is then supplied to the tank 1. A sodium sulfate soln., etc., are supplied from a line 14 to the concentrating chamber, anode chamber and cathode chamber and are discharged from a line 15 after the electrodialysis. The photosensitive material has at least one layer of monodisperse silver halide emulsions on a base and the equiv. concn. of the bromine ions in the developing soln. is controlled to the specified concn. of any of 6.0X10<-3> to 1.3X10<-2>mol/l in this case.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for processing silver halide color photographic light-sensitive materials, and more particularly to a continuous processing method in which a color developing solution is recycled and reused using an ion exchange membrane electrodialysis method. .

(Prior art) Silver halide color photography 4. (In a method for treating raw materials, the used treatment liquid is generally disposed of as an overflow liquid.

However, these used processing liquids, which are recovered and processed as waste liquids, have a large pollution load value and are not desirable from the viewpoint of environmental conservation, and the collection and delivery costs for their recovery cannot be ignored.

In particular, regarding the color development process of color photographic light-sensitive materials, it is highly alkaline and has a large organic pollution load expressed in BOD (biochemical oxygen demand), and the turbidity load of the waste liquid is extremely large, and the chemicals are expensive. From this point of view, various methods have been proposed to reduce waste liquid.

For example, a low replenishment throughput method has been carried out in which the composition of the color developer replenisher (hereinafter referred to as color developer replenisher) is adjusted to reduce the amount of replenishment.
-261741, 61-282841 and 6
No. 1-70552, etc. Adjustment of the replenisher composition in low replenishment processing means, for example, concentrating consumable components such as color developing agents and preservatives in the replenisher so that the necessary amount of components can be supplied even if the replenishment amount is reduced. Measures can be taken. Furthermore, when a silver halide color photographic photosensitive paulownia material is processed, bromine ions are released into the color developer, but in low replenishment processing, the concentration of bromide ions in the color developer increases. , resulting in suppression of development.

Therefore, in order to prevent this, measures are generally taken such as reducing the bromide concentration in the replenisher compared to normal replenishment processing. However, there are certain limits to this,
Accumulation of bromine ions can cause delays in development, and subtle fluctuations in bromine ion concentration can change photographic properties.
This tendency becomes even more pronounced in the processing of light-sensitive materials mainly containing silver iodobromide emulsions.

On the other hand, as a means for reducing waste liquid, a method of reusing a used processing liquid (overflow liquid) as a replenisher has also been investigated. If reuse becomes possible, the above-mentioned problems in waste liquid treatment will be solved, and the self-effective ingredients remaining in the overflow liquid can also be reused, making it easier to create a new replenisher. Compared to this, the amount of chemicals used is smaller, and further cost reduction can be achieved. Therefore, in order to make it possible to reuse used processing solutions, regeneration procedures typically involve redressing the fluctuations that occurred during processing, i.e., removing accumulated components that adversely affect photographic performance, and then expending them. Many studies have been conducted on so-called regeneration technology, in which the missing components are added and used again as a replenisher.

In the reproduction wave fIi, the conventional problem is how to effectively remove the accumulated components, and in the color development process, it is especially important to remove bromine ions that are eluted from the light-sensitive material and have a strong development inhibiting effect. It was a great challenge.

For example, Halogen removal method using ion exchange resin
MPTE J, u, 168-171 (1979)
, Japanese Patent Publication No. 55144240, 53-132343
It is proposed in the No.

However, this method requires large equipment such as a resin column, requires technology to control halogen ions, and can only be processed using a hatch type.Furthermore, a large amount of waste liquid is generated to regenerate the resin, so new methods are required for this waste liquid treatment. This poses a number of challenges.

Furthermore, a halogen removal method using ion-exchange membrane electrodialysis is described in Japanese Patent Publication No. 52459/1983 and Japanese Patent Application Laid-open No. 97432/1989, etc., and furthermore, a developer tank and an ion exchange membrane electrodialysis tank are connected, and the developing Bromine ions in the solution are detected and quantified, and based on the results, the amount of electricity supplied to the electrodialysis tank is controlled to remove halogen ions, particularly bromide ions, from the developer by dialysis so that the concentration is kept constant; JP-A-54-3 discloses a continuous processing method in which the overflow liquid is further added with a deficient processing agent component and used again as a replenishing liquid.
No. 7731, No. 56-27142, etc.

(Problem to be solved by the invention) According to the ion exchange membrane electrodialysis method, continuous operation is possible.
Since it is also possible to adjust the halogen ions, this method has the advantage of being easier to handle and requiring less equipment space than the ion exchange resin method. However, in continuous processing using the ion-exchange membrane electrodialysis method described above, when controlling the halogen ion concentration to be kept constant, there are problems such as fluctuations in current density, fluctuations in halogen detection accuracy, and fluctuations in developer solution. There is a problem in that subtle changes in concentration of halokene ions occur due to concentration, etc., and the resulting photographic performance (particularly sensitivity and gradation) tends to fluctuate, especially when processing silver halide color photographic materials.

Therefore, it is an object of the present invention to provide a method for processing silver halide color photographic materials that can stably obtain excellent photographic performance in a development waste solution regeneration processing system using ion-exchange membrane electrodialysis. purpose.

(Means for Solving the Problem) The above problem is achieved by a method of processing a silver halide color photographic light-sensitive material by an ion-exchange membrane electrodialysis method while regenerating a color developing solution. It has at least one layer of monodisperse silver halide emulsion on the support, and the equilibrium concentration of bromide ions in the developer is 6.
．． It has been found that the problem can be solved by a method for processing silver halide color photographic materials, which is characterized by controlling the concentration to a constant value of 0x10-3 to 1.3x10-2 mol/i. .

In particular, when the silver halide grains of the monodisperse emulsion are multi-structure grains, fluctuations in photographic properties due to running are stabilized and excellent running performance can be obtained.

Also, the replenishment amount of color developer is 200 to 1500 mffi/
When running with a relatively large replenishment amount of about m2, the accumulated concentration of halogen is in a range that is easy to control, and fluctuations in photographic properties due to running are small.

In a developer regeneration system using ion-exchange membrane electrodialysis, a color photographic material containing a monodisperse silver halide emulsion is processed according to the present invention, and the bromide ion concentration in the developer is reduced to 6. OX 10-'~1.3X10-
2 mol/i, preferably 8X10-' to 1.2X 10
It has been found that stable photographic performance can be obtained by controlling the concentration to a constant value of -2 mol/i.

By controlling the bromide ion concentration in the developer in the ion-exchange membrane electrodialysis method to a slightly higher concentration than conventional methods, it is surprisingly possible to suppress subtle changes in the concentration of halogen ions in the developer. This is probably because the composition of the developer is relatively highly active and highly suppressive, and because a color photosensitive material containing a monodisperse silver halide emulsion is used, it becomes even less susceptible to fluctuations in bromide ion concentration. It is presumed that this was due to an accident.

In the present invention, the bromide ion concentration in the developer is set to 6, OX
Controlling the concentration to a constant concentration of 10-3 to 1.3X10-3 mol/l means that the constant concentration to be controlled is within the above concentration range, and The constant concentration further includes varying within a certain range. The width of the fluctuation is ±lXl0− in terms of bromide ion concentration.
It is preferably within the range of 3 mol/Il, particularly ±0.5 x 10-3 mol/l.

The ion exchange IIU electrodialysis method to which the present invention is effectively applied is disclosed in Japanese Patent Publication No. 52-34939, Japanese Patent Publication No. 61-52459, Japanese Patent Publication No. 51-84636, Japanese Patent Publication No. 51-85722,
No. 51-97432, No. 52-119934, No. 5
No. 3-149331, No. 53-46732, No. 5.1
-9626, 54-19741, 53-723
No. 4, No. 52-146236, No. 52-143018
No. 54-58028, the concentration of bromide ions in the developer to be regenerated is measured and the concentration of bromide ions in the developer is determined to be within the above concentration range. Any electrodialysis method for developing waste liquid may be used as long as it is equipped with a device that adjusts the amount of current applied so that the concentration is .

Specifically, the desalination chamber of an ion-exchange membrane electrodialysis tank consists of multiple anion-exchange membranes and multiple cation-exchange membranes between the cathode and anode (the cathode side is a cation-exchange membrane, the anode side is a desalination chamber). A chamber partitioned by an anion exchange membrane) is connected to the developer tank l of the processing machine, and the developer is circulated between the demineralization chamber and the developer tank. The developer waste can be regenerated by passing a controlled amount of current so that the bromide ion concentration remains constant according to the present invention.

By alternately providing a plurality of cation exchange membranes and a plurality of anion exchange membranes between the cathode and the anode provided inside the ion exchange membrane dialysis tank body 11 for partition, a plurality of desalination chambers can be created. A plurality of flA contraction chambers are formed.

Further, a cathode chamber and an anode chamber are formed by partitioning by an ion exchange membrane provided adjacent to both electrode plates.

A developer is supplied to the desalting chamber from a supply line 12 and subjected to electrodialysis, then discharged from an outflow line 13 and supplied to a developer tank 1.

Further, a sodium sulfate solution and the like are supplied to the concentration chamber, anode chamber, and cathode chamber from the supply line I4, and discharged from the outflow line 15 after electrodialysis.

Examples of the material for the cathode of the ion exchange membrane dialysis tank include iron, nickel, stainless steel, etc., and examples of the 4A material for the anode include graphite, magnetite, Tetsudo, platinum metal, etc. There are no particular restrictions on cation exchange membranes, but
As the anion exchange membrane, an exchange membrane that selectively permeates monovalent anions, particularly bromide ions and iodine ions, is desirable.

The cathode chamber, anode chamber, and concentration chamber of the ion-exchange membrane dialysis tank contain an alkali solution such as sodium hydroxide solution or potassium hydroxide solution. 8 liquid, a solution of a salt such as sodium sulfate,
Or supply a solution of acid such as sulfuric acid. The concentration of these solutions should be approximately 0.1N, and there is no particular upper limit.
Usually one regulation or less is sufficient. A developer is supplied from a developer tank to the desalting chamber of the ion exchange membrane dialysis tank. The supply method may be such that the demineralization chambers are connected in parallel, or the demineralization chambers are connected in series.

When a developer whose processing capacity has decreased and is exhausted is poured into the demineralization chamber of an ion-exchange membrane dialysis tank and subjected to electrodialysis, the bromide and iodine ions in the developer pass through the anion-exchange membrane to the concentration chamber or It is moved to the anode chamber and removed. Further, cations (eg, sodium ions, etc.) in the developer are removed by moving to the concentration chamber or the cathode chamber through the cation exchange membrane.

Therefore, in the demineralization chamber, the concentration of bromide ions, iodine ions, cations, etc. decreases, and this liquid returns to the line 13.
By supplying the developer to the developer tank 1, the developer is circulated. The concentration of these ions increases in the concentration chamber and is discharged via line 15.

The current density for ion-exchange membrane electrodialysis varies depending on the characteristics of the ion-exchange membrane and the characteristics of the development waste solution, but is suitably 0.02^/dm2 to IOA/dm, more preferably 0.1 to 3A/dm2.

Alternatively, an amount of water corresponding to the amount of development processing can be supplied to the electrolyte solution (i-tank chamber solution) passing through the concentration chamber, and the electrolyte concentration of the concentration chamber solution can be maintained constant while being circulated.

On the other hand, as shown in Fig. 1, the overflow liquid of the developer is usually stored in the stock tank 21, and when a certain amount has been accumulated, it is transferred to the liquid preparation tank 22, the insufficient components are added as a regenerating agent from the tank 24, and optionally water is added. is added to make a specified amount (ili liquid amount), and the obtained liquid can be transferred to the replenisher stock tank 23 and reused as a developer replenisher.

The regeneration method of the present invention includes bromide ions, chloride ions, sulfate ions, thiocyanine ions, sulfite ions, carbonate ions,
This effect can be exerted on all ordinary developing solutions containing at least two or more types of ions among phosphate ions, borate ions, nitrate ions, phosphonate ions, bicarbonate ions, and the like.

The color developing solution used in the present invention contains a known aromatic primary amine color developing agent.

A preferred example is a p-phenylenecyamine derivative,
Representative examples are shown below, but the invention is not limited thereto.

D-IN, N-diethyl-p-phenylenecyagon D-22-agono 5-diethylaminotoluene D-32-amino-5-(N-ethyl-N-laurylamino)toluene D-44-(N --Ethyl-N-(β-human'oxyethyl)aminocoaniline 3 D-52-methyl-4-[N-ethyl-N[β-hydroxyethyl]amino]aniline D-64-amino-3-methyl- N-ethyl N-(β-
(methanesulfonamide)ethylcoaniline D-7N-(2-amino-5-dinithylan ξnophenylethyl)methanesulfonamide FD-8N, N-di'methyl-p-phenylenecyagon D-94-amino-3 -Methyl-N-ethyl N-methoxyethylaniline D-104-amino-3-methyl-N-ethyl N-β-
Polytoxyethylaniline D-114-acuno-3-methyl-N-ethyl N-β-
Butoxyethylaniline Among the above p-phenylenecyan derivatives, Exemplified Compound D-5 is particularly preferred.

Further, these p-phenylenecyamine derivatives may be salts such as sulfate, hydrochloride, sulfite, and p-toluenesulfonate. The amount of the aromatic primary amine color developing agent used is preferably about 0.1 g to about 20 g, more preferably about 0.5 g per 11 color developing solutions.
~10g concentration.

In addition, the color developer contains thorium sulfite, preservative,
Sulfites such as potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, and carbonyl sulfite adducts can be added as necessary.

The preferable amount of preservative added is 0.5 per color developer IN.
g to 10 g, more preferably 1 g to 5 g.

In addition, as compounds that directly preserve the aromatic primary amino color developing agent, various hydroxylagons, hyaloxamic acids described in Japanese Patent Application No. 61-186559, and compounds described in Japanese Patent Application No. 61-170756 can be used. Shidrazine and hydrazides, No. 61-188742 and No. 61-20325
Phenols described in No. 3, α-hydroxyketones and α-aminoketones described in No. 61-188741, and/
Alternatively, it is preferable to add various types of #N described in No. 61-180616. In addition, when used in combination with the above compounds, Japanese Patent Application No. 61-147823, No. 61-166674, No. 6
No. 1-165621, No. 61-164515, No. 61
-170789, monoamines described in 61168159, etc., 61-173595, 61-1
Diamines described in No. 64515, No. 61-186560, etc., No. 61-165621, and No. 61-169
Polyamines described in No. 789, boria compounds described in No. 61-188619, nitroxy radicals described in No. 61-197760, No. 61-186561, and 6
Alcohols described in No. 1-197419, No. 61-19
Oximes described in No. 8987 and No. 61-26514
It is preferable to use the tertiary amines described in No. 9.

Other preservatives include various metals described in JP-A-57-44148 and JP-A-57-53749;
Salicylic acids described in No. 180588, JP-A-54-35
Alkanolamines described in No. 32, JP-A-56-94
349, U.S. Patent No. 3,
The aromatic polyhydroxy compound described in No. 746,544 may be contained if necessary. Particularly preferred is the addition of an aromatic polyhydroxy compound.

The color developer used in the present invention is preferably p119
-12, more preferably 9-11.0, and the color developer may contain other known developer components.

In order to retain the above-mentioned pu, it is preferable to use various buffering agents.

Specific examples of buffering agents include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, Sodium tetraborate (borax), potassium tetraborate, 0-
Sodium hydroxybenzoate (sodium salicylate), potassium 0-hydroxybenzoate, 5-sulfo-2
Examples include sodium hydroxybenzoate (sodium 5-sulfosalicylate) and potassium 5-sulfo-2-hydroxybenzoate (5-sulfotrilium phosphate). However, the present invention is not limited to these compounds.

The amount of the buffer added to the color developing solution is preferably 0.1 mole f71 or more, particularly 0.1 mole/N-
Particularly preferred is 0.4 mol/l.

In addition, various caloric acid agents can be used in the color developer as agents for preventing precipitation of calcium and magnesium, or to improve the stability of the color developer.

As the chelating agent, organic acid compounds are preferred, such as aminopolycarboxylic acids, organic phosphonic acids, and phosphonocarboxylic acids.

Specific examples are shown below, but the invention is not limited to these.

Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenethiaminetetraacetic acid, N,N,,N-trimethylenephosphonic acid, ethylenediamine-N,N,N'N'-tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid, 1.2-diaminopropane tetraacetic acid, hydroxyethyliminodiacetic acid, glycol ether cyagon tetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2
-phosphonobutane-1,2,4-1-licarboxylic acid, 1
8 Hydroxyethylidene-1,1-diphosphonic acid, N
N'-bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid.

Two or more of these chelating agents may be used in combination, if necessary.

These chelating agents may be added in an amount sufficient to sequester metal ions in the color developer.

For example II! , about 0.1 g to 10 g.

Any development accelerator can be added to the color developing solution if necessary. However, the color developing solution of the present invention preferably does not substantially contain Hensyl alcohol from the viewpoints of pollution, liquid preparation properties, and color staining and viscosity. here"
By "substantially" is meant no more than 2, preferably no, per developer solution IN.

Other development accelerators include Japanese Patent Publications No. 37-16088, No. 37-5987, No. 38-7826, No. 44-
No. 12380, No. 459019 and U.S. Patent No. 3.8
Thioether compounds represented in No. 13,247 etc.
The p-phenylenecyamine compounds shown in JP-A-52-49829 and JP-A-50-45554 are also
Quaternary ammonium salts shown in Japanese Patent Publication No. 0-137726, Japanese Patent Publication No. 44-30074, Japanese Patent Publication No. 56456826 and Japanese Patent Publication No. 52-43429, etc., U.S. Patent No. 2.49
No. 4,903, No. 3.128.182, No. 4,230
, No. 796, No. 3,253,919, Special Publication No. 1979-1
No. 1431, U.S. Patent No. 2,482,546;
Amine compounds described in Japanese Patent Publications No. 596,926 and No. 3,582,346, Japanese Patent Publication No. 37-16088, No. 42
-25201, U.S. Patent No. 3.128.183, Japanese Patent Publication No. 41-11431, Japanese Patent Publication No. 42-23883, and U.S. Patent No. 3.532.501. -Pyrazolidones, imidazoles, etc. can be added as necessary.

In the present invention, any antifoggant can be added if necessary. As antifoggants, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide, and organic antifoggants can be used. Examples of organic antifoggants include henctriazole, 6-nidrohenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrohencito I
J 7 Sol, 5-chloro-hensitriazole, 2
Typical examples include nitrogen-containing heterocyclic compounds such as -thiazolyl-benzigoazole, 2-thiazolylmethyl-penzimidazole, indazole, hydroxyazaindolizine, and adenine.

The color developing solution used in the present invention may contain a fluorescent whitening agent. As the fluorescent whitening agent, 4°4'-diamino-2,2'-disulfostylhene compounds are preferred.

Addition amount is 0-5g/I! , preferably 0.1g to 4g
/j! It is.

Furthermore, various surfactants such as alkylsulfonic acids, arylsulfonic acids, aliphatic carboxylic acids, and aromatic carboxylic acids may be added as necessary.

The processing temperature of the color developing solution of the present invention is 20 to 50°C, preferably 30 to 45°C. The treatment time is 20 seconds to 5 minutes, preferably 1 minute and 30 seconds to 4 minutes. It is preferable that the amount of replenishment is small, but it is 100 to 2000 mf per 1 m2 of photosensitive material.
f1° is preferably 200 to 1500 mffi. More preferably, it is 1300 ml-1000 mQ.

Further, the color developing bath may be divided into two or more baths as necessary, and the color developing replenisher may be replenished from the first bath or the last bath, thereby shortening the developing time and reducing the amount of replenishment.

The processing method of the present invention can also be used for color reversal processing. The black-and-white developer used at this time is a so-called black-and-white first developer used in the commonly known reversal processing of color photosensitive materials. Various well-known additives that are used in black-and-white developing solutions used in processing solutions for black-and-white silver halide light-sensitive materials can be included in the black-and-white first developer for color reversal light-sensitive materials.

Typical additives include developing agents such as 1-phenyl-3-pyrazolidone, metol and hydroquinone;
Preservatives such as sulfites, accelerators from alkalis such as sulfur hydroxide, sodium carbonate, potassium carbonate, etc.
Inorganic or organic inhibitors such as potassium bromide, 2-methylhenzimidazole, methylhentthiazole, water softeners such as polyphosphate, trace amounts of iodide, and mercapto compounds inhibit development. I can give you some medicine.

In the present invention, used color developing solution (overflow solution)
contains a regenerating agent and reuses it as a color developer replenisher.

In principle, a regenerating agent is added to a used color developing solution (overflow solution) for the purpose of replenishing components consumed during color development processing.

The regenerant for color developer replenisher used in the present invention includes:
In principle, it contains the same type of color developing agent, pH buffering agent, and chelating agent as used in the color developing solution, as well as other components as necessary, such as preservatives, development accelerators, optical brighteners, etc. It is preferable. The amount of these drugs may also be set to compensate for the consumed components. The amount of these regenerants added is 0.001 to 0.02 mol, pl+ of color developing agent per liter of amphibiotic replenisher obtained.
Buffer is 0.01-0.2 mol, chelating agent is 0.00
The amount of the preservative is preferably 1 to 0.02 mol, and the preservative is 0.01 to 0.03 mol.

In the present invention, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the treatment tank with the air. Further, if necessary, concentration can be corrected by appropriately adding water when preparing a color developer replenisher for the amount of liquid evaporated in the developing bath.

In the present invention, desilvering treatment is performed after color development. Typical desilvering processes are shown below, but the process is not limited to these.

1, (color development) - bleach fixing 2, (- bleach fixing 3, (- bleach = bleach fixing 4, (fixing - bleach fixing 5, (- bleaching - bleach fixing fixing 66 (〃 - bleach fixing - bleaching 7. (- Bleach-Fixing Constant Fixation If the above desilvering process is performed in two or more steps, a water washing or rinsing bath may be provided between both steps.Also, color development) - Process and desilvering process A conditioning, washing or stopping bath can also be provided in between.

In the above processing steps, each of the bleaching, bleach-fixing, and fixing processing baths may be one bath, or two or more processing baths may be used. How to refill each treatment bath:
Normally, the replenisher solution for each processing bath is replenished into the corresponding processing bath, but when the bleach-fix bath consists of multiple processing baths, the replenisher solution is added to the final bath and the overflow solution is added to the pre-bath. Replenishment may be carried out in a so-called counter-current manner, or in a so-called forward flow manner, in which a replenisher is added to the first bath and the overflow liquid is introduced into a subsequent bath. Further, in steps 3 and 4, the overflow liquid of the bleach bath or fixing bath, which is a pre-bath, can be introduced into the bleach-fixing bath to replenish the fixing component or the bleaching component to the bleach-fixing bath. Further, in step 5, the overflow liquid of the bleaching bath and the overflow liquid of the fixing bath may be respectively introduced into the bleach-fixing bath. Also, in steps 6 and 7, components of a subsequent bleach or fix bath may be introduced into the bleach-fix solution.

Bleaching agents in the bleach bath or bleach-fixing bath of the present invention include polyvalent transition metal ion compounds such as iron (■), cobalt (■), chromium (Vl), manganese (■), and copper (11); Peroxides, quinones, nitrobenzenes, etc. are used. For example, ferricyanide dichromate, iron (I
[[) or cobalt (■) organic acid chelate compound,
Ferric chloride, persulfates, hydrogen peroxide, permanganates,
Henzoquinone etc. can be used. Among these compounds, it is preferable to use organic acid ferric complex salts from the viewpoints of pollution, safety, etc., and it is particularly preferable to use aminopolycarboxylic acid ferric complex salts. These aminopolycarboxylic acids and their examples include the above-mentioned compounds.

■, ethylenecyaminetetraacetic acid 2, diethylenetriaminetetraacetic acid 3, cyclohexanediaminetetraacetic acid 4, C1-propylenecyagontetraacetic acid 5, ethylenecyamine-N-(β-oxyethyl)-N,N',
N'-triacetic acid 6. 1.3-cyanopropane tetraacetic acid 6 7,14-diaminobutane tetraacetic acid 8. Glycol ether diamine tetraacetic acid 9, iminodiacetic acid 10, N-methyl-iminodiacetic acid 11, ethylenethiacaronetetrapropionic acid 12, N-(
2-acedoξdo) iminodiacetic acid 13, dihydroxyethylglycine 14, ethylene cyano diorthohydroxyphenyl acetate ξ-noboricarboxylic acid ferric complex salt may be used in the form of a complex salt, or ferric salts, such as ferric sulfate, ferric chloride,
A ferric ion complex salt may be formed in a bath liquid using an aminopolycarboxylic acid with ferric nitrate, ferric ammonium sulfate, ferric phosphate, or the like. When used in the form of a complex salt, one type of complex salt or two or more types of complex salts may be used. On the other hand, when forming a complex salt in a solution using a ferric salt and an aminopolycarboxylic acid, one or more types of ferric salts may be used. Furthermore, one type or two or more types of aminopolycarboxylic acids may be used. In any case, the aminopolycarboxylic acid may be used in excess of the amount required to form the ferric ion complex.

Further, the bleach solution or bleach-fix solution containing the above-mentioned ferric ion complex may contain a metal ion complex salt other than iron, such as copper or the like.

The amount of these bleaching agents added is preferably from 0.05 mol to 1 mol, particularly preferably from 0.1 mol to 0.5 mol, per bleach solution or bleach-fix solution lp.

The bleach or bleach-fix solution of the present invention may contain a regenerating agent such as a bromide, such as potassium bromide, sodium bromide, ammonium bromide, or a chloride, such as potassium chloride, sodium chloride, ammonium chloride. Can be done. In addition, pH buffers include nitrates such as sodium nitrate and ammonium nitrate, boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, and tartaric acid. It can contain one or more kinds of inorganic acids, organic acids, salts thereof, etc., which have the ability to

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their pre-bath, if necessary.

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893,858, German Pat.
, No. 290,812, No. 2,059,988, JP-A No. 53-32,736, No. 53-57,831, No. 5
No. 3-37,418, No. 53-72,623, No. 53
-95,630, 53-95,631, 53-
No. 104,232, No. 53-124,424, No. 53
-No. 141.623, No. 53-28,426, Research Disclosure+ -No., No. 17.129 (19
Compounds having a mercapto group or disulfide group described in JP-A No. 1978-140.129; thiazolidine derivatives described in JP-A No. 140-129-1987: Japanese Patent Publication No. 8,506-1983
No. 5220.832, JP 5332.735, U.S. Patent No. 3,706. Thiourea derivatives described in '561; West German Patent No. 1,127,715, JP-A-58
Iodide salts described in No. 16.235; West German Patent No. 966.4
Polyoxyethylene compounds described in No. 10, No. 2,748.430; Boriabin compounds described in Japanese Patent Publication No. 45-8836; Others No. 49-42.434, No. 4
9-59,644, No. 539 94.927, No. 54-35.727, No. 55-2
Compounds described in No. 6,506 and No. 58163.940 can be used. Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly preferred, as described in US Pat. No. 3,893,858 and West German Patent No. 1.
Compounds described in No. 290.812 and JP-A-53-95-630 are preferred.

Also preferred are the compounds described in US Pat. No. 4,552.1334. These bleach accelerators may be added to the photosensitive material. These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography.

Examples of fixing agents for bleach-fix solutions include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used, especially thiosulfates. Ammonium sulfate is the most widely used. As the preservative for the bleach-fix solution, it is preferable to use sulfites, bisulfites, carbonyl bisulfite adducts, or sulfinic acid compounds.

The pH of the bleaching solution or bleach-fixing solution of the present invention is not particularly limited, but when a ferric aminopericarboxylic acid complex 0 salt is used as a bleaching agent, the pH is preferably 3.0 to 8.0. The amount of replenishment of the bleaching solution or bleach-fixing solution of the present invention needs to be changed depending on the amount of coated silver on the photographic material to be processed.
00m [is preferable.

The processing method of the present invention comprises processing steps such as color development, bleaching, bleach-fixing, and fixing as described above.

Here, after the bleach-fixing or fixing process, processing steps such as water washing and stabilization are generally performed, but after a bath with fixing ability, stabilization processing is performed without substantial water washing. A simple treatment method can also be used.

The rinsing water used in the rinsing step may contain known additives, if necessary. For example, water softeners such as inorganic phosphoric acid, acupunate polycarboxylic acid, and organic phosphoric acid, disinfectants that prevent the growth of various bacteria and algae, and antifungal agents (e.g., isothiazolone, organochlorine disinfectants, henzoliazole, etc.) ), a drying load, a surfactant to prevent unevenness, etc. can be used. Or L,
E.

West, “Water Quality Cr1
teria'', Photo, Sci.

and Eng,, vol, 9. No, 6+
Compounds described in pages 344-359 (1965) and the like can also be used.

As the stabilizing liquid used in the stabilizing step, a processing liquid that stabilizes the dye image is used. For example, a solution having a buffering capacity of pl+3 to 6, a solution containing aldehyde (for example, formalin), etc. can be used. The stabilizing solution may contain ammonium compounds, metal compounds such as Bi and Aj2, optical brighteners, and clearing agents (for example, l
-hydroxyethylidene 1,1-diphosphonic acid), bactericides, antifouling agents, hardeners, surfactants, alkanolamines, and the like can be used.

Further, the water washing step and the stabilization step are preferably carried out by a multistage countercurrent method, and the number of stages is preferably 2 to 4 stages. The amount of replenishment is 1 to 50 times, preferably 2 to 30 times, and more preferably 2 to 15 times the amount brought in from the previous bath per unit area.

The water used in these washing steps or stabilization steps includes tap water, as well as Ca
It is preferable to use water that has been deionized to reduce Mg to 5 mg/1 or less, water that has been sterilized with halogen, an ultraviolet germicidal lamp, or the like.

In each of the above-mentioned processing steps for color photosensitive materials, when continuous processing is performed using an automatic processor, concentration of the processing solution may occur, especially when the processing amount is small or the opening area of the processing solution is large. becomes noticeable. In order to correct such concentration of the processing liquid, it is preferable to replenish an appropriate amount of water or correction liquid.

Further, the amount of waste liquid can be reduced by using a method in which the overflow liquid from the water washing step or the stabilization step flows into a pre-bath having a fixing ability.

The light-sensitive material of the present invention only needs to have at least one silver halide emulsion layer of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer on the support. There are no particular limitations on the number and order of the emulsion layers and non-photosensitive layers. A typical example is a silver halide photographic light-sensitive material having a light-sensitive layer on a support, which is composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. The photosensitive layer is a unit photosensitive layer that is sensitive to blue light, green light, or red light, and in multilayer silver halide color photographic light-sensitive materials, generally the arrangement of the unit photosensitive layers is A red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are disposed in this order from the support side. However, depending on the purpose, the above-mentioned installation order may be reversed, or the installation order may be such that different color-sensitive layers are sandwiched between the same color-sensitive layer.

Non-photosensitive layers such as various intermediate layers may be provided between the silver halide photosensitive layers and between the uppermost layer and the lowermost layer.

The intermediate layer includes JP-A Nos. 61-43748 and 59-1.
No. 13438, No. 59-113440, No. 61-20
Coupler, DIR compound, etc. as described in No. 037 and No. 61-20038 may be included,
It may also contain commonly used color mixing prevention agents, ultraviolet absorbers, stain inhibitors, and the like.

The plurality of halogen silver emulsion layers constituting each unit photosensitive layer are a high-speed emulsion layer and a low-speed emulsion layer, as described in German Patent No. 1,121,470 or British Patent No. 923.045. A two-layer structure can be preferably used. Usually, it is preferable to arrange the layers so that the photosensitivity decreases toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. In addition, as described in JP-A-57-112751, JP-A-62-200350, JP-A-62-206541, JP-A-62-206543, etc., a low-sensitivity emulsion layer is placed on the side away from the support. A high-sensitivity emulsion layer may be provided on the closer side.

As a specific example, from the side farthest from the support, low sensitivity blue sensitive layer (BL) / high sensitivity blue sensitive layer (BH) / high sensitivity green sensitive layer (GH) / low sensitivity green sensitive layer (GL) /High-sensitivity red-sensitive layer (RH)/Low-sensitivity red-sensitive layer (RL), or B H / B L / G L / G H / Rl-1 / RL
in the order of BH/BL/GH/GL/RL/RI-
They can be installed in the order of 1, etc.

Further, as described in Japanese Patent Publication No. 55-34932, from the side farthest from the support, the blue-sensitive layer/GH/R
They can also be arranged in the order of H/CL/RL. Furthermore, as described in JP-A Nos. 56-25738 and 62''63936, the blue-sensitive layer/G L/RL/G H/RH may be arranged in this order from the farthest side from the support. You can also do it.

In addition, as described in Japanese Patent Publication No. 49-15495, the upper layer is a silver halide emulsion layer with the highest sensitivity, the middle layer is a silver halide emulsion layer with a lower sensitivity, and the lower layer is a silver halide emulsion layer that is more sensitive than the middle layer. An example is an arrangement consisting of three layers having different photosensitivity, in which a silver halide emulsion layer with a low density is arranged, and the photosensitivity gradually decreases toward the support. Even when it is composed of three layers with different photosensitivity, as described in JP-A No. 59-202464,
In the same color-sensitive layer, medium-sensitivity emulsion layer/high-sensitivity emulsion layer/low-sensitivity emulsion layer may be arranged in this order from the side remote from the support.

As mentioned above, various layer structures and arrangements can be selected depending on the purpose of each photosensitive material.

Any of these layer arrangements can be used in the color photosensitive material of the present invention.

Swelling rate of the sensitive material of the present invention [Equilibrium swelling film thickness at (25°C1] 1□0 - dry total film thickness at 25°C 155% RH/dry total film thickness at 25°C 255% RH) x 100 )
is preferably 50 to 200%, more preferably 70 to 150%.

If the swelling ratio deviates from the above-mentioned value, the photographic properties will be more susceptible to fluctuations.

Furthermore, the swelling rate of the photosensitive material of the present invention is defined as the swelling rate T'/2, which is 172, which is the time taken to reach 90% of the saturated swollen film thickness in a color developing solution (38°C). Preferably, Tv2 is 15 seconds or less.

More preferably, T'/z is 9 seconds or less.

The light-sensitive material used in the present invention preferably contains a monodisperse silver halide emulsion in at least one layer, and preferably in all emulsion layers.

"Monodisperse silver halide grains" used in the present invention are those in which the shape of each silver halide grain appears uniform when an emulsion is observed using an electron microscope, the grain size is uniform, and the grain size is uniform. The ratio of the standard deviation S of the diameter distribution to the average particle diameter T is 0.20 or less, preferably 0.15 or less. Here, the standard deviation S of the particle size distribution is determined according to the following formula.

In addition, the average grain size T referred to here is the diameter in the case of spherical silver halide grains, or the diameter when the projected image is converted into a circular image of the circumferential area in the case of grains with shapes other than cubic or spherical. The average value of the diameter, where the individual particle size is ri and the number is ni, is 7 defined by the following formula.

Σn1ri Σni Note that the above particle size can be measured by various methods commonly used in the technical field for the above purpose. A typical method is Loveland's Particle Size Analysis Table JA.

S, T, M, Symposium on Light Microscopy 1955, pp. 94-122 or 8 "Theory of the Photographic Process" by Mies and James,
It is described in Chapter 2 of the 3rd edition, published by Macmillan (1966). The particle size can be measured using the particle's projected area or diameter approximation. If the particles are of substantially uniform shape, the particle size distribution can be described fairly accurately as diameter or projected area.

The relationship between grain size distribution is described in "Empirical relationship between sensitometric distribution and grain size distribution in photographic emulsions," The Photographic Journal, Vol. LXXIX, (1949) 33.
This can be determined using the method described in the Trivelli and Smith paper of 0-338@.

The preferred silver halide contained in the photographic emulsion layer of the color light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide, containing about 30 mol% or less of silver iodide. . Particularly preferred is silver iodobromide containing from about 2 mole percent to about 25 mole percent silver iodide.

Silver halide grains in photographic emulsions include those with regular crystals such as cubes, octahedrons, and tetradecahedrons, those with irregular crystal shapes such as spherical and plate shapes, and those with twin planes. may have crystal defects, or a composite form thereof.

The grain size of the silver halide may be as fine as about 0.2 microns or less, or as large as up to about 10 microns in projected area diameter.

Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (RD), No. 1764.
3 (December 1978), pp. 22-23, "■, Emulsion preparation an
d types)'', and the same No. 18716 (1
9'? November 9), 648 pages, graphic "Physics and Chemistry of Photography", published by Paul Montell (P.

Glafkides, Chemic et Ph1s
ique PhotographiquePaul M
ontel, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G, F, Duffin
Photographic Limulsion Ch.
emistry (Focal Press, 196
6)), “Production and Coating of Photographic Emulsions” by Zelikman et al.
Published by Focal Press (V, L, Zelikman
et al. Making and coating
Photographic Hmulsion + Fo
Cal Press 1964).

Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described by Gutoff, Photographic Science and Engineering.
nce and Engineering), No. 14
Vol. 248-257 (1970); U.S. Patent No. 4,
No. 434,226, No. 414,310, No. 4,4
33.04111, British Patent No. 4,439,520, and British Patent No. 2.112.157.

The crystal structure may be --like, the inside and outside may have different halogen compositions, it may have a silk-like structure, and silver halides with different 11 precepts may be joined by epitaxial bonding. Alternatively, it may be bonded with a compound other than silver halide, such as silver rhodan or lead oxide.

Also, mixtures of particles of various crystal forms may be used.

I Particularly preferred for the present invention are multi-structure particles (for example, 2- to 4-layer structure particles) in which the halogen compositions of the inside and outside are different. Specifically, there are emulsions made of double structure grains, emulsions made of core/shell grains, and the like. In addition, as for the halogen composition, it is preferable that the inside has a higher proportion of silver iodide than the outside (for example, the shell part), and the iodide! ! The difference in amount is preferably 1% or more, more preferably 2% or more, particularly preferably 5% or more.

In the present invention, in particular, the coating silver amount of the photosensitive material is 2 to 6 g/l11
It is preferable that it is 2.

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening and spectral sensitization. Additives used in such processes are Research Disclosure +-No.
17643 and No. 18716, and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two research publications, and the relevant descriptions are shown in the table below.

2 RD17643 Rro18716 chemical sensitizer
Page 23 Page 648 Right column Sensitivity enhancer
Same overlay photosensitizer, pages 23-24 Page 648 right column ~ Super sensitizer Page 649 right column Brightener Antifogging agent and stabilizer Light absorber, filter dye Ultraviolet absorber Anti-stain agent Page 25 right column Column Dye Image Stabilizers Page 25 Hardeners Page 26 Binder Pages 26 Plasticizers, Lubricants Page 27 Coating Aids, Pages 26-27 Surfactants 13 Anti-sphutic Agents Page 27 Same Various color couplers are used in civil engineering inventions Shiruko page 649 right column - page 24 page 650 left - right column 650 true left column page 651 left column ditto page 650 right column ditto page 25-26 page 24-245 page 649 right column ~ RD No. mentioned above, 17643
, ■C-G.

As a yellow coupler, for example, U.S. Patent Tube 3.93
No. 3,501, No. 4,022,620, No. 4,326
,02. ! No. 4,401,752, No. 4,24
No. 8,961, Special Publication No. 5810739, British Patent No. 1
, 425,020, 1,476.760, U.S. Patent No. 3,973.968, 4,314,023,
4.511,649, European Patent No. 249.473A
Preferably, those described in No.

As magenta couplers, 5-pyrazolone and pyrazoloazole compounds are preferred, and US Pat.
No. 0,619, No. 4,351,897, European Patent No. 7
No. 3.636, U.S. Patent No. 3,061,432, No. 3
, No. 725.064, RD No., 24220 (1
June 984), Japanese Patent Publication No. 6033552, RD N
o, 24230 (June 1984), JP-A-60-4
No. 3659, No. 61-72238, No. 60-3573
No. 0, No. 55118034, No. 60-185951, U.S. Patent No. 4,500,630, No. 4,54o, 6
s, + No. 4,556,630, W O (P CT
) Particularly preferred are those described in No. 88104795.

Cyan couplers include phenolic and naphthol couplers, and are disclosed in U.S. Patent No. 4,052,212.
No. 4,146,396, No. 4,228,233, No. 4,296,200, No. 2,369,929,
No. 2,801,171, No. 2,772,162, No. 2,895,826, No. 3,772,002, No. 3
, 758, 308, 4,334.011, 4.
, 327,173, West German Patent Publication No. 3.329.72
9, European Patent No. 121,365A, European Patent No. 249,45
3A, U.S. Patent No. 3,446,622, U.S. Patent No. 4,33
No. 3.999, No. 4,753,871, No. 4.45L
No. 559, No. 4,427,767, No. 4,690,8
No. 89, No. 4,254,212, No. 4,296.19
No. 9, JP-A No. 61-42658, etc. are preferred.

Colored couplers for correcting unnecessary absorption of color-forming dyes are disclosed in RD No. 17643, ■-G section, U.S. Pat. , No. 929, 4,138
, 258 and British Patent No. 1,146,368 are preferred. Also, U.S. Patent No. 4,774.181
A coupler that corrects unnecessary absorption of a coloring dye from a fluorescent dye released during coupling, as described in US Pat. No. 4,
It is also preferable to use a coupler having as a leaving group a dye precursor group capable of forming a dye by reacting with a developing agent as described in No. 5 of 777.120.

Couplers whose coloring dyes have appropriate diffusivity include U.S. Patent No. 4,366.237 and British Patent No. 2,125.
, 570, European Patent No. 96,570, and German Patent Publication No. 3,234,533 are preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat. Nos. 3,451,820 and 4,080,211;
4.367.282, 4,409.320, 4,576.910, British Patent No. 2.102.173
It is stated in the number etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. The DIR coupler releasing the development inhibitor is RD17643 as previously described.
, Patents described in sections ■ to F, Japanese Patent Application Laid-Open No. 57-15194
No. 4, No. 57-154234, No. 60-184248
No. 63-37346, U.S. Patent No. 4,248,9
Preferably, those described in No. 62 and No. 4,782,012 are preferred.

British Patent No. 2,097,1406 is a coupler that releases a nucleating agent or a development accelerator imagewise during development.

Claims (3)

[Claims] (1) In a method of processing a silver halide color photographic light-sensitive material while regenerating a color developer by ion-exchange membrane electrodialysis, the silver halide color photographic light-sensitive material contains at least a monodisperse silver halide emulsion. on a single-layer support, and the equilibrium concentration of bromide ions in the developer is 6.0×
A method for processing a silver halide color photographic material, characterized in that the concentration is controlled to a constant concentration of 10^-^3 to 1.3 x 10^-^2 mol/l. (2) The processing method according to claim (1), wherein the silver halide grains of the monodisperse emulsion of the silver halide color photographic light-sensitive material are multi-structure grains. (3) Replenishment amount of color developer is 20 per 1 m^2 of photosensitive material.
Claim (1) characterized in that the volume is 0 to 1500 ml.
Or the processing method described in (2).